Methyl 3-[(E)-1-(4-amino­phen­yl)ethyl­­idene]di­thio­carbazate

The title compound, C₁₀H₁₃N₃S₂, was obtained from a condensation reaction of methyl dithio­carbazate and 4-amino­acetophenone. In the crystal structure, the nearly planar mol­ecule assumes an E configuration, the benzene ring and dithio­carbazate group being located on opposite sides of the N=C bond. C—H⋯π inter­actions and N—H⋯S hydrogen bonding are present in the crystal structure.

Related literature

For general background, see: Okabe et al. (1993); Shan et al. (2003); Jiang (2007). For related structures, see: Shan et al. (2006); Zhang et al. (2005). For synthesis, see: Hu et al. (2001).

Experimental

Crystal data

• C₁₀H₁₃N₃S₂

• M_r = 239.35

• Monoclinic, P 2₁ /n

• a = 10.8247 (12) Å

• b = 5.3673 (8) Å

• c = 20.4549 (14) Å

• β = 94.756 (12)°

• V = 1184.3 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.42 mm⁻¹

• T = 295 (2) K

• 0.32 × 0.22 × 0.20 mm

Data collection

• Rigaku R-AXIS RAPID IP diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.870, T_max = 0.926

• 10489 measured reflections

• 2682 independent reflections

• 1867 reflections with I > 2σ(I)

• R_int = 0.030

Refinement

• R[F² > 2σ(F²)] = 0.043

• wR(F²) = 0.124

• S = 1.07

• 2682 reflections

• 138 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S2^i	0.90	2.83	3.722 (3)	170
N3—H3N⋯S2^ii	0.94	2.59	3.483 (2)	159
C10—H10A⋯Cg^iii	0.96	2.80	3.538 (3)	134
Symmetry codes: (i) ; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+1, -z+1. Cg is the centroid of the benzene ring.

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

S1. Comment

As some phenylhydrazone derivatives have been shown to be potential DNA-damaging or mutagenic agents (Okabe et al., 1993), a series of new phenylhydrazone derivatives has been synthesized in our laboratory in past years, and several crystal structures of phenylhydrazone compounds have been determined by X-ray diffraction in order to research their structure-bioactivity relationship (Shan et al., 2003). Recent investigation discovered that sulfur-containing hydrazone compounds are benefit to promote the bioactivities of hydrazone (Jiang, 2007). As part of our ongoing investigation on hydrazone compounds, the title compound with dithiocarbazate component has recently been prepared and its crystal structure is reported here.

The structure of the title compound is shown in Fig. 1. The N2—C7 bond distance of 1.281 (3) Å indicates a typical C=N double bond. The molecule adopts an E configuration about the C=N double bond. The molecule has a nearly planar structure. The C8 atom is well co-planar with the benzene ring with a small atomic deviation of 0.028 (4) Å from the phenylmethylene mean plane. The dithiocarbazate moiety is slightly twisted to the phenylmethylene plane with a dihedral angle of 13.4 (1)°. The shorter N3—C9 bond distance of 1.345 (3) Å implies the N3 atom involved in the electron delocalization in the dithiocarbazate moiety.

It is notable that the N3—C9—S1 bond angle of 113.26 (15)° is much smaller than 120° expected for a sp² hybrid C atom and also much smaller than the corresponding N3—C9—S2 bond angle of 121.66 (16)°, which is similar to that found in related structures reported previously (Shan et al., 2006; Zhang et al., 2005).

Intermolecular C—H···π interaction is observed between C10-methyl group and the benzene ring of the adjacent molecule (Fig. 2), C10—H10a—Cgⁱ angle being 134° and C10···Cgⁱ and H10a···Cgⁱ separations being 3.538 (3) and 2.80 Å, respectively [where Cg is the centroid of the benzene ring and symmetry code (i) = 1 - x,1 - y,1 - z]. Molecules are also linked by intermolecular C—H···S hydrogen bonding (Table 1) to form the supra-molecular chain.

Related literature

For general background, see: Okabe et al. (1993); Shan et al. (2003); Jiang (2007). For related structures, see: Shan et al. (2006); Zhang et al. (2005). For synthesis, see: Hu et al. (2001).

S2. Experimental

Methyl dithiocarbazate was synthesized in the manner reported previously (Hu et al., 2001). Methyl dithiocarbazate (1.24 g, 10 mmol) and 4-aminoacetophenone (1.35 g, 10 mmol) were dissolved in ethanol (10 ml) and refluxed for 6 h. Yellow crystalline product appeared after cooling to room temperature. They were separated and washed with cold water three times. Single crystals of the title compound were obtained by recrystallization from a 2-propanol solution.

