Semiconducting La2AuP3, the Metallic Conductor Ce2AuP3, and other Rare‐Earth Gold Phosphides Ln2AuP3 with Two Closely Related Crystal Structures

The compounds Ln₂AuP₃ were synthesized by reaction of the elemental components in evacuated silica tubes. Their crystal structures were determined from single‐crystal diffractometer data. The compounds with Ln = La, Ce, and Pr crystallize with an orthorhombic U₂NiC₃ type structure (Pnma, Z = 4). The structure refinement for Ce₂AuP₃ resulted in a = 774.14(6) pm, b = 421.11(4) pm, c = 1612.3(1) pm, R = 0.019 for 1410 structure factors and 38 variable parameters. For Pr₂AuP₃ a residual of R = 0.024 was obtained. Nd₂AuP₃ crystallizes with a monoclinic distortion of this structure: P2₁/c, Z = 4, a = 416.14(4) pm, b = 768.87(6) pm, c = 1647.1(2) pm, β = 104.06(1)°, R = 0.022 for 1361 F values and 56 variables. The near‐neighbor coordinations of the two structures are nearly the same. In both structures the gold and phosphorus atoms form two‐dimensionally infinite nets, where the gold atoms are tetrahedrally coordinated by phosphorus atoms with Au–P distances varying between 245.8 and 284.2 pm. Two thirds of the phosphorus atoms form pairs with single‐bond distances varying between 217.7 and 218.9 pm. Thus, using oxidation numbers the structures can be rationalized with the formulas (Ln⁺³)₂[AuP₃]^–6 and (Ln⁺³)₂Au⁺¹(P₂)^–4P^–3. Accordingly, La₂AuP₃ is a diamagnetic semiconductor. Pr₂AuP₃ is semiconducting with an antiferromagnetic ground state, showing metamagnetism with a critical field of B_c = 0.5(± 0.1) T. In contrast, the cerium compound is a metallic conductor, even though its cell volume indicates that the cerium atoms are essentially trivalent, as is also suggested by the ferro‐ or ferrimagnetic behavior of the compound.     

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.     

Mono‐ and Dimethyl‐1,2,4‐Triazolate as Ligands for the Mercuric Ion in the Cationic Three‐dimensional Coordination Polymer of [Hg2(Mmt)(Dmt)2](NO3)(H2O)

Colourless crystals of [Hg₂(Mmt)(Dmt)₂](NO₃)(H₂O) were obtained from a reaction of mercuric nitrate with monomethyl‐ and dimethyl‐1,2,4‐triazolate (Mmt^? and Dmt^?, respectively). In the crystal structure (monoclinic, C2/c (no. 15), a = 2579.4(4), b = 1231.1(2), c = 1634.8(2) pm, β = 128.32(1)°, V = 4073.3(11)·10⁶·pm³, Z = 8, R₁ [I₀ > 2σ(I₀)]: 0.0355), half of the mercuric ions are essentially two‐coordinate (Hg–N: 210‐215 pm), the other half are tetrahedrally surrounded by N‐donor atoms (Hg–N: 221, 225 pm) of the Mmt^? and Dmt^? anions. These three‐N ligands construct a three‐dimensional framework.     

Drei Alkalimetall‐Erbium‐Thiophosphate: Von der Schichtstruktur bei KEr[P2S7] zur dreidimensionalen Vernetzung in NaEr[P2S6] und Cs3Er5[PS4]6

