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_1552219
_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, 1(F6 P1)'
_chemical_formula_sum            'C28 H29 Co F6 N4 O2 P'
_chemical_formula_weight         657.45
_chemical_name_systematic
'(tropolonato)-(tris(6-methyl-2-pyridylmethyl)amine)-cobalt(II) hexafluorophosphate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc21n7yx
_audit_creation_date             2018-04-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2019-08-07 deposited with the CCDC.    2019-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                86.195(3)
_cell_angle_beta                 72.635(3)
_cell_angle_gamma                84.222(3)
_cell_formula_units_Z            4
_cell_length_a                   13.2750(4)
_cell_length_b                   13.4480(5)
_cell_length_c                   16.9694(5)
_cell_measurement_reflns_used    8017
_cell_measurement_temperature    130.00(10)
_cell_measurement_theta_max      75.6360
_cell_measurement_theta_min      3.3050
_cell_volume                     2874.55(17)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      air
_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 1.000
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details
;
  1 omega  -30.00   11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0592   37.0000  -30.0000 41

  2 omega  -42.00   20.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0592   37.0000  120.0000 62

  3 omega  -83.00   -2.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0592  125.0000 -180.0000 81

  4 omega -112.00    4.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.0592  -19.0000  120.0000 116

  5 omega   45.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0592  -99.0000   90.0000 38

  6 omega   27.00  109.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -94.0000  120.0000 82

  7 omega   52.00   90.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -30.0000  120.0000 38

  8 omega   53.00  178.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063   15.0000   90.0000 125

  9 omega  128.00  177.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  111.0000    0.0000 49

 10 omega   89.00  169.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063   30.0000  150.0000 80

 11 omega   68.00  113.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063 -111.0000  -30.0000 45

 12 omega  102.00  138.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -77.0000  -90.0000 36

 13 omega   53.00  105.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063 -111.0000 -120.0000 52

 14 omega   55.00   94.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -45.0000  -90.0000 39

 15 omega   47.00   81.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -30.0000 -120.0000 34

 16 omega   38.00   93.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -45.0000 -180.0000 55

 17 omega   36.00   73.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -77.0000  -90.0000 37

 18 omega    4.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.0592  -99.0000   30.0000 56

 19 omega   45.00   97.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  -45.0000   90.0000 52

 20 omega   38.00  109.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063 -111.0000   90.0000 71

 21 omega   72.00   99.00   1.0000    6.5000
omega____ theta____ kappa____ phi______ frames
    -      110.2063  178.0000 -180.0000 27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1034417000
_diffrn_orient_matrix_UB_12      -0.0138793000
_diffrn_orient_matrix_UB_13      -0.0713830000
_diffrn_orient_matrix_UB_21      0.0262631000
_diffrn_orient_matrix_UB_22      0.1060117000
_diffrn_orient_matrix_UB_23      0.0117700000
_diffrn_orient_matrix_UB_31      0.0591762000
_diffrn_orient_matrix_UB_32      -0.0429645000
_diffrn_orient_matrix_UB_33      0.0618626000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21096
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.570
_diffrn_reflns_theta_min         3.306
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.859
_exptl_absorpt_correction_T_max  0.691
_exptl_absorpt_correction_T_min  0.443
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.519
_exptl_crystal_description       block
_exptl_crystal_F_000             1348
_exptl_crystal_preparation       'Crystallised from hot toluene'
_exptl_crystal_recrystallization_method 'Recrystallised from hot toluene'
_exptl_crystal_size_max          0.2077
_exptl_crystal_size_mid          0.1385
_exptl_crystal_size_min          0.0754
_refine_diff_density_max         1.192
_refine_diff_density_min         -0.466
_refine_diff_density_rms         0.055
_refine_ls_extinction_coef       0.00028(7)
_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   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     951
_refine_ls_number_reflns         11562
_refine_ls_number_restraints     369
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0634P)^2^+0.8696P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1069
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10215
_reflns_number_total             11562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00914k2.cif
_cod_data_source_block           2pf6-ii
_cod_original_cell_volume        2874.56(18)
_cod_database_code               1552219
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C28 H29 Co F6 N4 O2 P'
_chemical_oxdiff_usercomment     'Orange prism crystals from toluene'
_reflns_odcompleteness_completeness 99.99
_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. Restrained distances
 P1A-F1A = P1A-F2A = P1A-F3A = P1A-F4A = P1A-F5A = P1A-F6A
 1.59108 with sigma of 0.001
 P1B-F1B = P1B-F2B = P1B-F3B = P1B-F4B = P1B-F5B = P1B-F6B
 1.59108 with sigma of 0.001
 P1C-F1B = P1C-F2C = P1C-F3C = P1C-F4C = P1C-F5C = P1C-F6C
 1.59108 with sigma of 0.001
 F1A-F2A = F1A-F3A = F1A-F4A = F1A-F5A
 2.249787 with sigma of 0.001
 F6A-F2A = F6A-F3A = F6A-F4A = F6A-F5A
 2.249787 with sigma of 0.001
 F1B-F2B = F1B-F3B = F1B-F4B = F1B-F5B
 2.249787 with sigma of 0.001
 F6B-F2B = F6B-F3B = F6B-F4B = F6B-F5B
 2.249787 with sigma of 0.001
 F1C-F2C = F1C-F3C = F1C-F4C = F1C-F5C
 2.249787 with sigma of 0.001
 F6C-F2C = F6C-F3C = F6C-F4C = F6C-F5C
 2.249787 with sigma of 0.001
 F2A-F3A = F3A-F4A = F4A-F5A = F5A-F2A
 2.249787 with sigma of 0.001
 F2B-F3B = F3B-F4B = F4B-F5B = F5B-F2B
 2.249787 with sigma of 0.001
 F2C-F3C = F3C-F4C = F4C-F5C = F5C-F2C
 2.249787 with sigma of 0.001
 P2A-F7A = P2A-F8A = P2A-F9A = P2A-F10A = P2A-F11A = P2A-F12A
 1.59108 with sigma of 0.001
 P2B-F7B = P2B-F8B = P2B-F9B = P2B-F10B = P2B-F11B = P2B-F12B
 1.59108 with sigma of 0.001
 P2C-F7C = P2C-F8C = P2C-F9C = P2C-F10C = P2C-F11C = P2C-F12C
 1.59108 with sigma of 0.001
 F7A-F8A = F7A-F9A = F7A-F10A = F7A-F11A
 2.249787 with sigma of 0.001
 F7B-F8B = F7B-F9B = F7B-F10B = F7B-F11B
 2.249787 with sigma of 0.001
 F7C-F8C = F7C-F9C = F7C-F10C = F7C-F11C
 2.249787 with sigma of 0.001
 F12A-F8A = F12A-F9A = F12A-F10A = F12A-F11A
 2.249787 with sigma of 0.001
 F12B-F8B = F12B-F9B = F12B-F10B = F12B-F11B
 2.249787 with sigma of 0.001
 F12C-F8C = F12C-F9C = F12C-F10C = F12C-F11C
 2.249787 with sigma of 0.001
 F8A-F9A = F9A-F10A = F10A-F11A = F11A-F8A
 2.249787 with sigma of 0.001
 F8B-F9B = F9B-F10B = F10B-F11B = F11B-F8B
 2.249787 with sigma of 0.001
 F8C-F9C = F9C-F10C = F10C-F11C = F11C-F8C
 2.249787 with sigma of 0.001
 F2C-C44
 -3.15 with sigma of 0.001
 F8A-C22
 -3 with sigma of 0.005
3. Restrained planarity
 P1A, F2A, F3A, F4A, F5A
 with sigma of 0.1
 P1B, F2B, F3B, F4B, F5B
 with sigma of 0.1
 P1C, F2C, F3C, F4C, F5C
 with sigma of 0.1
 P2A, F8A, F9A, F10A, F11A
 with sigma of 0.1
 P2B, F8B, F9B, F10B, F11B
 with sigma of 0.1
 P2C, F8C, F9C, F10C, F11C
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
F2C \\sim F3C \\sim F4C \\sim F5C \\sim F2A \\sim F3A \\sim F4A \\sim F5A \\sim
F2B \\sim F3B \\sim F4B \\sim F5B: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
F8B \\sim F9B \\sim F10B \\sim F11B \\sim F8A \\sim F9A \\sim F10A \\sim F11A
\\sim F8C \\sim F9C \\sim F10C \\sim F11C: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Uanis(P1A) = Uanis(P1B) = Uanis(P1C)
Uanis(P2A) = Uanis(P2B) = Uanis(P2C)
Uanis(F1A) = Uanis(F1B) = Uanis(F1C)
Uanis(F6A) = Uanis(F6B) = Uanis(F6C)
Uanis(F7A) = Uanis(F7B) = Uanis(F7C)
Uanis(F12A) = Uanis(F12B) = Uanis(F12C)
5. Others
 1*[Sof(P1B)+Sof(F1B)+Sof(F2B)+Sof(F3B)+Sof(F4B)+Sof(F5B)+Sof(F6B)]+1*
 [Sof(P1C)+Sof(F1C)+Sof(F2C)+Sof(F3C)+Sof(F4C)+Sof(F5C)+Sof(F6C)]+1*[Sof(P1A)+
 Sof(F1A)+Sof(F2A)+Sof(F3A)+Sof(F4A)+Sof(F5A)+Sof(F6A)]=0.998 with esd of 0.001
 1*[Sof(P2A)+Sof(F7A)+Sof(F8A)+Sof(F9A)+Sof(F10A)+Sof(F11A)+Sof(F12A)]+1*
 [Sof(P2B)+Sof(F7B)+Sof(F8B)+Sof(F9B)+Sof(F10B)+Sof(F11B)+Sof(F12B)]+1*
 [Sof(P2C)+Sof(F7C)+Sof(F8C)+Sof(F9C)+Sof(F10C)+Sof(F11C)+Sof(F12C)]=1.0055
 with esd of 0.001
 Sof(P2A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(1)
 Sof(P1B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=FVAR(2)
 Sof(P1C)=Sof(F1C)=Sof(F2C)=Sof(F3C)=Sof(F4C)=Sof(F5C)=Sof(F6C)=FVAR(3)
 Sof(P1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(4)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(5)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1.414*
 FVAR(6)
 Sof(P2B)=Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(6)
 Sof(P2C)=Sof(F7C)=Sof(F8C)=Sof(F9C)=Sof(F10C)=Sof(F11C)=Sof(F12C)=FVAR(7)
6.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C19(H19A,H19B), C25(H25A,H25B), C41(H41A,H41B), C47(H47A,
 H47B), C53(H53A,H53B)
6.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), C31(H31), C32(H32), C33(H33),
  C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C43(H43), C44(H44),
 C45(H45), C49(H49), C50(H50), C51(H51)
6.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C54(H54A,H54B,
 H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              46214
_olex2_submission_special_instructions 'No special instructions were received'