Alkalimetallnitrido‐tecto‐metallate(VI) mit Netzwerken von Sechsringen spitzenverknüpfter Tetraeder [(MNN3/2)6] mit M = Mo,W der unerwarteten Zusammensetzung A9+x[M6N15] mit A = Rb,Cs und 0 < x < 1

Alkali Metal Nitrido Tecto Metallates(VI) with Networks of Six‐membered Rings of Corner‐sharing Tetrahedra [(MNN_3/2)₆] with M = Mo, W of the Unexpected Composition A_9+x[M₆N₁₅] with A = Rb, Cs and 0 < x < 1 Reactions of metal powders of Mo and W respectively with amides and azides of Rb and Cs lead to the compounds Rb_9+x[W₆N₁₅] and Cs_9+x[M₆N₁₅] with M = Mo, W and 0 < x < 1. The reactions are carried out at 650 °C in autoclaves for salt melts and are finished within 5 d. Crystals of the compounds are embedded in a matrix of the corresponding alkali metal. These metals result from the thermal decomposition of the amides and azides used in high molar ratios. The metals are washed out by liquid ammonia. Besides microcrystalline material of the above mentioned compounds single crystals suitable in size for x‐ray structure determinations were isolated. The compounds crystallize in the space group R3c (No. 167) with Z = 6 and the following lattice constants: Rb_9+x[W₆N₁₅]: a = 12.743(7) Å, c = 27.794(8) Å, c/a = 2.181 Cs_9+x[Mo₆N₁₅]: a = 13.104(5) Å, c = 28.430(9) Å, c/a = 2.170 Cs_9+x[W₆N₁₅]: a = 13.136(5) Å, c = 28.472(6) Å, c/a = 2.167 The metal centres of tetrahedra [MNN_3/2] are condensated to cyclohexane analogue six‐membered rings in chair‐form via nitrogen atoms and axial ones connect them to a three‐dimensional network. Nine – as to the formula unit – of the alkali metal atoms are located in vacancies of the anionic partial structure. The residual atoms with 0 < x < 1 centre the six‐membered rings and are coordinated planar hexagonal by N neighbours.     

Synthese und Struktur eines Caesiumoxonitridomonowolframates(VI), Cs7[WN1,5O2,5]2

Synthesis and Crystal Structure of a Cesium Oxo Nitrido Monotungstate(VI), Cs₇[WN_1.5O_2.5]₂ Mixtures of tungsten powder and WO₃ react with an excess of CsNH₂ in autoclaves at 650 °C to yield hygroscopic yellow crystals of cesium oxo nitrido tungstate(VI) Cs₇[WN_1.5O_2.5]₂ besides Cs₆[W₂N₄O₃] [1]. After the reaction the crystals are embedded in cesium metal (from thermal decomposition of CsNH₂), which was washed out by liquid ammonia. The crystals allowed a successful X‐ray structure determination. Cs₇[WN_1.5O_2.5]₂ crystallizes in the space group P2₁/c with the lattice parameters a = 6.766(1) Å, b = 11.205(3) Å, c = 22.299(4) Å, β = 91.05(1)° and Z = 4. The crystal structure is built up by isolated tetrahedra [WX₄] with X = N, O, which are separeted by cesium cations.     

Synthese und Kristallstrukturen der Nitridodiolato-Osmate(VI) PPh4[OsNCl2(O2C2H4)] und PPh4[OsNCl2(O2C2Me4)] · 2 THF

Syntheses and Crystal Structures of the Nitridodiolato Osmates(VI) PPh₄[OsNCl₂(O₂C₂H₄)] and PPh₄[OsNCl₂(O₂C₂Me₄)] · 2 THF The title compounds were prepared by the reaction of PPh₄[OsNCl₄] with glycole and pinacole, respectively, in CH₂Cl₂ and THF, respectively, in the presence of triethylamine, forming orange-red single crystals. According to the crystal structure determinations the compounds have ionic structures. In the anions the nitrido ligand occupies the apical position of the distorted tetragonal pyramid, and the two chlorine atoms and the two oxygen atoms of the diolato ligands are in equatorial positions. PPh₄[OsNCl₂(O₂C₂H₄)] : Space group P2₁/n, Z = 4, 3 331 observed unique reflections, R = 0.031. Lattice dimensions at 19°C: a = 1 750.3, b = 816.8, c = 1 816.5 pm, β = 95.16°. PPh₄[OsNCl₂(O₂C₂Me₄)] · 2 THF : Space group P1 , Z = 2, 5 238 observed unique reflections, R = 0.051. Lattice dimensions at -80°C: a = 898.9, b = 1 405.1, c = 1 518.6 pm, α = 93.66°, β = 92.89°, γ = 92.51°.     

