A new hybrid bismuth chloride semiconductor (C<sub>5</sub>H<sub>7</sub>BrN<sub>3</sub>)<sub>6</sub>(BiCl<sub>5</sub>)<sub>3</sub>: powder XRD, optical properties, and DFT investigation.
Jridi, Chaima; Elleuch, Nour; Shova, Sergiu; Lhoste, Jerome; Amiard, Frédéric; Boujelbene, Mohamed; RSC advances 16 (2026) 6299–6313; doi:10.1039/d5ra09478j

data_7251747
_publ_section_title
;
 A new hybrid bismuth chloride semiconductor
 (C<sub>5</sub>H<sub>7</sub>BrN<sub>3</sub>)<sub>6</sub>(BiCl<sub>5</sub>)<sub>3</sub>:
 powder XRD, optical properties, and DFT investigation.
;
_journal_issue                   7
_journal_name_full               'RSC advances'
_journal_page_first              6299
_journal_page_last               6313
_journal_paper_doi               10.1039/d5ra09478j
_journal_volume                  16
_journal_year                    2026
_chemical_formula_moiety         '3(Bi Cl5), 6(C5 H7 Br N3)'
_chemical_formula_sum            'C30 H42 Bi3 Br6 Cl15 N18'
_chemical_formula_weight         2292.96
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-16 deposited with the CCDC.	2026-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                114.469(4)
_cell_angle_beta                 92.108(4)
_cell_angle_gamma                92.067(4)
_cell_formula_units_Z            2
_cell_length_a                   10.9543(5)
_cell_length_b                   16.4575(7)
_cell_length_c                   19.2722(8)
_cell_measurement_reflns_used    4212
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.6000
_cell_measurement_theta_min      1.8670
_cell_volume                     3155.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.112a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.112a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.112a (Rigaku OD, 2025)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.1593
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -49.00 -23.00   1.00   75.00    --  -15.13 109.00 148.00   26
  2  \w    -12.00  14.00   1.00   75.00    --   17.63-109.00  52.00   26
  3  \w    -24.00  10.00   1.00   75.00    --  -15.13 -77.00  90.00   34
  4  \w    -74.00   4.00   1.00   75.00    --  -15.13 -38.00  30.00   78
  5  \w     27.00  87.00   1.00   75.00    --   17.63  38.00  30.00   60
  6  \w    -19.00   8.00   1.00   75.00    --   17.63 -99.00-150.00   27
  7  \w    -20.00  57.00   1.00   75.00    --   17.63 -99.00-120.00   77
  8  \w    -49.00  28.00   1.00   75.00    --   17.63 -57.00 -60.00   77
  9  \w      6.00  31.00   1.00   75.00    --   17.63  77.00 -90.00   25
 10  \w     35.00  60.00   1.00   75.00    --   17.63-109.00  52.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0643
_diffrn_reflns_av_unetI/netI     0.1174
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            26631
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.127
_exptl_absorpt_coefficient_mu    12.823
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53917
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.112a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.414
_exptl_crystal_description       block
_exptl_crystal_F_000             2124
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.929
_refine_diff_density_min         -1.642
_refine_diff_density_rms         0.186
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     610
_refine_ls_number_reflns         11118
_refine_ls_number_restraints     148
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1427
_refine_ls_R_factor_gt           0.0658
_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^)+(0.0447P)^2^+6.1994P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1193
_refine_ls_wR_factor_ref         0.1485
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5905
_reflns_number_total             11118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra09478j1.cif
_cod_data_source_block           shi_6739_mobo_auto
_cod_database_code               7251747
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C5H6N3Cl4Bi1
_chemical_oxdiff_usercomment     '3100 ma'
_shelx_estimated_absorpt_t_max   0.628
_shelx_estimated_absorpt_t_min   0.249
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
2. Restrained distances
 N3-N2
 2.78 with sigma of 0.02
 C6-C19
 1.46 with sigma of 0.02
 C8-C19
 2.36 with sigma of 0.02
 Br7A-C8A = Br7-C8
 1.85 with sigma of 0.02
 Br7A_$1-Br7A
 2.7 with sigma of 0.02
 Br7A-Br7A_$1
 3 with sigma of 0.01
 Br7-C8 \\sim Br7A-C8A
 with sigma of 0.02
 C13-C8 \\sim C13A-C8A
 with sigma of 0.02
 C13-N16 \\sim C13A-N16A
 with sigma of 0.02
 C8-C17 \\sim C8A-C17A
 with sigma of 0.02
 N16-C6 \\sim N16A-C6A
 with sigma of 0.02
 C17-C19 \\sim C17A-C19A
 with sigma of 0.02
 N2-C6 \\sim N2A-C6A
 with sigma of 0.02
 N3-C19 \\sim N3A-C19A
 with sigma of 0.02
 C6-C19 \\sim C6A-C19A
 with sigma of 0.02
 Br7-C13 \\sim Br7A-C13A
 with sigma of 0.04
 Br7-C17 \\sim Br7A-C17A
 with sigma of 0.04
 C13-C17 \\sim C13A-C17A
 with sigma of 0.04
 C13-C6 \\sim C13A-C6A
 with sigma of 0.04
 C8-N16 \\sim C8A-N16A
 with sigma of 0.04
 C8-C19 \\sim C8A-C19A
 with sigma of 0.04
 N16-N2 \\sim N16A-N2A
 with sigma of 0.04
 N16-C19 \\sim N16A-C19A
 with sigma of 0.04
 C17-N3 \\sim C17A-N3A
 with sigma of 0.04
 C17-C6 \\sim C17A-C6A
 with sigma of 0.04
 N2-C19 \\sim N2A-C19A
 with sigma of 0.04
 N3-C6 \\sim N3A-C6A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C02J) = Uanis(C23) = Uanis(C02K) = Uanis(C24) = Uanis(C01F)
Uanis(C14) = Uanis(C3) = Uanis(C1) = Uanis(C21) = Uanis(C2)
Uanis(N1) = Uanis(N01E)
Uanis(N8) = Uanis(N1)
Uanis(C9) = Uanis(N01S) = Uanis(C5) = Uanis(C12) = Uanis(C7) = Uanis(C18) =
Uanis(C10) = Uanis(C014) = Uanis(C11) = Uanis(C15)
Uanis(C8A) = Uanis(C7) = Uanis(C17A) = Uanis(C5)
Uanis(C13A) = Uanis(C4)
Uanis(C13) = Uanis(C12)
4. Rigid body (RIGU) restrains
 Br7, C13, C8, N16, C17, N2, N3, C6, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br7A, C13A, C8A, N16A, C17A, N2A, N3A, C6A, C19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N2A)=Sof(H2AA)=Sof(H2AB)=Sof(Br7A)=Sof(C8A)=Sof(C13A)=Sof(H13A)=Sof(C17A)=
 Sof(H17A)=Sof(N16A)=Sof(H16A)=Sof(C19A)=Sof(C6A)=Sof(N3A)=Sof(H3AA)=Sof(H3AB)=
 1-FVAR(1)
 Sof(Br7)=Sof(C13)=Sof(H13)=Sof(C8)=Sof(N16)=Sof(H16)=Sof(C17)=Sof(H17)=
 Sof(N2)=Sof(H2A)=Sof(H2B)=Sof(N3)=Sof(H3A)=Sof(H3B)=Sof(C6)=Sof(C19)=FVAR(1)
 Fixed Sof: Br3(0.75) Br6(0.25)
6.a Rotating group:
 N0K(H0KA,H0KB), N01R(H01C,H01D), N02L(H02C,H02E), N02N(H02A,H02B), N14(H14A,
 H14B), N10(H10A,H10B), N3(H3A,H3B), N3A(H3AA,H3AB)
6.b Aromatic/amide H refined with riding coordinates:
 C00X(H00X), C014(H014), N01E(H01E), C01O(H01O), N01S(H01S), C3(H3),
 N02D(H02D), C02J(H02J), C02K(H02K), C2(H2), N1(H1), N8(H8), C5(H5), C4(H4),
 C18(H18), C13(H13), N16(H16), C17(H17), C13A(H13A), C17A(H17A), N16A(H16A)
6.c X=CH2 refined with riding coordinates:
 N01A(H01A,H01B), N020(H02H,H02I), N02R(H02F,H02G), N29(H29A,H29B), N2(H2A,
 H2B), N2A(H2AA,H2AB)
;
_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 1.811
_oxdiff_exptl_absorpt_empirical_full_min 0.779