In the title compound, C
13H
12N
2OS
2, 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.
Supporting information
CCDC reference: 690926
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.033
- wR factor = 0.090
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
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.
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)
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).
Benzyl 3-[(
E)-furfurylidene]dithiocarbazate
top
Crystal data top
C13H12N2OS2 | Z = 2 |
Mr = 276.37 | F(000) = 288 |
Triclinic, P1 | Dx = 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 | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 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(Fo2) + (0.0446P)2 + 0.0525P] where P = (Fo2 + 2Fc2)/3 |
2324 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C13H12N2OS2 | γ = 97.910 (8)° |
Mr = 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 | Rint = 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 | Δρmax = 0.14 e Å−3 |
2324 reflections | Δρmin = −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 | Uiso*/Ueq | |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.14, −0.17 |
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. |
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).