No solid solution compounds in between the binaries: syntheses and crystal structures of Nb(Br0.62(4)Cl0.38(4))2Cl2 and NbI2Cl2
-
Olaf Reckeweg
and
Thomas Schleid
Abstract
The anion-mixed niobium tetrahalides Nb(Br0.62(4)Cl0.38(4))2Cl2 and NbI2Cl2 were obtained by heating NbBr5 with NbCl5 and NbI5 with NbCl5, respectively, in equimolar ratios with niobium metal in evacuated, torch-sealed silica ampoules at 720 K for 3 days. The orthorhombic title compounds form as very brittle black needles and were characterized by single-crystal X-ray diffraction [space group: Immm, Z=4; a=704.27(6), b=824.13(7), c=929.64(8) pm for Nb(Br0.62(4)Cl0.38(4))2Cl2 and a=753.76(6), b=829.38(7) and c=983.41(8) pm for NbI2Cl2]. Surprisingly enough, these mixed-anionic halides are not isostructural with either NbCl4, NbBr4 or NbI4, but crystallize isotypically with TaI2Cl2, thus being examples for differential site occupancy stabilized materials. Structural features of other niobium(IV) halides are compiled and compared to those of Nb(Br0.62(4)Cl0.38(4))2Cl2 and NbI2Cl2. Except for NbF4, they all exhibit chains of trans-edge connected [NbX6]2− octahedra, which allow Peierls distortions to form Nb–Nb single bonds. The packing of these chains differ, however, depending on the actual halide or mixed-halide combination.
Acknowledgments
We thank Prof. Dr. H.-Jürgen Meyer (Institut für Anorganische Chemie, Universität Tübingen) for the permission to use the data for NbI2Cl2 acquired in the frame of the research work performed for the doctoral thesis of O. R.
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Articles in the same Issue
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- Gérard Demazeau, 07.06.1943–03.11.2017
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- Erratum
- Berichtigung: Phosphanchalkogenide und ihre Metallkomplexe. II. Komplexe einiger Gold(I)-Halogenide mit Diphosphanmonochalkogeniden
Articles in the same Issue
- Frontmatter
- In this Issue
- Obituary
- Gérard Demazeau, 07.06.1943–03.11.2017
- Synthesis and reactivity of β-stannylated phenylalanines
- Synthesis of 2,4-diamino-6-aryl-5-pyrimidinecarbonitrile promoted by amino-functionalized CoFe2O4@SiO2 nanoparticles under conventional heating, microwave and ultrasound irradiations
- Heterocycles [h]-fused onto 4-oxoquinoline-3-carboxylic acid. Part XII: synthesis of 5-fluoro-7-oxodihydo[1,3,4]thiadiazino [5,6-h]quinoline-8-carboxylic acid and ester
- No solid solution compounds in between the binaries: syntheses and crystal structures of Nb(Br0.62(4)Cl0.38(4))2Cl2 and NbI2Cl2
- Rare earth-rich cadmium compounds RE10TCd3 (RE=Y, Tb, Dy, Ho, Er, Tm, Lu; T=Rh, Pd, Ir, Pt) with an ordered Co2Al5-type structure
- Aminkomplexe des Goldes, Teil 9: Gold(I)-halogenid-Komplexe mit primären und azyklischen sekundären Aminen und ihre Oxidation zu Gold(III)-Derivaten
- Erratum
- Berichtigung: Phosphanchalkogenide und ihre Metallkomplexe. II. Komplexe einiger Gold(I)-Halogenide mit Diphosphanmonochalkogeniden
