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

Abstract

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  

• C₆H₄ClN₃

• M _r = 153.57

• Orthorhombic,

• a = 22.8022 (11) Å

• b = 14.2637 (8) Å

• c = 8.2259 (4) Å

• V = 2675.4 (2) ų

• 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 ▶) T _min = 0.979, T _max = 1.000

• 1503 measured reflections

• 918 independent reflections

• 867 reflections with I > 2σ(I)

• R _int = 0.017

Refinement  

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.060

• S = 1.06

• 918 reflections

• 91 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

• Absolute structure: Flack (1983 ▶), 275 Friedel pairs

• Flack parameter: 0.00 (8)

Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

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.

Experimental

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

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

Figures

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.

Crystal data

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

Data collection

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

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	Flack parameter: 0.00 (8)

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 > 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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, º)

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)