Six-coordinate [CoIII(L)2]z (z = 1‒, 0, 1+) complexes of an azo-appended o-aminophenolate in amidate(2‒) and iminosemiquinonate π-radical (1‒) redox-levels: existence of valence-tautomerism
Rajput, Amit; Sharma, Anuj K.; Barman, Suman K.; Lloret, Francesc; Mukherjee, Rabi; Dalton Transactions  (2018) –; doi:10.1039/C8DT03257B

data_7047946
_publ_section_title
;
 Six-coordinate [CoIII(L)2]z (z = 1--, 0, 1+) complexes of an azo-appended
 o-aminophenolate in amidate(2--) and iminosemiquinonate \p-radical (1--)
 redox-levels: existence of valence-tautomerism
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/C8DT03257B
_journal_year                    2018
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C52 Co N6 O2, 3(F2 P0.33)'
_chemical_formula_sum            'C52 H58 Co F6 N6 O2 P'
_chemical_formula_weight         1002.98
_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_Hall           ' R 3 -2"c'
_space_group_name_H-M_alt        'R 3 c'
_symmetry_Int_Tables_number      161
_symmetry_space_group_name_Hall  'R 3 -2"c'
_symmetry_space_group_name_H-M   'R 3 c :H'
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-04
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.05.22 svn.r3414 for OlexSys, GUI svn.r5347)
;
_audit_update_record
;
2017-08-06 deposited with the CCDC.
2018-11-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   31.315(3)
_cell_length_b                   31.315(3)
_cell_length_c                   29.732(5)
_cell_measurement_reflns_used    4223
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      19.10
_cell_measurement_theta_min      2.25
_cell_volume                     25250(5)
_computing_cell_refinement       'SAINT v6.45A (Bruker, 2003)'
_computing_data_reduction        'SAINT v6.45A (Bruker, 2003)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.755
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1233
_diffrn_reflns_av_unetI/netI     0.0968
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            53813
_diffrn_reflns_theta_full        26.3720
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         2.03
_exptl_absorpt_coefficient_mu    0.395
_exptl_absorpt_correction_T_max  0.931
_exptl_absorpt_correction_T_min  0.4941
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.1872
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       BLOCK
_exptl_crystal_F_000             9444.9368
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.8397
_refine_diff_density_min         -0.6463
_refine_diff_density_rms         0.1031
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   -0.01(6)
_refine_ls_d_res_high            0.8000
_refine_ls_d_res_low             10.0182
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0419
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    98
_refine_ls_number_parameters     597
_refine_ls_number_reflns         8681
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.0389
_refine_ls_R_factor_all          0.1038
_refine_ls_R_factor_gt           0.0786
_refine_ls_shift/su_max          0.0070
_refine_ls_shift/su_mean         0.0002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1409P)^2^+5.9575P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1985
_refine_ls_wR_factor_ref         0.2197
_reflns_Friedel_coverage         0.514
_reflns_limit_h_max              33
_reflns_limit_h_min              -33
_reflns_limit_k_max              19
_reflns_limit_k_min              -19
_reflns_limit_l_max              37
_reflns_limit_l_min              -20
_reflns_number_gt                6646
_reflns_number_total             8681
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            c8dt03257b2.cif
_cod_data_source_block           10janc
_cod_database_code               7047946
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.936
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F4aa-F3a \\sim F4aa-F1a \\sim F4aa-F2a \\sim F3a-F1a \\sim F3a-F2a
 with sigma of 0.04
 F4aa-F1a \\sim F4aa-F2a
 with sigma of 0.04
 P1a-F4aa \\sim P1a-F3a \\sim P1a-F1a \\sim P1a-F2a
 with sigma of 0.02
 F4-F1 \\sim F4-F2 \\sim F4-F3 \\sim F4-F5 \\sim F6-F1 \\sim F6-F2 \\sim F6-F3
\\sim F6-F5 \\sim F1-F3 \\sim F1-F5
 \\sim F2-F3 \\sim F2-F5
 with sigma of 0.04
 P1-F4 \\sim P1-F6 \\sim P1-F1 \\sim P1-F2 \\sim P1-F3 \\sim P1-F5
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C23 \\sim C24: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C49 \\sim C50: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C48 \\sim C47: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(F4a) = Uanis(F4aa)
Uanis(F4a) = Uanis(F3a)
Uanis(F6) = Uanis(F1)
Uanis(C4) = Uanis(C5) = Uanis(C6) = Uanis(C3) = Uanis(C37) = Uanis(C36) =
Uanis(C38) = Uanis(C35)
Uanis(F1) = Uanis(F5)
4. Rigid body (RIGU) restrains
 F2a, P1a, F4aa, F3a, F1a
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F3a, F2a, P1a, F4aa, F1a
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P1a, F4aa, F1a, F2a
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F4a)=1-FVAR(1)
 Sof(F3a)=FVAR(1)
 Fixed Sof: P1(0.66667) F4(0.66667) F6(0.66667) F1(0.66667) F2(0.66667)
 F3(0.66667) F5(0.66667) F4aa(0.3333)
6.a Aromatic/amide H refined with riding coordinates:
 C19(H19), C18(H18), C44(H44), C42(H42), C43(H43), C33(H33), C45(H45),
 C23(H23), C48(H48), C16(H16), C17(H17), C39(H39), C22(H22), C13(H13), C26(H26),
  C7(H7), C49(H49), C24(H24), C52(H52), C51(H51), C50(H50), C25(H25)
6.b Idealised Me refined as rotating group:
 C30(H30a,H30b,H30c), C4(H4a,H4b,H4c), C32(H32a,H32b,H32c), C31(H31a,H31b,
 H31c), C5(H5a,H5b,H5c), C10(H10a,H10b,H10c), C6(H6a,H6b,H6c), C12(H12a,H12b,
 H12c), C38(H38a,H38b,H38c), C11(H11a,H11b,H11c), C36(H36a,H36b,H36c), C37(H37a,
 H37b,H37c)
;
_olex2_submission_special_instructions 'No special instructions were received'