Synthesis and crystal structure of 2,4-diiodo-6-[(2-morpholin-4-yl- ethylimino)-methyl]-phenolato-zinc(II)

Article abstract of DOI:10.1007/s10870-009-9612-2

One new complex, 2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)- methyl]- phenolato-zinc(II) has been designed and synthesized. The structure was determined by UV, IR and single X-ray crystallography study. The title complex C₂₆H₃₀O₄N₄I₄Zn crystallizes in the triclinic space group P - 1 with the cell parameters a = 9.938(2) A, b = 11.937(2) A, c = 14.527(3) A, α = 87.14(3)°, β = 79.03(3)°, γ = 76.20(3)°, V = 1565.1(5) A³ and Z = 2. The central zinc(II) is four coordinate and bonds to two nitrogen atoms and two oxygen atoms from two 3,5-diiodosalicylaldehyde- 2- morpholinoethylamine Schiff bases. The complex is linked into a column by weak intermolecular interactions.

Full text of DOI:10.1007/s10870-009-9612-2

J Chem Crystallogr (2009) 39:931–934
DOI 10.1007/s10870-009-9612-2
COMMUNICATION
Synthesis and Crystal Structure of 2,4-Diiodo-6-[(2-morpholin-4-
yl-ethylimino)-methyl]-phenolato-zinc(II)
Suo-Ping Xu Æ Peng-Cheng Lv Æ Rui-Qin Fang Æ
Lei Shi Æ Hai-Liang Zhu
Received: 19 March 2008 / Accepted: 21 August 2009 / Published online: 9 September 2009
Ó Springer Science+Business Media, LLC 2009
Abstract One new complex, 2,4-Diiodo-6-[(2-morpho-
lin-4-yl-ethylimino)- methyl]- phenolato-zinc(II) has been
designed and synthesized. The structure was determined by
UV, IR and single X-ray crystallography study. The title
complex C26H30O4N4I4Zn crystallizes in the triclinic space
determined by single X-ray analysis [1–4]. Zinc exists in
some native enzymes and is required by all organisms. Due
to their important biological relevance, many zinc com-
plexes with Schiff bases have been reported in recent years
[5–8]. Schiff bases derived from salicylaldehyde analogues
and the metal complexes thereof show a wide spectrum of
antimicrobial properties [9–12]. However, to our knowl-
edge, there are no structure reports of zinc(II) complexes of
the Schiff base that is the condensation product of reaction of
3,5-diiodosalicylaldehyde and 2-morpholinoethylamine. In
this paper, the complex, 2,4-Diiodo-6-[(2-morpholin-4-yl-
ethylimino)-methyl]-phenolato-zinc(II), is obtained from
the reaction of 2,4-Diiodo-6-[(2-morpholin-4-yl-ethyli-
mino)-methyl]-phenol and Zn(CH3COO)2Á2H2O. This study
reports crystal structure of 2,4-Diiodo-6-[(2-morpholin-4-
yl-ethylimino)-methyl]-phenolato-zinc(II) (Scheme 1).
˚
group P - 1 with the cell parameters a = 9.938(2) A,
˚
˚
b = 11.937(2) A, c = 14.527(3) A, a = 87.14(3)°, b =
3
˚
79.03(3)°, c = 76.20(3)°, V = 1565.1(5) A and Z = 2.
The central zinc(II) is four coordinate and bonds to two
nitrogen atoms and two oxygen atoms from two 3,5-diio-
dosalicylaldehyde-2- morpholinoethylamine Schiff bases.
The complex is linked into a column by weak intermo-
lecular interactions.
Keywords Crystal structure Á 3, 5-diiodosalicylaldehyde Á
2-morpholinoethylamine Á Zinc(II)
Introduction
Experimental
Zinc is an important element that is essential for life. Many
zinc(II) complexes have been prepared and structurally
The 3,5-diiodosalicylalidene was synthesized with sali-
cylaldehyde, KI and KIO3 [13]. The other chemicals
(reagent grade) used were commercially available. UV
