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_7716594
_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 F N6, 2(Cl O4), 1.5(H2 O)'
_chemical_formula_sum            'C25 H23 Cl2 Co F N6 O9.5'
_chemical_formula_weight         708.32
_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                105.4160(12)
_cell_angle_beta                 98.6806(12)
_cell_angle_gamma                107.2355(14)
_cell_formula_units_Z            4
_cell_length_a                   12.7950(2)
_cell_length_b                   14.1951(2)
_cell_length_c                   16.8217(2)
_cell_measurement_reflns_used    55905
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      72.1840
_cell_measurement_theta_min      2.8180
_cell_volume                     2724.14(8)
_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(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.966
_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   -126.00 -27.00   0.50    0.34    --  -47.23 -43.00 -84.00  198
  2  \w    -67.00 -38.00   0.50    0.34    --  -66.00 -79.00-148.83   58
  3  \w    -73.00 -47.00   0.50    1.37    --  -74.00 -76.00-119.70   52
  4  \w    -84.00 -57.00   0.50    1.37    --  -82.00 -71.00-144.10   54
  5  \w    -88.00 -59.00   0.50    1.37    --  -86.00 -77.00-105.09   58
  6  \w    -82.00 -56.00   0.50    1.37    --  -82.00 -76.00 -17.58   52
  7  \w    -84.00 -55.00   0.50    1.37    --  -82.00 -77.00  24.79   58
  8  \w    -72.00 -46.00   0.50    1.37    --  -74.00 -78.00  49.85   52
  9  \w    -76.00 -51.00   0.50    1.37    --  -78.00 -77.00 111.42   50
 10  \w    -85.00 -51.00   0.50    1.37    --  -78.00 -76.00  75.82   68
 11  \w    -92.00 -59.00   0.50    1.37    --  -86.00 -77.00  17.22   66
 12  \w    -84.00 -59.00   0.50    1.37    --  -86.00 -76.00 -21.86   50
 13  \w    -93.00 -60.00   0.50    1.37    --  -86.00 -74.00  51.44   66
 14  \w    -85.00 -60.00   0.50    1.37    --  -86.00 -74.00  60.93   50
 15  \w    -99.00 -64.00   0.50    1.37    --  -90.25 -74.00  91.85   70
 16  \w    -90.00 -65.00   0.50    1.37    --  -90.25 -73.00 152.43   50
 17  \w    -95.00 -64.00   0.50    1.37    --  -90.25 -78.00 108.81   62
 18  \w    -90.00 -64.00   0.50    1.37    --  -90.25 -76.00 165.87   52
 19  \w    -92.00 -65.00   0.50    1.37    --  -90.25 -73.00 145.87   54
 20  \w   -103.00 -66.00   0.50    1.37    --  -90.25 -69.00  67.80   74
 21  \w    -96.00 -63.00   0.50    1.37    --  -90.25 -77.00  45.81   66
 22  \w    -93.00 -64.00   0.50    1.37    --  -90.25 -75.00 -55.89   58
 23  \w    -99.00 -65.00   0.50    1.37    --  -90.25 -74.00-136.68   68
 24  \w    -96.00 -64.00   0.50    1.37    --  -90.25 -77.00-150.00   64
 25  \w    -95.00 -63.00   0.50    1.37    --  -90.25 -77.00-120.00   64
 26  \w   -114.00 -74.00   0.50    0.34    --  -47.23-125.00-150.00   80
 27  \w   -129.00 -95.00   0.50    1.37    --  -86.00 -76.00 -21.86   68
 28  \w   -126.00 -28.00   0.50    0.34    --  -47.23 -38.00   0.00  196
 29  \w    -38.00 -13.00   0.50    1.37    --  -90.25  43.00  67.00   50
 30  \w    -47.00  28.00   0.50    0.34    --  -47.23  43.00  67.00  150
 31  \w     -6.00  40.00   0.50    0.34    --   22.00  81.00  95.79   92
 32  \w     49.00  76.00   0.50    0.34    --   47.23  43.00  67.00   54
 33  \w     84.00 124.00   0.50    0.34    --   47.23  43.00  67.00   80
 34  \w     82.00 159.00   0.50    1.37    --   97.33  43.00  67.00  154
 35  \w     62.00  98.00   0.50    0.34    --   62.00  80.00 153.09   72
 36  \w     46.00  71.00   0.50    1.37    --   74.00  79.00  97.63   50
 37  \w     30.00  56.00   0.50    0.34    --   58.00  79.00  11.89   52
 38  \w     39.00  64.00   0.50    0.34    --   66.00  78.00 -17.87   50
 39  \w     38.00  67.00   0.50    0.34    --   66.00  79.00 -75.59   58
 40  \w     42.00  69.00   0.50    0.34    --   70.00  80.00 -57.73   54
 41  \w     27.00  52.00   0.50    0.34    --   54.00  78.00 -95.62   50
 42  \w     46.00  72.00   0.50    1.37    --   74.00  80.00-149.94   52
