1,2-Bis(1H-tetra­zol-5-yl)benzene dihydrate

Xu, H.-J.; Pan, Y.-J.; Cui, L.-J.

doi:10.1107/S1600536809018224

organic compounds

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Volume 65| Part 6| June 2009| Page o1331

doi:10.1107/S1600536809018224

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1,2-Bis(1H-tetrazol-5-yl)benzene dihydrate

Hai-Jun Xu,^a ^* Yi-Jie Pan ^a and Li-Jing Cui ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: xuhj@seu.edu.cn

(Received 11 May 2009; accepted 14 May 2009; online 20 May 2009)

The asymmetric unit of the title compound, C₈H₆N₈·2H₂O, contains one half-molecule, with the benzene ring on a centre of symmetry, and two uncoordinated water molecules. The benzene ring is oriented at a dihedral angle of 34.43 (12)° with respect to the tetrazole ring. Strong O—H⋯N hydrogen bonds link the water molecules to the N atoms of the tetrazole ring. In the crystal structure, strong intermolecular O—H⋯O and O—H⋯N hydrogen bonds link the molecules into a network. One of the water H atoms is disordered over two positions and was refined with occupancies of 0.50.

Related literature

For general background, see: Luo et al. (2006 ). For related structures, see: Guzei & Bikzhanova (2002 ); Pan et al. (2007 ).

Experimental

Crystal data

C₈H₆N₈·2H₂O
M_r = 286.27
Monoclinic, C 2/c
a = 14.510 (3) Å
b = 12.427 (3) Å
c = 7.2576 (15) Å
β = 96.29 (3)°
V = 1300.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 294 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.971, T_max = 0.979
5963 measured reflections
1276 independent reflections
1041 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.098
S = 1.06
1276 reflections
101 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O1W	0.91 (2)	1.78 (2)	2.682 (2)	171.9 (19)
O1W—H1WA⋯N2ⁱ	0.85	2.02	2.8658 (19)	173
O1W—H1WB⋯O2Wⁱⁱ	0.85	1.98	2.813 (2)	168
O2W—H2WA⋯N1	0.85	2.06	2.896 (2)	169
O2W—H2WB⋯O2Wⁱⁱⁱ	0.85	1.97	2.813 (3)	170
O2W—H2WC⋯O2W^iv	0.85	2.01	2.814 (3)	158
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z; (iv) $[-x+1, y, -z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC (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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018224/hk2687sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018224/hk2687Isup2.hkl

checkCIF report

Comment top

The tetrazole functional group has currently been received considerable attention mainly because of a wide range of applications in coordination chemistry, medicinal chemistry and materials science (Luo et al., 2006). However, there are a few crystal structure reports of organic tetrazolates compounds in the literature (Guzei & Bikzhanova, 2002). We reported herein the synthesis and the crystal structure of the title compound.

The asymmetric unit of the title compound contains one-half molecule, with benzene ring on a centre of symmetry, and two uncoordinated water molecules (Fig. 1). The bond lengths and angles are in accordance with the corresponding values reported (Pan et al., 2007). The benzene ring is oriented with respect to the tetrazole ring at a dihedral angle of 34.43 (12)°. Strong intramolecular O-H···N hydrogen bonds (Table 1) link the water molecules to the nitrogens of the tetrazole ring.

In the crystal structure, strong intermolecular O-H···O and O-H···N hydrogen bonds (Table 1) link the molecules into a network (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Luo et al. (2006). For related structures, see: Guzei, et al. (2002); Pan et al. (2007).

Experimental top

For the preparation of the title compound, phthalonitrile (1.28 g, 10 mmol), NH₄Cl (1.38 g, 26 mmol) and NaN₃ (1.69 g, 13 mmol) were dissolved in DMF (60 ml). The mixture was heated to 353 K, and stirred for 48 h. Then, it was cooled to room temperature and poured into cold water and acidified to pH = 2 with concentrated hydrochloric acid. After 12 h at 277 K, the suspension was filtrated, and the residue was washed with H₂O and H₂O/EtOH (1/1), and then dried. Crystals suitable for X-ray analysis were obtained from an EtOH solution.

