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

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ISSN: 2056-9890

1-(2-Phenyl­eth­yl)adamantane

aDepartment of Chemistry, Faculty of Technology, Tomas Bata University in Zlin, Nám. T. G. Masaryka 275, Zlín,762 72, Czech Republic, and bDepartment of Chemistry, Faculty of Science, Masaryk University in Brno, Kamenice 5, Brno-Bohunice, 625 00, Czech Republic
*Correspondence e-mail: rvicha@ft.utb.cz

(Received 24 May 2010; accepted 16 June 2010; online 23 June 2010)

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[Adkins, H. & Billica, H. R. (1948). J. Am. Chem. Soc. 70, 695-698.]). For some important properties of compounds bearing the adamantane scaffold, see: van der Schyf et al. (2009[Schyf, C. J. van der & Geldenhuys, W. J. (2009). Neurotherapeutics, 6, 175-186.]); van Bommel et al. (2001[Bommel, K. J. C. van, Metselaar, M. A., Werboom, W. & Reinhoudt, D. N. (2001). J. Org. Chem. 66, 5405-5412.]). For a related structure, see: Raine et al. (2002[Raine, A. L., Williams, C. M. & Bernhardt, P. V. (2002). Acta Cryst. E58, o1439-o1440.]).

[Scheme 1]

Experimental

Crystal data
  • C18H24

  • Mr = 240.37

  • Orthorhombic, P 21 21 21

  • 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[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.924, Tmax = 1.000

  • 11994 measured reflections

  • 1452 independent reflections

  • 1277 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C13–C18 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
C18—H18⋯Cg1i 0.95 2.64 3.529 (3) 156
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z].

Data collection: CrysAlis CCD (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and Mercury (Macrae et al., 2008[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.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. ORTEP diagram of the asymmetric unit showing the atom labelling scheme with atoms represented as 50% probability ellipsoids.
[Figure 2] 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 of gravity of C13–C18. H-atoms (except those which are involved in H-bonding) have been omitted for clarity. Symmetry codes: (i) -x + 1.5, -y + 1, z + 1/2; (ii) –x+2, y - 1/2, -z + 1/2.
1-(2-Phenylethyl)adamantane top
Crystal data top
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 top
Kuma KM-4-CCD
diffractometer
1452 independent reflections
Radiation source: fine-focus sealed tube1277 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
Detector resolution: 0.06 mm pixels mm-1θmax = 25.0°, θmin = 3.1°
ω scanh = 57
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
k = 88
Tmin = 0.924, Tmax = 1.000l = 3333
11994 measured reflections
Refinement top
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 = 1.30 w = 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
Crystal data top
C18H24V = 1389.55 (17) Å3
Mr = 240.37Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.4844 (5) ŵ = 0.06 mm1
b = 7.5109 (5) ÅT = 120 K
c = 28.5305 (19) Å0.40 × 0.20 × 0.20 mm
Data collection top
Kuma KM-4-CCD
diffractometer
1452 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
1277 reflections with I > 2σ(I)
Tmin = 0.924, Tmax = 1.000Rint = 0.043
11994 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.30Δρmax = 0.24 e Å3
1452 reflectionsΔρmin = 0.15 e Å3
163 parameters
Special details top

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) top
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)
H6A0.86400.03160.19900.027*
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)
H161.18601.20270.00140.038*
C170.9961 (5)0.9891 (4)0.00311 (9)0.0285 (7)
H170.90711.02380.02170.034*
C180.9604 (5)0.8312 (4)0.02684 (9)0.0275 (7)
H180.84770.75810.01780.033*
Atomic displacement parameters (Å2) top
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, º) top
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, º) top
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 code: (i) x1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formulaC18H24
Mr240.37
Crystal system, space groupOrthorhombic, P212121
Temperature (K)120
a, b, c (Å)6.4844 (5), 7.5109 (5), 28.5305 (19)
V3)1389.55 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.06
Crystal size (mm)0.40 × 0.20 × 0.20
Data collection
DiffractometerKuma KM-4-CCD
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.924, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
11994, 1452, 1277
Rint0.043
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.127, 1.30
No. of reflections1452
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.15

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C13–C18 ring.
D—H···AD—HH···AD···AD—H···A
C18—H18···Cg1i0.952.643.529 (3)156.3
Symmetry code: (i) x1/2, y+3/2, z.
 

Acknowledgements

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

References

First citationAdkins, H. & Billica, H. R. (1948). J. Am. Chem. Soc. 70, 695–698.  CrossRef CAS Web of Science
First citationBommel, K. J. C. van, Metselaar, M. A., Werboom, W. & Reinhoudt, D. N. (2001). J. Org. Chem. 66, 5405–5412.  Web of Science PubMed
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals
First citationMacrae, 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.  Web of Science CrossRef CAS IUCr Journals
First citationOxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.
First citationRaine, A. L., Williams, C. M. & Bernhardt, P. V. (2002). Acta Cryst. E58, o1439–o1440.  Web of Science CSD CrossRef IUCr Journals
First citationSchyf, C. J. van der & Geldenhuys, W. J. (2009). Neurotherapeutics, 6, 175–186.  CrossRef PubMed
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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