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

Asiri, A.M.; Ng, S.W.

doi:10.1107/S1600536809008691

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o760

doi:10.1107/S1600536809008691

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

Abdullah Mohamed Asiri ^a and Seik Weng Ng ^b ^*

^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 ). For the structure of the dimethyl ester analog, see: Ramazani et al. (2002 ).

Experimental

Crystal data

C₁₉H₁₈O₅
M_r = 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)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.04
3698 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008691/lh2784sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008691/lh2784Isup2.hkl

checkCIF report

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).

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

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

C₁₉H₁₈O₅	F(000) = 1376
M_r = 326.33	D_x = 1.344 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9911 reflections
a = 28.5156 (3) Å	θ = 2.7–28.7°
b = 7.5804 (1) Å	µ = 0.10 mm⁻¹
c = 18.5365 (2) Å	T = 123 K
β = 126.413 (1)°	Prism, yellow
V = 3224.54 (6) Å³	0.30 × 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 tube	R_int = 0.019
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
ω scans	h = −36→36
14849 measured reflections	k = −9→9
3698 independent reflections	l = −23→24

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0623P)² + 2.3553P] where P = (F_o² + 2F_c²)/3
3698 reflections	(Δ/σ)_max = 0.001
219 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₉H₁₈O₅	V = 3224.54 (6) Å³
M_r = 326.33	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 28.5156 (3) Å	µ = 0.10 mm⁻¹
b = 7.5804 (1) Å	T = 123 K
c = 18.5365 (2) Å	0.30 × 0.30 × 0.15 mm
β = 126.413 (1)°

