A new polymorph and two inclusion compounds of 9,9′-spiro­bifluorene

Douthwaite, R.E.; Taylor, A.; Whitwood, A.C.

doi:10.1107/S0108270105009479

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 5| May 2005| Pages o328-o331

doi:10.1107/S0108270105009479

A new polymorph and two inclusion compounds of 9,9′-spirobifluorene

Richard E. Douthwaite,^a ^* Andrew Taylor ^a and Adrian C. Whitwood ^a

^aDepartment of Chemistry, University of York, Heslington, York YO10 5DD, England
^*Correspondence e-mail: red4@york.ac.uk

(Received 9 February 2005; accepted 24 March 2005; online 30 April 2005)

Two new inclusion compounds of 9,9′-spirobifluorene (SBF) incorporating benzene [(I), C₂₅H₁₆·C₆H₆] and biphenyl [(II), C₂₅H₁₆·C₁₂H₁₀], and a new polymorph of SBF [(III), C₂₅H₁₆] are reported. All three exhibit C—H⋯π(arene) hydrogen bonds between adjacent SBF molecules. Compound (II) also contains biphenyl C—H to SBF π-arene interactions. Collectively, hydrogen bonding gives rise to a chain and a layered motif in compounds (I) and (II), respectively.

Comment

The synthesis of 9,9′-spirobifluorene (SBF) was first reported by Clarkson & Gomberg in 1930 , and the first single-crystal structure determination was reported four decades later by Schenk (1972 ). Exhibiting D_2d point symmetry, SBF is an unusual structural motif, which has prompted its use in molecular recognition (Alcazar & Diederich 1992 ) and catalytic applications (Poriel et al., 2003 ), and its incorporation into materials that exhibit unusual optoelectronic properties (Wong et al., 2002 ). We have recently been interested in using SBF as a structural motif in molecular solids and report here the structures of two inclusion compounds, (I) and (II), incorporating benzene and biphenyl, respectively. In the course of our study, we also determined the structure of a new polymorph of SBF, (III).

One of our initial aims had been to prepare co-crystals of SBF and fluorinated aromatics, including hexafluorobenzene, perfluoronaphthalene and perfluorobiphenyl, with the intention of investigating supramolecular structures akin to those derived from co-crystallization between planar hydro- and fluoroaromatics. However, in no case did co-crystals between SBF and fluoroaromatics result. We tentatively assigned this observation to repulsive (steric) interactions between SBF and fluoroaromatics, preventing the attractive molecular electric quadrupole moment interactions that result in parallel stacking in many perhydro/perfluoro aromatic co-crystals (Williams, 1993 ). However, we rationalized that it may be possible to prepare inclusion compounds incorporating SBF and hydroaromatics, because the relative quadrupole moments would give rise to attractive edge-to-face electrostatic interactions (Lowden & Chandler 1974 ; Shi & Bartell 1988 ) that could be sterically accessible for SBF. Indeed, co-crystallization of SBF and the hydroaromatics benzene and biphenyl gave the inclusion compounds (I) and (II), respectively, which exhibit a range of edge-to face C—H⋯π(arene) hydrogen bonds between the aromatic moieties.

The bond lengths and angles of the constituent molecules of (I)–(III) are not exceptional. Examination of the packing diagrams reveals structural motifs resulting from C—H⋯π(arene) interactions and, based on the C—H⋯A (A = acceptor) angles and H⋯A bond lengths, these are considered here as weak hydrogen bonds.

Compound (I) contains one molecule of SBF and one molecule of benzene in the asymmetric unit (Fig. 1). Hydrogen bonds are present between adjacent SBF molecules, resulting in an infinite chain motif (Fig. 2). The benzene molecules do not participate in any directional bonding, and there is no directional bonding nor any short contacts between the chains. Hydrogen-bonding details are shown in Fig. 2, and the distance between atom H4 in the molecule at (x, y, z) and Cg1 (the centroid of the C20–C25 benzene ring) in the symmetry-related molecule at (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z) is 2.67 Å (Table 1).

Compound (II) contains one molecule of SBF and one molecule of biphenyl in the asymmetric unit (Fig. 3) and exhibits several C—H⋯π(arene) hydrogen-bonding motifs (Fig. 4), which collectively result in a layered structure with planes parallel to the (011) direction (Table 2). In contrast with (I), adjacent SBF molecules at (x, y, z) and (1 − x, 1 − y, 2 − z) are connected via a pair of hydrogen bonds between atom H16 and the C2–C7 benzene ring (Fig. 4), with a H16⋯Cg2 (ring centroid of the C2–C7 ring) distance of 2.65 Å. Biphenyl distance of molecules connect SBF pairs via a series of C—H⋯π-arene interactions. Atom H29 in a biphenyl molecule at (1 − x, 2 − y, 1 − z) interacts in an asymmetric hydrogen bond with the arene moiety C8–C13 (centroid Cg3) of an SBF molecule at (x, y, z). In addition, biphenyl–SBF hydrogen bonding is present between atoms H3 and C27 of an SBF molecule at (x, y, z), and atoms C22 and H28, respectively, of a biphenyl molecule at (x, y, z), connecting pairs of SBF molecules into a chain motif. The chains can then be interpreted as precursors to a layer in the [011] plane via interaction of SBF and biphenyl atoms.

Compound (III) contains two molecules of SBF in the asymmetric unit (Fig. 5), in contrast to a single molecule observed by Schenk (1971), which aggregates through very short intermolecular C—C distances (3.22, 3.35 and 3.45 Å) from edge–edge π-interactions between phenyl groups. The new polymorph, (III), does not exhibit short C—C contacts, but SBF molecules of (III) participate in C—H⋯π interactions to give centrosymmetric SBF dimers (Fig. 6), with a H11A⋯Cg4 distance of 2.59 Å [Cg4 is the centroid of the C20A–C25A ring at (1-x, -y, 1-z); C11A—H11A = 0.95 Å, C11A⋯Cg4 = 3.495 Å and C11A—H11A⋯Cg4 = 160°]. Examination of the packing shows that layers of discrete SBF dimers are present parallel to the bc plane, separated by layers of SBF molecules that do not exhibit directional bonding (Fig. 6). In our study, all other solvent mixtures that we examined led to crystallization of the polymorph identified by Schenk (1971). This suggests that polymorph (III) is possibly metastable with respect to that described by Schenk (1971).

It is anticipated that the weak hydrogen-bonding motifs observed in compounds (I)–(III) are likely to be an important factor in determining the structures of molecular solids derived from SBF.

Figure 1
A view of the asymmetric unit of (I)

, showing the atom-numbering scheme and 50% probability displacement ellipsoids.

Figure 2
The hydrogen bonding in (I)

. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) and (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z), respectively. Inset: a view down the C4—H4 bond axis, showing the relative π-arene position.

Figure 3
A view of the asymmetric unit of (II)

, showing the atom-numbering scheme and 50% probability displacement ellipsoids.

Figure 4
The hydrogen bonding in (II)

. Atoms marked with an asterisk (*), a hash (#) or a prime (′) are at the symmetry positions (1 − x, 1 − y, 2 − z), (1 − x, 2 − y, −z) and (−1 + x, y, z), respectively.

Figure 5
A view of the asymmetric unit of (III)

, showing both SBF moieties and the atom-numbering scheme, with 50% probability displacement ellipsoids.

Figure 6
The hydrogen bonding in (III)

. Atoms marked with an asterisk (*), a hash (#) or a prime (′) are at the symmetry positions (1 − x, −y, 1 − z), (x, 1 + y, z) and (1 − x, 1 − y, 1 − z), respectively.

Experimental

Single crystals of (I)–(III) were grown by slow evaporation of SBF (20 mg) dissolved in benzene for (I), in pentane containing 1 equivalent of biphenyl for (II), and in a 1:1 mixture of hexafluorobenzene and dichloromethane for (III). All compounds melted in the range 470–473 K.

Compound (I)

Crystal data

C₂₅H₁₆·C₆H₆
M_r = 394.49
Monoclinic, P 2₁ /n
a = 10.7900 (6) Å
b = 18.4004 (10) Å
c = 10.8403 (6) Å
β = 92.8770 (10)°
V = 2149.5 (2) Å³
Z = 4
D_x = 1.219 Mg m⁻³
Mo Kα radiation
Cell parameters from 4471 reflections
θ = 2.2–27.4°
μ = 0.07 mm⁻¹
T = 115 (2) K
Block, colourless
0.2 × 0.2 × 0.2 mm

Data collection

Bruker SMART CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Bruker, 2000 )T_min = 0.893, T_max = 0.990
14 724 measured reflections
4921 independent reflections
3949 reflections with I > 2σ(I)
R_int = 0.024
θ_max = 27.5°
h = −14 → 13
k = −23 → 23
l = −14 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 1.02
4921 reflections
280 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.056P)² + 0.5085P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °) for (I)

Cg1 is the centroid of the C20–C25 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cg1ⁱ	0.95	2.67	3.61	172
C11—H11⋯C16ⁱⁱ	0.95	2.74	3.6196 (18)	154
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Compound (II)

Crystal data

C₂₅H₁₆·C₁₂H₁₀
M_r = 470.58
Triclinic, $[P \overline 1]$
a = 9.774 (4) Å
b = 11.427 (4) Å
c = 13.075 (5) Å
α = 71.339 (8)°
β = 83.106 (9)°
γ = 67.030 (7)°
V = 1273.8 (8) Å³
Z = 2
D_x = 1.227 Mg m⁻³
Mo Kα radiation
Cell parameters from 944 reflections
θ = 2.4–24.2°
μ = 0.07 mm⁻¹
T = 115 (2) K
Block, colourless
0.14 × 0.11 × 0.04 mm

Data collection

Bruker SMART CCD area detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Bruker, 2000)T_min = 0.985, T_max = 0.998
6971 measured reflections
4476 independent reflections
2416 reflections with I > 2σ(I)
R_int = 0.050
θ_max = 25.1°
h = −11 → 6
k = −13 → 13
l = −15 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.248
S = 0.92
4476 reflections
335 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.022 (6)

Table 2
Hydrogen-bond geometry (Å, °) for (II)

Cg2 is the centroid of the C2–C7 ring and Cg3 is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯Cg2ⁱ	0.95	2.65	3.57	162
C29—H29⋯Cg3ⁱⁱ	0.95	2.63	3.56	163
C3—H3⋯C27	0.95	2.80	3.692 (5)	157
C28—H28⋯C22	0.95	2.84	3.658 (6)	147
C12—H12⋯C31ⁱⁱⁱ	0.95	2.87	3.783 (5)	161
C31—H31⋯C19^iv	0.95	2.80	3.708 (5)	159
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y+2, -z; (iii) x-1, y, z; (iv) x+1, y, z.

Compound (III)

Crystal data

C₂₅H₁₆
M_r = 316.38
Monoclinic, P 2₁ /c
a = 18.2491 (17) Å
b = 11.1522 (10) Å
c = 18.6918 (17) Å
β = 117.907 (2)°
V = 3361.7 (5) Å³
Z = 8
D_x = 1.250 Mg m⁻³
Mo Kα radiation
Cell parameters from 7135 reflections
θ = 2.2–25.0°
μ = 0.07 mm⁻¹
T = 115 (2) K
Block, colourless
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Bruker, 2000)T_min = 0.970, T_max = 0.987
18 394 measured reflections
5925 independent reflections
4923 reflections with I > 2σ(I)
R_int = 0.027
θ_max = 25.0°
h = −16 → 21
k = −13 → 13
l = −22 → 18

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.119
S = 1.05
5925 reflections
451 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.075P)² + 0.6111P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.26 e Å⁻³

H atoms were placed in calculated positions and treated as riding, with C—H distances of 0.95 Å and U_iso(H) = 1.2U_eq(C). Compound (II) contains zero values in the weighting scheme, resulting from weak diffraction by this sample.

For all compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; structure solution: SHELXS97 (Sheldrick, 1997 ); structure refinement: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996 ); publication software: SHELXTL (Bruker, 2001 ).

Supporting information

Crystal structure: contains datablocks I, II, III, global. DOI: 10.1107/S0108270105009479/gg1249sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105009479/gg1249Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105009479/gg1249IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105009479/gg1249IIIsup4.hkl

Comment top

The synthesis of 9,9'-spirobifluorene (SBF) was first reported by Clarkson & Gomberg in 1930, and the first single-crystal structure determination was reported four decades later by Schenk (1971). Exhibiting D_2d point symmetry, SBF is an unusual structural motif, and this has prompted its use in molecular recognition (Alcazar & Diederich 1992) and catalytic applications (Poriel et al., 2003), and its incorporation into materials that exhibit unusual optoelectronic properties (Wong et al., 2002). We have recently been interested in using SBF as a structural motif in molecular solids and report here the structures of two inclusion compounds incorporating benzene, (I), and biphenyl, (II). In the course of our study, we also determined the structure of a new polymorph of SBF, (III).

One of our initial aims had been to prepare cocrystals of SBF and fluorinated aromatics, including hexafluorobenzene, perfluoronaphthalene and perfluorobiphenyl, with the intention of investigating supramolecular structures akin to those derived from cocrystallization between planar hydro- and fluoroaromatics. However, in no case did cocrystals between SBF and fluoroaromatics result. We tentatively assigned this observation to repulsive (steric) interactions between SBF and fluoroaromatics, preventing the attractive molecular electric quadrupole moment interactions that result in parallel stacking in many perhydro/perflouro aromatic cocrystals (Williams, 1993). However, we rationalized that it may be possible to prepare inclusion compounds incorporating SBF and hydroaromatics, because the relative quadrupole moments would give rise to attractive edge-to-face electrostatic interactions (Lowden & Chandler 1974; Shi & Bartell 1988) that could be sterically accessible for SBF. Indeed, cocrystallization of SBF and the hydroaromatics benzene and biphenyl gave the inclusion compounds (I) and (II), respectively, which exhibit a range of edge-to face C—H···π(arene) hydrogen bonds between the aromatic moieties.

The bond lengths and angles of the constituent molecules of (I)–(III) are not exceptional. Examination of the packing diagrams reveals structural motifs resulting from C—H···π(arene) interactions and, based on the C—H···A (A = acceptor) angles and H···A bond lengths, these are considered here as weak hydrogen bonds.

Compound (I) contains one molecule of SBF and one molecule of benzene in the asymmetric unit (Fig. 1). Hydrogen bonds are present between adjacent SBF molecules, resulting in an infinite chain motif (Fig. 2). The benzene molecules do not participate in any directional bonding, and there is no directional bonding nor any short contacts between the chains. Hydrogen-bonding details are shown in Fig. 2 and the distance between atom H4 in the molecule at (x, y, z) and Cg1 (the centroid of the C20–C25 phenyl ring) in the symmetry-related molecule at (−1/2 + x, 1/2 − y, −1/2 + z) is 2.67 Å (Table 1).

Compound (II) contains one molecule of SBF and one molecule of biphenyl in the asymmetric unit (Fig. 3) and exhibits several C—H···π(arene) hydrogen-bonding motifs (Fig. 4), which collectively result in a layered structure with planes parallel to the (011) direction (Table 2). In contrast with (I), adjacent SBF molecules at (x,y,z) and (1 − x, 1 − y, 2 − z) are connected via a pair of hydrogen bonds between atom H16 and the C2–C7 phenyl ring (Fig. 4), with H16···Cg2 (ring centroid of the C2–C7 ring) = 2.65 Å. Biphenyl molecules connect SBF pairs with a series of C—H···π-arene interactions. Atom H29 in a biphenyl molecule at (1 − x, 2 − y, 1 − z) interacts in an asymmetric hydrogen bond with the arene moiety C8–C13 (centroid Cg3) of an SBF molecule at (x, y, z). In addition, biphenyl–SBF hydrogen bonding is present between atoms H3 and C27 of an SBF molecule at (x, y, z), and atoms C22 and H28, respectively, of a biphenyl molecule at (x, y, z), connecting pairs of SBF molecules into a chain motif. The chains can then be interpreted as precursors to a layer in the [011] plane via interaction of SBF and biphenyl atoms.

Compound (III) contains two molecules of SBF in the asymmetric unit (Fig. 5a,b), in contrast with the single molecule observed by Schenk (1971), which aggregates through very short intermolecular C—C distances (3.22, 3.35 and 3.45 Å) from edge–edge π-interactions between phenyl groups. The new polymorph, (III), does not exhibit short C—C contacts, but one SBF molecule of (III) participates in directed interactions to give SBF dimers (Fig. 6), with H11A···C23A = 2.77 Å between molecules at (x, y, z) and (1 − x, −y, 1 − z), respectively, and with a C11A—H11A—C23A angle of 168°. However, the hydrogen bonding of H11A can also be described from atom H11A to the C22A–C24A ring, with H11A···centroid(C22A–C24A) = 2.64 Å. Examination of the packing shows that layers of discrete SBF dimers are present parallel to the bc plane, separated by layers of SBF molecules that do not exhibit directional bonding (Fig. 6). In our study, all other solvent mixtures that we examined led to crystallization of the polymorph identified by Schenk (1971). This suggests that polymorph (III) is possibly metastable with respect to that described by Schenk (1971).

It is anticipated that the weak hydrogen-bonding motifs observed in compounds (I)–(III) are likely to be an important factor in determining the structures of molecular solids derived from SBF.

Experimental top

Computing details top

For all compounds, data collection: SMART (Bruker, 2000). Cell refinement: SAINT-Plus (Bruker, 2000) for (I), (II); SMART for (III). Data reduction: SAINT-Plus for (I), (II); SAINT-Plus (Bruker, 2000) for (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

	Fig. 1. A view of the asymmetric unit of (I), showing the atom-numbering scheme and with 50% probability displacement ellipsoids.
	Fig. 2. The hydrogen bonding in (I). Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 1/2 − y, 1/2 + z) and (−1/2 + x, 1/2 − y, −1/2 + z), respectively. Inset: a view down the C4—H4 bond axis, showing the relative π-arene position.
	Fig. 3. A view of the asymmetric unit of (II), showing the atom-numbering scheme and with 50% probability displacement ellipsoids.
	Fig. 4. The hydrogen bonding in (II). Atoms marked with an asterisk (*),a hash (#), or a prime (') are at the symmetry positions (1 − x, 1 − y, 2 − z), (1 − x, 2 − y, −z) and (−1 + x, y, z), respectively.
	Fig. 5. A view of the asymmetric unit of (III), showing both SBF moieties and the atom-numbering scheme, with 50% probability displacement ellipsoids.
	Fig. 6. The hydrogen bonding in (III). Atoms marked with an asterisk (*), a hash (#), or a prime (') are at the symmetry positions (1 − x, −y, 1 − z), (x, 1 + y, z) and (1 − x, 1 − y, 1 − z), respectively.

(I) 9,9'-spirobifluorene–benzene (1/1) top

Crystal data top

C₂₅H₁₆·C₆H₆	F(000) = 832
M_r = 394.49	D_x = 1.219 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4471 reflections
a = 10.7900 (6) Å	θ = 2.2–27.4°
b = 18.4004 (10) Å	µ = 0.07 mm⁻¹
c = 10.8403 (6) Å	T = 115 K
β = 92.877 (1)°	Block, colourless
V = 2149.5 (2) Å³	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4921 independent reflections
Radiation source: fine-focus sealed tube	3949 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→13
T_min = 0.893, T_max = 0.990	k = −23→23
14724 measured reflections	l = −14→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.056P)² + 0.5085P] where P = (F_o² + 2F_c²)/3
4921 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₅H₁₆·C₆H₆	V = 2149.5 (2) Å³
M_r = 394.49	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.7900 (6) Å	µ = 0.07 mm⁻¹
b = 18.4004 (10) Å	T = 115 K
c = 10.8403 (6) Å	0.2 × 0.2 × 0.2 mm
β = 92.877 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4921 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3949 reflections with I > 2σ(I)
T_min = 0.893, T_max = 0.990	R_int = 0.024
14724 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.02	Δρ_max = 0.30 e Å⁻³
4921 reflections	Δρ_min = −0.18 e Å⁻³
280 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

	x	y	z	U_iso*/U_eq
C1	0.50192 (10)	0.25828 (6)	0.17051 (10)	0.0193 (2)
C2	0.44272 (10)	0.31068 (6)	0.07547 (11)	0.0203 (2)
C3	0.39191 (11)	0.29525 (7)	−0.04131 (11)	0.0241 (3)
H3	0.3893	0.2467	−0.0713	0.029*
C4	0.34474 (12)	0.35209 (7)	−0.11397 (11)	0.0277 (3)
H4	0.3100	0.3424	−0.1945	0.033*
C5	0.34784 (12)	0.42300 (7)	−0.06987 (12)	0.0293 (3)
H5	0.3147	0.4612	−0.1204	0.035*
C6	0.39881 (11)	0.43870 (7)	0.04723 (12)	0.0253 (3)
H6	0.4009	0.4873	0.0770	0.030*
C7	0.44683 (10)	0.38217 (6)	0.12016 (11)	0.0212 (2)
C8	0.50858 (10)	0.38196 (6)	0.24407 (11)	0.0212 (2)
C9	0.53906 (11)	0.43841 (7)	0.32586 (11)	0.0258 (3)
H9	0.5165	0.4871	0.3063	0.031*
C10	0.60317 (12)	0.42177 (7)	0.43678 (12)	0.0289 (3)
H10	0.6246	0.4596	0.4935	0.035*
C11	0.63641 (12)	0.35055 (7)	0.46591 (11)	0.0280 (3)
H11	0.6809	0.3404	0.5418	0.034*
C12	0.60502 (11)	0.29404 (7)	0.38478 (11)	0.0242 (3)
H12	0.6270	0.2453	0.4050	0.029*
C13	0.54144 (10)	0.31016 (6)	0.27452 (11)	0.0206 (2)
C14	0.41596 (11)	0.19683 (6)	0.20736 (10)	0.0202 (2)
C15	0.30392 (11)	0.20146 (7)	0.26408 (11)	0.0244 (3)
H15	0.2712	0.2473	0.2862	0.029*
C16	0.24010 (12)	0.13748 (8)	0.28803 (12)	0.0293 (3)
H16	0.1634	0.1398	0.3272	0.035*
C17	0.28752 (12)	0.07051 (7)	0.25527 (12)	0.0306 (3)
H17	0.2422	0.0275	0.2711	0.037*
C18	0.40041 (12)	0.06546 (7)	0.19962 (12)	0.0278 (3)
H18	0.4329	0.0195	0.1778	0.033*
C19	0.46484 (11)	0.12908 (6)	0.17648 (10)	0.0218 (2)
C20	0.58640 (11)	0.14067 (6)	0.12370 (10)	0.0217 (2)
C21	0.67396 (12)	0.09168 (7)	0.08289 (12)	0.0280 (3)
H21	0.6584	0.0409	0.0834	0.034*
C22	0.78442 (12)	0.11883 (7)	0.04149 (12)	0.0315 (3)
H22	0.8451	0.0861	0.0137	0.038*
C23	0.80788 (12)	0.19296 (7)	0.03999 (12)	0.0297 (3)
H23	0.8845	0.2103	0.0120	0.036*
C24	0.72001 (11)	0.24228 (7)	0.07912 (11)	0.0245 (3)
H24	0.7354	0.2931	0.0773	0.029*
C25	0.60990 (11)	0.21544 (6)	0.12066 (10)	0.0202 (2)
C26	0.51299 (14)	0.10350 (8)	0.55764 (13)	0.0367 (3)
H26	0.5384	0.0997	0.4752	0.044*
C27	0.39970 (13)	0.07605 (8)	0.58842 (13)	0.0343 (3)
H27	0.3474	0.0529	0.5272	0.041*
C28	0.36196 (12)	0.08211 (7)	0.70821 (13)	0.0304 (3)
H28	0.2835	0.0636	0.7289	0.036*
C29	0.43833 (13)	0.11503 (7)	0.79758 (12)	0.0300 (3)
H29	0.4128	0.1188	0.8799	0.036*
C30	0.55203 (14)	0.14247 (8)	0.76711 (13)	0.0355 (3)
H30	0.6045	0.1654	0.8284	0.043*
C31	0.58947 (13)	0.13661 (8)	0.64703 (14)	0.0374 (3)
H31	0.6677	0.1554	0.6262	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0181 (5)	0.0221 (6)	0.0176 (5)	0.0008 (4)	0.0012 (4)	−0.0007 (4)
C2	0.0166 (5)	0.0233 (6)	0.0211 (6)	0.0013 (4)	0.0030 (4)	0.0023 (4)
C3	0.0236 (6)	0.0261 (6)	0.0225 (6)	−0.0004 (5)	0.0007 (5)	−0.0012 (5)
C4	0.0261 (6)	0.0359 (7)	0.0210 (6)	0.0005 (5)	−0.0014 (5)	0.0026 (5)
C5	0.0280 (7)	0.0319 (7)	0.0282 (7)	0.0056 (5)	0.0031 (5)	0.0093 (5)
C6	0.0252 (6)	0.0218 (6)	0.0295 (6)	0.0025 (5)	0.0066 (5)	0.0015 (5)
C7	0.0172 (5)	0.0245 (6)	0.0222 (6)	−0.0003 (4)	0.0053 (4)	−0.0004 (4)
C8	0.0175 (5)	0.0253 (6)	0.0212 (6)	0.0000 (4)	0.0055 (4)	−0.0017 (4)
C9	0.0251 (6)	0.0258 (6)	0.0270 (6)	−0.0013 (5)	0.0070 (5)	−0.0049 (5)
C10	0.0267 (6)	0.0349 (7)	0.0254 (6)	−0.0056 (5)	0.0055 (5)	−0.0113 (5)
C11	0.0231 (6)	0.0410 (7)	0.0199 (6)	−0.0019 (5)	0.0004 (5)	−0.0034 (5)
C12	0.0202 (6)	0.0305 (6)	0.0220 (6)	0.0010 (5)	0.0023 (5)	−0.0001 (5)
C13	0.0166 (5)	0.0255 (6)	0.0199 (6)	−0.0009 (4)	0.0035 (4)	−0.0029 (4)
C14	0.0207 (6)	0.0242 (6)	0.0154 (5)	−0.0011 (4)	−0.0011 (4)	0.0008 (4)
C15	0.0226 (6)	0.0321 (7)	0.0186 (6)	0.0024 (5)	0.0003 (5)	−0.0007 (5)
C16	0.0227 (6)	0.0439 (8)	0.0216 (6)	−0.0037 (5)	0.0034 (5)	0.0049 (5)
C17	0.0314 (7)	0.0336 (7)	0.0266 (7)	−0.0092 (5)	0.0001 (5)	0.0075 (5)
C18	0.0315 (7)	0.0246 (6)	0.0270 (6)	−0.0013 (5)	0.0006 (5)	0.0023 (5)
C19	0.0229 (6)	0.0250 (6)	0.0174 (5)	0.0006 (4)	−0.0001 (4)	0.0009 (4)
C20	0.0242 (6)	0.0239 (6)	0.0169 (5)	0.0018 (5)	0.0010 (4)	0.0003 (4)
C21	0.0334 (7)	0.0250 (6)	0.0260 (6)	0.0059 (5)	0.0049 (5)	−0.0011 (5)
C22	0.0310 (7)	0.0365 (7)	0.0275 (7)	0.0127 (5)	0.0087 (5)	0.0003 (5)
C23	0.0246 (6)	0.0401 (8)	0.0252 (6)	0.0032 (5)	0.0078 (5)	0.0053 (5)
C24	0.0245 (6)	0.0281 (6)	0.0211 (6)	0.0005 (5)	0.0029 (5)	0.0032 (5)
C25	0.0212 (6)	0.0241 (6)	0.0152 (5)	0.0032 (4)	0.0006 (4)	0.0001 (4)
C26	0.0441 (8)	0.0401 (8)	0.0267 (7)	−0.0033 (6)	0.0089 (6)	−0.0018 (6)
C27	0.0375 (8)	0.0351 (7)	0.0296 (7)	−0.0049 (6)	−0.0056 (6)	−0.0006 (5)
C28	0.0239 (6)	0.0301 (7)	0.0372 (7)	−0.0003 (5)	0.0033 (5)	0.0016 (5)
C29	0.0371 (7)	0.0259 (6)	0.0276 (7)	−0.0006 (5)	0.0069 (5)	−0.0026 (5)
C30	0.0376 (8)	0.0358 (7)	0.0327 (7)	−0.0101 (6)	−0.0012 (6)	−0.0042 (6)
C31	0.0301 (7)	0.0427 (8)	0.0402 (8)	−0.0092 (6)	0.0093 (6)	−0.0013 (6)

Geometric parameters (Å, º) top

C1—C13	1.5220 (15)	C16—C17	1.3872 (19)
C1—C2	1.5275 (15)	C16—H16	0.9500
C1—C25	1.5277 (15)	C17—C18	1.3893 (18)
C1—C14	1.5281 (15)	C17—H17	0.9500
C2—C3	1.3836 (16)	C18—C19	1.3907 (17)
C2—C7	1.4016 (16)	C18—H18	0.9500
C3—C4	1.3904 (17)	C19—C20	1.4727 (16)
C3—H3	0.9500	C20—C21	1.3938 (17)
C4—C5	1.3893 (19)	C20—C25	1.3997 (16)
C4—H4	0.9500	C21—C22	1.3875 (18)
C5—C6	1.3883 (18)	C21—H21	0.9500
C5—H5	0.9500	C22—C23	1.3874 (19)
C6—C7	1.3909 (17)	C22—H22	0.9500
C6—H6	0.9500	C23—C24	1.3939 (17)
C7—C8	1.4691 (17)	C23—H23	0.9500
C8—C9	1.3944 (17)	C24—C25	1.3826 (16)
C8—C13	1.4029 (16)	C24—H24	0.9500
C9—C10	1.3909 (18)	C26—C27	1.379 (2)
C9—H9	0.9500	C26—C31	1.382 (2)
C10—C11	1.3909 (19)	C26—H26	0.9500
C10—H10	0.9500	C27—C28	1.3847 (19)
C11—C12	1.3926 (17)	C27—H27	0.9500
C11—H11	0.9500	C28—C29	1.3800 (19)
C12—C13	1.3802 (16)	C28—H28	0.9500
C12—H12	0.9500	C29—C30	1.3820 (19)
C14—C15	1.3862 (16)	C29—H29	0.9500
C14—C19	1.4008 (16)	C30—C31	1.386 (2)
C15—C16	1.3948 (18)	C30—H30	0.9500
C15—H15	0.9500	C31—H31	0.9500

C13—C1—C2	101.29 (9)	C17—C16—C15	120.67 (12)
C13—C1—C25	113.29 (9)	C17—C16—H16	119.7
C2—C1—C25	112.81 (9)	C15—C16—H16	119.7
C13—C1—C14	114.94 (9)	C16—C17—C18	120.89 (12)
C2—C1—C14	113.87 (9)	C16—C17—H17	119.6
C25—C1—C14	101.21 (9)	C18—C17—H17	119.6
C3—C2—C7	120.87 (11)	C17—C18—C19	118.62 (12)
C3—C2—C1	128.36 (11)	C17—C18—H18	120.7
C7—C2—C1	110.76 (10)	C19—C18—H18	120.7
C2—C3—C4	118.75 (11)	C18—C19—C14	120.56 (11)
C2—C3—H3	120.6	C18—C19—C20	130.92 (11)
C4—C3—H3	120.6	C14—C19—C20	108.50 (10)
C5—C4—C3	120.65 (12)	C21—C20—C25	120.12 (11)
C5—C4—H4	119.7	C21—C20—C19	131.36 (11)
C3—C4—H4	119.7	C25—C20—C19	108.51 (10)
C6—C5—C4	120.77 (12)	C22—C21—C20	118.47 (12)
C6—C5—H5	119.6	C22—C21—H21	120.8
C4—C5—H5	119.6	C20—C21—H21	120.8
C5—C6—C7	118.90 (12)	C23—C22—C21	121.19 (12)
C5—C6—H6	120.6	C23—C22—H22	119.4
C7—C6—H6	120.6	C21—C22—H22	119.4
C6—C7—C2	120.07 (11)	C22—C23—C24	120.61 (12)
C6—C7—C8	131.34 (11)	C22—C23—H23	119.7
C2—C7—C8	108.57 (10)	C24—C23—H23	119.7
C9—C8—C13	120.21 (11)	C25—C24—C23	118.38 (12)
C9—C8—C7	131.39 (11)	C25—C24—H24	120.8
C13—C8—C7	108.38 (10)	C23—C24—H24	120.8
C10—C9—C8	118.48 (12)	C24—C25—C20	121.22 (11)
C10—C9—H9	120.8	C24—C25—C1	127.88 (11)
C8—C9—H9	120.8	C20—C25—C1	110.89 (10)
C11—C10—C9	121.00 (11)	C27—C26—C31	119.80 (13)
C11—C10—H10	119.5	C27—C26—H26	120.1
C9—C10—H10	119.5	C31—C26—H26	120.1
C10—C11—C12	120.56 (12)	C26—C27—C28	120.23 (13)
C10—C11—H11	119.7	C26—C27—H27	119.9
C12—C11—H11	119.7	C28—C27—H27	119.9
C13—C12—C11	118.75 (12)	C29—C28—C27	120.02 (12)
C13—C12—H12	120.6	C29—C28—H28	120.0
C11—C12—H12	120.6	C27—C28—H28	120.0
C12—C13—C8	121.00 (11)	C28—C29—C30	119.90 (13)
C12—C13—C1	127.98 (11)	C28—C29—H29	120.0
C8—C13—C1	110.99 (10)	C30—C29—H29	120.0
C15—C14—C19	120.52 (11)	C29—C30—C31	120.00 (13)
C15—C14—C1	128.67 (11)	C29—C30—H30	120.0
C19—C14—C1	110.81 (10)	C31—C30—H30	120.0
C14—C15—C16	118.72 (11)	C26—C31—C30	120.04 (13)
C14—C15—H15	120.6	C26—C31—H31	120.0
C16—C15—H15	120.6	C30—C31—H31	120.0

C13—C1—C2—C3	178.21 (11)	C13—C1—C14—C19	−125.38 (11)
C25—C1—C2—C3	56.79 (15)	C2—C1—C14—C19	118.41 (11)
C14—C1—C2—C3	−57.84 (15)	C25—C1—C14—C19	−2.92 (12)
C13—C1—C2—C7	−0.64 (11)	C19—C14—C15—C16	−0.95 (17)
C25—C1—C2—C7	−122.06 (10)	C1—C14—C15—C16	179.32 (11)
C14—C1—C2—C7	123.31 (10)	C14—C15—C16—C17	−0.27 (18)
C7—C2—C3—C4	−0.01 (17)	C15—C16—C17—C18	1.0 (2)
C1—C2—C3—C4	−178.76 (11)	C16—C17—C18—C19	−0.46 (19)
C2—C3—C4—C5	−0.40 (18)	C17—C18—C19—C14	−0.77 (18)
C3—C4—C5—C6	0.45 (19)	C17—C18—C19—C20	177.58 (12)
C4—C5—C6—C7	−0.07 (19)	C15—C14—C19—C18	1.49 (17)
C5—C6—C7—C2	−0.33 (17)	C1—C14—C19—C18	−178.74 (10)
C5—C6—C7—C8	178.11 (12)	C15—C14—C19—C20	−177.20 (10)
C3—C2—C7—C6	0.38 (17)	C1—C14—C19—C20	2.57 (13)
C1—C2—C7—C6	179.33 (10)	C18—C19—C20—C21	−1.1 (2)
C3—C2—C7—C8	−178.39 (10)	C14—C19—C20—C21	177.43 (12)
C1—C2—C7—C8	0.56 (12)	C18—C19—C20—C25	−179.55 (12)
C6—C7—C8—C9	−0.8 (2)	C14—C19—C20—C25	−1.05 (13)
C2—C7—C8—C9	177.82 (12)	C25—C20—C21—C22	0.95 (18)
C6—C7—C8—C13	−178.80 (12)	C19—C20—C21—C22	−177.37 (12)
C2—C7—C8—C13	−0.23 (13)	C20—C21—C22—C23	−0.2 (2)
C13—C8—C9—C10	0.54 (17)	C21—C22—C23—C24	−0.6 (2)
C7—C8—C9—C10	−177.31 (12)	C22—C23—C24—C25	0.75 (19)
C8—C9—C10—C11	0.02 (18)	C23—C24—C25—C20	0.00 (18)
C9—C10—C11—C12	−0.61 (19)	C23—C24—C25—C1	178.47 (11)
C10—C11—C12—C13	0.63 (18)	C21—C20—C25—C24	−0.86 (18)
C11—C12—C13—C8	−0.06 (17)	C19—C20—C25—C24	177.82 (10)
C11—C12—C13—C1	177.54 (11)	C21—C20—C25—C1	−179.57 (10)
C9—C8—C13—C12	−0.52 (17)	C19—C20—C25—C1	−0.89 (13)
C7—C8—C13—C12	177.78 (10)	C13—C1—C25—C24	−52.75 (16)
C9—C8—C13—C1	−178.50 (10)	C2—C1—C25—C24	61.59 (15)
C7—C8—C13—C1	−0.20 (13)	C14—C1—C25—C24	−176.34 (11)
C2—C1—C13—C12	−177.30 (11)	C13—C1—C25—C20	125.85 (11)
C25—C1—C13—C12	−56.22 (15)	C2—C1—C25—C20	−119.81 (11)
C14—C1—C13—C12	59.48 (15)	C14—C1—C25—C20	2.26 (12)
C2—C1—C13—C8	0.50 (12)	C31—C26—C27—C28	0.6 (2)
C25—C1—C13—C8	121.59 (11)	C26—C27—C28—C29	−0.7 (2)
C14—C1—C13—C8	−122.72 (11)	C27—C28—C29—C30	0.5 (2)
C13—C1—C14—C15	54.37 (16)	C28—C29—C30—C31	−0.3 (2)
C2—C1—C14—C15	−61.85 (15)	C27—C26—C31—C30	−0.3 (2)
C25—C1—C14—C15	176.83 (11)	C29—C30—C31—C26	0.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cg1ⁱ	0.95	2.67	3.61	172
C11—H11···C16ⁱⁱ	0.95	2.74	3.6196 (18)	154

