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The redetermination of the title compound, C12H10O3, agrees completely with the results previously reported by Pattabhi, Ragnuthan & Chacko [Acta Cryst. (1973), B34, 3118–3120], but with improved precision. In addition, now reported are intermolecular π–π, C—H...π and aryl C—H...O interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020080/cf6027sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020080/cf6027Isup2.hkl
Contains datablock I

CCDC reference: 155895

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.049
  • wR factor = 0.126
  • Data-to-parameter ratio = 25.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSMU_01 Alert C The ratio of given/expected absorption coefficient lies outside the range 0.99 <> 1.01 Calculated value of mu = 0.097 Value of mu given = 0.100 ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.782 0.997 Tmin' and Tmax expected: 0.941 0.997 RR' = 0.831 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

A search of the Cambridge Structural Database (Allen & Kennard, 1993) at the Chemical database service of the EPSRC (Fletcher et al., 1996) reveals that the structure of the title compound, (I), was first reported (NAPXAC10; Pattabhi et al., 1973) with R = 0.083 for 1623 reflections. The redetermination reported here with current refinement software and a more extensive set of intensity data yields a model of greater precision and improved R. Allowing for the different choice of unit cell (P21/n for P21/c) and atom-labelling scheme (Fig. 1), the results of the redetermination (Table 1) agree in all respects with those of Pattabhi et al. (1973).

A feature unremarked on in the original determination but replicated here was the variation in C—C bond lengths within the naphthalene ring system of the molecule. The bonds C1—C2, C4—C5, C6—C7 and C9—C10 at the corners of the ring system are in the range 1.3568 (19)–1.362 (2) Å (Table 1). The remainder are longer, ranging from 1.392 (2) to 1.4197 (18) Å. The difference between the bond lengths of the two groups is at least 0.03 Å and no less than 15 times the s.u.'s, and therefore significant and clearly of the type described elsewhere, e.g. for naphthalene (Brock & Dunitz, 1982).

The planarity of the molecule as a whole also merits comment. In addition to the undoubted planarity of the naphthalene group [maximum out of plane distance 0.0079 (13) Å for C7], the dihedral angles at the C11—C12 bond are clearly indicative of comparable planarity for the group comprising C11, C12 and O1 to O3 [maximum out of plane distance 0.0066 (9) for C11]. It is tempting then to estimate the angle between these planar entities by means of the dihedral angles at the C1—O1 bond which yield an average value of 5.88 (12)°. This, however, overestimates the value of 4.13 (5)° from mean-plane calculation because it fails to take account of the effect of the C1—O1—C11—C12 torsion angle which accounts for the difference. The departure from planarity is not in any case large.

As shown in Fig. 2, in which the essentially planar molecules are seen edge-on, the molecules are packed face-to-face to form layers parallel to (001) at z = 0 and 1/2. Three significant intermolecular contacts arise within the layers. The first of these is the previously reported centrosymmetrically hydrogen-bonded pair-wise association of the molecules (Fig. 1 and Table 2). The others, elucidated by PLATON (Spek, 1990), both involve the π system of the C3–C8 ring (with centroid Cg) of the naphthalene group. In one of these, the rings are found in centrosymmetrically related pairs and are then by definition parallel to one another within the pair (Fig. 3). This interaction is characterized by the perpendicular distance between the parallel planes (3.604 Å), the distance between their centroids [Cg···Cgi 4.028 Å; symmetry code: (i) 1 - x, 1 - y, -z] and the angle between these vectors (26.52°). Finally, there is an interaction of the form C11—H11B···Cgii [symmetry code: (ii) x, y - 1, z]. This is characterized by five parameters as: (I) the distance between H and the centroid of the π system (H..-Cgii 2.792 Å); (ii) the perpendicular distance from H to the plane of the aryl ring (H–perp 2.747 Å); (iii) the angle between these vectors (γ 10.28°); (iv) the angle C11—H11B.·Cgii (137.29°); and (v) the C11.·Cgii distance (3.56 Å).

