Reactions of [WES
3]
2- (E = S, O) with CuX (X = NCS, CN, I) in the presence of bix (bix = 1,4-bis(imidazole-1-ylmethyl)benzene) in DMF or CH
3CN resulted in the formation of two novel 2D
3D interpenetrating coordinationpolymers [S
2W
2S
6Cu
4(bix)
2]
n (
1) and {[WS
4Cu
4(NCS)
2(bix)
3]·CH
3CN}
n (
2), a noninterpenetrating 3D polymer{[WS
4Cu
2(bix)]·DMF}
n (
3), and two 2D sheet polymers [WS
4Cu
3(CN)(bix)]
n (
4) and {[OWS
3Cu
3(bix)
2][I]·DMF·2H
2O}
n (
5), depending on the reaction temperature and the reagents used. Compound
1 contains a hexagonalprism of W
2Cu
4S
6 cluster core, which serves as a 4-connecting node to
link equivalent nodes via bix ligands,forming a 2D (4,4) net. In
2, a WCu
4S
4 core, which also acts as a 4-connecting node, connects the neighboringnodes either through single or double bix bridges, affording a different 2D (4,4) sheet. Inc
lined interpenetrationoccurs between two stacks of 2D sheets in the total structure of
1, while
2 involves a parallel interpenetrationbetween the adjacent layers, both creating a 3D network. Compounds
1 and
2 represent the first examples ofinterpenetrating (4,4) frameworks with clusters as nodes and bidentate pyridyl-based ligands as
linkers. Unlike
1and
2, compound
3 has a noninterpenetrating 3D network, which is composed of the inorganic 1D (WS
4Cu
2)
nchains
linked by cis and trans bix ligands. Compound
4 features an inorganic 1D (WS
4Cu
3)
n chain structure, whichis
linked by CN groups and bix ligands to form an infinite 2D network. Compound
5 is a 2D layer polymer withlarge inner cavities.