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Title: Zirconium tetrachloride revisited

We present that zirconium tetrachloride, ZrCl 4, is a strategic material with wide-ranging applications. Until now, only one crystallographic study on ZrCl 4has been reported [Krebs (1970).Z. Anorg. Allg. Chem.378, 263–272] and that was more than 40 years ago. The compound used for the previous determination was prepared from ZrO 2 and Cl 2–CCl 4, and single-crystal X-ray diffraction (SCXRD) studies on ZrCl 4 obtained from Zr metal have not yet been reported. In this context, we prepared ZrCl 4 from the reaction of Zr metal and Cl 2 gas in a sealed tube and investigated its structure at 100, 150, 200, 250, and 300 K. At 300 K, the SCXRD analysis indicates that ZrCl 4 crystallizes in the orthorhombic space group Pca2 1 [a= 6.262 (9),b= 7.402 (11),c= 12.039 (17) Å, andV= 558.0 (14) Å 3] and consists of infinite zigzag chains of edge-sharing ZrCl 6 octahedra. This chain motif is similar to that observed previously in ZrCl 4, but the structural parameters and space group differ. Finally, in the temperature range 100–300 K, no phase transformation was identified, while elongation of intra-chain Zr...Zr [3.950 (1) Å at 100 K and 3.968 (5) Å at 300 K] and inter-chainmore » Cl...Cl [3.630 (3) Å at 100 K and 3.687 (9) Å at 300 K] distances occurred.« less
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  1. Univ. of Nevada, Las Vegas, NV (United States). Department of Chemistry and Biochemistry
  2. Univ. of Nevada, Las Vegas, NV (United States). Department of Physics and Astronomy
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 2053-2296; ACSCGG; 658195
Grant/Contract Number:
AC04-94AL85000; NE0008449; NA0003525
Accepted Manuscript
Journal Name:
Acta Crystallographica. Section C, Structural Chemistry (Online)
Additional Journal Information:
Journal Name: Acta Crystallographica. Section C, Structural Chemistry (Online); Journal Volume: 74; Journal Issue: 3; Journal ID: ISSN 2053-2296
International Union of Crystallography
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; zirconium tetra­chloride; crystal structure; chain motif; temperature study
OSTI Identifier: