Putting a New Spin on Supramolecular Metallacycles: Co<sub>3</sub> Triangle and Co<sub>4</sub> Square Bearing Tetrazine-Based Radicals as Bridges.
Alexandropoulos, Dimitris I.; Dolinar, Brian S.; Vignesh, Kuduva R.; Dunbar, Kim R.; Journal of the American Chemical Society 139 (2017) 11040–11043; doi:10.1021/jacs.7b06925

data_4131574
_publ_section_title
;
 Putting a New Spin on Supramolecular Metallacycles: Co<sub>3</sub>
 Triangle and Co<sub>4</sub> Square Bearing Tetrazine-Based Radicals as
 Bridges.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11040
_journal_page_last               11043
_journal_paper_doi               10.1021/jacs.7b06925
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety
'C108 H76 Co4 N24 O8, 4.14(C2 H3 N1), 0.16(C2 N)'
_chemical_formula_sum            'C116.5 H88.26 Co4 N28.25 O8'
_chemical_formula_weight         2247.55
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.0961(16)
_cell_length_b                   33.161(3)
_cell_length_c                   34.712(3)
_cell_measurement_reflns_used    9283
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      23.184
_cell_measurement_theta_min      2.397
_cell_volume                     21981(3)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_data_collection       'APEX3(Bruker-AXS, 2015)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      200.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker PHOTON area detector'
_diffrn_measurement_method       '0.5\ \w and 0.5\ \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0778
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            132605
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        23.309
_diffrn_reflns_theta_max         23.309
_diffrn_reflns_theta_min         2.146
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.664
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7610
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1469 before and 0.0750 after correction. The Ratio of minimum to maximum transmission is 0.7610. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             9256
_exptl_crystal_size_max          0.375
_exptl_crystal_size_mid          0.255
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.584
_refine_diff_density_min         -0.496
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.165
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1665
_refine_ls_number_reflns         15800
_refine_ls_number_restraints     974
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.1228
_refine_ls_R_factor_gt           0.0876
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0370P)^2^+147.2740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1854
_refine_ls_wR_factor_ref         0.2024
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11632
_reflns_number_total             15800
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b06925_si_002.cif
_cod_data_source_block           Compound_2
_cod_original_formula_sum        'C116.50 H88.26 Co4 N28.25 O8'
_cod_database_code               4131574
_shelx_shelxl_version_number     2016/6
_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. Shared sites
{O3A, O3}
3. Restrained distances
 C7-C6 \\sim C7-C6A \\sim C55-C54 \\sim C55A-C54
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C1A \\sim C2A \\sim C3A
\\sim C4A \\sim C5A \\sim C6A: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O3 \\sim C16 \\sim C17 \\sim C21 \\sim C22 \\sim O3A \\sim O4A \\sim C22A \\sim
C23A \\sim C24A \\sim C20 \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim
C21A \\sim C16A \\sim C18 \\sim C19 \\sim O4 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C25A \\sim C26A \\sim
C27A \\sim C28A \\sim C29A \\sim C30A: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.02
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C31A \\sim C32A \\sim C33A
\\sim C34A \\sim C35A \\sim C36: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C55A \\sim C56A
\\sim C57A \\sim C58A \\sim C59A \\sim C60A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
N4S \\sim C7S \\sim C8S \\sim N4T \\sim C7T \\sim C8T: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02
