(1S) (–) α Pinene

Acta Cryst.(2001). E57, o1039±o1040 DOI: 10.1107/S1600536801016415 Bond and Davies C₁₀H₁₆

o1039

organic papers

Acta Crystallographica Section E

Structure Reports

Online ISSN 1600-5368

(1

S

)-(±)-

a

-Pinene

Andrew D. Bond* and John E. Davies

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 203 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.046 wRfactor = 0.103

Data-to-parameter ratio = 14.5

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

The crystal structure of (1S)-(ÿ)--pinene, C10H16, has been

determined at 203 (2) K by in situ crystal growth from the liquid.

Comment

-Pinene, (I), is very widely distributed in nature. It is present in the majority of essential oils derived from the Coniferae and it is the principal constituent of oil of turpentine. An account of its history and the determination of its structure using the techniques of classical organic chemistry is given by Simonsen & Owen (1947). This work forms part of a continuing study devoted to improving the techniques for determining the crystal structures of substances which are liquids at room temperature [see, for example, Davies & Bond (2001)].

Experimental

(1S)-(ÿ)--Pinene (99%) was obtained from the Aldrich Company and used without further puri®cation. The crystal was grown in a 0.4 mm glass capillary tube at 203 K (a temperature only slightly less than the melting point of the solid in the capillary tube). With the axis of the capillary parallel to the'axis and horizontal on the instru-ment, the crystal was obtained by moving a plug of solid material up and down the tube [the movement being controlled with the standard Z(height) adjustment of the goniometer head]. The data are 90.2% complete because the crystal melted during an attempt to move it into a different orientation for the ®nal set of frames. Previous attempts to reduce the temperature further for data collection resulted in the crystals being destroyed. Data were collected therefore at 203 (2) K. Crystal data

C10H16

Mr= 136.23

Orthorhombic,P212121

a= 7.1944 (6) AÊ

b= 7.5920 (3) AÊ

c= 15.9190 (15) AÊ

V= 869.49 (11) AÊ3

Z= 4

Dx= 1.041 Mg mÿ3

MoKradiation Cell parameters from 2466

re¯ections = 1.0±25.0

= 0.06 mmÿ1

T= 203 (2) K Cylinder, colourless 0.20 mm (radius)

Data collection

Nonius KappaCCD diffractometer Thin-slice!and'scans 3727 measured re¯ections 1379 independent re¯ections 1194 re¯ections withI> 2(I)

Rint= 0.050

max= 25.0

h=ÿ5!8

k=ÿ7!7

l=ÿ16!18 Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.046}

wR(F2_{) = 0.103}

S= 1.06 1379 re¯ections 95 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0279P)2

+ 0.1574P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.13 e AÊÿ3

min=ÿ0.15 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.096 (12)

H atoms were placed geometrically and re®ned using a riding model with an isotropic displacement parameter ®xed at 1.2Ueqof the

carbon to which they are attached. The absolute con®guration could not be determined reliably and was assigned according to the known con®guration of the sample. Friedel pairs were merged, therefore, prior to merging of other equivalent re¯ections in P212121; the

reported value ofRintcorresponds to merging in this space group.

Data collection:COLLECT(Nonius, 1998); cell re®nement:HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); software used to prepare material for publication:SHELXL97.

We thank the EPSRC for ®nancial assistance towards the purchase of the Nonius CCD diffractometer.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435.

Davies, J. E. & Bond, A. D. (2001).Acta Cryst.E57, o947±o949. Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). HKL DENZO and SCALEPACK. University of Texas, Southwestern Medical Center at Dallas, USA. Sheldrick, G. M. (1993).XP. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Simonsen, J. L. & Owen, L. N. (1947). The Terpenes, Vol. I, p. 105ff.

Cambridge: Cambridge University Press.

Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996).CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.

Figure 2

Projection onto (100) of the crystal structure of (I) (CAMERON; Watkin et al., 1996).

Figure 1

supporting information

sup-1

supporting information

Acta Cryst. (2001). E57, o1039–o1040 [doi:10.1107/S1600536801016415]

(1

S

)-(

–

)-

α

-Pinene

Andrew D. Bond and John E. Davies

S1. Comment

α-Pinene, (I), is very widely distributed in nature. It is present in the majority of essential oils derived from the Coniferae and it is the principal constituent of oil of turpentine. An account of its history and the determination of its structure using the techniques of classical organic chemistry is given by Simonsen & Owen (1947). This work forms part of a continuing study devoted to improving the techniques for determining the crystal structures of substances which are liquids at room temperature [see, for example, Davies & Bond (2001)].

