Anionische Fragmente aus h‐BN in der Struktur La6B4N10

Anionic Fragments of h‐BN in the Structure La₆B₄N₁₀ The compound La₆B₄N₁₀ was synthesized by solid state reactions at high temperatures. Crystals obtained for La₆B₄N₁₀ were systematically twinned and showed orthorhombic symmetry. An X‐ray crystal structure refinement on a needle shaped pseudo‐merohedral twin yielded the monoclinic space group P2₁/c, Z = 2, lattice parameters a = 971.89(6) pm, b = 1479.41(9) pm, c = 762.32(4) pm, β = 90.005(9)° and converged at R1 = 0.0352, wR2 = 0.0555 for all independent reflections. The structure of La₆(B₃N₆)(BN₃)N contains cyclic B₃N₆ ions with three exocyclic N atoms, carbonate ion like BN₃ units and nitride ions that can be considered as fragments or products of a nitration reaction of hexagonal boron nitride.     

La4N2S3: Ein neues Nitridsulfid des Lanthans mit beispielloser Kristallstruktur

La₄N₂S₃: A New Nitride Sulfide of Lanthanum with Unprecedented Crystal Structure The oxidation of lanthanum powder with sulfur and cesium azide (CsN₃) in the presence of lanthanum tribromide (LaBr₃) yields lanthanum nitride sulfide with the composition La₄N₂S₃ when appropriate molar ratios of the reactants are used. Additional cesium bromide (CsBr) as a flux secures fast reactions (7 d) at 900 °C in evacuated silica tubes as well as the formation of almost black single crystals. The orthorhombic crystal structure (Pnnm, Z = 2) was determined from single crystal X‐ray diffraction data (a = 641.98(4), b = 1581.42(9), c = 409.87(3) pm). Two crystallographically different La³⁺ cations are present, La1 resides in sixfold coordination of two N^3? and four S^2? anions forming a trigonal prism and La2 is coordinated by two N^3? and five S^2? in the shape of a monocapped trigonal prism. However, the main feature of the crystal structure comprises N^3?‐centred (La³⁺)₄ tetrahedra which arrange as pairs [N₂La₆]¹²⁺ of edge‐shared [NLa₄]⁹⁺ units and which are further connected via four vertices to form double chains . They get bundled along [001] like a hexagonal rod packing and are held together by two crystallographically different S^2? anions. Further motifs for the connectivity of [NM₄]⁹⁺ tetrahedra in crystal structures of nitride chalcogenides and halides of the rare‐earth elements (M = Sc, Y, La; Ce – Lu) with ratios of N : M = 1 : 2 are presented and discussed for comparison.     

(OLi2Ca4)3[ReN4]4, ein Nitridorhenat(VI)‐Oxid

(OLi₂Ca₄)₃[ReN₄]₄, a Nitridorhenate(VI) Oxide Black single crystals of (OLi₂Ca₄)₃[ReN₄]₄ were prepared from the elements (molar ratio Li : Ca : Re = 6 : 1 : 1) by reaction with molecular nitrogen at 900 °C; oxygen content results from a leak in the gas supply. The nitridorhenate(VI)‐oxide is an isotype of (OLi₂Ca₄)₃[MN₄]₄ (M = Mo^VI, W^VI). These compounds are obtained under similar reaction conditions in the presence of small amounts of oxygen containing impurities (Li‐/Ca‐hydroxides). The crystal structure of (OLi₂Ca₄)₃[ReN₄]₄ was determined by single crystal methods (cubic; I43d (# 220); a = 1315.88(9) pm; Z = 4) and can be derived from the Th₃P₄ type structure by hierarchical replacements: Th ≙ (OLi₂Ca₄)⁸⁺‐tetragonal bipyramids and P ≙ [Re^VIN₄]^6–‐tetrahedra.     

