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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2685.
Published online 2010 September 30. doi:  10.1107/S1600536810038389
PMCID: PMC2983114

1-(3,4-Dimethyl­benzyl­idene)-4-ethyl­thio­semicarbazide

Abstract

The title compound, C12H17N3S, was prepared by the reaction of 4-ethyl­thio­semicarbazide and 3,4-dimethyl­benzaldehyde. The dihedral angle between the thiourea unit and the benzene ring is 7.09 (8)°. In the crystal, inversion dimers linked by pairs of N—H(...)S hydrogen bonds occur.

Related literature

For applications of Schiff base compounds, see: Casas et al. (2000 [triangle]); Habermehl et al. (2006 [triangle]). For the structure of 4-ethyl-1-(4-methyl­benzyl­idene)thio­semicarbazide, see: Li & Jian (2010 [triangle]).

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Object name is e-66-o2685-scheme1.jpg

Experimental

Crystal data

  • C12H17N3S
  • M r = 235.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2685-efi1.jpg
  • a = 8.6659 (17) Å
  • b = 15.207 (3) Å
  • c = 9.993 (2) Å
  • β = 93.47 (3)°
  • V = 1314.5 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 293 K
  • 0.22 × 0.20 × 0.18 mm

Data collection

  • Bruker SMART CCD diffractometer
  • 12215 measured reflections
  • 3006 independent reflections
  • 2429 reflections with I > 2σ(I)
  • R int = 0.056

Refinement

  • R[F 2 > 2σ(F 2)] = 0.065
  • wR(F 2) = 0.206
  • S = 1.05
  • 3006 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810038389/lh5136sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038389/lh5136Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Schiff-bases have attracted attention because they can be utilized as effective ligands in coordination chemistry (Casas et al., 2000). They are important intermediates which have been reported to form chiral coordination compounds with many interesting properties (Habermehl et al., 2006). As part of our research on new Schiff-base compounds we synthesized the title compound (I), and have determined its crystal structure. The molecular structure is shown in Fig. 1. The dihedral angle between the benzene ring and the thiourea unit is 7.09 (8)°. The bond lengths and angles agree with those observed in 4-Ethyl-1-(4-methylbenzylidene)thiosemicarbazide (Li & Jian, 2010). In the crystal structure, centrosymmetric dimers are formed by pairs of intermolecular N—H···S hydrogen bonds.

Experimental

A mixture of the 4-ethylthiosemicarbazide (0.1 mol) and 3,4-dimethylbenzaldehyde (0.1 mol) was stirred in refluxing ethanol (30 mL) for 2 h to afford the title compound (0.085 mol, yield 85%). Single crystals suitable for X-ray measurements were obtained by recrystallization of a solution of the title compound in ethanol at room temperature.

Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93-0.97 Å; N-H = 0.86Å, and with Uiso = 1.2Ueq(C,N) or 1.2Ueq(Cmethyl).

Figures

Fig. 1.
The molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C12H17N3SF(000) = 504
Mr = 235.35Dx = 1.189 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2429 reflections
a = 8.6659 (17) Åθ = 3.3–27.5°
b = 15.207 (3) ŵ = 0.23 mm1
c = 9.993 (2) ÅT = 293 K
β = 93.47 (3)°Block, colorless
V = 1314.5 (5) Å30.22 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer2429 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
graphiteθmax = 27.5°, θmin = 3.3°
[var phi] and ω scansh = −11→11
12215 measured reflectionsk = −19→19
3006 independent reflectionsl = −12→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.206H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.1293P)2 + 0.2681P] where P = (Fo2 + 2Fc2)/3
3006 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.34 e Å3

Special details

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)

xyzUiso*/Ueq
S10.84996 (8)0.11266 (4)0.92188 (6)0.0702 (3)
N11.02915 (18)0.11306 (10)1.28935 (16)0.0480 (4)
N20.9879 (2)0.08927 (11)1.15935 (16)0.0532 (4)
H2A1.02350.04151.12690.064*
C91.1228 (2)0.06157 (13)1.35388 (19)0.0513 (4)
H9A1.15740.01151.31140.062*
N30.8377 (2)0.21192 (12)1.14109 (18)0.0581 (4)
H3A0.86300.21931.22490.070*
C41.1328 (3)0.15253 (16)1.5627 (2)0.0597 (5)
H4A1.06910.19471.52060.072*
C81.2782 (2)0.01920 (13)1.5576 (2)0.0544 (5)
H8A1.3120−0.02931.51080.065*
C31.1773 (2)0.07867 (13)1.49181 (19)0.0487 (4)
C100.8916 (2)0.14075 (13)1.08270 (19)0.0485 (4)
C71.3299 (2)0.03031 (14)1.6911 (2)0.0571 (5)
C61.2793 (3)0.10241 (17)1.7607 (2)0.0644 (6)
C51.1829 (3)0.16286 (18)1.6946 (2)0.0708 (6)
H5A1.15110.21201.74090.085*
C21.4415 (3)−0.0353 (2)1.7562 (3)0.0837 (8)
H2B1.4651−0.01881.84800.126*
H2C1.5348−0.03601.70920.126*
H2D1.3956−0.09271.75300.126*
C120.5844 (3)0.2822 (2)1.1272 (4)0.0950 (9)
H12A0.52390.32651.08000.143*
H12B0.59350.29631.22100.143*
H12C0.53480.22611.11490.143*
C110.7391 (3)0.27866 (18)1.0749 (3)0.0787 (7)
H11A0.72890.26630.97960.094*
H11B0.78810.33571.08680.094*
C11.3292 (4)0.1167 (3)1.9069 (3)0.0973 (11)
H1B1.28320.16981.93800.146*
H1C1.43970.12161.91660.146*
H1D1.29620.06791.95890.146*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0834 (5)0.0734 (4)0.0509 (4)0.0196 (3)−0.0188 (3)−0.0005 (2)
N10.0472 (8)0.0524 (8)0.0437 (8)0.0018 (6)−0.0027 (6)0.0016 (6)
N20.0575 (9)0.0541 (8)0.0464 (8)0.0123 (7)−0.0088 (7)−0.0005 (7)
C90.0536 (10)0.0496 (9)0.0496 (10)0.0050 (7)−0.0049 (8)0.0006 (8)
N30.0575 (9)0.0611 (10)0.0554 (9)0.0163 (8)0.0018 (7)0.0074 (7)
C40.0582 (11)0.0668 (13)0.0535 (11)0.0141 (9)−0.0015 (8)−0.0024 (9)
C80.0552 (10)0.0493 (9)0.0572 (11)−0.0028 (8)−0.0075 (8)0.0059 (8)
C30.0461 (9)0.0515 (9)0.0481 (9)−0.0020 (7)−0.0019 (7)0.0045 (8)
C100.0414 (9)0.0526 (9)0.0510 (10)0.0036 (7)−0.0019 (7)0.0086 (8)
C70.0505 (10)0.0641 (11)0.0554 (11)−0.0114 (8)−0.0088 (8)0.0156 (9)
C60.0523 (11)0.0943 (16)0.0459 (11)−0.0092 (10)−0.0025 (8)0.0010 (10)
C50.0677 (14)0.0861 (16)0.0580 (12)0.0112 (11)0.0003 (10)−0.0162 (11)
C20.0802 (16)0.0911 (18)0.0768 (16)0.0046 (13)−0.0208 (13)0.0262 (14)
C120.0636 (15)0.0908 (19)0.128 (3)0.0270 (14)−0.0117 (15)−0.0062 (18)
C110.0817 (16)0.0739 (15)0.0810 (16)0.0347 (13)0.0081 (12)0.0185 (12)
C10.089 (2)0.150 (3)0.0508 (14)−0.0023 (18)−0.0132 (13)−0.0072 (15)

Geometric parameters (Å, °)

S1—C101.681 (2)C7—C21.509 (3)
N1—C91.275 (2)C6—C51.383 (3)
N1—N21.375 (2)C6—C11.514 (3)
N2—C101.349 (2)C5—H5A0.9300
N2—H2A0.8600C2—H2B0.9600
C9—C31.453 (3)C2—H2C0.9600
C9—H9A0.9300C2—H2D0.9600
N3—C101.328 (3)C12—C111.468 (4)
N3—C111.459 (3)C12—H12A0.9600
N3—H3A0.8600C12—H12B0.9600
C4—C51.371 (3)C12—H12C0.9600
C4—C31.395 (3)C11—H11A0.9700
C4—H4A0.9300C11—H11B0.9700
C8—C71.392 (3)C1—H1B0.9600
C8—C31.395 (3)C1—H1C0.9600
C8—H8A0.9300C1—H1D0.9600
C7—C61.384 (3)
C9—N1—N2115.95 (16)C4—C5—C6122.0 (2)
C10—N2—N1120.03 (16)C4—C5—H5A119.0
C10—N2—H2A120.0C6—C5—H5A119.0
N1—N2—H2A120.0C7—C2—H2B109.5
N1—C9—C3122.03 (18)C7—C2—H2C109.5
N1—C9—H9A119.0H2B—C2—H2C109.5
C3—C9—H9A119.0C7—C2—H2D109.5
C10—N3—C11125.4 (2)H2B—C2—H2D109.5
C10—N3—H3A117.3H2C—C2—H2D109.5
C11—N3—H3A117.3C11—C12—H12A109.5
C5—C4—C3119.9 (2)C11—C12—H12B109.5
C5—C4—H4A120.0H12A—C12—H12B109.5
C3—C4—H4A120.0C11—C12—H12C109.5
C7—C8—C3121.9 (2)H12A—C12—H12C109.5
C7—C8—H8A119.0H12B—C12—H12C109.5
C3—C8—H8A119.0N3—C11—C12112.7 (2)
C8—C3—C4117.90 (18)N3—C11—H11A109.0
C8—C3—C9119.30 (18)C12—C11—H11A109.0
C4—C3—C9122.80 (18)N3—C11—H11B109.0
N3—C10—N2116.46 (17)C12—C11—H11B109.0
N3—C10—S1124.51 (14)H11A—C11—H11B107.8
N2—C10—S1119.02 (15)C6—C1—H1B109.5
C6—C7—C8119.00 (19)C6—C1—H1C109.5
C6—C7—C2121.4 (2)H1B—C1—H1C109.5
C8—C7—C2119.6 (2)C6—C1—H1D109.5
C5—C6—C7119.1 (2)H1B—C1—H1D109.5
C5—C6—C1119.6 (2)H1C—C1—H1D109.5
C7—C6—C1121.2 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···S1i0.862.653.4929 (18)168

Symmetry codes: (i) −x+2, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5136).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Casas, J. S., Garcia-Tasende, M. S. & Sordo, J. (2000). Coord. Chem. Rev.209, 197–261.
  • Habermehl, N. C., Angus, P. M. & Kilah, N. L. (2006). Inorg. Chem.45, 1445–1462. [PubMed]
  • Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1399. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography