Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _publ_contact_author ; Rufanov, Konstantin Laboratory of Coordinate Organometallic Compounds, Chair of Organic Chemistry, Department of Chemistry, M.V. Lomonossov State University of Moscow, Vorobevy Gory, 119899 Moscow, Russia ; _publ_contact_author_phone '007 909 631-0854' _publ_contact_author_fax '007 495 932-8846' _publ_contact_author_email JSU@CHEMIE.UNI-MARBURG.DE _publ_requested_coeditor_name ? _publ_contact_letter ? #============================================================================== # TITLE AND AUTHOR LIST _publ_section_title ; P-Amino-Cyclopentadienylidene-Phosphoranes versus P-Cyclopentadienyl-Imino-Phosphoranes - Tautomeric Protic Forms of a New Bidentate CpPN Ligand System ; loop_ _publ_author_name _publ_author_address A.R.Petrov ; Fachbereich Chemie Philipps-Universit\"at Marburg Hans-Meerwein-Strasse 35032 Marburg Germany ; K.A.Rufanov ; Laboratory of Coordinate Organometallic Compounds, Chair of Organic Chemistry, Department of Chemistry, M.V. Lomonossov State University of Moscow, Vorobevy Gory, 119899 Moscow, Russia ; B.Ziemer ; Institut f\"ur Chemie Humboldt-Universit\"at zu Berlin Brook-Taylor-Str. 2 D-12489 Berlin Germany ; P.Neubauer ; Institut f\"ur Chemie Humboldt-Universit\"at zu Berlin Brook-Taylor-Str. 2 D-12489 Berlin Germany ; V.V.Kotov ; Fachbereich Chemie Philipps-Universit\"at Marburg Hans-Meerwein-Strasse 35032 Marburg Germany ; ; J.Sundermeyer ; ; Fachbereich Chemie Philipps-Universit\"at Marburg Hans-Meerwein-Strasse 35032 Marburg Germany ; _publ_contact_author_name 'Prof. Joerg Sundermeyer' #=========================================================================== data_ruf10 _database_code_depnum_ccdc_archive 'CCDC 284188' _audit_creation_method SHELXL-97 _chemical_name_systematic ; P-(N-Adamantyl-1-amino)-cyclopentadienylidene- diphenylphosphorane ; _chemical_name_common ;P-(N-Adamantyl-1-amino)-cyclopentadienylidene- diphenylphosphorane ; _chemical_melting_point ? _chemical_formula_moiety 'C27 H30 N P' _chemical_formula_sum 'C27 H30 N P' _chemical_formula_weight 399.49 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 11.4180(16) _cell_length_b 9.7728(13) _cell_length_c 19.444(3) _cell_angle_alpha 90.00 _cell_angle_beta 99.072(18) _cell_angle_gamma 90.00 _cell_volume 2142.5(5) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 5000 _cell_measurement_theta_min 3.0 _cell_measurement_theta_max 25.0 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.24 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.238 _exptl_crystal_density_method none _exptl_crystal_F_000 856 _exptl_absorpt_coefficient_mu 0.142 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.9561 _exptl_absorpt_correction_T_max 0.9668 _exptl_absorpt_process_details ? _exptl_special_details ; During data collection the crystal was in cold N~2~ gas of the Cryostream Cooler (Oxford Cryosystems) mounted on a \f-axis diffractometer supplied with an area detector. ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed X-ray tube' _diffrn_radiation_monochromator 'planar graphite' _diffrn_measurement_device 'Stoe IPDS diffractometer' _diffrn_measurement_method '\f-oscill.,\f-incr.=1.3\%,176 exposures' _diffrn_detector_area_resol_mean 6.667 _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 13689 _diffrn_reflns_av_R_equivalents 0.0571 _diffrn_reflns_av_sigmaI/netI 0.0701 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.56 _diffrn_reflns_theta_max 25.25 _reflns_number_total 3872 _reflns_number_gt 2567 _reflns_threshold_expression I>2sigma(I) _computing_data_collection 'IPDS2.87 (Stoe & Cie, 1997)' _computing_cell_refinement 'IPDS2.87 (Stoe & Cie, 1997)' _computing_data_reduction 'IPDS2.87 (Stoe & Cie, 1997)' _computing_structure_solution 'SHELXS97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 1999)' _computing_publication_material 'SHELXL97 (Sheldrick, 1997)' _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^)+(0.0307P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0045(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3872 _refine_ls_number_parameters 383 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0637 _refine_ls_R_factor_gt 0.0343 _refine_ls_wR_factor_ref 0.0700 _refine_ls_wR_factor_gt 0.0647 _refine_ls_goodness_of_fit_ref 0.860 _refine_ls_restrained_S_all 0.860 _refine_ls_shift/su_max 0.006 _refine_ls_shift/su_mean 0.001 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 0.70474(15) 1.03589(18) 0.94872(9) 0.0189(4) Uani 1 1 d . . . C2 C 0.64479(14) 1.1326(2) 0.98596(10) 0.0223(4) Uani 1 1 d . . . H2 H 0.6065(17) 1.111(2) 1.0259(11) 0.030(6) Uiso 1 1 d . . . C3 C 0.65679(16) 1.2603(2) 0.95660(12) 0.0286(5) Uani 1 1 d . . . H3 H 0.6259(19) 1.348(2) 0.9736(12) 0.046(6) Uiso 1 1 d . . . C4 C 0.72153(17) 1.2458(2) 0.90112(11) 0.0281(5) Uani 1 1 d . . . H4 H 0.7429(18) 1.318(2) 0.8728(12) 0.043(7) Uiso 1 1 d . . . C5 C 0.75129(16) 1.1088(2) 0.89572(11) 0.0245(4) Uani 1 1 d . . . H5 H 0.7951(17) 1.072(2) 0.8624(11) 0.031(6) Uiso 1 1 d . . . C6 C 0.57570(14) 0.78858(19) 0.89561(9) 0.0196(4) Uani 1 1 d . . . C7 C 0.52791(16) 0.6590(2) 0.90415(11) 0.0285(5) Uani 1 1 d . . . H7 H 0.5540(15) 0.6052(19) 0.9472(10) 0.020(5) Uiso 1 1 d . . . C8 C 0.44421(19) 0.6058(3) 0.85117(13) 0.0404(6) Uani 1 1 d . . . H8 H 0.413(2) 0.516(3) 0.8571(13) 0.053(7) Uiso 1 1 d . . . C9 C 0.40716(18) 0.6792(3) 0.79122(13) 0.0412(6) Uani 1 1 d . . . H9 H 0.3543(17) 0.639(2) 0.7539(11) 0.035(6) Uiso 1 1 d . . . C10 C 0.45322(18) 0.8074(2) 0.78302(12) 0.0340(5) Uani 1 1 d . . . H10 H 0.4316(19) 0.861(2) 0.7422(13) 0.045(6) Uiso 1 1 d . . . C11 C 0.53713(15) 0.8631(2) 0.83498(10) 0.0239(4) Uani 1 1 d . . . H11 H 0.5699(17) 0.958(2) 0.8292(11) 0.036(6) Uiso 1 1 d . . . C12 C 0.82829(14) 0.77445(18) 0.94373(9) 0.0170(4) Uani 1 1 d . . . C13 C 0.93508(15) 0.84671(19) 0.95041(9) 0.0198(4) Uani 1 1 d . . . H13 H 0.9329(16) 0.944(2) 0.9591(10) 0.026(5) Uiso 1 1 d . . . C14 C 1.03999(16) 0.7787(2) 0.94660(10) 0.0245(5) Uani 1 1 d . . . H14 H 1.1081(17) 