data_str-307
_publ_requested_journal          BJOC
_publ_contact_author_name        'Thomas Strassner'
_publ_contact_author_address     
;Fachrichtung Chemie und Lebensmittelchemie
Professur fuer Physikalische Organische Chemie
TU Dresden
01062 Dresden
Germany
;
_publ_contact_author_email       thomas.strassner@chemie.tu-dresden.de
_publ_contact_author_phone       '+49 351 463 38535'
_publ_contact_author_fax         '+49 351 463 38571'
loop_
_publ_author_name
_publ_author_address
'Meyer, Dirk'
;Fachrichtung Chemie und Lebensmittelchemie
Professur fuer Physikalische Organische Chemie
TU Dresden
01062 Dresden
Germany
;
'Strassner, Thomas'
;Fachrichtung Chemie und Lebensmittelchemie
Professur fuer Physikalische Organische Chemie
TU Dresden
01062 Dresden
Germany
;
_publ_section_title              
;Methyl-Palladium Complexes with Pyrimidine-Functionalized N-Heterocyclic 
Carbene Ligands
;
_publ_section_abstract           
;
A series of methyl-palladium(II) complexes with pyrimidine-NHC 
ligands carrying different aryl- and alkyl substituents R 
([((pym)^(NHC-R))PdII(CH3)X] with X=Cl, CF3COO, CH3) has been 
prepared by transmetalation reactions from the corresponding 
silver complexes and chloro(methyl)(cyclooctadiene)palladium(II). 
The dimethyl(1-(2-pyrimidyl)-3-(2,6-diisopropylphenyl)imidazolin-2-
ylidene)palladium(II) complex was synthesized via the free 
carbene route. All complexes were fully characterized by 
standard methods and in three cases also by a solid state structure.
;
_publ_section_references         
;
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004).
enCIFer. J. Appl. Cryst. 37, 331-334.

Farrugia, L.J. (1997). J. Appl. Cryst. 30, 565. 

Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92-96.

Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).
J. Appl. Cryst. 36, 220--229.

COLLECT (2001)Data Collection Software for Nonius-kappa CCD devices. 
Bruker AXS: Delft, The Netherlands.

Sheldrick, G. M. (2008). Acta Crystallogr. A64, 112-122.

Bruker SADABS (2002). Area Detector Absorption and Other Corrections,
2.03. Delft, The Netherlands.

Spek, A. L. (2007). PLATON, A Multipurpose Crystallographic Tool, Utrecht
University, Utrecht, The Netherlands.
;
_audit_creation_method           SHELXL-97
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'C14 H12 Br Cl N4 Pd'
_chemical_formula_sum            'C14 H12 Br Cl N4 Pd'
_chemical_compound_source        synthesis
_exptl_crystal_recrystallization_method 'Acetonitrile/Diethyl ether'
_chemical_melting_point          475

_exptl_crystal_description       plate
_exptl_crystal_colour            colorless

_diffrn_ambient_temperature      198(2)
_chemical_formula_weight         458.04

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'
Br Br -0.2901 2.4595 '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'
Pd Pd -0.9988 1.0072 '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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/c'
_symmetry_int_tables_number      14
_chemical_absolute_configuration ?
_symmetry_space_group_name_Hall  '-P 2ybc'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   11.0550(8)
_cell_length_b                   8.0500(5)
_cell_length_c                   17.9200(10)
_cell_angle_alpha                90
_cell_angle_beta                 102.069(6)
_cell_angle_gamma                90
_cell_volume                     1559.50(17)
_cell_formula_units_Z            4
_cell_measurement_temperature    198(2)
_cell_measurement_reflns_used    112
_cell_measurement_theta_min      4.158
_cell_measurement_theta_max      20.621
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.951
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             888
_exptl_absorpt_coefficient_mu    3.920
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5018
_exptl_absorpt_correction_T_max  0.8281
_exptl_absorpt_process_details   'SADABS 2.03.(Sheldrick,Bruker AXS Inc.,2002)'

_exptl_special_details           
;
 ?
;
_diffrn_radiation_probe          ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       CCD
_diffrn_detector_area_resol_mean 9
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            18071
_diffrn_reflns_av_R_equivalents  0.0709
_diffrn_reflns_av_sigmaI/netI    0.0455
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         4.83
_diffrn_reflns_theta_max         26.40
_reflns_number_total             3175
_reflns_number_gt                2358
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_cell_refinement       'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)'
_computing_data_reduction        'EvalCCD (Duisenberg & Schreurs 1990-2000)'
_computing_structure_solution    'SIR92 (Altomare, 1994)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    
'Ortep III 1.0.3 (M.N.Burnett,C.K.Johnson,2000)'
_computing_publication_material  'XCIF 6.12 (Sheldrick, 1997)'

