Orthogonal magnetic orbitals in high spin Cu-VO units: structure, magnetism and EPR study of anisotropic heterometallic complexes.
Deng, Qing-Song; Zhang, Yu-Shuang; Wang, Ye-Xin; Xie, Yi; Fu, Peng-Xiang; Gao, Song; Liu, Zheng; Jiang, Shang-Da; Dalton transactions (Cambridge, England : 2003) 53 (2024) 13207–13215; doi:10.1039/d4dt01346h

data_7716686
_publ_section_title
;
 Orthogonal magnetic orbitals in high spin Cu-VO units: structure,
 magnetism and EPR study of anisotropic heterometallic complexes.
;
_journal_issue                   31
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13207
_journal_page_last               13215
_journal_paper_doi               10.1039/d4dt01346h
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C32 H24 Cu N2 O7 V'
_chemical_formula_sum            'C32 H24 Cu N2 O7 V'
_chemical_formula_weight         663.01
_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     direct
_audit_block_doi                 10.5517/ccdc.csd.cc2gyxzb
_audit_creation_date             2024-03-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-15 deposited with the CCDC.	2024-07-19 downloaded from the CCDC.
;
_cell_angle_alpha                71.938(2)
_cell_angle_beta                 84.339(2)
_cell_angle_gamma                83.891(2)
_cell_formula_units_Z            2
_cell_length_a                   7.3860(2)
_cell_length_b                   13.3981(4)
_cell_length_c                   15.4197(4)
_cell_measurement_reflns_used    16279
_cell_measurement_temperature    303.27(10)
_cell_measurement_theta_max      31.2270
_cell_measurement_theta_min      2.4050
_cell_volume                     1438.99(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.30a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.42.30a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.42.30a (Rigaku OD, 2021)'
_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    'SHELXS-1997  (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      303.27(10)
_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 0.800
_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    -52.00  10.00   0.50    1.30    --    3.98 -38.00   0.00  124
  2  \w    -40.00  13.00   0.50    1.30    --    3.98 -33.00  29.00  106
  3  \w    -15.00  36.00   0.50    1.30    --    3.98 -99.00   0.00  102
  4  \w    -68.00  12.00   0.50    1.30    --    3.98 -38.00 -90.00  160
  5  \w     -6.00  77.00   0.50    1.30    --    3.98  33.00-171.00  166
  6  \w    -18.00   7.00   0.50    1.30    --   -4.92 -99.00-150.00   50
  7  \w    -18.00   7.00   0.50    1.30    --   -4.92 -99.00  30.00   50
  8  \w    -17.00  17.00   0.50    1.30    --   -4.92 -99.00   0.00   68
;
_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      -0.0107033000
_diffrn_orient_matrix_UB_12      0.0485956000
_diffrn_orient_matrix_UB_13      0.0067347000
_diffrn_orient_matrix_UB_21      -0.0418602000
_diffrn_orient_matrix_UB_22      0.0202457000
_diffrn_orient_matrix_UB_23      -0.0193249000
_diffrn_orient_matrix_UB_31      -0.0354108000
_diffrn_orient_matrix_UB_32      -0.0122598000
_diffrn_orient_matrix_UB_33      0.0439718000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.800
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21737
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.800
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.932
_diffrn_reflns_theta_min         2.422
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.116
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67648
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.30a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.530
_exptl_crystal_description       block
_exptl_crystal_F_000             676
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.100
_refine_diff_density_min         -0.946
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     468
_refine_ls_number_reflns         7306
_refine_ls_number_restraints     987
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0812
_refine_ls_R_factor_gt           0.0718
_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^)+(0.0811P)^2^+5.0171P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2043
_refine_ls_wR_factor_ref         0.2086
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6037
_reflns_number_total             7306
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01346h2.cif
_cod_data_source_block           ov_8-31-t1_auto
_cod_depositor_comments
'Adding full bibliography for 7716686--7716689.cif.'
_cod_database_code               7716686
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONCuV
_shelx_estimated_absorpt_t_max   0.808
_shelx_estimated_absorpt_t_min   0.776
_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. Restrained distances
 N1-C26 \\sim N1-C26A
 with sigma of 0.02
 N2-C19 \\sim N2-C19A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C19-C26 \\sim C19A-C26A
 with sigma of 0.02
 C20-C25 \\sim C20A-C25A
 with sigma of 0.02
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 C25-C24 \\sim C25A-C24A
 with sigma of 0.02
 C24-C23 \\sim C24A-C23A
 with sigma of 0.02
 C23-C22 \\sim C23A-C22A
 with sigma of 0.02
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 C27-C32 \\sim C27A-C32A
 with sigma of 0.02
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C32-C31 \\sim C32A-C31A
 with sigma of 0.02
 C31-C30 \\sim C31A-C30A
 with sigma of 0.02
 C30-C29 \\sim C30A-C29A
 with sigma of 0.02
 C29-C28 \\sim C29A-C28A
 with sigma of 0.02
 N1-C19 \\sim N1-C19A
 with sigma of 0.04
 N1-C27 \\sim N1-C27A
 with sigma of 0.04
 N2-C20 \\sim N2-C20A
 with sigma of 0.04
 N2-C26 \\sim N2-C26A
 with sigma of 0.04
 C19-C25 \\sim C19A-C25A
 with sigma of 0.04
 C19-C21 \\sim C19A-C21A
 with sigma of 0.04
 C19-C27 \\sim C19A-C27A
 with sigma of 0.04
 C20-C24 \\sim C20A-C24A
 with sigma of 0.04
 C20-C22 \\sim C20A-C22A
 with sigma of 0.04
 C20-C26 \\sim C20A-C26A
 with sigma of 0.04
 C25-C23 \\sim C25A-C23A
 with sigma of 0.04
 C25-C21 \\sim C25A-C21A
 with sigma of 0.04
 C24-C22 \\sim C24A-C22A
 with sigma of 0.04
 C23-C21 \\sim C23A-C21A
 with sigma of 0.04
 C26-C32 \\sim C26A-C32A
 with sigma of 0.04
 C26-C28 \\sim C26A-C28A
 with sigma of 0.04
 C27-C31 \\sim C27A-C31A
 with sigma of 0.04
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 C32-C30 \\sim C32A-C30A
 with sigma of 0.04
 C32-C28 \\sim C32A-C28A
 with sigma of 0.04
 C31-C29 \\sim C31A-C29A
 with sigma of 0.04
 C30-C28 \\sim C30A-C28A
 with sigma of 0.04
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C32) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
5. Others
 Fixed Sof: C19(0.5) H19(0.5) C20(0.5) C25(0.5) H25(0.5) C24(0.5) H24(0.5)
 C23(0.5) H23(0.5) C22(0.5) H22(0.5) C21(0.5) H21(0.5) C26(0.5) H26(0.5)
 C27(0.5) C32(0.5) H32(0.5) C31(0.5) H31(0.5) C30(0.5) H30(0.5) C29(0.5)
 H29(0.5) C28(0.5) H28(0.5) C19A(0.5) H19A(0.5) C20A(0.5) C25A(0.5) H25A(0.5)
 C24A(0.5) H24A(0.5) C23A(0.5) H23A(0.5) C22A(0.5) H22A(0.5) C21A(0.5)
 H21A(0.5) C26A(0.5) H26A(0.5) C27A(0.5) C32A(0.5) H32A(0.5) C31A(0.5)
 H31A(0.5) C30A(0.5) H30A(0.5) C29A(0.5) H29A(0.5) C28A(0.5) H28A(0.5)
6.a Ternary CH refined with riding coordinates:
 C19(H19), C26(H26), C19A(H19A), C26A(H26A)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C8(H8), C14(H14), C15(H15), C17(H17), C25(H25), C24(H24),
 C23(H23), C22(H22), C21(H21), C32(H32), C31(H31), C30(H30), C29(H29), C28(H28),
  C25A(H25A), C24A(H24A), C23A(H23A), C22A(H22A), C21A(H21A), C32A(H32A),
 C31A(H31A), C30A(H30A), C29A(H29A), C28A(H28A)
6.c Fitted hexagon refined as free rotating group:
 C20(C25,C24,C23,C22,C21), C27(C32,C31,C30,C29,C28), C20A(C25A,C24A,C23A,C22A,
 C21A), C27A(C32A,C31A,C30A,C29A,C28A)
6.d Idealised Me refined as rotating group:
 C9(H9a,H9b,H9c), C18(H18a,H18b,H18c)
;
_shelx_res_checksum              72559
_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 1.615
_oxdiff_exptl_absorpt_empirical_full_min 0.575