Crystal structure of 7,8-benzocoumarin-4-acetic acid

Swamy, R.R.; Gowda, R.; Gowda, K.V.A.; Basanagouda, M.

doi:10.1107/S2056989015014103

organic compounds

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ISSN: 2056-9890

Volume 71| Part 8| August 2015| Pages o617-o618

https://doi.org/10.1107/S2056989015014103

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Crystal structure of 7,8-benzocoumarin-4-acetic acid

R. Ranga Swamy,^a Ramakrishna Gowda,^b ^* K. V. Arjuna Gowda ^c and Mahantesha Basanagouda ^d

^aDepartment of Physics, Sri Krishna Rajendra Silver Jubilee Institute of Technology, Bangalore 560 001, Karnataka, India, ^bDepartment of Physics, Govt. College for Women, Kolar 563 101, Karnataka, India, ^cDepartment of Physics, Govt. College for Women, Mandya 571 401, India, and ^dDepartment of Chemistry, P.C. Jabin Science College, Hubli 580 031, Karnataka, India
^*Correspondence e-mail: rkgowdaphy@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 25 July 2015; accepted 25 July 2015; online 31 July 2015)

The fused-ring system in the title compound [systematic name: 2-(2-oxo-2H-benzo[h]chromen-4-yl)acetic acid], C₁₅H₁₀O₄, is almost planar (r.m.s. deviation = 0.031 Å) and the C_ar—C—C=O (ar = aromatic) torsion angle for the side chain is −134.4 (3)°. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, generating [100] C(8) chains, where the acceptor atom is the exocyclic O atom of the fused-ring system. The packing is consolidated by a very weak C—H⋯O hydrogen bond to the same acceptor atom. Together, these interactions lead to undulating (001) layers in the crystal.

Keywords: crystal structure; coumarin; acetic acid; hydrogen bonding.

CCDC reference: 1415238

1. Related literature

For a related structure and background to coumarins, see: Basanagouda et al. (2009 ). For the synthesis, see: Laskowski & Clinton (1950 ).

2. Experimental

2.1. Crystal data

C₁₅H₁₀O₄
M_r = 254.23
Orthorhombic, P b c a
a = 13.4231 (4) Å
b = 8.9892 (3) Å
c = 18.8407 (6) Å
V = 2273.37 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

2.2. Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.961, T_max = 0.979
27493 measured reflections
2001 independent reflections
1356 reflections with I > 2σ(I)
R_int = 0.051

2.3. Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.138
S = 1.15
2001 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.82	1.84	2.626 (3)	160
C14—H14A⋯O4ⁱⁱ	0.97	2.57	3.503 (4)	161
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL2014.

Supporting information

CCDC reference: 1415238

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015014103/hb7471sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014103/hb7471Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015014103/hb7471Isup3.cml

checkCIF report

Related literature top

For a related structure and background to coumarins, see: Basanagouda et al. (2009). For the synthesis, see: Laskowski & Clinton (1950).

Experimental top

A mixture of citric acid 2 (1 mol) and conc. sulfuric acid (32 ml) was stirred for half an hour, then the temperature was slowly raised during an interval of 10–15 min and as soon as the evolution of gas slackened, the flask was removed from the bath, allowed to stand for 15 min till the reaction mixture became clear and free from carbon monoxide bubbles; this was then cooled to 10°C. To this solution, 1-naphthol (1 mol) was added at 10°C, drop wise. After the addition, the reaction mixture was stirred at room temperature for 48 h. The reaction mixture was then poured onto crushed ice, the separated solid was filtered and dissolved in saturated sodium bicarbonate solution which on acidification gave the title compound (Laskowski et al. 1950). Colourless blocks were recrystallised from acetic acid solution at room temperature.

Structure description top

For a related structure and background to coumarins, see: Basanagouda et al. (2009). For the synthesis, see: Laskowski & Clinton (1950).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top

	Fig. 1. ORTEP diagram of molecule (I) with 40% probability displacement ellipsoids.
	Fig. 2. The packing diagram of (I)·The dotted lines indicate hydrogen bonds. All H atoms which are not in interactions have been omitted for clarity.

