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In 1,3,5-triphenyl­adamantane, C28H28, (I), and 1,3,5,7-tetra­phenyl­adamantane, C34H32, (II), the mol­ecules possess symmetries 3 and \overline{4}, and are situated across threefold and fourfold improper axes, respectively. The mol­ecules aggregate by means of extensive C-H...[pi] inter­actions. In (I), the pyramidal shape of the mol­ecules dicta­tes the formation of dimers through a `sixfold phenyl embrace' pattern. The dimers are linked to six close neighbors and constitute a primitive cubic net [H...[pi] = 2.95 (2) and 3.02 (2) Å]. Compound (II) is isomorphous with tetra­phenyl derivatives EPh4 of group 14 (E = C-Pb) and ionic salts [EPh4][BPh4] (E = P, As and Sb). The multiple C-H...[pi] inter­actions arrange the mol­ecules into chains, with a concerted action of CH (phen­yl) and CH2 (adamantane) groups as donors [H...[pi] = 3.15 (2) and 3.44 (2) Å, respectively]. The additional inter­actions with the methyl­ene groups (four per mol­ecule) are presumably important for explaining the high melting point and insolubility of (II) compared with the EPh4 analogs.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109013456/sf3104sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109013456/sf3104Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109013456/sf3104IIsup3.hkl
Contains datablock II

CCDC references: 735135; 735136

Comment top

Derivatives of adamantane attract a broad interdisciplinary interest as rigid molecular scaffolds for sustaining the structures of polyfunctional species, which find various applications in the chemistry of supramolecular systems, macromolecules, dendrimers and polymers. Thus adamantanes substituted in the four available bridgehead positions represent a family of rigid tetrahedral building blocks for the synthesis of hydrogen- and coordination-bonded framework polymers, and they are paradigmatic for the general principles of crystal design. In particular, the fivefold-interpenetrated diamondoid framework of 1,3,5,7-adamantanetetracarboxylate (Ermer, 1988) was of paramount significance for the development of crystal engineering and for stimulating many further efforts in this field (Moulton & Zaworotko, 2001).

In recent years, considerable attention has been focused on the synthesis and utilization of nanosized adamantane derivatives extended by a rigid 1,4-phenylene spacer (Reichert & Mathias, 1994). Following this methodology, such species as carboxylates (Kim et al., 2001), phosphonates (Jones et al., 2006) and sulfonates (Hoffart et al., 2005) were accessible by functionalization of phenyl-substituted adamantanes. However, supramolecular relations in such systems may be complicated, and close alignment of large shape-complementary tectons of high molecular symmetry could be prevalent for the crystal packing. This mitigates against the preparation of very open structures and makes the synthesis more difficult owing to the very poor solubility of the organic tectons. When exploring the evident potential of the extended adamantanes for the development of framework solids (Chen et al., 2000), the structures of the simpler phenyl derivatives are particularly interesting. The latter may be considered as prototypal building blocks, which assemble into framework structures through C—H···π interactions between the multiple phenyl functions (Nishio et al., 1998). These interactions clearly define the elegant structure of 1,3-diphenyladamantane, which contains supramolecular helices (Tukada & Mochizuki, 2003). Even more illustrative supramolecular relations may be anticipated for rigid tri- and tetrasubstituted molecules since multivalency of the building blocks and inherently defined and proper binding geometry are equally important factors for organization of the framework. Concerted C—H···π interactions are presumably responsible for the unusual properties of a tetraphenyl derivative, which is an exceptionally high-melting (melting point 690–692 K) and insoluble solid (Newman, 1972). We have examined polyfunctional 1,3,5-triphenyladamantane, (I), and 1,3,5,7-tetraphenyladamantane, (II), and report their structures here.

Molecules of (I) have 3 symmetry in the crystalline state, with the C4/H4 group lying on a threefold axis (Fig. 1), and therefore there is only one independent phenyl group. It adopts a nearly eclipsed conformation to one of the C—C bonds of the adamantane carrier [e.g. C2i—C1—C5—C6 = -6.71 (16)°; symmetry code: (i) -x + y, -x + 1, z; see also Table 1], similar to the conformation in 1,3-diphenyladamantane (Tukada & Mochizuki, 2003).

