Lead(II) Tetracyanidoborates with Pb 2 O 2 Dimers Embedded in Network Structures

First lead(II) tetracyanidoborates were synthesized and the crystal structures of [Pb 2 (H 2 O) 4 {B(CN) 4 } 4 ] ( 1 ) and [Pb 2 (O 2 CCH 3 ) 2 {B(CN) 4 } 2 (C 2 H 5 OH) 2 ] ( 2 ) were determined by X‐ray diffraction. Both compounds contain dinuclear centrosymmetric Pb 2 O 2 cores. The Pb(II) ions in both compounds have heteroleptic holodirected coordination environments constituted by three O and five N atoms (O 3 N 5 ) in 1 different from that in 2 , which is constituted by four O and four N atoms (O 4 N 4 ). In 1 the bridging O atoms of the Pb 2 O 2 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 μ 2 ‐η 2 :η 1 fashion. In 2 , all four N atoms of the tetracyanidoborate anion are coordinated to neighboring Pb 2 O 2 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.