Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Inorg Chem. 2011 Jul 4;50(13):6297-303. doi: 10.1021/ic200696g. Epub 2011 Jun 7.
Dark green crystals of (NpO(2))(3)(OH)(SeO(3))(H(2)O)(2)·H(2)O (1) have been prepared by a hydrothermal reaction of neptunyl(V) and Na(2)SeO(4) in an aqueous solution at 150 °C, while green plates of Na(NpO(2))(SeO(3))(H(2)O) (2) have been synthesized by evaporation of a solution of neptunyl(V), H(2)SeO(4), and NaOH at room temperature. Both compounds have been characterized by single-crystal X-ray diffraction. The structure of compound contains three crystallographically unique Np atoms that are bonded to two O atoms to form a nearly linear O═Np═O NpO(2)(+) cation. Neighboring Np(5+) ions connect to each other through a bridging oxo ion from the neptunyl unit, a configuration known as cation-cation interactions (CCIs), to build a complex three-dimensional network. More specifically, each Np(1)O(2)(+), Np(2)O(2)(+), and Np(3)O(2)(+) cation is involved in three, five, and four CCIs with other units, respectively. The framework of neptunyl(V) pentagonal bipyramids is decorated by selenite trigonal pyramids with one-dimensional open channels where uncoordinated waters are trapped via hydrogen bonding interactions. Compound adopts uranophane-type (NpO(2))(SeO(3)) layers, which are separated by Na(+) cations and water molecules. Within each layer, neptunyl(V) pentagonal bipyramids share equatorial edges with each other to form a single chain that is further connected by both monodentate and bidentate selenite trigonal pyramids. Crystallographic data: compound, monoclinic, P2(1)/c, Z = 4, a = 6.6363(8) Å, b = 15.440(2) Å, c = 11.583(1) Å, β = 103.549(1)°, V = 1153.8(2) Å(3), R(F) = 0.0387 for I > 2σ(I); compound (2), monoclinic, C2/m, Z = 4, a = 14.874(4) Å, b = 7.271(2) Å, c = 6.758(2) Å, β = 112.005(4)°, V = 677.7(3) Å(3), R(F) = 0.0477 for I > 2σ(I).
深绿色的（NpO(2))(3)(OH)(SeO(3))(H(2)O)(2)·H(2)O（1）晶体是通过在 150°C 的水溶液中用五价镎和 Na(2)SeO(4)进行水热反应制备的，而绿色的 Na(NpO(2))(SeO(3))(H(2)O)（2）则是通过在室温下蒸发五价镎、H(2)SeO(4)和 NaOH 的溶液合成的。这两种化合物都通过单晶 X 射线衍射进行了表征。化合物的结构包含三个在晶体学上独特的 Np 原子，它们与两个 O 原子结合形成一个几乎线性的 O=Np=O NpO(2)(+)阳离子。相邻的 Np(5+)离子通过来自五价镎单元的桥接氧离子连接在一起，这种结构称为阳离子-阳离子相互作用（CCIs），从而构建了一个复杂的三维网络。更具体地说，每个 Np(1)O(2)(+)、Np(2)O(2)(+)和 Np(3)O(2)(+)阳离子分别与其他单元形成三个、五个和四个 CCIs。五价镎的五角双锥的框架被硒代三角锥所装饰，其中一维的开放通道中捕获了未配位的水，通过氢键相互作用。化合物采用铀矿型(NpO(2))(SeO(3))层，这些层被 Na(+)阳离子和水分子隔开。在每个层内，五价镎的五角双锥通过彼此共享赤道边缘形成单链，进一步通过单齿和双齿硒代三角锥连接。晶体学数据：化合物，单斜，P2(1)/c，Z = 4，a = 6.6363(8)Å，b = 15.440(2)Å，c = 11.583(1)Å，β = 103.549(1)°，V = 1153.8(2)Å(3)，R(F) = 0.0387（I > 2σ(I)）；化合物（2），单斜，C2/m，Z = 4，a = 14.874(4)Å，b = 7.271(2)Å，c = 6.758(2)Å，β = 112.005(4)°，V = 677.7(3)Å(3)，R(F) = 0.0477（I > 2σ(I)）。
