A Co8 Metallacycle Stabilized by Double Anion-π interactions
Alexandropoulos, Dimitris I.; Dolinar, Brian; Xie, Haomiao; Vignesh, Kuduva; Dunbar, Kim R.; Chemical Communications  (2019) –; doi:10.1039/C9CC04151F

data_7123842
_publ_section_title
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 A Co8 Metallacycle Stabilized by Double Anion-\p interactions
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC04151F
_journal_year                    2019
_chemical_formula_moiety
'C184 H136 Co8 N32 O16, 1.25(C H2 Cl2), 8(C F3 O3 S), C4 H10 O'
_chemical_formula_sum            'C197.25 H148.51 Cl2.51 Co8 F24 N32 O41 S8'
_chemical_formula_weight         4895.70
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_symmetry_space_group_name_Hall  'I -4'
_symmetry_space_group_name_H-M   'I -4'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc21wbt3
_audit_creation_date             2019-03-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-29 deposited with the CCDC.    2019-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   26.9720(7)
_cell_length_b                   26.9720(7)
_cell_length_c                   14.8470(4)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      26.79
_cell_measurement_theta_min      2.18
_cell_volume                     10801.0(5)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_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 0.998
_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_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            34484
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.110
_diffrn_reflns_theta_min         2.388
_exptl_absorpt_coefficient_mu    0.807
_exptl_absorpt_correction_T_max  0.9669
_exptl_absorpt_correction_T_min  0.8658
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0846 before and 0.0473 after correction.
The Ratio of minimum to maximum transmission is 0.8954.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4973
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.077
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 0 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     881
_refine_ls_number_reflns         11873
_refine_ls_number_restraints     700
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0411P)^2^+2.7401P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0749
_refine_ls_wR_factor_ref         0.0834
_reflns_Friedel_coverage         0.923
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                10469
_reflns_number_total             11873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc04151f2.cif
_cod_data_source_block           da76ca
_cod_original_cell_volume        10801.0(6)
_cod_database_code               7123842
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.807
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.50(2)
 0.516(12) -0.007(13) -0.012(12)
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. Shared sites
{C22, C22A}
4. Restrained distances
 C1C-C1B
 2.374 with sigma of 0.02
 C41-C40 \\sim C41A-C40
 with sigma of 0.01
 C39-C37 \\sim C39-C37A
 with sigma of 0.01
 C39-C32 \\sim C39-C32A
 with sigma of 0.01
 C23-C22 \\sim C23-C22A
 with sigma of 0.01
 Cl2-C49 \\sim Cl2A-C49A \\sim Cl1A-C49A \\sim Cl1-C49
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C41A \\sim C42A
\\sim C43A \\sim C44A \\sim C45A \\sim C46A: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C17A \\sim C18A
\\sim C19A \\sim C20A \\sim C21A \\sim C22A: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Cl1 \\sim Cl2 \\sim C49 \\sim Cl1A \\sim Cl2A \\sim C49A: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
O11 \\sim C1A \\sim C1B \\sim C1C \\sim C1D: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Cl1 \\sim Cl2 \\sim C49 \\sim Cl1A \\sim Cl2A \\sim C49A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C1F \\sim O12 \\sim C1G \\sim C1E \\sim C1H \\sim C1A \\sim O11 \\sim C1B \\sim
C1C \\sim C1D: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C32 \\sim C33 \\sim H33 \\sim C34 \\sim H34 \\sim C35 \\sim C36 \\sim C37 \\sim
C37A \\sim C36A \\sim H36A \\sim C35A \\sim H35A \\sim C34A \\sim H34A \\sim
C33A \\sim C32A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C22) = Uanis(C22A)
6. Same fragment restrains
{C32, C33, C34, C35, C36, C37} sigma for 1-2: 0.04, 1-3: 0.04
{C41, C42, C43, C44, C45, C46} sigma for 1-2: 0.04, 1-3: 0.04
{C17A, C18A, C19A, C20A, C21A, C22A} sigma for 1-2: 0.04, 1-3: 0.04
{C41A, C42A, C43A, C44A, C45A, C46A} sigma for 1-2: 0.04, 1-3: 0.04
as
{C17, C18, C19, C20, C21, C22}
7. Others
 Sof(Cl1)=Sof(Cl2)=Sof(C49)=Sof(H49A)=Sof(H49B)=FVAR(1)
 Sof(Cl1A)=Sof(Cl2A)=Sof(C49A)=Sof(H49C)=Sof(H49D)=FVAR(2)
 Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=
 Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=1-FVAR(3)
 Sof(C41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=
 Sof(H45)=Sof(C46)=Sof(H46)=FVAR(3)
 Sof(C37A)=Sof(C36A)=Sof(H36A)=Sof(C35A)=Sof(H35A)=Sof(C34A)=Sof(H34A)=
 Sof(C33A)=Sof(H33A)=Sof(C32A)=Sof(H32A)=1-FVAR(4)
 Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=
 Sof(C36)=Sof(H36)=Sof(C37)=FVAR(4)
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=
 Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=1-FVAR(5)
 Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=
 Sof(C21)=Sof(H21)=Sof(C22)=FVAR(5)
 Sof(O11)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=
 Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(H1DC)=0.25*(1-
 FVAR(7))
 Sof(O12)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=Sof(H1EC)=Sof(C1F)=Sof(H1FA)=Sof(H1FB)=
 Sof(C1G)=Sof(H1GA)=Sof(H1GB)=Sof(C1H)=Sof(H1HA)=Sof(H1HB)=Sof(H1HC)=0.25*
 FVAR(7)
8.a Free rotating group:
 O12(C1E,C1F,C1G,C1H), O11(C1A,C1B,C1C,C1D)
8.b Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C49A(H49C,H49D), C1F(H1FA,H1FB), C1G(H1GA,H1GB), C1B(H1BA,
 H1BB), C1C(H1CA,H1CB)
8.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C14(H14), C15(H15), C16(H16), C24(H24), C27(H27), C28(H28), C29(H29), C30(H30),
  C31(H31), C39(H39), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21),
 C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C42(H42), C43(H43), C44(H44),
  C45(H45), C46(H46), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A),
 C21A(H21A), C36A(H36A), C35A(H35A), C34A(H34A), C33A(H33A), C32A(H32A),
 C42A(H42A), C43A(H43A), C44A(H44A), C45A(H45A), C46A(H46A)
8.d Fitted hexagon refined as free rotating group:
 C37A(C36A,C35A,C34A,C33A,C32A)
8.e Idealised Me refined with riding coordinates:
 C1E(H1EA,H1EB,H1EC), C1H(H1HA,H1HB,H1HC), C1A(H1AA,H1AB,H1AC), C1D(H1DA,H1DB,
 H1DC)
;
_shelx_res_checksum              44141
_olex2_submission_special_instructions 'No special instructions were received'