1,3-Benzodioxol-2-one

The title compound, C₇H₄O₃, is the first cyclic carbonate of an aromatic diol whose structure has been elucidated by means of single-crystal X-ray analysis. The mol­ecule possesses crystallographic twofold rotation symmetry and non-crystallographic C_2v symmetry. The C—O single bonds are slightly longer than those in comparable cyclic carbonates derived from aliphatic vicinal diols. The crystal structure is built up from columns of π-stacked mol­ecules; the inversion-related mol­ecules are stacked along the b axis, with the centroids of the benzene rings separated by 3.631 (1) Å.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.030
• wR factor = 0.072
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

---

S1. Comment

The title compound, (I), was accidentally prepared on the attempted synthesis of an asymmetric spiro-orthocarbonate.

The molecule of (I) (Fig. 1) possesses crystallographic twofold symmetry, with atoms C1 and O1 lying on the twofold rotation axis. The C1═O1 bond length [1.191 (2) Å] is comparable to the corresponding distance observed in similar cyclic carbonates derived from aliphatic vicinal diols, but the C1—O2 [1.3660 (13) Å] distance between the carbonyl C atom and the diol O atom is found to be slightly longer (Darensbourg et al., 2003; Betz et al., 2007). The five-membered 1,3-dioxol-2-one ring, which contains the carbonate group, is essentially planar and as a result the molecule as a whole is planar.

In the crystal structure, the inversion-related molecules are stacked along the b axis in such a way that the centroids of the benzene rings are separated by 3.631 (1) Å [perpendicular distance 3.370 Å], indicating significant π-π interactions (Figs. 2,3,4)

Related literature

For the synthesis of an asymmetric spiro orthocarbonate, see: Komatsu et al. (1992). For related structures, see: Betz et al. (2007); Darensbourg et al. (2003).

S2. Experimental

The title compound was obtained accidentally on the attempted synthesis of an asymmetric spiro orthocarbonate according to a published procedure (Komatsu et al., 1992) by reacting 2,2-dichlorobenzo[1.3]dioxole (10 mmol, 1.91 g) and 1-(hydroxymethyl)-cyclobutane-1-ol (10 mmol, 1.02 g) in the presence of pyridine (20 mmol, 1.58 g) in dichloromethane (10 ml). Crystals suitable for X-ray analysis were obtained directly from the crystallized reaction product.

S3. Refinement

All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined to 0.025 (3) Ų.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The structure of one molecule of (I), with atom labels and anisotropic displacement ellipsoids (drawn at the 50% probability level) for non-H atoms.
	Fig. 2. The molecular packing of (I), viewed along [1 0 0].
	Fig. 3. The molecular packing of (I), viewed along [0 1 0].
	Fig. 4. The molecular packing of (I), viewed along [0 0 1].

1,3-Benzodioxol-2-one

Crystal data

C7H4O3	Z = 4
Mr = 136.10	F(000) = 280
Monoclinic, C2/c	Dx = 1.586 Mg m^−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 10.224 (3) Å	θ = 3.8–27.5°
b = 8.9132 (14) Å	µ = 0.13 mm^−1
c = 6.9636 (14) Å	T = 100 K
β = 116.053 (16)°	Rod, colourless
V = 570.1 (2) Å^3	0.18 × 0.07 × 0.06 mm

Data collection

Oxford Diffraction XCalibur diffractometer	654 independent reflections
Radiation source: fine-focus sealed tube	492 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω–scans	θmax = 27.5°, θmin = 3.8°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −11→13
Tmin = 0.982, Tmax = 0.994	k = −11→9
1617 measured reflections	l = −9→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: difference Fourier map
wR(F^2) = 0.072	Only H-atom displacement parameters refined
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0381P)^2] where P = (Fo^2 + 2Fc^2)/3
654 reflections	(Δ/σ)max = 0.001
48 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.0000	0.44258 (14)	0.2500	0.0311 (4)
O2	0.11806 (9)	0.22115 (9)	0.28638 (13)	0.0204 (3)
C1	0.0000	0.3090 (2)	0.2500	0.0213 (4)
C2	0.07241 (13)	0.07251 (13)	0.27193 (18)	0.0160 (3)
C3	0.15072 (14)	−0.05641 (13)	0.29563 (19)	0.0197 (3)
H3	0.2508	−0.0554	0.3260	0.025 (3)*
C4	0.07345 (13)	−0.18920 (14)	0.27216 (19)	0.0209 (3)
H4	0.1221	−0.2823	0.2867	0.025 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0363 (8)	0.0159 (8)	0.0426 (8)	0.000	0.0187 (7)	0.000
O2	0.0180 (5)	0.0165 (5)	0.0274 (5)	−0.0010 (4)	0.0107 (4)	0.0002 (4)
C1	0.0212 (10)	0.0224 (11)	0.0207 (9)	0.000	0.0097 (8)	0.000
C2	0.0193 (6)	0.0152 (7)	0.0144 (5)	−0.0033 (5)	0.0083 (5)	−0.0009 (4)
C3	0.0174 (6)	0.0221 (7)	0.0200 (6)	0.0030 (5)	0.0087 (5)	0.0000 (5)
C4	0.0251 (7)	0.0166 (7)	0.0221 (6)	0.0038 (5)	0.0114 (6)	0.0008 (5)

Geometric parameters (Å, º)

O1—C1	1.191 (2)	C3—C4	1.3922 (17)
O2—C1	1.3660 (13)	C3—H3	0.95
O2—C2	1.3935 (15)	C4—C4^i	1.394 (3)
C2—C3	1.3684 (17)	C4—H4	0.95
C2—C2^i	1.374 (2)
C1—O2—C2	106.92 (10)	C2—C3—C4	115.34 (12)
O1—C1—O2	124.98 (7)	C2—C3—H3	122.3
O2^i—C1—O2	110.04 (15)	C4—C3—H3	122.3
C3—C2—C2^i	122.89 (7)	C3—C4—C4^i	121.77 (7)
C3—C2—O2	129.05 (11)	C3—C4—H4	119.1
C2^i—C2—O2	108.06 (6)	C4^i—C4—H4	119.1

Symmetry code: (i) −x, y, −z+1/2.