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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1368.
Published online 2008 June 28. doi:  10.1107/S1600536808019053
PMCID: PMC2961711

4-(1H-Tetra­zol-5-yl)benzoic acid monohydrate

Abstract

The asymmetric unit of the title compound, C8H6N4O2·H2O, consists of one 4-(1H-tetra­zol-5-yl)benzoic acid mol­ecule and one water mol­ecule. Hydrogen-bonding and π–π stacking (centroid–centroid distance between tetra­zole and benzene rings = 3.78 Å) inter­actions link the mol­ecules into a three-dimensional network.

Related literature

For general background, see: James et al. (2003 [triangle]); Kitagawa & Matsuda (2007 [triangle]); Maspoch et al. (2007 [triangle]); Pan et al. (2006 [triangle]); Li et al. (2007 [triangle]). For related tetra­zole ligands, see: Demko et al. (2001 [triangle]).

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Object name is e-64-o1368-scheme1.jpg

Experimental

Crystal data

  • C8H6N4O2·H2O
  • M r = 208.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1368-efi1.jpg
  • a = 4.914 (2) Å
  • b = 5.219 (2) Å
  • c = 34.720 (13) Å
  • β = 91.00 (3)°
  • V = 890.4 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 293 (2) K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Rigaku AFC-7R diffractometer
  • Absorption correction: ψ scan (Psi in WinAFC Diffractometer Control Software; Rigaku 2002 [triangle]) T min = 0.927, T max = 1.000 (expected range = 0.917–0.988)
  • 3386 measured reflections
  • 1576 independent reflections
  • 1270 reflections with I > 2σ(I)
  • R int = 0.028
  • 3 standard reflections every 200 reflections intensity decay: 0.3%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.095
  • S = 1.01
  • 1576 reflections
  • 148 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: WinAFC Diffractometer Control Software (Rigaku, 2002 [triangle]); cell refinement: WinAFC Diffractometer Control Software; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019053/sj2513sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019053/sj2513Isup2.hkl

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

Acknowledgments

This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences and the Natural Science Foundation of Fujian Province (A0420002 and E0510029).

supplementary crystallographic information

Comment

The current interest in crystal engineering of metal-organic coordination polymers (MOCPs) stems not only from their intriguing variety of architectures and topologies but also from their characteristic physical and/or chemical properties, including ferroelectricity, luminescence, magnetism, nonlinear optics, and gas storage, (James, et al. 2003; Kitagawa, et al. 2007; Maspoch, et al. 2007; Pan, et al. 2006; Li, et al. 2007). Multifunctional organic ligands are necessary for constructing such frameworks. Tetrazoles are versatile ligands due to their many potential donor atoms. They can be synthesized easily by the reaction of a cyano group with NaN3 in the presence of ZnBr2 (Lewis acid) as a catalyst and water under reflux or hydrothermal reaction conditions (Demko, et al. 2001). Here, we report the synthesis and crystal structure of a new tetrazole [C8H6N4O2].H2O (I).

The asymmetric unit of (I), consists of one crystallographically independent 4–5H-tetrazolyl-benzenecarboxylate molecule and one lattice water molecule (Figure 1). The molecular skeleton of I is essentially planar and the dihedral angle between the tetrazole and benzene rings is 0.16 °. Two adjacent 4–5H-tetrazolyl-benzenecarboxylate molecules are linked to form a centrosymmetric dimer through O1—H1···O2 hydrogen bonds. These dimers are bridged by lattice water molecules through O1W—H1WA···N2 and O1W—H1WB···N3 hydrogen bonds to form a two-dimensional layer along the [0 1 0] and [7 0 1] directions, (Figure 2). The layers are organized further by π-π stacking interactions between the tetrazole and benzene rings to form a three-dimensional framework. The two rings involved in the π-π stacking interactions are nearly parallel to each other, with a dihedral angle of 0.15 ° between them. The Cg1···Cg2i distance is 3.78 Å where Cg1 and Cg2 are the centroids of the C1···C6 and C8/N1···N4 rings respectively (i = x-1, y, z).

Experimental

A mixture of zinc bromide (225 mg, 1.0 mmol), Na(4-cba) (4-Hcba = 4-cyanobenzoic acid) (65 mg, 1.0 mmol) and NaN3 (65 mg, 1.0 mmol) in 10 ml water were transferred into a Teflon-line stainless steel autoclave and heated to 413 K for 3 days, then cooled to room temperature at the rate of 1 K/h. The resulting solid powder was acidified with HCl (2M) to give the target product. Crystals were obtained by slow evaporation of the resulting solution.

