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

Luo, Y.-M.; Liu, X.-M.; Yuan, X.-Y.; Zhang, M.; Ng, S.W.

doi:10.1107/S1600536808022046

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1536

doi:10.1107/S1600536808022046

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

Yi-Ming Luo,^a Xing-Ming Liu,^a Xian-You Yuan,^b Min Zhang ^b and Seik Weng Ng ^c ^*

^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 ); Grosu et al. (1997 , 1998 ). For applications of this class of compounds, see: Wang et al. (1994 ); Yuan et al. (2005 ).

Experimental

Crystal data

C₁₂H₁₆O₄
M_r = 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)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.184
S = 1.14
1403 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2003 ); data reduction: SAINT; 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 ).

Supporting information

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

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

checkCIF report

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.

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

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

C₁₂H₁₆O₄	F(000) = 960
M_r = 224.25	D_x = 1.317 Mg m⁻³
Orthorhombic, C222₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 4610 reflections
a = 6.2654 (4) Å	θ = 2.4–27.0°
b = 10.4593 (6) Å	µ = 0.10 mm⁻¹
c = 34.5285 (19) Å	T = 173 K
V = 2262.7 (2) Å³	Block, colorless
Z = 8	0.46 × 0.42 × 0.21 mm

Data collection top

Bruker SMART 1000 diffractometer	1340 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 27.0°, θ_min = 2.4°
ϕ and ω scans	h = −7→7
5873 measured reflections	k = −13→11
1403 independent reflections	l = −24→44

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.184	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.059P)² + 10.1519P] where P = (F_o² + 2F_c²)/3
1403 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₂H₁₆O₄	V = 2262.7 (2) Å³
M_r = 224.25	Z = 8
Orthorhombic, C222₁	Mo Kα radiation
a = 6.2654 (4) Å	µ = 0.10 mm⁻¹
b = 10.4593 (6) Å	T = 173 K
c = 34.5285 (19) Å	0.46 × 0.42 × 0.21 mm

Data collection top

Bruker SMART 1000 diffractometer	1340 reflections with I > 2σ(I)
5873 measured reflections	R_int = 0.031
1403 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.184	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.059P)² + 10.1519P] where P = (F_o² + 2F_c²)/3
1403 reflections	Δρ_max = 0.25 e Å⁻³
145 parameters	Δρ_min = −0.41 e Å⁻³

