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_7128379
_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         'C38 H48 Co N6 O2, 0.99(Cl O4), C2 H6 O'
_chemical_formula_sum            'C40 H54 Cl0.99 Co N6 O6.97'
_chemical_formula_weight         824.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-16
_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                 106.546(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.049(2)
_cell_length_b                   10.4508(9)
_cell_length_c                   36.994(3)
_cell_measurement_reflns_used    9870
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.36
_cell_measurement_theta_min      2.95
_cell_volume                     9283.4(13)
_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 0.967
_diffrn_measured_fraction_theta_max 0.961
_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_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.967
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            9241
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.413
_diffrn_reflns_theta_min         2.125
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.476
_exptl_absorpt_correction_T_max  0.953
_exptl_absorpt_correction_T_min  0.823
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 85570 reflections, Rint = 0.0817
 (42756 with I > 3sig(I), Rint = 0.0707)
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.180
_exptl_crystal_description       rod
_exptl_crystal_F_000             3485
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of ethanol and hexanes  by slow evaporation'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.978
_refine_diff_density_min         -0.461
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     602
_refine_ls_number_reflns         9241
_refine_ls_number_restraints     689
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0835
_refine_ls_R_factor_gt           0.0772
_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^)+94.2009P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1786
_refine_ls_wR_factor_ref         0.1812
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8391
_reflns_number_total             9241
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc01991k2.cif
_cod_data_source_block           ml023_sq
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 7128379--7128380.cif.
;
_cod_original_cell_volume        9283.3(15)
_cod_database_code               7128379
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.886
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6527(17)
 0.3473(17)
2. 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, All C(H,H,H,H,H,H) groups, All O(H) groups
3. Restrained distances
 Cl1A-O6A \\sim Cl1A-O4A \\sim Cl1A-O5A \\sim Cl1A-O3A
 with sigma of 0.01
 O3A-O4A \\sim O3A-O5A \\sim O3A-O6A \\sim O4A-O5A \\sim O4A-O6A \\sim O5A-O6A
 with sigma of 0.01
 Cl1B-O6B \\sim Cl1B-O4B \\sim Cl1B-O5B \\sim Cl1B-O3B
 with sigma of 0.01
 O3B-O4B \\sim O3B-O5B \\sim O3B-O6B \\sim O4B-O5B \\sim O4B-O6B \\sim O5B-O6B
 with sigma of 0.01
 O7-C40 \\sim O7A-C40A
 with sigma of 0.01
 C40-C39 \\sim C40A-C39
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim Cl1A \\sim O3A \\sim Cl1B \\sim
O3B \\sim O4B \\sim O5B \\sim O6B \\sim O4A \\sim O5A \\sim O6A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C39 \\sim O7 \\sim H7 \\sim C40 \\sim H40A \\sim H40B \\sim C40A \\sim H40C
\\sim H40D \\sim O7A \\sim H7A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(Cl1A) = Uanis(Cl1B)
Uanis(O6A) = Uanis(O6B)
5. Rigid body (RIGU) restrains
 Cl1, O3, O4, O5, O6, Cl1A, O3A, Cl1B, O3B, O4B, O5B, O6B, O4A, O5A, O6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, O7, H7, C40, H40A, H40B, C40A, H40C, H40D, O7A, H7A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 2*[Sof(Co1)+Sof(O1)+Sof(O2)+Sof(N1)+Sof(N2)+Sof(N3)+Sof(N4)+Sof(N5)+Sof(N6)+
