4,5-Bis(1H-tetra­zol-5-yl)-1H-imidazole monohydrate

Guo, M.

doi:10.1107/S1600536809017899

organic compounds

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Volume 65| Part 6| June 2009| Page o1403

doi:10.1107/S1600536809017899

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4,5-Bis(1H-tetrazol-5-yl)-1H-imidazole monohydrate

Min Guo ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: seuwangwei@gmail.com

(Received 29 April 2009; accepted 12 May 2009; online 29 May 2009)

The title compound, C₅H₄N₁₀·H₂O, is composed of three five-membered rings that are essentially coplanar, the dihedral angles between the imidazole ring and the tetrazole rings being 3.5 (2) and 3.0 (2)°. In the crystal, intermolecular O—H⋯N, N—H⋯O and N—H⋯N hydrogen bonds lead to the formation of a three-dimensional network. An intramolecular N—H⋯N hydrogen bond is also present.

Related literature

For the example of a zinc complex by reaction of the title compound as ligand, see: Zhao et al. (2004 ).

Experimental

Crystal data

C₅H₄N₁₀·H₂O
M_r = 222.20
Monoclinic, P 2₁ /c
a = 15.607 (3) Å
b = 3.6706 (7) Å
c = 18.127 (7) Å
β = 119.13 (2)°
V = 907.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 294 K
0.08 × 0.08 × 0.03 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.892, T_max = 0.990
7767 measured reflections
1785 independent reflections
1362 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.201
S = 1.06
1785 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯N3ⁱ	0.91 (2)	2.12 (2)	3.014 (4)	169 (5)
O1W—H1W⋯N9ⁱⁱ	0.91 (2)	1.99 (2)	2.884 (4)	169 (5)
N2—H2A⋯O1Wⁱ	0.86	2.41	3.188 (4)	151
N7—H7A⋯N1ⁱⁱⁱ	0.86	2.10	2.799 (4)	139
N6—H6A⋯N10	0.86	1.95	2.711 (4)	146
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[-x+1, y+{\script{3\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x, -y, -z+1.

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/S1600536809017899/im2114sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017899/im2114Isup2.hkl

checkCIF report

Comment top

The crystal data show that in the title compound, C₅H₄N₁₀ × H₂O, the molecule is essentially planar with dihedral angles between imidazole and the tetrazole rings of 3.5 (2)° and 3.0 (2)°, respectively.

Intramolecular hydrogen bonds between the tetrazole rings determine the conformation of the molecule. It is also interesting to note that strong intermolecular have been found between the tetrazole and imidazole rings towards the solvent water molecules. This results in the formation of a three-dimensional network, as shown in Figure 2.

Related literature top

For the structure of a related zinc complex, see: Zhao et al. (2004).

Experimental top

NaN₃ (0.975 g,15 mmol) and NH₄Cl (0.587 g, 11 mmol) were added to a solution of (4,5-Dicyano)-imidazole (1.18 g,10 mmol) in DMF (25 ml) under magnetic stirring in an oil bath. The resulting mixture was heated to 90°C for 8 h until the starting material was fully consumed as shown with the help of TLC detection. The mixture was allowed to cool to room temperature and acidified to pH = 2 with 1M aqueous HCl. The resulting precipitate was collected, washed with a small amount of water and dried at 60°C for 12 h. Colorless crystals of the title compound suitable for X-ray diffraction were obtained from an ethanolic solution after one week.

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. The molecular structure of the title compound showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Three-dimensional network of the title compound viewed along a axis.

4,5-Bis(1H-tetrazol-5-yl)-1H-imidazole monohydrate top

Crystal data top

C₅H₄N₁₀·H₂O	F(000) = 456
M_r = 222.20	D_x = 1.627 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2076 reflections
a = 15.607 (3) Å	θ = 2.0–27.5°
b = 3.6706 (7) Å	µ = 0.13 mm⁻¹
c = 18.127 (7) Å	T = 294 K
β = 119.13 (2)°	Block, colorless
V = 907.1 (5) Å³	0.08 × 0.08 × 0.03 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	1785 independent reflections
Radiation source: fine-focus sealed tube	1362 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.6°
ω scans	h = −19→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −4→4
T_min = 0.892, T_max = 0.990	l = −22→22
7767 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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.201	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0998P)² + 1.6707P] where P = (F_o² + 2F_c²)/3
1785 reflections	(Δ/σ)_max < 0.001
153 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₅H₄N₁₀·H₂O	V = 907.1 (5) Å³
M_r = 222.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.607 (3) Å	µ = 0.13 mm⁻¹
b = 3.6706 (7) Å	T = 294 K
c = 18.127 (7) Å	0.08 × 0.08 × 0.03 mm
β = 119.13 (2)°

Data collection top

Rigaku SCXmini diffractometer	1785 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1362 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.990	R_int = 0.061
7767 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.201	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.60 e Å⁻³
1785 reflections	Δρ_min = −0.56 e Å⁻³
153 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
O1W	0.6668 (2)	1.0057 (9)	0.61964 (19)	0.0429 (8)
N5	0.4974 (2)	0.4374 (9)	0.67749 (19)	0.0313 (8)
N6	0.40302 (19)	0.3471 (9)	0.64859 (17)	0.0260 (7)
H6A	0.3794	0.2519	0.6783	0.031*
N9	0.2305 (2)	−0.0391 (9)	0.73314 (18)	0.0305 (7)
N10	0.2612 (2)	0.0904 (9)	0.68015 (18)	0.0267 (7)
N1	0.0913 (2)	0.2414 (9)	0.45237 (17)	0.0270 (7)
N7	0.1017 (2)	0.0035 (9)	0.61097 (18)	0.0302 (8)
H7A	0.0420	−0.0063	0.5709	0.036*
N8	0.1358 (2)	−0.0896 (10)	0.69193 (19)	0.0337 (8)
N4	0.5023 (2)	0.5693 (9)	0.61343 (19)	0.0294 (7)
N2	0.2075 (2)	0.4482 (8)	0.42653 (17)	0.0263 (7)
H2A	0.2371	0.5317	0.4006	0.032*
N3	0.4130 (2)	0.5680 (8)	0.54265 (17)	0.0267 (7)
C1	0.1142 (3)	0.3667 (11)	0.3940 (2)	0.0314 (9)
H1A	0.0688	0.3924	0.3371	0.038*
C5	0.3516 (2)	0.4283 (9)	0.5666 (2)	0.0201 (7)
C4	0.1794 (2)	0.1138 (9)	0.6055 (2)	0.0212 (7)
C2	0.2476 (2)	0.3706 (9)	0.5112 (2)	0.0209 (7)
C3	0.1767 (2)	0.2407 (9)	0.5288 (2)	0.0211 (7)
H1W	0.698 (3)	1.123 (14)	0.670 (2)	0.067 (16)*
H2W	0.635 (3)	1.117 (14)	0.568 (2)	0.069 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1W	0.0462 (18)	0.0463 (18)	0.0335 (17)	−0.0038 (14)	0.0172 (15)	0.0008 (14)
N5	0.0211 (15)	0.044 (2)	0.0262 (16)	−0.0073 (13)	0.0094 (13)	−0.0022 (14)
N6	0.0198 (14)	0.0368 (17)	0.0210 (14)	−0.0051 (13)	0.0095 (12)	0.0011 (12)
N9	0.0284 (16)	0.0370 (18)	0.0242 (15)	−0.0031 (13)	0.0114 (13)	0.0054 (13)
N10	0.0215 (14)	0.0366 (17)	0.0201 (14)	−0.0032 (13)	0.0088 (12)	0.0036 (13)
N1	0.0198 (14)	0.0370 (18)	0.0192 (14)	−0.0032 (13)	0.0055 (12)	0.0010 (13)
N7	0.0207 (15)	0.0437 (19)	0.0223 (15)	−0.0063 (13)	0.0074 (12)	0.0039 (13)
N8	0.0302 (17)	0.046 (2)	0.0254 (16)	−0.0057 (15)	0.0142 (14)	0.0056 (14)
N4	0.0236 (15)	0.0361 (18)	0.0273 (16)	−0.0066 (13)	0.0114 (13)	−0.0014 (13)
N2	0.0244 (15)	0.0352 (17)	0.0211 (15)	−0.0028 (13)	0.0125 (13)	0.0034 (13)
N3	0.0209 (14)	0.0338 (17)	0.0238 (15)	−0.0041 (13)	0.0097 (13)	0.0004 (13)
C1	0.0250 (18)	0.045 (2)	0.0185 (17)	−0.0020 (16)	0.0058 (15)	0.0032 (15)
C5	0.0208 (16)	0.0219 (16)	0.0199 (16)	−0.0018 (13)	0.0117 (14)	−0.0015 (13)
C4	0.0199 (16)	0.0236 (17)	0.0192 (16)	−0.0014 (14)	0.0087 (13)	0.0008 (13)
C2	0.0206 (16)	0.0222 (17)	0.0177 (16)	−0.0023 (13)	0.0076 (13)	−0.0028 (13)
C3	0.0168 (15)	0.0263 (18)	0.0193 (16)	0.0016 (13)	0.0081 (13)	0.0003 (14)

Geometric parameters (Å, º) top

O1W—H1W	0.91 (2)	N7—N8	1.339 (4)
O1W—H2W	0.91 (2)	N7—H7A	0.8600
N5—N4	1.294 (4)	N4—N3	1.359 (4)
N5—N6	1.343 (4)	N2—C1	1.313 (4)
N6—C5	1.335 (4)	N2—C2	1.375 (4)
N6—H6A	0.8600	N2—H2A	0.8600
N9—N8	1.303 (4)	N3—C5	1.332 (4)
N9—N10	1.352 (4)	C1—H1A	0.9300
N10—C4	1.336 (4)	C5—C2	1.450 (4)
N1—C1	1.351 (5)	C4—C3	1.446 (4)
N1—C3	1.378 (4)	C2—C3	1.378 (5)
N7—C4	1.327 (4)

H1W—O1W—H2W	125 (5)	C5—N3—N4	105.3 (3)
N4—N5—N6	105.9 (3)	N2—C1—N1	112.6 (3)
C5—N6—N5	109.3 (3)	N2—C1—H1A	123.7
C5—N6—H6A	125.4	N1—C1—H1A	123.7
N5—N6—H6A	125.4	N3—C5—N6	108.1 (3)
N8—N9—N10	109.7 (3)	N3—C5—C2	124.8 (3)
C4—N10—N9	104.4 (3)	N6—C5—C2	127.1 (3)
C1—N1—C3	107.0 (3)	N7—C4—N10	111.2 (3)
C4—N7—N8	105.6 (3)	N7—C4—C3	124.7 (3)
C4—N7—H7A	127.2	N10—C4—C3	124.1 (3)
N8—N7—H7A	127.2	N2—C2—C3	110.5 (3)
N9—N8—N7	109.1 (3)	N2—C2—C5	119.4 (3)
N5—N4—N3	111.4 (3)	C3—C2—C5	130.1 (3)
C1—N2—C2	104.8 (3)	C2—C3—N1	105.0 (3)
C1—N2—H2A	127.6	C2—C3—C4	133.1 (3)
C2—N2—H2A	127.6	N1—C3—C4	121.9 (3)

N4—N5—N6—C5	−0.3 (4)	C1—N2—C2—C3	0.1 (4)
N8—N9—N10—C4	0.1 (4)	C1—N2—C2—C5	179.6 (3)
N10—N9—N8—N7	0.2 (4)	N3—C5—C2—N2	2.9 (5)
C4—N7—N8—N9	−0.4 (4)	N6—C5—C2—N2	−175.6 (3)
N6—N5—N4—N3	0.0 (4)	N3—C5—C2—C3	−177.6 (4)
N5—N4—N3—C5	0.3 (4)	N6—C5—C2—C3	3.8 (6)
C2—N2—C1—N1	0.1 (4)	N2—C2—C3—N1	−0.2 (4)
C3—N1—C1—N2	−0.2 (5)	C5—C2—C3—N1	−179.6 (3)
N4—N3—C5—N6	−0.5 (4)	N2—C2—C3—C4	178.4 (3)
N4—N3—C5—C2	−179.2 (3)	C5—C2—C3—C4	−1.1 (6)
N5—N6—C5—N3	0.5 (4)	C1—N1—C3—C2	0.2 (4)
N5—N6—C5—C2	179.2 (3)	C1—N1—C3—C4	−178.6 (3)
N8—N7—C4—N10	0.5 (4)	N7—C4—C3—C2	178.5 (4)
N8—N7—C4—C3	−179.9 (3)	N10—C4—C3—C2	−1.9 (6)
N9—N10—C4—N7	−0.3 (4)	N7—C4—C3—N1	−3.1 (5)
N9—N10—C4—C3	−179.9 (3)	N10—C4—C3—N1	176.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···N3ⁱ	0.91 (2)	2.12 (2)	3.014 (4)	169 (5)
N2—H2A···O1Wⁱ	0.86	2.41	3.188 (4)	151
O1W—H1W···N9ⁱⁱ	0.91 (2)	1.99 (2)	2.884 (4)	169 (5)
N7—H7A···N1ⁱⁱⁱ	0.86	2.10	2.799 (4)	139
N6—H6A···N10	0.86	1.95	2.711 (4)	146

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y+3/2, −z+3/2; (iii) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₅H₄N₁₀·H₂O
M_r	222.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	15.607 (3), 3.6706 (7), 18.127 (7)
β (°)	119.13 (2)
V (Å³)	907.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.08 × 0.08 × 0.03

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.892, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	7767, 1785, 1362
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.201, 1.06
No. of reflections	1785
No. of parameters	153
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.56

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
O1W—H2W···N3ⁱ	0.91 (2)	2.12 (2)	3.014 (4)	169 (5)
N2—H2A···O1Wⁱ	0.86	2.41	3.188 (4)	151.0
O1W—H1W···N9ⁱⁱ	0.91 (2)	1.99 (2)	2.884 (4)	169 (5)
N7—H7A···N1ⁱⁱⁱ	0.86	2.10	2.799 (4)	138.5
N6—H6A···N10	0.86	1.95	2.711 (4)	146.1

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y+3/2, −z+3/2; (iii) −x, −y, −z+1.

Acknowledgements

The author is grateful to the Starter Fund of Southeast University for financial support to buy the CCD X-ray diffractometer.

References

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, H., Ye, Q., Wu, Q., Song, Y.-M., Liu, Y.-J. & Xiong, R.-G. (2004). Z. Anorg. Allg. Chem. 630, 1367–1370. Web of Science CSD CrossRef CAS Google Scholar