The most peculiar feature of the crystal packing of (I) is a pair-wise association of the molecules, leading to the formation of a tight `supramolecular cube' (Fig. 2). The dimer possesses 3 symmetry and it is supported by very characteristic C—H···π interactions between the six phenyl rings. Each pair of interacting rings adopts an interplanar angle of 73.55 (4)°. These weak interactions are directional and the H atom is situated almost exactly above the neighboring ring centroid [symmetry code: (iii) y - 1/3, -x + y+1/3, -z + 1/3], with an angle of the H···π axis to the plane of the aromatic ring of 83.1 (10)° (Table 2). Such a mode of shape-complementary association, often recognized as a `sixfold phenyl embrace', is characteristic for pyramidal triphenyl-substituted molecules, and it was observed for several triphenylphosphines (Scudder & Dance 2000), triphenylgermanium halogenides (Prince et al., 2002) and even for charged species, such as triphenyltelluronium cations (Närhi et al., 2004). A distance of 6.136 (2) Å between the centroids of adamantane frameworks indicates very tight coupling of the molecules constituting the dimer.

One additional group, C10/H10, is involved in an interdimer C—H···π interaction, which is comparable in strength to that above, with an H···πvi separation of 2.95 (2) Å [symmetry code: (vi) y, -x + y, -z; Fig. 3]. In total, six phenyl groups of the dimer provide connections to six closest neighbors. Thus the entire structure is very simple, and it may be regarded as a primitive cubic lattice with the supramolecular dimers as the net points. Alternatively, the structure may be described as a three-dimensional C—H···π phenyl stack of NbO topology, with bulky adamantane groups populating the framework cages.

Molecules of (II) have 4 symmetry in the crystal; they are situated on the improper fourfold axis passing through atoms C2 and C2i [symmetry code: (i) y, -x, z; Fig. 4], and display the expected tetrahedral geometry (Table 3) with the following angles subtended by the Cg—Ph vectors [Cg is the centroid of the adamantane group at (0,0,0)]: C4—Cg—C4ii = 106.74 (6)° and C4—Cg—C4iii = 110.86 (6)° [symmetry codes: (ii) -x, -y, z; (iii) -y, x, -z].

The structure is isomorphous with a family of tetraphenyl derivatives EPh4 of group 14 elements (E = C, Si, Ge, Sn and Pb; Claborn et al., 2002) and also with tetraphenylosmium(IV) (Stavropoulos et al., 1987). All the members of this family uniformly crystallize in the tetragonal space group P421c with very similar unit-cell parameters. Ionic salts of the type [EPh4][BPh4] (E = P, As and Sb) also adopt such a structure, while crystallizing in a supercell of P421c with ordered positions of the ionic counterparts (Lloyd & Brock, 1997). Thus (II) is a simple expanded analog of the above tetrahedral molecules, with a Cg···C(Ph) separation [3.1006 (16) Å] formally corresponding to the E—C bonds of EPh4. The structure of (II) is organized by means of very extensive C—H···π interactions, leading to a packing index of 70.4. Although the value resides exactly at the mid-point of the 65–75% range expected for organic solids (Dunitz, 1995), it only slightly exceeds the parameters for the related EPh4 structures, e.g. 69.3 for E = Si and 69.9 for E = C (Claborn et al., 2002). In this context, it is interesting to query why these materials are so different in view of their properties, since (II) possesses an exceptionally low solubility in all common solvents and also an incomparably high melting point.

