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_7713638
_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 I9.008, 0.5(C3 H9 S), 0.5(C3 H9 S0.8), 0.5(C3 H9 S0.7), 0.25(C S), 0.25(C6 S2), 0.5(C3 H9 S0.45), 0.525(S), 0.5(C2.5 H7.5 S0.5)'
_chemical_formula_sum            'C9 H21.75 Bi2 I9 S3'
_chemical_formula_weight         1786.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-16
_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                90
_cell_angle_beta                 91.878(2)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   19.0052(4)
_cell_length_b                   33.1993(8)
_cell_length_c                   22.8970(6)
_cell_measurement_reflns_used    16550
_cell_measurement_temperature    199.8(4)
_cell_measurement_theta_max      27.6490
_cell_measurement_theta_min      2.7360
_cell_volume                     14439.3(6)
_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      N~2~
_diffrn_ambient_temperature      199.8(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6249
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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      0.0278542000
_diffrn_orient_matrix_UB_12      -0.0033681000
_diffrn_orient_matrix_UB_13      0.0208137000
_diffrn_orient_matrix_UB_21      -0.0248630000
_diffrn_orient_matrix_UB_22      -0.0035596000
_diffrn_orient_matrix_UB_23      0.0218311000
_diffrn_orient_matrix_UB_31      -0.0002565000
_diffrn_orient_matrix_UB_32      -0.0208006000
_diffrn_orient_matrix_UB_33      -0.0071114000
_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  0.0564
_diffrn_reflns_av_unetI/netI     0.0583
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            49649
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         2.602
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    17.608
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.14722
_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    3.287
_exptl_crystal_description       plate
_exptl_crystal_F_000             12270
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.808
_refine_diff_density_min         -1.387
_refine_diff_density_rms         0.287
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     428
_refine_ls_number_reflns         13689
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0692
_refine_ls_R_factor_gt           0.0484
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0215P)^2^+456.2979P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0938
_refine_ls_wR_factor_ref         0.1004
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10712
_reflns_number_total             13689
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01650a3.cif
_cod_data_source_block           PhaseII
_cod_database_code               7713638
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S11-C8A \\sim S11-C7A \\sim S11-C5A
 with sigma of 0.02
 S12-C8A \\sim S12-C7A \\sim S12-C5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C8A) = Uiso(C7A) = Uiso(C5A)
4. Others
 Fixed Sof: S2(0.8) S3(0.7) S4(0.5) S5(0.5) S6(0.45) S7(0.3) S8(0.5) S9(0.2)
 C2AA(0.5) H2AA(0.5) H2AB(0.5) H2AC(0.5) S10(0.55) C5AA(0.5) S11(0.25)
 S12(0.25) C8A(0.5) C1(0.5) C5AB(0.5) C7A(0.5) C5A(0.5)
5.a Me refined with riding coordinates:
 C010(H01A,H01B,H01C), C011(H01D,H01E,H01F), C012(H01M,H01N,H01O), C013(H01G,
 H01H,H01I), C015(H01J,H01K,H01L), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C9(H9A,H9B,
 H9C), C10(H10A,H10B,H10C), C2(H2A,H2B,H2C), C2AA(H2AA,H2AB,H2AC), C3(H3A,H3B,
 H3C), C4(H4A,H4B,H4C), C8(H8A,H8B,H8C)
5.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              28267
_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 4.565
_oxdiff_exptl_absorpt_empirical_full_min 0.471