Ethyl 3-oxo-3H-benzo[f]chromene-2-carboxyl­ate

Vahini, M.V.; Devarajegowda, H.C.; Mahadevan, K.M.; Meenakshi, T.G.; Arunkashi, H.K.

doi:10.1107/S1600536810037840

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2658

doi:10.1107/S1600536810037840

Open

access

Ethyl 3-oxo-3H-benzo[f]chromene-2-carboxylate

M. Vindu Vahini,^a H. C. Devarajegowda,^b ^* K. M. Mahadevan,^c T. G. Meenakshi ^d and H. K. Arunkashi ^b

^aDepartment of Physics, Sri D Devaraja Urs Govt. First Grade College, Hunsur 571 105, Mysore District, Karnataka, India, ^bDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India, ^cDepartment of PG Studies in Pharmaceutical Chemistry, Kuvempu University Kadur P. G. Center, Kadur 577 548, Karnataka, India, and ^dDepartment of Physics, Y. Y. D. Govt. First Grade College, Belur 573 115, Hassan, Karnataka, India
^*Correspondence e-mail: devarajegowda@yahoo.com

(Received 6 September 2010; accepted 21 September 2010; online 30 September 2010)

In the title compound, C₁₆H₁₂O₄, the chromene ring system is almost planar [maximum deviation = 0.026 (1) Å] and makes dihedral angles of 1.24 (9) and 26.5 (2)° with the fused benzene ring and the plane of the ethyl carboxylate group, respectively.

Related literature

For general background to chromenes, see: Kendall et al. (1961 ); Rau & Brack (1963 ); Jones et al. (1985 ); Gikas et al. (2003 ); Miyata & Nalwa, (1997 ); Shibata (1994 ). For related structures, see: Lakshmi et al. (2006 ); Jiao et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₂O₄
M_r = 268.26
Monoclinic, P 2₁ /n
a = 14.6716 (11) Å
b = 4.5190 (5) Å
c = 19.3874 (18) Å
β = 90.218 (7)°
V = 1285.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.22 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: ψ scan (SADABS; Sheldrick, 2004 ) T_min = 0.981, T_max = 0.987
13075 measured reflections
2276 independent reflections
997 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.208
S = 1.04
2276 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037840/wn2410sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037840/wn2410Isup2.hkl

checkCIF report

Comment top

Chromenes are involved in the structures of molecules of biologically active compounds. Several chromene derivatives have been patented for a variety of industrial applications (Kendall et al., 1961; Rau & Brack,1963).

Chromenes also play a vital role in electrophotographic, electroluminescent devices and laser dyes. Several 3-substituted 7-hydroxycoumarins rank among the most efficient photostable laser dyes, emitting in the blue green region of the visible spectrum. The lasing range covered by chromene dyes is appreciably extended when the 3-substituent is a heterocyclic unit (Jones et al., 1985; Gikas et al., 2003). Benzo-annulated chromene derivativesare widely used in organic light-emitting devices and are used as electron-transporting emitters (Miyata & Nalwa et al., 1997; Shibata, 1994).

In the title compound (Fig. 1) the chromene ring system is almost planar [maximum deviation = 0.026 (1) Å] and makes dihedral angles of 1.24 (9)° and 26.5 (2)% with the fused benzene ring and the plane of the ethyl carboxylate group, respectively. The bond lengths and bond angles are in good agreement with those in related structures (Lakshmi et al., 2006; Jiao et al., 2009). The packing of the molecules, when viewed along b, is shown in Fig. 2.

Related literature top

For general background to chromenes, see: Kendall et al. (1961); Rau & Brack (1963); Jones et al. (1985); Gikas et al. (2003); Miyata & Nalwa, (1997); Shibata (1994). For related structures, see: Lakshmi et al. (2006); Jiao et al. (2009).

