# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is (c) The Royal Society of Chemistry 2009



data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'W. Bruce Turnbull'
_publ_contact_author_email       W.B.TURNBULL@LEEDS.AC.UK

_publ_section_title              
;
Neighbouring group participation vs. addition
to oxacarbenium ions: studies on the synthesis
of mycobacterial oligosaccharides
;
loop_
_publ_author_name
'W. Bruce Turnbull'
'Colin A. Kilner'
'Andrew Leach'
'Susanne A. Stalford'

# Attachment 'compound_8_CCDC_735329.CIF'

data_c:\docume~1\radcak\mydocu~1\xa\sh383\sh383
_database_code_depnum_ccdc_archive 'CCDC 735329'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C19 H20 O3 S'
_chemical_formula_weight         328.41

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'
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           ?
_symmetry_space_group_name_H-M   ?

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z'
'-x, y+1/2, -z+1/2'

_cell_length_a                   5.6114(4)
_cell_length_b                   11.6946(9)
_cell_length_c                   25.505(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1673.7(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             696
_exptl_absorpt_coefficient_mu    0.206
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  0.9523
_exptl_absorpt_correction_T_max  0.9898
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      150(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  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            12065
_diffrn_reflns_av_R_equivalents  0.0414
_diffrn_reflns_av_sigmaI/netI    0.0540
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_theta_min         2.96
_diffrn_reflns_theta_max         29.39
_reflns_number_total             4551
_reflns_number_gt                3551
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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^)+(0.0504P)^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    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.03(8)
_refine_ls_number_reflns         4551
_refine_ls_number_parameters     208
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0437
_refine_ls_wR_factor_ref         0.1051
_refine_ls_wR_factor_gt          0.0972
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_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
S1 S 0.17880(10) 0.67818(4) 0.04279(2) 0.03946(15) Uani 1 1 d . . .
C2 C 0.1977(3) 0.83122(16) 0.06029(8) 0.0294(4) Uani 1 1 d . . .
H2 H 0.2032 0.8827 0.0290 0.035 Uiso 1 1 calc R . .
C3 C -0.0055(3) 0.85990(13) 0.09803(7) 0.0220(4) Uani 1 1 d . . .
H3 H -0.1587 0.8231 0.0872 0.026 Uiso 1 1 calc R . .
C4 C 0.0919(3) 0.80888(14) 0.14957(8) 0.0245(4) Uani 1 1 d . . .
H4 H 0.1154 0.8717 0.1757 0.029 Uiso 1 1 calc R . .
C5 C 0.3379(3) 0.76035(15) 0.13333(8) 0.0312(4) Uani 1 1 d . . .
H5 H 0.4546 0.7595 0.1630 0.037 Uiso 1 1 calc R . .
C6 C 0.3166(4) 0.64398(16) 0.10610(9) 0.0387(5) Uani 1 1 d . . .
H6A H 0.2149 0.5912 0.1266 0.046 Uiso 1 1 calc R . .
H6B H 0.4753 0.6086 0.1012 0.046 Uiso 1 1 calc R . .
O7 O 0.4044(2) 0.83921(12) 0.09224(6) 0.0352(3) Uani 1 1 d . . .
O31 O -0.0312(2) 0.98034(9) 0.10513(5) 0.0266(3) Uani 1 1 d . . .
C32 C -0.1790(4) 1.03164(14) 0.06628(8) 0.0291(4) Uani 1 1 d . . .
