Coordination compound of cadmium acetate with the condensation product of salicylaldehyde and 3-(pyridin-2-yl)-5-(2-aminophenyl)-1H-1,2,4-triazole

Article abstract of DOI:10.1134/S1070328411010052

The cadmium(II) complex with the condensation product of salicylaldehyde and 3-(pyridine-2-yl)-5-(2-aminophenyl)-1H-1,2,4-triazole (H₂L), Cd₂(H₂L)₂(OAc)₄ ? 3EtOH, is synthesized. Its crystal structure

Full text of DOI:10.1134/S1070328411010052

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 2, pp. 117–121. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.N. Gusev, V.F. Shul’gin, M.A. Kiskin, I.L. Eremenko, 2011, published in Koordinatsionnaya Khimiya, 2011, Vol. 37, No. 2, pp. 119–123.
Coordination Compound of Cadmium Acetate
with the Condensation Product of Salicylaldehyde
and 3ꢀ(Pyridinꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1Hꢀ1,2,4ꢀtriazole
A. N. Guseva, V. F. Shul’gina, *, M. A. Kiskinb, and I. L. Eremenkob
a National Tavrida V. Vernadsky University, ul. Akad. Vernadsky 4, Simferopol, Ukraine
b Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
* Eꢀmail: vshul@crimea.edu
Received June 21, 2010
Abstract—The cadmium(II) complex with the condensation product of salicylaldehyde and 3ꢀ(pyridineꢀ2ꢀ
yl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1Hꢀ1,2,4ꢀtriazole (H2L), Cd2(H2L)2(OAc)4 · 3EtOH, is synthesized. Its crystal
...
structure is studied by Xꢀray diffraction analysis. In the centrosymmetric binuclear complex (Cd Cd
3.938(1) Å), the Cd atoms are bonded by two tridentate bridging acetate anions. Two other acetate anions are
terminal and coordinated by the monodentate mode. The coordination polyhedron of the Cd atom is a disꢀ
torted octahedron. The triazole ligands are bonded to the cadmium cations through the N atoms of the pyriꢀ
dine cycle and triazole ring.
DOI: 10.1134/S1070328411010052
Polyfunctional derivatives of 1,2,4ꢀtriazole form a laldehyde and 3ꢀ(pyridineꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ
new class of organic ligands. A variety of coordination 1Hꢀ1,2,4ꢀtriazole, Cd2(H2L)2(OAc)4
modes makes it possible to obtain related complexes
⋅
3EtOH (II).
interesting from the theoretical and practical point
EXPERIMENTAL
Complex II was synthesized in air in purified 96%
ethanol. Salicylaldehyde and Cd(OAc)2 2H2O
(reagent grade) were used. 3ꢀ(Pyridinꢀ2ꢀyl)ꢀ5ꢀ(2ꢀ
aminophenyl)ꢀ1Hꢀ1,2,4ꢀtriazole was synthesized
according to a procedure described earlier [7].
IR spectra were recorded in the range from 4000 to
400 cm–1 on a Nicolet Nexus 470 FTIR spectrophoꢀ
tometer using a standard molding procedure of the
sample with KBr.
NMR spectra were detected on a Bruker VXRꢀ400
spectrometer (400 MHz) using Me4Si as an internal
standard and DMSOꢀd6 as a solvent.
of views due to their unique magnetic, optical,
and biological properties [1–5]. The zinc complex
with 3ꢀ(pyridineꢀ2ꢀyl)ꢀ5ꢀ(2ꢀsalicylideneiminopheꢀ
⋅
nyl)ꢀ1Hꢀ1,2,4ꢀtriazole (
product of salicylaldehyde and 3ꢀ(pyridineꢀ2ꢀyl)ꢀ5ꢀ
(2ꢀaminophenyl)ꢀ1Hꢀ1,2,4ꢀtriazole H2L), has
I), which is the condensation
(
recently been described. This compound exhibits high
photoꢀ and electroluminescence activities [5].
According to the Xꢀray diffraction data, complex I has
a binuclear structure, and the zinc cations are coordiꢀ
nated by two bridging ligands existing in the doubly
coordinated form [6].
N
The cadmium content was calculated from the data
of trilonometric titration after the thermal decomposiꢀ
tion of a weighed sample. The nitrogen content was
determined by the Dumas micromethod.
