(E)-5-{4-[2-(5-Ethyl­pyridin-2-yl)eth­oxy]benzyl­idene}thia­zolidine-2,4-dione

Balakumaran, K.; Mosesbabu, J.; Anireddy, J.; Chakkaravarthi, G.

doi:10.1107/S2414314617018399

organic compounds

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ISSN: 2414-3146

Volume 3| Part 1| January 2018| x171839

https://doi.org/10.1107/S2414314617018399

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(E)-5-{4-[2-(5-Ethylpyridin-2-yl)ethoxy]benzylidene}thiazolidine-2,4-dione

K. Balakumaran,^a,^b ^* J. Mosesbabu,^a Jayashree Anireddy ^b and G. Chakkaravarthi ^c ^*

^aAnalytical Research, Custom Pharmaceutical Services, Dr. Reddy's Laboratories Ltd., Bollaram Road, Miyapur, Hyderabad 500 049, India, ^bCentre for Chemical Sciences & Technology, Institute of Science and Technology, Jawaharlal Nehru Technological University, Kukatpally, Hyderabad 500 085, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: balakumarank@drreddys.com, chakkaravarthi_2005@yahoo.com

Edited by O. Blacque, University of Zürich, Switzerland (Received 20 December 2017; accepted 23 December 2017; online 9 January 2018)

In the title compound, C₁₉H₁₈N₂O₃S, the thiazolidine ring makes dihedral angles of 46.97 (8) and 7.19 (9)° with the pyridine and benzene rings, respectively. The intramolecular structure is stabilized by a weak C—H⋯S hydrogen bond, which generates a S(6) graph-set motif, and a weak C—H⋯O contact. In the crystal, N—H⋯N and C—H⋯O hydrogen bonds leads to infinite one-dimensional chains along (201) and generate an R₂²(7) ring-set motif. The crystal structure is further consolidated by weak π–π [centroid-to-centroid distance = 3.8204 (10) Å] interactions.

Keywords: crystal structure; thiazolidinedione; hydrogen bonding.

CCDC reference: 1524386

Structure description

Thiazolidinediones are known to sensitize tissues to insulin have been developed and clinically used as antidiabetic agents. They have been shown to reduce plasma glucose and lipid levels and are used for the treatment of type 2 diabetes (Day, 1999 ; Spiegelman, 1998 ). In view of this biological importance, the crystal structure of the title compound (Fig. 1) been determined and the results are presented here.

Figure 1
The molecular structure of the title compound, with the atom labelling and 30% probability displacement ellipsoids.

The geometric parameters for the title compound agree with those of reported similar structures (Vijayakumar et al., 2012 ; Xiong et al., 2011 ). The thiazolidine ring is planar [r.m.s. deviation = 0.007 (1) Å] and makes dihedral angles of 46.97 (8) and 7.19 (9)° with the pyridine and benzene rings, respectively. The intramolecular structure is stabilized by a weak C—H⋯S hydrogen bond, which generates an S(6) graph-set motif (Fig. 1) and a weak C—H⋯O contact (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯S1	0.93	2.63	3.3166 (16)	131
C16—H16⋯O2	0.93	2.49	2.861 (2)	104
N2—H2⋯N1ⁱ	0.86 (1)	2.00 (1)	2.8474 (19)	169 (2)
C7—H7⋯O2ⁱⁱ	0.93	2.53	3.310 (2)	142
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

In the crystal, N—H⋯N and C—H⋯O hydrogen bonds generate an $[R_{2}^{2}]$ (7) motif (Figs. 2 and 3) and lead to the formation of infinite chains along (201). The structure is further consolidated by a weak π–π [centroid-to-centroid distance = 3.8204 (10) Å] interaction.

Figure 2
The crystal packing viewed along the a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
Partial packing of the crystal structure showing the $[R_{2}^{2}]$ (7) graph-set motif.

Synthesis and crystallization

4-[2-(5-Ethyl-2-pyridyl)ethoxy]benzaldehyde (600 mg, 2.32 mmol) and 2, 4- thiozolidindione (299 mg, 2.55 mmol) were dissolved in methanol (7 ml) together with a catalytic amount of piperidine (1.85 mmol). The yellow mixture was heated under reflux overnight. The suspension was acidified with acetic acid (140 mg, 2.3 mmol) and stirred for one additional hour after the addition of methanol (5 ml). The mixture was cooled in an ice bath, and the resulting solid was filtered, washed with methanol and dried under vacuum. Single crystals suitable for X-ray diffraction studies were obtained by slow evaporation of a solution of the title compound in dimethyl formamide at room temperature.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₈N₂O₃S
M_r	354.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.6756 (2), 13.6762 (3), 17.6561 (4)
β (°)	110.442 (2)
V (Å³)	1736.70 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.83
Crystal size (mm)	0.32 × 0.28 × 0.24

Data collection
Diffractometer	Bruker APEX2 CCD Diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.514, 0.668
No. of measured, independent and observed [I > 2σ(I)] reflections	6076, 3314, 2894
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.115, 1.05
No. of reflections	3314
No. of parameters	231
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS2016/6 (Sheldrick, 2008 ), SHELXL2016/6 (Sheldrick, 2015 and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1524386

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617018399/zq4025sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617018399/zq4025Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617018399/zq4025Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS2016/6 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016/6 (Sheldrick, 2015 and PLATON (Spek, 2009).

(E)-5-{4-[2-(5-Ethylpyridin-2-yl)ethoxy]benzylidene}thiazolidine- 2,4-dione top

Crystal data top

C₁₉H₁₈N₂O₃S	F(000) = 744
M_r = 354.41	D_x = 1.355 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 7.6756 (2) Å	Cell parameters from 2884 reflections
b = 13.6762 (3) Å	θ = 3.2–71.7°
c = 17.6561 (4) Å	µ = 1.83 mm⁻¹
β = 110.442 (2)°	T = 295 K
V = 1736.70 (7) Å³	Needle, colourless
Z = 4	0.32 × 0.28 × 0.24 mm

Data collection top

Bruker APEX2 CCD Diffractometer	2894 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.013
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 71.7°, θ_min = 4.2°
T_min = 0.514, T_max = 0.668	h = −9→4
6076 measured reflections	k = −16→16
3314 independent reflections	l = −19→21

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0648P)² + 0.3059P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3314 reflections	Δρ_max = 0.19 e Å⁻³
231 parameters	Δρ_min = −0.22 e Å⁻³

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. C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms, with C—H = 0.93 Å (aromatic CH), 0.97 Å for CH₂, or 0.96 Å (methyl CH), and with U_iso = 1.5Ueq(methyl C) and U_iso = 1.2Ueq(aromatic and methylene C). H atom for NH group was located in difference-Fourier maps and refined with a distance restraint N—H = 0.86 (1) Å.

