Reichelt Hendrik, Faunce Chester A, Paradies Henrich H
Joule Physics Laboratory, Materials Research Institute, The University of Salford, Greater Manchester M5 4WT, UK.
J Phys Chem A. 2007 Apr 5;111(13):2587-601. doi: 10.1021/jp068599y. Epub 2007 Mar 14.
A comprehensive structural characterization of the colorless and yellow forms of N-hydroxyphthalimide (NHP), the deuterated form (NDP), and the ethoxylated form (ethoxy-NHP) has been carried out using single-crystal X-ray diffraction, FTIR and Raman spectroscopies, and scanning electron microscopy. Both NHP and NDP forms crystallize in the monoclinic space group (P21/c, No. 14). The various forms of NHP differ in the way in which the molecules adjoin one another through their N-hydroxyl groups and how the carbonyls of the isoindole-1,3-dione ring differ through intermolecular hydrogen bonding. Although the hydrogen bonding about the b axis is virtually the same, the isoindole-1,3-dione ring experiences different twists for the two NHP forms. Both the colorless and yellow forms of NHP exhibit strong intermolecular hydrogen bonding between O(3) and H(1). In the yellow form, the N-hydroxyl group is significantly out of the plane (approximately 1.19 degrees ), but the N-hydroxyl group in the colorless form is only approximately 0.06 degrees out of the plane. Both forms of NHP reveal an infinite chain of intermolecular hydrogen-bonded molecules in the direction of the b axis; however, the molecules are ordered differently within the unit cells. The hydrogen-bond geometry for the yellow form of NHP is O(2)-H(1)...O(3), with an angle of 185 degrees , intermolecular distances of O(2)...O(3) = 2.68 A and H(1)...O(3) = 1.70 A, and an intramolecular hydrogen bond of O(1)...H(1) = 1.17 A. The colorless form of NHP shows an intermolecular hydrogen-bond geometry between O(3) and H(1) with a distance of 1.78 A; the O(2)-O(3) distance is 2.71 A. The O(2)-H(1)...O(3) angle is 159 degrees, and the intramolecular distance is O(1)...H(1) = 0.97 A. The N-ethoxy derivative of NHP crystallizes in an orthorhombic space group (Pnma, No. 62) and exhibits no hydrogen bonding, displaying a strong head-to-tail stacking of the planar rings along the needle axis direction.
利用单晶X射线衍射、傅里叶变换红外光谱（FTIR）、拉曼光谱以及扫描电子显微镜，对N-羟基邻苯二甲酰亚胺（NHP）的无色和黄色形式、氘代形式（NDP）以及乙氧基化形式（乙氧基-NHP）进行了全面的结构表征。NHP和NDP形式均结晶于单斜空间群（P21/c，编号14）。NHP的各种形式在分子通过其N-羟基相互邻接的方式以及异吲哚-1,3-二酮环的羰基通过分子间氢键的差异方面有所不同。尽管围绕b轴的氢键几乎相同，但异吲哚-1,3-二酮环在两种NHP形式中经历了不同的扭曲。NHP的无色和黄色形式在O(3)和H(1)之间均表现出强烈的分子间氢键。在黄色形式中，N-羟基显著偏离平面（约1.19度），但无色形式中的N-羟基仅偏离平面约0.06度。两种形式的NHP在b轴方向上均显示出分子间氢键连接分子的无限链；然而，分子在晶胞内的排列方式不同。NHP黄色形式的氢键几何结构为O(2)-H(1)...O(3)，角度为185度，分子间距离O(2)...O(3)=2.68 Å，H(1)...O(3)=1.70 Å，分子内氢键O(1)...H(1)=1.17 Å。NHP无色形式在O(3)和H(1)之间显示出分子间氢键几何结构，距离为1.78 Å；O(2)-O(3)距离为2.71 Å。O(2)-H(1)...O(3)角度为159度，分子内距离为O(1)...H(1)=0.97 Å。NHP的N-乙氧基衍生物结晶于正交空间群（Pnma，编号62），且不显示氢键，沿针轴方向呈现平面环的强烈头对头堆积。
