Acta Cryst. (2007). E63, o2820 [ doi:10.1107/S1600536807021381 ]
In the title compound, C6H11N3O2S, which is an example of a push-pull olefin, a network of N-H
O, C-HO and C-HN interactions help to establish the crystal packing.
2.5 mmol (150 mg) of 1,1-dimethylhydrazine was added at room temperature to 2.5 mmol (438 mg) of 3-ethoxy-2-methylsulfonylpropenenitrile (acrylonitrile) without any solvent. The reaction mixture became hot and after 10 min. of stirring ethanol (formed by the reaction) was removed and the crude product was recrystallized from ethyl acetate-hexane (1:4 v/v), to yield a light yellow powder (86%). Recrystallization from chloroform gave pink blocks of (I).
The H atoms were geometrically placed (C—H = 0.93–0.96 Å, N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXS97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: enCIFer (Allen et al., 2004).
![[Figure 1]](./hb2380fig1thm.gif)
| Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level (arbitrary spheres for the H atoms). |
![[Figure 2]](./hb2380fig2thm.gif)
| Fig. 2. Packing diagram of (I). Hydrogen-bond interactions are indicated by dashed lines. |
| C6H11N3O2S | F(000) = 400 |
| Mr = 189.24 | Dx = 1.425 Mg m−3 |
| Monoclinic, P21/c | Melting point: 421 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 11.526 (2) Å | Cell parameters from 5328 reflections |
| b = 6.881 (1) Å | θ = 3.5–27.9° |
| c = 11.577 (2) Å | µ = 0.33 mm−1 |
| β = 106.06 (3)° | T = 100 K |
| V = 882.4 (3) Å3 | Slab, pink |
| Z = 4 | 0.28 × 0.24 × 0.04 mm |
| Oxford Diffraction GEMINI R diffractometer | 1606 independent reflections |
| Radiation source: fine-focus sealed tube | 1310 reflections with I > 2σ(I) |
| graphite | Rint = 0.038 |
| Rotation method data acquisition using ω and phi scans | θmax = 25.3°, θmin = 4.2° |
| Absorption correction: analytical (Clark & Reid, 1995) | h = −13→13 |
| Tmin = 0.935, Tmax = 0.987 | k = −8→8 |
| 14473 measured reflections | l = −13→13 |
| 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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.152 | H-atom parameters constrained |
| S = 1.14 | w = 1/[σ2(Fo2) + (0.082P)2 + 1.0681P] where P = (Fo2 + 2Fc2)/3 |
| 1606 reflections | (Δ/σ)max = 0.003 |
| 113 parameters | Δρmax = 0.65 e Å−3 |
| 0 restraints | Δρmin = −0.43 e Å−3 |
| C6H11N3O2S | V = 882.4 (3) Å3 |
| Mr = 189.24 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.526 (2) Å | µ = 0.33 mm−1 |
| b = 6.881 (1) Å | T = 100 K |
| c = 11.577 (2) Å | 0.28 × 0.24 × 0.04 mm |
| β = 106.06 (3)° |
| Oxford Diffraction GEMINI R diffractometer | 1310 reflections with I > 2σ(I) |
| Absorption correction: analytical (Clark & Reid, 1995) | Rint = 0.038 |
| Tmin = 0.935, Tmax = 0.987 | θmax = 25.3° |
| 14473 measured reflections | Standard reflections: 0 |
| 1606 independent reflections |
| R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
| wR(F2) = 0.152 | Δρmax = 0.65 e Å−3 |
| S = 1.14 | Δρmin = −0.43 e Å−3 |
| 1606 reflections | Absolute structure: ? |
| 113 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2006) |
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 | ||
| S1 | 0.90922 (6) | 0.76365 (10) | 0.88325 (6) | 0.0210 (3) | |
| N1 | 0.6238 (2) | 0.8154 (4) | 0.6634 (2) | 0.0294 (6) | |
| N3 | 0.6663 (2) | 0.3452 (3) | 0.6091 (2) | 0.0226 (6) | |
| N2 | 0.7653 (2) | 0.2899 (4) | 0.7060 (2) | 0.0239 (6) | |
| H2A | 0.7844 | 0.1691 | 0.7171 | 0.029* | |
| C2 | 0.8065 (2) | 0.6173 (4) | 0.7816 (2) | 0.0221 (6) | |
| C1 | 0.7039 (3) | 0.7189 (4) | 0.7119 (2) | 0.0213 (6) | |
| C6 | 0.5527 (3) | 0.3072 (5) | 0.6390 (3) | 0.0280 (7) | |
| H6C | 0.4860 | 0.3464 | 0.5731 | 0.034* | |
| H6B | 0.5514 | 0.3794 | 0.7096 | 0.034* | |
| H6A | 0.5464 | 0.1709 | 0.6539 | 0.034* | |
| C3 | 0.8286 (3) | 0.4217 (4) | 0.7794 (2) | 0.0223 (6) | |
| H3A | 0.8966 | 0.3766 | 0.8369 | 0.027* | |
| C5 | 0.6735 (3) | 0.2423 (4) | 0.5005 (3) | 0.0256 (7) | |
| H5C | 0.6078 | 0.2823 | 0.4338 | 0.031* | |
| H5B | 0.6685 | 0.1048 | 0.5124 | 0.031* | |
| H5A | 0.7487 | 0.2724 | 0.4842 | 0.031* | |
| O1 | 1.02390 (17) | 0.6673 (3) | 0.91967 (17) | 0.0247 (5) | |
| O2 | 0.90420 (19) | 0.9546 (3) | 0.82968 (18) | 0.0287 (5) | |
| C4 | 0.8543 (3) | 0.7845 (4) | 1.0102 (3) | 0.0248 (7) | |
| H4C | 0.9053 | 0.8710 | 1.0673 | 0.030* | |
| H4B | 0.8542 | 0.6588 | 1.0462 | 0.030* | |
| H4A | 0.7736 | 0.8350 | 0.9864 | 0.030* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0198 (4) | 0.0233 (4) | 0.0185 (4) | −0.0014 (3) | 0.0031 (3) | 0.0009 (3) |
| N1 | 0.0256 (14) | 0.0259 (13) | 0.0308 (14) | 0.0016 (12) | −0.0021 (11) | −0.0010 (11) |
| N3 | 0.0220 (12) | 0.0246 (13) | 0.0186 (12) | 0.0045 (10) | 0.0011 (10) | −0.0013 (10) |
| N2 | 0.0258 (13) | 0.0223 (12) | 0.0215 (13) | 0.0062 (10) | 0.0029 (10) | 0.0018 (10) |
| C2 | 0.0199 (14) | 0.0256 (15) | 0.0186 (14) | 0.0013 (12) | 0.0020 (11) | 0.0018 (12) |
| C1 | 0.0206 (15) | 0.0246 (14) | 0.0175 (14) | −0.0047 (12) | 0.0030 (11) | −0.0033 (11) |
| C6 | 0.0265 (16) | 0.0295 (16) | 0.0277 (16) | −0.0008 (13) | 0.0071 (13) | 0.0000 (13) |
| C3 | 0.0212 (14) | 0.0273 (15) | 0.0177 (13) | 0.0003 (12) | 0.0041 (11) | 0.0014 (12) |
| C5 | 0.0255 (16) | 0.0286 (16) | 0.0204 (15) | 0.0016 (12) | 0.0026 (12) | −0.0047 (12) |
| O1 | 0.0213 (11) | 0.0276 (11) | 0.0234 (10) | 0.0002 (9) | 0.0030 (8) | 0.0022 (9) |
| O2 | 0.0302 (12) | 0.0242 (11) | 0.0275 (11) | −0.0044 (9) | 0.0011 (9) | 0.0041 (9) |
| C4 | 0.0241 (15) | 0.0287 (15) | 0.0201 (15) | −0.0011 (12) | 0.0036 (12) | −0.0052 (12) |
| S1—O1 | 1.434 (2) | C2—C1 | 1.418 (4) |
| S1—O2 | 1.447 (2) | C6—H6C | 0.9600 |
| S1—C2 | 1.740 (3) | C6—H6B | 0.9600 |
| S1—C4 | 1.759 (3) | C6—H6A | 0.9600 |
| N1—C1 | 1.150 (4) | C3—H3A | 0.9300 |
| N3—N2 | 1.413 (3) | C5—H5C | 0.9600 |
| N3—C5 | 1.465 (4) | C5—H5B | 0.9600 |
| N3—C6 | 1.468 (4) | C5—H5A | 0.9600 |
| N2—C3 | 1.317 (4) | C4—H4C | 0.9600 |
| N2—H2A | 0.8600 | C4—H4B | 0.9600 |
| C2—C3 | 1.371 (4) | C4—H4A | 0.9600 |
| O1—S1—O2 | 118.04 (13) | N3—C6—H6A | 109.5 |
| O1—S1—C2 | 109.30 (13) | H6C—C6—H6A | 109.5 |
| O2—S1—C2 | 107.24 (13) | H6B—C6—H6A | 109.5 |
| O1—S1—C4 | 107.89 (13) | N2—C3—C2 | 128.0 (3) |
| O2—S1—C4 | 107.64 (14) | N2—C3—H3A | 116.0 |
| C2—S1—C4 | 106.12 (14) | C2—C3—H3A | 116.0 |
| N2—N3—C5 | 109.0 (2) | N3—C5—H5C | 109.5 |
| N2—N3—C6 | 110.0 (2) | N3—C5—H5B | 109.5 |
| C5—N3—C6 | 112.5 (2) | H5C—C5—H5B | 109.5 |
| C3—N2—N3 | 120.5 (2) | N3—C5—H5A | 109.5 |
| C3—N2—H2A | 119.7 | H5C—C5—H5A | 109.5 |
| N3—N2—H2A | 119.7 | H5B—C5—H5A | 109.5 |
| C3—C2—C1 | 127.1 (3) | S1—C4—H4C | 109.5 |
| C3—C2—S1 | 119.0 (2) | S1—C4—H4B | 109.5 |
| C1—C2—S1 | 113.8 (2) | H4C—C4—H4B | 109.5 |
| N1—C1—C2 | 173.4 (3) | S1—C4—H4A | 109.5 |
| N3—C6—H6C | 109.5 | H4C—C4—H4A | 109.5 |
| N3—C6—H6B | 109.5 | H4B—C4—H4A | 109.5 |
| H6C—C6—H6B | 109.5 | ||
| C5—N3—N2—C3 | 134.3 (3) | O2—S1—C2—C1 | −32.2 (2) |
| C6—N3—N2—C3 | −101.9 (3) | C4—S1—C2—C1 | 82.6 (2) |
| O1—S1—C2—C3 | 21.2 (3) | N3—N2—C3—C2 | 5.4 (4) |
| O2—S1—C2—C3 | 150.3 (2) | C1—C2—C3—N2 | 6.4 (5) |
| C4—S1—C2—C3 | −94.9 (3) | S1—C2—C3—N2 | −176.5 (2) |
| O1—S1—C2—C1 | −161.3 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3A···O1 | 0.93 | 2.51 | 2.922 (4) | 107 |
| C5—H5C···N1i | 0.96 | 2.68 | 3.449 (5) | 138 |
| C6—H6A···N1ii | 0.96 | 2.60 | 3.475 (2) | 152 |
| C4—H4B···O1iii | 0.96 | 2.62 | 3.415 (4) | 141 |
| C3—H3A···O1iii | 0.93 | 2.73 | 3.482 (5) | 139 |
| C5—H5A···O1iv | 0.96 | 2.65 | 3.392 (3) | 135 |
| N2—H2A···O2ii | 0.86 | 2.19 | 2.944 (2) | 147 |
| C4—H4C···O2v | 0.96 | 2.50 | 3.399 (4) | 156 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+2, −y+1, −z+2; (iv) −x+2, y−1/2, −z+3/2; (v) −x+2, −y+2, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3A···O1 | 0.93 | 2.51 | 2.922 (4) | 107 |
| C5—H5C···N1i | 0.96 | 2.68 | 3.449 (5) | 138 |
| C6—H6A···N1ii | 0.96 | 2.60 | 3.475 (2) | 152 |
| C4—H4B···O1iii | 0.96 | 2.62 | 3.415 (4) | 141 |
| C3—H3A···O1iii | 0.93 | 2.73 | 3.482 (5) | 139 |
| C5—H5A···O1iv | 0.96 | 2.65 | 3.392 (3) | 135 |
| N2—H2A···O2ii | 0.86 | 2.19 | 2.944 (2) | 147 |
| C4—H4C···O2v | 0.96 | 2.50 | 3.399 (4) | 156 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+2, −y+1, −z+2; (iv) −x+2, y−1/2, −z+3/2; (v) −x+2, −y+2, −z+2. |
The authors thank the Grant Agency of the Slovak Republic, grant Nos. 1/2449/05, 1/1379/04 and APVT-20–007304, as well as the Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338.
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany
Chemla, D. & Zyss, J. (1987). Optical Properties of Organic Molecules and Crystals, Vol.1, pp. 23–187. New York: Academic Press.
Clark & Reid (1995). Please provide full reference.
Cook, A. G. (1969). Enamines: Syntheses, Structure and Reactions. New York: Marcel Dekker
Dyke, S. F. (1973). The Chemistry of Enamines. London: Cambridge University Press.
Nalwa, H. S., Watanabe, T. & Miyata, S. (1997). Nonlinear Optics of Organic Molecules and Polymers, pp. 87-329. Boca Ranton: CRC Press.
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
3-N,N-dimethylhydrazino-2-methylsulfonyl propenenitrile (Fig. 1) belongs to the so-called push-pull olefins. Push-pull alkenes are substituted ethylenes containing electron- donor groups (D) at one end and electron-acceptor groups (A) at the other end of the general formula D1D2C=CA1A2. These compounds very often contain alkoxy, amino, alkylamino, dialkylamino or (hetero)aryl groups as electron-donor groups and cyano, acetyl, alkylester, methylsulfonyl or NO2 groups as electron-acceptor groups. They are useful as starting reactants or intermediates for a lot of pharmaceutical, polymer and other syntheses (Cook, 1969, Dyke, 1973).
Due to the opposite character of the substituents, the olefinic C=C double bond order is reduced and accompanied by the increased bond orders of the bonds between the olefinic carbon atoms and their electron donor and electron acceptor groups, respectively. This leads to the substantial decrease of the rotational barrier about the C=C double bond and to the increase of an analogues barrier about the adjecent bonds. These changes are connected with the separation of the possitive and negative charges and electron delocalization within the π-electron system. Such compounds belong to the most developed structures in the search for new compounds with non-linear optics responses (Nalwa et al., 1997, Chemla & Zyss, 1987).