2-(2-Oxo-2H-benzo[h]chromen-4-yl)acetic acid top

Crystal data top

C₁₅H₁₀O₄	D_x = 1.486 Mg m⁻³
M_r = 254.23	Melting point: 463 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 13.4231 (4) Å	Cell parameters from 6795 reflections
b = 8.9892 (3) Å	θ = 2.6–27.0°
c = 18.8407 (6) Å	µ = 0.11 mm⁻¹
V = 2273.37 (12) Å³	T = 293 K
Z = 8	Block, colourless
F(000) = 1056	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2001 independent reflections
Radiation source: fine-focus sealed tube	1356 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω and φ scan	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→14
T_min = 0.961, T_max = 0.979	k = −10→10
27493 measured reflections	l = −22→22

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.0513P)² + 1.4242P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.138	(Δ/σ)_max < 0.001
S = 1.15	Δρ_max = 0.19 e Å⁻³
2001 reflections	Δρ_min = −0.21 e Å⁻³
173 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0072 (15)

Crystal data top

C₁₅H₁₀O₄	V = 2273.37 (12) Å³
M_r = 254.23	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.4231 (4) Å	µ = 0.11 mm⁻¹
b = 8.9892 (3) Å	T = 293 K
c = 18.8407 (6) Å	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2001 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1356 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.979	R_int = 0.051
27493 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.15	Δρ_max = 0.19 e Å⁻³
2001 reflections	Δρ_min = −0.21 e Å⁻³
173 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
C1	0.61455 (18)	0.5555 (3)	0.36390 (13)	0.0399 (6)
C2	0.53352 (18)	0.5222 (3)	0.32542 (13)	0.0437 (7)
H2	0.5206	0.5762	0.2843	0.052*
C3	0.46688 (18)	0.4072 (3)	0.34547 (14)	0.0425 (7)
C4	0.56434 (16)	0.3698 (3)	0.44910 (12)	0.0352 (6)
C5	0.63240 (16)	0.4753 (3)	0.42875 (13)	0.0373 (6)
C6	0.71549 (19)	0.5000 (3)	0.47401 (15)	0.0491 (7)
H6	0.7635	0.5697	0.4613	0.059*
C7	0.7255 (2)	0.4236 (4)	0.53509 (15)	0.0538 (8)
H7	0.7809	0.4412	0.5636	0.065*
C8	0.65443 (18)	0.3177 (3)	0.55708 (13)	0.0434 (7)
C9	0.6629 (2)	0.2399 (4)	0.62160 (15)	0.0567 (8)
H9	0.7168	0.2582	0.6514	0.068*
C10	0.5932 (3)	0.1385 (4)	0.64072 (16)	0.0649 (9)
