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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.060
• Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level B
            Crystal system given = orthorhombic
PLAT431_ALERT_2_B Short Inter HL..A  Contact  Cl     ..  N3      .       2.82 Ang.
PLAT915_ALERT_3_B Low Friedel Pair Coverage ......................         50 Perc.

Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0042 Ang

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.19
           From the CIF: _reflns_number_total                918
           Count of symmetry unique reflns          643
           Completeness (_total/calc)            142.77%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       275
           Fraction of Friedel pairs measured     0.428
           Are heavy atom types Z>Si present        yes
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT093_ALERT_1_G No su's on H-positions, refinement reported as .      mixed
PLAT158_ALERT_4_G The Input Unitcell is NOT Standard/Reduced .....          ?
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT850_ALERT_4_G Check Flack Parameter Exact Value 0.00 and su ..       0.08
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          84 Perc.
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. 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.

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).

S2. 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.

S3. 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).

Computing details

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

	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.

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

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) Å^3	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 F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0242P)^2] where P = (Fo^2 + 2Fc^2)/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)

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)

	U^11	U^22	U^33	U^12	U^13	U^23
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)