organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

trans-1,4-Di­methyl­cyclo­hexane

aChemical Crystallography, Central Chemistry Laboratory, University of Oxford, Oxford OX1 3TA, England
*Correspondence e-mail: Richard.Bream@pmb.ox.ac.uk

(Received 9 December 2005; accepted 16 December 2005; online 7 January 2006)

trans-1,4-Dimethyl­cyclo­hexane, C8H16, was studied as part of a project to develop a computer-controlled low-temperature crystal-growing device. The liquid crystallizes with the mol­ecule lying on a centre of symmetry, leading to Z′ = [{1 \over 2}].

Comment

trans-1,4-Dimethyl­cyclo­hexane, (I)[link] (Fig. 1[link]), was one of eight alkyl­cyclo­hexanes whose thermodynamic properties were published in 1949 (Huffman et al., 1949[Huffman, H. M., Todd, S. S. & Oliver, G. D. (1949). J. Am. Chem. Soc. 71, 584-592.]). That work reported a melting point of 236.217 K and showed no evidence for phase changes in the range down to liquid-nitro­gen temperatures.

[Scheme 1]

The sample used for the present study was one of several sealed in 0.2 mm Lindeman tubes for preliminary work carried out in 1979. Data had been collected at that time on a Stoe Weissenberg diffractometer and the structure solved, but it was not of a publishable quality (Courseille et al., 1979[Courseille, D., Hospital, M., Leroy, F. & Watkin, D. (1979). 5th European Crystallographic Meeting, Copenhagen, Denmark, p. 285.]).

The sample solidified spontaneously to a polycrystalline mass on flash cooling to 150 K. The temperature was then raised to 230 K and the sample zone-refined into a single-crystal using tandem computer-controlled heating elements. The temperature was then slowly reduced to 150 K for data collection.

The structure of (I)[link] consists of mol­ecules lying on centres of symmetry. This leads to the packing consisting of columns of mol­ecules lying along the b axis (Fig. 2[link]), with the mean plane of the mol­ecule inclined at 145° to that axis (Fig. 3[link]).

[Figure 1]
Figure 1
The structure of (I)[link], with displacement ellipsoids drawn at the 50% probability level and H atoms shown as spheres of arbitary radii. Unlabelled atoms are related to labelled atoms by a centre of symmetry.
[Figure 2]
Figure 2
A projection of (I)[link] along the b axis. The low specific gravity (0.98 Mg m−3) is explained by the open texture of the structure.
[Figure 3]
Figure 3
A projection of (I)[link] along the c axis, showing the mol­ecular stacks parallel to the b axis.

Experimental

The material was used as supplied by Aldrich Chemical Company Inc. in 1979.

Crystal data
  • C8H16

  • Mr = 112.22

  • Monoclinic, P 21 /c

  • a = 6.0843 (2) Å

  • b = 5.4818 (2) Å

  • c = 11.7629 (5) Å

  • β = 103.8918 (18)°

  • V = 380.85 (2) Å3

  • Z = 2

  • Dx = 0.978 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 882 reflections

  • θ = 1–27°

  • μ = 0.05 mm−1

  • T = 150 K

  • Cylinder, colourless

  • 1.00 (length) × 0.20 mm (diameter)

Data collection
  • Nonius KappaCCD area-detector diffractometer

  • ω scans

  • Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.])Tmin = 0.758, Tmax = 1.000

  • 4141 measured reflections

  • 862 independent reflections

  • 861 reflections with I > 3σ(I)

  • Rint = 0.027

  • θmax = 27.6°

  • h = −7 → 7

  • k = −7 → 6

  • l = −15 → 15

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.091

  • S = 0.99

  • 861 reflections

  • 13 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(F2) + ( 0.03P)2 + 0.07P] where P = (max(Fo2,0) + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.17 e Å−3

The H atoms were all located in a difference map and then repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry, with C—H distances in the range 0.93–0.98 Å, and on the displacement parameters, with Uiso(H) = 1.2–1.5 times Ueq of the parent atom, after which their positions were refined with riding constraints.

Data collection: COLLECT (Nonius, 2001[Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.]).; cell refinement: DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, C. K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.]); software used to prepare material for publication: CRYSTALS.

Supporting information


Comment top

trans-1,4-Dimethylcyclohexane, (I) (Fig. 1), was one of eight alkylcyclohexanes whose thermodynamic properties were published in 1949 (Huffman et al., 1949). That work reported a melting point of 236.217 K and showed no evidence for phase changes in the range down to liquid-nitrogen temperatures.

The sample used for the present study was one of several sealed in 0.2 mm Lindeman tubes for preliminary work carried out in 1979. Data had been collected at that time on a Stoe Weissenberg diffractometer and the structure solved, but it was not of a publishable quality (Courseille et al., 1979).

The sample solidified spontaneously to a polycrystalline mass on flash cooling to 150 K. The temperature was then raised to 230 K and the sample zone-refined into a single-crystal using tandem computer-controlled heating elements. The temperature was then slowly reduced to 150 K for data collection.

The structure of (I) consists of molecules lying on a centre of symmetry. This leads to the packing consisting of columns of molecules lying along the b axis (Fig. 2), with the plane of the molecule inclined at 145° to that axis (Fig. 3).

