4-Methyl­benzaldehyde thio­semi­carbazone

Zhang, J.; Geng, H.; Zhuang, L.; Wang, G.

doi:10.1107/S1600536809033297

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2244

doi:10.1107/S1600536809033297

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4-Methylbenzaldehyde thiosemicarbazone

Jian Zhang,^a Hao Geng,^a Ling-hua Zhuang ^a and Guo-wei Wang ^a ^*

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

(Received 13 August 2009; accepted 21 August 2009; online 26 August 2009)

The title compound, C₉H₁₁N₃S, was prepared by reacting 4-methylbenzaldehyde with thiosemicarbazide. An intramolecular N—H⋯N hydrogen bond helps to establish the observed molecular conformation. The crystal packing is realized by intermolecular N—H⋯S hydrogen bonds.

Related literature

For 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 ); Zhang et al. (2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₁N₃S
M_r = 193.27
Monoclinic, P 2₁ /c
a = 13.234 (3) Å
b = 8.221 (2) Å
c = 10.311 (2) Å
β = 111.15 (3)°
V = 1046.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.27 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 = 0.924, T_max = 0.974
1982 measured reflections
1898 independent reflections
1322 reflections with I > 2σ(I)
R_int = 0.032
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.146
S = 1.00
1898 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Sⁱ	0.86	2.54	3.389 (3)	168
N3—H3B⋯Sⁱⁱ	0.86	2.61	3.395 (3)	153
N3—H3A⋯N1	0.86	2.29	2.641 (4)	105
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033297/im2136sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033297/im2136Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones constitute an important class of N,S donor ligands due to their ability 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 the parent aldehyde or ketone moiety (Chimenti et al., 2007). Schiff bases in general show potential as antimicrobial and anticancer agents (Tarafder et al., 2000; Deschamps et al., 2003) and have therefore envisaged biochemical and pharmacological applications. We are focusing our synthetic and structural studies on new products of thiazole Schiff bases from thiosemicarbazones (Zhang et al., 2009). We herein report the crystal structure of the title compound (I).

The atom-numbering scheme of (I) is shown in Fig.1, and all bond lengths are within normal ranges (Allen et al., 1987).

The sulfur atom and the hydrazine nitrogen N1 are in trans position with respect to the C9–N2 bond. The molecular conformation is determined by a strong intramolecular hydrogen bond N3–H3A···N1(2.641 (3) A°).

The planar phenyl ring A (C2/C3/C4/C5/C6/C7, r.m.s. deviation 0.0115 (1) Å) and the pseudo five-membered ring B(N1/N2/C9/N3/H3A, r.m.s. deviation 0.035 (1) Å that is formed by the N3—H3A···N1 hydrogen bond enclose a dihedral angle of 14 (1)°. The dihedral angle between the thiourea group (N1/N2/C9/S) and the phenyl ring measures to 17 (2)°.

The crystal packing is realized by intermolecular N—H···S hydrogen bonds (Table 1, Fig. 1 and Fig.2).

Related literature top

For 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); Zhang et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of 4-methyl-benzaldehyde (1.20 g, 0.01 mol) and hydrazinecarbothioamide (0.91 g, 0.01 mol) in 20 ml of absolute methanol was refluxed for about 3 h. After cooling, the precipitated 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 at room temperature. 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), 1.79 (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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) showing the atom-numbering scheme and 30% displacement ellipsoids. The intramolecular hydrogen bond is shown as dashed lines.
	Fig. 2. Crystal packing of (I). Hydrogen bonds are drawn as dashed lines.

4-Methylbenzaldehyde thiosemicarbazone top

Crystal data top

C₉H₁₁N₃S	F(000) = 408
M_r = 193.27	D_x = 1.227 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27 reflections
a = 13.234 (3) Å	θ = 1–25°
b = 8.221 (2) Å	µ = 0.27 mm⁻¹
c = 10.311 (2) Å	T = 293 K
β = 111.15 (3)°	Block, colorless
V = 1046.2 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1322 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 25.3°, θ_min = 1.7°
ω/2θ scans	h = −15→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.924, T_max = 0.974	l = −11→12
1982 measured reflections	3 standard reflections every 200 reflections
1898 independent reflections	intensity decay: 9%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.07P)² + 0.38P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1898 reflections	Δρ_max = 0.26 e Å⁻³
120 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (4)

