# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2002 data_C14 H19 Cl1 O4 _database_code_CSD 188197 _journal_coden_Cambridge 182 loop_ _publ_author_name 'Singh, Vishwakarma' 'Mobin, Shaikh M.' 'Pal, Shantanu' _publ_contact_author_name 'Prof Vishwakarma Singh' _publ_contact_author_address ; Department of Chemistry Indian Institute of Technology Bombay Mumbai 400 076 INDIA ; _publ_contact_author_email 'VKS@ETHER.CHEM.IITB.AC.IN' _publ_requested_journal 'Chemical Communications' _publ_section_title ; Cycloaddition of cyclohexa-2,4-dienones with electron deficient 2 partners: a novel and stereoselective route to functionalised bicyclo [2.2.2] octenones ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ;1,7-dimethyl-5-hydroxy-5-chloromethyl- 2-carboethoxy bicyclo[2.2.2]oct-7-ene-6-one ; _chemical_formula_moiety ;1,7-dimethyl-5-hydroxy-5-chloromethyl- 2-carboethoxy bicyclo[2.2.2]oct-7-ene-6-one ; _chemical_formula_sum 'C14 H19 Cl O4' _chemical_formula_weight 286.74 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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'Orthorhombic' _symmetry_space_group_name_H-M 'P b c a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' _cell_length_a 10.3270(12) _cell_length_b 14.2240(14) _cell_length_c 20.1930(15) _cell_angle_alpha 90.000 _cell_angle_beta 90.000 _cell_angle_gamma 90.000 _cell_volume 2966.2(5) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 5.7100 _cell_measurement_theta_max 11.8400 _exptl_crystal_description Block _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.40 mm _exptl_crystal_size_mid 0.40 mm _exptl_crystal_size_min 0.35 mm _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.284 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1216 _exptl_absorpt_coefficient_mu 0.265 _exptl_absorpt_correction_type 'psi-scan' _exptl_absorpt_correction_T_min 0.982 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details ; psi-scan (North, Philips & Mathews, 1968) ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.70930 _diffrn_radiation_type ' MoK\a' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type Enraf-Nonius CAD-4 _diffrn_measurement_method \w/q-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 3600 _diffrn_standards_decay_% <3% _diffrn_reflns_number 2046 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0189 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.01 _diffrn_reflns_theta_max 24.91 _reflns_number_total 2046 _reflns_number_gt 1646 _reflns_threshold_expression >2sigma(I) _computing_data_collection Argus (Nonius, MACH3 software) _computing_cell_refinement Argus (Nonius, MACH3 software) _computing_data_reduction Maxus (Nonius software) _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics Ortep _computing_publication_material Shelx97 _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 