Symmetry breaking of A3M2X9-type perovskite derivatives induced by polar quaternary ammonium cations: achieving efficient nonlinear optical properties
Wu, Jia-Jing; Guo, Yue; Yao, Wen-Dong; Liu, Wen-Long; Guo, Sheng-Ping; Dalton Transactions  (2022) –; doi:10.1039/D2DT00451H

data_7709685
_publ_section_title
;
 Symmetry breaking of A3M2X9-type perovskite derivatives induced by polar
 quaternary ammonium cations: achieving efficient nonlinear optical
 properties
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00451H
_journal_year                    2022
_chemical_formula_moiety         'Bi2 Cl9, 3(C13 H22 N)'
_chemical_formula_sum            'C39 H66 Bi2 Cl9 N3'
_chemical_formula_weight         1313.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2021-12-30 deposited with the CCDC.	2022-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.581(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8858(10)
_cell_length_b                   22.8870(17)
_cell_length_c                   17.1739(12)
_cell_measurement_reflns_used    9722
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      35.7467
_cell_measurement_theta_min      2.5810
_cell_volume                     5059.7(6)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_av_unetI/netI     0.0598
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            38979
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.561
_diffrn_reflns_theta_min         1.780
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    7.451
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6148
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0865 before and 0.0714 after correction.
The Ratio of minimum to maximum transmission is 0.8246.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.725
_exptl_crystal_description       block
_exptl_crystal_F_000             2560
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.443
_refine_diff_density_min         -0.540
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Flack x determined using 3838 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.001(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.953
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         11392
_refine_ls_number_restraints     170
_refine_ls_restrained_S_all      0.969
_refine_ls_R_factor_all          0.0461
_refine_ls_R_factor_gt           0.0302
_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/[\s^2^(Fo^2^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0469
_refine_ls_wR_factor_ref         0.0502
_reflns_Friedel_coverage         0.946
_reflns_Friedel_fraction_full    0.958
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                9556
_reflns_number_total             11392
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00451h2.cif
_cod_data_source_block           aa
_cod_database_code               7709685
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.523
_shelx_estimated_absorpt_t_min   0.468
_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. Uiso/Uaniso restraints and constraints
N1 \\sim C7 \\sim C8 \\sim C12 \\sim C10 \\sim C6 \\sim C9 \\sim C13 \\sim C11
\\sim C1 \\sim C5 \\sim C2 \\sim C4 \\sim C3: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(C4) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim
Ueq, Uanis(C12) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C1) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C36(H36A,H36B), C20(H20A,H20B), C34(H34A,H34B), C38(H38A,
 H38B), C23(H23A,H23B), C25(H25A,H25B), C21(H21A,H21B), C7(H7A,H7B), C8(H8A,
 H8B), C12(H12A,H12B), C10(H10A,H10B)
3.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C19(H19), C31(H31), C18(H18), C16(H16), C15(H15), C28(H28),
 C17(H17), C29(H29), C30(H30), C1(H1), C3(H3), C4(H4), C2(H2), C5(H5)
3.c Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C26(H26A,H26B,H26C), C35(H35A,H35B,H35C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C37(H37A,H37B,H37C), C9(H9A,H9B,H9C), C13(H13A,
 H13B,H13C), C11(H11A,H11B,H11C)
;
_olex2_submission_special_instructions 'No special instructions were received'