F. Hajlaoui et al. / Polyhedron 28 (2009) 2113–2118
2117
Fig. 7. TG curve for the decomposition of (C
5
H
N
14 2
)[Cu(SO
4 2
) (H
2
O)
4
] ꢀ H
2
O in flowing air.
3
.2. Thermal behavior of the precursors
electrics at room temperature, stable within a wider temperature
range. Additional work with XRD, dielectric and thermocurrent
measurements are under way and will give more insight into the
structural and the physical characteristics of these materials [36].
Fig. 6 shows the successive powder patterns obtained during
the thermal decomposition of (C )[Cu(SO (H O) O, in
] ꢀ H
air in the temperature range 20–870 °C. The TG curve, carried out
with a heating rate of 15° Ch between 25 and 900 °C, appears
in Fig. 7. The first transformation occurs in the temperature range
H
5 14
N
2
4
)
2
2
4
2
ꢁ1
Appendix A. Supplementary data
7
1–202 °C. The weight loss of 20.7% is in agreement with the
departure of five water molecules (cal. weight loss of 20.1%), thus
leading to the anhydrous phase, (C )Cu(SO ), amorphous to
CCDC 718821 contains the supplementary crystallographic data
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
5
H
14
N
2
4
X-rays (Fig. 6). At 220 °C, some diffraction lines emerge from the
background. At this temperature no weight loss is observed in
the TG curve. From these observations, it was concluded that the
anhydrous phase crystallises. It can be noted that a similar thermal
References
II
behavior has already been observed for (C
4
H
14
N
2
)[M (H
2
O)
6
]-
II
(
SO
4
)
2
ꢀ 4H
2
O with M = Co and Ni templated by 1,4-butanedi-
[1] C.N.R. Rao, J.N. Behera, M. Dan, Chem. Soc. Rev. 35 (2006) 375.
[
[
[
[
2] L.F. Kirpichnikova, L.A. Shuvalov, N.R. Ivanov, B.N. Prasolov, E.F. Andreyev,
Ferroelectrics 96 (1989) 313.
3] A. Pietraszko, K. Lukaszewicz, L.F. Kirpichnikova, Polish J. Chem. 67 (1993)
1877.
4] L.F. Kirpichnikova, E.F. Andreev, N.R. Ivanov, L.A. Shuvalov, V.M. Varikash,
Kristallografiya 33 (1988) 1437.
5] A.N. Holden, B.T. Matthias, W.J. Merz, J.P. Remeika, Phys. Rev. 98 (1955) 546.
amine [32]. Unfortunately, high background contribution and
instability of diffracted intensities did not allow further structural
investigations of the compound. (C
and decomposes into CuSO (weight loss 65.38%). As shown in
Fig. 6, some diffraction lines appear to coexist with CuSO in the
temperature range 550–600 °C. They are attributed to Cu OSO
5 14 2 4
H N )Cu(SO ) is not stable
4
4
2
4
,
[6] N. Galesic, V.B. Jordanovska, Acta Crystallogr., Sect. C 48 (1992) 256.
[
[
[
7] M. Fleck, L. Bohaty, E. Tillmanns, Solid State Sci. 6 (2004) 469.
8] J.-X. Pan, G.-Y. Yang, Y.-Q. Sun, Acta Crystallogr., Sect. E 59 (2003) m286.
9] A. Rujiwatra, J. Limtrakul, Acta Crystallogr., Sect. E 61 (2005) m1403.
as also evidenced by the weight loss of 71.21% (cal. 73.29%) ob-
served in the TG curve at the inflection point (T = 590 °C). The final
transformation corresponds to the formation of copper oxide, CuO,
[10] S. Chaabouni, S. Kamoun, A. Daoud, T. Mhiri, Acta Crystallogr., Sect. C 52 (1996)
05.
5
2 4
which crystallises immediately after Cu OSO starts to decompose.
[
[
[
11] Y.-L. Fu, Z.-W. Xu, J.-L. Ren, S.W. Ng, Acta Crystallogr., Sect. E 61 (2005) m1639.
12] C.N. Morimoto, E.C. Lingafelter, Acta Crystallogr., Sect. B 26 (1970) 335.
13] V. Jordanovska, S. Aleksovska, J. Siftar, J. Thermal Anal. 38 (1992) 1563.
4
. Concluding remarks
The title compound templated by 2-methylpiperazine was pre-
[14] Y.-J. Zhao, X.-H. Li, S. Wang, Acta Crystallogr., Sect. E 61 (2005) m671.
[
15] I. Turel, I. Leban, M. Zupancic, P. Bukovec, K. Gruber, Acta Crystallogr., Sect. C
2 (1996) 2443.
16] M. Rademeyer, Acta Crystallogr., Sect. E 60 (2004) m993.
5
[
pared by the slow evaporation method and characterised by single
crystal X-ray diffraction, powder thermodiffractometry and ther-
mogravimetric analyses. It crystallises in the monoclinic system,
[17] W. Rekik, H. Naïli, T. Mhiri, T. Bataille, Acta Crystallogr., Sect. E 61 (2005) m629.
[
18] W. Rekik, H. Naïli, T. Bataille, T. Roisnel, T. Mhiri, Inorg. Chim. Acta 359 (2006)
954.
19] H. Naïli, W. Rekik, T. Bataille, T. Mhiri, Polyhedron 25 (2006) 3543.
3
[
space group P2
1
/n. The structure consists of [Cu(SO
4
)
2
(H O)
2 4
] units,
[20] Nonius, Kappa CCD Program Software, Nonius BV, Delft, The Netherlands,
1998.
built from copper (II) octahedron and two sulfate tetrahedra linked
by corner sharing, water molecules, and diprotonated 2-methylpi-
perazine cations connected together by hydrogen bonds only. The
thermal decomposition of the precursors leads to amorphous and
crystalline anhydrous phases, respectively. We believe that the
centric crystal structure of the title compound was expected from
the racemic character of the amine used in the synthesis. The use of
the chiral form of this amine (S or R) would allow us to obtain pos-
sible acentric organic–inorganic salts. More extensive studies using
this synthetic approach should giving rise to a new class of ferro-
[
21] Z. Otwinowski, W. Minor, C.W. Carter, R.M. Sweet (Eds.), Methods in
Enzymology, vol. 276, Academic Press, New York, 1997, p. 307.
22] J. de Meulenaer, H. Tompa, Acta Cryst. 19 (1965) 1014.
[
[23] L. Farrugia, J. Appl. Crystallogr. 32 (1999) 837.
[
24] G.M. Sheldrick, SHELXS-97, Programs for Crystal Solution, University of
Göttingen, Germany, 1997.
[
25] G.M. Sheldrick, SHELXL-97, Programs for Crystal Structure Refinement,
University of Göttingen, Germany, 1997.
[
[
[
26] M. Doran, A.J. Norquist, D. O’Hare, Chem. Commun. (2002) 2946.
27] T. Bataille, D. Louër, J. Mater. Chem. 12 (2002) 3487.
28] C. Ruiz-Valero, C. Cascales, B. Gomez-Lor, E. Gutierrez-Puebla, M. Iglesias, M.A.
Monge, N. Snejko, J. Mater. Chem. 12 (2002) 3073.