# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2002 data_global _audit_creation_date 02-07-25 _audit_creation_method CRYSTALS _publ_contact_letter ; These are the CIF format data (1 compound) for the paper "Synthesis and reactivity of the imidotungsten methyl cation [W(N2Npy)(NPh)Me]+: CO2 adds to the W=NPh bond and does not insert into the W-Me bond" B D Ward, E Clot, S Dubberley, L H Gade and P. Mountford ; _publ_contact_author ; Dr P. Mountford Inorganic Chemistry Laboratory South Parks Road Oxford OX1 3QR UK ; _publ_contact_author_phone '+44 1865 272679 _contact_author_fax '+44 1865 272690' _publ_contact_author_email Philip.Mountford@chem.ox.ac.uk data_COMPOUND_2 # Local code BDW5 _chemical_name_systematic ; [W{(2-C5NH4)C(Me)(CH2NSiMe3)2}(NPh)Me2] ; _publ_section_exptl_refinement ; No special details ; _cell_length_a 10.6452(2) _cell_length_b 16.4633(3) _cell_length_c 15.2794(2) _cell_angle_alpha 90.00 _cell_angle_beta 91.659(1) _cell_angle_gamma 90.00 _cell_volume 2676.67(8) _symmetry_cell_setting 'Monoclinic ' _symmetry_space_group_name_H-M 'P 1 21/n 1 ' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' '-x,-y,-z' '-x+1/2,y+1/2,-z+1/2' 'x+1/2,-y+1/2,z+1/2' loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source 'C ' 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International_Tables_Vol_IV_Table_2.2B' 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 'International_Tables_Vol_IV_Table_2.2B' 'N ' 0.0040 0.0030 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International_Tables_Vol_IV_Table_2.2B' 'W ' -1.4210 6.8720 29.0818 1.7203 15.4300 9.2259 14.4327 0.3217 5.1198 57.0560 9.8875 'International_Tables_Vol_IV_Table_2.2B' 'Si ' 0.0720 0.0710 6.2915 2.4386 3.0353 32.3337 1.9891 0.6785 1.5410 81.6937 1.1407 'International_Tables_Vol_IV_Table_2.2B' _chemical_formula_sum ' C23 H40 N4 Si2 W1 ' _chemical_formula_moiety ' C23 H40 N4 Si2 W1 ' _chemical_compound_source ; ? ; _chemical_formula_weight 612.62 _cell_measurement_temperature 150 _cell_measurement_reflns_used 6261 _cell_measurement_theta_min 2.910 _cell_measurement_theta_max 27.485 _cell_formula_units_Z 4 _exptl_crystal_description 'block ' _exptl_crystal_colour 'dark red' _exptl_crystal_size_min 0.10 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_max 0.30 _exptl_crystal_density_diffrn 1.52 _exptl_crystal_density_method none _exptl_crystal_density_meas 'not measured' _exptl_crystal_F_000 1227.09 _exptl_absorpt_coefficient_mu 4.42 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.413 _exptl_absorpt_correction_T_max 0.643 _diffrn_ambient_temperature 