Refinement

The H atoms bound to O1W, O1 and N1 were located in a difference Fourier synthesis and refined with isotropic displacement parameters and the O(N)—H distances restrained to a target value of 0.86 (1) Å, and with Uiso(H) of O1W being 1.2Ueq(O1W). The remaining aromatic H atoms were positioned geometrically and refined using a riding model with d(C-H) = 0.93Å, Uiso=1.2Ueq (C).

Figures

Fig. 1.
The molecular structure of I, with 30% probability displacement ellipsoids.
Fig. 2.
Packing of (I) into two-dimensional layers linked by O—H···N and O—H···O hydrogen bonds (green dashed lines).
Fig. 3.
A three-dimensional framework for (I) linked by the π-π stacking interactions (green dashed lines). Hydrogen bonds are shown as yellow dashed lines.

Crystal data

C8H6N4O2·H2OF000 = 432
Mr = 208.18Dx = 1.553 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 20 reflections
a = 4.914 (2) Åθ = 12–30º
b = 5.219 (2) ŵ = 0.12 mm1
c = 34.720 (13) ÅT = 293 (2) K
β = 91.00 (3)ºBlock, colorless
V = 890.4 (6) Å30.20 × 0.10 × 0.10 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometerRint = 0.028
Radiation source: rotating-anode generatorθmax = 25.0º
Monochromator: graphiteθmin = 3.5º
T = 293(2) Kh = −1→5
ω–2θ scansk = −6→6
Absorption correction: ψ scan(Psi in WinAFC Diffractometer Control Software; Rigaku 2002)l = −41→41
Tmin = 0.928, Tmax = 1.0003 standard reflections
3386 measured reflections every 200 reflections
1576 independent reflections intensity decay: 0.3%
1270 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095  w = 1/[σ2(Fo2) + (0.0403P)2 + 0.366P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
1576 reflectionsΔρmax = 0.17 e Å3
148 parametersΔρmin = −0.29 e Å3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O1W1.3075 (3)1.2115 (3)0.22404 (4)0.0510 (4)
H1WA1.400 (4)1.292 (4)0.2414 (5)0.061*
H1WB1.175 (3)1.304 (4)0.2153 (6)0.061*
O10.6331 (3)1.1354 (3)0.04240 (4)0.0456 (4)
H10.509 (4)1.157 (6)0.0242 (6)0.100*
O20.7482 (3)0.7840 (3)0.00986 (3)0.0453 (4)
N11.6033 (3)0.8366 (3)0.18939 (4)0.0363 (4)
H21.514 (4)0.965 (3)0.1990 (6)0.068*
N21.8032 (3)0.7255 (3)0.21010 (4)0.0429 (4)
N31.8788 (3)0.5272 (3)0.19041 (4)0.0439 (4)
N41.7318 (3)0.5062 (3)0.15713 (4)0.0396 (4)
C10.9801 (3)0.8752 (3)0.06869 (4)0.0301 (4)
C21.1494 (4)0.6629 (3)0.06537 (5)0.0345 (4)
H2A1.13500.55760.04380.041*
C31.3393 (4)0.6083 (3)0.09416 (5)0.0338 (4)
H3A1.45310.46690.09180.041*
C41.3602 (3)0.7647 (3)0.12651 (4)0.0289 (4)
C51.1923 (4)0.9778 (3)0.12961 (5)0.0340 (4)
H5A1.20761.08390.15110.041*
C61.0034 (3)1.0320 (3)0.10098 (5)0.0332 (4)
H6A0.89081.17420.10330.040*
C70.7755 (3)0.9317 (3)0.03801 (5)0.0319 (4)
C81.5608 (3)0.7022 (3)0.15704 (4)0.0297 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O1W0.0586 (9)0.0478 (9)0.0459 (8)0.0216 (7)−0.0217 (6)−0.0168 (6)
O10.0509 (8)0.0439 (8)0.0414 (7)0.0187 (7)−0.0173 (6)−0.0079 (6)
O20.0510 (8)0.0496 (8)0.0348 (7)0.0147 (7)−0.0156 (6)−0.0130 (6)
N10.0399 (9)0.0372 (9)0.0313 (8)0.0110 (7)−0.0114 (6)−0.0040 (6)
N20.0458 (9)0.0444 (9)0.0380 (8)0.0125 (8)−0.0152 (7)−0.0023 (7)
N30.0463 (9)0.0443 (9)0.0407 (8)0.0143 (8)−0.0138 (7)−0.0013 (7)
N40.0430 (9)0.0381 (9)0.0374 (8)0.0117 (7)−0.0102 (7)−0.0024 (7)
C10.0313 (9)0.0303 (9)0.0286 (8)0.0010 (7)−0.0027 (7)−0.0002 (7)
C20.0396 (10)0.0334 (10)0.0302 (9)0.0043 (8)−0.0055 (7)−0.0071 (7)
C30.0350 (9)0.0318 (9)0.0346 (9)0.0077 (8)−0.0052 (7)−0.0029 (7)
C40.0289 (8)0.0300 (9)0.0277 (8)0.0008 (7)−0.0035 (7)0.0016 (7)
C50.0399 (10)0.0323 (9)0.0294 (9)0.0050 (8)−0.0070 (7)−0.0064 (7)
C60.0360 (9)0.0297 (9)0.0337 (9)0.0080 (8)−0.0052 (7)−0.0027 (7)
C70.0333 (9)0.0326 (9)0.0296 (9)0.0035 (8)−0.0031 (7)−0.0011 (7)
C80.0322 (9)0.0285 (9)0.0284 (8)0.0020 (8)−0.0029 (7)0.0010 (7)

