Bis{1-[N-(2-methoxyphenyl)iminomethyl]naphthalen-2(1H)-onato-k 3O,N,O′}zinc(II) ethanol solvate

Article abstract of DOI:10.1107/S0108270105018044

In the crystal structure of the title compound, [Zn(C₁₈H ₁₄-NO₂)₂·C₂H₆O, the Zn atom displays a highly distorted octahedral coordination involving the O and N atoms of two molecules of the

Full text of DOI:10.1107/S0108270105018044

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
Bis{1-[N-(2-methoxyphenyl)imino-
methyl]naphthalen-2(1H)-onato-
j3O,N,O0}zinc(II) ethanol solvate
a
a
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Ivica „ilovic, * Dubravka Matkovic-Calogovic, Zora
b
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Popovic and Vibor Roje
Figure 1
A plot of the title compound. Displacement ellipsoids are drawn at the
50% probability level.
aLaboratory of General and Inorganic Chemistry, Department of Chemistry, Faculty of
Science, University of Zagreb, Ulica kralja Zvonimira 8, HR-10000 Zagreb, Croatia,
and bLaboratory for Physical Chemistry of Trace Elements, Division for Marine and
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Environmental Research, Ruer Boskovic Institute, Bijenicka 54, HR-10000 Zagreb,
Croatia
Ê
ZnÐO(oxo) bond lengths [1.9674 (18) and 1.9722 (18) A]. In
Correspondence e-mail: idilovic@chem.pmf.hr
the previously reported structure of bis(salicylal-o-anisidin-
ato)zinc(II) (Shol'nikova et al., 1970), the ZnÐO bond
Ê
distances were also found in a wide range (1.965±2.406 A).
Received 22 April 2005
Accepted 7 June 2005
Online 22 June 2005
Ê
The ZnÐN [2.025 (2) and 2.0260 (19) A] distances in (I) are
In the crystal structure of the title compound, [Zn(C18H14-
NO2)2]ÁC2H6O, the Zn atom displays a highly distorted
octahedral coordination involving the O and N atoms of two
molecules of the Schiff base 1-[N-(2-methoxyphenyl)imino-
methyl]naphthalen-2(1H)-one, which acts as an O,N,O0-
tridentate ligand. The ethanol molecule is bound to the
methoxy group of one ligand molecule via a hydrogen bond.
comparable with the corresponding values reported in the
literature (Mukherjee et al., 2000; Rajsekhar et al., 2003).
Delocalization of the ꢀ electrons accounts for the O11Ð
C12, O21ÐC22, N1ÐC111 and N2ÐC211 bond lengths
Ê
[1.285 (3), 1.305 (3), 1.299 (3) and 1.288 (3) A, respectively]
being intermediate between single- and double-bond values
(Allen et al., 1987). Bond lengths in the naphthalene moieties
are mostly as expected; shortening of the C13ÐC14 and
Ê
Comment
C23ÐC24 bonds [1.353 (4) and 1.342 (4) A] is consistent with
the quinoid effect (Exelby & Grinter, 1965).
Schiff bases derived from 2-hydroxy-1-naphthaldehyde are
interesting ligands with excellent donor abilities. Such deri-
vatives having N, O or other heteroatom donors are good
chelating agents (Elerman et al., 1992; Elmali et al., 1993;
The six-membered chelate rings, Zn1/O11/C12/C11/C111/
N1 and Zn1/O21/C22/C21/C211/N2, are almost planar. The
angles between the planes of the naphthalene rings and the
phenyl rings of the phenyliminomethyl substituents [40.11 (8)
and 53.55 (8)ꢀ] indicate non-planarity of the Schiff base
ligands.
In addition to van der Waals interactions, the crystal
packing in (I) is stabilized by weak intermolecular CÐHÁ Á ÁO
hydrogen bonds. The ethanol solvent molecule is linked to the
methoxy group of one ligand molecule by an OÐHÁ Á ÁO
hydrogen bond (Table 2).
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Bashirpoor et al., 1997; Cindric et al., 2004; Popovic, Roje,
Pavlovic, Matkovic-Calogovic & Giester, 2001; Popovic, Roje,
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Pavlovic, Matkovic-Calogovic, Rajic & Giester, 2001; Popovic
et al., 2004).
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Experimental
For the preparation of the ligand, 2-hydroxy-1-naphthaldehyde
(1.72 g, 10 mmol) and o-anisidine (1.23 g, 10 mmol) were dissolved in
ethanol (40 ml) and the solution was re¯uxed for 1 h. The resulting
yellow product was ®ltered off, washed with ethanol and dried in
vacuo (yield 2.12 g, 76.5%). Elemental analysis found (calculated) for
C18H15NO2: C 77.86 (77.96), H 5.68 (5.45), N 5.00% (5.05%). The title
compound was prepared by mixing zinc(II) acetate dihydrate (0.25 g,
1.14 mmol), the above ligand (0.63 g, 2.28 mmol) and triethylamine
(0.23 g, 2.28 mmol) in ethanol (45 ml). After re¯uxing for 3 h, the
reaction mixture was left to stand at room temperature for about a
week. Only a few yellow single crystals of (I) were obtained. After a
In the crystal structure of the title compound, (I), the Zn
atom displays a highly distorted octahedral coordination
involving four O and two N atoms of two molecules of the
Schiff base acting as a tridentate ligand (Fig. 1). Coordination
of the ZnII ion by the two methoxy O atoms is weakened,
which is re¯ected in the lengthening of the ZnÐO(methoxy)
Ê
distances [2.4778 (18) and 2.556 (2) A] in comparison with the
Acta Cryst. (2005). C61, m351±m352
DOI: 10.1107/S0108270105018044
# 2005 International Union of Crystallography m351

