Crystal structure of (E)-2-[1-(1,3-benzodioxol-5-yl)ethyl-idene]-N-ethyl-hydra-zine-1-carbo-thio-amide.

In the title compound, C12H15N3O2S, the 1,3-benzdioxole fragment is nearly planar [the maximum deviation being 0.0515 (14) Å], the N-N-C(=S)-N fragment is also nearly planar [the maximum deviation being 0.0480 (10) Å], and the dihedral angle between their mean planes is 23.49 (10)°. In the crystal, mol-ecules are linked by pairs of N-H⋯S hydrogen bonds, forming inversion dimers. The dimers are stacked along the a axis with neighbouring columns having the same direction; however, the mol-ecules show different orientations leading to a centrosymmetric arrangement. In the crystal, the methyl-ene group of the ethyl substituent and the terminal methyl H atoms are disordered over two sets of sites and were refined using a split model with an occupancy ratio of 0.5:0.5.

Related literature

For one of the first reports of the synthesis of thio­semicarbazone derivatives, see: Freund & Schander (1902 ▸). For one of the first reports of 3′,4′-(methyl­enedi­oxy)aceto­phenone extraction from the South American Aniba rosaeodora tree, see: Mors et al. (1957 ▸). For the crystal structures of two derivatives of the title compound, see: Oliveira et al. (2013 ▸, 2015 ▸).

Experimental

Crystal data

C12H15N3O2S

M = 265.33

Triclinic,

a = 5.7207 (3) Å

b = 10.6225 (6) Å

c = 10.8103 (6) Å

α = 83.908 (5)°

β = 79.913 (5)°

γ = 87.029 (5)°

V = 642.74 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.25 mm−1

T = 250 K

0.15 × 0.15 × 0.10 mm

Data collection

Stoe IPDS-1 diffractometer

9389 measured reflections

2811 independent reflections

2288 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.116

S = 1.03

2811 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.23 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 ▸); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013-2 (Sheldrick, 2015 ▸); molecular graphics: DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989015003837/xu5837sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015003837/xu5837Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015003837/xu5837Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015003837/xu5837fig1.tif

The mol­ecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level. Disorder is shown with full and open bonds.

Click here for additional data file.

. DOI: 10.1107/S2056989015003837/xu5837fig2.tif

Crystal structure of the title compound with hydrogen bonding shown as dashed lines (see Table 1 for details). Disordered atoms are not shown for clarity.

CCDC reference: 1051034

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H15N3O2S	Z = 2
Mr = 265.33	F(000) = 280
Triclinic, P1	Dx = 1.371 Mg m−3
a = 5.7207 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6225 (6) Å	Cell parameters from 9389 reflections
c = 10.8103 (6) Å	θ = 1.9–27.0°
α = 83.908 (5)°	µ = 0.25 mm−1
β = 79.913 (5)°	T = 250 K
γ = 87.029 (5)°	Parallelepiped, colourless
V = 642.74 (6) Å3	0.15 × 0.15 × 0.10 mm

Stoe IPDS-1 diffractometer	2288 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Stoe IPDS-1	Rint = 0.042
Graphite monochromator	θmax = 27.0°, θmin = 1.9°
φ scans	h = −7→7
9389 measured reflections	k = −13→13
2811 independent reflections	l = −13→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0649P)2 + 0.1118P] where P = (Fo2 + 2Fc2)/3
2811 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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)
C1	0.7435 (3)	0.18956 (14)	0.16339 (15)	0.0407 (3)
C2	0.8619 (3)	0.24715 (14)	0.24537 (15)	0.0428 (3)
H2	0.8352	0.3334	0.2575	0.051*
C3	1.0167 (3)	0.17309 (16)	0.30646 (16)	0.0457 (4)
C4	1.0618 (3)	0.04644 (16)	0.28893 (17)	0.0516 (4)
C5	0.9543 (4)	−0.01187 (16)	0.20857 (19)	0.0581 (5)
H5	0.9863	−0.0977	0.1962	0.070*
C6	0.7937 (3)	0.06224 (16)	0.14522 (17)	0.0515 (4)
H6	0.7174	0.0250	0.0887	0.062*
O1	1.1441 (2)	0.20752 (13)	0.39317 (13)	0.0621 (4)
C7	1.2882 (3)	0.0980 (2)	0.4229 (2)	0.0615 (5)
H7A	1.4562	0.1148	0.3917	0.074*
H7B	1.2668	0.0771	0.5146	0.074*
O2	1.2191 (3)	−0.00457 (13)	0.36476 (15)	0.0698 (4)
C8	0.5558 (3)	0.26302 (14)	0.10543 (15)	0.0407 (3)
C9	0.4637 (3)	0.21798 (17)	−0.00254 (18)	0.0541 (4)
H9A	0.3116	0.1794	0.0280	0.081*
H9B	0.5755	0.1560	−0.0415	0.081*
H9C	0.4440	0.2892	−0.0643	0.081*
N1	0.4771 (2)	0.36261 (12)	0.15902 (13)	0.0420 (3)
N2	0.2949 (2)	0.43540 (12)	0.11811 (13)	0.0432 (3)
H1N2	0.2234	0.4229	0.0560	0.052*
C10	0.2019 (3)	0.53176 (15)	0.18658 (16)	0.0461 (4)
S1	−0.03625 (8)	0.61725 (4)	0.15015 (5)	0.05451 (17)
N3	0.3122 (3)	0.55269 (18)	0.27906 (18)	0.0732 (5)
H1N3	0.4362	0.5027	0.2843	0.088*
C11	0.2171 (16)	0.6290 (8)	0.3858 (8)	0.071 (2)	0.5
H11A	0.1138	0.6987	0.3576	0.085*	0.5
H11B	0.1232	0.5758	0.4544	0.085*	0.5
C11'	0.2731 (18)	0.6716 (7)	0.3447 (8)	0.0675 (19)	0.5
H11C	0.2989	0.7447	0.2812	0.081*	0.5
H11D	0.1073	0.6766	0.3872	0.081*	0.5
C12	0.4155 (6)	0.6790 (3)	0.4304 (3)	0.1149 (12)
H12A	0.5616	0.6353	0.3959	0.172*	0.5
H12B	0.3914	0.6663	0.5219	0.172*	0.5
H12C	0.4259	0.7689	0.4032	0.172*	0.5
H12D	0.4978	0.5980	0.4444	0.172*	0.5
H12E	0.3205	0.7007	0.5092	0.172*	0.5
H12F	0.5307	0.7438	0.3993	0.172*	0.5

	U11	U22	U33	U12	U13	U23
C1	0.0423 (7)	0.0354 (7)	0.0438 (8)	0.0004 (6)	−0.0029 (6)	−0.0089 (6)
C2	0.0447 (8)	0.0345 (7)	0.0491 (8)	−0.0006 (6)	−0.0058 (6)	−0.0077 (6)
C3	0.0450 (8)	0.0449 (8)	0.0467 (8)	−0.0031 (6)	−0.0063 (6)	−0.0043 (6)
C4	0.0492 (9)	0.0433 (9)	0.0588 (10)	0.0060 (7)	−0.0064 (7)	0.0028 (7)
C5	0.0666 (11)	0.0355 (8)	0.0716 (12)	0.0095 (7)	−0.0103 (9)	−0.0106 (8)
C6	0.0577 (10)	0.0395 (8)	0.0594 (10)	0.0034 (7)	−0.0105 (8)	−0.0161 (7)
O1	0.0644 (8)	0.0599 (8)	0.0684 (8)	0.0018 (6)	−0.0293 (7)	−0.0074 (6)
C7	0.0524 (10)	0.0694 (12)	0.0607 (11)	0.0010 (9)	−0.0142 (8)	0.0083 (9)
O2	0.0699 (9)	0.0565 (8)	0.0853 (10)	0.0114 (6)	−0.0292 (7)	0.0024 (7)
C8	0.0417 (7)	0.0357 (7)	0.0449 (8)	−0.0012 (6)	−0.0050 (6)	−0.0095 (6)
C9	0.0538 (9)	0.0522 (10)	0.0617 (10)	0.0070 (7)	−0.0156 (8)	−0.0245 (8)
N1	0.0417 (6)	0.0370 (6)	0.0485 (7)	0.0033 (5)	−0.0086 (5)	−0.0108 (5)
N2	0.0430 (7)	0.0398 (7)	0.0501 (7)	0.0048 (5)	−0.0128 (5)	−0.0150 (5)
C10	0.0464 (8)	0.0403 (8)	0.0539 (9)	0.0033 (6)	−0.0106 (7)	−0.0150 (7)
S1	0.0481 (2)	0.0521 (3)	0.0700 (3)	0.01332 (18)	−0.02210 (19)	−0.0241 (2)
N3	0.0788 (11)	0.0749 (11)	0.0815 (11)	0.0404 (9)	−0.0444 (9)	−0.0480 (9)
C11	0.070 (4)	0.073 (5)	0.081 (6)	0.027 (4)	−0.029 (4)	−0.046 (4)
C11'	0.087 (5)	0.057 (4)	0.068 (5)	0.027 (3)	−0.032 (4)	−0.033 (3)
C12	0.109 (2)	0.133 (3)	0.122 (2)	0.029 (2)	−0.0365 (19)	−0.089 (2)

