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_4003891
_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(Bi14.99 Cl324 Rb138 Sb39.01)'
_chemical_formula_sum            'Bi2.5 Cl54 Rb23 Sb6.5'
_chemical_formula_weight         5193.79
_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'
_audit_creation_date             2020-08-17
_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                   12.95670(10)
_cell_length_b                   12.95670(10)
_cell_length_c                   111.7130(14)
_cell_measurement_reflns_used    50227
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      44.6750
_cell_measurement_theta_min      1.8040
_cell_volume                     16241.4(3)
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_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    -74.57 132.93   0.50  119.97    --  -34.83  73.75  68.87  415
  2  \w    -74.57 132.93   0.50  119.97    --  -34.83  73.75-118.18  415
  3  \w    -74.57 132.93   0.50  119.97    --  -34.83  73.75 -29.39  415
  4  \w    -74.57 132.93   0.50  119.97    --  -34.83  73.75 155.76  415
  5  \w    -99.49 108.51   0.50  119.97    --  -59.74  73.75  22.75  416
  6  \w    -74.57 132.93   0.50  119.97    --  -34.83  73.75 -72.71  415
  7  \w    -74.57 132.93   0.50  119.97    --  -34.83  73.75 113.88  415
  8  \w   -100.81 106.69   0.50  119.97    --  -61.07  73.75-154.07  415
  9  \w    -27.86 179.64   0.50  119.97    --   11.89  73.75 -25.74  415
 10  \w    -74.57 132.93   0.50  119.97    --  -34.83  73.75   9.31  415
 11  \w    -72.47 133.03   0.50  119.97    --  -33.73  73.75-160.74  411
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0190940000
_diffrn_orient_matrix_UB_12      0.0396043000
_diffrn_orient_matrix_UB_13      0.0020401000
_diffrn_orient_matrix_UB_21      -0.0067049667
_diffrn_orient_matrix_UB_22      -0.0234310333
_diffrn_orient_matrix_UB_23      0.0058687667
_diffrn_orient_matrix_UB_31      0.0598601667
_diffrn_orient_matrix_UB_32      0.0433310333
_diffrn_orient_matrix_UB_33      0.0013089333
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1364
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       168
_diffrn_reflns_limit_l_min       -168
_diffrn_reflns_number            291748
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.577
_diffrn_reflns_theta_min         1.641
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    17.266
_exptl_absorpt_correction_T_max  0.622
_exptl_absorpt_correction_T_min  0.052
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.186
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             13848
_exptl_crystal_recrystallization_method
'Solvothermal reaction in HCl at 160 degrees C'
_exptl_crystal_size_max          0.351
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.963
_refine_diff_density_min         -3.740
_refine_diff_density_rms         0.221
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.493(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         13184
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0808
_refine_ls_R_factor_gt           0.0582
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0192P)^2^+481.0651P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1111
_reflns_Friedel_coverage         0.796
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                10266
_reflns_number_total             13184
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c04491_si_002.cif
_cod_data_source_block           dp059_red_full
_cod_original_sg_symbol_H-M      'R 3 2'
_cod_original_formula_sum        'Bi2.50 Cl54 Rb23 Sb6.50'
_cod_database_code               4003891
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Rb7Sb2BiCl18
_shelx_estimated_absorpt_t_max   0.625
_shelx_estimated_absorpt_t_min   0.065
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.507(16)
 0.493(16)
2. Shared sites
{Bi6, Sb6}
{Bi4, Sb4}
{Bi3, Sb3}
{Sb2, Bi2}
{Bi1, Sb1}
3. Uiso/Uaniso restraints and constraints
Uanis(Bi6) = Uanis(Sb6)
Uanis(Bi4) = Uanis(Sb4)
Uanis(Bi3) = Uanis(Sb3)
Uanis(Sb2) = Uanis(Bi2)
Uanis(Bi1) = Uanis(Sb1)
4. Others
 Sof(Sb6)=0.5*(1-FVAR(2))
 Sof(Bi6)=0.5*FVAR(2)
 Sof(Sb4)=1-FVAR(2)
 Sof(Bi4)=FVAR(2)
 Sof(Sb3)=0.33333*(1-FVAR(4))
 Sof(Bi3)=0.33333*FVAR(4)
 Sof(Bi2)=0.33333*(1-FVAR(5))
 Sof(Sb2)=0.33333*FVAR(5)
 Sof(Sb1)=0.5*(1-FVAR(6))
 Sof(Bi1)=0.5*FVAR(6)
 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              19362
_shelx_hkl_checksum              81033
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.196
_oxdiff_exptl_absorpt_empirical_full_min 0.565