4-Carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide.

The mol-ecular structure of the title compound, C(13)H(18)N(4)O(3)S, (systematic name: ethyl N-{2-[4-(dimethyl-amino)benzo-yl]hydrazinethio-carbon-yl}carbamate) is stabilized by intra-molecular N-H⋯O=C hydrogen bonding arranged in an S(6) graph-set motif. In the crystal, inversion dimers connected via inter-molecular N-H⋯S=C hydrogen bonds [R(2) (2)(8) graph-set motif] form sheets parallel to the (21) plane. Dimers are also formed by the mol-ecules via weak inter-molecular N-H⋯S=C hydrogen bonds [R(2) (2)(10) graph-set motif] connecting the sheets.

Related literature

For examples of bioactive 1,4-diacyl substituted thio­semi­carbazides and their metal complexes, see: Angelusiu et al. (2009 ▶); Cunha et al. (2007 ▶); Qandil et al. (2006 ▶). For 4-aroyl-1-[4-(N,N-dimethyl­amino)benzo­yl]thio­semicarbazides as high affinity anion receptors, see: Liu & Jiang (2008 ▶). For the structures of related carbethoxy­thio­ureas, see: Dolzhenko et al. (2010 ▶). For the structures of related 1,4-diacyl thio­semicarbazides, see: Ali et al. (2004 ▶); Xue et al. (2006 ▶); Yamin & Yusof (2003 ▶); Yusof et al. (2003 ▶). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C13H18N4O3S

M = 310.37

Triclinic,

a = 7.876 (4) Å

b = 8.184 (4) Å

c = 12.086 (6) Å

α = 82.290 (12)°

β = 74.769 (11)°

γ = 84.469 (11)°

V = 743.3 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.23 mm−1

T = 100 K

0.24 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.946, T max = 0.982

5201 measured reflections

3379 independent reflections

2839 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.081

wR(F 2) = 0.218

S = 1.18

3379 reflections

205 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.84 e Å−3

Δρmin = −0.45 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810015576/ds2029sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015576/ds2029Isup2.hkl

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

C13H18N4O3S	Z = 2
Mr = 310.37	F(000) = 328
Triclinic, P1	Dx = 1.387 Mg m−3
Hall symbol: -P 1	Melting point: 474 K
a = 7.876 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.184 (4) Å	Cell parameters from 644 reflections
c = 12.086 (6) Å	θ = 2.5–27.4°
α = 82.290 (12)°	µ = 0.23 mm−1
β = 74.769 (11)°	T = 100 K
γ = 84.469 (11)°	Rod, colourless
V = 743.3 (7) Å3	0.24 × 0.10 × 0.08 mm

Bruker SMART APEX CCD diffractometer	3379 independent reflections
Radiation source: fine-focus sealed tube	2839 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −9→10
Tmin = 0.946, Tmax = 0.982	k = −10→10
5201 measured reflections	l = −12→15

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.218	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ2(Fo2) + (0.0987P)2 + 1.3625P] where P = (Fo2 + 2Fc2)/3
3379 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.84 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

