Methyl 2-cyano-2-(1,3-di­thian-2-yl­idene)acetate

Hamdouni, N.; Boudjada, A.; Meinnel, J.; Fiala, A.; Brahim Ladouani, H.; Lemallem, S.E.

doi:10.1107/S2414314617010185

organic compounds

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ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171018

https://doi.org/10.1107/S2414314617010185

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Methyl 2-cyano-2-(1,3-dithian-2-ylidene)acetate

Noudjoud Hamdouni,^a ^* Ali Boudjada,^a Jean Meinnel,^b Abdelali Fiala,^c Hayet Brahim Ladouani ^c and Salah Eddine Lemallem ^c

^aLaboratoire de Cristallographie, Département de Physique, Université Mentouri-Constantine, 25000 Constantine, Algeria, ^bUMR 6226 CNRS–Université Rennes 1 `Sciences Chimiques de Rennes', Equipe `Matière Condensée et Systèmes Electroactifs', Bâtiment 10C, Campus de Beaulieu, 263 Avenue du Général Leclerc, F-35042 Rennes, France, and ^cUnité de Recherche de Chimie de l'Environnement et Moléculaire, Structurale CHEMS, Université des frères Mentouri Constantine, Constantine, Algeria
^*Correspondence e-mail: n_hamdouni@yahoo.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 21 June 2017; accepted 8 July 2017; online 18 July 2017)

The title compound, C₈H₉NO₂S₂, contains a 1,3-dithiane ring which has a twist-boat conformation. In the crystal, there are no significant intermolecuar interactions present. The dihedral angle between the planes of the acetate group and the dithiane ring is 177.1 (2)°

Keywords: crystal structure; 1,3-dithiane; cyano; ketene dithioacetals.

CCDC reference: 1561034

Structure description

Ketene dithioacetals are useful intermediates in organic synthesis and have been used for the synthesis of heterocyclic compounds (Kolb, 1990 ; Ila et al., 2001 ). The synthesis of trifluoromethyl ketene dithioacetals plays an important role in the field of pharmaceuticals and agrochemicals (Gouault-Bironneau et al., 2012 ; Timoshenko & Portella, 2009 ). They have also been used to develop domino reactions owing to their ability to produce a wide range of substances of structural diversity and varied biological activities (Pan et al., 2013 ; Samai et al., 2012 ). The α-C ketene dithioacetals are reactive towards electrophiles (Okuyama, 1986 ; Okuyama, 1984 ). They act as a precursors for C—C bond formation at the α-C atom (Kouno et al., 1998 ; Minami et al., 1996 ). They have also been used for chlorination reactions to generated vinyl halides from α-acetyl ketene dithioacetals; these dithioacetals are further transformed into the corresponding α-ethynyl ketene dithioacetals (Liu et al., 2003 ; Dong et al., 2005 ). In the present study, we report the synthesis and crystal structure of the new title 1,3-dithian-2-ylidene derivative, which has a dipolar moment of the order of 6.8 Debye.

The molecular structure of the title compound is shown in Fig. 1. The 1,3-dithiane ring has a twist-boat conformation [puckering parameters: amplitude (Q) = 0.632 (3) Å, θ = 106.5 (3)° and φ = 114.3 (3)°]. In this ring, the two C—S bond lengths adjacent to the C4=C2 bond [1.381 (3) Å] are C4—S1 = 1.733 (2) Å and C4—S3 = 1.736 (2) Å. The geometric parameters and the deformation of the 1,3-dithiane ring are similar to those found for related structures. For example, in methyl 2-(diphenylmethyleneamino)-2-(1,3-dithian-2-ylidene)acetate (Dolling et al., 1993 ) or (3Z,6E)-dimethyl 3,7-dichloro-2,8-bis(1,3-dithian-2-ylidene)-5-(4-nitrophenyl)nona-3,6-diene-1,9-dioate (Zhao et al., 2007 ). In these two compounds, the C—S bond lengths vary from 1.736 to 1.758 Å and the C=C bond length varies from 1.349 to 1.366 Å. In both compounds, the 1,3-dithiane rings also have twist-boat conformations.

