6-(1H-Tetra­zol-5-yl)-1H-indole monohydrate

Ge, Y.-H.; Han, P.; Wei, P.; Ou-yang, P.-K.

doi:10.1107/S1600536811003990

organic compounds

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Volume 67| Part 3| March 2011| Page o692

doi:10.1107/S1600536811003990

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6-(1H-Tetrazol-5-yl)-1H-indole monohydrate

Yu-Hua Ge,^a,^b ^* Pei Han,^b Ping Wei ^a and Ping-Kai Ou-yang ^a

^aCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, Southeast Universiy, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: geyuhua@seu.edu.cn

(Received 4 January 2011; accepted 1 February 2011; online 23 February 2011)

In the title compound, C₉H₇N₅·H₂O, the tetrazole ring forms a dihedral angle of 1.82 (1)° with the mean plane of the indole fragment. In the crystal, molecules are linked by intermolecular O—H⋯N, N—H⋯O and N—H⋯N hydrogen bonds into a two-dimensional network parallel to (100). Addtional stabilization is provide by weak π–π interactions with a centroid–centroid distance of 3.698 (2) Å.

Related literature

For the synthesis and pharmacological activity of compounds containing indole and tetrazole groups, see: Itoh et al. (1995 ); Semenov (2002 ). For the synthesis of 6-cyanoindole, a starting material for the title compound, see: Frederick (1949 ).

Experimental

Crystal data

C₉H₇N₅·H₂O
M_r = 203.21
Monoclinic, P 2₁ /c
a = 17.175 (3) Å
b = 4.0653 (8) Å
c = 14.421 (3) Å
β = 107.59 (3)°
V = 959.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.20 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.737, T_max = 1.000
7430 measured reflections
1683 independent reflections
945 reflections with I > 2σ(I)
R_int = 0.120

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.131
S = 1.01
1683 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N2ⁱ	0.90 (4)	2.07 (4)	2.957 (4)	169 (4)
O1—H1B⋯N3ⁱⁱ	0.76 (5)	2.17 (5)	2.927 (5)	172 (5)
N4—H4N⋯O1	0.86	1.87	2.715 (4)	169
N5—H5N⋯N1ⁱⁱⁱ	0.86	2.17	3.019 (4)	171
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003990/lh5195sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003990/lh5195Isup2.hkl

checkCIF report

Comment top

In recent decades, there have been some reports on the compounds which are synthesized by the combination of the tetrazole and indole rings (Itoh et al.,1995) and property studies reveals that these compounds always perform unique pharmacological activities (Semenov et al., 2002). In order to obtain such compounds, we have attempted to synthesize the indole compounds with tetrazole as a substituent. Herein, we report the crystal structure of the title compound (I). The molecular structure of (1) is shown in Fig. 1.

The indole unit is essentially planar, with a mean deviation of 0.007 (8)Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle formed by the indole plane and the tetrazole ring is 1.82 (1)°. The crystal packing (Fig. 2) is stabilized by intermolecular O-H···N, N—H···O and N—H···N hydrogen bonds (Table 1). Further stabilization is provided by aromatic π–π interactions with a Cg1···Cg2(x, 1+y, z) distance of 3.698 (2) Å (Cg1 and Cg2 are the centroids of the N5/C4-C7 and C2-C4/C7-C9 rings, respectively).

Related literature top

For the synthesis and pharmacological activity of compounds containing indole and tetrazole groups, see: Itoh et al. (1995); Semenov et al. (2002). For the synthesis of 6-cyanoindole, a starting material for the title compound, see: Frederick (1949).

Experimental top

All chemicals used (reagent grade) were commercially available. 6-Cyanoindole was synthesized following the methods described by Frederick (1949). To the stirring DMF solution of NaN₃ and triethylamine, 6-cyanoindole was added. Then the mixture was heated to 120, about 1 h later, the solution was cooled to room temperature, and DMF was distilled in a vacuum. With some follow-up treatment, the crude product was recrystallized in methanol solution and seven days later, yellow prism crystal was obtained.

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) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. Part of the crystal structure with hydrogen bonds and π–π interactions shown as dashed lines. Only H atoms involed in hydrogen bonds are shown. CP denotes a ring centroid. [Symmetry codes: (i) x, y-1,z; (ii) -x+1, y+1/2, -z+1/2; (iii)x, -y+1/2, z-1/2; (iv) x, -y+3/2, z-1/2]

