Nona­decane 1,19 diol

Acta Cryst.(2001). E57, o485±o487 DOI: 101107/S1600536801007176 Nakamura, Uno and Ogawa C₁₉H₄₀O₂

o485

organic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Nonadecane-1,19-diol

Naotake Nakamura,a_{* Kenjiro}

Unoa_{and Yoshihiro Ogawa}b

a_{Department of Applied Chemistry, Faculty of}

Science and Engineering, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu, Shiga 525-8577, Japan, andb_{Department of}

Chemistry, Faculty of Science, Kumamoto University, 2-39-1, Kurokami, Kumamoto 860-8555, Japan

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 296 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.040 wRfactor = 0.137

Data-to-parameter ratio = 10.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the molecular structure of the title compound, C19H40O2,

one hydroxyl group adopts a gauche conformation with

respect to the hydrocarbon skeleton which is all-trans, whereas the other hydroxyl group adopts atransconformation. In the crystal, the molecules lie parallel to thebaxis, the longest axis, forming layers with thicknessb/2 in which the long axis of the molecule is normal to the layer plane. The packing is similar to that in the smectic A phase of liquid crystals. These features are similar to those of the homologues with an odd number of C atoms, but different from those with an even number of C atoms.

Comment

Long-chain aliphatic compounds have been studied by many researchers from the viewpoint of basic polymer science, as they have a simple chemical structure whose molecular skeleton is a straight hydrocarbon chain. Early crystal-lographic work on paraf®ns (MuÈller, 1928) demonstrated the rod-like conformation of these molecules in the crystalline state. This rod-like conformation is one of the typical features of liquid crystalline molecules. In addition, some long-chain aliphatic compounds form a layer structure in the crystalline state, which is similar to that of a smectic phase of liquid crystals. As a model for smectic liquid crystals, the structures of ten alkane-,!-diols containing from 10±18 and 21 C atoms have been investigated recently by Nakamura and co-workers: 1,10-decanediol (Nakamura & Sato, 1999a), 1,11-undecane-diol (Nakamuraet al., 1999), 1,12-dodecanediol (Nakamura & Setodoi, 1997), 1,13-tridecanediol (Nakamura et al., 1997), 1,14-tetradecanediol (Nakamura & Sato, 1999b),

1,15-penta-decanediol (Nakamura, Uno, Watanabe et al., 2000),

1,16-hexadecanediol (Nakamura & Yamamoto, 1994),

1,17-hepta-decanediol (Nakamura et al., 2001), octadecane-1,18-diol

(Nakamura & Watanabe, 2001) and 1,21-henicosanediol (Nakamura, Uno & Ogawa, 2000). In addition, phase transi-tions in alkane-,!-diols with 13±24 C atoms were studied and a linear relation between the longest unit-cell axis and number of C atoms was reported (Ogawa & Nakamura, 1999).

Fig. 1 shows the molecular structure of nonadecane-1,19-diol, (I). One hydroxyl group adopts agaucheconformation with respect to the hydrocarbon skeleton which is all-trans

[O1ÐC1ÐC2ÐC3 torsion angle ofÿ63.2 (4)_{], whereas the}

other hydroxyl group adopts a trans conformation [O2Ð

organic papers

o486

C19ÐC18ÐC17 torsion angle of 179.4 (2)_{]. The projection of}

the crystal structure of nonadecane-1,19-diol, (I), along thec

axis is shown in Fig. 2. The molecules lie parallel to thebaxis, forming layers with a thickness ofb/2 in which the long axis of the molecule is normal to the layer plane. The packing is similar to that in the smectic A phase of liquid crystals. The

molecules also form two different types of OÐH O

hydrogen bonds, one is interlayer and the other is intralayer. The donor±acceptor distances of interlayer and intralayer hydrogen bonds are 2.711 (2) and 2.779 (4) AÊ, respectively. These features are similar to those already reported for the homologues with an odd number of C atoms [torsion angles of

gauche conformation: 1,11-undecanediolÿ63.3 (3)_,

1,13-tri-decanediolÿ63.0 (3)_{, 1,15-pentadecanediolÿ63.2 (4),}

1,17-heptadecanediol ÿ63.3 (3) _{and 1,21-henicosanediol}

ÿ65.1 (5)_{; donor±acceptor distances of interlayer and}

intra-layer hydrogen bonds: 1,11-undecanediol 2.710 (2) and

2.775 (3) AÊ, 1,13-tridecanediol 2.713 (2) and 2.776 (4) AÊ, 1,15-pentadecanediol 2.713 (2) and 2.777 (3) AÊ, 1,17-hepta-decanediol 2.705 (2) and 2.782 (4) AÊ, and 1,21-henicosanediol 2.717 (3) and 2.778 (4) AÊ]. The CÐC distances are in the range 1.498 (3)±1.521 (3) AÊ and CÐCÐC angles are in the range 112.5 (2)±115.3 (2)_.

