# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2006


data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Martin Albrecht'
_publ_contact_author_address     
;
Chemistry Department
University of Fribourg
Organometallic Synthesis Lab
Chemin du Musee 9
Fribourg
1700
SWITZERLAND
;

_publ_contact_author_email       MARTIN.ALBRECHT@UNIFR.CH

_publ_section_title              
;
Mild and rational synthesis of palladium complexes
comprising C(4)-bound N-heterocyclic carbenes
;
loop_
_publ_author_name
'Evelyne Kluser'
'Antonia Neels'
'Martin Albrecht'
# Attachment 'compound2.CIF'

data_compound2
_database_code_depnum_ccdc_archive 'CCDC 615954'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H21 Br I N3 O Pd S'
_chemical_formula_weight         592.61

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'
I I -0.4742 1.8119 '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'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/n

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'

_cell_length_a                   10.6134(9)
_cell_length_b                   14.8459(16)
_cell_length_c                   12.0432(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 91.267(10)
_cell_angle_gamma                90.00
_cell_volume                     1897.1(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    6170
_cell_measurement_theta_min      1.65
_cell_measurement_theta_max      26.05

_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.35
_exptl_crystal_density_meas      none
_exptl_crystal_density_diffrn    2.075
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1136
_exptl_absorpt_coefficient_mu    4.826
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.227
_exptl_absorpt_correction_T_max  0.315
_exptl_absorpt_process_details   'MULABS, (PLATON03, Speck, 2003)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'STOE IPDS'
_diffrn_measurement_method       'phi oscillation'
_diffrn_detector_area_resol_mean 0.81\%A
_diffrn_standards_number         0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_decay_%        0
_diffrn_reflns_number            11103
_diffrn_reflns_av_R_equivalents  0.0573
_diffrn_reflns_av_sigmaI/netI    0.0701
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.18
_diffrn_reflns_theta_max         26.09
_reflns_number_total             3656
_reflns_number_gt                2369
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'EXPOSE (Stoe IPDS Software, 2000)'
_computing_cell_refinement       'CELL (Stoe IPDS Software, 2000)'
_computing_data_reduction        'INTEGRATE (Stoe IPDS Software, 2000)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'PLATON99 (Spek, 1990)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0783P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/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     SHELXL
_refine_ls_extinction_coef       0.0034(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         3656
_refine_ls_number_parameters     204
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0418
_refine_ls_wR_factor_ref         0.1252
_refine_ls_wR_factor_gt          0.1133
_refine_ls_goodness_of_fit_ref   0.912
_refine_ls_restrained_S_all      0.912
_refine_ls_shift/su_max          0.000
_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
I1 I 0.07688(6) 0.25993(4) 0.68104(5) 0.0412(2) Uani 1 1 d . . .
Pd1 Pd 0.30964(5) 0.25700(3) 0.72609(5) 0.01635(18) Uani 1 1 d . . .
Br1 Br 0.28689(8) 0.35688(5) 0.89305(7) 0.0282(2) Uani 1 1 d . . .
N1 N 0.5052(6) 0.2490(4) 0.7534(5) 0.0182(13) Uani 1 1 d . . .
N2 N 0.4378(5) 0.1955(4) 0.5297(5) 0.0171(13) Uani 1 1 d . . .