S3. Refinement

H atoms bonded to N atoms were located in a difference Fourier map and refined as riding in their as-found relative positions with U_iso(H) = 1.2U_eq(N). Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angles were refined to fit the electron density, U_iso(H) = 1.5U_eq(C). Aromatic H atoms were placed in calculated positions with C—H = 0.93 Å and refined in riding mode with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).
	Fig. 2. A diagram showing C—H···π interaction by dashed lines [symmetry code: (i) = 1 - x,1 - y,1 - z].

Methyl 3-[(E)-1-(4-aminophenyl)ethylidene]dithiocarbazate

Crystal data

C10H13N3S2	F(000) = 504
Mr = 239.35	Dx = 1.342 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4876 reflections
a = 10.8247 (12) Å	θ = 3.5–25.0°
b = 5.3673 (8) Å	µ = 0.42 mm^−1
c = 20.4549 (14) Å	T = 295 K
β = 94.756 (12)°	Prism, yellow
V = 1184.3 (2) Å^3	0.32 × 0.22 × 0.20 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer	2682 independent reflections
Radiation source: fine-focus sealed tube	1867 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 10.00 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ω scans	h = −14→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −6→6
Tmin = 0.870, Tmax = 0.926	l = −26→26
10489 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0597P)^2 + 0.2088P] where P = (Fo^2 + 2Fc^2)/3
2682 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.64254 (5)	0.21562 (12)	0.48386 (3)	0.0615 (2)
S2	0.88535 (6)	0.31459 (16)	0.42531 (3)	0.0800 (3)
N1	0.3499 (3)	0.7090 (5)	0.79285 (13)	0.0946 (8)
H1A	0.3635	0.8087	0.8281	0.114*
H1B	0.3062	0.5773	0.8021	0.114*
N2	0.72126 (16)	0.5566 (3)	0.57515 (8)	0.0535 (4)
N3	0.80638 (17)	0.5371 (4)	0.52873 (9)	0.0581 (5)
H3N	0.8845	0.6145	0.5342	0.070*
C1	0.63507 (19)	0.7276 (4)	0.66547 (10)	0.0482 (5)
C2	0.6266 (2)	0.9072 (4)	0.71383 (10)	0.0597 (6)
H2	0.6850	1.0346	0.7178	0.072*
C3	0.5336 (2)	0.9013 (5)	0.75625 (11)	0.0671 (6)
H3	0.5298	1.0257	0.7876	0.081*
C4	0.4458 (2)	0.7123 (5)	0.75263 (11)	0.0630 (6)
C5	0.4553 (2)	0.5303 (5)	0.70511 (13)	0.0691 (6)
H5	0.3980	0.4009	0.7017	0.083*
C6	0.5470 (2)	0.5376 (4)	0.66329 (12)	0.0615 (6)
H6	0.5509	0.4117	0.6323	0.074*
C7	0.73087 (18)	0.7311 (4)	0.61800 (10)	0.0483 (5)
C8	0.8278 (2)	0.9319 (4)	0.62278 (12)	0.0641 (6)
H8A	0.8693	0.9357	0.5831	0.096*
H8B	0.8870	0.8982	0.6593	0.096*
H8C	0.7891	1.0901	0.6290	0.096*
C9	0.78466 (19)	0.3662 (4)	0.48112 (10)	0.0539 (5)
C10	0.6466 (2)	−0.0091 (5)	0.41878 (12)	0.0720 (7)
H10A	0.6459	0.0760	0.3775	0.108*
H10B	0.5753	−0.1157	0.4186	0.108*
H10C	0.7206	−0.1074	0.4255	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0515 (3)	0.0747 (4)	0.0591 (3)	−0.0119 (3)	0.0090 (2)	−0.0129 (3)
S2	0.0592 (4)	0.1134 (6)	0.0703 (4)	−0.0144 (4)	0.0219 (3)	−0.0215 (4)
N1	0.0967 (18)	0.0956 (18)	0.0979 (17)	0.0018 (14)	0.0456 (14)	−0.0022 (15)
N2	0.0518 (10)	0.0545 (10)	0.0548 (9)	−0.0059 (8)	0.0083 (8)	−0.0056 (9)
N3	0.0511 (10)	0.0621 (11)	0.0621 (10)	−0.0118 (8)	0.0105 (8)	−0.0079 (9)
C1	0.0488 (11)	0.0440 (10)	0.0508 (10)	0.0030 (8)	−0.0019 (8)	−0.0002 (9)
C2	0.0680 (15)	0.0529 (12)	0.0571 (12)	−0.0071 (10)	−0.0020 (10)	−0.0078 (11)
C3	0.0838 (17)	0.0641 (15)	0.0537 (12)	0.0034 (13)	0.0067 (11)	−0.0091 (11)
C4	0.0675 (15)	0.0632 (14)	0.0598 (13)	0.0122 (11)	0.0133 (11)	0.0077 (12)
C5	0.0653 (15)	0.0559 (13)	0.0884 (17)	−0.0078 (11)	0.0197 (12)	−0.0053 (13)
C6	0.0618 (14)	0.0502 (12)	0.0738 (14)	−0.0067 (10)	0.0130 (11)	−0.0143 (11)
C7	0.0469 (11)	0.0439 (10)	0.0526 (11)	0.0002 (8)	−0.0057 (8)	0.0021 (9)
C8	0.0562 (13)	0.0563 (13)	0.0797 (15)	−0.0096 (10)	0.0048 (11)	−0.0079 (12)
C9	0.0477 (11)	0.0618 (13)	0.0525 (11)	−0.0013 (9)	0.0055 (9)	0.0025 (10)
C10	0.0718 (16)	0.0774 (17)	0.0662 (14)	−0.0118 (13)	0.0018 (12)	−0.0185 (13)

