supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

bt2936 scheme

Acta Cryst. (2009). E65, o1192    [ doi:10.1107/S1600536809015190 ]

(2,2-Dimethyl-1,3-dioxolan-4-yl)methyl 3-carboxypropanoate

P. Kus, M. Rojkiewicz, G. Zieba, M. Witoszek and P. G. Jones

Abstract top

In the title compound, C10H16O6, the five-membered ring has an envelope conformation. The packing involves hydrogen-bonded carboxylic acid inversion dimers and three C-H...O interactions.

Comment top

Isopropylidene groups are often used as protecting or activating units in polyhydroxyalkyl compounds used for synthesis of sugar-like derivatives; for a brief introduction and the structure of a related derivative, see the accompanying paper (Kuś et al., 2009).

Hemi-esters of succinic acid are often used for the synthesis of amphiphilic compounds with well organized structure (Osanai et al., 1997). Non-symmetrical esters of succinic acid have been used for the synthesis of prodrugs that release the corresponding drugs very slowly; e.g. steroid drugs (Scriba, 1995) or Phenytoin (Scriba, 1993). Solketal (D,L-isopropylideneglycerol, Aldrich) was used for the synthesis of compound 1.

The molecule of compound 1 is shown in Fig. 1. Bond lengths and angles may be regarded as normal. The chain C2 through to C7 has an approximately extended conformation (absolute torsion angles between 158 and 174°). The five-membered ring displays an envelope conformation, with local mirror symmetry about C8 and the midpoint of C6—C7.

The molecular packing (Fig. 2) is dominated by the formation of the well known carboxylic acid dimers via classical hydrogen bonding. Three further contacts, of the type C—H···O, link the molecules to a three-dimensional pattern.

Related literature top

For related literature, see: Osanai et al. (1997); Scriba (1993, 1995). The structure of a related derivative is reported in the preceeding paper, see: Kuś et al. (2009)

Experimental top

Compound 1 was obtained from solketal and succinic anhydride as described by Scriba (1993). Slow crystallization from petroleum ether gave crystals suitable for X-ray analysis. The analytical and spectroscopic data are consistent with the literature. M.p. 60° C. 1H NMR (CDCl3, 400 MHz): δ 4.32 (q, 1H), 4.21–4.05 (m, 3H), 3.75–3.72 (dd, 1H), 2.67 (t, 4H), 1.43 (s, 3H), 1.36 (s, 3H). 13C NMR (100 MHz): δ 207.34, 172.10, 110.03, 73.62, 66.39, 65.13, 31.03, 28.97, 26.78, 25.46. MS (ESI): m/z (%) = 231 (100) [M—H]-. IR: C═O at 1724, 1711 and 1694 cm-1 (s), C—O at 1234 cm-1 (m), 1,3-dioxalone at 975 cm-1 (s).

Refinement top

The OH hydrogen was refined freely. Methyl H atoms were identified in difference syntheses and refined as idealized rigid groups (C—H 0.98 Å, H—C—H 109.5°) allowed to rotate but not tip. Other H atoms were included at calculated positions and refined using a riding model, with fixed C—H bond lengths of 0.95 Å (CH, aromatic), 0.99 Å (CH2) and 1.00 Å (CH, sp3); Uiso(H) values were fixed at 1.2Ueq of the parent C atom (1.2Ueq for methyl H).

