Jacobs Danielle L, Chan Benny C, O'Connor Abby R
Department of Chemistry, Biochemistry and Physics, Rider University, 2083 Lawrenceville Road, Lawrenceville, NJ 08648, USA.
Acta Crystallogr C. 2013 Nov;69(Pt 11):1397-401. doi: 10.1107/S0108270113025341. Epub 2013 Oct 5.
The molecular and supramolecular structures are reported of N-[2-(pyridin-2-yl)ethyl]methanesulfonamide, C8H12N2O2S, (I), N-[2-(pyridin-2-yl)ethyl]benzenesulfonamide, C13H14N2O2S, (II), and N-[2-(pyridin-2-yl)ethyl]toluenesulfonamide, C14H16N2O2S, (III). Although (II) and (III) are almost structurally identical, the N(amide)-C(ethyl)-C(ethyl)-C(pyridinyl) torsion angles for (I) and (II) are more closely comparable, with magnitudes of 175.37 (15)° for (I) and 169.04 (19)° for (II). This angle decreases dramatically with an additional methyl group in the para position of the sulfonamide substituent, resulting in a value of 62.9 (2)° for (III). In each of the three compounds there is an N-H...N hydrogen bond between the sulfonamide of one molecule and the pyridine N atom of a neighbor. Compound (I) forms hydrogen-bonded dimers, (II) uses its hydrogen bonding to connect supramolecular layers, and the hydrogen bonding of (III) connects linear chains to form layers. For arene-substituted (II) and (III), the different conformations afforded by the variable dihedral angles promote intermolecular π-π stacking in the benzene-substituted structure (II), but distorted intramolecular T-shaped π-stacking in the toluene-substituted structure (III), with a centroid-to-centroid distance of 4.9296 (10) Å.
报道了N-[2-(吡啶-2-基)乙基]甲磺酰胺(C₈H₁₂N₂O₂S,(I))、N-[2-(吡啶-2-基)乙基]苯磺酰胺(C₁₃H₁₄N₂O₂S,(II))和N-[2-(吡啶-2-基)乙基]甲苯磺酰胺(C₁₄H₁₆N₂O₂S,(III))的分子和超分子结构。尽管(II)和(III)在结构上几乎相同,但(I)和(II)的N(酰胺)-C(乙基)-C(乙基)-C(吡啶基)扭转角更具可比性,(I)的值为175.37 (15)°,(II)的值为169.04 (19)°。该角度在磺酰胺取代基的对位有一个额外甲基时会急剧减小,(III)的值为62.9 (2)°。在这三种化合物中,每个分子的磺酰胺与相邻分子的吡啶N原子之间都存在N-H...N氢键。化合物(I)形成氢键二聚体,(II)利用其氢键连接超分子层,(III)的氢键连接线性链形成层。对于芳烃取代的(II)和(III),可变二面角提供的不同构象促进了苯取代结构(II)中的分子间π-π堆积,但在甲苯取代结构(III)中导致了扭曲的分子内T形π堆积,质心到质心距离为4.9296 (10) Å。