The above observations contrast with the structures of alkane-,!-diols with an even number of C atoms, as already reported. In the molecular structure of the homologues with an even number of C atoms, both hydroxyl groups adopt a

transconformation with respect to the skeleton, the confor-mation of which is also all-trans. The centrosymmetric mol-ecules form layers in which the long axis of the molecule is inclined to the layer plane and the layers are arranged in a zigzag manner among the neighbouring layers making a

Figure 2

The projection of the crystal structure of (I) along thecaxis. Dotted lines indicate the hydrogen bonding.

Figure 1

herring-bone motif. The molecules form only interlayer hydrogen bonds. This kind of structure had been observed not only in alkane-,!-diols with an even number of C atoms but also in several examples of ,!-alkanedibromides: 1,12-di-bromododecane (Kupleet al., 1981), 1,16-dibromohexadecane (Kobayashiet al., 1995) and 1,18-dibromooctadecane (Naka-muraet al., 1993). All these packings are similar to that of the smectic C structure of liquid crystals.

Experimental

The title compound was synthesized as described previously by Ogawa & Nakamura (1999). The single crystal used for analysis was grown by slow evaporation from a solution containing a mixture of methanol, ethyl acetate andn-heptane (1:1:2).

Crystal data

C19H40O2

Mr= 300.52

Orthorhombic,P212121

a= 7.213 (5) AÊ

b= 52.870 (3) AÊ

c= 5.061 (3) AÊ

V= 1930 (1) AÊ3

Z= 4

Dx= 1.034 Mg mÿ3

CuKradiation Cell parameters from 22

re¯ections = 9.1±15.2 = 0.49 mmÿ1

T= 296.2 K Plate, colorless 0.600.300.04 mm

Data collection

Rigaku AFC-5Rdiffractometer !scans

Absorption correction: (Northet al., 1968)

Tmin= 0.757,Tmax= 1.000

3390 measured re¯ections 2117 independent re¯ections 1367 re¯ections withF2_{> 2(F}2₎

Rint= 0.014

max= 70.6

h=ÿ2!8

k= 0!64

l=ÿ1!5 3 standard re¯ections

every 150 re¯ections intensity decay: 3.0%

Re®nement

Re®nement onF2

R(F) = 0.040

wR(F2_{) = 0.137}

S= 1.42 2110 re¯ections 197 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + {0.05[Max(Fo2,0) + 2Fc2]/3}2]

(/)max= 0.001

max= 0.09 e AÊÿ3

min=ÿ0.11 e AÊÿ3

Extinction correction: Zachariasen (1967), type 2, Gaussian isotropic Extinction coef®cient: 0.043 (5)

The methylene H atoms were located at idealized positions and were allowed to ride on the parent C atoms. The hydroxyl H atoms were located in difference syntheses and the positional parameters were allowed to re®ne for the ®nal re®nements. All H-atom isotropic displacement parameters were set at 1.2Ueqof the parent atom.

Data collection: MSC/AFC Diffractometer Control Software

(Molecular Structure Corporation, 1992); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Mole-cular Structure Corporation, 2000); program(s) used to solve struc-ture: SAPI91 (Fan, 1991); program(s) used to re®ne structure:

TEXSAN; software used to prepare material for publication:

TEXSAN.

References

Fan, H.-F. (1991).SAPI91. Rigaku Corporation, Tokyo, Japan.

Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

Kobayashi, H., Yamamoto, T. & Nakamura, N. (1995).Cryst. Res. Technol.30, 375±380.

Kuple, S., Seidei, I., Szulzewsky, K., Steger, U. & Steger, E. (1981).Cryst. Res. Technol.16, 349±356.

Molecular Structure Corporation (1992).MSC/AFC Diffractometer Control Software. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

Molecular Structure Corporation (2000).TEXSAN.Version 1.11. MSC, 9009 New Trails Drive, The Woodlands, TX 77381±5209, USA.

MuÈller, A. (1928).Proc. R.Soc. London Ser. A,120, 437±459. Nakamura, N. & Sato, T. (1999a).Acta Cryst.C55, 1685±1687. Nakamura, N. & Sato, T. (1999b).Acta Cryst.C55, 1687±1689. Nakamura, N. & Setodoi, S. (1997).Acta Cryst.C53, 1883±1885. Nakamura, N., Setodoi, S. & Ikeya, T. (1999).Acta Cryst.C55, 789±791. Nakamura, N., Tanihara, Y. & Takayama, T. (1997).Acta Cryst.C53, 253±255. Nakamura, N., Uno, K. & Ogawa, Y. (2000).Acta Cryst.C56, 1389±1390. Nakamura, N., Uno, K. & Ogawa, Y. (2001).Acta Cryst.C57, 585±586. Nakamura, N., Uno, K., Watanabe, R., Ikeya, T. & Ogawa, Y. (2000).Acta

Cryst.C56, 903±904.

Nakamura, N. & Watanabe, R. (2001).Acta Cryst.E57, o136±138. Nakamura, N. & Yamamoto, T. (1994).Acta Cryst.C50, 946±948.

Nakamura, N., Yamamoto, T., Kobayashi, H. & Yoshimura, Y. (1993).Cryst. Res. Technol.28, 953±957.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.

Ogawa, Y. & Nakamura, N. (1999).Bull. Chem. Soc. Jpn,72, 943±946. Zachariasen, W. H. (1967).Acta Cryst.23, 558±564.

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Acta Cryst. (2001). E57, o485–o487

supporting information

Acta Cryst. (2001). E57, o485–o487 [https://doi.org/10.1107/S1600536801007176]

Nonadecane-1,19-diol

Naotake Nakamura, Kenjiro Uno and Yoshihiro Ogawa

(I)

Crystal data

C19H40O2 Mr = 300.52

Orthorhombic, P212121 a = 7.213 (5) Å

b = 52.870 (3) Å

c = 5.061 (3) Å

V = 1930 (1) Å3 Z = 4

Dx = 1.034 Mg m−3

Cu Kα radiation, λ = 1.5418 Å Cell parameters from 22 reflections

θ = 9.1–15.2°

µ = 0.49 mm−1 T = 296 K Plate, colorless 0.6 × 0.3 × 0.04 mm

Data collection

Rigaku AFC-5R diffractometer

ω scans

Absorption correction: ψ

(North et al., 1968)

Tmin = 0.757, Tmax = 1.000 3390 measured reflections 2117 independent reflections

1367 reflections with F2 _{> 2σ(F}2₎ Rint = 0.014

θmax = 70.6° h = −2→8

k = 0→64

l = −1→5

3 standard reflections every 150 reflections intensity decay: 3.0%

Refinement

Refinement on F2 R[F2 _{> 2σ(F}2_{)] = 0.040} wR(F2_{) = 0.137} S = 1.42 2110 reflections 197 parameters

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + {0.05[Max(Fo2,0) + 2Fc2]/3}2] (Δ/σ)max = 0.001

Δρmax = 0.09 e Å−3 Δρmin = −0.11 e Å−3

Extinction correction: Zachariasen (1967), type 2, Gaussian isotropic

Extinction coefficient: 0.043 (5)

Special details Geometry. none

Refinement. Refinement using reflections with F2 _{> -3.0 σ(F}2_{). The weighted R-factor (wR) and goodness of fit (S) are} based on F2_{. R-factor (gt) are based on F. The threshold expression of F}2 _{> 2.0 σ(F}2_{) is used only for calculating R-factor} (gt).

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

x y z Uiso*/Ueq

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Acta Cryst. (2001). E57, o485–o487

O2 1.0635 (3) 0.22552 (3) 0.4290 (4) 0.0753 (6)

C1 0.9980 (5) −0.22781 (4) 0.5912 (6) 0.0716 (9)

C2 1.0529 (4) −0.20292 (4) 0.4731 (5) 0.0614 (7)

C3 0.9668 (4) −0.17984 (4) 0.6013 (5) 0.0528 (6)

C4 1.0383 (4) −0.15524 (4) 0.4877 (5) 0.0532 (6)

C5 0.9582 (4) −0.13159 (4) 0.6122 (5) 0.0514 (6)

C6 1.0362 (3) −0.10725 (4) 0.4999 (5) 0.0516 (6)

C7 0.9584 (4) −0.08339 (4) 0.6226 (5) 0.0519 (6)

C8 1.0380 (3) −0.05920 (4) 0.5089 (5) 0.0516 (6)

C9 0.9591 (3) −0.03524 (4) 0.6290 (5) 0.0522 (6)

C10 1.0394 (3) −0.01113 (4) 0.5130 (5) 0.0509 (6)

C11 0.9597 (3) 0.01295 (4) 0.6297 (5) 0.0509 (6)

C12 1.0398 (3) 0.03697 (4) 0.5114 (5) 0.0506 (6)

C13 0.9594 (3) 0.06115 (3) 0.6264 (5) 0.0512 (6)

C14 1.0396 (4) 0.08501 (4) 0.5060 (5) 0.0511 (6)

C15 0.9590 (3) 0.10942 (4) 0.6160 (5) 0.0516 (6)

C16 1.0399 (4) 0.13306 (4) 0.4919 (5) 0.0519 (6)

C17 0.9605 (3) 0.15773 (4) 0.5962 (5) 0.0533 (6)

C18 1.0466 (4) 0.18074 (4) 0.4654 (5) 0.0555 (6)

C19 0.9709 (4) 0.20556 (4) 0.5639 (6) 0.0595 (7)

H1a 1.0528 −0.2410 0.4904 0.0859*

H1b 0.8668 −0.2293 0.5841 0.0859*

H1o 1.179 (4) −0.2287 (5) 0.857 (6) 0.0809*

H2a 1.1838 −0.2014 0.4864 0.0737*

H2b 1.0179 −0.2030 0.2922 0.0737*

H2o 1.008 (4) 0.2390 (5) 0.484 (7) 0.0904*

H3a 0.8363 −0.1805 0.5763 0.0634*

H3b 0.9939 −0.1802 0.7850 0.0634*

H4a 1.1690 −0.1549 0.5105 0.0639*

H4b 1.0097 −0.1550 0.3045 0.0639*

H5a 0.8279 −0.1316 0.5850 0.0617*

H5b 0.9837 −0.1320 0.7963 0.0617*

H6a 1.1666 −0.1073 0.5265 0.0619*

H6b 1.0104 −0.1069 0.3159 0.0619*

H7a 0.8280 −0.0833 0.5956 0.0623*

H7b 0.9839 −0.0837 0.8067 0.0623*

H8a 1.1682 −0.0593 0.5375 0.0619*

H8b 1.0136 −0.0590 0.3245 0.0619*

H9a 0.8289 −0.0351 0.6010 0.0627*

H9b 0.9840 −0.0354 0.8133 0.0627*

H10a 1.1694 −0.0112 0.5428 0.0611*

H10b 1.0158 −0.0111 0.3283 0.0611*

H11a 0.8296 0.0130 0.6009 0.0611*

H11b 0.9840 0.0130 0.8142 0.0611*

H12a 1.1698 0.0370 0.5412 0.0607*

H12b 1.0162 0.0369 0.3267 0.0607*

H13a 0.8293 0.0611 0.5973 0.0614*

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Acta Cryst. (2001). E57, o485–o487

H14a 1.1695 0.0851 0.5372 0.0614*

H14b 1.0170 0.0846 0.3211 0.0614*

H15a 0.8290 0.1094 0.5859 0.0619*

H15b 0.9823 0.1099 0.8007 0.0619*

H16a 1.1697 0.1331 0.5236 0.0623*

H16b 1.0176 0.1324 0.3071 0.0623*

H17a 0.8307 0.1579 0.5643 0.0639*

H17b 0.9827 0.1586 0.7810 0.0639*

H18a 1.1763 0.1804 0.4976 0.0666*

H18b 1.0245 0.1797 0.2807 0.0666*

H19a 0.9920 0.2070 0.7486 0.0715*

H19b 0.8416 0.2064 0.5296 0.0715*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O1 0.089 (1) 0.0447 (8) 0.068 (1) −0.0057 (10) −0.005 (1) 0.0044 (8)

