supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2010). E66, o473-o474    [ doi:10.1107/S1600536810000644 ]

2-(2-Naphthyl)-1,3-dioxane

D. Thevenet, R. Neier and H. Stoeckli-Evans

Abstract top

The title compound, C14H14O2, crystallizes in the chiral monoclinic space group P21. This acetal is composed of a planar naphthalene ring with a 1,3-dioxane ring substituent, which has a chair conformation. In the crystal structure, symmetry-related molecules are connected via a weak C-H...O interaction to form a helical chain propagating in [010]. While there are no [pi]-[pi] stacking interactions present, there are weak C-H...[pi] interactions involving the naphthalene aromatic rings, which link the helical chains to form a two-dimensional network in the (011) plane.

Comment top

Acetals are the most commonly used protecting groups for carbonyl compounds in organic synthesis (Kocienski, 1994; Showler & Darley, 1967), and many methods have been developed for their deprotection (Cordes & Bull, 1974; Fujioka et al., 2004; Ates et al., 2003). The title 2-naphthaldehyde acetal (Newman & Dickson, 1970; Carmichael & Hug, 1986) was synthesized to investigate the scope of a new photochemical reaction capable of hydrolysing the acetal into an aldehyde (Thevenet & Neier, 2010). The NMR spectra of the unsubstituted 1,3-dioxane ring displays a complicated AA'BB'MN system (Buys & Eliel, 1970), and the X-ray crystal structure was helpful for the interpretation of the NMR spectra (Thevenet & Neier, 2010).

The structure of the title compound is illustrated in Fig. 1, and the geometrical parameters are given in the Supplementary information and the archived CIF. The bond lengths and angles are close to those in three similar compounds located in the Cambridge Crystal Structure Database (CSD, V 5.30, last update Sept. 2009; Allen, 2002). For example, methyl 2,3-di-O-acteyl-4,6-O-(2-naphthyl)methylene-α-D-galactopyranoside (Borbas et al., 2002), which also crystallized in the monoclinic space group P21, and where the naphthalene ring is planar and the two six-membered rings in the galactopyranoside unit have chair conformations.

In the crystal of the title compound symmetry related molecules are connected via a C—H···O interaction (Table 1) giving rise to the formation of helical chains propagating in [010]. These chains are further linked via weak C—H···π interactions to form a two-dimensional network in (011) - see Fig. 2 and Table 1 for details.

Related literature top

For information on commonly used protecting groups for carbonyl compounds, see: Kocienski (1994); Showler & Darley (1967). For methods for their deprotection, see: Cordes & Bull (1974); Fujioka et al. (2004); Ates et al. (2003). For kinetic and thermodynamic studies of acetals and ketals in the naphthalene series and other physical data, see: Newman & Dickson (1970); Carmichael & Hug (1986). For the synthesis of 2-naphthaldehyde acetal, see Gopinath et al. (2002). For details of the new photochemical reaction to hydrolyse the acetal into an aldehyde, see Thevenet & Neier (2010). For information on 1,3-dioxane ring related compounds, see: Buys & Eliel (1970). For the synthesis and crystal structure of a related compound, see: Borbas et al. (2002). For normal geometric parameters for molecular compounds, see: Allen (2002).

Experimental top

The title compound was synthesized using a modified strategy described by (Gopinath et al., 2002). To a solution of 2-naphthaldehyde (0.64 mmol), trimethylorthoformate (1.41 mmol) and 1,3-propanediol (5.12 mmol) in dry nitromethane (2 ml) was added tetrabutylammonium tribromide (0.025 mmol). The homogeneous reaction mixture was stirred at r.t. and the progress of the reaction monitored by TLC and GC. After completion of the reaction the mixture was poured into a solution of NaHCO3 (10 ml) and the products were extracted with diethyl ether (3 × 10 ml). The organic layer was separated, dried over anhydrous Na2SO4 and concentrated. The white solid obtained was purified by recrystallization in MeOH, giving colourless thin plate-like crystals of the title compound.

1H NMR 400 MHz (CDCl3) δ 7.97 (br s, 1H, H1'), 7.85 (m, 3H, H4',5',8'), 7.60 (dd, 1H, 3J3'-4' = 8.5 Hz, 3J3'-1' = 1.7 Hz, H3'), 7.48 (m, 2H, H6',7'), 5.68 (s, 1H, H1), 4.33 (dddd, 2H, 2J3e-3a;5e-5a = -11.7 Hz, 3J3e-4a;5e-4a = 5.0 Hz, 3J3e-4e;5e-4e = 1.5 Hz, 4J3e-5e = 3.0 Hz, H3e,5e), 4.06 (ddd, 2H, 2J3a-3e;5a-5e = -11.7 Hz, 3J3a-4a;5a-4a = 12.4 Hz, 3J3a-4e;5a-4e = 2.7 Hz, H3a,5a), 2.29( dtt, 1H, 2J4a-4e = -13.5 Hz, 3J4a-3a;4a-5a = 12.4 Hz, 3J4a-3e;4a-5e = 5.0 Hz, H4a), 1.50 (dtt, 1H, 2J4e-4a = -13.5 Hz, 3J4e-3a;4e-5a = 2.7 Hz, 3J4e-3e;4e-5e = 1.5 Hz, H4 e); 13C NMR 100 MHz (CDCl3) δ 136.1 (C2'), (133.6, 133.1) (C9',10'), (128.4, 128.1, 127.7) (C4',5',8'), (126.2, 126.0) (C6',7'), 125.3 (C1'), 123.8 (C3'), 101.8 (C1), 67.5 (C3,5), 25.9 (C4); HRMS (ESI, +): [M + Na]+ = 237.09. Note: The same numbering scheme has been used for the crystal structure (Fig. 1). The torsional angles of the 1,3-dioxane ring were measured to estimate the coupling constants according to the Karplus equation.

Refinement top

In the final cycles of refinement, in the absence of significant anomalous scattering effects, 944 (93%) Friedel pairs were merged and Δf" set to zero. The H-atoms could all be located in difference electron-density maps. In the final cycles of refinement they were included in calculated positions and treated as riding atoms: C—H = 0.95–1.0 Å, with Uiso(H) = 1.2Ueq(parent C-atom). Using the one-circle Stoe Image Plate Diffraction System it is not always possible to measure 100% of the Ewald sphere, and here only 93.7% of the data were accessible out to 50° in 2θ. This has little effect on the bond distances and angles when comparing their values with those of the related structure mentioned above (Borbas et al., 2002).

