Structures of Iodophenyltellurium(II) and Diiododi-(β-naphtyl)tellurium(IV)

The reactions between diphenyl ditelluride, (PhTe)₂, or di(β-naphtyl)ditelluride, (β-naphtylTe)₂, with equivalent amounts of iodine have been reinvestigated and the crystal and molecular structures of iodophenyltellurium(II), (PhTeI)₄, and diiododi-(β-naphtyl)tellurium(IV), (β-naphtyl)₂TeI₂, have been determined. The structure of iodophenyltellurium(II) (space group Cc, a = 13.850(5) Å, b = 13.852(3) Å, c = 16.494(6) Å and β = 101.69(2)°, Z = 4) is built up by four PhTeI units which are linked by weak Te–Te interactions with Te–Te distances between 3.152(5) Å and 3.182(4) Å. The angles between the tellurium atoms are approximately 90° giving an almost perfect square. Long range secondary bonds (Te–I: about 4.2 Å) link the tetrameric units to give an infinite two-dimensional network. Iodo(β-naphtyl)tellurium(II) is less stable than the phenyl derivative. Solutions of this compound decompose under formation of elemental tellurium and (β-naphtyl)₂TeI₂. (β-Naphtyl)₂TeI₂ crystallises in the monoclinic space group C 2/c (a = 21.198(6) Å, b = 5.8921(8) Å, c = 16.651(5) Å, β = 114.77(2)°). The tellurium atom is situated on a two-fold crystallographic axis and Te–I and Te–C bond lengths of 2.899(1) and 2.108(7) Å have been determined.     

The Crystal Structure of Tl2Te3 – a Reinvestigation

Crystals of the title compound were obtained by annealing a powder of Tl₂Te₃ in a vertical temperature gradient (230 °C–240 °C, 4 weeks). Tl₂Te₃ crystallizes in space group C2/c with lattice parameters of a = 13.275(1) Å, b = 6.562(1) Å, c = 7.918(1) Å, and β = 107.14°(2). The tellurium atoms form chains [Te₃^2–], consisting of interconnected linear triatomic · Te–^Te–Te · groups which are isosteric with XeF₂. The Te–Te distances of the XeF₂-like units are 3.02 Å, the connecting ones 2.83 Å.     

Die Kristallstruktur der Tieftemperaturmodifikation von Ag5Te2Cl

The Crystal Structure of the Low‐Temperature Form of Ag₅Te₂Cl Crystals of trimorphic Ag₅Te₂Cl were obtained by solid state reaction from a stoichiometric mixture of silver, tellurium, and tellurium(IV)chloride (480 °C, 4–10 days). The crystals were cooled down to –80 °C without decomposition and data collection was carried out at this temperature. The low temperature form of the title compound crystallizes in space group P2₁/c with lattice constants of a = 19.359(1) Å, b = 7.713(1) Å, c = 19.533(1) Å, β = 90.6°(1), V = 2916.4(1), and Z = 16. The refinement converged to residual values of R₁ = 0.0381 and wR₂ = 0.0847, respectively. Te and Cl atoms form empty, distorted octahedra interconnected by common vertices to give a 3D‐network. Ag atoms form clusters with Ag–Ag distances between 2.83 Å and 3.10 Å.     

Synthesis and structure of tetrakis(phenylenethiourea)tellurium(II) chloride dihydrochloride,C28H26N8S4Cl4Te

Reaction of tellurium(IV) with excess phenylenethiourea(2-mercaptobenzimidazole) in aqueous methanolic hydrochloric acid leads to the formation of Te(II) complex, tetrakis(phenylenethiourea)tellurium(II) chloride dihydrochloride. The characterisation and crystal structure of the complex are reported. The crystals are monoclinic, space group P2₁/c, a = 13.939(5), b = 26.523(9), c = 4.873(2) Å, β = 100.29(4)°, V = 1772.6 ų, M = 872.4, D_c = 1.651 g cm^?3, Z = 2, F(000) = 868, μ(MoK_α) = 1.298 mm^?1. Final R = 0.055 and R_W = 0.056 for 918 independent reflections. The tellurium atom in the molecule lies at the crystallographic centre of symmetry and is bonded to four phenylenethiourea sulphur atoms in a square planar arrangement with TeS(1) = 2.678(6), TeS(2) = 2.674(5) Å and S(1)TeS(2) is 90.5(3)°. The ligand behaves as a thione. Chlorine atoms remain outside the coordination sphere of the Te and stabilise the packing arrangement in the unit cell through hydrogen bondings to nitrogen atoms.     

The crystal structures of the 1-methyl-3,4-benzo-1-telluracyclopentane and 1-phenyl-1-telluracyclopentane cations in their tetraphenylborate salts,C8H8TeMe+ BPh4− and C4H8TePh+ BPh4−

The crystal structures of C₈H₈TeMe⁺ BPh₄^? (I) and C₄H₈TePh⁺ BPh₄^? (II) have been determined from three-dimensional X-ray counter data.I is monoclinic, space group P2₁/n with a 9.175(1), b 17.402(3), c 16.998(3) Å, β 98.92(6)°, Z = 4, R = 5.1% for 1641 observed reflections.II is triclinic, space group P$\text{1}$ with a 9.635(3), b 17.721(3), c 16.858(8) Å, α 89.77(2), β 104.36(4), γ 90.16(2)°, Z = 4, R = 9.0% for 6466 observed reflections.In both I and II tellurium is three-coordinate in a pyramidal geometry, with TeC distances in the range 2.07(1)–2.14(1) Å (I) and 2.10(1)–2.17(1) Å (II). In both structures short contacts of 3.4—3.5 Å occur between tellurium and carbon atoms of the tetraphenylborate anion.     

Synthesis,characterisation and crystal structure of polymeric chloro(diethyl telluride)copper(I), (Et2Te·CuCl)∞

Diethyl telludi reacts with both copper(I) and copper(II) chloride to give polymeric chloro(diethyl telluride)copper(I) which is characterised by elemental analysis and by its IR and ¹H NMR spectra. X-ray analysis shows that its structure contains infinite sheets in which two Et₂Te ligands are bridged between two di-μ-chlorodicopper(I) cores. The CuTe distances are 2.535(1) and 2.625(1) Å and the geometry around both copper and tellurium atoms in that of a distorted tetrahedron. The angels around copper range from 95.5(1) to 122.6(1)° and around tellurium from 95.6(1) to 130.5(1)°. The crystals are monoclinic, C2/c with a 19.761(11), b 7.114(4), c 11.76(7) Å, β 111.17(1)°, V 1542(2) ų, ?_calcd 2.45 ?_obsd 2.43 g/cm³Z = 8 for 1220 unique “observed” reflections and the structure refined to an R index of 0.0243.     

CuSeTeCl,CuSeTeBr und CuSeTeI: Verbindungen mit geordneten [SeTe]-Schrauben

CuSeTeCl, CuSeTeBr, and CuSeTeI: Compounds with ordered [SeTe] Screws The hitherto unknown copper(I) chalcogen halides CuSeTeCl, CuSeTeBr and CuSeTeI have been prepared and their crystal structures were determined. The compounds of general composition CuSeTeX crystallize in the monoclinic system, space group P2₁/n (No. 14), Z = 4, a = 7.9796(9), b = 4.7645(8), c = 10.843(3) Å, β = 104.12(1)°, V = 399.8(1) ų (X = Cl), a = 8.155(3), b = 4.765(2), c = 11.286(4) Å, β = 104.21(3)°, V = 425.1(3) ų (X = Br) and a = 8.4370(9) b = 4.7652(5), c = 11.996(2) Å, β = 103.178(9)°, V = 469.6(1) ų (X = I). The crystal structures show infinite onedimensional screws YY′ of chalcogen atoms, with Y = Se and Y′ = Te alternately. The coordinations of Se and Te in these compounds are quite different.     

The crystal structure of bisphenoxatelluronium dinitrate,C24H16O9N2Te2

Bisphenoxatelluronium dinitrate is monoelinie, P2₁/c: a = 11.638(4), b = 28.266(8), c = 8.546(3) å, β = 119.73(2)°, z = 4 at t = 22°. All atoms including hydrogen were located. The two ring systems, I and II, are folded along their Te-O axes, 147° and 163°, respectively. The average ring bond distances are: Te-C = 2.091, C-C = 1.377, C-O = 1.370 Å. Each Te is bonded to one NO₃ group, Te1-ON1 = 2.485(5), Te2-ON4 = 2.393(4) Å, and an oxygen bridge connects the ring systems, Te1-OB = 1.966(4), Te2-OB = 2.001(4) Å, Te1-OB-Te2 = 125.0(2)°. The bond distances and angles of the structure are compared to those of related compounds.     

