In the crystal structure of the title compound, C
13H
10O
4, 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
CCDC reference: 672801
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.038
- wR factor = 0.116
- Data-to-parameter ratio = 12.9
checkCIF/PLATON results
No syntax errors found
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
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.
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).
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).
2-Carboxy-1-naphthyl acetate
top
Crystal data top
C13H10O4 | Z = 2 |
Mr = 230.21 | F(000) = 240 |
Triclinic, P1 | Dx = 1.365 Mg m−3 |
Hall symbol: -P 1 | Melting point: 411 K |
a = 7.569 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.498 (1) Å | Cell parameters from 25 reflections |
c = 8.892 (1) Å | θ = 5.4–16.9° |
α = 100.78 (1)° | µ = 0.10 mm−1 |
β = 93.64 (1)° | T = 293 K |
γ = 91.56 (1)° | Irregular block, colourless |
V = 560.27 (12) Å3 | 0.50 × 0.23 × 0.13 mm |
Data collection top
Enraf–Nonius CAD-4 diffractometer | Rint = 0.010 |
Radiation source: fine-focus sealed tube | θmax = 25.1°, θmin = 2.3° |
Graphite monochromator | h = −9→9 |
ω–2θ scans | k = −9→10 |
2124 measured reflections | l = −10→0 |
1987 independent reflections | 3 standard reflections every 200 reflections |
1516 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-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 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C13H10O4 | γ = 91.56 (1)° |
Mr = 230.21 | V = 560.27 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.569 (1) Å | Mo Kα radiation |
b = 8.498 (1) Å | µ = 0.10 mm−1 |
c = 8.892 (1) Å | T = 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 reflections | 3 standard reflections every 200 reflections |
1987 independent reflections | intensity decay: <1% |
1516 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.14 e Å−3 |
1987 reflections | Δρmin = −0.30 e Å−3 |
154 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.20498 (18) | 0.67195 (18) | 0.10960 (16) | 0.0424 (4) | |
C2 | 0.17587 (18) | 0.53133 (18) | 0.16112 (16) | 0.0416 (4) | |
C3 | 0.21410 (19) | 0.38603 (19) | 0.06528 (17) | 0.0468 (4) | |
H3 | 0.1957 | 0.2900 | 0.0988 | 0.056* | |
C4 | 0.2771 (2) | 0.3831 (2) | −0.07489 (18) | 0.0506 (4) | |
H4 | 0.3015 | 0.2856 | −0.1354 | 0.061* | |
C5 | 0.30595 (19) | 0.5267 (2) | −0.12959 (16) | 0.0487 (4) | |
C6 | 0.3692 (2) | 0.5273 (2) | −0.27633 (19) | 0.0608 (5) | |
H6 | 0.3939 | 0.4311 | −0.3389 | 0.073* | |
C7 | 0.3940 (2) | 0.6671 (3) | −0.3258 (2) | 0.0724 (6) | |
H7 | 0.4348 | 0.6657 | −0.4225 | 0.087* | |
C8 | 0.3592 (3) | 0.8128 (3) | −0.2338 (2) | 0.0742 (6) | |
H8 | 0.3779 | 0.9077 | −0.2694 | 0.089* | |
C9 | 0.2978 (2) | 0.8182 (2) | −0.0910 (2) | 0.0628 (5) | |
H9 | 0.2746 | 0.9161 | −0.0305 | 0.075* | |
C10 | 0.26988 (18) | 0.6744 (2) | −0.03603 (17) | 0.0474 (4) | |
C12 | 0.2811 (2) | 0.88957 (19) | 0.31165 (19) | 0.0527 (4) | |
C13 | 0.2144 (3) | 1.0414 (2) | 0.3956 (2) | 0.0781 (6) | |
H13A | 0.0997 | 1.0594 | 0.3510 | 0.117* | 0.50 |
H13B | 0.2948 | 1.1287 | 0.3889 | 0.117* | 0.50 |
H13C | 0.2056 | 1.0343 | 0.5014 | 0.117* | 0.50 |
H13D | 0.3004 | 1.0889 | 0.4765 | 0.117* | 0.50 |
H13E | 0.1053 | 1.0195 | 0.4386 | 0.117* | 0.50 |
H13F | 0.1945 | 1.1140 | 0.3261 | 0.117* | 0.50 |
C20 | 0.10309 (18) | 0.52309 (17) | 0.31152 (16) | 0.0417 (4) | |
O10 | 0.16270 (14) | 0.81991 (12) | 0.19450 (12) | 0.0508 (3) | |
O11 | 0.41900 (17) | 0.83269 (15) | 0.33735 (15) | 0.0704 (4) | |
O21 | 0.08911 (17) | 0.38850 (14) | 0.34850 (13) | 0.0639 (4) | |
O22 | 0.05509 (16) | 0.65000 (13) | 0.39605 (12) | 0.0582 (3) | |
H22 | −0.0060 | 0.6349 | 0.4841 | 0.070* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0409 (8) | 0.0493 (9) | 0.0383 (8) | 0.0025 (6) | 0.0031 (6) | 0.0115 (6) |
C2 | 0.0386 (7) | 0.0520 (9) | 0.0357 (8) | 0.0020 (6) | 0.0031 (6) | 0.0123 (6) |
C3 | 0.0476 (8) | 0.0509 (9) | 0.0428 (8) | 0.0028 (7) | 0.0044 (7) | 0.0104 (7) |
C4 | 0.0481 (8) | 0.0589 (10) | 0.0429 (8) | 0.0056 (7) | 0.0060 (7) | 0.0035 (7) |
C5 | 0.0371 (8) | 0.0728 (11) | 0.0366 (8) | 0.0017 (7) | 0.0036 (6) | 0.0108 (7) |
C6 | 0.0526 (9) | 0.0897 (13) | 0.0420 (9) | 0.0040 (9) | 0.0106 (7) | 0.0144 (9) |
C7 | 0.0659 (11) | 0.1106 (17) | 0.0469 (10) | −0.0015 (11) | 0.0157 (8) | 0.0273 (11) |
C8 | 0.0765 (13) | 0.0933 (15) | 0.0648 (12) | −0.0064 (11) | 0.0155 (10) | 0.0435 (11) |
C9 | 0.0688 (11) | 0.0692 (12) | 0.0566 (10) | −0.0013 (9) | 0.0127 (8) | 0.0258 (9) |
C10 | 0.0405 (8) | 0.0636 (10) | 0.0419 (8) | −0.0009 (7) | 0.0042 (6) | 0.0197 (7) |
C12 | 0.0637 (10) | 0.0455 (9) | 0.0511 (9) | −0.0050 (8) | 0.0121 (8) | 0.0134 (7) |
C13 | 0.0923 (15) | 0.0567 (11) | 0.0830 (14) | 0.0045 (10) | 0.0197 (11) | 0.0024 (10) |
C20 | 0.0432 (8) | 0.0456 (8) | 0.0383 (8) | 0.0042 (6) | 0.0054 (6) | 0.0122 (6) |
O10 | 0.0589 (7) | 0.0492 (6) | 0.0480 (6) | 0.0071 (5) | 0.0091 (5) | 0.0162 (5) |
O11 | 0.0671 (8) | 0.0618 (8) | 0.0761 (9) | 0.0029 (6) | −0.0066 (7) | 0.0011 (6) |
O21 | 0.0883 (9) | 0.0547 (7) | 0.0583 (7) | 0.0167 (6) | 0.0303 (6) | 0.0254 (6) |
O22 | 0.0801 (8) | 0.0535 (7) | 0.0442 (6) | 0.0015 (6) | 0.0240 (6) | 0.0115 (5) |
Geometric parameters (Å, º) top
C1—C2 | 1.375 (2) | C8—H8 | 0.9300 |
C1—O10 | 1.3967 (18) | C9—C10 | 1.413 (2) |
C1—C10 | 1.417 (2) | C9—H9 | 0.9300 |
C2—C3 | 1.411 (2) | C12—O11 | 1.189 (2) |
