Synthesis and catalytic activity of nickel(II) complexes containing NCN pincer ligands
Ashwin G. Nair; Roy T. McBurney; Mark R.D. Gatus; D.Barney Walker; Mohan Bhadbhade; Barbara A. Messerle; Journal of Organometallic Chemistry 845 (2017) 63–70; doi:10.1016/j.jorganchem.2017.02.025

data_4032688
_publ_section_title
;
 Synthesis and catalytic activity of nickel(II) complexes containing NCN
 pincer ligands
;
_journal_name_full               'Journal of Organometallic Chemistry'
_journal_page_first              63
_journal_page_last               70
_journal_paper_doi               10.1016/j.jorganchem.2017.02.025
_journal_volume                  845
_journal_year                    2017
_chemical_formula_moiety         'C26 H32 N12 Ni, 2(C24 H20 B)'
_chemical_formula_sum            'C74 H72 B2 N12 Ni'
_chemical_formula_weight         1209.76
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_symmetry_space_group_name_Hall  '-P 2yac'
_symmetry_space_group_name_H-M   'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_cell_angle_alpha                90
_cell_angle_beta                 118.202(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.4252(19)
_cell_length_b                   12.5805(9)
_cell_length_c                   24.392(2)
_cell_measurement_reflns_used    2090
_cell_measurement_temperature    150.02
_cell_measurement_theta_max      17.887
_cell_measurement_theta_min      2.553
_cell_volume                     6335.0(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.02
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1770
_diffrn_reflns_av_unetI/netI     0.2310
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            54119
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.345
_diffrn_reflns_theta_min         1.876
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.361
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5758
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1903 before and 0.0707 after correction.
The Ratio of minimum to maximum transmission is 0.7724.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       plate
_exptl_crystal_F_000             2552
_exptl_crystal_size_max          0.101
_exptl_crystal_size_mid          0.076
_exptl_crystal_size_min          0.024
_refine_diff_density_max         1.086
_refine_diff_density_min         -1.355
_refine_diff_density_rms         0.106
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.162
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     899
_refine_ls_number_reflns         14127
_refine_ls_number_restraints     896
_refine_ls_restrained_S_all      1.143
_refine_ls_R_factor_all          0.3076
_refine_ls_R_factor_gt           0.1380
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3634
_refine_ls_wR_factor_ref         0.4603
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4839
_reflns_number_total             14127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            J-Org-Chem-2017-845-63-70-1.cif
