78
A. Trzesowska-Kruszynska / Journal of Molecular Structure 1017 (2012) 72–78
absorption bands arise from the transitions between
orbitals and can be attributed to transitions of d ? d character, ad-
mixed with ? d ligand-to-metal charge-transfer transition
(LMCT) due to participation of -bonding orbitals of the furan ring.
a
- and b-spin
bridge Crystallographic Data Centre (CCDC), 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 (0)1223 336033; email: depos-
it@ccdc.cam.ac.uk). Supplementary data associated with this
p
p
These transitions are mainly associated with transitions to the
vacant bLUMO + 2. The higher energy absorption bands are related
with the
p ? d and p ?
pꢂ ligand-to-metal, ligand–ligand charge-
transfer and interligand transitions.
References
[1] F.H. Allen, Acta Crystallogr. B58 (2002) 380.
[2] Á. García-Raso, J.J. Fiol, A. López-Zafra, A. Cabrero, I. Mata, E. Molins,
Polyhedron 18 (1999) 871.
[3] I. Sßakıyan, Trans. Met. Chem. 32 (2007) 131.
[4] X. Feng, C.-Z. Xie, L.-Y. Wang, Y.-F. Wang, L.-F. Ma, J. Chem. Crystallogr. 38
(2008) 619.
[5] N.M. Hosny, F.I. El-Dossoki, J. Chem. Eng. Data 53 (2008) 2567.
[6] N.A. Nawar, A.-H.M. Shallaby, N.M. Hosny, M.M. Mostafa, Trans. Met. Chem. 26
(2001) 180.
[7] D. Chakraborty, P.K. Bhattacharya, J. Inorg. Biochem. 39 (1990) 1.
[8] M. Kruppa, B. König, Chem. Rev. 106 (2006) 3520.
[9] I.S. MacPherson, M.E.P. Murphy, Cell. Mol. Life Sci. 64 (2007) 2887.
[10] Z.-Y. Sun, R. Yuan, Y.-Q. Chai, L. Xu, X.-X. Gan, W.-J. Xu, Anal. Bioanal. Chem.
378 (2004) 490.
[11] A. Datta, S. Walia, B.S. Parmar, J. Agric. Food Chem. 49 (2001) 4726.
[12] P.Y. Nikolov, V.A. Yaylayan, J. Agric. Food Chem. 59 (2011) 6099.
[13] S. Kumar, D.N. Dhar, P.N. Saxena, J. Sci. Ind. Res. 68 (2009) 181.
[14] Cie STOE, X-RED, version 1.18. STOE & Cie GmbH, Darmstadt, Germany, 1999.
[15] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.
3.3. Thermal stability
_
The complex compound 1 is stable up to 70 °C in the air atmo-
sphere and its decomposition is a multi-stage process. The initial
step of the thermal decomposition occurs within the temperature
range of 70–220 °C. The DTA (140 °C, 210 °C) and DTG (minima
at 140 °C, 190 °C) curves indicate that there are two sub-processes.
This first endothermic step is attributed to the removal of water
molecules. The mass spectrum of the thermal decomposition
shows the ion current signals m/z = 17 and 18 which correspond
to the molecular mass of OH+, H2O+, respectively. According to
the detected gaseous products, in the second stage the decomposi-
tion of the organic ligand and removal of the water molecules
begin simultaneously. The succeeding stage is exothermic. This
step of the decomposition is characterised by strong, narrow peaks
on the DTA curve (320 °C) and three minima on the DTG curves
(270 °C, 305 °C and 340 °C) and the biggest mass loss. The main
volatile products of decomposition and fragmentation processes
include C+, O+, COþ2 , CO2H+, OH+, H2O+, C2H2þ, CH2O+, C2H6O+ and
[16] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
[17] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B37 (1988) 785.
[18] M. Head-Gordon, T. Head-Gordon, Chem. Phys. Lett. 220 (1994) 122.
[19] Gaussian 03, Revision E.01., 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, 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, Inc., Pittsburgh, PA, 2004.
C3Hþ. During heating over 400 °C the compound decomposition
3
finishes with forming the copper(II) oxide as a final product.
4. Conclusions
The mononuclear Cu(II) complex has been prepared with the
bidentate glycine Schiff base ligand obtained in situ from the fur-
an-2-carbaldehyde and glycine. The complex molecule possesses
rather unusual ligand coordination. The results of structural analy-
sis and quantum–mechanical calculations indicate the existence of
[20] S.F. Boys, F. Bernardi, Mol. Phys. 19 (1970) 553.