Synthese und Struktur von Cs11[(WN2,5O1,5)2](N3)2, ein Caesiumoxonitridomonowolframat(VI)-azid

Synthesis and Structure of Cs₁₁[(WN_2,5O_1,5)₂](N₃)₂, a Cesium Oxo Nitrido Monotungstate(VI) Azide Cs₁₁[(WN_2,5O_1,5)₂](N₃)₂ results from the reaction of a mixture of CsNH₂, W and WO₃ at 620 °C in autoclaves. It crystallizes monoclinic in the space group C2/m with the lattice parameters a = 12.421(4) Å, b = 11.568(6) Å, c = 10.516(4) Å, β = 118.71(3)° and Z = 4. The crystal structure is built up by isolated tetrahedra [WX₄] with X = N, O, which are connected by cesium cations. Between the cesium ions lie azide ions separated from the anions [WX₄]. The tungsten atoms and azide ions together build up the motif of a distorted arrangement of the CsCl structure type.     

Darstellung,Schwingungsspektrum und Kristallstruktur von (n‐Bu4N)2[(W6Cl)F] · 2 CH2Cl2 und 19F‐NMR‐spektroskopischer Nachweis der gemischten Clusteranionen [(W6Cl)FCl]2–, n = 1–6

Synthesis, Vibrational Spectra, and Crystal Structure of ( n ‐Bu₄N)₂[(W₆Cl )F ] · 2 CH₂Cl₂ and ¹⁹F NMR Spectroscopic Evidence of the Mixed Cluster Anions [(W₆Cl )F Cl ]^2–, n = 1–6 The reaction of (n‐Bu₄N)₂[(W₆Cl)Cl] with CF₃COOH in dichloromethane gives intermediately a mixture of the cluster anions [(W₆Cl)(CF₃COO)Cl]^2–, n = 1–6. By treatment with NH₄F the outer sphere coordinated trifluoracetato ligands are easily substituted and the components of the series [(W₆Cl)FCl], n = 1–6 are formed and characterized by their distinct ¹⁹F NMR chemical shifts. An X‐ray structure determination has been performed on a single crystal of (n‐Bu₄N)₂[(W₆Cl)F] · 2 CH₂Cl₂ (orthorhombic, space group Pbca, a = 15.628(4), b = 17.656(3), c = 20.687(4) Å, Z = 4). The low temperatur IR (60 K) and Raman (20 K) spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(WW) = 1.89, f_d(WF) = 2.43 and f_d(WCl) = 0.93 mdyn/Å.     

Synthese und Kristallstrukturen der heteronuklearen Nitrido‐Komplexe [(Me2PhP)3(MeCN)ClRe≡N–MCl5] mit M = Sn und Zr

Synthesis and Structures of the Dinuclear Nitrido Complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] with M = Sn and Zr The water sensitive complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] (M = Sn ( 1 ) und Zr ( 2 )) are obtained in dichloromethane from [ReNCl₂(PMe₂Ph)₃] and the acetonitrile adducts of SnCl₄ or ZrCl₄. The compounds crystallize as dichloromethane solvate isotypically with [(Me₂PhP)₃(MeCN)ClRe≡N–TiCl₅] · CH₂Cl₂ in the space group P2₁/n. From toluene crystallize monoclinic crystals of 1 · MeCN · C₇H₈. In the diamagnetic complexes 1 and 2 an anion [MCl₅]^– coordinates to the nitrido ligand of the cationic complex [ReNCl(MeCN)(PMe₂Ph)₃]⁺. The resulting nitrido bridges Re≡N–M are almost linear and asymmetric with Re–N = 169.5 pm, Sn–N = 230.1 pm and Re–N–Sn = 164.5° for 1 and Re–N = 168.4 pm, Zr–N = 237.2 pm and Re–N–Zr = 165.6° for 2 . The phosphine ligands at the Re atom are in a meridional arrangement.     

