(E)-1-[4-(Dimethyl­amino)benzyl­idene]thio­semicarbazide

Sun, Y.; Fu, S.; Zhang, J.; Wang, X.; Wang, D.

doi:10.1107/S1600536808043778

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o237

doi:10.1107/S1600536808043778

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(E)-1-[4-(Dimethylamino)benzylidene]thiosemicarbazide

Yuying Sun,^a Shizhou Fu,^b Junhong Zhang,^b Xiao Wang ^b ^* and Daqi Wang ^b

^aAnalytical and Testing Center of Beihua Univerisity, Jilin 132013, People's Republic of China, and ^bDepartment of Chemistry, Liaocheng University, Liaocheng 250059, People's Republic of China
^*Correspondence e-mail: wdq@lcu.edu.cn

(Received 28 November 2008; accepted 23 December 2008; online 8 January 2009)

In the title molecule, C₁₀H₁₄N₄S, the thiorea plane and benzene ring form a dihedral angle of 16.0 (3) Å. In the crystal structure, intermolecular N—H⋯S hydrogen bonds link the molecules into ribbons extended in the [100] direction; these incorporate inversion dimers.

Related literature

For the biomedical properties of thiosemicarbazones, see: Beraldo & Gambino (2004 ); Bondock et al. (2007 ). For the crystal structure of the related compound benzyl N′-(2-chlorobenzylidene)hydrazinecarbodithioate, see Shi et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₄N₄S
M_r = 222.31
Monoclinic, P 2₁ /n
a = 5.6984 (13) Å
b = 8.9493 (14) Å
c = 22.813 (2) Å
β = 93.860 (2)°
V = 1160.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 (2) K
0.50 × 0.48 × 0.26 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.884, T_max = 0.937
5769 measured reflections
2047 independent reflections
1435 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.110
S = 1.02
2047 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.17 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—H3A⋯S1ⁱ	0.86	2.84	3.408 (2)	125
N3—H3B⋯S1ⁱⁱ	0.86	2.57	3.417 (2)	168
Symmetry codes: (i) x-1, y, z; (ii) -x+2, -y, -z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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: 10.1107/S1600536808043778/cv2492sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043778/cv2492Isup2.hkl

checkCIF report

Comment top

The title compound (I) is a derivative of thiosemicarbazones, which are important for drug design (Beraldo & Gambino, 2004) and for synthesis of heterocyclic rings (Bondock et al., 2007).

In (I) (Fig.1), all bond lengths and angles are normal and comparable to those observed in the related compound (Shi et al., 2008). The dihedral angle between the C9/C10/N4 plane and the benzene ring is 10.14 (3) °. The thiorea plane and benzene ring form a dihedral angle of 15.97 (3) °. The C1=S1 bond length of 1.674 (2) Å is intermediate between the values of 1.82 Å for a C—S single bond and 1.56 Å for a C=S double bond. The C=N—N angle in the molecule of 115.69 (19)° is significantly smaller than the ideal value of 120° expected for sp² -hybridized N atoms. This is probably a consequence of repulsion between the nitrogen lone pairs and the adjacent N bonds.

In the crystal, the intermolecular N—H···S hydrogen bonds (Table 1) link the molecules into ribbons extended in direction [100].

Related literature top

For the biomedical properties of thiosemicarbazones, see: Beraldo & Gambino (2004); Bondock et al. (2007). For the crystal structure of related benzyl N^'-(2-chlorobenzylidene)hydrazinecarbodithioate, see Shi et al. (2008).

Experimental top

N,N' –Dimethylaminobenzaldehyde (0.5 mmol), thiosemicarbazide (0.5 mmol) and 10 ml e thanol were mixed in 50 ml flask. After stirring 30 min at 373 K, the resulting mixture was recrystalized from ethanol, affording the title compound as a orange crystalline solid. Elemental analysis: calculated for C₁₀H₁₄N₄S: C 54.03, H 6.35, N 25.20%; found: C 54.38, H 6.54, N 25.27%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (I) showing the atomic numbering scheme and 30% probability displacement ellipsoids.

(E)-1-[4-(Dimethylamino)benzylidene]thiosemicarbazide top

Crystal data top

C₁₀H₁₄N₄S	F(000) = 472
M_r = 222.31	D_x = 1.272 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.6984 (13) Å	Cell parameters from 2093 reflections
b = 8.9493 (14) Å	θ = 2.5–25.9°
c = 22.813 (2) Å	µ = 0.25 mm⁻¹
β = 93.860 (2)°	T = 298 K
V = 1160.7 (3) Å³	Block, orange
Z = 4	0.50 × 0.48 × 0.26 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2047 independent reflections
Radiation source: fine-focus sealed tube	1435 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.884, T_max = 0.937	k = −10→10
5769 measured reflections	l = −27→17