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

(II) 9,9'-spirobifluorene–biphenyl (1/1) top

Crystal data top

C₂₅H₁₆·C₁₂H₁₀	Z = 2
M_r = 470.58	F(000) = 496
Triclinic, P1	D_x = 1.227 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.774 (4) Å	Cell parameters from 944 reflections
b = 11.427 (4) Å	θ = 2.4–24.2°
c = 13.075 (5) Å	µ = 0.07 mm⁻¹
α = 71.339 (8)°	T = 115 K
β = 83.106 (9)°	Block, colourless
γ = 67.030 (7)°	0.14 × 0.11 × 0.04 mm
V = 1273.8 (8) Å³

Data collection top

Bruker SMART CCD area detector diffractometer	4476 independent reflections
Radiation source: fine-focus sealed tube	2416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→6
T_min = 0.985, T_max = 0.998	k = −13→13
6971 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.079	H-atom parameters constrained
wR(F²) = 0.248	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
4476 reflections	Δρ_max = 0.33 e Å⁻³
335 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: Please provide, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (6)

Crystal data top

C₂₅H₁₆·C₁₂H₁₀	γ = 67.030 (7)°
M_r = 470.58	V = 1273.8 (8) Å³
Triclinic, P1	Z = 2
a = 9.774 (4) Å	Mo Kα radiation
b = 11.427 (4) Å	µ = 0.07 mm⁻¹
c = 13.075 (5) Å	T = 115 K
α = 71.339 (8)°	0.14 × 0.11 × 0.04 mm
β = 83.106 (9)°

Data collection top

Bruker SMART CCD area detector diffractometer	4476 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2416 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.998	R_int = 0.050
6971 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	0 restraints
wR(F²) = 0.248	H-atom parameters constrained
S = 0.92	Δρ_max = 0.33 e Å⁻³
4476 reflections	Δρ_min = −0.29 e Å⁻³
335 parameters

Special details top

Experimental. The crystals were small and diffracted weakly resulting in a poor quality data set.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3594 (4)	0.7724 (3)	0.7315 (2)	0.0254 (8)
C2	0.5255 (4)	0.6915 (3)	0.7212 (2)	0.0264 (8)
C3	0.6458 (4)	0.7082 (3)	0.7525 (2)	0.0309 (9)
H3	0.6311	0.7786	0.7814	0.037*
C4	0.7887 (4)	0.6195 (3)	0.7407 (3)	0.0352 (9)
H4	0.8725	0.6301	0.7608	0.042*
C5	0.8092 (4)	0.5155 (3)	0.6998 (3)	0.0376 (9)
H5	0.9071	0.4556	0.6924	0.045*
C6	0.6885 (4)	0.4978 (3)	0.6696 (2)	0.0338 (9)
H6	0.7032	0.4260	0.6424	0.041*
C7	0.5463 (4)	0.5870 (3)	0.6799 (2)	0.0300 (9)
C8	0.3987 (4)	0.5965 (3)	0.6522 (2)	0.0282 (8)
C9	0.3595 (4)	0.5203 (3)	0.6057 (2)	0.0347 (9)
H9	0.4323	0.4433	0.5913	0.042*
C10	0.2101 (4)	0.5604 (3)	0.5809 (3)	0.0370 (9)
H10	0.1809	0.5102	0.5484	0.044*
C11	0.1031 (4)	0.6723 (3)	0.6027 (2)	0.0356 (9)
H11	0.0023	0.6988	0.5836	0.043*
C12	0.1422 (4)	0.7459 (3)	0.6522 (2)	0.0327 (9)
H12	0.0687	0.8214	0.6686	0.039*
C13	0.2904 (4)	0.7073 (3)	0.6773 (2)	0.0275 (8)
C14	0.3164 (3)	0.7563 (3)	0.8499 (2)	0.0264 (8)
C15	0.3362 (3)	0.6394 (3)	0.9331 (2)	0.0290 (8)
H15	0.3776	0.5554	0.9196	0.035*
C16	0.2942 (4)	0.6480 (3)	1.0363 (3)	0.0362 (9)
H16	0.3059	0.5691	1.0942	0.043*
C17	0.2351 (4)	0.7707 (3)	1.0561 (3)	0.0372 (9)
H17	0.2080	0.7746	1.1275	0.045*
C18	0.2151 (4)	0.8876 (3)	0.9728 (3)	0.0345 (9)
H18	0.1736	0.9715	0.9863	0.041*
C19	0.2569 (3)	0.8793 (3)	0.8694 (3)	0.0283 (8)
C20	0.2507 (3)	0.9838 (3)	0.7664 (3)	0.0289 (8)
C21	0.1995 (4)	1.1219 (3)	0.7429 (3)	0.0372 (9)
H21	0.1602	1.1635	0.7980	0.045*
C22	0.2073 (4)	1.1969 (3)	0.6371 (3)	0.0404 (10)
H22	0.1709	1.2912	0.6194	0.049*
C23	0.2673 (4)	1.1369 (3)	0.5563 (3)	0.0420 (10)
H23	0.2725	1.1903	0.4845	0.050*
C24	0.3196 (4)	0.9994 (3)	0.5797 (3)	0.0341 (9)
H24	0.3604	0.9581	0.5246	0.041*
C25	0.3114 (4)	0.9235 (3)	0.6849 (3)	0.0282 (8)
C26	0.7446 (4)	0.9565 (3)	0.8318 (3)	0.0282 (8)
C27	0.6081 (4)	1.0320 (3)	0.7779 (3)	0.0364 (9)
H27	0.5224	1.0139	0.8077	0.044*
C28	0.5956 (4)	1.1330 (3)	0.6819 (3)	0.0389 (9)
H28	0.5018	1.1823	0.6467	0.047*
C29	0.7172 (4)	1.1628 (3)	0.6367 (3)	0.0377 (9)
H29	0.7084	1.2313	0.5703	0.045*
C30	0.8534 (4)	1.0907 (3)	0.6902 (3)	0.0357 (9)
H30	0.9383	1.1103	0.6605	0.043*
C31	0.8655 (4)	0.9908 (3)	0.7862 (3)	0.0324 (9)
H31	0.9588	0.9440	0.8223	0.039*
C32	0.7616 (4)	0.8427 (3)	0.9315 (3)	0.0304 (9)
C33	0.6389 (4)	0.8290 (3)	0.9948 (3)	0.0392 (9)
H33	0.5427	0.8954	0.9747	0.047*
C34	0.6548 (4)	0.7211 (4)	1.0855 (3)	0.0440 (10)
H34	0.5698	0.7145	1.1269	0.053*
C35	0.7936 (5)	0.6224 (4)	1.1167 (3)	0.0463 (10)
H35	0.8045	0.5478	1.1787	0.056*
C36	0.9163 (4)	0.6345 (4)	1.0558 (3)	0.0459 (10)
H36	1.0123	0.5683	1.0767	0.055*
C37	0.9000 (4)	0.7420 (3)	0.9651 (3)	0.0366 (9)
H37	0.9856	0.7478	0.9242	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.022 (2)	0.0263 (18)	0.0305 (19)	−0.0098 (16)	−0.0011 (15)	−0.0111 (15)
C2	0.020 (2)	0.0281 (19)	0.0271 (18)	−0.0062 (16)	0.0015 (15)	−0.0075 (15)
C3	0.024 (2)	0.035 (2)	0.0300 (19)	−0.0088 (18)	0.0000 (16)	−0.0075 (16)
C4	0.023 (2)	0.040 (2)	0.035 (2)	−0.0090 (18)	−0.0004 (16)	−0.0049 (18)
C5	0.023 (2)	0.042 (2)	0.035 (2)	−0.0008 (18)	0.0014 (17)	−0.0092 (18)
C6	0.033 (2)	0.032 (2)	0.0287 (19)	−0.0025 (18)	0.0030 (17)	−0.0115 (16)
C7	0.028 (2)	0.0265 (19)	0.0261 (18)	−0.0043 (18)	0.0041 (16)	−0.0048 (15)
C8	0.028 (2)	0.0288 (19)	0.0270 (19)	−0.0110 (17)	0.0022 (16)	−0.0074 (16)
C9	0.040 (2)	0.0289 (19)	0.033 (2)	−0.0110 (18)	0.0007 (18)	−0.0090 (16)
C10	0.045 (3)	0.040 (2)	0.032 (2)	−0.025 (2)	0.0001 (18)	−0.0068 (17)
C11	0.032 (2)	0.047 (2)	0.030 (2)	−0.020 (2)	0.0015 (17)	−0.0085 (18)
C12	0.029 (2)	0.036 (2)	0.0307 (19)	−0.0093 (18)	0.0009 (16)	−0.0104 (17)
C13	0.029 (2)	0.0266 (19)	0.0236 (18)	−0.0107 (17)	0.0027 (16)	−0.0032 (15)
C14	0.0168 (19)	0.031 (2)	0.033 (2)	−0.0076 (16)	−0.0015 (16)	−0.0127 (17)
C15	0.024 (2)	0.0247 (19)	0.035 (2)	−0.0069 (16)	0.0010 (16)	−0.0082 (16)
C16	0.030 (2)	0.044 (2)	0.027 (2)	−0.0094 (18)	−0.0004 (16)	−0.0054 (17)
C17	0.030 (2)	0.054 (2)	0.030 (2)	−0.015 (2)	0.0065 (17)	−0.019 (2)
C18	0.029 (2)	0.033 (2)	0.042 (2)	−0.0085 (17)	0.0048 (17)	−0.0173 (18)
C19	0.020 (2)	0.033 (2)	0.034 (2)	−0.0086 (17)	−0.0053 (16)	−0.0137 (16)
C20	0.021 (2)	0.029 (2)	0.038 (2)	−0.0111 (17)	0.0012 (16)	−0.0098 (17)
C21	0.025 (2)	0.033 (2)	0.053 (2)	−0.0090 (18)	0.0027 (18)	−0.0158 (19)
C22	0.027 (2)	0.030 (2)	0.061 (3)	−0.0105 (18)	0.0006 (19)	−0.009 (2)
C23	0.032 (2)	0.039 (2)	0.048 (2)	−0.0155 (19)	−0.0021 (19)	−0.0003 (19)
C24	0.028 (2)	0.033 (2)	0.039 (2)	−0.0105 (18)	−0.0043 (17)	−0.0069 (17)
C25	0.021 (2)	0.0277 (19)	0.033 (2)	−0.0071 (16)	−0.0026 (16)	−0.0069 (16)
C26	0.026 (2)	0.0289 (19)	0.032 (2)	−0.0093 (17)	−0.0009 (16)	−0.0130 (16)
C27	0.025 (2)	0.031 (2)	0.048 (2)	−0.0086 (18)	0.0005 (18)	−0.0087 (18)
C28	0.027 (2)	0.034 (2)	0.051 (2)	−0.0082 (18)	−0.0108 (19)	−0.0075 (19)
C29	0.042 (3)	0.033 (2)	0.036 (2)	−0.012 (2)	−0.0024 (19)	−0.0087 (17)
C30	0.028 (2)	0.042 (2)	0.036 (2)	−0.0122 (19)	0.0031 (17)	−0.0115 (18)
C31	0.020 (2)	0.037 (2)	0.037 (2)	−0.0070 (17)	−0.0010 (17)	−0.0102 (18)
C32	0.027 (2)	0.032 (2)	0.036 (2)	−0.0100 (18)	−0.0039 (17)	−0.0157 (17)
C33	0.031 (2)	0.036 (2)	0.050 (2)	−0.0115 (19)	0.0054 (19)	−0.0161 (19)
C34	0.046 (3)	0.046 (2)	0.045 (2)	−0.023 (2)	0.015 (2)	−0.018 (2)
C35	0.057 (3)	0.041 (2)	0.037 (2)	−0.018 (2)	−0.001 (2)	−0.0065 (18)
C36	0.038 (3)	0.043 (2)	0.045 (2)	−0.008 (2)	−0.006 (2)	−0.006 (2)
C37	0.027 (2)	0.038 (2)	0.039 (2)	−0.0073 (19)	−0.0027 (17)	−0.0076 (18)

Geometric parameters (Å, º) top

C1—C14	1.526 (4)	C19—C20	1.476 (4)
C1—C25	1.528 (4)	C20—C21	1.395 (4)
C1—C13	1.534 (4)	C20—C25	1.399 (4)
C1—C2	1.538 (4)	C21—C22	1.386 (5)
C2—C3	1.387 (4)	C21—H21	0.9500
C2—C7	1.398 (4)	C22—C23	1.390 (5)
C3—C4	1.395 (4)	C22—H22	0.9500
C3—H3	0.9500	C23—C24	1.388 (4)
C4—C5	1.390 (5)	C23—H23	0.9500
C4—H4	0.9500	C24—C25	1.384 (4)
C5—C6	1.391 (5)	C24—H24	0.9500
C5—H5	0.9500	C26—C31	1.396 (4)
C6—C7	1.388 (4)	C26—C27	1.399 (4)
C6—H6	0.9500	C26—C32	1.488 (4)
C7—C8	1.484 (5)	C27—C28	1.386 (5)
C8—C9	1.389 (4)	C27—H27	0.9500
C8—C13	1.403 (4)	C28—C29	1.377 (5)
C9—C10	1.394 (5)	C28—H28	0.9500
C9—H9	0.9500	C29—C30	1.392 (5)
C10—C11	1.389 (4)	C29—H29	0.9500
C10—H10	0.9500	C30—C31	1.381 (4)
C11—C12	1.390 (4)	C30—H30	0.9500
C11—H11	0.9500	C31—H31	0.9500
C12—C13	1.386 (4)	C32—C37	1.397 (4)
C12—H12	0.9500	C32—C33	1.405 (5)
C14—C15	1.387 (4)	C33—C34	1.382 (5)
C14—C19	1.391 (4)	C33—H33	0.9500
C15—C16	1.386 (4)	C34—C35	1.387 (5)
C15—H15	0.9500	C34—H34	0.9500
C16—C17	1.390 (4)	C35—C36	1.386 (5)
C16—H16	0.9500	C35—H35	0.9500
C17—C18	1.387 (4)	C36—C37	1.379 (4)
C17—H17	0.9500	C36—H36	0.9500
C18—C19	1.387 (4)	C37—H37	0.9500
C18—H18	0.9500

C14—C1—C25	101.8 (2)	C18—C19—C14	120.5 (3)
C14—C1—C13	113.2 (2)	C18—C19—C20	131.1 (3)
C25—C1—C13	115.6 (3)	C14—C19—C20	108.4 (3)
C14—C1—C2	110.6 (2)	C21—C20—C25	120.3 (3)
C25—C1—C2	115.7 (3)	C21—C20—C19	130.7 (3)
C13—C1—C2	100.4 (2)	C25—C20—C19	108.9 (3)
C3—C2—C7	120.9 (3)	C22—C21—C20	118.3 (3)
C3—C2—C1	127.7 (3)	C22—C21—H21	120.9
C7—C2—C1	111.2 (3)	C20—C21—H21	120.9
C2—C3—C4	118.7 (3)	C21—C22—C23	121.3 (3)
C2—C3—H3	120.6	C21—C22—H22	119.3
C4—C3—H3	120.6	C23—C22—H22	119.3
C5—C4—C3	120.3 (3)	C24—C23—C22	120.5 (3)
C5—C4—H4	119.9	C24—C23—H23	119.8
C3—C4—H4	119.9	C22—C23—H23	119.8
C4—C5—C6	121.0 (3)	C25—C24—C23	118.7 (3)
C4—C5—H5	119.5	C25—C24—H24	120.6
C6—C5—H5	119.5	C23—C24—H24	120.6
C7—C6—C5	118.8 (3)	C24—C25—C20	120.9 (3)
C7—C6—H6	120.6	C24—C25—C1	129.1 (3)
C5—C6—H6	120.6	C20—C25—C1	110.0 (3)
C6—C7—C2	120.3 (3)	C31—C26—C27	116.8 (3)
C6—C7—C8	131.2 (3)	C31—C26—C32	121.3 (3)
C2—C7—C8	108.5 (3)	C27—C26—C32	121.9 (3)
C9—C8—C13	120.9 (3)	C28—C27—C26	121.2 (3)
C9—C8—C7	131.1 (3)	C28—C27—H27	119.4
C13—C8—C7	108.0 (3)	C26—C27—H27	119.4
C8—C9—C10	118.0 (3)	C29—C28—C27	121.0 (3)
C8—C9—H9	121.0	C29—C28—H28	119.5
C10—C9—H9	121.0	C27—C28—H28	119.5
C11—C10—C9	121.2 (3)	C28—C29—C30	118.6 (3)
C11—C10—H10	119.4	C28—C29—H29	120.7
C9—C10—H10	119.4	C30—C29—H29	120.7
C10—C11—C12	120.6 (3)	C31—C30—C29	120.3 (3)
C10—C11—H11	119.7	C31—C30—H30	119.9
C12—C11—H11	119.7	C29—C30—H30	119.9
C13—C12—C11	118.8 (3)	C30—C31—C26	122.0 (3)
C13—C12—H12	120.6	C30—C31—H31	119.0
C11—C12—H12	120.6	C26—C31—H31	119.0
C12—C13—C8	120.4 (3)	C37—C32—C33	116.6 (3)
C12—C13—C1	128.1 (3)	C37—C32—C26	121.6 (3)
C8—C13—C1	111.5 (3)	C33—C32—C26	121.7 (3)
C15—C14—C19	121.0 (3)	C34—C33—C32	121.5 (3)
C15—C14—C1	128.2 (3)	C34—C33—H33	119.2
C19—C14—C1	110.8 (3)	C32—C33—H33	119.2
C16—C15—C14	118.4 (3)	C33—C34—C35	120.6 (4)
C16—C15—H15	120.8	C33—C34—H34	119.7
C14—C15—H15	120.8	C35—C34—H34	119.7
C15—C16—C17	120.7 (3)	C36—C35—C34	118.8 (3)
C15—C16—H16	119.6	C36—C35—H35	120.6
C17—C16—H16	119.6	C34—C35—H35	120.6
C18—C17—C16	120.8 (3)	C37—C36—C35	120.5 (4)
C18—C17—H17	119.6	C37—C36—H36	119.7
C16—C17—H17	119.6	C35—C36—H36	119.7
C19—C18—C17	118.6 (3)	C36—C37—C32	122.0 (3)
C19—C18—H18	120.7	C36—C37—H37	119.0
C17—C18—H18	120.7	C32—C37—H37	119.0

C14—C1—C2—C3	−62.9 (4)	C16—C17—C18—C19	−0.7 (5)
C25—C1—C2—C3	52.1 (4)	C17—C18—C19—C14	0.5 (5)
C13—C1—C2—C3	177.2 (3)	C17—C18—C19—C20	−179.4 (3)
C14—C1—C2—C7	113.5 (3)	C15—C14—C19—C18	−0.4 (5)
C25—C1—C2—C7	−131.4 (3)	C1—C14—C19—C18	−177.7 (3)
C13—C1—C2—C7	−6.3 (3)	C15—C14—C19—C20	179.5 (3)
C7—C2—C3—C4	0.8 (5)	C1—C14—C19—C20	2.3 (4)
C1—C2—C3—C4	176.9 (3)	C18—C19—C20—C21	−0.7 (6)
C2—C3—C4—C5	−0.9 (5)	C14—C19—C20—C21	179.3 (3)
C3—C4—C5—C6	0.2 (5)	C18—C19—C20—C25	178.0 (3)
C4—C5—C6—C7	0.7 (5)	C14—C19—C20—C25	−2.0 (4)
C5—C6—C7—C2	−0.8 (5)	C25—C20—C21—C22	1.5 (5)
C5—C6—C7—C8	178.1 (3)	C19—C20—C21—C22	180.0 (3)
C3—C2—C7—C6	0.0 (5)	C20—C21—C22—C23	−1.3 (5)
C1—C2—C7—C6	−176.7 (3)	C21—C22—C23—C24	0.7 (5)
C3—C2—C7—C8	−179.1 (3)	C22—C23—C24—C25	−0.2 (5)
C1—C2—C7—C8	4.2 (3)	C23—C24—C25—C20	0.4 (5)
C6—C7—C8—C9	−1.5 (6)	C23—C24—C25—C1	179.4 (3)
C2—C7—C8—C9	177.5 (3)	C21—C20—C25—C24	−1.0 (5)
C6—C7—C8—C13	−178.9 (3)	C19—C20—C25—C24	−179.8 (3)
C2—C7—C8—C13	0.0 (3)	C21—C20—C25—C1	179.8 (3)
C13—C8—C9—C10	2.5 (5)	C19—C20—C25—C1	0.9 (4)
C7—C8—C9—C10	−174.7 (3)	C14—C1—C25—C24	−178.8 (3)
C8—C9—C10—C11	−0.6 (5)	C13—C1—C25—C24	−55.7 (5)
C9—C10—C11—C12	−1.4 (5)	C2—C1—C25—C24	61.2 (4)
C10—C11—C12—C13	1.4 (5)	C14—C1—C25—C20	0.4 (3)
C11—C12—C13—C8	0.5 (5)	C13—C1—C25—C20	123.5 (3)
C11—C12—C13—C1	−180.0 (3)	C2—C1—C25—C20	−119.6 (3)
C9—C8—C13—C12	−2.5 (5)	C31—C26—C27—C28	2.2 (5)
C7—C8—C13—C12	175.3 (3)	C32—C26—C27—C28	−176.3 (3)
C9—C8—C13—C1	177.9 (3)	C26—C27—C28—C29	−0.5 (5)
C7—C8—C13—C1	−4.3 (3)	C27—C28—C29—C30	−0.9 (5)
C14—C1—C13—C12	68.8 (4)	C28—C29—C30—C31	0.4 (5)
C25—C1—C13—C12	−48.0 (4)	C29—C30—C31—C26	1.4 (5)
C2—C1—C13—C12	−173.2 (3)	C27—C26—C31—C30	−2.6 (5)
C14—C1—C13—C8	−111.6 (3)	C32—C26—C31—C30	175.9 (3)
C25—C1—C13—C8	131.5 (3)	C31—C26—C32—C37	−19.9 (5)
C2—C1—C13—C8	6.4 (3)	C27—C26—C32—C37	158.5 (3)
C25—C1—C14—C15	−178.7 (3)	C31—C26—C32—C33	162.0 (3)
C13—C1—C14—C15	56.6 (4)	C27—C26—C32—C33	−19.5 (5)
C2—C1—C14—C15	−55.2 (4)	C37—C32—C33—C34	−0.1 (5)
C25—C1—C14—C19	−1.6 (3)	C26—C32—C33—C34	178.1 (3)
C13—C1—C14—C19	−126.4 (3)	C32—C33—C34—C35	−0.2 (5)
C2—C1—C14—C19	121.8 (3)	C33—C34—C35—C36	0.6 (5)
C19—C14—C15—C16	0.5 (5)	C34—C35—C36—C37	−0.8 (5)
C1—C14—C15—C16	177.2 (3)	C35—C36—C37—C32	0.6 (5)
C14—C15—C16—C17	−0.6 (5)	C33—C32—C37—C36	−0.2 (5)
C15—C16—C17—C18	0.8 (5)	C26—C32—C37—C36	−178.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···Cg2ⁱ	0.95	2.65	3.57	162
C29—H29···Cg3ⁱⁱ	0.95	2.63	3.56	163
C3—H3···C27	0.95	2.80	3.692 (5)	157
C28—H28···C22	0.95	2.84	3.658 (6)	147
C12—H12···C31ⁱⁱⁱ	0.95	2.87	3.783 (5)	161
C31—H31···C19^iv	0.95	2.80	3.708 (5)	159

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+2, −z; (iii) x−1, y, z; (iv) x+1, y, z.

