1,17-Hepta­decane­diol

In the title compound, C₁₇H₃₆O₂, one of the hydroxyl groups has a gauche conformation with respect to the hydro­carbon skeleton, which is all-trans, whereas the other has a trans conformation. The molecular shape is rod-like and the compound has a rotator phase in which mol­ecules are assured greater motional freedom, as in liquid crystals. In addition, the mol­ecules arranged along the longest axis, b, form layers which are very similar to those of the smectic A liquid crystals.

S1. Comment

The crystallographic investigation of long chain organic molecules has been carried out since the early days of X-ray crystallography; for example, early work on paraffins (Müller, 1928) demonstrated the rod-like conformation of these molecules in the crystalline state. The structures of nine α,ω-alkanediols containing from 10 through 16, 18 and 21 carbon atoms have been recently investigated as a models for polymers and/or smectic liquid crystals by Nakamura and his coworkers: 1,10-decanediol (Nakamura & Sato, 1999a), 1,11-undecanediol (Nakamura et al., 1999), 1,12-dodecanediol (Nakamura & Setodoi, 1997), 1,13-tridecanediol (Nakamura et al., 1997), 1,14-tetradecanediol (Nakamura & Sato, 1999b), 1,15-pentadecanediol (Nakamura, Uno, Watanabe et al., 2000), 1,16-hexadecanediol (Nakamura & Yamamoto, 1994), 1,18-octadecanediol (Nakamura & Watanabe, 2001) and 1,21-henicosanediol (Nakamura, Uno & Ogawa et al., 2000). The results showed a consistent distinction between the structures with even numbers of carbon atoms and odd numbers of carbon atoms. In the α,ω-alkanediols with even numbers of carbon atoms, the hydroxyl groups showed all-trans conformation with respect to the skeleton. In these structures, the molecules are arranged in layers in a herring-bone fashion similar to smectic C liquid crystals. In contrast, in structures of the α,ω-alkanediols with odd numbers of carbon atoms, one hydroxyl group adopts a gauche conformation with respect to the hydrocarbon skeleton, whereas the other hydroxyl group adopts a trans conformation. In these structures, the molecules form a layer structure which is similar to that found in smectic A liquid crystals. In addition, phase transitions in α,ω-alkanediols from C₁₃ through C₂₄ were studied and a linear relation between the longest unit-cell length and number of carbon atoms was reported using powder X-ray diffraction (Ogawa & Nakamura, 1999). \sch

Fig. 1 shows the molecular structure of 1,17-heptadecanediol, (I). Except for the length of the b axis, the longest one, no appreciable differences are observed between the crystal data obtained in this study and those of homologues with odd numbers of carbon atoms reported previously. The terminal torsion angles O1—C1—C2—C3 and O2—C17—C16—C15 are 63.3 (3) and -179.3 (2)°, respectively. This means that the former has gauche conformation and the latter trans. An existence of gauche conformation in the molecules is a typical feature of the structures of α,ω-alkanediols with an odd number of carbon atoms. The molecules arranged along the b axis forming layers with a thickness of a/2, as can be seen in Fig. 2. It must be noted that this layer structure is quite similar to the smectic A structure of liquid crystals. This structure of (I), as well as the homologues with odd numbers of carbon atoms, has two different types of hydrogen bond, one is interlayer and the other is intralayer. The donor-acceptor distances of interlayer and intralayer hydrogen bonds are 2.782 (4) and 2.705 (2) Å, respectively. The values of torsion angle of gauche conformation observed in this study are in good agreement with those of α,ω-alkanediol structures containing other odd numbers of carbon atoms [e.g. 1,11-undecanediol 63.3 (3)°, 1,15-pentadecanediol 63.2 (4)° and 1,21-henicosanediol 65.1 (5)°]. The distances of both hydrogen bonds are also comparable to those of 1,11-undecanediol [2.775 (3) and 2.710 (2) Å], 1,13-tridecanediol [2.776 (4) and 2.713 (2) Å], 1,15-pentadecanediol [2.777 (3) and 2.713 (2) Å] and 1,21-henicosanediol [2.778 (4) and 2.717 (3) Å].

