Issue 48, 2020

K4(PO2F2)2(S2O7): first fluorooxophosphorsulfate with mixed-anion [S2O7]2− and [PO2F2] groups

Abstract

Mixed-anion compounds are among the most promising systems to design functional materials with enhanced properties. Among the phosphate–sulfate species, the [SO4]2− and [PO2F2] tetrahedra are known and give rise to structural versatility. However, to date, the crystal structures of phosphate–sulfates with the coexistence of two distinct anion groups ([S2O7]2− and [PO2F2]) in one compound are unknown. Here, a novel type of fluorooxophosphorsulfate, K4(PO2F2)2(S2O7) (KSPOF), is designed and synthesized via a high-temperature method in a closed system. The crystal structure is derived from single-crystal X-ray diffraction (C2/c, a = 13.000(10) Å, b = 7.5430(10) Å, c = 19.010(10) Å, β = 130.070(10)°, and Z = 4). It is the first fluorooxophosphorsulfate with mixed-anion building units ([S2O7]2− and [PO2F2]) and a unique drum-like cluster was found, which enriches the diversity of structures for fluorooxophosphorsulfate systems. Furthermore, the theoretical calculations indicate that KSPOF possesses moderate birefringence, which mainly originates from the distorted [PO2F2] tetrahedron.

Graphical abstract: K4(PO2F2)2(S2O7): first fluorooxophosphorsulfate with mixed-anion [S2O7]2− and [PO2F2]− groups

Supplementary files

Article information

Article type
Paper
Submitted
23 Sep 2020
Accepted
03 Nov 2020
First published
03 Nov 2020

Dalton Trans., 2020,49, 17658-17664

K4(PO2F2)2(S2O7): first fluorooxophosphorsulfate with mixed-anion [S2O7]2− and [PO2F2] groups

W. Zhang, W. Jin, Z. Yang and S. Pan, Dalton Trans., 2020, 49, 17658 DOI: 10.1039/D0DT03307C

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