Low-energy fragmentations of five isomeric [H3, C,N, O2] +· ions

The low-energy fragmentation characteristics of the [H₃,C,N,O₂]^+· isomers [H₃CNO₂]^+· (a), [H₂C?N(O)OH]^+· (b), [H₃CONO]^+· (c), [HC(O)NHOH]^+· (d) and [HC(OH)?NOH]^+· (e) were studied in detail by metastable ion mass spectrometry. In agreement with most earlier observations, appearance energy measurements established the potential energy surface of the isomers a, b and c, showing the intricate interrelations between them. It was concluded that a isomerizes into b prior to fragmentation by loss of ^·OH and H₂O and into c before loss of ^·H and H₃CO^· moreover, the reverse reactions do not take place on the metastable time-frame. The dominant metastable process for isomers d and e (obtained via HCN loss from glyoxime) was generation of [H₂NOH]^+·. For isomer e this process was proposed to involved a rate-determining isomerization into d. It was concluded that isomers d and e do not intercommunicate with ions a, b and c prior to fragmentation. Neutralization-reionization mass spectrometry indicated that the enol form of formohydroxamic acid as well as the keto counterpart are stable in the gas phase.     

Neue Oxonium-Bromochalkogenate(IV) — Darstellung,Struktur und Eigenschaften von [H3O][TeBr5] · 3C4H8O2 und [H3O]2[SeBr6]

New Oxonium Bromochalcogenates(IV) — Synthesis, Structure, and Properties of [H₃O][TeBr₅] · 3 C₄H₈O₂ and [H₃O]₂[SeBr₆] Dark red crystals of the composition [H₃O][TeBr₅] · 3 C₄H₈O₂ ( 1 ) were isolated from a saturated solution of TeBr₄ in 1,4-dioxane containing a small amount of water. In this compound (space group P2₁/m, a = 8.922(4) Å, b = 13.204(7) Å, c = 9.853(5) Å, β = 91.82(4)° at 150 K) a square pyramidal [TeBr₅]^? anion has been isolated for the first time. The coordination sphere of the anion is completed to a distorted octahedron by weak interaction with a dioxane molecule of the cationic system. The [H₃O]⁺ cations are connected to chains by dioxane molecules. At room temperature the compound is stable only in its mother liquor. Crystalline [H₃O]₂[SeBr₆] ( 2 ) (space group Fm3m, a = 10.421(1) Å at 170 K) is a bromoselenous acid of high symmetry. The [H₃O]⁺ ion is only weakly coordinated by Br atoms of the anion. The anions are isolated octahedral [SeBr₆]^2? units. The structure is isotypic to the K₂[PtCl₆] structure. Despite being a halogenochalcogen(IV) acid, 2 exhibits a remarkable thermal stability. Both oxonium compounds were characterized by single-crystal X-ray structure analyses. Vibrational spectra of 2 are reported.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

Zur Koordination des Aluminiums in den Calciumaluminathydraten 2 CaO · Al2O3 · 8 H2O und CaO · Al2O3 · 10 H2O

On the Coordination of Al in the Calcium Aluminate Hydrates 2 CaO · Al₂O₃ · 8 H₂O and CaO · Al₂O₃ · 10 H₂O By investigations with high-resolution ²⁷Al-NMR in solids it is shown that in the compound 2 CaO · Al₂O₃ · 8 H₂O the Al merely exist in octahedral coordination. According to this and considering its structural relationship with 4 CaO · Al₂O₃ · 19 H₂O the dicalcium aluminate hydrate is proposed to be formulated as [Ca₂Al(OH)₆][Al(OH)₃ (H₂O)₃]OH. Likewise for the compound CaO · Al₂O₃ · 10 H₂O the octahedral coordination of the Al is proved by ²⁷Al-NMR. This result corresponds with literature according to which a constitution as cyclohexaaluminate Ca₃[Al₆(OH)₂₄] · 18 H₂O is proposed.     