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

	x	y	z	U_iso*/U_eq
O1	0.8999 (6)	0.8806 (3)	0.63367 (9)	0.0263 (8)
O2	0.7606 (6)	0.6825 (3)	0.61705 (10)	0.0271 (8)
O3	0.3975 (7)	0.9308 (4)	0.71647 (11)	0.0410 (10)
H3O	0.4584	0.9956	0.7073	0.061*
O4	0.6297 (7)	0.6260 (4)	0.71881 (12)	0.0509 (12)
H4O	0.7073	0.5941	0.7361	0.076*
C1	0.8416 (8)	0.7994 (4)	0.60313 (13)	0.0223 (10)
H1	0.7304	0.8424	0.5869	0.027*
C2	1.0363 (7)	0.7728 (4)	0.57852 (12)	0.0216 (9)
C3	1.1598 (8)	0.8734 (5)	0.56544 (13)	0.0259 (10)
H3	1.1272	0.9583	0.5732	0.031*
C4	1.3332 (8)	0.8500 (5)	0.54074 (13)	0.0283 (11)
H4	1.4162	0.9193	0.5313	0.034*
C5	1.3830 (9)	0.7266 (5)	0.53020 (14)	0.0304 (11)
H5	1.5014	0.7107	0.5137	0.036*
C6	1.2612 (9)	0.6257 (5)	0.54353 (13)	0.0289 (10)
H6	1.2966	0.5406	0.5364	0.035*
C7	1.0871 (8)	0.6485 (4)	0.56740 (12)	0.0225 (10)
H7	1.0023	0.5791	0.5762	0.027*
C8	0.7140 (9)	0.9151 (4)	0.65602 (14)	0.0266 (11)
H8A	0.6150	0.9651	0.6396	0.032*
H8B	0.7578	0.9698	0.6780	0.032*
C9	0.5640 (8)	0.7038 (5)	0.63773 (14)	0.0282 (11)
H9A	0.5098	0.6214	0.6479	0.034*
H9B	0.4556	0.7391	0.6198	0.034*
C10	0.5989 (8)	0.7970 (4)	0.67141 (12)	0.0210 (9)
C11	0.3785 (8)	0.8368 (5)	0.68698 (14)	0.0287 (11)
H11A	0.2913	0.8713	0.6655	0.034*
H11B	0.3045	0.7608	0.6975	0.034*
C12	0.7350 (8)	0.7357 (5)	0.70299 (13)	0.0300 (11)
H12A	0.8744	0.7098	0.6920	0.036*
H12B	0.7618	0.7987	0.7238	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0287 (17)	0.0241 (16)	0.0261 (15)	−0.0100 (16)	0.0061 (15)	−0.0039 (13)
O2	0.0310 (18)	0.0194 (15)	0.0310 (16)	−0.0038 (16)	0.0109 (15)	−0.0052 (13)
O3	0.045 (2)	0.039 (2)	0.039 (2)	0.001 (2)	0.011 (2)	−0.0089 (17)
O4	0.046 (2)	0.057 (3)	0.049 (2)	0.018 (2)	0.018 (2)	0.031 (2)
C1	0.027 (2)	0.020 (2)	0.020 (2)	−0.002 (2)	0.0019 (18)	0.0012 (17)
C2	0.020 (2)	0.026 (2)	0.0188 (19)	0.0006 (19)	−0.0012 (17)	−0.0025 (18)
C3	0.032 (3)	0.025 (2)	0.0204 (19)	−0.001 (2)	0.000 (2)	−0.0016 (18)
C4	0.025 (2)	0.037 (3)	0.024 (2)	−0.008 (2)	0.0047 (19)	0.000 (2)
C5	0.024 (2)	0.042 (3)	0.025 (2)	0.000 (2)	0.006 (2)	−0.006 (2)
C6	0.031 (3)	0.030 (2)	0.025 (2)	0.003 (2)	0.000 (2)	−0.0081 (19)
C7	0.030 (2)	0.016 (2)	0.0219 (19)	−0.0002 (19)	0.000 (2)	0.0024 (16)
C8	0.038 (3)	0.0165 (19)	0.025 (2)	−0.006 (2)	0.007 (2)	−0.0024 (18)
C9	0.027 (3)	0.025 (2)	0.032 (2)	−0.009 (2)	0.008 (2)	−0.0056 (19)
C10	0.023 (2)	0.0186 (19)	0.0213 (19)	0.0015 (19)	0.0029 (18)	0.0017 (16)
C11	0.023 (2)	0.033 (3)	0.031 (2)	0.006 (2)	0.000 (2)	0.000 (2)
C12	0.025 (2)	0.042 (3)	0.023 (2)	0.014 (2)	0.004 (2)	0.006 (2)

Geometric parameters (Å, º) top

O1—C1	1.403 (5)	C5—H5	0.9500
O1—C8	1.443 (6)	C6—C7	1.388 (7)
O2—C1	1.409 (5)	C6—H6	0.9500
O2—C9	1.441 (6)	C7—H7	0.9500
O3—C11	1.421 (6)	C8—C10	1.526 (6)
O3—H3O	0.8400	C8—H8A	0.9900
O4—C12	1.432 (7)	C8—H8B	0.9900
O4—H4O	0.8399	C9—C10	1.534 (6)
C1—C2	1.512 (6)	C9—H9A	0.9900
C1—H1	1.0000	C9—H9B	0.9900
C2—C3	1.382 (7)	C10—C12	1.526 (6)
C2—C7	1.392 (6)	C10—C11	1.539 (7)
C3—C4	1.403 (7)	C11—H11A	0.9900
C3—H3	0.9500	C11—H11B	0.9900
C4—C5	1.377 (7)	C12—H12A	0.9900
C4—H4	0.9500	C12—H12B	0.9900
C5—C6	1.381 (8)

