Co(III) complexes of the pentadentate NHC ligand PY4Im: carbene-induced <i>trans</i> influences and the non-disappearing <sup>13</sup>C NMR peak.
Ismael, Fouad; Fleming, Cassandra L.; Christopher, Timothy D.; Söhnel, Tilo; Zhou, Yuchen; Krenske, Elizabeth H.; Gahan, Lawrence R.; Blackman, Allan G.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 12688–12697; doi:10.1039/d4dt01579g

data_7716593
_publ_section_title
;
 Co(III) complexes of the pentadentate NHC ligand PY4Im: carbene-induced
 <i>trans</i> influences and the non-disappearing <sup>13</sup>C NMR peak.
;
_journal_issue                   30
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12688
_journal_page_last               12697
_journal_paper_doi               10.1039/d4dt01579g
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C25 H20 Co N15, C2 H6 O S'
_chemical_formula_sum            'C27 H26 Co N15 O S'
_chemical_formula_weight         667.62
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-07-05
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-06 deposited with the CCDC.	2024-07-10 downloaded from the CCDC.
;
_cell_angle_alpha                89.394(2)
_cell_angle_beta                 66.838(3)
_cell_angle_gamma                71.033(3)
_cell_formula_units_Z            4
_cell_length_a                   13.4885(5)
_cell_length_b                   15.3951(5)
_cell_length_c                   16.3964(4)
_cell_measurement_reflns_used    14696
_cell_measurement_temperature    120.0(4)
_cell_measurement_theta_max      72.1790
_cell_measurement_theta_min      2.9730
_cell_volume                     2933.37(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.962
_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    -43.00  -3.00   0.50    2.49    --  -47.23 112.00-115.00   80
  2  \w    -36.00 -11.00   0.50    9.95    --  -90.25 111.00-180.00   50
  3  \w    -49.00 -12.00   0.50    9.95    --  -90.25 111.00-150.00   74
  4  \w    -66.00  27.00   0.50    2.49    --  -47.23  57.00-120.00  186
  5  \w    -50.00 -16.00   0.50    9.95    --  -90.25  45.00-180.00   68
  6  \w    -49.00 -13.00   0.50    9.95    --  -90.25  45.00-150.00   72
  7  \w    -71.00 -46.00   0.50    9.95    --  -90.25 112.00-115.00   50
  8  \w    -78.00 -52.00   0.50    9.95    --  -90.25 111.00-180.00   52
  9  \w    -87.00 -39.00   0.50    9.95    --  -90.25 178.00   0.00   96
 10  \w    -51.00 -16.00   0.50    9.95    --  -90.25  45.00 150.00   70
 11  \w   -120.00 -81.00   0.50    9.95    --  -90.25-112.00 151.00   78
 12  \w   -120.00 -92.00   0.50    2.49    --  -47.23-125.00 -60.00   56
 13  \w   -116.00 -74.00   0.50    2.49    --  -47.23 -57.00-150.00   84
 14  \w   -107.00 -26.00   0.50    2.49    --  -47.23 -57.00-120.00  162
 15  \w   -107.00 -74.00   0.50    9.95    --  -90.25 -77.00-180.00   66
 16  \w   -124.00 -88.00   0.50    2.49    --  -47.23-125.00-150.00   72
 17  \w   -158.00-109.00   0.50    9.95    --  -90.25 -77.00-180.00   98
 18  \w   -167.00 -69.00   0.50    9.95    --  -90.25 -45.00-150.00  196
 19  \w     25.00  90.00   0.50    2.49    --   47.23-112.00 151.00  130
 20  \w     61.00 109.00   0.50    9.95    --   97.33-112.00 151.00   96
 21  \w     66.00  96.00   0.50    9.95    --   97.33-111.00 120.00   60
 22  \w     66.00 109.00   0.50    9.95    --   97.33-111.00  60.00   86
 23  \w     72.00  97.00   0.50    9.95    --   97.33 -95.00 -30.00   50
 24  \w     71.00 107.00   0.50    9.95    --   97.33-111.00 -60.00   72
 25  \w     56.00 109.00   0.50    9.95    --   97.33-111.00-120.00  106
