Triiodide-Induced Band-Edge Reconstruction of a Lead-Free Perovskite-Derivative Hybrid for Strong Light Absorption
Zhang, Weichuan; Liu, Xitao; Li, Lina; Sun, Zhihua; Han, Shiguo; Wu, Zhenyue; Luo, Junhua; Chemistry of Materials 30 (2018) 4081–; doi:10.1021/acs.chemmater.8b01200

data_4003362
_publ_section_title
;
 Triiodide-Induced Band-Edge Reconstruction of a Lead-Free
 Perovskite-Derivative Hybrid for Strong Light Absorption
;
_journal_issue                   12
_journal_name_full               'Chemistry of Materials'
_journal_page_first              4081
_journal_paper_doi               10.1021/acs.chemmater.8b01200
_journal_volume                  30
_journal_year                    2018
_chemical_formula_moiety         'Bi2 I9, 1.5(C12 H28 N2)'
_chemical_formula_sum            'C18 H42 Bi2 I9 N3'
_chemical_formula_weight         1860.60
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-01-25
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.1506(6)
_cell_length_b                   8.6004(2)
_cell_length_c                   16.1217(4)
_cell_measurement_reflns_used    4466
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.9600
_cell_measurement_theta_min      3.9990
_cell_volume                     4180.47(16)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5594
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.972
_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   -122.00   6.00   1.00    2.75    --  -40.15 -19.00 -60.00  128
  2  \w     32.00 134.00   1.00   11.03    --  106.29 -45.00  60.00  102
  3  \w     94.00 178.00   1.00   11.03    --  106.29 125.00  90.00   84
  4  \w     31.00 122.00   1.00   11.03    --  106.29-125.00-120.00   91
  5  \w    -70.00 -33.00   1.00    2.75    --  -40.15  57.00  90.00   37
  6  \w   -122.00   6.00   1.00    2.75    --  -40.15 -19.00  90.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0169213000
_diffrn_orient_matrix_UB_12      -0.0600578000
_diffrn_orient_matrix_UB_13      0.0842792000
_diffrn_orient_matrix_UB_21      -0.0462527000
_diffrn_orient_matrix_UB_22      0.0266148000
_diffrn_orient_matrix_UB_23      0.0379608000
_diffrn_orient_matrix_UB_31      -0.0135437000
_diffrn_orient_matrix_UB_32      -0.1666256000
_diffrn_orient_matrix_UB_33      -0.0244225000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            12801
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.382
_diffrn_reflns_theta_min         4.015
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    68.611
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16295
_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_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.956
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             3256
_refine_diff_density_max         1.135
_refine_diff_density_min         -1.139
_refine_diff_density_rms         0.220
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         4379
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0476P)^2^+11.7450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1065
_refine_ls_wR_factor_ref         0.1177
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3333
_reflns_number_total             4379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm8b01200_si_002.cif
_cod_data_source_block           WeiChuanZhang-23-(C6H13N)3Bi2I9
_cod_database_code               4003362
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Bi I C N H'
_reflns_odcompleteness_completeness 99.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1-C2 = C2-C3 = C3-N1 = N1-C4 = C4-C5 = C5-C1
 1.5 with sigma of 0.01
 C7-C8 = C8-C9 = C9-N3 = N3-C10 = C10-C11 = C11-C7
 1.5 with sigma of 0.01
 C13-C14 = C14-C15 = C15-N2 = N2-C16 = C16-C17 = C17-C13
 1.5 with sigma of 0.01
 C1-C6
 1.5 with sigma of 0.01
 C7-C12
 1.5 with sigma of 0.01
 C13-C18
 1.5 with sigma of 0.01
3. Rigid bond restraints
 C11, C4, C13, C1, C8, C16, C18, C2, C6, C5, C12, N3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C11 \\sim C4 \\sim C13 \\sim C1 \\sim C8 \\sim C16 \\sim C18 \\sim C2 \\sim C6
\\sim C5 \\sim C12 \\sim N3: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
5. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H15A(0.5) H15B(0.5) H2C(0.5) H2D(0.5) H3C(0.5)
 H3D(0.5) H9A(0.5) H9B(0.5) H11A(0.5) H11B(0.5) H4A(0.5) H4B(0.5) H13(0.5)
 H1(0.5) H8A(0.5) H8B(0.5) H3A(0.5) H3B(0.5) H14A(0.5) H14B(0.5) H16A(0.5)
 H16B(0.5) H17A(0.5) H17B(0.5) H18A(0.5) H18B(0.5) H18C(0.5) H2A(0.5) H2B(0.5)
 H6A(0.5) H6B(0.5) H6C(0.5) H5A(0.5) H5B(0.5) H12A(0.5) H12B(0.5) H12C(0.5)
 H10A(0.5) H10B(0.5) H7(0.5)
6.a Riding coordinates:
 C12(H12A,H12B,H12C)
6.b Ternary CH refined with riding coordinates:
 C13(H13), C1(H1), C7(H7)
6.c Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C15(H15A,H15B), N2(H2C,H2D), N3(H3C,H3D), C9(H9A,H9B), C11(H11A,
 H11B), C4(H4A,H4B), C8(H8A,H8B), C3(H3A,H3B), C14(H14A,H14B), C16(H16A,H16B),
 C17(H17A,H17B), C2(H2A,H2B), C5(H5A,H5B), C10(H10A,H10B)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C6(H6A,H6B,H6C)
;
_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 3.319
_oxdiff_exptl_absorpt_empirical_full_min 0.602