MII(C4H12N2)[B2P3O12(OH)] (MII = Co,Zn): Synthesis and Crystal Structure of Novel Open Framework Borophosphates

Two novel borophosphates, M^II(C₄H₁₂N₂)[B₂P₃O₁₂(OH)] (M^II = Co, Zn), exhibiting open frameworks, have been synthesized by hydrothermal reactions (T = 165 °C). The crystal structures of the isotypic compounds have been determined both at 293 K (orthorhombic, Ima2 (no. 46), Z = 4; M^II = Co: a = 12.4635(4) Å, b = 9.4021(4) Å, c = 11.4513(5) Å, V = 1341.90 ų, R₁ = 0.0202, wR₂ = 0.0452, 2225 observed reflections with I > 2σ(I); M^II = Zn: a = 12.4110(9) Å, b = 9.4550(5) Å, c = 11.4592(4) Å, V = 1344.69 ų, R₁ = 0.0621, wR₂ = 0.0926, 1497 observed reflections with I > 2σ(I)). Distorted CoO₆‐octahedra and ZnO₅‐square‐pyramids, respectively, share common oxygen‐corners with BO₄‐, PO₄‐ and (HO)PO₃‐tetrahedra. The tetrahedral groups are linked via common corners to form infinite loop‐branched borophosphate chains [B₂P₃O₁₂(OH)^4–]. The open framework of M^II‐coordination polyhedra and tetrahedral borophosphate chains contains a three‐dimensional system of interconnected structural channels running along [100], [011] and [011], respectively, which are occupied by di‐protonated piperazinium ions.     

(Ni3–xMgx)[B3P3O12(OH)6] · 6 H2O (x ≈ 1.5): A Novel BorophosphateHydrate Containing Isolated Six‐Membered Rings of Tetrahedra

A novel borophosphate‐hydrate, (Ni_3–xMg_x)[B₃P₃O₁₂(OH)₆] · 6 H₂O (x ≈ 1.5), has been prepared by hydrothermal synthesis (T = 170 °C) from a mixture of NiCl₂ · 6 H₂O, Mg(OH)₂, B₂O₃ and H₃PO₄. The crystal structure was determined at 293 K from single‐crystal X‐ray diffraction data (trigonal, R3c (no. 167), a = 14.957(10) Å, c = 13.812(6) Å, V = 2676(2) ų, Z = 6, R₁ = 0.0276, wR₂ = 0.0714 for 779 observed reflections with I > 2σ(I)). The crystal structure contains unbranched six‐membered rings [B₃P₃O₁₂(OH)₆]^6– of alternating corner linked borate and phosphate tetrahedra, which are stacked along [001] and connected via M^IIO₂(OH)₂(H₂O)₂ coordination polyhedra. Hydrogen bonding between the tetrahedral six‐membered rings and M^IIO₂(OH)₂(H₂O)₂ octahedra leads to a further cross‐linking. With respect to the arrangement of isolated six‐membered tetrahedral rings the crystal structure of this borophosphate‐hydrate is closely related to the cyclo‐hexasilicate dioptase, Cu₆[Si₆O₁₈] · 6 H₂O.     

Synthese und Kristallstruktur von Vanadium(III)‐borophosphat,V2[B(PO4)3]

Synthesis and Crystal Structure of Vanadium(III) Borophosphate, V₂[B(PO₄)₃] By reaction of boron phosphate, BPO₄, and vanadium(IV)‐oxide, VO₂, at 1050 °C a hitherto unknown vanadium(III)‐borophosphate is formed. Its composition was found to be V₂BP₃O₁₂, its structure was elucidated by single crystal X‐ray diffraction, the cell parameters are: a = b = 13.9882Å; c = 7.4515Å; α = β = 90°, γ = 120°; Z = 6; space group: P6 3/m. Noteworthy features of the structure are V₂O₉ units (two V^IIIO₆ octahedra connected via their faces) and isolated trisphosphatoborate groups, B(PO₄)₃. By shared oxide ions, the aforementioned groups are interconnected, thus forming a three dimensional network. The structural relation between the title compound and an analogous chromium compound is discussed.     

RbFe[BP2O8(OH)]: Ein neues Borophosphat mit offen-verzweigten Vierer-Einfach-Tetraederketten

RbFe[BP₂O₈(OH)]: A New Borophosphate Containing Open-Branched Tetrahedral Vierer-Einfach Chains RbFe[BP₂O₈(OH)] is formed under mild hydrothermal conditions (T = 165–170 °C) from a mixture of RbOH_(aq), FeCl₂ · 4 H₂O, H₃BO₃ and H₃PO₄. The crystal structure of the monoclinic compound was solved by x-ray single crystal methods (space group P2₁/c, No. 14): a = 935.8(5) pm, b = 833.9(6) pm, c = 965.6(5) pm; β = 101.69(4)°; Z = 4. The anionic partial structure contains open-branched vierer-einfach chains [BP₂O₈(OH)]^4–, which are formed by alternating borate and phosphate tetrahedra sharing common corners. Fe³⁺ is in an octahedral coordination (FeO₅(OH)), while Rb⁺ is irregularly coordinated by ten oxygen-functions of neighbouring tetrahedra.     

Isotype Borophosphate MII(C2H10N2)[B2P3O12(OH)] (MII = Mg,Mn, Fe,Ni, Cu,Zn): Verbindungen mit Tetraeder‐Schichtverbänden

Isotypic Borophosphates M^II(C₂H₁₀N₂)[B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn): Compounds containing Tetrahedral Layers The isotypic compounds M^II(C₂H₁₀N₂) · [B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn) were prepared under hydrothermal conditions (T = 170 °C) from mixtures of the metal chloride (chloride hydrate, resp.), Ethylenediamine, H₃BO₃ and H₃PO₄. The orthorhombic crystal structures (Pbca, No. 61, Z = 8) were determined by X‐ray single crystal methods (Mg(C₂H₁₀N₂)[B₂P₃O₁₂(OH)]: a = 936.81(2) pm, b = 1221.86(3) pm, c = 2089.28(5) pm) and Rietveld‐methods (M^II = Mn: a = 931.91(4) pm, b = 1234.26(4) pm, c = 2129.75(7) pm, Fe: a = 935.1(3) pm, b = 1224.8(3) pm, c = 2088.0(6) pm, Ni: a = 939.99(3) pm, b = 1221.29(3) pm, c = 2074.05(7) pm, Cu: a = 941.38(3) pm, b = 1198.02(3) pm, c = 2110.01(6) pm, Zn: a = 935.06(2) pm, b = 1221.33(2) pm, c = 2094.39(4) pm), respectively. The anionic part of the structure contains tetrahedral layers, consisting of three‐ and nine‐membered rings. The M^II‐ions are in a distorted octahedral or tetragonal‐bipyramidal [4 + 2] (copper) coordination formed by oxygen functions of the tetrahedral layers. The resulting three‐dimensional structure contains channels running along [010]. Protonated Ethylenediamine ions are fixed within the channels by hydrogen bonds.     

Drei neue Selenoborato-closo-dodekaborate: Synthesen und Kristallstrukturen von Rb8[B12(BSe3)6], Rb4Hg2[B12(BSe3)6] und Cs4Hg2[B12(BSe3)6]

Three Novel Selenoborato- closo -dodecaborates: Syntheses and Crystal Structures of Rb₈[B₁₂(BSe₃)₆], Rb₄Hg₂[B₁₂(BSe₃)₆], and Cs₄Hg₂[B₁₂(BSe₃)₆] The three selenoborates Rb₈[B₁₂(BSe₃)₆] (P1, a = 10.512(5) Å, b = 10.450(3) Å, c = 10.946(4) Å, α = 104.53(3)°, β = 91.16(3)°, γ = 109.11(3)°, Z = 1), Cs₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.860(2) Å, b = 10.740(2) Å, c = 11.078(2) Å, α = 99.94(3)°, β = 90.81(3)°, γ = 115.97(3)°, Z = 1), and Rb₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.593(2) Å, b = 10.458(2) Å, c = 11.131(2) Å, α = 99.25(3)°, β = 91.16(3)°, γ = 116.30(3)°, Z = 1) were prepared from the metal selenides, amorphous boron and selenium by solid state reactions at 700 °C. These new chalcogenoborates contain B₁₂ icosahedra completely saturated with six trigonal-planar BSe₃ entities functioning as bidentate ligands to form a persubstituted closo-dodecaborate anion. The two isotypic compounds Rb₄Hg₂[B₁₂(BSe₃)₆] and Cs₄Hg₂[B₁₂(BSe₃)₆] are the first selenoborate structures containing a transition metal which are characterized by single crystal diffraction.     