(III) 9,9'-spirobifluorene top

Crystal data top

C₂₅H₁₆	F(000) = 1328
M_r = 316.38	D_x = 1.250 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7135 reflections
a = 18.2491 (17) Å	θ = 2.2–25.0°
b = 11.1522 (10) Å	µ = 0.07 mm⁻¹
c = 18.6918 (17) Å	T = 115 K
β = 117.907 (2)°	Block, colourless
V = 3361.7 (5) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	5925 independent reflections
Radiation source: fine-focus sealed tube	4923 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→21
T_min = 0.970, T_max = 0.987	k = −13→13
18394 measured reflections	l = −22→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.075P)² + 0.6111P] where P = (F_o² + 2F_c²)/3
5925 reflections	(Δ/σ)_max < 0.001
451 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₅H₁₆	V = 3361.7 (5) Å³
M_r = 316.38	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.2491 (17) Å	µ = 0.07 mm⁻¹
b = 11.1522 (10) Å	T = 115 K
c = 18.6918 (17) Å	0.30 × 0.20 × 0.20 mm
β = 117.907 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5925 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4923 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.987	R_int = 0.027
18394 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.05	Δρ_max = 0.32 e Å⁻³
5925 reflections	Δρ_min = −0.26 e Å⁻³
451 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1A	0.48307 (8)	0.08141 (12)	0.30687 (8)	0.0212 (3)
C2A	0.41847 (8)	0.08646 (12)	0.21798 (8)	0.0205 (3)
C3A	0.41290 (9)	0.16745 (13)	0.15972 (9)	0.0239 (3)
H3A	0.4554	0.2250	0.1714	0.029*
C4A	0.34386 (9)	0.16308 (13)	0.08359 (9)	0.0270 (3)
H4A	0.3396	0.2170	0.0425	0.032*
C5A	0.28098 (9)	0.08008 (13)	0.06733 (9)	0.0266 (3)
H5A	0.2330	0.0803	0.0159	0.032*
C6A	0.28740 (9)	−0.00284 (13)	0.12513 (9)	0.0241 (3)
H6A	0.2447	−0.0600	0.1134	0.029*
C7A	0.35741 (8)	−0.00123 (12)	0.20079 (9)	0.0204 (3)
C8A	0.38263 (8)	−0.07718 (12)	0.27302 (8)	0.0200 (3)
C9A	0.34980 (9)	−0.18325 (13)	0.28534 (9)	0.0245 (3)
H9A	0.3013	−0.2176	0.2429	0.029*
C10A	0.38924 (9)	−0.23759 (13)	0.36064 (9)	0.0262 (3)
H10A	0.3681	−0.3109	0.3694	0.031*
C11A	0.45941 (9)	−0.18660 (13)	0.42380 (9)	0.0256 (3)
H11A	0.4845	−0.2240	0.4755	0.031*
C12A	0.49277 (9)	−0.08160 (13)	0.41162 (9)	0.0232 (3)
H12A	0.5408	−0.0469	0.4544	0.028*
C13A	0.45469 (8)	−0.02841 (12)	0.33597 (8)	0.0197 (3)
C14A	0.57348 (8)	0.07093 (12)	0.32530 (8)	0.0216 (3)
C15A	0.61024 (9)	−0.01923 (13)	0.30235 (9)	0.0265 (3)
H15A	0.5779	−0.0823	0.2678	0.032*
C16A	0.69603 (10)	−0.01529 (15)	0.33115 (10)	0.0324 (4)
H16A	0.7226	−0.0765	0.3164	0.039*
C17A	0.74258 (9)	0.07759 (15)	0.38125 (10)	0.0342 (4)
H17A	0.8009	0.0785	0.4011	0.041*
C18A	0.70545 (9)	0.16900 (15)	0.40286 (9)	0.0314 (4)
H18A	0.7377	0.2330	0.4364	0.038*
C19A	0.61999 (9)	0.16559 (13)	0.37459 (9)	0.0250 (3)
C20A	0.56417 (9)	0.24707 (13)	0.38783 (8)	0.0253 (3)
C21A	0.57800 (11)	0.35786 (15)	0.42620 (10)	0.0334 (4)
H21A	0.6322	0.3911	0.4525	0.040*
C22A	0.51153 (11)	0.41903 (14)	0.42552 (10)	0.0354 (4)
H22A	0.5200	0.4960	0.4499	0.043*
C23A	0.43278 (11)	0.36873 (14)	0.38954 (10)	0.0327 (4)
H23A	0.3882	0.4107	0.3909	0.039*
C24A	0.41849 (10)	0.25798 (13)	0.35161 (9)	0.0272 (3)
H24A	0.3646	0.2236	0.3273	0.033*
C25A	0.48423 (9)	0.19836 (12)	0.34987 (8)	0.0224 (3)
C1B	0.08706 (8)	0.32021 (12)	0.30371 (8)	0.0211 (3)
C2B	0.11992 (8)	0.44239 (12)	0.34300 (8)	0.0213 (3)
C3B	0.18597 (9)	0.50740 (13)	0.34576 (9)	0.0257 (3)
H3B	0.2199	0.4749	0.3245	0.031*
C4B	0.20147 (9)	0.62072 (14)	0.38020 (9)	0.0294 (4)
H4B	0.2465	0.6663	0.3825	0.035*
C5B	0.15185 (9)	0.66872 (13)	0.41157 (9)	0.0290 (4)
H5B	0.1626	0.7473	0.4337	0.035*
C6B	0.08703 (9)	0.60285 (13)	0.41074 (9)	0.0252 (3)
H6B	0.0541	0.6348	0.4333	0.030*
C7B	0.07122 (8)	0.48902 (12)	0.37622 (8)	0.0211 (3)
C8B	0.00665 (8)	0.40109 (12)	0.36429 (8)	0.0212 (3)
C9B	−0.05425 (9)	0.40126 (13)	0.38967 (9)	0.0255 (3)
H9B	−0.0598	0.4672	0.4190	0.031*
C10B	−0.10633 (9)	0.30303 (14)	0.37106 (9)	0.0280 (3)
H10B	−0.1473	0.3012	0.3889	0.034*
C11B	−0.10000 (9)	0.20726 (14)	0.32696 (9)	0.0269 (3)
H11B	−0.1371	0.1414	0.3142	0.032*
C12B	−0.03953 (9)	0.20684 (13)	0.30111 (9)	0.0237 (3)
H12B	−0.0351	0.1416	0.2707	0.028*
C13B	0.01369 (8)	0.30354 (12)	0.32088 (8)	0.0202 (3)
C14B	0.06703 (8)	0.32124 (12)	0.21458 (9)	0.0217 (3)
C15B	0.01069 (9)	0.39212 (13)	0.15238 (9)	0.0258 (3)
H15B	−0.0250	0.4452	0.1612	0.031*
C16B	0.00736 (9)	0.38404 (14)	0.07670 (9)	0.0301 (4)
H16B	−0.0313	0.4317	0.0333	0.036*
C17B	0.06009 (10)	0.30675 (15)	0.06387 (9)	0.0317 (4)
H17B	0.0579	0.3037	0.0121	0.038*
C18B	0.11556 (9)	0.23435 (14)	0.12566 (9)	0.0290 (4)
H18B	0.1512	0.1814	0.1167	0.035*
C19B	0.11819 (8)	0.24055 (13)	0.20140 (9)	0.0237 (3)
C20B	0.16787 (8)	0.17357 (13)	0.27676 (9)	0.0234 (3)
C21B	0.22251 (9)	0.07821 (14)	0.29378 (10)	0.0302 (4)
H21B	0.2340	0.0465	0.2529	0.036*
C22B	0.25995 (10)	0.02992 (14)	0.37091 (10)	0.0324 (4)
H22B	0.2978	−0.0348	0.3831	0.039*
C23B	0.24265 (9)	0.07531 (14)	0.43082 (10)	0.0302 (4)
H23B	0.2689	0.0415	0.4836	0.036*
C24B	0.18715 (9)	0.16979 (13)	0.41394 (9)	0.0252 (3)
H24B	0.1749	0.2002	0.4546	0.030*
C25B	0.15017 (8)	0.21866 (12)	0.33707 (9)	0.0218 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0192 (7)	0.0244 (7)	0.0225 (7)	−0.0028 (6)	0.0118 (6)	−0.0010 (6)
C2A	0.0188 (7)	0.0230 (7)	0.0227 (7)	0.0016 (5)	0.0123 (6)	−0.0023 (6)
C3A	0.0240 (7)	0.0235 (7)	0.0287 (8)	0.0007 (6)	0.0160 (6)	0.0000 (6)
C4A	0.0306 (8)	0.0274 (8)	0.0261 (8)	0.0059 (6)	0.0158 (7)	0.0036 (6)
C5A	0.0227 (7)	0.0321 (8)	0.0235 (8)	0.0069 (6)	0.0094 (6)	−0.0014 (6)
C6A	0.0179 (7)	0.0272 (7)	0.0280 (8)	−0.0002 (6)	0.0114 (6)	−0.0049 (6)
C7A	0.0189 (7)	0.0229 (7)	0.0241 (7)	0.0010 (5)	0.0142 (6)	−0.0027 (6)
C8A	0.0173 (7)	0.0228 (7)	0.0249 (7)	0.0006 (5)	0.0140 (6)	−0.0033 (6)
C9A	0.0195 (7)	0.0273 (8)	0.0314 (8)	−0.0028 (6)	0.0157 (6)	−0.0035 (6)
C10A	0.0262 (8)	0.0238 (7)	0.0387 (9)	−0.0002 (6)	0.0235 (7)	0.0018 (6)
C11A	0.0256 (8)	0.0289 (8)	0.0292 (8)	0.0045 (6)	0.0187 (7)	0.0051 (6)
C12A	0.0200 (7)	0.0288 (8)	0.0237 (7)	−0.0002 (6)	0.0125 (6)	−0.0020 (6)
C13A	0.0189 (7)	0.0213 (7)	0.0243 (7)	0.0002 (5)	0.0146 (6)	−0.0020 (6)
C14A	0.0198 (7)	0.0263 (7)	0.0215 (7)	−0.0025 (6)	0.0121 (6)	0.0031 (6)
C15A	0.0245 (8)	0.0292 (8)	0.0297 (8)	−0.0008 (6)	0.0159 (7)	0.0012 (6)
C16A	0.0271 (8)	0.0396 (9)	0.0377 (9)	0.0055 (7)	0.0212 (7)	0.0087 (7)
C17A	0.0188 (7)	0.0500 (10)	0.0352 (9)	−0.0025 (7)	0.0139 (7)	0.0124 (8)
C18A	0.0248 (8)	0.0436 (9)	0.0260 (8)	−0.0126 (7)	0.0120 (7)	0.0024 (7)
C19A	0.0243 (7)	0.0326 (8)	0.0204 (7)	−0.0074 (6)	0.0125 (6)	0.0013 (6)
C20A	0.0311 (8)	0.0282 (8)	0.0215 (7)	−0.0083 (6)	0.0163 (6)	−0.0008 (6)
C21A	0.0447 (10)	0.0339 (8)	0.0306 (8)	−0.0187 (7)	0.0251 (8)	−0.0078 (7)
C22A	0.0603 (11)	0.0254 (8)	0.0334 (9)	−0.0091 (8)	0.0326 (9)	−0.0061 (7)
C23A	0.0467 (10)	0.0290 (8)	0.0308 (8)	0.0059 (7)	0.0251 (8)	0.0024 (7)
C24A	0.0303 (8)	0.0282 (8)	0.0247 (8)	0.0022 (6)	0.0143 (7)	0.0016 (6)
C25A	0.0266 (7)	0.0234 (7)	0.0195 (7)	−0.0029 (6)	0.0127 (6)	0.0018 (6)
C1B	0.0171 (7)	0.0234 (7)	0.0252 (7)	0.0002 (6)	0.0119 (6)	0.0000 (6)
C2B	0.0167 (7)	0.0245 (7)	0.0216 (7)	0.0025 (6)	0.0080 (6)	0.0025 (6)
C3B	0.0174 (7)	0.0316 (8)	0.0278 (8)	0.0009 (6)	0.0104 (6)	0.0029 (6)
C4B	0.0186 (7)	0.0314 (8)	0.0334 (8)	−0.0048 (6)	0.0082 (6)	0.0027 (7)
C5B	0.0249 (8)	0.0251 (8)	0.0288 (8)	−0.0021 (6)	0.0057 (7)	−0.0025 (6)
C6B	0.0227 (7)	0.0263 (7)	0.0247 (8)	0.0031 (6)	0.0095 (6)	−0.0016 (6)
C7B	0.0172 (7)	0.0240 (7)	0.0207 (7)	0.0031 (5)	0.0077 (6)	0.0022 (6)
C8B	0.0164 (7)	0.0249 (7)	0.0219 (7)	0.0029 (6)	0.0087 (6)	0.0018 (6)
C9B	0.0227 (7)	0.0280 (8)	0.0302 (8)	0.0043 (6)	0.0160 (6)	−0.0005 (6)
C10B	0.0200 (7)	0.0356 (8)	0.0341 (8)	0.0023 (6)	0.0172 (7)	0.0022 (7)
C11B	0.0206 (7)	0.0297 (8)	0.0319 (8)	−0.0040 (6)	0.0135 (6)	0.0000 (6)
C12B	0.0215 (7)	0.0252 (7)	0.0265 (8)	0.0009 (6)	0.0130 (6)	−0.0009 (6)
C13B	0.0161 (7)	0.0236 (7)	0.0220 (7)	0.0033 (5)	0.0099 (6)	0.0035 (6)
C14B	0.0183 (7)	0.0230 (7)	0.0259 (8)	−0.0045 (6)	0.0122 (6)	−0.0010 (6)
C15B	0.0238 (7)	0.0244 (7)	0.0286 (8)	−0.0031 (6)	0.0117 (6)	0.0007 (6)
C16B	0.0281 (8)	0.0311 (8)	0.0275 (8)	−0.0066 (7)	0.0101 (7)	0.0046 (6)
C17B	0.0335 (9)	0.0406 (9)	0.0255 (8)	−0.0110 (7)	0.0175 (7)	−0.0022 (7)
C18B	0.0262 (8)	0.0354 (9)	0.0321 (8)	−0.0050 (6)	0.0192 (7)	−0.0054 (7)
C19B	0.0189 (7)	0.0279 (8)	0.0278 (8)	−0.0043 (6)	0.0140 (6)	−0.0025 (6)
C20B	0.0167 (7)	0.0277 (8)	0.0290 (8)	−0.0021 (6)	0.0133 (6)	−0.0019 (6)
C21B	0.0245 (8)	0.0348 (8)	0.0367 (9)	0.0034 (7)	0.0190 (7)	−0.0042 (7)
C22B	0.0254 (8)	0.0321 (8)	0.0414 (9)	0.0094 (7)	0.0170 (7)	0.0024 (7)
C23B	0.0257 (8)	0.0325 (8)	0.0319 (8)	0.0041 (6)	0.0130 (7)	0.0052 (7)
C24B	0.0221 (7)	0.0291 (8)	0.0278 (8)	0.0008 (6)	0.0146 (6)	−0.0003 (6)
C25B	0.0162 (7)	0.0242 (7)	0.0281 (8)	−0.0013 (5)	0.0130 (6)	−0.0020 (6)