w=1/[\s^2^(Fo^2^)+(0.0587P)^2^+1.3839P] 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_number_reflns 2046 _refine_ls_number_parameters 228 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0619 _refine_ls_R_factor_gt 0.0474 _refine_ls_wR_factor_ref 0.1279 _refine_ls_wR_factor_gt 0.1195 _refine_ls_goodness_of_fit_ref 1.101 _refine_ls_restrained_S_all 1.101 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cl1 Cl 0.03078(9) 0.21612(7) 0.50435(5) 0.0941(4) Uani 1 d . . . O3 O 0.3592(2) 0.22027(13) 0.35319(11) 0.0703(7) Uani 1 d . . . O4 O 0.08004(19) 0.16797(14) 0.35460(11) 0.0613(6) Uani 1 d . . . O1 O 0.2777(3) -0.10804(19) 0.22647(14) 0.1109(11) Uani 1 d . . . O2 O 0.3830(3) -0.14703(14) 0.31643(12) 0.0803(7) Uani 1 d . . . C1 C 0.2203(5) -0.2290(4) 0.1570(3) 0.159(3) Uani 1 d . . . H1A H 0.2461 -0.2867 0.1362 0.238 Uiso 1 calc R . . H1B H 0.1987 -0.1836 0.1237 0.238 Uiso 1 calc R . . H1C H 0.1461 -0.2402 0.1846 0.238 Uiso 1 calc R . . C2 C 0.3175(6) -0.1963(4) 0.1941(3) 0.147(2) Uani 1 d . . . H2A H 0.3928 -0.1851 0.1665 0.177 Uiso 1 calc R . . H2B H 0.3406 -0.2425 0.2274 0.177 Uiso 1 calc R . . C3 C 0.3148(3) -0.0935(2) 0.28645(16) 0.0588(8) Uani 1 d . . . C4 C 0.2631(3) -0.00251(19) 0.31368(14) 0.0482(7) Uani 1 d . . . C5 C 0.1417(3) -0.0199(2) 0.35667(16) 0.0523(7) Uani 1 d . . . C6 C 0.1515(3) 0.03881(18) 0.42035(14) 0.0482(7) Uani 1 d . . . C7 C 0.1755(3) 0.14194(18) 0.40179(13) 0.0484(7) Uani 1 d . . . C8 C 0.3097(3) 0.14636(18) 0.36795(13) 0.0490(7) Uani 1 d . . . C9 C 0.3686(3) 0.05001(18) 0.35499(13) 0.0475(6) Uani 1 d . . . C10 C 0.4984(3) 0.0591(3) 0.31945(19) 0.0623(8) Uani 1 d . . . C11 C 0.3763(3) 0.0067(2) 0.42319(14) 0.0523(7) Uani 1 d . . . C12 C 0.2675(3) 0.00251(19) 0.45807(14) 0.0500(7) Uani 1 d . . . C13 C 0.2526(4) -0.0382(3) 0.52558(19) 0.0698(10) Uani 1 d . . . C14 C 0.1794(3) 0.2097(3) 0.45969(19) 0.0625(8) Uani 1 d . . . H5A H 0.136(2) -0.086(2) 0.3688(12) 0.046(7) Uiso 1 d . . . H4 H 0.240(2) 0.0371(16) 0.2765(12) 0.035(6) Uiso 1 d . . . H5 H 0.065(3) -0.0040(17) 0.3337(13) 0.045(7) Uiso 1 d . . . H10B H 0.537(3) -0.002(2) 0.3163(16) 0.072(10) Uiso 1 d . . . H14 H 0.241(3) 0.190(2) 0.4897(15) 0.057(9) Uiso 1 d . . . H6 H 0.072(3) 0.0356(18) 0.4477(13) 0.050(7) Uiso 1 d . . . H14A H 0.199(3) 0.273(2) 0.4452(15) 0.060(9) Uiso 1 d . . . H11 H 0.454(3) -0.0164(18) 0.4397(14) 0.056(8) Uiso 1 d . . . H13B H 0.184(3) -0.084(2) 0.5233(15) 0.068(9) Uiso 1 d . . . H10 H 0.483(3) 0.087(2) 0.2740(16) 0.069(9) Uiso 1 d . . . H13 H 0.330(4) -0.065(2) 0.5412(18) 0.087(12) Uiso 1 d . . . H13A H 0.222(4) 0.006(3) 0.555(2) 0.088(13) Uiso 1 d . . . H10A H 0.558(3) 0.099(2) 0.3433(16) 0.084(11) Uiso 1 d . . . H111 H 0.085(4) 0.228(3) 0.3468(17) 0.088(12) Uiso 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 Cl1 