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_7719612
_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 I6 N3'
_chemical_formula_moiety         'Bi I6, 3(C7 H16 N)'
_chemical_formula_sum            'C21 H48 Bi I6 N3'
_chemical_formula_weight         1313.00
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_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                   22.1606(7)
_cell_length_b                   20.0231(7)
_cell_length_c                   8.5783(3)
_cell_measurement_reflns_used    6933
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.0960
_cell_measurement_theta_min      1.8370
_cell_volume                     3806.4(2)
_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 0.998
_diffrn_measured_fraction_theta_max 0.950
_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    -14.00  11.00   0.50   46.10    --   10.00 -10.00  98.00   50
  2  \w    -35.00 -10.00   0.50   46.10    --  -10.20 -10.00  98.00   50
  3  \w    -17.00  99.00   0.50   46.10    --   10.00  82.00  30.00  232
  4  \w     13.00  99.00   0.50   46.10    --   10.00  77.00 -60.00  172
  5  \w    -20.00  27.00   0.50   46.10    --   10.00  57.00   0.00   94
  6  \w      4.00  52.00   0.50   46.10    --  -10.20  38.00   0.00   96
;
_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      0.0204533000
_diffrn_orient_matrix_UB_12      -0.0268550000
_diffrn_orient_matrix_UB_13      -0.0107926000
_diffrn_orient_matrix_UB_21      -0.0245138000
_diffrn_orient_matrix_UB_22      -0.0227567000
_diffrn_orient_matrix_UB_23      -0.0016045000
_diffrn_orient_matrix_UB_31      -0.0022617000
_diffrn_orient_matrix_UB_32      0.0039676000
_diffrn_orient_matrix_UB_33      -0.0819663000
_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  0.0410
_diffrn_reflns_av_unetI/netI     0.0834
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            23033
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.084
_diffrn_reflns_theta_min         1.838
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    9.511
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12794
_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            red
_exptl_crystal_density_diffrn    2.291
_exptl_crystal_description       crystalline
_exptl_crystal_F_000             2384
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.769
_refine_diff_density_min         -0.641
_refine_diff_density_rms         0.123
_refine_ls_abs_structure_details
;
 Flack x determined using 1480 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.030(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.930
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         7626
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      0.926
_refine_ls_R_factor_all          0.0911
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0172P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0473
_refine_ls_wR_factor_ref         0.0538
_reflns_Friedel_coverage         0.711
_reflns_Friedel_fraction_full    0.958
_reflns_Friedel_fraction_max     0.859
_reflns_number_gt                4665
_reflns_number_total             7626
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01876e2.cif
_cod_data_source_block           ss125_solvent_270223
_cod_depositor_comments
'Adding full bibliography for 7719611--7719613.cif.'
_cod_database_code               7719612
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N Bi I'
_reflns_odcompleteness_completeness 99.43
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
N1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C7 \\sim C6: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C19 \\sim N3 \\sim C15 \\sim C18 \\sim C16 \\sim C17 \\sim C21 \\sim C20:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 N1, C1, C2, C3, C4, C5, C7, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, N3, C15, C18, C16, C17, C21, C20
 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:
 C11(H11), C2(H2), C4(H4), C9(H9), C18(H18), C16(H16)
4.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C1(H1C,H1D), C10(H10A,H10B), C8(H8A,H8B), N2(H2A,H2B), C3(H3A,
 H3B), C5(H5A,H5B), C12(H12A,H12B), C19(H19A,H19B), N3(H3C,H3D), C15(H15A,H15B),
  C17(H17A,H17B)
4.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C7(H7A,H7B,H7C), C6(H6A,H6B,H6C),
 C21(H21A,H21B,H21C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              33846
_shelx_hkl_checksum              97424
_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 3.701
_oxdiff_exptl_absorpt_empirical_full_min 0.448