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_7720187
_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 Cl2 Cu2 N4 P4'
_chemical_formula_sum            'C92 H68 Cl2 Cu2 N4 P4'
_chemical_formula_weight         1551.36
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-17
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-10-24 deposited with the CCDC.	2026-01-14 downloaded from the CCDC.
;
_cell_angle_alpha                98.066(4)
_cell_angle_beta                 98.273(5)
_cell_angle_gamma                112.512(5)
_cell_formula_units_Z            2
_cell_length_a                   13.9102(8)
_cell_length_b                   17.6178(8)
_cell_length_c                   17.7983(9)
_cell_measurement_reflns_used    4368
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.4540
_cell_measurement_theta_min      2.7580
_cell_volume                     3895.3(4)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.957
_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   -103.00 -75.00   0.50    0.05    --  -39.95-142.00 -43.00   56
  2  \w    -44.00 -15.00   0.50    0.05    --  -39.95 128.00-158.00   58
  3  \w    -78.00 -52.00   0.50    0.05    --  -39.95 142.00  12.00   52
  4  \w     36.00  85.00   0.50    0.05    --   39.95-128.00 126.00   98
  5  \w     70.00 109.00   0.50    0.05    --   39.95-142.00 -43.00   78
  6  \w   -133.00-108.00   0.50    0.20    --  -94.50-142.00 -43.00   50
  7  \w    -54.00 -28.00   0.50    0.20    --  -94.50 128.00-158.00   52
  8  \w    -71.00 -29.00   0.50    0.20    --  -94.50 142.00  12.00   84
  9  \w   -133.00 -86.00   0.50    0.20    --  -94.50-128.00 126.00   94
 10  \w     86.00 112.00   0.50    0.20    --  108.87-128.00 126.00   52
 11  \w    104.00 129.00   0.50    0.20    --  108.87 142.00  12.00   50
 12  \w    133.00 174.00   0.50    0.20    --  108.87 128.00-158.00   82
 13  \w     44.00 120.00   0.50    0.20    --  108.87-142.00 -43.00  152
 14  \w    -21.00  35.00   0.50    0.05    --  -39.95  19.00-180.00  112
 15  \w    -17.00  43.00   0.50    0.05    --  -39.95  19.00   0.00  120
 16  \w    -41.00  41.00   0.50    0.05    --  -39.95  37.00 -60.00  164
 17  \w      3.00  34.00   0.50    0.05    --  -39.95  19.00-150.00   62
 18  \w    -27.00  43.00   0.50    0.05    --  -39.95  19.00 120.00  140
 19  \w      5.00 113.00   0.50    0.05    --   39.95  77.00-150.00  216
 20  \w    -51.00 -15.00   0.50    0.20    --  -94.50  45.00   0.00   72
 21  \w    -85.00 -28.00   0.50    0.20    --  -94.50  77.00  30.00  114
 22  \w    -51.00 -15.00   0.50    0.20    --  -94.50  45.00  90.00   72
 23  \w    -43.00 -18.00   0.50    0.20    --  -94.50  45.00  60.00   50
 24  \w    -51.00 -18.00   0.50    0.20    --  -94.50  45.00 150.00   66
 25  \w   -135.00 -66.00   0.50    0.20    --  -94.50 -45.00-180.00  138
 26  \w    -50.00 -16.00   0.50    0.20    --  -94.50  45.00 -30.00   68
 27  \w     37.00  63.00   0.50    0.20    --  108.87-125.00   0.00   52
 28  \w    143.00 176.00   0.50    0.20    --  108.87 125.00-120.00   66
 29  \w     29.00  57.00   0.50    0.20    --  108.87 -94.00 120.00   56
 30  \w     57.00 107.00   0.50    0.20    --  108.87-106.00  16.33  100
 31  \w     67.00 111.00   0.50    0.20    --  108.87-125.00  90.00   88
 32  \w    143.00 178.00   0.50    0.20    --  108.87  30.00-150.00   70
 33  \w     76.00 163.00   0.50    0.20    --  108.87  30.00  90.00  174
 34  \w     72.00 131.00   0.50    0.20    --  108.87  30.00-150.00  118
 35  \w     39.00  70.00   0.50    0.20    --  108.87 -61.00   0.00   62
 36  \w     36.00  71.00   0.50    0.20    --  108.87 -61.00-150.00   70
 37  \w     38.00  71.00   0.50    0.20    --  108.87 -61.00 150.00   66
 38  \w     29.00 107.00   0.50    0.20    --  108.87-107.00 -38.01  156
 39  \w     95.00 132.00   0.50    0.20    --  108.87 125.00-120.00   74
 40  \w     34.00 111.00   0.50    0.20    --  108.87-125.00-120.00  154
 41  \w    122.00 169.00   0.50    0.20    --  108.87  45.00 150.00   94
 42  \w     53.00  80.00   0.50    0.20    --  108.87 -77.00 120.00   54
 43  \w     64.00 111.00   0.50    0.20    --  108.87-125.00   0.00   94
 44  \w    119.00 178.00   0.50    0.20    --  108.87  61.00 -90.00  118
 45  \w     39.00  67.00   0.50    0.20    --  108.87 -61.00  90.00   56
 46  \w     84.00 168.00   0.50    0.20    --  108.87  45.00 -60.00  168
 47  \w     35.00  96.00   0.50    0.20    --  108.87-125.00 -90.00  122
 48  \w     63.00 106.00   0.50    0.20    --  108.87 -77.00  30.00   86
 49  \w     90.00 173.00   0.50    0.20    --  108.87  45.00   0.00  166
 50  \w     71.00 110.00   0.50    0.20    --  108.87-125.00-150.00   78
 51  \w     54.00  91.00   0.50    0.20    --  108.87 -94.00 -60.00   74