CuClS0.94Te1.06 und CuBrS0.92Te1.08, zwei neue Kupfer(I)-chalkogenhalogenide mit neutralen [STe]-Schrauben

CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08, Two New Copper(I) Chalcogen Halides Containing Neutral [STe] Screws CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08 are two new, isotypic compounds of general composition CuXYY′ (X = halide, Y, Y′ = chalcogen) with a mixed chalcogen substructure. They crystallize in the monoclinic system, space group P2₁/n (No. 14), a = 7.878(2), b = 4.727(1), c = 10.759(2) Å, β = 103.97(2)°, V = 388.8(2) ų (CuClS_0.94Te_1.06) and a = 8.043(3), b = 4.746(2), c = 11.240(4) Å, β = 103.46(3)°, V = 417.3(3) ų (CuBrS_0.92Te_1.08), both with Z = 4. The crystal structures are dominated by ordered [STe^±0]-screws. From a crystal chemical point of view the sulfur and tellurium atoms are significantly different. The melting points are 341 °C (CuClS_0.94Te_1.06) and 336 °C (CuBrS_0.92Te_1.08). The compounds CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) are compared and discussed.     

Synthese,Struktur und Reaktionen von Vanadiumsäureestern VO(OR)3: Umesterung und Reaktion mit Oxalsäure

Synthesis, Structure, and Reactions of Vanadium Acid Esters VO(OR)₃: Transesterification and Reaction with Oxalic Acid The reaction of tert.‐Butyl Vanadate VO(O‐tert.Bu)₃ ( 1 ) with H₂C₂O₄ in the primary alcohols ethanol and propanol results in the formation of (ROH)(RO)₂OV^V(C₂O₄)V^VO(OR)₂(HOR) (with R = C₂H₅ 2 and R = C₃H₇ 3 ). Compounds 2 and 3 are the first structurally characterized neutral, binuclear oxo‐oxalato‐complexes with pentavalent vanadium. The two vanadium atoms are connected by a bisbidentate oxalate group. The {VO₆} coordination at each vanadium site is completed by a terminal oxo group, an alcohol ligand and two alcoxide groups. The binuclear molecules are connected to chains by hydrogen bonding. In the case of 2 a reversible isomorphic phase transition in the temperature range of –90 °C to –130 °C is observed. From methanolic solution the polymeric Methyl Vanadate [VO(OMe)₃] ( 4 ) was obtained by transesterification. A report on the crystal structures of 1 , 2 and 3 as well as a redetermination of the structure of 4 is given. Crystal data: 1, orthorhombic, Cmc2₁, a = 16.61(2) Å, b = 9.274(6) Å, c = 10.784(7) Å, V = 1662(2) ų, Z = 4, d_c = 1.144 gcm^–1; 2 (–90 ° C) , monoclinic, I2/a, a = 33.502(4) Å, b = 7.193(1) Å, c = 15.903(2) Å und β = 143.060(3)°, V = 2303(1) ų, Z = 4, d_c = 1.425 gcm^–1; 2 (–130 ° C) , monoclinic, I2/a, a = 33.274(4) Å, b = 7.161(1) Å, c = 47.554(5) Å, β = 142.798(2)°, V = 6851(1) ų, Z = 12, d_c = 1.438 gcm^–1; 3 , triklinic, P1, a = 9.017(5) Å, b = 9.754(5) Å, c = 16.359(9) Å, α = 94.87(2)°, β = 93.34(2)°, γ = 90.42(2)°, V = 1431(1) ų, Z = 2, d_c = 1.340 gcm^–1; 4 , triklinic, P1, a = 8.443(2) Å, b = 8.545(2) Å, c = 9.665(2) Å, α = 103.202(5)°, β = 96.476(5)°, γ = 112.730(4)°, V = 610.2(2)ų, Z = 4, d_c = 1.742 gcm^–1.     

