Hexadentate Technetium-99m Bis(thiosemicarbazonato) Complexes: Synthesis, Characterisation and Biodistribution
Kelderman, Cormac; Davey, Patrick; Ma, Michelle; de Veer, Michael; Salimova, Ekaterina; Donnelly, Paul Stephen; Paterson, Brett Michael; Dalton Transactions  (2022) –; doi:10.1039/D2DT01264B

data_7710692
_publ_section_title
;
 Hexadentate Technetium-99m Bis(thiosemicarbazonato) Complexes: Synthesis,
 Characterisation and Biodistribution
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01264B
_journal_year                    2022
_chemical_formula_moiety
'2(C19 H40 N8 S2), 4(H2 O), 1.333(C2.25 H5.25 N0.75 O0.75)'
_chemical_formula_sum            'C41 H95 N17 O5 S4'
_chemical_formula_weight         1034.57
_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             2021-12-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-01-26 deposited with the CCDC.	2022-06-30 downloaded from the CCDC.
;
_cell_angle_alpha                97.556(2)
_cell_angle_beta                 111.701(2)
_cell_angle_gamma                110.673(2)
_cell_formula_units_Z            2
_cell_length_a                   13.9656(4)
_cell_length_b                   15.2212(4)
_cell_length_c                   16.5693(4)
_cell_measurement_reflns_used    18776
_cell_measurement_temperature    122.99(10)
_cell_measurement_theta_max      31.4480
_cell_measurement_theta_min      3.3620
_cell_volume                     2919.43(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      122.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_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     -5.00  21.00   0.50   10.00    --    7.87  19.00  30.00   52
  2  \w     33.00  83.00   0.50   10.00    --    7.87  19.00  30.00  100
  3  \w    -12.00  65.00   0.50   10.00    --   -8.50  38.00-120.00  154
  4  \w    -15.00  11.00   0.50   10.00    --    7.87 -99.00-120.00   52
  5  \w    -20.00  25.00   0.50   10.00    --   -8.50 -99.00 -90.00   90
  6  \w    -23.00   3.00   0.50   10.00    --   -8.50 -99.00 -30.00   52
  7  \w    -57.00  21.00   0.50   10.00    --    7.87 -77.00 120.00  156
  8  \w     -8.00  21.00   0.50   10.00    --   -8.50 -99.00 150.00   58
  9  \w    -72.00  14.00   0.50   10.00    --   -8.50 -77.00  60.00  172
 10  \w    -80.00 -18.00   0.50   10.00    --   -8.50 -38.00 120.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0282021000
_diffrn_orient_matrix_UB_12      0.0105614000
_diffrn_orient_matrix_UB_13      0.0479800000
_diffrn_orient_matrix_UB_21      0.0026075000
_diffrn_orient_matrix_UB_22      0.0479307000
_diffrn_orient_matrix_UB_23      0.0056544000
_diffrn_orient_matrix_UB_31      -0.0537367000
_diffrn_orient_matrix_UB_32      -0.0178810000
_diffrn_orient_matrix_UB_33      0.0009446000
_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  0.0394
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            41859
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         3.345
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.216
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87315
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.81a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             1128
_exptl_crystal_recrystallization_method
'Vapour diffusion of water into a DMF solution of the compound.'
_exptl_crystal_size_max          0.299
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.036
_refine_diff_density_max         0.963
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     775
_refine_ls_number_reflns         11457
_refine_ls_number_restraints     41
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0498
_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^)+(0.0535P)^2^+2.5032P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1268
_refine_ls_wR_factor_ref         0.1336
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9300
_reflns_number_total             11457
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01264b2.cif
_cod_data_source_block           hexbis(etsc)
_cod_original_cell_volume        2919.42(14)
_cod_database_code               7710692
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.938
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.82
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All H(H,H,H) groups, All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O61-H61
 0.88 with sigma of 0.02
 O59-H59A
 0.88 with sigma of 0.02
 O59-H59
 0.88 with sigma of 0.02
 O60-H60
 0.88 with sigma of 0.02
 O60-H60A
 0.88 with sigma of 0.02
 O62-H62
 0.88 with sigma of 0.02
 O62-H62A
 0.88 with sigma of 0.02
 O60-H60B
 0.88 with sigma of 0.02
 O59-H59B
 0.88 with sigma of 0.02
 O61-H61B
 0.88 with sigma of 0.02
 O61-H61A
 0.88 with sigma of 0.02
 H59B-O60
 1.96 with sigma of 0.04
 H61B-O59
 1.96 with sigma of 0.04
 H60B-O62
 1.96 with sigma of 0.04
 H59A-H59
 1.38 with sigma of 0.04
 H62-H62B
 1.38 with sigma of 0.04
 H62B-H62A
 1.38 with sigma of 0.04
 H62A-H62
 1.38 with sigma of 0.04
 H60-H60A
 1.38 with sigma of 0.04
 H59-H59A
 1.38 with sigma of 0.04
 H61-H61A
 1.38 with sigma of 0.04
 H60A-H60B
 1.38 with sigma of 0.04
 H60-H60B
 1.38 with sigma of 0.04
 H59-H59B
 1.38 with sigma of 0.04
 H59A-H59B
 1.38 with sigma of 0.04
 H61A-H61B
 1.38 with sigma of 0.04
 H61-H61B
 1.38 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C20) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: H60A(0.75) H62A(0.75) H59A(0.75) O3(0.375) C15(0.75) H15A(0.75)
 H15B(0.75) H15C(0.75) C11(0.75) H11A(0.75) H11B(0.75) H11C(0.75) C4(0.375)
 H4(0.375) N2(0.25) O2(0.25) C20(0.25) H20(0.25) C30(0.25) H30A(0.25)
 H30B(0.25) H30C(0.25) C27(0.25) H27A(0.25) H27B(0.25) H27C(0.25) O3'(0.375)
 C4'(0.375) H4'(0.375) H62B(0.25) H61A(0.75) H60B(0.25) H59B(0.25) H61B(0.25)
 N5(0.75)
5.a Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C9(H9A,H9B), C39(H39A,H39B), C37(H37A,H37B), C28(H28A,H28B),
 C18(H18A,H18B), C47(H47A,H47B), C10(H10A,H10B), C8(H8A,H8B), C57(H57A,H57B)
5.b Aromatic/amide H refined with riding coordinates:
 N46(H46), C4(H4), C20(H20), C4'(H4')
5.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C55(H55A,H55B,H55C), C50(H50A,H50B,H50C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C53(H53A,H53B,H53C), C51(H51A,H51B,H51C), C26(H26A,
 H26B,H26C), C54(H54A,H54B,H54C), C52(H52A,H52B,H52C), C19(H19A,H19B,H19C),
 C22(H22A,H22B,H22C), C29(H29A,H29B,H29C), C23(H23A,H23B,H23C), C58(H58A,H58B,
 H58C), C48(H48A,H48B,H48C), C15(H15A,H15B,H15C), C11(H11A,H11B,H11C), C30(H30A,
 H30B,H30C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              11814
_shelx_hkl_checksum              12496
_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 1.266
_oxdiff_exptl_absorpt_empirical_full_min 0.631