1-(3,5-Dichloro­phen­yl)-1H-1,2,3,4-tetra­zole

Kalkhambkar, R.G.; Gayathri, D.; Gupta, V.K.; Kant, R.; Jeong, Y.T.

doi:10.1107/S1600536812001225

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o433

doi:10.1107/S1600536812001225

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1-(3,5-Dichlorophenyl)-1H-1,2,3,4-tetrazole

Rajesh G. Kalkhambkar,^a D. Gayathri,^b Vivek K. Gupta,^c Rajni Kant ^c and Yeon Tae Jeong ^d ^*

^aDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad 580 001, Karnataka, India, ^bDepartment of Physics, Dr M.G.R. Educational and Research Institute, Dr M.G.R. University, Maduravoyal, Chennai 600 095, India, ^cX-ray Crystallography Laboratory, Post Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^dDepartment of Image Science and Engineering, Pukyong National University, Busan 608 739, Republic of Korea
^*Correspondence e-mail: ytjeong@pknu.ac.kr

(Received 8 January 2012; accepted 11 January 2012; online 18 January 2012)

In the title compound, C₇H₄Cl₂N₄, the dihedral angle between the tetrazole and benzene rings is 17.2 (2)°. In the crystal, C—H⋯N interactions link the molecules into a flattened helical chain along the b axis.

Related literature

For related structures, see: Baek et al. (2012 ); Matsunaga et al. (1999 ); Lyakhov et al. (2000 , 2001 ). For the synthesis, see: Su et al. (2006 ).

Experimental

Crystal data

C₇H₄Cl₂N₄
M_r = 215.04
Monoclinic, P 2₁ /c
a = 3.8362 (2) Å
b = 9.0524 (3) Å
c = 24.8876 (11) Å
β = 91.956 (4)°
V = 863.76 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.699, T_max = 0.869
16772 measured reflections
1692 independent reflections
1451 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.114
S = 1.17
1692 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N2ⁱ	0.93	2.61	3.423 (5)	147
C7—H7⋯N1ⁱ	0.93	2.53	3.424 (5)	161
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001225/is5049sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001225/is5049Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812001225/is5049Isup3.cml

checkCIF report

Comment top

In continuation of our work on tetrazole based heterocycles, we are here in reporting the crystal structure of the title compound.

Bond lengths and angles are comparable with the similar crystal structures (Baek et al., 2012; Lyakhov et al., 2000, 2001; Matsunaga et al., 1999). The tetrazole and phenyl rings are planar, with a maximum out-of-plane deviation of 0.007 (2) Å for each ring (r.m.s. deviation for each ring = 0.005 Å). The two rings are not coplanar with a dihedral angle being 17.2 (2)°. Chlorine atoms Cl1 and Cl2 deviate -0.002 (4) and 0.057 (5) Å, respectively, from the benzene plane. The crystal packing is stabilized by C—H···N intermolecular interactions, wherein atoms C1 and C7 act as a donor to N2 and N1, respectively, generating C(4) and C(6) chains along [010].

Related literature top

For related structures, see: Baek et al. (2012); Matsunaga et al. (1999); Lyakhov et al. (2000, 2001). For the synthesis, see: Su et al. (2006).

Experimental top

The title compound was synthesized from the known procedure reported by Su et al. (2006). Fine white diffraction quality crystals were obtained from the slow evaporation of its solution in ethanol.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The molecular packing of the title compound, showing intermolecular interactions. For clarity, hydrogen atoms not involved in hydrogen bonding have been omitted.

1-(3,5-Dichlorophenyl)-1H-1,2,3,4-tetrazole top

Crystal data top

C₇H₄Cl₂N₄	F(000) = 432
M_r = 215.04	D_x = 1.654 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7140 reflections
a = 3.8362 (2) Å	θ = 4.0–29.0°
b = 9.0524 (3) Å	µ = 0.70 mm⁻¹
c = 24.8876 (11) Å	T = 293 K
β = 91.956 (4)°	Block, white
V = 863.76 (7) Å³	0.3 × 0.2 × 0.2 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1692 independent reflections
Radiation source: fine-focus sealed tube	1451 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 4.0°
ω scans	h = −4→4
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
T_min = 0.699, T_max = 0.869	l = −30→30
16772 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0229P)² + 1.3257P] where P = (F_o² + 2F_c²)/3
1692 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₇H₄Cl₂N₄	V = 863.76 (7) Å³
M_r = 215.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8362 (2) Å	µ = 0.70 mm⁻¹
b = 9.0524 (3) Å	T = 293 K
c = 24.8876 (11) Å	0.3 × 0.2 × 0.2 mm
β = 91.956 (4)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1692 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1451 reflections with I > 2σ(I)
T_min = 0.699, T_max = 0.869	R_int = 0.048
16772 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.17	Δρ_max = 0.31 e Å⁻³
1692 reflections	Δρ_min = −0.25 e Å⁻³
118 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.8151 (11)	0.8952 (4)	0.22313 (15)	0.0569 (10)
H1	0.7634	0.8155	0.2450	0.068*
C2	0.5993 (8)	0.7942 (3)	0.13392 (12)	0.0332 (7)
C3	0.4810 (8)	0.8412 (4)	0.08358 (13)	0.0389 (7)
H3	0.4966	0.9397	0.0734	0.047*
C4	0.3391 (8)	0.7360 (4)	0.04919 (12)	0.0410 (8)
C5	0.3089 (8)	0.5895 (4)	0.06386 (13)	0.0405 (8)
H5	0.2125	0.5202	0.0401	0.049*
C6	0.4258 (8)	0.5491 (3)	0.11477 (13)	0.0378 (7)
C7	0.5739 (8)	0.6494 (3)	0.15071 (12)	0.0348 (7)
H7	0.6533	0.6204	0.1848	0.042*
N1	0.9600 (10)	1.0175 (4)	0.23973 (13)	0.0619 (9)
N2	0.9905 (10)	1.1003 (4)	0.19516 (15)	0.0682 (10)
N3	0.8690 (10)	1.0311 (3)	0.15319 (13)	0.0655 (10)
N4	0.7517 (7)	0.9004 (3)	0.17044 (11)	0.0379 (6)
Cl1	0.1904 (3)	0.78829 (13)	−0.01453 (4)	0.0645 (3)
Cl2	0.3786 (3)	0.36798 (10)	0.13489 (4)	0.0639 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.084 (3)	0.043 (2)	0.042 (2)	−0.014 (2)	−0.0130 (19)	0.0013 (16)
C2	0.0334 (16)	0.0344 (16)	0.0319 (16)	−0.0010 (13)	0.0023 (12)	−0.0025 (13)
C3	0.0421 (18)	0.0371 (18)	0.0375 (17)	−0.0027 (14)	−0.0005 (14)	0.0056 (14)
C4	0.0377 (17)	0.054 (2)	0.0309 (16)	−0.0017 (15)	−0.0021 (13)	0.0045 (15)
C5	0.0388 (18)	0.0460 (19)	0.0367 (17)	−0.0075 (15)	−0.0016 (14)	−0.0061 (15)
C6	0.0403 (17)	0.0319 (16)	0.0414 (18)	−0.0016 (14)	0.0022 (14)	−0.0008 (14)
C7	0.0375 (17)	0.0351 (17)	0.0317 (16)	−0.0022 (13)	−0.0007 (13)	0.0018 (13)
N1	0.087 (3)	0.0454 (18)	0.052 (2)	−0.0120 (18)	−0.0179 (17)	−0.0070 (15)
N2	0.096 (3)	0.0420 (18)	0.065 (2)	−0.0217 (18)	−0.015 (2)	−0.0050 (17)
N3	0.103 (3)	0.0397 (17)	0.053 (2)	−0.0251 (18)	−0.0099 (19)	0.0065 (15)
N4	0.0451 (15)	0.0307 (14)	0.0375 (14)	−0.0040 (12)	−0.0038 (12)	−0.0002 (11)
Cl1	0.0754 (7)	0.0796 (7)	0.0374 (5)	−0.0070 (6)	−0.0160 (4)	0.0084 (5)
Cl2	0.0968 (8)	0.0353 (5)	0.0589 (6)	−0.0147 (5)	−0.0059 (5)	0.0006 (4)

Geometric parameters (Å, º) top

C1—N1	1.300 (5)	C4—Cl1	1.733 (3)
C1—N4	1.326 (4)	C5—C6	1.379 (4)
C1—H1	0.9300	C5—H5	0.9300
C2—C7	1.381 (4)	C6—C7	1.383 (4)
C2—C3	1.384 (4)	C6—Cl2	1.726 (3)
C2—N4	1.434 (4)	C7—H7	0.9300
C3—C4	1.380 (4)	N1—N2	1.347 (5)
C3—H3	0.9300	N2—N3	1.291 (4)
C4—C5	1.382 (5)	N3—N4	1.342 (4)

N1—C1—N4	110.3 (3)	C4—C5—H5	121.0
N1—C1—H1	124.9	C5—C6—C7	122.3 (3)
N4—C1—H1	124.9	C5—C6—Cl2	119.0 (2)
C7—C2—C3	122.7 (3)	C7—C6—Cl2	118.7 (2)
C7—C2—N4	118.4 (3)	C2—C7—C6	117.3 (3)
C3—C2—N4	118.8 (3)	C2—C7—H7	121.3
C4—C3—C2	117.4 (3)	C6—C7—H7	121.3
C4—C3—H3	121.3	C1—N1—N2	105.1 (3)
C2—C3—H3	121.3	N3—N2—N1	110.9 (3)
C3—C4—C5	122.2 (3)	N2—N3—N4	106.5 (3)
C3—C4—Cl1	119.3 (3)	C1—N4—N3	107.2 (3)
C5—C4—Cl1	118.4 (3)	C1—N4—C2	131.3 (3)
C6—C5—C4	118.0 (3)	N3—N4—C2	121.5 (3)
C6—C5—H5	121.0

C7—C2—C3—C4	−1.3 (5)	N4—C1—N1—N2	−0.8 (5)
N4—C2—C3—C4	179.3 (3)	C1—N1—N2—N3	0.0 (5)
C2—C3—C4—C5	1.0 (5)	N1—N2—N3—N4	0.7 (5)
C2—C3—C4—Cl1	−179.5 (2)	N1—C1—N4—N3	1.2 (5)
C3—C4—C5—C6	0.0 (5)	N1—C1—N4—C2	179.6 (3)
Cl1—C4—C5—C6	−179.6 (2)	N2—N3—N4—C1	−1.2 (4)
C4—C5—C6—C7	−0.8 (5)	N2—N3—N4—C2	−179.7 (3)
C4—C5—C6—Cl2	178.0 (3)	C7—C2—N4—C1	−16.1 (5)
C3—C2—C7—C6	0.6 (5)	C3—C2—N4—C1	163.4 (4)
N4—C2—C7—C6	180.0 (3)	C7—C2—N4—N3	162.1 (3)
C5—C6—C7—C2	0.5 (5)	C3—C2—N4—N3	−18.4 (5)
Cl2—C6—C7—C2	−178.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N2ⁱ	0.93	2.61	3.423 (5)	147
C7—H7···N1ⁱ	0.93	2.53	3.424 (5)	161

Symmetry code: (i) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₄Cl₂N₄
M_r	215.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	3.8362 (2), 9.0524 (3), 24.8876 (11)
β (°)	91.956 (4)
V (Å³)	863.76 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.699, 0.869
No. of measured, independent and observed [I > 2σ(I)] reflections	16772, 1692, 1451
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.114, 1.17
No. of reflections	1692
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.25

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N2ⁱ	0.93	2.609	3.423 (5)	147
C7—H7···N1ⁱ	0.93	2.531	3.424 (5)	161

Symmetry code: (i) −x+2, y−1/2, −z+1/2.

Acknowledgements

YTJ is grateful for the support provided by the second stage of BK21 Program. RK thanks the DST, New Delhi, India, for the X-ray data collection facility.

References

Baek, K., Gayathri, D., Gupta, V. K., Kant, R. & Jeong, Y. T. (2012). Acta Cryst. E68, o394. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lyakhov, A. S., Gaponik, P. N., Voitekhovich, S. V., Ivashkevich, L. S., Kulak, A. A. & Ivashkevich, O. A. (2001). Acta Cryst. C57, 1436–1437. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lyakhov, A. S., Ivashkevich, D. O., Gaponik, P. N., Grigoriev, Y. V. & Ivashkevich, L. S. (2000). Acta Cryst. C56, 256–257. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Matsunaga, T., Ohno, Y., Akutsu, Y., Arai, M., Tamura, M. & Iida, M. (1999). Acta Cryst. C55, 129–131. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, W. K., Hong, Z., Shan, W. G. & Zhang, X. X. (2006). Eur. J. Org. Chem. pp. 2723–2726. Web of Science CrossRef Google Scholar