Lead(II) Tetracyanidoborates with Pb₂O₂ Dimers Embedded in Network Structures

Abstract

First lead(II) tetracyanidoborates were synthesized and the crystal structures of [Pb2(H2O)4{B(CN)4}4] (1) and [Pb2(O2CCH3)2{B(CN)4}2(C2H5OH)2] (2) were determined by X‐ray diffraction. Both compounds contain dinuclear centrosymmetric Pb2O2 cores. The Pb(II) ions in both compounds have heteroleptic holodirected coordination environments constituted by three O and five N atoms (O3N5) in 1 different from that in 2, which is constituted by four O and four N atoms (O4N4). In 1 the bridging O atoms of the Pb2O2 unit belong to the water ligands, whereas in 2 one O atom of each of the two acetate ligands has the bridging functionality whereas the second one is terminally bonded, i. e. the acetate ligand coordinates in a μ2‐η2:η1 fashion. In 2, all four N atoms of the tetracyanidoborate anion are coordinated to neighboring Pb2O2 units, whereas in 1 free cyanido groups exist. Nevertheless, in both structures the dinuclear Pb units are three‐dimensionally interconnected, i. e. they are Pb(II) coordination networks. On heating compound 1 loses the aqua ligands and anhydrous Pb[B(CN)4]2 forms.

Ψ-Polyhedral symbols for coordination geometries of lead(II) with a stereochemically active lone pair

“…Among recently published articles, several show an active lone pair, with a large number in É-TRPS-9 (Chakraborty & Mohanta, 2017;Chen et al, 2011;Cheng et al, 2014;Fan & Zhu, 2007;Gao et al, 2019;Hall et al, 2000;Harrowfield et al, 2003;Hayati et al, 2018;Hosseini et al, 2013;Jennifer & Muthiah, 2014;Jin, 2020;Kowalik et al, 2017; S3) and É-SAPRS-9 (Chen et al, 2011;Cuenot et al, 2008;Li et al, 2021;Lyczko et al, 2020;Masternak et al, 2005;Morsali, 2005;Pang et al, 2019;Shahverdizadeh et al, 2008;Schwade et al, 2015;Siegesmund et al, 2021;Song et al, 2014;Tang & Wen, 2021;Weil, 2015;Yan et al, 2013;Zhang & Lu, 2005;Zhu et al, 2016) (Table S4) geometries, along with a few in É-CUS-9 (Etaiw et al, 2018;Fan & Zhu, 2006;Imran et al, letters to the editor Acta Cryst. (2021).…”