Three Alkali‐Metal Erbium Thiophosphates: From the Layered Structure of KEr[P₂S₇] to the Three‐Dimensional Cross‐Linkage in NaEr[P₂S₆] and Cs₃Er₅[PS₄]₆ The three alkali‐metal erbium thiophosphates NaEr[P₂S₆], KEr[P₂S₇], and Cs₃Er₅[PS₄] show a small selection of the broad variety of thiophosphate units: from ortho‐thiophosphate [PS₄]^3? and pyro‐thiophosphate [S₃P–S–PS₃]^4? with phosphorus in the oxidation state +V to the [S₃P–PS₃]^3? anion with a phosphorus‐phosphorus bond (d(P–P) = 221 pm) and tetravalent phosphorus. In spite of all differences, a whole string of structural communities can be shown, in particular for coordination and three‐dimensional linkage as well as for the phosphorus‐sulfur distances (d(P–S) = 200 – 213 pm). So all three compounds exhibit eightfold coordinated Er³⁺ cations and comparably high‐coordinated alkali‐metal cations (CN(Na⁺) = 8, CN(K⁺) = 9+1, and CN(Cs⁺) ≈ 10). NaEr[P₂S₆] crystallizes triclinically ( ; a = 685.72(5), b = 707.86(5), c = 910.98(7) pm, α = 87.423(4), β = 87.635(4), γ = 88.157(4)°; Z = 2) in the shape of rods, as well as monoclinic KEr[P₂S₇] (P2₁/c; a = 950.48(7), b = 1223.06(9), c = 894.21(6) pm, β = 90.132(4)°; Z = 4). The crystal structure of Cs₃Er₅[PS₄] can also be described monoclinically (C2/c; a = 1597.74(11), b = 1295.03(9), c = 2065.26(15) pm, β = 103.278(4)°; Z = 4), but it emerges as irregular bricks. All crystals show the common pale pink colour typical for transparent erbium(III) compounds.     

[Gd(OH)(H2O)(b18c6)]I(I3)(CH3CN), a New Cationic In‐cavity Complex with Iodide and Triiodide as Anions

Single crystals of [Gd(OH)(H₂O)(b18c6)]I(I₃)(CH₃CN) were obtained from an acetonitrile solution of GdI₃, I₂ and benzo‐18‐crown‐6. The crystal structure (monoclinic, P2₁/a (no. 14), Z = 4, a = 1233.8(1) pm, b = 1925.0(2) pm, c = 1252.3(1) pm, β = 104.375(7)°) contains hydroxide bridged cationic dimers and iodide as well as triiodide as anions.     

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.     

Phosphaniminato‐Acetato‐Komplexe von Cobalt und Cadmium mit M4N4‐Heterocuban‐Struktur

Phosphoraneiminato‐Acetato Complexes of Cobalt and Cadmium with M₄N₄ Heterocubane Structure The phosphoraneiminato‐acetato complexes [M(NPEt₃)(O₂C–CH₃)]₄ with M = Co and Cd are formed from the anhydrous metal(II) acetates with excess Me₃SiNPEt₃ at 180 °C. By crystallization from diethyl ether blue, moisture sensitive single crystals of [Co(NPEt₃) · (O₂C–CH₃)]₄ can be obtained, while colourless single crystals of [Cd(NPEt₃)(O₂C–CH₃)]₄ · 2 CH₂Cl₂ originate from dichloromethane solution. In vacuo the intercalary CH₂Cl₂ is released. The complexes are characterized by their IR spectra and by crystal structure analyses. In both complexes the metal atoms are associated via μ₃–N bridges of the (NPEt₃^–) groups to form heterocubanes. In the cobalt complex the acetato ligands are bonded in a semichelate fashion with a short Co–O and a long Co–O bond each (Co–O distances in average 199.5 and 257.4 pm). In the cadmium complex the acetato groups form almost symmetrical chelates (Cd–O distances in average 232.1 and 237.8 pm); this leads to a distorted trigonal‐bipyramidal arrangement at the cadmium atoms. [Co(NPEt₃)(O₂C–CH₃)]₄: Space group P 1, Z = 4, lattice dimensions at –60 °C: a = 1110.1(2), b = 2051.3(5), c = 2169.5(4) pm, α = 100.03(2)°, β = 103.404(15)°, γ = 97.63(2)°, R = 0.0480. [Cd(NPEt₃)(O₂C–CH₃)]₄ · 2 CH₂Cl₂: Space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1550.2(1), b = 2101.1(1), c = 1706.1(1) pm, β = 91.09(1)°, R = 0.0311.     

