4-Methyl-benzaldehyde thio-semi-carbazone.

The title compound, C(9)H(11)N(3)S, was prepared by reacting 4-methyl-benzaldehyde with thio-semicarbazide. An intra-molecular N-H⋯N hydrogen bond helps to establish the observed mol-ecular conformation. The crystal packing is realized by inter-molecular 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 = 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) 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[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.146

S = 1.00

1898 reflections

120 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −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.

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

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

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

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

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 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)

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.

	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)

	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)

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)

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

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) .