As noted above, the crystallographic centres of symmetry are involved in relationships between molecules within the layers. The layers themselves are related instead by the operation of the crystallographic n-glides, and equivalently by the crystallographic twofold screw axes. he tilt of the molecules relative to (010) therefore alternates from one layer to the next to yield a crisscross effect overall. The only interaction of any significance between the layers is the weak hydrogen-bond-type contact C5—H5.·O2 (Table 2).

Experimental top

As reported by Fries (1921), basic hydrolysis of methyl 2-naphthalenyloxyethanoate prepared by reaction of 2-naphthol and methyl bromoethanoate yielded (I), which was recrystallized from 1% aqueous hydrochloric acid solution [m.p. 432–433 K (literature value 428 K)].

Refinement top

Aryl and methylene H atoms were placed in calculated positions with C—H = 0.93 and 0.97 Å, respectively, and refined with a riding model with Uiso equal to 1.2Ueq of the C atomto which they are attached. The hydroxy H (H3A) atom was found in a difference map and refined isotropically in the usual manner.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The centrosymmetric hydrogen-bonded dimer of (I). All non-H of the asymmetric unit and selected non-H atoms of the symmetry related molecule [symmetry code: (i) -x + 2, -y - 1, -z] are labelled. Non-H atoms are shown as 50% probability ellipsoids and H atoms are shown as open circles. Dashed lines represent H···O contacts.
[Figure 2] Fig. 2. Part of a layer of molecules of (I) parallel to (001). The representation of the atoms is the same as in Fig. 1 and dashed lines represent intermolecular contacts (see text).
[Figure 3] Fig. 3. A ππ stacked pair of molecules of (I). The representation of the atoms is the same as in Figs. 1 and 2, and selected atoms are labelled [symmetry code: (i) 1 - x, 1 - y, -z].
2-Naphthalenyloxyethanoic acid top
Crystal data top
C12H10O3F(000) = 424
Mr = 202.20Dx = 1.354 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 12.3112 (10) ÅCell parameters from 1594 reflections
b = 6.8401 (5) Åθ = 3.0–25.5°
c = 13.1658 (10) ŵ = 0.10 mm1
β = 116.507 (2)°T = 295 K
V = 992.14 (13) Å3Needle, colourless
Z = 40.60 × 0.10 × 0.03 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
3577 independent reflections
Radiation source: fine-focus sealed tube1511 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ϕ and ω scansθmax = 32.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 1815
Tmin = 0.782, Tmax = 0.997k = 109
9994 measured reflectionsl = 1916
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 0.82 w = 1/[σ2(Fo2) + (0.059P)2]
where P = (Fo2 + 2Fc2)/3
3577 reflections(Δ/σ)max < 0.001
140 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C12H10O3V = 992.14 (13) Å3
Mr = 202.20Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.3112 (10) ŵ = 0.10 mm1
b = 6.8401 (5) ÅT = 295 K
c = 13.1658 (10) Å0.60 × 0.10 × 0.03 mm
β = 116.507 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
3577 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1511 reflections with I > 2σ(I)
Tmin = 0.782, Tmax = 0.997Rint = 0.043
9994 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 0.82Δρmax = 0.18 e Å3
3577 reflectionsΔρmin = 0.20 e Å3
140 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

