Synthesis, Crystal Structures, and DFT Calculations of Three New Cyano(phenylsulfonyl)indoles and a Key Synthetic Precursor Compound

Crystals

William L. Montgomery¹  Justin M. Lopchuk¹  Gordon W. Gribble¹  Jerry P. Jasinski² 

[1] Department of Chemistry, Dartmouth College, Hanover, NH 03755-3564, USA; E-Mails:;Department of Chemistry, Keene State College, Keene, NH 03435-2001, USA

关键词: crystal structure;    indole;    phenylsulfonyl;    cyano;    nitrile;    DFT molecular orbital calculations;    frontier molecular orbitals;   

DOI  :  10.3390/cryst5030376

来源: mdpi

【 摘 要 】

Three cyano-1-(phenylsulfonyl)indole derivatives, 3-cyano-1-(phenylsulfonyl)indole, (I), 2-cyano-1-(phenylsulfonyl)indole, (II), and 2,3-dicyano-1-(phenylsulfonyl)indole, (III), and a key synthetic precursor 1-(phenylsulfonyl)-1-(1,1-dimethylethyl)indole-3-carboxamide, (IV), have been synthesized and their structures determined by single crystal X-ray crystallography. (I), C₁₅H₁₀N₂O₂S, is orthorhombic with space group P 2₁2₁2₁ and cell constants: a = 4.9459(3) Å, b = 10.5401(7) Å, c = 25.0813(14) Å, V = 1307.50(14) ų and Z = 4. (II), C₁₅H₁₀N₂O₂S, is monoclinic with space group C 2/c and cell constants: a = 18.062(2) Å, b = 11.293(2) Å, c = 15.922(3) Å, α = 90°, β = 124.49(2)°, γ = 90°, V = 2676.7 ų and Z = 8. (III), C₁₆H₉N₃O₂S, is triclinic with space group P-1 and cell constants: a = 8.1986(8) Å, b = 9.6381(11) Å, c = 9.8113(5) Å, α = 95.053(6)°, β = 101.441(6)°, γ = 108.071(9)°, V = 713.02(11) ų and Z = 2. (IV), C₁₉H₂₀N₂O₃S, is orthorhombic with space group P ccn and cell constants: a = 13.7605(8) Å, b = 27.3177(14) Å, c = 9.7584(6) Å, α = 90°, β = 90°, γ =90°, V = 3668.2(4) ų and Z = 8. All four compounds have the same indole nitrogen phenylsulfonyl substituent and (I), (II), and (III) are nitrile derivatives. (IV) is a tert-butylamide. In the crystals, the dihedral angle between the mean planes of the indole and phenylsulfonyl groups are 85.4(2)° (I), 87.2(7)° (II), 75.1(7)° (III), and 88.6(2)° (IV), respectively. Additionally, DFT geometry-optimized molecular orbital calculations were performed and frontier molecular orbitals of each compound are displayed. Correlation between the calculated molecular orbital energies (eV) for the surfaces of the frontier molecular orbitals to the electronic excitation transitions from the absorption spectra of each compound has been proposed.

【 授权许可】

CC BY   
© 2015 by the authors; licensee MDPI, Basel, Switzerland.