4-[(2H-Tetra­zol-2-yl)meth­yl]benzonitrile

Xing, Z.; Qu, Z.-R.

doi:10.1107/S1600536808000809

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o445

doi:10.1107/S1600536808000809

Open

access

4-[(2H-Tetrazol-2-yl)methyl]benzonitrile

Zheng Xing ^a and Zhi-Rong Qu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: quzr@seu.edu.cn

(Received 14 December 2007; accepted 8 January 2008; online 16 January 2008)

The title compound, C₉H₇N₅, was synthesized by reaction of 4-(bromomethyl)benzonitrile and 2H-tetrazole in the presence of KOH. The relative orientation of the planar tetrazole ring and the methylbenzonitrile moiety is (−)-anticlinal. The crystal packing is dominated by van der Waals interactions.

Related literature

For the chemisty of tetrazoles, see: Bethel et al. (1999 ); Wu et al. (2005 ); Zhang et al. (2006 ); Jin et al. (1994 ).

Experimental

Crystal data

C₉H₇N₅
M_r = 185.20
Triclinic, $[P \overline 1]$
a = 5.7514 (8) Å
b = 7.4029 (10) Å
c = 11.3511 (12) Å
α = 81.088 (3)°
β = 77.844 (3)°
γ = 72.600 (5)°
V = 448.64 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.20 × 0.12 × 0.02 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.980, T_max = 0.996
4114 measured reflections
1720 independent reflections
923 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.156
S = 0.92
1720 reflections
132 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: 10.1107/S1600536808000809/kp2157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000809/kp2157Isup2.hkl

checkCIF report

Comment top

Tetrazoles has been the subject of investigations during the last 20 years (Bethel et al., 1999). In recent years, tetrazoles have found a wide range of applications in coordination chemistry due to their role as mono- or bidentate ligands and strong networking ability (Wu et al., 2005; Zhang et al., 2006). Nitrile derivatives have found many industrial applications. For example, phthalonitriles have been used as starting materials for phthalocyanines (Jin et al., 1994). The title compound, is a new tetrazole derivative. We now report the synthesis and crystal structure analysis of 4-((2H-tetrazol-2-yl)methyl)benzonitrile (Fig. 1). The overall molecular conformation is defined by the torsion angle N1—N4—C8—C5 of -92.05 (10)°.

Related literature top

For the chemisty of tetrazoles, see: Bethel et al. (1999); Wu et al. (2005); Zhang et al. (2006); Jin et al. (1994).

Experimental top

The ligand 4-((2H-tetrazol-2-yl)methyl)benzonitrile was synthesized by reaction of 4-(bromomethyl)benzonitrile (1.95 g, 0.01 mol) and 2H-tetrazole (0.7 g, 0.01 mol) and KOH (0.56 g, 0.01 mol) in methanol (20 ml) reacted at 353 K with stirring for 24 h. A mixture of 4-((2H-tetrazol-2-yl)methyl)benzonitrile (18.5 mg, 0.1 mmol) and water (15 ml) and ethanol (15 ml) sealed in a glass were maintained at 293 K. Crystals suitable for X-ray ananlysis were obtained after 2 d.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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. A view of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

4-[(2H-Tetrazol-2-yl)methyl]benzonitrile top

Crystal data top

C₉H₇N₅	Z = 2
M_r = 185.20	F(000) = 192
Triclinic, P1	D_x = 1.371 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7514 (8) Å	Cell parameters from 655 reflections
b = 7.4029 (10) Å	θ = 3.3–27.4°
c = 11.3511 (12) Å	µ = 0.09 mm⁻¹
α = 81.088 (3)°	T = 293 K
β = 77.844 (3)°	Block, colourless
γ = 72.600 (5)°	0.20 × 0.12 × 0.02 mm
V = 448.64 (10) Å³

Data collection top

Rigaku Mercury2 diffractometer	1720 independent reflections
Radiation source: fine-focus sealed tube	923 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
CCD_Profile_fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
T_min = 0.980, T_max = 0.996	l = −13→13
4114 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.053	w = 1/[σ²(F_o²) + (0.0718P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.156	(Δ/σ)_max < 0.001
S = 0.92	Δρ_max = 0.17 e Å⁻³
1720 reflections	Δρ_min = −0.16 e Å⁻³
132 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.044 (14)
Secondary atom site location: difference Fourier map

