Supplementary Material for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Michael Coogan' _publ_contact_author_address ; Chemistry Department Cardiff University Main Building Park Place Cardiff Wales/Cymru CF10 3AT UNITED KINGDOM ; _publ_contact_author_email COOGANMP@CF.AC.UK _publ_section_title ; Synthesis And Partial Kinetic Resolution Of 5-Alkylidene-1,3-Dioxane-4,6-Diones, An Easily Accessible Family Of Axially Chiral Alkenes. ; loop_ _publ_author_name 'Michael Coogan' 'Meritxell Casadesus' 'Li-ling Ooi.' # Attachment 'C21H20O5.cif' data_C21H20O5 _database_code_depnum_ccdc_archive 'CCDC 611771' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 5-(4-Methoxybenzylidene)-2-methyl-2-(2-phenylethyl)-1,3-dioxane-4,6-dione ; _chemical_name_common ;5-(4-Methoxybenzylidene)-2-methyl-2-(2-phenylethyl)-1,3- dioxane-4,6-dione ; _chemical_melting_point 91 _chemical_formula_moiety 'C21 H20 O5' _chemical_formula_sum 'C21 H20 O5' _chemical_formula_weight 352.37 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x-1/2, -y-1/2, z' _cell_length_a 9.6549(2) _cell_length_b 12.9703(3) _cell_length_c 14.7696(4) _cell_angle_alpha 90.00 _cell_angle_beta 108.6430(10) _cell_angle_gamma 90.00 _cell_volume 1752.50(7) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 10907 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.485 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.336 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 744 _exptl_absorpt_coefficient_mu 0.095 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9812 _exptl_absorpt_correction_T_max 0.9812 _exptl_absorpt_process_details 'Sortav (Blessing, 1995)' _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 KappaCCD _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 20365 _diffrn_reflns_av_R_equivalents 0.0826 _diffrn_reflns_av_sigmaI/netI 0.0716 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.14 _diffrn_reflns_theta_max 27.48 _reflns_number_total 3980 _reflns_number_gt 2773 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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^)+(0.0459P)^2^+0.3958P] 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 3980 _refine_ls_number_parameters 237 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0899 _refine_ls_R_factor_gt 0.0524 _refine_ls_wR_factor_ref 0.1171 _refine_ls_wR_factor_gt 0.1052 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _refine_ls_shift/su_max 0.002 _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 0.7618(2) 0.46708(19) 0.46664(16) 0.0532(6) Uani 1 1 d . . . H1 H 0.7452 0.5228 0.4227 0.064 Uiso 1 1 calc R . . C2 C 0.6984(2) 0.4687(2) 0.53858(19) 0.0697(8) Uani 1 1 d . . . H2 H 0.6402 0.5258 0.5443 0.084 Uiso 1 1 calc R . . C3 C 0.7197(3) 0.3879(3) 0.60162(17) 0.0739(9) Uani 1 1 d . . . H3 H 0.6758 0.3890 0.6507 0.089 Uiso 1 1 calc R . . C4 C 0.8044(3) 0.3053(2) 0.59379(15) 0.0655(7) Uani 1 1 d . . . H4 H 0.8182 0.2490 0.6369 0.079 Uiso 1 1 calc R . . C5 C 0.8701(2) 