organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

1-Chloro-1H-1,2,3-benzotriazole

aDepartment of Pharmacy, The First Affiliated Hospital, Chengdu Medical College, Chengdu 610500, People's Republic of China
*Correspondence e-mail: zhenglinli326@163.com

(Received 14 October 2012; accepted 30 October 2012; online 24 November 2012)

The title compound, C6H4ClN3, is essentially planar, with a maximum deviation of 0.007 (3) Å. In the crystal, a short contact of 2.818 (3) Å is observed between N and Cl atoms of adjacent mol­ecules.

Related literature

For related structures of benzotriazole derivatives, see: Jebas et al. (2012[Jebas, S. R., Selvarathy Grace, P., Ravindran Durai Nayagam, B. & Schollmeyer, D. (2012). Acta Cryst. E68, o2239.]); Guo et al. (2012[Guo, T., Cao, G. & Xu, S. (2012). Acta Cryst. E68, o1409.]); Selvarathy et al. (2012[Selvarathy Grace, P., Jebas, S. R., Ravindran Durai Nayagam, B. & Schollmeyer, D. (2012). Acta Cryst. E68, o1132.]); Xu & Shen (2012[Xu, S. & Shen, Y. (2012). Acta Cryst. E68, o1066.]). For applications of the title compound, see: Hunter et al. (2006[Hunter, R., Caira, M. & Stellenboom, N. (2006). J. Org. Chem. 71, 8268-8271.]) and references cited therein. For the biological activity of benzotriazole derivatives, see: Gaikwad et al. (2012[Gaikwad, N. D., Patil, S. V. & Bodade, V. D. (2012). Bioorg. Med. Chem. Lett. 22, 3449-3454.]); Dubey et al. (2011[Dubey, A., Srivastava, S. K. & Srivastava, S. D. (2011). Bioorg. Med. Chem. Lett. 21, 569-573.]).

[Scheme 1]

Experimental

Crystal data
  • C6H4ClN3

  • Mr = 153.57

  • Orthorhombic, F d d 2

  • a = 22.8022 (11) Å

  • b = 14.2637 (8) Å

  • c = 8.2259 (4) Å

  • V = 2675.4 (2) Å3

  • Z = 16

  • Mo Kα radiation

  • μ = 0.48 mm−1

  • T = 293 K

  • 0.42 × 0.34 × 0.32 mm

Data collection
  • Agilent Xcalibur Eos diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.979, Tmax = 1.000

  • 1503 measured reflections

  • 918 independent reflections

  • 867 reflections with I > 2σ(I)

  • Rint = 0.017

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.060

  • S = 1.06

  • 918 reflections

  • 91 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.15 e Å−3

  • Δρmin = −0.16 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 275 Friedel pairs

  • Flack parameter: 0.00 (8)

Data collection: CrysAlis PRO (Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Benzotriazole derivates are an important class of heterocylic compounds with essential applications in the organic synthesis and medicinal chemistry. In the synthetic chemistry, 1-chloro-1H-benzo[d][1,2,3]triazole is an important oxidation and chlorination reagent. Recently, 1-chloro-1H-benzo[d][1,2,3]triazole has been used in the synthesis of unsymmetrical disulfides (Hunter et al., 2006). Meanwhile, benzotriazole derivates derivates exhibit numerous essential bioactivitities, especially in antimicrobial (Gaikwad, et al., 2012) and antibubercular activities (Dubey et al. 2011). Most recently, several crystal structures of title compound derivates have been reported (Jebas et al., 2012; Guo et al., 2012; Selvarathy et al., 2012; Xu & Shen 2012), but crystal data of 1-chloro-1H-benzo[d][1,2,3]triazole has not been investigated. Herein, we report the synthesis and crystal structure of the title compound.

The molecular structure of 1-chloro-1H-benzo[d][1,2,3]triazole is shown in Fig. 1. The bond lengths and angles are within normal ranges. In the crystal, the short contact of 2.818 (3) Å between N and Cl atoms of adjacent molecules occurs.

Related literature top

For related structures of benzotriazole derivatives, see: Jebas et al. (2012); Guo et al. (2012); Selvarathy et al. (2012); Xu & Shen (2012). For applications of the title compound, see: Hunter et al. (2006) and references cited therein. For the biological activity of benzotriazole derivatives, see: Gaikwad et al. (2012); Dubey et al. (2011).