Binding H2, N2, H-, and BH3 to transition-metal sulfur sites: synthesis and properties of [RuL(PR3)(N2Me2S2)] Complexes (L=eta2-H2, H-, BH3; R=Cy, iPr)

The reactions of [Ru(N₂)(PR₃)(‘N₂Me₂S₂’)] [‘N₂Me₂S₂’=1,2‐ethanediamine‐N,N′‐dimethyl‐N,N′‐bis(2‐benzenethiolate)(2?)] [ 1 a (R=iPr), 1 b (R=Cy)] and [μ‐N₂{Ru(N₂)(PiPr₃)(‘N₂Me₂S₂’)}₂] ( 1 c ) with H₂, NaBH₄, and NBu₄BH₄, intended to reduce the N₂ ligands, led to substitution of N₂ and formation of the new complexes [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PR₃)(‘N₂Me₂S₂’)] [ 3 a (R=iPr), 3 b (R=Cy)], and [Ru(H)(PR₃)(‘N₂Me₂S₂’)]^? [ 4 a (R=iPr), 4 b (R=Cy)]. The BH₃ and hydride complexes 3 a , 3 b , 4 a , and 4 b were obtained subsequently by rational synthesis from 1 a or 1 b and BH₃?THF or LiBEt₃H. The primary step in all reactions probably is the dissociation of N₂ from the N₂ complexes to give coordinatively unsaturated [Ru(PR₃)(‘N₂Me₂S₂’)] fragments that add H₂, BH₄^?, BH₃, or H^?. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PiPr₃)(‘N₂Me₂S₂’)] ( 3 a ), [Li(THF)₂][Ru(H)(PiPr₃)(‘N₂Me₂S₂’)] ([Li(THF)₂]‐ 4 a ), and NBu₄[Ru(H)(PCy₃)(‘N₂Me₂S₂’)] (NBu₄‐ 4 b ) were determined by X‐ray crystal structure analysis. Measurements of the NMR relaxation time T₁ corroborated the η² bonding mode of the H₂ ligands in 2 a (T₁=35 ms) and 2 b (T₁=21 ms). The H,D coupling constants of the analogous HD complexes HD‐ 2 a (¹J(H,D)=26.0 Hz) and HD‐ 2 b (¹J(H,D)=25.9 Hz) enabled calculation of the H? D distances, which agreed with the values found by X‐ray crystal structure analysis ( 2 a : 92 pm (X‐ray) versus 98 pm (calculated), 2 b : 99 versus 98 pm). The BH₃ entities in 3 a and 3 b bind to one thiolate donor of the [Ru(PR₃)(‘N₂Me₂S₂’)] fragment and through a B‐H‐Ru bond to the Ru center. The hydride complex anions 4 a and 4 b are extremely Brønsted basic and are instantanously protonated to give the η²‐H₂ complexes 2 a and 2 b .     

Structure and Bonding of La2NiBi

La₂NiBi was synthesized by heating a cold pressed pellet of the elements in a sealed and evacuated silica tube at 1070 K. The structure was determined via powder and single crystal X‐ray diffraction. La₂NiBi crystallizes orthorhombically, in the space group Pnma: a = 838.88(6), b = 455.61(11), c = 1210.4(2) pm and V = 0.46261(14) nm³ (wR = 0.1002, 1001 F² values, 26 variables, Z = 4). La₂NiBi represents a higher congener of La₂NiSb and adopts a ternary ordered version of the Bi₃Ni structure type. Similar to La₂NiSb, the nickel atoms form infinite zigzag chains (259 pm Ni–Ni) with trigonal‐prismatic lanthanum coordination. One rectangular face of the lanthanum prism is capped by a bismuth atom (333.08–364.74 pm La–Bi, 281.18 pm Ni–Bi). These zigzag chains run along the b axis. DFT based band structure calculations and DOS representations suggest metallic behavior. This was confirmed via temperature dependent impedance spectroscopic measurements. A Seebeck coefficient of –10 μV · K^–1 in the temperature range up to 873 K substantiates this finding. Thermal analyses show that the compound is stable up to 873 K under inert gas conditions and degrades at higher temperatures. The magnetic measurements show almost no grain boundary nickel impurities characterizing La₂NiBi as a weak Pauli paramagnet.     

Platinum‐Indium Polyanions in the Structures of LaPtIn4 and LnPtIn3 (Ln = La,Ce, Pr,Nd, Sm) and Structure Refinement of Ce2Pt2In

The title compounds were prepared by reacting the elements in an arc‐melting furnace and subsequent annealing. The LaRuSn₃ type structure of the new compounds LnPtIn₃ (Ln = La, Ce, Pr, Nd, Sm) was refined from single crystal X‐ray data for LaPtIn₃: Pm3n, a = 980.4(2) pm, wR2 = 0.0271, 399 F² values, 15 variables. Striking structural motifs of LaPtIn₃ are condensed distorted trigonal [PtIn₆] prisms with Pt–In distances of 269 pm. The lanthanum atoms occupy large cavities within the polyhedral network. Besides Pt–In bonding In–In bonding also plays an important role in LaPtIn₃ with In–In distances of 299 and 327 pm. The La1 position is occupied only to 91%, resulting in a composition La_0.98(1)PtIn₃. The La1 atoms show an extremely large displacement parameter indicating a rattling of these atoms in the In₁₂ cages. The so far most indium rich compound in the ternary system lanthanum‐platinum‐indium is LaPtIn₄ which was characterized on the basis of Guinier powder data: YNiAl₄‐type, Cmcm, a = 455.1(2) pm, b = 1687.5(5) pm, and c = 738.3(2) pm. The platinum atoms in LaPtIn₄ center trigonal prisms with the composition [La₂In₄]. Together with the indium atoms the platinum atoms form a complex three‐dimensional [PtIn₄] polyanion in which the lanthanum atoms occupy large hexagonal tubes. The structure of Ce₂Pt₂In is confirmed: Mo₂FeB₂‐type, P4/mbm, a = 779.8(1) pm, c = 388.5(1) pm, wR2 = 0.0466, 433 F² values, 12 parameters. It is built up from CsCl and AlB₂ related slabs with the compositions CeIn and CePt₂, respectively. Chemical bonding in the [PtIn₃] and [PtIn₄] polyanions of LaPtIn₃ and LaPtIn₄ is discussed.     

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.     

Sulfate und Hydrogensulfate des Erbiums: Er(HSO4)3-I,Er(HSO4)3-II,Er(SO4)(HSO4) und Er2(SO4)3

Sulfates and Hydrogensulfates of Erbium: Er(HSO₄)₃-I, Er(HSO₄)₃-II, Er(SO₄)(HSO₄), and Er₂(SO₄)₃ Rod shaped light pink crystals of Er(HSO₄)₃-I (orthorhombic, Pbca, a = 1195.0(1) pm, b = 949.30(7) pm, c = 1644.3(1) pm) grow from a solution of Er₂(SO₄)₃ in conc. H₂SO₄ at 250 °C. From slightly diluted solutions (85%) which contain Na₂SO₄, brick shaped light pink crystals of Er(HSO₄)₃-II (monoclinic, P2₁/n, a = 520.00(5) pm, b = 1357.8(1) pm, c = 1233.4(1) pm, β = 92.13(1)°) were obtained at 250 °C and crystals of the same colour of Er(SO₄)(HSO₄) (monoclinic, P2₁/n, a = 545.62(6) pm, b = 1075.6(1) pm, c = 1053.1(1) pm, β = 104.58(1)°) at 60 °C. In both hydrogensulfates, Er³⁺ is surrounded by eight oxygen atoms. In Er(HSO₄)₃-I layers of HSO₄^– groups are connected only via hydrogen bridges, while Er(HSO₄)₃-II consists of a threedimensional polyhedra network. In the crystal structure of Er(SO₄)(HSO₄) Er³⁺ is sevenfold coordinated by oxygen atoms, which belong to four SO₄^2–- and three HSO₄^–-tetrahedra, respectively. The anhydrous sulfate, Er₂(SO₄)₃, cannot be prepared from H₂SO₄ solutions but crystallizes from a NaCl-melt. The coordination number of Er³⁺ in Er₂(SO₄)₃ (orthorhombic, Pbcn, a = 1270.9(1) pm, b = 913.01(7) pm, c = 921.67(7) pm) is six. The octahedral coordinationpolyhedra are connected via all vertices to the SO₄^2–-tetrahedra.     