 26  \w     63.00 102.00   0.50    9.95    --   97.33-111.00-180.00   78
 27  \w     33.00  59.00   0.50    9.95    --   97.33 -61.00-180.00   52
 28  \w     27.00  58.00   0.50    9.95    --   97.33-111.00-180.00   62
 29  \w     23.00  48.00   0.50    9.95    --   97.33 -45.00-120.00   50
 30  \w     26.00  78.00   0.50    9.95    --   97.33 -77.00 -60.00  104
 31  \w     29.00 100.00   0.50    9.95    --   97.33-111.00 -90.00  142
 32  \w     32.00  63.00   0.50    9.95    --   97.33 -61.00   0.00   62
 33  \w     30.00  62.00   0.50    9.95    --   97.33-111.00  60.00   64
 34  \w     46.00 100.00   0.50    9.95    --   97.33 -77.00  90.00  108
 35  \w     20.00  49.00   0.50    9.95    --   97.33 -45.00  60.00   58
 36  \w     20.00  46.00   0.50    9.95    --   97.33 -45.00   0.00   52
 37  \w     26.00  68.00   0.50    9.95    --   97.33 -61.00 -30.00   84
 38  \w     25.00 105.00   0.50    9.95    --   97.33 -95.00 -60.00  160
 39  \w     23.00  49.00   0.50    9.95    --   97.33-111.00 -60.00   52
 40  \w     18.00  46.00   0.50    9.95    --   97.33 -95.00 -30.00   56
 41  \w     20.00  46.00   0.50    9.95    --   97.33 -45.00 -30.00   52
 42  \w     20.00  45.00   0.50    9.95    --   97.33 -45.00  30.00   50
 43  \w     27.00  62.00   0.50    9.95    --   97.33-111.00 120.00   70
 44  \w    149.00 174.00   0.50    9.95    --   97.33  45.00 -30.00   50
 45  \w    104.00 140.00   0.50    9.95    --   97.33 112.00-115.00   72
 46  \w    104.00 177.00   0.50    9.95    --   97.33 111.00-180.00  146
 47  \w    106.00 138.00   0.50    9.95    --   97.33  45.00 -30.00   64
 48  \w    105.00 146.00   0.50    9.95    --   97.33 178.00 150.00   82
 49  \w     63.00  89.00   0.50    9.95    --   97.33 178.00 150.00   52
 50  \w     24.00 102.00   0.50    2.49    --   47.23  77.00 150.00  156
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0756083000
_diffrn_orient_matrix_UB_12      -0.0502245000
_diffrn_orient_matrix_UB_13      -0.0961908000
_diffrn_orient_matrix_UB_21      -0.0915577000
_diffrn_orient_matrix_UB_22      0.0595181000
_diffrn_orient_matrix_UB_23      -0.0310579000
_diffrn_orient_matrix_UB_31      0.0589327000
_diffrn_orient_matrix_UB_32      0.0730680000
_diffrn_orient_matrix_UB_33      -0.0204918000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0756
_diffrn_reflns_av_unetI/netI     0.0708
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            40399
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.959
_diffrn_reflns_theta_min         2.958
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.688
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.512
_exptl_crystal_description       block
_exptl_crystal_F_000             1376
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.908
_refine_diff_density_min         -1.054
_refine_diff_density_rms         0.095
_refine_ls_extinction_coef       0.00062(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     824
_refine_ls_number_reflns         11274
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0888
_refine_ls_R_factor_gt           0.0712
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1037P)^2^+3.7869P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1851
_refine_ls_wR_factor_ref         0.1972
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8868
_reflns_number_total             11274
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01579g2.cif
_cod_data_source_block           fi-020-dmso
_cod_depositor_comments
'Adding full bibliography for 7716587--7716594.cif.'
_cod_original_cell_volume        2933.38(18)
_cod_database_code               7716593
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C25 H20 Co N9'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C70-C71 = C70'-C71'
 2.62 with sigma of 0.02
 O1-C70 = O1-C71 = O1'-C70' = O1'-C71'
 2.64 with sigma of 0.001
 C30-C46 \\sim C30-C46A
 with sigma of 0.01
 C30-C41 \\sim C30-C41A
 with sigma of 0.01
 S1-C70 \\sim S1'-C70' \\sim S1-C71 \\sim S1'-C71'
 with sigma of 0.001
 S1-O1 \\sim S1'-O1'
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
N83 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50: within 2A with sigma of
0.002 and sigma for terminal atoms of 0.01 within 2A
N41 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45: within 2A with sigma of
0.002 and sigma for terminal atoms of 0.01 within 2A
Uanis(N83) = Uanis(N83A)
Uanis(C46) = Uanis(C46A)
Uanis(C47) = Uanis(C47A)
Uanis(C48) = Uanis(C48A)
Uanis(C49) = Uanis(C49A)
Uanis(C50) = Uanis(C50A)
Uanis(N41) = Uanis(N41A)
Uanis(C41) = Uanis(C41A)
Uanis(C42) = Uanis(C42A)
Uanis(C43) = Uanis(C43A)
Uanis(C44) = Uanis(C44A)
Uanis(C45) = Uanis(C45A)
Uanis(C72) = Uanis(C72')
Uanis(O2) = Uanis(O2')
Uanis(S2) = Uanis(S2')
Uanis(C73) = Uanis(C73')
Uanis(S1) = Uanis(S1')
Uanis(O1) = Uanis(O1')
Uanis(C70) = Uanis(C70') = Uanis(C71) = Uanis(C71')
4. Others
 Sof(C46A)=Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(H49A)=
 Sof(C50A)=Sof(H50A)=Sof(N83A)=Sof(S2')=Sof(O2')=Sof(C72')=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=Sof(C73')=Sof(H73D)=Sof(H73E)=Sof(H73F)=1-FVAR(1)
 Sof(C46)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49)=Sof(C50)=
 Sof(H50)=Sof(N83)=Sof(S2)=Sof(O2)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=FVAR(1)
 Sof(O1')=Sof(C71')=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C70')=Sof(H70D)=
 Sof(H70E)=Sof(H70F)=Sof(S1')=1-FVAR(2)
 Sof(S1)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(H71C)=Sof(O1)=FVAR(2)
 Fixed Sof: H30(0.5) H30A(0.5) C41(0.5) C42(0.5) H42(0.5) C43(0.5) H43(0.5)
 C44(0.5) H44(0.5) C45(0.5) H45(0.5) N41(0.5) C41A(0.5) C42A(0.5) H42A(0.5)
 C43A(0.5) H43A(0.5) C44A(0.5) H44A(0.5) C45A(0.5) H45A(0.5) N41A(0.5)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5), C29(H29), C30(H30), C30(H30A)
5.b Me refined with riding coordinates:
 C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C71'(H71D,H71E,H71F), C70'(H70D,
 H70E,H70F)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23),
  C24(H24), C25(H25), C27(H27), C28(H28), C32(H32), C33(H33), C34(H34),
 C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43), C44(H44),
  C45(H45), C42A(H42A), C43A(H43A), C44A(H44A), C45A(H45A), C47(H47), C48(H48),
 C49(H49), C50(H50), C47A(H47A), C48A(H48A), C49A(H49A), C50A(H50A)
5.d Fitted hexagon refined as free rotating group:
 C41(C42,C43,C44,C45,N41), C41A(C42A,C43A,C44A,C45A,N41A), C46(C47,C48,C49,C50,
 N83), C46A(C47A,C48A,C49A,C50A,N83A)
5.e Idealised Me refined as rotating group:
 C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C72'(H72D,H72E,H72F), C73'(H73D,
 H73E,H73F)
;
_shelx_res_checksum              75442
_shelx_hkl_checksum              94253
_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 3.561
_oxdiff_exptl_absorpt_empirical_full_min 0.469