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level.

In the crystal of the title compound, there are no significant directional intermolecuar interactions present (Fig. 2).

Figure 2
A view along the a axis of the crystal packing of the title compound.

Synthesis and crystallization

In a three-necked round-bottomed flask swept by a nitrogen current and equipped with a dropping funnel containing 1,3-dibromopropane, a suspension of K₂CO₃ (42 g, 0.3 mol) mixed with the corresponding active methylene compound, NCCH₂COOCH₃ (0.15 mol) in DMF (50 ml), was stirred with a magnetic stirrer. Carbon disulfide (9 ml, 0.15 mol) was added all at once, at room temperature. Stirring was continued for 10 min, after which 1,3-dibromopropane (0.12 mol) was added dropwise over a period of 20 min. After further stirring for 7 h at room temperature, ice-cold water (500 ml) was added to the reaction mixture. The precipitate that formed was filtered off, dried and then dissolved in ethanol, giving pale-yellow needle-like crystals on slow evaporation of the solvent.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₈H₉NO₂S₂
M_r	215.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.4927 (6), 15.2501 (19), 8.5522 (9)
β (°)	94.923 (9)
V (Å³)	973.61 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.51
Crystal size (mm)	0.28 × 0.17 × 0.03

Data collection
Diffractometer	Agilent Technologies Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.842, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6282, 3076, 1740
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.754

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.155, 1.00
No. of reflections	3076
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.40
Computer programs: CrysAlis PRO (Agilent, 2013), SIR92 (Altomare et al., 1994 ), SHELXL97 (Sheldrick, 2008 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ), WinGX (Farrugia, 2012 ).

Structural data

CCDC reference: 1561034

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617010185/su5381sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010185/su5381Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010185/su5381Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).

Methyl 2-cyano-2-(1,3-dithian-2-ylidene)acetate top

Crystal data top

C₈H₉NO₂S₂	F(000) = 448
M_r = 215.28	D_x = 1.469 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 1541 reflections
a = 7.4927 (6) Å	θ = 3.7–28.9°
b = 15.2501 (19) Å	µ = 0.51 mm⁻¹
c = 8.5522 (9) Å	T = 293 K
β = 94.923 (9)°	Needle, pale yellow
V = 973.61 (18) Å³	0.28 × 0.17 × 0.03 mm
Z = 4

Data collection top

Agilent Technologies Xcalibur Eos diffractometer	3076 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1740 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 8.02 pixels mm^-1	θ_max = 32.4°, θ_min = 3.0°
ω scans	h = −6→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −10→22
T_min = 0.842, T_max = 1.000	l = −12→10
6282 measured reflections