spectra were recorded on a U-3000 Spectrophotometer. IR
spectra were recorded on a Nexus 870 FT-IR. The crystal
structure of the complex was determined using Enraf–
Nonius CAD-4 four-circle single crystal X-ray diffrac-
tometer instrument. Melting points were measured on a
Boetius micro melting point apparatus.
S.-P. Xu Á H.-L. Zhu
Key Laboratory of Anhui Educational Department,
Anhui University of Technology, Maanshan 243002,
People’s Republic of China
e-mail: XSP62@xznu.edu.cn
S.-P. Xu
School of Chemistry and Chemical Engineering,
Xuzhou Normal University, Xuzhou 221116,
People’s Republic of China
Synthesis of the Complex
P.-C. Lv Á R.-Q. Fang Á L. Shi Á H.-L. Zhu (&)
School of Life Sciences, Nanjing University, Nanjing 210093,
People’s Republic of China
For the preparation of the title complex, equimolar quanti-
ties (0.4 mmol) of 3,5-diiodo-salicylaldehyde and 2-mor-
pholinoethylamine along with 0.2 mmol of Zn(CH3COO)2Á
e-mail: zhuhl@nju.edu.cn
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J Chem Crystallogr (2009) 39:931–934
Scheme 1 Synthesis of the
complex
O
N
H
I
I
C
N
Zn
N
O
I
2
CHO
+ 2
H2N
N
Zn2+
O
+
O
OH
C
H
I
I
I
N
O
2H2O were dissolved in methanol (10 mL). The mixture
was stirred at room temperature for 30 min to give a clear
light yellow solution. After standing for 3 days at room
temperature, the precipitate was separated by filtration, the
title complex, 2,4-Diiodo-6-[(2-morpholin-4-yl-ethyli-
mino)-methyl]-phenol-zinc(II) was obtained, which was
recrystallized from acetonitrile to give yellow cubic crystals
after 3 days at room temperature. The complex was washed
three times with methanol, and dried in a vacuum desiccator
containing anhydrous CaCl2. The yield is 70%, m.p: 249–
250 °C. UV (k nm): 259, 397. Selected IR data (cm–1, KBr):
1630(s), 1446(s), 1218(s), 1113(s), 672(s).
Table 1 Experimental crystallographic data
Empirical formula
C26H30O4N4I4Zn
Formula weight
Temperature
1035.51
293(2) K
˚
0.71073 A
Wavelength
Crystal system
Space group
Triclinic
P - 1
˚
a = 9.938(2)A
Cell dimensions
˚
b = 11.937(2)A
˚
c = 14.527(3)A
a = 87.14(3)°
b = 79.03(3)°
c = 76.20(3)°
X-ray Crystal Structure Determination
3
˚
Volume
V = 1565.1(5) A
A single crystal of the title complex with dimensions
0.30 9 0.20 9 0.10 mm was chosen for X-ray diffraction
study. The data were collected with graphite monochro-
Z
2
Density (calculated)
Absorption coefficient
F000
2.197 Mg/m3
4.767 mm–1
976
˚
mated Mo Ka radiation (k = 0.71073 A) using x-2h scan
technique. The structure was solved using direct methods
and refined by full-matrix least-squares techniques. All non-
hydrogen atoms were assigned anisotropic displacement
parameters in the refinement. All hydrogen atoms were
added at calculated positions and refined using a riding
model. The structure was solved by direct methods using
program SHELXS-97 [14] and refined by fullmatrix least-
squares techniques on F2 with SHELXL-97 [15] (semiem-
pirical absorption corrections were applied using the
SADABS program). The crystal used for the diffraction
study showed no decomposition during data collection. The
crystal data and refinement data are listed in Table 1.
Selected bond lengths and bond angles are given in Table 2.
Crystal size
0.30 9 0.20 9 0.10 mm
1.43–26.00°
–11 B h B 12
–13 B k B 14
0 B l B 17
Theta range for data collection