Crystal data top

C₉H₁₁N₃S	V = 1046.2 (4) Å³
M_r = 193.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.234 (3) Å	µ = 0.27 mm⁻¹
b = 8.221 (2) Å	T = 293 K
c = 10.311 (2) Å	0.30 × 0.20 × 0.10 mm
β = 111.15 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1322 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.032
T_min = 0.924, T_max = 0.974	3 standard reflections every 200 reflections
1982 measured reflections	intensity decay: 9%
1898 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
1898 reflections	Δρ_min = −0.20 e Å⁻³
120 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
S	0.48277 (7)	0.09017 (9)	0.81196 (7)	0.0534 (3)
N1	0.34064 (18)	−0.0455 (3)	0.4236 (2)	0.0438 (6)
C1	−0.0005 (3)	−0.2600 (6)	−0.1894 (3)	0.0788 (12)
H1B	−0.0374	−0.3614	−0.1934	0.118*
H1C	0.0324	−0.2593	−0.2585	0.118*
H1D	−0.0514	−0.1721	−0.2067	0.118*
N2	0.40264 (19)	−0.0458 (3)	0.5647 (2)	0.0456 (6)
H2A	0.4275	−0.1358	0.6065	0.055*
C2	0.0863 (3)	−0.2397 (5)	−0.0467 (3)	0.0560 (9)
N3	0.3955 (2)	0.2299 (3)	0.5633 (3)	0.0630 (8)
H3A	0.3650	0.2263	0.4743	0.076*
H3B	0.4078	0.3222	0.6054	0.076*
C3	0.1264 (3)	−0.0877 (4)	0.0043 (3)	0.0614 (9)
H3C	0.1006	0.0034	−0.0513	0.074*
C4	0.2041 (3)	−0.0681 (4)	0.1365 (3)	0.0553 (8)
H4A	0.2302	0.0352	0.1678	0.066*
C5	0.2429 (2)	−0.2018 (4)	0.2222 (3)	0.0445 (7)
C6	0.2060 (2)	−0.3553 (4)	0.1705 (3)	0.0521 (8)
H6A	0.2329	−0.4465	0.2255	0.063*
C7	0.1289 (3)	−0.3741 (4)	0.0370 (3)	0.0565 (9)
H7A	0.1056	−0.4779	0.0036	0.068*
C8	0.3157 (2)	−0.1842 (4)	0.3664 (3)	0.0452 (7)
H8A	0.3446	−0.2770	0.4180	0.054*
C9	0.4235 (2)	0.0939 (3)	0.6353 (3)	0.0420 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0798 (6)	0.0472 (5)	0.0282 (4)	−0.0056 (4)	0.0134 (4)	−0.0039 (3)
N1	0.0512 (15)	0.0501 (15)	0.0282 (11)	−0.0033 (11)	0.0121 (10)	−0.0016 (10)
C1	0.071 (2)	0.116 (3)	0.0399 (18)	−0.014 (2)	0.0086 (17)	−0.015 (2)
N2	0.0603 (16)	0.0443 (14)	0.0268 (11)	−0.0011 (12)	0.0094 (11)	−0.0010 (10)
C2	0.0497 (19)	0.081 (2)	0.0362 (16)	−0.0065 (17)	0.0143 (14)	−0.0080 (16)
N3	0.100 (2)	0.0425 (15)	0.0339 (13)	0.0016 (14)	0.0082 (14)	−0.0005 (11)
C3	0.068 (2)	0.067 (2)	0.0419 (17)	−0.0007 (18)	0.0119 (16)	0.0070 (16)
C4	0.064 (2)	0.055 (2)	0.0386 (16)	−0.0061 (16)	0.0082 (14)	−0.0039 (14)
C5	0.0452 (17)	0.0530 (18)	0.0342 (14)	−0.0006 (14)	0.0131 (12)	−0.0056 (13)
C6	0.0556 (19)	0.0562 (19)	0.0423 (17)	−0.0015 (15)	0.0151 (14)	−0.0060 (15)
C7	0.057 (2)	0.066 (2)	0.0451 (17)	−0.0113 (16)	0.0169 (15)	−0.0190 (16)
C8	0.0516 (18)	0.0476 (18)	0.0332 (14)	0.0002 (14)	0.0115 (13)	−0.0019 (13)
C9	0.0492 (17)	0.0438 (16)	0.0320 (14)	−0.0015 (13)	0.0135 (12)	−0.0018 (13)

