Square-planar imido complexes of cobalt: synthesis, reactivity and computational study.
Reyna, Jackson A.; Krishnan, V. Mahesh; Silva Villatoro, Roberto; Arman, Hadi D.; Stoian, Sebastian A.; Tonzetich, Zachary J.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 12128–12137; doi:10.1039/d4dt01483a

data_7716571
_publ_section_title
;
 Square-planar imido complexes of cobalt: synthesis, reactivity and
 computational study.
;
_journal_issue                   29
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12128
_journal_page_last               12137
_journal_paper_doi               10.1039/d4dt01483a
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C28 H47 Co N2 P2'
_chemical_formula_sum            'C28 H47 Co N2 P2'
_chemical_formula_weight         532.54
_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     dual
_audit_creation_date             2022-04-02
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-02-23 deposited with the CCDC.	2024-06-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8666(12)
_cell_length_b                   13.3021(8)
_cell_length_c                   14.6700(13)
_cell_measurement_reflns_used    5112
_cell_measurement_temperature    100.01(16)
_cell_measurement_theta_max      72.4220
_cell_measurement_theta_min      4.4820
_cell_volume                     2859.7(4)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(16)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.990
_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    -25.00  70.00   0.50   17.45    --   46.62 -77.00-105.00  190
  2  \w     34.00 101.00   0.50   69.81    --  106.69 -77.00-105.00  134
  3  \w     34.00  71.00   0.50   69.81    --  106.69 -61.00 -60.00   74
  4  \w     34.00  71.00   0.50   69.81    --  106.69 -61.00 -90.00   74
  5  \w     34.00  71.00   0.50   69.81    --  106.69 -61.00 -30.00   74
  6  \w     34.00  71.00   0.50   69.81    --  106.69 -61.00  30.00   74
  7  \w     34.00  71.00   0.50   69.81    --  106.69 -61.00  60.00   74
  8  \w     34.00  71.00   0.50   69.81    --  106.69 -61.00  90.00   74
  9  \w     83.00 178.00   0.50   69.81    --  106.69  77.00  20.00  190
 10  \w    101.00 178.00   0.50   69.81    --  106.69  77.00  60.00  154
 11  \w    101.00 178.00   0.50   69.81    --  106.69  77.00 120.00  154
 12  \w     34.00 111.00   0.50   69.81    --  106.69-125.00-120.00  154
 13  \w     23.00 120.00   0.50   17.45    --   46.62  77.00  20.00  194
 14  \w    -51.00 -16.00   0.50   69.81    --  -88.50  45.00-150.00   70
 15  \w    -70.00  26.00   0.50   17.45    --  -46.62  77.00  20.00  192
 16  \w    -51.00 -16.00   0.50   69.81    --  -88.50  45.00  30.00   70
 17  \w   -101.00 -15.00   0.50   69.81    --  -88.50  77.00  20.00  172
 18  \w   -120.00 -32.00   0.50   17.45    --  -46.62 -37.00 120.00  176
 19  \w   -119.00 -87.00   0.50   17.45    --  -46.62-125.00  60.00   64
 20  \w   -119.00 -23.00   0.50   17.45    --  -46.62 -77.00-105.00  192
 21  \w   -160.00 -65.00   0.50   69.81    --  -88.50 -77.00-105.00  190
 22  \w   -160.00 -91.00   0.50   69.81    --  -88.50 -61.00 -30.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0542707000
_diffrn_orient_matrix_UB_12      -0.0721603000
_diffrn_orient_matrix_UB_13      -0.0389713000
_diffrn_orient_matrix_UB_21      -0.0229136000
_diffrn_orient_matrix_UB_22      0.0654147000
_diffrn_orient_matrix_UB_23      -0.0930977000
_diffrn_orient_matrix_UB_31      0.0870174000
_diffrn_orient_matrix_UB_32      0.0627604000
_diffrn_orient_matrix_UB_33      0.0521885000
_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  0.0969
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12532
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.996
_diffrn_reflns_theta_min         4.489
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.882
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.825
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       needle
_exptl_crystal_F_000             1144
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.772
_refine_diff_density_min         -0.540
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         2698
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0909
_refine_ls_R_factor_gt           0.0859
_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^)+(0.0100P)^2^+24.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1546
_refine_ls_wR_factor_ref         0.1566
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2383
_reflns_number_total             2698
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01483a2.cif
_cod_data_source_block           hpd520
_cod_depositor_comments
'Adding full bibliography for 7716570--7716574.cif.'
_cod_database_code               7716571
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Co P N O H C'
_chemical_oxdiff_usercomment     'green sample'
_shelx_estimated_absorpt_t_max   0.794
_shelx_estimated_absorpt_t_min   0.539
_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
 C12A-C17A = C15A-C14A = C14A-C13A
 1.37 with sigma of 0.02
 C12A-C13A
 1.38 with sigma of 0.02
 C17A-C16A = C16A-C15A
 1.36 with sigma of 0.02
 C12A-C14A
 2.38 with sigma of 0.04
 C17A-C15A
 2.36 with sigma of 0.04
 C12A-C16A = C16A-C14A = C15A-C13A
 2.37 with sigma of 0.04
 C12A-C17A \\sim C17A-C16A \\sim C16A-C15A \\sim C15A-C14A \\sim C14A-C13A
\\sim C13A-C12A
 with sigma of 0.02
 C12A-C14A \\sim C12A-C16A \\sim C14A-C16A \\sim C15A-C17A \\sim C15A-C13A
\\sim C13A-C17A
 with sigma of 0.04
3. Restrained planarity
 C12A, C17A, C16A, C15A, C14A, C13A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C12A \\sim C17A \\sim C16A \\sim C15A \\sim C14A \\sim C13A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(N2A) = Uanis(Co1)
5. Rigid body (RIGU) restrains
 C12A, C17A, C16A, C15A, C14A, C13A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: N2A(0.5) C12A(0.5) C17A(0.5) H17A(0.5) C16A(0.5) H16A(0.5)
 C15A(0.5) H15A(0.5) C14A(0.5) H14A(0.5) C13A(0.5) H13A(0.5)
7.a Riding coordinates:
 C2(H2)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
7.c Aromatic/amide H refined with riding coordinates:
 C17A(H17A), C16A(H16A), C15A(H15A), C14A(H14A), C13A(H13A)
7.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C),
 C10(H10A,H10B,H10C), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              18348
_shelx_hkl_checksum              11196
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.292
_oxdiff_exptl_absorpt_empirical_full_min 0.449