(Z)-1-[2-(Trifluoro­meth­yl)benzyl­idene]thio­semicarbazide

Chen, X.; Jing, Z.-L.

doi:10.1107/S1600536811047623

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3369

https://doi.org/10.1107/S1600536811047623

Open

access

(Z)-1-[2-(Trifluoromethyl)benzylidene]thiosemicarbazide

Xin Chen ^a and Zuo-Liang Jing ^a ^*

^aCollege of Sciences, Tianjin University of Science and Technology, Tianjin 300222, People's Republic of China
^*Correspondence e-mail: jzl74@tust.edu.cn

(Received 10 October 2011; accepted 10 November 2011; online 19 November 2011)

In the crystal structure of the title compound, C₉H₈F₃N₃S, all atoms except for two of the F atoms are located on a mirror plane. In the crystal, the molecules are connected by N—H⋯S hydrogen bonds, forming a molecular tape along the a axis.

Related literature

For general background to metal complexes with Shiff bases, see: Kahwa et al. (1986 ); Deng et al. (2005 ). For related structures, see: Guo et al. (2006 ); Jing et al. (2005 ); Santos et al. (2001 ); Yu et al. (2005 ).

Experimental

Crystal data

C₉H₈F₃N₃S
M_r = 247.24
Orthorhombic, P n m a
a = 8.628 (2) Å
b = 6.9795 (17) Å
c = 18.222 (4) Å
V = 1097.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 294 K
0.40 × 0.40 × 0.30 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.886, T_max = 0.912
5953 measured reflections
1228 independent reflections
869 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.113
S = 1.07
1228 reflections
101 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 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
N3—H3B⋯S1ⁱ	0.88 (4)	2.54 (4)	3.418 (3)	174 (3)
N2—H2A⋯S1ⁱⁱ	0.82 (3)	2.61 (3)	3.430 (2)	173 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{5\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{5\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); 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 I, global. DOI: https://doi.org/10.1107/S1600536811047623/is2791sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811047623/is2791Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811047623/is2791Isup3.cml

checkCIF report

Comment top

Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands (Yu et al., 2005; Deng et al., 2005; Jing, Fan et al., 2005; Guo, Sun et al., 2006), we report the synthesis and structure of the title compound, (I). In the molecular structure of the title compound (Fig. 1), the expected geometric parameters are observed. The molecules are associated via weak intermolecular N—H···S hydrogen-bonding interactions (Table 1) to form a supramolecular network as illustrated in Fig. 2.

Related literature top

For general background to metal complexes with Shiff bases, see: Kahwa et al. (1986); Deng et al. (2005). For related structures, see: Guo et al. (2006); Jing et al. (2005); Santos et al. (2001); Yu et al. (2005).

Experimental top

An anhydrous ethanol solution(50 mL) of thiosemicarbazide (0.91 g, 10 mmol) was added to an anhydrous ethanol solution(50 mL) of 2-(trifluoromethyl)benzaldehyde (1.74 g, 10 mmol) and the mixture was stirred at 350 K for 6 h under N₂, whereupon a straw colorless solution appeared. The solvent was removed and the residue recrystallized from anhydrous ethanol. The product was isolated and then dried in vacuo to give pure (I) in 77% yield (Fig. 3). The colorless single crystals suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution of (I).

Structure description top

For general background to metal complexes with Shiff bases, see: Kahwa et al. (1986); Deng et al. (2005). For related structures, see: Guo et al. (2006); Jing et al. (2005); Santos et al. (2001); Yu et al. (2005).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound viewed down the b axis, showing intermolecular hydrogen bonds (dashed lines).
	Fig. 3. The synthetic scheme of the title compound.

(Z)-1-[2-(Trifluoromethyl)benzylidene]thiosemicarbazide top

Crystal data top

C₉H₈F₃N₃S	F(000) = 504
M_r = 247.24	D_x = 1.497 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2111 reflections
a = 8.628 (2) Å	θ = 2.6–26.2°
b = 6.9795 (17) Å	µ = 0.31 mm⁻¹
c = 18.222 (4) Å	T = 294 K
V = 1097.2 (5) Å³	Block, colorless
Z = 4	0.40 × 0.40 × 0.30 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1228 independent reflections
Radiation source: fine-focus sealed tube	869 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 7.31 pixels mm^-1	θ_max = 26.4°, θ_min = 2.2°
phi and ω scans	h = −10→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −7→8
T_min = 0.886, T_max = 0.912	l = −22→22
5953 measured reflections

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0497P)² + 0.3737P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1228 reflections	Δρ_max = 0.19 e Å⁻³
101 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: 0.0104 (19)

