organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Benzyl 3-[(E)-furfuryl­­idene]di­thio­carbazate

aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 28 April 2008; accepted 3 May 2008; online 10 May 2008)

In the title compound, C13H12N2OS2, the mol­ecule assumes an E configuration, with the furan ring and dithio­carbazate units located on opposite sides of the N=C double bond. In the crystal structure, mol­ecules are linked via two inter­molecular N—H⋯S hydrogen bonds to form centrosymmetric dimers.

Related literature

For general background, see: Okabe et al. (1993[Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678-1680.]). For related structures, see: Shan et al. (2006[Shan, S., Zhang, Y.-L. & Xu, D.-J. (2006). Acta Cryst. E62, o1567-o1569.], 2008[Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008). Acta Cryst. E64, o1014.]). For the synthesis and background, see: Hu et al. (2001[Hu, W., Sun, N. & Yang, Z. (2001). Chem. J. Chin. Univ. 22, 2014-2017.]).

[Scheme 1]

Experimental

Crystal data
  • C13H12N2OS2

  • Mr = 276.37

  • Triclinic, [P \overline 1]

  • a = 4.8331 (11) Å

  • b = 12.040 (3) Å

  • c = 12.549 (3) Å

  • α = 108.203 (7)°

  • β = 99.704 (9)°

  • γ = 97.910 (8)°

  • V = 669.5 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.39 mm−1

  • T = 295 (2) K

  • 0.42 × 0.36 × 0.32 mm

Data collection
  • Rigaku R-AXIS RAPID IP diffractometer

  • Absorption correction: none

  • 7084 measured reflections

  • 2324 independent reflections

  • 1799 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.090

  • S = 1.07

  • 2324 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2N⋯S1i 0.86 2.56 3.3761 (19) 158
Symmetry code: (i) -x+2, -y, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998[Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

Hydrazone and its derivatives have shown the potential application in biological field (Okabe et al., 1993). As part of our ongoing investigation on anti-cancer compounds (Hu et al., 2001), the title compound, (I), has been prepared in our laboratory and its crystal structure is presented here.

The N1—C5 distance indicates a typical C=N double bond. The furan and dithiocarbazate moieties are located on the opposite positions of the C=N bond, thus the molecule assumes an E-configuration, which agrees with that found in methyl (β-N-phenylmethylene)dithiocarbazate (Shan et al., 2006).

In the molecule of (I), the furan ring is slightly twisted with respect to the dithiocarbazate plane with a dihedral angle of 7.58 (14)°, whereas the phenyl ring of the thioester group is nearly perpendicular to the dithiocarbazate plane with a dihedral angle of 85.51 (5)°. This is similar to that found in a related structure, benzyl 3-[(E)-phenylmethylene]dithiocarbazate (Shan et al., 2008).

In the crystal of (I), adjacent molecules are linked by intermolecular N—H···S hydrogen bonding into inversion dimers (Fig. 1 and Table 1).

Related literature top

For general background, see: Okabe et al. (1993). For related structures, see: Shan et al. (2006, 2008). For the synthesis and background, see: Hu et al. (2001).

Experimental top

Benzyl dithiocarbazate was synthesized as described previously (Hu et al., 2001). Benzyl dithiocarbazate (1.98 g, 10 mmol) and furfural (0.96 g, 10 mmol) were dissolved in ethanol (40 ml) and the solution was refluxed for 12 h. A yellow crystalline product appeared after cooling to room temperature; it was separated and washed with cold water three times. Yellow prisms of (I) were obtained by recrystallization from an ethanol solution.

Refinement top

The H atoms were placed in calculated positions with C—H = 0.97 (methylene), 0.93Å (aromatic) and N—H = 0.86 Å, and refined as riding with 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 inversion dimer in the crystal of (I) drawn with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonding [symmetry code: (i) 2 - x,-y,1 - z].
Benzyl 3-[(E)-furfurylidene]dithiocarbazate top
Crystal data top
C13H12N2OS2Z = 2
Mr = 276.37F(000) = 288
Triclinic, P1Dx = 1.371 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.8331 (11) ÅCell parameters from 3836 reflections
b = 12.040 (3) Åθ = 1.8–25.0°
c = 12.549 (3) ŵ = 0.39 mm1
α = 108.203 (7)°T = 295 K
β = 99.704 (9)°Prism, yellow
γ = 97.910 (8)°0.42 × 0.36 × 0.32 mm
V = 669.5 (3) Å3
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
1799 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
Graphite monochromatorθmax = 25.0°, θmin = 1.8°
Detector resolution: 10.00 pixels mm-1h = 55
ω scansk = 1413
7084 measured reflectionsl = 1414
2324 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0446P)2 + 0.0525P]
where P = (Fo2 + 2Fc2)/3
2324 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C13H12N2OS2γ = 97.910 (8)°
Mr = 276.37V = 669.5 (3) Å3
Triclinic, P1Z = 2
a = 4.8331 (11) ÅMo Kα radiation
b = 12.040 (3) ŵ = 0.39 mm1
c = 12.549 (3) ÅT = 295 K
α = 108.203 (7)°0.42 × 0.36 × 0.32 mm
β = 99.704 (9)°
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
1799 reflections with I > 2σ(I)
7084 measured reflectionsRint = 0.024
2324 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.07Δρmax = 0.14 e Å3
2324 reflectionsΔρmin = 0.17 e Å3
163 parameters
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
S11.03544 (13)0.02756 (5)0.32307 (4)0.0669 (2)
S20.84716 (12)0.18647 (4)0.27822 (4)0.06143 (19)
O10.4143 (3)0.41877 (12)0.56065 (11)0.0662 (4)
N10.6602 (3)0.22213 (13)0.48240 (13)0.0533 (4)
N20.7837 (3)0.12309 (13)0.45371 (13)0.0569 (4)
H2N0.79430.08070.49760.068*
C10.4147 (4)0.33502 (16)0.61307 (15)0.0527 (5)
C20.2854 (5)0.36601 (19)0.70185 (17)0.0640 (5)
H20.25920.32420.75160.077*
C30.1967 (5)0.47383 (19)0.70534 (19)0.0711 (6)
H30.10110.51680.75740.085*
C40.2776 (5)0.50159 (19)0.61914 (19)0.0720 (6)
H40.24520.56870.60110.086*
C50.5457 (4)0.23599 (17)0.56929 (16)0.0548 (5)
H50.54790.17930.60540.066*
C60.8870 (4)0.09223 (16)0.35868 (15)0.0510 (5)
C71.0091 (5)0.11971 (19)0.15901 (17)0.0647 (5)
H7A1.21070.12290.18720.078*
H7B0.91450.03680.11890.078*
C80.9740 (4)0.19026 (17)0.07913 (16)0.0560 (5)
C90.7422 (5)0.1560 (2)0.01297 (19)0.0764 (6)
H90.60640.08770.02580.092*
C100.7056 (7)0.2192 (3)0.0861 (2)0.0916 (8)
H100.54690.19390.14760.110*
C110.9002 (8)0.3183 (3)0.0689 (3)0.0931 (9)
H110.87500.36160.11820.112*
C121.1348 (7)0.3554 (2)0.0210 (3)0.0979 (9)
H121.26950.42350.03250.117*
C131.1712 (5)0.2906 (2)0.0954 (2)0.0795 (6)
H131.33060.31590.15650.095*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0906 (4)0.0557 (3)0.0675 (3)0.0399 (3)0.0222 (3)0.0265 (2)
S20.0790 (4)0.0596 (3)0.0632 (3)0.0369 (3)0.0240 (3)0.0313 (2)
O10.0945 (11)0.0586 (8)0.0640 (8)0.0373 (7)0.0296 (7)0.0313 (7)
N10.0610 (10)0.0490 (9)0.0560 (9)0.0254 (8)0.0127 (8)0.0206 (7)
N20.0722 (11)0.0519 (9)0.0595 (9)0.0302 (8)0.0188 (8)0.0275 (7)
C10.0573 (12)0.0517 (11)0.0549 (10)0.0174 (9)0.0118 (9)0.0244 (9)
C20.0741 (14)0.0667 (13)0.0656 (12)0.0244 (11)0.0285 (11)0.0316 (10)
C30.0787 (15)0.0672 (14)0.0736 (14)0.0314 (12)0.0303 (12)0.0187 (11)
C40.0920 (17)0.0575 (13)0.0773 (14)0.0389 (12)0.0243 (12)0.0253 (11)
