N,N′-Substituted thioureas and their metal complexes: syntheses, structures and electronic properties
Al-Riyahee, Ali A. A.; Horton, Peter N.; Coles, Simon J.; Berry, Colin; Horrocks, Paul D.; Pope, Simon J. A.; Amoroso, Angelo J.; Dalton Transactions  (2022) –; doi:10.1039/D1DT04091J

data_7709464
_publ_section_title
;
 &#x000D; N,N&#x2032;-Substituted thioureas and their metal complexes:
 syntheses, structures and electronic properties
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT04091J
_journal_year                    2022
_chemical_formula_moiety         'C14 H18 N6 S2 Zn, 2(Cl O4)'
_chemical_formula_sum            'C14 H18 Cl2 N6 O8 S2 Zn'
_chemical_formula_weight         598.73
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-05-26
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2021-05-07 deposited with the CCDC.	2022-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.109(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.1243(2)
_cell_length_b                   11.4452(3)
_cell_length_c                   18.1830(5)
_cell_measurement_reflns_used    10977
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.4960
_cell_measurement_theta_min      2.0540
_cell_volume                     1066.21(6)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega -109.00   71.00   0.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000    0.0000    0.0000 360

  2 omega  -69.00   22.00   0.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000  -72.0000  150.0000 182

  3 omega  -57.00   14.00   0.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000  -72.0000  -30.0000 142

  4 omega  -79.00   19.00   0.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000  -54.0000    0.0000 196

  5 omega  -27.00    1.00   0.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000   72.0000  -90.0000 56

  6 omega  -22.00    3.00   0.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000  -72.0000 -180.0000 50

  7 omega  -94.00   32.00   0.5000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.0000   18.0000  -60.0000 252
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with HF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ detector'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_UB_11      -0.0536030000
_diffrn_orient_matrix_UB_12      0.0571268000
_diffrn_orient_matrix_UB_13      -0.0006776000
_diffrn_orient_matrix_UB_21      0.1038893000
_diffrn_orient_matrix_UB_22      0.0191469000
_diffrn_orient_matrix_UB_23      -0.0221728000
_diffrn_orient_matrix_UB_31      -0.0741879000
_diffrn_orient_matrix_UB_32      -0.0144352000
_diffrn_orient_matrix_UB_33      -0.0320877000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, HF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0074
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            7361
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.548
_diffrn_reflns_theta_min         2.103
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    1.656
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80208
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.865
_exptl_crystal_description       Prism
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.417
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.021(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         7361
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0880P)^2^+0.2970P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1058
_refine_ls_wR_factor_ref         0.1100
_reflns_Friedel_coverage         0.902
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                7240
_reflns_number_total             7361
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04091j2.cif
_cod_data_source_block           4_2014ncs0935
_cod_database_code               7709464
_chemical_oxdiff_formula         'C34 H50 N6 O2 S2 Zn (ClO4)2'
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.839
_diffrn_oxdiff_twin_integration_method simultaneous
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6516(14) 0.3484(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N1-H1A = N1-H1B = N2-H2 = N11-H11A = N11-H11B = N12-H12
 0.87 with sigma of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C13(H13), C14(H14), C16(H16)
4.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              87973
_shelx_hkl_checksum              7551
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'