作者：李志强¹, 黄江华¹, 雷萍¹, 郑绪东¹, 韩敬美¹, 尚善斋¹, 王程娅¹, 龚为民¹, 汤建国¹, 李晖²

作者单位：1. 云南中烟工业有限责任公司, 云南 昆明 650231;
2. 四川大学化学工程学院, 四川 成都 610065

关键词：烟碱;苹果酸;共晶;晶体结构;能量框架

摘要：

以探究烟碱-苹果酸盐晶体结构为目的，采用溶液反应法制备获得烟碱-苹果酸盐，溶液重结晶得到烟碱-苹果酸盐的单晶体。通过单晶X射线衍射分析法解析得到烟碱-苹果酸盐由一个加氢的烟碱阳离子（二价）与一个苹果酸阴离子（二价）组成，其化学计量式为C₁₄H₂₀N₂O₅，其中烟碱与苹果酸分子以离子键和氢键结合。晶胞参数为：正交晶系，P2₁2₁2₁空间群，a=7.629 3（16） Å，b=8.160 4（12） Å，c=24.030（4） Å，α=β=γ=90.00°。相互作用能分析结果表明：在以烟碱为中心，3.8 Å距离范围内，烟碱分子与周围分子存在12种不同的相互作用能。其中，烟碱分子与最近的苹果酸分子由于形成N2-H2…O2氢键而具有最大的总相互作用能（–23.4 kJ/mol）。能量框架研究结果表明：烟碱-苹果酸盐总体能量框架主要由形如正方体的能量框架单体组合而成，在正方体能量框架单体内部有较小的相互作用能（圆柱体半径较小）连接。该研究制备得到烟碱-苹果酸盐及其单晶体，通过实验与理论分析相结合的方式，系统分析烟碱-苹果酸盐的晶体结构，探究共晶中烟碱与苹果酸分子间的相互作用关系。

Preparation and crystal structure theoretical analysis of nicotine-malate
LI Zhiqiang¹, HUANG Jianghua¹, LEI Ping¹, ZHENG Xudong¹, HAN Jingmei¹, SHANG Shanzhai¹, WANG Chengya¹, GONG Weimin¹, TANG Jianguo¹, LI Hui²
1. China Tobacco Yunnan Industrial Co., Ltd., Kunming 650231, China;
2. School of Chemical Engineering, Sichuan University, Chengdu 610065, China
Abstract: The purpose of this study is to analyze the structures of nicotine-malate and its monocrystal which have been prepared by antisolvent diffusion and solution recrystallization, respectively. The result of single crystal X-ray diffraction analysis is that the nicotine-malate structure is composed of a hydrogenated nicotinic cation (divalent) and a malic acid anion (divalent). Its stoichiometric formula is C₁₄H₂₀N₂O₅, and nicotine binds to malic acid molecules by ionic bond and hydrogen bond. Nicotine-malate structure belongs to orthorhombic crystal system with space group P2₁2₁2₁, and the cell parameters are a=7.629 3(16) Å, b=8.160 4(12) Å, c=24.030(4) Å, α=β=γ=90.00°. The analysis of interaction energy shows that there are twelve different interaction energies between nicotine and surrounding molecules in the range of 3.8 Å with nicotine as the center. Among them, N2-H2…O2 hydrogen bonds formed by nicotine molecules and recent malic acid molecules have the maximum total interaction energy (-23.4 kJ/mol). The research results of energy framework show that the overall energy frame of nicotine-malic acid crystal is mainly composed of energy frame monomers, which are shaped like cubes. Inside the energy frame monomers, there is small interaction energy (cylinders with small radius) connection. In this study, the nicotine-malate and its monocrystal were prepared, and the structure of nicotine-malate was systematically analyzed by combining experimental and theoretical analysis, and the interaction between nicotine and malic acid in eutectic was explored.
Keywords: nicotine;malic acid;co-crystal;crystal structure;energy framework
2019, 45(10):53-61  收稿日期: 2019-06-19;收到修改稿日期: 2019-08-23
基金项目: 云南省基础研究-青年基金项目（2017FD238）；云南中烟科技计划重大专项（2018XY01）
作者简介: 李志强(1986-),男,云南楚雄州人,工程师,硕士,主要从事新型烟草制品研究
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