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 ▶); 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,

• a = 7.5081 (17) Å

• b = 9.6045 (14) Å

• c = 10.984 (2) Å

• β = 108.49 (2)°

• V = 751.2 (3) ų

• 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[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 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

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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.

Supplementary Material

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

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) .

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 U_iso(H) assigned to 1.2U_eq(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

C7H6ClN3	F(000) = 344
Mr = 167.60	Dx = 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

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

Refinement

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(Fo2) + (0.0381P)2 + 0.0967P] where P = (Fo2 + 2Fc2)/3
1530 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

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