H32A H -0.3455 1.0056 0.0708 0.035 Uiso 1 1 calc R . .
H32B H -0.1246 1.0084 0.0309 0.035 Uiso 1 1 calc R . .
C33 C -0.1671(3) 1.16027(14) 0.07140(7) 0.0255(4) Uani 1 1 d . . .
C34 C -0.3489(4) 1.22704(16) 0.05120(8) 0.0360(5) Uani 1 1 d . . .
H34 H -0.4823 1.1914 0.0351 0.043 Uiso 1 1 calc R . .
C35 C -0.3385(4) 1.34607(17) 0.05414(9) 0.0400(5) Uani 1 1 d . . .
H35 H -0.4659 1.3908 0.0407 0.048 Uiso 1 1 calc R . .
C36 C -0.1430(4) 1.39905(16) 0.07655(9) 0.0380(5) Uani 1 1 d . . .
H36 H -0.1350 1.4801 0.0784 0.046 Uiso 1 1 calc R . .
C37 C 0.0400(4) 1.33310(18) 0.09611(10) 0.0444(6) Uani 1 1 d . . .
H37 H 0.1752 1.3689 0.1114 0.053 Uiso 1 1 calc R . .
C38 C 0.0280(4) 1.21439(16) 0.09368(9) 0.0365(5) Uani 1 1 d . . .
H38 H 0.1551 1.1699 0.1074 0.044 Uiso 1 1 calc R . .
O41 O -0.0724(2) 0.72807(11) 0.17002(5) 0.0272(3) Uani 1 1 d . . .
C42 C -0.0094(4) 0.68790(19) 0.22152(8) 0.0394(5) Uani 1 1 d . . .
H42A H 0.0041 0.7531 0.2461 0.047 Uiso 1 1 calc R . .
H42B H 0.1458 0.6477 0.2204 0.047 Uiso 1 1 calc R . .
C43 C -0.2017(4) 0.60779(16) 0.23933(8) 0.0312(4) Uani 1 1 d . . .
C44 C -0.2504(5) 0.5107(2) 0.21088(10) 0.0467(6) Uani 1 1 d . . .
H44 H -0.1582 0.4945 0.1806 0.056 Uiso 1 1 calc R . .
C45 C -0.4301(6) 0.4362(2) 0.22521(13) 0.0686(9) Uani 1 1 d . . .
H45 H -0.4602 0.3698 0.2048 0.082 Uiso 1 1 calc R . .
C46 C -0.5634(5) 0.4580(3) 0.26849(15) 0.0741(11) Uani 1 1 d . . .
H46 H -0.6858 0.4064 0.2785 0.089 Uiso 1 1 calc R . .
C47 C -0.5226(5) 0.5530(3) 0.29738(12) 0.0715(10) Uani 1 1 d . . .
H47 H -0.6179 0.5682 0.3274 0.086 Uiso 1 1 calc R . .
C48 C -0.3392(5) 0.6296(2) 0.28322(9) 0.0529(7) Uani 1 1 d . . .
H48 H -0.3103 0.6960 0.3038 0.063 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
S1 0.0444(3) 0.0284(2) 0.0455(3) -0.0091(2) 0.0044(3) 0.0049(2)
C2 0.0255(9) 0.0259(8) 0.0366(11) -0.0013(8) 0.0074(8) -0.0035(8)
C3 0.0201(8) 0.0178(7) 0.0280(10) 0.0004(7) 0.0005(8) -0.0025(6)
C4 0.0180(8) 0.0218(8) 0.0336(10) 0.0015(7) -0.0007(7) -0.0031(6)
C5 0.0192(8) 0.0276(9) 0.0469(12) 0.0018(8) -0.0022(9) -0.0012(8)
C6 0.0314(10) 0.0261(8) 0.0586(14) -0.0022(9) 0.0013(11) 0.0073(8)
O7 0.0186(6) 0.0354(7) 0.0516(9) 0.0021(7) 0.0057(6) -0.0042(5)
O31 0.0307(7) 0.0195(5) 0.0295(7) -0.0001(5) -0.0042(6) 0.0023(5)
C32 0.0319(9) 0.0228(8) 0.0325(10) 0.0033(7) -0.0088(9) -0.0034(8)
C33 0.0289(9) 0.0228(8) 0.0248(9) 0.0029(7) 0.0012(8) -0.0002(8)
C34 0.0335(11) 0.0307(9) 0.0438(12) 0.0034(9) -0.0128(10) -0.0003(8)
C35 0.0437(12) 0.0288(9) 0.0476(13) 0.0047(9) -0.0095(11) 0.0073(9)
C36 0.0497(13) 0.0209(8) 0.0433(12) -0.0015(8) 0.0005(11) 0.0013(9)
C37 0.0394(11) 0.0298(10) 0.0640(16) -0.0118(11) -0.0103(12) -0.0032(9)
C38 0.0307(10) 0.0269(9) 0.0520(14) -0.0040(9) -0.0124(10) 0.0040(8)
O41 0.0217(6) 0.0295(6) 0.0304(7) 0.0100(6) -0.0024(5) -0.0033(5)
C42 0.0413(11) 0.0425(11) 0.0343(12) 0.0145(9) -0.0133(10) -0.0094(10)
C43 0.0342(10) 0.0332(10) 0.0263(10) 0.0113(8) -0.0034(9) 0.0014(8)
C44 0.0576(14) 0.0443(13) 0.0383(12) 0.0042(10) 0.0033(11) -0.0112(10)
C45 0.0728(19) 0.0588(16) 0.074(2) 0.0277(15) -0.0188(18) -0.0345(15)
C46 0.0366(14) 0.090(2) 0.096(3) 0.069(2) -0.0076(16) -0.0086(15)
C47 0.0595(18) 0.098(2) 0.0568(18) 0.0485(18) 0.0306(15) 0.0342(18)
C48 0.0752(18) 0.0501(13) 0.0334(12) 0.0124(11) 0.0056(13) 0.0209(14)

