New bis-pyrazolate zinc(ii) complexes as potential anticancer drugs: from structure to anticancer activity
Hasić, Rušid; Serezlić, Majda Kolenović; Caković, Angelina; Bogojeski, Jovana; Nikodijević, Danijela; Milutinović, Milena; Stanojević, Aleksandra; Čavić, Milena; Egorov, Andrei V.; Komolkin, Andrei V.; Kornyakov, Ilya V.; Scheurer, Andreas; Puchta, Ralph; Soldatović, Tanja V.; New Journal of Chemistry 49 (2025) 3617–3632; doi:10.1039/D5NJ00043B

data_7063639
_publ_section_title
;
 New bis-pyrazolate zinc(ii) complexes as potential anticancer drugs: from
 structure to anticancer activity
;
_journal_issue                   9
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              3617
_journal_page_last               3632
_journal_paper_doi               10.1039/D5NJ00043B
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C19 H25 Cl2 N5 Zn, 2.459(H2 O)'
_chemical_formula_sum            'C19 H29.92 Cl2 N5 O2.46 Zn'
_chemical_formula_weight         504.03
_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
_audit_creation_date             2024-02-28
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-03-12 deposited with the CCDC.	2025-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                67.436(3)
_cell_angle_beta                 84.168(3)
_cell_angle_gamma                75.427(4)
_cell_formula_units_Z            2
_cell_length_a                   10.0761(4)
_cell_length_b                   11.1556(5)
_cell_length_c                   11.5131(4)
_cell_measurement_reflns_used    10571
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      79.4310
_cell_measurement_theta_min      4.1450
_cell_volume                     1156.60(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.959
_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   -116.00 -38.00   0.50    0.70    --  -47.51 -28.00  44.00  156
  2  \w    -12.00  14.00   0.50    0.70    --  -47.51  28.00-153.00   52
  3  \w     37.00 118.00   0.50    0.70    --   47.51  28.00-153.00  162
  4  \w   -176.00-109.00   0.50    2.00    -- -106.00 -28.00  44.00  134
  5  \w    141.00 178.00   0.50    2.00    --  113.25  28.00-153.00   74
  6  \w    111.00 138.00   0.50    2.00    --  113.25  28.00-153.00   54
  7  \w    -57.00  24.00   0.50    0.70    --  -47.51  57.00 -30.00  162
  8  \w   -110.00 -85.00   0.50    0.70    --  -47.51-125.00 -30.00   50
  9  \w     76.00 117.00   0.50    0.70    --   47.51 125.00-120.00   82
 10  \w    -21.00   4.00   0.50    0.70    --   47.51 -28.00  44.00   50
 11  \w    -27.00  19.00   0.50    0.70    --   47.51 -19.00 -90.00   92
 12  \w    -22.00  68.00   0.50    0.70    --   47.51 -77.00-180.00  180
 13  \w    -70.00 -36.00   0.50    2.00    -- -106.00  61.00-180.00   68
 14  \w   -118.00 -93.00   0.50    2.00    -- -106.00 -30.00   0.00   50
 15  \w    -83.00 -42.00   0.50    2.00    -- -106.00 144.00-175.07   82
 16  \w   -120.00 -93.00   0.50    2.00    -- -106.00 136.00 -16.32   54
 17  \w   -131.00 -99.00   0.50    2.00    -- -106.00 -77.00   0.00   64
 18  \w    -76.00 -33.00   0.50    2.00    -- -106.00 125.00 -90.00   86
 19  \w   -107.00 -78.00   0.50    2.00    -- -106.00 125.00 -30.00   58
 20  \w   -108.00 -83.00   0.50    2.00    -- -106.00 109.00  55.12   50
 21  \w    -71.00 -33.00   0.50    2.00    -- -106.00  61.00   0.00   76
 22  \w   -111.00 -82.00   0.50    2.00    -- -106.00 125.00-180.00   58
 23  \w   -108.00 -80.00   0.50    2.00    -- -106.00 110.00  96.43   56
 24  \w   -142.00-107.00   0.50    2.00    -- -106.00 -30.00 -90.00   70
 25  \w   -126.00-101.00   0.50    2.00    -- -106.00 144.00-108.68   50
 26  \w    -64.00 -36.00   0.50    2.00    -- -106.00 109.00  55.12   56
 27  \w   -176.00-136.00   0.50    2.00    -- -106.00 -30.00   0.00   80
 28  \w   -177.00-139.00   0.50    2.00    -- -106.00 -77.00   0.00   76
 29  \w   -111.00 -85.00   0.50    2.00    -- -106.00 125.00 -90.00   52
 30  \w    -68.00 -42.00   0.50    2.00    -- -106.00 144.00-108.68   52
 31  \w   -126.00 -89.00   0.50    2.00    -- -106.00 144.00 109.55   74
 32  \w    -82.00 -56.00   0.50    2.00    -- -106.00 144.00 109.55   52
