# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Uwe Rosenthal' 'Perdita Arndt' 'Wolfgang Baumann' 'Vladimir V. Burlakov' 'Eluvathingal Jemmis' 'Pattiyil Parameswaran' 'Anke Spannenberg' _publ_contact_author_name 'ProfD Uwe Rosenthal' _publ_contact_author_address ; Chemistry Leibniz-IFOK at the University of RostockI Buchbinderstr. 5-6 Rostock MV D-18055 GERMANY ; _publ_contact_author_email UWE.ROSENTHAL@IFOK.UNI-ROSTOCK.DE _publ_requested_journal 'Chemical Communications' _publ_section_title ; Reduction of 1,4-Dichloro-but-2-yne by Titanocene to the 1,2,3-Butatriene. Formation of the 1-Titana-cyclo-pent-3-yne and the 2,5-Dititana-bicyclo[2.2.0]hex-1(4)-ene ; data_ks248 _database_code_depnum_ccdc_archive 'CCDC 239591' _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C24 H24 Ti2' _chemical_formula_weight 408.23 _chemical_melting_point ? _chemical_compound_source ? 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' Ti Ti 0.2776 0.4457 '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 8.687(2) _cell_length_b 7.887(2) _cell_length_c 13.353(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.17(3) _cell_angle_gamma 90.00 _cell_volume 914.9(4) _cell_formula_units_Z 2 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 5000 _cell_measurement_theta_min 4 _cell_measurement_theta_max 20 _exptl_crystal_description prism _exptl_crystal_colour 'dark green' _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.4 _exptl_crystal_size_min 0.3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.482 _exptl_crystal_density_method ? _exptl_crystal_F_000 424 _exptl_absorpt_coefficient_mu 0.877 _exptl_absorpt_correction_type no _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(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 STOE-IPDS _diffrn_measurement_method 'laser scanned imaging plate' _diffrn_standards_number 50-200 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 360 _diffrn_standards_decay_% ? _diffrn_reflns_number 2621 _diffrn_reflns_av_R_equivalents 0.0196 _diffrn_reflns_av_sigmaI/netI 0.0321 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.80 _diffrn_reflns_theta_max 24.22 _reflns_number_total 1429 _reflns_number_observed 1221 _reflns_observed_criterion >2sigma(I) _computing_data_collection STOE-EXPOSE _computing_cell_refinement STOE-CELL _computing_data_reduction STOE-INTEGRATE _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics XP _computing_publication_material SHELXL-93 _refine_special_details ; Refinement on F^2^ for ALL reflections except for 1 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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^)+(0.0484P)^2^+0.6738P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1428 _refine_ls_number_parameters 126 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0437 _refine_ls_R_factor_obs 0.0364 _refine_ls_wR_factor_all 0.0963 _refine_ls_wR_factor_obs 0.0888 _refine_ls_goodness_of_fit_all 1.051 _refine_ls_goodness_of_fit_obs 