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In the title compound, C12H15N3O2S, the 1,3-benzdioxole fragment is nearly planar [the maximum deviation being 0.0515 (14) Å], the N—N—C(=S)—N fragment is also nearly planar [the maximum deviation being 0.0480 (10) Å], and the dihedral angle between their mean planes is 23.49 (10)°. In the crystal, mol­ecules are linked by pairs of N—H...S hydrogen bonds, forming inversion dimers. The dimers are stacked along the a axis with neighbouring columns having the same direction; however, the mol­ecules show different orientations leading to a centrosymmetric arrangement. In the crystal, the methyl­ene group of the ethyl substituent and the terminal methyl H atoms are disordered over two sets of sites and were refined using a split model with an occupancy ratio of 0.5:0.5.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015003837/xu5837sup1.cif
Contains datablocks I, publication_text

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989015003837/xu5837Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015003837/xu5837Isup3.cml
Supplementary material

CCDC reference: 1051034

Key indicators

  • Single-crystal X-ray study
  • T = 250 K
  • Mean [sigma](C-C) = 0.002 Å
  • Disorder in main residue
  • R factor = 0.039
  • wR factor = 0.116
  • Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 -- C10 .. 6.6 su PLAT234_ALERT_4_C Large Hirshfeld Difference C11 -- C12 .. 0.16 Ang. PLAT241_ALERT_2_C High Ueq as Compared to Neighbors for ..... C12 Check PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 3.529 Check PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 8 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 6 Note
Alert level G PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 Report PLAT154_ALERT_1_G The su's on the Cell Angles are Equal .......... 0.00500 Degree PLAT230_ALERT_2_G Hirshfeld Test Diff for C11' -- C12 .. 6.0 su PLAT300_ALERT_4_G Atom Site Occupancy of *C11 is Constrained at 0.500 Check PLAT300_ALERT_4_G Atom Site Occupancy of *C11' is Constrained at 0.500 Check PLAT301_ALERT_3_G Main Residue Disorder ............ Percentage = 6 Note PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 2 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 6 ALERT level C = Check. Ensure it is not caused by an omission or oversight 7 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Structural commentary top

Concerning our inter­est and on going research on thio­semicarbazone derivatives from natural products, we report herein the synthesis and crystal structure of 1-(2H-1,3-benzodioxol-5-yl)ethanone 4-ethyl­thio­semicarbazide. The carbonyl­ated precursor is a secondary metabolite from Amazonian Magnoliid trees that belong to the Lauraceae family, the Aniba rosaeodora, (Mors et al., 1957).

The molecular structure of the title compound, which matches the asymmetric unit, is not planar [the mean deviation from planarity for non-H atoms, and excluding the disordered C11/C11' entity, amounts to 0.3794 (17) Å for C5]. The maximum deviation from the mean plane of the non-H atoms of the 1,3-benzodioxole fragment amounts to 0.0515 (14) Å for C7 and for the N1/N2/C10/S1/N3 fragment amounts 0.0480 (10) Å for N2, with the dihedral angle between the planes being 23.49 (10)°.

In the crystal, the molecules are connected by pairs of N2—H1N2···S1 inter­molecular hydrogen bonds building dimers. The dimers are stacked along a-axis and although the neighbour columns have the same direction, the dimeric units show different orientations leading to a centrosymmetric structure (Figure 2 and Table 1).

Synthesis and crystallization top

Starting materials are commercially available and were used without further purification. The synthesis of the title compound was adapted from a previously procedure (Freund & Schander, 1902). In a hydro­chloric acid catalized reaction, a mixture of 3',4'-(methyl­ene­dioxy)­aceto­phenone (10 mmol) and 4-ethyl-3-thio­semicarbazide (10 mmol) in ethanol (80 mL) was refluxed for 4 h. After cooling and filtering, the title compound was obtained. Colourless crystal grown in DMSO by the slow evaporation of the solvent.

Refinement top

The C—H H atoms were positioned with idealized geometry (methyl H atoms were allowed to rotate but not to tip) and refined isotropic with Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms) using a riding model with C—H = 0.94 Å for aromatic, C—H = 0.98 Å for methyl­ene and C—H = 0.97 Å for methyl H atoms. The N—H H atoms were located in a difference map and were refined isotropic with varying coordinates in the beginning. Finally, the N—H distances were set to ideal values of 0.87 Å and they were refined isotropic with Uiso(H) = 1.2Ueq(N) using a riding model. The methyl­ene C atom C11 is disordered in two orientations and were refined using a split model with occupancy of 0.5:0.5.

Related literature top

For one of the first reports of the synthesis of thiosemicarbazone derivatives, see: Freund & Schander (1902). For one of the first reports of 3',4'-(methylenedioxy)acetophenone extraction from the South American Aniba rosaeodora tree, see: Mors et al. (1957). For the crystal structures of two derivatives of the title compound, see: Oliveira et al. (2013, 2015).

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: SHELXL2013-2 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level. Disorder is shown with full and open bonds.
[Figure 2] Fig. 2. Crystal structure of the title compound with hydrogen bonding shown as dashed lines (see Table 1 for details). Disordered atoms are not shown for clarity.
(E)-2-[1-(Benzo[d][1,3]dioxol-5-yl)ethylidene]-N-ethylhydrazine-1-carbothioamide top
Crystal data top
C12H15N3O2SZ = 2
Mr = 265.33F(000) = 280
Triclinic, P1Dx = 1.371 Mg m3
a = 5.7207 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.6225 (6) ÅCell parameters from 9389 reflections
c = 10.8103 (6) Åθ = 1.9–27.0°
α = 83.908 (5)°µ = 0.25 mm1
β = 79.913 (5)°T = 250 K
γ = 87.029 (5)°Parallelepiped, colourless
V = 642.74 (6) Å30.15 × 0.15 × 0.10 mm
Data collection top
Stoe IPDS-1
diffractometer
2288 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Stoe IPDS-1Rint = 0.042
Graphite monochromatorθmax = 27.0°, θmin = 1.9°
ϕ scansh = 77
9389 measured reflectionsk = 1313
2811 independent reflectionsl = 1313
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0649P)2 + 0.1118P]
where P = (Fo2 + 2Fc2)/3
2811 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C12H15N3O2Sγ = 87.029 (5)°
Mr = 265.33V = 642.74 (6) Å3
Triclinic, P1Z = 2
a = 5.7207 (3) ÅMo Kα radiation
b = 10.6225 (6) ŵ = 0.25 mm1
c = 10.8103 (6) ÅT = 250 K
α = 83.908 (5)°0.15 × 0.15 × 0.10 mm
β = 79.913 (5)°
Data collection top
Stoe IPDS-1
diffractometer
2288 reflections with I > 2σ(I)
9389 measured reflectionsRint = 0.042
2811 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.03Δρmax = 0.28 e Å3
2811 reflectionsΔρmin = 0.23 e Å3
173 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*/UeqOcc. (<1)
C10.7435 (3)0.18956 (14)0.16339 (15)0.0407 (3)
C20.8619 (3)0.24715 (14)0.24537 (15)0.0428 (3)
H20.83520.33340.25750.051*
C31.0167 (3)0.17309 (16)0.30646 (16)0.0457 (4)
C41.0618 (3)0.04644 (16)0.28893 (17)0.0516 (4)
C50.9543 (4)0.01187 (16)0.20857 (19)0.0581 (5)
H50.98630.09770.19620.070*
C60.7937 (3)0.06224 (16)0.14522 (17)0.0515 (4)
H60.71740.02500.08870.062*
O11.1441 (2)0.20752 (13)0.39317 (13)0.0621 (4)
C71.2882 (3)0.0980 (2)0.4229 (2)0.0615 (5)
H7A1.45620.11480.39170.074*
H7B1.26680.07710.51460.074*
O21.2191 (3)0.00457 (13)0.36476 (15)0.0698 (4)
C80.5558 (3)0.26302 (14)0.10543 (15)0.0407 (3)
C90.4637 (3)0.21798 (17)0.00254 (18)0.0541 (4)
H9A0.31160.17940.02800.081*
H9B0.57550.15600.04150.081*
H9C0.44400.28920.06430.081*
N10.4771 (2)0.36261 (12)0.15902 (13)0.0420 (3)
N20.2949 (2)0.43540 (12)0.11811 (13)0.0432 (3)
H1N20.22340.42290.05600.052*
C100.2019 (3)0.53176 (15)0.18658 (16)0.0461 (4)
S10.03625 (8)0.61725 (4)0.15015 (5)0.05451 (17)
N30.3122 (3)0.55269 (18)0.27906 (18)0.0732 (5)
H1N30.43620.50270.28430.088*
C110.2171 (16)0.6290 (8)0.3858 (8)0.071 (2)0.5
H11A0.11380.69870.35760.085*0.5
H11B0.12320.57580.45440.085*0.5
C11'0.2731 (18)0.6716 (7)0.3447 (8)0.0675 (19)0.5
H11C0.29890.74470.28120.081*0.5
H11D0.10730.67660.38720.081*0.5
C120.4155 (6)0.6790 (3)0.4304 (3)0.1149 (12)
H12A0.56160.63530.39590.172*0.5
H12B0.39140.66630.52190.172*0.5
H12C0.42590.76890.40320.172*0.5
H12D0.49780.59800.44440.172*0.5
H12E0.32050.70070.50920.172*0.5
H12F0.53070.74380.39930.172*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0423 (7)0.0354 (7)0.0438 (8)0.0004 (6)0.0029 (6)0.0089 (6)
C20.0447 (8)0.0345 (7)0.0491 (8)0.0006 (6)0.0058 (6)0.0077 (6)
C30.0450 (8)0.0449 (8)0.0467 (8)0.0031 (6)0.0063 (6)0.0043 (6)
C40.0492 (9)0.0433 (9)0.0588 (10)0.0060 (7)0.0064 (7)0.0028 (7)
C50.0666 (11)0.0355 (8)0.0716 (12)0.0095 (7)0.0103 (9)0.0106 (8)
C60.0577 (10)0.0395 (8)0.0594 (10)0.0034 (7)0.0105 (8)0.0161 (7)
O10.0644 (8)0.0599 (8)0.0684 (8)0.0018 (6)0.0293 (7)0.0074 (6)
C70.0524 (10)0.0694 (12)0.0607 (11)0.0010 (9)0.0142 (8)0.0083 (9)
O20.0699 (9)0.0565 (8)0.0853 (10)0.0114 (6)0.0292 (7)0.0024 (7)
C80.0417 (7)0.0357 (7)0.0449 (8)0.0012 (6)0.0050 (6)0.0095 (6)
C90.0538 (9)0.0522 (10)0.0617 (10)0.0070 (7)0.0156 (8)0.0245 (8)
N10.0417 (6)0.0370 (6)0.0485 (7)0.0033 (5)0.0086 (5)0.0108 (5)
N20.0430 (7)0.0398 (7)0.0501 (7)0.0048 (5)0.0128 (5)0.0150 (5)
C100.0464 (8)0.0403 (8)0.0539 (9)0.0033 (6)0.0106 (7)0.0150 (7)
S10.0481 (2)0.0521 (3)0.0700 (3)0.01332 (18)0.02210 (19)0.0241 (2)
N30.0788 (11)0.0749 (11)0.0815 (11)0.0404 (9)0.0444 (9)0.0480 (9)
C110.070 (4)0.073 (5)0.081 (6)0.027 (4)0.029 (4)0.046 (4)
C11'0.087 (5)0.057 (4)0.068 (5)0.027 (3)0.032 (4)0.033 (3)
C120.109 (2)0.133 (3)0.122 (2)0.029 (2)0.0365 (19)0.089 (2)
Geometric parameters (Å, º) top
C1—C61.395 (2)N1—N21.3730 (18)
C1—C21.410 (2)N2—C101.358 (2)
C1—C81.483 (2)N2—H1N20.8699
C2—C31.364 (2)C10—N31.315 (2)
C2—H20.9400C10—S11.6792 (17)
C3—O11.372 (2)N3—C111.489 (9)
C3—C41.383 (2)N3—C11'1.501 (9)
C4—C51.363 (3)N3—H1N30.8700
C4—O21.375 (2)C11—C121.453 (10)
C5—C61.401 (3)C11—H11A0.9800
C5—H50.9400C11—H11B0.9800
