Do­decane 1,12 di­thiol

organic papers

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Structure Reports Online

ISSN 1600-5368

Dodecane-1,12-dithiol

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) = 0.002 AÊ Rfactor = 0.039 wRfactor = 0.138

Data-to-parameter ratio = 18.9

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, C12H26S2, the

hydrocarbon skeleton has an all-trans conformation. The terminal SÐH bond is in the gauche conformation with respect to the skeleton. In the crystal structure, the molecules are arranged along thecaxis, the longest axis, forming layers in which the long axis of the molecule is inclined to the layer plane as in the smectic C layer structure of liquid crystals. The mercapto groups do not form hydrogen bonds. These features are similar to those of the homologues with an even number of C atoms containing more than four C atoms.

Comment

In biology, the mercapto group plays an important role in maintaining the structure of a protein or hormone, for example, making a disul®de bond. As a material, long-chain alkanethiols with a terminal mercapto group have been used as ligands which form self-assembled monolayers in soft lithography (Xia & Whitesides, 1998). On the other hand, the crystal structures of alkane-,!-dithiols which have the mercapto group at both ends of the hydrocarbon skeleton have attracted attention as basic models for smectic liquid crystals. The overall molecular shape can be regarded as rod-like, which is one of the typical features of liquid crystalline molecules. In the crystalline state, the molecules form layers similar to those of the smectic liquid crystals. The melting-point alternation in the alkane-,!-dithiols with 2±10 C atoms has been investigated (Thalladiet al., 2000). In that study, the crystal structures of the alkane-,!-dithiols were analyzed at 130 K by X-ray diffraction using single crystals grown using a miniature zone-melting procedure. Alkane-,!-dithiols containing more than four C atoms haveP1 as space group for an even number of C atoms, andP2/cfor an odd number of C atoms. Recently, the crystal structure of icosane-1,20-dithiol, (I), was analyzed at 296 K using a single-crystal which was grown by a slow evaporation method (Nakamuraet al., 2001a). In this paper, the crystal structure of dodecane-1,12-dithiol is reported.

The molecular structure of (I) is depicted in Fig. 1. The hydrocarbon skeleton has an all-transconformation and the molecule is centrosymmetric. The terminal S1ÐH1sbond is in the gauche conformation with respect to the skeleton [the C2ÐC1ÐS1ÐH1s torsion angle is 65 (1)_{]. In the crystal}

structure of (I), the molecules are arranged along thec axis forming layers in which the long axis of the molecule is inclined to the layer plane, as is shown in Fig. 2. This packing is very similar to that of the smectic C structure of liquid crystals. The nearest neighboring mercapto S atom distance is the interlayer S1 S1i _{[symmetry code: (i) 2ÿx, ÿy, 1ÿz],}

whose value is 3.5552 (8) AÊ; the S1ÐH1s S1i _{angle is}

80 (1)_{. These results show the mercapto groups do not form}

hydrogen bonds. Apart from the length of the c axis, the longest axis, no major differences were observed between the crystal data obtained here and those of homologues with an even number of C atoms containing more than four C atoms (Thalladiet al., 2000; Nakamuraet al., 2001a).

Investigations of model compounds for smectic liquid crystals have been reported. The molecular and crystal structures of eleven alkane-,!-diols with 10±19 and 21 C atoms have been analyzed by single-crystal X-ray diffraction in our laboratory. The structural differences between compounds with an even number of C atoms and those with an odd number of C atoms were analysed and discussed from the viewpoint of smectic liquid crystals. In the alkane-,!-diols with an even number of C atoms, the molecules form layers in a herring-bone arrangement, just as in the chiral smectic C mesophase of liquid crystals (Nakamura & Sato, 1999a, b; Nakamura & Setodoi, 1997; Nakamura & Yamamoto, 1994;

Nakamura & Watanabe, 2001). On the other hand, in the alkane-,!-diols with an odd number of C atoms, the mol-ecules form a layer structure which is very similar to that of the smectic A mesophase in liquid crystals (Nakamuraet al., 1997, 1999; Nakamura, Uno, Watanabeet al., 2000; Nakamura, Uno & Ogawa, 2000; Nakamuraet al., 2001b,c).

As a result, alkane-,!-diols with an odd number of C atoms, alkane-,!-dithiols with an even number of C atoms, and alkane-,!-diols with an even number of C atoms could be regarded as model compounds for smectic A, smectic C and chiral smectic C liquid crystals, respectively.

Experimental

Dodecane-1,12-dithiol was synthesized from 1,12-dibromododecane (Tokyo Kasei Co.) according to the procedure of Urquhart et al. (1955). The single crystal used for analysis was grown by slow evaporation from a benzene±ethanol (1:3) solution at low tempera-ture (283 K).

