# Supplementary Information (SI) for Dalton Transactions.
# 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_LH2Br
_database_code_depnum_ccdc_archive 'CCDC 2401175'
loop_
_audit_author_name
_audit_author_address
'Stephen Mansell'
;Heriot Watt University
United Kingdom
;
_audit_update_record             
;
2025-08-11 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_audit_creation_date             2023-06-02
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C19 H19 N2, Br'
_chemical_formula_sum            'C19 H19 Br N2'
_chemical_formula_weight         355.27
_chemical_absolute_configuration ?
_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 0.0181 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'
Br Br -0.6763 1.2805 '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'

_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      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   11.1141(2)
_cell_length_b                   12.0398(3)
_cell_length_c                   12.4524(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1666.27(7)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    1469
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      50.77
_cell_measurement_theta_min      5.11
_shelx_estimated_absorpt_T_max   0.556
_shelx_estimated_absorpt_T_min   0.425
_exptl_absorpt_coefficient_mu    3.329
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6287
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0959 before and 0.0573 after correction. The Ratio of minimum to maximum transmission is 0.8343. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.416
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0305
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            29705
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.185
_diffrn_reflns_theta_min         5.110
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.736
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                3261
_reflns_number_total             3273
_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 V8.40B (?, 2016)'
_computing_data_collection       'Bruker Apex4 v2022.10-0 (Bruker, 2022)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'XT (Sheldrick, 2015)'
_refine_diff_density_max         0.182
_refine_diff_density_min         -0.330
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details 
;
 Flack x determined using 1377 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.029(6)
_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     200
_refine_ls_number_reflns         3273
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0197
_refine_ls_R_factor_gt           0.0196
_refine_ls_restrained_S_all      1.108
_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)+1.4972P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0479
_refine_ls_wR_factor_ref         0.0480
_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
2.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C16(H16), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_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
N1 N 0.5495(2) 0.43191(19) 0.32686(18) 0.0170(5) Uani 1 1 d . . . . .
N2 N 0.3855(2) 0.51965(19) 0.36432(17) 0.0179(5) Uani 1 1 d . . . . .
C1 C 0.8172(2) 0.5099(2) 0.4166(2) 0.0185(6) Uani 1 1 d . . . . .
H1 H 0.873692 0.497144 0.477892 0.022 Uiso 1 1 calc R . . . .
C2 C 0.8824(2) 0.5695(2) 0.3271(2) 0.0172(5) Uani 1 1 d . . . . .
C3 C 0.9851(3) 0.5370(3) 0.2718(2) 0.0225(6) Uani 1 1 d . . . . .
H3 H 1.025317 0.469872 0.289584 0.027 Uiso 1 1 calc R . . . .
C4 C 1.0278(3) 0.6049(3) 0.1894(2) 0.0266(7) Uani 1 1 d . . . . .
H4 H 1.098790 0.584658 0.151661 0.032 Uiso 1 1 calc R . . . .
C5 C 0.9678(3) 0.7017(3) 0.1623(2) 0.0262(7) Uani 1 1 d . . . . .
H5 H 0.996329 0.745359 0.104123 0.031 Uiso 1 1 calc R . . . .
C6 C 0.8667(2) 0.7360(2) 0.2185(2) 0.0219(6) Uani 1 1 d . . . . .
H6 H 0.826497 0.802944 0.199856 0.026 Uiso 1 1 calc R . . . .
C7 C 0.8255(2) 0.6702(2) 0.3028(2) 0.0174(5) Uani 1 1 d . . . . .
C8 C 0.7269(2) 0.6868(2) 0.3797(2) 0.0180(6) Uani 1 1 d . . . . .
C9 C 0.6469(3) 0.7749(2) 0.3926(2) 0.0239(6) Uani 1 1 d . . . . .
H9 H 0.649305 0.837173 0.345786 0.029 Uiso 1 1 calc R . . . .
C10 C 0.5632(3) 0.7696(3) 0.4759(3) 0.0295(7) Uani 1 1 d . . . . .
H10 H 0.507882 0.828853 0.486009 0.035 Uiso 1 1 calc R . . . .
C11 C 0.5598(3) 0.6784(3) 0.5442(2) 0.0288(7) Uani 1 1 d . . . . .
H11 H 0.502022 0.676070 0.600347 0.035 Uiso 1 1 calc R . . . .
C12 C 0.6400(2) 0.5902(3) 0.5317(2) 0.0243(6) Uani 1 1 d . . . . .
H12 H 0.637673 0.528186 0.578760 0.029 Uiso 1 1 calc R . . . .
C13 C 0.7233(2) 0.5952(2) 0.4488(2) 0.0185(5) Uani 1 1 d . . . . .
C14 C 0.7640(3) 0.3976(3) 0.3795(3) 0.0251(6) Uani 1 1 d . . . . .
H14A H 0.830812 0.349233 0.355551 0.030 Uiso 1 1 calc R . . . .
H14B H 0.725404 0.361246 0.441944 0.030 Uiso 1 1 calc R . . . .
C15 C 0.6715(2) 0.4058(3) 0.2885(2) 0.0247(6) Uani 1 1 d . . . . .
H15A H 0.697392 0.464130 0.237477 0.030 Uiso 1 1 calc R . . . .
H15B H 0.669443 0.334376 0.249211 0.030 Uiso 1 1 calc R . . . .
C16 C 0.4913(3) 0.5269(2) 0.3141(2) 0.0191(6) Uani 1 1 d . . . . .
H16 H 0.520036 0.589760 0.275747 0.023 Uiso 1 1 calc R . . . .
C17 C 0.4785(3) 0.3603(3) 0.3866(2) 0.0211(6) Uani 1 1 d . . . . .
H17 H 0.497979 0.286490 0.407142 0.025 Uiso 1 1 calc R . . . .
C18 C 0.3764(2) 0.4156(3) 0.40978(19) 0.0207(5) Uani 1 1 d . . . . .
H18 H 0.310241 0.387911 0.450059 0.025 Uiso 1 1 calc R . . . .
C19 C 0.2939(3) 0.6069(3) 0.3682(3) 0.0274(7) Uani 1 1 d . . . . .
H19A H 0.222151 0.578718 0.404998 0.041 Uiso 1 1 calc GR . . . .
H19B H 0.272625 0.629194 0.294975 0.041 Uiso 1 1 calc GR . . . .
H19C H 0.325568 0.671173 0.407385 0.041 Uiso 1 1 calc GR . . . .
Br1 Br 0.39505(3) 0.58866(2) 0.06832(2) 0.02182(8) 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
N1 C15 1.471(3) . ?
N1 C16 1.324(4) . ?
N1 C17 1.386(4) . ?
N2 C16 1.334(4) . ?
N2 C18 1.379(4) . ?
N2 C19 1.464(4) . ?
C1 H1 1.0000 . ?
C1 C2 1.511(4) . ?
C1 C13 1.518(4) . ?
C1 C14 1.546(4) . ?
C2 C3 1.389(4) . ?
C2 C7 1.401(4) . ?
C3 H3 0.9500 . ?
C3 C4 1.395(4) . ?
C4 H4 0.9500 . ?
C4 C5 1.384(5) . ?
C5 H5 0.9500 . ?
C5 C6 1.386(4) . ?
C6 H6 0.9500 . ?
C6 C7 1.393(4) . ?
C7 C8 1.469(4) . ?
C8 C9 1.394(4) . ?
C8 C13 1.399(4) . ?
C9 H9 0.9500 . ?
C9 C10 1.395(4) . ?
C10 H10 0.9500 . ?
C10 C11 1.389(5) . ?
C11 H11 0.9500 . ?
C11 C12 1.395(5) . ?
C12 H12 0.9500 . ?
C12 C13 1.387(4) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C14 C15 1.533(4) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C16 H16 0.9500 . ?
C17 H17 0.9500 . ?
C17 C18 1.347(4) . ?
C18 H18 0.9500 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 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
C16 N1 C15 126.6(3) . . ?
C16 N1 C17 108.9(2) . . ?
C17 N1 C15 124.5(3) . . ?
C16 N2 C18 108.5(2) . . ?
C16 N2 C19 125.6(2) . . ?
C18 N2 C19 125.9(2) . . ?
C2 C1 H1 109.5 . . ?
C2 C1 C13 101.7(2) . . ?
C2 C1 C14 112.2(2) . . ?
C13 C1 H1 109.5 . . ?
C13 C1 C14 114.0(2) . . ?
C14 C1 H1 109.5 . . ?
C3 C2 C1 128.8(3) . . ?
C3 C2 C7 120.5(3) . . ?
C7 C2 C1 110.7(2) . . ?
C2 C3 H3 120.7 . . ?
C2 C3 C4 118.6(3) . . ?
C4 C3 H3 120.7 . . ?
C3 C4 H4 119.7 . . ?
C5 C4 C3 120.5(3) . . ?
C5 C4 H4 119.7 . . ?
C4 C5 H5 119.4 . . ?
C4 C5 C6 121.3(3) . . ?
C6 C5 H5 119.4 . . ?
C5 C6 H6 120.8 . . ?
C5 C6 C7 118.5(3) . . ?
C7 C6 H6 120.8 . . ?
C2 C7 C8 108.3(2) . . ?
C6 C7 C2 120.5(3) . . ?
C6 C7 C8 131.3(3) . . ?
C9 C8 C7 130.9(3) . . ?
C9 C8 C13 120.7(3) . . ?
C13 C8 C7 108.4(2) . . ?
C8 C9 H9 120.8 . . ?
C8 C9 C10 118.4(3) . . ?
C10 C9 H9 120.8 . . ?
C9 C10 H10 119.7 . . ?
C11 C10 C9 120.6(3) . . ?
C11 C10 H10 119.7 . . ?
C10 C11 H11 119.5 . . ?
C10 C11 C12 121.1(3) . . ?
C12 C11 H11 119.5 . . ?
C11 C12 H12 120.8 . . ?
C13 C12 C11 118.5(3) . . ?
C13 C12 H12 120.8 . . ?
C8 C13 C1 110.5(2) . . ?
C12 C13 C1 128.7(3) . . ?
C12 C13 C8 120.7(3) . . ?
C1 C14 H14A 108.5 . . ?
C1 C14 H14B 108.5 . . ?
H14A C14 H14B 107.5 . . ?
C15 C14 C1 114.9(3) . . ?
C15 C14 H14A 108.5 . . ?
C15 C14 H14B 108.5 . . ?
N1 C15 C14 113.1(2) . . ?
N1 C15 H15A 109.0 . . ?
N1 C15 H15B 109.0 . . ?
C14 C15 H15A 109.0 . . ?
C14 C15 H15B 109.0 . . ?
H15A C15 H15B 107.8 . . ?
N1 C16 N2 108.5(2) . . ?
N1 C16 H16 125.7 . . ?
N2 C16 H16 125.7 . . ?
N1 C17 H17 126.6 . . ?
C18 C17 N1 106.8(3) . . ?
C18 C17 H17 126.6 . . ?
N2 C18 H18 126.3 . . ?
C17 C18 N2 107.4(2) . . ?
C17 C18 H18 126.3 . . ?
N2 C19 H19A 109.5 . . ?
N2 C19 H19B 109.5 . . ?
N2 C19 H19C 109.5 . . ?
H19A C19 H19B 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 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
N1 C17 C18 N2 0.1(3) . . . . ?
C1 C2 C3 C4 178.4(3) . . . . ?
C1 C2 C7 C6 -176.4(2) . . . . ?
C1 C2 C7 C8 4.5(3) . . . . ?
C1 C14 C15 N1 -83.4(3) . . . . ?
C2 C1 C13 C8 5.2(3) . . . . ?
C2 C1 C13 C12 -176.1(3) . . . . ?
C2 C1 C14 C15 -60.5(3) . . . . ?
C2 C3 C4 C5 -1.2(4) . . . . ?
C2 C7 C8 C9 177.2(3) . . . . ?
C2 C7 C8 C13 -1.0(3) . . . . ?
C3 C2 C7 C6 3.9(4) . . . . ?
C3 C2 C7 C8 -175.2(2) . . . . ?
C3 C4 C5 C6 2.6(4) . . . . ?
C4 C5 C6 C7 -0.7(4) . . . . ?
C5 C6 C7 C2 -2.5(4) . . . . ?
C5 C6 C7 C8 176.3(3) . . . . ?
C6 C7 C8 C9 -1.8(5) . . . . ?
C6 C7 C8 C13 -180.0(3) . . . . ?
C7 C2 C3 C4 -2.0(4) . . . . ?
C7 C8 C9 C10 -178.1(3) . . . . ?
C7 C8 C13 C1 -2.8(3) . . . . ?
C7 C8 C13 C12 178.4(2) . . . . ?
C8 C9 C10 C11 0.0(4) . . . . ?
C9 C8 C13 C1 178.8(2) . . . . ?
C9 C8 C13 C12 0.0(4) . . . . ?
C9 C10 C11 C12 0.2(5) . . . . ?
C10 C11 C12 C13 -0.3(4) . . . . ?
C11 C12 C13 C1 -178.4(3) . . . . ?
C11 C12 C13 C8 0.2(4) . . . . ?
C13 C1 C2 C3 173.8(3) . . . . ?
C13 C1 C2 C7 -5.8(3) . . . . ?
C13 C1 C14 C15 54.5(3) . . . . ?
C13 C8 C9 C10 -0.1(4) . . . . ?
C14 C1 C2 C3 -63.9(4) . . . . ?
C14 C1 C2 C7 116.5(2) . . . . ?
C14 C1 C13 C8 -115.9(3) . . . . ?
C14 C1 C13 C12 62.8(4) . . . . ?
C15 N1 C16 N2 -177.2(2) . . . . ?
C15 N1 C17 C18 177.4(2) . . . . ?
C16 N1 C15 C14 108.8(3) . . . . ?
C16 N1 C17 C18 -0.4(3) . . . . ?
C16 N2 C18 C17 0.2(3) . . . . ?
C17 N1 C15 C14 -68.6(4) . . . . ?
C17 N1 C16 N2 0.5(3) . . . . ?
C18 N2 C16 N1 -0.5(3) . . . . ?
C19 N2 C16 N1 -179.3(2) . . . . ?
C19 N2 C18 C17 179.0(3) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'


####################################################################### 
# 
# 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_3_CeLBrN
_database_code_depnum_ccdc_archive 'CCDC 2401176'
loop_
_audit_author_name
_audit_author_address
'Stephen Mansell'
;Heriot Watt University
United Kingdom
;
_audit_update_record             
;
2025-08-11 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_audit_creation_date             2024-08-01
_audit_creation_method           
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C50 H70 Br2 Ce2 N6 Si4'
_chemical_formula_sum            'C50 H70 Br2 Ce2 N6 Si4'
_chemical_formula_weight         1307.54
_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 0.0181 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'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ce Ce -1.8482 9.6596 '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'
Si Si 0.2541 0.3302 '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/n 1'
_space_group_name_Hall           '-P 2yn'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   11.4996(3)
_cell_length_b                   11.3835(3)
_cell_length_c                   21.0457(5)
_cell_angle_alpha                90
_cell_angle_beta                 95.4860(10)
_cell_angle_gamma                90
_cell_volume                     2742.38(12)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9898
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      72.14
_cell_measurement_theta_min      4.22
_shelx_estimated_absorpt_T_max   0.576
_shelx_estimated_absorpt_T_min   0.167
_exptl_absorpt_coefficient_mu    15.494
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.4885
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1021 before and 0.0512 after correction. The Ratio of minimum to maximum transmission is 0.6482. 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    1.583
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1308
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0339
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            30621
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.139
_diffrn_reflns_theta_min         4.220
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean ?
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5317
_reflns_number_total             5386
_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 V8.40B (?, 2016)'
_computing_data_collection       'Bruker Apex4 v2022.10-0 (Bruker, 2022)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.743
_refine_diff_density_min         -0.834
_refine_diff_density_rms         0.087
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         5386
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0194
_refine_ls_R_factor_gt           0.0191
_refine_ls_restrained_S_all      1.064
_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)+(0.0254P)²+1.7353P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0480
_refine_ls_wR_factor_ref         0.0481
_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
2.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_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
Ce1 Ce 0.49258(2) 0.59435(2) 0.60217(2) 0.00711(5) Uani 1 1 d . . . . .
Br1 Br 0.65036(2) 0.54710(2) 0.49987(2) 0.01116(6) Uani 1 1 d . . . . .
Si1 Si 0.19972(4) 0.64629(5) 0.64369(2) 0.01160(11) Uani 1 1 d . . . . .
Si2 Si 0.30061(4) 0.80402(5) 0.54899(2) 0.01166(11) Uani 1 1 d . . . . .
N1 N 0.63942(14) 0.32707(15) 0.65833(7) 0.0117(3) Uani 1 1 d . . . . .
N2 N 0.45852(14) 0.28448(15) 0.65598(8) 0.0127(3) Uani 1 1 d . . . . .
N3 N 0.31505(13) 0.69330(15) 0.60425(8) 0.0113(3) Uani 1 1 d . . . . .
C1 C 0.69623(17) 0.59082(17) 0.69025(10) 0.0117(4) Uani 1 1 d . . . . .
C2 C 0.60900(16) 0.62197(19) 0.73120(9) 0.0130(4) Uani 1 1 d . . . . .
C3 C 0.56991(18) 0.5633(2) 0.78502(10) 0.0209(5) Uani 1 1 d . . . . .
H3 H 0.592649 0.484510 0.794558 0.025 Uiso 1 1 calc R U . . .
C4 C 0.4986(2) 0.6228(3) 0.82291(11) 0.0289(6) Uani 1 1 d . . . . .
H4 H 0.475812 0.585698 0.860209 0.035 Uiso 1 1 calc R U . . .