Synthesis,Structure, and Stability of Cs4ZrO4

The colorless Cs₄ZrO₄ is obtained from the reaction of stoichiometric proportions of Cs, CsO₂, and finely divided ZrO₂ in a sealed Ag container at 400–650°C for several days. Regrinding and re-reaction provide a single phase sample. The compound is monoclinic (P2₁/c, Z = 4, a = 7.172 (1) Å, b = 19.907 (1) Å, c = 7.157 (1) Å, β = 113.1 (1)Å, R = 0.032) and isostructural with Cs₄PbO₄, with isolated ZrO₄^4? tetrahedra (d(Zr–O) = 1.97 Å). The compound decomposes to Cs₂ZrO₃ (a) in the presence of excess oxygen or CsO₂, (b) in high vacuum near 275°C, or (c) in a sealed container at about 730 ± 10°C.     

New Heptafluorozirconates and ‐hafnates AIBIIZr(Hf)F7 (AI = Rb,Tl; BII = Ca,Cd) – Synthesis,Structures, and Structural Relationships

Four new ABZrF₇ heptafluorozirconates (A = Rb, Tl; B = Ca, Cd) and their homologous heptafluorohafnates, all colorless, orthorhombic Cmcm (n^o63), Z = 4, have been synthesized by heating stoichiometric mixtures of RbF or TlF, CaF₂ or CdF₂ and ZrF₄ (HfF₄) in sealed platinum tubes at temperature ranging from 550 °C (Tl) to 600 °C (Rb). The crystal structures of both RbCdZrF₇ and TlCdZrF₇ have been solved from single‐crystal X‐rays diffraction data. Rietveld refinements were performed from X‐rays powder patterns for RbCaZrF₇ and TlCaZrF₇. In this series of heptafluorides, both B²⁺ and Zr⁴⁺ cations exhibit a pentagonal bipyramidal 7‐coordination. Their structural relationships with other heptafluorozirconates A^IB^IIZrF₇ as well as β‐KYb₂F₇ are discussed. RbCaZrF₇: a = 6.863(1) Å, b = 11.130(1) Å, c = 8.485(1) Å; TlCaZrF₇: a = 6.868(1) Å, b = 11.165(1) Å, c = 8.486(1) Å; RbCdZrF₇: a = 6.780(1) Å, b = 11.054(4) Å, c = 8.420(4) Å; TlCdZrF₇: a = 6.784(3) Å, b = 11.099(2) Å, c = 8.424(9) Å.     

Synthesis of unusual mixed ligand tellurium(IV) dithiocarbamates with perchlorate. Crystal and molecular structure of perchloratotris(diethyldithiocarbamato)tellurium(IV)

Synthetic and structural aspects of perchlorato complexes of tellurium(IV) with different dithiocarbamates (dtc) [(R₁R₂NCS₂) where R₁ = R₂ = methyl, ethyl, n-propyl, i-propyl; R₁R₂ = (CH₂)₅(piperidine), C₂H₄OC₂H₄ (morpholine)] are reported. The crystal structure of TeL₃ClO₄ (where L = diethyl dtc) has been determined. The crystals of the complex are monoclinic, space group P2₁/n, a = 11.379(3), b = 17.745(7), c = 14.016(8) Å, γ = 103.30(2)°, V = 2754.2 ų, F(000) = 1352, D_X = 1.61 mg M−3. The final R and R_w values are 0.047 and 0.058, respectively for 5224 unique reflections. Tellurium displays a distorted dodecahedral stereochemistry formed by two interposing trapezoids, one resulting from the four sulphurs of two L groups and the other from the two sulphurs of the third L and the two oxygens of the perchlorate ion. The average TeS distance 2.648(2) Å is close to that reported in other tris(dithiocarbamato)tellurium(IV) complexes. The perchlorate is weakly coordinated to tellurium(IV), with the average TeO distance being 2.994(8) Å. The unusual coordination of perchlorate (as a bidentate ligand) to tellurium(IV) dithiocarbamate is reported for the first time.     

Cu3SbS3: Zur Kristallstruktur und Polymorphie

Cu₃SbS₃: Crystal Structure and Polymorphism The hitherto unknown crystal structure of β-Cu₃SbS₃ at room temperature could be determined from a twinned crystal. The compound crystallizes in the monoclinic system, space group P2₁/c (No. 14), with a = 7.808(1), b = 10.233(2) and c = 13.268(2) Å, β = 90.31(1)°, V = 1 060.1(2) ų, Z = 8. An Extended-Hückel-Calculation shows weak bonding interactions between copper atoms which are coordinated trigonal planar. At ?9°C a first order phase transition occurs and the crystals disintegrate. The low-temperature modification (γ) crystallizes in the orthorhombic system with a = 7.884(2), b = 10.219(2) and c = 6.623(2) Å, V = 533.6(2) ų (?100°C). At 121°C a phase transition of higher order is observed. The high-temperature polymorph (α) of Cu₃SbS₃ is orthorhombic again. From high-temperature precession photographs the space groups Pnma (No. 62) or Pna2₁ (No. 33) can be derived. The lattice constants at 200°C are a = 7.828(3), b = 10.276(4) and c = 6.604(3) Å, V = 531.2(2) ų.     