[21] S. Miertu, E. Scrocco, J. Tomasi, Chem. Phys. 55 (1981) 117.
[22] M. Cossi, V. Barone, R. Cammi, J. Tomasi, Chem. Phys. Lett. 255 (1996) 327.
[23] E. Runge, E.K.U. Gross, Phys. Rev. Lett. 52 (1984) 997.
[24] M.E. Casida, C. Jamorski, K.C. Casida, D.R. Salahub, J. Chem. Phys. 108 (1998)
4439.
[25] R. Bauernschmitt, R. Ahlrichs, Chem. Phys. Lett. 256 (1996) 454.
[26] A. Frisch, R.D. Dennington II, T.A., Keith, A.B. Nielsen and A.J. Holder,
GaussView, Revision 03, Gaussian, Inc., Carnegie, PA, 2003.
weak C@Oꢀ ꢀ ꢀ
p interactions governing the crystal structure.
Although the attempts to obtain and isolate the pure ligand,
N0-(2-furfurylidene)glycine, were unsuccessful, the results of MP2
and DFT calculations suggest that if such amino acid Schiff base
exist, it will form the zwitterion in the solid-state. According to
the analysis of the known structural data, the existence of a chiral
centre seems to be crucial to obtain the amino acid Schiff base in
the crystalline form.
[27] Data processing Module, Copyright
Version 1.4.
Ó 1994–1998 SETARAM – FRANCE;
[28] J.E. Gautrot, P. Hodge, D. Cupertino, M. Helliwell, New J. Chem. 30 (2006) 1801.
[29] O.B. Berryman, D.W. Johnson, Chem. Commun. (2009) 3143.
[30] M. Egli, S. Sarkhel, Acc. Chem. Res. 40 (2007) 197.
[31] Y.N. Imai, Y. Inoue, I. Nakanishi, K. Kitaura, Protein Sci. 17 (2008) 1129.
[32] B.L. Schottel, H.T. Chifotides, K.R. Dunbar, Chem. Soc. Rev. 37 (2008) 68.
[33] A. Bondi, J. Phys. Chem. 68 (1964) 441.
Acknowledgments
[34] X. Yang, D. Wu, J.D. Ranford, J.J. Vittal, Cryst. Growth Des. 5 (2005) 41.
[35] B.M. Draškovic´, G.A. Bogdanovic´, M.A. Neelakantan, A.-C. Chamayou, S.
Thalamuthu, Y.S. Avadhut, J. Schmedt auf der Günne, S. Banerjee, C. Janiak,
Cryst. Growth Des. 10 (2010) 1665.
This work was financed by funds allocated by the Ministry of
Science and Higher Education to the Institute of General and
Ecological Chemistry, Technical University of Lodz, Poland (Grant
No. IP 2010 043770). The GAUSSIAN03 calculations were carried
out in the Academic Computer Centre CYFRONET of the AGH Uni-
versity of Science and Technology in Cracow, Poland (Grant No.
MNiSW/SGI3700/PŁódzka/040/2008).
[36] S. Panchanan, R. Hämäläinen, P.S. Roy, J. Chem. Soc., Dalton Trans. (1994) 2381.
}
_
_
[37] Y. Ozcan, S. Ide, I. Sßakıyan, E. Logoglu, J. Mol. Struct. 658 (2003) 207.
[38] Z. Qiu, L. Li, Y. Liu, T. Xu, D. Wang, Acta Crystallogr. E64 (2008) m745.
[39] M.J. O’Donnell, Acc. Chem. Res. 37 (2004) 506.
[40] J. Hernández-Toribio, R. Gómez Arrayás, J.C. Carretero, Chem. Eur. J. 17 (2011)
6334.
[41] J. Hernández-Toribio, R. Gómez Arrayás, J.C. Carretero, J. Am. Chem. Soc. 130
(2008) 16150.
Appendix A. Supplementary material
[42] C. Sßenol, Z. Hayvali, H. Dal, T. Hökelek, J. Mol. Struct. 997 (2011) 53.
[43] B.S. Creaven, M. Devereux, D. Karcz, A. Kellett, M. McCann, A. Noble, M. Walsh,
J. Inorg. Biochem. 103 (2009) 1196.
CCDC-848630 (1) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge