1-Chloro­methyl-1H-1,2,3-benzotriazole

Zhu, X.; Zhang, Y.-J.; Zhang, C.-X.; Li, G.-S.; Qian, H.-Y.

doi:10.1107/S1600536810046052

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3173

https://doi.org/10.1107/S1600536810046052

Open

access

1-Chloromethyl-1H-1,2,3-benzotriazole

Xue-wen Zhu,^a,^b ^* Ying-Jun Zhang,^b Chun-Xia Zhang,^b Gang-Sen Li ^b and Heng-Yu Qian ^b

^aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China, and ^bKey Laboratory of Surface and Interface Science of Henan School of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China
^*Correspondence e-mail: zhuxuew@126.com

(Received 24 October 2010; accepted 8 November 2010; online 13 November 2010)

In the title compound, C₇H₆ClN₃, the benzotriazole ring is essentially planar with a maximum deviation of 0.0110 (15)Å, and makes a dihedral angle of 0.46 (8)° with the benzene ring. In the crystal, molecules are linked through intermolecular C—H⋯N hydrogen bonds, forming chains along the c axis.

Related literature

For bond-length data, see: Alkorta et al. (2004 ); Wang et al. (2008 ). For applications of 1-(chloromethyl)benzotriazole, see: Katritzky et al. (1996 ). For the preparation of the title compound, see: Burckhalter et al. (1952 ). For the biological activity of benzotriazole derivatives, see: Jiao et al. (2005 ).

Experimental

Crystal data

C₇H₆ClN₃
M_r = 167.60
Monoclinic, P 2₁ /c
a = 7.5081 (17) Å
b = 9.6045 (14) Å
c = 10.984 (2) Å
β = 108.49 (2)°
V = 751.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 293 K
0.21 × 0.20 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.914, T_max = 0.922
2865 measured reflections
1530 independent reflections
1218 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.088
S = 1.06
1530 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯N3ⁱ	0.97	2.47	3.360 (2)	152
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046052/fl2325sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046052/fl2325Isup2.hkl

checkCIF report

Comment top

Benzotriazole derivatives exhibit a good degree of anti-inflammatory, diuretic and antihypertensive activities (Jiao et al., 2005). The title compound (common name: 1-(chloromethyl)-benzotriazole), as one of the derivatives of benzotriazole, has been synthesized (Burckhalter et al., 1952)and used to synthesize 1-(mercaptomethyl)benzotriazole and other derivates(Katritzky et al. 1996). Now, we report herein the crystal structure of the benzotriazole derivative, (I).

The asymmetric unit of (I) comprises of one molecule of the compound (Fig. 1). The bond lengths and angles are found to have normal values (Alkorta et al, 2004; Wang et al., 2008). The benzotriazole ring is essentially planar with the maximum deviation form planarity being 0.0110 (15)Å for atom N1. The dihedral angle formed by the ring 1 (N1/N2/N3/C6/C1) and the ring 2 (C1/C2/C3/C4/C5/C6) is 0.46 (8)°. In the chloromethyl group, the C—Cl and C—N bond lengths are 1.7951 (18)Å and 1.424 (2) Å, respectively (Fig. 1). There is a C—H···N intermolecular interaction (Table 1, Fig. 2) stabilizing the observed molecular conformation, and the structure is further stalilized by pi···pi contacts involving both of the aromatic rings (Cg(1)—C(g)2 = 3.7003 (14) Å, which Cg(1) is the centroid of the ring 1 and Cg(2) is the centroid of the ring 2).

Related literature top

For bond-length data, see: Alkorta et al. (2004); Wang et al. (2008). For applications of 1-(chloromethyl)benzotriazole, see: Katritzky et al. (1996). For the preparation of the title compound, see: Burckhalter et al. (1952). For the biological activity of benzotriazole derivatives, see: Jiao et al. (2005).

Experimental top

The title compound was synthesized from 1-hydroxymethylbenzotriazole and thionyl chloride as described in the literature with a yield of 78% (Burckhalter et al., 1952). To 12 g of 1-hydroxymethylbenzotriazole kept at ice-bath temperature, 40 ml of thionyl chloride was added dropwise. The mixture was then stirred and refluxed for 90 minutes. Excess thionyl chloride was removed by distillation, last traces by heating for 15 minutes with 50 ml of methanol. After cooling and collecting on a funnel, the product was then recrystallized from benzene. Crystal suitable for X-ray diffraction analysis was obtained by crystallization from methanol.

Structure description top

For bond-length data, see: Alkorta et al. (2004); Wang et al. (2008). For applications of 1-(chloromethyl)benzotriazole, see: Katritzky et al. (1996). For the preparation of the title compound, see: Burckhalter et al. (1952). For the biological activity of benzotriazole derivatives, see: Jiao et al. (2005).

