4-Cyano­benzaldehyde thio­semi­carbazone

Wu, D.-H.; Zhang, Y.-H.; Li, Z.-F.; Li, Y.-H.

doi:10.1107/S1600536808041792

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o107

doi:10.1107/S1600536808041792

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4-Cyanobenzaldehyde thiosemicarbazone

De-Hong Wu,^a ^* You-Hong Zhang,^a Zhu-Feng Li ^a and Yong-Hua Li ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: wudh1971@sohu.com

(Received 29 October 2008; accepted 9 December 2008; online 13 December 2008)

The molecule of the title compound, C₉H₈N₄S, adopts an E configuration about both the C=N and C—NH bonds. In the crystal structure, adjacent molecules are linked by intermolecular N—H⋯S hydrogen-bonding interactions, forming chains running parallel to the b axis.

Related literature

For a general background to thiosemicarbazone compounds, see: Casas et al. (2000 ); Tarafder et al. (2000 ); Deschamps et al. (2003 ); Liu et al. (1999 ); Wu et al. (2000 ). For reference structural data, see: Sutton (1965 ).

Experimental

Crystal data

C₉H₈N₄S
M_r = 204.26
Monoclinic, P 2₁ /c
a = 12.284 (6) Å
b = 8.209 (4) Å
c = 10.058 (3) Å
β = 92.20 (3)°
V = 1013.5 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 291 (2) K
0.25 × 0.17 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.94, T_max = 0.96
10019 measured reflections
2309 independent reflections
1596 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.109
S = 1.01
2309 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1ⁱ	0.86	2.50	3.355 (2)	171
N1—H1B⋯S1ⁱⁱ	0.86	2.63	3.399 (3)	150
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: 10.1107/S1600536808041792/rz2264sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041792/rz2264Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones constitute an important class of N,S donors due to their propensity to react with a wide range of metals (Casas et al., 2000). Schiff bases show potential as antimicrobial and anticancer agents (Tarafder et al., 2000; Deschamps et al., 2003) and so have biochemical and pharmacological applications. It has been postulated that extensive electron delocalization in the thiosemicarbazone moiety helps the free thiosemicarbazone ligands and their metal complexes to exhibit SHG (second harmonic generation) efficiency (Liu et al., 1999; Wu et al., 2000). As part of a research on non-linear optical materials, specifically thiosemicarbazones and their metal complexes, we report here the crystal structure of a new Schiff base compound derived from thiosemicarbazide and 4-cyanobenzaldehyde.

In the title compound (Fig. 1), the thiosemicarbazone moiety is nearly planar (maximum deviation 0.113 (2) Å for atom N2) and shows an E configuration about both the C1═N2 and C2═N3 bonds. The molecule is not strictly planar, the dihedral angle between the thiosemicarbazone moiety and the phenyl ring being 15.8 (6)°. The C—S bond distance of 1.689 (2) Å agrees well with similar bonds in related compounds, being intermediate between the value of 1.82Å for a C—S single bond and 1.56 Å for a C═S double bond (Sutton, 1965). The C1—N2 bond distance (1.344 (3)Å) is indicative of some double-bond character, suggesting extensive electron delocalization in the whole molecule. The C1—N1 bond distance of 1.316 (3)Å is also indicative of some double-bond character. All the bond distances except for the C6—C9 bond length (1.447 (3) Å) fall within the normal range. In the crystal packing, adjacent molecules are linked by N—H···S hydrogen bonds (Table 1) to form chains running parallel to the b axis.

Related literature top

For a general background to thiosemicarbazone compounds, see: Casas et al. (2000); Tarafder et al. (2000); Deschamps et al. (2003); Liu et al. (1999); Wu et al. (2000). For reference structural data, see: Sutton (1965).

