2-(1H-Tetra­zol-5-yl)benzonitrile

Xing, Z.; Han, G.-F.; Zhu, W.-F.; Zhao, Y.-Y.

doi:10.1107/S1600536808008027

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o816

doi:10.1107/S1600536808008027

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2-(1H-Tetrazol-5-yl)benzonitrile

Zheng Xing,^a Guang-Fan Han,^a ^* Wei-Feng Zhu ^a and Yu-Yuan Zhao ^a

^aSchool of Materials Science and Engineering, Jiangsu University of Science, and Technology, Zhenjiang, Jiangsu 212003, People's Republic of China
^*Correspondence e-mail: gf552002@yahoo.com.cn

(Received 4 March 2008; accepted 25 March 2008; online 10 April 2008)

The title compound, C₈H₅N₅, was synthesized from phthalonitrile. The benzonitrile and tetrazole rings are inclined at a dihedral angle of 37.14 (11)°. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the tetrazole rings of adjacent molecules, forming chains along the a axis.

Related literature

For backgound to the chemisty of tetrazoles, see: Bekhit et al. (2004 ); Aykut İkizler & Sancak (1992 , 1995 , 1998 ); Rajasekaran & Thampi (2004 ); Satyanarayana et al. (2006 ); Schmidt & Schieffer (2003 ); Upadhayaya et al. (2004 ); Wexler et al. (1996 ).

Experimental

Crystal data

C₈H₅N₅
M_r = 171.17
Monoclinic, P 2₁ /n
a = 4.9281 (10) Å
b = 6.5420 (13) Å
c = 24.867 (5) Å
β = 95.27 (3)°
V = 798.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.25 × 0.07 × 0.07 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.993, T_max = 0.996
6844 measured reflections
1553 independent reflections
1167 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.138
S = 1.10
1553 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N5ⁱ	0.92 (3)	1.91 (3)	2.820 (2)	172 (2)
N2—H2⋯N4ⁱ	0.92 (3)	2.60 (3)	3.374 (2)	142 (2)
Symmetry code: (i) x-1, y, z.

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, New_Global_Publ_Block. DOI: 10.1107/S1600536808008027/sj2471sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008027/sj2471Isup2.hkl

checkCIF report

Comment top

Nitriles are close relatives of azoles and hydrazones and are parent compounds for the preparation of various functional organic materials having triazole, imidazole or tetrazole rings (Aykut İkizler & Sancak, 1992, 1995, 1998). Tetrazoles find wide application in the synthesis of medicinal products such as antihypertensive agents (Wexler et al., 1996; Schmidt & Schieffer, 2003; Satyanarayana et al., 2006), resolvents (Bekhit et al., 2004), anaesthetics (Rajasekaran & Thampi, 2004) and antifungal agents (Upadhayaya et al., 2004). We report herein the crystal structure of the title compound, 2-(1H-tetrazol-5-yl)benzonitrile, Fig 1 with its crystal packing shown in Figure 2, Table 1.

Related literature top

For backgound to the chemisty of tetrazoles, see: Bekhit et al. (2004); Aykut İkizler & Sancak, (1992, 1995, 1998); Rajasekaran & Thampi (2004); Satyanarayana et al. (2006); Schmidt & Schieffer (2003); Upadhayaya et al. (2004); Wexler et al. (1996).

Experimental top

Phthalonitrile (1.28 g, 0.01 mol), sodium azide (0.975 g, 0.015 mol), ammonium chloride (0.605 g, 0.011 mol) and DMF (15 ml) were added in a flask and reacted at 120 °C with stirring for 24 h. A mass of white solid was collected after solvents removed. The crude product was recrystallized by slowly evaporating a mixed solution of ethanol and water (2:1) to yield colorless prism-like crystals, suitable for X-ray analysis.

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 title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the c axis. Hydrogen bonds are drawn as dashed lines.