Data collection top

Bruker SMART APEX diffractometer	3453 reflections with I > 2σ(I)
14849 measured reflections	R_int = 0.019
3698 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
3698 reflections	Δρ_min = −0.29 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O1	0.62940 (3)	0.55357 (10)	0.45186 (5)	0.01852 (17)
O2	0.50133 (4)	0.28978 (12)	0.34344 (6)	0.0312 (2)
O3	0.59191 (3)	0.24695 (10)	0.38235 (5)	0.02188 (18)
O4	0.46280 (3)	0.74298 (11)	0.29129 (5)	0.02427 (19)
O5	0.46291 (3)	0.79011 (11)	0.41127 (5)	0.02219 (18)
C1	0.65404 (4)	0.50737 (13)	0.53927 (7)	0.0168 (2)
C2	0.70965 (5)	0.42956 (14)	0.58737 (7)	0.0204 (2)
H2	0.7282	0.4094	0.5592	0.025*
C3	0.73670 (4)	0.38328 (15)	0.67493 (7)	0.0213 (2)
H3	0.7734	0.3256	0.7067	0.026*
C4	0.71080 (4)	0.42003 (14)	0.71938 (7)	0.0185 (2)
C5	0.73888 (5)	0.37331 (15)	0.81041 (7)	0.0230 (2)
H5	0.7749	0.3117	0.8419	0.028*
C6	0.71465 (5)	0.41601 (16)	0.85348 (7)	0.0251 (2)
H6	0.7339	0.3839	0.9145	0.030*
C7	0.66120 (5)	0.50753 (16)	0.80743 (7)	0.0232 (2)
H7	0.6454	0.5407	0.8383	0.028*
C8	0.63177 (4)	0.54922 (14)	0.71821 (7)	0.0191 (2)
H8	0.5953	0.6080	0.6876	0.023*
C9	0.65548 (4)	0.50523 (13)	0.67154 (7)	0.0162 (2)
C10	0.62585 (4)	0.54314 (13)	0.57807 (7)	0.0159 (2)
C11	0.56863 (4)	0.62474 (13)	0.52185 (7)	0.0166 (2)
H11	0.5517	0.6760	0.5481	0.020*
C12	0.53990 (4)	0.62713 (13)	0.43245 (7)	0.0173 (2)
C13	0.56717 (4)	0.53746 (14)	0.39323 (7)	0.0180 (2)
H13	0.5530	0.5992	0.3360	0.022*
C14	0.54901 (4)	0.34276 (15)	0.37069 (7)	0.0193 (2)
C15	0.58056 (5)	0.06142 (14)	0.35676 (8)	0.0238 (2)
H15A	0.5534	0.0495	0.2907	0.029*
H15B	0.5631	0.0029	0.3834	0.029*
C16	0.63836 (6)	−0.01934 (18)	0.39174 (10)	0.0373 (3)
H16A	0.6331	−0.1447	0.3758	0.056*
H16B	0.6646	−0.0070	0.4571	0.056*
H16C	0.6552	0.0409	0.3652	0.056*
C17	0.48480 (4)	0.72331 (13)	0.37016 (7)	0.0178 (2)
C18	0.41183 (5)	0.90167 (15)	0.35647 (7)	0.0234 (2)
H18A	0.3810	0.8389	0.3012	0.028*
H18B	0.4219	1.0111	0.3393	0.028*
C19	0.39141 (5)	0.94429 (16)	0.41299 (8)	0.0275 (3)
H19A	0.3586	1.0269	0.3806	0.041*
H19B	0.4234	0.9981	0.4695	0.041*
H19C	0.3789	0.8357	0.4257	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0179 (4)	0.0226 (4)	0.0170 (3)	−0.0018 (3)	0.0114 (3)	−0.0014 (3)
O2	0.0211 (4)	0.0299 (5)	0.0412 (5)	−0.0049 (3)	0.0177 (4)	−0.0129 (4)
O3	0.0194 (4)	0.0195 (4)	0.0260 (4)	−0.0008 (3)	0.0130 (3)	−0.0048 (3)
O4	0.0234 (4)	0.0296 (4)	0.0181 (4)	0.0041 (3)	0.0114 (3)	0.0033 (3)
O5	0.0202 (4)	0.0256 (4)	0.0192 (4)	0.0079 (3)	0.0108 (3)	0.0024 (3)
C1	0.0174 (5)	0.0157 (4)	0.0170 (4)	−0.0031 (4)	0.0101 (4)	−0.0024 (4)
C2	0.0180 (5)	0.0216 (5)	0.0246 (5)	−0.0010 (4)	0.0143 (4)	−0.0039 (4)
C3	0.0155 (5)	0.0214 (5)	0.0243 (5)	0.0015 (4)	0.0104 (4)	−0.0006 (4)
C4	0.0161 (5)	0.0169 (5)	0.0202 (5)	−0.0019 (4)	0.0095 (4)	−0.0007 (4)
C5	0.0175 (5)	0.0233 (5)	0.0216 (5)	−0.0006 (4)	0.0079 (4)	0.0034 (4)
C6	0.0226 (5)	0.0308 (6)	0.0169 (5)	−0.0041 (4)	0.0091 (4)	0.0033 (4)
C7	0.0232 (5)	0.0291 (6)	0.0202 (5)	−0.0041 (4)	0.0144 (4)	−0.0010 (4)
C8	0.0178 (5)	0.0211 (5)	0.0195 (5)	−0.0015 (4)	0.0116 (4)	−0.0007 (4)
C9	0.0158 (4)	0.0149 (4)	0.0174 (5)	−0.0025 (3)	0.0095 (4)	−0.0012 (3)
C10	0.0156 (4)	0.0144 (4)	0.0174 (5)	−0.0011 (3)	0.0096 (4)	−0.0014 (3)
C11	0.0175 (5)	0.0151 (4)	0.0190 (5)	−0.0005 (4)	0.0117 (4)	−0.0009 (4)
C12	0.0178 (5)	0.0162 (5)	0.0188 (5)	0.0000 (4)	0.0113 (4)	−0.0005 (4)
C13	0.0165 (5)	0.0212 (5)	0.0152 (4)	0.0003 (4)	0.0088 (4)	−0.0007 (4)
C14	0.0190 (5)	0.0230 (5)	0.0159 (4)	0.0000 (4)	0.0103 (4)	−0.0031 (4)
C15	0.0234 (5)	0.0187 (5)	0.0268 (5)	−0.0021 (4)	0.0135 (5)	−0.0060 (4)
C16	0.0255 (6)	0.0254 (6)	0.0442 (7)	0.0049 (5)	0.0115 (6)	−0.0061 (5)
C17	0.0182 (5)	0.0158 (4)	0.0191 (5)	−0.0013 (4)	0.0109 (4)	−0.0006 (4)
C18	0.0202 (5)	0.0216 (5)	0.0248 (5)	0.0067 (4)	0.0114 (4)	0.0037 (4)
C19	0.0271 (6)	0.0222 (5)	0.0356 (6)	0.0032 (4)	0.0200 (5)	−0.0018 (5)

