The First Aqua Pentafluoro Manganates(III) – Syntheses and Structures

For the first time aqua pentafluoro manganate(III) compounds with different organic N-cations have been prepared and their crystal structures have been determined: N,N′-DMenH₂[MnF₅(H₂O)] · H₂O 1 (N,N′-DMen = N,N′-Dimethylethylenediamine), space group P2₁/c, a = 916.0, b = 1004.8, c = 1247.9 pm, β = 106.03°, R = 0.035; NMpipzH₂ · [MnF₅(H₂O)] · H₂O 2 (NMpipz = N-Methylpiperazine), space group P2₁/n, a = 757.7, b = 1261.9, c = 1197.1 pm, β = 105.09°, R = 0.027; N,N′-DMpipzH₂[MnF₅(H₂O)] · 2 HF 3 (N,N′-DMpipz = N,N′-Dimethylpiperazine), space group P1, a = 677.1, b = 863.9, c = 1187.7 pm, α = 79.18°, β = 81.63° γ = 67.62°, R = 0.026; and N,N-DMenH₂[MnF₅(H₂O)] · 1/2 HF 4 (N,N-DMen = N,N-Dimethylethylenediamine), space group P1, a = 859.3, b = 1086.5, c = 1092.0 pm, α = 86.96°, β = 78.52° γ = 89.01°, R = 0.035. In all compounds the [MnF₅(H₂O)]^2– octahedra are connected via H-bonds forming 3 D and 2 D network arrangements. The anions are strongly elongated by the Jahn-Teller effect. The FTIR spectra are presented.     

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).     

IV Dodekaedrische [Mo(CN)8]‐Koordination in den cyanoverbrückten Cobalt‐ und Nickel‐Amminkomplexen MII2(NH3)8[Mo(CN)8] · 1,5 H2O (MII = Co,Ni) und Ni2(NH3)9[Mo(CN)8] · 2 H2O

Crystal Structures of Octacyanomolybdates(IV). IV Dodecahedral [Mo(CN)₈] Coordination of the Cyano‐Bridged Cobalt and Nickel Ammin Complexes M^II₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (M^II = Co, Ni) and Ni₂(NH₃)₉[Mo(CN)₈] · 2 H₂O At single crystals of the hydrated cyano complexes Co₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (a = 910.0(4), b = 1671(2), c = 1501(1) pm, β = 93.76(6)°) and Ni₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (a = 899.9(9), b = 1654.7(4), c = 1488(1) pm, β = 94.01°), isostructurally crystallizing in space group P2₁/c, Z = 4, and of trigonal Ni₂(NH₃)₉[Mo(CN)₈] · 2 H₂O (a = 955.1(1), c = 2326.7(7) pm, P3₁, Z = 3), X‐ray structure determinations were performed at 168 resp. 153 K. The [Mo(CN)₈]^4– groups of the three compounds, prepared at about 275 K and easily decomposing, show but slightly distorted dodecahedral coordination (mean distances Mo–C: 216.3, 215.4 and 216.1 pm). Within the monoclinic complexes the anions twodimensionally form cyano bridges to the ammin cations [M(NH₃)₄]²⁺ and are connected with the resulting [MN₆] octahedra (Co–N: 215.1 pm, Ni–N: 209.8 pm) into strongly puckered layers. The trigonal complex exhibits a chain structure, as one [Ni(NH₃)₅]²⁺ cation is only bound as terminal octahedron (Ni–N: 212.0 pm). Details and the influence of hydrogen bridges are discussed.     

Jahn‐Teller‐Ordnung in pipzH2[Mn2F8], einem Fluoromanganat(III) mit neuer Schichtstruktur

Jahn‐Teller Ordering in pipzH₂[Mn₂F₈], a Fluoromanganate(III) with a New Layer Structure From a solution of (pipzH₂)[MnF₂(HPO₄)(H₂O)]·(H₂PO₄) in concentrated hydrofluoric acid the title compound could be crystallized and was characterized by X‐ray crystallography: monoclinic, space group P2₁/n, Z = 8, a = 13.275(1), 10.400(1), c = 14.928(1) Å, β = 112.337(8), R = 0.0265. The structure shows a new type of anionic layers [Mn₂F₈] built of dimers of edge‐sharing [MnF₆] octahedra linked via common vertices, alternating with layers of piperazinium(2+) cations. A dense network of hydrogen bonds N–H···F achieves a strong 3D interconnection. Strong elongation of the [MnF₆] octahedra is observed due to the Jahn‐Teller effect.The long axes show parallel (ferrodistortive) orientation within the dimers, but the ordering between the dimers is antiferrodistorive. A possible mechanism of formation is discussed on the basis of precursor structures.     