6-(1H-Tetrazol-5-yl)-1H-indole monohydrate top

Crystal data top

C₉H₇N₅·H₂O	F(000) = 424
M_r = 203.21	D_x = 1.406 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2795 reflections
a = 17.175 (3) Å	θ = 3.1–27.5°
b = 4.0653 (8) Å	µ = 0.10 mm⁻¹
c = 14.421 (3) Å	T = 293 K
β = 107.59 (3)°	Needle, colorless
V = 959.8 (3) Å³	0.20 × 0.05 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1683 independent reflections
Radiation source: fine-focus sealed tube	945 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.120
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −4→4
T_min = 0.737, T_max = 1.000	l = −17→17
7430 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0398P)²] where P = (F_o² + 2F_c²)/3
1683 reflections	(Δ/σ)_max < 0.001
144 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₇N₅·H₂O	V = 959.8 (3) Å³
M_r = 203.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.175 (3) Å	µ = 0.10 mm⁻¹
b = 4.0653 (8) Å	T = 293 K
c = 14.421 (3) Å	0.20 × 0.05 × 0.05 mm
β = 107.59 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1683 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	945 reflections with I > 2σ(I)
T_min = 0.737, T_max = 1.000	R_int = 0.120
7430 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.15 e Å⁻³
1683 reflections	Δρ_min = −0.19 e Å⁻³
144 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
O1	0.0699 (2)	−0.0517 (10)	0.1761 (2)	0.0720 (10)
H1A	0.088 (2)	−0.161 (10)	0.132 (3)	0.095 (17)*
H1B	0.033 (3)	0.048 (11)	0.147 (3)	0.10 (2)*
N1	0.19161 (16)	−0.0016 (7)	0.5257 (2)	0.0453 (8)
N2	0.12138 (17)	−0.1708 (7)	0.5143 (2)	0.0518 (9)
N3	0.08061 (16)	−0.1971 (7)	0.4227 (2)	0.0509 (9)
N4	0.12440 (15)	−0.0389 (7)	0.37351 (19)	0.0415 (8)
H4N	0.1108	−0.0189	0.3113	0.062*
N5	0.32387 (16)	0.6304 (7)	0.21458 (19)	0.0442 (8)
H5N	0.2898	0.6026	0.1576	0.066*
C1	0.19266 (19)	0.0829 (8)	0.4367 (2)	0.0349 (8)
C2	0.25600 (18)	0.2697 (8)	0.4122 (2)	0.0325 (8)
C3	0.25007 (18)	0.3476 (8)	0.3176 (2)	0.0349 (8)
H3	0.2048	0.2852	0.2666	0.042*
C4	0.31364 (19)	0.5219 (8)	0.3008 (2)	0.0346 (8)
C5	0.3976 (2)	0.7902 (8)	0.2348 (2)	0.0436 (9)
H5	0.4185	0.8834	0.1884	0.052*
C6	0.4357 (2)	0.7929 (8)	0.3320 (2)	0.0394 (9)
H6	0.4862	0.8864	0.3636	0.047*
C7	0.38315 (18)	0.6239 (8)	0.3762 (2)	0.0339 (8)
C8	0.38770 (19)	0.5422 (8)	0.4718 (2)	0.0403 (9)
H8	0.4327	0.6052	0.5231	0.048*
C9	0.32503 (18)	0.3679 (8)	0.4894 (2)	0.0382 (9)
H9	0.3280	0.3136	0.5530	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.057 (2)	0.112 (3)	0.0391 (17)	0.0266 (19)	0.0019 (15)	−0.0135 (18)
N1	0.0348 (18)	0.058 (2)	0.0385 (18)	−0.0073 (16)	0.0049 (14)	0.0043 (16)
N2	0.0431 (19)	0.069 (2)	0.040 (2)	−0.0068 (17)	0.0080 (16)	0.0037 (17)
N3	0.0424 (19)	0.064 (2)	0.045 (2)	−0.0102 (16)	0.0113 (16)	0.0047 (17)
N4	0.0327 (16)	0.056 (2)	0.0329 (16)	−0.0036 (15)	0.0047 (14)	0.0050 (15)
N5	0.0454 (18)	0.057 (2)	0.0279 (16)	0.0038 (16)	0.0071 (13)	0.0024 (14)
C1	0.032 (2)	0.037 (2)	0.032 (2)	0.0057 (16)	0.0037 (16)	−0.0009 (16)
C2	0.0322 (19)	0.034 (2)	0.0292 (19)	0.0031 (16)	0.0062 (15)	−0.0008 (15)
C3	0.0297 (18)	0.043 (2)	0.030 (2)	0.0060 (17)	0.0047 (15)	−0.0045 (16)
C4	0.038 (2)	0.040 (2)	0.0256 (19)	0.0101 (18)	0.0093 (16)	0.0014 (16)
C5	0.038 (2)	0.046 (2)	0.048 (2)	0.0017 (19)	0.0154 (18)	0.0049 (19)
C6	0.0371 (19)	0.045 (2)	0.034 (2)	−0.0005 (18)	0.0075 (17)	0.0021 (17)
C7	0.034 (2)	0.037 (2)	0.0288 (19)	0.0045 (16)	0.0072 (16)	−0.0011 (16)
C8	0.035 (2)	0.051 (2)	0.029 (2)	−0.0065 (17)	0.0010 (16)	−0.0045 (17)
C9	0.041 (2)	0.047 (2)	0.0240 (19)	−0.0011 (18)	0.0052 (16)	−0.0010 (16)

Geometric parameters (Å, º) top

O1—H1A	0.90 (4)	C2—C9	1.417 (4)
O1—H1B	0.77 (4)	C3—C4	1.383 (4)
N1—C1	1.333 (4)	C3—H3	0.9300
N1—N2	1.355 (3)	C4—C7	1.413 (4)
N2—N3	1.298 (3)	C5—C6	1.355 (4)
N3—N4	1.344 (3)	C5—H5	0.9300
N4—C1	1.344 (4)	C6—C7	1.429 (4)
N4—H4N	0.8600	C6—H6	0.9300
N5—C5	1.374 (4)	C7—C8	1.397 (4)
N5—C4	1.380 (4)	C8—C9	1.375 (4)
N5—H5N	0.8600	C8—H8	0.9300
C1—C2	1.456 (4)	C9—H9	0.9300
C2—C3	1.373 (4)

H1A—O1—H1B	106 (4)	N5—C4—C3	130.1 (3)
C1—N1—N2	106.5 (3)	N5—C4—C7	107.0 (3)
N3—N2—N1	110.6 (3)	C3—C4—C7	122.9 (3)
N2—N3—N4	106.4 (2)	C6—C5—N5	110.5 (3)
C1—N4—N3	109.3 (3)	C6—C5—H5	124.8
C1—N4—H4N	125.3	N5—C5—H5	124.8
N3—N4—H4N	125.3	C5—C6—C7	106.6 (3)
C5—N5—C4	108.7 (3)	C5—C6—H6	126.7
C5—N5—H5N	125.7	C7—C6—H6	126.7
C4—N5—H5N	125.7	C8—C7—C4	118.2 (3)
N1—C1—N4	107.2 (3)	C8—C7—C6	134.5 (3)
N1—C1—C2	126.7 (3)	C4—C7—C6	107.3 (3)
N4—C1—C2	126.2 (3)	C9—C8—C7	119.4 (3)
C3—C2—C9	120.6 (3)	C9—C8—H8	120.3
C3—C2—C1	121.7 (3)	C7—C8—H8	120.3
C9—C2—C1	117.7 (3)	C8—C9—C2	121.0 (3)
C2—C3—C4	117.8 (3)	C8—C9—H9	119.5
C2—C3—H3	121.1	C2—C9—H9	119.5
C4—C3—H3	121.1

C1—N1—N2—N3	1.0 (4)	C2—C3—C4—N5	179.7 (3)
N1—N2—N3—N4	−0.8 (4)	C2—C3—C4—C7	−0.6 (4)
N2—N3—N4—C1	0.2 (4)	C4—N5—C5—C6	−0.7 (4)
N2—N1—C1—N4	−0.9 (4)	N5—C5—C6—C7	0.1 (4)
N2—N1—C1—C2	179.6 (3)	N5—C4—C7—C8	−179.8 (3)
N3—N4—C1—N1	0.4 (4)	C3—C4—C7—C8	0.5 (5)
N3—N4—C1—C2	179.9 (3)	N5—C4—C7—C6	−0.8 (3)
N1—C1—C2—C3	−178.9 (3)	C3—C4—C7—C6	179.4 (3)
N4—C1—C2—C3	1.6 (5)	C5—C6—C7—C8	179.2 (3)
N1—C1—C2—C9	1.5 (5)	C5—C6—C7—C4	0.4 (3)
N4—C1—C2—C9	−177.9 (3)	C4—C7—C8—C9	−0.2 (5)
C9—C2—C3—C4	0.4 (5)	C6—C7—C8—C9	−178.8 (3)
C1—C2—C3—C4	−179.1 (3)	C7—C8—C9—C2	0.1 (5)
C5—N5—C4—C3	−179.4 (3)	C3—C2—C9—C8	−0.2 (5)
C5—N5—C4—C7	0.9 (3)	C1—C2—C9—C8	179.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N2ⁱ	0.90 (4)	2.07 (4)	2.957 (4)	169 (4)
O1—H1B···N3ⁱⁱ	0.76 (5)	2.17 (5)	2.927 (5)	172 (5)
N4—H4N···O1	0.86	1.87	2.715 (4)	169
N5—H5N···N1ⁱⁱⁱ	0.86	2.17	3.019 (4)	171

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

Experimental details

Crystal data
Chemical formula	C₉H₇N₅·H₂O
M_r	203.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	17.175 (3), 4.0653 (8), 14.421 (3)
β (°)	107.59 (3)
V (Å³)	959.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.05 × 0.05

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.737, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7430, 1683, 945
R_int	0.120
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.131, 1.01
No. of reflections	1683
No. of parameters	144
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N2ⁱ	0.90 (4)	2.07 (4)	2.957 (4)	169 (4)
O1—H1B···N3ⁱⁱ	0.76 (5)	2.17 (5)	2.927 (5)	172 (5)
N4—H4N···O1	0.86	1.87	2.715 (4)	169
N5—H5N···N1ⁱⁱⁱ	0.86	2.17	3.019 (4)	171

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

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Frederick, C. U. (1949). J. Am. Chem. Soc. 71, 761–766. PubMed Web of Science Google Scholar
Itoh, F., Yukishige, K. & Wajima, M. (1995). Chem. Pharm. Bull. 43, 230–235. CrossRef CAS PubMed Web of Science Google Scholar
Rigaku. (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Semenov, B. B. (2002). Russ. Chem. Bull. 51, 357–358. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536811003990

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