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Acta Cryst. (2013). E69, o644    [ doi:10.1107/S1600536813008398 ]

1-(2H-1,3-Benzodioxol-5-yl)ethanone thiosemicarbazone

A. B. de Oliveira, R. L. de Farias, C. Näther, I. Jess and L. Bresolin

Abstract top

In the title compound, C10H11N3O2S, the 1,3-benzodioxole and hydrazinecarbothioamide fragments are nearly planar [(mean deviations from planarity for non-H atoms of 0.0325 (12) Å and 0.0707 (10) Å, respectively] and subtend a dihedral angle of 29.06 (5)°. In the crystal, molecules are linked by pairs of almost linear N-H...S hydrogen bonds, forming inversion dimers. These dimers are additionally connected by weaker and strongly bent N-H...S interactions into chains along [101]. There is one additional weak N-H...O contact which, if considered as an interaction, leads to the formation of a three-dimensional network.

Comment top

Thiosemicarbazone derivatives have a wide range of pharmacological properties. For example, 3',4'-(methylenedioxy)acetophenone thiosemicarbazone derivatives show cytotoxic activity against KB cells (Silva et al., 1998). As part of our study on the synthesis of thiosemicarbazone derivatives, we report herein the crystal structure of a new 3',4'-(methylenedioxy)acetophenone thiosemicarbazone derivative.

In the crystal structure of the title compound, C10H11N3O2S, the molecules are twisted and consists of two nearly planar parts, a benzo[1,3]dioxole fragment and a hydrazinecarbothioamide fragment (mean deviations from planarity for non-H atoms 0.0325 (12) Å and 0.0707 (10) Å, respectively), which subtend a dihedral angle of 29.06 (5)° (Fig. 1). The molecule shows an E conformation for the atoms about the N3—N2 and N2—C1 bonds, which is also observed in the crystal structures of other thiosemicarbazone derivatives (de Oliveira et al., 2012).

In the crystal structure the molecules are linked by pairs of N—H···S hydrogen bonds into inversion related dimers (Fig. 2 and Table 1). These dimers are further connected by centrosymmetric pairs of weak N—H···S interactions into chains extending along [101] (Fig. 2). Finally, there is one N—H···O contact between that NH2 hydrogen atom which is not involved in N—H···S bonding and the dioxole oxygen O1 (Table 1). If this contact is considered as an interaction the chains are additionally linked into a three-dimensional network (Fig. 2).

In the crystal structure the benzo[1,3]dioxole fragments are oriented nearly perpendicular to [001] and are stacked above each other along this direction by the c-glide plane with a repetition period of c/2 = 3.5645 (7) Å implying π-π stacking.

Related literature top

For the adapted synthesis of the title compound, see: de Oliveira et al. (2012). For the pharmacological activity of 3',4'-(methylenedioxy)acetophenone thiosimecarbazone derivatives, see: Silva et al. (1998).

Experimental top

All starting materials are commercially available and were used without further purification. The synthesis was adapted from a procedure reported previously (de Oliveira et al., 2012). The hydrochloric acid catalyzed reaction of 3',4'-(methylenedioxy)acetophenone (10 mmol) and thiosemicarbazide (10 mmol) in a 3:1 mixture of ethanol and water (100 ml) was refluxed for 6 h. After cooling and filtering crystals suitable for X-ray diffraction were obtained.

Elemental analysis: Calc. 50.62% for C, 4.67% for H, 17.71% for N and 13.51% for S; found 50.72% for C, 4.66% for H, 17.70% for N and 13.47% for S. The melting point was determined by differential scanning calorimetry to 187° C and the enthalpy of fusion amount to 25.9 kJ/mol. After melting the compound decomposes.

Refinement top

All H atoms were located in a Fourier map. C-bonded H atoms were then geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C(CH), C(CH2)) or 1.5Ueq(C) and AFIX 136 for the methyl group. The N-bonded H atoms were only adjusted to N—H = 0.88 Å and were then refined as riding with Uiso(H) = 1.2 Ueq(N).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-RED32 (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. Crystal structure of the title compound in a view along the a axis with hydrogen bonds shown as dashed lines.
1-(2H-1,3-Benzodioxol-5-yl)ethanone thiosemicarbazone top
Crystal data top
C10H11N3O2SF(000) = 496
Mr = 237.28Dx = 1.461 Mg m3
Monoclinic, P21/cMelting point: 460.2 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.1423 (12) ÅCell parameters from 8000 reflections
b = 26.065 (5) Åθ = 3–27.9°
c = 7.1289 (14) ŵ = 0.29 mm1
β = 109.07 (3)°T = 200 K
V = 1078.7 (4) Å3Block, yellow
Z = 40.3 × 0.2 × 0.2 mm
Data collection top
Stoe IPDS-1
diffractometer
2018 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.046
Graphite monochromatorθmax = 27.0°, θmin = 3.1°
φ scansh = 77
12310 measured reflectionsk = 3333
2315 independent reflectionsl = 99
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)] = 0.037H-atom parameters constrained
wR(F2) = 0.107 w = 1/[σ2(Fo2) + (0.0692P)2 + 0.2915P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2315 reflectionsΔρmax = 0.29 e Å3
147 parametersΔρmin = 0.32 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.047 (8)
Crystal data top
C10H11N3O2SV = 1078.7 (4) Å3
Mr = 237.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.1423 (12) ŵ = 0.29 mm1
b = 26.065 (5) ÅT = 200 K
c = 7.1289 (14) Å0.3 × 0.2 × 0.2 mm
β = 109.07 (3)°
Data collection top
Stoe IPDS-1
diffractometer
2018 reflections with I > 2σ(I)
12310 measured reflectionsRint = 0.046
2315 independent reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.107Δρmax = 0.29 e Å3
S = 1.04Δρmin = 0.32 e Å3
2315 reflectionsAbsolute structure: ?
147 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
N10.2311 (2)0.43475 (5)0.0548 (2)0.0326 (3)
H1N10.27650.40320.04310.049*
H2N10.09170.44610.00940.049*
C10.3775 (3)0.46661 (5)0.1778 (2)0.0229 (3)
S10.31425 (7)0.528178 (13)0.21371 (6)0.03093 (17)
N20.5891 (2)0.44885 (4)0.28111 (18)0.0252 (3)
H1N20.66850.46730.38400.030*
N30.6401 (2)0.39750 (4)0.26964 (18)0.0230 (3)
C20.8498 (2)0.38377 (5)0.3628 (2)0.0205 (3)
C31.0366 (3)0.42034 (6)0.4726 (3)0.0332 (4)
H3A1.04300.44890.38500.050*
H3B1.18490.40240.51510.050*
H3C1.00390.43360.58920.050*
C40.8967 (2)0.32787 (5)0.3605 (2)0.0201 (3)
C51.1206 (3)0.30922 (6)0.4082 (2)0.0276 (3)
H51.24500.33290.43940.033*
C61.1679 (3)0.25646 (6)0.4115 (3)0.0320 (4)
H61.32090.24400.44210.038*
C70.9848 (3)0.22397 (5)0.3689 (2)0.0250 (3)
O10.9848 (2)0.17122 (4)0.36822 (19)0.0362 (3)
C80.7485 (3)0.15623 (6)0.3202 (3)0.0329 (4)
H8A0.70260.13450.19970.039*
H8B0.72670.13620.43080.039*
O20.6109 (2)0.20154 (4)0.2866 (2)0.0409 (3)
C90.7615 (3)0.24196 (5)0.3209 (2)0.0241 (3)
C100.7108 (3)0.29321 (5)0.3141 (2)0.0242 (3)
H100.55620.30490.27950.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0320 (7)0.0199 (6)0.0367 (8)0.0067 (5)0.0014 (6)0.0073 (5)
C10.0269 (7)0.0175 (6)0.0227 (7)0.0036 (5)0.0060 (6)0.0011 (5)
S10.0335 (3)0.0145 (2)0.0383 (3)0.00688 (13)0.00280 (18)0.00235 (13)
N20.0285 (7)0.0133 (6)0.0287 (7)0.0050 (4)0.0022 (5)0.0034 (4)
N30.0278 (6)0.0128 (5)0.0255 (6)0.0044 (4)0.0049 (5)0.0015 (4)
C20.0231 (7)0.0162 (6)0.0226 (7)0.0011 (5)0.0079 (6)0.0007 (5)
