Diaryl dithiocarbamates: synthesis, oxidation to thiuram disulfides, Co(iii) complexes [Co(S2CNAr2)3] and their use as single source precursors to CoS2
Sarker, Jagodish C.; Nash, Rosie; Boonrungsiman, Suwimon; Pugh, David; Hogarth, Graeme; Dalton Transactions  (2022) –; doi:10.1039/D2DT01767A

data_7710992
_publ_section_title
;
 Diaryl dithiocarbamates: synthesis, oxidation to thiuram disulfides,
 Co(iii) complexes [Co(S2CNAr2)3] and their use as single source
 precursors to CoS2
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01767A
_journal_year                    2022
_chemical_formula_moiety         'C42 H36 Co1 N3 O3 S6'
_chemical_formula_sum            'C42 H36 Co N3 O3 S6'
_chemical_formula_weight         882.03
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-11-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2022-05-27 deposited with the CCDC.	2022-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   13.9005(7)
_cell_length_b                   13.9005(7)
_cell_length_c                   37.791(2)
_cell_measurement_reflns_used    3651
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.2130
_cell_measurement_theta_min      2.7340
_cell_volume                     6323.8(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.79a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.79a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.79a (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)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000'
_diffrn_measured_fraction_theta_full 0.998
_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    -79.00  -7.00   0.50   50.00    --   -9.10 -60.00 150.00  144
  2  \w    -43.00  79.00   0.50   50.00    --   -9.10  57.00 120.00  244
  3  \w    -27.00   0.00   0.50   50.00    --   -9.10 -60.00 -30.00   54
  4  \w     55.00  80.00   0.50   50.00    --   -9.10  60.00  30.00   50
  5  \w    -18.00  20.00   0.50   50.00    --   -9.10 -57.00 150.00   76
  6  \w    -98.00  24.00   0.50   50.00    --   -9.10 -60.00 -60.00  244
  7  \w    -98.00  52.00   0.50   50.00    --   -9.10 -19.00 -30.00  300
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC12 \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with VHF Varimax confocal mirrors and an AFC12 goniometer and HyPix 6000 detector'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0173121000
_diffrn_orient_matrix_UB_12      0.0384230000
_diffrn_orient_matrix_UB_13      -0.0046673000
_diffrn_orient_matrix_UB_21      -0.0221796000
_diffrn_orient_matrix_UB_22      -0.0045908000
_diffrn_orient_matrix_UB_23      0.0172274000
_diffrn_orient_matrix_UB_31      0.0517685000
_diffrn_orient_matrix_UB_32      0.0443827000
_diffrn_orient_matrix_UB_33      0.0058395000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0959
_diffrn_reflns_av_unetI/netI     0.0542
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            29688
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.486
_diffrn_reflns_theta_min         2.741
_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    0.746
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70880
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.79a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       'brown, opaque blade'
_exptl_crystal_F_000             2736
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.769
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3225
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1003
_refine_ls_R_factor_gt           0.0596
_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^)+(0.0813P)^2^+21.1956P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1474
_refine_ls_wR_factor_ref         0.1671
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2145
_reflns_number_total             3225
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01767a2.cif
_cod_data_source_block           Compound_3e
_cod_original_cell_volume        6323.8(7)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7710992
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C42 H39 N3 O3 CoS6'
_chemical_oxdiff_usercomment     JCS_117
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O1B) \\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.01
Uanis(O1A) = Uanis(O1B)
3. Others
 Sof(O1B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=
 Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=1-FVAR(1)
 Sof(O1A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C5A(H5A), C7A(H7A), C3B(H3B), C4B(H4B), C5B(H5B),
 C7B(H7B), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14)
4.b Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C8B(H8BA,H8BB,H8BC)
;
_shelx_res_checksum              41852
_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 2.403
_oxdiff_exptl_absorpt_empirical_full_min 0.354