State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, P R China.
Inorg Chem. 2011 Feb 7;50(3):1073-8. doi: 10.1021/ic101713y. Epub 2011 Jan 4.
Three new open-framework metal borophosphates, [Na(6)Co(3)B(2)P(5)O(21)Cl]·H(2)O (JIS-4), K(5)Mn(2)B(2)P(5)O(19)(OH)(2) (JIS-5), (NH(4))(8)[Co(2)B(4)P(8)O(30)(OH)(4)] (JIS-6), have been prepared under ionothermal conditions using ionic liquid 1-ethyl-3-methylimidazolium ([Emim]Br) as the solvent. They are the first examples of metalloborophosphate prepared by the ionothermal method. Their structures are determined by single-crystal X-ray diffraction. The 3-D open framework of JIS-4 is made of CoO(5)Cl octahedra, CoO(5) square pyramids, and PO(4) and BO(4) tetrahedra forming 12-ring channels along the [010] direction. It is noted that JIS-4 is the first 3-D open-framework structure in the family of borophosphate with the B/P ratio of 2/5, which features a borophosphate cluster anionic partial structure. Such cluster anionic partial structures connect with MnO(6) octahedra and MnO(5) trigonal bipyramids resulting in the formation of the 2-D layer structure of JIS-5 with the same B/P ratio as JIS-4. The 2-D layer structure of JIS-6 belongs to the largest family of borophosphate with a B/P ratio of 1/2 which features a unique 1-D chain anionic partial structure. Crystal data for JIS-4, orthorhombic, Pnma, a = 14.0638(8) Å, b = 9.8813(7) Å, c = 14.0008(10) Å, V = 1945.7(2) Å(3), and Z = 2; for JIS-5, monoclinic, P2(1)/n, a = 14.4939(3) Å, b = 9.2539(3) Å, c = 14.8031(4) Å, β = 101.4600(10)°, V = 1945.88(9) Å(3), and Z = 4. For JIS-6, triclinic, P1, a = 9.6928(3) Å, b = 9.8747(3) Å, c = 10.0125(2) Å, α = 62.057(2)°, β = 82.456(2)°, γ = 76.095(2)°, V = 821.60(4) Å(3), and Z = 1.
三种新型的开放骨架金属硼磷酸盐，[Na(6)Co(3)B(2)P(5)O(21)Cl]·H(2)O (JIS-4)、K(5)Mn(2)B(2)P(5)O(19)(OH)(2) (JIS-5)和(NH(4))(8)[Co(2)B(4)P(8)O(30)(OH)(4)] (JIS-6)，在离子液体 1-乙基-3-甲基咪唑溴([Emim]Br)作为溶剂的条件下，通过离子热法制备得到。它们是首例通过离子热法制备的金属硼磷酸盐。其结构通过单晶 X 射线衍射确定。JIS-4 的 3-D 开放骨架由 CoO(5)Cl 八面体、CoO(5)四方锥和 PO(4)和 BO(4)四面体组成，沿[010]方向形成 12 元环通道。值得注意的是，JIS-4 是硼磷酸盐家族中第一个具有 B/P 比为 2/5 的 3-D 开放骨架结构，其特征是硼磷酸盐簇阴离子部分结构。这种簇阴离子部分结构与 MnO(6)八面体和 MnO(5)三角双锥连接，形成与 JIS-4 相同的 B/P 比的 JIS-5 的 2-D 层状结构。JIS-6 的 2-D 层状结构属于硼磷酸盐家族中具有独特的 1-D 链阴离子部分结构的最大家族，其 B/P 比为 1/2。晶体数据 JIS-4，正交晶系，Pnma，a = 14.0638(8) Å，b = 9.8813(7) Å，c = 14.0008(10) Å，V = 1945.7(2) Å(3)，Z = 2；JIS-5，单斜晶系，P2(1)/n，a = 14.4939(3) Å，b = 9.2539(3) Å，c = 14.8031(4) Å，β = 101.4600(10)°，V = 1945.88(9) Å(3)，Z = 4。JIS-6，三斜晶系，P1，a = 9.6928(3) Å，b = 9.8747(3) Å，c = 10.0125(2) Å，α = 62.057(2)°，β = 82.456(2)°，γ = 76.095(2)°，V = 821.60(4) Å(3)，Z = 1。
