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_7716590
_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 H21 Co N6 O, 2(Cl O4), 2.75(H2 O)'
_chemical_formula_sum            'C25 H26.5 Cl2 Co N6 O11.75'
_chemical_formula_weight         728.85
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-06-17
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-18 deposited with the CCDC.	2024-07-10 downloaded from the CCDC.
;
_cell_angle_alpha                99.034(2)
_cell_angle_beta                 105.917(2)
_cell_angle_gamma                107.125(2)
_cell_formula_units_Z            2
_cell_length_a                   9.0704(2)
_cell_length_b                   12.1819(3)
_cell_length_c                   14.3572(3)
_cell_measurement_reflns_used    10795
_cell_measurement_temperature    104(1)
_cell_measurement_theta_max      72.2330
_cell_measurement_theta_min      3.9530
_cell_volume                     1408.29(6)
_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(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.946
_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    -18.00  65.00   0.50    2.05    --   47.23 -57.00 -60.00  166
  2  \w     70.00  96.00   0.50    8.21    --   97.33 -95.00  30.00   52
  3  \w     84.00 109.00   0.50    8.21    --   97.33-111.00   0.00   50
  4  \w     81.00 106.00   0.50    8.21    --   97.33-138.00   1.00   50
  5  \w     74.00 103.00   0.50    8.21    --   97.33-111.00  30.00   58
  6  \w     64.00  89.00   0.50    2.05    --   47.23-138.00   1.00   50
  7  \w     50.00 109.00   0.50    8.21    --   97.33-111.00 -90.00  118
  8  \w     61.00  92.00   0.50    8.21    --   97.33-111.00 -60.00   62
  9  \w     42.00 107.00   0.50    8.21    --   97.33-111.00-180.00  130
 10  \w     30.00 103.00   0.50    8.21    --   97.33 -77.00 -90.00  146
 11  \w     33.00  67.00   0.50    8.21    --   97.33 -61.00-180.00   68
 12  \w     20.00  46.00   0.50    8.21    --   97.33 -45.00-180.00   52
 13  \w     24.00  51.00   0.50    8.21    --   97.33 -45.00 -30.00   54
 14  \w     29.00  64.00   0.50    8.21    --   97.33 -61.00  30.00   70
 15  \w     39.00  64.00   0.50    8.21    --   97.33 -61.00  60.00   50
 16  \w     20.00  45.00   0.50    8.21    --   97.33 -45.00 120.00   50
 17  \w     25.00  61.00   0.50    8.21    --   97.33 -61.00 150.00   72
 18  \w     20.00  50.00   0.50    8.21    --   97.33 -45.00 150.00   60
 19  \w     84.00 109.00   0.50    8.21    --   97.33-111.00 150.00   50
 20  \w     48.00 116.00   0.50    8.21    --   97.33-131.00 176.00  136
 21  \w     37.00  80.00   0.50    2.05    --   47.23-131.00 176.00   86
 22  \w     25.00  64.00   0.50    8.21    --   97.33-111.00 150.00   78
 23  \w     20.00  51.00   0.50    8.21    --   97.33 -45.00  60.00   62
 24  \w     20.00  51.00   0.50    8.21    --   97.33 -45.00  30.00   62
 25  \w     19.00  66.00   0.50    8.21    --   97.33 -95.00  30.00   94
 26  \w     35.00  61.00   0.50    8.21    --   97.33-111.00   0.00   52
 27  \w     24.00  56.00   0.50    8.21    --   97.33-111.00  30.00   64
 28  \w     93.00 126.00   0.50    8.21    --   97.33  61.00  30.00   66
 29  \w    130.00 165.00   0.50    8.21    --   97.33  61.00  30.00   70
 30  \w     88.00 134.00   0.50    8.21    --   97.33 138.00  62.00   92
 31  \w    112.00 146.00   0.50    8.21    --   97.33 178.00 -30.00   68
 32  \w    106.00 132.00   0.50    8.21    --   97.33 131.00-112.00   52
 33  \w    114.00 144.00   0.50    8.21    --   97.33 178.00-180.00   60
 34  \w     62.00  98.00   0.50    8.21    --   97.33 178.00 -30.00   72
 35  \w     62.00  91.00   0.50    8.21    --   97.33 178.00-180.00   58
 36  \w    -26.00  35.00   0.50    2.05    --  -47.23  19.00-180.00  122
 37  \w    -43.00 -18.00   0.50    8.21    --  -90.25  45.00-150.00   50
 38  \w    -50.00 -14.00   0.50    8.21    --  -90.25  45.00 -60.00   72
 39  \w    -39.00 -14.00   0.50    8.21    --  -90.25 111.00 -30.00   50
