Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal SOciety of Chemistry 2002 data_biwo2b _database_code_CSD 160647 _journal_coden_Cambridge 186 loop_ _publ_author_name 'Schenk, Wolfdieter A.' 'Kiefer, W.' 'Kluglein, Matthias' 'Moigno, D.' 'Vedder, Birgit' _publ_contact_author_name 'Dr Wolfdieter A Schenk' _publ_contact_author_address ; Institut fur Anorganische Chemie Universitat Wurzburg Am Hubland Wurzberg D-97074 GERMANY ; _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Synthesis, structure, DTF calculations, and full vibrational analysis of the prototypical thioformaldehyde complex mer-[W(CO)3(Me2PC2H4PMe2)(eta2-S=CH2)] ; _publ_contact_author_phone '+49 931 8885259' _publ_contact_author_fax '+49 931 8884605' _publ_contact_author_email 'wolfdieter.schenk@mail.uni-wuerzburg.de' _publ_requested_journal '?' _publ_requested_coeditor_name 'Matthias Kluglein, Birgit Wolfsberger' _publ_contact_letter ; Please consider this CIF submission for publication in ; _publ_section_exptl_prep ; Crystals were grown at by diffusion of n-pentane into a toluene solution ; _publ_section_exptl_refinement ; The positions of the hydrogen atoms on C-1 were determined from the electron density about C-1, and not by calculation ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Tricarbonyl-bis(dimethylphosphino)ethane-thioformaldehyde-tungsten] ; _chemical_name_common ? _chemical_melting_point 74 _chemical_formula_moiety ? _chemical_formula_sum 'C10 H18 O3 P2 S W' _chemical_formula_weight 464.09 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' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'W' 'W' -0.8490 6.8722 '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 9.1843(5) _cell_length_b 12.4238(7) _cell_length_c 13.6206(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.4830(10) _cell_angle_gamma 90.00 _cell_volume 1554.11(15) _cell_formula_units_Z 4 _cell_measurement_temperature 130(2) _cell_measurement_reflns_used 6336 _cell_measurement_theta_min 2.685 _cell_measurement_theta_max 27.082 _exptl_crystal_description 'prism' _exptl_crystal_colour 'orange' _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.984 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 888 _exptl_absorpt_coefficient_mu 7.767 _exptl_absorpt_correction_type 'empirical' _exptl_absorpt_correction_T_min 0.5106 _exptl_absorpt_correction_T_max 0.5106 _exptl_absorpt_process_details 'empirical' _exptl_special_details ; ? ; _diffrn_ambient_temperature 130(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 'Bruker SMART Apex with D8-Goniometer' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0.2 _diffrn_standards_interval_time 5 _diffrn_standards_decay_% 0 _diffrn_reflns_number 25623 _diffrn_reflns_av_R_equivalents 0.0295 _diffrn_reflns_av_sigmaI/netI 0.0161 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.22 _diffrn_reflns_theta_max 27.11 _reflns_number_total 3414 _reflns_number_gt 3257 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Smart 