Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2002 data_1a _database_code_CSD 190033 _journal_coden_Cambridge 182 loop_ _publ_author_name 'Nathalie Merceron' 'Antoine Baceiredo' 'Heinz Gornitzka' 'Guy Bertrand' _publ_contact_author_name 'Prof Guy Bertrand' _publ_contact_author_address ; Chemistry UCRiverside UCR/CNRS Joint Laboratory Riverside CA 92521-0403 UNITED STATES OF AMERICA ; _publ_contact_author_email 'GBERTRAN@MAIL.UCR.EDU' _publ_requested_journal 'Chemical Communications' _publ_section_title ; C-Phosphanyl-C-chloroiminium salts as masked electrophilc Carbenes ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C17 H36 Cl3 F3 N3 O3 P S' _chemical_formula_weight 556.87 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' 'F' 'F' 0.0171 0.0103 '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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Fdd2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'x+1/4, -y+1/4, z+1/4' '-x+1/4, y+1/4, z+1/4' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' 'x+1/4, -y+3/4, z+3/4' '-x+1/4, y+3/4, z+3/4' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' 'x+3/4, -y+1/4, z+3/4' '-x+3/4, y+1/4, z+3/4' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' 'x+3/4, -y+3/4, z+1/4' '-x+3/4, y+3/4, z+1/4' _cell_length_a 22.8346(14) _cell_length_b 58.461(3) _cell_length_c 8.0890(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 10798.3(11) _cell_formula_units_Z 16 _cell_measurement_temperature 193(2) _cell_measurement_reflns_used 6574 _cell_measurement_theta_min 2.263 _cell_measurement_theta_max 29.097 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.1 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.6 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.370 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4672 _exptl_absorpt_coefficient_mu 0.519 _exptl_absorpt_correction_type 'semi-empirical' _exptl_absorpt_correction_T_min 0.572921 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details 'SADABS (Bruker-AXS)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 193(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 '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_% ? _diffrn_reflns_number 32802 _diffrn_reflns_av_R_equivalents 0.0512 _diffrn_reflns_av_sigmaI/netI 0.0309 _diffrn_reflns_limit_h_min -28 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min -72 _diffrn_reflns_limit_k_max 72 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 1.39 _diffrn_reflns_theta_max 26.37 _reflns_number_total 5505 _reflns_number_gt 4806 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0700P)^2^+0.0000P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.02(6) _refine_ls_number_reflns 5505 _refine_ls_number_parameters 307 _refine_ls_number_restraints 43 _refine_ls_R_factor_all 0.0481 _refine_ls_R_factor_gt 0.0399 _refine_ls_wR_factor_ref 0.1000 _refine_ls_wR_factor_gt 0.0960 _refine_ls_goodness_of_fit_ref 1.014 _refine_ls_restrained_S_all 1.012 _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 C1 C 0.93826(11) 0.19788(4) 1.0538(3) 0.0282(5) Uani 1 1 d . . . Cl1 Cl 0.99986(3) 0.182457(10) 1.00458(9) 0.03712(16) Uani 1 1 d . . . N1 N 0.94656(10) 0.21874(3) 1.0991(3) 0.0321(5) Uani 1 1 d . . . C2 C 0.89854(13) 0.23256(4) 1.1703(4) 0.0411(7) Uani 1 1 d . . . H2A H 0.8641 0.2228 1.1875 0.062 Uiso 1 1 calc R . . H2B H 0.8886 0.2450 1.0942 0.062 Uiso 1 1 calc R . . H2C H 0.9111 0.2390 1.2764 0.062 Uiso 1 1 calc R . . C3 C 1.00398(13) 0.23055(4) 1.0890(4) 0.0410(7) Uani 1 1 d . . . H3A H 1.0313 0.2236 1.1678 0.061 Uiso 1 1 calc R . . H3B H 0.9989 0.2468 1.1157 0.061 Uiso 1 1 calc R . . H3C H 1.0197 0.2291 0.9767 0.061 Uiso 1 1 calc R . . P1 P 0.86481(3) 0.182987(10) 1.06215(8) 0.02670(15) Uani 1 1 d . . . N2 N 0.88066(8) 0.15536(3) 1.0306(3) 0.0272(4) Uani 1 1 d . . . C4 C 0.87239(12) 0.13948(4) 1.1734(4) 0.0337(6) Uani 1 1 d . . . H4 H 0.8746 0.1236 1.1277 0.040 Uiso 1 1 calc R . . C5 C 0.81295(13) 0.14162(5) 1.2556(4) 0.0436(7) Uani 1 1 d . . . H5A H 0.8095 0.1567 1.3076 0.065 Uiso 1 1 calc R . . H5B H 0.8088 0.1297 1.3399 0.065 Uiso 1 1 calc R . . H5C H 0.7821 0.1398 1.1723 0.065 Uiso 1 1 calc R . . C6 C 0.92233(13) 0.14168(5) 1.2986(4) 0.0462(7) Uani 1 1 d . . . H6A H 0.9598 0.1387 1.2435 0.069 Uiso 1 1 calc R . . H6B H 0.9166 0.1306 1.3880 0.069 Uiso 1 1 calc R . . H6C H 0.9226 0.1572 1.3446 0.069 Uiso 1 1 calc R . . C7 C 0.89672(11) 0.14487(4) 0.8694(3) 0.0299(5) Uani 1 1 d . . . H7 H 0.9059 0.1576 0.7906 0.036 Uiso 1 1 calc R . . C8 C 0.95071(12) 0.12935(5) 0.8794(4) 0.0409(7) Uani 1 1 d . . . H8A H 0.9835 0.1379 0.9275 0.061 Uiso 1 1 calc R . . H8B H 0.9613 0.1241 0.7682 0.061 Uiso 1 1 calc R . . H8C H 0.9419 0.1161 0.9491 0.061 Uiso 1 1 calc R . . C9 C 0.84512(12) 0.13129(5) 0.7978(4) 0.0426(7) Uani 1 1 d . . . H9A H 0.8368 0.1181 0.8690 0.064 Uiso 1 1 calc R . . H9B H 0.8551 0.1259 0.6865 0.064 Uiso 1 1 calc R . . H9C H 0.8105 0.1411 0.7923 0.064 Uiso 1 1 calc R . . N3 N 0.83748(8) 0.19543(3) 0.8916(3) 0.0304(5) Uani 1 1 d DU A . C10 C 0.77291(11) 0.20082(5) 0.8915(4) 0.0428(7) Uani 1 1 d DU . . H10A H 0.7640 0.2043 0.7731 0.051 Uiso 0.40(4) 1 calc PR A 1 H10B H 0.7638 0.2098 0.7895 0.051 Uiso 0.60(4) 1 calc PR A 2 C11 C 0.7332(10) 0.1810(3) 0.932(4) 0.048(5) Uani 0.40(4) 1 d PDU A 1 H11A H 0.7469 0.1673 0.8744 0.072 Uiso 0.40(4) 1 calc PR A 1 H11B H 0.6932 0.1845 0.8970 0.072 Uiso 0.40(4) 1 calc PR A 1 H11C H 0.7337 0.1782 1.0518 0.072 Uiso 0.40(4) 1 calc PR A 1 C12 C 0.7564(7) 0.2223(3) 0.982(4) 0.064(6) Uani 0.40(4) 1 d PDU A 1 H12A H 0.7820 0.2348 0.9461 0.096 Uiso 0.40(4) 1 calc PR A 1 H12B H 0.7608 0.2199 1.1009 0.096 Uiso 0.40(4) 1 calc PR A 1 H12C H 0.7156 0.2262 0.9568 0.096 Uiso 0.40(4) 1 calc PR A 1 C11' C 0.7370(6) 0.1791(2) 0.888(3) 0.046(3) Uani 0.60(4) 1 d PDU A 2 H11D H 0.7490 0.1697 0.7943 0.069 Uiso 0.60(4) 1 calc PR A 2 H11E H 0.6954 0.1830 0.8779 0.069 Uiso 0.60(4) 1 calc PR A 2 H11F H 0.7433 0.1706 0.9913 0.069 Uiso 0.60(4) 1 calc PR A 2 C12' C 0.7558(5) 0.2153(3) 1.043(2) 0.066(3) Uani 0.60(4) 1 d PDU A 2 H12D H 0.7785 0.2295 1.0434 0.099 Uiso 0.60(4) 1 calc PR A 2 H12E H 0.7640 0.2066 1.1442 0.099 Uiso 0.60(4) 1 calc PR A 2 H12F H 0.7139 0.2189 1.0379 0.099 Uiso 0.60(4) 1 calc PR A 2 C13 C 0.87037(11) 0.20160(4) 0.7401(3) 0.0319(5) Uani 1 1 d D . . H13 H 0.9114 0.1960 0.7556 0.038 Uiso 1 1 calc R A . C14 C 0.84637(14) 0.18995(5) 0.5840(4) 0.0431(7) Uani 1 1 d D A . H14A H 0.8394 0.1737 0.6068 0.065 Uiso 1 1 calc R . . H14B H 0.8749 0.1914 0.4942 0.065 Uiso 1 1 calc R . . H14C H 0.8095 0.1973 0.5516 0.065 Uiso 1 1 calc R . . C15 C 0.87377(14) 0.22760(5) 0.7146(4) 0.0458(7) Uani 1 1 d D A . H15A H 0.8343 0.2337 0.6979 0.069 Uiso 1 1 calc R . . H15B H 0.8979 0.2309 0.6173 0.069 Uiso 1 1 calc R . . H15C H 0.8914 0.2347 0.8124 0.069 Uiso 1 1 calc R . . S1 S 0.04156(3) 0.206523(11) 0.51962(9) 0.03654(16) Uani 1 1 d . . . O1 O 0.09046(10) 0.21492(4) 0.4258(4) 0.0577(6) Uani 1 1 d . . . O2 O -0.01403(9) 0.20809(4) 0.4360(3) 0.0488(5) Uani 1 1 d . . . O3 O 0.04111(12) 0.21341(4) 0.6890(3) 0.0578(6) Uani 1 1 d . . . C16 C 0.05383(12) 0.17567(5) 0.5294(4) 0.0400(6) Uani 1 1 d . . . F1 F 0.00857(9) 0.16507(3) 0.6016(3) 0.0595(5) Uani 1 1 d . . . F2 F 0.10184(10) 0.17053(3) 0.6152(3) 0.0684(6) Uani 1 1 d . . . F3 F 0.06059(10) 0.16666(3) 0.3809(3) 0.0606(5) Uani 1 1 d . . . C17 C 0.6479(2) 0.20546(9) 0.4848(9) 0.1010(18) Uani 1 1 d U . . H17A H 0.6304 0.2068 0.5964 0.121 Uiso 1 1 calc R . . H17B H 0.6160 0.2072 0.4030 0.121 Uiso 1 1 calc R . . Cl2 Cl 0.69822(5) 0.227595(18) 0.45695(18) 0.0823(3) Uani 1 1 d U . . Cl3 Cl 0.67774(7) 0.17879(2) 0.4645(2) 0.1169(6) Uani 1 1 d U . . 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 0.0292(12) 0.0296(11) 0.0257(13) 0.0024(10) -0.0028(10) -0.0034(9) Cl1 0.0266(3) 0.0375(3) 0.0472(4) 0.0001(3) -0.0001(3) -0.0040(2) N1 0.0384(12) 0.0286(10) 0.0295(12) 0.0023(8) -0.0053(9) -0.0088(9) C2 0.0496(17) 0.0286(12) 0.0451(18) -0.0062(12) 0.0024(14) -0.0003(11) C3 0.0455(16) 0.0330(12) 0.0443(17) 0.0004(12) -0.0043(13) -0.0181(11) P1 0.0250(3) 0.0258(3) 0.0292(3) -0.0014(2) 0.0015(3) -0.0017(2) N2 0.0251(10) 0.0249(9) 0.0316(12) -0.0002(8) -0.0014(9) -0.0019(7) C4 0.0370(14) 0.0279(12) 0.0362(15) 0.0034(10) 0.0023(11) -0.0048(10) C5 0.0383(15) 0.0441(14) 0.0483(18) 0.0040(13) 0.0108(14) -0.0104(12) C6 0.0418(16) 0.0551(16) 0.0416(18) 0.0138(14) -0.0056(14) 0.0023(13) C7 0.0285(13) 0.0295(11) 0.0318(13) -0.0013(10) 0.0006(11) 0.0019(10) C8 0.0339(15) 0.0336(13) 0.0552(19) -0.0016(12) 0.0033(13) 0.0065(11) C9 0.0369(14) 0.0402(13) 0.0506(19) -0.0136(13) -0.0044(13) -0.0041(11) N3 0.0203(10) 0.0334(10) 0.0375(12) 0.0021(9) -0.0012(9) 0.0043(8) C10 0.0219(13) 0.0504(15) 0.0562(19) 0.0034(14) -0.0015(13) 0.0106(11) C11 0.027(6) 0.054(6) 0.063(13) -0.016(6) 0.017(6) 0.003(4) C12 0.033(5) 0.042(6) 0.117(14) -0.015(7) -0.012(7) 0.028(5) C11' 0.012(3) 0.065(5) 0.062(9) -0.010(4) 0.004(4) 0.005(3) C12' 0.043(4) 0.051(5) 0.104(8) -0.012(5) 0.002(5) 0.024(4) C13 0.0270(12) 