1-Benzyl-1H-benzotriazole

Abstract

In the title compound, C₁₃H₁₁N₃, the benzotriazole ring system is essentially planar, with a maximum deviation of 0.0173 (18) Å, and forms a dihedral angle of 75.08 (8)Å with the phenyl ring. In the crystal, pairs of weak C—H⋯N hydrogen bonds form inversion dimers. In addition, there are weak C—H⋯π(arene) inter­actions and weak π–π stacking inter­actions, with a centroid–centroid distance of 3.673 (11) Å.

Related literature  

For the biological activity of benzotriazole derivatives, see: Katarzyna et al. (2005 ▶); Sarala et al. (2007 ▶). For their applications, see: Kopec et al. (2008 ▶); Krawczyk & Gdaniec (2005 ▶); Smith et al. (2001 ▶); Sha et al. (1996 ▶). For a related structure, see: Ravindran et al. (2009 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental  

Crystal data  

• C₁₃H₁₁N₃

• M _r = 209.25

• Monoclinic,

• a = 11.5734 (10) Å

• b = 5.9705 (4) Å

• c = 16.1202 (14) Å

• β = 106.490 (4)°

• V = 1068.07 (15) ų

• Z = 4

• Cu Kα radiation

• μ = 0.64 mm⁻¹

• T = 193 K

• 0.30 × 0.20 × 0.10 mm

Data collection  

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ▶; Wiehl & Schollmeyer, 1994 ▶) T _min = 0.832, T _max = 0.939

• 2125 measured reflections

• 2020 independent reflections

• 1788 reflections with I > 2σ(I)

• R _int = 0.108

• 3 standard reflections every 60 min intensity decay: 2%

Refinement  

• R[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 0.138

• S = 1.12

• 2020 reflections

• 145 parameters

• H-atom parameters constrained

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶; Wiehl & Schollmeyer, 1994 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812010951/lh5426Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯N1i	0.95	2.62	3.513 (3)	158
C14—H14⋯Cgii	0.95	2.69	3.583 (2)	157

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Benzotriazole derivatives show biological activities such as anti-inflammatory, diuretic, antiviral and are antihypertensive agents (Katarzyna et al., 2005; Sarala et al., 2007). They are used as corrosion inhibitors, antifreeze agents, ultraviolet light stabilizer for plastics and as antifoggants in photography (Krawczyk & Gdaniec, 2005; Smith et al., 2001). N-Aryloxy derivatives of benzotriazole have anti-mycobacterial activity (Kopec et al., 2008). Benzotriazole possessing three vicinal N atoms, is used as an antifouling and antiwear reagent (Sha et al., 1996). These applications of benzotriazole compounds prompted us to synthesize the title compound and herein we report the crystal structure.

In (I) (Fig 1), the bond lengths (Allen et al., 1987) and bond angles have normal values. The benzotriazole ring system is essentially planar with a maximum deviation of 0.0173 (18) Å for atom N3. The mean plane of the benzotriazole ring system (N1—N3/C4—C9) forms a dihedral angle of 75.08 (8) Å with the mean plane of the phenyl ring (C11—C16).

In the crystal, pairs of weak C—H···N hydrogen bonds form centrosymmetric dimers (Fig. 2). In addition, there are weak π–π stacking interactions between ring N1-N3/C4/C9 and ring C4—C9(1-x, 1-y, 1-z) with a centroid-centroid distance of 3.673 (11)Å.

Experimental

A mixture of the sodium salt of benzotriazole (0.148 g, 1 mmol) benzyl chloride (0.126 g, 1 mmol) in ethanol and water (5 ml) were heated at 333K with continous stirring for 4 h. The mixture was kept aside for slow evaporation. After two weeks crystals of (I) suitable for X-ray diffraction were formed.

Refinement

H atoms were positioned geometrically [C—H = 0.95 (aromatic) or 0.99 Å (methylene)] and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of (I) with displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C13H11N3	F(000) = 440
Mr = 209.25	Dx = 1.301 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.5734 (10) Å	θ = 55–68°
b = 5.9705 (4) Å	µ = 0.64 mm−1
c = 16.1202 (14) Å	T = 193 K
β = 106.490 (4)°	Block, colourless
V = 1068.07 (15) Å3	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1788 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.108
Graphite monochromator	θmax = 70.0°, θmin = 4.0°
ω/2θ scans	h = 0→14
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971; Wiehl & Schollmeyer, 1994)	k = 0→7
Tmin = 0.832, Tmax = 0.939	l = −19→18
2125 measured reflections	3 standard reflections every 60 min
2020 independent reflections	intensity decay: 2%

