Differential transmetallation of complexes of the anti-cancer thiosemicarbazone, Dp4e4mT: effects on anti-proliferative efficacy, redox activity, oxy-myoglobin and oxy-hemoglobin oxidation.
Dharmasivam, Mahendiran; Kaya, Busra; Wijesinghe, Tharushi P.; Richardson, Vera; Harmer, Jeffrey R.; Gonzalvez, Miguel A.; Lewis, William; Azad, Mahan Gholam; Bernhardt, Paul V.; Richardson, Des R.; Chemical science 15 (2024) 974–990; doi:10.1039/d3sc05723b

data_1570562
_publ_section_title
;
 Differential transmetallation of complexes of the anti-cancer
 thiosemicarbazone, Dp4e4mT: effects on anti-proliferative efficacy, redox
 activity, oxy-myoglobin and oxy-hemoglobin oxidation.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              974
_journal_page_last               990
_journal_paper_doi               10.1039/d3sc05723b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C30 H34 N10 Ni S2, 2(Cl), H2 O'
_chemical_formula_sum            'C30 H36 Cl2 N10 Ni O S2'
_chemical_formula_weight         746.42
_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             2018-10-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-17 deposited with the CCDC.	2023-12-07 downloaded from the CCDC.
;
_cell_angle_alpha                94.82(2)
_cell_angle_beta                 92.36(2)
_cell_angle_gamma                107.67(3)
_cell_formula_units_Z            2
_cell_length_a                   9.141(3)
_cell_length_b                   14.090(4)
_cell_length_c                   14.188(3)
_cell_measurement_reflns_used    738
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.7590
_cell_measurement_theta_min      5.1360
_cell_volume                     1730.7(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.5861
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.942
_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    -45.00  34.00   1.00   30.00    --  -39.89  38.00 120.00   79
  2  \w    -79.00 -51.00   1.00   30.00    --  -39.89 178.00-150.00   28
  3  \w    -57.00  26.00   1.00   30.00    --  -39.89  57.00 -60.00   83
  4  \w    -84.00  36.00   1.00   30.00    --  -39.89  19.00-120.00  120
  5  \w     57.00 130.00   1.00   30.00    --   39.89 178.00 120.00   73
  6  \w     80.00 130.00   1.00   30.00    --   39.89 178.00 -90.00   50
  7  \w     57.00  86.00   1.00  120.00    --  108.56 -30.00 -60.00   29
  8  \w     37.00  94.00   1.00  120.00    --  108.56 -45.00  60.00   57
  9  \w     36.00  97.00   1.00  120.00    --  108.56 -45.00 120.00   61
 10  \w     43.00 118.00   1.00  120.00    --  108.56-125.00 150.00   75
 11  \w     31.00  87.00   1.00  120.00    --  108.56 -30.00-180.00   56
 12  \w     27.00 110.00   1.00  120.00    --  108.56 -95.00 -60.00   83
 13  \w     98.00 125.00   1.00  120.00    --  108.56 125.00 -90.00   27
 14  \w     85.00 178.00   1.00  120.00    --  108.56  30.00   0.00   93
 15  \w     34.00  98.00   1.00  120.00    --  108.56 -45.00 -90.00   64
 16  \w     59.00 117.00   1.00  120.00    --  108.56-125.00 -90.00   58
 17  \w     35.00  93.00   1.00  120.00    --  108.56 -45.00   0.00   58
 18  \w     69.00  97.00   1.00  120.00    --  108.56-125.00-150.00   28
 19  \w     57.00  82.00   1.00  120.00    --  108.56 -61.00-150.00   25
 20  \w    102.00 129.00   1.00  120.00    --  108.56 125.00-180.00   27
 21  \w     50.00 101.00   1.00  120.00    --  108.56 -95.00  30.00   51
 22  \w     85.00 177.00   1.00  120.00    --  108.56  30.00  90.00   92
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova-Duo, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0345128000
_diffrn_orient_matrix_UB_12      0.0176234000
_diffrn_orient_matrix_UB_13      -0.1031422000
_diffrn_orient_matrix_UB_21      -0.1729235000
_diffrn_orient_matrix_UB_22      -0.0280451000
_diffrn_orient_matrix_UB_23      0.0161855000
_diffrn_orient_matrix_UB_31      0.0186916000
_diffrn_orient_matrix_UB_32      0.1104828000
_diffrn_orient_matrix_UB_33      0.0321221000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_wavelength_determination fundamental
_diffrn_reflns_av_R_equivalents  0.1703
_diffrn_reflns_av_unetI/netI     0.2578
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11803
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.368
_diffrn_reflns_theta_min         4.322
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    3.690
_exptl_absorpt_correction_T_max  0.999
_exptl_absorpt_correction_T_min  0.804
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.432
_exptl_crystal_description       block
_exptl_crystal_F_000             776
_exptl_crystal_recrystallization_method 'crystallised from methanol'
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.036
_exptl_crystal_size_min          0.016
_refine_diff_density_max         1.144
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.967
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     422
_refine_ls_number_reflns         6761
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.967
_refine_ls_R_factor_all          0.2326
_refine_ls_R_factor_gt           0.1045
_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^)+(0.0781P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2267
_refine_ls_wR_factor_ref         0.2878
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2584
_reflns_number_total             6761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05723b2.cif
_cod_data_source_block           drr18_s1677
_cod_depositor_comments
'Adding full bibliography for 1570562--1570567.cif.'
_cod_original_cell_volume        1730.8(9)
_cod_database_code               1570562
_sydney_internal_submission_code drr18_s1677
_sydney_internal_submission_date 2018-09-21
_sydney_internal_submission_number s1677
_sydney_internal_client_code     dm1
_sydney_internal_client_email    mahendiran.dharmasivam@sydney.edu.au
_sydney_internal_client_name     'Mahendiran Dharmasivam'
_sydney_internal_supervisor_code drr
_sydney_internal_supervisor_name 'Des Richardson'
_sydney_internal_collection_date 2018-09-24
_sydney_internal_collection_user wlew0588
_sydney_internal_process_date    2018-09-27
_sydney_internal_process_user    wlew0588
_sydney_internal_solution_date   2018-09-27
_sydney_internal_solution_user   wlew0588
_sydney_internal_refine_date     2018-10-04
_sydney_internal_refine_user     wlew0588
_sydney_internal_check_and_archive_date 2018-10-05
_sydney_internal_check_user      wlew0588
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30H34N10S2Ni H2Cl2 H2O'
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.757
_reflns_odcompleteness_completeness 99.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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.a Free rotating group:
 O1(H1A,H1B)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N22(H22), C1(H1), C2(H2A), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10),
 C11(H11), C21(H21), C22(H22A), C23(H23), C24(H24), C28(H28), C29(H29),
 C30(H30), C31(H31)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C34(H34A,H34B,H34C), C36(H36A,H36B,
 H36C)
;
_shelx_res_checksum              29022
_shelx_hkl_checksum              1267
_olex2_date_sample_data_collection 2018-10-24
_olex2_date_sample_submission    2018-09-19
_olex2_exptl_crystal_mounting_method 'in paratone on a loop'
_olex2_submission_original_sample_id Ni(Dp4e4mT)2
_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 2.396
_oxdiff_exptl_absorpt_empirical_full_min 0.328