La3OCl[AsO3]2: Ein Lanthan‐Oxidchlorid‐Oxoarsenat(III) mit “lone‐pair”‐Kanalstruktur

La₃OCl[AsO₃]₂: A Lanthanum Oxide Chloride Oxoarsenate(III) with a “Lone‐Pair” Channel Structure La₃OCl[AsO₃]₂ was prepared by the solid‐state reaction between La₂O₃ and As₂O₃ using LaCl₃ and CsCl as fluxing agents in evacuated silica ampoules at 850 °C. The colourless crystals with pillar‐shaped habit crystallize tetragonally (a = 1299.96(9), c = 558.37(5) pm, c/a = 0.430) in the space group P4₂/mnm (no. 136) with four formula units per unit cell. The crystal structure contains two crystallographically different La³⁺ cations. (La1)³⁺ is coordinated by six oxygen atoms and two chloride anions in the shape of a bicapped trigonal prism (CN = 8), whereas (La2)³⁺ carries eight oxygen atoms and one Cl^? anion arranged in the shape of tricapped trigonal prism (CN = 9). The isolated pyramidal [AsO₃]^3? anions (d(As–O) = 175–179 pm) consist of three oxygen atoms (O2 and two O3), which surround the As³⁺ cations together with the free, non‐binding electron pair (lone pair) Ψ¹‐tetrahedrally (?(O–As–O) = 95°, 3×). One of the three crystallographically independent oxygen atoms (O1), however, is exclusively coordinated by four (La2)³⁺ cations in the shape of a real tetrahedron (d(O–La) = 236 pm, 4×). These [(O1)(La2)₄]¹⁰⁺ tetrahedra form endless chains in the direction of the c axis through trans‐edge condensation. Empty channels, constituted by the lone‐pair electrons of the Cl^? anions and the As³⁺ cations in the Ψ¹‐tetrahedral oxoarsenate(III) anions [AsO₃]^3?, run parallel to [001] as well.     

Über den H‐ und A‐Typ von La2[Si2O7]

On the H‐ and A‐Type Structure of La₂[Si₂O₇] By thermal decomposition of La₃F₃[Si₃O₉] at 700 °C in a CsCl flux single crystals of a new form of La₂[Si₂O₇] have been found which is called H type (triclinic, P1; a = 681.13(4), b = 686.64(4), c = 1250.23(8) pm, α = 82.529(7), β = 88.027(6), γ = 88.959(6)°; V_m = 87.223(9) cm³/mol, D_x = 5.113(8) g/cm³, Z = 4) continuing Felsche's nomenclature. It crystallizes isotypically to the triclinic K₂[Cr₂O₇] in a structure closely related to that of A–La₂[Si₂O₇] (tetragonal, P4₁; a = 683.83(7), c = 2473.6(4) pm; V_m = 87.072(9) cm³/mol, D_x = 5.122(8) g/cm³, Z = 8). For comparison, the latter has been refined from single crystal data, too. Both the structures can be described as sequence of layers of each of two crystallographically different [Si₂O₇]^6– anions always built up of two corner‐linked [SiO4] tetrahedra in eclipsed conformation with non‐linear Si–O–Si bridges (∢(Si–O–Si) = 128–132°) piled up in [001] direction and aligned almost parallel to the c axis. They differ only in layer sequence: Whereas the double tetrahedra of the disilicate units are tilted alternating to the left and in view direction ([010]; stacking sequence: AB) in H–La₂[Si₂O₇], after layer B there follow due to the 4₁ screw axis layers with anions tilted to the right and tilted against view direction ([010]; stacking sequence: ABA′B′) in A–La₂[Si₂O₇]. The extremely irregular coordination polyhedra around each of the four crystallographically independent La³⁺ cations in both forms (H and A type) consist of eight to ten oxygen atoms in spacing intervals of 239 to 330 pm. The possibility of more or less ordered intermediate forms will be discussed.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

La4B14O27: Ein Lanthan‐ultra‐Oxoborat mit Raumnetzstruktur

La₄B₁₄O₂₇: A Lanthanum ultra‐Oxoborate with a Framework Structure Single crystals of La₄B₁₄O₂₇ could be synthesized by the reaction of La₂O₃, LaCl₃ and B₂O₃ with an access of CsCl as fluxing agent in gastightly sealed platinum ampoules within twenty days at 710 °C and appear as colourless, transparent and waterresistant platelets. The new lanthanum oxoborate La₄B₁₄O₂₇ (monoclinic, C2/c; a = 1120.84(9), b = 641.98(6), c = 2537.2(2) pm, β = 100.125(8)°; Z = 4) is built of a three‐dimensional boron‐oxygen framework containing seven crystallographically different boron atoms. Four of these B³⁺ cations are surrounded by four O^2? anions tetrahedrally, whereas the other three have only three oxygen neighbours with nearly plane triangular coordination figures. Three of the [BO₄]^5? tetrahedra form [B₃O₉]^9? rings by cyclic vertex‐condensation, which are further linked via [BO₃]^3? units to infinite layers. Two of these layers connect via one [B₂O₇]^8? unit of two corner‐shared [BO₄]^5? tetrahedra to double layers, which themselves build up a three‐dimensional framework together with chains consisting of two [BO₄]^5? tetrahedra and one [BO₃]^3? triangle. One of the two crystallographically independent La³⁺ cations (La1) is surrounded by ten O^2? anions and resides within the oxoborate double layers. (La2)³⁺ shows a (8+2)‐fold coordination of O^2? anions and occupies channels along the [110] direction.     

