混合价聚金属氧酸盐的晶体和分子结构(英文)

Synthesis and Crystal Structure of a Mixed-valence Dodecamolybdophosphate

以碘化氮甲基喹啉和钼磷酸为原料合成了混合价化合物[C10 H10 N]4 PMo12 O4 0 ,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[C10 H10 N]4 PMo12 O4 0 (CH3 )2 NH的晶体.测定了化合物的分子结构,属单斜晶系,空间群P2 1/n,a =14.846(4),b =12.5 0 8(2 ),c =1.75 89(3)nm,β =97.98(2)°,V =3.2 35 (1)nm3 ,Mr =2 44 4.10,Dcald=2.5 1g·cm-3 ,μ =2 3.15cm-1,F(0 0 0 ) =2 34 6,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 =0.0 6 0.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 0.0 0 45nm.

The mixed_valence compound, [C 10 H 10 N] 4PMo 12 O 40 , has been synthesized from N_methylquinoline iodide and molybdophosphoric acid, and the crystals of [C 10 H 10 N] 4PMo 12 O 40 ·(CH 3) 2NH crystallized from DMF solution by diffusing water vapor into the solution. The crystal structure has been determined, monoclinic system, space group P2 1/n, a =14.846(4), b =12.508(2), c =1.7589(3) nm, β =97.98(2)°, V =3.235(1) nm 3, Mr =2444.10, D c =2.51g cm -3 ,μ =23.15 cm -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 MoO 6 octehadra of the anion are extended in z direction and the Mo atoms are shifted toward the O d atoms about 0.0045nm after it was reduced.