1-(2H-1,3-Benzodioxol-5-yl)ethanone thio­semicarbazone

In the title compound, C₁₀H₁₁N₃O₂S, the 1,3-benzodioxole and hydrazinecarbothio­amide fragments are nearly planar [(mean deviations from planarity for non-H atoms of 0.0325 (12) Å and 0.0707 (10) Å, respectively] and subtend a dihedral angle of 29.06 (5)°. In the crystal, mol­ecules are linked by pairs of almost linear N—H...S hydrogen bonds, forming inversion dimers. These dimers are additionally connected by weaker and strongly bent N—H...S inter­actions into chains along [101]. There is one additional weak N—H...O contact which, if considered as an inter­action, leads to the formation of a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.037
• wR factor = 0.107
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C1      ..        6.0 su
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.4
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1N1   ..  O1      ..       2.66 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         29
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          5

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          3
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

Thiosemicarbazone derivatives have a wide range of pharmacological properties. For example, 3',4'-(methylenedioxy)acetophenone thiosemicarbazone derivatives show cytotoxic activity against KB cells (Silva et al., 1998). As part of our study on the synthesis of thiosemicarbazone derivatives, we report herein the crystal structure of a new 3',4'-(methylenedioxy)acetophenone thiosemicarbazone derivative.

In the crystal structure of the title compound, C₁₀H₁₁N₃O₂S, the molecules are twisted and consists of two nearly planar parts, a benzo[1,3]dioxole fragment and a hydrazinecarbothioamide fragment (mean deviations from planarity for non-H atoms 0.0325 (12) Å and 0.0707 (10) Å, respectively), which subtend a dihedral angle of 29.06 (5)° (Fig. 1). The molecule shows an E conformation for the atoms about the N3—N2 and N2—C1 bonds, which is also observed in the crystal structures of other thiosemicarbazone derivatives (de Oliveira et al., 2012).

In the crystal structure the molecules are linked by pairs of N—H···S hydrogen bonds into inversion related dimers (Fig. 2 and Table 1). These dimers are further connected by centrosymmetric pairs of weak N—H···S interactions into chains extending along [101] (Fig. 2). Finally, there is one N—H···O contact between that NH₂ hydrogen atom which is not involved in N—H···S bonding and the dioxole oxygen O1 (Table 1). If this contact is considered as an interaction the chains are additionally linked into a three-dimensional network (Fig. 2).

In the crystal structure the benzo[1,3]dioxole fragments are oriented nearly perpendicular to [001] and are stacked above each other along this direction by the c-glide plane with a repetition period of c/2 = 3.5645 (7) Å implying π-π stacking.

Related literature

For the adapted synthesis of the title compound, see: de Oliveira et al. (2012). For the pharmacological activity of 3',4'-(methylenedioxy)acetophenone thiosimecarbazone derivatives, see: Silva et al. (1998).

S2. Experimental

All starting materials are commercially available and were used without further purification. The synthesis was adapted from a procedure reported previously (de Oliveira et al., 2012). The hydrochloric acid catalyzed reaction of 3',4'-(methylenedioxy)acetophenone (10 mmol) and thiosemicarbazide (10 mmol) in a 3:1 mixture of ethanol and water (100 ml) was refluxed for 6 h. After cooling and filtering crystals suitable for X-ray diffraction were obtained.

Elemental analysis: Calc. 50.62% for C, 4.67% for H, 17.71% for N and 13.51% for S; found 50.72% for C, 4.66% for H, 17.70% for N and 13.47% for S. The melting point was determined by differential scanning calorimetry to 187° C and the enthalpy of fusion amount to 25.9 kJ/mol. After melting the compound decomposes.

S3. Refinement

All H atoms were located in a Fourier map. C-bonded H atoms were then geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with U_iso(H) = 1.2U_eq(C(CH), C(CH₂)) or 1.5U_eq(C) and AFIX 136 for the methyl group. The N-bonded H atoms were only adjusted to N—H = 0.88 Å and were then refined as riding with U_iso(H) = 1.2 U_eq(N).

Computing details

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-RED32 (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 40% probability level.
	Fig. 2. Crystal structure of the title compound in a view along the a axis with hydrogen bonds shown as dashed lines.

