Hybrid Inorganic–Organic 1D and 2D Frameworks with [As 6 V 15 O 42 ] 6– Polyoxoanions as Building Blocks

Three novel heteropolyoxovanadates, [Ni(2,2′‐bpy) 3 ] 2 [{Ni(en) 2 }As 6 V 15 O 42 (H 2 O)] · 9.5H 2 O ( 1 ), [Zn 2 (dien) 3 (H 2 O) 2 ] 1/2 {[Zn 2 (dien) 3 ]As 6 V 15 O 42 (H 2 O)} · 2H 2 O ( 2 ), and [Co(enMe) 2 ] 3 [As 6 V 15 O 42 (H 2 O)] · 2H 2 O ( 3 ), were hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction. Crystal data: 1 , monoclinic, P 2 1 / n , a = 14.0324(9) Å, b = 13.9900(8) Å, c = 30.5785(19) Å, β = 102.861(1)°, Z = 2; 2 , monoclinic, P 2 1 / c , a = 13.361(5) Å, b = 23.979(8) Å, c = 22.873(8) Å, β = 102.459(4)°, Z = 4; 3 , triclinic, P $\bar {1}$ , a = 13.2976(1) Å, b = 15.0583(1) Å, c = 20.1661(2) Å, α = 85.620(8)°, β = 79.553(9)°, γ = 65.087(9)°, Z = 2. Compound 1 consists of 1D [{Ni(en) 2 }As 6 V 15 O 42 (H 2 O)] 4– chains and [Ni(2,2′‐bpy) 3 ] 2+ cations, in which the chain host has a molecular recognition ability for the chiral guest cations. Compound 2 is constructed from linking of the [As 6 V 15 O 42 ] 6– polyoxoanions and novel dinuclear [Zn 2 (dien) 3 ] 4+ cations into the first 1D helical As–V–O cluster chain. Compound 3 is the first 2D framework based on [As 6 V 15 O 42 ] 6– polyoxoanions as building blocks. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)