Crystal data

C12H26S2

Mr= 234.46

Triclinic,P1

a= 4.221 (1) AÊ

b= 5.430 (1) AÊ

c= 15.615 (2) AÊ = 85.65 (1) = 86.68 (2) = 83.51 (1)

V= 354.1 (1) AÊ3

Z= 1

Dx= 1.099 Mg mÿ3

Cu Kradiation Cell parameters from 22

re¯ections = 9.7±21.4 = 3.12 mmÿ1

T= 296.2 K Plate, colorless 0.600.250.17 mm

Acta Cryst.(2001). E57, o508±o510 Nakamura, Uno and Ogawa C₁₂H₂₆S₂

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organic papers

Figure 2

The projection of the crystal structure of (I) along theaaxis.

Figure 1

organic papers

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Data collection

Rigaku AFC-5Rdiffractometer !±2scans

Absorption correction: scan (Northet al., 1968)

Tmin= 0.406,Tmax= 0.589 1972 measured re¯ections 1287 independent re¯ections 1173 re¯ections withF2_{> 2(F}2₎

Rint= 0.041 max= 70.6

h=ÿ4!5

k=ÿ6!2

l=ÿ19!19 3 standard re¯ections

every 150 re¯ections intensity decay: 9%

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.039}

wR(F2_{) = 0.138}

S= 1.67 1287 re¯ections 68 parameters

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

w= 1/[2_(F

o2) + {0.07[Max(Fo2,0) +

2Fc2]/3}2]

(/)max< 0.001 max= 0.14 e AÊÿ3 min=ÿ0.18 e AÊÿ3

Extinction correction: Zachariasen (1967) type 2 Gaussian isotropic Extinction coef®cient: 0.31 (9)

The methylene H atoms were positioned at idealized positions and were allowed to ride on the parent C atoms. The mercapto H atom was located in a difference map and the positional parameters were allowed to re®ne during the ®nal re®nement. All H-atom isotropic displacement parameters were ®xed 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:MULTAN88 (Debaerdemaekeret al., 1988); program(s) used to re®ne structure: TEXSAN; software used to prepare material for publication:TEXSAN.

References

Debaerdemaeker, T., Germain, G., Main, P., Refaat, L. S., Tate, C. & Woolfson, M. M. (1988).MULTAN88. Universities of York, England, and Louvain, Belgium.

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

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.

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. (2001a).Acta Cryst.E57, o505±507. Nakamura, N., Uno, K. & Ogawa, Y. (2001b).Acta Cryst.C57, 585±586. Nakamura, N., Uno, K. & Ogawa, Y. (2001c).Acta Cryst.E57, o485±487. 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.

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

Thalladi, V. R., Boese, R. & Weiss, H. C. (2000).J. Am. Chem. Soc.122, 1186± 1190.

Urquhart, G. G., Gates, J. W. & Connor, R. (1955).Org. Synth.III, pp. 363± 365.

Xia, Y. & Whitesides, G. M. (1998).Angew. Chem. Int. Ed. Engl.37, 550± 575.

supporting information

sup-1 Acta Cryst. (2001). E57, o508–o510

supporting information

Acta Cryst. (2001). E57, o508–o510 [https://doi.org/10.1107/S160053680100719X]

Dodecane-1,12-dithiol

Naotake Nakamura, Kenjiro Uno and Yoshihiro Ogawa

(I)

Crystal data C12H26S2 Mr = 234.46 Triclinic, P1 Hall symbol: -P 1 a = 4.221 (1) Å b = 5.430 (1) Å c = 15.615 (2) Å α = 85.65 (1)° β = 86.68 (2)° γ = 83.51 (1)° V = 354.1 (1) Å3

Z = 1 F(000) = 130 Dx = 1.099 Mg m−3 Melting point: 304.4 K Cu Kα radiation, λ = 1.5418 Å Cell parameters from 22 reflections θ = 9.7–21.4°

µ = 3.12 mm−1 T = 296 K Plate, colourless 0.60 × 0.25 × 0.17 mm

Data collection Rigaku AFC5R

diffractometer ω–2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.406, Tmax = 0.589 1972 measured reflections 1287 independent reflections

1173 reflections with F2 _{> 2σ(F}2₎ Rint = 0.041

θmax = 70.6° h = −4→5 k = −6→2 l = −19→19

3 standard reflections every 150 reflections intensity decay: 9%

Refinement Refinement on F2 R[F2 _{> 2σ(F}2_{)] = 0.039} wR(F2_{) = 0.138} S = 1.67 1287 reflections 68 parameters

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + {0.07[Max(Fo2,0) + 2Fc2]/3}2] (Δ/σ)max < 0.001

Δρmax = 0.14 e Å−3 Δρmin = −0.18 e Å−3

Extinction correction: Zachariasen (1967) type 2 Gaussian isotropic

Extinction coefficient: 0.31 (9)

Special details

supporting information

sup-2 Acta Cryst. (2001). E57, o508–o510

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

x y z Uiso*/Ueq

S1 0.8479 (1) 0.21309 (9) 0.57724 (3) 0.0798 (2)

