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_7719613
_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 Br6 N3'
_chemical_formula_moiety         'Bi Br6, 3(C7 H16 N)'
_chemical_formula_sum            'C21 H48 Bi Br6 N3'
_chemical_formula_weight         1031.06
_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             2024-10-23
_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                   21.4465(5)
_cell_length_b                   19.4530(4)
_cell_length_c                   8.1701(2)
_cell_measurement_reflns_used    8900
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.7150
_cell_measurement_theta_min      1.8980
_cell_volume                     3408.56(13)
_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 1.000
_diffrn_measured_fraction_theta_max 0.951
_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    -70.00 -44.00   0.50   40.45    --   10.00  21.00-107.00   52
  2  \w    -89.00 -64.00   0.50   40.45    --  -10.20  21.00-107.00   50
  3  \w    -12.00  19.00   0.50   40.45    --   10.00  77.00   0.00   62
  4  \w      5.00  31.00   0.50   40.45    --   10.00  77.00 -60.00   52
  5  \w     67.00  99.00   0.50   40.45    --   10.00  77.00   0.00   64
  6  \w    -79.00  35.00   0.50   40.45    --   10.00 -77.00-180.00  228
  7  \w     28.00  54.00   0.50   40.45    --   10.00  77.00   0.00   52
  8  \w    -38.00  16.00   0.50   40.45    --  -10.20 -82.00-120.00  108
  9  \w    -80.00 -54.00   0.50   40.45    --  -10.20 -82.00-120.00   52
 10  \w    -35.00 -10.00   0.50   40.45    --  -10.20  21.00-107.00   50
;
_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      0.0219741000
_diffrn_orient_matrix_UB_12      0.0253774000
_diffrn_orient_matrix_UB_13      0.0236507000
_diffrn_orient_matrix_UB_21      -0.0235698000
_diffrn_orient_matrix_UB_22      0.0255019000
_diffrn_orient_matrix_UB_23      -0.0043084000
_diffrn_orient_matrix_UB_31      -0.0074574000
_diffrn_orient_matrix_UB_32      -0.0058805000
_diffrn_orient_matrix_UB_33      0.0834329000
_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  0.0417
_diffrn_reflns_av_unetI/netI     0.0631
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            23702
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.906
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.114
_diffrn_reflns_theta_min         1.899
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    12.220
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25498
_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            yellow
_exptl_crystal_density_diffrn    2.009
_exptl_crystal_description       crystalline
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.571
_refine_diff_density_min         -0.850
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 1680 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.057(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.978
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         6824
_refine_ls_number_restraints     335
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.0647
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0183P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0475
_refine_ls_wR_factor_ref         0.0515
_reflns_Friedel_coverage         0.693
_reflns_Friedel_fraction_full    0.942
_reflns_Friedel_fraction_max     0.848
_reflns_number_gt                5129
_reflns_number_total             6824
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01876e2.cif
_cod_data_source_block           ss95_261222
_cod_depositor_comments
'Adding full bibliography for 7719611--7719613.cif.'
_cod_database_code               7719613
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N Bi Br'
_reflns_odcompleteness_completeness 99.45
_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, All N(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C1 \\sim N1-C26
 with sigma of 0.02
 C5-C7 \\sim C22-C27
 with sigma of 0.04
 C3-C7 \\sim C24-C27
 with sigma of 0.04
 N1-C5 \\sim N1-C22
 with sigma of 0.02
 C3-C2 \\sim C24-C25
 with sigma of 0.02
 C1-C6 \\sim C26-C28
 with sigma of 0.04
 C3-C4 \\sim C24-C23
 with sigma of 0.02
 C1-C2 \\sim C26-C25
 with sigma of 0.02
 C5-C4 \\sim C22-C23
 with sigma of 0.02
 C3-C6 \\sim C24-C28
 with sigma of 0.04
 C2-C6 \\sim C25-C28
 with sigma of 0.02
 C2-C4 \\sim C25-C23
 with sigma of 0.04
 C4-C7 \\sim C23-C27
 with sigma of 0.02
 N1-C2 \\sim N1-C25
 with sigma of 0.04
 N1-C4 \\sim N1-C23
 with sigma of 0.04
 C3-C1 \\sim C24-C26
 with sigma of 0.04
 C3-C5 \\sim C24-C22
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C22 \\sim N1 \\sim C1 \\sim C5 \\sim C26 \\sim C2 \\sim C4 \\sim C25 \\sim C23
\\sim C3 \\sim C6 \\sim C7 \\sim C24 \\sim C28 \\sim C27: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C24, N1, C1, C5, C26, C22, C2, C4, C25, C23, C3, C6, C7, C28, C27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H1BC)=Sof(H1BD)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C25)=Sof(H25)=Sof(C23)=Sof(H23)=Sof(C28)=
 Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C2)=Sof(H2)=Sof(C4)=Sof(H4)=Sof(C6)=Sof(H6A)=
 Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C16(H16), C9(H9), C18(H18), C2(H2), C11(H11), C4(H4), C25(H25), C23(H23)
6.b Secondary CH2 refined with riding coordinates:
 N3(H3C,H3D), N1(H1AA,H1AB), N1(H1BC,H1BD), N2(H2A,H2B), C17(H17A,H17B),
 C15(H15A,H15B), C10(H10A,H10B), C19(H19A,H19B), C8(H8A,H8B), C3(H3A,H3B),
 C1(H1A,H1B), C5(H5A,H5B), C12(H12A,H12B), C24(H24A,H24B), C26(H26A,H26B),
 C22(H22A,H22B)
6.c Me refined with riding coordinates:
 C21(H21A,H21B,H21C), C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C6(H6A,H6B,
 H6C), C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C28(H28A,H28B,H28C), C27(H27A,H27B,
 H27C)
;
_shelx_res_checksum              12988
_shelx_hkl_checksum              87595
_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 2.198
_oxdiff_exptl_absorpt_empirical_full_min 0.503