Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb23BiIIIxSbIII7‒xSbV2Cl54 (0 ≤ x ≤ 7)
Benin, Bogdan M.; McCall, Kyle M.; Wörle, Michael; Borgeaud, Dominique; Vonderach, Thomas; Sakhatskyi, Kostiantyn; Yakunin, Sergii; Günther, Detlef; Kovalenko, Maksym V.; Chemistry of Materials  (2021) –; doi:10.1021/acs.chemmater.0c04491

data_4003894
_publ_section_title
;
 Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D
 Metal-Halides Rb23BiIIIxSbIII7--xSbV2Cl54 (0 &#x2264; x &#x2264; 7)
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.0c04491
_journal_year                    2021
_chemical_formula_moiety         '0.17(Bi39.74 Cl324 Rb138 Sb14.26)'
_chemical_formula_sum            'Bi6.62 Cl54 Rb23 Sb2.38'
_chemical_formula_weight         5553.61
_space_group_crystal_system      trigonal
_space_group_IT_number           155
_space_group_name_Hall           'R 3 2"'
_space_group_name_H-M_alt        'R 3 2 :H'
_atom_sites_solution_primary     dual
_audit_creation_date             2020-08-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   12.9752(6)
_cell_length_b                   12.9752(6)
_cell_length_c                   112.438(7)
_cell_measurement_reflns_used    5157
_cell_measurement_temperature    298
_cell_measurement_theta_max      31.3840
_cell_measurement_theta_min      1.6150
_cell_volume                     16393.5(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      298.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.949
_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      2.18 182.00   0.30   43.42    --   28.00  73.93 -25.82  600
  2  \w      2.18 182.00   0.30   43.43    --   28.00  73.93  94.18  600
  3  \w      2.18 182.00   0.30   43.41    --   28.00  73.93-145.82  600
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0973
_diffrn_reflns_av_unetI/netI     0.0547
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       156
_diffrn_reflns_limit_l_min       -160
_diffrn_reflns_number            62871
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.525
_diffrn_reflns_theta_min         1.630
_exptl_absorpt_coefficient_mu    22.719
_exptl_absorpt_correction_T_max  0.04195
_exptl_absorpt_correction_T_min  0.01734
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019) Spherical absorption correction using equivalent radius of 0.15 mm and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    3.375
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             14640
_exptl_crystal_recrystallization_method
'Solvothermal reaction in HCl at 160 degrees'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.05
_refine_diff_density_max         6.069
_refine_diff_density_min         -3.405
_refine_diff_density_rms         0.384
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.50(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         11380
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.1204
_refine_ls_R_factor_gt           0.0864
_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^)+(0.0973P)^2^+1152.8619P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2231
_refine_ls_wR_factor_ref         0.2438
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.914
_reflns_number_gt                8129
_reflns_number_total             11380
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c04491_si_003.cif
_cod_data_source_block           km3
_cod_original_cell_volume        16393.5(18)
_cod_original_sg_symbol_H-M      'R 3 2'
_cod_database_code               4003894
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.396
_shelx_estimated_absorpt_t_min   0.064
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.50(2)
 0.50(2)
2. Shared sites
{Bi4, Sb4}
3. Uiso/Uaniso restraints and constraints
Uanis(Bi4) = Uanis(Sb4)
4. Others
 Sof(Sb4)=1-FVAR(1)
 Sof(Bi4)=FVAR(1)
 Fixed Sof: Rb11(0.33333) Rb12(0.66667) Rb13(0.33333) Rb14(0.16667)
 Rb15(0.33333) Cl16(0.33333) Cl17(0.33333) Cl18(0.33333) Cl19(0.33333)
 Cl20(0.33333) Cl21(0.33333) Cl22(0.33333) Cl23(0.33333) Cl24(0.33333)
;
_shelx_res_checksum              72354
_shelx_hkl_checksum              84470
_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
- Detector area scaling
;