research communications
of 4,5-dimethyl-1,3-dioxol-2-one
aDepartment of Chemistry and Biochemistry, Lamar University, Beaumont, TX 77710, USA, and bDepartment of Chemistry, Tulane University, 6400 Freret Street, New Orleans, Louisiana 70118-5698, USA
*Correspondence e-mail: donahue@tulane.edu
The planar title compound 4,5-dimethyl-1,3-dioxol-2-one, C5H6O3, 1, crystallizes with its molecular C2 axis coincident with a crystallographic mirror plane in P21/m. In the plane defined by the b axis and an ac face diagonal, antiparallel linear strands of 1, formed by simple translation, associate to form sheets with close H⋯H and O⋯O intermolecular contacts. Between the sheets, parallel strands of 1 place the carbonyl O atom near the five-membered ring centroid of a neighboring molecule with close O⋯O and O⋯C contacts.
Keywords: crystal structure; carbonate; dioxolene ligand.
CCDC reference: 2207848
1. Chemical context
4,5-Dimethyl-1,3-dioxol-2-one, 1 (Fig. 1 and scheme), is a simple derivative of vinylene carbonate, 2a, that has attracted recent attention as a key component of non-aqueous electrolyte blends for advanced Li ion batteries (Park et al., 2021; Liu et al., 2017; Kotani & Kadota, 2016; Xu et al., 2010). Its 4-chloromethyl and 4-bromomethyl derivatives, 3, have significance in the pharmaceutical industry as building elements in the preparation of antibiotics such as prulifloxacin (Cao et al., 2013), cefuroxime variants (Webber, 1987), and ampicillin (Sakamoto et al., 1984; Xiao, 2004). In principle, by analogy to the usefulness that the related 4,5-dimethyl-1,3-dithiol-2-one, 4a, enjoys as a masked form of the dimethyldithiolene ligand (Chandrasekaran et al., 2009), 1 could function as a protected form of the dimethyldioxolene(2−) ligand, 5, that is liberated by straightforward base hydrolysis.
Although a few coordination complexes with the dimethyldioxolene ligand are known, they have been prepared by α-diketone to a low-valent metal precursor (Chisholm et al., 1983) or by an obscure route involving the reductive coupling of CO(g) with methyl ligands (Hofmann et al., 1985). This context of demonstrated usefulness and unrealized, but plausible, possibility for 1 persuaded us to undertake a study of its utility as a dioxolene ligand precursor. In an early research stage, serendipitously obtained diffraction-quality crystals of 1 provided an opportunity for characterization by X-ray diffraction, details of which are reported herein.
of the corresponding2. Structural commentary
Compound 1 crystallizes in the monoclinic P21/m upon a crystallographic mirror plane that coincides with the carbonyl bond (Fig. 1).
3. Supramolecular features
Molecules of 1 are aligned as one-dimensional strands by simple translation along one of the diagonals of the ac face of the (Fig. 2). The C=O oxygen atom of 1 forms close contacts of 2.53 Å with the hydrogen atoms from each of the methyl groups of the molecule aligned before or behind (Table 1), at a distance that approaches the sum of the van der Waals radii of the elements (Batsanov, 2001). These strands are further organized into two-dimensional sheets through side-by-side placement but with an alternating orientation of the polarized, carbonyl end of the molecules (Fig. 2). The b axis defines the 2nd dimension of these sheets. Between strands within these sheets, interatomic H⋯H separations are 2.89 and 3.05 Å, while nearest O⋯O distances between rings are 3.3962 (13) Å. Fig. 3 presents a perspective of these sheets that is approximately along the b axis of the cell such that the close stacking between them is visible.