Geometric parameters (Å, °)

O1W—H1WA0.858 (10)C1—C21.392 (2)
O1W—H1WB0.859 (10)C1—C71.482 (2)
O1—C71.283 (2)C2—C31.385 (2)
O1—H10.877 (10)C2—H2A0.9300
O2—C71.250 (2)C3—C41.391 (2)
N1—C81.337 (2)C3—H3A0.9300
N1—N21.339 (2)C4—C51.390 (2)
N1—H20.872 (10)C4—C81.471 (2)
N2—N31.298 (2)C5—C61.378 (2)
N3—N41.356 (2)C5—H5A0.9300
N4—C81.324 (2)C6—H6A0.9300
C1—C61.391 (2)
H1WA—O1W—H1WB111 (2)C4—C3—H3A120.0
C7—O1—H1113 (2)C5—C4—C3119.78 (15)
C8—N1—N2109.02 (14)C5—C4—C8120.84 (15)
C8—N1—H2130.9 (16)C3—C4—C8119.38 (15)
N2—N1—H2119.7 (15)C6—C5—C4120.14 (15)
N3—N2—N1106.08 (14)C6—C5—H5A119.9
N2—N3—N4111.08 (14)C4—C5—H5A119.9
C8—N4—N3105.55 (14)C5—C6—C1120.35 (16)
C6—C1—C2119.63 (15)C5—C6—H6A119.8
C6—C1—C7120.49 (15)C1—C6—H6A119.8
C2—C1—C7119.88 (15)O2—C7—O1123.55 (15)
C3—C2—C1120.02 (16)O2—C7—C1120.08 (15)
C3—C2—H2A120.0O1—C7—C1116.37 (14)
C1—C2—H2A120.0N4—C8—N1108.27 (14)
C2—C3—C4120.08 (16)N4—C8—C4126.17 (15)
C2—C3—H3A120.0N1—C8—C4125.55 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.877 (10)1.744 (10)2.620 (2)176 (3)
O1W—H1WA···N2ii0.858 (10)2.234 (16)2.957 (2)142 (2)
O1W—H1WB···N3iii0.859 (10)2.046 (10)2.903 (2)175 (2)

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+7/2, y+1/2, −z+1/2; (iii) x−1, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2513).

References

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  • Kitagawa, S. & Matsuda, R. (2007). Coord. Chem. Rev.251, 2490–2509.
  • Li, X.-L., Chen, K., Liu, Y., Wang, Z.-X., Wang, T.-W., Zuo, J.-L., Li, Y.-Z., Wang, Y., Zhu, J.-S., Liu, J.-M., Song, Y. & You, X.-Z. (2007). Angew. Chem. Int. Ed.46, 6820–6823. [PubMed]
  • Maspoch, D., Ruiz-Molina, D. & Veciana, J. (2007). Chem. Soc. Rev.36, 770–818. [PubMed]
  • Pan, L., Parker, B., Huang, X., Olson, D. H., Lee, J. Y. & Li, J. (2006). J. Am. Chem. Soc.128, 4180–4180. [PubMed]
  • Rigaku (2002). WinAFC Diffractometer Control Software Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2004). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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