The reaction of silver(I) nitrate with 5-phenyl-2-(2′-pyridyl)-7,8- benzo-6,5-dihydro-1,3,6-triazaindolizine

Article abstract of DOI:10.1134/S1070328411080033

The complex of silver(I) with the condensation product of benzaldehyde and 3-(pyridin-2-yl)-5-(2-aminophenyl)-1H-1,2,4-triazole (L), [AgL ₂]NO₃ (I), was synthesized. The reaction of L with silver(I) nitrate was found to afford 2-(2′-

Full text of DOI:10.1134/S1070328411080033

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 8, pp. 589–593. © 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. 8, pp. 589–593.
The Reaction of Silver(I) Nitrate with 5ꢀPhenylꢀ2ꢀ(2'ꢀPyridyl)ꢀ
7,8ꢀBenzoꢀ6,5ꢀDihydroꢀ1,3,6ꢀTriazaindolizine
A. N. Guseva, V. F. Shul’gina, *, M. A. Kiskinb, and I. L. Eremenkob
a Taurida National Vernadsky University, ul. Yaltinskaya 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 November 15, 2010
Abstract—The complex of silver(I) with the condensation product of benzaldehyde and 3ꢀ(pyridinꢀ2ꢀyl)ꢀ5ꢀ
(2ꢀaminophenyl)ꢀ1
nitrate was found to afford 2ꢀ(2'ꢀpyridyl)ꢀ1,4ꢀdihydroꢀ
Hꢀ1,2,4ꢀtriazole (L), [AgL2]NO3 (I), was synthesized. The reaction of L with silver(I)
5
Hꢀ1,3,4ꢀbenzotriazepinꢀ5ꢀone along with complex
I. The compounds synthesized were characterized by Xꢀray diffraction analysis.
DOI: 10.1134/S1070328411080033
1,2,4ꢀTriazole derivatives represent an interesting
class of organic ligands used for the synthesis of variꢀ was added with stirring to a solution of 3ꢀ(pyridinꢀ2ꢀ
Synthesis of L. Benzaldehyde (445 mg, 4.2 mmol)
ous coordination compounds, which evoke increased yl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1
interest as novel materials, first of all, magnetic and 4 mmol) in 96% ethanol (20 ml) heated to 60–70
Hꢀ1,2,4ꢀtriazole (948 mg,
°С.
optical materials [1, 2]. The variation of substituents in The reaction mixture was stirred on heating with a
the triazole ring makes it possible to change their spaꢀ reflux condenser for 1 h. The solution was cooled, and
tial and electronic structures in a wide range, attaining the precipitate formed was filtered off, washed with
the improvement of the physicochemical characterisꢀ cold ethanol, and dried in air. Colorless crystals were
tics. The coordination compounds of zinc and cadꢀ obtained. The yield was 988 mg (76%), mp = 216
mium with the condensation product of salicylaldeꢀ
hyde and 3ꢀ(pyridinꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1
°
C.
1H NMR,
δ, ppm: 8.62 d (1Harom), 8.07 d (1Harom),
Hꢀ
7.89 dt (1Harom), 7.79 d (1Harom), 7.69 s (1Harom),
7.44–7.36 m (5Harom + (C2–H), 7.29 dt (1Harom),
6.99 d (N–H), 6.92 d (1Harom), 6.86 t (1Harom).
1,2,4ꢀtriazole exhibiting intense photoꢀ and electroluꢀ
minescence have been described recently [3]. It was
shown that, depending on the complexing metal, the
IR,
(N–С–N), 1528, 1480.
Synthesis of bis[5ꢀphenylꢀ2ꢀ(2'ꢀpyridiyl)ꢀ7,8ꢀ
ν ν(NH), 3034 ν(С–Н), 1624
, cm–1: 3296
ligand can exist in two forms: linear azomethine (А)
ν
and cyclic dihydrotriazaindolizine (В) forms [4]
benzoꢀ6,5ꢀdihydroꢀ1,3,6ꢀtriazaindolizine]silver(I) nitꢀ
rate, [AgL2]NO3 (I). Silver nitrate (253 mg, 1.5 mmol)
was added to a suspension of L (975 mg, 3 mmol) in
MeOH (10 ml), and the mixture was stirred for 2 h on
heating with a reflux condenser. The resulting solution
was evaporated to half a volume. The precipitate
formed was left overnight under the mother liquor,
then filtered off, washed with methanol, and dried in
N
N N
N
N
N
N N
N
H
H
NH
OH
HO
(A)
(B)
air. The yield of complex I was 836 mg (68%).
