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In the crystal structure of the title compound, C13H10O4, mol­ecules are linked through centrosymmetrically related O—H...O hydrogen bonds by carboxyl pairing. Methyl H atoms of the acet­oxy group are disordered over two equally occupied sites. The compound was prepared for the study of the relationship between conformation and reactivity in hydrolysis reactions of esters bearing neighboring catalytic groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053433/bh2141sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053433/bh2141Isup2.hkl
Contains datablock I

CCDC reference: 672801

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.038
  • wR factor = 0.116
  • Data-to-parameter ratio = 12.9

checkCIF/PLATON results

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Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 100 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 1000 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 6
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Intramolecular carboxyl group catalysis on ester hydrolysis involves the carboxyl group acting as general base or general acid. In cases where the leaving group is activated, like 2,4-dinitro acetyl salicylic acid (Fersht & Kirby, 1968) or esters of naphthalic acid (Barros et al., 2001), nucleophilic attack has been reported. General acid-base catalysis is evidently highly efficient in enzyme active sites, but in only a handful of model systems. The common feature of these efficient intramolecular model systems is the development of a strong intramolecular hydrogen bond in the product, and thus in the transition state leading to it. We are interested in the effect of the proximity and conformation of the reactive groups in ester hydrolysis catalyzed by the acid group and we have selected naphthalene rings to anchor the reactive groups, since significant effects have been reported in naphthalene derivatives. Thus, we prepared a series of naphthoic esters bearing neighboring carboxyl group in different special relationships. Here we report the structure of 1-acetoxy-2-naphthoic acid, (I).

A projection of the crystal structure of (I) is shown in Fig. 1 and the selected bond lengths and angles are given in Table 1. The acid group plane O21/C20/O22 is 3.35° less planar in relation to the mean aromatic plane than the same group in 2-naphthoic acid (Fitzgerald & Gerkin, 1993). The C1—C2—C20 and O10—C1—C10 angles are wider and narrower, respectively, than the equivalent angles in 2-naphthoic acid (Fitzgerald & Gerkin, 1993) and α-naphthyl acetate (Gu et al., 2001). These results are indicative of some repulsive interaction between O22 and O10 atoms. Conversely, the dihedral angle between the aromatic mean plane C1···C10 and the ester group O10/O11/C12/C13 is 80.34 (5)°, while the equivalent angle in α-naphthyl acetate is 86.5° (Gu et al., 2001). This decrease in dihedral angle could be the result of the short separation between O22 and C12, 2.860 (2) Å, which may indicate an attractive interaction, which can account for the high reactivity in solution detected in some preliminary kinetic studies.

The main feature in the crystal structure of (I) is the dimeric structure formed by intermolecular hydrogen bond. The molecules are linked through centrosymmetrically related O—H···O hydrogen bonds by carboxyl pairing (Fig. 2).

Related literature top

For related literature, see: Barros et al. (2001); Bergeron et al. (1996); Fersht & Kirby (1968); Fitzgerald & Gerkin (1993); Gu et al. (2001).

Experimental top

The title compound was prepared by a procedure similar to that reported by Bergeron et al. (1996) for the preparation of 3-acetoxy-2-naphthoic acid. Concentrated sulfuric acid (10 drops) were added to a refluxing mixture of 1-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 pale crystals melt at 411–412 K.

Refinement top

H atoms bonded to C atoms were added at calculated positions, with C—H = 0.96 (methyl CH3) or 0.93 Å (aromatic CH), and Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl group. For the methyl group, H atoms are disordered over two positions, by rotation about C12—C13. Both positions were idealized, with site occupancies fixed to 1/2. H atom of the acid group was found in a difference map and treated as riding on O22, with Uiso(H22) = 1.2Ueq(O22).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with labeling scheme. Displacement ellipsoids are shown at the 40% probability level for non H atoms. Methyl H atoms of the acetoxy group are disordered over two positions, but a single orientation is shhown.
[Figure 2] Fig. 2. Packing of (I) showing the molecules connected through hydrogen bonds and stacked along axis [010].
2-Carboxy-1-naphthyl acetate top
Crystal data top
C13H10O4Z = 2
Mr = 230.21F(000) = 240
Triclinic, P1Dx = 1.365 Mg m3
Hall symbol: -P 1Melting point: 411 K
a = 7.569 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.498 (1) ÅCell parameters from 25 reflections
c = 8.892 (1) Åθ = 5.4–16.9°
α = 100.78 (1)°µ = 0.10 mm1
β = 93.64 (1)°T = 293 K
γ = 91.56 (1)°Irregular block, colourless
V = 560.27 (12) Å30.50 × 0.23 × 0.13 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.010
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 2.3°
Graphite monochromatorh = 99
ω–2θ scansk = 910
2124 measured reflectionsl = 100
1987 independent reflections3 standard reflections every 200 reflections
1516 reflections with I > 2σ(I) intensity decay: <1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0621P)2 + 0.0777P]
where P = (Fo2 + 2Fc2)/3
1987 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C13H10O4γ = 91.56 (1)°
Mr = 230.21V = 560.27 (12) Å3
Triclinic, P1Z = 2
a = 7.569 (1) ÅMo Kα radiation
b = 8.498 (1) ŵ = 0.10 mm1
c = 8.892 (1) ÅT = 293 K
α = 100.78 (1)°0.50 × 0.23 × 0.13 mm
β = 93.64 (1)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.010
2124 measured reflections3 standard reflections every 200 reflections
1987 independent reflections intensity decay: <1%
1516 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.04Δρmax = 0.14 e Å3
1987 reflectionsΔρmin = 0.30 e Å3
154 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.20498 (18)0.67195 (18)0.10960 (16)0.0424 (4)
C20.17587 (18)0.53133 (18)0.16112 (16)0.0416 (4)
C30.21410 (19)0.38603 (19)0.06528 (17)0.0468 (4)
H30.19570.29000.09880.056*
C40.2771 (2)0.3831 (2)0.07489 (18)0.0506 (4)
H40.30150.28560.13540.061*
C50.30595 (19)0.5267 (2)0.12959 (16)0.0487 (4)
C60.3692 (2)0.5273 (2)0.27633 (19)0.0608 (5)
H60.39390.43110.33890.073*
C70.3940 (2)0.6671 (3)0.3258 (2)0.0724 (6)
H70.43480.66570.42250.087*
C80.3592 (3)0.8128 (3)0.2338 (2)0.0742 (6)
H80.37790.90770.26940.089*
C90.2978 (2)0.8182 (2)0.0910 (2)0.0628 (5)
H90.27460.91610.03050.075*
C100.26988 (18)0.6744 (2)0.03603 (17)0.0474 (4)
C120.2811 (2)0.88957 (19)0.31165 (19)0.0527 (4)
C130.2144 (3)1.0414 (2)0.3956 (2)0.0781 (6)
H13A0.09971.05940.35100.117*0.50
H13B0.29481.12870.38890.117*0.50
H13C0.20561.03430.50140.117*0.50
H13D0.30041.08890.47650.117*0.50
H13E0.10531.01950.43860.117*0.50
H13F0.19451.11400.32610.117*0.50
C200.10309 (18)0.52309 (17)0.31152 (16)0.0417 (4)
O100.16270 (14)0.81991 (12)0.19450 (12)0.0508 (3)
O110.41900 (17)0.83269 (15)0.33735 (15)0.0704 (4)
O210.08911 (17)0.38850 (14)0.34850 (13)0.0639 (4)
O220.05509 (16)0.65000 (13)0.39605 (12)0.0582 (3)