Crystal data top

C₉H₈F₃N₃S	V = 1097.2 (5) Å³
M_r = 247.24	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 8.628 (2) Å	µ = 0.31 mm⁻¹
b = 6.9795 (17) Å	T = 294 K
c = 18.222 (4) Å	0.40 × 0.40 × 0.30 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1228 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	869 reflections with I > 2σ(I)
T_min = 0.886, T_max = 0.912	R_int = 0.028
5953 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.19 e Å⁻³
1228 reflections	Δρ_min = −0.20 e Å⁻³
101 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	0.72882 (8)	0.2500	1.28034 (4)	0.0803 (4)
F1	0.0437 (2)	0.2500	0.91939 (12)	0.0999 (8)
F2	0.15033 (14)	0.0964 (2)	1.00795 (8)	0.0891 (5)
N1	0.6005 (2)	0.2500	1.07458 (11)	0.0465 (6)
N2	0.5981 (2)	0.2500	1.14995 (12)	0.0519 (6)
H2A	0.513 (4)	0.2500	1.1704 (16)	0.062*
N3	0.8620 (3)	0.2500	1.14879 (15)	0.0726 (9)
H3A	0.862 (4)	0.2500	1.098 (2)	0.087*
H3B	0.953 (5)	0.2500	1.1704 (19)	0.087*
C1	0.1665 (3)	0.2500	0.96416 (18)	0.0636 (8)
C2	0.3177 (3)	0.2500	0.92383 (15)	0.0490 (7)
C3	0.3171 (4)	0.2500	0.84755 (17)	0.0691 (9)
H3	0.2231	0.2500	0.8226	0.083*
C4	0.4530 (4)	0.2500	0.80832 (18)	0.0847 (11)
H4	0.4510	0.2500	0.7573	0.102*
C5	0.5928 (4)	0.2500	0.84529 (17)	0.0775 (10)
H5	0.6851	0.2500	0.8189	0.093*
C6	0.5970 (3)	0.2500	0.92107 (16)	0.0561 (8)
H6	0.6922	0.2500	0.9451	0.067*
C7	0.4604 (3)	0.2500	0.96217 (14)	0.0428 (6)
C8	0.4682 (3)	0.2500	1.04285 (14)	0.0442 (6)
H8	0.3777	0.2500	1.0706	0.053*
C9	0.7324 (3)	0.2500	1.18753 (16)	0.0538 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0329 (4)	0.1575 (10)	0.0504 (4)	0.000	−0.0050 (3)	0.000
F1	0.0416 (10)	0.161 (2)	0.0973 (15)	0.000	−0.0225 (9)	0.000
F2	0.0515 (7)	0.1089 (12)	0.1070 (11)	−0.0201 (7)	0.0044 (7)	0.0278 (10)
N1	0.0349 (11)	0.0577 (15)	0.0469 (12)	0.000	0.0003 (9)	0.000
N2	0.0282 (11)	0.0807 (18)	0.0468 (12)	0.000	0.0005 (9)	0.000
N3	0.0300 (11)	0.132 (3)	0.0555 (14)	0.000	−0.0005 (11)	0.000
C1	0.0383 (14)	0.082 (2)	0.071 (2)	0.000	−0.0100 (13)	0.000
C2	0.0419 (13)	0.0487 (16)	0.0565 (15)	0.000	−0.0049 (12)	0.000
C3	0.0595 (18)	0.091 (3)	0.0566 (17)	0.000	−0.0154 (14)	0.000
C4	0.074 (2)	0.129 (3)	0.0511 (17)	0.000	−0.0017 (17)	0.000
C5	0.062 (2)	0.113 (3)	0.0578 (18)	0.000	0.0124 (15)	0.000
C6	0.0410 (14)	0.069 (2)	0.0587 (16)	0.000	0.0015 (12)	0.000
C7	0.0381 (13)	0.0409 (15)	0.0495 (14)	0.000	−0.0003 (11)	0.000
C8	0.0305 (12)	0.0507 (16)	0.0513 (14)	0.000	0.0019 (10)	0.000
C9	0.0321 (12)	0.074 (2)	0.0554 (15)	0.000	−0.0012 (11)	0.000

Geometric parameters (Å, º) top

S1—C9	1.691 (3)	C2—C3	1.390 (4)
F1—C1	1.338 (3)	C2—C7	1.416 (3)
F2—C1	1.343 (2)	C3—C4	1.373 (5)
N1—C8	1.279 (3)	C3—H3	0.9300
N1—N2	1.374 (3)	C4—C5	1.381 (5)
N2—C9	1.346 (3)	C4—H4	0.9300
N2—H2A	0.82 (3)	C5—C6	1.381 (4)
N3—C9	1.322 (3)	C5—H5	0.9300
N3—H3A	0.93 (4)	C6—C7	1.397 (4)
N3—H3B	0.88 (4)	C6—H6	0.9300
C1—F2ⁱ	1.343 (2)	C7—C8	1.472 (3)
C1—C2	1.497 (4)	C8—H8	0.9300

C8—N1—N2	116.0 (2)	C3—C4—C5	119.4 (3)
C9—N2—N1	119.7 (2)	C3—C4—H4	120.3
C9—N2—H2A	122 (2)	C5—C4—H4	120.3
N1—N2—H2A	118 (2)	C6—C5—C4	120.7 (3)
C9—N3—H3A	122 (2)	C6—C5—H5	119.7
C9—N3—H3B	121 (2)	C4—C5—H5	119.7
H3A—N3—H3B	117 (3)	C5—C6—C7	120.9 (3)
F1—C1—F2ⁱ	106.24 (16)	C5—C6—H6	119.5
F1—C1—F2	106.24 (16)	C7—C6—H6	119.5
F2ⁱ—C1—F2	105.8 (3)	C6—C7—C2	118.0 (2)
F1—C1—C2	113.0 (3)	C6—C7—C8	119.8 (2)
F2ⁱ—C1—C2	112.47 (15)	C2—C7—C8	122.2 (2)
F2—C1—C2	112.47 (15)	N1—C8—C7	119.5 (2)
C3—C2—C7	119.8 (3)	N1—C8—H8	120.3
C3—C2—C1	119.2 (3)	C7—C8—H8	120.3
C7—C2—C1	121.0 (2)	N3—C9—N2	117.1 (2)
C4—C3—C2	121.2 (3)	N3—C9—S1	123.3 (2)
C4—C3—H3	119.4	N2—C9—S1	119.5 (2)
C2—C3—H3	119.4

C8—N1—N2—C9	180.000 (1)	C5—C6—C7—C2	0.000 (2)
F1—C1—C2—C3	0.000 (2)	C5—C6—C7—C8	180.000 (1)
F2ⁱ—C1—C2—C3	−120.30 (18)	C3—C2—C7—C6	0.000 (2)
F2—C1—C2—C3	120.30 (18)	C1—C2—C7—C6	180.000 (1)
F1—C1—C2—C7	180.000 (1)	C3—C2—C7—C8	180.000 (1)
F2ⁱ—C1—C2—C7	59.70 (18)	C1—C2—C7—C8	0.000 (1)
F2—C1—C2—C7	−59.70 (18)	N2—N1—C8—C7	180.000 (1)
C7—C2—C3—C4	0.000 (2)	C6—C7—C8—N1	0.000 (1)
C1—C2—C3—C4	180.000 (1)	C2—C7—C8—N1	180.000 (1)
C2—C3—C4—C5	0.000 (2)	N1—N2—C9—N3	0.000 (2)
C3—C4—C5—C6	0.000 (2)	N1—N2—C9—S1	180.0
C4—C5—C6—C7	0.000 (2)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···S1ⁱⁱ	0.88 (4)	2.54 (4)	3.418 (3)	174 (3)
N2—H2A···S1ⁱⁱⁱ	0.82 (3)	2.61 (3)	3.430 (2)	173 (3)

Symmetry codes: (ii) x+1/2, y, −z+5/2; (iii) x−1/2, y, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₉H₈F₃N₃S
M_r	247.24
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	294
a, b, c (Å)	8.628 (2), 6.9795 (17), 18.222 (4)
V (Å³)	1097.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.40 × 0.40 × 0.30

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.886, 0.912
No. of measured, independent and observed [I > 2σ(I)] reflections	5953, 1228, 869
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.113, 1.07
No. of reflections	1228
No. of parameters	101
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), 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—H3B···S1ⁱ	0.88 (4)	2.54 (4)	3.418 (3)	174 (3)
N2—H2A···S1ⁱⁱ	0.82 (3)	2.61 (3)	3.430 (2)	173 (3)

Symmetry codes: (i) x+1/2, y, −z+5/2; (ii) x−1/2, y, −z+5/2.

Acknowledgements

This work was supported by the Tianjn University of Science and Technology Research Fund (No. 20090216).

References

Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deng, Q.-L., Yu, M., Chen, X., Diao, C.-H., Jing, Z.-L. & Fan, Z. (2005). Acta Cryst. E61, o2545–o2546. Web of Science CSD CrossRef IUCr Journals Google Scholar
Guo, M.-J., Sun, J.-C., Jing, Z.-L., Yu, M. & Chen, X. (2006). Acta Cryst. E62, o820–o821. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jing, Z.-L., Fan, Z., Yu, M., Chen, X. & Deng, Q.-L. (2005). Acta Cryst. E61, o3208–o3209. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kahwa, I. A., Selbin, J., Hsieh, T. C.-Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185. CrossRef CAS Web of Science Google Scholar
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, M., Chen, X. & Jing, Z.-L. (2005). Acta Cryst. E61, o1345–o1346. Web of Science CSD CrossRef IUCr Journals Google Scholar