Crystal data top

C₉H₇N₅	γ = 72.600 (5)°
M_r = 185.20	V = 448.64 (10) Å³
Triclinic, P1	Z = 2
a = 5.7514 (8) Å	Mo Kα radiation
b = 7.4029 (10) Å	µ = 0.09 mm⁻¹
c = 11.3511 (12) Å	T = 293 K
α = 81.088 (3)°	0.20 × 0.12 × 0.02 mm
β = 77.844 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1720 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	923 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.996	R_int = 0.045
4114 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	Δρ_max = 0.17 e Å⁻³
1720 reflections	Δρ_min = −0.16 e Å⁻³
132 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
N2	1.0618 (5)	0.2439 (4)	0.4265 (2)	0.0821 (8)
C1	0.3315 (4)	0.9248 (4)	0.9005 (2)	0.0554 (6)
C2	0.4374 (4)	0.7403 (3)	0.8573 (2)	0.0502 (6)
C3	0.6613 (4)	0.6272 (3)	0.8855 (2)	0.0547 (7)
H3	0.7445	0.6703	0.9324	0.066*
C4	0.7606 (4)	0.4506 (3)	0.8438 (2)	0.0560 (7)
H4	0.9121	0.3749	0.8622	0.067*
C5	0.6377 (4)	0.3841 (3)	0.7748 (2)	0.0525 (6)
C6	0.4133 (5)	0.4976 (4)	0.7479 (2)	0.0621 (7)
H6	0.3292	0.4541	0.7018	0.075*
C7	0.3128 (5)	0.6752 (4)	0.7891 (2)	0.0606 (7)
H7	0.1613	0.7510	0.7708	0.073*
C8	0.7485 (5)	0.1932 (3)	0.7266 (2)	0.0611 (7)
H8A	0.8329	0.1040	0.7865	0.073*
H8B	0.6176	0.1460	0.7124	0.073*
N1	0.8605 (4)	0.2339 (4)	0.5064 (2)	0.0764 (7)
C9	1.2358 (6)	0.2213 (5)	0.4920 (3)	0.0730 (9)
N3	1.1596 (4)	0.1945 (3)	0.6083 (2)	0.0703 (7)
N4	0.9239 (4)	0.2044 (3)	0.61371 (17)	0.0550 (6)
N5	0.2481 (4)	1.0719 (3)	0.9343 (2)	0.0770 (8)
H9	1.385 (6)	0.208 (5)	0.462 (3)	0.116 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0782 (17)	0.103 (2)	0.0630 (15)	−0.0277 (15)	−0.0037 (14)	−0.0081 (13)
C1	0.0509 (14)	0.0546 (15)	0.0616 (16)	−0.0117 (13)	−0.0132 (12)	−0.0098 (13)
C2	0.0510 (14)	0.0511 (14)	0.0485 (13)	−0.0148 (12)	−0.0083 (11)	−0.0038 (11)
C3	0.0527 (15)	0.0602 (16)	0.0554 (15)	−0.0151 (12)	−0.0162 (12)	−0.0101 (12)
C4	0.0481 (14)	0.0594 (15)	0.0569 (15)	−0.0083 (12)	−0.0081 (12)	−0.0091 (12)
C5	0.0569 (15)	0.0506 (14)	0.0493 (14)	−0.0184 (12)	−0.0030 (12)	−0.0045 (11)
C6	0.0635 (17)	0.0629 (17)	0.0672 (17)	−0.0183 (14)	−0.0200 (13)	−0.0144 (13)
C7	0.0489 (14)	0.0657 (17)	0.0690 (17)	−0.0118 (12)	−0.0165 (12)	−0.0113 (13)
C8	0.0634 (16)	0.0532 (15)	0.0625 (15)	−0.0163 (13)	0.0032 (13)	−0.0118 (12)
N1	0.0705 (16)	0.0940 (18)	0.0654 (15)	−0.0193 (14)	−0.0167 (13)	−0.0102 (13)
C9	0.063 (2)	0.087 (2)	0.070 (2)	−0.0270 (17)	0.0022 (17)	−0.0190 (16)
N3	0.0574 (14)	0.0879 (17)	0.0730 (16)	−0.0225 (12)	−0.0144 (12)	−0.0204 (13)
N4	0.0550 (13)	0.0549 (12)	0.0575 (13)	−0.0148 (10)	−0.0104 (10)	−0.0124 (10)
N5	0.0703 (16)	0.0659 (16)	0.0962 (18)	−0.0046 (13)	−0.0285 (13)	−0.0211 (13)

