# 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 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_email np.argade@ncl.res.in _publ_contact_author_name 'N. P. Argade' loop_ _publ_author_name N.Argade R.Patel V.Puranik # Attachment '- 5.cif' ##Title:Regio- and Stereoselective Selenium Dioxide Allylic ##Oxidation of (E)-Dialkyl Alkylidenesuccinates: Direct Proof ##for the Proposed Ene Reaction Followed by [2,3] Sigma Tropic ##Shift Mechanism: Synthesis of Natural and Unnatural Butenolides ##Communicated to J.AM.Chem.Soc. ##By Ramesh M. Patel,Vedavati G. Puranik and Narshinha P. Argade. ##Division of Organic Chemistry and Center for Materials Charecterization, ##National Chemical Laboratory Pune-411 008, India data_C10H12O4compound19 _database_code_depnum_ccdc_archive 'CCDC 813260' #TrackingRef '- 5.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'Fused Butenolides' _chemical_melting_point '..... degree Centigrade' _chemical_formula_moiety 'C10 H12 O4' _chemical_formula_sum 'C10 H12 O4' _chemical_formula_weight 196.20 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 C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 18.7250(10) _cell_length_b 10.4070(9) _cell_length_c 12.1150(14) _cell_angle_alpha 90.00 _cell_angle_beta 122.3020(10) _cell_angle_gamma 90.00 _cell_volume 1995.5(3) _cell_formula_units_Z 8 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 1995 _cell_measurement_theta_min 2.342 _cell_measurement_theta_max 26.061 _exptl_crystal_description Plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.34 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.306 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 832 _exptl_absorpt_coefficient_mu 0.101 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9654 _exptl_absorpt_correction_T_max 0.9937 _exptl_absorpt_process_details 'Bruker SADABS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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_device ' Bruker Smart APEX' _diffrn_measurement_method 'Omega Scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4885 _diffrn_reflns_av_R_equivalents 0.0159 _diffrn_reflns_av_sigmaI/netI 0.0170 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.34 _diffrn_reflns_theta_max 25.00 _reflns_number_total 1753 _reflns_number_gt 1552 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'BRUKER SMART' _computing_cell_refinement 'BRUKER SAINT' _computing_data_reduction 'BRUKER SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0547P)^2^+1.1461P] 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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1753 _refine_ls_number_parameters 128 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0539 _refine_ls_R_factor_gt 0.0483 _refine_ls_wR_factor_ref 0.1197 _refine_ls_wR_factor_gt 0.1156 _refine_ls_goodness_of_fit_ref 1.071 _refine_ls_restrained_S_all 1.071 _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 O1' O 0.12348(8) 0.23165(12) 0.32571(12) 0.0550(4) Uani 1 1 d . . . O1 O 0.08721(10) 0.42545(14) 0.22948(14) 0.0693(4) Uani 1 1 d . . . O2 O 0.14737(9) 0.74538(13) 0.48272(18) 0.0729(5) Uani 1 1 d . . . H2 H 0.1853 0.7924 0.4920 0.109 Uiso 1 1 calc R . . O3 O 0.23445(9) 0.59431(12) 0.49463(16) 0.0686(5) Uani 1 1 d . . . C1 C 0.16847(11) 0.62593(17) 0.48398(17) 0.0479(4) Uani 1 1 d . . . C2 C 0.10412(12) 0.53243(17) 0.47211(19) 0.0524(5) Uani 1 1 d . . . H2A H 0.1032 0.5353 0.5514 0.063 Uiso 1 1 calc R . . H2B H 0.0488 0.5585 0.4003 0.063 Uiso 1 1 calc R . . C2' C 0.10797(11) 0.35964(18) 0.32407(17) 0.0481(4) Uani 1 1 d . . . C3' C 0.12049(10) 0.39739(17) 0.44956(16) 0.0442(4) Uani 1 1 d . . . C4' C 0.14528(10) 0.29440(17) 0.52579(17) 0.0461(4) Uani 1 1 d . . . C5 C 0.14839(11) 0.18115(17) 0.45250(18) 0.0481(4) Uani 1 1 d . . . H5 H 0.2065 0.1490 0.4962 0.058 Uiso 1 1 calc R . . C6 C 0.16171(15) 0.2708(2) 0.65867(19) 0.0678(6) Uani 1 1 d . . . H6A H 0.1476 0.3467 0.6895 0.081 Uiso 1 1 calc R . . H6B H 0.2211 0.2518 0.7191 0.081 Uiso 1 1 calc R . . C7 C 0.10741(17) 0.1566(2) 0.6521(2) 0.0769(7) Uani 1 1 d . . . H7A H 0.1242 0.1321 0.7400 0.092 Uiso 1 1 calc R . . H7B H 0.0486 0.1826 0.6060 0.092 Uiso 1 1 calc R . . C8 C 0.11633(14) 0.0416(2) 0.5835(2) 0.0696(6) Uani 1 1 d . . . H8A H 0.0810 -0.0279 0.5811 0.084 Uiso 1 1 calc R . . H8B H 0.1745 0.0122 0.6322 0.084 Uiso 1 1 calc R . . C9 C 0.09092(12) 0.07500(17) 0.4451(2) 0.0563(5) Uani 1 1 d . . . H9A H 0.0964 0.0001 0.4025 0.068 Uiso 1 1 calc R . . H9B H 0.0326 0.1033 0.3950 0.068 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 O1' 0.0698(8) 0.0507(8) 0.0571(8) -0.0054(6) 0.0423(7) -0.0037(6) O1 0.0845(10) 0.0747(10) 0.0597(9) 0.0169(8) 0.0459(8) 0.0074(8) O2 0.0725(10) 0.0378(8) 0.1200(14) -0.0010(8) 0.0591(10) -0.0014(6) O3 0.0591(8) 0.0391(8) 0.1106(12) -0.0003(7) 0.0473(8) -0.0032(6) C1 0.0549(11) 0.0372(10) 0.0493(10) -0.0008(8) 0.0263(8) -0.0010(8) C2 0.0606(11) 0.0438(10) 0.0613(11) -0.0035(9) 0.0383(9) -0.0048(8) C2' 0.0488(10) 0.0511(11) 0.0508(10) 0.0038(9) 0.0308(8) -0.0033(8) C3' 0.0447(9) 0.0429(10) 0.0488(10) -0.0030(8) 0.0274(8) -0.0081(7) C4' 0.0446(9) 0.0463(10) 0.0465(10) -0.0024(8) 0.0238(8) -0.0083(8) C5 0.0455(9) 0.0457(10) 0.0553(10) 0.0016(8) 0.0283(8) 0.0004(8) C6 0.0878(15) 0.0639(14) 0.0479(11) 0.0008(10) 0.0339(11) -0.0054(11) C7 0.1013(17) 0.0789(16) 0.0660(14) 0.0138(12) 0.0550(13) -0.0051(13) C8 0.0753(14) 0.0519(12) 0.0860(16) 0.0170(11) 0.0460(12) -0.0033(10) C9 0.0568(11) 0.0431(11) 0.0724(13) -0.0025(9) 0.0367(10) -0.0045(8) _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 O1' C2' 1.361(2) . ? O1' C5 1.445(2) . ? O1 C2' 1.207(2) . ? O2 C1 1.302(2) . ? O2 H2 0.8200 . ? O3 C1 1.217(2) . ? C1 C2 1.495(3) . ? C2 C3' 1.494(2) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C2' C3' 1.463(2) . ? C3' C4' 1.326(2) . ? C4' C6 1.489(3) . ? C4' C5 1.495(3) . ? C5 C9 1.511(2) . ? C5 H5 0.9800 . ? C6 C7 1.538(3) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C8 1.516(3) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 C9 1.518(3) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? 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' O1' C5 108.46(13) . . ? C1 O2 H2 109.5 . . ? O3 C1 O2 122.95(17) . . ? O3 C1 C2 123.69(16) . . ? O2 C1 C2 113.36(16) . . ? C3' C2 C1 113.34(15) . . ? C3' C2 H2A 108.9 . . ? C1 C2 H2A 108.9 . . ? C3' C2 H2B 108.9 . . ? C1 C2 H2B 108.9 . . ? H2A C2 H2B 107.7 . . ? O1 C2' O1' 121.80(17) . . ? O1 C2' C3' 128.74(18) . . ? O1' C2' C3' 109.46(15) . . ? C4' C3' C2' 107.99(16) . . ? C4' C3' C2 131.47(17) . . ? C2' C3' C2 120.53(16) . . ? C3' C4' C6 132.81(18) . . ? C3' C4' C5 109.49(16) . . ? C6 C4' C5 117.43(16) . . ? O1' C5 C4' 104.58(14) . . ? O1' C5 C9 112.82(14) . . ? C4' C5 C9 111.04(15) . . ? O1' C5 H5 109.4 . . ? C4' C5 H5 109.4 . . ? C9 C5 H5 109.4 . . ? C4' C6 C7 108.82(17) . . ? C4' C6 H6A 109.9 . . ? C7 C6 H6A 109.9 . . ? C4' C6 H6B 109.9 . . ? C7 C6 H6B 109.9 . . ? H6A C6 H6B 108.3 . . ? C8 C7 C6 112.02(19) . . ? C8 C7 H7A 109.2 . . ? C6 C7 H7A 109.2 . . ? C8 C7 H7B 109.2 . . ? C6 C7 H7B 109.2 . . ? H7A C7 H7B 107.9 . . ? C7 C8 C9 111.29(17) . . ? C7 C8 H8A 109.4 . . ? C9 C8 H8A 109.4 . . ? C7 C8 H8B 109.4 . . ? C9 C8 H8B 109.4 . . ? H8A C8 H8B 108.0 . . ? C5 C9 C8 108.00(16) . . ? C5 C9 H9A 110.1 . . ? C8 C9 H9A 110.1 . . ? C5 C9 H9B 110.1 . . ? C8 C9 H9B 110.1 . . ? H9A C9 H9B 108.4 . . ? 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 O3 C1 C2 C3' -10.8(3) . . . . ? O2 C1 C2 C3' 169.68(17) . . . . ? C5 O1' C2' O1 178.87(16) . . . . ? C5 O1' C2' C3' -1.19(18) . . . . ? O1 C2' C3' C4' -178.40(18) . . . . ? O1' C2' C3' C4' 1.67(19) . . . . ? O1 C2' C3' C2 2.5(3) . . . . ? O1' C2' C3' C2 -177.48(14) . . . . ? C1 C2 C3' C4' 109.8(2) . . . . ? C1 C2 C3' C2' -71.3(2) . . . . ? C2' C3' C4' C6 -175.06(19) . . . . ? C2 C3' C4' C6 4.0(3) . . . . ? C2' C3' C4' C5 -1.41(19) . . . . ? C2 C3' C4' C5 177.61(17) . . . . ? C2' O1' C5 C4' 0.35(17) . . . . ? C2' O1' C5 C9 121.14(16) . . . . ? C3' C4' C5 O1' 0.71(18) . . . . ? C6 C4' C5 O1' 175.46(15) . . . . ? C3' C4' C5 C9 -121.26(17) . . . . ? C6 C4' C5 C9 53.5(2) . . . . ? C3' C4' C6 C7 