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

Li, Y.-F.; Jian, F.-F.

doi:10.1107/S1600536810018386

organic compounds

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Volume 66| Part 6| June 2010| Page o1397

https://doi.org/10.1107/S1600536810018386

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

Yu-Feng Li ^a and Fang-Fang Jian ^b ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 13 May 2010; accepted 18 May 2010; online 22 May 2010)

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 R₂²(8) loop.

Related literature

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

Experimental

Crystal data

C₁₁H₁₆N₄S
M_r = 236.34
Monoclinic, P 2₁ /n
a = 10.517 (2) Å
b = 12.873 (3) Å
c = 10.552 (2) Å
β = 119.19 (3)°
V = 1247.3 (4) Å³
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[F² > 2σ(F²)] = 0.055
wR(F²) = 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

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) -x+1, -y, -z.

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810018386/hb5446sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018386/hb5446Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

Data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); data reduction: SAINT (Bruker 1997); 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 structure of (I) showing 30% probability displacement ellipsoids.

1-(4-(Dimethylamino)benzylidene)-4-methylthiosemicarbazide top

Crystal data top

C₁₁H₁₆N₄S	F(000) = 504
M_r = 236.34	D_x = 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 top

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

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) = 0.178	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.1186P)² + 0.111P] where P = (F_o² + 2F_c²)/3
2847 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₁₆N₄S	V = 1247.3 (4) Å³
M_r = 236.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.517 (2) Å	µ = 0.24 mm⁻¹
b = 12.873 (3) Å	T = 293 K
c = 10.552 (2) Å	0.22 × 0.20 × 0.18 mm
β = 119.19 (3)°

Data collection top

Bruker SMART CCD diffractometer	2391 reflections with I > 2σ(I)
11842 measured reflections	R_int = 0.031
2847 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.12	Δρ_max = 0.43 e Å⁻³
2847 reflections	Δρ_min = −0.26 e Å⁻³
145 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₆N₄S
M_r	236.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.517 (2), 12.873 (3), 10.552 (2)
β (°)	119.19 (3)
V (Å³)	1247.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11842, 2847, 2391
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.178, 1.12
No. of reflections	2847
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.26

Computer programs: SMART (Bruker 1997), SAINT (Bruker 1997), 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
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) −x+1, −y, −z.

References

Bruker (1997). SMART and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Girgis, A. S. (2006). J. Chem. Res. pp. 81–85. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1397

https://doi.org/10.1107/S1600536810018386

Open

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