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_7715614
_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         'C30 H30 Co N12 O2, B2 F8'
_chemical_formula_sum            'C30 H30 B2 Co F8 N12 O2'
_chemical_formula_weight         823.21
_space_group_crystal_system      orthorhombic
_space_group_IT_number           70
_space_group_name_Hall           '-F 2uv 2vw'
_space_group_name_H-M_alt        'F d d d :2'
_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
;
2024-02-14 deposited with the CCDC.	2024-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.1032(8)
_cell_length_b                   17.2017(10)
_cell_length_c                   30.254(2)
_cell_measurement_reflns_used    1411
_cell_measurement_temperature    250.0(7)
_cell_measurement_theta_max      25.6520
_cell_measurement_theta_min      2.6890
_cell_volume                     6819.2(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_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 n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      250.0(7)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9653
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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    -96.00  -6.00   1.00   20.00    --  -27.28 -57.00  60.00   90
  2  \w    -49.00  42.00   1.00   20.00    --  -27.28  57.00-150.00   91
  3  \w   -100.00 -38.00   1.00   20.00    --  -27.28 -19.00 150.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0182799000
_diffrn_orient_matrix_UB_12      -0.0241386000
_diffrn_orient_matrix_UB_13      -0.0172871000
_diffrn_orient_matrix_UB_21      -0.0332399000
_diffrn_orient_matrix_UB_22      0.0301519000
_diffrn_orient_matrix_UB_23      -0.0069793000
_diffrn_orient_matrix_UB_31      0.0385595000
_diffrn_orient_matrix_UB_32      0.0145178000
_diffrn_orient_matrix_UB_33      -0.0142198000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0645
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            9778
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.500
_diffrn_reflns_theta_min         2.066
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.598
_exptl_absorpt_correction_T_max  0.999
_exptl_absorpt_correction_T_min  0.988
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'lustrous black'
_exptl_crystal_density_diffrn    1.604
_exptl_crystal_description       plate
_exptl_crystal_F_000             3352
_exptl_crystal_size_max          0.584
_exptl_crystal_size_mid          0.204
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.361
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     161
_refine_ls_number_reflns         2602
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.1363
_refine_ls_R_factor_gt           0.0844
_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^)+(0.0509P)^2^+45.7583P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1751
_refine_ls_wR_factor_ref         0.1964
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1620
_reflns_number_total             2602
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00465e2.cif
_cod_data_source_block           db30b_250_autored
_cod_depositor_comments
'Adding full bibliography for 7715611--7715614.cif.'
_cod_original_sg_symbol_H-M      'F d d d'
_cod_database_code               7715614
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H32B2CoF8N12O2
_reflns_odcompleteness_completeness 99.40
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C00C) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N006) \\sim Ueq, Uanis(C007) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C0)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
2. Others
 Fixed Sof: N006(0.5) C007(0.5) H00C(0.5) O00G(0.5) C00H(0.5) H00E(0.5)
 H00G(0.5) H00H(0.5) C1(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C0(0.5) N2(0.5)
3.a Ternary CH refined with riding coordinates:
 C00C(H00C)
3.b Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00B(H00B), C00D(H00D), C00F(H00F)
3.c Idealised Me refined as rotating group:
 C00H(H00E,H00G,H00H), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              4384
_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 1.148
_oxdiff_exptl_absorpt_empirical_full_min 0.905