Syntheses and Structures of S4N4(OCH3)2 and CH3OS4N4(O)Cl

The reaction of S₄N₄Cl₂ with CH₃OH gives S₄N₄(OCH₃)₂, a simple dimethoxoderivative of S₄N₄. Its overall geometry is analogous to other compounds of the S₄N₄X₂ type. The chlorination of S₄N₄(OCH₃)₂ leads to the oxidation of one sulfur atom to S^VI and CH₃OS₄N₄(O)Cl is formed. The compounds were characterized by ir spectroscopy and their crystal structures were determined from single crystal diffraction data collected at ?153°C. The presence of S^VI in the molecule of CH₃OS₄N₄(O)Cl is manifested by a marked shortening of the bonds formed by this atom as compared with S₄N₄Cl₂ and S₄N₄(OCH₃)₂.     

Density Functional Theoretical Study of Polynitrogen Compounds N5+Y− (Y=B(CF3)4, BF4, PF6 and B(N3)4)

The structures and the stabilities of polynitrogen compounds N₅⁺Y^? [Y=B(CF₃)₄, BF₄, PF₆, and B(N₃)₄], as the potential high energy density compounds, have been investigated at the B3LYP/6‐31G(d,p) and B3LYP/6‐311+G(d,p) levels. On the basis of our geometry optimization calculations, the structural properties of the N₅⁺Y^? compounds are discussed, and it is found that the combination of the N₅⁺ cation and the Y^? anions leads to distortion of the structures of the Y^? anions. Based on the TS calculations for the N₂‐loss dissociations of the N₅⁺Y^? compounds, the stabilities of these compounds are discussed, and the following conclusion can be drawn that among the four compounds, N₅⁺B(CF₃)₄^? is the most stable one and N₅⁺B(N₃)₄^? is the most unstable, and the relative stability of these compounds is always consistent using different basis sets. From these discussions, it is revealed that there are close correlations between the stuctrual distortions of the Y^? anions and the stabilities of the N₅⁺Y^? compounds, and between the nitrogen content in the compounds and the stabilities of the N₅⁺Y^? compounds.     

Polynitrogen chemistry: preparation and characterization of (N5)2SnF6, N5SnF5, and N5B(CF3)4

Metathetical processes were used to convert N5SbF6 into N5[B(CF3)4] and (N5)2SnF6. The latter salt is especially noteworthy because it contains two N5+ ions per anion, thus demonstrating that salts with touching polynitrogen cations can be prepared. This constitutes an important milestone towards our ultimate goal of synthesizing a stable, ionic nitrogen allotrope. The stepwise decomposition of (N5)2SnF6 yielded N5SnF5. Multinuclear NMR spectra show that in HF the SnF5- ion exists as a mixture of Sn2F(10)(2-) and Sn4F(20)(4-) ions. Attempts to isolate FN5 from the thermolysis of (N5)2SnF6 were unsuccessful, yielding only the expected decomposition products, FN3, N2, trans-N2F2, NF3, and N2.     

N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions

Single-crystal X-ray structure analyses of N(nPr)₄[B₅O₆(OH)₄][B(OH)₃]₂,1, and N(nBu)₄ [B₅O₆(OH)₄][B(OH)₃]₂,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B₅O₆(OH)₄]^– ionsand B(OH)₃ molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr) ₄ ⁺ and N(nBu) ₄ ⁺ ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP2₁/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, =106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, =107.04(1)° (238 K). The results obtained by both¹¹B and¹³C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).Author for correspondence. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages).     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

Sulfate und Hydrogensulfate des Erbiums: Er(HSO4)3-I,Er(HSO4)3-II,Er(SO4)(HSO4) und Er2(SO4)3

