# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_sr22074_0ma
_database_code_depnum_ccdc_archive 'CCDC 2232423'
_audit_update_record             
;
2022-12-22 deposited with the CCDC.	2023-02-23 downloaded from the CCDC.
;
_audit_creation_date             2022-12-22
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
loop_
_audit_author_email
carsten.streb@uni-mainz.de
_chemical_name_common            ?
_chemical_name_systematic        
;
 ? 
;
_chemical_formula_moiety         
'C16 H48 La O8 S8, O32 V12, Cl, C8 H24 N4, 4(C H3 O0.6 S0.6), 4(C H3 O0.41 S0.41)'
_chemical_formula_sum            'C32 H96 Cl La N4 O44 S12 V12'
_chemical_formula_weight         2411.48
_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'
Cl Cl 0.1484 0.1585 '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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.3005 0.5294 '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      tetragonal
_space_group_IT_number           85
_space_group_name_H-M_alt        'P 4/n'
_space_group_name_Hall           '-P 4a'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y+1/2, x, z'
'-x+1/2, -y+1/2, z'
'y, -x+1/2, z'
'-x, -y, -z'
'y-1/2, -x, -z'
'x-1/2, y-1/2, -z'
'-y, x-1/2, -z'

_cell_length_a                   19.7197(10)
_cell_length_b                   19.7197(10)
_cell_length_c                   10.9727(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4266.9(5)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9990
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      26.84
_cell_measurement_theta_min      2.78
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.147
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6522
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1295 before and 0.0893 after correction. The Ratio of minimum to maximum transmission is 0.8748. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.877
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2420
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_exptl_special_details           
;
 ? 
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0922
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            57952
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.075
_diffrn_reflns_theta_min         1.856
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4416
_reflns_number_total             4698
_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       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_refine_diff_density_max         0.822
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.094
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         4698
_refine_ls_number_restraints     54
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0308
_refine_ls_restrained_S_all      1.072
_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)+(0.0227P)²+7.4265P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0694
_refine_ls_wR_factor_ref         0.0723
_refine_special_details          
;
 Refined as a 2-component twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.5454(8)
 0.4546(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 S3-O6 \\sim S3A-O6A
 with sigma of 0.02
 S3-C8 \\sim S3A-C8A
 with sigma of 0.02
 C8-C2 \\sim C8A-C2A
 with sigma of 0.04
 S3-C2 \\sim S3A-C2A
 with sigma of 0.02
 O6-C8 \\sim O6A-C8A
 with sigma of 0.04
 O6-C2 \\sim O6A-C2A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Uanis(S3) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C2) \\sim
Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(S3A) \\sim Ueq, Uanis(O6A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C2A)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Others
 Sof(S3A)=Sof(O6A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C2A)=Sof(H2AA)=
 Sof(H2AB)=Sof(H2AC)=1-FVAR(1)
 Sof(S3)=Sof(O6)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C2)=Sof(H2A)=Sof(H2B)=
 Sof(H2C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), N2(H2D,H2E)
6.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C17(H17A,H17B,H17C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C),
 C2(H2A,H2B,H2C), C5(H5A,H5B,H5C), C8A(H8AA,H8AB,H8AC), C2A(H2AA,H2AB,H2AC)
;
_atom_sites_solution_hydrogens   geom
_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
La1 La 0.2500 0.7500 0.0000 0.01467(9) Uani 1 4 d S T P . .
V2 V 0.33161(3) 0.41688(3) 0.54143(6) 0.01618(13) Uani 1 1 d . . . . .
V3 V 0.18927(3) 0.43039(3) 0.52701(6) 0.01699(14) Uani 1 1 d . . . . .
V4 V 0.20635(4) 0.36380(3) 0.77736(6) 0.01694(14) Uani 1 1 d . . . . .
S7 S 0.29500(7) 0.61465(6) 0.22052(11) 0.0321(3) Uani 1 1 d . . . . .
O9 O 0.38002(13) 0.35992(13) 0.6524(2) 0.0172(6) Uani 1 1 d . . . . .
O7 O 0.26339(14) 0.42983(14) 0.4302(2) 0.0209(6) Uani 1 1 d . . . . .
O10 O 0.16397(16) 0.50758(15) 0.5356(3) 0.0255(6) Uani 1 1 d . . . . .
O11 O 0.18915(15) 0.42136(15) 0.8750(2) 0.0233(6) Uani 1 1 d . . . . .
O13 O 0.36584(16) 0.48971(15) 0.5582(3) 0.0235(6) Uani 1 1 d . . . . .
C1 C 0.4052(3) 0.7721(3) 0.2803(4) 0.0500(17) Uani 1 1 d . . . . .
H1A H 0.3592 0.7623 0.3091 0.075 Uiso 1 1 calc GR . . . .
H1B H 0.4306 0.7953 0.3447 0.075 Uiso 1 1 calc GR . . . .
H1C H 0.4280 0.7295 0.2594 0.075 Uiso 1 1 calc GR . . . .
O4 O 0.25621(18) 0.67910(14) 0.1919(2) 0.0269(6) Uani 1 1 d . . . . .
C17 C 0.2372(3) 0.5470(2) 0.2030(5) 0.0441(13) Uani 1 1 d . . . . .
H17A H 0.1954 0.5572 0.2477 0.066 Uiso 1 1 calc GR . . . .
H17B H 0.2573 0.5052 0.2352 0.066 Uiso 1 1 calc GR . . . .
H17C H 0.2267 0.5409 0.1164 0.066 Uiso 1 1 calc GR . . . .
O3 O 0.36848(16) 0.78034(17) 0.0526(3) 0.0299(7) Uani 1 1 d . . . . .
S2 S 0.40105(6) 0.82465(6) 0.14973(10) 0.0268(2) Uani 1 1 d . . . . .
Cl1 Cl 0.2500 0.2500 0.58252(17) 0.0295(4) Uani 1 4 d S T P . .
O2 O 0.25788(14) 0.41592(13) 0.6511(2) 0.0178(5) Uani 1 1 d . . . . .
O5 O 0.16381(14) 0.29325(14) 0.8301(2) 0.0192(6) Uani 1 1 d . . . . .
C3 C 0.2624(2) 0.3630(2) 0.1168(4) 0.0245(9) Uani 1 1 d . . . . .
H3A H 0.2618 0.3323 0.0454 0.029 Uiso 1 1 calc R . . . .
H3B H 0.2803 0.4075 0.0900 0.029 Uiso 1 1 calc R . . . .
O1 O 0.12996(14) 0.38475(14) 0.4323(2) 0.0197(6) Uani 1 1 d . . . . .
S3 S 0.48909(13) 0.93207(13) -0.2505(2) 0.0422(8) Uani 0.595(5) 1 d D U . A -1
C4 C 0.3715(2) 0.3087(2) 0.1654(4) 0.0241(9) Uani 1 1 d . . . . .
H4A H 0.4055 0.3086 0.2318 0.029 Uiso 1 1 calc R . . . .
H4B H 0.3883 0.3387 0.0996 0.029 Uiso 1 1 calc R . . . .
C9 C 0.4880(2) 0.8270(3) 0.1122(4) 0.0322(10) Uani 1 1 d . . . . .
H9A H 0.5134 0.8483 0.1788 0.048 Uiso 1 1 calc GR . . . .
H9B H 0.4944 0.8533 0.0373 0.048 Uiso 1 1 calc GR . . . .
H9C H 0.5047 0.7807 0.0997 0.048 Uiso 1 1 calc GR . . . .
O6 O 0.5219(11) 0.8900(8) -0.1573(19) 0.083(8) Uani 0.595(5) 1 d D U . A -1
C8 C 0.5442(7) 0.9999(5) -0.2902(12) 0.061(4) Uani 0.595(5) 1 d D U . A -1
H8A H 0.5785 0.9836 -0.3476 0.092 Uiso 0.595(5) 1 calc GR . . A -1
H8B H 0.5665 1.0171 -0.2166 0.092 Uiso 0.595(5) 1 calc GR . . A -1
H8C H 0.5178 1.0364 -0.3281 0.092 Uiso 0.595(5) 1 calc GR . . A -1
C2 C 0.4321(7) 0.9851(10) -0.1638(19) 0.056(4) Uani 0.595(5) 1 d D U . A 1
H2A H 0.4308 1.0274 -0.1171 0.083 Uiso 0.595(5) 1 calc GR . . A 1
H2B H 0.4079 0.9496 -0.1189 0.083 Uiso 0.595(5) 1 calc GR . . A 1
H2C H 0.4103 0.9920 -0.2431 0.083 Uiso 0.595(5) 1 calc GR . . A 1
N2 N 0.3068(2) 0.3347(2) 0.2117(3) 0.0306(9) Uani 1 1 d . . . . .
H2D H 0.3154 0.3675 0.2680 0.037 Uiso 1 1 calc R . . . .
H2E H 0.2845 0.3005 0.2502 0.037 Uiso 1 1 calc R . . . .
C5 C 0.2989(4) 0.6128(3) 0.3837(5) 0.0616(19) Uani 1 1 d . . . . .
H5A H 0.3297 0.6483 0.4124 0.092 Uiso 1 1 calc GR . . . .
H5B H 0.3155 0.5684 0.4105 0.092 Uiso 1 1 calc GR . . . .
H5C H 0.2535 0.6206 0.4172 0.092 Uiso 1 1 calc GR . . . .
S3A S 0.51748(18) 0.9601(2) -0.1859(3) 0.0435(12) Uani 0.405(5) 1 d D U . A 1
O6A O 0.5258(12) 0.8845(7) -0.189(2) 0.035(4) Uani 0.405(5) 1 d D U . A 1
C8A C 0.4325(14) 0.9751(19) -0.139(3) 0.113(16) Uani 0.405(5) 1 d D U . A -1
H8AA H 0.4488 0.9665 -0.0564 0.169 Uiso 0.405(5) 1 calc GR . . A -1
H8AB H 0.3862 0.9575 -0.1480 0.169 Uiso 0.405(5) 1 calc GR . . A -1
H8AC H 0.4325 1.0240 -0.1551 0.169 Uiso 0.405(5) 1 calc GR . . A -1
C2A C 0.5049(9) 0.9815(8) -0.3431(12) 0.049(4) Uani 0.405(5) 1 d D U . A 1
H2AA H 0.4660 0.9562 -0.3752 0.073 Uiso 0.405(5) 1 calc GR . . A 1
H2AB H 0.5456 0.9698 -0.3898 0.073 Uiso 0.405(5) 1 calc GR . . A 1
H2AC H 0.4961 1.0303 -0.3504 0.073 Uiso 0.405(5) 1 calc GR . . A 1


_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 O4 2.531(3) . ?
La1 O4 2.531(3) 8_665 ?
La1 O4 2.531(3) 6_565 ?
La1 O4 2.531(3) 3_565 ?
La1 O3 2.480(3) . ?
La1 O3 2.480(3) 8_665 ?
La1 O3 2.480(3) 6_565 ?
La1 O3 2.480(3) 3_565 ?
V2 V3 2.8638(10) 4 ?
V2 V3 2.8240(10) . ?
V2 O9 1.912(3) . ?
V2 O7 1.834(3) . ?
V2 O13 1.598(3) . ?
V2 O2 1.888(3) . ?
V2 O1 1.840(3) 4 ?
V3 V2 2.8637(10) 2 ?
V3 V4 3.0633(9) . ?
V3 O9 1.955(3) 2 ?
V3 O7 1.807(3) . ?
V3 O10 1.605(3) . ?
V3 O2 1.941(3) . ?
V3 O1 1.805(3) . ?
V4 O9 1.921(3) 2 ?
V4 O11 1.597(3) . ?
V4 O2 2.002(3) . ?
V4 O5 1.725(3) . ?
V4 O5 1.889(3) 4 ?
S7 O4 1.516(3) . ?
S7 C17 1.766(5) . ?