Computing details top

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

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom numbering scheme and displacement dllipsoids drawn at the 30% probability level.
	Fig. 2. Packing diagram viewed paralled to the c axis. Hydrogen bonds are indicated by dashed lines.

1-Chloromethyl-1H-1,2,3-benzotriazole top

Crystal data top

C₇H₆ClN₃	F(000) = 344
M_r = 167.60	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 409.5 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.7107 Å
a = 7.5081 (17) Å	Cell parameters from 1327 reflections
b = 9.6045 (14) Å	θ = 3.6–26.4°
c = 10.984 (2) Å	µ = 0.44 mm⁻¹
β = 108.49 (2)°	T = 293 K
V = 751.2 (3) Å³	Block, colourless
Z = 4	0.21 × 0.20 × 0.19 mm

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	1218 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.016
Graphite monochromator	θ_max = 26.4°, θ_min = 3.6°
ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −12→9
T_min = 0.914, T_max = 0.922	l = −8→13
2865 measured reflections	2865 standard reflections every 0 min
1530 independent reflections	intensity decay: none

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0381P)² + 0.0967P] where P = (F_o² + 2F_c²)/3
1530 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₇H₆ClN₃	V = 751.2 (3) Å³
M_r = 167.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5081 (17) Å	µ = 0.44 mm⁻¹
b = 9.6045 (14) Å	T = 293 K
c = 10.984 (2) Å	0.21 × 0.20 × 0.19 mm
β = 108.49 (2)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	1218 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	R_int = 0.016
T_min = 0.914, T_max = 0.922	2865 standard reflections every 0 min
2865 measured reflections	intensity decay: none
1530 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	Δρ_max = 0.23 e Å⁻³
1530 reflections	Δρ_min = −0.16 e Å⁻³
100 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
Cl1	0.28373 (7)	0.06214 (5)	0.48763 (5)	0.0569 (2)
N1	0.12629 (19)	0.31134 (15)	0.42214 (12)	0.0387 (3)
C6	0.2688 (2)	0.44038 (19)	0.63087 (16)	0.0411 (4)
H6A	0.2580	0.3716	0.6877	0.049*
N2	0.0960 (2)	0.34462 (18)	0.29614 (13)	0.0509 (4)
C7	0.0840 (2)	0.17530 (18)	0.45677 (18)	0.0436 (4)
H7A	−0.0195	0.1369	0.3878	0.052*
H7B	0.0453	0.1810	0.5329	0.052*
N3	0.1527 (2)	0.47155 (18)	0.29024 (14)	0.0534 (4)
C2	0.2235 (2)	0.52323 (19)	0.41342 (16)	0.0403 (4)
C1	0.2084 (2)	0.42052 (17)	0.49813 (15)	0.0332 (4)
C4	0.3611 (3)	0.6730 (2)	0.5873 (2)	0.0557 (5)
H4A	0.4140	0.7581	0.6204	0.067*
C3	0.3011 (3)	0.6533 (2)	0.4584 (2)	0.0514 (5)
H3B	0.3111	0.7231	0.4023	0.062*
C5	0.3451 (3)	0.5681 (2)	0.67153 (19)	0.0504 (5)
H5A	0.3884	0.5860	0.7592	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0606 (3)	0.0432 (3)	0.0670 (4)	0.0114 (2)	0.0204 (3)	0.0072 (2)
N1	0.0447 (8)	0.0379 (8)	0.0319 (7)	0.0053 (6)	0.0098 (6)	0.0008 (6)
C6	0.0460 (10)	0.0417 (10)	0.0365 (9)	0.0045 (8)	0.0142 (8)	0.0023 (8)
N2	0.0602 (10)	0.0574 (11)	0.0318 (8)	0.0121 (8)	0.0099 (7)	0.0023 (7)
C7	0.0432 (10)	0.0380 (10)	0.0489 (10)	0.0000 (8)	0.0135 (8)	−0.0045 (8)
N3	0.0648 (11)	0.0583 (11)	0.0393 (8)	0.0149 (9)	0.0198 (8)	0.0126 (8)
C2	0.0421 (10)	0.0433 (10)	0.0390 (9)	0.0114 (8)	0.0178 (8)	0.0094 (8)
C1	0.0325 (8)	0.0337 (9)	0.0348 (9)	0.0063 (7)	0.0125 (7)	0.0021 (7)
C4	0.0531 (12)	0.0403 (11)	0.0729 (13)	−0.0051 (9)	0.0188 (10)	−0.0092 (11)
C3	0.0534 (12)	0.0393 (11)	0.0682 (13)	0.0027 (9)	0.0286 (10)	0.0137 (10)
C5	0.0539 (11)	0.0513 (12)	0.0432 (10)	0.0019 (9)	0.0114 (9)	−0.0100 (9)

