Catena-poly[[(benzoato-κO)silver(I)]-μ-2-aminopyrimidine- κ2N1:N3]

Article abstract of DOI:10.1107/S0108270104024424

The molecular structure and the formation of [Ag(C₇H ₅O₂) (C₄H₅N₃)] _n were investigated. The sample compound is a polymer based on a a mononuclear silver(I)-centered fragment. It was proposed that intermolecular hydrogen bonding in the sample influenced the formation of the chain polymer. In the sample, the 2-aminopyrimidine-Ag^I cation propagated as a zigzag chain along the axis, with the anionic benzoate ligands extending laterally, attached not only by the Ag-O bonds but also through intramolecular N-H···O hydrogen bonds.

Full text of DOI:10.1107/S0108270104024424

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
pyridine as a bidentate ligand and the benzoate anion as the
counter-ion to obtain a mononuclear silver(I) complex,
namely bis(2-aminopyridine-ꢀN1)(benzoato-ꢀO)silver(I), (II)
(Zhu et al., 2003). In order to investigate the relationship
between the starting materials and the resulting structures, we
used the tridentate ligand 2-aminopyrimidine instead of the
bidentate ligand 2-aminopyridine to obtain the title
compound, (I). As expected, the structure of (I) consists of
one-dimensional chains and is thus entirely different from that
of (II).
ISSN 0108-2701
catena-Poly[[(benzoato-jO)silver(I)]-
l-2-aminopyrimidine-j2N1:N3]
Zhong-Lu Youa,b and Hai-Liang Zhua*
Complex (I) is
a
polymeric 2-aminopyrimidine±AgI
aDepartment of Chemistry, Fuyang Normal College, Fuyang, Anhui 236041, People's
Republic of China, and bDepartment of Chemistry, Lanzhou University, Lanzhou
730000, People's Republic of China
compound (Fig. 1). The smallest repeat unit for the complex
contains a 2-aminopyrimidine±AgI cation and a benzoate
anion. The AgI atom is in a distorted trigonal coordination
environment and is three-coordinated by two N atoms of two
different but symmetry-related 2-aminopyrimidine ligands
and by one O atom of one benzoate anion. The angles
subtended at atom Ag1 [136.15 (15), 125.40 (16) and
98.38 (15)ꢀ, respectively; Table 1] are comparable to the
corresponding values observed in (II). In (I), the smallest of
these angles is O1ÐAg1ÐN2, which forms part of a six-atom
ring (including an H atom) closed by the N1ÐH1AÁ Á ÁO1
hydrogen bond.
Correspondence e-mail: hailiang_zhu@163.com
Received 26 August 2004
Accepted 29 September 2004
Online 11 November 2004
The title complex, [Ag(C7H5O2)(C4H5N3)]n, is a polymer
based on a mononuclear silver(I)-centered fragment. The AgI
atom is trigonally coordinated by two N atoms from two
2-aminopyrimidine ligands and one O atom from one
benzoate anion, giving zigzag polymeric chains with an
[±AgÐNÐCÐN±]n backbone running along the a axis. It is
proposed that intermolecular hydrogen bonding drives the
formation of the chain polymer.
Ê
The mean AgÐN bond length is 2.291 (4) A in (I) and
Ê
2.218 (4) A in (II). The AgÐO bond length in (I) [2.313 (4) A]
Ê
Ê
is comparable to the value of 2.344 (4) A in (II). The coordi-
nation geometry around the Ag atom in (II) is approximately
trigonal and is thus qualitatively the same pattern as that
found in (I).
Comment
In the extended structure of (I), the 2-aminopyrimidine±
AgI cation propagates as a zigzag chain along the a axis
(Fig. 2), with the anionic benzoate ligands extending laterally,
attached not only by the AgÐO bonds but also through
intramolecular NÐHÁ Á ÁO hydrogen bonds (Table 2).
In (II), the layered structure is mediated by the formation of
intermolecular hydrogen bonds. In contrast, in (I), the
Inorganic supramolecular chemistry, and in particular the
construction of polymeric silver(I) coordination networks, is
an active area of research (Xu et al., 2001; Yaghi & Li, 1996;
Khlobystov et al., 2001). The primary reason for interest in
silver(I) compounds is their ability to afford functional solid
materials with potentially controllable properties and novel
molecular structures. Recent developments in supramolecular
chemistry have made it possible to select building units for
assembly into structures with speci®c network topologies
(Blake et al., 2000; Melcer et al., 2001). Crystal engineering of
coordination polymeric networks based on multidentate
ligands is a growing area of coordination and supramolecular
chemistry. Recently, we have focused our attention on the
assembly of silver(I) ions with ¯exible ligands, since they can
adopt diverse coordination modes according to the geometric
needs of the silver(I) ions (You, Yang et al., 2004; You, Zhu &
Liu, 2004). As reported previously, we have used 2-amino-
Figure 1
The structure and atom-numbering scheme of (I). Displacement
ellipsoids are drawn at the 30% probability level. Atoms labeled with
the suf®x A are at the symmetry position (1 + x, y, z). Dashed lines
indicate intramolecular interactions.
Acta Cryst. (2004). C60, m623±m624
DOI: 10.1107/S0108270104024424
# 2004 International Union of Crystallography m623

