Methyl 3-[(E)-furfuryl­idene]dithio­carbazate

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

doi:10.1107/S1600536808012506

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o970

doi:10.1107/S1600536808012506

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Methyl 3-[(E)-furfurylidene]dithiocarbazate

Shang Shan,^a ^* Shan-Heng Wang,^a Ying-Li Xu,^a Pei-Jin Xie ^a and Yu-Liang Tian ^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 31 March 2008; accepted 29 April 2008; online 3 May 2008)

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.

Related literature

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

Crystal data

C₇H₈N₂OS₂
M_r = 200.27
Triclinic, $[P \overline 1]$
a = 4.0866 (8) Å
b = 8.8698 (12) Å
c = 12.8453 (15) Å
α = 93.970 (14)°
β = 91.856 (12)°
γ = 98.293 (12)°
V = 459.21 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 294 (2) K
0.34 × 0.28 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.850, T_max = 0.950 (expected range = 0.804–0.899)
4733 measured reflections
1608 independent reflections
1349 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.096
S = 1.09
1608 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.86	2.65	3.4892 (17)	165
Symmetry code: (i) -x, -y+1, -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/S1600536808012506/xu2417sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012506/xu2417Isup2.hkl

checkCIF report

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.

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 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

C₇H₈N₂OS₂	Z = 2
M_r = 200.27	F(000) = 208
Triclinic, P1	D_x = 1.448 Mg m⁻³
Hall symbol: -P 1	Melting point = 414–416 K
a = 4.0866 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8698 (12) Å	Cell parameters from 2276 reflections
c = 12.8453 (15) Å	θ = 2.0–25.0°
α = 93.970 (14)°	µ = 0.53 mm⁻¹
β = 91.856 (12)°	T = 294 K
γ = 98.293 (12)°	Prism, yellow
V = 459.21 (12) Å³	0.34 × 0.28 × 0.20 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1608 independent reflections
Radiation source: fine-focus sealed tube	1349 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 1.6°
ω scans	h = −4→4
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
T_min = 0.850, T_max = 0.950	l = −15→14
4733 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0598P)²] where P = (F_o² + 2F_c²)/3
1608 reflections	(Δ/σ)_max = 0.001
110 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₇H₈N₂OS₂	γ = 98.293 (12)°
M_r = 200.27	V = 459.21 (12) Å³
Triclinic, P1	Z = 2
a = 4.0866 (8) Å	Mo Kα radiation
b = 8.8698 (12) Å	µ = 0.53 mm⁻¹
c = 12.8453 (15) Å	T = 294 K
α = 93.970 (14)°	0.34 × 0.28 × 0.20 mm
β = 91.856 (12)°

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)
T_min = 0.850, T_max = 0.950	R_int = 0.030
4733 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.09	Δρ_max = 0.19 e Å⁻³
1608 reflections	Δρ_min = −0.28 e Å⁻³
110 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	0.20815 (13)	0.27619 (5)	0.50863 (4)	0.0516 (2)
S2	0.38692 (13)	0.20142 (5)	0.28541 (4)	0.0506 (2)
N1	0.1859 (4)	0.45265 (16)	0.35473 (12)	0.0464 (4)
H1	0.1098	0.5149	0.3988	0.056*
N2	0.2353 (4)	0.49265 (16)	0.25394 (11)	0.0449 (4)
O1	0.3206 (4)	0.60245 (14)	0.05809 (10)	0.0553 (4)
C1	0.2537 (4)	0.3197 (2)	0.38518 (14)	0.0407 (4)
C2	0.4665 (5)	0.0393 (2)	0.35393 (17)	0.0557 (5)
H2A	0.6311	0.0720	0.4090	0.084*
H2B	0.5448	−0.0343	0.3062	0.084*
H2C	0.2659	−0.0063	0.3831	0.084*
C3	0.1483 (5)	0.6216 (2)	0.23454 (16)	0.0502 (5)
H3	0.0577	0.6772	0.2875	0.060*
C4	0.1847 (5)	0.6835 (2)	0.13501 (16)	0.0481 (5)
C5	0.1076 (7)	0.8131 (3)	0.09881 (19)	0.0685 (6)
H5	0.0139	0.8886	0.1360	0.082*
C6	0.1961 (6)	0.8126 (3)	−0.00661 (18)	0.0673 (6)
H6	0.1705	0.8873	−0.0523	0.081*
C7	0.3227 (6)	0.6849 (3)	−0.02770 (17)	0.0608 (6)
H7	0.4018	0.6557	−0.0920	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0714 (4)	0.0502 (3)	0.0359 (3)	0.0125 (2)	0.0107 (2)	0.0105 (2)
S2	0.0694 (4)	0.0482 (3)	0.0378 (3)	0.0171 (2)	0.0114 (2)	0.0072 (2)
N1	0.0681 (10)	0.0401 (8)	0.0326 (9)	0.0104 (7)	0.0108 (7)	0.0056 (7)
N2	0.0614 (10)	0.0393 (8)	0.0352 (9)	0.0078 (7)	0.0060 (7)	0.0077 (7)
O1	0.0837 (10)	0.0443 (7)	0.0418 (8)	0.0168 (7)	0.0145 (7)	0.0112 (6)
C1	0.0456 (10)	0.0405 (9)	0.0345 (10)	0.0013 (8)	0.0024 (8)	0.0026 (8)
C2	0.0701 (14)	0.0467 (11)	0.0534 (13)	0.0161 (9)	0.0056 (10)	0.0087 (9)
C3	0.0655 (13)	0.0478 (11)	0.0390 (11)	0.0114 (9)	0.0094 (9)	0.0051 (9)
C4	0.0631 (12)	0.0419 (10)	0.0419 (11)	0.0129 (9)	0.0072 (9)	0.0076 (8)
C5	0.0988 (17)	0.0596 (13)	0.0577 (14)	0.0391 (12)	0.0168 (12)	0.0165 (11)
C6	0.0947 (17)	0.0596 (13)	0.0544 (15)	0.0224 (12)	0.0054 (12)	0.0278 (11)
C7	0.0875 (16)	0.0583 (12)	0.0393 (12)	0.0115 (11)	0.0109 (10)	0.0173 (9)