C6—H60.9400C11'—C121.347 (10)
O1—C71.432 (2)C11'—H11C0.9800
C7—O21.420 (3)C11'—H11D0.9800
C7—H7A0.9800C12—H12A0.9700
C7—H7B0.9800C12—H12B0.9700
C8—N11.2832 (19)C12—H12C0.9700
C8—C91.493 (2)C12—H12D0.9700
C9—H9A0.9700C12—H12E0.9700
C9—H9B0.9700C12—H12F0.9700
C9—H9C0.9700
C6—C1—C2119.34 (15)C10—N2—N1117.50 (13)
C6—C1—C8121.30 (15)C10—N2—H1N2115.4
C2—C1—C8119.22 (13)N1—N2—H1N2126.9
C3—C2—C1117.54 (14)N3—C10—N2115.66 (15)
C3—C2—H2121.2N3—C10—S1123.92 (12)
C1—C2—H2121.2N2—C10—S1120.41 (13)
C2—C3—O1127.54 (15)C10—N3—C11126.2 (4)
C2—C3—C4122.40 (16)C10—N3—C11'123.1 (4)
O1—C3—C4110.05 (15)C10—N3—H1N3113.3
C5—C4—O2128.69 (16)C11—N3—H1N3119.0
C5—C4—C3121.73 (16)C11'—N3—H1N3121.5
O2—C4—C3109.57 (17)C12—C11—N3108.7 (6)
C4—C5—C6116.86 (15)C12—C11—H11A110.0
C4—C5—H5121.6N3—C11—H11A110.0
C6—C5—H5121.6C12—C11—H11B110.0
C1—C6—C5122.10 (17)N3—C11—H11B110.0
C1—C6—H6118.9H11A—C11—H11B108.3
C5—C6—H6118.9C12—C11'—N3114.0 (6)
C3—O1—C7105.38 (14)C12—C11'—H11C108.7
O2—C7—O1108.49 (15)N3—C11'—H11C108.7
O2—C7—H7A110.0C12—C11'—H11D108.7
O1—C7—H7A110.0N3—C11'—H11D108.7
O2—C7—H7B110.0H11C—C11'—H11D107.6
O1—C7—H7B110.0C11—C12—H12A109.5
H7A—C7—H7B108.4C11—C12—H12B109.5
C4—O2—C7105.90 (14)H12A—C12—H12B109.5
N1—C8—C1114.42 (14)C11—C12—H12C109.5
N1—C8—C9124.48 (15)H12A—C12—H12C109.5
C1—C8—C9121.04 (13)H12B—C12—H12C109.5
C8—C9—H9A109.5C11'—C12—H12D109.5
C8—C9—H9B109.5C11'—C12—H12E109.5
H9A—C9—H9B109.5H12D—C12—H12E109.5
C8—C9—H9C109.5C11'—C12—H12F109.5
H9A—C9—H9C109.5H12D—C12—H12F109.5
H9B—C9—H9C109.5H12E—C12—H12F109.5
C8—N1—N2120.07 (14)
C6—C1—C2—C31.9 (2)C6—C1—C8—N1159.25 (15)
C8—C1—C2—C3173.75 (14)C2—C1—C8—N116.3 (2)
C1—C2—C3—O1177.54 (15)C6—C1—C8—C918.1 (2)
C1—C2—C3—C41.0 (2)C2—C1—C8—C9166.30 (15)
C2—C3—C4—C50.3 (3)C1—C8—N1—N2176.84 (12)
O1—C3—C4—C5179.06 (16)C9—C8—N1—N20.4 (2)
C2—C3—C4—O2178.38 (15)C8—N1—N2—C10173.15 (14)
O1—C3—C4—O20.34 (19)N1—N2—C10—N36.2 (2)
O2—C4—C5—C6177.85 (17)N1—N2—C10—S1174.75 (11)
C3—C4—C5—C60.6 (3)N2—C10—N3—C11164.2 (4)
C2—C1—C6—C51.7 (3)S1—C10—N3—C1116.8 (5)
C8—C1—C6—C5173.86 (16)N2—C10—N3—C11'165.3 (4)
C4—C5—C6—C10.4 (3)S1—C10—N3—C11'13.8 (5)
C2—C3—O1—C7176.90 (16)C10—N3—C11—C12153.3 (4)
C4—C3—O1—C74.46 (18)C11'—N3—C11—C1261.3 (15)
C3—O1—C7—O27.55 (19)C10—N3—C11'—C12175.3 (4)
C5—C4—O2—C7176.35 (19)C11—N3—C11'—C1279.0 (15)
C3—C4—O2—C75.04 (19)N3—C11'—C12—C1173.0 (13)
O1—C7—O2—C47.8 (2)N3—C11—C12—C11'68.3 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···S1i0.872.723.5842 (14)175
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···S1i0.872.723.5842 (14)175.2
Symmetry code: (i) x, y+1, z.
 

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