Methyl 2-(2-amino-1,3-thia­zol-4-yl)-2-[(Z)-methoxy­carbonyl­methoxy­imino]ethano­ate

Shahzad Sharif; M Nawaz Tahir; Islam Ullah Khan; Sarfraz Ahmad; Manan Ayub Salariya

doi:10.1107/S1600536809007661

. 2009 Mar 6;65(Pt 4):o713. doi: 10.1107/S1600536809007661

Methyl 2-(2-amino-1,3-thiazol-4-yl)-2-[(Z)-methoxycarbonylmethoxyimino]ethanoate

Shahzad Sharif ^a, M Nawaz Tahir ^b,^*, Islam Ullah Khan ^a, Sarfraz Ahmad ^c, Manan Ayub Salariya ^c

PMCID: PMC2969052 PMID: 21582450

Abstract

In the molecule of the title compound, C₉H₁₁N₃O₅S, the thiazole ring is oriented at dihedral angles of 87.33 (3) and 87.18 (3)° with respect to the planar (r.m.s. deviations 0.0136 and 0.0139 Å) methyl ester groups. The dihedral angle between the methyl ester groups is 44.20 (3)°. In the crystal structure, intermolecular N—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds link the molecules along the a axis, through R ₂ ²(8) and R ₂ ²(22) ring motifs, forming infinite two-dimensional polymeric sheets. π–π Contacts between the thiazole rings [centroid–centroid distance = 3.536 (2) Å] may further stabilize the structure.

Related literature

For general background, see: Fu et al. (2005 ▶); Saprykina et al. (2006 ▶). For a related structure, see: Cheng (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶). For ring motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₉H₁₁N₃O₅S
M _r = 273.27
Monoclinic,
a = 12.240 (2) Å
b = 5.7500 (8) Å
c = 19.887 (3) Å
β = 120.016 (8)°
V = 1211.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.22 × 0.08 × 0.06 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.975, T _max = 0.982
10459 measured reflections
2168 independent reflections
1102 reflections with I > 2σ(I)
R _int = 0.100

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.124
S = 1.01
2168 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.25 e Å⁻³

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 for Windows (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/S1600536809007661/hk2639sup1.cif

e-65-0o713-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007661/hk2639Isup2.hkl

e-65-0o713-Isup2.hkl^{(104.4KB, 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
N2—H2A⋯N1ⁱ	0.86	2.22	3.057 (5)	163
N2—H2B⋯O5ⁱⁱ	0.86	2.27	3.097 (5)	160
C6—H6A⋯O3ⁱⁱⁱ	0.96	2.53	3.408 (5)	152
C6—H6C⋯O4^iv	0.96	2.51	3.385 (6)	152

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

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer and for technical support, respectively.

supplementary crystallographic information

Comment

The title compound belongs to thiazole group of organic compounds. Thiazole derivatives have been widely used as intermediates for the syntheses of pharmaceutical active products (Saprykina et al., 2006). 2-Amino thiazole derivatives are the special compounds, which are used for the syntheses of antibiotics (Fu et al., 2005) such as cephalosporins. We report herein the crystal structure of the title compound, (I), which was obtained by alkolysis of mica ester (S-2-benzothiazolyl(Z)-2-(2-aminothiazole -4-yl)-2-methoxy-carbonylmethoxyiminothioacetate) in methanol.

In the molecule of (I), (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. (I) is different from (Z)-(2-amino- thiazol-1-ium-4-yl)-2-(t-butoxycarbonylmethoxyimino)acetate monohydrate, (II) (Cheng, 2007), due to the attachements at carboxylate groups. In (I), ring A (S1/N1/C1-C3) is, of course, planar, and it is oriented with respect to the planar methyl ester moieties (O1/O2/C5/C6) and (O4/O5/C8/C9) at dihedral angles of 87.33 (3) and 87.18 (3) °, respectively, while the dihedral angle between the methyl ester moieties is 44.20 (3)°.

In the crystal structure, intermolecular N-H···N, N-H···O and C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The N-H···N hydrogen bonds link the molecules into dimers by forming the R₂²(8) ring motifs (Bernstein et al., 1995), then N-H···O hydrogen bonds connect the dimers by forming R₂²(22) ring motifs, and C-H···O hydrogen bonds interlink the dimers along the a axis forming infinite two-dimensional polymeric sheets. The π-π contact between the thiazole rings, Cg1—Cg1ⁱ [symmetry code: (i) -x, 1 - y, 1 - z, where Cg1 is centroid of the ring A (S1/N1/C1-C3)] may further stabilize the structure, with centroid-centroid distance of 3.536 (2) Å.

Experimental

For the preparation of the title compound, mica ester, S-2-benzo- thiazolyl-(Z)-2-(2-aminothiazole-4-yl)-2-methoxy-carbonylmethoxyimino- thioacetate) (1.0 g, 2.195 mmol) was suspended in methanol (10 ml). The suspension was heated, stirred at pH = 6.5 for 15 min. The clear transparent mixture was allowed to cool at room temperature from which light yellow crystals were obtained after 3 d.