2-(4-Oxo-3-phenyl-1,3-thia­zolidin-2-yl­idene)malononitrile

Sakka, O.K.; Fleita, D.H.; Harrison, W.T.A.

doi:10.1107/S160053681300216X

organic compounds

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Volume 69| Part 3| March 2013| Page o350

doi:10.1107/S160053681300216X

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2-(4-Oxo-3-phenyl-1,3-thiazolidin-2-ylidene)malononitrile

Ola K. Sakka,^a ^* Daisy H. Fleita ^a and William T. A. Harrison ^b

^aDepartment of Chemistry, American University in Cairo, PO Box 74, New Cairo 11835, Egypt, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 16 January 2013; accepted 22 January 2013; online 6 February 2013)

In the title compound, C₁₂H₇N₃OS, the essentially planar thiazole ring (r.m.s. deviation = 0.022 Å) forms dihedral angles of 84.88 (9) and 1.8 (3)° with the phenyl ring and the –C(CN)₂ group (r.m.s. deviation = 0.003 Å), respectively. The molecule has approximate local C_s symmetry. In the crystal, molecules are linked via C—H⋯N hydrogen bonds, forming chains propagating along [101]. The crystal studied was found to be an inversion twin with a refined 0.63 (1):0.37 (1) domain ratio.

Related literature

For background to 1,3-thiazolidin-4-ones and their properties, see: Singh et al. (1981 ); Liesen et al. (2010 ); Kocabalkanli et al. (2001 ); Kumar et al. (2007 ). For further synthetic details, see: Mohareb et al. (2012 ). For a related structure, see: Pomés Hernández et al. (1996 ).

Experimental

Crystal data

C₁₂H₇N₃OS
M_r = 241.27
Monoclinic, C c
a = 17.0305 (8) Å
b = 9.5638 (6) Å
c = 7.1651 (4) Å
β = 104.199 (4)°
V = 1131.37 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 298 K
0.20 × 0.13 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
2136 measured reflections
2136 independent reflections
1397 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.086
S = 1.01
2136 reflections
156 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 835 Friedel pairs
Flack parameter: 0.37 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯N2ⁱ	0.93	2.62	3.504 (5)	159
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997), SCALEPACK and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681300216X/lh5577sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681300216X/lh5577Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681300216X/lh5577Isup3.cml

checkCIF report

Comment top

1,3-Thiazolidin-4-ones are heterocyclic compounds that have an atom of sulfur and nitrogen at positions 1 and 3, respectively and a carbonyl group at position 4. Their presence in penicillin was the first recognition of their occurrence in nature (Singh et al., 1981). They have found uses as antibacterial (Liesen et al., 2010), antimicrobial (Kocabalkanli et al., 2001) and anti-inflammatory agents (Kumar et al., 2007). In continuation of our studies on this family of compounds, we now report the synthesis and crystal structure of the title compound, (I).

The heterocyclic ring (C1/C2/S1/C3/N1) in (I) is close to planar (r.m.s. deviation = 0.022 Å) and subtends dihedral angles with the phenyl ring and the C(CN)₂ group (r.m.s. deviation = 0.003 Å) of 84.88 (9) and 1.8 (3)°, respectively. An alternative analysis of the heterocyclic ring as a shallow envelope sees the S atom in the flap position displaced by 0.090 (5) Å from the other atoms (r.m.s. deviation = 0.004 Å). The molecule has approximate local C_s symmetry.

There is a short intermolecular contact [2.903 (2) Å] from the O atom of the carbonyl group to the centre of a nearby heterocyclic ring (symmetry: x, 1 - x, z - 1/2), but given the non-aromatic nature of the ring, this can hardly be regarded as a bond. No other significant intermolecular contacts occur in the crystal.

For a related structure, in which the thiazole ring was also found to be almost planar, see Pomés Hernández et al. (1996).

Related literature top

For background to 1,3-thiazolidin-4-ones and their properties, see: Singh et al. (1981); Liesen et al. (2010); Kocabalkanli et al. (2001); Kumar et al. (2007). For further synthetic details, see: Mohareb et al. (2012). For a related structure, see: Pomés Hernández et al. (1996).

Experimental top

To a solution of malononitrile (0.66 g, 0.01 mol) dissolved in dimethylformamide (15 ml), potassium hydroxide pellets (0.56 g, 0.01 mol) and phenylisothiocyanate (1.35 g, 0.01 mol) were added. The reaction mixture was covered and stirred at room temperature overnight. N'-(2-chloroacetyl)-2-cyanoacetohydrazide (1.75 g, 0.01 mol) (Mohareb et al., 2012) was stirred in the following day, and the solution was covered for another night, after which the reaction mixture was poured onto ice, neutralized with dil. HCl and the precipitated solid filtered off. Yellow blocks were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level.

