3-Acet­oxy-2-naphthoic acid

Souza, B.S.; Vitto, R.; Nome, F.; Kirby, A.J.; Bortoluzzi, A.J.

doi:10.1107/S1600536810040365

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2848

https://doi.org/10.1107/S1600536810040365

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3-Acetoxy-2-naphthoic acid

Bruno S. Souza,^a Ramon Vitto,^a Faruk Nome,^a Anthony J. Kirby ^b and Adailton J. Bortoluzzi ^a ^*

^aDepto. de Química, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, Santa Catarina, Brazil, and ^bUniversity Chemical Laboratory, Cambridge University, Cambridge CB2 1EW, England
^*Correspondence e-mail: adajb@qmc.ufsc.br

(Received 29 September 2010; accepted 8 October 2010; online 20 October 2010)

In the title compound, C₁₃H₁₀O₄, an analog of acetylsalicylic acid, the naphthalene unit is twisted slightly due to ortho disubstitution [dihedral angle between conjugated rings system in the naphthalene unit = 2.0 (2)°]. The mean planes of the carboxylic and ester groups are almost coplanar and perpendicular, respectively, to the mean plane of the conjugated aromatic system, making dihedral angles of 8.9 (3) and 89.3 (1)°. In the crystal, molecules are paired through their carboxylic groups by the typical centrosymmetric O—H⋯O interactions with R₂²(8) hydrogen-bond motifs. In addition, several weak C—H⋯O intermolecular contacts are also observed. Finally, the molecules are stacked along crystallographic [100] and [010] directions.

Related literature

This work was undertaken as part of our study on the relationship between conformation and reactivity in the hydrolysis reactions of esters bearing neighboring catalytic groups. For the synthesis, see: Bergeron et al. (1996 ). For related structures, see: Souza et al. (2007 ); Gu et al. (2001 ); Wilson (2002). Besides electronic effects, intramolecular reactions depend on the spatial relationship of the reacting groups, see: Orth et al. (2010 ).

Experimental

Crystal data

C₁₃H₁₀O₄
M_r = 230.21
Monoclinic, P 2₁ /n
a = 10.235 (2) Å
b = 4.739 (2) Å
c = 23.0873 (16) Å
β = 101.060 (11)°
V = 1099.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.50 × 0.33 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
1999 measured reflections
1950 independent reflections
1214 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.204
S = 1.05
1950 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.91	1.74	2.636 (3)	171
C7—H7⋯O4ⁱⁱ	0.93	2.71	3.368 (5)	128
C13—H13B⋯O4ⁱⁱⁱ	0.96	2.52	3.435 (5)	160
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: SET4 in CAD-4 Software; data reduction: HELENA (Spek, 1996 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810040365/rk2238sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040365/rk2238Isup2.hkl

checkCIF report

Comment top

Besides electronic effects, intramolecular reactions depend on the spatial relationship of the reacting groups (Orth et al., 2010). Subtle changes in the structure of similar compounds may lead to different relationships between nucleophilic-electrophilic centers within similar molecules, leading to different reaction mechanisms in solution. On this basis, we are currently studying the hydrolysis of a series of structurally related naphthyl esters. In a previous report (Souza et al., 2007), we published the structure of 2-carboxy-1-naphthyl acetate, a naphthoic acid bearing an ortho-ester group. In that structure, the dihedral angle between the aromatic mean plane and the ester group is 80.34 (5)°, considerably smaller than the one observed in α-naphthyl acetate (86.50°) (Gu et al., 2001), and we explained this difference in terms of an attractive interaction between the ester and the acid groups in 2-carboxy-1-naphthyl acetate. In the current work, we report the structure of 3-acetoxy-2-naphthoic acid I (Fig. 1), C₁₃H₁₀O₄, an acetylsalicylic analog. In this system the dihedral angle between acetoxy and aromatic mean planes is 89.3 (1)°, while the carboxylic acid group and naphthalene ring are almost coplanar with dihedral angle of 8.9 (3)°. Packing is controlled by carboxylic acid dimer formation, involving centrosymmetric O2–H···O1 interactions (R²₂(8) hydrogen bond pattern, Fig. 2). Several weak C–H···O intermolecular contacts are also observed. Finally, the molecules are stacked along crystallographic [100] and [010] directions (Fig. 3).

Related literature top

This work was undertaken as part of our study on the relationship between conformation and reactivity in the hydrolysis reactions of esters bearing neighboring catalytic groups. For the synthesis, see: Bergeron et al. (1996). For related structures, see: Souza et al. (2007); Gu et al. (2001); Wilson (2002). Besides electronic effects, intramolecular reactions depend on the spatial relationship of the reacting groups, see: Orth et al. (2010).

