data_ch1ppx1_0m _publ_contact_author_name 'Peter Portius' _publ_contact_author_address ; Department of Chemistry, University of Sheffield Brook Hill, Sheffield S3 7HF, UK ; _publ_contact_author_email 'peter.portius@sheffield.ac.uk' _publ_contact_author_fax '+44 (0)114-22-29346' _publ_contact_author_phone '+44 (0)114-22-29385' _publ_requested_journal 'Inorganic Chemistry' _publ_section_title ; Experimental and Theoretical Characterisation of the Hexaazidophosphate(V) Ion ; _publ_author_name ; P. Portius P. W. Fowler H. Adams T. Z. Todorova ; _publ_author_address ; Department of Chemistry, University of Sheffield Brook Hill, Sheffield S3 7HF, UK ; _publ_section_abstract ; (PPN)[P(N3)6] (2) was synthesized by metathesis of Na[P(N3)6] (1) and (PPN)N3 (PPN+ = {(Ph3P)2N}+), allowing for the isolation and full characterization of a stable hexaazidophosphate(V) salt by 31P and 14N NMR, UV absorption, IR and Raman spectroscopy,elemental and thermal analyses, X-ray diffraction and Hartree-Fock and density functional theory calculations. The colorless single crystals of 2 are triclinic, space group P1-, a = 9.6296(9), b = 9.8158(9), c = 10.1414(10) Angstrom, alpha = 92.635(5), beta = 93.437(5), gamma = 92.105(4) deg, Z = 1. The [P(N3)6]- ion of 2 is isolated in the solid state and adopts S6 symmetry both in the crystal and in solution. TGA and DSC measurements reveal a surprising thermal stability of 2 (T dec ca. 200 deg Celsius). No friction sensitivity was encountered. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; bis(triphenylphosphoranylidene)ammonium hexakis(azido)phosphate ; _chemical_name_common PPN-Hexaazidophosphate _chemical_melting_point 474 _chemical_formula_moiety 'C36 H30 N P2, N18 P' _chemical_formula_sum 'C36 H30 N19 P3' _chemical_formula_weight 821.70 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 Triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.6269(9) _cell_length_b 9.8158(9) _cell_length_c 10.1414(10) _cell_angle_alpha 92.635(5) _cell_angle_beta 93.437(5) _cell_angle_gamma 92.105(4) _cell_volume 954.83(16) _cell_formula_units_Z 1 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 7906 _cell_measurement_theta_min 2.21 _cell_measurement_theta_max 19.16 _exptl_crystal_description PRISM _exptl_crystal_colour colourless _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.429 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 424 _exptl_absorpt_coefficient_mu 0.213 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9349 _exptl_absorpt_correction_T_max 0.9708 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 100 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 16811 _diffrn_reflns_av_R_equivalents 0.0277 _diffrn_reflns_av_sigmaI/netI 0.0262 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 28.31 _reflns_number_total 4674 _reflns_number_gt 4070 