(I) top

Crystal data top

C₈H₅N₅	F(000) = 352
M_r = 171.17	D_x = 1.424 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6584 reflections
a = 4.9281 (10) Å	θ = 3.1–28.8°
b = 6.5420 (13) Å	µ = 0.10 mm⁻¹
c = 24.867 (5) Å	T = 293 K
β = 95.27 (3)°	Prism, colorless
V = 798.3 (3) Å³	0.25 × 0.07 × 0.07 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	1553 independent reflections
Radiation source: fine-focus sealed tube	1167 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.993, T_max = 0.996	l = −30→30
6844 measured reflections

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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.138	w = 1/[σ²(F_o²) + (0.0619P)² + 0.1285P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1553 reflections	Δρ_max = 0.21 e Å⁻³
122 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.044 (14)

Crystal data top

C₈H₅N₅	V = 798.3 (3) Å³
M_r = 171.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.9281 (10) Å	µ = 0.10 mm⁻¹
b = 6.5420 (13) Å	T = 293 K
c = 24.867 (5) Å	0.25 × 0.07 × 0.07 mm
β = 95.27 (3)°

Data collection top

Rigaku SCXmini diffractometer	1553 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1167 reflections with I > 2σ(I)
T_min = 0.993, T_max = 0.996	R_int = 0.061
6844 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.21 e Å⁻³
1553 reflections	Δρ_min = −0.24 e Å⁻³
122 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
C1	0.5249 (4)	0.5054 (3)	0.13602 (8)	0.0345 (5)
C2	0.6569 (4)	0.5277 (3)	0.08892 (8)	0.0403 (5)
C3	0.6021 (5)	0.6960 (4)	0.05536 (10)	0.0548 (7)
H3	0.6925	0.7116	0.0244	0.066*
C4	0.4141 (5)	0.8390 (4)	0.06821 (11)	0.0608 (7)
H4	0.3762	0.9509	0.0457	0.073*
C5	0.2821 (5)	0.8174 (4)	0.11410 (11)	0.0539 (6)
H5	0.1537	0.9140	0.1223	0.065*
C6	0.3384 (4)	0.6532 (3)	0.14819 (9)	0.0441 (6)
H6	0.2504	0.6416	0.1796	0.053*
C7	0.5736 (4)	0.3299 (3)	0.17202 (8)	0.0323 (5)
C8	0.8482 (5)	0.3773 (4)	0.07280 (9)	0.0476 (6)
N1	0.9990 (5)	0.2612 (4)	0.05847 (9)	0.0701 (7)
N2	0.3814 (3)	0.2405 (3)	0.19806 (7)	0.0399 (5)
N3	0.4920 (3)	0.0893 (3)	0.22916 (8)	0.0480 (5)
N4	0.7498 (3)	0.0881 (3)	0.22217 (7)	0.0458 (5)
N5	0.8068 (3)	0.2363 (3)	0.18650 (7)	0.0380 (5)
H2	0.195 (6)	0.253 (4)	0.1939 (10)	0.072 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0263 (10)	0.0405 (11)	0.0363 (11)	0.0019 (9)	0.0016 (8)	0.0010 (9)
C2	0.0345 (12)	0.0463 (12)	0.0407 (12)	0.0040 (10)	0.0062 (9)	0.0018 (10)
C3	0.0598 (16)	0.0595 (15)	0.0473 (14)	0.0110 (12)	0.0171 (12)	0.0137 (12)
C4	0.0658 (17)	0.0558 (15)	0.0611 (17)	0.0139 (13)	0.0072 (14)	0.0187 (13)
C5	0.0491 (14)	0.0480 (14)	0.0642 (16)	0.0144 (11)	0.0041 (12)	−0.0003 (12)
C6	0.0397 (12)	0.0507 (13)	0.0425 (13)	0.0070 (10)	0.0069 (10)	−0.0014 (10)
C7	0.0221 (9)	0.0434 (11)	0.0319 (11)	0.0004 (8)	0.0055 (8)	−0.0021 (9)
C8	0.0476 (13)	0.0573 (15)	0.0395 (13)	0.0069 (12)	0.0127 (10)	0.0069 (11)
N1	0.0705 (15)	0.0809 (15)	0.0623 (15)	0.0288 (13)	0.0242 (12)	0.0062 (12)
N2	0.0203 (9)	0.0531 (11)	0.0468 (11)	0.0024 (8)	0.0058 (8)	0.0107 (8)
N3	0.0306 (9)	0.0600 (12)	0.0540 (12)	0.0029 (9)	0.0074 (8)	0.0166 (10)
N4	0.0296 (9)	0.0583 (12)	0.0494 (11)	0.0047 (8)	0.0042 (8)	0.0139 (9)
N5	0.0238 (8)	0.0510 (10)	0.0400 (10)	0.0035 (8)	0.0065 (7)	0.0070 (8)

