Formation of a Cationic Vinylimido Group upon C-H Activation of Nitriles by Trialkylamines in the Presence of TaCl5.
Rahman, Md Mamdudur; Smith, Mark D.; Peryshkov, Dmitry V.; Inorganic chemistry 55 (2016) 5101–5103; doi:10.1021/acs.inorgchem.6b00677

data_4347836
_publ_section_title
;
 Formation of a Cationic Vinylimido Group upon C-H Activation of Nitriles
 by Trialkylamines in the Presence of TaCl5.
;
_journal_issue                   11
_journal_name_full               'Inorganic chemistry'
_journal_page_first              5101
_journal_page_last               5103
_journal_paper_doi               10.1021/acs.inorgchem.6b00677
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C8 H12 Cl4 N2 Ta, C8 H20 N, 1(C2 H3 N1)'
_chemical_formula_sum            'C18 H35 Cl4 N4 Ta'
_chemical_formula_weight         630.25
_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             2016-01-20
_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                   17.6001(6)
_cell_length_b                   17.6001(6)
_cell_length_c                   33.3526(13)
_cell_measurement_reflns_used    9431
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.292
_cell_measurement_theta_min      2.314
_cell_volume                     10331.4(6)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEXII v2014.9-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            103734
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        28.318
_diffrn_reflns_theta_max         28.318
_diffrn_reflns_theta_min         2.167
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    4.680
_exptl_absorpt_correction_T_max  0.2958
_exptl_absorpt_correction_T_min  0.2024
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0849 before and 0.0511 after correction.
The Ratio of minimum to maximum transmission is 0.6842.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_description       cube
_exptl_crystal_F_000             4992
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.742
_refine_diff_density_min         -0.673
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         6440
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0205
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0183P)^2^+23.9478P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0421
_refine_ls_wR_factor_ref         0.0454
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5402
_reflns_number_total             6440
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00677_si_002.cif
_cod_data_source_block           md3087
_cod_original_cell_volume        10331.4(8)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4347836
_shelx_estimated_absorpt_t_max   0.521
_shelx_estimated_absorpt_t_min   0.426
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N3S-C5S
 1.13 with sigma of 0.005
 C5S-C6S
 1.45 with sigma of 0.005
 N3S-C6S
 2.58 with sigma of 0.01
 N1S-C1S
 1.13 with sigma of 0.005
 C1S-C2S
 1.45 with sigma of 0.005
 N1S-C2S
 2.58 with sigma of 0.01
 N2S-C3S
 1.13 with sigma of 0.005
 C3S-C4S
 1.45 with sigma of 0.005
 N2S-C4S
 2.58 with sigma of 0.01
 N4S-C7S
 1.13 with sigma of 0.005
 C7S-C8S
 1.45 with sigma of 0.005
 N4S-C8S
 2.58 with sigma of 0.01
3. Others
 1*[Sof(N1S)+Sof(C1S)+Sof(C2S)+Sof(H2SA)+Sof(H2SB)+Sof(H2SC)]+1*[Sof(N2S)+
 Sof(C3S)+Sof(C4S)+Sof(H4SA)+Sof(H4SB)+Sof(H4SC)]+1*[Sof(N3S)+Sof(C5S)+Sof(C6S)+
 Sof(H6SA)+Sof(H6SB)+Sof(H6SC)]+1*[Sof(N4S)+Sof(C7S)+Sof(C8S)+Sof(H8SA)+
 Sof(H8SB)+Sof(H8SC)]=1 with esd of 0.0001
 Sof(N1S)=Sof(C1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=FVAR(1)
 Sof(N2S)=Sof(C3S)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=FVAR(2)
 Sof(N3S)=Sof(C5S)=Sof(C6S)=Sof(H6SA)=Sof(H6SB)=Sof(H6SC)=FVAR(3)
 Sof(N4S)=Sof(C7S)=Sof(C8S)=Sof(H8SA)=Sof(H8SB)=Sof(H8SC)=FVAR(4)
 Fixed Uiso: N1S(0.1) C1S(0.1) C2S(0.1) N2S(0.1) C3S(0.1) C4S(0.1) N3S(0.1)
 C5S(0.1) C6S(0.1) N4S(0.1) C7S(0.1) C8S(0.1)
4.a Ternary CH refined with riding coordinates:
 N3(H3), C11(H11), C14(H14)
4.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B)
4.c Idealised Me refined with riding coordinates:
 C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC), C6S(H6SA,H6SB,H6SC), C8S(H8SA,H8SB,
 H8SC)
4.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C12(H12A,
 H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              47674
_shelx_hkl_checksum              52818
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'