The primary supramolecular pattern is a one-dimensional chain, running along the c axis, in which the molecules are stacked like the pieces of a puzzle, yielding concerted cycles of four edge-to-face phenyl–phenyl interactions [C5—H5···πv = 3.15 (2) Å, symmetry code: (v) y, -x, -z + 1; Figs. 5 and 6]. In the chain, the molecules of (II) are related by translation along the c-axis direction [7.2032 (6) Å] and are packed even more closely than in tetraphenylmethane [7.287 (2) Å; Robbins et al., 1975]. The interchain bonding occurs by means of double C6/H6,C7/H7···πvi [symmetry code: (vi) y + 1/2, x - 1/2, z + 1/2] interactions, yielding a typical herringbone arrangement of the phenyl groups (Fig. 6 and Table 4). These interactions are consistent with those in tetraphenyllead [H···π = 3.28 Å; C···π = 3.949 and 3.958 Å; Preut & Huber, 1993] and are somewhat stronger than those in tetraphenylmethane (H···π = 3.43 and 3.73 Å; C···π = 4.166 and 4.306 Å).

The set of C—H···π interactions affords a three-dimensional stack (Fig. 7) and this motif is common for all the present family. The most notable feature of the packing, which is applicable to adamantane (II) only, is a set of directional C2—H2···πv contacts with the methylene group [H···π = 3.44 (2) Å and C—H···π = 177.6 (15)°; Fig. 5]. Such distal interactions are unlikely to be attributed to hydrogen bonding and presumably they originate in very weak dispersion forces. However, the cooperative effect of four such geometrically favored interactions per molecule of (II) may be significant (Suezawa et al., 2001). This contributes to the overall energy of the supramolecular structure as an additional force compared with the isomorphous tetraphenyl derivatives of group 14. The fact that the concerted interactions C5—H5—πv and C2—H2—πv facilitate the densest interaction between the molecules may be applicable for other phenyl-substituted adamantanes as a special type of `supramolecular synthon' organizing molecules in the solid state. In (I), such interactions are negated by the formation of the more prevalent `sixfold phenyl embrace' pattern and there are no close contacts with the methylene group. However, the aforementioned interactions are relevant for 1,3-diphenyladamantane [C—H···π = 3.39 Å (Ph) and 3.52 Å (CH2); Tukada & Mochizuki, 2003], 1,3,5,7-tetrakis(4-phosphonophenyl)adamantane [C—H···π = 3.28 Å (Ph) and 3.52 Å (CH2); Jones et al., 2006] and 1,3,5,7-tetrakis(4-ethynylphenyl)adamantane [C—H···π = 3.55 Å (Ph) and 3.52 Å (CH2); Galoppini & Gilardi, 1999].

In brief, the title structures are important as general and basic prototypes for intermolecular interactions between extended polyaryl-substituted adamantanes, which are currently arousing growing interest as molecular scaffolds in supramolecular chemistry. A comparison of (II) and a series of isomorphous tetraphenyl-substituted molecules allows the postulation of the significance of the weakest forces, such as methylene–π interactions.

Related literature top

For related literature, see: Chen et al. (2000); Claborn et al. (2002); Dunitz (1995); Ermer (1988); Galoppini & Gilardi (1999); Hoffart et al. (2005); Jones et al. (2006); Kim et al. (2001); Lloyd & Brock (1997); Moulton & Zaworotko (2001); Narhi et al. (2004); Newman (1972); Nishio et al. (1998); Preut & Huber (1993); Prince et al. (2002); Reichert & Mathias (1994); Robbins et al. (1975); Scudder & Dance (2000); Stavropoulos et al. (1987); Suezawa et al. (2001).

Experimental top

Compounds (I) and (II) were synthesized in a 15–20 g scale by Friedel–Crafts reaction of 1-bromoadamantane and benzene in the presence of tert-butyl bromide using procedure of Newman (1972). Crude (I) was repeatedly washed with ether to remove traces of mono- and diphenyladamantanes and then crystallized from hot toluene as large colorless prisms. Compound (II), which is insoluble in all common solvents, was purified from partially phenylated adamantanes by continuous extraction with hot toluene in a Soxhlet apparatus. For crystallization, the resulting colorless powder (15 mg) and xylene (8 ml, mixture of isomers) were sealed in a Pyrex tube and heated at 473 K for 2 d. Slow cooling to room temperature over a period of 70 h provides small colorless prisms of (II) in a quantitative yield.

Refinement top

For (II), the Friedel-related reflections were merged. For both structures, all the H atoms were found in intermediate difference Fourier maps and were refined fully with isotropic displacement parameters [for (I), C—H (phenyl) = 0.957 (16)–0.986 (15) Å and C—H (aliphatic) = 1.006 (14)–1.034(14) Å; for (II) C—H (phenyl) = 0.94 (2)–1.00 (2) Å and C—H (aliphatic) = 0.984 (19)–1.009 (18) Å].

Computing details top

Data collection: SMART-NT (Bruker, 1998) for (I); IPDS Software (Stoe & Cie, 2000) for (II). Cell refinement: SAINT-NT (Bruker, 1999) for (I); IPDS Software (Stoe & Cie, 2000) for (II). Data reduction: SAINT-NT (Bruker, 1999) for (I); IPDS Software (Stoe & Cie, 2000) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Diamond (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. The threefold axis lies along the C4—H4 direction. [Symmetry codes: (i) -x + y, -x + 1, z; (ii) -y + 1, x - y + 1, z.]
[Figure 2] Fig. 2. The supramolecular cube formed by two molecules of (I) by means of concerted C—H···π interactions (shown as dashed lines) of six phenyl groups. Atoms C4 and C4v are situated on the improper threefold axis. [Symmetry codes: (iii) y - 1/3, -x + y + 1/3, -z + 1/3; (iv) x - y + 2/3, x + 1/3, -z + 1/3; (v) -x + 2/3, -y + 4/3, -z + 1/3.]
[Figure 3] Fig. 3. A view of the structure of (I), showing C—H···π interactions (dashed lines) between the neighboring dimeric supramolecular entities. The same connectivity occurs also in the direction which is orthogonal to the plane of the drawing. [Symmetry code: (vi) y, -x + y, -z.]
[Figure 4] Fig. 4. The structure of (II), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 35% probability level. The improper fourfold axis passes through atoms C2 and C2i. [Symmetry codes: (i) y, -x, -z; (ii) -x, -y, z; (iii) -y, x, -z.]
[Figure 5] Fig. 5. Multiple C—H···π interactions between pairs of molecules of (II), which lead to the formation of one-dimensional chains. Note the concerted interaction employing pairs of aromatic and aliphatic CH groups. [Symmetry codes: (iv) -y, x, 1 - z; (v) y, -x, -z + 1.]
[Figure 6] Fig. 6. A view of the structure of (II), showing chains running along the c-axis direction. The C—H···π interactions between the chains produce a characteristic herringbone phenyl motif (which is shown with bold shaded bonds). [Symmetry codes: (v) y, -x, -z + 1; (vi) y + 1/2, x - 1/2, z + 1/2.]
[Figure 7] Fig. 7. Projection of the structure of (II) on to the ab plane. The dashed lines indicate C—H···π interactions.
(I) 1,3,5-Triphenyladamantane top
Crystal data top
C28H28Dx = 1.248 Mg m3
Mr = 364.50Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 3995 reflections
a = 13.0230 (4) Åθ = 2.1–26.6°
c = 19.8046 (13) ŵ = 0.07 mm1
V = 2908.8 (2) Å3T = 173 K
Z = 6Prism, colorless
F(000) = 11760.24 × 0.23 × 0.16 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
1345 independent reflections
Radiation source: fine-focus sealed tube1039 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 26.6°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1615
Tmin = 0.978, Tmax = 0.989k = 169
3995 measured reflectionsl = 2024
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)] = 0.039Hydrogen site location: difference Fourier map
wR(F2) = 0.103All H-atom parameters refined
S = 1.04 w = 1/[σ2(Fo2) + (0.0478P)2 + 1.6227P]
where P = (Fo2 + 2Fc2)/3
1345 reflections(Δ/σ)max < 0.001
123 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C28H28Z = 6
Mr = 364.50Mo Kα radiation
Trigonal, R3µ = 0.07 mm1
a = 13.0230 (4) ÅT = 173 K
c = 19.8046 (13) Å0.24 × 0.23 × 0.16 mm
V = 2908.8 (2) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer
1345 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1039 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.989Rint = 0.027
3995 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.103All H-atom parameters refined
S = 1.04Δρmax = 0.20 e Å3
1345 reflectionsΔρmin = 0.20 e Å3
123 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
C10.23727 (11)0.54185 (11)0.03772 (6)0.0197 (3)
C20.36207 (11)0.57327 (11)0.06270 (6)0.0194 (3)
C30.23791 (12)0.54424 (12)0.04037 (6)0.0229 (3)
C40.33330.66670.06534 (11)0.0229 (5)
C50.14844 (11)0.41950 (11)0.06478 (6)0.0204 (3)
C60.06223 (11)0.40124 (12)0.11271 (6)0.0232 (3)
C70.01017 (12)0.28992 (12)0.14072 (7)0.0273 (3)
C80.00033 (12)0.19410 (12)0.12051 (7)0.0275 (3)
C90.08318 (12)0.21003 (12)0.07195 (7)0.0260 (3)
C100.15614 (12)0.32061 (12)0.04463 (7)0.0242 (3)
H2A0.3615 (11)0.5722 (11)0.1135 (7)0.022 (4)*
H2B0.3831 (12)0.5109 (12)0.0456 (7)0.024 (3)*
H3A0.2542 (12)0.4803 (13)0.0592 (7)0.027 (4)*
H3B0.1559 (13)0.5255 (12)0.0568 (7)0.025 (4)*
H40.33330.66670.1161 (12)0.022 (6)*
H60.0525 (12)0.4657 (13)0.1282 (7)0.025 (4)*
H70.0680 (13)0.2811 (12)0.1751 (7)0.028 (4)*
H80.0503 (13)0.1156 (14)0.1410 (7)0.033 (4)*
H90.0922 (12)0.1449 (13)0.0574 (7)0.026 (4)*
H100.2155 (12)0.3292 (12)0.0115 (7)0.025 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0204 (7)0.0200 (6)0.0183 (6)0.0097 (5)0.0010 (5)0.0010 (5)
C20.0211 (7)0.0199 (7)0.0176 (6)0.0104 (5)0.0001 (5)0.0001 (5)
C30.0251 (7)0.0240 (7)0.0193 (7)0.0120 (6)0.0021 (5)0.0031 (5)
C40.0272 (8)0.0272 (8)0.0142 (10)0.0136 (4)0.0000.000
C50.0191 (7)0.0210 (7)0.0195 (6)0.0089 (6)0.0046 (5)0.0019 (5)
C60.0228 (7)0.0208 (7)0.0246 (7)0.0099 (6)0.0008 (5)0.0018 (5)
C70.0234 (7)0.0269 (7)0.0267 (7)0.0090 (6)0.0022 (6)0.0012 (6)
C80.0274 (7)0.0203 (7)0.0280 (7)0.0069 (6)0.0032 (6)0.0034 (6)
C90.0296 (8)0.0213 (7)0.0284 (7)0.0138 (6)0.0061 (6)0.0035 (6)
C100.0239 (7)0.0245 (7)0.0244 (7)0.0121 (6)0.0011 (6)0.0027 (5)
Geometric parameters (Å, º) top
C1—C51.5236 (17)C5—C101.3989 (17)
C1—C2i1.5331 (17)C6—C71.3897 (19)
C1—C21.5455 (17)C6—H60.960 (14)
C1—C31.5467 (17)C7—C81.3809 (19)
C2—H2A1.006 (14)C7—H70.979 (15)
C2—H2B1.034 (14)C8—C91.381 (2)
C3—C41.5329 (15)C8—H80.986 (15)
C3—H3A1.027 (14)C9—C101.3788 (19)
C3—H3B1.022 (14)C9—H90.957 (16)
C4—H41.01 (2)C10—H100.976 (15)
C5—C61.3967 (17)
C5—C1—C2i112.20 (10)C3i—C4—H4108.82 (9)
C5—C1—C2108.20 (10)C3—C4—H4108.82 (9)
C2i—C1—C2108.26 (11)C3ii—C4—H4108.82 (9)
C5—C1—C3111.49 (10)C6—C5—C10117.30 (12)