Geometric parameters (Å, º) top

C1—C6	1.386 (3)	C5—H5	0.9300
C1—C2	1.399 (3)	C6—H6	0.9300
C1—C7	1.462 (3)	C7—N5	1.323 (2)
C2—C3	1.393 (3)	C7—N2	1.331 (2)
C2—C8	1.445 (3)	C8—N1	1.142 (3)
C3—C4	1.375 (3)	N2—N3	1.340 (2)
C3—H3	0.9300	N2—H2	0.92 (3)
C4—C5	1.372 (3)	N3—N4	1.298 (2)
C4—H4	0.9300	N4—N5	1.361 (2)
C5—C6	1.381 (3)

C6—C1—C2	118.61 (19)	C6—C5—H5	119.8
C6—C1—C7	119.24 (18)	C5—C6—C1	120.5 (2)
C2—C1—C7	122.13 (17)	C5—C6—H6	119.7
C3—C2—C1	120.31 (19)	C1—C6—H6	119.7
C3—C2—C8	117.86 (19)	N5—C7—N2	107.65 (17)
C1—C2—C8	121.81 (19)	N5—C7—C1	128.31 (17)
C4—C3—C2	119.7 (2)	N2—C7—C1	123.99 (17)
C4—C3—H3	120.1	N1—C8—C2	177.8 (2)
C2—C3—H3	120.1	C7—N2—N3	109.61 (16)
C5—C4—C3	120.3 (2)	C7—N2—H2	130.9 (16)
C5—C4—H4	119.9	N3—N2—H2	118.7 (16)
C3—C4—H4	119.9	N4—N3—N2	106.16 (16)
C4—C5—C6	120.5 (2)	N3—N4—N5	110.25 (16)
C4—C5—H5	119.8	C7—N5—N4	106.33 (15)

C6—C1—C2—C3	0.4 (3)	C6—C1—C7—N5	−141.7 (2)
C7—C1—C2—C3	179.22 (19)	C2—C1—C7—N5	39.5 (3)
C6—C1—C2—C8	−178.3 (2)	C6—C1—C7—N2	35.6 (3)
C7—C1—C2—C8	0.5 (3)	C2—C1—C7—N2	−143.2 (2)
C1—C2—C3—C4	−1.1 (4)	N5—C7—N2—N3	−0.1 (2)
C8—C2—C3—C4	177.7 (2)	C1—C7—N2—N3	−177.85 (18)
C2—C3—C4—C5	0.5 (4)	C7—N2—N3—N4	0.3 (2)
C3—C4—C5—C6	0.7 (4)	N2—N3—N4—N5	−0.4 (2)
C4—C5—C6—C1	−1.3 (4)	N2—C7—N5—N4	−0.2 (2)
C2—C1—C6—C5	0.8 (3)	C1—C7—N5—N4	177.48 (19)
C7—C1—C6—C5	−178.05 (19)	N3—N4—N5—C7	0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N5ⁱ	0.92 (3)	1.91 (3)	2.820 (2)	172 (2)
N2—H2···N4ⁱ	0.92 (3)	2.60 (3)	3.374 (2)	142 (2)

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₅N₅
M_r	171.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.9281 (10), 6.5420 (13), 24.867 (5)
β (°)	95.27 (3)
V (Å³)	798.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.07 × 0.07

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.993, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	6844, 1553, 1167
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.138, 1.10
No. of reflections	1553
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N5ⁱ	0.92 (3)	1.91 (3)	2.820 (2)	172 (2)
N2—H2···N4ⁱ	0.92 (3)	2.60 (3)	3.374 (2)	142 (2)

Symmetry code: (i) x−1, y, z.

Acknowledgements

This project was supported by Jiangsu Education Department of China (No. 05KJB350031)

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