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_7047944
_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'
_chemical_formula_sum            'C52 H58 Co N6 O2'
_chemical_formula_weight         857.97
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c 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                   22.556(5)
_cell_length_b                   12.003(2)
_cell_length_c                   16.456(3)
_cell_measurement_reflns_used    5683
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.0
_cell_measurement_theta_min      1.9
_cell_volume                     4455.3(15)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0823
_diffrn_reflns_av_unetI/netI     0.0831
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            22478
_diffrn_reflns_point_group_measured_fraction_full 0.865
_diffrn_reflns_point_group_measured_fraction_max 0.865
_diffrn_reflns_theta_full        25.023
_diffrn_reflns_theta_max         25.023
_diffrn_reflns_theta_min         1.922
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.433
_exptl_absorpt_correction_T_max  0.970
_exptl_absorpt_correction_T_min  0.958
_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_colour_primary    black
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prism
_exptl_crystal_F_000             1820
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.757
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 1786 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.007(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     593
_refine_ls_number_reflns         6811
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0491
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0487P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1056
_refine_ls_wR_factor_ref         0.1143
_reflns_Friedel_coverage         0.667
_reflns_Friedel_fraction_full    0.721
_reflns_Friedel_fraction_max     0.721
_reflns_number_gt                5683
_reflns_number_total             6811
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt03257b2.cif
_cod_data_source_block           5sepa
_cod_original_cell_volume        4455.1(16)
_cod_database_code               7047944
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.959
_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
 C38A-C37A \\sim C38A-C36A \\sim C38-C37 \\sim C38-C36 \\sim C37A-C36A \\sim
C37-C36
 with sigma of 0.04
 C35-C38A \\sim C35-C38 \\sim C35-C37A \\sim C35-C37 \\sim C35-C36A \\sim
C35-C36 \\sim C35-C34
 with sigma of 0.02
3. Others
 Sof(C36)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C38)=Sof(H38D)=Sof(H38E)=Sof(H38F)=
 Sof(C37)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(1)
 Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C37A)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C43(H43), C13(H13), C26(H26), C45(H45), C25(H25), C48(H48), C18(H18),
 C33(H33), C7(H7), C17(H17), C19(H19), C52(H52), C24(H24), C16(H16), C50(H50),
 C42(H42), C44(H44), C49(H49), C51(H51), C22(H22), C23(H23), C39(H39)
4.b Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C12(H12A,H12B,H12C), C4(H4A,H4B,H4C), C32(H32A,H32B,
 H32C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C31(H31A,H31B,H31C), C11(H11A,H11B,
 H11C), C10(H10A,H10B,H10C), C38A(H38A,H38B,H38C), C37A(H37A,H37B,H37C),
 C36A(H36A,H36B,H36C), C36(H36D,H36E,H36F), C38(H38D,H38E,H38F), C37(H37D,H37E,
 H37F)
;
_shelx_res_checksum              29297
_olex2_submission_special_instructions 'No special instructions were received'