124.5(2) . . . . ? C5 C4' C6 C7 -48.7(2) . . . . ? C4' C6 C7 C8 50.0(3) . . . . ? C6 C7 C8 C9 -58.8(3) . . . . ? O1' C5 C9 C8 -172.96(15) . . . . ? C4' C5 C9 C8 -55.9(2) . . . . ? C7 C8 C9 C5 60.4(2) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.203 _refine_diff_density_min -0.185 _refine_diff_density_rms 0.051 # Attachment '- 10.cif' ##Title:Regio- and Stereoselective Selenium Dioxide Allylic ##Oxidation of (E)-Dialkyl Alkylidenesuccinates: Direct Proof ##for the Proposed Ene Reaction Followed by [2,3] Sigma Tropic ##Shift Mechanism: Synthesis of Natural and Unnatural Butenolides ##Communicated to J.AM.Chem.Soc. ##By Ramesh M. Patel,Vedavati G. Puranik and Narshinha P. Argade. ##Division of Organic Chemistry and Center for Materials Charecterization, ##National Chemical Laboratory Pune-411 008, India data_C11H16O4compound21 _database_code_depnum_ccdc_archive 'CCDC 813261' #TrackingRef '- 10.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'Fused Butenolides' _chemical_melting_point '128-130 degree Centigrade' _chemical_formula_moiety 'C11 H16 O4' _chemical_formula_sum 'C11 H16 O4' _chemical_formula_weight 212.24 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 P21/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 6.1283(7) _cell_length_b 8.0991(10) _cell_length_c 22.952(3) _cell_angle_alpha 90.00 _cell_angle_beta 92.622(2) _cell_angle_gamma 90.00 _cell_volume 1138.0(2) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 1088 _cell_measurement_theta_min 2.667 _cell_measurement_theta_max 20.682 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.239 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 456 _exptl_absorpt_coefficient_mu 0.094 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9651 _exptl_absorpt_correction_T_max 0.9957 _exptl_absorpt_process_details 'Bruker SADABS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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_device ' Bruker Smart APEX' _diffrn_measurement_method 'Omega Scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5472 _diffrn_reflns_av_R_equivalents 0.0347 _diffrn_reflns_av_sigmaI/netI 0.0401 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max 25.00 _reflns_number_total 1990 _reflns_number_gt 1385 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'BRUKER SMART' _computing_cell_refinement 'BRUKER SAINT' _computing_data_reduction 'BRUKER SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0650P)^2^+0.4111P] 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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1990 _refine_ls_number_parameters 138 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0906 _refine_ls_R_factor_gt 0.0617 _refine_ls_wR_factor_ref 0.1649 _refine_ls_wR_factor_gt 0.1502 _refine_ls_goodness_of_fit_ref 1.092 _refine_ls_restrained_S_all 1.092 _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 O1' O -0.0824(3) 0.4550(2) 0.92462(9) 0.0591(6) Uani 1 1 d . . . O1 O -0.0367(4) 0.7269(3) 0.93339(10) 0.0715(7) Uani 1 1 d . . . O2 O 0.4600(4) 0.9702(2) 0.92272(9) 0.0709(7) Uani 1 1 d . . . H2 H 0.4810 1.0379 0.9489 0.106 Uiso 1 1 calc R . . O3 O 0.4629(4) 0.7966(2) 0.99757(9) 0.0655(6) Uani 1 1 d . . . C1 C 0.4453(5) 0.8235(4) 0.94508(14) 0.0522(7) Uani 1 1 d . . . C2 C 0.4135(5) 0.6883(3) 0.90133(13) 0.0548(8) Uani 1 1 d . . . H2A H 0.5550 0.6464 0.8911 0.066 Uiso 1 1 calc R . . H2B H 0.3414 0.7327 0.8662 0.066 Uiso 1 1 calc R . . C2' C 0.0418(5) 0.5919(4) 0.92838(12) 0.0510(7) Uani 1 1 d . . . C3' C 0.2777(5) 0.5470(3) 0.92406(12) 0.0467(7) Uani 1 1 d . . . H3' H 0.3358 0.5193 0.9633 0.056 Uiso 1 1 calc R . . C4' C 0.2598(4) 0.3869(3) 0.88890(12) 0.0465(7) Uani 1 1 d . . . H4' H 0.3892 0.3178 0.8966 0.056 Uiso 1 1 calc R . . C5 C 0.0613(5) 0.3116(3) 0.91637(13) 0.0531(8) Uani 1 1 d . . . H5 H 0.1061 0.2662 0.9546 0.064 Uiso 1 1 calc R . . C6 C 0.2216(5) 0.4149(4) 0.82407(13) 0.0573(8) Uani 1 1 d . . . H6A H 0.3600 0.4403 0.8072 0.069 Uiso 1 1 calc R . . H6B H 0.1266 0.5097 0.8180 0.069 Uiso 1 1 calc R . . C7 C 0.1198(6) 0.2669(4) 0.79242(15) 