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_4135045
_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         'C28 H34 N5 Ni'
_chemical_formula_sum            'C28 H34 N5 Ni'
_chemical_formula_weight         499.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.198(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   51.354(6)
_cell_length_b                   5.7125(7)
_cell_length_c                   17.328(2)
_cell_measurement_reflns_used    9963
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.07
_cell_measurement_theta_min      2.35
_cell_volume                     5075.4(10)
_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 0.986
_diffrn_measured_fraction_theta_max 0.986
_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  0.0850
_diffrn_reflns_av_unetI/netI     0.0449
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       59
_diffrn_reflns_limit_h_min       -60
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            40928
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.164
_diffrn_reflns_theta_max         25.164
_diffrn_reflns_theta_min         2.354
_diffrn_source                   'micro-focus X-ray tube'
_diffrn_source_type              'INCOATEC ImuS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.790
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5620
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.1258 before and 0.0880 after correction. 
The Ratio of minimum to maximum transmission is 0.7542. 
;
_exptl_crystal_colour            'clear violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_description       plate
_exptl_crystal_F_000             2120
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.719
_refine_diff_density_min         -0.761
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         4486
_refine_ls_number_restraints     351
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0672
_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^)+(0.0624P)^2^+43.2597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1602
_refine_ls_wR_factor_ref         0.1703
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3654
_reflns_number_total             4486
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c03244_si_002.cif
_cod_data_source_block           mo_0719_amtbu
_cod_original_cell_volume        5075.5(10)
_cod_database_code               4135045
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.764
_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
 C22-C17 \\sim C22Y-C17 \\sim C22X-C17
 with sigma of 0.01
 C28Y-C25Y \\sim C28-C25 \\sim C28X-C25X
 with sigma of 0.01
 C27-C22 \\sim C27X-C22X \\sim C27Y-C22Y
 with sigma of 0.01
 C27-C26 \\sim C27X-C26X \\sim C27Y-C26Y
 with sigma of 0.01
 C26-C25 \\sim C26X-C25X \\sim C26Y-C25Y
 with sigma of 0.01
 C25X-C24X \\sim C25-C24 \\sim C25Y-C24Y
 with sigma of 0.01
 C24X-C23X \\sim C24-C23 \\sim C24Y-C23Y
 with sigma of 0.01
 C23X-C22X \\sim C23-C22 \\sim C23Y-C22Y
 with sigma of 0.01
 C24-C28 \\sim C26-C28
 with sigma of 0.01
 C25X-C24X \\sim C26X-C25X
 with sigma of 0.01
 C24X-C28X \\sim C26X-C28X
 with sigma of 0.01
 C24Y-C28Y \\sim C26Y-C28Y
 with sigma of 0.01
3. Restrained planarity
 C22, C23, C24, C25, C26, C27
 with sigma of 0.005
 C22X, C23X, C24X, C25X, C26X, C27X
 with sigma of 0.005
 C22Y, C23Y, C24Y, C25Y, C26Y, C27Y
 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C17:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C25X \\sim C26X \\sim C27X \\sim C22X \\sim C23X \\sim C24X \\sim C28X \\sim
C17: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C27Y \\sim C22Y \\sim C23Y \\sim C24Y \\sim C25Y \\sim C26Y \\sim C28Y \\sim
C17: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25Y) = Uanis(C25X) = Uanis(C25)
Uanis(C28X) = Uanis(C28Y) = Uanis(C28)
Uanis(C22) = Uanis(C22X) = Uanis(C22Y)
5. Rigid body (RIGU) restrains
 C22, C23, C24, C25, C26, C27, C28, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C25X, C26X, C27X, C22X, C23X, C24X, C28X, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C27Y, C22Y, C23Y, C24Y, C25Y, C26Y, C28Y, C17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Fixed Sof: C22(0.5) C23(0.5) H23(0.5) C24(0.5) H24(0.5) C25(0.5) C26(0.5)
 H26(0.5) C27(0.5) H27(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C25X(0.25)
 C26X(0.25) H26X(0.25) C27X(0.25) H27X(0.25) C22X(0.25) C23X(0.25) H23X(0.25)
 C24X(0.25) H24X(0.25) C28X(0.25) H28D(0.25) H28E(0.25) H28F(0.25) C27Y(0.25)
 H27Y(0.25) C22Y(0.25) C23Y(0.25) H23Y(0.25) C24Y(0.25) H24Y(0.25) C25Y(0.25)
 C26Y(0.25) H26Y(0.25) C28Y(0.25) H28G(0.25) H28H(0.25) H28I(0.25)
7.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15), C23(H23), C24(H24),
 C26(H26), C27(H27), C26X(H26X), C27X(H27X), C23X(H23X), C24X(H24X), C27Y(H27Y),
  C23Y(H23Y), C24Y(H24Y), C26Y(H26Y)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C19(H19A,
 H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C28(H28A,H28B,H28C),
 C28X(H28D,H28E,H28F), C28Y(H28G,H28H,H28I)
;
_shelx_res_checksum              58069
_shelx_hkl_checksum              54230
_olex2_submission_special_instructions 'No special instructions were received'