# Copyright The Royal Society of Chemistry, 1998 # CCDC Number: 182/1088 data_DWDC6_8 # TITLE AND AUTHOR LIST _publ_section_title ; Stereoselective suloxidation of \a-mannopyranosyl thioglycosides: the exo-anomeric effect in action ; loop_ _publ_author_name _publ_author_address 'Crich, David C.' ; Department of Chemistry (m/c 111) University of Illinois at Chicago 845 W. Taylor Street Chicago, Illinois 60607 USA ; 'Mataka, Jan' ; Department of Chemistry (m/c 111) University of Illinois at Chicago 845 W. Taylor Street Chicago, Illinois 60607 USA ; 'Sun, Sanxing' ; Department of Chemistry (m/c 111) University of Illinois at Chicago 845 W. Taylor Street Chicago, Illinois 60607 USA ; 'Wink, Donald J.' ; Department of Chemistry (m/c 111) University of Illinois at Chicago 845 W. Taylor Street Chicago, Illinois 60607 USA ; 'Lam, K.-C.' ; University of Delaware Department of Chemistry and Biochemistry Academy Street Newark, DE 19716 USA ; 'Rheingold, A. L.' ; University of Delaware Department of Chemistry and Biochemistry Academy Street Newark, DE 19716 USA ; # SUBMISSION DETAILS _publ_contact_author_name 'Dr. David C. Crich' _publ_contact_author_address ; Department of Chemistry (m/c 111) University of Illinois at Chicago 845 W. Taylor Street Chicago, Illinois 60607 USA ; _publ_contact_author_email dcrich@uic.edu _publ_contact_author_fax '(312)9960431' _publ_contact_author_phone '(312)9965189' # ----- MATERIAL RELEVANT TO THE COMPOUND 20 ----- data_DWDC6 _audit_creation_method SHELXL _chemical_name_systematic ; 1-Deoxy-2,3;4,6-diisopropylidene-1-thia- 1-\a-D-mannopyranoside S-Oxide ; _chemical_name_common ; Compound 20: Mannosyl diacetonide ethyl sulfone ; _chemical_formula_analytical 'C14 H23 O6 S1' _chemical_formula_moiety 'C14 H23 O6 S1' _chemical_formula_structural 'C14 H23 O6 S1' _chemical_formula_sum 'C14 H23 O6 S1' _chemical_formula_weight 319.4 _chemical_melting_point 'not measured' _computing_data_collection 'CAD-4 MS-DOS control software' _computing_cell_refinement 'CAD-4 MS-DOS control software' _computing_data_reduction xtal_DIFDAT_ABSORB_SORTRF_ADDREF _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement xtal_CRYLSQ _computing_molecular_graphics xtal _computing_publication_material xtal_BONDLA_CIFIO _cell_length_a 11.282(7) _cell_length_b 9.766(10) _cell_length_c 15.555(12) _cell_angle_alpha 90.00(9) _cell_angle_beta 99.73(6) _cell_angle_gamma 90.00(9) _cell_volume 1689(2) _cell_formula_units_Z 4 _cell_measurement_temperature 293 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 4.51 _cell_measurement_theta_max 9.59 _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M p_1_21_1 _symmetry_space_group_name_Hall p_2yb loop_ _symmetry_equiv_pos_as_xyz +x,+y,+z -x,1/2+y,-z _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.20 _exptl_crystal_density_diffrn 1.323 _exptl_crystal_density_meas none _exptl_crystal_F_000 