Organic‐Inorganic Hybrid Supramolecular Assemblies Based on Isomers [HxAs2Mo6O26](6–x)– Clusters

The arsenomolybdates [H₂As₂Mo₆O₂₆(H₂O)] · (H₂biyb)₂ · 2H₂O ( 1 ) and [H₃As₂Mo₆O₂₆] · (H₃pt)₂ ( 2 ) [biyb = 1,4‐bis(imidazol‐1‐ylmethyl)benzene, pt = 4′‐(3′′‐pyridyl)‐2,3′:6′3′′‐terpyridine] were synthesized via hydrothermal method. The structures of the compounds were characterized by single‐crystal X‐ray diffraction analyses, elemental analyses, IR spectroscopy, and TG analysis. Compounds 1 and 2 exhibit two isomeric forms of [H_xAs₂Mo₆O₂₆]^(6–x)–. The structure of 1 is constructed from the B‐type [H₂As₂Mo₆O₂₆(H₂O)]^4– polyanions and free biyb ligands via weak interactions to form 3D supramolecular framework with a {3 · 4 · 5³ · 6}{3 · 4³ · 5²}{3 · 5 · 6}²{3 · 5²}² topology structure. In compound 2 , the A‐type [H₃As₂Mo₆O₂₆]^3– clusters are surrounded by pt ligands through hydrogen bond interactions forming 3D supramolecular framework with a {4³ · 6³}²{4⁶ · 6⁶ · 8³} topology structure. The electrochemical behaviors, electrocatalytic and photocatalytic activities of 1 and 2 are detected.     

[TMPA]4[Si8O20] · 34 H2O and [DDBO]4[Si8O20] · 32 H2O are heteronetwork clathrates with 1,1,4,4-tetramethylpiperazinium (TMPA) and 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane (DDBO) guest cations

[TMPA]₄[Si₈O₂₀] · 34 H₂O ( 1 ) and [DDBO]₄[Si₈O₂₀] · 32 H₂O ( 2 ) have been prepared by crystallization from aqueous solutions of the respective quaternary alkylammonium hydroxide and SiO₂. The crystal structures have been determined by single-crystal X-ray diffraction. 1 : Monoclinic, a = 16.056(2), b = 22.086(6), c = 22.701(2) Å, β = 90.57(1)° (T = 210 K), space group C2/c, Z = 4. 2 : Monoclinic, a = 14.828(9), b = 20.201(7), c = 15.519(5) Å, β = 124.13(4)° (T = 255 K), space group P2₁/c, Z = 2. The polyhydrates are structurally related host-guest compounds with three-dimensional host frameworks composed of oligomeric [Si₈O₂₀]^8? anions and H₂O molecules which are linked via hydrogen bonds. The silicate anions possess a cube-shaped double four-ring structure and a characteristic local environment formed by 24 H₂O molecules and six cations (TMPA, [C₈H₂₀N₂]²⁺, or DDBO, [C₈H₁₈N₂]²⁺). The cations themselves reside as guest species in large, irregular, cage-like voids. Studies employing ²⁹Si NMR spectroscopy and the trimethylsilylation method have revealed that the saturated aqueous solutions of 1 and 2 contain high proportions of double four-ring silicate anions. Such anions are also abundant species in the saturated solution of the heteronetwork clathrate [DMPI]₆[Si₈O₁₈(OH)₂] · 48.5 H₂O ( 3 ) with 1,1-dimethylpiperidinium (DMPI, [C₇H₁₆N]⁺) guest cations.     

Structures of decomposing and non-decomposing gas-phase [C4H6O]+· radical cations,and their [C2H2O]+· and [C3H6]+· product ions

The structures of gas-phase [C₄H₆O]^+· radical cations and their daughter ions of composition [C₂H₂O]^+· and [C₃H₆]^+· were investigated by using collisionally activated dissociation, metastable ion measurement, kinetic energy release and collisional ionization tandem mass spectrometric techniques. Electron ionization (70 eV) of ethoxyacetylene, methyl vinyl ketone, crotonaldehyde and 1-methoxyallene yields stable [C₄H₆O]^+· ions, whereas the cyclic C₄H₆O compounds undergo ring opening to stable distonic ions. The structures of [C₂H₃O]^+· ions produced by 70-eV ionization of several C₄H₆O compounds are identical with that of the ketene radical cation. The [C₃H₆]^+· ions generated from crotonaldehyde, methacrylaldehyde, and cyclopropanecarboxaldehyde have structures similar to that of the propene radical cations, whereas those ions generated from the remainder of the [C₄H₆O]^+· ions studied here produced a mixed population of cyclopropane and propene radical cations.     

N—H...O and O—H...O hydrogen‐bonded supramolecular networks in 4‐chloroanilinium, 2‐hydroxyanilinium and 3‐hydroxyanilinium hydrogen phthalates

The title salts, 4‐chloroanilinium hydrogen phthalate (PCAHP), C₆H₇ClN⁺·C₈H₅O₄⁻, 2‐hydroxyanilinium hydrogen phthalate (2HAHP), C₆H₈NO⁺·C₈H₅O₄⁻, and 3‐hydroxyanilinium hydrogen phthalate (3HAHP), C₆H₈NO⁺·C₈H₅O₄⁻, all crystallize in the space group P2₁/c. The asymmetric unit of 2HAHP contains two independent ion pairs. The hydrogen phthalate ions of 2HAHP and 3HAHP show a short intramolecular O—H...O hydrogen bond, with O...O distances ranging from 2.3832 (15) to 2.3860 (14) Å. N—H...O and O—H...O hydrogen bonds, together with short C—H...O contacts in PCAHP and 3HAHP, generate extended hydrogen‐bond networks. PCAHP forms a two‐dimensional supramolecular sheet extending in the (100) plane, whereas 2HAHP has a supramolecular chain running parallel to the [100] direction and 3HAHP has a two‐dimensional network extending parallel to the (001) plane.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

New coordination modes in potassium edta salts: K2[H2edta]·2H2O,K3[Hedta]·2H2O and K4[edta]·3.92H2O

Three potassium edta (edta is ethylenediaminetetraacetic acid, H₄Y) salts which have different degrees of ionization of the edta anion, namely dipotassium 2‐({2‐[bis(carboxylatomethyl)azaniumyl]ethyl}(carboxylatomethyl)azaniumyl)acetate dihydrate, 2K⁺·C₁₀H₁₄N₂O₈²⁻·2H₂O, (I), tripotassium 2,2′‐({2‐[bis(carboxylatomethyl)amino]ethyl}ammonio)diacetate dihydrate, 3K⁺·C₁₀H₁₃N₂O₈³⁻·2H₂O, (II), and tetrapotassium 2,2′,2′′,2′′′‐(ethane‐1,2‐diyldinitrilo)tetraacetate 3.92‐hydrate, 4K⁺·C₁₀H₁₂N₂O₈⁴⁻·3.92H₂O, (III), were obtained in crystalline form from water solutions after mixing edta with potassium hydroxide in different molar ratios. In (II), a new mode of coordination of the edta anion to the metal is observed. The HY³⁻ anion contains one deprotonated N atom coordinated to K⁺ and the second N atom is involved in intramolecular bifurcated N—H...O and N—H...N hydrogen bonds. The overall conformation of the HY³⁻ anions is very similar to that of the Y⁴⁻ anions in (III), although a slightly different spatial arrangement of the –CH₂COO⁻ groups in relation to (III) is observed, whereas the H₂Y²⁻ anions in (I) adopt a distinctly different geometry. The preferred synclinal conformation of the –NCH₂CH₂N– moiety was found for all edta anions. In all three crystals, the anions and water molecules are arranged in three‐dimensional networks linked via O—H...O and C—H...O [and N—H...O in (I) and (II)] hydrogen bonds. K...O interactions also contribute to the three‐dimensional polymeric architecture of the salts.     

Synthesis, characterization and thermal analysis of 1:1 and 2:3 lanthanide(III) citrates

The synthesis and characterization of lanthanide(III) citrates with stoichiometries 1:1 and 2:3; [LnL·xH₂O] and [Ln₂(LH)₃·2H₂O], Ln=La, Ce, Pr, Nd, Sm and Eu are reported. L stands for (C₆O₇H₅)^3? and LH for (C₆O₇H₆)^2?. Infrared absorption spectra of both series evidence coordination of carboxylate groups through symmetric bridges or chelation. X-ray powder patterns show the amorphous character of [LnL·xH₂O]. The compounds [Ln₂LH₃·2H₂O] are crystalline and isomorphous. Emission spectra of Eu compounds suggest C _2v symmetry for the coordination polyhedron of [LnL·xH₂O] and C _4v for [Ln₂(LH)₃·2H₂O]. Thermal analyses (TG-DTG-DTA) were carried out for both series. The thermal analysis patterns of the two series are quite different and both fit in a 4-step model of thermal decomposition, with lanthanide oxides as final products.     

