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Acta Cryst. (2008). E64, o970    [ doi:10.1107/S1600536808012506 ]

Methyl 3-[(E)-furfurylidene]dithiocarbazate

S. Shan, S.-H. Wang, Y.-L. Xu, P.-J. Xie and Y.-L. Tian

Abstract top

The molecule of the title Schiff base compound, C7H8N2OS2, prepared by the reaction of methyl dithiocarbazate and furfural in an ethanol solution under reflux, adopts an E configuration; the dithiocarbazate and furan units are located on opposite sides of the C=N double bond. The planar dithiocarbazate group is twisted slightly with respect to the furan ring, making a dihedral angle of 5.2 (1)°. Adjacent molecules are linked by N-H...S hydrogen bonding to form a supramolecular dimer across an inversion center.

Comment top

Since some hydrazone derivatives have shown the potential bioactivity as DNA-damaging or mutagenic agents (Okabe et al., 1993), a lots of new hydrazone compounds has been synthesized in our laboratory (Shan et al., 2002, 2003). As part of the ongoing investigation on hydrazone, we present here the crystal structure of the title compound.

The molecular structure is shown in Fig. 1. The N2═C3 bond distance of 1.284 (2) Å clearly indicates the double bond character for the Schiff base compound. The molecule adopts an E configuration, the carbazate and furan moieties located on the opposite positions of the N2═C3 bond; similar to that found in a related structure (Chen et al., 2007). The dithiocarbazate moiety is well co-planar, the maximum atomic deviation being 0.037 (1) Å (S2), and the dithiocarbazate mean plane is slightly twisted with respect to the furan plane by a smaller dihedral angle of 5.2 (1)°. This shows the whole molecule is nearly co-planar.

Inter-molecular N—H···S hydrogen bonding links adjacent molecules to form the centro-symmetric supra-molecular dimmer (Fig. 1 and Table 1).

Related literature top

For general background, see: Okabe et al. (1993); Shan et al. (2002, 2003). For a related structure, see: Chen et al. (2007). For the synthesis, see: Hu et al. (2001).

Experimental top

Methyl dithiocarbazate was synthesized in the manner reported previously (Hu et al., 2001). Methyl dithiocarbazate (1.24 g, 10 mmol) and furfural (0.96 g, 10 mmol) were dissolved in ethanol (10 ml) and refluxed for 4 h. Yellow crystalline product appeared after cooling to room temperature. They were separated and washed with cold water. Single crystals of the title compound were obtained by recrystallization from an ethanol solution.

Refinement top

Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angle was refined to fit electron density, Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions with C—H = 0.93 and N—H = 0.86 Å, and refined in the riding mode, Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 40% probability displacement ellipsoids (arbitrary spheres for H atoms) [symmetry code: (i) -x, 1 - y, 1 - z].
Methyl 3-[(E)-furfurylidene]dithiocarbazate top
Crystal data top
C7H8N2OS2Z = 2
Mr = 200.27F000 = 208
Triclinic, P1Dx = 1.448 Mg m−3
Hall symbol: -P 1Melting point = 414–416 K
a = 4.0866 (8) ÅMo Kα radiation
λ = 0.71073 Å
b = 8.8698 (12) ÅCell parameters from 2276 reflections
c = 12.8453 (15) Åθ = 2.0–25.0º
α = 93.970 (14)ºµ = 0.53 mm−1
β = 91.856 (12)ºT = 294 (2) K
γ = 98.293 (12)ºPrism, yellow
V = 459.21 (12) Å30.34 × 0.28 × 0.20 mm
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		1608 independent reflections
Radiation source: fine-focus sealed tube1349 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
Detector resolution: 10.0 pixels mm-1θmax = 25.2º
T = 294(2) Kθmin = 1.6º
ω scansh = −4→4
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −10→10
Tmin = 0.850, Tmax = 0.950l = −15→14
4733 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.096  w = 1/[σ2(Fo2) + (0.0598P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max = 0.001
1608 reflectionsΔρmax = 0.19 e Å−3
110 parametersΔρmin = −0.28 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C7H8N2OS2γ = 98.293 (12)º
Mr = 200.27V = 459.21 (12) Å3
Triclinic, P1Z = 2
a = 4.0866 (8) ÅMo Kα
b = 8.8698 (12) ŵ = 0.53 mm−1
c = 12.8453 (15) ÅT = 294 (2) K
α = 93.970 (14)º0.34 × 0.28 × 0.20 mm
β = 91.856 (12)º
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		1608 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1349 reflections with I > 2σ(I)
Tmin = 0.850, Tmax = 0.950Rint = 0.030
4733 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031110 parameters
wR(F2) = 0.096H-atom parameters constrained
S = 1.09Δρmax = 0.19 e Å−3
1608 reflectionsΔρmin = −0.28 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.20815 (13)0.27619 (5)0.50863 (4)0.0516 (2)
S20.38692 (13)0.20142 (5)0.28541 (4)0.0506 (2)
N10.1859 (4)0.45265 (16)0.35473 (12)0.0464 (4)
H10.10980.51490.39880.056*
N20.2353 (4)0.49265 (16)0.25394 (11)0.0449 (4)
O10.3206 (4)0.60245 (14)0.05809 (10)0.0553 (4)
C10.2537 (4)0.3197 (2)0.38518 (14)0.0407 (4)
C20.4665 (5)0.0393 (2)0.35393 (17)0.0557 (5)
H2A0.63110.07200.40900.084*
H2B0.5448−0.03430.30620.084*
H2C0.2659−0.00630.38310.084*
C30.1483 (5)0.6216 (2)0.23454 (16)0.0502 (5)
H30.05770.67720.28750.060*
C40.1847 (5)0.6835 (2)0.13501 (16)0.0481 (5)
C50.1076 (7)0.8131 (3)0.09881 (19)0.0685 (6)
H50.01390.88860.13600.082*
C60.1961 (6)0.8126 (3)−0.00661 (18)0.0673 (6)
H60.17050.8873−0.05230.081*
C70.3227 (6)0.6849 (3)−0.02770 (17)0.0608 (6)
H70.40180.6557−0.09200.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0714 (4)0.0502 (3)0.0359 (3)0.0125 (2)0.0107 (2)0.0105 (2)
S20.0694 (4)0.0482 (3)0.0378 (3)0.0171 (2)0.0114 (2)0.0072 (2)
N10.0681 (10)0.0401 (8)0.0326 (9)0.0104 (7)0.0108 (7)0.0056 (7)
N20.0614 (10)0.0393 (8)0.0352 (9)0.0078 (7)0.0060 (7)0.0077 (7)
O10.0837 (10)0.0443 (7)0.0418 (8)0.0168 (7)0.0145 (7)0.0112 (6)
C10.0456 (10)0.0405 (9)0.0345 (10)0.0013 (8)0.0024 (8)0.0026 (8)
C20.0701 (14)0.0467 (11)0.0534 (13)0.0161 (9)0.0056 (10)0.0087 (9)
C30.0655 (13)0.0478 (11)0.0390 (11)0.0114 (9)0.0094 (9)0.0051 (9)
C40.0631 (12)0.0419 (10)0.0419 (11)0.0129 (9)0.0072 (9)0.0076 (8)
C50.0988 (17)0.0596 (13)0.0577 (14)0.0391 (12)0.0168 (12)0.0165 (11)
C60.0947 (17)0.0596 (13)0.0544 (15)0.0224 (12)0.0054 (12)0.0278 (11)
C70.0875 (16)0.0583 (12)0.0393 (12)0.0115 (11)0.0109 (10)0.0173 (9)
Geometric parameters (Å, °) top
S1—C11.6675 (18)C2—H2B0.9600
S2—C11.7500 (19)C2—H2C0.9600
S2—C21.800 (2)C3—C41.430 (3)
N1—N21.379 (2)C3—H30.9300
N1—C11.331 (2)C4—C51.344 (3)
N1—H10.8600C5—C61.413 (3)
N2—C31.284 (2)C5—H50.9300
O1—C41.361 (2)C6—C71.327 (4)
O1—C71.364 (2)C6—H60.9300
C2—H2A0.9600C7—H70.9300
C1—S2—C2101.98 (9)N2—C3—C4122.79 (19)
C1—N1—N2121.34 (16)N2—C3—H3118.6
C1—N1—H1119.3C4—C3—H3118.6
N2—N1—H1119.3C5—C4—O1109.57 (17)
C3—N2—N1114.59 (16)C5—C4—C3132.1 (2)
C4—O1—C7106.45 (15)O1—C4—C3118.37 (16)
N1—C1—S1120.76 (14)C4—C5—C6106.8 (2)
N1—C1—S2114.05 (13)C4—C5—H5126.6
S1—C1—S2125.19 (11)C6—C5—H5126.6
S2—C2—H2A109.5C7—C6—C5106.67 (19)
S2—C2—H2B109.5C7—C6—H6126.7
H2A—C2—H2B109.5C5—C6—H6126.7
S2—C2—H2C109.5C6—C7—O1110.5 (2)
H2A—C2—H2C109.5C6—C7—H7124.8
H2B—C2—H2C109.5O1—C7—H7124.8
C1—N1—N2—C3177.62 (17)N2—C3—C4—C5179.2 (2)
N2—N1—C1—S1177.32 (12)N2—C3—C4—O1−0.7 (3)
N2—N1—C1—S2−3.0 (2)O1—C4—C5—C60.7 (3)
C2—S2—C1—N1178.23 (14)C3—C4—C5—C6−179.2 (2)
C2—S2—C1—S1−2.13 (15)C4—C5—C6—C7−0.5 (3)
N1—N2—C3—C4179.09 (17)C5—C6—C7—O10.1 (3)
C7—O1—C4—C5−0.6 (2)C4—O1—C7—C60.3 (3)
C7—O1—C4—C3179.25 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.862.653.4892 (17)165
Symmetry codes: (i) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.862.653.4892 (17)165
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

The project was supported by the Natural Science Foundation of Zhejiang Province, China (grant No. M203027).

references
References top

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