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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2853.
Published online 2010 October 20. doi:  10.1107/S1600536810040663
PMCID: PMC3009006

4-Methyl-1-(4-methylbenzylidene)thio­semicarbazide

Abstract

The title compound, C10H13N3S, prepared by the reaction of 4-methyl­benzaldehyde and 4-methyl­thio­semicarbazide, is approximately planar (r.m.s. deviation for the non-H atoms = 0.032 Å). Its conformation is stabilized by an intra­molecular N—H(...)N hydrogen bond, generating an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H(...)S hydrogen bonds occur. Further weak N—H(...)S links connect the dimers into (100) sheets.

Related literature

For related structures, see: Li & Jian (2010 [triangle]); Li et al. (2009 [triangle]).

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Object name is e-66-o2853-scheme1.jpg

Experimental

Crystal data

  • C10H13N3S
  • M r = 207.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2853-efi1.jpg
  • a = 9.1139 (18) Å
  • b = 13.689 (3) Å
  • c = 9.1195 (18) Å
  • β = 91.92 (3)°
  • V = 1137.1 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 293 K
  • 0.25 × 0.23 × 0.20 mm

Data collection

  • Bruker SMART CCD diffractometer
  • 10620 measured reflections
  • 2585 independent reflections
  • 1739 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.146
  • S = 1.14
  • 2585 reflections
  • 127 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.19 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/S1600536810040663/hb5666sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040663/hb5666Isup2.hkl

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

supplementary crystallographic information

Experimental

A mixture of the 4-methylbenzaldehyde (0.10 mol) and 4-methylthiosemicarbazide (0.10 mol) was stirred in refluxing ethanol (10 mL) for 4 h to afford the title compound (0.078 mol, yield 78%). Colourless bars of (I) were obtained by recrystallization from 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(H) = 1.2Ueq(C,N) or 1.5Ueq(Cmethyl).

Figures

Fig. 1.
The structure of (I) showing 30% probability displacement ellipsoids.

Crystal data

C10H13N3SF(000) = 440
Mr = 207.29Dx = 1.211 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1840 reflections
a = 9.1139 (18) Åθ = 3.3–25.2°
b = 13.689 (3) ŵ = 0.25 mm1
c = 9.1195 (18) ÅT = 293 K
β = 91.92 (3)°Bar, colorless
V = 1137.1 (4) Å30.25 × 0.23 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer1739 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
graphiteθmax = 27.5°, θmin = 3.5°
phi and ω scansh = −11→11
10620 measured reflectionsk = −16→17
2585 independent reflectionsl = −11→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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0782P)2 + 0.0376P] where P = (Fo2 + 2Fc2)/3
2585 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.19 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
S10.32325 (7)0.10479 (4)1.03876 (5)0.0635 (2)
N30.52576 (18)0.10902 (11)0.66835 (16)0.0500 (4)
N20.48287 (19)0.08528 (11)0.80716 (16)0.0546 (4)
H2A0.52760.03960.85550.065*
N10.30549 (18)0.20245 (12)0.78748 (16)0.0577 (4)
H1A0.33750.21390.70150.069*
C20.3712 (2)0.13330 (14)0.86754 (17)0.0480 (4)
C40.6920 (2)0.08023 (14)0.47593 (18)0.0484 (4)
C70.8095 (2)0.11507 (15)0.1996 (2)0.0549 (5)
C30.6335 (2)0.06052 (14)0.6196 (2)0.0536 (5)
H3B0.67570.01130.67740.064*
C90.6309 (2)0.14953 (15)0.3821 (2)0.0603 (5)
H9A0.54960.18510.41030.072*
C50.8110 (2)0.02762 (16)0.4281 (2)0.0612 (5)
H5A0.8527−0.02040.48830.073*
C60.8688 (2)0.04527 (18)0.2926 (2)0.0656 (6)
H6A0.94930.00930.26360.079*
C80.6893 (3)0.16642 (16)0.2469 (2)0.0640 (6)
H8A0.64670.21370.18590.077*
C100.8716 (3)0.1343 (2)0.0510 (2)0.0766 (7)
H10A0.95420.09210.03700.115*
H10B0.90260.20120.04540.115*
H10C0.79760.1217−0.02400.115*
C10.1832 (3)0.2597 (2)0.8363 (3)0.0953 (10)
H1B0.15370.30530.76110.143*
H1C0.21210.29460.92390.143*
H1D0.10260.21710.85640.143*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0813 (4)0.0682 (4)0.0421 (3)0.0139 (3)0.0186 (2)0.00603 (19)
N30.0541 (10)0.0515 (9)0.0452 (8)−0.0020 (7)0.0137 (7)0.0010 (6)
N20.0613 (11)0.0587 (9)0.0444 (8)0.0068 (8)0.0135 (7)0.0048 (6)
N10.0608 (11)0.0644 (10)0.0491 (8)0.0117 (8)0.0193 (7)0.0127 (7)
C20.0525 (11)0.0490 (10)0.0430 (9)−0.0033 (8)0.0081 (7)−0.0011 (7)
C40.0456 (11)0.0519 (10)0.0481 (10)−0.0013 (8)0.0075 (7)−0.0004 (7)
C70.0503 (12)0.0649 (12)0.0501 (10)−0.0083 (9)0.0095 (8)0.0013 (8)
C30.0548 (12)0.0547 (11)0.0517 (10)0.0023 (9)0.0086 (8)0.0040 (8)
C90.0606 (14)0.0608 (13)0.0605 (12)0.0157 (10)0.0146 (9)0.0079 (9)
C50.0540 (13)0.0715 (13)0.0586 (11)0.0135 (10)0.0102 (8)0.0107 (9)
C60.0510 (13)0.0826 (15)0.0644 (12)0.0124 (10)0.0180 (9)0.0041 (10)
C80.0682 (15)0.0639 (13)0.0603 (11)0.0094 (10)0.0104 (9)0.0147 (9)
C100.0778 (17)0.0945 (17)0.0587 (13)−0.0095 (14)0.0226 (11)0.0069 (11)
C10.096 (2)0.108 (2)0.0849 (16)0.0483 (16)0.0451 (14)0.0415 (14)