0.8246(19) 0.9543(10) 0.024(5) Uiso 1 1 d . . . C15 C 1.03935(16) 0.6397(2) 0.93326(10) 0.0252(4) Uani 1 1 d . . . H15 H 1.1137(18) 0.593(2) 0.9326(11) 0.034(6) Uiso 1 1 d . . . C16 C 0.93366(16) 0.5671(2) 0.92466(10) 0.0231(4) Uani 1 1 d . . . H16 H 0.9327(16) 0.469(2) 0.9149(10) 0.026(5) Uiso 1 1 d . . . C17 C 0.82851(15) 0.63410(19) 0.93013(9) 0.0204(4) Uani 1 1 d . . . H17 H 0.7566(16) 0.5799(19) 0.9247(10) 0.022(5) Uiso 1 1 d . . . C18 C 0.74010(14) 0.80960(18) 1.10347(9) 0.0176(4) Uani 1 1 d . . . C19 C 0.83015(17) 0.9273(2) 1.11102(10) 0.0228(4) Uani 1 1 d . . . H19A H 0.8816(18) 0.924(2) 1.0755(11) 0.034(6) Uiso 1 1 d . . . H19B H 0.7850(16) 1.014(2) 1.1046(10) 0.025(5) Uiso 1 1 d . . . C20 C 0.90643(17) 0.9233(2) 1.18338(10) 0.0290(5) Uani 1 1 d . . . H20 H 0.9607(16) 0.998(2) 1.1854(10) 0.024(5) Uiso 1 1 d . . . C21 C 0.97210(18) 0.7871(3) 1.19410(12) 0.0346(5) Uani 1 1 d . . . H21A H 1.0198(17) 0.785(2) 1.2421(12) 0.037(6) Uiso 1 1 d . . . H21B H 1.0258(17) 0.772(2) 1.1603(11) 0.032(6) Uiso 1 1 d . . . C22 C 0.88153(17) 0.6698(2) 1.18802(11) 0.0300(5) Uani 1 1 d . . . H22 H 0.9207(16) 0.583(2) 1.1938(10) 0.021(5) Uiso 1 1 d . . . C23 C 0.8008(2) 0.6875(2) 1.24289(11) 0.0329(5) Uani 1 1 d . . . H23A H 0.7414(18) 0.612(2) 1.2403(11) 0.036(6) Uiso 1 1 d . . . H23B H 0.8473(17) 0.6834(19) 1.2888(12) 0.031(6) Uiso 1 1 d . . . C24 C 0.73561(17) 0.8244(2) 1.23214(10) 0.0268(5) Uani 1 1 d . . . H24 H 0.6864(17) 0.837(2) 1.2673(11) 0.031(5) Uiso 1 1 d . . . C25 C 0.66012(16) 0.8267(2) 1.15920(10) 0.0223(4) Uani 1 1 d . . . H25A H 0.6158(18) 0.916(2) 1.1514(11) 0.039(6) Uiso 1 1 d . . . H25B H 0.6008(15) 0.749(2) 1.1551(10) 0.022(5) Uiso 1 1 d . . . C26 C 0.82606(19) 0.9419(2) 1.23843(11) 0.0313(5) Uani 1 1 d . . . H26A H 0.7876(17) 1.028(2) 1.2312(10) 0.031(6) Uiso 1 1 d . . . H26B H 0.8750(16) 0.943(2) 1.2857(11) 0.027(5) Uiso 1 1 d . . . C27 C 0.80699(17) 0.6735(2) 1.11481(11) 0.0231(4) Uani 1 1 d . . . H27A H 0.7465(15) 0.6010(19) 1.1090(9) 0.015(5) Uiso 1 1 d . . . H27B H 0.8583(16) 0.6651(19) 1.0824(11) 0.024(5) Uiso 1 1 d . . . N N 0.66160(13) 0.80918(15) 1.03438(8) 0.0183(3) Uani 1 1 d . . . H1 H 0.5921(18) 0.809(2) 1.0356(10) 0.023(6) Uiso 1 1 d . . . P P 0.69374(4) 0.86022(5) 0.95869(2) 0.01584(12) Uani 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 C1 0.0208(9) 0.0170(9) 0.0178(10) 0.0002(8) -0.0002(7) 0.0008(8) C2 0.0174(8) 0.0239(10) 0.0246(11) 0.0012(9) 0.0002(8) 0.0019(8) C3 0.0242(10) 0.0212(11) 0.0385(13) -0.0012(10) -0.0006(9) 0.0024(8) C4 0.0294(10) 0.0217(10) 0.0307(12) 0.0083(9) -0.0033(9) -0.0049(9) C5 0.0257(10) 0.0257(11) 0.0215(11) -0.0001(9) 0.0021(8) -0.0043(8) C6 0.0143(8) 0.0224(10) 0.0217(10) -0.0059(8) 0.0017(7) 0.0027(7) C7 0.0245(9) 0.0286(12) 0.0316(12) -0.0016(10) 0.0024(9) -0.0055(9) C8 0.0332(11) 0.0377(14) 0.0488(15) -0.0117(11) 0.0019(11) -0.0154(10) C9 0.0279(10) 0.0548(16) 0.0368(13) -0.0208(12) -0.0079(10) -0.0057(11) C10 0.0276(10) 0.0471(14) 0.0245(12) -0.0068(11) -0.0048(9) 0.0080(10) C11 0.0187(8) 0.0302(11) 0.0222(10) -0.0039(9) 0.0015(8) 0.0063(9) C12 0.0193(9) 0.0186(10) 0.0128(9) -0.0019(7) 0.0017(7) -0.0008(7) C13 0.0231(9) 0.0161(10) 0.0197(10) 0.0001(8) 0.0015(7) -0.0013(8) C14 0.0182(9) 0.0260(11) 0.0289(12) 0.0028(9) 0.0030(8) -0.0029(8) C15 0.0223(9) 0.0288(11) 0.0251(11) 0.0017(9) 0.0058(8) 0.0061(9) C16 0.0305(10) 0.0183(11) 0.0197(10) -0.0006(8) 0.0011(8) 0.0038(8) C17 0.0224(9) 0.0209(9) 0.0173(10) -0.0010(8) 0.0015(7) -0.0035(8) C18 0.0175(8) 0.0204(9) 0.0149(9) 0.0012(8) 0.0029(7) -0.0011(7) C19 0.0238(10) 0.0271(11) 0.0175(10) 0.0000(9) 0.0028(8) -0.0058(8) C20 0.0265(10) 0.0404(13) 0.0192(11) -0.0002(9) 0.0004(8) -0.0142(9) C21 0.0233(10) 0.0572(15) 0.0226(12) 0.0036(11) 0.0012(10) 0.0035(10) C22 0.0317(10) 0.0329(13) 0.0247(11) 0.0060(9) 0.0018(9) 0.0104(9) C23 0.0395(12) 0.0391(13) 0.0197(11) 0.0095(10) 0.0031(10) -0.0033(10) C24 0.0293(10) 0.0361(13) 0.0171(10) -0.0004(9) 0.0102(9) -0.0008(9) C25 0.0209(9) 0.0249(12) 0.0223(10) -0.0008(8) 0.0069(8) -0.0010(8) C26 0.0374(11) 0.0376(13) 0.0176(11) -0.0044(10) 0.0009(9) -0.0043(10) C27 0.0235(9) 0.0254(12) 0.0214(11) 0.0012(8) 0.0067(9) 0.0035(8) N 0.0137(8) 0.0235(8) 0.0178(8) -0.0005(7) 0.0024(6) -0.0029(6) P 0.0163(2) 0.0160(2) 0.0148(2) -0.0009(2) 0.00078(17) -0.0015(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 C5 1.423(3) . ? C1 C2 1.429(3) . ? C1 P 1.7345(18) . ? C2 C3 1.389(3) . ? C2 H2 0.97(2) . ? C3 C4 1.408(3) . ? C3 H3 1.00(2) . ? C4 C5 1.389(3) . ? C4 H4 0.95(2) . ? C5 H5 0.95(2) . ? C6 C11 1.396(3) . ? C6 C7 1.399(3) . ? C6 P 1.8138(17) . ? C7 C8 1.391(3) . ? C7 H7 0.993(19) . ? C8 C9 1.377(3) . ? C8 H8 0.96(2) . ? C9 C10 1.378(3) . ? C9 H9 0.95(2) . ? C10 C11 1.389(3) . ? C10 H10 0.95(2) . ? C11 H11 1.01(2) . ? C12 C17 1.397(2) . ? C12 C13 1.397(2) . ? C12 P 1.8134(17) . ? C13 C14 1.382(3) . ? C13 H13 0.97(2) . ? C14 C15 1.382(3) . ? C14 H14 0.890(19) . ? C15 C16 1.387(3) . ? C15 H15 0.96(2) . ? C16 C17 1.386(3) . ? C16 H16 0.98(2) . ? C17 H17 0.969(19) . ? C18 N 1.493(2) . ? C18 C25 1.532(3) . ? C18 C27 1.533(3) . ? C18 C19 1.534(2) . ? C19 C20 1.534(3) . ? C19 H19A 0.98(2) . ? C19 H19B 0.993(19) . ? C20 C21 1.526(3) . ? C20 C26 1.527(3) . ? C20 H20 0.95(2) . ? C21 C22 1.536(3) . ? C21 H21A 1.00(2) . ? C21 H21B 0.98(2) . ? C22 C23 1.526(3) . ? C22 C27 1.539(3) . ? C22 H22 0.956(19) . ? C23 C24 1.529(3) . ? C23 H23A 1.00(2) . ? C23 H23B 0.96(2) . ? C24 C26 1.536(3) . ? C24 C25 1.539(3) . ? C24 H24 0.96(2) . ? C25 H25A 1.01(2) . ? C25 H25B 1.011(19) . ? C26 H26A 0.95(2) . ? C26 H26B 1.00(2) . ? C27 H27A 0.983(18) . ? C27 H27B 0.93(2) . ? N P 1.6491(17) . ? N H1 0.80(2) . ? 