Single-ion anisotropy and exchange coupling in cobalt(ii)-radical complexes: insights from magnetic and ab initio studies
Gransbury, Gemma K.; Boulon, Marie-Emmanuelle; Mole, Richard A.; Gable, Robert W.; Moubaraki, Boujemaa; Murray, Keith S.; Sorace, Lorenzo; Soncini, Alessandro; Boskovic, Colette; Chemical Science  (2019) –; doi:10.1039/C9SC00914K

data_1552215
_publ_section_title
;
 Single-ion anisotropy and exchange coupling in cobalt(ii)-radical
 complexes: insights from magnetic and ab initio studies
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC00914K
_journal_year                    2019
_chemical_formula_moiety         'C28 H29 Co N4 O2, F6 P'
_chemical_formula_sum            'C28 H29 Co F6 N4 O2 P'
_chemical_formula_weight         657.45
_chemical_name_systematic
'(tropolonato)-(tris(6-methyl-2-pyridylmethyl)amine)-cobalt(II) hexafluorophosphate'
_chemical_properties_physical    paramagnetic
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc21n7zy
_audit_creation_date             2018-05-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2019-08-07 deposited with the CCDC.    2019-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.9290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.56610(10)
_cell_length_b                   14.0025(2)
_cell_length_c                   21.2941(3)
_cell_measurement_reflns_used    8756
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      73.9260
_cell_measurement_theta_min      4.1390
_cell_volume                     2841.78(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      130.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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   -110.00 -20.00   1.00    1.00    --  -41.87 -57.00 120.00   90
  2  \w    -86.00 -48.00   1.00    1.00    --  -41.87 125.00 -30.00   38
  3  \w    -68.00  31.00   1.00    1.00    --  -41.87  57.00 -90.00   99
  4  \w    -49.00  32.00   1.00    1.00    --  -41.87  38.00  60.00   81
  5  \w      3.00  30.00   1.00    1.00    --   41.87 -99.00 -30.00   27
  6  \w     35.00  79.00   1.00    7.28    --  105.57 -30.00 -90.00   44
  7  \w     32.00  91.00   1.00    7.28    --  105.57 -30.00-150.00   59
  8  \w     48.00 105.00   1.00    7.28    --  105.57 -94.00  60.00   57
  9  \w     34.00  90.00   1.00    7.28    --  105.57-125.00  60.00   56
 10  \w     87.00 114.00   1.00    7.28    --  105.57-121.00-153.00   27
 11  \w     26.00  83.00   1.00    7.28    --  105.57 -94.00 150.00   57
 12  \w    105.00 160.00   1.00    7.28    --  105.57  45.00 120.00   55
 13  \w     80.00 171.00   1.00    7.28    --  105.57  45.00-120.00   91
 14  \w     34.00  88.00   1.00    7.28    --  105.57 -45.00  30.00   54
 15  \w     55.00  84.00   1.00    7.28    --  105.57 -30.00 -30.00   29
 16  \w     91.00 135.00   1.00    7.28    --  105.57-152.00  46.00   44
 17  \w     40.00  66.00   1.00    7.28    --  105.57-152.00  46.00   26
 18  \w     68.00 103.00   1.00    7.28    --  105.57 -61.00 120.00   35
 19  \w     80.00 172.00   1.00    7.28    --  105.57  45.00-180.00   92
 20  \w     30.00 138.00   1.00    7.28    --  105.57 -77.00-150.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0348984000
_diffrn_orient_matrix_UB_12      -0.0981604000
_diffrn_orient_matrix_UB_13      0.0273858000
_diffrn_orient_matrix_UB_21      0.0468384000
_diffrn_orient_matrix_UB_22      0.0362931000
_diffrn_orient_matrix_UB_23      0.0668001000
_diffrn_orient_matrix_UB_31      -0.1507055000
_diffrn_orient_matrix_UB_32      0.0339688000
_diffrn_orient_matrix_UB_33      0.0077640000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            20711
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.048
_diffrn_reflns_theta_min         3.782
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.926
_exptl_absorpt_correction_T_max  0.982
_exptl_absorpt_correction_T_min  0.250
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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 reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.537
_exptl_crystal_description       prism
_exptl_crystal_F_000             1348
_exptl_crystal_recrystallization_method 'Crystallised from toluene'
_exptl_crystal_size_max          0.357
_exptl_crystal_size_mid          0.257
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.262
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         5667
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0333
_refine_ls_R_factor_gt           0.0316
_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^)+(0.0480P)^2^+0.7564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0817
_refine_ls_wR_factor_ref         0.0831
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5398
_reflns_number_total             5667
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00914k2.cif
_cod_data_source_block           2pf6-i
_cod_database_code               1552215
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         CoC28H29N4O2PF6
_chemical_oxdiff_usercomment     'Red-orange prism shaped crystals from toluene'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C19(H19A,H19B), C25(H25A,H25B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C17(H17), C21(H21), C22(H22), C23(H23)
2.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              88828
_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 1.553
_oxdiff_exptl_absorpt_empirical_full_min 0.780