# Supplementary Information (SI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mf-1-32b_abs_a
_database_code_depnum_ccdc_archive 'CCDC 2415084'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT369_mf-1-32b_abs_a      
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_c     .       1.53 Ang.
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
# Added during the CSD deposition process: Tuesday 07 January 2025 12:07 AM
# end Validation Reply Form

_audit_creation_date             2024-04-04
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C9 H6 F3 La O9, 9(H2 O)'
_chemical_formula_sum            'C9 H24 F3 La O18'
_chemical_formula_weight         616.19
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C9 H24 F3 La O18'
_chemical_oxdiff_usercomment     'solvent:acetone and water'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3'
_space_group_name_Hall           '-R 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   14.5860(3)
_cell_length_b                   14.5860(3)
_cell_length_c                   17.4069(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     3207.19(14)
_cell_formula_units_Z            6
_cell_measurement_reflns_used    2592
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      74.8660
_cell_measurement_theta_min      3.5670
_shelx_estimated_absorpt_T_max   0.596
_shelx_estimated_absorpt_T_min   0.342
_exptl_absorpt_coefficient_mu    16.480
_exptl_absorpt_correction_T_max  0.725
_exptl_absorpt_correction_T_min  0.404
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            green
_exptl_crystal_colour_lustre     ?
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.914
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1836
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-2 -2 -10 0.0167
2 1 11 0.0175
0 -4 -10 0.0202
-7 -2 -1 0.0180
-5 4 9 0.0273
5 -4 -9 0.0273
-5 9 0 0.0488
4 -9 -1 0.0297
6 3 4 0.0406
-3 1 -11 0.0201

_exptl_crystal_size_max          0.083
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.035
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-1.7033 -1.9410 -10.4219 -0.0880 -0.3618 -0.9281
2.1759 1.0407 10.5926 0.1083 0.4469 0.8880
-0.3873 -4.2174 -9.5102 -0.0308 -0.1223 -0.9920
-6.6714 -2.4233 -1.1882 0.8427 -0.2012 -0.4995
-4.8798 4.3757 9.2964 0.5765 -0.1388 0.8052
4.8798 -4.3757 -9.2964 -0.5765 0.1388 -0.8052
-4.6066 9.4688 -0.3545 -0.1960 -0.8224 0.5341
4.1056 -9.3723 -1.4490 0.1720 0.7231 -0.6690
5.9578 2.7880 3.7534 -0.6913 0.2451 0.6797
-3.1875 1.0426 -10.6067 -0.1491 -0.6253 -0.7660

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            3641
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.404
_diffrn_reflns_theta_min         4.325
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.949
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     33.00  80.00   0.50    0.40    --  105.30 -73.00 -46.00   94
  2  ω     38.00  65.00   0.50    0.40    --  105.30 -61.00   0.00   54
  3  ω     33.00  61.00   0.50    0.40    --  105.30 -61.00  30.00   56
  4  ω     40.00  66.00   0.50    0.40    --  105.30 -61.00 120.00   52
  5  ω    147.00 173.00   0.50    0.40    --  105.30  30.00  90.00   52
  6  ω     94.00 120.00   0.50    0.40    --  105.30  30.00  90.00   52
  7  ω    -17.00  30.00   0.50    0.20    --   47.26 -19.00 -30.00   94
  8  ω     36.00 107.00   0.50    0.40    --  105.30-103.00 -74.00  142
  9  ω   -107.00 -37.00   0.50    0.20    --  -47.26 -51.00 152.00  140
 10  ω   -154.00 -92.00   0.50    0.40    --  -91.75 -94.00  30.00  124
 11  ω    -49.00 -23.00   0.50    0.40    --  -91.75  45.00   0.00   52
 12  ω    -49.00 -28.00   0.50    0.40    --  -91.75  45.00 120.00   42
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1073514000
_diffrn_orient_matrix_UB_12      -0.0714561000
_diffrn_orient_matrix_UB_13      0.0392989000
_diffrn_orient_matrix_UB_21      0.0460983000
_diffrn_orient_matrix_UB_22      -0.0629714000
_diffrn_orient_matrix_UB_23      0.0389094000
_diffrn_orient_matrix_UB_31      0.0349414000
_diffrn_orient_matrix_UB_32      0.0759915000
_diffrn_orient_matrix_UB_33      0.0691880000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1378
_reflns_number_total             1419
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.133
_refine_diff_density_min         -0.905
_refine_diff_density_rms         0.121
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     119
_refine_ls_number_reflns         1419
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0314
_refine_ls_restrained_S_all      1.078
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0400P)²+21.4064P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0805
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.5 times of:
  All H(H) groups, All O(H,H) groups
2. Restrained distances
 O6-H6A = O6-H6B
 0.84 with sigma of 0.02
 H6A-H6B
 1.34 with sigma of 0.04
 O7-H7A = O7-H7B
 0.84 with sigma of 0.02
 H7A-H7B
 1.34 with sigma of 0.04
 O8-H8A = O8-H8B
 0.84 with sigma of 0.02
 H8A-H8B
 1.34 with sigma of 0.04
 O9-H9A = O9-H9B
 0.84 with sigma of 0.02
 H9A-H9B
 1.34 with sigma of 0.04
;
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
La1 La 0.333333 0.666667 0.42538(2) 0.01167(14) Uani 1 3 d S T P . .
O1 O 0.3290(2) 0.4876(2) 0.41326(15) 0.0155(5) Uani 1 1 d . . . . .
C2 C 0.2552(3) 0.4124(3) 0.3763(2) 0.0151(7) Uani 1 1 d . . . . .
C3 C 0.2352(3) 0.3084(3) 0.3764(2) 0.0156(7) Uani 1 1 d . . . . .
C4 C 0.1490(3) 0.2274(3) 0.3386(2) 0.0169(8) Uani 1 1 d . . . . .
O5 O 0.1221(2) 0.1298(2) 0.34090(15) 0.0151(5) Uani 1 1 d . . . . .
F6 F 0.29941(18) 0.28508(18) 0.41856(13) 0.0196(5) Uani 1 1 d . . . . .
O6 O 0.4664(2) 0.6693(2) 0.51684(17) 0.0221(6) Uani 1 1 d D . . . .
H6A H 0.472(4) 0.621(3) 0.536(3) 0.033 Uiso 1 1 d D U . . .
H6B H 0.510(4) 0.727(2) 0.536(3) 0.033 Uiso 1 1 d D U . . .
O7 O 0.7474(3) 0.6046(3) 0.41228(19) 0.0264(7) Uani 1 1 d D . . . .
H7A H 0.6819(19) 0.580(6) 0.408(5) 0.08(3) Uiso 1 1 d D . . . .
H7B H 0.772(6) 0.664(4) 0.434(5) 0.118 Uiso 1 1 d D U . . .
O8 O 0.5290(2) 0.4904(2) 0.40290(18) 0.0231(6) Uani 1 1 d D . . . .
H8A H 0.475(3) 0.492(4) 0.419(3) 0.035 Uiso 1 1 d D U . . .
H8B H 0.508(4) 0.456(4) 0.361(2) 0.035 Uiso 1 1 d D U . . .
O9 O 0.8658(3) 0.8087(3) 0.46199(17) 0.0249(6) Uani 1 1 d D . . . .
H9A H 0.902(4) 0.837(4) 0.422(2) 0.037 Uiso 1 1 d D U . . .
H9B H 0.838(4) 0.845(4) 0.475(3) 0.037 Uiso 1 1 d D U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
La1 O1 2.590(3) . ?
La1 O1 2.590(3) 2_665 ?
La1 O1 2.590(3) 3_565 ?
La1 O5 2.528(3) 16 ?
La1 O5 2.528(3) 18 ?
La1 O5 2.528(3) 17 ?
La1 O6 2.495(3) . ?
La1 O6 2.495(3) 2_665 ?
La1 O6 2.495(3) 3_565 ?
O1 C2 1.262(5) . ?
C2 C3 1.394(5) . ?
C2 C4 1.528(5) 16 ?
C3 C4 1.387(6) . ?
C3 F6 1.361(4) . ?
C4 O5 1.274(5) . ?
O6 H6A 0.823(19) . ?
O6 H6B 0.83(2) . ?
O7 H7A 0.84(2) . ?
O7 H7B 0.84(2) . ?
O8 H8A 0.851(19) . ?
O8 H8B 0.846(19) . ?
O9 H9A 0.84(2) . ?
O9 H9B 0.840(19) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 La1 O1 119.344(16) 2_665 . ?
O1 La1 O1 119.344(16) 3_565 . ?
O1 La1 O1 119.341(16) 3_565 2_665 ?
O5 La1 O1 62.36(8) 18 3_565 ?
O5 La1 O1 62.36(8) 17 2_665 ?
O5 La1 O1 68.21(8) 17 . ?
O5 La1 O1 131.86(8) 18 . ?
O5 La1 O1 68.21(8) 18 2_665 ?
O5 La1 O1 131.87(8) 16 2_665 ?
O5 La1 O1 131.87(8) 17 3_565 ?
O5 La1 O1 62.35(8) 16 . ?
O5 La1 O1 68.22(8) 16 3_565 ?
O5 La1 O5 78.13(9) 18 17 ?
O5 La1 O5 78.13(9) 18 16 ?
O5 La1 O5 78.13(9) 16 17 ?
O6 La1 O1 144.98(9) 2_665 . ?
O6 La1 O1 144.98(9) 3_565 2_665 ?
O6 La1 O1 72.18(9) . . ?
O6 La1 O1 69.09(9) . 2_665 ?
O6 La1 O1 69.09(9) 2_665 3_565 ?
O6 La1 O1 72.18(9) 3_565 3_565 ?
O6 La1 O1 72.18(9) 2_665 2_665 ?
O6 La1 O1 144.98(9) . 3_565 ?
O6 La1 O1 69.09(9) 3_565 . ?
O6 La1 O5 137.30(9) . 18 ?
O6 La1 O5 82.97(9) . 17 ?
O6 La1 O5 82.97(9) 3_565 16 ?
O6 La1 O5 137.30(9) 2_665 16 ?
O6 La1 O5 137.30(9) 3_565 17 ?
O6 La1 O5 82.97(9) 2_665 18 ?
O6 La1 O5 134.45(9) 2_665 17 ?
O6 La1 O5 134.45(9) . 16 ?
O6 La1 O5 134.45(9) 3_565 18 ?
O6 La1 O6 83.65(11) 2_665 3_565 ?
O6 La1 O6 83.65(11) 3_565 . ?
O6 La1 O6 83.65(11) 2_665 . ?
C2 O1 La1 119.8(2) . . ?
O1 C2 C3 124.7(4) . . ?
O1 C2 C4 116.8(3) . 16 ?
C3 C2 C4 118.6(3) . 16 ?
C4 C3 C2 122.3(4) . . ?
F6 C3 C2 118.4(3) . . ?
F6 C3 C4 119.1(3) . . ?
C3 C4 C2 118.9(3) . 16 ?
O5 C4 C2 115.7(3) . 16 ?
O5 C4 C3 125.4(4) . . ?
C4 O5 La1 121.6(2) . 16 ?
La1 O6 H6A 132(4) . . ?
La1 O6 H6B 118(4) . . ?
H6A O6 H6B 110(4) . . ?
H7A O7 H7B 107(5) . . ?
H8A O8 H8B 104(4) . . ?
H9A O9 H9B 107(4) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
La1 O1 C2 C3 -169.2(3) . . . . ?
La1 O1 C2 C4 11.4(4) . . . 16 ?
O1 C2 C3 C4 175.8(4) . . . . ?
O1 C2 C3 F6 -0.4(6) . . . . ?
C2 C3 C4 C2 4.8(6) . . . 16 ?
C2 C3 C4 O5 -174.8(4) . . . . ?
C2 C4 O5 La1 18.9(4) 16 . . 16 ?
C3 C4 O5 La1 -161.5(3) . . . 16 ?
C4 C2 C3 C4 -4.7(6) 16 . . . ?
C4 C2 C3 F6 179.1(3) 16 . . . ?
F6 C3 C4 C2 -179.1(3) . . . 16 ?
F6 C3 C4 O5 1.4(6) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.334
_oxdiff_exptl_absorpt_empirical_full_min 0.821
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mf-1-16a_abs-m_a_sq
_database_code_depnum_ccdc_archive 'CCDC 2415087'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_audit_creation_date             2024-05-24
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         
'Br5 C15 La O10, C12 H12 N2, 0.75[], 0.25[], 0.5[], 0.5[], 0.5[], 0.5[]'
_chemical_formula_sum            'C27 H15.50 Br5 La N2 O11.75'
_chemical_formula_weight         1094.37
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   12.011(2)
_cell_length_b                   26.422(5)
_cell_length_c                   10.489(2)
_cell_angle_alpha                90
_cell_angle_beta                 108.86(3)
_cell_angle_gamma                90
_cell_volume                     3150.0(12)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    910
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.31
_cell_measurement_theta_min      1.94
_shelx_estimated_absorpt_T_max   0.860
_shelx_estimated_absorpt_T_min   0.511
_exptl_absorpt_coefficient_mu    7.764
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6190
_exptl_absorpt_correction_type   Multi-Scan
_exptl_absorpt_process_details   
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1325 before and 0.0431 after correction.
The Ratio of minimum to maximum transmission is 0.8300.
The λ/2 correction factor is 0.0015.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.308
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             2070
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0577
_diffrn_reflns_av_unetI/netI     0.0540
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.777
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            20124
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.777
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.656
_diffrn_reflns_theta_min         1.541
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.777
_diffrn_measurement_detector_type 'Dectris Eiger2 9M'
_diffrn_measurement_device_type  'MX1 Beamline Australian Synchrotron'
_diffrn_measurement_method       'Omega Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.710917
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5022
_reflns_number_total             6303
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'XDS (Kabsch, 2010)'
_computing_data_collection       'AS QEGUI'
_computing_data_reduction        'XDS (Kabsch, 2010)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         7.133
_refine_diff_density_min         -3.615
_refine_diff_density_rms         0.241
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     406
_refine_ls_number_reflns         6303
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0746
_refine_ls_R_factor_gt           0.0605
_refine_ls_restrained_S_all      1.038
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0918P)²+28.6375P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1583
_refine_ls_wR_factor_ref         0.1710
_refine_special_details          ?
_olex2_refinement_description    
;
1.a Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C44(H44A,H44B)
1.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C33(H33), C34(H34), C35(H35), C38(H38), C39(H39), C40(H40), C41(H41)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C2 C 0.4939(7) 0.5376(3) 0.0981(8) 0.0213(16) Uani 1 1 d . . . . .
C3 C 0.4022(8) 0.5049(3) 0.0497(8) 0.0222(17) Uani 1 1 d . . . . .
C4 C 0.4000(8) 0.4679(3) -0.0478(8) 0.0244(17) Uani 1 1 d . . . . .
O5 O 0.3155(5) 0.4382(2) -0.0975(6) 0.0271(13) Uani 1 1 d . . . . .
Br6 Br 0.27442(8) 0.50900(3) 0.11815(9) 0.0282(2) Uani 1 1 d . . . . .
O7 O 0.8562(5) 0.5717(2) 0.5420(6) 0.0258(13) Uani 1 1 d . . . . .
C8 C 0.9236(8) 0.5377(3) 0.5308(8) 0.0238(17) Uani 1 1 d . . . . .
C9 C 0.9841(8) 0.5034(3) 0.6310(8) 0.0232(17) Uani 1 1 d . . . . .
C10 C 1.0567(8) 0.4651(3) 0.6073(8) 0.0230(17) Uani 1 1 d . . . . .
O11 O 1.1099(5) 0.4325(2) 0.6915(6) 0.0276(13) Uani 1 1 d . . . . .
La1 La 0.70106(4) 0.60796(2) 0.31756(5) 0.02038(15) Uani 1 1 d . . . . .
O1 O 0.5016(6) 0.5721(2) 0.1827(6) 0.0264(13) Uani 1 1 d . . . . .
Br12 Br 0.97136(9) 0.50886(3) 0.80501(9) 0.0310(2) Uani 1 1 d . . . . .
O13 O 0.6569(6) 0.5123(2) 0.3658(6) 0.0268(13) Uani 1 1 d . . . . .
C14 C 0.5824(8) 0.5039(3) 0.4240(8) 0.0229(17) Uani 1 1 d . . . . .
C15 C 0.5179(8) 0.4590(3) 0.4185(8) 0.0233(17) Uani 1 1 d . . . . .
C16 C 0.4456(8) 0.4510(3) 0.4952(8) 0.0257(18) Uani 1 1 d . . . . .
O17 O 0.3949(5) 0.4101(2) 0.5033(6) 0.0251(13) Uani 1 1 d . . . . .
Br18 Br 0.53833(9) 0.40517(3) 0.30784(9) 0.0309(2) Uani 1 1 d . . . . .
C19 C 0.8253(9) 0.7575(3) 0.5895(9) 0.032(2) Uani 1 1 d . . . . .
C20 C 0.7675(9) 0.7174(3) 0.5071(9) 0.030(2) Uani 1 1 d . . . . .
C21 C 0.6338(9) 0.7211(4) 0.4408(10) 0.035(2) Uani 1 1 d . . . . .
C22 C 0.5748(10) 0.7626(4) 0.4659(12) 0.047(3) Uani 1 1 d . . . . .
C23 C 0.6309(10) 0.7997(3) 0.5622(10) 0.036(2) Uani 1 1 d . . . . .
C24 C 0.7645(9) 0.7961(4) 0.6279(10) 0.035(2) Uani 1 1 d . . . . .
O25 O 0.8154(6) 0.6786(2) 0.4819(6) 0.0287(13) Uani 1 1 d . . . . .
O26 O 0.5878(6) 0.6853(2) 0.3606(7) 0.0352(15) Uani 1 1 d . . . . .
O27 O 0.5816(7) 0.8359(3) 0.5999(8) 0.0417(17) Uani 1 1 d . . . . .
O28 O 0.8092(7) 0.8317(2) 0.7087(7) 0.0382(16) Uani 1 1 d . . . . .
Br29 Br 0.99157(10) 0.75776(4) 0.65807(14) 0.0513(3) Uani 1 1 d . . . . .
Br30 Br 0.41232(13) 0.76937(6) 0.36925(19) 0.0793(5) Uani 1 1 d . . . . .
N31 N 0.0212(7) 0.6424(3) -0.1109(8) 0.0342(18) Uani 1 1 d . . . . .
C32 C -0.0750(9) 0.6429(4) -0.2202(10) 0.038(2) Uani 1 1 d . . . . .
H32 H -0.068099 0.652378 -0.304717 0.046 Uiso 1 1 calc R U . . .
C33 C -0.1831(8) 0.6302(3) -0.2125(9) 0.0298(19) Uani 1 1 d . . . . .
H33 H -0.251427 0.632051 -0.289763 0.036 Uiso 1 1 calc R U . . .
C34 C -0.1904(8) 0.6146(3) -0.0908(9) 0.0275(18) Uani 1 1 d . . . . .
H34 H -0.264632 0.605747 -0.083175 0.033 Uiso 1 1 calc R U . . .
C35 C -0.0900(8) 0.6118(4) 0.0216(9) 0.0288(19) Uani 1 1 d . . . . .
H35 H -0.095622 0.600275 0.105071 0.035 Uiso 1 1 calc R U . . .
C36 C 0.0182(8) 0.6258(3) 0.0122(9) 0.0259(18) Uani 1 1 d . . . . .
C37 C 0.1265(9) 0.6281(3) 0.1292(10) 0.031(2) Uani 1 1 d . . . . .
C38 C 0.1224(9) 0.6220(4) 0.2611(10) 0.040(2) Uani 1 1 d . . . . .
H38 H 0.050584 0.615273 0.277538 0.047 Uiso 1 1 calc R U . . .
C39 C 0.2287(10) 0.6263(5) 0.3668(12) 0.053(3) Uani 1 1 d . . . . .
H39 H 0.229388 0.621680 0.456874 0.064 Uiso 1 1 calc R U . . .
C40 C 0.3308(9) 0.6370(4) 0.3433(11) 0.044(3) Uani 1 1 d . . . . .
H40 H 0.402210 0.639725 0.416190 0.052 Uiso 1 1 calc R U . . .
C41 C 0.3301(10) 0.6437(4) 0.2140(12) 0.044(3) Uani 1 1 d . . . . .
H41 H 0.400434 0.652855 0.196849 0.053 Uiso 1 1 calc R U . . .
N42 N 0.2306(7) 0.6374(3) 0.1121(9) 0.0354(18) Uani 1 1 d . . . . .
C43 C 0.2336(10) 0.6357(6) -0.0289(13) 0.057(3) Uani 1 1 d . . . . .
H43A H 0.308178 0.650703 -0.032238 0.069 Uiso 1 1 calc R U . . .
H43B H 0.230433 0.600085 -0.059158 0.069 Uiso 1 1 calc R U . . .
C44 C 0.1362(11) 0.6631(6) -0.1169(14) 0.058(3) Uani 1 1 d . . . . .
H44A H 0.138027 0.660749 -0.210427 0.070 Uiso 1 1 calc R U . . .
H44B H 0.142952 0.699238 -0.090695 0.070 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C2 C3 1.361(12) . ?
C2 C4 1.536(11) 3_665 ?
C2 O1 1.256(10) . ?
C3 C4 1.410(12) . ?
C3 Br6 1.896(8) . ?
C4 O5 1.253(11) . ?
O5 La1 2.562(6) 3_665 ?
O7 C8 1.241(10) . ?
O7 La1 2.664(6) . ?
C8 C9 1.399(11) . ?
C8 C10 1.544(11) 3_766 ?
C9 C10 1.410(12) . ?
C9 Br12 1.886(8) . ?
C10 O11 1.252(10) . ?
O11 La1 2.539(6) 3_766 ?
La1 O1 2.539(6) . ?
La1 O13 2.665(6) . ?
La1 O17 2.546(6) 3_666 ?
La1 O25 2.609(6) . ?
La1 O26 2.574(6) . ?
La1 O27 2.712(7) 4_575 ?
La1 O28 2.549(7) 4_575 ?
O13 C14 1.255(10) . ?
C14 C15 1.407(12) . ?
C14 C16 1.560(11) 3_666 ?
C15 C16 1.377(12) . ?
C15 Br18 1.902(8) . ?
C16 O17 1.258(11) . ?
C19 C20 1.401(13) . ?
C19 C24 1.387(14) . ?
C19 Br29 1.891(10) . ?
C20 C21 1.533(14) . ?
C20 O25 1.246(11) . ?
C21 C22 1.377(15) . ?
C21 O26 1.268(11) . ?
C22 C23 1.412(14) . ?
C22 Br30 1.894(11) . ?
C23 C24 1.531(15) . ?
C23 O27 1.255(11) . ?
C24 O28 1.264(12) . ?
N31 C32 1.339(13) . ?
N31 C36 1.376(11) . ?
N31 C44 1.506(14) . ?
C32 H32 0.9500 . ?
C32 C33 1.368(14) . ?
C33 H33 0.9500 . ?
C33 C34 1.371(13) . ?
C34 H34 0.9500 . ?
C34 C35 1.389(13) . ?
C35 H35 0.9500 . ?
C35 C36 1.384(13) . ?
C36 C37 1.473(13) . ?
C37 C38 1.409(14) . ?
C37 N42 1.342(13) . ?
C38 H38 0.9500 . ?
C38 C39 1.399(15) . ?
C39 H39 0.9500 . ?
C39 C40 1.356(17) . ?
C40 H40 0.9500 . ?
C40 C41 1.364(17) . ?
C41 H41 0.9500 . ?
C41 N42 1.332(14) . ?
N42 C43 1.492(14) . ?
C43 H43A 0.9900 . ?
C43 H43B 0.9900 . ?
C43 C44 1.430(17) . ?
C44 H44A 0.9900 . ?
C44 H44B 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 C2 C4 118.3(7) . 3_665 ?
O1 C2 C3 126.3(8) . . ?
O1 C2 C4 115.5(7) . 3_665 ?
C2 C3 C4 122.3(8) . . ?
C2 C3 Br6 118.6(6) . . ?
C4 C3 Br6 119.1(6) . . ?
C3 C4 C2 119.4(8) . 3_665 ?
O5 C4 C2 116.7(7) . 3_665 ?
O5 C4 C3 123.9(8) . . ?
C4 O5 La1 119.3(5) . 3_665 ?
C8 O7 La1 117.9(5) . . ?
O7 C8 C9 126.5(8) . . ?
O7 C8 C10 115.2(7) . 3_766 ?
C9 C8 C10 118.3(7) . 3_766 ?
C8 C9 C10 122.2(8) . . ?
C8 C9 Br12 119.5(6) . . ?
C10 C9 Br12 118.2(6) . . ?
C9 C10 C8 119.4(7) . 3_766 ?
O11 C10 C8 115.5(7) . 3_766 ?
O11 C10 C9 125.1(8) . . ?
C10 O11 La1 121.5(5) . 3_766 ?
O5 La1 O7 116.98(19) 3_665 . ?
O5 La1 O13 75.93(18) 3_665 . ?
O5 La1 O25 143.8(2) 3_665 . ?
O5 La1 O26 130.2(2) 3_665 . ?
O5 La1 O27 68.7(2) 3_665 4_575 ?
O7 La1 O13 67.46(19) . . ?
O7 La1 O27 165.8(2) . 4_575 ?
O11 La1 O5 64.9(2) 3_766 3_665 ?
O11 La1 O7 60.23(18) 3_766 . ?
O11 La1 O13 81.00(19) 3_766 . ?
O11 La1 O17 124.92(19) 3_766 3_666 ?
O11 La1 O25 92.3(2) 3_766 . ?
O11 La1 O26 150.5(2) 3_766 . ?
O11 La1 O27 115.8(2) 3_766 4_575 ?
O11 La1 O28 69.8(2) 3_766 4_575 ?
O1 La1 O5 62.33(19) . 3_665 ?
O1 La1 O7 128.55(19) . . ?
O1 La1 O11 121.1(2) . 3_766 ?
O1 La1 O13 62.76(19) . . ?
O1 La1 O17 76.75(19) . 3_666 ?
O1 La1 O25 146.63(19) . . ?
O1 La1 O26 86.4(2) . . ?
O1 La1 O27 65.6(2) . 4_575 ?
O1 La1 O28 120.6(2) . 4_575 ?
O13 La1 O27 126.5(2) . 4_575 ?
O17 La1 O5 130.82(19) 3_666 3_665 ?
O17 La1 O7 68.57(19) 3_666 . ?
O17 La1 O13 61.10(18) 3_666 . ?
O17 La1 O25 85.03(19) 3_666 . ?
O17 La1 O26 68.2(2) 3_666 . ?
O17 La1 O27 118.7(2) 3_666 4_575 ?
O17 La1 O28 149.9(2) 3_666 4_575 ?
O25 La1 O7 66.68(19) . . ?
O25 La1 O13 130.32(19) . . ?
O25 La1 O27 100.8(2) . 4_575 ?
O26 La1 O7 112.9(2) . . ?
O26 La1 O13 124.8(2) . . ?
O26 La1 O25 60.8(2) . . ?
O26 La1 O27 63.1(2) . 4_575 ?
O28 La1 O5 78.3(2) 4_575 3_665 ?
O28 La1 O7 108.0(2) 4_575 . ?
O28 La1 O13 147.2(2) 4_575 . ?
O28 La1 O25 67.2(2) 4_575 . ?
O28 La1 O26 87.5(2) 4_575 . ?
O28 La1 O27 59.2(2) 4_575 4_575 ?
C2 O1 La1 120.4(5) . . ?
C14 O13 La1 118.5(5) . . ?
O13 C14 C15 126.8(8) . . ?
O13 C14 C16 116.2(7) . 3_666 ?
C15 C14 C16 116.9(7) . 3_666 ?
C14 C15 Br18 118.5(6) . . ?
C16 C15 C14 123.2(7) . . ?
C16 C15 Br18 118.1(6) . . ?
C15 C16 C14 119.2(7) . 3_666 ?
O17 C16 C14 115.2(7) . 3_666 ?
O17 C16 C15 125.6(8) . . ?
C16 O17 La1 123.8(5) . 3_666 ?
C20 C19 Br29 119.3(7) . . ?
C24 C19 C20 122.1(9) . . ?
C24 C19 Br29 118.5(7) . . ?
C19 C20 C21 118.0(8) . . ?
O25 C20 C19 125.6(9) . . ?
O25 C20 C21 116.3(8) . . ?
C22 C21 C20 119.5(9) . . ?
O26 C21 C20 115.0(8) . . ?
O26 C21 C22 125.5(10) . . ?
C21 C22 C23 122.2(10) . . ?
C21 C22 Br30 118.5(8) . . ?
C23 C22 Br30 119.3(8) . . ?
C22 C23 C24 117.9(9) . . ?
O27 C23 C22 126.1(10) . . ?
O27 C23 C24 116.0(9) . . ?
C19 C24 C23 119.3(8) . . ?
O28 C24 C19 126.3(10) . . ?
O28 C24 C23 114.3(9) . . ?
C20 O25 La1 123.3(6) . . ?
C21 O26 La1 124.5(6) . . ?
C23 O27 La1 120.5(7) . 4_576 ?
C24 O28 La1 126.8(7) . 4_576 ?
C32 N31 C36 122.0(8) . . ?
C32 N31 C44 120.6(8) . . ?
C36 N31 C44 117.3(9) . . ?
N31 C32 H32 119.3 . . ?
N31 C32 C33 121.3(9) . . ?
C33 C32 H32 119.3 . . ?
C32 C33 H33 120.8 . . ?
C32 C33 C34 118.4(9) . . ?
C34 C33 H33 120.8 . . ?
C33 C34 H34 119.8 . . ?
C33 C34 C35 120.5(9) . . ?
C35 C34 H34 119.8 . . ?
C34 C35 H35 119.9 . . ?
C36 C35 C34 120.2(8) . . ?
C36 C35 H35 119.9 . . ?
N31 C36 C35 117.5(8) . . ?
N31 C36 C37 119.0(8) . . ?
C35 C36 C37 123.3(8) . . ?
C38 C37 C36 120.8(9) . . ?
N42 C37 C36 120.4(8) . . ?
N42 C37 C38 118.8(9) . . ?
C37 C38 H38 121.4 . . ?
C39 C38 C37 117.2(10) . . ?
C39 C38 H38 121.4 . . ?
C38 C39 H39 119.4 . . ?
C40 C39 C38 121.3(11) . . ?
C40 C39 H39 119.4 . . ?
C39 C40 H40 120.2 . . ?
C39 C40 C41 119.5(10) . . ?
C41 C40 H40 120.2 . . ?
C40 C41 H41 120.1 . . ?
N42 C41 C40 119.8(11) . . ?
N42 C41 H41 120.1 . . ?
C37 N42 C43 116.7(9) . . ?
C41 N42 C37 123.3(9) . . ?
C41 N42 C43 119.7(9) . . ?
N42 C43 H43A 109.6 . . ?
N42 C43 H43B 109.6 . . ?
H43A C43 H43B 108.1 . . ?
C44 C43 N42 110.3(10) . . ?
C44 C43 H43A 109.6 . . ?
C44 C43 H43B 109.6 . . ?
N31 C44 H44A 109.4 . . ?
N31 C44 H44B 109.4 . . ?
C43 C44 N31 111.0(10) . . ?
C43 C44 H44A 109.4 . . ?
C43 C44 H44B 109.4 . . ?
H44A C44 H44B 108.0 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 C3 C4 C2 2.4(14) . . . 3_665 ?
C2 C3 C4 O5 -177.7(8) . . . . ?
C2 C4 O5 La1 -17.8(10) 3_665 . . 3_665 ?
C3 C2 O1 La1 158.8(7) . . . . ?
C3 C4 O5 La1 162.3(6) . . . 3_665 ?
C4 C2 C3 C4 -2.3(13) 3_665 . . . ?
C4 C2 C3 Br6 176.8(6) 3_665 . . . ?
C4 C2 O1 La1 -20.4(9) 3_665 . . . ?
Br6 C3 C4 C2 -176.7(6) . . . 3_665 ?
Br6 C3 C4 O5 3.1(12) . . . . ?
O7 C8 C9 C10 178.4(9) . . . . ?
O7 C8 C9 Br12 -2.7(13) . . . . ?
C8 C9 C10 C8 3.5(15) . . . 3_766 ?
C8 C9 C10 O11 -177.6(9) . . . . ?
C8 C10 O11 La1 26.2(10) 3_766 . . 3_766 ?
C9 C10 O11 La1 -152.8(7) . . . 3_766 ?
C10 C8 C9 C10 -3.5(14) 3_766 . . . ?
C10 C8 C9 Br12 175.4(6) 3_766 . . . ?
La1 O7 C8 C9 -158.9(7) . . . . ?
La1 O7 C8 C10 22.9(10) . . . 3_766 ?
La1 O13 C14 C15 156.7(7) . . . . ?
La1 O13 C14 C16 -20.0(9) . . . 3_666 ?
O1 C2 C3 C4 178.5(8) . . . . ?
O1 C2 C3 Br6 -2.4(12) . . . . ?
Br12 C9 C10 C8 -175.3(6) . . . 3_766 ?
Br12 C9 C10 O11 3.6(13) . . . . ?
O13 C14 C15 C16 173.8(9) . . . . ?
O13 C14 C15 Br18 -2.4(13) . . . . ?
C14 C15 C16 C14 9.7(14) . . . 3_666 ?
C14 C15 C16 O17 -173.0(8) . . . . ?
C14 C16 O17 La1 -16.2(10) 3_666 . . 3_666 ?
C15 C16 O17 La1 166.4(7) . . . 3_666 ?
C16 C14 C15 C16 -9.5(14) 3_666 . . . ?
C16 C14 C15 Br18 174.3(6) 3_666 . . . ?
Br18 C15 C16 C14 -174.1(6) . . . 3_666 ?
Br18 C15 C16 O17 3.2(12) . . . . ?
C19 C20 C21 C22 -1.3(14) . . . . ?
C19 C20 C21 O26 175.6(9) . . . . ?
C19 C20 O25 La1 -176.9(7) . . . . ?
C19 C24 O28 La1 -166.5(7) . . . 4_576 ?
C20 C19 C24 C23 -9.3(14) . . . . ?
C20 C19 C24 O28 175.0(9) . . . . ?
C20 C21 C22 C23 -6.9(17) . . . . ?
C20 C21 C22 Br30 174.0(7) . . . . ?
C20 C21 O26 La1 3.7(11) . . . . ?
C21 C20 O25 La1 2.8(11) . . . . ?
C21 C22 C23 C24 7.1(17) . . . . ?
C21 C22 C23 O27 -172.9(11) . . . . ?
C22 C21 O26 La1 -179.6(9) . . . . ?
C22 C23 C24 C19 1.0(14) . . . . ?
C22 C23 C24 O28 177.2(10) . . . . ?
C22 C23 O27 La1 168.8(9) . . . 4_576 ?
C23 C24 O28 La1 17.6(12) . . . 4_576 ?
C24 C19 C20 C21 9.5(14) . . . . ?
C24 C19 C20 O25 -170.8(9) . . . . ?
C24 C23 O27 La1 -11.2(11) . . . 4_576 ?
O25 C20 C21 C22 179.0(10) . . . . ?
O25 C20 C21 O26 -4.1(12) . . . . ?
O26 C21 C22 C23 176.5(10) . . . . ?
O26 C21 C22 Br30 -2.6(16) . . . . ?
O27 C23 C24 C19 -179.0(9) . . . . ?
O27 C23 C24 O28 -2.8(13) . . . . ?
Br29 C19 C20 C21 -173.5(7) . . . . ?
Br29 C19 C20 O25 6.2(13) . . . . ?
Br29 C19 C24 C23 173.6(7) . . . . ?
Br29 C19 C24 O28 -2.1(14) . . . . ?
Br30 C22 C23 C24 -173.8(7) . . . . ?
Br30 C22 C23 O27 6.2(16) . . . . ?
N31 C32 C33 C34 -2.7(15) . . . . ?
N31 C36 C37 C38 166.3(9) . . . . ?
N31 C36 C37 N42 -12.0(13) . . . . ?
C32 N31 C36 C35 -3.2(14) . . . . ?
C32 N31 C36 C37 -177.6(9) . . . . ?
C32 N31 C44 C43 -147.1(12) . . . . ?
C32 C33 C34 C35 -0.3(13) . . . . ?
C33 C34 C35 C36 1.4(14) . . . . ?
C34 C35 C36 N31 0.2(13) . . . . ?
C34 C35 C36 C37 174.4(8) . . . . ?
C35 C36 C37 C38 -7.8(14) . . . . ?
C35 C36 C37 N42 173.9(9) . . . . ?
C36 N31 C32 C33 4.5(15) . . . . ?
C36 N31 C44 C43 36.5(16) . . . . ?
C36 C37 C38 C39 -178.1(10) . . . . ?
C36 C37 N42 C41 174.9(9) . . . . ?
C36 C37 N42 C43 -10.7(13) . . . . ?
C37 C38 C39 C40 1.4(18) . . . . ?
C37 N42 C43 C44 46.1(15) . . . . ?
C38 C37 N42 C41 -3.5(14) . . . . ?
C38 C37 N42 C43 170.9(10) . . . . ?
C38 C39 C40 C41 0.1(19) . . . . ?
C39 C40 C41 N42 -3.2(17) . . . . ?
C40 C41 N42 C37 5.0(16) . . . . ?
C40 C41 N42 C43 -169.2(11) . . . . ?
C41 N42 C43 C44 -139.3(11) . . . . ?
N42 C37 C38 C39 0.3(15) . . . . ?
N42 C43 C44 N31 -57.4(16) . . . . ?
C44 N31 C32 C33 -171.7(11) . . . . ?
C44 N31 C36 C35 173.2(10) . . . . ?
C44 N31 C36 C37 -1.3(14) . . . . ?

