Electronic structure of cobalt valence tautomeric molecules in different environments.
Mishra, Esha; Ekanayaka, Thilini K.; Panagiotakopoulos, Theodoros; Le, Duy; Rahman, Talat S.; Wang, Ping; McElveen, Kayleigh A.; Phillips, Jared P.; Zaid Zaz, M.; Yazdani, Saeed; N'Diaye, Alpha T; Lai, Rebecca Y.; Streubel, Robert; Cheng, Ruihua; Shatruk, Michael; Dowben, Peter A.; Nanoscale 15 (2023) 2044–2053; doi:10.1039/d2nr06834f

data_1568190
_publ_section_title
;
 Electronic structure of cobalt valence tautomeric molecules in different
 environments.
;
_journal_issue                   5
_journal_name_full               Nanoscale
_journal_page_first              2044
_journal_page_last               2053
_journal_paper_doi               10.1039/d2nr06834f
_journal_volume                  15
_journal_year                    2023
_chemical_formula_moiety         'C46 H54 Co N2 O4 S2, C3.5 H4'
_chemical_formula_sum            'C49.5 H58 Co N2 O4 S2'
_chemical_formula_weight         868.03
_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
_audit_creation_date             2022-11-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-20 deposited with the CCDC.	2022-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                73.710(2)
_cell_angle_beta                 82.873(2)
_cell_angle_gamma                83.416(2)
_cell_formula_units_Z            1
_cell_length_a                   8.0196(2)
_cell_length_b                   10.2784(3)
_cell_length_c                   15.7772(4)
_cell_measurement_reflns_used    10120
_cell_measurement_temperature    229.99(10)
_cell_measurement_theta_max      32.2830
_cell_measurement_theta_min      2.5640
_cell_volume                     1234.28(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (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    'XT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      230.0(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.874
_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    -39.00  44.00   0.50   38.20    --   17.00 -78.00   1.00  166
  2  \w    -44.00  19.00   0.50   38.20    --  -17.46  78.00 126.00  126
  3  \w    -34.00  10.00   0.50   38.20    --  -17.46 -78.00   1.00   88
  4  \w     23.00  55.00   0.50   38.20    --   17.00  57.00  90.00   64
  5  \w     51.00  79.00   0.50   38.20    --   17.00 178.00 -60.00   56
  6  \w     53.00  92.00   0.50   38.20    --   17.00 178.00 -90.00   78
  7  \w     49.00  94.00   0.50   38.20    --   17.00 178.00 -30.00   90
  8  \w     -5.00  56.00   0.50   38.20    --   17.00  57.00 -60.00  122
  9  \w    -14.00  12.00   0.50   38.20    --  -17.46 -77.00 -60.00   52
 10  \w    -17.00  57.00   0.50   38.20    --  -17.46  57.00  90.00  148
 11  \w    -25.00   0.00   0.50   38.20    --  -17.46 -77.00-120.00   50
 12  \w    -25.00   0.00   0.50   38.20    --  -17.46 -77.00-180.00   50
 13  \w    -56.00   6.00   0.50   38.20    --  -17.46 -57.00 -90.00  124
 14  \w    -24.00   1.00   0.50   38.20    --  -17.46 -77.00  90.00   50
;
_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      0.0523647000
_diffrn_orient_matrix_UB_12      0.0335575000
_diffrn_orient_matrix_UB_13      0.0186778000
_diffrn_orient_matrix_UB_21      0.0114237000
_diffrn_orient_matrix_UB_22      -0.0597528000
_diffrn_orient_matrix_UB_23      0.0352581000
_diffrn_orient_matrix_UB_31      0.0716143000
_diffrn_orient_matrix_UB_32      -0.0225618000
_diffrn_orient_matrix_UB_33      -0.0249468000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0448
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.874
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            23495
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.874
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.272
_diffrn_reflns_theta_min         2.072
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.474
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.525
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (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            dark-blue
_exptl_crystal_colour_primary    dark-blue
_exptl_crystal_density_diffrn    1.168
_exptl_crystal_description       plate
_exptl_crystal_F_000             460
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/dichloromethane'
_exptl_crystal_size_max          0.231
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.044
_refine_diff_density_max         1.240
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         8310
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0816
_refine_ls_R_factor_gt           0.0625
_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^)+(0.1256P)^2^+0.2158P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1940
_refine_ls_wR_factor_ref         0.2085
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6232
_reflns_number_total             8310
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nr06834f2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 1568190.cif.'
_cod_original_formula_sum        'C49.50 H58 Co N2 O4 S2'
_cod_database_code               1568190
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CoS2N2O4C51H60
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C26-C27
 1.5 with sigma of 0.005
 C26-H26
 0.96 with sigma of 0.001
 C25-H26
 2 with sigma of 0.005
3. Others
 Fixed Sof: C24(0.5) H24(0.5) C25(0.5) H25(0.5) C26(0.5) C27(0.25) H27A(0.25)
 H27B(0.25) H27C(0.25) H26(0.25)
4.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C22(H22),
 C23(H23), C24(H24), C25(H25)
4.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              41643
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.701
_oxdiff_exptl_absorpt_empirical_full_min 0.717