Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global #=================================================================== _journal_coden_cambridge 222 _audit_creation_date 13-Aug-07 _audit_creation_method 'PLATON option' _audit_update_record ; 14-Aug-07 Updated by the Author E.H. Text writing by E.H. Checkcif OK 14-Aug-07 Updated by the Author E.H. ; _publ_contact_author_name ; Fritz Kuhn ; _publ_contact_author_address ; Institut fur Anorganische und Analytische Chemie Technischen Universitat Munchen Lichtenbergstrasse 4 Garching D-85747 GERMANY ; _publ_contact_author_email FRITZ.KUEHN@CH.TUM.DE _publ_requested_journal 'Dalton Trans.' _publ_requested_category ? _publ_requested_coeditor_name ? _publ_contact_letter ; Date of submission: August 2007 ; _publ_section_title ; Ansa-bridged h5-Cyclopentadienyl Molybdenum and Tungsten Complexes: Synthesis, Structure and Application in Olefin Epoxidation ; loop_ _publ_author_name _publ_author_address 'Jin Zhao.' ; Department Chemie, Lehrstuhl fur Anorganische Chemie, Technische Universitat Munchen, Lichtenbergstrasse 4, D-85747 Garching bei Munchen, Germany. ; 'Jain, K. R.' ; Department Chemie, Lehrstuhl fur Anorganische Chemie, Technische Universitat Munchen, Lichtenbergstrasse 4, D-85747 Garching bei Munchen, Germany. ; 'Herdtweck, E.' ; Department Chemie, Lehrstuhl fur Anorganische Chemie, Technische Universitat Munchen, Lichtenbergstrasse 4, D-85747 Garching bei Munchen, Germany. ; 'Kuhn, F. E.' ; Department Chemie, Lehrstuhl fur Anorganische Chemie, Technische Universitat Munchen, Lichtenbergstrasse 4, D-85747 Garching bei Munchen, Germany. ; _publ_section_abstract ; Ansa-bridged h5-cyclopentadienyl molybdenum and tungsten tricarbonyl complexes of formula... ; _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). SIR92, J. Appl. Cryst. 27, 435-436. Farrugia, L. J. (1999). WinGX (Version 1.70.01 January 2005), J. Appl. Cryst. 32, 837-838. Nonius (2001a). Data Collection Software for Nonius Kappa-CCD devices. Nonius BV, Delft, The Netherlands. Nonius (2001b). DENZO Processing Software for Nonius Kappa-CCD devices, Nonius BV, Delft, The Netherlands. Sheldrick, G. M. (1998). SHELXL97, University of Gottingen, Gottingen, Germany. Spek, A. L. (2007). PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. ; #=================================================================== data_ZHAO-4470-123 _database_code_depnum_ccdc_archive 'CCDC 658844' #=================================================================== #=================================================================== # 5. CHEMICAL DATA #=================================================================== _chemical_name_systematic ; ; _chemical_name_common ? _chemical_formula_moiety 'C12 H12 O3 W' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C12 H12 O3 W' _chemical_formula_weight 388.06 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source W W -0.8490 6.8722 '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' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #=================================================================== # 6. CRYSTAL DATA #=================================================================== _symmetry_cell_setting Monoclinic _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_space_group_name_H-M 'P 21/c' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x,1/2+y,1/2-z 3 -x,-y,-z 4 x,1/2-y,1/2+z _cell_length_a 