N
N
N
N
H
Zn
O
O
Synthesis of H2L
. Salicylaldehyde (0.512 g,
Zn
H
4.2 mmol) was added with stirring to a solution of
3ꢀ(pyridineꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1Hꢀ1,2,4ꢀtriaꢀ
zole (0.948 g, 4 mmol) in EtOH (20 ml) heated to 60–
N
N
N
N
N
70 С. The reaction mixture was stirred on heating with
°
a reflux condenser for 1 h. The solution was cooled,
and the precipitate that formed was filtered off,
(I)
In this work we present the results of studying the washed with cool ethanol, and dried in air. Colorless
coordination compound of cadmium acetate with the crystals with mp = 237 were obtained. The yield was
°
С
molecular form of the condensation product of salicyꢀ 1.18 g (87%).
117

118
GUSEV et al.
Table 1. Selected crystallographic data and experimental characterꢀ
istics for complex II
in EtOH (10 ml), and the mixture was stirred on heating for
2 h. A precipitate that formed was left to stay overnight under
the mother liquor, then filtered off, washed with ethanol,
and dried in air. The yield of the complex was 1.4 g (75%).
Recrystallization from 96% ethanol gave light yellow crystals
of prismatic habitus suitable for Xꢀray diffraction analysis.
Parameter
Molecular weight
Value
1281.92
150(2)
Temperature, K
Crystal size, mm
Crystal system
Space group
For C54H60Cd2N10O13
0.40
Monoclinic
2/
×
0.20 0.20
×
anal. calcd. (%):
Found (%):
Cd, 17.54;
Cd, 17.22;
N, 10.92.
N, 11.18.
C
c
IR,
ν
, cm–1 : 3300
ν
(NH), 3060
ν
(С–Нarom), 1630
a
,
Å
Å
Å
26.1536(10)
21.4975(8)
10.0212(4)
97.3050(10)
5588.6(4)
4
ν
(C–N), 1548 νas(СОО–), 1420 νs(СОО–), 1284
b,
ν
(Сarom–O)
.
Xꢀray diffraction analysis. An experimental array of
c,
reflection was obtained by the standard method [8–
10] on a Bruker SMART APEX II automated diffracꢀ
tometer equipped with a CCD detector and a monoꢀ
β
, deg
V
,
Å3
chromatic radiation source (Mo
K
radiation,
λ
=
α
0.71073 Å). The structure of complex II was solved by
a direct method and refined in the fullꢀmatrix anisoꢀ
tropic approximation for all nonꢀhydrogen atoms.
Hydrogen atoms of the carbonꢀcontaining ligands
were geometrically generated and refined in the riding
model. The calculations were performed using the
SHELXꢀ97 program package. The crystallographic
parameters and Xꢀray diffraction experimental
parameters are given in Table 1. Selected bond lengths
and bond angles are listed in Table 2. The complete set
of Xꢀray diffraction data was deposited with the Camꢀ
bridge Crystallographic Data Centre (no. 783744;
Z
ρcalcd, g/cm3
, cm–1
(000)
, deg
1.524
μ
8.33
F
2616
θ
1.23–30.61
Ranges of indices
37
≤
h
≤
33, –30
–14
22493
int = 0.0208)
6942
≤
k 30,
≤
≤
l 11
≤
Total number of reflections
deposit@ccdc.cam.ac.uk;
ac.uk/data_request/cif).
http://www.ccdc.cam.
Number of independent reflections
8343 (R
Number of reflections with
Tmin Tmax
I
≥
2σ(I)
RESULTS AND DISCUSSION
/
0.7317/0.8511
370
The study of the condensation product of salicylaꢀ
ldehyde with 3ꢀ(pyridineꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ
1Hꢀ1,2,4ꢀtrLiazole and the related complexes showed
that the compound can exist in two isomeric forms:
linear azomethine (
dolizine (
Number of refined parameters
Goodnessꢀofꢀfit
1.026
R
R
(I
≥
2
σ
(
I
))
R
1 = 0.0376, wR2 = 0.1283
1 = 0.0471. wR2 = 0.1441
–1.203/1.813
A
) and cyclic dihydrotriazainꢀ
B)
(all data
)
R
Δρmin/Δ
ρmax, е
Å–3
N
N
N
N
1H NMR,
, ppm: 10.1 s (br, OH), 8.65 d (1Harom),
δ
N
N
N
N
N
NH
H
8.12 d (1Harom), 7.90 dt (1Harom), 7.80 d (1Harom),
7.40 m (2Harom), 7.20 m (2Harom + (C2–H)), 6.95 m
(2Hatom + (N–H)), 6.85 t (1Harom), 6.80 t (1Harom). IR,
HO
OH
ν
, cm–1: 3380
(С–N), 1292
ν
(OH), 3270
(С–O).
