Crystalline inclusion compounds of 1-(9-anthryloxy)anthraquinone as a host compound: X-ray structural characterization and π–π interaction modes in the crystal enclathrating benzene as a guest
Crystalline inclusion compounds of 1-(9-anthryloxy)anthraquinone as a host compound: X-ray structural characterization and π–π interaction modes in the crystal enclathrating benzene as a guest
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1-(9-蒽氧基)蒽醌作为主体化合物的晶体包合物：以苯为客体的晶体的X射线结构表征和π-π相互作用模式
DOI：
10.1039/p29960001139
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发表时间：
1996
期刊：
影响因子：
--
通讯作者：
S. Hayashi
中科院分区：
文献类型：
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作者：
K. Ochiai;Y. Mazaki;S. Nishikiori;Keiji Kobayashi;S. Hayashi
用X-射线结晶学、差示扫描量热法和核磁共振氢谱研究了由构象柔性主体化合物1-(9-苯甲氧基)蒽醌(1)衍生的笼状晶体(1)(C6H6)和(1)2(氢醌)(C6H6)的包结性质。配合物(1)(C6H6)是一种真正的笼合物：苯嵌入由分子间面对面π-π重叠(π-π；晶体参数：p21/c，a=16.882(2)，b=8.970(1)，c=16.405(2)A，β=91.53(2)°，Z=4，Dc=1.280 g·cm~(-3)。晶体数据：PL，a=11.779(3)，b=12.747(2)，c=8.818(1)A，α=107.14(1)，β=92.59(3)，γ=101.86(3)°，Z=L，Dc=1.335 g cm-3。这两个主组分通过氢键(O-O；2.908，2.912 A)和唯一的正交C-H-π-H-C(C-π；3.2A)和面对面的π-π相互作用(π-π；3.43 A)。苯被保留在主晶格中，最高可达173°C。晶体数据：P_1，a=15.566(5)，b=15.625(5)，c=11.571(2)A，α=98.21(2)，β=94.20(2)，γ=132.74(2)°，Z=4，Dc=1.337 g cm~(-3)。作为温度的函数测量的四极回波线形可以用绕主要对称轴的面内60°跳跃来解释。(1)(C6D6)和(1)2(对苯二酚)(C6D6)的60°跃迁的活化参数分别为9.4和19kJ·mol-1。
Inclusion properties of the clathrate crystals, (1)(C6H6) and (1)2(hydroquinone)(C6H6), derived from a conformationally flexible host compound 1-(9-anthryloxy)anthraquinone (1), have been investigated by means of X-ray crystallography, DSC analysis and 2H NMR spectroscopy. Complex (1)(C6H6) is a true clathrate: benzene is embedded in a host lattice constituted of the intermolecular face-to-face π–π overlap (π–π; 3.54 A) of the anthraquinone rings of 1. Crystal data: P21/c, a= 16.882(2), b= 8.970(1), c= 16.405(2)A, β= 91.53(2)°, Z= 4, Dc= 1.280 g cm–3. The crystal structure of a three-component clathrate (1)2(hydroquinone)(C6H6) shows the rigid two-component host lattice composed of 1 and hydroquinone. Crystal data: Pl, a= 11.779(3), b= 12.747(2), c= 8.818(1)A, α= 107.14(1), β= 92.59(3), γ= 101.86(3)°, Z= l, Dc= 1.335 g cm–3. The two host components are linked by the hydrogen bonds (O–O; 2.908, 2.912 A) as well as the unique orthogonal C–H–π–H–C (C–π; 3.2 A) and face-to-face π–π interactions (π–π; 3.43 A). Benzene is retained within the host lattice up to 173 °C. The crystal structure of guest-free host 1 has also been determined. Crystal data: P1, a= 15.566(5), b= 15.625(5), c= 11.571(2)A, α= 98.21(2), β= 94.20(2), γ= 132.74(2)°, Z= 4, Dc= 1.337 g cm –3. 2H NMR spectroscopy has been used to study the molecular motion of [2H6]benzene in the clathrates. Quadrapole echo line shapes, measured as a function of temperature, could be accounted for in terms of an in-plane 60° jump about the major symmetry axis. The activation parameters for a 60° jump are 9.4 and 19 kJ mol–1 for (1)(C6D6) and (1)2(hydroquinone)(C6D6), respectively.