In the present work we describe the results of studyꢀ
ing the reaction of silver(I) nitrate with the molecular
form of the condensation product of benzaldehyde
For C40H32N11O3Ag
anal. calcd., %: C, 56.54;
H, 3.90;
H, 4.03;
N, 18.78.
and 3ꢀ(pyridinꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1
Hꢀ1,2,4ꢀ
Found, %:
C, 56.32;
N, 18.51.
triazole (ligand ).
L
IR,
(N–C–N), 1550, 1500, 1392, 1308.
Synthesis of 2ꢀ(2'ꢀpyridyl)ꢀ1,4ꢀdihydroꢀ5
triazole was synthesized according to a described proꢀ benzotriazepinꢀ5ꢀone (II). A methanolic solution
cedure [5]. obtained in the synthesis of was evaporated to dryꢀ
ν
, cm–1: 3262
ν
(NH), 3060
ν
(C–Harom), 1622
EXPERIMENTAL
3ꢀ(Pyridinꢀ2ꢀyl)ꢀ5ꢀ(2ꢀaminophenyl)ꢀ1
ν
Hꢀ1,2,4ꢀ
Hꢀ1,3,4ꢀ
I
589

590
GUSEV et al.
Selected crystallographic data and characteristics of Xꢀray diffraction experiment for compounds
I
and II
Value
Parameter
I
II
Formula
C40H32AgN11O3
822.64
C13H10N4O
238.25
Molecular weight
Crystal size, mm
Temperature, K
Crystal system
0.30
×
0.30
×
0.15
0.30
×
0.10
150(2)
Monoclinic
21/
× 0.10
173(2)
Triclinic
Space group
P
n
P1
Cell parameters:
a
, Å
, Å
9.8983(7)
11.9763(11)
5.4108(5)
16.8193(15)
90
b
13.3266(9)
15.2977(11)
66.656(1)
80.081(1)
70.051(1)
1740.0(2)
2
c
, Å
, deg
, deg
, deg
, Å3
α
β
96.933(2)
90
γ
V
1081.94(17)
4
Z
ρcalcd, g/cm3
1.570
1.463
μ
, cm–1
63.8
9.9
F(000)
840
496
θ
Range, deg
1.45–28.44
1.98–30.62
Ranges of indices
13
≤
h
≤
13, –17
≤
k
≤
17, –20
≤
l
≤
20 –17
≤
h
≤
17, –7 7, –24
≤
k
≤
≤ l ≤ 21
Total number of reflections/indepenꢀ
18469/8728 (
R
int = 0.0208)
8288/3299 (Rint = 0.0427)
dent reflections with
I ≥ 2σ(I)
Tmin Tmax
/
0.8316/0.9103
496
0.9710/0.9902
171
Number of refined parameters
Goodnessꢀofꢀfit
1.058
1.009
R
R
(
I
≥
2
σ
(
I
))
R
1 = 0.0432, wR2 = 0.1287
1 = 0.0518, wR2 = 0.1381
–0.926/2.945
R
1 = 0.0524, wR2 = 0.1267
1 = 0.0832, wR2 = 0.1443
–0.309/0.342
(all data)
R
R
Δρmin
/
Δρmax, e
Å–3
ness. The dry residue was recrystallized from pyridine. KBr. NMR spectra were measured on a Bruker VXRꢀ
Yellow needleꢀlike crystals of compound II were isoꢀ
lated. The yield was 45 mg (6%), mp = 245°C (mp =
248°C [6]).
1H NMR,
δ, ppm: 10.22 s (N–H), 8.79 s (N–H),
8.65 d (1Harom), 8.01 d (1Harom), 7.93 t (1Harom), 7.73 d
(1Harom), 7.54 t (1Harom), 7.39 t (1Harom), 7.09 d
(1Harom), 6.95 t (1Harom).
400 spectrometer (400 MHz) using Me4Si as an interꢀ
nal standard and DMSOꢀd6 as a solvent.
