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

Hu, B.; Li, Y.-X.

doi:10.1107/S1600536807064434

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o221

https://doi.org/10.1107/S1600536807064434

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

Bin Hu ^a ^* and Yong-Xiu Li ^a

^aResearch Centre for Rare Earth and Micro/Nano Functional Materials, Nan Chang University, Nan Chang 330047, People's Republic of China
^*Correspondence e-mail: hbii@yahoo.cn

(Received 19 November 2007; accepted 29 November 2007; online 6 December 2007)

The title compound, C₉H₇N₅, is non-planar with a dihedral angle between the substituted benzene and tetrazole rings of 71.13 (9)°. Molecules are connected in centrosymmetric dimers by weak C—H⋯N interactions [C⋯N is 3.548 (5) Å]; these are the only interactions of significance in the crystal structure.

Related literature

For the applications of tetrazole derivatives as ligands in coordination chemistry, see: Huang et al. (2006 ); Fu & Zhao (2007 ); Hu et al. (2007 ).

Experimental

Crystal data

C₉H₇N₅
M_r = 185.20
Monoclinic, P 2₁ /c
a = 12.213 (11) Å
b = 13.724 (13) Å
c = 5.549 (5) Å
β = 102.24 (2)°
V = 909.0 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.22 × 0.15 × 0.1 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.97, T_max = 1.00 (expected range = 0.961–0.991)
6450 measured reflections
1493 independent reflections
1185 reflections with I > 2σ(I)
R_int = 0.098

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.187
S = 1.05
1493 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.15 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, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999 ); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064434/gg2054sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064434/gg2054Isup2.hkl

checkCIF report

Comment top

Ligands containing tetrazole groups could serve as potential multidentate or bridging building blocks for the construction of polymeric structures as they possess several possible donor N atoms (Huang et al.,2006). The tetrazole functional group has found a wide range of applications in coordination chemistry as ligand in coordination chemistry, in medicinal chemistry as a metabolically stable surrogate for a carboxylic acid group, and in materials science as high density energy materials (Fu et al., 2007). We originally attempted to synthesize complexes featuring Mn metal chains by reaction of the MnCl₂.4H₂O with 2-(bromomethyl)benzonitrile and 2H-tetrazole ligand. Unfortunately, we obtained only the title compound and we report herein the crystal structure of the title compound, 2-[(2H-tetrazol-2-yl)methyl]benzonitrile (I) (Fig.1).

In the title molecule the bond lengths and angles are in normal ranges (Hu et al., 2007). The phenyl ring is twisted away from coplanarity with the tetrazole ring and forms dihedral angles of 71.13 (9)°.

Related literature top

For the applications of tetrazole derivatives as ligands in coordination chemistry, see: Huang et al. (2006); Fu & Zhao (2007); Hu et al., (2007).

Experimental top

A mixture of 2-(bromomethyl)benzonitrile (39.2 mg, 0.2 mmol), 2H-tetrazole(14 mg, 0.2 mmol), KOH(11.2 mg, 0.2 mmol), MnCl₂.4H₂O (20 mg, 0.1 mmol), 2 ml me thanol and 0.3 ml H₂O were placed in a thick Pyrex tube (ca 20 cm in length). The tube was frozen with liquid N₂, evacuated under vacuum and sealed by heat. The tube was then placed into oven at 75 °C for 3 days to give colorless block crystals of the title complex.

Structure description top

For the applications of tetrazole derivatives as ligands in coordination chemistry, see: Huang et al. (2006); Fu & Zhao (2007); Hu et al., (2007).

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 1999).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

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

Crystal data top

C₉H₇N₅	F(000) = 384
M_r = 185.20	D_x = 1.353 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 356 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.213 (11) Å	Cell parameters from 7893 reflections
b = 13.724 (13) Å	θ = 3.4–27.5°
c = 5.549 (5) Å	µ = 0.09 mm⁻¹
β = 102.24 (2)°	T = 293 K
V = 909.0 (15) Å³	Block, colorless
Z = 4	0.22 × 0.15 × 0.1 mm

Data collection top

Rigaku SCXmini diffractometer	1493 independent reflections
Radiation source: fine-focus sealed tube	1185 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.098
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.0°, θ_min = 3.4°
ω scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.97, T_max = 1.00	l = −6→6
6450 measured reflections