150 _diffrn_standards_interval_time 'not measured' _diffrn_standards_interval_count 'not measured' _diffrn_standards_number 'not measured' _diffrn_standards_decay_% 'not measured' _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method 'CCD' _diffrn_reflns_number 12044 _reflns_number_total 6111 _diffrn_reflns_av_R_equivalents 0.01 _reflns_number_gt 4338 _diffrn_reflns_theta_min 2.91 _diffrn_reflns_theta_max 27.47 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _reflns_limit_h_min -13 _reflns_limit_h_max 13 _reflns_limit_k_min 0 _reflns_limit_k_max 21 _reflns_limit_l_min 0 _reflns_limit_l_max 19 _refine_diff_density_min -0.60 _refine_diff_density_max 1.19 _reflns_threshold_expression >3.00\s(I) _refine_ls_number_reflns 4338 _refine_ls_number_parameters 272 _refine_ls_R_factor_gt 0.0227 _refine_ls_wR_factor_ref 0.0106 _refine_ls_goodness_of_fit_ref 1.2430 _refine_ls_shift/su_max 0.01 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme 'Chebychev polynomial' _refine_ls_weighting_details ; Chebychev polynomial with 2 parameters, Carruthers & Watkin , 1979, 0.828E-01-.519 ; _refine_ls_hydrogen_treatment 'riding model' _atom_sites_solution_primary 'direct methods' _atom_sites_solution_hydrogens geometric _refine_ls_matrix_type full _refine_ls_number_restraints 0 _refine_ls_abs_structure_flack none _refine_ls_extinction_coef 71.1(39) _refine_ls_extinction_method 'Larson 1970 Crystallographic Computing eq 22' _computing_data_collection ; KappaCCD software 'Collect' (Nonius, 2000) ; _computing_data_reduction ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_cell_refinement ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_structure_solution 'SIR92 (Altomare, et al., 1994)' _computing_structure_refinement ; CRYSTALS Issue 10 (Watkin et al., 1996) ; _computing_molecular_graphics 'CAMERON (Watkin, Prout and Pearce, 1996)' _computing_publication_material ; CRYSTALS Issue 10 (Watkin et al., 1996) ; loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type W1 0.237863(6) 0.247246(7) 0.386340(4) 0.0172 1.0000 Uani N1 0.10629(18) 0.30981(11) 0.39420(12) 0.0216 1.0000 Uani N2 0.22724(17) 0.1635(1) 0.48039(11) 0.0207 1.0000 Uani N3 0.19528(16) 0.15889(11) 0.2965(1) 0.0201 1.0000 Uani N4 0.43910(17) 0.19381(11) 0.37012(11) 0.0222 1.0000 Uani Si1 0.11065(6) 0.16617(4) 0.56007(4) 0.0261 1.0000 Uani Si2 0.10304(5) 0.16757(4) 0.20055(4) 0.0227 1.0000 Uani C1 0.0234(2) 0.37564(12) 0.39351(13) 0.0197 1.0000 Uani C2 0.0675(2) 0.45246(14) 0.37170(16) 0.0290 1.0000 Uani C3 -0.0154(3) 0.51753(15) 0.36860(17) 0.0368 1.0000 Uani C4 -0.1399(3) 