3-Methoxy­benzaldehyde thio­semi­carbazone

Zhang, J.; Wu, L.; Zhuang, L.; Wang, G.

doi:10.1107/S160053680901040X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o884

doi:10.1107/S160053680901040X

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3-Methoxybenzaldehyde thiosemicarbazone

Jian Zhang,^a Lin-ping Wu,^a Ling-hua Zhuang ^b and Guo-wei Wang ^a ^*

^aDepartment of Light Chemical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kingwell2004@sina.com.cn

(Received 10 March 2009; accepted 20 March 2009; online 28 March 2009)

The title compound, C₉H₁₁N₃OS, was prepared by the reaction of 3-methoxybenzaldehyde and thiosemicarbazide. The benzylidene ring and the thiosemicarbazone fragment are slightly twisted, making a dihedral angle of 14.1 (1)°. A weak intramolecular N—H⋯N hydrogen bond may influence the conformation of the molecule. Intermolecular N—H⋯S hydrogen bonds build up a three-dimensional network.

Related literature

For a general background to thiosemicarbazone compounds, see: Casas et al. (2000 ); Tarafder et al. (2000 ); Ferrari et al. (2000 ); Deschamps et al. (2003 ); Maccioni et al. (2003 ); Chimenti et al.(2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₁N₃OS
M_r = 209.27
Monoclinic, P 2₁ /c
a = 11.814 (2) Å
b = 5.6760 (11) Å
c = 15.248 (3) Å
β = 90.29 (3)°
V = 1022.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.908, T_max = 0.969
1946 measured reflections
1852 independent reflections
1494 reflections with I > 2σ(I)
R_int = 0.017
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.110
S = 1.06
1852 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.86	2.57	3.370 (2)	156
N3—H3B⋯S1ⁱⁱ	0.86	2.57	3.411 (2)	166
N3—H3A⋯N1	0.86	2.25	2.611 (3)	105
Symmetry codes: (i) -x+1, -y+3, -z+1; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901040X/dn2432sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901040X/dn2432Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones constitute an important class of N,S donor ligands due to their propensity to react with a wide range of metals (Casas et al., 2000). Thiosemicarbazones exhibit various biological activities and have therefore attracted considerable pharmaceutical interest (Maccioni et al., 2003; Ferrari et al., 2000). They have been evaluated as antiviral, antibacterial and anticancer therapeutics. Thiosemicarbazones belong to a large group of thiourea derivatives, whose biological activities are a function of parent aldehyde or ketone moiety (Chimenti et al., 2007). Schiff bases show potential as antimicrobial and anticancer agents (Tarafder et al., 2000; Deschamps et al., 2003) and so have biochemical and pharmacological applications. We here report the crystal structure of the title compound (I).

The sulfur atom and the hydrazine nitrogen N1 are in trans position with respect to the C9–N2 bond. This conformation may be induced by the weak intramolecular N-H···N hydrogen bond (Fig. 1, Table 1). All bond lengths are within normal ranges (Allen et al., 1987).

At first glance the molecule is roughly planar with the largest deviation from the mean plane being -0.272 (3) Å at N3, however the benzaldehyde ring and the thiosemicarbazone fragment are twisted with respect to each other making a dihedral angle of 14.1 (1)°.

The molecules are connected by intermolecular N—H···S hydrogen bonds which build up a three dimensional network (Table 1, Fig.2).

Related literature top

For a general background to thiosemicarbazone compounds, see: Casas et al. (2000); Tarafder et al. (2000); Ferrari et al. (2000); Deschamps et al. (2003); Maccioni et al. (2003); Chimenti et al.(2007). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of 3-methoxybenzaldehyde (1.36 g, 0.01 mol) and hydrazinecarbothioamide (0.91 g, 0.01 mol) in 20 ml of absolute methanol was refluxed for about 3 h. On cooling, the solid separated was filtered and recrystallized from ethyl acetate. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of ethyl acetate. ¹H NMR (DMSO, δ, p.p.m.) 11.39 (s, 1 H), 8.17 (s, 1 H), 8.02 (s,2 H), 7.42 (m, 1 H), 7.30 (t, 2 H), 6.99 (t,1 H), 3.79 (t, 3 H).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme and 30% displacement ellipsoids. H atoms are represented as smal sphere of arbitrary radii. Intramolecular hydrogen bond is shown as dashed line.
	Fig. 2. Partial packing view showing the N-H···S hydrogen bonds network. H atoms not involved in hydrogen bonding have been omitted for clarity. H bonds are shown as dashed lines. [Symmetry codes: (i) -x+1, -y+3, -z+1; (ii) -x+1, y-1/2, -z+1/2]