 40  \w    -82.00 -57.00   0.50    2.05    --  -47.23 138.00  62.00   50
 41  \w    -82.00 -57.00   0.50    8.21    --  -90.25 138.00  62.00   50
 42  \w    -82.00 -51.00   0.50    8.21    --  -90.25 111.00 -30.00   62
 43  \w    -77.00 -52.00   0.50    2.05    --  -47.23 131.00-112.00   50
 44  \w   -169.00 -85.00   0.50    8.21    --  -90.25 -30.00 -60.00  168
 45  \w   -123.00 -21.00   0.50    2.05    --  -47.23 -77.00 -90.00  204
 46  \w    -71.00 -31.00   0.50    2.05    --  -47.23 -57.00-180.00   80
 47  \w   -117.00 -92.00   0.50    2.05    --  -47.23-138.00   1.00   50
 48  \w   -117.00 -84.00   0.50    2.05    --  -47.23-125.00  90.00   66
 49  \w   -123.00 -69.00   0.50    2.05    --  -47.23-131.00 176.00  108
 50  \w   -125.00 -78.00   0.50    8.21    --  -90.25-131.00 176.00   94
 51  \w   -160.00 -70.00   0.50    8.21    --  -90.25 -61.00-120.00  180
 52  \w   -147.00 -71.00   0.50    8.21    --  -90.25 -61.00-180.00  152
;
_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      0.0781789000
_diffrn_orient_matrix_UB_12      -0.0322459000
_diffrn_orient_matrix_UB_13      0.0965158000
_diffrn_orient_matrix_UB_21      0.0047326000
_diffrn_orient_matrix_UB_22      0.1162237000
_diffrn_orient_matrix_UB_23      0.0634155000
_diffrn_orient_matrix_UB_31      -0.1719531000
_diffrn_orient_matrix_UB_32      -0.0649587000
_diffrn_orient_matrix_UB_33      0.0025269000
_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  0.0519
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            17589
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.390
_diffrn_reflns_theta_min         3.931
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.208
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49502
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.719
_exptl_crystal_description       block
_exptl_crystal_F_000             747
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.041
_refine_diff_density_min         -0.937
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         5283
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0474
_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^)+(0.0715P)^2^+1.2817P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1247
_refine_ls_wR_factor_ref         0.1271
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4843
_reflns_number_total             5283
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01579g2.cif
_cod_data_source_block           fi-co-002
_cod_depositor_comments
'Adding full bibliography for 7716587--7716594.cif.'
_cod_original_formula_sum        'C25 H26.50 Cl2 Co N6 O11.75'
_cod_database_code               7716590
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C25 H22 Co N6 O'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All O(H,H,H,H,H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Shared sites
{O2, O2A}
{O4, O4A}
{Cl1, Cl1A}
3. Restrained distances
 O12-H12A = O12-H12B = O11-H11B = O11-H11A
 0.85 with sigma of 0.02
 Cl1-O2 = Cl1-O3 = Cl1-O4 = Cl1-O5 = Cl1A-O3A = Cl1A-O5A
 1.44 with sigma of 0.002
 H12A-H12B
 1.34 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
O2 \\sim O3 \\sim O4 \\sim O5 \\sim O3A \\sim O4A: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002 within 2A
Uanis(O2) = Uanis(O2A)
Uanis(O3) = Uanis(O3A)
Uanis(O4) = Uanis(O4A)
Uanis(O5) = Uanis(O5A)
Uanis(Cl1) = Uanis(Cl1A)
5. Others
 Sof(Cl1A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=1-FVAR(1)
 Sof(Cl1)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(O5)=FVAR(1)
 Fixed Sof: O12(0.75) H12A(0.75) H12B(0.75)
6.a Free rotating group:
 O1(H1)
6.b Ternary CH refined with riding coordinates:
 C4(H4), C5(H5)
6.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)
;
_shelx_res_checksum              78306
_shelx_hkl_checksum              37908
_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 5.853
_oxdiff_exptl_absorpt_empirical_full_min 0.256