混合价聚金属氧酸盐的晶体和分子结构

以碘化氮甲基喹啉和钼磷酸为原料合成了混合价化合物C10H10N]4PMo12O40,在DMF溶液中用水蒸气扩散法进行了重结晶,得到了分子组成为C10H10N]4PMo12O40(CH3)2NH的晶体.测定了化合物的分子结构,属单斜晶系,空间群P21/n, a=14.846(4), b=12.508(2), c=1.7589(3)nm, β=97.98(2)°, V=3.235(1)nm3, Mr=2444.10, Dcald=2.51g.cm-3,μ=23.15cm-1, F(000)=2346, Z=2.结构由直接法解出.对4375个可观察到的衍射点(I>3σ(I))]进行最小二乘法修正后得R=0.060.阴离子具有Keggin结构,但还原后阴离子中的MoO6八面体在z-轴方向上伸长且Mo原子向Od原子移动大约0.0045nm.

Synthesis and Crystal Structure of a Mixed-valence Dodecamolybdophosphate

The mixed-valence compound,C10H10N]4PMo12O40,has been synthesized from N-methylquinoline iodide and molybdophosphoric acid, and the crystals of C10H10N]4PMo12O40.(CH3)2NH crystallized from DMF solution by diffusing water vapor into the solution. The crystal structure has been determined, monoclinic system, space group P21/n, a=14.846(4), b=12.508(2), c=1.7589(3)nm, β=97.98(2)°, V=3.235(1)nm3, Mr=2444.10, Dc=2.51gcm-3,μ=23.15cm-1, F(000)=2346, and Z=2. The structure was determined by direct method. The least-square refinement based on 4375 observed reflections I>3σ(I)] converged to R=0.060. The anion has the Keggin structure, but the MoO6 octehadra of the anion are extended in z direction and the Mo atoms are shifted toward the Od atoms about 0.0045nm after it was reduced.