Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101176X/ci6040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680101176X/ci6040Isup2.hkl |
CCDC reference: 170922
A solution of 2-naphthyloxyethanoic acid (5.06 g, 0.025 mol), prepared according to a published procedure (Howie et al., 2000), and thionyl chloride (7.5 ml, 0.1 mol) in CHCl3 (10 ml) was refluxed for 1.5 h and cooled. A mixture of N-bromosuccinimide (4.45 g, 0.025 mol) and aqueous HBr (48%, 2 drops) in CH2Cl2 (10 ml) was added, the mixture refluxed for 2 h, cooled, poured onto cold 2-propanol (50 ml) with stirring and left for 2 h. The solution was rotary evaporated to leave a colourless residue, which was separated by chromatography on silica. 1-Methylethyl 2-[(1-bromo-2-naphthyl)oxy]ethanoate was recrystallized from 2-propanol; 2.2 g, m.p. 331–332 K. Crystals for the X-ray study were grown by slow evaporation of a 2-propanol solution. 1H NMR (400 MHz, CDCl3, p.p.m.): d 1.23 (d, 6H, J = 6.1 Hz, Me), 4.76 (s, 2H, CH2), 5.11 (sept, J = 6.1 Hz, CH), 7.14 (d, 1H, J = 9.2hz), 7.39 (ddd, 1H, J = 1.0, 6.8, ca 8 Hz), 7.54 (ddd, 1H, J = 1.4, 6.8, 8.6 Hz), 7.65 (d, 2H, J = 8.6 Hz), 8.11 (dd, 1H, J = 1.0, 8.6 Hz). IR (KBr, cm-1): 2980, 1736, 1624, 1597, 1504, 1464, 1445, 1374, 1383, 1287, 1209, 1178, 1096, 936, 906, 804, 765, 744,709, 641, 596, 518, 414.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX in OSCAIL (McArdle, 1994, 2000) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).
C15H15BrO3 | F(000) = 328 |
Mr = 323.18 | Dx = 1.573 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3369 (4) Å | Cell parameters from 4552 reflections |
b = 4.7557 (2) Å | θ = 1.0–27.5° |
c = 14.2208 (7) Å | µ = 3.01 mm−1 |
β = 102.4951 (18)° | T = 120 K |
V = 682.52 (5) Å3 | Plate, colourless |
Z = 2 | 0.35 × 0.08 × 0.02 mm |
Enraf Nonius KappaCCD diffractometer | 2792 independent reflections |
Radiation source: fine-focus sealed tube | 2507 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ϕ–ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) | h = −13→13 |
Tmin = 0.633, Tmax = 0.633 | k = −6→5 |
4741 measured reflections | l = −16→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0509P)2 + 0.545P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2792 reflections | Δρmax = 0.79 e Å−3 |
174 parameters | Δρmin = −0.96 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.015 (16), 1058 Friedel pairs |
C15H15BrO3 | V = 682.52 (5) Å3 |
Mr = 323.18 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.3369 (4) Å | µ = 3.01 mm−1 |
b = 4.7557 (2) Å | T = 120 K |
c = 14.2208 (7) Å | 0.35 × 0.08 × 0.02 mm |
β = 102.4951 (18)° |