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.0675P)^2^+0.2521P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4674 _refine_ls_number_parameters 265 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0452 _refine_ls_R_factor_gt 0.0385 _refine_ls_wR_factor_ref 0.1082 _refine_ls_wR_factor_gt 0.1031 _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_restrained_S_all 1.037 _refine_ls_shift/su_max 0.000 _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 P1 P 0.40344(3) 0.40715(3) 0.40326(3) 0.01828(10) Uani 1 1 d . . . N1 N 0.5000 0.5000 0.5000 0.0234(3) Uani 1 2 d S . . C1 C 0.48752(14) 0.36607(14) 0.25342(13) 0.0215(3) Uani 1 1 d . . . C2 C 0.46742(16) 0.23897(15) 0.18569(15) 0.0280(3) Uani 1 1 d . . . H2 H 0.4082 0.1705 0.2185 0.034 Uiso 1 1 calc R . . C3 C 0.53467(18) 0.21333(16) 0.06979(16) 0.0342(4) Uani 1 1 d . . . H3 H 0.5208 0.1271 0.0234 0.041 Uiso 1 1 calc R . . C4 C 0.62150(17) 0.31234(18) 0.02161(16) 0.0339(3) Uani 1 1 d . . . H4 H 0.6671 0.2940 -0.0574 0.041 Uiso 1 1 calc R . . C5 C 0.64175(17) 0.43759(18) 0.08844(16) 0.0341(3) Uani 1 1 d . . . H5 H 0.7012 0.5055 0.0550 0.041 Uiso 1 1 calc R . . C6 C 0.57580(16) 0.46520(15) 0.20443(15) 0.0274(3) Uani 1 1 d . . . H6 H 0.5908 0.5515 0.2504 0.033 Uiso 1 1 calc R . . C7 C 0.24557(14) 0.49146(13) 0.36041(14) 0.0213(3) Uani 1 1 d . . . C8 C 0.17440(16) 0.47070(15) 0.23684(15) 0.0279(3) Uani 1 1 d . . . H8 H 0.2096 0.4116 0.1710 0.033 Uiso 1 1 calc R . . C9 C 0.05141(17) 0.53730(18) 0.21085(17) 0.0350(4) Uani 1 1 d . . . H9 H 0.0023 0.5233 0.1270 0.042 Uiso 1 1 calc R . . C10 C 0.00012(16) 0.62382(17) 0.30633(17) 0.0338(4) Uani 1 1 d . . . H10 H -0.0843 0.6685 0.2878 0.041 Uiso 1 1 calc R . . C11 C 0.07124(16) 0.64559(16) 0.42868(17) 0.0319(3) Uani 1 1 d . . . H11 H 0.0360 0.7055 0.4938 0.038 Uiso 1 1 calc R . . C12 C 0.19408(15) 0.57971(15) 0.45612(15) 0.0264(3) Uani 1 1 d . . . H12 H 0.2431 0.5947 0.5400 0.032 Uiso 1 1 calc R . . C13 C 0.35722(14) 0.24998(13) 0.47750(14) 0.0215(3) Uani 1 1 d . . . C14 C 0.44907(16) 0.20070(15) 0.57392(15) 0.0285(3) Uani 1 1 d . . . H14 H 0.5336 0.2502 0.6000 0.034 Uiso 1 1 calc R . . C15 C 0.41654(19) 0.07894(17) 0.63174(18) 0.0372(4) Uani 1 1 d . . . H15 H 0.4786 0.0457 0.6981 0.045 Uiso 1 1 calc R . . C16 C 0.29405(19) 0.00571(16) 0.59305(18) 0.0375(4) Uani 1 1 d . . . H16 H 0.2725 -0.0778 0.6325 0.045 Uiso 1 1 calc R . . C17 C 0.20312(17) 0.05397(15) 0.49711(18) 0.0331(3) Uani 1 1 d . . . H17 H 0.1193 0.0033 0.4706 0.040 Uiso 1 1 calc R . . C18 C 0.23354(15) 0.17645(15) 0.43896(15) 0.0269(3) Uani 1 1 d . . . H18 H 0.1705 0.2097 0.3735 0.032 Uiso 1 1 calc R . . P2 P 0.0000 1.0000 1.0000 0.02086(12) Uani 1 2 d S . . N2 N 0.02182(13) 0.82178(12) 0.95423(12) 0.0252(3) Uani 1 1 d . . . N3 N 0.07223(12) 0.79521(11) 0.84799(12) 0.0246(3) Uani 1 1 d . . . N4 N 0.11726(15) 0.76121(13) 0.75179(14) 0.0330(3) Uani 1 1 d . . . N5 N 0.18113(12) 1.03448(12) 0.97276(13) 0.0258(3) Uani 1 1 d . . . N6 N 0.21278(12) 1.14099(13) 0.92150(13) 0.0269(3) Uani 1 1 d . . . N7 N 0.25187(15) 1.23704(16) 0.87526(17) 0.0418(4) Uani 1 1 d . . . N8 N 0.04321(13) 0.96408(12) 1.17043(12) 0.0251(3) Uani 1 1 d . . . N9 N 0.15480(13) 0.91176(12) 1.19686(12) 0.0252(3) Uani 1 1 d . . . N10 N 0.25484(15) 0.86464(15) 1.23111(14) 0.0359(3) 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 P1 0.01959(17) 0.01520(17) 0.01970(17) -0.00090(12) 0.00005(12) 0.00002(12) N1 0.0249(8) 0.0206(8) 0.0237(8) -0.0021(6) -0.0019(6) -0.0012(6) C1 0.0223(6) 0.0208(6) 0.0210(6) -0.0016(5) 0.0000(5) 0.0036(5) C2 0.0327(8) 0.0219(7) 0.0290(7) -0.0029(5) 0.0007(6) 0.0028(5) C3 0.0424(9) 0.0286(8) 0.0310(8) -0.0090(6) 0.0007(7) 0.0109(6) C4 0.0347(8) 0.0432(9) 0.0250(7) -0.0018(6) 0.0056(6) 0.0140(7) C5 0.0340(8) 0.0394(9) 0.0300(8) 0.0021(6) 0.0097(6) 0.0023(7) C6 0.0302(7) 0.0259(7) 0.0262(7) -0.0012(5) 0.0049(6) 0.0000(5) C7 0.0205(6) 0.0184(6) 0.0251(7) 0.0030(5) 0.0007(5) 0.0002(5) C8 0.0285(7) 0.0293(7) 0.0255(7) 0.0019(6) -0.0012(6) 0.0000(6) C9 0.0287(8) 0.0433(9) 0.0326(8) 0.0109(7) -0.0074(6) 0.0012(6) C10 0.0250(7) 0.0344(8) 0.0435(9) 0.0150(7) 0.0002(6) 0.0069(6) C11 0.0293(8) 0.0294(8) 0.0382(8) 0.0041(6) 0.0052(6) 0.0090(6) C12 0.0258(7) 0.0250(7) 0.0284(7) 0.0012(5) 0.0006(6) 0.0040(5) C13 0.0241(6) 0.0164(6) 0.0242(6) -0.0015(5) 0.0047(5) 0.0005(5) C14 0.0335(8) 0.0226(7) 0.0294(7) 0.0039(6) 0.0004(6) -0.0014(6) C15 0.0470(10) 0.0279(8) 0.0374(9) 0.0113(7) 0.0024(7) 0.0007(7) C16 0.0492(10) 0.0221(7) 0.0431(9) 0.0047(6) 0.0193(8) -0.0026(6) C17 0.0313(8) 0.0226(7) 0.0461(9) -0.0049(6) 0.0170(7) -0.0056(6) C18 0.0244(7) 0.0225(7) 0.0338(8) -0.0025(6) 0.0060(6) -0.0013(5) P2 0.0223(2) 0.0166(2) 0.0236(2) 0.00182(17) 0.00015(18) 0.00110(17) N2 0.0311(6) 0.0177(5) 0.0271(6) 0.0008(4) 0.0032(5) 0.0014(4) N3 0.0258(6) 0.0164(5) 0.0310(6) 0.0007(5) -0.0006(5) -0.0009(4) N4 0.0423(8) 0.0226(6) 0.0345(7) -0.0022(5) 0.0079(6) 0.0000(5) N5 0.0236(6) 0.0220(6) 0.0322(6) 0.0049(5) 0.0023(5) 0.0008(4) N6 0.0219(6) 0.0272(6) 0.0312(6) 0.0047(5) -0.0026(5) -0.0021(5) N7 0.0297(7) 0.0395(8) 0.0564(10) 0.0212(7) -0.0047(6) -0.0071(6) N8 0.0277(6) 0.0231(6) 0.0247(6) 0.0036(5) -0.0002(5) 0.0042(5) N9 0.0322(6) 0.0212(6) 0.0217(6) -0.0012(4) -0.0014(5) 0.0034(5) N10 0.0391(8) 0.0411(8) 0.0272(7) -0.0030(6) -0.0052(6) 0.0152(6) _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 P1 N1 1.5503(3) . ? P1 C7 1.7971(14) . ? P1 C13 1.8003(14) . ? P1 C1 1.8006(14) . ? N1 P1 1.5503(3) 2_666 ? C1 C6 1.397(2) . ? C1 C2 1.3976(19) . ? C2 C3 1.393(2) . ? C2 H2 0.9500 . ? C3 C4 1.384(3) . ? C3 H3 0.9500 . ? C4 C5 1.378(2) . ? C4 H4 0.9500 . ? C5 C6 1.390(2) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 C8 1.3945(19) . ? C7 C12 1.396(2) . ? C8 C9 1.391(2) . ? C8 H8 0.9500 . ? C9 C10 1.384(3) . ? C9 H9 0.9500 . ? C10 