The atom C6 is disordered over two sites with occupancy ratio 0.9:0.1, corresponding to a second conformation of the five-membered ring. An appropriate set of similarity restraints was used to ensure stability of refinement.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The title compound in the crystal structure. Displacement ellipsoids represent 50% probability levels.
[Figure 2] Fig. 2. Packing diagram of the title compound. H atoms not involved in H bonding (thick dashed lines) are omitted for clarity. The interaction H7B···O5, which links the five-membered rings parallel to the c axis (the view direction), is not shown.
2,2-Dimethyl-1,3-dioxolan-4-ylmethyl 3-carboxypropanoate top
Crystal data top
C10H16O6Dx = 1.359 Mg m−3
Mr = 232.23Melting point: 333 K
Monoclinic, P21/cCu Kα radiation
λ = 1.54184 Å
a = 20.7650 (12) ÅCell parameters from 7029 reflections
b = 5.7007 (3) Åθ = 4.3–75.7º
c = 9.6964 (7) ŵ = 0.96 mm−1
β = 98.658 (5)ºT = 100 K
V = 1134.73 (12) Å3Block, colourless
Z = 40.2 × 0.1 × 0.1 mm
F000 = 496
Data collection top
Oxford Diffraction Xcalibur
diffractometer with an Atlas (Nova) detector		2304 independent reflections
Radiation source: Nova (Cu) X-ray Source2170 reflections with I > 2σ(I)
Monochromator: mirrorRint = 0.028
Detector resolution: 10.3543 pixels mm-1θmax = 74.5º
T = 100 Kθmin = 4.3º
ω scansh = −25→25
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		k = −7→6
Tmin = 0.880, Tmax = 1.000l = −10→12
10581 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.125  w = 1/[σ2(Fo2) + (0.0399P)2 + 1.0966P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.015
2304 reflectionsΔρmax = 0.27 e Å−3
156 parametersΔρmin = −0.25 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C10H16O6V = 1134.73 (12) Å3
Mr = 232.23Z = 4
Monoclinic, P21/cCu Kα
a = 20.7650 (12) ŵ = 0.96 mm−1
b = 5.7007 (3) ÅT = 100 K
c = 9.6964 (7) Å0.2 × 0.1 × 0.1 mm
β = 98.658 (5)º
Data collection top
Oxford Diffraction Xcalibur
diffractometer with an Atlas (Nova) detector		2304 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		2170 reflections with I > 2σ(I)
Tmin = 0.880, Tmax = 1.000Rint = 0.028
10581 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0514 restraints
wR(F2) = 0.125H atoms treated by a mixture of
independent and constrained refinement
S = 1.14Δρmax = 0.27 e Å−3
2304 reflectionsΔρmin = −0.25 e Å−3
156 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
xyzUiso*/UeqOcc. (<1)
O10.44071 (7)−0.1502 (2)0.58989 (15)0.0287 (3)
H010.4643 (14)−0.164 (5)0.533 (3)0.047 (8)*
O20.47778 (6)0.2189 (2)0.59298 (14)0.0278 (3)
C10.44377 (9)0.0675 (3)0.63543 (19)0.0243 (4)
C20.40364 (9)0.1107 (3)0.7496 (2)0.0265 (4)
H2A0.42990.07010.84030.032*
H2B0.36530.00550.73560.032*
C30.38031 (9)0.3632 (3)0.75537 (19)0.0258 (4)
H3A0.35990.38490.84050.031*
H3B0.41830.46970.76200.031*
C40.33223 (9)0.4289 (3)0.6303 (2)0.0258 (4)
O30.32078 (7)0.3156 (3)0.52376 (14)0.0340 (4)
O40.30257 (6)0.6315 (2)0.65113 (14)0.0295 (3)
C50.26115 (10)0.7325 (4)0.5323 (2)0.0339 (5)
