Cs5[Na{W4N10}]: The first framework nitridotungstate(VI)

Cs₅[Na{W₄N₁₀}] was prepared from a mixture of NaNH₂, CsNH₂ and tungsten powder (molar ration 1 : 10 : 4) at 700°C in autoclaves. After the reaction is finished the nitride is embedded in an alkali metal matrix. Dark red crystals were isolated by washing out the alkali metal with liquid ammonia at room temperature. The structure of Cs₅[Na{W₄N₁₀}] was solved by X-ray single crystal data: I4₁ (No. 80), Z = 4, a = 13.926(3) Å, c = 8.723(3) Å, Z(F) ≥ 3σ(F) = 1535, Z(Variables) = 63, R/R_w = 0.040/0.052. The compound is highly sensitive against moisture giving oxotungstates and ammonia. It contains a framework of tetrahedra [WNN_3/2^1.5?]. Sodium shares four terminal nitrogen ligands. Including sodium a distorted, β-cristobalite type arrangement [Na{W₄N₁₀}^5?] results. It contains caesium in all interstices formed by twelve nitrogen ligands in so-called Friauf polyhedra.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

Cs4[Sc6C]Cl13 und Cs4[Pr6(C2)]I13 — zwei Beispiele für das fehlende Bindeglied bei der Verknüpfung der Baueinheiten [M6Z]XX

Cs₄[Sc₆C]Cl₁₃ and Cs₄[Pr₆(C₂)]I₁₃ — Two Examples for the Missing Link in the Connectivity of [M₆Z]X X Building Units Cs₄[Sc₆C]Cl₁₃ (tetragonal, I4₁/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, R_w = 0.026) and Cs₄[Pr₆(C₂)]I₁₃ (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, R_w = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl₃ and PrI₃, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc₆C] and [Pr₆(C₂)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xⁱ and 6 X^a; X = Cl or I). The connection is carried out via the motif [M₆Z]XXXX (M = Sc and Pr; Z = C and C₂, respectively) and is thereby the missing link of the motifs of connection for the composition A_x[M₆Z]X₁₃. Analogous interconnection of [TiO₆] octahedra is found in the anatase-type of structure of TiO₂.     

Synthese und Kristallstruktur von Na10[P4(NH)6N4](NH2)6(NH3)0,5 mit dem adamantanartig aufgebauten Anion [P4(NH)6N4]4−

Synthesis and Crystal Structure of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 with an Adamantane-like Anion [P₄(NH)₆N₄]^4? Crystals of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 were obtained by the reaction of P₃N₅ with NaNH₂ (molar ratio 1:20) within 5 d at 600°C in autoclaves. The following data characterize X-ray investigations: Fm3 m, Z = 8, a = 15.423(2) Å, Z(F) = 261 with F ≥ 3 σ(F) Z(Variables) = 27, R/R_w = 0.086/0.089 The compound contains the hitherto unknown anion [P₄(NH)₆N₄]^4?, which resembles adamantane. The total structure can be described as follows: The centers of gravity of units of [Na₈(NH₂)₆(NH₃)]²⁺ – 8Na⁺ on the corners of a cube, 6NH₂^? on the ones of an inscribed octahedron with NH₃ in the center – follow the motif of a cubic-closest packed arrangement. Units of [Na₁₂(NH₂)₆]⁶⁺ – 12Na⁺ on the corners of a cuboctahedron and 6NH₂^? on the ones of an inscribed octahedron – occupy all octahedral and those of [P₄(NH)₆N₄]^4? all tetrahedral sites.     

The crystal structure of tris (ethylenediamine), cobalt(III) hexacyanoferrate(III)dihydrate,Co(C2H8N2)3[Fe(CN)6] · 2H2O

The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2_l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)₃ Q(CN)₆ · H₂O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous.     

Na2Mn(NH2)4: Ein neuer Schichtenstrukturtyp

Na₂Mn(NH₂)₄: A New Type of Layered Structure The structure of Na₂Mn(NH₂)₄ was solved by X-ray single crystal data including H-positions: P2₁/c, Z = 4, a = 6.331(1) Å, b = 14.542(3) Å, c = 7.212(1) Å, β = 116.29(1)°, Z(F ≥ 3σ = (F)) = 1343, Z(parameters) = 96, R/R_W = 0.023/0.029. The compound crystallizes in a new type of structure. Within layered blocks the amide ions are arranged with the motif of a hexagonal closest packing of spheres. Within these blocks alternating layers contain sodium in all octahedral sites and manganese in an ordered way in a quarter of tetrahedral sites.     

