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_7716592
_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
'C26 H20 Co N7 S, 3(Cl0.5 O2), 0.5(C N S), 1.834(H2 O)'
_chemical_formula_sum            'C26.5 H23.67 Cl1.5 Co N7.5 O7.83 S1.5'
_chemical_formula_weight         732.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_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                90
_cell_angle_beta                 104.524(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.4803(2)
_cell_length_b                   24.2535(4)
_cell_length_c                   19.8778(3)
_cell_measurement_reflns_used    19200
_cell_measurement_temperature    104.0(9)
_cell_measurement_theta_max      72.0790
_cell_measurement_theta_min      4.0700
_cell_volume                     5824.55(17)
_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      104.0(9)
_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 0.998
_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    -42.00  33.00   0.50    0.84    --  -46.98  38.00   0.00  150
  2  \w     -5.00  33.00   0.50    0.84    --  -46.98  38.00 -90.00   76
  3  \w    -41.00 -16.00   0.50    0.84    --  -46.98  38.00 -90.00   50
  4  \w    -50.00 -17.00   0.50    3.38    --  -90.25  45.00 -90.00   66
  5  \w    -51.00 -26.00   0.50    3.38    --  -90.25  45.00-150.00   50
  6  \w    -43.00 -12.00   0.50    3.38    --  -90.25  45.00-180.00   62
  7  \w    -70.00 -17.00   0.50    3.38    --  -90.25  61.00 -90.00  106
  8  \w    -66.00 -23.00   0.50    0.84    --  -46.98  88.00 -16.00   86
  9  \w    -51.00 -26.00   0.50    3.38    --  -90.25  45.00  60.00   50
 10  \w    -83.00 -48.00   0.50    3.38    --  -90.25 111.00 -30.00   70
 11  \w   -122.00 -70.00   0.50    3.38    --  -90.25  88.00 -16.00  104
 12  \w   -111.00 -85.00   0.50    3.38    --  -90.25 -30.00-120.00   52
 13  \w   -125.00-100.00   0.50    0.84    --  -46.98 -88.00-133.00   50
 14  \w    -14.00  40.00   0.50    0.84    --   46.98 -88.00-133.00  108
 15  \w     73.00 101.00   0.50    3.38    --   97.33 -88.00-133.00   56
 16  \w     32.00  58.00   0.50    3.38    --   97.33 -61.00 -90.00   52
 17  \w     29.00  63.00   0.50    3.38    --   97.33 -61.00 -60.00   68
 18  \w     36.00 104.00   0.50    3.38    --   97.33 -77.00-120.00  136
 19  \w     22.00  50.00   0.50    3.38    --   97.33 -45.00 -60.00   56
 20  \w     20.00  51.00   0.50    3.38    --   97.33 -45.00 -90.00   62
 21  \w     29.00  56.00   0.50    3.38    --   97.33 -61.00 -30.00   54
 22  \w     20.00  47.00   0.50    3.38    --   97.33 -45.00 -30.00   54
 23  \w     26.00  71.00   0.50    3.38    --   97.33 -61.00  60.00   90
 24  \w     29.00  62.00   0.50    3.38    --   97.33 -61.00 120.00   66
 25  \w     27.00  53.00   0.50    3.38    --   97.33 -61.00 150.00   52
 26  \w     30.00  62.00   0.50    3.38    --   97.33 -61.00  90.00   64
 27  \w     23.00 104.00   0.50    3.38    --   97.33 -77.00  60.00  162
 28  \w    102.00 176.00   0.50    3.38    --   97.33  88.00 -16.00  148
 29  \w    110.00 136.00   0.50    3.38    --   97.33 111.00  30.00   52
 30  \w    -15.00  40.00   0.50    0.84    --   46.98 -38.00 -30.00  110
 31  \w   -124.00 -77.00   0.50    0.84    --  -46.98-125.00  90.00   94
 32  \w   -123.00 -78.00   0.50    0.84    --  -46.98-125.00 -60.00   90
 33  \w   -148.00-123.00   0.50    3.38    --  -90.25 -88.00-133.00   50
 34  \w   -168.00-143.00   0.50    3.38    --  -90.25 -30.00-120.00   50
;
_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      -0.0880000000
_diffrn_orient_matrix_UB_12      0.0148812000
_diffrn_orient_matrix_UB_13      -0.0669527000
_diffrn_orient_matrix_UB_21      0.0212369000
_diffrn_orient_matrix_UB_22      -0.0553432000
_diffrn_orient_matrix_UB_23      -0.0325813000
_diffrn_orient_matrix_UB_31      -0.0897724000
_diffrn_orient_matrix_UB_32      -0.0274265000
_diffrn_orient_matrix_UB_33      0.0294095000
_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  0.0417
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            24073
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.725
_diffrn_reflns_theta_min         3.645
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.457
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65298
_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_density_diffrn    1.671
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2995
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.711
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     440
_refine_ls_number_reflns         5279
_refine_ls_number_restraints     81
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0435P)^2^+16.3009P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1003
_refine_ls_wR_factor_ref         0.1014
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5071
_reflns_number_total             5279
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01579g2.cif
_cod_data_source_block           fi-008_pl_pl
_cod_depositor_comments
'Adding full bibliography for 7716587--7716594.cif.'
_cod_original_formula_sum        'C26.50 H23.67 Cl1.50 Co N7.50 O7.83 S1.50'
_cod_database_code               7716592
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C26 H20 Co N6 S N'
_shelx_estimated_absorpt_t_max   0.468
_shelx_estimated_absorpt_t_min   0.347
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 Cl1-O3 \\sim Cl1-O4 \\sim Cl1-O5 \\sim Cl1-O6 \\sim Cl1A-O3A \\sim Cl1A-O4A
\\sim Cl1-O5A \\sim Cl1-O6A
 with sigma of 0.02
 O3-O4 \\sim O3-O5 \\sim O3-O6 \\sim O4-O5 \\sim O4-O6 \\sim O5-O6 \\sim
O3A-O4A \\sim O3A-O5A \\sim O3A-O6A ~
 O4A-O5A \\sim O4A-O6A \\sim O5A-O6A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O3 \\sim O4 \\sim O5 \\sim O6: within 2A with sigma of 0.006 and sigma for
terminal atoms of 0.003 within 2A
Uanis(O3) = Uanis(O3A)
Uanis(O4) = Uanis(O4A)
Uanis(O5) = Uanis(O5A)
Uanis(O6) = Uanis(O6A)
Uanis(Cl1) = Uanis(Cl1A)
4. Others
 Sof(Cl1A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=1-FVAR(1)
 Sof(Cl1)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=FVAR(1)
 Sof(O11)=Sof(H11A)=Sof(H11B)=FVAR(2)
5.a Free rotating group:
 O10(H10A,H10B), O11(H11A,H11B)
5.b Ternary CH refined with riding coordinates:
 C6(H6), C10(H10)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C23(H23), C24(H24), C25(H25),
  C26(H26)
;
_shelx_res_checksum              85361
_shelx_hkl_checksum              27015
_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 1.608
_oxdiff_exptl_absorpt_empirical_full_min 0.697