0.50687(15) 0.38618(18) 0.0356 1.0000 Uani C5 -0.1836(2) 0.43054(16) 0.40947(18) 0.0346 1.0000 Uani C6 -0.1028(2) 0.36493(15) 0.41378(15) 0.0290 1.0000 Uani C7 0.3051(2) 0.32113(13) 0.27299(13) 0.0269 1.0000 Uani C8 0.3512(2) 0.32977(14) 0.47298(14) 0.0273 1.0000 Uani C9 0.53839(19) 0.2426(2) 0.35656(12) 0.0285 1.0000 Uani C10 0.6569(2) 0.21364(17) 0.33946(16) 0.0336 1.0000 Uani C11 0.6748(2) 0.13045(19) 0.33521(18) 0.0391 1.0000 Uani C12 0.5740(2) 0.07971(17) 0.35014(15) 0.0307 1.0000 Uani C13 0.4563(2) 0.11259(13) 0.36734(14) 0.0225 1.0000 Uani C14 0.3419(2) 0.06276(14) 0.38534(14) 0.0252 1.0000 Uani C15 0.3715(2) -0.02865(14) 0.38796(17) 0.0310 1.0000 Uani C16 0.2926(2) 0.08577(13) 0.47581(15) 0.0248 1.0000 Uani C17 0.2401(2) 0.07519(12) 0.31209(15) 0.0264 1.0000 Uani C18 -0.0387(3) 0.12820(18) 0.5087(2) 0.0512 1.0000 Uani C19 0.0881(2) 0.26955(13) 0.60582(15) 0.0309 1.0000 Uani C20 0.1575(3) 0.09837(17) 0.65424(19) 0.0498 1.0000 Uani C21 0.0135(3) 0.07131(16) 0.18181(18) 0.0399 1.0000 Uani C22 -0.01582(17) 0.2509(2) 0.20680(13) 0.0302 1.0000 Uani C23 0.2017(2) 0.18346(19) 0.10303(15) 0.0383 1.0000 Uani H21 0.1582 0.46038 0.35847 0.0360 1.0000 Uiso H31 0.0163 0.57277 0.35333 0.0442 1.0000 Uiso H41 -0.1992 0.55392 0.38250 0.0433 1.0000 Uiso H51 -0.2743 0.42279 0.42274 0.0410 1.0000 Uiso H61 -0.1339 0.31020 0.43150 0.0358 1.0000 Uiso H71 0.3860 0.29812 0.25228 0.0351 1.0000 Uiso H72 0.3188 0.37871 0.29208 0.0351 1.0000 Uiso H73 0.2406 0.31964 0.22411 0.0351 1.0000 Uiso H81 0.4380 0.30757 0.48086 0.0354 1.0000 Uiso H82 0.3110 0.33390 0.53118 0.0354 1.0000 Uiso H83 0.3548 0.38488 0.44561 0.0354 1.0000 Uiso H91 0.52550 0.3027 0.35899 0.0351 1.0000 Uiso H101 0.7286 0.25165 0.33032 0.0433 1.0000 Uiso H111 0.7589 0.10737 0.32158 0.0461 1.0000 Uiso H121 0.5851 0.01941 0.34874 0.0375 1.0000 Uiso H151 0.2930 -0.05954 0.40021 0.0395 1.0000 Uiso H152 0.4362 -0.03974 0.43521 0.0395 1.0000 Uiso H153 0.4043 -0.04614 0.33025 0.0395 1.0000 Uiso H161 0.3661 0.08748 0.51811 0.0315 1.0000 Uiso H162 0.2330 0.04232 0.49377 0.0315 1.0000 Uiso H171 0.1656 0.04149 0.32722 0.0338 1.0000 Uiso H172 0.2755 0.05497 0.25623 0.0338 1.0000 Uiso H181 -0.1069 0.12886 0.5523 0.0621 1.0000 Uiso H182 -0.0261 0.07141 0.4875 0.0621 1.0000 Uiso H183 -0.0628 0.16398 0.4581 0.0621 1.0000 Uiso H191 0.0213 0.26798 0.65049 0.0391 1.0000 Uiso H192 0.1688 0.28862 0.63397 0.0391 1.0000 Uiso H193 0.0623 0.30770 0.55764 0.0391 1.0000 Uiso H201 0.0914 0.09979 0.69937 0.0624 1.0000 Uiso H202 0.2390 0.11798 0.68071 0.0624 1.0000 Uiso H203 0.1678 0.04143 0.63281 0.0624 1.0000 Uiso H211 -0.0395 