Zirconium tetrachloride revisited

doi:10.1107/S205322961800219X

Title: Zirconium tetrachloride revisited

Abstract

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 300more » K] distances occurred.« less

Authors:

Borjas Nevarez, Rosendo ^[1]; Balasekaran, Samundeeswari Mariappan ^[1];

^[2]; Weck, Philippe ^[3]; Poineau, Frederic ^[1]

Univ. of Nevada, Las Vegas, NV (United States). Department of Chemistry and Biochemistry
Univ. of Nevada, Las Vegas, NV (United States). Department of Physics and Astronomy
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Publication Date:: 2018-02-19

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)

OSTI Identifier:: 1429669

Report Number(s):: SAND-2017-11627J
Journal ID: ISSN 2053-2296; ACSCGG; 658195

Grant/Contract Number:: AC04-94AL85000; NE0008449; NA0003525

Resource 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

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

Citation Formats


                    Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, and Poineau, Frederic. Zirconium tetrachloride revisited.  United States: N. p., 2018. 
        Web.  doi:10.1107/S205322961800219X.

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                    Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, & Poineau, Frederic. Zirconium tetrachloride revisited.  United States.  doi:10.1107/S205322961800219X.

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                    Borjas Nevarez, Rosendo, Balasekaran, Samundeeswari Mariappan, Kim, Eunja, Weck, Philippe, and Poineau, Frederic. Mon .  
        "Zirconium tetrachloride revisited".  United States.  doi:10.1107/S205322961800219X.  https://www.osti.gov/servlets/purl/1429669.

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@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}

}

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Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

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DOI: 10.1107/S205322961800219X

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Figures / Tables:

Table 1: Crystal data and refinement quality factors for ZrCl₄

All figures and tables (7 total)

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Works referencing / citing this record:

CCDC 1822235: Experimental Crystal Structure Determination: REWBED : Non-CSD Structure
dataset, February 2018

Nevarez, R.; Balasekaran, S.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55s3

CCDC 1822236: Experimental Crystal Structure Determination: REWBIH : Non-CSD Structure
dataset, February 2018

Nevarez, R. Borjas; Balasekaran, S. M.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55t4

CCDC 1822237: Experimental Crystal Structure Determination: REWBON : Non-CSD Structure
dataset, February 2018

Nevarez, R. Borjas; Balasekaran, S. M.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55v5

CCDC 1822238: Experimental Crystal Structure Determination: REWBUT : Non-CSD Structure Space Group: P c a 21 (29), Cell: a 6.253(5)Å b 7.383(6)Å c 12.017(9)Å, α 90° β 90° γ 90°
dataset, February 2018

Borjas Nevarez, R.; Balasekaran, S. M.; Kim, E.
The Cambridge Crystallographic Data Centre, vp
DOI: 10.5517/ccdc.csd.cc1z55w6

CCDC 1822239: Experimental Crystal Structure Determination: REWCAA : Non-CSD Structure
dataset, February 2018

Nevarez, R. Borjas; Balasekaran, S. M.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55x7

Figures / Tables found in this record:

Table 3: Con't (p. 6)

Table 4 (p. 8)

Table 5 (p. 8)

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Bis(tetraphenylarsonium) hexachloridozirconate(IV) acetonitrile tetrasolvate

Journal Article Borjas, Rosendo ; Mariappan Balasekaran, Samundeeswari ; Poineau, Frederic - IUCrData

The bis(tetraphenylarsonium) hexachloridozirconate(IV) salt, (AsPh ₄ ) ₂ [ZrCl ₆ ] (Ph = C ₆ H ₅ ), was prepared more than 25 years ago [Esmadi & Sutcliffe (1991). Indian J. Chem. 30 A , 99–101], but its crystal structure was never reported. By following a similar experimental procedure, the compound was synthesized and its crystal structure was investigated as a acetonitrile tetrasolvate, (As(C ₆ H ₅ ) ₄ ) ₂ [ZrCl ₆ ]·4CH ₃ CN, by single-crystal X –ray diffraction. The [ZrCl ₆ ] ²⁻ anion adopts a slightly distorted octahedral coordination sphere, with Zr—Cl bond lengths of 2.4586 (6), 2.4723 (6),more »« less
DOI: 10.1107/S241431461800528X
Cation distributions within a cluster framework. Synthesis and structure of the carbon- and boron-centered zirconium cluster compounds KZr/sub 6/Cl/sub 15/C and CsKZr/sub 6/Cl/sub 15/B

Journal Article Ziebarth, R P ; Corbett, J D - J. Am. Chem. Soc.; (United States)

The structures of the isotypic KZr/sub 6/Cl/sub 15/C and CsKZr/sub 6/Cl/sub 15/B have been established by single-crystal X-ray diffraction in space group Pmma, Z = 4 (R = 3.1, 3.9%, R/sub w/ = 3.2, 3.6%, respectively). These contain a matrix of Z-centered Zr/sub 6/Cl/sub 12/Z clusters linked together by trans-chlorine atoms to form separate linear and zigzag chains that are interconnected into a three-dimensional network by four additional bridging chlorides. This (Zr/sub 6/Cl/sub 12/Z)Cl/sub 6/2/ framework affords three types of chloride environments for the cations, a smaller one (a) of ten-coordination occupied by potassium or rubidium and a pair ofmore »« less
DOI: 10.1021/ja00250a015
REACTION OF ZIRCONIUM HYDRIDE WITH CARBON TETRACHLORIDE (in Japanese)