Synthese,Kristallstruktur und FTIR-Spektren der Oxoniumfluorometallate DienH2(H3O)[AlF6] und DienH2(H3O)[FeF6]

Synthesis, Crystal Structure, and FTIR Spectra of the Oxoniumfluorometallates DienH₂(H₃O)[AlF₆] and DienH₂(H₃O)[FeF₆] Single crystals of the compounds DienH₂(H₃O)[AlF₆] and DienH₂(H₃O)[FeF₆] (Dien = Diethylenediamine or Piperazine) were obtained from aqueous HF solution. The compounds are isotypic and crystallize in the monoclinic space group P2₁/c, Z = 8 with the unit cell parameters a = 1333.7(3), b = 1261.8(3), c = 1234.5(2) pm, β = 115.79(3)° (Al compound) and a = 1354.0(3), b = 1267.5(3), c = 1255.9(3) pm, β = 115.48(3)° (Fe compound). The crystal structure consists of isolated [MF₆]^3? anions, H₃O⁺ and DienH₂²⁺ cations. The [MF₆]^3? octahedra are connected via very strong O? H … F and N? H … F-bridges forming a three dimensional network structure. This strong hydrogen bonding was confirmed by the FTIR spectra.     

Doppelkettenstruktur von (pipzH2)[MnF2(HPO4)(H2O)](H2PO4)

By adding piperazine to a hydrofluoric and phosphoric acid solution of Manganese(III) fluoride, the fluoride phosphate (pipzH₂)[MnF₂(HPO₄)(H₂O)](H₂PO₄) can be crystallized. Its structure is built by piperazinium(2+) cations, (H₂PO₄)^? anions, and an anionic double‐chain of [HPO₄] tetrahedra and [MnO₃F₂(H₂O)] octahedra. The structure is triclinic, space group P , Z = 2, a = 622.97(4), b = 923.46(6), c = 1183.62(7) pm, α = 98.343(6)°, β = 100.747(7)°, γ = 107.642(5)°, R = 0.0289. It is worth noting that a ferrodistortive Jahn‐Teller order is observed with [MnO₃F₂(H₂O)] octahedra strongly elongated along the F–Mn–OH₂ axes perpendicular to the chain plane. The structure is stabilized by very strong hydrogen bonds.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

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.     

Oxyfluorinated compounds with an open structure XVI. Synthesis,structure determination and magnetic properties of Fe4F3(PO4)(HPO4)4(H2O)4(N2C3H12) [ULM-15]

Fe₄F₃(PO₄)(HPO₄)₄(H₂O)₄(N₂C₃H₁₂) (labelled ULM-15) was prepared hydrothermally (7 days, 453 K, autogenous pressure) in the presence of 1,3-diaminopropane as organic template. Its structure was determined by single crystal X-ray diffraction. ULM-15 is monoclinic (Space group C2/c (no 15)) with lattice parameters a = 24.176(1) , b = 14.558(1) , c = 7.186(1) , β = 102.3(1)°, V = 2470.8(3) ³, Z = 4. Its three-dimensional framework is constituted from corner-sharing FeX₆ (X = O, F, H₂O) octahedra and tetrahedral PO₄ and HPO₄ groups. The structure presents trans-chains of FeO₄F₂ octahedra related to ferric dimers [Fe₂O₈F₂(H₂O)₂] by tetrahedral units. They delimit 16-membered rings channels along [001] in which the diprotonated amines are inserted. ULM-15 shows 3D antiferromagnetic behaviour below T_N ≈ 22 K.     

Molekül- und Kristallstruktur von Ytterbium(III)-triaqua-trinitrat,Yb(H2O)3(NO3)3

Molecular and Crystal Structure of Ytterbium(III)-triaqua-trinitrate, Yb(H₂O)₃(NO₃)₃ Yb(H₂O)₃(NO₃)₃ crystallizes from a concentrated solution of Yb₂O₃ in nitric acid in a vacuum desiccator at ambient temperature as colourless single crystals. The crystal structure was determined from single crystal four-circle diffractometer data (R3 , Z = 6, a = 1175.5(1), c = 1117.7(2) pm, V_m = 134.25 cm³/mol, R = 3.0%, R_w = 2.9%). The structure may be viewed at as a heavily compressed packing of [Yb(H₂O)₃(NO₃)₃] molecules. Yb³⁺ is coordinated by three bidentate nitrate ligands and three water molecules so that a tricapped trigonal prism (C.N. 9) of oxygen atoms results as the coordination polyhedron.     

Synthesis,Structure, and Polarized Optical Spectra of a New Fluoromanganate(III): [(H3N(CH2)2)2NH2]2[MnF5(H2O)]3

The synthesis and crystal structure of a new fluoromanganate(III), [(H₃N(CH₂)₂)₂NH₂]₂[MnF₅(H₂O)]₃, is reported. The unit cell is unusually large: monoclinic, P2₁/c (no. 14), a = 41.0512(13) Å; b = 9.6469(4) Å; c = 12.8021(7) Å; β = 91.927(4)°; Z = 8, R = 0.0627 and wR₂ = 0.1347. The [MnF₅(H₂O)]^2– anions are octahedral with a strong distortion along the F–Mn OH₂ axes due to the Jahn-Teller effect. A very rich intermolecular hydrogen bond framework is present, leading to chains of octahedra linked by double-hydrogen bonds. The polarized optical spectra on single crystals are explained in terms of the intraconfigurational d⁴ transitions split by a ligand field of C_4v symmetry.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Peroxofluorokomplexe der Übergangsmetalle. III,Darstellung, Kristallstruktur und Schwingungsspektren von K6Ta3(O2)3OF13 · H2O mit einem μ-Oxo-diperoxo-octafluoroditantalat(V)-Anion

Transition Metal Peroxofluoro Complexes. III. Preparation, Crystal Structure, and Vibrational Spectra of K₆Ta₃(O₂)₃OF₁₃ · H₂O Containing a m?-Oxo-diperoxo-octafluoroditantalate(V) Anion K₆Ta₃(O₂)₃OF₁₃ · H₂O has been prepared from solution and his crystal structure was determined by X-ray single crystal investigation: Space group Pnma, lattice constants a = 1 653.6 pm, b = 883.5 pm, c = 1 365.8 pm, Z = 4, R = 0.033. The compound yields [Ta(O₂)F₅]^2? groups as well as m?-oxo-bridged [Ta₂O(O₂)₂F₈]^4? anions with very diffrent O? O distances within the peroxo groups (139 pm vs. 164 and 175 pm) correlating well with the i.r. and Raman spectra. The different bonding in connection with an oxo-bridge is discussed.     

Variation of 2 D Hydrogen Bond Topology in Diaqua-tetrafluoromanganates(III): 2-picoH[MnF4(H2O)2], TMEDAH2[MnF4(H2O)2]2, and TMBDAH2[MnF4(H2O)2]2

The crystal structures of three new diaqua-tetrafluoro-manganate(III) compounds with different organic N-cations have been determined: 2-picoH[MnF₄(H₂O)₂] 1 (2-pico = 2-methyl-pyridine), space group P2₁/c, a = 9.439, b = 13.662, c = 7.641 Å, β = 91.31°; R = 0.059; TMEDAH₂[MnF₄(H₂O)₂]₂ 2 (TMEDA = N,N,N′,N′-tetramethyl ethane diamine), space group P2₁/c, a = 5.421, b = 15.970, c = 9.677 Å, β = 96.37°, R = 0.031, and TMBDAH₂[MnF₄(H₂O)₂]₂ 3 (TMBDA = N,N,N′,N′-tetramethyl-1,4-butane-diamine), space group P2₁/n, a = 12.631, b = 5.577, c = 12.976 Å, β = 98.10°, R = 0.040. All three compounds show 2 D H-bonding networks of [MnF₄(H₂O)₂]^– anions separated by the organic cations. However, the topology of the anionic H-bonding nets is different for each compound. The anions are strongly elongated by the Jahn-Teller effect and are arranged in a ferrodistortive way in compounds 1 and 2 , whereas in compound 3 the arrangement is described as in a herringbone-like antiferrodistortive variant.     

