catena-Poly[[silver(I)-μ-dipyrazin-2-ylamine] perchlorate monohydrate]

Wei Feng Song; Chong-Qing Wan; Jianfeng Liu

doi:10.1107/S1600536809037532

. 2009 Oct 10;65(Pt 11):m1339. doi: 10.1107/S1600536809037532

catena-Poly[[silver(I)-μ-dipyrazin-2-ylamine] perchlorate monohydrate]

Wei Feng Song ^a,^*, Chong-Qing Wan ^b, Jianfeng Liu ^a

PMCID: PMC2970971 PMID: 21578095

Abstract

In the title complex, {[Ag(C₈H₇N₅)]ClO₄·H₂O}_n, the multidentate dipyrazin-2-ylamine acts as a μ₂-bridging link with an anti–syn configuration, assembling the Ag^I ions into a zigzag chain structure. The Ag^I ion is linearly coordinated by two dipyrazin-2-ylamine ligands through two pyrazine N atoms. (ClO₄ ⁻)⋯π(pyrazine) [O⋯centroid distances of 3.612 (3) and 3.664 (1) Å] and π–π interactions [centroid–centroid distance = 3.518 (2) Å] as well as O—H⋯O and N—H⋯O hydrogen-bonds assemble the chains into a three-dimensional supramolecular aggregation.

Related literature

For oligo-α-pyridylamino metal-organic frameworks, see: Clérac et al. (2000 ▶); Chem et al. (2006 ▶). For other dipyrazin-2-ylamine (Hdpza)–metal complexes, see: Ismayilov et al. (2007 ▶). For supramolecular assemblies related to N-rich heterocycles, see: Egli & Sarkhel (2007 ▶); Mooibroek et al. (2008 ▶).

Experimental

Crystal data

[Ag(C₈H₇N₅)]ClO₄·H₂O
M _r = 398.52
Orthorhombic,
a = 9.035 (4) Å
b = 15.188 (6) Å
c = 18.556 (7) Å
V = 2546.4 (17) Å³
Z = 8
Mo Kα radiation
μ = 1.82 mm⁻¹
T = 293 K
0.51 × 0.41 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.36, T _max = 0.58
16026 measured reflections
3144 independent reflections
1786 reflections with I > 2σ(I)
R _int = 0.088

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.222
S = 1.01
3144 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 1.68 e Å⁻³
Δρ_min = −1.19 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037532/bg2275sup1.cif

e-65-m1339-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037532/bg2275Isup2.hkl

e-65-m1339-Isup2.hkl^{(154.4KB, 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
N5—H5⋯O1W	0.82	2.12	2.911 (1)	162
O1W—H1WB⋯O3ⁱ	0.89	2.21	3.036 (9)	154
O1W—H1WA⋯O2ⁱⁱ	0.89	2.45	3.306 (14)	161
O1W—H1WA⋯O1ⁱⁱ	0.89	2.51	3.063 (11)	121

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

Acknowledgments

The authors are grateful for financial support from the Science and Technology Program of Guangdong Province (2006B36701002).

supplementary crystallographic information

Comment

The oligo-α-pyridylamino ligands are widely employed in the construction of diverse interesting metal-organic frameworks (Clérac et al., 2000, Chem et al., 2006). By using one or both nitrogen ligation sites in each heteroaromatic ring attached to the rotatable C–N(amine) bond, dipyrazin-2-ylamine (Hdpza) has led to several Cu(II), Co(II), Ni(II) and Cr(II) complexes (Ismayilov et al., 2007). Notably, π–acidic aromatic rings such as these N-rich heterocycles have been demonstrated to play an important role in supramolecular assemblies through anion–π interaction, which is of current interest (Egli et al., 2007, Mooibroek et al., 2008).

The asymmetric unit in the title silver(I) complex ([Ag(Hdpza)]⁺.ClO₄^-.H₂O)_∞ consists of an [Ag(Hdpza)]⁺ cationic group, accompanied by one perchlorate anion and one water solvate (Fig.1). Each Ag^I center is surrounded by two Hdpza with two 4-pyrazinyl N atoms [N1 and N3ⁱ, (i): –x + 3/2, -y + 1, z – 1/2] bonding to the metal, while the ligand exhibits as a µ₂-bridging mode with the two 4-pyrazinyl N atoms as bonding sites to link the Ag^I ions into an infinite chain structure along the c axis (Fig.2). Cationic chains are stacked along the a axis and interconnect through π–π interactions (Fig. 2). In addition, a O_(perchl)···π_(pyrazine) interaction combines with O-H···O and N-H···O hydrogen-bonds (Table 1) to assemble the infinite chain motifs into a three-dimensional supramolecular structure .

Lattice water molecules and perchlorate anions are embedded within the interstices through O—H_(water)···O_(perchl) and N—H_(amine)···O_(water) H-bonding. The ClO₄^- anion simultaneously links three neighbouring chains through weak C—H···O_(perchl) (C···O span: 3.446 (1) Å - 3.499 (2) Å ) and O_(perchl) ···π interactions (O2···Cg: 3.612 (3) Å; O3···Cg: 3.664 (1) Å; Cg:the pyrazinyl ring centroid)

Experimental

Hdpza was synthesized following literature procedures (Ismayilov et al., 2007). A mixture of Hdpza (100 mg, 0.58 mmol) and AgClO₄.xH₂O (172 mg) in methanol (40 ml) was stirred for five hours at room temperature. The resulting clear solution was filtered and then left to stand in air for about 7 days. Brown crystals suitable for X-ray diffraction (97.1 mg, 42% yield, on the basis of Hdpza) were obtained.