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Acta Cryst. (2007). C63, o468-o473
https://doi.org/10.1107/S0108270107027606
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C—H...π inter­actions in five ethynyl-substituted [2.2]paracyclo­phanes: further examples of the `7,11' packing pattern

P. G. Jones, I. Dix and H. Hopf
The monosubstituted derivative 4-ethynyl[2.2]paracyclo­phane, C18H16, (I), and the four disubstituted isomers, 4,12-, (II), 4,13-, (III), 4,15-, (IV), and 4,16-diethynyl[2.2]paracyclo­phane, (V), all C20H16, show the usual distortions of the [2.2]paracyclo­phane framework. The crystal packing is analyzed in terms of C—H...π inter­actions, some with H...π as short as 2.47 Å, in which the cyclo­phane rings and/or the triple-bond systems may act as acceptors. For compounds (I) and (IV), the known `7,11'-type cyclo­phane packing is observed, with a herring-bone pattern of mol­ecules in a layer structure.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107027606/gd3118sup1.cif
Contains datablocks I, II, III, IV, V, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107027606/gd3118Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107027606/gd3118IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107027606/gd3118IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107027606/gd3118IVsup5.hkl
Contains datablock IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107027606/gd3118Vsup6.hkl
Contains datablock V

CCDC references: 659133; 659134; 659135; 659136; 659137

Comment top

We recently described the syntheses of 4-ethynyl[2.2]paracyclophane, (I), and the four isomeric disubstituted derivatives, 4,12-diethynyl-, (II), 4,13-diethynyl-, (III), 4,15-diethynyl-, (IV), and 4,16-diethynyl[2.2]paracyclophane, (V) (Bondarenko et al., 2004). These molecules are interesting building blocks for molecular scaffolding (Hopf & Dix, 2006). We are also interested in the structures of paracyclophane derivatives and, in particular, in their packing, and have presented a description of C—H···π interactions (Desiraju & Steiner, 1999) in some pseudo-geminally substituted derivatives (El Shaieb et al., 2003). Here, we present the crystal structures of compounds (I)–(V). The disubstituted compounds (II), (III), (IV) and (V) represent the substitution patterns pseudo-para, pseudo-meta, pseudo-geminal and pseudo-ortho, respectively. To the best of our knowledge, this is the first time that all four possible isomers with a given substituent have been structurally characterized by X-ray methods.

The molecules of compounds (I)–(V) are shown in Figs. 1–5. Those of (I), (III) and (V) are chiral, although all bulk samples were racemates. Nevertheless, compounds (III), (IV) and (V) crystallize by chance in chiral space groups. Compound (II) crystallizes with two independent molecules, each of which displays imposed inversion symmetry; for this reason, the standard IUPAC numbering cannot be fully implemented for (II). For compound (V), the enantiomer in Fig. 5 is opposite to that in the scheme.

Bond lengths and angles may be considered normal. In particular, the molecules show the distortions typical of [2.2]paracyclophane systems, e.g. lengthened C—C bonds and widened angles in the bridges, narrowed ring bond angles at the bridgehead atoms, and boatlike distortion of the rings (the bridgehead atoms lie significantly out of the plane of the other four ring atoms). These dimensions are summarized in Table 1. In the pseudo-geminal isomer, (IV), the separations between the atoms of the eclipsed triple-bond systems are C4···C15 3.170 (2), C17···C19 3.371 (2) and C18···C20 3.642 (3) Å. We have utilized such close contacts in related derivatives with double bonds to form ladderanes (see, for example, Hopf et al., 2005).

The molecular packing of all five compounds can be analysed in terms of C—H···π interactions, where the acceptor system can be the triple bond or the π electron density of the rings (Desiraju & Steiner, 1999). A summary of the observed contacts is given in Table 2. The packing of compound (I) involves layers of molecules parallel to the ab plane at z ≈ 1/4, 3/4, etc. One such layer is shown in Fig. 6. The molecules adopt a herringbone-type pattern, within which the three C—H···π interactions are accommodated. We have previously pointed out (El Shaieb et al., 2003) that many simple derivatives of [2.2]paracyclophane display a common combination of two axis lengths, one of ca 7.5 Å and the other of ca 11.5 Å. These values are consistent with the formation of hydrogen-bonded layers such as that observed for (I). Because the molecules are approximately equidimensional, mutual rotations within the layer can be tolerated without disturbing the overall pattern, and thus different types of H atom (bridge or ring) can act as donors. The substituents play a less important role: in general, they are directed perpendicularly away from the layers, and thus determine the interlayer interactions and, in turn, the space group and third axis length. The only requirement is that the substituents should not be too large or themselves determine the most important secondary interactions. In compound (I), the ethynyl substituent is even capable of accepting a hydrogen bond within the layer without disturbing the 7,11 pattern.

For the ring systems, it is not always clear whether the whole ring or only a part of it is the `true' acceptor of the hydrogen bond. For compound (I), the acceptor system of hydrogen bond No. 2 might be better expressed as the triangle of atoms C11/C12/C16 forming one angled end of the `boat'. For this grouping, the hydrogen-bond parameters would be 2.69 Å and 168°, shorter and more linear than the formal contact to the ring centroid.

The packing of compound (II) is shown in Fig. 7. It too involves a layer structure, but the 7,11 pattern is not observed. Instead, hydrogen bonds 1 and 2 (the latter involving an ethynyl acceptor) combine in layers parallel to (101). The other two hydrogen bonds are formed between layers. The acceptor for hydrogen bond 3 might be better expressed as the centroid of atoms C5–C7 (2.66 Å and 134°). Hydrogen bond 4 is a borderline case.

The 31 axis of compound (III) is clearly recognisable the packing diagram shown in Fig. 8. Within the 31 helices, the short hydrogen bond No. 1, with an ethynyl H atom as donor, links successive molecules (the `true' acceptor might be the centroid of atoms C11/C12/C16, with hydrogen-bond parameters of 2.56 Å, 138°). The other three hydrogen bonds, one short and two long, link adjacent helices. It is noteworthy that hydrogen bond 3 is from an ethynyl group to a symmetry equivalent of the same group.

With compound (IV), we return to the 7,11 pattern (Fig. 9), with one very short hydrogen bond (No. 1). The ethynyl groups play no role within the layer, but instead are involved in interlayer contacts.

Compound (V) crystallizes, like (III), in the space group P31. The packing diagram (Fig. 10) shows that the helices are assembled via a different type of hydrogen bond from those in (III), with a ring H atom as donor to the symmetry equivalent of the same ring. The first impression is that this is the only significant interaction (no other centroids or triple bonds appear to be involved in short contacts), but closer inspection reveals that the atom grouping C11/C12/C16 is the acceptor for hydrogen bond 2, which links adjacent helices.

Related literature top

For related literature, see: Bondarenko et al. (2004); Desiraju & Steiner (1999); El Shaieb, Narayanan, Hopf, Dix, Fischer, Jones, Ernst & Ibrom (2003); Hopf & Dix (2006); Hopf et al. (2005); Sheldrick (1997).

Experimental top

The preparations of compounds (I)–(V) from the aldehyde precursors by Wittig, Corey-Fuchs and Bestmann reactions, including characterization by spectroscopic and analytical methods, were described previously by us (Bondarenko et al., 2004).

Refinement top

Acetylenic H atoms were refined freely. Other H atoms were included using a riding model, with C—H bond lengths fixed at 0.99 Å (methylene) or 0.95 Å (Csp2) and with Uiso(H) = 1.2Ueq(C). For compounds (III)–(V), which crystallize in non-centrosymmetric space groups, the anomalous scattering was negligible, and Friedel opposite reflections were therefore merged. For this reason, the Flack parameters are indeterminate. For compounds (III) and (V), this additionally means that the space groups P31 and P32 could not be distinguished. For consistency, P31 was chosen for both, which means that the enantiomer of (V) is opposite to that shown in the scheme (as noted in the Comment section). For compounds (III)–(V), and additionally for compound (I), which diffracted weakly, restraints to displacement parameters were employed (SIMU and DELU instructions in SHELXL97; Sheldrick, 1997) to improve the ratio of `observed' reflections to parameters (which would otherwise be less than 10).

Structure description top

We recently described the syntheses of 4-ethynyl[2.2]paracyclophane, (I), and the four isomeric disubstituted derivatives, 4,12-diethynyl-, (II), 4,13-diethynyl-, (III), 4,15-diethynyl-, (IV), and 4,16-diethynyl[2.2]paracyclophane, (V) (Bondarenko et al., 2004). These molecules are interesting building blocks for molecular scaffolding (Hopf & Dix, 2006). We are also interested in the structures of paracyclophane derivatives and, in particular, in their packing, and have presented a description of C—H···π interactions (Desiraju & Steiner, 1999) in some pseudo-geminally substituted derivatives (El Shaieb et al., 2003). Here, we present the crystal structures of compounds (I)–(V). The disubstituted compounds (II), (III), (IV) and (V) represent the substitution patterns pseudo-para, pseudo-meta, pseudo-geminal and pseudo-ortho, respectively. To the best of our knowledge, this is the first time that all four possible isomers with a given substituent have been structurally characterized by X-ray methods.

The molecules of compounds (I)–(V) are shown in Figs. 1–5. Those of (I), (III) and (V) are chiral, although all bulk samples were racemates. Nevertheless, compounds (III), (IV) and (V) crystallize by chance in chiral space groups. Compound (II) crystallizes with two independent molecules, each of which displays imposed inversion symmetry; for this reason, the standard IUPAC numbering cannot be fully implemented for (II). For compound (V), the enantiomer in Fig. 5 is opposite to that in the scheme.

Bond lengths and angles may be considered normal. In particular, the molecules show the distortions typical of [2.2]paracyclophane systems, e.g. lengthened C—C bonds and widened angles in the bridges, narrowed ring bond angles at the bridgehead atoms, and boatlike distortion of the rings (the bridgehead atoms lie significantly out of the plane of the other four ring atoms). These dimensions are summarized in Table 1. In the pseudo-geminal isomer, (IV), the separations between the atoms of the eclipsed triple-bond systems are C4···C15 3.170 (2), C17···C19 3.371 (2) and C18···C20 3.642 (3) Å. We have utilized such close contacts in related derivatives with double bonds to form ladderanes (see, for example, Hopf et al., 2005).

The molecular packing of all five compounds can be analysed in terms of C—H···π interactions, where the acceptor system can be the triple bond or the π electron density of the rings (Desiraju & Steiner, 1999). A summary of the observed contacts is given in Table 2. The packing of compound (I) involves layers of molecules parallel to the ab plane at z ≈ 1/4, 3/4, etc. One such layer is shown in Fig. 6. The molecules adopt a herringbone-type pattern, within which the three C—H···π interactions are accommodated. We have previously pointed out (El Shaieb et al., 2003) that many simple derivatives of [2.2]paracyclophane display a common combination of two axis lengths, one of ca 7.5 Å and the other of ca 11.5 Å. These values are consistent with the formation of hydrogen-bonded layers such as that observed for (I). Because the molecules are approximately equidimensional, mutual rotations within the layer can be tolerated without disturbing the overall pattern, and thus different types of H atom (bridge or ring) can act as donors. The substituents play a less important role: in general, they are directed perpendicularly away from the layers, and thus determine the interlayer interactions and, in turn, the space group and third axis length. The only requirement is that the substituents should not be too large or themselves determine the most important secondary interactions. In compound (I), the ethynyl substituent is even capable of accepting a hydrogen bond within the layer without disturbing the 7,11 pattern.

For the ring systems, it is not always clear whether the whole ring or only a part of it is the `true' acceptor of the hydrogen bond. For compound (I), the acceptor system of hydrogen bond No. 2 might be better expressed as the triangle of atoms C11/C12/C16 forming one angled end of the `boat'. For this grouping, the hydrogen-bond parameters would be 2.69 Å and 168°, shorter and more linear than the formal contact to the ring centroid.

The packing of compound (II) is shown in Fig. 7. It too involves a layer structure, but the 7,11 pattern is not observed. Instead, hydrogen bonds 1 and 2 (the latter involving an ethynyl acceptor) combine in layers parallel to (101). The other two hydrogen bonds are formed between layers. The acceptor for hydrogen bond 3 might be better expressed as the centroid of atoms C5–C7 (2.66 Å and 134°). Hydrogen bond 4 is a borderline case.

The 31 axis of compound (III) is clearly recognisable the packing diagram shown in Fig. 8. Within the 31 helices, the short hydrogen bond No. 1, with an ethynyl H atom as donor, links successive molecules (the `true' acceptor might be the centroid of atoms C11/C12/C16, with hydrogen-bond parameters of 2.56 Å, 138°). The other three hydrogen bonds, one short and two long, link adjacent helices. It is noteworthy that hydrogen bond 3 is from an ethynyl group to a symmetry equivalent of the same group.

With compound (IV), we return to the 7,11 pattern (Fig. 9), with one very short hydrogen bond (No. 1). The ethynyl groups play no role within the layer, but instead are involved in interlayer contacts.

Compound (V) crystallizes, like (III), in the space group P31. The packing diagram (Fig. 10) shows that the helices are assembled via a different type of hydrogen bond from those in (III), with a ring H atom as donor to the symmetry equivalent of the same ring. The first impression is that this is the only significant interaction (no other centroids or triple bonds appear to be involved in short contacts), but closer inspection reveals that the atom grouping C11/C12/C16 is the acceptor for hydrogen bond 2, which links adjacent helices.

For related literature, see: Bondarenko et al. (2004); Desiraju & Steiner (1999); El Shaieb, Narayanan, Hopf, Dix, Fischer, Jones, Ernst & Ibrom (2003); Hopf & Dix (2006); Hopf et al. (2005); Sheldrick (1997).