5.622' _computing_cell_refinement 'Smart 5.620' _computing_data_reduction 'Saint Plus' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material 'shelxl-97' _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^)+(0.0222P)^2^+1.5144P] 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 3414 _refine_ls_number_parameters 166 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0205 _refine_ls_R_factor_gt 0.0189 _refine_ls_wR_factor_ref 0.0449 _refine_ls_wR_factor_gt 0.0444 _refine_ls_goodness_of_fit_ref 1.135 _refine_ls_restrained_S_all 1.135 _refine_ls_shift/su_max 0.001 _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 W1 W 0.017325(12) 0.676190(8) 0.269575(8) 0.01491(5) Uani 1 1 d . . . S1 S 0.21050(9) 0.59371(6) 0.16630(6) 0.02334(16) Uani 1 1 d . . . P1 P -0.10754(8) 0.76788(6) 0.40615(6) 0.01656(15) Uani 1 1 d . . . P2 P 0.22894(8) 0.73197(6) 0.37431(6) 0.01700(15) Uani 1 1 d . . . O1 O -0.0126(3) 0.45555(18) 0.38484(19) 0.0338(6) Uani 1 1 d . . . O2 O -0.3149(3) 0.6549(2) 0.20961(19) 0.0351(6) Uani 1 1 d . . . O3 O 0.0388(3) 0.90414(18) 0.16460(19) 0.0347(6) Uani 1 1 d . . . C1 C 0.0318(3) 0.5888(3) 0.1219(2) 0.0204(6) Uani 1 1 d . . . C2 C 0.1688(3) 0.8353(2) 0.4610(2) 0.0205(6) Uani 1 1 d . . . H2A H 0.2421 0.8437 0.5142 0.025 Uiso 1 1 calc R . . H2B H 0.1588 0.9052 0.4267 0.025 Uiso 1 1 calc R . . C3 C 0.0223(3) 0.8024(2) 0.5047(2) 0.0197(6) Uani 1 1 d . . . H3A H -0.0170 0.8625 0.5442 0.024 Uiso 1 1 calc R . . H3B H 0.0361 0.7396 0.5485 0.024 Uiso 1 1 calc R . . C4 C -0.1952(4) 0.8963(2) 0.3782(3) 0.0267(7) Uani 1 1 d . . . H4A H -0.2404 0.9249 0.4376 0.040 Uiso 1 1 calc R . . H4B H -0.2699 0.8855 0.3274 0.040 Uiso 1 1 calc R . . H4C H -0.1222 0.9474 0.3545 0.040 Uiso 1 1 calc R . . C5 C -0.2500(3) 0.6945(3) 0.4701(3) 0.0246(7) Uani 1 1 d . . . H5A H -0.2103 0.6269 0.4960 0.037 Uiso 1 1 calc R . . H5B H -0.3301 0.6787 0.4243 0.037 Uiso 1 1 calc R . . H5C H -0.2864 0.7383 0.5244 0.037 Uiso 1 1 calc R . . C6 C 0.3119(4) 0.6292(3) 0.4521(3) 0.0278(7) Uani 1 1 d . . . H6A H 0.3503 0.5712 0.4110 0.042 Uiso 1 1 calc R . . H6B H 0.2386 0.5999 0.4966 0.042 Uiso 1 1 calc R . . H6C H 0.3915 0.6612 0.4906 0.042 Uiso 1 1 calc R . . C7 C 0.3838(3) 0.7940(3) 0.3143(3) 0.0254(7) Uani 1 1 d . . . H7A H 0.4555 0.8164 0.3639 0.038 Uiso 1 1 calc R . . H7B H 0.3510 0.8571 0.2770 0.038 Uiso 1 1 calc R . . H7C H 0.4285 0.7421 0.2695 0.038 Uiso 1 1 calc R . . C11 C 0.0010(3) 0.5356(2) 0.3419(2) 0.0207(6) Uani 1 1 d . . . C12 C -0.1938(3) 0.6621(2) 0.2284(2) 0.0218(6) Uani 1 1 d . . . C13 C 0.0345(4) 0.8203(2) 0.2003(2) 0.0217(7) Uani 1 1 d . . . H1A H 0.011(4) 0.633(3) 0.070(3) 0.024(9) Uiso 1 1 d . . . H1B H -0.006(4) 0.531(3) 0.118(3) 0.028(10) Uiso 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 W1 0.01490(7) 0.01497(7) 0.01489(7) -0.00001(4) 0.00228(5) -0.00012(4) S1 0.0220(4) 0.0248(4) 0.0233(4) -0.0021(3) 0.0049(3) 0.0009(3) P1 0.0153(4) 0.0170(3) 0.0175(4) -0.0005(3) 0.0026(3) 0.0012(3) P2 0.0147(4) 0.0174(3) 0.0189(4) 0.0000(3) 