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_7044018
_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         '2(C34 H43 N2), Br4 Ni [+ solvent]'
_chemical_formula_sum            'C68 H86 Br4 N4 Ni'
_chemical_formula_weight         1337.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-02-01
_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                 103.2084(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.2529(4)
_cell_length_b                   17.8637(4)
_cell_length_c                   18.7897(3)
_cell_measurement_reflns_used    17399
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      29.0840
_cell_measurement_theta_min      1.8770
_cell_volume                     7271.7(2)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.7909
_diffrn_measured_fraction_theta_max 0.9982
_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     -4.00  94.00   1.00   33.00    --   24.94  77.00 120.00   98
  2  \w      6.00  93.00   1.00   33.00    --   24.94  57.00  90.00   87
  3  \w    -44.00  54.00   1.00   33.00    --   24.94 -77.00   0.00   98
  4  \w    -44.00  54.00   1.00   33.00    --   24.94 -77.00-180.00   98
  5  \w     -4.00  94.00   1.00   33.00    --   24.94  77.00-150.00   98
  6  \w     -4.00  94.00   1.00   33.00    --   24.94  77.00  30.00   98
  7  \w    -20.00  65.00   1.00   33.00    --   24.94 -99.00 -60.00   85
  8  \w    -46.00  47.00   1.00   33.00    --   24.94 -38.00  60.00   93
  9  \w     -4.00  94.00   1.00   33.00    --   24.94  77.00 -60.00   98
 10  \w      7.00  85.00   1.00   33.00    --   24.94-133.00 145.75   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0189987000
_diffrn_orient_matrix_UB_12      0.0197862000
_diffrn_orient_matrix_UB_13      -0.0191705000
_diffrn_orient_matrix_UB_21      0.0132085000
_diffrn_orient_matrix_UB_22      0.0203056000
_diffrn_orient_matrix_UB_23      0.0322243000
_diffrn_orient_matrix_UB_31      0.0231582000
_diffrn_orient_matrix_UB_32      -0.0278070000
_diffrn_orient_matrix_UB_33      0.0098754000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0597
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            83727
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.11
_diffrn_reflns_theta_min         1.59
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.502
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.616
_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 blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       fragment
_exptl_crystal_F_000             2760
_exptl_crystal_size_max          0.296
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.019
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.572
_refine_diff_density_rms         0.084
_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     357
_refine_ls_number_reflns         10702
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0427P)^2^+10.0313P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0909
_refine_ls_wR_factor_ref         0.0963
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8207
_reflns_number_total             10702
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt03099a2.cif
_cod_data_source_block           compound_14
_cod_database_code               7044018
_chemical_oxdiff_formula         'C75 H94 Br4 N4 Ni'
_reflns_odcompleteness_completeness 79.09
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     32.78
_olex2_date_sample_data_collection 2017-01-31
_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), 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), C34(H34A,H34B,H34C)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.224
_oxdiff_exptl_absorpt_empirical_full_min 0.824
_shelx_shelxl_version_number     2016/4