Synthese und Charakterisierung von Aquapentachloroplatinaten(IV) – Struktur von [K(18-Krone-6)][PtCl5(H2O)]

Synthesis and Characterization of Aquapentachloroplatinates(IV) – Structure of [K(18-crown-6)][PtCl₅(H₂O)] The crown ether complex of the aquapentachloroplatinic acid of the composition [H₁₃O₆][PtCl₅(H₄O₂)] · 2(18-cr-6) ( 2 ) reacts with K₂CO₃ and [NⁿBu₄]OH in aqueous solution to give [K(18-cr-6)][PtCl₅(H₂O)] ( 5 a ) and [NⁿBu₄][PtCl₅(H₂O)] · ¹/₂ (18-cr-6) · H₂O ( 5 b ), respectively. Both compounds were characterized by microanalysis, vibrational (IR, Raman) and NMR (¹H, ¹³C, ¹⁹⁵Pt) spectroscopy. The X-ray structure analysis of 5 a (orthorhombic, pnma; a = 16,550(4), b = 18,044(3), c = 7,415(1) Å; Z = 4; R1 = 0,0183; wR2 = 0,0414) reveals that the crystal is threaded by chains built up of [PtCl₅(H₂O)]^? and [K(18-cr-6)]⁺ units. There are tight K …? Cl contacts (d(K? Cl1)) = 3,0881(9) Å and O_W? H? O_cr hydrogen bridges (d(O1 …? O2) = 2,806(3) Å) between these units. The coordination polyhedron [PtCl₅O] has approximately C_4v symmetry.     

Differences and similarities among hypoxanthinium nitrate hydrate structures

Crystals of hypoxanthinium (6‐oxo‐1H,7H‐purin‐9‐ium) nitrate hydrates were investigated by means of X‐ray diffraction at different temperatures. The data for hypoxanthinium nitrate monohydrate (C₅H₅N₄O⁺·NO₃^?·H₂O, Hx1 ) were collected at 20, 105 and 285 K. The room‐temperature phase was reported previously [Schmalle et al. (1990). Acta Cryst. C 46 , 340–342] and the low‐temperature phase has not been investigated yet. The structure underwent a phase transition, which resulted in a change of space group from Pmnb to P2₁/n at lower temperature and subsequently in nonmerohedral twinning. The structure of hypoxanthinium dinitrate trihydrate (H₃O⁺·C₅H₅N₄O⁺·2NO₃^?·2H₂O, Hx2 ) was determined at 20 and 100 K, and also has not been reported previously. The Hx2 structure consists of two types of layers: the `hypoxanthinium nitrate monohydrate' layers (HX) observed in Hx1 and layers of Zundel complex H₃O⁺·H₂O interacting with nitrate anions (OX). The crystal can be considered as a solid solution of two salts, i.e. hypoxanthinium nitrate monohydrate, C₅H₅N₄O⁺·NO₃^?·H₂O, and oxonium nitrate monohydrate, H₃O⁺(H₂O)·NO₃^?.     

Zeolite-Y enslaved manganese(III) complexes as heterogeneous catalysts

Traditional catalytic procedures for oxidation of phenol produce environmentally undesirable wastes. As a consequence, there is a clear demand for development of an environmentally benign catalytic route for the selective oxidation of phenol. A series of zeolite-Y enslaved Mn(III) complexes with Schiff bases derived from vanillin furoic-2-carboxylic acid hydrazone (VFCH), vanillin thiophene-2-carboxylic acid hydrazone (VTCH), ethylvanillin thiophene-2-carboxylic acid hydrazone (EVTCH), and/or ethylvanillin furoic-2-carboxylic acid hydrazone have been synthesized and characterized by physico-chemical techniques. Catalytic oxidations of phenol using 30% H₂O₂ as an oxidant over [Mn(VTCH)₂·2H₂O]⁺-Y, [Mn(VFCH)₂·2H₂O]⁺-Y, and [Mn(EVTCH)₂·2H₂O]⁺-Y under mild conditions were studied. These zeolite-Y enslaved Mn(III) complexes are stable and recyclable under current reaction conditions.     

