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_7710995
_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         'C30 H28 N2 S4'
_chemical_formula_sum            'C30 H28 N2 S4'
_chemical_formula_weight         544.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-07-15
_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                 104.692(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8983(3)
_cell_length_b                   12.7382(3)
_cell_length_c                   18.6419(7)
_cell_measurement_reflns_used    27858
_cell_measurement_temperature    100
_cell_measurement_theta_max      32.8950
_cell_measurement_theta_min      2.2660
_cell_volume                     2733.04(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (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
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.934
_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  69.00   0.50    5.00    --  -20.40  60.00 -90.00  254
  2  \w    -58.00  69.00   0.50    5.00    --  -20.40  60.00-150.00  254
  3  \w    -58.00  69.00   0.50    5.00    --  -20.40  60.00 -30.00  254
  4  \w    -58.00  69.00   0.50    5.00    --  -20.40  60.00 120.00  254
  5  \w   -110.00  17.00   0.50    5.00    --  -20.40 -60.00-180.00  254
  6  \w   -110.00  17.00   0.50    5.00    --  -20.40 -60.00   0.00  254
  7  \w   -110.00  17.00   0.50    5.00    --  -20.40 -60.00 120.00  254
  8  \w   -110.00  17.00   0.50    5.00    --  -20.40 -60.00 -60.00  254
  9  \w   -110.00  17.00   0.50    5.00    --  -20.40 -60.00-150.00  254
 10  \w   -110.00  17.00   0.50    5.00    --  -20.40 -60.00-120.00  254
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC12 \k goniometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_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      -0.0083283000
_diffrn_orient_matrix_UB_12      -0.0219200000
_diffrn_orient_matrix_UB_13      -0.0359326000
_diffrn_orient_matrix_UB_21      0.0316004000
_diffrn_orient_matrix_UB_22      -0.0452875000
_diffrn_orient_matrix_UB_23      0.0156316000
_diffrn_orient_matrix_UB_31      -0.0522645000
_diffrn_orient_matrix_UB_32      -0.0238455000
_diffrn_orient_matrix_UB_33      0.0034020000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  mirror
_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  0.0651
_diffrn_reflns_av_unetI/netI     0.0325
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.934
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            92783
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.305
_diffrn_reflns_theta_min         2.259
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.370
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81332
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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    1.324
_exptl_crystal_description       plate
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     638
_refine_ls_number_reflns         9857
_refine_ls_number_restraints     62
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0530
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0446P)^2^+0.6631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0952
_refine_ls_wR_factor_ref         0.1037
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8119
_reflns_number_total             9857
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01767a2.cif
_cod_data_source_block           Compound_2b
_cod_database_code               7710995
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H28 N2 S4'
_chemical_oxdiff_usercomment     JCS_09
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.947
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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. Restrained distances
 C8A-C13A = C12A-C13A = C24A-C25A = C26A-C27A = C28A-C29A
 1.36 with sigma of 0.01
 C25A-C26A = C27A-C28A = C29A-C24A
 1.36 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C14A) \\sim Ueq, Uanis(C30A) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.01
Uanis(C4A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C12A)
\\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C29A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.005
Uanis(C6A) = Uanis(C10A) = Uanis(C13A) = Uanis(C24A)
4. Others
 Sof(S1A)=Sof(S2A)=Sof(S3A)=Sof(S4A)=Sof(N1A)=Sof(N2A)=Sof(C1A)=Sof(C2A)=
 Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=
 Sof(H10A)=Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=
 Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(C16A)=Sof(C17A)=Sof(C18A)=
 Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=
 Sof(H22A)=Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=
 Sof(H29A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(S1)=Sof(S2)=Sof(S3)=Sof(S4)=Sof(N1)=Sof(N2)=Sof(C1)=Sof(C2)=Sof(H2)=
 Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=
 Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(C12)=
 Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=
 Sof(C16)=Sof(C17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(C21)=
 Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(C28)=Sof(H28)=Sof(C29)=
 Sof(H29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
5.a Me refined with riding coordinates:
 C14A(H14D,H14E,H14F), C30A(H30D,H30E,H30F)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13),
 C18(H18), C19(H19), C21(H21), C22(H22), C25(H25), C26(H26), C28(H28), C29(H29),
  C2A(H2A), C3A(H3A), C5A(H5A), C6A(H6A), C9A(H9A), C10A(H10A), C12A(H12A),
 C13A(H13A), C18A(H18A), C19A(H19A), C21A(H21A), C22A(H22A), C25A(H25A),
 C26A(H26A), C28A(H28A), C29A(H29A)
5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C23(H23A,H23B,H23C), C30(H30A,H30B,
 H30C), C7A(H7AA,H7AB,H7AC), C23A(H23D,H23E,H23F)
;
_shelx_res_checksum              23833
_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 2.104
_oxdiff_exptl_absorpt_empirical_full_min 0.571