Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity.
Corcos, Amanda R.; Villanueva, Omar; Walroth, Richard C.; Sharma, Savita K.; Bacsa, John; Lancaster, Kyle M.; MacBeth, Cora E.; Berry, John F.; Journal of the American Chemical Society 138 (2016) 1796–1799; doi:10.1021/jacs.5b12643

data_4130012
_publ_section_title
;
 Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand:
 Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex
 with Divergent Catalytic Reactivity.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1796
_journal_page_last               1799
_journal_paper_doi               10.1021/jacs.5b12643
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C21 H22 Co N4 O2, 2(C8 H20 N)'
_chemical_formula_sum            'C37 H62 Co N6 O2'
_chemical_formula_weight         681.85
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-10-06
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.421(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.150(5)
_cell_length_b                   16.151(7)
_cell_length_c                   22.239(10)
_cell_measurement_reflns_used    9948
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      29.775
_cell_measurement_theta_min      2.27
_cell_volume                     3879(3)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'APEX2 v2014.11 (Bruker, 2014)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0433
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            80214
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         31.504
_diffrn_reflns_theta_min         2.269
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           35
_diffrn_source_voltage           45
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.480
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6858
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0628 before and 0.0441 after correction.
The Ratio of minimum to maximum transmission is 0.9188.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.168
_exptl_crystal_description       block
_exptl_crystal_F_000             1476
_exptl_crystal_size_max          0.692
_exptl_crystal_size_mid          0.43
_exptl_crystal_size_min          0.396
_refine_diff_density_max         0.869
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     466
_refine_ls_number_reflns         12882
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0721
_refine_ls_R_factor_gt           0.0482
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0642P)^2^+1.7145P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1210
_refine_ls_wR_factor_ref         0.1353
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9540
_reflns_number_total             12882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b12643_si_001.cif
_cod_data_source_block           (Et4N)2(2)
_cod_database_code               4130012
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.732
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C19A-C18 \\sim C19B-C18
 with sigma of 0.003
3. Uiso/Uaniso restraints and constraints
Uanis(C5SA) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(N1SA) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C19A) = Uanis(C19B)
Uanis(N1SA) = Uanis(N1SB)
Uanis(C3SA) = Uanis(C3SB)
Uanis(C7SA) = Uanis(C7SB)
Uanis(C1SA) = Uanis(C1SB)
Uanis(C5SA) = Uanis(C5SB)
Uanis(C4SA) = Uanis(C4SB)
Uanis(C8SA) = Uanis(C8SB)
Uanis(C2SA) = Uanis(C2SB)
Uanis(C6SA) = Uanis(C6SB)
4. Rigid body (RIGU) restrains
 C18, C19A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2SA, N1SA, C1SA, C3SA, C5SA, C7SA, C4SA, C6SA, C8SA
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Same fragment restrains
{N1SB, C1SB, C2SB, C3SB, C4SB, C5SB, C6SB, C7SB, C8SB} sigma for 1-2: 0.002,
1-3: 0.002
as
{N1SA, C1SA, C2SA, C3SA, C4SA, C5SA, C6SA, C7SA, C8SA}
6. Others
 Sof(H18A)=Sof(C19B)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(1)
 Sof(H18)=Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(1)
 Sof(N1SB)=Sof(C1SB)=Sof(H1SC)=Sof(H1SD)=Sof(C2SB)=Sof(H2SD)=Sof(H2SE)=
 Sof(H2SF)=Sof(C3SB)=Sof(H3SC)=Sof(H3SD)=Sof(C4SB)=Sof(H4SD)=Sof(H4SE)=
 Sof(H4SF)=Sof(C5SB)=Sof(H5SC)=Sof(H5SD)=Sof(C6SB)=Sof(H6SD)=Sof(H6SE)=
 Sof(H6SF)=Sof(C7SB)=Sof(H7SC)=Sof(H7SD)=Sof(C8SB)=Sof(H8SD)=Sof(H8SE)=
 Sof(H8SF)=1-FVAR(2)
 Sof(N1SA)=Sof(C1SA)=Sof(H1SA)=Sof(H1SB)=Sof(C2SA)=Sof(H2SA)=Sof(H2SB)=
 Sof(H2SC)=Sof(C3SA)=Sof(H3SA)=Sof(H3SB)=Sof(C4SA)=Sof(H4SA)=Sof(H4SB)=
 Sof(H4SC)=Sof(C5SA)=Sof(H5SA)=Sof(H5SB)=Sof(C6SA)=Sof(H6SA)=Sof(H6SB)=
 Sof(H6SC)=Sof(C7SA)=Sof(H7SA)=Sof(H7SB)=Sof(C8SA)=Sof(H8SA)=Sof(H8SB)=
 Sof(H8SC)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C8(H8), C18(H18), C18(H18A)
7.b Secondary CH2 refined with riding coordinates:
 C1SA(H1SA,H1SB), C3SA(H3SA,H3SB), C5SA(H5SA,H5SB), C7SA(H7SA,H7SB), C1SB(H1SC,
 H1SD), C3SB(H3SC,H3SD), C5SB(H5SC,H5SD), C7SB(H7SC,H7SD), C9S(H9SA,H9SB),
 C11S(H11A,H11B), C13S(H13A,H13B), C15S(H15A,H15B)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15)
7.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C19A(H19A,H19B,H19C), C19B(H19D,H19E,
 H19F), C20(H20A,H20B,H20C), C2SA(H2SA,H2SB,H2SC), C4SA(H4SA,H4SB,H4SC),
 C6SA(H6SA,H6SB,H6SC), C8SA(H8SA,H8SB,H8SC), C2SB(H2SD,H2SE,H2SF), C4SB(H4SD,
 H4SE,H4SF), C6SB(H6SD,H6SE,H6SF), C8SB(H8SD,H8SE,H8SF), C10S(H10D,H10E,H10F),
 C12S(H12A,H12B,H12C), C14S(H14A,H14B,H14C), C16S(H16A,H16B,H16C)
;
_shelx_res_checksum              91464
_shelx_hkl_checksum              61080
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id SS-1-61A
_olex2_submission_special_instructions 'No special instructions were received'