Crystal structure of 3,4-dimethyl 2-(tert-butyl­amino)-5-[2-oxo-4-(thio­morpholin-4-yl)-2H-chromen-3-yl]furan-3,4-di­carboxyl­ate ethyl acetate hemisolvate

Tetsuji Moriguchi; Venkataprasad Jalli; Suvratha Krishnamurthy; Akihiko Tsuge; Kenji Yoza

doi:10.1107/S2056989015021970

. 2015 Nov 28;71(Pt 12):o1003–o1004. doi: 10.1107/S2056989015021970

Crystal structure of 3,4-dimethyl 2-(tert-butylamino)-5-[2-oxo-4-(thiomorpholin-4-yl)-2H-chromen-3-yl]furan-3,4-dicarboxylate ethyl acetate hemisolvate

Tetsuji Moriguchi ^a,^*, Venkataprasad Jalli ^a, Suvratha Krishnamurthy ^a, Akihiko Tsuge ^a, Kenji Yoza ^b

PMCID: PMC4719946 PMID: 26870465

Abstract

In the title hemisolvate, C₂₅H₂₈N₂O₇S·0.5C₄H₈O₂, the thiomorpholine ring adopts a chair conformation, with the exocyclic N—C bond in an equatorial orientation. The dihedral angle between the coumarin ring system (r.m.s. deviation = 0.044 Å) and the furan ring is 64.84 (6)°. An intramolecular N—H⋯O hydrogen bond closes an S(6) ring. The ethyl acetate solvent molecule is disordered about a crystallographic inversion centre. In the crystal, the components are linked by C—H⋯O and C—H⋯S hydrogen bonds, generating a three-dimensional network.

Keywords: crystal structure, coumarins, thiomorpholine ring, hydrogen bonding

Related literature

For the syntheses and properties of coumarins, see: Arango et al. (2010 ▸); Chodankar & Seshadri (1985 ▸); Khan & Kulkarni (1999 ▸); Kitamura et al. (2005 ▸); Luo et al. (2012 ▸); Sawa et al. (2006 ▸); Schiedel et al. (2001 ▸); Udaya Kumari et al. (2000 ▸); Zen et al. (2014 ▸).

Experimental

Crystal data

C₂₅H₂₈N₂O₇S·0.5C₄H₈O₂
M _r = 544.61
Monoclinic,
a = 14.3733 (17) Å
b = 16.1159 (19) Å
c = 11.7019 (14) Å
β = 95.007 (1)°
V = 2700.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 90 K
0.50 × 0.40 × 0.25 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.853, T _max = 0.958
25410 measured reflections
4757 independent reflections
4316 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.086
S = 1.02
4757 reflections
375 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015021970/hb7531sup1.cif

e-71-o1003-sup1.cif^{(27.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021970/hb7531Isup2.hkl

e-71-o1003-Isup2.hkl^{(233KB, hkl)}

Click here for additional data file.^{(11KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015021970/hb7531Isup3.cml

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

. DOI: 10.1107/S2056989015021970/hb7531fig1.tif

Molecular configuration and atom-numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity.

Click here for additional data file.^{(1.9MB, tif)}

. DOI: 10.1107/S2056989015021970/hb7531fig2.tif

Crystal packing diagram of the title compound.

Click here for additional data file.^{(15.3KB, tif)}

. DOI: 10.1107/S2056989015021970/hb7531fig3.tif

Chemical scheme of title compound with solvent molecule. In the cystal system the main molecule and solvent molecule was found in 1:0.5 ratio.

Click here for additional data file.^{(16.2KB, tif)}

. DOI: 10.1107/S2056989015021970/hb7531fig4.tif

Synthesis of title compound (I).

CCDC reference: 1432824

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
N2—H13⋯O4	0.86	2.25	2.8255 (17)	125
C3—H2⋯O6ⁱ	0.93	2.41	3.325 (2)	167
C12—H9⋯O4ⁱⁱ	0.97	2.44	3.1531 (18)	130
C12—H10⋯O1S ⁱⁱⁱ	0.97	2.48	3.208 (5)	132
C19—H15⋯O3	0.96	2.42	3.0090 (19)	119
C23—H23⋯S1^iv	0.96	2.78	3.5639 (17)	139
C25—H26⋯S1^v	0.96	2.83	3.7406 (18)	159

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

Acknowledgments

We are grateful to the Center for Instrumental Analysis, Kyushu Institute of Technology (KITCIA) for the X-ray analysis. This research was supported financially by JSPS KAKENH grant No. 15 K05611.

supplementary crystallographic information

S1. Structural commentary

Coumarins analogs having furan heterocycle have gained significant importance because of their properties as anti-leishmania panamensis, dyes and fluorescent sensors. For the activity related reports of furyl coumarins, see: Arango et al. (2010); Zen et al. (2014); Schiedel et al. (2001); Kitamura et al. (2005). Natural furyl coumarin derivatives extracted from plants such as microminutin, micromelin, psoralen, 8-methoxypsoralen have important properties in medicinal chemistry and bio photochemistry. For the activity related reports of natural furyl coumarins, see: Luo et al. (2012). It was well documented that by introducing a heteroaromatic substituent at 3-position the absorption and emission maxima of coumarin scaffold can be improved because of extended π conjugation and consequently their optoelectronic properties can be improved. Due to their versatile properties a variety of 3-heteroaryl coumarin derivatives have been synthesized and tested for their optoelectronic properties. For the optoelectronic properties of coumarin derivatives, see: Sawa et al. (2006). For the synthesis related reports of 3-furyl coumarin derivatives, see: Chodankar et al. (1985); Khan & Kulkarni (1999); Udaya Kumari et al. (2000). Thus, the elucidation of the crystal structures of coumarin derivatives has attracted much attention. Here,we report the crystal structure of the title compound, (I).

S2. Synthesis and crystallization,

A solution of 4-thiomorpholino-3-formyl coumarin (1 mmol), dmethyl acetylenedicarboxylate (1 mmol), t-butyl isocyanide (1 mmol) were refluxed at 80°C for 3h. The volatiles were removed under reduced pressure. The crude reaction mixture was subjected to column chromatography using EtOAc/Hexane mobile phase. The title compound was isolated as yellow color solid with 80% yield. Yellow prisms were obtained by vapour diffusion method at room temperature, i.e., hexane vapour was allowed to diffuse into an EtOAc solution of 4-thiomorpholino-3-(2-N-t-butylamino-3,4-dimethylcarboxylate-5-furyl) 2H-1-benzopyran-2-one at room temperature.

mp 107-109 °C; IR; ν_max(KBr) 3288, 1732, 1728, 1667, 1658, 1618, 1418, 1240, 1041 cm^-1; δ_H (500 MHz CDCl₃) 7.69 (1 H, d), 7.52 (1 H, t), 7.28-7.33 (2 H, dd), 7.05 (1 H, s), 3.78 (3 H, s), 3.75 (3 H, s), 3.39-3.48 (4 H, m), 2.77-2.81 (4 H, m), 1.44 (9 H, s); δ_C (125 MHz, CDCl₃) 165.6, 163.9, 163.0, 161.2, 160.6, 153.4, 138.2, 132.4, 125.1, 123.7, 118.7, 118.1, 117.7, 103.6, 87.8, 53.2, 52.7, 51.8, 51.3, 28.0; LCMS: MH⁺, 501.