Experimental top

The title compound was synthesized by refluxing 4-cyanobenzaldehyde (1.05 g, 8 mmol) and thiosemicarbazide (0.73 g, 8 mmol) in absolute ethanol (40 ml) for 6 h. After cooling to room temperature, the white solid formed was isolated and dried under vacuum (1.47 g, yield 90%). Single crystals suitable for X-ray structure analysis were obtained by slow evaporation of a methanol solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

4-Cyanobenzaldehyde thiosemicarbazone top

Crystal data top

C₉H₈N₄S	F(000) = 424
M_r = 204.26	D_x = 1.339 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1740 reflections
a = 12.284 (6) Å	θ = 2.5–27.5°
b = 8.209 (4) Å	µ = 0.28 mm⁻¹
c = 10.058 (3) Å	T = 291 K
β = 92.20 (3)°	Block, colourless
V = 1013.5 (8) Å³	0.25 × 0.17 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2309 independent reflections
Radiation source: fine-focus sealed tube	1596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.94, T_max = 0.96	l = −12→13
10019 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0258P)² + 0.6908P] where P = (F_o² + 2F_c²)/3
2309 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₈N₄S	V = 1013.5 (8) Å³
M_r = 204.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.284 (6) Å	µ = 0.28 mm⁻¹
b = 8.209 (4) Å	T = 291 K
c = 10.058 (3) Å	0.25 × 0.17 × 0.15 mm
β = 92.20 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2309 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1596 reflections with I > 2σ(I)
T_min = 0.94, T_max = 0.96	R_int = 0.055
10019 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.01	Δρ_max = 0.17 e Å⁻³
2309 reflections	Δρ_min = −0.19 e Å⁻³
127 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
C1	0.07786 (19)	0.5792 (3)	0.6753 (2)	0.0446 (6)
C2	0.18757 (19)	0.2982 (3)	0.4587 (2)	0.0454 (6)
H2	0.1575	0.2048	0.4946	0.054*
C3	0.26310 (18)	0.2841 (3)	0.3506 (2)	0.0426 (6)
C4	0.30116 (19)	0.1304 (3)	0.3163 (2)	0.0482 (6)
H4	0.2748	0.0384	0.3583	0.058*
C5	0.3781 (2)	0.1135 (3)	0.2198 (2)	0.0532 (7)
H5	0.4029	0.0108	0.1964	0.064*
C6	0.4175 (2)	0.2517 (3)	0.1588 (2)	0.0509 (6)
C7	0.3777 (2)	0.4058 (3)	0.1891 (2)	0.0541 (7)
H7	0.4028	0.4973	0.1452	0.065*
C8	0.3008 (2)	0.4214 (3)	0.2846 (2)	0.0500 (6)
H8	0.2740	0.5239	0.3052	0.060*
C9	0.5021 (2)	0.2377 (4)	0.0632 (3)	0.0616 (7)
N1	0.1138 (2)	0.7144 (3)	0.6221 (2)	0.0717 (8)
H1A	0.1485	0.7106	0.5496	0.086*
H1B	0.1026	0.8065	0.6600	0.086*
N2	0.09749 (15)	0.4384 (2)	0.61235 (17)	0.0436 (5)
H2A	0.0694	0.3490	0.6396	0.052*
N3	0.16254 (15)	0.4379 (2)	0.50426 (18)	0.0441 (5)
N4	0.5709 (2)	0.2293 (3)	−0.0102 (3)	0.0853 (9)
S1	0.01195 (6)	0.57476 (8)	0.81966 (6)	0.0544 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0526 (14)	0.0390 (12)	0.0423 (12)	0.0019 (12)	0.0033 (11)	0.0001 (11)
C2	0.0475 (14)	0.0477 (14)	0.0414 (13)	−0.0021 (12)	0.0063 (11)	−0.0010 (11)
C3	0.0399 (13)	0.0479 (14)	0.0402 (12)	−0.0015 (11)	0.0030 (10)	−0.0042 (10)
C4	0.0505 (14)	0.0477 (14)	0.0467 (13)	−0.0025 (12)	0.0053 (12)	−0.0032 (11)
C5	0.0533 (15)	0.0568 (17)	0.0498 (14)	0.0051 (13)	0.0050 (12)	−0.0093 (12)
C6	0.0463 (14)	0.0659 (17)	0.0406 (13)	0.0036 (14)	0.0050 (11)	−0.0039 (13)
C7	0.0540 (15)	0.0593 (17)	0.0496 (14)	−0.0012 (14)	0.0094 (12)	0.0056 (13)
C8	0.0533 (15)	0.0469 (14)	0.0500 (14)	0.0026 (13)	0.0072 (11)	−0.0046 (12)
C9	0.0626 (17)	0.0696 (19)	0.0535 (15)	0.0057 (15)	0.0115 (14)	0.0018 (14)
N1	0.112 (2)	0.0411 (13)	0.0645 (15)	−0.0058 (13)	0.0407 (14)	−0.0043 (11)
N2	0.0546 (12)	0.0375 (11)	0.0396 (10)	0.0007 (10)	0.0111 (9)	−0.0008 (9)
N3	0.0492 (11)	0.0464 (12)	0.0372 (10)	0.0016 (10)	0.0068 (8)	−0.0027 (9)
N4	0.088 (2)	0.091 (2)	0.0797 (18)	0.0167 (17)	0.0398 (16)	0.0100 (16)
S1	0.0765 (5)	0.0431 (3)	0.0448 (3)	0.0083 (4)	0.0184 (3)	0.0010 (3)

Geometric parameters (Å, º) top

C1—N1	1.316 (3)	C5—H5	0.9300
C1—N2	1.344 (3)	C6—C7	1.394 (4)
C1—S1	1.689 (2)	C6—C9	1.447 (3)
C2—N3	1.277 (3)	C7—C8	1.378 (3)
C2—C3	1.461 (3)	C7—H7	0.9300
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.394 (3)	C9—N4	1.146 (3)
C3—C8	1.396 (3)	N1—H1A	0.8600
C4—C5	1.387 (3)	N1—H1B	0.8600
C4—H4	0.9300	N2—N3	1.374 (2)
C5—C6	1.385 (4)	N2—H2A	0.8600

N1—C1—N2	117.7 (2)	C5—C6—C9	120.1 (3)
N1—C1—S1	123.15 (19)	C7—C6—C9	118.9 (2)
N2—C1—S1	119.15 (18)	C8—C7—C6	119.4 (2)
N3—C2—C3	120.5 (2)	C8—C7—H7	120.3
N3—C2—H2	119.8	C6—C7—H7	120.3
C3—C2—H2	119.8	C7—C8—C3	120.4 (2)
C4—C3—C8	119.5 (2)	C7—C8—H8	119.8
C4—C3—C2	119.0 (2)	C3—C8—H8	119.8
C8—C3—C2	121.4 (2)	N4—C9—C6	178.1 (3)
C5—C4—C3	120.5 (2)	C1—N1—H1A	120.0
C5—C4—H4	119.7	C1—N1—H1B	120.0
C3—C4—H4	119.7	H1A—N1—H1B	120.0
C6—C5—C4	119.1 (2)	C1—N2—N3	119.73 (19)
C6—C5—H5	120.4	C1—N2—H2A	120.1
C4—C5—H5	120.4	N3—N2—H2A	120.1
C5—C6—C7	121.0 (2)	C2—N3—N2	116.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.50	3.355 (2)	171
N1—H1B···S1ⁱⁱ	0.86	2.63	3.399 (3)	150

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

Experimental details

Crystal data
Chemical formula	C₉H₈N₄S
M_r	204.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	12.284 (6), 8.209 (4), 10.058 (3)
β (°)	92.20 (3)
V (Å³)	1013.5 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.25 × 0.17 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.94, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	10019, 2309, 1596
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.109, 1.01
No. of reflections	2309
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19

Computer programs: CrystalClear (Rigaku, 2005), 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
N2—H2A···S1ⁱ	0.86	2.50	3.355 (2)	170.7
N1—H1B···S1ⁱⁱ	0.86	2.63	3.399 (3)	150.2

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

Acknowledgements

The authors thank the Start-up Projects for Postdoctoral Research Funds of Southeast University (grant No. 1112000048).

References

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