0.0729(10) Uani 1 1 d . . . H7A H 0.0972 0.2927 0.7513 0.087 Uiso 1 1 calc R . . H7B H 0.2188 0.1737 0.7959 0.087 Uiso 1 1 calc R . . C8 C -0.0953(6) 0.2211(4) 0.81718(15) 0.0711(10) Uani 1 1 d . . . H8 H -0.1914 0.3176 0.8137 0.085 Uiso 1 1 calc R . . C9 C -0.0620(5) 0.1806(4) 0.88146(15) 0.0671(9) Uani 1 1 d . . . H9A H -0.2037 0.1649 0.8978 0.081 Uiso 1 1 calc R . . H9B H 0.0171 0.0771 0.8854 0.081 Uiso 1 1 calc R . . C10 C -0.2070(7) 0.0791(6) 0.7840(2) 0.1156(17) Uani 1 1 d . . . H10A H -0.1168 -0.0177 0.7873 0.173 Uiso 1 1 calc R . . H10B H -0.2287 0.1086 0.7436 0.173 Uiso 1 1 calc R . . H10C H -0.3457 0.0569 0.8002 0.173 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 O1' 0.0496(12) 0.0541(12) 0.0744(14) -0.0096(10) 0.0126(10) -0.0101(10) O1 0.0641(15) 0.0552(13) 0.0955(18) -0.0123(12) 0.0073(13) 0.0075(11) O2 0.0957(18) 0.0516(13) 0.0641(14) 0.0129(11) -0.0113(13) -0.0165(13) O3 0.0854(16) 0.0521(12) 0.0576(14) 0.0071(11) -0.0108(11) -0.0119(11) C1 0.0466(17) 0.0516(18) 0.058(2) 0.0113(15) -0.0068(14) -0.0072(13) C2 0.0503(18) 0.0572(18) 0.0565(18) 0.0043(15) -0.0007(14) -0.0098(15) C2' 0.0500(18) 0.0547(18) 0.0483(18) -0.0041(14) 0.0030(13) -0.0029(15) C3' 0.0508(17) 0.0473(15) 0.0411(15) 0.0039(13) -0.0061(12) -0.0024(13) C4' 0.0431(16) 0.0434(15) 0.0525(17) 0.0036(13) -0.0031(13) 0.0032(13) C5 0.0611(19) 0.0452(16) 0.0532(18) 0.0037(14) 0.0040(14) -0.0056(14) C6 0.062(2) 0.0575(18) 0.0529(19) -0.0022(15) 0.0093(15) -0.0039(15) C7 0.087(3) 0.073(2) 0.058(2) -0.0144(18) 0.0047(18) -0.0023(19) C8 0.065(2) 0.071(2) 0.076(2) -0.0214(19) -0.0080(18) -0.0052(17) C9 0.064(2) 0.0533(18) 0.084(2) -0.0073(17) 0.0067(18) -0.0151(16) C10 0.103(3) 0.119(4) 0.123(4) -0.056(3) -0.011(3) -0.031(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 O1' C2' 1.345(3) . ? O1' C5 1.475(3) . ? O1 C2' 1.202(3) . ? O2 C1 1.299(3) . ? O2 H2 0.8200 . ? O3 C1 1.224(3) . ? C1 C2 1.493(4) . ? C2 C3' 1.522(4) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C2' C3' 1.499(4) . ? C3' C4' 1.529(4) . ? C3' H3' 0.9800 . ? C4' C6 1.513(4) . ? C4' C5 1.523(4) . ? C4' H4' 0.9800 . ? C5 C9 1.511(4) . ? C5 H5 0.9800 . ? C6 C7 1.521(4) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C8 1.505(5) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 C9 1.516(5) . ? C8 C10 1.525(5) . ? C8 H8 0.9800 . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? 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' O1' C5 108.6(2) . . ? C1 O2 H2 109.5 . . ? O3 C1 O2 123.2(3) . . ? O3 C1 C2 122.3(3) . . ? O2 C1 C2 114.5(3) . . ? C1 C2 C3' 112.2(2) . . ? C1 C2 H2A 109.2 . . ? C3' C2 H2A 109.2 . . ? C1 C2 H2B 109.2 . . ? C3' C2 H2B 109.2 . . ? H2A C2 H2B 107.9 . . ? O1 C2' O1' 121.9(3) . . ? O1 C2' C3' 128.2(3) . . ? O1' C2' C3' 109.9(2) . . ? C2' C3' C2 112.6(2) . . ? C2' C3' C4' 101.3(2) . . ? C2 C3' C4' 119.0(2) . . ? C2' C3' H3' 107.8 . . ? C2 C3' H3' 107.8 . . ? C4' C3' H3' 107.8 . . ? C6 C4' C5 112.1(2) . . ? C6 C4' C3' 113.3(2) . . ? C5 C4' C3' 99.2(2) . . ? C6 C4' H4' 110.6 . . ? C5 C4' H4' 110.6 . . ? C3' C4' H4' 110.6 . . ? O1' C5 C9 109.5(2) . . ? O1' C5 C4' 103.3(2) . . ? C9 C5 C4' 116.8(2) . . ? O1' C5 H5 109.0 . . ? C9 C5 H5 109.0 . . ? C4' C5 H5 109.0 . . ? C4' C6 C7 113.2(3) . . ? C4' C6 H6A 108.9 . . ? C7 C6 H6A 108.9 . . ? C4' C6 H6B 108.9 . . ? C7 C6 H6B 108.9 . . ? H6A C6 H6B 107.8 . . ? C8 C7 C6 111.2(3) . . ? C8 C7 H7A 109.4 . . ? C6 C7 H7A 109.4 . . ? C8 C7 H7B 109.4 . . ? C6 C7 H7B 109.4 . . ? H7A C7 H7B 108.0 . . ? C7 C8 C9 109.9(3) . . ? C7 C8 C10 112.2(3) . . ? C9 C8 C10 111.1(3) . . ? C7 C8 H8 107.8 . . ? C9 C8 H8 107.8 . . ? C10 C8 H8 107.8 . . ? C5 C9 C8 113.9(3) . . ? C5 C9 H9A 108.8 . . ? C8 C9 H9A 108.8 . . ? C5 C9 H9B 108.8 . . ? C8 C9 H9B 108.8 . . ? H9A C9 H9B 107.7 . . ? C8 C10 H10A 109.5 . . ? C8 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C8 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? 