Acta Cryst. (2008). E64, o592 [ doi:10.1107/S1600536808004054 ]
The title compound, C16H14N2OS2, is an example of a push-pull butadiene in which the electron-releasing and electron-withdrawing attachments on either end of the butadiene chain enhance the conjugation in the system. The molecules are linked by intermolecular C-H
N interactions.
2-[3,3-Bis(methyl sulfanyl)-2-(4-methyl benzoyl)-2- propylidene] malononitrile was obtained by the Knoevenagel condensation reaction of 3,3-bis (methyl sulfanyl)-2-(4-methyl benzoyl)-acrylaldehyde (1.33 g., 5 mmol) with malononitrile (500 mg., 7.5 mmol) (Anabha et al., 2006). Single crystals suitable for X-ray diffraction studies were grown by slow evaporation using solutions containing chloroform and hexane in the ratio 1:2. Pale yellow coloured crystals were obtained after two days.
The position of all H atoms were geometrically fixed and treated with riding atoms, with C—H distances of 0.93 or 0.96 A. Their isotropic displacement parameters were defined as Uiso= 1.5Ueq of the adjacent atom for the methyl H atoms and Uiso = 1.2Ueq for all other atoms. The 1210 Friedel opposites were not merged, and the choice of absolute structure was determined by the Flack parameter (Flack, 1983) of 0.11 (12). For the inverted structure the Flack parameter refined to 0.84 (12).
Data collection: XPRESS (Mac Science, 2002); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).
![[Figure 1]](./pv2055fig1thm.gif)
| Fig. 1. An ORTEPII (Johnson, 1976) view of (I) showing the atom-labeling scheme; displacement ellipsoids are drawn at 50% probability level. |
![[Figure 2]](./pv2055fig2thm.gif)
| Fig. 2. A view of the unit cell packing of (I) showing intermolecular interactions in the ac plane. |
| C16H14N2OS2 | F000 = 656 |
| Mr = 314.41 | Dx = 1.257 Mg m−3 |
| Monoclinic, C2 | Mo Kα radiation λ = 0.71070 Å |
| Hall symbol: C 2y | Cell parameters from 4224 reflections |
| a = 16.6050 (13) Å | θ = 3.5–25.5º |
| b = 10.760 (2) Å | µ = 0.32 mm−1 |
| c = 9.905 (2) Å | T = 295 (2) K |
| β = 110.09 (2)º | Block, pale yellow |
| V = 1662.0 (5) Å3 | 0.25 × 0.25 × 0.20 mm |
| Z = 4 |
| MacScience DIPLabo 32001 diffractometer | 2717 independent reflections |
| Radiation source: fine-focus sealed tube | 2583 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.035 |
| Detector resolution: 10.0 pixels mm-1 | θmax = 25.5º |
| T = 295(2) K | θmin = 3.5º |
| ω scans | h = −20→20 |
| Absorption correction: none | k = −11→11 |
| 4433 measured reflections | l = −11→11 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.1066P)2 + 0.5386P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.156 | (Δ/σ)max < 0.001 |
| S = 1.11 | Δρmax = 0.30 e Å−3 |
| 2717 reflections | Δρmin = −0.28 e Å−3 |
| 194 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 1 restraint | Extinction coefficient: 0.015 (3) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
| Secondary atom site location: difference Fourier map | Flack parameter: 0.11 (12) |
| C16H14N2OS2 | V = 1662.0 (5) Å3 |
| Mr = 314.41 | Z = 4 |
| Monoclinic, C2 | Mo Kα |
| a = 16.6050 (13) Å | µ = 0.32 mm−1 |
| b = 10.760 (2) Å | T = 295 (2) K |
| c = 9.905 (2) Å | 0.25 × 0.25 × 0.20 mm |
| β = 110.09 (2)º |
| MacScience DIPLabo 32001 diffractometer | 2717 independent reflections |
| Absorption correction: none | 2583 reflections with I > 2σ(I) |
| 4433 measured reflections | Rint = 0.035 |
| R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
| wR(F2) = 0.156 | Δρmax = 0.30 e Å−3 |
| S = 1.11 | Δρmin = −0.28 e Å−3 |
| 2717 reflections | Absolute structure: Flack (1983) |
| 194 parameters | Flack parameter: 0.11 (12) |
| 1 restraint |
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 | 0.33194 (6) | 0.02065 (9) | 0.76965 (9) | 0.0543 (3) | |
| S2 | 0.16024 (7) | −0.08895 (12) | 0.75086 (11) | 0.0689 (4) | |
| C5 | 0.1681 (2) | −0.0204 (3) | 1.1171 (4) | 0.0458 (8) | |
| C13 | 0.3562 (2) | 0.0395 (4) | 1.0845 (3) | 0.0471 (7) | |
| H13 | 0.3801 | 0.0925 | 1.0344 | 0.057* | |
| C9 | 0.2833 (2) | −0.0289 (3) | 0.9991 (3) | 0.0430 (7) | |
| C8 | 0.2276 (2) | −0.0956 (4) | 1.0693 (3) | 0.0471 (8) | |
| C14 | 0.3959 (2) | 0.0379 (4) | 1.2301 (3) | 0.0508 (8) | |
| C10 | 0.2604 (2) | −0.0317 (3) | 0.8523 (4) | 0.0468 (7) | |
| O1 | 0.2346 (2) | −0.2092 (3) | 1.0871 (3) | 0.0680 (8) | |
| C4 | 0.1194 (3) | −0.0773 (4) | 1.1895 (5) | 0.0622 (10) | |
| H4 | 0.1228 | −0.1628 | 1.2041 | 0.075* | |
| C6 | 0.1602 (3) | 0.1060 (4) | 1.0927 (5) | 0.0592 (10) | |
| H6 | 0.1916 | 0.1447 | 1.0428 | 0.071* | |
| C16 | 0.4673 (2) | 0.1193 (4) | 1.2927 (4) | 0.0553 (9) | |
| C15 | 0.3732 (3) | −0.0373 (4) | 1.3306 (4) | 0.0588 (10) | |
| C3 | 0.0660 (3) | −0.0065 (5) | 1.2394 (5) | 0.0716 (12) | |
| H3 | 0.0341 | −0.0452 | 1.2882 | 0.086* | |
| C2 | 0.0592 (3) | 0.1204 (6) | 1.2184 (5) | 0.0729 (13) | |
| N1 | 0.3560 (3) | −0.0944 (5) | 1.4132 (4) | 0.0905 (14) | |
| N2 | 0.5237 (3) | 0.1858 (5) | 1.3400 (5) | 0.0795 (12) | |
| C11 | 0.2658 (3) | 0.1102 (5) | 0.6206 (5) | 0.0724 (12) | |
| H11A | 0.2391 | 0.0562 | 0.5405 | 0.109* | |
| H11B | 0.3003 | 0.1705 | 0.5942 | 0.109* | |
| H11C | 0.2223 | 0.1521 | 0.6470 | 0.109* | |
| C12 | 0.1815 (4) | −0.1799 (6) | 0.6150 (5) | 0.0828 (15) | |
| H12A | 0.1970 | −0.1258 | 0.5508 | 0.124* | |
| H12B | 0.1311 | −0.2261 | 0.5620 | 0.124* | |
| H12C | 0.2278 | −0.2364 | 0.6595 | 0.124* | |
| C7 | 0.1061 (3) | 0.1753 (5) | 1.1419 (6) | 0.0738 (13) | |
| H7 | 0.1008 | 0.2602 | 1.1236 | 0.089* | |
| C1 | 0.0013 (5) | 0.2004 (8) | 1.2746 (9) | 0.105 (2) | |
| H1A | −0.0539 | 0.1616 | 1.2510 | 0.157* | |
| H1B | −0.0052 | 0.2812 | 1.2311 | 0.157* | |
| H1C | 0.0267 | 0.2085 | 1.3771 | 0.157* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0555 (5) | 0.0664 (6) | 0.0453 (5) | −0.0047 (4) | 0.0227 (4) | −0.0002 (4) |
| S2 | 0.0532 (5) | 0.0949 (9) | 0.0551 (5) | −0.0188 (5) | 0.0141 (4) | −0.0181 (5) |
| C5 | 0.0452 (17) | 0.046 (2) | 0.0481 (17) | −0.0059 (12) | 0.0189 (14) | −0.0031 (13) |
| C13 | 0.0479 (16) | 0.054 (2) | 0.0413 (16) | −0.0045 (14) | 0.0172 (13) | −0.0025 (13) |
| C9 | 0.0473 (17) | 0.0434 (18) | 0.0393 (15) | −0.0042 (12) | 0.0162 (13) | −0.0027 (11) |
| C8 | 0.0526 (18) | 0.049 (2) | 0.0410 (16) | −0.0073 (14) | 0.0176 (14) | −0.0026 (13) |
| C14 | 0.0494 (17) | 0.063 (2) | 0.0405 (15) | 0.0010 (16) | 0.0163 (13) | −0.0063 (15) |
| C10 | 0.0491 (18) | 0.0487 (19) | 0.0456 (17) | −0.0060 (13) | 0.0202 (14) | −0.0053 (13) |
| O1 | 0.090 (2) | 0.0475 (19) | 0.081 (2) | −0.0027 (14) | 0.0481 (17) | −0.0039 (13) |
| C4 | 0.062 (2) | 0.062 (3) | 0.072 (2) | 0.0035 (18) | 0.036 (2) | 0.0115 (19) |
| C6 | 0.053 (2) | 0.052 (3) | 0.077 (3) | −0.0072 (15) | 0.0284 (19) | −0.0051 (17) |
| C16 | 0.0472 (19) | 0.071 (2) | 0.0447 (18) | −0.0072 (17) | 0.0118 (15) | −0.0098 (16) |
| C15 | 0.062 (2) | 0.065 (3) | 0.0454 (18) | −0.0017 (17) | 0.0130 (16) | −0.0001 (17) |
| C3 | 0.069 (3) | 0.076 (4) | 0.085 (3) | 0.0031 (19) | 0.047 (2) | 0.010 (2) |
| C2 | 0.052 (2) | 0.090 (4) | 0.079 (3) | −0.002 (2) | 0.026 (2) | −0.024 (2) |
| N1 | 0.104 (3) | 0.112 (4) | 0.052 (2) | −0.021 (3) | 0.023 (2) | 0.015 (2) |
| N2 | 0.062 (2) | 0.105 (4) | 0.065 (2) | −0.020 (2) | 0.0144 (19) | −0.016 (2) |
| C11 | 0.083 (3) | 0.077 (3) | 0.056 (2) | −0.003 (2) | 0.024 (2) | 0.016 (2) |
| C12 | 0.089 (3) | 0.096 (4) | 0.060 (3) | −0.033 (3) | 0.022 (2) | −0.026 (2) |
| C7 | 0.071 (3) | 0.052 (3) | 0.107 (4) | −0.0002 (18) | 0.041 (3) | −0.010 (2) |
| C1 | 0.090 (4) | 0.104 (5) | 0.140 (6) | −0.002 (3) | 0.065 (4) | −0.036 (4) |
| S1—C10 | 1.751 (3) | C6—H6 | 0.9300 |
| S1—C11 | 1.790 (5) | C16—N2 | 1.142 (6) |
| S2—C10 | 1.734 (3) | C15—N1 | 1.135 (6) |
| S2—C12 | 1.795 (5) | C3—C2 | 1.381 (8) |
| C5—C6 | 1.379 (6) | C3—H3 | 0.9300 |
| C5—C4 | 1.393 (5) | C2—C7 | 1.390 (7) |
| C5—C8 | 1.475 (5) | C2—C1 | 1.531 (7) |
| C13—C14 | 1.364 (5) | C11—H11A | 0.9600 |
| C13—C9 | 1.421 (5) | C11—H11B | 0.9600 |
| C13—H13 | 0.9300 | C11—H11C | 0.9600 |
| C9—C10 | 1.372 (5) | C12—H12A | 0.9600 |
| C9—C8 | 1.515 (4) | C12—H12B | 0.9600 |
| C8—O1 | 1.235 (5) | C12—H12C | 0.9600 |
| C14—C15 | 1.430 (6) | C7—H7 | 0.9300 |
| C14—C16 | 1.433 (5) | C1—H1A | 0.9600 |
| C4—C3 | 1.383 (6) | C1—H1B | 0.9600 |
| C4—H4 | 0.9300 | C1—H1C | 0.9600 |
| C6—C7 | 1.380 (6) | ||
| C10—S1—C11 | 103.7 (2) | C2—C3—C4 | 121.4 (4) |
| C10—S2—C12 | 103.4 (2) | C2—C3—H3 | 119.3 |
| C6—C5—C4 | 119.2 (4) | C4—C3—H3 | 119.3 |
| C6—C5—C8 | 121.2 (3) | C3—C2—C7 | 118.0 (4) |
| C4—C5—C8 | 119.6 (3) | C3—C2—C1 | 122.0 (5) |
| C14—C13—C9 | 128.7 (3) | C7—C2—C1 | 119.9 (6) |
| C14—C13—H13 | 115.6 | S1—C11—H11A | 109.5 |
| C9—C13—H13 | 115.6 | S1—C11—H11B | 109.5 |
| C10—C9—C13 | 120.8 (3) | H11A—C11—H11B | 109.5 |
| C10—C9—C8 | 119.1 (3) | S1—C11—H11C | 109.5 |
| C13—C9—C8 | 120.1 (3) | H11A—C11—H11C | 109.5 |
| O1—C8—C5 | 122.6 (3) | H11B—C11—H11C | 109.5 |
| O1—C8—C9 | 119.4 (3) | S2—C12—H12A | 109.5 |
| C5—C8—C9 | 118.0 (3) | S2—C12—H12B | 109.5 |
| C13—C14—C15 | 126.6 (3) | H12A—C12—H12B | 109.5 |
| C13—C14—C16 | 118.5 (3) | S2—C12—H12C | 109.5 |
| C15—C14—C16 | 115.0 (3) | H12A—C12—H12C | 109.5 |
| C9—C10—S2 | 118.9 (3) | H12B—C12—H12C | 109.5 |
| C9—C10—S1 | 120.2 (3) | C6—C7—C2 | 121.2 (5) |
| S2—C10—S1 | 120.88 (19) | C6—C7—H7 | 119.4 |
| C3—C4—C5 | 119.9 (4) | C2—C7—H7 | 119.4 |
| C3—C4—H4 | 120.1 | C2—C1—H1A | 109.5 |
| C5—C4—H4 | 120.1 | C2—C1—H1B | 109.5 |
| C5—C6—C7 | 120.3 (4) | H1A—C1—H1B | 109.5 |
| C5—C6—H6 | 119.9 | C2—C1—H1C | 109.5 |
| C7—C6—H6 | 119.9 | H1A—C1—H1C | 109.5 |
| N2—C16—C14 | 178.5 (5) | H1B—C1—H1C | 109.5 |
| N1—C15—C14 | 178.0 (5) | ||
| C14—C13—C9—C10 | −169.0 (4) | C8—C9—C10—S1 | −169.0 (3) |
| C14—C13—C9—C8 | 13.6 (6) | C12—S2—C10—C9 | −138.8 (3) |
| C6—C5—C8—O1 | −178.5 (4) | C12—S2—C10—S1 | 40.6 (3) |
| C4—C5—C8—O1 | 2.1 (6) | C11—S1—C10—C9 | −136.9 (3) |
| C6—C5—C8—C9 | 3.1 (5) | C11—S1—C10—S2 | 43.7 (3) |
| C4—C5—C8—C9 | −176.3 (3) | C6—C5—C4—C3 | −1.9 (6) |
| C10—C9—C8—O1 | 80.2 (5) | C8—C5—C4—C3 | 177.5 (4) |
| C13—C9—C8—O1 | −102.4 (4) | C4—C5—C6—C7 | 1.3 (7) |
| C10—C9—C8—C5 | −101.3 (4) | C8—C5—C6—C7 | −178.1 (4) |
| C13—C9—C8—C5 | 76.1 (4) | C5—C4—C3—C2 | 0.5 (7) |
| C9—C13—C14—C15 | 1.7 (6) | C4—C3—C2—C7 | 1.6 (8) |
| C9—C13—C14—C16 | −177.8 (4) | C4—C3—C2—C1 | −179.2 (5) |
| C13—C9—C10—S2 | −167.0 (3) | C5—C6—C7—C2 | 0.9 (8) |
| C8—C9—C10—S2 | 10.4 (5) | C3—C2—C7—C6 | −2.3 (8) |
| C13—C9—C10—S1 | 13.6 (5) | C1—C2—C7—C6 | 178.5 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C12—H12B···N2i | 0.96 | 2.49 | 3.3871 | 155 |
| Symmetry codes: (i) x−1/2, y−1/2, z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C12—H12B···N2i | 0.96 | 2.49 | 3.3871 | 155 |
| Symmetry codes: (i) x−1/2, y−1/2, z−1. |
The authors acknowledge the National Single Crystal Diffractometer Facility, Department of Studies in Physics, University of Mysore, Manasagangothri for help with the data collection. One of the authors (JN) is grateful to UGC, New Delhi, Government of India, for providing a teaching fellowship.
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Due to the presence of electron releasing alkyl sulfanyl groups and electron withdrawing nitrile groups on the terminal carbon atoms of butadiene moiety, these molecules are considered as push pull butadienes. The push pull substitution alters the polyene state of the unsubstituted butadiene with balanced pi-charge distribution to a polymethine structure with alternating charge densities at the carbon atoms (Dahne, 1978). The title compound, (I), was synthesized and its crystal structure determination was carried out in order to elucidate the molecular conformation to understand the influence of aroyl groups on the stereochemistry of the butadiene molecule in continuation of research in the synthesis of pyridine derivatives (Anabha & Asokan, 2006). A perspective view of (I) is shown in Fig. 1. The crystal structure of (I) shows that the double bonds in the aroyl substituted butadiene are arranged in a transoid manner. Bond lengths C9—C10 and C13—C14 indicate their double bond character while C8—C9 is a single bond. Moreover, the double bonds C9—C10 and C13—C14 and shortening of C10—S2 bond length shows the electronic effects on the push pull system. Crystal structures of other butadiene compounds reported also show similar geometric parameters (Dastidar et al., 1993; Michalik et al., 2002; Freier et al., 1999; Homrighausen & Krause Bauer, 2004). The hydrogen-bond interactions of the type C—H···N stabilize the three dimensional structure along the ac plane (Fig. 2).