_cod_data_source_block           1
_cod_original_cell_volume        6334.9(9)
_cod_database_code               4032688
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 N1C'-C1C' \\sim N1C-C1C
 with sigma of 0.02
 N3C-C8C \\sim N3C'-C8C'
 with sigma of 0.02
 N2C'-N1C' \\sim N2C-N1C
 with sigma of 0.02
 C2C-C1C \\sim C3C-C2C \\sim C2C'-C1C' \\sim C3C'-C2C'
 with sigma of 0.02
 N3C-C5C \\sim N3C'-C5C' \\sim N2C-C4C \\sim N2C'-C4C'
 with sigma of 0.02
 C5C'-C4C' \\sim C5C-C4C
 with sigma of 0.02
 Ni0A-N1C'_$1 \\sim Ni0A-N1C_$1
 with sigma of 0.02
 Ni0A-C8C_$1 \\sim Ni0A-C8C'_$1
 with sigma of 0.02
 C13C-C12C \\sim C12C-C11C
 with sigma of 0.02
 N5C-N6C \\sim N6C'-N5C'
 with sigma of 0.02
 N5C-C13C \\sim N6C'-C11'
 with sigma of 0.02
 C1C-N2C \\sim C1C'-N2C'
 with sigma of 0.02
 N2C'-N1C' \\sim N2C-N1C \\sim N1C'-C1C' \\sim N1C-C1C
 with sigma of 0.02
 N4D'-C9D' \\sim N4D-C9D
 with sigma of 0.02
 N4D-C9D \\sim N4D'-C9D'
 with sigma of 0.02
 C9D-C10D \\sim C9D'-C102
 with sigma of 0.02
 N4D'-C102 \\sim C10D-N4D
 with sigma of 0.02
 N5D-C10D \\sim N5D-N6D \\sim N5D-C13D
 with sigma of 0.02
 N5D-C10D \\sim N5D'-C102
 with sigma of 0.02
 C9D-N5D \\sim N5D'-C9D'
 with sigma of 0.02
 N5D'-C102 \\sim N5D-C10D
 with sigma of 0.02
 C102-N6D' \\sim C10D-N6D
 with sigma of 0.02
 C112-C102 \\sim C10D-C13D
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(N4C) = Uanis(C1C')
Uanis(C7C') = Uanis(C2C)
Uanis(N1D) = Uanis(N3D')
Uanis(N2D') = Uanis(N3D)
Uanis(C6D) = Uanis(C3D')
Uanis(C2D') = Uanis(C7D)
4. Rigid body (RIGU) restrains
 C11B, C12B, H12B, C13B, H13B, C14B, H14B, C15B, H15B, C16B, H16B, C21B, C22B,
 H22B, C23B, H23B, C24B, H24B, C25B, H25B, C26B, H26B, C31B, H31B, C32B, H32B,
 C33B, H33B, C34B, H34B, C35B, H35B, C36B, C41B, C42B, H42B, C43B, H43B, C44B,
 H44B, C45B, H45B, C46B, B1B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C9', C10', C11', C12', C13', Ni0A, N1C', N2C', N3C', N4C', N5C', N6C', C1C',
 C2C', C3C', C4C', C5C', C6C', C7C', C8C', N1C, N2C, N3C, N4C, N5C, N6C, C1C,
 C2C, C3C, C4C, C5C, C6C, C8C, C9C, C10C, C11C, C12C, C13C, C7C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C102, C112, C122, C132, Ni1A, N1D', N2D', N3D', N4D', N5D', N6D', C1D', C2D',
 C3D', C4D', C5D', C6D', C7D', C8D', C9D', N2D, N6D, N4D, N1D, N3D, N5D, C3D,
 C11D, C7D, C1D, C5D, C9D, C13D, C2D, C4D, C6D, C8D, C10D, C12D
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C11A, C12A, H12A, C13A, H13A, C14A, H14A, C15A, H15A, C16A, H16A, C21A, C22A,
 H22A, C23A, H23A, C24A, H24A, C25A, H25A, C26A, H26A, C31A, C32A, H32A, C33A,
 H33A, C34A, H34A, C35A, H35A, C36A, H36A, C41A, C42A, H42A, C43A, H43A, C44A,
 H44A, C45A, H45A, C46A, H46A, B1A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: C102(0.5) H10A(0.5) H10B(0.5) N2D'(0.5) C3D'(0.5) H3D'(0.5)
 C2D'(0.5) H2D'(0.5) C1D'(0.5) H1D'(0.5) N1D'(0.5) N5D'(0.5) N6D'(0.5)
 C132(0.5) H132(0.5) C122(0.5) H122(0.5) C112(0.5) H112(0.5) C4D'(0.5)
 H4DC(0.5) H4DD(0.5) C5D'(0.5) H5DC(0.5) H5DD(0.5) C6D'(0.5) H6D'(0.5)
 N3D'(0.5) C8D'(0.5) N4D'(0.5) C7D'(0.5) H7D'(0.5) C9D'(0.5) H9DC(0.5)
 H9DD(0.5) C9'(0.5) H9'A(0.5) H9'B(0.5) C10'(0.5) H10E(0.5) H10F(0.5) N1C'(0.5)
 N2C'(0.5) N3C'(0.5) N4C'(0.5) N5C'(0.5) C13'(0.5) H13'(0.5) C12'(0.5)
 H12'(0.5) C11'(0.5) H11'(0.5) N6C'(0.5) C1C'(0.5) H1C'(0.5) C2C'(0.5)
 H2C'(0.5) C3C'(0.5) H3C'(0.5) C4C'(0.5) H4CC(0.5) H4CD(0.5) C5C'(0.5)
 H5CC(0.5) H5CD(0.5) C6C'(0.5) H6C'(0.5) C7C'(0.5) H7C'(0.5) C8C'(0.5) N6D(0.5)
 N5D(0.5) C13D(0.5) H5FA(0.5) C12D(0.5) H28(0.5) C11D(0.5) H9DE(0.5) N1C(0.5)
 N2C(0.5) N3D(0.5) C6D(0.5) H6D(0.5) C7D(0.5) H7D(0.5) N4D(0.5) C8D(0.5)
 N3C(0.5) N4C(0.5) N6C(0.5) C11C(0.5) H11(0.5) C12C(0.5) H8IA(0.5) C13C(0.5)
 H9IA(0.5) N5C(0.5) C3D(0.5) H3D(0.5) N1D(0.5) N2D(0.5) C1D(0.5) H1D(0.5)
 C2D(0.5) H2D(0.5) C1C(0.5) H1C(0.5) C2C(0.5) H2C(0.5) C5D(0.5) H5DA(0.5)
 H5DB(0.5) C3C(0.5) H3C(0.5) C9D(0.5) H9DA(0.5) H9DB(0.5) C4C(0.5) H4CA(0.5)
 H4CB(0.5) C5C(0.5) H5CA(0.5) H5CB(0.5) C6C(0.5) H6C(0.5) C4D(0.5) H4DA(0.5)
 H4DB(0.5) C8C(0.5) C9C(0.5) H9CA(0.5) H9CB(0.5) C10C(0.5) H10C(0.5) H10D(0.5)
 C10D(0.5) H4EA(0.5) H4EB(0.5) C7C(0.5) H7C(0.5)
 Fixed Uiso: N5D'(0.05) N6D'(0.05) C132(0.05) C122(0.05) C112(0.05) N5C'(0.05)
 C13'(0.05) C12'(0.05) C11'(0.05) N6C'(0.05) N6D(0.05) N5D(0.05) C13D(0.05)
 C12D(0.05) C11D(0.05) N6C(0.05) C11C(0.05) C12C(0.05) C13C(0.05) N5C(0.05)
6.a Secondary CH2 refined with riding coordinates:
 C102(H10A,H10B), C4D'(H4DC,H4DD), C5D'(H5DC,H5DD), C9D'(H9DC,H9DD), C9'(H9'A,
 H9'B), C10'(H10E,H10F), C4C'(H4CC,H4CD), C5C'(H5CC,H5CD), C5D(H5DA,H5DB),
 C9D(H9DA,H9DB), C4C(H4CA,H4CB), C5C(H5CA,H5CB), C4D(H4DA,H4DB), C9C(H9CA,H9CB),
  C10C(H10C,H10D), C10D(H4EA,H4EB)
6.b Aromatic/amide H refined with riding coordinates:
 C3D'(H3D'), C2D'(H2D'), C1D'(H1D'), C132(H132), C122(H122), C112(H112),
 C6D'(H6D'), C7D'(H7D'), C13'(H13'), C12'(H12'), C11'(H11'), C1C'(H1C'),
 C2C'(H2C'), C3C'(H3C'), C6C'(H6C'), C7C'(H7C'), C13D(H5FA), C12D(H28),
 C11D(H9DE), C6D(H6D), C7D(H7D), C11C(H11), C12C(H8IA), C13C(H9IA), C12A(H12A),
 C13A(H13A), C14A(H14A), C15A(H15A), C16A(H16A), C22A(H22A), C23A(H23A),
 C24A(H24A), C25A(H25A), C26A(H26A), C32A(H32A), C33A(H33A), C34A(H34A),
 C35A(H35A), C36A(H36A), C42A(H42A), C43A(H43A), C44A(H44A), C45A(H45A),
 C46A(H46A), C3D(H3D), C1D(H1D), C2D(H2D), C12B(H12B), C13B(H13B), C14B(H14B),
 C15B(H15B), C16B(H16B), C22B(H22B), C23B(H23B), C24B(H24B), C25B(H25B),
 C26B(H26B), C31B(H31B), C32B(H32B), C33B(H33B), C34B(H34B), C35B(H35B),
 C42B(H42B), C43B(H43B), C44B(H44B), C45B(H45B), C46B(H46B), C1C(H1C), C2C(H2C),
  C3C(H3C), C6C(H6C), C7C(H7C)
6.c Fitted pentagon refined as free rotating group:
 N2D'(C3D',C2D',C1D',N1D'), N5D'(N6D',C132,C122,C112), C6D'(N3D',C8D',N4D',
 C7D'), N5C'(C13',C12',C11',N6C'), N6D(N5D,C13D,C12D,C11D), N3D(C6D,C7D,N4D,
 C8D), N6C(C11C,C12C,C13C,N5C), C3D(N1D,N2D,C1D,C2D)
;
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'