Sulfates and Hydrogensulfates of Erbium: Er(HSO₄)₃-I, Er(HSO₄)₃-II, Er(SO₄)(HSO₄), and Er₂(SO₄)₃ Rod shaped light pink crystals of Er(HSO₄)₃-I (orthorhombic, Pbca, a = 1195.0(1) pm, b = 949.30(7) pm, c = 1644.3(1) pm) grow from a solution of Er₂(SO₄)₃ in conc. H₂SO₄ at 250 °C. From slightly diluted solutions (85%) which contain Na₂SO₄, brick shaped light pink crystals of Er(HSO₄)₃-II (monoclinic, P2₁/n, a = 520.00(5) pm, b = 1357.8(1) pm, c = 1233.4(1) pm, β = 92.13(1)°) were obtained at 250 °C and crystals of the same colour of Er(SO₄)(HSO₄) (monoclinic, P2₁/n, a = 545.62(6) pm, b = 1075.6(1) pm, c = 1053.1(1) pm, β = 104.58(1)°) at 60 °C. In both hydrogensulfates, Er³⁺ is surrounded by eight oxygen atoms. In Er(HSO₄)₃-I layers of HSO₄^– groups are connected only via hydrogen bridges, while Er(HSO₄)₃-II consists of a threedimensional polyhedra network. In the crystal structure of Er(SO₄)(HSO₄) Er³⁺ is sevenfold coordinated by oxygen atoms, which belong to four SO₄^2–- and three HSO₄^–-tetrahedra, respectively. The anhydrous sulfate, Er₂(SO₄)₃, cannot be prepared from H₂SO₄ solutions but crystallizes from a NaCl-melt. The coordination number of Er³⁺ in Er₂(SO₄)₃ (orthorhombic, Pbcn, a = 1270.9(1) pm, b = 913.01(7) pm, c = 921.67(7) pm) is six. The octahedral coordinationpolyhedra are connected via all vertices to the SO₄^2–-tetrahedra.     

Die Kristallstruktur von B(OC2H4)3N

Zusammenfassung B(OC₂H₄)₃N kristallisiert in der Raumgruppe P ca2₁ mit den Gitterkonstantena=11,46,b=6,62,c=9,79 Å undZ=4. Die Struktur konnte mit direkten Methoden und mit sukzessivenFouriersynthesen aufgeklärt werden [570 F(hkl), R=9,8%]. Bor befindet sich in tetraedrischer Umgebung von Sauerstoff (B–O 1,431, 1,432, 1,475 Å) und Stickstoff (B–N 1,693 Å). In der Struktur bestehen zwischen den Komplexen keine Wasserstoffbrücken.

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The crystal structure ofB(OC ₂H₄)₃ N. Triethanolamine complexes, IV

B(OC₂H₄)₃N crystallizes in space group P ca2₁ with cell dimensionsa=11.46,b=6.62,c=9.79 Å andZ=4. The structure has been solved by direct methods and byFourier syntheses [570 F(hkl), R=9.8%]. Boron is tetrahedrally surrounded by oxygen (B–O 1.431, 1.432, 1.475 Å) and nitrogen atoms (B–N 1.693 Å). In the structure no hydrogen bonds exist between the complexes.

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Bemerkungen zu den Kristallstrukturbestimmungen von Boratran,B(OC2H4)3N

Normal probability plot analysis is applied to two independent structure parameter sets of B(OC₂H₄)₃N (Mattes, Fenske andTebbe ¹;Follner ²). Error analysis of intensity data (Follner) carried out with normal probability plots lead to individual weights for a least-squares structure refinement. The cell dimensions of B(OC₂H₄)₃N have been redetermined fromGuinier diffractometer measurements [a=11.388 (4),b=6.572 (3),c=9.688 (5) Å].

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ChemInform Abstract: Stability and Energetics of Metastable Molecules: Tetraazatetrahedrane (N4), Hexaazabenzene (N6), and Octaazacubane (N8)

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Binary pnictogen azides--an experimental and theoretical study: [As(N3)4]-, [Sb(N3)4]-, and [Bi(N3)5(dmso)]2-

[PPh(4)][EI(4)] (E=As, Sb, Bi) salts were reacted with four and five equivalents of AgN(3) to form tetraazidopnictates and pentaazidopnictates of the type [PPh(4)][E(N(3))(4)] and [PPh(4)](2)[E(N(3))(5)], respectively. The synthesis of [PPh(4)][P(N(3))(4)] was also attempted from the reaction of P(N(3))(3) with [PPh(4)]N(3), but it yielded only the starting materials. Herein, we report the synthesis and structure elucidation of [PPh(4)][E(N(3))](4) (E=As, Sb) and pentaazidobismuthate, stabilized as the dimethyl sulfoxide (DMSO) anion adduct, [PPh(4)](2)[Bi(N(3))(5)(dmso)]. Successive anion formation along the series E(N(3))(3)+nN(3)(-) (n=1-3) and E(N(3))(5)+N(3)(-) was studied by density functional theory.