Crystal structure of 4-azido­methyl-6-isopropyl-2H-chromen-2-one

M S Krishnamurthy; Noor Shahina Begum; D Shamala; K Shivashankar

doi:10.1107/S2056989015004387

. 2015 Mar 7;71(Pt 4):o227–o228. doi: 10.1107/S2056989015004387

Crystal structure of 4-azidomethyl-6-isopropyl-2H-chromen-2-one

M S Krishnamurthy ^a, Noor Shahina Begum ^a,^*, D Shamala ^a, K Shivashankar ^a

PMCID: PMC4438796 PMID: 26029427

Abstract

In the title molecule, C₁₃H₁₃N₃O₂, the benzopyran ring system is essentially planar, with a maximum deviation of 0.017 (1) Å. In the crystal, weak C—H⋯O hydrogen bonds link molecules into ladders along [010]. In addition, π–π interactions between inversion-related molecules, with centroid–centroid distances in the range 3.679 (2)–3.876 (2) Å, complete a two-dimensional network parallel to (001).

Keywords: crystal structure, 2H-chromen-2-one, π–π interactions, hydrogen bonding

Related literature

For therapeutic properties of coumarin derivatives, see: Lacy & O’Kennedy (2004 ▸); Mustafa et al. (2011 ▸). For the biological activity of 2H-chromen-2-ones, see: Naik et al. (2012 ▸). For applications of organic azides, see: Kusanur et al. (2010 ▸). For structural features of coumarins, see: Moorthy et al. (2003 ▸). For related structures, see: Gowda et al. (2010 ▸); Fun et al. (2011 ▸); Nagarajaiah et al. (2013 ▸). graphic file with name e-71-0o227-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₃N₃O₂
M _r = 243.26
Triclinic,
a = 6.895 (2) Å
b = 7.862 (2) Å
c = 11.592 (4) Å
α = 72.218 (6)°
β = 79.662 (5)°
γ = 82.430 (6)°
V = 586.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▸) T _min = 0.983, T _max = 0.985
3059 measured reflections
2026 independent reflections
1644 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.150
S = 1.07
2026 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 1998 ▸); cell refinement: SAINT (Bruker, 1998 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015004387/lh5754sup1.cif

e-71-0o227-sup1.cif^{(141KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015004387/lh5754Isup2.hkl

e-71-0o227-Isup2.hkl^{(111.5KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015004387/lh5754Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015004387/lh5754fig1.tif

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015004387/lh5754fig2.tif

Part of the crystal structure with weak hydrogen bonds shown as dashed lines. Only H atoms involved in hydrogen bonds are shown.

CCDC reference: 1051846

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C5H5O2ⁱ	0.95	2.56	3.498(2)	168
C13H13CO2ⁱⁱ	0.98	2.55	3.524(3)	172

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

Acknowledgments

MSK thanks the UGC for a UGC–BSR meritorious fellowship. KSS and DS are thankful to the Council of Scientific and Industrial Research, New Delhi, India, for financial assistance [grant No. 02 (0172)/13/EMR-II].

supplementary crystallographic information

S1. Comment

Coumarins are of great interest due to their biological properties (Lacy & Kennedy 2004). In particular, their physiological, bacteriostatic and anti- tumour activity (Mustafa et al., 2011) makes these compounds attractive for further backbone derivatization and screening for their therapeutic properties. In view of their extensive natural occurrence and biocompatibility, 2H-chromen-2-ones have been found to exhibit variety of biological activities (Naik et al., 2012). In addition, organic azides are an important class of 1,3-dipoles, which have been recently recognized as crucial functional groups in click chemistry (Kusanur et al., 2010). In view of the above, the title compound was isolated and the crystal structure is presented herein.

In the title compound (Fig. 1), the benzopyran ring system is essentially planar with a maximum deviation of 0.017 (1)Å for atom C10. Atom N1 of the azido group deviates by 0.168 (2)Å from the mean-plane of the benzopyran ring system while atoms N2 and N3, deviate by -0.489 (1) and -1.013 (2)Å, respectively from the opposite face of this ring system. In the crystal, weak C—H···O hydrogen bonds link molecules into ladders along [010] (Table 1, Fig.2). In addition, π–π interactions between inversion related molecules, with centroid–centroid distances in the range 3.679 (2)–3.876 (2)Å, complete a two-dimensional network parallel to (001).

S2. Experimental

4-Bromomethyl-6-isopropylcoumarin (0.01 mol) was taken in acetone (20 ml) in a round bottomed flask. To this, sodium azide (0.012 mol, 0.78 g) in 5 ml of water was added drop wise with stirring for 3 hrs (reaction was monitored by TLC). The reaction mixture was poured into ice cold water, separated solid was filtered and recrystallized from ethyl acetate. (Yield 85%; colorless solid; mp 360 K).