C11 1.385(2) . ? C10 H10 0.9500 . ? C11 C12 1.388(2) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.394(2) . ? C13 C18 1.3952(19) . ? C14 C15 1.389(2) . ? C14 H14 0.9500 . ? C15 C16 1.385(2) . ? C15 H15 0.9500 . ? C16 C17 1.381(3) . ? C16 H16 0.9500 . ? C17 C18 1.392(2) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? P2 N5 1.8040(12) 2_577 ? P2 N5 1.8040(12) . ? P2 N8 1.8071(12) 2_577 ? P2 N8 1.8071(12) . ? P2 N2 1.8121(12) 2_577 ? P2 N2 1.8121(12) . ? N2 N3 1.2290(18) . ? N3 N4 1.1325(18) . ? N5 N6 1.2254(17) . ? N6 N7 1.1341(18) . ? N8 N9 1.2282(17) . ? N9 N10 1.1266(18) . ? 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 P1 C7 110.33(5) . . ? N1 P1 C13 110.80(5) . . ? C7 P1 C13 108.06(6) . . ? N1 P1 C1 111.00(5) . . ? C7 P1 C1 108.34(6) . . ? C13 P1 C1 108.22(6) . . ? P1 N1 P1 180.00(2) 2_666 . ? C6 C1 C2 119.46(13) . . ? C6 C1 P1 118.36(10) . . ? C2 C1 P1 122.18(11) . . ? C3 C2 C1 119.61(14) . . ? C3 C2 H2 120.2 . . ? C1 C2 H2 120.2 . . ? C4 C3 C2 120.57(14) . . ? C4 C3 H3 119.7 . . ? C2 C3 H3 119.7 . . ? C5 C4 C3 119.91(15) . . ? C5 C4 H4 120.0 . . ? C3 C4 H4 120.0 . . ? C4 C5 C6 120.44(15) . . ? C4 C5 H5 119.8 . . ? C6 C5 H5 119.8 . . ? C5 C6 C1 120.02(14) . . ? C5 C6 H6 120.0 . . ? C1 C6 H6 120.0 . . ? C8 C7 C12 119.99(13) . . ? C8 C7 P1 122.28(11) . . ? C12 C7 P1 117.73(10) . . ? C9 C8 C7 119.38(14) . . ? C9 C8 H8 120.3 . . ? C7 C8 H8 120.3 . . ? C10 C9 C8 120.45(14) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C9 C10 C11 120.29(14) . . ? C9 C10 H10 119.9 . . ? C11 C10 H10 119.9 . . ? C10 C11 C12 119.91(15) . . ? C10 C11 H11 120.0 . . ? C12 C11 H11 120.0 . . ? C11 C12 C7 119.97(14) . . ? C11 C12 H12 120.0 . . ? C7 C12 H12 120.0 . . ? C14 C13 C18 119.89(13) . . ? C14 C13 P1 118.66(10) . . ? C18 C13 P1 121.44(11) . . ? C15 C14 C13 119.79(14) . . ? C15 C14 H14 120.1 . . ? C13 C14 H14 120.1 . . ? C16 C15 C14 120.29(16) . . ? C16 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? C17 C16 C15 120.05(15) . . ? C17 C16 H16 120.0 . . ? C15 C16 H16 120.0 . . ? C16 C17 C18 120.40(14) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C17 C18 C13 119.58(14) . . ? C17 C18 H18 120.2 . . ? C13 C18 H18 120.2 . . ? N5 P2 N5 180.000(1) 2_577 . ? N5 P2 N8 91.04(6) 2_577 2_577 ? N5 P2 N8 88.96(6) . 2_577 ? N5 P2 N8 88.96(6) 2_577 . ? N5 P2 N8 91.04(6) . . ? N8 P2 N8 180.000(1) 2_577 . ? N5 P2 N2 89.14(6) 2_577 2_577 ? N5 P2 N2 90.86(6) . 2_577 ? N8 P2 N2 89.08(6) 2_577 2_577 ? N8 P2 N2 90.92(6) . 2_577 ? N5 P2 N2 90.86(6) 2_577 . ? N5 P2 N2 89.14(6) . . ? N8 P2 N2 90.92(6) 2_577 . ? N8 P2 N2 89.08(6) . . ? N2 P2 N2 180.0 2_577 . ? N3 N2 P2 117.44(9) . . ? N4 N3 N2 175.12(14) . . ? N6 N5 P2 118.03(10) . . ? N7 N6 N5 175.02(15) . . ? N9 N8 P2 117.95(10) . . ? N10 N9 N8 174.65(15) . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.610 _refine_diff_density_min -0.316 _refine_diff_density_rms 0.063