TY - JOUR
T1 - Crystallographic and Theoretical Investigation on the Nature and Characteristics of Type i C=S···S=C Interactions
AU - Shukla, Rahul
AU - Chopra, Deepak
N1 - Funding Information:
We would like to thank the reviewers for their comments and suggestions which helped us considerably in improving the manuscript. R.S. thanks DST for INSPIRE-PhD Fellowship. R.S. also thanks Prof. T.N. Guru Row (IISc Bangalore) for providing the computational facility in his laboratory. D.C. thanks IISER Bhopal for the research infrastructure and DSTSERB for research funding.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/12/7
Y1 - 2016/12/7
N2 - In this study, we have performed an extensive crystallographic and theoretical analysis to explore the nature and characteristics of C=S···S=C interactions. A Cambridge Structural Database study revealed the abundance of C=S···S=C interactions wherein more than 70% of the crystal structures can be categorized as Type I chalcogen-chalcogen interactions. The binding energies for these contacts range in magnitudes from +2.02 kcal/mol (highly destabilized) to -1.67 kcal/mol (stabilized). Ab initio studies on (X2CS)2 models systems where X = -H, -NH2, -OH, -F, -Cl reveals that C=S···S=C are governed by the presence of negative σ-holes for X = -NH2, -OH, while the presence of a positive electrostatic region on sulfur is observed for the halogen substituted complexes. These interactions are of dispersive nature with electrostatics contributing to the destabilization in some cases.
AB - In this study, we have performed an extensive crystallographic and theoretical analysis to explore the nature and characteristics of C=S···S=C interactions. A Cambridge Structural Database study revealed the abundance of C=S···S=C interactions wherein more than 70% of the crystal structures can be categorized as Type I chalcogen-chalcogen interactions. The binding energies for these contacts range in magnitudes from +2.02 kcal/mol (highly destabilized) to -1.67 kcal/mol (stabilized). Ab initio studies on (X2CS)2 models systems where X = -H, -NH2, -OH, -F, -Cl reveals that C=S···S=C are governed by the presence of negative σ-holes for X = -NH2, -OH, while the presence of a positive electrostatic region on sulfur is observed for the halogen substituted complexes. These interactions are of dispersive nature with electrostatics contributing to the destabilization in some cases.
UR - http://www.scopus.com/inward/record.url?scp=85002528066&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.6b01530
DO - 10.1021/acs.cgd.6b01530
M3 - Article
AN - SCOPUS:85002528066
SN - 1528-7483
VL - 16
SP - 6734
EP - 6742
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 12
ER -