Cd3[B2P4O14(OH)4]: A 3D Open‐Framework Cadmium Borophosphate with Unique Twisted 8‐Ring Channels

Abstract. The cadmium borophosphate compound Cd₃[B₂P₄O₁₄(OH)₄] was synthesized under mild hydrothermal conditions. The crystal structure was determined by single‐crystal X‐ray diffraction [triclinic, space group P$\bar{1}$ (no. 2), a = 5.4362(11) Å, b = 8.2190(16) Å, c = 8.3918(17) Å, and α = 111.87(3)°, β = 104.63(3)°, γ = 90.73(3)°, V = 334.29(12) ų and Z = 1]. The 3D open framework of the title compound is constructed from BO₃(OH) tetrahedra and 2D layers along the [100] direction. The resulting framework contains twisted eight‐membered rings that form 1D channels.     

Das erste Vanadium(III)‐Borophosphat: Darstellung und Kristallstruktur von CsV3(H2O)2[B2P4O16(OH)4]

The First Vanadium(III) Borophosphate: Synthesis and Crystal Structure of CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] was prepared under mild hydrothermal conditions (T = 165 °C) from mixtures of CsOH_(aq), VCl₃, H₃BO₃, and H₃PO₄ (molar ratio 1 : 1 : 1 : 2). The crystal structure was determined by X‐ray single crystal methods (monoclinic; space group C2/m, No. 12): a = 958.82(15) pm, b = 1840.8(4) pm, c = 503.49(3) pm; β = 110.675(4)°; Z = 2. The anionic partial structure contains oligomeric units [BP₂O₈(OH)₂]^5–, which are built up by a central BO₂(OH)₂ tetrahedron and two PO₄ tetrahedra sharing common corners. V^III is octahedrally coordinated by oxygen of adjacent phosphate tetrahedra and OH groups of borate tetrahedra as well as oxygen of phosphate tetrahedra and H₂O molecules, respectively (coordination octahedra VO₄(OH)₂ and VO₄(H₂O)₂). The oxidation state +3 for vanadium was confirmed by measurements of the magnetic susceptibility. The trimeric borophosphate groups are connected via vanadium centres to form layers with octahedra‐tetrahedra ring systems, which are likewise linked via V^III‐coordination octahedra. Overall, a three‐dimensional framework constructed from VO₄(OH)₂ and VO₄(H₂O)₂ octahedra as well as BO₂(OH)₂ and PO₄ tetrahedra results. The structure contains channels running along [001], which are occupied by Cs⁺ in a distorted octahedral coordination (CsO₄(H₂O)₂).     

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.     

Alkalimolybdotellurate: Darstellung und Kristallstruktur von Rb6[TeMo6O24] · 10H2O und Rb6[TeMo6O24] · Te(OH)6 · 6H2O

