NC12H8(NH)2[Gd(N3C12H8)4] und [Gd(N3C12H8)3(N3C12H9)]·PhCN: Ein Beitrag zur Reaktivität und Kristallchemie homoleptischer Selten‐Erd‐Pyridylbenzimidazolate

NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] and [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN: A Contribution to the Reactivity and Crystal Chemistry of Homoleptic Pyridylbenzimidazolates of the Rare Earth Elements Transparent colourless crystals of the compound NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] were obtained by solvent‐free reaction of gadolinium metal with molten 2‐(2‐Pyridyl)‐benzimidazole. Transparent yellow crystals of the compound [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN were obtained by further reacting NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] with benzonitrile thermally. Both compounds exhibit homoleptic pure nitrogen coordinations of gadolinium, the PhCN ligand is not coordinating. Whilst NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] is salt like and consists of (NC₁₂H₈(NH)₂)⁺ and [Gd(N₃C₁₂H₈)₄]^— ions, [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN has a molecular structure of uncharged [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)] units.     

First Homoleptic Rare Earth Carbazolates: Synthesis,Crystal Structures,Spectroscopic and Thermal Investigations of Divalent 1[Ln(NC12H8)2] with Ln = Europium and Ytterbium

The compounds [Ln(NC₁₂H₈)₂], Ln = Eu and Yb, were obtained in solvent free reactions of the rare earth elements europium and ytterbium with the amine carbazole. Single crystals of both compounds were grown from the melt syntheses, no recrystallization from solvents was necessary. The new compounds are the first examples of homoleptic carbazolates of the rare earth elements furthermore exhibiting divalent lanthanides. In absence of any solvent, carbazole as the sole coordination partner shows η⁶‐π‐coordination in addition to the μ₁‐ and μ₂‐coordination of the nitrogen atoms. This results in a one‐dimensional chain structure of dimers with a formal C.N. of 6 for the rare earth elements and thus being low for divalent lanthanides. The products were investigated by X‐ray single crystal and powder diffraction, Mid IR, Far IR and Raman spectroscopy, and with DTA/TG regarding their thermal behaviour. Both compounds [Ln(NC₁₂H₈)₂], Ln = Eu (1) and Yb (2) , crystallize isotypic in the triclinic space group P1.     

[Yb(NH3)8][Yb(Pyr)6] – Elektrid‐induzierte Synthese und Kristallisation aus flüssigem Ammoniak

[Yb(NH₃)₈][Yb(Pyr)₆]: Electride Induced Synthesis and Crystallization from Liquid Ammonia Single crystalline yellow [Yb(NH₃)₈][Yb(Pyr)₆] (Pyr^? = pyrrolate anion, C₄H₄N^?) was obtained by the reaction of ytterbium metal with pyrrole (C₄H₄NH) in liquid ammonia at ?35 °C. Significant excess of ammonia together with avoiding a pyrrole excess prevents formation of the molecular compound [Yb(Pyr)₃(PyrH)₂(NH₃)₂]. [Yb(NH₃)₈][Yb(Pyr)₆] consists of two homoleptic ionic units and rapidly decomposes if removed from the ammonia atmosphere, viz. it shows an ammonia vapour pressure >1 bar.     