ν
(NH), 3056 ν(С–Н), 1629
ν
ν
(
A)
(B)
According to the data of 1H NMR spectroscopy, in
solutions compound H2L exists in the cyclic form. The
spectrum contains no signal of the hydrogen atom of
the triazole cycle, which usually appears at 13–
Synthesis of diꢀ
yphenyl)ꢀ2ꢀ(2'ꢀpyridyl)ꢀ7,8ꢀbenzoꢀ6,5ꢀdihydroꢀ1,3,6ꢀtriazꢀ
aindolizine]dicadmium
Cd2(H2L)2(OAc)4 · 3EtOH (II)
µ
ꢀacetatoꢀdiacetatoꢀbis[5ꢀ(2'ꢀhydroxꢀ
(solvate
with
ethanol),
2H2O (0.8 g,
.
Cd(OAc)2
⋅
3 mmol) was added to a suspension of H2L (1.05 g, 3 mmol) 14 ppm, but the signal of the H atom of the secondary
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COORDINATION COMPOUND OF CADMIUM ACETATE
119
Table 2. Selected bond lengths and bond angles for complex II*
Bond
Cd(1)–O(4)
d
,
Å
Bond
N(3)–N(4)
d, Å
2.2497(19)
2.279(2)
2.307(2)
2.328(2)
2.3717(18)
2.587(2)
1.338(3)
1.349(3)
1.340(3)
1.367(3)
1.322(3)
1.352(2)
1.349(3)
1.470(3)
1.367(3)
1.459(3)
1.257(3)
1.264(3)
1.242(4)
1.283(3)
1.354(3)
Cd(1)–O(1)
Cd(1)–N(1)
Cd(1)–O(2)#1
Cd(1)–N(2)
Cd(1)–O(2)
N(1)–C(5)
N(4)–C(11)
N(4)–C(22)
N(5)–C(21)
N(5)–C(22)
O(1)–C(1)
O(2)–C(1)
O(3)–C(3)
O(4)–C(3)
O(5)–C(28)
N(1)–C(9)
N(2)–C(11)
N(2)–C(10)
N(3)–C(10)
Angle
ω
, deg
Angle
ω
, deg
O(4)Cd(1)O(1)
O(4)Cd(1)N(1)
O(1)Cd(1)N(1)
O(4)Cd(1)O(2)#1
O(1)Cd(1)O(2)#1
N(1)Cd(1)O(2)#1
O(4)Cd(1)N(2)
O(1)Cd(1)N(2)
N(1)Cd(1)N(2)
O(2)#1Cd(1)N(2)
O(4)Cd(1)O(2)
O(1)Cd(1)O(2)
N(1)Cd(1)O(2)
O(2)#1Cd(1)O(2)
N(2)Cd(1)O(2)
Cd(1)O(2)#1Cd(1)#1
C(5)N(1)C(9)
86.59(7)
125.63(7)
147.17(7)
103.82(7)
92.80(7)
85.81(7)
99.15(7)
98.32(7)
72.73(7)
155.00(7)
138.77(7)
53.43(7)
95.41(7)
72.35(8)
96.57(7)
106.37(8)
C(5)N(1)Cd(1)
C(9)N(1)Cd(1)
C(11)N(2)C(10)
C(11)N(2)Cd(1)
C(10)N(2)Cd(1)
C(10)N(3)N(4)
C(11)N(4)N(3)
C(11)N(4)C(18)
N(3)N(4)C(18)
C(17)N(5)C(18)
O(1)C(1)O(2)
O(1)C(1)C(2)
O(2)C(1)C(2)
O(3)C(3)O(4)
O(3)C(3)C(4)
O(4)C(3)C(4)
123.28(17)
117.70(15)
103.14(19)
144.93(15)
111.62(14)
101.85(18)
111.59(18)
127.71(19)
120.68(18)
126.1(2)
122.0(3)
118.2(3)
119.8(3)
121.8(2)
121.1(3)
117.1(3)
118.8(2)
#1
* Symmetry transformations of equivalent atoms: –x, y, –z + 3/2.
amine is observed at 6.95 ppm. In addition, the singlet (Fig. 1, Table 2) coordinated by the 32ꢀс type [12]. Two
signal of the C(2)–H proton of dihydrotriazaindolizꢀ more acetate anions are coordinated according to the
ine is observed at 7.2 ppm. This region is characteristic monodentate type (Cd(1)–O(4) 2.2497(19) Å).
of the related heterocyclic systems [11].
The heterocyclic ligand H2L is coordinated by the
bidentate mode and bound to the cadmium cation
through the N(1) atom of the pyridine cycle and the
N(2) atom of the triazole cycle, which is not characꢀ
teristic of nonfunctional triazoles. The Cd(1)–N(2)
bond (2.3717(18) Å) is substantially longer than
Cd(1)–N(1) (2.307(2) Å).