11.2909(1) _cell_length_b 8.1047(1) _cell_length_c 12.9838(2) _cell_angle_alpha 90 _cell_angle_beta 107.4344(5) _cell_angle_gamma 90 _cell_volume 1133.56(2) _cell_formula_units_Z 4 _cell_measurement_temperature 123(1) _cell_measurement_reflns_used 13543 _cell_measurement_theta_min 1.89 _cell_measurement_theta_max 25.38 _exptl_crystal_description fragment _exptl_crystal_colour yellow _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 2.274 _exptl_crystal_density_method none _exptl_crystal_F_000 728 _exptl_absorpt_coefficient_mu 10.178 _exptl_absorpt_correction_type refdelf _exptl_absorpt_correction_T_min 0.049 _exptl_absorpt_correction_T_max 0.162 _exptl_absorpt_process_details '(applied during the scaling procedure; Nonius, 2001b)' _exptl_special_details ; Diffractometer operator E. Herdtweck scanspeed 2 x 8 s per film repetition 1 dx 40 517 films measured in 10 data sets set 1: phi-scan with delta_phi = 1.0 set 2 to 10: omega-scans with delta_omega = 1.0 ; _publ_section_exptl_prep ; The crystal was fixed in a capillary with perfluorinated ether and transferred to the diffractometer. ; _publ_section_exptl_refinement ; Solution and refinements with the program WinGX; Farrugia (1999). Hydrogen atoms could not be located in the difference Fourier maps and were calculated in ideal positions (riding model). ; #=================================================================== # 7. EXPERIMENTAL DATA #=================================================================== _diffrn_ambient_temperature 123(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'NONIUS FR 591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device ' \k-geometry diffractometer ' _diffrn_measurement_device_type ' Nonius \k-CCD diffractometer' _diffrn_measurement_method ' phi- and omega-rotation ' _diffrn_detector ' CCD plate ' _diffrn_detector_area_resol_mean 18 # 9 for binned mode _diffrn_standards_decay_% 0 # number of measured reflections (redundant set) _diffrn_reflns_number 23404 _diffrn_reflns_av_R_equivalents 0.0500 _diffrn_reflns_av_sigmaI/netI 0.0176 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.89 _diffrn_reflns_theta_max 25.38 _reflns_number_total 2081 _reflns_number_gt 1994 # number of observed reflections (> n sig(I)) _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Kappa-CCD Control Software (Nonius, 2001a)' _computing_cell_refinement 'DENZO (Nonius, 2001b)' _computing_data_reduction 'DENZO (Nonius, 2001b)' _computing_structure_solution 'SIR92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1998)' _computing_molecular_graphics 'PLATON (Spek, 2007)' _computing_publication_material 'PLATON (Spek, 2007)' #=================================================================== # 8. REFINEMENT DATA #=================================================================== _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 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 sigma _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0091P)^2^+2.9712P] 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 SHELXL _refine_ls_extinction_coef 0.00440(13) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2081 _refine_ls_number_parameters 146 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0175 _refine_ls_R_factor_gt 0.0164 _refine_ls_wR_factor_ref 0.0382 _refine_ls_wR_factor_gt 0.0378 _refine_ls_goodness_of_fit_ref 1.162 _refine_ls_restrained_S_all 1.162 