 Sof(C1)+Sof(C2)+Sof(C3)+Sof(H3)+Sof(C4)+Sof(C5)+Sof(H5)+Sof(C6)+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)+Sof(C11)+Sof(C12)+Sof(H12A)+Sof(H12B)+Sof(H12C)+
 Sof(C13)+Sof(H13A)+Sof(H13B)+Sof(H13C)+Sof(C14)+Sof(H14A)+Sof(H14B)+Sof(H14C)+
 Sof(C15)+Sof(C16)+Sof(H16)+Sof(C17)+Sof(H17)+Sof(C18)+Sof(H18)+Sof(C19)+
 Sof(H19)+Sof(C20)+Sof(C21)+Sof(C22)+Sof(C23)+Sof(H23)+Sof(C24)+Sof(C25)+
 Sof(H25)+Sof(C26)+Sof(C27)+Sof(H27A)+Sof(H27B)+Sof(H27C)+Sof(C28)+Sof(H28A)+
 Sof(H28B)+Sof(H28C)+Sof(C29)+Sof(H29A)+Sof(H29B)+Sof(H29C)+Sof(C30)+Sof(C31)+
 Sof(H31A)+Sof(H31B)+Sof(H31C)+Sof(C32)+Sof(H32A)+Sof(H32B)+Sof(H32C)+Sof(C33)+
 Sof(H33A)+Sof(H33B)+Sof(H33C)+Sof(C34)+Sof(C35)+Sof(H35)+Sof(C36)+Sof(H36)+
 Sof(C37)+Sof(H37)+Sof(C38)+Sof(H38)+Sof(C39)+Sof(Q1)+Sof(Q2)+Sof(Q3)+Sof(Q4)+
 Sof(Q5)+Sof(Q6)+Sof(Q7)+Sof(Q8)+Sof(Q9)+Sof(Q10)]+3*[Sof(Co1)+Sof(O1)+Sof(O2)+
 Sof(N1)+Sof(N2)+Sof(N3)+Sof(N4)+Sof(N5)+Sof(N6)+Sof(C1)+Sof(C2)+Sof(C3)+
 Sof(H3)+Sof(C4)+Sof(C5)+Sof(H5)+Sof(C6)+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)+Sof(C11)+Sof(C12)+Sof(H12A)+Sof(H12B)+Sof(H12C)+Sof(C13)+Sof(H13A)+
 Sof(H13B)+Sof(H13C)+Sof(C14)+Sof(H14A)+Sof(H14B)+Sof(H14C)+Sof(C15)+Sof(C16)+
 Sof(H16)+Sof(C17)+Sof(H17)+Sof(C18)+Sof(H18)+Sof(C19)+Sof(H19)+Sof(C20)+
 Sof(C21)+Sof(C22)+Sof(C23)+Sof(H23)+Sof(C24)+Sof(C25)+Sof(H25)+Sof(C26)+
 Sof(C27)+Sof(H27A)+Sof(H27B)+Sof(H27C)+Sof(C28)+Sof(H28A)+Sof(H28B)+Sof(H28C)+
 Sof(C29)+Sof(H29A)+Sof(H29B)+Sof(H29C)+Sof(C30)+Sof(C31)+Sof(H31A)+Sof(H31B)+
 Sof(H31C)+Sof(C32)+Sof(H32A)+Sof(H32B)+Sof(H32C)+Sof(C33)+Sof(H33A)+Sof(H33B)+
 Sof(H33C)+Sof(C34)+Sof(C35)+Sof(H35)+Sof(C36)+Sof(H36)+Sof(C37)+Sof(H37)+
 Sof(C38)+Sof(H38)+Sof(C39)+Sof(Q1)+Sof(Q2)+Sof(Q3)+Sof(Q4)+Sof(Q5)+Sof(Q6)+
 Sof(Q7)+Sof(Q8)+Sof(Q9)+Sof(Q10)]+4*[Sof(Co1)+Sof(O1)+Sof(O2)+Sof(N1)+Sof(N2)+
 Sof(N3)+Sof(N4)+Sof(N5)+Sof(N6)+Sof(C1)+Sof(C2)+Sof(C3)+Sof(H3)+Sof(C4)+
 Sof(C5)+Sof(H5)+Sof(C6)+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)+Sof(C11)+
 Sof(C12)+Sof(H12A)+Sof(H12B)+Sof(H12C)+Sof(C13)+Sof(H13A)+Sof(H13B)+Sof(H13C)+
 Sof(C14)+Sof(H14A)+Sof(H14B)+Sof(H14C)+Sof(C15)+Sof(C16)+Sof(H16)+Sof(C17)+
 Sof(H17)+Sof(C18)+Sof(H18)+Sof(C19)+Sof(H19)+Sof(C20)+Sof(C21)+Sof(C22)+
 Sof(C23)+Sof(H23)+Sof(C24)+Sof(C25)+Sof(H25)+Sof(C26)+Sof(C27)+Sof(H27A)+
 Sof(H27B)+Sof(H27C)+Sof(C28)+Sof(H28A)+Sof(H28B)+Sof(H28C)+Sof(C29)+Sof(H29A)+
 Sof(H29B)+Sof(H29C)+Sof(C30)+Sof(C31)+Sof(H31A)+Sof(H31B)+Sof(H31C)+Sof(C32)+
 Sof(H32A)+Sof(H32B)+Sof(H32C)+Sof(C33)+Sof(H33A)+Sof(H33B)+Sof(H33C)+Sof(C34)+
 Sof(C35)+Sof(H35)+Sof(C36)+Sof(H36)+Sof(C37)+Sof(H37)+Sof(C38)+Sof(H38)+
 Sof(C39)+Sof(Q1)+Sof(Q2)+Sof(Q3)+Sof(Q4)+Sof(Q5)+Sof(Q6)+Sof(Q7)+Sof(Q8)+
 Sof(Q9)+Sof(Q10)]=1 with esd of 0.005
 Sof(Cl1)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=FVAR(1)
 Sof(Cl1A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=FVAR(2)
 Sof(Cl1B)=Sof(O3B)=Sof(O4B)=Sof(O5B)=Sof(O6B)=FVAR(3)
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(O7A)=Sof(H7A)=
 1-FVAR(4)
 Sof(O7)=Sof(H7)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 FVAR(4)
7.a Free rotating group:
 Cl1(O3,O4,O5,O6)
7.b Secondary CH2 refined with riding coordinates:
 C40(H40A,H40B), C40A(H40C,H40D)
7.c Me refined with riding coordinates:
 C39(H39D,H39E,H39F), C39(H39A,H39B,H39C)
7.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C16(H16), C17(H17), C18(H18), C19(H19), C23(H23), C25(H25),
 C35(H35), C36(H36), C37(H37), C38(H38)
7.e 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), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C)
7.f Idealised tetrahedral OH refined as rotating group:
 O7(H7), O7A(H7A)
;
_shelx_res_checksum              66794
_shelx_hkl_checksum              55732
_shelx_fab_checksum              23055
_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-11-5-4
_olex2_submission_special_instructions 'No special instructions were received'