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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3173.
Published online 2010 November 13. doi:  10.1107/S1600536810046052
PMCID: PMC3011609

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

Abstract

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 [triangle]); Wang et al. (2008 [triangle]). For applications of 1-(chloro­meth­yl)benzotriazole, see: Katritzky et al. (1996 [triangle]). For the preparation of the title compound, see: Burckhalter et al. (1952 [triangle]). For the biological activity of benzotriazole derivatives, see: Jiao et al. (2005 [triangle]).

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Object name is e-66-o3173-scheme1.jpg

Experimental

Crystal data

  • C7H6ClN3
  • M r = 167.60
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3173-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.088
  • S = 1.06
  • 1530 reflections
  • 100 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.16 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046052/fl2325Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms were included in calculated positions and refined as riding atoms with fixed C—H distances [C—H = 0.97Å for CH2, and 0.93Å for aromatic CH] and Uiso(H) assigned to 1.2Ueq(C) of their bonding carbon atom.

Figures

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.

Crystal data

C7H6ClN3F(000) = 344
Mr = 167.60Dx = 1.482 Mg m3
Monoclinic, P21/cMelting point: 409.5 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.7107 Å
a = 7.5081 (17) ÅCell parameters from 1327 reflections
b = 9.6045 (14) Åθ = 3.6–26.4°
c = 10.984 (2) ŵ = 0.44 mm1
β = 108.49 (2)°T = 293 K
V = 751.2 (3) Å3Block, colourless
Z = 40.21 × 0.20 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer1218 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray SourceRint = 0.016
graphiteθmax = 26.4°, θmin = 3.6°
ω scansh = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)k = −12→9
Tmin = 0.914, Tmax = 0.922l = −8→13
2865 measured reflections2865 standard reflections every 0 min
1530 independent reflections intensity decay: none

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0381P)2 + 0.0967P] where P = (Fo2 + 2Fc2)/3
1530 reflections(Δ/σ)max < 0.001
100 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.16 e Å3

Special details

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)

xyzUiso*/Ueq
Cl10.28373 (7)0.06214 (5)0.48763 (5)0.0569 (2)
N10.12629 (19)0.31134 (15)0.42214 (12)0.0387 (3)
C60.2688 (2)0.44038 (19)0.63087 (16)0.0411 (4)
H6A0.25800.37160.68770.049*
N20.0960 (2)0.34462 (18)0.29614 (13)0.0509 (4)
C70.0840 (2)0.17530 (18)0.45677 (18)0.0436 (4)
H7A−0.01950.13690.38780.052*
H7B0.04530.18100.53290.052*
N30.1527 (2)0.47155 (18)0.29024 (14)0.0534 (4)
C20.2235 (2)0.52323 (19)0.41342 (16)0.0403 (4)
C10.2084 (2)0.42052 (17)0.49813 (15)0.0332 (4)
C40.3611 (3)0.6730 (2)0.5873 (2)0.0557 (5)
H4A0.41400.75810.62040.067*
C30.3011 (3)0.6533 (2)0.4584 (2)0.0514 (5)
H3B0.31110.72310.40230.062*
C50.3451 (3)0.5681 (2)0.67153 (19)0.0504 (5)
H5A0.38840.58600.75920.061*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0606 (3)0.0432 (3)0.0670 (4)0.0114 (2)0.0204 (3)0.0072 (2)
N10.0447 (8)0.0379 (8)0.0319 (7)0.0053 (6)0.0098 (6)0.0008 (6)
C60.0460 (10)0.0417 (10)0.0365 (9)0.0045 (8)0.0142 (8)0.0023 (8)
N20.0602 (10)0.0574 (11)0.0318 (8)0.0121 (8)0.0099 (7)0.0023 (7)
C70.0432 (10)0.0380 (10)0.0489 (10)0.0000 (8)0.0135 (8)−0.0045 (8)
N30.0648 (11)0.0583 (11)0.0393 (8)0.0149 (9)0.0198 (8)0.0126 (8)
C20.0421 (10)0.0433 (10)0.0390 (9)0.0114 (8)0.0178 (8)0.0094 (8)
C10.0325 (8)0.0337 (9)0.0348 (9)0.0063 (7)0.0125 (7)0.0021 (7)
C40.0531 (12)0.0403 (11)0.0729 (13)−0.0051 (9)0.0188 (10)−0.0092 (11)
C30.0534 (12)0.0393 (11)0.0682 (13)0.0027 (9)0.0286 (10)0.0137 (10)
C50.0539 (11)0.0513 (12)0.0432 (10)0.0019 (9)0.0114 (9)−0.0100 (9)

Geometric parameters (Å, °)

Cl1—C71.7950 (18)C7—H7B0.9700
N1—C11.360 (2)N3—C21.380 (2)
N1—N21.3674 (19)C2—C11.385 (2)
N1—C71.424 (2)C2—C31.401 (3)
C6—C51.367 (3)C4—C31.356 (3)
C6—C11.396 (2)C4—C51.399 (3)
C6—H6A0.9300C4—H4A0.9300
N2—N31.299 (2)C3—H3B0.9300
C7—H7A0.9700C5—H5A0.9300
C1—N1—N2109.78 (14)N3—C2—C3130.89 (17)
C1—N1—C7129.74 (13)C1—C2—C3120.79 (16)
N2—N1—C7120.34 (14)N1—C1—C2104.75 (14)
C5—C6—C1115.31 (17)N1—C1—C6132.87 (15)
C5—C6—H6A122.3C2—C1—C6122.38 (16)
C1—C6—H6A122.3C3—C4—C5121.34 (18)
N3—N2—N1108.53 (14)C3—C4—H4A119.3
N1—C7—Cl1111.25 (12)C5—C4—H4A119.3
N1—C7—H7A109.4C4—C3—C2117.14 (17)
Cl1—C7—H7A109.4C4—C3—H3B121.4
N1—C7—H7B109.4C2—C3—H3B121.4
Cl1—C7—H7B109.4C6—C5—C4123.04 (18)
H7A—C7—H7B108.0C6—C5—H5A118.5
N2—N3—C2108.61 (14)C4—C5—H5A118.5
N3—C2—C1108.32 (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—N1179.33 (15)
C1—N1—C7—Cl1−84.43 (19)N3—C2—C1—C6179.77 (15)
N2—N1—C7—Cl190.74 (16)C3—C2—C1—C6−0.1 (3)
N1—N2—N3—C20.7 (2)C5—C6—C1—N1−179.59 (17)
N2—N3—C2—C10.1 (2)C5—C6—C1—C2−0.4 (2)
N2—N3—C2—C3179.91 (18)C5—C4—C3—C2−0.3 (3)
N2—N1—C1—C21.27 (18)N3—C2—C3—C4−179.37 (18)
C7—N1—C1—C2176.84 (16)C1—C2—C3—C40.4 (3)
N2—N1—C1—C6−179.43 (17)C1—C6—C5—C40.5 (3)
C7—N1—C1—C6−3.9 (3)C3—C4—C5—C6−0.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7A···N3i0.972.473.360 (2)152

Symmetry codes: (i) −x, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2325).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography