#------------------------------------------------------------------------------
#$Date: 2016-02-16 22:30:59 +0200 (Tue, 16 Feb 2016) $
#$Revision: 176467 $
#$URL: svn://www.crystallography.net/cod/cif/4/11/40/4114075.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_4114075
loop_
_publ_author_name
'Alexandra K. de K. Lewis'
'Stephen Caddick'
'F. Geoffrey N. Cloke'
'Norman C. Billingham'
'Peter B. Hitchcock'
'John Leonard'
_publ_section_title
;
 Synthetic, Structural, and Mechanistic Studies on the Oxidative Addition
 of Aromatic Chlorides to a Palladium (N-Heterocyclic Carbene) Complex:
 Relevance to Catalytic Amination
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10066
_journal_page_last               10073
_journal_paper_doi               10.1021/ja035565k
_journal_volume                  125
_journal_year                    2003
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         '(C30 H47 Cl1 N4 O2 Pd1).1/2(C6 D6)'
_chemical_formula_sum            'C33 H47 Cl D3 N4 O2 Pd'
_chemical_formula_weight         679.6
_chemical_name_common
;
[PdCl(C3H2N2tBu2)2(C6H4COOMe)].1/2C6D6)
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.2
_audit_creation_date             2002-11-15T09:53:41-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90.684(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9479(2)
_cell_length_b                   13.4003(2)
_cell_length_c                   25.1111(3)
_cell_measurement_reflns_used    38748
_cell_measurement_temperature    223(2)
_cell_measurement_theta_max      25.682
_cell_measurement_theta_min      3.705
_cell_measurement_wavelength     0.71073
_cell_volume                     3347.19(9)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_data_reduction
'HKL Denzo and Scalepack (Otwinowski & Minor 1997)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      223(2)
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       CCD
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            46363
_diffrn_reflns_theta_full        25.67
_diffrn_reflns_theta_max         25.67
_diffrn_reflns_theta_min         3.75
_exptl_absorpt_coefficient_mu    0.668
_exptl_absorpt_correction_T_max  0.8853
_exptl_absorpt_correction_T_min  0.7556
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38]
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       prism
_exptl_crystal_F_000             1420
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.491
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    riding
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         6214
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0287
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0302P)²+3.5199P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0684
_refine_ls_wR_factor_ref         0.0709
_reflns_number_gt                5614
_reflns_number_total             6214
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja035565ksi20030619_094203.cif
_cod_data_source_block           nov2002
_cod_original_formula_sum        'C33 H47 D3 Cl N4 O2 Pd'
_cod_database_code               4114075
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
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
Pd Pd 0.542371(16) 0.183024(12) 0.352923(6) 0.02166(6) Uani 1 1 d .
Cl Cl 0.62511(7) 0.35270(4) 0.34439(3) 0.04037(15) Uani 1 1 d .
O1 O 0.39944(18) -0.33197(12) 0.36859(7) 0.0386(4) Uani 1 1 d .
O2 O 0.2001(2) -0.27641(15) 0.39480(10) 0.0642(6) Uani 1 1 d .
N1 N 0.82773(18) 0.08689(14) 0.35600(8) 0.0312(4) Uani 1 1 d .
N2 N 0.75500(19) 0.09687(14) 0.27457(8) 0.0313(4) Uani 1 1 d .
N3 N 0.25491(18) 0.27879(14) 0.34921(7) 0.0270(4) Uani 1 1 d .
N4 N 0.33180(18) 0.27882(14) 0.43005(7) 0.0247(4) Uani 1 1 d .
C1 C 0.7240(2) 0.12462(16) 0.32566(9) 0.0266(5) Uani 1 1 d .
C2 C 0.9129(3) 0.0312(2) 0.32452(12) 0.0454(7) Uani 1 1 d .
H2 H 0.989 -0.0045 0.3363 0.054 Uiso 1 1 calc R
C3 C 0.8678(3) 0.0371(2) 0.27460(12) 0.0439(7) Uani 1 1 d .
H3 H 0.9059 0.0061 0.2447 0.053 Uiso 1 1 calc R
C4 C 0.8507(2) 0.09711(19) 0.41511(10) 0.0365(6) Uani 1 1 d .
C5 C 0.7693(3) 0.0180(2) 0.44372(11) 0.0474(7) Uani 1 1 d .
H5A H 0.7947 -0.0476 0.431 0.071 Uiso 1 1 calc R
H5B H 0.6743 0.0289 0.4367 0.071 Uiso 1 1 calc R
H5C H 0.7868 0.0223 0.4817 0.071 Uiso 1 1 calc R
C6 C 0.8151(3) 0.2013(2) 0.43296(12) 0.0482(7) Uani 1 1 d .
H6A H 0.8697 0.2493 0.414 0.072 Uiso 1 1 calc R
H6B H 0.832 0.2075 0.4709 0.072 Uiso 1 1 calc R
H6C H 0.7208 0.2139 0.4254 0.072 Uiso 1 1 calc R
C7 C 1.0004(3) 0.0819(3) 0.42792(14) 0.0606(9) Uani 1 1 d .
H7A H 1.0528 0.1319 0.4095 0.091 Uiso 1 1 calc R
H7B H 1.0278 0.0159 0.4164 0.091 Uiso 1 1 calc R
H7C H 1.0155 0.0882 0.466 0.091 Uiso 1 1 calc R
C8 C 0.6802(3) 0.12030(19) 0.22342(10) 0.0365(6) Uani 1 1 d .
C9 C 0.6256(3) 0.2250(2) 0.22485(11) 0.0545(8) Uani 1 1 d .
H9A H 0.6991 0.2717 0.2298 0.082 Uiso 1 1 calc R
H9B H 0.5634 0.2313 0.2541 0.082 Uiso 1 1 calc R
H9C H 0.5791 0.2394 0.1915 0.082 Uiso 1 1 calc R
C10 C 0.5705(3) 0.0412(2) 0.21530(11) 0.0524(7) Uani 1 1 d .
H10A H 0.6112 -0.0246 0.2147 0.079 Uiso 1 1 calc R
H10B H 0.5237 0.0533 0.1818 0.079 Uiso 1 1 calc R
H10C H 0.5071 0.0449 0.2443 0.079 Uiso 1 1 calc R
C11 C 0.7783(3) 0.1135(2) 0.17694(11) 0.0493(7) Uani 1 1 d .
H11A H 0.8152 0.0466 0.1752 0.074 Uiso 1 1 calc R
H11B H 0.8506 0.1611 0.1823 0.074 Uiso 1 1 calc R
H11C H 0.7311 0.1285 0.1439 0.074 Uiso 1 1 calc R
C12 C 0.3619(2) 0.24700(15) 0.37966(8) 0.0232(4) Uani 1 1 d .
C13 C 0.1665(2) 0.33291(19) 0.37989(10) 0.0352(6) Uani 1 1 d .
H13 H 0.0873 0.3642 0.3678 0.042 Uiso 1 1 calc R
C14 C 0.2139(2) 0.33267(18) 0.42960(10) 0.0340(5) Uani 1 1 d .
H14 H 0.1742 0.3636 0.4591 0.041 Uiso 1 1 calc R
C15 C 0.2315(2) 0.26895(19) 0.29001(9) 0.0338(5) Uani 1 1 d .
C16 C 0.3052(4) 0.3534(2) 0.26305(11) 0.0559(8) Uani 1 1 d .
H16A H 0.2732 0.4167 0.2767 0.084 Uiso 1 1 calc R
H16B H 0.2887 0.3504 0.2249 0.084 Uiso 1 1 calc R
H16C H 0.4008 0.3473 0.2702 0.084 Uiso 1 1 calc R
C17 C 0.2764(3) 0.1672(2) 0.27089(11) 0.0488(7) Uani 1 1 d .
H17A H 0.2267 0.1158 0.2894 0.073 Uiso 1 1 calc R
H17B H 0.3718 0.1591 0.2781 0.073 Uiso 1 1 calc R
H17C H 0.2594 0.1615 0.2329 0.073 Uiso 1 1 calc R
C18 C 0.0798(3) 0.2756(2) 0.27848(12) 0.0508(7) Uani 1 1 d .