1.108 _refine_ls_restrained_S_all 1.102 _refine_ls_restrained_S_obs 1.108 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group C1 C 0.5383(3) 0.4308(3) 0.0130(2) 0.0252(6) Uani 1 d . . C2 C 0.3043(3) 0.6062(4) -0.0402(2) 0.0304(7) Uani 1 d . . C3 C 0.3261(4) 0.2460(6) 0.1572(2) 0.0501(10) Uani 1 d . . H3 H 0.4237(4) 0.2148(6) 0.1836(2) 0.060 Uiso 1 calc R . C4 C 0.2598(5) 0.4096(5) 0.1571(2) 0.0608(12) Uani 1 d . . H4 H 0.3040(5) 0.5099(5) 0.1841(2) 0.073 Uiso 1 calc R . C5 C 0.1163(4) 0.3954(5) 0.1096(3) 0.0530(10) Uani 1 d . . H5 H 0.0457(4) 0.4853(5) 0.0978(3) 0.064 Uiso 1 calc R . C6 C 0.0963(4) 0.2329(5) 0.0836(3) 0.0524(9) Uani 1 d . . H6 H 0.0079(4) 0.1886(5) 0.0508(3) 0.063 Uiso 1 calc R . C7 C 0.2212(4) 0.1414(4) 0.1113(3) 0.0485(9) Uani 1 d . . H7 H 0.2341(4) 0.0231(4) 0.1007(3) 0.058 Uiso 1 calc R . C8 C 0.1838(6) 0.1624(7) -0.1318(3) 0.083(2) Uani 1 d . . H8 H 0.0843(6) 0.1191(7) -0.1171(3) 0.100 Uiso 1 calc R . C9 C 0.2155(4) 0.3100(6) -0.1799(3) 0.0557(10) Uani 1 d . . H9 H 0.1418(4) 0.3894(6) -0.2037(3) 0.067 Uiso 1 calc R . C10 C 0.3699(4) 0.3244(4) -0.1881(2) 0.0450(8) Uani 1 d . . H10 H 0.4216(4) 0.4161(4) -0.2196(2) 0.054 Uiso 1 calc R . C11 C 0.4400(4) 0.1912(4) -0.1454(2) 0.0474(9) Uani 1 d . . H11 H 0.5480(4) 0.1735(4) -0.1420(2) 0.057 Uiso 1 calc R . C12 C 0.3288(7) 0.0838(5) -0.1073(3) 0.079(2) Uani 1 d . . H12 H 0.3447(7) -0.0197(5) -0.0724(3) 0.094 Uiso 1 calc R . Ti1 Ti 0.30943(5) 0.33562(6) -0.01248(3) 0.0233(2) Uani 1 d . . H2A H 0.2953(35) 0.6449(38) -0.1038(26) 0.036(9) Uiso 1 d . . H2B H 0.2555(36) 0.6721(36) 0.0048(23) 0.027(8) 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 C1 0.0291(15) 0.0231(13) 0.0233(14) -0.0015(11) 0.0032(12) -0.0008(10) C2 0.035(2) 0.029(2) 0.027(2) 0.0033(13) 0.0032(14) 0.0105(13) C3 0.032(2) 0.094(3) 0.025(2) 0.024(2) 0.0011(14) 0.006(2) C4 0.097(3) 0.061(2) 0.024(2) -0.018(2) 0.033(2) -0.039(2) C5 0.049(2) 0.070(3) 0.040(2) 0.019(2) 0.026(2) 0.024(2) C6 0.032(2) 0.080(3) 0.045(2) 0.013(2) 0.009(2) -0.011(2) C7 0.062(2) 0.042(2) 0.042(2) 0.016(2) 0.015(2) -0.006(2) C8 0.075(3) 0.125(5) 0.050(3) -0.049(3) 0.019(2) -0.068(3) C9 0.053(2) 0.086(3) 0.028(2) -0.015(2) -0.012(2) 0.006(2) C10 0.061(2) 0.052(2) 0.022(2) -0.0051(15) 0.004(2) 0.003(2) C11 0.056(2) 0.049(2) 0.037(2) -0.019(2) 0.003(2) 0.016(2) C12 0.176(5) 0.020(2) 0.041(2) -0.010(2) 0.003(3) -0.008(3) Ti1 0.0259(3) 0.0236(3) 0.0204(3) 0.0005(2) 0.0025(2) 0.0006(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 C1 C1 1.325(5) 3_665 ? C1 C2 1.443(4) 3_665 ? C1 Ti1 2.152(3) . ? C1 Ti1 2.268(3) 3_665 ? C2 C1 1.443(4) 3_665 ? C2 Ti1 2.167(3) . ? C3 C7 1.373(5) . ? C3 C4 1.413(6) . ? C3 Ti1 2.377(3) . ? C4 C5 1.401(5) . ? C4 Ti1 2.379(3) . ? C5 C6 1.339(6) . ? C5 Ti1 2.389(3) . ? C6 C7 1.353(5) . ? C6 Ti1 2.397(3) . ? C7 Ti1 2.382(3) . ? C8 C9 1.358(6) . ? C8 C12 1.441(7) . ? C8 Ti1 2.364(3) . ? C9 C10 1.351(5) . ? C9 Ti1 2.386(3) . ? C10 C11 1.340(5) . ? C10 Ti1 2.406(3) . ? C11 C12 1.383(6) . ? C11 Ti1 2.397(3) . ? C12 Ti1 2.362(4) . ? Ti1 C1 2.268(3) 3_665 ? 