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
Ag1ÐN3i
Ag1ÐO1
2.237 (4)
2.313 (4)
Ag1ÐN2
2.345 (4)
N3iÐAg1ÐO1
N3iÐAg1ÐN2
136.15 (15)
125.40 (16)
O1ÐAg1ÐN2
98.38 (15)
Symmetry code: (i) 1 ‡ x; y; z.
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N1ÐH1BÁ Á ÁO2ii
0.90
0.90
1.99
1.93
2.843 (7)
2.825 (6)
157
177
N1ÐH1AÁ Á ÁO1
Symmetry code: (ii) x 1; y; z.
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.057
wR(F2) = 0.125
S = 1.18
2297 re¯ections
w = 1/[ꢅ2(F2o) + (0.0468P)2
+ 0.8969P]
where P = (F2o + 2Fo2)/3
(Á/ꢅ)max < 0.001
3
Ê
Áꢆmax = 0.80 e A
3
Ê
0.74 e A
154 parameters
H-atom parameters constrained
Áꢆmin
=
Figure 2
The crystal packing of (I), viewed along the a axis.
All H atoms were placed in idealized positions and allowed to ride
Ê
on their parent atoms (NÐH = 0.90 A and CÐH = 0.96 A), with
Ê
hydrogen bonds are located within each of the chains. The H
atoms of the amine groups are disposed in such a way as to
obviate a link to the O atoms of another chain. We propose
that it is this fundamental difference in the arrangement of the
non-covalent interactions in (I) that gives rise to a chain
structure rather than to discrete molecules in layers or another
arrangement mediated by non-covalent interactions.
2
Uiso(H) values ®xed at 0.08 A .
Ê
Data collection: SMART (Bruker, 1998); cell re®nement: SMART;
data reduction: SAINT (Bruker, 1998); program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997a); molecular graphics:
SHELXTL (Sheldrick, 1997b).
The authors thank the Education Of®ce of Anhui Province,
People's Republic of China, for research grant No.
2004kj300zd.
Experimental
Ag2O (0.1 mmol, 23.2 mg) and benzoic acid (0.2 mmol, 24.4 mg) were
dissolved in a 30% aqueous ammonia solution (10 ml), and the
resulting solution was stirred for ca 15 min to give a clear colorless
solution. To this solution was added an acetonitrile solution (5 ml) of
2-aminopyrimidine (0.1 mmol, 9.5 mg) with stirring. The mixture was
stirred for 1 h, and the resulting colorless solution was kept in the
dark at room temperature for 8 d. Colorless block-shaped crystals
formed on slow evaporation of the solvent.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FA1091). Services for accessing these data are
described at the back of the journal.
References
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Crystal data
3
[Ag(C7H5O2)(C4H5N3)]
Mr = 324.09
Monoclinic, P21=n
Ê
a = 6.457 (3) A
Dx = 1.910 Mg m
Mo Kꢂ radiation
Cell parameters from 1213
re¯ections
ꢃ = 2.2±25.3ꢀ
ꢄ = 1.78 mm
T = 293 (2) K
Ê
b = 25.594 (7) A
Ê
Inorg. Chem. 40, 4641±4648.
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
1
c = 7.111 (3) A
ꢁ = 106.488 (3)ꢀ
È
Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of
3
Ê
V = 1126.8 (8) A
Z = 4
Block, colorless
0.28 Â 0.25 Â 0.22 mm
È
Gottingen, Germany.
Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison,
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Data collection
Bruker SMART CCD area-detector
diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.636, Tmax = 0.695
5115 measured re¯ections
2297 independent re¯ections
1870 re¯ections with I > 2ꢅ(I)
Rint = 0.041
ꢃmax = 26.5ꢀ
h = 7 ! 8
k = 23 ! 32
l = 6 ! 8
ꢁ
m624 You and Zhu [Ag(C7H5O2)(C4H5N3)]
Acta Cryst. (2004). C60, m623±m624