_platon_squeeze_details          ?
_platon_squeeze_special_details  ?
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.146 0.689 0.532 42 12 ' '
2 0.146 0.811 1.032 41 11 ' '
3 0.195 0.575 0.677 16 6 ' '
4 0.195 0.925 0.177 16 6 ' '
5 0.406 0.200 0.796 9 0 ' '
6 0.406 0.300 0.296 9 0 ' '
7 0.594 0.700 0.704 10 0 ' '
8 0.594 0.800 0.204 10 0 ' '
9 0.853 0.189 0.968 42 12 ' '
10 0.853 0.311 0.468 42 12 ' '
11 0.805 0.075 0.822 15 6 ' '
12 0.805 0.425 0.322 15 6 ' '

_platon_squeeze_void_probe_radius 1.20
# end Validation Reply Form
_olex2_submission_special_instructions 'No special instructions were received'
# start Validation Reply Form
_vrf_DIFMX02_mf-1-16a_abs-m_a_sq 
;
PROBLEM: The maximum difference density is > 0.1*ZMAX*0.75
RESPONSE: The high maximum density difference is due to absorption from the heavy La and Br atoms. The largest residual electron density occurs 1.29 Ang from Br30.
;
_vrf_PLAT029_mf-1-16a_abs-m_a_sq 
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.970 Why?  
RESPONSE: The crystal was measured using the MX1 beamline of the Australian Synchrotron due to the small size and weak diffraction. Data was collected only via rotation about the omega axis, which does not allow complete data to be collected due to the low triclinic symmetry of the crystal.
;
_vrf_PLAT097_mf-1-16a_abs-m_a_sq 
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       7.13 eA-3  
RESPONSE: The high maxiumum residual electron density is due to absorption from the heavy La and Br atoms.
;
_vrf_PLAT360_mf-1-16a_abs-m_a_sq 
;
PROBLEM: Short  C(sp3)-C(sp3) Bond  C43      - C44      .       1.43 Ang.  
RESPONSE: Analysis of 89 structures in the CCDC shows the range of C-C bond lengths equivalent to the C43-C44 bond in DiQ2+ ranges from 1.404-1.540 Ang. The measure C43-C44 bond length falls within this observed range.
;
_vrf_PLAT369_mf-1-16a_abs-m_a_sq 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_b     .       1.54 Ang.  
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
_vrf_PLAT971_mf-1-16a_abs-m_a_sq 
;
PROBLEM: Check Calcd Resid. Dens.  1.29Ang From Br30            7.16 eA-3  
RESPONSE: The high residual electron density is due to absorption from the heavy La and Br atoms.
;
_vrf_PLAT972_mf-1-16a_abs-m_a_sq 
;
PROBLEM: Check Calcd Resid. Dens.  0.78Ang From Br30           -3.57 eA-3  
RESPONSE: The high residual electron density is due to absorption from the heavy La and Br atoms.
;
_vrf_PLAT973_mf-1-16a_abs-m_a_sq 
;
PROBLEM: Check Calcd Positive Resid. Density on       La1       2.04 eA-3  
RESPONSE: The high residual electron density is due to absorption from the heavy La and Br atoms.
;
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mf-1-15a_1_twin_auto_abs_a_sq
_database_code_depnum_ccdc_archive 'CCDC 2415085'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT369_mf-1-15a_1_twin_auto_abs_a_sq 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_b     .       1.54 Ang.
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
# Added during the CSD deposition process: Tuesday 07 January 2025 12:07 AM
# end Validation Reply Form

_audit_creation_date             2024-04-08
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C15 Cl5 La O10, C12 H12 N2, 3(H2 O)'
_chemical_formula_sum            'C27 H18 Cl5 La N2 O13'
_chemical_formula_weight         894.59
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C27 H18 Cl5 La N2 O13'
_chemical_oxdiff_usercomment     'Solvent:actone and water'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   11.8532(2)
_cell_length_b                   26.2857(4)
_cell_length_c                   10.5597(2)
_cell_angle_alpha                90
_cell_angle_beta                 107.882(2)
_cell_angle_gamma                90
_cell_volume                     3131.14(10)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    11246
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.7160
_cell_measurement_theta_min      3.3660
_shelx_estimated_absorpt_T_max   0.357
_shelx_estimated_absorpt_T_min   0.210
_exptl_absorpt_coefficient_mu    15.105
_exptl_absorpt_correction_T_max  0.548
_exptl_absorpt_correction_T_min  0.214
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.898
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       prism
_exptl_crystal_F_000             1760
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
1 -15 -3 0.0565
-4 -14 0 0.0685
-7 -4 4 0.0751
5 -7 -5 0.0669
-1 15 4 0.0297
5 14 -1 0.0383
3 -5 5 0.0532
-2 15 -2 0.0357
-3 6 -4 0.0420
-2 -9 -5 0.0513
2 -16 1 0.0586
7 -9 -2 0.0660
-6 -6 -1 0.0637
-7 4 1 0.0538
2 -6 -6 0.0516
-2 -16 1 0.0665
-4 -10 5 0.0732
3 0 5 0.0481

_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.086
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
0.7741 -14.6394 -3.4988 0.0033 0.1864 -0.9825
-4.1200 -14.2321 0.2670 -0.0150 -0.5376 -0.8431
-6.8723 -4.0096 4.3752 -0.0255 -0.9940 -0.1062
5.1445 -7.3975 -5.3466 0.0194 0.7954 -0.6057
-0.8215 14.6028 3.5272 -0.0034 -0.1933 0.9811
4.6000 13.6108 -0.7521 0.0168 0.6114 0.7911
3.4816 -4.9921 4.5450 0.9914 -0.0254 0.1285
-2.4397 14.8898 -1.7565 -0.7958 0.0196 0.6052
-3.4734 5.8714 -4.4225 -0.9969 0.0255 -0.0738
-2.2926 -9.0817 -4.5439 -0.5431 0.0147 -0.8395
2.0760 -15.8432 1.0967 0.7053 -0.0172 -0.7087
6.5595 -8.9010 -1.6763 0.6283 0.6638 -0.4057
-6.3906 -6.2708 -0.9783 -0.5679 -0.5982 -0.5653
-7.3734 3.5634 0.7584 -0.6872 -0.7253 0.0419
2.2209 -6.0476 -6.4111 -0.4153 0.6016 -0.6824
-2.4688 -16.0225 1.4819 0.3287 -0.4795 -0.8137
-3.5176 -10.3281 5.2140 0.5414 -0.7873 -0.2952
3.3325 0.1631 4.9700 0.9051 -0.0235 0.4246

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19634
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.800
_diffrn_reflns_theta_min         3.363
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -85.00 -13.00   0.50    0.20    --  -54.99 125.00  60.00  144
  2  ω    -77.00 -39.00   0.50    0.20    -- -106.00 111.00 -30.00   76
  3  ω    -81.00 -22.00   0.50    0.20    -- -106.00 111.00-180.00  118
  4  ω    -65.00 -38.00   0.50    0.20    -- -106.00  63.00  30.00   54
  5  ω    -55.00 -29.00   0.50    0.20    -- -106.00  63.00 -60.00   52
  6  ω    -48.00 -23.00   0.50    0.20    -- -106.00  50.00 -90.00   50
  7  ω    -56.00 -26.00   0.50    0.20    -- -106.00  50.00-150.00   60
  8  ω    -50.00 -24.00   0.50    0.20    -- -106.00  50.00-180.00   52
  9  ω    -52.00 -26.00   0.50    0.20    -- -106.00  50.00-120.00   52
 10  ω    -52.00 -26.00   0.50    0.20    -- -106.00  50.00 150.00   52
 11  ω    -19.00  18.00   0.50    0.20    --  -54.99  34.00  59.00   74
 12  ω     49.00  97.00   0.50    0.20    --  109.99-111.00 150.00   96
 13  ω      0.00  32.00   0.50    0.10    --    0.00 -99.00-180.00   64
 14  ω   -109.00   4.00   0.50    0.20    --  -54.99 -34.00 -98.00  226
 15  ω   -111.00 -74.00   0.50    0.20    --  -54.99-125.00  60.00   74
 16  ω   -136.00 -74.00   0.50    0.20    --  -54.99-125.00  30.00  124
 17  ω   -176.00 -47.00   0.50    0.20    -- -106.00 -34.00 -98.00  258
 18  ω   -143.00-112.00   0.50    0.20    --  -54.99 -34.00 -98.00   62
 19  ω   -142.00 -86.00   0.50    0.20    --  -54.99 -99.00 -30.00  112
 20  ω    -83.00 -32.00   0.50    0.10    --    0.00 -34.00 -98.00  102
 21  ω     36.00  62.00   0.50    0.20    --  109.99 -77.00  90.00   52
 22  ω     67.00  93.00   0.50    0.20    --  109.99 -77.00  90.00   52
 23  ω     33.00  71.00   0.50    0.20    --  109.99 -63.00  30.00   76
 24  ω     32.00  61.00   0.50    0.20    --  109.99 -63.00 -30.00   58
 25  ω     32.00  57.00   0.50    0.20    --  109.99 -63.00 -90.00   50
 26  ω     34.00  69.00   0.50    0.20    --  109.99 -63.00-120.00   70
 27  ω     28.00  53.00   0.50    0.20    --  109.99 -50.00-120.00   50
 28  ω     28.00  96.00   0.50    0.20    --  109.99 -77.00 -30.00  136
 29  ω     28.00  53.00   0.50    0.20    --  109.99 -50.00-150.00   50
 30  ω     29.00  56.00   0.50    0.20    --  109.99 -50.00   0.00   54
 31  ω     31.00  57.00   0.50    0.20    --  109.99 -50.00  90.00   52
 32  ω     30.00  56.00   0.50    0.20    --  109.99 -50.00 150.00   52
 33  ω     45.00  70.00   0.50    0.20    --   54.99  35.00  58.00   50
 34  ω     44.00  69.00   0.50    0.20    --   54.99  34.00  59.00   50
 35  ω      5.00  50.00   0.50    0.10    --    0.00  34.00  59.00   90
 36  ω    -37.00  -4.00   0.50    0.10    --    0.00  34.00  59.00   66
 37  ω     65.00 102.00   0.50    0.20    --  109.99  34.00  59.00   74
 38  ω    145.00 173.00   0.50    0.20    --  109.99 111.00 -60.00   56
 39  ω    103.00 161.00   0.50    0.20    --  109.99 111.00 -90.00  116
 40  ω    114.00 140.00   0.50    0.20    --  109.99 111.00 -60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0939777000
_diffrn_orient_matrix_UB_12      -0.0239051000
_diffrn_orient_matrix_UB_13      0.1198805000
_diffrn_orient_matrix_UB_21      0.0955217000
_diffrn_orient_matrix_UB_22      0.0088224000
_diffrn_orient_matrix_UB_23      -0.0690687000
_diffrn_orient_matrix_UB_31      0.0265945000
_diffrn_orient_matrix_UB_32      0.0527759000
_diffrn_orient_matrix_UB_33      0.0658631000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5627
_reflns_number_total             5950
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         2.078
_refine_diff_density_min         -1.790
_refine_diff_density_rms         0.113
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     436
_refine_ls_number_reflns         5950
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0409
_refine_ls_R_factor_gt           0.0375
_refine_ls_restrained_S_all      1.045
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0396P)²+11.3662P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.0910
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 O45-H45A = O45-H45B
 0.84 with sigma of 0.02
 H45A-H45B
 1.34 with sigma of 0.04
 O46-H46A = O46-H46B
 0.84 with sigma of 0.02
 H46A-H46B
 1.34 with sigma of 0.04
3.a Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C44(H44A,H44B)
3.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C33(H33), C34(H34), C35(H35), C38(H38), C39(H39), C40(H40), C41(H41)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C2 C 0.4956(3) 0.53822(14) 0.5977(4) 0.0156(8) Uani 1 1 d . . . . .
C3 C 0.3964(3) 0.50742(15) 0.5430(4) 0.0170(8) Uani 1 1 d . . . . .
C4 C 0.3943(3) 0.47015(15) 0.4474(4) 0.0157(8) Uani 1 1 d . . . . .
O5 O 0.3070(2) 0.44206(11) 0.3934(3) 0.0188(6) Uani 1 1 d . . . . .
Cl6 Cl 0.27244(8) 0.51583(4) 0.59523(10) 0.0217(2) Uani 1 1 d . . . . .
O7 O 0.8557(2) 0.57350(10) 1.0369(3) 0.0180(6) Uani 1 1 d . . . . .
C8 C 0.9219(3) 0.53791(15) 1.0268(4) 0.0163(8) Uani 1 1 d . . . . .
C9 C 0.9735(4) 0.50178(16) 1.1250(4) 0.0206(8) Uani 1 1 d . . . . .
C10 C 1.0503(3) 0.46474(15) 1.1061(4) 0.0176(8) Uani 1 1 d . . . . .
La1 La 0.70517(2) 0.60840(2) 0.81508(2) 0.01293(8) Uani 1 1 d . . . . .
O1 O 0.5033(2) 0.57259(10) 0.6819(3) 0.0179(6) Uani 1 1 d . . . . .
O11 O 1.1018(2) 0.43189(10) 1.1905(3) 0.0188(6) Uani 1 1 d . . . . .
Cl12 Cl 0.95105(9) 0.50700(4) 1.27932(9) 0.0226(2) Uani 1 1 d . . . . .
O13 O 0.6591(2) 0.51169(10) 0.8649(3) 0.0192(6) Uani 1 1 d . . . . .
C14 C 0.5824(4) 0.50382(15) 0.9229(4) 0.0169(8) Uani 1 1 d . . . . .
C15 C 0.5204(4) 0.45869(16) 0.9201(4) 0.0194(8) Uani 1 1 d . . . . .
C16 C 0.4440(3) 0.45119(15) 0.9972(4) 0.0165(8) Uani 1 1 d . . . . .
O17 O 0.3951(2) 0.40971(10) 1.0076(3) 0.0188(6) Uani 1 1 d . . . . .
Cl18 Cl 0.54276(9) 0.40827(4) 0.82366(10) 0.0237(2) Uani 1 1 d . . . . .
C19 C 0.8345(4) 0.74065(15) 0.5808(4) 0.0187(8) Uani 1 1 d . . . . .
C20 C 0.7764(4) 0.78073(14) 0.5011(4) 0.0170(8) Uani 1 1 d . . . . .
C21 C 0.6413(4) 0.77888(16) 0.4411(4) 0.0232(9) Uani 1 1 d . . . . .
C22 C 0.5804(4) 0.73833(19) 0.4756(6) 0.0358(12) Uani 1 1 d . . . . .
C23 C 0.6370(4) 0.70011(15) 0.5650(4) 0.0213(9) Uani 1 1 d . . . . .
C24 C 0.7727(4) 0.70142(15) 0.6215(4) 0.0168(8) Uani 1 1 d . . . . .
O25 O 0.8252(2) 0.81993(10) 0.4731(3) 0.0184(6) Uani 1 1 d . . . . .
O26 O 0.5947(3) 0.81443(11) 0.3642(3) 0.0226(6) Uani 1 1 d . . . . .
O27 O 0.5861(3) 0.66458(11) 0.6043(3) 0.0226(6) Uani 1 1 d . . . . .
O28 O 0.8194(3) 0.66684(10) 0.7011(3) 0.0190(6) Uani 1 1 d . . . . .
Cl29 Cl 0.98843(8) 0.74024(4) 0.63841(10) 0.0235(2) Uani 1 1 d . . . . .
Cl30 Cl 0.42773(12) 0.73617(6) 0.4025(2) 0.0783(7) Uani 1 1 d . . . . .
N31 N 0.0229(3) 0.64789(13) 0.3933(3) 0.0210(7) Uani 1 1 d . . . . .
C32 C -0.0728(4) 0.64828(16) 0.2842(4) 0.0236(9) Uani 1 1 d . . . . .
H32 H -0.066723 0.662126 0.203486 0.028 Uiso 1 1 calc R U . . .
C33 C -0.1800(4) 0.62874(16) 0.2885(4) 0.0219(9) Uani 1 1 d . . . . .
H33 H -0.248218 0.629822 0.212255 0.026 Uiso 1 1 calc R U . . .
C34 C -0.1853(4) 0.60764(15) 0.4062(4) 0.0197(8) Uani 1 1 d . . . . .
H34 H -0.258346 0.594628 0.412023 0.024 Uiso 1 1 calc R U . . .
C35 C -0.0840(4) 0.60532(14) 0.5167(4) 0.0174(8) Uani 1 1 d . . . . .
H35 H -0.086849 0.589213 0.596197 0.021 Uiso 1 1 calc R U . . .
C36 C 0.0203(4) 0.62660(15) 0.5097(4) 0.0183(8) Uani 1 1 d . . . . .
C37 C 0.1280(4) 0.62994(15) 0.6271(4) 0.0190(8) Uani 1 1 d . . . . .
C38 C 0.1237(4) 0.62331(16) 0.7545(4) 0.0222(9) Uani 1 1 d . . . . .
H38 H 0.050337 0.616584 0.770048 0.027 Uiso 1 1 calc R U . . .
C39 C 0.2283(4) 0.62653(17) 0.8611(5) 0.0254(9) Uani 1 1 d . . . . .
H39 H 0.227109 0.620485 0.949317 0.030 Uiso 1 1 calc R U . . .
C40 C 0.3335(4) 0.63856(17) 0.8374(5) 0.0266(9) Uani 1 1 d . . . . .
H40 H 0.404753 0.641468 0.909328 0.032 Uiso 1 1 calc R U . . .
C41 C 0.3342(4) 0.64625(16) 0.7096(4) 0.0233(9) Uani 1 1 d . . . . .
H41 H 0.405773 0.655307 0.692676 0.028 Uiso 1 1 calc R U . . .
N42 N 0.2336(3) 0.64101(13) 0.6078(4) 0.0209(7) Uani 1 1 d . . . . .
C43 C 0.2384(4) 0.64396(18) 0.4701(4) 0.0270(10) Uani 1 1 d . . . . .
H43A H 0.237169 0.609314 0.432948 0.032 Uiso 1 1 calc R U . . .
H43B H 0.312507 0.660988 0.468647 0.032 Uiso 1 1 calc R U . . .
C44 C 0.1331(4) 0.67363(18) 0.3884(5) 0.0292(10) Uani 1 1 d . . . . .
H44A H 0.136008 0.708635 0.423869 0.035 Uiso 1 1 calc R U . . .
H44B H 0.134079 0.675768 0.295170 0.035 Uiso 1 1 calc R U . . .
O45 O 0.7908(4) 0.43844(17) 0.7556(5) 0.0537(11) Uani 1 1 d D . . . .
H45A H 0.833(6) 0.4630(19) 0.744(8) 0.080 Uiso 1 1 d D U . . .
H45B H 0.735(5) 0.450(3) 0.782(8) 0.080 Uiso 1 1 d D U . . .
O46 O 0.9104(4) 0.35842(18) 0.9265(6) 0.0586(12) Uani 1 1 d D . . . .
H46A H 0.900(7) 0.3902(11) 0.908(9) 0.088 Uiso 1 1 d D U . . .
H46B H 0.978(4) 0.356(3) 0.984(7) 0.088 Uiso 1 1 d D U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C2 C3 1.398(5) . ?
C2 C4 1.537(5) 3_666 ?
C2 O1 1.251(5) . ?
C3 C4 1.401(6) . ?
C3 Cl6 1.736(4) . ?
C4 O5 1.256(5) . ?
O5 La1 2.536(3) 3_666 ?
O7 C8 1.247(5) . ?
O7 La1 2.636(3) . ?
C8 C9 1.400(6) . ?
C8 C10 1.538(5) 3_767 ?
C9 C10 1.389(6) . ?
C9 Cl12 1.735(4) . ?
C10 O11 1.256(5) . ?
La1 O1 2.554(3) . ?
La1 O11 2.538(3) 3_767 ?
La1 O13 2.686(3) . ?
La1 O17 2.553(3) 3_667 ?
La1 O25 2.627(3) 4_576 ?
La1 O26 2.552(3) 4_576 ?
La1 O27 2.683(3) . ?
La1 O28 2.578(3) . ?
O13 C14 1.259(5) . ?
C14 C15 1.391(6) . ?
C14 C16 1.540(5) 3_667 ?
C15 C16 1.405(6) . ?
C15 Cl18 1.740(4) . ?
C16 O17 1.255(5) . ?
C19 C20 1.392(6) . ?
C19 C24 1.406(6) . ?
C19 Cl29 1.738(4) . ?
C20 C21 1.532(6) . ?
C20 O25 1.260(5) . ?
C21 C22 1.397(6) . ?
C21 O26 1.250(5) . ?
C22 C23 1.400(6) . ?
C22 Cl30 1.737(5) . ?
C23 C24 1.535(6) . ?
C23 O27 1.249(5) . ?
C24 O28 1.246(5) . ?
N31 C32 1.345(5) . ?
N31 C36 1.359(5) . ?
N31 C44 1.486(5) . ?
C32 H32 0.9500 . ?
C32 C33 1.384(6) . ?
C33 H33 0.9500 . ?
C33 C34 1.380(6) . ?
C34 H34 0.9500 . ?
C34 C35 1.395(6) . ?
C35 H35 0.9500 . ?
C35 C36 1.380(6) . ?
C36 C37 1.484(6) . ?
C37 C38 1.373(6) . ?
C37 N42 1.360(5) . ?
C38 H38 0.9500 . ?
C38 C39 1.398(6) . ?
C39 H39 0.9500 . ?
C39 C40 1.381(7) . ?
C40 H40 0.9500 . ?
C40 C41 1.367(7) . ?
C41 H41 0.9500 . ?
C41 N42 1.344(6) . ?
N42 C43 1.475(6) . ?
C43 H43A 0.9900 . ?
C43 H43B 0.9900 . ?
C43 C44 1.500(6) . ?
C44 H44A 0.9900 . ?
C44 H44B 0.9900 . ?
O45 H45A 0.85(2) . ?
O45 H45B 0.85(2) . ?
O46 H46A 0.86(2) . ?
O46 H46B 0.84(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 C2 C4 118.4(3) . 3_666 ?
O1 C2 C3 125.5(4) . . ?
O1 C2 C4 116.1(3) . 3_666 ?
C2 C3 C4 122.0(4) . . ?
C2 C3 Cl6 118.8(3) . . ?
C4 C3 Cl6 119.2(3) . . ?
C3 C4 C2 119.6(3) . 3_666 ?
O5 C4 C2 115.7(3) . 3_666 ?
O5 C4 C3 124.7(4) . . ?
C4 O5 La1 121.4(2) . 3_666 ?
C8 O7 La1 117.2(2) . . ?
O7 C8 C9 126.0(4) . . ?
O7 C8 C10 115.4(3) . 3_767 ?
C9 C8 C10 118.6(3) . 3_767 ?
C8 C9 Cl12 119.0(3) . . ?
C10 C9 C8 121.7(4) . . ?
C10 C9 Cl12 119.1(3) . . ?
C9 C10 C8 119.7(3) . 3_767 ?
O11 C10 C8 115.0(3) . 3_767 ?
O11 C10 C9 125.3(4) . . ?
O5 La1 O7 115.59(9) 3_666 . ?
O5 La1 O1 62.29(9) 3_666 . ?
O5 La1 O11 64.74(9) 3_666 3_767 ?
O5 La1 O13 73.39(9) 3_666 . ?
O5 La1 O17 128.61(9) 3_666 3_667 ?
O5 La1 O25 143.33(9) 3_666 4_576 ?
O5 La1 O26 134.11(9) 3_666 4_576 ?
O5 La1 O27 72.08(9) 3_666 . ?
O5 La1 O28 78.72(9) 3_666 . ?
O7 La1 O13 67.63(8) . . ?
O7 La1 O27 165.72(9) . . ?
O1 La1 O7 128.71(9) . . ?
O1 La1 O13 63.03(9) . . ?
O1 La1 O25 147.92(8) . 4_576 ?
O1 La1 O27 65.22(9) . . ?
O1 La1 O28 120.01(9) . . ?
O11 La1 O7 60.40(9) 3_767 . ?
O11 La1 O1 122.14(9) 3_767 . ?
O11 La1 O13 81.28(9) 3_767 . ?
O11 La1 O17 124.43(9) 3_767 3_667 ?
O11 La1 O25 89.88(9) 3_767 4_576 ?
O11 La1 O26 149.16(9) 3_767 4_576 ?
O11 La1 O27 117.30(9) 3_767 . ?
O11 La1 O28 68.36(9) 3_767 . ?
O17 La1 O7 67.90(9) 3_667 . ?
O17 La1 O1 76.51(9) 3_667 . ?
O17 La1 O13 60.74(9) 3_667 . ?
O17 La1 O25 87.19(9) 3_667 4_576 ?
O17 La1 O27 117.82(9) 3_667 . ?
O17 La1 O28 152.10(9) 3_667 . ?
O25 La1 O7 66.31(8) 4_576 . ?
O25 La1 O13 131.10(8) 4_576 . ?
O25 La1 O27 100.17(9) 4_576 . ?
O26 La1 O7 110.22(9) 4_576 . ?
O26 La1 O1 87.29(9) 4_576 . ?
O26 La1 O13 124.37(9) 4_576 . ?
O26 La1 O17 67.39(9) 4_576 3_667 ?
O26 La1 O25 60.82(9) 4_576 4_576 ?
O26 La1 O27 63.85(9) 4_576 . ?
O26 La1 O28 89.84(9) 4_576 . ?
O27 La1 O13 126.64(9) . . ?
O28 La1 O7 108.24(9) . . ?
O28 La1 O13 145.39(9) . . ?
O28 La1 O25 67.03(9) . 4_576 ?
O28 La1 O27 60.16(9) . . ?
C2 O1 La1 120.6(2) . . ?
C10 O11 La1 121.0(2) . 3_767 ?
C14 O13 La1 118.1(2) . . ?
O13 C14 C15 125.8(4) . . ?
O13 C14 C16 116.1(3) . 3_667 ?
C15 C14 C16 118.1(3) . 3_667 ?
C14 C15 C16 122.5(4) . . ?
C14 C15 Cl18 119.2(3) . . ?
C16 C15 Cl18 118.2(3) . . ?
C15 C16 C14 119.1(3) . 3_667 ?
O17 C16 C14 116.2(3) . 3_667 ?
O17 C16 C15 124.7(4) . . ?
C16 O17 La1 123.9(2) . 3_667 ?
C20 C19 C24 122.2(4) . . ?
C20 C19 Cl29 119.2(3) . . ?
C24 C19 Cl29 118.5(3) . . ?
C19 C20 C21 119.1(4) . . ?
O25 C20 C19 125.7(4) . . ?
O25 C20 C21 115.2(3) . . ?
C22 C21 C20 118.3(4) . . ?
O26 C21 C20 116.2(4) . . ?
O26 C21 C22 125.4(4) . . ?
C21 C22 C23 123.0(4) . . ?
C21 C22 Cl30 117.4(3) . . ?
C23 C22 Cl30 119.6(3) . . ?
C22 C23 C24 118.3(4) . . ?
O27 C23 C22 125.5(4) . . ?
O27 C23 C24 116.3(4) . . ?
C19 C24 C23 118.7(3) . . ?
O28 C24 C19 125.1(4) . . ?
O28 C24 C23 116.2(3) . . ?
C20 O25 La1 122.5(3) . 4_575 ?
C21 O26 La1 125.1(3) . 4_575 ?
C23 O27 La1 120.2(3) . . ?
C24 O28 La1 124.1(3) . . ?
C32 N31 C36 122.0(4) . . ?
C32 N31 C44 119.1(4) . . ?
C36 N31 C44 118.8(4) . . ?
N31 C32 H32 119.7 . . ?
N31 C32 C33 120.7(4) . . ?
C33 C32 H32 119.7 . . ?
C32 C33 H33 120.8 . . ?
C34 C33 C32 118.3(4) . . ?
C34 C33 H33 120.8 . . ?
C33 C34 H34 119.8 . . ?
C33 C34 C35 120.3(4) . . ?
C35 C34 H34 119.8 . . ?
C34 C35 H35 120.2 . . ?
C36 C35 C34 119.5(4) . . ?
C36 C35 H35 120.2 . . ?
N31 C36 C35 119.0(4) . . ?
N31 C36 C37 118.6(4) . . ?
C35 C36 C37 122.3(4) . . ?
C38 C37 C36 122.0(4) . . ?
N42 C37 C36 118.9(4) . . ?
N42 C37 C38 119.1(4) . . ?
C37 C38 H38 120.3 . . ?
C37 C38 C39 119.4(4) . . ?
C39 C38 H38 120.3 . . ?
C38 C39 H39 120.2 . . ?
C40 C39 C38 119.7(4) . . ?
C40 C39 H39 120.2 . . ?
C39 C40 H40 120.3 . . ?
C41 C40 C39 119.5(4) . . ?
C41 C40 H40 120.3 . . ?
C40 C41 H41 119.9 . . ?
N42 C41 C40 120.1(4) . . ?
N42 C41 H41 119.9 . . ?
C37 N42 C43 118.3(4) . . ?
C41 N42 C37 122.2(4) . . ?
C41 N42 C43 119.3(4) . . ?
N42 C43 H43A 110.0 . . ?
N42 C43 H43B 110.0 . . ?
N42 C43 C44 108.5(4) . . ?
H43A C43 H43B 108.4 . . ?
C44 C43 H43A 110.0 . . ?
C44 C43 H43B 110.0 . . ?
N31 C44 C43 109.2(3) . . ?
N31 C44 H44A 109.8 . . ?
N31 C44 H44B 109.8 . . ?
C43 C44 H44A 109.8 . . ?
C43 C44 H44B 109.8 . . ?
H44A C44 H44B 108.3 . . ?
H45A O45 H45B 109(4) . . ?
H46A O46 H46B 106(5) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 C3 C4 C2 1.1(6) . . . 3_666 ?
C2 C3 C4 O5 -178.7(4) . . . . ?
C2 C4 O5 La1 -14.9(4) 3_666 . . 3_666 ?
C3 C2 O1 La1 163.6(3) . . . . ?
C3 C4 O5 La1 165.0(3) . . . 3_666 ?
C4 C2 C3 C4 -1.1(6) 3_666 . . . ?
C4 C2 C3 Cl6 178.9(3) 3_666 . . . ?
C4 C2 O1 La1 -16.3(4) 3_666 . . . ?
Cl6 C3 C4 C2 -178.9(3) . . . 3_666 ?
Cl6 C3 C4 O5 1.2(6) . . . . ?
O7 C8 C9 C10 -177.2(4) . . . . ?
O7 C8 C9 Cl12 -3.0(6) . . . . ?
C8 C9 C10 C8 -1.5(7) . . . 3_767 ?
C8 C9 C10 O11 178.3(4) . . . . ?
C8 C10 O11 La1 24.9(4) 3_767 . . 3_767 ?
C9 C10 O11 La1 -155.0(3) . . . 3_767 ?
C10 C8 C9 C10 1.5(7) 3_767 . . . ?
C10 C8 C9 Cl12 175.6(3) 3_767 . . . ?
La1 O7 C8 C9 -154.2(3) . . . . ?
La1 O7 C8 C10 27.1(4) . . . 3_767 ?
La1 O13 C14 C15 158.4(3) . . . . ?
La1 O13 C14 C16 -21.2(4) . . . 3_667 ?
O1 C2 C3 C4 179.0(4) . . . . ?
O1 C2 C3 Cl6 -0.9(6) . . . . ?
Cl12 C9 C10 C8 -175.6(3) . . . 3_767 ?
Cl12 C9 C10 O11 4.2(6) . . . . ?
O13 C14 C15 C16 174.0(4) . . . . ?
O13 C14 C15 Cl18 -2.9(6) . . . . ?
C14 C15 C16 C14 6.5(6) . . . 3_667 ?
C14 C15 C16 O17 -172.9(4) . . . . ?
C14 C16 O17 La1 -13.4(5) 3_667 . . 3_667 ?
C15 C16 O17 La1 166.0(3) . . . 3_667 ?
C16 C14 C15 C16 -6.4(6) 3_667 . . . ?
C16 C14 C15 Cl18 176.7(3) 3_667 . . . ?
Cl18 C15 C16 C14 -176.6(3) . . . 3_667 ?
Cl18 C15 C16 O17 4.0(6) . . . . ?
C19 C20 C21 C22 3.9(6) . . . . ?
C19 C20 C21 O26 -176.0(4) . . . . ?
C19 C20 O25 La1 178.1(3) . . . 4_575 ?
C19 C24 O28 La1 165.2(3) . . . . ?
C20 C19 C24 C23 6.0(6) . . . . ?
C20 C19 C24 O28 -174.0(4) . . . . ?
C20 C21 C22 C23 1.7(8) . . . . ?
C20 C21 C22 Cl30 -178.2(4) . . . . ?
C20 C21 O26 La1 -4.8(5) . . . 4_575 ?
C21 C20 O25 La1 -2.5(5) . . . 4_575 ?
C21 C22 C23 C24 -3.4(8) . . . . ?
C21 C22 C23 O27 176.1(5) . . . . ?
C22 C21 O26 La1 175.3(4) . . . 4_575 ?
C22 C23 C24 C19 -0.3(6) . . . . ?
C22 C23 C24 O28 179.7(4) . . . . ?
C22 C23 O27 La1 -166.1(4) . . . . ?
C23 C24 O28 La1 -14.9(5) . . . . ?
C24 C19 C20 C21 -7.8(6) . . . . ?
C24 C19 C20 O25 171.5(4) . . . . ?
C24 C23 O27 La1 13.5(5) . . . . ?
O25 C20 C21 C22 -175.5(4) . . . . ?
O25 C20 C21 O26 4.6(6) . . . . ?
O26 C21 C22 C23 -178.4(5) . . . . ?
O26 C21 C22 Cl30 1.7(8) . . . . ?
O27 C23 C24 C19 -179.9(4) . . . . ?
O27 C23 C24 O28 0.1(6) . . . . ?
Cl29 C19 C20 C21 175.0(3) . . . . ?
Cl29 C19 C20 O25 -5.6(6) . . . . ?
Cl29 C19 C24 C23 -176.8(3) . . . . ?
Cl29 C19 C24 O28 3.1(6) . . . . ?
Cl30 C22 C23 C24 176.4(4) . . . . ?
Cl30 C22 C23 O27 -4.0(8) . . . . ?
N31 C32 C33 C34 -1.7(6) . . . . ?
N31 C36 C37 C38 160.6(4) . . . . ?
N31 C36 C37 N42 -17.9(6) . . . . ?
C32 N31 C36 C35 -0.8(6) . . . . ?
C32 N31 C36 C37 -177.1(4) . . . . ?
C32 N31 C44 C43 -144.3(4) . . . . ?
C32 C33 C34 C35 -1.3(6) . . . . ?
C33 C34 C35 C36 3.3(6) . . . . ?
C34 C35 C36 N31 -2.2(6) . . . . ?
C34 C35 C36 C37 173.9(4) . . . . ?
C35 C36 C37 C38 -15.5(6) . . . . ?
C35 C36 C37 N42 166.0(4) . . . . ?
C36 N31 C32 C33 2.9(6) . . . . ?
C36 N31 C44 C43 38.5(5) . . . . ?
C36 C37 C38 C39 179.5(4) . . . . ?
C36 C37 N42 C41 177.9(4) . . . . ?
C36 C37 N42 C43 -6.2(5) . . . . ?
C37 C38 C39 C40 2.9(6) . . . . ?
C37 N42 C43 C44 44.5(5) . . . . ?
C38 C37 N42 C41 -0.7(6) . . . . ?
C38 C37 N42 C43 175.2(4) . . . . ?
C38 C39 C40 C41 -1.2(7) . . . . ?
C39 C40 C41 N42 -1.5(6) . . . . ?
C40 C41 N42 C37 2.5(6) . . . . ?
C40 C41 N42 C43 -173.4(4) . . . . ?
C41 N42 C43 C44 -139.4(4) . . . . ?
N42 C37 C38 C39 -1.9(6) . . . . ?
N42 C43 C44 N31 -58.9(5) . . . . ?
C44 N31 C32 C33 -174.2(4) . . . . ?
C44 N31 C36 C35 176.2(4) . . . . ?
C44 N31 C36 C37 -0.1(6) . . . . ?