C1—O1—C8	110.1 (4)	O1—C8—H8A	109.3
C1—O2—C9	110.1 (4)	C10—C8—H8A	109.3
C11—O3—H3O	109.0	O1—C8—H8B	109.3
C12—O4—H4O	108.9	C10—C8—H8B	109.3
O1—C1—O2	111.3 (3)	H8A—C8—H8B	108.0
O1—C1—C2	108.9 (4)	O2—C9—C10	110.6 (4)
O2—C1—C2	108.8 (4)	O2—C9—H9A	109.5
O1—C1—H1	109.3	C10—C9—H9A	109.5
O2—C1—H1	109.3	O2—C9—H9B	109.5
C2—C1—H1	109.3	C10—C9—H9B	109.5
C3—C2—C7	119.5 (4)	H9A—C9—H9B	108.1
C3—C2—C1	119.7 (4)	C8—C10—C12	109.0 (4)
C7—C2—C1	120.8 (4)	C8—C10—C9	108.6 (4)
C2—C3—C4	120.0 (5)	C12—C10—C9	110.7 (4)
C2—C3—H3	120.0	C8—C10—C11	109.1 (4)
C4—C3—H3	120.0	C12—C10—C11	111.4 (4)
C5—C4—C3	120.0 (5)	C9—C10—C11	108.0 (4)
C5—C4—H4	120.0	O3—C11—C10	111.3 (4)
C3—C4—H4	120.0	O3—C11—H11A	109.4
C4—C5—C6	120.2 (5)	C10—C11—H11A	109.4
C4—C5—H5	119.9	O3—C11—H11B	109.4
C6—C5—H5	119.9	C10—C11—H11B	109.4
C5—C6—C7	120.1 (5)	H11A—C11—H11B	108.0
C5—C6—H6	120.0	O4—C12—C10	110.6 (4)
C7—C6—H6	120.0	O4—C12—H12A	109.5
C6—C7—C2	120.3 (4)	C10—C12—H12A	109.5
C6—C7—H7	119.9	O4—C12—H12B	109.5
C2—C7—H7	119.9	C10—C12—H12B	109.5
O1—C8—C10	111.4 (4)	H12A—C12—H12B	108.1

C8—O1—C1—O2	−64.2 (5)	C1—C2—C7—C6	177.4 (4)
C8—O1—C1—C2	175.9 (4)	C1—O1—C8—C10	56.9 (5)
C9—O2—C1—O1	65.2 (5)	C1—O2—C9—C10	−58.0 (5)
C9—O2—C1—C2	−174.9 (4)	O1—C8—C10—C12	70.6 (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—C7	132.3 (4)	O2—C9—C10—C8	50.6 (5)
O2—C1—C2—C7	10.9 (6)	O2—C9—C10—C12	−69.0 (5)
C7—C2—C3—C4	0.8 (7)	O2—C9—C10—C11	168.7 (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—O3	62.5 (5)
C3—C4—C5—C6	0.7 (8)	C9—C10—C11—O3	−175.6 (4)
C4—C5—C6—C7	0.5 (8)	C8—C10—C12—O4	178.6 (4)
C5—C6—C7—C2	−1.0 (7)	C9—C10—C12—O4	−62.0 (5)
C3—C2—C7—C6	0.3 (7)	C11—C10—C12—O4	58.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O3ⁱ	0.84	2.19	2.644 (6)	114

Symmetry code: (i) x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆O₄
M_r	224.25
Crystal system, space group	Orthorhombic, C222₁
Temperature (K)	173
a, b, c (Å)	6.2654 (4), 10.4593 (6), 34.5285 (19)
V (Å³)	2262.7 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.46 × 0.42 × 0.21

Data collection
Diffractometer	Bruker SMART 1000 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5873, 1403, 1340
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.184, 1.14
No. of reflections	1403
No. of parameters	145
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.059P)² + 10.1519P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
O4—H4O···O3ⁱ	0.84	2.19	2.644 (6)	113.9

Symmetry code: (i) x+1/2, y−1/2, 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

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