C9S \\sim N5S \\sim C10S: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C10S \\sim C9S \\sim N5S \\sim N5T \\sim C9T \\sim C10T: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(O3A) = Uanis(O3)
5. Same fragment restrains
{O3A, O4A, C16A, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A,
C27A, C28A, C29A, C30A} sigma for 1-2: 0.02, 1-3: 0.04
as
{O3, O4, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29,
C30}
6. Others
 1*[Sof(O3)+Sof(O4)+Sof(C16)+Sof(H16)+Sof(C17)+Sof(H17)+Sof(C18)+Sof(H18)+
 Sof(C19)+Sof(H19)+Sof(C20)+Sof(H20)+Sof(C21)+Sof(C22)+Sof(C23)+Sof(H23)+
 Sof(C24)+Sof(C25)+Sof(C26)+Sof(H26)+Sof(C27)+Sof(H27)+Sof(C28)+Sof(H28)+
 Sof(C29)+Sof(H29)+Sof(C30)+Sof(H30)+Sof(O3A)+Sof(O4A)+Sof(C16A)+Sof(H16A)+
 Sof(C17A)+Sof(H17A)+Sof(C18A)+Sof(H18A)+Sof(C19A)+Sof(H19A)+Sof(C20A)+
 Sof(H20A)+Sof(C21A)+Sof(C22A)+Sof(C23A)+Sof(H23A)+Sof(C24A)+Sof(C25A)+
 Sof(C26A)+Sof(H26A)+Sof(C27A)+Sof(H27A)+Sof(C28A)+Sof(H28A)+Sof(C29A)+
 Sof(H29A)+Sof(C30A)+Sof(H30A)]+1*[Sof(N5S)+Sof(C9S)+Sof(C10S)+Sof(H10A)+
 Sof(H10B)+Sof(H10C)]+1*[Sof(N5T)+Sof(C9T)+Sof(C10T)]=1 with esd of 0
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=1-FVAR(1)
 Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=
 Sof(H5)=Sof(C6)=FVAR(1)
 Sof(O3A)=Sof(O4A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(C22A)=Sof(C23A)=
 Sof(H23A)=Sof(C24A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=
 Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=1-FVAR(2)
 Sof(O3)=Sof(O4)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=
 Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(C22)=Sof(C23)=Sof(H23)=
 Sof(C24)=Sof(C25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=
 Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=FVAR(2)
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=
 Sof(H34A)=Sof(C35A)=Sof(H35A)=1-FVAR(3)
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=
 Sof(C35)=Sof(H35)=FVAR(3)
 Sof(C55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=
 Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=1-FVAR(4)
 Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=
 Sof(H59)=Sof(C60)=Sof(H60)=FVAR(4)
 Sof(N4S)=Sof(C7S)=Sof(C8S)=Sof(H8SA)=Sof(H8SB)=Sof(H8SC)=FVAR(5)
 Sof(N5S)=Sof(C9S)=Sof(C10S)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(6)
 Sof(N4T)=Sof(C7T)=Sof(C8T)=Sof(H8TA)=Sof(H8TB)=Sof(H8TC)=FVAR(7)
 Sof(N5T)=Sof(C9T)=Sof(C10T)=FVAR(8)
7.a Free rotating group:
 N4S(C7S,C8S), N5S(C9S,C10S), N4T(C7T,C8T), N5T(C9T,C10T)
7.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C38(H38), C41(H41),
 C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49),
  C50(H50), C53(H53), C61(H61), C62(H62), C63(H63), C64(H64), C69(H69),
 C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C81(H81),
  C82(H82), C83(H83), C84(H84), C85(H85), C86(H86), C87(H87), C88(H88),
 C93(H93), C94(H94), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99),
 C100(H100), C105(H105), C106(H106), C107(H107), C108(H108), C1(H1), C2(H2),
 C3(H3), C4(H4), C5(H5), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20),
 C23(H23), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
  C33(H33), C34(H34), C35(H35), C56(H56), C57(H57), C58(H58), C59(H59),
 C60(H60), C1A(H1A), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C16A(H16A),
 C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A), C23A(H23A), C26A(H26A),
 C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A), C31A(H31A), C32A(H32A),
 C33A(H33A), C34A(H34A), C35A(H35A), C56A(H56A), C57A(H57A), C58A(H58A),
 C59A(H59A), C60A(H60A)
7.c Fitted hexagon refined as free rotating group:
 C16(C17,C18,C19,C20,C21), C1A(C2A,C3A,C4A,C5A,C6A), C16A(C17A,C18A,C19A,C20A,
 C21A), C31A(C32A,C33A,C34A,C35A,C36), C55A(C56A,C57A,C58A,C59A,C60A)
7.d Idealised Me refined as rotating group:
 C8S(H8SA,H8SB,H8SC), C10S(H10A,H10B,H10C), C2S(H2SA,H2SB,H2SC), C8T(H8TA,H8TB,
 H8TC), C4S(H4SA,H4SB,H4SC), C6S(H6SA,H6SB,H6SC)
;
_shelx_res_checksum              33785
_shelx_hkl_checksum              86847
_olex2_submission_special_instructions 'No special instructions were received'