Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020080/cf6027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020080/cf6027Isup2.hkl |
CCDC reference: 155895
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)].
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.
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.
C12H10O3 | F(000) = 424 |
Mr = 202.20 | Dx = 1.354 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.3112 (10) Å | Cell parameters from 1594 reflections |
b = 6.8401 (5) Å | θ = 3.0–25.5° |
c = 13.1658 (10) Å | µ = 0.10 mm−1 |
β = 116.507 (2)° | T = 295 K |
V = 992.14 (13) Å3 | Needle, colourless |
Z = 4 | 0.60 × 0.10 × 0.03 mm |
Bruker SMART 1000 CCD diffractometer | 3577 independent reflections |
Radiation source: fine-focus sealed tube | 1511 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 32.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −18→15 |
Tmin = 0.782, Tmax = 0.997 | k = −10→9 |
9994 measured reflections | l = −19→16 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H 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 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C12H10O3 | V = 992.14 (13) Å3 |
Mr = 202.20 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.3112 (10) Å | µ = 0.10 mm−1 |
b = 6.8401 (5) Å | T = 295 K |
c = 13.1658 (10) Å | 0.60 × 0.10 × 0.03 mm |
β = 116.507 (2)° |
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 = 0.997 | Rint = 0.043 |
9994 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.82 | Δρmax = 0.18 e Å−3 |
3577 reflections | Δρmin = −0.20 e Å−3 |
140 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.79229 (12) | 0.19222 (19) | 0.02361 (12) | 0.0404 (3) | |
C2 | 0.71463 (13) | 0.27454 (19) | −0.07653 (11) | 0.0413 (3) | |
H2 | 0.7021 | 0.2159 | −0.1446 | 0.050* | |
C3 | 0.65258 (12) | 0.44997 (19) | −0.07742 (11) | 0.0365 (3) | |
C4 | 0.57137 (13) | 0.5404 (2) | −0.17977 (12) | 0.0444 (4) | |
H4 | 0.5581 | 0.4842 | −0.2487 | 0.053* | |
C5 | 0.51216 (14) | 0.7081 (2) | −0.17937 (13) | 0.0542 (4) | |
H5 | 0.4585 | 0.7649 | −0.2476 | 0.065* | |
C6 | 0.53180 (16) | 0.7949 (2) | −0.07700 (14) | 0.0621 (5) | |
H6 | 0.4911 | 0.9096 | −0.0772 | 0.074* | |
C7 | 0.61011 (14) | 0.7133 (2) | 0.02353 (13) | 0.0547 (4) | |
H7 | 0.6226 | 0.7737 | 0.0912 | 0.066* | |
C8 | 0.67273 (12) | 0.53836 (19) | 0.02683 (11) | 0.0401 (3) | |
C9 | 0.75357 (13) | 0.4456 (2) | 0.12874 (12) | 0.0463 (4) | |
H9 | 0.7670 | 0.5009 | 0.1979 | 0.056* | |
C10 | 0.81189 (13) | 0.2779 (2) | 0.12773 (12) | 0.0462 (4) | |
H10 | 0.8648 | 0.2195 | 0.1957 | 0.055* | |
O1 | 0.85899 (9) | 0.02366 (14) | 0.03510 (8) | 0.0512 (3) | |
C11 | 0.83497 (13) | −0.07882 (19) | −0.06582 (12) | 0.0442 (4) | |
