Structural Chemistry of Magnesium Acetates
Table 4. Structure type and acetate group functions.
I
II
III
IV
V
VI
VII
VIII
O-donor/Mga)
Structureb)
OAc function
Terminal
4
M
4
M
2
3D
1.33
O
1
1D
1
1D
0.67
1D
0
3D
Dc)
1
2
2
Bidentate bridge
2
2
3
3
3
2
4
2
3
3
2
O bridged)
3
3
Tridentate bridge
Chelating bridg-
ing
Chelating double
bridging
5
4
1
1
1
Average denticity
1
1
2.33
2.50
2.50
2.67
3.17
a) The number of neutral O-donor molecules (H2O, ROH, HOAc) per magnesium atom. b) M: molecular, 1D: chain, O: oligomeric, 3D: three
dimensional structure. c) D: the denticity of OAc group. d) The second oxygen atom of the OAc group acts as an acceptor in the hydrogen
bond.
ing oxygen atoms. If only one bridging oxygen atom is present,
Mg···Mg distances are in a typical range of 3.54–3.78 Å (struc-
References
tures IV, VI, VII, and VIII). The Mg···Mg distances are no-
ticeably shorter, 3.14–3.24 Å, if two bridging oxygen atoms
are between two magnesium atoms (structures V, VII, and
VIII). Three oxygen bridges between two magnesium atoms
result in a very short Mg···Mg distance, 3.017 Å for
Mg1···Mg3’ in structure VIII (see Figure 7).
[1] K. Kawabata, T. Yamada, H. Yoshimatsu, A. Osaka, Y. Miura, J.
Ceram. Soc. Jpn. 2002, 110, 696.
[2] S. C. Park, J. K. Chung, Y. J. Lima, S. G. Kang, K. J. Song, C. J.
Kim, C. J. Kim, Phys. C 2008, 468, 1817.
[3] J. K. Chung, W. J. Kim, Y. J. Lim, S. C. Park, C. J. Kim, Int. J.
Mod. Phys. B 2009, 23, 3515.
[4] J. D. Bass, C. Boissiere, L. Nicole, D. Grosso, C. Sanchez, Chem.
Mater. 2008, 20, 5550.
[5] S. W. Bian, J. Baltrusaitis, P. Galhotra, V. H. Grassian, J. Mater.
Chem. 2010, 20, 8705.
[6] S. . Ruediger, E. Kemnitz, Dalton Trans. 2008, 1117.
[7] K. M. Fromm, Coord. Chem. Rev. 2008, 252, 856.
[8] D. E. Irish, J. Semmler, N. J. Taylor, G. E. Toogood, Acta Crys-
tallogr. Sect. C 1991, 47, 2322.
Conclusions
In this paper, the data on structural chemistry of magnesium
acetates including solvates with water, alcohols, and acetic
acid were obtained due to achievements in the synthesis and
X-ray single crystal investigation using synchrotron radiation.
In some cases, the former data on phase compositions, unit
cell parameters and space groups were confirmed, whereas, in
other cases, the data were corrected, especially for the compo-
sitions of the solvates.
The structural data obtained were discussed in terms of the
number of neutral O-donor ligands per magnesium atom, coor-
dination environment of magnesium atoms, structural func-
tions of acetate groups, and hydrogen bonding systems. It was
shown that the decrease in the number of neutral O-donor li-
gands per magnesium atom results in an increase of the
average denticity of acetate groups with formation of oligo-
meric, one-, or three-dimensional structures. In the extreme
case of a donor free Mg(OAc)2, CNMg = 7 was observed for
the first time for a family of magnesium acetates. Since molec-
[9] L. Walter-Lévy, I. Soleilhavoup, M. P. M. de Wolff, C. R. Acad.
Sci. 1959, 249, 1234.
[10] D. Dionysiou, M. Tsianou, G. Botsaris, Ind. Eng. Chem. Res.
2000, 39, 4192.
[11] K. Isa, M. Nogawa, Thermochim. Acta 1984, 75, 197.
[12] H. H. Emons, W. Falkenberg, B. Hahne, H. Holldorf, H.-H. Sey-
fahrt, Krist. Technol. 1975, 10, 1221.
[13] F. Winkler, H. H. Emons, Krist. Technol. 1969, 4, 511.
[14] I. Zlateva, M. Spasova, Z. Anorg. Allg. Chem. 1983, 497, 229.
[15] A. L. Hector, T. A. Mayer, Acta Crystallogr., Sect. E 2002, 58,
m628.
[16] W. F. Linke, in Solubilities: Inorganic and Metal-Organic Com-
pounds (Ed.: D. Van Nostrand Co.), vol. 1, 4th ed., ACS: Wash-
ington, D. C., Princeton 1958, pp. 508.
[17] PDF-2 Database (Sets 1–51 and 70–89), JCPDS; a) PDF-No. 14–
827, b) PDF-No. 14–833, c) PDF-No. 14–802, d) PDF-No. 14–
826, e) PDF-No. 14–828, f) PDF-No. 35–1717, g) PDF-No. 35–
1718.
ular structures potentially exhibit a better solubility as com- [18] V. K. Trunov, N. O. Endeladze, J. Struct. Chem. 1986, 27, 812.
[19] J. Shankar, P. G. Khubchandani, V. M. Padmanabhan, Proc. In-
dian Acad. Sci. Sect. A 1957, 45, 117.
[20] I. Zlateva, M. Spasova, M. Angelova, Bulg. Acad. Sci. Dep.
Chem. 1981, 13, 234.
[21] C. W. Bock, A. Kaufman, J. P. Glusker, Inorg. Chem. 1994, 33,
pared to oligomeric or even polymeric ones, magnesium acet-
ates with a higher number of neutral O-donor ligands in their
structure seem to be the better choice to act as precursors in
the sol-gel synthesis.
419.
[22] C. H. L. Kennard, G. Smith, E. J. O’Reilly, B. J. Reynolds,
Acknowledgement
T. C. W. Mak, J. Chem. Soc., Dalton Trans. 1988, 2357.
This work was funded by the German Ministry of Economics and
Technology (grant 0329800).
Received: June 8, 2012
Published Online: July 10, 2012
Z. Anorg. Allg. Chem. 2012, 1265–1273
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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