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_1552220
_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         'C27 H24 Br4 Co0.06 N4 O2 Zn0.94'
_chemical_formula_sum            'C27 H24 Br4 Co0.06 N4 O2 Zn0.94'
_chemical_formula_weight         821.12
_chemical_name_systematic
(3,4,5,6-tetrabromocatecholato)-(tris(6-methyl-2-pyridylmethyl)amine)-cobalt(II):zinc(II)
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc21n7xw
_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
;
2019-08-07 deposited with the CCDC.    2019-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.5500(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.3060(2)
_cell_length_b                   13.5277(2)
_cell_length_c                   18.5746(3)
_cell_measurement_reflns_used    11416
_cell_measurement_temperature    130.00(10)
_cell_measurement_theta_max      76.8690
_cell_measurement_theta_min      4.0250
_cell_volume                     2838.06(8)
_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      130.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9969
_diffrn_measured_fraction_theta_max 0.9887
_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  10.00   1.00    1.00    --  -40.81  38.00  90.00   60
  2  \w    -46.00  25.00   1.00    1.00    --  -40.81  38.00 -90.00   71
  3  \w     23.00  91.00   1.00    1.00    --   40.81-125.00   0.00   68
  4  \w     35.00 116.00   1.00    2.50    --  113.00-111.00 -60.00   81
  5  \w     77.00 105.00   1.00    2.50    --  113.00 -94.00-150.00   28
  6  \w     39.00  72.00   1.00    2.50    --  113.00 -30.00 -60.00   33
  7  \w     34.00 144.00   1.00    2.50    --  113.00 -77.00 -30.00  110
  8  \w     90.00 116.00   1.00    2.50    --  113.00-111.00  60.00   26
  9  \w     42.00 143.00   1.00    2.50    --  113.00 -61.00 120.00  101
 10  \w     85.00 177.00   1.00    2.50    --  113.00  45.00 120.00   92
 11  \w    105.00 177.00   1.00    2.50    --  113.00 111.00  60.00   72
 12  \w     97.00 178.00   1.00    2.50    --  113.00  30.00-120.00   81
 13  \w     82.00 178.00   1.00    2.50    --  113.00  30.00-180.00   96
 14  \w     39.00  86.00   1.00    1.00    --   40.81-125.00-180.00   47
 15  \w     30.00  58.00   1.00    2.50    --  113.00 -94.00-150.00   28
 16  \w     37.00  68.00   1.00    2.50    --  113.00-111.00  60.00   31
 17  \w     38.00 116.00   1.00    2.50    --  113.00-111.00 150.00   78
 18  \w     58.00 123.00   1.00    2.50    --  113.00 178.00 150.00   65
 19  \w   -122.00  -5.00   1.00    1.00    --  -40.81 -19.00  90.00  117
;
_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      0.0540835000
_diffrn_orient_matrix_UB_12      -0.1008685000
_diffrn_orient_matrix_UB_13      -0.0186044000
_diffrn_orient_matrix_UB_21      0.0573640000
_diffrn_orient_matrix_UB_22      0.0466672000
_diffrn_orient_matrix_UB_23      -0.0656021000
_diffrn_orient_matrix_UB_31      0.1112307000
_diffrn_orient_matrix_UB_32      0.0249650000
_diffrn_orient_matrix_UB_33      0.0473826000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            20997
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.061
_diffrn_reflns_theta_min         4.044
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.279
_exptl_absorpt_correction_T_max  0.540
_exptl_absorpt_correction_T_min  0.224
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.922
_exptl_crystal_description       block
_exptl_crystal_F_000             1599.3
_exptl_crystal_recrystallization_method
'Crystallised from hot DMF/diethyl ether (1:2)'
_exptl_crystal_size_max          0.255
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.105
_refine_diff_density_max         0.418
_refine_diff_density_min         -0.700
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         5938
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0255
_refine_ls_R_factor_gt           0.0237
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0342P)^2^+1.3943P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0622
_refine_ls_wR_factor_ref         0.0634
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5622
_reflns_number_total             5938
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00914k2.cif
_cod_data_source_block           1-co5-zn95
_cod_database_code               1552220
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C27 H24 Br4 Co0.047 N4 O2 Zn0.953'
_chemical_oxdiff_usercomment     'Co-doped Zn roughly 0.05. orange block'
_shelx_estimated_absorpt_t_max   0.477
_shelx_estimated_absorpt_t_min   0.227
_reflns_odcompleteness_completeness 99.69
_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. Shared sites
{Zn1, Co}
3. Uiso/Uaniso restraints and constraints
Uanis(Zn1) = Uanis(Co)
4. Others
 Sof(Co)=1-FVAR(1)
 Sof(Zn1)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C18(H18A,H18B), C24(H24A,H24B)
5.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C14(H14), C15(H15), C16(H16), C20(H20), C21(H21),
 C22(H22)
5.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              37678
_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 1.581
_oxdiff_exptl_absorpt_empirical_full_min 0.732