0.0020(3) -0.0004(3) O1 0.0447(15) 0.0209(11) 0.0359(14) 0.0069(10) 0.0102(12) -0.0011(10) O2 0.0228(14) 0.0507(15) 0.0318(14) -0.0116(12) -0.0029(11) 0.0024(11) O3 0.0486(16) 0.0235(12) 0.0319(14) 0.0084(10) 0.0014(12) -0.0031(11) C1 0.0193(16) 0.0217(15) 0.0202(16) -0.0014(13) -0.0009(12) -0.0021(12) C2 0.0208(16) 0.0205(14) 0.0200(16) -0.0046(12) 0.0008(12) -0.0034(11) C3 0.0206(16) 0.0201(14) 0.0184(15) -0.0023(12) 0.0033(12) -0.0003(12) C4 0.0292(18) 0.0230(15) 0.0281(18) 0.0004(13) 0.0041(14) 0.0118(13) C5 0.0179(16) 0.0293(16) 0.0266(17) -0.0022(13) 0.0052(13) -0.0013(12) C6 0.0234(17) 0.0267(16) 0.0333(19) 0.0029(14) -0.0063(14) 0.0020(13) C7 0.0176(16) 0.0288(16) 0.0300(18) -0.0030(14) 0.0058(13) -0.0046(13) C11 0.0184(15) 0.0222(15) 0.0216(16) -0.0032(12) 0.0037(12) 0.0009(12) C12 0.0178(16) 0.0247(15) 0.0230(16) -0.0027(12) 0.0041(13) 0.0027(12) C13 0.0206(16) 0.0255(16) 0.0190(16) -0.0025(12) -0.0003(13) 0.0017(12) _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 W1 C11 2.011(3) . ? W1 C12 2.021(3) . ? W1 C13 2.031(3) . ? W1 C1 2.290(3) . ? W1 P1 2.4716(7) . ? W1 S1 2.4937(8) . ? W1 P2 2.4992(8) . ? S1 C1 1.745(3) . ? P1 C5 1.823(3) . ? P1 C4 1.826(3) . ? P1 C3 1.838(3) . ? P2 C7 1.818(3) . ? P2 C6 1.822(3) . ? P2 C2 1.833(3) . ? O1 C11 1.161(4) . ? O2 C12 1.142(4) . ? O3 C13 1.150(4) . ? C1 H1A 0.92(4) . ? C1 H1B 0.80(4) . ? C2 C3 1.532(4) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C5 H5C 0.9800 . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? 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 C11 W1 C12 89.18(13) . . ? C11 W1 C13 178.35(12) . . ? C12 W1 C13 91.45(13) . . ? C11 W1 C1 91.36(12) . . ? C12 W1 C1 77.18(12) . . ? C13 W1 C1 90.27(12) . . ? C11 W1 P1 89.69(9) . . ? C12 W1 P1 78.39(9) . . ? C13 W1 P1 88.94(9) . . ? C1 W1 P1 155.53(8) . . ? C11 W1 S1 88.61(9) . . ? C12 W1 S1 119.55(9) . . ? C13 W1 S1 92.41(9) . . ? C1 W1 S1 42.52(8) . . ? P1 W1 S1 161.94(3) . . ? C11 W1 P2 91.26(9) . . ? C12 W1 P2 157.20(9) . . ? C13 W1 P2 87.57(9) . . ? C1 W1 P2 125.59(8) . . ? P1 W1 P2 78.82(3) . . ? S1 W1 P2 83.25(3) . . ? C1 S1 W1 62.49(11) . . ? C5 P1 C4 102.70(16) . . ? C5 P1 C3 103.41(15) . . ? C4 P1 C3 103.32(15) . . ? C5 P1 W1 117.94(11) . . ? C4 P1 W1 116.88(11) . . ? C3 P1 W1 110.79(10) . . ? C7 P2 C6 103.52(16) . . ? C7 P2 C2 103.52(15) . . ? C6 P2 C2 104.05(16) . . ? C7 P2 W1 117.93(12) . . ? C6 P2 W1 117.20(11) . . ? C2 P2 W1 108.97(11) . . ? S1 C1 W1 74.99(12) . . ? S1 C1 H1A 116(2) . . ? W1 C1 H1A 113(2) . . ? S1 C1 H1B 117(3) . . ? W1 C1 H1B 117(3) . . ? H1A C1 H1B 113(3) . . ? C3 C2 P2 109.5(2) . . ? C3 C2 H2A 109.8 . . ? P2 C2 H2A 109.8 . . ? C3 C2 H2B 109.8 . . ? P2 C2 H2B 109.8 . . ? H2A C2 H2B 108.2 . . ? C2 C3 P1 110.2(2) . . ? C2 C3 H3A 109.6 . . ? P1 C3 H3A 109.6 . . ? C2 C3 H3B 109.6 . . ? P1 C3 H3B 109.6 . . ? H3A C3 H3B 108.1 . . ? P1 C4 H4A 109.5 . . ? P1 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? P1 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? P1 C5 H5A 109.5 . . ? P1 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? P1 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? P2 C6 H6A 109.5 . . ? P2 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? P2 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? P2 C7 H7A 109.5 . . ? P2 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? P2 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? O1 C11 W1 177.9(3) . . ? O2 C12 W1 176.8(3) . . ? O3 C13 W1 176.3(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 C11 W1 S1 C1 93.52(15) . . . . ? C12 W1 S1 C1 5.26(16) . . . . ? C13 W1 S1 C1 -87.78(16) . . . . ? P1 W1 S1 C1 178.26(14) . . . . ? P2 W1 S1 C1 -175.04(13) . . . . ? C11 W1 P1 C5 -35.11(16) . . . . ? C12 W1 P1 C5 54.12(16) . . . . ? C13 W1 P1 C5 145.82(16) . . . . ? C1 W1 P1 C5 57.5(3) . . . . ? S1 W1 P1 C5 -119.67(15) . . . . ? P2 W1 P1 C5 -126.45(13) . . . . ? C11 W1 P1 C4 -158.33(16) . . . . ? C12 W1 P1 C4 -69.11(16) . . . . ? C13 W1 P1 C4 22.59(16) . . . . ? C1 W1 P1 C4 -65.7(3) . . . . ? S1 W1 P1 C4 117.10(15) . . . . ? P2 W1 P1 C4 110.32(14) . . . . ? C11 W1 P1 C3 83.72(14) . . . . ? C12 W1 P1 C3 172.94(14) . . . . ? C13 W1 P1 C3 -95.36(14) . . . . ? C1 W1 P1 C3 176.3(2) . . . . ? S1 W1 P1 C3 -0.85(15) . . . . ? P2 W1 P1 C3 -7.63(11) . . . . ? C11 W1 P2 C7 136.43(15) . . . . ? C12 W1 P2 C7 -132.7(3) . . . . ? C13 W1 P2 C7 -44.74(15) . . . . ? C1 W1 P2 C7 43.85(17) . . . . ? P1 W1 P2 C7 -134.14(13) . . . . ? S1 W1 P2 C7 47.97(13) . . . . ? C11 W1 P2 C6 11.68(16) . . . . ? C12 W1 P2 C6 102.6(3) . . . . ? C13 W1 P2 C6 -169.49(16) . . . . ? C1 W1 P2 C6 -80.89(17) . . . . ? P1 W1 P2 C6 101.11(14) . . . . ? S1 W1 P2 C6 -76.77(13) . . . . ? C11 W1 P2 C2 -106.05(14) . . . . ? C12 W1 P2 C2 -15.2(3) . . . . ? C13 W1 P2 C2 72.78(14) . . . . ? C1 W1 P2 C2 161.37(15) . . . . ? P1 W1 P2 C2 -16.62(11) . . . . ? S1 W1 P2 C2 165.49(11) . . . . ? C11 W1 C1 S1 -86.46(13) . . . . ? C12 W1 C1 S1 -175.31(15) . . . . ? C13 W1 C1 S1 93.26(13) . . . . ? P1 W1 C1 S1 -178.70(11) . . . . ? P2 W1 C1 S1 6.06(16) . . . . ? C7 P2 C2 C3 170.2(2) . . . . ? C6 P2 C2 C3 -81.9(2) . . . . ? W1 P2 C2 C3 43.9(2) . . . . ? P2 C2 C3 P1 -51.4(3) . . . . ? C5 P1 C3 C2 163.6(2) . . . . ? C4 P1 C3 C2 -89.6(2) . . . . ? W1 P1 C3 C2 36.3(2) . . . . ? C12 W1 C11 O1 -45(8) . . . . ? C13 W1 C11 O1 68(10) . . . . ? C1 W1 C11 O1 -122(8) . . . . ? P1 W1 C11 O1 34(8) . . . . ? S1 W1 C11 O1 -164(8) . . . . ? P2 W1 C11 O1 113(8) . . . . ? C11 W1 C12 O2 68(5) . . . . ? C13 W1 C12 O2 -110(5) . . . . ? C1 W1 C12 O2 160(5) . . . . ? P1 W1 C12 O2 -21(5) . . . . ? S1 W1 C12 O2 156(5) . . . . ? P2 W1 C12 O2 -23(5) . . . . ? C11 W1 C13 O3 -48(8) . . . . ? C12 W1 C13 O3 64(5) . . . . ? C1 W1 C13 O3 142(5) . . . . ? P1 W1 C13 O3 -14(5) . . . . ? S1 W1 C13 O3 -176(5) . . . . ? P2 W1 C13 O3 -93(5) . . . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.11 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 1.304 _refine_diff_density_min -0.431 _refine_diff_density_rms 0.117