Khan M. Ishaque, Cevik Sabri, Powell Douglas, Li Sichu, O'Connor Charles J.
Department of Biological, Chemical, and Physical Sciences, Illinois Institute of Technology, Chicago, Illinois 60616, Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, and Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148.
Inorg Chem. 1998 Jan 12;37(1):81-86. doi: 10.1021/ic970971o.
The hydrothermal reaction of a mixture of vanadyl acetylacetonate (VO(acac)(2)), Na(2)SO(4), 2,2'-bipyridine (2,2'-bpy), and H(2)O for 48 h at 160 degrees C gives brown crystals of [V(2)O(2)(OH)(2)(SO(4))(2,2'-bpy)(2)] (1) in 70% yield. The structure of 1 consists of ribbons constructed from the infinite inorganic chains, -{V(2)O(2)(OH)(2)}-&mgr;(2)-SO(4){V(2)O(2)(OH)(2)}-SO(4), incorporating organic (2,2'-bipyridine) ligands. The inorganic chains are composed of the pairs of edge-sharing octahedra joined by {SO(4)} tetrahedra through octahedral-tetrahedral corner sharing. The octahedral geometry around each vanadium(IV) ion is defined by {VO(2)(OH)(2)N(2)} with each V(IV) center coordinated to a terminal oxo group, two &mgr;(2)-OH groups, two nitrogen donor atoms from a chelating 2,2'-bipyridine ligand, and an oxygen donor atom from a &mgr;(2)-SO(4)(2)(-) ligand. Crystal data for 1: monoclinic space group P2(1)/n (No. 14), a = 11.7937(2) Å, b = 12.1161(3) Å, c = 15.5763(2) Å, beta = 93.750(2) degrees, Z = 4. 1 constitutes the first example of a fully reduced vanadosulfate (V/O/SO(4)) based solid incorporating both the organic and inorganic ligands. The novel solid exhibits Curie-Weiss paramagnetism at high temperature (T > 140 K) and short-range antiferromagnetic coupling between the V(IV) centers at lower temperature.
将乙酰丙酮氧钒（VO(acac)(2)）、Na(2)SO(4)、2,2'-联吡啶（2,2'-bpy）和H(2)O的混合物在160℃下进行水热反应48小时，以70%的产率得到棕色晶体[V(2)O(2)(OH)(2)(SO(4))(2,2'-bpy)(2)]（1）。1的结构由由无限无机链-{V(2)O(2)(OH)(2)}-&mgr;(2)-SO(4){V(2)O(2)(OH)(2)}-SO(4)构成的条带组成，其中包含有机（2,2'-联吡啶）配体。无机链由通过八面体-四面体角共享由{SO(4)}四面体连接的边缘共享八面体对组成。每个钒（IV）离子周围的八面体几何结构由{VO(2)(OH)(2)N(2)}定义，每个V（IV）中心与一个末端氧基团、两个&mgr;(2)-OH基团、来自螯合2,2'-联吡啶配体的两个氮供体原子以及来自&mgr;(2)-SO(4)(2)(-)配体的一个氧供体原子配位。1的晶体数据：单斜空间群P2(1)/n（编号14），a = 11.7937(2) Å，b = 12.1161(3) Å，c = 15.5763(2) Å，β = 93.750(2)°，Z = 4。1是第一个同时包含有机和无机配体的完全还原的钒硫酸盐（V/O/SO(4)）基固体的例子。这种新型固体在高温（T > 140 K）下表现出居里-外斯顺磁性，在低温下V（IV）中心之间存在短程反铁磁耦合。
