(5-n-Hexyl-2-hydroxymethyl-1,3-dioxan-2-yl)methanol

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

doi:10.1107/S1600536810041401

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2917

https://doi.org/10.1107/S1600536810041401

Open

access

(5-n-Hexyl-2-hydroxymethyl-1,3-dioxan-2-yl)methanol

Min Zhang,^a Xian-You Yuan ^a and Seik Weng Ng ^b ^*

^aDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou Hunan 425100, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 13 October 2010; accepted 14 October 2010; online 23 October 2010)

In the title compound, C₁₂H₂₄O₄, the dioxane ring adopts a chair conformation; the n-hexyl chain, which occupies an equatorial position, has an extended zigzag conformation. In the crystal, molecules are connected by O—H⋯O hydrogen-bonds into a zigzag chain running along the b axis, giving rise to a herringbone pattern.

Related literature

For a related structure, see: Luo et al. (2008 ).

Experimental

Crystal data

C₁₂H₂₄O₄
M_r = 232.31
Monoclinic, P 2₁ /n
a = 13.6602 (10) Å
b = 5.9370 (5) Å
c = 16.4268 (12) Å
β = 97.737 (1)°
V = 1320.10 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.40 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
7438 measured reflections
2862 independent reflections
1755 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.173
S = 1.06
2862 reflections
154 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4ⁱ	0.84 (1)	1.86 (1)	2.664 (2)	162 (3)
O4—H4⋯O3ⁱⁱ	0.85 (1)	1.81 (1)	2.630 (2)	164 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y-1, z.

Data collection: SMART (Bruker, 2003 ); 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810041401/bt5377sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041401/bt5377Isup2.hkl

checkCIF report

Comment top

A previous study reported the crystal structure of 5,5-bis(hydroxylmethyl)-2-phenylmethyl-1,3-dioxane, which was synthesized by the condensation of 2,2-bis(hydroxymethyl)-1,3-propanediol and an aromatic aldehyde (benzaldehyde) (Luo et al., 2008). A variation of the synthesis with an aliphatic aldehyde under similar reaction conditions yielded a 1,3-dixoxane having the hydroxyl groups connected to another atom of the chair-shaped ring. In the molecule of the C₁₂H₂₄O₄(Scheme I, Fig. 1), the n-hexyl chain, which occupies an equatorial position, has an extended zigzag conformation. The hydroxy unit of one molecule is a hydrogen-bond donor to the hydroxy unit of an adjacent molecule so that the two O–H···O hydrogen bonds give rise to a herring-bone ribbon that runs along the b-axis of the monoclinic unit cell (Fig. 2).

Related literature top

For a related structure, see: Luo et al. (2008).

Experimental top

2,2-Bis(hydroxymethyl)-1,3-propanediol (13.0 g, 96 mmol) and N,N-dimethylformamide (100 ml) were heated until the 2,2-bis(hydroxymethyl)-1,3-propanediol dissolved completely. n-Heptanal (10.1 g, 89 mmol) and p-toluenesulfonic acid monohydrate (1 g, 5 mmol) were added. The solution was heated 363–373 K 5 h. The solution was cooled and ethyl acetate (100 ml) was added to dissolve the residue after DMF was removed by evaporation. The solution was washed successively with water and 5% sodium bicarbonate (50 ml); the solution was dried over sodium sulfate. The solvent was evaporated to give a solid that was recrystallized from ethyl acetate to yield 16.5 g (70%) of colorless crystals.

Structure description top

For a related structure, see: Luo et al. (2008).

Computing details top

Data collection: SMART (Bruker, 2003); 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, 2010).

Figures top

	Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₂H₂₄O₄ at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded ribbon structure.

