organic compounds
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
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); 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
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2010); cell 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: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812044820/xu5634sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044820/xu5634Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044820/xu5634Isup3.cml
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.
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).
Data collection: CrysAlis PRO (Agilent, 2010); cell
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).Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. Plane-to-plane stacking of alternate molecules parallel to the α axis. |
C6H4ClN3 | Dx = 1.525 Mg m−3 |
Mr = 153.57 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Fdd2 | Cell parameters from 738 reflections |
a = 22.8022 (11) Å | θ = 3.0–28.5° |
b = 14.2637 (8) Å | µ = 0.48 mm−1 |
c = 8.2259 (4) Å | T = 293 K |
V = 2675.4 (2) Å3 | Block, colourless |
Z = 16 | 0.42 × 0.34 × 0.32 mm |
F(000) = 1248 |
Agilent Xcalibur Eos diffractometer | 918 independent reflections |
Radiation source: fine-focus sealed tube | 867 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 16.0874 pixels mm-1 | θmax = 25.2°, θmin = 3.0° |
ω scans | h = −15→27 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −16→8 |
Tmin = 0.979, Tmax = 1.000 | l = −9→9 |
1503 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-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 reflections | Δρmax = 0.15 e Å−3 |
91 parameters | Δρmin = −0.16 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 275 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (8) |
C6H4ClN3 | V = 2675.4 (2) Å3 |
Mr = 153.57 | Z = 16 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 22.8022 (11) Å | µ = 0.48 mm−1 |
b = 14.2637 (8) Å | T = 293 K |
c = 8.2259 (4) Å | 0.42 × 0.34 × 0.32 mm |
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 = 1.000 | Rint = 0.017 |
1503 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.060 | Δρmax = 0.15 e Å−3 |
S = 1.06 | Δρmin = −0.16 e Å−3 |
918 reflections | Absolute structure: Flack (1983), 275 Friedel pairs |
91 parameters | Absolute structure parameter: 0.00 (8) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Cl | 0.31785 (3) | 0.13250 (5) | −0.13509 (9) | 0.0508 (2) | |
N1 | 0.37734 (9) | 0.18891 (16) | −0.0618 (3) | 0.0436 (6) | |
N2 | 0.43133 (10) | 0.15132 (19) | −0.0788 (3) | 0.0544 (7) | |
N3 | 0.46849 (10) | 0.20933 (18) | −0.0121 (4) | 0.0537 (7) | |
C1 | 0.37873 (11) | 0.27246 (19) | 0.0179 (3) | 0.0369 (6) | |
C2 | 0.43801 (11) | 0.2849 (2) | 0.0484 (3) | 0.0402 (7) | |
C3 | 0.45739 (14) | 0.3651 (2) | 0.1311 (4) | 0.0538 (8) | |
H3 | 0.4969 | 0.3751 | 0.1531 | 0.065* | |
C4 | 0.41526 (15) | 0.4282 (2) | 0.1780 (4) | 0.0577 (9) | |
H4 | 0.4265 | 0.4822 | 0.2330 | 0.069* | |
C5 | 0.35617 (14) | 0.4133 (2) | 0.1453 (4) | 0.0550 (8) | |
H5 | 0.3292 | 0.4581 | 0.1796 | 0.066* | |
C6 | 0.33580 (13) | 0.3357 (2) | 0.0649 (4) | 0.0459 (8) | |
H6 | 0.2962 | 0.3262 | 0.0435 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0413 (4) | 0.0522 (4) | 0.0587 (4) | −0.0073 (4) | −0.0014 (4) | −0.0109 (4) |
N1 | 0.0307 (12) | 0.0452 (15) | 0.0549 (15) | −0.0005 (12) | −0.0016 (12) | −0.0116 (13) |
N2 | 0.0396 (15) | 0.0519 (17) | 0.072 (2) | 0.0078 (12) | 0.0062 (13) | −0.0114 (15) |
N3 | 0.0327 (12) | 0.0566 (16) | 0.0719 (16) | 0.0032 (14) | −0.0019 (13) | −0.0092 (13) |
C1 | 0.0367 (15) | 0.0383 (16) | 0.0358 (14) | 0.0036 (14) | −0.0016 (12) | 0.0000 (13) |
C2 | 0.0368 (15) | 0.0404 (16) | 0.0434 (14) | −0.0002 (13) | −0.0010 (14) | 0.0022 (13) |
C3 | 0.0494 (18) | 0.057 (2) | 0.0545 (19) | −0.0129 (16) | −0.010 (2) | −0.0014 (17) |
C4 | 0.079 (2) | 0.0376 (18) | 0.0566 (19) | −0.0060 (18) | −0.002 (2) | −0.0069 (15) |
C5 | 0.0570 (19) | 0.0439 (19) | 0.064 (2) | 0.0099 (16) | 0.0071 (18) | −0.0067 (18) |
C6 | 0.0385 (15) | 0.0440 (19) | 0.0551 (18) | 0.0071 (14) | −0.0006 (14) | −0.0004 (16) |
Cl—N1 | 1.688 (2) | C3—C4 | 1.371 (4) |
N1—N2 | 1.350 (3) | C3—H3 | 0.9300 |
N1—C1 | 1.360 (3) | C4—C5 | 1.390 (4) |
N2—N3 | 1.305 (3) | C4—H4 | 0.9300 |
N3—C2 | 1.376 (4) | C5—C6 | 1.371 (4) |
C1—C2 | 1.386 (3) | C5—H5 | 0.9300 |
C1—C6 | 1.386 (4) | C6—H6 | 0.9300 |
C2—C3 | 1.403 (4) | ||
N2—N1—C1 | 112.1 (2) | C4—C3—H3 | 121.6 |
N2—N1—Cl | 120.4 (2) | C2—C3—H3 | 121.6 |
C1—N1—Cl | 127.46 (18) | C3—C4—C5 | 121.6 (3) |
N3—N2—N1 | 107.3 (2) | C3—C4—H4 | 119.2 |
N2—N3—C2 | 108.7 (2) | C5—C4—H4 | 119.2 |
N1—C1—C2 | 102.8 (2) | C6—C5—C4 | 123.0 (3) |
N1—C1—C6 | 133.5 (3) | C6—C5—H5 | 118.5 |
C2—C1—C6 | 123.7 (3) | C4—C5—H5 | 118.5 |
N3—C2—C1 | 109.1 (3) | C5—C6—C1 | 114.9 (3) |
N3—C2—C3 | 131.0 (3) | C5—C6—H6 | 122.5 |
C1—C2—C3 | 120.0 (3) | C1—C6—H6 | 122.5 |
C4—C3—C2 | 116.8 (3) |
Experimental details
Crystal data | |
Chemical formula | C6H4ClN3 |
Mr | 153.57 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 293 |
a, b, c (Å) | 22.8022 (11), 14.2637 (8), 8.2259 (4) |
V (Å3) | 2675.4 (2) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.42 × 0.34 × 0.32 |
Data collection | |
Diffractometer | Agilent Xcalibur Eos diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2010) |
Tmin, Tmax | 0.979, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1503, 918, 867 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.060, 1.06 |
No. of reflections | 918 |
No. of parameters | 91 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.16 |
Absolute structure | Flack (1983), 275 Friedel pairs |
Absolute structure parameter | 0.00 (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
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.