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_7709469
_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_absolute_configuration ad
_chemical_formula_moiety         'C17 H25 Cu N5 O2 S2, Cl O4, 0.5(H2 O)'
_chemical_formula_sum            'C17 H26 Cl Cu N5 O6.5 S2'
_chemical_formula_weight         567.54
_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             2016-06-07
_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                 90.462(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3999(3)
_cell_length_b                   14.2258(4)
_cell_length_c                   13.3826(3)
_cell_measurement_reflns_used    18211
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.5500
_cell_measurement_theta_min      2.1960
_cell_volume                     2360.59(10)
_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
'CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)'
_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 0.995
_diffrn_measurement_details
;
  1 omega  -99.00   25.00   0.5000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.0000  -72.0000 -150.0000 248

  2 omega  -73.00   49.00   0.5000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.0000    0.0000 -150.0000 244

  3 omega  -72.00   25.00   0.5000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.0000  -72.0000   30.0000 194

  4 omega  -14.00   64.00   0.5000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.0000   54.0000  150.0000 156
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with VHF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_UB_11      -0.0133219000
_diffrn_orient_matrix_UB_12      0.0179241000
_diffrn_orient_matrix_UB_13      -0.0479200000
_diffrn_orient_matrix_UB_21      0.0553482000
_diffrn_orient_matrix_UB_22      -0.0004259000
_diffrn_orient_matrix_UB_23      -0.0130563000
_diffrn_orient_matrix_UB_31      -0.0057212000
_diffrn_orient_matrix_UB_32      -0.0465534000
_diffrn_orient_matrix_UB_33      -0.0183986000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0414
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            30299
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         2.230
_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    1.261
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59658
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.597
_exptl_crystal_description       rod
_exptl_crystal_F_000             1172
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.249
_refine_diff_density_min         -0.796
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Flack x determined using 3317 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     681
_refine_ls_number_reflns         10291
_refine_ls_number_restraints     157
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0572
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1052P)^2^+0.6975P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1509
_refine_ls_wR_factor_ref         0.1579
_reflns_Friedel_coverage         0.834
_reflns_Friedel_fraction_full    0.942
_reflns_Friedel_fraction_max     0.900
_reflns_number_gt                8684
_reflns_number_total             10291
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt04091j2.cif
_cod_data_source_block           21_2015ncs0006
_cod_original_cell_volume        2360.59(11)
_cod_original_formula_sum        'C17 H26 Cl Cu N5 O6.50 S2'
_cod_database_code               7709469
_chemical_oxdiff_formula         'C30 H32 N10 O8 S4 Cu Cl'
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.853
_reflns_odcompleteness_completeness 99.46
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.50
_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
 C29-C34 \\sim C29-C34A
 with sigma of 0.02
 C29-C35 \\sim C29-C35A \\sim C29-C36 \\sim C29-C36A \\sim C29-C37 \\sim
C29-C37A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C29, C34, C35, C36, C37, C34A, C35A, C36A, C37A, Cl51, O51, O52, O53, O54,
 Cl52, O51A, O52A, O53A, O54A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C34, C35, C36, C37} sigma for 1-2: 0.02, 1-3: 0.04
as
{C34A, C35A, C36A, C37A}
{Cl51, O51, O52, O53, O54} sigma for 1-2: 0.02, 1-3: 0.04
as
{Cl52, O51A, O52A, O53A, O54A}
5. Others
 Sof(Cl52)=Sof(O51A)=Sof(O52A)=Sof(O53A)=Sof(O54A)=1-FVAR(1)
 Sof(Cl51)=Sof(O51)=Sof(O52)=Sof(O53)=Sof(O54)=FVAR(1)
 Sof(C34A)=Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C36A)=Sof(H36D)=
 Sof(H36E)=Sof(H36F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(2)
 Sof(C34)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(2)
6.a Free rotating group:
 O61(H61A,H61B)
6.b Me refined with riding coordinates:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C35A(H35D,H35E,
 H35F), C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), N2(H2A), N3(H3A), N4(H4A), N5(H5), C22(H22), C23(H23),
  C24(H24), N22(H22A), N23(H23A), N24(H24A), N25(H25)
6.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              62442
_shelx_hkl_checksum              80878
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'