3-Methoxybenzaldehyde thiosemicarbazone top

Crystal data top

C₉H₁₁N₃OS	F(000) = 440
M_r = 209.27	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27 reflections
a = 11.814 (2) Å	θ = 1–25°
b = 5.6760 (11) Å	µ = 0.29 mm⁻¹
c = 15.248 (3) Å	T = 293 K
β = 90.29 (3)°	Block, colorless
V = 1022.5 (3) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1494 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 25.3°, θ_min = 1.7°
ω/2θ scans	h = −14→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.908, T_max = 0.969	l = −18→18
1946 measured reflections	3 standard reflections every 200 reflections
1852 independent reflections	intensity decay: 9%

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0521P)² + 0.3815P] where P = (F_o² + 2F_c²)/3
1852 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₉H₁₁N₃OS	V = 1022.5 (3) Å³
M_r = 209.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.814 (2) Å	µ = 0.29 mm⁻¹
b = 5.6760 (11) Å	T = 293 K
c = 15.248 (3) Å	0.30 × 0.20 × 0.10 mm
β = 90.29 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1494 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.017
T_min = 0.908, T_max = 0.969	3 standard reflections every 200 reflections
1946 measured reflections	intensity decay: 9%
1852 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
1852 reflections	Δρ_min = −0.26 e Å⁻³
128 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.51511 (6)	1.47619 (10)	0.35880 (3)	0.0442 (2)
O1	0.85492 (14)	0.6407 (3)	0.83956 (9)	0.0496 (5)
N1	0.66878 (15)	1.0213 (3)	0.50804 (11)	0.0369 (4)
N2	0.60984 (16)	1.2149 (3)	0.47967 (11)	0.0407 (5)
H2	0.5936	1.3268	0.5155	0.049*
N3	0.59915 (18)	1.0451 (4)	0.34546 (12)	0.0497 (5)
H3A	0.6324	0.9237	0.3674	0.060*
H3B	0.5800	1.0463	0.2910	0.060*
C1	0.9085 (2)	0.4449 (6)	0.88050 (16)	0.0614 (8)
H1A	0.9862	0.4377	0.8627	0.092*
H1B	0.8706	0.3024	0.8634	0.092*
H1C	0.9049	0.4624	0.9430	0.092*
C2	0.84356 (18)	0.6327 (4)	0.75008 (14)	0.0383 (5)
C3	0.77906 (17)	0.8120 (4)	0.71427 (13)	0.0366 (5)
H3	0.7479	0.9264	0.7505	0.044*
C4	0.76070 (17)	0.8221 (4)	0.62447 (13)	0.0350 (5)
C5	0.8097 (2)	0.6510 (4)	0.57024 (14)	0.0428 (6)
H5	0.7982	0.6566	0.5099	0.051*
C6	0.8741 (2)	0.4764 (4)	0.60621 (16)	0.0503 (6)
H6	0.9071	0.3642	0.5700	0.060*
C7	0.8914 (2)	0.4638 (4)	0.69715 (16)	0.0472 (6)
H7	0.9346	0.3430	0.7214	0.057*
C8	0.69256 (18)	1.0136 (4)	0.58932 (13)	0.0379 (5)
H8	0.6663	1.1311	0.6265	0.045*
C9	0.57769 (17)	1.2279 (4)	0.39499 (13)	0.0332 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0643 (4)	0.0374 (3)	0.0309 (3)	0.0090 (3)	−0.0081 (3)	0.0035 (2)
O1	0.0534 (10)	0.0621 (12)	0.0333 (8)	0.0106 (9)	−0.0062 (7)	0.0109 (8)
N1	0.0429 (10)	0.0363 (10)	0.0315 (9)	0.0058 (9)	−0.0045 (8)	0.0024 (8)
N2	0.0555 (12)	0.0378 (11)	0.0286 (9)	0.0118 (9)	−0.0091 (8)	−0.0020 (8)
N3	0.0732 (14)	0.0442 (12)	0.0315 (9)	0.0164 (11)	−0.0128 (9)	−0.0056 (9)
C1	0.0631 (16)	0.077 (2)	0.0444 (14)	0.0194 (15)	−0.0057 (12)	0.0225 (14)
C2	0.0335 (11)	0.0471 (14)	0.0343 (11)	−0.0031 (10)	−0.0041 (9)	0.0072 (10)
C3	0.0338 (11)	0.0429 (13)	0.0331 (11)	0.0020 (10)	0.0002 (9)	0.0024 (10)
C4	0.0331 (11)	0.0380 (12)	0.0340 (11)	−0.0035 (10)	−0.0043 (9)	0.0045 (10)
C5	0.0526 (14)	0.0413 (14)	0.0346 (11)	0.0013 (11)	−0.0061 (10)	−0.0020 (10)
C6	0.0622 (16)	0.0432 (14)	0.0454 (13)	0.0109 (12)	−0.0051 (12)	−0.0084 (11)
C7	0.0517 (14)	0.0401 (13)	0.0497 (14)	0.0076 (11)	−0.0091 (11)	0.0061 (11)
C8	0.0389 (11)	0.0439 (13)	0.0309 (11)	0.0039 (10)	−0.0012 (9)	0.0002 (10)
C9	0.0372 (11)	0.0357 (12)	0.0266 (10)	−0.0032 (10)	−0.0024 (8)	0.0015 (9)

Geometric parameters (Å, º) top

S1—C9	1.683 (2)	C2—C7	1.377 (3)
O1—C2	1.371 (2)	C2—C3	1.382 (3)
O1—C1	1.422 (3)	C3—C4	1.386 (3)
N1—C8	1.270 (3)	C3—H3	0.9300
N1—N2	1.370 (2)	C4—C5	1.402 (3)
N2—C9	1.346 (3)	C4—C8	1.454 (3)
N2—H2	0.8600	C5—C6	1.363 (3)
N3—C9	1.309 (3)	C5—H5	0.9300
N3—H3A	0.8600	C6—C7	1.402 (3)
N3—H3B	0.8600	C6—H6	0.9300
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	C8—H8	0.9300
C1—H1C	0.9600

C2—O1—C1	116.9 (2)	C4—C3—H3	119.9
C8—N1—N2	116.44 (18)	C3—C4—C5	119.4 (2)
C9—N2—N1	119.16 (18)	C3—C4—C8	118.6 (2)
C9—N2—H2	120.4	C5—C4—C8	122.00 (19)
N1—N2—H2	120.4	C6—C5—C4	119.8 (2)
C9—N3—H3A	120.0	C6—C5—H5	120.1
C9—N3—H3B	120.0	C4—C5—H5	120.1
H3A—N3—H3B	120.0	C5—C6—C7	120.9 (2)
O1—C1—H1A	109.5	C5—C6—H6	119.6
O1—C1—H1B	109.5	C7—C6—H6	119.6
H1A—C1—H1B	109.5	C2—C7—C6	119.1 (2)
O1—C1—H1C	109.5	C2—C7—H7	120.5
H1A—C1—H1C	109.5	C6—C7—H7	120.5
H1B—C1—H1C	109.5	N1—C8—C4	120.3 (2)
O1—C2—C7	124.6 (2)	N1—C8—H8	119.8
O1—C2—C3	114.8 (2)	C4—C8—H8	119.8
C7—C2—C3	120.6 (2)	N3—C9—N2	117.1 (2)
C2—C3—C4	120.2 (2)	N3—C9—S1	124.11 (16)
C2—C3—H3	119.9	N2—C9—S1	118.78 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.57	3.370 (2)	156
N3—H3B···S1ⁱⁱ	0.86	2.57	3.411 (2)	166
N3—H3A···N1	0.86	2.25	2.611 (3)	105

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃OS
M_r	209.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.814 (2), 5.6760 (11), 15.248 (3)
β (°)	90.29 (3)
V (Å³)	1022.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.908, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	1946, 1852, 1494
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.110, 1.06
No. of reflections	1852
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.26

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.57	3.370 (2)	155.5
N3—H3B···S1ⁱⁱ	0.86	2.57	3.411 (2)	165.6
N3—H3A···N1	0.86	2.25	2.611 (3)	104.9

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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