O2 0.092 (1) 0.0371 (7) 0.097 (1) 0.0021 (9) 0.022 (1) 0.0010 (8)

C1 0.102 (2) 0.044 (1) 0.069 (2) −0.004 (1) −0.010 (2) −0.008 (1)

C2 0.086 (2) 0.044 (1) 0.054 (1) 0.005 (1) 0.005 (2) −0.0027 (10)

C3 0.060 (1) 0.0402 (9) 0.059 (1) 0.002 (1) −0.001 (2) −0.001 (1)

C4 0.057 (1) 0.043 (1) 0.060 (1) 0.002 (1) 0.003 (2) 0.0021 (10)

C5 0.055 (1) 0.0394 (9) 0.060 (1) 0.002 (1) 0.000 (2) 0.001 (1)

C6 0.053 (1) 0.0409 (10) 0.061 (1) 0.000 (1) 0.003 (2) 0.0032 (9)

C7 0.053 (1) 0.0402 (10) 0.062 (1) 0.002 (1) 0.000 (2) 0.002 (1)

C8 0.052 (1) 0.0389 (10) 0.064 (1) 0.002 (1) 0.004 (2) 0.0025 (9)

C9 0.053 (1) 0.0408 (10) 0.063 (1) 0.002 (1) 0.002 (2) 0.001 (1)

C10 0.053 (1) 0.0382 (9) 0.062 (1) 0.002 (1) 0.002 (1) 0.0003 (10)

C11 0.052 (1) 0.0399 (9) 0.061 (1) 0.003 (1) 0.002 (1) 0.001 (1)

C12 0.052 (1) 0.0391 (9) 0.061 (1) 0.001 (1) 0.001 (2) 0.0016 (9)

C13 0.052 (1) 0.0391 (9) 0.062 (1) 0.002 (1) 0.003 (2) −0.001 (1)

C14 0.054 (1) 0.0383 (10) 0.061 (1) −0.001 (1) 0.001 (2) 0.0011 (9)

C15 0.053 (1) 0.0403 (10) 0.062 (1) 0.002 (1) 0.004 (2) −0.001 (1)

C16 0.055 (1) 0.0385 (9) 0.063 (1) −0.002 (1) 0.002 (2) −0.0008 (9)

C17 0.056 (1) 0.0398 (9) 0.064 (1) 0.003 (1) 0.001 (2) −0.003 (1)

C18 0.060 (1) 0.0379 (9) 0.068 (2) 0.001 (1) 0.004 (2) −0.0013 (10)

C19 0.064 (2) 0.0375 (9) 0.077 (2) 0.000 (1) 0.005 (2) 0.001 (1)

Geometric parameters (Å, º)

O1—C1 1.424 (3) C9—C10 1.518 (3)

O2—C19 1.423 (3) C10—C11 1.516 (3)

C1—C2 1.498 (3) C11—C12 1.518 (3)

C2—C3 1.515 (3) C12—C13 1.520 (3)

C3—C4 1.513 (3) C13—C14 1.516 (3)

C4—C5 1.514 (3) C14—C15 1.521 (3)

C5—C6 1.515 (3) C15—C16 1.516 (3)

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Acta Cryst. (2001). E57, o485–o487

C7—C8 1.516 (3) C17—C18 1.518 (3)

C8—C9 1.516 (3) C18—C19 1.506 (3)

O1—C1—C2 112.5 (2) C10—C11—C12 113.8 (2)

C1—C2—C3 115.3 (2) C11—C12—C13 114.0 (2)

C2—C3—C4 112.9 (2) C12—C13—C14 113.6 (2)

C3—C4—C5 114.9 (2) C13—C14—C15 114.4 (2)

C4—C5—C6 113.8 (2) C14—C15—C16 113.6 (2)

C5—C6—C7 114.6 (2) C15—C16—C17 114.8 (2)

C6—C7—C8 114.0 (2) C16—C17—C18 112.5 (2)

C7—C8—C9 114.2 (2) C17—C18—C19 113.9 (2)

C8—C9—C10 113.8 (2) O2—C19—C18 108.5 (2)

C9—C10—C11 114.2 (2)