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The crystal structure of (1S)-(−)-α-pinene, C10H16, has been determined at 203 (2) K by in situ crystal growth from the liquid.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016415/cv6064sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016415/cv6064Isup2.hkl
Contains datablock I

CCDC reference: 176009

Key indicators

  • Single-crystal X-ray study
  • T = 203 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.046
  • wR factor = 0.103
  • Data-to-parameter ratio = 14.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.03 From the CIF: _reflns_number_total 1379 From the CIF: _diffrn_reflns_limit_ max hkl 8. 7. 18. From the CIF: _diffrn_reflns_limit_ min hkl -5. -7. -16. TEST1: Expected hkl limits for theta max Calculated maximum hkl 8. 9. 18. Calculated minimum hkl -8. -9. -18. ALERT: Expected hkl max differ from CIF values REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.03 From the CIF: _reflns_number_total 1379 Count of symmetry unique reflns 915 Completeness (_total/calc) 150.71% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 464 Fraction of Friedel pairs measured 0.507 Are heavy atom types Z>Si present no ALERT: MoKa measured Friedel data cannot be used to determine absolute structure in a light-atom study EXCEPT under VERY special conditions. It is preferred that Friedel data is merged in such cases.

Comment top

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)].

Experimental top

(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.

Refinement top

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 P212121; the reported value of Rint corresponds to merging in this space group.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: 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 refine structure: SHELXL97 (Sheldrick 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
[Figure 2] Fig. 2. Projection onto (100) of the crystal structure of (I) (CAMERON; Watkin et al., 1996).
(1S)-(-)-α-Pinene top
Crystal data top
C10H16Dx = 1.041 Mg m3
Mr = 136.23Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, P212121Cell parameters from 2466 reflections
a = 7.1944 (6) Åθ = 1.0–25.0°
b = 7.5920 (3) ŵ = 0.06 mm1
c = 15.9190 (15) ÅT = 203 K
V = 869.49 (11) Å3Cylinder, colourless
Z = 40.20 mm (radius)
F(000) = 304
Data collection top
Nonius KappaCCD
diffractometer
Rint = 0.050
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 3.7°
Thin–slice ω and ϕ scansh = 58
3727 measured reflectionsk = 77
1379 independent reflectionsl = 1618
1194 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0279P)2 + 0.1574P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1379 reflectionsΔρmax = 0.13 e Å3
95 parametersΔρmin = 0.15 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.096 (12)
Crystal data top
C10H16V = 869.49 (11) Å3
Mr = 136.23Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.1944 (6) ŵ = 0.06 mm1
b = 7.5920 (3) ÅT = 203 K
c = 15.9190 (15) Å0.20 mm (radius)
Data collection top
Nonius KappaCCD
diffractometer
1194 reflections with I > 2σ(I)
3727 measured reflectionsRint = 0.050
1379 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.103H-atom parameters constrained
S = 1.06Δρmax = 0.13 e Å3
1379 reflectionsΔρmin = 0.15 e Å3
95 parameters
Special details top

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 F2, conventional R-factors R are based