metal-organic compounds
period of time, the crystals deteriorated into a yellow powder.
Elemental analysis found (calculated) for C36H28N2O4Zn: C 70.28
(69.96), H 5.04 (4.57), N 4.32% (4.53%). Elemental analyses (CHN)
were performed at the Central Analytical Laboratory of the Ruer
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.056
wR(F2) = 0.165
S = 1.03
9462 re¯ections
w = 1/[ꢆ2(Fo2) + (0.1019P)2
+ 0.0196P]
2
where P = (Fo + 2Fc2)/3
(Á/ꢆ)max < 0.001
Ï
Â
Boskovic Institute, Zagreb, Croatia.
3
Ê
Áꢇmax = 0.69 e A
3
Ê
0.63 e A
419 parameters
H-atom parameters constrained
Áꢇmin
=
Crystal data
[Zn(C18H14NO2)2]ÁC2H6O
Z = 2
Dx = 1.352 Mg m
Mo Kꢁ radiation
3
Mr = 664.06
Triclinic, P1
a = 10.2078 (15) A
All H atoms were positioned geometrically, each riding on their
Ê
carrier atom, with CÐH distances in the range 0.93±0.97 A and an
Ê
OÐH distance of 0.82 A, and with Uiso(H) = 1.5 (for methyl and
Ê
Ê
Ê
Cell parameters from 60
re¯ections
b = 10.9122 (14) A
ꢄ = 10.2±18.0ꢀ
ꢅ = 0.80 mm
T = 295 K
hydroxyl H atoms) or 1.2 (for methylene and aromatic H atoms)
times Ueq of the parent atom.
c = 16.7214 (10) A
1
ꢁ = 96.550 (16)ꢀ
ꢂ = 98.113 (8)ꢀ
ꢃ = 115.592 (12)ꢀ
Data collection: STADI4 (Stoe & Cie, 1995); cell re®nement:
STADI4; data reduction: X-RED (Stoe & Cie, 1995); program(s)
used to solve structure: SHELXS97 (Sheldrick, 1997); program(s)
used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular
graphics: PLATON (Spek, 2003); software used to prepare material
for publication: SHELXL97.
Needle, yellow
0.58 Â 0.11 Â 0.09 mm
3
Ê
V = 1630.8 (4) A
Data collection
Philips PW1100 diffractometer,
upgraded by Stoe
! scans
Absorption correction: scan
(X-RED; Stoe & Cie, 1995)
Tmin = 0.90, Tmax = 0.93
9774 measured re¯ections
9462 independent re¯ections
5673 re¯ections with I > 2ꢆ(I)
Rint = 0.091
ꢄmax = 30.0ꢀ
h = 14 ! 14
k = 15 ! 15
l = 0 ! 23
The authors thank the Ministry of Science, Education and
Sports of the Republic of Croatia for ®nancial support (grant
Nos. 0119632 and 0119633).
5 standard re¯ections
frequency: 120 min
intensity decay: 4.1%
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: AV1245). Services for accessing these data are
described at the back of the journal.
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
References
Zn1ÐO11
Zn1ÐO12