684 _exptl_absorpt_process_details none _exptl_adsorpt_correction_type none _exptl_absorpt_coefficient_mu 0.214 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Enraf-Nonius CAD-4' _diffrn_measurement_method \w--2\q _diffrn_standards_number 3 _diffrn_standards_interval_time 600 _diffrn_standards_decay_% 10.5 _diffrn_ambient_temperature 293 _diffrn_reflns_number 3371 _diffrn_reflns_av_R_equivalents 0.0398 _diffrn_reflns_av_sigmaI/netI 0.0779 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.33 _diffrn_reflns_theta_max 20.10 _reflns_number_total 3163 _reflns_number_observed 1884 _reflns_observed_criterion >2sigma(I) _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0582P)^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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0031(9) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.46(15) _refine_ls_number_reflns 3163 _refine_ls_number_parameters 380 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0830 _refine_ls_R_factor_obs 0.0412 _refine_ls_wR_factor_all 0.1214 _refine_ls_wR_factor_obs 0.0984 _refine_ls_goodness_of_fit_all 1.032 _refine_ls_goodness_of_fit_obs 1.131 _refine_ls_restrained_S_all 1.032 _refine_ls_restrained_S_obs 1.131 _refine_ls_shift/esd_max 0.004 _refine_ls_shift/esd_mean 0.001 _refine_diff_density_max 0.261 _refine_diff_density_min -0.160 _refine_diff_density_rms 0.038 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' 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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group S1 S 0.6128(2) 0.3795(2) 1.12454(12) 0.0734(7) Uani 1 d . . C1' C 0.5456(8) 0.2702(9) 1.1971(5) 0.086(3) Uani 1 d . . H1'1 H 0.4650(8) 0.2447(9) 1.1695(5) 0.104 Uiso 1 calc R . H1'2 H 0.5927(8) 0.1871(9) 1.2087(5) 0.104 Uiso 1 calc R . C2' C 0.5403(8) 0.3425(11) 1.2807(6) 0.104(3) Uani 1 d . . H2'1 H 0.5045(8) 0.2835(11) 1.3185(6) 0.156 Uiso 1 calc R . H2'2 H 0.4927(8) 0.4240(11) 1.2691(6) 0.156 Uiso 1 calc R . H2'3 H 0.6202(8) 0.3666(11) 1.3083(6) 0.156 Uiso 1 calc R . O1' O 0.7463(5) 0.3889(7) 1.1568(3) 0.099(2) Uani 1 d . . C1 C 0.6026(6) 0.2601(7) 1.0308(4) 0.056(2) Uani 1 d . . H1 H 0.6567(6) 0.1829(7) 1.0486(4) 0.067 Uiso 1 calc R . C2 C 0.6466(6) 0.3329(8) 0.9557(4) 0.057(2) Uani 1 d . . H2 H 0.7122(6) 0.3949(8) 0.9796(4) 0.068 Uiso 1 calc R . C3 C 0.5550(6) 0.4119(7) 0.8927(4) 0.053(2) Uani 1 d . . H3 H 0.5467(6) 0.5053(7) 0.9139(4) 0.064 Uiso 1 calc R . C4 C 0.4326(6) 0.3379(7) 0.8784(4) 0.048(2) Uani 1 d . . H4 H 0.4369(6) 0.2533(7) 0.8452(4) 0.058 Uiso 1 calc R . C5 C 0.3980(6) 0.3067(8) 0.9661(4) 0.054(2) Uani 1 d . . C6 C 0.2753(7) 0.2378(9) 0.9502(5) 0.069(2) Uani 1 d . . H6A H 0.2782(7) 0.1537(9) 0.9175(5) 0.082 Uiso 1 calc R . H6B H 0.2500(7) 0.2162(9) 1.0052(5) 0.082 Uiso 1 calc R . C10 C 0.2239(7) 0.3706(10) 0.8202(5) 0.069(2) Uani 1 d . . C11 C 0.1405(7) 0.4907(9) 0.7892(6) 0.096(3) Uani 