Geometric parameters (Å, º) top

O1—C1	1.3747 (12)	C8—C9	1.4181 (14)
O1—C13	1.4336 (12)	C8—H8	0.9500
O2—C14	1.2039 (13)	C9—C10	1.4354 (13)
O3—C14	1.3255 (13)	C10—C11	1.4534 (13)
O3—C15	1.4579 (13)	C11—C12	1.3438 (14)
O4—C17	1.2102 (13)	C11—H11	0.9500
O5—C17	1.3384 (12)	C12—C17	1.4763 (14)
O5—C18	1.4532 (12)	C12—C13	1.5056 (14)
C1—C10	1.3868 (14)	C13—C14	1.5376 (15)
C1—C2	1.4068 (14)	C13—H13	1.0000
C2—C3	1.3660 (15)	C15—C16	1.4978 (16)
C2—H2	0.9500	C15—H15A	0.9900
C3—C4	1.4229 (15)	C15—H15B	0.9900
C3—H3	0.9500	C16—H16A	0.9800
C4—C5	1.4176 (15)	C16—H16B	0.9800
C4—C9	1.4251 (14)	C16—H16C	0.9800
C5—C6	1.3692 (16)	C18—C19	1.5050 (16)
C5—H5	0.9500	C18—H18A	0.9900
C6—C7	1.4101 (16)	C18—H18B	0.9900
C6—H6	0.9500	C19—H19A	0.9800
C7—C8	1.3754 (15)	C19—H19B	0.9800
C7—H7	0.9500	C19—H19C	0.9800