S7 C5 1.792(5) . ?
O9 V3 1.955(3) 4 ?
O9 V4 1.921(3) 4 ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1C 0.9800 . ?
C1 S2 1.770(5) . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 0.9800 . ?
O3 S2 1.520(3) . ?
S2 C9 1.765(5) . ?
O5 V4 1.889(3) 2 ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C3 C4 1.510(6) 2 ?
C3 N2 1.470(5) . ?
O1 V2 1.840(3) 2 ?
S3 O6 1.467(13) . ?
S3 C8 1.777(12) . ?
S3 C2 1.806(14) . ?
S3 S3A 1.059(4) . ?
S3 O6A 1.366(15) . ?
S3 C8A 1.86(3) . ?
S3 C2A 1.442(14) . ?
C4 C3 1.510(6) 4 ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C4 N2 1.466(5) . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?
O6 S3A 1.420(14) . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C8 S3A 1.484(10) . ?
C8 C2A 1.034(18) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C2 S3A 1.771(14) . ?
N2 H2D 0.9100 . ?
N2 H2E 0.9100 . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 0.9800 . ?
S3A O6A 1.500(14) . ?
S3A C8A 1.777(19) . ?
S3A C2A 1.793(13) . ?
C8A H8AA 0.9800 . ?
C8A H8AB 0.9800 . ?
C8A H8AC 0.9800 . ?
C2A H2AA 0.9800 . ?
C2A H2AB 0.9800 . ?
C2A H2AC 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
O4 La1 O4 133.83(8) . 6_565 ?
O4 La1 O4 133.83(8) 6_565 3_565 ?
O4 La1 O4 67.36(12) . 3_565 ?
O4 La1 O4 133.83(8) . 8_665 ?
O4 La1 O4 133.83(8) 3_565 8_665 ?
O4 La1 O4 67.36(12) 6_565 8_665 ?
O3 La1 O4 70.22(9) 3_565 6_565 ?
O3 La1 O4 83.91(11) . . ?
O3 La1 O4 136.54(9) 3_565 8_665 ?
O3 La1 O4 73.65(11) 6_565 8_665 ?
O3 La1 O4 83.91(11) 3_565 3_565 ?
O3 La1 O4 136.54(9) . 6_565 ?
O3 La1 O4 70.22(9) 6_565 . ?
O3 La1 O4 73.65(11) 8_665 6_565 ?
O3 La1 O4 83.91(11) 8_665 8_665 ?
O3 La1 O4 70.22(9) . 8_665 ?
O3 La1 O4 73.65(11) 3_565 . ?
O3 La1 O4 136.54(9) 8_665 . ?
O3 La1 O4 73.65(11) . 3_565 ?
O3 La1 O4 136.54(9) 6_565 3_565 ?
O3 La1 O4 83.91(11) 6_565 6_565 ?
O3 La1 O4 70.22(9) 8_665 3_565 ?
O3 La1 O3 153.07(14) 3_565 . ?
O3 La1 O3 93.11(3) 3_565 8_665 ?
O3 La1 O3 93.11(3) 3_565 6_565 ?
O3 La1 O3 153.07(14) 6_565 8_665 ?
O3 La1 O3 93.11(3) 8_665 . ?
O3 La1 O3 93.11(3) 6_565 . ?
V3 V2 V3 137.89(4) . 4 ?
O9 V2 V3 42.79(8) . 4 ?
O9 V2 V3 125.97(8) . . ?
O7 V2 V3 38.80(8) . . ?
O7 V2 V3 124.32(9) . 4 ?
O7 V2 O9 150.65(12) . . ?
O7 V2 O2 81.99(11) . . ?
O7 V2 O1 93.13(12) . 4 ?
O13 V2 V3 109.98(12) . . ?
O13 V2 V3 112.09(12) . 4 ?
O13 V2 O9 104.12(13) . . ?
O13 V2 O7 105.15(14) . . ?
O13 V2 O2 105.14(14) . . ?
O13 V2 O1 106.60(14) . 4 ?
O2 V2 V3 43.20(8) . . ?
O2 V2 V3 123.49(8) . 4 ?
O2 V2 O9 88.43(11) . . ?
O1 V2 V3 125.24(9) 4 . ?
O1 V2 V3 37.78(8) 4 4 ?
O1 V2 O9 80.51(12) 4 . ?
O1 V2 O2 148.06(12) 4 . ?
V2 V3 V2 131.25(4) . 2 ?
V2 V3 V4 78.47(3) . . ?
V2 V3 V4 74.89(2) 2 . ?
O9 V3 V2 113.95(8) 2 . ?
O9 V3 V2 41.64(8) 2 2 ?
O9 V3 V4 37.39(8) 2 . ?
O7 V3 V2 128.28(9) . 2 ?
O7 V3 V2 39.50(8) . . ?
O7 V3 V4 115.83(9) . . ?
O7 V3 O9 144.30(12) . 2 ?
O7 V3 O2 81.25(12) . . ?
O10 V3 V2 114.50(12) . 2 ?
O10 V3 V2 113.28(12) . . ?
O10 V3 V4 112.83(11) . . ?
O10 V3 O9 106.64(14) . 2 ?
O10 V3 O7 106.98(14) . . ?
O10 V3 O2 108.36(13) . . ?
O10 V3 O1 107.78(14) . . ?
O2 V3 V2 41.75(8) . . ?
O2 V3 V2 111.76(8) . 2 ?
O2 V3 V4 39.74(8) . . ?
O2 V3 O9 77.13(11) . 2 ?
O1 V3 V2 38.64(9) . 2 ?
O1 V3 V2 129.00(9) . . ?
O1 V3 V4 111.95(9) . . ?
O1 V3 O9 80.22(11) . 2 ?
O1 V3 O7 100.52(12) . . ?
O1 V3 O2 141.48(12) . . ?
O9 V4 V3 38.16(8) 2 . ?
O9 V4 O2 76.46(11) 2 . ?
O11 V4 V3 105.87(11) . . ?
O11 V4 O9 102.48(13) . 2 ?
O11 V4 O2 101.95(13) . . ?
O11 V4 O5 101.06(14) . 4 ?
O11 V4 O5 104.17(14) . . ?
O2 V4 V3 38.30(8) . . ?
O5 V4 V3 126.40(9) . . ?
O5 V4 V3 119.88(9) 4 . ?
O5 V4 O9 152.11(11) 4 2 ?
O5 V4 O9 92.47(12) . 2 ?
O5 V4 O2 84.24(12) 4 . ?
O5 V4 O2 153.29(12) . . ?
O5 V4 O5 96.07(18) . 4 ?
O4 S7 C17 106.6(2) . . ?
O4 S7 C5 104.2(2) . . ?
C17 S7 C5 96.9(3) . . ?
V2 O9 V3 95.57(11) . 4 ?
V2 O9 V4 140.46(15) . 4 ?
V4 O9 V3 104.45(13) 4 4 ?
V3 O7 V2 101.70(12) . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
S2 C1 H1A 109.5 . . ?
S2 C1 H1B 109.5 . . ?
S2 C1 H1C 109.5 . . ?
S7 O4 La1 131.27(17) . . ?
S7 C17 H17A 109.5 . . ?
S7 C17 H17B 109.5 . . ?
S7 C17 H17C 109.5 . . ?
H17A C17 H17B 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
S2 O3 La1 134.42(18) . . ?
O3 S2 C1 104.5(2) . . ?
O3 S2 C9 105.2(2) . . ?
C9 S2 C1 99.2(3) . . ?
V2 O2 V3 95.05(10) . . ?
V2 O2 V4 146.87(16) . . ?
V3 O2 V4 101.96(13) . . ?
V4 O5 V4 140.27(16) . 2 ?
H3A C3 H3B 108.1 . . ?
C4 C3 H3A 109.6 2 . ?
C4 C3 H3B 109.6 2 . ?
N2 C3 H3A 109.6 . . ?
N2 C3 H3B 109.6 . . ?
N2 C3 C4 110.2(3) . 2 ?
V3 O1 V2 103.57(12) . 2 ?
O6 S3 C8 109.1(10) . . ?
O6 S3 C2 103.6(11) . . ?
O6 S3 C8A 93.8(14) . . ?
C8 S3 C2 94.2(7) . . ?
C8 S3 C8A 100.6(13) . . ?
C2 S3 C8A 10.3(16) . . ?
S3A S3 O6 66.1(9) . . ?
S3A S3 C8 56.5(5) . . ?
S3A S3 C2 71.0(6) . . ?
S3A S3 O6A 75.2(10) . . ?
S3A S3 C8A 68.9(13) . . ?
S3A S3 C2A 90.3(8) . . ?
O6A S3 O6 14.3(18) . . ?
O6A S3 C8 108.4(11) . . ?
O6A S3 C2 117.7(13) . . ?
O6A S3 C8A 107.8(16) . . ?
O6A S3 C2A 134.5(12) . . ?
C2A S3 O6 141.1(11) . . ?
C2A S3 C8 35.6(7) . . ?
C2A S3 C2 96.6(9) . . ?
C2A S3 C8A 106.5(12) . . ?
C3 C4 H4A 109.5 4 . ?
C3 C4 H4B 109.5 4 . ?
H4A C4 H4B 108.1 . . ?
N2 C4 C3 110.5(4) . 4 ?
N2 C4 H4A 109.5 . . ?
N2 C4 H4B 109.5 . . ?
S2 C9 H9A 109.5 . . ?
S2 C9 H9B 109.5 . . ?
S2 C9 H9C 109.5 . . ?
H9A C9 H9B 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
S3A O6 S3 43.0(3) . . ?
S3 C8 H8A 109.5 . . ?
S3 C8 H8B 109.5 . . ?
S3 C8 H8C 109.5 . . ?
H8A C8 H8B 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
S3A C8 S3 36.5(3) . . ?
S3A C8 H8A 124.6 . . ?
S3A C8 H8B 73.0 . . ?
S3A C8 H8C 121.9 . . ?
C2A C8 S3 54.3(10) . . ?
C2A C8 H8A 92.4 . . ?
C2A C8 H8B 157.0 . . ?
C2A C8 H8C 67.8 . . ?
C2A C8 S3A 89.0(12) . . ?
S3 C2 H2A 141.7 . . ?
S3 C2 H2B 98.9 . . ?
S3 C2 H2C 83.4 . . ?
H2A C2 H2B 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
S3A C2 S3 34.4(3) . . ?
S3A C2 H2A 109.5 . . ?
S3A C2 H2B 109.5 . . ?
S3A C2 H2C 109.5 . . ?
C3 N2 H2D 108.8 . . ?
C3 N2 H2E 108.8 . . ?
C4 N2 C3 113.9(3) . . ?
C4 N2 H2D 108.8 . . ?
C4 N2 H2E 108.8 . . ?
H2D N2 H2E 107.7 . . ?
S7 C5 H5A 109.5 . . ?
S7 C5 H5B 109.5 . . ?
S7 C5 H5C 109.5 . . ?
H5A C5 H5B 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
S3 S3A O6 70.9(9) . . ?
S3 S3A C8 87.0(7) . . ?
S3 S3A C2 74.6(7) . . ?
S3 S3A O6A 61.7(9) . . ?
S3 S3A C8A 77.3(15) . . ?
S3 S3A C2A 53.5(6) . . ?
O6 S3A C8 131.6(10) . . ?
O6 S3A C2 107.4(11) . . ?
O6 S3A O6A 14.1(18) . . ?
O6 S3A C8A 99.0(15) . . ?
O6 S3A C2A 116.8(11) . . ?
C8 S3A C2 107.2(9) . . ?
C8 S3A O6A 118.2(11) . . ?
C8 S3A C8A 117.9(13) . . ?
C8 S3A C2A 35.2(7) . . ?
C2 S3A C8A 10.7(17) . . ?
C2 S3A C2A 86.3(9) . . ?