Enraf Nonius KappaCCD diffractometer | 2792 independent reflections |
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) | 2507 reflections with I > 2σ(I) |
Tmin = 0.633, Tmax = 0.633 | Rint = 0.052 |
4741 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.112 | Δρmax = 0.79 e Å−3 |
S = 1.08 | Δρmin = −0.96 e Å−3 |
2792 reflections | Absolute structure: Flack (1983) |
174 parameters | Absolute structure parameter: 0.015 (16), 1058 Friedel pairs |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.88045 (4) | 0.46057 (13) | 0.29285 (3) | 0.02619 (15) | |
C1 | 0.6839 (4) | 0.9920 (14) | 0.0722 (3) | 0.0231 (11) | |
C2 | 0.6901 (5) | 1.0579 (11) | −0.0237 (4) | 0.0299 (12) | |
H2 | 0.6318 | 1.1956 | −0.0579 | 0.036* | |
C3 | 0.7779 (5) | 0.9277 (16) | −0.0677 (3) | 0.0326 (13) | |
H3 | 0.7810 | 0.9748 | −0.1321 | 0.039* | |
C4 | 0.8640 (6) | 0.7234 (12) | −0.0176 (4) | 0.0314 (12) | |
H4 | 0.9241 | 0.6309 | −0.0492 | 0.038* | |
C5 | 0.8636 (5) | 0.6537 (11) | 0.0763 (4) | 0.0246 (10) | |
H5 | 0.9242 | 0.5179 | 0.1093 | 0.029* | |
C6 | 0.7714 (5) | 0.7869 (10) | 0.1238 (3) | 0.0214 (10) | |
C7 | 0.7635 (5) | 0.7257 (10) | 0.2203 (3) | 0.0217 (9) | |
C8 | 0.6723 (5) | 0.8543 (10) | 0.2632 (3) | 0.0214 (10) | |
C9 | 0.5840 (5) | 1.0563 (11) | 0.2109 (4) | 0.0265 (11) | |
H9 | 0.5199 | 1.1446 | 0.2398 | 0.032* | |
C10 | 0.5916 (5) | 1.1235 (11) | 0.1188 (4) | 0.0267 (11) | |
H10 | 0.5334 | 1.2621 | 0.0850 | 0.032* | |
O1 | 0.6745 (3) | 0.7845 (8) | 0.3571 (2) | 0.0265 (8) | |
C11 | 0.5798 (4) | 0.9111 (11) | 0.4034 (3) | 0.0249 (12) | |
H11A | 0.5779 | 1.1165 | 0.3919 | 0.030* | |
H11B | 0.6068 | 0.8793 | 0.4737 | 0.030* | |
C12 | 0.4420 (5) | 0.7905 (10) | 0.3663 (3) | 0.0241 (10) | |
O2 | 0.3540 (3) | 0.9384 (11) | 0.4023 (2) | 0.0237 (7) | |
O3 | 0.4171 (4) | 0.5876 (9) | 0.3152 (3) | 0.0351 (9) | |
C13 | 0.2134 (5) | 0.8627 (11) | 0.3683 (3) | 0.0257 (11) | |
H13 | 0.2043 | 0.6535 | 0.3641 | 0.031* | |
C14 | 0.1424 (4) | 0.974 (2) | 0.4428 (3) | 0.0339 (11) | |
H14A | 0.1766 | 0.8804 | 0.5045 | 0.051* | |
H14B | 0.0472 | 0.9375 | 0.4219 | 0.051* | |
H14C | 0.1574 | 1.1773 | 0.4503 | 0.051* | |
C15 | 0.1626 (5) | 0.9914 (16) | 0.2690 (3) | 0.0306 (12) | |
H15A | 0.1718 | 1.1964 | 0.2733 | 0.046* | |
H15B | 0.0690 | 0.9423 | 0.2458 | 0.046* | |
H15C | 0.2142 | 0.9184 | 0.2242 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0219 (2) | 0.0277 (2) | 0.0278 (2) | 0.0042 (3) | 0.00291 (15) | 0.0021 (3) |
C1 | 0.0177 (19) | 0.026 (3) | 0.0236 (19) | −0.002 (2) | 0.0009 (15) | 0.001 (3) |
C2 | 0.029 (3) | 0.027 (3) | 0.030 (3) | −0.009 (2) | −0.001 (2) | 0.003 (2) |
C3 | 0.041 (3) | 0.033 (4) | 0.024 (2) | −0.009 (3) | 0.0070 (19) | 0.003 (3) |
C4 | 0.037 (3) | 0.029 (3) | 0.029 (3) | −0.010 (2) | 0.009 (2) | −0.006 (2) |
C5 | 0.020 (2) | 0.023 (2) | 0.029 (2) | 0.0004 (18) | 0.0019 (19) | −0.001 (2) |
C6 | 0.019 (2) | 0.020 (2) | 0.023 (2) | −0.0048 (17) | 0.0005 (18) | −0.002 (2) |
C7 | 0.017 (2) | 0.022 (2) | 0.024 (2) | −0.0012 (18) | 0.0015 (18) | −0.001 (2) |
C8 | 0.021 (2) | 0.022 (2) | 0.022 (2) | −0.0016 (17) | 0.0048 (19) | −0.0026 (18) |
C9 | 0.017 (2) | 0.027 (3) | 0.034 (3) | 0.0025 (17) | 0.004 (2) | −0.003 (2) |
C10 | 0.019 (2) | 0.027 (3) | 0.030 (3) | 0.0007 (19) | −0.004 (2) | 0.006 (2) |
O1 | 0.0238 (18) | 0.034 (2) | 0.0227 (17) | 0.0080 (15) | 0.0066 (14) | 0.0031 (16) |
C11 | 0.023 (2) | 0.028 (4) | 0.025 (2) | 0.0073 (19) | 0.0073 (16) | −0.005 (2) |
C12 | 0.030 (3) | 0.020 (3) | 0.023 (2) | 0.0027 (19) | 0.007 (2) | 0.000 (2) |
O2 | 0.0210 (14) | 0.0277 (18) | 0.0229 (13) | 0.0001 (19) | 0.0055 (11) | −0.005 (2) |
O3 | 0.032 (2) | 0.031 (2) | 0.043 (2) | −0.0020 (17) | 0.0094 (17) | −0.0116 (18) |
C13 | 0.024 (2) | 0.029 (2) | 0.023 (2) | −0.0035 (18) | 0.0049 (19) | −0.0020 (19) |
C14 | 0.024 (2) | 0.051 (3) | 0.029 (2) | 0.002 (4) | 0.0108 (17) | −0.011 (4) |
C15 | 0.026 (2) | 0.036 (3) | 0.029 (2) | −0.002 (3) | 0.0050 (17) | −0.003 (3) |
Br1—C7 | 1.891 (5) | C10—H10 | 0.9500 |
C1—C2 | 1.414 (7) | O1—C11 | 1.426 (5) |
C1—C10 | 1.419 (7) | C11—C12 | 1.521 (7) |
C1—C6 | 1.422 (7) | C11—H11A | 0.9900 |
C2—C3 | 1.358 (8) | C11—H11B | 0.9900 |
C2—H2 | 0.9500 | C12—O3 | 1.201 (6) |
C3—C4 | 1.404 (9) | C12—O2 | 1.337 (6) |
C3—H3 | 0.9500 | O2—C13 | 1.474 (6) |
C4—C5 | 1.376 (7) | C13—C14 | 1.510 (7) |
C4—H4 | 0.9500 | C13—C15 | 1.524 (7) |
C5—C6 | 1.430 (7) | C13—H13 | 1.0000 |
C5—H5 | 0.9500 | C14—H14A | 0.9800 |
C6—C7 | 1.422 (6) | C14—H14B | 0.9800 |
C7—C8 | 1.374 (6) | C14—H14C | 0.9800 |
C8—O1 | 1.371 (6) | C15—H15A | 0.9800 |
C8—C9 | 1.420 (7) | C15—H15B | 0.9800 |
C9—C10 | 1.367 (7) | C15—H15C | 0.9800 |
C9—H9 | 0.9500 | ||
C2—C1—C10 | 121.8 (5) | C8—O1—C11 | 118.6 (4) |
C2—C1—C6 | 119.6 (5) | O1—C11—C12 | 111.4 (4) |
C10—C1—C6 | 118.6 (4) | O1—C11—H11A | 109.3 |
C3—C2—C1 | 121.2 (5) | C12—C11—H11A | 109.3 |
C3—C2—H2 | 119.4 | O1—C11—H11B | 109.3 |
C1—C2—H2 | 119.4 | C12—C11—H11B | 109.3 |
C2—C3—C4 | 119.7 (5) | H11A—C11—H11B | 108.0 |
C2—C3—H3 | 120.2 | O3—C12—O2 | 125.4 (5) |
C4—C3—H3 | 120.2 | O3—C12—C11 | 125.1 (4) |
C5—C4—C3 | 121.6 (5) | O2—C12—C11 | 109.4 (4) |
C5—C4—H4 | 119.2 | C12—O2—C13 | 116.7 (4) |
C3—C4—H4 | 119.2 | O2—C13—C14 | 106.1 (4) |
C4—C5—C6 | 119.6 (5) | O2—C13—C15 | 108.9 (4) |
