Spectroscopic and thermodynamic characterization of a cobalt-verdazyl valence tautomeric system. influence of crystal structure, solvent and counterion.
Brook, David J. R.; DaRos, Jeffrey; Ponnekanti, Aamani; Agrestini, Stefano; Pellegrin, Eric; Dalton transactions (Cambridge, England : 2003) 53 (2024) 7536–7545; doi:10.1039/d4dt00465e

data_7715611
_publ_section_title
;
 Spectroscopic and thermodynamic characterization of a cobalt-verdazyl
 valence tautomeric system. influence of crystal structure, solvent and
 counterion.
;
_journal_issue                   17
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7536
_journal_page_last               7545
_journal_paper_doi               10.1039/d4dt00465e
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '4(F3 Sb0.5), C30 H30 Co N12 O2, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C30.5 H31 Cl Co F12 N12 O2 Sb2'
_chemical_formula_weight         1163.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-13 deposited with the CCDC.	2024-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.966(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0686(7)
_cell_length_b                   29.208(2)
_cell_length_c                   16.0218(12)
_cell_measurement_reflns_used    9884
_cell_measurement_temperature    301.0
_cell_measurement_theta_max      30.43
_cell_measurement_theta_min      2.97
_cell_volume                     4118.3(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      301.0
_diffrn_detector                 'Bruker Photon II area detector'
_diffrn_detector_area_resol_mean 8
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0749
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            162266
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.469
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           20.0
_diffrn_source_power             0.9
_diffrn_source_target            Mo
_diffrn_source_type              'Bruker Quest Eco'
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.866
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6120
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.877
_exptl_crystal_description       needle
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.775
_refine_diff_density_min         -0.904
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.178
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     615
_refine_ls_number_reflns         8413
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.180
_refine_ls_R_factor_all          0.0878
_refine_ls_R_factor_gt           0.0776
_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^)+(0.0430P)^2^+23.1366P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1649
_refine_ls_wR_factor_ref         0.1701
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7314
_reflns_number_total             8413
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00465e2.cif
_cod_data_source_block           db_nov12_2020_0m
_cod_depositor_comments
'Adding full bibliography for 7715611--7715614.cif.'
_cod_original_formula_sum        'C30.50 H31 Cl Co F12 N12 O2 Sb2'
_cod_database_code               7715611
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.835
_shelx_estimated_absorpt_t_min   0.522
_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
 Sb3-F10 = Sb3-F11 = Sb3-F12 = Sb3-F13 = Sb3-F14 = Sb3-F15
 1.86 with sigma of 0.02
 C31-Cl1 = C31-Cl2
 1.77 with sigma of 0.02
 F10-F11 = F10-F13 = F10-F14 = F10-F15
 2.63 with sigma of 0.04
 F11-F12 = F11-F13 = F11-F15 = F12-F13 = F12-F14 = F12-F15 = F13-F14 = F14-F15
 2.63 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C31) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(F8)=Sof(F7)=1-FVAR(1)
 Sof(F7A)=Sof(F8A)=FVAR(1)
 Fixed Sof: Sb3(0.5) Cl2(0.5) Cl1(0.5) F10(0.5) F15(0.5) F11(0.5) F13(0.5)
 F14(0.5) F12(0.5) C31(0.5) H31A(0.5) H31B(0.5)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C28(H28)
5.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B)
5.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C11(H11), C9(H9), C12(H12), C4(H4), C22(H22), C26(H26), C10(H10),
 C24(H24), C25(H25), C19(H19), C5(H5), C21(H21), C7(H7), C20(H20), C6(H6)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C29(H29A,H29B,H29C), C14(H14A,H14B,H14C), C30(H30A,H30B,
 H30C)
;
_shelx_res_checksum              2218
_olex2_submission_special_instructions 'No special instructions were received'