Second harmonic generation from symmetry breaking stimulated by mixed organic cations in zero-dimensional hybrid metal halides.
Cao, Jindong; Liu, Kunjie; Quan, Mingzhen; Hou, An; Jiang, Xingxing; Lin, Zheshuai; Zhao, Jing; Liu, Quanlin; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt01209c

data_7713318
_publ_section_title
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 Second harmonic generation from symmetry breaking stimulated by mixed
 organic cations in zero-dimensional hybrid metal halides.
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_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt01209c
_journal_year                    2023
_chemical_formula_moiety         'Bi Br6, C9 H12.5 O S, C9 H15 N3'
_chemical_formula_sum            'C18 H27.5 Bi Br6 N3 O S'
_chemical_formula_weight         1022.43
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc2fbyh7
_audit_creation_date             2023-02-27
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
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2023-02-27 deposited with the CCDC.	2023-06-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8987(6)
_cell_length_b                   16.3369(12)
_cell_length_c                   17.8274(14)
_cell_measurement_reflns_used    7842
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      26.38
_cell_measurement_theta_min      2.28
_cell_volume                     2882.9(4)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0763
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            40191
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.990
_diffrn_reflns_theta_max         24.990
_diffrn_reflns_theta_min         2.285
_exptl_absorpt_coefficient_mu    14.520
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    2.356
_exptl_crystal_description       block
_exptl_crystal_F_000             1894
_refine_diff_density_max         1.459
_refine_diff_density_min         -1.420
_refine_diff_density_rms         0.144
_refine_ls_abs_structure_details
;
 Flack x determined using 1657 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.031(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         5067
_refine_ls_number_restraints     135
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0376
_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/[\s^2^(Fo^2^)+(0.0430P)^2^+5.6286P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0838
_refine_ls_wR_factor_ref         0.0891
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4294
_reflns_number_total             5067
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01209c2.cif
_cod_data_source_block           mo_0918_2_0ma-publish
_cod_original_formula_sum        'C18 H27.50 Bi Br6 N3 O S'
_cod_database_code               7713318
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C16-C14 = C13-C12 = C0AA-C17
 1.36 with sigma of 0.02
 H2A-H3
 2.2 with sigma of 0.02
 H2B-H3
 2.2 with sigma of 0.02
3. Rigid bond restraints
 C14, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C16, C14, C15, C13, C12, C0AA, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C13, C12, C18A, O1, C17, C16, C0AA, C14, C15, C10, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C13, C14, C16, C17, C12, C0AA, C18A, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1, O1, C10, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C17 \\sim C0AA \\sim C12 \\sim C13 \\sim C14 \\sim C16 \\sim C15: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O1 \\sim S1 \\sim C11 \\sim C10: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C14) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C16) \\sim Ueq:
with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C18A) = Uanis(C0AA)
Uanis(C14) = Uanis(C15) = Uanis(C16) = Uanis(C17) = Uanis(C0AA) = Uanis(C12) =
Uanis(C13) = Uanis(C18A) = Uanis(C11) = Uanis(C10)
5. Others
 1*[Sof(C0AA)+Sof(C18A)+Sof(H12)]+1*[Sof(C0AA)+Sof(C18A)+Sof(H12)]=1 with esd
 of 0.01
 Sof(C0AA)=Sof(H12)=1-FVAR(1)
 Sof(C18A)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C1(H1C,H1D), C3(H3A,H3B), C4(H4A,H4B), C2(H2A,H2B)
6.b Aromatic/amide H refined with riding coordinates:
 N3(H3), C8(H8), C7(H7), C9(H9), C6(H6), C12(H12), C13(H13), C16(H16), C17(H17)
6.c Fitted hexagon refined as free rotating group:
 C18A(C12,C13,C14,C16,C17)
6.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C10(H10A,H10B,H10C), C15(H15A,H15B,H15C)
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_olex2_submission_special_instructions 'No special instructions were received'