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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1736.
Published online 2010 June 23. doi:  10.1107/S1600536810023251
PMCID: PMC3007015

1-(2-Phenyl­eth­yl)adamantane

Abstract

In the title compound, C18H24, the adamantane cage consists of three fused cyclo­hexane rings in almost ideal chair conformations, with C—C—C angles in the range 108.0 (14)–111.1 (15)°. The phenyl and 1-adamantyl substituents adopt anti orientations with a C—C—C—C torsion angle of 177.10 (16)°. In the crystal packing, the mol­ecules are linked by weak C—H(...)π inter­actions into chains along the a axis.

Related literature

The title compound was prepared according to a modified procedure of Adkins & Billica (1948 [triangle]). For some important properties of compounds bearing the adamantane scaffold, see: van der Schyf et al. (2009 [triangle]); van Bommel et al. (2001 [triangle]). For a related structure, see: Raine et al. (2002 [triangle]).

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Object name is e-66-o1736-scheme1.jpg

Experimental

Crystal data

  • C18H24
  • M r = 240.37
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1736-efi4.jpg
  • a = 6.4844 (5) Å
  • b = 7.5109 (5) Å
  • c = 28.5305 (19) Å
  • V = 1389.55 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.06 mm−1
  • T = 120 K
  • 0.40 × 0.20 × 0.20 mm

Data collection

  • Kuma KM-4-CCD diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 [triangle]) T min = 0.924, T max = 1.000
  • 11994 measured reflections
  • 1452 independent reflections
  • 1277 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.127
  • S = 1.30
  • 1452 reflections
  • 163 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810023251/ez2215sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023251/ez2215Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial support of this work by the Czech Ministry of Education, project No. MSM 7088352101, and by the Tomas Bata Foundation is gratefully acknowledged.

supplementary crystallographic information

Comment

Adamantane is a molecule with an elegant structure and unique properties. The addition of the highly lipophilic adamantane cage to a known biologically active compound can significantly improve the pharmacokinetic profile of the resulting molecule, e.g. its oral bioavailability (van der Schyf et al. 2009). Moreover, the relatively stable host–guest interactions of the adamantane scaffold with β-cyclodextrin might increase the solubility of non-polar substances in polar media (van Bommel et al. 2001). Both these characteristics have an important role in drug design. This structure represents one of the few low-molecular-weight molecules bearing an adamantane moiety that has no polar function group. Therefore, this compound may be used as a standard molecule for investigations of non-polar interactions.

The asymmetric unit of the title compound consists of a single molecule (Fig. 1). The benzene ring is nearly planar with a maximum deviation from the best plane being 0.007 (2) Å for C16. The torsion angles describing mutual alignment of the 1-adamantyl and phenyl substituents C18—C13—C12—C11, C13—C12—C11—C1 and C12—C11—C1—C2 are -73.4 (2), -177.10 (16) and 179.59 (16)°, respectively. In the crystal packing, the molecules are arranged into chains parallel to the a-axis linked by weak C—H···π interactions (Fig. 2, Table 1).

Experimental

The title compound was prepared according to a modified literature procedure published by Adkins & Billica (1948). 2-(1-Adamantyl)-2-benzyl-1,3-dithiane (0.33 mmol, 114 mg) was dissolved in 5 ml of dioxane and a large excess of Raney nickel catalyst was added to this solution. The reaction mixture was stirred and refluxed under Ar atmosphere. Further portions of Raney nickel were added until the starting material was completely consumed (monitored by GC). Subsequently, the Raney nickel was filtered off, the filtrate was diluted with water and extracted with diethyl ether. The combined organic layers were washed twice with brine and dried over Na2SO4. The required product was obtained after evaporation of solvent in vacuum as a colorless crystalline powder (72 mg, 91%, mp 318–324 K). The crystal used for data collection was grown by spontaneous evaporation from deuterochloroform at room temperature.

