catena-Poly[[(nitrato-κ2 O,O′)silver(I)]-μ3-4-pyridone-κ3 O:O:O]

Xian-Ge Wu; Jun-Xia Xiao; Liang Qin

doi:10.1107/S1600536809019138

. 2009 May 29;65(Pt 6):m685–m686. doi: 10.1107/S1600536809019138

catena-Poly[[(nitrato-κ² O,O′)silver(I)]-μ₃-4-pyridone-κ³ O:O:O]

Xian-Ge Wu ^a,^*, Jun-Xia Xiao ^a, Liang Qin ^a

PMCID: PMC2969665 PMID: 21583044

Abstract

In the title complex, [Ag(NO₃)(C₅H₅NO)]_n, the Ag^I atom is coordinated by two O atoms from two different 4-pyridone ligands and two O atoms from one nitrate anion, displaying a nearly planar coordination geometry. The O atoms of two 4-pyridone ligands bridge two symmetrically related AgNO₃ units, forming a dimer, with an Ag⋯Ag separation of 3.680 (2) Å. Neighbouring dimers are linked into an infinite chain through weak Ag⋯O interactions [2.765 (2) Å], Ag⋯Ag interactions [3.1511 (4) Å] and π–π stacking interactions [centroid–centroid distance = 3.623 (4) Å]. N—H⋯O and C—H⋯O hydrogen bonds assemble these chains into a three-dimensional network.

Related literature

For general background to hydroxypyridines, see: Deng et al. (2005 ▶); Holis & Lippard (1983 ▶); John & Urland (2006 ▶); Klausmeyer & Beckles (2007 ▶). For related structures, see: Deisenhofer & Michel (1998 ▶); Gao et al. (2004 ▶); Leng & Ng (2007 ▶); Li, Yan et al. (2005 ▶); Li, Yin et al. (2005 ▶); Pan & Xu (2004 ▶); Wu et al. (2003 ▶).

Experimental

Crystal data

[Ag(NO₃)(C₅H₅NO)]
M _r = 264.98
Monoclinic,
a = 19.3509 (7) Å
b = 3.6232 (1) Å
c = 21.2600 (8) Å
β = 102.174 (2)°
V = 1457.06 (9) Å³
Z = 8
Mo Kα radiation
μ = 2.74 mm⁻¹
T = 296 K
0.26 × 0.23 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.508, T _max = 0.575
11458 measured reflections
1678 independent reflections
1557 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.020
wR(F ²) = 0.054
S = 1.07
1678 reflections
112 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019138/hy2199sup1.cif

e-65-0m685-sup1.cif^{(12.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019138/hy2199Isup2.hkl

e-65-0m685-Isup2.hkl^{(82.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ag1—O1ⁱ	2.3259 (15)
Ag1—O1	2.3493 (16)
Ag1—O1ⁱⁱ	2.7652 (18)
Ag1—O2	2.4132 (19)
Ag1—O3	2.5437 (18)
Ag1—Ag1ⁱⁱⁱ	3.1511 (4)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2^iv	0.93	2.46	3.343 (3)	160
N1—H1⋯O4^v	0.89 (3)	2.21 (2)	2.965 (3)	143 (3)
N1—H1⋯O4^iv	0.89 (3)	2.45 (2)	3.121 (3)	133 (3)

Open in a new tab

Symmetry codes: (iv) Inline graphic ; (v) .

Acknowledgments

The authors acknowledge the Guangdong Natural Science Foundation (SN. 8452606101000739) for supporting this work.

supplementary crystallographic information

Comment

Hydroxypyridines (PyOH), such as 2-, 3- and 4-PyOH, have attracted great attention in the field of crystal engineering as good candidates for the construction of supramolecular systems because they are bifunctional ligands that are not only capable of coordinating to metal ions but can also form classical hydrogen bonds as both donors and acceptors (Holis & Lippard, 1983; Klausmeyer & Beckles, 2007). 4-PyOH has two tautomers, dominated by the presence of keto form in polar solvents (Deng et al., 2005; John & Urland, 2006). Thus, the protonated N atom can act as hydrogen bond donor and the PyOH uses O atom to coordinate to metal. However, the coordination chemistry of 4-PyOH ligand is still underveloped and only a few complexes have been structurally characterized in recent years (Gao et al., 2004; Leng & Ng, 2007; Li, Yan et al., 2005). In order to gain further insight into the metal-binding modes of the 4-PyOH ligand, we introduced Ag^I ion into the coordination system of the 4-PyOH ligand. In the present paper, the Ag^I ion only coordinates via the unfavoured O atom of 4-pyridone ligand, producing the title one-dimensional coordination polymer, which exhibits a three-dimensional hydrogen-bonded architecture.

The coordination environment of Ag^I centre is shown in Fig. 1. Each Ag^I atom is coordinated by two O atoms from two different 4-pyridone ligands and two O atoms from one nitrate anion (Table 1), displaying a nearly planar coordination geometry. Two 1H-pyridin-4-one ligands use their O atoms to bridge two symmetrically related AgNO₃ units to form a dimer, with an Ag···Ag separation of 3.680 (2)Å. The adjacent dimers are linked through weak Ag···Ag interactions [3.1511 (4)Å] into a one-dimensional polymeric chain, which is also stabilized by weak Ag···O interactions [2.765 (2)Å] and intrachain π–π interactions (Fig. 2). The centroid–centroid and interplanar distances between adjacent pyridyl rings are 3.623 (4) and 3.301 (4)Å, respectively, thus indicating a weak π–π contact (Deisenhofer & Michel, 1998; Li, Yin et al., 2005; Pan & Xu, 2004; Wu et al., 2003). The polymeric chain shows a staircase-like array, with an Ag···Ag···Ag angle of 63.51 (4)° between three successive Ag atoms along the chain. Such an array in the chain may be explained to avoid steric hindrance. N—H···O hydrogen bonds between the ligand N atoms and the nitrate O atoms (Table 2) link adjacent chains to furnish a lamellar layer. The interlayer N—H···O and C—H···O hydrogen bonds (Table 2) further assemble the neighbouring layers, giving rise to a three-dimensional supramolecular network (Fig. 3).

Experimental

A mixture of silver nitrate (0.17 g, 1 mmol), 4-hydroxypyridine (0.095 g, 1 mmol), NaOH (0.02 g, 0.5 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon-lined reactor, which was heated to 433 K for 3 d and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dried in air (yield 0.18 g, 69.2%).