Xꢀray diffraction analysis. Experimental sets of
reflections for compounds I and II were obtained by a
standard method [7] on a Bruker SMART APEX II
diffractometer equipped with a CCD detector and a
monochromatic radiation source
0.71073 Å). Structures and II were solved by a direct
method and refined in the fullꢀmatrix anisotropic
(MoKα, λ =
I
IR spectra were recorded in the range from 4000 to
400 cm–1 on a Nicolet Nexus 470 FTꢀIR spectrometer
using a standard procedure of pressing a sample with approximation for all nonꢀhydrogen atoms. Hydrogen
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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2011

THE REACTION OF SILVER(I) NITRATE
591
C(16)
C(15)
C(17)
C(18)
C(19)
C(14)
C(4)
C(3)
N(3)
C(20)
N(5)
C(2)
N(4)
C(7)
C(5)
C(6)
C(13)
C(12)
N(1)
N(2)
C(1)
C(30)
C(29)
C(8)
C(9)
C(31)
C(32)
Ag(1)
C(11)
C(28)
C(10)
C(27)
N(9)
N(7)
C(33)
C(21)
N(6)
C(26)
O(1S)
N(10)
C(36)
C(22)
O(2S)
C(25)
C(24)
C(34)
C(37)
N(8)
C(40)
C(39)
N(1S)
C(23)
O(3S)
C(38)
Fig. 1. Molecular structure of complex
lengths Ag(1)–N(6) 2.260(2), Ag(1)–N(2) 2.320(2), Ag(1)–N(1) 2.404(2), Ag(1)–N(7) 2.478(2), N(1
N(1 )–O(2 ) 1.216(4), N(1 )–O(3 ) 1.303(5) Å and bond angles N(6)Ag(1)N(2) 144.73(8)°, N(6)Ag(1)N(1) 130.77(7)°,
N(2)Ag(1)N(1) 72.00(7)°, N(6)Ag(1)N(7) 73.57(7)°, N(2)Ag(1)N(7) 105.36(7)°, N(1)Ag(1)N(7) 141.68(7)°.
I
(hydrogen atoms are not shown, thermal ellipsoids with 30% probability). Selected bond
S
)–O(1 ) 1.169(4),
S
S
S
S
S
atoms were calculated geometrically and refined in the amine at 6.99 ppm. In addition, the singlet signal of
riding model. The calculations were performed using the C2–H proton of dihydrotriazaindolizine
the SHELXꢀ97 program package [8]. The crystalloꢀ is observed at 7.35 ppm, which lies in the range of
graphic parameters and Xꢀray diffraction details are chemical shifts characteristic of related heterocyclic
given in the table. The full sets of Xꢀray structural data systems [9].
for compounds I and II were deposited with the Camꢀ
The reaction of studied ligand L with silver(I)
nitrate in anhydrous methanol affords the cationic
complex [AgL2]NO3 (I). According to the data of IR
bridge Crystallographic Data Centre (nos. 798563 (I)
and 798564 (II)).
spectroscopy, the coordination of dihydrotriazainꢀ
dolizine is not accompanied by the transition to the
azomethine form. The most part of bands assigned to
vibrations of the groups of ligand L undergo an insigꢀ
nificant shift.
RESULTS AND DISCUSSION
The results of studies of the condensation product
of benzaldehyde with 3ꢀ(pyridinꢀ2ꢀyl)ꢀ5ꢀ(2ꢀamiꢀ
nophenyl)ꢀ1
H
ꢀ1,2,4ꢀtriazole (L) show that the comꢀ
The structure of complex
I was established by Xꢀray
pound exists in the cyclic dihydrotriazaindolizine diffraction analysis. The complex has the cationic
1
form
B. The H NMR spectrum of the compound structure. The coordination sphere of the silver(I)
contains no signal of the hydrogen atom of the triazole atom formed by the nitrogen atoms of the pyridyl rings
cycle, which usually appears at 13–14 ppm, and (N(1), N(6)) and triazole fragments (N(2), N(7)) has
exhibits the signal of the hydrogen atom of secondary the geometry of a distorted tetrahedron (Fig. 1). The
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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592
GUSEV et al.
