2-(1,2,3,4-Tetra­hydro­naphthalen-1-yl­idene)hydrazinecarbothio­amide

Oliveira, A.B. de; Silva, C.S.; Feitosa, B.R.S.; Näther, C.; Jess, I.

doi:10.1107/S1600536812033302

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2581

https://doi.org/10.1107/S1600536812033302

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2-(1,2,3,4-Tetrahydronaphthalen-1-ylidene)hydrazinecarbothioamide

Adriano Bof de Oliveira,^a ^* Cecília Santos Silva,^a Bárbara Regina Santos Feitosa,^a Christian Näther ^b and Inke Jess ^b

^aDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, Campus, 49100-000 São Cristóvão-SE, Brazil, and ^bInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
^*Correspondence e-mail: adriano@daad-alumni.de

(Received 11 June 2012; accepted 23 July 2012; online 28 July 2012)

The molecular structure of the title compound, C₁₁H₁₃N₃S, is not planar: the maximum deviation from the mean plane of the non-H atoms is 0.521 (2) Å for an aliphatic C atom, which corresponds to an envelope conformation for the non-aromatic ring. The hydrazinecarbothioamide substituent and the benzene ring have maximum deviations from the mean planes through the non-H atoms of 0.0288 (16) and 0.0124 (27) Å, respectively, and the dihedral angle between the two planes is 8.84 (13)°. In the crystal, molecules are linked into chains along [1-10] by pairs of N—H⋯S hydrogen bonds between molecules related by centres of symmetry.

Related literature

For the synthesis of the title compound and the pharmacological activity of ketonethiosemicrabazones, see: Thanigaimalai et al. (2011 ). For crystal structures of other thiosemicarbazone derivatives with pharmacological activity, see: Pederzolli et al. (2011 ); Bittencourt et al. (2012 ).

Experimental

Crystal data

C₁₁H₁₃N₃S
M_r = 219.30
Monoclinic, C 2/c
a = 15.4388 (11) Å
b = 5.5781 (3) Å
c = 26.338 (2) Å
β = 102.940 (6)°
V = 2210.6 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Stoe IPDS-1 diffractometer
7673 measured reflections
2402 independent reflections
2019 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.126
S = 1.08
2402 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯S1ⁱ	0.89	2.71	3.5606 (14)	161
N3—H1N3⋯S1ⁱⁱ	0.89	2.45	3.3351 (16)	171
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y, -z+1.

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: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812033302/fy2063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812033302/fy2063Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812033302/fy2063Isup3.cml

checkCIF report

Comment top

Thiosemicarbazone derivatives have a wide range of pharmacological properties. For example, ketonethiosemicarbazones show pharmacological activity against melanogenesis in melanoma B16 cells (Thanigaimalai et al., 2011). As part of our study on the synthesis of thiosemicarbazone derivatives, we report herein the crystal structure of 2-(3,4-dihydronaphthalen-1(2H)-ylidene)hydrazinecarbothioamide.

In the crystal structure of the title compound the maximum deviation from the least squares plane through all non-hydrogen atoms is 0.5205 (23) Å for C3, which is in agreement with the envelope conformation observed for the non-aromatic ring (Fig. 1).

The molecule shows an trans conformation for the atoms about the C1—N1/N1—N2/N2—C11 bonds. The mean deviations from the least squares planes for the N1/N2/C11/N3/S1 and C5/C6/C7/C8/C9/C10 fragments amount to 0.0288 (16) Å for N2 and 0.0124 (27) Å for C7, respectively, and the dihedral angle between the two planes is 8.84 (13)°. The trans conformation for the thiosemicarbazone fragment is also observed in other structures (Pederzolli et al., 2011 and Bittencourt et al., 2012).

The molecules are connected via centrosymmetric pairs of N—H···S hydrogen bonds, forming a one-dimensional H-bonded polymer along [1 -1 0] (Fig. 2 and Table 1).

Related literature top

For the synthesis of the title compound and the pharmacological activity of ketonethiosemicrabazones, see: Thanigaimalai et al. (2011). For crystal structures of other thiosemicarbazone derivatives with pharmacological activity, see: Pederzolli et al. (2011); Bittencourt et al. (2012).

Experimental top

All starting materials were commercially available and were used without further purification. The synthesis was adapted from a procedure reported previously (Thanigaimalai et al., 2011). The hydrochloric acid catalyzed reaction of 1-tetralone (10 mmol) and thiosemicarbazide (10 mmol) in a 3:1 mixture of ethanol and water (100 ml) was refluxed for 7 h. After cooling and filtering, crystals suitable for X-ray diffraction were obtained by recrystallization from tetrahydrofurane.

Structure description top

The molecules are connected via centrosymmetric pairs of N—H···S hydrogen bonds, forming a one-dimensional H-bonded polymer along [1 -1 0] (Fig. 2 and Table 1).

For the synthesis of the title compound and the pharmacological activity of ketonethiosemicrabazones, see: Thanigaimalai et al. (2011). For crystal structures of other thiosemicarbazone derivatives with pharmacological activity, see: Pederzolli et al. (2011); Bittencourt et al. (2012).

Computing details top

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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 40% probability level.
	Fig. 2. Crystal structure of the title compound with view along the crystallographic c axis, showing the N—H···S hydrogen bonding as dashed lines.

2-(1,2,3,4-Tetrahydronaphthalen-1-ylidene)hydrazinecarbothioamide top

Crystal data top

C₁₁H₁₃N₃S	Z = 8
M_r = 219.30	F(000) = 928
Monoclinic, C2/c	D_x = 1.318 Mg m⁻³
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 15.4388 (11) Å	µ = 0.26 mm⁻¹
b = 5.5781 (3) Å	T = 293 K
c = 26.338 (2) Å	Block, yellow
β = 102.940 (6)°	0.3 × 0.2 × 0.2 mm
V = 2210.6 (3) Å³

Data collection top

Stoe IPDS-1 diffractometer	2019 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Stoe IPDS-1	R_int = 0.043
Graphite monochromator	θ_max = 27.0°, θ_min = 3.4°
φ scans	h = −19→19
7673 measured reflections	k = −6→7
2402 independent reflections	l = −29→33

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0611P)² + 0.6719P] where P = (F_o² + 2F_c²)/3
2402 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₁H₁₃N₃S	V = 2210.6 (3) Å³
M_r = 219.30	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.4388 (11) Å	µ = 0.26 mm⁻¹
b = 5.5781 (3) Å	T = 293 K
c = 26.338 (2) Å	0.3 × 0.2 × 0.2 mm
β = 102.940 (6)°

Data collection top

Stoe IPDS-1 diffractometer	2019 reflections with I > 2σ(I)
7673 measured reflections	R_int = 0.043
2402 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.08	Δρ_max = 0.19 e Å⁻³
2402 reflections	Δρ_min = −0.21 e Å⁻³
136 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.29958 (11)	0.7852 (3)	0.39372 (7)	0.0547 (4)
C2	0.21106 (12)	0.8320 (4)	0.40609 (8)	0.0651 (5)
H2A	0.2187	0.9398	0.4357	0.078*
H2B	0.1869	0.6825	0.4157	0.078*
C3	0.14622 (13)	0.9414 (4)	0.36024 (9)	0.0748 (6)
H3A	0.1336	0.8271	0.3318	0.090*
H3B	0.0909	0.9779	0.3702	0.090*
C4	0.18397 (16)	1.1667 (4)	0.34255 (10)	0.0803 (6)
H4A	0.1438	1.2255	0.3113	0.096*
H4B	0.1882	1.2883	0.3693	0.096*
C5	0.27389 (14)	1.1280 (3)	0.33150 (7)	0.0647 (5)
C6	0.30605 (19)	1.2810 (4)	0.29776 (9)	0.0837 (6)
H6	0.2709	1.4078	0.2821	0.100*
C7	0.3882 (2)	1.2473 (5)	0.28746 (10)	0.0920 (7)
H7	0.4087	1.3528	0.2654	0.110*
C8	0.43993 (17)	1.0605 (5)	0.30923 (10)	0.0881 (7)
H8	0.4950	1.0357	0.3013	0.106*
C9	0.41110 (15)	0.9082 (4)	0.34300 (9)	0.0761 (6)
H9	0.4472	0.7820	0.3581	0.091*
C10	0.32796 (12)	0.9407 (3)	0.35500 (7)	0.0583 (4)
N1	0.35565 (10)	0.6249 (3)	0.41497 (6)	0.0566 (4)
N2	0.33609 (9)	0.4805 (3)	0.45306 (6)	0.0580 (4)
H1N2	0.2861	0.4818	0.4646	0.070*
C11	0.39552 (11)	0.3092 (3)	0.47378 (7)	0.0540 (4)
N3	0.46628 (10)	0.2886 (3)	0.45383 (7)	0.0680 (5)
H1N3	0.5063	0.1731	0.4636	0.082*
H2N3	0.4719	0.4075	0.4323	0.082*
S1	0.37784 (3)	0.13624 (10)	0.52278 (2)	0.0675 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0598 (9)	0.0488 (9)	0.0579 (9)	0.0039 (7)	0.0182 (7)	0.0021 (7)
C2	0.0643 (10)	0.0616 (11)	0.0741 (12)	0.0111 (8)	0.0254 (9)	0.0117 (9)
C3	0.0649 (11)	0.0767 (13)	0.0823 (14)	0.0139 (10)	0.0152 (10)	0.0063 (11)
C4	0.0913 (14)	0.0677 (13)	0.0816 (14)	0.0220 (11)	0.0186 (11)	0.0137 (11)
C5	0.0867 (13)	0.0505 (10)	0.0566 (10)	0.0006 (9)	0.0153 (9)	0.0002 (8)
C6	0.1232 (19)	0.0616 (12)	0.0656 (12)	−0.0012 (12)	0.0197 (12)	0.0117 (10)
C7	0.128 (2)	0.0829 (16)	0.0730 (14)	−0.0202 (15)	0.0384 (14)	0.0123 (12)
C8	0.0951 (16)	0.0975 (17)	0.0812 (15)	−0.0122 (14)	0.0396 (13)	0.0123 (13)
C9	0.0788 (13)	0.0780 (14)	0.0779 (13)	0.0020 (10)	0.0310 (11)	0.0133 (11)
C10	0.0706 (10)	0.0515 (9)	0.0546 (9)	−0.0013 (8)	0.0178 (8)	0.0023 (8)
N1	0.0617 (8)	0.0545 (8)	0.0578 (8)	0.0057 (6)	0.0226 (6)	0.0075 (7)
N2	0.0561 (8)	0.0595 (9)	0.0641 (8)	0.0119 (6)	0.0257 (7)	0.0127 (7)
C11	0.0531 (8)	0.0519 (9)	0.0604 (10)	0.0071 (7)	0.0199 (7)	0.0017 (7)
N3	0.0628 (9)	0.0686 (10)	0.0820 (11)	0.0186 (7)	0.0362 (8)	0.0212 (8)
S1	0.0622 (3)	0.0737 (4)	0.0741 (3)	0.0200 (2)	0.0316 (2)	0.0242 (2)

Geometric parameters (Å, º) top

C1—N1	1.282 (2)	C6—H6	0.9300
C1—C10	1.478 (2)	C7—C8	1.359 (4)
C1—C2	1.497 (2)	C7—H7	0.9300
C2—C3	1.514 (3)	C8—C9	1.374 (3)
C2—H2A	0.9700	C8—H8	0.9300
C2—H2B	0.9700	C9—C10	1.401 (3)
C3—C4	1.503 (3)	C9—H9	0.9300
C3—H3A	0.9700	N1—N2	1.3722 (19)
C3—H3B	0.9700	N2—C11	1.352 (2)
C4—C5	1.497 (3)	N2—H1N2	0.8899
C4—H4A	0.9700	C11—N3	1.319 (2)
C4—H4B	0.9700	C11—S1	1.6818 (17)
C5—C10	1.393 (3)	N3—H1N3	0.8900
C5—C6	1.401 (3)	N3—H2N3	0.8900
C6—C7	1.368 (4)

N1—C1—C10	115.77 (15)	C7—C6—H6	119.4
N1—C1—C2	125.91 (16)	C5—C6—H6	119.4
C10—C1—C2	118.28 (15)	C8—C7—C6	120.3 (2)
C1—C2—C3	111.69 (16)	C8—C7—H7	119.8
C1—C2—H2A	109.3	C6—C7—H7	119.8
C3—C2—H2A	109.3	C7—C8—C9	120.1 (2)
C1—C2—H2B	109.3	C7—C8—H8	119.9
C3—C2—H2B	109.3	C9—C8—H8	119.9
H2A—C2—H2B	107.9	C8—C9—C10	120.8 (2)
C4—C3—C2	110.56 (19)	C8—C9—H9	119.6
C4—C3—H3A	109.5	C10—C9—H9	119.6
C2—C3—H3A	109.5	C5—C10—C9	119.00 (18)
C4—C3—H3B	109.5	C5—C10—C1	120.42 (16)
C2—C3—H3B	109.5	C9—C10—C1	120.53 (17)
H3A—C3—H3B	108.1	C1—N1—N2	119.39 (14)
C5—C4—C3	112.39 (17)	C11—N2—N1	118.00 (13)
C5—C4—H4A	109.1	C11—N2—H1N2	115.5
C3—C4—H4A	109.1	N1—N2—H1N2	126.4
C5—C4—H4B	109.1	N3—C11—N2	116.66 (15)
C3—C4—H4B	109.1	N3—C11—S1	123.15 (13)
H4A—C4—H4B	107.9	N2—C11—S1	120.19 (12)
C10—C5—C6	118.5 (2)	C11—N3—H1N3	122.2
C10—C5—C4	120.74 (17)	C11—N3—H2N3	113.4
C6—C5—C4	120.78 (19)	H1N3—N3—H2N3	124.3
C7—C6—C5	121.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···S1ⁱ	0.89	2.71	3.5606 (14)	161
N3—H1N3···S1ⁱⁱ	0.89	2.45	3.3351 (16)	171

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃N₃S
M_r	219.30
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.4388 (11), 5.5781 (3), 26.338 (2)
β (°)	102.940 (6)
V (Å³)	2210.6 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Stoe IPDS1
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7673, 2402, 2019
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.126, 1.08
No. of reflections	2402
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: X-AREA (Stoe & Cie, 2008), X-RED32 (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···S1ⁱ	0.89	2.71	3.5606 (14)	161.0
N3—H1N3···S1ⁱⁱ	0.89	2.45	3.3351 (16)	171.1

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

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig–Holstein, Germany. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. CSS acknowledges CAPES for the award of a scholarship.

References

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