1-Benz­yloxy-1H-benzotriazole

Jebas, S.R.; Selvarathy Grace, P.; Ravindran Durai Nayagam, B.; Schollmeyer, D.

doi:10.1107/S1600536812028395

organic compounds

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Volume 68| Part 7| July 2012| Page o2239

https://doi.org/10.1107/S1600536812028395

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1-Benzyloxy-1H-benzotriazole

Samuel Robinson Jebas,^a P. Selvarathy Grace,^b B. Ravindran Durai Nayagam ^b ^* and Dieter Schollmeyer ^c

^aDepartment of Physics, Sethupathy Government Arts College, Ramanathapuram 623 502, Tamilnadu, India, ^bDepartment of Chemistry, Popes College, Sawyerpuram 628 251, Tamilnadu, India, and ^cInstitut für Organische Chemie, Universität Mainz, Duesbergweg 10–14, 55099 Mainz, Germany
^*Correspondence e-mail: b_ravidurai@yahoo.com

(Received 19 June 2012; accepted 22 June 2012; online 30 June 2012)

In the title compound, C₁₃H₁₁N₃O, the dihedral angle between the benzotriazole ring system [maximum deviation = 0.027 (16) Å] and the benzene ring is 10.28 (9)°. The C—C—O—N bond adopts an anti conformation [torsion angle = −177.11 (16)°]. In the crystal, the molecules interact via weak C—H⋯π interactions and aromatic π–π stacking [centroid-to-centroid distance = 3.731 (12) Å].

Related literature

For a related structure and background to benzotriazoles, see: Selvarathy Grace et al. (2012 ).

Experimental

Crystal data

C₁₃H₁₁N₃O
M_r = 225.25
Orthorhombic, P b c a
a = 11.2417 (5) Å
b = 7.8381 (8) Å
c = 25.3933 (18) Å
V = 2237.5 (3) Å³
Z = 8
Cu Kα radiation
μ = 0.72 mm⁻¹
T = 193 K
0.51 × 0.45 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (CORINC; Wiehl & Schollmeyer, 1994 ) T_min = 0.84, T_max = 0.99
2125 measured reflections
2125 independent reflections
1867 reflections with I > 2σ(I)
R_int = 0.000
3 standard reflections every 60 min intensity decay: 3%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.163
S = 1.12
2125 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C12–C17 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯Cg1ⁱ	0.95	2.86	3.685 (2)	145
C16—H16⋯Cg1ⁱⁱ	0.95	2.99	3.691 (3)	132
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: CORINC (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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812028395/hb6865sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028395/hb6865Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028395/hb6865Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of benzotriazole derivatives with possible biological activities (Selvarathy Grace et al., 2012) we now report the crystal structure of the title compound (I).

The benzotriazole ring is essentially planar with the maximum deviation from planarity being 0.027 (16) Å for atom N2. The mean plane of the benzotriazole ring (N1–N3/C4–C9 forms a dihedral angle of 10.28 (9)° with the mean plane of the phenyl ring (C12–C17).

The crystal packing features π–π stacking interactions with the centroid-centroid distance of 3.731 (12) Å [symmetry code: 1 - x, -y, 1 - z], together with weak C—H···π interactions. Molecules are stacked along the b axis (Fig 2).

Related literature top

For a related structure and background to benzotriazoles, see: Selvarathy Grace et al. (2012).

Experimental top

A mixture of sodium salt of 1-hydroxy benzotriazole (0.157 g, 1 mmol) and benzyl chloride (0.126 g, 1 mmol) in ethanol and water (10 ml), were heated at 333 K with stirring for 6 h. The mixture was kept aside for slow evaporation. After a week, colourless blocks were obtained.

Structure description top

As part of our ongoing studies of benzotriazole derivatives with possible biological activities (Selvarathy Grace et al., 2012) we now report the crystal structure of the title compound (I).

For a related structure and background to benzotriazoles, see: Selvarathy Grace et al. (2012).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: CORINC (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).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis.