Experimental top

The title compound was prepared by following the procedure reported by Bergeron et al., (1996). Concentrated sulfuric acid (10 drops) was added to a refluxing mixture of 3-hydroxy-2-naphthoic acid (3.50 g, 18.6 mmol) in acetic anhydride (8 ml, 89.7 mmol). The mixture was kept under reflux for 10 additional minutes and, after cooling to room temperature, the pale solid was filtered off and recrystallized in aqueous ethanol. The 10 mg of the prepared 3-acetoxy-2-naphthoic acid were dissolved in 5 ml of dry CHCl₃ in a 10 ml glass vial and the flask was kept in a saturated petroleum ether (313-333 K) atmosphere at 293 K, giving the title compound as pale yellow crystals that melt at 458-459 K.

Structure description top

This work was undertaken as part of our study on the relationship between conformation and reactivity in the hydrolysis reactions of esters bearing neighboring catalytic groups. For the synthesis, see: Bergeron et al. (1996). For related structures, see: Souza et al. (2007); Gu et al. (2001); Wilson (2002). Besides electronic effects, intramolecular reactions depend on the spatial relationship of the reacting groups, see: Orth et al. (2010).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: SET4 in CAD-4 Software (Enraf–Nonius, 1989); data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.

Figures top

	Fig. 1. The molecular structure of the title compound with the atom labeling scheme. Displacement ellipsoids are shown at the 40% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. Molecules paired by centrosymmetric R²₂(8) hydrogen bonds.
	Fig. 3. Molecules of I stacked along [100] direction (top) and along [010] direction (bottom).