O(3)
N(4)
C(13)
N(5)
C(4)
C(6)
C(12)
C(3)
C(11)
N(2)
C(5)
C(10)
C(2)
C(7)
N(1)
C(1)
C(8)
C(9)
Fig. 2. Molecular structure of compound II (thermal ellipsoids with 30% probability). Selected bond lengths N(1)–C(5)
1.3410(19), N(1)–C(1) 1.345(2), N(2)–C(6) 1.3827(19), N(2)–C(7) 1.4100(18), O(3)–C(13) 1.2357918), N(4)–C(13)
1.355(2), N(4)–N(5) 1.4008(17), N(5)–C(6) 1.2831(19) Åand bond angles C(6)N(2)C(7) 122.66(12)°, C(13)N(4)N(5)
130.25(13)°, C(6)N(5)N(4) 119.55(13)°, N(5)C(6)N(2) 128.15.15(13)°, N(4)C(13)C(12) 121.72(13)°.
Ag–N(1) and Ag–N(6) bonds (2.404(2) and lope (Fig. 2). The dihedral angle between the hydraꢀ
2.478(2) Å) are substantially longer than the Ag–N(2) zone fragment and the base of the envelope is 47.66°.
and Ag–N(7) bonds (2.320(2) and 2.260(2) Å), The bond lengths and bond angles in molecule II are
respectively).
close to standard values [10].
The triazole, iminophenyl, and pyridyl cycles lie
almost in the same plane, and the phenyl fragment is
turned relatively to the iminophenyl ring by 89.29°.
The N(2)–N(3) bond (1.355(3) Å) is somewhat
shorter than the standard ordinary bond N–N
(1.451 Å), which can be due to the delocalization of
the double bond in the triazole fragment.
The C(14)–N(4) bond (1.476(3) Å) is noticeably
elongated, and other bonds in the organic ligand have
usual values [10].
The data on the synthesis of dihydroꢀ5Hꢀ1,3,4ꢀ
benzotriazepinꢀ5ꢀones were published; however, the
structures of similar compounds were established only
by spectral methods. The authors [5, 9] ascribe the
structure of 3,4ꢀdihydroꢀ5Hꢀ1,3,4ꢀbenzotriazepinꢀ5ꢀ
ones to compounds of this type. In studied compound
II, the C(6)–N(2) bond lengths (1.3827(19) Å) is
characteristic of the carbon–nitrogen ordinary bond,
whereas C(6)–N(5) (1.2831(19) Å) is typical of the
azomethine bond. Thus, the Xꢀray diffraction data
indicate that compound II has the 1,4ꢀdihydrobenzoꢀ
triazepinone form.
The outerꢀsphere nitrate anion in complex
I is
asymmetric. The N–O bonds differ noticeably in
length (1.169(4), 1.216(4), 1.303(5) Å) due to the forꢀ
mation of hydrogen bonds between the oxygen atoms
and the hydrogen atoms of the NH groups of two adjaꢀ
An attempt to synthesize compound II by the
recrystallization of L from a pyridine–ethanol mixture
did not give the desired result. Perhaps, the coordinaꢀ
tion of the nitrogen atom by the silver cation favors the
primary hydrolytic cleavage of the triazole cycle folꢀ
lowed by the closure of the sevenꢀmembered cycle of
triazepinone. Similar rearrangements of azomethine
systems in coordination compounds were described in
the literature but are met rather rarely [11].
cent molecules: O(2S)···N(10) (x, y, z) 2.893,
O(3S)···N(5) ( y – 1, ) 2.917 Å. Owing to a decrease
x,
z
in symmetry of the
− anion due to the formation of
NO3
strong hydrogen bonds, no intense band with an
absorption maximum at 1380 cm–1 is observed, which
is characteristic of outerꢀsphere nitrate anions.
An interesting result was obtained by the study of
the mother liquor after the synthesis of complex
I.
2(2'ꢀPyridyl)ꢀ1,4ꢀdihydroꢀ5 ꢀ1,3,4ꢀbenzotriazepinꢀ
H
ACKNOWLEDGMENTS
5ꢀone (II) was isolated, and its structure was conꢀ
firmed by direct Xꢀray diffraction analysis. It was
This work was supported by the Division of Chemꢀ
found that the sevenꢀmembered nitrogenꢀcontaining istry and Materials Science of the Russian Academy of
heterocycle has the conformation of a distorted enveꢀ Sciences.
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THE REACTION OF SILVER(I) NITRATE
593
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