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 C5 C1 C2 107.41(17) . . ? C5 C1 P 128.22(15) . . ? C2 C1 P 123.29(15) . . ? C3 C2 C1 107.46(18) . . ? C3 C2 H2 127.4(12) . . ? C1 C2 H2 125.1(12) . . ? C2 C3 C4 108.80(18) . . ? C2 C3 H3 124.9(13) . . ? C4 C3 H3 126.3(13) . . ? C5 C4 C3 108.62(19) . . ? C5 C4 H4 125.6(14) . . ? C3 C4 H4 125.8(14) . . ? C4 C5 C1 107.71(19) . . ? C4 C5 H5 125.4(13) . . ? C1 C5 H5 126.9(13) . . ? C11 C6 C7 119.66(17) . . ? C11 C6 P 118.13(14) . . ? C7 C6 P 122.10(14) . . ? C8 C7 C6 119.1(2) . . ? C8 C7 H7 120.3(10) . . ? C6 C7 H7 120.6(10) . . ? C9 C8 C7 121.0(2) . . ? C9 C8 H8 120.4(14) . . ? C7 C8 H8 118.5(14) . . ? C8 C9 C10 120.0(2) . . ? C8 C9 H9 120.3(13) . . ? C10 C9 H9 119.6(13) . . ? C9 C10 C11 120.3(2) . . ? C9 C10 H10 123.0(14) . . ? C11 C10 H10 116.7(14) . . ? C10 C11 C6 120.0(2) . . ? C10 C11 H11 120.1(11) . . ? C6 C11 H11 119.9(11) . . ? C17 C12 C13 119.10(16) . . ? C17 C12 P 120.73(13) . . ? C13 C12 P 120.03(13) . . ? C14 C13 C12 120.20(17) . . ? C14 C13 H13 121.9(11) . . ? C12 C13 H13 117.8(11) . . ? C13 C14 C15 120.23(18) . . ? C13 C14 H14 119.4(12) . . ? C15 C14 H14 120.3(12) . . ? C14 C15 C16 120.28(18) . . ? C14 C15 H15 119.1(12) . . ? C16 C15 H15 120.6(12) . . ? C17 C16 C15 119.75(18) . . ? C17 C16 H16 119.7(11) . . ? C15 C16 H16 120.6(11) . . ? C16 C17 C12 120.38(17) . . ? C16 C17 H17 117.5(11) . . ? C12 C17 H17 122.1(11) . . ? N C18 C25 107.24(13) . . ? N C18 C27 110.00(15) . . ? C25 C18 C27 109.38(16) . . ? N C18 C19 112.73(15) . . ? C25 C18 C19 108.40(15) . . ? C27 C18 C19 109.02(15) . . ? C20 C19 C18 110.10(16) . . ? C20 C19 H19A 109.3(11) . . ? C18 C19 H19A 112.0(12) . . ? C20 C19 H19B 110.2(11) . . ? C18 C19 H19B 107.7(11) . . ? H19A C19 H19B 107.5(16) . . ? C21 C20 C26 110.17(18) . . ? C21 C20 C19 110.08(17) . . ? C26 C20 C19 108.84(16) . . ? C21 C20 H20 111.1(11) . . ? C26 C20 H20 109.8(12) . . ? C19 C20 H20 106.8(12) . . ? C20 C21 C22 109.29(16) . . ? C20 C21 H21A 109.0(12) . . ? C22 C21 H21A 108.6(12) . . ? C20 C21 H21B 112.5(12) . . ? C22 C21 H21B 109.0(12) . . ? H21A C21 H21B 108.4(16) . . ? C23 C22 C21 109.55(18) . . ? C23 C22 C27 109.70(16) . . ? C21 C22 C27 108.72(17) . . ? C23 C22 H22 110.0(12) . . ? C21 C22 H22 110.8(11) . . ? C27 C22 H22 108.1(11) . . ? C22 C23 C24 109.81(17) . . ? C22 C23 H23A 111.1(13) . . ? C24 C23 H23A 109.2(12) . . ? C22 C23 H23B 109.7(12) . . ? C24 C23 H23B 110.4(12) . . ? H23A C23 H23B 106.6(17) . . ? C23 C24 C26 109.64(17) . . ? C23 C24 C25 109.20(17) . . ? C26 C24 C25 109.52(17) . . ? C23 C24 H24 109.9(12) . . ? C26 C24 H24 108.1(12) . . ? C25 C24 H24 110.4(12) . . ? C18 C25 C24 109.90(15) . . ? C18 C25 H25A 109.1(13) . . ? C24 C25 H25A 110.2(12) . . ? C18 C25 H25B 109.2(11) . . ? C24 C25 H25B 109.4(10) . . ? H25A C25 H25B 109.0(15) . . ? C20 C26 C24 109.03(17) . . ? C20 C26 H26A 108.5(13) . . ? C24 C26 H26A 111.1(12) . . ? C20 C26 H26B 109.6(11) . . ? C24 C26 H26B 110.9(11) . . ? H26A C26 H26B 107.6(17) . . ? C18 C27 C22 110.11(16) . . ? C18 C27 H27A 106.5(10) . . ? C22 C27 H27A 111.4(10) . . ? C18 C27 H27B 109.4(12) . . ? C22 C27 H27B 108.0(11) . . ? H27A C27 H27B 111.4(15) . . ? C18 N P 128.00(12) . . ? C18 N H1 115.7(15) . . ? P N H1 112.8(15) . . ? N P C1 115.43(8) . . ? N P C12 108.47(8) . . ? C1 P C12 111.19(9) . . ? N P C6 103.92(8) . . ? C1 P C6 111.44(8) . . ? C12 P C6 105.73(8) . . ? 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 C5 C1 C2 C3 -0.87(19) . . . . ? P C1 C2 C3 -169.83(13) . . . . ? C1 C2 C3 C4 0.8(2) . . . . ? C2 C3 C4 C5 -0.4(2) . . . . ? C3 C4 C5 C1 -0.1(2) . . . . ? C2 C1 C5 C4 0.6(2) . . . . ? P C1 C5 C4 168.84(13) . . . . ? C11 C6 C7 C8 1.2(3) . . . . ? P C6 C7 C8 -174.93(16) . . . . ? C6 C7 C8 C9 -0.7(3) . . . . ? C7 C8 C9 C10 0.1(4) . . . . ? C8 C9 C10 C11 0.1(3) . . . . ? C9 C10 C11 C6 0.4(3) . . . . ? C7 C6 C11 C10 -1.1(3) . . . . ? P C6 C11 C10 175.22(15) . . . . ? C17 C12 C13 C14 -2.8(3) . . . . ? P C12 C13 C14 172.90(15) . . . . ? C12 C13 C14 C15 2.7(3) . . . . ? C13 C14 C15 C16 -1.0(3) . . . . ? C14 C15 C16 C17 -0.6(3) . . . . ? C15 C16 C17 C12 0.5(3) . . . . ? C13 C12 C17 C16 1.2(3) . . . . ? P C12 C17 C16 -174.46(14) . . . . ? N C18 C19 C20 179.06(16) . . . . ? C25 C18 C19 C20 60.5(2) . . . . ? C27 C18 C19 C20 -58.5(2) . . . . ? C18 C19 C20 C21 59.2(2) . . . . ? C18 C19 C20 C26 -61.6(2) . . . . ? C26 C20 C21 C22 60.0(2) . . . . ? C19 C20 C21 C22 -60.0(2) . . . . ? C20 C21 C22 C23 -59.4(2) . . . . ? C20 C21 C22 C27 60.4(2) . . . . ? C21 C22 C23 C24 59.6(2) . . . . ? C27 C22 C23 C24 -59.7(2) . . . . ? C22 C23 C24 C26 -59.8(2) . . . . ? C22 C23 C24 C25 60.2(2) . . . . ? N C18 C25 C24 178.60(15) . . . . ? C27 C18 C25 C24 59.34(19) . . . . ? C19 C18 C25 C24 -59.41(19) . . . . ? C23 C24 C25 C18 -60.1(2) . . . . ? C26 C24 C25 C18 59.9(2) . . . . ? C21 C20 C26 C24 -60.0(2) . . . . ? C19 C20 C26 C24 60.8(2) . . . . ? C23 C24 C26 C20 59.5(2) . . . . ? C25 C24 C26 C20 -60.3(2) . . . . ? N C18 C27 C22 -176.17(15) . . . . ? C25 C18 C27 C22 -58.6(2) . . . . ? C19 C18 C27 C22 59.7(2) . . . . ? C23 C22 C27 C18 58.9(2) . . . . ? C21 C22 C27 C18 -60.9(2) . . . . ? C25 C18 N P 150.80(14) . . . . ? C27 C18 N P -90.34(18) . . . . ? C19 C18 N P 31.6(2) . . . . ? C18 N P C1 -72.82(17) . . . . ? C18 N P C12 52.68(17) . . . . ? C18 N P C6 164.84(15) . . . . ? C5 C1 P N 167.65(15) . . . . ? C2 C1 P N -25.80(17) . . . . ? C5 C1 P C12 43.56(19) . . . . ? C2 C1 P C12 -149.89(14) . . . . ? C5 C1 P C6 -74.13(18) . . . . ? C2 C1 P C6 92.43(16) . . . . ? C17 C12 P N 69.72(16) . . . . ? C13 C12 P N -105.91(15) . . . . ? C17 C12 P C1 -162.33(14) . . . . ? C13 C12 P C1 22.04(18) . . . . ? C17 C12 P C6 -41.23(17) . . . . ? C13 C12 P C6 143.14(15) . . . . ? C11 C6 P N 146.37(14) . . . . ? C7 C6 P N -37.39(17) . . . . ? C11 C6 P C1 21.44(17) . . . . ? C7 C6 P C1 -162.33(15) . . . . ? C11 C6 P C12 -99.50(15) . . . . ? C7 C6 P C12 76.74(17) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.25 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.291 _refine_diff_density_min -0.324 _refine_diff_density_rms 0.041 #-----------------END data_ruf18 _database_code_depnum_ccdc_archive 'CCDC 284189' _audit_creation_method SHELXL-97 _chemical_name_systematic ; P-(N-2,6-diisopropylanilino)-cyclopentadienylidene- diphenylphosphorane ; _chemical_name_common ;P-(N-2,6-diisopropylanilino)-cyclopentadienylidene- diphenylphosphorane ; _chemical_melting_point ? _chemical_formula_moiety 'C29 H32 N P' _chemical_formula_sum 'C29 H32 N P' _chemical_formula_weight 425.53 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 9.781(2) _cell_length_b 23.416(2) _cell_length_c 10.692(3) _cell_angle_alpha 90.00 _cell_angle_beta 99.73(2) _cell_angle_gamma 90.00 _cell_volume 2413.6(9) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 3000 _cell_measurement_theta_min 2.5 _cell_measurement_theta_max 25.0 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.80 _exptl_crystal_size_min 0.32 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.171 _exptl_crystal_density_method none _exptl_crystal_F_000 912 _exptl_absorpt_coefficient_mu 0.130 _exptl_absorpt_correction_type refdelf _exptl_absorpt_correction_T_min 0.9033 _exptl_absorpt_correction_T_max 0.9597 _exptl_absorpt_process_details ; The correction was carried out by ABSCOR (Stoe, 1997), a modification of DIFABS (Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158-166. In contrary to DIFABS, ABSCOR loads F^2^ values instead of F ones. ; _exptl_special_details ; During data collection the crystal was in cold N~2~ gas of the Cryostream Cooler (Oxford Cryosystems) mounted on a \f-axis diffractometer supplied with an area detector. ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed X-ray tube' _diffrn_radiation_monochromator 'planar graphite' _diffrn_measurement_device 'Stoe IPDS diffractometer' _diffrn_measurement_method '\f-oscill.,\f-incr.=1.4\%,174 exposures' _diffrn_detector_area_resol_mean 6.667 _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 16846 _diffrn_reflns_av_R_equivalents 0.0673 _diffrn_reflns_av_sigmaI/netI 0.0483 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -27 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.28 _diffrn_reflns_theta_max 25.93 _reflns_number_total 4597 _reflns_number_gt 3757 _reflns_threshold_expression I>2sigma(I) _computing_data_collection 'IPDS2.87 (Stoe & Cie, 1997)' _computing_cell_refinement 'IPDS2.87 (Stoe & Cie, 1997)' _computing_data_reduction 'IPDS2.87 (Stoe & Cie, 1997)' _computing_structure_solution 'SHELXS97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 1999)' _computing_publication_material 'SHELXL97 (Sheldrick, 1997)' _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^)+(0.0695P)^2^+0.0426P] 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 4597 _refine_ls_number_parameters 287 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0504 _refine_ls_R_factor_gt 0.0396 _refine_ls_wR_factor_ref 0.1065 _refine_ls_wR_factor_gt 0.1016 _refine_ls_goodness_of_fit_ref 1.030 _refine_ls_restrained_S_all 1.030 _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 -0.06088(14) 0.42009(6) 1.01990(13) 0.0166(3) Uani 1 1 d . . . C2 C -0.19185(14) 0.44410(7) 0.96676(14) 0.0214(3) Uani 1 1 d . . . H2 H -0.2249 0.4506 0.8792 0.026 Uiso 1 1 calc R . . C3 C -0.26207(15) 0.45627(7) 1.06535(15) 0.0236(3) Uani 1 1 d . . . H3 H -0.3522 0.4724 1.0571 0.028 Uiso 1 1 calc R . . C4 C -0.17699(17) 0.44061(7) 1.18047(15) 0.0258(3) Uani 1 1 d . . . H4 H -0.2001 0.4450 1.2628 0.031 Uiso 1 1 calc R . . C5 C -0.05426(16) 0.41783(6) 1.15366(14) 0.0212(3) Uani 1 1 d . . . H5 H 0.0205 0.4034 1.2137 0.025 Uiso 1 1 calc R . . C6 C 0.19731(14) 0.36089(6) 1.04061(13) 0.0187(3) Uani 1 1 d . . . C7 C 0.23369(16) 0.30363(7) 1.06147(16) 0.0272(4) Uani 1 1 d . . . H7 H 0.1792 0.2745 1.0155 0.033 Uiso 1 1 calc R . . C8 C 0.35036(19) 0.28936(8) 1.15005(19) 0.0405(4) Uani 1 1 d . . . H8 H 0.3752 0.2504 1.1648 0.049 Uiso 1 1 calc R . . C9 C 0.42984(18) 0.33181(9) 1.2164(2) 0.0441(5) Uani 1 1 d . . . H9 H 0.5094 0.3219 1.2764 0.053 Uiso 1 1 calc R . . C10 C 0.39476(18) 0.38818(8) 1.19627(19) 0.0401(5) Uani 1 1 d . . . H10 H 0.4497 0.4171 1.2426 0.048 Uiso 1 1 calc R . . C11 C 0.27929(16) 0.40312(7) 1.10841(16) 0.0279(4) Uani 1 1 d . . . H11 H 0.2558 0.4422 1.0943 0.033 Uiso 1 1 calc R . . C12 C -0.03848(14) 0.31984(6) 0.85966(13) 0.0172(3) Uani 1 1 d . . . C13 C 0.02221(15) 0.28396(7) 0.77968(14) 0.0224(3) Uani 1 1 d . . . H13 H 0.1127 0.2920 0.7632 0.027 Uiso 1 1 calc R . . C14 C -0.04921(17) 0.23691(7) 0.72463(15) 0.0283(3) Uani 1 1 d . . . H14 H -0.0077 0.2129 0.6700 0.034 Uiso 1 1 calc R . . C15 C -0.18091(17) 0.22452(7) 0.74842(16) 0.0317(4) Uani 1 1 d . . . H15 H -0.2298 0.1923 0.7096 0.038 Uiso 1 1 calc R . . C16 C -0.24092(16) 0.25916(7) 0.82884(17) 0.0308(4) Uani 1 1 d . . . H16 H -0.3309 0.2505 0.8458 0.037 Uiso 1 1 calc R . . C17 C -0.17018(15) 0.30654(7) 0.88490(15) 0.0228(3) Uani 1 1 d . . . H17 H -0.2116 0.3300 0.9406 0.027 Uiso 1 1 calc R . . C18 C 0.10774(14) 0.40550(6) 0.69644(13) 0.0166(3) Uani 1 1 d . . . C19 C 0.24600(14) 0.39627(6) 0.68178(14) 0.0188(3) Uani 1 1 d . . . C20 C 0.27049(16) 0.37385(7) 0.56621(15) 0.0247(3) Uani 1 1 d . . . H20 H 0.3632 0.3671 0.5542 0.030 Uiso 1 1 calc R . . C21 C 0.16239(16) 0.36143(7) 0.46947(14) 0.0267(3) Uani 1 1 d . . . H21 H 0.1807 0.3451 0.3927 0.032 Uiso 1 1 calc R . . C22 C 0.02673(16) 0.37284(7) 0.48446(14) 0.0239(3) Uani 1 1 d . . . H22 H -0.0469 0.3650 0.4166 0.029 Uiso 1 1 calc R . . C23 C -0.00340(14) 0.39556(6) 0.59678(13) 0.0180(3) Uani 1 1 d . . . C24 C 0.36862(14) 0.41133(7) 0.78404(15) 0.0225(3) Uani 1 1 d . . . H24 H 0.3309 0.4262 0.8590 0.027 Uiso 1 1 calc R . . C25 C 0.45962(16) 0.35962(8) 0.82797(17) 0.0329(4) Uani 1 1 d . . . H25A H 0.4023 0.3293 0.8553 0.049 Uiso 1 1 calc R . . H25B H 0.5317 0.3707 0.8990 0.049 Uiso 1 1 calc R . . H25C H 0.5032 0.3457 0.7577 0.049 Uiso 1 1 calc R . . C26 C 0.45533(16) 0.45899(7) 0.73759(17) 0.0304(4) Uani 1 1 d . . . H26A H 0.4967 0.4450 0.6661 0.046 Uiso 1 1 calc R . . H26B H 0.5291 0.4706 0.8068 0.046 Uiso 1 1 calc R . . H26C H 0.3956 0.4918 0.7103 0.046 Uiso 1 1 calc R . . C27 C -0.15176(14) 0.41164(7) 0.60943(14) 0.0205(3) Uani 1 1 d . . . H27 H -0.1618 0.4049 0.6998 0.025 Uiso 1 1 calc R . . C28 C -0.17519(17) 0.47522(8) 0.58293(17) 0.0328(4) Uani 1 1 d . . . H28A H -0.1091 0.4974 0.6430 0.049 Uiso 1 1 calc R . . H28B H -0.2700 0.4854 0.5926 0.049 Uiso 1 1 calc R . . H28C H -0.1616 0.4837 0.4961 0.049 Uiso 1 1 calc R . . C29 C -0.26194(16) 0.37536(8) 0.52664(17) 0.0325(4) Uani 1 1 d . . . H29A H -0.2600 0.3832 0.4369 0.049 Uiso 1 1 calc R . . H29B H -0.3537 0.3848 0.5459 0.049 Uiso 1 1 calc R . . H29C H -0.2426 0.3348 0.5441 0.049 Uiso 1 1 calc R . . N N 0.07561(11) 0.42507(5) 0.81651(11) 0.0157(3) Uani 1 1 d D . . H1 H 0.0900(16) 0.4610(6) 0.8372(15) 0.019 Uiso 1 1 d D . . P P 0.04375(3) 0.383747(15) 0.93312(3) 0.01388(12) Uani 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 C1 0.0178(7) 0.0145(8) 0.0175(7) -0.0014(5) 0.0029(5) 0.0004(5) C2 0.0227(7) 0.0218(9) 0.0187(7) -0.0037(6) 0.0000(6) 0.0051(6) C3 0.0207(7) 0.0197(8) 0.0319(8) -0.0044(6) 0.0086(6) 0.0030(6) C4 0.0380(9) 0.0206(9) 0.0223(8) 0.0002(6) 0.0150(6) 0.0026(6) C5 0.0287(8) 0.0174(8) 0.0172(7) 0.0010(5) 0.0034(6) 0.0025(6) C6 0.0166(7) 0.0184(8) 0.0209(7) 0.0045(6) 0.0026(5) 0.0023(5) C7 0.0261(8) 0.0200(9) 0.0337(9) 0.0032(6) 0.0002(6) 0.0033(6) C8 0.0376(10) 0.0269(11) 0.0526(12) 0.0112(8) -0.0048(8) 0.0128(7) C9 0.0276(9) 0.0403(12) 0.0560(12) 0.0138(9) -0.0171(8) 0.0068(8) C10 0.0286(9) 0.0340(11) 0.0502(11) 0.0054(8) -0.0151(8) -0.0041(7) C11 0.0245(8) 0.0206(9) 0.0346(9) 0.0055(7) -0.0062(6) 0.0001(6) C12 0.0200(7) 0.0128(7) 0.0183(7) 0.0019(5) 0.0017(5) -0.0003(5) C13 0.0258(8) 0.0174(8) 0.0252(8) -0.0003(6) 0.0078(6) -0.0002(6) C14 0.0395(9) 0.0176(9) 0.0277(8) -0.0046(6) 0.0060(7) 0.0009(7) C15 0.0369(9) 0.0172(9) 0.0379(9) -0.0031(7) -0.0022(7) -0.0071(6) C16 0.0222(8) 0.0219(9) 0.0474(10) -0.0006(7) 0.0036(7) -0.0057(6) C17 0.0210(7) 0.0175(8) 0.0305(8) 0.0010(6) 0.0061(6) 0.0002(6) C18 0.0198(7) 0.0132(8) 0.0177(7) 0.0018(5) 0.0062(5) -0.0006(5) C19 0.0191(7) 0.0149(8) 0.0230(7) 0.0013(6) 0.0053(6) -0.0005(5) C20 0.0215(7) 0.0268(9) 0.0279(8) -0.0020(6) 0.0099(6) 0.0029(6) C21 0.0305(8) 0.0314(10) 0.0198(7) -0.0038(6) 0.0090(6) 0.0025(7) C22 0.0246(7) 0.0282(9) 0.0183(7) -0.0014(6) 0.0014(6) -0.0006(6) C23 0.0191(7) 0.0174(8) 0.0177(7) 0.0037(5) 0.0040(5) 0.0003(5) C24 0.0161(7) 0.0240(9) 0.0281(8) -0.0042(6) 0.0057(6) -0.0003(5) C25 0.0236(8) 0.0310(10) 0.0409(10) -0.0004(8) -0.0036(7) 0.0023(7) C26 0.0215(8) 0.0270(10) 0.0440(10) -0.0062(7) 0.0090(7) -0.0046(6) C27 0.0166(7) 0.0270(9) 0.0175(7) 0.0008(6) 0.0019(5) -0.0001(6) C28 0.0257(8) 0.0295(10) 0.0427(10) 0.0044(7) 0.0044(7) 0.0072(7) C29 0.0200(8) 0.0422(11) 0.0347(9) -0.0070(8) 0.0028(6) -0.0052(7) N 0.0177(6) 0.0121(7) 0.0175(6) -0.0013(5) 0.0038(5) -0.0004(4) P 0.01358(18) 0.0125(2) 0.01529(19) 0.00042(13) 0.00170(13) 0.00078(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 C1 C5 1.422(2) . ? C1 C2 1.426(2) . ? C1 P 1.7184(14) . ? C2 C3 1.382(2) . ? C2 H2 0.9500 . ? C3 C4 1.413(2) . ? C3 H3 0.9500 . ? C4 C5 1.387(2) . ? C4 H4 0.9500 . ? C5 H5 0.9500 . ? C6 C7 1.395(2) . ? C6 C11 1.396(2) . ? C6 P 1.8111(15) . ? C7 C8 1.395(2) . ? C7 H7 0.9500 . ? C8 C9 1.382(3) . ? C8 H8 0.9500 . ? C9 C10 1.372(3) . ? C9 H9 0.9500 . ? C10 C11 1.386(2) . ? C10 H10 0.9500 . ? C11 H11 0.9500 . ? C12 C17 1.3952(19) . ? C12 C13 1.400(2) . ? C12 P 1.8137(15) . ? C13 C14 1.382(2) . ? C13 H13 0.9500 . ? C14 C15 1.385(2) . ? C14 H14 0.9500 . ? C15 C16 1.383(2) . ? C15 H15 0.9500 . ? C16 C17 1.389(2) . ? C16 H16 0.9500 . ? C17 H17 0.9500 . ? C18 C19 1.4042(19) . ? C18 C23 1.407(2) . ? C18 N 1.4467(18) . ? C19 C20 1.400(2) . ? C19 C24 1.521(2) . ? C20 C21 1.379(2) . ? C20 H20 0.9500 . ? C21 C22 1.389(2) . ? C21 H21 0.9500 . ? C22 C23 1.390(2) . ? C22 H22 0.9500 . ? C23 C27 1.5271(19) . ? C24 C25 1.529(2) . ? C24 C26 1.534(2) . ? C24 H24 1.0000 . ? C25 H25A 0.9800 . ? C25 H25B 0.9800 . ? C25 H25C 0.9800 . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? C27 C28 1.526(2) . ? C27 C29 1.531(2) . ? C27 H27 1.0000 . ? C28 H28A 0.9800 . ? C28 H28B 0.9800 . ? C28 H28C 0.9800 . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? N P 1.6490(12) . ? N H1 0.875(14) . ? 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 C5 C1 C2 107.48(12) . . ? C5 C1 P 126.50(11) . . ? C2 C1 P 123.84(11) . . ? C3 C2 C1 107.84(13) . . ? C3 C2 H2 126.1 . . ? C1 C2 H2 126.1 . . ? C2 C3 C4 108.40(13) . . ? C2 C3 H3 125.8 . . ? C4 C3 H3 125.8 . . ? C5 C4 C3 108.82(13) . . ? C5 C4 H4 125.6 . . ? C3 C4 H4 125.6 . . ? C4 C5 C1 107.44(13) . . ? C4 C5 H5 126.3 . . ? C1 C5 H5 126.3 . . ? C7 C6 C11 119.27(14) . . ? C7 C6 P 123.17(12) . . ? C11 C6 P 117.52(11) . . ? C8 C7 C6 119.73(16) . . ? C8 C7 H7 120.1 . . ? C6 C7 H7 120.1 . . ? C9 C8 C7 120.07(17) . . ? C9 C8 H8 120.0 . . ? C7 C8 H8 120.0 . . ? C10 C9 C8 120.50(16) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C9 C10 C11 120.18(17) . . ? C9 C10 H10 119.9 . . ? C11 C10 H10 119.9 . . ? C10 C11 C6 120.25(16) . . ? C10 C11 H11 119.9 . . ? C6 C11 H11 119.9 . . ? C17 C12 C13 118.99(14) . . ? C17 C12 P 117.18(11) . . ? C13 C12 P 123.83(11) . . ? C14 C13 C12 120.17(14) . . ? C14 C13 H13 119.9 . . ? C12 C13 H13 119.9 . . ? C13 C14 C15 120.51(15) . . ? C13 C14 H14 119.7 . . ? C15 C14 H14 119.7 . . ? C16 C15 C14 119.79(15) . . ? C16 C15 H15 120.1 . . ? C14 C15 H15 120.1 . . ? C15 C16 C17 120.26(14) . . ? C15 C16 H16 119.9 . . ? C17 C16 H16 119.9 . . ? C16 C17 C12 120.26(14) . . ? C16 C17 H17 119.9 . . ? C12 C17 H17 119.9 . . ? C19 C18 C23 121.69(13) . . ? C19 C18 N 120.36(12) . . ? C23 C18 N 117.94(11) . . ? C20 C19 C18 117.90(13) . . ? C20 C19 C24 119.31(13) . . ? C18 C19 C24 122.77(13) . . ? C21 C20 C19 121.14(14) . . ? C21 C20 H20 119.4 . . ? C19 C20 H20 119.4 . . ? C20 C21 C22 119.94(14) . . ? C20 C21 H21 120.0 . . ? C22 C21 H21 120.0 . . ? C21 C22 C23 121.30(14) . . ? C21 C22 H22 119.4 . . ? C23 C22 H22 119.4 . . ? C22 C23 C18 117.92(13) . . ? C22 C23 C27 120.95(13) . . ? C18 C23 C27 121.08(12) . . ? C19 C24 C25 112.62(13) . . ? C19 C24 C26 110.34(13) . . ? C25 C24 C26 110.52(13) . . ? C19 C24 H24 107.7 . . ? C25 C24 H24 107.7 . . ? C26 C24 H24 107.7 . . ? C24 C25 H25A 109.5 . . ? C24 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? C24 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? C24 C26 H26A 109.5 . . ? C24 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C24 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C28 C27 C23 109.83(12) . . ? C28 C27 C29 111.42(14) . . ? C23 C27 C29 113.49(13) . . ? C28 C27 H27 107.3 . . ? C23 C27 H27 107.3 . . ? C29 C27 H27 107.3 . . ? C27 C28 H28A 109.5 . . ? C27 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C27 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C27 C29 H29A 109.5 . . ? C27 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C27 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C18 N P 125.60(10) . . ? C18 N H1 118.7(10) . . ? P N H1 114.5(11) . . ? N P C1 108.88(7) . . ? N P C6 114.26(6) . . ? C1 P C6 108.02(7) . . ? N P C12 106.46(6) . . ? C1 P C12 112.42(7) . . ? C6 P C12 106.89(7) . . ? 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 C5 C1 C2 C3 0.28(17) . . . . ? P C1 C2 C3 164.44(11) . . . . ? C1 C2 C3 C4 0.35(18) . . . . ? C2 C3 C4 C5 -0.88(19) . . . . ? C3 C4 C5 C1 1.04(18) . . . . ? C2 C1 C5 C4 -0.82(17) . . . . ? P C1 C5 C4 -164.44(12) . . . . ? C11 C6 C7 C8 0.5(2) . . . . ? P C6 C7 C8 -177.15(13) . . . . ? C6 C7 C8 C9 -0.3(3) . . . . ? C7 C8 C9 C10 0.2(3) . . . . ? C8 C9 C10 C11 -0.3(3) . . . . ? C9 C10 C11 C6 0.5(3) . . . . ? C7 C6 C11 C10 -0.6(2) . . . . ? P C6 C11 C10 177.16(14) . . . . ? C17 C12 C13 C14 1.5(2) . . . . ? P C12 C13 C14 -178.16(12) . . . . ? C12 C13 C14 C15 -0.4(2) . . . . ? C13 C14 C15 C16 -0.6(3) . . . . ? C14 C15 C16 C17 0.5(3) . . . . ? C15 C16 C17 C12 0.6(2) . . . . ? C13 C12 C17 C16 -1.6(2) . . . . ? P C12 C17 C16 178.10(12) . . . . ? C23 C18 C19 C20 -3.3(2) . . . . ? N C18 C19 C20 175.97(13) . . . . ? C23 C18 C19 C24 174.76(14) . . . . ? N C18 C19 C24 -6.0(2) . . . . ? C18 C19 C20 C21 0.3(2) . . . . ? C24 C19 C20 C21 -177.81(15) . . . . ? C19 C20 C21 C22 2.0(3) . . . . ? C20 C21 C22 C23 -1.4(3) . . . . ? C21 C22 C23 C18 -1.4(2) . . . . ? C21 C22 C23 C27 175.93(15) . . . . ? C19 C18 C23 C22 3.8(2) . . . . ? N C18 C23 C22 -175.43(13) . . . . ? C19 C18 C23 C27 -173.53(13) . . . . ? N C18 C23 C27 7.2(2) . . . . ? C20 C19 C24 C25 -60.88(19) . . . . ? C18 C19 C24 C25 121.10(15) . . . . ? C20 C19 C24 C26 63.14(18) . . . . ? C18 C19 C24 C26 -114.87(15) . . . . ? C22 C23 C27 C28 -96.09(17) . . . . ? C18 C23 C27 C28 81.19(17) . . . . ? C22 C23 C27 C29 29.4(2) . . . . ? C18 C23 C27 C29 -153.36(14) . . . . ? C19 C18 N P -90.70(15) . . . . ? C23 C18 N P 88.59(15) . . . . ? C18 N P C1 -153.09(11) . . . . ? C18 N P C6 86.06(12) . . . . ? C18 N P C12 -31.67(12) . . . . ? C5 C1 P N -143.02(13) . . . . ? C2 C1 P N 55.87(14) . . . . ? C5 C1 P C6 -18.42(15) . . . . ? C2 C1 P C6 -179.53(12) . . . . ? C5 C1 P C12 99.27(14) . . . . ? C2 C1 P C12 -61.84(14) . . . . ? C7 C6 P N -120.23(13) . . . . ? C11 C6 P N 62.12(13) . . . . ? C7 C6 P C1 118.45(13) . . . . ? C11 C6 P C1 -59.20(13) . . . . ? C7 C6 P C12 -2.74(14) . . . . ? C11 C6 P C12 179.61(11) . . . . ? C17 C12 P N -121.56(12) . . . . ? C13 C12 P N 58.08(14) . . . . ? C17 C12 P C1 -2.42(14) . . . . ? C13 C12 P C1 177.22(12) . . . . ? C17 C12 P C6 115.94(12) . . . . ? C13 C12 P C6 -64.42(14) . . . . ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 25.93 _diffrn_measured_fraction_theta_full 0.976 _refine_diff_density_max 0.304 _refine_diff_density_min -0.287 _refine_diff_density_rms 0.049 #-----------------END # CIF of the ealier published structure # CCDC Number: 263440 data_ruf12a _database_code_depnum_ccdc_archive 'CCDC 263440' _audit_creation_method SHELXL-97 _chemical_name_systematic ; P-(N-Adamantyl-1-amino)-2,3,4,5-tetramethylcyclopentadienylidene- dimethylphosphorane ; _chemical_name_common Aminophosphorane _chemical_melting_point ? _chemical_formula_moiety 'C21 H34 N P' _chemical_formula_sum 'C21 H34 N P' _chemical_formula_weight 331.46 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 10.5823(16) _cell_length_b 13.135(3) _cell_length_c 13.845(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1924.5(6) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 5000 _cell_measurement_theta_min 3.0 _cell_measurement_theta_max 25.0 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.52 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.28 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.144 _exptl_crystal_density_method none _exptl_crystal_F_000 728 _exptl_absorpt_coefficient_mu 0.144 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.9289 _exptl_absorpt_correction_T_max 0.9608 _exptl_absorpt_process_details ? _exptl_special_details ; During data collection the crystal was in cold N~2~ gas of the Cryostream Cooler (Oxford Cryosystems) mounted on a \f-axis diffractometer supplied with an area detector. ; _diffrn_ambient_temperature 180(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 'Stoe IPDS diffractometer' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 12951 _diffrn_reflns_av_R_equivalents 0.0332 _diffrn_reflns_av_sigmaI/netI 0.0308 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.94 _diffrn_reflns_theta_max 25.24 _reflns_number_total 3468 _reflns_number_gt 3170 _reflns_threshold_expression I>2sigma(I) _computing_data_collection 'IPDS2.87 (Stoe & Cie, 1997)' _computing_cell_refinement 'IPDS2.87 (Stoe & Cie, 1997)' _computing_data_reduction 'IPDS2.87 (Stoe & Cie, 1997)' _computing_structure_solution 'SHELXS97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1997)' _computing_molecular_graphics 'DIAMOND (Brandenburg, 1999)' _computing_publication_material 'SHELXL97 (Sheldrick, 1997)' _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^)+(0.0421P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.009(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.02(7) _refine_ls_number_reflns 3468 _refine_ls_number_parameters 345 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0316 _refine_ls_R_factor_gt 0.0270 _refine_ls_wR_factor_ref 0.0627 _refine_ls_wR_factor_gt 0.0611 _refine_ls_goodness_of_fit_ref 0.995 _refine_ls_restrained_S_all 0.995 _refine_ls_shift/su_max 0.008 _refine_ls_shift/su_mean 0.001 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 0.80838(12) 0.75709(10) -0.06403(11) 0.0210(3) Uani 1 1 d . . . C2 C 0.82849(13) 0.83532(11) -0.13565(11) 0.0217(3) Uani 1 1 d . . . C3 C 0.87257(14) 0.78802(11) -0.21800(11) 0.0234(3) Uani 1 1 d . . . C4 C 0.88061(14) 0.68093(11) -0.20053(12) 0.0250(3) Uani 1 1 d . . . C5 C 0.84399(13) 0.66143(11) -0.10679(12) 0.0235(3) Uani 1 1 d . . . C6 C 0.80835(19) 0.94796(12) -0.12457(15) 0.0363(4) Uani 1 1 d . . . H6A H 0.724(2) 0.9657(15) -0.1099(15) 0.039(5) Uiso 1 1 d . . . H6B H 0.862(2) 0.9792(16) -0.0718(17) 0.047(6) Uiso 1 1 d . . . H6C H 0.829(2) 0.9795(16) -0.1888(16) 0.041(5) Uiso 1 1 d . . . C7 C 0.91261(18) 0.83722(14) -0.31131(13) 0.0340(4) Uani 1 1 d . . . H7A H 0.867(2) 0.8046(17) -0.3698(18) 0.052(6) Uiso 1 1 d . . . H7B H 0.887(3) 0.9186(19) -0.3125(19) 0.061(7) Uiso 1 1 d . . . H7C H 1.003(3) 0.8311(19) -0.327(2) 0.061(7) Uiso 1 1 d . . . C8 C 0.9208(2) 0.60418(16) -0.27515(15) 0.0404(4) Uani 1 1 d . . . H8A H 0.939(3) 0.539(2) -0.242(2) 0.073(8) Uiso 1 1 d . . . H8B H 0.995(3) 0.628(2) -0.314(2) 0.081(9) Uiso 1 1 d . . . H8C H 0.862(3) 0.598(2) -0.325(2) 0.080(9) Uiso 1 1 d . . . C9 C 0.84144(17) 0.55845(11) -0.05883(16) 0.0356(4) Uani 1 1 d . . . H9A H 0.761(2) 0.5316(15) -0.0491(16) 0.045(5) Uiso 1 1 d . . . H9B H 0.897(2) 0.5126(18) -0.0952(17) 0.053(6) Uiso 1 1 d . . . H9C H 0.876(2) 0.5575(14) 0.0160(16) 0.039(5) Uiso 1 1 d . . . C10 C 0.65007(17) 0.67973(16) 0.09506(15) 0.0367(4) Uani 1 1 d . . . H10A H 0.641(2) 0.6810(17) 0.160(2) 0.051(6) Uiso 1 1 d . . . H10B H 0.683(3) 0.613(2) 0.088(2) 0.068(8) Uiso 1 1 d . . . H10C H 0.577(3) 0.6967(18) 0.0621(19) 0.062(7) Uiso 1 1 d . . . C11 C 0.6913(2) 0.89176(15) 0.07988(15) 0.0378(4) Uani 1 1 d . . . H11A H 0.656(2) 0.8866(17) 0.1402(18) 0.048(6) Uiso 1 1 d . . . H11B H 0.629(2) 0.9010(17) 0.0388(18) 0.049(6) Uiso 1 1 d . . . H11C H 0.747(3) 0.9457(17) 0.0733(18) 0.054(6) Uiso 1 1 d . . . C12 C 0.91877(13) 0.74750(11) 0.22722(10) 0.0216(3) Uani 1 1 d . . . C13 C 0.82505(16) 0.80898(12) 0.28823(13) 0.0286(3) Uani 1 1 d . . . H13A H 0.8279(18) 0.8826(14) 0.2681(14) 0.029(5) Uiso 1 1 d . . . H13B H 0.733(2) 0.7836(13) 0.2745(13) 0.033(5) Uiso 1 1 d . . . C14 C 0.85715(18) 0.79736(12) 0.39623(13) 0.0326(4) Uani 1 1 d . . . H14 H 0.7994(19) 0.8358(15) 0.4341(16) 0.039(5) Uiso 1 1 d . . . C15 C 0.9913(2) 0.83711(16) 0.41436(14) 0.0404(5) Uani 1 1 d . . . H15A H 1.011(2) 0.8238(17) 0.4874(18) 0.047(6) Uiso 1 1 d . . . H15B H 0.998(2) 0.9063(19) 0.3994(17) 0.052(6) Uiso 1 1 d . . . C16 C 1.08592(17) 0.77589(16) 0.35439(12) 0.0377(4) Uani 1 1 d . . . H16 H 1.1755(19) 0.7983(13) 0.3675(13) 0.027(4) Uiso 1 1 d . . . C17 C 1.05259(15) 0.78837(13) 0.24672(12) 0.0303(4) Uani 1 1 d . . . H17A H 1.1165(19) 0.7522(15) 0.2054(14) 0.032(5) Uiso 1 1 d . . . H17B H 1.0550(19) 0.8642(14) 0.2246(14) 0.033(5) Uiso 1 1 d . . . C18 C 0.91249(17) 0.63478(12) 0.25619(13) 0.0300(4) Uani 1 1 d . . . H18A H 0.831(2) 0.6062(18) 0.2448(17) 0.051(6) Uiso 1 1 d . . . H18B H 0.976(2) 0.5997(15) 0.2184(15) 0.034(5) Uiso 1 1 d . . . C19 C 0.94445(18) 0.62309(13) 0.36418(13) 0.0347(4) Uani 1 1 d . . . H19 H 0.943(2) 0.5499(16) 0.3836(15) 0.042(5) Uiso 1 1 d . . . C20 C 0.84886(18) 0.68495(14) 0.42326(13) 0.0356(4) Uani 1 1 d . . . H20A H 0.763(2) 0.6599(13) 0.4134(14) 0.033(5) Uiso 1 1 d . . . H20B H 0.870(2) 0.6724(16) 0.4932(17) 0.044(6) Uiso 1 1 d . . . C21 C 1.07827(19) 0.66332(16) 0.38133(15) 0.0412(4) Uani 1 1 d . . . H21A H 1.095(2) 0.6560(17) 0.448(2) 0.058(6) Uiso 1 1 d . . . H21B H 1.141(3) 0.6195(19) 0.3428(19) 0.062(7) Uiso 1 1 d . . . N N 0.89575(11) 0.76004(10) 0.12231(9) 0.0257(3) Uani 1 1 d . . . HN H 0.9616(19) 0.7586(14) 0.0879(13) 0.027(4) Uiso 1 1 d . . . P P 0.76632(3) 0.77106(3) 0.05552(3) 0.02227(11) Uani 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 C1 0.0195(6) 0.0220(6) 0.0215(7) 0.0003(6) -0.0019(6) -0.0002(5) C2 0.0157(7) 0.0232(7) 0.0260(8) 0.0015(6) -0.0027(6) -0.0010(5) C3 0.0171(7) 0.0313(8) 0.0218(8) 0.0013(6) -0.0030(6) 0.0021(6) C4 0.0182(7) 0.0294(7) 0.0273(8) -0.0043(6) -0.0028(6) 0.0027(6) C5 0.0195(7) 0.0221(7) 0.0288(8) 0.0009(6) -0.0046(6) 0.0022(5) C6 0.0426(10) 0.0238(8) 0.0425(11) 0.0034(7) 0.0089(9) 0.0018(7) C7 0.0293(9) 0.0464(10) 0.0263(9) 0.0066(7) 0.0005(8) -0.0019(7) C8 0.0429(11) 0.0440(10) 0.0344(10) -0.0119(8) -0.0039(9) 0.0124(9) C9 0.0376(10) 0.0212(7) 0.0479(11) 0.0026(7) 0.0015(9) 0.0022(6) C10 0.0228(8) 0.0510(11) 0.0364(11) 0.0094(8) 0.0023(8) -0.0088(7) C11 0.0334(10) 0.0456(10) 0.0343(11) -0.0013(7) 0.0044(8) 0.0162(8) C12 0.0176(6) 0.0284(8) 0.0189(7) -0.0007(6) 0.0026(6) -0.0003(5) C13 0.0277(8) 0.0302(8) 0.0278(8) -0.0016(6) 0.0072(7) 0.0040(7) C14 0.0382(9) 0.0331(8) 0.0266(8) -0.0051(6) 0.0112(8) -0.0007(6) C15 0.0507(12) 0.0440(10) 0.0266(10) -0.0046(8) 0.0010(8) -0.0133(9) C16 0.0291(8) 0.0574(10) 0.0266(9) 0.0014(8) -0.0045(7) -0.0126(8) C17 0.0228(8) 0.0428(10) 0.0254(8) -0.0003(7) 0.0011(7) -0.0050(7) C18 0.0299(9) 0.0285(8) 0.0317(9) -0.0034(7) 0.0028(8) 0.0010(7) C19 0.0384(10) 0.0315(9) 0.0344(10) 0.0057(7) 0.0010(8) 0.0011(7) C20 0.0382(10) 0.0408(9) 0.0279(9) 0.0029(7) 0.0087(8) -0.0059(7) C21 0.0363(10) 0.0575(11) 0.0299(10) 0.0089(8) -0.0051(8) 0.0070(8) N 0.0158(6) 0.0408(7) 0.0204(6) -0.0003(6) 0.0042(5) 0.0015(5) P 0.01585(17) 0.02831(17) 0.02266(18) 0.00156(15) 0.00148(15) 0.00133(13) _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 C5 1.439(2) . ? C1 C2 1.444(2) . ? C1 P 1.7239(15) . ? C2 C3 1.380(2) . ? C2 C6 1.503(2) . ? C3 C4 1.430(2) . ? C3 C7 1.505(2) . ? C4 C5 1.378(2) . ? C4 C8 1.505(2) . ? C5 C9 1.507(2) . ? C6 H6A 0.95(2) . ? C6 H6B 1.01(2) . ? C6 H6C 1.00(2) . ? C7 H7A 1.04(2) . ? C7 H7B 1.10(2) . ? C7 H7C 0.99(3) . ? C8 H8A 1.00(3) . ? C8 H8B 1.01(3) . ? C8 H8C 0.93(4) . ? C9 H9A 0.93(2) . ? C9 H9B 0.98(3) . ? C9 H9C 1.10(2) . ? C10 P 1.8034(18) . ? C10 H10A 0.90(3) . ? C10 H10B 0.95(3) . ? C10 H10C 0.93(3) . ? C11 P 1.8047(18) . ? C11 H11A 0.92(3) . ? C11 H11B 0.88(3) . ? C11 H11C 0.93(2) . ? C12 N 1.4821(18) . ? C12 C13 1.533(2) . ? C12 C18 1.535(2) . ? C12 C17 1.538(2) . ? C13 C14 1.541(2) . ? C13 H13A 1.007(19) . ? C13 H13B 1.05(2) . ? C14 C20 1.526(2) . ? C14 C15 1.534(3) . ? C14 H14 0.95(2) . ? C15 C16 1.529(3) . ? C15 H15A 1.05(2) . ? C15 H15B 0.94(2) . ? C16 C21 1.527(3) . ? C16 C17 1.541(2) . ? C16 H16 1.01(2) . ? C17 H17A 1.00(2) . ? C17 H17B 1.042(19) . ? C18 C19 1.541(2) . ? C18 H18A 0.96(3) . ? C18 H18B 0.97(2) . ? C19 C21 1.530(3) . ? C19 C20 1.534(3) . ? C19 H19 1.00(2) . ? C20 H20A 0.97(2) . ? C20 H20B 1.01(2) . ? C21 H21A 0.94(3) . ? C21 H21B 1.03(3) . ? N P 1.6589(13) . ? N HN 0.84(2) . ? 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 C5 C1 C2 107.48(13) . . ? C5 C1 P 123.74(11) . . ? C2 C1 P 128.44(11) . . ? C3 C2 C1 107.27(12) . . ? C3 C2 C6 125.15(14) . . ? C1 C2 C6 127.58(15) . . ? C2 C3 C4 108.86(14) . . ? C2 C3 C7 127.66(14) . . ? C4 C3 C7 123.42(14) . . ? C5 C4 C3 108.99(13) . . ? C5 C4 C8 126.97(15) . . ? C3 C4 C8 124.03(16) . . ? C4 C5 C1 107.38(13) . . ? C4 C5 C9 125.92(14) . . ? C1 C5 C9 126.70(15) . . ? C2 C6 H6A 113.4(12) . . ? C2 C6 H6B 113.2(12) . . ? H6A C6 H6B 106.0(17) . . ? C2 C6 H6C 106.6(12) . . ? H6A C6 H6C 106.8(18) . . ? H6B C6 H6C 110.7(17) . . ? C3 C7 H7A 111.2(13) . . ? C3 C7 H7B 111.0(14) . . ? H7A C7 H7B 105.9(18) . . ? C3 C7 H7C 115.1(16) . . ? H7A C7 H7C 105(2) . . ? H7B C7 H7C 108.5(19) . . ? C4 C8 H8A 108.4(16) . . ? C4 C8 H8B 112.3(17) . . ? H8A C8 H8B 112(2) . . ? C4 C8 H8C 112.3(19) . . ? H8A C8 H8C 114(2) . . ? H8B C8 H8C 98(2) . . ? C5 C9 H9A 114.8(13) . . ? C5 C9 H9B 108.3(14) . . ? H9A C9 H9B 113.1(19) . . ? C5 C9 H9C 114.8(10) . . ? H9A C9 H9C 99.3(17) . . ? H9B C9 H9C 106.1(18) . . ? P C10 H10A 111.2(15) . . ? P C10 H10B 109.3(16) . . ? H10A C10 H10B 99(2) . . ? P C10 H10C 105.2(15) . . ? H10A C10 H10C 113(2) . . ? H10B C10 H10C 119(2) . . ? P C11 H11A 106.4(14) . . ? P C11 H11B 109.3(15) . . ? H11A C11 H11B 107(2) . . ? P C11 H11C 111.9(15) . . ? H11A C11 H11C 114(2) . . ? H11B C11 H11C 108(2) . . ? N C12 C13 112.03(12) . . ? N C12 C18 110.86(12) . . ? C13 C12 C18 109.65(13) . . ? N C12 C17 106.53(11) . . ? C13 C12 C17 108.37(13) . . ? C18 C12 C17 109.30(13) . . ? C12 C13 C14 109.87(13) . . ? C12 C13 H13A 109.5(11) . . ? C14 C13 H13A 111.0(11) . . ? C12 C13 H13B 109.5(10) . . ? C14 C13 H13B 110.5(10) . . ? H13A C13 H13B 106.4(15) . . ? C20 C14 C15 110.03(17) . . ? C20 C14 C13 108.74(14) . . ? C15 C14 C13 109.22(14) . . ? C20 C14 H14 110.0(12) . . ? C15 C14 H14 108.9(12) . . ? C13 C14 H14 110.0(12) . . ? C16 C15 C14 109.77(15) . . ? C16 C15 H15A 107.7(13) . . ? C14 C15 H15A 106.8(13) . . ? C16 C15 H15B 109.9(15) . . ? C14 C15 H15B 111.5(15) . . ? H15A C15 H15B 111.1(19) . . ? C21 C16 C15 109.99(16) . . ? C21 C16 C17 109.10(15) . . ? C15 C16 C17 108.64(16) . . ? C21 C16 H16 106.8(10) . . ? C15 C16 H16 111.4(10) . . ? C17 C16 H16 110.9(11) . . ? C12 C17 C16 110.08(13) . . ? C12 C17 H17A 110.8(11) . . ? C16 C17 H17A 110.3(11) . . ? C12 C17 H17B 107.7(11) . . ? C16 C17 H17B 112.3(11) . . ? H17A C17 H17B 105.5(16) . . ? C12 C18 C19 109.88(13) . . ? C12 C18 H18A 112.0(14) . . ? C19 C18 H18A 108.6(14) . . ? C12 C18 H18B 106.6(12) . . ? C19 C18 H18B 108.9(12) . . ? H18A C18 H18B 110.8(18) . . ? C21 C19 C20 110.16(16) . . ? C21 C19 C18 108.62(14) . . ? C20 C19 C18 108.67(15) . . ? C21 C19 H19 107.9(13) . . ? C20 C19 H19 110.8(13) . . ? C18 C19 H19 110.7(12) . . ? C14 C20 C19 110.12(14) . . ? C14 C20 H20A 110.2(11) . . ? C19 C20 H20A 111.1(11) . . ? C14 C20 H20B 112.5(12) . . ? C19 C20 H20B 106.3(13) . . ? H20A C20 H20B 106.5(17) . . ? C16 C21 C19 110.22(15) . . ? C16 C21 H21A 109.2(14) . . ? C19 C21 H21A 106.8(15) . . ? C16 C21 H21B 112.5(14) . . ? C19 C21 H21B 108.8(14) . . ? H21A C21 H21B 109(2) . . ? C12 N P 133.77(10) . . ? C12 N HN 114.5(12) . . ? P N HN 111.7(12) . . ? N P C1 108.23(7) . . ? N P C10 109.63(8) . . ? C1 P C10 113.38(8) . . ? N P C11 109.61(9) . . ? C1 P C11 112.73(8) . . ? C10 P C11 103.16(11) . . ? 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 C5 C1 C2 C3 0.78(16) . . . . ? P C1 C2 C3 174.26(11) . . . . ? C5 C1 C2 C6 -178.26(16) . . . . ? P C1 C2 C6 -4.8(2) . . . . ? C1 C2 C3 C4 0.20(17) . . . . ? C6 C2 C3 C4 179.27(15) . . . . ? C1 C2 C3 C7 -177.23(15) . . . . ? C6 C2 C3 C7 1.8(3) . . . . ? C2 C3 C4 C5 -1.16(18) . . . . ? C7 C3 C4 C5 176.40(14) . . . . ? C2 C3 C4 C8 177.81(16) . . . . ? C7 C3 C4 C8 -4.6(3) . . . . ? C3 C4 C5 C1 1.62(17) . . . . ? C8 C4 C5 C1 -177.31(16) . . . . ? C3 C4 C5 C9 -178.67(14) . . . . ? C8 C4 C5 C9 2.4(3) . . . . ? C2 C1 C5 C4 -1.49(16) . . . . ? P C1 C5 C4 -175.35(11) . . . . ? C2 C1 C5 C9 178.81(14) . . . . ? P C1 C5 C9 5.0(2) . . . . ? N C12 C13 C14 -177.29(12) . . . . ? C18 C12 C13 C14 59.19(17) . . . . ? C17 C12 C13 C14 -60.05(16) . . . . ? C12 C13 C14 C20 -59.89(18) . . . . ? C12 C13 C14 C15 60.19(18) . . . . ? C20 C14 C15 C16 59.1(2) . . . . ? C13 C14 C15 C16 -60.2(2) . . . . ? C14 C15 C16 C21 -59.1(2) . . . . ? C14 C15 C16 C17 60.3(2) . . . . ? N C12 C17 C16 -178.65(14) . . . . ? C13 C12 C17 C16 60.63(17) . . . . ? C18 C12 C17 C16 -58.82(17) . . . . ? C21 C16 C17 C12 59.06(19) . . . . ? C15 C16 C17 C12 -60.85(19) . . . . ? N C12 C18 C19 176.67(12) . . . . ? C13 C12 C18 C19 -59.11(18) . . . . ? C17 C12 C18 C19 59.54(17) . . . . ? C12 C18 C19 C21 -60.33(18) . . . . ? C12 C18 C19 C20 59.52(18) . . . . ? C15 C14 C20 C19 -58.51(19) . . . . ? C13 C14 C20 C19 61.1(2) . . . . ? C21 C19 C20 C14 57.9(2) . . . . ? C18 C19 C20 C14 -60.9(2) . . . . ? C15 C16 C21 C19 58.7(2) . . . . ? C17 C16 C21 C19 -60.4(2) . . . . ? C20 C19 C21 C16 -58.00(19) . . . . ? C18 C19 C21 C16 60.92(19) . . . . ? C13 C12 N P -37.3(2) . . . . ? C18 C12 N P 85.55(17) . . . . ? C17 C12 N P -155.63(13) . . . . ? C12 N P C1 -167.82(14) . . . . ? C12 N P C10 -43.70(17) . . . . ? C12 N P C11 68.86(16) . . . . ? C5 C1 P N 72.55(13) . . . . ? C2 C1 P N -99.96(13) . . . . ? C5 C1 P C10 -49.30(15) . . . . ? C2 C1 P C10 138.18(13) . . . . ? C5 C1 P C11 -166.05(13) . . . . ? C2 C1 P C11 21.44(16) . . . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.24 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.153 _refine_diff_density_min -0.196 _refine_diff_density_rms 0.031