Defining the oxidation site in Cu(II) and Ni(II) Complexes of ligands combining amido, phenolato and pyridine donors
Wang, Guanqi; Philouze, Christian; Berthiol, Florian; Moreau, Yohann; Jarjayes, Olivier; Thomas, Fabrice; Dalton Transactions  (2025) –; doi:10.1039/D5DT02056E

data_7719895
_publ_section_title
;
 Defining the oxidation site in Cu(II) and Ni(II) Complexes of ligands
 combining amido, phenolato and pyridine donors
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02056E
_journal_year                    2025
_chemical_formula_moiety
'C27 H28 Cu N3 O3, 2(C16 H36 N), 1.75[CH2Cl2], 0.3[H2O]'
_chemical_formula_sum            'C60.75 H104.1 Cl3.5 Cu N5 O3.3'
_chemical_formula_weight         1145.00
_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             2024-06-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec141 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-06-13 deposited with the CCDC.	2025-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                102.46(3)
_cell_angle_beta                 97.36(3)
_cell_angle_gamma                93.73(3)
_cell_formula_units_Z            2
_cell_length_a                   13.536(3)
_cell_length_b                   15.206(3)
_cell_length_c                   16.497(3)
_cell_measurement_reflns_used    73581
_cell_measurement_temperature    200
_cell_measurement_theta_max      27.500
_cell_measurement_theta_min      1.278
_cell_volume                     3273.2(12)
_computing_cell_refinement       EvalCCD
_computing_data_collection       Collect
_computing_data_reduction        EvalCCD
_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_temperature      200
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.904
_diffrn_measurement_device       '\k-geometry 4 circles diffractometer'
_diffrn_measurement_device_type  'Bruker-AXS-enraf-nonius KappaAPEXII'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'Montel optic'
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0733
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.904
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            73580
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         1.278
_diffrn_source                   'Incoatec ISG250'
_diffrn_source_target            Mo
_diffrn_source_type              'Microfocus sealed tube'
_exptl_absorpt_coefficient_mu    0.521
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.716216
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.1577 before and 0.0649 after correction.
The Ratio of minimum to maximum transmission is 0.7162.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.162
_exptl_crystal_description       block
_exptl_crystal_F_000             1237
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.402
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     667
_refine_ls_number_reflns         13593
_refine_ls_number_restraints     181
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.1209
_refine_ls_R_factor_gt           0.0767
_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^)+(0.0628P)^2^+3.8341P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1704
_refine_ls_wR_factor_ref         0.1972
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9169
_reflns_number_total             13593
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02056e2.cif
_cod_data_source_block           sad_CCDC2
_cod_original_cell_volume        3273.5(12)
_cod_original_formula_sum        'C60.75 H104.10 Cl3.50 Cu N5 O3.30'
_cod_database_code               7719895
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.859
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C56-C57
 1.53 with sigma of 0.02
 C57-C58A
 1.53 with sigma of 0.02
 C58A-C59A
 1.53 with sigma of 0.02
 C59A-C57
 2.5 with sigma of 0.02
 C58A-C56
 2.5 with sigma of 0.02
 C57-N5
 2.5 with sigma of 0.02
 C58B-C57
 1.53 with sigma of 0.02
 C59B-C58B
 1.53 with sigma of 0.02
 C59B-C57
 2.5 with sigma of 0.02
 C49-C51B
 2.5 with sigma of 0.02
 C49-C51A
 2.5 with sigma of 0.02
 C50B-C48
 2.5 with sigma of 0.02
 C50A-C48
 2.5 with sigma of 0.02
 C49-C50A
 1.5 with sigma of 0.02
 C49-C50B
 1.5 with sigma of 0.02
 C50B-C51B
 1.5 with sigma of 0.02
 C50A-C51A
 1.5 with sigma of 0.02
3. Rigid bond restraints
 N5, C44, C52, C48, C56, C45, C53, C49, C57, C46, C54, C50A, C58A, C47, C55,
 C51A, C59A, C50A, C50B, C51A, C51B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N5 \\sim C44 \\sim C52 \\sim C48 \\sim C56 \\sim C45 \\sim C53 \\sim C49 \\sim
C57 \\sim C46 \\sim C54 \\sim C50A \\sim C58A \\sim C47 \\sim C55 \\sim C51A
\\sim C59A \\sim C50A \\sim C50B \\sim C51A \\sim C51B: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
5. Others
 Sof(H57C)=Sof(H57D)=Sof(C58B)=Sof(H58C)=Sof(H58D)=Sof(C59B)=Sof(H59D)=
 Sof(H59E)=Sof(H59F)=1-FVAR(1)
 Sof(H57A)=Sof(H57B)=Sof(C59A)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C58A)=
 Sof(H58A)=Sof(H58B)=FVAR(1)
 Sof(H49C)=Sof(H49D)=Sof(C50A)=Sof(H50A)=Sof(H50B)=Sof(C51A)=Sof(H51A)=
 Sof(H51B)=Sof(H51C)=1-FVAR(2)
 Sof(H49A)=Sof(H49B)=Sof(C50B)=Sof(H50C)=Sof(H50D)=Sof(C51B)=Sof(H51D)=
 Sof(H51E)=Sof(H51F)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C32(H32A,H32B), C44(H44A,H44B), C36(H36A,H36B), C40(H40A,
 H40B), C52(H52A,H52B), C54(H54A,H54B), C41(H41A,H41B), C45(H45A,H45B),
 C30(H30A,H30B), C53(H53A,H53B), C37(H37A,H37B), C29(H29A,H29B), C42(H42A,H42B),
  C46(H46A,H46B), C34(H34A,H34B), C33(H33A,H33B), C48(H48A,H48B), C56(H56A,
 H56B), C38(H38A,H38B), C49(H49C,H49D), C49(H49A,H49B), C57(H57A,H57B),
 C57(H57C,H57D), C50A(H50A,H50B), C58A(H58A,H58B), C58B(H58C,H58D), C50B(H50C,
 H50D)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C9(H9), C3(H3), C19(H19), C10(H10), C16(H16), C17(H17), C12(H12),
 C18(H18), C11(H11)
6.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C31(H31A,H31B,H31C), C27(H27A,H27B,H27C), C21(H21A,H21B,
 H21C), C25(H25A,H25B,H25C), C23(H23A,H23B,H23C), C26(H26A,H26B,H26C), C47(H47A,
 H47B,H47C), C43(H43A,H43B,H43C), C35(H35A,H35B,H35C), C55(H55A,H55B,H55C),
 C39(H39A,H39B,H39C), C59A(H59A,H59B,H59C), C51A(H51A,H51B,H51C), C59B(H59D,
 H59E,H59F), C51B(H51D,H51E,H51F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 151 electrons were 
found in a volume of 436\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1.75[CH2Cl2], 0.3[H2O] per Asymmetric Unit 
which account for 153 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              39096
_shelx_hkl_checksum              97233
_shelx_fab_checksum              10800
_olex2_submission_special_instructions 'No special instructions were received'