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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
Authors:
 [1] ;  [1] ; ORCiD logo [2] ;  [3] ;  [1]
  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):
SAND-2017-11627J
Journal ID: ISSN 2053-2296; ACSCGG; 658195
Grant/Contract Number:
AC04-94AL85000; NE0008449; NA0003525
Type:
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
Publisher:
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
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; zirconium tetra­chloride; crystal structure; chain motif; temperature study
OSTI Identifier:
1429669

Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, and Poineau, Frederic. Zirconium tetrachloride revisited. United States: N. p., Web. doi:10.1107/S205322961800219X.
Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, & Poineau, Frederic. Zirconium tetrachloride revisited. United States. doi:10.1107/S205322961800219X.
Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, and Poineau, Frederic. 2018. "Zirconium tetrachloride revisited". United States. doi:10.1107/S205322961800219X.
@article{osti_1429669,
title = {Zirconium tetrachloride revisited},
author = {Borjas Nevarez, Rosendo and Balasekaran, Samundeeswari Mariappan and Kim, Eunja and Weck, Philippe and Poineau, Frederic},
abstractNote = {We present that zirconium tetrachloride, ZrCl4, is a strategic material with wide-ranging applications. Until now, only one crystallographic study on ZrCl4has 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 ZrO2 and Cl2–CCl4, and single-crystal X-ray diffraction (SCXRD) studies on ZrCl4 obtained from Zr metal have not yet been reported. In this context, we prepared ZrCl4 from the reaction of Zr metal and Cl2 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 ZrCl4 crystallizes in the orthorhombic space group Pca21 [a= 6.262 (9),b= 7.402 (11),c= 12.039 (17) Å, andV= 558.0 (14) Å3] and consists of infinite zigzag chains of edge-sharing ZrCl6 octahedra. This chain motif is similar to that observed previously in ZrCl4, 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-chain Cl...Cl [3.630 (3) Å at 100 K and 3.687 (9) Å at 300 K] distances occurred.},
doi = {10.1107/S205322961800219X},
journal = {Acta Crystallographica. Section C, Structural Chemistry (Online)},
number = 3,
volume = 74,
place = {United States},
year = {2018},
month = {2}
}