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 O3 C1 C2 C3' 34.0(4) . . . . ? O2 C1 C2 C3' -148.2(3) . . . . ? C5 O1' C2' O1 177.6(3) . . . . ? C5 O1' C2' C3' -1.2(3) . . . . ? O1 C2' C3' C2 -24.1(4) . . . . ? O1' C2' C3' C2 154.6(2) . . . . ? O1 C2' C3' C4' -152.3(3) . . . . ? O1' C2' C3' C4' 26.4(3) . . . . ? C1 C2 C3' C2' 71.5(3) . . . . ? C1 C2 C3' C4' -170.3(2) . . . . ? C2' C3' C4' C6 80.1(3) . . . . ? C2 C3' C4' C6 -43.8(4) . . . . ? C2' C3' C4' C5 -39.0(3) . . . . ? C2 C3' C4' C5 -162.9(2) . . . . ? C2' O1' C5 C9 -150.0(2) . . . . ? C2' O1' C5 C4' -24.9(3) . . . . ? C6 C4' C5 O1' -80.7(3) . . . . ? C3' C4' C5 O1' 39.2(3) . . . . ? C6 C4' C5 C9 39.6(3) . . . . ? C3' C4' C5 C9 159.5(3) . . . . ? C5 C4' C6 C7 -46.7(3) . . . . ? C3' C4' C6 C7 -158.0(3) . . . . ? C4' C6 C7 C8 58.2(4) . . . . ? C6 C7 C8 C9 -59.1(4) . . . . ? C6 C7 C8 C10 176.8(3) . . . . ? O1' C5 C9 C8 74.1(3) . . . . ? C4' C5 C9 C8 -42.8(4) . . . . ? C7 C8 C9 C5 51.5(4) . . . . ? C10 C8 C9 C5 176.2(3) . . . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.151 _refine_diff_density_min -0.171 _refine_diff_density_rms 0.040 data_C7H8O4compound8 _database_code_depnum_ccdc_archive 'CCDC 819769' #TrackingRef '4896_web_deposit_cif_file_0_NarshinhaPArgade_1301638585.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common Butenolides _chemical_melting_point '130-132 degree Centigrade' _chemical_formula_moiety 'C7 H8 O4' _chemical_formula_sum 'C7 H8 O4' _chemical_formula_weight 156.13 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 P21/c 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 5.0397(3) _cell_length_b 14.3513(10) _cell_length_c 10.3160(7) _cell_angle_alpha 90.00 _cell_angle_beta 98.1180(10) _cell_angle_gamma 90.00 _cell_volume 738.64(8) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 3185 _cell_measurement_theta_min 2.447 _cell_measurement_theta_max 28.136 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.08 _exptl_crystal_size_mid 0.02 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.404 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 328 _exptl_absorpt_coefficient_mu 0.117 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9910 _exptl_absorpt_correction_T_max 0.9983 _exptl_absorpt_process_details 'Bruker SADABS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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_device ' Bruker Smart APEX' _diffrn_measurement_method 'Omega Scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6969 _diffrn_reflns_av_R_equivalents 0.0217 _diffrn_reflns_av_sigmaI/netI 0.0137 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.45 _diffrn_reflns_theta_max 25.00 _reflns_number_total 1291 _reflns_number_gt 1233 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'BRUKER SMART' _computing_cell_refinement 'BRUKER SAINT' _computing_data_reduction 'BRUKER SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0726P)^2^+0.6566P] 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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1291 _refine_ls_number_parameters 102 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0678 _refine_ls_R_factor_gt 0.0658 _refine_ls_wR_factor_ref 0.1702 _refine_ls_wR_factor_gt 0.1684 _refine_ls_goodness_of_fit_ref 1.110 _refine_ls_restrained_S_all 1.110 _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 O1' O 0.6114(4) 0.06645(15) 0.2135(2) 0.0620(6) Uani 1 1 d . . . O1 O 0.7059(4) 0.21705(14) 0.2490(2) 0.0569(6) Uani 1 1 d . . . O2 O 0.0616(4) 0.29193(13) 0.5790(2) 0.0572(6) Uani 1 1 d . . . H2 H -0.0461 0.2849 0.6309 0.086 Uiso 1 1 calc R . . O3 O 0.0134(5) 0.13940(14) 0.5551(2) 0.0691(7) Uani 1 1 d . . . C1 C 0.1165(5) 0.21024(18) 0.5301(2) 0.0398(6) Uani 1 1 d . . . C2 C 0.3230(6) 0.2213(2) 0.4399(3) 0.0514(8) Uani 1 1 d . . . H2A H 0.2637 0.2705 0.3780 0.062 Uiso 1 1 calc R . . H2B H 0.4881 0.2423 0.4915 0.062 Uiso 1 1 calc R . . C2' C 0.5809(5) 0.14779(19) 0.2719(2) 0.0432(6) Uani 1 1 d . . . C3' C 0.3858(5) 0.13763(17) 0.3640(2) 0.0386(6) Uani 1 1 d . . . C4' C 0.3033(6) 0.05069(19) 0.3579(3) 0.0488(7) Uani 1 1 d . . . H4' H 0.1777 0.0262 0.4065 0.059 Uiso 1 1 calc R . . C5' C 0.4381(7) -0.0033(2) 0.2627(3) 0.0593(8) Uani 1 1 d . . . H5' H 