Synthesis and crystal structures of two silver(I) complexes derived from 2-amino-4-methylpyridine with 2-aminobenzoic acid and nicotinic acid

Article abstract of DOI:10.3109/10799890903555608

The reaction of Ag₂O and 2-amino-4-methylpyridine (AMP) with 2-aminobenzoic acid (HAC) and nicotinic acid (HNA), respectively, afforded two silver(I) complexes, [Ag(AMP)₂] AC (1) and [Ag(AMP)(NA)] _nnH₂O (2). Both complexes were characterized by elemental analyses and X-ray single-crystal diffraction. Complex (1) is a mononuclear silver(I) complex, in which the Ag atom is in a linear geometry, while complex (2) is a pyridine-3-carboxylate bridged polynuclear silver(I) complex, in which the Ag atom is in a distorted triangular geometry. Both crystals are stabilized by intermolecular hydrogen bonds. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.3109/10799890903555608

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Synthesis and Crystal Structures of Two Silver(I)
Complexes Derived from 2-Amino-4-methylpyridine
with 2-Aminobenzoic Acid and Nicotinic Acid
Feng-Wu Wang a , Yi-Jun Wei a & Qi-Yong Zhu a
a Department of Chemistry , Huainan Normal College , Huainan, P. R. China
Published online: 16 Feb 2010.
To cite this article: Feng-Wu Wang , Yi-Jun Wei & Qi-Yong Zhu (2010) Synthesis and Crystal Structures of Two Silver(I)
Complexes Derived from 2-Amino-4-methylpyridine with 2-Aminobenzoic Acid and Nicotinic Acid, Synthesis and Reactivity
in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:2, 129-133
To link to this article: http://dx.doi.org/10.3109/10799890903555608
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:129–133, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.3109/10799890903555608
Synthesis and Crystal Structures of Two Silver(I) Complexes
Derived from 2-Amino-4-methylpyridine with
2-Aminobenzoic Acid and Nicotinic Acid
Feng-Wu Wang, Yi-Jun Wei, and Qi-Yong Zhu
Department of Chemistry, Huainan Normal College, Huainan, P. R. China
EXPERIMENTAL
The reaction of Ag2O and 2-amino-4-methylpyridine (AMP)
with 2-aminobenzoic acid (HAC) and nicotinic acid (HNA), re-
Materials and Measurements
All the starting materials for synthesis were of analytical
spectively, afforded two silver(I) complexes, [Ag(AMP)2]·AC (1)
and [Ag(AMP)(NA)]n·nH2O (2). Both complexes were character-
ized by elemental analyses and X-ray single-crystal diffraction.
Complex (1) is a mononuclear silver(I) complex, in which the Ag
atom is in a linear geometry, while complex (2) is a pyridine-3-
carboxylate bridged polynuclear silver(I) complex, in which the
Ag atom is in a distorted triangular geometry. Both crystals are
stabilized by intermolecular hydrogen bonds.
grade as purchased from Aldrich and were used without further
purification. Elemental analyses were carried out on a Perkin-
Elmer model 240 analyzer.
Synthesis of [Ag(AMP)2]·AC (1)
Ag2O (0.1 mmol, 23.2 mg) and HAC (0.2 mmol, 27.5 mg)
were dissolved in a 30% ammonia solution (10 ml) and stirred
for 30 min to give a clear colorless solution. To the above solu-
tion was added with stirring a methanol solution (3 mL) of AMP
(0.2 mmol, 21.6 mg). The mixture was stirred for another 30 min,
and the resulting clear solution was kept in dark at room tem-
perature for a week. Colorless block-shaped crystals of (1) were
formed. The crystals were isolated by filtration. Yield: 31% on
the basis of Ag2O. Anal. calcd. for C19H22AgN5O2(FW 460.3):
C, 49.6; H, 4.8; N, 15.2. Found: C, 49.1; H, 5.0; N, 15.5%.
Keywords crystal structure, hydrogen bonding, silver, synthesis
INTRODUCTION
In the last few years, there have been major advances in
the synthesis of complex structures, including polymers, two-
dimensional sheets, helices, and cages, through the use of dy-
namic coordination chemistry.[1−6] Among the metal ions, sil-
ver is of particular interest in the self-assembly of complex
structures since it is a labile metal center with versatile coor-
dination modes.[7−9] 2-aminobenzoic acid (HAC) and nicotinic
acid (HNA) are two versatile ligands in the synthesis of silver(I)
complexes, which readily adopt bridging modes.[10,11] 2-amino-
4-methylpyridine (AMP) is also a useful ligand in the synthesis
of silver(I) complexes.[12,13] In order to investigate the aggre-
gates of such components, in this paper, two silver(I) complexes
have been synthesized and structurally characterized.
Synthesis of [Ag(AMP)(NA)]n·nH2O (2)
Complex (2) was synthesized by a similar method as that
described for (1), with HAC replaced by HNA (0.2 mmol, 24.5
mg), yielding colorless block-shaped crystals. Yield: 45% on the
basis of Ag2O. Anal. calcd. for C12H14AgN3O3 (FW 356.1): C,
40.5; H, 4.0; N, 11.8. Found: C, 41.0; H, 4.1; N, 11.5%.
Crystal Structure Determination
Diffraction intensities for the complexes were collected at
298(2) K using a Bruker SMART APEX 1000 area-detector with
˚
MoKa radiation (λ = 0.71073 A). The collected data were re-
duced using the SAINT program,[14] and multi-scan absorption
corrections were performed using the SADABS program.[15]
The structures were solved by direct methods and refined against
F2 by full-matrix least-squares methods using the SHELXTL
program.[16] Non-hydrogen atoms were refined with anisotropic
displacement parameters. The amino H atoms in both complexes
and the water H atoms in (2) were located in difference Fourier
maps and refined isotropically, with N–H and O–H distances
Received 12 September 2009; accepted 10 November 2009.
The authors thank the Natural Science Foundation of the Educa-
tion Office of Anhui Province, P. R. China, for research grant No.
KJ2007A126ZC.
Address correspondence to Yi-Jun Wei, Department of Chemistry,
Huainan, 232001, China. E-mail: huainanweiyijun@163.com
129