Experimental top

The material was used as supplied by Aldrich Chemical Company Inc. in 1979.

Refinement top

The H atoms were all located in a difference map and then repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry, with C—H distances in the range 0.93–0.98 Å, and on the displacement parameters, with Uiso(H) = 1.2–1.5 times Ueq of the parent atom, after which their positions were refined with riding constraints.

Computing details top

Data collection: COLLECT (Nonius, 2001).; cell refinement: DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 50% probability level and H atoms shown as spheres of arbitary radii.
[Figure 2] Fig. 2. A projection of (I) along the b axis. The low specific gravity (0.98) is explained by the open texture of the structure.
[Figure 3] Fig. 3. A projection of (I) along the c axis, showing the molecular stacks parallel to the b axis.
Trans-1,4 dimethyl cyclohexane top
Crystal data top
C8H16Dx = 0.978 Mg m3
Mr = 112.22Melting point: 236.217 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.0843 (2) ÅCell parameters from 882 reflections
b = 5.4818 (2) Åθ = 1–27°
c = 11.7629 (5) ŵ = 0.05 mm1
β = 103.8918 (18)°T = 150 K
V = 380.85 (2) Å3Cylinder, colourless
Z = 21.00 × 0.20 (radius) mm
F(000) = 128
Data collection top
Nonius KappaCCD area-detector
diffractometer
861 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 27.6°, θmin = 3.5°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
h = 77
Tmin = 0.758, Tmax = 1.000k = 76
4141 measured reflectionsl = 1515
862 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.091 w = 1/[σ2(F2) + ( 0.03P)2 + 0.07P]
where P = (max(Fo2,0) + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.000356
861 reflectionsΔρmax = 0.19 e Å3
13 parametersΔρmin = 0.17 e Å3
0 restraints
Crystal data top
C8H16V = 380.85 (2) Å3
Mr = 112.22Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.0843 (2) ŵ = 0.05 mm1
b = 5.4818 (2) ÅT = 150 K
c = 11.7629 (5) Å1.00 × 0.20 (radius) mm
β = 103.8918 (18)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
862 independent reflections
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
861 reflections with I > 3σ(I)
Tmin = 0.758, Tmax = 1.000Rint = 0.027
4141 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 0.99Δρmax = 0.19 e Å3
861 reflectionsΔρmin = 0.17 e Å3
13 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.22877 (14)0.08561 (16)0.56580 (7)0.0289
C20.13233 (14)0.14820 (17)0.43681 (7)0.0323
C30.03582 (15)0.04284 (17)0.62583 (8)0.0331
C40.39112 (15)0.28192 (18)0.62800 (9)0.0389
H110.31320.06960.57010.0332*
H210.05540.30790.43250.0369*
H220.25820.16750.39750.0380*
H310.04500.20010.62700.0402*
H320.09870.00870.70790.0404*
H410.45780.23510.71160.0558*
H420.31050.43790.62740.0552*
H430.51490.30770.58920.0549*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.02890.02680.03030.00420.00540.0008
C20.03330.03450.03020.00020.00980.0043
C30.03700.03830.02430.00060.00780.0002
C40.03560.03600.04180.00140.00280.0019
Geometric parameters (Å, º) top
C1—C21.5286 (12)C2—H220.991
C1—C31.5264 (12)C3—H310.994
C1—C41.5238 (12)C3—H320.990
C1—H110.989C4—H411.003
C2—C3i1.5246 (12)C4—H420.985
C2—H210.988C4—H430.980
C2—C1—C3109.82 (7)C1—C3—C2i112.54 (7)
C2—C1—C4111.60 (7)C1—C3—H31108.1
C3—C1—C4111.61 (7)C2i—C3—H31109.0
C2—C1—H11108.4C1—C3—H32109.5
C3—C1—H11107.0C2i—C3—H32109.4
C4—C1—H11108.3H31—C3—H32108.1
C1—C2—C3i112.25 (7)C1—C4—H41110.7
C1—C2—H21108.3C1—C4—H42110.2
C3i—C2—H21109.2H41—C4—H42108.2
C1—C2—H22109.4C1—C4—H43111.1
C3i—C2—H22110.6H41—C4—H43108.6
H21—C2—H22106.9H42—C4—H43108.0
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC8H16
Mr112.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)6.0843 (2), 5.4818 (2), 11.7629 (5)
β (°) 103.8918 (18)
V3)380.85 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.05
Crystal size (mm)1.00 × 0.20 (radius)
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.758, 1.000
No. of measured, independent and
observed [I > 3σ(I)] reflections
4141, 862, 861
Rint0.027
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.091, 0.99
No. of reflections861
No. of parameters13
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.17

Computer programs: COLLECT (Nonius, 2001)., DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.

 

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals
First citationBetteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, C. K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals
First citationCourseille, D., Hospital, M., Leroy, F. & Watkin, D. (1979). 5th European Crystallographic Meeting, Copenhagen, Denmark, p. 285.
First citationHuffman, H. M., Todd, S. S. & Oliver, G. D. (1949). J. Am. Chem. Soc. 71, 584–592. CrossRef CAS Web of Science
First citationNonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
First citationWatkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.

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ISSN: 2056-9890
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