Ag[B(SO₄)₂] – Synthesis, Crystal Structure, and Characterization of the First Precious‐Metal Borosulfate

Abstract

The reaction of Ag(NO 3 ) with H 3 BO 3 in oleum (20 % SO 3 ) yielded single crystals of Ag[B(SO 4 ) 2 ] [tetragonal, P 4/ ncc, Z = 4, a = 8.6679(5) Å, c = 7.2897(5) Å, V = 547.69(7) Å 3 ]. In Ag[B(SO 4 ) 2 ], infinite anionic chains, according to the Niggli formula ∞ 1 [B(SO 4 ) 4/2 ] – , are found in tetragonal‐rod packing with charge compensation by Ag I cations. The chains are built by central boron atoms coordinated through oxygen atoms to four bidentate bridging SO 4 tetrahedra. Terminal oxygen atoms of the SO 4 tetrahedra coordinate to the silver cations in the form of slightly distorted square prisms. Magnetochemical investigations reveal the expected closed‐shell behavior of d 10 cations. DFT investigations of the solid‐state structure corroborate the experimental findings and permit the assignment of vibrational spectroscopic data.