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_7047945
_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_formula_moiety         'C52 H58 Co N6 O2, C10 H10 Co, C2 H3 N'
_chemical_formula_sum            'C64 H71 Co2 N7 O2'
_chemical_formula_weight         1088.13
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-02
_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                90
_cell_formula_units_Z            4
_cell_length_a                   22.6297(14)
_cell_length_b                   14.1505(9)
_cell_length_c                   17.5120(11)
_cell_measurement_reflns_used    6689
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.0
_cell_measurement_theta_min      1.8
_cell_volume                     5607.7(6)
_computing_cell_refinement       'SAINT v6.45A (Bruker, 2003)'
_computing_data_collection       'Bruker SMART'
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0706
_diffrn_reflns_av_unetI/netI     0.0755
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            28318
_diffrn_reflns_point_group_measured_fraction_full 0.823
_diffrn_reflns_point_group_measured_fraction_max 0.823
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.800
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.642
_exptl_absorpt_correction_T_max  0.960
_exptl_absorpt_correction_T_min  0.938
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
R(int) was 0.0678 before and 0.0430 after correction.
The Ratio of minimum to maximum transmission is 0.2956.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.289
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2296
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.641
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 1942 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.027(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     720
_refine_ls_number_reflns         8128
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0636
_refine_ls_R_factor_gt           0.0484
_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^)+(0.0577P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1125
_reflns_Friedel_coverage         0.590
_reflns_Friedel_fraction_full    0.633
_reflns_Friedel_fraction_max     0.633
_reflns_number_gt                6689
_reflns_number_total             8128
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03257b2.cif
_cod_data_source_block           1octa
_cod_database_code               7047945
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.948
_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
 C36-C37 \\sim C36-C38 \\sim C37-C38 \\sim C38A-C37A \\sim C38A-C36A \\sim
C37A-C36A
 with sigma of 0.04
 C35-C34 \\sim C35-C36 \\sim C35-C37 \\sim C35-C38 \\sim C35-C38A \\sim
C35-C37A \\sim C35-C36A
 with sigma of 0.02
3. Others
 Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C26(H26), C33(H33), C7(H7), C16(H16), C48(H48), C45(H45), C49(H49), C58(H58),
 C19(H19), C61(H61), C42(H42), C62(H62), C44(H44), C60(H60), C43(H43), C22(H22),
  C13(H13), C64(H64), C57(H57), C23(H23), C52(H52), C56(H56), C17(H17),
 C39(H39), C50(H50), C18(H18), C63(H63), C55(H55), C24(H24), C59(H59), C51(H51),
  C25(H25)
4.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C5(H5A,H5B,
 H5C), C30(H30A,H30B,H30C), C6(H6A,H6B,H6C), C4(H4A,H4B,H4C), C11(H11A,H11B,
 H11C), C10(H10A,H10B,H10C), C53(H53A,H53B,H53C), C36(H36A,H36B,H36C), C37(H37A,
 H37B,H37C), C38(H38A,H38B,H38C), C38A(H38D,H38E,H38F), C37A(H37D,H37E,H37F),
 C36A(H36D,H36E,H36F)
;
_shelx_res_checksum              46072
_olex2_submission_special_instructions 'No special instructions were received'