Synthese,Kristallstruktur und thermischer Abbau von Mg(H2O)6[B12H12] · 6 H2O

Synthesis, Crystal Structure, and Thermal Decomposition of Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O By reaction of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with MgCO₃ and subsequent isothermic evaporation of the resulting solution to dryness, colourless, bead‐shaped single crystals of the dodecahydrate of magnesium dodecahydro closo‐dodecaborate Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O (cubic, F4₁32; a = 1643.21(9) pm, Z = 8) emerge. The crystal structure is best described as a NaTl‐type arrangement in which the centers of gravity of the quasi‐icosahedral [B₁₂H₁₂]^2— anions (d(B—B) = 178—180 pm, d(B—H) = 109 pm) occupy the positions of Tl^— while the Mg²⁺ cations occupy the Na⁺ positions. A direct coordinative influence of the [B₁₂H₁₂]^2— units at the Mg²⁺ cations is however not noticeable. The latter are octahedrally coordinated by six water molecules forming isolated hexaaqua complex cations [Mg(H₂O)₆]²⁺ (d(Mg—O) = 206 pm, 6×). In addition, six “zeolitic” water molecules are located in the crystal structure for the formation of a strong O—H^δ+···^δ—O‐hydrogen bridge‐bonding system. The evidence of weak B—H^δ—···^δ+H—O‐hydrogen bonds between water molecules and anionic [B₁₂H₁₂]^2— clusters is also considered. Investigations on the dodecahydrate Mg[B₁₂H₁₂] · 12 H₂O (≡ Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O) by DTA/TG measurements showed that its dehydration takes place in two steps within a temperature range of 71 and 76 °C as well as at 202 °C, respectively. Thermal treatment eventually leads to the anhydrous magnesium dodecahydro closo‐dodecaborate Mg[B₁₂H₁₂].     

Neuartige Synthese eines Lanthanoidtrialkyls – Charakterisierung und Kristallstruktur von Yb(CH2tBu)3(thf)2

Novel Synthesis of a Lanthanide Trialkyl – Characterization and Crystal Structure of Yb(CH₂ t Bu)₃(thf)₂ The solvated ytterbium alkyl Yb(CH₂tBu)₃(thf)₂ ( 1 ) was obtained in moderate yield from the reaction of ytterbium metal with neopentyl iodide. Ruby‐red air‐sensitive crystals of 1 were characterized by melting point, elemental analysis, IR, NMR, and UV/Vis spectroscopy and by X‐ray crystallography. In the solid state the ytterbium atom shows a trigonal bipyramidal coordination with the neopentyl groups and the THF ligands occupying equatorial and axial positions, respectively.     

Synthese,Kristallstruktur und thermischer Abbau von Cs1,5[Re3I3Cl7,5(H2O)1,5]

Synthesis, Crystal Structure and Thermal Behaviour of Cs_1,5[Re₃I₃Cl_7,5(H₂O)_1,5] Dark brown tetrahedra of Cs_1,5[Re₃I₃Cl_7,5(H₂O)_1,5] crystallize on slow cooling of a hot saturated solution of ReI₃ and CsCl in conc. hydrochlorid acid. The crystal structure (cubic, P4 3m (No. 215), a = 1241.06(3)pm, V_m = 287.8(1) cm³mol^?1, Z = 4, R = 0.067, R_w = 0.037) is built up from isolated building units [Re₃I₃Cl_7,5(H₂O)_1,5]^1,5? with statistical distribution of chloride ions and water molecules in the in plane, terminal positions. Consistent with the result based on the X-ray analysis, the IR-spectrum shows one band for the OH stretching frequencies of the water molecules coordinated to the Re₃ triangle at 3240 cm^?1. The anions are arranged in the fashion of a cubic closest packing with the cesium ions occupying all octahedral and one quarter of the tetrahedral interstices. Temperature-dependent Guinier-Simon photographs in connection with DTA/TG investigations reveal that Cs_1,5[Re₃I₃Cl_7,5(H₂O)_1,5] releases water at 190°C accompanied with a structural transition and the dehydration product decomposes at 370°C to Cs₂ReCl_6?xI_x, Re₃I_3+yCl_6?y and rhenium metal.     

Nitridsulfidchloride der Lanthanide: III. Synthese und Kristallstruktur von Pr5N3S2Cl2