(5-n-Hexyl-2-hydroxymethyl-1,3-dioxan-2-yl)methanol top

Crystal data top

C₁₂H₂₄O₄	F(000) = 512
M_r = 232.31	D_x = 1.169 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2106 reflections
a = 13.6602 (10) Å	θ = 2.5–27.0°
b = 5.9370 (5) Å	µ = 0.09 mm⁻¹
c = 16.4268 (12) Å	T = 173 K
β = 97.737 (1)°	Prism, colorless
V = 1320.10 (18) Å³	0.40 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1755 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 27.1°, θ_min = 1.8°
ω scans	h = −17→17
7438 measured reflections	k = −7→7
2862 independent reflections	l = −20→14

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0932P)²] where P = (F_o² + 2F_c²)/3
2862 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.32 e Å⁻³
2 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₂₄O₄	V = 1320.10 (18) Å³
M_r = 232.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.6602 (10) Å	µ = 0.09 mm⁻¹
b = 5.9370 (5) Å	T = 173 K
c = 16.4268 (12) Å	0.40 × 0.25 × 0.20 mm
β = 97.737 (1)°

Data collection top

Bruker SMART APEX diffractometer	1755 reflections with I > 2σ(I)
7438 measured reflections	R_int = 0.041
2862 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	2 restraints
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.32 e Å⁻³
2862 reflections	Δρ_min = −0.24 e Å⁻³
154 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.21236 (8)	1.1104 (2)	0.46544 (7)	0.0274 (3)
O2	0.08583 (9)	1.3743 (2)	0.45699 (9)	0.0449 (4)
O3	0.25706 (13)	1.7500 (2)	0.65335 (8)	0.0449 (4)
H3	0.2562 (18)	1.699 (4)	0.7006 (8)	0.063 (8)*
O4	0.24968 (15)	1.1821 (2)	0.68721 (8)	0.0551 (5)
H4	0.257 (2)	1.051 (2)	0.6681 (16)	0.083 (9)*
C1	0.22572 (13)	1.4192 (3)	0.56451 (10)	0.0259 (4)
C2	0.29973 (15)	1.5895 (3)	0.60499 (12)	0.0358 (5)
H2A	0.3529	1.5084	0.6402	0.043*
H2B	0.3302	1.6693	0.5618	0.043*
C3	0.17790 (16)	1.2926 (3)	0.62952 (12)	0.0390 (5)
H3A	0.1398	1.3998	0.6590	0.047*
H3B	0.1313	1.1794	0.6024	0.047*
C4	0.14640 (15)	1.5360 (3)	0.50544 (12)	0.0387 (5)
H4A	0.1046	1.6292	0.5369	0.046*
H4B	0.1780	1.6370	0.4687	0.046*
C5	0.27918 (13)	1.2561 (3)	0.51385 (11)	0.0275 (4)
H5A	0.3173	1.3429	0.4774	0.033*
H5B	0.3264	1.1648	0.5512	0.033*
C6	0.14157 (13)	1.2334 (3)	0.41238 (11)	0.0321 (5)
H6	0.1756	1.3257	0.3737	0.039*
C7	0.07331 (14)	1.0673 (4)	0.36474 (12)	0.0391 (5)
H7A	0.0179	1.1508	0.3333	0.047*
H7B	0.0452	0.9678	0.4040	0.047*
C8	0.12197 (14)	0.9224 (3)	0.30569 (12)	0.0342 (5)
H8A	0.1780	0.8402	0.3368	0.041*
H8B	0.1489	1.0211	0.2655	0.041*
C9	0.05174 (14)	0.7536 (4)	0.25968 (13)	0.0393 (5)
H9A	0.0248	0.6562	0.3002	0.047*
H9B	−0.0043	0.8368	0.2290	0.047*
C10	0.09718 (14)	0.6053 (4)	0.20005 (11)	0.0355 (5)
H10A	0.1277	0.7026	0.1615	0.043*
H10B	0.1505	0.5148	0.2311	0.043*
C11	0.02531 (15)	0.4480 (4)	0.15108 (14)	0.0457 (6)
H11A	−0.0268	0.5389	0.1186	0.055*
H11B	−0.0069	0.3545	0.1897	0.055*
C12	0.07088 (17)	0.2939 (4)	0.09337 (13)	0.0473 (6)
H12A	0.1047	0.3843	0.0558	0.071*
H12B	0.0189	0.2039	0.0617	0.071*
H12C	0.1185	0.1936	0.1252	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0304 (7)	0.0258 (7)	0.0243 (6)	0.0012 (5)	−0.0030 (5)	−0.0047 (5)
O2	0.0375 (8)	0.0450 (9)	0.0482 (9)	0.0139 (7)	−0.0091 (7)	−0.0197 (7)
O3	0.0890 (12)	0.0223 (7)	0.0231 (7)	−0.0018 (7)	0.0063 (8)	−0.0032 (6)
O4	0.1172 (14)	0.0244 (8)	0.0241 (7)	−0.0002 (9)	0.0109 (8)	0.0009 (6)
C1	0.0359 (10)	0.0209 (9)	0.0211 (9)	−0.0008 (7)	0.0041 (7)	−0.0013 (7)
C2	0.0487 (12)	0.0298 (11)	0.0290 (10)	−0.0094 (9)	0.0054 (9)	−0.0058 (8)
C3	0.0559 (13)	0.0301 (11)	0.0349 (11)	−0.0091 (9)	0.0200 (10)	−0.0060 (8)
C4	0.0477 (12)	0.0305 (11)	0.0352 (11)	0.0093 (9)	−0.0046 (9)	−0.0078 (8)
C5	0.0278 (9)	0.0316 (10)	0.0221 (9)	−0.0014 (7)	−0.0002 (7)	−0.0045 (7)
C6	0.0344 (10)	0.0338 (11)	0.0259 (10)	0.0041 (8)	−0.0038 (8)	−0.0051 (8)
C7	0.0301 (10)	0.0468 (13)	0.0373 (11)	0.0054 (9)	−0.0064 (9)	−0.0119 (9)
C8	0.0335 (10)	0.0400 (12)	0.0269 (9)	−0.0021 (9)	−0.0034 (8)	−0.0051 (8)
C9	0.0288 (10)	0.0498 (13)	0.0364 (11)	0.0018 (9)	−0.0059 (9)	−0.0127 (9)
C10	0.0338 (10)	0.0437 (12)	0.0282 (10)	−0.0045 (9)	0.0014 (8)	−0.0039 (9)
C11	0.0353 (11)	0.0528 (14)	0.0464 (12)	−0.0015 (10)	−0.0035 (9)	−0.0196 (10)
C12	0.0541 (13)	0.0490 (14)	0.0388 (12)	−0.0057 (11)	0.0059 (11)	−0.0131 (10)

