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

Abstract

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.

Related literature  

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

Experimental  

Crystal data  

• C₁₅H₁₀O₄

• M _r = 254.23

• Orthorhombic,

• a = 13.4231 (4) Å

• b = 8.9892 (3) Å

• c = 18.8407 (6) Å

• V = 2273.37 (12) ų

• Z = 8

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 293 K

• 0.35 × 0.30 × 0.25 mm

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

Refinement  

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 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

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.

Supplementary Material

CCDC reference: 1415238

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1O4i	0.82	1.84	2.626(3)	160
C14H14AO4ii	0.97	2.57	3.503(4)	161

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

S1. Experimental

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.

S2. Refinement

All the H atoms in (I) were positioned geometrically and refined using a riding model with bond lengths 0.97 \%A (for methylene), 0.96 \%A (for methyl and 0.86 \%A (for amine). The U\ĩso\~(H) = 1.5U\~eq\~(C) for methyl and U\ĩso\~(H) = 1.2U\~eq\~(C) for all other carbon bound H atoms.

Figures

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.

Crystal data

C15H10O4	Dx = 1.486 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0513P)2 + 1.4242P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.138	(Δ/σ)max < 0.001
S = 1.15	Δρmax = 0.19 e Å−3
2001 reflections	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.