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

	x	y	z	U_iso*/U_eq
C1	0.2212 (3)	0.88704 (17)	0.36053 (12)	0.0697 (6)
H1A	0.119617	0.845372	0.359311	0.105*
H1B	0.203120	0.909732	0.306865	0.105*
H1C	0.226556	0.942020	0.395081	0.105*
C2	0.4006 (3)	0.83058 (16)	0.39245 (11)	0.0587 (5)
H2A	0.501190	0.871525	0.389495	0.070*
H2B	0.392555	0.774043	0.358220	0.070*
C3	0.4456 (2)	0.79665 (12)	0.47862 (10)	0.0442 (4)
C4	0.5414 (2)	0.85396 (13)	0.54435 (11)	0.0508 (4)
H4	0.584151	0.915343	0.536308	0.061*
C5	0.5742 (2)	0.82076 (12)	0.62190 (11)	0.0494 (4)
H5	0.638544	0.859367	0.666206	0.059*
C6	0.5099 (2)	0.72919 (12)	0.63283 (9)	0.0420 (3)
C7	0.3879 (2)	0.70610 (12)	0.49544 (10)	0.0444 (4)
H7	0.323915	0.666059	0.452054	0.053*
C8	0.5444 (3)	0.68656 (13)	0.71561 (10)	0.0527 (4)
H8A	0.602405	0.735354	0.756531	0.063*
H8B	0.426978	0.667993	0.720636	0.063*
C9	0.6681 (3)	0.59875 (13)	0.72869 (10)	0.0500 (4)
H9A	0.605655	0.547305	0.691233	0.060*
H9B	0.781431	0.615675	0.719115	0.060*
C10	0.7955 (2)	0.47641 (11)	0.82902 (9)	0.0407 (3)
C11	0.8401 (2)	0.44784 (12)	0.90892 (9)	0.0441 (4)
H11	0.814895	0.489596	0.945378	0.053*
C12	0.9210 (2)	0.35853 (12)	0.93485 (9)	0.0447 (4)
H12	0.950844	0.340781	0.988757	0.054*
C13	0.9592 (2)	0.29401 (11)	0.88119 (10)	0.0416 (3)
C14	0.9161 (3)	0.32535 (13)	0.80174 (10)	0.0521 (4)
H14	0.941577	0.283999	0.765103	0.063*
C15	0.8372 (3)	0.41527 (13)	0.77520 (10)	0.0521 (4)
H15	0.812238	0.434561	0.721943	0.062*
C16	1.0401 (2)	0.19743 (11)	0.90231 (10)	0.0453 (4)
H16	1.042094	0.160700	0.858298	0.054*
C17	1.1124 (2)	0.15138 (11)	0.97345 (10)	0.0418 (3)
C18	1.2431 (3)	0.07767 (14)	1.11410 (11)	0.0561 (4)
C19	1.1908 (2)	0.05152 (12)	0.97676 (10)	0.0447 (4)
N1	0.41797 (19)	0.67230 (10)	0.57002 (8)	0.0433 (3)
N2	1.2580 (2)	0.01780 (10)	1.05478 (9)	0.0493 (3)
H2	1.310 (3)	−0.0389 (10)	1.0662 (14)	0.076 (7)*
O1	0.71184 (17)	0.56551 (9)	0.80991 (6)	0.0499 (3)
O2	1.1955 (2)	0.00511 (9)	0.91897 (8)	0.0638 (4)
O3	1.2938 (3)	0.06030 (13)	1.18489 (8)	0.0859 (6)
S1	1.13659 (7)	0.19066 (3)	1.07087 (3)	0.05382 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0856 (15)	0.0638 (12)	0.0490 (10)	0.0104 (11)	0.0101 (10)	0.0119 (9)
C2	0.0670 (11)	0.0661 (12)	0.0466 (10)	0.0021 (9)	0.0245 (9)	0.0125 (9)
C3	0.0437 (8)	0.0469 (9)	0.0432 (8)	0.0048 (7)	0.0168 (7)	0.0076 (7)
C4	0.0541 (10)	0.0378 (8)	0.0571 (10)	−0.0033 (7)	0.0151 (8)	0.0061 (7)
C5	0.0530 (9)	0.0399 (8)	0.0458 (9)	0.0013 (7)	0.0051 (7)	−0.0032 (7)
C6	0.0472 (8)	0.0381 (8)	0.0378 (8)	0.0093 (6)	0.0110 (6)	0.0023 (6)
C7	0.0494 (9)	0.0443 (8)	0.0370 (8)	−0.0022 (7)	0.0121 (7)	−0.0008 (6)
C8	0.0703 (11)	0.0491 (10)	0.0365 (8)	0.0144 (8)	0.0160 (8)	0.0037 (7)
C9	0.0609 (10)	0.0511 (10)	0.0363 (8)	0.0125 (8)	0.0149 (7)	0.0087 (7)
C10	0.0448 (8)	0.0378 (8)	0.0372 (8)	0.0018 (6)	0.0113 (6)	0.0024 (6)
C11	0.0558 (9)	0.0418 (8)	0.0359 (7)	0.0060 (7)	0.0173 (7)	0.0004 (6)
C12	0.0544 (9)	0.0434 (8)	0.0369 (7)	0.0045 (7)	0.0168 (7)	0.0071 (6)
C13	0.0453 (8)	0.0383 (8)	0.0402 (8)	−0.0002 (6)	0.0138 (6)	0.0024 (6)
C14	0.0691 (11)	0.0472 (9)	0.0386 (8)	0.0113 (8)	0.0172 (8)	−0.0028 (7)
C15	0.0702 (11)	0.0507 (10)	0.0331 (8)	0.0125 (8)	0.0152 (7)	0.0039 (7)
C16	0.0545 (9)	0.0385 (8)	0.0446 (9)	0.0017 (7)	0.0194 (7)	−0.0004 (7)
C17	0.0463 (8)	0.0353 (8)	0.0442 (8)	−0.0008 (6)	0.0161 (7)	−0.0007 (6)
C18	0.0675 (11)	0.0511 (10)	0.0437 (9)	0.0124 (8)	0.0118 (8)	−0.0005 (8)
C19	0.0547 (9)	0.0357 (8)	0.0442 (8)	0.0010 (7)	0.0178 (7)	0.0005 (7)
N1	0.0523 (8)	0.0371 (7)	0.0393 (7)	−0.0003 (5)	0.0144 (6)	0.0014 (5)
N2	0.0638 (9)	0.0385 (7)	0.0431 (7)	0.0105 (6)	0.0157 (6)	0.0018 (6)
O1	0.0683 (8)	0.0447 (6)	0.0353 (6)	0.0153 (5)	0.0164 (5)	0.0064 (5)
O2	0.1034 (11)	0.0441 (7)	0.0466 (7)	0.0170 (7)	0.0294 (7)	0.0017 (6)
O3	0.1260 (14)	0.0805 (11)	0.0395 (7)	0.0390 (10)	0.0140 (8)	0.0028 (7)
S1	0.0694 (3)	0.0445 (3)	0.0435 (2)	0.01282 (19)	0.0146 (2)	−0.00351 (17)

