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_4128100
_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             2018-03-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   30.049(2)
_cell_length_b                   30.049(2)
_cell_length_c                   53.137(4)
_cell_measurement_reflns_used    9946
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      50.07
_cell_measurement_theta_min      2.94
_cell_volume                     47980(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 0.965
_diffrn_measured_fraction_theta_max 0.965
_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     0.1534
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_number            10591
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        47.500
_diffrn_reflns_theta_max         47.500
_diffrn_reflns_theta_min         2.941
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.383
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            GREEN
_exptl_crystal_density_diffrn    0.638
_exptl_crystal_description       STICK
_exptl_crystal_F_000             9648
_refine_diff_density_max         0.473
_refine_diff_density_min         -0.251
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1702 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.486(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.963
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     692
_refine_ls_number_reflns         10591
_refine_ls_number_restraints     578
_refine_ls_restrained_S_all      1.314
_refine_ls_R_factor_all          0.1487
_refine_ls_R_factor_gt           0.0992
_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^)+(0.1628P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2509
_refine_ls_wR_factor_ref         0.2712
_reflns_Friedel_coverage         0.893
_reflns_Friedel_fraction_full    0.959
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                5423
_reflns_number_total             10591
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02375_si_002.cif
_cod_data_source_block           100K
_cod_original_cell_volume        47980(8)
_cod_database_code               4128100
_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-C67 = O6-C67
 1.2 with sigma of 0.02
 C67-C68
 1.45 with sigma of 0.02
 O5-C68 = O6-C68
 2.4 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
 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
 1.4 with sigma of 0.02
 C53-C55 = C54-C56 = C55-C57 = C56-C58 = C57-C53 = C58-C54
 2.4 with sigma of 0.02
 C49-C41
 1.45 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
 2.8 with sigma of 0.01
 C52-C49
 1.5 with sigma of 0.01
 C60-C62
 2.8 with sigma of 0.01
 C40-C39
 1.4 with sigma of 0.01
 C53-O3
 1.3 with sigma of 0.02
 H52B-H42
 1.8 with sigma of 0.02
 H52B-H42 = H62C-H56
 1.9 with sigma of 0.02
 H47B-H46B
 1.8 with sigma of 0.02
 O3-C53
 1.35 with sigma of 0.01
 C39-O1
 1.35 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
 O5, O6, C67, C68
 with sigma of 0.1
 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
4. Rigid bond restraints
 C38, C35
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C25, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C27, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C48, C46
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C48, C47
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C48, C45
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C57, C59
 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
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(C18) \\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(C54) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C35) = Uanis(C38)
Uanis(C27) = Uanis(C26)
Uanis(C48) = Uanis(C47) = Uanis(C45) = Uanis(C46)
Uanis(C59) = Uanis(C62) = Uanis(C61) = Uanis(C60)
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              26608
_shelx_hkl_checksum              97780
_olex2_submission_special_instructions 'No special instructions were received'