The above observations contrast with the structures of even number of carbon α,ω-alkanediols. The all-trans structures contain only one type hydrogen bond. The centrosymmetric molecules are arranged in a zigzag manner making a herring-bone motif. This kind of structure had been observed not only in α,ω-alkanediols with even numbers of carbon atoms but also in several examples of α,ω-alkanedibromides: 1,12-dibromododecane (Kuple et al., 1981), 1,16-dibromohexadecane (Kobayashi et al., 1995) and 1,18-dibromooctadecane (Nakamura et al., 1993). All these structures are similar to the smectic C structure of liquid crystals.

Related literature

For related literature, see: Kobayashi et al. (1995); Kuple et al. (1981); Müller (1928); Nakamura & Sato (1999a, 1999b); Nakamura & Setodoi (1997); Nakamura & Watanabe (2001); Nakamura & Yamamoto (1994); Nakamura et al. (1993, 1999); Nakamura, Tanihara & Takayama (1997); Nakamura, Uno & Ogawa (2000); Nakamura, Uno, Watanabe, Ikeya & Ogawa (2000); Ogawa & Nakamura (1999).

S2. Experimental

The title compound was synthesized as previously described (Ogawa & Nakamura, 1999). The single-crystal used for analysis was grown by slow evaporation from a solution containing a mixture of methanol, ethyl acetate and n-heptane (1:1:3).

S3. Refinement

The methylene H atoms were located at idealized positions, and were allowed to ride on the parent carbon atoms. The hydrogen isotropic displacement parameters were set to be 1.2U_eq of the parent carbon atom. The hydroxyl H atoms were located from a difference Fourier map, and were allowed to refine isotropically for the final refinements.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

Figures

Fig. 1. An ORTEPII (Johnson, 1976) view of the title molecule showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Fig. 2. The projection of the crystal structure along the c axis. Dotted lines indicate the hydrogen bond.

(I)

Crystal data

C17H36O2	Dx = 1.037 Mg m^−3
Mr = 272.47	Cu Kα radiation, λ = 1.5418 Å
Orthorhombic, P212121	Cell parameters from 24 reflections
a = 7.197 (4) Å	θ = 9.3–16.2°
b = 47.756 (2) Å	µ = 0.50 mm^−1
c = 5.076 (3) Å	T = 296 K
V = 1744 (1) Å^3	Plate, colorless
Z = 4	0.8 × 0.4 × 0.02 mm
F(000) = 616.00

Data collection

Rigaku AFC5R diffractometer	1335 reflections with I > 2.0σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.043
Graphite monochromator	θmax = 70.6°, θmin = 2.8°
ω scans	h = −2→8
Absorption correction: ψ scans (North,Phillips & Mathews,1968)	k = −1→58
Tmin = 0.882, Tmax = 0.999	l = −1→6
3140 measured reflections	3 standard reflections every 150 reflections
1929 independent reflections	intensity decay: 1.4%

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.054	w = 1/[σ^2(Fo) + 0.00063|Fo|^2]
S = 1.36	(Δ/σ)max = 0.0004
1335 reflections	Δρmax = 0.13 e Å^−3
180 parameters	Δρmin = −0.21 e Å^−3

Special details

Experimental. none

Geometry. none

Refinement. None

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

	x	y	z	Uiso*/Ueq
O1	0.0537 (3)	−0.22814 (3)	0.1416 (4)	0.0639 (5)
O2	0.0643 (3)	0.22311 (3)	0.5720 (4)	0.0726 (6)
C1	−0.0039 (4)	−0.22534 (4)	0.4087 (5)	0.0667 (8)
C2	0.0520 (4)	−0.19783 (4)	0.5280 (5)	0.0596 (6)
C3	−0.0346 (3)	−0.17231 (4)	0.4006 (4)	0.0506 (6)
C4	0.0377 (3)	−0.14503 (4)	0.5136 (4)	0.0496 (6)
C5	−0.0426 (3)	−0.11891 (4)	0.3896 (4)	0.0491 (6)
C6	0.0368 (3)	−0.09195 (4)	0.5020 (5)	0.0487 (6)
C7	−0.0424 (3)	−0.06553 (4)	0.3802 (5)	0.0493 (6)
C8	0.0384 (3)	−0.03881 (4)	0.4937 (4)	0.0487 (6)
C9	−0.0411 (3)	−0.01218 (4)	0.3756 (4)	0.0495 (5)
C10	0.0394 (3)	0.01444 (4)	0.4918 (4)	0.0494 (6)
C11	−0.0401 (3)	0.04115 (4)	0.3767 (5)	0.0485 (6)
C12	0.0396 (3)	0.06759 (4)	0.4963 (5)	0.0491 (6)
C13	−0.0402 (3)	0.09456 (4)	0.3862 (4)	0.0488 (6)
C14	0.0403 (3)	0.12079 (4)	0.5101 (5)	0.0500 (6)
C15	−0.0388 (3)	0.14802 (4)	0.4053 (4)	0.0504 (6)
C16	0.0472 (4)	0.17350 (4)	0.5363 (5)	0.0528 (6)
C17	−0.0281 (4)	0.20100 (4)	0.4375 (5)	0.0552 (7)
H1a	−0.1354	−0.2269	0.4159	0.0800*
H1b	0.0506	−0.2400	0.5087	0.0800*
H1o	0.170 (4)	−0.2260 (6)	0.144 (7)	0.09 (1)*
H2a	0.0171	−0.1980	0.7085	0.0715*
H2b	0.1832	−0.1962	0.5144	0.0715*
H2o	0.025 (5)	0.2378 (6)	0.488 (8)	0.12 (1)*
H3a	−0.0081	−0.1727	0.2173	0.0607*
H3b	−0.1653	−0.1730	0.4264	0.0607*
H4a	0.0095	−0.1447	0.6964	0.0595*
H4b	0.1687	−0.1446	0.4903	0.0595*
H5a	−0.0176	−0.1194	0.2059	0.0589*
H5b	−0.1732	−0.1189	0.4173	0.0589*
H6a	0.0119	−0.0916	0.6858	0.0584*
H6b	0.1674	−0.0920	0.4741	0.0584*
H7a	−0.0177	−0.0659	0.1963	0.0592*
H7b	−0.1729	−0.0654	0.4084	0.0592*
H8a	0.0148	−0.0386	0.6778	0.0584*
H8b	0.1687	−0.0389	0.4638	0.0584*
H9a	−0.0167	−0.0123	0.1916	0.0594*
H9b	−0.1716	−0.0121	0.4042	0.0594*
H10a	0.0159	0.0144	0.6760	0.0592*
H10b	0.1698	0.0144	0.4619	0.0592*
H11a	−0.0154	0.0413	0.1929	0.0582*
H11b	−0.1706	0.0411	0.4049	0.0582*
H12a	0.0164	0.0672	0.6805	0.0590*
H12b	0.1699	0.0676	0.4660	0.0590*
H13a	−0.0160	0.0951	0.2023	0.0586*
H13b	−0.1706	0.0945	0.4150	0.0586*
H14a	0.0172	0.1201	0.6943	0.0600*
H14b	0.1705	0.1208	0.4796	0.0600*
H15a	−0.0159	0.1490	0.2212	0.0605*
H15b	−0.1690	0.1482	0.4362	0.0605*
H16a	0.0243	0.1724	0.7204	0.0634*
H16b	0.1773	0.1731	0.5052	0.0634*
H17a	−0.1578	0.2020	0.4709	0.0662*
H17b	−0.0064	0.2026	0.2535	0.0662*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.089 (2)	0.0396 (7)	0.0634 (9)	−0.0068 (9)	0.003 (1)	−0.0031 (7)
O2	0.093 (1)	0.0346 (7)	0.090 (1)	0.0019 (8)	−0.026 (1)	−0.0007 (7)
C1	0.094 (2)	0.0385 (10)	0.068 (2)	−0.004 (1)	0.008 (1)	0.009 (1)
C2	0.086 (2)	0.0419 (10)	0.051 (1)	0.003 (1)	−0.005 (2)	0.0036 (9)
C3	0.059 (1)	0.0372 (9)	0.055 (1)	0.0005 (10)	−0.002 (1)	−0.0007 (9)
C4	0.056 (1)	0.0384 (9)	0.054 (1)	−0.0001 (10)	−0.003 (2)	−0.0029 (8)
C5	0.054 (1)	0.0370 (9)	0.056 (1)	0.0011 (9)	−0.001 (2)	−0.0021 (8)
C6	0.050 (1)	0.0371 (9)	0.059 (1)	−0.0002 (9)	−0.003 (1)	−0.0042 (8)
C7	0.051 (1)	0.0361 (9)	0.061 (1)	0.0017 (9)	−0.002 (2)	−0.0027 (9)
C8	0.052 (1)	0.0359 (9)	0.059 (1)	0.0002 (9)	−0.001 (1)	−0.0023 (9)
C9	0.052 (1)	0.0362 (9)	0.060 (1)	0.001 (1)	−0.003 (1)	−0.0008 (9)
C10	0.053 (1)	0.0362 (9)	0.059 (1)	0.000 (1)	−0.002 (1)	−0.0014 (9)
C11	0.051 (1)	0.0360 (9)	0.059 (1)	0.0012 (9)	−0.001 (2)	−0.0005 (9)
C12	0.053 (1)	0.0358 (9)	0.059 (1)	0.0007 (10)	−0.001 (1)	0.0008 (8)
C13	0.051 (1)	0.0366 (9)	0.058 (1)	0.0014 (9)	−0.002 (2)	0.0006 (8)
C14	0.053 (1)	0.0356 (9)	0.061 (1)	−0.0011 (9)	0.000 (2)	0.0008 (8)
C15	0.054 (1)	0.0371 (9)	0.060 (1)	0.0014 (10)	−0.001 (2)	0.0006 (9)
C16	0.059 (1)	0.0351 (9)	0.064 (1)	0.0012 (10)	−0.003 (2)	0.0026 (9)
C17	0.061 (2)	0.0365 (9)	0.069 (1)	0.0022 (10)	−0.004 (1)	0.0005 (9)