The crystal structures of 1-allyl-1-bromo-3,4-benzo-1-telluracyclopentane [C8H8Te(C3H5)Br], 1-phenacyl-1-bromo-3,4-benzo-1-telluracyclopentane [C8H8Te(C8H7O)Br] and 1-deuteromethyl-1-iodo-3,4-benzo-1-telluracyclopentane [C8H8Te(CD3)I]; the trans effect in organotellurium bromides and iodides

The crystal structures of the title compounds have been determined from three-dimensional X-ray counter data.C₈H₈Te(CH₂CHCH₂)Br (I) is orthorhombic, space group Pbca with a 9.642(1), b 25.586(7), c 9.680(3) Å, Z = 8. The structure has been refined to R 5.2% for 1262 observed reflections.C₈H₈Te(CH₂COPh)Br (II) is orthorhombic, space group Pccn with a 23.593(6), b 14.337(3), c 9.180(2) Å, Z = 8. R = 5.5% for 1374 reflections.C₈H₈Te(CD₃)I (III) is orthorhombic, space group Pbca with a 11.200(3), b 15.976(2), c 23.328(3) Å, Z = 16. R = 5.6% for 2142 reflections.In I and II, tellurium is coordinated in an approximately octahedral geometry by the organic residues and three halogen contacts, with TeC and TeBr distances in the ranges 2.14(1)–2.19(1) Å and 3.328(2)–3.368(2) Å in (I) and 2.12(1)–2.18(1) Å and 3.292(2)–3.391(2) Å in II.In III, each of the two crystallographically independent complexes has tellurium coordinated in a distorted octahedral geometry. The TeC bond lengths are 2.10(2)–2.16(2) Å. In each case two TeI distances are in the range 3.596(2)–3.688(2) Å and a third, longer interaction (3.870(2) and 4.112(2) Å) completes the coordination.In each of the structures I–III the three covalent TeC bonds are oriented cis within the octahedra and exert a trans bond-lengthening effect on the Tehalogen interactions, precluding covalent-type bonding; the structures are essentially ionic, (C₈H₈TeR)⁺ cations and halide anions forming extended arrays.     

A square‐planar tellurium(II) complex with Te,Te′‐chelating ligands

While exploring the chemistry of tellurium‐containing dichalcogenidoimidodiphosphinate ligands, the first all‐tellurium member of a series of related square‐planar E^II(E′)₄ complexes (E and E′ are group 16 elements), namely bis(P,P,P′,P′‐tetraphenylditelluridoimidodiphosphinato‐κ²Te,Te′)tellurium(II) (systematic name: 2,2,4,4,8,8,10,10‐octaphenyl‐1λ³,5,6λ⁴,7λ³,11‐pentatellura‐3,9‐diaza‐2λ⁵,4λ⁵,8λ⁵,10λ⁵‐tetraphosphaspiro[5.5]undeca‐1,3,7,9‐tetraene), C₄₈H₄₀N₂P₄Te₅, was obtained unexpectedly. The formally Te^II centre is situated on a crystallographic inversion centre and is Te,Te′‐chelated to two anionic [(TePPh₂)₂N]⁻ ligands in an anti conformation. The central Te^II(Te)₄ unit is approximately square planar [Te—Te—Te = 93.51 (3) and 86.49 (3)°], with Te—Te bond lengths of 2.9806 (6) and 2.9978 (9) Å.     

