Synthesis, structure and biological properties of a series of dicopper(bis-thiosemicarbazone) complexes
Cebotari, Diana; Calancea, Sergiu; Garbuz, Olga; Balan, Greta; Marrot, Jérôme; Shova, Sergiu; Guérineau, Vincent; Touboul, David; Tsapkov, Victor; Gulea, Aurelian; Floquet, Sébastien; New Journal of Chemistry 48 (2024) 12043–12053; doi:10.1039/D4NJ00342J

data_7063245
_publ_section_title
;
 Synthesis, structure and biological properties of a series of
 dicopper(bis-thiosemicarbazone) complexes
;
_journal_issue                   26
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              12043
_journal_page_last               12053
_journal_paper_doi               10.1039/D4NJ00342J
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety
'C28.147 H34 Cu4 N12 O4 S4, 2(Cl O4), 2(Cl O3.5), 2(H2 O), 4(C2 H6 O)'
_chemical_formula_sum            'C36.15 H62 Cl4 Cu4 N12 O25 S4'
_chemical_formula_weight         1588.97
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-06-03 deposited with the CCDC.	2024-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                102.963(9)
_cell_angle_beta                 95.669(9)
_cell_angle_gamma                99.977(9)
_cell_formula_units_Z            1
_cell_length_a                   9.0820(11)
_cell_length_b                   11.3880(11)
_cell_length_c                   16.0107(16)
_cell_measurement_reflns_used    3515
_cell_measurement_temperature    160.05(10)
_cell_measurement_theta_max      26.1040
_cell_measurement_theta_min      1.9150
_cell_volume                     1572.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_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_environment      N~2~
_diffrn_ambient_temperature      160.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1593
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -14.00  11.00   1.00   30.00    --  -15.44  45.00  50.00   25
  2  \w      1.00  67.00   1.00   30.00    --   17.94  45.00  50.00   66
  3  \w    -50.00  35.00   1.00   30.00    --   17.94 -45.00 -99.00   85
  4  \w    -71.00 -42.00   1.00   30.00    --  -15.44-178.00 -60.00   29
  5  \w    -71.00 -39.00   1.00   30.00    --  -15.44-178.00  30.00   32
  6  \w     10.00  39.00   1.00   30.00    --   17.94  77.00-120.00   29
  7  \w    -51.00  34.00   1.00   30.00    --   17.94 -38.00-180.00   85
  8  \w      0.00  27.00   1.00   30.00    --   17.94  77.00 -30.00   27
  9  \w     -9.00  37.00   1.00   30.00    --   17.94  77.00 120.00   46
 10  \w     -4.00  35.00   1.00   30.00    --   17.94  77.00-180.00   39
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0162938000
_diffrn_orient_matrix_UB_12      0.0628243000
_diffrn_orient_matrix_UB_13      0.0229010000
_diffrn_orient_matrix_UB_21      0.0740866000
_diffrn_orient_matrix_UB_22      0.0061599000
_diffrn_orient_matrix_UB_23      -0.0112212000
_diffrn_orient_matrix_UB_31      -0.0258085000
_diffrn_orient_matrix_UB_32      0.0165224000
_diffrn_orient_matrix_UB_33      -0.0382053000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_unetI/netI     0.0882
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12761
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.025
_diffrn_reflns_theta_max         25.025
_diffrn_reflns_theta_min         1.873
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.721
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73842
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.109a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_density_diffrn    1.678
_exptl_crystal_description       plate
_exptl_crystal_F_000             811
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.027
_refine_diff_density_min         -1.342
_refine_diff_density_rms         0.183
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     401
_refine_ls_number_reflns         5542
_refine_ls_number_restraints     156
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1271
_refine_ls_R_factor_gt           0.0934
_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^)+(0.1244P)^2^+13.7792P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2290
_refine_ls_wR_factor_ref         0.2540
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3945
_reflns_number_total             5542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj00342j2.cif
_cod_data_source_block           shi_5018_roru_auto
_cod_depositor_comments
'Adding full bibliography for 7063243--7063248.cif.'
_cod_database_code               7063245
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H30N6O8S2Cu2
_chemical_oxdiff_usercomment     DC_251
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.626
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O14-C18
 2.5 with sigma of 0.01
 O14X-C18X
 2.5 with sigma of 0.01
 O14X-C17X = O14-C17 = O13X-C15X = O13-C15
 1.4 with sigma of 0.01
 C18-C17 = C18X-C17X
 1.52 with sigma of 0.01
 C16-C15 = C16X-C15X
 1.52 with sigma of 0.01
 C16-O13
 2.5 with sigma of 0.01
 O13X-C16X
 2.5 with sigma of 0.01
 C10X-C8X \\sim C8X-C9X
 with sigma of 0.01
 C9-C10 \\sim C10-C8
 with sigma of 0.01
 C9X-C10X \\sim C10X-C8X
 with sigma of 0.01
 C7-C8 \\sim C7-C10X \\sim C7-C10 \\sim C7-C9X \\sim C7-C9 \\sim C7-C8X
 with sigma of 0.01
 C10-C8 \\sim C8-C9
 with sigma of 0.01
 Cl2-O8 \\sim Cl2-O9 \\sim Cl2-O10 \\sim Cl2-O7 \\sim Cl2-O12 \\sim Cl2-O11
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C7 \\sim C9X \\sim C10 \\sim C10X \\sim C8 \\sim C8X \\sim C9: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
Uanis(C16X) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C18X)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C15X) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C9X) = Uanis(C9) = Uanis(C8X) = Uanis(C8) = Uanis(C10X) = Uanis(C10)
Uanis(C16) = Uanis(C16X)
Uanis(O14X) = Uanis(O14)
Uanis(C17X) = Uanis(C17)
Uanis(C18X) = Uanis(C18)
Uanis(O13X) = Uanis(O13)
Uanis(C15) = Uanis(C15X)
4. Others
 Sof(C10X)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C8X)=Sof(H8XA)=Sof(H8XB)=
 Sof(H8XC)=Sof(C9)=Sof(C9X)=Sof(H9XA)=Sof(H9XB)=Sof(H9XC)=1-FVAR(1)
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(1)
 Sof(O12)=1-FVAR(2)
 Sof(O11)=FVAR(2)
 Sof(O14)=Sof(H14)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=1-FVAR(3)
 Sof(C17X)=Sof(H17C)=Sof(H17D)=Sof(O14X)=Sof(H14X)=Sof(C18X)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=FVAR(3)
 Sof(O13)=Sof(H13A)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=1-FVAR(4)
 Sof(O13X)=Sof(H13X)=Sof(C15X)=Sof(H15C)=Sof(H15D)=Sof(C16X)=Sof(H16D)=
 Sof(H16E)=Sof(H16F)=FVAR(4)
 Fixed Sof: H2A(0.5) H5(0.5) O9(0.5) O8(0.5) O10(0.5)
5.a Riding coordinates:
 O2(H2), O40(H40A,H40B), N2(H2A), N5(H5), N6(H6A,H6B), O14(H14), N3(H3A,H3B),
 O13(H13A), C18(H18A,H18B,H18C), C10X(H10A,H10B,H10C), C8X(H8XA,H8XB,H8XC),
 C16(H16A,H16B,H16C), C9(H9A,H9B,H9C), C10(H10D,H10E,H10F), C8(H8A,H8B,H8C),
 O14X(H14X), C18X(H18D,H18E,H18F), O13X(H13X), C16X(H16D,H16E,H16F)
5.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C17(H17A,H17B), C17X(H17C,H17D), C15X(H15C,H15D)
5.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C11(H11)
5.d Idealised Me refined as rotating group:
 C9X(H9XA,H9XB,H9XC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              33202
_shelx_hkl_checksum              59804
_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 1.448
_oxdiff_exptl_absorpt_empirical_full_min 0.846