The dihydrotriazaindolizine form of the ligand was
found for the crystal structure of its complex with cadꢀ
mium(II) acetate. According to the Xꢀray diffraction
data, the complex is binuclear and crystallizes as a solꢀ
vate with three ethanol molecules. The molecule of
the complex is centrosymmetric. The cadmium atoms
(
Cd⋅⋅⋅Cd 3.938(1) Å) are bonded by two tridentate
The cadmium ion coordinates four oxygen atoms
bridging acetate anions (Cd(1)–O(1) 2.279(2), of the acetate anions and two nitrogen atoms of triazꢀ
Cd(1)–O(2)#1 2.329(2), Cd(1)–O(2) 2.587(2) Å) ole arranged at the vertices of the strongly distorted
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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120
GUSEV et al.
C(21)
C(20)
C(22)
C(23)
C(24)
C(7)
C(8)
O(5)
N(3)
C(19)
C(6)
C(9)
C(5)
C(18)
N(5)
O(2)
Cd(1)#1
C(10)
N(4)
C(11)
N(1)
C(2)
N(2)
C(1)
C(17)
C(12)
Cd(1)
O(2)#1
C(13)
O(1)
O(3)
C(16)
O(4)
C(4)
C(15)
C(14)
C(3)
Fig. 1. Molecular structure of complex II (hydrogen atoms are omitted, thermal ellipsoids at 30% probability).
octahedron. The fourꢀmembered Cd2O2 cycle is asymꢀ
metric and noticeably bent. The dihedral angle
between the О(2)–Сd(1)–O(2)#1 and О(2)–Сd(1)#1–
One of the outerꢀsphere ethanol molecules is disorꢀ
dered. The crystalline lattice is stabilized by the system
of intermolecular hydrogen bonds (Table 3) and nonꢀ
valent interactions between the conjugated nitrogenꢀ
containing heterocycles of the adjacent molecules of
the complex, whose planes are almost parallel and lie
O(2)#1 planes is 14.8
72.35(8)
almost in the same plane, and the 2ꢀhydroxyphenyl
fragment is turned relative to the pyridyl ring by 89.1
°
, and the OCdO bond angle is
°
. The triazole, phenyl, and pyridyl cycles lie
at a distance of ~3.5
Å
( ꢀstacking interactions)
π
°
(Fig. 2).
(Fig. 1). The N(3)–N(4) bond (1.352(3) Å) is noticeꢀ
ably shorter than the standard nitrogen–nitrogen
ordinary bond (1.451 Å) [13], which can be due to
double bond delocalization in the triazole fragment.
The C(18)–N(4) bond (1.470(3) Å) is appreciably
elongated compared to the standard value. The other
bonds in the organic ligands have standard values.
Thus, the studies performed show that the reaction
of 3ꢀ(pyridineꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1Hꢀ1,2,4ꢀ
triazole with salicylaldehyde affords dihydroꢀ1,3,6ꢀ
triazaindolizine heterocyclic system, which is retained
upon coordination by the cadmium cation. The reacꢀ
tion with zinc acetate results in the decomposition of
the heterocycle and coordination of functionalized
Table 3. Hydrogen bond geometry in structure II
Distance
, Å
Contact D–H⋅⋅⋅
A
Angle DHA, deg
Coordinates of atom A
D–H
H
⋅⋅⋅
A
D⋅⋅⋅A
N(5)–H(5)⋅⋅⋅O(4)
O(5) –H(5 ⋅⋅⋅O(3)
0.88
0.84
2.14
1.81
3.013(3)
2.645(3)
2.061(5)
2.893(5)
172
179
–x + 1/2, –y + 1/2, –z + 2
B)
x,
x,
x,
y,
y,
y,
z
z
z
+ 1
O(5)⋅⋅⋅O(2S)*
O(4)⋅⋅⋅O(1S)*
* Hydrogen atoms of ethanol molecules were not found.
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COORDINATION COMPOUND OF CADMIUM ACETATE
121
Cd(1)
Cd(1)
Cd(1)
Cd(1)
Fig. 2. Fragment of the molecular packing of crystalline complex II
.
Vernadskogo, Ser. Biologiya I Khimiya, 2009. vol. 22,
no. 61, p. 154.
triazole in the doubly deprotonated azomethine form
(complex I).
7. Baldwin, J., Pat. 4.198.513 USA. Assignee: Merck &
Co., Inc. Rahway (NJ, USA), 1980.
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