Benzyl­triethyl­ammonium 2,2,2,4‐tetra­chloro‐2,5‐di­hydro‐1,2λ5‐oxatellurole

The geometry around the Te atom in the anion in C₁₃H₂₂N⁺·C₃H₃Cl₄OTe^? is distorted pseudo‐octahedral with three Cl atoms and the O atom forming the equatorial plane, and the C atom lying opposite the tellurium lone pair. Distances and angles are: Te—O 2.0120 (18), Te—C 2.072 (2), Te—Cl 2.5239 (7), 2.5283 (7) and 2.5577 (7) Å; O—Te—C 81.61 (9), O—Te—Cl 90.69 (6), 90.99 (6) and 168.13 (5), C—Te—Cl 87.13 (8), 86.64 (8) and 86.59 (8), and Cl—Te—Cl 87.02 (2), 90.00 (3) and 173.24 (3)°. The anions are arranged in an infinite zigzag chain parallel to the a axis through a secondary Te?Cl bond [3.8391 (8) Å].     

Synthesis and Crystal Structure of α‐ThTe3

The binary thorium tritelluride, α‐ThTe₃, was synthesized by solid‐state methods at 1223 K. From a single‐crystal X‐ray diffraction study the material crystallizes in the TiS₃ structure type with two formula units in space group C²_2h–P2₁/m of the monoclinic system in a cell with lattice constants a = 6.1730 (4) Å, b = 4.3625(3) Å, c = 10.4161(6) Å, and β = 97.756(3)° (at 100 K). The asymmetric unit of this compound comprises one Th atom and three Te atoms each with site symmetry m. Each Th atom is coordinated to eight Te atoms in a bicapped trigonal‐pyramidal arrangement. Th–Te distances range from 3.1708(4) Å to 3.2496(6) Å. The structure features a Te–Te interaction 2.7631(8) Å in length, which is typical for a Te–Te single bond. Thus α‐ThTe₃ may be charge balanced and formulated as Th⁴⁺Te^2–Te₂^2–.     

Synthesis and crystal structure of two fluorophosphated compounds with different infinite sheets: Sr2Ga(HPO4)(PO4)F2 and Sr2Fe2(HPO4)(PO4)2F2

New compounds, Sr₂Ga(HPO₄)(PO₄)F₂ and Sr₂Fe₂(HPO₄)(PO₄)₂F₂, have been prepared by hydrothermal synthesis (700°C, 180 MPa, 24 h) and characterized by single-crystal X-ray diffraction. Sr₂Ga(HPO₄)(PO₄)F₂ crystallizes in the monoclinic space group P2₁/n with a = 8.257(1) Å, b = 7.205(1) Å, c = 13.596(2) Å, β = 108.02(1)°, V = 769.2(2) ų and Z = 4 and Sr₂Fe₂(HPO₄)(PO₄)₂F₂ in the triclinic space group P2₁/n with a = 8.072(1) Å, b = 8.794(1) Å, c = 8.885(1) Å, α = 102.46(1)°, β = 115.95(1)°, γ = 89.95(1)°, V = 550.6(1) ų and Z = 2. Structures are both based on different sheets involving corner-linkage between octahedra and tetrahedra. The sheets are linked by Sr²⁺ cations. Structural relationships exist between the descloizite mineral and the title compounds.     

Synthese und Kristallstrukturen der homoleptischen Phosphaniminato‐Kationen [E(NPPh3)3]+ (E = S,Se, Te) mit Iodid und Triiodid als Gegenionen

Synthesis and Crystal Structures of the homoleptic Phosphoraneiminato Cations [E(NPPh₃)₃]⁺ (E = S, Se, Te) with Iodide and Triiodide Counter Ions N‐Iod‐triphenylphosphaneimine, INPPh₃, reacts with the chalcogenes sulfur, selenium and tellurium in boiling tetrahydrofuran to give the phosphoraneiminato complexes [E(NPPh₃)₃]⁺[¹/₂ I₃^–, ¹/₂ I^–] · THF (E = S ( 1 ), E = Se ( 2 )) and [Te(NPPh₃)₃]⁺I₃^– ( 3 ), respectively. The componds form red crystals which are characterized by IR spectroscopy and by crystal structure determinations. The homoleptic cations [E(NPPh₃)₃]⁺ have pyramidal structures with short EN and PN bond lengths, corresponding to double bonds. 1 : Space group Pa 3, Z = 8, lattice dimensions at –80 °C: a = b = c = 2192.9(1) pm, R₁ = 0.0299. 2 : Space group Pa 3, Z = 8, lattice dimensions at –80 °C: a = b = c = 2202.5(1) pm, R₁ = 0.0357. 3 : Space group Pca2₁, Z = 4, lattice dimensions at –90 °C; a = 1075.8(2); b = 1988.8(4); c = 2437.2(3) pm, R₁ = 0.0443.