5,6-Dimethyl-1,2,9,10-tetra­hydro­pyrano[3,2-f]chromene-3,8-dione

Goswami, S.K.; Hanton, L.R.; McAdam, C.J.; Moratti, S.C.; Simpson, J.

doi:10.1107/S1600536812027699

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2216

https://doi.org/10.1107/S1600536812027699

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5,6-Dimethyl-1,2,9,10-tetrahydropyrano[3,2-f]chromene-3,8-dione

Shailesh K. Goswami,^a Lyall R. Hanton,^a C. John McAdam,^a Stephen C. Moratti ^a and Jim Simpson ^a ^*

^aDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

(Received 18 June 2012; accepted 18 June 2012; online 27 June 2012)

The title molecule, C₁₄H₁₄O₄, lies on a twofold rotation axis that bisects the central benzene ring, with only one half-molecule in the asymmetric unit. The pyranone systems adopt distorted twist- boat conformations, with the two methylene C atoms displaced by 0.537 (1) and 0.163 (2) Å from the best-fit plane through the remaining five C and O atoms (r.m.s. deviation = 0.073 Å). In the crystal, bifurcated C—H⋯(O,O) hydrogen bonds link pairs of adjacent molecules in an obverse fashion, stacking molecules along c. These contacts are further stabilized by very weak π–π interactions between adjacent benzene rings with centroid–centroid distances of 4.1951 (4) Å. Additional C—H⋯O contacts link these stacks, giving a three-dimensional network.

Related literature

For the synthesis, see: Lecea et al. (2010 ). For details of the Cambridge Structural Database, see: Allen (2002 ) and for related structures, see: Cameron et al. (2011 ); Goswami et al. (2011 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₄O₄
M_r = 246.25
Monoclinic, C 2/c
a = 16.0726 (2) Å
b = 8.7982 (1) Å
c = 8.0555 (1) Å
β = 96.1134 (7)°
V = 1132.65 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 92 K
0.53 × 0.50 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2011 ) T_min = 0.570, T_max = 0.748
9744 measured reflections
2989 independent reflections
2358 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.148
S = 1.08
2989 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C61—H61A⋯O1ⁱ	0.98	2.54	3.3907 (11)	145
C2—H2A⋯O1ⁱⁱ	0.99	2.60	3.4301 (12)	142
C2—H2A⋯O2ⁱⁱ	0.99	2.64	3.4813 (10)	143
C2—H2B⋯O1ⁱⁱⁱ	0.99	2.44	3.3528 (11)	154
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, -y-{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2011); cell refinement: APEX2 (Bruker, 2011) and SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ) and TITAN2000 (Hunter & Simpson, 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN2000; molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ), PLATON (Spek, 2009 ) and publCIF (Westrip 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812027699/bt5941sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027699/bt5941Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027699/bt5941Isup3.cml

checkCIF report

Comment top

Our current research interests involve the preparation of redox monomers for the synthesis of electroactive gels. The title compound (I), a chromene-dione was obtained as a by-product of the synthesis of the desired 6-hydroxy-7,8-dimethylchroman-2-one as previously reported by Lecea et al. (2010). The chromene-dione (I) provides access to an exciting new redox-active cross-linker in three steps through ring opening, oxidation and condensation reactions.

The asymmetric unit of the title compound contains only one half of the molecule, which lies on a twofold rotation axis that bisects the central benzene ring (Fig 1) The pyranone ring systems adopt distorted twist boat conformations, with the C2 and C3 methylene carbon atoms displaced by 0.537 (1) and 0.163 (2) Å respectively from the best fit plane through C1/(O1)/O2/C5/C4 which has an r.m.s. deviation 0.073 Å. A search of the Cambridge Database (Allen, 2002) revealed no comparable compounds, with or without substitution on the benzene ring. However we have previously reported closely related chroman-2-one derivatives without a second pyranone ring system (Goswami et al., 2011, Cameron et al., 2011). Bond lengths in the structure are not unusual (Allen et al., 1987) and are comparable to those in the chroman-2-one compounds mentioned previously.

In the crystal structure, bifurcated C2–H2A···O1 hydrogen bonds link pairs of adjacent molecules in an obverse fashion stacking molecules along c. Very weak π–π interactions, Cg···Cg = 4.1951 (4) Å, between adjacent benzene rings bolster these contacts further, Fig. 2. Additional C–H···O contacts, Table 1, generate layers of molecules in planes parallel to (1,0,1), Fig 3 while the overall result of this series of contacts is an extended three dimensional network, Fig. 4.

Related literature top

For the synthesis, see: Lecea et al. (2010). For details of the Cambridge Structural Database, see: Allen (2002) and for related structures, see: Cameron et al. (2011); Goswami et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was obtained as a by-product from a Friedel-Crafts type addition reaction of 2,3-dimethylhydroquinone with acrylic acid during the synthesis of 6-hydroxy-7,8-dimethylchroman-2-one (Lecea et al., 2010). Following work-up according to the literature, X-ray quality crystals of (I) were obtained from dichloromethane solution.

Structure description top

For the synthesis, see: Lecea et al. (2010). For details of the Cambridge Structural Database, see: Allen (2002) and for related structures, see: Cameron et al. (2011); Goswami et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: APEX2 (Bruker, 2011) and SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip 2010).

Figures top

	Fig. 1. The structure of (I) with ellipsoids drawn at the 50% probability level.
	Fig. 2. Bifurcated C–H···O hydrogen bonds (dashed lines), augmented by π–π stacking interactions (dotted lines) stacking molecules along c.
	Fig. 3. Layers of molecules in planes parallel to (101). Hydrogen bonds are drawn as dashed lines.
	Fig. 4. Overall packing of (I) with hydrogen bonds drawn as dashed lines.

5,6-dimethyl-1,2,9,10-tetrahydropyrano[3,2-f]chromene-3,8-dione top

Crystal data top

C₁₄H₁₄O₄	F(000) = 520
M_r = 246.25	D_x = 1.444 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3955 reflections
a = 16.0726 (2) Å	θ = 2.6–38.3°
b = 8.7982 (1) Å	µ = 0.11 mm⁻¹
c = 8.0555 (1) Å	T = 92 K
β = 96.1134 (7)°	Rectangular block, yellow
V = 1132.65 (2) Å³	0.53 × 0.50 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2989 independent reflections
Radiation source: fine-focus sealed tube	2358 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
φ & ω scans	θ_max = 39.3°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2011)	h = −27→26
T_min = 0.570, T_max = 0.748	k = −14→7
9744 measured reflections	l = −13→14

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0702P)² + 0.4368P] where P = (F_o² + 2F_c²)/3
2989 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₄H₁₄O₄	V = 1132.65 (2) Å³
M_r = 246.25	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.0726 (2) Å	µ = 0.11 mm⁻¹
b = 8.7982 (1) Å	T = 92 K
c = 8.0555 (1) Å	0.53 × 0.50 × 0.22 mm
β = 96.1134 (7)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2989 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2011)	2358 reflections with I > 2σ(I)
T_min = 0.570, T_max = 0.748	R_int = 0.038
9744 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.08	Δρ_max = 0.47 e Å⁻³
2989 reflections	Δρ_min = −0.38 e Å⁻³
83 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.76307 (4)	−0.03359 (9)	0.53742 (9)	0.02826 (17)
C1	0.70230 (5)	−0.04789 (10)	0.61199 (10)	0.01983 (16)
O2	0.64973 (4)	0.07377 (7)	0.61147 (8)	0.01902 (14)
C2	0.68037 (5)	−0.18492 (10)	0.70770 (10)	0.02081 (16)
H2A	0.6997	−0.1700	0.8274	0.025*
H2B	0.7099	−0.2745	0.6682	0.025*
C3	0.58596 (5)	−0.21578 (9)	0.68795 (10)	0.01919 (15)
H3A	0.5684	−0.2533	0.5737	0.023*
H3B	0.5728	−0.2952	0.7681	0.023*
C4	0.53894 (4)	−0.07275 (8)	0.71898 (9)	0.01485 (14)
C5	0.57500 (4)	0.06647 (8)	0.68637 (9)	0.01470 (14)
C6	0.53839 (4)	0.20612 (8)	0.71558 (9)	0.01519 (14)
C61	0.57956 (5)	0.35308 (10)	0.67541 (12)	0.02167 (17)
H61A	0.6030	0.4022	0.7792	0.033*
H61B	0.5380	0.4204	0.6156	0.033*
H61C	0.6245	0.3325	0.6053	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0216 (3)	0.0340 (4)	0.0307 (3)	0.0048 (2)	0.0097 (2)	0.0013 (3)
C1	0.0175 (3)	0.0226 (4)	0.0194 (3)	0.0039 (2)	0.0021 (2)	−0.0023 (3)
O2	0.0158 (2)	0.0186 (3)	0.0232 (3)	0.00139 (18)	0.0047 (2)	0.0013 (2)
C2	0.0214 (3)	0.0204 (4)	0.0207 (3)	0.0070 (3)	0.0026 (3)	0.0000 (3)
C3	0.0220 (3)	0.0143 (3)	0.0212 (3)	0.0028 (2)	0.0018 (2)	−0.0018 (2)
C4	0.0165 (3)	0.0124 (3)	0.0152 (3)	0.0007 (2)	−0.0003 (2)	−0.0005 (2)
C5	0.0140 (3)	0.0145 (3)	0.0154 (3)	0.0003 (2)	0.0009 (2)	0.0001 (2)
C6	0.0150 (3)	0.0122 (3)	0.0178 (3)	−0.0004 (2)	−0.0007 (2)	0.0006 (2)
C61	0.0196 (3)	0.0149 (3)	0.0302 (4)	−0.0028 (2)	0.0012 (3)	0.0024 (3)

