Crystal structure of ethyl (4R)-2-amino-7-hy­droxy-4-phenyl-4H-chromene-3-carboxyl­ate

Joel T Mague; Shaaban K Mohamed; Mehmet Akkurt; Sabry H H Younes; Mustafa R Albayati

doi:10.1107/S2056989015012013

. 2015 Jun 27;71(Pt 7):o519–o520. doi: 10.1107/S2056989015012013

Crystal structure of ethyl (4R)-2-amino-7-hydroxy-4-phenyl-4H-chromene-3-carboxylate

Joel T Mague ^a, Shaaban K Mohamed ^b,^c, Mehmet Akkurt ^d, Sabry H H Younes ^e, Mustafa R Albayati ^f,^*

PMCID: PMC4518989 PMID: 26279941

Abstract

In the title compound, C₁₈H₁₇NO₄, the dihedral angle between the phenyl ring and the fused six-membered ring is 77.65 (4)°. The conformation of the molecule is determined in part by an intramolecular N—H⋯O hydrogen bond between the amino H atom and the carbonyl O atom, forming an S(6) motif. In the crystal, molecules are linked into N—H⋯O hydrogen-bonded inversion dimers which are then connected into chains along [001], forming a two-dimensional network parallel to (100) via O—H⋯O hydrogen bonds. C—H⋯O interactions further contribute to the crystal stability. The ethyl group is disordered over two sets of sites in a 0.801 (5):0.199 (5) ratio.

Keywords: crystal structure, amino chromenes, 4H-chromene, hydrogen bonding

Related literature

For background to the synthesis and biological activity of molecules having a 4H-chromene or 4H-benzochromene residue, see: Kiyani & Ghorbani (2014 ▸); Kale et al. (2013 ▸); Sabry et al. (2011 ▸); Kidwai et al. (2010 ▸); Mungra et al. (2011 ▸); Cingolani et al. (1969 ▸); Wu et al. (2003 ▸); Perrella et al. (1994 ▸); Patil et al. (1993 ▸); Emmadi et al. (2012 ▸); Wang et al. (2003 ▸); Armesto et al. (1989 ▸). graphic file with name e-71-0o519-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₇NO₄
M _r = 311.32
Monoclinic,
a = 31.5071 (7) Å
b = 5.8582 (1) Å
c = 21.2249 (5) Å
β = 130.180 (1)°
V = 2993.11 (11) Å³
Z = 8
Cu Kα radiation
μ = 0.81 mm⁻¹
T = 150 K
0.22 × 0.18 × 0.02 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T _min = 0.91, T _max = 0.98
11241 measured reflections
2891 independent reflections
2348 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.101
S = 1.05
2891 reflections
227 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 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/S2056989015012013/qm2111sup1.cif

e-71-0o519-sup1.cif^{(364.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012013/qm2111Isup2.hkl

e-71-0o519-Isup2.hkl^{(231.5KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015012013/qm2111Isup3.cml

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

. DOI: 10.1107/S2056989015012013/qm2111fig1.tif

The title molecule with labeling scheme and 50% probability ellipsoids. Only one orientation of the disordered ethyl group is shown.

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

b . DOI: 10.1107/S2056989015012013/qm2111fig2.tif

Packing viewed down the b axis. N—H⋯O and O—H⋯O hydrogen bonds are shown, respectively as blue and red dotted lines.

CCDC reference: 1408238

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C11H11AO2ⁱ	0.99	2.58	3.312(3)	131
C6H6O1ⁱⁱ	0.95	2.56	3.4736(17)	163
N1H1BO3	0.88(2)	1.998(19)	2.6840(18)	133.7(16)
N1H1AO2ⁱⁱ	0.93(2)	2.15(2)	3.0710(18)	169.6(17)
O2H2AO3ⁱⁱⁱ	0.90(2)	1.83(2)	2.7331(15)	179(2)

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

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

Besides the various biological properties of 2-Amino-4H-Chromenes, they also act as important synthetic building blocks for various bio-active molecules (Kiyani & Ghorbani, 2014; Kale et al., 2013; Sabry et al., 2011; Kidwai et al., 2010). During the last decade, such compounds had shown interesting pharmacological properties such as antimicrobial and anti-tuberculosis agents (Mungra et al., 2011), anticoagulant (Cingolani et al., 1969), anticancer (Wu et al., 2003), antitumour (Perrella, et al., 1994), cytotoxic and anti-HIV activities (Patil et al., 1993; Emmadi, et al., 2012). Also, chromenes are also structural features of various natural products (Wang et al., 2003) and possess useful photochemical properties (Armesto et al., 1989).

In the title molecule, the dihedral angle between the phenyl ring (C13–C18) and the C2–C7 ring is 77.65 (4)°. A puckering analysis of the heterocyclic ring gave Q = 0.118 (2) Å, θ = 95.1 (8)° and φ = 352.0 (8)°. The conformation of the molecule is determined in part by an intramolecular N1—H1B···O3 hydrogen bond. Pairwise N1—H1A···O2ⁱ (i: 1 - x, -y, 1 - z) hydrogen bonds form dimers which are then connected into chains via O2—H2A···O3ⁱⁱ (ii: x, 1 - y, -1/2 + z) hydrogen bonds (Table 1 and Fig. 2).

S2. Experimental

The title compound was synthesized by the reaction of (E)-ethyl 3-(phenyl)-2-cyanoacrylate (1 mmol, 201 mg) and 1,3-Benzenediol (1 mmol, 110 mg) catalyzed by Et₃N in 10 ml e thanol at the refuxing temperature. After cooling, the solvent was removed under reduced pressure and the residue was washed with cold ethanol and recrystallized from ethanol to afford pure colourless crystals suitable for X-ray diffraction in 92% yeild and M.p 491 K.