4-Methyl-2-phenyl­pent-2-enal thio­semicarbazone

Anitha, L.; Saritha, S.R.; Layana, S.R.; Sithambaresan, M.; Sudarsanakumar, M.R.

doi:10.1107/S241431461900436X

organic compounds

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ISSN: 2414-3146

Volume 4| Part 4| April 2019| x190436

https://doi.org/10.1107/S241431461900436X

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4-Methyl-2-phenylpent-2-enal thiosemicarbazone

L. Anitha,^a S. R. Saritha,^a S. R. Layana,^a M. Sithambaresan ^b ^* and M. R. Sudarsanakumar ^a

^aDepartment of Chemistry, Mahatma Gandhi College, University of Kerala, Thiruvananthapuram 695 004, Kerala, India, and ^bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka
^*Correspondence e-mail: msithambaresan@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 30 March 2019; accepted 31 March 2019; online 5 April 2019)

In the title compound, C₁₃H₁₇N₃S, the dihedral angle between the thiosemicarbazone moiety [maximum deviation = 0.055 (2) Å] and the phenyl ring is 53.15 (12)°. In the crystal, N—H⋯S hydrogen bonds generate (100) layers, with the S atom accepting two such bonds.

Keywords: crystal structure; thiosemicarbazone; 4-methyl-2-phenyl-2-pentenal.

CCDC reference: 1906787

Structure description

Thiosemicarbazones are a family of nitrogen–sulfur donor ligands with a wide range of biological applications due in part to their ability to form terdentate chelates with transition metal ions (e.g. Scovill et al., 1982 ; Joseph et al., 2004 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

The C1=S1 [1.689 (3) Å], C2=N3 [1.270 (3) Å], N2—N3 [1.376 (3) Å] and C1—N2 [1.352 (3) Å] bond lengths show good agreement with the equivalent data for related structures (Palenik et al., 1974 ; Nandi et al., 1984 ). The title molecule exists in the E and Z configurations with respect to the C2=N2 and C3=C4 bonds, respectively. The thiosemicarbazone moiety is almost planar as a result of the extended conjugation along the moiety [maximum deviation = 0.055 (2) Å for N2] and subtends a dihedral angle of 53.15 (12)° with the pendant C8–C13 phenyl ring.

In the crystal, the molecules are linked by pairwise N1—H1A⋯S1 hydrogen bonds (Table 1), generating inversion dimers (Fig. 2). The dimers are linked into (100) sheets by N2—H2A⋯S1 bonds. There are no significant π–π interactions present in this crystal.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.86 (2)	2.56 (2)	3.409 (3)	168 (3)
N2—H2A⋯S1ⁱⁱ	0.88 (2)	2.59 (2)	3.456 (2)	167 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ .

Figure 2
N—H⋯S hydrogen-bonding interactions (dashed lines) in the title compound.

Synthesis and crystallization

A mixture of thiosemicarbazide (0.091 g; 1 mmol) and 4-methyl-2-phenyl-2-pentenal (0.18 g; 1 mmol) was refluxed in 30 ml methanol for 2–3 h. The resultant solution was concentrated and cooled to room temperature. A precipitate formed with a yield of 56% and was filtered and washed with methanol. Brown block-shaped crystals were grown by slow evaporation using ethanol as the solvent, m.p. = 199–202°C. Analysis calculated for C₁₃H₁₇N₃S: C 63.07; H 6.87; N 16.97; S 12.94%; found: C 62.92; H 7.18; N 16.91; S 12.58%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₇N₃S
M_r	247.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	30.3184 (13), 11.0972 (5), 8.0354 (3)
β (°)	93.127 (5)
V (Å³)	2699.5 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.22
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXIII CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.611, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	15555, 2373, 1723
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.135, 1.06
No. of reflections	2373
No. of parameters	168
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.22
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT2014 (Sheldrick, 2015a ), DIAMOND (Brandenburg, 2010 ), SHELXL2014 (Sheldrick, 2015b ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1906787

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461900436X/hb4290sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461900436X/hb4290Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461900436X/hb4290Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010).

