Dinuclear copper(I) halide complexes containing unsymmetric diphosphine: structure, photophysical and photocatalytic hydrogen production properties.
Li, Shi-Ji; Liu, Li; Zhong, Xin-Xin; Li, Fa-Bao; Li, Feng-Yan; Qin, Hai-Mei; Dalton transactions (Cambridge, England : 2003) 55 (2026) 3043–3054; doi:10.1039/d5dt02914g

data_7720188
_publ_section_title
;
 Dinuclear copper(I) halide complexes containing unsymmetric diphosphine:
 structure, photophysical and photocatalytic hydrogen production
 properties.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3043
_journal_page_last               3054
_journal_paper_doi               10.1039/d5dt02914g
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C92 H68 Br2 Cu2 N4 P4'
_chemical_formula_sum            'C92 H68 Br2 Cu2 N4 P4'
_chemical_formula_weight         1640.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-22
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2025-10-29 deposited with the CCDC.	2026-01-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.677(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7953(2)
_cell_length_b                   31.6104(4)
_cell_length_c                   25.5744(6)
_cell_measurement_reflns_used    25124
_cell_measurement_temperature    150
_cell_measurement_theta_max      74.2160
_cell_measurement_theta_min      3.2910
_cell_volume                     8602.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_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      150
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.953
_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   -123.00 -13.00   0.50    0.50    --  -39.95 -31.00 169.00  220
  2  \w    -36.00  37.00   0.50    0.50    --  -39.95  31.00 -30.00  146
  3  \w    -28.00  -3.00   0.50    0.50    --   39.95 -31.00 169.00   50
  4  \w   -118.00 -62.00   0.50    2.00    --  -94.50 -31.00 169.00  112
  5  \w     73.00 171.00   0.50    2.00    --  108.87  31.00 -30.00  196
  6  \w     67.00 110.00   0.50    0.50    --   39.95 178.00-150.00   86
  7  \w     22.00  48.00   0.50    0.50    --   39.95 -57.00  60.00   52
  8  \w     70.00 117.00   0.50    0.50    --   39.95 178.00  90.00   94
  9  \w    -41.00 -16.00   0.50    2.00    --  -94.50  45.00  30.00   50
 10  \w    -50.00 -19.00   0.50    2.00    --  -94.50  45.00  90.00   62
 11  \w    -51.00 -22.00   0.50    2.00    --  -94.50  45.00 150.00   58
 12  \w    -66.00 -27.00   0.50    2.00    --  -94.50  77.00 150.00   78
 13  \w    -47.00 -21.00   0.50    2.00    --  -94.50  45.00 120.00   52
 14  \w    -46.00 -21.00   0.50    2.00    --  -94.50  61.00  90.00   50
 15  \w    -60.00 -35.00   0.50    2.00    --  -94.50  61.00  60.00   50
 16  \w     34.00  59.00   0.50    2.00    --  108.87 -61.00-120.00   50
 17  \w     42.00  72.00   0.50    2.00    --  108.87 -77.00-150.00   60
 18  \w     76.00 102.00   0.50    2.00    --  108.87 -77.00-150.00   52
 19  \w     35.00 106.00   0.50    2.00    --  108.87 -77.00 120.00  142
 20  \w     42.00  68.00   0.50    2.00    --  108.87 -61.00-180.00   52
 21  \w     56.00 104.00   0.50    2.00    --  108.87 -94.00  90.00   96
 22  \w     36.00  79.00   0.50    2.00    --  108.87-125.00-180.00   86
 23  \w     34.00  59.00   0.50    2.00    --  108.87 -61.00 -60.00   50
 24  \w     41.00  93.00   0.50    2.00    --  108.87 -77.00 -90.00  104
 25  \w     84.00 110.00   0.50    2.00    --  108.87-125.00-180.00   52
 26  \w    102.00 175.00   0.50    2.00    --  108.87 125.00-180.00  146
 27  \w     34.00  69.00   0.50    2.00    --  108.87 -61.00 150.00   70
 28  \w     37.00  68.00   0.50    2.00    --  108.87 -61.00-150.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0799797000
_diffrn_orient_matrix_UB_12      0.0070332000
_diffrn_orient_matrix_UB_13      0.0551310000
_diffrn_orient_matrix_UB_21      0.1013783000
_diffrn_orient_matrix_UB_22      0.0221598000
_diffrn_orient_matrix_UB_23      -0.0259729000
_diffrn_orient_matrix_UB_31      -0.0653803000
_diffrn_orient_matrix_UB_32      0.0428508000
_diffrn_orient_matrix_UB_33      0.0044119000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_unetI/netI     0.0453
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            51260
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.386
_diffrn_reflns_theta_min         2.796
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.746
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.19476
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.49a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             3344
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.762
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     937
_refine_ls_number_reflns         16734
_refine_ls_number_restraints     94
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0830P)^2^+1.1441P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1372
_refine_ls_wR_factor_ref         0.1471
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12879
_reflns_number_total             16734
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02914g2.cif
_cod_data_source_block           lsj-kb--br
_cod_database_code               7720188
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Br Si P'
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.875
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 C45, C91
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C11, C21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C85, C79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C41, C89
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C77, C87, C21, C39, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C85 \\sim C79: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C41 \\sim C89: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C45 \\sim C91: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C11 \\sim C21: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C77 \\sim C87 \\sim C21 \\sim C39 \\sim C41: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(C45) \\sim Ueq, Uanis(C91) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C85) \\sim Ueq, Uanis(C79) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C11) \\sim Ueq, Uanis(C21) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C41) \\sim Ueq, Uanis(C89) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C77) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C41) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C16(H16), C28(H28), C32(H32), C40(H40), C54(H54), C58(H58),
 C60(H60), C62(H62), C66(H66), C68(H68), C70(H70), C74(H74), C76(H76), C78(H78),
  C80(H80), C82(H82), C84(H84), C86(H86), C88(H88), C90(H90), C92(H92),
 C23(H23), C47(H47), C3(H3), C49(H49), C25(H25), C51(H51), C13(H13), C53(H53),
 C27(H27), C55(H55), C7(H7), C57(H57), C29(H29), C59(H59), C15(H15), C61(H61),
 C31(H31), C63(H63), C2(H2), C65(H65), C33(H33), C67(H67), C17(H17), C69(H69),
 C35(H35), C71(H71), C9(H9), C73(H73), C37(H37), C75(H75), C19(H19), C77(H77),
 C39(H39), C79(H79), C5(H5), C81(H81), C41(H41), C83(H83), C21(H21), C85(H85),
 C43(H43), C87(H87), C11(H11), C89(H89), C45(H45), C91(H91)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              50306
_shelx_hkl_checksum              33536
_shelx_fab_checksum              34012
_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 5.992
_oxdiff_exptl_absorpt_empirical_full_min 0.508