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0628P)2 + 0.3976P] where P = (Fo2 + 2Fc2)/3
2020 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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
N1	0.42315 (15)	0.1763 (3)	0.37392 (11)	0.0331 (4)
N2	0.40768 (14)	0.2958 (3)	0.30376 (10)	0.0312 (4)
N3	0.35886 (13)	0.4957 (3)	0.31508 (10)	0.0255 (4)
C4	0.34149 (14)	0.5049 (3)	0.39488 (11)	0.0232 (4)
C5	0.29338 (17)	0.6694 (3)	0.43720 (12)	0.0291 (4)
H5	0.2638	0.8079	0.4105	0.035*
C6	0.29158 (18)	0.6177 (4)	0.52002 (13)	0.0345 (5)
H6	0.2588	0.7231	0.5513	0.041*
C7	0.33691 (17)	0.4130 (4)	0.55981 (12)	0.0332 (5)
H7	0.3349	0.3858	0.6174	0.040*
C8	0.38387 (17)	0.2517 (4)	0.51801 (13)	0.0324 (5)
H8	0.4147	0.1145	0.5453	0.039*
C9	0.38385 (15)	0.3007 (3)	0.43252 (12)	0.0256 (4)
C10	0.33293 (16)	0.6650 (3)	0.24689 (12)	0.0300 (4)
H10A	0.3745	0.6244	0.2031	0.036*
H10B	0.3648	0.8114	0.2721	0.036*
C11	0.19948 (16)	0.6862 (3)	0.20336 (11)	0.0254 (4)
C12	0.13833 (19)	0.8816 (3)	0.21182 (13)	0.0343 (5)
H12	0.1804	1.0015	0.2461	0.041*
C13	0.0167 (2)	0.9019 (4)	0.17048 (15)	0.0425 (5)
H13	−0.0246	1.0354	0.1769	0.051*
C14	−0.04510 (19)	0.7302 (4)	0.12006 (15)	0.0434 (6)
H14	−0.1285	0.7459	0.0912	0.052*
C15	0.01477 (19)	0.5340 (4)	0.11147 (13)	0.0376 (5)
H15	−0.0276	0.4148	0.0769	0.045*
C16	0.13627 (17)	0.5127 (3)	0.15333 (12)	0.0310 (4)
H16	0.1769	0.3778	0.1478	0.037*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0330 (9)	0.0294 (9)	0.0363 (9)	0.0057 (7)	0.0088 (7)	−0.0014 (7)
N2	0.0301 (8)	0.0319 (9)	0.0331 (9)	0.0056 (7)	0.0113 (7)	−0.0050 (7)
N3	0.0241 (7)	0.0282 (8)	0.0260 (8)	0.0022 (6)	0.0099 (6)	−0.0012 (6)
C4	0.0192 (8)	0.0264 (9)	0.0247 (9)	−0.0029 (7)	0.0072 (6)	−0.0010 (7)
C5	0.0314 (9)	0.0262 (10)	0.0323 (10)	0.0010 (8)	0.0133 (8)	−0.0016 (8)
C6	0.0370 (10)	0.0374 (11)	0.0331 (10)	−0.0026 (9)	0.0164 (8)	−0.0062 (9)
C7	0.0329 (10)	0.0446 (12)	0.0232 (9)	−0.0092 (9)	0.0097 (7)	0.0026 (8)
C8	0.0303 (9)	0.0327 (11)	0.0322 (10)	−0.0045 (8)	0.0059 (8)	0.0069 (8)
C9	0.0213 (8)	0.0250 (9)	0.0294 (9)	−0.0012 (7)	0.0055 (7)	0.0002 (7)
C10	0.0289 (9)	0.0354 (11)	0.0288 (9)	−0.0016 (8)	0.0130 (8)	0.0051 (8)
C11	0.0285 (9)	0.0303 (10)	0.0212 (8)	0.0005 (7)	0.0129 (7)	0.0064 (7)
C12	0.0410 (11)	0.0291 (10)	0.0356 (11)	0.0025 (9)	0.0155 (9)	0.0016 (9)
C13	0.0417 (12)	0.0384 (12)	0.0501 (13)	0.0146 (10)	0.0174 (10)	0.0082 (10)
C14	0.0303 (10)	0.0581 (15)	0.0403 (12)	0.0073 (10)	0.0074 (9)	0.0125 (11)
C15	0.0372 (11)	0.0433 (12)	0.0319 (10)	−0.0057 (9)	0.0090 (8)	−0.0009 (9)
C16	0.0345 (10)	0.0298 (10)	0.0315 (10)	0.0027 (8)	0.0137 (8)	0.0010 (8)

Geometric parameters (Å, º)

N1—N2	1.306 (2)	C10—C11	1.509 (2)
N1—C9	1.376 (2)	C10—H10A	0.9900
N2—N3	1.354 (2)	C10—H10B	0.9900
N3—C4	1.358 (2)	C11—C16	1.387 (3)
N3—C10	1.460 (2)	C11—C12	1.391 (3)
C4—C9	1.388 (3)	C12—C13	1.382 (3)
C4—C5	1.399 (3)	C12—H12	0.9500
C5—C6	1.376 (3)	C13—C14	1.376 (3)
C5—H5	0.9500	C13—H13	0.9500
C6—C7	1.411 (3)	C14—C15	1.388 (3)
C6—H6	0.9500	C14—H14	0.9500
C7—C8	1.373 (3)	C15—C16	1.382 (3)
C7—H7	0.9500	C15—H15	0.9500
C8—C9	1.409 (3)	C16—H16	0.9500
C8—H8	0.9500
N2—N1—C9	108.00 (16)	N3—C10—H10A	109.2
N1—N2—N3	108.93 (15)	C11—C10—H10A	109.2
N2—N3—C4	110.05 (15)	N3—C10—H10B	109.2
N2—N3—C10	120.85 (15)	C11—C10—H10B	109.2
C4—N3—C10	129.11 (15)	H10A—C10—H10B	107.9
N3—C4—C9	104.45 (16)	C16—C11—C12	118.97 (18)
N3—C4—C5	132.60 (17)	C16—C11—C10	120.57 (17)
C9—C4—C5	122.94 (17)	C12—C11—C10	120.46 (18)
C6—C5—C4	115.70 (18)	C13—C12—C11	120.2 (2)
C6—C5—H5	122.2	C13—C12—H12	119.9
C4—C5—H5	122.2	C11—C12—H12	119.9
C5—C6—C7	121.96 (19)	C14—C13—C12	120.5 (2)
C5—C6—H6	119.0	C14—C13—H13	119.8
C7—C6—H6	119.0	C12—C13—H13	119.8
C8—C7—C6	122.18 (18)	C13—C14—C15	119.8 (2)
C8—C7—H7	118.9	C13—C14—H14	120.1
C6—C7—H7	118.9	C15—C14—H14	120.1
C7—C8—C9	116.38 (18)	C16—C15—C14	119.8 (2)
C7—C8—H8	121.8	C16—C15—H15	120.1
C9—C8—H8	121.8	C14—C15—H15	120.1
N1—C9—C4	108.56 (16)	C15—C16—C11	120.71 (19)
N1—C9—C8	130.63 (18)	C15—C16—H16	119.6
C4—C9—C8	120.80 (18)	C11—C16—H16	119.6
N3—C10—C11	111.88 (15)
C9—N1—N2—N3	−0.1 (2)	N3—C4—C9—C8	177.98 (16)
N1—N2—N3—C4	−0.4 (2)	C5—C4—C9—C8	−2.1 (3)
N1—N2—N3—C10	179.31 (15)	C7—C8—C9—N1	−179.62 (19)
N2—N3—C4—C9	0.78 (18)	C7—C8—C9—C4	1.9 (3)
C10—N3—C4—C9	−178.94 (17)	N2—N3—C10—C11	106.88 (18)
N2—N3—C4—C5	−179.12 (18)	C4—N3—C10—C11	−73.4 (2)
C10—N3—C4—C5	1.2 (3)	N3—C10—C11—C16	−67.4 (2)
N3—C4—C5—C6	−179.41 (18)	N3—C10—C11—C12	113.53 (19)
C9—C4—C5—C6	0.7 (3)	C16—C11—C12—C13	−0.3 (3)
C4—C5—C6—C7	0.8 (3)	C10—C11—C12—C13	178.74 (17)
C5—C6—C7—C8	−1.0 (3)	C11—C12—C13—C14	−0.5 (3)
C6—C7—C8—C9	−0.4 (3)	C12—C13—C14—C15	0.8 (3)
N2—N1—C9—C4	0.6 (2)	C13—C14—C15—C16	−0.3 (3)
N2—N1—C9—C8	−178.05 (18)	C14—C15—C16—C11	−0.5 (3)
N3—C4—C9—N1	−0.84 (19)	C12—C11—C16—C15	0.9 (3)
C5—C4—C9—N1	179.07 (17)	C10—C11—C16—C15	−178.22 (17)

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···N1i	0.95	2.62	3.513 (3)	158
C14—H14···Cgii	0.95	2.69	3.583 (2)	157

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