Geometric parameters (Å, º)

O1—C1	1.424 (3)	C8—C9	1.518 (3)
O2—C17	1.423 (3)	C9—C10	1.517 (3)
C1—C2	1.501 (3)	C10—C11	1.515 (3)
C2—C3	1.514 (3)	C11—C12	1.514 (3)
C3—C4	1.516 (3)	C12—C13	1.517 (3)
C4—C5	1.512 (3)	C13—C14	1.517 (3)
C5—C6	1.520 (3)	C14—C15	1.516 (3)
C6—C7	1.517 (3)	C15—C16	1.519 (3)
C7—C8	1.516 (3)	C16—C17	1.507 (3)
O1—C1—C2	112.8 (2)	C9—C10—C11	114.3 (2)
C1—C2—C3	115.0 (2)	C10—C11—C12	113.8 (2)
C2—C3—C4	112.9 (2)	C11—C12—C13	114.6 (2)
C3—C4—C5	114.9 (2)	C12—C13—C14	113.8 (2)
C4—C5—C6	113.5 (2)	C13—C14—C15	114.8 (2)
C5—C6—C7	114.2 (2)	C14—C15—C16	112.4 (2)
C6—C7—C8	113.6 (2)	C15—C16—C17	114.0 (2)
C7—C8—C9	114.2 (2)	O2—C17—C16	108.6 (2)
C8—C9—C10	113.9 (2)
O1—C1—C2—C3	63.3 (3)	O2—C17—C16—C15	−179.3 (2)