Computing details top

Data collection: EXPOSE in IPDS-I (Stoe & Cie, 2000); cell refinement: CELL in IPDS-I (Stoe & Cie, 2000); data reduction: INTEGRATE in IPDS-I (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title compound, with displacement ellipoids drawn at the 50% probabilty level.
[Figure 2] Fig. 2. A view along the a axis of the crystal packing of the title compound. The C—H···O and C—H···π interactions are shown as dotted cyan and black lines, respectively. [The blue balls represent the centroids of the two aromatic rings; H-atoms not involved in the C—H···O and C—H···π interactions have been omitted for clarity; the C—H···π interactions are shown for one molecule only; see Table 1 for details].
2-(2-Naphthyl)-1,3-dioxane top
Crystal data top
C14H14O2F(000) = 228
Mr = 214.25Dx = 1.279 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 4553 reflections
a = 7.5351 (6) Åθ = 2.1–26.0°
b = 7.8575 (8) ŵ = 0.08 mm−1
c = 9.4057 (9) ÅT = 173 K
β = 92.839 (11)°Plate, colourless
V = 556.20 (9) Å30.38 × 0.30 × 0.08 mm
Z = 2
Data collection top
Stoe IPDS
diffractometer		951 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
graphiteθmax = 26.0°, θmin = 2.2°
φ rotation scansh = −8→8
4461 measured reflectionsk = −9→9
1098 independent reflectionsl = −11→11
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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0412P)2]
where P = (Fo2 + 2Fc2)/3
1098 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.13 e Å−3
1 restraintΔρmin = −0.11 e Å−3
Crystal data top
C14H14O2V = 556.20 (9) Å3
Mr = 214.25Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.5351 (6) ŵ = 0.08 mm−1
b = 7.8575 (8) ÅT = 173 K
c = 9.4057 (9) Å0.38 × 0.30 × 0.08 mm
β = 92.839 (11)°
Data collection top
Stoe IPDS
diffractometer		951 reflections with I > 2σ(I)
4461 measured reflectionsRint = 0.024
1098 independent reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.0241 restraint
wR(F2) = 0.061H-atom parameters constrained
S = 1.05Δρmax = 0.13 e Å−3
1098 reflectionsΔρmin = −0.11 e Å−3
145 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. In the final cycles of refinement, in the absence of significant anomalous scattering effects, 944 (93%) Friedel pairs were merged and Δf " set to zero. The H-atoms could all be located in difference electron-density maps. In the final cycles of refinement they were included in calculated positions and treated as riding atoms: C—H = 0.95 - 1.0 Å, with Uiso(H) = 1.2Ueq(parent C-atoms). Using the one-circle Stoe Image Plate Diffraction System it is not always possible to measure 100% of the Ewald sphere, and here only 93.7% of the data were accessible out to 50° in 2θ.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O21.16506 (19)0.57058 (16)0.43163 (12)0.0337 (4)
O61.33418 (18)0.38156 (15)0.57014 (12)0.0295 (4)
C11.1616 (2)0.4392 (2)0.53276 (17)0.0251 (5)
C1'0.9100 (2)0.46504 (19)0.69218 (16)0.0239 (5)
C2'1.0796 (2)0.5075 (2)0.66364 (16)0.0240 (5)
C31.2305 (3)0.5057 (3)0.30168 (18)0.0417 (7)
C3'1.1796 (3)0.6163 (2)0.75664 (17)0.0277 (6)
C41.4131 (3)0.4321 (3)0.32815 (19)0.0400 (7)
C4'1.1073 (3)0.6764 (2)0.87667 (18)0.0297 (6)
C51.4128 (3)0.3067 (3)0.44944 (18)0.0348 (6)
C5'0.8555 (3)0.6908 (2)1.03543 (18)0.0309 (6)
C6'0.6865 (3)0.6467 (2)1.06380 (18)0.0316 (6)
C7'0.5852 (3)0.5438 (2)0.96939 (18)0.0328 (6)
C8'0.6551 (2)0.4853 (2)0.84779 (18)0.0284 (5)
C9'0.8310 (2)0.52609 (19)0.81562 (16)0.0236 (5)
C10'0.9334 (2)0.63231 (19)0.91039 (17)0.0239 (5)
H11.088400.342500.493200.0300*
H1'0.843500.393200.628100.0290*
H3'1.297200.647500.735400.0330*
H3A1.149000.416700.262500.0500*
H3E1.234800.598700.230900.0500*
H4'1.175500.749400.938600.0360*
H4A1.450600.374100.241100.0480*
H4E1.498900.524500.351600.0480*
H5'0.922100.761601.100200.0370*
H5A1.536300.271700.475900.0420*
H5E1.345000.204000.419100.0420*
H6'0.636600.686201.148600.0380*
H7'0.467000.514600.990200.0390*