0.07617 0.12696 0.0498 1.0000 Uiso H212 -0.0416 0.06100 0.23253 0.0498 1.0000 Uiso H213 0.0738 0.02518 0.17591 0.0498 1.0000 Uiso H221 -0.06626 0.2536 0.15063 0.0383 1.0000 Uiso H222 0.02826 0.3039 0.21699 0.0383 1.0000 Uiso H223 -0.07292 0.2399 0.25625 0.0383 1.0000 Uiso H231 0.1464 0.18826 0.04929 0.0490 1.0000 Uiso H232 0.2518 0.23447 0.11104 0.0490 1.0000 Uiso H233 0.2601 0.13635 0.09659 0.0490 1.0000 Uiso 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 0.01658(4) 0.01740(4) 0.01751(4) 0.00054(6) 0.000983(19) 0.00129(6) N1 0.0221(8) 0.0223(8) 0.0206(8) 0.0010(7) 0.0023(6) -0.0004(7) N2 0.0235(8) 0.0190(7) 0.0198(8) 0.0007(7) 0.0024(6) 0.0032(7) N3 0.0200(8) 0.0198(8) 0.0203(8) 0.0018(6) -0.0034(6) 0.0015(7) N4 0.0207(8) 0.0258(8) 0.0201(8) -0.0010(6) 0.0001(6) 0.0017(7) Si1 0.0273(3) 0.0225(3) 0.0289(3) 0.0032(2) 0.0085(2) 0.0017(2) Si2 0.0199(3) 0.0275(3) 0.0206(3) -0.0017(2) -0.0020(2) 0.0025(2) C1 0.022(1) 0.0213(9) 0.0157(9) -0.0007(7) 0.0001(7) 0.0054(8) C2 0.0304(12) 0.022(1) 0.0352(12) 0.0009(9) 0.0041(9) 0.0022(9) C3 0.0456(14) 0.0251(11) 0.0401(14) 0.006(1) 0.0059(11) 0.008(1) C4 0.0372(12) 0.0307(11) 0.0390(13) -0.0014(9) 0.001(1) 0.016(1) C5 0.0253(11) 0.0388(14) 0.0400(14) -0.003(1) 0.006(1) 0.011(1) C6 0.0279(12) 0.0266(11) 0.0327(12) -0.0008(9) 0.0061(9) 0.0027(9) C7 0.029(1) 0.0295(11) 0.0225(11) 0.0066(8) 0.0088(9) -0.0038(9) C8 0.0306(11) 0.025(1) 0.026(1) -0.0091(9) -0.0018(9) -0.0038(9) C9 0.0254(9) 0.0364(14) 0.0238(8) -0.0019(12) 0.0000(7) -0.0022(12) C10 0.023(1) 0.0483(13) 0.0295(12) -0.0028(11) 0.0009(8) -0.005(1) C11 0.0226(11) 0.0601(17) 0.0348(13) -0.0015(13) 0.0032(9) 0.0107(12) C12 0.0271(11) 0.0388(12) 0.0262(11) -0.001(1) 0.0010(9) 0.008(1) C13 0.0201(11) 0.0284(11) 0.0188(9) -0.0001(8) -0.0031(7) 0.0039(9) C14 0.021(1) 0.0264(11) 0.0278(11) -0.0002(8) -0.0025(8) 0.0037(8) C15 0.0300(11) 0.025(1) 0.0384(12) -0.0023(9) -0.0033(9) 0.0077(9) C16 0.027(1) 0.0220(9) 0.026(1) 0.0048(9) 0.0038(8) 0.0054(9) C17 0.0289(11) 0.0185(9) 0.0314(11) -0.0030(8) -0.0064(9) 0.0020(9) C18 0.0275(12) 0.0395(14) 0.087(2) -0.0110(15) 0.0138(14) -0.0046(11) C19 0.0380(11) 0.0303(13) 0.0253(9) -0.0002(8) 0.0124(8) 0.0036(8) C20 0.074(2) 0.0412(14) 0.0360(14) 0.0159(11) 0.0269(14) 0.0150(14) C21 0.0412(15) 0.0369(14) 0.0404(15) -0.000(1) -0.0163(12) -0.0017(11) C22 0.0246(8) 0.0355(9) 0.0302(8) -0.0046(18) -0.0066(7) 0.0095(17) C23 0.0263(12) 0.0690(18) 0.020(1) -0.0032(11) 0.0015(9) 0.0008(12) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag W1 . N1 . 1.7455(18) yes W1 . N2 . 1.9968(17) yes W1 . N3 . 2.0416(17) yes W1 . N4 . 