H10	0.5996	0.0882	0.6836	0.078*
C11	0.5123 (2)	0.1087 (3)	0.59706 (16)	0.0579 (8)
H11	0.4654	0.0381	0.6107	0.069*
C12	0.5010 (2)	0.1822 (3)	0.53436 (14)	0.0466 (7)
H12	0.4465	0.1618	0.5055	0.056*
C13	0.57165 (17)	0.2887 (3)	0.51328 (12)	0.0377 (6)
C14	0.6857 (2)	0.6737 (3)	0.33961 (16)	0.0508 (7)
H14A	0.6521	0.7373	0.3056	0.061*
H14B	0.7041	0.7347	0.3800	0.061*
C15	0.7782 (2)	0.6133 (3)	0.30629 (14)	0.0461 (7)
O1	0.75750 (14)	0.5102 (2)	0.25935 (11)	0.0661 (6)
H1	0.8094	0.4790	0.2419	0.099*
O2	0.86066 (15)	0.6547 (3)	0.31854 (12)	0.0770 (7)
O3	0.48342 (11)	0.33699 (19)	0.40811 (9)	0.0407 (5)
O4	0.39440 (14)	0.3648 (2)	0.31208 (10)	0.0597 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0375 (13)	0.0406 (15)	0.0415 (15)	0.0035 (11)	0.0080 (11)	−0.0058 (12)
C2	0.0450 (14)	0.0481 (16)	0.0378 (14)	0.0073 (13)	0.0017 (12)	0.0011 (12)
C3	0.0388 (14)	0.0516 (16)	0.0373 (15)	0.0069 (13)	−0.0039 (12)	−0.0045 (13)
C4	0.0280 (12)	0.0415 (14)	0.0363 (14)	0.0034 (11)	−0.0024 (10)	−0.0093 (11)
C5	0.0331 (12)	0.0410 (14)	0.0378 (14)	0.0009 (11)	0.0020 (10)	−0.0089 (12)
C6	0.0383 (14)	0.0575 (18)	0.0514 (17)	−0.0072 (13)	−0.0008 (12)	−0.0126 (15)
C7	0.0418 (16)	0.070 (2)	0.0491 (17)	0.0035 (14)	−0.0135 (12)	−0.0190 (16)
C8	0.0407 (14)	0.0504 (16)	0.0392 (15)	0.0126 (13)	−0.0036 (12)	−0.0106 (13)
C9	0.0597 (18)	0.070 (2)	0.0404 (17)	0.0230 (17)	−0.0100 (13)	−0.0061 (15)
C10	0.081 (2)	0.070 (2)	0.0435 (17)	0.0267 (19)	0.0038 (17)	0.0085 (16)
C11	0.068 (2)	0.0504 (18)	0.0547 (19)	0.0103 (15)	0.0165 (16)	0.0071 (15)
C12	0.0495 (15)	0.0457 (16)	0.0445 (16)	0.0037 (13)	0.0046 (13)	−0.0031 (14)
C13	0.0370 (13)	0.0408 (14)	0.0353 (14)	0.0081 (11)	0.0010 (11)	−0.0061 (12)
C14	0.0524 (16)	0.0466 (16)	0.0535 (17)	−0.0014 (13)	0.0087 (13)	−0.0011 (14)
C15	0.0453 (16)	0.0492 (17)	0.0438 (16)	−0.0035 (14)	0.0011 (12)	0.0035 (14)
O1	0.0475 (11)	0.0796 (15)	0.0714 (14)	−0.0079 (10)	0.0161 (10)	−0.0237 (13)
O2	0.0480 (12)	0.0937 (18)	0.0894 (17)	−0.0085 (12)	−0.0036 (11)	−0.0217 (14)
O3	0.0328 (9)	0.0511 (11)	0.0381 (10)	−0.0020 (8)	−0.0040 (7)	−0.0016 (8)
O4	0.0484 (11)	0.0761 (15)	0.0545 (12)	−0.0047 (10)	−0.0200 (9)	0.0020 (11)