3-Acetoxy-2-naphthoic acid top

Crystal data top

C₁₃H₁₀O₄	F(000) = 480
M_r = 230.21	D_x = 1.391 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.235 (2) Å	θ = 6.5–18.5°
b = 4.739 (2) Å	µ = 0.10 mm⁻¹
c = 23.0873 (16) Å	T = 295 K
β = 101.060 (11)°	Block, pale yellow
V = 1099.0 (5) Å³	0.50 × 0.33 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.026
Radiation source: fine-focus sealed tube	θ_max = 25.1°, θ_min = 1.8°
Graphite monochromator	h = −11→12
ω–/2θ scans	k = −5→0
1999 measured reflections	l = −27→0
1950 independent reflections	3 standard reflections every 200 reflections
1214 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.204	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1252P)² + 0.1035P] where P = (F_o² + 2F_c²)/3
1950 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₃H₁₀O₄	V = 1099.0 (5) Å³
M_r = 230.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.235 (2) Å	µ = 0.10 mm⁻¹
b = 4.739 (2) Å	T = 295 K
c = 23.0873 (16) Å	0.50 × 0.33 × 0.10 mm
β = 101.060 (11)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.026
1999 measured reflections	3 standard reflections every 200 reflections
1950 independent reflections	intensity decay: 1%
1214 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.204	H-atom parameters constrained
S = 1.05	Δρ_max = 0.26 e Å⁻³
1950 reflections	Δρ_min = −0.26 e Å⁻³
155 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.5573 (3)	0.3368 (7)	0.18259 (12)	0.0566 (8)
H1	0.6184	0.4763	0.1779	0.068*
C2	0.4810 (3)	0.2182 (6)	0.13351 (12)	0.0518 (7)
C3	0.3930 (3)	−0.0003 (6)	0.14168 (12)	0.0540 (8)
C4	0.3780 (3)	−0.0817 (7)	0.19648 (14)	0.0632 (9)
H4	0.3170	−0.2222	0.2006	0.076*
C5	0.4544 (3)	0.0454 (7)	0.24728 (13)	0.0599 (8)
C6	0.4428 (3)	−0.0331 (9)	0.30541 (14)	0.0737 (10)
H6	0.3804	−0.1680	0.3110	0.088*
C7	0.5213 (4)	0.0861 (9)	0.35239 (15)	0.0806 (11)
H7	0.5127	0.0308	0.3901	0.097*
C8	0.6136 (4)	0.2872 (9)	0.34600 (14)	0.0815 (11)
H8	0.6669	0.3659	0.3792	0.098*
C9	0.6278 (3)	0.3735 (8)	0.29060 (13)	0.0736 (10)
H9	0.6906	0.5097	0.2863	0.088*
C10	0.5463 (3)	0.2538 (7)	0.24028 (12)	0.0564 (8)
C11	0.4918 (3)	0.3266 (7)	0.07423 (12)	0.0543 (7)
C12	0.2108 (3)	−0.0557 (7)	0.06310 (13)	0.0583 (8)
C13	0.1651 (3)	−0.2253 (8)	0.00866 (15)	0.0770 (10)
H13A	0.0772	−0.1662	−0.0098	0.115*
H13B	0.1635	−0.4215	0.0188	0.115*
H13C	0.2250	−0.1974	−0.0181	0.115*
O1	0.4153 (2)	0.2552 (5)	0.02898 (9)	0.0680 (7)
O2	0.5866 (2)	0.5076 (6)	0.07447 (9)	0.0768 (8)
H2	0.5764	0.5907	0.0385	0.092*
O3	0.32733 (19)	−0.1555 (4)	0.09356 (9)	0.0623 (6)
O4	0.1549 (2)	0.1389 (6)	0.07911 (10)	0.0802 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0497 (15)	0.073 (2)	0.0460 (16)	0.0003 (15)	0.0077 (12)	0.0016 (14)
C2	0.0447 (14)	0.0656 (18)	0.0458 (15)	0.0087 (13)	0.0105 (12)	0.0041 (13)
C3	0.0466 (15)	0.0625 (18)	0.0508 (16)	0.0069 (14)	0.0043 (12)	0.0017 (14)
C4	0.0547 (17)	0.071 (2)	0.0629 (19)	−0.0013 (15)	0.0080 (14)	0.0167 (16)
C5	0.0536 (17)	0.073 (2)	0.0530 (17)	0.0156 (16)	0.0112 (13)	0.0124 (15)
C6	0.073 (2)	0.096 (3)	0.0540 (19)	0.0135 (19)	0.0171 (16)	0.0212 (18)
C7	0.089 (2)	0.105 (3)	0.050 (2)	0.029 (2)	0.0195 (18)	0.0172 (19)
C8	0.089 (2)	0.109 (3)	0.0429 (18)	0.021 (2)	0.0032 (16)	−0.0017 (18)
C9	0.071 (2)	0.097 (3)	0.0500 (18)	0.0015 (19)	0.0058 (15)	−0.0016 (17)
C10	0.0523 (16)	0.070 (2)	0.0465 (16)	0.0156 (15)	0.0082 (13)	0.0037 (14)
C11	0.0464 (15)	0.0720 (19)	0.0457 (16)	0.0021 (15)	0.0116 (12)	−0.0024 (14)
C12	0.0507 (16)	0.067 (2)	0.0567 (17)	0.0070 (15)	0.0100 (13)	0.0112 (16)
C13	0.069 (2)	0.092 (3)	0.064 (2)	0.0046 (19)	−0.0036 (15)	−0.0056 (18)
O1	0.0652 (13)	0.0970 (16)	0.0415 (11)	−0.0110 (12)	0.0096 (9)	−0.0044 (11)
O2	0.0623 (13)	0.120 (2)	0.0481 (12)	−0.0266 (14)	0.0093 (9)	0.0100 (12)
O3	0.0549 (12)	0.0653 (13)	0.0612 (13)	0.0042 (10)	−0.0029 (9)	0.0011 (10)
O4	0.0618 (13)	0.1063 (19)	0.0698 (15)	0.0223 (14)	0.0057 (11)	−0.0064 (13)

Geometric parameters (Å, º) top

C1—C2	1.368 (4)	C7—H7	0.9300
C1—C10	1.414 (4)	C8—C9	1.377 (5)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.409 (4)	C9—C10	1.412 (4)
C2—C11	1.486 (4)	C9—H9	0.9300
C3—C4	1.359 (4)	C11—O1	1.227 (3)
C3—O3	1.393 (3)	C11—O2	1.295 (3)
C4—C5	1.413 (4)	C12—O4	1.181 (4)
C4—H4	0.9300	C12—O3	1.349 (3)
C5—C10	1.395 (4)	C12—C13	1.490 (4)
C5—C6	1.419 (4)	C13—H13A	0.9600
C6—C7	1.344 (5)	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—C8	1.370 (5)	O2—H2	0.9071

C2—C1—C10	122.0 (3)	C7—C8—H8	119.9
C2—C1—H1	119.0	C9—C8—H8	119.9
C10—C1—H1	119.0	C8—C9—C10	119.6 (4)
C1—C2—C3	118.0 (3)	C8—C9—H9	120.2
C1—C2—C11	119.3 (3)	C10—C9—H9	120.2
C3—C2—C11	122.7 (3)	C5—C10—C9	119.6 (3)
C4—C3—O3	118.0 (3)	C5—C10—C1	118.9 (3)
C4—C3—C2	121.5 (3)	C9—C10—C1	121.5 (3)
O3—C3—C2	120.3 (2)	O1—C11—O2	122.8 (3)
C3—C4—C5	120.6 (3)	O1—C11—C2	122.8 (3)
C3—C4—H4	119.7	O2—C11—C2	114.4 (2)
C5—C4—H4	119.7	O4—C12—O3	122.9 (3)
C10—C5—C4	118.9 (3)	O4—C12—C13	126.3 (3)
C10—C5—C6	118.4 (3)	O3—C12—C13	110.7 (3)
C4—C5—C6	122.7 (3)	C12—C13—H13A	109.5
C7—C6—C5	120.5 (4)	C12—C13—H13B	109.5
C7—C6—H6	119.8	H13A—C13—H13B	109.5
C5—C6—H6	119.8	C12—C13—H13C	109.5
C6—C7—C8	121.6 (3)	H13A—C13—H13C	109.5
C6—C7—H7	119.2	H13B—C13—H13C	109.5
C8—C7—H7	119.2	C11—O2—H2	109.2
C7—C8—C9	120.3 (3)	C12—O3—C3	118.3 (2)

C10—C1—C2—C3	−2.4 (4)	C6—C5—C10—C9	2.1 (4)
C10—C1—C2—C11	176.4 (3)	C4—C5—C10—C1	1.8 (4)
C1—C2—C3—C4	3.6 (4)	C6—C5—C10—C1	−179.1 (3)
C11—C2—C3—C4	−175.2 (3)	C8—C9—C10—C5	−1.3 (5)
C1—C2—C3—O3	−170.7 (2)	C8—C9—C10—C1	179.8 (3)
C11—C2—C3—O3	10.5 (4)	C2—C1—C10—C5	−0.3 (4)
O3—C3—C4—C5	172.3 (2)	C2—C1—C10—C9	178.6 (3)
C2—C3—C4—C5	−2.1 (5)	C1—C2—C11—O1	−170.7 (3)
C3—C4—C5—C10	−0.6 (5)	C3—C2—C11—O1	8.0 (5)
C3—C4—C5—C6	−179.7 (3)	C1—C2—C11—O2	7.7 (4)
C10—C5—C6—C7	−1.7 (5)	C3—C2—C11—O2	−173.5 (2)
C4—C5—C6—C7	177.4 (3)	O4—C12—O3—C3	−8.7 (4)
C5—C6—C7—C8	0.5 (6)	C13—C12—O3—C3	171.9 (3)
C6—C7—C8—C9	0.3 (6)	C4—C3—O3—C12	98.6 (3)
C7—C8—C9—C10	0.1 (5)	C2—C3—O3—C12	−86.8 (3)
C4—C5—C10—C9	−177.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.91	1.74	2.636 (3)	171
C7—H7···O4ⁱⁱ	0.93	2.71	3.368 (5)	128
C13—H13B···O4ⁱⁱⁱ	0.96	2.52	3.435 (5)	160

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀O₄
M_r	230.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	10.235 (2), 4.739 (2), 23.0873 (16)
β (°)	101.060 (11)
V (Å³)	1099.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.33 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1999, 1950, 1214
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.204, 1.05
No. of reflections	1950
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.26

Computer programs: SET4 in CAD-4 Software (Enraf–Nonius, 1989), HELENA (Spek, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.91	1.74	2.636 (3)	170.7
C7—H7···O4ⁱⁱ	0.93	2.71	3.368 (5)	128
C13—H13B···O4ⁱⁱⁱ	0.96	2.52	3.435 (5)	160

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

Acknowledgements

The authors thank the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Instituto Nacional de Ciência e Tecnologia (INCT) – Catálise for financial assistance. We also thank Dr J. E. Davies for his important contribution to this work.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bergeron, R. J., Wiegand, J., Wollenweber, M., McManis, J. S., Algee, S. E. & Ratliff-Thompson, K. (1996). J. Med. Chem. 39, 1575–1581. CrossRef CAS PubMed Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Gu, W., Abdallah, D. J. & Weiss, R. G. (2001). Photochem. Photobiol. A, 139, 79–87. Web of Science CSD CrossRef CAS Google Scholar
Orth, E. S., Brandão, T. A. S., Souza, B. S., Pliego, J. R., Vaz, B. G., Eberlin, M. N., Kirby, A. J. & Nome, F. (2010). J. Am. Chem. Soc. 132, 8513–8523. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Souza, B. S., Bortoluzzi, A. J. & Nome, F. (2007). Acta Cryst. E63, o4523. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (1996). HELENA. University of Utrecht, The Netherlands. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wilson, C. C. (2002). New J. Chem. 26, 1733–1739. Web of Science CSD CrossRef CAS Google Scholar