_platon_squeeze_details          ?
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.288 0.719 0.104 27 9 '2 H2O'
2 0.577 0.699 0.205 15 2 ' '
3 0.436 0.199 0.300 16 2 ' '
4 0.720 0.220 0.398 25 9 ' '
5 0.288 0.781 0.604 27 9 '2 H2O'
6 0.577 0.801 0.705 15 2 ' '
7 0.436 0.301 0.800 16 2 ' '
8 0.720 0.280 0.898 25 9 ' '

_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.637
_oxdiff_exptl_absorpt_empirical_full_min 0.651
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mf-1-34b_1p25-mask_smrt_abs_twin_twin1_hklf5_a
_database_code_depnum_ccdc_archive 'CCDC 2415092'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_audit_creation_date             2024-05-01
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C15 H6 Br4 La O9, 0.5(C14 H12 N2), 2(C3 H6 O)'
_chemical_formula_sum            'C28 H24 Br4 La N O11'
_chemical_formula_weight         1009.03
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C28 H24 Br4 La N O11 '
_chemical_oxdiff_usercomment     'rectangle, purpleish'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   10.8019(4)
_cell_length_b                   12.6028(5)
_cell_length_c                   13.3338(5)
_cell_angle_alpha                109.799(3)
_cell_angle_beta                 90.154(3)
_cell_angle_gamma                108.366(3)
_cell_volume                     1608.68(11)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9579
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      78.5960
_cell_measurement_theta_min      13.1340
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    16.604
_exptl_absorpt_correction_T_max  0.614
_exptl_absorpt_correction_T_min  0.194
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.083
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             968
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
6 1 2 0.0180
-6 -1 -2 0.0200
2 -8 4 0.0802
-2 8 -5 0.0933
-5 7 -5 0.0830
-5 -1 6 0.0102
5 1 -6 0.0314
2 5 2 0.0593
0 -4 -5 0.0644
2 0 8 0.0151
-2 0 -7 0.0241

_exptl_crystal_size_max          0.192
_exptl_crystal_size_mid          0.048
_exptl_crystal_size_min          0.039
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
5.6103 0.9682 2.4533 -0.1167 -0.4852 0.8666
-5.5943 -1.0235 -2.4216 0.1153 0.4793 -0.8700
1.7231 -8.0473 4.2980 -0.1887 -0.7900 -0.5834
-2.1631 8.0113 -4.5073 0.1986 0.8311 0.5195
-4.6586 6.6048 -5.1841 0.2326 0.9720 0.0347
-4.7921 -0.8031 6.3001 -0.8741 0.2087 -0.4386
4.8786 1.0606 -6.1416 0.8508 -0.2030 0.4846
2.4951 5.0500 1.9084 -0.2894 0.0704 0.9546
-0.0823 -4.4285 -4.8371 0.6946 -0.1671 -0.6997
1.5727 -0.2614 7.7378 -0.8333 -0.3454 0.4315
-1.8294 -0.1654 -7.4130 0.7998 0.3315 -0.5004

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  ?
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12428
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.057
_diffrn_reflns_theta_min         3.550
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     86.00 111.00   0.50    0.20    --  113.25-125.00-180.00   50
  2  ω     48.00  74.00   0.50    0.20    --  113.25-125.00-180.00   52
  3  ω     52.00 109.00   0.50    0.20    --  113.25-125.00 -60.00  114
  4  ω     55.00 106.00   0.50    0.20    --  113.25-105.00  58.77  102
  5  ω     45.00  82.00   0.50    0.20    --  113.25-125.00 120.00   74
  6  ω     48.00  92.00   0.50    0.20    --  113.25-125.00  60.00   88
  7  ω     65.00 106.00   0.50    0.20    --  113.25-102.00 -39.00   82
  8  ω     81.00 106.00   0.50    0.20    --  113.25 -94.00-150.00   50
  9  ω     42.00  77.00   0.50    0.20    --  113.25 -94.00-150.00   70
 10  ω     53.00 107.00   0.50    0.20    --  113.25-103.00-172.15  108
 11  ω      9.00  74.00   0.50    0.10    --   47.26-102.00 -39.00  130
 12  ω     58.00  91.00   0.50    0.20    --  113.25 -94.00   0.00   66
 13  ω     73.00 106.00   0.50    0.20    --  113.25 -94.00  60.00   66
 14  ω     71.00 104.00   0.50    0.20    --  113.25 -94.00  90.00   66
 15  ω     43.00  68.00   0.50    0.20    --  113.25 -61.00  90.00   50
 16  ω     43.00  70.00   0.50    0.20    --  113.25 -61.00 -30.00   54
 17  ω     67.00  92.00   0.50    0.20    --  113.25 -77.00 -60.00   50
 18  ω     47.00  91.00   0.50    0.20    --  113.25 -77.00 -90.00   88
 19  ω     42.00  67.00   0.50    0.20    --  113.25 -61.00-150.00   50
 20  ω    124.00 166.00   0.50    0.20    --  113.25  15.00 -90.00   84
 21  ω    137.00 171.00   0.50    0.20    --  113.25  15.00-150.00   68
 22  ω    105.00 165.00   0.50    0.20    --  113.25  30.00   0.00  120
 23  ω    100.00 127.00   0.50    0.20    --  113.25  15.00-150.00   54
 24  ω     43.00 116.00   0.50    0.10    --   47.26  38.00  90.00  146
 25  ω    127.00 152.00   0.50    0.20    --  113.25  45.00 120.00   50
 26  ω     99.00 172.00   0.50    0.20    --  113.25  77.00  90.00  146
 27  ω    138.00 165.00   0.50    0.20    --  113.25 102.00  63.00   54
 28  ω     95.00 151.00   0.50    0.20    --  113.25 125.00   0.00  112
 29  ω     95.00 159.00   0.50    0.20    --  113.25 125.00 -30.00  128
 30  ω    103.00 177.00   0.50    0.20    --  113.25 125.00 -90.00  148
 31  ω    -43.00  15.00   0.50    0.10    --  -47.26  38.00  30.00  116
 32  ω    -21.00  21.00   0.50    0.10    --  -47.26  19.00 150.00   84
 33  ω    -21.00  28.00   0.50    0.10    --  -47.26  19.00  90.00   98
 34  ω    -41.00  10.00   0.50    0.10    --  -47.26 102.00  63.00  102
 35  ω    -72.00 -46.00   0.50    0.10    --  -47.26 102.00  63.00   52
 36  ω    -75.00 -50.00   0.50    0.20    --  -91.75 102.00  63.00   50
 37  ω    -63.00 -23.00   0.50    0.20    --  -91.75  61.00  60.00   80
 38  ω    -50.00 -20.00   0.50    0.20    --  -91.75  45.00   0.00   60
 39  ω    -51.00 -24.00   0.50    0.20    --  -91.75  45.00 -90.00   54
 40  ω    -46.00 -20.00   0.50    0.20    --  -91.75  45.00-150.00   52
 41  ω   -156.00-129.00   0.50    0.20    --  -91.75-102.00 -39.00   54
 42  ω   -116.00 -48.00   0.50    0.10    --  -47.26 -38.00 -30.00  136
 43  ω   -113.00 -86.00   0.50    0.20    --  -91.75-102.00 -39.00   54
 44  ω   -161.00-105.00   0.50    0.20    --  -91.75 -61.00  30.00  112
 45  ω   -141.00 -80.00   0.50    0.20    --  -91.75 -30.00  60.00  122
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0352168000
_diffrn_orient_matrix_UB_12      -0.0309126000
_diffrn_orient_matrix_UB_13      -0.1158984000
_diffrn_orient_matrix_UB_21      -0.0871257000
_diffrn_orient_matrix_UB_22      0.0663231000
_diffrn_orient_matrix_UB_23      -0.0246952000
_diffrn_orient_matrix_UB_31      0.1187237000
_diffrn_orient_matrix_UB_32      0.1169217000
_diffrn_orient_matrix_UB_33      0.0355903000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                11705
_reflns_number_total             12428
_reflns_special_details          
;
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         2.731
_refine_diff_density_min         -2.753
_refine_diff_density_rms         0.312
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.370
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         12428
_refine_ls_number_restraints     353
_refine_ls_R_factor_all          0.1037
_refine_ls_R_factor_gt           0.1017
_refine_ls_restrained_S_all      1.352
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2876
_refine_ls_wR_factor_ref         0.2919
_refine_special_details          
;
 Refined as a 2-component twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.411(3)
 0.589(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C38-C39
 1.35 with sigma of 0.02
 C31-C38 = C39-C40
 1.43 with sigma of 0.02
 C35-C36
 1.51 with sigma of 0.02
 N33-C35 = N37-C36
 1.48 with sigma of 0.02
 C30-H30 = C34-H34
 0.95 with sigma of 0.0001
 C30-N37_$1 \\sim C34-N33 \\sim C30_$1-N37 \\sim C34_$1-N33_$1
 with sigma of 0.02
 N33-C32 \\sim C32-N37_$1 \\sim C32_$1-N37 \\sim C32_$1-N33_$1
 with sigma of 0.02
 C30-C31 \\sim C34-C40_$1 \\sim C30_$1-C31_$1 \\sim C34_$1-C40
 with sigma of 0.02
 O45A-C47A \\sim O45A-C47B
 with sigma of 0.01
 C46A-C47A \\sim C47A-C48A \\sim C46B-C47B \\sim C47B-C48B
 with sigma of 0.02
 O45A-C46A \\sim O45B-C46B \\sim O45A-C48A \\sim O45B-C48B
 with sigma of 0.04
4. Restrained planarity
 C42, C43, O41, C44
 with sigma of 0.1
 O45A, C46A, C47A, C48A
 with sigma of 0.1
 O45B, C46B, C47B, C48B
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C32 \\sim C34 \\sim C31 \\sim N33 \\sim C35 \\sim C39 \\sim
C36 \\sim N37 \\sim C38 \\sim C40: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(C31) = Uanis(N37)
Uanis(C40) = Uanis(N33)
Uanis(C38) = Uanis(C36)
Uanis(C35) = Uanis(C39)
6. Rigid body (RIGU) restrains
 C42, C43, C44, O41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O19, C20, C21, C22, O23, Br24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, C14, C15, C16, O17, Br18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O7, C8, C9, C10, O11, Br12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2, C3, C4, O5, Br6, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C30, C32, C34, C31, N33, C35, C39, C36, N37, C38, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O45A, C46A, C47A, C48A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O45B, C46B, C47B, C48B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(O45B)=Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47B)=Sof(C48B)=
 Sof(H48D)=Sof(H48E)=Sof(H48F)=1-FVAR(1)
 Sof(O45A)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47A)=Sof(C48A)=
 Sof(H48A)=Sof(H48B)=Sof(H48C)=FVAR(1)
 Fixed Sof: C31(0.5) N33(0.5) C35(0.5) H35A(0.5) H35B(0.5) C36(0.5) H36A(0.5)
 H36B(0.5) N37(0.5) C38(0.5) H38(0.5) C39(0.5) H39(0.5) C40(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C36(H36A,H36B)
8.b Aromatic/amide H refined with riding coordinates:
 C38(H38), C39(H39), C29(H29)
8.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C42(H42A,H42B,H42C), C44(H44A,H44B,
 H44C), C46A(H46A,H46B,H46C), C48A(H48A,H48B,H48C), C46B(H46D,H46E,H46F),
 C48B(H48D,H48E,H48F)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C31 C 0.068(5) 0.146(6) 0.614(7) 0.031(9) Uani 0.5 1 d D U P A -1
N33 N 0.162(4) -0.008(2) 0.538(3) 0.052(9) Uani 0.5 1 d D U P A -1
C35 C 0.116(3) -0.1407(19) 0.492(2) 0.040(3) Uani 0.5 1 d D U P A -1
H35A H 0.062102 -0.172735 0.541303 0.048 Uiso 0.5 1 calc R U P A -1
H35B H 0.193912 -0.167461 0.485914 0.048 Uiso 0.5 1 calc R U P A -1
C36 C 0.037(4) -0.193(6) 0.382(4) 0.036(4) Uani 0.5 1 d D U P A -1
H36A H 0.089263 -0.161763 0.330925 0.043 Uiso 0.5 1 calc R U P A -1
H36B H 0.010431 -0.280971 0.354261 0.043 Uiso 0.5 1 calc R U P A -1
N37 N -0.080(4) -0.153(5) 0.399(6) 0.031(9) Uani 0.5 1 d D U P A -1
C38 C -0.047(4) 0.181(6) 0.616(4) 0.036(4) Uani 0.5 1 d D U P A -1
H38 H -0.037442 0.260385 0.661821 0.043 Uiso 0.5 1 calc R U P A -1
C39 C -0.167(3) 0.114(2) 0.560(2) 0.040(3) Uani 0.5 1 d D U P A -1
H39 H -0.240226 0.140724 0.566713 0.048 Uiso 0.5 1 calc R U P A -1
C40 C -0.172(6) -0.002(3) 0.490(4) 0.052(9) Uani 0.5 1 d D U P A -1
La1 La 0.70133(4) 0.38562(4) 0.21167(4) 0.0199(3) Uani 1 1 d . . . . .
O1 O 1.2395(7) 0.6340(6) 0.6107(6) 0.0257(14) Uani 1 1 d . . . . .
C2 C 1.1322(9) 0.5706(9) 0.5530(9) 0.0244(18) Uani 1 1 d . . . . .
C3 C 1.1040(9) 0.5505(9) 0.4449(8) 0.0229(18) Uani 1 1 d . . . . .
C4 C 0.9771(10) 0.4880(9) 0.3888(9) 0.0247(18) Uani 1 1 d . . . . .
O5 O 0.9426(7) 0.4759(7) 0.2949(6) 0.0246(14) Uani 1 1 d . . . . .
Br6 Br 1.24268(10) 0.61615(10) 0.37260(9) 0.0282(3) Uani 1 1 d . . . . .
O7 O 1.1646(7) 0.6743(6) -0.0573(6) 0.0258(14) Uani 1 1 d . . . . .
C8 C 1.0847(9) 0.5971(9) -0.0275(8) 0.0210(17) Uani 1 1 d . . . . .
C9 C 0.9920(9) 0.6186(9) 0.0435(9) 0.0223(18) Uani 1 1 d . . . . .
C10 C 0.9086(9) 0.5295(9) 0.0741(8) 0.0209(17) Uani 1 1 d . . . . .
O11 O 0.8237(7) 0.5426(6) 0.1380(6) 0.0251(14) Uani 1 1 d . . . . .
Br12 Br 0.98192(10) 0.77479(9) 0.10100(9) 0.0268(3) Uani 1 1 d . . . . .
O13 O 0.4704(7) -0.2330(6) -0.0573(7) 0.0263(14) Uani 1 1 d . . . . .
C14 C 0.4910(9) -0.1241(9) -0.0271(8) 0.0222(17) Uani 1 1 d . . . . .
C15 C 0.5850(9) -0.0356(9) 0.0555(9) 0.0238(18) Uani 1 1 d . . . . .
C16 C 0.5977(9) 0.0852(9) 0.0893(8) 0.0229(18) Uani 1 1 d . . . . .
O17 O 0.6737(7) 0.1681(7) 0.1677(6) 0.0259(14) Uani 1 1 d . . . . .
Br18 Br 0.69231(11) -0.08315(10) 0.13155(10) 0.0328(3) Uani 1 1 d . . . . .
O19 O 0.3142(7) 0.4472(6) 0.6267(6) 0.0253(14) Uani 1 1 d . . . . .
C20 C 0.3959(9) 0.4658(8) 0.5627(8) 0.0207(17) Uani 1 1 d . . . . .
C21 C 0.3946(9) 0.3874(9) 0.4601(9) 0.0237(19) Uani 1 1 d . . . . .
C22 C 0.4915(9) 0.4130(9) 0.3955(9) 0.0231(18) Uani 1 1 d . . . . .
O23 O 0.4965(7) 0.3437(6) 0.3035(6) 0.0253(14) Uani 1 1 d . . . . .
Br24 Br 0.25263(11) 0.24211(10) 0.40648(10) 0.0362(3) Uani 1 1 d . . . . .
O25 O 0.5508(7) 0.4978(7) 0.1613(7) 0.0287(15) Uani 1 1 d . . . . .
C26 C 0.4161(12) 0.5921(14) 0.1111(12) 0.041(3) Uani 1 1 d . . . . .
H26A H 0.367672 0.629425 0.166434 0.062 Uiso 1 1 calc R U . . .
H26B H 0.364577 0.561542 0.040502 0.062 Uiso 1 1 calc R U . . .
H26C H 0.500576 0.651656 0.111779 0.062 Uiso 1 1 calc R U . . .
C27 C 0.4393(11) 0.4917(11) 0.1332(9) 0.031(2) Uani 1 1 d . . . . .
C28 C 0.3237(12) 0.3830(13) 0.1225(14) 0.050(4) Uani 1 1 d . . . . .
H28A H 0.254593 0.407677 0.161214 0.075 Uiso 1 1 calc R U . . .
H28B H 0.350876 0.331881 0.152838 0.075 Uiso 1 1 calc R U . . .
H28C H 0.290096 0.338456 0.046399 0.075 Uiso 1 1 calc R U . . .
C29 C 0.2947(16) 0.1817(14) 0.6565(14) 0.050(3) Uani 1 1 d . U . . .
H29 H 0.377224 0.233035 0.696944 0.060 Uiso 1 1 calc R U . . .
C30 C 0.1922(10) 0.2205(4) 0.6685(7) 0.038(2) Uani 1 1 d D U . . .
H30 H 0.1998(18) 0.2997(5) 0.7130(13) 0.045 Uiso 1 1 d D U . . .
C32 C 0.0603(15) 0.0366(12) 0.5321(12) 0.045(3) Uani 1 1 d D U . . .
C34 C 0.2834(4) 0.0686(6) 0.5864(13) 0.068(5) Uani 1 1 d D U . . .
H34 H 0.3580(5) 0.0436(7) 0.573(4) 0.082 Uiso 1 1 d D U . . .
O41 O 0.418(3) -0.0913(19) 0.356(2) 0.20(2) Uani 1 1 d . . . . .
C42 C 0.3359(15) -0.039(2) 0.2250(16) 0.073(6) Uani 1 1 d . . . . .
H42A H 0.380705 0.014262 0.187248 0.109 Uiso 1 1 calc R U . . .
H42B H 0.254975 -0.023238 0.247079 0.109 Uiso 1 1 calc R U . . .
H42C H 0.314191 -0.122409 0.176937 0.109 Uiso 1 1 calc R U . . .
C43 C 0.4239(15) -0.0164(19) 0.3217(17) 0.068(5) Uani 1 1 d . . . . .
C44 C 0.5214(14) 0.1054(14) 0.3747(15) 0.050(3) Uani 1 1 d . . . . .
H44A H 0.593239 0.117973 0.330665 0.075 Uiso 1 1 calc R U . . .
H44B H 0.556577 0.113253 0.445646 0.075 Uiso 1 1 calc R U . . .
H44C H 0.478623 0.165347 0.382747 0.075 Uiso 1 1 calc R U . . .
O45A O 0.005(2) 0.040(3) 0.250(3) 0.047(6) Uani 0.55(4) 1 d D . P B 1
C46A C 0.128(3) 0.084(2) 0.113(2) 0.044(6) Uani 0.55(4) 1 d D . P B 1
H46A H 0.114966 -0.002037 0.079841 0.066 Uiso 0.55(4) 1 calc R U P B 1
H46B H 0.218351 0.126993 0.147432 0.066 Uiso 0.55(4) 1 calc R U P B 1
H46C H 0.110166 0.113791 0.057663 0.066 Uiso 0.55(4) 1 calc R U P B 1
C47A C 0.034(2) 0.102(2) 0.196(2) 0.043(6) Uani 0.55(4) 1 d D . P B 1
C48A C -0.018(3) 0.203(2) 0.210(3) 0.054(8) Uani 0.55(4) 1 d D . P B 1
H48A H -0.082193 0.181332 0.147908 0.082 Uiso 0.55(4) 1 calc R U P B 1
H48B H 0.055057 0.275322 0.214328 0.082 Uiso 0.55(4) 1 calc R U P B 1
H48C H -0.060122 0.219054 0.275630 0.082 Uiso 0.55(4) 1 calc R U P B 1
O45B O 0.005(2) 0.020(2) 0.281(2) 0.029(5) Uani 0.45(4) 1 d D . P B 2
C46B C 0.053(5) 0.105(3) 0.146(3) 0.055(10) Uani 0.45(4) 1 d D . P B 2
H46D H -0.001260 0.035233 0.085976 0.083 Uiso 0.45(4) 1 calc R U P B 2
H46E H 0.144236 0.107309 0.147819 0.083 Uiso 0.45(4) 1 calc R U P B 2
H46F H 0.048128 0.178302 0.137850 0.083 Uiso 0.45(4) 1 calc R U P B 2
C47B C 0.003(2) 0.098(3) 0.250(2) 0.038(7) Uani 0.45(4) 1 d D . P B 2
C48B C -0.051(3) 0.194(2) 0.313(3) 0.040(7) Uani 0.45(4) 1 d D . P B 2
H48D H -0.112814 0.203143 0.264278 0.060 Uiso 0.45(4) 1 calc R U P B 2
H48E H 0.020929 0.270240 0.344771 0.060 Uiso 0.45(4) 1 calc R U P B 2
H48F H -0.097619 0.171976 0.369468 0.060 Uiso 0.45(4) 1 calc R U P B 2


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C31 C38 1.43(2) . ?
C31 C30 1.40(5) . ?
C31 C32 1.42(6) . ?
N33 C35 1.48(2) . ?
N33 C32 1.40(4) . ?
N33 C34 1.36(4) . ?
C35 H35A 0.9900 . ?
C35 H35B 0.9900 . ?
C35 C36 1.51(3) . ?
C36 H36A 0.9900 . ?
C36 H36B 0.9900 . ?
C36 N37 1.48(2) . ?
C38 H38 0.9500 . ?
C38 C39 1.35(3) . ?
C39 H39 0.9500 . ?
C39 C40 1.43(2) . ?
La1 O1 2.562(8) 2_766 ?
La1 O5 2.565(7) . ?
La1 O7 2.560(7) 2_765 ?
La1 O11 2.510(7) . ?
La1 O13 2.535(8) 2_655 ?
La1 O17 2.519(7) . ?
La1 O19 2.502(8) 2_666 ?
La1 O23 2.528(7) . ?
La1 O25 2.680(7) . ?
O1 C2 1.252(13) . ?
C2 C3 1.391(15) . ?
C2 C4 1.545(14) 2_766 ?
C3 C4 1.405(14) . ?
C3 Br6 1.904(10) . ?
C4 O5 1.249(13) . ?
O7 C8 1.259(12) . ?
C8 C9 1.406(14) . ?
C8 C10 1.530(13) 2_765 ?
C9 C10 1.383(14) . ?
C9 Br12 1.894(10) . ?
C10 O11 1.264(13) . ?
O13 C14 1.236(13) . ?
C14 C15 1.391(15) . ?
C14 C16 1.555(13) 2_655 ?
C15 C16 1.394(14) . ?
C15 Br18 1.890(9) . ?
C16 O17 1.254(13) . ?
O19 C20 1.253(12) . ?
C20 C21 1.387(15) . ?
C20 C22 1.540(13) 2_666 ?
C21 C22 1.387(14) . ?
C21 Br24 1.885(10) . ?
C22 O23 1.255(13) . ?
O25 C27 1.231(14) . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?
C26 H26C 0.9800 . ?
C26 C27 1.485(17) . ?
C27 C28 1.497(18) . ?
C28 H28A 0.9800 . ?
C28 H28B 0.9800 . ?
C28 H28C 0.9800 . ?
C29 H29 0.9500 . ?
C29 C30 1.333(19) . ?
C29 C34 1.381(19) . ?
C30 H30 0.95000(17) . ?
C32 C32 1.41(3) 2_556 ?
C34 H34 0.9500(2) . ?
O41 C43 1.17(2) . ?
C42 H42A 0.9800 . ?
C42 H42B 0.9800 . ?
C42 H42C 0.9800 . ?
C42 C43 1.49(2) . ?
C43 C44 1.49(3) . ?
C44 H44A 0.9800 . ?
C44 H44B 0.9800 . ?
C44 H44C 0.9800 . ?
O45A C47A 1.20(4) . ?
C46A H46A 0.9800 . ?
C46A H46B 0.9800 . ?
C46A H46C 0.9800 . ?
C46A C47A 1.52(2) . ?
C47A C48A 1.51(2) . ?
C48A H48A 0.9800 . ?
C48A H48B 0.9800 . ?
C48A H48C 0.9800 . ?
O45B C47B 1.20(4) . ?
C46B H46D 0.9800 . ?
C46B H46E 0.9800 . ?
C46B H46F 0.9800 . ?
C46B C47B 1.51(3) . ?
C47B C48B 1.51(3) . ?
C48B H48D 0.9800 . ?
C48B H48E 0.9800 . ?
C48B H48F 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C30 C31 C38 126(4) . . ?
C30 C31 C32 117(3) . . ?
C32 C31 C38 116(4) . . ?
C32 N33 C35 112(3) . . ?
C34 N33 C35 128(3) . . ?
C34 N33 C32 119.9(18) . . ?
N33 C35 H35A 108.9 . . ?
N33 C35 H35B 108.9 . . ?
N33 C35 C36 114(3) . . ?
H35A C35 H35B 107.7 . . ?
C36 C35 H35A 108.9 . . ?
C36 C35 H35B 108.9 . . ?
C35 C36 H36A 110.7 . . ?
C35 C36 H36B 110.7 . . ?
H36A C36 H36B 108.8 . . ?
N37 C36 C35 105(4) . . ?
N37 C36 H36A 110.7 . . ?
N37 C36 H36B 110.7 . . ?
C31 C38 H38 116.4 . . ?
C39 C38 C31 127(4) . . ?
C39 C38 H38 116.4 . . ?
C38 C39 H39 123.3 . . ?
C38 C39 C40 113(4) . . ?
C40 C39 H39 123.3 . . ?
O1 La1 O5 61.4(2) 2_766 . ?
O1 La1 O25 131.7(2) 2_766 . ?
O5 La1 O25 127.8(2) . . ?
O7 La1 O1 117.9(2) 2_765 2_766 ?
O7 La1 O5 73.9(2) 2_765 . ?
O7 La1 O25 109.3(2) 2_765 . ?
O11 La1 O1 127.8(2) . 2_766 ?
O11 La1 O5 70.5(2) . . ?
O11 La1 O7 62.3(2) . 2_765 ?
O11 La1 O13 104.0(2) . 2_655 ?
O11 La1 O17 134.5(3) . . ?
O11 La1 O23 136.2(2) . . ?
O11 La1 O25 66.8(2) . . ?
O13 La1 O1 127.5(2) 2_655 2_766 ?
O13 La1 O5 148.2(2) 2_655 . ?
O13 La1 O7 76.0(2) 2_655 2_765 ?
O13 La1 O25 72.4(2) 2_655 . ?
O17 La1 O1 74.0(2) . 2_766 ?
O17 La1 O5 98.3(2) . . ?
O17 La1 O7 72.2(2) . 2_765 ?
O17 La1 O13 62.5(2) . 2_655 ?
O17 La1 O23 85.9(2) . . ?
O17 La1 O25 133.1(2) . . ?
O19 La1 O1 66.8(2) 2_666 2_766 ?
O19 La1 O5 80.6(2) 2_666 . ?
O19 La1 O7 145.2(2) 2_666 2_765 ?
O19 La1 O11 87.2(2) 2_666 . ?
O19 La1 O13 131.0(2) 2_666 2_655 ?
O19 La1 O17 135.8(2) 2_666 . ?
O19 La1 O23 63.1(2) 2_666 . ?
O19 La1 O25 68.9(2) 2_666 . ?
O23 La1 O1 71.2(2) . 2_766 ?
O23 La1 O5 128.8(2) . . ?
O23 La1 O7 151.4(2) . 2_765 ?
O23 La1 O13 77.6(2) . 2_655 ?
O23 La1 O25 72.5(2) . . ?
C2 O1 La1 122.2(6) . 2_766 ?
O1 C2 C3 126.4(9) . . ?
O1 C2 C4 114.8(9) . 2_766 ?
C3 C2 C4 118.8(9) . 2_766 ?
C2 C3 C4 122.7(9) . . ?
C2 C3 Br6 118.1(7) . . ?
C4 C3 Br6 119.1(8) . . ?
C3 C4 C2 118.2(9) . 2_766 ?
O5 C4 C2 115.8(9) . 2_766 ?
O5 C4 C3 126.0(9) . . ?
C4 O5 La1 122.6(6) . . ?
C8 O7 La1 121.4(6) . 2_765 ?
O7 C8 C9 125.3(9) . . ?
O7 C8 C10 115.9(9) . 2_765 ?
C9 C8 C10 118.8(9) . 2_765 ?
C8 C9 Br12 119.2(7) . . ?
C10 C9 C8 122.1(9) . . ?
C10 C9 Br12 118.7(8) . . ?
C9 C10 C8 119.1(9) . 2_765 ?
O11 C10 C8 115.4(8) . 2_765 ?
O11 C10 C9 125.5(9) . . ?
C10 O11 La1 123.3(6) . . ?
C14 O13 La1 123.3(6) . 2_655 ?
O13 C14 C15 126.3(9) . . ?
O13 C14 C16 115.5(9) . 2_655 ?
C15 C14 C16 118.2(9) . 2_655 ?
C14 C15 C16 123.1(9) . . ?
C14 C15 Br18 118.2(7) . . ?
C16 C15 Br18 118.5(7) . . ?
C15 C16 C14 118.5(9) . 2_655 ?
O17 C16 C14 115.1(9) . 2_655 ?
O17 C16 C15 126.3(9) . . ?
C16 O17 La1 123.3(6) . . ?
C20 O19 La1 121.4(6) . 2_666 ?
O19 C20 C21 126.2(9) . . ?
O19 C20 C22 115.8(9) . 2_666 ?
C21 C20 C22 118.0(9) . 2_666 ?
C20 C21 Br24 118.0(7) . . ?
C22 C21 C20 122.7(9) . . ?
C22 C21 Br24 119.3(8) . . ?
C21 C22 C20 119.3(9) . 2_666 ?
O23 C22 C20 115.8(9) . 2_666 ?
O23 C22 C21 124.9(9) . . ?
C22 O23 La1 120.8(6) . . ?
C27 O25 La1 146.6(8) . . ?
H26A C26 H26B 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
C27 C26 H26A 109.5 . . ?
C27 C26 H26B 109.5 . . ?
C27 C26 H26C 109.5 . . ?
O25 C27 C26 121.0(11) . . ?
O25 C27 C28 120.4(11) . . ?
C26 C27 C28 118.6(10) . . ?
C27 C28 H28A 109.5 . . ?
C27 C28 H28B 109.5 . . ?
C27 C28 H28C 109.5 . . ?
H28A C28 H28B 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
C30 C29 H29 119.3 . . ?
C30 C29 C34 121.5(12) . . ?
C34 C29 H29 119.3 . . ?
C31 C30 H30 116(3) . . ?
N37 C30 C31 10(8) 2_556 . ?
N37 C30 H30 118(2) 2_556 . ?
C29 C30 C31 121(2) . . ?
C29 C30 N37 119.0(19) . 2_556 ?
C29 C30 H30 122.3(16) . . ?
N33 C32 C31 117(2) . . ?
N33 C32 C40 18(3) . 2_556 ?
N33 C32 C32 121.5(17) . 2_556 ?
N37 C32 C31 10(8) 2_556 . ?
N37 C32 N33 116(3) 2_556 . ?
N37 C32 C40 117.5(17) 2_556 2_556 ?
N37 C32 C32 121.8(17) 2_556 2_556 ?
C40 C32 C31 121(3) 2_556 . ?
C32 C32 C31 119(2) 2_556 . ?
C32 C32 C40 119(2) 2_556 2_556 ?
N33 C34 C40 18(4) . 2_556 ?
N33 C34 C29 118.4(17) . . ?
N33 C34 H34 120.1(19) . . ?
C40 C34 H34 116(3) 2_556 . ?
C29 C34 C40 119.6(17) . 2_556 ?
C29 C34 H34 121.5(14) . . ?
H42A C42 H42B 109.5 . . ?
H42A C42 H42C 109.5 . . ?
H42B C42 H42C 109.5 . . ?
C43 C42 H42A 109.5 . . ?
C43 C42 H42B 109.5 . . ?
C43 C42 H42C 109.5 . . ?
O41 C43 C42 122(2) . . ?
O41 C43 C44 119.7(16) . . ?
C44 C43 C42 118.3(17) . . ?
C43 C44 H44A 109.5 . . ?
C43 C44 H44B 109.5 . . ?
C43 C44 H44C 109.5 . . ?
H44A C44 H44B 109.5 . . ?
H44A C44 H44C 109.5 . . ?
H44B C44 H44C 109.5 . . ?
H46A C46A H46B 109.5 . . ?
H46A C46A H46C 109.5 . . ?
H46B C46A H46C 109.5 . . ?
C47A C46A H46A 109.5 . . ?
C47A C46A H46B 109.5 . . ?
C47A C46A H46C 109.5 . . ?
O45A C47A C46A 122(2) . . ?
O45A C47A C48A 122(3) . . ?
C48A C47A C46A 116(3) . . ?
C47A C48A H48A 109.5 . . ?
C47A C48A H48B 109.5 . . ?
C47A C48A H48C 109.5 . . ?
H48A C48A H48B 109.5 . . ?
H48A C48A H48C 109.5 . . ?
H48B C48A H48C 109.5 . . ?
H46D C46B H46E 109.5 . . ?
H46D C46B H46F 109.5 . . ?
H46E C46B H46F 109.5 . . ?
C47B C46B H46D 109.5 . . ?
C47B C46B H46E 109.5 . . ?
C47B C46B H46F 109.5 . . ?
O45B C47B C46B 122(3) . . ?
O45B C47B C48B 122(3) . . ?
C48B C47B C46B 116(4) . . ?
C47B C48B H48D 109.5 . . ?
C47B C48B H48E 109.5 . . ?
C47B C48B H48F 109.5 . . ?
H48D C48B H48E 109.5 . . ?
H48D C48B H48F 109.5 . . ?
H48E C48B H48F 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C31 C38 C39 C40 -3(10) . . . . ?
N33 C35 C36 N37 -61(6) . . . . ?
C35 N33 C32 C31 149(5) . . . . ?
C35 N33 C32 N37 160(5) . . . 2_556 ?
C35 N33 C32 C40 -102(8) . . . 2_556 ?
C35 N33 C32 C32 -13(4) . . . 2_556 ?
C35 N33 C34 C40 104(11) . . . 2_556 ?
C35 N33 C34 C29 -157(3) . . . . ?
C38 C31 C30 N37 -96(27) . . . 2_556 ?
C38 C31 C30 C29 -176(7) . . . . ?
C38 C31 C32 N33 -171(6) . . . . ?
C38 C31 C32 N37 100(25) . . . 2_556 ?
C38 C31 C32 C40 169(6) . . . 2_556 ?
C38 C31 C32 C32 -8(10) . . . 2_556 ?
La1 O1 C2 C3 -161.6(8) 2_766 . . . ?
La1 O1 C2 C4 19.3(11) 2_766 . . 2_766 ?
La1 O7 C8 C9 -169.1(8) 2_765 . . . ?
La1 O7 C8 C10 10.8(11) 2_765 . . 2_765 ?
La1 O13 C14 C15 -178.7(8) 2_655 . . . ?
La1 O13 C14 C16 0.9(12) 2_655 . . 2_655 ?
La1 O19 C20 C21 -164.7(8) 2_666 . . . ?
La1 O19 C20 C22 16.2(11) 2_666 . . 2_666 ?
La1 O25 C27 C26 -176.9(9) . . . . ?
La1 O25 C27 C28 4(2) . . . . ?
O1 C2 C3 C4 -173.2(10) . . . . ?
O1 C2 C3 Br6 4.2(14) . . . . ?
C2 C3 C4 C2 -5.9(16) . . . 2_766 ?
C2 C3 C4 O5 173.3(10) . . . . ?
C2 C4 O5 La1 8.2(12) 2_766 . . . ?
C3 C4 O5 La1 -171.0(7) . . . . ?
C4 C2 C3 C4 5.9(16) 2_766 . . . ?
C4 C2 C3 Br6 -176.6(7) 2_766 . . . ?
Br6 C3 C4 C2 176.7(7) . . . 2_766 ?
Br6 C3 C4 O5 -4.2(14) . . . . ?
O7 C8 C9 C10 -178.9(10) . . . . ?
O7 C8 C9 Br12 0.3(14) . . . . ?
C8 C9 C10 C8 -1.2(16) . . . 2_765 ?
C8 C9 C10 O11 179.6(9) . . . . ?
C8 C10 O11 La1 10.7(11) 2_765 . . . ?
C9 C10 O11 La1 -170.1(7) . . . . ?
C10 C8 C9 C10 1.2(16) 2_765 . . . ?
C10 C8 C9 Br12 -179.6(7) 2_765 . . . ?
Br12 C9 C10 C8 179.6(7) . . . 2_765 ?
Br12 C9 C10 O11 0.4(14) . . . . ?
O13 C14 C15 C16 -176.2(10) . . . . ?
O13 C14 C15 Br18 -0.6(15) . . . . ?
C14 C15 C16 C14 -4.1(16) . . . 2_655 ?
C14 C15 C16 O17 174.7(10) . . . . ?
C14 C16 O17 La1 -6.4(11) 2_655 . . . ?
C15 C16 O17 La1 174.8(8) . . . . ?
C16 C14 C15 C16 4.1(16) 2_655 . . . ?
C16 C14 C15 Br18 179.7(7) 2_655 . . . ?
Br18 C15 C16 C14 -179.7(7) . . . 2_655 ?
Br18 C15 C16 O17 -0.9(14) . . . . ?
O19 C20 C21 C22 -177.7(10) . . . . ?
O19 C20 C21 Br24 3.7(14) . . . . ?
C20 C21 C22 C20 -1.4(16) . . . 2_666 ?
C20 C21 C22 O23 177.9(9) . . . . ?
C20 C22 O23 La1 11.7(11) 2_666 . . . ?
C21 C22 O23 La1 -167.7(8) . . . . ?
C22 C20 C21 C22 1.4(16) 2_666 . . . ?
C22 C20 C21 Br24 -177.2(7) 2_666 . . . ?
Br24 C21 C22 C20 177.2(7) . . . 2_666 ?
Br24 C21 C22 O23 -3.4(15) . . . . ?
C30 C31 C38 C39 176(7) . . . . ?
C30 C31 C32 N33 23(10) . . . . ?
C30 C31 C32 N37 -66(17) . . . 2_556 ?
C30 C31 C32 C40 3(10) . . . 2_556 ?
C30 C31 C32 C32 -174(5) . . . 2_556 ?
C30 C29 C34 N33 -7(3) . . . . ?
C30 C29 C34 C40 14(4) . . . 2_556 ?
C32 C31 C38 C39 11(13) . . . . ?
C32 C31 C30 N37 69(20) . . . 2_556 ?
C32 C31 C30 C29 -11(10) . . . . ?
C32 N33 C35 C36 49(4) . . . . ?
C32 N33 C34 C40 -79(8) . . . 2_556 ?
C32 N33 C34 C29 20(4) . . . . ?
C34 N33 C35 C36 -134(4) . . . . ?
C34 N33 C32 C31 -28(6) . . . . ?
C34 N33 C32 N37 -17(6) . . . 2_556 ?
C34 N33 C32 C40 81(8) . . . 2_556 ?
C34 N33 C32 C32 170(3) . . . 2_556 ?
C34 C29 C30 C31 3(6) . . . . ?
C34 C29 C30 N37 -8(5) . . . 2_556 ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.264
_oxdiff_exptl_absorpt_empirical_full_min 0.357
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
_oxdiff_twin_reflns_isolated
_oxdiff_twin_reflns_overlapped
_twin_individual_twin_lattice_type
_twin_individual_twin_matrix_11
_twin_individual_twin_matrix_12
_twin_individual_twin_matrix_13
_twin_individual_twin_matrix_21
_twin_individual_twin_matrix_22
_twin_individual_twin_matrix_23
_twin_individual_twin_matrix_31
_twin_individual_twin_matrix_32
_twin_individual_twin_matrix_33
1 0.411(3) 5604 13942 ref 1.0000 0.0000 0.0000 0.0000 1.0000 0.0000 0.0000
0.0000 1.0000
2 0.589(3) 5373 13942 nmt 0.9912 -0.0234 0.0029 0.0375 1.0117 0.0054 -0.0188
-0.0075 0.9950

_twin_special_details            
;
Component 2 rotated by 1.7500° 
around [-0.19 0.15 0.97] (reciprocal) or [-0.06 0.43 0.90] (direct)
;
# start Validation Reply Form
_vrf_PLAT084_mf-1-34b_1p25-mask_smrt_abs_twin_twin1_hklf5_a 
;
PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.29 Report
RESPONSE: The quality of the structure refinement is limited due to use of a twinned crystal and residual X-ray absorption due to the heavy La atom. 
;
_vrf_PLAT241_mf-1-34b_1p25-mask_smrt_abs_twin_twin1_hklf5_a 
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of        C34 Check 
RESPONSE: This occurs from positional disorder of the cation about the centre of inversion.
;
_vrf_PLAT244_mf-1-34b_1p25-mask_smrt_abs_twin_twin1_hklf5_a 
;
PROBLEM: Low    'Solvent' Ueq as Compared to Neighbors of        C43 Check 
RESPONSE: This occurs due to putative disorder of the acetone molecule. Refinement of a disorder model for this solvent was attempted with C43 in two positions, however a satisfactory refinement could not be obtained instead leading to NDP at the two possible sites of C43.
;
_vrf_PLAT250_mf-1-34b_1p25-mask_smrt_abs_twin_twin1_hklf5_a 
;
PROBLEM: Large U3/U1 Ratio for <U(i,j)> Tensor(Resd    2)        3.2 Note  
RESPONSE: This occurs from positional disorder of the cation about the centre of inversion.
;
_vrf_PLAT369_mf-1-34b_1p25-mask_smrt_abs_twin_twin1_hklf5_a 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_d     .       1.54 Ang.  
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
# end Validation Reply Form
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mf-1-15b_2_1-mask_smrt_abs_a
_database_code_depnum_ccdc_archive 'CCDC 2415086'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT420_mf-1-15b_2_1-mask_smrt_abs_a 
;
PROBLEM: D-H Bond Without Acceptor  O45      --H45B     .     Please Check
RESPONSE: The refined positions for H atoms of solvent H2O molecules contained i
;
_vrf_PLAT369_mf-1-15b_2_1-mask_smrt_abs_a 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_c     .       1.55 Ang.
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
# Added during the CSD deposition process: Tuesday 07 January 2025 12:07 AM
# end Validation Reply Form

_audit_creation_date             2024-04-17
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C15 Cl5 La O10, C12 H12 N2, 3(H2 O)'
_chemical_formula_sum            'C27 H18 Cl5 La N2 O13'
_chemical_formula_weight         894.59
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C27 H18 N2 O13 Cl5 La '
_chemical_oxdiff_usercomment     'Purple plate in oil'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   11.7957(3)
_cell_length_b                   26.3110(5)
_cell_length_c                   10.5813(3)
_cell_angle_alpha                90
_cell_angle_beta                 108.089(3)
_cell_angle_gamma                90
_cell_volume                     3121.67(14)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    12510
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.1670
_cell_measurement_theta_min      3.3460
_shelx_estimated_absorpt_T_max   0.474
_shelx_estimated_absorpt_T_min   0.255
_exptl_absorpt_coefficient_mu    15.151
_exptl_absorpt_correction_T_max  0.552
_exptl_absorpt_correction_T_min  0.325
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.903
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             1760
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-6 11 0 0.0393
5 -11 0 0.0245
2 2 -7 0.0748
-3 -1 7 0.0471
-5 -13 -1 0.0301
6 -10 -2 0.0318
4 -11 2 0.0257
-5 11 -1 0.0412
-6 10 3 0.0403
-2 -14 -3 0.0347
-7 -6 3 0.0306
2 14 3 0.0395
-2 15 -2 0.0449
4 4 -6 0.0664
5 12 0 0.0274
6 10 -1 0.0317

