Bis(μ-4-chlorobenzoato-k2O:O)bis-[(2-aminopyridine-kN) silver(I)]

Article abstract of DOI:10.1107/S0108270104003609

The crystal structure of title silver-carboxylate complex with 2-amino-pyridine was discussed. It was observed that the compound lies about an inversion center and the Ag atom is three-coordinate by two O atoms and One N atom from three different ligands. The 4-chlorobenzoate anion acts as a monodonor ligand, briding two inversion-related Ag atoms of the compound into a dimer. It was also observed that there are weak intermolecular N-H···O hydrogen bonds in the structure.

Full text of DOI:10.1107/S0108270104003609

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
Bis(l-4-chlorobenzoato-j2O:O)bis-
[(2-aminopyridine-jN)silver(I)]
Hai-Liang Zhu,* Xiao-Yang Qiu, Song Yang, Si-Chang
Shao, Ji-Long Ma and Lin Sun
Department of Chemistry, Fuyang Normal College, Fuyang, Anhui 236041, People's
Republic of China
Figure 1
Correspondence e-mail: hailiang_zhu@fync.edu.cn
The structure of (I), showing the atom-numbering scheme. Displacement
ellipsoids are drawn at the 30% probability level and H atoms are shown
as small spheres of arbitrary radii. Atoms labelled with the suf®x A are at
the symmetry position (2 x, y, z).
Received 4 February 2004
Accepted 16 February 2004
Online 11 March 2004
Ê
[2.103 (5) A; Zhu et al., 2003b], but is close to that found in
Ê
4-¯uorobenzoatosilver(I) [2.512 (4) A; Zhu, Zeng et al., 2003].
Ê
The AgÐN bond length [2.137 (4) A] is comparable with
those in similar silver complexes with pyridine derivatives that
we have investigated. All other bond lengths (Table 1) in (I)
are within normal ranges (Allen et al., 1987).
The title compound, [Ag2(C7H4ClO2)2(C5H6N2)2], lies about
an inversion centre and the Ag atom is three-coordinated by
two O atoms and one N atom from three different ligands. The
4-chlorobenzoate anion acts as a monodonor ligand, bridging
two inversion-related Ag atoms of the compound into a dimer.
There are weak intermolecular NÐHÁ Á ÁO hydrogen bonds in
the structure.
Some pyramidalization is shown by atom O1, which is
i
Ê
0.407 (3) A out of the plane through atoms C1, Ag1 and Ag1
[symmetry code: (i) 2 x, y, z]. The two exocyclic angles
about O1 are strongly asymmetric, with Ag1ÐO1ÐC1 of
138.0 (3)ꢀ being much larger than Ag1iÐO1ÐC1 of 107.6 (3)ꢀ,
and this seems to be caused by the N2ÐH2Á Á ÁO2i attraction
on one side and the H3Á Á ÁH12 steric repulsion on the other.
As is shown in (I), the benzoate carboxyl group acts as a
monodonor bridging two Ag atoms, forming the title dimeric
dinuclear complex.
Comment
Pyridine and its derivative metal complexes are of much
current interest in coordination chemistry. Indeed, many
monomers, dimers and polymers have been prepared and
structurally determined. Recently, we reported a few silver(I)
complexes with pyridine and pyridine derivatives (Zhu et al.,
2001, 2003a; Zhu, Liu et al., 2003; Zhu, Yang et al., 2003; Zhu,
Zhang, Sun et al., 2003; Zhu, Zeng et al., 2003). Some of the
complexes (Zhu et al., 2001) have high cytotoxicity. To further
our work in this ®eld, we report here the crystal structure of
the title silver±carboxylate complex, (I), with 2-amino-
pyridine.
The central Ag2O2 four-membered coordination ring has a
rectangular geometry, with the Ag1ÐO1 distance of
i
2.589 (3) A being noticeably longer than Ag1ÐO1 of
Ê
i
Ê
2.191 (3) A. The O1ÐAg1ÐO1 bond angle must be related
to the Ag1ÐO1ÐAg1i angle and the planarity of the central
ring, while the asymmetry of the exocyclic bond angles about
Ag1 is related to the planarity of the bonds to Ag and the
different interactions in which the two sides of the amino-
Ê
pyridine ligand are involved, namely the H1Á Á ÁH12 (2.71 A)
contact on the side of the narrower O1ÐAg1ÐN1 [120.4 (1)ꢀ]
angle and the N2ÐH2AÁ Á ÁO2A intramolecular hydrogen
bond on the side of the larger N1ÐAg1ÐO1i [156.8 (1)ꢀ]
angle. The ring is on a plane which makes a dihedral angle of
42.4 (2)ꢀ with benzene and 38.1 (2)ꢀ with pyridine; the two
aromatic rings are approximately coplanar, the dihedral angle
they form being only 12.4 (2)ꢀ. The displacement from perfect
coplanarity is probably caused by steric hindrance between
the two organic ligands, which is also related to the more
pronounced displacement from coplanarity which these
ligands show with respect to the central coordination ring.
The intramolecular C3ÐH3Á Á ÁO1 and C7ÐH7Á Á ÁO2 inter-
actions, the HÁ Á ÁO distances of which are signi®cantly less
In compound (I), the Ag atom is three-coordinated by two
O atoms from different 4-chlorobenzoate anions and one N
atom from the 2-aminopyridine ligand. This AgO2N coordi-
nation forms a Y-shaped geometry at Ag1, with the three
angles subtended at the Ag atom being 82.80 (12), 120.37 (12)
ꢀ
Ê
and 156.79 (13) . The Ag1ÐO1 bond length of 2.589 (3) A is
much longer than that in bis[aqua(4-chlorobenzoato)silver(I)]
m170 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270104003609
Acta Cryst. (2004). C60, m170±m171

