Unconventional Method for Fabricating Valence Tautomeric Materials: Integrating Redox Center within a Metal-Organic Framework.
Li, Bao; Zhao, Yu-Meng; Kirchon, Angelo; Pang, Jian-Dong; Yang, Xin-Yu; Zhuang, Gui-Lin; Zhou, Hong-Cai; Journal of the American Chemical Society 141 (2019) 6822–6826; doi:10.1021/jacs.9b02375

data_4128102
_publ_section_title
;
 Unconventional Method for Fabricating Valence Tautomeric Materials:
 Integrating Redox Center within a Metal-Organic Framework.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6822
_journal_page_last               6826
_journal_paper_doi               10.1021/jacs.9b02375
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C68 H77 Co2 N4 O6'
_chemical_formula_sum            'C68 H77 Co2 N4 O6'
_chemical_formula_weight         1164.20
_space_group_crystal_system      tetragonal
_space_group_IT_number           120
_space_group_name_Hall           'I -4 -2c'
_space_group_name_H-M_alt        'I -4 c 2'
_symmetry_space_group_name_Hall  'I -4 -2c'
_symmetry_space_group_name_H-M   'I -4 c 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   31.034(2)
_cell_length_b                   31.034(2)
_cell_length_c                   53.217(4)
_cell_measurement_reflns_used    4086
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      39.71
_cell_measurement_theta_min      2.61
_cell_volume                     51254(6)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.2147
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_number            3095
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        28.499
_diffrn_reflns_theta_max         28.499
_diffrn_reflns_theta_min         2.848
_exptl_absorpt_coefficient_mu    2.231
_exptl_crystal_colour            GREEN
_exptl_crystal_density_diffrn    0.604
_exptl_crystal_description       STICK
_exptl_crystal_F_000             9840
_refine_diff_density_max         0.251
_refine_diff_density_min         -0.197
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 280 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.45(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.841
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     740
_refine_ls_number_reflns         3095
_refine_ls_number_restraints     1098
_refine_ls_restrained_S_all      1.427
_refine_ls_R_factor_all          0.2233
_refine_ls_R_factor_gt           0.1127
_refine_ls_shift/su_max          1.152
_refine_ls_shift/su_mean         0.026
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2529
_refine_ls_wR_factor_ref         0.3129
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                1030
_reflns_number_total             3095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02375_si_002.cif
_cod_data_source_block           250K
_cod_original_cell_volume        51254(8)
_cod_database_code               4128102
_shelx_shelxl_version_number     2014/7
_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
 O5-C68 = O6-C68
 2.4 with sigma of 0.02
 O5-C67 = O6-C67
 1.2 with sigma of 0.02
 C67-C68
 1.45 with sigma of 0.02
 O5-O6
 2.1 with sigma of 0.02
 C8-C7 = C7-C6 = C6-N2 = N2-C10 = C10-C9 = C9-C8
 1.44 with sigma of 0.01
 C7-C13
 2.6 with sigma of 0.03
 C9-C13
 2.6 with sigma of 0.03
 N2-C9 = C10-C8 = C9-C7 = C8-C6 = C7-N2 = C6-C10
 2.45 with sigma of 0.01
 C1-C2 = C2-C3 = C3-C4 = C4-C5 = C5-N1 = N1-C1
 1.44 with sigma of 0.01
 N1-C2 = C1-C3 = C2-C4 = C3-C5 = C4-N1
 2.45 with sigma of 0.01
 C11-C12 = C12-C13 = C13-C14 = C14-C15 = C15-C16 = C16-C11
 1.44 with sigma of 0.01
 C11-C13 = C12-C14 = C13-C15 = C14-C16 = C15-C11 = C16-C12
 2.45 with sigma of 0.01
 C20-C21 = C21-C22 = C22-C23 = C23-C24 = C24-N3 = N3-C20
 1.44 with sigma of 0.01
 N3-C21 = C20-C22 = C21-C23 = C22-C24 = C23-N3 = C24-C20
 2.45 with sigma of 0.01
 N4-C25 = C25-C26 = C26-C27 = C27-C28 = C28-C29 = C29-N4
 1.44 with sigma of 0.01
 N4-C26 = C25-C27 = C26-C28 = C27-C29 = C28-N4 = C29-C25