0.0365(12) 0.0324(14) 0.0051(11) -0.0029(11) 0.0010(10) C14 0.0419(15) 0.0528(16) 0.0345(16) 0.0014(13) -0.0073(13) -0.0008(12) C15 0.0493(17) 0.0387(14) 0.0492(19) 0.0101(13) 0.0009(15) 0.0019(12) S1 0.0387(3) 0.0324(3) 0.0386(4) 0.0038(3) -0.0031(3) -0.0004(3) O1 0.0438(13) 0.0525(12) 0.0768(18) 0.0159(12) 0.0006(12) -0.0126(10) O2 0.0357(11) 0.0587(12) 0.0519(13) 0.0093(10) -0.0024(10) 0.0059(9) O3 0.0904(18) 0.0411(11) 0.0420(13) -0.0009(10) -0.0091(13) 0.0017(11) C16 0.0389(16) 0.0349(12) 0.0461(18) 0.0037(12) -0.0034(14) -0.0012(10) F1 0.0709(13) 0.0434(9) 0.0641(13) 0.0041(9) 0.0146(11) -0.0150(9) F2 0.0654(13) 0.0561(11) 0.0836(16) 0.0095(11) -0.0258(12) 0.0167(9) F3 0.0790(14) 0.0499(10) 0.0530(12) -0.0122(9) 0.0062(10) 0.0096(9) C17 0.051(2) 0.112(4) 0.141(5) 0.013(4) -0.014(3) -0.008(2) Cl2 0.0831(7) 0.0610(5) 0.1027(9) -0.0219(6) -0.0032(7) 0.0042(5) Cl3 0.1314(12) 0.0630(6) 0.1564(15) 0.0206(7) -0.0824(11) -0.0113(7) _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 N1 1.287(3) . ? C1 Cl1 1.718(3) . ? C1 P1 1.891(2) . ? N1 C2 1.479(4) . ? N1 C3 1.484(3) . ? P1 N2 1.6745(19) . ? P1 N3 1.680(2) . ? N2 C7 1.487(3) . ? N2 C4 1.494(3) . ? C4 C5 1.516(4) . ? C4 C6 1.531(4) . ? C7 C8 1.533(4) . ? C7 C9 1.534(4) . ? N3 C13 1.482(3) . ? N3 C10 1.508(3) . ? C10 C12 1.500(10) . ? C10 C11 1.509(12) . ? C10 C11' 1.510(8) . ? C10 C12' 1.539(9) . ? C13 C14 1.536(4) . ? C13 C15 1.536(3) . ? S1 O3 1.428(2) . ? S1 O1 1.437(2) . ? S1 O2 1.441(2) . ? S1 C16 1.827(3) . ? C16 F3 1.320(4) . ? C16 F2 1.332(3) . ? C16 F1 1.339(3) . ? C17 Cl3 1.709(5) . ? C17 Cl2 1.745(5) . ? 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 N1 C1 Cl1 116.28(19) . . ? N1 C1 P1 123.8(2) . . ? Cl1 C1 P1 119.52(13) . . ? C1 N1 C2 121.3(2) . . ? C1 N1 C3 123.7(2) . . ? C2 N1 C3 115.0(2) . . ? N2 P1 N3 111.89(11) . . ? N2 P1 C1 104.30(10) . . ? N3 P1 C1 95.78(10) . . ? C7 N2 C4 116.95(18) . . ? C7 N2 P1 125.78(17) . . ? C4 N2 P1 117.00(17) . . ? N2 C4 C5 113.6(2) . . ? N2 C4 C6 111.4(2) . . ? C5 C4 C6 111.7(2) . . ? N2 C7 C8 113.3(2) . . ? N2 C7 C9 110.8(2) . . ? C8 C7 C9 109.4(2) . . ? C13 N3 C10 116.4(2) . . ? C13 N3 P1 126.60(16) . . ? C10 N3 P1 117.05(19) . . ? C12 C10 N3 114.8(6) . . ? C12 C10 C11 112.7(10) . . ? N3 C10 C11 115.3(11) . . ? C12 C10 C11' 125.0(10) . . ? N3 C10 C11' 110.8(6) . . ? C11 C10 C11' 14.5(14) . . ? C12 C10 C12' 24.5(8) . . ? N3 C10 C12' 111.2(5) . . ? C11 C10 C12' 95.4(10) . . ? C11' C10 C12' 109.6(7) . . ? N3 C13 C14 113.0(2) . . ? N3 C13 C15 112.2(2) . . ? C14 C13 C15 110.3(2) . . ? O3 S1 O1 114.58(16) . . ? O3 S1 O2 115.22(16) . . ? O1 S1 O2 114.51(15) . . ? O3 S1 C16 103.76(14) . . ? O1 S1 C16 103.94(14) . . ? O2 S1 C16 102.60(13) . . ? F3 C16 F2 106.7(2) . . ? F3 C16 F1 107.6(2) . . ? F2 C16 F1 107.7(3) . . ? F3 C16 S1 111.8(2) . . ? F2 C16 S1 111.81(19) . . ? F1 C16 S1 110.9(2) . . ? Cl3 C17 Cl2 113.7(3) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.547 _refine_diff_density_min -0.319 _refine_diff_density_rms 0.061 #===END