organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

aChemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah, Saudi Arabia, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 5 March 2009; accepted 10 March 2009; online 14 March 2009)

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.

Related literature

For a review on 2H-naphthopyrans, see: Crano & Guglielmetti (1999[Crano, J. C. & Guglielmetti, R. J. (1999). Organic Photochromic and Thermochomic Compounds, Vol. 1, Main Photochromic Families. Berlin: Springer.]). For the structure of the dimethyl ester analog, see: Ramazani et al. (2002[Ramazani, A., Noshiranzadeh, N., Kaffashy, S., Morsali, A., Jamali, F. & Gouranlou, F. (2002). Z. Kristallogr. New Cryst. Struct. 217, 231-232.]).

[Scheme 1]

Experimental

Crystal data
  • C19H18O5

  • Mr = 326.33

  • Monoclinic, C 2/c

  • a = 28.5156 (3) Å

  • b = 7.5804 (1) Å

  • c = 18.5365 (2) Å

  • β = 126.413 (1)°

  • V = 3224.54 (6) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 123 K

  • 0.30 × 0.30 × 0.15 mm

Data collection
  • Bruker SMART APEX diffractometer

  • Absorption correction: none

  • 14849 measured reflections

  • 3698 independent reflections

  • 3453 reflections with I > 2σ(I)

  • Rint = 0.019

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.108

  • S = 1.04

  • 3698 reflections

  • 219 parameters

  • H-atom parameters constrained

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


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 m3
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 mm1
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
Graphite monochromatorθmax = 27.5°, θmin = 1.8°
ω scansh = 3636
14849 measured reflectionsk = 99
3698 independent reflectionsl = 2324
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 = 1.04 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 Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C19H18O5V = 3224.54 (6) Å3
Mr = 326.33Z = 8
Monoclinic, C2/cMo Kα radiation
a = 28.5156 (3) ŵ = 0.10 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.108H-atom parameters constrained
S = 1.04Δρmax = 0.25 e Å3
3698 reflectionsΔρmin = 0.29 e Å3
219 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.

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)
H16A0.63310.14470.37580.056*
H16B0.66460.00700.45710.056*
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, º) 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—C1035.53 (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—C12168.35 (10)
C10—C1—C2—C31.55 (16)C10—C11—C12—C17172.92 (9)
C1—C2—C3—C42.99 (16)C10—C11—C12—C132.62 (14)
C2—C3—C4—C5179.58 (10)C1—O1—C13—C1249.75 (11)
C2—C3—C4—C90.52 (16)C1—O1—C13—C1475.44 (10)
C3—C4—C5—C6177.24 (10)C11—C12—C13—O134.20 (13)
C9—C4—C5—C62.86 (16)C17—C12—C13—O1141.64 (9)
C4—C5—C6—C70.03 (17)C11—C12—C13—C1490.16 (11)
C5—C6—C7—C82.39 (18)C17—C12—C13—C1494.01 (11)
C6—C7—C8—C91.78 (17)C15—O3—C14—O22.74 (16)
C7—C8—C9—C41.13 (15)C15—O3—C14—C13174.88 (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—C8176.69 (9)O1—C13—C14—O322.54 (11)
C5—C4—C9—C10176.53 (9)C12—C13—C14—O3147.02 (9)
C3—C4—C9—C103.37 (15)C14—O3—C15—C16170.34 (10)
O1—C1—C10—C9175.02 (9)C18—O5—C17—O44.22 (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—O44.91 (15)
C8—C9—C10—C1175.33 (9)C11—C12—C17—O57.61 (14)
C4—C9—C10—C14.73 (15)C13—C12—C17—O5176.80 (9)
C8—C9—C10—C111.79 (16)C17—O5—C18—C19173.96 (9)

Experimental details

Crystal data
Chemical formulaC19H18O5
Mr326.33
Crystal system, space groupMonoclinic, C2/c
Temperature (K)123
a, b, c (Å)28.5156 (3), 7.5804 (1), 18.5365 (2)
β (°) 126.413 (1)
V3)3224.54 (6)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.30 × 0.15
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
14849, 3698, 3453
Rint0.019
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.108, 1.04
No. of reflections3698
No. of parameters219
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.29

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

 

Acknowledgements

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

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCrano, J. C. & Guglielmetti, R. J. (1999). Organic Photochromic and Thermochomic Compounds, Vol. 1, Main Photochromic Families. Berlin: Springer.  Google Scholar
First citationRamazani, A., Noshiranzadeh, N., Kaffashy, S., Morsali, A., Jamali, F. & Gouranlou, F. (2002). Z. Kristallogr. New Cryst. Struct. 217, 231–232.  CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds