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The title compound, C18H20, provides the first structurally characterized example of an alkynyl-substituted adamantane free from cocrystallized solvent or guest mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021542/ww6041sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021542/ww6041Isup2.hkl
Contains datablock I

CCDC reference: 202357

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.057
  • wR factor = 0.194
  • Data-to-parameter ratio = 14.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(12) - C(13) = 1.43 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Due to the increasing number of nano machines (Balzani et al., 2000; Kelly, 2001) and devices (Rukavishnikov et al., 1999) containing acetylene units attached to bulky caged carbocycles, we have been investigating new routes to achieving one-step synthesis of such systems. Recently, we discovered that the title compound, (I), could be obtained, via a novel metal-mediated process, from phenylacetylene and 1-iodoadamantane (Williams & Raine, 2002). It comprises adamantyl and phenyl groups bridged by a single acetylene residue.

Although structurally characterized examples of substituted adamantanes abound (more than 150 examples in the Cambridge Structural Database; Allen, 2002), there is but one molecule where the substituent is an alkyne attached to the bridgehead C atom. This compound, namely the symmetrical dumb-bell-shaped molecule 1,8-bis(1-adamantyl)-1,3,5,7-octatetrayne, (II), has been found to exhibit a number of interesting structural and non-linear optical properties. Significantly, all structures of (II) have been found to include a cocrystallized guest molecule, such as 2-butanone, crocetin dialdehyde, cyclohexanol and trans-β-8'-apocarotenal (Müller et al., 2000). It was found that (II) exhibits a distinctly bowed conformation of its nominally linear tetra-yne moiety, and the cocrystallized guest molecule appears to have an important influence on the observed conformation of its host (II). We were interested in the conformation of the simple analogue (I), which bears the same ethynyladamantyl group and, to this end, we have been successful in crystallizing (I) in a solvent-free form.

Compound (I) comprises adamantyl and phenyl groups bridged by a single acetylene residue. There is little apparent strain in the molecule and the bond lengths (Table 1) are as expected for a compound of its type. The adamantyl (1.50—1.54 Å) and phenyl C—C bond lengths (1.36–1.40 Å) for the aromatic ring are typical. The (adamantyl)—C1—C11—C12 and C11—C12—C13—(phenyl) angles (Table 1) are both close to linear, although the latter exhibits a small deviation therefrom. There are no hydrogen-bonding interactions in hydrocarbon (I). The closest intermolecular contacts are H9B···H18(-x + 1,+y − 1/2,-z + 1/2) (2.44 Å), H2A···H14(x,-y + 1/2,+z + 1/2) (2.53 Å) and H6B···H7A(-x + 1,-y,-z) (2.53 Å).

In conclusion, in the absence of any cocrystallized guest molecule, we have found that the nominally rod-shaped (I) exhibits an effectively distortionless conformation.

Experimental top

The synthesis of the title compound will be reported separately (Williams & Raine, 2002). Crystals were obtained by slow evaporation of a petroleum spirit (313–333 K) solution of the compound.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. ORTEP-3 plot (Farrugia, 1997) of (I), with ellipsoids at the 30% probability level.
(I) top
Crystal data top
C18H20F(000) = 512
Mr = 236.34Dx = 1.157 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 9.050 (1) Åθ = 9.8–13.9°
b = 14.224 (1) ŵ = 0.07 mm1
c = 11.081 (1) ÅT = 296 K
β = 107.986 (9)°Prism, colourless
V = 1356.7 (2) Å30.50 × 0.27 × 0.10 mm
Z = 4
Data collection top
Enraf-Nonius CAD-4
diffractometer
1381 reflections with I > 2σ(I)
Radiation source: Enraf-Nonius CAD-4Rint = 0.028
Graphite monochromatorθmax = 25.0°, θmin = 2.4°
ω–2θ scansh = 010
Absorption correction: ψ scan
(North et al., 1968)
k = 016
Tmin = 0.911, Tmax = 0.991l = 1312
2542 measured reflections3 standard reflections every 120 min
2385 independent reflections intensity decay: 4%
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)] = 0.057H-atom parameters constrained
wR(F2) = 0.194 w = 1/[σ2(Fo2) + (0.038P)2 + 2.0561P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
2385 reflectionsΔρmax = 0.17 e Å3
164 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.023 (3)
Crystal data top
C18H20V = 1356.7 (2) Å3
Mr = 236.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.050 (1) ŵ = 0.07 mm1
b = 14.224 (1) ÅT = 296 K
c = 11.081 (1) Å0.50 × 0.27 × 0.10 mm
β = 107.986 (9)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
1381 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.028
Tmin = 0.911, Tmax = 0.9913 standard reflections every 120 min
2542 measured reflections intensity decay: 4%
2385 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.194H-atom parameters constrained
S = 1.15Δρmax = 0.17 e Å3
2385 reflectionsΔρmin = 0.17 e Å3
164 parameters
Special details top

Experimental. Number of psi-scan sets used was 2 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.

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
C10.4831 (4)0.1407 (3)0.1793 (3)0.0426 (9)
C20.4019 (4)0.1943 (3)0.2620 (4)0.0508 (10)
H2A0.4760.20770.34440.061*
H2B0.36170.25360.2220.061*
C30.2694 (5)0.1348 (3)0.2781 (4)0.0548 (11)
H30.21820.16960.33040.066*
C40.1514 (5)0.1148 (3)0.1500 (4)0.0620 (12)
H4A0.11040.17340.10820.074*
H4B0.06570.07860.16110.074*
C50.2306 (5)0.0598 (3)0.0692 (4)0.0614 (12)
H50.1550.04620.01360.074*
C60.3625 (5)0.1196 (3)0.0506 (4)0.0562 (11)
H6A0.32070.17810.00880.067*
H6B0.41170.08620.00310.067*
C70.5451 (5)0.0472 (3)0.2460 (4)0.0572 (11)
H7A0.59660.01210.19550.069*
H7B0.62050.05990.3280.069*
C80.4122 (5)0.0108 (3)0.2638 (5)0.0639 (12)
H80.4530.06990.30660.077*
C90.2953 (6)0.0320 (3)0.1347 (5)0.0691 (14)
H9A0.34560.06690.08310.083*
H9B0.21140.07020.14540.083*
C100.3316 (6)0.0439 (3)0.3438 (4)0.0659 (13)
H10A0.24710.00680.35540.079*
H10B0.40480.05680.42670.079*
C110.6127 (4)0.1958 (3)0.1605 (4)0.0493 (10)
C120.7184 (4)0.2388 (3)0.1455 (4)0.0488 (10)
C130.8431 (4)0.2901 (3)0.1222 (3)0.0412 (9)
C140.8467 (4)0.3048 (3)0.0016 (4)0.0494 (10)
H140.76840.27980.06950.059*
C150.9647 (5)0.3560 (3)0.0246 (4)0.0558 (12)
H150.96480.36580.10750.067*
C161.0815 (5)0.3926 (3)0.0743 (4)0.0573 (12)
H161.16060.42740.05840.069*
C171.0820 (5)0.3778 (3)0.1971 (4)0.0550 (11)
H171.16220.40210.26420.066*
C180.9641 (4)0.3272 (3)0.2213 (4)0.0485 (10)
H180.96540.31770.30470.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0360 (19)0.049 (2)0.047 (2)0.0009 (17)0.0188 (17)0.0012 (18)
C20.049 (2)0.053 (3)0.054 (2)0.002 (2)0.0200 (19)0.005 (2)
C30.050 (2)0.063 (3)0.061 (3)0.002 (2)0.032 (2)0.008 (2)
C40.042 (2)0.075 (3)0.072 (3)0.003 (2)0.022 (2)0.004 (2)
C50.056 (3)0.074 (3)0.050 (3)0.018 (2)0.012 (2)0.006 (2)
C60.055 (2)0.073 (3)0.044 (2)0.010 (2)0.0210 (19)0.002 (2)
C70.055 (3)0.053 (3)0.064 (3)0.010 (2)0.020 (2)0.001 (2)
C80.072 (3)0.046 (3)0.078 (3)0.004 (2)0.028 (3)0.008 (2)
C90.077 (3)0.055 (3)0.086 (4)0.020 (2)0.041 (3)0.019 (3)
C100.077 (3)0.072 (3)0.057 (3)0.005 (3)0.031 (2)0.007 (2)
C110.047 (2)0.055 (3)0.048 (2)0.001 (2)0.0182 (19)0.0050 (19)
C120.044 (2)0.053 (3)0.055 (3)0.000 (2)0.0231 (19)0.004 (2)
C130.0369 (19)0.045 (2)0.045 (2)0.0022 (17)0.0168 (17)0.0001 (18)
C140.045 (2)0.059 (3)0.041 (2)0.002 (2)0.0074 (18)0.002 (2)
C150.059 (3)0.066 (3)0.050 (2)0.000 (2)0.026 (2)0.010 (2)
C160.055 (3)0.058 (3)0.067 (3)0.007 (2)0.031 (2)0.003 (2)
C170.047 (2)0.057 (3)0.058 (3)0.006 (2)0.012 (2)0.011 (2)
C180.050 (2)0.056 (3)0.045 (2)0.002 (2)0.0205 (19)0.0043 (19)
Geometric parameters (Å, º) top
C1—C111.477 (5)C8—C91.523 (6)
C1—C61.534 (5)C8—C101.524 (6)
C1—C71.541 (5)C8—H80.9800
C1—C21.542 (5)C9—H9A0.9700
C2—C31.523 (5)C9—H9B0.9700
C2—H2A0.9700C10—H10A0.9700
C2—H2B0.9700C10—H10B0.9700
C3—C101.506 (6)C11—C121.190 (5)
C3—C41.517 (6)C12—C131.433 (5)
C3—H30.9800C13—C181.393 (5)
C4—C51.524 (6)C13—C141.398 (5)
C4—H4A0.9700C14—C151.379 (5)
C4—H4B0.9700C14—H140.9300
C5—C91.521 (6)C15—C161.369 (6)
C5—C61.530 (6)C15—H150.9300
C5—H50.9800C16—C171.376 (6)
C6—H6A0.9700C16—H160.9300
C6—H6B0.9700C17—C181.380 (5)
C7—C81.521 (6)C17—H170.9300
C7—H7A0.9700C18—H180.9300
C7—H7B0.9700
C11—C1—C6110.0 (3)C1—C7—H7B109.6
C11—C1—C7109.8 (3)H7A—C7—H7B108.1
C6—C1—C7109.0 (3)C7—C8—C9109.5 (4)
C11—C1—C2111.5 (3)C7—C8—C10109.8 (4)
C6—C1—C2108.4 (3)C9—C8—C10109.2 (4)
C7—C1—C2108.1 (3)C7—C8—H8109.5
C3—C2—C1109.4 (3)C9—C8—H8109.5
C3—C2—H2A109.8C10—C8—H8109.5
C1—C2—H2A109.8C5—C9—C8109.4 (4)
C3—C2—H2B109.8C5—C9—H9A109.8
C1—C2—H2B109.8C8—C9—H9A109.8
H2A—C2—H2B108.2C5—C9—H9B109.8
C10—C3—C4110.0 (4)C8—C9—H9B109.8
C10—C3—C2110.1 (3)H9A—C9—H9B108.3
C4—C3—C2110.3 (3)C3—C10—C8109.4 (3)
C10—C3—H3108.8C3—C10—H10A109.8
C4—C3—H3108.8C8—C10—H10A109.8
C2—C3—H3108.8C3—C10—H10B109.8
C3—C4—C5108.8 (3)C8—C10—H10B109.8
C3—C4—H4A109.9H10A—C10—H10B108.2
C5—C4—H4A109.9C12—C11—C1179.0 (4)
C3—C4—H4B109.9C11—C12—C13177.8 (5)
C5—C4—H4B109.9C18—C13—C14117.8 (3)
H4A—C4—H4B108.3C18—C13—C12121.5 (3)
C9—C5—C4110.0 (4)C14—C13—C12120.7 (4)
C9—C5—C6109.9 (4)C15—C14—C13120.9 (4)
C4—C5—C6108.8 (4)C15—C14—H14119.6
C9—C5—H5109.4C13—C14—H14119.6
C4—C5—H5109.4C16—C15—C14120.3 (4)
C6—C5—H5109.4C16—C15—H15119.9
C5—C6—C1110.1 (3)C14—C15—H15119.9
C5—C6—H6A109.6C15—C16—C17119.9 (4)
C1—C6—H6A109.6C15—C16—H16120.0
C5—C6—H6B109.6C17—C16—H16120.0
C1—C6—H6B109.6C16—C17—C18120.3 (4)
H6A—C6—H6B108.1C16—C17—H17119.8
C8—C7—C1110.2 (3)C18—C17—H17119.8
C8—C7—H7A109.6C17—C18—C13120.7 (4)
C1—C7—H7A109.6C17—C18—H18119.6
C8—C7—H7B109.6C13—C18—H18119.6