0.0735(6) 0.1000(8) 0.1087(8) -0.0324(6) 0.0322(6) -0.0059(5) O3 0.0748(14) 0.0468(12) 0.0894(17) -0.0009(11) 0.0188(12) -0.0185(10) O4 0.0609(12) 0.0427(11) 0.0803(15) 0.0064(11) -0.0130(11) -0.0013(10) O1 0.144(3) 0.0971(19) 0.0913(19) -0.0502(16) -0.0471(18) 0.0567(18) O2 0.1044(18) 0.0467(12) 0.0897(17) 0.0054(11) -0.0078(14) 0.0162(12) C1 0.112(4) 0.123(4) 0.240(8) -0.101(5) -0.035(4) 0.010(3) C2 0.174(5) 0.131(4) 0.136(4) -0.091(4) -0.054(4) 0.075(4) C3 0.0697(19) 0.0472(16) 0.060(2) -0.0046(15) -0.0069(15) 0.0011(15) C4 0.0587(17) 0.0382(14) 0.0477(15) 0.0017(13) -0.0081(14) 0.0010(13) C5 0.0497(17) 0.0385(15) 0.069(2) 0.0009(14) -0.0115(15) -0.0049(13) C6 0.0422(15) 0.0447(15) 0.0577(17) 0.0011(13) 0.0020(13) -0.0073(12) C7 0.0473(15) 0.0429(14) 0.0550(17) -0.0020(12) 0.0004(13) -0.0036(12) C8 0.0517(15) 0.0473(16) 0.0481(16) -0.0019(12) -0.0017(12) -0.0108(13) C9 0.0485(15) 0.0477(15) 0.0462(16) 0.0024(12) 0.0022(12) -0.0043(12) C10 0.0550(19) 0.068(2) 0.064(2) 0.0057(19) 0.0120(16) -0.0013(17) C11 0.0484(17) 0.0555(17) 0.0531(17) 0.0030(14) -0.0081(15) -0.0048(14) C12 0.0523(16) 0.0484(15) 0.0492(16) 0.0051(13) -0.0040(14) -0.0098(13) C13 0.071(2) 0.079(3) 0.060(2) 0.014(2) -0.0004(19) -0.017(2) C14 0.0578(19) 0.058(2) 0.072(2) -0.0121(17) 0.0095(17) -0.0108(16) _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 Cl1 C14 1.782(3) . ? O3 C8 1.207(3) . ? O4 C7 1.420(3) . ? O4 H111 0.87(4) . ? O1 C3 1.287(4) . ? O1 C2 1.475(5) . ? O2 C3 1.201(3) . ? C1 C2 1.336(6) . ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 C4 1.504(4) . ? C4 C5 1.544(4) . ? C4 C9 1.562(4) . ? C4 H4 0.97(2) . ? C5 C6 1.536(4) . ? C5 H5A 0.97(3) . ? C5 H5 0.94(3) . ? C6 C12 1.511(4) . ? C6 C7 1.534(4) . ? C6 H6 0.99(3) . ? C7 C14 1.515(4) . ? C7 C8 1.546(4) . ? C8 C9 1.522(4) . ? C9 C11 1.510(4) . ? C9 C10 1.526(4) . ? C10 H10B 0.96(3) . ? C10 H10 1.01(3) . ? C10 H10A 0.97(4) . ? C11 C12 1.327(4) . ? C11 H11 0.93(3) . ? C12 C13 1.489(5) . ? C13 H13B 0.96(3) . ? C13 H13 0.95(4) . ? C13 H13A 0.92(4) . ? C14 H14 0.93(3) . ? C14 H14A 0.96(3) . ? 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 C7 O4 H111 109(2) . . ? C3 O1 C2 118.1(3) . . ? C2 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? C1 C2 O1 109.6(4) . . ? C1 C2 H2A 109.8 . . ? O1 C2 H2A 109.8 . . ? C1 C2 H2B 109.8 . . ? O1 C2 H2B 109.8 . . ? H2A C2 H2B 108.2 . . ? O2 C3 O1 123.2(3) . . ? O2 C3 C4 124.7(3) . . ? O1 C3 C4 112.1(3) . . ? C3 C4 C5 110.9(2) . . ? C3 C4 C9 111.0(2) . . ? C5 C4 C9 110.0(2) . . ? C3 C4 H4 107.8(13) . . ? C5 C4 H4 109.0(14) . . ? C9 C4 H4 108.1(13) . . ? C6 C5 C4 109.3(2) . . ? C6 C5 H5A 108.6(15) . . ? C4 C5 H5A 110.0(15) . . ? C6 C5 H5 109.7(15) . . ? C4 C5 H5 111.3(15) . . ? H5A C5 H5 108(2) . . ? C12 C6 C7 108.8(2) . . ? C12 C6 C5 106.8(2) . . ? C7 C6 C5 109.0(2) . . ? C12 C6 H6 111.0(15) . . ? C7 C6 H6 108.3(15) . . ? C5 C6 H6 112.9(15) . . ? O4 C7 C14 111.7(3) . . ? O4 C7 C6 107.5(2) . . ? C14 C7 C6 115.1(3) . . ? O4 C7 C8 108.3(2) . . ? C14 C7 C8 106.9(2) . . ? C6 C7 C8 106.9(2) . . ? O3 C8 C9 124.9(2) . . ? O3 C8 C7 121.6(2) . . ? C9 C8 C7 113.4(2) . . ? C11 C9 C8 103.4(2) . . ? C11 C9 C10 114.6(3) . . ? C8 C9 C10 110.8(2) . . ? C11 C9 C4 109.2(2) . . ? C8 C9 C4 104.1(2) . . ? C10 C9 C4 113.7(3) . . ? C9 C10 H10B 108.7(19) . . ? C9 C10 H10 108.8(17) . . ? H10B C10 H10 111(3) . . ? C9 C10 H10A 112(2) . . ? H10B C10 H10A 108(3) . . ? H10 C10 H10A 108(3) . . ? C12 C11 C9 117.2(3) . . ? C12 C11 H11 121.8(17) . . ? C9 C11 H11 121.0(17) . . ? C11 C12 C13 126.2(3) . . ? C11 C12 C6 112.8(2) . . ? C13 C12 C6 120.8(3) . . ? C12 C13 H13B 107.1(18) . . ? C12 C13 H13 112(2) . . ? H13B C13 H13 112(3) . . ? C12 C13 H13A 111(2) . . ? H13B C13 H13A 104(3) . . ? H13 C13 H13A 111(3) . . ? C7 C14 Cl1 113.6(2) . . ? C7 C14 H14 109.2(19) . . ? Cl1 C14 H14 106.2(19) . . ? C7 C14 H14A 111.3(18) . . ? Cl1 C14 H14A 106.6(17) . . ? H14 C14 H14A 110(3) . . ? 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 C3 O1 C2 C1 141.4(5) . . . . ? C2 O1 C3 O2 2.1(6) . . . . ? C2 O1 C3 C4 -177.9(4) . . . . ? O2 C3 C4 C5 -81.6(4) . . . . ? O1 C3 C4 C5 98.5(3) . . . . ? O2 C3 C4 C9 41.0(4) . . . . ? O1 C3 C4 C9 -138.9(3) . . . . ? C3 C4 C5 C6 135.8(3) . . . . ? C9 C4 C5 C6 12.6(3) . . . . ? C4 C5 C6 C12 -63.7(3) . . . . ? C4 C5 C6 C7 53.7(3) . . . . ? C12 C6 C7 O4 167.4(2) . . . . ? C5 C6 C7 O4 51.3(3) . . . . ? C12 C6 C7 C14 -67.4(3) . . . . ? C5 C6 C7 C14 176.5(2) . . . . ? C12 C6 C7 C8 51.2(3) . . . . ? C5 C6 C7 C8 -64.9(3) . . . . ? O4 C7 C8 O3 71.0(3) . . . . ? C14 C7 C8 O3 -49.6(4) . . . . ? C6 C7 C8 O3 -173.4(3) . . . . ? O4 C7 C8 C9 -108.2(2) . . . . ? C14 C7 C8 C9 131.2(3) . . . . ? C6 C7 C8 C9 7.5(3) . . . . ? O3 C8 C9 C11 122.2(3) . . . . ? C7 C8 C9 C11 -58.7(3) . . . . ? O3 C8 C9 C10 -1.1(4) . . . . ? C7 C8 C9 C10 178.0(2) . . . . ? O3 C8 C9 C4 -123.7(3) . . . . ? C7 C8 C9 C4 55.4(3) . . . . ? C3 C4 C9 C11 -80.0(3) . . . . ? C5 C4 C9 C11 43.2(3) . . . . ? C3 C4 C9 C8 170.2(2) . . . . ? C5 C4 C9 C8 -66.7(3) . . . . ? C3 C4 C9 C10 49.4(3) . . . . ? C5 C4 C9 C10 172.6(2) . . . . ? C8 C9 C11 C12 55.1(3) . . . . ? C10 C9 C11 C12 175.9(3) . . . . ? C4 C9 C11 C12 -55.2(3) . . . . ? C9 C11 C12 C13 179.1(3) . . . . ? C9 C11 C12 C6 2.8(4) . . . . ? C7 C6 C12 C11 -60.1(3) . . . . ? C5 C6 C12 C11 57.4(3) . . . . ? C7 C6 C12 C13 123.3(3) . . . . ? C5 C6 C12 C13 -119.2(3) . . . . ? O4 C7 C14 Cl1 60.5(3) . . . . ? C6 C7 C14 Cl1 -62.5(4) . . . . ? C8 C7 C14 Cl1 178.9(2) . . . . ? _diffrn_measured_fraction_theta_max 0.697 _diffrn_reflns_theta_full 24.91 _diffrn_measured_fraction_theta_full 0.697 _refine_diff_density_max 0.270 _refine_diff_density_min -0.188 _refine_diff_density_rms 0.039