Penta‐Ammoniates of Aluminium Halides: The Crystal Structures of AlX3·5NH3 with X = Cl,Br, I

Colourless crystals grow in the colder part of a glass ampoule when AlX₃·5NH₃ with X = Cl, Br, I is heated for 3—6 d to 330 °C (Cl), 350 °C (Br) and 400 °C (I), respectively. The chloride forms hexagonal prisms while the bromide and iodide were obtained as a bunch of lancet‐like crystals. The chloride and bromide crystallize isotypic whereas the iodide has an own structure type. All three are related to the motif of the K₂PtCl₆ type. So the formula of the ammoniates may be written as X₂[Al(NH₃)₅X] ≙ [Al(NH₃)₅X]X₂. The compounds are characterized by the following crystallographic data AlCl₃·5NH₃: Pnma, Z = 4, a = 13.405 (1)Å, b = 10.458 (1)Å, c = 6.740 (2)Å AlBr₃·5NH₃: Pnma, Z = 4, a = 13.808 (2)Å, b = 10.827 (1)Å, c = 6.938 (1)Å AlI₃·5NH₃: Cmcm, Z = 4, a = 9.106 (2)Å, b = 11.370 (2)Å, c = 11.470 (2)Å For the chloride and the bromide the structure determinations were successful including hydrogen positions. All three compounds contain octahedral molecular cations [Al(NH₃)₅X]²⁺ located in distorted cubes formed by the remaining 2X^— ions. The orientation of the octahedra to each other is clearly different for those with X = Cl, Br in comparison to the one with X = I.     

Synthese und Kristallstruktur der Monoammoniakate von Lithiumhalogeniden: LiBr·NH3 und LiI·NH3

Syntheses and Crystal Structures of the Monoammoniates of Lithium Halides: LiBr·NH₃ and LiI·NH₃ Crystals of LiBr·NH₃ and LiI·NH₃ sufficient in size and quality for X‐ray structure determinations were obtained in autoclaves by the reaction of Li with NH₄Br and LiH with NH₄I at 523 K and 423 K respectively. Lattice constants obtained from X‐ray single crystal data are: LiBr·NH₃: P2₁/n, a = 7, 077(2)Å, b = 7, 026(2)Å, c = 7, 490(2)Å β = 114, 84(3)°, Z = 4 LiI·NH₃: P2₁, a = 4, 493(1)Å, b = 6, 077(1)Å, c = 7, 512(2)Å β = 107, 15(3)°, Z = 2 The ammoniates contain different structural building units. Both of them contain layers of connected tetrahedra Li(NH₃)X_3/3 with X = Br, I. Tetrahedra‐double units with a common Br‐Br edge occur, whilst for the iodide all tetrahedra are exclusively vertex connected to puckered layers. IR‐ and Raman‐spectroscopic measurements show, that only weak H‐bridges N‐H···X are present and that the NH₃‐ligands are in fixed positions at room temperature.     

Hexamincyclotriphosphazenhemiammoniakat,P3N3(NH2)6 · 0,5 NH3, ein Produkt der Hochdruckammonolyse von weißem Phosphor

Hexaminecyclotriphosphazenehemiammoniate, P₃N₃(NH₂)₆ · 0.5 NH₃, a Product of High Pressure Ammonolysis of White Phosphorus White phosphorus gives at NH₃-pressures ≥5 kbar and temperatures above 250°C in a disproportionation reaction P₃N₃(NH₂)₆ · 0.5 NH₃; besides these products red phosphorus is formed. The yield on P₃N₃(NH₂)₆ · 0.5 NH₃ increases with T and is about 70–80% at 400°C as to the disproportionation reaction of the amount of white phosphorus. X-ray structure determination was successful on single crystals of P₃N₃(NH₂)₆ · 0.5 NH₃. Pbca, N = 8 a = 11.395(3) Å, b = 12.935(4) Å, c = 12.834(4) Å R = 0.035, R_w = 0.041 with w = 1, N (F_o²) ≥ 3σ(F_o²) = 1371, N(Var.) = 166. The molecules are connected by N? H? N-bridgebonds with 3.04 Å ≤ d(N …? N) ≤ 3,19 Å and d (N? H) = 0.87 Å. The compound is furthermore characterized by IR-data and its thermical behaviour.     

Vergleich der Kristallstrukturen der Tetraammoniakate von Lithiumhalogeniden,LiBr·4NH3 und LiI·4NH3, mit der Struktur von Tetramethylammoniumiodid,N(CH3)4I

A Comparison of the Crystal Structures of the Tetraammoniates of Lithium Halides, LiBr·4NH₃ and LiI·4NH₃, with the Structure of Tetramethylammonium Iodide, N(CH₃)₄I Crystals of the tetraammoniates of LiBr and LiI sufficient in size for X‐ray structure determinations were obtained by slow evaporation of NH₃ at room temperature from a clear solution of the halides in liquid ammonia. The compounds crystallize in the space group Pnma (No. 62) with four formula units in the unit cell: LiBr·4NH₃: a = 11.947(5)Å, b = 7.047(4)Å, c = 9.472(3)Å LiI·4NH₃: a = 12.646(3)Å, b = 7.302 (1)Å, c = 9.790(2)Å For N(CH₃)₄I the structure was now successfully solved including the hydrogen positions of the methyl groups. N(CH₃)₄I: P4/nmm (No. 129), Z = 2, a = 7.948(1)Å, c = 5.738(1)Å The ammoniates of LiBr and LiI crystallize isotypic in a strongly distorted arrangement of the CsCl motif. Even N(CH₃)₄I has an CsCl‐like structure. Both structure types differ mainly in their orientation of the [Li(NH₃)₄]⁺ — resp. [N(CH₃)₄]⁺ — cations with respect to the surrounding “cube” of anions.     

Kaliumamidotrioxogermanate(IV) – Wasserstoff-Brückenbindungen in K3GeO3NH2 und K3GeO3NH2 · KNH2

Potassium Amido Trioxo Germanates(IV) – Hydrogen Bridge Bonds in K₃GeO₃NH₂ and K₃GeO₃NH₂ · KNH₂ Colorless crystals of K₃GeO₃NH₂ and of K₃GeO₃NH₂ · KNH₂ were obtained by the reaction of KNH₂ with GeO₂ in supercritical ammonia at 450°C and p = 6 kbar in high-pressure autoclaves within 15 resp. 5 days. The crystal structures of both compounds were solved by X-ray single crystal methods. K₃GeO₃NH₂: P1 , a = 6.390(1) Å, b = 6.684(1) Å, c = 7.206(1) Å, α = 96.47(1)°, β = 101.66(1)°, γ = 91.66(1)°, Z = 2, R/R_w = 0.020/0.022, N(I) ≥ 2σ(I) = 3023, N(Var.) = 82 K₃GeO₃NH₂ · KNH₂: P2₁/c, a = 10.982(6) Å, b = 6.429(1) Å, c = 12.256(8) Å, β = 106.12(1)°, Z = 4, R/R_w = 0.022/0.029, N(F) ≥ 3σ(F) = 1745, N(Var.) = 107. In K₃GeO₃NH₂ tetrahedral ions GeO₃NH₂^3? are connected to chains by N? H …? O bridge bonds with 2.18 Å ≤ d(H …? O) ≤ 2.40 Å for d(N? H) ? 1.0 Å and by potassium ions while in K₃GeO₃NH₂ · KNH₂ bridge bonds between NH₂ groups of GeO₃NH₂^3? and NH₂^? ions as acceptors occur with 2.41 Å ≤ d((N? )H …? NH₂^?) ≤ 2.61 Å for d(N? H) ? 1.0 Å.     