4-Methyl-2-phenylpent-2-enal thiosemicarbazone top

Crystal data top

C₁₃H₁₇N₃S	F(000) = 1056
M_r = 247.35	D_x = 1.217 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 30.3184 (13) Å	Cell parameters from 5545 reflections
b = 11.0972 (5) Å	θ = 3.2–27.9°
c = 8.0354 (3) Å	µ = 0.22 mm⁻¹
β = 93.127 (5)°	T = 296 K
V = 2699.5 (2) Å³	Block, brown
Z = 8	0.15 × 0.15 × 0.10 mm

Data collection top

Bruker Kappa APEXIII CMOS diffractometer	2373 independent reflections
Radiation source: fine-focus sealed tube	1723 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ω and φ scan	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −36→36
T_min = 0.611, T_max = 0.746	k = −13→13
15555 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0658P)² + 1.9983P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2373 reflections	Δρ_max = 0.47 e Å⁻³
168 parameters	Δρ_min = −0.22 e Å⁻³
4 restraints

Special details top

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. All H atoms bound to carbon atoms were placed in calculated positions with C—H = 0.93–0.96 Å and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The N–H hydrogen atoms of the molecule were located from difference maps and N—H was restrained to 0.85 ±0.02 Å and the H···H distance to 1.38±0.02.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.73348 (9)	0.8377 (2)	0.2590 (3)	0.0333 (6)
C2	0.67138 (9)	0.8558 (2)	0.6111 (3)	0.0383 (7)
H2	0.6881	0.9141	0.6689	0.046*
C3	0.63249 (8)	0.8067 (2)	0.6863 (3)	0.0326 (6)
C4	0.62187 (9)	0.8526 (2)	0.8338 (3)	0.0386 (7)
H4	0.6408	0.9123	0.8769	0.046*
C5	0.58446 (9)	0.8221 (3)	0.9380 (3)	0.0412 (7)
H5	0.5688	0.7521	0.8896	0.049*
C6	0.60133 (12)	0.7917 (4)	1.1154 (4)	0.0690 (10)
H6A	0.6193	0.7204	1.1141	0.104*
H6B	0.5767	0.7779	1.1832	0.104*
H6C	0.6187	0.8575	1.1606	0.104*
C7	0.55250 (11)	0.9280 (3)	0.9420 (4)	0.0649 (10)
H7A	0.5680	0.9982	0.9836	0.097*
H7B	0.5291	0.9089	1.0135	0.097*
H7C	0.5403	0.9436	0.8314	0.097*
C8	0.60645 (8)	0.7130 (2)	0.5914 (3)	0.0318 (6)
C9	0.62684 (9)	0.6100 (2)	0.5307 (3)	0.0383 (7)