H8'0.584700.416400.784000.0340*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0500 (9)0.0289 (6)0.0225 (6)0.0088 (6)0.0049 (5)0.0012 (5)
O60.0283 (8)0.0376 (7)0.0228 (5)0.0058 (6)0.0027 (5)−0.0007 (5)
C10.0269 (11)0.0239 (8)0.0244 (8)−0.0013 (6)0.0008 (7)0.0000 (6)
C1'0.0245 (11)0.0228 (8)0.0240 (8)−0.0016 (6)−0.0023 (7)0.0007 (6)
C2'0.0265 (11)0.0229 (8)0.0225 (8)−0.0003 (7)0.0012 (7)0.0021 (7)
C30.0679 (17)0.0358 (9)0.0220 (8)0.0095 (10)0.0084 (9)0.0013 (8)
C3'0.0224 (11)0.0303 (9)0.0307 (9)−0.0050 (7)0.0031 (7)−0.0032 (7)
C40.0533 (16)0.0374 (10)0.0306 (9)−0.0015 (9)0.0158 (9)−0.0061 (8)
C4'0.0273 (12)0.0299 (9)0.0317 (9)−0.0050 (7)−0.0007 (7)−0.0058 (7)
C50.0371 (13)0.0395 (10)0.0283 (9)0.0069 (8)0.0077 (8)−0.0053 (8)
C5'0.0345 (14)0.0286 (9)0.0298 (9)0.0016 (7)0.0026 (8)−0.0023 (7)
C6'0.0322 (12)0.0327 (9)0.0309 (8)0.0066 (8)0.0105 (7)0.0024 (7)
C7'0.0230 (12)0.0382 (11)0.0377 (9)0.0031 (7)0.0063 (8)0.0075 (8)
C8'0.0222 (11)0.0316 (9)0.0313 (8)−0.0035 (8)0.0004 (7)0.0029 (7)
C9'0.0222 (11)0.0226 (8)0.0257 (8)0.0007 (6)−0.0005 (7)0.0051 (6)
C10'0.0242 (11)0.0211 (7)0.0264 (8)0.0010 (7)0.0013 (7)0.0007 (6)
Geometric parameters (Å, °) top
O2—C11.405 (2)C8'—C9'1.411 (2)
O2—C31.434 (2)C9'—C10'1.421 (2)
O6—C11.405 (2)C1—H11.0000
O6—C51.433 (2)C1'—H1'0.9500
C1—C2'1.504 (2)C3—H3A0.9900
C1'—C2'1.360 (2)C3—H3E0.9900
C1'—C9'1.415 (2)C3'—H3'0.9500
C2'—C3'1.414 (2)C4—H4A0.9900
C3—C41.502 (3)C4—H4E0.9900
C3'—C4'1.362 (3)C4'—H4'0.9500
C4—C51.508 (3)C5—H5A0.9900
C4'—C10'1.407 (3)C5—H5E0.9900
C5'—C6'1.359 (3)C5'—H5'0.9500
C5'—C10'1.417 (2)C6'—H6'0.9500
C6'—C7'1.399 (3)C7'—H7'0.9500
C7'—C8'1.363 (2)C8'—H8'0.9500
C1—O2—C3109.55 (14)C9'—C1'—H1'119.00
C1—O6—C5110.36 (13)O2—C3—H3A110.00
O2—C1—O6110.99 (13)O2—C3—H3E110.00
O2—C1—C2'108.32 (13)C4—C3—H3A110.00
O6—C1—C2'108.84 (13)C4—C3—H3E110.00
C2'—C1'—C9'121.09 (14)H3A—C3—H3E108.00
C1—C2'—C1'120.15 (14)C2'—C3'—H3'120.00
C1—C2'—C3'119.63 (14)C4'—C3'—H3'120.00
C1'—C2'—C3'120.22 (15)C3—C4—H4A110.00
O2—C3—C4110.27 (15)C3—C4—H4E110.00
C2'—C3'—C4'119.98 (19)C5—C4—H4A110.00
C3—C4—C5109.96 (18)C5—C4—H4E110.00
C3'—C4'—C10'121.12 (17)H4A—C4—H4E108.00
O6—C5—C4110.33 (18)C3'—C4'—H4'119.00
C6'—C5'—C10'120.74 (16)C10'—C4'—H4'119.00
C5'—C6'—C7'120.65 (17)O6—C5—H5A110.00
C6'—C7'—C8'120.42 (19)O6—C5—H5E110.00
C7'—C8'—C9'120.64 (16)C4—C5—H5A110.00
C1'—C9'—C8'122.48 (14)C4—C5—H5E110.00
C1'—C9'—C10'118.47 (14)H5A—C5—H5E108.00
C8'—C9'—C10'119.06 (14)C6'—C5'—H5'120.00
C4'—C10'—C5'122.42 (15)C10'—C5'—H5'120.00
C4'—C10'—C9'119.09 (14)C5'—C6'—H6'120.00
C5'—C10'—C9'118.49 (15)C7'—C6'—H6'120.00
O2—C1—H1110.00C6'—C7'—H7'120.00
O6—C1—H1110.00C8'—C7'—H7'120.00
C2'—C1—H1110.00C7'—C8'—H8'120.00
C2'—C1'—H1'119.00C9'—C8'—H8'120.00
C3—O2—C1—O664.83 (17)O2—C3—C4—C551.9 (2)
C3—O2—C1—C2'−175.74 (14)C2'—C3'—C4'—C10'−0.1 (3)
C1—O2—C3—C4−58.4 (2)C3—C4—C5—O6−50.8 (2)
C5—O6—C1—O2−64.14 (17)C3'—C4'—C10'—C5'179.07 (16)
C5—O6—C1—C2'176.74 (14)C3'—C4'—C10'—C9'−1.3 (2)
C1—O6—C5—C456.5 (2)C10'—C5'—C6'—C7'−0.6 (3)
O2—C1—C2'—C1'104.47 (17)C6'—C5'—C10'—C4'179.42 (16)
O2—C1—C2'—C3'−75.40 (18)C6'—C5'—C10'—C9'−0.2 (2)
O6—C1—C2'—C1'−134.75 (15)C5'—C6'—C7'—C8'0.4 (3)
O6—C1—C2'—C3'45.38 (19)C6'—C7'—C8'—C9'0.6 (2)
C9'—C1'—C2'—C1179.19 (14)C7'—C8'—C9'—C1'178.60 (15)
C9'—C1'—C2'—C3'−0.9 (2)C7'—C8'—C9'—C10'−1.4 (2)
C2'—C1'—C9'—C8'179.59 (15)C1'—C9'—C10'—C4'1.6 (2)
C2'—C1'—C9'—C10'−0.5 (2)C1'—C9'—C10'—C5'−178.80 (14)
C1—C2'—C3'—C4'−178.90 (15)C8'—C9'—C10'—C4'−178.48 (15)
C1'—C2'—C3'—C4'1.2 (2)C8'—C9'—C10'—C5'1.2 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1'—H1'···O2i0.952.603.349 (2)136
C5'—H5'···Cg1ii0.952.703.555 (2)151
C4'—H4'···Cg2ii0.952.923.776 (2)150
C3—H3A···Cg1i0.992.993.927 (2)159
Symmetry codes: (i) −x+2, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1'—H1'···O2i0.952.603.349 (2)136
C5'—H5'···Cg1ii0.952.703.555 (2)151
C4'—H4'···Cg2ii0.952.923.776 (2)150
C3—H3A···Cg1i0.992.993.927 (2)159
Symmetry codes: (i) −x+2, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+2.
Acknowledgements top

