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

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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.067
• wR factor = 0.185
• Data-to-parameter ratio = 9.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O3     -   H3O    ...          ?

Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT417_ALERT_2_C Short Inter D-H..H-D       H3O    ..  H4O     ..       2.13 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.96
           From the CIF: _reflns_number_total               1403
           Count of symmetry unique reflns         1424
           Completeness (_total/calc)             98.53%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. 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).

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).

S2. 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.

S3. 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, U_iso(H) = 1.2U_eq(C). The H-atoms of the hydroxyl groups were placed at calculated positions and then refined as riding; O—H = 0.84 Å and U_iso(H) = 1.5U_eq(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

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

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

Crystal data

C12H16O4	F(000) = 960
Mr = 224.25	Dx = 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) Å^3	Block, colorless
Z = 8	0.46 × 0.42 × 0.21 mm

Data collection

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

Refinement

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

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O3^i	0.84	2.19	2.644 (6)	114

Symmetry code: (i) x+1/2, y−1/2, z.