Synthesis and crystal structures of four new dihydropyridine derivatives

Jasinski, J. P. and Guild, Curtis J. and Pek, A. E. and Samshuddin, S. and Narayana, B. and Yathirajan, H. S. and Butcher, Ray J. (2013) Synthesis and crystal structures of four new dihydropyridine derivatives. Journal of Chemical Crystallography, 43 (8). pp. 429-442. ISSN 1572-8854

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Four new Hantzsch 1,4-dihydropyridine derivatives, dimethyl 4-(4-hydroxy-3-methoxyphenyl)-2,6-dimethyl-1,4-dihydropyridine-3, 5-dicarboxylate, (I), dimethyl 4-(4-bromophenyl)-2,6-dimethyl-1,4- dihydropyridine-3,5-dicarboxylate, (II), dimethyl 4-(3-bromo-4-methoxyphenyl)-2, 6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate, (III), and dimethyl 2-(2,5-dimethoxyphenyl)-4,6-dimethyl-1,2-dihydropyridine-3,5-dicarboxylate, (IV), have been synthesized and examined by X-ray crystallography, B3LYP/6-31 G (d) molecular orbital calculations and Hirshfeld surface and fingerprint plots. (I), C18H20NO6, is monoclinic with space group P21/n and cell constants a = 9.60810(10) à , b = 7.41900(10) à , c = 24.1821(3) à , = 94.1970(10), V = 1719.14(4) à 3, and Z = 4. (II), C17H15BrN2O6, is orthorhombic with space group P212121 and cell constants a = 11.8865(5) à , b = 13.1157(4) à , c = 21.9515(9) à , V = 3422.2(2) à 3, and Z = 8. (III), C 18H20BrNO5, is orthorhombic with space group Pbca and cell constants a = 8.55470(10) à , b = 15.5248(2) à , 27.0657(5) à , V = 3594.60(9) à 3, and Z = 8. (IV), C 19H23NO6, is orthorhombic with space group Pbca and cell constants a = 11.6798(3) à , b = 13.6319(3) à , 23.0976(5) à , V = 3677.55(15) à 3, and Z = 8. The first three have the same 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate skeleton with different substituted phenyl ligands attached to the 4-site of the dihydropyridine ring. The fourth derivative (IV) consists of a related 4,6-dimethyl-1,2-dihydropyridine-3,5-dicarboxylate skeleton with 2,5-dimethoxyphenyl and methyl ligands attached to the 2 and 4 sites of the 1,2-dihydropyridine ring. The dihedral angle between the mean planes of the dihydropyridine and benzene rings is 89.6(2) (I), 86.0(6) or 87.2(9) (II), 87.7(6) (III), and 87.3(8) (IV), respectively. O-H··· (I), N-H···O (II), N-H···O (IV) hydrogen bonds and weak N-H···O, C-H···O (I), C-H···O (II), N-H···O (III), C-H···O (IV) intermolecular hydrogen bond interactions help stabilize crystal packing in each of their unit cells. A comparison of the angles between mean planes of the benzene rings in the crystals and with the DFT theoretical calculation as well as inclusion of weak intermolecular hydrogen bond interactions has been included for each molecule. Hirshfeld surface analysis for visually analyzing intermolecular interactions in crystal structures employing 3D molecular surface contours and 2D fingerprint plots have also been used to examine molecular shapes. Molecular orbital diagrams provide visual representations of the top level molecular orbital surfaces in each compound. Graphical Abstract: Synthesis, crystal structures, density functional theory (DFT), Hirshfeld and molecular orbital surface calculations of four new dihydropyridine derivitives. Figure not available: see fulltext.

Item Type: Article
Subjects: C Chemical Science > Chemistry
Divisions: Department of > Chemistry
Depositing User: Arshiya Kousar Library Assistant
Date Deposited: 20 Sep 2019 05:48
Last Modified: 11 Aug 2022 09:51

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