Experimental top

To a stirring solution of benzotriazole (10 g) in 50 ml of 50% acetic acid aqueous solution was added sodium hypochlorite solution (30 ml) at room temperature dropwise. After dropping, the solution was diluted with water (100 ml) to precipitate the product. The mixture was filtered, washed with water to afford 1-chloro-1H-benzo[d][1,2,3]triazole (8.5 g)as white solid. The single crystals of 1-chloro-1H-benzo[d][1,2,3]triazole were recrystallized from acetone at room temperature.

Refinement top

H atoms were included in idealized positions and refined using a riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Plane-to-plane stacking of alternate molecules parallel to the α axis.
1-Chloro-1H-1,2,3-benzotriazole top
Crystal data top
C6H4ClN3Dx = 1.525 Mg m3
Mr = 153.57Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2Cell parameters from 738 reflections
a = 22.8022 (11) Åθ = 3.0–28.5°
b = 14.2637 (8) ŵ = 0.48 mm1
c = 8.2259 (4) ÅT = 293 K
V = 2675.4 (2) Å3Block, colourless
Z = 160.42 × 0.34 × 0.32 mm
F(000) = 1248
Data collection top
Agilent Xcalibur Eos
diffractometer
918 independent reflections
Radiation source: fine-focus sealed tube867 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
Detector resolution: 16.0874 pixels mm-1θmax = 25.2°, θmin = 3.0°
ω scansh = 1527
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
k = 168
Tmin = 0.979, Tmax = 1.000l = 99
1503 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.060 w = 1/[σ2(Fo2) + (0.0242P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
918 reflectionsΔρmax = 0.15 e Å3
91 parametersΔρmin = 0.16 e Å3
1 restraintAbsolute structure: Flack (1983), 275 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (8)
Crystal data top
C6H4ClN3V = 2675.4 (2) Å3
Mr = 153.57Z = 16
Orthorhombic, Fdd2Mo Kα radiation
a = 22.8022 (11) ŵ = 0.48 mm1
b = 14.2637 (8) ÅT = 293 K
c = 8.2259 (4) Å0.42 × 0.34 × 0.32 mm
Data collection top
Agilent Xcalibur Eos
diffractometer
918 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
867 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 1.000Rint = 0.017
1503 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.060Δρmax = 0.15 e Å3
S = 1.06Δρmin = 0.16 e Å3
918 reflectionsAbsolute structure: Flack (1983), 275 Friedel pairs
91 parametersAbsolute structure parameter: 0.00 (8)
1 restraint
Special details top

