Zirconium tetrachloride is a strategic material with wide applications. Until now, only one crystallographic study on ZrCl4 has been reported and it was more than 40 years ago. The compound used for the previous determination was prepared from ZrO2 and Cl2-CCl4, single-crystal X-ray diffraction (SCXRD) studies on ZrCl4 obtained from Zr metal have not been reported yet. 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 ZrCl4 to crystallize in the orthorhombic space group Pca21 (300 K, a = 6.262(9) Å, b = 7.402(11) Å, c = 12.039(17) Å, v = 558.0(14) Å3) and to consist of infinite zigzag chains of edge-sharing ZrCl6 octahedra. This chain motif is similar to the one previously observed in ZrCl4 but structural parameters and space group differ. In the temperature range 100 K and 300 K, no phase transformation was identified while elongation of intra-chain (Zr(1)---Zr(1) = 3.950(1) Å at 100 K and 3.968(5) Å at 300 K) and inter-chain distances (Cl(1)---Cl(2*) = 3.630(3) Å at 100 K and 3.689(8) Å at 300 K) occurred.

Crystal structure of zirconium tetrachloride revisited

255th National Meeting (2018)

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