(5E)-5-(4-Hydr­oxy-3-methoxy­benzyl­idene)-2-thioxo-1,3-thia­zolidin-4-one methanol monosolvate

Durre Shahwar; M Nawaz Tahir; Muhammad Asam Raza; Maria Saddaf; Sana Majeed

doi:10.1107/S1600536809039567

. 2009 Oct 3;65(Pt 11):o2638. doi: 10.1107/S1600536809039567

(5E)-5-(4-Hydroxy-3-methoxybenzylidene)-2-thioxo-1,3-thiazolidin-4-one methanol monosolvate

Durre Shahwar ^a, M Nawaz Tahir ^b,^*, Muhammad Asam Raza ^a, Maria Saddaf ^a, Sana Majeed ^a

PMCID: PMC2971307 PMID: 21578253

Abstract

In the title compound, C₁₁H₉NO₃S₂·CH₄O, the dihedral angle between the aromatic rings is 3.57 (16)° and intramolecular O—H⋯O and C—H⋯S interactions occur. In the crystal, the thiazolidin-4-one molecules are linked by N—H⋯O hydrogen bonds, forming chains. The hydrogen-bond motifs lead to S(5), S(6) and R ₃ ³(8) ring motifs. There exist C=O⋯π interactions between the heterocyclic rings and π–π interactions between the heterocyclic and benzene rings at distances of 3.455 (2) and 3.602 (2) Å, respectively. The methanol solvent molecule is disordered over two sets of sites in a 0.542 (9):0.458 (9) ratio.

Related literature

For related structures, see: Barreiro et al. (2007 ▶); Shahwar et al. (2009 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₉NO₃S₂·CH₄O
M _r = 299.35
Orthorhombic,
a = 17.731 (2) Å
b = 11.7528 (14) Å
c = 6.5715 (6) Å
V = 1369.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 296 K
0.26 × 0.13 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.942, T _max = 0.955
7574 measured reflections
2472 independent reflections
1807 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.070
S = 1.02
2472 reflections
185 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ▶), 829 Friedal Pairs
Flack parameter: 0.01 (8)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809039567/hb5118sup1.cif

e-65-o2638-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039567/hb5118Isup2.hkl

e-65-o2638-Isup2.hkl^{(119KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.88 (3)	2.21 (3)	2.641 (3)	109 (3)
C2—H2⋯S1	0.93	2.66	3.349 (3)	132
O1—H1⋯O4Aⁱ	0.88 (3)	1.85 (3)	2.622 (7)	145 (3)
N1—H1N⋯O1ⁱⁱ	0.86	2.05	2.899 (3)	169
O4A—H4A⋯O3ⁱⁱⁱ	0.96 (8)	1.79 (8)	2.744 (7)	173 (7)
C12A—H12A⋯O3^iv	0.96	2.37	3.150 (5)	139

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the C1–C6 benzene ring.

Acknowledgments

MAR greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing him with a Scholaship under the Indigenous PhD Program (PIN 042–111212-PS2–200).

supplementary crystallographic information

Comment

We have recently reported the crystal structure of (5Z)-5-(2-Hydroxybenzylidene)-2-thioxo-1,3-thiazolidin-4-one - methanol (1:0.5) (Shahwar et al., 2009). In continuation of synthesizing various derivatives of rhodanine, the title compound (I, Fig. 1), is being reported.

The crystal structure of (II) 5-(4-Hydroxybenzylidene)-2-thioxo-1,3-thiazolidin-4-one dimethylsulfoxide solvate (Barreiro, et al., 2007) has been published. The title compound (I) differs from (II) due to attachment of methoxy group adjacent to the hydroxy group and due to solvate i.e methanol instead of dimethylsulfoxide.

In the title molecule there exist interamolecular H-bondings of O—H···O, C—H···O and S—H···O types (Table 1, Fig. 1) forming two S(5) and one S(6) ring motif (Bernstein et al., 1995). The role of disordered methanol solvate is to interlink the molecules through O—H···O type of H-bondings forming R₃³(8) ring motifs (Fig. 2). The molecules are stabilized in the form of infinite one dimensional polymeric chains. There exist π–π interactions between the centroids of heterocyclic ring Cg1 (C8/C9/N1/C10/S1) and the benzene ring Cg2 (C1—C6). The distance between the centroids Cg1 →Cg2 is 3.455 (2) Å due to symmetry (x, y, ∓1 + z) and for Cg2 →Cg1 is 3.602 (2) Å due to symmetry (1/2 - x, ∓1/2 + y, ∓1/2 + z), respectively. The molecules may also be stabilized due C==O···π interaction (Table 1). The methanol molecule is disordered over two sites with an occupancy ratio of 0.542 (9):0.458 (9).

Experimental

Rhodanine (0.266 g, 0.2 mol), 4-hydroxy-3-methoxybenzaldehyde (0.304 g, 0.2 mol) and K₂CO₃ (0.553 g, 0.4 mol) were dissolved in 10 ml distilled water at room temperature. The stirring was continued for 24 h and reaction was monitored by TLC. The precipitates were formed during neutalization of the reaction mixture with 5% HCl. The precipitates were filtered off and washed with saturated solution of NaCl. The crude material obtained was recrystalized in methanol to affoard dark brown needles of (I).