1 d . . H11A H 0.1559(7) 0.5221(9) 0.7337(6) 0.145 Uiso 1 calc R . H11B H 0.1550(7) 0.5640(9) 0.8309(6) 0.145 Uiso 1 calc R . H11C H 0.0584(7) 0.4615(9) 0.7837(6) 0.145 Uiso 1 calc R . C12 C 0.2107(8) 0.2561(11) 0.7549(5) 0.098(3) Uani 1 d . . H12A H 0.2325(8) 0.2882(11) 0.7014(5) 0.148 Uiso 1 calc R . H12B H 0.1288(8) 0.2251(11) 0.7442(5) 0.148 Uiso 1 calc R . H12C H 0.2625(8) 0.1817(11) 0.7773(5) 0.148 Uiso 1 calc R . C13 C 0.6922(7) 0.3045(9) 0.8183(5) 0.063(2) Uani 1 d . . C14 C 0.6536(8) 0.2048(9) 0.7456(6) 0.092(3) Uani 1 d . . H14A H 0.7114(8) 0.1320(9) 0.7488(6) 0.138 Uiso 1 calc R . H14B H 0.6483(8) 0.2509(9) 0.6906(6) 0.138 Uiso 1 calc R . H14C H 0.5764(8) 0.1675(9) 0.7509(6) 0.138 Uiso 1 calc R . C15 C 0.8145(7) 0.3659(10) 0.8151(6) 0.096(3) Uani 1 d . . H15A H 0.8731(7) 0.2941(10) 0.8179(6) 0.144 Uiso 1 calc R . H15B H 0.8363(7) 0.4267(10) 0.8637(6) 0.144 Uiso 1 calc R . H15C H 0.8117(7) 0.4160(10) 0.7617(6) 0.144 Uiso 1 calc R . O2 O 0.6906(4) 0.2362(5) 0.9000(4) 0.0667(15) Uani 1 d . . O3 O 0.6066(4) 0.4133(5) 0.8140(3) 0.0594(14) Uani 1 d . . O4 O 0.3428(4) 0.4274(5) 0.8330(3) 0.0620(15) Uani 1 d . . O5 O 0.4836(4) 0.2076(5) 1.0087(3) 0.0577(13) Uani 1 d . . O6 O 0.1937(4) 0.3328(6) 0.9016(3) 0.074(2) Uani 1 d . . S21 S 1.0952(2) 0.3063(3) 0.17120(13) 0.0876(8) Uani 1 d . . C21' C 1.0455(9) 0.4722(10) 0.1373(6) 0.095(3) Uani 1 d . . H21A H 0.9793(9) 0.4977(10) 0.1665(6) 0.115 Uiso 1 calc R . H21B H 1.1104(9) 0.5368(10) 0.1549(6) 0.115 Uiso 1 calc R . C22' C 1.0051(10) 0.4823(13) 0.0403(5) 0.138(5) Uani 1 d . . H22A H 0.9791(10) 0.5741(13) 0.0253(5) 0.208 Uiso 1 calc R . H22B H 0.9396(10) 0.4200(13) 0.0227(5) 0.208 Uiso 1 calc R . H22C H 1.0708(10) 0.4591(13) 0.0111(5) 0.208 Uiso 1 calc R . O21' O 1.2087(6) 0.2768(10) 0.1364(3) 0.160(4) Uani 1 d . . C21 C 1.1525(7) 0.3485(7) 0.2879(4) 0.058(2) Uani 1 d . . H21 H 1.2167(7) 0.4164(7) 0.2889(4) 0.069 Uiso 1 calc R . C22 C 1.2095(6) 0.2188(9) 0.3297(5) 0.061(2) Uani 1 d . . H22 H 1.2431(6) 0.1647(9) 0.2865(5) 0.073 Uiso 1 calc R . C23 C 1.1298(6) 0.1298(8) 0.3753(5) 0.055(2) Uani 1 d . . H23 H 1.0881(6) 0.0637(8) 0.3334(5) 0.066 Uiso 1 calc R . C24 C 1.0379(6) 0.2110(7) 0.4134(4) 0.044(2) Uani 1 d . . H24 H 1.0789(6) 0.2619(7) 0.4641(4) 0.053 Uiso 1 calc R . C25 C 0.9755(6) 0.3120(8) 0.3471(4) 0.053(2) Uani 1 d . . C26 C 0.8819(7) 0.3857(9) 0.3891(5) 0.063(2) Uani 1 d . . H26A H 0.9212(7) 0.4393(9) 0.4382(5) 0.076 Uiso 1 calc R . H26B H 0.8363(7) 0.4477(9) 0.3472(5) 0.076 Uiso 1 calc R . C30 C 0.8592(6) 0.1901(8) 0.4761(5) 0.059(2) Uani 1 d . . C31 C 0.7664(7) 0.0843(9) 0.4834(6) 0.084(3) Uani 1 d . . H31A H 0.8008(7) 0.0139(9) 0.5230(6) 0.125 Uiso 1 calc R . H31B H 0.7385(7) 0.0451(9) 0.4271(6) 0.125 Uiso 1 calc R . H31C H 0.7001(7) 0.1259(9) 0.5051(6) 0.125 Uiso 1 calc R . C32 C 0.9108(7) 0.2506(8) 0.5658(4) 0.069(2) Uani 1 d . . H32A H 0.9479(7) 0.1792(8) 0.6034(4) 