Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary Amines: A Combined Effort
Tokmic, Kenan; Jackson, Bailey J.; Salazar, Andrea; Woods, Toby J.; Fout, Alison R.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b07368

data_4126408
_publ_contact_author
; 
Alison R. Fout 
University of Illinois 
School of Chemical Sciences 
A406 CLSL, Box 54-6 
600 South Mathews Avenue 
Urbana, Illinois  61801 
USA 
;
_publ_section_title
;
 Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary
 Amines: A Combined Effort
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b07368
_journal_year                    2017
_chemical_formula_moiety
; 
C47 H48 Co N5 O 
;
_chemical_formula_sum            'C23.5 H24 Co0.5 N2.5 O0.5'
_chemical_formula_weight         378.92
_chemical_name_systematic
; 
? 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-03-21
_audit_creation_method
; 
Olex2 1.2 
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155) 
;
_audit_update_record
; 
? 
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.6141(9)
_cell_length_b                   19.4717(7)
_cell_length_c                   8.0534(3)
_cell_measurement_reflns_used    9673
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.69
_cell_measurement_theta_min      2.66
_cell_volume                     3859.8(2)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2014.9-0 (Bruker, 2014)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2014/2, SADABS V2014/4, TWINABS V2012/1 
(Bruker, 2012 & 2014) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'XCIF V2014-2 (Bruker, 2014)'
_computing_structure_refinement
; 
SHELX-2014-6 (Sheldrick, 2014) 
Olex2 1.2.6 (Dolomanov et. al., 2009) 
;
_computing_structure_solution    'SHELX-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker Photon 100 area detector'
_diffrn_detector_type            'photon counter area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'Bruker D8 Venture/Photon 100'
_diffrn_measurement_device_type  'Bruker D8 Venture/Photon 100'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'microfocus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  cd62asa
_diffrn_reflns_av_R_equivalents  0.0495
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            26577
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        21.773
_diffrn_reflns_theta_max         21.773
_diffrn_reflns_theta_min         2.661
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.488
_exptl_absorpt_correction_T_max  0.98751
_exptl_absorpt_correction_T_min  0.95765
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker, 2014)'
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1600
_exptl_crystal_id                cd62zsa
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (0 -1 2) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_recrystallization_method
'Crystals were obtained from a slow evaporation of an diethyl ether solution.'
_exptl_crystal_size_max          0.136
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.590
_refine_diff_density_min         -0.625
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     270
_refine_ls_number_reflns         2378
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0394
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0481P)^2^+5.6646P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0963
_refine_ls_wR_factor_ref         0.1010
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2097
_reflns_number_total             2378
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07368_si_003.cif
_cod_data_source_block           cd63zsa
_cod_original_formula_sum        'C23.50 H24 Co0.50 N2.50 O0.50'
_cod_database_code               4126408
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.937
_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. Restrained distances 
 O1-C27 \\sim O1-C28 
 with sigma of 0.02 
3. Others 
 Fixed Sof: H27A(0.5) H27B(0.5) H29A(0.5) H29C(0.5) H29B(0.5) H28A(0.5) 
 H28B(0.5) H26A(0.5) H26B(0.5) H26C(0.5) 
4.a Secondary CH2 refined with riding coordinates: 
 C27(H27A,H27B), C28(H28A,H28B) 
4.b Aromatic/amide H refined with riding coordinates: 
 C9(H9), C21(H21), C25(H25), C6(H6), C3(H3), C5(H5), C4(H4), C24(H24), 
 C22(H22), C14(H14), C23(H23), C16(H16), C10(H10) 
4.c Idealised Me refined as rotating group: 
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C29(H29A,H29C, 
 H29B), C26(H26A,H26B,H26C) 
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'