Geometric parameters (Å, º) top

O1—C1	1.2065 (10)	C3—H3B	0.9900
C1—O2	1.3634 (10)	C4—C5	1.3920 (10)
C1—C2	1.4934 (13)	C4—C4ⁱ	1.3962 (14)
O2—C5	1.4018 (9)	C5—C6	1.3931 (10)
C2—C3	1.5329 (11)	C6—C6ⁱ	1.4058 (14)
C2—H2A	0.9900	C6—C61	1.5033 (11)
C2—H2B	0.9900	C61—H61A	0.9800
C3—C4	1.5025 (11)	C61—H61B	0.9800
C3—H3A	0.9900	C61—H61C	0.9800

O1—C1—O2	116.80 (8)	C5—C4—C4ⁱ	118.34 (4)
O1—C1—C2	126.11 (8)	C5—C4—C3	118.59 (7)
O2—C1—C2	117.07 (7)	C4ⁱ—C4—C3	123.06 (4)
C1—O2—C5	121.45 (6)	C4—C5—C6	123.53 (7)
C1—C2—C3	112.01 (7)	C4—C5—O2	120.97 (6)
C1—C2—H2A	109.2	C6—C5—O2	115.40 (6)
C3—C2—H2A	109.2	C5—C6—C6ⁱ	118.10 (4)
C1—C2—H2B	109.2	C5—C6—C61	121.25 (7)
C3—C2—H2B	109.2	C6ⁱ—C6—C61	120.66 (4)
H2A—C2—H2B	107.9	C6—C61—H61A	109.5
C4—C3—C2	110.14 (7)	C6—C61—H61B	109.5
C4—C3—H3A	109.6	H61A—C61—H61B	109.5
C2—C3—H3A	109.6	C6—C61—H61C	109.5
C4—C3—H3B	109.6	H61A—C61—H61C	109.5
C2—C3—H3B	109.6	H61B—C61—H61C	109.5
H3A—C3—H3B	108.1

O1—C1—O2—C5	176.44 (7)	C4ⁱ—C4—C5—O2	−174.81 (8)
C2—C1—O2—C5	−4.87 (11)	C3—C4—C5—O2	5.95 (11)
O1—C1—C2—C3	−142.07 (9)	C1—O2—C5—C4	−19.48 (11)
O2—C1—C2—C3	39.38 (10)	C1—O2—C5—C6	164.02 (7)
C1—C2—C3—C4	−49.20 (9)	C4—C5—C6—C6ⁱ	1.15 (14)
C2—C3—C4—C5	27.91 (10)	O2—C5—C6—C6ⁱ	177.55 (8)
C2—C3—C4—C4ⁱ	−151.29 (9)	C4—C5—C6—C61	−179.02 (7)
C4ⁱ—C4—C5—C6	1.40 (14)	O2—C5—C6—C61	−2.62 (11)
C3—C4—C5—C6	−177.84 (7)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C61—H61A···O1ⁱⁱ	0.98	2.54	3.3907 (11)	145
C2—H2A···O1ⁱⁱⁱ	0.99	2.60	3.4301 (12)	142
C2—H2A···O2ⁱⁱⁱ	0.99	2.64	3.4813 (10)	143
C2—H2B···O1^iv	0.99	2.44	3.3528 (11)	154

Symmetry codes: (ii) −x+3/2, y+1/2, −z+3/2; (iii) x, −y, z+1/2; (iv) −x+3/2, −y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄O₄
M_r	246.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	92
a, b, c (Å)	16.0726 (2), 8.7982 (1), 8.0555 (1)
β (°)	96.1134 (7)
V (Å³)	1132.65 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.53 × 0.50 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2011)
T_min, T_max	0.570, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	9744, 2989, 2358
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.891

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.148, 1.08
No. of reflections	2989
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.38

Computer programs: APEX2 (Bruker, 2011) and SAINT (Bruker, 2011), SAINT (Bruker, 2011), SHELXS97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C61—H61A···O1ⁱ	0.98	2.54	3.3907 (11)	145.0
C2—H2A···O1ⁱⁱ	0.99	2.60	3.4301 (12)	141.9
C2—H2A···O2ⁱⁱ	0.99	2.64	3.4813 (10)	142.5
C2—H2B···O1ⁱⁱⁱ	0.99	2.44	3.3528 (11)	153.7

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x, −y, z+1/2; (iii) −x+3/2, −y−1/2, −z+1.

Acknowledgements

We thank the New Economy Research Fund (grant No. UOO-X0808) for support of this work and the University of Otago for the purchase of the diffractometer.

References

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