1-(4-Meth­oxy­benzyl­idene)-4-methyl­thiosemicarbazide

Li, Y.-F.

doi:10.1107/S1600536810038882

organic compounds

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Volume 66| Part 11| November 2010| Page o2728

https://doi.org/10.1107/S1600536810038882

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1-(4-Methoxybenzylidene)-4-methylthiosemicarbazide

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 27 September 2010; accepted 29 September 2010; online 9 October 2010)

The title compound, C₁₀H₁₃N₃OS, was prepared by the reaction of 4-methoxybenzaldehyde and 4-methylthiosemicarbazide. The dihedral angle between the benzene ring and the thiourea unit is 8.64 (7)° and an intramolecular N—H⋯N hydrogen bond generates an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R₂²(8) loops. The dimers are linked into (001) sheets by further N—H⋯S links.

Related literature

For background to Schiff bases, see: Casas et al. (2000 ). For a related structure, see: Li & Jian (2010 ).

Experimental

Crystal data

C₁₀H₁₃N₃OS
M_r = 223.29
Orthorhombic, P b c a
a = 13.397 (3) Å
b = 9.1271 (18) Å
c = 18.799 (4) Å
V = 2298.6 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
20742 measured reflections
2627 independent reflections
1746 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.146
S = 0.94
2627 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.29 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	2.28	2.661 (2)	107
N1—H1A⋯S1ⁱ	0.86	2.86	3.4718 (18)	130
N2—H2A⋯S1ⁱⁱ	0.86	2.59	3.4359 (17)	169
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) -x+2, -y+2, -z+1.

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/S1600536810038882/hb5659sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810038882/hb5659Isup2.hkl

checkCIF report

Comment top

Schiff-base have attracted much attention because they can be utilized as effective ligands to be coordination compounds in coordination chemistry. (Casas et al., 2000). As part of our research for new Schiff-base compounds we synthesized the title compound (I), and describe its structure here. In the molecule structure, the dihedral angle between the benzene ring and the thiourea unit is [8.64 (7)°].

Bond lengths and angles agree with those observed in related compounds (Li & Jian, 2010).

Related literature top

For background to Schiff bases, see: Casas et al. (2000). For a related structure, see: Li & Jian (2010).

Experimental top

A mixture of 4-methylthiosemicarbazide (0.1 mol) and 4-methoxybenzaldehyde (0.1 mol) was stirred in refluxing ethanol (30 mL) for 2 h to afford the title compound (0.090 mol, yield 90%). Colourless bars of (I) were obtained by recrystallization from ethanol at room temperature.

Structure description top

Bond lengths and angles agree with those observed in related compounds (Li & Jian, 2010).

For background to Schiff bases, see: Casas et al. (2000). For a related structure, see: Li & Jian (2010).

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.

1-(4-Methoxybenzylidene)-4-methylthiosemicarbazide top

Crystal data top

C₁₀H₁₃N₃OS	D_x = 1.290 Mg m⁻³
M_r = 223.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2650 reflections
a = 13.397 (3) Å	θ = 3.2–27.2°
b = 9.1271 (18) Å	µ = 0.26 mm⁻¹
c = 18.799 (4) Å	T = 293 K
V = 2298.6 (8) Å³	Bar, colorless
Z = 8	0.25 × 0.22 × 0.18 mm
F(000) = 944

Data collection top

Bruker SMART CCD area-detector diffractometer	1746 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.061
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
phi and ω scans	h = −17→17
20742 measured reflections	k = −11→11
2627 independent reflections	l = −24→24

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2627 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₀H₁₃N₃OS	V = 2298.6 (8) Å³
M_r = 223.29	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.397 (3) Å	µ = 0.26 mm⁻¹
b = 9.1271 (18) Å	T = 293 K
c = 18.799 (4) Å	0.25 × 0.22 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1746 reflections with I > 2σ(I)
20742 measured reflections	R_int = 0.061
2627 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 0.94	Δρ_max = 0.17 e Å⁻³
2627 reflections	Δρ_min = −0.29 e Å⁻³
136 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	0.89733 (4)	1.04305 (5)	0.58910 (3)	0.0579 (2)
C7	0.89674 (13)	0.2105 (2)	0.33447 (9)	0.0442 (4)
N3	0.88845 (12)	0.66880 (17)	0.48831 (8)	0.0467 (4)
C4	0.92228 (14)	0.4806 (2)	0.40190 (10)	0.0456 (4)
O1	0.88816 (11)	0.08431 (16)	0.29666 (7)	0.0577 (4)
N2	0.91161 (12)	0.80887 (17)	0.50939 (9)	0.0509 (4)
H2A	0.9558	0.8577	0.4862	0.061*
C8	0.85569 (15)	0.2343 (2)	0.40146 (9)	0.0483 (5)
H8A	0.8197	0.1606	0.4240	0.058*
C2	0.86618 (14)	0.8710 (2)	0.56577 (10)	0.0450 (4)
N1	0.79800 (13)	0.79216 (17)	0.59919 (8)	0.0567 (5)
H1A	0.7848	0.7061	0.5831	0.068*
C9	0.86880 (15)	0.3681 (2)	0.43415 (10)	0.0484 (5)
H9A	0.8412	0.3836	0.4789	0.058*
C3	0.93581 (15)	0.6236 (2)	0.43363 (10)	0.0505 (5)
H3B	0.9819	0.6866	0.4129	0.061*
C5	0.96339 (16)	0.4532 (2)	0.33528 (10)	0.0550 (5)
H5A	1.0006	0.5259	0.3130	0.066*
C10	0.83329 (19)	−0.0329 (2)	0.32630 (13)	0.0661 (6)
H10A	0.8337	−0.1143	0.2940	0.099*
H10B	0.7657	−0.0023	0.3345	0.099*
H10C	0.8631	−0.0619	0.3706	0.099*
C6	0.95017 (17)	0.3214 (2)	0.30188 (10)	0.0584 (5)
H6A	0.9773	0.3063	0.2569	0.070*
C1	0.7442 (2)	0.8428 (3)	0.66153 (12)	0.0832 (8)
H1B	0.6985	0.7681	0.6769	0.125*
H1C	0.7077	0.9301	0.6499	0.125*
H1D	0.7907	0.8636	0.6990	0.125*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0564 (4)	0.0466 (3)	0.0707 (4)	−0.0056 (2)	0.0113 (2)	−0.0107 (2)
C7	0.0415 (9)	0.0505 (10)	0.0405 (9)	−0.0008 (7)	0.0004 (7)	−0.0047 (8)
N3	0.0450 (9)	0.0478 (9)	0.0473 (8)	−0.0012 (7)	0.0014 (7)	−0.0062 (7)
C4	0.0398 (10)	0.0524 (10)	0.0446 (10)	−0.0010 (8)	0.0011 (8)	−0.0025 (8)
O1	0.0616 (9)	0.0578 (8)	0.0537 (8)	−0.0079 (6)	0.0076 (6)	−0.0105 (7)
N2	0.0492 (10)	0.0480 (9)	0.0557 (9)	−0.0070 (7)	0.0083 (7)	−0.0079 (7)
C8	0.0510 (11)	0.0498 (10)	0.0441 (10)	−0.0016 (9)	0.0055 (8)	0.0060 (8)
C2	0.0393 (9)	0.0470 (10)	0.0488 (10)	0.0024 (8)	−0.0009 (8)	−0.0009 (8)
N1	0.0623 (11)	0.0511 (9)	0.0568 (10)	−0.0110 (8)	0.0156 (8)	−0.0102 (8)
C9	0.0512 (11)	0.0553 (11)	0.0386 (9)	0.0006 (9)	0.0067 (8)	0.0011 (8)
C3	0.0456 (11)	0.0534 (11)	0.0524 (11)	−0.0051 (9)	0.0023 (9)	−0.0020 (9)
C5	0.0572 (12)	0.0587 (12)	0.0492 (10)	−0.0129 (9)	0.0156 (9)	−0.0027 (9)
C10	0.0698 (16)	0.0533 (12)	0.0751 (14)	−0.0098 (10)	0.0038 (12)	−0.0050 (10)
C6	0.0602 (13)	0.0689 (13)	0.0462 (10)	−0.0105 (10)	0.0168 (9)	−0.0102 (9)
C1	0.099 (2)	0.0764 (14)	0.0739 (14)	−0.0251 (14)	0.0394 (15)	−0.0209 (13)

