# Electronic Supplementary Material (ESI) for Organic and Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2011


data_global
_journal_name_full               Org.Biomol.Chem.

_journal_coden_Cambridge         0177

_publ_contact_author_name        'Han, Jianlin'
_publ_contact_author_email       hanjl@nju.edu.cn

_publ_section_title              
;
Ligand-free palladium-catalyzed intramolecular Heck reaction
of b-hydrogen-containing secondary benzylic bromides
;
loop_
_publ_author_name
'Wei Zhou'
'Guanghui An'
'Guangqian Zhang'
'Jianlin Han'
'Yi Pan'

# Attachment '2a.cif'

data_291211b
_database_code_depnum_ccdc_archive 'CCDC 780714'
#TrackingRef '2a.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H19 N O2 S'
_chemical_formula_sum            'C18 H19 N O2 S'
_chemical_formula_weight         313.40

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'
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   P2(1)/c
_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                   10.879(7)
_cell_length_b                   8.725(6)
_cell_length_c                   17.898(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 92.108(9)
_cell_angle_gamma                90.00
_cell_volume                     1697.6(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    291(2)
_cell_measurement_reflns_used    2381
_cell_measurement_theta_min      2.59
_cell_measurement_theta_max      22.34

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.22
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             664
_exptl_absorpt_coefficient_mu    0.197
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9470
_exptl_absorpt_correction_T_max  0.9580
_exptl_absorpt_process_details   'SADABS; Bruker, 2000'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      291(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker Smart Aepex CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8886
_diffrn_reflns_av_R_equivalents  0.0495
_diffrn_reflns_av_sigmaI/netI    0.0863
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         1.87
_diffrn_reflns_theta_max         26.00
_reflns_number_total             3334
_reflns_number_gt                2087
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (Bruker, 2000)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker, 2000)'
_computing_structure_solution    'SHELXTL (Bruker, 2000)'
_computing_structure_refinement  SHELXTL
_computing_molecular_graphics    SHELXTL
_computing_publication_material  SHELXTL

_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^)+(0.0671P)^2^] 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     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3334
_refine_ls_number_parameters     201
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0985
_refine_ls_R_factor_gt           0.0650
_refine_ls_wR_factor_ref         0.1506
_refine_ls_wR_factor_gt          0.1438
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_restrained_S_all      1.049
_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
C1 C 0.6263(3) 0.6312(4) 0.22512(18) 0.0465(8) Uani 1 1 d . . .
H1 H 0.5863 0.7254 0.2249 0.056 Uiso 1 1 calc R . .
C2 C 0.6233(3) 0.5395(4) 0.28589(19) 0.0478(8) Uani 1 1 d . . .
H2 H 0.5834 0.5719 0.3281 0.057 Uiso 1 1 calc R . .
C3 C 0.6790(3) 0.3989(4) 0.28524(18) 0.0457(8) Uani 1 1 d . . .
H3 H 0.6751 0.3360 0.3270 0.055 Uiso 1 1 calc R . .
C4 C 0.7403(3) 0.3488(4) 0.22458(19) 0.0451(8) Uani 1 1 d . . .
C5 C 0.7466(3) 0.4428(4) 0.16296(18) 0.0451(8) Uani 1 1 d . . .
H5 H 0.7889 0.4115 0.1214 0.054 Uiso 1 1 calc R . .
C6 C 0.6889(3) 0.5846(4) 0.16360(18) 0.0454(8) Uani 1 1 d . . .
H6 H 0.6925 0.6486 0.1222 0.054 Uiso 1 1 calc R . .
C7 C 0.7974(3) 0.1915(3) 0.22447(16) 0.0402(7) Uani 1 1 d . . .
H7 H 0.7994 0.1516 0.2757 0.048 Uiso 1 1 calc R . .
C8 C 0.9242(3) 0.1818(4) 0.19538(17) 0.0422(7) Uani 1 1 d . . .
C9 C 1.0304(3) 0.2685(4) 0.22982(17) 0.0465(8) Uani 1 1 d . . .
H9A H 1.1051 0.2358 0.2077 0.070 Uiso 1 1 calc R . .
H9B H 1.0357 0.2490 0.2826 0.070 Uiso 1 1 calc R . .
H9C H 1.0188 0.3762 0.2212 0.070 Uiso 1 1 calc R . .
C10 C 0.9286(3) 0.0855(4) 0.13941(18) 0.0444(8) Uani 1 1 d . . .
H10 H 0.9990 0.0679 0.1127 0.053 Uiso 1 1 calc R . .
C11 C 0.7236(3) 0.0780(4) 0.17347(19) 0.0469(8) Uani 1 1 d . . .
H11A H 0.6858 -0.0011 0.2031 0.056 Uiso 1 1 calc R . .
H11B H 0.6596 0.1313 0.1446 0.056 Uiso 1 1 calc R . .
C12 C 0.7440(3) 0.1572(4) -0.00480(17) 0.0419(7) Uani 1 1 d . . .
C13 C 0.6257(3) 0.2128(4) -0.01315(17) 0.0439(7) Uani 1 1 d . . .
H13 H 0.5594 0.1543 0.0016 0.053 Uiso 1 1 calc R . .
C14 C 0.6072(3) 0.3552(4) -0.04351(18) 0.0435(8) Uani 1 1 d . . .
H14 H 0.5271 0.3918 -0.0495 0.052 Uiso 1 1 calc R . .
C15 C 0.7024(3) 0.4463(4) -0.06545(16) 0.0412(7) Uani 1 1 d . . .
C16 C 0.8201(3) 0.3896(4) -0.05527(16) 0.0413(7) Uani 1 1 d . . .
H16 H 0.8862 0.4500 -0.0686 0.050 Uiso 1 1 calc R . .
C17 C 0.8423(3) 0.2451(4) -0.02577(16) 0.0430(7) Uani 1 1 d . . .
H17 H 0.9222 0.2079 -0.0202 0.052 Uiso 1 1 calc R . .
C18 C 0.6790(3) 0.6018(4) -0.09931(18) 0.0467(8) Uani 1 1 d . . .
H18A H 0.5949 0.6084 -0.1172 0.070 Uiso 1 1 calc R . .
H18B H 0.7324 0.6169 -0.1402 0.070 Uiso 1 1 calc R . .
H18C H 0.6949 0.6793 -0.0622 0.070 Uiso 1 1 calc R . .
N1 N 0.8144(2) 0.0107(3) 0.12372(15) 0.0439(6) Uani 1 1 d . . .
O2 O 0.87011(19) -0.0942(3) 0.00206(12) 0.0468(6) Uani 1 1 d . . .
O3 O 0.65465(19) -0.0988(3) 0.04003(12) 0.0434(5) Uani 1 1 d . . .
S1 S 0.76981(7) -0.02208(9) 0.03692(4) 0.0411(2) Uani 1 1 d . . .

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
C1 0.0455(18) 0.0420(18) 0.0506(19) -0.0104(14) -0.0181(15) 0.0164(15)
C2 0.0402(17) 0.0518(19) 0.0521(19) -0.0119(16) 0.0116(14) 0.0087(16)
C3 0.0456(17) 0.0467(18) 0.0442(17) 0.0154(14) -0.0075(14) 0.0001(16)
C4 0.0448(18) 0.0395(16) 0.0503(19) -0.0016(13) -0.0065(15) 0.0017(14)
C5 0.0486(19) 0.0444(18) 0.0424(17) -0.0108(14) 0.0020(14) 0.0059(15)
C6 0.0417(16) 0.0475(18) 0.0458(18) 0.0153(14) -0.0131(14) -0.0022(15)
C7 0.0455(18) 0.0382(16) 0.0367(15) 0.0075(13) 0.0015(13) -0.0016(14)
C8 0.0433(17) 0.0419(18) 0.0407(16) 0.0048(13) -0.0072(13) 0.0036(14)
C9 0.0523(19) 0.0445(18) 0.0417(17) -0.0105(14) -0.0129(15) -0.0010(15)
C10 0.0443(18) 0.0468(18) 0.0416(17) -0.0006(13) -0.0066(14) 0.0020(15)
C11 0.0476(18) 0.0437(19) 0.0501(19) -0.0060(14) 0.0117(14) -0.0154(15)
C12 0.0402(17) 0.0436(17) 0.0413(16) -0.0033(13) -0.0059(14) 0.0006(14)
C13 0.0435(18) 0.0455(18) 0.0425(16) -0.0064(14) -0.0024(14) 0.0052(15)
C14 0.0373(16) 0.0441(17) 0.0486(18) -0.0072(14) -0.0053(14) 0.0132(15)
C15 0.0450(17) 0.0415(18) 0.0373(15) -0.0049(12) 0.0029(13) 0.0121(14)
C16 0.0370(15) 0.0503(19) 0.0368(16) 0.0015(13) 0.0031(12) -0.0072(15)
C17 0.0403(17) 0.0483(18) 0.0405(17) -0.0007(13) 0.0014(14) 0.0012(14)
C18 0.0478(18) 0.0437(18) 0.0491(19) 0.0043(14) 0.0089(15) 0.0134(15)
N1 0.0435(15) 0.0463(16) 0.0419(14) 0.0016(11) 0.0008(12) 0.0007(12)
O2 0.0469(12) 0.0455(13) 0.0476(13) -0.0057(10) -0.0020(10) -0.0010(10)
O3 0.0444(12) 0.0409(11) 0.0444(12) 0.0005(9) -0.0050(9) -0.0089(10)
S1 0.0411(4) 0.0401(4) 0.0418(4) -0.0058(3) -0.0023(3) -0.0006(3)