Geometric parameters (Å, º) top

O1—C6	1.415 (2)	C6—C7	1.503 (3)
O1—C5	1.421 (2)	C6—H6	1.0000
O2—C6	1.403 (2)	C7—C8	1.516 (3)
O2—C4	1.436 (2)	C7—H7A	0.9900
O3—C2	1.415 (2)	C7—H7B	0.9900
O3—H3	0.84 (1)	C8—C9	1.517 (3)
O4—C3	1.428 (3)	C8—H8A	0.9900
O4—H4	0.85 (1)	C8—H8B	0.9900
C1—C2	1.519 (2)	C9—C10	1.511 (3)
C1—C4	1.521 (3)	C9—H9A	0.9900
C1—C3	1.523 (2)	C9—H9B	0.9900
C1—C5	1.525 (2)	C10—C11	1.507 (3)
C2—H2A	0.9900	C10—H10A	0.9900
C2—H2B	0.9900	C10—H10B	0.9900
C3—H3A	0.9900	C11—C12	1.510 (3)
C3—H3B	0.9900	C11—H11A	0.9900
C4—H4A	0.9900	C11—H11B	0.9900
C4—H4B	0.9900	C12—H12A	0.9800
C5—H5A	0.9900	C12—H12B	0.9800
C5—H5B	0.9900	C12—H12C	0.9800