Experimental top

A mixture of 2-hydroxy-1-naphthaldehyde (2.9 mmol), an equivalent amount of diethyl malonate (2.9 mmol), and a catalytic amount of piperidine in ethanol (30 ml) was refluxed for 30 minutes on a water bath. After the reaction was complete, the reaction mixture was cooled to room temperature and poured into crushed ice with stirring. The precipitate obtained was then filtered, washed with water, dried and recrystallized using ethanol to yield the pure title compound as a white-yellow crystalline solid. Yield 90%; m.p. 388 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. Packing of the molecules when viewed along b.

Ethyl 3-oxo-3H-benzo[f]chromene-2-carboxylate top

Crystal data top

C₁₆H₁₂O₄	F(000) = 560
M_r = 268.26	D_x = 1.386 Mg m⁻³
Monoclinic, P2₁/n	Melting point < 388 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 14.6716 (11) Å	Cell parameters from 2276 reflections
b = 4.5190 (5) Å	θ = 2.8–25.0°
c = 19.3874 (18) Å	µ = 0.10 mm⁻¹
β = 90.218 (7)°	T = 293 K
V = 1285.4 (2) Å³	Plate, colourless
Z = 4	0.22 × 0.15 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2276 independent reflections
Radiation source: fine-focus sealed tube	997 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: ψ scan (SADABS; Sheldrick, 2004)	h = −17→17
T_min = 0.981, T_max = 0.987	k = −5→5
13075 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.075	H-atom parameters constrained
wR(F²) = 0.208	w = 1/[σ²(F_o²) + (0.0891P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2276 reflections	Δρ_max = 0.17 e Å⁻³
182 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (4)

Crystal data top

C₁₆H₁₂O₄	V = 1285.4 (2) Å³
M_r = 268.26	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.6716 (11) Å	µ = 0.10 mm⁻¹
b = 4.5190 (5) Å	T = 293 K
c = 19.3874 (18) Å	0.22 × 0.15 × 0.12 mm
β = 90.218 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2276 independent reflections
Absorption correction: ψ scan (SADABS; Sheldrick, 2004)	997 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.987	R_int = 0.088
13075 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.208	H-atom parameters constrained
S = 1.04	Δρ_max = 0.17 e Å⁻³
2276 reflections	Δρ_min = −0.16 e Å⁻³
182 parameters

Special details top

Experimental. ¹H NMR (400 MHz, CDCl₃) δ(p.p.m.): 1.4 (s, 3H, CH₃), 4.4 (q, 2H, H2), 7.4 (m, 6H, ArH), 9.2 (s, 1H, CH): ¹³C NMR (300 MHz, CDCl₃) δ(p.p.m.): 163 (C=O ester), 160 (C=O pyrone), 150.4, 149.7, 148.7, 130.6, 126.6, 124.2, 124.0, 121.2, 121, 120, 114.5, 115, 58.8, 26: IR (KBr) ν(cm^-1): 1765 (s) (C=O), 1750 (s) (C=O ester): MS (m/z): 269 (M+1).

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.37862 (18)	−0.4741 (7)	−0.03118 (17)	0.0587 (9)
O2	0.19329 (19)	−0.8301 (8)	−0.17429 (17)	0.0700 (10)
O3	0.0829 (2)	−0.7805 (8)	−0.09664 (17)	0.0802 (12)
O4	0.3625 (2)	−0.8050 (8)	−0.11371 (17)	0.0777 (11)
C1	0.3450 (3)	−0.2819 (10)	0.0168 (2)	0.0518 (12)
C2	0.4098 (3)	−0.1524 (12)	0.0605 (3)	0.0657 (14)
H2	0.4714	−0.1975	0.0560	0.079*
C3	0.3813 (3)	0.0397 (11)	0.1094 (3)	0.0641 (14)
H3	0.4241	0.1276	0.1383	0.077*
C4	0.2879 (3)	0.1105 (10)	0.1176 (2)	0.0535 (13)
C5	0.2597 (4)	0.3160 (11)	0.1686 (2)	0.0671 (15)
H5	0.3025	0.4041	0.1975	0.081*
C6	0.1708 (4)	0.3826 (12)	0.1749 (3)	0.0731 (15)
H6	0.1527	0.5166	0.2086	0.088*
C7	0.1050 (4)	0.2543 (12)	0.1319 (3)	0.0765 (16)
H7	0.0439	0.3042	0.1367	0.092*
C8	0.1309 (3)	0.0572 (11)	0.0833 (3)	0.0634 (14)
H8	0.0868	−0.0285	0.0551	0.076*
C9	0.2229 (3)	−0.0214 (9)	0.0743 (2)	0.0467 (11)
C10	0.2530 (3)	−0.2264 (9)	0.0221 (2)	0.0444 (11)
C11	0.1960 (3)	−0.3847 (10)	−0.0243 (2)	0.0503 (12)
H11	0.1334	−0.3554	−0.0213	0.060*
C12	0.2266 (3)	−0.5729 (10)	−0.0719 (2)	0.0497 (12)
C13	0.3241 (3)	−0.6306 (12)	−0.0766 (2)	0.0545 (13)
C14	0.1601 (3)	−0.7379 (9)	−0.1150 (2)	0.0533 (12)
C15	0.1339 (3)	−1.0111 (12)	−0.2181 (3)	0.0715 (15)
H15A	0.0993	−1.1455	−0.1892	0.086*
H15B	0.1711	−1.1291	−0.2488	0.086*
C16	0.0699 (4)	−0.8298 (13)	−0.2596 (3)	0.0918 (18)
H16A	0.0327	−0.9573	−0.2876	0.138*
H16B	0.1038	−0.6984	−0.2887	0.138*
H16C	0.0317	−0.7164	−0.2294	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0418 (18)	0.068 (2)	0.066 (2)	0.0077 (16)	0.0000 (17)	−0.0002 (18)
O2	0.062 (2)	0.089 (3)	0.059 (2)	−0.0067 (18)	0.0089 (18)	−0.017 (2)
O3	0.046 (2)	0.119 (3)	0.075 (2)	−0.0087 (19)	0.0054 (18)	−0.028 (2)
O4	0.064 (2)	0.097 (3)	0.072 (2)	0.0201 (19)	0.0008 (19)	−0.021 (2)
C1	0.045 (3)	0.057 (3)	0.054 (3)	0.008 (2)	−0.002 (2)	0.005 (3)
C2	0.043 (3)	0.078 (4)	0.076 (4)	0.001 (3)	−0.010 (3)	0.009 (3)
C3	0.054 (3)	0.065 (4)	0.073 (4)	−0.009 (3)	−0.020 (3)	0.000 (3)
C4	0.064 (3)	0.054 (3)	0.043 (3)	−0.005 (2)	−0.005 (2)	0.013 (2)
C5	0.091 (4)	0.064 (4)	0.046 (3)	−0.011 (3)	−0.017 (3)	0.008 (3)
C6	0.092 (4)	0.072 (4)	0.056 (3)	0.005 (3)	0.008 (3)	−0.015 (3)
C7	0.082 (4)	0.089 (4)	0.059 (3)	0.010 (3)	0.020 (3)	−0.016 (3)
C8	0.058 (3)	0.067 (4)	0.065 (3)	−0.002 (3)	−0.004 (3)	0.006 (3)
C9	0.045 (3)	0.048 (3)	0.047 (3)	−0.001 (2)	0.003 (2)	0.012 (2)
C10	0.044 (3)	0.043 (3)	0.045 (3)	−0.001 (2)	0.001 (2)	0.009 (2)
C11	0.042 (3)	0.059 (3)	0.050 (3)	0.007 (2)	0.003 (2)	0.015 (3)
C12	0.043 (3)	0.057 (3)	0.049 (3)	0.005 (2)	−0.004 (2)	0.012 (3)
C13	0.049 (3)	0.065 (4)	0.050 (3)	0.009 (3)	−0.002 (3)	0.011 (3)
C14	0.055 (3)	0.052 (3)	0.052 (3)	0.005 (3)	0.001 (3)	0.004 (2)
C15	0.074 (3)	0.073 (4)	0.068 (3)	0.004 (3)	−0.008 (3)	−0.020 (3)
C16	0.110 (5)	0.090 (5)	0.075 (4)	0.006 (3)	−0.025 (3)	−0.005 (3)

Geometric parameters (Å, º) top

O1—C1	1.366 (5)	C6—H6	0.9300
O1—C13	1.381 (5)	C7—C8	1.353 (6)
O2—C14	1.318 (5)	C7—H7	0.9300
O2—C15	1.464 (5)	C8—C9	1.408 (6)
O3—C14	1.204 (5)	C8—H8	0.9300
O4—C13	1.208 (5)	C9—C10	1.443 (6)
C1—C10	1.376 (5)	C10—C11	1.420 (6)
C1—C2	1.400 (6)	C11—C12	1.333 (6)
C2—C3	1.352 (6)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.458 (6)
C3—C4	1.417 (6)	C12—C14	1.483 (6)
C3—H3	0.9300	C15—C16	1.481 (6)
C4—C9	1.400 (6)	C15—H15A	0.9700
C4—C5	1.419 (6)	C15—H15B	0.9700
C5—C6	1.345 (7)	C16—H16A	0.9600
C5—H5	0.9300	C16—H16B	0.9600
C6—C7	1.399 (7)	C16—H16C	0.9600

C1—O1—C13	123.3 (3)	C8—C9—C10	123.0 (4)
C14—O2—C15	117.5 (4)	C1—C10—C11	115.9 (4)
O1—C1—C10	121.5 (4)	C1—C10—C9	118.1 (4)
O1—C1—C2	115.6 (4)	C11—C10—C9	125.9 (4)
C10—C1—C2	122.9 (5)	C12—C11—C10	124.0 (4)
C3—C2—C1	118.7 (5)	C12—C11—H11	118.0
C3—C2—H2	120.6	C10—C11—H11	118.0
C1—C2—H2	120.6	C11—C12—C13	119.4 (4)
C2—C3—C4	121.7 (5)	C11—C12—C14	119.2 (4)
C2—C3—H3	119.1	C13—C12—C14	121.2 (5)
C4—C3—H3	119.1	O4—C13—O1	116.3 (4)
C9—C4—C3	119.5 (5)	O4—C13—C12	127.9 (5)
C9—C4—C5	119.8 (4)	O1—C13—C12	115.8 (4)
C3—C4—C5	120.7 (5)	O3—C14—O2	123.9 (4)
C6—C5—C4	119.7 (5)	O3—C14—C12	122.1 (4)
C6—C5—H5	120.2	O2—C14—C12	114.0 (4)
C4—C5—H5	120.2	O2—C15—C16	112.4 (4)
C5—C6—C7	121.3 (5)	O2—C15—H15A	109.1
C5—C6—H6	119.3	C16—C15—H15A	109.1
C7—C6—H6	119.3	O2—C15—H15B	109.1
C8—C7—C6	119.6 (5)	C16—C15—H15B	109.1
C8—C7—H7	120.2	H15A—C15—H15B	107.9
C6—C7—H7	120.2	C15—C16—H16A	109.5
C7—C8—C9	121.6 (5)	C15—C16—H16B	109.5
C7—C8—H8	119.2	H16A—C16—H16B	109.5
C9—C8—H8	119.2	C15—C16—H16C	109.5
C4—C9—C8	118.0 (4)	H16A—C16—H16C	109.5
C4—C9—C10	119.0 (4)	H16B—C16—H16C	109.5

