Acta Cryst. (2009). E65, o1331 [ doi:10.1107/S1600536809018224 ]
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-HO and O-HN 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.
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.
One of the H atoms bonded to O2W was disordered. During the refinement process, the disordered H atom was refined with occupancies of 0.50 and 0.50. H atom (for NH) was located in difference Fourier synthesis and refined isotropically. The remaining H atoms were positioned geometrically with O-H = 0.85 Å (for H2O) [Uiso(H) = 0.060 (15)-0.086 (9) Å2] and C-H = 0.93 Å, for aromatic H atoms and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
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).
![[Figure 1]](./hk2687fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./hk2687fig2thm.gif)
| Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
| C8H6N8·2H2O1 | F000 = 600 |
| Mr = 286.27 | Dx = 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 = 3.3–27.5º |
| b = 12.427 (3) Å | µ = 0.12 mm−1 |
| c = 7.2576 (15) Å | T = 294 K |
| β = 96.29 (3)º | Prism, colorless |
| V = 1300.7 (5) Å3 | 0.20 × 0.20 × 0.20 mm |
| Z = 4 |
| Rigaku SCXmini diffractometer | 1276 independent reflections |
| Radiation source: fine-focus sealed tube | 1041 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.044 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 26.0º |
| T = 294 K | θmin = 3.3º |
| ω scans | h = −17→17 |
| Absorption correction: multi-scan (Blessing, 1995) | k = −15→15 |
| Tmin = 0.971, Tmax = 0.979 | l = −8→8 |
| 5963 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.846P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.098 | (Δ/σ)max < 0.001 |
| S = 1.06 | Δρmax = 0.20 e Å−3 |
| 1276 reflections | Δρmin = −0.15 e Å−3 |
| 101 parameters | 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) |
| Secondary atom site location: difference Fourier map |
| C8H6N8·2H2O1 | V = 1300.7 (5) Å3 |
| Mr = 286.27 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| 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)º |
| Rigaku SCXmini diffractometer | 1276 independent reflections |
| Absorption correction: multi-scan (Blessing, 1995) | 1041 reflections with I > 2σ(I) |
| Tmin = 0.971, Tmax = 0.979 | Rint = 0.044 |
| 5963 measured reflections |
| R[F2 > 2σ(F2)] = 0.040 | 101 parameters |
| wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | Δρmax = 0.20 e Å−3 |
| 1276 reflections | Δρmin = −0.15 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | 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) |
| 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) |
| 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 codes: (i) −x+1, y, −z+1/2. |
| 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···O2Wiv | 0.85 | 1.97 | 2.813 (3) | 170 |
| O2W—H2WC···O2Wv | 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. |
| 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···O2Wiv | 0.85 | 2.01 | 2.814 (3) | 158 |
| 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. |
Blessing, R. H. (1995). Acta Cryst. A51, 33–38.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Guzei, I. A. & Bikzhanova, G. A. (2002). Acta Cryst. E58, o937–o939.
Luo, J., Zhang, X.-R., Cui, L.-L., Dai, W.-Q. & Liu, B.-S. (2006). Acta Cryst. C62, m614–m616.
Pan, W.-L., Chen, X.-Y. & Hu, C.-W. (2007). Acta Cryst. E63, o1606–o1608.
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
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.