Refinement top

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0578P)²] where P = (F_o² + 2F_c²)/3
3076 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³
0 constraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.48769 (9)	0.16638 (5)	0.33331 (8)	0.0486 (2)
S3	0.82543 (9)	0.07137 (6)	0.46302 (9)	0.0594 (3)
O2	0.3383 (2)	0.10646 (12)	0.8114 (2)	0.0458 (4)
O1	0.2734 (2)	0.17772 (14)	0.5839 (2)	0.0537 (5)
C2	0.5515 (3)	0.10466 (16)	0.6310 (3)	0.0360 (5)
N1	0.7540 (3)	0.0327 (2)	0.8531 (3)	0.0665 (8)
C1	0.3739 (3)	0.13390 (17)	0.6686 (3)	0.0386 (6)
C4	0.6154 (3)	0.11524 (15)	0.4855 (3)	0.0357 (5)
C8	0.1685 (3)	0.1339 (2)	0.8649 (4)	0.0567 (8)
H8A	0.1569	0.1106	0.9678	0.085*
H8B	0.0723	0.1126	0.7937	0.085*
H8C	0.164	0.1968	0.8687	0.085*
C3	0.6647 (3)	0.06433 (18)	0.7544 (3)	0.0427 (6)
C7	0.6114 (4)	0.1453 (2)	0.1655 (3)	0.0561 (8)
H7A	0.6058	0.083	0.1425	0.067*
H7B	0.5534	0.1759	0.0755	0.067*
C6	0.8063 (4)	0.1728 (2)	0.1858 (4)	0.0711 (10)
H6A	0.8571	0.1671	0.0857	0.085*
H6B	0.8124	0.2343	0.2152	0.085*
C5	0.9137 (4)	0.1229 (3)	0.3017 (5)	0.0970 (15)
H5A	1.0079	0.1618	0.3448	0.116*
H5B	0.9718	0.0774	0.2453	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0506 (4)	0.0592 (4)	0.0353 (4)	0.0148 (3)	−0.0001 (3)	0.0032 (3)
S3	0.0458 (4)	0.0808 (6)	0.0529 (5)	0.0241 (4)	0.0109 (3)	0.0159 (4)
O2	0.0390 (9)	0.0551 (11)	0.0442 (10)	0.0026 (9)	0.0084 (8)	0.0065 (10)
O1	0.0442 (10)	0.0666 (13)	0.0500 (11)	0.0146 (9)	0.0036 (8)	0.0112 (11)
C2	0.0326 (11)	0.0367 (12)	0.0385 (13)	−0.0006 (10)	0.0013 (10)	0.0006 (11)
N1	0.0526 (14)	0.093 (2)	0.0536 (15)	0.0132 (14)	0.0026 (12)	0.0237 (16)
C1	0.0373 (12)	0.0397 (13)	0.0383 (13)	−0.0041 (11)	0.0010 (10)	−0.0008 (12)
C4	0.0370 (11)	0.0309 (11)	0.0382 (13)	0.0003 (10)	−0.0035 (10)	−0.0015 (11)
C8	0.0416 (14)	0.0693 (19)	0.0615 (18)	−0.0008 (15)	0.0172 (13)	0.0024 (18)
C3	0.0368 (12)	0.0495 (15)	0.0420 (15)	0.0028 (12)	0.0041 (11)	0.0057 (13)
C7	0.0578 (17)	0.076 (2)	0.0345 (14)	0.0023 (16)	0.0042 (12)	−0.0018 (16)
C6	0.0625 (19)	0.087 (2)	0.065 (2)	−0.0043 (19)	0.0135 (17)	0.020 (2)
C5	0.0493 (17)	0.153 (4)	0.091 (3)	0.012 (2)	0.0211 (18)	0.062 (3)

Geometric parameters (Å, º) top

S1—C4	1.733 (2)	C8—H8A	0.96
S1—C7	1.803 (3)	C8—H8B	0.96
S3—C4	1.736 (2)	C8—H8C	0.96
S3—C5	1.765 (3)	C7—C6	1.515 (4)
O2—C1	1.339 (3)	C7—H7A	0.97
O2—C8	1.450 (3)	C7—H7B	0.97
O1—C1	1.202 (3)	C6—C5	1.440 (4)
C2—C4	1.381 (3)	C6—H6A	0.97
C2—C3	1.435 (3)	C6—H6B	0.97
C2—C1	1.465 (3)	C5—H5A	0.97
N1—C3	1.138 (3)	C5—H5B	0.97

C4—S1—C7	103.25 (13)	C6—C7—S1	114.6 (2)
C4—S3—C5	108.61 (15)	C6—C7—H7A	108.6
C1—O2—C8	116.5 (2)	S1—C7—H7A	108.6
C4—C2—C3	119.0 (2)	C6—C7—H7B	108.6
C4—C2—C1	123.6 (2)	S1—C7—H7B	108.6
C3—C2—C1	117.4 (2)	H7A—C7—H7B	107.6
O1—C1—O2	124.1 (2)	C5—C6—C7	114.1 (3)
O1—C1—C2	124.8 (2)	C5—C6—H6A	108.7
O2—C1—C2	111.1 (2)	C7—C6—H6A	108.7
C2—C4—S1	121.18 (18)	C5—C6—H6B	108.7
C2—C4—S3	116.27 (18)	C7—C6—H6B	108.7
S1—C4—S3	122.51 (15)	H6A—C6—H6B	107.6
O2—C8—H8A	109.5	C6—C5—S3	123.3 (2)
O2—C8—H8B	109.5	C6—C5—H5A	106.5
H8A—C8—H8B	109.5	S3—C5—H5A	106.5
O2—C8—H8C	109.5	C6—C5—H5B	106.5
H8A—C8—H8C	109.5	S3—C5—H5B	106.5
H8B—C8—H8C	109.5	H5A—C5—H5B	106.5
N1—C3—C2	179.5 (3)

C8—O2—C1—O004	−1.3 (4)	C1—C2—C4—S3	−177.10 (18)
C8—O2—C1—C2	177.8 (2)	C7—S1—C4—C2	−169.9 (2)
C4—C2—C1—O1	−8.2 (4)	C7—S1—C4—S3	7.9 (2)
C3—C2—C1—O1	170.7 (3)	C5—S3—C4—C2	−159.8 (2)
C4—C2—C1—O2	172.7 (2)	C5—S3—C4—S1	22.4 (3)
C3—C2—C1—O2	−8.4 (3)	C4—S1—C7—C6	−53.9 (3)
C3—C2—C4—S1	−178.08 (18)	S1—C7—C6—C5	66.7 (4)
C1—C2—C4—S1	0.8 (4)	C7—C6—C5—S3	−26.9 (6)
C3—C2—C4—S3	4.0 (3)	C4—S3—C5—C6	−16.1 (5)

Acknowledgements

We thank Mr F. Saidi, Engineer at the Laboratory of Crystallography, University Constantine 1, for assistance in collecting the X-ray data on the Xcalibur diffractometer.

Funding information

Funding for this research was provided by: Laboratoire de Cristallographie, Departement de Physique, Universite Constantine 1, Algeria.

References

Agilent (2013). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Dolling, W., Frost, K., Heinemann, F. & Hartung, H. (1993). Z. Naturforsch. Teil B, 48, 493–504. Google Scholar
Dong, D., Liu, Y., Zhao, Y., Qi, Y., Wang, Z. & Liu, Q. (2005). Synthesis, pp. 85–91. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gouault-Bironneau, S., Timoshenko, V. M., Grellepois, F. & Portella, C. (2012). J. Fluorine Chem. 134, 164–171. CAS Google Scholar
Ila, H., Junjappa, H. & Barun, O. (2001). J. Organomet. Chem. 624, 34–40. CrossRef CAS Google Scholar
Kolb, M. (1990). Synthesis, pp. 171–190. CrossRef Google Scholar
Kouno, R., Okauchi, T., Nakamura, M., Ichikawa, J. & Minami, T. (1998). J. Org. Chem. 63, 6239–6246. CrossRef CAS Google Scholar
Liu, Q., Che, G., Yu, H., Liu, Y., Zhang, J., Zhang, Q. & Dong, D. (2003). J. Org. Chem. 68, 9148–9150. CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Minami, T., Okauchi, T., Matsuki, H., Nakamura, M., Ichikawa, J. & Ishida, M. (1996). J. Org. Chem. 61, 8132–8140. CSD CrossRef CAS Google Scholar
Okuyama, T. (1984). J. Am. Chem. Soc. 106, 7134–7139. CrossRef CAS Google Scholar
Okuyama, T. (1986). Acc. Chem. Res. 19, 370–376. CrossRef CAS Google Scholar
Pan, L., Bi, X. & Liu, Q. (2013). Chem. Soc. Rev. 42, 1251–1286. CrossRef CAS Google Scholar
Samai, S., Nandi, G. C. & Singh, M. S. (2012). Tetrahedron, 68, 1247–1252. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Timoshenko, V. M. & Portella, C. (2009). J. Fluorine Chem. 130, 586–590. CrossRef CAS Google Scholar
Zhao, Y.-L., Chen, L., Liu, Q. & Li, D.-W. (2007). Synlett, pp. 37–42. CSD CrossRef Google Scholar