The role of the Pb2+ lone electron pair for bond valence sum analysis in mullite-type PbMBO4 (M = Al, Mn and Fe) compounds

Abstract

Abstract The bond valence sums (BVS) of the constituent atoms of three series of mullite-type compounds PbMn x Al1–x BO4, PbFe x Al1–x BO4 and PbMn x Fe1–x BO4 (x = 0 – 1) were analyzed with particular emphasis on lead. While the formal BVS of one bridging oxygen atom in the edge-sharing MO6 octahedron was found to be under-bonded, the other bridging atom is over-bonded. The lead atom showed always an over-bonded nature throughout the series and exhibited a different bonding strength than that of the expected valence. The stereoactivity of the 6s 2 lone electron pair (LEP) of the Pb2+ cation was monitored in terms of the absolute value of the eccentricity parameter (|Φ i |). Both calculated BVS and bond valence parameter (r 0i ) of Pb2+ cation showed a linear correlation with |Φ i |, thus corroborated the Wang–Liebau [Z. Kristallogr. 211 (1996) 437] hypothesis concerning the influence of lone-pair electrons on bond-valence parameters.