Direct-Bandgap 2D Silver-Bismuth Iodide Double Perovskite: The Structure-Directing Influence of an Oligothiophene Spacer Cation.
Jana, Manoj K.; Janke, Svenja M.; Dirkes, David J.; Dovletgeldi, Seyitliyev; Liu, Chi; Qin, Xixi; Gundogdu, Kenan; You, Wei; Blum, Volker; Mitzi, David B.; Journal of the American Chemical Society 141 (2019) 7955–7964; doi:10.1021/jacs.9b02909

data_4127220
_publ_section_title
;
 Direct-Bandgap 2D Silver-Bismuth Iodide Double Perovskite: The
 Structure-Directing Influence of an Oligothiophene Spacer Cation.
;
_journal_issue                   19
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7955
_journal_page_last               7964
_journal_paper_doi               10.1021/jacs.9b02909
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'Ag Bi I8, 2(C12 H18 N2 S2)'
_chemical_formula_sum            'C24 H36 Ag Bi I8 N4 S4'
_chemical_formula_weight         1840.86
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-02-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.266(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   28.951(3)
_cell_length_b                   6.0992(6)
_cell_length_c                   11.9821(12)
_cell_measurement_reflns_used    4907
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.45
_cell_measurement_theta_min      2.82
_cell_volume                     2114.1(4)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0252
_diffrn_reflns_av_unetI/netI     0.0152
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            15433
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.503
_diffrn_reflns_theta_min         2.816
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    10.681
_exptl_absorpt_correction_T_max  0.7588
_exptl_absorpt_correction_T_min  0.2561
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    2.892
_exptl_crystal_description       plate
_exptl_crystal_F_000             1652
_exptl_crystal_size_max          0.287
_exptl_crystal_size_mid          0.165
_exptl_crystal_size_min          0.032
_refine_diff_density_max         3.840
_refine_diff_density_min         -2.344
_refine_diff_density_rms         0.290
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     79
_refine_ls_number_reflns         2196
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0665
_refine_ls_R_factor_gt           0.0490
_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^)+(0.0675P)^2^+85.9339P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1339
_refine_ls_wR_factor_ref         0.1484
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1321
_reflns_number_total             2196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02909_si_003.cif
_cod_data_source_block           (AE2T)2AgBiI8_100K
_cod_depositor_comments
'Adding full bibliography for 4127220--4127221.cif.'
_cod_original_cell_volume        2114.2(4)
_cod_database_code               4127220
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.726
_shelx_estimated_absorpt_t_min   0.150
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H,H,H) groups
2. Shared sites
{Ag1, Bi1}
3. Restrained distances
 N4-C0AA \\sim N1-C0AA \\sim N3-C0AA
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(Ag1) = Uanis(Bi1)
5. Rigid body (RIGU) restrains
 C5, C6, C9, C10, C14, C13, C2, C1AA, C3, C4, C0AA, N1, N3, N4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1AA, C5, C6, C9, C10, C14, C13, C2, C3, C4, C0AA, N1, N3, N4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Ag1(0.25) Bi1(0.25) I3(0.5) I4(0.5) C2(0.5) H2(0.5) C3(0.5)
 H3(0.5) C5(0.5) C6(0.5) C9(0.5) C10(0.5) C13(0.5) H13(0.5) C14(0.5) H14(0.5)
 N1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) H0AA(0.5) H0AB(0.5) H0AC(0.5) H0AD(0.5)
 C1AA(0.5) H1AA(0.5) H1AB(0.5) C4(0.5) H4A(0.5) H4B(0.5) N3(0.25) H3A(0.25)
 H3B(0.25) H3C(0.25) N4(0.25) H4C(0.25) H4D(0.25) H4E(0.25)
 Fixed U11: Ag1(0.031941) Bi1(0.031941) I2(0.038393) I3(0.011659) I4(0.016494)
 Fixed U12: Ag1(0) Bi1(0) I2(0.000115) I3(0.000935) I4(-0.003534)
 Fixed U13: Ag1(-0.000103) Bi1(-0.000103) I2(-0.001044) I3(0.001235) I4(-
 0.000336)
 Fixed U22: Ag1(0.01329) Bi1(0.01329) I2(0.02478) I3(0.00733) I4(0.01308)
 Fixed U23: Ag1(0) Bi1(0) I2(0.00013) I3(0.00014) I4(0.00079)
 Fixed U33: Ag1(0.01727) Bi1(0.01727) I2(0.01221) I3(0.01356) I4(0.01152)
7.a Secondary CH2 refined with riding coordinates:
 C0AA(H0AA,H0AB), C0AA(H0AC,H0AD), C1AA(H1AA,H1AB), C4(H4A,H4B)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C13(H13), C14(H14)
7.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C), N3(H3A,H3B,H3C), N4(H4C,H4D,H4E)
;
_shelx_res_checksum              17822
_shelx_hkl_checksum              4165
_olex2_submission_special_instructions 'No special instructions were received'