organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

aSchool of Chemistry and Chemical Engineering, Central South University, Changsha 410083, People's Republic of China, bDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou 425100, People's Republic of China, and cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 10 July 2008; accepted 15 July 2008; online 19 July 2008)

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[Al-Mughaid, H., Grindley, T. B., Robertson, K. N. & Cameron, T. S. (2003). Can. J. Chem. 81, 505-516.]); Grosu et al. (1997[Grosu, I., Mager, S., Ple, G., Ple, N., Toscano, A., Mesaros, E. & Martinez, R. (1997). Liebigs Ann. pp. 2371-2377.], 1998[Grosu, I., Mager, S., Toupet, L., Ple, G., Mesaros, E. & Mihis, A. (1998). Acta Chem. Scand. 52, 366-371.]). For applications of this class of compounds, see: Wang et al. (1994[Wang, G., Yuan, X.-Y., Liu, Y.-C. & Lei, X.-G. (1994). J. Am. Oil Chem. Soc. 74, 727-730.]); Yuan et al. (2005[Yuan, X.-Y., Yang, N.-F., Luo, H.-A. & Liu, Y.-J. (2005). Chin. J. Org. Chem. 25, 1049-1052.]).

[Scheme 1]

Experimental

Crystal data
  • C12H16O4

  • Mr = 224.25

  • Orthorhombic, C 2221

  • 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)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.066

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O4—H4O⋯O3i 0.84 2.19 2.644 (6) 114
Symmetry code: (i) [x+{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] 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.
5,5-Bis(hydroxymethyl)-2-phenyl-1,3-dioxane top
Crystal data top
C12H16O4F(000) = 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 = 2.4–27.0°
b = 10.4593 (6) ŵ = 0.10 mm1
c = 34.5285 (19) ÅT = 173 K
V = 2262.7 (2) Å3Block, colorless
Z = 80.46 × 0.42 × 0.21 mm
Data collection top
Bruker SMART 1000
diffractometer
1340 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Graphite monochromatorθmax = 27.0°, θmin = 2.4°
ϕ and ω scansh = 77
5873 measured reflectionsk = 1311
1403 independent reflectionsl = 2444
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.059P)2 + 10.1519P]
where P = (Fo2 + 2Fc2)/3
1403 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
C12H16O4V = 2262.7 (2) Å3
Mr = 224.25Z = 8
Orthorhombic, C2221Mo Kα radiation
a = 6.2654 (4) ŵ = 0.10 mm1
b = 10.4593 (6) ÅT = 173 K
c = 34.5285 (19) Å0.46 × 0.42 × 0.21 mm
Data collection top
Bruker SMART 1000
diffractometer
1340 reflections with I > 2σ(I)
5873 measured reflectionsRint = 0.031
1403 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0660 restraints
wR(F2) = 0.184H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.059P)2 + 10.1519P]
where P = (Fo2 + 2Fc2)/3
1403 reflectionsΔρmax = 0.25 e Å3
145 parametersΔρmin = 0.41 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, º) top
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—O264.2 (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—C1058.0 (5)
C9—O2—C1—C2174.9 (4)O1—C8—C10—C1270.6 (5)
O1—C1—C2—C350.6 (5)O1—C8—C10—C950.1 (5)
O2—C1—C2—C3172.1 (4)O1—C8—C10—C11167.6 (4)
O1—C1—C2—C7132.3 (4)O2—C9—C10—C850.6 (5)
O2—C1—C2—C710.9 (6)O2—C9—C10—C1269.0 (5)
C7—C2—C3—C40.8 (7)O2—C9—C10—C11168.7 (4)
C1—C2—C3—C4176.2 (4)C8—C10—C11—O357.8 (5)
C2—C3—C4—C51.4 (7)C12—C10—C11—O362.5 (5)
C3—C4—C5—C60.7 (8)C9—C10—C11—O3175.6 (4)
C4—C5—C6—C70.5 (8)C8—C10—C12—O4178.6 (4)
C5—C6—C7—C21.0 (7)C9—C10—C12—O462.0 (5)
C3—C2—C7—C60.3 (7)C11—C10—C12—O458.2 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4O···O3i0.842.192.644 (6)114
Symmetry code: (i) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formulaC12H16O4
Mr224.25
Crystal system, space groupOrthorhombic, C2221
Temperature (K)173
a, b, c (Å)6.2654 (4), 10.4593 (6), 34.5285 (19)
V3)2262.7 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.46 × 0.42 × 0.21
Data collection
DiffractometerBruker SMART 1000
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5873, 1403, 1340
Rint0.031
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.184, 1.14
No. of reflections1403
No. of parameters145
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.059P)2 + 10.1519P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.25, 0.41

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4O···O3i0.842.192.644 (6)113.9
Symmetry code: (i) x+1/2, y1/2, z.
 

Acknowledgements

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.

References

First citationAl-Mughaid, H., Grindley, T. B., Robertson, K. N. & Cameron, T. S. (2003). Can. J. Chem. 81, 505–516.  Web of Science CSD CrossRef CAS Google Scholar
First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGrosu, I., Mager, S., Ple, G., Ple, N., Toscano, A., Mesaros, E. & Martinez, R. (1997). Liebigs Ann. pp. 2371–2377.  CrossRef Google Scholar
First citationGrosu, I., Mager, S., Toupet, L., Ple, G., Mesaros, E. & Mihis, A. (1998). Acta Chem. Scand. 52, 366–371.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWang, G., Yuan, X.-Y., Liu, Y.-C. & Lei, X.-G. (1994). J. Am. Oil Chem. Soc. 74, 727–730.  CrossRef Web of Science Google Scholar
First citationWestrip, S. P. (2008). publCIF. In preparation.  Google Scholar
First citationYuan, X.-Y., Yang, N.-F., Luo, H.-A. & Liu, Y.-J. (2005). Chin. J. Org. Chem. 25, 1049–1052.  CAS Google Scholar

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