Complexation-Induced Reduction of CuII to CuI Promoted by a Distorted Tetrahedral N4-Type Schiff-Base Ligand
Takeyama, Tomoyuki; Shirabe, Daisuke; Hamamoto, Nobutsugu; Ohta, Takehiro; Inorganics 13 (2025) 327–; doi:10.3390/inorganics13100327

data_1575971
_publ_section_title
;
 Complexation-Induced Reduction of CuII to CuI Promoted by a Distorted
 Tetrahedral N4-Type Schiff-Base Ligand
;
_journal_issue                   10
_journal_name_full               Inorganics
_journal_page_first              327
_journal_paper_doi               10.3390/inorganics13100327
_journal_volume                  13
_journal_year                    2025
_chemical_formula_moiety         'C52 H44 Cu2 N8, 2(C F3 O3 S)'
_chemical_formula_sum            'C54 H44 Cu2 F6 N8 O6 S2'
_chemical_formula_weight         1206.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-09-04 deposited with the CCDC.	2025-09-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.494(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.8459(3)
_cell_length_b                   19.8379(4)
_cell_length_c                   11.8919(3)
_cell_measurement_reflns_used    12339
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.5930
_cell_measurement_theta_min      2.2360
_cell_volume                     2478.95(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.956
_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     36.00  62.00   0.50    1.04    --  107.24 -57.00 -30.00   52
  2  \w     43.00  71.00   0.50    1.04    --  107.24-114.00-123.00   56
  3  \w     77.00 106.00   0.50    1.04    --  107.24-114.00-123.00   58
  4  \w     41.00  86.00   0.50    0.26    --   46.82-125.00-120.00   90
  5  \w     -5.00  26.00   0.50    0.26    --  -46.82  14.00-154.00   62
  6  \w    -10.00  26.00   0.50    0.26    --  -46.82  19.00   0.00   72
  7  \w    -10.00  29.00   0.50    0.26    --  -46.82  19.00  60.00   78
  8  \w    -14.00  25.00   0.50    0.26    --  -46.82  19.00 -30.00   78
  9  \w    -60.00 -32.00   0.50    1.04    -- -103.00  57.00 -90.00   56
 10  \w   -112.00 -69.00   0.50    1.04    -- -103.00 125.00 -90.00   86
 11  \w    -60.00 -35.00   0.50    1.04    -- -103.00 125.00 -90.00   50
 12  \w    -60.00 -30.00   0.50    1.04    -- -103.00  57.00   0.00   60
 13  \w   -174.00 -93.00   0.50    1.04    -- -103.00 -14.00  34.00  162
 14  \w   -161.00 -92.00   0.50    1.04    -- -103.00-128.00 -25.00  138
 15  \w   -118.00 -89.00   0.50    0.26    --  -47.70-128.00 -25.00   58
 16  \w    -13.00  21.00   0.50    0.26    --  -47.70  19.00-120.00   68
 17  \w    -61.00 -36.00   0.50    1.04    -- -103.00  57.00 -60.00   50
 18  \w     42.00  71.00   0.50    1.04    --  107.24 -57.00-150.00   58
 19  \w     54.00  79.00   0.50   13.48    --   47.70  14.00-155.00   50
 20  \w   -111.00 -61.00   0.50    0.20    --  -47.70-143.00 164.00  100
 21  \w     51.00  78.00   0.50    0.20    --   47.70-125.00  30.00   54
 22  \w   -135.00 -94.00   0.50    1.00    -- -103.00 -57.00 150.00   82
 23  \w   -174.00-140.00   0.50    1.00    -- -103.00 -57.00 150.00   68
 24  \w    -61.00 -36.00   0.50    1.00    -- -103.00  57.00 -30.00   50
 25  \w     75.00 104.00   0.50    1.00    --  107.24 -99.00  30.00   58
 26  \w    139.00 174.00   0.50    1.00    --  107.24   0.00-180.00   70
 27  \w     67.00  92.00   0.50    1.00    --  107.24 -99.00 120.00   50
 28  \w     40.00  66.00   0.50    1.00    --  107.24 -99.00 120.00   52
 29  \w     60.00 100.00   0.50    1.00    --  107.24 -99.00   0.00   80
 30  \w    138.00 164.00   0.50    1.00    --  107.24   0.00  60.00   52