Pniktogenidostannate(IV) mit isolierten Tetraeder‐Anionen: Neue Vertreter (E1)4(E2)2[Sn(E15)4] (mit E1 = Na,K; E2 = Ca,Sr, Ba; E15 = P,As, Sb,Bi) vom Na6[ZnO4]‐Typ und die Überstrukturvariante von K4Sr2[SnAs4]

Pnictogenidostannates(IV) with Discrete Tetrahedral Anions: New Representatives (E1)₄(E2)₂[Sn(E15)₄] (with E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) of the Na₆[ZnO₄] Type and the Superstructure Variant of K₄Sr₂[SnAs₄] The silvery to dark metallic lustrous compounds (E1)₄(E2)₂[Sn(E15)₄] (E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) were prepared from melts of stoichiometric mixtures of the elements. They crystallize in the Na₆[ZnO₄]‐type structure (hexagonal, space group: P6₃mc, Z = 2; Na₄Ca₂[SnP₄]: a = 938.94(7), c = 710.09(8) pm; K₄Sr₂[SnAs₄]: a = 1045.0(2), c = 767.0(1) pm; K₄Ba₂[SnP₄]: a = 1029.1(6), c = 780.2(4) pm; K₄Ba₂[SnAs₄]: a = 1051.3(1), c = 795.79(7) pm; K₄Ba₂[SnSb₄]: a = 1116.9(2), c = 829.2(1) pm; K₄Ba₂[SnBi₄]: a = 1139.5(2), c = 832.0(2) pm). The anionic partial structure consists of tetrahedra [Sn(E15)₄]^8– orientated all in the same direction along [001]. In the cationic partial structure one of the two cation positions is occupied statistically by alkali and alkaline earth metal atoms. Up to now only for K₄Sr₂[SnAs₄] a second modification could be isolated, forming a superstructure type with three times the unit cell volume (hexagonal, space group: P6₃cm, Z = 6; a = 1801.3(2), c = 767.00(9) pm) and an ordered cationic partial structure.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Synthese und Struktur der Nitrido‐Komplexe [(n‐Bu)4N]2[{(L)Cl4Re≡N}2PtCl2] (L = THF und H2O) und [(n‐Bu)4N]2[(H2O)Cl4Re≡N‐PtCl(μ‐Cl)]2

Synthesis and Crystal Structure of the Nitrido Complexes [(n‐Bu)₄N]₂[{(L)Cl₄Re≡N}₂PtCl₂] (L = THF und H₂O) and [(n‐Bu)₄N]₂[(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂ The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}_2—PtCl₂] ( 1a ) is obtained by the reaction of [(n‐Bu)₄N][ReNCl₄] with [PtCl₂(C₆H₅CN)₂] in THF/CH₂Cl₂. It forms red crystals with the composition 1a · 2 CH₂Cl₂ crystallizing in the tetragonal space group I4₁/a with a = 3186.7(2); c = 1311.2(1) pm and Z = 8. If the reaction of the educts is carried out without THF, however under exposure to air the compound [(n‐Bu)₄N]₂[{(H₂O)Cl₄Re≡N}₂PtCl₂] ( 1b ) is obtained as red trigonal crystals with the space group R3 and a = 3628.3(3), c = 1231.4(1) pm and Z = 9. In the centrosymmetric complex anions [{(L)Cl₄Re≡N}₂PtCl₂]^2— a linear PtCl₂moiety is connected in a trans arrangement with two complex fragments [(L)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡dqN‐Pt. For Pt^II such results a square‐planar coordination PtCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 169.5 pm and Pt‐N = 188.8 pm ( 1a ), respectively, Re‐N = 165.6 pm and Pt‐N = 194.1 pm ( 1b ). By the reaction of [(n‐Bu)₄N][ReNCl₄] with PtCl₄ in CH₂Cl₂ platinum is reduced forming the heterometallic Re^VI/Pt^II complex, [(n‐Bu)₄N]₂[(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂ ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 2012.9(1); b = 1109.0(2); c = 2687.4(4) pm; β = 111.65(1)° and Z = 4. In the central unit ClPt(μ‐Cl)₂PtCl of the anionic complex [(H₂O)Cl₄Re≡N‐PtCl(μ‐Cl)]₂^2— with the symmetry C₂ the coordination of the Pt atoms is completed by two nitrido bridges Re≡N‐Pt to nitrido complex fragments [(H₂O)Cl₄Re≡N] ^— forming a square‐planar arrangement for the Pt atoms. The distances in the linear nitrido bridges are Re‐N = 165.9 pm and Pt‐N = 190.1 pm.     

Ba4[WN4]Cl2: The first nitridotungstate(VI) chloride

Transparent yellow crystals of Ba₄[WN₄]Cl₂ were grown at 850°C by the reaction of Ba(NH₂)₂ with W in a KCl melt under flowing nitrogen. The compound crystallizes monoclinic in P2₁/m and Z = 2 with the cell parameters a = 8.447(4) Å, b = 6.143(2) Å, c = 10.727(6) Å and β = 99.04(4)°. The crystal structure contains isolated anions [WN₄]^6? and Cl^?. It is the first nitridotungstate(VI) chloride reported so far.     

Über RhSCl ein hexamerer,molekularer Rhodium(III)‐Komplex mit SCl2‐Liganden

About RhSCl₅ — a Hexameric, Molecular Rhodium(III) Complex with SCl₂ Ligands Needle‐shaped red crystals of RhSCl₅ were obtained by reaction of Rh metall or RhI₃ with SCl₂ in a closed silica ampoule. In the monoclinic crystal structure the Rh atoms are octahedrally coordinated by 5 Cl atoms and a SCl₂ ligand. In each case six RhCl₅(SCl₂) groups are connected with each other by two common edges of Cl atoms to form hexameric molecules [RhCl₃(SCl₂)]₆. In the pseudohexagonal unit cell (monoclinic, space group C2/c, a = 26.215(5) Å, b = 6.7750(10) Å, c = 26.868(5) Å, β = 119.06(3)°, Z = 4) the molecules are stacked in columns and form a hexagonal rod package.     

[{ReN(Me2PhP)(Et2dtc)Cl}2{ReN(Et22tc)2}2{SbCl3}2] — ein neuer vierkerniger Rheniumkomplex mit asymmetrischen Nitridobrücken

[{ReN(Me₂PhP)(Et₂dtc)Cl}₂{ReN(Et₂dtc)₂}₂{SbCl₃}₂] — a Novel Tetranuclear Rhenium Complex with Asymmetric Nitrido Bridges The reaction of [ReN(Et₂dtc)₂(Me2₂hP)] (Me₂PhP = dimethylphenylphosphine, Et₂dtc^‐ = diethyldithiocarbamate) with SbCl₃ in dichloromethane results in the formation of [{ReN(Me₂PhP)(Et2₂tc)Cl}₂{ReN(Et₂dtc)₂}₂{SbCl₃}₂]. A {Re≡N‐}₄ ring with asymmetric nitrido bridges is stabilised by the co‐ordination of SbCl₃ onto the chloro ligands and sulphur atoms of the dithiocarbamates. The compound decomposes upon heating in acetonitrile and the fragments of the tetrameric complex re‐arrange to form [ReN‐(Me₂PhP)(Et₂dtc)Cl]₄ and [ReN(Et₂dtc)₂]. The multinuclear rhenium compounds have been studied by X‐ray crystallography. The 8‐membered {Re≡N‐}₄ ring system in [{ReN(Me₂PhP)(Et₂dtc)Cl}2₂ReN(Et₂dtc)₂}₂{SbCl₃}₂] is almost planar, while that of [ReN(Me₂PhP)(Et₂dtc)Cl]₄ is clearly V‐shaped when viewed down either diagonal Re…Re axis. A dihedral angle of 47.88(2)° has been found between the contributing planes.     

Synthesis and Structure of (NH4)2[(AuI4)(MI4)] (M = Ga,In)

The compounds (NH₄)₂[(AuI₄)(MI₄)] (M = Ga, In) were obtained in sealed glass ampoules by reaction of I₂, NH₄I, Au and Ga or In as air‐sensitive black crystals. Both compounds crystallize in the orthorhombic space group Pnma (No. 62) and are isotypic: (NH₄)₂[(AuI₄)(GaI₄)], a = 12.619(2), b = 20.625(5) and c = 7.693(2) Å; (NH₄)₂[(AuI₄)(InI₄)], a = 12.587(2), b = 20.606(5) and c = 7.696(2) Å. The structures can be described as constituted of NH₄⁺ cations and anionic zig zag chains of alternating tetrahedral MI₄^– (M = In, Ga) and square planar AuI₄^– units running along [010]. Within the chains, the MI₄^– ions form weak interactions with two of their I atoms to the AuI₄^– ions resulting in strongly elongated AuI₆ octahedra.     

K10[Co4O9], ein neues Oxocobaltat(II) mit oligomerem Anion

K₁₀[Co₄O₉], a New Oligooxocobaltate(II) For the first time dark-red single crystals of K₁₀[Co₄O₉] were obtained by heating mixtures of KO_0.48 and CdO (molar ratio 2.7:1) in closed Co-cylinders at 450°C during 73 d. Structure solution and refinement (four-circle diffractometer data, Mo Kα , 2 996 out of 2 996 I_o(hkl), R = 5.20%, R_w = 3.03%) confirm the space-group P1 and show structural relationship with Na₁₀[Co₄O₉] [2]. The lattice constants are a = 667.84(5) pm, b = 917.91(9) pm, c = 908.49(7) pm, α = 119.400(7)°, β = 90.851(7)°, γ = 110.260(6)°, Z = 1 . (powder data (Guinier-Simon), standard deviations in parentheses) MAPLE calculations are made and a comparative survey of MAPLE values of oxocobaltates(II) is given.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.     

(Me2NH2)[(Ph3Sn)3(MoO4)2], ein Triorganozinnmolybdat mit Schichtstruktur

(Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂], a Triorganotin Molybdate with Layer Structure The reaction of [(Ph₃Sn)₂MoO₄] with (Me₂NH₂)Cl in an acetonitrile/water mixture leads to the formation of (Me₂NH₂)[(Ph₃Sn)₃(MoO₄)₂] ( 1 ). ( 1 ) crystallizes in the space group Pca2₁ with a = 1967.0(4), b = 1353.1(2) and c = 2176.6(5) pm. In the crystal structure of 1 Ph₃SnO₂ bipyramides and MoO₄ tetrahedra are linked by corner sharing to give a layer structure. Additionally the layers are connected by O···H···N hydrogen bridges between MoO₄ groups and [Me₂NH₂]⁺ ions to give a 3D network structure.     

SnAl2OCl6, ein quaternäres Oxidchlorid mit kantenverknüpften [Al4O2Cl10]‐Tetrameren und [(SnCl2/2Cl5)2]‐Dimeren

SnAl₂OCl₆, a Quaternary Oxide‐Chloride with Edge‐Sharing [Al₄O₂Cl₁₀] Tetramers and [(SnCl_2/2Cl₅)₂] Dimers Single crystals of SnAl₂OCl₆ were obtained from the educts SnCl₂ and AlCl₃ (obviously containing an oxidic impurity) in silica ampoules with the aid of the Bridgman technique. According to single‐crystal structure analysis, SnAl₂OCl₆ crystallizes with the monoclinic system (P2₁/n, Z = 4, a = 942.3(2), b = 1225.8(2), c = 948.4(3) pm, β = 96.42(2)°). Characteristic structural features are centrosymmetric tetramers [Al₄O₂Cl₁₀] and [(SnCl_2/2Cl₅)₂] dimers which are connected via common edges, finally building up a three‐dimensional structure.     

Ternäre Alkalimetall‐Übergangsmetall‐Acetylide der Zusammensetzung A2MC2 mit A = Rb,Cs und M = Pd,Pt

Ternary Alkali Metal Transition Metal Acetylides A₂MC₂ with A = Rb, Cs, and M = Pd, Pt By the reaction of Rb₂C₂ and Cs₂C₂ with palladium or platinum powder in sealed glass ampoules at 653 K ternary acetylides A₂MC₂ (A = Rb, Cs; M = Pd, Pt) were obtained. Their crystal structures were solved and refined by means of X‐ray powder investigations (Na₂PdC₂ structure type, P 3 m1, Z = 1). The crystal structures are characterised by [M(C₂)_2/2^2–] chains separated by the alkali metals. Raman spectroscopic investigations revealed wave numbers of the C–C stretching vibrations between 1833 and 1842 cm^–1, which are in good agreement with the results of the analogous sodium and potassium compounds.     

The X‐ray Crystal Structures of Hg(C6F4X‐p)2 (X = NH2, OMe,or Me) – Two Examples of Supramolecular Lewis Acid/Base Complexes

The X‐ray crystal structures of Hg(C₆F₄X‐p)₂ (X = NH₂, OMe, or Me) show the compounds to have almost linear C–Hg–C stereochemistry (X = NH₂, 176.3(4)°; X = OMe, 179.5(2)°; X = Me, 176.3(2)°), and the two tetrafluoroaryl rings rotated ca. 52–62° with respect to each other. Substantial conjugation of NH₂ and OMe groups with the aromatic rings is evident from N–C and O–C(Ar) distances. For X = NH₂ or OMe, two weak N(O)–Hg coordination interactions per mercury lead to a two dimensional supramolecular chain structure containing pairs of π‐stacked aromatic rings at near van der Waals contact distances rotated at 62.2° (X = NH₂) or 52.9° (X = OMe) to each other. In Hg(C₆F₄Me‐p)₂, which does not have potential donor atoms, no supramolecular structure is obtained, the molecules being laterally displaced from one another.