130
F.-W. WANG ET AL.
TABLE 1
Crystallographic and experimental data for complexes (1) and
(2)
Complexes
(1)
(2)
Formula
C19H22AgN5O2 C12H14AgN3O3
FW
460.3
356.1
Crystal shape/color
Crystal size/mm
Crystal system
Space group
block/colorless
block/colorless
0.20×0.18×0.17 0.43×0.40×0.38
Monoclinic
P21/c
Monoclinic
Cc
˚
a/A
16.229(1)
7.070(1)
17.979(1)
112.412(2)
1907.1(3)
4
10.756(2)
8.718(2)
14.599(3)
107.711(3)
1304.1(5)
4
˚
b/A
˚
c/A
β/◦
V /A
Z
3
˚
FIG. 1. Molecular structure of (1) with 30% probability thermal ellipsoids.
H atoms not related to the hydrogen bonding are omitted. Hydrogen bond as
dashed lines. Atoms with the suffixes A and B are at the positions 1 +x, y, z
and −x, 1 −y, −z, respectively.
T /K
298(2)
1.081
1.603
298(2)
1.553
1.814
µ/mm−1(Mo-Kα)
Dc/g cm−3
Reflections/parameters 4125/330
Independent reflections 3497
2139/629
2086
712
0.555
0.590
RESULTS AND DISCUSSION
Preparation of the Complexes
F(000)
Tmin
936
The reaction of Ag2O with HAC and HNA, respectively,
forms the corresponding silver(I) carboxylates.[10,17,18] The sil-
ver(I) carboxylates are readily react with organic compounds
containing N atoms, forming versatile structures.[19,20] In this
paper, the AMP was added to the silver(I) carboxylates, yield-
ing two polynuclear silver(I) complexes. The elemental analy-
ses confirm the formulae of the complexes. The crystals of both
complexes are stable in dark, soluble in 30% ammonia solution
and acetonitrile.
0.813
0.837
1.059
Tmax
Goodness of fit on F2
1.057
R1, wR2 [I ≥ 2σ(I)]a) 0.0278, 0.0721
0.0503, 0.0203
0.0507, 0.0210
ꢀ
R1, wR2 (all data)a)
0.0346, 0.0762
ꢀ
ꢀ
aR1
w(Fo2)2]1/2
=
||Fo| − |Fc||/ |Fo|, wR2 = [ w(Fo2 − Fc2)2/
ꢀ
.
˚
restrained to 0.90(1) and 0.85(1) A, respectively. All other hy-
drogen atoms were placed in geometrically idealized positions
and constrained to ride on their parent atoms. The crystallo-
graphic data for the complexes are summarized in Table 1. The
coordinate bond lengths and angles are listed in Table 2. Hydro-
gen bonds are listed in Table 3.
Structure Description of the Two Complexes
The molecular structure of (1) is shown in Figure 1. The
complex consists of a mononuclear silver(I) complex cation and
. . .
a 2-aminobenzoate anion. An intramolecular N4−H4B O1
hydrogen bond is observed between the two moieties. The Ag
atom in the cation is coordinated by two N atoms from two
AMP ligands, forming a linear geometry, with the N1-Ag1-
N3 bond angle of 177.7(1)◦. The coordinate bond lengths are
comparable with the values observed in other similar silver(I)
complexes.[11,21] The dihedral angle between the two pyridine
rings is 28.2(3)◦.
TABLE 2
◦
˚
Selected bond lengths (A) and angles ( ) for the complexes (1)
and (2)
(1)
In the crystal structure of the complex, the AC anions are
Ag1 N1
N3 Ag1 N1
2.1080(18) Ag1 N3
177.66(7)
2.1077(18)
2.259(2)
. . .
linked to the silver(I) cations through N−H O hydrogen
. . .
bonds. The aggregates are further linked through N−H O hy-
drogen bonds, forming layers parallel to the bc plane, as shown
in Figure 2.
(2)
Ag1 N1
Ag1 O1A
N1 Ag1 N3
2.206(2)
2.447(2)
Ag1 N3
The molecular structure of (2) is shown in Figure 3. The
smallest repeat unit of the complex consists of an Ag atom,
an AC ligand, an AMP ligand, and a water molecule of
crystallization. The water molecule is linked to the silver(I)
131.90(10) N1 Ag1 O1A 130.78(9)
N3 Ag1 O1A 95.30(9)