0.103 Uiso 1 calc R . H32B H 0.8471(7) 0.2914(8) 0.5908(4) 0.103 Uiso 1 calc R . H32C H 0.9696(7) 0.3191(8) 0.5592(4) 0.103 Uiso 1 calc R . C33 C 1.3237(7) 0.1326(9) 0.4524(5) 0.065(2) Uani 1 d . . C34 C 1.4192(7) 0.0411(10) 0.4236(6) 0.109(3) Uani 1 d . . H34A H 1.4309(7) -0.0385(10) 0.4603(6) 0.164 Uiso 1 calc R . H34B H 1.4935(7) 0.0907(10) 0.4282(6) 0.164 Uiso 1 calc R . H34C H 1.3934(7) 0.0134(10) 0.3642(6) 0.164 Uiso 1 calc R . C35 C 1.3555(9) 0.1744(11) 0.5473(6) 0.114(4) Uani 1 d . . H35A H 1.3706(9) 0.0940(11) 0.5830(6) 0.171 Uiso 1 calc R . H35B H 1.2900(9) 0.2249(11) 0.5639(6) 0.171 Uiso 1 calc R . H35C H 1.4263(9) 0.2307(11) 0.5551(6) 0.171 Uiso 1 calc R . O22 O 1.3017(4) 0.2526(5) 0.4009(3) 0.0669(15) Uani 1 d . . O23 O 1.2117(4) 0.0581(5) 0.4392(3) 0.0673(15) Uani 1 d . . O24 O 0.9529(4) 0.1202(4) 0.4413(3) 0.0509(13) Uani 1 d . . O25 O 1.0634(5) 0.4075(5) 0.3288(3) 0.0614(13) Uani 1 d . . O26 O 0.8036(4) 0.2894(6) 0.4177(3) 0.0656(14) Uani 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 S1 0.092(2) 0.0692(15) 0.0539(12) 0.0058(12) -0.0006(11) -0.0137(13) C1' 0.133(8) 0.074(7) 0.051(5) -0.001(5) 0.011(5) -0.026(6) C2' 0.105(7) 0.121(10) 0.093(7) 0.015(6) 0.034(6) 0.009(6) O1' 0.096(4) 0.132(5) 0.063(3) 0.008(4) -0.006(3) -0.044(4) C1 0.053(5) 0.048(5) 0.059(5) 0.015(4) -0.010(4) -0.007(4) C2 0.055(5) 0.055(6) 0.059(4) 0.006(4) 0.004(4) 0.004(4) C3 0.061(5) 0.049(5) 0.052(5) -0.002(4) 0.014(4) 0.000(4) C4 0.059(5) 0.044(5) 0.040(4) 0.009(3) 0.004(3) 0.007(4) C5 0.047(5) 0.065(5) 0.047(4) 0.026(4) 0.003(4) 0.014(4) C6 0.065(6) 0.093(7) 0.050(5) 0.008(5) 0.018(4) 0.001(5) C10 0.060(6) 0.073(6) 0.074(6) 0.003(6) 0.014(5) -0.008(5) C11 0.064(6) 0.105(8) 0.115(8) 0.038(6) 0.000(5) 0.022(6) C12 0.086(7) 0.130(9) 0.073(6) 0.002(6) -0.004(5) -0.008(6) C13 0.068(6) 0.059(6) 0.060(5) 0.005(5) 0.008(4) 0.008(5) C14 0.101(7) 0.091(7) 0.086(7) -0.028(6) 0.018(5) 0.008(6) C15 0.064(6) 0.122(9) 0.109(7) 0.005(6) 0.036(5) -0.008(6) O2 0.068(4) 0.059(4) 0.076(4) 0.010(3) 0.018(3) 0.019(3) O3 0.064(3) 0.061(4) 0.056(3) 0.009(3) 0.018(3) 0.006(3) O4 0.056(3) 0.069(4) 0.060(3) 0.014(3) 0.005(3) 0.012(3) O5 0.071(4) 0.051(3) 0.049(3) 0.012(3) 0.004(3) -0.005(3) O6 0.050(3) 0.104(5) 0.068(3) 0.015(3) 0.012(3) 0.013(3) S21 0.113(2) 0.102(2) 0.0490(12) 0.0019(14) 0.0156(12) 0.010(2) C21' 0.108(8) 0.097(8) 0.081(7) 0.013(5) 0.013(6) 0.008(6) C22' 0.129(9) 0.219(13) 0.063(7) 0.055(7) 0.003(6) 0.039(9) O21' 0.162(6) 0.272(10) 0.057(4) 0.025(5) 0.050(4) 0.115(7) C21 0.067(5) 0.050(6) 0.058(5) 0.003(4) 0.015(4) -0.007(4) C22 0.058(5) 0.067(6) 0.058(5) -0.007(5) 0.014(5) -0.016(5) C23 0.052(5) 0.049(5) 0.061(5) -0.001(4) 0.005(5) -0.009(4) C24 0.039(4) 0.048(5) 0.044(4) -0.010(4) 0.006(4) 0.002(4) C25 0.050(4) 0.049(5) 0.064(4) 0.013(4) 0.020(4) 0.009(5) C26 0.056(5) 0.058(5) 0.073(5) 0.012(5) 0.003(4) 0.009(5) C30 0.042(5) 0.066(6) 