Tuning the Reactivity of Terminal Nickel(III)-Oxygen Adducts for C-H Bond Activation.
Pirovano, Paolo; Farquhar, Erik R.; Swart, Marcel; McDonald, Aidan R.; Journal of the American Chemical Society 138 (2016) 14362–14370; doi:10.1021/jacs.6b08406

data_4130981
_publ_section_title
;
 Tuning the Reactivity of Terminal Nickel(III)-Oxygen Adducts for C-H Bond
 Activation.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14362
_journal_page_last               14370
_journal_paper_doi               10.1021/jacs.6b08406
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C8 H20 N, C23 H21 N4 Ni O5'
_chemical_formula_sum            'C31 H41 N5 Ni O5'
_chemical_formula_weight         622.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.1470(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.8415(9)
_cell_length_b                   11.2027(6)
_cell_length_c                   17.1224(8)
_cell_measurement_reflns_used    9911
_cell_measurement_temperature    100
_cell_measurement_theta_max      33.15
_cell_measurement_theta_min      2.18
_cell_volume                     3233.0(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX 3 (Bruker, 2015) '
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'XP (Bruker, 2008-2014)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'DUO Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX DUO KAPPA'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0238
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            55443
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         33.226
_diffrn_reflns_theta_min         2.183
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.645
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.6940
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0602 before and 0.0562 after correction.
The Ratio of minimum to maximum transmission is 0.9297.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_description       needle
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.368
_refine_diff_density_min         -0.997
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.030(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         12180
_refine_ls_number_restraints     32
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0555
_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^)+(0.0589P)^2^+7.1834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1351
_refine_ls_wR_factor_ref         0.1389
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                11146
_reflns_number_total             12180
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b08406_si_003.cif
_cod_data_source_block           tcd472_sq
_cod_database_code               4130981
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.882
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.970(16) 0.030(16)
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. Restrained distances
 C38-C40A
 2.4 with sigma of 0.01
 C40-C37A
 2.4 with sigma of 0.01
 N33-C34 \\sim N33-C36A \\sim N33-C38A \\sim N33-C40A \\sim N33-C36 \\sim
N33-C40 \\sim N33-C34A \\sim N33-
 C38
 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
Uanis(N33) = Uanis(C38) = Uanis(C39) = Uanis(C36A) = Uanis(C34) = Uanis(C38A) =
Uanis(C36) = Uanis(C40) = Uanis(C40A) = Uanis(C34A) = Uanis(C37) = Uanis(C35) =
Uanis(C39A) = Uanis(C37A) = Uanis(C41) = Uanis(C41A) = Uanis(C35A)
5. Others
 Fixed Sof: C34A(0.5) H34A(0.5) H34B(0.5) C35A(0.5) H35A(0.5) H35B(0.5)
 H35C(0.5) C36A(0.5) H36A(0.5) H36B(0.5) C37A(0.5) H37A(0.5) H37B(0.5)
 H37C(0.5) C38A(0.5) H38A(0.5) H38B(0.5) C39A(0.5) H39A(0.5) H39B(0.5)
 H39C(0.5) C40A(0.5) H40A(0.5) H40B(0.5) C41A(0.5) H41A(0.5) H41B(0.5)
 H41C(0.5) C34(0.5) H34C(0.5) H34D(0.5) C35(0.5) H35D(0.5) H35E(0.5) H35F(0.5)
 C36(0.5) H36C(0.5) H36D(0.5) C37(0.5) H37D(0.5) H37E(0.5) H37F(0.5) C38(0.5)
 H38C(0.5) H38D(0.5) C39(0.5) H39D(0.5) H39E(0.5) H39F(0.5) C40(0.5) H40C(0.5)
 H40D(0.5) C41(0.5) H41D(0.5) H41E(0.5) H41F(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C34A(H34A,H34B), C36A(H36A,H36B), C38A(H38A,H38B), C40A(H40A,H40B), C34(H34C,
 H34D), C36(H36C,H36D), C38(H38C,H38D), C40(H40C,H40D)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C23(H23), C24(H24),
 C25(H25)
6.c Idealised Me refined as rotating group:
 C35A(H35A,H35B,H35C), C37A(H37A,H37B,H37C), C39A(H39A,H39B,H39C), C41A(H41A,
 H41B,H41C), C35(H35D,H35E,H35F), C37(H37D,H37E,H37F), C39(H39D,H39E,H39F),
 C41(H41D,H41E,H41F), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              15517
_shelx_hkl_checksum              71836
_shelx_fab_checksum              92331
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method 'Mitegen holder in oil'
_olex2_submission_original_sample_id PP472
_olex2_submission_special_instructions 'No special instructions were received'