(S,Z)-3-Phenyl-2-[(1,1,1-tri­chloro-7-meth­oxy-2,7-dioxohept-3-en-4-yl)amino]­propanoic acid monohydrate

Alex Fabiani Claro Flores; Juliano Rosa de Menezes Vicenti; Lucas Pizzuti; Patrick Teixeira Campos

doi:10.1107/S1600536814000154

. 2014 Jan 18;70(Pt 2):o169–o170. doi: 10.1107/S1600536814000154

(S,Z)-3-Phenyl-2-[(1,1,1-trichloro-7-methoxy-2,7-dioxohept-3-en-4-yl)amino]propanoic acid monohydrate

Alex Fabiani Claro Flores ^a,^*, Juliano Rosa de Menezes Vicenti ^a, Lucas Pizzuti ^b, Patrick Teixeira Campos ^c

PMCID: PMC3998325 PMID: 24764886

Abstract

In the title compound, C₁₇H₁₈Cl₃NO₅·H₂O, intramolecular N—H⋯O and C—H⋯Cl hydrogen bonds form S(6) and S(5) ring motifs, respectively. The chiral organic molecule is connected to the solvent water molecule by a short O—H⋯O hydrogen bond. In the crystal, a weak C—H⋯Cl interaction connects the organic molecules along [100] while the water molecules act as bridges between the organic molecules in both the [100] and [010] directions, generating layers parallel to the ab plane.

Related literature

For the synthesis of the title compound and a similar crystal structure, see: Flores et al. (2008 ▶). For information about levulinic acid and the biological properties of its derivatives, see: Flores et al. (2013 ▶); Hachuła et al. (2013 ▶); Lo & Ng (2008 ▶). For short intermolecular hydrogen-bond interactions, see: Pojarová et al. (2010 ▶). For intramolecular hydrogen-bonding systems, see: da Costa et al. (2013 ▶). graphic file with name e-70-0o169-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₈Cl₃NO₅·H₂O
M _r = 440.69
Triclinic,
a = 5.6684 (16) Å
b = 8.601 (3) Å
c = 10.336 (3) Å
α = 87.720 (19)°
β = 85.696 (17)°
γ = 85.649 (17)°
V = 500.8 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 296 K
0.98 × 0.30 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: Gaussian (XPREP; Bruker, 2006 ▶) T _min = 0.881, T _max = 1
13424 measured reflections
6020 independent reflections
4784 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.105
S = 1.04
6020 reflections
256 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack parameter determined using 1984 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▶)
Absolute structure parameter: 0.04 (2)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814000154/pk2509sup1.cif

e-70-0o169-sup1.cif^{(414.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814000154/pk2509Isup2.hkl

e-70-0o169-Isup2.hkl^{(329.9KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814000154/pk2509Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=979612

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Cl1ⁱ	0.97	2.94	3.774 (3)	145
O33—H33B⋯O91ⁱⁱ	0.87 (6)	1.89 (6)	2.766 (4)	177 (5)
N41—H41⋯O21	0.83 (5)	2.05 (6)	2.672 (3)	131 (5)
O33—H33A⋯O21ⁱⁱⁱ	0.76 (6)	2.06 (6)	2.815 (3)	171 (6)
O92—H92⋯O33	0.89 (5)	1.66 (5)	2.542 (4)	175 (5)
C3—H3⋯Cl1	0.93	2.55	3.031 (3)	112

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

Acknowledgments

The authors are grateful for financial support from the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Universal grant 6577818477962764–01), the Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul (FAPERGS, PqG grant 1016236) and the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES-PROEX).

supplementary crystallographic information

1. Comment

Dielectrophiles derived from levulinic acid (Hachuła et al., 2013; Lo & Ng, 2008) belong to an important class of organic synthetic intermediates for the synthesis of a variety of heterocyclic compounds. Such precursors are used to produce pyrrolidinones, pyrrolones, pyrazoles and pyrimidines with very interesting biological activities (Flores et al., 2008; Flores et al., 2013). As a part of our studies, we report in this paper the crystal structure of (S,Z)-3-phenyl-2-(1,1,1-trichloro-7–2,7-dioxo-3-hepten- 4-ylamine)propanoic acid, obtained from the reaction between methyl 7,7,7-trichloro-4-methoxy-6-oxo-3-heptenoate and L-phenylalanine.

In the crystal structure of the title compound, the asymmetric unit is composed of the whole chiral organic molecule, C₁₇H₁₈Cl₃NO₅, connected to a water molecule (Fig.1). This connection consists of a short intermolecular hydrogen bond interaction involving the hydrogen atom of the carboxylic acid fragment [O92—H92···O33, 2.542 (4) Å; Pojarová et al., 2010]. Additionally, S(6) and S(5) ring motifs are formed by two distinct intramolecular hydrogen bonding systems, N41—H41···O21 [2.672 (3) Å] and C3—H3···Cl1 [3.031 (3) Å], respectively, thereby stabilizing the structure (da Costa et al., 2013).

There is also a weak C6—H6A···Cl1ⁱ intermolecular interaction [3.774 (3) Å] connecting organic molecules along the [100] crystallographic direction. The water molecules act as a bridging element in the crystal structure by expanding its dimensionality in both [100] and [010] crystallographic directions. The intermolecular hydrogen bond interactions generate bidimensional layers parallel to the ab plane. Each atom of the water molecule is connected to different groups on adjacent organic molecules: carboxylic acid [O92—H92···O33, 2.542 (4) Å and O33—H33B···O91ⁱⁱ, 2.766 (4) Å] and ketone [O33—H33A···O21ⁱⁱⁱ, 2.815 (3) Å]. Symmetry codes: (i) x–1, y, z; (ii) x + 1, y, z; (iii) x, y + 1, z. A super cell central projection of the crystal structure can be viewed in Fig. 2, which depicts a crystal packing diagram as viewed along the crystallographic a axis.

2. Experimental

To a stirred solution of methyl 7,7,7-trichloro-4-methoxy-6-oxo-3-heptenoate (5 mmol, 1.52 g) and L-phenylalanine (5.5 mmol, 0.91 g), at 25 °C, was added a solution of 1 mol·L^-1 NaOH. There was an immediate formation of a yellow precipitate and the mixture was further stirred for 30 minutes. A solution of 50% HCl was added until the pH ≈ 1, when there was complete precipitation of the yellow solid. The solid was extracted with ethyl acetate, and this solution was dried over anhydrous MgSO₄. The ethyl acetate was removed on a rotary evaporator to give the product as a yellow solid. Yield: 79%. m. p. 120 – 123 °C. ¹H NMR (400 MHz, DMSO-D₆, TMS): δ 2.17 (m, 2H, CH₂), 2.44 (m, 2H, CH₂), 3.06 (dd, 1H, ³J=9.1 Hz, ²J=14 Hz, CH₂Ph), 3.37 (dd, 1H, ³J=9.1 Hz, ²J=14 Hz, CH₂Ph), 3.66 (s, 3H, OMe), 4.53 (m, 1H, CH_chiral), 5.60 (s, 1H, =CH), 7.22–7.33 (m, 5H, Ph), 10.9 (d, 1H, ³J = 10 Hz, NH) p.p.m.; ¹³C NMR (100 MHz, DMSO-D₆): δ 26.8, 31.5, 39.9, 52.2, 58.1, 86.0, 96.9, 127.5, 128.9, 129.5, 135.4, 169.9, 172.0, 173.2, 181.2 p.p.m.. Crystals were grown from a methanol solution, which was slowly evaporated at room temperature.