#------------------------------------------------------------------------------
#$Date: 2016-03-21 17:04:53 +0200 (Mon, 21 Mar 2016) $
#$Revision: 178767 $
#$URL: svn://www.crystallography.net/cod/cif/4/10/21/4102147.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4102147
loop_
_publ_author_name
'Dmitry Shabashov'
'Olafs Daugulis'
_publ_section_title
;
 Auxiliary-Assisted Palladium-Catalyzed Arylation and Alkylation of sp2
 and sp3 Carbon-Hydrogen Bonds
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3965
_journal_page_last               3972
_journal_paper_doi               10.1021/ja910900p
_journal_volume                  132
_journal_year                    2010
_chemical_formula_moiety         'C19 H23 Br2 N3 O Pd, C H2 Cl2'
_chemical_formula_sum            'C20 H25 Br2 Cl2 N3 O Pd'
_chemical_formula_weight         660.55
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_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
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                94.143(1)
_cell_angle_beta                 96.995(1)
_cell_angle_gamma                96.737(1)
_cell_formula_units_Z            2
_cell_length_a                   9.9480(9)
_cell_length_b                   10.5972(9)
_cell_length_c                   11.8562(10)
_cell_measurement_reflns_used    4193
_cell_measurement_temperature    223(2)
_cell_measurement_theta_max      25.07
_cell_measurement_theta_min      1.74
_cell_volume                     1227.27(18)
_computing_cell_refinement       'SAINT v7.12A (Bruker-Nonius, 2004)'
_computing_data_collection       'APEX2 v1.0-27 (Bruker-Nonius, 2005)'
_computing_data_reduction        'SAINT v7.12A (Bruker-Nonius, 2004)'
_computing_structure_refinement  'SHELXL v6.12 (G.M. Sheldrick, 2001)'
_computing_structure_solution    'SHELXS v6.12 (G.M. Sheldrick, 2001)'
_diffrn_ambient_temperature      223(2)
_diffrn_detector_area_resol_mean 4K
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'Bruker-Nonius APEX II CCD'
_diffrn_measurement_method       CCD
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0332
_diffrn_reflns_av_sigmaI/netI    0.0151
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            6222
_diffrn_reflns_theta_full        25.07
_diffrn_reflns_theta_max         25.07
_diffrn_reflns_theta_min         1.74
_diffrn_standards_decay_%        0.0
_exptl_absorpt_coefficient_mu    4.246
_exptl_absorpt_correction_T_max  0.9901
_exptl_absorpt_correction_T_min  0.5997
_exptl_absorpt_correction_type   empirical
_exptl_crystal_colour            'Very dark green'
_exptl_crystal_density_diffrn    1.788
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.30
_refine_diff_density_max         2.231
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    noref
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         4279
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.0337
_refine_ls_R_factor_gt           0.0286
_refine_ls_shift/su_max          0.014
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0464P)²+2.0551P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0786
_refine_ls_wR_factor_ref         0.0822
_reflns_number_gt                3477
_reflns_number_total             4279
_reflns_threshold_expression     >4sigma(I)
_cod_data_source_file            ja910900p_si_002.cif
_cod_data_source_block           k1161
_cod_database_code               4102147
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Pd Pd 0.51295(2) 0.81789(2) 0.25208(2) 0.02374(9) Uani 1 1 d . . .
Br1 Br 0.33366(4) 0.64064(4) 0.18858(3) 0.03832(12) Uani 1 1 d . . .
Br2 Br 0.68577(4) 1.00420(4) 0.31579(3) 0.03894(12) Uani 1 1 d . . .
O1 O 0.7901(3) 0.6433(3) 0.0934(3) 0.0588(9) Uani 1 1 d . . .
N1 N 0.5461(3) 0.7462(3) 0.4189(2) 0.0291(6) Uani 1 1 d . . .
N2 N 0.6569(3) 0.7094(3) 0.2246(2) 0.0310(7) Uani 1 1 d . . .
N3 N 0.2559(3) 0.9491(3) 0.2903(3) 0.0327(7) Uani 1 1 d . . .
C1 C 0.4886(4) 0.7678(4) 0.5113(3) 0.0375(9) Uani 1 1 d . . .
H1 H 0.4238 0.8257 0.5101 0.045 Uiso 1 1 calc R . .
C2 C 0.5191(4) 0.7086(4) 0.6111(3) 0.0429(10) Uani 1 1 d . . .
H2 H 0.4768 0.7274 0.6760 0.051 Uiso 1 1 calc R . .