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 > 2σ(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
S1	0.25106 (11)	0.89905 (11)	1.00357 (7)	0.0123 (3)
O1	0.6976 (3)	1.2062 (3)	0.7276 (2)	0.0147 (6)
O2	0.4814 (3)	1.1658 (3)	0.6437 (2)	0.0152 (6)
O3	0.1155 (3)	0.9455 (3)	0.6162 (2)	0.0146 (6)
N1	0.4741 (4)	1.0685 (4)	0.8327 (3)	0.0106 (6)
H1N	0.534 (7)	1.072 (7)	0.878 (5)	0.037 (15)*
N2	0.2296 (4)	0.9931 (4)	0.7882 (3)	0.0123 (6)
H2N	0.262 (6)	1.043 (6)	0.719 (4)	0.017 (11)*
N3	0.0781 (4)	0.9079 (4)	0.8084 (3)	0.0138 (7)
H3N	0.005 (6)	0.926 (5)	0.866 (4)	0.011 (10)*
N4	−0.6011 (4)	0.5754 (4)	0.7533 (3)	0.0218 (8)
C1	0.9562 (5)	1.3511 (5)	0.6447 (3)	0.0151 (8)
H1A	0.9156	1.4354	0.6979	0.023*
H1B	1.0341	1.3997	0.5730	0.023*
H1C	1.0207	1.2596	0.6803	0.023*
C2	0.7995 (5)	1.2877 (5)	0.6182 (3)	0.0138 (7)
H2A	0.7274	1.3800	0.5879	0.017*
H2B	0.8385	1.2083	0.5601	0.017*
C3	0.5467 (5)	1.1491 (4)	0.7259 (3)	0.0109 (7)
C4	0.3184 (4)	0.9900 (4)	0.8667 (3)	0.0119 (7)
C6	0.0248 (4)	0.8950 (4)	0.7109 (3)	0.0109 (7)
C7	−0.1384 (4)	0.8092 (4)	0.7270 (3)	0.0108 (7)
C8	−0.2115 (5)	0.8174 (4)	0.6328 (3)	0.0122 (7)
H8	−0.1558	0.8778	0.5619	0.015*
C9	−0.3619 (5)	0.7403 (5)	0.6401 (3)	0.0137 (7)
H9	−0.4079	0.7473	0.5743	0.016*
C10	−0.4491 (5)	0.6506 (4)	0.7447 (3)	0.0127 (7)
C11	−0.3746 (5)	0.6417 (5)	0.8393 (3)	0.0145 (7)
H11	−0.4295	0.5811	0.9104	0.017*
C12	−0.2221 (5)	0.7201 (5)	0.8304 (3)	0.0124 (7)
H12	−0.1742	0.7129	0.8955	0.015*
C13	−0.6896 (5)	0.4845 (5)	0.8622 (4)	0.0228 (9)
H13A	−0.6084	0.3962	0.8853	0.034*
H13B	−0.7933	0.4363	0.8527	0.034*
H13C	−0.7266	0.5600	0.9219	0.034*
C14	−0.6706 (5)	0.5756 (5)	0.6535 (3)	0.0172 (8)
H14A	−0.6649	0.6861	0.6103	0.026*
H14B	−0.7935	0.5456	0.6789	0.026*
H14C	−0.6004	0.4953	0.6037	0.026*