_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
S1 C6 1.834(2) . ?
S1 C2 1.8477(19) . ?
C2 O7 1.420(2) . ?
C2 C3 1.530(2) . ?
C2 H2 1.0000 . ?
C3 O31 1.4274(19) . ?
C3 C4 1.544(3) . ?
C3 H3 1.0000 . ?
C4 O41 1.419(2) . ?
C4 C5 1.549(2) . ?
C4 H4 1.0000 . ?
C5 O7 1.445(2) . ?
C5 C6 1.533(3) . ?
C5 H5 1.0000 . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
O31 C32 1.424(2) . ?
C32 C33 1.511(2) . ?
C32 H32A 0.9900 . ?
C32 H32B 0.9900 . ?
C33 C34 1.384(3) . ?
C33 C38 1.386(3) . ?
C34 C35 1.395(3) . ?
C34 H34 0.9500 . ?
C35 C36 1.383(3) . ?
C35 H35 0.9500 . ?
C36 C37 1.378(3) . ?
C36 H36 0.9500 . ?
C37 C38 1.391(3) . ?
C37 H37 0.9500 . ?
C38 H38 0.9500 . ?
O41 C42 1.439(2) . ?
C42 C43 1.499(3) . ?
C42 H42A 0.9900 . ?
C42 H42B 0.9900 . ?
C43 C44 1.375(3) . ?
C43 C48 1.383(3) . ?
C44 C45 1.382(3) . ?
C44 H44 0.9500 . ?
C45 C46 1.358(5) . ?
C45 H45 0.9500 . ?
C46 C47 1.352(5) . ?
C46 H46 0.9500 . ?
C47 C48 1.412(4) . ?
C47 H47 0.9500 . ?
C48 H48 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
C6 S1 C2 88.52(9) . . ?
O7 C2 C3 103.49(14) . . ?
O7 C2 S1 104.44(13) . . ?
C3 C2 S1 108.76(12) . . ?
O7 C2 H2 113.1 . . ?
C3 C2 H2 113.1 . . ?
S1 C2 H2 113.1 . . ?
O31 C3 C2 111.80(14) . . ?
O31 C3 C4 108.02(14) . . ?
C2 C3 C4 100.78(14) . . ?
O31 C3 H3 111.9 . . ?
C2 C3 H3 111.9 . . ?
C4 C3 H3 111.9 . . ?
O41 C4 C3 109.88(14) . . ?
O41 C4 C5 115.66(14) . . ?
C3 C4 C5 103.27(15) . . ?
O41 C4 H4 109.3 . . ?
C3 C4 H4 109.3 . . ?
C5 C4 H4 109.3 . . ?
O7 C5 C6 104.96(17) . . ?
O7 C5 C4 100.95(14) . . ?
C6 C5 C4 112.15(16) . . ?
O7 C5 H5 112.7 . . ?
C6 C5 H5 112.7 . . ?
C4 C5 H5 112.7 . . ?
C5 C6 S1 103.79(13) . . ?
C5 C6 H6A 111.0 . . ?
S1 C6 H6A 111.0 . . ?
C5 C6 H6B 111.0 . . ?
S1 C6 H6B 111.0 . . ?
H6A C6 H6B 109.0 . . ?
C2 O7 C5 99.41(13) . . ?
C32 O31 C3 112.73(13) . . ?
O31 C32 C33 109.48(15) . . ?
O31 C32 H32A 109.8 . . ?
C33 C32 H32A 109.8 . . ?
O31 C32 H32B 109.8 . . ?
C33 C32 H32B 109.8 . . ?
H32A C32 H32B 108.2 . . ?
C34 C33 C38 118.49(16) . . ?
C34 C33 C32 119.79(17) . . ?
C38 C33 C32 121.65(17) . . ?
C33 C34 C35 120.80(19) . . ?
C33 C34 H34 119.6 . . ?
C35 C34 H34 119.6 . . ?
C36 C35 C34 120.14(19) . . ?
C36 C35 H35 119.9 . . ?
C34 C35 H35 119.9 . . ?
C37 C36 C35 119.33(18) . . ?
C37 C36 H36 120.3 . . ?
C35 C36 H36 120.3 . . ?
C36 C37 C38 120.4(2) . . ?
C36 C37 H37 119.8 . . ?
C38 C37 H37 119.8 . . ?
C33 C38 C37 120.80(18) . . ?
C33 C38 H38 119.6 . . ?
C37 C38 H38 119.6 . . ?
C4 O41 C42 113.15(14) . . ?
O41 C42 C43 107.69(16) . . ?
O41 C42 H42A 110.2 . . ?
C43 C42 H42A 110.2 . . ?
O41 C42 H42B 110.2 . . ?
C43 C42 H42B 110.2 . . ?
H42A C42 H42B 108.5 . . ?
C44 C43 C48 117.9(2) . . ?
C44 C43 C42 120.0(2) . . ?
C48 C43 C42 122.1(2) . . ?
C43 C44 C45 121.8(3) . . ?
C43 C44 H44 119.1 . . ?
C45 C44 H44 119.1 . . ?
C46 C45 C44 119.9(3) . . ?
C46 C45 H45 120.1 . . ?
C44 C45 H45 120.1 . . ?
C47 C46 C45 120.3(3) . . ?
C47 C46 H46 119.9 . . ?
C45 C46 H46 119.9 . . ?
C46 C47 C48 120.4(3) . . ?
C46 C47 H47 119.8 . . ?
C48 C47 H47 119.8 . . ?
C43 C48 C47 119.8(3) . . ?
C43 C48 H48 120.1 . . ?
C47 C48 H48 120.1 . . ?

