264
B. Schröder et al. / Journal of Molecular Structure 1004 (2011) 257–264
Appendix A. Supplementary material
3500.0
3000.0
2500.0
2000.0
1500.0
1000.0
500.0
Supplementary data associated with this article can be found, in
References
[1] L. Beyer, J. Hartung, R. Widera, Tetrahedron 40 (1984) 405.
[2] J. Hartung, G. Weber, L. Beyer, R. Szargan, Z. Anorg. Allg. Chem. 523 (1985) 153.
[3] U. Abram, R. Münze, J. Hartung, L. Beyer, R. Kirmse, K. Köhler, J. Stach, H. Behm,
R.T. Beursken, Inorg. Chem. 28 (1989) 834.
[4] H.J. Henkel, D. Labes, V. Hagen, Pharmazie 38 (1983) 342.
[5] J.W. Ensinck, C. Shepard, R.J. Dudl, R.H. Williams, J. Clin. Endo. Metab. 35 (1972)
463.
[6] S.L. Jeffcoate, N.J. White, Clin. Endo. Metab. 38 (1974) 155.
[7] M.A.V. Ribeiro da Silva, L.M.N.B.F. Santos, B. Schröder, L. Beyer, J. Chem.
Thermodyn. 36 (2004) 555.
[8] M.A.V. Ribeiro da Silva, L.M.N.B.F. Santos, B. Schröder, J. Chem. Thermodyn. 38
(2006) 1455.
[9] M.A.V. Ribeiro da Silva, L.M.N.B.F. Santos, B. Schröder, J. Chem. Thermodyn. 36
(2004) 753.
ˇ
[10] U. Braun, R. Richter, J. Sieler, L. Beyer, I. Leban, L. Golic, Acta Cryst. C44 (1988)
0.0
355–357.
0
500
1000 1500
2000
2500 3000 3500
ˇ
[11] U. Braun, J. Sieler, R. Richter, I. Leban, L. Golic, Cryst. Res. Technol. 23 (1988) 35.
Calculated Vibrational Frequencies / cm-1
[12] L.R. Gomes, J.N. Low, A. Quesada, L.M.N.B.F. Santos, M.A.A. Rocha, B. Schröder, J.
Mol. Struct. 936 (2009) 37.
[13] M.A.V. Ribeiro da Silva, Isabel M.M. Monteiro, L.M.N.B.F. Santos, B. Schröder, J.
Chem. Thermodyn. 39 (2007) 767.
[14] L.R. Gomes, J.N. Low, M.A.A. Rocha, L.M.N.B.F. Santos, B. Schröder, P. Brandão, C.
Matos, J. Neves, J. Mol. Struct. 990 (2011) 86.
Fig. 11. Plot of the experimental solid state vibrational frequencies,
function of the calculated (B3LYP/6-311+G(d) level of theory) gas phase unscaled
vibrational frequencies, (theo) of 1. (exp) = .96 (theo).
m(exp) as
m
m
m
[15] M.E. Wieser, M. Berglund, Pure Appl. Chem. 81 (2009) 2131.
[16] Bruker, Smart APEX (version 5.62), SAINT (Version 6.02), SHELXTL (Version
6.10) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA,
2004.
[17] G.M. Sheldrick, SADABS – Bruker Nonius Area Detector Scaling and Absorption
Correction – V2.10, 2003.
[18] P. McArdle, K. Gilligan, D. Cunningham, R. Dark, M. Mahon, CrystEngComm 6
(2004) 303.
[19] G.M. Sheldrick, SHELXS-97 and SHELXL-97, University of Göttingen, Germany,
1997.
While in 1 two bands can be attributed to mNH, in 2 and 3 only a
single signal appears, whereas it is completely missing in 4, as it is
expected for the consecutive substitution of a primary amino
group ANH2 with a secondary ANHEt, and finally tertiary ANEt2.