C3 C 0.6107(4) 0.6239(4) 0.6127(3) 0.0439(10) Uani 1 1 d . . .
H3 H 0.6309 0.5821 0.6788 0.053 Uiso 1 1 calc R . .
C4 C 0.6766(4) 0.5971(4) 0.5162(3) 0.0349(8) Uani 1 1 d . . .
C5 C 0.7731(4) 0.5101(4) 0.5118(4) 0.0462(10) Uani 1 1 d . . .
H5 H 0.7975 0.4655 0.5754 0.055 Uiso 1 1 calc R . .
C6 C 0.8302(4) 0.4915(4) 0.4149(4) 0.0510(11) Uani 1 1 d . . .
H6 H 0.8948 0.4337 0.4129 0.061 Uiso 1 1 calc R . .
C7 C 0.7966(4) 0.5555(4) 0.3165(4) 0.0434(10) Uani 1 1 d . . .
H7 H 0.8384 0.5394 0.2509 0.052 Uiso 1 1 calc R . .
C8 C 0.7019(3) 0.6422(3) 0.3167(3) 0.0308(8) Uani 1 1 d . . .
C9 C 0.6404(3) 0.6617(3) 0.4182(3) 0.0295(7) Uani 1 1 d . . .
C10 C 0.6979(4) 0.7026(4) 0.1195(3) 0.0374(9) Uani 1 1 d . . .
C11 C 0.6151(4) 0.7724(4) 0.0310(3) 0.0365(8) Uani 1 1 d . . .
C12 C 0.5207(4) 0.8573(3) 0.0842(3) 0.0313(8) Uani 1 1 d . . .
H12A H 0.4289 0.8409 0.0413 0.038 Uiso 1 1 calc R . .
H12B H 0.5553 0.9473 0.0813 0.038 Uiso 1 1 calc R . .
C13 C 0.5327(5) 0.6696(5) -0.0555(4) 0.0544(12) Uani 1 1 d . . .
H13A H 0.4691 0.6166 -0.0176 0.082 Uiso 1 1 calc R . .
H13B H 0.5941 0.6173 -0.0885 0.082 Uiso 1 1 calc R . .
H13C H 0.4825 0.7097 -0.1154 0.082 Uiso 1 1 calc R . .
C14 C 0.7157(5) 0.8556(5) -0.0298(4) 0.0524(11) Uani 1 1 d . . .
H14A H 0.7685 0.9209 0.0248 0.079 Uiso 1 1 calc R . .
H14B H 0.6654 0.8956 -0.0896 0.079 Uiso 1 1 calc R . .
H14C H 0.7766 0.8028 -0.0629 0.079 Uiso 1 1 calc R . .
C15 C 0.3569(4) 0.9143(3) 0.2759(3) 0.0296(7) Uani 1 1 d . . .
C16 C 0.1139(3) 0.9684(4) 0.3037(3) 0.0358(8) Uani 1 1 d . . .
C17 C 0.0665(5) 0.8721(5) 0.3828(5) 0.0616(13) Uani 1 1 d . . .
H17A H 0.1187 0.8922 0.4578 0.092 Uiso 1 1 calc R . .
H17B H 0.0800 0.7874 0.3530 0.092 Uiso 1 1 calc R . .
H17C H -0.0296 0.8746 0.3883 0.092 Uiso 1 1 calc R . .
C18 C 0.0329(4) 0.9415(6) 0.1854(4) 0.0613(14) Uani 1 1 d . . .
H18A H 0.0353 0.8536 0.1576 0.092 Uiso 1 1 calc R . .
H18B H 0.0727 0.9978 0.1340 0.092 Uiso 1 1 calc R . .
H18C H -0.0610 0.9560 0.1892 0.092 Uiso 1 1 calc R . .
C19 C 0.1144(5) 1.1042(5) 0.3510(5) 0.0611(13) Uani 1 1 d . . .
H19A H 0.1658 1.1175 0.4268 0.092 Uiso 1 1 calc R . .
H19B H 0.0213 1.1211 0.3552 0.092 Uiso 1 1 calc R . .
H19C H 0.1565 1.1617 0.3016 0.092 Uiso 1 1 calc R . .
C20 C 0.9282(5) 0.3541(5) 0.0649(4) 0.0553(12) Uani 1 1 d . . .
H20A H 0.9659 0.3327 -0.0056 0.066 Uiso 1 1 calc R . .
H20B H 0.8669 0.4187 0.0499 0.066 Uiso 1 1 calc R . .
Cl1 Cl 0.83622(16) 0.21816(14) 0.10493(17) 0.0964(6) Uani 1 1 d . . .
Cl2 Cl 1.06040(11) 0.41605(13) 0.17127(11) 0.0614(3) Uani 1 1 d . . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N2 Pd C15 175.26(13) . . ?
N2 Pd C12 84.22(13) . . ?
C15 Pd C12 95.96(14) . . ?
N2 Pd N1 80.80(11) . . ?
C15 Pd N1 98.97(12) . . ?
C12 Pd N1 165.02(12) . . ?
N2 Pd Br1 91.43(9) . . ?
C15 Pd Br1 83.84(10) . . ?
C12 Pd Br1 89.90(11) . . ?
N1 Pd Br1 90.54(8) . . ?
N2 Pd Br2 91.27(9) . . ?
C15 Pd Br2 93.47(10) . . ?
C12 Pd Br2 89.76(11) . . ?
N1 Pd Br2 90.51(8) . . ?
Br1 Pd Br2 177.234(16) . . ?
C1 N1 C9 119.6(3) . . ?
C1 N1 Pd 130.9(3) . . ?
C9 N1 Pd 109.5(2) . . ?
C10 N2 C8 126.6(3) . . ?
C10 N2 Pd 118.1(2) . . ?
C8 N2 Pd 115.3(2) . . ?
C15 N3 C16 169.1(4) . . ?
N1 C1 C2 123.1(4) . . ?
C3 C2 C1 118.6(4) . . ?
C2 C3 C4 121.0(4) . . ?
C5 C4 C3 124.0(4) . . ?
C5 C4 C9 119.1(4) . . ?
C3 C4 C9 116.9(3) . . ?
C6 C5 C4 119.2(4) . . ?
C5 C6 C7 122.7(4) . . ?
C8 C7 C6 120.2(4) . . ?
C7 C8 N2 126.0(3) . . ?
C7 C8 C9 117.5(3) . . ?
N2 C8 C9 116.5(3) . . ?
N1 C9 C4 120.7(3) . . ?
N1 C9 C8 117.9(3) . . ?
C4 C9 C8 121.3(3) . . ?
O1 C10 N2 124.3(3) . . ?
O1 C10 C11 121.2(3) . . ?
N2 C10 C11 114.5(3) . . ?
C13 C11 C12 110.7(3) . . ?
C13 C11 C14 109.1(3) . . ?
C12 C11 C14 108.9(3) . . ?
C13 C11 C10 106.7(3) . . ?
C12 C11 C10 113.0(3) . . ?
C14 C11 C10 108.3(3) . . ?
C11 C12 Pd 109.1(2) . . ?
N3 C15 Pd 168.2(3) . . ?
N3 C16 C19 108.0(3) . . ?
N3 C16 C17 106.1(3) . . ?
C19 C16 C17 113.1(4) . . ?
N3 C16 C18 106.3(3) . . ?
C19 C16 C18 111.8(4) . . ?
C17 C16 C18 111.2(4) . . ?
Cl2 C20 Cl1 111.0(3) . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Pd N2 1.981(3) . ?
Pd C15 1.993(4) . ?
Pd C12 2.072(3) . ?
Pd N1 2.171(3) . ?
Pd Br1 2.4411(5) . ?
Pd Br2 2.4690(5) . ?
O1 C10 1.228(4) . ?
N1 C1 1.314(5) . ?
N1 C9 1.372(4) . ?
N2 C10 1.357(5) . ?
N2 C8 1.403(4) . ?
N3 C15 1.137(4) . ?
N3 C16 1.476(4) . ?
C1 C2 1.397(5) . ?
C2 C3 1.352(6) . ?
C3 C4 1.413(6) . ?
C4 C5 1.410(6) . ?
C4 C9 1.421(5) . ?
C5 C6 1.354(6) . ?
C6 C7 1.416(6) . ?
C7 C8 1.391(5) . ?
C8 C9 1.427(5) . ?
C10 C11 1.540(5) . ?
C11 C13 1.528(6) . ?
C11 C12 1.533(5) . ?
C11 C14 1.536(6) . ?
C16 C19 1.506(6) . ?
C16 C17 1.509(6) . ?
C16 C18 1.520(6) . ?
C20 Cl2 1.739(5) . ?
C20 Cl1 1.742(5) . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 Pd N1 C1 179.9(4) . . . . ?
C15 Pd N1 C1 -4.9(4) . . . . ?
C12 Pd N1 C1 179.7(5) . . . . ?
Br1 Pd N1 C1 -88.7(3) . . . . ?
Br2 Pd N1 C1 88.7(3) . . . . ?
N2 Pd N1 C9 -2.8(2) . . . . ?
C15 Pd N1 C9 172.4(2) . . . . ?
C12 Pd N1 C9 -3.0(6) . . . . ?
Br1 Pd N1 C9 88.6(2) . . . . ?
Br2 Pd N1 C9 -94.0(2) . . . . ?
C15 Pd N2 C10 91.7(15) . . . . ?
C12 Pd N2 C10 -0.8(3) . . . . ?
N1 Pd N2 C10 179.3(3) . . . . ?
Br1 Pd N2 C10 88.9(3) . . . . ?
Br2 Pd N2 C10 -90.4(3) . . . . ?
C15 Pd N2 C8 -85.6(15) . . . . ?
C12 Pd N2 C8 -178.1(3) . . . . ?
N1 Pd N2 C8 2.0(2) . . . . ?
Br1 Pd N2 C8 -88.3(2) . . . . ?
Br2 Pd N2 C8 92.3(2) . . . . ?
C9 N1 C1 C2 0.3(6) . . . . ?
Pd N1 C1 C2 177.3(3) . . . . ?
N1 C1 C2 C3 -0.9(6) . . . . ?
C1 C2 C3 C4 1.2(6) . . . . ?
C2 C3 C4 C5 180.0(4) . . . . ?
C2 C3 C4 C9 -0.9(6) . . . . ?
C3 C4 C5 C6 180.0(4) . . . . ?
C9 C4 C5 C6 0.9(6) . . . . ?
C4 C5 C6 C7 -0.4(7) . . . . ?
C5 C6 C7 C8 0.3(7) . . . . ?
C6 C7 C8 N2 -178.3(4) . . . . ?
C6 C7 C8 C9 -0.7(6) . . . . ?
C10 N2 C8 C7 -0.3(6) . . . . ?
Pd N2 C8 C7 176.6(3) . . . . ?
C10 N2 C8 C9 -177.9(4) . . . . ?
Pd N2 C8 C9 -0.9(4) . . . . ?
C1 N1 C9 C4 0.1(5) . . . . ?
Pd N1 C9 C4 -177.6(3) . . . . ?
C1 N1 C9 C8 -179.2(3) . . . . ?
Pd N1 C9 C8 3.2(4) . . . . ?
C5 C4 C9 N1 179.4(3) . . . . ?
C3 C4 C9 N1 0.3(5) . . . . ?
C5 C4 C9 C8 -1.3(5) . . . . ?
C3 C4 C9 C8 179.5(3) . . . . ?
C7 C8 C9 N1 -179.5(3) . . . . ?
N2 C8 C9 N1 -1.7(5) . . . . ?
C7 C8 C9 C4 1.2(5) . . . . ?
N2 C8 C9 C4 179.0(3) . . . . ?
C8 N2 C10 O1 -6.4(7) . . . . ?
Pd N2 C10 O1 176.7(3) . . . . ?
C8 N2 C10 C11 171.4(3) . . . . ?
Pd N2 C10 C11 -5.5(4) . . . . ?
O1 C10 C11 C13 67.0(5) . . . . ?
N2 C10 C11 C13 -110.9(4) . . . . ?
O1 C10 C11 C12 -171.0(4) . . . . ?
N2 C10 C11 C12 11.1(5) . . . . ?
O1 C10 C11 C14 -50.3(5) . . . . ?
N2 C10 C11 C14 131.8(4) . . . . ?
C13 C11 C12 Pd 108.6(3) . . . . ?
C14 C11 C12 Pd -131.5(3) . . . . ?
C10 C11 C12 Pd -11.1(4) . . . . ?
N2 Pd C12 C11 6.7(3) . . . . ?
C15 Pd C12 C11 -168.6(3) . . . . ?
N1 Pd C12 C11 6.9(7) . . . . ?
Br1 Pd C12 C11 -84.8(3) . . . . ?
Br2 Pd C12 C11 98.0(3) . . . . ?
C16 N3 C15 Pd -14(3) . . . . ?
N2 Pd C15 N3 20(3) . . . . ?
C12 Pd C15 N3 111.6(15) . . . . ?
N1 Pd C15 N3 -67.2(15) . . . . ?
Br1 Pd C15 N3 22.4(15) . . . . ?
Br2 Pd C15 N3 -158.3(15) . . . . ?
C15 N3 C16 C19 172.9(18) . . . . ?
C15 N3 C16 C17 51.5(19) . . . . ?
C15 N3 C16 C18 -66.9(19) . . . . ?