H of C—H in calculated positions and refined with a riding model. Hydroxyl found in difference map and refined isotropically in the usual manner.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.79229 (12)0.19222 (19)0.02361 (12)0.0404 (3)
C20.71463 (13)0.27454 (19)0.07653 (11)0.0413 (3)
H20.70210.21590.14460.050*
C30.65258 (12)0.44997 (19)0.07742 (11)0.0365 (3)
C40.57137 (13)0.5404 (2)0.17977 (12)0.0444 (4)
H40.55810.48420.24870.053*
C50.51216 (14)0.7081 (2)0.17937 (13)0.0542 (4)
H50.45850.76490.24760.065*
C60.53180 (16)0.7949 (2)0.07700 (14)0.0621 (5)
H60.49110.90960.07720.074*
C70.61011 (14)0.7133 (2)0.02353 (13)0.0547 (4)
H70.62260.77370.09120.066*
C80.67273 (12)0.53836 (19)0.02683 (11)0.0401 (3)
C90.75357 (13)0.4456 (2)0.12874 (12)0.0463 (4)
H90.76700.50090.19790.056*
C100.81189 (13)0.2779 (2)0.12773 (12)0.0462 (4)
H100.86480.21950.19570.055*
O10.85899 (9)0.02366 (14)0.03510 (8)0.0512 (3)
C110.83497 (13)0.07882 (19)0.06582 (12)0.0442 (4)
H11A0.85490.00230.11560.053*
H11B0.74960.11250.10520.053*
C120.91077 (13)0.2611 (2)0.03524 (12)0.0408 (3)
O20.97923 (10)0.30728 (14)0.06142 (9)0.0534 (3)
O30.89432 (10)0.36239 (16)0.12538 (9)0.0535 (3)
H3A0.9313 (17)0.474 (3)0.1063 (14)0.082 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0427 (8)0.0345 (7)0.0431 (8)0.0062 (6)0.0183 (7)0.0015 (6)
C20.0468 (9)0.0393 (8)0.0367 (8)0.0031 (6)0.0176 (6)0.0057 (6)
C30.0360 (8)0.0359 (7)0.0368 (8)0.0003 (6)0.0156 (6)0.0009 (6)
C40.0426 (9)0.0493 (9)0.0382 (8)0.0038 (7)0.0152 (7)0.0018 (6)
C50.0525 (10)0.0589 (10)0.0456 (9)0.0187 (8)0.0168 (7)0.0071 (8)
C60.0688 (11)0.0550 (10)0.0602 (11)0.0270 (8)0.0268 (9)0.0015 (8)
C70.0633 (11)0.0528 (9)0.0463 (9)0.0142 (8)0.0228 (8)0.0078 (7)
C80.0412 (8)0.0389 (8)0.0402 (8)0.0023 (6)0.0182 (6)0.0038 (6)
C90.0506 (9)0.0513 (9)0.0343 (8)0.0061 (7)0.0164 (7)0.0073 (7)
C100.0496 (9)0.0481 (9)0.0359 (8)0.0095 (7)0.0147 (7)0.0011 (6)
O10.0616 (7)0.0423 (6)0.0417 (6)0.0171 (5)0.0160 (5)0.0024 (4)
C110.0495 (9)0.0382 (8)0.0432 (8)0.0070 (6)0.0192 (7)0.0029 (6)
C120.0445 (8)0.0347 (7)0.0455 (9)0.0007 (6)0.0221 (7)0.0012 (7)
O20.0659 (7)0.0442 (6)0.0445 (6)0.0159 (5)0.0197 (6)0.0005 (5)
O30.0696 (8)0.0418 (6)0.0450 (6)0.0141 (5)0.0218 (5)0.0027 (5)
Geometric parameters (Å, º) top
C1—C21.3580 (19)C7—C81.4135 (19)
C1—O11.3840 (16)C7—H70.930
C1—C101.4091 (18)C8—C91.4146 (19)
C2—C31.4197 (18)C9—C101.3568 (19)
C2—H20.930C9—H90.930
C3—C41.4125 (18)C10—H100.930
C3—C81.4167 (17)O1—C111.4118 (15)
C4—C51.361 (2)C11—C121.5005 (19)
C4—H40.930C11—H11A0.970
C5—C61.392 (2)C11—H11B0.970
C5—H50.930C12—O21.2134 (15)
C6—C71.362 (2)C12—O31.3097 (16)
C6—H60.930O3—H3A0.87 (2)
C2—C1—O1125.30 (12)C7—C8—C9123.49 (12)
C2—C1—C10120.84 (12)C7—C8—C3118.31 (12)
O1—C1—C10113.86 (12)C9—C8—C3118.19 (12)
C1—C2—C3120.10 (12)C10—C9—C8121.41 (12)
C1—C2—H2119.9C10—C9—H9119.3
C3—C2—H2119.9C8—C9—H9119.3
C4—C3—C8118.73 (12)C9—C10—C1119.98 (13)
C4—C3—C2121.80 (12)C9—C10—H10120.0
C8—C3—C2119.46 (12)C1—C10—H10120.0
C5—C4—C3121.18 (13)C1—O1—C11116.48 (10)
C5—C4—H4119.4O1—C11—C12108.42 (11)
C3—C4—H4119.4O1—C11—H11A110.0
C4—C5—C6120.11 (14)C12—C11—H11A110.0
C4—C5—H5119.9O1—C11—H11B110.0
C6—C5—H5119.9C12—C11—H11B110.0
C7—C6—C5120.54 (14)H11A—C11—H11B108.4
C7—C6—H6119.7O2—C12—O3124.52 (13)
C5—C6—H6119.7O2—C12—C11123.74 (12)
C6—C7—C8121.12 (13)O3—C12—C11111.74 (13)
C6—C7—H7119.4C12—O3—H3A110.8 (11)
C8—C7—H7119.4
O1—C1—C2—C3179.00 (12)C4—C3—C8—C9179.54 (12)
C10—C1—C2—C30.5 (2)C2—C3—C8—C90.84 (19)
C1—C2—C3—C4179.82 (13)C7—C8—C9—C10179.87 (14)
C1—C2—C3—C80.2 (2)C3—C8—C9—C100.8 (2)
C8—C3—C4—C50.6 (2)C8—C9—C10—C10.1 (2)
C2—C3—C4—C5179.76 (14)C2—C1—C10—C90.5 (2)
C3—C4—C5—C60.6 (2)O1—C1—C10—C9179.00 (13)
C4—C5—C6—C70.0 (3)C2—C1—O1—C116.1 (2)
C5—C6—C7—C80.4 (3)C10—C1—O1—C11174.35 (12)
C6—C7—C8—C9178.97 (15)C1—O1—C11—C12177.02 (11)
C6—C7—C8—C30.4 (2)O1—C11—C12—O20.55 (19)
C4—C3—C8—C70.2 (2)O1—C11—C12—O3179.07 (11)
C2—C3—C8—C7179.79 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2i0.87 (2)1.79 (2)2.6586 (14)174.6 (18)
C5—H5···O2ii0.932.653.3220 (19)129
Symmetry codes: (i) x+2, y1, z; (ii) x1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC12H10O3
Mr202.20
Crystal system, space groupMonoclinic, P21/n
Temperature (K)295
a, b, c (Å)12.3112 (10), 6.8401 (5), 13.1658 (10)
β (°) 116.507 (2)
V3)992.14 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.60 × 0.10 × 0.03
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.782, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
9994, 3577, 1511
Rint0.043
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.126, 0.82
No. of reflections3577
No. of parameters140
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.20

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
C1—C21.3580 (19)C5—C61.392 (2)
C1—O11.3840 (16)C6—C71.362 (2)
C1—C101.4091 (18)C7—C81.4135 (19)
C2—C31.4197 (18)C8—C91.4146 (19)
C3—C41.4125 (18)C9—C101.3568 (19)
C3—C81.4167 (17)O3—H3A0.87 (2)
C4—C51.361 (2)
C12—O3—H3A110.8 (11)
C2—C1—O1—C116.1 (2)O1—C11—C12—O20.55 (19)
C10—C1—O1—C11174.35 (12)O1—C11—C12—O3179.07 (11)
C1—O1—C11—C12177.02 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2i0.87 (2)1.79 (2)2.6586 (14)174.6 (18)
C5—H5···O2ii0.932.653.3220 (19)129.3
Symmetry codes: (i) x+2, y1, z; (ii) x1/2, y+1/2, z1/2.
 

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