Copper-based homometallic and heterometallic binuclear complexes for electrocatalytic CO<sub>2</sub> reduction.
Xie, Xin-Ling; Chen, Feng; Wang, Wen-Wen; Lyu, Lei-Yan; Sun, Meng-Jiao; Zhang, Teng; Cao, Rong; Chemical communications (Cambridge, England) 61 (2025) 13485–13488; doi:10.1039/d5cc04378f

data_7134899
_publ_section_title
;
 Copper-based homometallic and heterometallic binuclear complexes for
 electrocatalytic CO<sub>2</sub> reduction.
;
_journal_issue                   71
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              13485
_journal_page_last               13488
_journal_paper_doi               10.1039/d5cc04378f
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety
'0.5(C24 H30 Cl Cu N4 Ni O8), 0.5(C24 H30 Cu N4 Ni O4), 1.5(Cl O4)'
_chemical_formula_sum            'C24 H30 Cl2 Cu N4 Ni O12'
_chemical_formula_weight         759.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-07-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-07-10 deposited with the CCDC.	2025-08-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.6310(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7242(2)
_cell_length_b                   12.36530(10)
_cell_length_c                   14.6102(2)
_cell_measurement_reflns_used    14993
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.1690
_cell_measurement_theta_min      4.4890
_cell_volume                     2909.65(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.962
_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    -67.00  25.00   0.50    0.21    --  -47.77  69.00  18.00  184
  2  \w    -70.00 -33.00   0.50    0.85    -- -105.00  61.00 120.00   74
  3  \w    -66.00 -33.00   0.50    0.85    -- -105.00  61.00  60.00   66
  4  \w    -70.00 -39.00   0.50    0.85    -- -105.00  61.00 150.00   62
  5  \w    -85.00 -32.00   0.50    0.85    -- -105.00  69.00  18.00  106
  6  \w    -71.00 -46.00   0.50    0.85    -- -105.00  61.00 -30.00   50
  7  \w    -71.00 -46.00   0.50    0.85    -- -105.00  61.00-120.00   50
  8  \w    -83.00 -57.00   0.50    0.85    -- -105.00 125.00  30.00   52
  9  \w   -174.00-112.00   0.50    0.85    -- -105.00 -30.00 120.00  124
 10  \w    -53.00 -27.00   0.50    0.21    --  -47.77 -69.00-114.00   52
 11  \w   -109.00 -61.00   0.50    0.21    --  -47.77 -69.00-114.00   96
 12  \w   -154.00-129.00   0.50    0.85    -- -105.00 -69.00-114.00   50
 13  \w   -118.00 -74.00   0.50    0.21    --  -47.77-125.00 -30.00   88
 14  \w   -110.00 -79.00   0.50    0.21    --  -47.77-125.00   0.00   62
 15  \w    -28.00  26.00   0.50    0.21    --   47.77 -19.00-120.00  108
 16  \w     21.00  48.00   0.50    0.21    --   47.77 -69.00-114.00   54
 17  \w    -23.00   8.00   0.50    0.21    --   47.77 -69.00-114.00   62
 18  \w     38.00  67.00   0.50    0.85    --  108.17 -61.00 -60.00   58
 19  \w     70.00  95.00   0.50    0.85    --  108.17 -77.00  60.00   50
 20  \w     38.00  71.00   0.50    0.85    --  108.17 -61.00 -90.00   66
 21  \w     42.00  80.00   0.50    0.85    --  108.17 -69.00-114.00   76
 22  \w     39.00  64.00   0.50    0.85    --  108.17 -61.00-180.00   50
 23  \w     98.00 173.00   0.50    0.85    --  108.17  45.00 -60.00  150
 24  \w    117.00 152.00   0.50    0.85    --  108.17  45.00 -30.00   70
 25  \w     89.00 176.00   0.50    0.85    --  108.17  69.00  18.00  174
 26  \w    148.00 174.00   0.50    0.85    --  108.17  45.00  60.00   52
 27  \w     94.00 137.00   0.50    0.85    --  108.17  45.00  60.00   86
 28  \w     49.00  74.00   0.50    0.21    --   47.77  69.00  18.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0283
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20684
_diffrn_reflns_point_group_measured_fraction_full 0.784
_diffrn_reflns_point_group_measured_fraction_max 0.734
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.176
_diffrn_reflns_theta_min         2.743
_exptl_absorpt_coefficient_mu    4.018
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65293
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.118a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.734
_exptl_crystal_description       block
_exptl_crystal_F_000             1556
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.427
_refine_diff_density_min         -0.395
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.35(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     842
_refine_ls_number_reflns         9056
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0605P)^2^+0.9969P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1006
_refine_ls_wR_factor_ref         0.1038
_reflns_Friedel_coverage         0.524
_reflns_Friedel_fraction_full    0.568
_reflns_Friedel_fraction_max     0.505
_reflns_number_gt                8371
_reflns_number_total             9056
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04378f2.cif
_cod_data_source_block           pc
_cod_depositor_comments
'Adding full bibliography for 7134898--7134901.cif.'
_cod_database_code               7134899
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.824
_shelx_estimated_absorpt_t_min   0.500
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.65(2)
 0.35(2)
2. 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, All O(H,H) groups
3. Restrained distances
 O5-H5A = O5-H5B = O6-H6A = O6-H6B = O8-H8A = O8-H8B = O12-H12A = O12-H12B
 0.82 with sigma of 0.02
4. Others
 Sof(H16C)=Sof(H16D)=Sof(C41B)=Sof(H41C)=Sof(H41D)=Sof(H43C)=Sof(H43D)=1-FVAR(1)
 Sof(H16A)=Sof(H16B)=Sof(C41A)=Sof(H41A)=Sof(H41B)=Sof(H43A)=Sof(H43B)=FVAR(1)
 Sof(H32C)=Sof(H32D)=Sof(H39C)=Sof(H39D)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=1-FVAR(2)
 Sof(H32A)=Sof(H32B)=Sof(H39A)=Sof(H39B)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C16(H16C,H16D), C20(H20A,H20B), C25(H25A,H25B), C29(H29A,
 H29B), C32(H32A,H32B), C32(H32C,H32D), C39(H39A,H39B), C39(H39C,H39D),
 C41A(H41A,H41B), C41B(H41C,H41D), C43(H43A,H43B), C43(H43C,H43D), C44(H44A,
 H44B), C47(H47A,H47B), C48(H48A,H48B), C8A(H8AA,H8AB), C8B(H8BA,H8BB)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13), C15(H15),
 C24(H24), C31(H31), C34(H34), C35(H35), C36(H36), C37(H37), C42(H42), C45(H45)
5.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C40(H40A,H40B,H40C), C46(H46A,H46B,
 H46C)
;
_shelx_res_checksum              69554
_shelx_hkl_checksum              31015
_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
;