 33  \w    -71.00 -41.00   0.50    2.00    -- -106.00 125.00-180.00   60
 34  \w    -72.00 -36.00   0.50    2.00    -- -106.00 125.00 -30.00   72
 35  \w   -126.00 -92.00   0.50    2.00    -- -106.00 144.00-175.07   68
 36  \w     43.00  75.00   0.50    2.00    --  113.25 -94.00-180.00   64
 37  \w    101.00 149.00   0.50    2.00    --  113.25  15.00 120.00   96
 38  \w     43.00  69.00   0.50    2.00    --  113.25 -61.00  30.00   52
 39  \w     43.00 105.00   0.50    2.00    --  113.25 -77.00 -30.00  124
 40  \w     42.00 104.00   0.50    2.00    --  113.25 -94.00  60.00  124
 41  \w     53.00 103.00   0.50    2.00    --  113.25 -77.00-180.00  100
 42  \w     42.00  86.00   0.50    2.00    --  113.25 -94.00 -60.00   88
 43  \w     44.00 100.00   0.50    2.00    --  113.25 -94.00 120.00  112
 44  \w     45.00  70.00   0.50    2.00    --  113.25 -61.00-150.00   50
 45  \w     45.00  70.00   0.50    2.00    --  113.25 -61.00 120.00   50
 46  \w    126.00 176.00   0.50    2.00    --  113.25 125.00  30.00  100
 47  \w     44.00  69.00   0.50    2.00    --  113.25 -61.00-180.00   50
 48  \w     76.00 115.00   0.50    2.00    --  113.25 125.00  30.00   78
 49  \w    118.00 175.00   0.50    2.00    --  113.25  45.00 150.00  114
 50  \w    109.00 175.00   0.50    2.00    --  113.25  30.00 -90.00  132
 51  \w    153.00 178.00   0.50    2.00    --  113.25  15.00 120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1475324000
_diffrn_orient_matrix_UB_12      0.0849040000
_diffrn_orient_matrix_UB_13      -0.0307476000
_diffrn_orient_matrix_UB_21      0.0335954000
_diffrn_orient_matrix_UB_22      0.1036071000
_diffrn_orient_matrix_UB_23      0.0433434000
_diffrn_orient_matrix_UB_31      0.0454140000
_diffrn_orient_matrix_UB_32      0.0754107000
_diffrn_orient_matrix_UB_33      -0.1348076000
_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  0.0435
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            15818
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.187
_diffrn_reflns_theta_min         4.158
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.823
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88718
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (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    1.447
_exptl_crystal_description       prism
_exptl_crystal_F_000             525
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.486
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     311
_refine_ls_number_reflns         4845
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0317
_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^)+(0.0240P)^2^+0.7582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0767
_refine_ls_wR_factor_ref         0.0792
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4272
_reflns_number_total             4845
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00043b2.cif
_cod_data_source_block           2ver0-26329_iii
_cod_depositor_comments
'Adding full bibliography for 7063638--7063639.cif.'
_cod_database_code               7063639
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'Zn Cl2 C19 H25 N5'
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.832
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(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
 H4B-O4
 0.96 with sigma of 0.02
 H3B-O3
 0.96 with sigma of 0.02
 H1A-O1
 0.96 with sigma of 0.02
 H1B-O1
 0.96 with sigma of 0.02
 H2A-O2
 0.96 with sigma of 0.02
 O3-H3A
 0.96 with sigma of 0.02
 H2B-O2
 0.96 with sigma of 0.02
 H4A-O4
 0.96 with sigma of 0.02
 H1B-H1A
 1.52 with sigma of 0.04
 H4A-H4B
 1.52 with sigma of 0.04
 H3B-H3A
 1.52 with sigma of 0.04
 H2B-H2A
 1.52 with sigma of 0.04
3. Others
 Sof(O2)=Sof(H2A)=Sof(H2B)=Sof(O4)=Sof(H4A)=Sof(H4B)=1-FVAR(1)
 Sof(O3)=Sof(H3A)=Sof(H3B)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 N1(H1), N5(H5), C2(H2), C3(H3), C4(H4), C7(H7), C14(H14)
4.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              60776
_shelx_hkl_checksum              60726
_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 2.097
_oxdiff_exptl_absorpt_empirical_full_min 0.480