 31  \w     45.00  96.00   0.50    1.00    --  107.24 -99.00 150.00  102
 32  \w     40.00  65.00   0.50    1.00    --  107.24 -57.00   0.00   50
 33  \w   -148.00-122.00   0.50    1.00    -- -103.00-114.00-123.00   52
 34  \w    -13.00  12.00   0.50    0.50    --  -47.70  19.00  30.00   50
 35  \w     18.00  45.00   0.50    0.50    --   47.70 -38.00 -60.00   54
 36  \w    -61.00 -36.00   0.50    1.00    -- -103.00  57.00-120.00   50
 37  \w   -105.00 -80.00   0.50    1.00    -- -103.00-114.00-123.00   50
 38  \w    129.00 155.00   0.50    1.00    --  107.24  57.00  60.00   52
 39  \w     35.00  68.00   0.50    1.00    --  107.24 -57.00-180.00   66
 40  \w     93.00 119.00   0.50    1.00    --  107.24  57.00  60.00   52
 41  \w     77.00 103.00   0.50    1.00    --  107.24 -99.00 -90.00   52
 42  \w    104.00 129.00   0.50    1.00    --  107.24 128.00  49.00   50
 43  \w     95.00 120.00   0.50    1.00    --  107.24 143.00-140.00   50
 44  \w   -118.00 -93.00   0.50    0.50    --  -47.70-128.00 -25.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0036237000
_diffrn_orient_matrix_UB_12      -0.0758430000
_diffrn_orient_matrix_UB_13      0.0260447000
_diffrn_orient_matrix_UB_21      0.0532273000
_diffrn_orient_matrix_UB_22      -0.0161357000
_diffrn_orient_matrix_UB_23      -0.0932169000
_diffrn_orient_matrix_UB_31      0.1365103000
_diffrn_orient_matrix_UB_32      0.0042910000
_diffrn_orient_matrix_UB_33      0.1093765000
_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  0.0481
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            20762
_diffrn_reflns_point_group_measured_fraction_full 0.628
_diffrn_reflns_point_group_measured_fraction_max 0.596
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.943
_diffrn_reflns_theta_min         2.227
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.578
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66237
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.616
_exptl_crystal_description       plate
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.543
_refine_diff_density_min         -0.714
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     707
_refine_ls_number_reflns         6236
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0452
_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^)+(0.0609P)^2^+3.8705P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1140
_refine_ls_wR_factor_ref         0.1157
_reflns_Friedel_coverage         0.245
_reflns_Friedel_fraction_full    0.262
_reflns_Friedel_fraction_max     0.235
_reflns_number_gt                5834
_reflns_number_total             6236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2485093.cif
_cod_data_source_block           241011_cubph6mepycf3so3_auto
_cod_database_code               1575971
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C54H44N8O6F6Cu2S2
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.820
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C47(H47), C19(H19), C45(H45), C6(H6), C48(H48), C30(H30), C21(H21),
 C32(H32), C49(H49), C40(H40), C28(H28), C14(H14), C22(H22), C11(H11), C23(H23),
  C10(H10), C2(H2), C16(H16), C34(H34), C15(H15), C37(H37), C42(H42), C3(H3),
 C41(H41), C36(H36), C35(H35), C43(H43), C9(H9), C17(H17), C8(H8), C29(H29)
2.b Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C26(H26A,H26B,H26C), C51(H51A,H51B,H51C), C25(H25A,H25B,
 H25C)
;
_shelx_res_checksum              72014
_shelx_hkl_checksum              54713
_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 2.760
_oxdiff_exptl_absorpt_empirical_full_min 0.582