A comparative conformational study of (C₆H₅O)₂P(O)(NHC(S)NHCH₂C₆H₅) and analogous X-ray structures: energy calculations (solid-state/gas phase)

Abstract

The crystal structure of diphenyl (benzylcarbamothioyl)phosphoramide, (C₆H₅O)₂P(O)(NHC(S)NHCH₂C₆H₅), is reported. In the P(O)NHC(S)NH moiety the conformations are −ap/+ap/−sp, based on the O = P-N-C/P-N-C-N/P-N-C = S torsion angles (ap = antiperiplanar and sp = synperiplanar), which are different from the conformations of similar moiety in analogous structures retrieved from the Cambridge Structural Database (CSD). The calculated energies of the most stable seven conformers of the title compound (gas phase) are compared with the conformer found in the crystal structure, and the latter shows a relatively high energy value. In the crystal structure, a double-layered two-dimensional supramolecular assembly, along the bc plane, is mediated through (N-H···)(N-H···)O = P and π···π interactions, with cooperation from C-H···π, C-H···O and C-H···S. Energy framework calculations show the significant role of N-H···O hydrogen bonds in the c direction and the weak interactions with mainly dispersion component in the other two directions. The hydrogen bonds and weak interactions were confirmed by the quantum theory of atoms in molecules (AIM).

Graphical Abstract

Keywords:

• N-phosphorylated thiourea
• conformation
• crystal structure
• energy calculation
• energy framework
• hydrogen bond pattern

Acknowledgments

The partial support of this work by Ferdowsi University of Mashhad (research project 3/49072) is gratefully acknowledged. The authors appreciatively acknowledge the Cambridge Crystallographic Data Centre for access to the CSD Enterprise suite. The crystallographic experiment used infrastructure supported by Operational Programme Research, Development and Education financed by European Structural and Investment Funds and the Czech Ministry of Education, Youth and Sports (Project No. SOLID21 CZ.02.1.01/0.0/0.0/16_019/0000760).

Disclosure statement

The authors state no potential conflict of interests.

Supplementary material

CCDC number 2120531 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via: http://www.ccdc.cam.ac.uk/data-request/cif.

Additional information

Funding

The partial support of this work by Ferdowsi University of Mashhad (research project 3/49072) is gratefully acknowledged. The authors appreciatively acknowledge the Cambridge Crystallographic Data Centre for access to the CSD Enterprise suite. The crystallographic experiment used infrastructure supported by Operational Programme Research, Development and Education financed by European Structural and Investment Funds and the Czech Ministry of Education, Youth and Sports (Project No. SOLID21 CZ.02.1.01/0.0/0.0/16_019/0000760).