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 C1 C1 C2 135.1(3) 3_665 3_665 ? C1 C1 Ti1 77.4(2) 3_665 . ? C2 C1 Ti1 147.5(2) 3_665 . ? C1 C1 Ti1 67.8(2) 3_665 3_665 ? C2 C1 Ti1 67.3(2) 3_665 3_665 ? Ti1 C1 Ti1 145.24(13) . 3_665 ? C1 C2 Ti1 74.9(2) 3_665 . ? C7 C3 C4 106.2(3) . . ? C7 C3 Ti1 73.5(2) . . ? C4 C3 Ti1 72.8(2) . . ? C5 C4 C3 106.9(3) . . ? C5 C4 Ti1 73.3(2) . . ? C3 C4 Ti1 72.7(2) . . ? C6 C5 C4 107.9(3) . . ? C6 C5 Ti1 74.1(2) . . ? C4 C5 Ti1 72.5(2) . . ? C5 C6 C7 109.7(3) . . ? C5 C6 Ti1 73.4(2) . . ? C7 C6 Ti1 73.0(2) . . ? C6 C7 C3 109.4(4) . . ? C6 C7 Ti1 74.1(2) . . ? C3 C7 Ti1 73.0(2) . . ? C9 C8 C12 107.3(4) . . ? C9 C8 Ti1 74.3(2) . . ? C12 C8 Ti1 72.2(2) . . ? C10 C9 C8 108.3(4) . . ? C10 C9 Ti1 74.4(2) . . ? C8 C9 Ti1 72.5(2) . . ? C11 C10 C9 110.5(4) . . ? C11 C10 Ti1 73.5(2) . . ? C9 C10 Ti1 72.8(2) . . ? C10 C11 C12 108.7(4) . . ? C10 C11 Ti1 74.1(2) . . ? C12 C11 Ti1 71.7(2) . . ? C11 C12 C8 105.3(3) . . ? C11 C12 Ti1 74.5(2) . . ? C8 C12 Ti1 72.3(2) . . ? C1 Ti1 C2 72.65(10) . . ? C1 Ti1 C1 34.76(13) . 3_665 ? C2 Ti1 C1 37.90(10) . 3_665 ? C1 Ti1 C12 108.1(2) . . ? C2 Ti1 C12 137.57(13) . . ? C1 Ti1 C12 129.7(2) 3_665 . ? C1 Ti1 C8 137.14(14) . . ? C2 Ti1 C8 116.4(2) . . ? C1 Ti1 C8 137.35(14) 3_665 . ? C12 Ti1 C8 35.5(2) . . ? C1 Ti1 C3 84.22(11) . . ? C2 Ti1 C3 117.19(14) . . ? C1 Ti1 C3 102.15(12) 3_665 . ? C12 Ti1 C3 104.88(15) . . ? C8 Ti1 C3 119.8(2) . . ? C1 Ti1 C4 86.22(13) . . ? C2 Ti1 C4 85.27(14) . . ? C1 Ti1 C4 84.90(11) 3_665 . ? C12 Ti1 C4 136.88(14) . . ? C8 Ti1 C4 134.33(14) . . ? C3 Ti1 C4 34.56(14) . . ? C1 Ti1 C7 114.44(12) . . ? C2 Ti1 C7 138.22(13) . . ? C1 Ti1 C7 135.51(11) 3_665 . ? C12 Ti1 C7 81.66(14) . . ? C8 Ti1 C7 87.0(2) . . ? C3 Ti1 C7 33.52(13) . . ? C4 Ti1 C7 55.77(13) . . ? C1 Ti1 C9 119.41(13) . . ? C2 Ti1 C9 85.21(14) . . ? C1 Ti1 C9 105.29(13) 3_665 . ? C12 Ti1 C9 56.71(15) . . ? C8 Ti1 C9 33.2(2) . . ? C3 Ti1 C9 152.55(15) . . ? C4 Ti1 C9 148.2(2) . . ? C7 Ti1 C9 119.07(14) . . ? C1 Ti1 C5 118.27(13) . . ? C2 Ti1 C5 84.73(13) . . ? C1 Ti1 C5 104.61(13) 3_665 . ? C12 Ti1 C5 125.7(2) . . ? C8 Ti1 C5 104.5(2) . . ? C3 Ti1 C5 56.60(12) . . ? C4 Ti1 C5 34.17(14) . . ? C7 Ti1 C5 54.94(13) . . ? C9 Ti1 C5 114.65(14) . . ? C1 Ti1 C6 138.43(11) . . ? C2 Ti1 C6 114.15(13) . . ? C1 Ti1 C6 136.68(13) 3_665 . ? C12 Ti1 C6 93.4(2) . . ? C8 Ti1 C6 79.04(14) . . ? C3 Ti1 C6 55.54(12) . . ? C4 Ti1 C6 55.30(13) . . ? C7 Ti1 C6 32.90(13) . . ? C9 Ti1 C6 102.16(14) . . ? C5 Ti1 C6 32.50(14) . . ? C1 Ti1 C11 81.02(12) . . ? C2 Ti1 C11 110.54(13) . . ? C1 Ti1 C11 96.12(12) 3_665 . ? C12 Ti1 C11 33.77(15) . . ? C8 Ti1 C11 56.26(15) . . ? C3 Ti1 C11 122.48(13) . . ? C4 Ti1 C11 155.35(15) . . ? C7 Ti1 C11 111.24(13) . . ? C9 Ti1 C11 55.04(12) . . ? C5 Ti1 C11 159.00(14) . . ? C6 Ti1 C11 127.14(14) . . ? _refine_diff_density_max 0.392 _refine_diff_density_min -0.234 _refine_diff_density_rms 0.058