C5 C 0.45874(19) 0.7369(3) 0.80782(11) 0.0291(6) Uani 1 1 d . . . . .
H5 H 0.410195 0.775629 0.835321 0.035 Uiso 1 1 calc R U . . .
C6 C 0.48838(17) 0.7936(2) 0.75429(11) 0.0210(5) Uani 1 1 d . . . . .
H6 H 0.457240 0.868964 0.743280 0.025 Uiso 1 1 calc R U . . .
C7 C 0.56628(16) 0.73786(19) 0.71560(9) 0.0139(4) Uani 1 1 d . . . . .
C8 C 0.63055(16) 0.78143(18) 0.66511(9) 0.0124(4) Uani 1 1 d . . . . .
C9 C 0.63285(19) 0.89227(19) 0.63491(11) 0.0188(4) Uani 1 1 d . . . . .
H9 H 0.577316 0.950998 0.642782 0.023 Uiso 1 1 calc R U . . .
C10 C 0.7164(2) 0.9137(2) 0.59409(12) 0.0227(5) Uani 1 1 d . . . . .
H10 H 0.718996 0.988195 0.573961 0.027 Uiso 1 1 calc R U . . .
C11 C 0.79885(19) 0.8268(2) 0.58144(10) 0.0215(5) Uani 1 1 d . . . . .
H11 H 0.856202 0.844259 0.553207 0.026 Uiso 1 1 calc R U . . .
C12 C 0.79777(17) 0.71798(19) 0.60900(9) 0.0156(4) Uani 1 1 d . . . . .
H12 H 0.852765 0.660044 0.599186 0.019 Uiso 1 1 calc R U . . .
C13 C 0.71380(16) 0.69215(18) 0.65244(9) 0.0113(4) Uani 1 1 d . . . . .
C14 C 0.77615(17) 0.48640(19) 0.69832(10) 0.0155(4) Uani 1 1 d . . . . .
H14A H 0.772483 0.454631 0.741874 0.019 Uiso 1 1 calc R U . . .
H14B H 0.857166 0.513652 0.695220 0.019 Uiso 1 1 calc R U . . .
C15 C 0.75036(17) 0.38619(18) 0.65045(10) 0.0135(4) Uani 1 1 d . . . . .
H15A H 0.747995 0.418033 0.606571 0.016 Uiso 1 1 calc R U . . .
H15B H 0.814533 0.328004 0.655874 0.016 Uiso 1 1 calc R U . . .
C16 C 0.53098(16) 0.37423(19) 0.64358(9) 0.0114(4) Uani 1 1 d . . . . .
C17 C 0.63327(18) 0.21281(18) 0.67945(10) 0.0159(4) Uani 1 1 d . . . . .
H17 H 0.697199 0.162642 0.692391 0.019 Uiso 1 1 calc R U . . .
C18 C 0.51903(18) 0.18619(19) 0.67816(10) 0.0166(4) Uani 1 1 d . . . . .
H18 H 0.486557 0.113719 0.690211 0.020 Uiso 1 1 calc R U . . .
C19 C 0.33120(17) 0.28579(19) 0.64506(10) 0.0179(4) Uani 1 1 d . . . . .
H19A H 0.304965 0.220339 0.617024 0.027 Uiso 1 1 calc R U . . .
H19B H 0.305499 0.360172 0.624894 0.027 Uiso 1 1 calc R U . . .
H19C H 0.297694 0.277752 0.685942 0.027 Uiso 1 1 calc R U . . .
C20 C 0.25677(18) 0.5570(2) 0.71533(10) 0.0177(4) Uani 1 1 d . . . . .
H20A H 0.323695 0.510069 0.704745 0.027 Uiso 1 1 calc R U . . .
H20B H 0.195032 0.504757 0.727633 0.027 Uiso 1 1 calc R U . . .
H20C H 0.281287 0.609822 0.750893 0.027 Uiso 1 1 calc R U . . .
C21 C 0.11183(18) 0.7713(2) 0.67267(10) 0.0195(4) Uani 1 1 d . . . . .
H21A H 0.163040 0.822846 0.700128 0.029 Uiso 1 1 calc R U . . .
H21B H 0.050157 0.740063 0.696976 0.029 Uiso 1 1 calc R U . . .
H21C H 0.076503 0.816039 0.635998 0.029 Uiso 1 1 calc R U . . .
C22 C 0.09475(17) 0.5488(2) 0.59389(10) 0.0178(4) Uani 1 1 d . . . . .
H22A H 0.055796 0.594337 0.558497 0.027 Uiso 1 1 calc R U . . .
H22B H 0.036178 0.517920 0.620399 0.027 Uiso 1 1 calc R U . . .
H22C H 0.137644 0.483372 0.576840 0.027 Uiso 1 1 calc R U . . .
C23 C 0.16563(18) 0.7906(2) 0.49140(10) 0.0202(4) Uani 1 1 d . . . . .
H23A H 0.168837 0.848277 0.457059 0.030 Uiso 1 1 calc R U . . .
H23B H 0.096309 0.805127 0.513944 0.030 Uiso 1 1 calc R U . . .
H23C H 0.161443 0.711255 0.473198 0.030 Uiso 1 1 calc R U . . .
C24 C 0.2995(2) 0.95504(19) 0.58540(11) 0.0200(4) Uani 1 1 d . . . . .
H24A H 0.226627 0.966439 0.605220 0.030 Uiso 1 1 calc R U . . .
H24B H 0.305349 1.014283 0.552068 0.030 Uiso 1 1 calc R U . . .
H24C H 0.366040 0.963015 0.617877 0.030 Uiso 1 1 calc R U . . .
C25 C 0.43125(17) 0.79756(19) 0.50097(10) 0.0158(4) Uani 1 1 d . . . . .
H25A H 0.503057 0.806820 0.529580 0.024 Uiso 1 1 calc R U . . .
H25B H 0.425886 0.860919 0.469298 0.024 Uiso 1 1 calc R U . . .
H25C H 0.432541 0.721596 0.479139 0.024 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
Ce1 Br1 2.9941(2) . ?
Ce1 Br1 3.0383(2) 3_666 ?
Ce1 Si2 3.3690(5) . ?
Ce1 N3 2.3357(15) . ?
Ce1 C1 2.8446(19) . ?
Ce1 C2 2.9275(19) . ?
Ce1 C7 2.9494(19) . ?
Ce1 C8 2.8992(19) . ?
Ce1 C13 2.8837(18) . ?
Ce1 C16 2.676(2) . ?
Si1 N3 1.7161(17) . ?
Si1 C20 1.883(2) . ?
Si1 C21 1.880(2) . ?
Si1 C22 1.883(2) . ?
Si2 N3 1.7123(17) . ?
Si2 C23 1.882(2) . ?
Si2 C24 1.883(2) . ?
Si2 C25 1.890(2) . ?
N1 C15 1.466(3) . ?
N1 C16 1.366(2) . ?
N1 C17 1.379(3) . ?
N2 C16 1.359(3) . ?
N2 C18 1.375(3) . ?
N2 C19 1.460(3) . ?
C1 C2 1.428(3) . ?
C1 C13 1.427(3) . ?
C1 C14 1.502(3) . ?
C2 C3 1.424(3) . ?
C2 C7 1.435(3) . ?
C3 H3 0.9500 . ?
C3 C4 1.375(4) . ?
C4 H4 0.9500 . ?
C4 C5 1.404(4) . ?
C5 H5 0.9500 . ?
C5 C6 1.369(4) . ?
C6 H6 0.9500 . ?
C6 C7 1.417(3) . ?
C7 C8 1.439(3) . ?
C8 C9 1.414(3) . ?
C8 C13 1.439(3) . ?
C9 H9 0.9500 . ?
C9 C10 1.371(4) . ?
C10 H10 0.9500 . ?
C10 C11 1.412(4) . ?
C11 H11 0.9500 . ?
C11 C12 1.368(3) . ?
C12 H12 0.9500 . ?
C12 C13 1.422(3) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C14 C15 1.532(3) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C17 H17 0.9500 . ?
C17 C18 1.346(3) . ?
C18 H18 0.9500 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
C24 H24A 0.9800 . ?
C24 H24B 0.9800 . ?
C24 H24C 0.9800 . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 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
Br1 Ce1 Br1 73.776(6) . 3_666 ?
Br1 Ce1 Si2 108.134(10) . . ?
Br1 Ce1 Si2 81.233(10) 3_666 . ?
N3 Ce1 Br1 81.61(4) . 3_666 ?
N3 Ce1 Br1 133.71(4) . . ?
N3 Ce1 Si2 28.17(4) . . ?
N3 Ce1 C1 131.39(6) . . ?
N3 Ce1 C2 104.71(6) . . ?
N3 Ce1 C7 84.36(5) . . ?
N3 Ce1 C8 94.49(6) . . ?
N3 Ce1 C13 123.30(6) . . ?
N3 Ce1 C16 124.25(6) . . ?
C1 Ce1 Br1 144.01(4) . 3_666 ?
C1 Ce1 Br1 87.03(4) . . ?
C1 Ce1 Si2 134.35(4) . . ?
C1 Ce1 C2 28.61(6) . . ?
C1 Ce1 C7 47.58(5) . . ?
C1 Ce1 C8 48.10(5) . . ?
C1 Ce1 C13 28.83(6) . . ?
C2 Ce1 Br1 151.77(4) . 3_666 ?
C2 Ce1 Br1 115.56(4) . . ?
C2 Ce1 Si2 117.33(4) . . ?
C2 Ce1 C7 28.26(6) . . ?
C7 Ce1 Br1 122.31(4) . . ?
C7 Ce1 Br1 163.70(4) . 3_666 ?
C7 Ce1 Si2 90.29(4) . . ?
C8 Ce1 Br1 96.76(4) . . ?
C8 Ce1 Br1 161.38(4) . 3_666 ?
C8 Ce1 Si2 86.79(4) . . ?
C8 Ce1 C2 46.81(6) . . ?
C8 Ce1 C7 28.47(6) . . ?
C13 Ce1 Br1 149.60(4) . 3_666 ?
C13 Ce1 Br1 76.06(4) . . ?
C13 Ce1 Si2 112.05(4) . . ?
C13 Ce1 C2 46.30(5) . . ?
C13 Ce1 C7 46.69(5) . . ?
C13 Ce1 C8 28.81(5) . . ?
C16 Ce1 Br1 88.48(4) . . ?
C16 Ce1 Br1 78.18(4) . 3_666 ?
C16 Ce1 Si2 148.67(4) . . ?
C16 Ce1 C1 71.01(6) . . ?
C16 Ce1 C2 75.63(6) . . ?
C16 Ce1 C7 103.26(6) . . ?
C16 Ce1 C8 118.23(6) . . ?
C16 Ce1 C13 97.45(6) . . ?
Ce1 Br1 Ce1 106.225(6) . 3_666 ?
N3 Si1 C20 109.22(9) . . ?
N3 Si1 C21 112.65(9) . . ?
N3 Si1 C22 113.49(9) . . ?
C21 Si1 C20 107.79(10) . . ?
C21 Si1 C22 106.90(10) . . ?
C22 Si1 C20 106.46(10) . . ?
N3 Si2 Ce1 40.09(5) . . ?
N3 Si2 C23 113.45(9) . . ?
N3 Si2 C24 113.55(9) . . ?
N3 Si2 C25 107.70(9) . . ?
C23 Si2 Ce1 129.06(8) . . ?
C23 Si2 C24 107.42(10) . . ?
C23 Si2 C25 107.53(10) . . ?
C24 Si2 Ce1 122.77(7) . . ?
C24 Si2 C25 106.84(10) . . ?
C25 Si2 Ce1 67.73(6) . . ?
C16 N1 C15 125.41(17) . . ?
C16 N1 C17 111.73(17) . . ?
C17 N1 C15 122.80(16) . . ?
C16 N2 C18 112.15(17) . . ?
C16 N2 C19 125.87(17) . . ?
C18 N2 C19 121.93(17) . . ?
Si1 N3 Ce1 125.17(9) . . ?
Si2 N3 Ce1 111.74(8) . . ?
Si2 N3 Si1 121.93(9) . . ?
C2 C1 Ce1 78.92(11) . . ?
C2 C1 C14 125.84(19) . . ?
C13 C1 Ce1 77.11(11) . . ?
C13 C1 C2 106.32(17) . . ?
C13 C1 C14 125.81(18) . . ?
C14 C1 Ce1 122.79(12) . . ?
C1 C2 Ce1 72.47(11) . . ?
C1 C2 C7 109.58(18) . . ?
C3 C2 Ce1 122.42(13) . . ?
C3 C2 C1 131.0(2) . . ?
C3 C2 C7 119.08(19) . . ?
C7 C2 Ce1 76.72(11) . . ?
C2 C3 H3 120.6 . . ?
C4 C3 C2 118.8(2) . . ?
C4 C3 H3 120.6 . . ?
C3 C4 H4 119.2 . . ?
C3 C4 C5 121.6(2) . . ?
C5 C4 H4 119.2 . . ?
C4 C5 H5 119.3 . . ?
C6 C5 C4 121.3(2) . . ?
C6 C5 H5 119.3 . . ?
C5 C6 H6 120.6 . . ?
C5 C6 C7 118.9(2) . . ?
C7 C6 H6 120.6 . . ?
C2 C7 Ce1 75.02(11) . . ?
C2 C7 C8 107.27(17) . . ?
C6 C7 Ce1 124.37(13) . . ?
C6 C7 C2 120.1(2) . . ?
C6 C7 C8 131.9(2) . . ?
C8 C7 Ce1 73.82(11) . . ?
C7 C8 Ce1 77.70(11) . . ?
C9 C8 Ce1 118.87(13) . . ?
C9 C8 C7 132.2(2) . . ?
C9 C8 C13 120.37(19) . . ?
C13 C8 Ce1 75.00(10) . . ?
C13 C8 C7 106.94(18) . . ?
C8 C9 H9 120.5 . . ?
C10 C9 C8 119.0(2) . . ?
C10 C9 H9 120.5 . . ?
C9 C10 H10 119.4 . . ?
C9 C10 C11 121.1(2) . . ?
C11 C10 H10 119.4 . . ?
C10 C11 H11 119.3 . . ?
C12 C11 C10 121.4(2) . . ?
C12 C11 H11 119.3 . . ?
C11 C12 H12 120.2 . . ?
C11 C12 C13 119.6(2) . . ?
C13 C12 H12 120.2 . . ?
C1 C13 Ce1 74.06(11) . . ?
C1 C13 C8 109.60(17) . . ?
C8 C13 Ce1 76.19(10) . . ?
C12 C13 Ce1 118.25(12) . . ?
C12 C13 C1 131.81(19) . . ?
C12 C13 C8 118.54(19) . . ?
C1 C14 H14A 108.3 . . ?
C1 C14 H14B 108.3 . . ?
C1 C14 C15 115.91(16) . . ?
H14A C14 H14B 107.4 . . ?
C15 C14 H14A 108.3 . . ?
C15 C14 H14B 108.3 . . ?
N1 C15 C14 112.53(16) . . ?
N1 C15 H15A 109.1 . . ?
N1 C15 H15B 109.1 . . ?
C14 C15 H15A 109.1 . . ?
C14 C15 H15B 109.1 . . ?
H15A C15 H15B 107.8 . . ?
N1 C16 Ce1 124.11(14) . . ?
N2 C16 Ce1 132.94(13) . . ?
N2 C16 N1 102.95(17) . . ?
N1 C17 H17 126.7 . . ?
C18 C17 N1 106.62(18) . . ?
C18 C17 H17 126.7 . . ?
N2 C18 H18 126.7 . . ?
C17 C18 N2 106.55(18) . . ?
C17 C18 H18 126.7 . . ?
N2 C19 H19A 109.5 . . ?
N2 C19 H19B 109.5 . . ?
N2 C19 H19C 109.5 . . ?
H19A C19 H19B 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
Si1 C20 H20A 109.5 . . ?
Si1 C20 H20B 109.5 . . ?
Si1 C20 H20C 109.5 . . ?
H20A C20 H20B 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
Si1 C21 H21A 109.5 . . ?
Si1 C21 H21B 109.5 . . ?
Si1 C21 H21C 109.5 . . ?
H21A C21 H21B 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
Si1 C22 H22A 109.5 . . ?
Si1 C22 H22B 109.5 . . ?
Si1 C22 H22C 109.5 . . ?
H22A C22 H22B 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
Si2 C23 H23A 109.5 . . ?
Si2 C23 H23B 109.5 . . ?
Si2 C23 H23C 109.5 . . ?
H23A C23 H23B 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
Si2 C24 H24A 109.5 . . ?
Si2 C24 H24B 109.5 . . ?
Si2 C24 H24C 109.5 . . ?
H24A C24 H24B 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
Si2 C25 H25A 109.5 . . ?
Si2 C25 H25B 109.5 . . ?
Si2 C25 H25C 109.5 . . ?
H25A C25 H25B 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 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
Ce1 Si2 N3 Si1 -168.27(16) . . . . ?
Ce1 C1 C2 C3 118.1(2) . . . . ?
Ce1 C1 C2 C7 -68.41(13) . . . . ?
Ce1 C1 C13 C8 68.58(13) . . . . ?
Ce1 C1 C13 C12 -113.9(2) . . . . ?
Ce1 C1 C14 C15 7.2(2) . . . . ?
Ce1 C2 C3 C4 -96.8(2) . . . . ?
Ce1 C2 C7 C6 121.36(17) . . . . ?
Ce1 C2 C7 C8 -67.34(13) . . . . ?
Ce1 C7 C8 C9 118.0(2) . . . . ?
Ce1 C7 C8 C13 -69.92(12) . . . . ?
Ce1 C8 C9 C10 -89.7(2) . . . . ?
Ce1 C8 C13 C1 -67.19(13) . . . . ?
Ce1 C8 C13 C12 114.91(16) . . . . ?
N1 C17 C18 N2 0.3(2) . . . . ?
C1 C2 C3 C4 168.6(2) . . . . ?
C1 C2 C7 Ce1 65.65(13) . . . . ?
C1 C2 C7 C6 -172.99(17) . . . . ?
C1 C2 C7 C8 -1.7(2) . . . . ?
C1 C14 C15 N1 -67.3(2) . . . . ?
C2 C1 C13 Ce1 -74.19(13) . . . . ?
C2 C1 C13 C8 -5.6(2) . . . . ?
C2 C1 C13 C12 171.92(19) . . . . ?
C2 C1 C14 C15 107.8(2) . . . . ?
C2 C3 C4 C5 3.5(3) . . . . ?
C2 C7 C8 Ce1 68.16(13) . . . . ?
C2 C7 C8 C9 -173.8(2) . . . . ?
C2 C7 C8 C13 -1.8(2) . . . . ?
C3 C2 C7 Ce1 -119.94(17) . . . . ?
C3 C2 C7 C6 1.4(3) . . . . ?
C3 C2 C7 C8 172.72(17) . . . . ?
C3 C4 C5 C6 0.6(3) . . . . ?
C4 C5 C6 C7 -3.6(3) . . . . ?
C5 C6 C7 Ce1 94.6(2) . . . . ?
C5 C6 C7 C2 2.6(3) . . . . ?
C5 C6 C7 C8 -166.2(2) . . . . ?
C6 C7 C8 Ce1 -122.0(2) . . . . ?
C6 C7 C8 C9 -4.0(4) . . . . ?
C6 C7 C8 C13 168.1(2) . . . . ?
C7 C2 C3 C4 -4.4(3) . . . . ?
C7 C8 C9 C10 170.4(2) . . . . ?
C7 C8 C13 Ce1 71.81(13) . . . . ?
C7 C8 C13 C1 4.6(2) . . . . ?
C7 C8 C13 C12 -173.28(16) . . . . ?
C8 C9 C10 C11 0.6(3) . . . . ?
C9 C8 C13 Ce1 -114.99(17) . . . . ?
C9 C8 C13 C1 177.82(17) . . . . ?
C9 C8 C13 C12 -0.1(3) . . . . ?
C9 C10 C11 C12 0.5(3) . . . . ?
C10 C11 C12 C13 -1.4(3) . . . . ?
C11 C12 C13 Ce1 90.3(2) . . . . ?
C11 C12 C13 C1 -176.2(2) . . . . ?
C11 C12 C13 C8 1.2(3) . . . . ?
C13 C1 C2 Ce1 72.89(13) . . . . ?
C13 C1 C2 C3 -169.1(2) . . . . ?
C13 C1 C2 C7 4.5(2) . . . . ?
C13 C1 C14 C15 -90.7(2) . . . . ?
C13 C8 C9 C10 -0.8(3) . . . . ?
C14 C1 C2 Ce1 -122.64(19) . . . . ?
C14 C1 C2 C3 -4.6(3) . . . . ?
C14 C1 C2 C7 168.95(18) . . . . ?
C14 C1 C13 Ce1 121.33(19) . . . . ?
C14 C1 C13 C8 -170.09(18) . . . . ?
C14 C1 C13 C12 7.4(3) . . . . ?
C15 N1 C16 Ce1 -3.7(3) . . . . ?
C15 N1 C16 N2 176.88(17) . . . . ?
C15 N1 C17 C18 -177.33(17) . . . . ?
C16 N1 C15 C14 70.6(2) . . . . ?
C16 N1 C17 C18 0.1(2) . . . . ?
C16 N2 C18 C17 -0.6(2) . . . . ?
C17 N1 C15 C14 -112.4(2) . . . . ?
C17 N1 C16 Ce1 178.97(13) . . . . ?
C17 N1 C16 N2 -0.4(2) . . . . ?
C18 N2 C16 Ce1 -178.66(14) . . . . ?
C18 N2 C16 N1 0.7(2) . . . . ?
C19 N2 C16 Ce1 4.1(3) . . . . ?
C19 N2 C16 N1 -176.60(17) . . . . ?
C19 N2 C18 C17 176.73(18) . . . . ?
C20 Si1 N3 Ce1 29.31(13) . . . . ?
C20 Si1 N3 Si2 -164.04(11) . . . . ?
C21 Si1 N3 Ce1 149.05(10) . . . . ?
C21 Si1 N3 Si2 -44.30(14) . . . . ?
C22 Si1 N3 Ce1 -89.29(12) . . . . ?
C22 Si1 N3 Si2 77.35(13) . . . . ?
C23 Si2 N3 Ce1 123.46(10) . . . . ?
C23 Si2 N3 Si1 -44.81(14) . . . . ?
C24 Si2 N3 Ce1 -113.52(10) . . . . ?
C24 Si2 N3 Si1 78.21(13) . . . . ?
C25 Si2 N3 Ce1 4.57(11) . . . . ?
C25 Si2 N3 Si1 -163.70(11) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'

####################################################################### 
# 
# 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_7_NdLN2
_database_code_depnum_ccdc_archive 'CCDC 2401179'
loop_
_audit_author_name
_audit_author_address
'Stephen Mansell'
;Heriot Watt University
United Kingdom
;
_audit_update_record             
;
2025-08-11 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_audit_creation_date             2024-10-07
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C31 H53 N4 Nd Si4'
_chemical_formula_sum            'C31 H53 N4 Nd Si4'
_chemical_formula_weight         738.37
_chemical_absolute_configuration ?
_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 0.0181 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'
Nd Nd -3.1807 10.9079 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.2541 0.3302 '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      orthorhombic
_space_group_IT_number           29
_space_group_name_H-M_alt        'P c a 21'
_space_group_name_Hall           'P 2c -2ac'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'x+1/2, -y, z'
'-x+1/2, y, z+1/2'

_cell_length_a                   12.9276(2)
_cell_length_b                   16.4136(3)
_cell_length_c                   16.8458(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3574.48(11)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9614
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.06
_cell_measurement_theta_min      4.35
_shelx_estimated_absorpt_T_max   0.705
_shelx_estimated_absorpt_T_min   0.211
_exptl_absorpt_coefficient_mu    12.555
_exptl_absorpt_correction_T_max  0.9054
_exptl_absorpt_correction_T_min  0.1279
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1405 before and 0.0777 after correction. The Ratio of minimum to maximum transmission is 0.1413. 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    1.372
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1532
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0695
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            76590
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.166
_diffrn_reflns_theta_min         2.623
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.947
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.927
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                6757
_reflns_number_total             7357
_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker Apex4 v2022.10-0 (Bruker, 2022)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 (Sheldrick, 2015)'
_refine_diff_density_max         6.371
_refine_diff_density_min         -3.749
_refine_diff_density_rms         0.685
_refine_ls_abs_structure_details 
;
 Twinning involves inversion, so Flack parameter cannot be determined
;
_refine_ls_abs_structure_Flack   ?
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         7357
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0698
_refine_ls_restrained_S_all      1.018
_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)+(0.1652P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1775
_refine_ls_wR_factor_ref         0.1819
_refine_special_details          
;
 Refined as a 4-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.858(7)
 0.0004(9) 0.142(7) -0.0000(9)
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.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C17(H17), C18(H18)
3.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_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
Nd1 Nd 0.53788(3) 0.26254(3) 0.56280(6) 0.0108(2) Uani 1 1 d . . . . .
Si1 Si 0.31296(19) 0.20358(14) 0.46327(14) 0.0145(5) Uani 1 1 d . . . . .
Si2 Si 0.4423(2) 0.31488(17) 0.36685(15) 0.0160(5) Uani 1 1 d . . . . .
Si3 Si 0.62727(19) 0.07620(15) 0.54753(15) 0.0177(6) Uani 1 1 d . . . . .
Si4 Si 0.53827(18) 0.08944(19) 0.70830(18) 0.0184(6) Uani 1 1 d . . . . .
N1 N 0.4511(6) 0.3508(6) 0.7456(5) 0.0162(19) Uani 1 1 d . . . . .
N2 N 0.3422(6) 0.3902(5) 0.6591(4) 0.0147(15) Uani 1 1 d . . . . .
N3 N 0.4236(7) 0.2628(4) 0.4547(5) 0.0138(17) Uani 1 1 d . . . . .
N4 N 0.5607(6) 0.1325(5) 0.6165(5) 0.0163(15) Uani 1 1 d . . . . .
C1 C 0.6574(7) 0.3650(5) 0.6656(5) 0.0128(17) Uani 1 1 d . . . . .
C2 C 0.7344(6) 0.3246(6) 0.6185(6) 0.0158(17) Uani 1 1 d . . . . .
C3 C 0.8089(8) 0.2637(5) 0.6373(7) 0.017(2) Uani 1 1 d . . . . .
H3 H 0.810067 0.239323 0.688419 0.020 Uiso 1 1 calc R . . . .
C4 C 0.8797(7) 0.2404(5) 0.5799(7) 0.018(3) Uani 1 1 d . . . . .
H4 H 0.930186 0.200525 0.592799 0.022 Uiso 1 1 calc R . . . .
C5 C 0.8791(8) 0.2745(6) 0.5021(7) 0.019(2) Uani 1 1 d . . . . .
H5 H 0.929097 0.257799 0.464111 0.023 Uiso 1 1 calc R . . . .
C6 C 0.8055(7) 0.3318(5) 0.4824(6) 0.0157(17) Uani 1 1 d . . . . .
H6 H 0.804642 0.354438 0.430542 0.019 Uiso 1 1 calc R . . . .
C7 C 0.7311(7) 0.3570(5) 0.5392(5) 0.0154(18) Uani 1 1 d . . . . .
C8 C 0.6540(8) 0.4206(6) 0.5376(5) 0.0160(18) Uani 1 1 d . . . . .
C9 C 0.6240(7) 0.4787(6) 0.4791(5) 0.0155(18) Uani 1 1 d . . . . .
H9 H 0.651135 0.475672 0.426745 0.019 Uiso 1 1 calc R . . . .
C10 C 0.5556(8) 0.5389(7) 0.4991(6) 0.017(2) Uani 1 1 d . . . . .
H10 H 0.534341 0.576737 0.459673 0.020 Uiso 1 1 calc R . . . .
C11 C 0.5157(8) 0.5462(6) 0.5771(6) 0.0178(19) Uani 1 1 d . . . . .
H11 H 0.469284 0.589306 0.589365 0.021 Uiso 1 1 calc R . . . .
C12 C 0.5437(6) 0.4911(6) 0.6358(6) 0.014(2) Uani 1 1 d . . . . .
H12 H 0.516510 0.495963 0.688012 0.017 Uiso 1 1 calc R . . . .
C13 C 0.6138(6) 0.4274(5) 0.6167(5) 0.0101(16) Uani 1 1 d . . . . .
C14 C 0.6432(8) 0.3585(6) 0.7548(6) 0.0161(19) Uani 1 1 d . . . . .
H14A H 0.642709 0.414059 0.777655 0.019 Uiso 1 1 calc R . . . .
H14B H 0.703315 0.329195 0.777446 0.019 Uiso 1 1 calc R . . . .
C15 C 0.5442(7) 0.3146(7) 0.7799(6) 0.019(2) Uani 1 1 d . . . . .
H15A H 0.548589 0.256776 0.763384 0.022 Uiso 1 1 calc R . . . .
H15B H 0.538663 0.315887 0.838511 0.022 Uiso 1 1 calc R . . . .
C16 C 0.4226(7) 0.3391(6) 0.6685(6) 0.0150(17) Uani 1 1 d . . . . .
C17 C 0.3895(7) 0.4082(6) 0.7830(6) 0.019(2) Uani 1 1 d . . . . .
H17 H 0.394309 0.426171 0.836502 0.023 Uiso 1 1 calc R . . . .
C18 C 0.3206(7) 0.4333(6) 0.7271(6) 0.0207(19) Uani 1 1 d . . . . .
H18 H 0.267761 0.472951 0.733740 0.025 Uiso 1 1 calc R . . . .
C19 C 0.2879(8) 0.4031(7) 0.5846(6) 0.025(2) Uani 1 1 d . . . . .
H19A H 0.284948 0.461587 0.573000 0.037 Uiso 1 1 calc GR . . . .
H19B H 0.217468 0.381465 0.588770 0.037 Uiso 1 1 calc GR . . . .
H19C H 0.324675 0.375016 0.541689 0.037 Uiso 1 1 calc GR . . . .
C20 C 0.2940(7) 0.1748(5) 0.5690(7) 0.0215(18) Uani 1 1 d . . . . .
H20A H 0.229644 0.143745 0.574419 0.032 Uiso 1 1 calc GR . . . .
H20B H 0.289921 0.224222 0.601561 0.032 Uiso 1 1 calc GR . . . .
H20C H 0.352346 0.141401 0.586790 0.032 Uiso 1 1 calc GR . . . .
C21 C 0.1888(9) 0.2557(7) 0.4333(8) 0.023(2) Uani 1 1 d . . . . .
H21A H 0.130609 0.218204 0.440802 0.034 Uiso 1 1 calc GR . . . .
H21B H 0.192821 0.271713 0.377340 0.034 Uiso 1 1 calc GR . . . .
H21C H 0.178439 0.304272 0.466203 0.034 Uiso 1 1 calc GR . . . .
C22 C 0.3215(8) 0.1075(6) 0.4035(6) 0.022(2) Uani 1 1 d . . . . .
H22A H 0.262001 0.072646 0.415619 0.033 Uiso 1 1 calc GR . . . .
H22B H 0.385549 0.078623 0.416911 0.033 Uiso 1 1 calc GR . . . .
H22C H 0.321474 0.120944 0.346864 0.033 Uiso 1 1 calc GR . . . .
C23 C 0.3868(7) 0.4205(6) 0.3723(6) 0.020(2) Uani 1 1 d . . . . .
H23A H 0.399492 0.448979 0.322114 0.030 Uiso 1 1 calc GR . . . .
H23B H 0.419724 0.450474 0.415824 0.030 Uiso 1 1 calc GR . . . .
H23C H 0.312097 0.417225 0.381860 0.030 Uiso 1 1 calc GR . . . .
C24 C 0.3854(10) 0.2669(6) 0.2738(7) 0.027(3) Uani 1 1 d . . . . .
H24A H 0.402154 0.300782 0.227615 0.041 Uiso 1 1 calc GR . . . .
H24B H 0.310089 0.262902 0.279296 0.041 Uiso 1 1 calc GR . . . .
H24C H 0.414584 0.212325 0.266417 0.041 Uiso 1 1 calc GR . . . .
C25 C 0.5848(8) 0.3226(7) 0.3428(6) 0.022(2) Uani 1 1 d . . . . .
H25A H 0.594986 0.362214 0.299926 0.032 Uiso 1 1 calc GR . . . .
H25B H 0.610567 0.269220 0.325849 0.032 Uiso 1 1 calc GR . . . .
H25C H 0.622754 0.340449 0.390043 0.032 Uiso 1 1 calc GR . . . .
C26 C 0.6524(8) 0.1433(6) 0.4595(6) 0.025(2) Uani 1 1 d . . . . .
H26A H 0.693120 0.113253 0.420129 0.037 Uiso 1 1 calc GR . . . .
H26B H 0.690810 0.191709 0.476505 0.037 Uiso 1 1 calc GR . . . .
H26C H 0.586399 0.159917 0.435945 0.037 Uiso 1 1 calc GR . . . .
C27 C 0.5548(9) -0.0145(7) 0.5063(8) 0.022(2) Uani 1 1 d . . . . .
H27A H 0.583254 -0.064710 0.528971 0.034 Uiso 1 1 calc GR . . . .
H27B H 0.562256 -0.015735 0.448423 0.034 Uiso 1 1 calc GR . . . .
H27C H 0.481415 -0.010022 0.520152 0.034 Uiso 1 1 calc GR . . . .
C28 C 0.7563(8) 0.0411(6) 0.5854(7) 0.028(2) Uani 1 1 d . . . . .
H28A H 0.746068 0.002141 0.628753 0.042 Uiso 1 1 calc GR . . . .
H28B H 0.795628 0.088063 0.604887 0.042 Uiso 1 1 calc GR . . . .
H28C H 0.794673 0.014759 0.542253 0.042 Uiso 1 1 calc GR . . . .
C29 C 0.6493(9) 0.1084(7) 0.7798(7) 0.028(2) Uani 1 1 d . . . . .
H29A H 0.629088 0.091055 0.833216 0.043 Uiso 1 1 calc GR . . . .
H29B H 0.666001 0.166673 0.780358 0.043 Uiso 1 1 calc GR . . . .
H29C H 0.710050 0.077396 0.762594 0.043 Uiso 1 1 calc GR . . . .
C30 C 0.5230(9) -0.0248(7) 0.7071(8) 0.031(2) Uani 1 1 d . . . . .
H30A H 0.510898 -0.044371 0.761251 0.046 Uiso 1 1 calc GR . . . .
H30B H 0.586147 -0.049763 0.686001 0.046 Uiso 1 1 calc GR . . . .
H30C H 0.464137 -0.039527 0.673417 0.046 Uiso 1 1 calc GR . . . .
C31 C 0.4130(9) 0.1256(7) 0.7561(7) 0.025(2) Uani 1 1 d . . . . .
H31A H 0.416933 0.117653 0.813686 0.038 Uiso 1 1 calc GR . . . .
H31B H 0.354857 0.094110 0.734760 0.038 Uiso 1 1 calc GR . . . .
H31C H 0.402681 0.183487 0.744472 0.038 Uiso 1 1 calc GR . . . .


_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
Nd1 Si3 3.280(2) . ?
Nd1 N3 2.345(9) . ?
Nd1 N4 2.337(9) . ?
Nd1 C1 2.866(9) . ?
Nd1 C2 2.894(8) . ?
Nd1 C7 2.967(8) . ?
Nd1 C8 3.027(9) . ?
Nd1 C13 3.018(8) . ?
Nd1 C16 2.641(9) . ?
Si1 N3 1.735(9) . ?
Si1 C20 1.859(11) . ?
Si1 C21 1.888(12) . ?
Si1 C22 1.874(10) . ?
Si2 N3 1.727(8) . ?
Si2 C23 1.879(11) . ?
Si2 C24 1.903(12) . ?
Si2 C25 1.891(10) . ?
Si3 N4 1.716(8) . ?
Si3 C26 1.875(11) . ?
Si3 C27 1.891(12) . ?
Si3 C28 1.877(10) . ?
Si4 N4 1.725(9) . ?
Si4 C29 1.899(11) . ?
Si4 C30 1.885(12) . ?
Si4 C31 1.903(12) . ?
N1 C15 1.462(12) . ?
N1 C16 1.363(13) . ?
N1 C17 1.385(13) . ?
N2 C16 1.344(12) . ?
N2 C18 1.375(12) . ?
N2 C19 1.455(12) . ?
C1 C2 1.436(12) . ?
C1 C13 1.431(12) . ?
C1 C14 1.517(13) . ?
C2 C3 1.425(13) . ?
C2 C7 1.438(13) . ?
C3 H3 0.9500 . ?
C3 C4 1.384(15) . ?
C4 H4 0.9500 . ?
C4 C5 1.424(16) . ?
C5 H5 0.9500 . ?
C5 C6 1.378(14) . ?
C6 H6 0.9500 . ?
C6 C7 1.419(12) . ?
C7 C8 1.442(14) . ?
C8 C9 1.426(13) . ?
C8 C13 1.434(13) . ?
C9 H9 0.9500 . ?
C9 C10 1.367(15) . ?
C10 H10 0.9500 . ?
C10 C11 1.417(14) . ?
C11 H11 0.9500 . ?
C11 C12 1.389(15) . ?
C12 H12 0.9500 . ?
C12 C13 1.421(12) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C14 C15 1.529(14) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C17 H17 0.9500 . ?
C17 C18 1.360(15) . ?
C18 H18 0.9500 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
C24 H24A 0.9800 . ?
C24 H24B 0.9800 . ?
C24 H24C 0.9800 . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 0.9800 . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?
C26 H26C 0.9800 . ?
C27 H27A 0.9800 . ?
C27 H27B 0.9800 . ?
C27 H27C 0.9800 . ?
C28 H28A 0.9800 . ?
C28 H28B 0.9800 . ?
C28 H28C 0.9800 . ?
C29 H29A 0.9800 . ?
C29 H29B 0.9800 . ?
C29 H29C 0.9800 . ?
C30 H30A 0.9800 . ?
C30 H30B 0.9800 . ?
C30 H30C 0.9800 . ?
C31 H31A 0.9800 . ?
C31 H31B 0.9800 . ?
C31 H31C 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
N3 Nd1 Si3 99.37(19) . . ?
N3 Nd1 C1 143.9(2) . . ?
N3 Nd1 C2 143.6(3) . . ?
N3 Nd1 C7 115.2(3) . . ?
N3 Nd1 C8 101.7(3) . . ?
N3 Nd1 C13 115.9(2) . . ?
N3 Nd1 C16 99.6(3) . . ?
N4 Nd1 Si3 30.0(2) . . ?
N4 Nd1 N3 112.4(3) . . ?
N4 Nd1 C1 103.5(3) . . ?
N4 Nd1 C2 94.9(3) . . ?
N4 Nd1 C7 115.0(3) . . ?
N4 Nd1 C8 140.7(3) . . ?
N4 Nd1 C13 131.4(3) . . ?
N4 Nd1 C16 104.2(3) . . ?
C1 Nd1 Si3 113.87(17) . . ?
C1 Nd1 C2 28.9(2) . . ?
C1 Nd1 C7 47.2(3) . . ?
C1 Nd1 C8 46.7(3) . . ?
C1 Nd1 C13 28.0(2) . . ?
C2 Nd1 Si3 92.55(19) . . ?
C2 Nd1 C7 28.4(3) . . ?
C2 Nd1 C8 46.2(3) . . ?
C2 Nd1 C13 45.7(2) . . ?
C7 Nd1 Si3 100.39(19) . . ?
C7 Nd1 C8 27.8(3) . . ?
C7 Nd1 C13 45.4(2) . . ?
C8 Nd1 Si3 127.8(2) . . ?
C13 Nd1 Si3 138.17(17) . . ?
C13 Nd1 C8 27.4(2) . . ?
C16 Nd1 Si3 134.1(2) . . ?
C16 Nd1 C1 67.5(3) . . ?
C16 Nd1 C2 96.3(3) . . ?
C16 Nd1 C7 108.5(3) . . ?
C16 Nd1 C8 88.1(3) . . ?
C16 Nd1 C13 63.5(3) . . ?
N3 Si1 C20 109.3(4) . . ?
N3 Si1 C21 115.1(5) . . ?
N3 Si1 C22 112.2(4) . . ?
C20 Si1 C21 105.0(5) . . ?
C20 Si1 C22 108.0(4) . . ?
C22 Si1 C21 106.7(5) . . ?
N3 Si2 C23 111.2(4) . . ?
N3 Si2 C24 116.6(5) . . ?
N3 Si2 C25 110.7(5) . . ?
C23 Si2 C24 105.9(5) . . ?
C23 Si2 C25 108.7(5) . . ?
C25 Si2 C24 103.2(5) . . ?
N4 Si3 Nd1 42.9(3) . . ?
N4 Si3 C26 107.8(5) . . ?
N4 Si3 C27 115.1(5) . . ?
N4 Si3 C28 112.4(5) . . ?
C26 Si3 Nd1 64.9(3) . . ?
C26 Si3 C27 104.9(5) . . ?
C26 Si3 C28 107.1(5) . . ?
C27 Si3 Nd1 126.0(4) . . ?
C28 Si3 Nd1 125.0(3) . . ?
C28 Si3 C27 108.9(5) . . ?
N4 Si4 C29 112.0(5) . . ?
N4 Si4 C30 114.6(5) . . ?
N4 Si4 C31 113.2(5) . . ?
C29 Si4 C31 108.9(6) . . ?
C30 Si4 C29 104.4(5) . . ?
C30 Si4 C31 103.0(5) . . ?
C16 N1 C15 122.8(9) . . ?
C16 N1 C17 111.9(8) . . ?
C17 N1 C15 124.8(9) . . ?
C16 N2 C18 112.3(8) . . ?
C16 N2 C19 124.5(8) . . ?
C18 N2 C19 123.1(8) . . ?
Si1 N3 Nd1 117.0(4) . . ?
Si2 N3 Nd1 125.3(5) . . ?
Si2 N3 Si1 117.6(5) . . ?
Si3 N4 Nd1 107.0(4) . . ?
Si3 N4 Si4 118.1(5) . . ?
Si4 N4 Nd1 134.5(4) . . ?
C2 C1 Nd1 76.6(5) . . ?
C2 C1 C14 126.8(8) . . ?
C13 C1 Nd1 81.9(5) . . ?
C13 C1 C2 106.5(8) . . ?
C13 C1 C14 125.0(8) . . ?
C14 C1 Nd1 119.5(6) . . ?
C1 C2 Nd1 74.5(5) . . ?
C1 C2 C7 108.8(8) . . ?
C3 C2 Nd1 114.7(6) . . ?
C3 C2 C1 132.1(9) . . ?
C3 C2 C7 119.1(9) . . ?
C7 C2 Nd1 78.6(5) . . ?
C2 C3 H3 120.5 . . ?
C4 C3 C2 119.0(10) . . ?
C4 C3 H3 120.5 . . ?
C3 C4 H4 119.0 . . ?
C3 C4 C5 122.1(9) . . ?
C5 C4 H4 119.0 . . ?
C4 C5 H5 120.2 . . ?
C6 C5 C4 119.5(9) . . ?
C6 C5 H5 120.2 . . ?
C5 C6 H6 119.8 . . ?
C5 C6 C7 120.4(9) . . ?
C7 C6 H6 119.8 . . ?
C2 C7 Nd1 73.0(5) . . ?
C2 C7 C8 107.8(8) . . ?
C6 C7 Nd1 120.6(6) . . ?
C6 C7 C2 119.8(8) . . ?
C6 C7 C8 131.9(8) . . ?
C8 C7 Nd1 78.4(5) . . ?
C7 C8 Nd1 73.8(5) . . ?
C9 C8 Nd1 122.4(6) . . ?
C9 C8 C7 133.2(9) . . ?
C9 C8 C13 119.4(9) . . ?
C13 C8 Nd1 75.9(5) . . ?
C13 C8 C7 106.9(8) . . ?
C8 C9 H9 120.4 . . ?
C10 C9 C8 119.3(9) . . ?
C10 C9 H9 120.4 . . ?
C9 C10 H10 119.1 . . ?
C9 C10 C11 121.7(9) . . ?
C11 C10 H10 119.1 . . ?
C10 C11 H11 119.7 . . ?
C12 C11 C10 120.7(9) . . ?
C12 C11 H11 119.7 . . ?
C11 C12 H12 120.5 . . ?
C11 C12 C13 118.9(9) . . ?
C13 C12 H12 120.5 . . ?
C1 C13 Nd1 70.1(5) . . ?
C1 C13 C8 109.7(8) . . ?
C8 C13 Nd1 76.6(5) . . ?
C12 C13 Nd1 121.4(5) . . ?
C12 C13 C1 130.3(9) . . ?
C12 C13 C8 120.0(9) . . ?
C1 C14 H14A 108.7 . . ?
C1 C14 H14B 108.7 . . ?
C1 C14 C15 114.1(8) . . ?
H14A C14 H14B 107.6 . . ?
C15 C14 H14A 108.7 . . ?
C15 C14 H14B 108.7 . . ?
N1 C15 C14 112.8(9) . . ?
N1 C15 H15A 109.0 . . ?
N1 C15 H15B 109.0 . . ?
C14 C15 H15A 109.0 . . ?
C14 C15 H15B 109.0 . . ?
H15A C15 H15B 107.8 . . ?
N1 C16 Nd1 123.8(6) . . ?
N2 C16 Nd1 130.8(7) . . ?
N2 C16 N1 103.5(8) . . ?
N1 C17 H17 127.2 . . ?
C18 C17 N1 105.5(9) . . ?
C18 C17 H17 127.2 . . ?
N2 C18 H18 126.6 . . ?
C17 C18 N2 106.7(8) . . ?
C17 C18 H18 126.6 . . ?
N2 C19 H19A 109.5 . . ?
N2 C19 H19B 109.5 . . ?
N2 C19 H19C 109.5 . . ?
H19A C19 H19B 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
Si1 C20 H20A 109.5 . . ?
Si1 C20 H20B 109.5 . . ?
Si1 C20 H20C 109.5 . . ?
H20A C20 H20B 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
Si1 C21 H21A 109.5 . . ?
Si1 C21 H21B 109.5 . . ?
Si1 C21 H21C 109.5 . . ?
H21A C21 H21B 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
Si1 C22 H22A 109.5 . . ?
Si1 C22 H22B 109.5 . . ?
Si1 C22 H22C 109.5 . . ?
H22A C22 H22B 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
Si2 C23 H23A 109.5 . . ?
Si2 C23 H23B 109.5 . . ?
Si2 C23 H23C 109.5 . . ?
H23A C23 H23B 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
Si2 C24 H24A 109.5 . . ?
Si2 C24 H24B 109.5 . . ?
Si2 C24 H24C 109.5 . . ?
H24A C24 H24B 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
Si2 C25 H25A 109.5 . . ?
Si2 C25 H25B 109.5 . . ?
Si2 C25 H25C 109.5 . . ?
H25A C25 H25B 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 109.5 . . ?
Si3 C26 H26A 109.5 . . ?
Si3 C26 H26B 109.5 . . ?
Si3 C26 H26C 109.5 . . ?
H26A C26 H26B 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
Si3 C27 H27A 109.5 . . ?
Si3 C27 H27B 109.5 . . ?
Si3 C27 H27C 109.5 . . ?
H27A C27 H27B 109.5 . . ?
H27A C27 H27C 109.5 . . ?
H27B C27 H27C 109.5 . . ?
Si3 C28 H28A 109.5 . . ?
Si3 C28 H28B 109.5 . . ?
Si3 C28 H28C 109.5 . . ?
H28A C28 H28B 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
Si4 C29 H29A 109.5 . . ?
Si4 C29 H29B 109.5 . . ?
Si4 C29 H29C 109.5 . . ?
H29A C29 H29B 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
Si4 C30 H30A 109.5 . . ?
Si4 C30 H30B 109.5 . . ?
Si4 C30 H30C 109.5 . . ?
H30A C30 H30B 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
Si4 C31 H31A 109.5 . . ?
Si4 C31 H31B 109.5 . . ?
Si4 C31 H31C 109.5 . . ?
H31A C31 H31B 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 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
Nd1 Si3 N4 Si4 -173.4(8) . . . . ?
Nd1 C1 C2 C3 -109.5(10) . . . . ?
Nd1 C1 C2 C7 71.9(6) . . . . ?
Nd1 C1 C13 C8 -67.0(6) . . . . ?
Nd1 C1 C13 C12 114.8(9) . . . . ?
Nd1 C1 C14 C15 -16.6(11) . . . . ?
Nd1 C2 C3 C4 93.9(9) . . . . ?
Nd1 C2 C7 C6 -116.0(8) . . . . ?
Nd1 C2 C7 C8 71.4(6) . . . . ?
Nd1 C7 C8 C9 -119.4(11) . . . . ?
Nd1 C7 C8 C13 69.4(6) . . . . ?
Nd1 C8 C9 C10 90.2(10) . . . . ?
Nd1 C8 C13 C1 62.8(6) . . . . ?
Nd1 C8 C13 C12 -118.7(7) . . . . ?
N1 C17 C18 N2 0.6(11) . . . . ?
C1 C2 C3 C4 -175.0(9) . . . . ?
C1 C2 C7 Nd1 -69.1(6) . . . . ?
C1 C2 C7 C6 174.9(8) . . . . ?
C1 C2 C7 C8 2.3(10) . . . . ?
C1 C14 C15 N1 -55.3(13) . . . . ?
C2 C1 C13 Nd1 73.4(6) . . . . ?
C2 C1 C13 C8 6.4(9) . . . . ?
C2 C1 C13 C12 -171.8(9) . . . . ?
C2 C1 C14 C15 -111.8(11) . . . . ?
C2 C3 C4 C5 -1.2(14) . . . . ?
C2 C7 C8 Nd1 -67.7(6) . . . . ?
C2 C7 C8 C9 172.9(10) . . . . ?
C2 C7 C8 C13 1.7(9) . . . . ?
C3 C2 C7 Nd1 112.1(8) . . . . ?
C3 C2 C7 C6 -3.8(12) . . . . ?
C3 C2 C7 C8 -176.5(8) . . . . ?
C3 C4 C5 C6 -0.7(15) . . . . ?
C4 C5 C6 C7 0.3(14) . . . . ?
C5 C6 C7 Nd1 -85.0(9) . . . . ?
C5 C6 C7 C2 2.0(13) . . . . ?
C5 C6 C7 C8 172.5(9) . . . . ?
C6 C7 C8 Nd1 120.9(10) . . . . ?
C6 C7 C8 C9 1.5(17) . . . . ?
C6 C7 C8 C13 -169.8(9) . . . . ?
C7 C2 C3 C4 3.4(13) . . . . ?
C7 C8 C9 C10 -171.7(10) . . . . ?
C7 C8 C13 Nd1 -67.9(6) . . . . ?
C7 C8 C13 C1 -5.0(10) . . . . ?
C7 C8 C13 C12 173.4(8) . . . . ?
C8 C9 C10 C11 1.6(15) . . . . ?
C9 C8 C13 Nd1 119.5(8) . . . . ?
C9 C8 C13 C1 -177.7(8) . . . . ?
C9 C8 C13 C12 0.7(13) . . . . ?
C9 C10 C11 C12 -1.1(16) . . . . ?
C10 C11 C12 C13 0.4(14) . . . . ?
C11 C12 C13 Nd1 -92.5(9) . . . . ?
C11 C12 C13 C1 177.8(9) . . . . ?
C11 C12 C13 C8 -0.3(13) . . . . ?
C13 C1 C2 Nd1 -77.2(6) . . . . ?
C13 C1 C2 C3 173.2(9) . . . . ?
C13 C1 C2 C7 -5.3(9) . . . . ?
C13 C1 C14 C15 84.9(12) . . . . ?
C13 C8 C9 C10 -1.4(14) . . . . ?
C14 C1 C2 Nd1 117.0(9) . . . . ?
C14 C1 C2 C3 7.4(16) . . . . ?
C14 C1 C2 C7 -171.1(9) . . . . ?
C14 C1 C13 Nd1 -120.5(9) . . . . ?
C14 C1 C13 C8 172.5(8) . . . . ?
C14 C1 C13 C12 -5.7(15) . . . . ?
C15 N1 C16 Nd1 -6.7(14) . . . . ?
C15 N1 C16 N2 -172.5(9) . . . . ?
C15 N1 C17 C18 172.0(10) . . . . ?