Computing details top

Data collection: XSCANS (Siemens, 1991) for (I); SMART (Bruker, 1998) for (II), (III), (IV), (V). Cell refinement: XSCANS for (I); SAINT (Bruker, 1998) for (II), (III), (IV), (V). Data reduction: XSCANS for (I); SAINT for (II), (III), (IV), (V). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The two independent molecules of compound (II) (each with inversion symmetry), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The label for atom C4' has been omitted for clarity.
[Figure 3] Fig. 3. The molecular structure of compound (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. The molecular structure of compound (4), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 5] Fig. 5. The molecular structure of compound (5), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 6] Fig. 6. A packing diagram for compound (I), viewed perpendicular to the ab plane. Hydrogen bonds are shown as dashed lines and are numbered according to Table 2. The packing is of the 7,11 type (see text).
[Figure 7] Fig. 7. A packing diagram for compound (II), viewed perpendicular to (101) in the region x,z ≈ 1/4. Hydrogen bonds are shown as dashed lines and are numbered according to Table 2. The top horizontal row of molecules involves only the first independent molecule, the next row only the second independent molecule, etc.
[Figure 8] Fig. 8. A packing diagram for compound (III), viewed parallel to the c axis. Hydrogen bonds are shown as dashed lines (dotted for the long bent hydrogen bond No. 4).
[Figure 9] Fig. 9. A packing diagram for compound (IV), viewed perpendicular to the ab plane. Hydrogen bonds are shown as dashed lines [Two types - please define]. The packing is of the 7,11 type (see text).
[Figure 10] Fig. 10. A packing diagram for compound (V), viewed parallel to the c axis. Hydrogen bonds are shown as dashed lines (thick for the short hydrogen bond No. 1 and thin for the long hydrogen bond No. 2).
(I) 4-Ethynyl[2.2]paracyclophane top
Crystal data top
C18H16F(000) = 496
Mr = 232.31Dx = 1.232 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 62 reflections
a = 7.6538 (14) Åθ = 3.7–12.4°
b = 11.022 (2) ŵ = 0.07 mm−1
c = 15.056 (3) ÅT = 173 K
β = 99.561 (16)°Tablet, colourless
V = 1252.4 (4) Å30.6 × 0.3 × 0.18 mm
Z = 4
Data collection top
Siemens P4
diffractometer		Rint = 0.024
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 3.3°
Graphite monochromatorh = 0→9
ω scansk = −13→5
3461 measured reflectionsl = −17→17
2191 independent reflections3 standard reflections every 247 reflections
1267 reflections with I > 2σ(I) intensity decay: none
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)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0531P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.86(Δ/σ)max < 0.001
2191 reflectionsΔρmax = 0.19 e Å−3
168 parametersΔρmin = −0.17 e Å−3
167 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.010 (2)
Crystal data top
C18H16V = 1252.4 (4) Å3
Mr = 232.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.6538 (14) ŵ = 0.07 mm−1
b = 11.022 (2) ÅT = 173 K
c = 15.056 (3) Å0.6 × 0.3 × 0.18 mm
β = 99.561 (16)°
Data collection top
Siemens P4
diffractometer		Rint = 0.024
3461 measured reflections3 standard reflections every 247 reflections
2191 independent reflections intensity decay: none
1267 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.042167 restraints
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 0.86Δρmax = 0.19 e Å−3
2191 reflectionsΔρmin = −0.17 e Å−3
168 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 > 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
C10.3240 (3)0.3294 (2)0.07414 (14)0.0463 (6)
H1A0.26520.37610.02130.056*
H1B0.35850.24950.05250.056*
C20.4959 (2)0.3996 (2)0.11990 (13)0.0360 (5)
H2A0.59410.34080.13520.043*
H2B0.53070.45820.07620.043*
C30.4704 (2)0.46641 (18)0.20368 (13)0.0283 (5)
C40.3583 (2)0.56743 (17)0.20060 (13)0.0275 (5)
C50.2775 (2)0.59538 (18)0.27469 (12)0.0302 (5)
H50.19930.66280.27140.036*
C60.3091 (2)0.52675 (19)0.35289 (13)0.0297 (5)
C70.4514 (2)0.44587 (19)0.36174 (12)0.0304 (5)
H70.49480.41090.41880.036*
C80.5296 (2)0.41630 (18)0.28807 (13)0.0299 (5)
H80.62570.36070.29530.036*
C90.1697 (2)0.5179 (2)0.41273 (13)0.0402 (6)
H9A0.09950.59370.40760.048*
H9B0.22870.50970.47610.048*
C100.0411 (3)0.4069 (2)0.38758 (15)0.0473 (6)
H10A0.06850.34380.43460.057*
H10B−0.08230.43410.38720.057*
C110.0544 (2)0.3517 (2)0.29722 (14)0.0351 (5)
C120.1664 (3)0.25412 (19)0.29033 (14)0.0383 (5)
H120.19680.20080.34010.046*
C130.2342 (2)0.2335 (2)0.21217 (14)0.0371 (5)
H130.30900.16550.20860.045*
C140.1946 (2)0.3106 (2)0.13905 (13)0.0343 (5)
C150.0537 (2)0.39093 (19)0.13934 (13)0.0354 (5)
H150.00500.43250.08560.042*
C16−0.0156 (2)0.41044 (19)0.21755 (13)0.0347 (5)
H16−0.11230.46470.21670.042*
C170.3047 (2)0.63154 (19)0.11716 (14)0.0333 (5)
C180.2613 (3)0.6839 (2)0.04844 (15)0.0422 (6)
H180.225 (3)0.727 (2)−0.0080 (14)0.055 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0454 (12)0.0519 (16)0.0416 (13)0.0006 (12)0.0069 (10)−0.0146 (11)
C20.0321 (11)0.0374 (14)0.0398 (12)0.0049 (10)0.0098 (9)0.0008 (10)
C30.0208 (9)0.0271 (12)0.0370 (11)−0.0039 (9)0.0048 (8)0.0009 (9)
C40.0225 (9)0.0252 (12)0.0332 (10)−0.0040 (9)0.0001 (8)−0.0007 (9)
C50.0227 (9)0.0240 (12)0.0419 (12)0.0002 (9)−0.0002 (9)−0.0067 (10)
C60.0254 (9)0.0298 (12)0.0327 (11)−0.0045 (9)0.0011 (8)−0.0065 (9)
C70.0250 (10)0.0327 (12)0.0308 (11)−0.0053 (9)−0.0030 (8)0.0017 (9)
C80.0206 (9)0.0275 (12)0.0402 (11)−0.0008 (9)0.0014 (8)0.0010 (9)
C90.0360 (11)0.0476 (15)0.0372 (12)−0.0020 (11)0.0063 (10)−0.0103 (11)
C100.0374 (11)0.0581 (17)0.0498 (13)−0.0113 (12)0.0173 (10)−0.0021 (12)
C110.0246 (10)0.0371 (14)0.0437 (12)−0.0127 (10)0.0060 (9)−0.0014 (10)
C120.0316 (11)0.0337 (14)0.0468 (13)−0.0093 (10)−0.0013 (10)0.0077 (11)
C130.0296 (11)0.0275 (13)0.0520 (13)−0.0003 (9)0.0002 (10)−0.0059 (10)
C140.0295 (10)0.0334 (13)0.0379 (11)−0.0042 (10)−0.0005 (9)−0.0101 (10)
C150.0273 (10)0.0341 (13)0.0406 (12)−0.0056 (10)−0.0068 (9)−0.0022 (10)
C160.0182 (9)0.0336 (13)0.0513 (13)−0.0024 (9)0.0023 (9)−0.0034 (10)
C170.0303 (11)0.0298 (13)0.0385 (12)0.0017 (9)0.0019 (9)−0.0028 (10)
C180.0472 (13)0.0377 (14)0.0400 (13)0.0049 (12)0.0023 (11)0.0005 (12)
Geometric parameters (Å, º) top
C1—C141.517 (3)C9—C101.576 (3)
C1—C21.582 (3)C9—H9A0.9900
C1—H1A0.9900C9—H9B0.9900
C1—H1B0.9900C10—C111.509 (3)
C2—C31.501 (3)C10—H10A0.9900
C2—H2A0.9900C10—H10B0.9900
C2—H2B0.9900C11—C161.390 (3)
C3—C81.391 (2)C11—C121.390 (3)
C3—C41.401 (3)C12—C131.382 (3)
C4—C51.397 (3)C12—H120.9500
C4—C171.440 (3)C13—C141.384 (3)
C5—C61.386 (3)C13—H130.9500
C5—H50.9500C14—C151.396 (3)
C6—C71.397 (3)C15—C161.386 (3)
C6—C91.509 (3)C15—H150.9500
C7—C81.384 (3)C16—H160.9500
C7—H70.9500C17—C181.183 (3)
C8—H80.9500C18—H180.97 (2)
C14—C1—C2111.79 (16)C6—C9—H9A109.1
C14—C1—H1A109.3C10—C9—H9A109.1
C2—C1—H1A109.3C6—C9—H9B109.1
C14—C1—H1B109.3C10—C9—H9B109.1
C2—C1—H1B109.3H9A—C9—H9B107.8
H1A—C1—H1B107.9C11—C10—C9113.36 (16)
C3—C2—C1112.98 (15)C11—C10—H10A108.9
C3—C2—H2A109.0C9—C10—H10A108.9
C1—C2—H2A109.0C11—C10—H10B108.9
C3—C2—H2B109.0C9—C10—H10B108.9
C1—C2—H2B109.0H10A—C10—H10B107.7
H2A—C2—H2B107.8C16—C11—C12116.7 (2)
C8—C3—C4116.79 (18)C16—C11—C10121.1 (2)
C8—C3—C2120.30 (19)C12—C11—C10120.91 (19)
C4—C3—C2121.77 (17)C13—C12—C11121.0 (2)
C5—C4—C3119.90 (18)C13—C12—H12119.5
C5—C4—C17119.22 (18)C11—C12—H12119.5
C3—C4—C17120.19 (18)C12—C13—C14120.8 (2)
C6—C5—C4121.32 (18)C12—C13—H13119.6
C6—C5—H5119.3C14—C13—H13119.6
C4—C5—H5119.3C13—C14—C15117.03 (19)
C5—C6—C7116.91 (18)C13—C14—C1121.05 (19)
C5—C6—C9120.10 (17)C15—C14—C1120.2 (2)
C7—C6—C9121.25 (18)C16—C15—C14120.40 (19)
C8—C7—C6120.54 (18)C16—C15—H15119.8
C8—C7—H7119.7C14—C15—H15119.8
C6—C7—H7119.7C15—C16—C11120.93 (19)
C7—C8—C3121.33 (18)C15—C16—H16119.5
C7—C8—H8119.3C11—C16—H16119.5
C3—C8—H8119.3C18—C17—C4179.6 (2)
C6—C9—C10112.45 (16)C17—C18—H18179.9 (15)
C14—C1—C2—C3−18.7 (3)C7—C6—C9—C10−73.5 (2)
C1—C2—C3—C899.3 (2)C6—C9—C10—C11−13.9 (3)
C1—C2—C3—C4−68.1 (2)C9—C10—C11—C16−73.5 (2)
C8—C3—C4—C5−15.3 (3)C9—C10—C11—C1293.4 (2)
C2—C3—C4—C5152.46 (18)C16—C11—C12—C1313.5 (3)
C8—C3—C4—C17174.15 (17)C10—C11—C12—C13−153.96 (19)
C2—C3—C4—C17−18.0 (3)C11—C12—C13—C141.0 (3)
C3—C4—C5—C61.7 (3)C12—C13—C14—C15−14.7 (3)
C17—C4—C5—C6172.24 (17)C12—C13—C14—C1150.44 (19)
C4—C5—C6—C713.2 (3)C2—C1—C14—C13−68.3 (3)
C4—C5—C6—C9−151.97 (18)C2—C1—C14—C1596.4 (2)
C5—C6—C7—C8−14.3 (3)C13—C14—C15—C1613.9 (3)
C9—C6—C7—C8150.72 (18)C1—C14—C15—C16−151.41 (19)
C6—C7—C8—C30.5 (3)C14—C15—C16—C110.6 (3)
C4—C3—C8—C714.4 (3)C12—C11—C16—C15−14.3 (3)
C2—C3—C8—C7−153.61 (18)C10—C11—C16—C15153.16 (19)
C5—C6—C9—C1091.0 (2)
(II) 4,12-Diethynyl[2.2]paracyclophane top
Crystal data top
C20H16Z = 2
Mr = 256.33F(000) = 272
Triclinic, P1Dx = 1.263 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.6316 (10) ÅCell parameters from 3408 reflections
b = 7.8177 (10) Åθ = 2–28°
c = 12.4446 (16) ŵ = 0.07 mm−1
α = 78.125 (2)°T = 143 K
β = 72.339 (2)°Prism, colourless
γ = 73.971 (2)°0.42 × 0.28 × 0.26 mm
V = 673.90 (15) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		2953 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
Graphite monochromatorθmax = 28.5°, θmin = 1.7°
Detector resolution: 8.192 pixels mm-1h = −10→10
ω scansk = −10→8
5064 measured reflectionsl = −16→16
3383 independent 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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.073P)2 + 0.1405P]
where P = (Fo2 + 2Fc2)/3
3383 reflections(Δ/σ)max < 0.001
189 parametersΔρmax = 0.35 e Å−3
0 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C20H16γ = 73.971 (2)°
Mr = 256.33V = 673.90 (15) Å3
Triclinic, P1Z = 2
a = 7.6316 (10) ÅMo Kα radiation
b = 7.8177 (10) ŵ = 0.07 mm−1
c = 12.4446 (16) ÅT = 143 K
α = 78.125 (2)°0.42 × 0.28 × 0.26 mm
β = 72.339 (2)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		2953 reflections with I > 2σ(I)
5064 measured reflectionsRint = 0.030
3383 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.35 e Å−3
3383 reflectionsΔρmin = −0.23 e Å−3
189 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 > 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
C1−0.29585 (15)0.12460 (15)0.69765 (9)0.0220 (2)
H1A−0.41180.07810.73100.026*
H1B−0.32180.24470.72100.026*
C2−0.12894 (15)−0.00650 (15)0.74753 (9)0.0207 (2)
H2A−0.08780.06040.79130.025*
H2B−0.1771−0.10650.80050.025*
C30.03919 (14)−0.08282 (14)0.65501 (8)0.0185 (2)
C40.17681 (14)0.01575 (13)0.59413 (9)0.0180 (2)
C50.28086 (14)−0.01550 (14)0.48280 (9)0.0188 (2)
H50.37320.05130.44220.023*
C60.25060 (14)−0.14330 (14)0.43092 (9)0.0187 (2)
C70.14599 (15)−0.26576 (14)0.50073 (9)0.0200 (2)
H70.1463−0.37010.47280.024*
C80.04156 (15)−0.23477 (14)0.61105 (9)0.0203 (2)
H8−0.0293−0.31840.65730.024*
C90.19561 (15)0.16540 (15)0.63745 (9)0.0210 (2)
C100.21447 (18)0.29073 (17)0.67032 (10)0.0281 (3)
H100.230 (3)0.392 (3)0.6952 (15)0.048 (5)*
C1'0.86046 (17)0.28377 (17)0.03764 (11)0.0287 (3)
H1'10.90600.30020.10050.034*
H1'20.97100.2245−0.01900.034*
C2'0.71548 (16)0.15666 (15)0.08652 (10)0.0250 (2)
H2'10.75860.05370.04260.030*
H2'20.71500.10860.16670.030*
C3'0.51609 (15)0.25307 (14)0.08092 (9)0.0197 (2)
C4'0.40181 (14)0.37610 (14)0.15719 (9)0.0185 (2)
C5'0.25753 (15)0.51451 (14)0.12501 (9)0.0203 (2)
H5'0.18050.59630.17680.024*
C6'0.22560 (14)0.53366 (15)0.01792 (9)0.0217 (2)
C7'0.30971 (16)0.38834 (16)−0.04408 (9)0.0236 (2)
H7'0.26900.3837−0.10820.028*
C8'0.45248 (16)0.25044 (15)−0.01283 (9)0.0226 (2)
H8'0.50770.1527−0.05600.027*
C9'0.44786 (15)0.37435 (14)0.26161 (9)0.0215 (2)
C10'0.48740 (18)0.37135 (16)0.34783 (10)0.0270 (3)
H10'0.520 (3)0.367 (3)0.4182 (16)0.051 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0207 (5)0.0245 (5)0.0183 (5)−0.0001 (4)−0.0047 (4)−0.0050 (4)
C20.0202 (5)0.0242 (5)0.0162 (5)−0.0044 (4)−0.0043 (4)−0.0010 (4)
C30.0175 (5)0.0197 (5)0.0168 (4)−0.0026 (4)−0.0060 (4)0.0002 (4)
C40.0178 (4)0.0177 (5)0.0189 (5)−0.0025 (4)−0.0075 (4)−0.0012 (4)
C50.0161 (4)0.0198 (5)0.0192 (5)−0.0033 (4)−0.0048 (4)−0.0007 (4)
C60.0162 (4)0.0199 (5)0.0182 (5)0.0004 (4)−0.0054 (4)−0.0032 (4)
C70.0202 (5)0.0170 (5)0.0236 (5)−0.0014 (4)−0.0089 (4)−0.0033 (4)
C80.0196 (5)0.0183 (5)0.0223 (5)−0.0044 (4)−0.0069 (4)0.0010 (4)
C90.0202 (5)0.0230 (5)0.0193 (5)−0.0045 (4)−0.0059 (4)−0.0012 (4)
C100.0340 (6)0.0257 (6)0.0277 (6)−0.0078 (5)−0.0105 (5)−0.0051 (4)
C1'0.0214 (5)0.0294 (6)0.0329 (6)−0.0042 (4)−0.0115 (5)0.0052 (5)
C2'0.0237 (5)0.0189 (5)0.0273 (5)−0.0002 (4)−0.0054 (4)−0.0002 (4)
C3'0.0215 (5)0.0160 (4)0.0195 (5)−0.0062 (4)−0.0031 (4)0.0012 (4)
C4'0.0192 (5)0.0180 (5)0.0179 (5)−0.0073 (4)−0.0034 (4)0.0004 (4)
C5'0.0175 (5)0.0208 (5)0.0213 (5)−0.0060 (4)−0.0025 (4)−0.0018 (4)
C6'0.0165 (5)0.0244 (5)0.0242 (5)−0.0075 (4)−0.0065 (4)0.0022 (4)
C7'0.0253 (5)0.0294 (6)0.0199 (5)−0.0144 (4)−0.0065 (4)0.0002 (4)
C8'0.0265 (5)0.0210 (5)0.0202 (5)−0.0105 (4)−0.0013 (4)−0.0029 (4)
C9'0.0224 (5)0.0185 (5)0.0217 (5)−0.0054 (4)−0.0042 (4)−0.0004 (4)
C10'0.0324 (6)0.0242 (5)0.0250 (5)−0.0058 (5)−0.0106 (5)−0.0007 (4)
Geometric parameters (Å, º) top
C1—C6i1.5157 (14)C1'—C6'ii1.5160 (16)
C1—C21.5985 (15)C1'—C2'1.5911 (16)
C1—H1A0.9900C1'—H1'10.9900
C1—H1B0.9900C1'—H1'20.9900
C2—C31.5138 (14)C2'—C3'1.5158 (15)
C2—H2A0.9900C2'—H2'10.9900
C2—H2B0.9900C2'—H2'20.9900
C3—C81.4000 (15)C3'—C8'1.3988 (15)
C3—C41.4123 (14)C3'—C4'1.4130 (15)
C4—C51.4051 (14)C4'—C5'1.4053 (14)
C4—C91.4419 (14)C4'—C9'1.4420 (15)
C5—C61.3971 (14)C5'—C6'1.3974 (15)
C5—H50.9500C5'—H5'0.9500
C6—C71.4027 (15)C6'—C7'1.3984 (16)
C6—C1i1.5157 (14)C6'—C1'ii1.5160 (16)
C7—C81.3946 (15)C7'—C8'1.3915 (16)
C7—H70.9500C7'—H7'0.9500
C8—H80.9500C8'—H8'0.9500
C9—C101.1944 (16)C9'—C10'1.1937 (16)
C10—H100.957 (18)C10'—H10'0.971 (19)
C6i—C1—C2113.00 (8)C6'ii—C1'—C2'112.86 (9)
C6i—C1—H1A109.0C6'ii—C1'—H1'1109.0
C2—C1—H1A109.0C2'—C1'—H1'1109.0
C6i—C1—H1B109.0C6'ii—C1'—H1'2109.0
C2—C1—H1B109.0C2'—C1'—H1'2109.0
H1A—C1—H1B107.8H1'1—C1'—H1'2107.8
C3—C2—C1112.38 (8)C3'—C2'—C1'112.70 (9)
C3—C2—H2A109.1C3'—C2'—H2'1109.1
C1—C2—H2A109.1C1'—C2'—H2'1109.1
C3—C2—H2B109.1C3'—C2'—H2'2109.1
C1—C2—H2B109.1C1'—C2'—H2'2109.1
H2A—C2—H2B107.9H2'1—C2'—H2'2107.8
C8—C3—C4117.16 (9)C8'—C3'—C4'116.89 (10)
C8—C3—C2120.23 (9)C8'—C3'—C2'120.63 (10)
C4—C3—C2121.24 (9)C4'—C3'—C2'121.34 (10)
C5—C4—C3119.85 (9)C5'—C4'—C3'119.87 (9)
C5—C4—C9118.38 (9)C5'—C4'—C9'119.55 (9)
C3—C4—C9121.22 (9)C3'—C4'—C9'120.11 (9)
C6—C5—C4120.98 (10)C6'—C5'—C4'121.00 (10)
C6—C5—H5119.5C6'—C5'—H5'119.5
C4—C5—H5119.5C4'—C5'—H5'119.5
C5—C6—C7117.52 (9)C5'—C6'—C7'117.09 (10)
C5—C6—C1i119.93 (9)C5'—C6'—C1'ii120.52 (10)
C7—C6—C1i121.45 (9)C7'—C6'—C1'ii121.15 (10)
C8—C7—C6120.22 (10)C8'—C7'—C6'120.66 (10)
C8—C7—H7119.9C8'—C7'—H7'119.7
C6—C7—H7119.9C6'—C7'—H7'119.7
C7—C8—C3121.27 (10)C7'—C8'—C3'121.18 (10)
C7—C8—H8119.4C7'—C8'—H8'119.4
C3—C8—H8119.4C3'—C8'—H8'119.4
C10—C9—C4178.10 (12)C10'—C9'—C4'179.33 (12)
C9—C10—H10178.9 (11)C9'—C10'—H10'179.0 (11)
C6i—C1—C2—C30.37 (13)C6'ii—C1'—C2'—C3'−7.49 (14)
C1—C2—C3—C8−83.73 (12)C1'—C2'—C3'—C8'92.85 (12)
C1—C2—C3—C482.56 (12)C1'—C2'—C3'—C4'−74.54 (13)
C8—C3—C4—C513.75 (14)C8'—C3'—C4'—C5'−14.18 (14)
C2—C3—C4—C5−152.94 (10)C2'—C3'—C4'—C5'153.66 (10)
C8—C3—C4—C9−174.87 (9)C8'—C3'—C4'—C9'173.77 (9)
C2—C3—C4—C918.44 (14)C2'—C3'—C4'—C9'−18.39 (15)
C3—C4—C5—C6−0.07 (15)C3'—C4'—C5'—C6'−0.46 (15)
C9—C4—C5—C6−171.69 (9)C9'—C4'—C5'—C6'171.63 (9)
C4—C5—C6—C7−13.95 (15)C4'—C5'—C6'—C7'14.87 (15)
C4—C5—C6—C1i154.25 (10)C4'—C5'—C6'—C1'ii−152.57 (10)
C5—C6—C7—C814.20 (14)C5'—C6'—C7'—C8'−14.64 (15)
C1i—C6—C7—C8−153.81 (10)C1'ii—C6'—C7'—C8'152.71 (10)
C6—C7—C8—C3−0.41 (15)C6'—C7'—C8'—C3'−0.11 (16)
C4—C3—C8—C7−13.60 (15)C4'—C3'—C8'—C7'14.55 (15)
C2—C3—C8—C7153.24 (10)C2'—C3'—C8'—C7'−153.38 (10)
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z.
(III) 4,13-Diethynyl[2.2]paracyclophane top
Crystal data top
C20H16Dx = 1.237 Mg m−3
Mr = 256.33Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31Cell parameters from 5139 reflections
Hall symbol: P 31θ = 2–28°
a = 11.8823 (12) ŵ = 0.07 mm−1
c = 8.4426 (12) ÅT = 143 K
V = 1032.3 (2) Å3Irregular tablet, colourless
Z = 30.40 × 0.20 × 0.08 mm
F(000) = 408
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1536 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.081
Graphite monochromatorθmax = 28.3°, θmin = 2.0°
Detector resolution: 8.192 pixels mm-1h = −15→15
ω scansk = −15→15
13844 measured reflectionsl = −11→11
1719 independent 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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0585P)2 + 0.013P]
where P = (Fo2 + 2Fc2)/3
1719 reflections(Δ/σ)max < 0.001
189 parametersΔρmax = 0.22 e Å−3
185 restraintsΔρmin = −0.14 e Å−3
Crystal data top
C20H16Z = 3
Mr = 256.33Mo Kα radiation
Trigonal, P31µ = 0.07 mm−1
a = 11.8823 (12) ÅT = 143 K
c = 8.4426 (12) Å0.40 × 0.20 × 0.08 mm
V = 1032.3 (2) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1536 reflections with I > 2σ(I)
13844 measured reflectionsRint = 0.081
1719 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035185 restraints
wR(F2) = 0.088H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.22 e Å−3
1719 reflectionsΔρmin = −0.14 e Å−3
189 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 > 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.

The compound crystallizes by chance in a chiral space group. In the absence of significant anomalous scattering, Friedel opposite reflections were merged and the Flack parameter is thus meaningless.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.38463 (19)0.52599 (19)0.2228 (2)0.0288 (4)
H1A0.47090.56250.17180.035*
H1B0.36510.59730.23590.035*
C20.27775 (19)0.41697 (19)0.1114 (2)0.0279 (4)
H2A0.20070.42820.10680.034*
H2B0.31300.42770.00280.034*
C30.23642 (18)0.28075 (17)0.1699 (2)0.0237 (4)
C40.32029 (19)0.22918 (18)0.1641 (2)0.0243 (4)
C50.30519 (18)0.13403 (18)0.2743 (2)0.0249 (4)
H50.36240.09990.27050.030*
C60.20789 (18)0.08875 (17)0.3890 (2)0.0245 (4)
C70.10905 (18)0.11972 (17)0.3691 (2)0.0244 (4)
H70.03170.07590.43010.029*
C80.12385 (17)0.21385 (18)0.2609 (2)0.0244 (4)
H80.05590.23330.24840.029*
C90.2258 (2)0.03632 (19)0.5445 (2)0.0298 (4)
H9A0.28450.00080.52780.036*
H9B0.1407−0.03580.58000.036*
C100.28428 (19)0.14386 (19)0.6790 (2)0.0276 (4)
H10A0.21500.12790.75600.033*
H10B0.35310.13660.73630.033*
C110.34088 (18)0.28007 (18)0.6133 (2)0.0236 (4)
C120.26351 (18)0.33750 (17)0.6053 (2)0.0228 (4)
H120.19380.31120.67810.027*
C130.28619 (18)0.43301 (17)0.4927 (2)0.0233 (4)
C140.38900 (19)0.47263 (17)0.3841 (2)0.0247 (4)
C150.48119 (17)0.43557 (18)0.4172 (2)0.0266 (4)
H150.56160.47610.36200.032*
C160.45747 (19)0.34053 (19)0.5294 (2)0.0276 (4)
H160.52140.31660.54900.033*
C170.43427 (19)0.28743 (19)0.0645 (2)0.0278 (4)
C180.5296 (2)0.3360 (2)−0.0167 (3)0.0344 (4)
H180.611 (2)0.371 (2)−0.100 (3)0.025 (5)*
C190.19045 (19)0.47211 (18)0.4727 (2)0.0261 (4)
C200.1076 (2)0.4989 (2)0.4533 (3)0.0318 (4)
H200.040 (3)0.516 (3)0.440 (3)0.049 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0319 (10)0.0230 (9)0.0280 (9)0.0110 (8)−0.0003 (8)0.0027 (7)
C20.0334 (10)0.0277 (10)0.0235 (9)0.0158 (8)−0.0011 (8)0.0039 (7)
C30.0268 (9)0.0232 (9)0.0183 (8)0.0104 (7)−0.0047 (7)−0.0035 (7)
C40.0260 (9)0.0244 (9)0.0204 (8)0.0110 (7)−0.0007 (7)−0.0031 (7)
C50.0254 (9)0.0227 (9)0.0269 (9)0.0122 (7)−0.0025 (7)−0.0045 (7)
C60.0267 (9)0.0169 (8)0.0253 (9)0.0075 (7)−0.0030 (7)−0.0035 (6)
C70.0238 (9)0.0196 (8)0.0230 (9)0.0057 (7)0.0000 (7)−0.0045 (7)
C80.0211 (8)0.0278 (9)0.0230 (8)0.0113 (8)−0.0062 (7)−0.0082 (7)
C90.0363 (11)0.0213 (9)0.0304 (10)0.0134 (8)−0.0009 (8)0.0024 (7)
C100.0319 (10)0.0282 (9)0.0236 (9)0.0156 (8)−0.0036 (7)0.0022 (7)
C110.0255 (9)0.0225 (8)0.0215 (8)0.0108 (7)−0.0073 (7)−0.0027 (7)
C120.0239 (8)0.0214 (8)0.0205 (8)0.0094 (7)−0.0037 (7)−0.0036 (7)
C130.0259 (9)0.0193 (8)0.0219 (8)0.0092 (7)−0.0056 (7)−0.0040 (6)
C140.0260 (9)0.0171 (8)0.0253 (9)0.0065 (7)−0.0035 (7)−0.0025 (7)
C150.0198 (9)0.0237 (9)0.0292 (10)0.0056 (7)−0.0013 (7)−0.0040 (7)
C160.0243 (9)0.0272 (9)0.0318 (10)0.0132 (8)−0.0068 (7)−0.0045 (8)
C170.0292 (10)0.0283 (9)0.0275 (9)0.0156 (8)−0.0012 (7)−0.0019 (8)
C180.0354 (11)0.0350 (10)0.0328 (10)0.0175 (9)0.0062 (9)0.0011 (8)
C190.0321 (10)0.0232 (9)0.0227 (9)0.0135 (8)−0.0009 (7)−0.0011 (7)
C200.0385 (11)0.0320 (10)0.0318 (10)0.0227 (9)0.0019 (8)0.0033 (8)
Geometric parameters (Å, º) top
C1—C141.514 (3)C9—H9A0.9900
C1—C21.591 (3)C9—H9B0.9900
C1—H1A0.9900C10—C111.514 (3)
C1—H1B0.9900C10—H10A0.9900
C2—C31.520 (3)C10—H10B0.9900
C2—H2A0.9900C11—C161.394 (3)
C2—H2B0.9900C11—C121.394 (3)
C3—C81.396 (3)C12—C131.400 (3)
C3—C41.408 (3)C12—H120.9500
C4—C51.405 (3)C13—C141.407 (3)
C4—C171.443 (3)C13—C191.438 (3)
C5—C61.393 (3)C14—C151.398 (3)
C5—H50.9500C15—C161.390 (3)
C6—C71.405 (3)C15—H150.9500
C6—C91.513 (3)C16—H160.9500
C7—C81.385 (3)C17—C181.197 (3)
C7—H70.9500C18—H181.09 (2)
C8—H80.9500C19—C201.188 (3)
C9—C101.587 (3)C20—H200.93 (3)
C14—C1—C2111.79 (15)C10—C9—H9A109.1
C14—C1—H1A109.3C6—C9—H9B109.1
C2—C1—H1A109.3C10—C9—H9B109.1
C14—C1—H1B109.3H9A—C9—H9B107.8
C2—C1—H1B109.3C11—C10—C9112.32 (16)
H1A—C1—H1B107.9C11—C10—H10A109.1
C3—C2—C1112.12 (15)C9—C10—H10A109.1
C3—C2—H2A109.2C11—C10—H10B109.1
C1—C2—H2A109.2C9—C10—H10B109.1
C3—C2—H2B109.2H10A—C10—H10B107.9
C1—C2—H2B109.2C16—C11—C12116.89 (17)
H2A—C2—H2B107.9C16—C11—C10122.23 (17)
C8—C3—C4117.17 (17)C12—C11—C10119.46 (17)
C8—C3—C2119.51 (17)C11—C12—C13121.53 (17)
C4—C3—C2122.02 (17)C11—C12—H12119.2
C5—C4—C3119.61 (17)C13—C12—H12119.2
C5—C4—C17118.91 (17)C12—C13—C14119.81 (17)
C3—C4—C17120.68 (17)C12—C13—C19118.64 (17)
C6—C5—C4121.23 (17)C14—C13—C19120.66 (17)
C6—C5—H5119.4C15—C14—C13116.74 (17)
C4—C5—H5119.4C15—C14—C1120.55 (18)
C5—C6—C7117.16 (17)C13—C14—C1121.37 (17)
C5—C6—C9120.12 (17)C16—C15—C14121.31 (17)
C7—C6—C9121.29 (17)C16—C15—H15119.3
C8—C7—C6120.32 (17)C14—C15—H15119.3
C8—C7—H7119.8C15—C16—C11120.69 (17)
C6—C7—H7119.8C15—C16—H16119.7
C7—C8—C3121.42 (17)C11—C16—H16119.7
C7—C8—H8119.3C18—C17—C4179.3 (2)
C3—C8—H8119.3C17—C18—H18173.4 (12)
C6—C9—C10112.64 (15)C20—C19—C13177.0 (2)
C6—C9—H9A109.1C19—C20—H20177.2 (18)
C14—C1—C2—C3−18.1 (2)C6—C9—C10—C11−14.7 (2)
C1—C2—C3—C897.2 (2)C9—C10—C11—C16−73.0 (2)
C1—C2—C3—C4−69.5 (2)C9—C10—C11—C1293.0 (2)
C8—C3—C4—C5−14.5 (3)C16—C11—C12—C1313.7 (3)
C2—C3—C4—C5152.45 (17)C10—C11—C12—C13−153.03 (18)
C8—C3—C4—C17175.86 (17)C11—C12—C13—C140.2 (3)
C2—C3—C4—C17−17.2 (3)C11—C12—C13—C19169.42 (17)
C3—C4—C5—C60.5 (3)C12—C13—C14—C15−14.1 (3)
C17—C4—C5—C6170.32 (17)C19—C13—C14—C15176.86 (16)
C4—C5—C6—C713.6 (3)C12—C13—C14—C1152.79 (17)
C4—C5—C6—C9−152.86 (18)C19—C13—C14—C1−16.3 (3)
C5—C6—C7—C8−13.7 (2)C2—C1—C14—C1597.6 (2)
C9—C6—C7—C8152.61 (17)C2—C1—C14—C13−68.8 (2)
C6—C7—C8—C3−0.4 (3)C13—C14—C15—C1614.4 (3)
C4—C3—C8—C714.5 (3)C1—C14—C15—C16−152.59 (19)
C2—C3—C8—C7−152.73 (17)C14—C15—C16—C11−0.6 (3)
C5—C6—C9—C1093.5 (2)C12—C11—C16—C15−13.5 (3)
C7—C6—C9—C10−72.4 (2)C10—C11—C16—C15152.85 (18)
(IV) 4,15-Diethynyl[2.2]paracyclophane top
Crystal data top
C20H16F(000) = 272
Mr = 256.33Dx = 1.220 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 4465 reflections
a = 7.6187 (10) Åθ = 2–28°
b = 10.8231 (16) ŵ = 0.07 mm−1
c = 8.6293 (12) ÅT = 143 K
β = 101.230 (6)°Irregular prism, colourless
V = 697.93 (17) Å30.40 × 0.20 × 0.18 mm
Z = 2
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1706 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.049
Graphite monochromatorθmax = 28.3°, θmin = 2.4°
Detector resolution: 8.192 pixels mm-1h = −10→10
ω scansk = −14→14
7442 measured reflectionsl = −11→11
1821 independent 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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.071P)2 + 0.0161P]
where P = (Fo2 + 2Fc2)/3
1821 reflections(Δ/σ)max < 0.001
189 parametersΔρmax = 0.26 e Å−3
185 restraintsΔρmin = −0.16 e Å−3
Crystal data top
C20H16V = 697.93 (17) Å3
Mr = 256.33Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.6187 (10) ŵ = 0.07 mm−1
b = 10.8231 (16) ÅT = 143 K
c = 8.6293 (12) Å0.40 × 0.20 × 0.18 mm
β = 101.230 (6)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1706 reflections with I > 2σ(I)
7442 measured reflectionsRint = 0.049
1821 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036185 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.26 e Å−3
1821 reflectionsΔρmin = −0.16 e Å−3
189 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 > 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.

