Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates.
Martinez, Gabriel Espinosa; Ocampo, Cristian; Park, Yun Ji; Fout, Alison R.; Journal of the American Chemical Society 138 (2016) 4290–4293; doi:10.1021/jacs.5b12827

data_4130024
_publ_section_title
;
 Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen
 and Halogen Surrogates.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4290
_journal_page_last               4293
_journal_paper_doi               10.1021/jacs.5b12827
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety
; 
C44 H45 Cl3 N4 Ni, C6 H6, C4 H8 O, 0.8(C6 H6), 0.2(C5 H12) 
;
_chemical_formula_sum            'C59.8 H66.2 Cl3 N4 Ni O'
_chemical_formula_weight         1022.06
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-12-03
_audit_creation_method
; 
Olex2 1.2 
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103) 
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   26.8014(17)
_cell_length_b                   26.8014(17)
_cell_length_c                   30.1916(19)
_cell_measurement_reflns_used    9822
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      24.79
_cell_measurement_theta_min      2.38
_cell_volume                     21687(2)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2013.10-0 (Bruker, 2013)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2013/3, SADABS V2012/1, TWINABS V2012/1 
(Bruker, 2012 & 2013) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELX-2014-6 (Sheldrick, 2014)'
_computing_structure_solution    'SHELX-2014-6 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Bruker APEXII CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa/ApexII CCD'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  cm91q
_diffrn_reflns_av_R_equivalents  0.0879
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            183569
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.398
_diffrn_reflns_theta_min         1.016
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.549
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8725
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014) was used for absorption correction. 
wR2(int) was 0.0676 before and 0.0625 after correction. 
The Ratio of minimum to maximum transmission is 0.8725. 
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       rod
_exptl_crystal_F_000             8640
_exptl_crystal_id                cm91q
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (1, 0, 2) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.274
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.077
_refine_diff_density_max         0.507
_refine_diff_density_min         -0.702
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     653
_refine_ls_number_reflns         9982
_refine_ls_number_restraints     382
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0733P)^2^+17.5947P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1180
_refine_ls_wR_factor_ref         0.1256
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7586
_reflns_number_total             9982
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b12827_si_002.cif
_cod_data_source_block           cm91qsa
_cod_original_cell_volume        21687(3)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4130024
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.864
_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. Uiso/Uaniso restraints and constraints 
C50 \\sim C50B \\sim C51 \\sim C51B \\sim C52 \\sim C52B \\sim C53 \\sim C53B 
\\sim C54 \\sim C54B \\sim C55 \\sim C55B: within 1.7A with sigma of 0.01 and 
sigma for terminal atoms of 0.02 
O60 \\sim O60B \\sim C60 \\sim C60B \\sim C61 \\sim C61B \\sim C62 \\sim C62B 
\\sim C63 \\sim C63B: within 1.7A with sigma of 0.01 and sigma for terminal 
atoms of 0.02 
Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) 
\\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C50B) \\sim Ueq, 
Uanis(C51B) \\sim Ueq, Uanis(C52B) \\sim Ueq, Uanis(C53B) \\sim Ueq, 
Uanis(C54B) \\sim Ueq, Uanis(C55B) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
3. Same fragment restrains 
{C50, C51, C52, C53, C54, C55} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{C50B, C51B, C52B, C53B, C54B, C55B} 
{O60, C60, C61, C62, C63} sigma for 1-2: 0.01, 1-3: 0.04 
as 
{O60B, C60B, C61B, C62B, C63B} 
4. Others 
 Sof(C50B)=Sof(H50B)=Sof(C51B)=Sof(H51B)=Sof(C52B)=Sof(H52B)=Sof(C53B)= 
 Sof(H53B)=Sof(C54B)=Sof(H54B)=Sof(C55B)=Sof(H55B)=1-FVAR(1) 
 Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)= 
 Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=FVAR(1) 
 Sof(O60B)=Sof(C60B)=Sof(H60C)=Sof(H60D)=Sof(C61B)=Sof(H61C)=Sof(H61D)= 
 Sof(C62B)=Sof(H62C)=Sof(H62D)=Sof(C63B)=Sof(H63C)=Sof(H63D)=1-FVAR(2) 
 Sof(O60)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)= 
 Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=FVAR(2) 
5.a Ternary CH refined with riding coordinates: 
 C27(H27), C30(H30), C39(H39), C42(H42) 
5.b Secondary CH2 refined with riding coordinates: 
 C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C60B(H60C, 
 H60D), C61B(H61C,H61D), C62B(H62C,H62D), C63B(H63C,H63D) 
5.c Aromatic/amide H refined with riding coordinates: 
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C15(H15), 
 C16(H16), C17(H17), C18(H18), C23(H23), C24(H24), C25(H25), C35(H35), 
C36(H36), C37(H37), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), 
 C50B(H50B), C51B(H51B), C52B(H52B), C53B(H53B), C54B(H54B), C55B(H55B) 
5.d Fitted hexagon refined as free rotating group: 
 C50(C51,C52,C53,C54,C55), C50B(C51B,C52B,C53B,C54B,C55B) 
5.e Idealised Me refined as rotating group: 
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C32(H32A,H32B, 
 H32C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), 
C44(H44A,H44B,H44C) 
;
_smtbx_masks_special_details
; 
There were a total of 44.5 electrons masked per asymmetric unit. 
These correspond to 0.8 benzene molecule and 0.2 pentane molecule 
sitting in a symmetry position. 
;
_olex2_submission_special_instructions 'No special instructions were received'