C16 N1 C15 C14 76.5(14) . . . . ?
C16 N1 C17 C18 -0.4(12) . . . . ?
C16 N2 C18 C17 -0.6(11) . . . . ?
C17 N1 C15 C14 -95.0(12) . . . . ?
C17 N1 C16 Nd1 165.8(7) . . . . ?
C17 N1 C16 N2 0.0(11) . . . . ?
C18 N2 C16 Nd1 -164.0(7) . . . . ?
C18 N2 C16 N1 0.4(11) . . . . ?
C19 N2 C16 Nd1 12.1(13) . . . . ?
C19 N2 C16 N1 176.6(9) . . . . ?
C19 N2 C18 C17 -176.9(9) . . . . ?
C20 Si1 N3 Nd1 15.3(6) . . . . ?
C20 Si1 N3 Si2 -166.3(5) . . . . ?
C21 Si1 N3 Nd1 133.1(5) . . . . ?
C21 Si1 N3 Si2 -48.5(7) . . . . ?
C22 Si1 N3 Nd1 -104.5(5) . . . . ?
C22 Si1 N3 Si2 73.9(6) . . . . ?
C23 Si2 N3 Nd1 -89.7(6) . . . . ?
C23 Si2 N3 Si1 92.1(5) . . . . ?
C24 Si2 N3 Nd1 148.8(5) . . . . ?
C24 Si2 N3 Si1 -29.4(7) . . . . ?
C25 Si2 N3 Nd1 31.3(6) . . . . ?
C25 Si2 N3 Si1 -146.9(5) . . . . ?
C26 Si3 N4 Nd1 -0.1(5) . . . . ?
C26 Si3 N4 Si4 -173.5(5) . . . . ?
C27 Si3 N4 Nd1 -116.8(5) . . . . ?
C27 Si3 N4 Si4 69.8(7) . . . . ?
C28 Si3 N4 Nd1 117.8(4) . . . . ?
C28 Si3 N4 Si4 -55.6(7) . . . . ?
C29 Si4 N4 Nd1 -83.8(7) . . . . ?
C29 Si4 N4 Si3 87.4(6) . . . . ?
C30 Si4 N4 Nd1 157.5(6) . . . . ?
C30 Si4 N4 Si3 -31.3(7) . . . . ?
C31 Si4 N4 Nd1 39.8(8) . . . . ?
C31 Si4 N4 Si3 -149.0(6) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.858(7)
2 0.0004(9)
3 0.142(7)
4 -0.0000(9)



# start Validation Reply Form
_vrf_PLAT097_5_LaLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       9.95 eA-3  
RESPONSE: The structures for all LnLN2 compounds (Ln = La, Ce and Nd in this 
paper, Ln = La in P-1 in a previous paper) all feature large Q peaks. This 
is despite crystallising in several different space groups (Ln = La in this 
paper: Pca21, Ln = Ce: P 21/c, Ln = Nd: Pca21). We have looked for 
non-merohedral twinning, but have not been able to model the data any better 
than that presented here. We have used Cu radiation, which although not ideal 
for heavy atoms, has worked satisfactorily with small crystals of other rare 
earth complexes (for example, the Ce Br bridged structure in this paper, the 
Nd Br bridged structure in a previous paper), so believe the problem is 
inherent with the way this class of compounds crystallise. 
;
_vrf_PLAT971_6_CeLN2             
;
PROBLEM: Check Calcd Resid. Dens.  1.32Ang From Ce1             7.88 eA-3  
RESPONSE: Please see response to 5_LaN2. We believe that it is mostly 
likely due to a small amount of residual, unmodelled twinning. We have 
checked our absorption correction and we have used Cu radiation 
successfully for other rare earth structures.
;
_vrf_PLAT094_6_CeLN2             
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       4.82 Report
RESPONSE: Please see above.
;
_vrf_PLAT097_6_CeLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       7.72 eA-3  
RESPONSE: Please see above response.
;
_vrf_PLAT097_7_NdLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       6.37 eA-3  
RESPONSE: RESPONSE: Please see response to 5_LaN2. We believe that it is mostly 
likely due to a small amount of residual, unmodelled twinning. We have 
checked our absorption correction and we have used Cu radiation 
successfully for other rare earth structures.
;
# 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_5_LaLN2
_database_code_depnum_ccdc_archive 'CCDC 2401177'
loop_
_audit_author_name
_audit_author_address
'Stephen Mansell'
;Heriot Watt University
United Kingdom
;
_audit_update_record             
;
2025-08-11 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_audit_creation_date             2024-09-01
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C31 H53 La N4 Si4'
_chemical_formula_sum            'C31 H53 La N4 Si4'
_chemical_formula_weight         733.04
_chemical_absolute_configuration ?
_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 0.0181 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'
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'
Si Si 0.2541 0.3302 '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      orthorhombic
_space_group_IT_number           29
_space_group_name_H-M_alt        'P c a 21'
_space_group_name_Hall           'P 2c -2ac'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'x+1/2, -y, z'
'-x+1/2, y, z+1/2'

_cell_length_a                   12.9434(2)
_cell_length_b                   16.4994(2)
_cell_length_c                   16.8840(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3605.72(8)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9915
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      74.316
_cell_measurement_theta_min      6.812
_shelx_estimated_absorpt_T_max   0.301
_shelx_estimated_absorpt_T_min   0.250
_exptl_absorpt_coefficient_mu    10.616
_exptl_absorpt_correction_T_max  0.7538
_exptl_absorpt_correction_T_min  0.5212
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1072 before and 0.0558 after correction.
The Ratio of minimum to maximum transmission is 0.6914.
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    1.350
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.167
_exptl_crystal_size_min          0.149
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            80345
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.986
_diffrn_reflns_theta_min         2.617
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       ?
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_reflns_Friedel_coverage         0.927
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                6715
_reflns_number_total             7433
_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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker Apex4 v2022.10-0 (Bruker, 2022)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'XT (Sheldrick, 2015)'
_refine_diff_density_max         9.955
_refine_diff_density_min         -2.790
_refine_diff_density_rms         0.599
_refine_ls_abs_structure_details 
;
 Twinning involves inversion, so Flack parameter cannot be determined
;
_refine_ls_abs_structure_Flack   ?
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         7433
_refine_ls_number_restraints     13
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0704
_refine_ls_restrained_S_all      1.058
_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)+(0.1397P)²+9.8308P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1775
_refine_ls_wR_factor_ref         0.1833
_refine_special_details          
;
 Refined as a 4-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.628(10)
 0.0014(19) 0.370(10) 0.0008(19)
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. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C17(H17), C18(H18)
4.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C27(H27C,H27A,H27B), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_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
La1 La 0.46212(4) 0.73742(3) 0.70136(6) 0.0110(2) Uani 1 1 d . . . . .
Si1 Si 0.5578(3) 0.6854(2) 0.8974(2) 0.0180(7) Uani 1 1 d . . . . .
N1 N 0.5487(8) 0.6493(7) 0.5178(7) 0.019(2) Uani 1 1 d . . . . .
C1 C 0.3430(9) 0.6346(6) 0.5980(7) 0.014(2) Uani 1 1 d . . . . .
Si2 Si 0.6872(2) 0.79652(18) 0.80064(19) 0.0173(6) Uani 1 1 d . . . . .
N2 N 0.6582(8) 0.6093(6) 0.6047(6) 0.0174(19) Uani 1 1 d . . . . .
C2 C 0.2657(8) 0.6753(7) 0.6463(8) 0.016(2) Uani 1 1 d . U . . .
Si3 Si 0.3733(2) 0.92400(18) 0.71678(19) 0.0193(7) Uani 1 1 d . . . . .
N3 N 0.5761(9) 0.7372(6) 0.8097(7) 0.018(2) Uani 1 1 d . . . . .
C3 C 0.1889(10) 0.7368(6) 0.6267(8) 0.020(3) Uani 1 1 d . . . . .
H3 H 0.186080 0.760270 0.575359 0.024 Uiso 1 1 calc R . . . .
Si4 Si 0.4614(2) 0.9102(2) 0.5554(2) 0.0206(7) Uani 1 1 d . . . . .
N4 N 0.4390(9) 0.8678(7) 0.6488(7) 0.023(2) Uani 1 1 d . . . . .
C4 C 0.1215(10) 0.7594(7) 0.6843(9) 0.025(4) Uani 1 1 d . . . . .
H4 H 0.072023 0.799953 0.671776 0.030 Uiso 1 1 calc R . . . .
C5 C 0.1203(9) 0.7262(8) 0.7626(8) 0.020(2) Uani 1 1 d . . . . .
H5 H 0.070306 0.743488 0.800193 0.024 Uiso 1 1 calc R . . . .
C6 C 0.1942(8) 0.6679(7) 0.7826(8) 0.019(2) Uani 1 1 d . . . . .
H6 H 0.195165 0.644907 0.834236 0.023 Uiso 1 1 calc R . . . .
C7 C 0.2681(9) 0.6432(7) 0.7249(7) 0.017(2) Uani 1 1 d . . . . .
C8 C 0.3465(9) 0.5785(7) 0.7265(7) 0.017(2) Uani 1 1 d . . . . .
C9 C 0.3752(9) 0.5221(6) 0.7858(7) 0.016(2) Uani 1 1 d . . . . .
H9 H 0.347525 0.525824 0.837757 0.020 Uiso 1 1 calc R . . . .
C10 C 0.4448(10) 0.4612(8) 0.7661(8) 0.019(2) Uani 1 1 d . . . . .
H10 H 0.466842 0.424123 0.805636 0.022 Uiso 1 1 calc R . . . .
C11 C 0.4838(10) 0.4535(7) 0.6869(8) 0.021(3) Uani 1 1 d . . . . .
H11 H 0.528587 0.409888 0.673935 0.025 Uiso 1 1 calc R . . . .
C12 C 0.4567(8) 0.5094(7) 0.6291(7) 0.012(2) Uani 1 1 d . . . . .
H12 H 0.485200 0.505652 0.577411 0.015 Uiso 1 1 calc R . . . .
C13 C 0.3859(9) 0.5722(6) 0.6479(7) 0.013(2) Uani 1 1 d . . . . .
C14 C 0.3575(10) 0.6413(7) 0.5097(7) 0.019(2) Uani 1 1 d . . . . .
H14A H 0.297080 0.670007 0.487130 0.023 Uiso 1 1 calc R . . . .
H14B H 0.358499 0.586054 0.486954 0.023 Uiso 1 1 calc R . . . .
C15 C 0.4555(8) 0.6855(8) 0.4838(8) 0.018(3) Uani 1 1 d . . . . .
H15A H 0.460467 0.684150 0.425341 0.022 Uiso 1 1 calc R . . . .
H15B H 0.451052 0.742998 0.500363 0.022 Uiso 1 1 calc R . . . .
C16 C 0.5759(9) 0.6604(7) 0.5953(7) 0.017(2) Uani 1 1 d . U . . .
C17 C 0.6104(10) 0.5919(8) 0.4813(8) 0.021(3) Uani 1 1 d . . . . .
H17 H 0.605905 0.574015 0.427932 0.025 Uiso 1 1 calc R . . . .
C18 C 0.6787(10) 0.5662(8) 0.5373(8) 0.025(3) Uani 1 1 d . . . . .
H18 H 0.730656 0.526053 0.530741 0.030 Uiso 1 1 calc R . . . .
C19 C 0.7112(11) 0.5965(8) 0.6792(8) 0.031(3) Uani 1 1 d . . . . .
H19A H 0.704407 0.539623 0.694954 0.047 Uiso 1 1 calc GR . . . .
H19B H 0.680550 0.631297 0.719931 0.047 Uiso 1 1 calc GR . . . .
H19C H 0.784486 0.610023 0.672992 0.047 Uiso 1 1 calc GR . . . .
C20 C 0.4160(10) 0.6776(9) 0.9217(8) 0.025(3) Uani 1 1 d . . . . .
H20A H 0.405812 0.637031 0.963304 0.037 Uiso 1 1 calc GR . . . .
H20B H 0.377673 0.661501 0.874159 0.037 Uiso 1 1 calc GR . . . .
H20C H 0.390799 0.730348 0.940161 0.037 Uiso 1 1 calc GR . . . .
C21 C 0.6133(10) 0.5798(8) 0.8915(8) 0.024(3) Uani 1 1 d . . . . .
H21A H 0.606715 0.553222 0.943108 0.036 Uiso 1 1 calc GR . . . .
H21B H 0.686432 0.582908 0.876717 0.036 Uiso 1 1 calc GR . . . .
H21C H 0.575595 0.548538 0.851490 0.036 Uiso 1 1 calc GR . . . .
C22 C 0.6147(13) 0.7329(8) 0.9907(9) 0.031(3) Uani 1 1 d . . . . .
H22A H 0.595748 0.700166 1.036856 0.046 Uiso 1 1 calc GR . . . .
H22B H 0.587510 0.787963 0.997071 0.046 Uiso 1 1 calc GR . . . .
H22C H 0.690148 0.735076 0.986033 0.046 Uiso 1 1 calc GR . . . .
C23 C 0.8122(12) 0.7444(8) 0.8312(9) 0.026(3) Uani 1 1 d . . . . .
H23A H 0.870129 0.782066 0.824712 0.039 Uiso 1 1 calc GR . . . .
H23B H 0.823374 0.696566 0.797910 0.039 Uiso 1 1 calc GR . . . .
H23C H 0.807467 0.727746 0.886831 0.039 Uiso 1 1 calc GR . . . .
C24 C 0.6781(11) 0.8928(8) 0.8599(8) 0.027(3) Uani 1 1 d . . . . .
H24A H 0.740249 0.925517 0.851203 0.041 Uiso 1 1 calc GR . . . .
H24B H 0.672172 0.879550 0.916339 0.041 Uiso 1 1 calc GR . . . .
H24C H 0.617078 0.923528 0.843173 0.041 Uiso 1 1 calc GR . . . .
C25 C 0.7067(9) 0.8263(6) 0.6948(10) 0.024(2) Uani 1 1 d . . . . .
H25A H 0.766806 0.862145 0.690639 0.036 Uiso 1 1 calc GR . . . .
H25B H 0.645117 0.854753 0.675500 0.036 Uiso 1 1 calc GR . . . .
H25C H 0.718252 0.777655 0.662684 0.036 Uiso 1 1 calc GR . . . .
C26 C 0.2450(10) 0.9592(7) 0.6781(9) 0.032(4) Uani 1 1 d . . . . .
H26A H 0.200873 0.975327 0.722544 0.047 Uiso 1 1 calc GR . . . .
H26B H 0.211862 0.915073 0.648748 0.047 Uiso 1 1 calc GR . . . .
H26C H 0.255349 1.005664 0.642788 0.047 Uiso 1 1 calc GR . . . .
C27 C 0.3472(10) 0.8574(8) 0.8052(9) 0.028(3) Uani 1 1 d . . . . .
H27C H 0.304422 0.886897 0.843452 0.042 Uiso 1 1 calc GR . . . .
H27A H 0.412768 0.842212 0.830092 0.042 Uiso 1 1 calc GR . . . .
H27B H 0.310712 0.808366 0.788031 0.042 Uiso 1 1 calc GR . . . .
C28 C 0.4465(11) 1.0147(8) 0.7586(9) 0.024(3) Uani 1 1 d . . . . .
H28A H 0.413191 1.064971 0.741088 0.036 Uiso 1 1 calc GR . . . .
H28B H 0.518039 1.013587 0.739638 0.036 Uiso 1 1 calc GR . . . .
H28C H 0.445897 1.012265 0.816603 0.036 Uiso 1 1 calc GR . . . .
C29 C 0.4747(11) 1.0244(9) 0.5579(11) 0.032(3) Uani 1 1 d . . . . .
H29A H 0.484586 1.044826 0.503919 0.048 Uiso 1 1 calc GR . . . .
H29B H 0.534356 1.039286 0.590516 0.048 Uiso 1 1 calc GR . . . .
H29C H 0.411934 1.048253 0.580540 0.048 Uiso 1 1 calc GR . . . .
C30 C 0.3506(11) 0.8913(9) 0.4852(9) 0.030(3) Uani 1 1 d . . . . .
H30A H 0.371074 0.906732 0.431390 0.044 Uiso 1 1 calc GR . . . .
H30B H 0.290770 0.923583 0.501555 0.044 Uiso 1 1 calc GR . . . .
H30C H 0.332366 0.833614 0.486145 0.044 Uiso 1 1 calc GR . . . .
C31 C 0.5861(11) 0.8747(10) 0.5076(9) 0.031(3) Uani 1 1 d . . . . .
H31A H 0.580551 0.879939 0.449902 0.046 Uiso 1 1 calc GR . . . .
H31B H 0.598481 0.817834 0.521399 0.046 Uiso 1 1 calc GR . . . .
H31C H 0.643643 0.907964 0.526679 0.046 Uiso 1 1 calc GR . . . .


_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 C1 2.881(11) . ?
La1 C2 2.894(11) . ?
La1 Si3 3.297(3) . ?
La1 N3 2.351(12) . ?
La1 N4 2.346(11) . ?
La1 C7 2.980(11) . ?
La1 C8 3.048(11) . ?
La1 C13 3.036(10) . ?
La1 C16 2.644(12) . ?
Si1 N3 1.725(11) . ?
Si1 C20 1.885(14) . ?
Si1 C21 1.886(14) . ?
Si1 C22 1.908(15) . ?
N1 C15 1.463(15) . ?
N1 C16 1.367(17) . ?
N1 C17 1.384(16) . ?
C1 C2 1.455(15) . ?
C1 C13 1.442(15) . ?
C1 C14 1.506(16) . ?
Si2 N3 1.746(11) . ?