C1—C6	1.395 (2)	N1—N2	1.3730 (18)
C1—C2	1.410 (2)	N2—C10	1.358 (2)
C1—C8	1.483 (2)	N2—H1N2	0.8699
C2—C3	1.364 (2)	C10—N3	1.315 (2)
C2—H2	0.9400	C10—S1	1.6792 (17)
C3—O1	1.372 (2)	N3—C11	1.489 (9)
C3—C4	1.383 (2)	N3—C11'	1.501 (9)
C4—C5	1.363 (3)	N3—H1N3	0.8700
C4—O2	1.375 (2)	C11—C12	1.453 (10)
C5—C6	1.401 (3)	C11—H11A	0.9800
C5—H5	0.9400	C11—H11B	0.9800
C6—H6	0.9400	C11'—C12	1.347 (10)
O1—C7	1.432 (2)	C11'—H11C	0.9800
C7—O2	1.420 (3)	C11'—H11D	0.9800
C7—H7A	0.9800	C12—H12A	0.9700
C7—H7B	0.9800	C12—H12B	0.9700
C8—N1	1.2832 (19)	C12—H12C	0.9700
C8—C9	1.493 (2)	C12—H12D	0.9700
C9—H9A	0.9700	C12—H12E	0.9700
C9—H9B	0.9700	C12—H12F	0.9700
C9—H9C	0.9700
C6—C1—C2	119.34 (15)	C10—N2—N1	117.50 (13)
C6—C1—C8	121.30 (15)	C10—N2—H1N2	115.4
C2—C1—C8	119.22 (13)	N1—N2—H1N2	126.9
C3—C2—C1	117.54 (14)	N3—C10—N2	115.66 (15)
C3—C2—H2	121.2	N3—C10—S1	123.92 (12)
C1—C2—H2	121.2	N2—C10—S1	120.41 (13)
C2—C3—O1	127.54 (15)	C10—N3—C11	126.2 (4)
C2—C3—C4	122.40 (16)	C10—N3—C11'	123.1 (4)
O1—C3—C4	110.05 (15)	C10—N3—H1N3	113.3
C5—C4—O2	128.69 (16)	C11—N3—H1N3	119.0
C5—C4—C3	121.73 (16)	C11'—N3—H1N3	121.5
O2—C4—C3	109.57 (17)	C12—C11—N3	108.7 (6)
C4—C5—C6	116.86 (15)	C12—C11—H11A	110.0
C4—C5—H5	121.6	N3—C11—H11A	110.0
C6—C5—H5	121.6	C12—C11—H11B	110.0
C1—C6—C5	122.10 (17)	N3—C11—H11B	110.0
C1—C6—H6	118.9	H11A—C11—H11B	108.3
C5—C6—H6	118.9	C12—C11'—N3	114.0 (6)
C3—O1—C7	105.38 (14)	C12—C11'—H11C	108.7
O2—C7—O1	108.49 (15)	N3—C11'—H11C	108.7
O2—C7—H7A	110.0	C12—C11'—H11D	108.7
O1—C7—H7A	110.0	N3—C11'—H11D	108.7
O2—C7—H7B	110.0	H11C—C11'—H11D	107.6
O1—C7—H7B	110.0	C11—C12—H12A	109.5
H7A—C7—H7B	108.4	C11—C12—H12B	109.5
C4—O2—C7	105.90 (14)	H12A—C12—H12B	109.5
N1—C8—C1	114.42 (14)	C11—C12—H12C	109.5
N1—C8—C9	124.48 (15)	H12A—C12—H12C	109.5
C1—C8—C9	121.04 (13)	H12B—C12—H12C	109.5
C8—C9—H9A	109.5	C11'—C12—H12D	109.5
C8—C9—H9B	109.5	C11'—C12—H12E	109.5
H9A—C9—H9B	109.5	H12D—C12—H12E	109.5
C8—C9—H9C	109.5	C11'—C12—H12F	109.5
H9A—C9—H9C	109.5	H12D—C12—H12F	109.5
H9B—C9—H9C	109.5	H12E—C12—H12F	109.5
C8—N1—N2	120.07 (14)
C6—C1—C2—C3	−1.9 (2)	C6—C1—C8—N1	159.25 (15)
C8—C1—C2—C3	173.75 (14)	C2—C1—C8—N1	−16.3 (2)
C1—C2—C3—O1	−177.54 (15)	C6—C1—C8—C9	−18.1 (2)
C1—C2—C3—C4	1.0 (2)	C2—C1—C8—C9	166.30 (15)
C2—C3—C4—C5	0.3 (3)	C1—C8—N1—N2	−176.84 (12)
O1—C3—C4—C5	179.06 (16)	C9—C8—N1—N2	0.4 (2)
C2—C3—C4—O2	−178.38 (15)	C8—N1—N2—C10	173.15 (14)
O1—C3—C4—O2	0.34 (19)	N1—N2—C10—N3	6.2 (2)
O2—C4—C5—C6	177.85 (17)	N1—N2—C10—S1	−174.75 (11)
C3—C4—C5—C6	−0.6 (3)	N2—C10—N3—C11	−164.2 (4)
C2—C1—C6—C5	1.7 (3)	S1—C10—N3—C11	16.8 (5)
C8—C1—C6—C5	−173.86 (16)	N2—C10—N3—C11'	165.3 (4)
C4—C5—C6—C1	−0.4 (3)	S1—C10—N3—C11'	−13.8 (5)
C2—C3—O1—C7	−176.90 (16)	C10—N3—C11—C12	−153.3 (4)
C4—C3—O1—C7	4.46 (18)	C11'—N3—C11—C12	−61.3 (15)
C3—O1—C7—O2	−7.55 (19)	C10—N3—C11'—C12	−175.3 (4)
C5—C4—O2—C7	176.35 (19)	C11—N3—C11'—C12	79.0 (15)
C3—C4—O2—C7	−5.04 (19)	N3—C11'—C12—C11	−73.0 (13)
O1—C7—O2—C4	7.8 (2)	N3—C11—C12—C11'	68.3 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···S1i	0.87	2.72	3.5842 (14)	175

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H1N2S1i	0.87	2.72	3.5842(14)	175

Symmetry code: (i) .