Geometric parameters (Å, °)

S1—C21.6813 (17)C3—H3B0.9300
N3—C31.277 (2)C9—C81.378 (3)
N3—N21.376 (2)C9—H9A0.9300
N2—C21.345 (2)C5—C61.381 (3)
N2—H2A0.8600C5—H5A0.9300
N1—C21.326 (2)C6—H6A0.9300
N1—C11.444 (3)C8—H8A0.9300
N1—H1A0.8600C10—H10A0.9600
C4—C91.382 (3)C10—H10B0.9600
C4—C51.385 (3)C10—H10C0.9600
C4—C31.456 (2)C1—H1B0.9600
C7—C61.376 (3)C1—H1C0.9600
C7—C81.383 (3)C1—H1D0.9600
C7—C101.509 (2)
C3—N3—N2116.28 (16)C6—C5—C4121.15 (18)
C2—N2—N3120.22 (16)C6—C5—H5A119.4
C2—N2—H2A119.9C4—C5—H5A119.4
N3—N2—H2A119.9C7—C6—C5121.32 (19)
C2—N1—C1123.79 (16)C7—C6—H6A119.3
C2—N1—H1A118.1C5—C6—H6A119.3
C1—N1—H1A118.1C9—C8—C7121.85 (19)
N1—C2—N2117.22 (15)C9—C8—H8A119.1
N1—C2—S1123.41 (14)C7—C8—H8A119.1
N2—C2—S1119.37 (14)C7—C10—H10A109.5
C9—C4—C5117.71 (17)C7—C10—H10B109.5
C9—C4—C3122.18 (17)H10A—C10—H10B109.5
C5—C4—C3120.09 (17)C7—C10—H10C109.5
C6—C7—C8117.33 (18)H10A—C10—H10C109.5
C6—C7—C10121.6 (2)H10B—C10—H10C109.5
C8—C7—C10121.1 (2)N1—C1—H1B109.5
N3—C3—C4121.71 (18)N1—C1—H1C109.5
N3—C3—H3B119.1H1B—C1—H1C109.5
C4—C3—H3B119.1N1—C1—H1D109.5
C8—C9—C4120.63 (18)H1B—C1—H1D109.5
C8—C9—H9A119.7H1C—C1—H1D109.5
C4—C9—H9A119.7

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···N30.862.272.644 (2)107
N1—H1A···S1i0.862.893.4869 (16)128
N2—H2A···S1ii0.862.573.4205 (18)171

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5666).

References

  • Bruker (1997). SMART and SAINT Bruker AXS, Inc., Madison, Wisconsin, USA.
  • Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1397. [PMC free article] [PubMed]
  • Li, Y.-F., Liu, H.-X. & Jian, F.-F. (2009). Acta Cryst. E65, o2959. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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