Phenolato Ti(IV) Hexacoordinate Complexes as Anticancer Chemotherapy: Enhancement of Solubility, Hydrolytic Stability, and Cytotoxicity
Taha, Mohammad; Tshuva, Edit Y.; Dalton Transactions  (2023) –; doi:10.1039/D3DT00984J

data_7712922
_publ_section_title
;
 Phenolato Ti(IV) Hexacoordinate Complexes as Anticancer Chemotherapy:
 Enhancement of Solubility, Hydrolytic Stability, and Cytotoxicity
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00984J
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H26 Br2 N2 O4 Ti, C H4 O'
_chemical_formula_sum            'C23 H30 Br2 N2 O5 Ti'
_chemical_formula_weight         622.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-18
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-05-18 deposited with the CCDC.	2023-05-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.8428(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.9779(2)
_cell_length_b                   12.62848(15)
_cell_length_c                   23.5892(4)
_cell_measurement_reflns_used    35278
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      29.2630
_cell_measurement_theta_min      2.2550
_cell_volume                     5010.34(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.847
_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    -58.00 -31.00   0.50   95.00    --    8.48 -10.00-119.00   54
  2  \w    -22.00  71.00   0.50   95.00    --   -9.57  10.00  53.00  186
  3  \w    -90.00 -41.00   0.50   95.00    --   -9.57 -10.00-119.00   98
  4  \w    -58.00  37.00   0.50   95.00    --    8.48 -77.00 150.00  190
  5  \w    -12.00  85.00   0.50   95.00    --    8.48  37.00 150.00  194
  6  \w    -23.00  48.00   0.50   95.00    --    8.48 -99.00-150.00  142
  7  \w     -5.00  22.00   0.50   95.00    --   -9.57 -99.00 120.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0247166000
_diffrn_orient_matrix_UB_12      -0.0062496000
_diffrn_orient_matrix_UB_13      -0.0265556000
_diffrn_orient_matrix_UB_21      -0.0341696000
_diffrn_orient_matrix_UB_22      0.0035071000
_diffrn_orient_matrix_UB_23      0.0141647000
_diffrn_orient_matrix_UB_31      -0.0006361000
_diffrn_orient_matrix_UB_32      0.0557156000
_diffrn_orient_matrix_UB_33      -0.0038766000
_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  0.0262
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.847
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            69225
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.797
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.620
_diffrn_reflns_theta_min         1.982
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.568
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.557
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.55a (Rigaku Oxford Diffraction, 2022)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.650
_exptl_crystal_description       plate
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.071
_refine_diff_density_max         1.093
_refine_diff_density_min         -0.658
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Flack x determined using 7824 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1221
_refine_ls_number_reflns         24633
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0362
_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^)+(0.0445P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0718
_refine_ls_wR_factor_ref         0.0755
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.743
_reflns_number_gt                20146
_reflns_number_total             24633
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00984j2.cif
_cod_data_source_block           mohammadt4d
_cod_database_code               7712922
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C23H30Br2N2O5Ti
_chemical_oxdiff_usercomment     L5Ti
_shelx_estimated_absorpt_t_max   0.786
_shelx_estimated_absorpt_t_min   0.416
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Fixed Sof: O4MB(0.3) H4MB(0.3) C4MB(0.3) H4MA(0.3) H4MC(0.3) H4MD(0.3)
 O4MA(0.7) H4ME(0.7) C4MA(0.7) H4MF(0.7) H4MG(0.7) H4MH(0.7)
3.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C30(H30A,H30B), C31(H31A,H31B),
  C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,
 H36B), C37(H37A,H37B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B),
 C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B),
  C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,
 H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C19(H19), C21(H21), C25(H25), C27(H27), C41(H41), C43(H43),
 C47(H47), C49(H49), C63(H63), C65(H65), C69(H69), C71(H71), C85(H85), C87(H87)
3.c Tetrahedral OH refined with riding coordinates:
 O1M(H1M), O2M(H2M), O4MB(H4MB), O4MA(H4ME)
3.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C22(H22A,H22B,H22C), C29(H29A,H29B,H29C), C44(H44A,H44B,
 H44C), C51(H51A,H51B,H51C), C66(H66A,H66B,H66C), C73(H73A,H73B,H73C), C88(H88A,
 H88B,H88C), C1M(H1MA,H1MB,H1MC), C2M(H2MA,H2MB,H2MC), C3M(H3MA,H3MB,H3MC),
 C4MB(H4MA,H4MC,H4MD), C4MA(H4MF,H4MG,H4MH)
3.e Idealised tetrahedral OH refined as rotating group:
 O3M(H3M)
;
_shelx_res_checksum              61550
_shelx_hkl_checksum              66665
_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 1.336
_oxdiff_exptl_absorpt_empirical_full_min 0.851