Index ranges
Reflections collected
6509
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I [ 2 r(I)]
R indices (all data)
6131[R(int) = 0.0401]
6131/96/340
1.098
R1 = 0.0548, wR2 = 0.1513
R1 = 0.0806, wR2 = 0.1951
None
Extinction correction
Largest diff. peak and hole
Deposition number
-3
˚
0.999 and –1.007e. A
CCDC 675135
Results and Discussion
from two 3,5-diiodosalicylaldehyde-2-morpholinoethyla-
mine Schiff bases. Each Schiff base acts as a bidentate
ligand. The zinc atom is in a distorted tetrahedral environ-
ment with the N2–Zn–N4 angle [152.7(4)°] significantly
The title crystal structure consists of a mononuclear com-
plex (Fig. 1). The central zinc(II) atom is four coordinate
and bonds to two nitrogen atoms and two oxygen atoms
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J Chem Crystallogr (2009) 39:931–934
933
˚
Table 2 Selected bond lengths (A) and angles (°)
Table 3 The IÁÁÁI contracts for title comound
IÁÁÁI contracts
˚
Atoms
Length
Atoms
Length
d(IÁÁÁI) A
Zn–O(4)
1.957(7)
2.006(8)
Angles
Zn–O(2)
1.994(7)
2.021(9)
Angles
I(1)ÁÁÁI(4a)
I(1)ÁÁÁI(4b)
I(2)ÁÁÁI(3a)
I(2)ÁÁÁI(3c)
I(3)ÁÁÁI(2d)
I(3)ÁÁÁI(2c)
I(4)ÁÁÁI(1d)
I(4)ÁÁÁI(1b)
3.999
3.836
4.274
3.890
4.274
3.890
3.999
3.836
Zn–N(2)
Zn–N(4)
Atoms
Atoms
O(4)–Zn–O(2)
O(4)–Zn–N(4)
O(2)–Zn–N(2)
C(13)–O(2)–Zn
C(7)–N(2)–Zn
C(26)–O(4)–Zn
105.0(3)
94.2(3)
O(4)–Zn–N(2)
O(2)–Zn–N(4)
N(2)–Zn–N(4)
C(19)–N(4)–Zn
C(6)–N(2)–Zn
C(20)–N(4)–Zn
102.9(3)
101.6(3)
152.7(4)
122.0(6)
122.1(7)
120.6(7)
94.4(3)
127.3(7)
121.3(7)
127.7(6)
Symmetry code: (a) x, y – 1, z; (b) 2 – x, 1 – y, 2 – z; (c) 2 - x,
2 – y, 1 - z; (d) x, y ? 1, z
˚
˚
N(2.006 A 2.021 A) bond lengths are in normal range. In
the crystal structure of the complex the atoms of the phenyl
ring plane A(C8/C9/C10/C11/C12/C13) and the chelate
ring formed by the same ligand plane B (O2/Zn/N2/C7/
C13/C8) are nearly coplanar with a dihedral angle of 4.2°.
This is true of the corresponding planes in the other ligand,
phenyl ring plane C (C21/C22/C23/C24/C25/C26) and
chelate ring plane D (O4/Zn/N4/C20/C21/C26), which have
a dihedral angle of 2.8°. If the two chelate planes, planes B
and D, are compared the dihedral angle is 80.2°. In the title
crystal structure, the 2-morpholinoethylamine groups bon-
ded to N2 and N4 are skewed, as indicated by the torsion
angles separately being N2–C6–C5–N1 = 111.7° and
N4–C19–C18–N3 = 110.5°. The intermolecular IÁÁÁI con-
Fig. 1 A view of the zinc complex, showing 30% probability
displacement ellipsoids (arbitrary spheres for the H atoms)
˚
tracts are between 3.836 and 4.274 A (Table 3), which
larger than the other angles about zinc. It is probably due
to the short C=N bond and steric interactions between
connect the molecules to form an three-dimentional
network (Figure 2).
˚
the morpholines. The Zn–O(1.957 A 1.994 A) and Zn–
˚
Fig. 2 The packing structure of the zinc complex along the c-axis, showing the formation of column by weak intermolecular IÁÁÁI interactions
123

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J Chem Crystallogr (2009) 39:931–934
Acknowledgments The work was co-financed by grant (Project
30772627) from National Natural Science Foundation of China, and
by grant (Project 070416274X) from Anhui Natural Science Foun-
dation, Anhui Province, China.
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