2.3357(18) yes W1 . C7 . 2.250(2) yes W1 . C8 . 2.228(2) yes N1 . C1 . 1.397(3) yes N2 . Si1 . 1.7641(18) yes N2 . C16 . 1.460(3) yes N3 . Si2 . 1.7471(17) yes N3 . C17 . 1.475(3) yes N4 . C9 . 1.348(3) yes N4 . C13 . 1.350(3) yes Si1 . C18 . 1.860(3) yes Si1 . C19 . 1.858(2) yes Si1 . C20 . 1.877(3) yes Si2 . C21 . 1.867(3) yes Si2 . C22 . 1.871(3) yes Si2 . C23 . 1.866(3) yes C1 . C2 . 1.393(3) yes C1 . C6 . 1.399(3) yes C2 . C3 . 1.388(3) yes C3 . C4 . 1.371(4) yes C4 . C5 . 1.390(4) yes C5 . C6 . 1.382(3) yes C9 . C10 . 1.380(3) yes C10 . C11 . 1.385(4) yes C11 . C12 . 1.384(4) yes C12 . C13 . 1.397(3) yes C13 . C14 . 1.500(3) yes C14 . C15 . 1.538(3) yes C14 . C16 . 1.540(3) yes C14 . C17 . 1.549(3) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . W1 . N2 . 107.19(8) yes N1 . W1 . N3 . 107.68(8) yes N2 . W1 . N3 . 88.61(7) yes N1 . W1 . N4 . 165.89(7) yes N2 . W1 . N4 . 83.55(7) yes N3 . W1 . N4 . 81.19(7) yes N1 . W1 . C7 . 90.45(8) yes N2 . W1 . C7 . 162.36(8) yes N3 . W1 . C7 . 86.40(7) yes N4 . W1 . C7 . 78.97(7) yes N1 . W1 . C8 . 91.21(9) yes N2 . W1 . C8 . 91.97(8) yes N3 . W1 . C8 . 160.03(8) yes N4 . W1 . C8 . 79.05(8) yes C7 . W1 . C8 . 87.06(8) yes W1 . N1 . C1 . 164.76(16) yes W1 . N2 . Si1 . 122.36(9) yes W1 . N2 . C16 . 122.26(14) yes Si1 . N2 . C16 . 113.63(14) yes W1 . N3 . Si2 . 127.9(1) yes W1 . N3 . C17 . 119.53(13) yes Si2 . N3 . C17 . 112.51(13) yes W1 . N4 . C9 . 121.17(17) yes W1 . N4 . C13 . 120.13(15) yes C9 . N4 . C13 . 118.5(2) yes N2 . Si1 . C18 . 108.08(12) yes N2 . Si1 . C19 . 112.5(1) yes C18 . Si1 . C19 . 110.39(12) yes N2 . Si1 . C20 . 109.72(11) yes C18 . Si1 . C20 . 109.17(16) yes C19 . Si1 . C20 . 106.90(13) yes N3 . Si2 . C21 . 109.4(1) yes N3 . Si2 . C22 . 112.43(9) yes C21 . Si2 . C22 . 106.69(12) yes N3 . Si2 . C23 . 111.5(1) yes C21 . Si2 . C23 . 107.06(13) yes C22 . Si2 . C23 . 109.58(12) yes N1 . C1 . C2 . 119.29(18) yes N1 . C1 . C6 . 120.7(2) yes C2 . C1 . C6 . 120.0(2) yes C1 . C2 . C3 . 119.4(2) yes C2 . C3 . C4 . 120.8(2) yes C3 . C4 . C5 . 119.9(2) yes C4 . C5 . C6 . 120.4(2) yes C1 . C6 . C5 . 119.5(2) yes N4 . C9 . C10 . 123.3(3) yes C9 . C10 . C11 . 118.6(3) yes C10 . C11 . C12 . 118.7(2) yes C11 . C12 . C13 . 120.1(2) yes N4 . C13 . C12 . 120.8(2) yes N4 . C13 . C14 . 115.09(18) yes C12 . C13 . C14 . 124.1(2) yes C13 . C14 . C15 . 111.91(18) yes C13 . C14 . C16 . 109.23(18) yes C15 . C14 . C16 . 106.99(18) yes C13 . C14 . C17 . 110.49(18) yes C15 . C14 . C17 . 106.66(18) yes C16 . C14 . C17 . 111.52(17) yes N2 . C16 . C14 . 115.72(18) yes N3 . C17 . C14 . 117.14(17) yes