An alternative description of the third dimension of the packing is that the one-dimensional strands noted above translate as a whole along the a axis of the cell with an offset that places the carbonyl oxygen atom of one molecule of one strand near the five-membered ring centroid of a neighboring molecule (Fig. 4). In contrast to the intrasheet strands depicted in Fig. 2, which are antiparallel, the neighboring intersheet strands are all oriented in the same direction. The closest intermolecular C⋯C and C⋯O contacts between these parallel strands are the Cc⋯Co separation of 3.3413 (16) Å, the Oc⋯Cc spacing of 3.3452 (18) Å, and the Or⋯Co distance of 3.3742 (13) Å (c = carbonyl, o = olefin, r = ring). It is likely that the electrostatic interactions of polarized bonds, e.g., placement of the negative end of the δ(–)O=Cδ(+) carbonyl dipole above the positive end of the same bond in the sheet below, exert a decisive role in guiding the organization and spacing of one molecular plane over another. An end-on view of these sheets in space-filling presentation mode emphasizes the packing efficiency imposed by these cumulative intermolecular interactions (Fig. 5).
4. Database survey
Of the relatively few vinylene carbonates that have been structurally characterized, only 1 and the parent compound 2a (Cser, 1974) are simple, symmetrically substituted variants. All other structurally identified compounds bearing this moiety are more complex organic molecules that have been prepared and studied as angiotensin II receptor blockers (Yanagisawa et al., 1996; Dams et al., 2015; Zhang et al., 2017). Despite its ostensible similarity to 1, compound 2a crystallizes in a rather different fashion. Although arranged into extended sheets, which also contain the b axis, molecules of 2a are not organized into discernible linear strands but instead are twisted relative to their neighbors so as to accommodate multiple C—H⋯O hydrogen-bonding interactions (Fig. 6). A glide plane, rather than simple translation, relates one molecule of 2a to another in the horizontal direction (Fig. 6). As their different space groups would necessitate, the packing arrangements for vinylene trithiocarbonate (2b, CSD refcode LAGMUC; Mereiter & Rosenau, 2005) and vinylene triselenolate (2c, SELOLS; Lyubovskaya et al., 1976) contrast greatly with 2a. The former reveals linear strands of molecules arranged in sheets with a parallel orientation of all strands. Intermolecular π–π stacking interactions appear to be the decisive packing force between sheets. The latter, when viewed along the b axis of the cell, reveals a herringbone-like pattern in the arrangement of molecules.
Compounds similar to 1 with methyl substituents at the 4 and 5 positions of the ring include 4a, already noted, and the all-sulfur form, 4b (DMTHTN; Smith & Luss, 1980). Compound 4b occurs in the same (No. 62, Pnma) as 2c with a qualitatively similar packing arrangement that differs in having the herringbone pattern visible when viewed along the cell's a axis. Compound 4a crystallizes in P21/c on a general position with similar generalities of description pertinent to its packing pattern as found for 2a. However, adjacent strands of 4b that are generated by the glide plane operation are slightly out of plane relative to one another. The selenium analogue (6) of 1 and 4a has not been characterized crystallographically but is a target of current study in our laboratory.
5. Synthesis and crystallization
The sample of 4,5-dimethyl-1,3-dioxol-2-one used in this study was purchased from AK Scientific, Inc. and recrystallized by evaporation of a MeOH solution from a test tube at room temperature.
6. Refinement
Crystal data, data collection and structure . Hydrogen atoms are added in calculated positions and refined with isotropic displacement parameters that are approximately 1.5 times those of the carbon atom to which they are attached. The C—H distances are fixed at 0.98 Å.
details are summarized in Table 2Supporting information
CCDC reference: 2207848
https://doi.org/10.1107/S2056989022009239/gg4011sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989022009239/gg4011Isup2.cml
Data collection: SMART (Bruker, 2000); cell
SMART (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C5H6O3 | F(000) = 120 |
Mr = 114.10 | Dx = 1.479 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 3.8283 (10) Å | Cell parameters from 2113 reflections |
b = 10.972 (2) Å | θ = 3.2–28.3° |
c = 6.1096 (10) Å | µ = 0.12 mm−1 |
β = 93.523 (2)° | T = 100 K |
V = 256.15 (10) Å3 | Block, white |
Z = 2 | 0.27 × 0.21 × 0.16 mm |
Bruker SMART APEX diffractometer | 636 independent reflections |
Radiation source: fine-focus sealed tube | 617 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
π and ο scans | θmax = 28.3°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −4→4 |
Tmin = 0.967, Tmax = 0.980 | k = −14→14 |
2310 measured reflections | l = −8→8 |
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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0345P)2 + 0.0767P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
636 reflections | Δρmax = 0.30 e Å−3 |
42 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.22 (2) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. Hydrogen atoms were added in calculated positions and refined with isotropic displacement parameters that are approximately 1.5 times those of the carbon atom to which they are attached. The C–H distances assumed were 0.98 Å. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.1654 (3) | 0.250000 | 0.67266 (16) | 0.0247 (3) | |
O2 | −0.08340 (16) | 0.35049 (6) | 0.94742 (10) | 0.0174 (2) | |
C1 | 0.0147 (3) | 0.250000 | 0.8382 (2) | 0.0177 (3) | |
C2 | −0.2444 (2) | 0.31041 (8) | 1.13620 (13) | 0.0156 (2) | |
C3 | −0.3662 (2) | 0.40519 (8) | 1.28542 (15) | 0.0190 (2) | |
H3A | −0.479500 | 0.366409 | 1.407001 | 0.028* | |
H3B | −0.534168 | 0.458611 | 1.204840 | 0.028* | |
H3C | −0.165882 | 0.453408 | 1.343402 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0293 (6) | 0.0271 (5) | 0.0186 (5) | 0.000 | 0.0091 (4) | 0.000 |
O2 | 0.0204 (4) | 0.0160 (4) | 0.0162 (4) | −0.0002 (2) | 0.0045 (2) | 0.0011 (2) |
C1 | 0.0185 (6) | 0.0176 (6) | 0.0169 (6) | 0.000 | 0.0008 (4) | 0.000 |
C2 | 0.0145 (4) | 0.0180 (5) | 0.0145 (4) | −0.0006 (3) | 0.0020 (3) | 0.0009 (3) |
C3 | 0.0206 (5) | 0.0168 (4) | 0.0199 (4) | 0.0004 (3) | 0.0044 (3) | −0.0027 (3) |
O1—C1 | 1.1949 (16) | C2—C3 | 1.4773 (12) |
O2—C1 | 1.3537 (10) | C3—H3A | 0.9800 |
O2—C2 | 1.4110 (10) | C3—H3B | 0.9800 |
C2—C2i | 1.3257 (18) | C3—H3C | 0.9800 |
C1—O2—C2 | 107.30 (7) | C2—C3—H3A | 109.5 |
O1—C1—O2i | 125.46 (5) | C2—C3—H3B | 109.5 |
O1—C1—O2 | 125.46 (5) | H3A—C3—H3B | 109.5 |
O2i—C1—O2 | 109.07 (10) | C2—C3—H3C | 109.5 |
C2i—C2—O2 | 108.16 (4) | H3A—C3—H3C | 109.5 |
C2i—C2—C3 | 134.74 (5) | H3B—C3—H3C | 109.5 |
O2—C2—C3 | 117.09 (7) | ||
C2—O2—C1—O1 | −178.43 (12) | C1—O2—C2—C2i | −0.72 (8) |
C2—O2—C1—O2i | 1.19 (12) | C1—O2—C2—C3 | 178.50 (8) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O1ii | 0.98 | 2.53 | 3.4976 (13) | 171 |
Symmetry code: (ii) x−1, y, z+1. |
Acknowledgements
The Louisiana Board of Regents is thanked for enhancement grant LEQSF–(2002–03)–ENH–TR–67 with which Tulane University's Bruker SMART APEX CCD X-ray diffractometer was purchased. Tulane University is acknowledged for its ongoing support with operational costs for the diffraction facility.
Funding information
Funding for this research was provided by: Louisiana Board of Regents (award No. LEQSF-(2002-03)-ENH-TR-67).
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