Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence.
McNeece, Andrew J.; Jesse, Kate; Xie, Jiaze; Filatov, Alexander S.; Anderson, John S.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c03244

data_4135046
_publ_section_title
;
 Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via
 Ligand-Based Redox Non-Innocence.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c03244
_journal_year                    2020
_chemical_formula_moiety         'C58 H68 F6 N10 Ni2 O6 S2'
_chemical_formula_sum            'C58 H68 F6 N10 Ni2 O6 S2'
_chemical_formula_weight         1296.76
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-12-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                71.701(12)
_cell_angle_beta                 76.170(11)
_cell_angle_gamma                69.672(13)
_cell_formula_units_Z            2
_cell_length_a                   12.197(6)
_cell_length_b                   15.166(8)
_cell_length_c                   21.970(11)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      19.93
_cell_measurement_theta_min      2.83
_cell_volume                     3579(3)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics
;
OLEX2: a complete structure solution, refinement and analysis program 
Dolomanov et al., 2009

Mercury: visualization and analysis of crystal structures
Macrae, et al., 2006

O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann.
J. Appl. Cryst. (2009). 42, 339-341;

C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
M. Towler and J. van de Streek, J. Appl. Cryst. (2006). 39, 453-457.
;
_computing_publication_material
;
 APEX3 v.2015.5-2 (Bruker AXS Inc., 2015)
 OLEX2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'XL-2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2014/5 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON 100'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            CMOS
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0758
_diffrn_reflns_av_unetI/netI     0.0739
_diffrn_reflns_Laue_measured_fraction_full 0.958
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            18028
_diffrn_reflns_point_group_measured_fraction_full 0.958
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        18.809
_diffrn_reflns_theta_max         18.809
_diffrn_reflns_theta_min         2.146
_diffrn_source                   'micro-focus X-ray tube'
_diffrn_source_type              'INCOATEC ImuS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.649
_exptl_absorpt_correction_T_max  0.7443
_exptl_absorpt_correction_T_min  0.3798
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.1452 before and 0.1060 after correction. 
The Ratio of minimum to maximum transmission is 0.6569.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.203
_exptl_crystal_description       block
_exptl_crystal_F_000             1352
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.22
_refine_diff_density_max         1.482
_refine_diff_density_min         -0.993
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     883
_refine_ls_number_reflns         5349
_refine_ls_number_restraints     1703
_refine_ls_restrained_S_all      0.917
_refine_ls_R_factor_all          0.1917
_refine_ls_R_factor_gt           0.1592
_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^)+(0.0290P)^2^+178.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3329
_refine_ls_wR_factor_ref         0.3534
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3820
_reflns_number_total             5349
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c03244_si_003.cif
_cod_data_source_block           Ni
_cod_database_code               4135046
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.870
_shelx_estimated_absorpt_t_min   0.800
_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
 S1-C61 = S4-C62
 1.81 with sigma of 0.005
 F2-C61
 1.32 with sigma of 0.01
 F6A-C62A = F6-C62
 1.32 with sigma of 0.01
 S1A-O2A \\sim S1-O2
 with sigma of 0.01
 S1A-C61A \\sim S1-C61
 with sigma of 0.01
 F2A-C61A \\sim F3-C61 \\sim F1-C61 \\sim F3A-C61A \\sim F2-C61 \\sim F1A-C61A
 with sigma of 0.005
 F3-F1 \\sim F1-F2 \\sim F3-F2
 with sigma of 0.005
 F2A-F1A \\sim F1A-F3A \\sim F2A-F3A
 with sigma of 0.005
 S4-O4 \\sim S4A-O4A
 with sigma of 0.01
 S4-C62 \\sim S4A-C62A
 with sigma of 0.01
 F4-C62 \\sim F6-C62 \\sim F5-C62 \\sim F5A-C62A \\sim F4A-C62A \\sim F6A-C62A
 with sigma of 0.01
 F4-F6 \\sim F6-F5 \\sim F4-F5
 with sigma of 0.01
 F4A-F6A \\sim F6A-F5A \\sim F4A-F5A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Others
 Sof(S1A)=Sof(O2A)=Sof(C61A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(S1)=Sof(O2)=Sof(C61)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(S4A)=Sof(O4A)=Sof(C62A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(2)
 Sof(S4)=Sof(O4)=Sof(C62)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15), C19(H19), C20(H20),
 C22(H22), C23(H23), C39(H39), C40(H40), C42(H42), C43(H43), C46(H46), C47(H47),
  C51(H51), C52(H52), C54(H54), C55(H55)
6.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C24(H24A,
 H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C)
;
_shelx_res_checksum              70514
_shelx_hkl_checksum              50012
_shelx_fab_checksum              7106
_olex2_submission_special_instructions 'No special instructions were received'