Bildung und Struktur des [{η2‐tBu2P–P}Pt(PHtBu2)(PPh3)]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XX Formation and Structure of [{η²‐^tBu₂P–P}Pt(PH^tBu₂)(PPh₃)] [{η²‐^tBu₂P¹–P²}Pt(P³Ph₃)(P⁴Ph₃)] ( 2 ) reacts with ^tBu₂PH exchanging only the P³Ph₃ group to give [{η²‐^tBu₂P¹–P²}Pt(P³H^tBu₂)(P⁴Ph₃)] ( 1 ). The crystal stucture determination of 1 together with its ³¹P{¹H} NMR data allow for an unequivocal assignment of the coupling constants in related Pt complexes. 1 crystallizes in the triclinic space group P1 (no. 2) with a = 1030.33(15), b = 1244.46(19), c = 1604.1(3) pm, α = 86.565(17)°, β = 80.344(18)°, γ = 74.729(17)°.     

Structural Patterns and Dimensionality in Magnesium Borophosphates: The Crystal Structures of Mg2(H2O)[BP3O9(OH)4] and Mg(H2O)2[B2P2O8(OH)2]·H2O

Hydrothermal investigations in the system MgO/B₂O₃/P₂O₅(/H₂O) yielded two new magnesium borophosphates, Mg₂(H₂O)[BP₃O₉(OH)₄] and Mg(H₂O)₂[B₂P₂O₈(OH)₂]·H₂O. The crystal structures were solved by means of single crystal X‐ray diffraction. While the acentric crystal structure of Mg₂(H₂O)[BP₃O₉(OH)₄] (orthorhombic, P2₁2₁2₁ (No. 19), a = 709.44(5) pm, b = 859.70(4) pm, c = 1635.1(1) pm, V = 997.3(3) × 10⁶ pm³, Z = 4) contains 1D infinite chains of magnesium coordination octahedra interconnected by a borophosphate tetramer, Mg(H₂O)₂[B₂P₂O₈(OH)₂]·H₂O (monoclinic, P2₁/c (No. 14), a = 776.04(5) pm, b = 1464.26(9) pm, c = 824.10(4) pm, β = 90.25(1)°, V = 936.44(9) × 10⁶ pm³,Z = 4) represents the first layered borophosphate with 6³ net topology. The structures are discussed and classified in terms of structural systematics.     

The Monohydrate of Basic Mercuric Nitrate, [Hg(OH)](NO3)(H2O)

Colourless single crystals of [Hg(OH)](NO₃)(H₂O) were obtained by slow evaporation of an aqueous solution of Hg(NO₃)₂ and Bi(NO₃)₃. The crystal structure (orthorhombic, Pbca, Z = 8, a = 943.2(2), b = 697.6(1), c = 1349.0(2) pm, R₁(all) = 0.0780) contains [Hg(OH)] = …OH–Hg–OH–Hg… zig zag chains (O–Hg–O angle: 168°, Hg–O–Hg angle: 112°, Hg–OH distance: 212 pm) to which one water molecule is attached loosely. The [Hg(OH)](H₂O) chains are connected via bis‐monodentate‐bridging nitrate ions to corrugated layers that are stacked in the [001] direction. Hg²⁺ has an effective 2+2+2(+1) coordination.     

Synthesis and Characterization of Three Zinc Phosphonates Based on 5‐Phosphonoisophthalic Acid, (HO2C)2C6H3PO3H2

Three new Zn‐phosphonates based on 5‐phosphonoisophthalic acid, (HO₂C)₂C₆H₃PO₃H₂ (H₄L), [Zn₂(H₂O)(O₂C)₂C₆H₃PO₃] · H₂O ( 1 ), Zn₂(H₂O)₂(O₂C)₂C₆H₃PO₃ ( 2 ), and KZn[H(O₂C)₂C₆H₃PO₃] ( 3 ) have been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction ( 1 : triclinic, , a = 742.49(3) pm, b = 846.37(4) pm, c = 992.84(4) pm, α = 80.936(2)°, β = 81.574(2)°, γ = 73.139(3)°, V = 586.28(4) · 10⁶ pm³, R1 = 0.0583, wR2 = 0.1347 (for I > 2σ(I)); 2 : monoclinic, P2₁/m, a = 464.78(9) pm, b = 1329.2(3) pm, c = 974.5(3) pm, β = 95.80(3)°, V = 599.0(2) · 10⁶ pm³, R1 = 0.0395, wR2 = 0.1086 (for I > 2σ(I)); 3 : monoclinic, P2₁/c, a = 501.9(1) pm, b = 2489.9(5) pm, c = 946.2(5) pm, β = 105.38(3)°, V = 1140.0(7) · 10⁶ pm³, R1 = 0.0365, wR2 = 0.0848 (for I > 2σ(I))). The title compounds 1 and 2 have the same chemical composition but exhibit different structures and are therefore polymorphs. Thus, in compound 1 , isolated ZnO₄‐tetrahedra, and in 2 , infinite double‐chains of corner‐sharing ZnO₆ polyhedra are observed. In, KZn[H(O₂C)₂C₆H₃PO₃] ( 3 ) K⁺‐ions have been incorporated into the structure leading to the formation of a bimetallic inorganic‐organic hybrid compound.     