C1—O1—C13	114.11 (8)	C17—C12—C13	117.40 (9)
C14—O3—C15	118.05 (9)	O1—C13—C12	110.92 (8)
C17—O5—C18	115.78 (8)	O1—C13—C14	110.70 (8)
O1—C1—C10	120.89 (9)	C12—C13—C14	112.17 (8)
O1—C1—C2	116.68 (9)	O1—C13—H13	107.6
C10—C1—C2	122.38 (9)	C12—C13—H13	107.6
C3—C2—C1	119.33 (9)	C14—C13—H13	107.6
C3—C2—H2	120.3	O2—C14—O3	126.07 (10)
C1—C2—H2	120.3	O2—C14—C13	123.27 (10)
C2—C3—C4	121.11 (10)	O3—C14—C13	110.62 (9)
C2—C3—H3	119.4	O3—C15—C16	106.18 (9)
C4—C3—H3	119.4	O3—C15—H15A	110.5
C5—C4—C3	121.31 (10)	C16—C15—H15A	110.5
C5—C4—C9	119.24 (9)	O3—C15—H15B	110.5
C3—C4—C9	119.45 (9)	C16—C15—H15B	110.5
C6—C5—C4	120.73 (10)	H15A—C15—H15B	108.7
C6—C5—H5	119.6	C15—C16—H16A	109.5
C4—C5—H5	119.6	C15—C16—H16B	109.5
C5—C6—C7	120.10 (10)	H16A—C16—H16B	109.5
C5—C6—H6	119.9	C15—C16—H16C	109.5
C7—C6—H6	119.9	H16A—C16—H16C	109.5
C8—C7—C6	120.64 (10)	H16B—C16—H16C	109.5
C8—C7—H7	119.7	O4—C17—O5	123.96 (10)
C6—C7—H7	119.7	O4—C17—C12	123.61 (9)
C7—C8—C9	120.54 (10)	O5—C17—C12	112.40 (8)
C7—C8—H8	119.7	O5—C18—C19	106.24 (9)
C9—C8—H8	119.7	O5—C18—H18A	110.5
C8—C9—C4	118.64 (9)	C19—C18—H18A	110.5
C8—C9—C10	122.48 (9)	O5—C18—H18B	110.5
C4—C9—C10	118.88 (9)	C19—C18—H18B	110.5
C1—C10—C9	118.67 (9)	H18A—C18—H18B	108.7
C1—C10—C11	117.45 (9)	C18—C19—H19A	109.5
C9—C10—C11	123.82 (9)	C18—C19—H19B	109.5
C12—C11—C10	119.55 (9)	H19A—C19—H19B	109.5
C12—C11—H11	120.2	C18—C19—H19C	109.5
C10—C11—H11	120.2	H19A—C19—H19C	109.5
C11—C12—C17	123.91 (9)	H19B—C19—H19C	109.5
C11—C12—C13	118.54 (9)

C13—O1—C1—C10	−35.53 (13)	C4—C9—C10—C11	178.15 (9)
C13—O1—C1—C2	146.96 (9)	C1—C10—C11—C12	14.50 (14)
O1—C1—C2—C3	179.02 (9)	C9—C10—C11—C12	−168.35 (10)
C10—C1—C2—C3	1.55 (16)	C10—C11—C12—C17	−172.92 (9)
C1—C2—C3—C4	−2.99 (16)	C10—C11—C12—C13	2.62 (14)
C2—C3—C4—C5	−179.58 (10)	C1—O1—C13—C12	49.75 (11)
C2—C3—C4—C9	0.52 (16)	C1—O1—C13—C14	−75.44 (10)
C3—C4—C5—C6	177.24 (10)	C11—C12—C13—O1	−34.20 (13)
C9—C4—C5—C6	−2.86 (16)	C17—C12—C13—O1	141.64 (9)
C4—C5—C6—C7	−0.03 (17)	C11—C12—C13—C14	90.16 (11)
C5—C6—C7—C8	2.39 (18)	C17—C12—C13—C14	−94.01 (11)
C6—C7—C8—C9	−1.78 (17)	C15—O3—C14—O2	2.74 (16)
C7—C8—C9—C4	−1.13 (15)	C15—O3—C14—C13	−174.88 (8)
C7—C8—C9—C10	178.81 (10)	O1—C13—C14—O2	159.77 (10)
C5—C4—C9—C8	3.41 (15)	C12—C13—C14—O2	35.29 (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—C10	3.37 (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—C9	2.35 (15)	C18—O5—C17—C12	174.06 (9)
O1—C1—C10—C11	2.28 (14)	C11—C12—C17—O4	170.68 (10)
C2—C1—C10—C11	179.65 (9)	C13—C12—C17—O4	−4.91 (15)
C8—C9—C10—C1	175.33 (9)	C11—C12—C17—O5	−7.61 (14)
C4—C9—C10—C1	−4.73 (15)	C13—C12—C17—O5	176.80 (9)
C8—C9—C10—C11	−1.79 (16)	C17—O5—C18—C19	173.96 (9)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈O₅
M_r	326.33
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	123
a, b, c (Å)	28.5156 (3), 7.5804 (1), 18.5365 (2)
β (°)	126.413 (1)
V (Å³)	3224.54 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.30 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14849, 3698, 3453
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.04
No. of reflections	3698
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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