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_7720186
_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 Cu2 I2 N4 P4, 0.5[CH2Cl2]'
_chemical_formula_sum            'C92.5 H69 Cl Cu2 I2 N4 P4'
_chemical_formula_weight         1776.72
_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             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                90
_cell_angle_beta                 100.159(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8695(2)
_cell_length_b                   31.6715(4)
_cell_length_c                   25.5960(5)
_cell_measurement_reflns_used    32487
_cell_measurement_temperature    150
_cell_measurement_theta_max      73.9560
_cell_measurement_theta_min      2.7770
_cell_volume                     8673.4(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 2014/5 (Sheldrick, 2014)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.968
_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    -62.00  29.00   0.50    0.35    --  -39.95  63.00 -35.00  182
  2  \w   -109.00 -18.00   0.50    0.35    --  -39.95 -63.00-172.00  182
  3  \w    -74.00 -49.00   0.50    1.41    --  -94.50  63.00 -35.00   50
  4  \w   -165.00-134.00   0.50    1.41    --  -94.50 -63.00-172.00   62
  5  \w     81.00 173.00   0.50    1.41    --  108.87  63.00 -35.00  184
  6  \w     34.00  74.00   0.50    1.41    --  108.87 -63.00-172.00   80
  7  \w     63.00 114.00   0.50    0.35    --   39.95 178.00  90.00  102
  8  \w     63.00 123.00   0.50    0.35    --   39.95 178.00-150.00  120
  9  \w     18.00  44.00   0.50    0.35    --   39.95 -77.00 120.00   52
 10  \w   -172.00 -85.00   0.50    1.41    --  -94.50 -94.00 -60.00  174
 11  \w    -51.00 -19.00   0.50    1.41    --  -94.50  45.00 -60.00   64
 12  \w    -86.00 -50.00   0.50    1.41    --  -94.50 125.00 -60.00   72
 13  \w     34.00 109.00   0.50    1.41    --  108.87-125.00-150.00  150
 14  \w     35.00 106.00   0.50    1.41    --  108.87 -77.00 120.00  142
 15  \w     34.00  66.00   0.50    1.41    --  108.87 -61.00 120.00   64
 16  \w    143.00 177.00   0.50    1.41    --  108.87 125.00   0.00   68
 17  \w     34.00  64.00   0.50    1.41    --  108.87-125.00 150.00   60
 18  \w     96.00 123.00   0.50    1.41    --  108.87 125.00   0.00   54
 19  \w     38.00  63.00   0.50    1.41    --  108.87 -61.00-120.00   50
 20  \w     95.00 128.00   0.50    1.41    --  108.87 125.00-150.00   66
 21  \w    138.00 178.00   0.50    1.41    --  108.87 125.00-150.00   80
 22  \w     47.00 106.00   0.50    1.41    --  108.87 -77.00 -90.00  118
 23  \w     34.00  59.00   0.50    1.41    --  108.87-125.00-180.00   50
 24  \w     69.00  99.00   0.50    1.41    --  108.87-125.00-180.00   60
 25  \w     34.00  61.00   0.50    1.41    --  108.87 -61.00 -30.00   54
 26  \w    145.00 175.00   0.50    1.41    --  108.87  61.00-120.00   60
 27  \w     97.00 130.00   0.50    1.41    --  108.87  61.00-120.00   66
;
_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      -0.0045231000
_diffrn_orient_matrix_UB_12      0.0085065000
_diffrn_orient_matrix_UB_13      0.0588998000
_diffrn_orient_matrix_UB_21      0.0985923000
_diffrn_orient_matrix_UB_22      0.0350772000
_diffrn_orient_matrix_UB_23      0.0009311000
_diffrn_orient_matrix_UB_31      -0.1048315000
_diffrn_orient_matrix_UB_32      0.0325923000
_diffrn_orient_matrix_UB_33      -0.0164367000
_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  0.0459
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            56659
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.047
_diffrn_reflns_theta_min         2.790
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.524
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68959
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       block
_exptl_crystal_F_000             3572
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.275
_refine_diff_density_min         -1.688
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     937
_refine_ls_number_reflns         17055
_refine_ls_number_restraints     696
_refine_ls_restrained_S_all      1.154
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0611
_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^)+(0.1221P)^2^+4.6043P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1885
_refine_ls_wR_factor_ref         0.1961
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14204
_reflns_number_total             17055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02914g2.cif
_cod_data_source_block           lsj-7-16
_cod_original_formula_sum        'C92.50 H69 Cl Cu2 I2 N4 P4'
_cod_database_code               7720186
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Si P I'
_shelx_estimated_absorpt_t_max   0.806
_shelx_estimated_absorpt_t_min   0.705
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 C89, C91, C79, C87, C11, C54
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C50, C59, C65, C19, C43, C45
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C52, C7, C71, C39, C41, C85
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C66, C74, C92, C49, C27, C15, C9, C37, C75, N3, C70, C67, C5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C30, C72, C51, C69, C35, C83
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C21, C33, C22, C64, C3, C77
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C42, C82, C31, C17, C81, C57
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C89 \\sim C91 \\sim C79 \\sim C87 \\sim C11 \\sim C54: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C50 \\sim C59 \\sim C65 \\sim C19 \\sim C43 \\sim C45: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C52 \\sim C7 \\sim C71 \\sim C39 \\sim C41 \\sim C85: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
N3 \\sim C66 \\sim C70 \\sim C74 \\sim C92 \\sim C49 \\sim C27 \\sim C15 \\sim
C9 \\sim C37 \\sim C75 \\sim C5: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C30 \\sim C72 \\sim C51 \\sim C69 \\sim C35 \\sim C83: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C21 \\sim C33 \\sim C22 \\sim C64 \\sim C3 \\sim C77: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C82 \\sim C42 \\sim C57 \\sim C81 \\sim C17 \\sim C31: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C89) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C87)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C54) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C50) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C52) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C85) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C66) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(C37) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C70)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C30) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C83) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C64)
\\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C77) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C42) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C17)
\\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C57) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C20(H20), C26(H26), C28(H28), C34(H34), C40(H40), C44(H44), C56(H56),
 C58(H58), C60(H60), C62(H62), C64(H64), C68(H68), C72(H72), C76(H76), C78(H78),
  C80(H80), C82(H82), C84(H84), C86(H86), C88(H88), C90(H90), C92(H92),
 C23(H23), C47(H47), C3(H3), 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              52705
_shelx_hkl_checksum              76833
_shelx_fab_checksum              32306
_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 1.348
_oxdiff_exptl_absorpt_empirical_full_min 0.788