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0287P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3175
_refine_ls_number_parameters     191
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0574
_refine_ls_R_factor_gt           0.0311
_refine_ls_wR_factor_ref         0.0675
_refine_ls_wR_factor_gt          0.0605
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_restrained_S_all      1.098
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000

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
Pd1 Pd 0.32789(3) -0.09949(3) 0.534173(16) 0.02460(9) Uani 1 1 d . . .
Br2 Br -0.07617(5) 0.36349(6) 0.74202(3) 0.05984(17) Uani 1 1 d . . .
Cl1 Cl 0.42662(10) -0.34376(12) 0.58529(6) 0.0388(3) Uani 1 1 d . . .
N3 N 0.3907(3) -0.1286(3) 0.42947(16) 0.0264(7) Uani 1 1 d . . .
N1 N 0.2950(3) 0.1240(4) 0.41048(17) 0.0319(8) Uani 1 1 d . . .
N4 N 0.3769(3) 0.0108(4) 0.31113(17) 0.0374(8) Uani 1 1 d . . .
N2 N 0.1979(3) 0.2437(4) 0.48675(18) 0.0370(8) Uani 1 1 d . . .
C4 C 0.3589(3) -0.0032(4) 0.3809(2) 0.0278(8) Uani 1 1 d . . .
C6 C 0.4727(4) -0.2540(5) 0.3322(2) 0.0382(10) Uani 1 1 d . . .
H6A H 0.5146 -0.3437 0.3141 0.046 Uiso 1 1 calc R . .
C14 C 0.2595(4) -0.0637(5) 0.6299(2) 0.0353(10) Uani 1 1 d . . .
H14A H 0.2733 0.0518 0.6468 0.053 Uiso 1 1 calc R . .
H14B H 0.3017 -0.1382 0.6703 0.053 Uiso 1 1 calc R . .
H14C H 0.1706 -0.0875 0.6187 0.053 Uiso 1 1 calc R . .
C1 C 0.2619(3) 0.1036(5) 0.4795(2) 0.0304(8) Uani 1 1 d . . .
C5 C 0.4484(4) -0.2558(5) 0.4047(2) 0.0348(9) Uani 1 1 d . . .
H5A H 0.4731 -0.3484 0.4372 0.042 Uiso 1 1 calc R . .
C9 C 0.1841(4) 0.3774(6) 0.6070(3) 0.0509(12) Uani 1 1 d . . .
H9A H 0.2618 0.4292 0.6086 0.061 Uiso 1 1 calc R . .
C8 C 0.1328(3) 0.2782(5) 0.5467(2) 0.0328(9) Uani 1 1 d . . .
C11 C 0.0101(4) 0.3295(5) 0.6625(2) 0.0374(10) Uani 1 1 d . . .
C7 C 0.4347(4) -0.1194(5) 0.2874(2) 0.0397(10) Uani 1 1 d . . .
H7A H 0.4497 -0.1176 0.2371 0.048 Uiso 1 1 calc R . .
C13 C 0.0172(4) 0.2122(5) 0.5423(3) 0.0473(12) Uani 1 1 d . . .
H13A H -0.0205 0.1493 0.4987 0.057 Uiso 1 1 calc R . .
C12 C -0.0442(4) 0.2362(5) 0.6002(3) 0.0460(11) Uani 1 1 d . . .
H12A H -0.1238 0.1889 0.5975 0.055 Uiso 1 1 calc R . .
C10 C 0.1226(4) 0.4014(6) 0.6653(3) 0.0523(12) Uani 1 1 d . . .
H10A H 0.1587 0.4686 0.7077 0.063 Uiso 1 1 calc R . .
C3 C 0.1932(5) 0.3481(6) 0.4236(3) 0.0560(13) Uani 1 1 d . . .
H3A H 0.1544 0.4539 0.4164 0.067 Uiso 1 1 calc R . .
C2 C 0.2524(4) 0.2732(5) 0.3754(3) 0.0492(12) Uani 1 1 d . . .
H2A H 0.2633 0.3131 0.3274 0.059 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Pd1 0.02685(15) 0.02401(15) 0.02296(15) 0.00100(13) 0.00520(11) 0.00093(13)
Br2 0.0690(4) 0.0614(4) 0.0579(3) 0.0104(2) 0.0335(3) 0.0204(3)
Cl1 0.0537(6) 0.0322(5) 0.0329(5) 0.0090(4) 0.0146(5) 0.0125(5)
N3 0.0316(17) 0.0243(17) 0.0231(16) 0.0012(13) 0.0051(14) 0.0011(14)
N1 0.0396(19) 0.0280(19) 0.0288(17) 0.0083(14) 0.0092(15) 0.0083(15)
N4 0.050(2) 0.037(2) 0.0248(18) 0.0055(14) 0.0066(17) 0.0029(16)
N2 0.043(2) 0.0336(19) 0.037(2) 0.0063(15) 0.0120(16) 0.0136(16)
C4 0.029(2) 0.028(2) 0.025(2) 0.0002(16) 0.0022(17) -0.0023(16)
C6 0.057(3) 0.033(2) 0.026(2) -0.0042(17) 0.013(2) 0.006(2)
C14 0.043(2) 0.038(2) 0.028(2) 0.0042(17) 0.0145(19) 0.0124(19)
C1 0.0289(19) 0.034(2) 0.0284(19) -0.0003(18) 0.0061(16) 0.0039(18)
C5 0.043(2) 0.029(2) 0.031(2) -0.0018(17) 0.0033(19) 0.0031(19)
C9 0.028(2) 0.061(3) 0.064(3) -0.018(2) 0.011(2) -0.013(2)
C8 0.026(2) 0.028(2) 0.043(2) 0.0017(18) 0.0052(18) 0.0096(17)
C11 0.038(2) 0.033(2) 0.043(3) 0.0067(19) 0.012(2) 0.0132(19)
C7 0.059(3) 0.038(3) 0.023(2) -0.0049(18) 0.011(2) -0.003(2)
C13 0.037(2) 0.045(3) 0.057(3) -0.020(2) 0.004(2) -0.004(2)
C12 0.035(2) 0.039(3) 0.067(3) -0.008(2) 0.018(2) -0.008(2)
C10 0.038(2) 0.068(3) 0.049(3) -0.023(2) 0.005(2) -0.013(2)
C3 0.074(3) 0.038(3) 0.060(3) 0.022(2) 0.023(3) 0.026(2)
C2 0.063(3) 0.040(3) 0.046(3) 0.018(2) 0.015(2) 0.020(2)

