# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _publ_contact_author_email DAVID.HODGSON@CHEM.OX.AC.UK _publ_contact_author_name 'Dr David Hodgson' _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_address ; Department of Chemistry Dyson Perrins Laboratory University of Oxford South Parks Road Oxford OX1 3QY UNITED KINGDOM ; _publ_section_title ; Use of allene in 1,3-dipolar addition to a carbonyl ylide: syntheses of 3-hydroxy-cis-nemorensic acid and nemorensic acid ; loop_ _publ_author_name D.Hodgson 'F.Le Strat' data_ARC557 _database_code_depnum_ccdc_archive 'CCDC 225241' _chemical_name_common ; (1'R*,5'R*,7'R*)-dispiro(1,3-dioxolane-2,2'-(1',5'-dimethyl- 8'-oxa-bicyclo(3.2.1)octane)-7',2''-oxirane) ; #============================================================= # Diffractometer details #============================================================= _diffrn_measurement_device_type ; Nonius KappaCCD ; _diffrn_radiation_monochromator graphite _computing_data_collection ; KappaCCD software 'Collect' (Nonius, 2000) ; _computing_data_reduction ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_cell_refinement ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; #============================================================= # General computing #============================================================= _computing_structure_refinement ; CRYSTALS (Watkin et al, 2001) ; _computing_publication_material ; CRYSTALS (Watkin et al, 2001) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' _chemical_name_systematic ; [1'R*,5'R*,7'R*]-dispiro[1,3-dioxolane-2,2'-(1',5'-dimethyl-8'-oxa- bicyclo[3.2.1]octane)-7',2''-oxirane] ; _chemical_melting_point 77C _refine_ls_matrix_type full _atom_sites_solution_primary direct _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment noref #============================================================= _cell_length_a 12.7237(3) _cell_angle_alpha 90 _cell_length_b 8.2796(2) _cell_angle_beta 99.5173(11) _cell_length_c 10.8451(2) _cell_angle_gamma 90 _cell_volume 1126.8 _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1 ' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x,y+1/2,-z+1/2 x,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source 'C ' 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 International_Tables_Vol_IV_Table_2.2B 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 International_Tables_Vol_IV_Table_2.2B 'O ' 0.0080 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 International_Tables_Vol_IV_Table_2.2B _chemical_formula_sum ' C12 H18 O4 ' _chemical_formula_moiety ' C12 H18 O4 ' _chemical_compound_source ; synthesis as described ; _chemical_formula_weight 226.27 _cell_measurement_reflns_used 11736 _cell_measurement_theta_min 5 _cell_measurement_theta_max 28 _cell_measurement_temperature 150 _cell_formula_units_Z 4 _exptl_crystal_description ' fragment ' _exptl_crystal_colour ' colourless ' _exptl_crystal_preparation ' 10% CH2Cl2:petrol ' _exptl_crystal_size_min 0.20 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_max 0.65 _exptl_crystal_density_diffrn 1.334 _exptl_crystal_density_meas ? _exptl_crystal_F_000 488 _exptl_absorpt_coefficient_mu 0.099 _diffrn_measurement_method \w _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Denzo/Scalepack (Otwinowski & Minor, 1996) ; _exptl_absorpt_correction_T_min 0.94 _exptl_absorpt_correction_T_max 0.98 _diffrn_standards_interval_time 0 _diffrn_standards_interval_count 0 _diffrn_standards_number 0 _diffrn_standards_decay_% 0.00 _diffrn_ambient_temperature 150 _diffrn_reflns_number 11736 _reflns_number_total 2548 #2728 unique reflections including absences _diffrn_reflns_av_R_equivalents 0.025 _diffrn_measured_fraction_theta_max 0.998 _reflns_number_gt 1914 _diffrn_reflns_theta_min 5.19 _diffrn_reflns_theta_max 27.45 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _reflns_limit_h_min -16 _reflns_limit_h_max 16 _reflns_limit_k_min 0 _reflns_limit_k_max 10 _reflns_limit_l_min 0 _reflns_limit_l_max 14 _refine_diff_density_min -0.28 _refine_diff_density_max 0.32 _reflns_threshold_expression >3.00\s(I) _refine_ls_number_reflns 1914 _refine_ls_number_parameters 145 _refine_ls_R_factor_gt 0.0422 _refine_ls_wR_factor_ref 0.0549 _refine_ls_goodness_of_fit_ref 1.0276 _refine_ls_shift/su_max 0.011630 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Chebychev polynomial with 3 parameters (Carruthers & Watkin , 1979) 1.39 0.752 0.881 ; _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 # Uequiv = arithmetic mean of Ui # i.e. Ueqiv = (U1+U2+U3)/3 loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type O1 0.33075(7) 0.67320(11) 0.42478(8) 0.0217 1.0000 Uani C1 0.28996(11) 0.78009(16) 0.51230(12) 0.0239 1.0000 Uani C2 0.16859(12) 0.78578(19) 0.47495(14) 0.0313 1.0000 Uani C3 0.12012(11) 0.61742(19) 0.47964(14) 0.0303 1.0000 Uani C4 0.1805(1) 0.49342(17) 0.41500(13) 0.0243 1.0000 Uani C5 0.3027(1) 0.51217(15) 0.45767(12) 0.0207 1.0000 Uani C6 0.3306(1) 0.51877(17) 0.60107(12) 0.0250 1.0000 Uani C7 0.32478(12) 0.69523(19) 0.63771(12) 0.0291 1.0000 Uani C8 0.33957(14) 0.94431(19) 0.50183(15) 0.0357 1.0000 Uani O2 0.15825(9) 0.51583(14) 0.28277(9) 0.0356 1.0000 Uani O3 0.14671(9) 0.33499(13) 0.44016(11) 0.0358 1.0000 Uani C9 0.0961(2) 0.3855(2) 0.2296(2) 0.0646 1.0000 Uani C10 0.09889(15) 0.2618(2) 0.32694(18) 0.0464 1.0000 Uani C11 0.36584(12) 0.39313(18) 0.39402(15) 0.0313 1.0000 Uani O4 0.28791(9) 0.39802(15) 0.6745(1) 0.0379 1.0000 Uani C12 0.40180(12) 0.4031(2) 0.67571(15) 0.0381 1.0000 Uani H21 0.1384 0.8584 0.5339 0.0372 1.0000 Uiso H22 0.1504 0.8292 0.3880 0.0372 1.0000 Uiso H31 0.1230 0.5851 0.5690 0.0363 1.0000 Uiso H32 0.0442 0.6204 0.4369 0.0363 1.0000 Uiso H71 0.3959 0.7354 0.6796 0.0348 1.0000 Uiso H72 0.2712 0.7115 0.6945 0.0348 1.0000 Uiso H81 0.3131 1.0209 0.5610 0.0423 1.0000 Uiso H82 0.4189 0.9353 0.5232 0.0423 1.0000 Uiso H83 0.3196 0.9854 0.4144 0.0423 1.0000 Uiso H91 0.0211 0.4216 0.2008 0.0700 1.0000 Uiso H92 0.1262 0.3411 0.1571 0.0700 1.0000 Uiso H101 0.0250 0.2255 0.3330 0.0573 1.0000 Uiso H102 0.1421 0.1670 0.3076 0.0573 1.0000 Uiso H111 0.3471 0.2807 0.4161 0.0381 1.0000 Uiso H112 0.4437 0.4118 0.4224 0.0381 1.0000 Uiso H113 0.3485 0.4080 0.3014 0.0381 1.0000 Uiso H121 0.4508 0.4400 0.7523 0.0450 1.0000 Uiso H122 0.4373 0.3161 0.6335 0.0450 1.0000 Uiso 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 O1 0.0263(4) 0.0207(5) 0.0189(4) -0.0004(3) 0.0058(3) -0.0049(4) C1 0.0271(6) 0.0226(6) 0.0219(6) -0.0033(5) 0.0035(5) -0.0018(5) C2 0.0275(7) 0.0266(7) 0.0388(8) -0.0036(6) 0.0025(6) 0.0037(5) C3 0.0200(6) 0.0316(8) 0.0391(8) -0.0006(6) 0.0044(5) -0.0006(5) C4 0.0232(6) 0.0225(6) 0.0262(6) 0.0015(5) 0.0013(5) -0.0051(5) C5 0.0214(6) 0.0184(6) 0.0227(6) 0.0019(5) 0.0044(5) -0.0030(5) C6 0.0232(6) 0.0301(7) 0.0219(6) 0.0076(5) 0.0038(5) -0.0040(5) C7 0.0330(7) 0.0343(8) 0.0196(6) -0.0025(5) 0.0033(5) -0.0028(6) C8 0.0425(8) 0.0251(7) 0.0381(8) -0.0039(6) 0.0028(6) -0.0093(6) O2 0.0410(6) 0.0372(6) 0.0253(5) -0.0029(4) -0.0037(4) -0.0152(5) O3 0.0324(5) 0.0255(5) 0.0476(6) 0.0049(5) 0.0006(5) -0.0120(4) C9 0.0822(15) 0.0303(9) 0.0625(12) -0.0039(8) -0.0434(11) -0.0103(9) C10 0.052(1) 0.0391(9) 0.052(1) -0.0201(8) 0.0212(8) -0.0232(8) C11 0.0285(7) 0.0273(7) 0.0396(8) -0.0065(6) 0.0097(6) -0.0010(6) O4 0.0356(6) 0.0442(7) 0.0340(5) 0.0186(5) 0.0061(4) -0.0073(5) C12 0.0312(8) 0.0439(9) 0.0374(8) 0.0167(7) -0.0002(6) 0.0007(7) _refine_ls_extinction_method None loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag O1 . C1 . 