中心对称型4,4’-双(N’-取代酰基硫脲基)取代联苯类衍生物的 合成及其晶体结构

以苯甲酸和2,4-二氯苯氧乙酸为原料合成取代酰基异硫氰酸酯, 再分别与4,4’-联苯二胺和3,3’-二甲基-4,4’-联苯二胺反应, 合成了3种中心对称型4,4’-双(N’-取代酰基硫脲基)取代联苯类衍生物. 产物结构经紫外光谱、红外光谱和核磁共振谱确认, 并用X射线单晶衍射分析法测定了化合物4,4’-双(N’-苯甲酰基硫脲基)联苯的晶体结构, 该晶体属于三斜晶系, P-1空间群, 晶胞参数: a＝0.53447(11) nm, b＝1.03086(13) nm, c＝1.15550(13) nm, α＝98.24(3)°, β＝96.95(3)°, γ＝99.43(3)°, Z＝2, Dc＝1.379 g/cm3, V＝0.61472(16) nm3, F(000)＝266, R1＝0.0506, wR2＝0.1335. 该分子呈中心对称分布, 存在两种分子内氢键N—H…O和C—H…S, 形成了毗邻的两个六元环结构, 同时通过分子间氢键N—H…S在分子间形成的R22(8)环把分子连接成无限延伸的一维链状结构, 再通过两种CH-π相互作用形成三维超分子结构.

Synthesis and Crystal Structure of Centrosymmetric 4,4'-Bis(N'-substituted acylthioureido)biphenyls

Three centrosymmetric 4,4’-bis(N’-substituted acylthioureido)biphenyls were synthesized by the reaction of acyl isothiocyanates with 4,4’-biaminobiphenyl or 3,3’-dimethyl-4,4’-biaminobiphenyl. The structures of the target compounds were confirmed by UV, IR and 1H NMR spectra. And the crystal structure of the compound 4,4’-bis(N’-benzoylthioureido)biphenyl was resolved by an X-ray single crystal diffraction method, which belongs to triclinic system with space group P-1 and a＝0.53447(11) nm, b＝1.03086(13) nm, c＝1.15550(13) nm, α＝98.24(3)°, β＝96.95(3)°, γ＝99.43(3)°, Z＝2, Dc＝1.379 g/cm3, V＝0.61472(16) nm3, F(000)＝266, R1＝0.0506 and wR2＝0.1335 for 1761 observed reflections with I＞2σ(I). The molecule structure is centrosymmetric, and there are two types of intramolecular hydrogen bonds N—H…O and C—H…S, which form two edged six-membered rings. The intermolecular N—H…S hydrogen bonds form R22(8) rings and link the molecules into ribbons, then two kinds of CH-π interactions between the adjacent ribbons result in a 3D supramolecular structure.