SYNTHESIS AND CRYSTAL STRUCTURES OF SILVER(I) COMPLEXES
131
TABLE 3 ◦
˚
Hydrogen bond distances (A) and angles ( ) for the complexes (1) and (2)
D H· · · A
d(D H)
d(H· · · A)
d(D · · · A)
Angle (D H· · · A)
(1)
N4 H4A· · ·O2i
N2 H2B· · ·O1ii
N2 H2A· · ·O2iii
N5 H5B· · ·O1iv
N5 H5A· · ·O2
N4 H4B· · ·O1
(2)
0.897(10)
0.897(10)
0.893(10)
0.879(10)
0.88(2)
2.39(3)
3.267(3)
3.166(3)
2.874(2)
2.924(3)
2.656(3)
2.988(3)
168(3)
166(3)
167(3)
159(3)
131(2)
169(3)
2.288(11)
1.996(12)
2.087(15)
2.00(2)
0.898(10)
2.10(3)
O3 H3B· · ·O1
N2 H2A· · ·O2v
N2 H2B· · ·O3vi
O3 H3A· · ·O2vii
0.85(3)
0.89(4)
0.89(3)
0.86(4)
1.95(3)
2.15(4)
2.07(4)
1.98(4)
2.787(4)
3.025(4)
2.923(4)
2.811(4)
169(4)
171(5)
161(4)
165(5)
Symmetry codes for i) −x, 1 −y, 1 −z; ii) x, 3/2 −y, 1/2 +z; iii) −x, 1/2 +y, 1/2 −z; iv) x, −1 +y, z; v) −x, 1 −y, 1 −z.
. . .
complex molecule through intramolecular O3−H3B O1 hy- as evidenced by the coordinate bond angles. The bond angles
drogen bond. The AMP ligands linked to the silver(I) moieties of N1-Ag1-N3 and N1-Ag1-O1A are 131.9(1) and 130.8(1)◦,
through the Ag-N(pyridine) coordination bonds. The HAC lig- respectively, which deviates from the ideal value of 120◦ for
and acts as a bridging group, which coordinates to two Ag atoms a perfect triangular geometry. The N3-Ag1-O1A bond angle
through the pyridine N atom and one phenolate O atom.
of 95.3(1)◦ is also deviates from the ideal value of 120◦ for a
Each Ag atom in the complex is three-coordinated in a dis- perfect triangular geometry. The coordinate bond lengths are
torted triangular geometry, with one N and one O atoms from comparable with those of (1), and also comparable with the
two AC ligands, and with one pyridine N atom of one AMP values observed in other similar silver(I) complexes.[22,23]
ligand. The triangular geometry of the coordination is distorted,
In the crystal structure of the complex, the molecules are
. . .
. . .
linked through intermolecular N−H O and O−H O hydro-
gen bonds, forming a three-dimensional network, as shown in
Figure 4.
FIG. 3. Molecular structure of (2) with 30% probability thermal ellipsoids.
H atoms not related to the hydrogen bonding are omitted. Hydrogen bond as
dashed lines. Atoms with the suffixes A, B and C are at the positions −x, 1 −y,
1 −z; x, 3/2 −y, −1/2 +z; and −x, −1/2 +y, 3/2 −z, respectively.
FIG. 2. Molecular packing of (1), viewed along the b axis.

132
F.-W. WANG ET AL.
FIG. 4. Molecular packing of (2), viewed along the a axis.
CONCLUSION
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A mononuclear silver(I) complex and a polynuclear silver(I)
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a versatile ligand in the synthesis of silver(I) complexes, which
readily adopt bridging modes in the coordination. The coordina-
tion of the 2-aminobenzoic acid and 2-amino-4-methylpyridine
indicates that the pyridine N atom readily coordinates to the Ag
atom, while the amino N atom seldom coordinates to the Ag
atom. Instead, the amino N atoms contribute to the formation of
hydrogen bonds, and stabilize the crystal structures.
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Supplementary Material
CCDC 741187 and 741188 contain the supplementary
crystallographic data for (1) and (2), respectively. These
data can be obtained free of charge via http://www.ccdc.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallographic
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(+44)1223-336-033; or email: deposit@ccdc.cam.ac.uk.
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