catena-[[(nitrato-κO)silver(I)]-μ-1,10-phenanthroline-5,6-dione-κ4 O,O′:N,N′]

Xiao Jing; Yu-Lan Zhu; Kui-Rong Ma; Li Cao; Shuai Shao

doi:10.1107/S1600536811020939

. 2011 Jun 18;67(Pt 7):m957–m958. doi: 10.1107/S1600536811020939

catena-[[(nitrato-κO)silver(I)]-μ-1,10-phenanthroline-5,6-dione-κ⁴ O,O′:N,N′]

Xiao Jing ^a, Yu-Lan Zhu ^b,^*, Kui-Rong Ma ^b, Li Cao ^b, Shuai Shao ^a

PMCID: PMC3151901 PMID: 21836936

Abstract

In the title one-dimensional coordination polymer, [Ag(NO₃)(C₁₂H₆N₂O₂)]_n, the Ag^I atom is pentacoordinated by two N atoms from a 1,10-phenanthroline-5,6-dione (phen-dione) ligand, one O atom from the nitrate anion and two O atoms from another phen-dione ligand. The coordination environment around silver is slightly distorted square-pyramidal. Interestingly, the Ag—O distances to the phen-dione ligand are different [Ag—O = 2.612 (6) and 2.470 (5) Å]. The one-dimensional chains run parallel to [101] and are further interconnected by weak hydrogen bonds (C—H⋯O) and π–π stacking interactions [centroid–centroid distances 3.950 (4) and 3.792 (4) Å], forming a three-dimensional supramolecular network.

Related literature

For the use of 1,10-phenanthroline-5,6-dione (phen-dione) as an efficient chelating ligand establishing coordination polymers, see: Calderazzo et al. (2002 ▶); Wu et al. (1996 ▶); Liu & Xu (2006 ▶); Li et al. (2005 ▶). For examples of complexes with N,O-coordination of phen-dione, see: Paw & Eisenberg (1997 ▶); Ruiz et al. (1999 ▶); Shavaleev et al. (2003 ▶). For the synthesis of phen-dione, see: Paw & Eisenberg (1997 ▶). For the structure of a related phen-dione complex of Ag^I, see: Onuegbu et al. (2009 ▶). For a comparison of Ag—O bond lengths, see: Young & Hanton (2008 ▶); Sun et al. (2010 ▶); Wang et al. (2011 ▶).

Experimental

Crystal data

[Ag(NO₃)(C₁₂H₆N₂O₂)]
M _r = 380.07
Monoclinic,
a = 9.5058 (14) Å
b = 10.4647 (15) Å
c = 12.1615 (17) Å
β = 99.766 (2)°
V = 1192.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.72 mm⁻¹
T = 296 K
0.3 × 0.2 × 0.1 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.66, T _max = 0.84
6626 measured reflections
2307 independent reflections
1374 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.124
S = 1.00
2307 reflections
190 parameters
32 restraints
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −1.05 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020939/im2282sup1.cif

e-67-0m957-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020939/im2282Isup2.hkl

e-67-0m957-Isup2.hkl^{(113.4KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O4ⁱ	0.93	2.37	3.21 (1)	149

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant Nos. 20671038 and 20975043) and Jiangsu Key Laboratory for the Chemistry of Low-Dimensional Materials (grant No. JSKC09061).

supplementary crystallographic information

Comment

1, 10-phenanthroline-5,6-dione (phen-dione) is an efficient chelating ligand exhibiting two types of coordinating atoms (N and O) that are electronically coupled due to conjugation throughout the ligand. While phen-dione usually binds to metals through N atoms, in some cases both the N and O atoms are used simultaneously (Paw & Eisenberg,1997; Ruiz et al., 1999; Shavaleev et al., 2003).

In this paper we report the synthesis and characterization of the title compound, [Ag(phen-dione)(NO₃)]_n (1). Single-crystal X-ray diffraction study of 1 reveals the asymmetric unit to consist of one Ag (I) ion, one phen-dione ligand and one nitrate anion (Fig. 1). The silver atom is coordinated to two N atoms of a 1,10-phenanthroline-5,6-dione (phen-dione), one O atom from the nitrate anion and two O atoms from another phen-dione ligand giving rise to a slightly distorted square-pyramidal coordination sphere. The corresponding Ag–N bond distances are 2.445 (6) Å for Ag–N(1), 2.287 (6) Å for Ag–N(2) and Ag–O bond distances are observed to 2.474 (6) Å for Ag–O(1 A), 2.438 (7) Å for Ag–O(3) and 2.612 (6) Å for Ag–O(2 A). The latter bond length is longer than Ag–O(1 A) and Ag–O(3), but is well–matched to other examples reported in the literature (Young & Hanton, 2008; Wang et al., 2011; Sun et al., 2010).

In compound 1, the basic building units with a [AgN₂O₃]center are firstly interconnected to each other to produce a one-dimensional chain by additional Ag—O(1 A) and Ag—O(2 A) bonds (Fig. 2). Then the adjacent one-dimensional chains are further linked to each other to form three-dimensional network structure by the weak hydrogen bond C (1)–H(1)···O(4) (3.184 Å) between a CH function of a pyridine and an oxygen atom of the nitrate anion and π–π stacking interactions (Fig. 3). Two types of aromatic stacking interactions in 1 are observed between pyridine ring I (N (1), C (10), C (9), C (8), C (7), C (11)) and pyridine ring II (N (1), C (10), C (9), C (8), C (7), C (11)). There is one close distance between the centroids of pyridine I and II and another between two neighboring pyridine I moieties. The respective centroid-to-centroid distances are 3.950 (4) Å and 3.792 (4) Å.

The combination of coordinative bonds, hydrogen bonds, and π–π stacking interactions assemble the one-dimensional chain into a complicated three-dimensional supramolecular network.

Experimental

The title compound was synthesized according to the following steps: a solution of silver (I) nitrate (0.068 g, 0.4 mmol) and phen-dione (0.0212 g, 0.1 mmol) in methanol (8 ml) was stirred for 2 h. After filtering, the filtrate was left at room temperature for about two weeks. Yellow block shaped crystals of 1 were collected by vacuum filtration, washed thoroughly with methanol dried in air (yield 23% based on silver).