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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o742.
Published online 2010 March 3. doi:  10.1107/S1600536810003788
PMCID: PMC2983818

5-(4-Chloro­phen­yl)-1H-tetra­zole

Abstract

The two independent mol­ecules of the title compound, C7H5ClN4, both lie on a twofold rotation axis that passes through the centroids of the five- and six-membered rings and the attached Cl C atom. One molecule is nearly planar [dihedral angle between rings = 0.22 (6)°], whereas the other is significantly twisted [dihedral angle = 17.38 (6)°]. In the crystal, adjacent mol­ecules are linked by N—H(...)N hydrogen bonds into a chain structure.

Related literature

For the synthesis, see: Xu et al. (2009 [triangle]). For a related structure, see: Luo et al. (2006 [triangle]).

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Object name is e-66-0o742-scheme1.jpg

Experimental

Crystal data

  • C7H5ClN4
  • M r = 180.60
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o742-efi1.jpg
  • a = 9.4596 (19) Å
  • b = 11.437 (2) Å
  • c = 7.2988 (15) Å
  • β = 107.91 (3)°
  • V = 751.4 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.45 mm−1
  • T = 291 K
  • 0.21 × 0.14 × 0.11 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.912, T max = 0.952
  • 7237 measured reflections
  • 1720 independent reflections
  • 1194 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.135
  • S = 1.05
  • 1720 reflections
  • 118 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.77 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 [triangle]); 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/S1600536810003788/ng2726sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003788/ng2726Isup2.hkl

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

Acknowledgments

The authors thank Liaoning University of Traditional Chinese Medicine for supporting this study.

supplementary crystallographic information

Comment

The tetrazole functional group attracted considerable attention over recent years, because of both the intriguing architectures in coordination chemistry and the potential applications in medicinal chemistry and materials science (Luo et al., 2006). Herein, we reported the synthesis and the crystal structure of the title compound.

In the asymmetric unit of the title compound, C7H5ClN4, contains two half molecules of 5-(4-Chlorophenyl)-1H-tetrazole. In these two molecules, the centres of bezene and tetrazole rings locate on the symmetry plane, with the dihedral angle of 0.22 (6)° and 17.38 (6)°, respectively.

A one-dimensional chain structure is built up by N—H···N hydrogen bonds between the imino groups of the title compound.

Experimental

For the preparation of the title compound, 4-chlorobenzonitrile (13.7 g, 0.10 mol), ammonium chloride (13.4 g, 0.25 mmol) and NaN3 (7.8 g, 0.12 mol) were dissolved in DMF (120 ml). The mixture was heated to reflux stirred for 24 h under stirring. Then, it was cooled to room temperature and poured into cold water and acidified to pH = 2 with concentrated hydrochloric acid. The suspension was filtrated, and the residue was washed with water and ethanol for several times, and then dried (11.1 g, 61.8 %). Crystals suitable for X-ray analysis were obtained by recrystallization in the EtOH solution.

Refinement

Due to the title compound molecules located on the symmetry planes, the H atoms bound to N atoms were disordered into two positions with the occupancies of 0.5, respectively. H atoms bound to N atoms were located in a difference Fourier map and refined freely. H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic) and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms. Dashed lines indicate the hydrogen bonds.
Fig. 2.
A partial packing view, showing one-dimensional chain structure. Dashed lines indicate the hydrogen bonds.

Crystal data

C7H5ClN4F(000) = 368
Mr = 180.60Dx = 1.596 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 5352 reflections
a = 9.4596 (19) Åθ = 3.1–27.5°
b = 11.437 (2) ŵ = 0.45 mm1
c = 7.2988 (15) ÅT = 291 K
β = 107.91 (3)°Block, colorless
V = 751.4 (3) Å30.21 × 0.14 × 0.11 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer1720 independent reflections
Radiation source: fine-focus sealed tube1194 reflections with I > 2σ(I)
graphiteRint = 0.038
ω scanθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −12→12
Tmin = 0.912, Tmax = 0.952k = −14→14
7237 measured reflectionsl = −9→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0807P)2] where P = (Fo2 + 2Fc2)/3
1720 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.77 e Å3
0 restraintsΔρmin = −0.24 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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*/UeqOcc. (<1)
C10.00000.7724 (3)0.25000.0340 (7)
C20.1238 (2)0.7123 (2)0.3612 (3)0.0375 (5)
H10.20670.75300.43580.045*
C30.1235 (2)0.59197 (19)0.3606 (3)0.0331 (5)
H20.20680.55180.43500.040*
C40.00000.5293 (3)0.25000.0282 (6)
C50.00000.4029 (3)0.25000.0288 (6)
C60.5000−0.0727 (3)0.75000.0296 (6)
C70.3680 (2)−0.0135 (2)0.6704 (3)0.0389 (5)
H40.2797−0.05440.61880.047*
C80.3688 (2)0.1065 (2)0.6683 (3)0.0354 (5)
H50.28090.14710.61190.042*
C90.50000.1681 (2)0.75000.0258 (6)
C100.50000.2975 (3)0.75000.0267 (6)
Cl10.00000.92391 (7)0.25000.0492 (3)
Cl20.5000−0.22534 (7)0.75000.0464 (3)
N10.1109 (2)0.33285 (16)0.3488 (2)0.0349 (4)
H30.19340.34930.43180.050 (15)*0.50
N20.0660 (2)0.22079 (17)0.3089 (3)0.0418 (5)
N30.3941 (2)0.36603 (16)0.6406 (3)0.0349 (4)
H60.322 (5)0.352 (4)0.545 (6)0.016 (9)*0.50
N40.4364 (2)0.47685 (17)0.6842 (3)0.0398 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0332 (14)0.0274 (17)0.0377 (15)0.0000.0056 (12)0.000
C20.0313 (10)0.0320 (12)0.0424 (11)−0.0035 (8)0.0011 (9)−0.0024 (9)
C30.0270 (9)0.0298 (12)0.0349 (10)0.0000 (8)−0.0016 (8)0.0017 (8)
C40.0267 (13)0.0285 (17)0.0270 (13)0.0000.0046 (11)0.000
C50.0305 (13)0.0261 (15)0.0266 (12)0.0000.0038 (11)0.000
C60.0365 (14)0.0215 (15)0.0272 (13)0.0000.0047 (12)0.000
C70.0324 (11)0.0310 (12)0.0456 (12)−0.0054 (8)0.0006 (10)−0.0066 (9)
C80.0242 (9)0.0328 (12)0.0408 (11)0.0009 (8)−0.0021 (8)−0.0002 (9)
C90.0292 (13)0.0219 (15)0.0238 (12)0.0000.0044 (11)0.000
C100.0248 (12)0.0282 (16)0.0244 (12)0.0000.0037 (11)0.000
Cl10.0465 (5)0.0241 (5)0.0709 (6)0.0000.0090 (4)0.000
Cl20.0591 (5)0.0225 (5)0.0503 (5)0.0000.0061 (4)0.000
N10.0332 (8)0.0275 (10)0.0356 (9)0.0027 (7)−0.0019 (8)0.0001 (7)
N20.0437 (10)0.0245 (10)0.0456 (10)0.0031 (8)−0.0036 (8)0.0027 (8)
N30.0329 (9)0.0257 (10)0.0374 (9)0.0008 (7)−0.0018 (8)0.0000 (7)
N40.0381 (9)0.0259 (10)0.0450 (10)0.0016 (8)−0.0027 (8)0.0002 (8)

Geometric parameters (Å, °)

C1—C21.385 (3)C7—C81.373 (3)
C1—C2i1.385 (3)C7—H40.9300
C1—Cl11.732 (3)C8—C91.392 (2)
C2—C31.376 (3)C8—H50.9300
C2—H10.9300C9—C8ii1.392 (2)
C3—C41.397 (3)C9—C101.480 (4)
C3—H20.9300C10—N3ii1.328 (3)
C4—C3i1.397 (3)C10—N31.328 (3)
C4—C51.446 (4)N1—N21.353 (3)
C5—N1i1.340 (3)N1—H30.8492
C5—N11.340 (3)N2—N2i1.280 (4)
C6—C7ii1.382 (3)N3—N41.338 (3)
C6—C71.382 (3)N3—H60.83 (4)
C6—Cl21.746 (3)N4—N4ii1.288 (3)
C2—C1—C2i120.5 (3)C8—C7—H4120.4
C2—C1—Cl1119.77 (15)C6—C7—H4120.4
C2i—C1—Cl1119.77 (15)C7—C8—C9120.55 (19)
C3—C2—C1119.6 (2)C7—C8—H5119.7
C3—C2—H1120.2C9—C8—H5119.7
C1—C2—H1120.2C8—C9—C8ii119.2 (3)
C2—C3—C4121.05 (19)C8—C9—C10120.38 (13)
C2—C3—H2119.5C8ii—C9—C10120.38 (14)
C4—C3—H2119.5N3ii—C10—N3107.6 (3)
C3—C4—C3i118.2 (3)N3ii—C10—C9126.18 (13)
C3—C4—C5120.88 (14)N3—C10—C9126.18 (13)
C3i—C4—C5120.88 (14)C5—N1—N2107.97 (18)
N1i—C5—N1106.6 (3)C5—N1—H3130.3
N1i—C5—C4126.70 (14)N2—N1—H3121.5
N1—C5—C4126.70 (14)N2i—N2—N1108.73 (11)
C7ii—C6—C7121.3 (3)C10—N3—N4107.51 (18)
C7ii—C6—Cl2119.34 (14)C10—N3—H6131 (3)
C7—C6—Cl2119.34 (14)N4—N3—H6120 (3)
C8—C7—C6119.1 (2)N4ii—N4—N3108.67 (11)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H3···N30.85 (1)2.05 (1)2.889 (2)172 (1)
N3—H6···N10.83 (3)2.08 (4)2.889 (2)165.7 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2726).

References

  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Luo, J., Zhang, X.-R., Cui, L.-L., Dai, W.-Q. & Liu, B.-S. (2006). Acta Cryst. C62, m614–m616. [PubMed]
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalClear Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xu, H.-J., Pan, Y.-J. & Cui, L.-J. (2009). Acta Cryst. E65, o1331. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography