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

Li, Y.-F.

doi:10.1107/S1600536810040663

organic compounds

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

Yu-Feng Li ^a ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 30 September 2010; accepted 11 October 2010; online 20 October 2010)

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 ); Li et al. (2009 ).

Experimental

Crystal data

C₁₀H₁₃N₃S
M_r = 207.29
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.044
wR(F²) = 0.146
S = 1.14
2585 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N3	0.86	2.27	2.644 (2)	107
N1—H1A⋯S1ⁱ	0.86	2.89	3.4869 (16)	128
N2—H2A⋯S1ⁱⁱ	0.86	2.57	3.4205 (18)	171
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+2.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810040663/hb5666sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040663/hb5666Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

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

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

Crystal data top

C₁₀H₁₃N₃S	F(000) = 440
M_r = 207.29	D_x = 1.211 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1840 reflections
a = 9.1139 (18) Å	θ = 3.3–25.2°
b = 13.689 (3) Å	µ = 0.25 mm⁻¹
c = 9.1195 (18) Å	T = 293 K
β = 91.92 (3)°	Bar, colorless
V = 1137.1 (4) Å³	0.25 × 0.23 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1739 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 27.5°, θ_min = 3.5°
phi and ω scans	h = −11→11
10620 measured reflections	k = −16→17
2585 independent reflections	l = −11→11

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0782P)² + 0.0376P] where P = (F_o² + 2F_c²)/3
2585 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₀H₁₃N₃S	V = 1137.1 (4) Å³
M_r = 207.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1139 (18) Å	µ = 0.25 mm⁻¹
b = 13.689 (3) Å	T = 293 K
c = 9.1195 (18) Å	0.25 × 0.23 × 0.20 mm
β = 91.92 (3)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.14	Δρ_max = 0.28 e Å⁻³
2585 reflections	Δρ_min = −0.19 e Å⁻³
127 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	U_iso*/U_eq
S1	0.32325 (7)	0.10479 (4)	1.03876 (5)	0.0635 (2)
N3	0.52576 (18)	0.10902 (11)	0.66835 (16)	0.0500 (4)
N2	0.48287 (19)	0.08528 (11)	0.80716 (16)	0.0546 (4)
H2A	0.5276	0.0396	0.8555	0.065*
N1	0.30549 (18)	0.20245 (12)	0.78748 (16)	0.0577 (4)
H1A	0.3375	0.2139	0.7015	0.069*
C2	0.3712 (2)	0.13330 (14)	0.86754 (17)	0.0480 (4)
C4	0.6920 (2)	0.08023 (14)	0.47593 (18)	0.0484 (4)
C7	0.8095 (2)	0.11507 (15)	0.1996 (2)	0.0549 (5)
C3	0.6335 (2)	0.06052 (14)	0.6196 (2)	0.0536 (5)
H3B	0.6757	0.0113	0.6774	0.064*
C9	0.6309 (2)	0.14953 (15)	0.3821 (2)	0.0603 (5)
H9A	0.5496	0.1851	0.4103	0.072*
C5	0.8110 (2)	0.02762 (16)	0.4281 (2)	0.0612 (5)
H5A	0.8527	−0.0204	0.4883	0.073*
C6	0.8688 (2)	0.04527 (18)	0.2926 (2)	0.0656 (6)
H6A	0.9493	0.0093	0.2636	0.079*
C8	0.6893 (3)	0.16642 (16)	0.2469 (2)	0.0640 (6)
H8A	0.6467	0.2137	0.1859	0.077*
C10	0.8716 (3)	0.1343 (2)	0.0510 (2)	0.0766 (7)
H10A	0.9542	0.0921	0.0370	0.115*
H10B	0.9026	0.2012	0.0454	0.115*
H10C	0.7976	0.1217	−0.0240	0.115*
C1	0.1832 (3)	0.2597 (2)	0.8363 (3)	0.0953 (10)
H1B	0.1537	0.3053	0.7611	0.143*
H1C	0.2121	0.2946	0.9239	0.143*
H1D	0.1026	0.2171	0.8564	0.143*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0813 (4)	0.0682 (4)	0.0421 (3)	0.0139 (3)	0.0186 (2)	0.00603 (19)
N3	0.0541 (10)	0.0515 (9)	0.0452 (8)	−0.0020 (7)	0.0137 (7)	0.0010 (6)
N2	0.0613 (11)	0.0587 (9)	0.0444 (8)	0.0068 (8)	0.0135 (7)	0.0048 (6)
N1	0.0608 (11)	0.0644 (10)	0.0491 (8)	0.0117 (8)	0.0193 (7)	0.0127 (7)
C2	0.0525 (11)	0.0490 (10)	0.0430 (9)	−0.0033 (8)	0.0081 (7)	−0.0011 (7)
C4	0.0456 (11)	0.0519 (10)	0.0481 (10)	−0.0013 (8)	0.0075 (7)	−0.0004 (7)
C7	0.0503 (12)	0.0649 (12)	0.0501 (10)	−0.0083 (9)	0.0095 (8)	0.0013 (8)
C3	0.0548 (12)	0.0547 (11)	0.0517 (10)	0.0023 (9)	0.0086 (8)	0.0040 (8)
C9	0.0606 (14)	0.0608 (13)	0.0605 (12)	0.0157 (10)	0.0146 (9)	0.0079 (9)
C5	0.0540 (13)	0.0715 (13)	0.0586 (11)	0.0135 (10)	0.0102 (8)	0.0107 (9)
C6	0.0510 (13)	0.0826 (15)	0.0644 (12)	0.0124 (10)	0.0180 (9)	0.0041 (10)
C8	0.0682 (15)	0.0639 (13)	0.0603 (11)	0.0094 (10)	0.0104 (9)	0.0147 (9)
C10	0.0778 (17)	0.0945 (17)	0.0587 (13)	−0.0095 (14)	0.0226 (11)	0.0069 (11)
C1	0.096 (2)	0.108 (2)	0.0849 (16)	0.0483 (16)	0.0451 (14)	0.0415 (14)

Geometric parameters (Å, º) top

S1—C2	1.6813 (17)	C3—H3B	0.9300
N3—C3	1.277 (2)	C9—C8	1.378 (3)
N3—N2	1.376 (2)	C9—H9A	0.9300
N2—C2	1.345 (2)	C5—C6	1.381 (3)
N2—H2A	0.8600	C5—H5A	0.9300
N1—C2	1.326 (2)	C6—H6A	0.9300
N1—C1	1.444 (3)	C8—H8A	0.9300
N1—H1A	0.8600	C10—H10A	0.9600
C4—C9	1.382 (3)	C10—H10B	0.9600
C4—C5	1.385 (3)	C10—H10C	0.9600
C4—C3	1.456 (2)	C1—H1B	0.9600
C7—C6	1.376 (3)	C1—H1C	0.9600
C7—C8	1.383 (3)	C1—H1D	0.9600
C7—C10	1.509 (2)

C3—N3—N2	116.28 (16)	C6—C5—C4	121.15 (18)
C2—N2—N3	120.22 (16)	C6—C5—H5A	119.4
C2—N2—H2A	119.9	C4—C5—H5A	119.4
N3—N2—H2A	119.9	C7—C6—C5	121.32 (19)
C2—N1—C1	123.79 (16)	C7—C6—H6A	119.3
C2—N1—H1A	118.1	C5—C6—H6A	119.3
C1—N1—H1A	118.1	C9—C8—C7	121.85 (19)
N1—C2—N2	117.22 (15)	C9—C8—H8A	119.1
N1—C2—S1	123.41 (14)	C7—C8—H8A	119.1
N2—C2—S1	119.37 (14)	C7—C10—H10A	109.5
C9—C4—C5	117.71 (17)	C7—C10—H10B	109.5
C9—C4—C3	122.18 (17)	H10A—C10—H10B	109.5
C5—C4—C3	120.09 (17)	C7—C10—H10C	109.5
C6—C7—C8	117.33 (18)	H10A—C10—H10C	109.5
C6—C7—C10	121.6 (2)	H10B—C10—H10C	109.5
C8—C7—C10	121.1 (2)	N1—C1—H1B	109.5
N3—C3—C4	121.71 (18)	N1—C1—H1C	109.5
N3—C3—H3B	119.1	H1B—C1—H1C	109.5
C4—C3—H3B	119.1	N1—C1—H1D	109.5
C8—C9—C4	120.63 (18)	H1B—C1—H1D	109.5
C8—C9—H9A	119.7	H1C—C1—H1D	109.5
C4—C9—H9A	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.86	2.27	2.644 (2)	107
N1—H1A···S1ⁱ	0.86	2.89	3.4869 (16)	128
N2—H2A···S1ⁱⁱ	0.86	2.57	3.4205 (18)	171

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃S
M_r	207.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.1139 (18), 13.689 (3), 9.1195 (18)
β (°)	91.92 (3)
V (Å³)	1137.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.25 × 0.23 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10620, 2585, 1739
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.146, 1.14
No. of reflections	2585
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.19

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.86	2.27	2.644 (2)	107
N1—H1A···S1ⁱ	0.86	2.89	3.4869 (16)	128
N2—H2A···S1ⁱⁱ	0.86	2.57	3.4205 (18)	171

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

References

Bruker (1997). SMART and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1397. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, Y.-F., Liu, H.-X. & Jian, F.-F. (2009). Acta Cryst. E65, o2959. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2853

https://doi.org/10.1107/S1600536810040663

Open

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