The compound crystallizes by chance in a chiral space group. In the absence of significant anomalous scattering, Friedel opposites were merged and the Flack parameter is thus meaningless.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1−0.0018 (2)0.37404 (17)0.7711 (2)0.0277 (3)
H1A−0.03790.31610.84800.033*
H1B−0.09830.43590.74220.033*
C20.1770 (2)0.44218 (17)0.8517 (2)0.0289 (4)
H2A0.14640.52250.89440.035*
H2B0.23950.39170.94130.035*
C30.3022 (2)0.46428 (15)0.73761 (18)0.0228 (3)
C40.4525 (2)0.38759 (15)0.73720 (17)0.0222 (3)
C50.51507 (19)0.36971 (16)0.59655 (18)0.0235 (3)
H50.61540.31760.59660.028*
C60.4328 (2)0.42705 (16)0.45668 (18)0.0253 (3)
C70.3143 (2)0.52349 (16)0.4689 (2)0.0274 (3)
H70.27710.57720.38150.033*
C80.2501 (2)0.54185 (15)0.6075 (2)0.0266 (3)
H80.16980.60800.61370.032*
C90.4407 (2)0.3700 (2)0.2981 (2)0.0322 (4)
H9A0.56660.34960.29450.039*
H9B0.39800.43100.21360.039*
C100.3231 (2)0.24869 (18)0.26524 (19)0.0288 (3)
H10A0.26240.24720.15280.035*
H10B0.40210.17540.28490.035*
C110.18376 (19)0.24126 (16)0.36865 (18)0.0226 (3)
C120.0380 (2)0.32237 (16)0.34748 (19)0.0250 (3)
H12−0.00780.35600.24600.030*
C13−0.0398 (2)0.35376 (14)0.4754 (2)0.0248 (3)
H13−0.13580.41130.46040.030*
C140.0197 (2)0.30306 (15)0.62436 (19)0.0229 (3)
C150.1327 (2)0.19907 (14)0.63414 (18)0.0220 (3)
C160.2166 (2)0.17150 (14)0.50695 (19)0.0220 (3)
H160.29730.10390.51550.026*
C170.5339 (2)0.31673 (17)0.87298 (19)0.0254 (3)
C180.6094 (3)0.2580 (2)0.9827 (2)0.0352 (4)
H180.667 (3)0.211 (3)1.070 (3)0.063 (8)*
C190.1768 (2)0.12835 (16)0.77758 (19)0.0272 (3)
C200.2099 (3)0.06603 (19)0.8933 (2)0.0373 (4)
H200.234 (3)0.008 (3)0.980 (3)0.054 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0234 (7)0.0275 (8)0.0340 (8)−0.0019 (7)0.0103 (6)−0.0044 (7)
C20.0244 (7)0.0343 (9)0.0284 (8)−0.0004 (7)0.0064 (6)−0.0080 (7)
C30.0207 (6)0.0206 (7)0.0257 (7)−0.0033 (6)0.0013 (5)−0.0051 (6)
C40.0186 (6)0.0231 (7)0.0238 (7)−0.0045 (6)0.0016 (5)−0.0030 (6)
C50.0175 (6)0.0262 (8)0.0273 (7)−0.0036 (6)0.0054 (5)−0.0024 (7)
C60.0218 (7)0.0285 (8)0.0263 (7)−0.0091 (6)0.0065 (6)−0.0009 (6)
C70.0258 (8)0.0249 (8)0.0292 (8)−0.0062 (6)−0.0006 (6)0.0056 (7)
C80.0218 (7)0.0207 (7)0.0352 (8)−0.0024 (6)0.0001 (6)−0.0031 (6)
C90.0314 (8)0.0420 (10)0.0248 (7)−0.0106 (8)0.0093 (6)−0.0015 (7)
C100.0299 (8)0.0321 (8)0.0254 (7)−0.0025 (7)0.0075 (6)−0.0018 (7)
C110.0205 (6)0.0215 (7)0.0254 (7)−0.0027 (6)0.0034 (5)−0.0026 (6)
C120.0225 (7)0.0225 (7)0.0278 (7)−0.0035 (6)−0.0005 (6)0.0020 (6)
C130.0174 (7)0.0187 (7)0.0369 (8)−0.0012 (5)0.0018 (6)−0.0012 (6)
C140.0175 (6)0.0205 (7)0.0313 (8)−0.0041 (6)0.0062 (6)−0.0030 (6)
C150.0196 (6)0.0187 (7)0.0268 (7)−0.0038 (6)0.0022 (6)−0.0001 (6)
C160.0195 (6)0.0165 (6)0.0291 (7)−0.0010 (5)0.0025 (5)−0.0021 (6)
C170.0235 (7)0.0260 (8)0.0264 (7)−0.0016 (6)0.0046 (6)−0.0032 (6)
C180.0355 (9)0.0386 (10)0.0310 (9)0.0072 (8)0.0056 (7)0.0044 (8)
C190.0283 (8)0.0224 (8)0.0307 (8)−0.0035 (6)0.0049 (6)−0.0025 (6)
C200.0480 (11)0.0298 (9)0.0316 (9)−0.0043 (8)0.0015 (8)0.0033 (7)
Geometric parameters (Å, º) top
C1—C141.517 (2)C9—H9A0.9900
C1—C21.586 (2)C9—H9B0.9900
C1—H1A0.9900C10—C111.516 (2)
C1—H1B0.9900C10—H10A0.9900
C2—C31.517 (2)C10—H10B0.9900
C2—H2A0.9900C11—C161.393 (2)
C2—H2B0.9900C11—C121.399 (2)
C3—C81.396 (2)C12—C131.393 (2)
C3—C41.415 (2)C12—H120.9500
C4—C51.401 (2)C13—C141.390 (2)
C4—C171.436 (2)C13—H130.9500
C5—C61.393 (2)C14—C151.410 (2)
C5—H50.9500C15—C161.405 (2)
C6—C71.397 (3)C15—C191.438 (2)
C6—C91.514 (2)C16—H160.9500
C7—C81.392 (3)C17—C181.191 (3)
C7—H70.9500C18—H180.95 (3)
C8—H80.9500C19—C201.191 (3)
C9—C101.584 (3)C20—H200.96 (3)
C14—C1—C2112.24 (12)C10—C9—H9A109.1
C14—C1—H1A109.2C6—C9—H9B109.1
C2—C1—H1A109.2C10—C9—H9B109.1
C14—C1—H1B109.2H9A—C9—H9B107.9
C2—C1—H1B109.2C11—C10—C9112.05 (14)
H1A—C1—H1B107.9C11—C10—H10A109.2
C3—C2—C1112.56 (13)C9—C10—H10A109.2
C3—C2—H2A109.1C11—C10—H10B109.2
C1—C2—H2A109.1C9—C10—H10B109.2
C3—C2—H2B109.1H10A—C10—H10B107.9
C1—C2—H2B109.1C16—C11—C12117.22 (14)
H2A—C2—H2B107.8C16—C11—C10120.24 (14)
C8—C3—C4117.01 (14)C12—C11—C10121.24 (15)
C8—C3—C2120.04 (14)C13—C12—C11119.93 (14)
C4—C3—C2121.36 (14)C13—C12—H12120.0
C5—C4—C3119.69 (14)C11—C12—H12120.0
C5—C4—C17117.85 (14)C14—C13—C12121.62 (15)
C3—C4—C17122.17 (14)C14—C13—H13119.2
C6—C5—C4121.16 (14)C12—C13—H13119.2
C6—C5—H5119.4C13—C14—C15117.12 (14)
C4—C5—H5119.4C13—C14—C1120.23 (15)
C5—C6—C7117.12 (14)C15—C14—C1121.21 (14)
C5—C6—C9120.75 (16)C16—C15—C14119.21 (14)
C7—C6—C9120.87 (15)C16—C15—C19119.58 (14)
C8—C7—C6120.78 (15)C14—C15—C19120.93 (14)
C8—C7—H7119.6C11—C16—C15121.40 (14)
C6—C7—H7119.6C11—C16—H16119.3
C7—C8—C3120.85 (15)C15—C16—H16119.3
C7—C8—H8119.6C18—C17—C4176.63 (17)
C3—C8—H8119.6C17—C18—H18178.6 (17)
C6—C9—C10112.28 (13)C20—C19—C15177.47 (18)
C6—C9—H9A109.1C19—C20—H20174.0 (17)
C14—C1—C2—C322.3 (2)C6—C9—C10—C1119.4 (2)
C1—C2—C3—C864.0 (2)C9—C10—C11—C16−97.61 (19)
C1—C2—C3—C4−101.20 (18)C9—C10—C11—C1269.0 (2)
C8—C3—C4—C5−15.2 (2)C16—C11—C12—C1315.7 (2)
C2—C3—C4—C5150.48 (15)C10—C11—C12—C13−151.23 (16)
C8—C3—C4—C17171.22 (14)C11—C12—C13—C14−2.3 (2)
C2—C3—C4—C17−23.2 (2)C12—C13—C14—C15−13.9 (2)
C3—C4—C5—C60.6 (2)C12—C13—C14—C1152.54 (15)
C17—C4—C5—C6174.47 (15)C2—C1—C14—C13−99.26 (17)
C4—C5—C6—C714.3 (2)C2—C1—C14—C1566.7 (2)
C4—C5—C6—C9−153.02 (15)C13—C14—C15—C1616.4 (2)
C5—C6—C7—C8−14.6 (2)C1—C14—C15—C16−149.91 (15)
C9—C6—C7—C8152.71 (16)C13—C14—C15—C19−169.66 (14)
C6—C7—C8—C3−0.1 (2)C1—C14—C15—C1924.0 (2)
C4—C3—C8—C715.0 (2)C12—C11—C16—C15−13.1 (2)
C2—C3—C8—C7−150.84 (16)C10—C11—C16—C15154.03 (15)
C5—C6—C9—C1070.55 (19)C14—C15—C16—C11−3.1 (2)
C7—C6—C9—C10−96.3 (2)C19—C15—C16—C11−177.07 (14)
(V) 4,16-Diethynyl[2.2]paracyclophane top
Crystal data top
C20H16Dx = 1.190 Mg m−3
Mr = 256.33Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31Cell parameters from 5471 reflections
Hall symbol: P 31θ = 2–28°
a = 12.5475 (12) ŵ = 0.07 mm−1
c = 7.8705 (10) ÅT = 143 K
V = 1073.1 (2) Å3Needle, colourless
Z = 30.45 × 0.12 × 0.11 mm
F(000) = 408
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1311 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
Graphite monochromatorθmax = 26.4°, θmin = 1.9°
Detector resolution: 8.192 pixels mm-1h = −15→15
ω scansk = −15→15
14432 measured reflectionsl = −9→9
1462 independent 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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0692P)2 + 0.073P]
where P = (Fo2 + 2Fc2)/3
1462 reflections(Δ/σ)max < 0.001
189 parametersΔρmax = 0.27 e Å−3
185 restraintsΔρmin = −0.12 e Å−3
Crystal data top
C20H16Z = 3
Mr = 256.33Mo Kα radiation
Trigonal, P31µ = 0.07 mm−1
a = 12.5475 (12) ÅT = 143 K
c = 7.8705 (10) Å0.45 × 0.12 × 0.11 mm
V = 1073.1 (2) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1311 reflections with I > 2σ(I)
14432 measured reflectionsRint = 0.037
1462 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037185 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.27 e Å−3
1462 reflectionsΔρmin = −0.12 e Å−3
189 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 > 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.