S2. Experimental

(1S)-(-)-α-Pinene (99%) was obtained from the Aldrich Company and used without further purification. The crystal was grown in a 0.4 mm glass capillary tube at 203 K (a temperature only slightly less than the melting point of the solid in the capillary tube). With the axis of the capillary parallel to the φ axis and horizontal on the instrument, the crystal was obtained by moving a plug of solid material up and down the tube [the movement being controlled with the standard Z

(height) adjustment of the goniometer head]. The data are 90.2% complete because the crystal MELTED during an attempt to move it into a different orientation for the final set of frames. Previous attempts to reduce the temperature further for data collection resulted in the crystals being destroyed. Data were collected therefore at 203 (2) K.

S3. Refinement

H atoms were placed geometrically and refined using a riding model with an isotropic displacement parameter fixed at 1.2Ueq for the carbon to which they are attached. The absolute configuration could not be determined reliably and was

assigned according to the known configuration of the sample. Friedel pairs were merged therefore prior to merging in

Figure 1

The asymmetric unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).

supporting information

sup-3

(1S)-(-)-α-Pinene

Crystal data

C10H16 Mr = 136.23

Orthorhombic, P212121 a = 7.1944 (6) Å

b = 7.5920 (3) Å

c = 15.9190 (15) Å

V = 869.49 (11) Å3 Z = 4

F(000) = 304

Dx = 1.041 Mg m−3

Mo Kα radiation, λ = 0.7107 Å Cell parameters from 2466 reflections

θ = 1.0–25.0°

µ = 0.06 mm−1 T = 203 K

Cylinder, colourless 0.20 mm (radius)

Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube Thin–slice ω and φ scans

3727 measured reflections 1379 independent reflections

1194 reflections with I > 2σ(I)

Rint = 0.050

θmax = 25.0°, θmin = 3.7° h = −5→8

k = −7→7

l = −16→18

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.046} wR(F2_{) = 0.103} S = 1.06 1379 reflections 95 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0279P)2 + 0.1574P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.13 e Å−3

Δρmin = −0.15 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.096 (12)

Special details

Experimental. Crystal grown in a 0.4 mm Lindemann tube at 203 K. Friedel pairs were merged prior to merging in P212121; the value of Rint reported corresponds to merging of the data in this space group. The absolute configuration

was assigned from the known configuration of the sample. The data are only 90.2% complete because the crystal MELTED during an attempt to move it into a different orientation for the final set of frames!

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based

on F, with F set to zero for negative F2_{. The threshold expression of}

F2 _{> σ(F}2_{) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R}

-factors based on F2 _{are statistically about twice as large as those based on F, and R- factors based on ALL data will be}

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

x y z Uiso*/Ueq

C1 0.8184 (3) −0.0414 (3) 0.34005 (13) 0.0381 (5) H1 0.8467 −0.1469 0.3058 0.046* C2 0.7443 (3) −0.0758 (3) 0.42735 (12) 0.0389 (5) C3 0.7112 (3) 0.0642 (3) 0.47423 (13) 0.0432 (6)

H3 0.6684 0.0501 0.5296 0.052*

C4 0.7418 (3) 0.2465 (3) 0.43954 (13) 0.0434 (5) H4A 0.8282 0.3111 0.4758 0.052* H4B 0.6236 0.3107 0.4385 0.052* C5 0.8211 (3) 0.2352 (3) 0.35071 (13) 0.0397 (5)