0.066(6) -0.004(5) 0.001(5) 0.001(5) C31 0.051(5) 0.099(7) 0.108(7) 0.014(5) 0.031(5) -0.005(5) C32 0.073(5) 0.071(6) 0.067(6) -0.002(5) 0.028(4) 0.018(5) C33 0.050(6) 0.071(7) 0.072(6) 0.013(5) 0.008(4) -0.009(5) C34 0.058(6) 0.139(9) 0.137(9) 0.014(8) 0.034(6) 0.023(6) C35 0.139(9) 0.132(9) 0.063(7) 0.009(6) -0.005(6) 0.001(7) O22 0.062(3) 0.068(4) 0.068(3) 0.006(3) 0.004(3) -0.016(3) O23 0.052(3) 0.070(4) 0.081(4) 0.018(3) 0.013(3) 0.001(3) O24 0.039(3) 0.054(3) 0.063(3) 0.003(3) 0.017(3) -0.003(3) O25 0.074(3) 0.056(4) 0.057(3) 0.002(3) 0.020(3) -0.001(3) O26 0.047(3) 0.078(4) 0.072(3) 0.015(3) 0.009(3) 0.016(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 S1 O1' 1.508(6) . ? S1 C1' 1.810(8) . ? S1 C1 1.855(7) . ? C1' C2' 1.490(10) . ? C1 O5 1.424(8) . ? C1 C2 1.521(9) . ? C2 O2 1.427(8) . ? C2 C3 1.510(9) . ? C3 O3 1.442(7) . ? C3 C4 1.541(9) . ? C4 O4 1.431(7) . ? C4 C5 1.512(8) . ? C5 O5 1.446(8) . ? C5 C6 1.521(9) . ? C6 O6 1.430(8) . ? C10 O6 1.414(9) . ? C10 O4 1.434(9) . ? C10 C12 1.501(11) . ? C10 C11 1.530(11) . ? C13 O3 1.430(8) . ? C13 O2 1.438(8) . ? C13 C14 1.501(10) . ? C13 C15 1.513(10) . ? S21 O21' 1.500(6) . ? S21 C21' 1.765(9) . ? S21 C21 1.867(7) . ? C21' C22' 1.504(11) . ? C21 O25 1.402(8) . ? C21 C22 1.516(10) . ? C22 O22 1.423(8) . ? C22 C23 1.512(9) . ? C23 O23 1.422(8) . ? C23 C24 1.505(9) . ? C24 O24 1.426(7) . ? C24 C25 1.512(9) . ? C25 O25 1.424(8) . ? C25 C26 1.515(10) . ? C26 O26 1.413(8) . ? C30 O26 1.402(8) . ? C30 O24 1.438(8) . ? C30 C31 1.489(10) . ? C30 C32 1.537(9) . ? C33 O22 1.418(9) . ? C33 O23 1.442(8) . ? C33 C35 1.515(11) . ? C33 C34 1.525(11) . ? 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 O1' S1 C1' 109.2(4) . . ? O1' S1 C1 103.1(4) . . ? C1' S1 C1 98.2(4) . . ? C2' C1' S1 110.3(6) . . ? O5 C1 C2 113.6(5) . . ? O5 C1 S1 110.3(5) . . ? C2 C1 S1 109.0(5) . . ? O2 C2 C3 102.4(5) . . ? O2 C2 C1 110.5(6) . . ? C3 C2 C1 117.4(6) . . ? O3 C3 C2 103.0(5) . . ? O3 C3 C4 111.3(5) . . ? C2 C3 C4 110.6(6) . . ? O4 C4 C5 107.4(5) . . ? O4 C4 C3 109.1(5) . . ? C5 C4 C3 109.0(5) . . ? O5 C5 C4 107.1(5) . . ? O5 C5 C6 107.3(6) . . ? C4 C5 C6 108.0(5) . . ? O6 C6 C5 106.6(6) . . ? O6 C10 O4 109.8(6) . . ? O6 C10 C12 113.6(7) . . ? O4 C10 C12 111.4(7) . . ? O6 C10 C11 104.7(7) . . ? O4 C10 C11 104.9(7) . . ? C12 C10 C11 111.9(7) . . ? O3 C13 O2 106.1(6) . . ? O3 C13 C14 109.9(6) . . ? O2 C13 C14 108.6(7) . . ? O3 C13 C15 108.4(7) . . ? O2 C13 C15 111.1(6) . . ? C14 C13 C15 112.5(7) . . ? C2 O2 C13 106.7(5) . . ? C13 O3 C3 108.6(5) . . ? C4 O4 C10 113.5(5) . . ? C1 O5 C5 113.5(5) . . ? C10 O6 C6 114.3(6) . . ? O21' S21 C21' 108.4(5) . . ? O21' S21 C21 102.5(4) . . ? C21' S21 C21 97.4(4) . . ? C22' C21' S21 112.7(7) . . ? O25 C21 C22 115.7(6) . . ? O25 C21 S21 112.0(5) . . ? C22 C21 S21 106.6(5) . . ? O22 C22 C23 100.5(6) . . ? O22 C22 C21 110.0(6) . . ? C23 C22 C21 116.0(6) . . ? O23 C23 C24 113.2(6) . . ? O23 C23 C22 104.1(6) . . ? C24 C23 C22 112.7(6) . . ? O24 C24 C23 109.6(5) . . ? O24 C24 C25 110.8(5) . . ? C23 C24 C25 110.3(5) . . ? O25 C25 C24 107.7(5) . . ? O25 C25 C26 109.5(6) . . ? C24 C25 C26 107.1(5) . . ? O26 C26 C25 109.8(7) . . ? O26 C30 O24 111.2(6) . . ? O26 C30 C31 106.6(6) . . ? O24 C30 C31 105.7(6) . . ? O26 C30 C32 112.4(6) . . ? O24 C30 C32 109.5(6) . . ? C31 C30 C32 111.1(7) . . ? O22 C33 O23 105.8(6) . . ? O22 C33 C35 108.6(7) . . ? O23 C33 C35 109.4(7) . . ? O22 C33 C34 112.5(7) . . ? O23 C33 C34 107.9(7) . . ? C35 C33 C34 112.4(7) . . ? C33 O22 C22 106.5(5) . . ? C23 O23 C33 107.5(5) . . ? C24 O24 C30 113.2(5) . . ? C21 O25 C25 113.5(5) . . ? C30 O26 C26 115.4(5) . . ? # ----- MATERIAL RELEVANT TO THE COMPOUND 22 ----- data_DWDC8 _audit_creation_method SHELXL-97 _chemical_name_systematic ; 'S-Ethyl 4,6-Benzylidene-1-deoxy-1- thia-\a-D-mannopyranoside S-Oxide' ; _chemical_name_common ; 'Compound 22: Mannosyl benzylidene ethyl sulfone' ; _chemical_formula_analytical 'C15 H20 O6 S1' _chemical_formula_moiety 'C15 H20 O6 S1' _chemical_formula_structural 'C15 H20 O6 S1' _chemical_formula_sum 'C15 H20 O6 S1' _chemical_formula_weight 328.39 _chemical_melting_point 'not measured' _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M p_1_21_1 _symmetry_space_group_name_Hall p_2yb loop_ _symmetry_equiv_pos_as_xyz +x,+y,+z -x,1/2+y,-z _cell_length_a 5.1509(2) _cell_length_b 12.9187(4) _cell_length_c 11.4762(5) _cell_angle_alpha 90.00 _cell_angle_beta 95.554(2) _cell_angle_gamma 90.00 _cell_volume 760.07(8) _cell_formula_units_Z 2 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 1874 _cell_measurement_theta_min 2 _cell_measurement_theta_max 25 _exptl_crystal_description Needle _exptl_crystal_colour Colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.435 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 348 _exptl_absorpt_coefficient_mu 0.240 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_reflns_number 2613 _diffrn_reflns_av_R_equivalents 0.1236 _diffrn_reflns_av_sigmaI/netI 0.0878 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max 23.99 _reflns_number_total 1718 _reflns_number_gt 1551 _reflns_threshold_expression >2sigma(I) _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^)+(0.0900P)^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 -0.3(3) _refine_ls_number_reflns 1718 _refine_ls_number_parameters 199 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1039 _refine_ls_R_factor_gt 0.0864 _refine_ls_wR_factor_ref 0.2847 _refine_ls_wR_factor_gt 0.2582 _refine_ls_goodness_of_fit_ref 2.415 _refine_ls_restrained_S_all 2.414 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.001 loop_ _atom_type_symbol #ActaC _atom_type_description #ActaC _atom_type_oxidation_number _atom_type_number_in_cell _atom_type_scat_dispersion_real #ActaC _atom_type_scat_dispersion_imag #ActaC _atom_type_scat_source #ActaC C ? 