H11A | 0.8549 | 0.0023 | −0.1156 | 0.053* | |
H11B | 0.7496 | −0.1125 | −0.1052 | 0.053* | |
C12 | 0.91077 (13) | −0.2611 (2) | −0.03524 (12) | 0.0408 (3) | |
O2 | 0.97923 (10) | −0.30728 (14) | 0.06142 (9) | 0.0534 (3) | |
O3 | 0.89432 (10) | −0.36239 (16) | −0.12538 (9) | 0.0535 (3) | |
H3A | 0.9313 (17) | −0.474 (3) | −0.1063 (14) | 0.082 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0427 (8) | 0.0345 (7) | 0.0431 (8) | 0.0062 (6) | 0.0183 (7) | −0.0015 (6) |
C2 | 0.0468 (9) | 0.0393 (8) | 0.0367 (8) | 0.0031 (6) | 0.0176 (6) | −0.0057 (6) |
C3 | 0.0360 (8) | 0.0359 (7) | 0.0368 (8) | −0.0003 (6) | 0.0156 (6) | −0.0009 (6) |
C4 | 0.0426 (9) | 0.0493 (9) | 0.0382 (8) | 0.0038 (7) | 0.0152 (7) | −0.0018 (6) |
C5 | 0.0525 (10) | 0.0589 (10) | 0.0456 (9) | 0.0187 (8) | 0.0168 (7) | 0.0071 (8) |
C6 | 0.0688 (11) | 0.0550 (10) | 0.0602 (11) | 0.0270 (8) | 0.0268 (9) | 0.0015 (8) |
C7 | 0.0633 (11) | 0.0528 (9) | 0.0463 (9) | 0.0142 (8) | 0.0228 (8) | −0.0078 (7) |
C8 | 0.0412 (8) | 0.0389 (8) | 0.0402 (8) | 0.0023 (6) | 0.0182 (6) | −0.0038 (6) |
C9 | 0.0506 (9) | 0.0513 (9) | 0.0343 (8) | 0.0061 (7) | 0.0164 (7) | −0.0073 (7) |
C10 | 0.0496 (9) | 0.0481 (9) | 0.0359 (8) | 0.0095 (7) | 0.0147 (7) | 0.0011 (6) |
O1 | 0.0616 (7) | 0.0423 (6) | 0.0417 (6) | 0.0171 (5) | 0.0160 (5) | −0.0024 (4) |
C11 | 0.0495 (9) | 0.0382 (8) | 0.0432 (8) | 0.0070 (6) | 0.0192 (7) | −0.0029 (6) |
C12 | 0.0445 (8) | 0.0347 (7) | 0.0455 (9) | 0.0007 (6) | 0.0221 (7) | −0.0012 (7) |
O2 | 0.0659 (7) | 0.0442 (6) | 0.0445 (6) | 0.0159 (5) | 0.0197 (6) | 0.0005 (5) |
O3 | 0.0696 (8) | 0.0418 (6) | 0.0450 (6) | 0.0141 (5) | 0.0218 (5) | −0.0027 (5) |
C1—C2 | 1.3580 (19) | C7—C8 | 1.4135 (19) |
C1—O1 | 1.3840 (16) | C7—H7 | 0.930 |
C1—C10 | 1.4091 (18) | C8—C9 | 1.4146 (19) |
C2—C3 | 1.4197 (18) | C9—C10 | 1.3568 (19) |
C2—H2 | 0.930 | C9—H9 | 0.930 |
C3—C4 | 1.4125 (18) | C10—H10 | 0.930 |
C3—C8 | 1.4167 (17) | O1—C11 | 1.4118 (15) |
C4—C5 | 1.361 (2) | C11—C12 | 1.5005 (19) |
C4—H4 | 0.930 | C11—H11A | 0.970 |
C5—C6 | 1.392 (2) | C11—H11B | 0.970 |
C5—H5 | 0.930 | C12—O2 | 1.2134 (15) |
C6—C7 | 1.362 (2) | C12—O3 | 1.3097 (16) |
C6—H6 | 0.930 | O3—H3A | 0.87 (2) |
C2—C1—O1 | 125.30 (12) | C7—C8—C9 | 123.49 (12) |
C2—C1—C10 | 120.84 (12) | C7—C8—C3 | 118.31 (12) |
O1—C1—C10 | 113.86 (12) | C9—C8—C3 | 118.19 (12) |
C1—C2—C3 | 120.10 (12) | C10—C9—C8 | 121.41 (12) |
C1—C2—H2 | 119.9 | C10—C9—H9 | 119.3 |
C3—C2—H2 | 119.9 | C8—C9—H9 | 119.3 |
C4—C3—C8 | 118.73 (12) | C9—C10—C1 | 119.98 (13) |
C4—C3—C2 | 121.80 (12) | C9—C10—H10 | 120.0 |
C8—C3—C2 | 119.46 (12) | C1—C10—H10 | 120.0 |
C5—C4—C3 | 121.18 (13) | C1—O1—C11 | 116.48 (10) |
C5—C4—H4 | 119.4 | O1—C11—C12 | 108.42 (11) |
C3—C4—H4 | 119.4 | O1—C11—H11A | 110.0 |
C4—C5—C6 | 120.11 (14) | C12—C11—H11A | 110.0 |
C4—C5—H5 | 119.9 | O1—C11—H11B | 110.0 |
C6—C5—H5 | 119.9 | C12—C11—H11B | 110.0 |
C7—C6—C5 | 120.54 (14) | H11A—C11—H11B | 108.4 |
C7—C6—H6 | 119.7 | O2—C12—O3 | 124.52 (13) |
C5—C6—H6 | 119.7 | O2—C12—C11 | 123.74 (12) |
C6—C7—C8 | 121.12 (13) | O3—C12—C11 | 111.74 (13) |
C6—C7—H7 | 119.4 | C12—O3—H3A | 110.8 (11) |
C8—C7—H7 | 119.4 | ||
O1—C1—C2—C3 | −179.00 (12) | C4—C3—C8—C9 | 179.54 (12) |
C10—C1—C2—C3 | 0.5 (2) | C2—C3—C8—C9 | −0.84 (19) |
C1—C2—C3—C4 | 179.82 (13) | C7—C8—C9—C10 | −179.87 (14) |
C1—C2—C3—C8 | 0.2 (2) | C3—C8—C9—C10 | 0.8 (2) |
C8—C3—C4—C5 | −0.6 (2) | C8—C9—C10—C1 | −0.1 (2) |
C2—C3—C4—C5 | 179.76 (14) | C2—C1—C10—C9 | −0.5 (2) |
C3—C4—C5—C6 | 0.6 (2) | O1—C1—C10—C9 | 179.00 (13) |
C4—C5—C6—C7 | 0.0 (3) | C2—C1—O1—C11 | −6.1 (2) |
C5—C6—C7—C8 | −0.4 (3) | C10—C1—O1—C11 | 174.35 (12) |
C6—C7—C8—C9 | −178.97 (15) | C1—O1—C11—C12 | −177.02 (11) |
C6—C7—C8—C3 | 0.4 (2) | O1—C11—C12—O2 | 0.55 (19) |
C4—C3—C8—C7 | 0.2 (2) | O1—C11—C12—O3 | −179.07 (11) |
C2—C3—C8—C7 | 179.79 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2i | 0.87 (2) | 1.79 (2) | 2.6586 (14) | 174.6 (18) |
C5—H5···O2ii | 0.93 | 2.65 | 3.3220 (19) | 129 |
Symmetry codes: (i) −x+2, −y−1, −z; (ii) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H10O3 |
Mr | 202.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 12.3112 (10), 6.8401 (5), 13.1658 (10) |
β (°) | 116.507 (2) |
V (Å3) | 992.14 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.60 × 0.10 × 0.03 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.782, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9994, 3577, 1511 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.126, 0.82 |
No. of reflections | 3577 |
No. of parameters | 140 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.20 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
C1—C2 | 1.3580 (19) | C5—C6 | 1.392 (2) |
C1—O1 | 1.3840 (16) | C6—C7 | 1.362 (2) |
C1—C10 | 1.4091 (18) | C7—C8 | 1.4135 (19) |
C2—C3 | 1.4197 (18) | C8—C9 | 1.4146 (19) |
C3—C4 | 1.4125 (18) | C9—C10 | 1.3568 (19) |
C3—C8 | 1.4167 (17) | O3—H3A | 0.87 (2) |
C4—C5 | 1.361 (2) | ||
C12—O3—H3A | 110.8 (11) | ||
C2—C1—O1—C11 | −6.1 (2) | O1—C11—C12—O2 | 0.55 (19) |
C10—C1—O1—C11 | 174.35 (12) | O1—C11—C12—O3 | −179.07 (11) |
C1—O1—C11—C12 | −177.02 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2i | 0.87 (2) | 1.79 (2) | 2.6586 (14) | 174.6 (18) |
C5—H5···O2ii | 0.93 | 2.65 | 3.3220 (19) | 129.3 |
Symmetry codes: (i) −x+2, −y−1, −z; (ii) x−1/2, −y+1/2, z−1/2. |
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).