1-(2H-1,3-Benzodioxol-5-yl)ethanone thiosemicarbazone

Crystal data

C10H11N3O2S	F(000) = 496
Mr = 237.28	Dx = 1.461 Mg m^−3
Monoclinic, P21/c	Melting point: 460.2 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.1423 (12) Å	Cell parameters from 8000 reflections
b = 26.065 (5) Å	θ = 3–27.9°
c = 7.1289 (14) Å	µ = 0.29 mm^−1
β = 109.07 (3)°	T = 200 K
V = 1078.7 (4) Å^3	Block, yellow
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection

Stoe IPDS-1 diffractometer	2018 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 27.0°, θmin = 3.1°
φ scans	h = −7→7
12310 measured reflections	k = −33→33
2315 independent reflections	l = −9→9

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0692P)^2 + 0.2915P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2315 reflections	Δρmax = 0.29 e Å^−3
147 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.047 (8)

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
N1	0.2311 (2)	0.43475 (5)	0.0548 (2)	0.0326 (3)
H1N1	0.2765	0.4032	0.0431	0.049*
H2N1	0.0917	0.4461	−0.0094	0.049*
C1	0.3775 (3)	0.46661 (5)	0.1778 (2)	0.0229 (3)
S1	0.31425 (7)	0.528178 (13)	0.21371 (6)	0.03093 (17)
N2	0.5891 (2)	0.44885 (4)	0.28111 (18)	0.0252 (3)
H1N2	0.6685	0.4673	0.3840	0.030*
N3	0.6401 (2)	0.39750 (4)	0.26964 (18)	0.0230 (3)
C2	0.8498 (2)	0.38377 (5)	0.3628 (2)	0.0205 (3)
C3	1.0366 (3)	0.42034 (6)	0.4726 (3)	0.0332 (4)
H3A	1.0430	0.4489	0.3850	0.050*
H3B	1.1849	0.4024	0.5151	0.050*
H3C	1.0039	0.4336	0.5892	0.050*
C4	0.8967 (2)	0.32787 (5)	0.3605 (2)	0.0201 (3)
C5	1.1206 (3)	0.30922 (6)	0.4082 (2)	0.0276 (3)
H5	1.2450	0.3329	0.4394	0.033*
C6	1.1679 (3)	0.25646 (6)	0.4115 (3)	0.0320 (4)
H6	1.3209	0.2440	0.4421	0.038*
C7	0.9848 (3)	0.22397 (5)	0.3689 (2)	0.0250 (3)
O1	0.9848 (2)	0.17122 (4)	0.36822 (19)	0.0362 (3)
C8	0.7485 (3)	0.15623 (6)	0.3202 (3)	0.0329 (4)
H8A	0.7026	0.1345	0.1997	0.039*
H8B	0.7267	0.1362	0.4308	0.039*
O2	0.6109 (2)	0.20154 (4)	0.2866 (2)	0.0409 (3)
C9	0.7615 (3)	0.24196 (5)	0.3209 (2)	0.0241 (3)
C10	0.7108 (3)	0.29321 (5)	0.3141 (2)	0.0242 (3)
H10	0.5562	0.3049	0.2795	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0320 (7)	0.0199 (6)	0.0367 (8)	0.0067 (5)	−0.0014 (6)	−0.0073 (5)
C1	0.0269 (7)	0.0175 (6)	0.0227 (7)	0.0036 (5)	0.0060 (6)	0.0011 (5)
S1	0.0335 (3)	0.0145 (2)	0.0383 (3)	0.00688 (13)	0.00280 (18)	−0.00235 (13)
N2	0.0285 (7)	0.0133 (6)	0.0287 (7)	0.0050 (4)	0.0022 (5)	−0.0034 (4)
N3	0.0278 (6)	0.0128 (5)	0.0255 (6)	0.0044 (4)	0.0049 (5)	−0.0015 (4)
C2	0.0231 (7)	0.0162 (6)	0.0226 (7)	0.0011 (5)	0.0079 (6)	−0.0007 (5)
C3	0.0258 (8)	0.0250 (7)	0.0475 (10)	−0.0039 (6)	0.0101 (7)	−0.0084 (6)
C4	0.0220 (7)	0.0168 (6)	0.0204 (6)	0.0039 (5)	0.0056 (5)	0.0008 (5)
C5	0.0219 (7)	0.0230 (7)	0.0363 (8)	0.0034 (5)	0.0073 (6)	0.0012 (6)
C6	0.0251 (7)	0.0269 (8)	0.0429 (9)	0.0116 (6)	0.0095 (7)	0.0044 (6)
C7	0.0331 (8)	0.0172 (7)	0.0246 (7)	0.0099 (5)	0.0092 (6)	0.0030 (5)
O1	0.0434 (7)	0.0165 (5)	0.0473 (7)	0.0112 (4)	0.0129 (6)	0.0045 (4)
C8	0.0487 (10)	0.0156 (7)	0.0349 (9)	0.0047 (6)	0.0145 (8)	0.0013 (6)
O2	0.0333 (6)	0.0141 (5)	0.0703 (9)	−0.0002 (4)	0.0100 (6)	−0.0022 (5)
C9	0.0262 (7)	0.0161 (6)	0.0281 (7)	0.0012 (5)	0.0064 (6)	−0.0006 (5)
C10	0.0209 (7)	0.0170 (7)	0.0324 (8)	0.0043 (5)	0.0058 (6)	−0.0006 (5)