Geometric parameters (Å, º) top

S1—C2	1.683 (2)	C2—N1	1.322 (2)
C7—O1	1.358 (2)	N1—C1	1.451 (3)
C7—C6	1.383 (3)	N1—H1A	0.8600
C7—C8	1.391 (3)	C9—H9A	0.9300
N3—C3	1.277 (2)	C3—H3B	0.9300
N3—N2	1.374 (2)	C5—C6	1.368 (3)
C4—C5	1.391 (3)	C5—H5A	0.9300
C4—C9	1.391 (3)	C10—H10A	0.9600
C4—C3	1.446 (3)	C10—H10B	0.9600
O1—C10	1.413 (2)	C10—H10C	0.9600
N2—C2	1.347 (2)	C6—H6A	0.9300
N2—H2A	0.8600	C1—H1B	0.9600
C8—C9	1.378 (3)	C1—H1C	0.9600
C8—H8A	0.9300	C1—H1D	0.9600

O1—C7—C6	115.63 (16)	C4—C9—H9A	119.2
O1—C7—C8	124.96 (17)	N3—C3—C4	124.16 (18)
C6—C7—C8	119.40 (17)	N3—C3—H3B	117.9
C3—N3—N2	114.88 (16)	C4—C3—H3B	117.9
C5—C4—C9	117.63 (17)	C6—C5—C4	121.34 (17)
C5—C4—C3	118.95 (17)	C6—C5—H5A	119.3
C9—C4—C3	123.42 (17)	C4—C5—H5A	119.3
C7—O1—C10	118.68 (15)	O1—C10—H10A	109.5
C2—N2—N3	121.08 (16)	O1—C10—H10B	109.5
C2—N2—H2A	119.5	H10A—C10—H10B	109.5
N3—N2—H2A	119.5	O1—C10—H10C	109.5
C9—C8—C7	119.47 (18)	H10A—C10—H10C	109.5
C9—C8—H8A	120.3	H10B—C10—H10C	109.5
C7—C8—H8A	120.3	C5—C6—C7	120.48 (17)
N1—C2—N2	117.22 (17)	C5—C6—H6A	119.8
N1—C2—S1	123.74 (15)	C7—C6—H6A	119.8
N2—C2—S1	119.04 (15)	N1—C1—H1B	109.5
C2—N1—C1	123.65 (17)	N1—C1—H1C	109.5
C2—N1—H1A	118.2	H1B—C1—H1C	109.5
C1—N1—H1A	118.2	N1—C1—H1D	109.5
C8—C9—C4	121.67 (17)	H1B—C1—H1D	109.5
C8—C9—H9A	119.2	H1C—C1—H1D	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.86	2.28	2.661 (2)	107
N1—H1A···S1ⁱ	0.86	2.86	3.4718 (18)	130
N2—H2A···S1ⁱⁱ	0.86	2.59	3.4359 (17)	169

Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+2, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₃OS
M_r	223.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	13.397 (3), 9.1271 (18), 18.799 (4)
V (Å³)	2298.6 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.25 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	20742, 2627, 1746
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.146, 0.94
No. of reflections	2627
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.29

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	2.28	2.661 (2)	107
N1—H1A···S1ⁱ	0.86	2.86	3.4718 (18)	130
N2—H2A···S1ⁱⁱ	0.86	2.59	3.4359 (17)	169

Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+2, −y+2, −z+1.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casas, J. S., Garcia-T, M. S. & Sordo, J. (2000). Coord. Chem. Rev. 209, 197–261. Web of Science CrossRef CAS Google Scholar
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1399. 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 o2728

https://doi.org/10.1107/S1600536810038882

Open

access