0.5476 -0.0529 0.3084 0.071 Uiso 1 1 calc R . . C6 C 0.2537(9) -0.0432(3) 0.1511(4) 0.0815(11) Uani 1 1 d . . . H6A H 0.1411 0.0052 0.1093 0.122 Uiso 1 1 calc R . . H6B H 0.1444 -0.0905 0.1829 0.122 Uiso 1 1 calc R . . H6C H 0.3567 -0.0701 0.0891 0.122 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 O1' 0.0623(13) 0.0663(13) 0.0643(13) -0.0148(11) 0.0326(11) -0.0009(10) O1 0.0549(12) 0.0661(14) 0.0566(12) -0.0038(10) 0.0316(10) -0.0138(10) O2 0.0617(13) 0.0566(13) 0.0611(13) -0.0116(10) 0.0352(10) -0.0060(9) O3 0.0817(16) 0.0519(13) 0.0866(17) 0.0061(11) 0.0571(13) -0.0031(11) C1 0.0354(13) 0.0488(15) 0.0368(13) 0.0015(11) 0.0110(10) -0.0009(11) C2 0.0517(16) 0.0547(17) 0.0540(16) -0.0139(13) 0.0289(13) -0.0161(13) C2' 0.0390(14) 0.0538(16) 0.0391(13) -0.0034(11) 0.0130(11) -0.0005(11) C3' 0.0349(12) 0.0481(15) 0.0344(12) 0.0007(10) 0.0108(10) -0.0023(10) C4' 0.0524(16) 0.0486(16) 0.0484(15) 0.0003(12) 0.0175(12) -0.0044(12) C5' 0.070(2) 0.0507(17) 0.0598(18) 0.0002(14) 0.0174(15) 0.0057(14) C6 0.108(3) 0.066(2) 0.072(2) -0.0180(18) 0.021(2) -0.011(2) _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 O1' C2' 1.333(3) . ? O1' C5' 1.466(4) . ? O1 C2' 1.217(3) . ? O2 C1 1.321(3) . ? O2 H2 0.8200 . ? O3 C1 1.187(3) . ? C1 C2 1.499(3) . ? C2 C3' 1.492(4) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C2' C3' 1.468(3) . ? C3' C4' 1.314(4) . ? C4' C5' 1.488(4) . ? C4' H4' 0.9300 . ? C5' C6 1.488(5) . ? C5' H5' 0.9800 . ? C6 H6A 0.9600 . ? C6 H6B 0.9600 . ? C6 H6C 0.9600 . ? 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' O1' C5' 109.2(2) . . ? C1 O2 H2 109.5 . . ? O3 C1 O2 123.7(2) . . ? O3 C1 C2 126.1(2) . . ? O2 C1 C2 110.1(2) . . ? C3' C2 C1 117.2(2) . . ? C3' C2 H2A 108.0 . . ? C1 C2 H2A 108.0 . . ? C3' C2 H2B 108.0 . . ? C1 C2 H2B 108.0 . . ? H2A C2 H2B 107.2 . . ? O1 C2' O1' 122.1(2) . . ? O1 C2' C3' 128.2(2) . . ? O1' C2' C3' 109.7(2) . . ? C4' C3' C2' 107.5(2) . . ? C4' C3' C2 134.5(2) . . ? C2' C3' C2 118.1(2) . . ? C3' C4' C5' 110.8(2) . . ? C3' C4' H4' 124.6 . . ? C5' C4' H4' 124.6 . . ? O1' C5' C4' 102.9(2) . . ? O1' C5' C6 109.4(3) . . ? C4' C5' C6 114.7(3) . . ? O1' C5' H5' 109.9 . . ? C4' C5' H5' 109.9 . . ? C6 C5' H5' 109.9 . . ? C5' C6 H6A 109.5 . . ? C5' C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C5' C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? 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 O3 C1 C2 C3' 6.5(5) . . . . ? O2 C1 C2 C3' -173.1(2) . . . . ? C5' O1' C2' O1 179.1(3) . . . . ? C5' O1' C2' C3' 0.1(3) . . . . ? O1 C2' C3' C4' -179.3(3) . . . . ? O1' C2' C3' C4' -0.3(3) . . . . ? O1 C2' C3' C2 1.0(4) . . . . ? O1' C2' C3' C2 180.0(2) . . . . ? C1 C2 C3' C4' -1.6(5) . . . . ? C1 C2 C3' C2' 178.0(2) . . . . ? C2' C3' C4' C5' 0.4(3) . . . . ? C2 C3' C4' C5' -180.0(3) . . . . ? C2' O1' C5' C4' 0.2(3) . . . . ? C2' O1' C5' C6 122.5(3) . . . . ? C3' C4' C5' O1' -0.4(3) . . . . ? C3' C4' C5' C6 -119.1(3) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.503 _refine_diff_density_min -0.163 _refine_diff_density_rms 0.051 # Attachment 'web_deposit_cif_file_1_NarshinhaPArgade_1301638585.cif' ##Title:Regio- and Stereoselective Selenium Dioxide Allylic ##Oxidation of (E)-Dialkyl Alkylidenesuccinates: Direct Proof ##for the Proposed Ene Reaction Followed by [2,3] Sigma Tropic ##Shift Mechanism: Synthesis of Natural and Unnatural Butenolides ##Communicated to J.AM.Chem.Soc. ##By Ramesh M. Patel,Vedavati G. Puranik and Narshinha P. Argade. ##Division of Organic Chemistry and Center for Materials Charecterization, ##National Chemical Laboratory Pune-411 008, India data_C11H16O4compound25 _database_code_depnum_ccdc_archive 'CCDC 819770' #TrackingRef 'web_deposit_cif_file_1_NarshinhaPArgade_1301638585.