H18A H 0.0344 0.2207 0.2959 0.076 Uiso 1 1 calc R
H18B H 0.0637 0.2718 0.2404 0.076 Uiso 1 1 calc R
H18C H 0.0455 0.3384 0.2919 0.076 Uiso 1 1 calc R
C19 C 0.4134(2) 0.26735(19) 0.48068(9) 0.0328(5) Uani 1 1 d .
C20 C 0.4715(3) 0.1633(2) 0.48418(10) 0.0436(7) Uani 1 1 d .
H20A H 0.3991 0.1149 0.4841 0.065 Uiso 1 1 calc R
H20B H 0.5239 0.1569 0.5168 0.065 Uiso 1 1 calc R
H20C H 0.5289 0.1515 0.4539 0.065 Uiso 1 1 calc R
C21 C 0.5216(3) 0.3474(2) 0.48095(12) 0.0545(8) Uani 1 1 d .
H21A H 0.4798 0.4127 0.4785 0.082 Uiso 1 1 calc R
H21B H 0.5801 0.3377 0.4508 0.082 Uiso 1 1 calc R
H21C H 0.5739 0.343 0.5137 0.082 Uiso 1 1 calc R
C22 C 0.3221(3) 0.2816(3) 0.52849(11) 0.0602(9) Uani 1 1 d .
H22A H 0.2842 0.3483 0.5277 0.09 Uiso 1 1 calc R
H22B H 0.3739 0.2727 0.5611 0.09 Uiso 1 1 calc R
H22C H 0.25 0.2329 0.5271 0.09 Uiso 1 1 calc R
C23 C 0.4706(2) 0.03965(16) 0.36093(8) 0.0226(4) Uani 1 1 d .
C24 C 0.3439(2) 0.01948(17) 0.38210(10) 0.0319(5) Uani 1 1 d .
H24 H 0.29 0.0735 0.3925 0.038 Uiso 1 1 calc R
C25 C 0.2944(2) -0.07608(18) 0.38840(10) 0.0327(5) Uani 1 1 d .
H25 H 0.208 -0.0853 0.4024 0.039 Uiso 1 1 calc R
C26 C 0.3705(2) -0.15855(17) 0.37438(9) 0.0261(5) Uani 1 1 d .
C27 C 0.4971(2) -0.14148(17) 0.35399(9) 0.0271(5) Uani 1 1 d .
H27 H 0.5512 -0.196 0.3446 0.033 Uiso 1 1 calc R
C28 C 0.5452(2) -0.04583(17) 0.34726(9) 0.0272(5) Uani 1 1 d .
H28 H 0.6313 -0.0373 0.333 0.033 Uiso 1 1 calc R
C29 C 0.3131(2) -0.25944(18) 0.38067(9) 0.0322(5) Uani 1 1 d .
C30 C 0.3512(3) -0.43326(18) 0.37381(12) 0.0478(7) Uani 1 1 d .
H30A H 0.327 -0.4456 0.4105 0.072 Uiso 1 1 calc R
H30B H 0.4214 -0.4794 0.3635 0.072 Uiso 1 1 calc R
H30C H 0.273 -0.4427 0.3509 0.072 Uiso 1 1 calc R
C31 C 0.9074(3) 0.4256(2) 0.50705(12) 0.0473(7) Uani 1 1 d .
H31 H 0.8434 0.3749 0.5118 0.057 Uiso 1 1 calc R
C32 C 0.9093(3) 0.4783(2) 0.46005(12) 0.0475(7) Uani 1 1 d .
H32 H 0.8472 0.4631 0.4327 0.057 Uiso 1 1 calc R
C33 C 1.0017(3) 0.5533(2) 0.45295(12) 0.0474(7) Uani 1 1 d .
H33 H 1.0027 0.5898 0.421 0.057 Uiso 1 1 calc R
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 0 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.006 '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
C23 Pd C1 89.12(8) .
C23 Pd C12 92.91(8) .
C1 Pd C12 177.94(8) .
C23 Pd Cl 179.27(6) .
C1 Pd Cl 91.52(6) .
C12 Pd Cl 86.45(6) .
C29 O1 C30 116.6(2) .
C2 N1 C1 110.1(2) .
C2 N1 C4 121.7(2) .
C1 N1 C4 128.20(19) .
C1 N2 C3 110.4(2) .
C1 N2 C8 128.60(19) .
C3 N2 C8 120.9(2) .
C12 N3 C13 110.32(18) .
C12 N3 C15 129.24(18) .
C13 N3 C15 120.25(19) .
C14 N4 C12 110.55(18) .
C14 N4 C19 120.65(18) .
C12 N4 C19 128.67(18) .
N2 C1 N1 104.04(19) .
N2 C1 Pd 127.69(17) .
N1 C1 Pd 127.09(16) .
C3 C2 N1 107.7(2) .
C2 C3 N2 107.5(2) .
C6 C4 N1 110.1(2) .
C6 C4 C5 112.1(2) .
N1 C4 C5 109.1(2) .
C6 C4 C7 107.0(2) .
N1 C4 C7 109.3(2) .
C5 C4 C7 109.3(2) .
C9 C8 N2 110.4(2) .
C9 C8 C10 113.0(3) .
N2 C8 C10 108.2(2) .
C9 C8 C11 107.9(2) .
N2 C8 C11 108.9(2) .
C10 C8 C11 108.4(2) .
N3 C12 N4 103.94(17) .
N3 C12 Pd 127.43(15) .
N4 C12 Pd 128.10(15) .
C14 C13 N3 107.6(2) .
C13 C14 N4 107.5(2) .
N3 C15 C16 107.8(2) .
N3 C15 C17 110.39(19) .
C16 C15 C17 112.7(2) .
N3 C15 C18 108.7(2) .
C16 C15 C18 110.7(2) .
C17 C15 C18 106.6(2) .
C20 C19 C21 112.3(2) .
C20 C19 N4 110.18(19) .
C21 C19 N4 107.8(2) .
C20 C19 C22 107.5(2) .
C21 C19 C22 109.6(2) .
N4 C19 C22 109.4(2) .
C24 C23 C28 114.5(2) .
C24 C23 Pd 122.12(16) .
C28 C23 Pd 123.35(15) .
C25 C24 C23 123.1(2) .
C24 C25 C26 120.8(2) .
C27 C26 C25 117.6(2) .
C27 C26 C29 123.0(2) .
C25 C26 C29 119.3(2) .
C28 C27 C26 121.2(2) .
C27 C28 C23 122.7(2) .
O2 C29 O1 122.3(2) .
O2 C29 C26 124.6(2) .
O1 C29 C26 113.1(2) .
C33 C31 C32 120.4(3) 3_766
C31 C32 C33 120.2(3) .
C31 C33 C32 119.4(3) 3_766
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Pd C23 2.060(2) .
Pd C1 2.091(2) .
Pd C12 2.106(2) .
Pd Cl 2.4284(6) .
O1 C29 1.334(3) .
O1 C30 1.446(3) .
O2 C29 1.204(3) .
N1 C2 1.385(3) .
N1 C1 1.372(3) .
N1 C4 1.505(3) .
N2 C1 1.374(3) .
N2 C3 1.379(3) .
N2 C8 1.510(3) .
N3 C12 1.371(3) .
N3 C13 1.381(3) .
N3 C15 1.508(3) .
N4 C14 1.377(3) .
N4 C12 1.372(3) .
N4 C19 1.508(3) .
C2 C3 1.329(4) .
C4 C6 1.509(4) .
C4 C5 1.520(4) .
C4 C7 1.534(3) .
C8 C9 1.505(4) .
C8 C10 1.533(4) .
C8 C11 1.533(3) .
C13 C14 1.329(4) .
C15 C16 1.513(4) .
C15 C17 1.515(4) .
C15 C18 1.535(4) .
C19 C20 1.511(3) .
C19 C21 1.520(4) .
C19 C22 1.526(3) .
C23 C24 1.400(3) .
C23 C28 1.410(3) .
C24 C25 1.382(3) .
C25 C26 1.387(3) .
C26 C27 1.384(3) .
C26 C29 1.477(3) .
C27 C28 1.379(3) .
C31 C33 1.373(4) 3_766
C31 C32 1.376(4) .
C32 C33 1.375(4) .
C33 C31 1.373(4) 3_766