C4—C5—H5 | 120.2 | C14—C13—C15 | 112.7 (5) |
C6—C5—H5 | 120.2 | O2—C13—H13 | 109.7 |
C1—C6—C7 | 118.4 (4) | C14—C13—H13 | 109.7 |
C1—C6—C5 | 118.3 (4) | C15—C13—H13 | 109.7 |
C7—C6—C5 | 123.3 (4) | C13—C14—H14A | 109.5 |
C8—C7—C6 | 121.7 (4) | C13—C14—H14B | 109.5 |
C8—C7—Br1 | 118.3 (4) | H14A—C14—H14B | 109.5 |
C6—C7—Br1 | 120.0 (3) | C13—C14—H14C | 109.5 |
O1—C8—C7 | 117.2 (4) | H14A—C14—H14C | 109.5 |
O1—C8—C9 | 123.2 (4) | H14B—C14—H14C | 109.5 |
C7—C8—C9 | 119.6 (4) | C13—C15—H15A | 109.5 |
C10—C9—C8 | 119.8 (5) | C13—C15—H15B | 109.5 |
C10—C9—H9 | 120.1 | H15A—C15—H15B | 109.5 |
C8—C9—H9 | 120.1 | C13—C15—H15C | 109.5 |
C9—C10—C1 | 121.9 (5) | H15A—C15—H15C | 109.5 |
C9—C10—H10 | 119.1 | H15B—C15—H15C | 109.5 |
C1—C10—H10 | 119.1 |
Experimental details
Crystal data | |
Chemical formula | C15H15BrO3 |
Mr | 323.18 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 10.3369 (4), 4.7557 (2), 14.2208 (7) |
β (°) | 102.4951 (18) |
V (Å3) | 682.52 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.01 |
Crystal size (mm) | 0.35 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Enraf Nonius KappaCCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.633, 0.633 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4741, 2792, 2507 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.112, 1.08 |
No. of reflections | 2792 |
No. of parameters | 174 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.79, −0.96 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.015 (16), 1058 Friedel pairs |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX in OSCAIL (McArdle, 1994, 2000) and ORTEP-3 for Windows (Farrugia, 1997), CIFTAB (Sheldrick, 1997).
The title compound, (1), was obtained by the reaction sequence shown in the reaction scheme below. Of particular interest in this scheme were the products of reaction of (2) with N-bromosuccinimide and the competition between bromination of the aromatic ring and the methylene group, α to the carbonyl group. NMR spectroscopy of the final reaction mixture clearly showed that reaction occurred completely in the aromatic ring: no indications for 2-bromo-2-(2-naphthyloxy)ethanoic acid were found.
The asymmetric unit of (1) is shown in Fig. 1 with the numbering scheme; intramolecular C—H···Br are present (C5—H5···Br1, Table 1) although not shown in this diagram.
Molecules of (1) are linked by C—H···π interactions, viz. C4—H4···π. The C1–C6 ring is the acceptor at (2 - x, -1/2 + y, -z), with a C4–centroid distance of 4.146 (7) Å. These are represented in Fig. 2, which shows the zigzag of the resultant chain parallel to the (010) direction (Spek 2001).