4-Methyl­benzaldehyde thio­semi­carbazone

Abstract

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,

• a = 13.234 (3) Å

• b = 8.221 (2) Å

• c = 10.311 (2) Å

• β = 111.15 (3)°

• V = 1046.2 (4) ų

• 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[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

All H atoms were positioned geometrically, with C—H = 0.93 Å and N—H = 0.86 °, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C), where x= 1.5 for methyl H and x = 1.2 for methylene H atoms.

Figures

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.

Crystal data

C9H11N3S	F(000) = 408
Mr = 193.27	Dx = 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

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

Refinement

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(Fo2) + (0.07P)2 + 0.38P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
1898 reflections	Δρmax = 0.26 e Å−3
120 parameters	Δρmin = −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)

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.