Nitride Sulfide Chlorides of the Lanthanides. III. Synthesis and Crystal Structure of Pr₅N₃S₂Cl₂ By reacting praseodymium with sulfur, sodium azide and praseodymium trichloride in sealed, evacuated silica tubes (850°C, 7 d), the nitride sulfide chloride Pr₅N₃S₂Cl₂ is obtained in case of a 4:2:1:1 molar ratio of the reactants (Pr:S:NaN₃:PrCl₃). A slight excess of trichloride or the addition of NaCl as a flux supports the yield of brownish red, rod-shaped transparent crystals which prove to be stable against hydrolysis. The crystal structure (monoclinic, C2/m (no. 12), a = 1540.2(1), b = 400.92(3), c = 1656.3(1) pm, β = 101.24(1)°, Z = 4, R = 0.039, R_w = 0.028) was determined by means of X-ray single crystal data. Thus five crystallographically different cations (Pr³⁺) are present which with three distinct kinds of nitride anions (N^3?) build up two types of translationally commensurate chains from interconnected [NPr₄] tetrahedra. With an additional edge per “chain-link” in chain I, two single chains [NPr_3/3^ePr_1/1^t]³⁺ (?[NPr₂]³⁺) of cis-edge connected [NPr₄] tetrahedra (known from the Sm₄N₂S₃-type structure) are condensed into the double chain [(N1){(Pr1)_(2+2)/(2+2)^e,e(Pr2)_(2+1)/(2+1)^e,v}(N2)(Pr3)_1/1^t]³⁺ (?[N₂Pr₃]³⁺). Chain II consists of two single chains [NPr_2/2^vPr_2/1^t] ⁶⁺ (?[NPr₃]⁶⁺) of vertex-connected [NPr₄] tetrahedra (known from the Sm₃NS₃-type structure), which are condensed to the double chain [(N3)(Pr4)_2/2^e(Pr5)_2/2^v]³⁺ (?[NPr₂]³⁺) via an additional edge per “chain-link” too. Both types of chains are bundled along [010] like a closest packing of rods. Four crystallographically different but by X-ray diffraction indistinguishable anions S^2? and Cl^? hold both cationic double chains together and also adjust the charge balance in a molar ratio of 1 : 1.     

Darstellung und Kristallstruktur von LnAl3Br12 (Ln = La,Ce, Pr,Nd, Sm,Gd) und thermischer Abbau zu LnBr3

Preparation and Crystal Structure of LnAl₃Br₁₂ (Ln = La, Ce, Pr, Nd, Sm, Gd) and Thermal Decomposition to LnBr₃ LnAl₃Br₁₂ (Ln = La, Ce, Pr, Nd, Sm, Gd) was prepared in crystalline form for the first time. The crystal structures of LaAl₃Br₁₂, PrAl₃Br₁₂, and NdAl₃Br₁₂ were determined on single crystals by X-ray methods. The isotypic compounds crystallize with trigonal symmetry, space group P 3₁12, Z = 3. A structural comparison to lanthanoide chloroaluminates of equal composition is given and thermal decomposition of LnAl₃Br₁₂ (Ln = Nd) to the corresponding lanthanoide tribromide is described.     

Synthese und Kristallstrukturen von Bromid—Thiosilicaten Ln3Br[SiS4]2 der Lanthanide (Ln = La,Ce, Pr,Nd, Sm,Gd)

Synthesis and Crystal Structures of Lanthanide Bromide Thiosilicates Ln₃Br[SiS₄]₂ (Ln = La, Ce, Pr, Nd, Sm, Gd) Single crystals of the bromide—thiosilicates Ln₃Br[SiS₄]₂ were prepared by reaction of lanthanide metal (Ln = La, Ce, Pr, Nd, Sm, Gd), sulfur, silicon and bromine in quartz glass tubes. The thiosilicates crystallize in the monoclinic spacegroup C2/c (Z = 4) isotypically to the iodide analogues Ln₃I(SiS₄)₂ and the A—type chloride—oxosilicates Ln₃Cl[SiO₄]₂ with the following lattice constants: La₃Br[SiS₄]₂: a = 1583.3(4) pm, b = 783.0(1) pm, c = 1098.2(3) pm, β = 97.33(3)° Ce₃Br[SiS₄]₂: a = 1570.4(3) pm, b = 776.5(2) pm, c = 1092.2(2) pm, β = 97.28(2)° Pr₃Br[SiS₄]₂: a = 1562.6(3) pm, b = 770.1(2) pm, c = 1088.9(2) pm, β = 97.50(2)° Nd₃Br[SiS₄]₂: a = 1561.4(4) pm, b = 766.0(1) pm, c = 1085.3(2) pm, β = 97.66(3)° Sm₃Br[SiS₄]₂: a = 1555.4(3) pm, b = 758.5(2) pm, c = 1079.9(2) pm, β = 98.28(2)° Gd₃Br[SiS₄]₂: a = 1556.5(3) pm, b = 750.8(1) pm, c = 1074.5(2) pm, β = 99.26(2)° In the crystal structures the bromide ions form chains along [001] with trigonal planar coordination by lanthanide cations, while the [SiS₄]^4‐—building units display isolated distorted tetrahedra.     