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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0432P)² + 0.4004P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2047 reflections	Δρ_max = 0.17 e Å⁻³
137 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: 0.027 (3)

Crystal data top

C₁₀H₁₄N₄S	V = 1160.7 (3) Å³
M_r = 222.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.6984 (13) Å	µ = 0.25 mm⁻¹
b = 8.9493 (14) Å	T = 298 K
c = 22.813 (2) Å	0.50 × 0.48 × 0.26 mm
β = 93.860 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2047 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1435 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.937	R_int = 0.037
5769 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.02	Δρ_max = 0.17 e Å⁻³
2047 reflections	Δρ_min = −0.20 e Å⁻³
137 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
N1	0.9364 (3)	0.1808 (2)	0.14592 (8)	0.0544 (5)
H1	1.0442	0.2390	0.1611	0.065*
N2	0.7454 (3)	0.1467 (2)	0.17756 (8)	0.0497 (5)
N3	0.7772 (3)	0.0474 (2)	0.06910 (8)	0.0583 (6)
H3A	0.6548	0.0349	0.0887	0.070*
H3B	0.7820	0.0093	0.0346	0.070*
N4	0.0633 (3)	0.1090 (2)	0.39241 (9)	0.0621 (6)
S1	1.20240 (11)	0.15551 (9)	0.05735 (3)	0.0708 (3)
C1	0.9570 (4)	0.1249 (2)	0.09195 (9)	0.0473 (5)
C2	0.7371 (4)	0.2136 (3)	0.22678 (9)	0.0510 (6)
H2	0.8539	0.2829	0.2374	0.061*
C3	0.5554 (4)	0.1872 (2)	0.26677 (9)	0.0470 (5)
C4	0.5549 (4)	0.2699 (3)	0.31838 (10)	0.0560 (6)
H4	0.6676	0.3441	0.3253	0.067*
C5	0.3937 (4)	0.2457 (3)	0.35945 (10)	0.0573 (6)
H5	0.3985	0.3044	0.3932	0.069*
C6	0.2228 (4)	0.1346 (2)	0.35143 (9)	0.0483 (5)
C7	0.2210 (4)	0.0514 (3)	0.29886 (9)	0.0528 (6)
H7	0.1082	−0.0226	0.2916	0.063*
C8	0.3831 (4)	0.0782 (3)	0.25809 (9)	0.0507 (6)
H8	0.3771	0.0217	0.2238	0.061*
C9	−0.1011 (4)	−0.0139 (3)	0.38610 (12)	0.0684 (7)
H9A	−0.1877	−0.0074	0.3486	0.103*
H9B	−0.2082	−0.0092	0.4168	0.103*
H9C	−0.0166	−0.1067	0.3887	0.103*
C10	0.0832 (6)	0.1853 (3)	0.44832 (12)	0.0900 (10)
H10A	0.2193	0.1495	0.4711	0.135*
H10B	−0.0549	0.1664	0.4690	0.135*
H10C	0.0984	0.2908	0.4419	0.135*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0517 (11)	0.0650 (13)	0.0474 (11)	−0.0059 (9)	0.0093 (9)	−0.0067 (10)
N2	0.0506 (10)	0.0566 (12)	0.0425 (10)	0.0063 (9)	0.0089 (8)	0.0035 (9)
N3	0.0458 (10)	0.0862 (15)	0.0438 (11)	−0.0059 (10)	0.0098 (8)	−0.0078 (10)
N4	0.0661 (12)	0.0674 (14)	0.0547 (12)	−0.0014 (10)	0.0186 (10)	−0.0096 (10)
S1	0.0521 (4)	0.0967 (6)	0.0658 (5)	−0.0157 (3)	0.0204 (3)	−0.0145 (4)
C1	0.0442 (12)	0.0545 (14)	0.0433 (12)	0.0065 (10)	0.0034 (9)	0.0047 (10)
C2	0.0608 (13)	0.0469 (13)	0.0454 (13)	0.0028 (11)	0.0048 (11)	0.0003 (10)
C3	0.0582 (13)	0.0433 (13)	0.0396 (12)	0.0080 (10)	0.0041 (10)	0.0000 (10)
C4	0.0701 (15)	0.0447 (13)	0.0541 (14)	−0.0055 (11)	0.0105 (12)	−0.0073 (11)
C5	0.0776 (16)	0.0499 (14)	0.0455 (13)	0.0010 (12)	0.0125 (12)	−0.0134 (11)
C6	0.0521 (12)	0.0480 (13)	0.0450 (13)	0.0087 (10)	0.0042 (10)	−0.0018 (10)
C7	0.0521 (12)	0.0561 (15)	0.0499 (13)	−0.0030 (11)	0.0018 (10)	−0.0084 (11)
C8	0.0583 (13)	0.0545 (14)	0.0389 (12)	0.0055 (11)	−0.0010 (10)	−0.0095 (10)
C9	0.0647 (15)	0.0705 (17)	0.0714 (17)	−0.0004 (13)	0.0154 (13)	0.0057 (14)
C10	0.118 (2)	0.088 (2)	0.0690 (19)	−0.0113 (18)	0.0441 (17)	−0.0195 (16)

Geometric parameters (Å, º) top

N1—C1	1.342 (3)	C4—C5	1.372 (3)
N1—N2	1.380 (2)	C4—H4	0.9300
N1—H1	0.8600	C5—C6	1.396 (3)
N2—C2	1.276 (3)	C5—H5	0.9300
N3—C1	1.315 (3)	C6—C7	1.411 (3)
N3—H3A	0.8600	C7—C8	1.375 (3)
N3—H3B	0.8600	C7—H7	0.9300
N4—C6	1.366 (3)	C8—H8	0.9300
N4—C10	1.445 (3)	C9—H9A	0.9600
N4—C9	1.446 (3)	C9—H9B	0.9600
S1—C1	1.674 (2)	C9—H9C	0.9600
C2—C3	1.445 (3)	C10—H10A	0.9600
C2—H2	0.9300	C10—H10B	0.9600
C3—C8	1.389 (3)	C10—H10C	0.9600
C3—C4	1.391 (3)

C1—N1—N2	121.22 (18)	C4—C5—H5	119.5
C1—N1—H1	119.4	C6—C5—H5	119.5
N2—N1—H1	119.4	N4—C6—C5	121.3 (2)
C2—N2—N1	115.69 (19)	N4—C6—C7	121.8 (2)
C1—N3—H3A	120.0	C5—C6—C7	116.9 (2)
C1—N3—H3B	120.0	C8—C7—C6	121.1 (2)
H3A—N3—H3B	120.0	C8—C7—H7	119.5
C6—N4—C10	120.6 (2)	C6—C7—H7	119.5
C6—N4—C9	121.0 (2)	C7—C8—C3	121.8 (2)
C10—N4—C9	117.4 (2)	C7—C8—H8	119.1
N3—C1—N1	116.51 (19)	C3—C8—H8	119.1
N3—C1—S1	123.55 (17)	N4—C9—H9A	109.5
N1—C1—S1	119.94 (17)	N4—C9—H9B	109.5
N2—C2—C3	123.3 (2)	H9A—C9—H9B	109.5
N2—C2—H2	118.3	N4—C9—H9C	109.5
C3—C2—H2	118.3	H9A—C9—H9C	109.5
C8—C3—C4	116.9 (2)	H9B—C9—H9C	109.5
C8—C3—C2	123.7 (2)	N4—C10—H10A	109.5
C4—C3—C2	119.3 (2)	N4—C10—H10B	109.5
C5—C4—C3	122.3 (2)	H10A—C10—H10B	109.5
C5—C4—H4	118.9	N4—C10—H10C	109.5
C3—C4—H4	118.9	H10A—C10—H10C	109.5
C4—C5—C6	121.1 (2)	H10B—C10—H10C	109.5

C1—N1—N2—C2	−175.76 (19)	C9—N4—C6—C5	−175.0 (2)
N2—N1—C1—N3	5.8 (3)	C10—N4—C6—C7	173.9 (2)
N2—N1—C1—S1	−174.31 (15)	C9—N4—C6—C7	5.8 (3)
N1—N2—C2—C3	−177.43 (18)	C4—C5—C6—N4	179.4 (2)
N2—C2—C3—C8	5.5 (3)	C4—C5—C6—C7	−1.4 (3)
N2—C2—C3—C4	−177.3 (2)	N4—C6—C7—C8	−179.8 (2)
C8—C3—C4—C5	0.4 (3)	C5—C6—C7—C8	0.9 (3)
C2—C3—C4—C5	−177.0 (2)	C6—C7—C8—C3	0.2 (3)
C3—C4—C5—C6	0.7 (4)	C4—C3—C8—C7	−0.8 (3)
C10—N4—C6—C5	−6.9 (4)	C2—C3—C8—C7	176.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S1ⁱ	0.86	2.84	3.408 (2)	125
N3—H3B···S1ⁱⁱ	0.86	2.57	3.417 (2)	168

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₄S
M_r	222.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	5.6984 (13), 8.9493 (14), 22.813 (2)
β (°)	93.860 (2)
V (Å³)	1160.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.50 × 0.48 × 0.26

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.884, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	5769, 2047, 1435
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.110, 1.02
No. of reflections	2047
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.20

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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···S1ⁱ	0.86	2.84	3.408 (2)	125.0
N3—H3B···S1ⁱⁱ	0.86	2.57	3.417 (2)	168.4

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

Acknowledgements

The authors acknowledge the financial support of the University Student Science and Technology Culture Foundation of Liaocheng University (grant No. SRT07012HX2).

References

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