C2i—C1—C3107.91 (10)C6—C5—C1122.85 (11)
C2—C1—C3108.68 (10)C10—C5—C1119.73 (11)
C1ii—C2—C1112.09 (11)C7—C6—C5121.14 (12)
C1ii—C2—H2A109.5 (7)C7—C6—H6117.9 (8)
C1—C2—H2A108.5 (8)C5—C6—H6121.0 (8)
C1ii—C2—H2B108.1 (7)C8—C7—C6120.33 (13)
C1—C2—H2B110.1 (7)C8—C7—H7120.9 (8)
H2A—C2—H2B108.6 (10)C6—C7—H7118.7 (8)
C4—C3—C1109.69 (12)C7—C8—C9119.26 (13)
C4—C3—H3A109.7 (8)C7—C8—H8120.0 (9)
C1—C3—H3A110.4 (8)C9—C8—H8120.7 (9)
C4—C3—H3B110.6 (7)C10—C9—C8120.58 (13)
C1—C3—H3B108.6 (8)C10—C9—H9118.8 (8)
H3A—C3—H3B107.8 (11)C8—C9—H9120.6 (8)
C3i—C4—C3110.11 (9)C9—C10—C5121.35 (12)
C3i—C4—C3ii110.11 (9)C9—C10—H10118.4 (8)
C3—C4—C3ii110.11 (9)C5—C10—H10120.2 (8)
C5—C1—C2—C1ii179.82 (8)C2i—C1—C5—C10177.26 (11)
C2i—C1—C2—C1ii58.36 (16)C2—C1—C5—C1063.37 (14)
C3—C1—C2—C1ii58.60 (13)C3—C1—C5—C1056.10 (15)
C5—C1—C3—C4176.75 (9)C10—C5—C6—C72.05 (18)
C2i—C1—C3—C459.61 (12)C1—C5—C6—C7174.07 (11)
C2—C1—C3—C457.57 (12)C5—C6—C7—C81.3 (2)
C1—C3—C4—C3i61.40 (13)C6—C7—C8—C90.3 (2)
C1—C3—C4—C3ii60.21 (13)C7—C8—C9—C101.07 (19)
C2i—C1—C5—C66.71 (16)C8—C9—C10—C50.27 (19)
C2—C1—C5—C6112.66 (13)C6—C5—C10—C91.27 (18)
C3—C1—C5—C6127.88 (13)C1—C5—C10—C9174.98 (11)
Symmetry codes: (i) x+y, x+1, z; (ii) y+1, xy+1, z.
(II) 1,3,5,7-Tetraphenyladamantane top
Crystal data top
C34H32Dx = 1.235 Mg m3
Mr = 440.60Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421cCell parameters from 4632 reflections
a = 12.8260 (11) Åθ = 3.2–28.0°
c = 7.2032 (6) ŵ = 0.07 mm1
V = 1184.97 (17) Å3T = 213 K
Z = 2Prism, colorless
F(000) = 4720.26 × 0.23 × 0.22 mm
Data collection top
Stoe IPDS
diffractometer
643 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 28.0°, θmin = 3.2°
ϕ oscillation scansh = 167
4632 measured reflectionsk = 1616
822 independent reflectionsl = 88
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: difference Fourier map
wR(F2) = 0.084All H-atom parameters refined
S = 0.92 w = 1/[σ2(Fo2) + (0.0621P)2]
where P = (Fo2 + 2Fc2)/3
822 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C34H32Z = 2
Mr = 440.60Mo Kα radiation
Tetragonal, P421cµ = 0.07 mm1
a = 12.8260 (11) ÅT = 213 K
c = 7.2032 (6) Å0.26 × 0.23 × 0.22 mm
V = 1184.97 (17) Å3
Data collection top
Stoe IPDS
diffractometer
643 reflections with I > 2σ(I)
4632 measured reflectionsRint = 0.028
822 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.084All H-atom parameters refined
S = 0.92Δρmax = 0.24 e Å3
822 reflectionsΔρmin = 0.14 e Å3
110 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
C10.09921 (11)0.00935 (12)0.1255 (2)0.0206 (3)
C20.00000.00000.2467 (3)0.0208 (4)
C30.10631 (12)0.08913 (11)0.0023 (2)0.0214 (3)
C40.19290 (11)0.02061 (13)0.2568 (2)0.0243 (4)
C50.19726 (14)0.10637 (15)0.3787 (3)0.0321 (4)
C60.27811 (15)0.11675 (17)0.5066 (3)0.0411 (5)
C70.35595 (16)0.04211 (19)0.5169 (3)0.0462 (5)
C80.35344 (15)0.04244 (18)0.3983 (3)0.0423 (5)
C90.27237 (12)0.05320 (15)0.2690 (3)0.0317 (4)
H20.0065 (17)0.0629 (14)0.325 (3)0.031 (5)*
H3A0.1715 (13)0.0861 (13)0.076 (3)0.017 (4)*
H3B0.1113 (14)0.1522 (15)0.080 (3)0.022 (4)*
H50.1415 (16)0.1612 (15)0.377 (3)0.032 (5)*