白硼钙石的合成新方法及其热化学研究(英)

0IntroductionTherearemanykindsofhydratedcalciumbo-rates,bothnaturalandsynthetic.Someofthemarematerialsusedinglass,potteryandporcelainenamelindustry,especiallyinunalkaliglassindustry.4CaO·5B2O3·7H2O,calledpriceite,isacalciumboratemin-eral,notfoundinCaO-B…     

Imidazole Coordinated Sandwich‐type Antimony Poly‐oxotungstates Na9[{Na(H2O)2}3{M(C3H4N2)}3(SbW9O33)2]·xH2O (M=NiII,CoII, ZnII,MnII)

The imidazole covalently coordinated sandwich‐type heteropolytungstates Na₉[{Na(H₂O)₂}₃{M(C₃H₄N₂)}₃‐ (SbW₉O₃₃)₂]·xH₂O (M=Ni^II, x=32; M=Co^II, x=32; M=Zn^II, x=33; M=Mn^II, x=34) were obtained by the reaction of Na₂WO₄·2H₂O, SbCl₃·6H₂O, NiCl₂·6H₂O [MnSO₄·H₂O, Co(NO₃)₂·6H₂O, ZnSO₄·7H₂O] and imidazole at pH≈7.5. The structure of Na₉[{Na(H₂O)₂}₃{Ni(C₃H₄N₂)}₃(SbW₉O₃₃)₂]·32H₂O was determined by single crystal X‐ray diffraction. Polyanion [{Na(H₂O)₂}₃{Ni(C₃H₄N₂)}₃(SbW₉O₃₃)₂}₃]^9? has approximate C_3v symmetry, imidazole coordinated six‐nuclear cluster [{Na(H₂O)₂}₃{Ni(C₃H₄N₂)}₃]⁹⁺ is encapsulated between two (α‐SbW₉O₃₃)^9?, the three rings of imidazole in the polyanion are perpendicular to the horizontal plane formed by six metals (Na‐Ni‐Na‐Ni‐Na‐Ni) in the central belt, and π‐stacking interactions exist between imidazoles of neighboring polyanions with dihedral angel of 60°. The compounds were also characterized by IR, UV‐Vis spectra, TG and DSC, and the thermal decomposition mechanism of the four compounds was suggested by TG curves.     

Synthesis, Characterization and Thermochemistry of 2MgO：B2O3：1.5H2O

Introduction　　 2MgO·B2 O3(Mg2 B2 O5)and 2MgO·B2 O3·H2 Omightbepreparedaswhiskermaterials .12MgO·B2 O3·H2 OnamedszaibelyiteisamagnesiumboratemineralwithastructuralformulaofMg2 [B2 O4 (OH) 2 ].2 Itisdifficulttosynthesizethiscompoundinthelaboratory .Recently ,weobtainedasimilarcompound 2MgO·B2 O3·1 5H2 Owhenwetriedtopreparewhiskerof 2MgO·B2 O3·H2 Obythephasetransformationof 2MgO·2B2 O3·MgCl2 ·14H2 OinH3BO3solutionunderhydrothermalcondition .Itishope fultopreparewh…     

Preparation,Crystal Structure and Vibrational Spectra of Ca2P2O6·2H2O and [Ca(H2O)3(H2P2O6)]·0.5(C12H24O6)·H2O

The calcium salts Ca₂P₂O₆ · 2H₂O ( 1 ) and [Ca(H₂O)₃(H₂P₂O₆)] · 0.5(C₁₂H₂₄O₆) · H₂O ( 2 ) were prepared and structurally characterized by single‐crystal X‐ray diffraction. Compound 1 crystallizes in the orthorhombic space group Pbca and compound 2 in the monoclinic space group P2₁/n. The crystal structure of compound 1 consists of chains of edge‐sharing [CaO₇] polyhedra linked by hypodiphosphate(IV) anions to form a three‐dimensional network. The crystal structure of compound 2 consists of alternated layers of crown ether and water molecules and respective ionic units. Within the layers of ionic units the Ca²⁺ cations are octahedrally coordinated by three monodentate dihydrogenhypodiphosphate(IV) anions and three water molecules. The IR/Raman spectra of the title compounds were recorded and interpreted, especially with respect to the [P₂O₆]^4– and [H₂P₂O₆]^2– groups. The phase purity of 2 was verified by powder diffraction measurements.     

The Water-Rich Iodidobismuthate (H3O)Rb3BiI7·4H2O

Red cuboid crystals of the water-rich iodidobismuthate(III) (H₃O)Rb₃BiI₇ · 4H₂O crystallize from a solution of RbI and BiIO in concentrated aqueous HI at ambient conditions. X-ray diffraction reveale an orthorhombic structure with space group Pnma (no. 62). In the crystal structure, [BiI₆]^3– octahedra are arranged in layers parallel to (010). Nine-fold coordinated Rb⁺ and additional I^– ions connect the iodidobismuthate(III) groups into a three-dimensional framework, which hosts protonated water complexes ¹_∞[H₁₁O₅]⁺, i.e. infinite zigzag chains of hydrogen-bonded water molecules and oxonium cations. (H₃O)Rb₃BiI₇ · 4H₂O decomposes in air at ambient temperature within few days, resulting in fragmentation and amorphization of the crystals. Fast and complete dehydration occurs between 50 °C and 100 °C. Hydrates like this are possible intermediates in the slow hydrolysis of bismuth-based halide perovskites, which are currently discussed as lead-free alternatives to the solar cell absorber material methylammonium lead triiodide (MAPI).     

Das Lanthan‐Dodekahydro‐closo‐Dodekaborat‐Hydrat [La(H2O)9]2[B12H12]3·15 H2O und sein Oxonium‐Chlorid‐Derivat [La(H2O)9](H3O)Cl2[B12H12]·H2O

The Lanthanum Dodecahydro‐closo‐Dodecaborate Hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O and its Oxonium‐Chloride Derivative [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic La₂O₃ and after isothermic evaporation colourless, face‐rich single crystals of a water‐rich lanthanum(III) dodecahydro‐closo‐dodecaborate hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O are isolated. The compound crystallizes in the trigonal system with the centrosymmetric space group (a = 1189.95(2), c = 7313.27(9) pm, c/a = 6.146; Z = 6; measuring temperature: 100 K). The crystal structure of [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O can be characterized by two of each other independent, one into another posed motives of lattice components. The [B₁₂H₁₂]²⁻ anions (d(B–B) = 177–179 pm; d(B–H) = 105–116 pm) are arranged according to the samarium structure, while the La³⁺ cations are arranged according to the copper structure. The lanthanum cations are coordinated in first sphere by nine oxygen atoms from water molecules in form of a threecapped trigonal prism (d(La–O) = 251–262 pm). A coordinative influence of the [B₁₂H₁₂]²⁻ anions on La³⁺ has not been determined. Since “zeolitic” water of hydratation is also present, obviously the classical H–O^δ–···^+δH–O‐hydrogen bonds play a significant role in the stabilization of the crystal structure. During the conversion of an aqueous solution of (H₃O)₂[B₁₂H₁₂] with lanthanum trichloride an anion‐mixed salt with the composition [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O is obtained. The compound crystallizes in the hexagonal system with the non‐centrosymmetric space group (a = 808.84(3), c = 2064.51(8) pm, c/a = 2.552; Z = 2; measuring temperature: 293 K). The crystal structure can be characterized as a layer‐like structure, in which [B₁₂H₁₂]²⁻ anions and H₃O⁺ cations alternate with layers of [La(H₂O)₉]³⁺ cations (d(La–O) = 252–260 pm) and Cl⁻ anions along [001]. The [B₁₂H₁₂]²⁻ (d(B–B) = 176–179 pm; d(B–H) = 104–113 pm) and Cl⁻ anions exhibit no coordinative influence on La³⁺. Hydrogen bonds are formed between the H₃O⁺ cations and [B₁₂H₁₂]²⁻ anions, also between the water molecules of [La(H₂O)₉]³⁺ and Cl⁻ anions, which contribute to the stabilization of the crystal structure.