Temperature symmetry breaking and properties of lead-free organic-inorganic hybrids: antimony(III) iodide and bismuth(III) iodide: (S(CH3)3)3[Sb2I9] and (S(CH3)3)3[Bi2I9]
Szklarz, Przemyslaw; Gągor, Anna; Jakubas, Ryszard; Medycki, Wojciech; Bator, Grazyna; Dalton Transactions  (2023) –; doi:10.1039/D3DT01650A

data_7713639
_publ_section_title
;
 Temperature symmetry breaking and properties of lead-free
 organic-inorganic hybrids: antimony(III) iodide and bismuth(III) iodide:
 (S(CH3)3)3[Sb2I9] and (S(CH3)3)3[Bi2I9]
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01650A
_journal_year                    2023
_chemical_formula_moiety
'Bi2 I9, 2.25(C3 H9 S), 0.25(C3 H9 S0.8), 0.375(S), 0.25(C3 H9 S0.5), 0.25(C3 H9 S0.2)'
_chemical_formula_sum            'C9 H27 Bi2 I9 S3'
_chemical_formula_weight         1791.54
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-05-18 deposited with the CCDC.	2023-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                89.063(2)
_cell_angle_beta                 88.081(2)
_cell_angle_gamma                60.273(2)
_cell_formula_units_Z            8
_cell_length_a                   18.8536(5)
_cell_length_b                   18.9933(4)
_cell_length_c                   22.6857(6)
_cell_measurement_reflns_used    15557
_cell_measurement_temperature    99.9(10)
_cell_measurement_theta_max      29.1360
_cell_measurement_theta_min      2.7700
_cell_volume                     7050.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6249
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -23.00  84.20   0.80   35.00    --   13.31  77.00  60.00  134
  2  \w     -1.00  94.20   0.80   35.00    --   13.31  77.00 -90.00  119
  3  \w    -47.00  57.00   0.80   35.00    --  -14.40  77.00 150.00  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0315183000
_diffrn_orient_matrix_UB_12      0.0069353000
_diffrn_orient_matrix_UB_13      0.0210103000
_diffrn_orient_matrix_UB_21      0.0216720000
_diffrn_orient_matrix_UB_22      0.0068478000
_diffrn_orient_matrix_UB_23      0.0220715000
_diffrn_orient_matrix_UB_31      -0.0203809000
_diffrn_orient_matrix_UB_32      0.0418852000
_diffrn_orient_matrix_UB_33      -0.0070780000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0608
_diffrn_reflns_av_unetI/netI     0.1126
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            48474
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         2.490
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    18.028
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.14192
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    3.376
_exptl_crystal_description       plate
_exptl_crystal_F_000             6176
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.07
_refine_diff_density_max         5.884
_refine_diff_density_min         -4.095
_refine_diff_density_rms         0.604
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.173
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         26743
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.173
_refine_ls_R_factor_all          0.1320
_refine_ls_R_factor_gt           0.1016
_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^)+(0.0384P)^2^+1164.6615P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2139
_refine_ls_wR_factor_ref         0.2290
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20438
_reflns_number_total             26743
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01650a3.cif
_cod_data_source_block           PhaseIII
_cod_database_code               7713639
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Bi2I9C9S3H27
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-C36 = C37-C35 = C36-C35
 2.8 with sigma of 0.005
 S12-C37 = S12-C36 = S12-C35
 1.7 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uiso(C36) = Uiso(C35) = Uiso(C37)
4. Others
 Fixed Sof: S9(0.8) S3A(0.8) S2A(0.5) S5(0.5) S2(0.2) S1A(0.2)
5.a Fixed occupancy and ADP/Uiso:
 C37, C36, C35
5.b Me refined with riding coordinates:
 C15(H15A,H15B,H15C), C33(H33A,H33B,H33C), C14(H14A,H14B,H14C), C23(H23A,H23B,
 H23C), C10(H10A,H10B,H10C), C7(H7A,H7B,H7C), C11(H11A,H11B,H11C), C31(H31A,
 H31B,H31C), C18(H18A,H18B,H18C), C5(H5A,H5B,H5C), C20(H20A,H20B,H20C),
 C21(H21A,H21B,H21C), C26(H26A,H26B,H26C), C25(H25A,H25B,H25C), C4(H4A,H4B,H4C),
  C28(H28A,H28B,H28C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C22(H22A,H22B,H22C),
 C30(H30A,H30B,H30C), C34(H34A,H34B,H34C), C29(H29A,H29B,H29C), C3(H3A,H3B,H3C),
  C2(H2A,H2B,H2C), C27(H27A,H27B,H27C), C17(H17A,H17B,H17C), C16(H16A,H16B,
 H16C), C12(H12A,H12B,H12C), C6(H6A,H6B,H6C), C13(H13A,H13B,H13C), C32(H32A,
 H32B,H32C), C24(H24A,H24B,H24C), C19(H19A,H19B,H19C)
5.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C36(H36A,H36B,H36C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              85152
_olex2_date_sample_data_collection 2021-04-27
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.947
_oxdiff_exptl_absorpt_empirical_full_min 0.527