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_7063246
_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         'C36 H54 Cl2 Cu4 N12 O12 S4, 2(H2 O)'
_chemical_formula_sum            'C36 H58 Cl2 Cu4 N12 O14 S4'
_chemical_formula_weight         1336.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-29
_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                90
_cell_angle_beta                 106.121(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.4884(6)
_cell_length_b                   14.4023(5)
_cell_length_c                   18.7364(7)
_cell_measurement_reflns_used    3354
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.6980
_cell_measurement_theta_min      2.1780
_cell_volume                     3496.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1593
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_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      8.00  85.00   1.00   15.00    --   17.79  70.00-124.00   77
  2  \w    -49.00  32.00   1.00   15.00    --   17.79 -70.00 103.00   81
  3  \w    -37.00  -5.00   1.00   15.00    --  -15.29 -77.00 -90.00   32
  4  \w     -9.00  23.00   1.00   15.00    --   17.79  77.00-150.00   32
  5  \w     -8.00  21.00   1.00   15.00    --   17.79  77.00  90.00   29
;
_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      0.0345224000
_diffrn_orient_matrix_UB_12      0.0382096000
_diffrn_orient_matrix_UB_13      0.0082627000
_diffrn_orient_matrix_UB_21      0.0117857000
_diffrn_orient_matrix_UB_22      -0.0064084000
_diffrn_orient_matrix_UB_23      -0.0342844000
_diffrn_orient_matrix_UB_31      -0.0408257000
_diffrn_orient_matrix_UB_32      0.0303950000
_diffrn_orient_matrix_UB_33      -0.0175955000
_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  0.0589
_diffrn_reflns_av_unetI/netI     0.0801
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            20532
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.811
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.450
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.99612
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.269
_exptl_crystal_description       prism
_exptl_crystal_F_000             1368
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.172
_refine_diff_density_min         -0.556
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     330
_refine_ls_number_reflns         6108
_refine_ls_number_restraints     64
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1293
_refine_ls_R_factor_gt           0.0895
_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^)+(0.1243P)^2^+12.8767P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2399
_refine_ls_wR_factor_ref         0.2679
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3822
_reflns_number_total             6108
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj00342j2.cif
_cod_data_source_block           shi_4991_roru_auto
_cod_depositor_comments
'Adding full bibliography for 7063243--7063248.cif.'
_cod_database_code               7063246
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H21Cu2N7O4S2
_chemical_oxdiff_usercomment     DC_250
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.670
_reflns_odcompleteness_completeness 91.29
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C8X-C10X \\sim C8A-C10A
 with sigma of 0.01
 C13X-C12X \\sim C12X-C11X
 with sigma of 0.01
 C10X-C13X \\sim C12X-C10X \\sim C11C-C10A \\sim C10A-C11B \\sim C10X-C11X
\\sim C10A-C11A
 with sigma of 0.01
 C11B-C11C \\sim C11C-C11A
 with sigma of 0.01
 C11C-C11A \\sim C11A-C11B
 with sigma of 0.01
 C18-C8X \\sim C7A-C8A \\sim C8X-C5 \\sim C8A-C7B \\sim C18-C6A \\sim C7A-C6A
\\sim C5-C6B \\sim C7B-C6B
 with sigma of 0.01
 C11X-C13X \\sim C13X-C12X
 with sigma of 0.01
 C6A-C8A \\sim C8A-C6B
 with sigma of 0.01
 C6A-C8X \\sim C8X-C6B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C8X) \\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C11X) = Uanis(C11C) = Uanis(C12X) = Uanis(C13X) = Uanis(C11B) =
Uanis(C11A)
Uanis(C10X) = Uanis(C10A)
Uanis(C5) = Uanis(C7B) = Uanis(C18) = Uanis(C7A)
Uanis(C8X) = Uanis(C8A)
4. Others
 Fixed Sof: O1W(0.5) H1WA(0.5) H1WB(0.5) O2W(0.5) H2WA(0.5) H2WB(0.5) H3B(0.5)
 H3A(0.5) C5(0.5) H5(0.5) C7B(0.5) H7B(0.5) C7A(0.5) H7A(0.5) C8A(0.5) C8X(0.5)
 C10A(0.5) C10X(0.5) C11C(0.5) H11J(0.5) H11K(0.5) H11L(0.5) C11A(0.5)
 H11G(0.5) H11H(0.5) H11I(0.5) C11X(0.5) H11D(0.5) H11E(0.5) H11F(0.5)
 C11B(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C12X(0.5) H12A(0.5) H12B(0.5)
 H12C(0.5) C13X(0.5) H13A(0.5) H13B(0.5) H13C(0.5) C18(0.5) H18(0.5)
5.a Riding coordinates:
 O1W(H1WA,H1WB), O2W(H2WA,H2WB), C11C(H11J,H11K,H11L), C11A(H11G,H11H,H11I),
 C11X(H11D,H11E,H11F), C11B(H11A,H11B,H11C), C12X(H12A,H12B,H12C), C13X(H13A,
 H13B,H13C)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
5.c Aromatic/amide H refined with riding coordinates:
 N1A(H1A), N1B(H1B), N3B(H3B), N3A(H3A), C5(H5), C5B(H5B), C5A(H5A), C7B(H7B),
 C7A(H7A), C18(H18)
5.d Idealised Me refined as rotating group:
 C3(H3C,H3D,H3E), C13A(H13G,H13H,H13I), C13B(H13D,H13E,H13F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              66360
_shelx_hkl_checksum              10131
_shelx_fab_checksum              60415
_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 1.065
_oxdiff_exptl_absorpt_empirical_full_min 0.933