Computing details top

Data collection: CrystalClear (Rigaku/MSC (2005); cell refinement: CrystalClear Rigaku/MSC (2005); data reduction: CrystalClear (Rigaku/MSC (2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

1,2-Bis(1H-tetrazol-5-yl)benzene dihydrate top

Crystal data top

C₈H₆N₈·2H₂O	F(000) = 600
M_r = 286.27	D_x = 1.462 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5656 reflections
a = 14.510 (3) Å	θ = 3.3–27.5°
b = 12.427 (3) Å	µ = 0.12 mm⁻¹
c = 7.2576 (15) Å	T = 294 K
β = 96.29 (3)°	Prism, colorless
V = 1300.7 (5) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	1276 independent reflections
Radiation source: fine-focus sealed tube	1041 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −17→17
Absorption correction: multi-scan (Blessing, 1995)	k = −15→15
T_min = 0.971, T_max = 0.979	l = −8→8
5963 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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0394P)² + 0.846P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1276 reflections	Δρ_max = 0.20 e Å⁻³
101 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0220 (19)

Crystal data top

C₈H₆N₈·2H₂O	V = 1300.7 (5) Å³
M_r = 286.27	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.510 (3) Å	µ = 0.12 mm⁻¹
b = 12.427 (3) Å	T = 294 K
c = 7.2576 (15) Å	0.20 × 0.20 × 0.20 mm
β = 96.29 (3)°

Data collection top

Rigaku SCXmini diffractometer	1276 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	1041 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.979	R_int = 0.044
5963 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.20 e Å⁻³
1276 reflections	Δρ_min = −0.15 e Å⁻³
101 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	Occ. (<1)
O1W	0.20523 (9)	−0.46870 (10)	0.4630 (2)	0.0479 (4)
H1WA	0.1982	−0.5343	0.4316	0.086 (9)*
H1WB	0.1528	−0.4390	0.4684	0.084 (9)*
O2W	0.52104 (9)	−0.10467 (11)	−0.0561 (2)	0.0467 (4)
H2WA	0.4931	−0.1528	−0.0003	0.076 (8)*
H2WB	0.5036	−0.0452	−0.0135	0.060 (15)*	0.50
H2WC	0.4968	−0.1163	−0.1663	0.078 (19)*	0.50
N1	0.40777 (10)	−0.24613 (11)	0.1426 (2)	0.0332 (4)
N2	0.33249 (10)	−0.18460 (11)	0.1621 (2)	0.0397 (4)
N3	0.27393 (10)	−0.23572 (12)	0.2522 (2)	0.0417 (4)
N4	0.31147 (10)	−0.33246 (12)	0.2923 (2)	0.0353 (4)
H4A	0.2797 (14)	−0.3834 (17)	0.350 (3)	0.053 (6)*
C1	0.45124 (10)	−0.43665 (12)	0.2407 (2)	0.0264 (4)
C2	0.40490 (11)	−0.53513 (12)	0.2324 (2)	0.0308 (4)
H2A	0.3404	−0.5358	0.2205	0.037*
C3	0.45222 (11)	−0.63163 (13)	0.2414 (2)	0.0327 (4)
H3A	0.4198	−0.6963	0.2360	0.039*
C4	0.39372 (11)	−0.33838 (12)	0.2258 (2)	0.0277 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1W	0.0353 (8)	0.0370 (8)	0.0737 (10)	−0.0091 (6)	0.0168 (7)	−0.0132 (7)
O2W	0.0504 (9)	0.0396 (8)	0.0527 (9)	−0.0046 (6)	0.0166 (7)	0.0005 (7)
N1	0.0323 (8)	0.0253 (7)	0.0421 (9)	0.0035 (6)	0.0052 (6)	0.0021 (6)
N2	0.0379 (9)	0.0283 (8)	0.0528 (10)	0.0071 (6)	0.0040 (7)	0.0015 (7)
N3	0.0321 (9)	0.0304 (8)	0.0630 (11)	0.0082 (6)	0.0067 (8)	−0.0009 (7)
N4	0.0271 (8)	0.0262 (7)	0.0537 (10)	0.0020 (6)	0.0103 (7)	0.0017 (7)
C1	0.0265 (8)	0.0235 (8)	0.0298 (9)	0.0009 (6)	0.0059 (6)	0.0010 (7)
C2	0.0250 (9)	0.0280 (9)	0.0401 (10)	−0.0024 (6)	0.0065 (7)	−0.0014 (7)
C3	0.0357 (9)	0.0225 (8)	0.0408 (10)	−0.0050 (7)	0.0082 (8)	−0.0005 (7)
C4	0.0235 (8)	0.0255 (8)	0.0341 (9)	−0.0011 (6)	0.0026 (7)	−0.0017 (7)

Geometric parameters (Å, º) top

O1W—H1WA	0.8500	C1—C2	1.394 (2)
O1W—H1WB	0.8501	C1—C1ⁱ	1.407 (3)
O2W—H2WA	0.8499	C1—C4	1.476 (2)
O2W—H2WB	0.8500	C2—C3	1.380 (2)
O2W—H2WC	0.8500	C2—H2A	0.9300
N1—N2	1.353 (2)	C3—C3ⁱ	1.378 (3)
N2—N3	1.294 (2)	C3—H3A	0.9300
N3—N4	1.339 (2)	C4—N1	1.322 (2)
N4—H4A	0.91 (2)	C4—N4	1.338 (2)

H1WA—O1W—H1WB	110.3	C2—C1—C4	117.17 (14)
H2WA—O2W—H2WB	105.2	C1ⁱ—C1—C4	124.17 (8)
H2WA—O2W—H2WC	99.2	C3—C2—C1	121.71 (15)
H2WB—O2W—H2WC	112.4	C3—C2—H2A	119.1
C4—N1—N2	105.99 (13)	C1—C2—H2A	119.1
N3—N2—N1	110.96 (14)	C3ⁱ—C3—C2	119.65 (9)
N2—N3—N4	106.06 (13)	C3ⁱ—C3—H3A	120.2
C4—N4—N3	109.19 (14)	C2—C3—H3A	120.2
C4—N4—H4A	130.1 (13)	N1—C4—N4	107.80 (14)
N3—N4—H4A	120.6 (13)	N1—C4—C1	129.54 (15)
C2—C1—C1ⁱ	118.65 (9)	N4—C4—C1	122.58 (14)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1W	0.91 (2)	1.78 (2)	2.682 (2)	171.9 (19)
O1W—H1WA···N2ⁱⁱ	0.85	2.02	2.8658 (19)	173
O1W—H1WB···O2Wⁱⁱⁱ	0.85	1.98	2.813 (2)	168
O2W—H2WA···N1	0.85	2.06	2.896 (2)	169
O2W—H2WB···O2W^iv	0.85	1.97	2.813 (3)	170
O2W—H2WC···O2W^v	0.85	2.01	2.814 (3)	158

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

Experimental details

Crystal data
Chemical formula	C₈H₆N₈·2H₂O
M_r	286.27
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	14.510 (3), 12.427 (3), 7.2576 (15)
β (°)	96.29 (3)
V (Å³)	1300.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.971, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5963, 1276, 1041
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.098, 1.06
No. of reflections	1276
No. of parameters	101
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.15

Computer programs: CrystalClear (Rigaku/MSC (2005), CrystalClear Rigaku/MSC (2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1W	0.91 (2)	1.78 (2)	2.682 (2)	171.9 (19)
O1W—H1WA···N2ⁱ	0.85	2.02	2.8658 (19)	173.1
O1W—H1WB···O2Wⁱⁱ	0.85	1.98	2.813 (2)	167.6
O2W—H2WA···N1	0.85	2.06	2.896 (2)	169.0
O2W—H2WB···O2Wⁱⁱⁱ	0.85	1.97	2.813 (3)	169.5
O2W—H2WC···O2W^iv	0.85	2.01	2.814 (3)	157.9

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

Acknowledgements

HJX acknowledges a start-up grant from Southeast University, China.

References

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