(1S)-(–)-β-Pinene

The crystal structure of (1S)-(−)-β-pinene, C₁₀H₁₆, has been determined at 185 (2) K by in situ growth from the liquid.

Key indicators

• Single-crystal X-ray study
• T = 185 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.060
• wR factor = 0.155
• Data-to-parameter ratio = 18.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.78
         From the CIF: _reflns_number_total               1747
         Count of symmetry unique reflns         1100
         Completeness (_total/calc)            158.82%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       647
         Fraction of Friedel pairs measured     0.588
         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.

---

S1. Comment

β-Pinene, (I), occurs in nature in the majority of the oils in which α-pinene is found; the percentage present however is very variable and is, as a rule, considerably less than that of the latter. For an account of the history of β-pinene and the determination of its structure using the techniques of classical organic chemistry, see 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)-(-)-β-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 201 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 crystal was cooled subsequently to 185 (2) K for data collection.

S3. Refinement

H atoms were placed geometrically and refined using a riding model with an isotropic displacement parameter fixed at 1.2U_eq 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 R_int corresponds to merging in this space group.

Computing details

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

	Fig. 1. The asymmetric unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
	Fig. 2. Projection onto (100) of the crystal structure of (I) (CAMERON; Watkin et al., 1996).

(1S)-(-)-β-Pinene

Crystal data

C10H16	Dx = 1.034 Mg m^−3
Mr = 136.23	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, P212121	Cell parameters from 3825 reflections
a = 7.5079 (3) Å	θ = 1.0–26.7°
b = 9.3361 (8) Å	µ = 0.06 mm^−1
c = 12.4875 (11) Å	T = 185 K
V = 875.30 (11) Å^3	Cylinder, colourless
Z = 4	0.20 mm (radius)
F(000) = 304

Data collection

Nonius KappaCCD diffractometer	Rint = 0.081
Radiation source: fine-focus sealed tube	θmax = 26.8°, θmin = 3.9°
Thin–slice ω and ϕ scans	h = −9→9
4164 measured reflections	k = −11→11
1747 independent reflections	l = −15→15
1498 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0527P)^2 + 0.2821P] where P = (Fo^2 + 2Fc^2)/3
1747 reflections	(Δ/σ)max = 0.004
93 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

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 R_int reported corresponds to merging of the data in this space group. The absolute configuration was assigned from the known configuration of the sample.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8191 (3)	0.1927 (2)	0.77499 (17)	0.0373 (5)
H1	0.8311	0.0972	0.7396	0.045*
C2	0.7957 (3)	0.1898 (2)	0.89424 (17)	0.0375 (5)
C3	0.8058 (4)	0.3355 (2)	0.94799 (19)	0.0468 (6)
H3A	0.9198	0.3423	0.9876	0.056*
H3B	0.7080	0.3431	1.0009	0.056*
C4	0.7930 (4)	0.4633 (2)	0.86954 (19)	0.0480 (6)
H4A	0.6755	0.5101	0.8781	0.058*
H4B	0.8859	0.5344	0.8878	0.058*
C5	0.8159 (3)	0.4177 (2)	0.75372 (18)	0.0418 (5)
H5	0.8254	0.4979	0.7009	0.050*
C6	0.6809 (3)	0.2971 (2)	0.72334 (16)	0.0365 (5)
C7	0.9645 (3)	0.3039 (3)	0.7468 (2)	0.0477 (6)
H7A	1.0586	0.3142	0.8018	0.057*
H7B	1.0162	0.2922	0.6744	0.057*
C8	0.4944 (3)	0.3017 (3)	0.77088 (19)	0.0505 (6)
H8B	0.4308	0.2134	0.7526	0.076*
H8C	0.4298	0.3842	0.7418	0.076*
H8D	0.5025	0.3106	0.8489	0.076*
C9	0.6662 (4)	0.2773 (3)	0.60259 (19)	0.0557 (7)
H9B	0.6054	0.1867	0.5872	0.084*
H9C	0.7858	0.2755	0.5711	0.084*
H9D	0.5981	0.3568	0.5719	0.084*
C10	0.7721 (4)	0.0701 (3)	0.9487 (2)	0.0482 (6)
H10B	0.7693	−0.0192	0.9123	0.072*
H10C	0.7578	0.0733	1.0242	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0373 (10)	0.0307 (9)	0.0439 (12)	0.0025 (10)	0.0046 (9)	−0.0010 (9)
C2	0.0309 (10)	0.0384 (10)	0.0433 (11)	0.0020 (9)	−0.0042 (8)	0.0034 (9)
C3	0.0561 (14)	0.0482 (14)	0.0362 (12)	−0.0005 (12)	−0.0059 (11)	−0.0002 (9)
C4	0.0619 (16)	0.0368 (11)	0.0452 (14)	−0.0034 (11)	−0.0035 (11)	−0.0050 (9)
C5	0.0480 (13)	0.0346 (10)	0.0428 (12)	−0.0009 (10)	0.0044 (11)	0.0043 (9)
C6	0.0391 (11)	0.0382 (10)	0.0321 (10)	0.0007 (10)	0.0014 (8)	0.0003 (9)
C7	0.0374 (12)	0.0502 (14)	0.0555 (14)	−0.0026 (10)	0.0107 (10)	0.0004 (13)
C8	0.0386 (12)	0.0696 (17)	0.0435 (13)	0.0054 (13)	−0.0017 (9)	0.0025 (13)
C9	0.0717 (18)	0.0591 (15)	0.0363 (12)	−0.0023 (15)	0.0015 (12)	0.0010 (10)
C10	0.0533 (15)	0.0446 (12)	0.0468 (13)	0.0030 (11)	−0.0080 (11)	0.0082 (11)