H220.00600.63490.48410.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0409 (8)0.0493 (9)0.0383 (8)0.0025 (6)0.0031 (6)0.0115 (6)
C20.0386 (7)0.0520 (9)0.0357 (8)0.0020 (6)0.0031 (6)0.0123 (6)
C30.0476 (8)0.0509 (9)0.0428 (8)0.0028 (7)0.0044 (7)0.0104 (7)
C40.0481 (8)0.0589 (10)0.0429 (8)0.0056 (7)0.0060 (7)0.0035 (7)
C50.0371 (8)0.0728 (11)0.0366 (8)0.0017 (7)0.0036 (6)0.0108 (7)
C60.0526 (9)0.0897 (13)0.0420 (9)0.0040 (9)0.0106 (7)0.0144 (9)
C70.0659 (11)0.1106 (17)0.0469 (10)0.0015 (11)0.0157 (8)0.0273 (11)
C80.0765 (13)0.0933 (15)0.0648 (12)0.0064 (11)0.0155 (10)0.0435 (11)
C90.0688 (11)0.0692 (12)0.0566 (10)0.0013 (9)0.0127 (8)0.0258 (9)
C100.0405 (8)0.0636 (10)0.0419 (8)0.0009 (7)0.0042 (6)0.0197 (7)
C120.0637 (10)0.0455 (9)0.0511 (9)0.0050 (8)0.0121 (8)0.0134 (7)
C130.0923 (15)0.0567 (11)0.0830 (14)0.0045 (10)0.0197 (11)0.0024 (10)
C200.0432 (8)0.0456 (8)0.0383 (8)0.0042 (6)0.0054 (6)0.0122 (6)
O100.0589 (7)0.0492 (6)0.0480 (6)0.0071 (5)0.0091 (5)0.0162 (5)
O110.0671 (8)0.0618 (8)0.0761 (9)0.0029 (6)0.0066 (7)0.0011 (6)
O210.0883 (9)0.0547 (7)0.0583 (7)0.0167 (6)0.0303 (6)0.0254 (6)
O220.0801 (8)0.0535 (7)0.0442 (6)0.0015 (6)0.0240 (6)0.0115 (5)
Geometric parameters (Å, º) top
C1—C21.375 (2)C8—H80.9300
C1—O101.3967 (18)C9—C101.413 (2)
C1—C101.417 (2)C9—H90.9300
C2—C31.411 (2)C12—O111.189 (2)
C2—C201.491 (2)C12—O101.364 (2)
C3—C41.359 (2)C12—C131.483 (2)
C3—H30.9300C13—H13A0.9600
C4—C51.412 (2)C13—H13B0.9600
C4—H40.9300C13—H13C0.9600
C5—C101.414 (2)C13—H13D0.9600
C5—C61.419 (2)C13—H13E0.9600
C6—C71.354 (3)C13—H13F0.9600
C6—H60.9300C20—O211.2514 (17)
C7—C81.392 (3)C20—O221.2700 (18)
C7—H70.9300O22—H220.9613
C8—C91.373 (3)
C2—C1—O10121.68 (12)O11—C12—O10122.40 (15)
C2—C1—C10122.05 (14)O11—C12—C13126.65 (17)
O10—C1—C10116.18 (13)O10—C12—C13110.95 (16)
C1—C2—C3118.25 (13)C12—C13—H13A109.5
C1—C2—C20123.76 (13)C12—C13—H13B109.5
C3—C2—C20117.98 (13)H13A—C13—H13B109.5
C4—C3—C2121.56 (15)C12—C13—H13C109.5
C4—C3—H3119.2H13A—C13—H13C109.5
C2—C3—H3119.2H13B—C13—H13C109.5
C3—C4—C5120.68 (15)C12—C13—H13D109.5
C3—C4—H4119.7H13A—C13—H13D141.1
C5—C4—H4119.7H13B—C13—H13D56.3
C4—C5—C10119.17 (13)H13C—C13—H13D56.3
C4—C5—C6121.96 (16)C12—C13—H13E109.5
C10—C5—C6118.86 (16)H13A—C13—H13E56.3
C7—C6—C5120.44 (18)H13B—C13—H13E141.1
C7—C6—H6119.8H13C—C13—H13E56.3
C5—C6—H6119.8H13D—C13—H13E109.5
C6—C7—C8120.88 (17)C12—C13—H13F109.5
C6—C7—H7119.6H13A—C13—H13F56.3
C8—C7—H7119.6H13B—C13—H13F56.3
C9—C8—C7120.75 (18)H13C—C13—H13F141.1
C9—C8—H8119.6H13D—C13—H13F109.5
C7—C8—H8119.6H13E—C13—H13F109.5
C8—C9—C10119.83 (18)O21—C20—O22122.29 (13)
C8—C9—H9120.1O21—C20—C2117.85 (13)
C10—C9—H9120.1O22—C20—C2119.85 (13)
C9—C10—C5119.24 (14)C12—O10—C1117.11 (12)
C9—C10—C1122.48 (16)C20—O22—H22115.8
C5—C10—C1118.28 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O22—H22···O21i0.961.702.6517 (15)173
Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC13H10O4
Mr230.21
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.569 (1), 8.498 (1), 8.892 (1)
α, β, γ (°)100.78 (1), 93.64 (1), 91.56 (1)
V3)560.27 (12)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.50 × 0.23 × 0.13
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2124, 1987, 1516
Rint0.010
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.116, 1.04
No. of reflections1987
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.30

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), HELENA (Spek, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O22—H22···O21i0.961.702.6517 (15)173.0
Symmetry code: (i) x, y+1, z+1.
 

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