Journal Article Hata, T ; Maekawa, T - Nippon Kagaku Zasshi (Japan) Formerly Nippon Kagaku Kaishi (1921- 47) Merged with Kogyo Kagaku Zasshi to form Nippon Kagaku Kaishi

The reaction of ZrH/sub 2/ with CCl/sub 4/ was studied over the temperature range from room temperature to 250 deg C. Below the boiling point of CCl/sub 4/ the reaction products were ZrCl/sub 4/ and C/sub 2/Cl/sub 6/, but above the boiling point they were ZrCl/sub 4/ and carbon. (auth)
DOI: 10.1246/nikkashi1948.81.4_677
Electron spin resonance and optical studies on the radiolysis of carbon tetrachloride. II. Structure and reaction of CCl ter dot minus sub 4 radical anion in tetramethylsilane low-temperature solids

Journal Article muto, H ; Nunome, K - Journal of Chemical Physics; (USA)

An electron spin resonance (ESR) and optical study of carbon tetrachloride radical anion has been made to provide for a better understanding of the radiolysis of CCl{sub 4}, following CCl{sup {center dot}+}{sub 4} cation previously studied. It was found that the anion was metastably trapped in tetramethylsilane (TMS) matrices {gamma} irradiated at 4 or 77 K. The {ital g} tensor and the hyperfine coupling tensors of all atoms of the radical were determined from ESR spectral simulation by using {sup 12} CCl{sub 4} and the {sup 13}C enriched compound: {ital g}{sub {parallel}}=2.004--5, {ital g}{sub 1}=2.015,({ital A}{sub {parallel}},{ital A}{sub {perpendicular}}) =(24.3,more »« less
DOI: 10.1063/1.460559
Thermal decomposition of carbon tetrachloride

Journal Article Michael, J V ; Lim, K P ; Kumaran, S S ; ... - Journal of Physical Chemistry; (United States)

The first rate measurements of the thermal dissociation of CCl[sub 4] are reported. Three detection techniques were used in monitoring the reaction rate for various dilutions over a wide temperature range: (i) ARAS of product Cl atoms in reflected shock waves using 3.2--6.4 ppM of CCl[sub 4] in Ar over 1084--1705 K and 150--908 Torr, (ii) decay of CCl[sub 4] by molecular absorption of O-atom resonance radiation in reflected shock waves using 48--173 ppM of CCl[sub 4] in Ar over 1192--1733 K and 219--855 Torr, and (iii) laser schlieren density gradients in incident shock waves using 0.5 and 2% CCl[submore »« less
DOI: 10.1021/j100111a032

Other research related to this record:

CCDC 1822235: Experimental Crystal Structure Determination: REWBED : Non-CSD Structure
dataset, February 2018

Nevarez, R.; Balasekaran, S.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55s3
This dataset is a supplement to the current record

CCDC 1822236: Experimental Crystal Structure Determination: REWBIH : Non-CSD Structure
dataset, February 2018

Nevarez, R. Borjas; Balasekaran, S. M.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55t4
This dataset is a supplement to the current record

CCDC 1822237: Experimental Crystal Structure Determination: REWBON : Non-CSD Structure
dataset, February 2018

Nevarez, R. Borjas; Balasekaran, S. M.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55v5
This dataset is a supplement to the current record

CCDC 1822238: Experimental Crystal Structure Determination: REWBUT : Non-CSD Structure Space Group: P c a 21 (29), Cell: a 6.253(5)Å b 7.383(6)Å c 12.017(9)Å, α 90° β 90° γ 90°
dataset, February 2018

Borjas Nevarez, R.; Balasekaran, S. M.; Kim, E.
The Cambridge Crystallographic Data Centre, vp
DOI: 10.5517/ccdc.csd.cc1z55w6
This dataset is a supplement to the current record

CCDC 1822239: Experimental Crystal Structure Determination: REWCAA : Non-CSD Structure
dataset, February 2018

Nevarez, R. Borjas; Balasekaran, S. M.; Kim, E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1z55x7
This dataset is a supplement to the current record

Similar Records
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dataset (5)

Title: Zirconium tetrachloride revisited

Abstract

Citation Formats

Figures / Tables:

CCDC 1822235: Experimental Crystal Structure Determination: REWBED : Non-CSD Structure dataset, February 2018

CCDC 1822236: Experimental Crystal Structure Determination: REWBIH : Non-CSD Structure dataset, February 2018

CCDC 1822237: Experimental Crystal Structure Determination: REWBON : Non-CSD Structure dataset, February 2018

CCDC 1822238: Experimental Crystal Structure Determination: REWBUT : Non-CSD Structure Space Group: P c a 21 (29), Cell: a 6.253(5)Å b 7.383(6)Å c 12.017(9)Å, α 90° β 90° γ 90° dataset, February 2018

CCDC 1822239: Experimental Crystal Structure Determination: REWCAA : Non-CSD Structure dataset, February 2018

CCDC 1822235: Experimental Crystal Structure Determination: REWBED : Non-CSD Structure
dataset, February 2018

CCDC 1822236: Experimental Crystal Structure Determination: REWBIH : Non-CSD Structure
dataset, February 2018

CCDC 1822237: Experimental Crystal Structure Determination: REWBON : Non-CSD Structure
dataset, February 2018

CCDC 1822238: Experimental Crystal Structure Determination: REWBUT : Non-CSD Structure Space Group: P c a 21 (29), Cell: a 6.253(5)Å b 7.383(6)Å c 12.017(9)Å, α 90° β 90° γ 90°
dataset, February 2018

CCDC 1822239: Experimental Crystal Structure Determination: REWCAA : Non-CSD Structure
dataset, February 2018