Refinement

Hydrogen atoms were positioned geometrically and refined as riding using standard SHELXTL constraints, with their Uiso set to either 1.2Ueq of their parent atoms. In the absence of significant anomalous scattering, Friedel pairs were merged.

Figures

Fig. 1.
ORTEP diagram of the asymmetric unit showing the atom labelling scheme with atoms represented as 50% probability ellipsoids.
Fig. 2.
A partial view of the crystal packing viewed along the b-axis showing the arrangement of the molecules into chains parallel to the a-axis stabilized by weak C—H···π interactions (dotted lines). Cg1 is the center ...

Crystal data

C18H24Dx = 1.149 Mg m3
Mr = 240.37Melting point: 321 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5446 reflections
a = 6.4844 (5) Åθ = 3.1–27.2°
b = 7.5109 (5) ŵ = 0.06 mm1
c = 28.5305 (19) ÅT = 120 K
V = 1389.55 (17) Å3Block, colourless
Z = 40.40 × 0.20 × 0.20 mm
F(000) = 528

Data collection

Kuma KM-4-CCD diffractometer1452 independent reflections
Radiation source: fine-focus sealed tube1277 reflections with I > 2σ(I)
graphiteRint = 0.043
Detector resolution: 0.06 mm pixels mm-1θmax = 25.0°, θmin = 3.1°
ω scanh = −5→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)k = −8→8
Tmin = 0.924, Tmax = 1.000l = −33→33
11994 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.30w = 1/[σ2(Fo2) + (0.0705P)2 + 0.0787P] where P = (Fo2 + 2Fc2)/3
1452 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.15 e Å3

Special details

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 > 2σ(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)

xyzUiso*/Ueq
C10.8116 (4)0.4428 (3)0.14870 (8)0.0172 (6)
C20.6166 (4)0.4772 (3)0.17845 (9)0.0207 (6)
H2A0.64020.58120.19910.025*
H2B0.49930.50520.15750.025*
C30.5633 (4)0.3148 (3)0.20840 (8)0.0206 (6)
H30.43660.34000.22720.025*
C40.5236 (4)0.1543 (3)0.17589 (9)0.0232 (6)
H4A0.48870.04820.19490.028*
H4B0.40590.18030.15490.028*
C50.7167 (4)0.1176 (3)0.14680 (8)0.0212 (6)
H50.69130.01370.12570.025*
C60.8974 (4)0.0749 (3)0.17999 (9)0.0222 (6)
H6A0.8640−0.03160.19900.027*
H6B1.02300.04900.16150.027*
C70.9363 (4)0.2344 (3)0.21230 (8)0.0195 (6)
H71.05450.20720.23370.023*
C80.9892 (4)0.3977 (3)0.18208 (8)0.0182 (6)
H8A1.01710.50100.20270.022*
H8B1.11540.37310.16370.022*
C90.7437 (4)0.2729 (4)0.24146 (8)0.0217 (6)
H9A0.76930.37560.26240.026*
H9B0.70970.16830.26110.026*
C100.7703 (4)0.2808 (3)0.11744 (9)0.0208 (6)
H10A0.65480.30760.09590.025*
H10B0.89410.25540.09830.025*
C110.8577 (4)0.6112 (3)0.12008 (8)0.0219 (6)
H11A0.73590.63770.10040.026*
H11B0.87500.71180.14210.026*
C121.0478 (5)0.6040 (4)0.08826 (9)0.0283 (7)
H12A1.17010.57270.10730.034*
H12B1.02840.50920.06460.034*
C131.0866 (5)0.7775 (4)0.06375 (8)0.0234 (6)
C141.2499 (5)0.8876 (4)0.07581 (8)0.0302 (7)
H141.33890.85390.10070.036*
C151.2855 (5)1.0453 (4)0.05228 (9)0.0349 (8)
H151.39691.11970.06150.042*
C161.1596 (5)1.0957 (4)0.01530 (9)0.0317 (7)
H161.18601.2027−0.00140.038*
C170.9961 (5)0.9891 (4)0.00311 (9)0.0285 (7)
H170.90711.0238−0.02170.034*
C180.9604 (5)0.8312 (4)0.02684 (9)0.0275 (7)
H180.84770.75810.01780.033*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0173 (14)0.0180 (13)0.0163 (11)−0.0001 (11)0.0018 (10)−0.0003 (10)
C20.0141 (13)0.0236 (14)0.0244 (13)0.0037 (11)0.0005 (12)−0.0009 (11)
C30.0150 (14)0.0257 (14)0.0212 (12)0.0006 (11)0.0051 (11)0.0004 (11)
C40.0187 (15)0.0262 (14)0.0247 (12)−0.0028 (12)−0.0013 (12)0.0051 (11)
C50.0238 (15)0.0188 (13)0.0210 (12)−0.0015 (12)−0.0036 (11)−0.0037 (11)
C60.0196 (14)0.0202 (13)0.0269 (13)0.0012 (12)0.0022 (12)0.0028 (11)
C70.0157 (14)0.0246 (14)0.0184 (12)0.0004 (12)−0.0023 (11)0.0037 (11)
C80.0155 (13)0.0214 (13)0.0177 (11)−0.0004 (11)0.0010 (11)−0.0020 (11)
C90.0196 (15)0.0278 (15)0.0176 (11)−0.0020 (13)0.0016 (11)0.0017 (10)
C100.0199 (15)0.0237 (14)0.0187 (11)0.0010 (12)−0.0007 (11)−0.0012 (10)
C110.0216 (14)0.0217 (14)0.0223 (12)0.0016 (12)−0.0002 (12)0.0007 (11)
C120.0275 (16)0.0289 (15)0.0284 (13)0.0014 (14)0.0050 (13)0.0058 (12)
C130.0252 (16)0.0248 (14)0.0201 (12)−0.0005 (12)0.0029 (11)0.0015 (11)
C140.0302 (16)0.0415 (18)0.0190 (12)−0.0061 (15)−0.0020 (12)0.0030 (12)
C150.040 (2)0.0352 (17)0.0291 (14)−0.0181 (15)−0.0039 (14)−0.0028 (13)
C160.0468 (19)0.0250 (14)0.0235 (13)−0.0047 (15)0.0047 (13)0.0029 (12)
C170.0307 (17)0.0317 (15)0.0232 (13)0.0030 (14)−0.0002 (14)0.0046 (11)
C180.0237 (16)0.0283 (15)0.0306 (14)−0.0033 (13)−0.0027 (12)0.0000 (12)

Geometric parameters (Å, °)

C1—C101.532 (3)C8—H8B0.9900
C1—C81.532 (3)C9—H9A0.9900
C1—C111.535 (3)C9—H9B0.9900
C1—C21.544 (3)C10—H10A0.9900
C2—C31.529 (3)C10—H10B0.9900
C2—H2A0.9900C11—C121.532 (4)
C2—H2B0.9900C11—H11A0.9900
C3—C91.535 (4)C11—H11B0.9900
C3—C41.542 (3)C12—C131.500 (4)
C3—H31.0000C12—H12A0.9900
C4—C51.527 (4)C12—H12B0.9900
C4—H4A0.9900C13—C141.387 (4)
C4—H4B0.9900C13—C181.393 (4)
C5—C101.525 (3)C14—C151.381 (4)
C5—C61.540 (4)C14—H140.9500
C5—H51.0000C15—C161.387 (4)
C6—C71.533 (3)C15—H150.9500
C6—H6A0.9900C16—C171.373 (4)
C6—H6B0.9900C16—H160.9500
C7—C91.528 (4)C17—C181.385 (4)
C7—C81.538 (3)C17—H170.9500
C7—H71.0000C18—H180.9500
C8—H8A0.9900
C10—C1—C8108.5 (2)C1—C8—H8B109.5
C10—C1—C11112.24 (18)C7—C8—H8B109.5
C8—C1—C11111.5 (2)H8A—C8—H8B108.0
C10—C1—C2108.1 (2)C7—C9—C3109.08 (18)
C8—C1—C2108.09 (18)C7—C9—H9A109.9
C11—C1—C2108.3 (2)C3—C9—H9A109.9
C3—C2—C1111.0 (2)C7—C9—H9B109.9
C3—C2—H2A109.4C3—C9—H9B109.9
C1—C2—H2A109.4H9A—C9—H9B108.3
C3—C2—H2B109.4C5—C10—C1110.99 (19)
C1—C2—H2B109.4C5—C10—H10A109.4
H2A—C2—H2B108.0C1—C10—H10A109.4
C2—C3—C9109.5 (2)C5—C10—H10B109.4
C2—C3—C4108.97 (18)C1—C10—H10B109.4
C9—C3—C4109.7 (2)H10A—C10—H10B108.0
C2—C3—H3109.6C12—C11—C1116.3 (2)
C9—C3—H3109.6C12—C11—H11A108.2
C4—C3—H3109.6C1—C11—H11A108.2
C5—C4—C3109.3 (2)C12—C11—H11B108.2
C5—C4—H4A109.8C1—C11—H11B108.2
C3—C4—H4A109.8H11A—C11—H11B107.4
C5—C4—H4B109.8C13—C12—C11112.4 (2)
C3—C4—H4B109.8C13—C12—H12A109.1
H4A—C4—H4B108.3C11—C12—H12A109.1
C10—C5—C4109.9 (2)C13—C12—H12B109.1
C10—C5—C6109.4 (2)C11—C12—H12B109.1
C4—C5—C6109.09 (18)H12A—C12—H12B107.9
C10—C5—H5109.5C14—C13—C18117.6 (2)
C4—C5—H5109.5C14—C13—C12122.0 (2)
C6—C5—H5109.5C18—C13—C12120.4 (3)
C7—C6—C5109.4 (2)C15—C14—C13121.2 (3)
C7—C6—H6A109.8C15—C14—H14119.4
C5—C6—H6A109.8C13—C14—H14119.4
C7—C6—H6B109.8C14—C15—C16120.4 (3)
C5—C6—H6B109.8C14—C15—H15119.8
H6A—C6—H6B108.2C16—C15—H15119.8
C9—C7—C6109.9 (2)C17—C16—C15119.2 (3)
C9—C7—C8109.7 (2)C17—C16—H16120.4
C6—C7—C8108.84 (18)C15—C16—H16120.4
C9—C7—H7109.5C16—C17—C18120.3 (3)
C6—C7—H7109.5C16—C17—H17119.9
C8—C7—H7109.5C18—C17—H17119.9
C1—C8—C7110.9 (2)C17—C18—C13121.3 (3)
C1—C8—H8A109.5C17—C18—H18119.4
C7—C8—H8A109.5C13—C18—H18119.4

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C13–C18 ring.
D—H···AD—HH···AD···AD—H···A
C18—H18···Cg1i0.952.643.529 (3)156

Symmetry codes: (i) x−1/2, −y+3/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2215).

References

  • Adkins, H. & Billica, H. R. (1948). J. Am. Chem. Soc.70, 695–698.
  • Bommel, K. J. C. van, Metselaar, M. A., Werboom, W. & Reinhoudt, D. N. (2001). J. Org. Chem.66, 5405–5412. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst.41, 466–470.
  • Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Yarnton, England.
  • Raine, A. L., Williams, C. M. & Bernhardt, P. V. (2002). Acta Cryst. E58, o1439–o1440.
  • Schyf, C. J. van der & Geldenhuys, W. J. (2009). Neurotherapeutics, 6, 175–186. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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