H9	0.6569	0.5981	0.5543	0.046*
C10	0.60319 (11)	0.5259 (3)	0.4366 (4)	0.0488 (8)
H10	0.6174	0.4584	0.3966	0.059*
C11	0.55885 (12)	0.5411 (3)	0.4016 (4)	0.0554 (9)
H11	0.5430	0.4845	0.3375	0.066*
C12	0.53782 (10)	0.6413 (3)	0.4624 (4)	0.0523 (8)
H12	0.5076	0.6514	0.4401	0.063*
C13	0.56145 (9)	0.7264 (3)	0.5560 (3)	0.0402 (7)
H13	0.5470	0.7936	0.5956	0.048*
N1	0.71567 (10)	0.7372 (3)	0.2016 (4)	0.0586 (8)
N2	0.71870 (8)	0.8787 (2)	0.4043 (3)	0.0389 (6)
N3	0.68323 (7)	0.8216 (2)	0.4694 (3)	0.0369 (6)
S1	0.77299 (2)	0.91402 (6)	0.16283 (9)	0.0398 (3)
H1A	0.7209 (9)	0.709 (3)	0.105 (3)	0.063 (10)*
H2A	0.7316 (8)	0.940 (2)	0.457 (3)	0.045 (8)*
H1B	0.6953 (8)	0.704 (3)	0.245 (3)	0.048 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0404 (15)	0.0315 (15)	0.0279 (15)	0.0029 (12)	0.0019 (12)	0.0007 (12)
C2	0.0447 (17)	0.0358 (15)	0.0343 (16)	−0.0075 (13)	0.0028 (13)	−0.0050 (13)
C3	0.0395 (15)	0.0304 (14)	0.0280 (14)	−0.0002 (12)	0.0014 (11)	−0.0011 (12)
C4	0.0446 (16)	0.0336 (15)	0.0379 (17)	−0.0035 (13)	0.0041 (13)	−0.0042 (13)
C5	0.0513 (18)	0.0384 (16)	0.0348 (16)	−0.0021 (13)	0.0101 (13)	−0.0056 (13)
C6	0.086 (3)	0.084 (3)	0.0379 (19)	−0.003 (2)	0.0090 (17)	0.0054 (18)
C7	0.065 (2)	0.063 (2)	0.068 (2)	0.0127 (17)	0.0193 (18)	−0.0117 (19)
C8	0.0422 (16)	0.0322 (15)	0.0217 (13)	−0.0010 (12)	0.0071 (11)	0.0030 (11)
C9	0.0476 (17)	0.0335 (15)	0.0342 (15)	−0.0005 (12)	0.0051 (13)	0.0016 (12)
C10	0.071 (2)	0.0356 (16)	0.0407 (17)	−0.0073 (15)	0.0081 (15)	−0.0059 (14)
C11	0.078 (2)	0.0484 (19)	0.0391 (18)	−0.0258 (18)	0.0012 (16)	−0.0064 (15)
C12	0.0470 (18)	0.065 (2)	0.0441 (18)	−0.0146 (16)	−0.0035 (14)	0.0077 (16)
C13	0.0466 (17)	0.0412 (16)	0.0331 (16)	−0.0027 (13)	0.0040 (13)	0.0036 (13)
N1	0.078 (2)	0.0532 (18)	0.0479 (18)	−0.0259 (15)	0.0292 (15)	−0.0187 (15)
N2	0.0449 (14)	0.0393 (14)	0.0333 (14)	−0.0106 (11)	0.0095 (11)	−0.0079 (11)
N3	0.0440 (14)	0.0381 (13)	0.0290 (13)	−0.0063 (11)	0.0068 (10)	−0.0008 (10)
S1	0.0449 (4)	0.0393 (4)	0.0361 (4)	−0.0001 (3)	0.0096 (3)	0.0032 (3)

Geometric parameters (Å, º) top

C1—N1	1.312 (4)	C7—H7B	0.9600
C1—N2	1.352 (3)	C7—H7C	0.9600
C1—S1	1.689 (3)	C8—C13	1.386 (4)
C2—N3	1.270 (3)	C8—C9	1.401 (4)
C2—C3	1.459 (4)	C9—C10	1.377 (4)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.345 (4)	C10—C11	1.369 (4)
C3—C8	1.490 (3)	C10—H10	0.9300
C4—C5	1.485 (4)	C11—C12	1.384 (5)
C4—H4	0.9300	C11—H11	0.9300
C5—C7	1.524 (4)	C12—C13	1.383 (4)
C5—C6	1.526 (4)	C12—H12	0.9300
C5—H5	0.9800	C13—H13	0.9300
C6—H6A	0.9600	N1—H1A	0.859 (17)
C6—H6B	0.9600	N1—H1B	0.816 (16)
C6—H6C	0.9600	N2—N3	1.376 (3)
C7—H7A	0.9600	N2—H2A	0.881 (17)

N1—C1—N2	116.1 (3)	H7A—C7—H7C	109.5
N1—C1—S1	123.6 (2)	H7B—C7—H7C	109.5
N2—C1—S1	120.2 (2)	C13—C8—C9	117.6 (2)
N3—C2—C3	122.3 (2)	C13—C8—C3	121.2 (2)
N3—C2—H2	118.9	C9—C8—C3	121.1 (2)
C3—C2—H2	118.9	C10—C9—C8	121.2 (3)
C4—C3—C2	117.5 (2)	C10—C9—H9	119.4
C4—C3—C8	124.7 (2)	C8—C9—H9	119.4
C2—C3—C8	117.8 (2)	C11—C10—C9	120.3 (3)
C3—C4—C5	129.6 (3)	C11—C10—H10	119.8
C3—C4—H4	115.2	C9—C10—H10	119.8
C5—C4—H4	115.2	C10—C11—C12	119.5 (3)
C4—C5—C7	110.0 (2)	C10—C11—H11	120.2
C4—C5—C6	110.5 (2)	C12—C11—H11	120.2
C7—C5—C6	109.4 (3)	C13—C12—C11	120.4 (3)
C4—C5—H5	109.0	C13—C12—H12	119.8
C7—C5—H5	109.0	C11—C12—H12	119.8
C6—C5—H5	109.0	C12—C13—C8	120.9 (3)
C5—C6—H6A	109.5	C12—C13—H13	119.6
C5—C6—H6B	109.5	C8—C13—H13	119.6
H6A—C6—H6B	109.5	C1—N1—H1A	122 (2)
C5—C6—H6C	109.5	C1—N1—H1B	123 (2)
H6A—C6—H6C	109.5	H1A—N1—H1B	114 (2)
H6B—C6—H6C	109.5	C1—N2—N3	118.4 (2)
C5—C7—H7A	109.5	C1—N2—H2A	120.8 (19)
C5—C7—H7B	109.5	N3—N2—H2A	120.7 (19)
H7A—C7—H7B	109.5	C2—N3—N2	117.9 (2)
C5—C7—H7C	109.5

N3—C2—C3—C4	−177.4 (3)	C3—C8—C9—C10	−177.1 (2)
N3—C2—C3—C8	0.3 (4)	C8—C9—C10—C11	−0.6 (4)
C2—C3—C4—C5	179.3 (3)	C9—C10—C11—C12	−0.4 (4)
C8—C3—C4—C5	1.8 (5)	C10—C11—C12—C13	0.8 (5)
C3—C4—C5—C7	−112.3 (3)	C11—C12—C13—C8	−0.3 (4)
C3—C4—C5—C6	126.8 (3)	C9—C8—C13—C12	−0.6 (4)
C4—C3—C8—C13	51.8 (4)	C3—C8—C13—C12	177.5 (2)
C2—C3—C8—C13	−125.7 (3)	N1—C1—N2—N3	−7.6 (4)
C4—C3—C8—C9	−130.1 (3)	S1—C1—N2—N3	172.97 (18)
C2—C3—C8—C9	52.4 (3)	C3—C2—N3—N2	175.9 (2)
C13—C8—C9—C10	1.1 (4)	C1—N2—N3—C2	175.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86 (2)	2.56 (2)	3.409 (3)	168 (3)
N2—H2A···S1ⁱⁱ	0.88 (2)	2.59 (2)	3.456 (2)	167 (2)

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

Acknowledgements

The authors thank SAIF, Chennai, India, for the data collection and Professor M. R. P. Kurup, Department of Applied Chemistry, Cochi University of Science and Technology, India for the use of DIAMONDsoftware.

Funding information

Funding for this research was provided by: University of Kerala, Thiruvananthapuram, India in the form of a Junior Research Fellowship..

References

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Joseph, M., Suni, V., Prathapachandra Kurup, M. R., Nethaji, M., Kishore, A. & Bhat, S. G. (2004). Polyhedron, 23, 3069–3080. Web of Science CSD CrossRef CAS Google Scholar
Nandi, A. K., Chaudhuri, S., Mazumdar, S. K. & Ghosh, S. (1984). Acta Cryst. C40, 1193–1196. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Palenik, G. J., Rendle, D. F. & Carter, W. S. (1974). Acta Cryst. B30, 2390–2395. CSD CrossRef IUCr Journals Web of Science Google Scholar
Scovill, J. P., Klayman, D. L. & Franchino, C. F. (1982). J. Med. Chem. 25, 1261–1264. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar