Microwave synthesis and crystal structure of 2-hydroxy-3-iodobenzaldehyde- copper (II)

Article abstract of DOI:10.1007/s10870-010-9920-6

One new complex, 2-hydroxy-3-iodo-benzaldehyde-copper (II) has been designed and microwave synthesized. The structure was determined by UV, IR and single X-ray crystallography study. The title complex C₁₄H ₈CuI₂O₄ crystallizes in the orthorhombic space group Pna21 with the cell parameters a = 12.7897(12) A, b = 6.1132(8) A, c = 19.5114(18) A, V = 1525.5(3) A³ and Z = 4. The central copper (II) is four-coordinated by four oxygen atoms from two 3-iodosalicylaldehyde. The complex is linked into rhombic crystals by weak intermolecular interactions. Springer Science+Business Media, LLC 2010.

Full text of DOI:10.1007/s10870-010-9920-6

J Chem Crystallogr (2011) 41:82–84
DOI 10.1007/s10870-010-9920-6
COMMUNICATION
Microwave Synthesis and Crystal Structure of 2-Hydroxy-3-iodo-
benzaldehyde-copper (II)
Suo-Ping Xu
Ban-Feng Ruan
•
Xiao-Liang Wang
Hai-Liang Zhu
•
Jian-Feng Tang
•
•
Received: 21 March 2010 / Accepted: 28 November 2010 / Published online: 14 December 2010
Ó Springer Science+Business Media, LLC 2010
Abstract One new complex, 2-hydroxy-3-iodo-benzalde-
hyde-copper (II) has been designed and microwave synthe-
sized. The structure was determined by UV, IR and single
X-ray crystallography study. The title complex C H CuI O
2-hydroxy-3-iodo-benzaldehyde-copper (II), is obtained
from 2-hydroxy-3-iodo-benzaldehyde and Cu(CH COO) Á
3
2
H O by microwave synthesis. The study will report crystal
2
structure of 2-hydroxy-3-iodo-benzaldehyde-copper (II)
(Scheme 1).
14
8
2 4
crystallizes in the orthorhombic space group Pna2 with the
1
˚
cell parameters a = 12.7897(12) A, b = 6.1132(8) A, c =
˚
3
˚ ˚
9.5114(18) A, V = 1525.5(3) A and Z = 4. The central
1
copper (II) is four-coordinated by four oxygen atoms from
two 3-iodosalicylaldehyde. The complex is linked into
rhombic crystals by weak intermolecular interactions.
Experimental
The 2-hydroxy-3-iodo-benzaldehyde was synthesized with
salicylaldehyde, KI and KIO [9]. The other chemicals
3
Keywords Crystal structure Á 3-iodosalicylaldehyde Á
Microwave synthesis Á Copper (II)
(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 complex was determined using SMART 1000
CCD diffractometer instrument. Melting points were
measured on a Boetius micro melting point apparatus.
Introduction
Copper is an important life-required element. Many copper
(
II) complexes were prepared and structurally determined
Synthesis of the Complex
by single X-ray analysis [1–4]. Copper element exists in
some native enzymes and is required by creatures. Due to
their important relevant biological behaviors, many copper
complexes with Schiff base have been reported in recent
years [5–8]. However, to our knowledge, there are no
structure reports about copper (II) complexes with
Copper (II) acetate and two equivalent molar of 2-hydroxy-
3-iodo-benzaldehyde were mixed together and microwave
radiated 3 min in 250 W. Then, the breen powder was
dissolved in DMF and stood still in air for 2 weeks. Large
rhombic crystals were precipitated. They were filtered and
washed with ethanol and dried in a vacuum desiccator
2
-hydroxy-3-iodo-benzaldehyde. In this paper, the complex,
containing anhydrous CaCl . The yield is 75%, m.p:
2
3
48–350 °C. UV (k nm): 256, 410. Selected IR data
S.-P. Xu Á X.-L. Wang Á J.-F. Tang Á B.-F. Ruan Á
H.-L. Zhu (&)
State Key Laboratory of Pharmaceutical Biotechnology,
Nanjing University, Nanjing 210093, China
e-mail: zhuhl@nju.edu.cn
-1
(
cm , KBr): 3443 (w), 1591 (s), 1501 (m), 1422 (s), 1403
s), 1329 (m), 1216 (m), 750 (m), 674 (m).
(
X-ray Crystal Structure Determinations
S.-P. Xu
School of Chemistry and Chemical Engineering,
Xuzhou Normal University, Xuzhou 221116, China
A single crystal of the title complex with dimensions
0.17 9 0.15 9 0.15 mm was chosen for X-ray diffraction
1
23

J Chem Crystallogr (2011) 41:82–84
83
O
I
Table 2 Selected bond lengths (A) and angles (°)
˚
O
microwave
50W 3min
O
2
+
Cu(CH COO) ·H O
Cu
3
2
2
O
OH
2
O
Atoms
Length
Atoms
Length
I
I
Cu–O4
Cu–O1
I1–C4
1.891(9)
1.946(9)
2.110(14)
1.268(18)
1.237(15)
Cu–O2
Cu–O3
I2–C11
O2–C3
O4–C10
1.896(10)
1.953(9)
Scheme 1 Synthesis of the complex
2.110(14)
1.307(16)
1.288(15)
O1–C1
O3–C8
Table 1 Experimental crystallographic data
Empirical formula
C
14 8
H CuI
2
O
4
Atoms
Angles
Atoms
Angles
Formula weight
Temperature
557.54
O4–Cu–O2
O2–Cu–O1
O2–Cu–O3
C1–O1–Cu
C8–O3–Cu
179.5(5)
92.7(4)
O4–Cu–O1
O4–Cu–O3
O1–Cu–O3
C3–O2–Cu
C10–O4–Cu
86.8(4)
93.0(4)
298(2) K
˚
Wavelength
0.71073 A
Orthorhombic
Pna2
87.5(4)
179.5(5)
128.4(9)
126.3(8)
Crystal system
Space group
126.0(9)
125.6(8)
1
˚
a = 12.7897(12) A
Cell dimensions
˚
b = 6.1132(8) A
˚
c = 19.5114(18) A
3
˚
V = 1525.5(3) A
Volume
Z
4
3
Density(calculated)
Absorption coefficient
2.428 Mg/m
-
1
5.490 mm
1036
F
000
Crystal size
0.17 9 0.15 9 0.15 mm
2.09–27.00°
Theta range for data collection
Index ranges
-16 B h B 15, -3 B k B 7,
24 B l B 23
-
Reflections collected
7855
Independent reflections
Data/restraints/parameters
3252 [R(int) = 0.0464]
3252/1/190
Fig. 1 A view of the title complex, showing 30% probability
displacement ellipsoids (arbitrary spheres for the H atoms)
2
Goodness-of-fit on F
1.031
Final R indices [I [ 2 r(I)]
R indices(all data)
R1 = 0.0532, wR2 = 0.1269
R1 = 0.0855, wR2 = 0.1506
None
Results and Discussion
Extinction correction
Largest diff. peak and hole
Deposition number
The title crystal structure consists of mononuclear complex
-3
˚
1.625 and -1.049 e A
(
Fig. 1). The central copper (II) atom is four-coordinated
by four oxygen atoms from two 3-iodosalicylaldehyde. The
-iodosalicylaldehyde is bidentate ligand. The copper atom
CCDC
3
is in a distorted tetrahedral environment. The Cu–O bonds
with the lengths of 1.891(9), 1.896(10), 1.946(9) and
˚
1.953(9) A are in normal range [11–13]. In the crystal
study. The data were collected with graphite monochro-
˚
mated Mo Ka radiation (k = 0.71073 A) using x-2h scan
structure of complex, the atoms of phenyl ring plane A
(C2/C3/C4/C5/C6/C7) and plane B (O2/Cu/O1/C1/C2/C3),
display an almost coplanar configuration with the dihedral
angle being 3.8(4)°. The plane B (O2/Cu/O1/C1/C2/C3)
and plane C (O4/Cu/O3/C8/C9/C10) display coplanar
configuration with the dihedral angle being 0.2(1)°. The
plane C (O4/Cu/O3/C8/C9/C10) and plane D (C9/C10/
C11/C12/C13/C14) display an almost coplanar configura-
tion with the dihedral angle being 5.3(2)°. In the title
crystal structure indicated by the torsion angles sepa-
rately being O4–Cu–O1–C1 = 174.69(3)°, O2–Cu–O1–
C1 = -5.4(6)° and O3–Cu–O1–C1 = -117.0(4)°. X-ray
technique. The structure was solved using direct methods
and refined by full-matrix least-squares techniques. All
non-hydrogen atoms were assigned anisotropic displace-
ment parameters in the refinement. All hydrogen atoms
were added at calculated positions and refined using a
2
riding model. The structures were refined on F using
SHELXTL-97 10]. 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.
123

8
4
J Chem Crystallogr (2011) 41:82–84
Acknowledgments The work was co-financed by grants (Projects
3
0772627) from National Natural Science Foundation of China and
Projects 09KJD150005) from Natural Science Foundation of Jiangsu
(
Province, China.
References
1
2
. You ZL, Zhu HL (2004) Z Kristallogr 630(15):2754–2760
. Roth A, Spielberg ET, Plass W (2007) Inorg Chem 46(11):
4
362–4364
3
4
5
6
. Xu S.-P, Shi L, Lv P.-C, Fang R.-Q, Zhu H.-L (2009) J Coord
Chem 62(12):2048–2057
. Liu J, Zhang T.-X, Lu T.-B, Qu L.-H, Zhou H, Zhang Q.-L, Ji
L.-N (2002) J Inorg Biochem 91(1):269–276
. Li C.-H, Wang Q, Xu Y.-Q, Hu C.-W (2008) Chin J Struct Chem
2
7(2):187–190
. Shi L, Ge H.-M, Tan S.-H, Li H.-Q, Song Y.-C, Zhu H.-L, Tan
R.-X (2007) Eur J Med Chem 42:558–564
Fig. 2 The packing structure of complex along the b-axis, showing
the formation of column by weak I_I intermolecular interactions
7. Peng L.-L, Ye J.-C (2004) J Hubei Norm Univ (Nat Sci) 24(4):
6–88
8
8
. Xu S.-P, Shi L, Lv P.-C, Fang R.-Q, Zhu H.-L (2009) J Coord
Chem 62(12):2048–2057
analysis reveals that intermolecular hydrogen bond
˚
9. Xu S.-P, Zhu G.-Z, Fang R.-Q, Li X.-L, Zhu H.-L (2009) Chin J
Struct Chem 28(1):87–93
0. Sheldrick GM (2008) Acta Cryst A 64:112–122
1. Akitsu T, Einaga Y (2004) Acta Crystallogr C60:m640–m642
2. Akitsu T, Einaga Y (2004) Acta Crystallogr E60:m1605–m1607
C(1)-H(1)_O(3) (the bond length is 3.493(2) A and the
1
1
1
bond angle is 171.0(7)°) and molecules participate to form
weak intermolecular interactions, which join the constitu-
ents into a three-dimensional network structure (Fig. 2).
13. Akitsu T, Einaga Y (2004) Acta Crystallogr E60:m1552–m1554
1
23