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common chromene _chemical_melting_point '143-145degree Centigrade' _chemical_formula_moiety 'C11 H16 O4' _chemical_formula_sum 'C11 H16 O4' _chemical_formula_weight 212.24 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 P21/c 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 10.4595(10) _cell_length_b 8.2649(8) _cell_length_c 13.4821(13) _cell_angle_alpha 90.00 _cell_angle_beta 110.602(2) _cell_angle_gamma 90.00 _cell_volume 1090.95(18) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 1800 _cell_measurement_theta_min 2.946 _cell_measurement_theta_max 25.999 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.292 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 456 _exptl_absorpt_coefficient_mu 0.098 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9687 _exptl_absorpt_correction_T_max 0.9918 _exptl_absorpt_process_details 'Bruker SADABS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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_device ' Bruker Smart APEX' _diffrn_measurement_method 'Omega Scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5199 _diffrn_reflns_av_R_equivalents 0.0211 _diffrn_reflns_av_sigmaI/netI 0.0245 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 12 _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 2.08 _diffrn_reflns_theta_max 24.99 _reflns_number_total 1916 _reflns_number_gt 1569 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'BRUKER SMART' _computing_cell_refinement 'BRUKER SAINT' _computing_data_reduction 'BRUKER SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0507P)^2^+0.2075P] 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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1916 _refine_ls_number_parameters 138 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0495 _refine_ls_R_factor_gt 0.0395 _refine_ls_wR_factor_ref 0.1071 _refine_ls_wR_factor_gt 0.0998 _refine_ls_goodness_of_fit_ref 1.047 _refine_ls_restrained_S_all 1.047 _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 O1' O 0.80984(11) 0.03506(12) 0.99718(9) 0.0437(3) Uani 1 1 d . . . O1 O 0.96184(12) -0.07877(13) 1.13492(9) 0.0523(3) Uani 1 1 d . . . O2 O 0.85148(12) 0.61793(14) 1.10905(11) 0.0591(4) Uani 1 1 d . . . H2 H 0.8882 0.7068 1.1145 0.089 Uiso 1 1 calc R . . O3 O 1.05931(12) 0.52994(14) 1.12889(11) 0.0603(4) Uani 1 1 d . . . C1 C 0.94268(16) 0.50287(18) 1.11638(12) 0.0407(4) Uani 1 1 d . . . C2' C 0.91990(16) 0.04374(18) 1.08452(13) 0.0409(4) Uani 1 1 d . . . C3' C 0.98562(16) 0.20611(19) 1.11379(13) 0.0454(4) Uani 1 1 d . . . H3'1 H 1.0333 0.2337 1.0660 0.054 Uiso 1 1 calc R . . H3'2 H 1.0523 0.2017 1.1851 0.054 Uiso 1 1 calc R . . C4' C 0.87996(15) 0.33684(18) 1.10806(12) 0.0388(4) Uani 1 1 d . . . H4' H 0.8527 0.3227 1.1700 0.047 Uiso 1 1 calc R . . C5' C 0.74927(15) 0.31761(18) 1.00824(12) 0.0393(4) Uani 1 1 d . . . H5' H 0.7339 0.4200 0.9691 0.047 Uiso 1 1 calc R . . C6' C 0.76879(16) 0.18664(18) 0.93626(12) 0.0420(4) Uani 1 1 d . . . H6' H 0.8415 0.2197 0.9104 0.050 Uiso 1 1 calc R . . C7 C 0.62388(17) 0.2832(2) 1.03692(15) 0.0548(5) Uani 1 1 d . . . H7A H 0.6394 0.1863 1.0801 0.066 Uiso 1 1 calc R . . H7B H 0.6094 0.3724 1.0785 0.066 Uiso 1 1 calc R . . C8 C 0.49723(18) 0.2606(3) 0.93931(18) 0.0676(6) Uani 1 1 d . . . H8A H 0.4203 0.2365 0.9612 0.081 Uiso 1 1 calc R . . H8B H 0.4775 0.3608 0.8994 0.081 Uiso 1 1 calc R . . C9 C 0.51276(18) 0.1259(2) 0.86826(15) 0.0621(5) Uani 1 1 d . . . H9 H 0.5219 0.0237 0.9071 0.074 Uiso 1 1 calc R . . C10 C 0.64159(19) 0.1502(2) 0.84265(14) 0.0566(5) Uani 1 1 d . . . H10A H 0.6576 0.0533 0.8082 0.068 Uiso 1 1 calc R . . H10B H 0.6262 0.2385 0.7923 0.068 Uiso 1 1 calc R . . C11 C 0.3867(2) 0.1134(3) 0.7676(2) 0.1027(10) Uani 1 1 d . . . H11A H 0.3085 0.0870 0.7860 0.154 Uiso 1 1 calc R . . H11B H 0.4007 0.0304 0.7227 0.154 Uiso 1 1 calc R . . H11C H 0.3717 0.2151 0.7308 0.154 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 O1' 0.0513(7) 0.0238(6) 0.0543(7) -0.0011(5) 0.0165(6) -0.0018(4) O1 0.0621(7) 0.0256(6) 0.0644(7) 0.0036(5) 0.0161(6) 0.0038(5) O2 0.0516(7) 0.0253(6) 0.0966(10) -0.0094(6) 0.0213(7) -0.0022(5) O3 0.0483(7) 0.0355(7) 0.0973(10) 0.0016(6) 0.0258(7) -0.0074(5) C1 0.0455(9) 0.0273(8) 0.0464(9) -0.0022(7) 0.0125(7) -0.0028(7) C2' 0.0443(9) 0.0285(9) 0.0517(9) -0.0019(7) 0.0191(8) 0.0007(7) C3' 0.0445(9) 0.0280(9) 