Er2(CO3)2(C2O4)(H2O)2 — Synthese,Kristallstruktur und thermischer Abbau eines Carbonat‐Oxalat‐Hydrates des Erbiums

Er₂(CO₃)₂(C₂O₄)(H₂O)₂ — Synthesis, Crystal Structure and the Thermal Decomposition of a Carbonate‐Oxalate‐Hydrate of Erbium The hydrothermal reaction of an equimolar ratio of Er₂O₃ with the aminoacid L‐cysteine in evacuated glass ampoules in H₂O at 130 °C gave transparent, pink crystals of the formula Er₂(CO₃)₂(C₂O₄)(H₂O)₂. It crystallises in the monoclinic space group Cm (Z = 2, a = 777.3(2) pm, b = 1492.0(3) pm, c = 473.09(8) pm, b = 90.12(9)°). The thermal decomposition of Er₂(CO₃)₂(C₂O₄)(H₂O)₂ was investigated.     

Hydrogendiazid Synthese und Kristallstruktur von PPh4[N3HN3]

Hydrogen Diazide – Synthesis and Crystal Structure of PPh₄[N₃HN₃] PPh₄[N₃HN₃] has been prepared from PPh₄N₃ and Me₃SiN₃ by the reaction with water or ethanol forming colourless nonexplosive crystal needles, which were characterized by IR spectroscopy and by a crystal structure determination. Space group C2/c, Z = 12, lattice dimensions at –70 °C: a = 3782.4(3), b = 727.8(2), c = 2512.4(2) pm, β = 110.13(1)°, R = 0.0841. The [N₃HN₃]^– ion is characterized by an asymmetric N–H…N hydrogen bridge with a NN distance of 272(1) pm.     

Synthese und Kristallstruktur von Rb8[P4N6(NH)4](NH2)2 mit dem adamantanartigen Anion [P4N6(NH)4]6−

Synthesis and Crystal Structure of Rb₈[P₄N₆(NH)₄](NH₂)₂ with the Adamantane-like Anion [P₄N₆(NH)₄]^6? RbNH₂ reacts with P₃N₅ (molar ratio 6:1) at 400°C within 5 d to colourless Rb₈[P₄N₆(NH)₄](NH₂)₂. Suitable crystals for a X-ray structure determination were obtained: The compound contains adamantane-like molecular anions [P₄N₆(NH)₄]^6?. Their centres of gravity are arranged in a distorted hexagonal primitive array. All trigonal prisms of this array contain one amide ion. Rubidium ions connect the anions irregularly.     

Darstellung,Kristallstruktur, thermischer Abbau und Schwingungsspektren von [Co(NH3)6]2[Be4O(CO3)6] · 10 H2O

Preparation, Crystal Structure, Thermal Decomposition, and Vibrational Spectra of [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O is a suitable compound for the quantitative determination of beryllium. It can be obtained by reaction of aqueous solutions of carbonatoberyllate with [Co(NH₃)₆]Cl₃. The crystal structure (trigonal‐rhombohedral, R3c (Nr. 161), a = 1071,6(1) pm, c = 5549,4(9) pm, V_EZ = 5519(1) · 10⁶ pm³, Z = 6, R1(I ≥ 2σ(I)) = 0,037, wR2(I ≥ 2σ(I)) = 0,094) contains [Co(NH₃)₆]³⁺‐ and [Be₄O(CO₃)₆]^6–‐ions, which are directly hydrogen bonded as well as with water molecules. The complex cations and anions occupy the positions of a distorted anti‐CaF₂‐type. The thermal decomposition, IR and Raman spectra are presented and discussed.     

