Synthesis and Characterization of Novel V/O/SO4 Chains Incorporating 2,2'-Bipyridine Ligands: Crystal Structure of [V2O2(OH)2(SO4)(2,2'-bpy)

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• 作者：M. Ishaque Khan ; Sabri Cevik ; Douglas Powell ; Sichu Li ; and Charles J. O'Connor
• 刊名：Inorganic Chemistry
• 出版年：1998
• 出版时间：January 12, 1998
• 年：1998
• 卷：37
• 期：1
• 页码：81 - 86
• 全文大小：181K
• 年卷期：v.37,no.1(January 12, 1998)
• ISSN：1520-510X

文摘

The hydrothermal reaction of a mixture of vanadyl acetylacetonate(VO(acac)₂), Na₂SO₄,2,2'-bipyridine (2,2'-bpy), and H₂O for 48 h at 160 ages/entities/deg.gif">C gives brown crystals of[V₂O₂(OH)₂(SO₄)(2,2'-bpy)₂](1) in 70% yield. Thestructure of 1 consists of ribbons constructed from theinfinite inorganic chains,[-{V₂O₂(OH)₂}-ages/entities/mgr.gif">₂-SO₄{V₂O₂(OH)₂}-SO₄]_{ages/entities/infin.gif">}, incorporatingorganic (2,2'-bipyridine) ligands. The inorganic chains arecomposed of the pairsof edge-sharing octahedra joined by{SO₄} tetrahedra throughoctahedral-tetrahedral corner sharing. Theoctahedralgeometry around each vanadium(IV) ion is defined by{VO₂(OH)₂N₂} with eachV^IV center coordinated to aterminal oxo group, two ages/entities/mgr.gif">₂-OH groups, two nitrogen donoratoms from a chelating 2,2'-bipyridine ligand, and anoxygen donor atom from aages/entities/mgr.gif">₂-SO₄^2- ligand.Crystal data for 1: monoclinic space groupP2₁/n (No. 14), a=11.7937(2) Å, b = 12.1161(3) Å, c= 15.5763(2) Å, ages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 93.750(2)ages/entities/deg.gif">, Z = 4.1 constitutes the first example ofa fully reduced vanadosulfate (V/O/SO₄) based solidincorporating both the organic and inorganic ligands.Thenovel solid exhibits Curie-Weiss paramagnetism at high temperature(T > 140 K) and short-range antiferromagneticcoupling between the V^IV centers at lowertemperature.