 2.45 with sigma of 0.01
 C30-C31 = C31-C32 = C32-C33 = C33-C34 = C34-C35 = C35-C30
 1.45 with sigma of 0.01
 C30-C32 = C31-C33 = C32-C34 = C33-C35 = C34-C30 = C35-C31
 2.45 with sigma of 0.01
 C39-C40 = C40-C41 = C41-C42 = C42-C43 = C43-C44 = C44-C39
 1.4 with sigma of 0.02
 C39-C41 = C40-C42 = C41-C43 = C42-C44 = C43-C39 = C44-C40
 2.4 with sigma of 0.02
 C53-C54 = C54-C55 = C55-C56 = C56-C57 = C57-C58 = C58-C53
 1.45 with sigma of 0.02
 C53-C55 = C54-C56 = C55-C57 = C56-C58 = C57-C53 = C58-C54
 2.45 with sigma of 0.02
 C49-C41
 1.5 with sigma of 0.01
 C49-C40
 2.45 with sigma of 0.01
 C49-C42
 2.45 with sigma of 0.01
 C63-C55
 1.45 with sigma of 0.01
 C63-C54
 2.45 with sigma of 0.01
 C57-C59
 1.45 with sigma of 0.01
 C65-C63
 1.45 with sigma of 0.01
 C59-C62
 1.45 with sigma of 0.01
 C63-C64
 1.5 with sigma of 0.01
 C48-C45
 1.5 with sigma of 0.01
 C61-C59
 1.5 with sigma of 0.01
 C60-C59
 1.5 with sigma of 0.01
 C61-C60
 2.8 with sigma of 0.01
 C50-C49
 1.5 with sigma of 0.01
 C51-C49
 1.5 with sigma of 0.01
 C49-C52
 1.5 with sigma of 0.01
 C50-C51
 2.7 with sigma of 0.01
 C60-C62
 2.8 with sigma of 0.01
 C58-O3
 2.45 with sigma of 0.01
 O3-C54
 2.45 with sigma of 0.01
 O2-C40
 1.3 with sigma of 0.02
 O2-C41
 2.4 with sigma of 0.01
 O1-C39
 1.3 with sigma of 0.02
 C54-O4
 1.3 with sigma of 0.01
 C53-O3
 1.35 with sigma of 0.01
 C39-C40
 1.4 with sigma of 0.01
 O2-Co02
 2 with sigma of 0.02
 O2-C39
 2.45 with sigma of 0.02
 C48-C47
 1.5 with sigma of 0.02
 C65-C66 = C47-C46
 2.5 with sigma of 0.02
 O1-C40
 2.45 with sigma of 0.02
 O1-C44
 2.45 with sigma of 0.02
 C41-O2
 2.45 with sigma of 0.02
 O4-C53
 2.45 with sigma of 0.02
 O4-C55
 2.45 with sigma of 0.02
 C53-C54
 1.45 with sigma of 0.02
 C11-C2
 2.45 with sigma of 0.02
 C11-C4
 2.45 with sigma of 0.02
 C54-C53
 1.45 with sigma of 0.01
 C52-C49
 1.3 with sigma of 0.01
 C46-C48
 1.5 with sigma of 0.01
 C52-C50
 2.6 with sigma of 0.02
 C52-C51
 2.6 with sigma of 0.02
 C48-C43
 1.45 with sigma of 0.01
 C50-C52
 2.5 with sigma of 0.01
 C51-C52
 2.5 with sigma of 0.01
 C41-C42
 1.4 with sigma of 0.01
 C41-C43
 2.45 with sigma of 0.01
 C41-C52
 2.5 with sigma of 0.01
 C42-C43
 1.4 with sigma of 0.01
 C59-C61
 1.5 with sigma of 0.01
 C61-C62
 2.45 with sigma of 0.02
 C66-C63
 1.5 with sigma of 0.02
 C12-C17
 1.45 with sigma of 0.02
 C19-C14
 1.45 with sigma of 0.01
 C11-C17
 2.45 with sigma of 0.02
 C13-C17
 2.45 with sigma of 0.02
 C23-C30
 2.45 with sigma of 0.02
 C21-C30
 2.45 with sigma of 0.02
 C31-C36
 1.45 with sigma of 0.02
 C30-C36
 2.45 with sigma of 0.03
 C36-C32
 2.45 with sigma of 0.03
 C38-C35
 1.45 with sigma of 0.01
 C38-C30
 2.45 with sigma of 0.02
 C38-C34
 2.45 with sigma of 0.02
 C22-C30
 1.45 with sigma of 0.01
 C39-O1
 1.35 with sigma of 0.01
 C40-C39
 1.4 with sigma of 0.01
 C1-C2 \\sim C3-C4 \\sim C5-N1
 with sigma of 0.02
 C39-C40 \\sim C41-C42 \\sim C43-C44
 with sigma of 0.02
 C34-C35 \\sim C30-C31 \\sim C32-C33
 with sigma of 0.02
 C6-N2 \\sim C10-C9 \\sim C8-C7
 with sigma of 0.02
 C24-N3 \\sim C20-C21 \\sim C23-C22
 with sigma of 0.02
 C31-C30 \\sim C35-C34 \\sim C33-C32
 with sigma of 0.02
 C28-C27 \\sim C26-C25 \\sim N4-C29
 with sigma of 0.02
 C62-C59 \\sim C60-C61
 with sigma of 0.02
 C59-C62 \\sim C61-C60
 with sigma of 0.02
 N4-C29 \\sim C28-C27 \\sim C26-C25
 with sigma of 0.02
 C49-C52 \\sim C50-C51
 with sigma of 0.02
 C62-C60 \\sim C59-C61
 with sigma of 0.02
3. Restrained planarity
 C39, C40, C41, C42, C43, C44
 with sigma of 0.01
 C8, C7, C6, N2, C10, C9
 with sigma of 0.01
 C1, C2, C3, C4, C5, N1
 with sigma of 0.01
 C28, C27, C26, C25, N4, C29
 with sigma of 0.01
 C36, C31, C30, C35, C34, C33, C32, C37, C38
 with sigma of 0.1
 C49, C41, C42, C40
 with sigma of 0.01
 C42, C43, C44, C48
 with sigma of 0.01
 C55, C54, C53, C58, C57, C56, C59, C63
 with sigma of 0.01
 C22, C30, C31, C32, C27, C33, C34, C35
 with sigma of 0.01
 O3, C53, C54, C58
 with sigma of 0.1
 O2, C40, C39, C41
 with sigma of 0.1
 O1, C39, C40, C44
 with sigma of 0.1
 C16, C12, C11, C3
 with sigma of 0.1
 C11, C3, C2, C4
 with sigma of 0.1
 C17, C12, C11, C13
 with sigma of 0.1
 C11, C16, C18, C15
 with sigma of 0.1
 C15, C14, C13, C19
 with sigma of 0.1
 C12, C11, C16, C15, C14, C13
 with sigma of 0.1
 C24, C23, C22, C21, C20, N3
 with sigma of 0.1
 C21, C22, C30, C23
 with sigma of 0.1
 O5, C67, C68, O6
 with sigma of 0.1
 C14, C15, C16, C11, C12, C13
 with sigma of 0.1
 C19, C14, C15, C13
 with sigma of 0.1
 C17, C11, C12, C13
 with sigma of 0.1
 C8, C13, C7, C9
 with sigma of 0.1
4. Rigid bond restraints
 C38, C35
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C8 \\sim C7 \\sim C6 \\sim N2 \\sim C10 \\sim C9: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim N1: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
C57 \\sim C59 \\sim C61 \\sim C62 \\sim C60: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C43 \\sim C48 \\sim C45 \\sim C47 \\sim C46: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C38 \\sim C35: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C20 \\sim C54 \\sim C18 \\sim C11 \\sim C36 \\sim C32 \\sim C53 \\sim C27 \\sim
C58 \\sim C21 \\sim C7 \\sim C8 \\sim C19 \\sim C16 \\sim C66 \\sim C22 \\sim
C13 \\sim C28 \\sim C56 \\sim C51 \\sim C10 \\sim C33 \\sim C59 \\sim C41 \\sim
C40 \\sim C42 \\sim C39 \\sim C9 \\sim C48 \\sim C2 \\sim C52 \\sim C64 \\sim
C60 \\sim C37 \\sim C65 \\sim C1 \\sim C61 \\sim C12 \\sim C31 \\sim C17 \\sim
C30 \\sim C15 \\sim C38 \\sim C14 \\sim C23 \\sim C57 \\sim C6 \\sim C68 \\sim
C43 \\sim C46 \\sim C45 \\sim C47 \\sim C25 \\sim C49 \\sim C63 \\sim C3 \\sim
C24 \\sim C55 \\sim C29 \\sim C50 \\sim C34 \\sim C4 \\sim C5 \\sim C35 \\sim
C26 \\sim C44 \\sim C62 \\sim C67 \\sim O1 \\sim O3 \\sim O2 \\sim O4 \\sim O6
\\sim O5 \\sim N1 \\sim N2 \\sim N3 \\sim N4 \\sim Co01 \\sim Co02: within 2A
with sigma of 0.0001 and sigma for terminal atoms of 0.02
Uanis(Co01) \\sim Ueq, Uanis(Co02) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C32) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C37) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C12) \\sim Ueq,
Uanis(C15) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C36) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C57) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C45)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N3) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C68) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C17) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C38) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C38) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O4) \\sim
Ueq, Uanis(O6) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C65) \\sim Ueq,
Uanis(C29) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C64) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C11) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(Co01) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
6.a Aromatic/amide H refined with riding coordinates:
 C20(H20), C58(H58), C21(H21), C7(H7), C28(H28), C56(H56), C10(H10), C42(H42),
 C9(H9), C2(H2), C1(H1), C23(H23), C6(H6), C25(H25), C24(H24), C29(H29), C4(H4),
  C5(H5), C26(H26), C44(H44)
6.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C36(H36A,H36B,H36C), C19(H19A,H19B,H19C), C66(H66A,H66B,
 H66C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C64(H64A,H64B,H64C), C60(H60A,
 H60B,H60C), C37(H37A,H37B,H37C), C65(H65A,H65B,H65C), C61(H61A,H61B,H61C),
 C17(H17A,H17B,H17C), C38(H38A,H38B,H38C), C68(H68A,H68B,H68C), C46(H46A,H46B,
 H46C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C50(H50A,H50B,H50C), C62(H62A,
 H62B,H62C)
;
_shelx_res_checksum              96952
_shelx_hkl_checksum              89073
_olex2_submission_special_instructions 'No special instructions were received'