1-[4-(Dimethyl­amino)benzyl­idene]-4-methyl­thio­semicarbazide

Abstract

In the title compound, C₁₁H₁₆N₄S, an intra­molecular N—H⋯N hydrogen bond generates an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H⋯S bonds occur, generating an R ₂ ²(8) loop.

Related literature

For a related structure, see: Girgis (2006 ▶).

Experimental

Crystal data

• C₁₁H₁₆N₄S

• M _r = 236.34

• Monoclinic,

• a = 10.517 (2) Å

• b = 12.873 (3) Å

• c = 10.552 (2) Å

• β = 119.19 (3)°

• V = 1247.3 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.24 mm⁻¹

• T = 293 K

• 0.22 × 0.20 × 0.18 mm

Data collection

• Bruker SMART CCD diffractometer

• 11842 measured reflections

• 2847 independent reflections

• 2391 reflections with I > 2σ(I)

• R _int = 0.031

Refinement

• R[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 0.178

• S = 1.12

• 2847 reflections

• 145 parameters

• H-atom parameters constrained

• Δρ_max = 0.43 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker 1997 ▶); cell refinement: SAINT (Bruker 1997 ▶); 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
N4—H4A⋯N2	0.86	2.22	2.613 (2)	108
N3—H3A⋯S1i	0.86	2.59	3.3890 (16)	155

Symmetry code: (i) .

supplementary crystallographic information

Experimental

A mixture of 4-(dimethylamino)benzaldehyde (0.10 mol), and 4-methylthiosemicarbazide (0.10 mol) was stirred in refluxing ethanol (10 ml) for 4 h to afford the title compound (0.083 mol, yield 83%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93-0.97 Å; N—H = 0.86Å and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Figures

Fig. 1.

The structure of (I) showing 30% probability displacement ellipsoids.

Crystal data

C11H16N4S	F(000) = 504
Mr = 236.34	Dx = 1.259 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2391 reflections
a = 10.517 (2) Å	θ = 3.2–27.5°
b = 12.873 (3) Å	µ = 0.24 mm−1
c = 10.552 (2) Å	T = 293 K
β = 119.19 (3)°	Block, colorless
V = 1247.3 (4) Å3	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2391 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
graphite	θmax = 27.5°, θmin = 3.2°
phi and ω scans	h = −13→11
11842 measured reflections	k = −15→16
2847 independent reflections	l = −13→13

Refinement

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) = 0.178	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.1186P)2 + 0.111P] where P = (Fo2 + 2Fc2)/3
2847 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
S1	0.60342 (4)	0.15360 (4)	0.05021 (6)	0.0595 (2)
N2	0.17952 (14)	0.12707 (11)	−0.13146 (16)	0.0468 (3)
N3	0.32723 (14)	0.10421 (10)	−0.05970 (16)	0.0491 (4)
H3A	0.3569	0.0426	−0.0272	0.059*
C6	−0.06129 (17)	0.06639 (12)	−0.20701 (17)	0.0435 (4)
N4	0.36809 (16)	0.27166 (11)	−0.09695 (18)	0.0537 (4)
H4A	0.2749	0.2772	−0.1463	0.064*
C3	−0.36590 (17)	0.09210 (14)	−0.32393 (17)	0.0481 (4)
C7	−0.13111 (19)	0.15789 (12)	−0.2769 (2)	0.0495 (4)
H7A	−0.0763	0.2116	−0.2848	0.059*
C10	0.42361 (17)	0.17963 (13)	−0.04141 (17)	0.0433 (4)
C9	0.09536 (17)	0.05248 (12)	−0.13907 (18)	0.0448 (4)
H9A	0.1355	−0.0119	−0.1002	0.054*
C5	−0.14729 (19)	−0.01233 (13)	−0.1990 (2)	0.0501 (4)
H5A	−0.1036	−0.0746	−0.1543	0.060*
C8	−0.27852 (19)	0.17078 (14)	−0.3344 (2)	0.0537 (4)
H8A	−0.3215	0.2327	−0.3812	0.064*
C4	−0.29596 (19)	−0.00089 (14)	−0.2553 (2)	0.0529 (4)
H4B	−0.3502	−0.0552	−0.2478	0.063*
N1	−0.51338 (16)	0.10490 (14)	−0.38125 (18)	0.0634 (4)
C2	−0.5998 (2)	0.0282 (2)	−0.3574 (3)	0.0758 (6)
H2B	−0.5423	−0.0329	−0.3152	0.114*
H2C	−0.6834	0.0107	−0.4484	0.114*
H2D	−0.6313	0.0560	−0.2929	0.114*
C11	0.4544 (2)	0.36333 (16)	−0.0797 (3)	0.0730 (6)
H12A	0.3912	0.4207	−0.1293	0.109*
H12B	0.5174	0.3507	−0.1201	0.109*
H12C	0.5120	0.3795	0.0216	0.109*
C1	−0.5822 (2)	0.2016 (2)	−0.4442 (3)	0.0929 (8)
H1A	−0.5142	0.2460	−0.4541	0.139*
H1B	−0.6138	0.2345	−0.3828	0.139*
H1C	−0.6647	0.1893	−0.5381	0.139*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0340 (3)	0.0526 (3)	0.0744 (4)	−0.00233 (15)	0.0127 (2)	−0.00072 (19)
N2	0.0336 (7)	0.0484 (7)	0.0547 (8)	0.0008 (5)	0.0187 (6)	0.0001 (6)
N3	0.0335 (6)	0.0439 (7)	0.0637 (8)	0.0010 (5)	0.0188 (6)	0.0032 (6)
C6	0.0375 (8)	0.0465 (8)	0.0464 (8)	−0.0018 (6)	0.0205 (6)	−0.0026 (6)
N4	0.0395 (7)	0.0477 (8)	0.0626 (9)	−0.0017 (5)	0.0160 (6)	0.0071 (6)
C3	0.0382 (8)	0.0593 (10)	0.0458 (8)	−0.0015 (6)	0.0197 (6)	−0.0050 (7)
C7	0.0438 (9)	0.0455 (9)	0.0594 (10)	−0.0032 (6)	0.0253 (8)	0.0021 (7)
C10	0.0382 (7)	0.0455 (8)	0.0436 (8)	−0.0027 (6)	0.0180 (6)	−0.0032 (6)
C9	0.0391 (8)	0.0437 (8)	0.0504 (8)	−0.0006 (6)	0.0210 (6)	−0.0012 (6)
C5	0.0446 (9)	0.0455 (8)	0.0572 (10)	−0.0021 (6)	0.0226 (8)	0.0055 (7)
C8	0.0447 (9)	0.0481 (9)	0.0653 (11)	0.0052 (7)	0.0245 (8)	0.0049 (7)
C4	0.0433 (9)	0.0567 (9)	0.0582 (10)	−0.0095 (7)	0.0245 (8)	0.0025 (7)
N1	0.0370 (8)	0.0805 (11)	0.0677 (10)	−0.0010 (7)	0.0218 (7)	0.0000 (8)
C2	0.0468 (10)	0.1131 (18)	0.0689 (12)	−0.0167 (11)	0.0293 (9)	−0.0044 (12)
C11	0.0597 (12)	0.0529 (10)	0.0951 (16)	−0.0073 (9)	0.0289 (11)	0.0121 (10)
C1	0.0477 (11)	0.0861 (17)	0.128 (2)	0.0166 (11)	0.0301 (13)	−0.0016 (16)