N3 N 0.3448(6) 0.0812(4) 0.4551(5) 0.0180(13) Uani 1 1 d . . .
C1 C 0.5492(7) 0.2327(4) 0.8569(7) 0.0210(16) Uani 1 1 d . . .
H1A H 0.4924 0.2327 0.9168 0.025 Uiso 1 1 calc R . .
C2 C 0.6739(8) 0.2161(5) 0.8776(7) 0.0262(19) Uani 1 1 d . . .
H2A H 0.7033 0.2031 0.9509 0.031 Uiso 1 1 calc R . .
C3 C 0.7562(8) 0.2183(5) 0.7919(7) 0.0277(19) Uani 1 1 d . . .
H3A H 0.8430 0.2061 0.8055 0.033 Uiso 1 1 calc R . .
C4 C 0.7138(7) 0.2379(5) 0.6871(7) 0.0238(17) Uani 1 1 d . . .
H4A H 0.7709 0.2422 0.6276 0.029 Uiso 1 1 calc R . .
C5 C 0.5836(7) 0.2516(4) 0.6686(6) 0.0199(16) Uani 1 1 d . . .
C6 C 0.5301(7) 0.2675(5) 0.5530(6) 0.0188(16) Uani 1 1 d . . .
H6A H 0.4887 0.3272 0.5485 0.023 Uiso 1 1 calc R . .
H6B H 0.5982 0.2657 0.4981 0.023 Uiso 1 1 calc R . .
C7 C 0.3342(7) 0.1796(5) 0.5964(6) 0.0187(16) Uani 1 1 d . . .
C8 C 0.2758(7) 0.1059(5) 0.5455(6) 0.0207(16) Uani 1 1 d . . .
H8A H 0.2009 0.0775 0.5693 0.025 Uiso 1 1 calc R . .
C9 C 0.4428(7) 0.1368(5) 0.4478(6) 0.0180(15) Uani 1 1 d . . .
H9A H 0.5056 0.1345 0.3928 0.022 Uiso 1 1 calc R . .
C10 C 0.3128(8) 0.0068(5) 0.3778(6) 0.0228(18) Uani 1 1 d . . .
H10A H 0.3110 -0.0501 0.4223 0.027 Uiso 1 1 calc R . .
C11 C 0.1825(9) 0.0207(6) 0.3278(8) 0.042(2) Uani 1 1 d . . .
H11A H 0.1801 0.0774 0.2863 0.063 Uiso 1 1 calc R . .
H11B H 0.1209 0.0229 0.3872 0.063 Uiso 1 1 calc R . .
H11C H 0.1619 -0.0294 0.2775 0.063 Uiso 1 1 calc R . .
C12 C 0.4127(9) -0.0038(6) 0.2917(8) 0.038(2) Uani 1 1 d . . .
H12A H 0.4952 -0.0108 0.3287 0.057 Uiso 1 1 calc R . .
H12B H 0.4135 0.0497 0.2440 0.057 Uiso 1 1 calc R . .
H12C H 0.3942 -0.0572 0.2464 0.057 Uiso 1 1 calc R . .
S1 S 0.3185(2) 0.52670(15) 0.5300(2) 0.0407(6) Uani 1 1 d . . .
O1 O 0.3466(7) 0.4394(4) 0.4752(6) 0.0507(18) Uani 1 1 d . . .
C13 C 0.3944(12) 0.5251(8) 0.6629(9) 0.056(3) Uani 1 1 d . . .
H13A H 0.4856 0.5192 0.6541 0.084 Uiso 1 1 calc R . .
H13B H 0.3632 0.4740 0.7058 0.084 Uiso 1 1 calc R . .
H13C H 0.3763 0.5813 0.7021 0.084 Uiso 1 1 calc R . .
C14 C 0.1600(11) 0.5220(10) 0.5748(15) 0.094(5) Uani 1 1 d . . .
H14A H 0.1471 0.4664 0.6168 0.141 Uiso 1 1 calc R . .
H14C H 0.1026 0.5231 0.5100 0.141 Uiso 1 1 calc R . .
H14B H 0.1431 0.5740 0.6223 0.141 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
I1 0.0305(4) 0.0550(4) 0.0383(4) -0.0048(3) 0.0047(3) 0.0038(3)
Pd1 0.0164(3) 0.0186(3) 0.0142(3) -0.0018(2) 0.0024(2) 0.0002(2)
Br1 0.0306(5) 0.0318(4) 0.0226(4) -0.0097(3) 0.0077(3) 0.0017(3)
N1 0.023(3) 0.015(3) 0.017(3) -0.005(2) 0.007(3) 0.001(3)
N2 0.016(3) 0.017(3) 0.018(3) 0.002(2) -0.001(3) -0.002(2)
N3 0.022(3) 0.019(3) 0.012(3) -0.003(2) 0.000(3) 0.000(2)
C1 0.022(4) 0.020(3) 0.020(4) 0.000(3) -0.005(3) 0.000(3)
C2 0.036(5) 0.020(3) 0.022(4) -0.005(3) -0.007(4) -0.002(3)
C3 0.019(4) 0.027(4) 0.037(5) -0.010(3) -0.010(4) -0.003(3)
C4 0.020(4) 0.023(4) 0.028(5) -0.006(3) -0.002(4) -0.006(3)
C5 0.019(4) 0.012(3) 0.028(4) -0.007(3) -0.005(3) -0.007(3)
C6 0.021(4) 0.023(4) 0.012(4) 0.000(3) 0.003(3) -0.008(3)
C7 0.016(4) 0.020(3) 0.020(4) 0.003(3) -0.004(3) -0.002(3)
C8 0.021(4) 0.022(4) 0.019(4) -0.003(3) 0.005(3) -0.003(3)
C9 0.017(4) 0.021(3) 0.015(4) -0.004(3) -0.001(3) -0.002(3)
C10 0.033(5) 0.016(3) 0.019(4) -0.003(3) 0.003(4) -0.001(3)
C11 0.042(6) 0.037(5) 0.045(6) -0.016(4) -0.017(5) 0.001(4)
C12 0.047(6) 0.036(5) 0.031(5) -0.017(4) 0.010(5) -0.013(4)
S1 0.0358(14) 0.0360(12) 0.0502(16) 0.0013(11) -0.0018(12) -0.0037(10)
O1 0.054(5) 0.045(4) 0.053(5) -0.005(3) -0.001(4) -0.009(3)
C13 0.068(8) 0.069(7) 0.031(6) -0.007(5) -0.001(6) 0.000(6)
C14 0.037(7) 0.099(10) 0.148(16) -0.014(10) 0.036(9) -0.001(7)

_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
I1 Pd1 2.5179(8) . ?
Pd1 C7 1.961(8) . ?
Pd1 N1 2.098(6) . ?
Pd1 Br1 2.5142(9) . ?
N1 C5 1.332(10) . ?
N1 C1 1.343(10) . ?
N2 C9 1.319(9) . ?
N2 C7 1.396(10) . ?
N2 C6 1.472(9) . ?
N3 C9 1.332(9) . ?
N3 C8 1.375(10) . ?
N3 C10 1.479(9) . ?
C1 C2 1.363(11) . ?
C1 H1A 0.9500 . ?
C2 C3 1.367(12) . ?
C2 H2A 0.9500 . ?
C3 C4 1.362(11) . ?
C3 H3A 0.9500 . ?
C4 C5 1.410(11) . ?
C4 H4A 0.9500 . ?
C5 C6 1.511(10) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 C8 1.392(10) . ?
C8 H8A 0.9500 . ?
C9 H9A 0.9500 . ?
C10 C12 1.508(12) . ?
C10 C11 1.510(11) . ?
C10 H10A 1.0000 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
S1 O1 1.488(7) . ?
S1 C13 1.776(11) . ?
S1 C14 1.779(12) . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 H14A 0.9800 . ?
C14 H14C 0.9800 . ?
C14 H14B 0.9800 . ?

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
C7 Pd1 N1 86.8(3) . . ?
C7 Pd1 Br1 177.9(2) . . ?
N1 Pd1 Br1 91.15(16) . . ?
C7 Pd1 I1 89.2(2) . . ?
N1 Pd1 I1 175.92(16) . . ?
Br1 Pd1 I1 92.93(3) . . ?
C5 N1 C1 120.4(7) . . ?
C5 N1 Pd1 120.7(5) . . ?
C1 N1 Pd1 118.6(5) . . ?
C9 N2 C7 111.3(6) . . ?
C9 N2 C6 125.8(6) . . ?
C7 N2 C6 122.9(6) . . ?
C9 N3 C8 108.5(6) . . ?
C9 N3 C10 126.1(6) . . ?
C8 N3 C10 125.3(6) . . ?
N1 C1 C2 121.2(8) . . ?
N1 C1 H1A 119.4 . . ?
C2 C1 H1A 119.4 . . ?
C1 C2 C3 119.4(8) . . ?
C1 C2 H2A 120.3 . . ?
C3 C2 H2A 120.3 . . ?
C4 C3 C2 120.1(8) . . ?
C4 C3 H3A 119.9 . . ?
C2 C3 H3A 119.9 . . ?
C3 C4 C5 118.6(8) . . ?
C3 C4 H4A 120.7 . . ?
C5 C4 H4A 120.7 . . ?
N1 C5 C4 120.1(7) . . ?
N1 C5 C6 118.9(6) . . ?
C4 C5 C6 121.0(7) . . ?
N2 C6 C5 107.3(5) . . ?
N2 C6 H6A 110.3 . . ?
C5 C6 H6A 110.3 . . ?
N2 C6 H6B 110.3 . . ?
C5 C6 H6B 110.3 . . ?
H6A C6 H6B 108.5 . . ?
C8 C7 N2 103.2(6) . . ?
C8 C7 Pd1 138.2(6) . . ?
N2 C7 Pd1 118.6(5) . . ?
N3 C8 C7 108.6(7) . . ?
N3 C8 H8A 125.7 . . ?
C7 C8 H8A 125.7 . . ?
N2 C9 N3 108.4(7) . . ?
N2 C9 H9A 125.8 . . ?
N3 C9 H9A 125.8 . . ?
N3 C10 C12 110.8(6) . . ?
N3 C10 C11 110.2(6) . . ?
C12 C10 C11 113.0(8) . . ?
N3 C10 H10A 107.5 . . ?
C12 C10 H10A 107.5 . . ?
C11 C10 H10A 107.5 . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C10 C12 H12A 109.5 . . ?
C10 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C10 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
O1 S1 C13 107.2(5) . . ?
O1 S1 C14 107.5(6) . . ?
C13 S1 C14 98.0(7) . . ?
S1 C13 H13A 109.5 . . ?
S1 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
S1 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
S1 C14 H14A 109.5 . . ?
S1 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
S1 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
H14C C14 H14B 109.5 . . ?

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
C7 Pd1 N1 C5 39.6(5) . . . . ?
Br1 Pd1 N1 C5 -140.0(5) . . . . ?
I1 Pd1 N1 C5 37(3) . . . . ?
C7 Pd1 N1 C1 -134.1(5) . . . . ?
Br1 Pd1 N1 C1 46.2(5) . . . . ?
I1 Pd1 N1 C1 -137(2) . . . . ?
C5 N1 C1 C2 -1.7(10) . . . . ?
Pd1 N1 C1 C2 172.1(5) . . . . ?
N1 C1 C2 C3 1.6(11) . . . . ?
C1 C2 C3 C4 0.7(11) . . . . ?
C2 C3 C4 C5 -2.8(11) . . . . ?
C1 N1 C5 C4 -0.5(9) . . . . ?
Pd1 N1 C5 C4 -174.1(5) . . . . ?
C1 N1 C5 C6 178.2(6) . . . . ?
Pd1 N1 C5 C6 4.5(8) . . . . ?
C3 C4 C5 N1 2.7(10) . . . . ?
C3 C4 C5 C6 -175.9(6) . . . . ?
C9 N2 C6 C5 -120.5(7) . . . . ?
C7 N2 C6 C5 57.3(8) . . . . ?
N1 C5 C6 N2 -58.0(8) . . . . ?
C4 C5 C6 N2 120.7(7) . . . . ?
C9 N2 C7 C8 -0.8(8) . . . . ?
C6 N2 C7 C8 -178.8(6) . . . . ?
C9 N2 C7 Pd1 178.5(5) . . . . ?
C6 N2 C7 Pd1 0.4(8) . . . . ?
N1 Pd1 C7 C8 138.1(8) . . . . ?
Br1 Pd1 C7 C8 148(5) . . . . ?
I1 Pd1 C7 C8 -42.1(8) . . . . ?
N1 Pd1 C7 N2 -40.9(5) . . . . ?
Br1 Pd1 C7 N2 -31(6) . . . . ?
I1 Pd1 C7 N2 139.0(5) . . . . ?
C9 N3 C8 C7 -0.3(8) . . . . ?
C10 N3 C8 C7 -178.8(6) . . . . ?
N2 C7 C8 N3 0.6(8) . . . . ?
Pd1 C7 C8 N3 -178.4(6) . . . . ?
C7 N2 C9 N3 0.6(8) . . . . ?
C6 N2 C9 N3 178.6(6) . . . . ?
C8 N3 C9 N2 -0.2(8) . . . . ?
C10 N3 C9 N2 178.3(6) . . . . ?
C9 N3 C10 C12 4.5(10) . . . . ?
C8 N3 C10 C12 -177.3(7) . . . . ?
C9 N3 C10 C11 -121.4(8) . . . . ?
C8 N3 C10 C11 56.8(10) . . . . ?

_diffrn_measured_fraction_theta_max 0.972
_diffrn_reflns_theta_full        26.09
_diffrn_measured_fraction_theta_full 0.972
_refine_diff_density_max         1.252
_refine_diff_density_min         -1.914
_refine_diff_density_rms         0.202