 43  \w     78.00 103.00   0.50    0.34    --   70.00  79.00-174.10   50
 44  \w     33.00  71.00   0.50    0.34    --   58.00  78.00-160.20   76
 45  \w     42.00  67.00   0.50    0.34    --   70.00  79.00-174.10   50
 46  \w     17.00  42.00   0.50    0.34    --   50.00  90.00 -73.40   50
 47  \w     16.00  41.00   0.50    0.34    --   50.00  92.00 -42.24   50
 48  \w     28.00  57.00   0.50    0.34    --   54.00  77.00 -17.68   58
 49  \w     43.00  69.00   0.50    0.34    --   70.00  80.00  10.61   52
 50  \w     34.00  65.00   0.50    0.34    --   62.00  80.00  84.06   62
 51  \w     39.00  65.00   0.50    0.34    --   66.00  78.00  47.03   52
 52  \w     13.00  39.00   0.50    0.34    --   46.00  90.00  -7.27   52
 53  \w     16.00  41.00   0.50    0.34    --   50.00  92.00  53.54   50
 54  \w     17.00  42.00   0.50    0.34    --   50.00  90.00 111.27   50
 55  \w     36.00  62.00   0.50    0.34    --   62.00  77.00 147.62   52
 56  \w     35.00  61.00   0.50    0.34    --   62.00  80.00 153.09   52
 57  \w     17.00  42.00   0.50    0.34    --   50.00  90.00 156.82   50
 58  \w     16.00  41.00   0.50    0.34    --   50.00  92.00 172.05   50
 59  \w      4.00  29.00   0.50    0.34    --   38.00  95.00 145.48   50
 60  \w    -66.00 -36.00   0.50    0.34    --   14.00 170.00  23.21   60
 61  \w    -98.00 -56.00   0.50    0.34    --  -38.00 141.00 -10.30   84
 62  \w    -70.00 -44.00   0.50    1.37    --  -90.25 111.00 -90.00   52
 63  \w   -147.00-121.00   0.50    1.37    --  -90.25 -43.00 -84.00   52
 64  \w   -141.00-101.00   0.50    1.37    --  -90.25 -77.00-120.00   80
 65  \w   -147.00-102.00   0.50    1.37    --  -90.25 -77.00-150.00   90
 66  \w   -150.00 -65.00   0.50    1.37    --  -90.25 -76.00 -65.69  170
 67  \w   -131.00-102.00   0.50    1.37    --  -90.25 -77.00  45.81   58
 68  \w   -129.00-100.00   0.50    1.37    --  -90.25 -78.00 108.81   58
 69  \w   -131.00-105.00   0.50    1.37    --  -90.25 -73.00 152.43   52
 70  \w   -134.00-108.00   0.50    1.37    --  -90.25 -73.00 145.87   52
 71  \w   -139.00-114.00   0.50    1.37    --  -90.25 -74.00  91.85   50
 72  \w   -156.00-101.00   0.50    1.37    --  -86.00 -74.00  60.93  110
 73  \w   -152.00-112.00   0.50    1.37    --  -90.25 -69.00  67.80   80
 74  \w   -146.00 -65.00   0.50    1.37    --  -90.25 -72.00   0.27  162
 75  \w   -159.00-133.00   0.50    1.37    --  -90.25 -77.00  45.81   52
 76  \w   -163.00 -64.00   0.50    1.37    --  -90.25 -75.00  -9.73  198
 77  \w   -156.00 -63.00   0.50    1.37    --  -90.25 -77.00 -80.46  186
 78  \w   -148.00 -66.00   0.50    1.37    --  -90.25 -70.00-174.30  164
 79  \w   -160.00 -63.00   0.50    1.37    --  -90.25 -77.00-180.00  194
 80  \w   -163.00-118.00   0.50    1.37    --  -90.25 -75.00 -55.89   90
 81  \w   -158.00 -63.00   0.50    1.37    --  -90.25 -77.00  30.00  190
 82  \w   -164.00-108.00   0.50    1.37    --  -90.25 -74.00-136.68  112
 83  \w   -164.00 -63.00   0.50    1.37    --  -90.25 -77.00 -30.65  202
 84  \w    -61.00 -17.00   0.50    1.37    --  -90.25  61.00 150.00   88
 85  \w    -66.00 -15.00   0.50    1.37    --  -90.25 111.00 150.00  102
 86  \w      2.00  27.00   0.50    0.34    --   38.00  97.00-111.31   50
 87  \w    -29.00  32.00   0.50    0.34    --   47.23 -43.00 -84.00  122
 88  \w     19.00  45.00   0.50    1.37    --   97.33 -43.00 -84.00   52
 89  \w     22.00 101.00   0.50    1.37    --   97.33 -77.00-120.00  158
 90  \w     84.00 109.00   0.50    1.37    --   97.33-111.00 -60.00   50
 91  \w     54.00  88.00   0.50    0.34    --   47.23-125.00 -30.00   68
 92  \w     38.00  70.00   0.50    1.37    --   97.33 -61.00   0.00   64
 93  \w     81.00 109.00   0.50    1.37    --   97.33-111.00  60.00   56
 94  \w     58.00  92.00   0.50    1.37    --   97.33 -95.00 150.00   68
 95  \w     71.00 108.00   0.50    1.37    --   97.33-111.00 150.00   74
 96  \w     38.00  96.00   0.50    1.37    --   97.33 -95.00  90.00  116
 97  \w     50.00  76.00   0.50    1.37    --   97.33-111.00  60.00   52
 98  \w     20.00  46.00   0.50    1.37    --   97.33 -95.00 150.00   52
 99  \w     26.00  65.00   0.50    1.37    --   97.33-111.00 150.00   78
100  \w     29.00 109.00   0.50    1.37    --   97.33-111.00  90.00  160
101  \w     18.00  94.00   0.50    1.37    --   97.33 -95.00   0.00  152
102  \w     33.00  99.00   0.50    1.37    --   97.33-111.00   0.00  132
103  \w     25.00 106.00   0.50    1.37    --   97.33 -95.00-120.00  162
104  \w     42.00 101.00   0.50    1.37    --   97.33 -95.00-150.00  118
105  \w     28.00 105.00   0.50    1.37    --   97.33-111.00-150.00  154
106  \w     27.00  62.00   0.50    1.37    --   97.33-111.00 -60.00   70
107  \w   -163.00 -66.00   0.50    1.37    --  -90.25 -74.00-113.06  194
108  \w   -161.00 -65.00   0.50    1.37    --  -90.25 -76.00 128.10  192
109  \w   -163.00 -63.00   0.50    1.37    --  -90.25 -78.00 145.72  200
;
_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      -0.0648664000
_diffrn_orient_matrix_UB_12      -0.0602752000
_diffrn_orient_matrix_UB_13      0.0517825000
_diffrn_orient_matrix_UB_21      -0.0879575000
_diffrn_orient_matrix_UB_22      0.0534530000
_diffrn_orient_matrix_UB_23      -0.0076936000
_diffrn_orient_matrix_UB_31      -0.0707299000
_diffrn_orient_matrix_UB_32      -0.0893744000
_diffrn_orient_matrix_UB_33      -0.0829651000
_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  0.0354
_diffrn_reflns_av_unetI/netI     0.0180
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            86489
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.449
_diffrn_reflns_theta_min         2.814
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.425
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65891
_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    1.727
_exptl_crystal_description       block
_exptl_crystal_F_000             1444
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.096
_refine_diff_density_min         -0.690
_refine_diff_density_rms         0.061
_refine_ls_extinction_coef       0.00022(4)
_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   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     840
_refine_ls_number_reflns         10434
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0424P)^2^+3.6431P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0869
_refine_ls_wR_factor_ref         0.0876
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10033
_reflns_number_total             10434
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01579g2.cif
_cod_data_source_block           fi-017-f
_cod_depositor_comments
'Adding full bibliography for 7716587--7716594.cif.'
_cod_original_cell_volume        2724.15(7)
_cod_original_formula_sum        'C25 H23 Cl2 Co F N6 O9.50'
_cod_database_code               7716594
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C25 H20 Co N6 F Cl O4'
_shelx_estimated_absorpt_t_max   0.524
_shelx_estimated_absorpt_t_min   0.258
_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-O13 = Cl1-O13A = Cl1-O14 = Cl1-O14A = Cl1-O18 = Cl1-O18A
 1.44 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
O13 \\sim O14 \\sim O18 \\sim O13A \\sim O14A \\sim O18A: within 2A with sigma
of 0.002 and sigma for terminal atoms of 0.004 within 2A
4. Others
 Sof(O13A)=Sof(O14A)=Sof(O18A)=1-FVAR(1)
 Sof(O13)=Sof(O14)=Sof(O18)=FVAR(1)
5.a Free rotating group:
 O15(H15A,H15B), O16(H16A,H16B), O17(H17A,H17B)
5.b Ternary CH refined with riding coordinates:
 C6(H6), C1(H1), C1R(H1R), C2(H2)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16),
 C17(H17), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1G(H1G), C1H(H1H),
  C1I(H1I), C1J(H1J), C1P(H1P), C1T(H1T), C1V(H1V), C1W(H1W), C1Y(H1Y),
 C1Z(H1Z), C20(H20), C23(H23), C24(H24), C25(H25), C27(H27), C28(H28), C29(H29),
  C2A(H2A), C2B(H2B), C2C(H2C), C2D(H2D), C2E(H2E)
;
_shelx_res_checksum              17643
_shelx_hkl_checksum              93183
_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 1.380
_oxdiff_exptl_absorpt_empirical_full_min 0.718