5-(4-Chloro­benz­yl)-1H-tetra­zole

In the title compound, C₈H₇ClN₄, the phenyl and tetra­zole rings are inclined at a dihedral angle of 67.52 (6)°. In the crystal, mol­ecules are linked by an N—H⋯N hydrogen bond into a chain structure along [010]. π–π inter­actions with centroid–centroid distances of 3.526 (1) Å between adjacent tetra­zole rings further link the chains, forming a ribbon structure.

Related literature

For background to tetra­zole compounds, see: Kitagawa et al. (2004); Zhao et al. (2008); For the synthesis, see: Luo et al. (2006).

Experimental

Crystal data

• C₈H₇ClN₄

• M_r = 194.63

• Monoclinic, P 2₁ /c

• a = 14.654 (3) Å

• b = 4.9321 (10) Å

• c = 12.688 (3) Å

• β = 105.63 (3)°

• V = 883.1 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.39 mm⁻¹

• T = 293 K

• 0.40 × 0.38 × 0.15 mm

Data collection

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.860, T_max = 0.944

• 8039 measured reflections

• 2015 independent reflections

• 1546 reflections with I > 2σ(I)

• R_int = 0.025

Refinement

• R[F² > 2σ(F²)] = 0.033

• wR(F²) = 0.094

• S = 1.08

• 2015 reflections

• 122 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1⋯N1^i	0.90 (1)	1.92 (1)	2.8013 (15)	168 (2)
Symmetry code: (i) x, y+1, z.

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97.

Supporting information

S1. Comment

The tetrazole has attracted considerable interesting owing to their structural characterization in coordination chemistry and the extensively application in medicinal chemistry and materials science (Zhao et al. 2008; Kitagawa et al. 2004). Here, we report the synthesis and crystal structure of the title compound.

As shown in fig.1, the benzenyl plane and tetrazole rings form a dihedral angle about 67.52 (6) ° (Fig. 1). In the crystal packing, the molecules are linked by N—H···N hydrogen bonds into a chain structure alone [010] (Fig. 2, Table 1). The π—π interactions with distances of 3.526 (1) Å (center to center) between the adjacent tetrazole rings further link them to form ribbon structure (Fig. 3).

Related literature

For background to tetrazole compounds, see: Kitagawa et al. (2004); Zhao et al. (2008); For the synthesis, see: Luo et al. (2006).

S2. Experimental

The title compound was prepared as follows (Luo et al. 2006):2-(4-chlorophenyl)acetonitrile (6.06 g, 0.04 mol), NaN3 (3.9 g, 0.06 mol) and NH₄Cl (3.21 g, 0.06 mol) were dissolved in DMF (120 ml). The mixture was reflux for 20 h under stirring. Then, it was cooled to room temperature and the mixture was filtered. The solvent was evaporated and the residue was poured into cold water (30 ml) to give the title compound (4.32 g, 55.5 %). The crystals suitable for X-ray diffraction were obtained from 10 mL mixed solution of ethanol and water (1:1).

S3. Refinement

The anormal reflection data (-12 3 3) have been omitted during the refinement.H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic); C—H = 0.97 Å (methylene), and with U_iso(H) = 1.2U_eq(C). N-bounded H atom was found from Fourier map and was refined restrainedly with N—H = 0.90 Å.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.
	Fig. 2. A partial packing view, showing chain structure along [0 1 0].
	Fig. 3. A partial packing view, showing double chain structure forming by N—H···N hydrogen bonds and π—π intercations.

5-(4-Chlorobenzyl)-1H-tetrazole

Crystal data

C8H7ClN4	F(000) = 400
Mr = 194.63	Dx = 1.464 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6142 reflections
a = 14.654 (3) Å	θ = 3.3–25.1°
b = 4.9321 (10) Å	µ = 0.39 mm^−1
c = 12.688 (3) Å	T = 293 K
β = 105.63 (3)°	Block, colorless
V = 883.1 (3) Å^3	0.40 × 0.38 × 0.15 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2015 independent reflections
Radiation source: fine-focus sealed tube	1546 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→19
Tmin = 0.860, Tmax = 0.944	k = −6→6
8039 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.0994P] where P = (Fo^2 + 2Fc^2)/3
2015 reflections	(Δ/σ)max = 0.001
122 parameters	Δρmax = 0.18 e Å^−3
1 restraint	Δρmin = −0.33 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
C1	0.37038 (9)	0.2990 (3)	1.07319 (14)	0.0463 (4)
C2	0.29853 (11)	0.4022 (3)	1.11205 (14)	0.0503 (4)
H2	0.2911	0.3450	1.1791	0.060*
C3	0.23731 (10)	0.5923 (3)	1.05032 (13)	0.0465 (4)
H3	0.1891	0.6638	1.0768	0.056*
C4	0.24675 (9)	0.6773 (3)	0.95005 (12)	0.0380 (3)
C5	0.31899 (11)	0.5667 (3)	0.91227 (15)	0.0467 (4)
H5	0.3259	0.6203	0.8446	0.056*
C6	0.38090 (11)	0.3781 (3)	0.97347 (15)	0.0518 (4)
H6	0.4292	0.3057	0.9473	0.062*
C7	0.18309 (10)	0.8938 (3)	0.88444 (14)	0.0451 (4)
H7A	0.2059	1.0694	0.9149	0.054*
H7B	0.1887	0.8888	0.8100	0.054*
C8	0.08089 (9)	0.8704 (2)	0.88086 (11)	0.0311 (3)
Cl1	0.44739 (3)	0.06175 (9)	1.15206 (5)	0.0707 (2)
N1	0.03034 (8)	0.6471 (2)	0.87394 (9)	0.0347 (3)
N2	−0.06056 (8)	0.7269 (2)	0.86416 (10)	0.0393 (3)
N3	−0.06566 (8)	0.9885 (2)	0.86545 (10)	0.0404 (3)
N4	0.02296 (8)	1.0797 (2)	0.87674 (9)	0.0346 (3)
H1	0.0343 (11)	1.2592 (6)	0.8810 (12)	0.048 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0327 (7)	0.0365 (7)	0.0624 (10)	0.0041 (6)	0.0001 (6)	−0.0060 (7)
C2	0.0506 (9)	0.0497 (9)	0.0504 (10)	0.0101 (7)	0.0130 (7)	0.0055 (7)
C3	0.0416 (8)	0.0477 (9)	0.0531 (10)	0.0127 (7)	0.0176 (7)	0.0025 (7)
C4	0.0330 (6)	0.0302 (7)	0.0494 (9)	−0.0047 (6)	0.0090 (6)	−0.0018 (6)
C5	0.0424 (8)	0.0469 (9)	0.0548 (10)	−0.0032 (7)	0.0198 (7)	−0.0019 (7)
C6	0.0354 (7)	0.0486 (9)	0.0741 (12)	0.0022 (7)	0.0194 (8)	−0.0124 (8)
C7	0.0401 (7)	0.0327 (7)	0.0615 (10)	−0.0044 (6)	0.0119 (7)	0.0091 (7)
C8	0.0390 (6)	0.0224 (6)	0.0306 (7)	0.0005 (5)	0.0068 (5)	0.0001 (5)
Cl1	0.0512 (3)	0.0538 (3)	0.0907 (4)	0.0194 (2)	−0.0094 (2)	−0.0025 (2)
N1	0.0390 (6)	0.0229 (5)	0.0424 (7)	−0.0012 (5)	0.0115 (5)	−0.0019 (4)
N2	0.0390 (6)	0.0329 (6)	0.0473 (7)	−0.0002 (5)	0.0140 (5)	−0.0006 (5)
N3	0.0429 (6)	0.0337 (6)	0.0465 (7)	0.0059 (5)	0.0153 (5)	0.0025 (5)
N4	0.0461 (6)	0.0209 (5)	0.0366 (7)	0.0024 (5)	0.0107 (5)	0.0003 (4)

Geometric parameters (Å, º)

C1—C6	1.372 (2)	C6—H6	0.9300
C1—C2	1.375 (2)	C7—C8	1.4906 (19)
C1—Cl1	1.7423 (16)	C7—H7A	0.9700
C2—C3	1.385 (2)	C7—H7B	0.9700
C2—H2	0.9300	C8—N1	1.3169 (17)
C3—C4	1.381 (2)	C8—N4	1.3284 (17)
C3—H3	0.9300	N1—N2	1.3622 (16)
C4—C5	1.386 (2)	N2—N3	1.2927 (17)
C4—C7	1.5117 (19)	N3—N4	1.3449 (17)
C5—C6	1.383 (2)	N4—H1	0.8998 (11)
C5—H5	0.9300
C6—C1—C2	120.83 (14)	C5—C6—H6	120.3
C6—C1—Cl1	120.30 (12)	C8—C7—C4	115.34 (12)
C2—C1—Cl1	118.87 (14)	C8—C7—H7A	108.4
C1—C2—C3	119.32 (16)	C4—C7—H7A	108.4
C1—C2—H2	120.3	C8—C7—H7B	108.4
C3—C2—H2	120.3	C4—C7—H7B	108.4
C4—C3—C2	121.06 (13)	H7A—C7—H7B	107.5
C4—C3—H3	119.5	N1—C8—N4	107.77 (11)
C2—C3—H3	119.5	N1—C8—C7	127.54 (12)
C3—C4—C5	118.32 (14)	N4—C8—C7	124.55 (12)
C3—C4—C7	121.43 (13)	C8—N1—N2	106.44 (10)
C5—C4—C7	120.20 (14)	N3—N2—N1	110.23 (11)
C6—C5—C4	121.15 (16)	N2—N3—N4	106.11 (11)
C6—C5—H5	119.4	C8—N4—N3	109.45 (11)
C4—C5—H5	119.4	C8—N4—H1	131.0 (11)
C1—C6—C5	119.31 (14)	N3—N4—H1	119.5 (10)
C1—C6—H6	120.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1···N1^i	0.90 (1)	1.92 (1)	2.8013 (15)	168 (2)

Symmetry code: (i) x, y+1, z.