Nickel-Catalysed Direct C2-Arylation of N-Heterocyclic Carbene
Ghadwal, Rajendra S.; Ho, Nga Kim; Neumann, Beate; Stammler, Georg; Menezes da Silva, Vitor Hugo; Watanabe, Daniel; Braga, Ataualpa A. C.; Dalton Trans.  (2017) –; doi:10.1039/C7DT03099A

data_7044016
_publ_section_title
;
 Nickel-Catalysed Direct C2-Arylation of N-Heterocyclic Carbene
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT03099A
_journal_year                    2017
_chemical_formula_moiety         'C33 H41 N2, Br'
_chemical_formula_sum            'C33 H41 Br N2'
_chemical_formula_weight         545.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-23
_audit_creation_method
;
  Olex2 1.2-ac2
  (compiled 2012.03.27 svn.r2268, GUI svn.r4156)
;
_audit_update_record
;
2017-06-28 deposited with the CCDC.
2017-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.3846(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.08483(19)
_cell_length_b                   8.95600(6)
_cell_length_c                   22.48986(13)
_cell_measurement_reflns_used    39104
_cell_measurement_temperature    220.00(10)
_cell_measurement_theta_max      72.2560
_cell_measurement_theta_min      2.8990
_cell_volume                     6032.92(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      220.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9970
_diffrn_measured_fraction_theta_max 0.9962
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     16.00  52.00   1.00    1.00    --   42.33  57.00  60.00   36
  2  \w     55.00 111.00   1.00    1.00    --   42.33  57.00  60.00   56
  3  \w     83.00 111.00   1.00    2.50    --  111.00  61.00   0.00   28
  4  \w    112.00 178.00   1.00    2.50    --  111.00  77.00 -30.00   66
  5  \w    111.00 177.00   1.00    2.50    --  111.00  77.00 -90.00   66
  6  \w    117.00 145.00   1.00    2.50    --  111.00  61.00 -90.00   28
  7  \w    114.00 177.00   1.00    2.50    --  111.00  77.00-150.00   63
  8  \w    113.00 174.00   1.00    2.50    --  111.00  77.00-180.00   61
  9  \w     84.00 110.00   1.00    2.50    --  111.00  60.00-174.30   26
 10  \w     83.00 109.00   1.00    2.50    --  111.00  61.00-150.00   26
 11  \w     81.00 106.00   1.00    2.50    --  111.00  77.00-150.00   25
 12  \w     84.00 115.00   1.00    2.50    --  111.00  59.00-138.66   31
 13  \w     80.00 106.00   1.00    2.50    --  111.00  77.00 -90.00   26
 14  \w     83.00 109.00   1.00    2.50    --  111.00  61.00 -90.00   26
 15  \w     83.00 109.00   1.00    2.50    --  111.00  61.00 -60.00   26
 16  \w     83.00 109.00   1.00    2.50    --  111.00  61.00 -30.00   26
 17  \w    110.00 178.00   1.00    2.50    --  111.00  77.00   0.00   68
 18  \w    112.00 167.00   1.00    2.50    --  111.00  77.00  30.00   55
 19  \w    117.00 174.00   1.00    2.50    --  111.00  77.00  90.00   57
 20  \w     85.00 151.00   1.00    2.50    --  111.00  54.00 140.61   66
 21  \w     85.00 111.00   1.00    2.50    --  111.00  54.00 111.94   26
 22  \w     83.00 113.00   1.00    2.50    --  111.00  61.00 120.00   30
 23  \w     80.00 106.00   1.00    2.50    --  111.00  77.00  90.00   26
 24  \w     83.00 109.00   1.00    2.50    --  111.00  61.00  90.00   26
 25  \w     83.00 160.00   1.00    2.50    --  111.00  61.00  60.00   77
 26  \w     87.00 113.00   1.00    2.50    --  111.00  45.00  30.00   26
 27  \w     80.00 177.00   1.00    2.50    --  111.00  77.00  60.00   97
 28  \w     80.00 174.00   1.00    2.50    --  111.00  77.00 150.00   94
 29  \w     83.00 150.00   1.00    2.50    --  111.00  61.00 150.00   67
 30  \w     83.00 109.00   1.00    2.50    --  111.00  61.00  30.00   26
 31  \w     82.00 108.00   1.00    2.50    --  111.00  69.00  26.40   26
 32  \w     80.00 106.00   1.00    2.50    --  111.00  77.00   0.00   26
 33  \w     80.00 106.00   1.00    2.50    --  111.00  77.00 -30.00   26
 34  \w     80.00 150.00   1.00    2.50    --  111.00  77.00 -60.00   70
 35  \w     83.00 122.00   1.00    2.50    --  111.00  61.00-120.00   39