H5 0.8524 0.3495 0.3243 0.048*

C6 0.7035 (3) 0.1064 (3) 0.29525 (12) 0.0363 (5) C7 0.9778 (3) 0.0946 (3) 0.34910 (14) 0.0449 (5) H7A 1.0603 0.1021 0.3002 0.054* H7B 1.0483 0.0850 0.4016 0.054* C8 0.4934 (3) 0.1089 (3) 0.30463 (14) 0.0439 (5) H8A 0.4397 0.0156 0.2709 0.066* H8B 0.4457 0.2217 0.2859 0.066* H8C 0.4608 0.0911 0.3631 0.066* C9 0.7516 (3) 0.1208 (3) 0.20215 (13) 0.0531 (6) H9A 0.6926 0.0254 0.1717 0.080* H9D 0.8853 0.1135 0.1951 0.080* H9B 0.7075 0.2327 0.1805 0.080* C10 0.7134 (4) −0.2629 (3) 0.45502 (15) 0.0563 (7) H10D 0.6757 −0.2644 0.5135 0.084* H10A 0.8278 −0.3292 0.4485 0.084* H10B 0.6168 −0.3159 0.4208 0.084*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0322 (10) 0.0374 (12) 0.0447 (11) 0.0054 (8) −0.0009 (10) −0.0060 (9) C2 0.0323 (10) 0.0383 (13) 0.0461 (11) 0.0045 (10) −0.0050 (9) 0.0055 (9) C3 0.0411 (11) 0.0525 (15) 0.0361 (10) 0.0028 (11) 0.0007 (9) 0.0066 (9) C4 0.0455 (13) 0.0395 (13) 0.0452 (11) −0.0026 (10) −0.0005 (11) −0.0066 (8) C5 0.0380 (11) 0.0343 (11) 0.0468 (11) −0.0041 (9) 0.0015 (10) 0.0029 (9) C6 0.0347 (10) 0.0345 (11) 0.0396 (10) 0.0019 (9) −0.0009 (9) 0.0015 (9) C7 0.0293 (9) 0.0570 (13) 0.0485 (12) −0.0006 (11) 0.0012 (9) 0.0006 (12) C8 0.0339 (10) 0.0456 (13) 0.0520 (12) 0.0018 (10) −0.0041 (9) 0.0022 (11) C9 0.0535 (13) 0.0614 (15) 0.0445 (12) 0.0019 (13) 0.0015 (11) −0.0002 (11) C10 0.0542 (15) 0.0461 (15) 0.0685 (16) −0.0007 (12) −0.0062 (13) 0.0144 (11)

supporting information

sup-5

C1—C6 1.566 (3) C7—H7A 0.9800

C1—H1 0.9900 C7—H7B 0.9800

C2—C3 1.320 (3) C8—H8A 0.9700

C2—C10 1.504 (3) C8—H8B 0.9700

C3—C4 1.506 (3) C8—H8C 0.9700

C3—H3 0.9400 C9—H9A 0.9700

C4—C5 1.527 (3) C9—H9D 0.9700

C4—H4A 0.9800 C9—H9B 0.9700

C4—H4B 0.9800 C10—H10D 0.9700

C5—C7 1.553 (3) C10—H10A 0.9700

C5—C6 1.566 (3) C10—H10B 0.9700

C5—H5 0.9900

C2—C1—C7 106.91 (16) C8—C6—C5 118.33 (17) C2—C1—C6 110.86 (15) C9—C6—C5 112.36 (16) C7—C1—C6 87.46 (14) C1—C6—C5 84.57 (14)

C2—C1—H1 116.0 C1—C7—C5 85.55 (13)

C7—C1—H1 116.0 C1—C7—H7A 114.4

C6—C1—H1 116.0 C5—C7—H7A 114.4

C3—C2—C10 124.64 (19) C1—C7—H7B 114.4 C3—C2—C1 116.38 (17) C5—C7—H7B 114.4 C10—C2—C1 118.99 (18) H7A—C7—H7B 111.5 C2—C3—C4 120.40 (18) C6—C8—H8A 109.5

C2—C3—H3 119.8 C6—C8—H8B 109.5

C4—C3—H3 119.8 H8A—C8—H8B 109.5

C3—C4—C5 110.04 (16) C6—C8—H8C 109.5

C3—C4—H4A 109.7 H8A—C8—H8C 109.5

C5—C4—H4A 109.7 H8B—C8—H8C 109.5

C3—C4—H4B 109.7 C6—C9—H9A 109.5

C5—C4—H4B 109.7 C6—C9—H9D 109.5

H4A—C4—H4B 108.2 H9A—C9—H9D 109.5

C4—C5—C7 108.97 (17) C6—C9—H9B 109.5 C4—C5—C6 110.80 (16) H9A—C9—H9B 109.5 C7—C5—C6 87.34 (15) H9D—C9—H9B 109.5

C4—C5—H5 115.5 C2—C10—H10D 109.5

C7—C5—H5 115.5 C2—C10—H10A 109.5

C6—C5—H5 115.5 H10D—C10—H10A 109.5 C8—C6—C9 108.69 (17) C2—C10—H10B 109.5 C8—C6—C1 119.33 (17) H10D—C10—H10B 109.5 C9—C6—C1 111.94 (16) H10A—C10—H10B 109.5