Geometric parameters (Å, º)

C1—C2	1.500 (3)	C5—H5	1.0000
C1—C7	1.547 (3)	C6—C8	1.521 (3)
C1—C6	1.562 (3)	C6—C9	1.523 (3)
C1—H1	1.0000	C7—H7A	0.9900
C2—C10	1.320 (3)	C7—H7B	0.9900
C2—C3	1.519 (3)	C8—H8B	0.9800
C3—C4	1.547 (3)	C8—H8C	0.9800
C3—H3A	0.9900	C8—H8D	0.9800
C3—H3B	0.9900	C9—H9B	0.9800
C4—C5	1.517 (3)	C9—H9C	0.9800
C4—H4A	0.9900	C9—H9D	0.9800
C4—H4B	0.9900	C10—H10B	0.9500
C5—C7	1.543 (3)	C10—H10C	0.9500
C5—C6	1.562 (3)
C2—C1—C7	108.72 (19)	C8—C6—C9	108.85 (19)
C2—C1—C6	110.10 (16)	C8—C6—C1	117.88 (18)
C7—C1—C6	87.48 (15)	C9—C6—C1	112.40 (18)
C2—C1—H1	115.7	C8—C6—C5	118.79 (19)
C7—C1—H1	115.7	C9—C6—C5	112.03 (19)
C6—C1—H1	115.7	C1—C6—C5	85.34 (15)
C10—C2—C1	122.8 (2)	C5—C7—C1	86.49 (15)
C10—C2—C3	122.5 (2)	C5—C7—H7A	114.2
C1—C2—C3	114.62 (19)	C1—C7—H7A	114.2
C2—C3—C4	114.06 (19)	C5—C7—H7B	114.2
C2—C3—H3A	108.7	C1—C7—H7B	114.2
C4—C3—H3A	108.7	H7A—C7—H7B	111.4
C2—C3—H3B	108.7	C6—C8—H8B	109.5
C4—C3—H3B	108.7	C6—C8—H8C	109.5
H3A—C3—H3B	107.6	H8B—C8—H8C	109.5
C5—C4—C3	112.37 (19)	C6—C8—H8D	109.5
C5—C4—H4A	109.1	H8B—C8—H8D	109.5
C3—C4—H4A	109.1	H8C—C8—H8D	109.5
C5—C4—H4B	109.1	C6—C9—H9B	109.5
C3—C4—H4B	109.1	C6—C9—H9C	109.5
H4A—C4—H4B	107.9	H9B—C9—H9C	109.5
C4—C5—C7	109.2 (2)	C6—C9—H9D	109.5
C4—C5—C6	111.11 (19)	H9B—C9—H9D	109.5
C7—C5—C6	87.65 (16)	H9C—C9—H9D	109.5
C4—C5—H5	115.2	C2—C10—H10B	120.0
C7—C5—H5	115.2	C2—C10—H10C	120.0
C6—C5—H5	115.2	H10B—C10—H10C	120.0
C7—C1—C2—C10	−139.6 (2)	C2—C1—C6—C5	82.37 (18)
C6—C1—C2—C10	126.1 (2)	C7—C1—C6—C5	−26.65 (16)
C7—C1—C2—C3	39.0 (2)	C4—C5—C6—C8	36.4 (3)
C6—C1—C2—C3	−55.3 (2)	C7—C5—C6—C8	146.1 (2)
C10—C2—C3—C4	−167.5 (2)	C4—C5—C6—C9	164.8 (2)
C1—C2—C3—C4	14.0 (3)	C7—C5—C6—C9	−85.6 (2)
C2—C3—C4—C5	−13.3 (3)	C4—C5—C6—C1	−82.9 (2)
C3—C4—C5—C7	−40.4 (3)	C7—C5—C6—C1	26.72 (15)
C3—C4—C5—C6	54.7 (3)	C4—C5—C7—C1	84.6 (2)
C2—C1—C6—C8	−37.9 (3)	C6—C5—C7—C1	−26.96 (15)
C7—C1—C6—C8	−146.9 (2)	C2—C1—C7—C5	−83.43 (18)
C2—C1—C6—C9	−165.7 (2)	C6—C1—C7—C5	26.95 (16)
C7—C1—C6—C9	85.3 (2)