Si2 C23 1.904(15) . ?
Si2 C24 1.882(14) . ?
Si2 C25 1.871(16) . ?
N2 C16 1.367(14) . ?
N2 C18 1.368(15) . ?
N2 C19 1.447(17) . ?
C2 C3 1.459(16) . ?
C2 C7 1.429(17) . ?
Si3 N4 1.704(11) . ?
Si3 C26 1.876(13) . ?
Si3 C27 1.885(14) . ?
Si3 C28 1.908(14) . ?
C3 H3 0.9500 . ?
C3 C4 1.36(2) . ?
Si4 N4 1.750(13) . ?
Si4 C29 1.893(15) . ?
Si4 C30 1.887(14) . ?
Si4 C31 1.897(15) . ?
C4 H4 0.9500 . ?
C4 C5 1.43(2) . ?
C5 H5 0.9500 . ?
C5 C6 1.399(17) . ?
C6 H6 0.9500 . ?
C6 C7 1.426(16) . ?
C7 C8 1.473(17) . ?
C8 C9 1.416(16) . ?
C8 C13 1.427(17) . ?
C9 H9 0.9500 . ?
C9 C10 1.390(18) . ?
C10 H10 0.9500 . ?
C10 C11 1.435(18) . ?
C11 H11 0.9500 . ?
C11 C12 1.388(18) . ?
C12 H12 0.9500 . ?
C12 C13 1.418(16) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C14 C15 1.527(17) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C17 H17 0.9500 . ?
C17 C18 1.362(19) . ?
C18 H18 0.9500 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
C24 H24A 0.9800 . ?
C24 H24B 0.9800 . ?
C24 H24C 0.9800 . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 0.9800 . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?
C26 H26C 0.9800 . ?
C27 H27C 0.9800 . ?
C27 H27A 0.9800 . ?
C27 H27B 0.9800 . ?
C28 H28A 0.9800 . ?
C28 H28B 0.9800 . ?
C28 H28C 0.9800 . ?
C29 H29A 0.9800 . ?
C29 H29B 0.9800 . ?
C29 H29C 0.9800 . ?
C30 H30A 0.9800 . ?
C30 H30B 0.9800 . ?
C30 H30C 0.9800 . ?
C31 H31A 0.9800 . ?
C31 H31B 0.9800 . ?
C31 H31C 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
C1 La1 C2 29.2(3) . . ?
C1 La1 Si3 114.3(2) . . ?
C1 La1 C7 47.4(3) . . ?
C1 La1 C8 46.8(3) . . ?
C1 La1 C13 28.1(3) . . ?
C2 La1 Si3 92.8(2) . . ?
C2 La1 C7 28.1(3) . . ?
C2 La1 C8 46.3(3) . . ?
C2 La1 C13 45.7(3) . . ?
N3 La1 C1 143.8(3) . . ?
N3 La1 C2 143.2(4) . . ?
N3 La1 Si3 99.2(2) . . ?
N3 La1 C7 115.1(3) . . ?
N3 La1 C8 101.4(3) . . ?
N3 La1 C13 115.7(3) . . ?
N3 La1 C16 100.2(4) . . ?
N4 La1 C1 104.0(3) . . ?
N4 La1 C2 95.2(4) . . ?
N4 La1 Si3 29.5(3) . . ?
N4 La1 N3 112.1(4) . . ?
N4 La1 C7 114.9(4) . . ?
N4 La1 C8 141.1(4) . . ?
N4 La1 C13 132.0(4) . . ?
N4 La1 C16 104.8(4) . . ?
C7 La1 Si3 100.5(2) . . ?
C7 La1 C8 28.3(3) . . ?
C7 La1 C13 45.4(3) . . ?
C8 La1 Si3 128.4(2) . . ?
C13 La1 Si3 138.5(2) . . ?
C13 La1 C8 27.1(3) . . ?
C16 La1 C1 66.7(4) . . ?
C16 La1 C2 95.8(4) . . ?
C16 La1 Si3 134.2(2) . . ?
C16 La1 C7 108.0(3) . . ?
C16 La1 C8 87.4(3) . . ?
C16 La1 C13 63.1(3) . . ?
N3 Si1 C20 110.7(6) . . ?
N3 Si1 C21 111.1(5) . . ?
N3 Si1 C22 116.8(6) . . ?
C20 Si1 C21 108.6(6) . . ?
C20 Si1 C22 103.0(7) . . ?
C21 Si1 C22 106.1(6) . . ?
C16 N1 C15 122.3(11) . . ?
C16 N1 C17 111.6(10) . . ?
C17 N1 C15 125.5(12) . . ?
C2 C1 La1 75.9(6) . . ?
C2 C1 C14 127.3(10) . . ?
C13 C1 La1 82.0(6) . . ?
C13 C1 C2 105.4(10) . . ?
C13 C1 C14 125.7(10) . . ?
C14 C1 La1 119.3(7) . . ?
N3 Si2 C23 115.0(6) . . ?
N3 Si2 C24 112.0(5) . . ?
N3 Si2 C25 110.0(5) . . ?
C24 Si2 C23 106.9(6) . . ?
C25 Si2 C23 105.3(6) . . ?
C25 Si2 C24 107.2(6) . . ?
C16 N2 C18 112.0(10) . . ?
C16 N2 C19 124.0(10) . . ?
C18 N2 C19 123.7(10) . . ?
C1 C2 La1 74.9(6) . . ?
C1 C2 C3 131.5(12) . . ?
C3 C2 La1 115.2(7) . . ?
C7 C2 La1 79.3(7) . . ?
C7 C2 C1 109.6(10) . . ?
C7 C2 C3 118.9(11) . . ?
N4 Si3 C26 112.1(6) . . ?
N4 Si3 C27 107.8(6) . . ?
N4 Si3 C28 115.4(6) . . ?
C26 Si3 C27 107.3(6) . . ?
C26 Si3 C28 109.0(6) . . ?
C27 Si3 C28 104.7(6) . . ?
Si1 N3 La1 125.6(6) . . ?
Si1 N3 Si2 117.8(7) . . ?
Si2 N3 La1 116.6(5) . . ?
C2 C3 H3 121.1 . . ?
C4 C3 C2 117.8(12) . . ?
C4 C3 H3 121.1 . . ?
N4 Si4 C29 113.2(7) . . ?
N4 Si4 C30 111.9(6) . . ?
N4 Si4 C31 113.7(6) . . ?
C29 Si4 C31 103.9(7) . . ?
C30 Si4 C29 104.3(6) . . ?
C30 Si4 C31 109.2(7) . . ?
Si3 N4 La1 107.9(6) . . ?
Si3 N4 Si4 118.2(6) . . ?
Si4 N4 La1 133.4(6) . . ?
C3 C4 H4 117.9 . . ?
C3 C4 C5 124.3(11) . . ?
C5 C4 H4 117.9 . . ?
C4 C5 H5 120.7 . . ?
C6 C5 C4 118.6(12) . . ?
C6 C5 H5 120.7 . . ?
C5 C6 H6 120.3 . . ?
C5 C6 C7 119.3(12) . . ?
C7 C6 H6 120.3 . . ?
C2 C7 La1 72.6(6) . . ?
C2 C7 C8 107.5(10) . . ?
C6 C7 La1 120.5(8) . . ?
C6 C7 C2 121.0(11) . . ?
C6 C7 C8 131.0(10) . . ?
C8 C7 La1 78.5(6) . . ?
C7 C8 La1 73.3(6) . . ?
C9 C8 La1 122.4(8) . . ?
C9 C8 C7 132.1(11) . . ?
C9 C8 C13 121.1(11) . . ?
C13 C8 La1 76.0(6) . . ?
C13 C8 C7 106.3(10) . . ?
C8 C9 H9 120.8 . . ?
C10 C9 C8 118.4(11) . . ?
C10 C9 H9 120.8 . . ?
C9 C10 H10 119.5 . . ?
C9 C10 C11 121.0(11) . . ?
C11 C10 H10 119.5 . . ?
C10 C11 H11 119.8 . . ?
C12 C11 C10 120.5(11) . . ?
C12 C11 H11 119.8 . . ?
C11 C12 H12 120.3 . . ?
C11 C12 C13 119.5(11) . . ?
C13 C12 H12 120.3 . . ?
C1 C13 La1 70.0(6) . . ?
C8 C13 La1 76.9(6) . . ?
C8 C13 C1 110.8(10) . . ?
C12 C13 La1 120.8(7) . . ?
C12 C13 C1 129.8(11) . . ?
C12 C13 C8 119.5(11) . . ?
C1 C14 H14A 108.5 . . ?
C1 C14 H14B 108.5 . . ?
C1 C14 C15 114.9(10) . . ?
H14A C14 H14B 107.5 . . ?
C15 C14 H14A 108.5 . . ?
C15 C14 H14B 108.5 . . ?
N1 C15 C14 112.2(11) . . ?
N1 C15 H15A 109.2 . . ?
N1 C15 H15B 109.2 . . ?
C14 C15 H15A 109.2 . . ?
C14 C15 H15B 109.2 . . ?
H15A C15 H15B 107.9 . . ?
N1 C16 La1 124.6(8) . . ?
N2 C16 La1 130.7(8) . . ?
N2 C16 N1 103.3(10) . . ?
N1 C17 H17 126.9 . . ?
C18 C17 N1 106.2(11) . . ?
C18 C17 H17 126.9 . . ?
N2 C18 H18 126.6 . . ?
C17 C18 N2 106.8(11) . . ?
C17 C18 H18 126.6 . . ?
N2 C19 H19A 109.5 . . ?
N2 C19 H19B 109.5 . . ?
N2 C19 H19C 109.5 . . ?
H19A C19 H19B 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
Si1 C20 H20A 109.5 . . ?
Si1 C20 H20B 109.5 . . ?
Si1 C20 H20C 109.5 . . ?
H20A C20 H20B 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
Si1 C21 H21A 109.5 . . ?
Si1 C21 H21B 109.5 . . ?
Si1 C21 H21C 109.5 . . ?
H21A C21 H21B 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
Si1 C22 H22A 109.5 . . ?
Si1 C22 H22B 109.5 . . ?
Si1 C22 H22C 109.5 . . ?
H22A C22 H22B 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
Si2 C23 H23A 109.5 . . ?
Si2 C23 H23B 109.5 . . ?
Si2 C23 H23C 109.5 . . ?
H23A C23 H23B 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
Si2 C24 H24A 109.5 . . ?
Si2 C24 H24B 109.5 . . ?
Si2 C24 H24C 109.5 . . ?
H24A C24 H24B 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
Si2 C25 H25A 109.5 . . ?
Si2 C25 H25B 109.5 . . ?
Si2 C25 H25C 109.5 . . ?
H25A C25 H25B 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 109.5 . . ?
Si3 C26 H26A 109.5 . . ?
Si3 C26 H26B 109.5 . . ?
Si3 C26 H26C 109.5 . . ?
H26A C26 H26B 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
Si3 C27 H27C 109.5 . . ?
Si3 C27 H27A 109.5 . . ?
Si3 C27 H27B 109.5 . . ?
H27C C27 H27A 109.5 . . ?
H27C C27 H27B 109.5 . . ?
H27A C27 H27B 109.5 . . ?
Si3 C28 H28A 109.5 . . ?
Si3 C28 H28B 109.5 . . ?
Si3 C28 H28C 109.5 . . ?
H28A C28 H28B 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
Si4 C29 H29A 109.5 . . ?
Si4 C29 H29B 109.5 . . ?
Si4 C29 H29C 109.5 . . ?
H29A C29 H29B 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
Si4 C30 H30A 109.5 . . ?
Si4 C30 H30B 109.5 . . ?
Si4 C30 H30C 109.5 . . ?
H30A C30 H30B 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
Si4 C31 H31A 109.5 . . ?
Si4 C31 H31B 109.5 . . ?
Si4 C31 H31C 109.5 . . ?
H31A C31 H31B 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 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 C1 C2 C3 110.4(12) . . . . ?
La1 C1 C2 C7 -72.5(8) . . . . ?
La1 C1 C13 C8 66.7(8) . . . . ?
La1 C1 C13 C12 -114.0(11) . . . . ?
La1 C1 C14 C15 16.3(13) . . . . ?
La1 C2 C3 C4 -92.7(12) . . . . ?
La1 C2 C7 C6 115.6(10) . . . . ?
La1 C2 C7 C8 -71.4(8) . . . . ?
La1 C7 C8 C9 118.8(13) . . . . ?
La1 C7 C8 C13 -69.4(8) . . . . ?
La1 C8 C9 C10 -91.2(12) . . . . ?
La1 C8 C13 C1 -62.3(8) . . . . ?
La1 C8 C13 C12 118.2(10) . . . . ?
N1 C17 C18 N2 -1.2(14) . . . . ?
C1 C2 C3 C4 175.5(12) . . . . ?
C1 C2 C7 La1 69.6(7) . . . . ?
C1 C2 C7 C6 -174.8(10) . . . . ?
C1 C2 C7 C8 -1.8(12) . . . . ?
C1 C14 C15 N1 55.6(15) . . . . ?
C2 C1 C13 La1 -72.9(7) . . . . ?
C2 C1 C13 C8 -6.2(12) . . . . ?
C2 C1 C13 C12 173.1(11) . . . . ?
C2 C1 C14 C15 110.8(13) . . . . ?
C2 C3 C4 C5 -0.7(19) . . . . ?
C2 C7 C8 La1 67.4(7) . . . . ?
C2 C7 C8 C9 -173.8(12) . . . . ?
C2 C7 C8 C13 -2.0(12) . . . . ?
C3 C2 C7 La1 -112.9(10) . . . . ?
C3 C2 C7 C6 2.7(16) . . . . ?
C3 C2 C7 C8 175.7(10) . . . . ?
C3 C4 C5 C6 1(2) . . . . ?
C4 C5 C6 C7 -0.1(17) . . . . ?
C5 C6 C7 La1 85.1(12) . . . . ?
C5 C6 C7 C2 -2.0(17) . . . . ?
C5 C6 C7 C8 -173.1(12) . . . . ?
C6 C7 C8 La1 -120.6(12) . . . . ?
C6 C7 C8 C9 -2(2) . . . . ?
C6 C7 C8 C13 170.0(11) . . . . ?
C7 C2 C3 C4 -1.4(16) . . . . ?
C7 C8 C9 C10 172.3(12) . . . . ?
C7 C8 C13 La1 67.5(7) . . . . ?
C7 C8 C13 C1 5.2(13) . . . . ?
C7 C8 C13 C12 -174.3(10) . . . . ?
C8 C9 C10 C11 -2.4(18) . . . . ?
C9 C8 C13 La1 -119.6(11) . . . . ?
C9 C8 C13 C1 178.1(10) . . . . ?
C9 C8 C13 C12 -1.4(17) . . . . ?
C9 C10 C11 C12 3(2) . . . . ?
C10 C11 C12 C13 -3.0(18) . . . . ?
C11 C12 C13 La1 94.1(12) . . . . ?
C11 C12 C13 C1 -177.2(11) . . . . ?
C11 C12 C13 C8 2.1(16) . . . . ?
C13 C1 C2 La1 77.4(7) . . . . ?
C13 C1 C2 C3 -172.2(11) . . . . ?
C13 C1 C2 C7 4.9(12) . . . . ?
C13 C1 C14 C15 -85.6(14) . . . . ?
C13 C8 C9 C10 1.5(17) . . . . ?
C14 C1 C2 La1 -116.4(11) . . . . ?
C14 C1 C2 C3 -6(2) . . . . ?
C14 C1 C2 C7 171.1(11) . . . . ?
C14 C1 C13 La1 120.5(12) . . . . ?
C14 C1 C13 C8 -172.8(11) . . . . ?
C14 C1 C13 C12 6.6(19) . . . . ?
C15 N1 C16 La1 5.1(17) . . . . ?
C15 N1 C16 N2 172.8(11) . . . . ?
C15 N1 C17 C18 -171.2(12) . . . . ?
C16 N1 C15 C14 -75.4(16) . . . . ?
C16 N1 C17 C18 -0.2(15) . . . . ?
C16 N2 C18 C17 2.2(15) . . . . ?
C17 N1 C15 C14 94.6(15) . . . . ?
C17 N1 C16 La1 -166.2(8) . . . . ?
C17 N1 C16 N2 1.5(14) . . . . ?
C18 N2 C16 La1 164.3(9) . . . . ?
C18 N2 C16 N1 -2.3(13) . . . . ?
C19 N2 C16 La1 -10.2(17) . . . . ?
C19 N2 C16 N1 -176.8(11) . . . . ?
C19 N2 C18 C17 176.7(12) . . . . ?
C20 Si1 N3 La1 -31.6(8) . . . . ?
C20 Si1 N3 Si2 147.0(7) . . . . ?
C21 Si1 N3 La1 89.2(7) . . . . ?
C21 Si1 N3 Si2 -92.2(7) . . . . ?
C22 Si1 N3 La1 -148.9(7) . . . . ?
C22 Si1 N3 Si2 29.6(9) . . . . ?
C23 Si2 N3 La1 -133.4(6) . . . . ?
C23 Si2 N3 Si1 48.0(9) . . . . ?
C24 Si2 N3 La1 104.4(6) . . . . ?
C24 Si2 N3 Si1 -74.3(8) . . . . ?
C25 Si2 N3 La1 -14.7(7) . . . . ?
C25 Si2 N3 Si1 166.6(6) . . . . ?
C26 Si3 N4 La1 -117.9(6) . . . . ?
C26 Si3 N4 Si4 55.0(9) . . . . ?
C27 Si3 N4 La1 0.0(7) . . . . ?
C27 Si3 N4 Si4 172.9(7) . . . . ?
C28 Si3 N4 La1 116.5(6) . . . . ?
C28 Si3 N4 Si4 -70.5(9) . . . . ?
C29 Si4 N4 La1 -158.7(8) . . . . ?
C29 Si4 N4 Si3 30.6(9) . . . . ?
C30 Si4 N4 La1 83.7(9) . . . . ?
C30 Si4 N4 Si3 -87.0(8) . . . . ?
C31 Si4 N4 La1 -40.5(10) . . . . ?
C31 Si4 N4 Si3 148.7(7) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.628(10)
2 0.0014(19)
3 0.370(10)
4 0.0008(19)



# start Validation Reply Form
_vrf_PLAT097_5_LaLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       9.95 eA-3  
RESPONSE: The structures for all LnLN2 compounds (Ln = La, Ce and Nd in this 
paper, Ln = La in P-1 in a previous paper) all feature large Q peaks. This 
is despite crystallising in several different space groups (Ln = La in this 
paper: Pca21, Ln = Ce: P 21/c, Ln = Nd: Pca21). We have looked for 
non-merohedral twinning, but have not been able to model the data any better 
than that presented here. We have used Cu radiation, which although not ideal 
for heavy atoms, has worked satisfactorily with small crystals of other rare 
earth complexes (for example, the Ce Br bridged structure in this paper, the 
Nd Br bridged structure in a previous paper), so believe the problem is 
inherent with the way this class of compounds crystallise. 
;
_vrf_PLAT971_6_CeLN2             
;
PROBLEM: Check Calcd Resid. Dens.  1.32Ang From Ce1             7.88 eA-3  
RESPONSE: Please see response to 5_LaN2. We believe that it is mostly 
likely due to a small amount of residual, unmodelled twinning. We have 
checked our absorption correction and we have used Cu radiation 
successfully for other rare earth structures.
;
_vrf_PLAT094_6_CeLN2             
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       4.82 Report
RESPONSE: Please see above.
;
_vrf_PLAT097_6_CeLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       7.72 eA-3  
RESPONSE: Please see above response.
;
_vrf_PLAT097_7_NdLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       6.37 eA-3  
RESPONSE: RESPONSE: Please see response to 5_LaN2. We believe that it is mostly 
likely due to a small amount of residual, unmodelled twinning. We have 
checked our absorption correction and we have used Cu radiation 
successfully for other rare earth structures.
;
# 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_6_CeLN2
_database_code_depnum_ccdc_archive 'CCDC 2401178'
loop_
_audit_author_name
_audit_author_address
'Stephen Mansell'
;Heriot Watt University
United Kingdom
;
_audit_update_record             
;
2025-08-11 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_audit_creation_date             2024-08-12
_audit_creation_method           
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C31 H53 Ce N4 Si4'
_chemical_formula_sum            'C31 H53 Ce N4 Si4'
_chemical_formula_weight         734.25
_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 0.0181 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'
Ce Ce -1.8482 9.6596 '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'
Si Si 0.2541 0.3302 '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                   18.1504(6)
_cell_length_b                   11.7451(4)
_cell_length_c                   19.4041(7)
_cell_angle_alpha                90
_cell_angle_beta                 116.065(2)
_cell_angle_gamma                90
_cell_volume                     3715.8(2)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9866
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.24
_cell_measurement_theta_min      4.54
_shelx_estimated_absorpt_T_max   0.670
_shelx_estimated_absorpt_T_min   0.259
_exptl_absorpt_coefficient_mu    10.882
_exptl_absorpt_correction_T_max  0.5307
_exptl_absorpt_correction_T_min  0.2311
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1110 before and 0.0811 after correction.
The Ratio of minimum to maximum transmission is 0.4355.
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    1.312
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1524
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.04
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0685
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            90837
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.680
_diffrn_reflns_theta_min         2.710
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_source_current           1.1
_diffrn_source_power             0.055
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                6672
_reflns_number_total             7339
_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 V8.40B (?, 2016)'
_computing_data_collection       'Bruker Apex4 v2022.10-0 (Bruker, 2022)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         7.719
_refine_diff_density_min         -1.602
_refine_diff_density_rms         0.200
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     374
_refine_ls_number_reflns         7339
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0724
_refine_ls_restrained_S_all      1.062
_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)+(0.0966P)²+63.7095P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2005
_refine_ls_wR_factor_ref         0.2037
_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
2.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_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
Ce1 Ce 0.76649(2) 0.62098(4) 0.71321(2) 0.01665(16) Uani 1 1 d . . . . .
Si1 Si 0.59250(14) 0.80979(19) 0.60852(14) 0.0265(5) Uani 1 1 d . . . . .
N1 N 0.8852(4) 0.4555(6) 0.6490(4) 0.0232(14) Uani 1 1 d . . . . .
C1 C 0.9328(5) 0.6719(7) 0.7516(5) 0.0203(16) Uani 1 1 d . . . . .
Si2 Si 0.62529(13) 0.72339(19) 0.76452(13) 0.0234(5) Uani 1 1 d . . . . .
N2 N 0.7891(4) 0.4899(6) 0.5391(4) 0.0259(15) Uani 1 1 d . . . . .
C2 C 0.9238(5) 0.7212(7) 0.8151(4) 0.0203(16) Uani 1 1 d . . . . .
Si3 Si 0.79090(15) 0.35912(19) 0.83379(14) 0.0260(5) Uani 1 1 d . . . . .
N3 N 0.6499(4) 0.7320(6) 0.6893(4) 0.0217(14) Uani 1 1 d . . . . .
C3 C 0.9582(5) 0.6889(7) 0.8941(5) 0.0236(17) Uani 1 1 d . . . . .
H3 H 0.988948 0.620583 0.910973 0.028 Uiso 1 1 calc R U . . .
Si4 Si 0.67661(14) 0.36155(18) 0.66889(14) 0.0239(5) Uani 1 1 d . . . . .
N4 N 0.7476(4) 0.4334(6) 0.7481(4) 0.0225(14) Uani 1 1 d . . . . .
C4 C 0.9459(5) 0.7590(8) 0.9461(5) 0.0248(17) Uani 1 1 d . . . . .
H4 H 0.969949 0.738716 0.998857 0.030 Uiso 1 1 calc R U . . .
C5 C 0.8991(6) 0.8583(9) 0.9224(5) 0.033(2) Uani 1 1 d . . . . .
H5 H 0.891731 0.904059 0.959221 0.039 Uiso 1 1 calc R U . . .
C6 C 0.8631(5) 0.8916(7) 0.8457(5) 0.0276(18) Uani 1 1 d . . . . .
H6 H 0.831457 0.959350 0.830195 0.033 Uiso 1 1 calc R U . . .
C7 C 0.8746(5) 0.8221(7) 0.7908(5) 0.0215(16) Uani 1 1 d . . . . .
C8 C 0.8562(5) 0.8395(7) 0.7111(5) 0.0227(17) Uani 1 1 d . . . . .
C9 C 0.8178(5) 0.9315(7) 0.6616(6) 0.0301(19) Uani 1 1 d . . . . .
H9 H 0.793299 0.991246 0.677349 0.036 Uiso 1 1 calc R U . . .
C10 C 0.8164(6) 0.9335(8) 0.5909(6) 0.035(2) Uani 1 1 d . . . . .
H10 H 0.790456 0.995123 0.557227 0.042 Uiso 1 1 calc R U . . .
C11 C 0.8530(6) 0.8451(9) 0.5665(5) 0.034(2) Uani 1 1 d . . . . .
H11 H 0.852485 0.849285 0.517341 0.040 Uiso 1 1 calc R U . . .
C12 C 0.8897(5) 0.7524(7) 0.6141(5) 0.0251(17) Uani 1 1 d . . . . .
H12 H 0.911781 0.691822 0.596525 0.030 Uiso 1 1 calc R U . . .
C13 C 0.8939(4) 0.7486(6) 0.6884(5) 0.0190(15) Uani 1 1 d . . . . .
C14 C 0.9866(5) 0.5705(7) 0.7567(5) 0.0243(17) Uani 1 1 d . . . . .
H14A H 1.028974 0.562887 0.810383 0.029 Uiso 1 1 calc R U . . .
H14B H 1.015166 0.585504 0.724340 0.029 Uiso 1 1 calc R U . . .
C15 C 0.9402(5) 0.4573(7) 0.7316(5) 0.0243(17) Uani 1 1 d . . . . .
H15A H 0.980242 0.394282 0.744024 0.029 Uiso 1 1 calc R U . . .
H15B H 0.907714 0.444820 0.760660 0.029 Uiso 1 1 calc R U . . .
C16 C 0.8131(5) 0.5119(7) 0.6157(5) 0.0219(16) Uani 1 1 d . . . . .
C17 C 0.9057(6) 0.4007(8) 0.5971(6) 0.031(2) Uani 1 1 d . . . . .
H17 H 0.953363 0.356567 0.607891 0.038 Uiso 1 1 calc R U . . .
C18 C 0.8439(6) 0.4228(8) 0.5280(5) 0.032(2) Uani 1 1 d . . . . .
H18 H 0.839324 0.396385 0.480017 0.038 Uiso 1 1 calc R U . . .
C19 C 0.7151(6) 0.5331(9) 0.4751(5) 0.037(2) Uani 1 1 d . . . . .
H19A H 0.725999 0.544409 0.430370 0.056 Uiso 1 1 calc R U . . .
H19B H 0.699349 0.605762 0.489569 0.056 Uiso 1 1 calc R U . . .
H19C H 0.670507 0.477990 0.462441 0.056 Uiso 1 1 calc R U . . .
C20 C 0.6023(6) 0.9678(8) 0.6239(7) 0.041(2) Uani 1 1 d . . . . .
H20A H 0.575298 1.006666 0.574299 0.062 Uiso 1 1 calc R U . . .
H20B H 0.660442 0.988748 0.648866 0.062 Uiso 1 1 calc R U . . .
H20C H 0.576201 0.990498 0.656557 0.062 Uiso 1 1 calc R U . . .
C21 C 0.6230(6) 0.7756(8) 0.5298(5) 0.035(2) Uani 1 1 d . . . . .
H21A H 0.597876 0.830788 0.488038 0.053 Uiso 1 1 calc R U . . .
H21B H 0.604197 0.698742 0.510271 0.053 Uiso 1 1 calc R U . . .
H21C H 0.682837 0.779335 0.550079 0.053 Uiso 1 1 calc R U . . .
C22 C 0.4800(6) 0.7780(9) 0.5694(6) 0.040(2) Uani 1 1 d . . . . .
H22A H 0.449792 0.823440 0.523085 0.060 Uiso 1 1 calc R U . . .
H22B H 0.460870 0.797182 0.608029 0.060 Uiso 1 1 calc R U . . .
H22C H 0.470583 0.696921 0.556772 0.060 Uiso 1 1 calc R U . . .
C23 C 0.5435(6) 0.6177(9) 0.7502(6) 0.038(2) Uani 1 1 d . . . . .
H23A H 0.536978 0.610758 0.797542 0.057 Uiso 1 1 calc R U . . .
H23B H 0.558768 0.543659 0.737092 0.057 Uiso 1 1 calc R U . . .
H23C H 0.491706 0.643136 0.708431 0.057 Uiso 1 1 calc R U . . .
C24 C 0.5936(6) 0.8632(8) 0.7900(7) 0.037(2) Uani 1 1 d . . . . .
H24A H 0.586841 0.854503 0.837130 0.056 Uiso 1 1 calc R U . . .
H24B H 0.541563 0.887644 0.748149 0.056 Uiso 1 1 calc R U . . .
H24C H 0.635902 0.920457 0.798058 0.056 Uiso 1 1 calc R U . . .
C25 C 0.7195(5) 0.6722(8) 0.8517(5) 0.0278(18) Uani 1 1 d . . . . .
H25A H 0.707308 0.669014 0.896116 0.042 Uiso 1 1 calc R U . . .
H25B H 0.765008 0.724927 0.862333 0.042 Uiso 1 1 calc R U . . .
H25C H 0.734650 0.596074 0.841590 0.042 Uiso 1 1 calc R U . . .
C26 C 0.8833(6) 0.4336(9) 0.9077(5) 0.034(2) Uani 1 1 d . . . . .
H26A H 0.902964 0.392500 0.956481 0.052 Uiso 1 1 calc R U . . .
H26B H 0.868435 0.511535 0.914561 0.052 Uiso 1 1 calc R U . . .
H26C H 0.926615 0.435588 0.890526 0.052 Uiso 1 1 calc R U . . .
C27 C 0.8281(7) 0.2139(8) 0.8230(6) 0.043(3) Uani 1 1 d . . . . .
H27A H 0.856456 0.178111 0.873516 0.065 Uiso 1 1 calc R U . . .
H27B H 0.866092 0.221119 0.799639 0.065 Uiso 1 1 calc R U . . .
H27C H 0.781257 0.166785 0.790050 0.065 Uiso 1 1 calc R U . . .
C28 C 0.7190(7) 0.3396(10) 0.8797(7) 0.043(2) Uani 1 1 d . . . . .
H28A H 0.749753 0.310079 0.931932 0.065 Uiso 1 1 calc R U . . .
H28B H 0.675720 0.285584 0.849423 0.065 Uiso 1 1 calc R U . . .
H28C H 0.694381 0.413024 0.881706 0.065 Uiso 1 1 calc R U . . .
C29 C 0.6117(5) 0.4697(8) 0.5958(5) 0.031(2) Uani 1 1 d . . . . .
H29A H 0.577152 0.431025 0.547552 0.047 Uiso 1 1 calc R U . . .
H29B H 0.647370 0.524607 0.587004 0.047 Uiso 1 1 calc R U . . .
H29C H 0.576953 0.509705 0.614804 0.047 Uiso 1 1 calc R U . . .
C30 C 0.7231(5) 0.2632(7) 0.6216(6) 0.0297(19) Uani 1 1 d . . . . .
H30A H 0.683082 0.248701 0.568510 0.044 Uiso 1 1 calc R U . . .
H30B H 0.738379 0.191131 0.649793 0.044 Uiso 1 1 calc R U . . .
H30C H 0.772109 0.298908 0.621908 0.044 Uiso 1 1 calc R U . . .
C31 C 0.6013(6) 0.2731(9) 0.6863(7) 0.040(2) Uani 1 1 d . . . . .
H31A H 0.559440 0.244497 0.637230 0.060 Uiso 1 1 calc R U . . .
H31B H 0.575157 0.319481 0.711274 0.060 Uiso 1 1 calc R U . . .
H31C H 0.629735 0.208709 0.719449 0.060 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
Ce1 C1 2.837(8) . ?
Ce1 C2 2.913(7) . ?
Ce1 N3 2.352(7) . ?
Ce1 N4 2.374(7) . ?
Ce1 C7 3.017(8) . ?
Ce1 C8 3.049(8) . ?
Ce1 C13 2.968(7) . ?
Ce1 C16 2.710(8) . ?
Si1 N3 1.715(7) . ?
Si1 C20 1.875(10) . ?
Si1 C21 1.883(10) . ?
Si1 C22 1.877(10) . ?
N1 C15 1.470(11) . ?
N1 C16 1.350(10) . ?
N1 C17 1.377(11) . ?
C1 C2 1.435(11) . ?
C1 C13 1.432(11) . ?
C1 C14 1.515(11) . ?
Si2 N3 1.707(7) . ?
Si2 C23 1.859(10) . ?
Si2 C24 1.876(9) . ?
Si2 C25 1.898(9) . ?
N2 C16 1.376(10) . ?
N2 C18 1.359(11) . ?
N2 C19 1.462(12) . ?
C2 C3 1.429(11) . ?
C2 C7 1.433(11) . ?
Si3 N4 1.731(7) . ?
Si3 C26 1.875(10) . ?
Si3 C27 1.880(10) . ?
Si3 C28 1.890(10) . ?
C3 H3 0.9500 . ?
C3 C4 1.393(12) . ?
Si4 N4 1.730(7) . ?
Si4 C29 1.882(9) . ?
Si4 C30 1.890(9) . ?
Si4 C31 1.862(10) . ?
C4 H4 0.9500 . ?
C4 C5 1.397(13) . ?
C5 H5 0.9500 . ?
C5 C6 1.392(13) . ?
C6 H6 0.9500 . ?
C6 C7 1.429(12) . ?
C7 C8 1.445(12) . ?
C8 C9 1.410(12) . ?
C8 C13 1.439(11) . ?
C9 H9 0.9500 . ?
C9 C10 1.361(14) . ?
C10 H10 0.9500 . ?
C10 C11 1.422(15) . ?
C11 H11 0.9500 . ?
C11 C12 1.394(13) . ?
C12 H12 0.9500 . ?
C12 C13 1.411(11) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C14 C15 1.534(12) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C17 H17 0.9500 . ?
C17 C18 1.342(14) . ?
C18 H18 0.9500 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
C24 H24A 0.9800 . ?
C24 H24B 0.9800 . ?
C24 H24C 0.9800 . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 0.9800 . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?
C26 H26C 0.9800 . ?
C27 H27A 0.9800 . ?
C27 H27B 0.9800 . ?
C27 H27C 0.9800 . ?
C28 H28A 0.9800 . ?
C28 H28B 0.9800 . ?
C28 H28C 0.9800 . ?
C29 H29A 0.9800 . ?
C29 H29B 0.9800 . ?
C29 H29C 0.9800 . ?
C30 H30A 0.9800 . ?
C30 H30B 0.9800 . ?
C30 H30C 0.9800 . ?
C31 H31A 0.9800 . ?
C31 H31B 0.9800 . ?
C31 H31C 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
C1 Ce1 C2 28.9(2) . . ?
C1 Ce1 C7 47.2(2) . . ?
C1 Ce1 C8 46.6(2) . . ?
C1 Ce1 C13 28.5(2) . . ?
C2 Ce1 C7 27.9(2) . . ?
C2 Ce1 C8 45.5(2) . . ?
C2 Ce1 C13 45.9(2) . . ?
N3 Ce1 C1 134.2(2) . . ?
N3 Ce1 C2 116.0(2) . . ?
N3 Ce1 N4 109.9(2) . . ?
N3 Ce1 C7 89.8(2) . . ?
N3 Ce1 C8 88.3(2) . . ?
N3 Ce1 C13 112.7(2) . . ?
N3 Ce1 C16 130.9(2) . . ?
N4 Ce1 C1 113.0(2) . . ?
N4 Ce1 C2 113.8(2) . . ?
N4 Ce1 C7 136.8(2) . . ?
N4 Ce1 C8 158.4(2) . . ?
N4 Ce1 C13 137.4(2) . . ?
N4 Ce1 C16 83.6(2) . . ?
C7 Ce1 C8 27.6(2) . . ?
C13 Ce1 C7 45.8(2) . . ?
C13 Ce1 C8 27.6(2) . . ?
C16 Ce1 C1 70.1(2) . . ?
C16 Ce1 C2 98.7(2) . . ?
C16 Ce1 C7 112.6(2) . . ?
C16 Ce1 C8 93.2(2) . . ?
C16 Ce1 C13 67.7(2) . . ?
N3 Si1 C20 113.9(4) . . ?
N3 Si1 C21 110.5(4) . . ?
N3 Si1 C22 112.3(4) . . ?
C20 Si1 C21 107.4(5) . . ?
C20 Si1 C22 105.7(5) . . ?
C22 Si1 C21 106.6(5) . . ?
C16 N1 C15 124.5(7) . . ?
C16 N1 C17 113.3(7) . . ?
C17 N1 C15 122.1(7) . . ?
C2 C1 Ce1 78.5(4) . . ?
C2 C1 C14 125.0(7) . . ?
C13 C1 Ce1 80.9(4) . . ?
C13 C1 C2 106.4(7) . . ?
C13 C1 C14 127.7(7) . . ?
C14 C1 Ce1 115.6(5) . . ?
N3 Si2 C23 113.8(4) . . ?
N3 Si2 C24 113.5(4) . . ?
N3 Si2 C25 108.0(4) . . ?
C23 Si2 C24 107.8(5) . . ?
C23 Si2 C25 105.6(5) . . ?
C24 Si2 C25 107.6(4) . . ?
C16 N2 C19 126.2(7) . . ?
C18 N2 C16 111.9(7) . . ?
C18 N2 C19 121.9(8) . . ?
C1 C2 Ce1 72.6(4) . . ?
C3 C2 Ce1 117.2(5) . . ?
C3 C2 C1 130.8(8) . . ?
C3 C2 C7 119.2(7) . . ?
C7 C2 Ce1 80.1(4) . . ?
C7 C2 C1 109.9(7) . . ?
N4 Si3 C26 112.1(4) . . ?
N4 Si3 C27 112.5(4) . . ?
N4 Si3 C28 113.5(4) . . ?
C26 Si3 C27 105.3(5) . . ?
C26 Si3 C28 105.4(5) . . ?
C27 Si3 C28 107.4(5) . . ?
Si1 N3 Ce1 127.5(4) . . ?
Si2 N3 Ce1 110.4(3) . . ?
Si2 N3 Si1 122.1(4) . . ?
C2 C3 H3 120.4 . . ?
C4 C3 C2 119.1(8) . . ?
C4 C3 H3 120.4 . . ?
N4 Si4 C29 108.4(4) . . ?
N4 Si4 C30 114.3(4) . . ?
N4 Si4 C31 115.5(4) . . ?
C29 Si4 C30 108.1(4) . . ?
C31 Si4 C29 104.3(5) . . ?
C31 Si4 C30 105.5(4) . . ?
Si3 N4 Ce1 132.8(4) . . ?
Si4 N4 Ce1 110.1(3) . . ?
Si4 N4 Si3 117.0(4) . . ?
C3 C4 H4 119.3 . . ?
C3 C4 C5 121.5(8) . . ?
C5 C4 H4 119.3 . . ?
C4 C5 H5 119.4 . . ?
C6 C5 C4 121.2(8) . . ?
C6 C5 H5 119.4 . . ?
C5 C6 H6 120.6 . . ?
C5 C6 C7 118.9(8) . . ?
C7 C6 H6 120.6 . . ?
C2 C7 Ce1 72.0(4) . . ?
C2 C7 C8 106.7(7) . . ?
C6 C7 Ce1 122.9(5) . . ?
C6 C7 C2 120.1(8) . . ?
C6 C7 C8 132.5(8) . . ?
C8 C7 Ce1 77.5(4) . . ?
C7 C8 Ce1 75.0(4) . . ?
C9 C8 Ce1 123.2(5) . . ?
C9 C8 C7 130.6(8) . . ?
C9 C8 C13 121.3(8) . . ?
C13 C8 Ce1 73.0(4) . . ?
C13 C8 C7 107.7(7) . . ?
C8 C9 H9 120.5 . . ?
C10 C9 C8 119.0(9) . . ?
C10 C9 H9 120.5 . . ?
C9 C10 H10 119.3 . . ?
C9 C10 C11 121.3(8) . . ?
C11 C10 H10 119.3 . . ?
C10 C11 H11 119.8 . . ?
C12 C11 C10 120.4(9) . . ?
C12 C11 H11 119.8 . . ?
C11 C12 H12 120.1 . . ?
C11 C12 C13 119.9(8) . . ?
C13 C12 H12 120.1 . . ?
C1 C13 Ce1 70.7(4) . . ?
C1 C13 C8 109.1(7) . . ?
C8 C13 Ce1 79.3(4) . . ?
C12 C13 Ce1 119.0(5) . . ?
C12 C13 C1 132.8(7) . . ?
C12 C13 C8 118.1(7) . . ?
C1 C14 H14A 108.7 . . ?
C1 C14 H14B 108.7 . . ?
C1 C14 C15 114.3(7) . . ?
H14A C14 H14B 107.6 . . ?
C15 C14 H14A 108.7 . . ?
C15 C14 H14B 108.7 . . ?
N1 C15 C14 112.0(7) . . ?
N1 C15 H15A 109.2 . . ?
N1 C15 H15B 109.2 . . ?
C14 C15 H15A 109.2 . . ?
C14 C15 H15B 109.2 . . ?
H15A C15 H15B 107.9 . . ?
N1 C16 Ce1 115.6(5) . . ?
N1 C16 N2 101.9(7) . . ?
N2 C16 Ce1 142.5(5) . . ?
N1 C17 H17 127.3 . . ?
C18 C17 N1 105.3(8) . . ?
C18 C17 H17 127.3 . . ?
N2 C18 H18 126.2 . . ?
C17 C18 N2 107.6(8) . . ?
C17 C18 H18 126.2 . . ?
N2 C19 H19A 109.5 . . ?
N2 C19 H19B 109.5 . . ?
N2 C19 H19C 109.5 . . ?
H19A C19 H19B 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
Si1 C20 H20A 109.5 . . ?
Si1 C20 H20B 109.5 . . ?
Si1 C20 H20C 109.5 . . ?
H20A C20 H20B 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
Si1 C21 H21A 109.5 . . ?
Si1 C21 H21B 109.5 . . ?
Si1 C21 H21C 109.5 . . ?
H21A C21 H21B 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
Si1 C22 H22A 109.5 . . ?
Si1 C22 H22B 109.5 . . ?
Si1 C22 H22C 109.5 . . ?
H22A C22 H22B 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
Si2 C23 H23A 109.5 . . ?
Si2 C23 H23B 109.5 . . ?
Si2 C23 H23C 109.5 . . ?
H23A C23 H23B 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
Si2 C24 H24A 109.5 . . ?
Si2 C24 H24B 109.5 . . ?
Si2 C24 H24C 109.5 . . ?
H24A C24 H24B 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
Si2 C25 H25A 109.5 . . ?
Si2 C25 H25B 109.5 . . ?
Si2 C25 H25C 109.5 . . ?
H25A C25 H25B 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 109.5 . . ?
Si3 C26 H26A 109.5 . . ?
Si3 C26 H26B 109.5 . . ?
Si3 C26 H26C 109.5 . . ?
H26A C26 H26B 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
Si3 C27 H27A 109.5 . . ?
Si3 C27 H27B 109.5 . . ?
Si3 C27 H27C 109.5 . . ?
H27A C27 H27B 109.5 . . ?
H27A C27 H27C 109.5 . . ?
H27B C27 H27C 109.5 . . ?
Si3 C28 H28A 109.5 . . ?
Si3 C28 H28B 109.5 . . ?
Si3 C28 H28C 109.5 . . ?
H28A C28 H28B 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
Si4 C29 H29A 109.5 . . ?
Si4 C29 H29B 109.5 . . ?
Si4 C29 H29C 109.5 . . ?
H29A C29 H29B 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
Si4 C30 H30A 109.5 . . ?
Si4 C30 H30B 109.5 . . ?
Si4 C30 H30C 109.5 . . ?
H30A C30 H30B 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
Si4 C31 H31A 109.5 . . ?
Si4 C31 H31B 109.5 . . ?
Si4 C31 H31C 109.5 . . ?
H31A C31 H31B 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 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
Ce1 C1 C2 C3 111.2(8) . . . . ?
Ce1 C1 C2 C7 -72.2(5) . . . . ?
Ce1 C1 C13 C8 70.8(5) . . . . ?
Ce1 C1 C13 C12 -112.1(8) . . . . ?
Ce1 C1 C14 C15 6.4(9) . . . . ?
Ce1 C2 C3 C4 -96.4(8) . . . . ?
Ce1 C2 C7 C6 118.2(7) . . . . ?
Ce1 C2 C7 C8 -70.4(5) . . . . ?
Ce1 C7 C8 C9 121.1(9) . . . . ?
Ce1 C7 C8 C13 -66.2(5) . . . . ?
Ce1 C8 C9 C10 -89.1(9) . . . . ?
Ce1 C8 C13 C1 -65.1(5) . . . . ?
Ce1 C8 C13 C12 117.3(6) . . . . ?
N1 C17 C18 N2 0.6(10) . . . . ?
C1 C2 C3 C4 173.6(8) . . . . ?
C1 C2 C7 Ce1 67.3(5) . . . . ?
C1 C2 C7 C6 -174.5(7) . . . . ?
C1 C2 C7 C8 -3.1(8) . . . . ?
C1 C14 C15 N1 67.4(9) . . . . ?
C2 C1 C13 Ce1 -75.1(5) . . . . ?
C2 C1 C13 C8 -4.3(8) . . . . ?
C2 C1 C13 C12 172.8(8) . . . . ?
C2 C1 C14 C15 100.2(9) . . . . ?
C2 C3 C4 C5 1.7(12) . . . . ?
C2 C7 C8 Ce1 66.6(5) . . . . ?
C2 C7 C8 C9 -172.3(8) . . . . ?
C2 C7 C8 C13 0.4(8) . . . . ?
C3 C2 C7 Ce1 -115.7(7) . . . . ?
C3 C2 C7 C6 2.5(11) . . . . ?
C3 C2 C7 C8 173.9(7) . . . . ?
C3 C4 C5 C6 -0.3(13) . . . . ?
C4 C5 C6 C7 0.1(13) . . . . ?
C5 C6 C7 Ce1 86.0(9) . . . . ?
C5 C6 C7 C2 -1.2(12) . . . . ?
C5 C6 C7 C8 -170.0(8) . . . . ?
C6 C7 C8 Ce1 -123.5(9) . . . . ?
C6 C7 C8 C9 -2.4(15) . . . . ?
C6 C7 C8 C13 170.3(8) . . . . ?
C7 C2 C3 C4 -2.7(11) . . . . ?
C7 C8 C9 C10 172.2(8) . . . . ?
C7 C8 C13 Ce1 67.5(5) . . . . ?
C7 C8 C13 C1 2.4(8) . . . . ?
C7 C8 C13 C12 -175.2(7) . . . . ?
C8 C9 C10 C11 -0.2(13) . . . . ?
C9 C8 C13 Ce1 -119.0(7) . . . . ?
C9 C8 C13 C1 176.0(7) . . . . ?
C9 C8 C13 C12 -1.6(11) . . . . ?
C9 C10 C11 C12 1.6(14) . . . . ?
C10 C11 C12 C13 -3.0(13) . . . . ?
C11 C12 C13 Ce1 96.2(8) . . . . ?
C11 C12 C13 C1 -173.9(8) . . . . ?
C11 C12 C13 C8 2.9(11) . . . . ?
C13 C1 C2 Ce1 76.8(5) . . . . ?
C13 C1 C2 C3 -172.0(8) . . . . ?
C13 C1 C2 C7 4.6(8) . . . . ?
C13 C1 C14 C15 -92.1(10) . . . . ?
C13 C8 C9 C10 0.3(12) . . . . ?
C14 C1 C2 Ce1 -113.4(8) . . . . ?
C14 C1 C2 C3 -2.2(13) . . . . ?
C14 C1 C2 C7 174.4(7) . . . . ?
C14 C1 C13 Ce1 115.4(8) . . . . ?
C14 C1 C13 C8 -173.7(8) . . . . ?
C14 C1 C13 C12 3.4(14) . . . . ?
C15 N1 C16 Ce1 -4.6(10) . . . . ?
C15 N1 C16 N2 175.8(7) . . . . ?
C15 N1 C17 C18 -176.3(8) . . . . ?
C16 N1 C15 C14 -74.5(10) . . . . ?
C16 N1 C17 C18 -0.2(10) . . . . ?
C16 N2 C18 C17 -0.8(11) . . . . ?
C17 N1 C15 C14 101.1(9) . . . . ?
C17 N1 C16 Ce1 179.4(6) . . . . ?
C17 N1 C16 N2 -0.2(9) . . . . ?
C18 N2 C16 Ce1 -178.8(7) . . . . ?
C18 N2 C16 N1 0.7(9) . . . . ?
C19 N2 C16 Ce1 2.3(15) . . . . ?
C19 N2 C16 N1 -178.2(8) . . . . ?
C19 N2 C18 C17 178.1(8) . . . . ?
C20 Si1 N3 Ce1 -110.7(5) . . . . ?
C20 Si1 N3 Si2 71.1(6) . . . . ?
C21 Si1 N3 Ce1 10.3(6) . . . . ?
C21 Si1 N3 Si2 -167.9(5) . . . . ?
C22 Si1 N3 Ce1 129.2(5) . . . . ?
C22 Si1 N3 Si2 -49.0(6) . . . . ?
C23 Si2 N3 Ce1 -97.3(5) . . . . ?
C23 Si2 N3 Si1 81.2(6) . . . . ?
C24 Si2 N3 Ce1 138.8(4) . . . . ?
C24 Si2 N3 Si1 -42.7(6) . . . . ?
C25 Si2 N3 Ce1 19.6(4) . . . . ?
C25 Si2 N3 Si1 -162.0(4) . . . . ?
C26 Si3 N4 Ce1 -12.7(6) . . . . ?
C26 Si3 N4 Si4 166.3(4) . . . . ?
C27 Si3 N4 Ce1 -131.1(5) . . . . ?
C27 Si3 N4 Si4 47.9(6) . . . . ?
C28 Si3 N4 Ce1 106.6(6) . . . . ?
C28 Si3 N4 Si4 -74.4(6) . . . . ?
C29 Si4 N4 Ce1 -21.6(5) . . . . ?
C29 Si4 N4 Si3 159.2(4) . . . . ?
C30 Si4 N4 Ce1 99.1(4) . . . . ?
C30 Si4 N4 Si3 -80.1(5) . . . . ?
C31 Si4 N4 Ce1 -138.1(4) . . . . ?
C31 Si4 N4 Si3 42.7(6) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'



# start Validation Reply Form
_vrf_PLAT097_5_LaLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       9.95 eA-3  
RESPONSE: The structures for all LnLN2 compounds (Ln = La, Ce and Nd in this 
paper, Ln = La in P-1 in a previous paper) all feature large Q peaks. This 
is despite crystallising in several different space groups (Ln = La in this 
paper: Pca21, Ln = Ce: P 21/c, Ln = Nd: Pca21). We have looked for 
non-merohedral twinning, but have not been able to model the data any better 
than that presented here. We have used Cu radiation, which although not ideal 
for heavy atoms, has worked satisfactorily with small crystals of other rare 
earth complexes (for example, the Ce Br bridged structure in this paper, the 
Nd Br bridged structure in a previous paper), so believe the problem is 
inherent with the way this class of compounds crystallise. 
;
_vrf_PLAT971_6_CeLN2             
;
PROBLEM: Check Calcd Resid. Dens.  1.32Ang From Ce1             7.88 eA-3  
RESPONSE: Please see response to 5_LaN2. We believe that it is mostly 
likely due to a small amount of residual, unmodelled twinning. We have 
checked our absorption correction and we have used Cu radiation 
successfully for other rare earth structures.
;
_vrf_PLAT094_6_CeLN2             
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       4.82 Report
RESPONSE: Please see above.
;
_vrf_PLAT097_6_CeLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       7.72 eA-3  
RESPONSE: Please see above response.
;
_vrf_PLAT097_7_NdLN2             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       6.37 eA-3  
RESPONSE: RESPONSE: Please see response to 5_LaN2. We believe that it is mostly 
likely due to a small amount of residual, unmodelled twinning. We have 
checked our absorption correction and we have used Cu radiation 
successfully for other rare earth structures.
;
# end Validation Reply Form