O6A S3A C2 112.5(12) . . ?
O6A S3A C8A 105.9(15) . . ?
O6A S3A C2A 103.4(11) . . ?
C8A S3A C2A 96.1(13) . . ?
S3 O6A S3A 43.0(4) . . ?
S3 C8A H8AA 109.5 . . ?
S3 C8A H8AB 109.5 . . ?
S3 C8A H8AC 109.5 . . ?
S3A C8A S3 33.8(4) . . ?
S3A C8A H8AA 85.9 . . ?
S3A C8A H8AB 142.2 . . ?
S3A C8A H8AC 96.4 . . ?
H8AA C8A H8AB 109.5 . . ?
H8AA C8A H8AC 109.5 . . ?
H8AB C8A H8AC 109.5 . . ?
S3 C2A S3A 36.2(3) . . ?
S3 C2A H2AA 74.9 . . ?
S3 C2A H2AB 112.7 . . ?
S3 C2A H2AC 133.0 . . ?
C8 C2A S3 90.2(11) . . ?
C8 C2A S3A 55.8(9) . . ?
C8 C2A H2AA 165.0 . . ?
C8 C2A H2AB 76.3 . . ?
C8 C2A H2AC 80.4 . . ?
S3A C2A H2AA 109.5 . . ?
S3A C2A H2AB 109.5 . . ?
S3A C2A H2AC 109.5 . . ?
H2AA C2A H2AB 109.5 . . ?
H2AA C2A H2AC 109.5 . . ?
H2AB C2A H2AC 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
La1 O3 S2 C1 83.0(3) . . . . ?
La1 O3 S2 C9 -173.1(3) . . . . ?
V2 V3 O7 V2 -111.29(11) 2 . . . ?
V2 V3 O1 V2 110.22(11) . . . 2 ?
V3 V2 O7 V3 125.77(10) 4 . . . ?
V3 V2 O2 V3 -126.51(8) 4 . . . ?
V3 V2 O2 V4 -5.4(3) 4 . . . ?
V3 V2 O2 V4 121.1(3) . . . . ?
V3 V4 O5 V4 43.3(3) . . . 2 ?
V4 V3 O7 V2 -20.54(15) . . . . ?
V4 V3 O1 V2 17.42(14) . . . 2 ?
O9 V2 O7 V3 72.6(3) . . . . ?
O9 V2 O2 V3 -152.56(12) . . . . ?
O9 V2 O2 V4 -31.5(3) . . . . ?
O9 V3 O7 V2 -53.5(2) 2 . . . ?
O9 V3 O1 V2 -2.76(12) 2 . . 2 ?
O9 V4 O5 V4 62.3(3) 2 . . 2 ?
O7 V2 O2 V3 -0.38(12) . . . . ?
O7 V2 O2 V4 120.7(3) . . . . ?
O7 V3 O1 V2 140.97(13) . . . 2 ?
O10 V3 O7 V2 106.22(15) . . . . ?
O10 V3 O1 V2 -107.23(15) . . . 2 ?
O11 V4 O5 V4 165.8(2) . . . 2 ?
O13 V2 O7 V3 -103.18(16) . . . . ?
O13 V2 O2 V3 103.23(13) . . . . ?
O13 V2 O2 V4 -135.7(3) . . . . ?
C17 S7 O4 La1 -98.6(3) . . . . ?
O2 V2 O7 V3 0.42(13) . . . . ?
O2 V3 O7 V2 -0.41(12) . . . . ?
O2 V3 O1 V2 51.8(2) . . . 2 ?
O2 V4 O5 V4 -1.9(5) . . . 2 ?
O5 V4 O5 V4 -91.1(3) 4 . . 2 ?
C3 C4 N2 C3 -82.9(5) 4 . . . ?
O1 V2 O7 V3 148.69(14) 4 . . . ?
O1 V2 O2 V3 -83.4(2) 4 . . . ?
O1 V2 O2 V4 37.7(4) 4 . . . ?
O1 V3 O7 V2 -141.35(13) . . . . ?
S3 O6 S3A C8 -67.5(13) . . . . ?
S3 O6 S3A C2 66.2(9) . . . . ?
S3 O6 S3A O6A -47(7) . . . . ?
S3 O6 S3A C8A 73.1(15) . . . . ?
S3 O6 S3A C2A -28.4(10) . . . . ?
S3 C8 S3A O6 61.0(14) . . . . ?
S3 C8 S3A C2 -72.8(7) . . . . ?
S3 C8 S3A O6A 55.5(11) . . . . ?
S3 C8 S3A C8A -73.9(17) . . . . ?
S3 C8 S3A C2A -16.7(10) . . . . ?
S3 C8 C2A S3A 12.2(7) . . . . ?
S3 C2 S3A O6 -63.7(10) . . . . ?
S3 C2 S3A C8 81.8(7) . . . . ?
S3 C2 S3A O6A -49.8(11) . . . . ?
S3 C2 S3A C8A -103(10) . . . . ?
S3 C2 S3A C2A 53.2(6) . . . . ?
S3 S3A C2A C8 -159.1(13) . . . . ?
C4 C3 N2 C4 165.3(4) 2 . . . ?
O6 S3 C8 S3A -42.1(10) . . . . ?
O6 S3 C8 C2A 158.7(14) . . . . ?
O6 S3 C2 S3A 58.5(10) . . . . ?
O6 S3 S3A C8 136.2(11) . . . . ?
O6 S3 S3A C2 -115.0(12) . . . . ?
O6 S3 S3A O6A 12(2) . . . . ?
O6 S3 S3A C8A -104.3(15) . . . . ?
O6 S3 S3A C2A 148.1(11) . . . . ?
O6 S3 O6A S3A -49(7) . . . . ?
O6 S3 C8A S3A 62.6(10) . . . . ?
O6 S3 C2A C8 -33(2) . . . . ?
O6 S3 C2A S3A -50.4(15) . . . . ?
O6 S3A O6A S3 128(7) . . . . ?
O6 S3A C8A S3 -67.9(10) . . . . ?
O6 S3A C2A S3 34.0(12) . . . . ?
O6 S3A C2A C8 -125.1(14) . . . . ?
C8 S3 O6 S3A 37.7(8) . . . . ?
C8 S3 C2 S3A -52.4(6) . . . . ?
C8 S3 S3A O6 -136.2(11) . . . . ?
C8 S3 S3A C2 108.8(8) . . . . ?
C8 S3 S3A O6A -124.5(12) . . . . ?
C8 S3 S3A C8A 119.5(13) . . . . ?
C8 S3 S3A C2A 11.9(8) . . . . ?
C8 S3 O6A S3A 46.4(8) . . . . ?
C8 S3 C8A S3A -47.6(8) . . . . ?
C8 S3 C2A S3A -17.2(11) . . . . ?
C8 S3A O6A S3 -69.1(11) . . . . ?
C8 S3A C8A S3 79.6(11) . . . . ?
C8 S3A C2A S3 159.1(13) . . . . ?
C2 S3 O6 S3A -61.8(8) . . . . ?
C2 S3 C8 S3A 63.9(8) . . . . ?
C2 S3 C8 C2A -95.4(14) . . . . ?
C2 S3 S3A O6 115.0(12) . . . . ?
C2 S3 S3A C8 -108.8(8) . . . . ?
C2 S3 S3A O6A 126.8(14) . . . . ?
C2 S3 S3A C8A 10.7(17) . . . . ?
C2 S3 S3A C2A -96.9(10) . . . . ?
C2 S3 O6A S3A -58.8(10) . . . . ?
C2 S3 C8A S3A -100(10) . . . . ?
C2 S3 C2A C8 88.1(13) . . . . ?
C2 S3 C2A S3A 70.9(6) . . . . ?
C2 S3A O6A S3 56.7(11) . . . . ?
C2 S3A C8A S3 74(10) . . . . ?
C2 S3A C2A S3 -73.6(7) . . . . ?
C2 S3A C2A C8 127.3(12) . . . . ?
C5 S7 O4 La1 159.6(3) . . . . ?
S3A S3 C8 C2A -159.3(13) . . . . ?
S3A S3 C2A C8 17.2(11) . . . . ?
S3A C8 C2A S3 -12.2(7) . . . . ?
O6A S3 O6 S3A 127(7) . . . . ?
O6A S3 C8 S3A -57.2(12) . . . . ?
O6A S3 C8 C2A 143.5(16) . . . . ?
O6A S3 C2 S3A 61.0(12) . . . . ?
O6A S3 S3A O6 -12(2) . . . . ?
O6A S3 S3A C8 124.5(12) . . . . ?
O6A S3 S3A C2 -126.8(14) . . . . ?
O6A S3 S3A C8A -116.1(16) . . . . ?
O6A S3 S3A C2A 136.3(13) . . . . ?
O6A S3 C8A S3A 65.8(12) . . . . ?
O6A S3 C2A C8 -52(2) . . . . ?
O6A S3 C2A S3A -69.4(16) . . . . ?
O6A S3A C8A S3 -55.3(12) . . . . ?
O6A S3A C2A S3 38.7(11) . . . . ?
O6A S3A C2A C8 -120.4(14) . . . . ?
C8A S3 O6 S3A -65.0(13) . . . . ?
C8A S3 C8 S3A 55.7(13) . . . . ?
C8A S3 C8 C2A -103.5(15) . . . . ?
C8A S3 C2 S3A 76(10) . . . . ?
C8A S3 S3A O6 104.3(15) . . . . ?
C8A S3 S3A C8 -119.5(13) . . . . ?
C8A S3 S3A C2 -10.7(17) . . . . ?
C8A S3 S3A O6A 116.1(16) . . . . ?
C8A S3 S3A C2A -107.6(12) . . . . ?
C8A S3 O6A S3A -61.6(14) . . . . ?
C8A S3 C2A C8 85.2(17) . . . . ?
C8A S3 C2A S3A 68.1(14) . . . . ?
C8A S3A O6A S3 65.7(16) . . . . ?
C8A S3A C2A S3 -69.3(14) . . . . ?
C8A S3A C2A C8 131.6(17) . . . . ?
C2A S3 O6 S3A 57.4(16) . . . . ?
C2A S3 C8 S3A 159.3(13) . . . . ?
C2A S3 C2 S3A -88.0(8) . . . . ?
C2A S3 S3A O6 -148.1(11) . . . . ?
C2A S3 S3A C8 -11.9(8) . . . . ?
C2A S3 S3A C2 96.9(10) . . . . ?
C2A S3 S3A O6A -136.3(13) . . . . ?
C2A S3 S3A C8A 107.6(12) . . . . ?
C2A S3 O6A S3A 75.4(15) . . . . ?
C2A S3 C8A S3A -83.8(10) . . . . ?
C2A C8 S3A S3 16.7(10) . . . . ?
C2A C8 S3A O6 77.7(18) . . . . ?
C2A C8 S3A C2 -56.1(13) . . . . ?
C2A C8 S3A O6A 72.2(15) . . . . ?
C2A C8 S3A C8A -57.2(19) . . . . ?
C2A S3A O6A S3 -34.8(9) . . . . ?
C2A S3A C8A S3 50.5(7) . . . . ?


_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.5454(8)
2 0.4546(8)

####################################################################### 
# 
# 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_sr22159_0ma
_database_code_depnum_ccdc_archive 'CCDC 2232429'
_audit_update_record             
;
2022-12-22 deposited with the CCDC.	2023-02-23 downloaded from the CCDC.