Geometric parameters (Å, º) top

C1—C2	1.341 (3)	C8—C13	1.408 (3)
C1—C5	1.439 (3)	C9—C10	1.355 (4)
C1—C14	1.500 (4)	C9—H9	0.9300
C2—C3	1.419 (4)	C10—C11	1.389 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—O4	1.220 (3)	C11—C12	1.362 (4)
C3—O3	1.357 (3)	C11—H11	0.9300
C4—O3	1.365 (3)	C12—C13	1.404 (4)
C4—C5	1.372 (3)	C12—H12	0.9300
C4—C13	1.416 (3)	C14—C15	1.494 (4)
C5—C6	1.421 (3)	C14—H14A	0.9700
C6—C7	1.347 (4)	C14—H14B	0.9700
C6—H6	0.9300	C15—O2	1.190 (3)
C7—C8	1.410 (4)	C15—O1	1.311 (3)
C7—H7	0.9300	O1—H1	0.8200
C8—C9	1.407 (4)

C2—C1—C5	118.8 (2)	C10—C9—H9	119.7
C2—C1—C14	120.6 (2)	C8—C9—H9	119.7
C5—C1—C14	120.5 (2)	C9—C10—C11	120.8 (3)
C1—C2—C3	122.0 (2)	C9—C10—H10	119.6
C1—C2—H2	119.0	C11—C10—H10	119.6
C3—C2—H2	119.0	C12—C11—C10	120.5 (3)
O4—C3—O3	115.7 (2)	C12—C11—H11	119.8
O4—C3—C2	126.4 (3)	C10—C11—H11	119.8
O3—C3—C2	117.9 (2)	C11—C12—C13	120.1 (3)
O3—C4—C5	121.4 (2)	C11—C12—H12	120.0
O3—C4—C13	115.3 (2)	C13—C12—H12	120.0
C5—C4—C13	123.3 (2)	C12—C13—C8	119.6 (2)
C4—C5—C6	117.6 (2)	C12—C13—C4	123.1 (2)
C4—C5—C1	118.2 (2)	C8—C13—C4	117.4 (2)
C6—C5—C1	124.2 (2)	C15—C14—C1	113.6 (2)
C7—C6—C5	120.7 (3)	C15—C14—H14A	108.8
C7—C6—H6	119.6	C1—C14—H14A	108.8
C5—C6—H6	119.6	C15—C14—H14B	108.8
C6—C7—C8	121.9 (2)	C1—C14—H14B	108.8
C6—C7—H7	119.1	H14A—C14—H14B	107.7
C8—C7—H7	119.1	O2—C15—O1	123.3 (3)
C9—C8—C13	118.6 (3)	O2—C15—C14	125.3 (3)
C9—C8—C7	122.3 (3)	O1—C15—C14	111.3 (2)
C13—C8—C7	119.1 (2)	C15—O1—H1	109.5
C10—C9—C8	120.5 (3)	C3—O3—C4	121.5 (2)

C5—C1—C2—C3	−2.2 (4)	C9—C10—C11—C12	−0.6 (4)
C14—C1—C2—C3	177.5 (2)	C10—C11—C12—C13	0.2 (4)
C1—C2—C3—O4	−176.3 (3)	C11—C12—C13—C8	0.6 (4)
C1—C2—C3—O3	4.5 (4)	C11—C12—C13—C4	−179.6 (2)
O3—C4—C5—C6	−178.7 (2)	C9—C8—C13—C12	−0.9 (4)
C13—C4—C5—C6	1.8 (3)	C7—C8—C13—C12	179.3 (2)
O3—C4—C5—C1	2.3 (3)	C9—C8—C13—C4	179.2 (2)
C13—C4—C5—C1	−177.1 (2)	C7—C8—C13—C4	−0.5 (3)
C2—C1—C5—C4	−1.3 (3)	O3—C4—C13—C12	−0.4 (3)
C14—C1—C5—C4	179.1 (2)	C5—C4—C13—C12	179.1 (2)
C2—C1—C5—C6	179.9 (2)	O3—C4—C13—C8	179.4 (2)
C14—C1—C5—C6	0.2 (4)	C5—C4—C13—C8	−1.1 (3)
C4—C5—C6—C7	−1.0 (4)	C2—C1—C14—C15	−101.9 (3)
C1—C5—C6—C7	177.9 (2)	C5—C1—C14—C15	77.8 (3)
C5—C6—C7—C8	−0.6 (4)	C1—C14—C15—O2	−134.4 (3)
C6—C7—C8—C9	−178.4 (3)	C1—C14—C15—O1	47.6 (3)
C6—C7—C8—C13	1.3 (4)	O4—C3—O3—C4	177.3 (2)
C13—C8—C9—C10	0.5 (4)	C2—C3—O3—C4	−3.4 (3)
C7—C8—C9—C10	−179.7 (3)	C5—C4—O3—C3	0.1 (3)
C8—C9—C10—C11	0.3 (4)	C13—C4—O3—C3	179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82	1.84	2.626 (3)	160
C14—H14A···O4ⁱⁱ	0.97	2.57	3.503 (4)	161

Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82	1.84	2.626 (3)	160
C14—H14A···O4ⁱⁱ	0.97	2.57	3.503 (4)	161

Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

MB thanks the UGC–SWRO, Bangalore, for providing a Minor Research Project (reference No. 1415-MRP/14-15/KAKA067/UGC-SWRO) (Diary No. 1709). The authors also thank the SAIF IIT Madras, Chennai, for the data collection.

References

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