H5A0.23720.60730.47520.041*0.893 (8)
H5B0.28770.82050.47310.041*0.893 (8)
H5C0.27980.88860.51700.041*0.107 (8)
H5D0.26750.63540.45080.041*0.107 (8)
O50.16891 (7)0.7592 (3)0.65090 (18)0.0426 (4)
O60.10733 (7)0.9607 (3)0.48082 (18)0.0453 (4)
C60.21452 (11)0.8932 (4)0.5879 (3)0.0318 (7)0.893 (8)
H60.23851.00410.65730.038*0.893 (8)
C70.17233 (11)1.0302 (5)0.4709 (3)0.0459 (6)
H7A0.17791.20140.48520.055*0.893 (8)
H7B0.18390.98860.37860.055*0.893 (8)
H7C0.18961.15530.53710.055*0.107 (8)
H7D0.18011.06640.37490.055*0.107 (8)
C6'0.1934 (9)0.766 (4)0.523 (2)0.069 (10)*0.107 (8)
H6'0.16990.64850.45720.083*0.107 (8)
C80.10751 (10)0.8735 (4)0.6185 (2)0.0388 (5)
C90.10142 (14)1.0693 (5)0.7197 (3)0.0568 (7)
H9A0.10501.00540.81440.085*
H9B0.05901.14610.69520.085*
H9C0.13621.18410.71560.085*
C100.05421 (12)0.6939 (5)0.6160 (3)0.0532 (7)
H10A0.06090.56800.55080.080*
H10B0.01190.76860.58610.080*
H10C0.05520.62820.70970.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0314 (7)0.0253 (7)0.0316 (7)−0.0017 (6)0.0123 (6)−0.0010 (6)
O20.0279 (7)0.0250 (7)0.0322 (7)−0.0018 (5)0.0100 (5)−0.0003 (6)
C10.0223 (8)0.0241 (9)0.0256 (9)0.0016 (7)0.0007 (7)0.0022 (7)
C20.0272 (9)0.0277 (10)0.0254 (9)−0.0004 (7)0.0062 (7)0.0022 (8)
C30.0266 (9)0.0265 (10)0.0247 (9)0.0005 (7)0.0055 (7)−0.0011 (7)
C40.0233 (9)0.0273 (10)0.0285 (9)−0.0009 (7)0.0097 (7)0.0007 (8)
O30.0374 (8)0.0391 (8)0.0256 (7)0.0069 (6)0.0048 (6)−0.0039 (6)
O40.0263 (7)0.0284 (7)0.0337 (7)0.0036 (6)0.0043 (5)0.0010 (6)
C50.0313 (10)0.0355 (11)0.0351 (11)0.0064 (9)0.0060 (8)0.0049 (9)
O50.0274 (7)0.0484 (10)0.0538 (10)0.0046 (7)0.0119 (7)0.0075 (8)
O60.0294 (8)0.0545 (11)0.0509 (10)0.0047 (7)0.0020 (7)0.0003 (8)
C60.0259 (12)0.0271 (12)0.0427 (14)−0.0002 (9)0.0058 (9)−0.0001 (10)
C70.0337 (11)0.0421 (13)0.0610 (16)0.0041 (10)0.0038 (10)0.0111 (12)
C80.0279 (10)0.0437 (13)0.0449 (12)0.0028 (9)0.0057 (9)−0.0062 (10)
C90.0505 (15)0.0572 (17)0.0653 (17)0.0003 (13)0.0173 (13)−0.0208 (14)
C100.0335 (12)0.0614 (17)0.0661 (17)−0.0081 (12)0.0118 (11)−0.0125 (14)
Geometric parameters (Å, °) top
O1—C11.316 (2)C2—H2A0.9900
O2—C11.225 (2)C2—H2B0.9900
C1—C21.502 (3)C3—H3A0.9900
C2—C31.523 (3)C3—H3B0.9900
C3—C41.498 (3)C5—H5A0.9900
C4—O31.211 (2)C5—H5B0.9900
C4—O41.338 (2)C5—H5C0.9900
O4—C51.449 (2)C5—H5D0.9900
C5—C6'1.408 (16)C6—H61.0000
C5—C61.492 (3)C7—H7A0.9900
O5—C6'1.409 (17)C7—H7B0.9900
O5—C81.424 (3)C7—H7C0.9900
O5—C61.424 (3)C7—H7D0.9900
O6—C71.424 (3)C6'—H6'1.0000
O6—C81.424 (3)C9—H9A0.9800
C6—C71.537 (3)C9—H9B0.9800
C7—C6'1.629 (17)C9—H9C0.9800
C8—C91.505 (3)C10—H10A0.9800
C8—C101.505 (3)C10—H10B0.9800
O1—H010.80 (3)C10—H10C0.9800
O2—C1—O1123.58 (17)C6'—C5—H5B122.2
O2—C1—C2122.95 (17)O4—C5—H5B110.3
O1—C1—C2113.42 (16)C6—C5—H5B110.3
C1—C2—C3113.37 (16)H5A—C5—H5B108.5
C4—C3—C2112.54 (16)C6'—C5—H5C106.1
O3—C4—O4123.59 (18)O4—C5—H5C106.1
O3—C4—C3125.36 (18)H5A—C5—H5C137.6
O4—C4—C3111.05 (16)C6'—C5—H5D106.1
C4—O4—C5117.01 (16)O4—C5—H5D106.1
C6'—C5—O4124.8 (7)H5C—C5—H5D106.3
O4—C5—C6107.25 (17)O5—C6—H6110.3
C6'—O5—C8102.9 (7)C5—C6—H6110.3
C8—O5—C6106.90 (17)C7—C6—H6110.3
C7—O6—C8106.95 (17)O6—C7—H7A110.9
O5—C6—C5109.58 (19)C6—C7—H7A110.9
O5—C6—C7104.30 (18)O6—C7—H7B110.9
C5—C6—C7112.0 (2)C6—C7—H7B110.9
O6—C7—C6104.48 (19)H7A—C7—H7B108.9
O6—C7—C6'86.3 (7)O6—C7—H7C114.3
C5—C6'—O5115.5 (14)C6—C7—H7C77.1
C5—C6'—C7111.3 (13)C6'—C7—H7C114.3
O5—C6'—C7100.5 (11)O6—C7—H7D114.3
O6—C8—O5104.06 (17)C6—C7—H7D130.1
O6—C8—C9111.3 (2)C6'—C7—H7D114.3
O5—C8—C9110.8 (2)H7C—C7—H7D111.4
O6—C8—C10109.0 (2)C5—C6'—H6'109.7
O5—C8—C10108.9 (2)O5—C6'—H6'109.7
C9—C8—C10112.4 (2)C7—C6'—H6'109.7
C1—O1—H01109 (2)C8—C9—H9A109.5
C1—C2—H2A108.9C8—C9—H9B109.5
C3—C2—H2A108.9H9A—C9—H9B109.5
C1—C2—H2B108.9C8—C9—H9C109.5
C3—C2—H2B108.9H9A—C9—H9C109.5
H2A—C2—H2B107.7H9B—C9—H9C109.5
C4—C3—H3A109.1C8—C10—H10A109.5
C2—C3—H3A109.1C8—C10—H10B109.5
C4—C3—H3B109.1H10A—C10—H10B109.5
C2—C3—H3B109.1C8—C10—H10C109.5
H3A—C3—H3B107.8H10A—C10—H10C109.5
O4—C5—H5A110.3H10B—C10—H10C109.5
C6—C5—H5A110.3
O2—C1—C2—C330.0 (3)C5—C6—C7—C6'55.6 (9)
O1—C1—C2—C3−152.49 (16)O4—C5—C6'—O518 (2)
C1—C2—C3—C467.0 (2)C6—C5—C6'—O5−57.7 (14)
C2—C3—C4—O3−12.7 (3)O4—C5—C6'—C7131.5 (8)
C2—C3—C4—O4167.00 (15)C6—C5—C6'—C756.1 (12)
O3—C4—O4—C5−8.3 (3)C8—O5—C6'—C5160.9 (13)
C3—C4—O4—C5172.00 (16)C6—O5—C6'—C559.9 (15)
C4—O4—C5—C6'116.4 (12)C8—O5—C6'—C741.0 (13)
C4—O4—C5—C6157.92 (17)C6—O5—C6'—C7−60.0 (10)
C6'—O5—C6—C5−51.5 (9)O6—C7—C6'—C5179.6 (14)
C8—O5—C6—C5−142.17 (19)C6—C7—C6'—C5−60.5 (13)
C6'—O5—C6—C768.5 (9)O6—C7—C6'—O5−57.5 (11)
C8—O5—C6—C7−22.1 (2)C6—C7—C6'—O562.4 (11)
C6'—C5—C6—O553.2 (10)C7—O6—C8—O5−35.5 (2)
O4—C5—C6—O5−70.5 (2)C7—O6—C8—C983.9 (2)
C6'—C5—C6—C7−62.0 (10)C7—O6—C8—C10−151.6 (2)
O4—C5—C6—C7174.27 (18)C6'—O5—C8—O6−7.5 (11)
C8—O6—C7—C621.4 (3)C6—O5—C8—O635.9 (2)
C8—O6—C7—C6'54.2 (8)C6'—O5—C8—C9−127.2 (11)
O5—C6—C7—O60.5 (3)C6—O5—C8—C9−83.9 (2)
C5—C6—C7—O6118.9 (2)C6'—O5—C8—C10108.6 (11)
O5—C6—C7—C6'−62.8 (9)C6—O5—C8—C10152.0 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H01···O2i0.80 (3)1.86 (3)2.6582 (19)175 (3)
C3—H3A···O3ii0.992.363.211 (2)144
C2—H2B···O4iii0.992.573.489 (2)155
C7—H7B···O5iv0.992.603.506 (3)152
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, y−1, z; (iv) x, −y+3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H01···O2i0.80 (3)1.86 (3)2.6582 (19)175 (3)
C3—H3A···O3ii0.992.363.211 (2)144
C2—H2B···O4iii0.992.573.489 (2)155
C7—H7B···O5iv0.992.603.506 (3)152
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, y−1, z; (iv) x, −y+3/2, z−1/2.
Acknowledgements top

Financial support by the Polish State Committee for Scientific Research (grant No. R 05 043 03) is gratefully acknowledged.

references
References top

Kuś, P., Rojkiewicz, M., Zięba, G., Witoszek, M. & Jones, P. G. (2009). Acta Cryst. E65 [BT2935].

Osanai, S., Higami, M., Ono, Y. & Ohta, E. (1997). J. Mater. Chem. 7, 1405–1408.

Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.

Scriba, G. K. E. (1993). Arch. Pharm. (Weinheim), 326, 477–481.

Scriba, G. K. E. (1995). Arch. Pharm. (Weinheim), 328, 271–276.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.