0 30 .002 .002 'Int._Tables_Vol_IV_Tables_2.2B_and_2.3.1' H ? 0 40 0 0 'Int._Tables_Vol_IV_Tables_2.2B_and_2.3.1' O ? 0 12 .008 .006 'Int._Tables_Vol_IV_Tables_2.2B_and_2.3.1' S ? 0 2 .11 .124 'Int._Tables_Vol_IV_Tables_2.2B_and_2.3.1' 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 0.2898(5) 0.5464(2) 0.6479(2) 0.0263(8) Uani 1 1 d . . . O1 O 0.6480(14) 0.3455(6) 0.4537(7) 0.034(2) Uani 1 1 d . . . H1A H 0.6511 0.2809 0.4612 0.051 Uiso 1 1 calc R . . O2 O 0.1998(15) 0.2356(6) 0.4525(7) 0.031(2) Uani 1 1 d . . . H2A H 0.0616 0.2030 0.4609 0.046 Uiso 1 1 calc R . . O3 O 0.6628(13) 0.4023(6) 0.7040(7) 0.0246(18) Uani 1 1 d . . . O4 O 0.2323(13) 0.1776(5) 0.7013(7) 0.0222(17) Uani 1 1 d . . . O5 O 0.4510(14) 0.1981(6) 0.8893(7) 0.0290(19) Uani 1 1 d . . . O6 O 0.2419(15) 0.6181(5) 0.5455(7) 0.0291(19) Uani 1 1 d . . . C1 C 0.5476(18) 0.4598(8) 0.6032(9) 0.018(2) Uani 1 1 d . . . H1B H 0.6861 0.5027 0.5715 0.021 Uiso 1 1 calc R . . C2 C 0.4919(19) 0.3258(8) 0.7453(10) 0.022(2) Uani 1 1 d . . . H2B H 0.3340 0.3612 0.7705 0.026 Uiso 1 1 calc R . . C3 C 0.408(2) 0.2505(9) 0.6524(10) 0.028(3) Uani 1 1 d . . . H3A H 0.5632 0.2131 0.6271 0.033 Uiso 1 1 calc R . . C4 C 0.258(2) 0.3013(8) 0.5482(10) 0.023(3) Uani 1 1 d . . . H4A H 0.0931 0.3319 0.5725 0.028 Uiso 1 1 calc R . . C5 C 0.428(2) 0.3866(8) 0.5055(10) 0.025(3) Uani 1 1 d . . . H5A H 0.3210 0.4287 0.4455 0.030 Uiso 1 1 calc R . . C6 C 0.631(2) 0.2715(9) 0.8497(11) 0.029(3) Uani 1 1 d . . . H6B H 0.7891 0.2359 0.8272 0.035 Uiso 1 1 calc R . . H6C H 0.6847 0.3220 0.9124 0.035 Uiso 1 1 calc R . . C7 C 0.370(2) 0.1238(8) 0.7994(10) 0.025(3) Uani 1 1 d . . . H7A H 0.5239 0.0855 0.7742 0.029 Uiso 1 1 calc R . . C8 C 0.1781(17) 0.0498(10) 0.8469(9) 0.024(2) Uani 1 1 d . . . C9 C 0.108(2) 0.0561(11) 0.9623(10) 0.036(3) Uani 1 1 d . . . H9A H 0.1774 0.1094 1.0131 0.043 Uiso 1 1 calc R . . C10 C -0.061(2) -0.0143(9) 1.0007(12) 0.035(3) Uani 1 1 d . . . H10A H -0.0997 -0.0117 1.0799 0.042 Uiso 1 1 calc R . . C11 C -0.175(2) -0.0885(10) 0.9289(12) 0.034(3) Uani 1 1 d . . . H11A H -0.2972 -0.1351 0.9571 0.041 Uiso 1 1 calc R . . C12 C -0.112(2) -0.0959(10) 0.8116(10) 0.032(3) Uani 1 1 d . . . H12A H -0.1864 -0.1481 0.7605 0.038 Uiso 1 1 calc R . . C13 C 0.063(2) -0.0242(9) 0.7740(11) 0.031(3) Uani 1 1 d . . . H13A H 0.1038 -0.0267 0.6951 0.038 Uiso 1 1 calc R . . C14 C 0.490(2) 0.6164(9) 0.7595(11) 0.031(3) Uani 1 1 d . . . H14A H 0.5590 0.5681 0.8219 0.037 Uiso 1 1 calc R . . H14B H 0.6390 0.6486 0.7251 0.037 Uiso 1 1 calc R . . C15 C 0.326(3) 0.7002(9) 0.8115(11) 0.038(3) Uani 1 1 d . . . H15A H 0.4338 0.7378 0.8725 0.057 Uiso 1 1 calc R . . H15B H 0.1785 0.6680 0.8457 0.057 Uiso 1 1 calc R . . H15C H 0.2601 0.7485 0.7497 0.057 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 0.0288(12) 0.0297(14) 0.0202(17) -0.0004(13) 0.0015(10) 0.0064(12) O1 0.033(4) 0.037(4) 0.033(6) 0.002(4) 0.008(4) 0.000(4) O2 0.045(5) 0.034(4) 0.013(5) -0.005(3) 0.000(3) -0.015(3) O3 0.022(4) 0.029(4) 0.021(5) 0.006(4) -0.004(3) -0.003(3) O4 0.025(3) 0.027(4) 0.014(5) 0.005(3) -0.002(3) -0.001(3) O5 0.028(4) 0.043(4) 0.015(5) 0.001(4) 0.001(3) -0.004(4) O6 0.048(5) 0.025(4) 0.014(5) 0.005(3) 0.000(4) 0.002(4) C1 0.021(4) 0.028(5) 0.004(6) -0.003(4) 0.004(4) 0.006(4) C2 0.023(5) 0.028(6) 0.014(7) 0.002(5) -0.001(4) 0.001(4) C3 0.030(6) 0.038(7) 0.016(8) -0.005(5) 0.007(5) -0.003(5) C4 0.031(5) 0.027(6) 0.009(7) 0.001(4) -0.005(5) -0.001(4) C5 0.037(6) 0.026(6) 0.011(7) -0.004(5) -0.003(5) 0.005(5) C6 0.032(6) 0.030(6) 0.022(8) 0.008(5) -0.012(5) -0.012(5) C7 0.032(6) 0.029(5) 0.012(7) 0.000(5) 0.002(5) 0.002(5) C8 0.024(5) 0.030(6) 0.017(7) 0.004(5) 0.005(4) 0.007(5) C9 0.040(6) 0.055(8) 0.013(7) -0.001(6) 0.004(5) 0.006(6) C10 0.051(7) 0.033(6) 0.023(8) 0.006(5) 0.014(6) -0.005(6) C11 0.018(5) 0.043(7) 0.045(9) 0.016(6) 0.018(5) -0.002(5) C12 0.038(6) 0.048(7) 0.011(7) 0.006(6) 0.011(5) 0.003(6) C13 0.029(5) 0.042(7) 0.025(8) 0.001(6) 0.014(5) -0.007(5) C14 0.049(7) 0.027(6) 0.016(8) -0.004(5) -0.002(5) 0.009(5) C15 0.059(8) 0.041(7) 0.014(7) -0.001(5) 0.008(6) -0.003(6) _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 O6 1.497(7) . ? S1 C14 1.807(12) . ? S1 C1 1.847(9) . ? O1 C5 1.432(14) . ? O2 C4 1.398(12) . ? O3 C2 1.435(13) . ? O3 C1 1.452(12) . ? O4 C7 1.449(12) . ? O4 C3 1.457(14) . ? O5 C6 1.432(14) . ? O5 C7 1.441(13) . ? C1 C5 1.548(14) . ? C2 C3 1.476(15) . ? C2 C6 1.509(14) . ? C3 C4 1.509(15) . ? C4 C5 1.518(16) . ? C7 C8 1.515(16) . ? C8 C13 1.367(17) . ? C8 C9 1.409(16) . ? C9 C10 1.359(18) . ? C10 C11 1.360(19) . ? C11 C12 1.418(18) . ? C12 C13 1.388(17) . ? C14 C15 1.528(18) . ? 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 O6 S1 C14 106.6(5) . . ? O6 S1 C1 103.0(4) . . ? C14 S1 C1 97.1(5) . . ? C2 O3 C1 113.5(7) . . ? C7 O4 C3 109.5(7) . . ? C6 O5 C7 111.4(9) . . ? O3 C1 C5 111.6(7) . . ? O3 C1 S1 109.8(6) . . ? C5 C1 S1 108.9(6) . . ? O3 C2 C3 111.2(9) . . ? O3 C2 C6 108.8(8) . . ? C3 C2 C6 110.6(9) . . ? O4 C3 C2 107.2(9) . . ? O4 C3 C4 107.2(8) . . ? C2 C3 C4 112.2(9) . . ? O2 C4 C3 114.4(8) . . ? O2 C4 C5 105.9(9) . . ? C3 C4 C5 107.7(8) . . ? O1 C5 C4 111.7(8) . . ? O1 C5 C1 104.6(8) . . ? C4 C5 C1 114.3(9) . . ? O5 C6 C2 106.6(8) . . ? O5 C7 O4 108.8(8) . . ? O5 C7 C8 108.4(9) . . ? O4 C7 C8 107.1(8) . . ? C13 C8 C9 118.7(12) . . ? C13 C8 C7 118.7(10) . . ? C9 C8 C7 122.6(12) . . ? C10 C9 C8 119.7(13) . . ? C9 C10 C11 121.9(13) . . ? C10 C11 C12 119.7(11) . . ? C13 C12 C11 117.8(12) . . ? C8 C13 C12 122.1(12) . . ? C15 C14 S1 109.4(9) . . ? _diffrn_measured_fraction_theta_max 0.904 _diffrn_reflns_theta_full 23.99 _diffrn_measured_fraction_theta_full 0.904 _refine_diff_density_max 0.623 _refine_diff_density_min -0.517 _refine_diff_density_rms 0.133