我们报道了三种苦参碱衍生物的晶体结构,即,盐(1R,2R,9S,17S)-6-氧代-7,13-二氮杂四环[7.7.1.02,7.013,17]十七烷-13-铵(2E)-3-(3,4-二羟基苯基)丙-2-烯酸(苦参碱咖啡酸盐)倍半水合物,C15H25N2O+·C9H7O4-·1.5H2O(苦参碱-CA),和2-羟基苯甲酸酯(水杨酸酯)一水合物,C15H25N2O+·C7H5O3·H2O(苦参碱-SA),以及1.75水合物形式,(1R,2R,9S,17S)-7,13-重氮环[7.7.1.02,7.013,17]十七烷-6-酮1.75-水合物,C15H24N2O·1.75H2O(苦参碱-H)。每个衍生物表现出一致的分子构象的苦参碱核心,这明显不同于无水形式。值得注意的是,两种盐都在正交空间群P212121中结晶,具有一个阳离子和一个阴离子的不对称单元。在两个盐结构中,观察到苦参碱和酸之间的分子间质子转移,最终形成在叔胺N位点质子化的苦参碱阳离子。苦参碱-CA晶体堆积表现为由一维(1D)超分子螺旋链产生的三维(3D)网络,由N-H稳定..O和O-H..O氢键。在苦参碱-SA的情况下,苦参碱阳离子通过氢键与水杨酸根阴离子和水分子相互连接,也形成一维螺旋基序。水合物的结构形式,苦参碱-H,再次报道了无序的溶剂分子的精确定位。为了进一步阐明结构属性,采用Hirshfeld表面分析和指纹图谱,对这些晶体形式中的分子间接触和相互作用提供了细微差别的观点。
We report the crystal structures of three matrine derivatives, namely, the salts (1R,2R,9S,17S)-6-oxo-7,13-diazatetracyclo[7.7.1.02,7.013,17]heptadecan-13-ium (2E)-3-(3,4-dihydroxyphenyl)prop-2-enoate (matrine caffeinate) sesquihydrate, C15H25N2O+·C9H7O4-·1.5H2O (Matrine-CA), and the 2-hydroxybenzoate (salicylate) monohydrate, C15H25N2O+·C7H5O3-·H2O (Matrine-SA), as well as the 1.75-hydrate form, (1R,2R,9S,17S)-7,13-diazatetracyclo[7.7.1.02,7.013,17]heptadecan-6-one 1.75-hydrate, C15H24N2O·1.75H2O (Matrine-H). Each derivative exhibited a consistent molecular conformation for the matrine core, which is notably distinct from that of the anhydrous form. Notably, both salts crystallized in the orthorhombic space group P212121, with an asymmetric unit featuring one cation and one anion. Within the two salt structures, intermolecular proton transfer between matrine and the acid is observed, culminating in the formation of a matrine cation protonated at the tertiary amine N site. The Matrine-CA crystal packing is manifested as a three-dimensional (3D) network arising from one-dimensional (1D) supramolecular helical chains, stabilized by N-H...O and O-H...O hydrogen bonds. In the case of Matrine-SA, the matrine cation is interconnected via hydrogen bonds with salicylate anions and water molecules, also forming a 1D helical motif. The structure of the hydrate form, Matrine-H, is reported again with the disordered solvent molecules accurately located. To further elucidate the structural attributes, Hirshfeld surface analysis and fingerprint plots are employed, offering a nuanced perspective on the intermolecular contacts and interactions within these crystalline forms.