The compound crystallizes by chance in a chiral space group. In the absence of significant anomalous scattering, the Friedel opposite reflections were merged and the Flack parameter is thus meaningless.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.4525 (2)0.5701 (3)0.5217 (4)0.0467 (6)
H1A0.41920.54640.40520.051*
H1B0.41360.61370.57490.051*
C20.4176 (2)0.4496 (3)0.6277 (3)0.0431 (6)
H2A0.34690.43080.70260.047*
H2B0.39180.37950.54860.047*
C30.5241 (2)0.4632 (2)0.7351 (3)0.0336 (5)
C40.5642 (2)0.5382 (2)0.8805 (3)0.0331 (5)
C50.6870 (2)0.5902 (2)0.9345 (3)0.0313 (5)
H50.71400.64211.03160.038*
C60.7692 (2)0.5667 (2)0.8477 (3)0.0301 (5)
C70.7199 (2)0.4704 (2)0.7300 (3)0.0323 (5)
H70.76920.43850.68790.039*
C80.6002 (2)0.4214 (2)0.6745 (3)0.0352 (5)
H80.56910.35730.59260.042*
C90.9052 (2)0.6605 (2)0.8497 (3)0.0378 (5)
H9A0.95270.61690.85280.042*
H9B0.92470.71080.95420.042*
C100.9464 (2)0.7486 (2)0.6886 (3)0.0381 (5)
H10A1.00490.83390.72520.042*
H10B0.98990.72310.60780.042*
C110.8386 (2)0.7465 (2)0.5988 (3)0.0312 (5)
C120.7865 (2)0.6723 (2)0.4560 (3)0.0350 (5)
H120.83570.65180.38700.042*
C130.6651 (2)0.6282 (2)0.4130 (3)0.0391 (6)
H130.63190.57800.31510.047*
C140.5907 (2)0.6567 (2)0.5119 (3)0.0375 (5)
C150.6488 (2)0.7514 (2)0.6291 (3)0.0377 (6)
H150.60400.78590.67940.045*
C160.7723 (2)0.7972 (2)0.6747 (3)0.0341 (5)
C170.4861 (2)0.5759 (3)0.9650 (3)0.0422 (6)
C180.4248 (3)0.6080 (3)1.0396 (4)0.0646 (10)
H180.355 (4)0.612 (4)1.109 (5)0.094 (12)*
C190.8233 (2)0.8801 (2)0.8144 (3)0.0420 (6)
C200.8666 (3)0.9478 (3)0.9312 (4)0.0577 (8)
H200.904 (3)1.000 (4)1.028 (5)0.071 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0376 (13)0.0564 (16)0.0467 (14)0.0240 (12)−0.0007 (11)0.0151 (12)
C20.0344 (13)0.0431 (15)0.0456 (13)0.0149 (11)−0.0019 (11)0.0074 (11)
C30.0298 (11)0.0316 (12)0.0338 (10)0.0113 (10)0.0034 (9)0.0111 (9)
C40.0361 (12)0.0348 (12)0.0337 (11)0.0217 (10)0.0112 (9)0.0148 (9)
C50.0414 (13)0.0333 (12)0.0259 (9)0.0238 (11)0.0030 (8)0.0038 (8)
C60.0335 (12)0.0323 (11)0.0282 (10)0.0192 (10)0.0044 (8)0.0078 (9)
C70.0396 (12)0.0320 (11)0.0301 (10)0.0217 (10)0.0091 (9)0.0064 (9)
C80.0421 (13)0.0274 (11)0.0296 (11)0.0126 (10)0.0036 (9)0.0036 (9)
C90.0341 (12)0.0424 (13)0.0398 (12)0.0213 (11)−0.0014 (9)0.0011 (10)
C100.0311 (12)0.0357 (13)0.0449 (13)0.0147 (10)0.0054 (10)0.0006 (10)
C110.0311 (11)0.0270 (11)0.0339 (10)0.0134 (9)0.0076 (9)0.0081 (9)
C120.0393 (13)0.0345 (12)0.0296 (10)0.0173 (10)0.0115 (9)0.0081 (9)
C130.0440 (14)0.0392 (13)0.0281 (10)0.0163 (11)0.0032 (10)0.0078 (10)
C140.0386 (13)0.0434 (13)0.0325 (11)0.0221 (11)0.0017 (9)0.0146 (10)
C150.0423 (13)0.0397 (13)0.0412 (12)0.0280 (11)0.0108 (10)0.0149 (10)
C160.0401 (12)0.0275 (11)0.0362 (11)0.0181 (10)0.0081 (9)0.0082 (9)
C170.0484 (15)0.0516 (15)0.0367 (12)0.0325 (13)0.0105 (10)0.0133 (11)
C180.078 (2)0.100 (3)0.0531 (17)0.072 (2)0.0279 (16)0.0266 (17)
C190.0469 (14)0.0327 (13)0.0518 (14)0.0238 (12)0.0066 (11)−0.0003 (11)
C200.0678 (19)0.0527 (17)0.0627 (18)0.0378 (16)−0.0050 (16)−0.0181 (15)
Geometric parameters (Å, º) top
C1—C141.520 (3)C9—H9A0.9900
C1—C21.585 (4)C9—H9B0.9900
C1—H1A0.9900C10—C111.515 (3)
C1—H1B0.9900C10—H10A0.9900
C2—C31.518 (3)C10—H10B0.9900
C2—H2A0.9900C11—C121.396 (3)
C2—H2B0.9900C11—C161.408 (3)
C3—C81.383 (3)C12—C131.377 (4)
C3—C41.405 (3)C12—H120.9500
C4—C51.406 (3)C13—C141.392 (4)
C4—C171.446 (3)C13—H130.9500
C5—C61.386 (3)C14—C151.388 (4)
C5—H50.9500C15—C161.404 (4)
C6—C71.397 (3)C15—H150.9500
C6—C91.513 (3)C16—C191.427 (4)
C7—C81.379 (3)C17—C181.187 (4)
C7—H70.9500C18—H181.06 (4)
C8—H80.9500C19—C201.183 (4)
C9—C101.590 (3)C20—H200.96 (4)
C14—C1—C2112.44 (19)C10—C9—H9A109.1
C14—C1—H1A109.1C6—C9—H9B109.1
C2—C1—H1A109.1C10—C9—H9B109.1
C14—C1—H1B109.1H9A—C9—H9B107.9
C2—C1—H1B109.1C11—C10—C9112.52 (19)
H1A—C1—H1B107.8C11—C10—H10A109.1
C3—C2—C1112.2 (2)C9—C10—H10A109.1
C3—C2—H2A109.2C11—C10—H10B109.1
C1—C2—H2A109.2C9—C10—H10B109.1
C3—C2—H2B109.2H10A—C10—H10B107.8
C1—C2—H2B109.2C12—C11—C16117.2 (2)
H2A—C2—H2B107.9C12—C11—C10120.2 (2)
C8—C3—C4116.8 (2)C16—C11—C10121.2 (2)
C8—C3—C2120.1 (2)C13—C12—C11121.4 (2)
C4—C3—C2121.9 (2)C13—C12—H12119.3
C3—C4—C5119.9 (2)C11—C12—H12119.3
C3—C4—C17121.4 (2)C12—C13—C14120.5 (2)
C5—C4—C17118.3 (2)C12—C13—H13119.7
C6—C5—C4120.8 (2)C14—C13—H13119.7
C6—C5—H5119.6C15—C14—C13117.3 (2)
C4—C5—H5119.6C15—C14—C1120.1 (2)
C5—C6—C7117.1 (2)C13—C14—C1121.1 (2)
C5—C6—C9120.0 (2)C14—C15—C16121.3 (2)
C7—C6—C9121.24 (19)C14—C15—H15119.3
C8—C7—C6120.5 (2)C16—C15—H15119.3
C8—C7—H7119.7C15—C16—C11119.2 (2)
C6—C7—H7119.7C15—C16—C19119.8 (2)
C7—C8—C3121.7 (2)C11—C16—C19120.3 (2)
C7—C8—H8119.1C18—C17—C4177.6 (3)
C3—C8—H8119.1C17—C18—H18165 (2)
C6—C9—C10112.38 (19)C20—C19—C16178.8 (3)
C6—C9—H9A109.1C19—C20—H20176 (2)
C14—C1—C2—C316.1 (3)C6—C9—C10—C1117.5 (3)
C1—C2—C3—C8−95.5 (3)C9—C10—C11—C12−97.5 (2)
C1—C2—C3—C471.8 (3)C9—C10—C11—C1669.0 (3)
C8—C3—C4—C514.4 (3)C16—C11—C12—C13−13.9 (3)
C2—C3—C4—C5−153.2 (2)C10—C11—C12—C13153.1 (2)
C8—C3—C4—C17−173.2 (2)C11—C12—C13—C14−0.1 (3)
C2—C3—C4—C1719.1 (3)C12—C13—C14—C1514.3 (3)
C3—C4—C5—C6−1.2 (3)C12—C13—C14—C1−151.7 (2)
C17—C4—C5—C6−173.7 (2)C2—C1—C14—C15−93.7 (3)
C4—C5—C6—C7−13.5 (3)C2—C1—C14—C1371.8 (3)
C4—C5—C6—C9152.0 (2)C13—C14—C15—C16−14.5 (3)
C5—C6—C7—C814.9 (3)C1—C14—C15—C16151.7 (2)
C9—C6—C7—C8−150.4 (2)C14—C15—C16—C110.5 (3)
C6—C7—C8—C3−1.4 (3)C14—C15—C16—C19−170.0 (2)
C4—C3—C8—C7−13.3 (3)C12—C11—C16—C1513.5 (3)
C2—C3—C8—C7154.6 (2)C10—C11—C16—C15−153.4 (2)
C5—C6—C9—C10−95.2 (2)C12—C11—C16—C19−176.0 (2)
C7—C6—C9—C1069.6 (3)C10—C11—C16—C1917.1 (3)

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC18H16C20H16C20H16C20H16
Mr232.31256.33256.33256.33
Crystal system, space groupMonoclinic, P21/cTriclinic, P1Trigonal, P31Monoclinic, P21
Temperature (K)173143143143
a, b, c (Å)7.6538 (14), 11.022 (2), 15.056 (3)7.6316 (10), 7.8177 (10), 12.4446 (16)11.8823 (12), 11.8823 (12), 8.4426 (12)7.6187 (10), 10.8231 (16), 8.6293 (12)
α, β, γ (°)90, 99.561 (16), 9078.125 (2), 72.339 (2), 73.971 (2)90, 90, 12090, 101.230 (6), 90
V (Å3)1252.4 (4)673.90 (15)1032.3 (2)697.93 (17)
Z4232
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm−1)0.070.070.070.07
Crystal size (mm)0.6 × 0.3 × 0.180.42 × 0.28 × 0.260.40 × 0.20 × 0.080.40 × 0.20 × 0.18
Data collection
DiffractometerSiemens P4Bruker SMART 1000 CCD area-detectorBruker SMART 1000 CCD area-detectorBruker SMART 1000 CCD area-detector
Absorption correction––––
No. of measured, independent and
observed [I > 2σ(I)] reflections		3461, 2191, 1267 5064, 3383, 2953 13844, 1719, 1536 7442, 1821, 1706
Rint0.0240.0300.0810.049
(sin θ/λ)max (Å−1)0.5950.6710.6660.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.103, 0.86 0.045, 0.126, 1.08 0.035, 0.088, 1.02 0.036, 0.098, 1.07
No. of reflections2191338317191821
No. of parameters168189189189
No. of restraints1670185185
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.19, −0.170.35, −0.230.22, −0.140.26, −0.16