1-Benzyloxy-1H-benzotriazole top

Crystal data top

C₁₃H₁₁N₃O	F(000) = 944
M_r = 225.25	D_x = 1.337 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 11.2417 (5) Å	θ = 60–70°
b = 7.8381 (8) Å	µ = 0.72 mm⁻¹
c = 25.3933 (18) Å	T = 193 K
V = 2237.5 (3) Å³	Block, colourless
Z = 8	0.51 × 0.45 × 0.13 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1867 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.000
Graphite monochromator	θ_max = 70.0°, θ_min = 3.5°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (CORINC; Wiehl & Schollmeyer, 1994)	k = −9→0
T_min = 0.84, T_max = 0.99	l = 0→30
2125 measured reflections	3 standard reflections every 60 min
2125 independent reflections	intensity decay: 3%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.163	w = 1/[σ²(F_o²) + (0.0919P)² + 0.968P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2125 reflections	Δρ_max = 0.26 e Å⁻³
155 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (5)

Crystal data top

C₁₃H₁₁N₃O	V = 2237.5 (3) Å³
M_r = 225.25	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 11.2417 (5) Å	µ = 0.72 mm⁻¹
b = 7.8381 (8) Å	T = 193 K
c = 25.3933 (18) Å	0.51 × 0.45 × 0.13 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1867 reflections with I > 2σ(I)
Absorption correction: ψ scan (CORINC; Wiehl & Schollmeyer, 1994)	R_int = 0.000
T_min = 0.84, T_max = 0.99	3 standard reflections every 60 min
2125 measured reflections	intensity decay: 3%
2125 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.12	Δρ_max = 0.26 e Å⁻³
2125 reflections	Δρ_min = −0.23 e Å⁻³
155 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.59619 (14)	0.1616 (2)	0.41567 (6)	0.0319 (4)
N2	0.69169 (16)	0.0710 (2)	0.40089 (7)	0.0386 (5)
N3	0.74822 (17)	0.0253 (3)	0.44366 (6)	0.0390 (5)
C4	0.68515 (16)	0.0849 (3)	0.48621 (7)	0.0300 (4)
C5	0.70541 (19)	0.0634 (3)	0.54041 (8)	0.0363 (5)
H5	0.7724	0.0020	0.5531	0.044*
C6	0.6242 (2)	0.1348 (3)	0.57406 (8)	0.0395 (5)
H6	0.6348	0.1216	0.6110	0.047*
C7	0.5253 (2)	0.2276 (3)	0.55539 (8)	0.0390 (5)
H7	0.4719	0.2767	0.5802	0.047*
C8	0.50350 (18)	0.2493 (3)	0.50265 (9)	0.0342 (5)
H8	0.4366	0.3111	0.4900	0.041*
C9	0.58618 (17)	0.1744 (2)	0.46878 (7)	0.0285 (4)
O10	0.51465 (12)	0.21382 (19)	0.37887 (5)	0.0364 (4)
C11	0.56357 (18)	0.3549 (3)	0.34807 (8)	0.0373 (5)
H11A	0.6347	0.3171	0.3283	0.045*
H11B	0.5867	0.4503	0.3715	0.045*
C12	0.46776 (17)	0.4101 (3)	0.31104 (7)	0.0296 (5)
C13	0.47315 (18)	0.3682 (3)	0.25810 (8)	0.0352 (5)
H13	0.5377	0.3018	0.2453	0.042*
C14	0.3853 (2)	0.4220 (3)	0.22357 (8)	0.0400 (5)
H14	0.3901	0.3931	0.1873	0.048*
C15	0.29088 (19)	0.5177 (3)	0.24185 (9)	0.0398 (5)
H15	0.2310	0.5551	0.2181	0.048*
C16	0.28349 (19)	0.5589 (3)	0.29457 (9)	0.0403 (5)
H16	0.2177	0.6229	0.3073	0.048*
C17	0.37194 (18)	0.5069 (3)	0.32891 (8)	0.0357 (5)
H17	0.3673	0.5374	0.3651	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0274 (8)	0.0424 (9)	0.0260 (8)	0.0042 (7)	−0.0039 (6)	0.0034 (7)
N2	0.0322 (9)	0.0523 (11)	0.0314 (9)	0.0075 (8)	0.0002 (7)	−0.0007 (8)
N3	0.0316 (9)	0.0526 (11)	0.0330 (9)	0.0102 (8)	−0.0019 (7)	0.0024 (8)
C4	0.0233 (9)	0.0355 (10)	0.0311 (10)	−0.0005 (8)	−0.0026 (7)	0.0002 (8)
C5	0.0341 (10)	0.0432 (11)	0.0315 (10)	−0.0023 (9)	−0.0080 (8)	0.0044 (8)
C6	0.0417 (12)	0.0485 (12)	0.0284 (10)	−0.0087 (10)	−0.0031 (9)	−0.0010 (9)
C7	0.0376 (11)	0.0432 (12)	0.0361 (11)	−0.0059 (9)	0.0075 (9)	−0.0062 (9)
C8	0.0263 (9)	0.0357 (10)	0.0406 (10)	−0.0003 (8)	0.0011 (8)	0.0017 (8)
C9	0.0256 (9)	0.0327 (9)	0.0273 (9)	−0.0029 (8)	−0.0028 (7)	0.0015 (7)
O10	0.0279 (7)	0.0507 (9)	0.0307 (7)	−0.0054 (6)	−0.0097 (5)	0.0121 (6)
C11	0.0307 (10)	0.0430 (11)	0.0383 (11)	−0.0080 (9)	−0.0074 (8)	0.0124 (9)
C12	0.0260 (9)	0.0330 (10)	0.0299 (9)	−0.0056 (8)	−0.0038 (7)	0.0051 (7)
C13	0.0326 (11)	0.0393 (11)	0.0337 (11)	0.0015 (8)	0.0022 (8)	0.0015 (8)
C14	0.0492 (13)	0.0426 (11)	0.0283 (10)	−0.0043 (10)	−0.0074 (9)	0.0020 (8)
C15	0.0340 (11)	0.0382 (11)	0.0473 (13)	−0.0052 (9)	−0.0175 (9)	0.0095 (9)
C16	0.0278 (10)	0.0401 (11)	0.0530 (13)	0.0023 (9)	0.0001 (9)	0.0029 (10)
C17	0.0345 (11)	0.0409 (11)	0.0317 (10)	−0.0044 (9)	0.0018 (8)	0.0012 (8)