0.30463(19) 0.52224(14) 0.0496(6) Uani 1 1 d . . . H5 H 0.9299 0.2480 0.5176 0.059 Uiso 1 1 calc R . . C6 C 0.84918(19) 0.38539(16) 0.45782(13) 0.0398(5) Uani 1 1 d . . . C7 C 0.9187(2) 0.38798(15) 0.37947(13) 0.0380(5) Uani 1 1 d . . . H7A H 1.0080 0.4309 0.4012 0.046 Uiso 1 1 calc R . . H7B H 0.8501 0.4219 0.3227 0.046 Uiso 1 1 calc R . . C8 C 0.95944(19) 0.28298(14) 0.34975(12) 0.0341(4) Uani 1 1 d . . . H8A H 1.0508 0.2594 0.3982 0.041 Uiso 1 1 calc R . . H8B H 0.8816 0.2331 0.3492 0.041 Uiso 1 1 calc R . . C9 C 0.98092(17) 0.28218(13) 0.25267(12) 0.0283(4) Uani 1 1 d . . . C10 C 1.02600(18) 0.17787(13) 0.22651(13) 0.0308(4) Uani 1 1 d . . . H10A H 1.0369 0.1813 0.1629 0.046 Uiso 1 1 calc R . . H10B H 0.9510 0.1268 0.2263 0.046 Uiso 1 1 calc R . . H10C H 1.1193 0.1577 0.2734 0.046 Uiso 1 1 calc R . . C11 C 0.83638(17) 0.34575(12) 0.09814(12) 0.0253(4) Uani 1 1 d . . . C12 C 0.97902(17) 0.36642(12) 0.08350(12) 0.0243(4) Uani 1 1 d . . . C13 C 1.10211(17) 0.39182(13) 0.16966(12) 0.0255(4) Uani 1 1 d . . . C14 C 0.97766(18) 0.36571(12) -0.00879(12) 0.0261(4) Uani 1 1 d . . . H14 H 0.8818 0.3575 -0.0525 0.031 Uiso 1 1 calc R . . C15 C 1.08693(18) 0.37445(12) -0.05712(12) 0.0256(4) Uani 1 1 d . . . C16 C 1.03491(19) 0.37252(13) -0.15733(12) 0.0304(4) Uani 1 1 d . . . H16 H 0.9328 0.3662 -0.1891 0.036 Uiso 1 1 calc R . . C17 C 1.1280(2) 0.37960(14) -0.21091(13) 0.0340(4) Uani 1 1 d . . . H17 H 1.0900 0.3792 -0.2787 0.041 Uiso 1 1 calc R . . C18 C 1.27811(19) 0.38738(12) -0.16507(12) 0.0287(4) Uani 1 1 d . . . C19 C 1.33342(19) 0.38708(12) -0.06613(12) 0.0278(4) Uani 1 1 d . . . H19 H 1.4359 0.3907 -0.0347 0.033 Uiso 1 1 calc R . . C20 C 1.23810(18) 0.38150(12) -0.01363(12) 0.0275(4) Uani 1 1 d . . . H20 H 1.2766 0.3825 0.0541 0.033 Uiso 1 1 calc R . . C21 C 1.5165(2) 0.40669(15) -0.17965(13) 0.0389(5) Uani 1 1 d . . . H21A H 1.5361 0.4665 -0.1369 0.058 Uiso 1 1 calc R . . H21B H 1.5630 0.4169 -0.2291 0.058 Uiso 1 1 calc R . . H21C H 1.5562 0.3445 -0.1428 0.058 Uiso 1 1 calc R . . O1 O 0.84204(12) 0.31298(9) 0.18609(8) 0.0282(3) Uani 1 1 d . . . O2 O 1.08909(12) 0.35923(9) 0.25420(8) 0.0296(3) Uani 1 1 d . . . O3 O 1.20565(12) 0.44510(9) 0.17265(8) 0.0314(3) Uani 1 1 d . . . O4 O 0.71819(12) 0.35694(9) 0.03887(8) 0.0324(3) Uani 1 1 d . . . O5 O 1.36160(14) 0.39523(10) -0.22390(8) 0.0403(3) 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 0.0372(12) 0.0755(16) 0.0472(13) -0.0196(11) 0.0139(10) -0.0045(11) C2 0.0385(13) 0.116(2) 0.0569(17) -0.0320(16) 0.0183(12) 0.0019(14) C3 0.0393(13) 0.150(3) 0.0377(14) -0.0261(16) 0.0201(11) -0.0122(16) C4 0.0469(14) 0.118(2) 0.0319(12) -0.0009(13) 0.0123(11) -0.0118(14) C5 0.0372(11) 0.0826(16) 0.0288(11) -0.0062(11) 0.0103(9) -0.0040(11) C6 0.0230(9) 0.0659(14) 0.0286(10) -0.0154(9) 0.0054(8) -0.0106(9) C7 0.0314(10) 0.0517(12) 0.0323(10) -0.0107(9) 0.0120(8) -0.0110(9) C8 0.0235(9) 0.0502(12) 0.0282(10) 0.0012(8) 0.0077(8) -0.0021(8) C9 0.0153(8) 0.0400(10) 0.0282(9) 0.0002(7) 0.0049(7) -0.0026(7) C10 0.0223(9) 0.0369(10) 0.0326(10) 0.0014(8) 0.0080(8) -0.0004(7) C11 0.0213(9) 0.0231(8) 0.0307(10) -0.0034(7) 0.0074(8) 0.0011(7) C12 0.0207(8) 0.0233(8) 0.0282(9) 0.0004(7) 0.0067(7) 0.0011(6) C13 0.0203(8) 0.0283(9) 0.0299(10) -0.0030(7) 0.0109(7) 0.0017(7) C14 0.0224(8) 0.0214(8) 0.0324(10) 0.0013(7) 0.0056(7) 0.0004(7) C15 0.0261(9) 0.0220(8) 0.0284(9) 0.0006(7) 0.0085(7) 0.0017(7) C16 0.0277(9) 0.0316(10) 0.0298(10) 0.0005(7) 0.0062(8) -0.0008(7) C17 0.0355(10) 0.0412(11) 0.0243(9) -0.0007(8) 0.0080(8) -0.0032(8) C18 0.0327(10) 0.0277(9) 0.0294(10) 0.0002(7) 0.0150(8) -0.0022(7) C19 0.0241(8) 0.0290(9) 0.0297(10) 0.0019(7) 0.0076(7) 0.0003(7) C20 0.0276(9) 0.0307(9) 0.0230(9) 0.0032(7) 0.0063(7) 0.0035(7) C21 0.0344(11) 0.0481(12) 0.0394(11) -0.0010(9) 0.0190(9) -0.0075(9) O1 0.0179(6) 0.0396(7) 0.0272(7) 0.0004(5) 0.0074(5) 0.0008(5) O2 0.0201(6) 0.0398(7) 0.0279(7) -0.0037(5) 0.0064(5) -0.0059(5) O3 0.0223(6) 0.0369(7) 0.0369(7) -0.0081(5) 0.0121(5) -0.0069(5) O4 0.0203(6) 0.0401(7) 0.0337(7) 0.0009(5) 0.0045(5) 0.0015(5) O5 0.0357(7) 0.0589(9) 0.0298(7) -0.0005(6) 0.0155(6) -0.0068(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 C1 C2 1.386(3) . ? C1 C6 1.386(3) . ? C1 H1 0.9500 . ? C2 C3 1.373(4) . ? C2 H2 0.9500 . ? C3 C4 1.375(4) . ? C3 H3 0.9500 . ? C4 C5 1.395(3) . ? C4 H4 0.9500 . ? C5 C6 1.386(3) . ? C5 H5 0.9500 . ? C6 C7 1.512(2) . ? C7 C8 1.521(3) . ? C7 H7A 0.9900 . ? C7 H7B 0.9900 . ? C8 C9 1.513(2) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 O2 1.4404(19) . ? C9 O1 1.443(2) . ? C9 C10 1.509(2) . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 O4 1.2045(19) . ? C11 O1 1.351(2) . ? C11 C12 1.485(2) . ? C12 C14 1.359(2) . ? C12 C13 1.474(2) . ? C13 O3 1.2044(19) . ? C13 O2 1.3615(19) . ? C14 C15 1.455(2) . ? C14 H14 0.9500 . ? C15 C20 1.397(2) . ? C15 C16 1.403(2) . ? C16 C17 1.377(2) . ? C16 H16 0.9500 . ? C17 C18 1.394(2) . ? C17 H17 0.9500 . ? C18 O5 1.3649(19) . ? C18 C19 1.386(2) . ? C19 C20 1.382(2) . ? C19 H19 0.9500 . ? C20 H20 0.9500 . ? C21 O5 1.436(2) . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 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 C2 C1 C6 121.0(2) . . ? C2 C1 H1 119.5 . . ? C6 C1 H1 119.5 . . ? C3 C2 C1 120.1(2) . . ? C3 C2 H2 120.0 . . ? C1 C2 H2 120.0 . . ? C2 C3 C4 120.1(2) . . ? C2 C3 H3 119.9 . . ? C4 C3 H3 119.9 . . ? C3 C4 C5 119.7(3) . . ? C3 C4 H4 120.2 . . ? C5 C4 H4 120.2 . . ? C6 C5 C4 120.9(2) . . ? C6 C5 H5 119.5 . . ? C4 C5 H5 119.5 . . ? C5 C6 C1 118.20(18) . . ? C5 C6 C7 122.65(18) . . ? C1 C6 C7 119.15(19) . . ? C6 C7 C8 114.84(16) . . ? C6 C7 H7A 108.6 . . ? C8 C7 H7A 108.6 . . ? C6 C7 H7B 108.6 . . ? C8 C7 H7B 108.6 . . ? H7A C7 H7B 107.5 . . ? C9 C8 C7 113.97(15) . . ? C9 C8 H8A 108.8 . . ? C7 C8 H8A 108.8 . . ? C9 C8 H8B 108.8 . . ? C7 C8 H8B 108.8 . . ? H8A C8 H8B 107.7 . . ? O2 C9 O1 109.26(13) . . ? O2 C9 C10 111.05(13) . . ? O1 C9 C10 110.80(13) . . ? O2 C9 C8 107.38(13) . . ? O1 C9 C8 105.36(13) . . ? C10 