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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (17): 1692-1698. 上一篇    下一篇

研究论文

4-[(3-乙氧酰基-2-硫代)硫脲]-4 -[(3-乙氧酰基-2-硫代)硫脲]二苯醚配体的制备、晶体结构、量化计算、比热容、热力学性质研究

张新瑜1，张鹏娟2，宋纪蓉1,3，徐抗震1，班琦勋1，黄洁*,1   

  1. (1西北大学化工学院 陕西省物理无机化学重点实验室 西安 710069)
    (2山东兖矿国际焦化有限公司 兖州 272100)
    (3故宫博物院文保科技部 北京 100009)
  • 投稿日期:2010-01-15 修回日期:2010-03-26 发布日期:2010-05-13
  • 通讯作者: 黄洁 E-mail:huangjie@nwu.edu.cn
  • 基金资助:

    国家自然科学基金项目;陕西省自然科学基金

Synthesis, Crystal Structure, Theoretical Calculation, Specific Heat Capacity, and Thermodynamic Properties of 4-[(3-Ethoxyacyl-2- thio)thiourea]-4 -[(3-etoxyacyl-2-thio)thiourea]diphenyloxide

Zhang Xinyu1 Zhang Pengjuan2 Song Jirong1,3 Xü Kangzheng1 Ban Qixun1 Huang Jie*,1   

  1. (1 Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Department of Chemical Engineering, Northwest University, Xi an 710069)
    (2 Yankuang International Coking Company, Limited, Yanzhou 272100)
    (3 Conservation Technology Department, the Palace Museum, Beijing 100009)
  • Received:2010-01-15 Revised:2010-03-26 Published:2010-05-13
  • Contact: Jie Huang E-mail:huangjie@nwu.edu.cn

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通过4,4 -二氨基二苯醚与硫氰酸钾、氯甲酸乙酯在乙酸乙酯中反应, 合成了4-[(3-乙氧酰基-2-硫代)硫脲]-4 -[(3-乙氧酰基-2-硫代)硫脲]二苯醚, 用缓慢蒸发溶剂培养了标题化合物的单晶. 并用X射线单晶衍射法测定其晶体结构, 晶体属三斜系, 空间群P-1, 晶胞参数为: a＝0.8589(5) nm, b＝1.0519(6) nm, c＝1.2876(12) nm, α＝99.391(10)°, β＝91.689(11)°, γ＝95.756(11)°, V＝1.1407(11) nm3, Z＝2, Dc＝1.347 g•cm－3, F(000)＝484, μ＝0.272 cm－1, R1＝0.0490, wR2＝0.1032. 运用Gaussian 03程序, 采用HF/6-311G和B3LYP/6-311G两种计算方法对标题化合物进行了几何全优化和自然电荷计算, 对其成键情况及自然键轨道(NBO)进行了分析. 对化合物进行了热重分析和比热测定, 计算了热力学函数, 证明该化合物有良好的热稳定性.

关键词: 酰基硫脲, 晶体结构, 量子化学计算, 自然键轨道, 热分解, 比热容

4-[(3-Ethoxyacyl-2-thio)thiourea]-4 -[(3-ethoxyacyl-2-thio)thiourea]diphenyloxide was prepared via reaction of 4,4 -diaminodiphenyl ether with potassium sulfocyanate and ethyl chloroacetate in ethyl acetate. The single crystal of the title compound was cultured by slow evaporation method at room temperature. The crystal structure was determined with an X-ray diffractometer. It is a triclinic crystal, space group P-1 with a＝0.8589(5) nm, b＝1.0519(6) nm, c＝1.2876(12) nm, α＝99.391(10)°, β＝91.689(11)°, γ＝95.756(11)°, V＝1.1407(11) nm3, Z＝2, Dc＝1.347 g•cm－3, F(000)＝484, μ＝0.272 cm－1, R1＝0.0490, wR2＝0.1032. The theoretical investigation of the title compound as a structure unit was fully optimized by HF/6-311G and B3LYP/6-311G methods in Gaussian 03 package, and the atomic charges and natural bond orbital (NBO) analysis were also discussed. The thermal behavior of the title compound was studied under a non-isothermal condition by DSC method. The specific heat capacity of the title compound was determined with continuous Cp mode of mircocalorimeter.

Key words: acylthiourea, crystal structure, theoretical calculation, natural bond orbital, thermal behavior, heat capacity