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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1536.
Published online 2008 July 19. doi:  10.1107/S1600536808022046
PMCID: PMC2962161

5,5-Bis(hydroxy­meth­yl)-2-phenyl-1,3-dioxane

Abstract

In the title compound, C12H16O4, the 1,3-dioxane ring adopts a chair conformation; the 2-phenyl substitutent occupies an equatorial position. Adjacent mol­ecules are linked by O—H(...)O hydrogen bonds into a chain.

Related literature

For the crystal structures of similar 5-aryl-1,3-dioxanes, see: Al-Mughaid et al. (2003 [triangle]); Grosu et al. (1997 [triangle], 1998 [triangle]). For applications of this class of compounds, see: Wang et al. (1994 [triangle]); Yuan et al. (2005 [triangle]).

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Object name is e-64-o1536-scheme1.jpg

Experimental

Crystal data

  • C12H16O4
  • M r = 224.25
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1536-efi1.jpg
  • a = 6.2654 (4) Å
  • b = 10.4593 (6) Å
  • c = 34.5285 (19) Å
  • V = 2262.7 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 173 (2) K
  • 0.46 × 0.42 × 0.21 mm

Data collection

  • Bruker SMART 1000 diffractometer
  • Absorption correction: none
  • 5873 measured reflections
  • 1403 independent reflections
  • 1340 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.184
  • S = 1.14
  • 1403 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022046/wn2272sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022046/wn2272Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Key Subject Construction Project of Hunan Province (No. 2006-180), the Key Scientific Research Project of Hunan Provincial Education Department (No. 07 A023) and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The title compound was synthesized to be used as a precursor in organic syntheses. This class of compounds has useful insecticidal as well as anti-foaming properties (Yuan et al., 2005; Wang et al., 1994). The 1,3-dioxane ring adopts a chair conformation; the phenyl substitutent in the 2-position occupies an equatorial position (Fig. 1). Adjacent molecules are linked by O—H···O hydrogen bonds into a chain. The crystal structures of some similar 5-aryl-1,3-dioxanes have been reported (Al-Mughaid et al., 2003; Grosu et al. 1997; 1998).

Experimental

2,2-Bis(hydroxymethyl)-1,3-propanediol (4.0 g, 30 mmol) and DMF (20 ml) were heated to 353 K. Iodine (0.5 g in an active carbon load of 23.6% by mass) and benzaldehyde (30 ml) were added. The clear solution was heated at 353–363 K for 5 h. The solution was filtered hot and the solvent removed by evaporation. The residue was dissolved in diethyl ether (50 ml) and the solution washed with 5% aqueous sodium bicarbonate. The diethyl ether solution was dried over sodium sulfate. Removal of the solvent gave a solid that was recrystallized from ethyl acetate (yield 5.5 g, 80%); m.p. 408 K.

Refinement

In the absence of significant anomalous scattering effects, Friedel pairs were merged. Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, Uiso(H) = 1.2Ueq(C). The H-atoms of the hydroxyl groups were placed at calculated positions and then refined as riding; O—H = 0.84 Å and Uiso(H) = 1.5Ueq(O). For one of the two hydroxyl groups (O3), its hydrogen atom does not form a hydrogen bond to an adjacent acceptor atom. Other possibilities for placing hydrogen atoms on the two groups led to unacceptably short H···H interactions of less than 2 Å.

Figures

Fig. 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 70% level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C12H16O4F000 = 960
Mr = 224.25Dx = 1.317 Mg m3
Orthorhombic, C2221Mo Kα radiation λ = 0.71073 Å
Hall symbol: C 2c 2Cell parameters from 4610 reflections
a = 6.2654 (4) Åθ = 2.4–27.0º
b = 10.4593 (6) ŵ = 0.10 mm1
c = 34.5285 (19) ÅT = 173 (2) K
V = 2262.7 (2) Å3Block, colorless
Z = 80.46 × 0.42 × 0.21 mm

