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_1552221
_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_absolute_configuration ad
_chemical_formula_moiety         'C28 H29 Co N4 O2, F6 P, 1(C7 H8)'
_chemical_formula_sum            'C35 H37 Co F6 N4 O2 P'
_chemical_formula_weight         749.58
_chemical_name_systematic
'(tropolonato)-(tris(6-methyl-2-pyridylmethyl)amine)-cobalt(II) hexafluorophosphate toluene solvate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc21n811
_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
;
2019-02-09 deposited with the CCDC.    2019-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.897(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.7975(2)
_cell_length_b                   13.6880(2)
_cell_length_c                   13.4124(3)
_cell_measurement_reflns_used    8132
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      73.9200
_cell_measurement_theta_min      4.7210
_cell_volume                     1701.77(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 0.986
_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  29.00   1.00    1.00    --  -41.87  38.00  90.00   54
  2  \w    -49.00  21.00   1.00    1.00    --  -41.87  38.00-180.00   70
  3  \w    -80.00  -2.00   1.00    1.00    --  -41.87 125.00 -60.00   78
  4  \w     49.00  89.00   1.00    1.00    --   41.87-125.00-150.00   40
  5  \w     30.00  96.00   1.00    1.00    --   41.87  77.00-180.00   66
  6  \w     25.00  86.00   1.00    1.00    --   41.87  38.00 -60.00   61
  7  \w     76.00 125.00   1.00    3.88    --  105.57  61.00-180.00   49
  8  \w     29.00  90.00   1.00    3.88    --  105.57 -30.00-150.00   61
  9  \w     30.00  58.00   1.00    3.88    --  105.57 -30.00 150.00   28
 10  \w     73.00  99.00   1.00    3.88    --  105.57  77.00-150.00   26
 11  \w    111.00 177.00   1.00    3.88    --  105.57  77.00-150.00   66
 12  \w     39.00  98.00   1.00    3.88    --  105.57 -45.00-180.00   59
 13  \w     81.00 171.00   1.00    3.88    --  105.57  61.00 -90.00   90
 14  \w     60.00 118.00   1.00    3.88    --  105.57-125.00  90.00   58
 15  \w     40.00  88.00   1.00    3.88    --  105.57 -94.00   0.00   48
 16  \w     76.00 102.00   1.00    3.88    --  105.57  61.00-120.00   26
 17  \w     77.00 103.00   1.00    3.88    --  105.57  61.00-150.00   26
 18  \w    153.00 178.00   1.00    3.88    --  105.57  77.00-120.00   25
 19  \w     29.00  90.00   1.00    3.88    --  105.57 -30.00 -90.00   61
 20  \w     74.00  99.00   1.00    3.88    --  105.57  77.00-120.00   25
 21  \w    106.00 131.00   1.00    3.88    --  105.57  45.00 -30.00   25
 22  \w     81.00 106.00   1.00    3.88    --  105.57  45.00-120.00   25
 23  \w     84.00 150.00   1.00    3.88    --  105.57  45.00 -90.00   66
 24  \w     85.00 141.00   1.00    3.88    --  105.57  45.00-150.00   56
 25  \w     29.00  74.00   1.00    3.88    --  105.57 -30.00 -30.00   45
 26  \w     79.00 151.00   1.00    3.88    --  105.57  30.00 120.00   72
;
_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      0.0733382000
_diffrn_orient_matrix_UB_12      -0.0383847000
_diffrn_orient_matrix_UB_13      -0.0780049000
_diffrn_orient_matrix_UB_21      -0.1349261000
_diffrn_orient_matrix_UB_22      -0.0614913000
_diffrn_orient_matrix_UB_23      -0.0557257000
_diffrn_orient_matrix_UB_31      -0.0636157000
_diffrn_orient_matrix_UB_32      0.0861162000
_diffrn_orient_matrix_UB_33      -0.0744314000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0257
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            14355
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.080
_diffrn_reflns_theta_min         3.483
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.023
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.361
_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    1.463
_exptl_crystal_description       block
_exptl_crystal_F_000             774
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.079
_refine_diff_density_max         0.189
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2941 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.007(2)
_refine_ls_extinction_coef       0.0014(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     542
_refine_ls_number_reflns         6693
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0291
_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^)+(0.0506P)^2^+0.1895P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0764
_refine_ls_wR_factor_ref         0.0771
_reflns_Friedel_coverage         0.883
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                6551
_reflns_number_total             6693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00914k2.cif
_cod_data_source_block           2pf6-iv
_cod_database_code               1552221
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         CoC35H37N4O2PF6
_chemical_oxdiff_usercomment     'Red block from evaporation of toluene'
_reflns_odcompleteness_completeness 99.97
_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. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C1C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C2A \\sim C2B \\sim C2C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C3A \\sim C3B \\sim C3C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C4A \\sim C4B \\sim C4C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C5A \\sim C5B \\sim C5C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C6A \\sim C6B \\sim C6C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C7A \\sim C7B \\sim C7C: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
3. Others
 1*[Sof(C1A)+Sof(H1A)+Sof(C2A)+Sof(H2A)+Sof(C3A)+Sof(H3A)+Sof(C4A)+Sof(H4A)+
 Sof(C5A)+Sof(H5A)+Sof(C6A)+Sof(C7A)+Sof(H7AA)+Sof(H7AB)+Sof(H7AC)]+1*[Sof(C1B)+
 Sof(H1B)+Sof(C2B)+Sof(H2B)+Sof(C3B)+Sof(H3B)+Sof(C4B)+Sof(H4B)+Sof(C5B)+
 Sof(H5B)+Sof(C6B)+Sof(C7B)+Sof(H7BA)+Sof(H7BB)+Sof(H7BC)]+1*[Sof(C1C)+Sof(H1C)+
 Sof(C2C)+Sof(H2C)+Sof(C3C)+Sof(H3C)+Sof(C4C)+Sof(H4C)+Sof(C5C)+Sof(H5C)+
 Sof(C6C)+Sof(C7C)+Sof(H7CA)+Sof(H7CB)+Sof(H7CC)]=1 with esd of 0.0001
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=FVAR(1)
 Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(H7BC)=FVAR(2)
 Sof(C1C)=Sof(H1C)=Sof(C2C)=Sof(H2C)=Sof(C3C)=Sof(H3C)=Sof(C4C)=Sof(H4C)=
 Sof(C5C)=Sof(H5C)=Sof(C6C)=Sof(C7C)=Sof(H7CA)=Sof(H7CB)=Sof(H7CC)=FVAR(3)
4.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C19(H19A,H19B), C25(H25A,H25B)
4.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), C1A(H1A), C2A(H2A), C3A(H3A),
  C4A(H4A), C5A(H5A), C1B(H1B), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B),
 C1C(H1C), C2C(H2C), C3C(H3C), C4C(H4C), C5C(H5C)
4.c Fitted hexagon refined as free rotating group:
 C1A(C2A,C3A,C4A,C5A,C6A), C1B(C2B,C3B,C4B,C5B,C6B), C1C(C2C,C3C,C4C,C5C,C6C)
4.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C7A(H7AA,H7AB,
 H7AC), C7B(H7BA,H7BB,H7BC), C7C(H7CA,H7CB,H7CC)
;
_shelx_res_checksum              17038
_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 1.390
_oxdiff_exptl_absorpt_empirical_full_min 0.774