Valence tautomerism in a [2 ×2] Co<sub>4</sub> grid complex containing a ditopic arylazo ligand.
Bonanno, Nico M.; Watts, Zackery; Mauws, Cole; Patrick, Brian O.; Wiebe, Christopher R.; Shibano, Yuki; Sugisaki, Kenji; Matsuoka, Hideto; Shiomi, Daisuke; Sato, Kazunobu; Takui, Takeji; Lemaire, Martin T.; Chemical communications (Cambridge, England) 57 (2021) 6213–6216; doi:10.1039/d1cc01991k

data_7128380
_publ_section_title
;
 Valence tautomerism in a [2 \\times 2] Co<sub>4</sub> grid complex
 containing a ditopic arylazo ligand.
;
_journal_issue                   50
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              6213
_journal_page_last               6216
_journal_paper_doi               10.1039/d1cc01991k
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C128 H168 Co4 N24 O8'
_chemical_formula_sum            'C128 H168 Co4 N24 O8'
_chemical_formula_weight         2406.57
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-11 deposited with the CCDC.	2021-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   39.4401(13)
_cell_length_b                   39.4401(13)
_cell_length_c                   10.4150(5)
_cell_measurement_reflns_used    9856
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.67
_cell_measurement_theta_min      2.70
_cell_volume                     16200.8(11)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'Bruker-Nonius Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1084
_diffrn_reflns_av_unetI/netI     0.0981
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            40015
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        22.779
_diffrn_reflns_theta_max         22.779
_diffrn_reflns_theta_min         2.271
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.453
_exptl_absorpt_correction_T_max  0.991
_exptl_absorpt_correction_T_min  0.761
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1172 before and 0.0614 after correction. The ratio of minimum to maximum transmission is 0.7684. The \l/2 correction factor is not present.'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    0.987
_exptl_crystal_description       blade
_exptl_crystal_F_000             5104
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and acetonitrile  by slow evaporation'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.363
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Twinning involves inversion, so Flack parameter cannot be determined
;
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     834
_refine_ls_number_reflns         10379
_refine_ls_number_restraints     1551
_refine_ls_restrained_S_all      0.970
_refine_ls_R_factor_all          0.0926
_refine_ls_R_factor_gt           0.0681
_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^)+(0.0816P)^2^+35.9213P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1588
_refine_ls_wR_factor_ref         0.1693
_reflns_Friedel_coverage         0.877
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                7982
_reflns_number_total             10379
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01991k2.cif
_cod_data_source_block           ml021_sq
_cod_depositor_comments
'Adding full bibliography for 7128379--7128380.cif.'
_cod_original_cell_volume        16200.8(13)
_cod_database_code               7128380
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.858
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.60(3)
 0.012(10) 0.39(3) -0.000(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C21-C25 \\sim C21-C25A \\sim C53-C57
 with sigma of 0.01
 C26-C27 \\sim C27-C28 \\sim C28-C26 \\sim C26A-C27A \\sim C27A-C28A \\sim
C28A-C26A
 with sigma of 0.01
 C25-C26 \\sim C25-C27 \\sim C25-C28 \\sim C25A-C26A \\sim C25A-C27A \\sim
C25A-C28A
 with sigma of 0.01
 C7-C10 \\sim C8-C7 \\sim C9-C7
 with sigma of 0.01
 C8-C9 \\sim C9-C10 \\sim C10-C8
 with sigma of 0.01
 C9A-C7A \\sim C7A-C10A \\sim C8A-C7A
 with sigma of 0.01
 C8A-C9A \\sim C9A-C10A \\sim C10A-C8A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C46) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C9A) = Uanis(C9)
Uanis(C8A) = Uanis(C8)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C25A)=Sof(C28A)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(1)
 Sof(C25)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=Sof(C26)=Sof(H26D)=Sof(H26E)=Sof(H26F)=FVAR(1)
 Sof(C7A)=Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(2)
 Sof(C7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C15(H15), C17(H17), C20(H20), C22(H22), C35(H35), C37(H37),
 C47(H47), C49(H49), C52(H52), C54(H54)
7.b 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), C26A(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C58(H58A,H58B,
 H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C63(H63A,
 H63B,H63C), C64(H64A,H64B,H64C), C28A(H28D,H28E,H28F), C27A(H27D,H27E,H27F),
 C26(H26D,H26E,H26F), C10A(H10D,H10E,H10F), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,
 H9AC)
;
_shelx_res_checksum              95279
_shelx_hkl_checksum              79081
_shelx_fab_checksum              19372
_platon_squeeze_void_probe_radius 1.20
_olex2_diffrn_ambient_temperature_device Kryoflex
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in oil'
_olex2_submission_original_sample_id NB-11-2-24
_olex2_submission_special_instructions 'No special instructions were received'