C30.0258 (8)0.0250 (7)0.0475 (10)0.0039 (6)0.0101 (7)0.0084 (6)
C40.0220 (7)0.0168 (6)0.0204 (6)0.0039 (5)0.0056 (5)0.0008 (5)
C50.0219 (7)0.0230 (7)0.0363 (8)0.0034 (5)0.0073 (6)0.0012 (6)
C60.0251 (7)0.0269 (8)0.0429 (9)0.0116 (6)0.0095 (7)0.0044 (6)
C70.0331 (8)0.0172 (7)0.0246 (7)0.0099 (5)0.0092 (6)0.0030 (5)
O10.0434 (7)0.0165 (5)0.0473 (7)0.0112 (4)0.0129 (6)0.0045 (4)
C80.0487 (10)0.0156 (7)0.0349 (9)0.0047 (6)0.0145 (8)0.0013 (6)
O20.0333 (6)0.0141 (5)0.0703 (9)0.0002 (4)0.0100 (6)0.0022 (5)
C90.0262 (7)0.0161 (6)0.0281 (7)0.0012 (5)0.0064 (6)0.0006 (5)
C100.0209 (7)0.0170 (7)0.0324 (8)0.0043 (5)0.0058 (6)0.0006 (5)
Geometric parameters (Å, º) top
N1—C11.324 (2)C4—C101.408 (2)
N1—H1N10.8802C5—C61.404 (2)
N1—H2N10.8800C5—H50.9500
C1—N21.3494 (19)C6—C71.361 (2)
C1—S11.6901 (14)C6—H60.9500
N2—N31.3831 (16)C7—O11.3749 (17)
N2—H1N20.8800C7—C91.382 (2)
N3—C21.2921 (19)O1—C81.432 (2)
C2—C41.4864 (17)C8—O21.4261 (19)
C2—C31.500 (2)C8—H8A0.9900
C3—H3A0.9800C8—H8B0.9900
C3—H3B0.9800O2—C91.3704 (18)
C3—H3C0.9800C9—C101.3690 (19)
C4—C51.392 (2)C10—H100.9500
C1—N1—H1N1118.7C4—C5—H5119.0
C1—N1—H2N1117.9C6—C5—H5119.0
H1N1—N1—H2N1123.4C7—C6—C5117.03 (13)
N1—C1—N2118.10 (12)C7—C6—H6121.5
N1—C1—S1123.79 (12)C5—C6—H6121.5
N2—C1—S1118.11 (11)C6—C7—O1128.48 (14)
C1—N2—N3119.75 (12)C6—C7—C9121.67 (13)
C1—N2—H1N2116.1O1—C7—C9109.84 (13)
N3—N2—H1N2120.3C7—O1—C8105.81 (11)
C2—N3—N2116.40 (12)O2—C8—O1108.23 (12)
N3—C2—C4115.46 (12)O2—C8—H8A110.1
N3—C2—C3123.80 (13)O1—C8—H8A110.1
C4—C2—C3120.72 (13)O2—C8—H8B110.1
C2—C3—H3A109.5O1—C8—H8B110.1
C2—C3—H3B109.5H8A—C8—H8B108.4
H3A—C3—H3B109.5C9—O2—C8106.15 (13)
C2—C3—H3C109.5C10—C9—O2127.67 (14)
H3A—C3—H3C109.5C10—C9—C7122.40 (14)
H3B—C3—H3C109.5O2—C9—C7109.93 (12)
C5—C4—C10119.61 (13)C9—C10—C4117.38 (13)
C5—C4—C2121.26 (13)C9—C10—H10121.3
C10—C4—C2119.12 (12)C4—C10—H10121.3
C4—C5—C6121.91 (14)
N1—C1—N2—N35.7 (2)C6—C7—O1—C8178.09 (16)
S1—C1—N2—N3174.06 (10)C9—C7—O1—C80.96 (17)
C1—N2—N3—C2175.99 (13)C7—O1—C8—O21.91 (17)
N2—N3—C2—C4175.80 (11)O1—C8—O2—C92.14 (17)
N2—N3—C2—C32.5 (2)C8—O2—C9—C10177.54 (15)
N3—C2—C4—C5163.15 (13)C8—O2—C9—C71.57 (18)
C3—C2—C4—C518.5 (2)C6—C7—C9—C100.3 (2)
N3—C2—C4—C1018.52 (19)O1—C7—C9—C10178.77 (13)
C3—C2—C4—C10159.82 (14)C6—C7—C9—O2179.51 (15)
C10—C4—C5—C60.0 (2)O1—C7—C9—O20.39 (18)
C2—C4—C5—C6178.38 (14)O2—C9—C10—C4178.34 (15)
C4—C5—C6—C71.0 (2)C7—C9—C10—C40.7 (2)
C5—C6—C7—O1177.77 (15)C5—C4—C10—C90.8 (2)
C5—C6—C7—C91.2 (2)C2—C4—C10—C9177.57 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O1i0.882.663.2207 (17)123
N1—H2N1···S1ii0.882.533.4100 (18)175
N2—H1N2···S1iii0.882.843.5048 (15)134
Symmetry codes: (i) x1, y+1/2, z1/2; (ii) x, y+1, z; (iii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O1i0.882.663.2207 (17)122.7
N1—H2N1···S1ii0.882.533.4100 (18)174.8
N2—H1N2···S1iii0.882.843.5048 (15)133.8
Symmetry codes: (i) x1, y+1/2, z1/2; (ii) x, y+1, z; (iii) x+1, y+1, z+1.
Acknowledgements top

We gratefully acknowledge financial support by the State of Schleswig–Holstein, Germany. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. ABO acknowledges financial support through the FAPITEC/SE/FUNTEC/CNPq PPP 04/2011 program.

references
References top

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Oliveira, A. B. de, Silva, C. S., Feitosa, B. R. S., Näther, C. & Jess, I. (2012). Acta Cryst. E68, o2581.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Silva, M. J., Alves, A. J. & Nascimento, S. C. (1998). Il Farmaco, 53, 241–243.

Stoe & Cie (2008). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.