C6—O1—C5	111.39 (13)	O1—C6—H6	109.7
C6—O2—C4	112.06 (13)	C7—C6—H6	109.7
C2—O3—H3	109.7 (18)	C6—C7—C8	114.28 (15)
C3—O4—H4	106.1 (19)	C6—C7—H7A	108.7
C2—C1—C4	110.53 (16)	C8—C7—H7A	108.7
C2—C1—C3	110.16 (14)	C6—C7—H7B	108.7
C4—C1—C3	109.65 (15)	C8—C7—H7B	108.7
C2—C1—C5	108.80 (14)	H7A—C7—H7B	107.6
C4—C1—C5	107.08 (14)	C7—C8—C9	113.05 (16)
C3—C1—C5	110.57 (15)	C7—C8—H8A	109.0
O3—C2—C1	113.19 (15)	C9—C8—H8A	109.0
O3—C2—H2A	108.9	C7—C8—H8B	109.0
C1—C2—H2A	108.9	C9—C8—H8B	109.0
O3—C2—H2B	108.9	H8A—C8—H8B	107.8
C1—C2—H2B	108.9	C10—C9—C8	114.86 (16)
H2A—C2—H2B	107.8	C10—C9—H9A	108.6
O4—C3—C1	111.78 (16)	C8—C9—H9A	108.6
O4—C3—H3A	109.3	C10—C9—H9B	108.6
C1—C3—H3A	109.3	C8—C9—H9B	108.6
O4—C3—H3B	109.3	H9A—C9—H9B	107.5
C1—C3—H3B	109.3	C11—C10—C9	114.35 (16)
H3A—C3—H3B	107.9	C11—C10—H10A	108.7
O2—C4—C1	110.89 (15)	C9—C10—H10A	108.7
O2—C4—H4A	109.5	C11—C10—H10B	108.7
C1—C4—H4A	109.5	C9—C10—H10B	108.7
O2—C4—H4B	109.5	H10A—C10—H10B	107.6
C1—C4—H4B	109.5	C10—C11—C12	114.61 (17)
H4A—C4—H4B	108.0	C10—C11—H11A	108.6
O1—C5—C1	111.91 (13)	C12—C11—H11A	108.6
O1—C5—H5A	109.2	C10—C11—H11B	108.6
C1—C5—H5A	109.2	C12—C11—H11B	108.6
O1—C5—H5B	109.2	H11A—C11—H11B	107.6
C1—C5—H5B	109.2	C11—C12—H12A	109.5
H5A—C5—H5B	107.9	C11—C12—H12B	109.5
O2—C6—O1	111.11 (14)	H12A—C12—H12B	109.5
O2—C6—C7	108.74 (14)	C11—C12—H12C	109.5
O1—C6—C7	107.86 (15)	H12A—C12—H12C	109.5
O2—C6—H6	109.7	H12B—C12—H12C	109.5

C4—C1—C2—O3	62.40 (19)	C4—C1—C5—O1	−52.67 (19)
C3—C1—C2—O3	−58.9 (2)	C3—C1—C5—O1	66.74 (19)
C5—C1—C2—O3	179.70 (15)	C4—O2—C6—O1	60.4 (2)
C2—C1—C3—O4	−57.4 (2)	C4—O2—C6—C7	179.00 (16)
C4—C1—C3—O4	−179.27 (15)	C5—O1—C6—O2	−60.02 (18)
C5—C1—C3—O4	62.89 (19)	C5—O1—C6—C7	−179.11 (14)
C6—O2—C4—C1	−57.7 (2)	O2—C6—C7—C8	173.00 (17)
C2—C1—C4—O2	170.43 (14)	O1—C6—C7—C8	−66.4 (2)
C3—C1—C4—O2	−67.93 (19)	C6—C7—C8—C9	178.94 (17)
C5—C1—C4—O2	52.08 (19)	C7—C8—C9—C10	180.00 (18)
C6—O1—C5—C1	57.40 (18)	C8—C9—C10—C11	−176.53 (18)
C2—C1—C5—O1	−172.15 (14)	C9—C10—C11—C12	−178.08 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4ⁱ	0.84 (1)	1.86 (1)	2.664 (2)	162 (3)
O4—H4···O3ⁱⁱ	0.85 (1)	1.81 (1)	2.630 (2)	164 (3)

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₄O₄
M_r	232.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	13.6602 (10), 5.9370 (5), 16.4268 (12)
β (°)	97.737 (1)
V (Å³)	1320.10 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7438, 2862, 1755
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.173, 1.06
No. of reflections	2862
No. of parameters	154
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.24

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4ⁱ	0.84 (1)	1.86 (1)	2.664 (2)	162 (3)
O4—H4···O3ⁱⁱ	0.85 (1)	1.81 (1)	2.630 (2)	164 (3)

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x, y−1, z.

Acknowledgements

We thank the S&T Technology Planning Project of Hunan Province (No. 2010 N K3007), the Key Scientific Research Project of Hunan Provincial Education Department (No. 08 A023), the NSF of Hunan Province (09 J J3028), the Key Construction Project of Hunan Province (No. 2000–180) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Luo, Y.-M., Liu, X.-M., Yuan, X.-Y., Zhang, M. & Ng, S. W. (2008). Acta Cryst. E64, o1536. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar