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_7044019
_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         'C35 H45 Br Cu N3, 2(C7 H8)'
_chemical_formula_sum            'C49 H61 Br Cu N3'
_chemical_formula_weight         835.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-06-21
_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                82.7553(15)
_cell_angle_beta                 77.8500(15)
_cell_angle_gamma                65.2414(18)
_cell_formula_units_Z            2
_cell_length_a                   12.2492(2)
_cell_length_b                   12.9626(2)
_cell_length_c                   15.7524(3)
_cell_measurement_reflns_used    31311
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      31.1810
_cell_measurement_theta_min      1.8320
_cell_volume                     2218.37(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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0951
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  96.00   1.00   15.00    --   25.96  77.00  30.00  100
  2  \w      6.00  95.00   1.00   15.00    --   25.96  57.00-180.00   89
  3  \w    -43.00  47.00   1.00   15.00    --   25.96 -57.00 -90.00   90
  4  \w    -44.00  56.00   1.00   15.00    --   25.96 -77.00-180.00  100
  5  \w    -20.00  68.00   1.00   15.00    --   25.96 -99.00-120.00   88
  6  \w     -4.00  96.00   1.00   15.00    --   25.96  77.00 -60.00  100
  7  \w      0.00  98.00   1.00   15.00    --   25.96  38.00 150.00   98
  8  \w    -44.00  56.00   1.00   15.00    --   25.96 -77.00  90.00  100
  9  \w     -4.00  96.00   1.00   15.00    --   25.96  77.00-150.00  100
 10  \w    -20.00  68.00   1.00   15.00    --   25.96 -99.00  30.00   88
 11  \w    -99.00 -35.00   1.00   15.00    --  -23.50-178.00 120.00   64
 12  \w     35.00 102.00   1.00   15.00    --   25.96 178.00  90.00   67
 13  \w      6.00  95.00   1.00   15.00    --   25.96  57.00  30.00   89
 14  \w    -20.00  68.00   1.00   15.00    --   25.96 -99.00-180.00   88
 15  \w    -46.00  51.00   1.00   15.00    --   25.96 -38.00  90.00   97
 16  \w    -47.00  99.00   1.00   15.00    --   25.96   0.00-180.00  146
 17  \w    -47.00  99.00   1.00   15.00    --   25.96   0.00-150.00  146
 18  \w    -47.00  99.00   1.00   15.00    --   25.96   0.00-120.00  146
 19  \w    -47.00  66.00   1.00   15.00    --   25.96   0.00 -90.00  113
;
_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      0.0592196000
_diffrn_orient_matrix_UB_12      -0.0375146000
_diffrn_orient_matrix_UB_13      0.0075531000
_diffrn_orient_matrix_UB_21      -0.0261517000
_diffrn_orient_matrix_UB_22      -0.0213742000
_diffrn_orient_matrix_UB_23      0.0388593000
_diffrn_orient_matrix_UB_31      -0.0019628000
_diffrn_orient_matrix_UB_32      -0.0421123000
_diffrn_orient_matrix_UB_33      -0.0236281000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            100993
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.080
_diffrn_reflns_theta_min         1.732
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.428
_exptl_absorpt_correction_T_max  0.875
_exptl_absorpt_correction_T_min  0.633
_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    1.251
_exptl_crystal_description       fragment
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.433
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.109
_refine_diff_density_max         1.030
_refine_diff_density_min         -1.055
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     479
_refine_ls_number_reflns         13038
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0614
_refine_ls_R_factor_gt           0.0495
_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^)+(0.0607P)^2^+3.7449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1332
_refine_ls_wR_factor_ref         0.1403
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10831
_reflns_number_total             13038
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt03099a2.cif
_cod_data_source_block           compound_26
_cod_original_cell_volume        2218.39(8)
_cod_database_code               7044019
_chemical_oxdiff_formula         'C51 H60 N3 Cu Br'
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.01
_olex2_date_sample_data_collection 2017-06-06
_olex2_date_sample_submission    1496008800
_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. Uiso/Uaniso restraints and constraints
Uanis(C42) = Uanis(C49) = Uanis(C56)
Uanis(C48) = Uanis(C44) = Uanis(C37) = Uanis(C41) = Uanis(C51) = Uanis(C55)
Uanis(C53) = Uanis(C39) = Uanis(C46)
Uanis(C38) = Uanis(C40) = Uanis(C45) = Uanis(C47) = Uanis(C52) = Uanis(C54)
3. Same fragment restrains
{C36, C37, C38, C39, C40, C41, C42} sigma for 1-2: 0.02, 1-3: 0.04
as
{C43, C44, C45, C46, C47, C48, C49}
{C36, C37, C38, C39, C40, C41, C42} sigma for 1-2: 0.02, 1-3: 0.04
as
{C50, C51, C52, C53, C54, C55, C56}
4. Others
 Fixed Sof: C43(0.5) C44(0.5) H44(0.5) C45(0.5) H45(0.5) C46(0.5) H46(0.5)
 C47(0.5) H47(0.5) C48(0.5) H48(0.5) C49(0.5) H49A(0.5) H49B(0.5) H49C(0.5)
 C50(0.5) C51(0.5) H51(0.5) C52(0.5) H52(0.5) C53(0.5) H53(0.5) C54(0.5)
 H54(0.5) C55(0.5) H55(0.5) C56(0.5) H56A(0.5) H56B(0.5) H56C(0.5)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C22(H22), C25(H25)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20), C29(H29),
 C30(H30), C32(H32), C33(H33), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
  C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C51(H51), C52(H52),
 C53(H53), C54(H54), C55(H55)
5.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), C35(H35A,H35B,H35C), C42(H42A,H42B,H42C),
 C49(H49A,H49B,H49C), C56(H56A,H56B,H56C)
;
_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 1.420
_oxdiff_exptl_absorpt_empirical_full_min 0.523
_shelx_shelxl_version_number     2016/4