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Acta Cryst. (2009). E65, o760    [ doi:10.1107/S1600536809008691 ]

Diethyl 3H-naphtho[2,1-b]pyran-2,3-dicarboxylate

A. M. Asiri and S. W. Ng

Abstract top

The sp3-hybridized methine C atom in the title compound, C19H18O5, lies out of the mean plane of the remaining 13 atoms of the naphthopyran fused-ring system by 0.571 (1) Å, and its H atom occupies a pseudo-equatorial site.

Comment top

The molecular structure of the title compound is shown in Fig. 1.

Related literature top

For a review on 2H-naphthopyrans, see: Crano & Guglielmetti (1999). For the structure of the dimethyl ester analog, see: Ramazani et al. (2002).

Experimental top

Triphenylphosphine (13.1 g, 0.05 mol) and 2-hydroxy-1-naphthaldehyde (8.6 g, 0.05 mol) were dissolved in dichloromethane (100 ml). The solution was cooled to 263 K. Diethyl acetylenedicarboxylate (8.5 g, 0.05 mol) dissolved in dichloromethane (20 ml) was added over 20 min. The mixture was then stirred for 2 days. The solvent was removed under reduced pressure and the residue was purified by column chromatography over silica gel; ether-toulene was the eluent. The solvent was removed under reduced pressure and the product was obtained as bright yellow crystals by recrystallization from toulene (14.7 g, 90% yield).

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95-1.00 Å) and were included in the refinement in the riding model approximation, with Ueq(H) fixed at 1.2U(C) or 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellisoid plot (Barbour, 2001) of C19H18O5; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.
Diethyl 3H-naphtho[2,1-b]pyran-2,3-dicarboxylate top
Crystal data top
C19H18O5F(000) = 1376
Mr = 326.33Dx = 1.344 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9911 reflections
a = 28.5156 (3) Åθ = 2.7–28.7°
b = 7.5804 (1) ŵ = 0.10 mm−1
c = 18.5365 (2) ÅT = 123 K
β = 126.413 (1)°Prism, yellow
V = 3224.54 (6) Å30.30 × 0.30 × 0.15 mm
Z = 8
Data collection top
Bruker SMART APEX
diffractometer		3453 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
graphiteθmax = 27.5°, θmin = 1.8°
ω scansh = −36→36
14849 measured reflectionsk = −9→9
3698 independent reflectionsl = −23→24
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0623P)2 + 2.3553P]
where P = (Fo2 + 2Fc2)/3
3698 reflections(Δ/σ)max = 0.001
219 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C19H18O5V = 3224.54 (6) Å3
Mr = 326.33Z = 8
Monoclinic, C2/cMo Kα radiation
a = 28.5156 (3) ŵ = 0.10 mm−1
b = 7.5804 (1) ÅT = 123 K
c = 18.5365 (2) Å0.30 × 0.30 × 0.15 mm
β = 126.413 (1)°
Data collection top
Bruker SMART APEX
diffractometer		3453 reflections with I > 2σ(I)
14849 measured reflectionsRint = 0.019
3698 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.108Δρmax = 0.25 e Å−3
S = 1.03Δρmin = −0.29 e Å−3
3698 reflectionsAbsolute structure: ?
219 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.62940 (3)0.55357 (10)0.45186 (5)0.01852 (17)
O20.50133 (4)0.28978 (12)0.34344 (6)0.0312 (2)
O30.59191 (3)0.24695 (10)0.38235 (5)0.02188 (18)
O40.46280 (3)0.74298 (11)0.29129 (5)0.02427 (19)
O50.46291 (3)0.79011 (11)0.41127 (5)0.02219 (18)
C10.65404 (4)0.50737 (13)0.53927 (7)0.0168 (2)
C20.70965 (5)0.42956 (14)0.58737 (7)0.0204 (2)
H20.72820.40940.55920.025*
C30.73670 (4)0.38328 (15)0.67493 (7)0.0213 (2)
H30.77340.32560.70670.026*
C40.71080 (4)0.42003 (14)0.71938 (7)0.0185 (2)
C50.73888 (5)0.37331 (15)0.81041 (7)0.0230 (2)
H50.77490.31170.84190.028*
C60.71465 (5)0.41601 (16)0.85348 (7)0.0251 (2)
H60.73390.38390.91450.030*
C70.66120 (5)0.50753 (16)0.80743 (7)0.0232 (2)
H70.64540.54070.83830.028*
C80.63177 (4)0.54922 (14)0.71821 (7)0.0191 (2)
H80.59530.60800.68760.023*
C90.65548 (4)0.50523 (13)0.67154 (7)0.0162 (2)
C100.62585 (4)0.54314 (13)0.57807 (7)0.0159 (2)
C110.56863 (4)0.62474 (13)0.52185 (7)0.0166 (2)
H110.55170.67600.54810.020*
C120.53990 (4)0.62713 (13)0.43245 (7)0.0173 (2)
C130.56717 (4)0.53746 (14)0.39323 (7)0.0180 (2)
H130.55300.59920.33600.022*
C140.54901 (4)0.34276 (15)0.37069 (7)0.0193 (2)
C150.58056 (5)0.06142 (14)0.35676 (8)0.0238 (2)
H15A0.55340.04950.29070.029*
H15B0.56310.00290.38340.029*
C160.63836 (6)−0.01934 (18)0.39174 (10)0.0373 (3)