C50.0623 (12)0.0526 (11)0.0585 (11)0.0213 (9)0.0138 (9)0.0275 (9)
C60.0525 (11)0.0483 (11)0.0547 (10)0.0173 (9)0.0079 (8)0.0201 (8)
C70.0737 (14)0.0654 (13)0.0702 (12)0.0341 (11)0.0265 (11)0.0303 (10)
C80.0629 (13)0.0559 (12)0.0600 (11)0.0263 (10)0.0251 (10)0.0229 (9)
C90.0843 (17)0.0717 (15)0.0764 (14)0.0172 (12)0.0151 (13)0.0309 (12)
C100.117 (2)0.100 (2)0.0697 (15)0.0416 (18)0.0182 (14)0.0385 (15)
C110.132 (3)0.103 (2)0.0922 (19)0.065 (2)0.0647 (19)0.0602 (17)
C120.103 (2)0.0752 (17)0.142 (3)0.0230 (16)0.062 (2)0.0551 (18)
C130.0761 (16)0.0753 (16)0.0940 (16)0.0195 (13)0.0238 (13)0.0346 (13)
Geometric parameters (Å, º) top
S1—C61.6686 (18)C5—H50.9300
S2—C61.7477 (19)C7—C81.507 (3)
S2—C71.820 (2)C7—H7A0.9700
O1—C41.363 (2)C7—H7B0.9700
O1—C11.365 (2)C8—C131.369 (3)
N1—C51.280 (2)C8—C91.378 (3)
N1—N21.381 (2)C9—C101.369 (3)
N2—C61.336 (2)C9—H90.9300
N2—H2N0.8600C10—C111.348 (4)
C1—C21.345 (3)C10—H100.9300
C1—C51.428 (3)C11—C121.368 (4)
C2—C31.412 (3)C11—H110.9300
C2—H20.9300C12—C131.395 (4)
C3—C41.329 (3)C12—H120.9300
C3—H30.9300C13—H130.9300
C4—H40.9300
C6—S2—C7102.07 (9)C8—C7—S2107.15 (13)
C4—O1—C1106.12 (15)C8—C7—H7A110.3
C5—N1—N2114.92 (16)S2—C7—H7A110.3
C6—N2—N1120.90 (15)C8—C7—H7B110.3
C6—N2—H2N119.6S2—C7—H7B110.3
N1—N2—H2N119.6H7A—C7—H7B108.5
C2—C1—O1109.46 (17)C13—C8—C9117.6 (2)
C2—C1—C5131.99 (18)C13—C8—C7121.2 (2)
O1—C1—C5118.55 (16)C9—C8—C7121.1 (2)
C1—C2—C3107.23 (19)C10—C9—C8122.0 (2)
C1—C2—H2126.4C10—C9—H9119.0
C3—C2—H2126.4C8—C9—H9119.0
C4—C3—C2106.14 (18)C11—C10—C9119.8 (3)
C4—C3—H3126.9C11—C10—H10120.1
C2—C3—H3126.9C9—C10—H10120.1
C3—C4—O1111.05 (19)C10—C11—C12120.3 (3)
C3—C4—H4124.5C10—C11—H11119.9
O1—C4—H4124.5C12—C11—H11119.9
N1—C5—C1122.66 (18)C11—C12—C13119.7 (3)
N1—C5—H5118.7C11—C12—H12120.1
C1—C5—H5118.7C13—C12—H12120.1
N2—C6—S1121.22 (14)C8—C13—C12120.5 (2)
N2—C6—S2114.01 (13)C8—C13—H13119.7
S1—C6—S2124.76 (11)C12—C13—H13119.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···S1i0.862.563.3761 (19)158
Symmetry code: (i) x+2, y, z+1.

Experimental details

Crystal data
Chemical formulaC13H12N2OS2
Mr276.37
Crystal system, space groupTriclinic, P1
Temperature (K)295
a, b, c (Å)4.8331 (11), 12.040 (3), 12.549 (3)
α, β, γ (°)108.203 (7), 99.704 (9), 97.910 (8)
V3)669.5 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.39
Crystal size (mm)0.42 × 0.36 × 0.32
Data collection
DiffractometerRigaku R-AXIS RAPID IP
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7084, 2324, 1799
Rint0.024
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.090, 1.07
No. of reflections2324
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.17

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···S1i0.862.563.3761 (19)158
Symmetry code: (i) x+2, y, z+1.
 

Acknowledgements

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

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350.  CrossRef Web of Science IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
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First citationHu, W., Sun, N. & Yang, Z. (2001). Chem. J. Chin. Univ. 22, 2014–2017.  CAS Google Scholar
First citationOkabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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First citationShan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008). Acta Cryst. E64, o1014.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationShan, S., Zhang, Y.-L. & Xu, D.-J. (2006). Acta Cryst. E62, o1567–o1569.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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