4-(Dimethyl-amino)benzaldehyde 4-ethyl-thio-semicarbazone.

The title thio-semicarbazone derivative, C(12)H(18)N(4)S, features intra-molecular N-H⋯N and C-H⋯S hydrogen bonds which generate S(5) ring motifs. The dihedral angle between the benzene ring and the thio-urea unit is 6.30 (6)° indicating planarity in the mol-ecule. Inter-molecular N-H⋯S hydrogen bonds generate dimers with an R(2) (2)(8) ring motif. The methyl group of the N-ethyl residue is disordered and was refined with site occupancies of 0.521 (5) and 0.479 (5).

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures and applications see: Beraldo et al. (2001 ▶); Kayed et al. (2008 ▶); Valdes-Martinez et al. (1990 ▶).

Experimental

Crystal data

C12H18N4S

M = 250.36

Monoclinic,

a = 9.3687 (2) Å

b = 14.1872 (3) Å

c = 10.2318 (2) Å

β = 96.699 (1)°

V = 1350.68 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 100 (1) K

0.59 × 0.36 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.879, T max = 0.953

30229 measured reflections

6825 independent reflections

5566 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.119

S = 1.04

6825 reflections

176 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.74 e Å−3

Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037148/tk2323sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037148/tk2323Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H18N4S	F000 = 536
Mr = 250.36	Dx = 1.231 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9949 reflections
a = 9.3687 (2) Å	θ = 2.5–39.5º
b = 14.1872 (3) Å	µ = 0.23 mm−1
c = 10.2318 (2) Å	T = 100 (1) K
β = 96.699 (1)º	Block, yellow
V = 1350.68 (5) Å3	0.59 × 0.36 × 0.22 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	6825 independent reflections
Radiation source: fine-focus sealed tube	5566 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.036
T = 100(1) K	θmax = 37.0º
φ and ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2005)	h = −15→13
Tmin = 0.879, Tmax = 0.953	k = −24→20
30229 measured reflections	l = −15→17

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)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119	w = 1/[σ2(Fo2) + (0.0651P)2 + 0.2126P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
6825 reflections	Δρmax = 0.74 e Å−3
176 parameters	Δρmin = −0.39 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.16244 (2)	0.114147 (15)	−0.039117 (18)	0.01984 (6)
N1	−0.30894 (9)	0.10562 (6)	0.82869 (8)	0.02457 (15)
N2	−0.01025 (7)	0.10572 (5)	0.29168 (6)	0.01690 (12)
N3	0.02454 (7)	0.08428 (5)	0.16770 (6)	0.01731 (12)
N4	0.18487 (7)	0.20579 (5)	0.19197 (7)	0.01837 (12)
C1	−0.09174 (8)	0.13272 (6)	0.55310 (7)	0.01760 (13)
H1A	−0.0138	0.1680	0.5323	0.021*
C2	−0.14161 (8)	0.14561 (6)	0.67363 (7)	0.01834 (13)
H2A	−0.0977	0.1900	0.7319	0.022*
C3	−0.25861 (8)	0.09230 (6)	0.70986 (7)	0.01732 (13)
C4	−0.32165 (9)	0.02550 (6)	0.61854 (8)	0.01997 (14)
H4A	−0.3979	−0.0113	0.6396	0.024*
C5	−0.27073 (9)	0.01429 (6)	0.49756 (8)	0.01935 (14)
H5A	−0.3142	−0.0300	0.4388	0.023*
C6	−0.15624 (8)	0.06743 (5)	0.46132 (7)	0.01601 (12)
C7	−0.10836 (8)	0.05380 (6)	0.33282 (7)	0.01745 (13)
H7A	−0.1498	0.0062	0.2786	0.021*
C8	0.12430 (8)	0.13664 (6)	0.11598 (7)	0.01551 (12)
C9	0.29288 (10)	0.27026 (6)	0.15428 (9)	0.02484 (16)
H9A	0.2867	0.3279	0.2024	0.030*	0.521 (5)
H9B	0.2702	0.2848	0.0626	0.030*	0.521 (5)
H9C	0.2877	0.3291	0.1999	0.030*	0.479 (5)
H9D	0.2767	0.2823	0.0614	0.030*	0.479 (5)
C10A	0.4427 (11)	0.2356 (8)	0.1674 (8)	0.0361 (12)	0.521 (5)
H10A	0.5045	0.2841	0.1403	0.054*	0.521 (5)
H10B	0.4486	0.1810	0.1128	0.054*	0.521 (5)
H10C	0.4724	0.2192	0.2575	0.054*	0.521 (5)
C10B	0.4457 (14)	0.2268 (10)	0.1992 (9)	0.0394 (15)	0.479 (5)
H10D	0.4558	0.2160	0.2925	0.059*	0.479 (5)
H10E	0.5188	0.2698	0.1782	0.059*	0.479 (5)
H10F	0.4554	0.1681	0.1544	0.059*	0.479 (5)
C11	−0.43497 (11)	0.05588 (7)	0.86103 (10)	0.02942 (19)
H11A	−0.5107	0.0619	0.7898	0.044*
H11B	−0.4657	0.0823	0.9395	0.044*
H11C	−0.4121	−0.0096	0.8753	0.044*
C12	−0.24779 (10)	0.17816 (8)	0.91858 (9)	0.02932 (19)
H12A	−0.1452	0.1710	0.9325	0.044*
H12B	−0.2864	0.1722	1.0011	0.044*
H12C	−0.2713	0.2392	0.8815	0.044*
H1N4	0.1570 (14)	0.2111 (10)	0.2711 (14)	0.032 (3)*
H1N3	−0.0171 (15)	0.0353 (11)	0.1243 (14)	0.035 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.02294 (10)	0.02210 (11)	0.01529 (9)	−0.00401 (7)	0.00569 (6)	−0.00261 (6)
N1	0.0315 (4)	0.0243 (4)	0.0202 (3)	−0.0016 (3)	0.0121 (3)	−0.0011 (2)
N2	0.0198 (3)	0.0176 (3)	0.0137 (2)	−0.0005 (2)	0.0038 (2)	−0.0006 (2)
N3	0.0206 (3)	0.0178 (3)	0.0141 (2)	−0.0036 (2)	0.0043 (2)	−0.0018 (2)
N4	0.0212 (3)	0.0178 (3)	0.0166 (3)	−0.0039 (2)	0.0044 (2)	−0.0022 (2)
C1	0.0179 (3)	0.0185 (3)	0.0166 (3)	−0.0026 (2)	0.0028 (2)	−0.0005 (2)
C2	0.0199 (3)	0.0199 (3)	0.0152 (3)	−0.0015 (3)	0.0024 (2)	−0.0015 (2)
C3	0.0205 (3)	0.0157 (3)	0.0166 (3)	0.0026 (2)	0.0057 (2)	0.0018 (2)
C4	0.0215 (3)	0.0171 (3)	0.0226 (3)	−0.0025 (3)	0.0082 (3)	−0.0007 (3)
C5	0.0213 (3)	0.0167 (3)	0.0208 (3)	−0.0040 (2)	0.0060 (2)	−0.0031 (2)
C6	0.0181 (3)	0.0149 (3)	0.0153 (3)	−0.0008 (2)	0.0032 (2)	−0.0001 (2)
C7	0.0199 (3)	0.0168 (3)	0.0160 (3)	−0.0013 (2)	0.0034 (2)	−0.0013 (2)
C8	0.0162 (3)	0.0156 (3)	0.0148 (3)	0.0000 (2)	0.0017 (2)	0.0010 (2)
C9	0.0294 (4)	0.0199 (4)	0.0269 (4)	−0.0092 (3)	0.0107 (3)	−0.0057 (3)
C10A	0.0211 (12)	0.032 (2)	0.057 (3)	−0.0087 (13)	0.011 (2)	−0.015 (2)
C10B	0.0265 (14)	0.036 (2)	0.057 (4)	−0.0113 (14)	0.009 (3)	−0.011 (3)
C11	0.0374 (5)	0.0252 (4)	0.0291 (4)	−0.0005 (4)	0.0190 (4)	0.0033 (3)
C12	0.0275 (4)	0.0409 (6)	0.0199 (3)	0.0028 (4)	0.0037 (3)	−0.0083 (3)