	U11	U22	U33	U12	U13	U23
S1	0.0110 (4)	0.0190 (5)	0.0080 (4)	−0.0039 (3)	−0.0034 (3)	−0.0013 (3)
O1	0.0134 (12)	0.0172 (13)	0.0144 (13)	−0.0080 (10)	−0.0040 (10)	0.0009 (10)
O2	0.0169 (13)	0.0166 (13)	0.0141 (13)	−0.0069 (10)	−0.0066 (10)	0.0008 (10)
O3	0.0172 (13)	0.0185 (13)	0.0092 (12)	−0.0073 (10)	−0.0032 (10)	−0.0018 (10)
N1	0.0119 (14)	0.0123 (14)	0.0092 (14)	−0.0051 (11)	−0.0045 (12)	−0.0004 (11)
N2	0.0122 (14)	0.0179 (15)	0.0072 (14)	−0.0068 (12)	−0.0028 (11)	0.0024 (12)
N3	0.0067 (13)	0.0220 (17)	0.0128 (16)	−0.0060 (12)	−0.0001 (12)	−0.0032 (13)
N4	0.0201 (17)	0.0303 (19)	0.0176 (17)	−0.0149 (15)	−0.0078 (14)	0.0034 (14)
C1	0.0134 (16)	0.0133 (17)	0.0183 (19)	−0.0044 (13)	−0.0034 (14)	0.0004 (14)
C2	0.0167 (17)	0.0143 (17)	0.0107 (17)	−0.0068 (14)	−0.0019 (14)	−0.0010 (13)
C3	0.0129 (16)	0.0051 (15)	0.0149 (17)	−0.0016 (12)	−0.0018 (13)	−0.0045 (12)
C4	0.0110 (16)	0.0113 (16)	0.0133 (17)	0.0005 (13)	−0.0031 (13)	−0.0024 (13)
C6	0.0109 (15)	0.0101 (16)	0.0122 (17)	−0.0015 (13)	−0.0016 (13)	−0.0050 (13)
C7	0.0091 (15)	0.0122 (16)	0.0104 (16)	−0.0028 (13)	−0.0004 (13)	−0.0012 (13)
C8	0.0130 (16)	0.0089 (16)	0.0142 (17)	0.0012 (13)	−0.0012 (13)	−0.0048 (13)
C9	0.0164 (17)	0.0180 (18)	0.0108 (17)	−0.0025 (14)	−0.0078 (14)	−0.0064 (14)
C10	0.0129 (16)	0.0119 (16)	0.0144 (18)	−0.0030 (13)	−0.0040 (14)	−0.0025 (13)
C11	0.0159 (17)	0.0163 (18)	0.0106 (17)	−0.0069 (14)	−0.0024 (14)	0.0028 (14)
C12	0.0111 (16)	0.0180 (18)	0.0096 (16)	−0.0035 (13)	−0.0049 (13)	−0.0004 (13)
C13	0.0180 (19)	0.025 (2)	0.026 (2)	−0.0121 (16)	−0.0032 (16)	−0.0026 (17)
C14	0.0189 (18)	0.0167 (18)	0.021 (2)	−0.0042 (14)	−0.0125 (15)	−0.0029 (15)