Zwei neue Sulfidchloride der Lanthanide: Synthese und Kristallstruktur von Pr7S6Cl9 und Nd7S6Cl9

Two Novel Sulfide Chlorides of the Lanthanides: Synthesis and Crystal Structure of Pr₇S₆Cl₉ and Nd₇S₆Cl₉ The reactions of the elemental lanthanides (M = Pr and Nd, resp.) with sulfur and the respective trichlorides (MCl₃) in evacuated silica tubes (850 °C, 7 d) yield single-phase sulfide chlorides of the composition M₇S₆Cl₉ when appropriate molar ratios (4 : 6 : 3) of the reactants (M : S : MCl₃) are used. A slight excess of trichloride as a flux promotes the formation of lath-shaped transparent single crystals (Pr₇S₆Cl₉: pale green, Nd₇S₆Cl₉: pale violet) which prove to be water soluble and sensitive to hydrolysis. The crystal structure was determined from X-ray single-crystal data taking Nd₇S₆Cl₉ (monoclinic, P2/c (no. 13); a = 2425.0(9), b = 664.2(2), c = 691.8(2) pm, β = 97.43(3)°, Z = 2; R = 0.060, R_w = 0.048) as an example. According to Guinier powder data, Pr₇S₆Cl₉ crystallizes isotypically with a = 2441.6(9), b = 669.1(2), c = 696.3(2) pm, and β = 97.74(3)°. Thus four crystallographically independent cations (M³⁺) are present, each except for M2 coordinated by four S^2– but differing in the number of their next Cl^– neighbors. The figures of coordination are completed by four Cl^– about M1 (square antiprism, CN = 8) and by three Cl^– each about M3 and M4 (monocapped trigonal prisms, CN = 7, 2 Ç ). In contrast, M2 is coordinated by only two S^2– but five (plus one) Cl^– as bicapped trigonal prism (CN = 7 + 1). Eight crystallographically different anions, although indistinguishable by X-ray diffraction, exhibit coordination numbers of four (3 Ç S^2– and 1 Ç Cl^–) and three (4 Ç Cl^–) with respect to the cations. So PbO-analogous layers of the composition ²_∞{[(S6/7Cl_1/7)M_4/4]₇}⁸⁺ parallel (010) are formed, consisting of 6/7 of S^2– and only 1/7 of Cl^– as centering anions for the edge-shared (M³⁺)₄ tetrahedra for reasons of charge neutrality. These cationic layers are held together by alternatingly sheathed layers of Cl^– with only threefold coordinated anions.     

Abbau von Koordinationspolymeren bis zum Monomer und Konkurrenz von Polymerisation und Chemischer Schere an Carbazolaten von Yb und Eu mit N‐Phenylpiperazin

Degradation of Coordination Polymers to the Monomer and Competition of Polymerization and Chemical Scissors on Carbazolates of Yb and Eu with N‐Phenylpiperazine The coordination polymers , Ln = Yb, Eu, Cbz⁻ = carbazolate anion, C₁₂H₈N⁻, can be degraded by the use of strong N‐donor ligands like N‐phenylpiperazine (Phpip = (C₆H₅)C₄H₈NNH) as chemical scissors. The degradation process for the ytterbium containing polymer ends in the monomeric compound [Yb(Cbz)₃(Phpip)₂]·1/2Phpip and includes an oxidation step Yb^II → Yb^III. Thus the circle of reactions of Yb metal with carbazole (CbzH) starting in liquid NH₃ to the coordination polymer and ending with its degradation by the use of chemical scissors is resolved. Transformation on europium has been started on the base of both metals leading to coordination polymers of the same chemical formula. However already the prelude of reactions differs for Eu as the electride induced reaction of Eu metal with CbzH in liquid ammonia followed by Phpip treatment gives single crystalline [Eu₂(Cbz)₄(NH₃)₂(Phpip)₄]·2Phpip. This dimeric molecule contains Eu^II and ligands of all reaction steps, NH₃, Cbz⁻, Phpip, and is thereby an interesting starting point for the resolution of polymer formation and degradation as well as a competition of these counter reactions.     