Zn1ÐO21
Zn1ÐO22
Zn1ÐN1
Zn1ÐN2
O21ÐC22
N2ÐC211
1.9674 (18)
2.4778 (18)
1.9722 (18)
2.556 (2)
2.0260 (19)
2.025 (2)
1.305 (3)
N2ÐC212
N1ÐC111
N1ÐC112
O12ÐC113
O22ÐC213
O11ÐC12
C23ÐC24
C14ÐC13
1.420 (3)
1.299 (3)
1.423 (3)
1.363 (3)
1.378 (3)
1.285 (3)
1.342 (4)
1.353 (4)
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19.
Bashirpoor, M., Schmidt, H., Schulzke, C. & Rehde, D. (1997). Chem. Ber. 130,
651±657.
Â
Cindric, M., Strukan, N., Vrdoljak, V. & Kamenar, B. (2004). Z. Anorg. Allg.
Chem. 630, 585±590.
1.288 (3)
Elerman, Y., Fuess, H. & Paulus, H. (1992). Acta Cryst. C48, 40±42.
Elmali, A., Elerman, Y., Svoboda, I. & Fuess, H. (1993). Acta Cryst. C49, 965±
967.
Exelby, R. & Grinter, R. (1965). Chem. Rev. 65, 247±260.
Mukherjee, A. K., Samanta, C., Mukherjee, M. & Helliwell, M. (2000). Acta
Cryst. C56, 952±954.
O11ÐZn1ÐO21
O11ÐZn1ÐN2
O21ÐZn1ÐN2
O11ÐZn1ÐN1
O21ÐZn1ÐN1
109.25 (9)
104.67 (8)
90.74 (8)
91.26 (8)
107.75 (8)
N2ÐZn1ÐN1
150.26 (8)
155.69 (8)
92.20 (7)
85.80 (7)
70.78 (7)
O11ÐZn1ÐO12
O21ÐZn1ÐO12
N2ÐZn1ÐO12
N1ÐZn1ÐO12
Ï
Â
Â
 Â
Popovic, Z., Roje, V., Pavlovic, G., Matkovic-Calogovic, D. & Giester, G.
(2001). J. Mol. Struct. 597, 39±47.
Ï
Popovic, Z., Roje, V., Pavlovic, G., Matkovic-Calogovic, D., Rajic, M. &
Â
Giester, G. (2001). Inorg. Chim. Acta, 322, 65±73.
Â
Â
Â
Â
Ï
Popovic, Z., Roje, V., Pavlovic, G., Matkovic-Calogovic, D., Rajic, M. & Leban,
Â
I. (2004). Polyhedron, 23, 1293±1302.
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Table 2
Hydrogen-bond geometry (A, ).
Rajsekhar, G., Rao, C. P., Nattinen, K. & Rissanen, K. (2003). Inorg. Chem.
Commun. 6, 1156±1160.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
È
Gottingen, Germany.
Shol'nikova, L. M., Obodovskaya, A. E. & Shugam, E. A. (1970). Zh. Strukt.
Khim. (Russ. J. Struct. Chem.), 11, 54±61. (In Russian.)
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Stoe & Cie (1995). STADI4 (Version 1.05b) and X-RED (Version 1.05b). Stoe
& Cie, Darmstadt, Germany.
O31ÐH31Á Á ÁO21i
C23ÐH23Á Á ÁO31ii
C27ÐH27Á Á ÁO31iii
0.82
0.93
0.93
1.97
2.53
2.48
2.781 (4)
3.263 (6)
3.225 (6)
169
136
137
Symmetry codes: (i) x 1; y; z; (ii) x ‡ 1; y; z; (iii) x ‡ 1; y 1; z.
ꢁ
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m352 „ilovic et al. [Zn(C18H14NO2)2]ÁC2H6O
Acta Cryst. (2005). C61, m351±m352