1,2-Di-2-furylethane-1,2-dione

Jian, F.-F.; Wang, K.-F.; Zhuang, R.-R.

doi:10.1107/S1600536807063568

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o196

https://doi.org/10.1107/S1600536807063568

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1,2-Di-2-furylethane-1,2-dione

Fang-Fang Jian,^a ^* Ke-Fei Wang ^a and Rui-Rui Zhuang ^a

^aNew Materials and Function Coordination Chemistry Laboratory, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: ffj2003@163169.net

(Received 10 November 2007; accepted 26 November 2007; online 6 December 2007)

The title compound, C₁₀H₆O₄, lies across a twofold rotation axis through the midpoint of the C—C bond between the two carbonyl groups. The furan ring plane and the plane through all atoms are inclined at 23.88 (1)°. In the crystal structure, weak C—H⋯O hydrogen bonds form sheets in the bc plane and columns down the c axis.

Related literature

For background to the chemistry of vicinal polycarbonyl compounds, see: Rubin & White (1982 ); Beddoes et al. (1975 ). For related structures and bond-length data, see: Brown & Sadanaga (1965 ).

Experimental

Crystal data

C₁₀H₆O₄
M_r = 190.15
Orthorhombic, F d d 2
a = 14.903 (4) Å
b = 30.511 (6) Å
c = 3.7770 (8) Å
V = 1717.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 (2) K
0.25 × 0.22 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2069 measured reflections
537 independent reflections
473 reflections with I > 2σ(I)
R_int = 0.098
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.113
S = 1.14
537 reflections
65 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱ	0.93	2.61	3.435 (3)	149
C1—H1A⋯O2ⁱⁱ	0.93	2.82	3.322 (4)	115
C2—H2A⋯O1ⁱⁱⁱ	0.93	2.64	3.439 (3)	145
C3—H3A⋯O1^iv	0.93	2.70	3.074 (3)	105
Symmetry codes: (i) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{3\over 4}}]$ ; (ii) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (iii) $[x-{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063568/sj2428sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063568/sj2428Isup2.hkl

checkCIF report

Comment top

The structures of vicinal polycarbonyl compounds have been of interest for many years (Rubin & White, 1982). Bond lengths, bond angles, and torsion angles in such molecules can deviate from 'normal' values in order to minimize the repulsive interactions resulting from juxtaposition of dipolar carbonyl groups (Brown & Sadanaga,1965) and the steric interactions of the chain of carbonyl groups with the end groups present (Beddoes et al., 1975). We report here the crystal structure of the title vicinal dione compound (I), Fig 1.

The molecule lies about a twofold rotation axis at the mid-point of the C5—C5A bond (A = -x + 1/2, -y + 1/2, z). Bond lengths and angles are similar to those observed for benzil (Brown & Sadanaga,1965). The molecule is approximately planar with the maximum deviation from the plane through all atoms 0.954 (1)Å for the O1. The furan ring plane (O2, C2···C4) and the plane through all atoms are inclined at 23.88 (1)°. In the crystal structure, weak C—H···O hydrogen bonds, Table 1, form sheets in the bc plane and columns down the c axis.

Related literature top

For background to the chemistry of vicinal polycarbonyl compounds, see: Rubin & White (1982); Beddoes et al. (1975). For related structures, see: Brown & Sadanaga (1965). For bond-length data, see: Brown & Sadanaga (1965).

Experimental top

Furfural (1.92 g, 20.0 mmol) was added to water (20 ml) together with the N,N-dialkylbenzimidazolium salt (1.14 g, 4.0 mmol) and triethylamine (0.5 ml, 3.6 mmol) and the solution stirred vigorously for 2 h under reflux to afford the title compound (1.71 g, yield 70%). Single crystals suitable for X-ray measurements were obtained by recrystallization from THF at room temperature.

Structure description top

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level. Atoms labelled A are related to other atoms by the symmetry operation -x + 1/2, -y + 1/2, z.
	Fig. 2. The Crystal packing of (I), viewed down the c axis.

1,2-Di-2-furylethane-1,2-dione top

Crystal data top

C₁₀H₆O₄	F(000) = 784
M_r = 190.15	D_x = 1.471 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 25 reflections
a = 14.903 (4) Å	θ = 4–14°
b = 30.511 (6) Å	µ = 0.12 mm⁻¹
c = 3.7770 (8) Å	T = 293 K
V = 1717.4 (7) Å³	Block, colourless
Z = 8	0.25 × 0.22 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.098
Radiation source: fine-focus sealed tube	θ_max = 27.0°, θ_min = 2.7°
Graphite monochromator	h = −18→18
ω scans	k = −36→37
2069 measured reflections	l = −4→0
537 independent reflections	3 standard reflections every 100 reflections
473 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0528P)² + 0.6456P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max < 0.001
537 reflections	Δρ_max = 0.33 e Å⁻³
65 parameters	Δρ_min = −0.14 e Å⁻³
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.005 (2)

Crystal data top

C₁₀H₆O₄	V = 1717.4 (7) Å³
M_r = 190.15	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 14.903 (4) Å	µ = 0.12 mm⁻¹
b = 30.511 (6) Å	T = 293 K
c = 3.7770 (8) Å	0.25 × 0.22 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.098
2069 measured reflections	3 standard reflections every 100 reflections
537 independent reflections	intensity decay: none
473 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.113	H-atom parameters constrained
S = 1.14	Δρ_max = 0.33 e Å⁻³
537 reflections	Δρ_min = −0.14 e Å⁻³
65 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	0.31781 (10)	0.20624 (6)	0.2936 (8)	0.0645 (7)
O2	0.17183 (10)	0.15778 (5)	0.5125 (7)	0.0586 (6)
C1	0.09123 (18)	0.14450 (9)	0.6479 (12)	0.0668 (9)
H1A	0.0735	0.1154	0.6673	0.080*
C2	0.04119 (18)	0.17857 (9)	0.7488 (9)	0.0598 (8)
H2A	−0.0160	0.1775	0.8472	0.072*
C3	0.09224 (16)	0.21647 (8)	0.6764 (7)	0.0488 (6)
H3A	0.0751	0.2453	0.7178	0.059*
C4	0.17150 (13)	0.20269 (6)	0.5341 (7)	0.0409 (6)
C5	0.25168 (15)	0.22475 (6)	0.4110 (8)	0.0416 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0430 (8)	0.0496 (9)	0.1008 (17)	0.0044 (7)	0.0119 (12)	−0.0137 (11)
O2	0.0446 (8)	0.0400 (8)	0.0913 (15)	−0.0025 (7)	−0.0098 (10)	0.0031 (11)
C1	0.0514 (13)	0.0527 (13)	0.096 (2)	−0.0165 (11)	−0.0162 (17)	0.0175 (17)
C2	0.0439 (11)	0.0709 (16)	0.0646 (18)	−0.0134 (11)	−0.0013 (13)	0.0095 (15)
C3	0.0435 (11)	0.0518 (12)	0.0513 (13)	−0.0025 (10)	0.0012 (12)	−0.0029 (12)
C4	0.0393 (11)	0.0366 (10)	0.0468 (11)	−0.0013 (8)	−0.0081 (10)	0.0021 (11)
C5	0.0361 (10)	0.0406 (11)	0.0481 (12)	0.0017 (8)	−0.0032 (10)	−0.0034 (10)

Geometric parameters (Å, º) top

O1—C5	1.219 (3)	C2—H2A	0.9300
O2—C1	1.367 (4)	C3—C4	1.364 (3)
O2—C4	1.373 (2)	C3—H3A	0.9300
C1—C2	1.335 (4)	C4—C5	1.448 (3)
C1—H1A	0.9300	C5—C5ⁱ	1.541 (4)
C2—C3	1.411 (4)

C1—O2—C4	105.7 (2)	C4—C3—H3A	126.6
C2—C1—O2	111.5 (2)	C2—C3—H3A	126.6
C2—C1—H1A	124.2	C3—C4—O2	109.52 (19)
O2—C1—H1A	124.2	C3—C4—C5	134.25 (19)
C1—C2—C3	106.4 (2)	O2—C4—C5	116.23 (19)
C1—C2—H2A	126.8	O1—C5—C4	124.63 (19)
C3—C2—H2A	126.8	O1—C5—C5ⁱ	119.3 (2)
C4—C3—C2	106.9 (2)	C4—C5—C5ⁱ	116.0 (2)

C4—O2—C1—C2	0.5 (4)	C1—O2—C4—C5	178.9 (3)
O2—C1—C2—C3	−0.2 (4)	C3—C4—C5—O1	178.9 (3)
C1—C2—C3—C4	−0.1 (3)	O2—C4—C5—O1	−0.3 (4)
C2—C3—C4—O2	0.4 (3)	C3—C4—C5—C5ⁱ	−5.0 (4)
C2—C3—C4—C5	−178.9 (3)	O2—C4—C5—C5ⁱ	175.79 (18)
C1—O2—C4—C3	−0.5 (3)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱⁱ	0.93	2.61	3.435 (3)	149
C1—H1A···O2ⁱⁱⁱ	0.93	2.82	3.322 (4)	115
C2—H2A···O1^iv	0.93	2.64	3.439 (3)	145
C3—H3A···O1ⁱ	0.93	2.70	3.074 (3)	105

Symmetry codes: (i) −x+1/2, −y+1/2, z; (ii) x−1/4, −y+1/4, z+3/4; (iii) x−1/4, −y+1/4, z−1/4; (iv) x−1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₆O₄
M_r	190.15
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	293
a, b, c (Å)	14.903 (4), 30.511 (6), 3.7770 (8)
V (Å³)	1717.4 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.25 × 0.22 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2069, 537, 473
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.113, 1.14
No. of reflections	537
No. of parameters	65
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.14

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1990), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.93	2.61	3.435 (3)	148.5
C1—H1A···O2ⁱⁱ	0.93	2.82	3.322 (4)	115.1
C2—H2A···O1ⁱⁱⁱ	0.93	2.64	3.439 (3)	145.0
C3—H3A···O1^iv	0.93	2.70	3.074 (3)	104.8

Symmetry codes: (i) x−1/4, −y+1/4, z+3/4; (ii) x−1/4, −y+1/4, z−1/4; (iii) x−1/2, y, z+1/2; (iv) −x+1/2, −y+1/2, z.

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province (grant No. Y2006B08).

References

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