H60.2775 (16)0.1757 (17)0.584 (3)0.044 (6)*
H70.4126 (18)0.0507 (17)0.600 (4)0.052 (7)*
H80.409 (2)0.0955 (19)0.404 (4)0.054 (6)*
H90.2703 (16)0.1148 (15)0.187 (3)0.036 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0214 (7)0.0243 (7)0.0160 (7)0.0012 (6)0.0013 (6)0.0004 (6)
C20.0235 (10)0.0221 (10)0.0168 (10)0.0006 (9)0.0000.000
C30.0223 (7)0.0236 (7)0.0184 (8)0.0017 (5)0.0000 (7)0.0008 (7)
C40.0222 (7)0.0328 (8)0.0177 (9)0.0049 (6)0.0007 (6)0.0042 (7)
C50.0293 (8)0.0401 (10)0.0270 (10)0.0066 (7)0.0015 (7)0.0017 (8)
C60.0387 (10)0.0568 (12)0.0278 (10)0.0168 (9)0.0036 (9)0.0072 (11)
C70.0312 (9)0.0751 (15)0.0322 (11)0.0129 (10)0.0115 (9)0.0069 (11)
C80.0265 (9)0.0609 (13)0.0397 (12)0.0003 (8)0.0079 (9)0.0108 (11)
C90.0256 (8)0.0408 (10)0.0287 (10)0.0008 (7)0.0004 (8)0.0050 (8)
Geometric parameters (Å, º) top
C1—C41.536 (2)C5—C61.394 (3)
C1—C31.546 (2)C5—H51.00 (2)
C1—C21.548 (2)C6—C71.385 (3)
C1—C3i1.552 (2)C6—H60.94 (2)
C2—H20.987 (19)C7—C81.381 (3)
C3—H3A1.009 (18)C7—H70.95 (2)
C3—H3B0.984 (19)C8—C91.403 (3)
C4—C91.394 (2)C8—H80.99 (3)
C4—C51.409 (3)C9—H90.99 (2)
C4—C1—C3112.59 (12)C5—C4—C1119.24 (13)
C4—C1—C2107.63 (13)C6—C5—C4121.09 (18)
C3—C1—C2107.98 (11)C6—C5—H5118.2 (12)
C4—C1—C3i110.79 (12)C4—C5—H5120.8 (12)
C3—C1—C3i108.62 (11)C7—C6—C5120.4 (2)
C2—C1—C3i109.14 (11)C7—C6—H6122.0 (13)
C1ii—C2—C1111.33 (19)C5—C6—H6117.6 (13)
C1ii—C2—H2108.4 (12)C8—C7—C6119.53 (19)
C1—C2—H2109.1 (13)C8—C7—H7119.9 (14)
C1—C3—C1iii111.16 (14)C6—C7—H7120.5 (14)
C1—C3—H3A109.7 (10)C7—C8—C9120.4 (2)
C1iii—C3—H3A109.7 (10)C7—C8—H8120.1 (14)
C1—C3—H3B110.5 (11)C9—C8—H8119.6 (15)
C1iii—C3—H3B108.6 (10)C4—C9—C8121.12 (19)
H3A—C3—H3B107.1 (14)C4—C9—H9119.1 (12)
C9—C4—C5117.53 (16)C8—C9—H9119.8 (12)
C9—C4—C1123.15 (15)
C4—C1—C2—C1ii178.79 (13)C2—C1—C4—C560.75 (17)
C3—C1—C2—C1ii59.42 (10)C3i—C1—C4—C558.51 (19)
C3i—C1—C2—C1ii58.49 (10)C9—C4—C5—C60.0 (3)
C4—C1—C3—C1iii178.78 (14)C1—C4—C5—C6176.72 (17)
C2—C1—C3—C1iii60.10 (15)C4—C5—C6—C70.3 (3)
C3i—C1—C3—C1iii58.14 (12)C5—C6—C7—C80.5 (3)
C3—C1—C4—C93.1 (2)C6—C7—C8—C90.4 (3)
C2—C1—C4—C9115.82 (16)C5—C4—C9—C80.2 (3)
C3i—C1—C4—C9124.92 (17)C1—C4—C9—C8176.43 (16)
C3—C1—C4—C5179.64 (15)C7—C8—C9—C40.0 (3)
Symmetry codes: (i) y, x, z; (ii) x, y, z; (iii) y, x, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC28H28C34H32
Mr364.50440.60
Crystal system, space groupTrigonal, R3Tetragonal, P421c
Temperature (K)173213
a, b, c (Å)13.0230 (4), 13.0230 (4), 19.8046 (13)12.8260 (11), 12.8260 (11), 7.2032 (6)
α, β, γ (°)90, 90, 12090, 90, 90
V3)2908.8 (2)1184.97 (17)
Z62
Radiation typeMo KαMo Kα
µ (mm1)0.070.07
Crystal size (mm)0.24 × 0.23 × 0.160.26 × 0.23 × 0.22
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Stoe IPDS
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.978, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections
3995, 1345, 1039 4632, 822, 643
Rint0.0270.028
(sin θ/λ)max1)0.6300.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.103, 1.04 0.035, 0.084, 0.92
No. of reflections1345822
No. of parameters123110
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.20, 0.200.24, 0.14

Computer programs: SMART-NT (Bruker, 1998), IPDS Software (Stoe & Cie, 2000), SAINT-NT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Diamond (Brandenburg, 1999), WinGX (Farrugia, 1999).

Selected torsion angles (º) for (I) top
C2i—C1—C5—C10177.26 (11)C3—C1—C5—C1056.10 (15)
C2—C1—C5—C1063.37 (14)
Symmetry code: (i) x+y, x+1, z.
Geometry of C—H···π interactions (Å, °) for (I) top
ContactC···πH···πC—H···πϕa
C6—H6···πiii3.8598 (14)3.02 (2)147.0 (10)83.1 (10)
C10—H10···πvi3.8389 (13)2.95 (2)152.0 (10)81.0 (10)
Symmetry codes: (iii) y-1/3, -x+y+1/3, -z+1/3; (vi) y, -x+y, -z. Note: (a) ϕ is the angle of the H···π axis to the plane of the phenyl ring.
Selected torsion angles (º) for (II) top
C3—C1—C4—C5179.64 (15)C3i—C1—C4—C558.51 (19)
C2—C1—C4—C560.75 (17)
Symmetry code: (i) y, x, z.
Geometry of C—H···π interactions (Å, °) for (II). top
ContactC···πH···πC—H···πϕb
C5—H5···πv4.0164 (19)3.15 (2)145.1 (16)76.3 (18)
C2—H2···πv4.4207 (14)3.44 (2)177.6 (15)61.3 (16)
C6—H6···πvi3.926 (2)3.34 (2)122.3 (15)66.4 (16)
C7—H7···πvi3.836 (2)3.13 (2)132.5 (16)71.0 (18)
Symmetry codes: (v) y, -x, -z+1; (vi) y+1/2, x-1/2, z+1/2. Note: (b) ϕ is the angle of the H···π axis to the plane of the phenyl ring.
 

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