Geometric parameters (Å, º) top

S—C9	1.704 (3)	N3—H3A	0.8600
N1—C8	1.271 (4)	N3—H3B	0.8600
N1—N2	1.389 (3)	C3—C4	1.390 (4)
C1—C2	1.514 (4)	C3—H3C	0.9300
C1—H1B	0.9600	C4—C5	1.387 (4)
C1—H1C	0.9600	C4—H4A	0.9300
C1—H1D	0.9600	C5—C6	1.388 (4)
N2—C9	1.334 (3)	C5—C8	1.458 (4)
N2—H2A	0.8600	C6—C7	1.395 (4)
C2—C3	1.385 (5)	C6—H6A	0.9300
C2—C7	1.390 (5)	C7—H7A	0.9300
N3—C9	1.319 (3)	C8—H8A	0.9300

C8—N1—N2	116.1 (2)	C5—C4—C3	120.4 (3)
C2—C1—H1B	109.5	C5—C4—H4A	119.8
C2—C1—H1C	109.5	C3—C4—H4A	119.8
H1B—C1—H1C	109.5	C4—C5—C6	118.5 (3)
C2—C1—H1D	109.5	C4—C5—C8	121.9 (3)
H1B—C1—H1D	109.5	C6—C5—C8	119.5 (3)
H1C—C1—H1D	109.5	C5—C6—C7	120.7 (3)
C9—N2—N1	119.9 (2)	C5—C6—H6A	119.7
C9—N2—H2A	120.1	C7—C6—H6A	119.7
N1—N2—H2A	120.1	C2—C7—C6	120.8 (3)
C3—C2—C7	117.9 (3)	C2—C7—H7A	119.6
C3—C2—C1	121.4 (3)	C6—C7—H7A	119.6
C7—C2—C1	120.8 (3)	N1—C8—C5	121.8 (3)
C9—N3—H3A	120.0	N1—C8—H8A	119.1
C9—N3—H3B	120.0	C5—C8—H8A	119.1
H3A—N3—H3B	120.0	N3—C9—N2	117.5 (2)
C2—C3—C4	121.6 (3)	N3—C9—S	123.0 (2)
C2—C3—H3C	119.2	N2—C9—S	119.5 (2)
C4—C3—H3C	119.2

C8—N1—N2—C9	−173.6 (3)	C3—C2—C7—C6	2.8 (5)
C7—C2—C3—C4	−2.1 (5)	C1—C2—C7—C6	−177.7 (3)
C1—C2—C3—C4	178.4 (3)	C5—C6—C7—C2	−0.8 (5)
C2—C3—C4—C5	−0.7 (5)	N2—N1—C8—C5	174.4 (2)
C3—C4—C5—C6	2.8 (5)	C4—C5—C8—N1	5.3 (5)
C3—C4—C5—C8	−173.4 (3)	C6—C5—C8—N1	−170.9 (3)
C4—C5—C6—C7	−2.0 (5)	N1—N2—C9—N3	−8.5 (4)
C8—C5—C6—C7	174.2 (3)	N1—N2—C9—S	170.71 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.86	2.29	2.641 (4)	105
N2—H2A···Sⁱ	0.86	2.54	3.389 (3)	168
N3—H3B···Sⁱⁱ	0.86	2.61	3.395 (3)	153

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃S
M_r	193.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.234 (3), 8.221 (2), 10.311 (2)
β (°)	111.15 (3)
V (Å³)	1046.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
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	0.924, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	1982, 1898, 1322
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.146, 1.00
No. of reflections	1898
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.20

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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
N3—H3A···N1	0.86	2.29	2.641 (4)	104.5
N2—H2A···Sⁱ	0.86	2.54	3.389 (3)	167.6
N3—H3B···Sⁱⁱ	0.86	2.61	3.395 (3)	153.2

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

Acknowledgements

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

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