Coordination Chemistry of [Nb2(S2)2]4+ Clusters: Preparation and Crystal Structures of K4[Nb2(S2)2(C2O4)4] · 6 H2O and (NH4)6[Nb2(S2)2(C2O4)4](C2O4)

Bis(disulfido)bridged Nb^IV cluster oxalate complexes [Nb₂(S₂)₂(C₂O₄)₄]^4– were prepared by ligand substitution reaction from the aqua ion [Nb₂(μ‐S₂)₂(H₂O)₈]⁴⁺ and isolated as K₄[Nb₂(S₂)₂(C₂O₄)₄] · 6 H₂O ( 1 ), (NH₄)₆[Nb₂(S₂)₂(C₂O₄)₄](C₂O₄) ( 2 ) and Cs₄[Nb₂(S₂)₂(C₂O₄)₄] · 4 H₂O ( 3 ). The crystal structures of 1 and 2 were determined. The crystals of 1 belong to the space group P1, a = 720.94(7) pm, b = 983.64(10) pm, c = 1071.45(10) pm, α = 109.812(1)°, β = 91.586(2)°, γ = 105.257(2)°. The crystals of 2 are monoclinic, space group C2/c, a = 1567.9(2) pm, b = 1906.6(3) pm, c = 3000.9(4) pm, β = 95.502(2)°. The packing in 2 shows alternating layers of cluster anions and of ammonium/uncoordinated oxalates perpendicular to the [1 0 1] direction. Vibration spectra, electrochemistry and thermogravimetric properties of the complexes are also discussed.     

(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.     

Über das Tri(phosphorano)borazinium-Monokation [H3B3(NPEt3)3Cl2]+. Kristallstrukturen von Me3SiNPR3 · BH3 (R = Et,Ph), [H3B3(NPEt3)3Cl1,85Br0,15]Br · CCl4 und des Hydrolyseproduktes NH4[B5O6(OH)4] · 2 H2O

On the Tri(phosphorano)borazinium Monocation [H₃B₃(NPEt₃)₃Cl₂]⁺. Crystal Structures of Me₃SiNPR₃ · BH₃ (R = Et, Ph), [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄, and of the Product of Hydrolysis NH₄[B₅O₆(OH)₄] · 2 H₂O The crystal structures of the donor-acceptor complexes of the silylated phosphanimines with borane which are suitable as educts for the synthesis of tri(phosphorano)borazinium ions, Me₃SiNPR₃ · BH₃ (R = Et, Ph), are described. After addition of CCl₄ the reaction of Me₃SiNPEt₃ with HBBr₂ · SMe₂ in CH₂Cl₂ leads to the tri(phosphorano)borazinium monocation [H₃B₃(NPEt₃)₃Cl₂]⁺, which is characterized crystallographically as [H₃B₃ · (NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄. It complements the series of the tri(phosphorano) cations [H₃B₃(NPEt₃)₃]³⁺ and [H₄B₃(NPEt₃)₃]²⁺ by the monocation. NH₄[B₅O₆(OH)₄] · 2 H₂O can be isolated as product of hydrolysis of the tri(phosphorano)borazinium ions; its crystal structure is redetermined, because in the literature it is based on a wrong space group. Me₃SiNPEt₃ · BH₃ ( 1 ): Space group P1, Z = 4, lattice dimensions at 213 K: a = 710.9(4), b = 1465.9(3), c = 1536.0(3) pm, α = 107.05°, β = 99.40(3)°, γ = 97.41(3)°; R = 0.0740. Me₃SiNPPh₃ · BH₃ ( 2 ): Space group P2₁/c, Z = 4, lattice dimensions at 203 K: a = 934.6(1), b = 1398.6(1), c = 1626.1(1) pm, β = 103.52(1)°; R = 0.0556. [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄ ( 3 ): Space group P2₁/n, Z = 4, lattice dimensions at 223 K: a = 1237.9(3), b = 1214.1(3), c = 2402.4(4) pm, β = 93.52(1)°. 3 holds a B₃N₃ six-membered ring in a distorted boat conformation. NH₄[B₅O₆(OH)₄] · 2 H₂O ( 4 ): Space group Aba2, Z = 4, lattice dimensions at 273 K: a = 1131.3(1), b = 1103.0(1), c = 923.0(1) pm; R = 0.0564.     

