A bulk photovoltaic effect in a zero-dimensional room-temperature molecular ferroelectric [C<sub>8</sub>N<sub>2</sub>H<sub>22</sub>]<sub>1.5</sub>[Bi<sub>2</sub>I<sub>9</sub>].
Chen, Zhibo; Luo, Tianhong; Wen, Jinrong; Liu, Zhanqiang; Hou, Jingshan; Fang, Yongzheng; Zhang, Ganghua; Dalton transactions (Cambridge, England : 2003) 54 (2024) 267–273; doi:10.1039/d4dt02698e

data_7717430
_publ_section_title
;
 A bulk photovoltaic effect in a zero-dimensional room-temperature
 molecular ferroelectric
 [C<sub>8</sub>N<sub>2</sub>H<sub>22</sub>]<sub>1.5</sub>[Bi<sub>2</sub>I<sub>9</sub>].
;
_journal_issue                   1
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              267
_journal_page_last               273
_journal_paper_doi               10.1039/d4dt02698e
_journal_volume                  54
_journal_year                    2024
_chemical_formula_moiety         'Bi2 I9, 1.5(C8 H22 N2)'
_chemical_formula_sum            'C12 H33 Bi2 I9 N3'
_chemical_formula_weight         1779.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-03-06
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-18 deposited with the CCDC.	2024-11-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.581(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.5341(16)
_cell_length_b                   8.5135(8)
_cell_length_c                   23.945(2)
_cell_measurement_reflns_used    9993
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      27.53
_cell_measurement_theta_min      2.54
_cell_volume                     3557.5(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX5 V2023.9-2 (Bruker, 2023)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      193.0
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_measurement_specimen_support 'nylon loop'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_unetI/netI     0.0670
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            25936
_diffrn_reflns_point_group_measured_fraction_full 0.932
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.974
_diffrn_source_current           40.0
_diffrn_source_power             1.8
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    17.696
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4189
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1289 before and 0.0703 after correction.
The Ratio of minimum to maximum transmission is 0.5618.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    3.322
_exptl_crystal_description       block
_exptl_crystal_F_000             3076
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.771
_refine_diff_density_min         -1.611
_refine_diff_density_rms         0.320
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.48(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     566
_refine_ls_number_reflns         13527
_refine_ls_number_restraints     665
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.0678
_refine_ls_R_factor_gt           0.0468
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0513P)^2^+41.7253P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1299
_reflns_Friedel_coverage         0.862
_reflns_Friedel_fraction_full    0.868
_reflns_Friedel_fraction_max     0.860
_reflns_number_gt                10457
_reflns_number_total             13527
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02698e2.cif
_cod_data_source_block           240202lu_lgpz152634_0m
_cod_depositor_comments          'Adding full bibliography for 7717430.cif.'
_cod_original_sg_symbol_H-M      'P c'
_cod_database_code               7717430
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.843
_shelx_estimated_absorpt_t_min   0.225
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.52(3)
 0.48(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H,H) groups
3. Restrained distances
 N3-C5
 1.57 with sigma of 0.01
 C9-C11
 1.54 with sigma of 0.01
 N4-C11
 1.57 with sigma of 0.01
 N24-C18
 1.57 with sigma of 0.01
 N21A-C24A
 1.57 with sigma of 0.01
 C5-C10 = C13-C10 = C27-C13 = C27-C15 = C15-C14 = C8-C14 = C8-C7
 1.54 with sigma of 0.01
 N2-C25 \\sim N25A-C30A
 with sigma of 0.02
 C27-C13 \\sim C13-C10 \\sim C5-C10 \\sim C27-C15 \\sim C15-C14 \\sim C8-C14
\\sim C8-C7
 with sigma of 0.02
 N2-C25 \\sim N25A-C30A \\sim N24-C18 \\sim N21A-C24A
 with sigma of 0.02
 N24-C18 \\sim C18-C17 \\sim C26-C17 \\sim C28-C26 \\sim C32-C28 \\sim C32-C31
\\sim C31-C30
 with sigma of 0.01
 C24A-C18A \\sim N24-C18 \\sim C18-C17 \\sim C18A-C17A \\sim C26A-C17A \\sim
C26-C17 \\sim C28-C26 ~
 C28A-C26A \\sim C32-C28 \\sim C32A-C28A \\sim C32-C31 \\sim C32A-C31A \\sim
C31A-C30A \\sim C31-C30
 with sigma of 0.02
 C30-C25 \\sim C31-C30 \\sim C32-C31 \\sim C32-C28 \\sim C28-C26 \\sim C26-C17
\\sim C18-C17 \\sim C31A-
 C30A \\sim C32A-C31A \\sim C32A-C28A \\sim C28A-C26A \\sim C26A-C17A \\sim
C18A-C17A \\sim C24A-C18A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C4 \\sim C11 \\sim C6 \\sim C9 \\sim C5 \\sim C7 \\sim C8 \\sim C10 \\sim C16
\\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C18 \\sim N24 \\sim C17 \\sim C20
\\sim C19 \\sim C30 \\sim C31 \\sim C26 \\sim C32 \\sim C28 \\sim C27: within
2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C4 \\sim C11 \\sim C6 \\sim C9 \\sim C5 \\sim C7 \\sim C8 \\sim C10 \\sim C16
\\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C18 \\sim C17 \\sim C20 \\sim C19
\\sim C30 \\sim C31 \\sim C26 \\sim C32 \\sim C28 \\sim C27 \\sim C25 \\sim
C28A \\sim C18A \\sim C24A \\sim C17A \\sim C26A \\sim C32A \\sim C31A \\sim
C30A: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within
2A
C7 \\sim N22: within 1.6A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 1.6A
N3 \\sim N22: within 9.2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 9.2A
C17 \\sim C28A: within 2.3A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2.3A
C31A \\sim C32A: within 1.7A with sigma of 0.005 and sigma for terminal atoms
of 0.01 within 1.7A
N1 \\sim N4 \\sim N3 \\sim N24 \\sim N22 \\sim N21A \\sim N25A \\sim N2: within
2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(N3) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(N22) \\sim
Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C18A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C26A) \\sim Ueq,
Uanis(C32A) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C31A) \\sim Ueq,
Uanis(C30A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(N25A) \\sim Ueq,
Uanis(N21A) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(N24)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C31) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(N2)
\\sim Ueq, Uanis(N4) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(N2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N21A) \\sim Ueq, Uanis(N3) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(N21A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
5. Others
 Fixed Sof: C18(0.5) H18a(0.5) H18b(0.5) N24(0.5) H24a(0.5) H24b(0.5)
 H24c(0.5) C17(0.5) H17a(0.5) H17b(0.5) C30(0.5) H30a(0.5) H30b(0.5) C31(0.5)
 H31a(0.5) H31b(0.5) C26(0.5) H26a(0.5) H26b(0.5) C32(0.5) H32a(0.5) H32b(0.5)
 C28(0.5) H28a(0.5) H28b(0.5) C25(0.5) H25a(0.5) H25b(0.5) C28A(0.5) H28c(0.5)
 H28d(0.5) C18A(0.5) H18c(0.5) H18d(0.5) C24A(0.5) H24d(0.5) H24e(0.5)
 C17A(0.5) H17c(0.5) H17d(0.5) N21A(0.5) H21a(0.5) H21b(0.5) H21c(0.5)
 C26A(0.5) H26c(0.5) H26d(0.5) C32A(0.5) H32c(0.5) H32d(0.5) C31A(0.5)
 H31c(0.5) H31d(0.5) C30A(0.5) H30c(0.5) H30d(0.5) N25A(0.5) H25c(0.5)
 H25d(0.5) H25e(0.5) N2(0.5) H2a(0.5) H2b(0.5) H2c(0.5)
6.a Riding coordinates:
 C7(H7a,H7b), N25A(H25c,H25d,H25e), N2(H2a,H2b,H2c)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4d,H4e), C11(H11a,H11b), C6(H6a,H6b), C9(H9a,H9b), C5(H5a,H5b), C8(H8a,
 H8b), C10(H10a,H10b), C16(H16a,H16b), C12(H12a,H12b), C13(H13a,H13b), C14(H14a,
 H14b), C15(H15a,H15b), C18(H18a,H18b), C17(H17a,H17b), C20(H20a,H20b),
 C19(H19a,H19b), C30(H30a,H30b), C31(H31a,H31b), C26(H26a,H26b), C32(H32a,H32b),
  C28(H28a,H28b), C27(H27a,H27b), C25(H25a,H25b), C28A(H28c,H28d), C18A(H18c,
 H18d), C24A(H24d,H24e), C17A(H17c,H17d), C26A(H26c,H26d), C32A(H32c,H32d),
 C31A(H31c,H31d), C30A(H30c,H30d)
6.c Idealised Me refined as rotating group:
 N1(H1a,H1b,H1c), N4(H4a,H4b,H4c), N3(H3a,H3b,H3c), N24(H24a,H24b,H24c),
 N22(H22a,H22b,H22c), N21A(H21a,H21b,H21c)
;
_olex2_submission_special_instructions 'No special instructions were received'