;
_audit_creation_date             2022-12-22
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
loop_
_audit_author_email
carsten.streb@uni-mainz.de
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         
'C16 H48 La O8 S8, 4(Br0.25), O32 V12, C8 H24 N4, 4(C2 H6 O S)'
_chemical_formula_sum            'C32 H96 Br La N4 O44 S12 V12'
_chemical_formula_weight         2455.94
_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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.3005 0.5294 '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      tetragonal
_space_group_IT_number           85
_space_group_name_H-M_alt        'P 4/n'
_space_group_name_Hall           '-P 4a'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y+1/2, z'
'-y+1/2, x, z'
'y, -x+1/2, z'
'-x, -y, -z'
'x-1/2, y-1/2, -z'
'y-1/2, -x, -z'
'-y, x-1/2, -z'

_cell_length_a                   19.7295(7)
_cell_length_b                   19.7295(7)
_cell_length_c                   10.9901(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4277.9(4)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9891
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      25.63
_cell_measurement_theta_min      2.36
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.577
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5890
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1691 before and 0.0786 after correction. The Ratio of minimum to maximum transmission is 0.7903. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.907
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             2456
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0767
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            33977
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.682
_diffrn_reflns_theta_min         3.459
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3862
_reflns_number_total             4057
_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       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_refine_diff_density_max         1.549
_refine_diff_density_min         -1.293
_refine_diff_density_rms         0.161
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         4057
_refine_ls_number_restraints     200
_refine_ls_R_factor_all          0.0488
_refine_ls_R_factor_gt           0.0467
_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)+(0.0929P)²+6.4376P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1329
_refine_ls_wR_factor_ref         0.1350
_refine_special_details          
;
 Refined as a 2-component twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.5974(17)
 0.4026(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid bond restraints
 S3, O1, S2, C2, C1, C5, H1A, H1B, H1C, H5A, H5B, H5C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
S3 \\sim O1 \\sim S2 \\sim C2 \\sim C1 \\sim C5 \\sim H1A \\sim H1B \\sim H1C
\\sim H5A \\sim H5B \\sim H5C: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(O1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(S3) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(S2) \\sim Ueq, Uanis(C2) \\sim
Ueq, Uanis(C1) \\sim Ueq, Uanis(C5) \\sim Ueq, : with sigma of 0.1 and sigma
for terminal atoms of 0.2
5. Others
 Fixed Sof: Br02(0.23875) S2(0.45) S3(0.55) C1(0.45) H1A(0.45) H1B(0.45)
 H1C(0.45) C5(0.55) H5A(0.55) H5B(0.55) H5C(0.55) Br1(0.01125)
6.a Secondary CH2 refined with riding coordinates:
 N00K(H00D,H00E), C00M(H00F,H00G), C00U(H00H,H00I)
6.b Idealised Me refined as rotating group:
 C00W(H00A,H00B,H00C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C),
 C2(H2A,H2B,H2C), C1(H1A,H1B,H1C), C5(H5A,H5B,H5C)
;
_atom_sites_solution_hydrogens   geom
_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
La01 La 0.2500 0.7500 1.0000 0.02142(18) Uani 1 4 d S T P . .
Br02 Br 0.2500 0.2500 0.55777(16) 0.0250(3) Uani 0.955 4 d S T P . .
V003 V 0.17014(5) 0.41781(5) 0.54372(9) 0.0181(2) Uani 1 1 d . . . . .
V004 V 0.07041(5) 0.31275(5) 0.52959(9) 0.0184(2) Uani 1 1 d . . . . .
V005 V 0.13609(5) 0.29501(5) 0.77941(9) 0.0181(2) Uani 1 1 d . . . . .
S007 S 0.17654(11) 0.59858(10) 0.85094(19) 0.0398(4) Uani 1 1 d . . . . .
O009 O 0.1208(2) 0.3615(2) 0.6552(3) 0.0202(8) Uani 1 1 d . . . . .
O00A O 0.2380(2) 0.4305(2) 0.4333(3) 0.0221(9) Uani 1 1 d . . . . .
O00B O 0.08406(19) 0.2441(2) 0.6533(3) 0.0193(8) Uani 1 1 d . . . . .
O00C O 0.1158(2) 0.3719(2) 0.4356(3) 0.0193(8) Uani 1 1 d . . . . .
O00E O 0.1369(3) 0.4909(2) 0.5611(4) 0.0269(10) Uani 1 1 d . . . . .
O00F O -0.0068(2) 0.3385(3) 0.5389(4) 0.0301(11) Uani 1 1 d . . . . .
O00I O 0.0792(2) 0.3128(2) 0.8782(4) 0.0268(10) Uani 1 1 d . . . . .
N00K N 0.1930(3) 0.3349(3) 0.2142(5) 0.0283(12) Uani 1 1 d . . . . .
H00D H 0.2156 0.3010 0.2531 0.034 Uiso 1 1 calc R . . . .
H00E H 0.1842 0.3678 0.2699 0.034 Uiso 1 1 calc R . . . .
C00M C 0.1366(3) 0.2378(3) 0.1182(5) 0.0248(13) Uani 1 1 d . . . . .
H00F H 0.0920 0.2203 0.0914 0.030 Uiso 1 1 calc R . . . .
H00G H 0.1673 0.2386 0.0470 0.030 Uiso 1 1 calc R . . . .
O00Q O 0.2189(3) 0.6310(3) 0.9473(5) 0.0429(13) Uani 1 1 d . . . . .
C00U C 0.1287(3) 0.3083(3) 0.1687(6) 0.0269(14) Uani 1 1 d . . . . .
H00H H 0.1111 0.3386 0.1042 0.032 Uiso 1 1 calc R . . . .
H00I H 0.0951 0.3075 0.2358 0.032 Uiso 1 1 calc R . . . .
C00W C 0.2303(7) 0.5941(6) 0.7222(8) 0.068(4) Uani 1 1 d . . . . .
H00A H 0.2380 0.6399 0.6903 0.102 Uiso 1 1 calc GR . . . .
H00B H 0.2089 0.5662 0.6593 0.102 Uiso 1 1 calc GR . . . .
H00C H 0.2737 0.5739 0.7456 0.102 Uiso 1 1 calc GR . . . .
O4 O 0.1634(2) 0.2079(2) 0.8300(4) 0.0215(9) Uani 1 1 d . . . . .
S1 S 0.20613(13) 0.61441(11) 1.2204(2) 0.0477(5) Uani 1 1 d . . . . .
O2 O 0.2438(3) 0.6791(3) 1.1920(4) 0.0400(12) Uani 1 1 d . . . . .
C3 C 0.2666(6) 0.5467(5) 1.2045(11) 0.061(3) Uani 1 1 d . . . . .
H3A H 0.2736 0.5369 1.1179 0.092 Uiso 1 1 calc GR . . . .
H3B H 0.2494 0.5060 1.2454 0.092 Uiso 1 1 calc GR . . . .
H3C H 0.3098 0.5602 1.2414 0.092 Uiso 1 1 calc GR . . . .
C4 C 0.1729(4) 0.5117(4) 0.8906(7) 0.0390(17) Uani 1 1 d . . . . .
H4A H 0.2191 0.4935 0.8961 0.059 Uiso 1 1 calc GR . . . .
H4B H 0.1476 0.4868 0.8283 0.059 Uiso 1 1 calc GR . . . .
H4C H 0.1502 0.5067 0.9694 0.059 Uiso 1 1 calc GR . . . .
C6 C 0.2055(8) 0.6128(6) 1.3837(10) 0.086(4) Uani 1 1 d . . . . .
H6A H 0.2470 0.6339 1.4146 0.129 Uiso 1 1 calc GR . . . .
H6B H 0.2031 0.5657 1.4118 0.129 Uiso 1 1 calc GR . . . .
H6C H 0.1660 0.6378 1.4137 0.129 Uiso 1 1 calc GR . . . .
O1 O 0.1163(4) 0.4771(4) 0.1778(8) 0.071(2) Uani 1 1 d . U . . .
S2 S 0.0408(3) 0.4823(2) 0.1890(5) 0.0451(11) Uani 0.45 1 d . U . A 1
S3 S 0.0708(2) 0.5125(2) 0.2533(4) 0.0529(10) Uani 0.55 1 d . U . A -1
C2 C 0.0217(7) 0.5690(7) 0.1512(14) 0.090(4) Uani 1 1 d . U . A 1
H2A H 0.0072 0.5932 0.2247 0.135 Uiso 1 1 calc GR . . A 1
H2B H -0.0148 0.5702 0.0908 0.135 Uiso 1 1 calc GR . . A 1
H2C H 0.0622 0.5908 0.1177 0.135 Uiso 1 1 calc GR . . A 1
C1 C 0.0207(13) 0.4972(13) 0.349(2) 0.061(4) Uani 0.45 1 d . U . A 1
H1A H 0.0232 0.4543 0.3938 0.091 Uiso 0.45 1 calc GR U . A 1
H1B H -0.0252 0.5159 0.3558 0.091 Uiso 0.45 1 calc GR U . A 1
H1C H 0.0533 0.5294 0.3834 0.091 Uiso 0.45 1 calc GR U . A 1
C5 C 0.0058(11) 0.4615(14) 0.295(2) 0.083(5) Uani 0.55 1 d . U . A -1
H5A H -0.0123 0.4384 0.2231 0.124 Uiso 0.55 1 calc GR U . A -1
H5B H -0.0300 0.4888 0.3328 0.124 Uiso 0.55 1 calc GR U . A -1
H5C H 0.0221 0.4277 0.3535 0.124 Uiso 0.55 1 calc GR U . A -1
Br1 Br 0.2500 0.2500 0.503(3) 0.011(5) Uiso 0.045 4 d S T P . .


_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
La01 O00Q 2.494(6) 2_565 ?
La01 O00Q 2.494(6) 8_667 ?
La01 O00Q 2.494(6) 7_567 ?
La01 O00Q 2.494(6) . ?
La01 O2 2.534(5) 2_565 ?
La01 O2 2.534(5) . ?
La01 O2 2.534(5) 8_667 ?
La01 O2 2.534(5) 7_567 ?
Br02 Br1 0.60(3) . ?
V003 V004 2.8274(15) 4 ?
V003 V004 2.8623(15) . ?
V003 O009 1.919(4) . ?
V003 O00A 1.825(4) . ?
V003 O00B 1.892(4) 4 ?
V003 O00C 1.839(4) . ?
V003 O00E 1.596(5) . ?
V004 V003 2.8273(15) 3 ?
V004 V005 3.0561(15) . ?
V004 O009 1.954(4) . ?
V004 O00A 1.815(4) 3 ?
V004 O00B 1.938(4) . ?
V004 O00C 1.798(4) . ?
V004 O00F 1.609(5) . ?
V005 O009 1.917(4) . ?
V005 O00B 1.996(4) . ?
V005 O00I 1.601(4) . ?
V005 O4 1.885(4) . ?
V005 O4 1.729(4) 4 ?
S007 O00Q 1.493(6) . ?
S007 C00W 1.771(10) . ?
S007 C4 1.770(8) . ?
O00A V004 1.815(4) 4 ?
O00B V003 1.892(4) 3 ?
N00K H00D 0.9100 . ?
N00K H00E 0.9100 . ?
N00K C00M 1.486(8) 4 ?
N00K C00U 1.463(8) . ?
C00M N00K 1.486(8) 3 ?
C00M H00F 0.9900 . ?
C00M H00G 0.9900 . ?
C00M C00U 1.505(9) . ?
C00U H00H 0.9900 . ?
C00U H00I 0.9900 . ?
C00W H00A 0.9800 . ?
C00W H00B 0.9800 . ?
C00W H00C 0.9800 . ?
O4 V005 1.729(4) 3 ?
S1 O2 1.510(6) . ?
S1 C3 1.801(10) . ?
S1 C6 1.794(11) . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 H4A 0.9800 . ?
C4 H4B 0.9800 . ?
C4 H4C 0.9800 . ?
C6 H6A 0.9800 . ?
C6 H6B 0.9800 . ?
C6 H6C 0.9800 . ?
O1 S2 1.500(9) . ?
O1 S3 1.409(8) . ?
S2 S3 1.097(7) . ?
S2 C2 1.801(12) . ?
S2 C1 1.83(2) . ?
S2 C5 1.41(2) . ?
S3 C2 1.855(12) . ?
S3 C1 1.47(2) . ?
S3 C5 1.69(2) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1C 0.9800 . ?
C1 C5 0.97(3) . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 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
O00Q La01 O00Q 93.09(6) 2_565 8_667 ?
O00Q La01 O00Q 153.2(3) 8_667 7_567 ?
O00Q La01 O00Q 93.09(6) 2_565 7_567 ?
O00Q La01 O00Q 93.09(6) 8_667 . ?
O00Q La01 O00Q 153.2(3) 2_565 . ?
O00Q La01 O00Q 93.09(6) 7_567 . ?
O00Q La01 O2 84.1(2) 2_565 7_567 ?
O00Q La01 O2 136.43(17) 7_567 8_667 ?
O00Q La01 O2 73.5(2) . 7_567 ?
O00Q La01 O2 70.24(17) 7_567 7_567 ?
O00Q La01 O2 70.24(17) 8_667 8_667 ?
O00Q La01 O2 84.1(2) 8_667 2_565 ?
O00Q La01 O2 136.43(17) 8_667 7_567 ?
O00Q La01 O2 84.1(2) 7_567 . ?
O00Q La01 O2 84.1(2) . 8_667 ?
O00Q La01 O2 73.5(2) 2_565 8_667 ?
O00Q La01 O2 73.5(2) 7_567 2_565 ?
O00Q La01 O2 70.24(17) . . ?
O00Q La01 O2 73.5(2) 8_667 . ?
O00Q La01 O2 70.24(17) 2_565 2_565 ?
O00Q La01 O2 136.43(17) . 2_565 ?
O00Q La01 O2 136.43(17) 2_565 . ?
O2 La01 O2 133.87(15) 2_565 8_667 ?
O2 La01 O2 133.87(15) 2_565 7_567 ?
O2 La01 O2 133.87(15) 7_567 . ?
O2 La01 O2 133.87(15) 8_667 . ?
O2 La01 O2 67.3(2) 2_565 . ?
O2 La01 O2 67.3(2) 7_567 8_667 ?
V004 V003 V004 137.79(6) 4 . ?
O009 V003 V004 125.98(13) . 4 ?
O009 V003 V004 42.82(13) . . ?
O00A V003 V004 38.91(13) . 4 ?
O00A V003 V004 124.60(14) . . ?
O00A V003 O009 151.20(18) . . ?
O00A V003 O00B 81.97(18) . 4 ?
O00A V003 O00C 93.76(19) . . ?
O00B V003 V004 123.40(13) 4 . ?
O00B V003 V004 43.06(12) 4 4 ?
O00B V003 O009 88.49(18) 4 . ?
O00C V003 V004 37.59(13) . . ?
O00C V003 V004 125.83(14) . 4 ?
O00C V003 O009 80.31(18) . . ?
O00C V003 O00B 148.37(18) . 4 ?
O00E V003 V004 109.98(19) . 4 ?
O00E V003 V004 112.21(19) . . ?
O00E V003 O009 103.8(2) . . ?
O00E V003 O00A 104.9(2) . . ?
O00E V003 O00B 105.0(2) . 4 ?
O00E V003 O00C 106.4(2) . . ?
V003 V004 V003 131.38(6) 3 . ?
V003 V004 V005 75.09(4) . . ?
V003 V004 V005 78.57(4) 3 . ?
O009 V004 V003 41.89(12) . . ?
O009 V004 V003 114.14(12) . 3 ?
O009 V004 V005 37.43(12) . . ?
O00A V004 V003 128.80(15) 3 . ?
O00A V004 V003 39.15(13) 3 3 ?
O00A V004 V005 115.79(13) 3 . ?
O00A V004 O009 144.75(18) 3 . ?
O00A V004 O00B 80.94(18) 3 . ?
O00B V004 V003 111.88(12) . . ?
O00B V004 V003 41.79(12) . 3 ?
O00B V004 V005 39.72(12) . . ?
O00B V004 O009 77.15(17) . . ?
O00C V004 V003 38.59(13) . . ?
O00C V004 V003 129.56(14) . 3 ?
O00C V004 V005 112.29(13) . . ?
O00C V004 O009 80.38(17) . . ?
O00C V004 O00A 101.39(19) . 3 ?
O00C V004 O00B 141.98(18) . . ?
O00F V004 V003 112.9(2) . 3 ?
O00F V004 V003 114.7(2) . . ?
O00F V004 V005 112.38(18) . . ?
O00F V004 O009 106.3(2) . . ?
O00F V004 O00A 106.5(2) . 3 ?
O00F V004 O00B 108.0(2) . . ?
O00F V004 O00C 107.6(2) . . ?
O009 V005 V004 38.28(13) . . ?
O009 V005 O00B 76.63(17) . . ?
O00B V005 V004 38.35(12) . . ?
O00I V005 V004 106.66(17) . . ?
O00I V005 O009 102.9(2) . . ?
O00I V005 O00B 102.8(2) . . ?
O00I V005 O4 101.6(2) . . ?
O00I V005 O4 104.6(2) . 4 ?
O4 V005 V004 125.58(15) 4 . ?
O4 V005 V004 119.37(14) . . ?
O4 V005 O009 151.49(18) . . ?
O4 V005 O009 91.91(19) 4 . ?
O4 V005 O00B 83.83(18) . . ?
O4 V005 O00B 152.08(18) 4 . ?
O4 V005 O4 96.0(3) 4 . ?
O00Q S007 C00W 104.7(4) . . ?
O00Q S007 C4 105.2(4) . . ?
C00W S007 C4 100.0(5) . . ?
V003 O009 V004 95.29(17) . . ?
V005 O009 V003 140.4(2) . . ?
V005 O009 V004 104.3(2) . . ?
V004 O00A V003 101.94(19) 4 . ?
V003 O00B V004 95.15(16) 3 . ?
V003 O00B V005 147.2(2) 3 . ?
V004 O00B V005 101.9(2) . . ?
V004 O00C V003 103.81(19) . . ?
H00D N00K H00E 107.6 . . ?
C00M N00K H00D 108.7 4 . ?
C00M N00K H00E 108.7 4 . ?
C00U N00K H00D 108.7 . . ?
C00U N00K H00E 108.7 . . ?
C00U N00K C00M 114.2(5) . 4 ?
N00K C00M H00F 109.9 3 . ?
N00K C00M H00G 109.9 3 . ?
N00K C00M C00U 109.1(5) 3 . ?
H00F C00M H00G 108.3 . . ?
C00U C00M H00F 109.9 . . ?
C00U C00M H00G 109.9 . . ?
S007 O00Q La01 134.9(3) . . ?
N00K C00U C00M 111.6(5) . . ?
N00K C00U H00H 109.3 . . ?
N00K C00U H00I 109.3 . . ?
C00M C00U H00H 109.3 . . ?
C00M C00U H00I 109.3 . . ?
H00H C00U H00I 108.0 . . ?
S007 C00W H00A 109.5 . . ?
S007 C00W H00B 109.5 . . ?
S007 C00W H00C 109.5 . . ?
H00A C00W H00B 109.5 . . ?
H00A C00W H00C 109.5 . . ?
H00B C00W H00C 109.5 . . ?
V005 O4 V005 142.0(3) 3 . ?
O2 S1 C3 106.3(4) . . ?
O2 S1 C6 103.1(5) . . ?
C6 S1 C3 95.1(6) . . ?
S1 O2 La01 131.5(3) . . ?
S1 C3 H3A 109.5 . . ?
S1 C3 H3B 109.5 . . ?
S1 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
S007 C4 H4A 109.5 . . ?
S007 C4 H4B 109.5 . . ?
S007 C4 H4C 109.5 . . ?
H4A C4 H4B 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
S1 C6 H6A 109.5 . . ?
S1 C6 H6B 109.5 . . ?
S1 C6 H6C 109.5 . . ?
H6A C6 H6B 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
S3 O1 S2 44.2(3) . . ?
O1 S2 C2 104.7(6) . . ?
O1 S2 C1 107.8(10) . . ?
S3 S2 O1 63.5(5) . . ?
S3 S2 C2 75.2(6) . . ?
S3 S2 C1 53.8(10) . . ?
S3 S2 C5 83.7(13) . . ?
C2 S2 C1 91.4(9) . . ?
C5 S2 O1 122.2(10) . . ?
C5 S2 C2 111.3(12) . . ?
C5 S2 C1 31.6(14) . . ?
O1 S3 C2 105.9(7) . . ?
O1 S3 C1 138.3(10) . . ?
O1 S3 C5 110.4(11) . . ?
S2 S3 O1 72.3(5) . . ?
S2 S3 C2 69.9(6) . . ?
S2 S3 C1 89.3(12) . . ?
S2 S3 C5 56.2(11) . . ?
C1 S3 C2 101.8(10) . . ?
C1 S3 C5 34.7(12) . . ?
C5 S3 C2 97.3(9) . . ?
S2 C2 S3 34.9(3) . . ?
S2 C2 H2A 109.5 . . ?
S2 C2 H2B 109.5 . . ?
S2 C2 H2C 109.5 . . ?
S3 C2 H2A 86.9 . . ?
S3 C2 H2B 143.9 . . ?
S3 C2 H2C 93.8 . . ?
H2A C2 H2B 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
S2 C1 H1A 109.5 . . ?
S2 C1 H1B 109.5 . . ?
S2 C1 H1C 109.5 . . ?
S3 C1 S2 36.9(6) . . ?
S3 C1 H1A 120.1 . . ?
S3 C1 H1B 126.5 . . ?
S3 C1 H1C 72.7 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
C5 C1 S2 50.0(15) . . ?
C5 C1 S3 85.1(19) . . ?
C5 C1 H1A 72.2 . . ?
C5 C1 H1B 92.3 . . ?
C5 C1 H1C 155.3 . . ?
S2 C5 S3 40.1(6) . . ?
S2 C5 H5A 69.4 . . ?
S2 C5 H5B 122.7 . . ?
S2 C5 H5C 125.2 . . ?
S3 C5 H5A 109.5 . . ?
S3 C5 H5B 109.5 . . ?
S3 C5 H5C 109.5 . . ?
C1 C5 S2 98(2) . . ?
C1 C5 S3 60(2) . . ?
C1 C5 H5A 160.8 . . ?
C1 C5 H5B 63.8 . . ?
C1 C5 H5C 89.6 . . ?
H5A C5 H5B 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 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
V003 V004 O00C V003 -109.85(17) 3 . . . ?
V004 V003 O00A V004 -125.31(15) . . . 4 ?
V004 V003 O00C V004 124.04(15) 4 . . . ?
V004 V005 O4 V005 44.9(5) . . . 3 ?
V005 V004 O00C V003 -16.4(2) . . . . ?
O009 V003 O00A V004 -71.8(4) . . . 4 ?
O009 V003 O00C V004 -3.67(19) . . . . ?
O009 V004 O00C V003 3.61(19) . . . . ?
O009 V005 O4 V005 13.2(7) . . . 3 ?
O00A V003 O00C V004 147.9(2) . . . . ?
O00A V004 O00C V003 -140.6(2) 3 . . . ?
O00B V003 O00A V004 0.00(19) 4 . . 4 ?
O00B V003 O00C V004 67.2(4) 4 . . . ?
O00B V004 O00C V003 -50.7(4) . . . . ?
O00B V005 O4 V005 59.9(4) . . . 3 ?
O00C V003 O00A V004 -148.5(2) . . . 4 ?
O00E V003 O00A V004 103.5(2) . . . 4 ?
O00E V003 O00C V004 -105.3(2) . . . . ?
O00F V004 O00C V003 107.8(2) . . . . ?
O00I V005 O4 V005 161.7(4) . . . 3 ?
N00K C00M C00U N00K 57.1(7) 3 . . . ?
C00M N00K C00U C00M 81.6(8) 4 . . . ?