Geometric parameters (Å, º) top

Cl1—C7	1.7950 (18)	C7—H7B	0.9700
N1—C1	1.360 (2)	N3—C2	1.380 (2)
N1—N2	1.3674 (19)	C2—C1	1.385 (2)
N1—C7	1.424 (2)	C2—C3	1.401 (3)
C6—C5	1.367 (3)	C4—C3	1.356 (3)
C6—C1	1.396 (2)	C4—C5	1.399 (3)
C6—H6A	0.9300	C4—H4A	0.9300
N2—N3	1.299 (2)	C3—H3B	0.9300
C7—H7A	0.9700	C5—H5A	0.9300

C1—N1—N2	109.78 (14)	N3—C2—C3	130.89 (17)
C1—N1—C7	129.74 (13)	C1—C2—C3	120.79 (16)
N2—N1—C7	120.34 (14)	N1—C1—C2	104.75 (14)
C5—C6—C1	115.31 (17)	N1—C1—C6	132.87 (15)
C5—C6—H6A	122.3	C2—C1—C6	122.38 (16)
C1—C6—H6A	122.3	C3—C4—C5	121.34 (18)
N3—N2—N1	108.53 (14)	C3—C4—H4A	119.3
N1—C7—Cl1	111.25 (12)	C5—C4—H4A	119.3
N1—C7—H7A	109.4	C4—C3—C2	117.14 (17)
Cl1—C7—H7A	109.4	C4—C3—H3B	121.4
N1—C7—H7B	109.4	C2—C3—H3B	121.4
Cl1—C7—H7B	109.4	C6—C5—C4	123.04 (18)
H7A—C7—H7B	108.0	C6—C5—H5A	118.5
N2—N3—C2	108.61 (14)	C4—C5—H5A	118.5
N3—C2—C1	108.32 (16)

C1—N1—N2—N3	−1.26 (19)	N3—C2—C1—N1	−0.84 (18)
C7—N1—N2—N3	−177.32 (15)	C3—C2—C1—N1	179.33 (15)
C1—N1—C7—Cl1	−84.43 (19)	N3—C2—C1—C6	179.77 (15)
N2—N1—C7—Cl1	90.74 (16)	C3—C2—C1—C6	−0.1 (3)
N1—N2—N3—C2	0.7 (2)	C5—C6—C1—N1	−179.59 (17)
N2—N3—C2—C1	0.1 (2)	C5—C6—C1—C2	−0.4 (2)
N2—N3—C2—C3	179.91 (18)	C5—C4—C3—C2	−0.3 (3)
N2—N1—C1—C2	1.27 (18)	N3—C2—C3—C4	−179.37 (18)
C7—N1—C1—C2	176.84 (16)	C1—C2—C3—C4	0.4 (3)
N2—N1—C1—C6	−179.43 (17)	C1—C6—C5—C4	0.5 (3)
C7—N1—C1—C6	−3.9 (3)	C3—C4—C5—C6	−0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N3ⁱ	0.97	2.47	3.360 (2)	152

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₆ClN₃
M_r	167.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.5081 (17), 9.6045 (14), 10.984 (2)
β (°)	108.49 (2)
V (Å³)	751.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.21 × 0.20 × 0.19

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.914, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	2865, 1530, 1218
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.088, 1.06
No. of reflections	1530
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.16

Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N3ⁱ	0.97	2.47	3.360 (2)	152.3

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

We thank Yang Xiao-gan for the X-ray diffraction analysis.

References

Alkorta, I., Elguero, J., Jagerovic, N., Fruchier, A. & Yap, G. P. A. (2004). J. Heterocycl. Chem. 41, 285–289. CrossRef CAS Google Scholar
Burckhalter, J. H., Stephens, V. C. & Hall, L. A. R. (1952). J. Am. Chem. Soc. 74, 3868–3870. CrossRef CAS Web of Science Google Scholar
Jiao, K., Wang, Q.-X., Sun, W. & Jian, F.-F. (2005). J. Inorg. Biochem. 99, 1369–1375. Web of Science CSD CrossRef PubMed CAS Google Scholar
Katritzky, A. R., Ghiviriga, I., Oniciu, D. C. & Soti, F. (1996). J. Heterocycl. Chem. 33, 1927–1934. CrossRef CAS Google Scholar
Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. (2004). SADABS. University of Göttingen, Germany Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, S.-Q., Jian, F.-F. & Liu, H.-Q. (2008). Acta Cryst. E64, o1782. Web of Science CSD CrossRef IUCr Journals Google Scholar