Data collection

Bruker SMART 1000 diffractometer1340 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Monochromator: graphiteθmax = 27.0º
T = 173(2) Kθmin = 2.4º
[var phi] and ω scansh = −7→7
Absorption correction: Nonek = −13→11
5873 measured reflectionsl = −24→44
1403 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.184  w = 1/[σ2(Fo2) + (0.059P)2 + 10.1519P] where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
1403 reflectionsΔρmax = 0.25 e Å3
145 parametersΔρmin = −0.41 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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

xyzUiso*/Ueq
O10.8999 (6)0.8806 (3)0.63367 (9)0.0263 (8)
O20.7606 (6)0.6825 (3)0.61705 (10)0.0271 (8)
O30.3975 (7)0.9308 (4)0.71647 (11)0.0410 (10)
H3O0.45840.99560.70730.061*
O40.6297 (7)0.6260 (4)0.71881 (12)0.0509 (12)
H4O0.70730.59410.73610.076*
C10.8416 (8)0.7994 (4)0.60313 (13)0.0223 (10)
H10.73040.84240.58690.027*
C21.0363 (7)0.7728 (4)0.57852 (12)0.0216 (9)
C31.1598 (8)0.8734 (5)0.56544 (13)0.0259 (10)
H31.12720.95830.57320.031*
C41.3332 (8)0.8500 (5)0.54074 (13)0.0283 (11)
H41.41620.91930.53130.034*
C51.3830 (9)0.7266 (5)0.53020 (14)0.0304 (11)
H51.50140.71070.51370.036*
C61.2612 (9)0.6257 (5)0.54353 (13)0.0289 (10)
H61.29660.54060.53640.035*
C71.0871 (8)0.6485 (4)0.56740 (12)0.0225 (10)
H71.00230.57910.57620.027*
C80.7140 (9)0.9151 (4)0.65602 (14)0.0266 (11)
H8A0.61500.96510.63960.032*
H8B0.75780.96980.67800.032*
C90.5640 (8)0.7038 (5)0.63773 (14)0.0282 (11)
H9A0.50980.62140.64790.034*
H9B0.45560.73910.61980.034*
C100.5989 (8)0.7970 (4)0.67141 (12)0.0210 (9)
C110.3785 (8)0.8368 (5)0.68698 (14)0.0287 (11)
H11A0.29130.87130.66550.034*
H11B0.30450.76080.69750.034*
C120.7350 (8)0.7357 (5)0.70299 (13)0.0300 (11)
H12A0.87440.70980.69200.036*
H12B0.76180.79870.72380.036*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0287 (17)0.0241 (16)0.0261 (15)−0.0100 (16)0.0061 (15)−0.0039 (13)
O20.0310 (18)0.0194 (15)0.0310 (16)−0.0038 (16)0.0109 (15)−0.0052 (13)
O30.045 (2)0.039 (2)0.039 (2)0.001 (2)0.011 (2)−0.0089 (17)
O40.046 (2)0.057 (3)0.049 (2)0.018 (2)0.018 (2)0.031 (2)
C10.027 (2)0.020 (2)0.020 (2)−0.002 (2)0.0019 (18)0.0012 (17)
C20.020 (2)0.026 (2)0.0188 (19)0.0006 (19)−0.0012 (17)−0.0025 (18)
C30.032 (3)0.025 (2)0.0204 (19)−0.001 (2)0.000 (2)−0.0016 (18)
C40.025 (2)0.037 (3)0.024 (2)−0.008 (2)0.0047 (19)0.000 (2)
C50.024 (2)0.042 (3)0.025 (2)0.000 (2)0.006 (2)−0.006 (2)
C60.031 (3)0.030 (2)0.025 (2)0.003 (2)0.000 (2)−0.0081 (19)
C70.030 (2)0.016 (2)0.0219 (19)−0.0002 (19)0.000 (2)0.0024 (16)
C80.038 (3)0.0165 (19)0.025 (2)−0.006 (2)0.007 (2)−0.0024 (18)
C90.027 (3)0.025 (2)0.032 (2)−0.009 (2)0.008 (2)−0.0056 (19)
C100.023 (2)0.0186 (19)0.0213 (19)0.0015 (19)0.0029 (18)0.0017 (16)
C110.023 (2)0.033 (3)0.031 (2)0.006 (2)0.000 (2)0.000 (2)
C120.025 (2)0.042 (3)0.023 (2)0.014 (2)0.004 (2)0.006 (2)

Geometric parameters (Å, °)

O1—C11.403 (5)C5—H50.9500
O1—C81.443 (6)C6—C71.388 (7)
O2—C11.409 (5)C6—H60.9500
O2—C91.441 (6)C7—H70.9500
O3—C111.421 (6)C8—C101.526 (6)
O3—H3O0.8400C8—H8A0.9900
O4—C121.432 (7)C8—H8B0.9900
O4—H4O0.8399C9—C101.534 (6)
C1—C21.512 (6)C9—H9A0.9900
C1—H11.0000C9—H9B0.9900
C2—C31.382 (7)C10—C121.526 (6)
C2—C71.392 (6)C10—C111.539 (7)
C3—C41.403 (7)C11—H11A0.9900
C3—H30.9500C11—H11B0.9900
C4—C51.377 (7)C12—H12A0.9900
C4—H40.9500C12—H12B0.9900
C5—C61.381 (8)
C1—O1—C8110.1 (4)O1—C8—H8A109.3
C1—O2—C9110.1 (4)C10—C8—H8A109.3
C11—O3—H3O109.0O1—C8—H8B109.3
C12—O4—H4O108.9C10—C8—H8B109.3
O1—C1—O2111.3 (3)H8A—C8—H8B108.0
O1—C1—C2108.9 (4)O2—C9—C10110.6 (4)
O2—C1—C2108.8 (4)O2—C9—H9A109.5
O1—C1—H1109.3C10—C9—H9A109.5
O2—C1—H1109.3O2—C9—H9B109.5
C2—C1—H1109.3C10—C9—H9B109.5
C3—C2—C7119.5 (4)H9A—C9—H9B108.1
C3—C2—C1119.7 (4)C8—C10—C12109.0 (4)
C7—C2—C1120.8 (4)C8—C10—C9108.6 (4)
C2—C3—C4120.0 (5)C12—C10—C9110.7 (4)
C2—C3—H3120.0C8—C10—C11109.1 (4)
C4—C3—H3120.0C12—C10—C11111.4 (4)
C5—C4—C3120.0 (5)C9—C10—C11108.0 (4)
C5—C4—H4120.0O3—C11—C10111.3 (4)
C3—C4—H4120.0O3—C11—H11A109.4
C4—C5—C6120.2 (5)C10—C11—H11A109.4
C4—C5—H5119.9O3—C11—H11B109.4
C6—C5—H5119.9C10—C11—H11B109.4
C5—C6—C7120.1 (5)H11A—C11—H11B108.0
C5—C6—H6120.0O4—C12—C10110.6 (4)
C7—C6—H6120.0O4—C12—H12A109.5
C6—C7—C2120.3 (4)C10—C12—H12A109.5
C6—C7—H7119.9O4—C12—H12B109.5
C2—C7—H7119.9C10—C12—H12B109.5
O1—C8—C10111.4 (4)H12A—C12—H12B108.1
C8—O1—C1—O2−64.2 (5)C1—C2—C7—C6177.4 (4)
C8—O1—C1—C2175.9 (4)C1—O1—C8—C1056.9 (5)
C9—O2—C1—O165.2 (5)C1—O2—C9—C10−58.0 (5)
C9—O2—C1—C2−174.9 (4)O1—C8—C10—C1270.6 (5)
O1—C1—C2—C3−50.6 (5)O1—C8—C10—C9−50.1 (5)
O2—C1—C2—C3−172.1 (4)O1—C8—C10—C11−167.6 (4)
O1—C1—C2—C7132.3 (4)O2—C9—C10—C850.6 (5)
O2—C1—C2—C710.9 (6)O2—C9—C10—C12−69.0 (5)
C7—C2—C3—C40.8 (7)O2—C9—C10—C11168.7 (4)
C1—C2—C3—C4−176.2 (4)C8—C10—C11—O3−57.8 (5)
C2—C3—C4—C5−1.4 (7)C12—C10—C11—O362.5 (5)
C3—C4—C5—C60.7 (8)C9—C10—C11—O3−175.6 (4)
C4—C5—C6—C70.5 (8)C8—C10—C12—O4178.6 (4)
C5—C6—C7—C2−1.0 (7)C9—C10—C12—O4−62.0 (5)
C3—C2—C7—C60.3 (7)C11—C10—C12—O458.2 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4O···O3i0.842.192.644 (6)114

Symmetry codes: (i) x+1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2272).

References

  • Al-Mughaid, H., Grindley, T. B., Robertson, K. N. & Cameron, T. S. (2003). Can. J. Chem.81, 505–516.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (1997). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Grosu, I., Mager, S., Ple, G., Ple, N., Toscano, A., Mesaros, E. & Martinez, R. (1997). Liebigs Ann. pp. 2371–2377.
  • Grosu, I., Mager, S., Toupet, L., Ple, G., Mesaros, E. & Mihis, A. (1998). Acta Chem. Scand.52, 366–371.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, G., Yuan, X.-Y., Liu, Y.-C. & Lei, X.-G. (1994). J. Am. Oil Chem. Soc.74, 727–730.
  • Westrip, S. P. (2008). publCIF In preparation.
  • Yuan, X.-Y., Yang, N.-F., Luo, H.-A. & Liu, Y.-J. (2005). Chin. J. Org. Chem.25, 1049–1052.

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