C00W S007 O00Q La01 82.1(7) . . . . ?
O4 V005 O4 V005 -92.0(4) 4 . . 3 ?
C3 S1 O2 La01 98.8(6) . . . . ?
C4 S007 O00Q La01 -173.0(5) . . . . ?
C6 S1 O2 La01 -161.8(6) . . . . ?
O1 S2 S3 C2 115.1(6) . . . . ?
O1 S2 S3 C1 -142.0(10) . . . . ?
O1 S2 S3 C5 -130.9(10) . . . . ?
O1 S2 C2 S3 -56.9(6) . . . . ?
O1 S2 C1 S3 35.4(8) . . . . ?
O1 S2 C1 C5 -123(2) . . . . ?
O1 S2 C5 S3 53.1(10) . . . . ?
O1 S2 C5 C1 70(2) . . . . ?
O1 S3 C2 S2 63.8(6) . . . . ?
O1 S3 C1 S2 -61.9(15) . . . . ?
O1 S3 C1 C5 -45(3) . . . . ?
O1 S3 C5 S2 -50.2(8) . . . . ?
O1 S3 C5 C1 150(2) . . . . ?
S2 O1 S3 C2 -62.2(6) . . . . ?
S2 O1 S3 C1 67.7(18) . . . . ?
S2 O1 S3 C5 42.1(9) . . . . ?
S2 S3 C1 C5 16.4(19) . . . . ?
S2 S3 C5 C1 -160(2) . . . . ?
S2 C1 C5 S3 12.8(15) . . . . ?
S3 O1 S2 C2 64.9(7) . . . . ?
S3 O1 S2 C1 -31.5(9) . . . . ?
S3 O1 S2 C5 -62.7(16) . . . . ?
S3 S2 C1 C5 -158(3) . . . . ?
S3 S2 C5 C1 17(2) . . . . ?
S3 C1 C5 S2 -12.8(15) . . . . ?
C2 S2 S3 O1 -115.1(6) . . . . ?
C2 S2 S3 C1 102.9(10) . . . . ?
C2 S2 S3 C5 114.0(10) . . . . ?
C2 S2 C1 S3 -70.5(8) . . . . ?
C2 S2 C1 C5 131(2) . . . . ?
C2 S2 C5 S3 -71.4(8) . . . . ?
C2 S2 C5 C1 -54(2) . . . . ?
C2 S3 C1 S2 69.2(7) . . . . ?
C2 S3 C1 C5 86(2) . . . . ?
C2 S3 C5 S2 59.8(9) . . . . ?
C2 S3 C5 C1 -100(2) . . . . ?
C1 S2 S3 O1 142.0(10) . . . . ?
C1 S2 S3 C2 -102.9(10) . . . . ?
C1 S2 S3 C5 11.1(13) . . . . ?
C1 S2 C2 S3 51.9(9) . . . . ?
C1 S2 C5 S3 -17(2) . . . . ?
C1 S3 C2 S2 -84.8(12) . . . . ?
C1 S3 C5 S2 160(2) . . . . ?
C5 S2 S3 O1 130.9(10) . . . . ?
C5 S2 S3 C2 -114.0(10) . . . . ?
C5 S2 S3 C1 -11.1(13) . . . . ?
C5 S2 C2 S3 77.0(13) . . . . ?
C5 S2 C1 S3 158(3) . . . . ?
C5 S3 C2 S2 -49.9(11) . . . . ?
C5 S3 C1 S2 -16.4(19) . . . . ?


_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.5974(17)
2 0.4026(17)

####################################################################### 
# 
# 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_sr21055_0ma_c
_database_code_depnum_ccdc_archive 'CCDC 2235427'
_audit_update_record             
;
2023-01-10 deposited with the CCDC.	2023-02-23 downloaded from the CCDC.
;
_audit_creation_date             2023-01-10
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
loop_
_audit_author_email
carsten.streb@uni-mainz.de
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         
'C16 H48 Ba O8 S8, 2(Br0.5), O32 V12, 2(C2 H6 O S), C8 H16 N4, 2(C1.5 H4.5 O0.75 S0.65), 0.7(S1)'
_chemical_formula_sum            'C31 H85 Ba Br N4 O43.50 S12 V12'
_chemical_formula_weight         2423.27
_chemical_absolute_configuration unk
_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'
Ba Ba -0.3244 2.2819 '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'
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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.3005 0.5294 '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      tetragonal
_space_group_IT_number           81
_space_group_name_H-M_alt        'P -4'
_space_group_name_Hall           'P -4'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'y, -x, -z'
'-y, x, -z'

_cell_length_a                   19.6360(13)
_cell_length_b                   19.6360(13)
_cell_length_c                   10.9821(11)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4234.4(7)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9770
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.40
_cell_measurement_theta_min      2.36
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.566
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6749
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1475 before and 0.0677 after correction. The Ratio of minimum to maximum transmission is 0.9052. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.901
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2412
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0665
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            205894
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.583
_diffrn_reflns_theta_min         1.854
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                8149
_reflns_number_total             9764
_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       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         0.947
_refine_diff_density_min         -0.703
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details 
;
 Flack x determined using 3701 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.494(17)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     504
_refine_ls_number_reflns         9764
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0279
_refine_ls_restrained_S_all      1.107
_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)+(0.0308P)²+7.7668P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0701
_refine_ls_wR_factor_ref         0.0797
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C30) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O17) \\sim Ueq, Uanis(O17) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
3. Others
 Fixed Sof: Br1(0.45) Br2(0.05) S5(0.65) O20(0.75) C10(0.75) H10A(0.75)
 H10B(0.75) H10C(0.75) C14(0.75) H14A(0.75) H14B(0.75) H14C(0.75) S7(0.35)
4.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C33(H33A,H33B), C34(H34A,H34B)
4.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C15(H15A,
 H15B,H15C), C18(H18A,H18B,H18C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C10(H10A,H10B,H10C), C14(H14A,H14B,
 H14C)
;
_atom_sites_solution_hydrogens   geom
_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
Ba1 Ba 0.5000 0.5000 0.0000 0.0167(3) Uani 1 4 d S T P . .
S1 S 0.47291(16) 0.68450(16) -0.0949(4) 0.0286(8) Uani 1 1 d . . . . .
S3 S 0.47709(15) 0.39499(15) 0.2918(4) 0.0287(8) Uani 1 1 d . . . . .
O16 O 0.4354(4) 0.6184(4) -0.0652(11) 0.034(2) Uani 1 1 d . . . . .
O21 O 0.5288(4) 0.4223(4) 0.2039(11) 0.039(3) Uani 1 1 d . . . . .
C6 C 0.5203(6) 0.3695(6) 0.4228(14) 0.042(3) Uani 1 1 d . . . . .
H6A H 0.5348 0.4098 0.4687 0.062 Uiso 1 1 calc GR . . . .
H6B H 0.5603 0.3426 0.3999 0.062 Uiso 1 1 calc GR . . . .
H6C H 0.4900 0.3417 0.4735 0.062 Uiso 1 1 calc GR . . . .
C7 C 0.4550(6) 0.3129(6) 0.2412(17) 0.045(4) Uani 1 1 d . . . . .
H7A H 0.4950 0.2831 0.2458 0.068 Uiso 1 1 calc GR . . . .
H7B H 0.4391 0.3153 0.1568 0.068 Uiso 1 1 calc GR . . . .
H7C H 0.4187 0.2945 0.2929 0.068 Uiso 1 1 calc GR . . . .
C8 C 0.4103(7) 0.7469(6) -0.1160(15) 0.035(4) Uani 1 1 d . . . . .
H8A H 0.3829 0.7511 -0.0417 0.053 Uiso 1 1 calc GR . . . .
H8B H 0.3807 0.7338 -0.1841 0.053 Uiso 1 1 calc GR . . . .
H8C H 0.4320 0.7906 -0.1341 0.053 Uiso 1 1 calc GR . . . .
C9 C 0.5003(6) 0.6780(6) -0.2491(14) 0.034(3) Uani 1 1 d . . . . .
H9A H 0.4605 0.6736 -0.3024 0.052 Uiso 1 1 calc GR . . . .
H9B H 0.5296 0.6380 -0.2584 0.052 Uiso 1 1 calc GR . . . .
H9C H 0.5258 0.7191 -0.2713 0.052 Uiso 1 1 calc GR . . . .
Ba2 Ba 0.0000 1.0000 0.0000 0.0168(3) Uani 1 4 d S T P . .
S2 S 0.02746(16) 0.81555(16) 0.0949(4) 0.0281(8) Uani 1 1 d . . . . .
S4 S 0.10504(15) 0.97750(15) 0.2926(4) 0.0306(9) Uani 1 1 d . . . . .
O15 O 0.0785(4) 1.0297(4) 0.2049(12) 0.038(3) Uani 1 1 d . . . . .
O19 O 0.0639(4) 0.8817(4) 0.0698(10) 0.032(2) Uani 1 1 d . . . . .
C15 C 0.1872(5) 0.9538(6) 0.2325(18) 0.043(4) Uani 1 1 d . . . . .
H15A H 0.2120 0.9949 0.2078 0.064 Uiso 1 1 calc GR . . . .
H15B H 0.1811 0.9240 0.1618 0.064 Uiso 1 1 calc GR . . . .
H15C H 0.2133 0.9298 0.2954 0.064 Uiso 1 1 calc GR . . . .
C18 C 0.1336(6) 1.0247(7) 0.4232(12) 0.048(4) Uani 1 1 d . . . . .
H18A H 0.0948 1.0483 0.4604 0.072 Uiso 1 1 calc GR . . . .
H18B H 0.1677 1.0583 0.3980 0.072 Uiso 1 1 calc GR . . . .
H18C H 0.1537 0.9934 0.4826 0.072 Uiso 1 1 calc GR . . . .
C23 C 0.0014(6) 0.8226(6) 0.2475(16) 0.038(4) Uani 1 1 d . . . . .
H23A H -0.0306 0.8606 0.2556 0.056 Uiso 1 1 calc GR . . . .
H23B H 0.0412 0.8309 0.2992 0.056 Uiso 1 1 calc GR . . . .
H23C H -0.0209 0.7802 0.2728 0.056 Uiso 1 1 calc GR . . . .
C24 C 0.0935(6) 0.7530(6) 0.1152(15) 0.032(4) Uani 1 1 d . . . . .
H24A H 0.1305 0.7727 0.1638 0.048 Uiso 1 1 calc GR . . . .
H24B H 0.1112 0.7392 0.0355 0.048 Uiso 1 1 calc GR . . . .
H24C H 0.0748 0.7132 0.1574 0.048 Uiso 1 1 calc GR . . . .
Br1 Br 0.0000 0.5000 0.50850(10) 0.03528(18) Uani 0.9 2 d S T P . .
Br2 Br 0.0000 0.5000 0.4404(6) 0.0179(12) Uani 0.1 2 d S T P . .
V1 V -0.11371(9) 0.45141(9) 0.2290(2) 0.0147(5) Uani 1 1 d . . . . .
V2 V 0.17810(10) 0.56876(11) 0.4796(2) 0.0162(5) Uani 1 1 d . . . . .
V3 V -0.06872(11) 0.67802(9) 0.4797(2) 0.0162(5) Uani 1 1 d . . . . .
V4 V 0.04859(9) 0.38615(9) 0.2290(2) 0.0143(5) Uani 1 1 d . . . . .
V5 V 0.17167(8) 0.42480(9) 0.4653(2) 0.0158(5) Uani 1 1 d . . . . .
V6 V 0.07548(9) 0.67150(8) 0.4653(2) 0.0160(5) Uani 1 1 d . . . . .
O1 O -0.1255(4) 0.3848(4) 0.3541(9) 0.0171(18) Uani 1 1 d . . . . .
O2 O -0.0978(3) 0.7536(3) 0.4668(9) 0.024(2) Uani 1 1 d . . . . .
O3 O 0.0008(4) 0.6658(3) 0.3562(8) 0.0164(19) Uani 1 1 d . . . . .
O4 O 0.0682(4) 0.3300(4) 0.1284(9) 0.021(2) Uani 1 1 d . . . . .
O5 O -0.1273(4) 0.6314(4) 0.5744(9) 0.0194(19) Uani 1 1 d . . . . .
O6 O 0.1655(4) 0.4990(4) 0.3545(9) 0.0174(19) Uani 1 1 d . . . . .
O7 O 0.0868(4) 0.4609(4) 0.1794(9) 0.0181(19) Uani 1 1 d . . . . .
O8 O 0.1839(4) 0.4940(4) 0.5742(9) 0.022(2) Uani 1 1 d . . . . .
O9 O -0.0397(4) 0.4128(4) 0.1809(9) 0.0180(18) Uani 1 1 d . . . . .
O10 O 0.2454(4) 0.3926(4) 0.4450(10) 0.022(2) Uani 1 1 d . . . . .
O11 O 0.1151(4) 0.3749(4) 0.3542(9) 0.0167(18) Uani 1 1 d . . . . .
O12 O 0.0060(4) 0.6831(4) 0.5759(9) 0.0188(18) Uani 1 1 d . . . . .
O13 O 0.1314(4) 0.6269(4) 0.5734(9) 0.0196(19) Uani 1 1 d . . . . .
O17 O 0.2541(3) 0.5978(3) 0.4664(10) 0.024(2) Uani 1 1 d . U . . .
O18 O -0.1700(4) 0.4328(4) 0.1306(9) 0.0198(19) Uani 1 1 d . . . . .
S6 S 0.33848(18) 0.7247(2) 0.2510(5) 0.0526(10) Uani 1 1 d . . . . .
O22 O 0.3785(5) 0.7772(5) 0.1878(12) 0.050(3) Uani 1 1 d . . . . .
C25 C 0.3027(7) 0.6708(6) 0.1444(18) 0.057(5) Uani 1 1 d . . . . .
H25A H 0.3378 0.6403 0.1122 0.086 Uiso 1 1 calc GR . . . .
H25B H 0.2834 0.6978 0.0777 0.086 Uiso 1 1 calc GR . . . .
H25C H 0.2666 0.6439 0.1828 0.086 Uiso 1 1 calc GR . . . .
C26 C 0.2663(6) 0.7588(6) 0.3125(19) 0.051(5) Uani 1 1 d . . . . .
H26A H 0.2483 0.7938 0.2578 0.077 Uiso 1 1 calc GR . . . .
H26B H 0.2770 0.7792 0.3916 0.077 Uiso 1 1 calc GR . . . .
H26C H 0.2322 0.7228 0.3233 0.077 Uiso 1 1 calc GR . . . .
N1 N -0.0575(6) 0.4080(6) 0.7878(14) 0.043(3) Uani 1 1 d . . . . .
N2 N 0.0929(6) 0.4418(6) 0.7909(12) 0.037(3) Uani 1 1 d . . . . .
C29 C 0.1233(4) 0.5603(5) 0.8349(10) 0.025(3) Uani 1 1 d . . . . .
H29A H 0.1427 0.5900 0.8991 0.030 Uiso 1 1 calc R . . . .
H29B H 0.1567 0.5580 0.7674 0.030 Uiso 1 1 calc R . . . .
C30 C 0.1129(5) 0.4888(4) 0.8868(9) 0.028(3) Uani 1 1 d . U . . .
H30A H 0.1557 0.4728 0.9250 0.033 Uiso 1 1 calc R . . . .
H30B H 0.0772 0.4900 0.9504 0.033 Uiso 1 1 calc R . . . .
C33 C 0.0602(7) 0.3790(7) 0.8397(13) 0.052(4) Uani 1 1 d . . . . .
H33A H 0.0611 0.3439 0.7750 0.063 Uiso 1 1 calc R . . . .
H33B H 0.0885 0.3619 0.9078 0.063 Uiso 1 1 calc R . . . .
C34 C -0.0078(6) 0.3851(6) 0.8819(11) 0.058(5) Uani 1 1 d . . . . .
H34A H -0.0087 0.4179 0.9504 0.070 Uiso 1 1 calc R . . . .
H34B H -0.0227 0.3404 0.9139 0.070 Uiso 1 1 calc R . . . .
S5 S 0.15998(17) 0.77738(18) 0.7478(5) 0.0220(9) Uani 0.65 1 d . . . A 1
O20 O 0.1219(5) 0.7225(5) 0.8119(14) 0.034(3) Uani 0.75 1 d . . . A 1
C10 C 0.1970(8) 0.8270(7) 0.8660(19) 0.042(4) Uani 0.75 1 d . . . A 1
H10A H 0.1610 0.8458 0.9177 0.064 Uiso 0.75 1 calc GR . . A 1
H10B H 0.2235 0.8644 0.8302 0.064 Uiso 0.75 1 calc GR . . A 1
H10C H 0.2271 0.7983 0.9152 0.064 Uiso 0.75 1 calc GR . . A 1
C14 C 0.2370(5) 0.7413(6) 0.683(2) 0.032(4) Uani 0.75 1 d . . . A 1
H14A H 0.2679 0.7278 0.7490 0.048 Uiso 0.75 1 calc GR . . A 1
H14B H 0.2593 0.7753 0.6316 0.048 Uiso 0.75 1 calc GR . . A 1
H14C H 0.2253 0.7013 0.6342 0.048 Uiso 0.75 1 calc GR . . A 1
S7 S 0.1923(4) 0.7423(3) 0.8062(6) 0.0521(16) Uani 0.35 1 d . . . A -1
O0AA O 0.1084(4) 0.7448(4) 0.4460(10) 0.021(2) 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
Ba1 O16 2.744(7) . ?
Ba1 O16 2.744(7) 3_565 ?
Ba1 O16 2.744(7) 4_655 ?
Ba1 O16 2.744(7) 2_665 ?
Ba1 O21 2.769(10) 3_565 ?
Ba1 O21 2.769(10) . ?
Ba1 O21 2.769(10) 2_665 ?
Ba1 O21 2.769(10) 4_655 ?
S1 O16 1.527(8) . ?
S1 C8 1.752(13) . ?
S1 C9 1.781(15) . ?
S3 O21 1.501(10) . ?
S3 C6 1.744(15) . ?
S3 C7 1.760(14) . ?
Ba2 O15 2.789(11) . ?
Ba2 O15 2.789(11) 3_465 ?
Ba2 O15 2.789(11) 4_665 ?
Ba2 O15 2.789(11) 2_575 ?
Ba2 O19 2.749(8) . ?
Ba2 O19 2.749(8) 2_575 ?
Ba2 O19 2.749(8) 3_465 ?
Ba2 O19 2.749(8) 4_665 ?
S2 O19 1.507(8) . ?
S2 C23 1.758(18) . ?
S2 C24 1.800(12) . ?
S4 O15 1.500(10) . ?
S4 C15 1.804(13) . ?
S4 C18 1.798(12) . ?
Br1 Br2 0.748(6) . ?
V1 V2 3.054(3) 2_565 ?
V1 O1 1.911(9) . ?
V1 O6 1.970(9) 2_565 ?
V1 O7 1.881(8) 2_565 ?
V1 O9 1.721(8) . ?
V1 O18 1.590(8) . ?
V2 V1 3.054(3) 2_565 ?
V2 V5 2.834(3) . ?
V2 V6 2.856(3) . ?
V2 O1 1.949(9) 2_565 ?
V2 O6 1.957(8) . ?
V2 O8 1.802(9) . ?
V2 O13 1.791(9) . ?
V2 O17 1.604(7) . ?
V3 V4 3.054(3) 2_565 ?
V3 V5 2.861(3) 2_565 ?
V3 V6 2.839(3) . ?
V3 O2 1.597(7) . ?
V3 O3 1.940(9) . ?
V3 O5 1.801(9) . ?
V3 O11 1.952(9) 2_565 ?
V3 O12 1.810(9) . ?
V4 V3 3.054(3) 2_565 ?
V4 O3 1.982(8) 2_565 ?
V4 O4 1.608(9) . ?
V4 O7 1.737(8) . ?
V4 O9 1.887(8) . ?
V4 O11 1.909(9) . ?
V5 V3 2.861(3) 2_565 ?
V5 O5 1.847(9) 2_565 ?
V5 O6 1.902(9) . ?
V5 O8 1.826(9) . ?
V5 O10 1.596(8) . ?
V5 O11 1.919(9) . ?
V6 O1 1.917(9) 2_565 ?
V6 O3 1.897(8) . ?
V6 O12 1.841(9) . ?
V6 O13 1.839(9) . ?
V6 O0AA 1.592(8) . ?
O1 V2 1.949(9) 2_565 ?
O1 V6 1.917(9) 2_565 ?
O3 V4 1.982(8) 2_565 ?
O5 V5 1.847(9) 2_565 ?
O6 V1 1.970(9) 2_565 ?
O7 V1 1.881(8) 2_565 ?
O11 V3 1.952(9) 2_565 ?
S6 O22 1.470(11) . ?
S6 C25 1.727(16) . ?
S6 C26 1.706(13) . ?
N1 C29 1.526(15) 2_565 ?
N1 C34 1.491(17) . ?
N2 C30 1.454(16) . ?
N2 C33 1.489(16) . ?
C29 N1 1.526(15) 2_565 ?
C29 C30 1.530(13) . ?
C33 C34 1.418(18) . ?
S5 O20 1.489(12) . ?
S5 C10 1.780(17) . ?
S5 C14 1.814(13) . ?
S5 S7 1.135(9) . ?
O20 S7 1.438(12) . ?
C10 S7 1.791(15) . ?
C14 S7 1.61(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
O16 Ba1 O16 93.91(13) . 3_565 ?
O16 Ba1 O16 149.7(5) 3_565 4_655 ?
O16 Ba1 O16 93.91(13) . 4_655 ?
O16 Ba1 O16 93.91(13) 3_565 2_665 ?
O16 Ba1 O16 149.7(5) . 2_665 ?
O16 Ba1 O16 93.91(13) 4_655 2_665 ?
O16 Ba1 O21 140.6(3) . . ?
O16 Ba1 O21 82.5(3) 3_565 . ?
O16 Ba1 O21 140.6(3) 4_655 4_655 ?
O16 Ba1 O21 140.6(3) 3_565 3_565 ?
O16 Ba1 O21 69.5(3) . 2_665 ?
O16 Ba1 O21 82.5(3) 4_655 2_665 ?
O16 Ba1 O21 69.5(3) 4_655 3_565 ?
O16 Ba1 O21 82.5(3) 2_665 3_565 ?
O16 Ba1 O21 140.6(3) 2_665 2_665 ?
O16 Ba1 O21 73.0(3) 3_565 2_665 ?
O16 Ba1 O21 73.0(3) 4_655 . ?
O16 Ba1 O21 82.5(3) . 4_655 ?
O16 Ba1 O21 69.5(3) 3_565 4_655 ?
O16 Ba1 O21 73.0(3) . 3_565 ?
O16 Ba1 O21 69.5(3) 2_665 . ?
O16 Ba1 O21 73.0(3) 2_665 4_655 ?
O21 Ba1 O21 72.0(4) . 2_665 ?
O21 Ba1 O21 130.9(3) . 3_565 ?
O21 Ba1 O21 72.0(4) 3_565 4_655 ?
O21 Ba1 O21 130.9(3) 3_565 2_665 ?
O21 Ba1 O21 130.9(3) . 4_655 ?
O21 Ba1 O21 130.9(3) 2_665 4_655 ?
O16 S1 C8 106.5(5) . . ?
O16 S1 C9 106.8(6) . . ?
C8 S1 C9 97.8(7) . . ?
O21 S3 C6 107.7(5) . . ?