Geometric parameters (Å, º) top

C1—C2	1.506 (3)	C10—O1	1.3638 (19)
C1—H1A	0.9600	C10—C15	1.384 (2)
C1—H1B	0.9600	C10—C11	1.387 (2)
C1—H1C	0.9600	C11—C12	1.374 (2)
C2—C3	1.511 (2)	C11—H11	0.9300
C2—H2A	0.9700	C12—C13	1.398 (2)
C2—H2B	0.9700	C12—H12	0.9300
C3—C4	1.381 (2)	C13—C14	1.392 (2)
C3—C7	1.382 (2)	C13—C16	1.452 (2)
C4—C5	1.380 (2)	C14—C15	1.379 (2)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.384 (2)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.340 (2)
C6—N1	1.337 (2)	C16—H16	0.9300
C6—C8	1.508 (2)	C17—C19	1.486 (2)
C7—N1	1.337 (2)	C17—S1	1.7488 (16)
C7—H7	0.9300	C18—O3	1.196 (2)
C8—C9	1.498 (2)	C18—N2	1.365 (2)
C8—H8A	0.9700	C18—S1	1.7897 (19)
C8—H8B	0.9700	C19—O2	1.213 (2)
C9—O1	1.4281 (19)	C19—N2	1.371 (2)
C9—H9A	0.9700	N2—H2	0.862 (10)
C9—H9B	0.9700

C2—C1—H1A	109.5	H9A—C9—H9B	108.3
C2—C1—H1B	109.5	O1—C10—C15	124.86 (14)
H1A—C1—H1B	109.5	O1—C10—C11	115.53 (14)
C2—C1—H1C	109.5	C15—C10—C11	119.61 (15)
H1A—C1—H1C	109.5	C12—C11—C10	120.77 (15)
H1B—C1—H1C	109.5	C12—C11—H11	119.6
C1—C2—C3	113.09 (16)	C10—C11—H11	119.6
C1—C2—H2A	109.0	C11—C12—C13	120.81 (14)
C3—C2—H2A	109.0	C11—C12—H12	119.6
C1—C2—H2B	109.0	C13—C12—H12	119.6
C3—C2—H2B	109.0	C14—C13—C12	117.16 (15)
H2A—C2—H2B	107.8	C14—C13—C16	117.96 (15)
C4—C3—C7	116.41 (15)	C12—C13—C16	124.88 (15)
C4—C3—C2	122.65 (16)	C15—C14—C13	122.60 (16)
C7—C3—C2	120.92 (16)	C15—C14—H14	118.7
C5—C4—C3	120.41 (16)	C13—C14—H14	118.7
C5—C4—H4	119.8	C14—C15—C10	119.01 (15)
C3—C4—H4	119.8	C14—C15—H15	120.5
C4—C5—C6	119.07 (16)	C10—C15—H15	120.5
C4—C5—H5	120.5	C17—C16—C13	131.94 (16)
C6—C5—H5	120.5	C17—C16—H16	114.0
N1—C6—C5	121.44 (15)	C13—C16—H16	114.0
N1—C6—C8	116.24 (15)	C16—C17—C19	119.89 (15)
C5—C6—C8	122.30 (15)	C16—C17—S1	130.14 (13)
N1—C7—C3	124.28 (16)	C19—C17—S1	109.96 (11)
N1—C7—H7	117.9	O3—C18—N2	126.78 (18)
C3—C7—H7	117.9	O3—C18—S1	123.41 (15)
C9—C8—C6	110.28 (14)	N2—C18—S1	109.81 (13)
C9—C8—H8A	109.6	O2—C19—N2	123.91 (15)
C6—C8—H8A	109.6	O2—C19—C17	125.37 (15)
C9—C8—H8B	109.6	N2—C19—C17	110.72 (14)
C6—C8—H8B	109.6	C6—N1—C7	118.38 (14)
H8A—C8—H8B	108.1	C18—N2—C19	117.78 (14)
O1—C9—C8	108.90 (14)	C18—N2—H2	121.0 (16)
O1—C9—H9A	109.9	C19—N2—H2	121.2 (16)
C8—C9—H9A	109.9	C10—O1—C9	117.26 (13)
O1—C9—H9B	109.9	C17—S1—C18	91.72 (8)
C8—C9—H9B	109.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···S1	0.93	2.63	3.3166 (16)	131
C16—H16···O2	0.93	2.49	2.861 (2)	104
N2—H2···N1ⁱ	0.86 (1)	2.00 (1)	2.8474 (19)	169 (2)
C7—H7···O2ⁱⁱ	0.93	2.53	3.310 (2)	142

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

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