Wasserstoffbrückenbindungen in den Monoammoniakaten von Kalium‐ und Caesiumamid

Hydrogen Bonds in the Monoammoniates of Potassium and Cesium Amide X‐ray structure determination was carried out on the monoammoniates of potassium and cesium amide. Crystals of KNH₂ · NH₃ were grown from liquid NH₃ at 50 °C > T > 20 °C. They crystallize in the cold part of a pressure resistant glass apparatus. Single crystals of CsNH₂ · NH₃ were obtained by zone‐melting at —30 °C in x‐ray capillaries. The following data characterize the crystal chemistry of the compounds: KNH₂ · NH₃ Cmc2₁, Z = 4 21 °C a = 3, 938(1) Å, b = 10, 983(3) Å, c = 5, 847(1) Å CsNH₂ · NH₃ Pnma, Z = 4 30 °C a = 7, 103(1) Å, b = 5, 390(1) Å, c = 10, 106(2) Å For CsNH₂ · NH₃ all hydrogen atom positions were successfully refined. The structure of both ammoniates may be described by a distorted hexagonal close packed arrangement of cations with the NH₃ molecules in the octahedral and the NH₂^— anions in the trigonal bipyramidal interstices. The three H atoms of the NH₃ molecules are involved in hydrogen bridge bonds to two amide ions with d(N(NH₃)···N(NH₂^—)) = 2.60Å for the K and 3.19Å for the Cs compound and to a further NH₃ molecule with d(N(NH₃)···N(NH₃)) = 2.98Å for the K and 3.56Å for the Cs compound. Structural relationship of the ammoniates to the monohydrates of KOH and RbOH is discussed.     

From Isolated Polyanions to 1‐D Structure: Synthesis and Crystal Structure of Hybrid Fluorides {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2

Two new hybrid fluorides, {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · (H₃O)⁺ · [Al₇F₃₀]^9– ( I ) and {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · [Al₇F₂₉]^8– · (H₂O)₂ ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) ų, Z = 1, R = 0.0489, R_w = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) ų, Z = 1, R = 0.0327, R_w = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF₆ octahedra form a [Al₇F₃₀]^9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al₇F₂₉)_n^8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al₇F₃₀^9– heptamers in I and with three inorganic chains in II .     

Hydrogen Bonds in Rubidium Amide‐Ammonia(3/2), RbNH2·2/3NH3

Rubidium amide‐ammonia(3/2), RbNH₂·2/3NH₃, was synthesized from Rubidiumhydride, RbH, in liquid ammonia at ?78 °C. The compound crystallizes in the cubic space group I2₁3 with Z = 4, a = 10.0490(12) Å, and V = 1014.77(20) Å as isometric colorless crystals. The crystal structure was solved from single‐crystal X‐ray data. The structure contains a three‐dimensional network of amide anions and ammonia molecules, which are interconnected via hydrogen bonds.     

π‐Complexes of Copper(I) with Terminal Alkynes. Synthesis and Crystal Structure of [(HC≡CCH2NH3)(Cu2Br3)] π‐Complex

Crystals of the zwitterionic copper(I) π‐complex [(HC≡CCH₂NH₃)Cu₂Br₃] have been synthesized by interaction of CuBr with [HC≡CCH₂NH₃]Br in aqueous solution (pH < 1) and X‐ray studied. The crystals are monoclinic: space group P2₁/n, a = 6.722(4), b = 12.818(8), c = 9.907(3) Å, β = 100.25(4)°, V = 840.0(8) ų, Z = 4, R = 0.0592 for 3015 reflections. The crystal structure of the π‐complex contains isolated [(HC≡CCH₂NH₃)⁺(Cu₂Br₃)^?]₂ units which are incorporated into a framework by strong hydrogen N–H···Br and C≡C–H···Br bonds. The length of π‐coordinated propargylammonium C≡C bond is equal 1.216(8) Å and Cu(I)–(C≡C) distance equals 1.958(5) Å.     

Synthesis and Crystal Structure of Cesium Hexamminesodium Decahydro‐closo‐decaborate‐Ammonia(1/1), Cs[Na(NH3)6][B10H10]·NH3

Cs[Na(NH₃)₆][B₁₀H₁₀]·NH₃ was synthesised from cesium and disodium‐decahydro‐closo‐decaborate Na₂B₁₀H₁₀ in liquid ammonia, from which it crystallized in form of temperature sensitive colorless plates (triclinic, P1¯, a = 8.4787(7) Å, b = 13.272(1) Å, c = 17.139(2) Å, α = 88.564(1)°, β = 89.773(1)°, γ = 81.630(1)°, V = 1907.5(3) ų, Z = 4). The compound is the first example of an alkali metal boranate with two different types of cations. The decahydro‐closo‐decaborate dianions [B₁₀H₁₀]^2— and the cesium cations form a equation/tex2gif-stack-1.gif[Cs₂(B₁₀H₁₀)₂]^2— layer parallel to the ac plane. These layers are separated by N—H···N‐hydrogen bonded hexamminesodium cations.     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

A S8‐like [Sb8]8− Zintl Anion in the Ammoniate [K17(Sb8)2(NH2)] · 17.5NH3

The ammoniate [K₁₇(Sb₈)₂(NH₂)] · 17.5NH₃ was synthesized by reduction of antimony with potassium in liquid ammonia. Single crystals were isolated and characterized by low temperature X‐ray structure analysis. [K₁₇(Sb₈)₂(NH₂)] · 17.5NH₃ crystallizes in the space group P2₁/c (No. 14) with a = 12.976(1) Å, b = 24.536(1) Å, c = 22.858(1) Å and β = 99.17(1)°. The ammoniate contains crown‐shaped [Sb₈]^8? Zintl anions which are analogous to S₈ rings. The presence of amide NH₂^? as an additional anion is deduced from coordination observations and the close similarity of structural features to the structure of KNH₂.     

Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2

Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ were prepared by the reaction of Ni(NH₃)₂X₂ with NiX₂ at 350 °C in a steel autoclave. The crystal structures were determined by X‐ray powder diffraction using synchrotron radiation and refined by Rietveld methods. Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ are isotypic and crystallize in the space group I2/m with Z = 8 and for Ni(NH₃)Cl₂: a = 14.8976(3) Å, b = 3.56251(6) Å, c = 13.9229(3) Å, β = 106.301(1)°; Ni(NH₃)Br₂: a = 15.5764(1) Å, b = 3.74346(3) Å, c = 14.4224(1) Å, β = 105.894(1)°. The crystal structures are built up by two crystallographically distinct but chemically mostly equivalent polymeric octahedra double chains [NiX_3/3X_2/2(NH₃)] (X = Cl, Br) running along the short b‐axis. The octahedra NiX₅NH₃ share common edges therein. The crystal structures of the ammines Ni(NH₃)_mX₂ with m = 1, 2, 6 can be derived from that of the halides NiX₂ (X = Cl, Br) by successive fragmentation of its CdCl₂ like layers by NH₃.     

Cs2Ba(O3)4 · 2 NH3, das erste ionische Erdalkaliozonid

Cs₂Ba(O₃)₄ · 2 NH₃, the First Ionic Alkaline Earth Metal Ozonide Cs₂Ba(O₃)₄ · 2 NH₃ is the first ionic ozonide containing an alkaline earth metal cation. Its synthesis has been achieved via partial cation exchange of CsO₃ dissolved in liquid ammonia. According to a single crystal X‐ray structure determination (Pnnm; a = 6.312(2) Å, b = 12.975(3) Å, c = 8.045(2) Å; Z = 2; R₁ = 4.6%; 848 independent reflections) ozonide anions, cesium cations and ammonia molecules form a CsCl‐type arrangement, where Cs⁺ and NH₃ occupy one half of the cation sites, each. Ba²⁺ is coordinated by four ozonide groups and two ammonia molecules. Because of a short hydrogen bond to one of the terminal oxygen atoms, the respective O–O‐distance in the ozonide ion is longer than the other. The shortest intermolecular O–O‐distance ever observed in ionic ozonides has been found in this compound, which can be taken as a first clue for the radical ozonide anion to dimerize like the isoelectronic SO₂^– does.     

Synthese und Kristallstruktur des Lewis‐Säure/Base‐Addukts AlCl3·C3N3Cl3

Synthesis and Crystal Structure of the Lewis Acid‐Base Adduct AlCl₃·C₃N₃Cl₃ The reaction between cyanuric chloride (C₃N₃Cl₃) and the strong Lewis acid AlCl₃ yielded colorless crystals of the adduct AlCl₃·C₃N₃Cl₃. The crystal structure was determined by single crystal X‐ray diffraction at room temperature and was solved in the space group with Z = 4, a = 7.3802(7) Å, b = 9.688(1) Å, c = 16.272(2) Å, α = 72.80(1)°, β = 89.97(1)°, γ = 87.23(1)°, and V = 1110.0(2) ų. In the crystal structure, AlCl₃ is closely associated to the triazine ring with Al–N distances of 2.042(3) Å and 2.067(4) Å, respectively. The AlCl₃·C₃N₃Cl₃ units are connected with each other via intermolecular N···Cl donor–acceptor interactions, forming tape‐like arrangements in the ac‐plane, with tapes running parallel to the a‐axis.     

The Cocrystallization of the Cubic [Ta6Br12(H2O)6][CuBr2X2]·10H2O and Triclinic [Ta6Br12(H2O)6]X2·trans‐[Ta6Br12(OH)4(H2O)2]·18H2O (X = Cl,Br, NO3) Phases with the Coexistence of [Ta6Br12]2+ and [Ta6Br12]4+ in the Latter

Cubic [Ta₆Br₁₂(H₂O)₆][CuBr₂X₂]·10H₂O and triclinic [Ta₆Br₁₂(H₂O)₆]X₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O (X = Cl, Br, NO₃) cocrystallize in aqueous solutions of [Ta₆Br₁₂]²⁺ in the presence of Cu²⁺ ions. The crystal structures of [Ta₆Br₁₂(H₂O)₆]Cl₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 1 ) and [Ta₆Br₁₂(H₂O)₆]Br₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 3 )have been solved in the triclinic space group P&1macr; (No. 2). Crystal data: 1 , a = 9.3264(2) Å, b = 9.8272(2) Å, c = 19.0158(4) Å, α = 80.931(1)?, β = 81.772(2)?, γ = 80.691(1)?; 3 , a = 9.3399(2) Å, b = 9.8796(2) Å, c = 19.0494(4) Å; α = 81.037(1)?, β = 81.808(1)?, γ = 80.736(1)?. 1 and 3 consist of two octahedral differently charged cluster entities, [Ta₆Br₁₂]²⁺ in the [Ta₆Br₁₂(H₂O)₆]²⁺ cation and [Ta₆Br₁₂]⁴⁺ in trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]. Average bond distances in the [Ta₆Br₁₂(H₂O)₆]²⁺ cations: 1 , Ta‐Ta, 2.9243 Å; Ta‐Brⁱ , 2.607 Å; Ta‐O, 2.23 Å; 3 , Ta‐Ta, 2.9162 Å; Ta‐Brⁱ , 2.603 Å; Ta‐O, 2.24 Å. Average bond distances in trans‐[Ta₆‐Br₁₂(OH)₄(H₂O)₂]: 1 , Ta‐Ta, 3.0133 Å; Ta‐Brⁱ, 2.586 Å; Ta‐O(OH), 2.14 Å; Ta‐O(H₂O), 2.258(9) Å; 3 , Ta‐Ta, 3.0113 Å; Ta‐Brⁱ, 2.580 Å; Ta‐O(OH), 2.11 Å; Ta‐O(H₂O), 2.23(1) Å. The crystal packing results in short O···O contacts along the c axes. Under the same experimental conditions, [Ta₆Cl₁₂]²⁺ oxidized to [Ta₆Cl₁₂]⁴⁺ , whereas [Nb₆X₁₂]²⁺ clusters were not affected by the Cu²⁺ ion.     

[Sb11]3− and [As11]3−: Synthesis and Crystal Structure of Two New Ammoniates containing Trishomocubane‐like Polyanions

The ammoniates [K(18‐crown‐6)(NH₃)₂]₃Sb₁₁ · 5.5NH₃ ( 1 ) and [Cs(18‐crown‐6)]₂CsAs₁₁ · 8NH₃ ( 2 ) (18‐crown‐6 = 18C6: 1,4,7,10,13,16‐Hexaoxacyclooctadecan) were synthesized by either the reaction of K₃Sb₇ with SbPh₃ in liquid ammonia or by extraction of Cs₃As₁₁ with liquid ammonia. Single crystals were isolated and characterized by low temperature X‐ray structure analysis. [K(18‐crown‐6)(NH₃)₂]₃Sb₁₁ · 5.5NH₃ crystallizes in the space group with a = 13.31(2) Å, b = 15.161(2) Å, c = 22.521(3) Å, α = 99.23(1)°, β = 100.99(1)° and γ = 105.03(1)°. [Cs(18‐crown‐6)]₂CsAs₁₁ · 8NH₃ crystallizes in the monoclinic space group C2/c with a = 20.009(3) Å, b = 17.024(1) Å, c = 19.838(2) Å and β = 119.732(9)°. While 1 contains isolated [Sb₁₁]^3? anions and [K(18‐crown‐6)(NH₃)₂]⁺ complexes, cesium–arsenic contacts lead to one–dimensionally infinite chains in 2 .     

Metall-Schwefelstickstoff-Verbindungen. 17. Die Verbindungen HgN2S · NH3 und 2Hg(NH3)2I2 · S4N4

Metal Sulphur Nitrogen Compounds. 17. Compounds HgN₂S · NH₃ and Hg(NH₃)₂I₂ · S₄N₄ The crystal and molecular structures of the known compounds HgN₂S · NH₃ and of the new inclusion compound 2Hg(NH₃)₂I₂ · S₄N₄ are reported. HgN₂S · NH₃ is orthorhombic, space group Pbca with a = 5.548, b = 10.158, c = 14.919 Å, Z = 8. In the dimeric molecules two Hg atoms are bridged to form eight-membered rings . In addition, each Hg is coordinated by an NH₃ molecule and by an N atom of an adjacent ring. This results in a two-dimensional network. 2Hg(NH₃)₂I₂ · S₄N₄ is tetragonal, space group P4₂/nmc, a = 8.948, c = 13.188 Å, Z = 2. It is an inclusion compound with S₄N₄ molecules in the holes of the lattice of the large Hg(NH₃)₂I₂ tetrahedra.     

Tetraammonium Diglycinyl‐octamolybdate(VI) Dihydrate, (NH4)4[(NH3CH2CO)2(Mo8O28)] · 2 H2O

The reaction of ammonium heptamolybdate with hydrazine sulfate in an aqueous solution of glycine at room temperature yielded colorless crystals of (NH₄)₄[(NH₃CH₂CO)₂(Mo₈O₂₈)] · 2 H₂O. The crystal is monoclinic, space group C2/c (no. 15), a = 17.234 Å, b = 10.6892 Å, c = 18.598 Å, β = 108.280°, V = 3253.2 ų, Z = 4. The crystal structure contains ammonium cations and isolated octamolybdate(4–) anions, [(NH₃CH₂CO)₂(Mo₈O₂₈)]^4–, with two zwitterionic glycine molecules as ligands.     

Synthesis and Characterization of a Two‐Dimensional Zinc Phosphite,Zn3(tren)(HPO3)3·xH2O (x ≈ 0.5; tren = tris(2‐aminoethyl)amine)

A new zinc phosphite with the formula Zn₃(tren)(HPO₃)₃·xH₂O (x≈0.5) has been synthesized under hydrothermal conditions and characterized by FTIR, elemental analysis, powder X‐ray diffraction, single‐crystal X‐ray diffraction, thermogravimetric analysis and its fluorescent spectrum. The compound crystallizes in the triclinic system, space group (No.2), a = 10.1188(9) Å, b = 10.4194(9) Å, c = 10.5176(9) Å, α = 60.763(2)°, β = 70.6150(10)°, γ = 80.725(2)°, V = 912.77(14) ų, Z = 2. The structure consists of double crankshaft chains, which are linked by Zn‐O‐P bonds to form 8‐ and 12‐membered channels along the [100] direction. The claw‐like Zn‐centered complexes of Zn(N₄C₆H₁₈) as the supported templates, hang into the 12‐MR channels through Zn‐O‐P linkages with framework.