O21 S3 C7 106.9(7) . . ?
C6 S3 C7 96.7(7) . . ?
S1 O16 Ba1 123.6(4) . . ?
S3 O21 Ba1 125.4(4) . . ?
O15 Ba2 O15 72.5(4) . 2_575 ?
O15 Ba2 O15 72.5(4) 3_465 4_665 ?
O15 Ba2 O15 130.6(3) 4_665 2_575 ?
O15 Ba2 O15 130.6(3) 3_465 2_575 ?
O15 Ba2 O15 130.6(3) . 4_665 ?
O15 Ba2 O15 130.6(3) . 3_465 ?
O19 Ba2 O15 70.3(3) 2_575 4_665 ?
O19 Ba2 O15 72.5(3) 2_575 2_575 ?
O19 Ba2 O15 72.5(3) 4_665 4_665 ?
O19 Ba2 O15 72.5(3) . . ?
O19 Ba2 O15 142.0(3) . 4_665 ?
O19 Ba2 O15 81.4(3) 3_465 4_665 ?
O19 Ba2 O15 72.5(3) 3_465 3_465 ?
O19 Ba2 O15 142.0(3) 4_665 2_575 ?
O19 Ba2 O15 70.3(3) 4_665 . ?
O19 Ba2 O15 81.4(3) 2_575 . ?
O19 Ba2 O15 142.0(3) 2_575 3_465 ?
O19 Ba2 O15 81.4(3) 4_665 3_465 ?
O19 Ba2 O15 70.3(3) . 3_465 ?
O19 Ba2 O15 70.3(3) 3_465 2_575 ?
O19 Ba2 O15 81.4(3) . 2_575 ?
O19 Ba2 O15 142.0(3) 3_465 . ?
O19 Ba2 O19 147.6(5) . 2_575 ?
O19 Ba2 O19 94.46(13) . 4_665 ?
O19 Ba2 O19 94.46(13) 3_465 2_575 ?
O19 Ba2 O19 94.46(12) 4_665 2_575 ?
O19 Ba2 O19 94.46(13) . 3_465 ?
O19 Ba2 O19 147.6(5) 3_465 4_665 ?
O19 S2 C23 104.1(6) . . ?
O19 S2 C24 105.6(5) . . ?
C23 S2 C24 98.3(7) . . ?
O15 S4 C15 104.6(7) . . ?
O15 S4 C18 105.5(6) . . ?
C18 S4 C15 98.4(7) . . ?
S4 O15 Ba2 124.5(5) . . ?
S2 O19 Ba2 124.2(4) . . ?
O1 V1 V2 38.1(3) . 2_565 ?
O1 V1 O6 76.9(3) . 2_565 ?
O6 V1 V2 38.8(2) 2_565 2_565 ?
O7 V1 V2 119.7(3) 2_565 2_565 ?
O7 V1 O1 150.3(4) 2_565 . ?
O7 V1 O6 84.0(3) 2_565 2_565 ?
O9 V1 V2 124.7(3) . 2_565 ?
O9 V1 O1 91.2(4) . . ?
O9 V1 O6 150.2(4) . 2_565 ?
O9 V1 O7 94.44(16) . 2_565 ?
O18 V1 V2 107.1(3) . 2_565 ?
O18 V1 O1 104.3(4) . . ?
O18 V1 O6 103.3(4) . 2_565 ?
O18 V1 O7 102.1(4) . 2_565 ?
O18 V1 O9 106.1(5) . . ?
V5 V2 V1 78.59(8) . 2_565 ?
V5 V2 V6 132.08(8) . . ?
V6 V2 V1 75.52(8) . 2_565 ?
O1 V2 V1 37.3(3) 2_565 2_565 ?
O1 V2 V5 113.8(3) 2_565 . ?
O1 V2 V6 42.0(3) 2_565 . ?
O1 V2 O6 76.4(4) 2_565 . ?
O6 V2 V1 39.1(2) . 2_565 ?
O6 V2 V5 42.0(3) . . ?
O6 V2 V6 111.5(2) . . ?
O8 V2 V1 116.1(3) . 2_565 ?
O8 V2 V5 38.9(3) . . ?
O8 V2 V6 130.7(3) . . ?
O8 V2 O1 145.3(4) . 2_565 ?
O8 V2 O6 80.9(4) . . ?
O13 V2 V1 112.9(3) . 2_565 ?
O13 V2 V5 130.2(3) . . ?
O13 V2 V6 38.7(3) . . ?
O13 V2 O1 80.6(4) . 2_565 ?
O13 V2 O6 141.8(3) . . ?
O13 V2 O8 102.7(4) . . ?
O17 V2 V1 110.5(4) . 2_565 ?
O17 V2 V5 113.0(3) . . ?
O17 V2 V6 113.6(2) . . ?
O17 V2 O1 105.2(4) . 2_565 ?
O17 V2 O6 107.7(4) . . ?
O17 V2 O8 106.5(4) . . ?
O17 V2 O13 107.6(4) . . ?
V5 V3 V4 75.54(8) 2_565 2_565 ?
V6 V3 V4 78.57(8) . 2_565 ?
V6 V3 V5 132.04(8) . 2_565 ?
O2 V3 V4 110.5(4) . 2_565 ?
O2 V3 V5 113.5(2) . 2_565 ?
O2 V3 V6 113.2(2) . . ?
O2 V3 O3 107.8(4) . . ?
O2 V3 O5 107.2(4) . . ?
O2 V3 O11 105.4(4) . 2_565 ?
O2 V3 O12 106.9(4) . . ?
O3 V3 V4 39.4(2) . 2_565 ?
O3 V3 V5 111.8(2) . 2_565 ?
O3 V3 V6 41.7(2) . . ?
O3 V3 O11 76.6(4) . 2_565 ?
O5 V3 V4 113.2(3) . 2_565 ?
O5 V3 V5 38.9(3) . 2_565 ?
O5 V3 V6 130.3(3) . . ?
O5 V3 O3 142.2(3) . . ?
O5 V3 O11 80.7(4) . 2_565 ?
O5 V3 O12 102.1(4) . . ?
O11 V3 V4 37.3(3) 2_565 2_565 ?
O11 V3 V5 41.9(3) 2_565 2_565 ?
O11 V3 V6 113.7(3) 2_565 . ?
O12 V3 V4 116.3(3) . 2_565 ?
O12 V3 V5 130.1(3) . 2_565 ?
O12 V3 V6 39.4(3) . . ?
O12 V3 O3 81.1(3) . . ?
O12 V3 O11 145.0(4) . 2_565 ?
O3 V4 V3 38.4(2) 2_565 2_565 ?
O4 V4 V3 107.8(3) . 2_565 ?
O4 V4 O3 104.4(4) . 2_565 ?
O4 V4 O7 105.1(5) . . ?
O4 V4 O9 102.6(4) . . ?
O4 V4 O11 104.6(4) . . ?
O7 V4 V3 125.1(3) . 2_565 ?
O7 V4 O3 150.1(4) . 2_565 ?
O7 V4 O9 94.30(15) . . ?
O7 V4 O11 91.6(4) . . ?
O9 V4 V3 119.1(3) . 2_565 ?
O9 V4 O3 83.7(3) . 2_565 ?
O9 V4 O11 149.6(4) . . ?
O11 V4 V3 38.2(3) . 2_565 ?
O11 V4 O3 76.6(3) . 2_565 ?
V2 V5 V3 137.07(7) . 2_565 ?
O5 V5 V2 125.5(3) 2_565 . ?
O5 V5 V3 37.8(3) 2_565 2_565 ?
O5 V5 O6 147.4(3) 2_565 . ?
O5 V5 O11 80.5(4) 2_565 . ?
O6 V5 V2 43.5(3) . . ?
O6 V5 V3 122.1(2) . 2_565 ?
O6 V5 O11 87.0(4) . . ?
O8 V5 V2 38.3(3) . . ?
O8 V5 V3 125.5(3) . 2_565 ?
O8 V5 O5 94.7(4) . 2_565 ?
O8 V5 O6 81.8(4) . . ?
O8 V5 O11 150.7(4) . . ?
O10 V5 V2 111.3(3) . . ?
O10 V5 V3 111.6(3) . 2_565 ?
O10 V5 O5 106.4(4) . 2_565 ?
O10 V5 O6 105.8(4) . . ?
O10 V5 O8 105.5(4) . . ?
O10 V5 O11 103.5(4) . . ?
O11 V5 V2 124.8(3) . . ?
O11 V5 V3 42.8(3) . 2_565 ?
V3 V6 V2 137.11(7) . . ?
O1 V6 V2 42.8(3) 2_565 . ?
O1 V6 V3 124.9(3) 2_565 . ?
O3 V6 V2 122.6(2) . . ?
O3 V6 V3 42.9(3) . . ?
O3 V6 O1 87.7(4) . 2_565 ?
O12 V6 V2 125.0(3) . . ?
O12 V6 V3 38.6(3) . . ?
O12 V6 O1 150.6(3) . 2_565 ?
O12 V6 O3 81.4(3) . . ?
O13 V6 V2 37.5(3) . . ?
O13 V6 V3 125.5(3) . . ?
O13 V6 O1 80.3(4) . 2_565 ?
O13 V6 O3 147.2(3) . . ?
O13 V6 O12 94.3(4) . . ?
O0AA V6 V2 111.1(3) . . ?
O0AA V6 V3 111.8(3) . . ?
O0AA V6 O1 103.2(4) . 2_565 ?
O0AA V6 O3 106.5(4) . . ?
O0AA V6 O12 106.1(4) . . ?
O0AA V6 O13 105.9(4) . . ?
V1 O1 V2 104.6(4) . 2_565 ?
V1 O1 V6 142.2(4) . 2_565 ?
V6 O1 V2 95.2(5) 2_565 2_565 ?
V3 O3 V4 102.3(3) . 2_565 ?
V6 O3 V3 95.4(4) . . ?
V6 O3 V4 148.6(4) . 2_565 ?
V3 O5 V5 103.3(5) . 2_565 ?
V2 O6 V1 102.1(3) . 2_565 ?
V5 O6 V1 149.2(4) . 2_565 ?
V5 O6 V2 94.5(4) . . ?
V4 O7 V1 143.5(6) . 2_565 ?
V2 O8 V5 102.7(5) . . ?
V1 O9 V4 144.3(6) . . ?
V4 O11 V3 104.5(4) . 2_565 ?
V4 O11 V5 142.6(4) . . ?
V5 O11 V3 95.3(4) . 2_565 ?
V3 O12 V6 102.1(5) . . ?
V2 O13 V6 103.8(5) . . ?
O22 S6 C25 109.1(8) . . ?
O22 S6 C26 110.8(7) . . ?
C26 S6 C25 99.8(7) . . ?
C34 N1 C29 116.3(12) . 2_565 ?
C30 N2 C33 112.4(11) . . ?
N1 C29 C30 112.8(9) 2_565 . ?
N2 C30 C29 110.4(9) . . ?
C34 C33 N2 117.0(11) . . ?
C33 C34 N1 114.5(12) . . ?
O20 S5 C10 104.9(8) . . ?
O20 S5 C14 108.7(7) . . ?
C10 S5 C14 99.1(8) . . ?
S7 S5 O20 64.8(5) . . ?
S7 S5 C10 72.0(7) . . ?
S7 S5 C14 61.2(7) . . ?
S7 O20 S5 45.6(5) . . ?
S5 C10 S7 37.1(4) . . ?
S7 C14 S5 38.1(5) . . ?
S5 S7 O20 69.6(7) . . ?
S5 S7 C10 70.9(7) . . ?
S5 S7 C14 80.7(7) . . ?
O20 S7 C10 106.6(8) . . ?
O20 S7 C14 123.9(10) . . ?
C14 S7 C10 106.9(8) . . ?


_olex2_submission_special_instructions 'No special instructions were received'
