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_7713319
_publ_section_title
;
 Second harmonic generation from symmetry breaking stimulated by mixed
 organic cations in zero-dimensional hybrid metal halides.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt01209c
_journal_year                    2023
_chemical_formula_moiety         'Br6 Sb, C9.005 H12.227 O S, C9 H15 N3'
_chemical_formula_sum            'C18 H27.23 Br6 N3 O S Sb'
_chemical_formula_weight         934.98
_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.cc2fbyj8
_audit_creation_date             2023-03-08
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-03-08 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                   9.9212(3)
_cell_length_b                   16.2506(5)
_cell_length_c                   17.7298(5)
_cell_measurement_reflns_used    5824
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      26.16
_cell_measurement_theta_min      2.41
_cell_volume                     2858.50(15)
_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 0.991
_diffrn_measured_fraction_theta_max 0.991
_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  0.0503
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_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            26578
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.405
_exptl_absorpt_coefficient_mu    9.441
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.173
_exptl_crystal_description       block
_exptl_crystal_F_000             1765
_refine_diff_density_max         1.871
_refine_diff_density_min         -1.641
_refine_diff_density_rms         0.146
_refine_ls_abs_structure_details
;
 Flack x determined using 1778 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.018(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         4994
_refine_ls_number_restraints     69
_refine_ls_restrained_S_all      1.146
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0421
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0700P)^2^+5.2329P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1102
_refine_ls_wR_factor_ref         0.1132
_reflns_Friedel_coverage         0.769
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4562
_reflns_number_total             4994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01209c2.cif
_cod_data_source_block           c18h29n3ossbbr6-p212121-forpublish
_cod_database_code               7713319
_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
 H3B-H3A
 2.2 with sigma of 0.02
 H3B-H3
 2.2 with sigma of 0.02
3. Rigid bond restraints
 S1, O1
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S1, O1, C10, C11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
S1 \\sim O1: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
S1 \\sim O1 \\sim C10 \\sim C11: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
Uanis(C15) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C17A)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O1) \\sim Ueq, Uanis(S1) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(S1) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C13) = Uanis(C12) = Uanis(C17A) = Uanis(C15)
Uanis(C13) = Uanis(C12) = Uanis(C17A) = Uanis(C18A) = Uanis(C15) = Uanis(C14)
Uanis(C18B) = Uanis(C18A) = Uanis(C15) = Uanis(C14) = Uanis(C17A) = Uanis(C12)
= Uanis(C13) = Uanis(C11) = Uanis(C10)
Uanis(C17A) = Uanis(C17B)
Uanis(C18A) = Uanis(C18B)
Uanis(C17A) = Uanis(C17B) = Uanis(C16) = Uanis(C18A) = Uanis(C18B) = Uanis(C15)
= Uanis(C14) = Uanis(C13) = Uanis(C12) = Uanis(C11) = Uanis(C10)
5. Others
 1*[Sof(C17B)+Sof(H17B)]+1*[Sof(C17A)+Sof(H17A)]=1 with esd of 0.01
 1*[Sof(C18A)+Sof(H18A)+Sof(H15)]+1*[Sof(H15A)+Sof(C18B)+Sof(H18B)+Sof(H18C)]=
 1 with esd of 0.01
 1*[Sof(C17A)+Sof(H17A)]+1*[Sof(C17B)+Sof(H17B)]=0.0001 with esd of 1
 1*[Sof(C18A)+Sof(H18A)+Sof(H15)]+1*[Sof(H15A)+Sof(C18B)+Sof(H18B)+Sof(H18C)]=
 1 with esd of 0.0001
 1*[Sof(C17A)+Sof(H17A)]+1*[Sof(C17B)+Sof(H17B)]=1 with esd of 0.01
 1*[Sof(C18A)+Sof(H18A)+Sof(H15)]+1*[Sof(H15A)+Sof(C18B)+Sof(H18B)+Sof(H18C)]=
 1 with esd of 0.01
 1*[Sof(C18A)+Sof(H18A)+Sof(H15)]+1*[Sof(H15A)+Sof(C18B)+Sof(H18B)+Sof(H18C)]=
 1 with esd of 0.01
 Sof(C17B)=Sof(H17B)=FVAR(1)
 Sof(C17A)=Sof(H17A)=FVAR(2)
 Sof(C18A)=Sof(H18A)=Sof(H15)=FVAR(3)
 Sof(H15A)=Sof(C18B)=Sof(H18B)=Sof(H18C)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C18B(H18B,H18C), N1(H1A,H1B), C1(H1C,H1D), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,
 H4B)
6.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C17A(H17A), C18A(H18A), C15(H15), C15(H15A), C14(H14), C13(H13),
 C17B(H17B), N3(H3), C6(H6), C7(H7), C8(H8), C9(H9)
6.c Fitted hexagon refined as free rotating group:
 C17A(C18A,C15,C14,C13,C12)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_olex2_submission_special_instructions 'No special instructions were received'