TlCu5O(VO4)3 mit KCu5O(VO4)3‐Struktur – ein Thallium‐kupfer(II)‐oxidvanadat als Oxidationsprodukt einer Tl/Cu/V‐Legierung

TlCu₅O(VO₄)₃ with KCu₅O(VO₄)₃ Structure – a Thallium Copper(II) Oxide Vanadate as an Oxidation Product of a Tl/Cu/V Alloy Brown‐black crystals of the new oxide vanadate TlCu₅O(VO₄)₃ (triclinic, P1, a = 610.4(1) pm, b = 828.9(1) pm, c = 1075.3(1) pm, α = 97.70(1)°, β = 92.25(1)°, γ = 90.28(1)°, Z = 2) were obtained as a byproduct during the reaction of a Tl/Cu/V alloy with oxygen. The compound is isotypic with KCu₅O(VO₄)₃. All the crystals investigated were twins by non‐merohedry with [100] as the twin axis. The structure contains ladder shaped [Cu₁₀O₂₆]‐ribbons composed of edge‐ and corner‐sharing [CuO₅]‐polyhedra (tetragonal pyramids and trigonal bipyramids) and linked by vanadate groups. The thallium ions fill channels running along the a axis. No stereochemical activity of the thallium(I)‐lone pair is observed.     

Wasserfreie Selenite des Lanthans: Synthese und Kristallstruktur von La2(SeO3)3 und LaFSeO3

Anhydrous Selenites of Lanthanum: Syntheses and Crystal Structures of La₂(SeO₃)₃ and LaFSeO₃ Colorless single crystals of La₂(SeO₃)₃ were obtained via the decomposition of La₂(SeO₄)₃ in the presence of NaCl in sealed gold ampoules. The compound crystallizes in the orthorhombic system (Pnma, Z = 4, a = 846.7(1), b = 1428.6(1), c = 710.3(2) pm, R_all = 0.0223) and contains La³⁺ in tenfold coordination of oxygen atoms which belong to seven SeO₃^2– groups. Hence, three of the latter act as bidentate ligands. The reaction of LiF with La₂(SeO₄)₃ in sealed gold ampoules yielded colorless single crystals of LaFSeO₃ (monoclinic, P2₁/c, Z = 12, a = 1819.8(3), b = 715.75(8), c = 846.4(1) pm, β = 96.89(2)°, R_all = 0.0352). The crystal structure contains three crystallographically different La³⁺ ions. La1 is surrounded by six oxygen atoms from five SeO₃^2– groups and four fluoride ions, La2 is coordinated by two bidentate SeO₃^2– ions and seven fluoride ligands. La3 is surrounded by oxygen atoms only with the coordination number and polyhedron being almost the same as found for La³⁺ in La₂(SeO₃)₃. Furthermore, the crystal structures of both compounds are strongly influenced by the lone pairs of the SeO₃^2– groups.     