2-(4-Oxo-3-phenyl-1,3-thiazolidin-2-ylidene)malononitrile top

Crystal data top

C₁₂H₇N₃OS	F(000) = 496
M_r = 241.27	D_x = 1.416 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1133 reflections
a = 17.0305 (8) Å	θ = 2.9–27.5°
b = 9.5638 (6) Å	µ = 0.27 mm⁻¹
c = 7.1651 (4) Å	T = 298 K
β = 104.199 (4)°	Block, yellow
V = 1131.37 (11) Å³	0.20 × 0.13 × 0.05 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1397 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 27.5°, θ_min = 3.6°
ω scans	h = −21→22
2136 measured reflections	k = −12→11
2136 independent reflections	l = −9→9

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0223P)² + 0.0674P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.086	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 0.17 e Å⁻³
2136 reflections	Δρ_min = −0.18 e Å⁻³
156 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.008 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 835 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.37 (1)

Crystal data top

C₁₂H₇N₃OS	V = 1131.37 (11) Å³
M_r = 241.27	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 17.0305 (8) Å	µ = 0.27 mm⁻¹
b = 9.5638 (6) Å	T = 298 K
c = 7.1651 (4) Å	0.20 × 0.13 × 0.05 mm
β = 104.199 (4)°

Data collection top

Nonius KappaCCD diffractometer	1397 reflections with I > 2σ(I)
2136 measured reflections	R_int = 0.029
2136 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.086	Δρ_max = 0.17 e Å⁻³
S = 1.01	Δρ_min = −0.18 e Å⁻³
2136 reflections	Absolute structure: Flack (1983), 835 Friedel pairs
156 parameters	Absolute structure parameter: 0.37 (1)
2 restraints

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	0.40086 (17)	0.3723 (3)	0.3314 (5)	0.0435 (8)
C2	0.31911 (18)	0.3591 (4)	0.3709 (4)	0.0542 (9)
H2A	0.2827	0.3104	0.2657	0.065*
H2B	0.2969	0.4511	0.3830	0.065*
C3	0.43425 (18)	0.2567 (3)	0.6297 (4)	0.0357 (7)
C4	0.48151 (17)	0.1984 (3)	0.7933 (4)	0.0395 (8)
C5	0.4414 (2)	0.1387 (4)	0.9303 (5)	0.0487 (8)
C6	0.5676 (2)	0.1857 (3)	0.8434 (5)	0.0444 (8)
C7	0.54465 (17)	0.3210 (3)	0.4754 (4)	0.0368 (7)
C8	0.58860 (18)	0.4396 (4)	0.5395 (4)	0.0465 (8)
H8	0.5650	0.5143	0.5884	0.056*
C9	0.6685 (2)	0.4455 (5)	0.5297 (5)	0.0669 (11)
H9	0.6994	0.5242	0.5746	0.080*
C10	0.7026 (2)	0.3359 (5)	0.4543 (5)	0.0689 (13)
H10	0.7563	0.3411	0.4470	0.083*
C11	0.6581 (2)	0.2197 (5)	0.3901 (5)	0.0657 (12)
H11	0.6816	0.1456	0.3394	0.079*
C12	0.5784 (2)	0.2111 (4)	0.3998 (4)	0.0534 (10)
H12	0.5480	0.1318	0.3557	0.064*
S1	0.32943 (5)	0.26310 (9)	0.59038 (11)	0.0515 (3)
O1	0.41623 (12)	0.4253 (2)	0.1924 (3)	0.0585 (7)
N1	0.46104 (13)	0.3139 (3)	0.4828 (3)	0.0363 (6)
N2	0.40992 (18)	0.0906 (3)	1.0384 (5)	0.0703 (9)
N3	0.63584 (18)	0.1710 (3)	0.8969 (4)	0.0671 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0331 (18)	0.039 (2)	0.0570 (19)	−0.0008 (15)	0.0092 (15)	−0.0014 (17)
C2	0.036 (2)	0.071 (3)	0.0535 (19)	0.0005 (17)	0.0065 (14)	0.0031 (18)
C3	0.0287 (16)	0.0350 (19)	0.0452 (17)	−0.0036 (15)	0.0126 (13)	−0.0012 (14)
C4	0.0327 (18)	0.042 (2)	0.0459 (19)	0.0010 (14)	0.0142 (15)	0.0074 (15)
C5	0.0362 (19)	0.050 (2)	0.0577 (19)	0.0011 (16)	0.0074 (16)	0.0099 (17)
C6	0.040 (2)	0.048 (2)	0.0461 (17)	−0.0002 (16)	0.0109 (14)	0.0044 (17)
C7	0.0283 (17)	0.045 (2)	0.0386 (17)	−0.0005 (15)	0.0110 (13)	0.0027 (15)
C8	0.042 (2)	0.051 (2)	0.0490 (18)	−0.0055 (17)	0.0144 (14)	−0.0015 (16)
C9	0.047 (2)	0.095 (3)	0.060 (2)	−0.020 (2)	0.0139 (18)	0.007 (2)
C10	0.030 (2)	0.122 (4)	0.057 (2)	0.003 (2)	0.0147 (16)	0.012 (2)
C11	0.046 (2)	0.098 (3)	0.057 (2)	0.026 (2)	0.0199 (19)	0.003 (2)
C12	0.049 (2)	0.057 (3)	0.052 (2)	0.0062 (18)	0.0080 (17)	−0.0045 (15)
S1	0.0288 (4)	0.0603 (6)	0.0661 (5)	−0.0030 (5)	0.0131 (3)	0.0097 (5)
O1	0.0528 (15)	0.0679 (18)	0.0571 (13)	0.0059 (12)	0.0178 (10)	0.0173 (13)
N1	0.0280 (14)	0.0374 (16)	0.0442 (14)	−0.0027 (11)	0.0103 (11)	0.0005 (12)
N2	0.0528 (19)	0.085 (3)	0.076 (2)	−0.0039 (18)	0.0208 (15)	0.030 (2)
N3	0.040 (2)	0.092 (3)	0.067 (2)	0.0083 (17)	0.0091 (15)	0.0192 (18)

Geometric parameters (Å, º) top

C1—O1	1.202 (3)	C7—C12	1.372 (4)
C1—N1	1.412 (4)	C7—C8	1.374 (4)
C1—C2	1.492 (4)	C7—N1	1.439 (3)
C2—S1	1.792 (3)	C8—C9	1.381 (4)
C2—H2A	0.9700	C8—H8	0.9300
C2—H2B	0.9700	C9—C10	1.372 (6)
C3—N1	1.361 (4)	C9—H9	0.9300
C3—C4	1.367 (4)	C10—C11	1.361 (5)
C3—S1	1.739 (3)	C10—H10	0.9300
C4—C6	1.426 (4)	C11—C12	1.378 (5)
C4—C5	1.444 (5)	C11—H11	0.9300
C5—N2	1.142 (4)	C12—H12	0.9300
C6—N3	1.140 (4)

O1—C1—N1	122.6 (3)	C7—C8—C9	118.7 (3)
O1—C1—C2	126.5 (3)	C7—C8—H8	120.7
N1—C1—C2	110.9 (3)	C9—C8—H8	120.7
C1—C2—S1	108.3 (2)	C10—C9—C8	120.5 (4)
C1—C2—H2A	110.0	C10—C9—H9	119.8
S1—C2—H2A	110.0	C8—C9—H9	119.8
C1—C2—H2B	110.0	C11—C10—C9	120.1 (4)
S1—C2—H2B	110.0	C11—C10—H10	119.9
H2A—C2—H2B	108.4	C9—C10—H10	119.9
N1—C3—C4	126.1 (3)	C10—C11—C12	120.4 (4)
N1—C3—S1	112.7 (2)	C10—C11—H11	119.8
C4—C3—S1	121.2 (2)	C12—C11—H11	119.8
C3—C4—C6	127.1 (2)	C7—C12—C11	119.2 (4)
C3—C4—C5	117.8 (3)	C7—C12—H12	120.4
C6—C4—C5	115.1 (3)	C11—C12—H12	120.4
N2—C5—C4	179.5 (4)	C3—S1—C2	92.06 (15)
N3—C6—C4	174.6 (3)	C3—N1—C1	115.8 (2)
C12—C7—C8	121.1 (3)	C3—N1—C7	124.7 (2)
C12—C7—N1	119.5 (3)	C1—N1—C7	119.4 (2)
C8—C7—N1	119.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N2ⁱ	0.93	2.62	3.504 (5)	159

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₇N₃OS
M_r	241.27
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	17.0305 (8), 9.5638 (6), 7.1651 (4)
β (°)	104.199 (4)
V (Å³)	1131.37 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.20 × 0.13 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2136, 2136, 1397
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.086, 1.01
No. of reflections	2136
No. of parameters	156
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18
Absolute structure	Flack (1983), 835 Friedel pairs
Absolute structure parameter	0.37 (1)

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N2ⁱ	0.93	2.62	3.504 (5)	159

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Acknowledgements

The authors would like to thank the American University in Cairo for providing financial support to complete this work.

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