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_4003546
_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 Br10, 4(C8 H11 F N)'
_chemical_formula_sum            'C32 H44 Bi2 Br10 F4 N4'
_chemical_formula_weight         1777.77
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.2271(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.2017(6)
_cell_length_b                   14.1185(7)
_cell_length_c                   14.0742(7)
_cell_measurement_reflns_used    9834
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.30
_cell_measurement_theta_min      2.56
_cell_volume                     2414.5(2)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 10.4167
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0583
_diffrn_reflns_av_unetI/netI     0.0546
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_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       -16
_diffrn_reflns_number            35531
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.329
_diffrn_reflns_theta_min         2.116
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    15.596
_exptl_absorpt_correction_T_max  0.5619
_exptl_absorpt_correction_T_min  0.1505
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1774 before and 0.0851 after correction. The Ratio of minimum to maximum transmission is 0.2678. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.445
_exptl_crystal_description       plate
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.351
_exptl_crystal_size_mid          0.298
_exptl_crystal_size_min          0.116
_refine_diff_density_max         2.643
_refine_diff_density_min         -3.229
_refine_diff_density_rms         0.389
_refine_ls_abs_structure_details
;
 Flack x determined using 3278 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.024(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     471
_refine_ls_number_reflns         8688
_refine_ls_number_restraints     151
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0444
_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^)+(0.0965P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1277
_refine_ls_wR_factor_ref         0.1360
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                7657
_reflns_number_total             8688
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c01605_si_006.cif
_cod_data_source_block           compound5
_cod_database_code               4003546
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.265
_shelx_estimated_absorpt_t_min   0.073
_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
 C28B-C27 \\sim C28A-C27 \\sim C32A-C27 \\sim C32B-C27 \\sim C32A-C31A \\sim
C32B-C31B \\sim C31B-C30B
 \\sim C31A-C30A \\sim C30A-C29A \\sim C30B-C29B \\sim C29B-C28B \\sim C29A-C28A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C20) \\sim
Ueq, Uanis(C19) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, : with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(N2) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(N4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(N4) \\sim
Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C22) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
: with sigma of 0.01 and sigma for terminal atoms of 0.02
: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: F4A(0.5) C28A(0.5) H28A(0.5) C29A(0.5) H29A(0.5) C32A(0.5)
 H32A(0.5) C31B(0.5) H31B(0.5) C32B(0.5) H32B(0.5) C31A(0.5) H31A(0.5)
 C29B(0.5) H29B(0.5) F4B(0.5) C28B(0.5) H28B(0.5) C30A(0.5) C30B(0.5)
5.a Ternary CH refined with riding coordinates:
 C26(H26), C18(H18), C2(H2), C10(H10)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C23(H23), C21(H21), C24(H24), C15(H15), C20(H20), C16(H16),
 C28A(H28A), C5(H5), C29A(H29A), C8(H8), C32A(H32A), C31B(H31B), C32B(H32B),
 C7(H7), C12(H12), C13(H13), C31A(H31A), C29B(H29B), C28B(H28B)
5.c Idealised Me refined as rotating group:
 N3(H3A,H3B,H3C), N4(H4A,H4B,H4C), N2(H2A,H2B,H2C), N1(H1A,H1B,H1C), C9(H9A,
 H9B,H9C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C1(H1D,H1E,H1F)
;
_shelx_res_checksum              91230
_shelx_hkl_checksum              53471
_olex2_submission_special_instructions 'No special instructions were received'