La2Si2O7 im I—Typ: Gemäß La6[Si4O13][SiO4]2 kein echtes Lanthandisilicat

I‐Type La₂Si₂O₇: According to La₆[Si₄O₁₃][SiO₄]₂ not a Real Lanthanum Disilicate In attempts to synthesize lanthanum telluride silicate La₂Te[SiO₄] (from La, TeO₂, SiO₂ and CsCl, molar ratio: 1 : 1: 1 : 20, 950 °C, 7 d) or fluoride‐rich lanthanum fluoride silicates (from LaF₃, La₂O₃, SiO₂ and CsCl, molar ratio: 5 : 2 : 3 : 17, 700 °C, 7 d) in evacuated silica tubes, colourless lath‐shaped single crystals of hitherto unknown I‐type La₂Si₂O₇ (monoclinic, P2₁/c; a = 726.14(5), b = 2353.2(2), c = 1013.11(8) pm, β = 90.159(7)°) were found in the CsCl‐flux melts. Nevertheless, this new modification of lanthanum disilicate does not contain any discrete disilicate groups [Si₂O₇]^6‐ but formally three of them are dismutated into one catena‐tetrasilicate ([Si₄O₁₃]^10‐ unit of four vertex‐linked [SiO₄]^4‐ tetrahedra) and two ortho‐silicate anions (isolated [SiO₄]^4‐ tetrahedra) according to La₆[Si₄O₁₃][SiO₄]₂. This compound can be described as built up of alternating layers of these [SiO₄]^4‐ and the horseshoe‐shaped [Si₄O₁₃]^10‐ anions along [010]. Between and within the layers the high‐coordinated La ³⁺ cations (CN = 9 ‐ 11) are localized. The close structural relationship to the borosilicates M₃[BSiO₆][SiO₄](M = Ce ‐ Eu) is discussed and structural comparisons with other catena‐tetrasilicates are presented.     

Synthese,Struktur und Reaktivität von Tris‐, Bis‐ und Mono(2,4‐dimethylpentadienyl)‐Komplexen des Neodyms,Lanthans und des Yttriums

The tris(2,4‐dimethylpentadienyl) complexes [Ln(η⁵‐Me₂C₅H₅)₃] (Ln = Nd, La, Y) are obtained analytically pure by reaction of the tribromides LnBr₃·nTHF with the potassium compound K(Me₂C₅H₅)(thf)_n in THF in good yields. The structural characterization is carried out by X‐ray crystal structure analysis and NMR‐spectroscopically. The tris complexes can be transformed into the dimeric bis(2,4‐dimethylpentadienyl) complexes [Ln₂(η⁵‐Me₂C₅H₅)₄X₂] (Ln, X: Nd, Cl, Br, I; La, Br, I; Y, Br) by reaction with the trihalides THF solvates in the molar ratio 2:1 in toluene. Structure and bonding conditions are determined for selected compounds by X‐ray crystal structure analysis and NMR‐spectroscopically in general. The dimer‐monomer equilibrium existing in solution was investigated NMR‐spectroscopically in dependence of the donor strength of the solvent and could be established also by preparation of the corresponding monomer neutral ligand complexes [Ln(η⁵‐Me₂C₅H₅)₂X(L)] (Ln, X, L: Nd, Br, py; La, Cl, thf; Br, py; Y, Br, thf). Finally the possibilities for preparation of mono(2,4‐dimethylpentadienyl)lanthanoid(III)‐dibromid complexes are shown and the hexameric structure of the lanthanum complex [La₆(η⁵‐Me₂C₅H₅)₆Br₁₂(thf)₄] is proved by X‐ray crystal structure analysis.     

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.     

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.     

Gerüstverbindungen mit beweglichen LaIII‐Kationen: Synthesen,Kristallstrukturen und Strukturdynamik der Lanthan(III)‐Eisen(II)‐Sulfid‐Halogenide La53Fe12S90X3 (X = Cl,Br, I)

Framework Compounds with Mobile La^III Cations: Syntheses, Crystal Structures and Structural Dynamics of the Lanthanum(III) Iron(II) Sulfide Halides La₅₃Fe₁₂S₉₀X₃ (X = Cl, Br, I) Black crystals of La₅₃Fe₁₂S₉₀X₃ (X = Cl, Br, I) were synthesized from La₂S₃ and FeS in a reactive LaX₃ flux at 1320 K. The structures were determined by single‐crystal X‐ray diffraction. The compounds are isostructural, crystallizing in the rhombohedral space group with Z = 1 (La₅₃Fe₁₂S₉₀Cl₃: a = 14.0154(7), c = 21.888(1) Å, V = 3723.5(3) ų; La₅₃Fe₁₂S₉₀Br₃: a = 14.0048(9), c = 22.040(2) Å, V = 3743.6(4) ų; La₅₃Fe₁₂S₉₀I₃: a = 13.9805(8), c = 22.108(2) Å, V = 3742.2(4) ų). The structure adopted is a stuffed variant of the La₅₂Fe₁₂S₉₀ structure type. [Fe^II₂S₉] dimers of face‐sharing octahedra are linked by face‐ and vertex‐sharing bi‐ or tri‐capped [La^IIIS_6+n] trigonal prisms, forming a three‐dimensional framework containing cuboctahedral cavities of two sizes. The larger cavities, which remain empty in the structure of La₅₂Fe₁₂S₉₀, are filled by halide ions in La₅₃Fe₁₂S₉₀X₃. The smaller cavities accommodate numerous sites for disordered lanthanum cations, modelling a network of diffusion pathways through the structure. An analogous picture is obtained from the calculation of the periodic nodal surface (PNS): The PNS separates a labyrinth containing the framework atoms from a labyrinth containing the mobile lanthanum cations. Molecular dynamic simulations confirm a strong coupling between the motions of the mobile lanthanum ions and the neighbouring sulfide ions.     

Solvothermal Synthesis,Crystal Structure and Properties of a New Organic Templated Lanthanum Sulfate [C4N3H16][La(SO4)3(H2O)]

A new organic templated lanthanum sulfate [C₄N₃H₁₆][La(SO₄)₃(H₂O)] ( 1 ) has been solvothermally synthesized by using n‐butanol as solvent. The colorless block crystals were characterized by IR, TGA, ICP, and XRD. The structure was determined by single‐crystal X‐ray diffraction: Monoclinic, P2₁/c, a = 10.8878(19), b = 15.478(3), c = 9.9639(18) Å, β = 114.062(2)°, V=1533.2(5) ų, Z = 4]. Crystal structure analysis shows that the one dimensional chain of 1 consists of the LaO₉ polyhedra and the sulfate groups. Coordination water molecules link adjacent chains by using hydrogen bonds to generate 2D layers, whereas the organic amines are inserted between the layers. The formation of 1 demonstrates that solvents play an important role during the synthesis.     

Ca3[BN2]I3: The First Halide‐Rich Alkaline Earth Nitrido­borate with Isolated [BN2]3– Units

The title compound Ca₃[BN₂]I₃ was obtained from reactions of mixtures of the starting materials Ca₃[BN₂]₂ and CaI₂ in a 1:4 ratio in sealed Nb tubes at 1223 K. The crystal structure was solved from powder synchrotron diffraction data. Ca₃[BN₂]I₃ is the first example of a halide‐rich nitridoborate crystallizing in the rhombohedral space group R32 [no. 155, Pearson code: hR96; Z = 12; a = 16.70491(2) Å, c = 12.41024(2) Å]. The crystal structure is built up by two interpenetrating networks of condensed edge‐sharing [BN₂]@Ca₆ and [□]@I₆ trigonal antiprisms (□ = void). In Ca₃[BN₂]I₃ two crystallograhically distinct [BN₂]^3– anions are present with d(B1–N) = 1.393(2) Å and d(B2–N) = 1.369(9) Å. Their bond angles are practically linear, varying only slightly: N–B1–N = 179(1)° and N–B2–N = 180°. Vibrational spectra were interpreted based on the D_∞h symmetry of the discrete linear [N–B–N]^3– moieties, considering the site symmetry reduction and the presence of two distinct [BN₂]^3– groups.     

[(PhSnS3)2(CuPPhMe2)6], ein sechskerniger Kupfer(I)‐Komplex mit PhSnS3‐Liganden

[(PhSnS₃)₂(CuPPhMe₂)₆], a Hexanuclear Copper(I) Complex with PhSnS₃ Ligands Na₃[PhSnS₃] which is available by the cleavage of Ph₄Sn₄S₆ with Na₂S in aqueous THF reacts with the copper(I) complex [(PhPMe₂)bipyCuCl] to give the hexanuclear copper(I) compound [(PhSnS₃)₂(CuPPhMe₂)₆] ( 1 ). 1 crystallizes in the space group P2₁/n with a = 1343.4(3) pm, b = 1134.5(2) pm, c = 2353.0(7) pm, β = 98.04(3)° (at 220 K). The molecular structure of 1 consists of six Cu(PPhMe₂) groups which are bridged by two PhSnS₃ units. The copper atoms are coordinated by two sulfur atoms and a terminal phosphine ligand in nearly planar arrangement with Cu‐S distances ranging between 223.6(2) and 232.9(2) pm.