C2—C20 | 1.491 (2) | C12—O10 | 1.364 (2) |
C3—C4 | 1.359 (2) | C12—C13 | 1.483 (2) |
C3—H3 | 0.9300 | C13—H13A | 0.9600 |
C4—C5 | 1.412 (2) | C13—H13B | 0.9600 |
C4—H4 | 0.9300 | C13—H13C | 0.9600 |
C5—C10 | 1.414 (2) | C13—H13D | 0.9600 |
C5—C6 | 1.419 (2) | C13—H13E | 0.9600 |
C6—C7 | 1.354 (3) | C13—H13F | 0.9600 |
C6—H6 | 0.9300 | C20—O21 | 1.2514 (17) |
C7—C8 | 1.392 (3) | C20—O22 | 1.2700 (18) |
C7—H7 | 0.9300 | O22—H22 | 0.9613 |
C8—C9 | 1.373 (3) | | |
| | | |
C2—C1—O10 | 121.68 (12) | O11—C12—O10 | 122.40 (15) |
C2—C1—C10 | 122.05 (14) | O11—C12—C13 | 126.65 (17) |
O10—C1—C10 | 116.18 (13) | O10—C12—C13 | 110.95 (16) |
C1—C2—C3 | 118.25 (13) | C12—C13—H13A | 109.5 |
C1—C2—C20 | 123.76 (13) | C12—C13—H13B | 109.5 |
C3—C2—C20 | 117.98 (13) | H13A—C13—H13B | 109.5 |
C4—C3—C2 | 121.56 (15) | C12—C13—H13C | 109.5 |
C4—C3—H3 | 119.2 | H13A—C13—H13C | 109.5 |
C2—C3—H3 | 119.2 | H13B—C13—H13C | 109.5 |
C3—C4—C5 | 120.68 (15) | C12—C13—H13D | 109.5 |
C3—C4—H4 | 119.7 | H13A—C13—H13D | 141.1 |
C5—C4—H4 | 119.7 | H13B—C13—H13D | 56.3 |
C4—C5—C10 | 119.17 (13) | H13C—C13—H13D | 56.3 |
C4—C5—C6 | 121.96 (16) | C12—C13—H13E | 109.5 |
C10—C5—C6 | 118.86 (16) | H13A—C13—H13E | 56.3 |
C7—C6—C5 | 120.44 (18) | H13B—C13—H13E | 141.1 |
C7—C6—H6 | 119.8 | H13C—C13—H13E | 56.3 |
C5—C6—H6 | 119.8 | H13D—C13—H13E | 109.5 |
C6—C7—C8 | 120.88 (17) | C12—C13—H13F | 109.5 |
C6—C7—H7 | 119.6 | H13A—C13—H13F | 56.3 |
C8—C7—H7 | 119.6 | H13B—C13—H13F | 56.3 |
C9—C8—C7 | 120.75 (18) | H13C—C13—H13F | 141.1 |
C9—C8—H8 | 119.6 | H13D—C13—H13F | 109.5 |
C7—C8—H8 | 119.6 | H13E—C13—H13F | 109.5 |
C8—C9—C10 | 119.83 (18) | O21—C20—O22 | 122.29 (13) |
C8—C9—H9 | 120.1 | O21—C20—C2 | 117.85 (13) |
C10—C9—H9 | 120.1 | O22—C20—C2 | 119.85 (13) |
C9—C10—C5 | 119.24 (14) | C12—O10—C1 | 117.11 (12) |
C9—C10—C1 | 122.48 (16) | C20—O22—H22 | 115.8 |
C5—C10—C1 | 118.28 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H22···O21i | 0.96 | 1.70 | 2.6517 (15) | 173 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C13H10O4 |
Mr | 230.21 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 560.27 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.50 × 0.23 × 0.13 |
|
Data collection |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2124, 1987, 1516 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.596 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.116, 1.04 |
No. of reflections | 1987 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.30 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H22···O21i | 0.96 | 1.70 | 2.6517 (15) | 173.0 |
Symmetry code: (i) −x, −y+1, −z+1. |
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).