Band Gap-Tunable, Chiral Hybrid Metal Halides Displaying Second-Harmonic Generation
Dehnhardt, Natalie; Axt, Marleen; Zimmermann, Jonas; Yang, Meng; Mette, Gerson; Heine, Johanna; Chemistry of Materials  (2020) –; doi:10.1021/acs.chemmater.0c01605

data_4003547
_publ_section_title
;
 Band Gap-Tunable, Chiral Hybrid Metal Halides Displaying Second-Harmonic
 Generation
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.0c01605
_journal_year                    2020
_chemical_absolute_configuration syn
_chemical_formula_moiety         'Bi2 Cl10, 4(C8 H11 F N)'
_chemical_formula_sum            'C32 H44 Bi2 Cl10 F4 N4'
_chemical_formula_weight         1333.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-04-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.5476(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.7357(5)
_cell_length_b                   13.9008(6)
_cell_length_c                   13.9806(6)
_cell_measurement_reflns_used    9954
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.29
_cell_measurement_theta_min      2.28
_cell_volume                     2270.05(17)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 10.4167
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 QUEST area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0558
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            36302
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.307
_diffrn_reflns_theta_min         2.165
_exptl_absorpt_coefficient_mu    8.375
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.4565
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1054 before and 0.0786 after correction. The Ratio of minimum to maximum transmission is 0.6126. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.950
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.392
_exptl_crystal_size_mid          0.282
_exptl_crystal_size_min          0.17
_refine_diff_density_max         1.438
_refine_diff_density_min         -1.254
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
;
 Flack x determined using 3335 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(5)
_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     427
_refine_ls_number_reflns         8204
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0272
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+3.5911P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0610
_refine_ls_wR_factor_ref         0.0643
_reflns_Friedel_coverage         0.900
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                7435
_reflns_number_total             8204
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c01605_si_005.cif
_cod_data_source_block           compound4
_cod_database_code               4003547
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.330
_shelx_estimated_absorpt_t_min   0.138
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C8-C3 \\sim C8-C7 \\sim C7-C6 \\sim C6-C5 \\sim C5-C4 \\sim C4-C3 \\sim
C16-C11 \\sim C16-C15 \\sim C15-C14 ~
 C14-C13 \\sim C13-C12 \\sim C12-C11
 with sigma of 0.02
3. Others
 Fixed Sof: N4A(0.5) H4AA(0.5) H4AB(0.5) H4AC(0.5) F4B(0.5) F3A(0.5) C20A(0.5)
 H20A(0.5) C27B(0.5) C32B(0.5) H32B(0.5) C31B(0.5) H31B(0.5) C30B(0.5)
 C29B(0.5) H29B(0.5) C28B(0.5) H28B(0.5) C24A(0.5) H24A(0.5) C23A(0.5)
 H23A(0.5) C22A(0.5) C26A(0.5) H26A(0.5) C25A(0.5) H25A(0.5) H25B(0.5)
 H25C(0.5) C21A(0.5) H21A(0.5) F3B(0.5) C20B(0.5) H20B(0.5) C21B(0.5) H21B(0.5)
 C22B(0.5) C23B(0.5) H23B(0.5) C24B(0.5) H24B(0.5) C25B(0.5) H25D(0.5)
 H25E(0.5) H25F(0.5) F4A(0.5) N4B(0.5) H4BA(0.5) H4BB(0.5) H4BC(0.5) C26B(0.5)
 H26B(0.5) C27A(0.5) C32A(0.5) H32A(0.5) C31A(0.5) H31A(0.5) C30A(0.5)
 C29A(0.5) H29A(0.5) C28A(0.5) H28A(0.5)
4.a Ternary CH refined with riding coordinates:
 C18(H18), C2(H2), C10(H10), C26A(H26A), C26B(H26B)
4.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C20A(H20A), C32B(H32B), C31B(H31B), C29B(H29B), C28B(H28B),
 C15(H15), C13(H13), C12(H12), C5(H5), C24A(H24A), C4(H4), C23A(H23A),
 C21A(H21A), C16(H16), C20B(H20B), C21B(H21B), C23B(H23B), C24B(H24B),
 C32A(H32A), C31A(H31A), C29A(H29A), C28A(H28A)
4.c Fitted hexagon refined as free rotating group:
 C27B(C32B,C31B,C30B,C29B,C28B), C19(C20B,C21B,C22B,C23B,C24B), C27A(C32A,C31A,
 C30A,C29A,C28A)
4.d Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N2(H2A,H2B,H2C), N3(H3A,H3B,H3C), N4A(H4AA,H4AB,H4AC),
 C9(H9A,H9B,H9C), C1(H1D,H1E,H1F), C17(H17A,H17B,H17C), C25A(H25A,H25B,H25C),
 C25B(H25D,H25E,H25F), N4B(H4BA,H4BB,H4BC)
;
_shelx_res_checksum              69935
_shelx_hkl_checksum              46805
_olex2_submission_special_instructions 'No special instructions were received'