Benzyl 3-[(E)-furfuryl­idene]dithio­carbazate

Shan, S.; Tian, Y.-L.; Wang, S.-H.; Wang, W.-L.; Xu, Y.-L.

doi:10.1107/S160053680801307X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1024

doi:10.1107/S160053680801307X

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Benzyl 3-[(E)-furfurylidene]dithiocarbazate

Shang Shan,^a ^* Yu-Liang Tian,^a Shan-Heng Wang,^a Wen-Long Wang ^a and Ying-Li Xu ^a

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

Experimental

Crystal data

C₁₃H₁₂N₂OS₂
M_r = 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)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.090
S = 1.07
2324 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: PROCESS-AUTO; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801307X/hb2727sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801307X/hb2727Isup2.hkl

checkCIF report

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.

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

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

C₁₃H₁₂N₂OS₂	Z = 2
M_r = 276.37	F(000) = 288
Triclinic, P1	D_x = 1.371 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8331 (11) Å	Cell parameters from 3836 reflections
b = 12.040 (3) Å	θ = 1.8–25.0°
c = 12.549 (3) Å	µ = 0.39 mm⁻¹
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 tube	R_int = 0.024
Graphite monochromator	θ_max = 25.0°, θ_min = 1.8°
Detector resolution: 10.00 pixels mm^-1	h = −5→5
ω scans	k = −14→13
7084 measured reflections	l = −14→14
2324 independent 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0446P)² + 0.0525P] where P = (F_o² + 2F_c²)/3
2324 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₃H₁₂N₂OS₂	γ = 97.910 (8)°
M_r = 276.37	V = 669.5 (3) Å³
Triclinic, P1	Z = 2
a = 4.8331 (11) Å	Mo Kα radiation
b = 12.040 (3) Å	µ = 0.39 mm⁻¹
c = 12.549 (3) Å	T = 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 reflections	R_int = 0.024
2324 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	Δρ_max = 0.14 e Å⁻³
2324 reflections	Δρ_min = −0.17 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	1.03544 (13)	−0.02756 (5)	0.32307 (4)	0.0669 (2)
S2	0.84716 (12)	0.18647 (4)	0.27822 (4)	0.06143 (19)
O1	0.4143 (3)	0.41877 (12)	0.56065 (11)	0.0662 (4)
N1	0.6602 (3)	0.22213 (13)	0.48240 (13)	0.0533 (4)
N2	0.7837 (3)	0.12309 (13)	0.45371 (13)	0.0569 (4)
H2N	0.7943	0.0807	0.4976	0.068*
C1	0.4147 (4)	0.33502 (16)	0.61307 (15)	0.0527 (5)
C2	0.2854 (5)	0.36601 (19)	0.70185 (17)	0.0640 (5)
H2	0.2592	0.3242	0.7516	0.077*
C3	0.1967 (5)	0.47383 (19)	0.70534 (19)	0.0711 (6)
H3	0.1011	0.5168	0.7574	0.085*
C4	0.2776 (5)	0.50159 (19)	0.61914 (19)	0.0720 (6)
H4	0.2452	0.5687	0.6011	0.086*
C5	0.5457 (4)	0.23599 (17)	0.56929 (16)	0.0548 (5)
H5	0.5479	0.1793	0.6054	0.066*
C6	0.8870 (4)	0.09223 (16)	0.35868 (15)	0.0510 (5)
C7	1.0091 (5)	0.11971 (19)	0.15901 (17)	0.0647 (5)
H7A	1.2107	0.1229	0.1872	0.078*
H7B	0.9145	0.0368	0.1189	0.078*
C8	0.9740 (4)	0.19026 (17)	0.07913 (16)	0.0560 (5)
C9	0.7422 (5)	0.1560 (2)	−0.01297 (19)	0.0764 (6)
H9	0.6064	0.0877	−0.0258	0.092*
C10	0.7056 (7)	0.2192 (3)	−0.0861 (2)	0.0916 (8)
H10	0.5469	0.1939	−0.1476	0.110*
C11	0.9002 (8)	0.3183 (3)	−0.0689 (3)	0.0931 (9)
H11	0.8750	0.3616	−0.1182	0.112*
C12	1.1348 (7)	0.3554 (2)	0.0210 (3)	0.0979 (9)
H12	1.2695	0.4235	0.0325	0.117*
C13	1.1712 (5)	0.2906 (2)	0.0954 (2)	0.0795 (6)
H13	1.3306	0.3159	0.1565	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0906 (4)	0.0557 (3)	0.0675 (3)	0.0399 (3)	0.0222 (3)	0.0265 (2)
S2	0.0790 (4)	0.0596 (3)	0.0632 (3)	0.0369 (3)	0.0240 (3)	0.0313 (2)
O1	0.0945 (11)	0.0586 (8)	0.0640 (8)	0.0373 (7)	0.0296 (7)	0.0313 (7)
N1	0.0610 (10)	0.0490 (9)	0.0560 (9)	0.0254 (8)	0.0127 (8)	0.0206 (7)
N2	0.0722 (11)	0.0519 (9)	0.0595 (9)	0.0302 (8)	0.0188 (8)	0.0275 (7)
C1	0.0573 (12)	0.0517 (11)	0.0549 (10)	0.0174 (9)	0.0118 (9)	0.0244 (9)
C2	0.0741 (14)	0.0667 (13)	0.0656 (12)	0.0244 (11)	0.0285 (11)	0.0316 (10)
C3	0.0787 (15)	0.0672 (14)	0.0736 (14)	0.0314 (12)	0.0303 (12)	0.0187 (11)
C4	0.0920 (17)	0.0575 (13)	0.0773 (14)	0.0389 (12)	0.0243 (12)	0.0253 (11)
C5	0.0623 (12)	0.0526 (11)	0.0585 (11)	0.0213 (9)	0.0138 (9)	0.0275 (9)
C6	0.0525 (11)	0.0483 (11)	0.0547 (10)	0.0173 (9)	0.0079 (8)	0.0201 (8)
C7	0.0737 (14)	0.0654 (13)	0.0702 (12)	0.0341 (11)	0.0265 (11)	0.0303 (10)
C8	0.0629 (13)	0.0559 (12)	0.0600 (11)	0.0263 (10)	0.0251 (10)	0.0229 (9)
C9	0.0843 (17)	0.0717 (15)	0.0764 (14)	0.0172 (12)	0.0151 (13)	0.0309 (12)
C10	0.117 (2)	0.100 (2)	0.0697 (15)	0.0416 (18)	0.0182 (14)	0.0385 (15)
C11	0.132 (3)	0.103 (2)	0.0922 (19)	0.065 (2)	0.0647 (19)	0.0602 (17)
C12	0.103 (2)	0.0752 (17)	0.142 (3)	0.0230 (16)	0.062 (2)	0.0551 (18)
C13	0.0761 (16)	0.0753 (16)	0.0940 (16)	0.0195 (13)	0.0238 (13)	0.0346 (13)

