Acta Cryst. (2008). E64, o1785 [ doi:10.1107/S1600536808026032 ]
The title compound, C9H11N3O4·H2O, was prepared by the reaction of dehydroacetic acid and semicarbazide hydrochloride. It crystallizes in a zwitterionic form with cationic iminium and anionic enolate groups. In the crystal structure, the almost planar molecules are held together by N-H
O, O-HO and C-HO hydrogen bonds, some of them involving the water molecules.
A mixture of dehydroacetic acid (0.01 mol) and semicarbazide hydrochloride (0.01 mol), in ethanol (20 ml) was refluxed for 1 h. After cooling, filtration and drying, the compound dehydroacetic acid semicarbazide was obtained. A small quantity of this compound (10 mg) was dissolved in aqueous ethanol (95 / 12 ml), and the solution was then allowed to evaporate at room temperature. Prismatic yellow single crystals of the title compound were formed after 8 days.
The O—H distances of the water molecules were restrained to 0.85 (1) Å, to ensure chemically reasonable geometry, with Uiso fixed at 1.5Ueq(O). The iminium and ammino H atoms was located in a difference Fourier map and were refined isotropically. The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å) with Uiso(H) = 1.2Ueq(C), but were allowed to rotate freely about the C—C bonds. H7 atom was placed in a geometrically idealized position (C—H = 0.93 Å) and constrained to ride on its parent atom with Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).
![[Figure 1]](./wk2091fig1thm.gif)
| Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./wk2091fig2thm.gif)
| Fig. 2. The crystal packing of (I), viewed down the b axis. Dashed lines indicate the N—H···O and O—H···O interactions. |
| C9H11N3O4·H2O | F000 = 512 |
| Mr = 243.22 | Dx = 1.486 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2841 reflections |
| a = 7.1731 (4) Å | θ = 3.1–25.8º |
| b = 12.6590 (10) Å | µ = 0.12 mm−1 |
| c = 12.3698 (3) Å | T = 173 (2) K |
| β = 104.603 (6)º | Prism, yellow |
| V = 1086.95 (11) Å3 | 0.35 × 0.05 × 0.02 mm |
| Z = 4 |
| Nonius KappaCCD diffractometer | 1699 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.055 |
| Detector resolution: 9 pixels mm-1 | θmax = 27.5º |
| T = 173(2) K | θmin = 2.9º |
| CCD scans | h = −9→9 |
| Absorption correction: none | k = −16→15 |
| 11787 measured reflections | l = −15→16 |
| 2485 independent reflections |
| 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)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0289P)2 + 0.445P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 2485 reflections | Δρmax = 0.33 e Å−3 |
| 178 parameters | Δρmin = −0.26 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C9H11N3O4·H2O | V = 1086.95 (11) Å3 |
| Mr = 243.22 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 7.1731 (4) Å | µ = 0.12 mm−1 |
| b = 12.6590 (10) Å | T = 173 (2) K |
| c = 12.3698 (3) Å | 0.35 × 0.05 × 0.02 mm |
| β = 104.603 (6)º |
| Nonius KappaCCD diffractometer | 2485 independent reflections |
| Absorption correction: none | 1699 reflections with I > 2σ(I) |
| 11787 measured reflections | Rint = 0.055 |