on F, with F set to zero for negative F2. The threshold expression of

F2 > σ(F2) 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 even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8184 (3)0.0414 (3)0.34005 (13)0.0381 (5)
H10.84670.14690.30580.046*
C20.7443 (3)0.0758 (3)0.42735 (12)0.0389 (5)
C30.7112 (3)0.0642 (3)0.47423 (13)0.0432 (6)
H30.66840.05010.52960.052*
C40.7418 (3)0.2465 (3)0.43954 (13)0.0434 (5)
H4A0.82820.31110.47580.052*
H4B0.62360.31070.43850.052*
C50.8211 (3)0.2352 (3)0.35071 (13)0.0397 (5)
H50.85240.34950.32430.048*
C60.7035 (3)0.1064 (3)0.29525 (12)0.0363 (5)
C70.9778 (3)0.0946 (3)0.34910 (14)0.0449 (5)
H7A1.06030.10210.30020.054*
H7B1.04830.08500.40160.054*
C80.4934 (3)0.1089 (3)0.30463 (14)0.0439 (5)
H8A0.43970.01560.27090.066*
H8B0.44570.22170.28590.066*
H8C0.46080.09110.36310.066*
C90.7516 (3)0.1208 (3)0.20215 (13)0.0531 (6)
H9A0.69260.02540.17170.080*
H9D0.88530.11350.19510.080*
H9B0.70750.23270.18050.080*
C100.7134 (4)0.2629 (3)0.45502 (15)0.0563 (7)
H10D0.67570.26440.51350.084*
H10A0.82780.32920.44850.084*
H10B0.61680.31590.42080.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0322 (10)0.0374 (12)0.0447 (11)0.0054 (8)0.0009 (10)0.0060 (9)
C20.0323 (10)0.0383 (13)0.0461 (11)0.0045 (10)0.0050 (9)0.0055 (9)
C30.0411 (11)0.0525 (15)0.0361 (10)0.0028 (11)0.0007 (9)0.0066 (9)
C40.0455 (13)0.0395 (13)0.0452 (11)0.0026 (10)0.0005 (11)0.0066 (8)
C50.0380 (11)0.0343 (11)0.0468 (11)0.0041 (9)0.0015 (10)0.0029 (9)
C60.0347 (10)0.0345 (11)0.0396 (10)0.0019 (9)0.0009 (9)0.0015 (9)
C70.0293 (9)0.0570 (13)0.0485 (12)0.0006 (11)0.0012 (9)0.0006 (12)
C80.0339 (10)0.0456 (13)0.0520 (12)0.0018 (10)0.0041 (9)0.0022 (11)
C90.0535 (13)0.0614 (15)0.0445 (12)0.0019 (13)0.0015 (11)0.0002 (11)
C100.0542 (15)0.0461 (15)0.0685 (16)0.0007 (12)0.0062 (13)0.0144 (11)
Geometric parameters (Å, º) top
C1—C21.511 (3)C6—C81.519 (2)
C1—C71.549 (3)C6—C91.526 (3)
C1—C61.566 (3)C7—H7A0.9800
C1—H10.9900C7—H7B0.9800
C2—C31.320 (3)C8—H8A0.9700
C2—C101.504 (3)C8—H8B0.9700
C3—C41.506 (3)C8—H8C0.9700
C3—H30.9400C9—H9A0.9700
C4—C51.527 (3)C9—H9D0.9700
C4—H4A0.9800C9—H9B0.9700
C4—H4B0.9800C10—H10D0.9700
C5—C71.553 (3)C10—H10A0.9700
C5—C61.566 (3)C10—H10B0.9700
C5—H50.9900
C2—C1—C7106.91 (16)C8—C6—C5118.33 (17)
C2—C1—C6110.86 (15)C9—C6—C5112.36 (16)
C7—C1—C687.46 (14)C1—C6—C584.57 (14)
C2—C1—H1116.0C1—C7—C585.55 (13)
C7—C1—H1116.0C1—C7—H7A114.4
C6—C1—H1116.0C5—C7—H7A114.4
C3—C2—C10124.64 (19)C1—C7—H7B114.4
C3—C2—C1116.38 (17)C5—C7—H7B114.4
C10—C2—C1118.99 (18)H7A—C7—H7B111.5
C2—C3—C4120.40 (18)C6—C8—H8A109.5
C2—C3—H3119.8C6—C8—H8B109.5
C4—C3—H3119.8H8A—C8—H8B109.5
C3—C4—C5110.04 (16)C6—C8—H8C109.5
C3—C4—H4A109.7H8A—C8—H8C109.5
C5—C4—H4A109.7H8B—C8—H8C109.5
C3—C4—H4B109.7C6—C9—H9A109.5
C5—C4—H4B109.7C6—C9—H9D109.5
H4A—C4—H4B108.2H9A—C9—H9D109.5
C4—C5—C7108.97 (17)C6—C9—H9B109.5
C4—C5—C6110.80 (16)H9A—C9—H9B109.5
C7—C5—C687.34 (15)H9D—C9—H9B109.5
C4—C5—H5115.5C2—C10—H10D109.5
C7—C5—H5115.5C2—C10—H10A109.5
C6—C5—H5115.5H10D—C10—H10A109.5
C8—C6—C9108.69 (17)C2—C10—H10B109.5
C8—C6—C1119.33 (17)H10D—C10—H10B109.5
C9—C6—C1111.94 (16)H10A—C10—H10B109.5
C7—C1—C2—C347.0 (2)C2—C1—C6—C578.47 (17)
C6—C1—C2—C346.8 (2)C7—C1—C6—C528.68 (14)
C7—C1—C2—C10133.0 (2)C4—C5—C6—C839.8 (2)
C6—C1—C2—C10133.23 (19)C7—C5—C6—C8149.11 (18)
C10—C2—C3—C4178.2 (2)C4—C5—C6—C9167.80 (17)
C1—C2—C3—C41.8 (3)C7—C5—C6—C982.91 (18)
C2—C3—C4—C53.1 (3)C4—C5—C6—C180.69 (17)
C3—C4—C5—C744.7 (2)C7—C5—C6—C128.61 (14)
C3—C4—C5—C649.7 (2)C2—C1—C7—C582.15 (17)
C2—C1—C6—C841.1 (2)C6—C1—C7—C528.89 (14)
C7—C1—C6—C8148.23 (18)C4—C5—C7—C182.21 (17)
C2—C1—C6—C9169.60 (16)C6—C5—C7—C128.89 (14)
C7—C1—C6—C983.26 (18)

Experimental details

Crystal data
Chemical formulaC10H16
Mr136.23
Crystal system, space groupOrthorhombic, P212121
Temperature (K)203
a, b, c (Å)7.1944 (6), 7.5920 (3), 15.9190 (15)
V3)869.49 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.06
Crystal size (mm)0.20 (radius)
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3727, 1379, 1194
Rint0.050
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.103, 1.06
No. of reflections1379
No. of parameters95
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.13, 0.15

Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR92 (Altomare et al. 1994), SHELXL97 (Sheldrick 1997), SHELXL97.

 

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