Dichlorobis[2-(o-tolyliminiomethyl)phenolato-O]zinc(II)

Article abstract of DOI:10.1107/S0108270100009008

In the mononuclear title compound, [ZnCl₂(C₁₄H₁₃NO)₂], the Zn^II ion is located on a twofold axis of the monoclinic space group so that the whole molecule has a twofold symmetry. The Zn^II ion has a tetrahedral coordination consisting of two chlorine ions and the O atoms of the ligands. The coordination angles around zinc have values between 102.89 (8) (O-Zn-O) and 115.83 (5)° (Cl-Zn-O). The Zn-O and Zn-Cl bond lengths are 1.977 (2) and 2.2401 (7) angstroms, respectively. There are intra- and intermolecular hydrogen bonds in the structure.

Full text of DOI:10.1107/S0108270100009008

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
phenolate bridges and a trigonal bipyramidal coordination, as
reported in the literature cited above and the references
therein. We report here the structure of a new zinc complex,
(I), obtained from the reaction of a Schiff base with ZnCl2.
The [ZnCl2(C14H13NO)2] molecule has a twofold symmetry
with respect to the twofold rotation axis, on which the ZnII ion
is located. The tetrahedral coordination around the ZnII ion,
involving two Cl and two ligand O atoms, is slightly distorted;
the ZnÐCl and ZnÐO bond lengths are 2.2401 (7) and
ISSN 0108-2701
Dichlorobis[2-(o-tolyliminiomethyl)-
phenolato-O]zinc(II)
Ê
1.977 (2) A, respectively. The degree of distortion from ideal
a
a
a
È
DincËer Ulku, * Cengiz Arõcõ, M. Nawaz Tahir and Orhan
È
tetrahedral geometry is also given by the minimum
[102.89 (5)ꢁ for O1ÐZnÐO1i] and maximum [115.83 (5)ꢁ for
ClÐZnÐO1] coordination angles around zinc. The six-
membered rings of the ligand have usual values. The dihedral
angle between the two rings de®ned by the C1±C6 and
C8±C13 atoms is 20.29 (13)ꢁ. An inspection of the possible
hydrogen bonds indicate an intramolecular N1ÐH1Á Á ÁO1
Atakolb
aDepartment of Engineering Physics, Hacettepe University, Beytepe 06532, Ankara,
Turkey, and bDepartment of Chemistry, Ankara University, Besevler 06100, Ankara,
Turkey
Correspondence e-mail: dulku@hacettepe.edu.tr
Received 23 May 2000
Accepted 23 June 2000
Ê
hydrogen bond, with a DÐH distance of 2.600 (2) A, and two
intermolecular hydrogen bonds, C7ÐH7Á Á ÁCli and C9Ð
i
Ê
H9Á Á ÁCl , with DÐA distances of 3.6058 (17) and 3.766 (3) A,
In the mononuclear title compound, [ZnCl2(C14H13NO)2], the
ZnII ion is located on a twofold axis of the monoclinic space
group so that the whole molecule has a twofold symmetry. The
ZnII ion has a tetrahedral coordination consisting of two
chlorine ions and the O atoms of the ligands. The coordination
angles around zinc have values between 102.89 (8) (OÐZnÐ
O) and 115.83 (5)ꢁ (ClÐZnÐO). The ZnÐO and ZnÐCl
respectively [symmetry code: (i) x, y, 12 + z]. These hydrogen
bonds are rather weak interactions, as can be seen from the
details given in Table 2.
Ê
bond lengths are 1.977 (2) and 2.2401 (7) A, respectively.
There are intra- and intermolecular hydrogen bonds in the
structure.
Comment
The structures of zinc complexes having different ligands have
been a subject of interest in our laboratory. The coordination
properties and geometric parameters are available from the
crystal structure studies of tetraaquabis(p-nitrosalicyl-
ato)zinc(II) (Tahir et al., 1997), bis[1-(3-chloro-4-methyl-
phenyl)iminomethylbenzen-2-oxy-O,N]zinc(II) (Tatar, Canel
et al., 1999), [ꢀ-N,N0-bis(salicylidene)-1,3-propanediaminato]-
methanolatozinc(II) dichlorozinc(II) (Atakol et al., 1999) and
zinc(II) complexes of bidentate Schiff base ligands containing
Figure 1
PLATON (Spek, 1999) drawing of the title molecule with the atom-
numbering scheme. Displacement ellipsoids are drawn at the 50%
1
probability level [symmetry code: (i) 1 x, y,
z].
2
È
È
methoxyphenyl and nitrophenyl groups (Tatar, Ulku &
Atakol, 1999). Zinc is known to activate several enzymes,
which makes it an essential element in living organisms.
Experimental
To obtain the title compound, 2-(2-methylphenyliminomethyl)phenol
(0.211 g, 0.001 mmol) was dissolved in hot methanol (40 ml). ZnCl2
(0.069 g, 0.0005 mol) in hot methanol (20 ml) was then added and the
resulting solution set aside for 48 h. Crystals suitable for X-ray
measurements were ®ltered off and dried in air.
Crystal data
3
[ZnCl2(C14H13NO)2]
Mr = 558.808
Dx = 1.450 Mg m
Mo Kꢂ radiation
Cell parameters from 25
re¯ections
Monoclinic, C2=c
Ê
Ê
a = 16.0495 (11) A
b = 10.5240 (13) A
Therefore, its chemical and structural properties are
constantly under investigation. Among the zinc compounds,
there are monomeric complexes in which the Zn atom is
tetrahedrally coordinated, as well as dimeric complexes with
ꢃ = 11.80±20.98ꢁ
ꢀ = 1.197 mm
T = 295 K
1
Ê
c = 15.6324 (12) A
ꢁ = 104.232 (2)ꢁ
Ê
V = 2559.4 (4) A
Z = 4
3
Prism, yellow
0.35 Â 0.25 Â 0.15 mm
ꢀ
1298 # 2000 International Union of Crystallography Printed in Great Britain ± all rights reserved
Acta Cryst. (2000). C56, 1298±1299

metal-organic compounds
Data collection
Table 2
Hydrogen-bonding geometry (A, ).
ꢁ
Ê
Enraf±Nonius CAD-4 diffract-
ometer
!/2ꢃ scans
Absorption correction: empirical
via scans (Fair, 1990)
Tmin = 0.694, Tmax = 0.836
2565 measured re¯ections
2467 independent re¯ections
1929 re¯ections with I > 3ꢄ(I)
Rint = 0.010
max = 25.26ꢁ
ꢃ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
h = 18 ! 19
k = 12 ! 0
N1ÐH1Á Á ÁO1
C7ÐH7Á Á ÁCli
C9ÐH9Á Á ÁCli
0.95
0.95
0.95
1.8442
2.7056
2.8185
2.600 (2)
3.606 (2)
3.766 (3)
134
158
170
l = 18 ! 0
3 standard re¯ections
frequency: 120 min
intensity decay: 1.792%
Symmetry code: (i) x; y; 12 ‡ z.
Re®nement
Re®nement on F
R = 0.028
wR = 0.037
w = 1/[ꢄF2 + (0.02F)2 + 0.4], except
w = 0 if F2 < cutoff  ꢄF2 (cutoff
is 3.0)
Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1993); data
reduction: MolEN (Fair, 1990); program(s) used to solve structure:
SIR in MolEN; program(s) used to re®ne structure: LSFM in MolEN;
molecular graphics: PLATON99 (Spek, 1999); software used to
prepare material for publication: MolEN.
S = 1.04
(Á/ꢄ)max < 0.001
3
Ê
1929 re¯ections
159 parameters
H-atom parameters constrained
Áꢅmax = 0.27 e A
3
Ê
0.19 e A
Áꢅmin
=
The authors wish to acknowledge the purchase of the
CAD-4 diffractometer under grant DPT/TBAG1 of the
Scienti®c and Technical Research Council of Turkey.
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
ZnÐCl
ZnÐO1
O1ÐC1
2.2401 (7)
1.977 (2)
1.311 (3)
N1ÐC7
N1ÐC8
1.299 (3)
1.423 (3)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1401). Services for accessing these data are
described at the back of the journal.
ClÐZnÐO1
ClÐZnÐCli
ClÐZnÐO1i
106.14 (5)
110.16 (3)
115.83 (5)
O1ÐZnÐO1i
ZnÐO1ÐC1
C7ÐN1ÐC8
102.89 (8)
125.7 (1)
126.8 (2)
Symmetry code: (i) 1 x; y; 12 z.
References
È
È
Atakol, O., Tatar, L., Akay, M. A. & Ulku, D. (1999). Anal. Sci. 15, 199±200.
Enraf±Nonius (1993). CAD-4 EXPRESS. Version 1.1. Enraf±Nonius, Delft,
The Netherlands.
Fair, C. K. (1990). MolEN. Enraf±Nonius, Delft, The Netherlands.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Spek, A. L. (1999). PLATON99. University of Utrecht, The Netherlands.
Ê
H atoms were placed geometrically at distances of 0.95 A from
their parent atoms and were re®ned as riding with Uiso = 1.3Ueq(C).
The hydrogen-bond calculations were carried out with PARST95
È
È È
Tahir, M. N., Ulku, D., Movsumov, E. M. & Hokelek, T. (1997). Acta Cryst.
C53, 176±179.
Tatar, L., Canel, E., Atakol, O. & Ulku, D. (1999). Anal. Sci. 15, 103±104.
Ê
(Nardelli, 1995). The difference map clearly shows a peak 0.91 A
from the N atom and no residual density around oxygen.
È
È
Tatar, L., Ulku, D. & Atakol, O. (1999). Acta Cryst. C55, 508±510.
È
È
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Acta Cryst. (2000). C56, 1298±1299
DinËcer Ulku et al. [ZnCl2(C14H13NO)2] 1299
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