Geometric parameters (Å, º) top

S1—C6	1.6686 (18)	C5—H5	0.9300
S2—C6	1.7477 (19)	C7—C8	1.507 (3)
S2—C7	1.820 (2)	C7—H7A	0.9700
O1—C4	1.363 (2)	C7—H7B	0.9700
O1—C1	1.365 (2)	C8—C13	1.369 (3)
N1—C5	1.280 (2)	C8—C9	1.378 (3)
N1—N2	1.381 (2)	C9—C10	1.369 (3)
N2—C6	1.336 (2)	C9—H9	0.9300
N2—H2N	0.8600	C10—C11	1.348 (4)
C1—C2	1.345 (3)	C10—H10	0.9300
C1—C5	1.428 (3)	C11—C12	1.368 (4)
C2—C3	1.412 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.395 (4)
C3—C4	1.329 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—H13	0.9300
C4—H4	0.9300

C6—S2—C7	102.07 (9)	C8—C7—S2	107.15 (13)
C4—O1—C1	106.12 (15)	C8—C7—H7A	110.3
C5—N1—N2	114.92 (16)	S2—C7—H7A	110.3
C6—N2—N1	120.90 (15)	C8—C7—H7B	110.3
C6—N2—H2N	119.6	S2—C7—H7B	110.3
N1—N2—H2N	119.6	H7A—C7—H7B	108.5
C2—C1—O1	109.46 (17)	C13—C8—C9	117.6 (2)
C2—C1—C5	131.99 (18)	C13—C8—C7	121.2 (2)
O1—C1—C5	118.55 (16)	C9—C8—C7	121.1 (2)
C1—C2—C3	107.23 (19)	C10—C9—C8	122.0 (2)
C1—C2—H2	126.4	C10—C9—H9	119.0
C3—C2—H2	126.4	C8—C9—H9	119.0
C4—C3—C2	106.14 (18)	C11—C10—C9	119.8 (3)
C4—C3—H3	126.9	C11—C10—H10	120.1
C2—C3—H3	126.9	C9—C10—H10	120.1
C3—C4—O1	111.05 (19)	C10—C11—C12	120.3 (3)
C3—C4—H4	124.5	C10—C11—H11	119.9
O1—C4—H4	124.5	C12—C11—H11	119.9
N1—C5—C1	122.66 (18)	C11—C12—C13	119.7 (3)
N1—C5—H5	118.7	C11—C12—H12	120.1
C1—C5—H5	118.7	C13—C12—H12	120.1
N2—C6—S1	121.22 (14)	C8—C13—C12	120.5 (2)
N2—C6—S2	114.01 (13)	C8—C13—H13	119.7
S1—C6—S2	124.76 (11)	C12—C13—H13	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1ⁱ	0.86	2.56	3.3761 (19)	158

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂OS₂
M_r	276.37
Crystal system, space group	Triclinic, 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)
V (Å³)	669.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.42 × 0.36 × 0.32

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7084, 2324, 1799
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.07
No. of reflections	2324
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1ⁱ	0.86	2.56	3.3761 (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

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