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

Abstract

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,

• a = 5.6984 (13) Å

• b = 8.9493 (14) Å

• c = 22.813 (2) Å

• β = 93.860 (2)°

• V = 1160.7 (3) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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

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.

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
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) ; (ii) .

supplementary crystallographic information

Comment

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].

Experimental

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%.

Refinement

All H atoms were placed in geometrically idealized positions (N—H 0.86 and C—H= 0.93–0.96 Å) and treated as riding on their parent atoms, with U_iso(H) = 1.2 U_eq(C,N).

Figures

Fig. 1.

The molecular structure of (I) showing the atomic numbering scheme and 30% probability displacement ellipsoids.

Crystal data

C10H14N4S	F(000) = 472
Mr = 222.31	Dx = 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

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

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)] = 0.039	H-atom parameters constrained
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.0432P)2 + 0.4004P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2047 reflections	Δρmax = 0.17 e Å−3
137 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: 0.027 (3)

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
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 (Ų)

	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, °)

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, °)

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.