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 S1 C2 O7 31.17(13) . . . . ?
C6 S1 C2 C3 -78.82(14) . . . . ?
O7 C2 C3 O31 80.97(17) . . . . ?
S1 C2 C3 O31 -168.41(12) . . . . ?
O7 C2 C3 C4 -33.57(16) . . . . ?
S1 C2 C3 C4 77.05(14) . . . . ?
O31 C3 C4 O41 119.44(15) . . . . ?
C2 C3 C4 O41 -123.20(15) . . . . ?
O31 C3 C4 C5 -116.61(15) . . . . ?
C2 C3 C4 C5 0.75(16) . . . . ?
O41 C4 C5 O7 151.35(15) . . . . ?
C3 C4 C5 O7 31.29(17) . . . . ?
O41 C4 C5 C6 40.1(2) . . . . ?
C3 C4 C5 C6 -79.97(18) . . . . ?
O7 C5 C6 S1 -38.89(17) . . . . ?
C4 C5 C6 S1 69.84(18) . . . . ?
C2 S1 C6 C5 4.41(14) . . . . ?
C3 C2 O7 C5 55.24(16) . . . . ?
S1 C2 O7 C5 -58.54(14) . . . . ?
C6 C5 O7 C2 63.56(17) . . . . ?
C4 C5 O7 C2 -53.14(16) . . . . ?
C2 C3 O31 C32 86.33(18) . . . . ?
C4 C3 O31 C32 -163.67(13) . . . . ?
C3 O31 C32 C33 -171.39(15) . . . . ?
O31 C32 C33 C34 -158.22(17) . . . . ?
O31 C32 C33 C38 25.0(3) . . . . ?
C38 C33 C34 C35 -1.3(3) . . . . ?
C32 C33 C34 C35 -178.2(2) . . . . ?
C33 C34 C35 C36 1.2(3) . . . . ?
C34 C35 C36 C37 -0.3(3) . . . . ?
C35 C36 C37 C38 -0.4(4) . . . . ?
C34 C33 C38 C37 0.6(3) . . . . ?
C32 C33 C38 C37 177.4(2) . . . . ?
C36 C37 C38 C33 0.3(4) . . . . ?
C3 C4 O41 C42 -172.22(16) . . . . ?
C5 C4 O41 C42 71.4(2) . . . . ?
C4 O41 C42 C43 177.52(16) . . . . ?
O41 C42 C43 C44 60.0(3) . . . . ?
O41 C42 C43 C48 -118.1(2) . . . . ?
C48 C43 C44 C45 -0.2(3) . . . . ?
C42 C43 C44 C45 -178.4(2) . . . . ?
C43 C44 C45 C46 -0.1(4) . . . . ?
C44 C45 C46 C47 0.6(4) . . . . ?
C45 C46 C47 C48 -0.8(4) . . . . ?
C44 C43 C48 C47 0.0(3) . . . . ?
C42 C43 C48 C47 178.1(2) . . . . ?
C46 C47 C48 C43 0.5(4) . . . . ?

_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_theta_full        29.39
_diffrn_measured_fraction_theta_full 0.991
_refine_diff_density_max         0.331
_refine_diff_density_min         -0.281
_refine_diff_density_rms         0.045