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_1552216
_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 N4 O2 Zn, F6 P, 1.5(C7 H8)'
_chemical_formula_sum            'C38.5 H41 F6 N4 O2 P Zn'
_chemical_formula_weight         802.09
_chemical_name_systematic
'(tropolonato)-(tris(6-methyl-2-pyridylmethyl)amine)-zinc(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
_audit_block_doi                 10.5517/ccdc.csd.cc21n822
_audit_creation_date             2018-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-02-09 deposited with the CCDC.    2019-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.643(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5155(7)
_cell_length_b                   13.3294(5)
_cell_length_c                   18.3984(8)
_cell_measurement_reflns_used    6409
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      76.6940
_cell_measurement_theta_min      4.1100
_cell_volume                     3697.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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 0.984
_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    -50.00  35.00   1.00    1.50    --  -40.81  38.00 120.00   85
  2  \w    -65.00  33.00   1.00    1.50    --  -40.81  57.00   0.00   98
  3  \w   -108.00 -16.00   1.00    1.50    --  -40.81 -57.00-150.00   92
  4  \w    -34.00  14.00   1.00    1.50    --  -40.81  38.00-180.00   48
  5  \w     50.00  98.00   1.00    1.50    --   40.81-125.00-180.00   48
  6  \w     36.00  80.00   1.00    6.00    --  113.00 -30.00 -60.00   44
  7  \w     61.00 139.00   1.00    6.00    --  113.00  15.00-120.00   78
  8  \w    140.00 167.00   1.00    6.00    --  113.00  15.00-120.00   27
  9  \w     78.00 116.00   1.00    6.00    --  113.00-111.00 -90.00   38
 10  \w     87.00 116.00   1.00    6.00    --  113.00-111.00-180.00   29
 11  \w     54.00 168.00   1.00    6.00    --  113.00 -15.00-180.00  114
 12  \w     45.00 116.00   1.00    6.00    --  113.00-111.00  60.00   71
 13  \w     42.00 109.00   1.00    6.00    --  113.00 -94.00 -60.00   67
 14  \w     39.00  98.00   1.00    6.00    --  113.00 -45.00 -90.00   59
 15  \w     35.00  73.00   1.00    6.00    --  113.00-111.00-180.00   38
 16  \w     35.00  67.00   1.00    6.00    --  113.00-111.00 -90.00   32
 17  \w     35.00 159.00   1.00    6.00    --  113.00 -15.00 -30.00  124
 18  \w     40.00 136.00   1.00    6.00    --  113.00 -61.00 150.00   96
 19  \w     38.00  93.00   1.00    6.00    --  113.00 -45.00  60.00   55
 20  \w     34.00 136.00   1.00    6.00    --  113.00 -77.00  60.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0116548000
_diffrn_orient_matrix_UB_12      -0.1054763000
_diffrn_orient_matrix_UB_13      -0.0304958000
_diffrn_orient_matrix_UB_21      -0.1014173000
_diffrn_orient_matrix_UB_22      -0.0142571000
_diffrn_orient_matrix_UB_23      -0.0202155000
_diffrn_orient_matrix_UB_31      -0.0048805000
_diffrn_orient_matrix_UB_32      0.0448710000
_diffrn_orient_matrix_UB_33      -0.0780374000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0635
_diffrn_reflns_av_unetI/netI     0.0593
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28079
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.585
_diffrn_reflns_theta_min         4.137
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.941
_exptl_absorpt_correction_T_max  0.921
_exptl_absorpt_correction_T_min  0.576
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.441
_exptl_crystal_description       needle
_exptl_crystal_F_000             1660
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.652
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.046
_refine_diff_density_max         1.188
_refine_diff_density_min         -0.922
_refine_diff_density_rms         0.076
_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     486
_refine_ls_number_reflns         7737
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0516
_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^)+(0.0778P)^2^+1.2120P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1346
_refine_ls_wR_factor_ref         0.1501
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5932
_reflns_number_total             7737
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00914k2.cif
_cod_data_source_block           2-znpf6
_cod_original_formula_sum        'C38.50 H41 F6 N4 O2 P Zn'
_cod_database_code               1552216
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Zn1 N4 O2 C28 H29 P1 F6'
_chemical_oxdiff_usercomment     'Clear needles, pale yellow'
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_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
Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C35) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3. Others
 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)
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), C29(H29), C30(H30), C31(H31),
  C32(H32), C33(H33), C38(H38), C37(H37), C36(H36), C40(H40), C39(H39)
4.c Fitted hexagon refined as free rotating group:
 C34(C29,C30,C31,C32,C33), C38(C37,C36,C41,C40,C39)
4.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C35(H35A,H35B,
 H35C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              25022
_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 1.900
_oxdiff_exptl_absorpt_empirical_full_min 0.485