Geometric parameters (Å, º)

N1—C1	1.324 (2)	C4—C10	1.408 (2)
N1—H1N1	0.8802	C5—C6	1.404 (2)
N1—H2N1	0.8800	C5—H5	0.9500
C1—N2	1.3494 (19)	C6—C7	1.361 (2)
C1—S1	1.6901 (14)	C6—H6	0.9500
N2—N3	1.3831 (16)	C7—O1	1.3749 (17)
N2—H1N2	0.8800	C7—C9	1.382 (2)
N3—C2	1.2921 (19)	O1—C8	1.432 (2)
C2—C4	1.4864 (17)	C8—O2	1.4261 (19)
C2—C3	1.500 (2)	C8—H8A	0.9900
C3—H3A	0.9800	C8—H8B	0.9900
C3—H3B	0.9800	O2—C9	1.3704 (18)
C3—H3C	0.9800	C9—C10	1.3690 (19)
C4—C5	1.392 (2)	C10—H10	0.9500
C1—N1—H1N1	118.7	C4—C5—H5	119.0
C1—N1—H2N1	117.9	C6—C5—H5	119.0
H1N1—N1—H2N1	123.4	C7—C6—C5	117.03 (13)
N1—C1—N2	118.10 (12)	C7—C6—H6	121.5
N1—C1—S1	123.79 (12)	C5—C6—H6	121.5
N2—C1—S1	118.11 (11)	C6—C7—O1	128.48 (14)
C1—N2—N3	119.75 (12)	C6—C7—C9	121.67 (13)
C1—N2—H1N2	116.1	O1—C7—C9	109.84 (13)
N3—N2—H1N2	120.3	C7—O1—C8	105.81 (11)
C2—N3—N2	116.40 (12)	O2—C8—O1	108.23 (12)
N3—C2—C4	115.46 (12)	O2—C8—H8A	110.1
N3—C2—C3	123.80 (13)	O1—C8—H8A	110.1
C4—C2—C3	120.72 (13)	O2—C8—H8B	110.1
C2—C3—H3A	109.5	O1—C8—H8B	110.1
C2—C3—H3B	109.5	H8A—C8—H8B	108.4
H3A—C3—H3B	109.5	C9—O2—C8	106.15 (13)
C2—C3—H3C	109.5	C10—C9—O2	127.67 (14)
H3A—C3—H3C	109.5	C10—C9—C7	122.40 (14)
H3B—C3—H3C	109.5	O2—C9—C7	109.93 (12)
C5—C4—C10	119.61 (13)	C9—C10—C4	117.38 (13)
C5—C4—C2	121.26 (13)	C9—C10—H10	121.3
C10—C4—C2	119.12 (12)	C4—C10—H10	121.3
C4—C5—C6	121.91 (14)
N1—C1—N2—N3	−5.7 (2)	C6—C7—O1—C8	178.09 (16)
S1—C1—N2—N3	174.06 (10)	C9—C7—O1—C8	−0.96 (17)
C1—N2—N3—C2	175.99 (13)	C7—O1—C8—O2	1.91 (17)
N2—N3—C2—C4	175.80 (11)	O1—C8—O2—C9	−2.14 (17)
N2—N3—C2—C3	−2.5 (2)	C8—O2—C9—C10	−177.54 (15)
N3—C2—C4—C5	163.15 (13)	C8—O2—C9—C7	1.57 (18)
C3—C2—C4—C5	−18.5 (2)	C6—C7—C9—C10	−0.3 (2)
N3—C2—C4—C10	−18.52 (19)	O1—C7—C9—C10	178.77 (13)
C3—C2—C4—C10	159.82 (14)	C6—C7—C9—O2	−179.51 (15)
C10—C4—C5—C6	0.0 (2)	O1—C7—C9—O2	−0.39 (18)
C2—C4—C5—C6	178.38 (14)	O2—C9—C10—C4	178.34 (15)
C4—C5—C6—C7	−1.0 (2)	C7—C9—C10—C4	−0.7 (2)
C5—C6—C7—O1	−177.77 (15)	C5—C4—C10—C9	0.8 (2)
C5—C6—C7—C9	1.2 (2)	C2—C4—C10—C9	−177.57 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1^i	0.88	2.66	3.2207 (17)	123
N1—H2N1···S1^ii	0.88	2.53	3.4100 (18)	175
N2—H1N2···S1^iii	0.88	2.84	3.5048 (15)	134

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