Die Kristall- und MolekülStruktur von (S4N3)2SbCI5

The structure of (S₄N₃)₂SbCI₅ has been determined by X-ray methods using least-squares′ refinement. The compound crystallises monoclinic; C–P2₁/c, a = 9.24 Å, b = 17.77 Å, c = 11.29 Å, β = 110.06°, Z = 4. The antimony atom has a fivefold coordination the geometry being derived from a deformed octahedron, the S₄N-rings retained their planar shape.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsBr(acac)(PPh3)] und [OsBr(acac)(AsPh3)]

Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh₃)] and [OsBr(acac)(AsPh₃)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh₃ or AsPh₃ in ethanol the complexes [OsBr(acac)(PPh₃)] ( 1 ) and [OsBr(acac)(AsPh₃)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 2₁/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 2₁/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh₃ and AsPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm^–1.     

Darstellung und Strukturbestimmung zweier Salze der Trimetaphosphimsäure,K3(PO2NH)3 und Rb3(PO2NH)3

Synthesis and Structure Determination of Two Salts of the Trimetaphosphimic Acid, K₃(PO₂NH)₃ and Rb₃(PO₂NH)₃ The reaction between P₃N₅ and the corresponding alkalimetal hydroxide monohydrate under ammonothermal conditions (6 kbar, 450 °C after 10 d) in autoclaves leads to the salts of the trimetaphosphimic acid K₃(PO₂NH)₃ resp. Rb₃(PO₂NH)₃. The structure of K₃(PO₂NH)₃ was solved by single crystals X-ray methods. The isotypic structure of Rb₃(PO₂NH)₃ was solved by X-ray powder diffraction methods. K₃(PO₂NH)₃: R3 (No. 148), a = 12.615(3) Å, c = 10.224(2) Å, Z = 6, R₁/wR₂ = 0.0276/0.0726, N(F > 2σ(F)) = 769, N(Var.) = 51.Rb₃(PO₂NH)₃: R3 (No. 148), a = 12.9971(5) Å, c = 10.5485(5), Z = 6, R_Bragg(F) = 0.0626, 289 reflections. K₃(PO₂NH)₃ and Rb₃(PO₂NH)₃ contain six-membered rings P₃N₃ substituted by oxygen which are connected to double molecules by N–H … O bridge bonds. These twinmolecules are stacked in columns which form the motive of close packed rods. K⁺ resp. Rb⁺ are between these columns. They are coordinated by 6 O which belong to 5 different rings.     

Synthese und Struktur des ersten ternären Blei(II)-Oxocuprats(I): PbCu2O2

Synthesis and Structure of the First Ternary Lead(II) Copper(I) Oxide: PbCu₂O₂ PbCu₂O₂ can be prepared by solid state reaction or by precipitation from a basic aqueous solution. Single crystals of the new compound were prepared by recrystallisation from a molten mixture (PbO? Cu₂O) and investigated by X-ray diffractometer technique. PbCu₂O₂ crystallizes isotypically with the homologue silver compound PbAg₂O₂ (monoclinic with a = 8.22₃ Å, b = 8.28₉ Å, c = 6.01₅ Å, β = 132.6₂°, Z = 4, space group C? C 1 2/c 1). The crystallographic data from the X-ray investigation are reported. The structure is built by endless [PbO_4/4]- and [CuO_2/4]-chains. Pb²⁺ has a one-sided asymmetric coordination with four next oxygen neighbours and Cu⁺ forms a stretched dumbbell with two oxygen atoms.     

K3Au5Pb: eine Schichtstruktur mit [AuAu3/2]-Gold-Tetraedern und [Pb2/2]-Blei-Ketten

K₃Au₅Pb: Layers of [AuAu_3/2] Gold Tetrahedra and [Pb_2/2] Lead Chains Silver coloured, brittle single crystals of K₃Au₅Pb were synthesized by reaction of potassium azide with gold sponge and lead powder at T = 920 K. The structure of the compound (space group Imma, Z = 4, a = 5.646(1) Å, b = 19.500(4) Å, c = 8.412(1) Å) was determined from X-ray single-crystal diffractometry data. The gold lead partial structure consists of layers of [AuAu_3/2] tetrahedra and [Pb_2/2] zigzag chains with four-bonded lead atoms which are connected to a framework structure via Au–Pb contacts. The potassium atoms occupy channels within the gold lead partial structure.     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Zur Kenntnis der Oxocobaltate(II) Na4[CoO3], ein Nesocobaltat(II)

On the Knowledge of Oxocobaltates(II). Na₄[CoO₃], the First Nesocobaltate(II) Newly prepared transparent, blood red single crystals of Na₄[CoO₃] (Na₂O/?CoO’? Na:Co = 4.4:1, cobalt tube, 550°C, 20d, dry argon), crystallize triclinically, P1, a = 8.14₄, b = 6.22₀, c = 5.75₈ Å; α = 117.5, β = 89.9, γ = 111.2 (diffractometer data), Z = 2. There are carbonate-like, isolated [CoO₃] groups, respectively parameters and distances see text. 2358 symmetry independent reflections (automatical four cycle diffractometer PW 1100, Mo–Kα, graphite monochromator, 4° ? Θ ? 36°), R = 0.0597. The Madelung Part of the Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN and Mean Fictive Ionic Radii, MEFIR are calculated and discussed.     

Goldreiche Auride mit Caesium: Cs1,34Rb0,66RbAu7 und Cs1,60Rb0,40RbAu7

Gold-rich Aurides with Caesium: Cs_1.34Rb_0.66RbAu₇ and Cs_1.60Rb_0.40RbAu₇ Cs_1,60Rb_0,40RbAu₇, Raumgruppe Cmmm, Z = 2, a = 5,677(1) Å, b = 13,273(3) Å, c = 7,288(1) Å, R1/wR2 = 0,0392/0,0892, Z(F) ≥ 2σ(F) = 700 and Z(Var.) = 23. Silver coloured, brittle single crystals of Cs_1.34Rb_0.66RbAu₇ and Cs_1.60Rb_0.40RbAu₇ were obtained by the reaction of CsN₃, RbN₃ and gold sponge at 903 K. The structures were determined from X-ray single-crystal diffractometry data: Cs_1.34Rb_0.66RbAu₇, space group Cmmm, Z = 2, a = 5.657(1) Å, b = 13.265(4) Å, c = 7.281(2) Å, R1/wR2 = 0.0373/0,0628, N(F) ≥ 2σ(F) = 818 and N(var.) = 23.     

Halogenaustausch an Re3-Clustern: Ein neuer Syntheseweg für binäre und ternäre Rhenium(III)-bromide. Kristallstrukturen von Cs2[Re3Br11] und Cs3[Re3Br3Cl9]

Halogen Exchange at Re₃-Clusters: A New Synthetic Route to Binary and Ternary Rhenium(III) Bromides. Crystal Structures of Cs₂[Re₃Br₁₁] and Cs₃[Re₃Br₃Cl₉] The substitution of “inner” ligands in transition metal clusters in aqueous HX solutions is hitherto unknown. For the first time the substitution of bridging and terminal chloride for bromide ions was observed at rhenium clusters, [Re₃(μ-Cl^i,b)₃(Cl)(Cl^i,t)_(3?x)(H₂O^i,t)_x]^(3?x)? (x = 0–3), via the reaction of “ReCl₃ · 2 H₂O” in hot hydrobromic acid solution under an inert gas atmosphere. This establishes a new synthetic route to ternary Re(III) bromides as well as to ReBr₃. However, ternary Re(IV) bromides, A₂ReBr₆ (A = Rb, Cs), are dominating in the presence of oxygen, rhenium(III) bromides are only by-products. Dark brown rods of Cs₂[Re₃Br₁₁] are obtained from argon saturated, hot hydrobromic acid solutions of “ReCl₃ · 2 H₂O” and CsBr. The crystal structure (orthorhombic, Pnma (Nr. 62); a = 955.51(5); b = 1 610.29(10); c = 1 372.70(9); Z = 4; V_m = 318.0(2) cm³mol^?1; R = 0.084, R_w = 0.058) consists of defect clusters [Re₃BrBrBr□^i,t]^2? in which one in plane, terminal position is not occupied. The substitution of “inner” ligands has been observed in the case of chloride for bromide only, the Br^i,b and I^i,b ligands in ReBr₃ and ReI₃, respectively, are not substituted in hydrochloric acid even at temperatures as high as 100°C. Bordeaux red square pyramids of CsReBrCl₃ = Cs₃[Re₃(μ-Br^i,b)₃ClCl] are obtained from hot hydrochloric acid solutions of ReBr₃ · 2/3 H₂O upon evaporation. CsReBrCl₃ (orthorhombic, C2cm (Nr. 40); a = 1 419.0(1); b = 1 419.2(1); c = 1 080.30(8) pm; Z = 4; V_m = 327.6(3) cm³mol^?1; R = 0.033, R_w = 0.028) is isostructural to the corresponding chloride CsReCl₄.     

Synthese und Kristallstruktur eines Natrium-tetraoxonitridowolframats(VI), Na5WO4N

Synthesis and Crystal Structure of Sodium Tetraoxo Nitrido Tungstate(VI), Na₅WO₄N Colourless crystals of Na₅WO₄N are obtained besides Na₄WO₂N₂ [1] by the reaction of WO₃ with NaNH₂ (15:1) at 350°C ≥ T ≥ 750°C in autoclaves to prevent early decomposition of sodium amide. X-ray single crystal investigations are characterized by the following data:

• Na₅WO₄N: Cmc2₁ (No. 36), Z = 4
• a = 9.873(2) Å, b = 5.769(1) Å, c = 10.648(2) Å
• Z(F)≥ 3σ(F) = 2182, Z(Var.) = 55, R/R_w = 0.029/0.039

The structure contains the tetragonal pyramidal ion WO₄N^5? with nitrogen at the apex connected via Na⁺ ions irregularly coordinated by one nitrogen and four oxygen atoms of different anions.     

Zur Kristallchemie der Kupfer-Lanthanoid-Oxowolframate: (I) triklin-α-CuTbW2O8, (II) monoklin-CuInW2O8 und (III) monoklin-CuYW2O8

The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW₂O₈, (II): monoclinic-CuInW₂O₈ and (III): monoclinic-CuYW₂O₈ Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu²⁺ and Mo⁵⁺.     

Synthese und Kristallstruktur von Mangan(II)‐ und Zinkamid,Mn(NH2)2 und Zn(NH2)2

Synthesis and Crystal Structure of Manganese(II) and Zinc Amides, Mn(NH₂)₂ and Zn(NH₂)₂ Metal powders of manganese resp. zinc react with supercritical ammonia in autoclaves in the presence of a mineralizer Na₂Mn(NH₂)₄ resp. Na₂Zn(NH₂)₄_.0.5NH₃ to well crystallized ruby‐red Mn(NH₂)₂ (p(NH₃) = 100 bar, T = 130°C, 10 d) resp. colourless Zn(NH₂)₂ (p(NH₃) = 3.8 kbar, T = 250°C, 60 d). The structures including all H‐positions were solved by x‐ray single crystal data: Mn(NH₂)₂: I4₁/acd, Z = 32, a = 10.185(6) Å, c = 20.349(7) Å, N(F_o) with F > 3σ (F) = 313, N(parameter) = 45, R/R_w = 0.038/0.043. Zn(NH₂)₂: I4₁/acd, Z = 32, a = 9.973(3) Å, c = 19.644(5) Å, N(F_o) with F > 3σ (F) = 489, N(parameter) = 45, R/R_w = 0.038/0.043. Both compounds crystallize isotypic with Mg(NH₂)₂ [1] resp. Be(NH₂)₂ [2]. Nitrogen of the amide ions is distorted cubic close packed. One quarter of tetrahedral voids is occupied by Mn²⁺‐ resp. Zn²⁺‐ions in such an ordered way that units M₄(NH₂)₆(NH₂)_4/2 occur. The H‐atoms of the anions have such an orientation that the distance to neighboured cations is optimum.     

Darstellung und Struktur eines Ammoniumdiamidodioxophosphats(V), NH4PO2(NH2)2

Synthesis and Structure of an Ammonium Diamidodioxophosphate(V), NH₄PO₂(NH₂)₂ The ammonolysis of P₃N₅ under ammonothermal conditions (T = 400°C, p(NH₃) = 6 kbar, 14 d in autoclaves) in the presence of small definite amounts of water leads to the formation of NH₄PO₂(NH₂)₂. The structure was solved by single crystal X-ray methods. NH₄PO₂(NH₂)₂: P2₁/c (Nr. 14), a = 6.886(1) Å, b = 8.366(2) Å, c = 9.151(2) Å, β = 111.78(3)°, Z = 4, R₁/wR₂ = 0.026/0.072, Z(F > 2σ(F)) = 1183, N(variables) = 87. In NH₄PO₂(NH₂)₂ the anions [PO₂(NH₂)₂]^? are linked to chains by N? H …? N and N? H …? O bridge bonds. The ammonium ions are located between these chains and are donors for N? H …? O bridge bonds which connect the chains three-dimensionally.     

K2NaGaP2, Cs2NaGaP2, K2NaGaAs2, K2NaInP2 und K2NaInAs2, Verbindungen mit den SiS2-isosteren Polyanionen [MX4/2]3− (MGa,In; XP,As)

K₂NaGaP₂, Cs₂NaGaP₂, K₂NaGaAs₂, K₂NaInP₂ and K₂NaInAs₂, Compounds with the Polyanions [MX_4/2]^3? (M?Ga, In; X?P, As) isosteric with SiS₂ The title compounds are synthesized from stoichiometric mixtures of the elements or from Na, KP(KAs), Cs₄P₆ and MX (M?Ga, In; X?P, As) at 950K. They are isotypic and crystallize in the space group Ibam (No. 72) with Z=4. The anionic partial structure is characterized by infinite chains [MX_4/2]^3? which are isosteric to SiS₂. Vibrational spectra are measured and interpreted based on the symmetry D_4h-P(2/m 2/c)4₂/m of the isolated polymer chain [MX₂]^3?. A good agreement between observed and calculated frequencies is obtained by using a force field of the tetrameric fragment [M₄X₁₀]^18? (three four-membered M₂X₂ rings).