Well-Defined Palladium N-Heterocyclic Carbene Complexes: Direct C‒H Bond Arylation of Heteroarenes
Kumar, Anuj; Kumar, Manoj; Verma, Akhilesh K.; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.0c02024

data_4038897
_publ_section_title
;
 Well-Defined Palladium N-Heterocyclic Carbene Complexes: Direct C--H Bond
 Arylation of Heteroarenes
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.0c02024
_journal_year                    2020
_chemical_formula_moiety         'C38 H36 Cl3 N3 Pd'
_chemical_formula_sum            'C38 H36 Cl3 N3 Pd'
_chemical_formula_weight         747.45
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-12-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.614(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.7121(8)
_cell_length_b                   21.2886(8)
_cell_length_c                   16.5409(7)
_cell_measurement_reflns_used    9689
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      24.04
_cell_measurement_theta_min      2.33
_cell_volume                     7108.0(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_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  0.0872
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            308396
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.400
_diffrn_reflns_theta_min         2.161
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.778
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       needle
_exptl_crystal_F_000             3056
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.022
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.686
_refine_diff_density_min         -0.682
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     819
_refine_ls_number_reflns         17729
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0928
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0490P)^2^+7.6234P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1056
_refine_ls_wR_factor_ref         0.1241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11421
_reflns_number_total             17729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c02024_si_002.cif
_cod_data_source_block           av_ak_1_23a
_cod_database_code               4038897
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.977
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: H37C(0.5) H37D(0.5) H37A(0.5) H37B(0.5) C38B(0.5) H38A(0.5)
 H38B(0.5) H38C(0.5) H69C(0.5) H69D(0.5) H69A(0.5) H69B(0.5) C70B(0.5)
 H70A(0.5) H70B(0.5) H70C(0.5) C38A(0.5) H38D(0.5) H38E(0.5) H38F(0.5)
 C70A(0.5) H70D(0.5) H70E(0.5) H70F(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C27(H27A,H27B), C31(H31A,H31B), C37(H37C,H37D), C37(H37A,
 H37B), C59(H59A,H59B), C65(H65A,H65B), C69(H69C,H69D), C69(H69A,H69B),
 C75(H75A,H75B)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15),
 C16(H16), C18(H18), C22(H22), C23(H23), C24(H24), C33(H33), C34(H34), C35(H35),
  C43(H43), C44(H44), C45(H45), C47(H47), C48(H48), C49(H49), C52(H52),
 C54(H54), C55(H55), C56(H56), C61(H61), C62(H62), C63(H63), C71(H71), C72(H72),
  C73(H73)
3.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C28(H28A,H28B,H28C), C32(H32A,H32B,H32C), C38B(H38A,H38B,
 H38C), C60(H60A,H60B,H60C), C66(H66A,H66B,H66C), C70B(H70A,H70B,H70C),
 C76(H76A,H76B,H76C), C38A(H38D,H38E,H38F), C70A(H70D,H70E,H70F)
;
_shelx_res_checksum              22856
_shelx_hkl_checksum              4949
_olex2_submission_special_instructions 'No special instructions were received'