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 > 2sigma(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
xyzUiso*/Ueq
Cl0.31785 (3)0.13250 (5)0.13509 (9)0.0508 (2)
N10.37734 (9)0.18891 (16)0.0618 (3)0.0436 (6)
N20.43133 (10)0.15132 (19)0.0788 (3)0.0544 (7)
N30.46849 (10)0.20933 (18)0.0121 (4)0.0537 (7)
C10.37873 (11)0.27246 (19)0.0179 (3)0.0369 (6)
C20.43801 (11)0.2849 (2)0.0484 (3)0.0402 (7)
C30.45739 (14)0.3651 (2)0.1311 (4)0.0538 (8)
H30.49690.37510.15310.065*
C40.41526 (15)0.4282 (2)0.1780 (4)0.0577 (9)
H40.42650.48220.23300.069*
C50.35617 (14)0.4133 (2)0.1453 (4)0.0550 (8)
H50.32920.45810.17960.066*
C60.33580 (13)0.3357 (2)0.0649 (4)0.0459 (8)
H60.29620.32620.04350.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0413 (4)0.0522 (4)0.0587 (4)0.0073 (4)0.0014 (4)0.0109 (4)
N10.0307 (12)0.0452 (15)0.0549 (15)0.0005 (12)0.0016 (12)0.0116 (13)
N20.0396 (15)0.0519 (17)0.072 (2)0.0078 (12)0.0062 (13)0.0114 (15)
N30.0327 (12)0.0566 (16)0.0719 (16)0.0032 (14)0.0019 (13)0.0092 (13)
C10.0367 (15)0.0383 (16)0.0358 (14)0.0036 (14)0.0016 (12)0.0000 (13)
C20.0368 (15)0.0404 (16)0.0434 (14)0.0002 (13)0.0010 (14)0.0022 (13)
C30.0494 (18)0.057 (2)0.0545 (19)0.0129 (16)0.010 (2)0.0014 (17)
C40.079 (2)0.0376 (18)0.0566 (19)0.0060 (18)0.002 (2)0.0069 (15)
C50.0570 (19)0.0439 (19)0.064 (2)0.0099 (16)0.0071 (18)0.0067 (18)
C60.0385 (15)0.0440 (19)0.0551 (18)0.0071 (14)0.0006 (14)0.0004 (16)
Geometric parameters (Å, º) top
Cl—N11.688 (2)C3—C41.371 (4)
N1—N21.350 (3)C3—H30.9300
N1—C11.360 (3)C4—C51.390 (4)
N2—N31.305 (3)C4—H40.9300
N3—C21.376 (4)C5—C61.371 (4)
C1—C21.386 (3)C5—H50.9300
C1—C61.386 (4)C6—H60.9300
C2—C31.403 (4)
N2—N1—C1112.1 (2)C4—C3—H3121.6
N2—N1—Cl120.4 (2)C2—C3—H3121.6
C1—N1—Cl127.46 (18)C3—C4—C5121.6 (3)
N3—N2—N1107.3 (2)C3—C4—H4119.2
N2—N3—C2108.7 (2)C5—C4—H4119.2
N1—C1—C2102.8 (2)C6—C5—C4123.0 (3)
N1—C1—C6133.5 (3)C6—C5—H5118.5
C2—C1—C6123.7 (3)C4—C5—H5118.5
N3—C2—C1109.1 (3)C5—C6—C1114.9 (3)
N3—C2—C3131.0 (3)C5—C6—H6122.5
C1—C2—C3120.0 (3)C1—C6—H6122.5
C4—C3—C2116.8 (3)

Experimental details

Crystal data
Chemical formulaC6H4ClN3
Mr153.57
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)293
a, b, c (Å)22.8022 (11), 14.2637 (8), 8.2259 (4)
V3)2675.4 (2)
Z16
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.42 × 0.34 × 0.32
Data collection
DiffractometerAgilent Xcalibur Eos
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2010)
Tmin, Tmax0.979, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
1503, 918, 867
Rint0.017
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.060, 1.06
No. of reflections918
No. of parameters91
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.16
Absolute structureFlack (1983), 275 Friedel pairs
Absolute structure parameter0.00 (8)

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010).

 

Acknowledgements

This project was supported by Applied Basic Research Programs of Science & Technology Department of Sichuan Province (No. 2012JY0035) and the research fund of Chengdu Medical College, China (No. CYZ11–021).

References

First citationAgilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.
First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals
First citationDubey, A., Srivastava, S. K. & Srivastava, S. D. (2011). Bioorg. Med. Chem. Lett. 21, 569–573.  Web of Science CrossRef CAS PubMed
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationGaikwad, N. D., Patil, S. V. & Bodade, V. D. (2012). Bioorg. Med. Chem. Lett. 22, 3449–3454.  Web of Science CrossRef CAS PubMed
First citationGuo, T., Cao, G. & Xu, S. (2012). Acta Cryst. E68, o1409.  CSD CrossRef IUCr Journals
First citationHunter, R., Caira, M. & Stellenboom, N. (2006). J. Org. Chem. 71, 8268–8271.  Web of Science CrossRef PubMed CAS
First citationJebas, S. R., Selvarathy Grace, P., Ravindran Durai Nayagam, B. & Schollmeyer, D. (2012). Acta Cryst. E68, o2239.  CSD CrossRef IUCr Journals
First citationSelvarathy Grace, P., Jebas, S. R., Ravindran Durai Nayagam, B. & Schollmeyer, D. (2012). Acta Cryst. E68, o1132.  CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals
First citationXu, S. & Shen, Y. (2012). Acta Cryst. E68, o1066.  CSD CrossRef IUCr Journals

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