 36  \w     82.00 108.00   1.00    2.50    --  111.00  68.00 -61.97   26
 37  \w     80.00 176.00   1.00    2.50    --  111.00  77.00-120.00   96
 38  \w     80.00 106.00   1.00    2.50    --  111.00  77.00  30.00   26
 39  \w     80.00 106.00   1.00    2.50    --  111.00  77.00 120.00   26
 40  \w     23.00  68.00   1.00    1.00    --   42.33  38.00 -30.00   45
 41  \w      8.00 121.00   1.00    1.00    --   42.33  19.00-120.00  113
 42  \w     80.00 106.00   1.00    2.50    --  111.00  77.00-180.00   26
 43  \w     13.00 113.00   1.00    1.00    --   42.33  68.00 -18.86  100
 44  \w     42.00 114.00   1.00    2.50    --  111.00 -61.00-120.00   72
 45  \w     69.00 121.00   1.00    2.50    --  111.00-125.00 -30.00   52
 46  \w     62.00  95.00   1.00    2.50    --  111.00 -94.00-150.00   33
 47  \w     40.00 120.00   1.00    2.50    --  111.00-125.00-150.00   80
 48  \w     44.00 137.00   1.00    2.50    --  111.00 -77.00  30.00   93
 49  \w     66.00 119.00   1.00    2.50    --  111.00-125.00 120.00   53
 50  \w     60.00 117.00   1.00    1.00    --   42.33-178.00 120.00   57
 51  \w     30.00 102.00   1.00    2.50    --  111.00 -94.00   0.00   72
 52  \w      1.00  78.00   1.00    1.00    --   42.33 -99.00-150.00   77
 53  \w    -27.00  63.00   1.00    1.00    --   42.33 -57.00 -90.00   90
 54  \w    -44.00 -17.00   1.00    1.00    --  -42.33 -57.00-150.00   27
 55  \w    -71.00 -11.00   1.00    1.00    --  -42.33 -77.00-150.00   60
 56  \w    -59.00  26.00   1.00    1.00    --  -42.33  38.00 150.00   85
 57  \w    -64.00 -11.00   1.00    1.00    --  -42.33 -77.00  30.00   53
 58  \w    -84.00 -11.00   1.00    1.00    --  -42.33 -77.00 120.00   73
 59  \w    -81.00 -12.00   1.00    1.00    --  -42.33 -77.00 -30.00   69
 60  \w   -113.00 -97.00   1.00    1.00    --  -42.33 -77.00  30.00   16
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0470965000
_diffrn_orient_matrix_UB_12      0.0576490000
_diffrn_orient_matrix_UB_13      0.0093172000
_diffrn_orient_matrix_UB_21      -0.0047676000
_diffrn_orient_matrix_UB_22      0.0622192000
_diffrn_orient_matrix_UB_23      -0.0641611000
_diffrn_orient_matrix_UB_31      -0.0201121000
_diffrn_orient_matrix_UB_32      -0.1495998000
_diffrn_orient_matrix_UB_33      -0.0230852000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0248
_diffrn_reflns_av_unetI/netI     0.0102
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            54009
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.343
_diffrn_reflns_theta_min         2.951
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.008
_exptl_absorpt_correction_T_max  0.707
_exptl_absorpt_correction_T_min  0.591
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.201
_exptl_crystal_description       fragment
_exptl_crystal_F_000             2304.0
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.294
_exptl_crystal_size_min          0.216
_refine_diff_density_max         0.351
_refine_diff_density_min         -0.542
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     333
_refine_ls_number_reflns         5945
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0302
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0387P)^2^+5.2333P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0791
_refine_ls_wR_factor_ref         0.0795
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5801
_reflns_number_total             5945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt03099a2.cif
_cod_data_source_block           compound_3a
_cod_database_code               7044016
_chemical_oxdiff_formula         'C33 H41 Br N2'
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_date_sample_data_collection 2017-01-20
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C29(H29), C30(H30), C31(H31), C32(H32), C33(H33)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.252
_oxdiff_exptl_absorpt_empirical_full_min 0.830
_shelx_res_checksum              18947
_shelx_shelxl_version_number     2016/4