Electronic structure and reactivity of nickel(i) pincer complexes: their aerobic transformation to peroxo species and site selective C–H oxygenation
Rettenmeier, Christoph A.; Wadepohl, Hubert; Gade, Lutz H.; Chem. Sci. 7 (2016) 3533–; doi:10.1039/C5SC04644K

data_1542423
_publ_section_title
;
 Electronic structure and reactivity of nickel(i) pincer complexes: their
 aerobic transformation to peroxo species and site selective C--H
 oxygenation
;
_journal_issue                   6
_journal_name_full               'Chem. Sci.'
_journal_page_first              3533
_journal_paper_doi               10.1039/C5SC04644K
_journal_volume                  7
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H25 N3 Ni O4'
_chemical_formula_sum            'C18 H25 N3 Ni O4'
_chemical_formula_weight         406.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_cr67
_audit_creation_date
;
'Mon Apr 28 13:48:13 2014'
;
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2015-11-26 deposited with the CCDC.
2016-02-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.25709(10)
_cell_length_b                   16.6261(3)
_cell_length_c                   17.4692(2)
_cell_measurement_reflns_used    29975
_cell_measurement_temperature    110(1)
_cell_measurement_theta_max      28.5880
_cell_measurement_theta_min      3.6450
_cell_volume                     1817.34(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-15); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      110(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega   11.00   57.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
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  2 omega  -37.00   58.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -80.0000  179.2873 190

  3 omega   -4.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -76.0000 -126.8406 120

  4 omega   21.00   58.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -80.0000  -75.2412 74

  5 omega  -43.00   28.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -76.0000  102.3005 142

  6 omega   31.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
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  7 omega   29.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
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  8 omega   -4.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   77.0000  150.0000 200

  9 omega    5.00   32.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   57.0000   60.0000 54

 10 omega   68.00   95.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   57.0000 -120.0000 54

 11 omega  -42.00    8.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
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 12 omega   -4.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   77.0000   60.0000 200

 13 omega  -27.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -77.0000    0.0000 166

 14 omega   -3.00   93.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   77.0000  -60.0000 192

 15 omega  -39.00   17.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
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 16 omega   10.00   70.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   77.0000 -150.0000 120

 17 omega    2.00   32.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   38.0000   90.0000 60

 18 omega   47.00   74.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   38.0000   90.0000 54

 19 omega  -44.00  -17.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -38.0000  150.0000 54

 20 omega  -38.00  -11.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -77.0000  -60.0000 54

 21 omega   29.00   54.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -77.0000  -60.0000 50

 22 omega  -44.00    2.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -78.0000   52.5304 92

 23 omega    5.00   95.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   57.0000   90.0000 180

 24 omega  -43.00   47.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -57.0000  -30.0000 180

 25 omega    1.00   99.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   38.0000   30.0000 196

 26 omega  -47.00   70.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -19.0000    0.0000 234

 27 omega  -43.00   47.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -57.0000 -120.0000 180

 28 omega    1.00   99.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   38.0000 -150.0000 196

 29 omega   -4.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   77.0000   30.0000 200

 30 omega  -43.00   47.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -57.0000  120.0000 180

 31 omega  -44.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -77.0000  -30.0000 200

 32 omega    5.00   95.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   57.0000 -150.0000 180

 33 omega  -44.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -76.0000 -126.8406 200

 34 omega    5.00   95.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   57.0000  120.0000 180

 35 omega  -44.00   57.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -78.0000   52.5304 202

 36 omega    5.00   95.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   57.0000  -30.0000 180

 37 omega  -44.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -77.0000    0.0000 200

 38 omega  -44.00   56.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727  -77.0000  120.0000 200

 39 omega  -46.00  100.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727    8.0000  159.0000 292

 40 omega   -4.00   96.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727   77.0000  -90.0000 200

 41 omega  -47.00   99.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727    0.0000 -180.0000 292

 42 omega  -47.00   99.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727    0.0000 -150.0000 292

 43 omega  -47.00   15.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727    0.0000 -120.0000 124

 44 omega  -46.00  100.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       26.2727    8.0000  159.0000 292

;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_UB_11      -0.0060789000
_diffrn_orient_matrix_UB_12      0.0425776000
_diffrn_orient_matrix_UB_13      -0.0006388000
_diffrn_orient_matrix_UB_21      -0.1126233000
_diffrn_orient_matrix_UB_22      -0.0023965000
_diffrn_orient_matrix_UB_23      -0.0040710000
_diffrn_orient_matrix_UB_31      -0.0114511000
_diffrn_orient_matrix_UB_32      0.0004330000
_diffrn_orient_matrix_UB_33      0.0404044000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0945
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            155621
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.470
_diffrn_reflns_theta_min         3.383
_diffrn_source                   'microfocus X-Ray tube'
_exptl_absorpt_coefficient_mu    1.096
_exptl_absorpt_correction_T_max  0.904
_exptl_absorpt_correction_T_min  0.587
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.484
_exptl_crystal_description       irregular
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.353
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.922
_refine_diff_density_min         -0.680
_refine_diff_density_rms         0.148
_refine_ls_abs_structure_details
;
 Flack x determined using 2159 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         6454
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0577
_refine_ls_R_factor_gt           0.0451
_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^)+(0.0794P)^2^+0.4340P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1251
_refine_ls_wR_factor_ref         0.1319
_reflns_Friedel_coverage         0.753
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                5569
_reflns_number_total             6454
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc04644k2.cif
_cod_data_source_block           ga_cr67
_cod_depositor_comments
'Adding full bibliography for 1542422--1542426.cif.'
_cod_database_code               1542423
_audit_block_refno               2025
_audit_block_usercomment         'cr_ts40 orange irregular'
_chemical_oxdiff_formula         'C18 H25 N3 Ni1 O4'
_chemical_oxdiff_usercomment     'cr_ts40 orange irregular'
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.698
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_shelxl_version_number           2014/7
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C12(H12), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C7(H7A,H7B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C9(H9)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C)
;
_shelx_res_checksum              29146
_olex2_submission_special_instructions 'No special instructions were received'
_cell_oxdiff_length_a            6.25668(13)
_cell_oxdiff_length_b            16.6318(3)
_cell_oxdiff_length_c            17.46441(19)
_cell_oxdiff_angle_alpha         90.0016(12)
_cell_oxdiff_angle_beta          89.9963(13)
_cell_oxdiff_angle_gamma         90.0726(16)
_cell_oxdiff_volume              1817.34(5)
_cell_oxdiff_measurement_reflns_used 29975