S1—C8	1.6971 (7)	C6—C7	1.4508 (10)
N1—C3	1.3675 (10)	C7—H7A	0.9300
N1—C11	1.4466 (12)	C9—C10A	1.479 (10)
N1—C12	1.4528 (13)	C9—C10B	1.577 (13)
N2—C7	1.2864 (10)	C9—H9A	0.9600
N2—N3	1.3800 (9)	C9—H9B	0.9600
N3—C8	1.3494 (10)	C9—H9C	0.9600
N3—H1N3	0.890 (15)	C9—H9D	0.9600
N4—C8	1.3365 (10)	C10A—H10A	0.9600
N4—C9	1.4492 (11)	C10A—H10B	0.9600
N4—H1N4	0.883 (14)	C10A—H10C	0.9600
C1—C2	1.3810 (10)	C10B—H10D	0.9600
C1—C6	1.4045 (11)	C10B—H10E	0.9600
C1—H1A	0.9300	C10B—H10F	0.9600
C2—C3	1.4162 (11)	C11—H11A	0.9600
C2—H2A	0.9300	C11—H11B	0.9600
C3—C4	1.4111 (12)	C11—H11C	0.9600
C4—C5	1.3867 (11)	C12—H12A	0.9600
C4—H4A	0.9300	C12—H12B	0.9600
C5—C6	1.3961 (11)	C12—H12C	0.9600
C5—H5A	0.9300
C3—N1—C11	120.75 (8)	C10A—C9—H9A	110.5
C3—N1—C12	120.62 (8)	C10B—C9—H9A	106.9
C11—N1—C12	118.22 (7)	N4—C9—H9B	108.3
C7—N2—N3	115.40 (7)	C10A—C9—H9B	105.1
C8—N3—N2	119.20 (7)	C10B—C9—H9B	117.3
C8—N3—H1N3	121.2 (9)	H9A—C9—H9B	107.4
N2—N3—H1N3	119.6 (9)	N4—C9—H9C	110.0
C8—N4—C9	124.80 (7)	C10A—C9—H9C	110.3
C8—N4—H1N4	116.4 (9)	C10B—C9—H9C	107.1
C9—N4—H1N4	118.7 (9)	H9B—C9—H9C	105.7
C2—C1—C6	121.36 (7)	N4—C9—H9D	110.0
C2—C1—H1A	119.3	C10A—C9—H9D	100.8
C6—C1—H1A	119.3	C10B—C9—H9D	113.0
C1—C2—C3	121.05 (7)	H9A—C9—H9D	110.1
C1—C2—H2A	119.5	H9C—C9—H9D	108.4
C3—C2—H2A	119.5	C9—C10A—H10A	109.5
N1—C3—C4	121.35 (7)	C9—C10A—H10B	109.5
N1—C3—C2	121.11 (7)	C9—C10A—H10C	109.5
C4—C3—C2	117.53 (7)	C9—C10B—H10D	109.5
C5—C4—C3	120.47 (7)	C9—C10B—H10E	109.5
C5—C4—H4A	119.8	H10D—C10B—H10E	109.5
C3—C4—H4A	119.8	C9—C10B—H10F	109.5
C4—C5—C6	122.02 (7)	H10D—C10B—H10F	109.5
C4—C5—H5A	119.0	H10E—C10B—H10F	109.5
C6—C5—H5A	119.0	N1—C11—H11A	109.5
C5—C6—C1	117.54 (7)	N1—C11—H11B	109.5
C5—C6—C7	119.81 (7)	H11A—C11—H11B	109.5
C1—C6—C7	122.65 (7)	N1—C11—H11C	109.5
N2—C7—C6	121.90 (7)	H11A—C11—H11C	109.5
N2—C7—H7A	119.1	H11B—C11—H11C	109.5
C6—C7—H7A	119.1	N1—C12—H12A	109.5
N4—C8—N3	116.26 (6)	N1—C12—H12B	109.5
N4—C8—S1	124.10 (6)	H12A—C12—H12B	109.5
N3—C8—S1	119.62 (6)	N1—C12—H12C	109.5
N4—C9—C10A	116.8 (4)	H12A—C12—H12C	109.5
N4—C9—C10B	108.3 (4)	H12B—C12—H12C	109.5
N4—C9—H9A	108.4
C7—N2—N3—C8	178.60 (7)	C4—C5—C6—C7	−179.19 (8)
C6—C1—C2—C3	0.93 (12)	C2—C1—C6—C5	−1.47 (12)
C11—N1—C3—C4	−4.17 (13)	C2—C1—C6—C7	178.59 (8)
C12—N1—C3—C4	−176.68 (8)	N3—N2—C7—C6	179.78 (7)
C11—N1—C3—C2	175.45 (8)	C5—C6—C7—N2	174.99 (8)
C12—N1—C3—C2	2.93 (13)	C1—C6—C7—N2	−5.08 (12)
C1—C2—C3—N1	−179.39 (8)	C9—N4—C8—N3	−179.39 (8)
C1—C2—C3—C4	0.24 (12)	C9—N4—C8—S1	−1.06 (12)
N1—C3—C4—C5	178.80 (8)	N2—N3—C8—N4	1.21 (11)
C2—C3—C4—C5	−0.82 (12)	N2—N3—C8—S1	−177.20 (5)
C3—C4—C5—C6	0.26 (13)	C8—N4—C9—C10A	−81.0 (4)
C4—C5—C6—C1	0.88 (12)	C8—N4—C9—C10B	−90.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···S1i	0.891 (15)	2.613 (15)	3.4910 (7)	168.8 (12)
N4—H1N4···N2	0.885 (14)	2.193 (14)	2.6140 (10)	108.7 (11)
C9—H9B···S1	0.96	2.78	3.1225 (9)	102

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯S1i	0.891 (15)	2.613 (15)	3.4910 (7)	168.8 (12)
N4—H1N4⋯N2	0.885 (14)	2.193 (14)	2.6140 (10)	108.7 (11)
C9—H9B⋯S1	0.96	2.78	3.1225 (9)	102

Symmetry code: (i) .