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The halogenido stannates(II) [BMIm][Sn3Cl7] and [BMIm][Sn4Br9] are obtained by ionic‐liquid‐based synthesis with SnX2 and [BMIm]X (X=Cl, Br; [BMIm]=1‐butyl‐3‐methylimidazolium) near room temperature (45–50 °C). Both form colorless, moisture‐sensitive crystals and exhibit layered anionic networks. [BMIm][Sn3Cl7] contains "horseshoe"‐like ∞1(SnCl1/1Cl2/2) chains that are linked via [SnCl3]− anions to ∞2[Sn3Cl7]− zigzag‐planes. [BMIm][Sn4Br9] contains a complex ∞2[Sn4Br9]− network with altogether four different crystallographic Sn2+ sites and different coordination. For comparison with these complex halogenido stannates(II), PbCl2/PbBr2 are reacted with similar conditions, which, however, only results in [BMIm][PbCl3] containing ∞1[PbCl3]− chains. Beside the crystal structures, the thermal and optical properties are examined and feature certain emission of visible light for all title compounds at room temperature. Whereas the quantum yields of [BMIm][Sn4Br9] (3 %) and [BMIm][PbCl3] (21 %) are low, [BMIm][Sn3Cl7] shows surprisingly efficient photoluminescence with a quantum yield of 46 %. [ABSTRACT FROM AUTHOR]

The phosphorus interhalides [PBr4][IBr2] (1) and [PBr4]2[I5Br7] (2) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PBr4][IBr2] (1) consists of tetrahedral [PBr4]+ cations and linear [IBr2]− anions. [PBr4]2[I5Br7] (2) also contains [PBr4]+ cations as well as the iodine bromide anion [I5Br7]2−. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br2) of 96.8 wt% below 300 °C. For the ternary system P–Br–I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy. [ABSTRACT FROM AUTHOR]

[BMIm]2[{PbMn(CO)5)}6I8] (BMIm: 1-butyl-3-methylimidazolium) is obtained by ionic liquid mediated reaction of PbI2 and Mn2(CO)10. Central is a cubelike (Pb6I8) unit containing a nonfilled Pb6 octahedron. Each Pb of this (Pb6I8) unit is terminated on its outside by Mn(CO)5, exhibiting Pb--Mn metal-to-metal bonding (280 pm). Structurally, the (Pb6I8) unit is similar to the well-known octahedral (M6Xn) cluster-type family (M = Zr, Nb, Ta, Mo, W; X = Cl, Br, I). In contrast to most similar cluster compounds, such as W6Br12 ([W6Br8]Br2/1Br4/2, according to Niggli notation) or the carbonyl cluster [Sn6{Cr(CO5)6}]2-, however, the nonfilled central Pb6 octahedron in [{PbMn(CO)5)}6I8]2- does not exhibit any metal-to-metal bonding. Structure and bonding of the title compound are validated by single-crystal structure analysis, energy-dispersive X-ray analysis (EDX), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations. Based on the isolobal principle, electronegativity considerations, bond lengths, and DFT calculations including Mulliken population analysis and natural population analysis (NPA), in sum, the charge distribution of Pb is best reflected by an oxidation state of +1. [ABSTRACT FROM AUTHOR]

A novel modification of potassium nitrate is obtained subsequent to solvothermal reaction and crystallization at reduced temperature from diethylformamid (DEF) as solvent. δ-KNO3 crystallizes with the monoclinic space group P21/ c. Most intriguing is the coordination number of potassium and oxygen as expressed by the Niggli notation δ-K8/8[NO4/4O4/2] that differs from the known modifications of potassium nitrate (α-K9/9[NO9/3], β-K9/9[NO9/3], γ-K9/9[NO9/3]). Moreover, the stacking of the NO3- anions differentiates from the known KNO3 modifications. As only few crystals were obtained, the new modification is characterized by single-crystal structure analysis as well as by Fourier-transformed infrared spectroscopy. The latter reliably points to the presence of nitrate and shows a ν(N-O) vibration centered at 1384 cm-1, but with significantly different shape and band width as compared to α-K9/9[NO9/3] as a reference. [ABSTRACT FROM AUTHOR]

By reacting Mn2(CO)10 and TeI4 in the ionic liquid[BMIm][OTf] (1-butyl-3-methylimidazolium trifluromethanesulfonate), brick-red crystals of [BMIm][(Te2)3{Mn(CO)3}2{Mn(CO)4}3]are obtained. The title compound contains the carbonyl anion[(Te2)3{Mn(CO)3}2{Mn(CO)4}3]-. Herein, three formal Te22- units and two formal Mn(CO)3+ fragments establish a distorted heterocubane-like Te6Mn2 structure. Three edges of this heterocubane are furthermore capped by Mn(CO)4+ fragments. The resulting Te6Mn5 building unit, moreover, looks very similar to the P113- anion - the so-called ufosane. The mean distances Te-Te and Te-Mn are observed with 277.6 and 264.7 pm, respectively. In addition to single-crystal structure analysis, the title compound is characterized by infrared spectroscopy (FT-IR), thermogravimetry (TG) and energy-dispersive X-ray (EDX) analysis. [ABSTRACT FROM AUTHOR]

During outstanding research in the late 1950s in Munich, which led to the development of the Wacker process for converting ethene into acetaldehyde by catalysis of PdCl2, black insoluble nitrosyl‐palladium chloride (PdCl(NO)) was obtained. More than sixty years after its first synthesis, its crystal structure was now determined by X‐ray diffraction. PdCl(NO) (mP16, P21/c, a=10.2684(5), b=4.0737(2), c=7.8456(4) Å, β=111.125(1)°, wR2=0.0572) consists of distorted Pd4Cl4 octagons in chair arrangement to which four distorted Pd2Cl2 squares are annulated on every second edge. In this arrangement each of the two Pd atoms of the squares are connected to one N−O group, bonded alternatively up and down to the Pd atoms with a Pd−N−O angle of 129°. Such a square has the composition of the dimer which was found in the mass spectrum at 343.6 m/e. The octagons with four squares are interconnected to corrugated layers in the b‐c‐plane as a two‐dimensional polymer. [ABSTRACT FROM AUTHOR]

The phosphorus interhalides [PBr4][IBr2] (1) and [PBr4]2[I5Br7] (2) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PBr4][IBr2] (1) consists of tetrahedral [PBr4]+ cations and linear [IBr2]− anions. [PBr4]2[I5Br7] (2) also contains [PBr4]+ cations as well as the iodine bromide anion [I5Br7]2−. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br2) of 96.8 wt% below 300 °C. For the ternary system P–Br–I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy. [ABSTRACT FROM AUTHOR]