Synthese und Kristallstrukturen neuer komplexer Chloride der Lanthanide mit 3, 5‐Dimethylpyridiniumkationen: (3, 5‐Dimethylpyridinium)2[LnCl4(H2O)2]Cl (Ln = La,Pr) und (3, 5‐Dimethylpyridinium)3[TbCl6]

Preparation and Crystal Structures of New Complex Clorides of Lanthanides containing 3, 5‐Dimethylpyridinium Cations: (3, 5‐Dimethylpyridinium)₂[LnCl₄(H₂O)₂]Cl (Ln = La, Pr) and (3, 5‐Dimethylpyridinium)₃[TbCl₆] Crystals of the complex chlorides (3, 5‐dimethylpyridinium)₂[LaCl₄(H₂O)₂]Cl ( 1 ), (3, 5‐dimethylpyridinium)₂[PrCl₄(H₂O)₂]Cl ( 2 ) and (3, 5‐dimethylpyridinium)₃[TbCl₆] ( 3 ) have been prepared by reaction of LnCl₃ · x H₂O (Ln = La, Pr, Tb; x = 6‐7) with 3, 5‐dimethylpyridiniumchloride in ethanol/butanol solution. The crystal structures have been determined from single crystal X‐ray diffraction data. The compounds 1 and 2 are isotypic with each other and crystallize in the triclinic space group P1¯ (Z = 2). The 3, 5‐dimethylpyridinium cations are linked by hydrogen bonds to the anionic part of the structure built up by isolated chloride ions and strings of edge coupled triangulated dodecahedra [LnCl_4/2Cl₂(H₂O)₂]^—. The organic units are arranged forming a “π‐stacking”. 3 cristallizes monoclinically in the space group P2₁/c (Z = 4). The structure contains octahedral building units [TbCl₆]^3—. These octahedra are interconnected by the organic cations via hydrogen bonds forming chains parallel to [0 0 1].     

Saure Sulfate des Neodyms: Synthese und Kristallstruktur von (H5O2)(H3O)2Nd(SO4)3 und (H3O)2Nd(HSO4)3SO4

Acidic Sulfates of Neodymium: Synthesis and Crystal Structure of (H₅O₂)(H₃O)₂Nd(SO₄)₃ and (H₃O)₂Nd(HSO₄)₃SO₄ Light violett single crystals of (H₅O₂)(H₃O)₂ · Nd(SO₄)₃ are obtained by cooling of a solution prepared by dissolving neodymium oxalate in sulfuric acid (80%). According to X‐ray single crystal investigations there are H₃O⁺ ions and H₅O₂⁺ ions present in the monoclinic structure (P2₁/n, Z = 4, a = 1159.9(4), b = 710.9(3), c = 1594.7(6) pm, β = 96.75(4)°, R_all = 0.0260). Nd³⁺ is nine‐coordinate by oxygen atoms. The same coordination number is found for Nd³⁺ in the crystal structure of (H₃O)₂Nd(HSO₄)₃SO₄ (triclinic, P1, Z = 2, a = 910.0(1), b = 940.3(1), c = 952.6(1) pm, α = 100.14(1)°, β = 112.35(1)°, γ = 105.01(1)°, R_all = 0.0283). The compound has been prepared by the reaction of Nd₂O₃ with chlorosulfonic acid in the presence of air. In the crystal structure both sulfate and hydrogensulfate groups occur. In both compounds pronounced hydrogen bonding is observed.     