 52  \w     46.00  71.00   0.50    0.20    --  108.87 -61.00 -30.00   50
;
_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      0.0067587000
_diffrn_orient_matrix_UB_12      -0.0114310000
_diffrn_orient_matrix_UB_13      -0.0862151000
_diffrn_orient_matrix_UB_21      0.1196295000
_diffrn_orient_matrix_UB_22      0.0204780000
_diffrn_orient_matrix_UB_23      0.0238165000
_diffrn_orient_matrix_UB_31      -0.0268240000
_diffrn_orient_matrix_UB_32      -0.0940151000
_diffrn_orient_matrix_UB_33      -0.0040539000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1447
_diffrn_reflns_av_unetI/netI     0.1436
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            49291
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.675
_diffrn_reflns_theta_min         2.568
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.462
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76242
_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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.535
_refine_diff_density_min         -0.660
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     937
_refine_ls_number_reflns         15293
_refine_ls_number_restraints     1090
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1492
_refine_ls_R_factor_gt           0.0821
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0535P)^2^+3.6316P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1892
_refine_ls_wR_factor_ref         0.2290
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7785
_reflns_number_total             15293
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02914g2.cif
_cod_data_source_block           lsj-kb-cl-1
_cod_database_code               7720187
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Cl'
_shelx_estimated_absorpt_t_max   0.525
_shelx_estimated_absorpt_t_min   0.372
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 C14, C22, C28, C32, Cu2, P3, C34, C8, C44, C30, C46, C50, C40, C38, C52, C54,
 C56, C58, C00H, C26, C60, C48, N3, C24, P1, N1, N4, C36, C16, C42, Cl2, Cl1,
 P4, C4, C12, C10, C18, C20, Cu1, P2, C1, N2, C6, C68, C64, C66, C62, C83, C11,
 C81, C45, C5, C41, C43, C89, C87, C21, C85, C7, C35, C77, C39, C79, C69, C75,
 C84, C82, C47, C91, C90, C51, C59, C15, C29, C61, C33, C67, C49, C57, C23, C88,
  C53, C55, C73, C78, C2, C31, C86, C17, C71, C9, C3, C13, C80, C25, C63, C65,
 C37, C27, C19, C70, C76, C72, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N2, C20, C58, C86, C27, C69, C39, C5, C21, C85, C89, C45, C56
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
C14 \\sim C22 \\sim C28 \\sim C32 \\sim Cu2 \\sim P3 \\sim C34 \\sim C8 \\sim
C44 \\sim C30 \\sim C46 \\sim C50 \\sim C40 \\sim C38 \\sim C52 \\sim C54 \\sim
C56 \\sim C58 \\sim C00H \\sim C26 \\sim C60 \\sim C48 \\sim N3 \\sim C24 \\sim
P1 \\sim N1 \\sim N4 \\sim C36 \\sim C16 \\sim C42 \\sim Cl2 \\sim Cl1 \\sim P4
\\sim C4 \\sim C12 \\sim C10 \\sim C18 \\sim C20 \\sim Cu1 \\sim P2 \\sim C1
\\sim N2 \\sim C6 \\sim C68 \\sim C64 \\sim C66 \\sim C62 \\sim C83 \\sim C11
\\sim C81 \\sim C45 \\sim C5 \\sim C41 \\sim C43 \\sim C89 \\sim C87 \\sim C21
\\sim C85 \\sim C7 \\sim C35 \\sim C77 \\sim C39 \\sim C79 \\sim C69 \\sim C75
\\sim C84 \\sim C82 \\sim C47 \\sim C91 \\sim C90 \\sim C51 \\sim C59 \\sim C15
\\sim C29 \\sim C61 \\sim C33 \\sim C67 \\sim C49 \\sim C57 \\sim C23 \\sim C88
\\sim C53 \\sim C55 \\sim C73 \\sim C78 \\sim C2 \\sim C31 \\sim C86 \\sim C17
\\sim C71 \\sim C9 \\sim C3 \\sim C13 \\sim C80 \\sim C25 \\sim C63 \\sim C65
\\sim C37 \\sim C27 \\sim C19 \\sim C70 \\sim C76 \\sim C72 \\sim C74: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
N2 \\sim C20 \\sim C56 \\sim C58 \\sim C86 \\sim C27 \\sim C69 \\sim C39 \\sim
C5 \\sim C21 \\sim C85 \\sim C89 \\sim C45: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.002 within 2A
Uanis(N2) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C86)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C89)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C56) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.002
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C10(H10), C12(H12), C26(H26), C38(H38), C52(H52), C54(H54), C56(H56),
 C60(H60), C62(H62), C64(H64), C66(H66), C68(H68), C70(H70), C72(H72), C74(H74),
  C76(H76), C78(H78), C80(H80), C82(H82), C84(H84), C88(H88), C90(H90),
 C91(H91), C23(H23), C47(H47), C3(H3), C49(H49), C25(H25), C51(H51), C13(H13),
 C53(H53), 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)
;
_shelx_res_checksum              49992
_shelx_hkl_checksum              59043
_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 1.579
_oxdiff_exptl_absorpt_empirical_full_min 0.696