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_4131573
_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         'C81 H57 Co3 N18 O6, 1.5(C7 H8)'
_chemical_formula_sum            'C91.5 H72 Co3 N18 O6'
_chemical_formula_weight         1696.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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                 113.932(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.9034(18)
_cell_length_b                   11.6349(7)
_cell_length_c                   30.983(2)
_cell_measurement_reflns_used    9863
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      25.3314
_cell_measurement_theta_min      2.2657
_cell_volume                     8864.5(10)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      110.0
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.961
_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  0.0630
_diffrn_reflns_av_unetI/netI     0.0701
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            57247
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.369
_diffrn_reflns_theta_min         2.121
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.617
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7346
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1560 before and 0.0630 after correction. The Ratio of minimum to maximum transmission is 0.7346. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3504
_exptl_crystal_size_max          0.528
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.835
_refine_diff_density_min         -0.713
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1293
_refine_ls_number_reflns         16058
_refine_ls_number_restraints     572
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.1194
_refine_ls_R_factor_gt           0.0868
_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^)+(0.1048P)^2^+51.2690P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2157
_refine_ls_wR_factor_ref         0.2392
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11998
_reflns_number_total             16058
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b06925_si_002.cif
_cod_data_source_block           Compound_1
_cod_original_cell_volume        8864.6(10)
_cod_original_formula_sum        'C91.50 H72 Co3 N18 O6'
_cod_database_code               4131573
_shelx_shelxl_version_number     2016/6
_publ_section_exptl
;
Any special experimental details
;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9445(8)
 0.0555(8)
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
3. Uiso/Uaniso restraints and constraints
C60 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60A \\sim C55A
\\sim C56A \\sim C57A \\sim C58A \\sim C59A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C89 \\sim C90 \\sim C95 \\sim C94 \\sim C93 \\sim C92 \\sim C91 \\sim C89A
\\sim C90A \\sim C95A \\sim C94A \\sim C93A \\sim C92A \\sim C91A: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C10 \\sim C13 \\sim C11A \\sim H11A \\sim C12A \\sim H12A \\sim C14A \\sim C15A
\\sim C11 \\sim H11 \\sim C12 \\sim H12 \\sim C14 \\sim H14 \\sim C15: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C28A \\sim H32A \\sim C33A \\sim H33A \\sim C31 \\sim H31 \\sim C32 \\sim H32
\\sim C33 \\sim C32A: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Others
 Sof(H13A)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15)=1-FVAR(1)
 Sof(H13)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C14A)=Sof(H14A)=
 Sof(C15A)=Sof(H15A)=FVAR(1)
 Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=
 Sof(C32)=Sof(H32)=Sof(C33)=1-FVAR(2)
 Sof(C28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=
 Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=FVAR(2)
 Sof(C82A)=Sof(H82D)=Sof(H82E)=Sof(H82F)=Sof(C83A)=Sof(C88A)=Sof(H88A)=
 Sof(C87A)=Sof(H87A)=Sof(C86A)=Sof(H86A)=Sof(C85A)=Sof(H85A)=Sof(C84A)=
 Sof(H84A)=1-FVAR(3)
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C83)=Sof(C84)=Sof(H84)=Sof(C85)=
 Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=FVAR(3)
 Sof(C60A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57A)=
 Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=1-FVAR(4)
 Sof(C60)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=Sof(C58)=
 Sof(H58)=Sof(C59)=Sof(H59)=FVAR(4)
 Sof(C89A)=Sof(H89D)=Sof(H89E)=Sof(H89F)=Sof(C90A)=Sof(C95A)=Sof(H95A)=
 Sof(C94A)=Sof(H94A)=Sof(C93A)=Sof(H93A)=Sof(C92A)=Sof(H92A)=Sof(C91A)=
 Sof(H91A)=0.5*(1-FVAR(6))
 Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=Sof(C90)=Sof(C95)=Sof(H95)=Sof(C94)=
 Sof(H94)=Sof(C93)=Sof(H93)=Sof(C92)=Sof(H92)=Sof(C91)=Sof(H91)=0.5*FVAR(6)
5.a Free rotating group:
 C89(C90,C95,C94,C93,C92,C91), C82(C83,C84,C85,C86,C87,C88), C89A(C90A,C95A,
 C94A,C93A,C92A,C91A), C82A(C83A,C88A,C87A,C86A,C85A,C84A)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C13(H13), C13(H13A), C16(H16),
  C17(H17), C18(H18), C19(H19), C24(H24), C25(H25), C26(H26), C27(H27),
 C35(H35), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44),
  C45(H45), C46(H46), C51(H51), C52(H52), C53(H53), C54(H54), C62(H62),
 C65(H65), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72),
  C73(H73), C78(H78), C79(H79), C80(H80), C81(H81), C11A(H11A), C12A(H12A),
 C14A(H14A), C15A(H15A), C29A(H29A), C30A(H30A), C31A(H31A), C32A(H32A),
 C33A(H33A), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C11(H11),
 C12(H12), C14(H14), C15(H15), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
  C55A(H55A), C56A(H56A), C57A(H57A), C58A(H58A), C59A(H59A), C95(H95),
 C94(H94), C93(H93), C92(H92), C91(H91), C84(H84), C85(H85), C86(H86), C87(H87),
  C88(H88), C95A(H95A), C94A(H94A), C93A(H93A), C92A(H92A), C91A(H91A),
 C88A(H88A), C87A(H87A), C86A(H86A), C85A(H85A), C84A(H84A)
5.c Fitted hexagon refined as free rotating group:
 C60(C55,C56,C57,C58,C59), C60A(C55A,C56A,C57A,C58A,C59A)
5.d Idealised Me refined with riding coordinates:
 C89(H89A,H89B,H89C), C89A(H89D,H89E,H89F)
5.e Idealised Me refined as rotating group:
 C82(H82A,H82B,H82C), C82A(H82D,H82E,H82F)
;
_shelx_res_checksum              98869
_shelx_hkl_checksum              13586
_shelx_fab_checksum              12383
_olex2_submission_special_instructions 'No special instructions were received'