DSCM P27 NEW BINUCLEAR COMPOUNDS OF Zn(II) AND Mn(II) BASED ON

DIANILINEGLYOXIME AND ISOPHTHALIC ACID

D.V. Ureche1,2*, I.I. Bulhac1, A.P. Rija1,2, P.N. Bourosh2,3

1
Institute of Chemistry, Chisinau, Moldova; 2Tiraspol State University, Chisinau, Moldova;
3
Institute of Applied Physics, Chisinau, Moldova
*
E-mail: d.ureche@yahoo.com

From interactions of dianilineglyoxime (DanH2) and bridging ligand 1,3-benzendicarboxylic acid

with M(CH3COO)2 (M=Zn(II) or Mn(II)) in the molar ratio 2:1:2 have been obtained two new
binuclear complexes. The oximic ligand DanH2 has been synthesized by condensation of aniline
with dichloroglyoxime in the 2:1 molar ratio [1].
The structure of complexes were analized by using IR, NMR and X-ray data. The X-ray data
revealed that Zn(II) complex has the molecular formula [Zn2(DAnH2)2(1,3-
bdc)2(DMF)4]∙2DMF∙H2O (1) (Figure 1a), and Mn(II) – {[Mn2(DAnH2)2(1,3-
bdc)2(DMF)2(CH3OH)2][Mn2(DAnH2)2(1,3-bdc)2(DMF)4]∙2CH3OH} (2), the latter contains two
different molecular complexes (one is presented in Figure 1b).

a b
Fig. 1. The structure of molecular complex in 1 (a) and one of the molecular complexes in 2 (b).

In the IR spectra were found the following bands ʋ(C=O) = 1649 cm-1 (1,2), ʋ(N–CH3) = 1374 cm-1
(1) and 1375 cm-1 (2) , ʋ(OH) = 3317 cm-1 (1) and 3617 – 3301 cm-1 (2). In the 1H NMR spectrum
the peak for the imine group is observed at 2.5 ppm and in the 13C NMR spectrum the double signal
for the deprotonated (–COO-) groups of 1,3-bdc at 128.06 – 18.64 ppm is observed.
The compound 1 crystallized in monoclinic P2/n space group, while 2 – in triclinic P-1 space
group. The binuclear complex in 1 and the both crystallographically independent Mn(II) complexes
in 2 are centrosymmetric. The equatorial fragment of these complexes are similar
[M2(DAnH2)2(1,3-bdc)2]: to each metal atom the neutral chelate ligands DAnH2 coordinate
bidentate through their oximic nitrogen atoms, forming a 5-membered metallacycle, and these two
metal atoms are connected through two bideprotonated bridging ligands 1,3-bdc2-, that coordinates
with two oxygen atoms. Therefore, in these complexes, a metallic 16-membered macrocycle is
formed. This equatorial fragment in 1 and 2 is stabilized by four intramolecular O–H···O H-bonds,
in which as proton donors are involved the OH-groups of DAnH2, and as acceptors – the oxygen
atoms of carboxylic groups of 1,3-bdc2- ligand. The Zn(II) in 1 and Mn(II) in one of the complexes
in 2 coordinate monodentate in the axial position two DMF molecules, while the other Mn(II)
complex has in the axial positions one DMF and one methanole molecules. As a result the
octahedric coordination polyhedra of metal atoms in both compounds are formed by the N2O4 donor
sets with solvent molecules coordinated to metal atoms in axial positions.
We are still discussing the packing modes of components in the crystal networks of 1 and 2.

[1] A. Rija, I. Bulhac, E. Coropceanu et al. Chemistry Journal of Moldova, (2011), 6(2), 73-78.

138