0.0573(10) 0.0011(7) 0.0101(8) -0.0007(7) C4' 0.0440(9) 0.0265(8) 0.0464(8) -0.0018(7) 0.0163(7) -0.0039(6) C5' 0.0412(9) 0.0239(8) 0.0498(9) -0.0006(7) 0.0122(7) -0.0023(6) C6' 0.0513(9) 0.0286(8) 0.0475(9) 0.0024(7) 0.0190(8) -0.0019(7) C7 0.0455(10) 0.0503(11) 0.0713(12) -0.0115(9) 0.0239(9) -0.0014(8) C8 0.0399(10) 0.0629(13) 0.0931(15) -0.0108(11) 0.0146(10) -0.0018(9) C9 0.0509(11) 0.0399(10) 0.0772(13) -0.0010(9) 0.0000(9) -0.0087(8) C10 0.0755(13) 0.0350(10) 0.0500(10) -0.0040(8) 0.0107(9) -0.0004(8) C11 0.0794(16) 0.0699(17) 0.1130(19) -0.0187(15) -0.0230(15) -0.0059(13) _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 O1' C2' 1.3278(19) . ? O1' C6' 1.4766(18) . ? O1 C2' 1.2123(19) . ? O2 C1 1.3257(19) . ? O2 H2 0.8200 . ? O3 C1 1.1924(18) . ? C1 C4' 1.508(2) . ? C2' C3' 1.496(2) . ? C3' C4' 1.528(2) . ? C3' H3'1 0.9700 . ? C3' H3'2 0.9700 . ? C4' C5' 1.553(2) . ? C4' H4' 0.9800 . ? C5' C6' 1.515(2) . ? C5' C7 1.519(2) . ? C5' H5' 0.9800 . ? C6' C10 1.507(2) . ? C6' H6' 0.9800 . ? C7 C8 1.515(3) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 C9 1.514(3) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C9 C10 1.518(3) . ? C9 C11 1.527(3) . ? C9 H9 0.9800 . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? 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' O1' C6' 116.05(12) . . ? C1 O2 H2 109.5 . . ? O3 C1 O2 123.33(14) . . ? O3 C1 C4' 125.30(14) . . ? O2 C1 C4' 111.37(13) . . ? O1 C2' O1' 118.80(14) . . ? O1 C2' C3' 124.01(15) . . ? O1' C2' C3' 117.19(13) . . ? C2' C3' C4' 111.34(13) . . ? C2' C3' H3'1 109.4 . . ? C4' C3' H3'1 109.4 . . ? C2' C3' H3'2 109.4 . . ? C4' C3' H3'2 109.4 . . ? H3'1 C3' H3'2 108.0 . . ? C1 C4' C3' 110.59(13) . . ? C1 C4' C5' 112.64(12) . . ? C3' C4' C5' 111.84(12) . . ? C1 C4' H4' 107.2 . . ? C3' C4' H4' 107.2 . . ? C5' C4' H4' 107.2 . . ? C6' C5' C7 110.65(13) . . ? C6' C5' C4' 110.64(12) . . ? C7 C5' C4' 111.97(13) . . ? C6' C5' H5' 107.8 . . ? C7 C5' H5' 107.8 . . ? C4' C5' H5' 107.8 . . ? O1' C6' C10 107.13(12) . . ? O1' C6' C5' 109.17(12) . . ? C10 C6' C5' 113.63(14) . . ? O1' C6' H6' 108.9 . . ? C10 C6' H6' 108.9 . . ? C5' C6' H6' 108.9 . . ? C8 C7 C5' 111.80(15) . . ? C8 C7 H7A 109.3 . . ? C5' C7 H7A 109.3 . . ? C8 C7 H7B 109.3 . . ? C5' C7 H7B 109.3 . . ? H7A C7 H7B 107.9 . . ? C9 C8 C7 112.63(15) . . ? C9 C8 H8A 109.1 . . ? C7 C8 H8A 109.1 . . ? C9 C8 H8B 109.1 . . ? C7 C8 H8B 109.1 . . ? H8A C8 H8B 107.8 . . ? C8 C9 C10 110.36(15) . . ? C8 C9 C11 111.13(17) . . ? C10 C9 C11 111.40(19) . . ? C8 C9 H9 107.9 . . ? C10 C9 H9 107.9 . . ? C11 C9 H9 107.9 . . ? C6' C10 C9 115.39(14) . . ? C6' C10 H10A 108.4 . . ? C9 C10 H10A 108.4 . . ? C6' C10 H10B 108.4 . . ? C9 C10 H10B 108.4 . . ? H10A C10 H10B 107.5 . . ? C9 C11 H11A 109.5 . . ? C9 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C9 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? 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' O1' C2' O1 -176.63(14) . . . . ? C6' O1' C2' C3' 2.68(19) . . . . ? O1 C2' C3' C4' -133.15(16) . . . . ? O1' C2' C3' C4' 47.58(19) . . . . ? O3 C1 C4' C3' -2.1(2) . . . . ? O2 C1 C4' C3' 178.53(14) . . . . ? O3 C1 C4' C5' -128.04(18) . . . . ? O2 C1 C4' C5' 52.57(17) . . . . ? C2' C3' C4' C1 -168.80(13) . . . . ? C2' C3' C4' C5' -42.40(18) . . . . ? C1 C4' C5' C6' 118.27(14) . . . . ? C3' C4' C5' C6' -7.01(17) . . . . ? C1 C4' C5' C7 -117.80(15) . . . . ? C3' C4' C5' C7 116.92(15) . . . . ? C2' O1' C6' C10 -178.95(13) . . . . ? C2' O1' C6' C5' -55.50(17) . . . . ? C7 C5' C6' O1' -69.61(16) . . . . ? C4' C5' C6' O1' 55.07(16) . . . . ? C7 C5' C6' C10 49.89(18) . . . . ? C4' C5' C6' C10 174.58(13) . . . . ? C6' C5' C7 C8 -54.70(19) . . . . ? C4' C5' C7 C8 -178.62(14) . . . . ? C5' C7 C8 C9 57.5(2) . . . . ? C7 C8 C9 C10 -52.4(2) . . . . ? C7 C8 C9 C11 -176.52(19) . . . . ? O1' C6' C10 C9 72.63(17) . . . . ? C5' C6' C10 C9 -48.0(2) . . . . ? C8 C9 C10 C6' 48.1(2) . . . . ? C11 C9 C10 C6' 172.00(16) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.169 _refine_diff_density_min -0.119 _refine_diff_density_rms 0.032