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_1575970
_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         'C26 H22 Cu N4, C24 H20 B'
_chemical_formula_sum            'C50 H42 B Cu N4'
_chemical_formula_weight         773.22
_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             2025-03-28
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-09-04 deposited with the CCDC.	2025-09-25 downloaded from the CCDC.
;
_cell_angle_alpha                92.725(3)
_cell_angle_beta                 108.344(3)
_cell_angle_gamma                99.419(3)
_cell_formula_units_Z            2
_cell_length_a                   11.4008(3)
_cell_length_b                   11.5395(4)
_cell_length_c                   15.8744(6)
_cell_measurement_reflns_used    11075
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9320
_cell_measurement_theta_min      2.9380
_cell_volume                     1944.61(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 0.982
_diffrn_measured_fraction_theta_max 0.932
_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    -15.00  10.00   0.50    0.21    --   47.20 -19.00 -60.00   50
  2  \w    -15.00  43.00   0.50    0.21    --   47.20 -38.00 -30.00  116
  3  \w     92.00 152.00   0.50    0.82    --  107.24  95.00  15.00  120
  4  \w     39.00  66.00   0.50    0.82    --  107.24 -57.00 150.00   54
  5  \w     83.00 111.00   0.50    0.82    --  107.24-125.00 120.00   56
  6  \w     38.00 106.00   0.50    0.82    --  107.24 -99.00  60.00  136
  7  \w     48.00  75.00   0.50    0.82    --  107.24-125.00 120.00   54
  8  \w     68.00 106.00   0.50    0.82    --  107.24 -99.00 120.00   76
  9  \w     68.00  95.00   0.50    0.82    --  107.24 -99.00  30.00   54
 10  \w     38.00 106.00   0.50    0.82    --  107.24 -99.00 -30.00  136
 11  \w    -22.00  67.00   0.50    0.21    --   47.20 -95.00 -94.00  178
 12  \w     37.00  91.00   0.50    0.82    --  107.24 -99.00-180.00  108
 13  \w     37.00 100.00   0.50    0.82    --  107.24 -99.00-120.00  126
 14  \w     46.00 104.00   0.50    0.82    --  107.24 -95.00 -94.00  116
 15  \w    151.00 176.00   0.50    0.82    --  107.24   0.00-180.00   50
 16  \w    150.00 175.00   0.50    0.82    --  107.24  57.00-150.00   50
 17  \w     98.00 127.00   0.50    0.82    --  107.24  57.00-150.00   58
 18  \w     97.00 143.00   0.50    0.82    --  107.24  19.00 -60.00   92
 19  \w    113.00 157.00   0.50    0.82    --  107.24   0.00 -60.00   88
 20  \w    -36.00  25.00   0.50    0.21    --  -47.20  38.00 -60.00  122
 21  \w     -1.00  28.00   0.50    0.21    --  -47.20  19.00 -30.00   58
 22  \w    -33.00  22.00   0.50    0.21    --  -47.20  38.00-180.00  110
 23  \w   -113.00 -70.00   0.50    0.21    --  -47.20   0.00-150.00   86
 24  \w   -118.00 -74.00   0.50    0.21    --  -47.20   0.00 120.00   88
 25  \w    -60.00 -30.00   0.50    0.82    -- -103.00  57.00 120.00   60
 26  \w    -60.00 -30.00   0.50    0.82    -- -103.00  57.00 150.00   60
 27  \w    -60.00 -30.00   0.50    0.82    -- -103.00  57.00  90.00   60
 28  \w    -61.00 -35.00   0.50    0.82    -- -103.00  57.00 -30.00   52
 29  \w    -60.00 -30.00   0.50    0.82    -- -103.00  57.00-120.00   60
 30  \w    -75.00  14.00   0.50    0.21    --  -47.20  95.00  15.00  178
 31  \w    -80.00 -54.00   0.50    0.82    -- -103.00  95.00  15.00   52
 32  \w   -116.00 -91.00   0.50    0.82    -- -103.00 -19.00 150.00   50
 33  \w   -173.00-124.00   0.50    0.82    -- -103.00 -19.00 150.00   98
 34  \w   -172.00-145.00   0.50    0.82    -- -103.00 -77.00   0.00   54
 35  \w   -127.00 -82.00   0.50    0.82    -- -103.00 -77.00   0.00   90
 36  \w   -171.00 -89.00   0.50    0.82    -- -103.00 -57.00   0.00  164
 37  \w   -173.00 -83.00   0.50    0.82    -- -103.00 -95.00 -94.00  180
 38  \w   -163.00 -91.00   0.50    0.82    -- -103.00 -99.00 150.00  144
;
_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      -0.0429230000
_diffrn_orient_matrix_UB_12      0.0805774000
_diffrn_orient_matrix_UB_13      -0.0739526000
_diffrn_orient_matrix_UB_21      -0.0500082000
_diffrn_orient_matrix_UB_22      0.0714152000
_diffrn_orient_matrix_UB_23      0.0611723000
_diffrn_orient_matrix_UB_31      0.1291095000
_diffrn_orient_matrix_UB_32      0.0832338000
_diffrn_orient_matrix_UB_33      0.0368884000
_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  0.0336
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20474
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.708
_diffrn_reflns_theta_min         2.949
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.103
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81310
_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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       plate
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.315
_refine_diff_density_min         -0.661
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         7641
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0577
_refine_ls_R_factor_gt           0.0508
_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^)+(0.0920P)^2^+0.8470P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1370
_refine_ls_wR_factor_ref         0.1424
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6684
_reflns_number_total             7641
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2485092.cif
_cod_data_source_block           241011_cubph6mepybp4
_cod_database_code               1575970
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C50H42B1N4Cu1
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.888
_diffrn_oxdiff_digest_hkl
;
011dd3eb97d30f6cd09d0b61462462e2ff2196
;
_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:
 C38(H38), C44(H44), C19(H19), C37(H37), C17(H17), C34(H34), C46(H46),
 C42(H42), C14(H14), C40(H40), C50(H50), C32(H32), C23(H23), C28(H28), C43(H43),
  C16(H16), C36(H36), C47(H47), C11(H11), C6(H6), C31(H31), C8(H8), C41(H41),
 C15(H15), C35(H35), C48(H48), C10(H10), C30(H30), C49(H49), C21(H21), C2(H2),
 C9(H9), C29(H29), C4(H4), C3(H3), C22(H22)
2.b Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              20661
_shelx_hkl_checksum              2034
_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 1.272
_oxdiff_exptl_absorpt_empirical_full_min 0.715