| R[F2 > 2σ(F2)] = 0.048 | 178 parameters |
| wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | Δρmax = 0.33 e Å−3 |
| 2485 reflections | Δρmin = −0.26 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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.5343 (3) | −0.25527 (15) | 0.37044 (14) | 0.0287 (4) | |
| C2 | 0.7633 (2) | −0.06094 (14) | 0.56842 (14) | 0.0253 (4) | |
| C3 | 0.8032 (4) | −0.11552 (17) | 0.67854 (16) | 0.0476 (6) | |
| H3A | 0.7151 | −0.1734 | 0.6744 | 0.057* | |
| H3B | 0.7871 | −0.0666 | 0.7348 | 0.057* | |
| H3C | 0.9329 | −0.1418 | 0.6974 | 0.057* | |
| C4 | 0.8087 (2) | 0.04894 (13) | 0.55327 (13) | 0.0240 (4) | |
| C5 | 0.9088 (3) | 0.11044 (14) | 0.64744 (15) | 0.0292 (4) | |
| C6 | 0.8929 (3) | 0.26084 (15) | 0.52451 (15) | 0.0305 (4) | |
| C7 | 0.8054 (3) | 0.20520 (15) | 0.43545 (15) | 0.0316 (4) | |
| H7 | 0.7733 | 0.2375 | 0.3657 | 0.038* | |
| C8 | 0.7593 (2) | 0.09564 (14) | 0.44518 (14) | 0.0269 (4) | |
| C9 | 0.9441 (3) | 0.37503 (16) | 0.52619 (18) | 0.0422 (5) | |
| H9A | 0.9024 | 0.4034 | 0.452 | 0.051* | |
| H9B | 1.0812 | 0.3829 | 0.5527 | 0.051* | |
| H9C | 0.8817 | 0.4123 | 0.5749 | 0.051* | |
| N1 | 0.4877 (3) | −0.35801 (14) | 0.36960 (16) | 0.0397 (4) | |
| N2 | 0.6282 (2) | −0.21693 (12) | 0.47382 (13) | 0.0336 (4) | |
| N3 | 0.6811 (2) | −0.11234 (12) | 0.47752 (12) | 0.0272 (3) | |
| O1 | 0.9689 (2) | 0.08309 (11) | 0.74427 (10) | 0.0424 (4) | |
| O3 | 0.6744 (2) | 0.04451 (10) | 0.35702 (10) | 0.0369 (4) | |
| O2 | 0.9464 (2) | 0.21590 (10) | 0.62831 (10) | 0.0355 (3) | |
| O4 | 0.4983 (2) | −0.19779 (11) | 0.28793 (11) | 0.0414 (4) | |
| O1W | 0.6521 (3) | −0.10956 (13) | 0.12207 (12) | 0.0470 (4) | |
| H11W | 0.597 (4) | −0.131 (2) | 0.168 (2) | 0.071* | |
| H21W | 0.763 (4) | −0.103 (2) | 0.160 (2) | 0.071* | |
| H1A | 0.440 (3) | −0.3872 (19) | 0.308 (2) | 0.048 (7)* | |
| H1B | 0.514 (3) | −0.3924 (17) | 0.4326 (19) | 0.037 (6)* | |
| H2 | 0.650 (3) | −0.2591 (18) | 0.5351 (19) | 0.042 (6)* | |
| H3 | 0.656 (4) | −0.069 (2) | 0.410 (2) | 0.075 (8)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0301 (9) | 0.0304 (10) | 0.0238 (8) | −0.0033 (7) | 0.0036 (7) | −0.0023 (7) |
| C2 | 0.0258 (9) | 0.0274 (9) | 0.0222 (8) | 0.0011 (7) | 0.0049 (7) | 0.0004 (7) |
| C3 | 0.0780 (16) | 0.0371 (12) | 0.0232 (10) | −0.0137 (11) | 0.0043 (10) | 0.0025 (8) |
| C4 | 0.0260 (9) | 0.0241 (9) | 0.0203 (8) | 0.0006 (7) | 0.0028 (7) | −0.0015 (6) |
| C5 | 0.0318 (10) | 0.0288 (10) | 0.0254 (9) | −0.0014 (8) | 0.0042 (7) | −0.0023 (7) |
| C6 | 0.0341 (10) | 0.0264 (9) | 0.0306 (9) | −0.0012 (7) | 0.0073 (8) | 0.0002 (7) |
| C7 | 0.0379 (11) | 0.0283 (10) | 0.0256 (9) | 0.0005 (8) | 0.0023 (8) | 0.0046 (7) |
| C8 | 0.0283 (9) | 0.0260 (9) | 0.0237 (9) | 0.0027 (7) | 0.0016 (7) | −0.0001 (7) |
| C9 | 0.0557 (13) | 0.0270 (10) | 0.0417 (12) | −0.0078 (9) | 0.0082 (10) | −0.0023 (8) |
| N1 | 0.0568 (12) | 0.0304 (9) | 0.0295 (9) | −0.0110 (8) | 0.0063 (8) | −0.0035 (8) |
| N2 | 0.0488 (10) | 0.0240 (8) | 0.0243 (8) | −0.0078 (7) | 0.0023 (7) | 0.0014 (6) |