C13—O1—C1—C10	−1.5 (6)	C4—C9—C10—C1	−0.5 (6)
C13—O1—C1—C2	177.3 (4)	C8—C9—C10—C1	178.5 (4)
O1—C1—C2—C3	−179.9 (4)	C4—C9—C10—C11	178.0 (4)
C10—C1—C2—C3	−1.1 (7)	C8—C9—C10—C11	−3.1 (6)
C1—C2—C3—C4	0.5 (7)	C1—C10—C11—C12	−1.4 (6)
C2—C3—C4—C9	0.1 (7)	C9—C10—C11—C12	−179.9 (4)
C2—C3—C4—C5	−179.1 (5)	C10—C11—C12—C13	1.8 (6)
C9—C4—C5—C6	0.0 (7)	C10—C11—C12—C14	176.8 (4)
C3—C4—C5—C6	179.2 (4)	C1—O1—C13—O4	−176.1 (4)
C4—C5—C6—C7	−0.3 (7)	C1—O1—C13—C12	1.7 (6)
C5—C6—C7—C8	0.6 (8)	C11—C12—C13—O4	175.6 (5)
C6—C7—C8—C9	−0.5 (7)	C14—C12—C13—O4	0.8 (7)
C3—C4—C9—C8	−179.1 (4)	C11—C12—C13—O1	−1.8 (6)
C5—C4—C9—C8	0.1 (6)	C14—C12—C13—O1	−176.7 (4)
C3—C4—C9—C10	−0.1 (6)	C15—O2—C14—O3	−4.1 (7)
C5—C4—C9—C10	179.1 (4)	C15—O2—C14—C12	176.2 (4)
C7—C8—C9—C4	0.2 (7)	C11—C12—C14—O3	−22.9 (6)
C7—C8—C9—C10	−178.8 (4)	C13—C12—C14—O3	151.9 (4)
O1—C1—C10—C11	1.2 (6)	C11—C12—C14—O2	156.8 (4)
C2—C1—C10—C11	−177.5 (4)	C13—C12—C14—O2	−28.4 (6)
O1—C1—C10—C9	179.8 (4)	C14—O2—C15—C16	82.2 (5)
C2—C1—C10—C9	1.1 (6)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂O₄
M_r	268.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.6716 (11), 4.5190 (5), 19.3874 (18)
β (°)	90.218 (7)
V (Å³)	1285.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.22 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	ψ scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.981, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	13075, 2276, 997
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.208, 1.04
No. of reflections	2276
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1999).

Acknowledgements

The authors thank the DST, India, for funding under DST–FIST (Level II) for the X-ray diffraction facility at SSCU, IISc, Bangalore.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gikas, E., Parissi-Poulou, M., Kazanis, M. & Vavagianis, A. (2003). Anal. Chim. Acta, 489, 153–163. Web of Science CrossRef CAS Google Scholar
Jiao, Y.-H., Zhang, Q., Meng, F.-Y., Teng, L., Yuan, J. & Ng, S. W. (2009). Acta Cryst. E65, o775. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jones, G. II, Jackson, W. R., Choi, C. & Bergmark, W. R. (1985). J. Phys. Chem. 89, 294–300. CrossRef CAS Web of Science Google Scholar
Kendall, J. D., Duflin, G. E. & Waddington, H. R. J. (1961). Chem. Abstr. 55, 21927. Google Scholar
Lakshmi, S., Manvar, D., Parecha, A., Shah, A., Sridhar, M. A. & Shashidhara Prasad, J. (2006). Acta Cryst. E62, o2163–o2165. Web of Science CSD CrossRef IUCr Journals Google Scholar
Miyata, S. & Nalwa, H. S. (1997). Editors. Organic Electroluminescent Materials and Devices. Amsterdam: Gordon and Breach. Google Scholar
Rau, R. & Brack, A. (1963). Chem. Abstr. 58, 11506. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shibata, T. (1994). Japan Patent 6 122 874. Google Scholar