Experimental details

Crystal data
Chemical formulaC18H20
Mr236.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)9.050 (1), 14.224 (1), 11.081 (1)
β (°) 107.986 (9)
V3)1356.7 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.50 × 0.27 × 0.10
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.911, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
2542, 2385, 1381
Rint0.028
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.194, 1.15
No. of reflections2385
No. of parameters164
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.17

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
C1—C111.477 (5)C8—C91.523 (6)
C1—C61.534 (5)C8—C101.524 (6)
C1—C71.541 (5)C11—C121.190 (5)
C1—C21.542 (5)C12—C131.433 (5)
C2—C31.523 (5)C13—C181.393 (5)
C3—C101.506 (6)C13—C141.398 (5)
C3—C41.517 (6)C14—C151.379 (5)
C4—C51.524 (6)C15—C161.369 (6)
C5—C91.521 (6)C16—C171.376 (6)
C5—C61.530 (6)C17—C181.380 (5)
C7—C81.521 (6)
C11—C1—C6110.0 (3)C8—C7—C1110.2 (3)
C11—C1—C7109.8 (3)C7—C8—C9109.5 (4)
C6—C1—C7109.0 (3)C7—C8—C10109.8 (4)
C11—C1—C2111.5 (3)C9—C8—C10109.2 (4)
C6—C1—C2108.4 (3)C5—C9—C8109.4 (4)
C7—C1—C2108.1 (3)C3—C10—C8109.4 (3)
C3—C2—C1109.4 (3)C12—C11—C1179.0 (4)
C10—C3—C4110.0 (4)C11—C12—C13177.8 (5)
C10—C3—C2110.1 (3)C18—C13—C14117.8 (3)
C4—C3—C2110.3 (3)C18—C13—C12121.5 (3)
C3—C4—C5108.8 (3)C14—C13—C12120.7 (4)
C9—C5—C4110.0 (4)C15—C14—C13120.9 (4)
C9—C5—C6109.9 (4)C15—C16—C17119.9 (4)
C4—C5—C6108.8 (4)C16—C17—C18120.3 (4)
C5—C6—C1110.1 (3)C17—C18—C13120.7 (4)
 

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