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_1552217
_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         'C35 H44 N4 O2 Zn, F6 P, C7 H8'
_chemical_formula_sum            'C42 H52 F6 N4 O2 P Zn'
_chemical_formula_weight         855.21
_chemical_name_systematic
'(3,5-di-tert-butyl-catecholato)-(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
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc21n844
_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                 94.0310(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.56860(10)
_cell_length_b                   31.8810(4)
_cell_length_c                   22.0748(2)
_cell_measurement_reflns_used    28258
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      76.9350
_cell_measurement_theta_min      4.0420
_cell_volume                     8121.45(14)
_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 0.987
_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    -48.00  24.00   1.00    1.34    --  -40.81  38.00 -90.00   72
  2  \w    -72.00  44.00   1.00    1.34    --  -40.81   0.00  30.00  116
  3  \w     29.00  94.00   1.00    1.34    --   40.81-125.00  30.00   65
  4  \w     35.00  90.00   1.00    5.35    --  113.00 -30.00   0.00   55
  5  \w     44.00 147.00   1.00    5.35    --  113.00 -77.00  60.00  103
  6  \w     82.00 116.00   1.00    5.35    --  113.00-111.00 -30.00   34
  7  \w     39.00  97.00   1.00    5.35    --  113.00 -45.00  60.00   58
  8  \w     40.00  91.00   1.00    5.35    --  113.00 -30.00 -60.00   51
  9  \w    100.00 178.00   1.00    5.35    --  113.00  45.00 -30.00   78
 10  \w    138.00 178.00   1.00    5.35    --  113.00 111.00 -30.00   40
 11  \w    109.00 135.00   1.00    5.35    --  113.00 111.00 -30.00   26
 12  \w     34.00 171.00   1.00    5.35    --  113.00 -15.00 150.00  137
 13  \w     42.00 114.00   1.00    5.35    --  113.00-111.00 -90.00   72
 14  \w     78.00 109.00   1.00    5.35    --  113.00 -94.00-180.00   31
 15  \w     39.00 140.00   1.00    5.35    --  113.00 -61.00-120.00  101
 16  \w     36.00 116.00   1.00    5.35    --  113.00-111.00  60.00   80
 17  \w     38.00  63.00   1.00    5.35    --  113.00-111.00 -30.00   25
 18  \w     27.00  97.00   1.00    1.34    --   40.81-125.00-180.00   70
 19  \w     29.00  62.00   1.00    5.35    --  113.00 -94.00-180.00   33
 20  \w   -110.00 -64.00   1.00    1.34    --  -40.81-147.00 -65.00   46
;
_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      -0.0854557000
_diffrn_orient_matrix_UB_12      -0.0364128000
_diffrn_orient_matrix_UB_13      0.0072776000
_diffrn_orient_matrix_UB_21      -0.1009073000
_diffrn_orient_matrix_UB_22      0.0315403000
_diffrn_orient_matrix_UB_23      0.0001321000
_diffrn_orient_matrix_UB_31      -0.0185925000
_diffrn_orient_matrix_UB_32      -0.0037330000
_diffrn_orient_matrix_UB_33      -0.0695711000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            61398
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.329
_diffrn_reflns_theta_min         4.015
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.799
_exptl_absorpt_correction_T_max  0.830
_exptl_absorpt_correction_T_min  0.696
_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 dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.399
_exptl_crystal_description       block
_exptl_crystal_F_000             3576
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.273
_exptl_crystal_size_mid          0.202
_exptl_crystal_size_min          0.134
_refine_diff_density_max         0.842
_refine_diff_density_min         -0.782
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1082
_refine_ls_number_reflns         17012
_refine_ls_number_restraints     100
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0635P)^2^+5.5453P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1157
_refine_ls_wR_factor_ref         0.1191
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15515
_reflns_number_total             17012
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00914k2.cif
_cod_data_source_block           3-znpf6
_cod_database_code               1552217
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Zn1 O2 N4 P1 F6 C42 H52'
_chemical_oxdiff_usercomment     'blue blocks'
_reflns_odcompleteness_completeness 99.53
_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. Restrained distances
 P2A-F7A = P2A-F8A = P2A-F9A = P2A-F10A = P2A-F11A = P2A-F12A
 1.56553 with sigma of 0.001
 P2B-F7B = P2B-F8B = P2B-F9B = P2B-F10B = P2B-F11B = P2B-F12B
 1.56553 with sigma of 0.001
 F7A-F8A = F7A-F9A = F7A-F10A = F7A-F11A
 2.213659 with sigma of 0.001
 F7B-F8B = F7B-F9B = F7B-F10B = F7B-F11B
 2.213659 with sigma of 0.001
 F12A-F8A = F12A-F9A = F12A-F10A = F12A-F11A
 2.213659 with sigma of 0.001
 F12B-F8B = F12B-F9B = F12B-F10B = F12B-F11B
 2.213659 with sigma of 0.001
 F8A-F9A = F9A-F11A = F11A-F10A = F10A-F8A
 2.213659 with sigma of 0.001
 F8B-F9B = F9B-F11B = F11B-F10B = F10B-F8B
 2.213659 with sigma of 0.001
3. Restrained planarity
 P2A, F8A, F9A, F10A, F11A
 with sigma of 0.1
 P2B, F8B, F9B, F10B, F11B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
F7A \\sim F8A \\sim F9A \\sim F10A \\sim F11A \\sim F12A \\sim F7B \\sim F8B
\\sim F9B \\sim F10B \\sim F11B \\sim F12B: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Uanis(F7A) = Uanis(F7B)
Uanis(F12A) = Uanis(F12B)
5. Others
 Sof(P2B)=Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(1)
 Sof(P2A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(1)
 1(DFIX)=1(DFIX)=FVAR(2)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1.414*FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C26(H26A,H26B), C32(H32A,H32B), C55(H55A,H55B), C61(H61A,
 H61B), C67(H67A,H67B)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C16(H16), C17(H17), C18(H18), C22(H22), C23(H23), C24(H24),
 C28(H28), C29(H29), C30(H30), C39(H39), C41(H41), C51(H51), C52(H52), C53(H53),
  C57(H57), C58(H58), C59(H59), C63(H63), C64(H64), C65(H65), C71(H71),
 C72(H72), C73(H73), C74(H74), C75(H75), C78(H78), C79(H79), C80(H80), C81(H81),
  C82(H82)
6.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,
 H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C),
 C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C77(H77A,H77B,
 H77C), C84(H84A,H84B,H84C)
;
_shelx_res_checksum              2020
_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 2.383
_oxdiff_exptl_absorpt_empirical_full_min 0.621