Methyl 2-{[(4-hydroxy­phen­yl)(methoxy­carbon­yl)meth­yl]amino­carbon­yl}ethano­ate hemihydrate

M Fazli Mohammat; Zurina Shaameri; A Sazali Hamzah; N Kamarulzaman; Hoong-Kun Fun; Suchada Chantrapromma

doi:10.1107/S1600536808005552

. 2008 Mar 5;64(Pt 4):o663–o664. doi: 10.1107/S1600536808005552

Methyl 2-{[(4-hydroxyphenyl)(methoxycarbonyl)methyl]aminocarbonyl}ethanoate hemihydrate

M Fazli Mohammat ^a, Zurina Shaameri ^a, A Sazali Hamzah ^a, N Kamarulzaman ^a, Hoong-Kun Fun ^b,^*, Suchada Chantrapromma ^c,^‡

PMCID: PMC2961038 PMID: 21202059

Abstract

In the structure of the title compound, C₁₃H₁₅NO₆·0.5H₂O, the water O atom lies on a twofold rotation axis. The methoxycarbonylmethyl and amino groups are essentially coplanar and the methoxycarbonylmethyl group makes a dihedral angle of 79.73 (10)° with the mean plane of the hydroxyphenyl ring. The amino and methoxycarbonylmethyl groups are involved in an intramolecular N—H⋯O hydrogen bond which generates an S(5) ring motif. In the crystal structure, molecules are linked via N—H⋯O and O—H⋯O hydrogen bonds and weak C—H⋯O interactions into a two-dimensional network parallel to the ( Inline graphic 01) plane. The crystal structure is further stabilized by C—H⋯π interactions.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For details of the biological properties of compounds containing tetramic acid, see for example: Iida et al. (1986 ▶); Matkhalikova et al. (1969 ▶); Reddy & Rao (2006 ▶); Reiner (2007 ▶); Royles (1996 ▶). For the syntheses of compounds containing tetramic acid units, see for example: Steglich (1989 ▶); Royles (1996 ▶).

Experimental

Crystal data

C₁₃H₁₅NO₆·0.5H₂O
M _r = 290.27
Monoclinic,
a = 22.7764 (12) Å
b = 5.3046 (3) Å
c = 13.0686 (6) Å
β = 117.612 (3)°
V = 1399.11 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100.0 (1) K
0.41 × 0.19 × 0.04 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.956, T _max = 0.996
9426 measured reflections
2248 independent reflections
1884 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.090
S = 1.06
2248 reflections
200 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005552/sj2467sup1.cif

e-64-0o663-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005552/sj2467Isup2.hkl

e-64-0o663-Isup2.hkl^{(110.5KB, 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
O1W—H1W⋯O1ⁱ	0.95 (4)	1.86 (3)	2.803 (3)	170 (3)
N1—H1N1⋯O1W	0.91 (3)	2.14 (3)	3.002 (3)	157 (2)
N1—H1N1⋯O3	0.91 (3)	2.28 (3)	2.669 (3)	105 (2)
O6—H1O6⋯O2ⁱⁱ	0.89 (4)	1.75 (3)	2.638 (2)	171 (3)
C2—H2A⋯O1W	0.97	2.49	3.363 (3)	150
C2—H2B⋯O6ⁱⁱ	0.97	2.34	3.146 (3)	140
C6—H6B⋯O6ⁱⁱⁱ	0.96	2.49	3.420 (3)	162
C7—H7B⋯Cg1^iv	0.96	2.68	3.574 (3)	155
C10—H10⋯Cg1ⁱⁱ	0.93	3.01	3.717 (2)	134

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg1 is the centroid of the C8–C13 phenyl ring.

Acknowledgments

The authors acknowledge the generous support of both the Universiti Teknologi MARA and the Universiti Sains Malaysia as well as the financial support of the Ministry of Science, Technology and Innovation (E-Science grant No. SF0050–02-01–01). HKF and SC thank the Malaysian Government and Universiti Sains Malaysia for the Scientific Advancement Grant Allocation (SAGA) grant No. 304/PFIZIK/653003/A118.

supplementary crystallographic information

Comment

Natural products containing tetramic acid goups continue to attract the interest of chemists and biologists due to their challenging structures and remarkable biological properties (Iida et al., 1986; Matkhalikova et al., 1969; Reddy & Rao, 2006; Reiner, 2007; Royles, 1996). Among these, tetramic acids carrying an aromatic substituent on the ring are rarely found in nature (Reddy & Rao, 2006). The title compound, C₁₃H₁₅NO₆, can act as an essential intermediate in the synthesis of compounds responsible for the orange-yellow colour of plasmodia from Leocarpus fragilis (Steglich, 1989; Royles, 1995). We have synthesized the title compound and its structure is reported here.

The asymmetric unit of the title compound contains one molecule of C₁₃H₁₅NO₆ and half an H₂O molecule with the O1W atom lying on a twofold rotation axis, (Fig. 1). The methoxycarbonylmethyl [C4/C5/C7/O3/O5] and the C3/N1/C4 amino sections of the molecule are essentially coplanar with a dihedral angle of 3.12 (10)° between them. An intramolecular N1—H1N1···O3 hydrogen bond (Fig. 1) generates an S(5) ring motif (Bernstein et al., 1995) and contributes to this planarity.

In the 3-oxopropanoate moiety [C1–C3/C6/O1/O2/O4], atoms C1, C2, C6, O1 and O4 lie on the same plane with C1 deviating by a maximum of -0.017 (2) Å. Similarly atoms C3, O2, C4, C5, N1 and O3 lie on the same plane with the maximum deviation -0.058 (2) Å for C4. The dihedral angle between these two planes is 70.29 (11) Å. The methoxycarbonylmethyl moiety makes a dihedral angle of 79.73 (10) Å with the hydroxyphenyl ring. The water molecule links with the C₁₃H₁₅NO₆ molecule via an N1—H1N1···O1W hydrogen bond (Fig. 1). All bond lengths and angles show normal values (Allen et al., 1987).

In the crystal packing (Fig. 2), the molecules are stacked down both the [010] and [102] directions forming a two dimensional network parallel to the (-2 0 1) plane via N—H···O, O—H···O hydrogen bonds and weak C—H···O interactions (Table 1). The crystal is further stablized by C—H···π interactions (Table 1); Cg₁ is the centroid of the C8–C13 phenyl ring.

Experimental

The title compound was synthesized via condensation between an equimolar amount of hydroxyphenylglycine methylester (10.0 g, 60 mmol) and methylmalonate potassium salt (9.4 g, 60 mmol) in acetonitrile/water (140:40 ml) at 273 K. The mixture was stirred for 2 h in the presence of dicyclohexylcarbodiimide, which acted as a catalyst and a peptide-coupling agent. The white precipitate formed during the reaction was filtered and washed thoroughly with dichloromethane. The filtrate and the dichloromethane were combined and evaporated. The resulting crude product was partitioned between water and dichloromethane, and the dichloromethane extract was dried over anhydrous magnesium sulfate and evaporated. Colorless needle-shaped single crystals suitable for X-ray structure determination were obtained by slow evaporation of dichloromethane/petroleum ether (5:1 v/v) solution after several days (10.93 g, 65%).