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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o89.
Published online 2008 December 10. doi:  10.1107/S1600536808041482
PMCID: PMC2967996

3-(1H-Tetra­zol-5-yl)benzoic acid

Abstract

The title compound, C8H6N4O2, is a difunctional compound with a carboxyl­ate and a tetra­zole residue. In the crystal structure, mol­ecules are linked into two-dimensional sheets by inter­molecular N—H(...)O and O—H(...)N hydrogen bonds.

Related literature

For the applications of tetra­zoles, see: Chen & Tong (2007 [triangle]); Demko & Sharpless (2001 [triangle]). For related structures, see: Rizk et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-00o89-scheme1.jpg

Experimental

Crystal data

  • C8H6N4O2
  • M r = 190.17
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00o89-efi1.jpg
  • a = 5.2501 (10) Å
  • b = 16.805 (3) Å
  • c = 9.3290 (18) Å
  • β = 99.188 (3)°
  • V = 812.5 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 293 (2) K
  • 0.45 × 0.14 × 0.13 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan SADABS (Sheldrick, 2000 [triangle]) T min = 0.949, T max = 0.985
  • 5991 measured reflections
  • 1583 independent reflections
  • 1425 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.106
  • S = 1.07
  • 1583 reflections
  • 136 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041482/bt2829sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041482/bt2829Isup2.hkl

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

Tetrazoles have been extensively investigated in organic synthetic chemistry for several decades due to the fact that they have wide ranging applications in pharmaceuticals, especially explosives, photography, information recording systems, agriculture, and as precursors to a variety of heterocycles (Chen et al. 2007; Demko et al. 2001). They have also been used as a type of important multidentate ligands in coordination chemistry. Here, we report the crystal structure of a new tetrazole, 3-(1H-tetrazol-5-yl)benzoic acid.

The title compound, C8H6N4O2, is a difunctional compound with carboxylate and tetrazole groups. The C=O distance of the carboxylate is 1.216 (2) Å, which is much shorter than the C—O distance of 1.311 (2) Å. In the tetrazole group, the N=N distance is 1.288 (2) Å, and the N—N distances are 1.343 (2) and 1.358 (2) Å, respectively. The C—N distance is 1.333 (2) Å, being close to the C=N distance of 1.325 (2) Å, which is considered to have part double-bond character. In the crystalline state, the molecules are linked to two-dimensional hydrogen-bonding networks by intermolecular N—H···O and O—H···N hydrogen bonds. The N···O distance is 2.712 (2) Å, and the O···N distance is 2.666 (2) Å.

Experimental

A mixture of 3-cyanobenzoic acid (0.147 g, 1.0 mmol), Cd(NO3)2.6H2O (0.345 g, 1 mmol) and water (8 ml) was was heated in a 15-ml Teflon-lined autoclave at 160 ° for 3 days, followed by slow cooling (5 ° h-1) to room temperature. The resulting mixture was washed with water and collected. Then, the obtained solids were put into 20 ml water, and 10% Na2S aqueous solution was droped to the suspension liquid until that no precipitation appeared. The solution was filtered and the filtrate was acidified with 50% HCl solution until the pH value was 1.0. White products were filtered, washed with water, then dried and collected in 76.2% yield (0.145 g) based on 3-cyanobenzoic acid. Colorless block shaped crystals were collected from the filtrate after the second filtration.

Refinement

H atoms bonded to N and O atoms were located in a difference map and were freely refined. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with Uiso(H) = 1.2.

Figures

Fig. 1.
Structure of the title compound with 30% displacement ellipsoids.
Fig. 2.
The two-dimensional hydrogen bonding network of the title compound.
Fig. 3.
Packing of the title compound with view onto the ac plane.

Crystal data

C8H6N4O2F(000) = 392
Mr = 190.17Dx = 1.555 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 785 reflections
a = 5.2501 (10) Åθ = 2.4–28.0°
b = 16.805 (3) ŵ = 0.12 mm1
c = 9.3290 (18) ÅT = 293 K
β = 99.188 (3)°Block, colorless
V = 812.5 (3) Å30.45 × 0.14 × 0.13 mm
Z = 4

Data collection

Bruker APX CCD diffractometer1583 independent reflections
Radiation source: fine-focus sealed tube1425 reflections with I > 2σ(I)
graphiteRint = 0.018
phi and ω scanθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan SADABS (Sheldrick, 2000)h = −6→6
Tmin = 0.949, Tmax = 0.985k = −20→20
5991 measured reflectionsl = −11→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106w = 1/[σ2(Fo2) + (0.0592P)2 + 0.1634P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1583 reflectionsΔρmax = 0.19 e Å3
136 parametersΔρmin = −0.24 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.018 (3)

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
O10.0644 (2)0.36005 (6)0.68049 (12)0.0471 (3)
O20.3759 (2)0.42002 (6)0.58687 (13)0.0496 (3)
H2B0.410 (4)0.3707 (14)0.550 (2)0.082 (7)*
C10.1794 (3)0.42040 (8)0.65768 (15)0.0358 (3)
C20.1127 (3)0.50146 (7)0.70380 (15)0.0349 (3)
C3−0.0705 (3)0.51184 (8)0.79498 (16)0.0403 (4)
H3A−0.14990.46800.82960.048*
C4−0.1332 (3)0.58797 (9)0.83368 (16)0.0439 (4)
H4A−0.25390.59500.89550.053*
C5−0.0189 (3)0.65372 (8)0.78180 (16)0.0392 (3)
H5A−0.06400.70460.80810.047*
C60.1642 (3)0.64386 (7)0.68994 (14)0.0338 (3)
C70.2301 (2)0.56732 (8)0.65297 (14)0.0356 (3)
H7A0.35440.56020.59340.043*
C80.2910 (3)0.71171 (7)0.63149 (14)0.0338 (3)
N10.2597 (2)0.78846 (7)0.66034 (13)0.0402 (3)
N20.4101 (3)0.83282 (7)0.58804 (14)0.0453 (3)
N30.5310 (3)0.78398 (7)0.51637 (14)0.0445 (3)
N40.4608 (2)0.70804 (7)0.54077 (13)0.0394 (3)
H1A0.147 (4)0.8129 (12)0.716 (2)0.067 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0573 (7)0.0296 (5)0.0618 (7)−0.0056 (4)0.0317 (5)0.0017 (4)
O20.0616 (7)0.0266 (5)0.0718 (7)−0.0021 (4)0.0446 (6)−0.0037 (5)
C10.0416 (7)0.0290 (7)0.0408 (7)−0.0007 (5)0.0188 (6)0.0037 (5)
C20.0379 (7)0.0299 (7)0.0400 (7)0.0007 (5)0.0158 (6)0.0010 (5)
C30.0448 (8)0.0328 (7)0.0485 (8)−0.0023 (6)0.0231 (6)0.0013 (6)
C40.0468 (8)0.0408 (8)0.0510 (8)0.0015 (6)0.0285 (7)−0.0021 (6)
C50.0434 (8)0.0305 (7)0.0474 (8)0.0036 (5)0.0188 (6)−0.0048 (6)
C60.0374 (7)0.0285 (7)0.0380 (7)−0.0004 (5)0.0133 (5)−0.0002 (5)
C70.0394 (7)0.0311 (7)0.0406 (7)0.0002 (5)0.0195 (6)0.0003 (5)
C80.0383 (7)0.0266 (6)0.0388 (7)0.0026 (5)0.0131 (5)−0.0021 (5)
N10.0498 (7)0.0263 (6)0.0496 (7)0.0012 (5)0.0238 (6)−0.0017 (5)
N20.0564 (8)0.0290 (6)0.0559 (8)−0.0022 (5)0.0257 (6)0.0001 (5)
N30.0537 (7)0.0293 (6)0.0562 (8)−0.0026 (5)0.0260 (6)0.0005 (5)
N40.0470 (7)0.0263 (6)0.0504 (7)−0.0010 (5)0.0247 (5)−0.0010 (5)

Geometric parameters (Å, °)

O1—C11.2163 (16)C5—H5A0.9300
O2—C11.3112 (16)C6—C71.3898 (18)
O2—H2B0.93 (2)C6—C81.4684 (18)
C1—C21.4871 (18)C7—H7A0.9300
C2—C71.3868 (18)C8—N41.3254 (17)
C2—C31.3927 (19)C8—N11.3331 (17)
C3—C41.3833 (19)N1—N21.3430 (16)
C3—H3A0.9300N1—H1A0.94 (2)
C4—C51.381 (2)N2—N31.2882 (17)
C4—H4A0.9300N3—N41.3576 (16)
C5—C61.3961 (18)
C1—O2—H2B114.1 (14)C7—C6—C5119.03 (12)
O1—C1—O2122.47 (12)C7—C6—C8118.74 (11)
O1—C1—C2124.52 (12)C5—C6—C8122.22 (12)
O2—C1—C2113.01 (11)C2—C7—C6120.79 (12)
C7—C2—C3119.79 (12)C2—C7—H7A119.6
C7—C2—C1119.61 (11)C6—C7—H7A119.6
C3—C2—C1120.59 (11)N4—C8—N1106.91 (11)
C4—C3—C2119.44 (12)N4—C8—C6126.31 (11)
C4—C3—H3A120.3N1—C8—C6126.77 (12)
C2—C3—H3A120.3C8—N1—N2109.54 (11)
C5—C4—C3120.91 (12)C8—N1—H1A129.9 (12)
C5—C4—H4A119.5N2—N1—H1A120.5 (12)
C3—C4—H4A119.5N3—N2—N1106.56 (11)
C4—C5—C6120.02 (12)N2—N3—N4110.02 (11)
C4—C5—H5A120.0C8—N4—N3106.96 (10)
C6—C5—H5A120.0

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2B···N4i0.93 (2)1.76 (2)2.6664 (15)164 (2)
N1—H1A···O1ii0.94 (2)1.77 (2)2.7118 (16)179.1 (19)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2829).

References

  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, X.-M. & Tong, M.-L. (2007). Acc. Chem. Res.40, 162–170. [PubMed]
  • Demko, Z. P. & Sharpless, K. B. (2001). J. Org. Chem.66, 7945–7950. [PubMed]
  • Rizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359–362.
  • Sheldrick, G. M. (2000). SADABS, University of Göttingen.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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