C9 C8 112.76(14) . . ? C9 C10 H10A 109.5 . . ? C9 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C9 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? O4 C11 O1 118.32(14) . . ? O4 C11 C12 125.42(16) . . ? O1 C11 C12 116.25(14) . . ? C14 C12 C13 127.88(14) . . ? C14 C12 C11 115.64(15) . . ? C13 C12 C11 116.35(14) . . ? O3 C13 O2 117.61(15) . . ? O3 C13 C12 126.19(15) . . ? O2 C13 C12 115.90(13) . . ? C12 C14 C15 135.69(16) . . ? C12 C14 H14 112.2 . . ? C15 C14 H14 112.2 . . ? C20 C15 C16 117.08(15) . . ? C20 C15 C14 126.47(15) . . ? C16 C15 C14 116.42(15) . . ? C17 C16 C15 121.72(16) . . ? C17 C16 H16 119.1 . . ? C15 C16 H16 119.1 . . ? C16 C17 C18 119.60(16) . . ? C16 C17 H17 120.2 . . ? C18 C17 H17 120.2 . . ? O5 C18 C19 124.36(16) . . ? O5 C18 C17 115.49(15) . . ? C19 C18 C17 120.15(15) . . ? C20 C19 C18 119.37(16) . . ? C20 C19 H19 120.3 . . ? C18 C19 H19 120.3 . . ? C19 C20 C15 122.05(15) . . ? C19 C20 H20 119.0 . . ? C15 C20 H20 119.0 . . ? O5 C21 H21A 109.5 . . ? O5 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? O5 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C11 O1 C9 119.05(12) . . ? C13 O2 C9 118.69(12) . . ? C18 O5 C21 117.33(13) . . ? 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 -1.0(3) . . . . ? C1 C2 C3 C4 0.3(4) . . . . ? C2 C3 C4 C5 0.8(4) . . . . ? C3 C4 C5 C6 -1.1(3) . . . . ? C4 C5 C6 C1 0.3(3) . . . . ? C4 C5 C6 C7 179.76(19) . . . . ? C2 C1 C6 C5 0.8(3) . . . . ? C2 C1 C6 C7 -178.73(19) . . . . ? C5 C6 C7 C8 23.7(3) . . . . ? C1 C6 C7 C8 -156.82(17) . . . . ? C6 C7 C8 C9 160.82(15) . . . . ? C7 C8 C9 O2 55.51(18) . . . . ? C7 C8 C9 O1 -60.87(18) . . . . ? C7 C8 C9 C10 178.15(14) . . . . ? O4 C11 C12 C14 -21.8(2) . . . . ? O1 C11 C12 C14 159.08(14) . . . . ? O4 C11 C12 C13 154.33(16) . . . . ? O1 C11 C12 C13 -24.8(2) . . . . ? C14 C12 C13 O3 24.4(3) . . . . ? C11 C12 C13 O3 -151.18(16) . . . . ? C14 C12 C13 O2 -162.02(15) . . . . ? C11 C12 C13 O2 22.4(2) . . . . ? C13 C12 C14 C15 9.3(3) . . . . ? C11 C12 C14 C15 -175.06(17) . . . . ? C12 C14 C15 C20 3.8(3) . . . . ? C12 C14 C15 C16 -178.22(17) . . . . ? C20 C15 C16 C17 -1.4(2) . . . . ? C14 C15 C16 C17 -179.63(15) . . . . ? C15 C16 C17 C18 1.0(3) . . . . ? C16 C17 C18 O5 -179.28(15) . . . . ? C16 C17 C18 C19 0.5(3) . . . . ? O5 C18 C19 C20 178.28(15) . . . . ? C17 C18 C19 C20 -1.5(2) . . . . ? C18 C19 C20 C15 1.0(2) . . . . ? C16 C15 C20 C19 0.4(2) . . . . ? C14 C15 C20 C19 178.41(16) . . . . ? O4 C11 O1 C9 169.42(14) . . . . ? C12 C11 O1 C9 -11.4(2) . . . . ? O2 C9 O1 C11 47.56(18) . . . . ? C10 C9 O1 C11 -75.10(17) . . . . ? C8 C9 O1 C11 162.65(13) . . . . ? O3 C13 O2 C9 -169.90(14) . . . . ? C12 C13 O2 C9 16.0(2) . . . . ? O1 C9 O2 C13 -50.11(18) . . . . ? C10 C9 O2 C13 72.40(17) . . . . ? C8 C9 O2 C13 -163.90(13) . . . . ? C19 C18 O5 C21 -1.7(2) . . . . ? C17 C18 O5 C21 178.08(15) . . . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.195 _refine_diff_density_min -0.202 _refine_diff_density_rms 0.047