Geometric parameters (Å, º) top

S1—C1	1.6675 (18)	C2—H2B	0.9600
S2—C1	1.7500 (19)	C2—H2C	0.9600
S2—C2	1.800 (2)	C3—C4	1.430 (3)
N1—N2	1.379 (2)	C3—H3	0.9300
N1—C1	1.331 (2)	C4—C5	1.344 (3)
N1—H1	0.8600	C5—C6	1.413 (3)
N2—C3	1.284 (2)	C5—H5	0.9300
O1—C4	1.361 (2)	C6—C7	1.327 (4)
O1—C7	1.364 (2)	C6—H6	0.9300
C2—H2A	0.9600	C7—H7	0.9300

C1—S2—C2	101.98 (9)	N2—C3—C4	122.79 (19)
C1—N1—N2	121.34 (16)	N2—C3—H3	118.6
C1—N1—H1	119.3	C4—C3—H3	118.6
N2—N1—H1	119.3	C5—C4—O1	109.57 (17)
C3—N2—N1	114.59 (16)	C5—C4—C3	132.1 (2)
C4—O1—C7	106.45 (15)	O1—C4—C3	118.37 (16)
N1—C1—S1	120.76 (14)	C4—C5—C6	106.8 (2)
N1—C1—S2	114.05 (13)	C4—C5—H5	126.6
S1—C1—S2	125.19 (11)	C6—C5—H5	126.6
S2—C2—H2A	109.5	C7—C6—C5	106.67 (19)
S2—C2—H2B	109.5	C7—C6—H6	126.7
H2A—C2—H2B	109.5	C5—C6—H6	126.7
S2—C2—H2C	109.5	C6—C7—O1	110.5 (2)
H2A—C2—H2C	109.5	C6—C7—H7	124.8
H2B—C2—H2C	109.5	O1—C7—H7	124.8

C1—N1—N2—C3	177.62 (17)	N2—C3—C4—C5	179.2 (2)
N2—N1—C1—S1	177.32 (12)	N2—C3—C4—O1	−0.7 (3)
N2—N1—C1—S2	−3.0 (2)	O1—C4—C5—C6	0.7 (3)
C2—S2—C1—N1	178.23 (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—C4	179.09 (17)	C5—C6—C7—O1	0.1 (3)
C7—O1—C4—C5	−0.6 (2)	C4—O1—C7—C6	0.3 (3)
C7—O1—C4—C3	179.25 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.65	3.4892 (17)	165

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₈N₂OS₂
M_r	200.27
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	4.0866 (8), 8.8698 (12), 12.8453 (15)
α, β, γ (°)	93.970 (14), 91.856 (12), 98.293 (12)
V (Å³)	459.21 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.34 × 0.28 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.850, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	4733, 1608, 1349
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.096, 1.09
No. of reflections	1608
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.28

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
N1—H1···S1ⁱ	0.86	2.65	3.4892 (17)	165

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

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

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