Refinement top

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.187	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1044P)²] where P = (F_o² + 2F_c²)/3
1493 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₉H₇N₅	V = 909.0 (15) Å³
M_r = 185.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.213 (11) Å	µ = 0.09 mm⁻¹
b = 13.724 (13) Å	T = 293 K
c = 5.549 (5) Å	0.22 × 0.15 × 0.1 mm
β = 102.24 (2)°

Data collection top

Rigaku SCXmini diffractometer	1493 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1185 reflections with I > 2σ(I)
T_min = 0.97, T_max = 1.00	R_int = 0.098
6450 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.187	H-atom parameters constrained
S = 1.05	Δρ_max = 0.15 e Å⁻³
1493 reflections	Δρ_min = −0.16 e Å⁻³
127 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 > 2σ(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	0.15609 (14)	0.47882 (13)	−0.0640 (4)	0.0489 (6)
C2	0.10185 (16)	0.56933 (17)	−0.1044 (5)	0.0666 (7)
H2A	0.0506	0.5814	−0.2510	0.080*
C3	0.1252 (2)	0.64046 (15)	0.0756 (6)	0.0744 (9)
H3A	0.0890	0.7004	0.0505	0.089*
C4	0.2020 (2)	0.62302 (15)	0.2925 (6)	0.0710 (7)
H4A	0.2181	0.6716	0.4117	0.085*
C5	0.25499 (16)	0.53387 (14)	0.3331 (4)	0.0569 (6)
H5A	0.3059	0.5226	0.4806	0.068*
C6	0.23325 (13)	0.46083 (12)	0.1566 (3)	0.0432 (5)
C7	0.12946 (15)	0.40397 (17)	−0.2487 (4)	0.0569 (6)
C8	0.29305 (15)	0.36441 (12)	0.2059 (4)	0.0465 (6)
H8A	0.3078	0.3507	0.3813	0.056*
H8B	0.2454	0.3130	0.1212	0.056*
C9	0.51482 (17)	0.36439 (14)	−0.0975 (4)	0.0587 (6)
H9A	0.5480	0.3608	−0.2334	0.070*
N1	0.10778 (17)	0.34457 (16)	−0.3975 (4)	0.0754 (7)
N2	0.39950 (12)	0.36529 (9)	0.1217 (3)	0.0433 (5)
N3	0.49695 (14)	0.37893 (13)	0.2704 (3)	0.0630 (6)
N4	0.57203 (15)	0.37836 (15)	0.1306 (4)	0.0678 (6)
N5	0.40562 (14)	0.35604 (12)	−0.1126 (3)	0.0552 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0428 (10)	0.0547 (11)	0.0522 (12)	0.0003 (8)	0.0167 (9)	0.0067 (8)
C2	0.0547 (13)	0.0700 (14)	0.0783 (15)	0.0112 (10)	0.0212 (12)	0.0261 (13)
C3	0.0700 (16)	0.0464 (12)	0.119 (2)	0.0109 (10)	0.0484 (17)	0.0138 (13)
C4	0.0750 (16)	0.0529 (12)	0.0948 (19)	−0.0049 (10)	0.0396 (15)	−0.0139 (12)
C5	0.0562 (13)	0.0592 (12)	0.0584 (13)	−0.0083 (9)	0.0191 (11)	−0.0097 (9)
C6	0.0407 (10)	0.0452 (9)	0.0463 (11)	−0.0036 (7)	0.0153 (9)	0.0037 (8)
C7	0.0463 (11)	0.0757 (14)	0.0472 (12)	−0.0005 (10)	0.0066 (10)	0.0048 (10)
C8	0.0457 (11)	0.0477 (11)	0.0480 (11)	−0.0004 (7)	0.0139 (9)	0.0058 (8)
C9	0.0521 (13)	0.0689 (14)	0.0585 (14)	−0.0083 (9)	0.0196 (11)	−0.0109 (10)
N1	0.0696 (13)	0.0911 (15)	0.0605 (13)	0.0000 (10)	0.0024 (11)	−0.0086 (11)
N2	0.0433 (9)	0.0448 (9)	0.0411 (9)	0.0003 (6)	0.0072 (7)	0.0010 (6)
N3	0.0460 (11)	0.0896 (13)	0.0505 (11)	−0.0045 (8)	0.0034 (9)	−0.0062 (9)
N4	0.0452 (10)	0.0904 (13)	0.0682 (13)	−0.0071 (8)	0.0133 (10)	−0.0068 (10)
N5	0.0523 (11)	0.0683 (11)	0.0455 (10)	−0.0045 (7)	0.0115 (8)	−0.0056 (8)

Geometric parameters (Å, º) top

C1—C6	1.399 (3)	C6—C8	1.508 (3)
C1—C2	1.403 (3)	C7—N1	1.150 (3)
C1—C7	1.439 (3)	C8—N2	1.472 (3)
C2—C3	1.382 (4)	C8—H8A	0.9700
C2—H2A	0.9300	C8—H8B	0.9700
C3—C4	1.381 (4)	C9—N5	1.323 (3)
C3—H3A	0.9300	C9—N4	1.324 (3)
C4—C5	1.380 (3)	C9—H9A	0.9300
C4—H4A	0.9300	N2—N3	1.310 (2)
C5—C6	1.387 (3)	N2—N5	1.324 (3)
C5—H5A	0.9300	N3—N4	1.321 (3)

C6—C1—C2	120.24 (19)	C1—C6—C8	121.60 (17)
C6—C1—C7	120.39 (17)	N1—C7—C1	179.5 (2)
C2—C1—C7	119.35 (19)	N2—C8—C6	111.20 (14)
C3—C2—C1	119.4 (2)	N2—C8—H8A	109.4
C3—C2—H2A	120.3	C6—C8—H8A	109.4
C1—C2—H2A	120.3	N2—C8—H8B	109.4
C4—C3—C2	120.3 (2)	C6—C8—H8B	109.4
C4—C3—H3A	119.8	H8A—C8—H8B	108.0
C2—C3—H3A	119.8	N5—C9—N4	113.2 (2)
C5—C4—C3	120.3 (2)	N5—C9—H9A	123.4
C5—C4—H4A	119.9	N4—C9—H9A	123.4
C3—C4—H4A	119.9	N3—N2—N5	113.55 (16)
C4—C5—C6	120.8 (2)	N3—N2—C8	123.14 (17)
C4—C5—H5A	119.6	N5—N2—C8	123.26 (16)
C6—C5—H5A	119.6	N2—N3—N4	106.27 (18)
C5—C6—C1	118.86 (17)	N3—N4—C9	105.73 (18)
C5—C6—C8	119.54 (18)	C9—N5—N2	101.27 (16)

C6—C1—C2—C3	−0.1 (3)	C5—C6—C8—N2	−89.3 (2)
C7—C1—C2—C3	178.34 (18)	C1—C6—C8—N2	90.6 (2)
C1—C2—C3—C4	0.6 (3)	C6—C8—N2—N3	99.7 (2)
C2—C3—C4—C5	−0.9 (4)	C6—C8—N2—N5	−77.7 (2)
C3—C4—C5—C6	0.8 (3)	N5—N2—N3—N4	−0.3 (2)
C4—C5—C6—C1	−0.2 (3)	C8—N2—N3—N4	−177.94 (15)
C4—C5—C6—C8	179.64 (17)	N2—N3—N4—C9	0.1 (2)
C2—C1—C6—C5	−0.1 (3)	N5—C9—N4—N3	0.1 (3)
C7—C1—C6—C5	−178.51 (17)	N4—C9—N5—N2	−0.3 (2)
C2—C1—C6—C8	−179.96 (16)	N3—N2—N5—C9	0.38 (19)
C7—C1—C6—C8	1.6 (3)	C8—N2—N5—C9	178.00 (14)

Experimental details

Crystal data
Chemical formula	C₉H₇N₅
M_r	185.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.213 (11), 13.724 (13), 5.549 (5)
β (°)	102.24 (2)
V (Å³)	909.0 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.15 × 0.1

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.97, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	6450, 1493, 1185
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.187, 1.05
No. of reflections	1493
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1999).

Acknowledgements

This work was supported by a JiangXi Provincial Natural Science Foundation grant to Professor Yong-Xiu Li.

References

Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, m1955. Web of Science CSD CrossRef IUCr Journals Google Scholar
Huang, X.-H., Sheng, T.-L., Xiang, S.-C., Fu, R.-B., Hu, S.-M., Li, Y.-M. & Wu, X.-T. (2006). Inorg. Chem. Commun. 9, 1304–1307. Web of Science CSD CrossRef CAS Google Scholar
Hu, B., Xu, X.-B., Li, Y.-X. & Ye, H.-Y. (2007). Acta Cryst. E63, m2698. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Version 1.4.0. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1999). SHELXTL/PC. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar