Next Article in Journal
5-Azido-4-dimethylamino-1-methyl-1,2,4-triazolium Hexafluoridophosphate and Derivatives
Previous Article in Journal
H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds
Article Menu

Export Article

Open AccessArticle
Crystals 2016, 6(2), 17; doi:10.3390/cryst6020017

Synthesis, Crystal Structural Investigations, and DFT Calculations of Novel Thiosemicarbazones

Department of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
*
Author to whom correspondence should be addressed.
Academic Editor: Helmut Cölfen
Received: 8 January 2016 / Revised: 26 January 2016 / Accepted: 28 January 2016 / Published: 2 February 2016
(This article belongs to the Section Biomolecular Crystals)
View Full-Text   |   Download PDF [4503 KB, uploaded 2 February 2016]   |  

Abstract

The crystal and molecular structures of three new thiosemicarbazones, 2-[1-(2-hydroxy-5-methoxyphenyl)ethylidene]-N-methyl-hydrazinecarbothioamide monohydrate (1), 2-[1-(2-hydroxy-5-methoxyphenyl)ethylidene]-N-ethyl-hydrazinecarbothioamide (2) and 2-[1-(2-hydroxy-4-methoxyphenyl)ethylidene]-N-ethyl-hydrazinecarbothioamide acetonitrile solvate (3), are reported and confirmed by single crystal X-ray diffraction, NMR and UV-vis spectroscopic data. Compound (1), C11H15N3O2S·H2O, crystallizes in the monoclinic with space group P21/c, with cell parameters a = 8.2304(3) Å, b = 16.2787(6) Å, c = 9.9708(4) Å, and β = 103.355(4)°. Compound (2), C12H17N3O2S, crystallizes in the C2/c space group with cell parameters a = 23.3083(6) Å, b = 8.2956(2) Å, c = 13.5312(3) Å, β = 91.077(2)°. Compound (3), C11H15N3O2S·C2H3N, crystallizes in the triclinic P-1 space group with cell constants a = 8.9384(7) Å, b = 9.5167(8) Å, c = 10.0574(8) Å, α = 110.773(7)°, β = 92.413(6)°, and γ = 90.654(7)°. DFT B3LYP/6-31(G) geometry optimized molecular orbital calculations were also performed and frontier molecular orbitals of each compound are displayed. The correlations 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 have been proposed. Additionally, similar correlations observed among three closely related compounds, (4), 2-[1-(2-hydroxy-4-methoxyphenyl)ethylidene]-N-methyl-hydrazinecarbothioamide, (5), 2-[1-(2-hydroxy-6-methoxyphenyl)ethylidene]-N-methyl-hydrazinecarbothioamide acetonitrile monosolvate and (6), 2-[1-(2-hydroxy-6-methoxyphenyl)ethylidene]-N-ethyl-hydrazinecarbothioamide, examining structural differences from the substitution of the methoxy group from the phenyl ring (4, 5, or 6 position) and the substitution of the terminal amine (methyl or ethyl) to their frontier molecular orbital surfaces and from their Density Functional Theory (DFT) molecular orbital energies provide further support for the suggested assignments of the title compounds. View Full-Text
Keywords: thiosemicarbazones; crystal structure; hydrogen bonds; B3LYP 6-31(G); DFT molecular orbital calculations; frontier molecular orbitals thiosemicarbazones; crystal structure; hydrogen bonds; B3LYP 6-31(G); DFT molecular orbital calculations; frontier molecular orbitals
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Supplementary material

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Anderson, B.J.; Jasinski, J.P.; Freedman, M.B.; Millikan, S.P.; O’Rourke, K.A.; Smolenski, V.A. Synthesis, Crystal Structural Investigations, and DFT Calculations of Novel Thiosemicarbazones. Crystals 2016, 6, 17.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Crystals EISSN 2073-4352 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top