_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
C1 C2 1.351(5) . ?
C1 C6 1.377(5) . ?
C1 H1 0.9300 . ?
C2 C3 1.368(5) . ?
C2 H2 0.9300 . ?
C3 C4 1.367(5) . ?
C3 H3 0.9300 . ?
C4 C5 1.378(5) . ?
C4 C7 1.506(4) . ?
C5 C6 1.388(5) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C7 C8 1.495(4) . ?
C7 C11 1.551(4) . ?
C7 H7 0.9800 . ?
C8 C10 1.310(5) . ?
C8 C9 1.495(4) . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C10 N1 1.422(4) . ?
C10 H10 0.9300 . ?
C11 N1 1.476(4) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 C13 1.378(4) . ?
C12 C17 1.379(5) . ?
C12 S1 1.751(3) . ?
C13 C14 1.368(4) . ?
C13 H13 0.9300 . ?
C14 C15 1.374(5) . ?
C14 H14 0.9300 . ?
C15 C16 1.378(4) . ?
C15 C18 1.504(4) . ?
C16 C17 1.385(5) . ?
C16 H16 0.9300 . ?
C17 H17 0.9300 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
N1 S1 1.635(3) . ?
O2 S1 1.423(2) . ?
O3 S1 1.423(2) . ?

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
C2 C1 C6 119.7(3) . . ?
C2 C1 H1 120.1 . . ?
C6 C1 H1 120.1 . . ?
C1 C2 C3 120.0(3) . . ?
C1 C2 H2 120.0 . . ?
C3 C2 H2 120.0 . . ?
C4 C3 C2 121.5(3) . . ?
C4 C3 H3 119.2 . . ?
C2 C3 H3 119.2 . . ?
C3 C4 C5 119.0(3) . . ?
C3 C4 C7 120.4(3) . . ?
C5 C4 C7 120.6(3) . . ?
C4 C5 C6 119.2(3) . . ?
C4 C5 H5 120.4 . . ?
C6 C5 H5 120.4 . . ?
C1 C6 C5 120.5(3) . . ?
C1 C6 H6 119.8 . . ?
C5 C6 H6 119.8 . . ?
C8 C7 C4 116.0(3) . . ?
C8 C7 C11 102.9(2) . . ?
C4 C7 C11 112.2(3) . . ?
C8 C7 H7 108.5 . . ?
C4 C7 H7 108.5 . . ?
C11 C7 H7 108.5 . . ?
C10 C8 C9 126.2(3) . . ?
C10 C8 C7 111.2(3) . . ?
C9 C8 C7 122.5(3) . . ?
C8 C9 H9A 109.5 . . ?
C8 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C8 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
C8 C10 N1 112.9(3) . . ?
C8 C10 H10 123.5 . . ?
N1 C10 H10 123.5 . . ?
N1 C11 C7 105.4(2) . . ?
N1 C11 H11A 110.7 . . ?
C7 C11 H11A 110.7 . . ?
N1 C11 H11B 110.7 . . ?
C7 C11 H11B 110.7 . . ?
H11A C11 H11B 108.8 . . ?
C13 C12 C17 120.3(3) . . ?
C13 C12 S1 119.7(3) . . ?
C17 C12 S1 119.9(2) . . ?
C14 C13 C12 119.1(3) . . ?
C14 C13 H13 120.4 . . ?
C12 C13 H13 120.4 . . ?
C13 C14 C15 122.4(3) . . ?
C13 C14 H14 118.8 . . ?
C15 C14 H14 118.8 . . ?
C14 C15 C16 117.5(3) . . ?
C14 C15 C18 121.2(3) . . ?
C16 C15 C18 121.3(3) . . ?
C15 C16 C17 121.7(3) . . ?
C15 C16 H16 119.1 . . ?
C17 C16 H16 119.1 . . ?
C12 C17 C16 118.9(3) . . ?
C12 C17 H17 120.5 . . ?
C16 C17 H17 120.5 . . ?
C15 C18 H18A 109.5 . . ?
C15 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C15 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C10 N1 C11 107.3(3) . . ?
C10 N1 S1 119.6(2) . . ?
C11 N1 S1 117.5(2) . . ?
O2 S1 O3 119.95(14) . . ?
O2 S1 N1 106.77(14) . . ?
O3 S1 N1 106.01(13) . . ?
O2 S1 C12 108.75(15) . . ?
O3 S1 C12 108.01(14) . . ?
N1 S1 C12 106.61(14) . . ?

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
C6 C1 C2 C3 -2.0(5) . . . . ?
C1 C2 C3 C4 1.1(5) . . . . ?
C2 C3 C4 C5 0.4(5) . . . . ?
C2 C3 C4 C7 -178.1(3) . . . . ?
C3 C4 C5 C6 -1.0(5) . . . . ?
C7 C4 C5 C6 177.5(3) . . . . ?
C2 C1 C6 C5 1.4(5) . . . . ?
C4 C5 C6 C1 0.1(5) . . . . ?
C3 C4 C7 C8 -135.9(3) . . . . ?
C5 C4 C7 C8 45.7(4) . . . . ?
C3 C4 C7 C11 106.3(3) . . . . ?
C5 C4 C7 C11 -72.2(4) . . . . ?
C4 C7 C8 C10 -122.8(3) . . . . ?
C11 C7 C8 C10 0.1(3) . . . . ?
C4 C7 C8 C9 59.6(4) . . . . ?
C11 C7 C8 C9 -177.5(3) . . . . ?
C9 C8 C10 N1 174.6(3) . . . . ?
C7 C8 C10 N1 -2.9(4) . . . . ?
C8 C7 C11 N1 2.5(3) . . . . ?
C4 C7 C11 N1 127.9(3) . . . . ?
C17 C12 C13 C14 0.9(5) . . . . ?
S1 C12 C13 C14 177.8(2) . . . . ?
C12 C13 C14 C15 -0.7(5) . . . . ?
C13 C14 C15 C16 -0.5(5) . . . . ?
C13 C14 C15 C18 179.4(3) . . . . ?
C14 C15 C16 C17 1.5(4) . . . . ?
C18 C15 C16 C17 -178.4(3) . . . . ?
C13 C12 C17 C16 0.0(4) . . . . ?
S1 C12 C17 C16 -176.9(2) . . . . ?
C15 C16 C17 C12 -1.2(4) . . . . ?
C8 C10 N1 C11 4.6(4) . . . . ?
C8 C10 N1 S1 141.7(2) . . . . ?
C7 C11 N1 C10 -4.2(3) . . . . ?
C7 C11 N1 S1 -142.4(2) . . . . ?
C10 N1 S1 O2 50.3(3) . . . . ?
C11 N1 S1 O2 -176.7(2) . . . . ?
C10 N1 S1 O3 179.3(2) . . . . ?
C11 N1 S1 O3 -47.8(3) . . . . ?
C10 N1 S1 C12 -65.8(3) . . . . ?
C11 N1 S1 C12 67.2(3) . . . . ?
C13 C12 S1 O2 145.3(2) . . . . ?
C17 C12 S1 O2 -37.8(3) . . . . ?
C13 C12 S1 O3 13.7(3) . . . . ?
C17 C12 S1 O3 -169.5(2) . . . . ?
C13 C12 S1 N1 -99.9(3) . . . . ?
C17 C12 S1 N1 77.0(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.355
_refine_diff_density_min         -0.519
_refine_diff_density_rms         0.059