H16A0.6331−0.14470.37580.056*
H16B0.6646−0.00700.45710.056*
H16C0.65520.04090.36520.056*
C170.48480 (4)0.72331 (13)0.37016 (7)0.0178 (2)
C180.41183 (5)0.90167 (15)0.35647 (7)0.0234 (2)
H18A0.38100.83890.30120.028*
H18B0.42191.01110.33930.028*
C190.39141 (5)0.94429 (16)0.41299 (8)0.0275 (3)
H19A0.35861.02690.38060.041*
H19B0.42340.99810.46950.041*
H19C0.37890.83570.42570.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0179 (4)0.0226 (4)0.0170 (3)−0.0018 (3)0.0114 (3)−0.0014 (3)
O20.0211 (4)0.0299 (5)0.0412 (5)−0.0049 (3)0.0177 (4)−0.0129 (4)
O30.0194 (4)0.0195 (4)0.0260 (4)−0.0008 (3)0.0130 (3)−0.0048 (3)
O40.0234 (4)0.0296 (4)0.0181 (4)0.0041 (3)0.0114 (3)0.0033 (3)
O50.0202 (4)0.0256 (4)0.0192 (4)0.0079 (3)0.0108 (3)0.0024 (3)
C10.0174 (5)0.0157 (4)0.0170 (4)−0.0031 (4)0.0101 (4)−0.0024 (4)
C20.0180 (5)0.0216 (5)0.0246 (5)−0.0010 (4)0.0143 (4)−0.0039 (4)
C30.0155 (5)0.0214 (5)0.0243 (5)0.0015 (4)0.0104 (4)−0.0006 (4)
C40.0161 (5)0.0169 (5)0.0202 (5)−0.0019 (4)0.0095 (4)−0.0007 (4)
C50.0175 (5)0.0233 (5)0.0216 (5)−0.0006 (4)0.0079 (4)0.0034 (4)
C60.0226 (5)0.0308 (6)0.0169 (5)−0.0041 (4)0.0091 (4)0.0033 (4)
C70.0232 (5)0.0291 (6)0.0202 (5)−0.0041 (4)0.0144 (4)−0.0010 (4)
C80.0178 (5)0.0211 (5)0.0195 (5)−0.0015 (4)0.0116 (4)−0.0007 (4)
C90.0158 (4)0.0149 (4)0.0174 (5)−0.0025 (3)0.0095 (4)−0.0012 (3)
C100.0156 (4)0.0144 (4)0.0174 (5)−0.0011 (3)0.0096 (4)−0.0014 (3)
C110.0175 (5)0.0151 (4)0.0190 (5)−0.0005 (4)0.0117 (4)−0.0009 (4)
C120.0178 (5)0.0162 (5)0.0188 (5)0.0000 (4)0.0113 (4)−0.0005 (4)
C130.0165 (5)0.0212 (5)0.0152 (4)0.0003 (4)0.0088 (4)−0.0007 (4)
C140.0190 (5)0.0230 (5)0.0159 (4)0.0000 (4)0.0103 (4)−0.0031 (4)
C150.0234 (5)0.0187 (5)0.0268 (5)−0.0021 (4)0.0135 (5)−0.0060 (4)
C160.0255 (6)0.0254 (6)0.0442 (7)0.0049 (5)0.0115 (6)−0.0061 (5)
C170.0182 (5)0.0158 (4)0.0191 (5)−0.0013 (4)0.0109 (4)−0.0006 (4)
C180.0202 (5)0.0216 (5)0.0248 (5)0.0067 (4)0.0114 (4)0.0037 (4)
C190.0271 (6)0.0222 (5)0.0356 (6)0.0032 (4)0.0200 (5)−0.0018 (5)
Geometric parameters (Å, °) top
O1—C11.3747 (12)C8—C91.4181 (14)
O1—C131.4336 (12)C8—H80.9500
O2—C141.2039 (13)C9—C101.4354 (13)
O3—C141.3255 (13)C10—C111.4534 (13)
O3—C151.4579 (13)C11—C121.3438 (14)
O4—C171.2102 (13)C11—H110.9500
O5—C171.3384 (12)C12—C171.4763 (14)
O5—C181.4532 (12)C12—C131.5056 (14)
C1—C101.3868 (14)C13—C141.5376 (15)
C1—C21.4068 (14)C13—H131.0000
C2—C31.3660 (15)C15—C161.4978 (16)
C2—H20.9500C15—H15A0.9900
C3—C41.4229 (15)C15—H15B0.9900
C3—H30.9500C16—H16A0.9800
C4—C51.4176 (15)C16—H16B0.9800
C4—C91.4251 (14)C16—H16C0.9800
C5—C61.3692 (16)C18—C191.5050 (16)
C5—H50.9500C18—H18A0.9900
C6—C71.4101 (16)C18—H18B0.9900
C6—H60.9500C19—H19A0.9800
C7—C81.3754 (15)C19—H19B0.9800
C7—H70.9500C19—H19C0.9800
C1—O1—C13114.11 (8)C17—C12—C13117.40 (9)
C14—O3—C15118.05 (9)O1—C13—C12110.92 (8)
C17—O5—C18115.78 (8)O1—C13—C14110.70 (8)
O1—C1—C10120.89 (9)C12—C13—C14112.17 (8)
O1—C1—C2116.68 (9)O1—C13—H13107.6