| N3 | 0.0330 (8) | 0.0230 (8) | 0.0225 (7) | −0.0021 (6) | 0.0016 (6) | 0.0002 (6) |
| O1 | 0.0586 (9) | 0.0412 (8) | 0.0201 (6) | −0.0112 (7) | −0.0036 (6) | 0.0005 (6) |
| O3 | 0.0539 (9) | 0.0288 (7) | 0.0204 (6) | −0.0043 (6) | −0.0046 (6) | 0.0014 (5) |
| O2 | 0.0480 (8) | 0.0284 (7) | 0.0264 (7) | −0.0085 (6) | 0.0024 (6) | −0.0033 (5) |
| O4 | 0.0562 (9) | 0.0366 (8) | 0.0248 (7) | −0.0108 (7) | −0.0018 (6) | 0.0027 (6) |
| O1W | 0.0593 (10) | 0.0501 (10) | 0.0294 (8) | −0.0083 (8) | 0.0068 (7) | −0.0032 (7) |
| C1—O4 | 1.227 (2) | C6—C9 | 1.490 (3) |
| C1—N1 | 1.342 (2) | C7—C8 | 1.438 (3) |
| C1—N2 | 1.375 (2) | C7—H7 | 0.93 |
| C2—N3 | 1.304 (2) | C8—O3 | 1.282 (2) |
| C2—C4 | 1.452 (2) | C9—H9A | 0.96 |
| C2—C3 | 1.489 (2) | C9—H9B | 0.96 |
| C3—H3A | 0.96 | C9—H9C | 0.96 |
| C3—H3B | 0.96 | N1—H1A | 0.84 (3) |
| C3—H3C | 0.96 | N1—H1B | 0.87 (2) |
| C4—C8 | 1.423 (2) | N2—N3 | 1.375 (2) |
| C4—C5 | 1.434 (2) | N2—H2 | 0.91 (2) |
| C5—O1 | 1.217 (2) | N3—H3 | 0.98 (3) |
| C5—O2 | 1.394 (2) | O1W—H11W | 0.82 (3) |
| C6—C7 | 1.325 (3) | O1W—H21W | 0.82 (3) |
| C6—O2 | 1.368 (2) | ||
| O4—C1—N1 | 124.65 (17) | C6—C7—H7 | 119.5 |
| O4—C1—N2 | 121.02 (17) | C8—C7—H7 | 119.5 |
| N1—C1—N2 | 114.33 (16) | O3—C8—C4 | 122.81 (16) |
| N3—C2—C4 | 115.73 (15) | O3—C8—C7 | 119.05 (15) |
| N3—C2—C3 | 119.87 (17) | C4—C8—C7 | 118.13 (15) |
| C4—C2—C3 | 124.41 (16) | C6—C9—H9A | 109.5 |
| C2—C3—H3A | 109.5 | C6—C9—H9B | 109.5 |
| C2—C3—H3B | 109.5 | H9A—C9—H9B | 109.5 |
| H3A—C3—H3B | 109.5 | C6—C9—H9C | 109.5 |
| C2—C3—H3C | 109.5 | H9A—C9—H9C | 109.5 |
| H3A—C3—H3C | 109.5 | H9B—C9—H9C | 109.5 |
| H3B—C3—H3C | 109.5 | C1—N1—H1A | 118.7 (16) |
| C8—C4—C5 | 119.53 (16) | C1—N1—H1B | 118.7 (14) |
| C8—C4—C2 | 120.58 (15) | H1A—N1—H1B | 122 (2) |
| C5—C4—C2 | 119.87 (15) | N3—N2—C1 | 115.93 (15) |
| O1—C5—O2 | 113.83 (16) | N3—N2—H2 | 123.4 (14) |
| O1—C5—C4 | 128.74 (18) | C1—N2—H2 | 120.7 (14) |
| O2—C5—C4 | 117.43 (15) | C2—N3—N2 | 124.75 (15) |
| C7—C6—O2 | 121.43 (17) | C2—N3—H3 | 113.8 (17) |
| C7—C6—C9 | 126.21 (18) | N2—N3—H3 | 121.4 (17) |
| O2—C6—C9 | 112.36 (16) | C6—O2—C5 | 122.49 (14) |
| C6—C7—C8 | 120.93 (17) | H11W—O1W—H21W | 102 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.84 (2) | 2.18 (2) | 3.015 (2) | 176.3 (17) |
| N1—H1B···O1Wii | 0.87 (2) | 2.30 (2) | 3.075 (2) | 147.9 (19) |
| N2—H2···O1Wii | 0.91 (2) | 1.98 (2) | 2.839 (2) | 158 (2) |
| N3—H3···O3 | 0.98 (2) | 1.60 (3) | 2.476 (2) | 147 (2) |
| O1W—H11W···O4 | 0.82 (3) | 1.99 (3) | 2.796 (2) | 171 (3) |
| O1W—H21W···O1iii | 0.82 (3) | 2.00 (3) | 2.823 (2) | 178.0 (18) |
| C3—H3B···O1 | 0.96 | 2.29 | 2.812 (3) | 114 |
| C7—H7···O4iv | 0.93 | 2.49 | 3.294 (2) | 145 |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y−1/2, z+1/2; (iii) −x+2, −y, −z+1; (iv) −x+1, y+1/2, −z+1/2. |
| C2—N3 | 1.304 (2) | C4—C8 | 1.423 (2) |
| C2—C4 | 1.452 (2) | C8—O3 | 1.282 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.84 (2) | 2.18 (2) | 3.015 (2) | 176.3 (17) |
| N1—H1B···O1Wii | 0.87 (2) | 2.30 (2) | 3.075 (2) | 147.9 (19) |
| N2—H2···O1Wii | 0.91 (2) | 1.98 (2) | 2.839 (2) | 158 (2) |