Alkaline Molybdotellurates: Preparation and Crystal Structures of Rb₆[TeMo₆O₂₄] · 10H₂O and Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6H₂O Single crystals of Rb₆[TeMo₆O₂₄] · 10 H₂O and Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6 H₂O, respectively, were grown from aqueous solution. Rb₆[TeMo₆O₂₄] · 10 H₂O possesses the space group P1 . The lattice dimensions are a = 963.40(13), b = 972.56(12), c = 1 056.18(13) pm, α = 97.556(10), β = 113.445(9), γ = 102.075(10)°; Z = 1, 2 860 reflections, 215 parameters refined, R_g = 0.0257. The centrosymmetrical [TeMo₆O₂₄]^6? anions are stacked parallel to [010]. Rb(2) is coordinated with one exception by water molecules only. Folded chains consisting of [TeMo₆O₂₄]^6? anions and Rb(2) coordination polyhedra which are linked to pairs represent the prominent structural feature. Rb₆[TeMo₆O₂₄] · Te(OH)₆ · 6 H₂O crystallizes monoclinically in the space group C2/c with a = 1 886.4(3), b = 1 000.9(1), c = 2 126.5(3) pm, and β = 115.90(1)°; Z = 4, 3 206 reflections, 240 parameters refined, R_g = 0.0333. It is isostructural in high extent with (NH₄)₆[TeMo₆O₂₄] · Te(OH)₆ · 7 H₂O. Hydrogen bonds between Te(OH)₆ molecules and [TeMo₆O₂₄]^6? anions establish infinite strands. The [TeMo₆O₂₄]^6? anions gather around Te(OH)₆ providing channel-like voids extending parallel to [001].     

Synthesis and Crystal Structure of SrFe[BP2O8(OH)2]

SrFe[BP₂O₈(OH)₂] was synthesised under mild hydrothermal conditions. The crystal structure was determined from single–crystal X–ray diffraction data: triclinic, space group P (No. 2), a = 6.6704(12) Å, b = 6.6927(13) Å, c = 9.3891(19) Å, α = 109.829(5)°, β = 102.068(6)°, γ = 103.151(3)°, V = 364.74(12) ų and Z = 2. The crystal structure of SrFe[BP₂O₈(OH)₂] contains isolated borophosphate oligomers, [BP₂O₈(OH)₂]^5–, which are interconnected by Fe^IIIO₄(OH)₂ coordination octahedra. The resulting three–dimensional framework is characterised by elliptical channels running along [011]. Strontium takes positions inside the channels.     

[Ph2P(O)CH2Im][F3B(μ‐OH)BF3]. Erste strukturanalytische Charakterisierung des Hexafluoro(μ‐hydroxo)diborat‐Ions [1]

[Ph₂P(O)CH₂Im][F₃B(μ‐OH)BF₃]. First Structural Characterization of the Hexafluoro(μ‐hydroxo)diborate Ion [1] The hexafluoro(μ‐hydroxo)diborate ion has been isolated as it's Ph₂P(O)CH₂Im salt [Im = 2‐(1, 3, 4, 5‐tetramethylimidazolio)] ( 2 ) through basic hydrolysis of [Ph₂P(OBF₃)CH₂Im]BF₄ ( 1 ). The crystal structure of 2 · CH₂Cl₂ reveals the presence of ion pairs linked by unsymmetrical O‐H‐O hydrogen bonds.     

Synthese,Kristallstruktur und Eigenschaften der käfigartigen,sechsbasigen Säure P12S12N8(NH)6 · 14 H2O sowie ihrer Salze Li6[P12S12N14] · 26 H2O, (NH4)6[P12S12N14] · 10 H2O und K6[P12S12N14] · 8 H2O

Syntheses, Crystal Structure, and Properties of the Cage‐like, Hexaacidic P₁₂S₁₂N₈(NH)₆ · 14 H₂O and its Salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O, (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O, and K₆[P₁₂S₁₂N₁₄] · 8 H₂O The cage‐like acid P₁₂S₁₂N₈(NH)₆ · 14 H₂O was obtained by the reaction of KSCN with P₄S₁₀ via the formation of K₆[P₁₂S₁₂N₁₄] · 8 H₂O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O and (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O were synthesized. According to X‐ray single‐crystal structure analyses the compounds are built up by isosteric P–N cages [P₁₂S₁₂N^[3]₈N^[2]₆]^6–. Each of them is made up of twelve P₃N₃ rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m3; P₁₂S₁₂N₈(NH)₆ · 14 H₂O: P1, a = 1119.11(7), b = 1123.61(7), c = 1125.80(6) pm, α = 80.186(4), β = 60.391(4), γ = 60.605(4)°, Z = 1; Li₆[P₁₂S₁₂N₁₄] · 26 H₂O: Fm3, a = 1797.4(1) pm, Z = 4; (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O: P6₃, a = 1153.2(1), c = 2035.6(2) pm, Z = 2; K₆[P₁₂S₁₂N₁₄] · 8 H₂O: R3c, a = 1142.37(5), c = 6009.6(3) pm, Z = 6. In the crystal the cages of the acid are crosslinked via hydrate molecules by hydrogen bonds. The cations in the salts show a high‐mobility and are located between the cages.     

A New Sodium Borate: Na[B6O8(OH)3]·6H2O·H3BO3

The structure of [B₆H₉NaO₁₄, H₃BO₃, 6H₂O] was determined by single‐crystal X‐ray diffraction and further analyzed by FTIR spectroscopy and differential thermal/thermogravimetric analysis. The asymmetric unit contains Na–O polyhedra (distorted octahedron), [B₆O₈(OH)₃]^– fundamental building blocks, one free water molecule and one free H₃BO₃ molecule. In the hexaborate anion, three B₃O₃ rings are linked by a common oxygen atom with five trigonal and one tetrahedral boron atoms. The hexaborate group is also linked to the oxygenated environment of the sodium atom by three other six‐membered rings, each of which involve two boron atoms, three oxygen atoms, and sodium as the joint atom.     

Synthesis and Crystal Structure of {(NH4)xCo((3–x)/2)}(H2O)2[BP2O8] · (1 – x) H2O (x ≈ 0.5)

A borophosphate hydrate with general composition {(NH₄)_xCo_((3–x)/2)}(H₂O)₂[BP₂O₈] · (1 – x) H₂O (x ≈ 0.5) was prepared under mild hydrothermal conditions (T = 170 °C). The crystal structure of the purple title compound was refined in space group P6₅ (no. 170) as a merohedric twin (a = 949.14 pm, c = 1558.25 pm, R₁ = 0.037, wR₂ = 0.092 for all data). According to preliminary X‐ray investigations, vis‐spectra, and magnetic susceptibility measurements, a second blue coloured variant exhibits a superstructure of the title compound with a change in coordination numbers around cobalt from six and five to six and four. Both phases show reversible de‐/rehydration properties.     

Zu den Kristallstrukturen der Übergangsmetall(II)‐Dodekahydro‐closo‐Dodekaborat‐Hydrate Cu(H2O)5,5[B12H12]·2,5 H2O und Zn(H2O)6[B12H12]·6 H2O

On the Crystal Structures of the Transition‐Metal(II) Dodecahydro‐closo‐Dodecaborate Hydrates Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O and Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic copper(II) carbonate or zinc carbonate, blue lath‐shaped single crystals of the octahydrate Cu[B₁₂H₁₂]·8 H₂O (≡ Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O) and colourless face‐rich single crystals of the dodecahydrate Zn[B₁₂H₁₂]·12 H₂O (≡ Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O) could be isolated after isothermic evaporation. Copper(II) dodecahydro‐closo‐dodecaborate octahydrate crystallizes at room temperature in the monoclinic system with the non‐centrosymmetric space group Pm (Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O: a = 768.23(5), b = 1434.48(9), c = 777.31(5) pm, β = 90.894(6)°; Z = 2), whereas zinc dodecahydro‐closo‐dodecaborate dodecahydrate crystallizes cubic in the likewise non‐centrosymmetric space group F23 (Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O: a = 1637.43(9) pm; Z = 8). The crystal structure of Cu(H₂O)_5.5[B₁₂H₁₂]·2.5 H₂O can be described as a monoclinic distortion variant of the CsCl‐type arrangement. As characteristic feature the formation of isolated [Cu₂(H₂O)₁₁]⁴⁺ units as a condensate of two corner‐linked Jahn‐Teller distorted [Cu(H₂O)₆]²⁺ octahedra via an oxygen atom of crystal water can be considered. Since “zeolitic” water of hydratation is also present, obviously both classical H–O^δ?···^+δH–O and non‐classical B–H^δ?···^+δH–O hydrogen bonds play a significant role for the stabilization of the structure. A direct coordinative influence of the quasi‐icosahedral [B₁₂H₁₂]^2? anions on the Cu²⁺ cations has not been determined. The zinc compound Zn(H₂O)₆[B₁₂H₁₂]·6 H₂O crystallizes in a NaTl‐type related structure. Two crystallographically different [Zn(H₂O)₆]²⁺ octahedra are present, which only differ in their relative orientation within the packing of the [B₁₂H₁₂]^2? anions. The stabilization of the crystal structure takes place mainly via H–O^δ?···^+δH–O hydrogen bonds, since again the hydrogen atoms of the [B₁₂H₁₂]^2? anions have no direct coordinative influence on the Zn²⁺ cations.     

