Crystal structure of 4-azido­methyl-6-tert-butyl-2H-chromen-2-one

Nasseem El-Khatatneh; Chandra; D Shamala; K Shivashankar; Mukhokosi Emma Panzi; M Mahendra

doi:10.1107/S205698901500290X

. 2015 Mar 4;71(Pt 4):o218–o219. doi: 10.1107/S205698901500290X

Crystal structure of 4-azidomethyl-6-tert-butyl-2H-chromen-2-one

Nasseem El-Khatatneh ^a, Chandra ^a, D Shamala ^b, K Shivashankar ^b, Mukhokosi Emma Panzi ^a, M Mahendra ^a,^*

PMCID: PMC4438804 PMID: 26029422

Abstract

In the title compound, C₁₄H₁₅N₃O₂, one of the methyl C atoms of the tert-butyl group lies almost in the plane of the chromene ring system [deviation = −0.097 (2) Å], one lies above and one lies below [deviations = 1.460 (3) and 1.006 (3) Å, respectively]. The C—C—N—N torsion angle is 142.33 (17)°. In the crystal, moelcules are linked by weak C—H⋯O hydrogen bonds to generate C(6) chains propagating in the [010] direction.

Keywords: crystal structure, chromene, coumarin, hydrogen bonding

Related literature

For background to the biological properties of coumarins, see: Basanagouda et al. (2009 ▸); Liu et al. (2008 ▸); Mustafa et al. (2011 ▸); Ronad et al. (2008 ▸); Tian et al. (2000 ▸); Puttaraju et al. (2013 ▸). For a related structure, see: Chandra et al. (2014 ▸).

Experimental

Crystal data

C₁₄H₁₅N₃O₂
M _r = 257.29
Monoclinic,
a = 10.6816 (7) Å
b = 11.1416 (8) Å
c = 11.5409 (8) Å
β = 100.674 (4)°
V = 1349.72 (16) Å³
Z = 4
Cu Kα radiation
μ = 0.71 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker X8 Proteum diffractometer
5911 measured reflections
2165 independent reflections
1949 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.132
S = 1.04
2165 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 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: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901500290X/hb7363sup1.cif

e-71-0o218-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500290X/hb7363Isup2.hkl

e-71-0o218-Isup2.hkl^{(106.5KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supporting information file. DOI: 10.1107/S205698901500290X/hb7363Isup3.cml

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

. DOI: 10.1107/S205698901500290X/hb7363fig1.tif

Perspective diagram of the molecule with 50% probability displacement ellipsoids.

Click here for additional data file.^{(1.3MB, tif)}

b . DOI: 10.1107/S205698901500290X/hb7363fig2.tif

Packing diagram of the molecule viewed parallel to the b axis.

CCDC reference: 1048730

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C14H14AO2ⁱ	0.97	2.55	3.311(2)	135

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Symmetry code: (i) Inline graphic .

Acknowledgments

MM would like to thank UGC, New Delhi, Government of India, for the award of a project under the head F. No. 41–920/2012(SR) (dated: 25-07-2012). In addition, SD is 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

Coumarin and its substituents are of well known heterocyclic compounds, which have a variety of biologically activities; such as anti-tumour (Mustafa et al., 2011), anti-bacterial (Basanagouda et al., 2009; Liu et al., 2008) and analgesic (Ronad et al., 2008) agents. In addition, coumarin derivatives have been found to be very useful in many applications; such as nonlinear optical materials and as intermediates for the drug synthesis (Tian et al., 2000). In our previous work (Puttaraju et al., 2013), we have reported the synthesis, in vitro antimicrobial and anticancer activities of new coumarin derivatives substituted dihydrobenzo[4,5]imidazo[1,2-a]pyrimidin-4-ones. In continuation to this, we have synthesized the title compound to study its molecular and crystal structure.

In the molecular structure of the title compound (Fig. 1), the chromene moiety is almost planar, with the maximum deviation from the mean plane being 0.093 (2) Å for atom C10, respectively. The azidomethyl group is in anti-periplanar conformation with respect to the chromene moiety, as indicated by the torsion angle value of 172.35 (14)° (C3–C4–C14–N1). The bond lengths and angles are within normal ranges and are comparable to related structure (Chandra et al., 2014). The crystal structure features C—H···O hydrogen bonds, which link the molecules into [010] chains, as shown in Fig. 2.

S2. Experimental

6-tert-Butyl-4-bromomethylcoumarins (0.001 mmol. 0.5 g) were taken in 15 ml acetone in a round bottomed flask and stirred. To this, sodium azide (0.002 mol, 0.13 g) in 5 ml of water was added drop wise with stirring, which was continued for 3 hrs (reaction was monitored by TLC). The reaction mixture was poured in to ice cold water, separated solid was filtered and recrystallized from ethyl alcohol to get pale yelllow blocks of the title compound.