1.4547(15) yes O1 . C5 . 1.4401(15) yes C1 . C2 . 1.5310(19) yes C1 . C7 . 1.5299(18) yes C1 . C8 . 1.511(2) yes C2 . C3 . 1.529(2) yes C2 . H21 . 1.0000 no C2 . H22 . 1.0000 no C3 . C4 . 1.522(2) yes C3 . H31 . 1.0000 no C3 . H32 . 1.0000 no C4 . C5 . 1.5549(18) yes C4 . O2 . 1.4272(16) yes C4 . O3 . 1.4210(17) yes C5 . C6 . 1.5379(18) yes C5 . C11 . 1.5085(19) yes C6 . C7 . 1.519(2) yes C6 . O4 . 1.4394(16) yes C6 . C12 . 1.466(2) yes C7 . H71 . 1.0000 no C7 . H72 . 1.0000 no C8 . H81 . 1.0000 no C8 . H82 . 1.0000 no C8 . H83 . 1.0000 no O2 . C9 . 1.404(2) yes O3 . C10 . 1.413(2) yes C9 . C10 . 1.467(3) yes C9 . H91 . 1.000 no C9 . H92 . 1.000 no C10 . H101 . 1.0000 no C10 . H102 . 1.0000 no C11 . H111 . 1.0000 no C11 . H112 . 1.0000 no C11 . H113 . 1.0000 no O4 . C12 . 1.4476(19) yes C12 . H121 . 1.0000 no C12 . H122 . 1.0000 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C1 . O1 . C5 . 105.79(9) yes O1 . C1 . C2 . 107.4(1) yes O1 . C1 . C7 . 102.6(1) yes C2 . C1 . C7 . 112.37(12) yes O1 . C1 . C8 . 107.44(11) yes C2 . C1 . C8 . 111.60(12) yes C7 . C1 . C8 . 114.63(12) yes C1 . C2 . C3 . 110.98(12) yes C1 . C2 . H21 . 109.09 no C3 . C2 . H21 . 109.09 no C1 . C2 . H22 . 109.09 no C3 . C2 . H22 . 109.09 no H21 . C2 . H22 . 109.47 no C2 . C3 . C4 . 111.26(11) yes C2 . C3 . H31 . 109.02 no C4 . C3 . H31 . 109.02 no C2 . C3 . H32 . 109.02 no C4 . C3 . H32 . 109.02 no H31 . C3 . H32 . 109.47 no C3 . C4 . C5 . 110.62(11) yes C3 . C4 . O2 . 110.10(12) yes C5 . C4 . O2 . 108.00(11) yes C3 . C4 . O3 . 110.01(11) yes C5 . C4 . O3 . 110.78(11) yes O2 . C4 . O3 . 107.27(11) yes O1 . C5 . C4 . 107.2(1) yes O1 . C5 . C6 . 101.09(9) yes C4 . C5 . C6 . 110.9(1) yes O1 . C5 . C11 . 108.6(1) yes C4 . C5 . C11 . 112.35(11) yes C6 . C5 . C11 . 115.77(11) yes C5 . C6 . C7 . 106.6(1) yes C5 . C6 . O4 . 119.32(11) yes C7 . C6 . O4 . 118.95(12) yes C5 . C6 . C12 . 123.59(13) yes C7 . C6 . C12 . 122.42(13) yes O4 . C6 . C12 . 59.75(9) yes C1 . C7 . C6 . 103.2(1) yes C1 . C7 . H71 . 111.01 no C6 . C7 . H71 . 111.01 no C1 . C7 . H72 . 111.01 no C6 . C7 . H72 . 111.01 no H71 . C7 . H72 . 109.47 no C1 . C8 . H81 . 109.47 no C1 . C8 . H82 . 109.47 no H81 . C8 . H82 . 109.48 no C1 . C8 . H83 . 109.47 no H81 . C8 . H83 . 109.48 no H82 . C8 . H83 . 109.48 no C4 . O2 . C9 . 108.51(13) yes C4 . O3 . C10 . 109.23(12) yes O2 . C9 . C10 . 107.23(14) yes O2 . C9 . H91 . 110.03 no C10 . C9 . H91 . 110.0 no O2 . C9 . H92 . 110.0 no C10 . C9 . H92 . 110.03 no H91 . C9 . H92 . 109.47 no O3 . C10 . C9 . 106.35(13) yes O3 . C10 . H101 . 110.25 no C9 . C10 . H101 . 110.2 no O3 . C10 . H102 . 110.25 no C9 . C10 . H102 . 110.25 no H101 . C10 . H102 . 109.47 no C5 . C11 . H111 . 109.47 no C5 . C11 . H112 . 109.47 no H111 . C11 . H112 . 109.48 no C5 . C11 . H113 . 109.47 no H111 . C11 . H113 . 109.48 no H112 . C11 . H113 . 109.48 no C6 . O4 . C12 . 61.05(9) yes C6 . C12 . O4 . 59.20(9) yes C6 . C12 . H121 . 120.13 no O4 . C12 . H121 . 120.13 no C6 . C12 . H122 . 120.13 no O4 . C12 . H122 . 120.13 no H121 . C12 . H122 . 109.47 no