Geometric parameters (Å, º) top

N2—C9	1.326 (4)	C5—C8	1.502 (3)
N2—N1	1.325 (3)	C6—C7	1.380 (3)
C1—N5	1.141 (3)	C6—H6	0.9300
C1—C2	1.436 (3)	C7—H7	0.9300
C2—C7	1.379 (3)	C8—N4	1.463 (3)
C2—C3	1.381 (3)	C8—H8A	0.9700
C3—C4	1.375 (3)	C8—H8B	0.9700
C3—H3	0.9300	N1—N4	1.312 (3)
C4—C5	1.384 (3)	C9—N3	1.304 (3)
C4—H4	0.9300	C9—H9	0.84 (3)
C5—C6	1.379 (3)	N3—N4	1.324 (3)

C9—N2—N1	105.1 (2)	C2—C7—C6	119.9 (2)
N5—C1—C2	179.6 (3)	C2—C7—H7	120.0
C7—C2—C3	120.1 (2)	C6—C7—H7	120.0
C7—C2—C1	119.7 (2)	N4—C8—C5	111.39 (19)
C3—C2—C1	120.2 (2)	N4—C8—H8A	109.4
C4—C3—C2	119.6 (2)	C5—C8—H8A	109.4
C4—C3—H3	120.2	N4—C8—H8B	109.4
C2—C3—H3	120.2	C5—C8—H8B	109.4
C3—C4—C5	120.8 (2)	H8A—C8—H8B	108.0
C3—C4—H4	119.6	N4—N1—N2	106.5 (2)
C5—C4—H4	119.6	N3—C9—N2	113.6 (3)
C6—C5—C4	119.2 (2)	N3—C9—H9	122 (3)
C6—C5—C8	120.0 (2)	N2—C9—H9	124 (2)
C4—C5—C8	120.9 (2)	C9—N3—N4	102.1 (2)
C5—C6—C7	120.5 (2)	N1—N4—N3	112.7 (2)
C5—C6—H6	119.8	N1—N4—C8	123.1 (2)
C7—C6—H6	119.8	N3—N4—C8	124.1 (2)

C7—C2—C3—C4	0.8 (4)	C4—C5—C8—N4	−83.5 (3)
C1—C2—C3—C4	179.9 (2)	C9—N2—N1—N4	−0.6 (3)
C2—C3—C4—C5	−0.6 (4)	N1—N2—C9—N3	1.0 (3)
C3—C4—C5—C6	0.1 (4)	N2—C9—N3—N4	−1.0 (3)
C3—C4—C5—C8	178.5 (2)	N2—N1—N4—N3	0.0 (3)
C4—C5—C6—C7	0.1 (4)	N2—N1—N4—C8	177.3 (2)
C8—C5—C6—C7	−178.3 (2)	C9—N3—N4—N1	0.6 (3)
C3—C2—C7—C6	−0.6 (4)	C9—N3—N4—C8	−176.6 (2)
C1—C2—C7—C6	−179.7 (2)	C5—C8—N4—N1	−92.0 (3)
C5—C6—C7—C2	0.1 (4)	C5—C8—N4—N3	84.9 (3)
C6—C5—C8—N4	94.9 (3)

Experimental details

Crystal data
Chemical formula	C₉H₇N₅
M_r	185.20
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.7514 (8), 7.4029 (10), 11.3511 (12)
α, β, γ (°)	81.088 (3), 77.844 (3), 72.600 (5)
V (Å³)	448.64 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.12 × 0.02

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.980, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	4114, 1720, 923
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.156, 0.92
No. of reflections	1720
No. of parameters	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to ZRQ.

References

Bethel, P. A., Hill, M. S., Mahon, M. F. & Molloy, K. C. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 3507–3514. Web of Science CSD CrossRef Google Scholar
Jin, Z., Nolan, K., McArthur, C. R., Lever, A. B. P. & Leznoff, C. C. (1994). J. Organomet. Chem. 468, 205–212. CrossRef CAS Web of Science Google Scholar
Rigaku (2005). CrystalClear. Version 1.4.0. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, T., Yi, B. H. & Li, D. (2005). Inorg. Chem. 44, 4130–4132. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, X. M., Zhao, Y. F., Wu, H. S., Batten, S. R. & Ng, S. W. (2006). Dalton Trans. pp. 3170–3178. Web of Science CSD CrossRef Google Scholar