Tuning phase transition and fluorescence quenching in 0D organic-inorganic hybrid materials by precise organic cation modification.
Chen, Leqi; Zhou, Zining; Yang, Yawen; Ye, Qiong; Dalton transactions (Cambridge, England : 2003) 54 (2025) 5560–5567; doi:10.1039/d5dt00057b

data_7718284
_publ_section_title
;
 Tuning phase transition and fluorescence quenching in 0D
 organic-inorganic hybrid materials by precise organic cation
 modification.
;
_journal_issue                   13
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5560
_journal_page_last               5567
_journal_paper_doi               10.1039/d5dt00057b
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         '2(C6 H14 P), Br4 Mn'
_chemical_formula_sum            'C12 H28 Br4 Mn P2'
_chemical_formula_weight         608.86
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-02-09 deposited with the CCDC.	2025-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.22910(10)
_cell_length_b                   9.22910(10)
_cell_length_c                   27.9955(5)
_cell_measurement_reflns_used    9111
_cell_measurement_temperature    272.84(19)
_cell_measurement_theta_max      71.3560
_cell_measurement_theta_min      4.8380
_cell_volume                     2384.55(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      272.84(19)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -52.00 -25.00   0.50    0.05    --  -60.72 143.00 163.00   54
  2  \w    -97.00 -72.00   0.50    0.05    --  -74.13 143.00 163.00   50
  3  \w    -65.00 -40.00   0.50    0.05    --  -75.50 125.00  60.00   50
  4  \w    -78.00 -53.00   0.50    0.05    --  -60.72 127.00  -6.00   50
  5  \w    -93.00 -68.00   0.50    0.05    --  -75.50 127.00  -6.00   50
  6  \w   -104.00 -77.00   0.50    0.05    --  -75.50 125.00  60.00   54
  7  \w     76.00 124.00   0.50    0.05    --   75.18  30.00 120.00   96
  8  \w     69.00  94.00   0.50    0.05    --   75.18 143.00 163.00   50
  9  \w     76.00 123.00   0.50    0.05    --   75.12  30.00-150.00   94
 10  \w     31.00  68.00   0.50    0.05    --   60.54 -94.00 -30.00   74
 11  \w     56.00  81.00   0.50    0.05    --   60.54-127.00 -81.00   50
 12  \w     44.00  69.00   0.50    0.05    --   75.18-127.00 -81.00   50
 13  \w     45.00  95.00   0.50    0.05    --   60.54-143.00 108.00  100
 14  \w     34.00 105.00   0.50    0.05    --   75.12-143.00 108.00  142
 15  \w     46.00  82.00   0.50    0.05    --   75.12 -94.00 120.00   72
 16  \w     11.00  38.00   0.50    0.05    --   60.54 -30.00  30.00   54
 17  \w     11.00  36.00   0.50    0.05    --   60.54 -30.00  90.00   50
 18  \w     11.00  37.00   0.50    0.05    --   60.54 -30.00  60.00   52
 19  \w     12.00  37.00   0.50    0.05    --   60.54 -30.00   0.00   50
 20  \w     11.00  37.00   0.50    0.05    --   60.54 -30.00-120.00   52
 21  \w     12.00  38.00   0.50    0.05    --   60.54 -30.00-150.00   52
 22  \w   -115.00 -73.00   0.50    0.05    --  -75.50-125.00 -60.00   84
 23  \w   -118.00 -93.00   0.50    0.05    --  -74.13-125.00-150.00   50
 24  \w   -113.00 -75.00   0.50    0.05    --  -74.13-125.00-180.00   76
 25  \w   -100.00 -75.00   0.50    0.05    --  -75.50-127.00 -81.00   50
 26  \w   -112.00 -87.00   0.50    0.05    --  -74.13-143.00 108.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1128502000
_diffrn_orient_matrix_UB_12      -0.0281046000
_diffrn_orient_matrix_UB_13      -0.0394987000
_diffrn_orient_matrix_UB_21      -0.1122997000
_diffrn_orient_matrix_UB_22      -0.0428747000
_diffrn_orient_matrix_UB_23      0.0381939000
_diffrn_orient_matrix_UB_31      -0.0501769000
_diffrn_orient_matrix_UB_32      0.1588009000
_diffrn_orient_matrix_UB_33      0.0033440000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1177
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            16085
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.897
_diffrn_reflns_theta_min         5.046
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.530
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20963
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.129a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic yellowish black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.696
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1180
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.696
_refine_diff_density_min         -0.512
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 661 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(11)
_refine_ls_extinction_coef       0.00121(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     110
_refine_ls_number_reflns         2292
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0496
_refine_ls_R_factor_gt           0.0453
_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^)+(0.0842P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1338
_refine_ls_wR_factor_ref         0.1362
_reflns_Friedel_coverage         0.596
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                1984
_reflns_number_total             2292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00057b2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7718284--7718286.cif.'
_cod_original_cell_volume        2384.55(7)
_cod_database_code               7718284
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H P Mn Br '
_shelx_estimated_absorpt_t_max   0.345
_shelx_estimated_absorpt_t_min   0.294
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C5-C4
 1.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C4 \\sim C5 \\sim C6 \\sim C5A \\sim C6A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Same fragment restrains
{C4, C5A, C6A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C4, C5, C6}
5. Others
 Sof(H4BC)=Sof(H4BD)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=1-FVAR(1)
 Sof(H4AA)=Sof(H4AB)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6A)=Sof(H6B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4AA,H4AB), C4(H4BC,H4BD)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C5A(H5A)
6.c X=CH2 refined with riding coordinates:
 C6(H6A,H6B), C6A(H6AA,H6AB)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              72358
_shelx_hkl_checksum              19111
_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 3.400
_oxdiff_exptl_absorpt_empirical_full_min 0.445