Geometric parameters (Å, º)

S1—C9	1.743 (2)	C2—H2	0.9300
S1—C10	1.800 (2)	C3—C4	1.387 (4)
S2—C9	1.666 (2)	C3—H3	0.9300
N1—C4	1.378 (3)	C4—C5	1.388 (3)
N1—H1A	0.9008	C5—C6	1.364 (3)
N1—H1B	0.8793	C5—H5	0.9300
N2—C7	1.281 (3)	C6—H6	0.9300
N2—N3	1.381 (2)	C7—C8	1.501 (3)
N3—C9	1.345 (3)	C8—H8A	0.9600
N3—H3N	0.9399	C8—H8B	0.9600
C1—C2	1.390 (3)	C8—H8C	0.9600
C1—C6	1.394 (3)	C10—H10A	0.9600
C1—C7	1.478 (3)	C10—H10B	0.9600
C2—C3	1.383 (3)	C10—H10C	0.9600
C9—S1—C10	102.20 (11)	C4—C5—H5	119.4
C4—N1—H1A	112.9	C5—C6—C1	122.2 (2)
C4—N1—H1B	125.7	C5—C6—H6	118.9
H1A—N1—H1B	111.1	C1—C6—H6	118.9
C7—N2—N3	120.32 (17)	N2—C7—C1	114.74 (18)
C9—N3—N2	117.59 (17)	N2—C7—C8	125.9 (2)
C9—N3—H3N	119.2	C1—C7—C8	119.40 (18)
N2—N3—H3N	122.0	C7—C8—H8A	109.5
C2—C1—C6	116.4 (2)	C7—C8—H8B	109.5
C2—C1—C7	123.35 (19)	H8A—C8—H8B	109.5
C6—C1—C7	120.22 (19)	C7—C8—H8C	109.5
C3—C2—C1	121.6 (2)	H8A—C8—H8C	109.5
C3—C2—H2	119.2	H8B—C8—H8C	109.5
C1—C2—H2	119.2	N3—C9—S2	121.66 (16)
C2—C3—C4	121.0 (2)	N3—C9—S1	113.26 (15)
C2—C3—H3	119.5	S2—C9—S1	125.07 (14)
C4—C3—H3	119.5	S1—C10—H10A	109.5
N1—C4—C3	121.6 (2)	S1—C10—H10B	109.5
N1—C4—C5	120.8 (2)	H10A—C10—H10B	109.5
C3—C4—C5	117.5 (2)	S1—C10—H10C	109.5
C6—C5—C4	121.3 (2)	H10A—C10—H10C	109.5
C6—C5—H5	119.4	H10B—C10—H10C	109.5
C7—N2—N3—C9	−173.50 (19)	N3—N2—C7—C1	−178.93 (17)
C6—C1—C2—C3	−1.8 (3)	N3—N2—C7—C8	1.7 (3)
C7—C1—C2—C3	178.2 (2)	C2—C1—C7—N2	−177.2 (2)
C1—C2—C3—C4	1.0 (4)	C6—C1—C7—N2	2.9 (3)
C2—C3—C4—N1	−177.5 (2)	C2—C1—C7—C8	2.3 (3)
C2—C3—C4—C5	0.1 (4)	C6—C1—C7—C8	−177.7 (2)
N1—C4—C5—C6	177.3 (2)	N2—N3—C9—S2	−176.19 (15)
C3—C4—C5—C6	−0.3 (4)	N2—N3—C9—S1	5.0 (2)
C4—C5—C6—C1	−0.6 (4)	C10—S1—C9—N3	−176.49 (17)
C2—C1—C6—C5	1.6 (3)	C10—S1—C9—S2	4.73 (19)
C7—C1—C6—C5	−178.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S2^i	0.90	2.83	3.722 (3)	170
N3—H3N···S2^ii	0.94	2.59	3.483 (2)	159
C10—H10A···Cg^iii	0.96	2.80	3.538 (3)	134

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1.