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_1552218
_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, 1.5(C7 H8)'
_chemical_formula_sum            'C38.5 H41 Co F6 N4 O2 P'
_chemical_formula_weight         795.65
_chemical_name_systematic
'(tropolonato)-(tris(6-methyl-2-pyridylmethyl)amine)-cobalt(II) hexafluorophosphate toluene solvate'
_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.cc21n800
_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                 103.839(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4478(4)
_cell_length_b                   13.2858(3)
_cell_length_c                   18.4890(5)
_cell_measurement_reflns_used    4733
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      73.6210
_cell_measurement_theta_min      4.1100
_cell_volume                     3684.46(17)
_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 0.999
_diffrn_measured_fraction_theta_max 0.971
_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   -117.00 -52.00   1.00    4.00    --  -41.87 -77.00  90.00   65
  2  \w   -103.00 -18.00   1.00    4.00    --  -41.87 -38.00 -30.00   85
  3  \w    -58.00  -2.00   1.00    4.00    --  -41.87 125.00 120.00   56
  4  \w     25.00  74.00   1.00    4.00    --   41.87-125.00 -60.00   49
  5  \w     63.00  90.00   1.00   20.00    --  105.57 -94.00  60.00   27
  6  \w     44.00  91.00   1.00   20.00    --  105.57 -30.00  90.00   47
  7  \w     73.00 152.00   1.00   20.00    --  105.57  77.00 120.00   79
  8  \w     84.00 178.00   1.00   20.00    --  105.57  45.00  30.00   94
  9  \w     42.00  92.00   1.00   20.00    --  105.57 -45.00 -90.00   50
 10  \w     47.00  98.00   1.00   20.00    --  105.57 -45.00-150.00   51
 11  \w     31.00  63.00   1.00   20.00    --  105.57 -30.00 150.00   32
 12  \w     31.00  94.00   1.00   20.00    --  105.57 -94.00-120.00   63
;
_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      -0.0649174000
_diffrn_orient_matrix_UB_12      0.0754102000
_diffrn_orient_matrix_UB_13      0.0220499000
_diffrn_orient_matrix_UB_21      -0.0763642000
_diffrn_orient_matrix_UB_22      -0.0415858000
_diffrn_orient_matrix_UB_23      -0.0622719000
_diffrn_orient_matrix_UB_31      -0.0224481000
_diffrn_orient_matrix_UB_32      -0.0776240000
_diffrn_orient_matrix_UB_33      0.0547412000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0398
_diffrn_reflns_av_unetI/netI     0.0540
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            15359
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.846
_diffrn_reflns_theta_min         4.140
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.674
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.222
_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    1.434
_exptl_crystal_description       needle
_exptl_crystal_F_000             1648
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.667
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.614
_refine_diff_density_min         -0.453
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     539
_refine_ls_number_reflns         7246
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0561P)^2^+2.0667P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1270
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6172
_reflns_number_total             7246
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00914k2.cif
_cod_data_source_block           2pf6-iii
_cod_original_formula_sum        'C38.50 H41 Co F6 N4 O2 P'
_cod_database_code               1552218
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         CoC38.5H41N4O2PF6
_chemical_oxdiff_usercomment     'Red-orange needle crystals from toluene'
_reflns_odcompleteness_completeness 99.91
_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. Others
 Sof(C34B)=Sof(C29B)=Sof(H29B)=Sof(C30B)=Sof(H30B)=Sof(C31B)=Sof(H31B)=
 Sof(C32B)=Sof(H32B)=Sof(C33B)=Sof(H33B)=Sof(C35B)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=1-FVAR(1)
 Sof(C34A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=
 Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C35A)=Sof(H35A)=Sof(H35B)=
 Sof(H35C)=FVAR(1)
 Fixed Sof: C38(0.5) H38(0.5) C37(0.5) H37(0.5) C36(0.5) H36(0.5) C41(0.5)
 C40(0.5) H40(0.5) C39(0.5) H39(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C19(H19A,H19B), C25(H25A,H25B)
3.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), C29A(H29A), C30A(H30A),
 C31A(H31A), C32A(H32A), C33A(H33A), C29B(H29B), C30B(H30B), C31B(H31B),
 C32B(H32B), C33B(H33B), C38(H38), C37(H37), C36(H36), C40(H40), C39(H39)
3.c Fitted hexagon refined as free rotating group:
 C34A(C29A,C30A,C31A,C32A,C33A), C34B(C29B,C30B,C31B,C32B,C33B), C38(C37,C36,
 C41,C40,C39)
3.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C35A(H35A,H35B,
 H35C), C35B(H35D,H35E,H35F), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              9606
_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 1.440
_oxdiff_exptl_absorpt_empirical_full_min 0.773