The appearance of mCN(amine) in the spectrum depends on the sub-
stituent it carries. The lone pairs at the terminal NAC(S) nitrogen
and the enamine nitrogen interact with vicinal groups influencing
their vibrational modes, as can be seen by applying NBO.
[20] C.K. Johnson, M.N. Burnett, ORTEPIII for Windows, University of Glasgow,
Glasgow, UK, 1998.
[21] A.L. Spek, J. Appl. Cryst. 36 (2003) 7.
[22] A.D. Becke, J. Chem. Phys. 107 (1997) 8554.
[23] C. Lee, W. Yang, G.R. Parr, Phys. Rev. B 37 (1988) 785.
[24] W.J. Hehre, L. Radom, P.V.R. Schleyer, J.A. Pople, Ab Initio Molecular Orbital
Theory, Wiley, New York, 1986.
4. Conclusion
[25] R. Dennington II, T. Keith, J. Millam, GaussView, Version 4.1.2, Semichem, Inc.,
A set of N-(diethylaminothiocarbonyl)benzimido derivatives has
been structurally examined by solid state by single crystal X-ray dif-
fractometry. For substance 3, an intermolecular NHꢃ ꢃ ꢃS interaction
has been found, similar to the earlier reported substance 2 [11], for
which recently a polymorph has been reported [38]. The tempera-
ture, standard molar enthalpies, and entropies of fusion were mea-
sured and derived using differential scanning calorimetry. The
structural results for the set were further used in the interpretation
of thermophysical phase transition properties of the title com-
pounds. All compounds were further analysed by FTIR spectroscopy
and the experimental FTIR spectra were compared with the calcu-
lated ones at B3LYP/6-311+G(d) level of theory. A detailed molecular
picture of N-(diethylaminothiocarbonyl)benzimido derivatives was
obtained from Natural Bond Order (NBO) analysis. The combination
of the applied methods reveals a deeper insight into the structures of
this type of compound.
[26] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E.
Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y.
Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, GAUSSIAN 03, Revision D.02, Gaussian, Inc., Wallingford, CT, 2004.
[27] A.E. Reed, F.J. Weinhold, Chem. Phys. 78 (1983) 4066.
[28] A.E. Reed, L.A. Curtiss, F. Weinhold, Chem. Rev. 88 (1988) 899.
[29] NBO Version 3.1, E.D. Glendening, A.E. Reed, J.E. Carpenter, F. Weinhold.
[30] L.R. Gomes, L.M.N.B.F. Santos, J.A.P. Coutinho, B. Schröder, J.N. Low, Acta Cryst.
E66 (2010) o870.
[31] A.R.R.P. Almeida, M.J.S. Monte, J. Chem. Eng. Data 55 (2010) 3507.
[32] J.P. Merrick, D. Moran, L. Radom, J. Phys. Chem. A 111 (2007) 11683.
Acknowledgments
[33] TURBOMOLE V6.2 2010,
a Development of University of Karlsruhe and
Forschungszentrum Karlsruhe GmbH, 1989–2007, TURBOMOLE GmbH, since
[34] K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 97 (1997)
119.
[35] S. Behrendt, Leipzig, Univ., Dissertation A, 1979.
[36] A. Gryff-Keller, P. Szczecinski, Org. Magn. Reson. 11 (1978) 258.
[37] M.M. Turnbull, D.J. Nelson, W. Lekouses, M.L. Sarnov, K.A. Tartarini, T. Huang,
Tetrahedron 46 (1990) 6613.
[38] B. Schröder, L.R. Gomes, L.M.N.B.F. Santos, P. Brandão, J.N. Low, Acta Cryst. E67
(2011) o962.
The authors are grateful to Paula Brandão for performing the so-
lid state single crystal X-ray diffractometry data acquisition, Maria
Celeste Coimbra de Azevedo for the FTIR data acquisition and San-
dra Magina for the DSC measurements. B.S. acknowledges FCT and
the European Social Fund (ESF) under the third Community Sup-
port Framework (CSF) for the award of a Post-Doctoral Research
Grant (SFRH/BPD/38637/2007).