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.38 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.118 _refine_diff_density_min -0.864 _refine_diff_density_rms 0.101 #=================================================================== # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS #=================================================================== loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags W W Uani 0.19859(1) 0.49025(1) 0.23498(1) 1.000 0.0104(1) . . O1 O Uani 0.3237(2) 0.4993(3) 0.0500(2) 1.000 0.0198(8) . . O2 O Uani 0.0932(3) 0.8257(3) 0.1235(2) 1.000 0.0274(9) . . O3 O Uani -0.0805(2) 0.4165(3) 0.1181(2) 1.000 0.0286(9) . . C1 C Uani 0.2766(3) 0.4985(4) 0.1171(3) 1.000 0.0134(10) . . C2 C Uani 0.1338(3) 0.7058(4) 0.1655(3) 1.000 0.0178(11) . . C3 C Uani 0.0217(3) 0.4450(4) 0.1606(3) 1.000 0.0157(10) . . C4 C Uani 0.1863(3) 0.2250(4) 0.1620(3) 1.000 0.0155(10) . . C5 C Uani 0.3086(3) 0.1320(4) 0.1835(3) 1.000 0.0177(10) . . C6 C Uani 0.3681(3) 0.0829(4) 0.3012(3) 1.000 0.0195(10) . . C7 C Uani 0.4314(3) 0.2254(4) 0.3744(3) 1.000 0.0193(11) . . C8 C Uani 0.3467(3) 0.3642(4) 0.3814(2) 1.000 0.0147(10) . . C9 C Uani 0.2271(3) 0.3539(4) 0.3977(3) 1.000 0.0159(10) . . C10 C Uani 0.1866(4) 0.5150(4) 0.4112(3) 1.000 0.0168(11) . . C11 C Uani 0.2786(3) 0.6271(4) 0.4007(3) 1.000 0.0174(10) . . C12 C Uani 0.3775(3) 0.5344(4) 0.3836(3) 1.000 0.0165(10) . . H41 H Uiso 0.12970 0.15860 0.19080 1.000 0.0190 calc R H42 H Uiso 0.14800 0.23320 0.08290 1.000 0.0190 calc R H51 H Uiso 0.36780 0.20190 0.16020 1.000 0.0210 calc R H52 H Uiso 0.29400 0.03090 0.13860 1.000 0.0210 calc R H61 H Uiso 0.43040 -0.00450 0.30430 1.000 0.0230 calc R H62 H Uiso 0.30330 0.03550 0.32960 1.000 0.0230 calc R H71 H Uiso 0.47050 0.18160 0.44800 1.000 0.0230 calc R H72 H Uiso 0.49840 0.26960 0.34760 1.000 0.0230 calc R H91 H Uiso 0.18240 0.25510 0.39910 1.000 0.0190 calc R H101 H Uiso 0.11100 0.54320 0.42490 1.000 0.0200 calc R H111 H Uiso 0.27470 0.74400 0.40450 1.000 0.0210 calc R H121 H Uiso 0.45190 0.57870 0.37500 1.000 0.0200 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 W 0.0095(1) 0.0121(1) 0.0091(1) 0.0003(1) 0.0021(1) -0.0003(1) O1 0.0172(14) 0.0305(15) 0.0142(13) 0.0009(9) 0.0085(11) -0.0036(10) O2 0.0327(16) 0.0174(14) 0.0304(15) 0.0079(11) 0.0067(12) 0.0050(12) O3 0.0125(14) 0.0370(16) 0.0321(15) 0.0039(12) 0.0005(12) -0.0037(12) C1 0.0091(17) 0.0119(17) 0.0146(17) 0.0006(12) -0.0036(14) -0.0008(11) C2 0.0176(19) 0.0185(19) 0.0179(18) -0.0024(14) 0.0064(15) -0.0032(14) C3 0.0143(19) 0.0187(17) 0.0142(16) 0.0052(14) 0.0044(14) -0.0006(14) C4 0.0148(18) 0.0155(17) 0.0149(17) -0.0038(13) 0.0027(14) -0.0015(13) C5 0.0190(19) 0.0158(17) 0.0184(18) -0.0034(13) 0.0060(15) 0.0021(14) C6 0.0198(19) 0.0150(17) 0.0234(18) -0.0009(14) 0.0061(15) 0.0030(14) C7 0.0168(19) 0.0194(18) 0.0186(18) 0.0007(14) 0.0006(15) 0.0046(14) C8 0.0130(17) 0.0200(18) 0.0075(15) 0.0008(12) -0.0022(13) 0.0023(13) C9 0.0193(19) 0.0178(17) 0.0086(16) 0.0020(13) 0.0010(14) -0.0018(14) C10 0.019(2) 0.0226(19) 0.0090(16) -0.0025(13) 0.0047(14) 0.0040(14) C11 0.0203(19) 0.0168(17) 0.0109(16) -0.0025(13) -0.0017(14) 0.0008(14) C12 0.0111(18) 0.0205(17) 0.0144(17) -0.0012(14) -0.0014(14) -0.0032(14) #================================================================== # 10. MOLECULAR GEOMETRY #=================================================================== loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag W C1 1.983(4) . . yes W C2 2.001(3) . . yes W C3 1.975(4) . . yes W C4 2.337(3) . . yes W C8 2.356(3) . . yes W C9 2.320(4) . . yes W C10 2.341(4) . . yes W C11 2.348(4) . . yes W C12 2.366(4) . . yes O1 C1 1.149(4) . . yes O2 C2 1.141(4) . . yes O3 C3 1.144(4) . . yes C4 C5 1.524(5) . . no C5 C6 1.526(5) . . no C6 C7 1.530(5) . . no C7 C8 1.497(5) . . no C8 C9 1.431(5) . . no C8 C12 1.421(5) . . no C9 C10 1.412(5) . . no C10 C11 1.417(5) . . no C11 C12 1.418(5) . . no C4 H41 0.9900 . . no C4 H42 0.9900 . . no C5 H51 0.9900 . . no C5 H52 0.9900 . . no C6 H61 0.9900 . . no C6 H62 0.9900 . . no C7 H71 0.9900 . . no C7 H72 0.9900 . . no C9 H91 0.9500 . . no C10 H101 0.9500 . . no C11 H111 0.9500 . . no C12 H121 0.9500 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 W C2 79.02(14) . . . yes C1 W C3 104.29(15) . . . yes C1 W C4 72.79(13) . . . yes C1 W C8 105.40(13) . . . yes C1 W C9 138.30(13) . . . yes C1 W C10 157.06(15) . . . yes C1 W C11 123.62(13) . . . yes C1 W C12 98.99(14) . . . yes C2 W C3 76.24(14) . . . yes C2 W C4 130.62(14) . . . yes C2 W C8 144.84(13) . . . yes C2 W C9 139.34(13) . . . yes C2 W C10 104.21(13) . . . yes C2 W C11 89.37(13) . . . yes C2 W C12 110.07(13) . . . yes C3 W C4 72.69(13) . . . yes C3 W C8 133.12(13) . . . yes C3 W C9 101.59(14) . . . yes C3 W C10 98.49(15) . . . yes C3 W C11 126.23(14) . . . yes C3 W C12 156.67(14) . . . yes C4 W C8 82.52(12) . . . yes C4 W C9 84.62(12) . . . yes C4 W C10 117.48(12) . . . yes C4 W C11 140.01(12) . . . yes C4 W C12 113.73(12) . . . yes C8 W C9 35.62(12) . . . yes C8 W C10 58.89(13) . . . yes C8 W C11 58.67(11) . . . yes C8 W C12 35.03(11) . . . yes C9 W C10 35.26(12) . . . yes C9 W C11 58.67(12) . . . yes C9 W C12 58.51(12) . . . yes C10 W C11 35.18(13) . . . yes C10 W C12 58.34(14) . . . yes C11 W C12 35.00(12) . . . yes W C1 O1 178.0(3) . . . yes W C2 O2 177.5(3) . . . yes W C3 O3 179.0(3) . . . yes W C4 C5 116.1(2) . . . yes C4 C5 C6 114.5(3) . . . no C5 C6 C7 114.1(3) . . . no C6 C7 C8 114.6(3) . . . no W C8 C7 126.1(2) . . . yes W C8 C9 70.81(19) . . . yes W C8 C12 72.87(19) . . . yes C7 C8 C9 127.9(3) . . . no C7 C8 C12 125.0(3) . . . no C9 C8 C12 106.9(3) . . . no W C9 C8 73.56(18) . . . yes W C9 C10 73.2(2) . . . yes C8 C9 C10 108.6(3) . . . no W C10 C9 71.6(2) . . . yes W C10 C11 72.7(2) . . . yes C9 C10 C11 107.9(4) . . . no W C11 C10 72.1(2) . . . yes W C11 C12 73.2(2) . . . yes C10 C11 C12 108.1(3) . . . no W C12 C8 72.10(18) . . . yes W C12 C11 71.8(2) . . . yes C8 C12 C11 108.6(3) . . . no W C4 H41 108.00 . . . no W C4 H42 108.00 . . . no C5 C4 H41 108.00 . . . no C5 C4 H42 108.00 . . . no H41 C4 H42 107.00 . . . no C4 C5 H51 109.00 . . . no C4 C5 H52 109.00 . . . no C6 C5 H51 109.00 . . . no C6 C5 H52 109.00 . . . no H51 C5 H52 108.00 . . . no C5 C6 H61 109.00 . . . no C5 C6 H62 109.00 . . . no C7 C6 H61 109.00 . . . no C7 C6 H62 109.00 . . . no H61 C6 H62 108.00 . . . no C6 C7 H71 109.00 . . . no C6 C7 H72 109.00 . . . no C8 C7 H71 109.00 . . . no C8 C7 H72 109.00 . . . no H71 C7 H72 108.00 . . . no W C9 H91 119.00 . . . no C8 C9 H91 126.00 . . . no C10 C9 H91 126.00 . . . no W C10 H101 121.00 . . . no C9 C10 H101 126.00 . . . no C11 C10 H101 126.00 . . . no W C11 H111 120.00 . . . no C10 C11 H111 126.00 . . . no C12 C11 H111 126.00 . . . no W C12 H121 122.00 . . . no C8 C12 H121 126.00 . . . no C11 C12 H121 126.00 . . . no # End of Crystallographic Information File