(V)
Crystal data
Chemical formulaC20H16
Mr256.33
Crystal system, space groupTrigonal, P31
Temperature (K)143
a, b, c (Å)12.5475 (12), 12.5475 (12), 7.8705 (10)
α, β, γ (°)90, 90, 120
V (Å3)1073.1 (2)
Z3
Radiation typeMo Kα
µ (mm−1)0.07
Crystal size (mm)0.45 × 0.12 × 0.11
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		14432, 1462, 1311
Rint0.037
(sin θ/λ)max (Å−1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.101, 1.05
No. of reflections1462
No. of parameters189
No. of restraints185
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.27, −0.12

Computer programs: XSCANS (Siemens, 1991), SMART (Bruker, 1998), XSCANS, SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected dimensions of compounds (I)–(V) (Å, °) top
CompoundC—C bridge bond lengthsC—C—C bridge bond anglesC—C—C bridgehead bond anglesBridgehead deviations from planeC≡C bond lengthsC—C≡C bond angles
11.582 (3), 1.576 (3)111.8 (2), 113.0 (2), 112.5 (2), 113.4 (2)117.8 (2), 116.9 (2), 116.7 (2), 117.0 (2)0.162 (2), 0.148 (2), 0.150 (3), 0.154 (3)1.183 (3)179.6 (2)
21.599 (2), 1.591 (2)113.0 (1), 112.4 (1), 112.9 (1), 112.7 (1)117.2 (1), 117.5 (1), 116.9 (1), 117.1 (1)0.149 (2), 0.152 (2), 0.157 (2), 0.160 (2)1.194 (2), 1.194 (2)178.1 (1), 179.3 (1)
31.591 (3), 1.587 (3)111.8 (2), 112.1 (2), 112.6 (2), 112.3 (2)117.2 (2), 117.2 (2), 116.9 (2), 116.7 (2)0.158 (3), 0.148 (3), 0.147 (3), 0.156 (3)1.197 (3), 1.188 (3)179.3 (2), 177.0 (2)
41.586 (2), 1.584 (3)112.2 (1), 112.6 (1), 112.2 (1), 112.0 (1)117.0 (1), 117.1 (1), 117.2 (1), 117.1 (1)0.165 (2), 0.155 (2), 0.156 (2), 0.166 (2)1.191 (3), 1.191 (3)176.6 (2), 177.5 (2)
51.585 (4), 1.590 (3)112.4 (2), 112.2 (2), 112.4 (2), 112.5 (2)116.8 (2), 117.1 (2), 117.2 (2), 117.3 (2)0.150 (3), 0.153 (3), 0.150 (3), 0.154 (3)1.187 (4), 1.183 (4)177.6 (3), 178.8 (3)
Angles are rounded where necessary to nearest 0.1°. Unless otherwise specified (see below), atom labels for columns 2–7, respectively, are: C1—C2 and C9—C10; angles at C1, C2, C9 and C10; angles at C3, C6, C11 and C14; deviations of atoms C3, C6, C11 and C14 from ring planes calculated without bridgehead atoms; bond lengths C17≡C18 and C19≡C20; angles C4—C17≡C18 and C—C19≡C20. Exceptions: for compound (I), there is only one triple bond; for compound (II), values are given for the first and second independent half molecule, whereby atom labels can be taken from Fig. 2.
C—H···π interactions (Å, °) top
CompoundHydrogen-bond No.D—H···AH···AD—H···ASymmetry code
(I)1C13—H13···Cg12.67165(1-x, -1/2+y, 1/2-z)
2C5—H5···Cg22.86131(-x, 1/2+y, 1/2-z)
3C8—H8···Cg32.82130(1-x, -1/2+y, 1/2-z)
(II)1C2—H2B···Cg22.78173(-x, -y, 1-z)
2C1—H1B···Cg42.80164(-x, 1-y, 1-z)
3C10'—H10'···Cg12.68116(1-x, -y, 1-z)
4C2'—H2'2···Cg33.06147(1-x, -y, 1-z)
(III)1C20—H20···Cg22.60119(y-x, 1-x, -1/3+z)
2C7—H7···Cg12.56158(-y, x-y, 1/3+z)
3C18—H18···Cg32.91173(1+y-x, 1-x, -1/3+z)
4C5—H5···Cg42.97131(y-x, -x, -1/3+z)
(IV)1C8—H8···Cg22.47155(-x, 1/2+y, 1-z)
2C10—H10B···Cg12.86170(1-x, -1/2+y, 1-z)
3C20—H20···Cg32.75139(1-x, -1/2+y, 2-z)
4C12—H12···Cg42.91127(-x, 1/2+y, 1-z)
(V)1C7—H7···Cg12.43157(1-x+y, 1-x, -1/3+z)
2C20—H20···Cg22.78149(1-x+y, 2-x, 2/3+z)
C—H distances are normalized to 1.08 Å (Steiner, 1998). Cg1 is the centroid of atoms C4/C5/C7/C8; Cg2 is the centroid of atoms C12/C13/C15/C16; Cg3 is the midpoint of C17≡C18; Cg4 is the midpoint of C19≡C20. Exceptions for compound (II): Cg2 is the centroid of atoms C4'/C5'/C7'/C8'; Cg3 is the midpoint of C9—C10; Cg4 is the midpoint of C9'—C10'. Exception for compound (V): Cg2 is the centroid of atoms C11/C12/C16 (see text). Hydrogen-bond numbers are shown in the packing diagrams.
 

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