C1 0.6724 (4) 0.4926 (3) 0.62472 (9) 0.0636 (5)

C2 0.5533 (4) 0.4564 (3) 0.71735 (9) 0.0565 (4)

C3 0.4262 (4) 0.6976 (3) 0.75586 (9) 0.0564 (4)

C4 0.3053 (4) 0.6672 (3) 0.84879 (9) 0.0557 (4)

C5 0.1820 (4) 0.9076 (3) 0.88779 (9) 0.0553 (4)

C6 0.0612 (4) 0.8794 (3) 0.98058 (9) 0.0553 (4)

H1a 0.8289 0.6060 0.6217 0.0764*

H1b 0.4970 0.5616 0.5919 0.0764*

H1s 0.642 (6) 0.112 (5) 0.578 (2) 0.0958*

H2a 0.3870 0.3514 0.7203 0.0678*

H2b 0.7248 0.3790 0.7500 0.0678*

H3a 0.5931 0.8022 0.7525 0.0677*

H3b 0.2552 0.7744 0.7229 0.0677*

H4a 0.1367 0.5643 0.8520 0.0668*

H4b 0.4757 0.5885 0.8816 0.0668*

H5a 0.3507 1.0104 0.8844 0.0663*

H5b 0.0116 0.9860 0.8549 0.0663*

H6a −0.1070 0.7760 0.9854 0.0663*

H6b 0.2303 0.8063 1.0149 0.0663*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

S1 0.1056 (5) 0.0694 (4) 0.0623 (4) 0.0030 (3) 0.0156 (3) −0.0236 (2)

C1 0.086 (1) 0.0569 (8) 0.0455 (8) −0.0015 (7) 0.0102 (7) −0.0082 (6)

C2 0.0736 (10) 0.0523 (8) 0.0427 (8) −0.0022 (7) 0.0049 (6) −0.0098 (6)

C3 0.0705 (9) 0.0540 (8) 0.0432 (7) −0.0016 (6) 0.0052 (6) −0.0081 (6)

C4 0.0716 (10) 0.0517 (8) 0.0426 (8) −0.0017 (7) 0.0043 (6) −0.0091 (6)

C5 0.0701 (9) 0.0518 (8) 0.0426 (7) −0.0018 (6) 0.0049 (6) −0.0081 (6)

C6 0.0697 (9) 0.0525 (8) 0.0426 (8) −0.0026 (7) 0.0048 (6) −0.0087 (6)

Geometric parameters (Å, º)

S1—C1 1.804 (2) C2—H2a 0.95

C1—C2 1.509 (2) C2—H2b 0.95

C2—C3 1.513 (2) C3—H3a 0.95

C3—C4 1.513 (2) C3—H3b 0.95

C4—C5 1.508 (2) C4—H4a 0.95

C5—C6 1.510 (2) C4—H4b 0.95

C6—C6i _{1.511 (3) C5—H5a 0.95}

S1—H1s 1.08 (3) C5—H5b 0.95

C1—H1a 0.95 C6—H6a 0.95

supporting information

sup-3 Acta Cryst. (2001). E57, o508–o510

S(1)···S(1)ii _{3.5552 (8)}

S1—C1—C2 114.9 (1) C4—C3—H3a 108.3

C1—C2—C3 113.0 (1) C4—C3—H3b 108.3

C2—C3—C4 114.2 (1) H3a—C3—H3b 109.5

C3—C4—C5 114.4 (1) C3—C4—H4a 108.2

C4—C5—C6 114.8 (1) C3—C4—H4b 108.2

C5—C6—C6i _{114.6 (1) C5—C4—H4a 108.2}

C1—S1—H1s 100 (1) C5—C4—H4b 108.2

S1—C1—H1a 108.1 H4a—C4—H4b 109.5

S1—C1—H1b 108.1 C4—C5—H5a 108.1

C2—C1—H1a 108.1 C4—C5—H5b 108.1

C2—C1—H1b 108.1 C6—C5—H5a 108.1

H1a—C1—H1b 109.5 C6—C5—H5b 108.1

C1—C2—H2a 108.6 H5a—C5—H5b 109.5

C1—C2—H2b 108.6 C5—C6—H6a 109.5

C3—C2—H2a 108.6 C5—C6—H6b 109.5

C3—C2—H2b 108.6 C6i_{—C6—H6a 107.8}

H2a—C2—H2b 109.5 C6i_{—C6—H6b 105.8}

C2—C3—H3a 108.3 H6a—C6—H6b 109.5

C2—C3—H3b 108.3

S1—C1—C2—C3 176.6 (1) C4—C5—C6—C6i _{179.9 (2)}

C1—C2—C3—C4 −180.0 (1) C5—C6—C6i_—C5i _−180.0

C2—C3—C4—C5 179.3 (1) C2—C1—S1—H1s 65 (1)

C3—C4—C5—C6 −179.9 (1)