Geometric parameters (Å, °)

S1—C10	1.6852 (17)	C9—H9A	0.9300
N2—C9	1.282 (2)	C5—C4	1.383 (3)
N2—N3	1.3877 (19)	C5—H5A	0.9300
N3—C10	1.348 (2)	C8—H8A	0.9300
N3—H3A	0.8600	C4—H4B	0.9300
C6—C5	1.388 (2)	N1—C1	1.431 (3)
C6—C7	1.394 (2)	N1—C2	1.444 (3)
C6—C9	1.452 (2)	C2—H2B	0.9600
N4—C10	1.325 (2)	C2—H2C	0.9600
N4—C11	1.445 (2)	C2—H2D	0.9600
N4—H4A	0.8600	C11—H12A	0.9600
C3—N1	1.372 (2)	C11—H12B	0.9600
C3—C4	1.407 (2)	C11—H12C	0.9600
C3—C8	1.408 (2)	C1—H1A	0.9600
C7—C8	1.372 (2)	C1—H1B	0.9600
C7—H7A	0.9300	C1—H1C	0.9600
C9—N2—N3	115.50 (14)	C7—C8—H8A	119.4
C10—N3—N2	119.27 (14)	C3—C8—H8A	119.4
C10—N3—H3A	120.4	C5—C4—C3	120.64 (15)
N2—N3—H3A	120.4	C5—C4—H4B	119.7
C5—C6—C7	117.29 (14)	C3—C4—H4B	119.7
C5—C6—C9	119.74 (14)	C3—N1—C1	121.07 (17)
C7—C6—C9	122.92 (14)	C3—N1—C2	120.89 (18)
C10—N4—C11	124.08 (16)	C1—N1—C2	117.18 (18)
C10—N4—H4A	118.0	N1—C2—H2B	109.5
C11—N4—H4A	118.0	N1—C2—H2C	109.5
N1—C3—C4	121.59 (16)	H2B—C2—H2C	109.5
N1—C3—C8	121.31 (16)	N1—C2—H2D	109.5
C4—C3—C8	117.07 (14)	H2B—C2—H2D	109.5
C8—C7—C6	121.76 (15)	H2C—C2—H2D	109.5
C8—C7—H7A	119.1	N4—C11—H12A	109.5
C6—C7—H7A	119.1	N4—C11—H12B	109.5
N4—C10—N3	116.27 (14)	H12A—C11—H12B	109.5
N4—C10—S1	124.11 (13)	N4—C11—H12C	109.5
N3—C10—S1	119.61 (13)	H12A—C11—H12C	109.5
N2—C9—C6	121.42 (15)	H12B—C11—H12C	109.5
N2—C9—H9A	119.3	N1—C1—H1A	109.5
C6—C9—H9A	119.3	N1—C1—H1B	109.5
C4—C5—C6	121.98 (15)	H1A—C1—H1B	109.5
C4—C5—H5A	119.0	N1—C1—H1C	109.5
C6—C5—H5A	119.0	H1A—C1—H1C	109.5
C7—C8—C3	121.23 (16)	H1B—C1—H1C	109.5

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2	0.86	2.22	2.613 (2)	108
N3—H3A···S1i	0.86	2.59	3.3890 (16)	155

Symmetry codes: (i) −x+1, −y, −z.