C10—C1—C2122.38 (9)C12—C13—H13107.6
C3—C2—C1119.33 (9)C14—C13—H13107.6
C3—C2—H2120.3O2—C14—O3126.07 (10)
C1—C2—H2120.3O2—C14—C13123.27 (10)
C2—C3—C4121.11 (10)O3—C14—C13110.62 (9)
C2—C3—H3119.4O3—C15—C16106.18 (9)
C4—C3—H3119.4O3—C15—H15A110.5
C5—C4—C3121.31 (10)C16—C15—H15A110.5
C5—C4—C9119.24 (9)O3—C15—H15B110.5
C3—C4—C9119.45 (9)C16—C15—H15B110.5
C6—C5—C4120.73 (10)H15A—C15—H15B108.7
C6—C5—H5119.6C15—C16—H16A109.5
C4—C5—H5119.6C15—C16—H16B109.5
C5—C6—C7120.10 (10)H16A—C16—H16B109.5
C5—C6—H6119.9C15—C16—H16C109.5
C7—C6—H6119.9H16A—C16—H16C109.5
C8—C7—C6120.64 (10)H16B—C16—H16C109.5
C8—C7—H7119.7O4—C17—O5123.96 (10)
C6—C7—H7119.7O4—C17—C12123.61 (9)
C7—C8—C9120.54 (10)O5—C17—C12112.40 (8)
C7—C8—H8119.7O5—C18—C19106.24 (9)
C9—C8—H8119.7O5—C18—H18A110.5
C8—C9—C4118.64 (9)C19—C18—H18A110.5
C8—C9—C10122.48 (9)O5—C18—H18B110.5
C4—C9—C10118.88 (9)C19—C18—H18B110.5
C1—C10—C9118.67 (9)H18A—C18—H18B108.7
C1—C10—C11117.45 (9)C18—C19—H19A109.5
C9—C10—C11123.82 (9)C18—C19—H19B109.5
C12—C11—C10119.55 (9)H19A—C19—H19B109.5
C12—C11—H11120.2C18—C19—H19C109.5
C10—C11—H11120.2H19A—C19—H19C109.5
C11—C12—C17123.91 (9)H19B—C19—H19C109.5
C11—C12—C13118.54 (9)
C13—O1—C1—C10−35.53 (13)C4—C9—C10—C11178.15 (9)
C13—O1—C1—C2146.96 (9)C1—C10—C11—C1214.50 (14)
O1—C1—C2—C3179.02 (9)C9—C10—C11—C12−168.35 (10)
C10—C1—C2—C31.55 (16)C10—C11—C12—C17−172.92 (9)
C1—C2—C3—C4−2.99 (16)C10—C11—C12—C132.62 (14)
C2—C3—C4—C5−179.58 (10)C1—O1—C13—C1249.75 (11)
C2—C3—C4—C90.52 (16)C1—O1—C13—C14−75.44 (10)
C3—C4—C5—C6177.24 (10)C11—C12—C13—O1−34.20 (13)
C9—C4—C5—C6−2.86 (16)C17—C12—C13—O1141.64 (9)
C4—C5—C6—C7−0.03 (17)C11—C12—C13—C1490.16 (11)
C5—C6—C7—C82.39 (18)C17—C12—C13—C14−94.01 (11)
C6—C7—C8—C9−1.78 (17)C15—O3—C14—O22.74 (16)
C7—C8—C9—C4−1.13 (15)C15—O3—C14—C13−174.88 (8)
C7—C8—C9—C10178.81 (10)O1—C13—C14—O2159.77 (10)
C5—C4—C9—C83.41 (15)C12—C13—C14—O235.29 (14)
C3—C4—C9—C8−176.69 (9)O1—C13—C14—O3−22.54 (11)
C5—C4—C9—C10−176.53 (9)C12—C13—C14—O3−147.02 (9)
C3—C4—C9—C103.37 (15)C14—O3—C15—C16−170.34 (10)
O1—C1—C10—C9−175.02 (9)C18—O5—C17—O4−4.22 (15)
C2—C1—C10—C92.35 (15)C18—O5—C17—C12174.06 (9)
O1—C1—C10—C112.28 (14)C11—C12—C17—O4170.68 (10)
C2—C1—C10—C11179.65 (9)C13—C12—C17—O4−4.91 (15)
C8—C9—C10—C1175.33 (9)C11—C12—C17—O5−7.61 (14)
C4—C9—C10—C1−4.73 (15)C13—C12—C17—O5176.80 (9)
C8—C9—C10—C11−1.79 (16)C17—O5—C18—C19173.96 (9)
Acknowledgements top

We thank King Abdul Aziz University (grant No. 171/428) and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Crano, J. C. & Guglielmetti, R. J. (1999). Organic Photochromic and Thermochomic Compounds, Vol. 1, Main Photochromic Families. CITY OF PUBLICATION?: Springer.

Ramazani, A., Noshiranzadeh, N., Kaffashy, S., Morsali, A., Jamali, F. & Gouranlou, F. (2002). Z. Kristallogr. New Cryst. Struct. 217, 231–232.

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

Westrip, S. P. (2009). publCIF. In preparation.