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_7713637
_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         '2(Bi1 I4.5), 0.75(C4), 2(C3 S1), 0.083(S12)'
_chemical_formula_sum            'C9 Bi2 I9 S3'
_chemical_formula_weight         1764.33
_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_Hall           '-P 6c 2c'
_space_group_name_H-M_alt        'P 63/m m c'
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-27
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2023-05-18 deposited with the CCDC.	2023-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   9.7593(10)
_cell_length_b                   9.7593(10)
_cell_length_c                   23.153(3)
_cell_measurement_reflns_used    734
_cell_measurement_temperature    325.01(10)
_cell_measurement_theta_max      17.6640
_cell_measurement_theta_min      2.9760
_cell_volume                     1909.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      325.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6249
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.938
_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     -1.00  51.00   1.00   35.00    --   13.31 -99.00 120.00   52
  2  \w     -7.00  66.00   1.00   35.00    --   13.31  57.00-120.00   73
;
_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      0.0590043000
_diffrn_orient_matrix_UB_12      0.0460542000
_diffrn_orient_matrix_UB_13      0.0206301000
_diffrn_orient_matrix_UB_21      -0.0430375000
_diffrn_orient_matrix_UB_22      -0.0575026000
_diffrn_orient_matrix_UB_23      0.0214710000
_diffrn_orient_matrix_UB_31      0.0414410000
_diffrn_orient_matrix_UB_32      -0.0402186000
_diffrn_orient_matrix_UB_33      -0.0071270000
_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  0.0786
_diffrn_reflns_av_unetI/netI     0.0711
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5576
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.258
_diffrn_reflns_theta_min         2.565
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    16.637
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.00057
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    3.068
_exptl_crystal_description       plate
_exptl_crystal_F_000             1490
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.406
_refine_diff_density_min         -1.087
_refine_diff_density_rms         0.205
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     14
_refine_ls_number_reflns         981
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      3.355
_refine_ls_R_factor_all          0.2188
_refine_ls_R_factor_gt           0.0878
_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^)+(0.1808P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2820
_refine_ls_wR_factor_ref         0.3753
_reflns_Friedel_coverage         0.000
_reflns_number_gt                294
_reflns_number_total             981
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01650a3.cif
_cod_data_source_block           PhaseI
_cod_original_cell_volume        1909.8(5)
_cod_database_code               7713637
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Bi2I9S3C9H9
_olex2_refinement_description
;
1. Restrained distances
 S1-C1
 1.8 with sigma of 0.001
 S3-C1
 1.8 with sigma of 0.001
 S2-C2
 1.8 with sigma of 0.003
2. Others
 Fixed Sof: C2(0.25) C1(0.5) S1(0.08333) S3(0.08333) S2(0.08333)
3.a Everything fixed:
 C2, C1, S1, S3, S2
;
_shelx_res_checksum              57256
_olex2_date_sample_data_collection 2021-04-28
_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 324.231
_oxdiff_exptl_absorpt_empirical_full_min 0.187