Hexaaqua­magnesium(II) bis­{[2-(1-phenyl-1H-tetra­zol-5-yl)sulfan­yl]acetate}

Chun-Hua Fu; Xiang Zhou; Qing Yu; He-Dong Bian

doi:10.1107/S1600536810016983

. 2010 May 15;66(Pt 6):m657. doi: 10.1107/S1600536810016983

Hexaaquamagnesium(II) bis{[2-(1-phenyl-1H-tetrazol-5-yl)sulfanyl]acetate}

Chun-Hua Fu ^a, Xiang Zhou ^a, Qing Yu ^a,^*, He-Dong Bian ^a

PMCID: PMC2979576 PMID: 21579302

Abstract

The asymmetric unit of the title compound, [Mg(H₂O)₆](C₉H₇N₄O₂S)₂, contains one-half of a [Mg(H₂O)₆]²⁺ cation ( Inline graphic symmetry) and one uncoordinated 2-[(1-phenyl-1H-tetrazol-5-yl)sulfanyl]acetate anion. The Mg^II cation is coordinated by six water molecules, exhibiting a slightly distorted octahedral coordination. A two-dimensional network parallel to (001) is formed via extensive hydrogen-bonding interactions involving the water molecules as donors and the tetrazole N and carboxylate O atoms of the anion as acceptors. The shortest distance between two adjacent parallel benzene rings is 3.315 (2) Å. The dihedral angle between the benzene ring and the tetrazole ring is 40.98 (2)°.

Related literature

For general background, see: He et al. (2005 ▶); Yang et al. (2008 ▶). For synthetic details, see: D’Amico et al. (1957 ▶). For related structures with [Mg(H₂O)₆]²⁺ cations, see: Zhang et al. (2006 ▶); Zhou et al. (2008 ▶).

Experimental

Crystal data

[Mg(H₂O)₆](C₉H₇N₄O₂S)₂
M _r = 602.92
Triclinic,
a = 6.8380 (14) Å
b = 7.5220 (15) Å
c = 13.556 (3) Å
α = 92.57 (3)°
β = 99.14 (3)°
γ = 100.07 (3)°
V = 675.9 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.25 × 0.13 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.806, T _max = 0.931
3914 measured reflections
2347 independent reflections
1867 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.122
S = 1.02
2347 reflections
202 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); 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 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810016983/wm2320sup1.cif

e-66-0m657-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016983/wm2320Isup2.hkl

e-66-0m657-Isup2.hkl^{(115.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mg1—O3	2.039 (2)
Mg1—O5	2.061 (2)
Mg1—O4	2.093 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2	0.97 (5)	1.77 (6)	2.711 (3)	164 (5)
O3—H3B⋯O2ⁱ	0.75 (4)	2.00 (4)	2.727 (3)	162 (4)
O4—H4A⋯O1ⁱⁱ	0.77 (4)	2.13 (4)	2.899 (3)	172 (4)
O4—H4B⋯N4ⁱⁱⁱ	0.92 (4)	2.01 (4)	2.882 (3)	158 (4)
O5—H5A⋯N3ⁱⁱⁱ	0.84 (4)	2.08 (4)	2.896 (4)	164 (4)
O5—H5B⋯O1	0.84 (4)	1.85 (4)	2.682 (3)	172 (3)

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

Acknowledgments

We gratefully acknowledge the Natural Science Foundation of Guangxi (0832098) and the Program of Educational Innovation of Graduate Students (06020703M242).

supplementary crystallographic information

Comment

The design and synthesis of supramolecular complexes with a high-nuclearity and N-containing carboxylate ligands, especially tetrazole-containing ligands, has been a rapidly growing area of research due to their fascinating structures and interesting physical properties (He et al., 2005). Several transition metal and rare earths metal complexes with similar ligand systems were reported (Yang et al., 2008).

We are interested in the solid-state coordination chemistry of ligands derived from 2-(1-phenyl-1H-tetrazol-5-ylthio)acetic acid (HPsta). In order to understand the behavior of alkali earth metals with the HPsta ligand, we prepared the title compound, [Mg(H₂O)₆](Psta)₂, (I), the synthesis and structure of which are reported here.

As shown in Fig. 1, the asymmetric unit of (I) consists of one-half of a [Mg(H₂O)₆]²⁺ cation (site symmetry 1) and an uncoordinated 2-(1-phenyl-1H-tetrazol-5-ylthio)acetate monoanion. The Mg^II atom is coordinated by six water molecules in a slightly distorted octahedral coordination. The corresponding Mg—O distances (Table 1) are in agreement with similar complexes containing the [Mg(H₂O)]²⁺ cation (Zhang et al., 2006; Zhou et al., 2008). The dihedral angle between the benzene ring and the tetrazole ring is 40.98 (2) °. In the crystal structure, the two Psta groups are involved in a number of intermolecular hydrogen bonds (Table 2) involving the O and N atoms as acceptors and the coordinated water molecules as donor groups (Fig. 2; Table 2), leading to a layer structure extending parallel to (001). In addition, π—π stacking is observed with a shortest distance between two adjacent parallel benzene rings of 3.315 (2) Å.

Experimental

The ligand 2-(1-phenyl-1H-tetrazol-5-ylthio)acetic acid (HPsta) was synthesized according to the literature method (D'Amico et al., 1957). To prepare the title complex, the ligand HPsta (0.4 mmol,0.0944 g) was dissolved in methanol (6 ml) at 348 K and an aqueous solution (4 ml) containing MgCO₃ (0.0336 g, 0.4 mmol) was added. The resulting solution was stirred at 348 K for 4 h, then cooled to room temperature and filtered. Colorless, prismatic crystals suitable for X-ray diffraction were obtained by slow evaporation over several days, with a yield of 61%. Elemental analysis, found (%):C, 35.79; H, 4.38; O, 26.65; N, 18.52; S, 10.66 calc(%): 35.88; H, 4.32; O, 26.58; N, 18.60; S, 10.63.