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以V2O5,H3BO3,KSCN,NH2CH2CH2NHCH2CH2OH,CuCl.H2O和H2O为原料,按物质的量比1∶5∶2∶2∶2∶500在180℃条件下晶化,得到黑色块状晶体K4[(VO)12O6B18O38(OH)4].6(H3O).17H2O。单晶结构分析结果表明该化合物属正交晶系,Pbca空间群,晶胞参数a=1.9193(4)nm,b=1.8415(4)nm,c=1.9231(4)nm,V=6.797(2)nm3,Z=4,R=0.0564,WR2=0.1649。该化合物的结构主要由阴离子簇[(VO)12O6B18O38(OH)4]10-构成。该阴离子簇由B18O38(OH)4十八元环夹在两个以共边方式交替相连形成的V6O18簇中间,通过共用氧原子形成三明治式结构新颖的硼-钒-氧阴离子簇,结构中阴离子簇通过与K离子形成的静电引力以及分子间的大量氢键相互连接,形成三维网状结构。价态计算结果表明,结构中n(VⅣ):n(VⅤ)=8:4。
Crystallization with V2O5, H3BO3, KSCN, NH2CH2CH2NHCH2CH2OH, CuCl.H2O and H2O as raw materials at a mass ratio of 1: 5: 2: 2: 2: 500 at 180 ° C gave black massive crystals of K4 ) 12O6B18O38 (OH) 4] .6 (H3O) .17H2O. The results of single crystal structure analysis show that the compound belongs to the orthorhombic Pbca space group with a = 1.9193 (4) nm and b = 1.8415 (4) nm, c = 1.9231 ) nm3, Z = 4, R = 0.0564, WR2 = 0.1649. The structure of the compound is mainly composed of anionic clusters [(VO) 12O6B18O38 (OH) 4] 10-. The anion cluster is composed of 18-membered rings of B18O38 (OH) 4 sandwiched between two V6O18 clusters alternately connected in a common side manner, and forms a sandwich-type boron-vanadium-oxygen anion cluster by sharing oxygen atoms. The anion in the structure Clusters form a three-dimensional network by electrostatic attraction with K ions and a large number of hydrogen bonds between the molecules. The valence state calculation results show that n (VIV): n (V) = 8: 4 in the structure.