HSE is grateful to the XRD Application Laboratory, Microsystems Technology Division, Swiss Center for Electronics and Microtechnology, Neuchâtel, for access to the X-ray diffraction equipment.

references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

Ates, A., Gautier, A., Leroy, B., Plancher, J. M., Quesnel, Y., Vanherck, J. C. & Marko, I. E. (2003). Tetrahedron, 59, 8989–8999.

Borbas, A., Szoba, Z. B., Szilagyi, L., Benyei, A. & Liptak, A. (2002). Tetrahedron, 58, 5723–5732.

Buys, H. R. & Eliel, E. L. (1970). Tetrahedron Lett. 32, 2779–2782.

Carmichael, I. & Hug, G. L. (1986). J. Phys. Chem. Ref. Data, 15, 1–250.

Cordes, E. H. & Bull, H. G. (1974). Chem. Rev. 74, 581–603.

Fujioka, H., Sawama, Y., Murata, N., Okitsu, T., Kubo, O., Matsuda, S. & Kita, Y. (2004). J. Am. Chem. Soc. 126, 11800–11801.

Gopinath, R., Haque, S. J. & Patel, B. K. (2002). J. Org. Chem. 67, 5842–5845.

Kocienski, P. J. (1994). Carbonyl Protecting Groups, in Protecting Groups, ch. 5. New York: Thieme Medical Publishers.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.

Newman, M. S. & Dickson, R. E. (1970). J. Am. Chem. Soc. 92, 6880–6884.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Showler, A. J. & Darley, P. A. (1967). Chem. Rev. 67, 427–440.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Stoe & Cie (2000). IPDS-I. Stoe & Cie GmbH, Darmstadt, Germany.

Thevenet, D. & Neier, R. (2010). Org. Lett. In preparation.