_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

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
Pd1 C1 1.966(4) . ?
Pd1 C14 2.035(3) . ?
Pd1 N3 2.145(3) . ?
Pd1 Cl1 2.3407(10) . ?
Br2 C11 1.893(4) . ?
N3 C5 1.330(5) . ?
N3 C4 1.331(4) . ?
N1 C1 1.372(4) . ?
N1 C2 1.390(5) . ?
N1 C4 1.409(5) . ?
N4 C4 1.311(4) . ?
N4 C7 1.342(5) . ?
N2 C1 1.351(5) . ?
N2 C3 1.402(5) . ?
N2 C8 1.441(5) . ?
C6 C7 1.361(5) . ?
C6 C5 1.382(5) . ?
C6 H6A 0.9500 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C5 H5A 0.9500 . ?
C9 C8 1.367(6) . ?
C9 C10 1.374(6) . ?
C9 H9A 0.9500 . ?
C8 C13 1.371(5) . ?
C11 C10 1.363(6) . ?
C11 C12 1.375(6) . ?
C7 H7A 0.9500 . ?
C13 C12 1.368(6) . ?
C13 H13A 0.9500 . ?
C12 H12A 0.9500 . ?
C10 H10A 0.9500 . ?
C3 C2 1.332(6) . ?
C3 H3A 0.9500 . ?
C2 H2A 0.9500 . ?

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
C1 Pd1 C14 97.90(15) . . ?
C1 Pd1 N3 79.03(13) . . ?
C14 Pd1 N3 176.52(13) . . ?
C1 Pd1 Cl1 170.99(10) . . ?
C14 Pd1 Cl1 90.80(11) . . ?
N3 Pd1 Cl1 92.33(8) . . ?
C5 N3 C4 116.4(3) . . ?
C5 N3 Pd1 129.9(3) . . ?
C4 N3 Pd1 113.5(2) . . ?
C1 N1 C2 112.4(3) . . ?
C1 N1 C4 120.1(3) . . ?
C2 N1 C4 127.4(3) . . ?
C4 N4 C7 114.3(3) . . ?
C1 N2 C3 110.8(3) . . ?
C1 N2 C8 125.8(3) . . ?
C3 N2 C8 123.1(3) . . ?
N4 C4 N3 128.1(3) . . ?
N4 C4 N1 118.9(3) . . ?
N3 C4 N1 113.0(3) . . ?
C7 C6 C5 117.8(4) . . ?
C7 C6 H6A 121.1 . . ?
C5 C6 H6A 121.1 . . ?
Pd1 C14 H14A 109.5 . . ?
Pd1 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
Pd1 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
N2 C1 N1 103.3(3) . . ?
N2 C1 Pd1 142.5(3) . . ?
N1 C1 Pd1 114.0(2) . . ?
N3 C5 C6 120.4(4) . . ?
N3 C5 H5A 119.8 . . ?
C6 C5 H5A 119.8 . . ?
C8 C9 C10 119.5(4) . . ?
C8 C9 H9A 120.2 . . ?
C10 C9 H9A 120.2 . . ?
C9 C8 C13 120.0(4) . . ?
C9 C8 N2 120.8(4) . . ?
C13 C8 N2 119.2(4) . . ?
C10 C11 C12 120.1(4) . . ?
C10 C11 Br2 120.7(3) . . ?
C12 C11 Br2 119.1(3) . . ?
N4 C7 C6 123.0(4) . . ?
N4 C7 H7A 118.5 . . ?
C6 C7 H7A 118.5 . . ?
C12 C13 C8 120.3(4) . . ?
C12 C13 H13A 119.8 . . ?
C8 C13 H13A 119.8 . . ?
C13 C12 C11 119.4(4) . . ?
C13 C12 H12A 120.3 . . ?
C11 C12 H12A 120.3 . . ?
C11 C10 C9 120.3(4) . . ?
C11 C10 H10A 119.8 . . ?
C9 C10 H10A 119.8 . . ?
C2 C3 N2 108.1(4) . . ?
C2 C3 H3A 125.9 . . ?
N2 C3 H3A 125.9 . . ?
C3 C2 N1 105.3(4) . . ?
C3 C2 H2A 127.3 . . ?
N1 C2 H2A 127.3 . . ?

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
C1 Pd1 N3 C5 -174.4(4) . . . . ?
Cl1 Pd1 N3 C5 8.2(3) . . . . ?
C1 Pd1 N3 C4 0.8(3) . . . . ?
Cl1 Pd1 N3 C4 -176.6(2) . . . . ?
C7 N4 C4 N3 0.0(6) . . . . ?
C7 N4 C4 N1 -177.7(3) . . . . ?
C5 N3 C4 N4 0.4(6) . . . . ?
Pd1 N3 C4 N4 -175.5(3) . . . . ?
C5 N3 C4 N1 178.2(3) . . . . ?
Pd1 N3 C4 N1 2.3(4) . . . . ?
C1 N1 C4 N4 172.1(3) . . . . ?
C2 N1 C4 N4 -4.0(6) . . . . ?
C1 N1 C4 N3 -5.9(5) . . . . ?
C2 N1 C4 N3 178.0(4) . . . . ?
C3 N2 C1 N1 -0.5(5) . . . . ?
C8 N2 C1 N1 174.1(3) . . . . ?
C3 N2 C1 Pd1 174.3(4) . . . . ?
C8 N2 C1 Pd1 -11.1(7) . . . . ?
C2 N1 C1 N2 -0.1(4) . . . . ?
C4 N1 C1 N2 -176.8(3) . . . . ?
C2 N1 C1 Pd1 -176.7(3) . . . . ?
C4 N1 C1 Pd1 6.7(4) . . . . ?
C14 Pd1 C1 N2 3.4(5) . . . . ?
N3 Pd1 C1 N2 -178.3(5) . . . . ?
C14 Pd1 C1 N1 177.9(3) . . . . ?
N3 Pd1 C1 N1 -3.8(3) . . . . ?
C4 N3 C5 C6 0.0(5) . . . . ?
Pd1 N3 C5 C6 175.1(3) . . . . ?
C7 C6 C5 N3 -0.6(6) . . . . ?
C10 C9 C8 C13 4.2(7) . . . . ?
C10 C9 C8 N2 -176.8(4) . . . . ?
C1 N2 C8 C9 100.2(5) . . . . ?
C3 N2 C8 C9 -85.8(5) . . . . ?
C1 N2 C8 C13 -80.7(5) . . . . ?
C3 N2 C8 C13 93.3(5) . . . . ?
C4 N4 C7 C6 -0.7(6) . . . . ?
C5 C6 C7 N4 1.0(7) . . . . ?
C9 C8 C13 C12 -4.1(7) . . . . ?
N2 C8 C13 C12 176.8(4) . . . . ?
C8 C13 C12 C11 1.0(7) . . . . ?
C10 C11 C12 C13 2.0(7) . . . . ?
Br2 C11 C12 C13 179.5(3) . . . . ?
C12 C11 C10 C9 -1.9(7) . . . . ?
Br2 C11 C10 C9 -179.4(4) . . . . ?
C8 C9 C10 C11 -1.2(7) . . . . ?
C1 N2 C3 C2 1.0(6) . . . . ?
C8 N2 C3 C2 -173.8(4) . . . . ?
N2 C3 C2 N1 -1.0(5) . . . . ?
C1 N1 C2 C3 0.8(5) . . . . ?
C4 N1 C2 C3 177.1(4) . . . . ?

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        26.40
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         0.616
_refine_diff_density_min         -0.474
_refine_diff_density_rms         0.099