2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures of CF₃C(O)N(H)P(O)[N(CH₃)(CH₂C₆H₅)]₂ ( 1 ) and 4‐NO₂‐C₆H₄N(H)P(O)[4‐CH₃‐NC₅H₉]₂ ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. ¹³C NMR spectra were used for study of ²J(P,C) and ³J(P,C) coupling constants that were showed in the molecules containing N(C₂H₅)₂ and N(C₂H₅)(CH₂C₆H₅) moieties, ²J(P,C)>³J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC₄H₈. ²J(P,C) for N(C₂H₅)₂ moiety and in NC₄H₈ are nearly the same, but ³J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH₂R)(CH₂C₆H₅)]₂, ²J(P,CH₂)_benzylic>²J(P,CH₂)_aliphatic, in an agreement with our previous study.     

Ein anionischer Oxohydroxo‐Komplex mit Bismut(III): Na6[Bi2O2(OH)6](OH)2 · 4H2O

An Anionic Oxohydroxo Complex with Bismuth(III): Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O Colourless, plate‐like, air sensitive crystals of Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O are obtained by reaction of Bi₂O₃ or Bi(NO₃)₃ · 5H₂O in conc. NaOH (58 wt %) at 200 °C followed by slow cooling to room temperature. The crystal structure (triclinic, P 1¯, a = 684.0(2), b = 759.8(2), c = 822.7(2) pm, α = 92.45(3)°, ß = 90.40(3)°, γ = 115.60(2)°, Z = 1, R1, wR2 (all data), 0, 042, 0, 076) contains dimeric, anionic complexes [Bi₂O₂(OH)₆]^4— with bismuth in an ψ¹‐octahedral coordination of two oxo‐ and three hydroxo‐ligands. The thermal decomposition was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In the final of three steps the decomposition product is Na₃BiO₃.     

12‐Membered borophosphate rings in KNi5[P6B6O23(OH)13]

The title compound, potassium pentanickel hexaborophosphate tridecahydroxide, was synthesized under hydrothermal conditions from the NiCl₂–K₃PO₄–B₂O₃–K₂CO₃–H₂O system. The crystal structure was determined using single‐crystal X‐ray diffraction at 100 K. The KNi₅[P₆B₆O₂₃(OH)₁₃] phase is cubic. For the three crystallographically distinct Ni centers, two occupy sites with 3 symmetry, while the third Ni and the K atom are located on sites. The structure is built from alternating borate and phosphate tetrahedra forming 12‐membered puckered rings with K⁺ ions at the centers. These rings are arranged as in cubic dense sphere packing. A novel feature of the new crystal structure is the presence of linear trimers of face‐sharing [NiO₆] octahedra occupying the octahedral interstices of this sphere packing, and of single [NiO₆] octahedra in the tetrahedral interstices. All oxygen corners of the Ni octahedra are linked to phosphate or borate tetrahedra of the 12‐membered rings to form a mixed anionic framework.     

Synthesis,Characterization, and Crystal Structures of [N(CH3)4]2[B12H12] and [N(CH3)4]2[B12H12] · CH3CN

Bis(tetramethylammonium) dodecahydrododecaborate, [(CH₃)₄N]₂[B₁₂H₁₂], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN, were synthesized and characterized via Infrared, ¹H and ¹¹B NMR spectroscopy. [(CH₃)₄N]₂[B₁₂H₁₂] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F²) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH₃)₄N]₂[B₁₂H₁₂] and [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN at –70 and –15 °C, respectively.