| N3—H3···O3 | 0.98 (2) | 1.60 (3) | 2.476 (2) | 147 (2) |
| O1W—H11W···O4 | 0.82 (3) | 1.99 (3) | 2.796 (2) | 171 (3) |
| O1W—H21W···O1iii | 0.82 (3) | 2.00 (3) | 2.823 (2) | 178.0 (18) |
| C3—H3B···O1 | 0.96 | 2.29 | 2.812 (3) | 114 |
| C7—H7···O4iv | 0.93 | 2.49 | 3.294 (2) | 145 |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y−1/2, z+1/2; (iii) −x+2, −y, −z+1; (iv) −x+1, y+1/2, −z+1/2. |
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NLO materials play an important role in the field of fibre optic communications and optical signal processing. In the last two decades, extensive research has shown that organic crystals can exhibit nonlinear optical efficiencies which are two orders of magnitude higher than those of inorganic materials. Semicarbazones of substituted benzaldehydes and acetophenones were reported to be some of the potential organic NLO materials.
In this paper, the structure of the title compound (I), C9H13N3O5 is reported. The asymmetric unit of (I) contains one Dehydroacetic acid semicarbazide molecule and one water molecule (Fig. 1).
It is seen that the structure reported here adopts a zwitterion form, because, among other reasons, its N+—H bond distances [0.98 (3) Å] is comparable with those from similar zwitterions in the literature [1.11 (3) Å; 1.10 (3) Å] (Petek et al., 2006; Wojciechowski et al., 2003).
The bond distances shown in Table 1 indicate that the C2—N3 iminium bond length of 1.303 (2) Å agree with similar bond in related compounds (Girija & Begum, 2004a; Girija et al., 2004b). This distance is slightly longer than a typical C=N bond (1.269 Å); but much shorter than the single carbon-nitrogen (1.409 Å) (Gowda et al. 2007), because of the resonance.
The C8—O3 bond length [1.282 (2) Å] is intermediate between single and double carbon to oxygen bond lengths (1.362 Å, 1.222 Å) the carbon-carbon bond connecting the enol and imine groups exhibit intermediate distances between a single and a double bond, being closer to latter one. C4—C8 = 1.423 (2) Å, C2—C4 = 1.452 (2) Å, indicate the zwitterionic character of the title compound (Wojciechowski et al. 2003). The molecular configuration is determined by the presence of the intramolecular hydrogen bond O-···H—N+ (Table 2).
The main molecule in (I) is essentially planar, with a maximum deviation from the mean plane for the non-hydrogen atoms of 0.022 (2) Å. The iminium atom H3, participates in a strong intramolecular hydrogen bond with the enolate atom, O1 (Table 1), which generates an S(6) ring motif (Bernstein et al. 1995). Similar intramolecular hydrogen bonds were reported in the above-mentioned zwitterionic phenolates (Huang et al. 2006). This six-membered pseudocycle is almost planar, the maximum deviation from the mean plane being 0.012 Å for atom C2. The bond lengths and angles are in usual ranges (E)-1-(4-Hydroxybenzylidene) semicarbazide hemihydrate (Tai et al., 2007) and (E)-1-(4-Methoxybenzylidene) -semicarbazide (Liang et al., 2007).
The crystal structure of (I) is stabilized by N—H···O; O—H···O, and C—H···O hydrogen bonds (Fig. 2 and Table 2).