_exptl_crystal_size_max          0.124
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.058
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-5.5304 11.4135 0.3978 0.6994 0.0563 -0.7125
5.3505 -11.4981 0.0745 -0.7467 -0.0600 0.6625
2.3197 1.8273 -6.8303 0.7229 0.0566 0.6887
-2.8797 -0.6489 6.8477 -0.6486 -0.0507 -0.7595
-4.6491 -12.6736 -0.5670 0.0792 -0.9968 0.0091
5.9934 -10.4611 -2.3530 -0.4648 -0.0379 0.8846
4.4792 -11.3394 1.7886 -0.8884 -0.0711 0.4536
-4.6886 11.4340 -1.4337 0.8630 0.0691 -0.5004
-6.0331 9.5897 3.3163 0.3234 0.0267 -0.9459
-2.0327 -14.3555 -2.5196 0.0722 -0.9127 0.4023
-7.1214 -6.0942 2.5642 0.0644 -0.8064 -0.5879
1.6884 14.4028 2.7317 -0.0706 0.8922 -0.4462
-1.7219 14.9638 -2.3032 0.8390 0.4568 -0.2957
4.0189 4.3345 -6.4259 0.6100 0.3307 0.7201
5.1144 12.0468 0.1340 -0.0788 0.9940 0.0757
6.2786 9.6622 -1.1610 -0.0744 0.9428 0.3249

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1074
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            45204
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.871
_diffrn_reflns_theta_min         3.359
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     47.00  81.00   0.50    0.20    --  111.50-125.00  30.00   68
  2  ω     86.00 111.00   0.50    0.20    --  111.50-125.00  30.00   50
  3  ω     34.00  93.00   0.50    0.10    --   48.11-125.00 -30.00  118
  4  ω     41.00  85.00   0.50    0.10    --   48.11-125.00 -90.00   88
  5  ω     43.00 110.00   0.50    0.20    --  111.50-125.00-180.00  134
  6  ω     76.00 106.00   0.50    0.20    --  111.50-102.00 -55.35   60
  7  ω     58.00 107.00   0.50    0.20    --  111.50-125.00   0.00   98
  8  ω     82.00 107.00   0.50    0.20    --  111.50-102.00  30.22   50
  9  ω     46.00  72.00   0.50    0.20    --  111.50-102.00 -55.35   52
 10  ω     43.00  78.00   0.50    0.20    --  111.50-102.00  30.22   70
 11  ω     45.00 100.00   0.50    0.20    --  111.50 -94.00  30.00  110
 12  ω     77.00 106.00   0.50    0.20    --  111.50-103.00  84.75   58
 13  ω     48.00  73.00   0.50    0.20    --  111.50-103.00  84.75   50
 14  ω     58.00 107.00   0.50    0.20    --  111.50-112.00 177.42   98
 15  ω     77.00 102.00   0.50    0.20    --  111.50 -94.00 -30.00   50
 16  ω     42.00  70.00   0.50    0.20    --  111.50 -94.00 -30.00   56
 17  ω     53.00  95.00   0.50    0.20    --  111.50 -94.00 -90.00   84
 18  ω     41.00  67.00   0.50    0.20    --  111.50 -94.00-120.00   52
 19  ω     51.00 105.00   0.50    0.20    --  111.50 -94.00-150.00  108
 20  ω     79.00 105.00   0.50    0.20    --  111.50 -94.00-180.00   52
 21  ω     42.00  73.00   0.50    0.20    --  111.50 -94.00-180.00   62
 22  ω     76.00 102.00   0.50    0.20    --  111.50 -94.00-120.00   52
 23  ω     81.00 106.00   0.50    0.20    --  111.50 -93.00  71.15   50
 24  ω     79.00 104.00   0.50    0.20    --  111.50 -94.00 150.00   50
 25  ω     40.00  66.00   0.50    0.20    --  111.50 -93.00  71.15   52
 26  ω     -1.00  27.00   0.50    0.10    --   48.11 -19.00 -90.00   56
 27  ω     53.00  86.00   0.50    0.20    --  111.50 -77.00  60.00   66
 28  ω     41.00  69.00   0.50    0.20    --  111.50 -77.00  90.00   56
 29  ω     40.00  65.00   0.50    0.20    --  111.50 -61.00  90.00   50
 30  ω     40.00  65.00   0.50    0.20    --  111.50 -61.00  60.00   50
 31  ω     40.00  68.00   0.50    0.20    --  111.50 -61.00-120.00   56
 32  ω     40.00  69.00   0.50    0.20    --  111.50 -77.00-180.00   58
 33  ω     45.00  71.00   0.50    0.20    --  111.50 -61.00-150.00   52
 34  ω     41.00  67.00   0.50    0.20    --  111.50 -61.00 -90.00   52
 35  ω     43.00  71.00   0.50    0.20    --  111.50 -61.00 -60.00   56
 36  ω    102.00 153.00   0.50    0.20    --  111.50  15.00  30.00  102
 37  ω     99.00 146.00   0.50    0.20    --  111.50  61.00  90.00   94
 38  ω    102.00 140.00   0.50    0.20    --  111.50  45.00-120.00   76
 39  ω    101.00 151.00   0.50    0.20    --  111.50  30.00-180.00  100
 40  ω    118.00 144.00   0.50    0.20    --  111.50  61.00-180.00   52
 41  ω    149.00 178.00   0.50    0.20    --  111.50  61.00-180.00   58
 42  ω    149.00 176.00   0.50    0.20    --  111.50  45.00-120.00   54
 43  ω    104.00 177.00   0.50    0.20    --  111.50  30.00-120.00  146
 44  ω    115.00 178.00   0.50    0.20    --  111.50  15.00 -60.00  126
 45  ω    103.00 162.00   0.50    0.20    --  111.50  15.00 -30.00  118
 46  ω    102.00 164.00   0.50    0.20    --  111.50  30.00  60.00  124
 47  ω    109.00 167.00   0.50    0.20    --  111.50  30.00 150.00  116
 48  ω    -68.00  22.00   0.50    0.10    --  -48.11  77.00  90.00  180
 49  ω    -44.00  24.00   0.50    0.10    --  -48.11  38.00  60.00  136
 50  ω    -28.00  23.00   0.50    0.10    --  -48.11  19.00 150.00  102
 51  ω    -51.00 -26.00   0.50    0.20    --  -90.00  45.00 -60.00   50
 52  ω    -41.00  24.00   0.50    0.10    --  -48.11  38.00-180.00  130
 53  ω   -155.00 -86.00   0.50    0.20    --  -90.00 -30.00-150.00  138
 54  ω    -53.00 -13.00   0.50    0.10    --  -48.11 125.00-120.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0778618000
_diffrn_orient_matrix_UB_12      0.0279002000
_diffrn_orient_matrix_UB_13      -0.1248101000
_diffrn_orient_matrix_UB_21      0.0862003000
_diffrn_orient_matrix_UB_22      0.0455481000
_diffrn_orient_matrix_UB_23      0.0331674000
_diffrn_orient_matrix_UB_31      0.0734325000
_diffrn_orient_matrix_UB_32      -0.0239763000
_diffrn_orient_matrix_UB_33      -0.0823017000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5754
_reflns_number_total             6725
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         1.116
_refine_diff_density_min         -2.502
_refine_diff_density_rms         0.171
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     451
_refine_ls_number_reflns         6725
_refine_ls_number_restraints     9
_refine_ls_R_factor_all          0.0582
_refine_ls_R_factor_gt           0.0494
_refine_ls_restrained_S_all      1.141
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0656P)²+8.2914P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1311
_refine_ls_wR_factor_ref         0.1380
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 O45-H45A = O45-H45B
 0.84 with sigma of 0.02
 H45A-H45B
 1.34 with sigma of 0.04
 O46-H46A = O46-H46B
 0.84 with sigma of 0.02
 H46A-H46B
 1.34 with sigma of 0.04
 O47-H47A = O47-H47B
 0.84 with sigma of 0.02
 H47A-H47B
 1.34 with sigma of 0.04
3.a Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C44(H44A,H44B)
3.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C33(H33), C34(H34), C35(H35), C38(H38), C39(H39), C40(H40), C41(H41)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C2 C 0.5559(5) 0.4512(2) 1.0019(6) 0.0222(11) Uani 1 1 d . . . . .
C3 C 0.4808(5) 0.4584(2) 1.0788(6) 0.0205(11) Uani 1 1 d . . . . .
C4 C 0.4179(5) 0.5035(2) 1.0782(5) 0.0203(11) Uani 1 1 d . . . . .
O5 O 0.3419(3) 0.51129(15) 1.1363(4) 0.0193(8) Uani 1 1 d . . . . .
Cl6 Cl 0.45876(12) 0.40792(5) 1.17610(14) 0.0234(3) Uani 1 1 d . . . . .
O7 O 0.8993(3) 0.43130(15) 0.8106(4) 0.0203(8) Uani 1 1 d . . . . .
C8 C 0.9504(5) 0.4644(2) 0.8948(6) 0.0181(10) Uani 1 1 d . . . . .
C9 C 1.0280(5) 0.5014(2) 0.8766(5) 0.0175(10) Uani 1 1 d . . . . .
C10 C 1.0785(5) 0.5383(2) 0.9738(5) 0.0172(10) Uani 1 1 d . . . . .
O11 O 1.1439(3) 0.57354(14) 0.9629(4) 0.0197(8) Uani 1 1 d . . . . .
Cl12 Cl 1.05107(12) 0.50636(5) 0.72222(13) 0.0232(3) Uani 1 1 d . . . . .
La1 La 0.70515(3) 0.39107(2) 0.81410(3) 0.01457(11) Uani 1 1 d . . . . .
O1 O 0.6040(4) 0.40960(14) 0.9896(4) 0.0207(8) Uani 1 1 d . . . . .
O13 O 0.6940(4) 0.44225(15) 0.6075(4) 0.0217(8) Uani 1 1 d . . . . .
C14 C 0.6062(5) 0.4704(2) 0.5525(5) 0.0178(10) Uani 1 1 d . . . . .
C15 C 0.6039(5) 0.5075(2) 0.4577(6) 0.0202(11) Uani 1 1 d . . . . .
C16 C 0.5048(5) 0.5385(2) 0.4033(6) 0.0207(11) Uani 1 1 d . . . . .
O17 O 0.4977(4) 0.57263(14) 0.3193(4) 0.0207(8) Uani 1 1 d . . . . .
Cl18 Cl 0.72926(11) 0.51624(5) 0.40755(14) 0.0220(3) Uani 1 1 d . . . . .
C19 C 0.8348(5) 0.2595(2) 0.5798(6) 0.0198(11) Uani 1 1 d . . . . .
C20 C 0.7773(5) 0.2188(2) 0.5006(6) 0.0198(11) Uani 1 1 d . . . . .
C21 C 0.6416(5) 0.2216(2) 0.4387(6) 0.0228(11) Uani 1 1 d . . . . .
C22 C 0.5801(5) 0.2622(2) 0.4715(6) 0.0261(12) Uani 1 1 d . . . . .
C23 C 0.6360(5) 0.2999(2) 0.5621(6) 0.0209(11) Uani 1 1 d . . . . .
C24 C 0.7733(5) 0.2986(2) 0.6217(6) 0.0202(11) Uani 1 1 d . . . . .
O25 O 0.8273(4) 0.18002(14) 0.4747(4) 0.0209(8) Uani 1 1 d . . . . .
O26 O 0.5951(4) 0.18600(15) 0.3602(4) 0.0226(8) Uani 1 1 d . . . . .
O27 O 0.5853(4) 0.33586(15) 0.6006(4) 0.0243(8) Uani 1 1 d . . . . .
O28 O 0.8201(4) 0.33261(15) 0.7012(4) 0.0214(8) Uani 1 1 d . . . . .
Cl29 Cl 0.99040(12) 0.25941(5) 0.64130(14) 0.0237(3) Uani 1 1 d . . . . .
Cl30 Cl 0.42658(14) 0.26455(6) 0.39689(19) 0.0409(4) Uani 1 1 d . . . . .
N31 N 0.0236(4) 0.35168(18) 0.3945(5) 0.0212(9) Uani 1 1 d . . . . .
C32 C -0.0719(5) 0.3512(2) 0.2866(6) 0.0243(12) Uani 1 1 d . . . . .
H32 H -0.065847 0.336743 0.206673 0.029 Uiso 1 1 calc R U . . .
C33 C -0.1796(5) 0.3711(2) 0.2886(6) 0.0221(11) Uani 1 1 d . . . . .
H33 H -0.247341 0.370352 0.211235 0.026 Uiso 1 1 calc R U . . .
C34 C -0.1869(5) 0.3924(2) 0.4059(6) 0.0229(12) Uani 1 1 d . . . . .
H34 H -0.260517 0.405330 0.411141 0.027 Uiso 1 1 calc R U . . .
C35 C -0.0841(5) 0.3945(2) 0.5163(6) 0.0213(11) Uani 1 1 d . . . . .
H35 H -0.086708 0.411143 0.595078 0.026 Uiso 1 1 calc R U . . .
C36 C 0.0207(5) 0.3729(2) 0.5120(6) 0.0192(11) Uani 1 1 d . . . . .
C37 C 0.1288(5) 0.3693(2) 0.6298(6) 0.0201(11) Uani 1 1 d . . . . .
C38 C 0.1245(6) 0.3757(2) 0.7572(6) 0.0247(12) Uani 1 1 d . . . . .
H38 H 0.050665 0.382443 0.772386 0.030 Uiso 1 1 calc R U . . .
C39 C 0.2289(6) 0.3721(2) 0.8636(7) 0.0285(13) Uani 1 1 d . . . . .
H39 H 0.227295 0.378218 0.951506 0.034 Uiso 1 1 calc R U . . .
C40 C 0.3350(6) 0.3597(2) 0.8417(6) 0.0278(13) Uani 1 1 d . . . . .
H40 H 0.406286 0.356488 0.914206 0.033 Uiso 1 1 calc R U . . .
C41 C 0.3358(5) 0.3522(2) 0.7126(6) 0.0230(11) Uani 1 1 d . . . . .
H41 H 0.407451 0.342496 0.695979 0.028 Uiso 1 1 calc R U . . .
N42 N 0.2355(4) 0.35849(18) 0.6113(5) 0.0216(10) Uani 1 1 d . . . . .
C43 C 0.2412(6) 0.3557(3) 0.4746(6) 0.0276(13) Uani 1 1 d . . . . .
H43A H 0.316108 0.338958 0.474012 0.033 Uiso 1 1 calc R U . . .
H43B H 0.239641 0.390398 0.437737 0.033 Uiso 1 1 calc R U . . .
C44 C 0.1346(6) 0.3255(2) 0.3909(7) 0.0296(13) Uani 1 1 d . . . . .
H44A H 0.136326 0.323249 0.298160 0.035 Uiso 1 1 calc R U . . .
H44B H 0.137121 0.290614 0.426633 0.035 Uiso 1 1 calc R U . . .
O45 O 0.7895(5) 0.5607(2) 0.7543(6) 0.0423(12) Uani 1 1 d D . . . .
H45A H 0.750(8) 0.549(3) 0.802(9) 0.063 Uiso 1 1 d D U . . .
H45B H 0.819(9) 0.535(2) 0.728(10) 0.063 Uiso 1 1 d D U . . .
O46 O 0.9054(5) 0.6411(2) 0.9194(6) 0.0452(13) Uani 1 1 d D . . . .
H46A H 0.899(8) 0.612(2) 0.883(10) 0.068 Uiso 1 1 d D U . . .
H46B H 0.979(3) 0.646(4) 0.954(10) 0.068 Uiso 1 1 d D U . . .
O47 O 0.7666(6) 0.7322(3) 0.9083(8) 0.0615(17) Uani 1 1 d D . . . .
H47A H 0.807(8) 0.705(2) 0.920(13) 0.092 Uiso 1 1 d D U . . .
H47B H 0.694(3) 0.723(4) 0.891(14) 0.092 Uiso 1 1 d D U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C2 C3 1.389(8) . ?
C2 C4 1.549(8) 3_667 ?
C2 O1 1.257(7) . ?
C3 C4 1.399(8) . ?
C3 Cl6 1.748(6) . ?
C4 O5 1.251(7) . ?
O5 La1 2.714(4) 3_667 ?
O7 C8 1.256(7) . ?
O7 La1 2.534(4) . ?
C8 C9 1.392(7) . ?
C8 C10 1.533(7) 3_767 ?
C9 C10 1.404(8) . ?
C9 Cl12 1.742(5) . ?
C10 O11 1.235(7) . ?
O11 La1 2.645(4) 3_767 ?
La1 O1 2.547(4) . ?
La1 O13 2.536(4) . ?
La1 O17 2.556(4) 3_666 ?
La1 O25 2.635(4) 4_566 ?
La1 O26 2.535(4) 4_566 ?
La1 O27 2.689(4) . ?
La1 O28 2.576(4) . ?
O13 C14 1.260(7) . ?
C14 C15 1.393(8) . ?
C14 C16 1.538(7) 3_666 ?
C15 C16 1.395(8) . ?
C15 Cl18 1.735(6) . ?
C16 O17 1.249(7) . ?
C19 C20 1.398(8) . ?
C19 C24 1.406(8) . ?
C19 Cl29 1.747(6) . ?
C20 C21 1.532(8) . ?
C20 O25 1.251(7) . ?
C21 C22 1.395(8) . ?
C21 O26 1.259(7) . ?
C22 C23 1.393(8) . ?
C22 Cl30 1.737(6) . ?
C23 C24 1.545(8) . ?
C23 O27 1.254(7) . ?
C24 O28 1.235(7) . ?
N31 C32 1.331(8) . ?
N31 C36 1.373(7) . ?
N31 C44 1.490(7) . ?
C32 H32 0.9500 . ?
C32 C33 1.381(8) . ?
C33 H33 0.9500 . ?
C33 C34 1.388(8) . ?
C34 H34 0.9500 . ?
C34 C35 1.400(9) . ?
C35 H35 0.9500 . ?
C35 C36 1.374(8) . ?
C36 C37 1.484(8) . ?
C37 C38 1.375(8) . ?
C37 N42 1.363(7) . ?
C38 H38 0.9500 . ?
C38 C39 1.391(9) . ?
C39 H39 0.9500 . ?
C39 C40 1.380(9) . ?
C40 H40 0.9500 . ?
C40 C41 1.384(9) . ?
C41 H41 0.9500 . ?
C41 N42 1.337(8) . ?
N42 C43 1.470(8) . ?
C43 H43A 0.9900 . ?
C43 H43B 0.9900 . ?
C43 C44 1.518(9) . ?
C44 H44A 0.9900 . ?
C44 H44B 0.9900 . ?
O45 H45A 0.84(2) . ?
O45 H45B 0.85(2) . ?
O46 H46A 0.85(2) . ?
O46 H46B 0.85(2) . ?
O47 H47A 0.85(2) . ?
O47 H47B 0.86(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C3 C2 C4 119.1(5) . 3_667 ?
O1 C2 C3 124.8(5) . . ?
O1 C2 C4 116.1(5) . 3_667 ?
C2 C3 C4 123.2(5) . . ?
C2 C3 Cl6 118.6(4) . . ?
C4 C3 Cl6 118.1(4) . . ?
C3 C4 C2 117.4(5) . 3_667 ?
O5 C4 C2 116.0(5) . 3_667 ?
O5 C4 C3 126.6(5) . . ?
C4 O5 La1 118.1(4) . 3_667 ?
C8 O7 La1 121.0(3) . . ?
O7 C8 C9 125.3(5) . . ?
O7 C8 C10 114.8(5) . 3_767 ?
C9 C8 C10 119.9(5) . 3_767 ?
C8 C9 C10 122.0(5) . . ?
C8 C9 Cl12 118.9(4) . . ?
C10 C9 Cl12 118.8(4) . . ?
C9 C10 C8 118.1(5) . 3_767 ?
O11 C10 C8 116.1(5) . 3_767 ?
O11 C10 C9 125.8(5) . . ?
C10 O11 La1 116.6(3) . 3_767 ?
O7 La1 O5 81.23(12) . 3_667 ?
O7 La1 O11 60.31(12) . 3_767 ?
O7 La1 O1 124.13(13) . . ?
O7 La1 O13 64.59(13) . . ?
O7 La1 O17 122.10(12) . 3_666 ?
O7 La1 O25 89.43(12) . 4_566 ?
O7 La1 O26 148.86(13) . 4_566 ?
O7 La1 O27 117.09(12) . . ?
O7 La1 O28 68.56(12) . . ?
O11 La1 O5 67.40(12) 3_767 3_667 ?
O11 La1 O27 166.52(12) 3_767 . ?
O1 La1 O5 60.49(12) . 3_667 ?
O1 La1 O11 67.69(12) . 3_767 ?
O1 La1 O17 76.16(13) . 3_666 ?
O1 La1 O25 87.25(12) . 4_566 ?
O1 La1 O27 118.22(13) . . ?
O1 La1 O28 152.32(12) . . ?
O13 La1 O5 72.84(12) . 3_667 ?
O13 La1 O11 114.99(13) . 3_767 ?
O13 La1 O1 128.04(12) . . ?
O13 La1 O17 62.37(12) . 3_666 ?
O13 La1 O25 143.56(12) . 4_566 ?
O13 La1 O27 71.92(13) . . ?
O13 La1 O28 79.13(12) . . ?
O17 La1 O5 62.64(12) 3_666 3_667 ?
O17 La1 O11 128.07(12) 3_666 3_767 ?
O17 La1 O25 148.46(12) 3_666 4_566 ?
O17 La1 O27 65.16(12) 3_666 . ?
O17 La1 O28 120.28(13) 3_666 . ?
O25 La1 O5 130.63(12) 4_566 3_667 ?
O25 La1 O11 65.97(12) 4_566 3_767 ?
O25 La1 O27 101.41(12) 4_566 . ?
O26 La1 O5 124.91(12) 4_566 3_667 ?
O26 La1 O11 110.67(12) 4_566 3_767 ?
O26 La1 O1 68.23(13) 4_566 . ?
O26 La1 O13 134.26(13) 4_566 . ?
O26 La1 O17 87.58(13) 4_566 3_666 ?
O26 La1 O25 61.20(12) 4_566 4_566 ?
O26 La1 O27 64.05(13) 4_566 . ?
O26 La1 O28 89.20(13) 4_566 . ?
O27 La1 O5 126.03(12) . 3_667 ?
O28 La1 O5 145.46(12) . 3_667 ?
O28 La1 O11 108.56(12) . 3_767 ?
O28 La1 O25 67.28(12) . 4_566 ?
O28 La1 O27 60.19(12) . . ?
C2 O1 La1 124.8(4) . . ?
C14 O13 La1 121.7(3) . . ?
O13 C14 C15 125.0(5) . . ?
O13 C14 C16 115.2(5) . 3_666 ?
C15 C14 C16 119.8(5) . 3_666 ?
C14 C15 C16 122.2(5) . . ?
C14 C15 Cl18 119.0(4) . . ?
C16 C15 Cl18 118.7(4) . . ?
C15 C16 C14 118.0(5) . 3_666 ?
O17 C16 C14 116.8(5) . 3_666 ?
O17 C16 C15 125.2(5) . . ?
C16 O17 La1 120.4(4) . 3_666 ?
C20 C19 C24 123.2(5) . . ?
C20 C19 Cl29 118.7(4) . . ?
C24 C19 Cl29 117.9(4) . . ?
C19 C20 C21 117.9(5) . . ?
O25 C20 C19 125.6(5) . . ?
O25 C20 C21 116.5(5) . . ?
C22 C21 C20 119.0(5) . . ?
O26 C21 C20 115.5(5) . . ?
O26 C21 C22 125.5(6) . . ?
C21 C22 Cl30 117.6(5) . . ?
C23 C22 C21 123.0(6) . . ?
C23 C22 Cl30 119.5(5) . . ?
C22 C23 C24 118.6(5) . . ?
O27 C23 C22 126.0(6) . . ?
O27 C23 C24 115.4(5) . . ?
C19 C24 C23 117.7(5) . . ?
O28 C24 C19 125.4(5) . . ?
O28 C24 C23 116.9(5) . . ?
C20 O25 La1 121.3(4) . 4_565 ?
C21 O26 La1 125.3(4) . 4_565 ?
C23 O27 La1 120.1(4) . . ?
C24 O28 La1 124.1(4) . . ?
C32 N31 C36 121.9(5) . . ?
C32 N31 C44 119.3(5) . . ?
C36 N31 C44 118.7(5) . . ?
N31 C32 H32 119.3 . . ?
N31 C32 C33 121.4(5) . . ?
C33 C32 H32 119.3 . . ?
C32 C33 H33 120.7 . . ?
C32 C33 C34 118.7(6) . . ?
C34 C33 H33 120.7 . . ?
C33 C34 H34 120.5 . . ?
C33 C34 C35 119.0(5) . . ?
C35 C34 H34 120.5 . . ?
C34 C35 H35 119.6 . . ?
C36 C35 C34 120.7(6) . . ?
C36 C35 H35 119.6 . . ?
N31 C36 C35 118.3(5) . . ?
N31 C36 C37 118.6(5) . . ?
C35 C36 C37 123.0(5) . . ?
C38 C37 C36 122.1(5) . . ?
N42 C37 C36 118.9(5) . . ?
N42 C37 C38 118.9(5) . . ?
C37 C38 H38 120.3 . . ?
C37 C38 C39 119.5(6) . . ?
C39 C38 H38 120.3 . . ?
C38 C39 H39 119.9 . . ?
C40 C39 C38 120.1(6) . . ?
C40 C39 H39 119.9 . . ?
C39 C40 H40 120.5 . . ?
C39 C40 C41 119.0(6) . . ?
C41 C40 H40 120.5 . . ?
C40 C41 H41 120.1 . . ?
N42 C41 C40 119.8(6) . . ?
N42 C41 H41 120.1 . . ?
C37 N42 C43 118.5(5) . . ?
C41 N42 C37 122.5(5) . . ?
C41 N42 C43 118.9(5) . . ?
N42 C43 H43A 110.0 . . ?
N42 C43 H43B 110.0 . . ?
N42 C43 C44 108.5(5) . . ?
H43A C43 H43B 108.4 . . ?
C44 C43 H43A 110.0 . . ?
C44 C43 H43B 110.0 . . ?
N31 C44 C43 108.6(5) . . ?
N31 C44 H44A 110.0 . . ?
N31 C44 H44B 110.0 . . ?
C43 C44 H44A 110.0 . . ?
C43 C44 H44B 110.0 . . ?
H44A C44 H44B 108.4 . . ?
H45A O45 H45B 106(5) . . ?
H46A O46 H46B 107(5) . . ?
H47A O47 H47B 105(5) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 C3 C4 C2 -6.2(9) . . . 3_667 ?
C2 C3 C4 O5 173.9(6) . . . . ?
C2 C4 O5 La1 -20.8(6) 3_667 . . 3_667 ?
C3 C2 O1 La1 166.6(4) . . . . ?
C3 C4 O5 La1 159.1(5) . . . 3_667 ?
C4 C2 C3 C4 6.3(10) 3_667 . . . ?
C4 C2 C3 Cl6 -176.4(4) 3_667 . . . ?
C4 C2 O1 La1 -12.1(7) 3_667 . . . ?
Cl6 C3 C4 C2 176.5(4) . . . 3_667 ?
Cl6 C3 C4 O5 -3.4(8) . . . . ?
O7 C8 C9 C10 177.7(5) . . . . ?
O7 C8 C9 Cl12 4.5(8) . . . . ?
C8 C9 C10 C8 2.3(9) . . . 3_767 ?
C8 C9 C10 O11 -176.8(5) . . . . ?
C8 C10 O11 La1 27.3(6) 3_767 . . 3_767 ?
C9 C10 O11 La1 -153.6(5) . . . 3_767 ?
C10 C8 C9 C10 -2.3(9) 3_767 . . . ?
C10 C8 C9 Cl12 -175.6(4) 3_767 . . . ?
Cl12 C9 C10 C8 175.5(4) . . . 3_767 ?
Cl12 C9 C10 O11 -3.6(8) . . . . ?
La1 O7 C8 C9 -154.9(4) . . . . ?
La1 O7 C8 C10 25.1(6) . . . 3_767 ?
La1 O13 C14 C15 165.6(4) . . . . ?
La1 O13 C14 C16 -14.6(6) . . . 3_666 ?
O1 C2 C3 C4 -172.3(6) . . . . ?
O1 C2 C3 Cl6 5.0(8) . . . . ?
O13 C14 C15 C16 -178.1(5) . . . . ?
O13 C14 C15 Cl18 0.7(8) . . . . ?
C14 C15 C16 C14 -2.0(9) . . . 3_666 ?
C14 C15 C16 O17 179.2(5) . . . . ?
C14 C16 O17 La1 -15.3(6) 3_666 . . 3_666 ?
C15 C16 O17 La1 163.5(4) . . . 3_666 ?
C16 C14 C15 C16 2.1(9) 3_666 . . . ?
C16 C14 C15 Cl18 -179.1(4) 3_666 . . . ?
Cl18 C15 C16 C14 179.1(4) . . . 3_666 ?
Cl18 C15 C16 O17 0.4(8) . . . . ?
C19 C20 C21 C22 -4.8(8) . . . . ?
C19 C20 C21 O26 174.8(5) . . . . ?
C19 C20 O25 La1 -177.2(4) . . . 4_565 ?
C19 C24 O28 La1 -165.9(4) . . . . ?
C20 C19 C24 C23 -8.0(8) . . . . ?
C20 C19 C24 O28 173.0(5) . . . . ?
C20 C21 C22 C23 -2.3(9) . . . . ?
C20 C21 C22 Cl30 178.9(4) . . . . ?
C20 C21 O26 La1 5.2(7) . . . 4_565 ?
C21 C20 O25 La1 2.4(6) . . . 4_565 ?
C21 C22 C23 C24 4.3(9) . . . . ?
C21 C22 C23 O27 -176.3(6) . . . . ?
C22 C21 O26 La1 -175.2(5) . . . 4_565 ?
C22 C23 C24 C19 0.6(8) . . . . ?
C22 C23 C24 O28 179.7(5) . . . . ?
C22 C23 O27 La1 166.4(5) . . . . ?
C23 C24 O28 La1 15.1(7) . . . . ?
C24 C19 C20 C21 10.0(8) . . . . ?
C24 C19 C20 O25 -170.4(5) . . . . ?
C24 C23 O27 La1 -14.2(6) . . . . ?
O25 C20 C21 C22 175.5(5) . . . . ?
O25 C20 C21 O26 -4.8(7) . . . . ?
O26 C21 C22 C23 178.2(6) . . . . ?
O26 C21 C22 Cl30 -0.7(9) . . . . ?
O27 C23 C24 C19 -178.9(5) . . . . ?
O27 C23 C24 O28 0.3(7) . . . . ?
Cl29 C19 C20 C21 -175.3(4) . . . . ?
Cl29 C19 C20 O25 4.3(8) . . . . ?
Cl29 C19 C24 C23 177.3(4) . . . . ?
Cl29 C19 C24 O28 -1.8(8) . . . . ?
Cl30 C22 C23 C24 -176.9(4) . . . . ?
Cl30 C22 C23 O27 2.5(9) . . . . ?
N31 C32 C33 C34 0.5(9) . . . . ?
N31 C36 C37 C38 -160.7(5) . . . . ?
N31 C36 C37 N42 18.0(7) . . . . ?
C32 N31 C36 C35 -0.8(8) . . . . ?
C32 N31 C36 C37 176.6(5) . . . . ?
C32 N31 C44 C43 144.9(6) . . . . ?
C32 C33 C34 C35 2.3(8) . . . . ?
C33 C34 C35 C36 -4.4(8) . . . . ?
C34 C35 C36 N31 3.7(8) . . . . ?
C34 C35 C36 C37 -173.6(5) . . . . ?
C35 C36 C37 C38 16.5(8) . . . . ?
C35 C36 C37 N42 -164.7(5) . . . . ?
C36 N31 C32 C33 -1.2(9) . . . . ?
C36 N31 C44 C43 -39.2(7) . . . . ?
C36 C37 C38 C39 -179.7(5) . . . . ?
C36 C37 N42 C41 -176.6(5) . . . . ?
C36 C37 N42 C43 6.0(7) . . . . ?
C37 C38 C39 C40 -3.3(9) . . . . ?
C37 N42 C43 C44 -44.7(7) . . . . ?
C38 C37 N42 C41 2.2(8) . . . . ?
C38 C37 N42 C43 -175.2(5) . . . . ?
C38 C39 C40 C41 1.5(9) . . . . ?
C39 C40 C41 N42 2.1(9) . . . . ?
C40 C41 N42 C37 -4.0(8) . . . . ?
C40 C41 N42 C43 173.4(5) . . . . ?
C41 N42 C43 C44 137.8(5) . . . . ?
N42 C37 C38 C39 1.5(8) . . . . ?
N42 C43 C44 N31 59.4(7) . . . . ?
C44 N31 C32 C33 174.5(6) . . . . ?
C44 N31 C36 C35 -176.6(5) . . . . ?
C44 N31 C36 C37 0.8(8) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.580
_oxdiff_exptl_absorpt_empirical_full_min 0.683
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a
_database_code_depnum_ccdc_archive 'CCDC 2431639'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-03-17 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_audit_creation_date             2025-03-07
_audit_creation_method           
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7181)
;
_shelx_SHELXL_version_number     2019/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C12 H2 Br4 La O9, 0.5(C14 H12 N2),  10(H2 O)'
_chemical_formula_sum            'C19 H28 Br4 La N O19'
_chemical_formula_weight         1032.97
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C19 H28 Br4 La N O19'
_chemical_oxdiff_usercomment     'Small maroon block'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   10.7111(3)
_cell_length_b                   11.8605(4)
_cell_length_c                   13.2161(4)
_cell_angle_alpha                97.055(2)
_cell_angle_beta                 94.584(2)
_cell_angle_gamma                107.293(3)
_cell_volume                     1578.87(9)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    17983
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      79.0400
_cell_measurement_theta_min      3.4080
_shelx_estimated_absorpt_T_max   0.628
_shelx_estimated_absorpt_T_min   0.279
_exptl_absorpt_coefficient_mu    17.123
_exptl_absorpt_correction_T_max  0.741
_exptl_absorpt_correction_T_min  0.305
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear reddish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.173
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             996
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-4 0 -6 0.0168
4 0 6 0.0168
3 -7 0 0.0497
-4 7 -2 0.0372
-1 0 9 0.0194
1 0 -9 0.0194
-6 -2 3 0.0139
6 2 -3 0.0156

_exptl_crystal_size_max          0.097
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.03
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-3.8071 0.3790 -6.4663 0.0159 -0.2074 0.9781
3.8071 -0.3790 6.4663 -0.0159 0.2074 -0.9781
3.3435 -7.4978 -0.0844 -0.0785 0.9874 0.1375
-4.3550 7.0041 -2.1119 0.0774 -0.9757 0.2051
-0.9918 -0.2686 8.5393 -0.6636 -0.0535 -0.7462
0.9918 0.2686 -8.5393 0.6636 0.0535 0.7462
-5.7589 -2.0749 2.5377 -0.9125 -0.0720 0.4027
5.7147 2.0546 -2.9110 0.9300 0.0735 -0.3601

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0515
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26037
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.853
_diffrn_reflns_theta_min         3.395
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -49.00  24.00   0.50    0.50    --  -47.86  43.00-101.00  146
  2  ω   -119.00 -37.00   0.50    0.50    --  -47.86 -43.00 107.00  164
  3  ω   -119.00 -37.00   0.50    0.50    --  -47.86 -43.00 107.00  164
  4  ω    -23.00  49.00   0.50    0.50    --   47.86 -43.00 107.00  144
  5  ω   -161.00 -79.00   0.50    2.00    --  -90.00 -43.00 107.00  164
  6  ω    -49.00 -18.00   0.50    2.00    --  -90.00  43.00-101.00   62
  7  ω    101.00 178.00   0.50    2.00    --  111.50  43.00-101.00  154
  8  ω    -30.00  27.00   0.50    0.50    --  -47.86  19.00-180.00  114
  9  ω   -119.00 -26.00   0.50    0.50    --  -47.86 -77.00 -60.00  186
 10  ω    -86.00 -13.00   0.50    0.50    --  -47.86 125.00 -60.00  146
 11  ω     38.00 119.00   0.50    0.50    --   47.86  43.00-101.00  162
 12  ω     34.00  92.00   0.50    0.50    --   47.86-125.00 -30.00  116
 13  ω     -1.00  79.00   0.50    0.50    --   47.86 -99.00-180.00  160
 14  ω     34.00  92.00   0.50    0.50    --   47.86-125.00 150.00  116
 15  ω    -71.00 -18.00   0.50    2.00    --  -90.00  61.00  60.00  106
 16  ω     40.00  69.00   0.50    2.00    --  111.50 -61.00-120.00   58
 17  ω     44.00  70.00   0.50    2.00    --  111.50 -77.00  60.00   52
 18  ω    108.00 172.00   0.50    2.00    --  111.50  15.00   0.00  128
 19  ω    106.00 140.00   0.50    2.00    --  111.50  30.00-150.00   68
 20  ω    153.00 178.00   0.50    2.00    --  111.50  30.00-150.00   50
 21  ω    101.00 178.00   0.50    2.00    --  111.50  45.00 -60.00  154
 22  ω     45.00  71.00   0.50    2.00    --  111.50 -61.00 -90.00   52
 23  ω     40.00  70.00   0.50    2.00    --  111.50 -61.00 -60.00   60
 24  ω    104.00 165.00   0.50    2.00    --  111.50  30.00  60.00  122
 25  ω     47.00 103.00   0.50    2.00    --  111.50 -94.00-120.00  112
 26  ω     79.00 111.00   0.50    2.00    --  111.50-125.00-150.00   64
 27  ω     40.00  65.00   0.50    2.00    --  111.50 -61.00  60.00   50
 28  ω     48.00 105.00   0.50    2.00    --  111.50 -94.00-150.00  114
 29  ω     40.00 102.00   0.50    2.00    --  111.50 -94.00 -90.00  124
 30  ω     48.00  77.00   0.50    2.00    --  111.50-125.00-180.00   58
 31  ω     86.00 111.00   0.50    2.00    --  111.50-125.00-180.00   50
 32  ω    102.00 169.00   0.50    2.00    --  111.50  15.00  30.00  134
 33  ω     50.00  76.00   0.50    2.00    --  111.50 -94.00  60.00   52
 34  ω     79.00 105.00   0.50    2.00    --  111.50 -94.00  60.00   52
 35  ω     44.00  71.00   0.50    2.00    --  111.50 -61.00 -30.00   54
 36  ω     45.00  70.00   0.50    2.00    --  111.50 -94.00   0.00   50
 37  ω     74.00 100.00   0.50    2.00    --  111.50 -94.00   0.00   52
 38  ω     73.00 105.00   0.50    2.00    --  111.50 -94.00  30.00   64
 39  ω    104.00 137.00   0.50    2.00    --  111.50  77.00 -90.00   66
 40  ω    107.00 178.00   0.50    2.00    --  111.50  30.00-120.00  142
 41  ω     58.00 108.00   0.50    2.00    --  111.50-125.00   0.00  100
 42  ω    141.00 177.00   0.50    2.00    --  111.50  77.00 -90.00   72
 43  ω     68.00 104.00   0.50    2.00    --  111.50 -94.00 -30.00   72
 44  ω     41.00  97.00   0.50    2.00    --  111.50 -94.00-180.00  112
 45  ω     42.00  69.00   0.50    2.00    --  111.50 -77.00  90.00   54
 46  ω     42.00  69.00   0.50    2.00    --  111.50 -61.00-150.00   54
 47  ω     40.00  65.00   0.50    2.00    --  111.50 -61.00   0.00   50
 48  ω     41.00  66.00   0.50    2.00    --  111.50 -94.00  90.00   50
 49  ω     77.00 102.00   0.50    2.00    --  111.50 -94.00  90.00   50
 50  ω     50.00 105.00   0.50    2.00    --  111.50 -94.00 120.00  110
 51  ω     65.00 105.00   0.50    2.00    --  111.50 -94.00 150.00   80
 52  ω     42.00  67.00   0.50    2.00    --  111.50 -94.00  30.00   50
 53  ω     42.00  70.00   0.50    2.00    --  111.50-125.00-150.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1090644000
_diffrn_orient_matrix_UB_12      0.0598157000
_diffrn_orient_matrix_UB_13      -0.0631574000
_diffrn_orient_matrix_UB_21      0.0501743000
_diffrn_orient_matrix_UB_22      -0.1092726000
_diffrn_orient_matrix_UB_23      -0.0038710000
_diffrn_orient_matrix_UB_31      -0.0928809000
_diffrn_orient_matrix_UB_32      -0.0586325000
_diffrn_orient_matrix_UB_33      -0.1000177000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                6341
_reflns_number_total             6679
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection       
'CrysAlisPro system (CCD 43.111a 64-bit (release 27-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.859
_refine_diff_density_min         -2.257
_refine_diff_density_rms         0.149
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.118
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         6679
_refine_ls_number_restraints     212
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0382
_refine_ls_restrained_S_all      1.102
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0582P)²+3.5753P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1057
_refine_ls_wR_factor_ref         0.1070
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H35 of C35, H36 of C36, H26 of C26
 At 1.5 times of:
  All O(H,H) groups, H31 of C31, H27 of C27
2. Restrained distances
 C35-C36
 1.35 with sigma of 0.02
 C28-C35 = C36-C37
 1.43 with sigma of 0.02
 C32-C33
 1.51 with sigma of 0.02
 N30-C32 = N34-C33
 1.48 with sigma of 0.02
 C29-C28 = C37-C29_$1
 1.36 with sigma of 0.02
 C29_$1-N34 = C29-N30
 1.4 with sigma of 0.04
 N30-C31 = N34-C27_$1
 1.35 with sigma of 0.04
 H27-C27
 0.93 with sigma of 0.001
 H27-C26
 1.992 with sigma of 0.001
 H27-C28
 2.075 with sigma of 0.001
 H31-C31
 0.93 with sigma of 0.0005
 H31-C26
 2.021 with sigma of 0.0005
 H31-N30
 1.959 with sigma of 0.0005
 H31-H26
 2.32 with sigma of 0.0005
 O25-H25A = O25-H25B
 0.84 with sigma of 0.02
 H25A-H25B
 1.34 with sigma of 0.04
 O38-H38A = O38-H38B
 0.84 with sigma of 0.02
 H38A-H38B
 1.34 with sigma of 0.04
 O39-H39A = O39-H39B
 0.84 with sigma of 0.02
 H39A-H39B
 1.34 with sigma of 0.04
 O41-H41A = O41-H41B
 0.84 with sigma of 0.02
 H41A-H41B
 1.34 with sigma of 0.04
 O42-H42A = O42-H42B
 0.84 with sigma of 0.02
 H42A-H42B
 1.34 with sigma of 0.04
 O43-H43A = O43-H43B
 0.84 with sigma of 0.02
 H43A-H43B
 1.34 with sigma of 0.04
 O44-H44A = O44-H44B
 0.84 with sigma of 0.02
 H44A-H44B
 1.34 with sigma of 0.04
 O45-H45A = O45-H45B
 0.84 with sigma of 0.02
 H45A-H45B
 1.34 with sigma of 0.04
 O46-H46A = O46-H46B
 0.84 with sigma of 0.02
 H46A-H46B
 1.34 with sigma of 0.04
 H43A-O44
 2.12 with sigma of 0.04
 O5-H44A
 2.06 with sigma of 0.04
 H25A-H45B
 -2.2 with sigma of 0.02
 H38B-H45A
 -2.2 with sigma of 0.02
 C27-C28 \\sim C37-C31_$1
 with sigma of 0.02
 C28-C29 \\sim C37-C29_$1
 with sigma of 0.02
 C26-C28 \\sim C37-C26_$1
 with sigma of 0.04
 C29-N30 \\sim C29_$1-N34
 with sigma of 0.02
 N30-C31 \\sim N34-C27_$1
 with sigma of 0.02
 C28-N30 \\sim C37-N34
 with sigma of 0.04
3. Restrained planarity
 C26, C27, C28, C29, N30, C31
 with sigma of 0.1
 C36, C35, C28, C29, C29_$1, C37
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C26 \\sim C27 \\sim C29 \\sim C31 \\sim C28 \\sim N30 \\sim C32 \\sim C35 \\sim
N34 \\sim C33 \\sim C36 \\sim C37: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(N30) = Uanis(C37)
Uanis(C28) = Uanis(N34)
Uanis(C32) = Uanis(C36)
Uanis(C33) = Uanis(C35)
5. Rigid body (RIGU) restrains
 C26, C27, C29, C31, C28, N30, C32, C33, N34, C35, C36, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C28(0.5) N30(0.5) C32(0.5) H32A(0.5) H32B(0.5) C33(0.5) H33A(0.5)
 H33B(0.5) N34(0.5) C35(0.5) H35(0.5) C36(0.5) H36(0.5) C37(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C33(H33A,H33B)
7.b Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C26(H26)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C28 C 0.3727(14) 0.0226(15) 0.4161(11) 0.0284(11) Uani 0.5 1 d D U P A -1
N30 N 0.4616(19) -0.1396(13) 0.4002(12) 0.0263(11) Uani 0.5 1 d D U P A -1
C32 C 0.5842(18) -0.166(2) 0.4335(12) 0.028(3) Uani 0.5 1 d D U P A -1
H32A H 0.658345 -0.115456 0.402780 0.034 Uiso 0.5 1 calc R U P A -1
H32B H 0.574129 -0.250492 0.408483 0.034 Uiso 0.5 1 calc R U P A -1
C33 C 0.615(2) -0.1418(18) 0.5485(14) 0.035(3) Uani 0.5 1 d D U P A -1
H33A H 0.541724 -0.193950 0.578657 0.041 Uiso 0.5 1 calc R U P A -1
H33B H 0.695550 -0.162864 0.568015 0.041 Uiso 0.5 1 calc R U P A -1
N34 N 0.6356(14) -0.0146(14) 0.5925(10) 0.0284(11) Uani 0.5 1 d D U P A -1
C35 C 0.355(2) 0.1327(17) 0.4593(14) 0.035(3) Uani 0.5 1 d D U P A -1
H35 H 0.291279 0.163863 0.428517 0.041 Uiso 0.5 1 calc R U P A -1
C36 C 0.4338(17) 0.1888(19) 0.5469(12) 0.028(3) Uani 0.5 1 d D U P A -1
H36 H 0.429755 0.263120 0.580128 0.034 Uiso 0.5 1 calc R U P A -1
C37 C 0.525(2) 0.1327(16) 0.5887(15) 0.0263(11) Uani 0.5 1 d D U P A -1
La1 La 0.16045(3) 0.26504(2) 0.79180(2) 0.02134(9) Uani 1 1 d . . . . .
O1 O -0.1389(3) 0.6534(3) 1.0255(3) 0.0276(7) Uani 1 1 d . . . . .
C2 C -0.0787(5) 0.5791(4) 1.0096(3) 0.0220(9) Uani 1 1 d . . . . .
C3 C -0.0824(5) 0.5117(4) 0.9132(3) 0.0223(9) Uani 1 1 d . . . . .
C4 C -0.0065(5) 0.4376(4) 0.8974(3) 0.0227(9) Uani 1 1 d . . . . .
O5 O 0.0005(3) 0.3802(3) 0.8120(2) 0.0244(7) Uani 1 1 d D . . . .
Br6 Br -0.19605(5) 0.52678(5) 0.80218(4) 0.02894(13) Uani 1 1 d . . . . .
O7 O 0.5960(3) 0.6891(3) 1.1510(3) 0.0274(7) Uani 1 1 d . . . . .
C8 C 0.5455(5) 0.6040(4) 1.0784(4) 0.0232(9) Uani 1 1 d . . . . .
C9 C 0.4454(5) 0.5980(4) 1.0019(4) 0.0225(9) Uani 1 1 d . . . . .
C10 C 0.3958(5) 0.5004(4) 0.9244(3) 0.0229(9) Uani 1 1 d . . . . .
O11 O 0.3035(4) 0.4865(3) 0.8538(3) 0.0278(7) Uani 1 1 d . . . . .
Br12 Br 0.37248(5) 0.72562(5) 1.00680(4) 0.02799(13) Uani 1 1 d . . . . .
O13 O -0.1584(3) -0.0733(3) 0.3204(2) 0.0265(7) Uani 1 1 d . . . . .
C14 C -0.0863(5) -0.0333(4) 0.4049(3) 0.0223(9) Uani 1 1 d . . . . .
C15 C -0.0834(5) 0.0691(4) 0.4693(3) 0.0227(9) Uani 1 1 d . . . . .
C16 C -0.0036(5) 0.1058(5) 0.5651(3) 0.0236(9) Uani 1 1 d . . . . .
O17 O 0.0011(3) 0.1959(3) 0.6278(2) 0.0271(7) Uani 1 1 d . . . . .
Br18 Br -0.18995(5) 0.16173(5) 0.43001(4) 0.02708(12) Uani 1 1 d . . . . .
O19 O -0.1998(3) -0.1242(3) 1.0929(2) 0.0259(7) Uani 1 1 d . . . . .
C20 C -0.1109(5) -0.0646(4) 1.0466(3) 0.0242(9) Uani 1 1 d . . . . .
C21 C -0.1320(5) 0.0004(5) 0.9694(4) 0.0253(10) Uani 1 1 d . . . . .
C22 C -0.0298(5) 0.0643(5) 0.9203(3) 0.0250(10) Uani 1 1 d . . . . .
O23 O -0.0408(4) 0.1226(3) 0.8484(3) 0.0281(7) Uani 1 1 d . . . . .
Br24 Br -0.30622(5) 0.00352(5) 0.93510(4) 0.02751(12) Uani 1 1 d . . . . .
O25 O 0.2580(4) 0.3598(4) 0.6420(3) 0.0361(9) Uani 1 1 d D . . . .
H25A H 0.216(6) 0.363(6) 0.587(3) 0.054 Uiso 1 1 d D U . . .
H25B H 0.323(5) 0.421(4) 0.655(6) 0.054 Uiso 1 1 d D U . . .
C26 C 0.2875(5) -0.1513(4) 0.2813(4) 0.0330(11) Uani 1 1 d D U . . .
H26 H 0.225245 -0.194999 0.224099 0.040 Uiso 1 1 calc DR U . . .
C27 C 0.2824(5) -0.0437(5) 0.3251(4) 0.0320(11) Uani 1 1 d D U . . .
H27 H 0.220(2) -0.0112(14) 0.2980(16) 0.048 Uiso 1 1 d D U . . .
C29 C 0.4580(5) -0.0307(4) 0.4538(3) 0.0255(9) Uani 1 1 d D U . . .
C31 C 0.3831(5) -0.1988(4) 0.3192(4) 0.0341(11) Uani 1 1 d D U . . .
H31 H 0.3867(10) -0.2716(7) 0.2864(8) 0.051 Uiso 1 1 d D U . . .
O38 O 0.3694(10) 0.5832(8) 0.4641(5) 0.101(3) Uani 1 1 d D . . . .
H38A H 0.382(13) 0.605(14) 0.529(2) 0.151 Uiso 1 1 d D U . . .
H38B H 0.288(4) 0.543(12) 0.452(10) 0.151 Uiso 1 1 d D U . . .
O39 O 0.4913(7) 0.5287(6) 0.6444(5) 0.082(2) Uani 1 1 d D . . . .
H39A H 0.557(7) 0.519(12) 0.617(9) 0.123 Uiso 1 1 d D U . . .
H39B H 0.524(10) 0.578(10) 0.699(6) 0.123 Uiso 1 1 d D U . . .
O40 O 0.6276(4) 0.7203(4) 0.7931(4) 0.0456(10) Uani 1 1 d . . . . .
O41 O 0.4419(4) 0.8150(4) 0.7306(3) 0.0419(10) Uani 1 1 d D . . . .
H41A H 0.431(8) 0.879(4) 0.759(6) 0.063 Uiso 1 1 d D U . . .
H41B H 0.369(5) 0.762(5) 0.732(7) 0.063 Uiso 1 1 d D U . . .
O42 O 0.3860(5) 1.0271(5) 0.7897(3) 0.0451(11) Uani 1 1 d D . . . .
H42A H 0.304(3) 1.005(7) 0.772(6) 0.068 Uiso 1 1 d D U . . .
H42B H 0.399(7) 1.084(6) 0.839(5) 0.068 Uiso 1 1 d D U . . .
O43 O 0.2010(5) 0.6343(4) 0.7401(4) 0.0471(11) Uani 1 1 d D . . . .
H43A H 0.155(6) 0.584(5) 0.689(4) 0.071 Uiso 1 1 d D U . . .
H43B H 0.239(8) 0.594(6) 0.773(6) 0.071 Uiso 1 1 d D U . . .
O44 O -0.0237(8) 0.4510(6) 0.6100(4) 0.074(2) Uani 1 1 d D . . . .
H44A H -0.040(9) 0.421(9) 0.665(4) 0.111 Uiso 1 1 d D U . . .
H44B H -0.015(13) 0.394(7) 0.570(6) 0.111 Uiso 1 1 d D U . . .
O45 O 0.1403(6) 0.3755(6) 0.4529(4) 0.0598(14) Uani 1 1 d D . . . .
H45A H 0.097(5) 0.403(4) 0.412(5) 0.090 Uiso 1 1 d D U . . .
H45B H 0.140(10) 0.308(5) 0.424(4) 0.090 Uiso 1 1 d D U . . .
O46 O 0.1324(5) 0.1870(5) 0.2983(4) 0.0501(11) Uani 1 1 d D . . . .
H46A H 0.191(6) 0.201(9) 0.259(5) 0.075 Uiso 1 1 d D U . . .
H46B H 0.061(5) 0.179(9) 0.259(5) 0.075 Uiso 1 1 d D U . . .
O47 O -0.0940(5) 0.1874(5) 0.1782(4) 0.0518(12) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C28 C35 1.433(16) . ?
C28 C27 1.459(10) . ?
C28 C29 1.354(12) . ?
N30 C32 1.482(15) . ?
N30 C29 1.408(9) . ?
N30 C31 1.291(8) . ?
C32 C33 1.503(16) . ?
C33 N34 1.493(15) . ?
C35 C36 1.349(16) . ?
C36 C37 1.447(15) . ?
La1 O1 2.543(3) 2_567 ?
La1 O5 2.500(3) . ?
La1 O7 2.532(3) 2_667 ?
La1 O11 2.607(4) . ?
La1 O13 2.551(3) 2_556 ?
La1 O17 2.535(3) . ?
La1 O19 2.496(3) 2_557 ?
La1 O23 2.543(4) . ?
La1 O25 2.540(4) . ?
O1 C2 1.245(6) . ?
C2 C3 1.409(6) . ?
C2 C4 1.539(6) 2_567 ?
C3 C4 1.373(7) . ?
C3 Br6 1.891(4) . ?
C4 O5 1.263(6) . ?
O7 C8 1.260(6) . ?
C8 C9 1.393(6) . ?
C8 C10 1.544(7) 2_667 ?
C9 C10 1.388(6) . ?
C9 Br12 1.895(5) . ?
C10 O11 1.262(6) . ?
O13 C14 1.258(6) . ?
C14 C15 1.387(7) . ?
C14 C16 1.529(7) 2_556 ?
C15 C16 1.412(6) . ?
C15 Br18 1.889(5) . ?
C16 O17 1.255(6) . ?
O19 C20 1.257(7) . ?
C20 C21 1.396(7) . ?
C20 C22 1.535(7) 2_557 ?
C21 C22 1.391(8) . ?
C21 Br24 1.896(5) . ?
C22 O23 1.259(6) . ?
C26 C27 1.354(6) . ?
C26 C31 1.396(6) . ?
C29 C29 1.431(9) 2_656 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C35 C28 C27 116.2(10) . . ?
C29 C28 C35 127.5(13) . . ?
C29 C28 C27 116.2(12) . . ?
C29 N30 C32 111.4(11) . . ?
C31 N30 C32 122.3(11) . . ?
C31 N30 C29 125.0(11) . . ?
N30 C32 C33 111.2(16) . . ?
N34 C33 C32 112.9(17) . . ?
C36 C35 C28 115.1(19) . . ?
C35 C36 C37 118.2(18) . . ?
O1 La1 O11 65.49(12) 2_567 . ?
O1 La1 O13 141.81(12) 2_567 2_556 ?
O1 La1 O23 71.83(12) 2_567 . ?
O5 La1 O1 63.38(10) . 2_567 ?
O5 La1 O7 134.09(11) . 2_667 ?
O5 La1 O11 74.39(11) . . ?
O5 La1 O13 134.81(11) . 2_556 ?
O5 La1 O17 75.08(10) . . ?
O5 La1 O23 74.68(12) . . ?
O5 La1 O25 95.73(13) . . ?
O7 La1 O1 87.37(11) 2_667 2_567 ?
O7 La1 O11 61.03(11) 2_667 . ?
O7 La1 O13 90.24(11) 2_667 2_556 ?
O7 La1 O17 139.08(11) 2_667 . ?
O7 La1 O23 131.14(11) 2_667 . ?
O7 La1 O25 79.46(12) 2_667 . ?
O13 La1 O11 142.54(12) 2_556 . ?
O17 La1 O1 133.14(11) . 2_567 ?
O17 La1 O11 123.84(11) . . ?
O17 La1 O13 62.39(11) . 2_556 ?
O17 La1 O23 77.33(12) . . ?
O17 La1 O25 67.91(13) . . ?
O19 La1 O1 71.71(11) 2_557 2_567 ?
O19 La1 O5 125.44(11) 2_557 . ?
O19 La1 O7 68.85(12) 2_557 2_667 ?
O19 La1 O11 113.53(11) 2_557 . ?
O19 La1 O13 71.93(11) 2_557 2_556 ?
O19 La1 O17 122.60(12) 2_557 . ?
O19 La1 O23 62.78(11) 2_557 . ?
O19 La1 O25 138.57(13) 2_557 . ?
O23 La1 O11 135.11(11) . . ?
O23 La1 O13 81.51(12) . 2_556 ?
O25 La1 O1 134.06(13) . 2_567 ?
O25 La1 O11 69.66(12) . . ?
O25 La1 O13 82.52(13) . 2_556 ?
O25 La1 O23 145.23(11) . . ?
C2 O1 La1 120.3(3) . 2_567 ?
O1 C2 C3 124.6(4) . . ?
O1 C2 C4 116.7(4) . 2_567 ?
C3 C2 C4 118.7(4) . 2_567 ?
C2 C3 Br6 117.8(3) . . ?
C4 C3 C2 122.6(4) . . ?
C4 C3 Br6 119.5(3) . . ?
C3 C4 C2 118.5(4) . 2_567 ?
O5 C4 C2 115.7(4) . 2_567 ?
O5 C4 C3 125.8(4) . . ?
C4 O5 La1 122.2(3) . . ?
C8 O7 La1 116.5(3) . 2_667 ?
O7 C8 C9 125.8(4) . . ?
O7 C8 C10 115.3(4) . 2_667 ?
C9 C8 C10 118.8(4) . 2_667 ?
C8 C9 Br12 118.6(3) . . ?
C10 C9 C8 122.0(4) . . ?
C10 C9 Br12 119.4(3) . . ?
C9 C10 C8 119.2(4) . 2_667 ?
O11 C10 C8 114.7(4) . 2_667 ?
O11 C10 C9 126.1(4) . . ?
C10 O11 La1 114.6(3) . . ?
C14 O13 La1 122.7(3) . 2_556 ?
O13 C14 C15 124.8(4) . . ?
O13 C14 C16 115.4(4) . 2_556 ?
C15 C14 C16 119.8(4) . 2_556 ?
C14 C15 C16 121.5(4) . . ?
C14 C15 Br18 119.8(3) . . ?
C16 C15 Br18 118.7(4) . . ?
C15 C16 C14 118.6(4) . 2_556 ?
O17 C16 C14 116.8(4) . 2_556 ?
O17 C16 C15 124.6(4) . . ?
C16 O17 La1 122.6(3) . . ?
C20 O19 La1 122.4(3) . 2_557 ?
O19 C20 C21 124.6(5) . . ?
O19 C20 C22 116.3(4) . 2_557 ?
C21 C20 C22 119.1(5) . 2_557 ?
C20 C21 Br24 117.7(4) . . ?
C22 C21 C20 122.1(4) . . ?
C22 C21 Br24 120.1(3) . . ?
C21 C22 C20 118.8(4) . 2_557 ?
O23 C22 C20 115.1(5) . 2_557 ?
O23 C22 C21 126.1(4) . . ?
C22 O23 La1 121.2(3) . . ?
C27 C26 C31 120.8(4) . . ?
C26 C27 C28 120.7(7) . . ?
C28 C29 N30 119.3(6) . . ?
C28 C29 C29 116.6(7) . 2_656 ?
N30 C29 C29 124.1(7) . 2_656 ?
N30 C31 C26 117.7(6) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
O25 H25A O45 0.83(2) 1.93(2) 2.760(6) 173(8) . yes
O25 H25B O39 0.83(2) 1.90(4) 2.693(7) 159(8) . yes
O38 H38A O39 0.85(2) 2.29(13) 2.860(12) 125(14) . yes
O38 H38B O45 0.85(2) 2.14(9) 2.893(11) 147(15) . yes
O39 H39A O38 0.84(2) 1.91(7) 2.664(13) 149(12) 2_666 yes
O39 H39B O40 0.85(2) 1.95(5) 2.762(7) 161(13) . yes
O41 H41A O42 0.85(2) 1.96(3) 2.789(6) 166(9) . yes
O41 H41B O43 0.85(2) 2.00(2) 2.845(7) 177(9) . yes
O42 H42A O13 0.84(2) 2.30(7) 2.964(5) 136(8) 2_566 yes
O42 H42B O19 0.84(2) 2.53(7) 3.023(5) 118(6) 2_567 yes
O43 H43A O44 0.853(19) 2.18(3) 2.964(9) 154(7) . yes
O43 H43B O11 0.84(2) 2.00(2) 2.839(5) 172(9) . yes
O44 H44A O5 0.85(2) 2.10(3) 2.911(6) 157(8) . yes
O44 H44B O17 0.84(2) 2.61(9) 3.150(7) 124(8) . yes
O45 H45A O44 0.84(2) 2.15(4) 2.875(8) 145(6) 2_566 yes
O45 H45B O46 0.85(2) 2.03(3) 2.815(8) 153(6) . yes
O46 H46A O40 0.84(2) 2.10(4) 2.901(7) 160(9) 2_666 yes
O46 H46B O47 0.86(2) 1.94(3) 2.792(7) 171(10) . yes

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.796
_oxdiff_exptl_absorpt_empirical_full_min 0.591
# start Validation Reply Form
_vrf_PLAT306_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a 
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......        O40 Check 
RESPONSE: Despite repeated attempts, H atoms for solvent water molecules located in the framework voids (O40, O47) could not be positioned satisfactorily and have been omitted from the refinement.
;
_vrf_PLAT041_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a 
;
PROBLEM: Calc. and Reported SumFormula    Strings  Differ     Please Check 
RESPONSE: H atoms for water molecules located in the framework voids (O40, O47) have been omitted from the refinement. The reported sum formula includes these four H atoms bonded to O40 and O47.
;
_vrf_PLAT042_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a 
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check 
RESPONSE: H atoms for water molecules located in the framework voids (O40, O47) have been omitted from the refinement. The reported moiety formula includes these four H atoms bonded to O40 and O47.
;
_vrf_PLAT043_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a 
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       4.07 Check 
RESPONSE: H atoms for water molecules located in the framework voids (O40, O47) have been omitted from the refinement. The reported molecular weight includes these four H atoms.
;
_vrf_PLAT068_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a 
;
PROBLEM: Reported F000 Differs from Calcd (or Missing)...     Please Check 
RESPONSE: H atoms for water molecules located in the framework voids (O40, O47) have been omitted from the refinement. The reported F000 includes the contribution from these four H atoms.
;
_vrf_PLAT329_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a 
;
PROBLEM: Carbon Atom Hybridisation Unclear for ..........        C27 Check 
RESPONSE: C27 is sp2 hybridised. C27 bonds to C26, H27 and either C28 or N34 due to positional disorder of the cation around an inversion center giving rising to half occupany for C28 and N34.
;
_vrf_PLAT369_MPVK-MPF-2-044C_1_1-mask_smrt_abs_a 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_c     .       1.54 Ang.  
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
# end Validation Reply Form
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mpvk-mpf-2-044b_2_1-mask_smrt_abs_a
_database_code_depnum_ccdc_archive 'CCDC 2431638'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-03-17 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_audit_creation_date             2025-02-25
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         
'C24 H4 Cl8 La2 O18, C14 H12 N2, 4(C2 H3 N), 11(H2 O)'
_chemical_formula_sum            'C46 H50 Cl8 La2 N6 O29'
_chemical_formula_weight         1712.34
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C46 H50 Cl8 La2 N6 O29'
_chemical_oxdiff_usercomment     'Thin maroon plate'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
La La -1.4094 9.0376 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   13.0706(2)
_cell_length_b                   13.8311(2)
_cell_length_c                   18.0949(2)
_cell_angle_alpha                92.5410(10)
_cell_angle_beta                 90.2890(10)
_cell_angle_gamma                101.0080(10)
_cell_volume                     3207.56(8)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    35256
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      79.3900
_cell_measurement_theta_min      2.4570
_shelx_estimated_absorpt_T_max   0.508
_shelx_estimated_absorpt_T_min   0.112
_exptl_absorpt_coefficient_mu    14.001
_exptl_absorpt_correction_T_max  0.847
_exptl_absorpt_correction_T_min  0.165
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.773
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1700
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-6 6 6 0.0348
6 -7 -2 0.0450
0 -4 11 0.1372
-7 -3 -3 0.0204
7 2 4 0.0383
3 -9 2 0.0651
6 5 3 0.0310
-7 5 -4 0.0744
2 0 -12 0.1101
5 -6 -6 0.0657

_exptl_crystal_size_max          0.279
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.056
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-5.6697 5.9844 5.6314 0.0164 0.6869 -0.7265
5.7565 -7.4657 -1.6227 -0.0081 -0.3728 0.9279
0.0484 -3.7506 10.8530 0.0226 0.8583 0.5126
-6.6670 -3.3881 -3.2559 -0.9943 0.0254 -0.1035
7.1808 2.2666 3.5361 0.9721 -0.0250 0.2334
2.8045 -8.8431 1.5864 -0.3160 0.0070 0.9487
5.9225 4.6200 2.8583 0.9984 -0.0254 -0.0500
-7.4570 4.6752 -3.8205 -0.5068 0.0138 -0.8619
1.6340 0.2026 -11.5357 -0.1290 -0.9837 -0.1249
5.1830 -6.2017 -5.9799 -0.0898 -0.6939 0.7145

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0559
_diffrn_reflns_av_unetI/netI     0.0415
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            53712
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.765
_diffrn_reflns_theta_min         2.444
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -82.00  -2.00   0.50    1.00    --  -48.11 111.00 -61.00  160
  2  ω     24.00  84.00   0.50    1.00    --   48.11-111.00-155.00  120
  3  ω   -158.00 -81.00   0.50    2.50    --  -90.00-111.00-155.00  154
  4  ω    -63.00 -37.00   0.50    2.50    --  -90.00 111.00 -61.00   52
  5  ω     51.00  76.00   0.50    2.50    --  111.50-111.00-155.00   50
  6  ω    129.00 155.00   0.50    2.50    --  111.50 111.00 -61.00   52
  7  ω    -29.00  24.00   0.50    1.00    --  -48.11  19.00 120.00  106
  8  ω    -39.00 -14.00   0.50    1.00    --  -48.11 125.00 150.00   50
  9  ω    -83.00 -49.00   0.50    1.00    --  -48.11 125.00  30.00   68
 10  ω    -29.00  20.00   0.50    1.00    --  -48.11  19.00   0.00   98
 11  ω   -115.00 -89.00   0.50    1.00    --  -48.11 -38.00 -90.00   52
 12  ω   -118.00 -26.00   0.50    1.00    --  -48.11 -77.00-120.00  184
 13  ω    -30.00  25.00   0.50    1.00    --  -48.11  19.00-150.00  110
 14  ω    -84.00 -46.00   0.50    1.00    --  -48.11 125.00 150.00   76
 15  ω      4.00  79.00   0.50    1.00    --   48.11 -99.00   0.00  150
 16  ω    -25.00   0.00   0.50    1.00    --   48.11 -19.00 120.00   50
 17  ω    -50.00 -25.00   0.50    2.50    --  -90.00  45.00  60.00   50
 18  ω   -160.00 -84.00   0.50    2.50    --  -90.00 -58.00 -78.74  152
 19  ω     40.00  66.00   0.50    2.50    --  111.50 -61.00-120.00   52
 20  ω     41.00 103.00   0.50    2.50    --  111.50 -94.00 -30.00  124
 21  ω     79.00 105.00   0.50    2.50    --  111.50 -94.00-120.00   52
 22  ω    106.00 166.00   0.50    2.50    --  111.50  30.00   0.00  120
 23  ω     79.00 105.00   0.50    2.50    --  111.50 -94.00  90.00   52
 24  ω    120.00 173.00   0.50    2.50    --  111.50  15.00 120.00  106
 25  ω     43.00  71.00   0.50    2.50    --  111.50 -61.00   0.00   56
 26  ω    153.00 178.00   0.50    2.50    --  111.50  15.00  30.00   50
 27  ω    101.00 154.00   0.50    2.50    --  111.50  30.00-180.00  106
 28  ω    106.00 147.00   0.50    2.50    --  111.50  15.00 -30.00   82
 29  ω     45.00 109.00   0.50    2.50    --  111.50-125.00 120.00  128
 30  ω     43.00 104.00   0.50    2.50    --  111.50 -94.00 -90.00  122
 31  ω     51.00 107.00   0.50    2.50    --  111.50-103.00-175.00  112
 32  ω     47.00  72.00   0.50    2.50    --  111.50 -94.00   0.00   50
 33  ω     74.00 104.00   0.50    2.50    --  111.50 -94.00   0.00   60
 34  ω     90.00 176.00   0.50    2.50    --  111.50  77.00 -90.00  172
 35  ω     47.00  72.00   0.50    2.50    --  111.50 -94.00 120.00   50
 36  ω     74.00 104.00   0.50    2.50    --  111.50 -94.00 120.00   60
 37  ω     40.00 101.00   0.50    2.50    --  111.50 -94.00-150.00  122
 38  ω     55.00 104.00   0.50    2.50    --  111.50 -94.00 -60.00   98
 39  ω     48.00 110.00   0.50    2.50    --  111.50-125.00  90.00  124
 40  ω    151.00 176.00   0.50    2.50    --  111.50  45.00 -30.00   50
 41  ω     45.00  78.00   0.50    2.50    --  111.50 -77.00   0.00   66
 42  ω    101.00 147.00   0.50    2.50    --  111.50  45.00 -30.00   92
 43  ω     43.00  85.00   0.50    2.50    --  111.50-125.00-180.00   84
 44  ω     41.00  66.00   0.50    2.50    --  111.50 -61.00-150.00   50
 45  ω     42.00  71.00   0.50    2.50    --  111.50 -94.00-180.00   58
 46  ω     77.00 105.00   0.50    2.50    --  111.50 -94.00-180.00   56
 47  ω     97.00 157.00   0.50    2.50    --  111.50 125.00 -30.00  120
 48  ω    116.00 157.00   0.50    2.50    --  111.50  15.00 -90.00   82
 49  ω    105.00 163.00   0.50    2.50    --  111.50  61.00  60.00  116
 50  ω    102.00 175.00   0.50    2.50    --  111.50  45.00-150.00  146
 51  ω     50.00 101.00   0.50    2.50    --  111.50 -77.00-150.00  102
 52  ω     48.00  73.00   0.50    2.50    --  111.50 -77.00  90.00   50
 53  ω     71.00 101.00   0.50    2.50    --  111.50 -94.00  30.00   60
 54  ω    109.00 135.00   0.50    2.50    --  111.50  45.00 120.00   52
 55  ω     41.00  69.00   0.50    2.50    --  111.50 -61.00 -30.00   56
 56  ω     40.00  65.00   0.50    2.50    --  111.50 -61.00  60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0995473000
_diffrn_orient_matrix_UB_12      0.0720714000
_diffrn_orient_matrix_UB_13      0.0265484000
_diffrn_orient_matrix_UB_21      -0.0424949000
_diffrn_orient_matrix_UB_22      -0.0000553000
_diffrn_orient_matrix_UB_23      0.0792583000
_diffrn_orient_matrix_UB_31      0.0520101000
_diffrn_orient_matrix_UB_32      -0.0878008000
_diffrn_orient_matrix_UB_33      0.0166547000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                12904
_reflns_number_total             13646
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection       
'CrysAlisPro system (CCD 43.111a 64-bit (release 27-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         2.181
_refine_diff_density_min         -1.709
_refine_diff_density_rms         0.155
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     902
_refine_ls_number_reflns         13646
_refine_ls_number_restraints     182
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0463
_refine_ls_restrained_S_all      1.043
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0905P)²+3.0536P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1276
_refine_ls_wR_factor_ref         0.1294
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O19-H19A = O19-H19B
 0.84 with sigma of 0.02
 H19A-H19B
 1.34 with sigma of 0.04
 O50-H50A = O50-H50B
 0.84 with sigma of 0.02
 H50A-H50B
 1.34 with sigma of 0.04
 O79-H79A = O79-H79B
 0.84 with sigma of 0.02
 H79A-H79B
 1.34 with sigma of 0.04
 O80-H80A = O80-H80B
 0.84 with sigma of 0.02
 H80A-H80B
 1.34 with sigma of 0.04
 O81-H81A = O81-H81B
 0.84 with sigma of 0.02
 H81A-H81B
 1.34 with sigma of 0.04
 O82-H82A = O82-H82B
 0.84 with sigma of 0.02
 H82A-H82B
 1.34 with sigma of 0.04
 O83-H83A = O83-H83B
 0.84 with sigma of 0.02
 H83A-H83B
 1.34 with sigma of 0.04
 O84-H84A = O84-H84B
 0.84 with sigma of 0.02
 H84A-H84B
 1.34 with sigma of 0.04
 O85-H85A = O85-H85B
 0.84 with sigma of 0.02
 H85A-H85B
 1.34 with sigma of 0.04
 O86-H86A = O86-H86B
 0.84 with sigma of 0.02
 H86A-H86B
 1.34 with sigma of 0.04
 O87-H87A = O87-H87B
 0.84 with sigma of 0.02
 H87A-H87B
 1.34 with sigma of 0.04
 O88-H88A = O88-H88B
 0.84 with sigma of 0.02
 H88A-H88B
 1.34 with sigma of 0.04
 O89-H89A = O89-H89B
 0.84 with sigma of 0.02
 H89A-H89B
 1.34 with sigma of 0.04
 H79B-O80_$2
 1.92 with sigma of 0.04
 H83B-O38_$1
 2.02 with sigma of 0.04
3. Rigid body (RIGU) restrains
 N51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, N64, C65, C66
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C66(H66A,H66B)
4.b Aromatic/amide H refined with riding coordinates:
 C52(H52), C53(H53), C54(H54), C57(H57), C58(H58), C61(H61), C62(H62), C63(H63)
4.c Idealised Me refined as rotating group:
 C69(H69A,H69B,H69C), C72(H72A,H72B,H72C), C75(H75A,H75B,H75C), C78(H78A,H78B,
 H78C)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
La1 La 0.70466(2) 0.28901(2) 0.55777(2) 0.01993(8) Uani 1 1 d . . . . .
O1 O 0.3433(2) 0.5432(2) 0.41829(16) 0.0262(6) Uani 1 1 d . . . . .
La2 La 0.29435(2) 0.21665(2) 0.95687(2) 0.01782(7) Uani 1 1 d . . . . .
C2 C 0.4180(3) 0.5192(3) 0.4527(2) 0.0224(7) Uani 1 1 d . . . . .
C3 C 0.4679(3) 0.4421(3) 0.4322(2) 0.0241(7) Uani 1 1 d . . . . .
C4 C 0.5461(3) 0.4169(3) 0.4763(2) 0.0229(7) Uani 1 1 d . . . . .
O5 O 0.5913(2) 0.3461(2) 0.46275(15) 0.0251(5) Uani 1 1 d . . . . .
Cl6 Cl 0.43302(7) 0.37451(7) 0.35024(5) 0.02781(19) Uani 1 1 d . . . . .
O7 O 0.3764(2) -0.1177(2) 0.40111(15) 0.0282(6) Uani 1 1 d . . . . .
C8 C 0.4364(3) -0.0600(3) 0.4441(2) 0.0233(7) Uani 1 1 d . . . . .
C9 C 0.5125(3) 0.0192(3) 0.4220(2) 0.0238(7) Uani 1 1 d . . . . .
C10 C 0.5752(3) 0.0808(3) 0.4736(2) 0.0230(7) Uani 1 1 d . . . . .
O11 O 0.6429(2) 0.1554(2) 0.45868(15) 0.0260(6) Uani 1 1 d . . . . .
Cl12 Cl 0.52495(8) 0.04228(7) 0.32857(5) 0.0300(2) Uani 1 1 d . . . . .
O13 O 1.1778(2) 0.6249(2) 0.54086(15) 0.0246(5) Uani 1 1 d . . . . .
C14 C 1.0943(3) 0.5650(3) 0.5262(2) 0.0212(7) Uani 1 1 d . . . . .
C15 C 1.0309(3) 0.5105(3) 0.5775(2) 0.0229(7) Uani 1 1 d . . . . .
C16 C 0.9378(3) 0.4469(3) 0.5567(2) 0.0216(7) Uani 1 1 d . . . . .
O17 O 0.8765(2) 0.39786(19) 0.60010(15) 0.0239(5) Uani 1 1 d . . . . .
Cl18 Cl 1.07001(7) 0.52147(7) 0.66934(5) 0.02425(17) Uani 1 1 d . . . . .
O19 O 0.8469(2) 0.1889(2) 0.56752(19) 0.0329(6) Uani 1 1 d D . . . .
H19A H 0.836(4) 0.130(2) 0.551(3) 0.049 Uiso 1 1 d D U . . .
H19B H 0.906(3) 0.197(4) 0.589(3) 0.049 Uiso 1 1 d D U . . .
C20 C 0.4089(3) 0.2291(3) 0.7117(2) 0.0232(7) Uani 1 1 d . . . . .
C21 C 0.5067(3) 0.2626(3) 0.6788(2) 0.0220(7) Uani 1 1 d . . . . .
C22 C 0.6036(3) 0.2922(3) 0.7288(2) 0.0224(7) Uani 1 1 d . . . . .
C23 C 0.5918(3) 0.2947(3) 0.8044(2) 0.0226(7) Uani 1 1 d . . . . .
C24 C 0.4942(3) 0.2619(3) 0.8375(2) 0.0210(7) Uani 1 1 d . . . . .
C25 C 0.3973(3) 0.2297(3) 0.7874(2) 0.0226(7) Uani 1 1 d . . . . .
O26 O 0.5199(2) 0.2706(2) 0.61089(15) 0.0267(6) Uani 1 1 d . . . . .
O27 O 0.69042(19) 0.3138(2) 0.69561(15) 0.0238(5) Uani 1 1 d . . . . .
O28 O 0.4800(2) 0.2569(2) 0.90505(15) 0.0258(5) Uani 1 1 d . . . . .
O29 O 0.31083(19) 0.2058(2) 0.81981(14) 0.0227(5) Uani 1 1 d . . . . .
Cl30 Cl 0.30078(7) 0.19073(7) 0.65496(5) 0.02732(19) Uani 1 1 d . . . . .
Cl31 Cl 0.69806(7) 0.33598(7) 0.86228(5) 0.02917(19) Uani 1 1 d . . . . .
O32 O 0.6590(2) -0.0502(2) 1.07570(15) 0.0242(5) Uani 1 1 d . . . . .
C33 C 0.5846(3) -0.0225(3) 1.0439(2) 0.0216(7) Uani 1 1 d . . . . .
C34 C 0.5431(3) 0.0600(3) 1.0646(2) 0.0226(7) Uani 1 1 d . . . . .
C35 C 0.4608(3) 0.0864(3) 1.0248(2) 0.0198(7) Uani 1 1 d . . . . .
O36 O 0.4204(2) 0.15991(19) 1.04085(15) 0.0231(5) Uani 1 1 d . . . . .
Cl37 Cl 0.58961(7) 0.12974(7) 1.14367(5) 0.02667(18) Uani 1 1 d . . . . .
O38 O 0.6533(2) 0.60553(19) 1.08669(15) 0.0254(5) Uani 1 1 d . . . . .
C39 C 0.5792(3) 0.5534(3) 1.0496(2) 0.0229(7) Uani 1 1 d . . . . .
C40 C 0.5024(3) 0.4804(3) 1.0779(2) 0.0240(7) Uani 1 1 d . . . . .
C41 C 0.4247(3) 0.4248(3) 1.0327(2) 0.0210(7) Uani 1 1 d . . . . .
O42 O 0.3552(2) 0.35531(19) 1.05368(15) 0.0246(5) Uani 1 1 d . . . . .
Cl43 Cl 0.50559(8) 0.45812(7) 1.17150(5) 0.0323(2) Uani 1 1 d . . . . .
O44 O -0.1312(2) -0.10455(19) 1.09430(15) 0.0214(5) Uani 1 1 d . . . . .
C45 C -0.0674(3) -0.0541(3) 1.0536(2) 0.0197(7) Uani 1 1 d . . . . .
C46 C 0.0260(3) 0.0068(3) 1.0782(2) 0.0199(7) Uani 1 1 d . . . . .
C47 C 0.0945(3) 0.0614(3) 1.0300(2) 0.0201(7) Uani 1 1 d . . . . .
O48 O 0.1786(2) 0.11820(18) 1.04816(15) 0.0216(5) Uani 1 1 d . . . . .
Cl49 Cl 0.05762(6) 0.01354(6) 1.17155(4) 0.02165(16) Uani 1 1 d . . . . .
O50 O 0.1374(2) 0.3041(2) 0.96425(17) 0.0266(6) Uani 1 1 d D . . . .
H50A H 0.149(4) 0.3655(15) 0.970(3) 0.040 Uiso 1 1 d D U . . .
H50B H 0.083(3) 0.288(3) 0.938(3) 0.040 Uiso 1 1 d D U . . .
N51 N -0.0901(3) 0.6753(2) 0.78829(19) 0.0276(7) Uani 1 1 d . . . . .
C52 C -0.1705(3) 0.5992(3) 0.7771(2) 0.0293(8) Uani 1 1 d . . . . .
H52 H -0.203278 0.566785 0.818384 0.035 Uiso 1 1 calc R U . . .
C53 C -0.2063(3) 0.5675(3) 0.7064(3) 0.0311(8) Uani 1 1 d . . . . .
H53 H -0.261143 0.511943 0.699072 0.037 Uiso 1 1 calc R U . . .
C54 C -0.1618(3) 0.6171(3) 0.6468(2) 0.0296(8) Uani 1 1 d . . . . .
H54 H -0.188663 0.598161 0.598307 0.035 Uiso 1 1 calc R U . . .
C55 C -0.0765(3) 0.6958(3) 0.6575(2) 0.0275(8) Uani 1 1 d . . . . .
C56 C -0.0389(3) 0.7220(3) 0.7301(2) 0.0239(7) Uani 1 1 d . . . . .
C57 C -0.0290(4) 0.7518(3) 0.5975(2) 0.0348(9) Uani 1 1 d . . . . .
H57 H -0.053801 0.734666 0.548289 0.042 Uiso 1 1 calc R U . . .
C58 C 0.0511(3) 0.8292(3) 0.6107(2) 0.0355(9) Uani 1 1 d . . . . .
H58 H 0.081040 0.866351 0.570563 0.043 Uiso 1 1 calc R U . . .
C59 C 0.0475(3) 0.8010(3) 0.7425(2) 0.0265(8) Uani 1 1 d . . . . .
C60 C 0.0912(3) 0.8555(3) 0.6840(2) 0.0310(8) Uani 1 1 d . . . . .
C61 C 0.1751(3) 0.9367(3) 0.6997(3) 0.0373(9) Uani 1 1 d . . . . .
H61 H 0.205276 0.976173 0.660839 0.045 Uiso 1 1 calc R U . . .
C62 C 0.2119(3) 0.9573(3) 0.7707(3) 0.0368(9) Uani 1 1 d . . . . .
H62 H 0.266171 1.012529 0.781553 0.044 Uiso 1 1 calc R U . . .
C63 C 0.1698(3) 0.8974(3) 0.8267(3) 0.0324(9) Uani 1 1 d . . . . .
H63 H 0.196966 0.910762 0.875715 0.039 Uiso 1 1 calc R U . . .
N64 N 0.0915(3) 0.8210(2) 0.8127(2) 0.0286(7) Uani 1 1 d . . . . .
C65 C 0.0527(3) 0.7513(3) 0.8707(2) 0.0313(8) Uani 1 1 d . . . . .
H65A H 0.070396 0.783982 0.920104 0.038 Uiso 1 1 calc R U . . .
H65B H 0.087077 0.693503 0.866008 0.038 Uiso 1 1 calc R U . . .
C66 C -0.0627(3) 0.7180(3) 0.8634(2) 0.0297(8) Uani 1 1 d . . . . .
H66A H -0.087020 0.668070 0.900236 0.036 Uiso 1 1 calc R U . . .
H66B H -0.097619 0.774687 0.873316 0.036 Uiso 1 1 calc R U . . .
N67 N 0.2117(3) 0.1517(3) 0.3027(3) 0.0447(10) Uani 1 1 d . . . . .
C68 C 0.2728(4) 0.1739(3) 0.2590(3) 0.0363(9) Uani 1 1 d . . . . .
C69 C 0.3494(5) 0.2014(4) 0.2019(3) 0.0508(12) Uani 1 1 d . . . . .
H69A H 0.336344 0.152531 0.160355 0.076 Uiso 1 1 calc R U . . .
H69B H 0.419525 0.203823 0.222215 0.076 Uiso 1 1 calc R U . . .
H69C H 0.343957 0.266407 0.184564 0.076 Uiso 1 1 calc R U . . .
N70 N 0.2135(3) 0.3755(3) 0.5427(2) 0.0446(9) Uani 1 1 d . . . . .
C71 C 0.2627(4) 0.4134(4) 0.5943(3) 0.0416(11) Uani 1 1 d . . . . .
C72 C 0.3217(4) 0.4575(4) 0.6583(3) 0.0375(10) Uani 1 1 d . . . . .
H72A H 0.283197 0.436860 0.703030 0.056 Uiso 1 1 calc R U . . .
H72B H 0.333098 0.529499 0.656408 0.056 Uiso 1 1 calc R U . . .
H72C H 0.389083 0.436398 0.659111 0.056 Uiso 1 1 calc R U . . .
N73 N 0.7901(4) 0.9844(3) 0.5178(3) 0.0616(14) Uani 1 1 d . . . . .
C74 C 0.7347(4) 0.9099(4) 0.5257(3) 0.0490(12) Uani 1 1 d . . . . .
C75 C 0.6669(4) 0.8160(4) 0.5353(3) 0.0436(11) Uani 1 1 d . . . . .
H75A H 0.615305 0.802378 0.494856 0.065 Uiso 1 1 calc R U . . .
H75B H 0.630978 0.817962 0.582640 0.065 Uiso 1 1 calc R U . . .
H75C H 0.708283 0.763926 0.535055 0.065 Uiso 1 1 calc R U . . .
N76 N 0.6859(4) 0.0553(3) 0.8735(3) 0.0475(10) Uani 1 1 d . . . . .
C77 C 0.7151(4) 0.0724(3) 0.8147(3) 0.0420(11) Uani 1 1 d . . . . .
C78 C 0.7555(4) 0.0931(4) 0.7406(3) 0.0476(12) Uani 1 1 d . . . . .
H78A H 0.794492 0.042401 0.724043 0.071 Uiso 1 1 calc R U . . .
H78B H 0.801779 0.157902 0.741870 0.071 Uiso 1 1 calc R U . . .
H78C H 0.697288 0.092898 0.706195 0.071 Uiso 1 1 calc R U . . .
O79 O 0.0379(3) 0.2452(4) 0.6285(3) 0.0687(14) Uani 1 1 d D . . . .
H79A H 0.085(5) 0.260(7) 0.599(4) 0.103 Uiso 1 1 d D U . . .
H79B H 0.058(6) 0.220(5) 0.666(2) 0.103 Uiso 1 1 d D U . . .
O80 O 0.8941(2) 0.7735(2) 0.22810(18) 0.0367(7) Uani 1 1 d D . . . .
H80A H 0.843(3) 0.804(4) 0.233(3) 0.055 Uiso 1 1 d D U . . .
H80B H 0.937(3) 0.813(3) 0.203(3) 0.055 Uiso 1 1 d D U . . .
O81 O 0.2775(3) 0.7237(3) 0.67741(18) 0.0419(7) Uani 1 1 d D . . . .
H81A H 0.325(3) 0.763(3) 0.656(3) 0.063 Uiso 1 1 d D U . . .
H81B H 0.252(4) 0.684(4) 0.643(2) 0.063 Uiso 1 1 d D U . . .
O82 O 0.2322(3) 0.6403(2) 0.81242(17) 0.0349(7) Uani 1 1 d D . . . .
H82A H 0.258(5) 0.667(4) 0.773(2) 0.052 Uiso 1 1 d D U . . .
H82B H 0.230(5) 0.5804(16) 0.802(3) 0.052 Uiso 1 1 d D U . . .
O83 O 0.1890(3) 0.4321(2) 0.8146(2) 0.0477(9) Uani 1 1 d D . . . .
H83A H 0.167(5) 0.373(2) 0.795(4) 0.072 Uiso 1 1 d D U . . .
H83B H 0.249(3) 0.421(4) 0.831(3) 0.072 Uiso 1 1 d D U . . .
O84 O 0.2987(3) 0.6692(2) 0.95597(18) 0.0376(7) Uani 1 1 d D . . . .
H84A H 0.302(4) 0.666(5) 0.9093(11) 0.056 Uiso 1 1 d D U . . .
H84B H 0.358(3) 0.661(5) 0.970(3) 0.056 Uiso 1 1 d D U . . .
O85 O 0.1446(3) 0.5037(2) -0.01303(19) 0.0391(7) Uani 1 1 d D . . . .
H85A H 0.133(4) 0.514(4) 0.0322(14) 0.059 Uiso 1 1 d D U . . .
H85B H 0.206(3) 0.541(4) -0.017(3) 0.059 Uiso 1 1 d D U . . .
O86 O 0.9532(2) 0.2410(2) 0.88744(19) 0.0335(6) Uani 1 1 d D . . . .
H86A H 0.926(4) 0.268(4) 0.854(2) 0.050 Uiso 1 1 d D U . . .
H86B H 0.906(3) 0.228(4) 0.919(2) 0.050 Uiso 1 1 d D U . . .
O87 O 0.7992(2) 0.1726(2) 0.99180(19) 0.0385(7) Uani 1 1 d D . . . .
H87A H 0.768(4) 0.129(3) 0.960(3) 0.058 Uiso 1 1 d D U . . .
H87B H 0.761(4) 0.213(3) 1.006(3) 0.058 Uiso 1 1 d D U . . .
O88 O 0.0301(2) 0.5015(2) 0.11730(19) 0.0373(7) Uani 1 1 d D . . . .
H88A H 0.044(4) 0.548(3) 0.152(3) 0.056 Uiso 1 1 d D U . . .
H88B H -0.0361(15) 0.489(4) 0.119(3) 0.056 Uiso 1 1 d D U . . .
O89 O 0.9033(2) 0.3528(2) 0.76370(17) 0.0345(6) Uani 1 1 d D . . . .
H89A H 0.8378(16) 0.338(4) 0.756(3) 0.052 Uiso 1 1 d D U . . .
H89B H 0.928(4) 0.332(4) 0.724(2) 0.052 Uiso 1 1 d D U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
La1 O1 2.537(3) 2_666 ?
La1 O5 2.513(3) . ?
La1 O7 2.549(3) 2_656 ?
La1 O11 2.530(3) . ?
La1 O13 2.546(3) 2_766 ?
La1 O17 2.547(3) . ?
La1 O19 2.531(3) . ?
La1 O26 2.575(3) . ?
La1 O27 2.515(3) . ?
O1 C2 1.260(5) . ?
La2 O28 2.575(3) . ?
La2 O29 2.491(3) . ?
La2 O32 2.538(3) 2_657 ?
La2 O36 2.493(3) . ?
La2 O38 2.583(3) 2_667 ?
La2 O42 2.546(3) . ?
La2 O44 2.530(3) 2_557 ?
La2 O48 2.512(3) . ?
La2 O50 2.575(3) . ?
C2 C3 1.390(6) . ?
C2 C4 1.544(5) 2_666 ?
C3 C4 1.398(5) . ?
C3 Cl6 1.729(4) . ?
C4 O5 1.253(5) . ?
O7 C8 1.248(5) . ?
C8 C9 1.406(5) . ?
C8 C10 1.531(5) 2_656 ?
C9 C10 1.388(5) . ?
C9 Cl12 1.736(4) . ?
C10 O11 1.265(5) . ?
O13 C14 1.257(5) . ?
C14 C15 1.395(5) . ?
C14 C16 1.549(5) 2_766 ?
C15 C16 1.398(5) . ?
C15 Cl18 1.728(4) . ?
C16 O17 1.250(5) . ?
O19 H19A 0.842(19) . ?
O19 H19B 0.854(19) . ?
C20 C21 1.417(5) . ?
C20 C25 1.380(5) . ?
C20 Cl30 1.728(4) . ?
C21 C22 1.533(5) . ?
C21 O26 1.248(5) . ?
C22 C23 1.378(5) . ?
C22 O27 1.277(5) . ?
C23 C24 1.415(5) . ?
C23 Cl31 1.726(4) . ?
C24 C25 1.537(5) . ?
C24 O28 1.240(5) . ?
C25 O29 1.269(5) . ?
O32 C33 1.257(4) . ?
C33 C34 1.392(5) . ?
C33 C35 1.541(5) 2_657 ?
C34 C35 1.405(5) . ?
C34 Cl37 1.729(4) . ?
C35 O36 1.256(5) . ?
O38 C39 1.262(5) . ?
C39 C40 1.399(5) . ?
C39 C41 1.535(5) 2_667 ?
C40 C41 1.389(5) . ?
C40 Cl43 1.737(4) . ?
C41 O42 1.263(5) . ?
O44 C45 1.247(4) . ?
C45 C46 1.403(5) . ?
C45 C47 1.545(5) 2_557 ?
C46 C47 1.393(5) . ?
C46 Cl49 1.732(4) . ?
C47 O48 1.255(5) . ?
O50 H50A 0.836(19) . ?
O50 H50B 0.840(19) . ?
N51 C52 1.345(5) . ?
N51 C56 1.370(5) . ?
N51 C66 1.473(5) . ?
C52 H52 0.9500 . ?
C52 C53 1.383(6) . ?
C53 H53 0.9500 . ?
C53 C54 1.375(6) . ?
C54 H54 0.9500 . ?
C54 C55 1.408(6) . ?
C55 C56 1.409(5) . ?
C55 C57 1.435(6) . ?
C56 C59 1.423(5) . ?
C57 H57 0.9500 . ?
C57 C58 1.359(6) . ?
C58 H58 0.9500 . ?
C58 C60 1.431(6) . ?
C59 C60 1.387(6) . ?
C59 N64 1.387(5) . ?
C60 C61 1.429(6) . ?
C61 H61 0.9500 . ?
C61 C62 1.369(7) . ?
C62 H62 0.9500 . ?
C62 C63 1.388(7) . ?
C63 H63 0.9500 . ?
C63 N64 1.338(5) . ?
N64 C65 1.481(6) . ?
C65 H65A 0.9900 . ?
C65 H65B 0.9900 . ?
C65 C66 1.494(6) . ?
C66 H66A 0.9900 . ?
C66 H66B 0.9900 . ?
N67 C68 1.136(7) . ?
C68 C69 1.455(7) . ?
C69 H69A 0.9800 . ?
C69 H69B 0.9800 . ?
C69 H69C 0.9800 . ?
N70 C71 1.177(7) . ?
C71 C72 1.433(7) . ?
C72 H72A 0.9800 . ?
C72 H72B 0.9800 . ?
C72 H72C 0.9800 . ?
N73 C74 1.157(7) . ?
C74 C75 1.444(7) . ?
C75 H75A 0.9800 . ?
C75 H75B 0.9800 . ?
C75 H75C 0.9800 . ?
N76 C77 1.151(7) . ?
C77 C78 1.464(8) . ?
C78 H78A 0.9800 . ?
C78 H78B 0.9800 . ?
C78 H78C 0.9800 . ?
O79 H79A 0.83(2) . ?
O79 H79B 0.845(19) . ?
O80 H80A 0.860(19) . ?
O80 H80B 0.845(19) . ?
O81 H81A 0.85(2) . ?
O81 H81B 0.84(2) . ?
O82 H82A 0.869(19) . ?
O82 H82B 0.838(19) . ?
O83 H83A 0.87(2) . ?
O83 H83B 0.882(19) . ?
O84 H84A 0.844(19) . ?
O84 H84B 0.846(19) . ?
O85 H85A 0.842(19) . ?
O85 H85B 0.88(2) . ?
O86 H86A 0.840(19) . ?
O86 H86B 0.843(19) . ?
O87 H87A 0.86(2) . ?
O87 H87B 0.850(19) . ?
O88 H88A 0.869(19) . ?
O88 H88B 0.850(19) . ?
O89 H89A 0.851(19) . ?
O89 H89B 0.852(19) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 La1 O7 132.31(9) 2_666 2_656 ?
O1 La1 O13 84.31(9) 2_666 2_766 ?
O1 La1 O17 76.66(9) 2_666 . ?
O1 La1 O26 69.45(9) 2_666 . ?
O5 La1 O1 62.66(9) . 2_666 ?
O5 La1 O7 111.06(9) . 2_656 ?
O5 La1 O11 68.60(9) . . ?
O5 La1 O13 71.85(9) . 2_766 ?
O5 La1 O17 120.56(9) . . ?
O5 La1 O19 140.63(10) . . ?
O5 La1 O26 72.48(9) . . ?
O5 La1 O27 125.39(9) . . ?
O7 La1 O26 64.18(9) 2_656 . ?
O11 La1 O1 130.92(9) . 2_666 ?
O11 La1 O7 62.02(9) . 2_656 ?
O11 La1 O13 86.08(9) . 2_766 ?
O11 La1 O17 137.32(9) . . ?
O11 La1 O19 80.06(10) . . ?
O11 La1 O26 91.34(9) . . ?
O13 La1 O7 141.58(9) 2_766 2_656 ?
O13 La1 O17 62.27(8) 2_766 . ?
O13 La1 O26 142.56(9) 2_766 . ?
O17 La1 O7 128.38(9) . 2_656 ?
O17 La1 O26 131.26(9) . . ?
O19 La1 O1 145.45(9) . 2_666 ?
O19 La1 O7 71.36(9) . 2_656 ?
O19 La1 O13 83.13(10) . 2_766 ?
O19 La1 O17 68.99(9) . . ?
O19 La1 O26 133.18(10) . . ?
O27 La1 O1 73.03(9) . 2_666 ?
O27 La1 O7 76.56(9) . 2_656 ?
O27 La1 O11 137.98(9) . . ?
O27 La1 O13 134.82(8) . 2_766 ?
O27 La1 O17 74.53(8) . . ?
O27 La1 O19 93.83(10) . . ?
O27 La1 O26 62.87(8) . . ?
C2 O1 La1 120.9(2) . 2_666 ?
O28 La2 O38 66.15(9) . 2_667 ?
O29 La2 O28 63.15(8) . . ?
O29 La2 O32 73.43(9) . 2_657 ?
O29 La2 O36 121.81(9) . . ?
O29 La2 O38 72.59(9) . 2_667 ?
O29 La2 O42 132.53(9) . . ?
O29 La2 O44 72.73(8) . 2_557 ?
O29 La2 O48 134.23(8) . . ?
O29 La2 O50 98.57(9) . . ?
O32 La2 O28 75.08(9) 2_657 . ?
O32 La2 O38 136.80(9) 2_657 2_667 ?
O32 La2 O42 135.53(9) 2_657 . ?
O32 La2 O50 141.58(9) 2_657 . ?
O36 La2 O28 69.53(9) . . ?
O36 La2 O32 63.06(9) . 2_657 ?
O36 La2 O38 116.40(8) . 2_667 ?
O36 La2 O42 72.65(9) . . ?
O36 La2 O44 123.06(8) . 2_557 ?
O36 La2 O48 76.76(9) . . ?
O36 La2 O50 139.47(9) . . ?
O42 La2 O28 86.52(9) . . ?
O42 La2 O38 61.60(9) . 2_667 ?
O42 La2 O50 77.64(9) . . ?
O44 La2 O28 130.90(9) 2_557 . ?
O44 La2 O32 72.60(8) 2_557 2_657 ?
O44 La2 O38 120.30(8) 2_557 2_667 ?
O44 La2 O42 141.66(9) 2_557 . ?
O44 La2 O50 69.20(8) 2_557 . ?
O48 La2 O28 145.19(8) . . ?
O48 La2 O32 82.28(9) . 2_657 ?
O48 La2 O38 140.92(9) . 2_667 ?
O48 La2 O42 91.68(8) . . ?
O48 La2 O44 63.10(8) . 2_557 ?
O48 La2 O50 77.21(9) . . ?
O50 La2 O28 135.62(9) . . ?
O50 La2 O38 69.85(9) . 2_667 ?
O1 C2 C3 125.7(4) . . ?
O1 C2 C4 114.8(3) . 2_666 ?
C3 C2 C4 119.4(3) . 2_666 ?
C2 C3 C4 121.8(3) . . ?
C2 C3 Cl6 119.8(3) . . ?
C4 C3 Cl6 118.4(3) . . ?
C3 C4 C2 118.7(3) . 2_666 ?
O5 C4 C2 116.1(3) . 2_666 ?
O5 C4 C3 125.2(4) . . ?
C4 O5 La1 121.7(2) . . ?
C8 O7 La1 119.6(2) . 2_656 ?
O7 C8 C9 124.8(4) . . ?
O7 C8 C10 115.7(3) . 2_656 ?
C9 C8 C10 119.6(3) . 2_656 ?
C8 C9 Cl12 119.2(3) . . ?
C10 C9 C8 121.0(4) . . ?
C10 C9 Cl12 119.7(3) . . ?
C9 C10 C8 119.4(3) . 2_656 ?
O11 C10 C8 115.5(3) . 2_656 ?
O11 C10 C9 125.1(4) . . ?
C10 O11 La1 120.0(2) . . ?
C14 O13 La1 123.3(2) . 2_766 ?
O13 C14 C15 125.7(4) . . ?
O13 C14 C16 115.1(3) . 2_766 ?
C15 C14 C16 119.2(3) . 2_766 ?
C14 C15 C16 122.1(3) . . ?
C14 C15 Cl18 118.7(3) . . ?
C16 C15 Cl18 119.2(3) . . ?
C15 C16 C14 118.7(3) . 2_766 ?
O17 C16 C14 116.1(3) . 2_766 ?
O17 C16 C15 125.2(3) . . ?
C16 O17 La1 123.0(2) . . ?
La1 O19 H19A 120(4) . . ?
La1 O19 H19B 136(4) . . ?
H19A O19 H19B 104(4) . . ?
C21 C20 Cl30 118.7(3) . . ?
C25 C20 C21 121.9(3) . . ?
C25 C20 Cl30 119.3(3) . . ?
C20 C21 C22 118.8(3) . . ?
O26 C21 C20 124.4(3) . . ?
O26 C21 C22 116.8(3) . . ?
C23 C22 C21 119.1(3) . . ?
O27 C22 C21 115.9(3) . . ?
O27 C22 C23 125.1(3) . . ?
C22 C23 C24 121.9(3) . . ?
C22 C23 Cl31 120.3(3) . . ?
C24 C23 Cl31 117.7(3) . . ?
C23 C24 C25 118.9(3) . . ?
O28 C24 C23 124.8(3) . . ?
O28 C24 C25 116.3(3) . . ?
C20 C25 C24 119.0(3) . . ?
O29 C25 C20 124.5(3) . . ?
O29 C25 C24 116.5(3) . . ?
C21 O26 La1 119.9(2) . . ?
C22 O27 La1 122.1(2) . . ?
C24 O28 La2 120.7(2) . . ?
C25 O29 La2 122.8(2) . . ?
C33 O32 La2 121.3(2) . 2_657 ?
O32 C33 C34 125.8(3) . . ?
O32 C33 C35 115.2(3) . 2_657 ?
C34 C33 C35 119.0(3) . 2_657 ?
C33 C34 C35 121.8(3) . . ?
C33 C34 Cl37 119.6(3) . . ?
C35 C34 Cl37 118.5(3) . . ?
C34 C35 C33 119.2(3) . 2_657 ?
O36 C35 C33 116.2(3) . 2_657 ?
O36 C35 C34 124.6(3) . . ?
C35 O36 La2 122.5(2) . . ?
C39 O38 La2 113.7(2) . 2_667 ?
O38 C39 C40 125.2(4) . . ?
O38 C39 C41 115.6(3) . 2_667 ?
C40 C39 C41 119.3(3) . 2_667 ?
C39 C40 Cl43 119.0(3) . . ?
C41 C40 C39 121.5(3) . . ?
C41 C40 Cl43 119.5(3) . . ?
C40 C41 C39 119.2(3) . 2_667 ?
O42 C41 C39 115.7(3) . 2_667 ?
O42 C41 C40 125.1(3) . . ?
C41 O42 La2 115.3(2) . . ?
C45 O44 La2 122.0(2) . 2_557 ?
O44 C45 C46 124.7(3) . . ?
O44 C45 C47 116.5(3) . 2_557 ?
C46 C45 C47 118.7(3) . 2_557 ?
C45 C46 Cl49 118.8(3) . . ?
C47 C46 C45 122.2(3) . . ?
C47 C46 Cl49 118.9(3) . . ?
C46 C47 C45 119.0(3) . 2_557 ?
O48 C47 C45 115.3(3) . 2_557 ?
O48 C47 C46 125.7(3) . . ?
C47 O48 La2 123.1(2) . . ?
La2 O50 H50A 118(4) . . ?
La2 O50 H50B 125(3) . . ?
H50A O50 H50B 107(4) . . ?
C52 N51 C56 121.2(4) . . ?
C52 N51 C66 120.5(4) . . ?
C56 N51 C66 117.9(3) . . ?
N51 C52 H52 119.5 . . ?
N51 C52 C53 121.0(4) . . ?
C53 C52 H52 119.5 . . ?
C52 C53 H53 120.2 . . ?
C54 C53 C52 119.5(4) . . ?
C54 C53 H53 120.2 . . ?
C53 C54 H54 120.0 . . ?
C53 C54 C55 120.1(4) . . ?
C55 C54 H54 120.0 . . ?
C54 C55 C56 118.4(4) . . ?
C54 C55 C57 122.4(4) . . ?
C56 C55 C57 119.2(4) . . ?
N51 C56 C55 119.5(4) . . ?
N51 C56 C59 120.8(3) . . ?
C55 C56 C59 119.5(4) . . ?
C55 C57 H57 119.8 . . ?
C58 C57 C55 120.4(4) . . ?
C58 C57 H57 119.8 . . ?
C57 C58 H58 119.5 . . ?
C57 C58 C60 121.0(4) . . ?
C60 C58 H58 119.5 . . ?
C60 C59 C56 120.4(4) . . ?
N64 C59 C56 119.9(4) . . ?
N64 C59 C60 119.6(4) . . ?
C59 C60 C58 119.4(4) . . ?
C59 C60 C61 118.4(4) . . ?
C61 C60 C58 122.3(4) . . ?
C60 C61 H61 120.1 . . ?
C62 C61 C60 119.9(4) . . ?
C62 C61 H61 120.1 . . ?
C61 C62 H62 120.1 . . ?
C61 C62 C63 119.8(4) . . ?
C63 C62 H62 120.1 . . ?
C62 C63 H63 119.6 . . ?
N64 C63 C62 120.8(4) . . ?
N64 C63 H63 119.6 . . ?
C59 N64 C65 117.6(3) . . ?
C63 N64 C59 121.3(4) . . ?
C63 N64 C65 121.1(4) . . ?
N64 C65 H65A 109.6 . . ?
N64 C65 H65B 109.6 . . ?
N64 C65 C66 110.4(3) . . ?
H65A C65 H65B 108.1 . . ?
C66 C65 H65A 109.6 . . ?
C66 C65 H65B 109.6 . . ?
N51 C66 C65 109.8(3) . . ?
N51 C66 H66A 109.7 . . ?
N51 C66 H66B 109.7 . . ?
C65 C66 H66A 109.7 . . ?
C65 C66 H66B 109.7 . . ?
H66A C66 H66B 108.2 . . ?
N67 C68 C69 178.8(6) . . ?
C68 C69 H69A 109.5 . . ?
C68 C69 H69B 109.5 . . ?
C68 C69 H69C 109.5 . . ?
H69A C69 H69B 109.5 . . ?
H69A C69 H69C 109.5 . . ?
H69B C69 H69C 109.5 . . ?
N70 C71 C72 178.6(5) . . ?
C71 C72 H72A 109.5 . . ?
C71 C72 H72B 109.5 . . ?
C71 C72 H72C 109.5 . . ?
H72A C72 H72B 109.5 . . ?
H72A C72 H72C 109.5 . . ?
H72B C72 H72C 109.5 . . ?
N73 C74 C75 179.1(6) . . ?
C74 C75 H75A 109.5 . . ?
C74 C75 H75B 109.5 . . ?
C74 C75 H75C 109.5 . . ?
H75A C75 H75B 109.5 . . ?
H75A C75 H75C 109.5 . . ?
H75B C75 H75C 109.5 . . ?
N76 C77 C78 178.2(5) . . ?
C77 C78 H78A 109.5 . . ?
C77 C78 H78B 109.5 . . ?
C77 C78 H78C 109.5 . . ?
H78A C78 H78B 109.5 . . ?
H78A C78 H78C 109.5 . . ?
H78B C78 H78C 109.5 . . ?
H79A O79 H79B 112(5) . . ?
H80A O80 H80B 102(4) . . ?
H81A O81 H81B 103(4) . . ?
H82A O82 H82B 102(4) . . ?
H83A O83 H83B 96(4) . . ?
H84A O84 H84B 104(4) . . ?
H85A O85 H85B 100(4) . . ?
H86A O86 H86B 105(4) . . ?
H87A O87 H87B 112(4) . . ?
H88A O88 H88B 101(4) . . ?
H89A O89 H89B 102(4) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
La1 O1 C2 C3 -162.8(3) 2_666 . . . ?
La1 O1 C2 C4 17.5(4) 2_666 . . 2_666 ?
La1 O7 C8 C9 156.8(3) 2_656 . . . ?
La1 O7 C8 C10 -22.2(4) 2_656 . . 2_656 ?
La1 O13 C14 C15 175.2(3) 2_766 . . . ?
La1 O13 C14 C16 -5.0(4) 2_766 . . 2_766 ?
O1 C2 C3 C4 -175.9(4) . . . . ?
O1 C2 C3 Cl6 3.8(6) . . . . ?
La2 O32 C33 C34 170.0(3) 2_657 . . . ?
La2 O32 C33 C35 -11.2(4) 2_657 . . 2_657 ?
La2 O38 C39 C40 -145.7(3) 2_667 . . . ?
La2 O38 C39 C41 33.5(4) 2_667 . . 2_667 ?
La2 O44 C45 C46 -177.8(3) 2_557 . . . ?
La2 O44 C45 C47 1.6(4) 2_557 . . 2_557 ?
C2 C3 C4 C2 -3.7(6) . . . 2_666 ?
C2 C3 C4 O5 177.0(4) . . . . ?
C2 C4 O5 La1 12.8(4) 2_666 . . . ?
C3 C4 O5 La1 -167.9(3) . . . . ?
C4 C2 C3 C4 3.7(6) 2_666 . . . ?
C4 C2 C3 Cl6 -176.5(3) 2_666 . . . ?
Cl6 C3 C4 C2 176.5(3) . . . 2_666 ?
Cl6 C3 C4 O5 -2.8(5) . . . . ?
O7 C8 C9 C10 179.1(4) . . . . ?
O7 C8 C9 Cl12 1.1(6) . . . . ?
C8 C9 C10 C8 1.9(6) . . . 2_656 ?
C8 C9 C10 O11 -177.5(4) . . . . ?
C8 C10 O11 La1 -20.3(4) 2_656 . . . ?
C9 C10 O11 La1 159.2(3) . . . . ?
C10 C8 C9 C10 -2.0(6) 2_656 . . . ?
C10 C8 C9 Cl12 -179.9(3) 2_656 . . . ?
Cl12 C9 C10 C8 179.9(3) . . . 2_656 ?
Cl12 C9 C10 O11 0.5(6) . . . . ?
O13 C14 C15 C16 178.5(4) . . . . ?
O13 C14 C15 Cl18 -2.2(6) . . . . ?
C14 C15 C16 C14 1.4(6) . . . 2_766 ?
C14 C15 C16 O17 -178.3(4) . . . . ?
C14 C16 O17 La1 -2.3(4) 2_766 . . . ?
C15 C16 O17 La1 177.4(3) . . . . ?
C16 C14 C15 C16 -1.4(6) 2_766 . . . ?
C16 C14 C15 Cl18 177.9(3) 2_766 . . . ?
Cl18 C15 C16 C14 -177.9(3) . . . 2_766 ?
Cl18 C15 C16 O17 2.4(6) . . . . ?
C20 C21 C22 C23 -6.4(5) . . . . ?
C20 C21 C22 O27 174.3(3) . . . . ?
C20 C21 O26 La1 -164.2(3) . . . . ?
C20 C25 O29 La2 -176.8(3) . . . . ?
C21 C20 C25 C24 -3.7(5) . . . . ?
C21 C20 C25 O29 175.9(3) . . . . ?
C21 C22 C23 C24 6.2(5) . . . . ?
C21 C22 C23 Cl31 -175.4(3) . . . . ?
C21 C22 O27 La1 -7.4(4) . . . . ?
C22 C21 O26 La1 16.1(4) . . . . ?
C22 C23 C24 C25 -4.6(5) . . . . ?
C22 C23 C24 O28 175.5(4) . . . . ?
C23 C22 O27 La1 173.3(3) . . . . ?
C23 C24 C25 C20 3.2(5) . . . . ?
C23 C24 C25 O29 -176.4(3) . . . . ?
C23 C24 O28 La2 172.1(3) . . . . ?
C24 C25 O29 La2 2.8(4) . . . . ?
C25 C20 C21 C22 5.2(5) . . . . ?
C25 C20 C21 O26 -174.4(4) . . . . ?
C25 C24 O28 La2 -7.8(4) . . . . ?
O26 C21 C22 C23 173.3(3) . . . . ?
O26 C21 C22 O27 -6.1(5) . . . . ?
O27 C22 C23 C24 -174.6(3) . . . . ?
O27 C22 C23 Cl31 3.8(5) . . . . ?
O28 C24 C25 C20 -176.9(3) . . . . ?
O28 C24 C25 O29 3.5(5) . . . . ?
Cl30 C20 C21 C22 -177.2(3) . . . . ?
Cl30 C20 C21 O26 3.2(5) . . . . ?
Cl30 C20 C25 C24 178.7(3) . . . . ?
Cl30 C20 C25 O29 -1.7(5) . . . . ?
Cl31 C23 C24 C25 177.0(3) . . . . ?
Cl31 C23 C24 O28 -3.0(5) . . . . ?
O32 C33 C34 C35 178.8(4) . . . . ?
O32 C33 C34 Cl37 -3.9(6) . . . . ?
C33 C34 C35 C33 -0.2(6) . . . 2_657 ?
C33 C34 C35 O36 -179.8(4) . . . . ?
C33 C35 O36 La2 -9.5(4) 2_657 . . . ?
C34 C35 O36 La2 170.2(3) . . . . ?
C35 C33 C34 C35 0.2(6) 2_657 . . . ?
C35 C33 C34 Cl37 177.5(3) 2_657 . . . ?
Cl37 C34 C35 C33 -177.5(3) . . . 2_657 ?
Cl37 C34 C35 O36 2.8(5) . . . . ?
O38 C39 C40 C41 -178.6(4) . . . . ?
O38 C39 C40 Cl43 0.6(6) . . . . ?
C39 C40 C41 C39 -2.3(6) . . . 2_667 ?
C39 C40 C41 O42 177.2(4) . . . . ?
C39 C41 O42 La2 31.6(4) 2_667 . . . ?
C40 C41 O42 La2 -147.9(3) . . . . ?
C41 C39 C40 C41 2.3(6) 2_667 . . . ?
C41 C39 C40 Cl43 -178.5(3) 2_667 . . . ?
Cl43 C40 C41 C39 178.5(3) . . . 2_667 ?
Cl43 C40 C41 O42 -2.0(6) . . . . ?
O44 C45 C46 C47 179.9(3) . . . . ?
O44 C45 C46 Cl49 0.4(5) . . . . ?
C45 C46 C47 C45 -0.5(6) . . . 2_557 ?
C45 C46 C47 O48 179.1(3) . . . . ?
C45 C47 O48 La2 1.2(4) 2_557 . . . ?
C46 C47 O48 La2 -178.4(3) . . . . ?
C47 C45 C46 C47 0.5(6) 2_557 . . . ?
C47 C45 C46 Cl49 -178.9(2) 2_557 . . . ?
Cl49 C46 C47 C45 178.9(2) . . . 2_557 ?
Cl49 C46 C47 O48 -1.4(5) . . . . ?
N51 C52 C53 C54 -2.7(6) . . . . ?
N51 C56 C59 C60 -172.4(3) . . . . ?
N51 C56 C59 N64 10.6(6) . . . . ?
C52 N51 C56 C55 5.5(5) . . . . ?
C52 N51 C56 C59 -178.7(4) . . . . ?
C52 N51 C66 C65 145.6(4) . . . . ?
C52 C53 C54 C55 3.7(6) . . . . ?
C53 C54 C55 C56 -0.2(6) . . . . ?
C53 C54 C55 C57 -178.2(4) . . . . ?
C54 C55 C56 N51 -4.4(6) . . . . ?
C54 C55 C56 C59 179.8(4) . . . . ?
C54 C55 C57 C58 177.9(4) . . . . ?
C55 C56 C59 C60 3.5(6) . . . . ?
C55 C56 C59 N64 -173.6(3) . . . . ?
C55 C57 C58 C60 1.1(7) . . . . ?
C56 N51 C52 C53 -2.0(6) . . . . ?
C56 N51 C66 C65 -41.5(5) . . . . ?
C56 C55 C57 C58 0.0(6) . . . . ?
C56 C59 C60 C58 -2.4(6) . . . . ?
C56 C59 C60 C61 177.5(4) . . . . ?
C56 C59 N64 C63 -177.1(4) . . . . ?
C56 C59 N64 C65 6.4(5) . . . . ?
C57 C55 C56 N51 173.6(4) . . . . ?
C57 C55 C56 C59 -2.2(6) . . . . ?
C57 C58 C60 C59 0.1(7) . . . . ?
C57 C58 C60 C61 -179.8(4) . . . . ?
C58 C60 C61 C62 -178.5(4) . . . . ?
C59 C60 C61 C62 1.5(6) . . . . ?
C59 N64 C65 C66 -39.5(5) . . . . ?
C60 C59 N64 C63 5.8(6) . . . . ?
C60 C59 N64 C65 -170.7(4) . . . . ?
C60 C61 C62 C63 2.1(7) . . . . ?
C61 C62 C63 N64 -1.9(6) . . . . ?
C62 C63 N64 C59 -2.1(6) . . . . ?
C62 C63 N64 C65 174.3(4) . . . . ?
C63 N64 C65 C66 143.9(4) . . . . ?
N64 C59 C60 C58 174.7(4) . . . . ?
N64 C59 C60 C61 -5.4(6) . . . . ?
N64 C65 C66 N51 55.5(4) . . . . ?
C66 N51 C52 C53 170.8(4) . . . . ?
C66 N51 C56 C55 -167.4(3) . . . . ?
C66 N51 C56 C59 8.4(5) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.277
_oxdiff_exptl_absorpt_empirical_full_min 0.448
# start Validation Reply Form
_vrf_PLAT420_mpvk-mpf-2-044b_2_1-mask_smrt_abs_a 
;
PROBLEM: D-H Bond Without Acceptor  O84      --H84B     .     Please Check 
RESPONSE: The refined positions of the H atoms of O84 are tentative only.
;
_vrf_PLAT369_mpvk-mpf-2-044b_2_1-mask_smrt_abs_a 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_d     .       1.54 Ang.  
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
# end Validation Reply Form
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_MF-1-33B_1-mask_avg_abs_a
_database_code_depnum_ccdc_archive 'CCDC 2415090'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_audit_creation_date             2024-04-26
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_chemical_formula_moiety         
'C12 H2 Cl4 La O9, 0.5(C14 H12 N2), 2(C3 H6 O), H2 O'
_chemical_formula_sum            'C25 H22 Cl4 La N O12'
_chemical_formula_weight         809.168
_chemical_oxdiff_formula         'C25 H22 Cl4 La N O12'
_chemical_oxdiff_usercomment     'solvent:acetone and water'
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
_atom_type_scat_dispersion_source
C 0.01788 0.00908 2.31000 1.02000 1.58860 0.86500 20.84390 10.20750 0.56870
51.65120 0.21560 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
Cl 0.36457 0.70364 11.46040 7.19640 6.25560 1.64550 0.01040 1.16620 18.51940
47.77840 -9.55740 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
H 0.00000 0.00000 0.49300 0.32291 0.14019 0.04081 10.51090 26.12570 3.14236
57.79970 0.00304 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
La -1.36632 9.05284 20.57800 19.59900 11.37270 3.28719 2.94817 0.24448 18.77260
133.12399 2.14678 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
N 0.03110 0.01806 12.21260 3.13220 2.01250 1.16630 0.00570 9.89330 28.99750
0.58260 -11.52900 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
O 0.04960 0.03234 3.04850 2.28680 1.54630 0.86700 13.27710 5.70110 0.32390
32.90890 0.25080 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -x,-y,-z

_symmetry_Int_Tables_number      2
_cell_length_a                   10.7781(4)
_cell_length_b                   11.4423(4)
_cell_length_c                   12.9249(4)
_cell_angle_alpha                103.513(3)
_cell_angle_beta                 94.393(3)
_cell_angle_gamma                106.749(3)
_cell_volume                     1466.26(10)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    11172
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9550
_cell_measurement_theta_min      4.3370
_exptl_absorpt_coefficient_mu    15.186
_exptl_absorpt_correction_T_max  0.721
_exptl_absorpt_correction_T_min  0.362
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.833
_exptl_crystal_description       prism
_exptl_crystal_F_000             800.000
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-3 -5 1 0.0230
3 5 -2 0.0297
0 0 8 0.0438
0 -1 -8 0.0461
6 -5 0 0.0319
-6 5 0 0.0092
3 -6 5 0.0361
3 3 -7 0.0514
2 -7 0 0.0271

_exptl_crystal_size_max          0.105
_exptl_crystal_size_mid          0.059
_exptl_crystal_size_min          0.043
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-3.0370 -5.3038 0.5611 0.8025 0.2389 0.5467
3.1021 5.4133 -1.8363 -0.7126 -0.2123 -0.6686
0.0413 0.0985 8.0195 -0.6913 -0.2046 0.6930
-0.3410 -0.6213 -7.7478 0.7522 0.2228 -0.6201
6.3650 -4.8912 0.0905 -0.2844 0.9575 -0.0478
-6.4409 4.7131 0.2209 0.2837 -0.9547 0.0903
3.0179 -6.3291 5.3429 -0.2056 0.6958 0.6882
3.0360 3.1295 -7.1764 -0.0394 0.1273 -0.9911
2.2946 -7.2430 0.1100 0.4060 0.8532 0.3275

_diffrn_reflns_av_R_equivalents  0.0480
_diffrn_reflns_av_unetI/netI     0.0450
_diffrn_reflns_Laue_measured_fraction_full 0.9962
_diffrn_reflns_Laue_measured_fraction_max 0.9248
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            17670
_diffrn_reflns_point_group_measured_fraction_full 0.9962
_diffrn_reflns_point_group_measured_fraction_max 0.9248
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.92
_diffrn_reflns_theta_min         3.56
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9962
_diffrn_measured_fraction_theta_max 0.9248
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -24.00   6.00   0.50    0.20    --   47.26 -60.00 -53.00   60
  2  ω    -22.00   5.00   0.50    0.20    --   47.26 -19.00 -60.00   54
  3  ω     35.00  62.00   0.50    0.20    --   47.26 -60.00 -53.00   54
  4  ω     57.00 106.00   0.50    0.40    --  105.30-125.00  30.00   98
  5  ω     84.00 110.00   0.50    0.40    --  105.30-125.00   0.00   52
  6  ω     40.00 110.00   0.50    0.40    --  105.30-125.00 -30.00  140
  7  ω     39.00 108.00   0.50    0.40    --  105.30-106.00-131.44  138
  8  ω     34.00  79.00   0.50    0.40    --  105.30 -94.00-180.00   90
  9  ω     36.00  67.00   0.50    0.40    --  105.30-125.00-180.00   62
 10  ω     34.00  81.00   0.50    0.20    --   47.26-125.00 -60.00   94
 11  ω     83.00 109.00   0.50    0.40    --  105.30-125.00-180.00   52
 12  ω     59.00 106.00   0.50    0.40    --  105.30-105.00 171.31   94
 13  ω     54.00 101.00   0.50    0.40    --  105.30 -94.00  60.00   94
 14  ω     74.00 105.00   0.50    0.40    --  105.30 -94.00   0.00   62
 15  ω     33.00  70.00   0.50    0.40    --  105.30 -61.00 -60.00   74
 16  ω     36.00  68.00   0.50    0.40    --  105.30 -60.00 -53.00   64
 17  ω    107.00 134.00   0.50    0.40    --  105.30  30.00-120.00   54
 18  ω    137.00 165.00   0.50    0.40    --  105.30  30.00-120.00   56
 19  ω     40.00  70.00   0.50    0.40    --  105.30 -61.00  90.00   60
 20  ω    101.00 174.00   0.50    0.40    --  105.30  60.00  85.00  146
 21  ω     32.00 117.00   0.50    0.20    --   47.26  60.00  85.00  170
 22  ω    -32.00  -7.00   0.50    0.20    --  -47.26  60.00  85.00   50
 23  ω    -62.00 -37.00   0.50    0.20    --  -47.26  60.00  85.00   50
 24  ω    -64.00 -21.00   0.50    0.40    --  -91.75  61.00 150.00   86
 25  ω    -29.00  27.00   0.50    0.20    --  -47.26  19.00-120.00  112
 26  ω    -66.00 -41.00   0.50    0.40    --  -91.75  61.00 -90.00   50
 27  ω    -48.00 -23.00   0.50    0.40    --  -91.75  45.00 -60.00   50
 28  ω    -69.00 -20.00   0.50    0.40    --  -91.75  60.00  85.00   98
 29  ω    -50.00 -21.00   0.50    0.40    --  -91.75  45.00  90.00   58
 30  ω   -120.00 -35.00   0.50    0.20    --  -47.26 -38.00  90.00  170
 31  ω    -62.00 -27.00   0.50    0.40    --  -91.75 125.00 -90.00   70
 32  ω    -83.00 -23.00   0.50    0.40    --  -91.75 125.00-150.00  120
 33  ω   -119.00 -38.00   0.50    0.20    --  -47.26 -60.00 -53.00  162
 34  ω   -162.00-109.00   0.50    0.40    --  -91.75 -60.00 -53.00  106
 35  ω   -159.00-126.00   0.50    0.40    --  -91.75 -45.00-150.00   66
 36  ω   -121.00 -88.00   0.50    0.40    --  -91.75 -45.00-150.00   66
 37  ω   -111.00 -83.00   0.50    0.40    --  -91.75 -15.00-180.00   56
 38  ω   -166.00-140.00   0.50    0.40    --  -91.75 -15.00-180.00   52
 39  ω   -163.00 -80.00   0.50    0.40    --  -91.75 -45.00   0.00  166
 40  ω   -154.00 -90.00   0.50    0.40    --  -91.75 -94.00  60.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1157123000
_diffrn_orient_matrix_UB_12      -0.0939891000
_diffrn_orient_matrix_UB_13      -0.0844560000
_diffrn_orient_matrix_UB_21      0.0792772000
_diffrn_orient_matrix_UB_22      -0.0930550000
_diffrn_orient_matrix_UB_23      -0.0247818000
_diffrn_orient_matrix_UB_31      -0.0561431000
_diffrn_orient_matrix_UB_32      -0.0616759000
_diffrn_orient_matrix_UB_33      0.0874557000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              13
_reflns_limit_h_min              -13
_reflns_limit_k_max              13
_reflns_limit_k_min              -14
_reflns_limit_l_max              16
_reflns_limit_l_min              0
_reflns_number_gt                5383
_reflns_number_total             5739
_reflns_threshold_expression     I>=2u(I)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection       
'CrysAlisPro system (CCD 42.80a 64-bit (release 13-01-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         1.7369
_refine_diff_density_min         -1.7232
_refine_diff_density_rms         0.1388
_refine_ls_d_res_high            0.7915
_refine_ls_d_res_low             12.4160
_refine_ls_goodness_of_fit_ref   1.0331
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    38
_refine_ls_number_parameters     422
_refine_ls_number_reflns         5739
_refine_ls_number_restraints     131
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0381
_refine_ls_restrained_S_all      1.0206
_refine_ls_shift/su_max          -0.0009
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0750P)²+0.2416P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1016
_refine_ls_wR_factor_ref         0.1038
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C35-C36
 1.35 with sigma of 0.02
 C28-C35 = C36-C37
 1.43 with sigma of 0.02
 C32-C33
 1.51 with sigma of 0.02
 N30-C32 = N34-C33
 1.48 with sigma of 0.02
 O25-H25a = O25-H25b
 0.84 with sigma of 0.02
 H25a-H25b
 1.34 with sigma of 0.04
 O46-H46a = O46-H46b
 0.84 with sigma of 0.02
 H46a-H46b
 1.34 with sigma of 0.04
 C27-H27 = C31-H31
 0.95 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C26 \\sim C27 \\sim C29 \\sim C31 \\sim C28 \\sim C33 \\sim N34 \\sim N30 \\sim
C37 \\sim C32 \\sim C36 \\sim C35: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(C28) = Uanis(N34)
Uanis(C33) = Uanis(C35)
Uanis(N30) = Uanis(C37)
Uanis(C32) = Uanis(C36)
4. Rigid body (RIGU) restrains
 C39, C40, O38, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, C29, C31, C28, C33, N34, N30, C37, C32, C36, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C28(0.5) C33(0.5) H33a(0.5) H33b(0.5) N34(0.5) N30(0.5) C37(0.5)
 C32(0.5) H32a(0.5) H32b(0.5) C36(0.5) H36(0.5) C35(0.5) H35(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C33(H33a,H33b), C32(H32a,H32b)
6.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C36(H36), C35(H35)
6.c Idealised Me refined as rotating group:
 C39(H39a,H39b,H39c), C41(H41a,H41b,H41c), C43(H43a,H43b,H43c), C45(H45a,H45b,
 H45c)
;
_atom_sites_solution_primary     dual
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_group
C2 C 0.6086(3) 0.4732(3) 0.5506(3) 0.0206(7) Uani 1.000000 . . . .
C3 C 0.5549(4) 0.4044(4) 0.4449(3) 0.0221(7) Uani 1.000000 . . . .
C4 C 0.4431(3) 0.4207(4) 0.3937(3) 0.0209(7) Uani 1.000000 . . . .
O5 O 0.3785(3) 0.3511(3) 0.3046(2) 0.0246(5) Uani 1.000000 . . . .
Cl6 Cl 0.61461(8) 0.28528(9) 0.38278(7) 0.02486(19) Uani 1.000000 . . . .
O7 O 0.5833(2) 0.4694(2) 0.8082(2) 0.0227(5) Uani 1.000000 . . . .
C8 C 0.5386(3) 0.4806(3) 0.8951(3) 0.0202(7) Uani 1.000000 . . . .
C9 C 0.4122(3) 0.4119(4) 0.9064(3) 0.0209(7) Uani 1.000000 . . . .
C10 C 0.3681(3) 0.4243(3) 1.0061(3) 0.0204(7) Uani 1.000000 . . . .
O11 O 0.2578(2) 0.3613(3) 1.0224(2) 0.0230(5) Uani 1.000000 . . . .
La1 La 0.811875(17) 0.602386(18) 0.788278(15) 0.01845(9) Uani 1.000000 . . . .
O1 O 0.6976(2) 0.4540(3) 0.6068(2) 0.0235(5) Uani 1.000000 . . . .
Cl12 Cl 0.31030(8) 0.30305(10) 0.79440(7) 0.0302(2) Uani 1.000000 . . . .
O13 O 1.0106(2) 0.7647(2) 0.9133(2) 0.0236(5) Uani 1.000000 . . . .
C14 C 1.0126(4) 0.8752(4) 0.9576(3) 0.0221(7) Uani 1.000000 . . . .
C15 C 1.1099(3) 0.9641(4) 1.0382(3) 0.0228(7) Uani 1.000000 . . . .
C16 C 1.1026(3) 1.0853(4) 1.0843(3) 0.0225(7) Uani 1.000000 . . . .
O17 O 1.1840(3) 1.1671(3) 1.1594(2) 0.0249(6) Uani 1.000000 . . . .
Cl18 Cl 1.24296(8) 0.92328(9) 1.08303(8) 0.0269(2) Uani 1.000000 . . . .
O19 O 0.9685(2) 0.4914(3) 0.7027(2) 0.0238(5) Uani 1.000000 . . . .
C20 C 0.9848(3) 0.4899(4) 0.6080(3) 0.0211(7) Uani 1.000000 . . . .
C21 C 1.0254(4) 0.3988(4) 0.5382(3) 0.0226(7) Uani 1.000000 . . . .
C22 C 1.0420(3) 0.4019(4) 0.4332(3) 0.0210(7) Uani 1.000000 . . . .
O23 O 1.0791(3) 0.3243(3) 0.3667(2) 0.0244(6) Uani 1.000000 . . . .
Cl24 Cl 1.05326(10) 0.27649(10) 0.58479(8) 0.0322(2) Uani 1.000000 . . . .
O25 O 0.8367(3) 0.4299(3) 0.8703(3) 0.0326(7) Uani 1.000000 D . . .
H25a H 0.782(4) 0.389(5) 0.901(4) 0.0489(10) Uiso 1.000000 DR . . .
H25b H 0.899(4) 0.402(5) 0.869(5) 0.0489(10) Uiso 1.000000 DR . . .
C26 C 0.2762(5) 0.1512(4) 0.4422(4) 0.0371(10) Uani 1.000000 . U . .
H26 H 0.2169(5) 0.1939(4) 0.4252(4) 0.0445(11) Uiso 1.000000 R . . .
C27 C 0.2710(6) 0.0379(5) 0.3763(4) 0.0458(12) Uani 1.000000 D U . .
H27 H 0.209(3) -0.002(5) 0.312(2) 0.0550(14) Uiso 1.000000 DR . . .
C29 C 0.4538(5) 0.0303(4) 0.4881(3) 0.0331(9) Uani 1.000000 . U . .
C31 C 0.3694(5) 0.2041(4) 0.5350(4) 0.0338(9) Uani 1.000000 D U . .
H31 H 0.371(4) 0.2864(17) 0.573(3) 0.0406(11) Uiso 1.000000 DR . . .
O38 O 0.2480(5) -0.0456(7) 0.6109(4) 0.0954(19) Uani 1.000000 . U . .
C39 C 0.2596(8) -0.0446(8) 0.7906(6) 0.0702(18) Uani 1.000000 . U . .
H39a H 0.201(3) -0.115(4) 0.812(3) 0.105(3) Uiso 1.000000 GR . . .
H39b H 0.343(3) -0.061(5) 0.7797(14) 0.105(3) Uiso 1.000000 GR . . .
H39c H 0.276(5) 0.034(2) 0.8474(13) 0.105(3) Uiso 1.000000 GR . . .
C40 C 0.1979(5) -0.0327(5) 0.6903(4) 0.0418(11) Uani 1.000000 . U . .
C41 C 0.0692(5) -0.0088(5) 0.6900(5) 0.0452(12) Uani 1.000000 . U . .
H41a H 0.045(2) 0.009(4) 0.6220(14) 0.0678(17) Uiso 1.000000 GR . . .
H41b H 0.0021(10) -0.0836(15) 0.698(3) 0.0678(17) Uiso 1.000000 GR . . .
H41c H 0.0760(12) 0.064(2) 0.750(2) 0.0678(17) Uiso 1.000000 GR . . .
O42 O 0.6335(3) 0.2946(3) 0.9537(2) 0.0311(6) Uani 1.000000 . . . .
C43 C 0.7426(4) 0.3684(5) 1.1352(4) 0.0370(10) Uani 1.000000 . . . .
H43a H 0.779(2) 0.3115(5) 1.165(2) 0.0555(15) Uiso 1.000000 GR . . .
H43b H 0.8106(16) 0.422(3) 1.1054(8) 0.0555(15) Uiso 1.000000 GR . . .
H43c H 0.7127(9) 0.421(3) 1.1924(15) 0.0555(15) Uiso 1.000000 GR . . .
C44 C 0.6295(4) 0.2918(4) 1.0481(4) 0.0284(8) Uani 1.000000 . . . .
C45 C 0.5117(4) 0.2093(5) 1.0781(4) 0.0360(10) Uani 1.000000 . . . .
H45a H 0.4393(11) 0.179(3) 1.0178(11) 0.0541(15) Uiso 1.000000 GR . . .
H45b H 0.5318(12) 0.1370(19) 1.095(3) 0.0541(15) Uiso 1.000000 GR . . .
H45c H 0.486(2) 0.2579(11) 1.1413(18) 0.0541(15) Uiso 1.000000 GR . . .
O46 O 1.0146(3) 0.3045(3) 0.8488(3) 0.0339(7) Uani 1.000000 D . . .
H46a H 1.078(4) 0.316(6) 0.896(3) 0.0509(10) Uiso 1.000000 DR . . .
H46b H 1.047(5) 0.326(6) 0.796(3) 0.0509(10) Uiso 1.000000 DR . . .
C28 C 0.3757(13) -0.0153(11) 0.3934(11) 0.0253(19) Uani 0.500000 D U P -1
C33 C 0.6832(9) 0.1687(8) 0.6514(7) 0.0276(13) Uani 0.500000 D U P -1
H33a H 0.7376(9) 0.1922(8) 0.7229(7) 0.0331(15) Uiso 0.500000 R . P -1
H33b H 0.7282(9) 0.2244(8) 0.6084(7) 0.0331(15) Uiso 0.500000 R . P -1
N34 N 0.6607(10) 0.0338(9) 0.5955(9) 0.0253(19) Uani 0.500000 D U P -1
N30 N 0.458(3) 0.149(4) 0.561(2) 0.0275(14) Uani 0.500000 D U P -1
C37 C 0.542(4) -0.140(5) 0.445(3) 0.0275(14) Uani 0.500000 D U P -1
C32 C 0.5481(14) 0.181(2) 0.6633(15) 0.021(2) Uani 0.500000 D U P -1
H32a H 0.5064(14) 0.125(2) 0.7073(15) 0.025(3) Uiso 0.500000 R . P -1
H32b H 0.5586(14) 0.269(2) 0.7035(15) 0.025(3) Uiso 0.500000 R . P -1
C36 C 0.4494(14) -0.2038(19) 0.3490(15) 0.021(2) Uani 0.500000 D U P -1
H36 H 0.4421(14) -0.2860(19) 0.3064(15) 0.025(3) Uiso 0.500000 R . P -1
C35 C 0.3737(9) -0.1355(8) 0.3249(7) 0.0276(13) Uani 0.500000 D U P -1
H35 H 0.3152(9) -0.1685(8) 0.2586(7) 0.0331(15) Uiso 0.500000 R . P -1


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C2 C3 1.390(5) . ?
C2 C4 1.531(5) 2_666 ?
C2 O1 1.260(5) . ?
C3 C4 1.411(5) . ?
C3 Cl6 1.729(4) . ?
C4 O5 1.255(5) . ?
O5 La1 2.547(3) 2_666 ?
O7 C8 1.249(4) . ?
O7 La1 2.563(2) . ?
C8 C9 1.401(5) . ?
C8 C10 1.532(5) 2_667 ?
C9 C10 1.398(5) . ?
C9 Cl12 1.726(4) . ?
C10 O11 1.263(4) . ?
O11 La1 2.590(2) 2_667 ?
La1 O1 2.529(3) . ?
La1 O13 2.534(3) . ?
La1 O17 2.551(3) 2_777 ?
La1 O19 2.560(3) . ?
La1 O23 2.584(3) 2_766 ?
La1 O25 2.516(3) . ?
O13 C14 1.254(5) . ?
C14 C15 1.394(5) . ?
C14 C16 1.541(5) 2_777 ?
C15 C16 1.403(5) . ?
C15 Cl18 1.731(4) . ?
C16 O17 1.249(5) . ?
O19 C20 1.246(5) . ?
C20 C21 1.405(5) . ?
C20 C22 1.546(5) 2_766 ?
C21 C22 1.391(5) . ?
C21 Cl24 1.737(4) . ?
C22 O23 1.260(5) . ?
O25 H25a 0.832(18) . ?
O25 H25b 0.830(18) . ?
C26 H26 0.9500 . ?
C26 C27 1.358(7) . ?
C26 C31 1.393(7) . ?
C27 H27 0.9500(10) . ?
C27 C28 1.454(16) . ?
C27 N34 1.340(13) 2_656 ?
C29 C29 1.421(9) 2_656 ?
C29 C28 1.330(16) . ?
C29 N34 1.460(13) 2_656 ?
C29 N30 1.44(3) . ?
C29 C37 1.33(4) 2_656 ?
C31 H31 0.9500(10) . ?
C31 N30 1.35(3) . ?
C31 C37 1.41(4) 2_656 ?
O38 C40 1.195(6) . ?
C39 H39a 0.9800 . ?
C39 H39b 0.9800 . ?
C39 H39c 0.9800 . ?
C39 C40 1.464(9) . ?
C40 C41 1.489(7) . ?
C41 H41a 0.9800 . ?
C41 H41b 0.9800 . ?
C41 H41c 0.9800 . ?
O42 C44 1.231(5) . ?
C43 H43a 0.9800 . ?
C43 H43b 0.9800 . ?
C43 H43c 0.9800 . ?
C43 C44 1.495(6) . ?
C44 C45 1.486(6) . ?
C45 H45a 0.9800 . ?
C45 H45b 0.9800 . ?
C45 H45c 0.9800 . ?
O46 H46a 0.840(19) . ?
O46 H46b 0.843(18) . ?
C28 C35 1.445(12) . ?
C33 H33a 0.9900 . ?
C33 H33b 0.9900 . ?
C33 N34 1.483(11) . ?
C33 C32 1.517(14) . ?
N30 C32 1.485(15) . ?
C37 C36 1.428(16) . ?
C32 H32a 0.9900 . ?
C32 H32b 0.9900 . ?
C36 H36 0.9500 . ?
C36 C35 1.348(13) . ?
C35 H35 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C4 C2 C3 119.5(3) 2_666 . ?
O1 C2 C3 124.7(4) . . ?
O1 C2 C4 115.8(3) . 2_666 ?
C4 C3 C2 120.4(3) . . ?
Cl6 C3 C2 119.0(3) . . ?
Cl6 C3 C4 120.1(3) . . ?
C3 C4 C2 119.6(3) . 2_666 ?
O5 C4 C2 116.0(3) . 2_666 ?
O5 C4 C3 124.3(4) . . ?
La1 O5 C4 122.1(2) 2_666 . ?
La1 O7 C8 123.6(2) . . ?
C9 C8 O7 124.3(3) . . ?
C10 C8 O7 116.0(3) 2_667 . ?
C10 C8 C9 119.7(3) 2_667 . ?
C10 C9 C8 122.2(3) . . ?
Cl12 C9 C8 118.8(3) . . ?
Cl12 C9 C10 119.0(3) . . ?
C9 C10 C8 118.1(3) . 2_667 ?
O11 C10 C8 116.7(3) . 2_667 ?
O11 C10 C9 125.2(3) . . ?
La1 O11 C10 121.7(2) 2_667 . ?
O7 La1 O5 64.92(8) . 2_666 ?
O11 La1 O5 95.98(8) 2_667 2_666 ?
O11 La1 O7 61.83(8) 2_667 . ?
O1 La1 O5 62.67(8) . 2_666 ?
O1 La1 O7 70.94(8) . . ?
O1 La1 O11 132.77(8) . 2_667 ?
O13 La1 O5 126.13(9) . 2_666 ?
O13 La1 O7 136.39(8) . . ?
O13 La1 O11 74.67(8) . 2_667 ?
O13 La1 O1 152.38(8) . . ?
O17 La1 O5 64.27(8) 2_777 2_666 ?
O17 La1 O7 106.41(8) 2_777 . ?
O17 La1 O11 74.72(9) 2_777 2_667 ?
O17 La1 O1 121.56(9) 2_777 . ?
O17 La1 O13 62.07(8) 2_777 . ?
O19 La1 O5 128.51(8) . 2_666 ?
O19 La1 O7 119.51(8) . . ?
O19 La1 O11 133.05(8) . 2_667 ?
O19 La1 O1 70.95(8) . . ?
O19 La1 O13 87.50(8) . . ?
O19 La1 O17 133.45(9) . 2_777 ?
O23 La1 O5 80.95(9) 2_766 2_666 ?
O23 La1 O7 135.72(8) 2_766 . ?
O23 La1 O11 153.99(8) 2_766 2_667 ?
O23 La1 O1 68.56(8) 2_766 . ?
O23 La1 O13 86.26(9) 2_766 . ?
O23 La1 O17 80.81(8) 2_766 2_777 ?
O23 La1 O19 61.68(8) 2_766 . ?
O25 La1 O5 135.56(9) . 2_666 ?
O25 La1 O7 71.69(9) . . ?
O25 La1 O11 70.74(9) . 2_667 ?
O25 La1 O1 94.94(10) . . ?
O25 La1 O13 92.04(10) . . ?
O25 La1 O17 141.35(10) . 2_777 ?
O25 La1 O19 66.85(9) . . ?
O25 La1 O23 128.52(9) . 2_766 ?
La1 O1 C2 122.5(2) . . ?
C14 O13 La1 122.5(2) . . ?
C15 C14 O13 125.9(4) . . ?
C16 C14 O13 115.7(3) 2_777 . ?
C16 C14 C15 118.3(3) 2_777 . ?
C16 C15 C14 121.8(3) . . ?
Cl18 C15 C14 119.0(3) . . ?
Cl18 C15 C16 119.2(3) . . ?
C15 C16 C14 119.8(3) . 2_777 ?
O17 C16 C14 115.5(3) . 2_777 ?
O17 C16 C15 124.7(4) . . ?
C16 O17 La1 122.0(2) . 2_777 ?
C20 O19 La1 119.1(2) . . ?
C21 C20 O19 125.0(3) . . ?
C22 C20 O19 116.1(3) 2_766 . ?
C22 C20 C21 118.9(3) 2_766 . ?
C22 C21 C20 122.5(4) . . ?
Cl24 C21 C20 118.5(3) . . ?
Cl24 C21 C22 118.9(3) . . ?
C21 C22 C20 118.6(3) . 2_766 ?
O23 C22 C20 115.5(3) . 2_766 ?
O23 C22 C21 125.9(4) . . ?
C22 O23 La1 118.3(2) . 2_766 ?
H25a O25 La1 126(4) . . ?
H25b O25 La1 126(4) . . ?
H25b O25 H25a 108(4) . . ?
C27 C26 H26 120.4(3) . . ?
C31 C26 H26 120.4(3) . . ?
C31 C26 C27 119.2(4) . . ?
H27 C27 C26 122(4) . . ?
C28 C27 C26 119.4(7) . . ?
C28 C27 H27 117(4) . . ?
N34 C27 C26 122.2(6) 2_656 . ?
N34 C27 H27 115(4) 2_656 . ?
N34 C27 C28 17.5(7) 2_656 . ?
N34 C29 C28 17.4(7) 2_656 . ?
N30 C29 C28 121.2(12) . . ?
N30 C29 N34 117.7(11) . 2_656 ?
C37 C29 C28 121.2(16) 2_656 . ?
C37 C29 N34 117.8(14) 2_656 2_656 ?
C37 C29 N30 0(4) 2_656 . ?
H31 C31 C26 114(3) . . ?
N30 C31 C26 122.5(10) . . ?
N30 C31 H31 123(3) . . ?
C37 C31 C26 118.5(11) 2_656 . ?
C37 C31 H31 127(3) 2_656 . ?
C37 C31 N30 4.1(19) 2_656 . ?
H39b C39 H39a 109.5 . . ?
H39c C39 H39a 109.5 . . ?
H39c C39 H39b 109.5 . . ?
C40 C39 H39a 109.5 . . ?
C40 C39 H39b 109.5 . . ?
C40 C39 H39c 109.5 . . ?
C39 C40 O38 120.6(6) . . ?
C41 C40 O38 121.5(5) . . ?
C41 C40 C39 117.8(5) . . ?
H41a C41 C40 109.5 . . ?
H41b C41 C40 109.5 . . ?
H41b C41 H41a 109.5 . . ?
H41c C41 C40 109.5 . . ?
H41c C41 H41a 109.5 . . ?
H41c C41 H41b 109.5 . . ?
H43b C43 H43a 109.5 . . ?
H43c C43 H43a 109.5 . . ?
H43c C43 H43b 109.5 . . ?
C44 C43 H43a 109.5 . . ?
C44 C43 H43b 109.5 . . ?
C44 C43 H43c 109.5 . . ?
C43 C44 O42 121.6(4) . . ?
C45 C44 O42 120.4(4) . . ?
C45 C44 C43 118.0(4) . . ?
H45a C45 C44 109.5 . . ?
H45b C45 C44 109.5 . . ?
H45b C45 H45a 109.5 . . ?
H45c C45 C44 109.5 . . ?
H45c C45 H45a 109.5 . . ?
H45c C45 H45b 109.5 . . ?
H46b O46 H46a 107(4) . . ?
C29 C28 C27 118.0(8) . . ?
C35 C28 C27 121.0(11) . . ?
C35 C28 C29 118.7(12) . . ?
H33b C33 H33a 108.7 . . ?
N34 C33 H33a 110.6(6) . . ?
N34 C33 H33b 110.6(5) . . ?
C32 C33 H33a 110.6(8) . . ?
C32 C33 H33b 110.6(6) . . ?
C32 C33 N34 105.7(11) . . ?
C29 N34 C27 116.9(7) 2_656 2_656 ?
C33 N34 C27 124.8(10) . 2_656 ?
C33 N34 C29 117.8(9) . 2_656 ?
C31 N30 C29 117.5(13) . . ?
C32 N30 C29 113(3) . . ?
C32 N30 C31 129(2) . . ?
C31 C37 C29 121.6(16) 2_656 2_656 ?
C36 C37 C29 125(3) . 2_656 ?
C36 C37 C31 114(3) . 2_656 ?
N30 C32 C33 115.3(19) . . ?
H32a C32 C33 108.5(6) . . ?
H32a C32 N30 108(2) . . ?
H32b C32 C33 108.5(9) . . ?
H32b C32 N30 108.5(17) . . ?
H32b C32 H32a 107.5 . . ?
H36 C36 C37 123(2) . . ?
C35 C36 C37 113(3) . . ?
C35 C36 H36 123.5(10) . . ?
C36 C35 C28 124.2(13) . . ?
H35 C35 C28 117.9(7) . . ?
H35 C35 C36 117.9(10) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 C3 C4 C2 8.0(3) . . . 2_666 ?
C2 C3 C4 O5 -170.0(3) . . . . ?
C2 C4 C3 C2 8.0(3) 2_666 . . . ?
C2 C4 C3 Cl6 -179.8(3) 2_666 . . . ?
C2 C4 O5 La1 -6.6(4) . 2_666 2_666 . ?
C3 C4 O5 La1 -175.3(3) . . . 2_666 ?
O7 C8 C9 C10 177.6(4) . . . . ?
O7 C8 C9 Cl12 0.7(4) . . . . ?
O7 C8 C10 C9 -177.7(3) . . 2_667 2_667 ?
O7 C8 C10 O11 3.7(4) . . 2_667 2_667 ?
C8 C9 C10 C8 1.7(4) . . . 2_667 ?
C8 C9 C10 O11 -176.7(4) . . . . ?
C8 C10 C9 C8 1.7(3) 2_667 . . . ?
C8 C10 C9 Cl12 178.6(3) 2_667 . . . ?
C8 C10 O11 La1 -2.6(4) . 2_667 2_667 . ?
C9 C10 O11 La1 -178.9(3) . . . 2_667 ?
La1 O13 C14 C15 170.5(3) . . . . ?
La1 O13 C14 C16 -10.9(3) . . . 2_777 ?
La1 O17 C16 C14 12.8(3) . 2_777 2_777 . ?
La1 O17 C16 C15 167.3(3) 2_777 . . . ?
La1 O19 C20 C21 -155.4(3) . . . . ?
La1 O19 C20 C22 24.9(2) . . . 2_766 ?
La1 O23 C22 C20 -23.2(2) . 2_766 2_766 . ?
La1 O23 C22 C21 -155.9(3) 2_766 . . . ?
O13 C14 C15 C16 -178.9(4) . . . . ?
O13 C14 C15 Cl18 0.7(4) . . . . ?
O13 C14 C16 C15 178.8(3) . . 2_777 2_777 ?
O13 C14 C16 O17 -1.3(4) . . 2_777 2_777 ?
C14 C15 C16 C14 -2.6(4) . . . 2_777 ?
C14 C15 C16 O17 177.2(4) . . . . ?
C14 C16 C15 C14 -2.6(3) 2_777 . . . ?
C14 C16 C15 Cl18 177.8(3) 2_777 . . . ?
O19 C20 C21 C22 -179.9(4) . . . . ?
O19 C20 C21 Cl24 1.1(4) . . . . ?
O19 C20 C22 C21 180.0(3) . . 2_766 2_766 ?
O19 C20 C22 O23 -0.9(4) . . 2_766 2_766 ?
C20 C21 C22 C20 0.2(4) . . . 2_766 ?
C20 C21 C22 O23 179.3(3) . . . . ?
C20 C22 C21 C20 0.2(3) 2_766 . . . ?
C20 C22 C21 Cl24 179.2(3) 2_766 . . . ?
C26 C27 C28 C29 17.4(6) . . . . ?
C26 C27 C28 C35 -179.9(8) . . . . ?
C26 C27 N34 C29 -21.8(7) . . 2_656 . ?
C26 C27 N34 C33 165.8(7) . . 2_656 2_656 ?
C26 C31 N30 C29 -0.2(5) . . . . ?
C26 C31 N30 C32 -169(2) . . . . ?
C26 C31 C37 C29 -0.6(5) . . 2_656 . ?
C26 C31 C37 C36 179(3) . . 2_656 2_656 ?
C27 C28 C29 C29 172.2(7) . . . 2_656 ?
C27 C28 C29 N34 67.6(17) . . . 2_656 ?
C27 C28 C29 N30 -16(3) . . . . ?
C27 C28 C29 C37 -16(3) . . . 2_656 ?
C27 C28 C35 C36 -164.7(11) . . . . ?
C27 N34 C29 C29 -169.1(6) . 2_656 . 2_656 ?
C27 N34 C29 C28 -83.6(18) . 2_656 . . ?
C27 N34 C29 N30 23(2) . 2_656 . . ?
C27 N34 C29 C37 22(3) . 2_656 . 2_656 ?
C27 N34 C33 C32 -135.1(10) 2_656 . . . ?
C29 C29 C28 C35 9.2(8) 2_656 . . . ?
C29 C29 N34 C33 -3.8(7) . 2_656 . . ?
C29 C29 N30 C31 180(3) 2_656 . . . ?
C29 C29 N30 C32 -10.0(9) 2_656 . . . ?
C29 C29 C37 C31 -180(3) . 2_656 . 2_656 ?
C29 C29 C37 C36 -0.3(11) . 2_656 . . ?
C29 C28 C35 C36 -2.2(14) . . . . ?
C29 N34 C33 C32 37.2(9) 2_656 . . . ?
C29 N30 C31 C37 -3(10) . . . 2_656 ?
C29 N30 C32 C33 48(4) . . . . ?
C29 C37 C31 N30 177(11) . 2_656 . . ?
C29 C37 C36 C35 7(6) 2_656 . . . ?
C31 N30 C32 C33 -143(4) . . . . ?
C31 C37 C36 C35 -174(3) 2_656 . . . ?
C28 C35 C36 C37 -6(3) . . . . ?


