# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Dr Christopher Hyland' _publ_contact_author_email chris.hyland@utas.edu.au _publ_section_title ; Titanium-Mediated Rearrangment of Cyclopropenylmethyl Acetates to (E)-Halodienes ; loop_ _publ_author_name C.Hyland G.Gallego B.Yates A.Ariafard K.Tran D.Sandoval ; L.Choi ; F.-M.Tao Y.-H.Chen # Attachment 'csuf5-A-1.cif' data_csuf5_0m _database_code_depnum_ccdc_archive 'CCDC 737881' #TrackingRef 'csuf5-A-1.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; (E)-(2-chloro-3,4-dimethylpenta-1,3-dienyl)benzene ; _chemical_name_common (E)-(2-chloro-3,4-dimethylpenta-1,3-dienyl)benzene _chemical_melting_point ? _chemical_formula_moiety 'C13 H14 Cl N O2' _chemical_formula_sum 'C13 H14 Cl N O2' _chemical_formula_weight 251.70 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' N N 0.0061 0.0033 '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 monoclinic _symmetry_space_group_name_H-M P2(1)/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 13.0021(13) _cell_length_b 7.2565(7) _cell_length_c 14.3625(15) _cell_angle_alpha 90.00 _cell_angle_beta 111.3350(10) _cell_angle_gamma 90.00 _cell_volume 1262.2(2) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 3609 _cell_measurement_theta_min 4 _cell_measurement_theta_max 30.3 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.33 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.325 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 528 _exptl_absorpt_coefficient_mu 0.292 _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 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 'SMART 1K CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 9111 _diffrn_reflns_av_R_equivalents 0.0172 _diffrn_reflns_av_sigmaI/netI 0.0214 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 4.03 _diffrn_reflns_theta_max 30.62 _reflns_number_total 3699 _reflns_number_gt 3013 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX II (CCD2 - upgrade)' _computing_cell_refinement 'Bruker SMART (Bruker, 1997)' _computing_data_reduction 'XPREP (Broker-AXS, 2005)' _computing_structure_solution 'SHELXTL (Sheldrick, 2008)' _computing_structure_refinement 'SHELXTL (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 2008)' _computing_publication_material 'SHELXTL (Sheldrick, 2008)' _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^)+(0.1312P)^2^+1.3762P] 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 3699 _refine_ls_number_parameters 171 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0866 _refine_ls_R_factor_gt 0.0758 _refine_ls_wR_factor_ref 0.2348 _refine_ls_wR_factor_gt 0.2230 _refine_ls_goodness_of_fit_ref 1.083 _refine_ls_restrained_S_all 1.083 _refine_ls_shift/su_max 0.033 _refine_ls_shift/su_mean 0.005 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 0.91837(17) 0.2110(3) 0.48244(16) 0.0218(4) Uani 1 1 d . . . C2 C 0.81428(18) 0.1399(3) 0.42429(17) 0.0261(4) Uani 1 1 d . . . H2A H 0.7683 0.0942 0.4555 0.041(9) Uiso 1 1 calc R . . C3 C 0.77933(17) 0.1371(3) 0.32087(16) 0.0254(4) Uani 1 1 d . . . H3A H 0.7106 0.0892 0.2826 0.037(8) Uiso 1 1 calc R . . C4 C 0.84858(17) 0.2068(3) 0.27566(16) 0.0226(4) Uani 1 1 d . . . C5 C 0.95160(17) 0.2793(3) 0.32996(16) 0.0253(4) Uani 1 1 d . . . H5A H 0.9964 0.3269 0.2979 0.028(7) Uiso 1 1 calc R . . C6 C 0.98593(18) 0.2790(3) 0.43296(17) 0.0247(4) Uani 1 1 d . . . H6A H 1.0555 0.3249 0.4705 0.034(8) Uiso 1 1 calc R . . C7 C 0.96333(18) 0.2137(3) 0.59261(17) 0.0254(4) Uani 1 1 d . A . H1 H 1.044(3) 0.230(4) 0.623(2) 0.030(7) Uiso 1 1 d . . . C8 C 0.9094(2) 0.1912(4) 0.65419(18) 0.0311(5) Uani 1 1 d . . . C9 C 0.7917(2) 0.1336(4) 0.6329(2) 0.0237(5) Uani 0.75 1 d P A 1 C10 C 0.7128(3) 0.2623(4) 0.6063(2) 0.0253(5) Uani 0.75 1 d P A 1 C11 C 0.7685(3) -0.0703(3) 0.6402(2) 0.0396(6) Uani 1 1 d . . . H11A H 0.7029 -0.0842 0.6554 0.087(16) Uiso 1 1 calc R A 1 H11B H 0.8297 -0.1259 0.6921 0.103(19) Uiso 1 1 calc R A 1 H11C H 0.7582 -0.1293 0.5776 0.067(12) Uiso 1 1 calc R A 1 C12 C 0.5924(3) 0.2112(6) 0.5819(3) 0.0523(8) Uani 1 1 d . . . H12C H 0.5882 0.1006 0.6170 0.049(10) Uiso 1 1 calc R A 1 H12A H 0.5574 0.1911 0.5112 0.15(3) Uiso 1 1 calc R A 1 H12B H 0.5556 0.3095 0.6019 0.082(16) Uiso 1 1 calc R A 1 C13 C 0.7413(3) 0.4651(4) 0.6021(3) 0.0471(7) Uani 1 1 d . . . H13A H 0.6990 0.5385 0.6308 0.065(12) Uiso 1 1 calc R A 1 H13C H 0.7242 0.5010 0.5338 0.078(14) Uiso 1 1 calc R A 1 H13B H 0.8186 0.4835 0.6390 0.105(19) Uiso 1 1 calc R A 1 Cl1 Cl 0.98871(6) 0.19789(11) 0.78365(4) 0.0431(2) Uani 1 1 d . A . N1 N 0.81148(16) 0.2037(3) 0.16641(15) 0.0270(4) Uani 1 1 d . . . O1 O 0.86766(16) 0.2826(3) 0.12652(14) 0.0375(5) Uani 1 1 d . . . O2 O 0.72444(15) 0.1232(3) 0.11995(13) 0.0379(4) 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 0.0225(9) 0.0227(9) 0.0217(9) -0.0008(7) 0.0098(8) 0.0001(7) C2 0.0249(10) 0.0309(10) 0.0249(10) -0.0029(8) 0.0119(8) -0.0059(8) C3 0.0208(9) 0.0304(10) 0.0247(10) -0.0024(8) 0.0081(8) -0.0029(7) C4 0.0209(9) 0.0272(10) 0.0194(9) -0.0005(7) 0.0072(8) 0.0030(7) C5 0.0195(9) 0.0343(11) 0.0234(10) 0.0009(8) 0.0095(8) -0.0006(8) C6 0.0193(9) 0.0320(11) 0.0226(10) -0.0014(8) 0.0072(8) -0.0020(7) C7 0.0233(9) 0.0302(11) 0.0226(10) -0.0020(7) 0.0083(8) -0.0014(8) C8 0.0280(11) 0.0430(13) 0.0221(10) -0.0013(8) 0.0087(9) -0.0001(9) C9 0.0299(13) 0.0212(12) 0.0232(12) -0.0018(9) 0.0134(11) -0.0038(10) C10 0.0294(13) 0.0262(13) 0.0244(13) -0.0022(10) 0.0147(11) -0.0037(11) C11 0.0636(18) 0.0212(10) 0.0456(15) -0.0009(9) 0.0336(14) -0.0046(11) C12 0.0297(13) 0.078(2) 0.0524(19) -0.0116(16) 0.0190(13) -0.0064(13) C13 0.070(2) 0.0253(11) 0.0651(19) 0.0065(12) 0.0469(17) 0.0044(12) Cl1 0.0371(4) 0.0702(5) 0.0216(3) -0.0020(3) 0.0103(3) -0.0060(3) N1 0.0222(8) 0.0358(10) 0.0218(9) 0.0008(7) 0.0068(7) 0.0058(7) O1 0.0322(9) 0.0578(12) 0.0256(9) 0.0053(8) 0.0143(7) 0.0010(8) O2 0.0276(8) 0.0575(12) 0.0248(8) -0.0050(8) 0.0048(7) -0.0042(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 C1 C6 1.405(3) . ? C1 C2 1.405(3) . ? C1 C7 1.474(3) . ? C2 C3 1.386(3) . ? C2 H2A 0.9300 . ? C3 C4 1.383(3) . ? C3 H3A 0.9300 . ? C4 C5 1.385(3) . ? C4 N1 1.464(3) . ? C5 C6 1.381(3) . ? C5 H5A 0.9300 . ? C6 H6A 0.9300 . ? C7 C8 1.323(3) . ? C7 H1 0.98(3) . ? C8 C9 1.507(4) . ? C8 Cl1 1.768(2) . ? C9 C10 1.337(4) . ? C9 C11 1.521(4) . ? C10 C12 1.520(4) . ? C10 C13 1.524(4) . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 H12C 0.9600 . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C13 H13A 0.9600 . ? C13 H13C 0.9600 . ? C13 H13B 0.9600 . ? N1 O1 1.223(3) . ? N1 O2 1.232(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 C6 C1 C2 118.2(2) . . ? C6 C1 C7 117.47(19) . . ? C2 C1 C7 124.29(19) . . ? C3 C2 C1 120.78(19) . . ? C3 C2 H2A 119.6 . . ? C1 C2 H2A 119.6 . . ? C4 C3 C2 118.8(2) . . ? C4 C3 H3A 120.6 . . ? C2 C3 H3A 120.6 . . ? C3 C4 C5 122.4(2) . . ? C3 C4 N1 118.71(19) . . ? C5 C4 N1 118.90(19) . . ? C6 C5 C4 118.2(2) . . ? C6 C5 H5A 120.9 . . ? C4 C5 H5A 120.9 . . ? C5 C6 C1 121.6(2) . . ? C5 C6 H6A 119.2 . . ? C1 C6 H6A 119.2 . . ? C8 C7 C1 128.0(2) . . ? C8 C7 H1 116.6(19) . . ? C1 C7 H1 115.3(19) . . ? C7 C8 C9 130.1(2) . . ? C7 C8 Cl1 116.84(18) . . ? C9 C8 Cl1 112.42(17) . . ? C10 C9 C8 118.8(3) . . ? C10 C9 C11 123.2(3) . . ? C8 C9 C11 117.9(3) . . ? C9 C10 C12 121.0(3) . . ? C9 C10 C13 120.9(3) . . ? C12 C10 C13 118.1(3) . . ? 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 . . ? C10 C12 H12C 109.5 . . ? C10 C12 H12A 109.5 . . ? H12C C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12C C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? H13C C13 H13B 109.5 . . ? O1 N1 O2 123.8(2) . . ? O1 N1 C4 118.35(19) . . ? O2 N1 C4 117.86(19) . . ? _diffrn_measured_fraction_theta_max 0.947 _diffrn_reflns_theta_full 30.62 _diffrn_measured_fraction_theta_full 0.947 _refine_diff_density_max 2.390 _refine_diff_density_min -0.404 _refine_diff_density_rms 0.100