S1—C4	1.690 (4)	C2—H2A	0.9900
O1—C3	1.325 (4)	C2—H2B	0.9900
O1—C2	1.465 (4)	C6—C7	1.479 (5)
O2—C3	1.219 (4)	C7—C12	1.394 (5)
O3—C6	1.221 (4)	C7—C8	1.396 (5)
N1—C3	1.374 (5)	C8—C9	1.372 (5)
N1—C4	1.379 (4)	C8—H8	0.9500
N1—H1N	0.82 (6)	C9—C10	1.414 (5)
N2—C4	1.315 (5)	C9—H9	0.9500
N2—N3	1.390 (4)	C10—C11	1.407 (5)
N2—H2N	0.86 (5)	C11—C12	1.389 (5)
N3—C6	1.371 (5)	C11—H11	0.9500
N3—H3N	0.80 (4)	C12—H12	0.9500
N4—C10	1.372 (5)	C13—H13A	0.9800
N4—C14	1.450 (5)	C13—H13B	0.9800
N4—C13	1.458 (5)	C13—H13C	0.9800
C1—C2	1.507 (5)	C14—H14A	0.9800
C1—H1A	0.9800	C14—H14B	0.9800
C1—H1B	0.9800	C14—H14C	0.9800
C1—H1C	0.9800
C3—O1—C2	116.3 (3)	O3—C6—C7	123.2 (3)
C3—N1—C4	127.1 (3)	N3—C6—C7	116.7 (3)
C3—N1—H1N	112 (4)	C12—C7—C8	118.4 (3)
C4—N1—H1N	121 (4)	C12—C7—C6	123.7 (3)
C4—N2—N3	122.1 (3)	C8—C7—C6	117.9 (3)
C4—N2—H2N	124 (3)	C9—C8—C7	121.6 (3)
N3—N2—H2N	114 (3)	C9—C8—H8	119.2
C6—N3—N2	114.1 (3)	C7—C8—H8	119.2
C6—N3—H3N	119 (3)	C8—C9—C10	120.6 (3)
N2—N3—H3N	114 (3)	C8—C9—H9	119.7
C10—N4—C14	121.0 (3)	C10—C9—H9	119.7
C10—N4—C13	120.2 (3)	N4—C10—C11	121.3 (3)
C14—N4—C13	118.7 (3)	N4—C10—C9	121.0 (3)
C2—C1—H1A	109.5	C11—C10—C9	117.7 (3)
C2—C1—H1B	109.5	C12—C11—C10	121.0 (3)
H1A—C1—H1B	109.5	C12—C11—H11	119.5
C2—C1—H1C	109.5	C10—C11—H11	119.5
H1A—C1—H1C	109.5	C11—C12—C7	120.7 (3)
H1B—C1—H1C	109.5	C11—C12—H12	119.7
O1—C2—C1	106.0 (3)	C7—C12—H12	119.7
O1—C2—H2A	110.5	N4—C13—H13A	109.5
C1—C2—H2A	110.5	N4—C13—H13B	109.5
O1—C2—H2B	110.5	H13A—C13—H13B	109.5
C1—C2—H2B	110.5	N4—C13—H13C	109.5
H2A—C2—H2B	108.7	H13A—C13—H13C	109.5
O2—C3—O1	126.1 (3)	H13B—C13—H13C	109.5
O2—C3—N1	125.2 (3)	N4—C14—H14A	109.5
O1—C3—N1	108.7 (3)	N4—C14—H14B	109.5
N2—C4—N1	116.4 (3)	H14A—C14—H14B	109.5
N2—C4—S1	123.9 (3)	N4—C14—H14C	109.5
N1—C4—S1	119.7 (3)	H14A—C14—H14C	109.5
O3—C6—N3	120.0 (3)	H14B—C14—H14C	109.5
C4—N2—N3—C6	−166.5 (3)	N3—C6—C7—C8	169.8 (3)
C3—O1—C2—C1	176.1 (3)	C12—C7—C8—C9	0.0 (5)
C2—O1—C3—O2	−4.1 (5)	C6—C7—C8—C9	179.5 (3)
C2—O1—C3—N1	176.4 (3)	C7—C8—C9—C10	0.6 (5)
C4—N1—C3—O2	1.2 (6)	C14—N4—C10—C11	−175.8 (3)
C4—N1—C3—O1	−179.3 (3)	C13—N4—C10—C11	0.3 (6)
N3—N2—C4—N1	174.8 (3)	C14—N4—C10—C9	4.3 (6)
N3—N2—C4—S1	−6.0 (5)	C13—N4—C10—C9	−179.5 (4)
C3—N1—C4—N2	−0.2 (5)	C8—C9—C10—N4	178.9 (3)
C3—N1—C4—S1	−179.4 (3)	C8—C9—C10—C11	−0.9 (5)
N2—N3—C6—O3	5.2 (5)	N4—C10—C11—C12	−179.1 (4)
N2—N3—C6—C7	−178.5 (3)	C9—C10—C11—C12	0.8 (5)
O3—C6—C7—C12	165.6 (4)	C10—C11—C12—C7	−0.3 (6)
N3—C6—C7—C12	−10.6 (5)	C8—C7—C12—C11	−0.1 (5)
O3—C6—C7—C8	−13.9 (5)	C6—C7—C12—C11	−179.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1i	0.82 (6)	2.53 (6)	3.342 (3)	173 (5)
N3—H3N···S1ii	0.80 (4)	2.64 (5)	3.385 (4)	156 (4)
N2—H2N···O2	0.86 (5)	2.02 (5)	2.653 (4)	130 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1i	0.82 (6)	2.53 (6)	3.342 (3)	173 (5)
N3—H3N⋯S1ii	0.80 (4)	2.64 (5)	3.385 (4)	156 (4)
N2—H2N⋯O2	0.86 (5)	2.02 (5)	2.653 (4)	130 (4)

Symmetry codes: (i) ; (ii) .