_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.561
_oxdiff_exptl_absorpt_empirical_full_min 0.728
loop_
_restr_distance_atom_site_label_1
_restr_distance_atom_site_label_2
_restr_distance_site_symmetry_2
_restr_distance_target
_restr_distance_target_weight_param
_restr_distance_diff
O25 H25a 1 0.8400 0.0200 0.0085
O25 H25b 1 0.8400 0.0200 0.0102
H25a H25b 1 1.3400 0.0400 -0.0049
C27 H27 1 0.9500 0.0010 -0.0000
C31 H31 1 0.9500 0.0010 0.0000
O46 H46a 1 0.8400 0.0200 0.0005
O46 H46b 1 0.8400 0.0200 -0.0031
H46a H46b 1 1.3400 0.0400 -0.0112
C28 C35 1 1.4300 0.0200 -0.0148
N34 C33 1 1.4800 0.0200 -0.0029
N30 C32 1 1.4800 0.0200 -0.0047
C32 C33 1 1.5100 0.0200 -0.0075
C36 C37 1 1.4300 0.0200 0.0023
C35 C36 1 1.3500 0.0200 0.0018

loop_
_restr_RIGU_atom_site_label_1
_restr_RIGU_atom_site_label_2
_restr_RIGU_target_weight_param
_restr_RIGU_U13_diff
_restr_RIGU_U23_diff
_restr_RIGU_U33_diff
C26 C27 0.004000 -0.002719 -0.007853 -0.004401
C26 C31 0.004000 -0.005868 0.005911 -0.003888
C26 C28 0.004000 -0.000392 0.000752 0.005213
C26 N30 0.004000 -0.008839 0.007540 0.005891
C27 C29 0.004000 -0.004035 0.002903 -0.003360
C27 C31 0.004000 -0.013502 0.014436 0.000739
C27 C28 0.004000 -0.002233 0.007515 0.002642
C29 C31 0.004000 0.002841 -0.001099 -0.000680
C29 C28 0.004000 -0.001217 0.002465 0.001137
C29 N30 0.004000 0.001882 0.000704 0.002266
C29 C32 0.004000 -0.005328 0.016176 0.002217
C31 N30 0.004000 -0.008136 0.001731 0.004850
C31 C32 0.004000 -0.003348 0.005621 0.014815
O38 C39 0.004000 0.001560 0.029666 -0.010494
O38 C40 0.004000 -0.007014 0.012554 -0.000474
O38 C41 0.004000 -0.020921 0.002382 -0.003067
C39 C40 0.004000 0.004664 -0.003736 0.005716
C39 C41 0.004000 0.011127 0.019771 0.004817
C40 C41 0.004000 -0.003368 -0.001862 0.000212
C28 N30 0.004000 -0.001121 0.002476 0.001832
C33 N30 0.004000 -0.001438 0.001136 -0.007475
C33 C32 0.004000 0.002745 0.000975 -0.000201
N30 C32 0.004000 0.002794 0.006059 -0.000489

loop_
_restr_U_similar_atom_site_label_1
_restr_U_similar_atom_site_label_2
_restr_U_similar_weight_param
C26 C27 0.0400
C26 C31 0.0400
C27 C28 0.0400
C29 C28 0.0400
C29 N30 0.0400
C31 N30 0.0400
C33 C32 0.0400
N30 C32 0.0400
# start Validation Reply Form

_vrf_PLAT250_MF-1-33B_1-mask_avg_abs_a 
;
PROBLEM: Large U3/U1 Ratio for <U(i,j)> Tensor(Resd    2)        2.5 Note  
RESPONSE: This is due to positional disorder of the non-centrosymmetric cation around an inversion center.
;
_vrf_PLAT329_MF-1-33B_1-mask_avg_abs_a 
;
PROBLEM: Carbon Atom Hybridisation Unclear for ..........        C27 Check 
RESPONSE: C27 is sp2 hybridised. C27 bonds to C26, H27 and either C28 or N34 due to positional disorder of the cation around an inversion center giving rising to half occupany for C28 and N34.
;
_vrf_PLAT369_MF-1-33B_1-mask_avg_abs_a 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_a     .       1.53 Ang.  
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
# end Validation Reply Form
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_MF-1-16B_1-mask_smrt_abs_a
_database_code_depnum_ccdc_archive 'CCDC 2415088'
loop_
_audit_author_name
_audit_author_address
'Martin van Koeverden'
;The University of Melbourne
Australia
;
_audit_update_record             
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_audit_creation_date             2024-04-24
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_chemical_formula_moiety         'Br5 C15 La O10, C12 H12 N2, 3(H2 O)'
_chemical_formula_sum            'C27 H18 Br5 La N2 O13'
_chemical_formula_weight         1116.873
_chemical_oxdiff_formula         'C27 H18 Br5 La1 N2 O13'
_chemical_oxdiff_usercomment     'Solvent:actone and water'
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
_atom_type_scat_dispersion_source
Br -0.66955 1.28295 17.17890 5.23580 5.63770 3.98510 2.17230 16.57960 0.26090
41.43280 2.95570 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
C 0.01788 0.00908 2.31000 1.02000 1.58860 0.86500 20.84390 10.20750 0.56870
51.65120 0.21560 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
H 0.00000 0.00000 0.49300 0.32291 0.14019 0.04081 10.51090 26.12570 3.14236
57.79970 0.00304 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
La -1.36632 9.05284 20.57800 19.59900 11.37270 3.28719 2.94817 0.24448 18.77260
133.12399 2.14678 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
N 0.03110 0.01806 12.21260 3.13220 2.01250 1.16630 0.00570 9.89330 28.99750
0.58260 -11.52900 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'
O 0.04960 0.03234 3.04850 2.28680 1.54630 0.86700 13.27710 5.70110 0.32390
32.90890 0.25080 'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Brennan, Cowan, Rev. Sci. Instrum., 1992, 63, 850'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -x,y+1/2,-z+1/2
3 -x,-y,-z
4 x,-y-1/2,z-1/2

_symmetry_Int_Tables_number      14
_cell_length_a                   12.1099(1)
_cell_length_b                   26.3460(2)
_cell_length_c                   10.5165(1)
_cell_angle_alpha                90
_cell_angle_beta                 108.823(1)
_cell_angle_gamma                90
_cell_volume                     3175.82(5)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    33130
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      76.4930
_cell_measurement_theta_min      3.3590
_exptl_absorpt_coefficient_mu    18.392
_exptl_absorpt_correction_T_max  0.584
_exptl_absorpt_correction_T_min  0.153
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.336
_exptl_crystal_description       needle
_exptl_crystal_F_000             2110.207
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 -17 1 0.0240
-7 -3 -1 0.0512
7 2 -5 0.0441
-4 0 7 0.0667
6 3 2 0.0219
-8 -3 2 0.0418
-7 -3 0 0.0384
-2 17 0 0.0201
8 0 -3 0.0396
3 -16 0 0.0197

_exptl_crystal_size_max          0.169
_exptl_crystal_size_mid          0.072
_exptl_crystal_size_min          0.042
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
0.1287 -16.9713 0.7446 0.3295 0.9332 -0.1431
-6.6038 -3.2553 -1.4323 -0.5802 0.2058 -0.7880
7.1013 1.7144 -4.6838 -0.2833 0.1013 0.9537
-4.2437 0.0551 6.6285 0.7278 -0.2580 -0.6354
6.2908 3.2284 1.9154 0.6334 -0.2229 0.7410
-7.7266 -2.8366 1.6510 -0.1942 0.0673 -0.9787
-7.4417 -3.0792 0.3587 -0.3666 0.1283 -0.9215
-1.6639 16.6290 -0.1614 -0.3327 -0.9415 -0.0544
7.8118 0.2912 -2.9001 0.0444 0.1214 0.9916
3.0641 -15.7000 -0.3994 0.3237 0.9151 0.2404

_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9673
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            44705
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9673
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.72
_diffrn_reflns_theta_min         3.36
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.9673
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     71.00  96.00   0.50    0.14    --   48.11 161.00 -87.00   50
  2  ω     90.00 115.00   0.50    0.43    --  105.08 161.00 -87.00   50
  3  ω    -26.00  26.00   0.50    0.14    --  -48.11  19.00 -30.00  104
  4  ω    -26.00  21.00   0.50    0.14    --  -48.11  19.00  60.00   94
  5  ω    -27.00  23.00   0.50    0.14    --  -48.11  19.00 150.00  100
  6  ω    112.00 137.00   0.50    0.43    --  105.08 117.00 121.00   50
  7  ω    102.00 160.00   0.50    0.43    --  105.08 125.00 -30.00  116
  8  ω     73.00 103.00   0.50    0.14    --   48.11  38.00  90.00   60
  9  ω     41.00  67.00   0.50    0.43    --  105.08 -77.00  60.00   52
 10  ω     75.00 101.00   0.50    0.43    --  105.08 -77.00  60.00   52
 11  ω     44.00  71.00   0.50    0.43    --  105.08 -61.00  60.00   54
 12  ω     95.00 174.00   0.50    0.43    --  105.08  15.00 -60.00  158
 13  ω    122.00 178.00   0.50    0.43    --  105.08  30.00-150.00  112
 14  ω     65.00  91.00   0.50    0.43    --  105.08 -77.00-180.00   52
 15  ω     37.00 101.00   0.50    0.43    --  105.08 -77.00-150.00  128
 16  ω     38.00  68.00   0.50    0.43    --  105.08 -61.00 -90.00   60
 17  ω     34.00  70.00   0.50    0.43    --  105.08 -61.00 -60.00   72
 18  ω     34.00  59.00   0.50    0.43    --  105.08 -61.00   0.00   50
 19  ω     42.00  71.00   0.50    0.43    --  105.08 -61.00  90.00   58
 20  ω    -11.00  14.00   0.50    0.14    --   48.11 -19.00 120.00   50
 21  ω     36.00  62.00   0.50    0.43    --  105.08 -94.00 -60.00   52
 22  ω     81.00 108.00   0.50    0.14    --   48.11-161.00-117.00   54
 23  ω     65.00 135.00   0.50    0.43    --  105.08-161.00-117.00  140
 24  ω     81.00 112.00   0.50    0.43    --  105.08-125.00 -30.00   62
 25  ω     38.00  64.00   0.50    0.43    --  105.08-125.00 -30.00   52
 26  ω     34.00  59.00   0.50    0.14    --   48.11-117.00  34.00   50
 27  ω     84.00 109.00   0.50    0.43    --  105.08-125.00  90.00   50
 28  ω     85.00 112.00   0.50    0.43    --  105.08-125.00 120.00   54
 29  ω     36.00  62.00   0.50    0.43    --  105.08-125.00 120.00   52
 30  ω     39.00  72.00   0.50    0.43    --  105.08-125.00  90.00   66
 31  ω     65.00  94.00   0.50    0.43    --  105.08-117.00  34.00   58
 32  ω     81.00 106.00   0.50    0.43    --  105.08 -94.00 -60.00   50
 33  ω     81.00 106.00   0.50    0.43    --  105.08 -94.00-150.00   50
 34  ω    -82.00 -12.00   0.50    0.14    --  -48.11 117.00 121.00  140
 35  ω    -79.00 -22.00   0.50    0.43    --  -90.00 117.00 121.00  114
 36  ω    -84.00 -52.00   0.50    0.43    --  -90.00 125.00   0.00   64
 37  ω    -92.00 -66.00   0.50    0.14    --  -48.11 161.00 -87.00   52
 38  ω    -95.00 -70.00   0.50    0.43    --  -90.00 161.00 -87.00   50
 39  ω    -71.00 -18.00   0.50    0.43    --  -90.00  61.00 -30.00  106
 40  ω    -50.00 -19.00   0.50    0.43    --  -90.00  45.00 -90.00   62
 41  ω    -50.00 -18.00   0.50    0.43    --  -90.00  45.00-120.00   64
 42  ω    -45.00 -20.00   0.50    0.43    --  -90.00  45.00 -60.00   50
 43  ω    -50.00 -22.00   0.50    0.43    --  -90.00  45.00 120.00   56
 44  ω    -51.00 -26.00   0.50    0.43    --  -90.00  45.00 150.00   50
 45  ω   -163.00-125.00   0.50    0.43    --  -90.00 -15.00  90.00   76
 46  ω   -105.00 -80.00   0.50    0.43    --  -90.00 -15.00  90.00   50
 47  ω   -116.00 -28.00   0.50    0.14    --  -48.11 -77.00   0.00  176
 48  ω   -129.00-103.00   0.50    0.43    --  -90.00 -45.00 -60.00   52
 49  ω   -161.00-135.00   0.50    0.43    --  -90.00 -45.00 -60.00   52
 50  ω   -161.00 -72.00   0.50    0.43    --  -90.00 -77.00   0.00  178
 51  ω   -112.00 -78.00   0.50    0.43    --  -90.00-117.00  34.00   68
 52  ω   -119.00 -94.00   0.50    0.43    --  -90.00-161.00-117.00   50
 53  ω    -97.00 -49.00   0.50    0.14    --  -48.11-161.00-117.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0615885000
_diffrn_orient_matrix_UB_12      -0.0123968000
_diffrn_orient_matrix_UB_13      0.1493283000
_diffrn_orient_matrix_UB_21      0.0044237000
_diffrn_orient_matrix_UB_22      -0.0565182000
_diffrn_orient_matrix_UB_23      -0.0356149000
_diffrn_orient_matrix_UB_31      0.1193779000
_diffrn_orient_matrix_UB_32      0.0084835000
_diffrn_orient_matrix_UB_33      -0.0195089000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -15
_reflns_limit_k_max              33
_reflns_limit_k_min              0
_reflns_limit_l_max              13
_reflns_limit_l_min              0
_reflns_number_gt                6399
_reflns_number_total             6481
_reflns_threshold_expression     I>=2u(I)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         1.7433
_refine_diff_density_min         -1.7805
_refine_diff_density_rms         0.1426
_refine_ls_d_res_high            0.7921
_refine_ls_d_res_low             13.1730
_refine_ls_goodness_of_fit_ref   1.0592
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    22
_refine_ls_number_parameters     433
_refine_ls_number_reflns         6481
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0263
_refine_ls_R_factor_gt           0.0259
_refine_ls_restrained_S_all      1.0592
_refine_ls_shift/su_max          -0.0004
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0287P)²+10.6129P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0637
_refine_ls_wR_factor_ref         0.0640
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C43(H43a,H43b), C44(H44a,H44b)
2.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C33(H33), C34(H34), C35(H35), C38(H38), C39(H39), C40(H40), C41(H41)
;
_atom_sites_solution_primary     dual
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_refinement_flags_posn
La1 La 0.702198(15) 0.607880(6) 0.318635(17) 0.00979(6) Uani 1.000000 .
O1 O 0.5045(2) 0.57158(8) 0.1857(2) 0.0145(4) Uani 1.000000 .
C2 C 0.4965(3) 0.53734(12) 0.0997(3) 0.0121(6) Uani 1.000000 .
C3 C 0.4019(3) 0.50505(12) 0.0489(3) 0.0138(6) Uani 1.000000 .
C4 C 0.3977(3) 0.46865(12) -0.0498(3) 0.0134(6) Uani 1.000000 .
O5 O 0.3137(2) 0.43968(9) -0.1030(2) 0.0164(5) Uani 1.000000 .
Br6 Br 0.27591(3) 0.509495(13) 0.11717(3) 0.01601(8) Uani 1.000000 .
O7 O 0.8577(2) 0.57194(8) 0.5416(2) 0.0148(5) Uani 1.000000 .
C8 C 0.9243(3) 0.53742(12) 0.5295(3) 0.0132(6) Uani 1.000000 .
C9 C 0.9817(3) 0.50224(13) 0.6286(3) 0.0161(7) Uani 1.000000 .
C10 C 1.0548(3) 0.46504(12) 0.6071(3) 0.0138(6) Uani 1.000000 .
O11 O 1.1084(2) 0.43201(9) 0.6906(2) 0.0159(5) Uani 1.000000 .
Br12 Br 0.96747(3) 0.508029(13) 0.80236(3) 0.01697(8) Uani 1.000000 .
O13 O 0.6579(2) 0.51041(9) 0.3688(2) 0.0154(5) Uani 1.000000 .
C14 C 0.5816(3) 0.50305(12) 0.4239(3) 0.0136(6) Uani 1.000000 .
C15 C 0.5169(3) 0.45855(12) 0.4186(3) 0.0145(6) Uani 1.000000 .
C16 C 0.4421(3) 0.45191(12) 0.4936(3) 0.0131(6) Uani 1.000000 .
O17 O 0.3908(2) 0.41115(9) 0.5024(2) 0.0157(5) Uani 1.000000 .
Br18 Br 0.53304(3) 0.404024(13) 0.30748(4) 0.01899(8) Uani 1.000000 .
C19 C 0.8250(3) 0.75787(13) 0.5912(4) 0.0178(7) Uani 1.000000 .
C20 C 0.7690(3) 0.71784(12) 0.5091(3) 0.0150(6) Uani 1.000000 .
C21 C 0.6359(3) 0.72080(13) 0.4420(3) 0.0164(7) Uani 1.000000 .
C22 C 0.5767(3) 0.76193(13) 0.4712(4) 0.0210(7) Uani 1.000000 .
C23 C 0.6310(3) 0.79986(13) 0.5645(3) 0.0170(7) Uani 1.000000 .
C24 C 0.7644(3) 0.79733(12) 0.6284(3) 0.0166(7) Uani 1.000000 .
O25 O 0.8169(2) 0.67866(8) 0.4829(2) 0.0160(5) Uani 1.000000 .
O26 O 0.5916(2) 0.68497(9) 0.3629(2) 0.0178(5) Uani 1.000000 .
O27 O 0.5820(2) 0.83598(9) 0.6009(3) 0.0212(5) Uani 1.000000 .
O28 O 0.8104(2) 0.83190(9) 0.7096(2) 0.0187(5) Uani 1.000000 .
Br29 Br 0.99036(3) 0.759069(14) 0.65833(5) 0.02772(10) Uani 1.000000 .
Br30 Br 0.41451(4) 0.767009(17) 0.37887(5) 0.03804(12) Uani 1.000000 .
N31 N 0.0254(3) 0.64379(11) -0.1054(3) 0.0191(6) Uani 1.000000 .
C32 C -0.0706(3) 0.64435(14) -0.2136(4) 0.0212(7) Uani 1.000000 .
H32 H -0.0648(3) 0.65485(14) -0.2976(4) 0.0255(9) Uiso 1.000000 R
C33 C -0.1779(3) 0.63003(12) -0.2060(4) 0.0178(7) Uani 1.000000 .
H33 H -0.2457(3) 0.63123(12) -0.2830(4) 0.0213(8) Uiso 1.000000 R
C34 C -0.1843(3) 0.61381(12) -0.0828(4) 0.0171(7) Uani 1.000000 .
H34 H -0.2573(3) 0.60496(12) -0.0734(4) 0.0205(8) Uiso 1.000000 R
C35 C -0.0823(3) 0.61068(12) 0.0268(4) 0.0165(7) Uani 1.000000 .
H35 H -0.0852(3) 0.59748(12) 0.1097(4) 0.0198(8) Uiso 1.000000 R
C36 C 0.0226(3) 0.62654(12) 0.0160(3) 0.0156(6) Uani 1.000000 .
C37 C 0.1309(3) 0.62841(12) 0.1325(4) 0.0173(7) Uani 1.000000 .
C38 C 0.1302(3) 0.62331(15) 0.2628(4) 0.0247(8) Uani 1.000000 .
H38 H 0.0590(3) 0.61787(15) 0.2804(4) 0.0297(9) Uiso 1.000000 R
C39 C 0.2353(4) 0.62622(17) 0.3685(4) 0.0317(9) Uani 1.000000 .
H39 H 0.2366(4) 0.62046(17) 0.4582(4) 0.0381(11) Uiso 1.000000 R
C40 C 0.3372(3) 0.63745(15) 0.3429(4) 0.0285(9) Uani 1.000000 .
H40 H 0.4083(3) 0.64099(15) 0.4150(4) 0.0342(10) Uiso 1.000000 R
C41 C 0.3353(3) 0.64347(14) 0.2132(4) 0.0259(8) Uani 1.000000 .
H41 H 0.4050(3) 0.65176(14) 0.1948(4) 0.0310(10) Uiso 1.000000 R
N42 N 0.2346(3) 0.63765(11) 0.1115(3) 0.0203(6) Uani 1.000000 .
C43 C 0.2377(3) 0.63641(16) -0.0267(4) 0.0287(9) Uani 1.000000 .
H43a H 0.3115(3) 0.65151(16) -0.0303(4) 0.0345(10) Uiso 1.000000 R
H43b H 0.2337(3) 0.60086(16) -0.0584(4) 0.0345(10) Uiso 1.000000 R
C44 C 0.1361(3) 0.66582(16) -0.1149(4) 0.0295(9) Uani 1.000000 .
H44a H 0.1357(3) 0.66445(16) -0.2091(4) 0.0353(10) Uiso 1.000000 R
H44b H 0.1427(3) 0.70181(16) -0.0863(4) 0.0353(10) Uiso 1.000000 R
O45 O 0.2169(4) 0.73472(19) 0.5739(5) 0.0710(12) Uani 1.000000 .
O46 O 0.0820(5) 0.6439(2) 0.5537(7) 0.098(2) Uani 1.000000 .
O47 O 0.2073(4) 0.5663(2) 0.7226(5) 0.0782(16) Uani 1.000000 .


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
La1 O1 2.538(2) . ?
La1 O5 2.543(2) 3_665 ?
La1 O7 2.663(2) . ?
La1 O11 2.553(2) 3_766 ?
La1 O13 2.710(2) . ?
La1 O17 2.536(2) 3_666 ?
La1 O25 2.616(2) . ?
La1 O26 2.557(2) . ?
La1 O27 2.720(3) 4_575 ?
La1 O28 2.553(2) 4_575 ?
O1 C2 1.259(4) . ?
C2 C3 1.388(4) . ?
C2 C4 1.541(4) 3_665 ?
C3 C4 1.402(5) . ?
C3 Br6 1.888(3) . ?
C4 O5 1.250(4) . ?
O7 C8 1.249(4) . ?
C8 C9 1.401(5) . ?
C8 C10 1.538(4) 3_766 ?
C9 C10 1.387(5) . ?
C9 Br12 1.896(3) . ?
C10 O11 1.258(4) . ?
O13 C14 1.254(4) . ?
C14 C15 1.401(5) . ?
C14 C16 1.551(4) 3_666 ?
C15 C16 1.390(5) . ?
C15 Br18 1.901(3) . ?
C16 O17 1.259(4) . ?
C19 C20 1.393(5) . ?
C19 C24 1.399(5) . ?
C19 Br29 1.897(3) . ?
C20 C21 1.538(5) . ?
C20 O25 1.258(4) . ?
C21 C22 1.388(5) . ?
C21 O26 1.258(4) . ?
C22 C23 1.406(5) . ?
C22 Br30 1.894(4) . ?
C23 C24 1.538(5) . ?
C23 O27 1.245(4) . ?
C24 O28 1.250(4) . ?
N31 C32 1.339(5) . ?
N31 C36 1.366(4) . ?
N31 C44 1.493(5) . ?
C32 H32 0.9500 . ?
C32 C33 1.380(5) . ?
C33 H33 0.9500 . ?
C33 C34 1.389(5) . ?
C34 H34 0.9500 . ?
C34 C35 1.393(5) . ?
C35 H35 0.9500 . ?
C35 C36 1.376(5) . ?
C36 C37 1.479(5) . ?
C37 C38 1.379(5) . ?
C37 N42 1.366(5) . ?
C38 H38 0.9500 . ?
C38 C39 1.396(6) . ?
C39 H39 0.9500 . ?
C39 C40 1.377(6) . ?
C40 H40 0.9500 . ?
C40 C41 1.366(6) . ?
C41 H41 0.9500 . ?
C41 N42 1.346(5) . ?
N42 C43 1.466(5) . ?
C43 H43a 0.9900 . ?
C43 H43b 0.9900 . ?
C43 C44 1.496(6) . ?
C44 H44a 0.9900 . ?
C44 H44b 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O5 La1 O1 62.39(7) 3_665 . ?
O7 La1 O1 128.64(7) . . ?
O7 La1 O5 116.01(7) . 3_665 ?
O11 La1 O1 121.55(7) 3_766 . ?
O11 La1 O5 64.77(8) 3_766 3_665 ?
O11 La1 O7 59.89(7) 3_766 . ?
O13 La1 O1 62.56(7) . . ?
O13 La1 O5 75.15(7) . 3_665 ?
O13 La1 O7 67.66(7) . . ?
O13 La1 O11 81.61(7) . 3_766 ?
O17 La1 O1 76.61(7) 3_666 . ?
O17 La1 O5 129.82(7) 3_666 3_665 ?
O17 La1 O7 68.50(7) 3_666 . ?
O17 La1 O11 124.50(7) 3_666 3_766 ?
O17 La1 O13 60.33(7) 3_666 . ?
O25 La1 O1 146.94(7) . . ?
O25 La1 O5 144.22(7) . 3_665 ?
O25 La1 O7 66.29(7) . . ?
O25 La1 O11 91.50(7) . 3_766 ?
O25 La1 O13 130.05(7) . . ?
O25 La1 O17 85.37(7) . 3_666 ?
O26 La1 O1 86.75(7) . . ?
O26 La1 O5 131.34(8) . 3_665 ?
O26 La1 O7 112.65(7) . . ?
O26 La1 O11 149.73(7) . 3_766 ?
O26 La1 O13 124.68(7) . . ?
O26 La1 O17 68.75(8) . 3_666 ?
O26 La1 O25 60.75(7) . . ?
O27 La1 O1 65.64(7) 4_575 . ?
O27 La1 O5 69.61(8) 4_575 3_665 ?
O27 La1 O7 165.68(7) 4_575 . ?
O27 La1 O11 115.82(7) 4_575 3_766 ?
O27 La1 O13 126.39(7) 4_575 . ?
O27 La1 O17 119.13(8) 4_575 3_666 ?
O27 La1 O25 101.20(7) 4_575 . ?
O27 La1 O26 63.37(8) 4_575 . ?
O28 La1 O1 121.08(8) 4_575 . ?
O28 La1 O5 78.92(8) 4_575 3_665 ?
O28 La1 O7 107.27(7) 4_575 . ?
O28 La1 O11 68.98(7) 4_575 3_766 ?
O28 La1 O13 147.02(7) 4_575 . ?
O28 La1 O17 150.63(8) 4_575 3_666 ?
O28 La1 O25 67.26(8) 4_575 . ?
O28 La1 O26 87.89(8) 4_575 . ?
O28 La1 O27 59.80(8) 4_575 4_575 ?
C2 O1 La1 120.4(2) . . ?
C3 C2 O1 125.3(3) . . ?
C4 C2 O1 116.0(3) 3_665 . ?
C4 C2 C3 118.7(3) 3_665 . ?
C4 C3 C2 122.2(3) . . ?
Br6 C3 C2 118.9(2) . . ?
Br6 C3 C4 118.9(2) . . ?
C3 C4 C2 119.1(3) . 3_665 ?
O5 C4 C2 115.5(3) . 3_665 ?
O5 C4 C3 125.4(3) . . ?
C4 O5 La1 121.1(2) . 3_665 ?
C8 O7 La1 117.7(2) . . ?
C9 C8 O7 126.0(3) . . ?
C10 C8 O7 115.6(3) 3_766 . ?
C10 C8 C9 118.4(3) 3_766 . ?
C10 C9 C8 122.4(3) . . ?
Br12 C9 C8 119.1(2) . . ?
Br12 C9 C10 118.4(3) . . ?
C9 C10 C8 119.2(3) . 3_766 ?
O11 C10 C8 114.8(3) . 3_766 ?
O11 C10 C9 126.0(3) . . ?
C10 O11 La1 121.7(2) . 3_766 ?
C14 O13 La1 117.3(2) . . ?
C15 C14 O13 126.6(3) . . ?
C16 C14 O13 116.0(3) 3_666 . ?
C16 C14 C15 117.4(3) 3_666 . ?
C16 C15 C14 122.8(3) . . ?
Br18 C15 C14 119.3(2) . . ?
Br18 C15 C16 117.9(2) . . ?
C15 C16 C14 119.5(3) . 3_666 ?
O17 C16 C14 115.3(3) . 3_666 ?
O17 C16 C15 125.2(3) . . ?
C16 O17 La1 124.8(2) . 3_666 ?
C24 C19 C20 122.8(3) . . ?
Br29 C19 C20 119.2(3) . . ?
Br29 C19 C24 118.0(3) . . ?
C21 C20 C19 118.3(3) . . ?
O25 C20 C19 126.2(3) . . ?
O25 C20 C21 115.5(3) . . ?
C22 C21 C20 118.5(3) . . ?
O26 C21 C20 115.2(3) . . ?
O26 C21 C22 126.3(3) . . ?
C23 C22 C21 123.5(3) . . ?
Br30 C22 C21 117.8(3) . . ?
Br30 C22 C23 118.8(3) . . ?
C24 C23 C22 117.5(3) . . ?
O27 C23 C22 126.6(3) . . ?
O27 C23 C24 115.9(3) . . ?
C23 C24 C19 118.8(3) . . ?
O28 C24 C19 125.1(3) . . ?
O28 C24 C23 116.1(3) . . ?
C20 O25 La1 123.0(2) . . ?
C21 O26 La1 125.4(2) . . ?
C23 O27 La1 119.7(2) . 4_576 ?
C24 O28 La1 125.4(2) . 4_576 ?
C36 N31 C32 121.4(3) . . ?
C44 N31 C32 119.4(3) . . ?
C44 N31 C36 119.0(3) . . ?
H32 C32 N31 119.2(2) . . ?
C33 C32 N31 121.6(3) . . ?
C33 C32 H32 119.2(2) . . ?
H33 C33 C32 120.8(2) . . ?
C34 C33 C32 118.4(3) . . ?
C34 C33 H33 120.8(2) . . ?
H34 C34 C33 120.4(2) . . ?
C35 C34 C33 119.2(3) . . ?
C35 C34 H34 120.4(2) . . ?
H35 C35 C34 119.7(2) . . ?
C36 C35 C34 120.6(3) . . ?
C36 C35 H35 119.7(2) . . ?
C35 C36 N31 118.7(3) . . ?
C37 C36 N31 118.7(3) . . ?
C37 C36 C35 122.5(3) . . ?
C38 C37 C36 122.2(3) . . ?
N42 C37 C36 119.2(3) . . ?
N42 C37 C38 118.6(3) . . ?
H38 C38 C37 120.3(2) . . ?
C39 C38 C37 119.4(4) . . ?
C39 C38 H38 120.3(3) . . ?
H39 C39 C38 120.0(3) . . ?
C40 C39 C38 120.0(4) . . ?
C40 C39 H39 120.0(3) . . ?
H40 C40 C39 120.2(3) . . ?
C41 C40 C39 119.5(4) . . ?
C41 C40 H40 120.2(2) . . ?
H41 C41 C40 120.0(2) . . ?
N42 C41 C40 120.0(4) . . ?
N42 C41 H41 120.0(2) . . ?
C41 N42 C37 122.4(3) . . ?
C43 N42 C37 118.4(3) . . ?
C43 N42 C41 119.0(3) . . ?
H43a C43 N42 109.9(2) . . ?
H43b C43 N42 109.9(2) . . ?
H43b C43 H43a 108.3 . . ?
C44 C43 N42 108.9(3) . . ?
C44 C43 H43a 109.9(2) . . ?
C44 C43 H43b 109.9(2) . . ?
C43 C44 N31 109.5(3) . . ?
H44a C44 N31 109.8(2) . . ?
H44a C44 C43 109.8(2) . . ?
H44b C44 N31 109.8(2) . . ?
H44b C44 C43 109.8(2) . . ?
H44b C44 H44a 108.2 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
La1 O1 C2 C3 160.9(2) . . . . ?
La1 O1 C2 C4 -18.3(2) . . . 3_665 ?
La1 O5 C4 C2 15.6(2) . 3_665 3_665 . ?
La1 O5 C4 C3 164.4(2) 3_665 . . . ?
La1 O7 C8 C9 -156.6(2) . . . . ?
La1 O7 C8 C10 24.6(2) . . . 3_766 ?
La1 O11 C10 C8 -26.0(2) . 3_766 3_766 . ?
La1 O11 C10 C9 -153.6(2) 3_766 . . . ?
La1 O13 C14 C15 156.7(2) . . . . ?
La1 O13 C14 C16 -23.5(2) . . . 3_666 ?
La1 O17 C16 C14 15.7(2) . 3_666 3_666 . ?
La1 O17 C16 C15 163.5(2) 3_666 . . . ?
La1 O25 C20 C19 -177.4(2) . . . . ?
La1 O25 C20 C21 2.3(2) . . . . ?
La1 O26 C21 C20 3.6(2) . . . . ?
La1 O26 C21 C22 -177.4(3) . . . . ?
La1 O27 C23 C22 167.6(2) 4_576 . . . ?
La1 O27 C23 C24 -12.8(2) 4_576 . . . ?
La1 O28 C24 C19 -165.5(3) 4_576 . . . ?
La1 O28 C24 C23 15.5(3) 4_576 . . . ?
O1 C2 C3 C4 178.2(3) . . . . ?
O1 C2 C3 Br6 -3.0(4) . . . . ?
O1 C2 C4 C3 -178.2(3) . . 3_665 3_665 ?
O1 C2 C4 O5 1.9(3) . . 3_665 3_665 ?
C2 C3 C4 C2 2.6(3) . . . 3_665 ?
C2 C3 C4 O5 -177.4(3) . . . . ?
C2 C4 C3 C2 2.6(3) 3_665 . . . ?
C2 C4 C3 Br6 -176.3(2) 3_665 . . . ?
O7 C8 C9 C10 -179.8(3) . . . . ?
O7 C8 C9 Br12 -3.9(4) . . . . ?
O7 C8 C10 C9 179.9(3) . . 3_766 3_766 ?
O7 C8 C10 O11 -0.5(3) . . 3_766 3_766 ?
C8 C9 C10 C8 1.1(3) . . . 3_766 ?
C8 C9 C10 O11 -179.4(3) . . . . ?
C8 C10 C9 C8 1.1(3) 3_766 . . . ?
C8 C10 C9 Br12 -174.9(2) 3_766 . . . ?
O13 C14 C15 C16 173.5(3) . . . . ?
O13 C14 C15 Br18 -5.2(4) . . . . ?
O13 C14 C16 C15 -173.8(3) . . 3_666 3_666 ?
O13 C14 C16 O17 7.0(3) . . 3_666 3_666 ?
C14 C15 C16 C14 6.4(3) . . . 3_666 ?
C14 C15 C16 O17 -172.8(3) . . . . ?
C14 C16 C15 C14 6.4(3) 3_666 . . . ?
C14 C16 C15 Br18 -174.9(2) 3_666 . . . ?
C19 C20 C21 C22 -3.1(4) . . . . ?
C19 C20 C21 O26 175.9(3) . . . . ?
C19 C24 C23 C22 0.0(4) . . . . ?
C19 C24 C23 O27 -179.6(3) . . . . ?
C20 C21 C22 C23 -3.4(4) . . . . ?
C20 C21 C22 Br30 176.1(2) . . . . ?
C21 C22 C23 C24 4.9(4) . . . . ?
C21 C22 C23 O27 -175.5(3) . . . . ?
C22 C23 C24 O28 179.1(3) . . . . ?
N31 C32 C33 C34 -1.3(4) . . . . ?
N31 C36 C35 C34 -2.2(4) . . . . ?
N31 C36 C37 C38 164.4(3) . . . . ?
N31 C36 C37 N42 -12.7(4) . . . . ?
N31 C44 C43 N42 -57.7(4) . . . . ?
C32 C33 C34 C35 -2.5(4) . . . . ?
C33 C34 C35 C36 4.2(4) . . . . ?
C34 C35 C36 C37 174.2(3) . . . . ?
C35 C36 C37 C38 -12.0(4) . . . . ?
C35 C36 C37 N42 170.9(3) . . . . ?
C36 C37 C38 C39 -179.0(4) . . . . ?
C36 C37 N42 C41 175.2(3) . . . . ?
C36 C37 N42 C43 -10.7(4) . . . . ?
C37 C38 C39 C40 4.3(4) . . . . ?
C37 N42 C41 C40 3.6(4) . . . . ?
C37 N42 C43 C44 46.1(3) . . . . ?
C38 C39 C40 C41 -2.9(5) . . . . ?
C39 C40 C41 N42 -1.0(4) . . . . ?
C40 C41 N42 C43 -170.6(3) . . . . ?
C41 N42 C43 C44 -139.5(4) . . . . ?


# end Validation Reply Form
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.327
_oxdiff_exptl_absorpt_empirical_full_min 0.773
# start Validation Reply Form
_vrf_PLAT041_MF-1-16B_1-mask_smrt_abs_a 
;
PROBLEM: Calc. and Reported SumFormula    Strings  Differ     Please Check 
RESPONSE: The positions of H atoms for water molecules located in the framework voids could not be refined satisfactorily and have been omitted from the refinement. The H atoms have been included in the reported sum formula. 
;
_vrf_PLAT042_MF-1-16B_1-mask_smrt_abs_a 
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check 
RESPONSE: The positions of H atoms for water molecules located in the framework voids could not be refined satisfactorily and have been omitted from the refinement. The H atoms have been included in the reported moiety formula.
;
_vrf_PLAT043_MF-1-16B_1-mask_smrt_abs_a 
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PROBLEM: Calculated and Reported Mol. Weight Differ by ..       6.09 Check 
RESPONSE: The positions of H atoms for water molecules located in the framework voids could not be refined satisfactorily and have been omitted from the refinement. The H atoms have been included in the reported sum formula.
;
_vrf_PLAT068_MF-1-16B_1-mask_smrt_abs_a 
;
PROBLEM: Reported F000 Differs from Calcd (or Missing)...     Please Check 
RESPONSE: H atoms for water molecules located in the framework voids have been omitted from the refinement. The H atoms have been included in the reported sum formula with the reported F000 value reflecting the contribution from 6 addition H atoms per formula unit.
;
_vrf_PLAT306_MF-1-16B_1-mask_smrt_abs_a 
;
PROBLEM: Isolated Oxygen Atom (H-atoms Missing ?) .......        O45 Check 
RESPONSE: H atoms for solvent water molecules located in the framework voids (O45, O46, O47) could not be positioned satisfactorily and have been omitted from the refinement.
;
_vrf_PLAT369_MF-1-16B_1-mask_smrt_abs_a 
;
PROBLEM: Long   C(sp2)-C(sp2) Bond  C2       - C4_b     .       1.54 Ang.
RESPONSE: The oxidised dianionic state of tetraoxolenes is not aromatic, therefore the C-C bond between O-bound C atoms is a formal C-C single bond.
;
_vrf_PLAT430_MF-1-16B_1-mask_smrt_abs_a 
;
PROBLEM: Short Inter D...A Contact  O46      ..O47      .       2.81 Ang.  
RESPONSE: H atoms for solvent water molecules located in the framework voids (O45, O46, O47) could not be positioned satisfactorily and have been omitted from the refinement.
;
_vrf_PLAT431_MF-1-16B_1-mask_smrt_abs_a 
;
PROBLEM: Short Inter HL..A Contact  Br29     ..O45      .       3.21 Ang.  
RESPONSE: H atoms for solvent water molecules located in the framework voids (O45, O46, O47) could not be positioned satisfactorily and have been omitted from the refinement.
;