Two Alkali‐Metal Yttrium Tellurides: Single Crystals of Trigonal KYTe2 and Hexagonal RbYTe2

While attempting to synthesize the potassium and rubidium copper diyttrium tetratellurides KCuY₂Te₄ and RbCuY₂Te₄ in analogy to CsCuY₂Te₄ from 1:1:4‐molar mixtures of the elements (copper, yttrium and tellurium) with an excess of KBr or RbBr as flux and potassium or rubidium source, brown plate‐shaped crystals of KYTe₂ and RbYTe₂ with triangular cross‐section were obtained instead after 14 days at 900 °C in torch‐sealed evacuated silica tubes. These new ternary yttrium tellurides crystallize in the trigonal (KYTe₂) or hexagonal system (RbYTe₂) with space group R m (no. 166) or P6₃/mmc (no. 194), respectively. With unit cell dimensions of a = 439.51(2) pm, c = 2255.48(9) pm (c/a = 5.132) for KYTe₂ and a = 443.26(2) pm, c = 1729.15(7) pm (c/a = 3.901) for RbYTe₂, both crystal structures exhibit cadmium‐halide analogous layers spreading out parallel to the (001) planes, which are formed by edge‐condensation of the involved [YTe₆]^9– octahedra (d(Y³⁺–Te^2–) = 308–309 pm). Charge compensation and three‐dimensional linkage of these anionic layers are achieved by monovalent interlayer alkali‐metal cations residing in trigonal antiprismatic (K⁺ in α‐NaFeO₂‐type KYTe₂, d(K⁺–Te^2–) = 324 pm, 6×) or prismatic coordination (Rb⁺ in β‐RbScO₂‐type RbYTe₂, d(Rb⁺–Te^2–) = 365 pm, 6×) of six Te^2– ions each.     

Synthesis and Crystal Structure of Manganese(II) Bipyridine Carboxylato Complexes: [(bipy)2MnII(μ‐C2H5CO2)2MnII(bipy)2](ClO4)2 and [MnII(ClCH2CO2)(H2O)(bipy)2]ClO4 · H2O (bipy = 2,2′‐bipyridine)

Two manganese(II) bipyridine carboxylate complexes, [(bipy)₂Mn^II(μ‐C₂H₅CO₂)₂Mn^II(bipy)₂}₂](ClO₄)₂ ( 1 ), and [Mn^II(ClCH₂CO₂)(H₂O)(bipy)₂]ClO₄ · H₂O ( 2 ) were prepared. 1 crystallizes in the triclinic space group P 1 with a = 8.604(3), b = 12.062(3), c = 13.471(3) Å, α = 112.47(2), β = 93.86(2), γ = 92.87(3)°, V = 1211.1(6) ų and Z = 1. In the dimeric, cationic complex with a crystallographic center of symmetry two 2,2′‐bipyridine molecules chelate each manganese atom. These two metal fragments are then bridged by two propionato groups in a syn‐anti conformation. The Mn…Mn distance is 4.653 Å. 2 crystallizes in the monoclinic space group P2₁/c with a = 9.042(1), b = 13.891(1), c = 21.022(3) Å, β = 102.00(1)°, V = 2569.3(5) ų and Z = 4. 2  is a monomeric cationic complex in which two bipyridine ligands chelate the manganese atom in a cis fashion. A chloroacetato and an aqua ligand complete the six‐coordination. Only in 2 is the intermolecular packing controlled by weak π‐stacking besides C–H…π contacts between the bipyridine ligands.