Crystal structure of methyl 2-hy­droxy-5-[(4-oxo-4,5-di­hydro-1,3-thia­zol-2-yl)amino]benzoate

Shaaban K Mohamed; Joel T Mague; Mehmet Akkurt; Hajjaj H M Abdu-Allah; Mustafa R Albayati

doi:10.1107/S2056989015006416

. 2015 Apr 9;71(Pt 5):o282–o283. doi: 10.1107/S2056989015006416

Crystal structure of methyl 2-hydroxy-5-[(4-oxo-4,5-dihydro-1,3-thiazol-2-yl)amino]benzoate

Shaaban K Mohamed ^a,^b, Joel T Mague ^c, Mehmet Akkurt ^d, Hajjaj H M Abdu-Allah ^e, Mustafa R Albayati ^f,^*

PMCID: PMC4420109 PMID: 25995905

Abstract

The title compound, C₁₁H₁₀N₂O₄S, crystallized with two independent molecules (A and B) in the asymmetric unit. They differ primarily in the rotational orientation of the five-membered heterocyclic ring. In molecule A this ring is inclined to the benzene ring by 48.17 (8)°, while in molecule B the same dihedral angle is 23.07 (8)°. In each molecule there is an intramolecular O—H⋯O hydrogen bond involving the adjacent hydroxyl group and the ester carbonyl O atom. In the crystal, the A molecules are linked via pairs of N—H⋯N hydrogen bonds, forming inversion dimers. These dimers are linked to the B molecules via N—H.·O, C—H⋯O and C—H⋯S hydrogen bonds forming corrugated sheets lying parallel to (102).

Keywords: crystal structure, aminosalicylic acid, thiazolidinones, hydrogen bonding

Related literature

For pharmaceutical and chemotherapeutic properties of amino salicylic acid derivatives, see: Abdel-Alim et al. (2005 ▸); Abdu-Allah et al. (2005 ▸); Koelink et al. (2010 ▸). For general biological activities of thiazolidinone scaffold compounds, see: Tripathi et al. (2014 ▸).

Experimental

Crystal data

C₁₁H₁₀N₂O₄S
M _r = 266.27
Monoclinic,
a = 4.7787 (1) Å
b = 25.4128 (7) Å
c = 18.9599 (5) Å
β = 90.841 (1)°
V = 2302.24 (10) Å³
Z = 8
Cu Kα radiation
μ = 2.62 mm⁻¹
T = 150 K
0.16 × 0.12 × 0.09 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T _min = 0.76, T _max = 0.80
17982 measured reflections
4582 independent reflections
3972 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.089
S = 1.04
4582 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015006416/hg5436sup1.cif

e-71-0o282-sup1.cif^{(546.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015006416/hg5436Isup2.hkl

e-71-0o282-Isup2.hkl^{(251.3KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015006416/hg5436Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015006416/hg5436fig1.tif

The asymmetric unit for the title compound with labeling scheme and 50% probability ellipsoids. The intramolecular hydrogen bonds are shown as dotted lines.

Click here for additional data file.^{(1.3MB, tif)}

a . DOI: 10.1107/S2056989015006416/hg5436fig2.tif

Packing viewed down the a axis with O—H⋯O (red) N—H⋯O (blue), N—H⋯N (blue), C—H⋯O (black) and C—H⋯S (yellow) interactions shown as dotted lines.

Click here for additional data file.^{(1.4MB, tif)}

c . DOI: 10.1107/S2056989015006416/hg5436fig3.tif

Packing viewed down the c axis. Key to dotted lines as for Fig. 2.

CCDC reference: 1056711

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1AO2	0.84	1.87	2.6287(18)	150
O5H5AO6	0.84	1.92	2.6619(18)	147
N1H1NN2ⁱ	0.91	1.96	2.8624(19)	175
N3H3NO4ⁱⁱ	0.91	1.97	2.8703(18)	170
C11H11AO8ⁱⁱⁱ	0.99	2.39	3.371(2)	171
C5H5S2^iv	0.95	2.71	3.5043(18)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

supplementary crystallographic information

S1. Comment

5-Aminosalicylic acid (5-ASA) is a prototype drug that is commonly described for treatment of inflammatory bowel diseases (Abdel-Alim, et al., 2005; Abdu-Allah, et al., 2005). It was shown that 5-ASA has,also, chemopreventive and chemotherapeutic properties (Koelink, et al., 2010). On the other hand 4-thiazolidinone derivatives have attracted continuing interest over the years because of their diverse biological activities, such as anti-inflammatory, anti-proliferative, antiviral, anticonvulsant, anti-diabetic, anti-hyperlipidemic, cardiovascular, anti-tubercular, antifungal, and antibacterial (Tripathi, et al., 2014). Based in these findings, we were interested in the synthesis of hybrid molecules that combine both pharmacophores, therefore we report in this study the synthesis and crystal structure of the title compound.

The title compound contains two independent molecules in the asymmetric unit which differ primarily in the rotational orientation of the 5-membered, heterocyclic ring (Fig. 1). Each molecule contais a strong, intramolecular hydrogen bond (Table 1 and Fig. 1) which determines the orientation of the ester group. The molecules pack in a zigzag fashion (Fig. 3) assembled by intermolecular N—H···O, N—H···N, C—H···O and C—H···S interactions (Table 1 and Fig. 2)

S2. Experimental

A solution of methyl 5-[(chloroacetyl)amino]-2-hydroxybenzoate (2.3 g, 9.5 mmol) and ammonium thiocyanate (1.5 g, 19.7 mmol) in 40 ml ethanol was refluxed for 3 h and allowed to stand overnight. The mixture was evaporated and the residue was washed with water and then recrystallized from ethanol/water to give the title compound (2.13 g, 85% yield); R_f = 0.25 (hexane:ethyl acetate, 2:1). Mp. 481–482 K.