Aufbau und Abbau von (NH4)[BF4] und H3N‐BF3

Production and Decomposition of (NH₄)[BF₄] and H₃N‐BF₃ (NH₄)[BF₄] is produced as single crystals during the reaction of elemental boron and NH₄HF₂ (B : NH₄HF₂ = 1 : 2) and NH₄F (B : NH₄F = 1 : 4), respectively, in sealed copper ampoules at 300 °C. The crystal structure (baryte type, orthorhombic, Pnma, Z = 4) was redetermined at ambient temperature (a = 909.73(18), b = 569.77(10), c = 729.47(11) pm, R_all = 0.0361) and at 140 K (a = 887.3(2), b = 574.59(12), c = 717.10(12) pm, R_all = 0.0321). Isolated (NH₄)⁺ and [BF₄]^— tetrahedra are the important building units. The thermal behaviour of (NH₄)[BF₄] was investigated under inert (Ar, N₂) and reactive conditions (NH₃) with the aid of DTA/TG and DSC measurements and with in‐situ X‐ray powder diffraction as well. Finally, (NH₄)[BF₄] is decomposed yielding NH₃ and BF₃, BN is not produced under the current conditions. Colourless single crystals of H₃N‐BF₃ were prepared directly from the components NH₃ and BF₃. The crystal structure was determined anew at 293 and 170 K (orthorhombic, Pbca, Z = 8, a = 815.12(10), b = 805.91(14), c = 929.03(12) pm, R_all = 0.0367; a = 807.26(13), b = 800.48(10), c = 924.31(11) pm, R_all = 0.0292, T = 170 K). The crystal structure contains isolated molecules H₃N‐BF₃ in staggered conformation with a B‐N distance of 158 pm. The thermal behaviour of H₃N‐BF₃ was studied likewise.     

Two new groups of homoleptic rare earth pyridylbenzimidazolates: (NC12H8(NH)2)[Ln(N3C12H8)4] with Ln = Y,Tb, Yb,and [Ln(N3C12H8)2(N3C12H9)2][Ln(N3C12H8)4](N3C12H9)2 with Ln = La,Sm, Eu

The compounds (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y, Tb, Yb, and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), with Ln = La, Sm, Eu, were obtained by reactions of the group 3 metals yttrium and lanthanum as well as the lanthanides europium, samarium, terbium, and ytterbium with 2-(2-pyridyl)-benzimidazole. The reactions were carried out in melts of the amine without any solvent and led to two new groups of homoleptic rare earth pyridylbenzimidazolates. The trivalent rare earth atoms have an eightfold nitrogen coordination of four chelating pyridylbenzimidazolates giving an ionic structure with either pyridylbenzimidazolium or [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)](+) counterions. With Y, Eu, Sm, and Yb, single crystals were obtained whereas the La- and Tb-containing compounds were identified by powder methods. The products were investigated by X-ray single crystal or powder diffraction and MIR and far-IR spectroscopy, and with DTA/TG regarding their thermal behavior. They are another good proof of the value of solid-state reaction methods for the formation of homoleptic pnicogenides of the lanthanides. Despite their difference in the chemical formula, both types (NC(12)H(8)(NH)(2))[Ln(N(3)C(12)H(8))(4)], Ln = Y (1), Tb (2), Yb (3), and [Ln(N(3)C(12)H(8))(2)(N(3)C(12)H(9))(2)][Ln(N(3)C(12)H(8))(4)](N(3)C(12)H(9))(2), Ln = La (4), Sm (5), Eu (6), crystallize isotypic in the tetragonal space group I4(1). Crystal data for (1): T = 170(2) K, a = 1684.9(1) pm, c = 3735.0(3) pm, V = 10603.5(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.053, wR2 = 0.113. Crystal data for (3): T = 170(2) K, a = 1683.03(7) pm, c = 3724.3(2) pm, V = 10549.4(14) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.047, wR2 = 0.129. Crystal data for (5): T = 103(2) K, a = 1690.1(2) pm, c = 3759.5(4) pm, V = 10739(2) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.050, wR2 = 0.117. Crystal data for (6): T = 170(2) K, a = 1685.89(9) pm, c = 3760.0(3) pm, V = 10686.9(11) x 10(6) pm(3), R1 for F(o) > 4sigma(F(o)) = 0.060, wR2 = 0.144.