Diaqua­bis­[5-(2-pyridyl­meth­yl)tetra­zol­ato-κ2 N 1,N 5]zinc(II)

Yang Liu; Ya-Ling Li; Xiu-Guang Wang; En-Cui Yang

doi:10.1107/S1600536811019507

. 2011 May 28;67(Pt 6):m803. doi: 10.1107/S1600536811019507

Diaquabis[5-(2-pyridylmethyl)tetrazolato-κ² N ¹,N ⁵]zinc(II)

Yang Liu ^a, Ya-Ling Li ^a, Xiu-Guang Wang ^a, En-Cui Yang ^a,^*

PMCID: PMC3120314 PMID: 21754679

Abstract

In the title mononuclear complex, [Zn(C₇H₆N₅)₂(H₂O)₂], the Zn^II atom, located on an inversion centre, is in a distorted octahedral coordination geometry formed by four N atoms from two chelating 5-(2-pyridylmethyl)tetrazolate ligands and two O donors from two water molecules. Intermolecular O—H⋯N hydrogen bonds between the coordinated water molecule and the tetrazolyl group of the 5-(2-pyridylmethyl)tetrazolate ligand lead to the formation of a three-dimensional network.

Related literature

For metal-organic frameworks with tetrazolate ligands and their applications in magnetism, fluorescence and gas storage, see: Yang et al. (2011 ▶); Feng et al. (2010 ▶); Zhao et al. (2008 ▶); Panda et al. (2011 ▶). For metal complexes with in situ-generated 5-(2-pyridylmethyl)-tetrazolate ligands, see: Xu et al. (2009 ▶); Wang (2008 ▶).

Experimental

Crystal data

[Zn(C₇H₆N₅)₂(H₂O)₂]
M _r = 421.74
Monoclinic,
a = 6.6695 (4) Å
b = 13.8949 (8) Å
c = 10.8718 (5) Å
β = 127.055 (2)°
V = 804.05 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.57 mm⁻¹
T = 173 K
0.20 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.745, T _max = 0.885
3929 measured reflections
1388 independent reflections
1335 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.053
S = 1.05
1388 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 ▶) and DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019507/bt5553sup1.cif

e-67-0m803-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811019507/bt5553Isup2.hkl

e-67-0m803-Isup2.hkl^{(68.5KB, 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
O1—H1A⋯N4ⁱ	0.85	2.00	2.8395 (19)	171
O1—H1B⋯N2ⁱⁱ	0.85	2.16	2.9386 (18)	152

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

Acknowledgments

The authors gratefully acknowledge financial support from Tianjin Normal University.

supplementary crystallographic information

Comment

Design and construction of metal-organic frameworks (MOFs) with in situ generated tetrazolate ligands are of great interest due to their intriguing structures and topology (Zhao et al., 2008), promising applications in magnetism (Yang et al. 2011), luminscence (Feng et al. 2010), and gas storage (Panda et al. 2011) as well as the effectiveness, simplicity, and environmental friendliness of the in situ synthetic route. Up to date, lots of tetrazolyl-based MOFs have been reported with special interest on the tuning of the organic nitrile and metal ions (Xu et al. 2009; Wang et al., 2008). Herein, as our continuing investigations on the coordination chemistry of the tetrazolyl ligand, we report the crystal structure of a diaquazinc(II) complex with an in situ generated 5-(2-pyridylmethyl)-tetrazolate ligand.

The molecular structure of the title mononuclear complex is show Figure 1. The Zn^II ion in the mononuclear structure of I, locating on an inversion center, exhibits a slightly distorted octahedral geometry involoving four N donors from two in situ generated 5-(pyridin-2-ylmethyl)tetrazolate ligands, and two O atoms from a pair of coordinated water molecules. The flexible 5-(pyridin-2-ylmethyl)tetrazolate anion acts as a bidentate chelating ligand to coordinate with Zn^II through pyridyl and tetrazolyl N donors.

In the crystal structure, intermolecular O—H···N hydrogen bonds between the coordinated water molecules and the tetrazolyl group of 5-(2-pyridylmethyl)- tetrazolate ligand (Table 2) lead to the formation of a three-dimensional network (Figure 2).

Experimental

A mixture containing 2-(pyridin-2-yl)acetonitrile (26 mg, 0.2 mmol), Zn(NO₃)₂ (29.7 mg, 0.1 mmol), 1,3,5-benzenetricarboxylic acid (21.0 mg, 0.1 mmol), NaN₃ (13.0 mg, 0.2 mmol), and doubly deionized water (10.0 ml) was sealed in a Teflon-lined reactor (23.0 ml) and heated at 125 °C for 72 h. After the mixture was cooled to room temperature at a rate of 5.5°C/h, pale-yellow block-shaped crystals suitable for X-ray diffraction analysis were obtained. Yield: 56% based on Zn^II salt. Anal. Calcd.for C₁₄H₁₆N₁₀O₂Zn: C, 39.87; H, 3.82; N, 33.21%. Found: C, 39.85; H, 3.82; N, 33.24%.