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
than the sum of the van der Waals radii, are remarkable for the
conformation of the anionic ligand. In the crystal structure of
(I), the molecules are interconnected, in columns parallel to
the b axis, by intermolecular N2ÐH2BÐO2ii and N2Ð
H2AÁ Á ÁO2i hydrogen bonds [Table 2; symmetry code: (ii)
ꢀ
Ê
Ag1ÐN1
Ag1ÐO1i
2.137 (4)
2.191 (3)
Ag1ÐO1
2.589 (3)
N1ÐAg1ÐO1i
N1ÐAg1ÐO1
156.79 (13)
120.37 (12)
O1iÐAg1ÐO1
82.80 (12)
1
2
‡ x; 12 y; 12 ‡ z].
Symmetry code: (i) 2 x; y; z.
Experimental
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
Ag2O (0.5 mmol, 116 mg) and 4-chlorobenzoic acid (1 mmol, 157 mg)
were dissolved in a 30% aqueous ammonia solution (10 ml), and the
resulting solution was stirred for ca 10 min until a clear solution was
obtained. A solution of 2-aminopyridine (1 mmol, 94 mg) in aceto-
nitrile (2 ml) was added to the above solution. The resulting solution
was kept in air for 2 d with ammonia gas escaping. Colourless crystals
of (I) were collected and washed with water and acetonitrile in turn,
and then dried in a vacuum desiccator over CaCl2 (yield 44%).
Analysis calculated for C12H10AgClN2O2: C 40.31, H 2.82, N 7.83%;
found: C 39.95, H 2.88, N 7.69%.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH2AÁ Á ÁO2i
N2ÐH2BÁ Á ÁO2ii
C3ÐH3Á Á ÁO1
C7ÐH7Á Á ÁO2
0.86
0.86
0.93
0.93
2.29
2.16
2.49
2.52
3.141 (5)
2.990 (5)
2.789 (6)
2.815 (7)
170
163
99
99
Symmetry codes: (i) 2 x; y; z; (ii) ‡ x; 12 y; 21 ‡ z.
1
2
re®ne structure: SHELXL97 (Sheldrick, 1997a); molecular graphics:
SHELXTL (Sheldrick, 1997b); software used to prepare material for
publication: SHELXTL.
Crystal data
[Ag2(C7H4ClO2)2(C5H6N2)2]
Mr = 715.08
Mo Kꢁ radiation
Cell parameters from 1840
re¯ections
The authors thank the Education Of®ce of Anhui Province,
People's Republic of China, for research grant No.
2004kj300zd, and the Natural Science Foundation of Hubei
Province, People's Republic of China, for research grant No.
2003ABB010.
Monoclinic, P21=n
ꢂ = 2.8±22.2ꢀ
Ê
a = 14.366 (5) A
1
Ê
b = 5.545 (2) A
ꢃ = 1.84 mm
T = 298 (2) K
Ê
c = 15.530 (6) A
ꢀ = 92.360 (6)ꢀ
V = 1236.0 (8) A
Prism, colourless
0.42 Â 0.30 Â 0.09 mm
3
Ê
Z = 2
Dx = 1.921 Mg m
3
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1642). Services for accessing these data are
described at the back of the journal.
Data collection
Siemens SMART CCD area-
detector diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.512, Tmax = 0.852
5997 measured re¯ections
2179 independent re¯ections
1566 re¯ections with I > 2ꢄ(I)
Rint = 0.038
References
ꢂ
max = 25.0ꢀ
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È
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È
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Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.035
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2179 re¯ections
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3
Ê
Áꢅmax = 0.58 e A
3
Ê
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Ê
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Data collection: SMART (Siemens, 1996); cell re®nement:
SMART; data reduction: SAINT (Siemens, 1996); program(s) used to
solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to
ꢁ
Acta Cryst. (2004). C60, m170±m171
Hai-Liang Zhu et al.
[Ag2(C7H4ClO2)2(C5H6N2)2] m171