Understanding the effect of hydrogen bonding on the structural transition and emission properties in zero-dimensional hybrid metal halides: (3,5-DMP)3BiX6 (X = Cl, Br, I).
Sahoo, Subhasish; Rana, Rajanikanta; Srinivas, Chakali; Iyer, Parameswar Krishnan; Dash, Laxmipriya; Biswal, Himansu S.; Samal, Saroj L.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 15726–15744; doi:10.1039/d5dt01876e

data_7719611
_publ_section_title
;
 Understanding the effect of hydrogen bonding on the structural transition
 and emission properties in zero-dimensional hybrid metal halides:
 (3,5-DMP)3BiX6 (X = Cl, Br, I).
;
_journal_issue                   42
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              15726
_journal_page_last               15744
_journal_paper_doi               10.1039/d5dt01876e
_journal_volume                  54
_journal_year                    2025
_chemical_absolute_configuration 'C21 H48 Bi Cl6 N3'
_chemical_formula_moiety         'Bi Cl6, 3(C7 H16 N)'
_chemical_formula_sum            'C21 H48 Bi Cl6 N3'
_chemical_formula_weight         764.30
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-24
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.11.02 svn.ra8b101fa for OlexSys, GUI svn.r6635)
;
_audit_update_record
;
2025-07-28 deposited with the CCDC.	2025-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.9940(2)
_cell_length_b                   18.2868(5)
_cell_length_c                   22.7542(5)
_cell_measurement_reflns_used    9692
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.8750
_cell_measurement_theta_min      2.0960
_cell_volume                     3326.32(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.955
_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      1.00  26.00   0.50   13.56    --   10.00  80.00 -16.00   50
  2  \w    -10.00  19.00   0.50   13.56    --   10.00 -46.00  56.00   58
  3  \w     -9.00  28.00   0.50   13.56    --  -10.20  46.00-153.00   74
  4  \w     58.00  97.00   0.50   13.56    --   10.00  77.00  60.00   78
  5  \w      7.00  99.00   0.50   13.56    --   10.00  77.00 150.00  184
  6  \w    -13.00  94.00   0.50   13.56    --   10.00  77.00 -90.00  214
  7  \w     11.00  37.00   0.50   13.56    --   10.00  77.00  60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0337632000
_diffrn_orient_matrix_UB_12      -0.0351765000
_diffrn_orient_matrix_UB_13      0.0056011000
_diffrn_orient_matrix_UB_21      -0.0378013000
_diffrn_orient_matrix_UB_22      -0.0133562000
_diffrn_orient_matrix_UB_23      -0.0260974000
_diffrn_orient_matrix_UB_31      0.0727961000
_diffrn_orient_matrix_UB_32      0.0093818000
_diffrn_orient_matrix_UB_33      -0.0161333000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0666
_diffrn_reflns_av_unetI/netI     0.0678
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            21191
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.926
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.988
_diffrn_reflns_theta_min         1.790
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.796
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27600
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       crystalline
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_refine_diff_density_max         2.394
_refine_diff_density_min         -1.076
_refine_diff_density_rms         0.131
_refine_ls_abs_structure_details
;
 Flack x determined using 2030 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         6717
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0469
_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^)+(0.0679P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1147
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.720
_reflns_Friedel_fraction_full    0.973
_reflns_Friedel_fraction_max     0.888
_reflns_number_gt                5697
_reflns_number_total             6717
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01876e2.cif
_cod_data_source_block           ss87
_cod_depositor_comments
'Adding full bibliography for 7719611--7719613.cif.'
_cod_database_code               7719611
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N Bi Cl'
_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. Uiso/Uaniso restraints and constraints
N2 \\sim C12 \\sim C8 \\sim C11 \\sim C9 \\sim C14 \\sim C10 \\sim C13: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 N2, C12, C11, C8, C13, C14, C9, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Ternary CH refined with riding coordinates:
 C18(H18), C4(H4), C16(H16), C2(H2), C11(H11), C9(H9)
4.b Secondary CH2 refined with riding coordinates:
 N3(H3A,H3B), N1(H1A,H1B), C3(H3C,H3D), N2(H2A,H2B), C17(H17A,H17B), C19(H19A,
 H19B), C15(H15A,H15B), C1(H1C,H1D), C5(H5A,H5B), C12(H12A,H12B), C8(H8A,H8B),
 C10(H10A,H10B)
4.c Me refined with riding coordinates:
 C21(H21A,H21B,H21C), C6(H6A,H6B,H6C), C20(H20A,H20B,H20C), C7(H7A,H7B,H7C)
4.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              48371
_shelx_hkl_checksum              4271
_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 3.496
_oxdiff_exptl_absorpt_empirical_full_min 0.407