Geometric parameters (Å, º) top

N1—N2	1.341 (2)	O10—C11	1.462 (2)
N1—C9	1.357 (2)	C11—C12	1.494 (3)
N1—O10	1.3714 (19)	C11—H11A	0.9900
N2—N3	1.308 (2)	C11—H11B	0.9900
N3—C4	1.374 (3)	C12—C13	1.385 (3)
C4—C9	1.388 (3)	C12—C17	1.393 (3)
C4—C5	1.405 (3)	C13—C14	1.386 (3)
C5—C6	1.370 (3)	C13—H13	0.9500
C5—H5	0.9500	C14—C15	1.380 (3)
C6—C7	1.411 (3)	C14—H14	0.9500
C6—H6	0.9500	C15—C16	1.380 (3)
C7—C8	1.372 (3)	C15—H15	0.9500
C7—H7	0.9500	C16—C17	1.384 (3)
C8—C9	1.396 (3)	C16—H16	0.9500
C8—H8	0.9500	C17—H17	0.9500

N2—N1—C9	112.56 (15)	O10—C11—C12	106.54 (15)
N2—N1—O10	120.16 (15)	O10—C11—H11A	110.4
C9—N1—O10	126.85 (16)	C12—C11—H11A	110.4
N3—N2—N1	107.55 (16)	O10—C11—H11B	110.4
N2—N3—C4	108.00 (17)	C12—C11—H11B	110.4
N3—C4—C9	109.55 (17)	H11A—C11—H11B	108.6
N3—C4—C5	130.21 (19)	C13—C12—C17	118.63 (18)
C9—C4—C5	120.21 (18)	C13—C12—C11	120.70 (19)
C6—C5—C4	116.99 (19)	C17—C12—C11	120.66 (18)
C6—C5—H5	121.5	C12—C13—C14	120.7 (2)
C4—C5—H5	121.5	C12—C13—H13	119.7
C5—C6—C7	121.75 (19)	C14—C13—H13	119.7
C5—C6—H6	119.1	C15—C14—C13	120.04 (19)
C7—C6—H6	119.1	C15—C14—H14	120.0
C8—C7—C6	122.2 (2)	C13—C14—H14	120.0
C8—C7—H7	118.9	C16—C15—C14	119.99 (19)
C6—C7—H7	118.9	C16—C15—H15	120.0
C7—C8—C9	115.53 (19)	C14—C15—H15	120.0
C7—C8—H8	122.2	C15—C16—C17	119.9 (2)
C9—C8—H8	122.2	C15—C16—H16	120.0
N1—C9—C4	102.31 (16)	C17—C16—H16	120.0
N1—C9—C8	134.33 (18)	C16—C17—C12	120.70 (19)
C4—C9—C8	123.35 (18)	C16—C17—H17	119.7
N1—O10—C11	109.80 (14)	C12—C17—H17	119.7

C9—N1—N2—N3	−1.4 (2)	C5—C4—C9—C8	1.0 (3)
O10—N1—N2—N3	−174.41 (17)	C7—C8—C9—N1	177.9 (2)
N1—N2—N3—C4	1.5 (2)	C7—C8—C9—C4	−0.6 (3)
N2—N3—C4—C9	−1.2 (2)	N2—N1—O10—C11	−74.3 (2)
N2—N3—C4—C5	176.8 (2)	C9—N1—O10—C11	113.8 (2)
N3—C4—C5—C6	−178.2 (2)	N1—O10—C11—C12	−177.11 (16)
C9—C4—C5—C6	−0.3 (3)	O10—C11—C12—C13	−104.8 (2)
C4—C5—C6—C7	−0.7 (3)	O10—C11—C12—C17	76.1 (2)
C5—C6—C7—C8	1.1 (3)	C17—C12—C13—C14	0.3 (3)
C6—C7—C8—C9	−0.4 (3)	C11—C12—C13—C14	−178.85 (19)
N2—N1—C9—C4	0.7 (2)	C12—C13—C14—C15	−0.4 (3)
O10—N1—C9—C4	173.08 (18)	C13—C14—C15—C16	−0.4 (3)
N2—N1—C9—C8	−178.1 (2)	C14—C15—C16—C17	1.2 (3)
O10—N1—C9—C8	−5.7 (4)	C15—C16—C17—C12	−1.2 (3)
N3—C4—C9—N1	0.3 (2)	C13—C12—C17—C16	0.5 (3)
C5—C4—C9—N1	−177.93 (19)	C11—C12—C17—C16	179.64 (19)
N3—C4—C9—C8	179.28 (19)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C12–C17 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1ⁱ	0.95	2.86	3.685 (2)	145
C16—H16···Cg1ⁱⁱ	0.95	2.99	3.691 (3)	132

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁N₃O
M_r	225.25
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	193
a, b, c (Å)	11.2417 (5), 7.8381 (8), 25.3933 (18)
V (Å³)	2237.5 (3)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.51 × 0.45 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (CORINC; Wiehl & Schollmeyer, 1994)
T_min, T_max	0.84, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	2125, 2125, 1867
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.163, 1.12
No. of reflections	2125
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CORINC (Wiehl & Schollmeyer, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C12–C17 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1ⁱ	0.95	2.86	3.685 (2)	145
C16—H16···Cg1ⁱⁱ	0.95	2.99	3.691 (3)	132

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

References

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Selvarathy Grace, P., Jebas, S. R., Ravindran Durai Nayagam, B. & Schollmeyer, D. (2012). Acta Cryst. E68, o1132. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wiehl, L. & Schollmeyer, D. (1994). CORINC. University of Mainz, Germany. Google Scholar

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