Oxo-Phosphaniminato-Komplexe von Molybdän und Wolfram. Die Kristallstrukturen von [Mo(O)2(NPPh3)2] und [WO(NPPh3)3]2[W6O19]

Oxo-phosphoraneiminato Complexes of Molybdenum and Tungsten. Crystal Structures of [Mo(O)₂(NPPh₃)₂] and [WO(NPPh₃)₃]₂[W₆O₁₉] The dioxo-phosphoraneiminato complexes [Mo(O)₂(NPPh₃)₂] ( 1 ) and [W(O)₂(NPPh₃)₂] ( 2 ) originate from hydrolysis of the nitrido complexes [MN(NPPh₃)₃] (M = Mo, W). They form colourless crystals, which are characterized by IR and NMR spectroscopy as well as by mass spectrometry. According to the crystal structure analysis of 1 (space group Fdd2, Z = 8; lattice dimensions at –83 °C: a = 1953.3(1), b = 3275.8(3), c = 953.4(1) pm) there are monomeric molecules with tetrahedrally coordinated molybdenum atoms. The distances MoO of 171.2 pm and MoN of 185.9 pm correspond to double bonds. In dichloromethane solution 2 undergoes further hydrolysis with colourless crystals of [WO(NPPh₃)₃]₂[W₆O₁₉] ( 3 ) originating, which are characterized crystallographically (space group Pbcn, Z = 4; lattice dimensions at –50 °C: a = 3225.1(6), b = 1803.6(3), c = 1811.9(3) pm). 3 consists of cations [WO(NPPh₃)₃]⁺ with tetrahedrally coordinated tungsten atoms and of the known [W₆O₁₉]^2– anions. The tungsten atoms of the cations show distances WO of 171.8 pm and WN of 182 pm which correspond to double bonds as in 1 .     

Hydrothermal Synthesis and Crystal Structure of CaIn2(PO4)2(HPO4): An octahedral-tetrahedral framework ternary calcium indium(III) phosphate

The new ternary calcium indium(III) phosphate CaIn₂(PO₄)₂(HPO₄) with mixed octahedral-tetrahedral framework was synthesized through hydrothermal reaction of stoichiometric amounts of CaO and InCl₃ with excess of H₃PO₄ and H₂O at pH = 1. Single crystal x-ray diffraction studies show the compound to crystallize in monoclinic symmetry, space group P2₁/n (#14) with a = 657.08(6), b = 2023.7(2), c = 665.72(7) pm, β = 91.20(1)°, Z = 4 and R = 0.043. The framework is built up of dimers of edge-sharing InO₆ octahedra forming In₂O₁₀ units sharing all their OXO ligands with PO₄ tetrahedra, and HPO₄ groups.     

Kristallstruktur von Kaliumtriflat‐Butyrolacton, [K3(O3SCF3)3(O2C4H6)2]

Crystal Structure of Potassium Triflate‐butyrolactone, [K₃(O₃SCF₃)₃(O₂C₄H₆)₂] Single Crystals of [K₃(O₃SCF₃)₃(O₂C₄H₆)₂] ( 1 ) have been obtained as a by‐product from the reaction of KNPPh₃ with Yb(O₃SCF₃)₃ in THF with subsequent addition of butyrolactone. The structure of 1 consists of three symmetry‐independent potassium ions which are linked by the oxygen atoms of the triflate ions and the butyrolactone molecules to give a supramolecular structure with layers normal to the crystallographic b‐axis. The carbonyl oxygen atoms of both butyrolactone molecules show a μ₃‐bridging function between three K⁺ ions, one of them is, in addition, coordinated by the ring O‐atom in a chelate manner. 1 : Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 1155.0(1), b = 1537.2(1), c = 1531.1(1) pm, β = 100.623(7)°, R = 0.0484.