Geometric parameters (Å, º) top

C1A—C2A	1.5232 (19)	C1B—C25B	1.5249 (19)
C1A—C14A	1.5241 (19)	C1B—C13B	1.5271 (18)
C1A—C13A	1.5257 (19)	C1B—C14B	1.530 (2)
C1A—C25A	1.5269 (19)	C1B—C2B	1.5308 (19)
C2A—C3A	1.381 (2)	C2B—C3B	1.387 (2)
C2A—C7A	1.4022 (19)	C2B—C7B	1.401 (2)
C3A—C4A	1.392 (2)	C3B—C4B	1.386 (2)
C3A—H3A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.393 (2)	C4B—C5B	1.396 (2)
C4A—H4A	0.9500	C4B—H4B	0.9500
C5A—C6A	1.385 (2)	C5B—C6B	1.386 (2)
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—C7A	1.393 (2)	C6B—C7B	1.392 (2)
C6A—H6A	0.9500	C6B—H6B	0.9500
C7A—C8A	1.473 (2)	C7B—C8B	1.4676 (19)
C8A—C9A	1.393 (2)	C8B—C9B	1.398 (2)
C8A—C13A	1.4004 (19)	C8B—C13B	1.399 (2)
C9A—C10A	1.385 (2)	C9B—C10B	1.384 (2)
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.393 (2)	C10B—C11B	1.387 (2)
C10A—H10A	0.9500	C10B—H10B	0.9500
C11A—C12A	1.387 (2)	C11B—C12B	1.396 (2)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—C13A	1.384 (2)	C12B—C13B	1.381 (2)
C12A—H12A	0.9500	C12B—H12B	0.9500
C14A—C15A	1.384 (2)	C14B—C15B	1.384 (2)
C14A—C19A	1.397 (2)	C14B—C19B	1.399 (2)
C15A—C16A	1.398 (2)	C15B—C16B	1.390 (2)
C15A—H15A	0.9500	C15B—H15B	0.9500
C16A—C17A	1.388 (2)	C16B—C17B	1.394 (2)
C16A—H16A	0.9500	C16B—H16B	0.9500
C17A—C18A	1.385 (2)	C17B—C18B	1.384 (2)
C17A—H17A	0.9500	C17B—H17B	0.9500
C18A—C19A	1.393 (2)	C18B—C19B	1.396 (2)
C18A—H18A	0.9500	C18B—H18B	0.9500
C19A—C20A	1.470 (2)	C19B—C20B	1.473 (2)
C20A—C21A	1.391 (2)	C20B—C21B	1.389 (2)
C20A—C25A	1.399 (2)	C20B—C25B	1.403 (2)
C21A—C22A	1.386 (2)	C21B—C22B	1.383 (2)
C21A—H21A	0.9500	C21B—H21B	0.9500
C22A—C23A	1.388 (2)	C22B—C23B	1.393 (2)
C22A—H22A	0.9500	C22B—H22B	0.9500
C23A—C24A	1.387 (2)	C23B—C24B	1.391 (2)
C23A—H23A	0.9500	C23B—H23B	0.9500
C24A—C25A	1.385 (2)	C24B—C25B	1.382 (2)
C24A—H24A	0.9500	C24B—H24B	0.9500

C2A—C1A—C14A	116.92 (11)	C25B—C1B—C13B	113.10 (11)
C2A—C1A—C13A	101.54 (11)	C25B—C1B—C14B	101.58 (11)
C14A—C1A—C13A	111.72 (11)	C13B—C1B—C14B	116.34 (11)
C2A—C1A—C25A	110.83 (11)	C25B—C1B—C2B	114.43 (11)
C14A—C1A—C25A	101.51 (11)	C13B—C1B—C2B	101.11 (11)
C13A—C1A—C25A	114.93 (11)	C14B—C1B—C2B	110.86 (11)
C3A—C2A—C7A	121.20 (13)	C3B—C2B—C7B	120.68 (13)
C3A—C2A—C1A	128.16 (13)	C3B—C2B—C1B	128.45 (13)
C7A—C2A—C1A	110.52 (12)	C7B—C2B—C1B	110.83 (12)
C2A—C3A—C4A	118.71 (13)	C4B—C3B—C2B	118.61 (14)
C2A—C3A—H3A	120.6	C4B—C3B—H3B	120.7
C4A—C3A—H3A	120.6	C2B—C3B—H3B	120.7
C3A—C4A—C5A	120.38 (14)	C3B—C4B—C5B	120.89 (14)
C3A—C4A—H4A	119.8	C3B—C4B—H4B	119.6
C5A—C4A—H4A	119.8	C5B—C4B—H4B	119.6
C6A—C5A—C4A	120.89 (13)	C6B—C5B—C4B	120.67 (14)
C6A—C5A—H5A	119.6	C6B—C5B—H5B	119.7
C4A—C5A—H5A	119.6	C4B—C5B—H5B	119.7
C5A—C6A—C7A	119.07 (13)	C5B—C6B—C7B	118.63 (14)
C5A—C6A—H6A	120.5	C5B—C6B—H6B	120.7
C7A—C6A—H6A	120.5	C7B—C6B—H6B	120.7
C6A—C7A—C2A	119.63 (13)	C6B—C7B—C2B	120.48 (13)
C6A—C7A—C8A	131.88 (13)	C6B—C7B—C8B	131.10 (13)
C2A—C7A—C8A	108.49 (12)	C2B—C7B—C8B	108.39 (12)
C9A—C8A—C13A	119.89 (13)	C9B—C8B—C13B	120.11 (13)
C9A—C8A—C7A	131.73 (13)	C9B—C8B—C7B	131.07 (13)
C13A—C8A—C7A	108.33 (12)	C13B—C8B—C7B	108.81 (12)
C10A—C9A—C8A	118.71 (13)	C10B—C9B—C8B	118.37 (14)
C10A—C9A—H9A	120.6	C10B—C9B—H9B	120.8
C8A—C9A—H9A	120.6	C8B—C9B—H9B	120.8
C9A—C10A—C11A	121.12 (14)	C9B—C10B—C11B	121.38 (14)
C9A—C10A—H10A	119.4	C9B—C10B—H10B	119.3
C11A—C10A—H10A	119.4	C11B—C10B—H10B	119.3
C12A—C11A—C10A	120.36 (14)	C10B—C11B—C12B	120.50 (14)
C12A—C11A—H11A	119.8	C10B—C11B—H11B	119.8
C10A—C11A—H11A	119.8	C12B—C11B—H11B	119.8
C13A—C12A—C11A	118.73 (13)	C13B—C12B—C11B	118.39 (14)
C13A—C12A—H12A	120.6	C13B—C12B—H12B	120.8
C11A—C12A—H12A	120.6	C11B—C12B—H12B	120.8
C12A—C13A—C8A	121.14 (13)	C12B—C13B—C8B	121.23 (13)
C12A—C13A—C1A	128.07 (13)	C12B—C13B—C1B	127.94 (13)
C8A—C13A—C1A	110.74 (12)	C8B—C13B—C1B	110.79 (12)
C15A—C14A—C19A	121.37 (13)	C15B—C14B—C19B	120.95 (14)
C15A—C14A—C1A	128.05 (13)	C15B—C14B—C1B	128.62 (13)
C19A—C14A—C1A	110.51 (12)	C19B—C14B—C1B	110.36 (12)
C14A—C15A—C16A	118.42 (14)	C14B—C15B—C16B	118.64 (14)
C14A—C15A—H15A	120.8	C14B—C15B—H15B	120.7
C16A—C15A—H15A	120.8	C16B—C15B—H15B	120.7
C17A—C16A—C15A	120.31 (15)	C15B—C16B—C17B	120.69 (14)
C17A—C16A—H16A	119.8	C15B—C16B—H16B	119.7
C15A—C16A—H16A	119.8	C17B—C16B—H16B	119.7
C18A—C17A—C16A	121.17 (14)	C18B—C17B—C16B	120.75 (14)
C18A—C17A—H17A	119.4	C18B—C17B—H17B	119.6
C16A—C17A—H17A	119.4	C16B—C17B—H17B	119.6
C17A—C18A—C19A	118.88 (15)	C17B—C18B—C19B	118.82 (14)
C17A—C18A—H18A	120.6	C17B—C18B—H18B	120.6
C19A—C18A—H18A	120.6	C19B—C18B—H18B	120.6
C18A—C19A—C14A	119.83 (14)	C18B—C19B—C14B	120.10 (14)
C18A—C19A—C20A	131.31 (14)	C18B—C19B—C20B	131.20 (14)
C14A—C19A—C20A	108.86 (12)	C14B—C19B—C20B	108.70 (12)
C21A—C20A—C25A	120.05 (14)	C21B—C20B—C25B	120.06 (14)
C21A—C20A—C19A	131.54 (14)	C21B—C20B—C19B	131.44 (14)
C25A—C20A—C19A	108.35 (12)	C25B—C20B—C19B	108.46 (12)
C22A—C21A—C20A	119.04 (15)	C22B—C21B—C20B	119.22 (14)
C22A—C21A—H21A	120.5	C22B—C21B—H21B	120.4
C20A—C21A—H21A	120.5	C20B—C21B—H21B	120.4
C21A—C22A—C23A	120.56 (15)	C21B—C22B—C23B	120.61 (14)
C21A—C22A—H22A	119.7	C21B—C22B—H22B	119.7
C23A—C22A—H22A	119.7	C23B—C22B—H22B	119.7
C24A—C23A—C22A	120.78 (15)	C24B—C23B—C22B	120.49 (14)
C24A—C23A—H23A	119.6	C24B—C23B—H23B	119.8
C22A—C23A—H23A	119.6	C22B—C23B—H23B	119.8
C25A—C24A—C23A	118.80 (15)	C25B—C24B—C23B	118.95 (14)
C25A—C24A—H24A	120.6	C25B—C24B—H24B	120.5
C23A—C24A—H24A	120.6	C23B—C24B—H24B	120.5
C24A—C25A—C20A	120.71 (13)	C24B—C25B—C20B	120.66 (13)
C24A—C25A—C1A	128.57 (13)	C24B—C25B—C1B	128.75 (13)
C20A—C25A—C1A	110.66 (12)	C20B—C25B—C1B	110.57 (12)

C14A—C1A—C2A—C3A	−57.28 (19)	C25B—C1B—C2B—C3B	59.58 (19)
C13A—C1A—C2A—C3A	−179.10 (13)	C13B—C1B—C2B—C3B	−178.52 (14)
C25A—C1A—C2A—C3A	58.36 (18)	C14B—C1B—C2B—C3B	−54.56 (18)
C14A—C1A—C2A—C7A	126.77 (13)	C25B—C1B—C2B—C7B	−122.87 (13)
C13A—C1A—C2A—C7A	4.95 (14)	C13B—C1B—C2B—C7B	−0.97 (14)
C25A—C1A—C2A—C7A	−117.60 (12)	C14B—C1B—C2B—C7B	123.00 (13)
C7A—C2A—C3A—C4A	1.9 (2)	C7B—C2B—C3B—C4B	−1.6 (2)
C1A—C2A—C3A—C4A	−173.66 (13)	C1B—C2B—C3B—C4B	175.71 (14)
C2A—C3A—C4A—C5A	1.3 (2)	C2B—C3B—C4B—C5B	0.0 (2)
C3A—C4A—C5A—C6A	−2.8 (2)	C3B—C4B—C5B—C6B	1.6 (2)
C4A—C5A—C6A—C7A	1.0 (2)	C4B—C5B—C6B—C7B	−1.5 (2)
C5A—C6A—C7A—C2A	2.2 (2)	C5B—C6B—C7B—C2B	−0.1 (2)
C5A—C6A—C7A—C8A	−178.85 (14)	C5B—C6B—C7B—C8B	−177.87 (14)
C3A—C2A—C7A—C6A	−3.7 (2)	C3B—C2B—C7B—C6B	1.7 (2)
C1A—C2A—C7A—C6A	172.59 (12)	C1B—C2B—C7B—C6B	−176.11 (12)
C3A—C2A—C7A—C8A	177.14 (12)	C3B—C2B—C7B—C8B	179.92 (12)
C1A—C2A—C7A—C8A	−6.58 (15)	C1B—C2B—C7B—C8B	2.15 (15)
C6A—C7A—C8A—C9A	9.2 (3)	C6B—C7B—C8B—C9B	−5.8 (3)
C2A—C7A—C8A—C9A	−171.77 (14)	C2B—C7B—C8B—C9B	176.19 (14)
C6A—C7A—C8A—C13A	−173.50 (14)	C6B—C7B—C8B—C13B	175.47 (14)
C2A—C7A—C8A—C13A	5.53 (15)	C2B—C7B—C8B—C13B	−2.54 (15)
C13A—C8A—C9A—C10A	0.7 (2)	C13B—C8B—C9B—C10B	0.3 (2)
C7A—C8A—C9A—C10A	177.75 (14)	C7B—C8B—C9B—C10B	−178.33 (14)
C8A—C9A—C10A—C11A	1.4 (2)	C8B—C9B—C10B—C11B	−1.3 (2)
C9A—C10A—C11A—C12A	−2.0 (2)	C9B—C10B—C11B—C12B	1.0 (2)
C10A—C11A—C12A—C13A	0.5 (2)	C10B—C11B—C12B—C13B	0.3 (2)
C11A—C12A—C13A—C8A	1.6 (2)	C11B—C12B—C13B—C8B	−1.3 (2)
C11A—C12A—C13A—C1A	−175.52 (13)	C11B—C12B—C13B—C1B	176.30 (13)
C9A—C8A—C13A—C12A	−2.2 (2)	C9B—C8B—C13B—C12B	1.0 (2)
C7A—C8A—C13A—C12A	−179.87 (12)	C7B—C8B—C13B—C12B	179.90 (12)
C9A—C8A—C13A—C1A	175.37 (12)	C9B—C8B—C13B—C1B	−176.96 (12)
C7A—C8A—C13A—C1A	−2.31 (15)	C7B—C8B—C13B—C1B	1.94 (15)
C2A—C1A—C13A—C12A	175.90 (13)	C25B—C1B—C13B—C12B	−55.60 (19)
C14A—C1A—C13A—C12A	50.54 (19)	C14B—C1B—C13B—C12B	61.44 (19)
C25A—C1A—C13A—C12A	−64.43 (18)	C2B—C1B—C13B—C12B	−178.42 (14)
C2A—C1A—C13A—C8A	−1.46 (14)	C25B—C1B—C13B—C8B	122.18 (13)
C14A—C1A—C13A—C8A	−126.82 (12)	C14B—C1B—C13B—C8B	−120.77 (13)
C25A—C1A—C13A—C8A	118.22 (13)	C2B—C1B—C13B—C8B	−0.63 (14)
C2A—C1A—C14A—C15A	−60.07 (19)	C25B—C1B—C14B—C15B	177.33 (14)
C13A—C1A—C14A—C15A	56.28 (19)	C13B—C1B—C14B—C15B	54.08 (19)
C25A—C1A—C14A—C15A	179.24 (14)	C2B—C1B—C14B—C15B	−60.68 (18)
C2A—C1A—C14A—C19A	122.93 (13)	C25B—C1B—C14B—C19B	−5.61 (14)
C13A—C1A—C14A—C19A	−120.73 (13)	C13B—C1B—C14B—C19B	−128.87 (13)
C25A—C1A—C14A—C19A	2.24 (14)	C2B—C1B—C14B—C19B	116.37 (13)
C19A—C14A—C15A—C16A	1.4 (2)	C19B—C14B—C15B—C16B	−1.7 (2)
C1A—C14A—C15A—C16A	−175.31 (14)	C1B—C14B—C15B—C16B	175.06 (13)
C14A—C15A—C16A—C17A	−0.3 (2)	C14B—C15B—C16B—C17B	−0.4 (2)
C15A—C16A—C17A—C18A	−1.0 (2)	C15B—C16B—C17B—C18B	1.5 (2)
C16A—C17A—C18A—C19A	1.1 (2)	C16B—C17B—C18B—C19B	−0.4 (2)
C17A—C18A—C19A—C14A	0.0 (2)	C17B—C18B—C19B—C14B	−1.8 (2)
C17A—C18A—C19A—C20A	179.06 (14)	C17B—C18B—C19B—C20B	178.01 (14)
C15A—C14A—C19A—C18A	−1.2 (2)	C15B—C14B—C19B—C18B	2.8 (2)
C1A—C14A—C19A—C18A	175.99 (13)	C1B—C14B—C19B—C18B	−174.47 (12)
C15A—C14A—C19A—C20A	179.47 (13)	C15B—C14B—C19B—C20B	−176.96 (12)
C1A—C14A—C19A—C20A	−3.29 (16)	C1B—C14B—C19B—C20B	5.72 (15)
C18A—C19A—C20A—C21A	6.8 (3)	C18B—C19B—C20B—C21B	−5.4 (3)
C14A—C19A—C20A—C21A	−173.99 (15)	C14B—C19B—C20B—C21B	174.35 (15)
C18A—C19A—C20A—C25A	−176.15 (15)	C18B—C19B—C20B—C25B	176.87 (15)
C14A—C19A—C20A—C25A	3.03 (16)	C14B—C19B—C20B—C25B	−3.35 (16)
C25A—C20A—C21A—C22A	−0.5 (2)	C25B—C20B—C21B—C22B	−1.0 (2)
C19A—C20A—C21A—C22A	176.18 (15)	C19B—C20B—C21B—C22B	−178.47 (15)
C20A—C21A—C22A—C23A	2.2 (2)	C20B—C21B—C22B—C23B	0.6 (2)
C21A—C22A—C23A—C24A	−1.8 (2)	C21B—C22B—C23B—C24B	0.2 (2)
C22A—C23A—C24A—C25A	−0.3 (2)	C22B—C23B—C24B—C25B	−0.7 (2)
C23A—C24A—C25A—C20A	2.0 (2)	C23B—C24B—C25B—C20B	0.3 (2)
C23A—C24A—C25A—C1A	−174.94 (14)	C23B—C24B—C25B—C1B	179.00 (13)
C21A—C20A—C25A—C24A	−1.6 (2)	C21B—C20B—C25B—C24B	0.5 (2)
C19A—C20A—C25A—C24A	−178.98 (13)	C19B—C20B—C25B—C24B	178.54 (13)
C21A—C20A—C25A—C1A	175.85 (13)	C21B—C20B—C25B—C1B	−178.38 (13)
C19A—C20A—C25A—C1A	−1.56 (16)	C19B—C20B—C25B—C1B	−0.37 (16)
C2A—C1A—C25A—C24A	51.95 (19)	C13B—C1B—C25B—C24B	−49.85 (19)
C14A—C1A—C25A—C24A	176.82 (14)	C14B—C1B—C25B—C24B	−175.29 (14)
C13A—C1A—C25A—C24A	−62.44 (19)	C2B—C1B—C25B—C24B	65.23 (19)
C2A—C1A—C25A—C20A	−125.21 (13)	C13B—C1B—C25B—C20B	128.95 (13)
C14A—C1A—C25A—C20A	−0.33 (14)	C14B—C1B—C25B—C20B	3.51 (14)
C13A—C1A—C25A—C20A	120.40 (13)	C2B—C1B—C25B—C20B	−115.97 (13)

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₂₅H₁₆·C₆H₆	C₂₅H₁₆·C₁₂H₁₀	C₂₅H₁₆
M_r	394.49	470.58	316.38
Crystal system, space group	Monoclinic, P2₁/n	Triclinic, P1	Monoclinic, P2₁/c
Temperature (K)	115	115	115
a, b, c (Å)	10.7900 (6), 18.4004 (10), 10.8403 (6)	9.774 (4), 11.427 (4), 13.075 (5)	18.2491 (17), 11.1522 (10), 18.6918 (17)
α, β, γ (°)	90, 92.877 (1), 90	71.339 (8), 83.106 (9), 67.030 (7)	90, 117.907 (2), 90
V (Å³)	2149.5 (2)	1273.8 (8)	3361.7 (5)
Z	4	2	8
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.07	0.07	0.07
Crystal size (mm)	0.2 × 0.2 × 0.2	0.14 × 0.11 × 0.04	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer	Bruker SMART CCD area detector diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)	Multi-scan (SADABS; Bruker, 2000)	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.893, 0.990	0.985, 0.998	0.970, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	14724, 4921, 3949	6971, 4476, 2416	18394, 5925, 4923
R_int	0.024	0.050	0.027
(sin θ/λ)_max (Å⁻¹)	0.650	0.596	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.02	0.079, 0.248, 0.92	0.041, 0.119, 1.05
No. of reflections	4921	4476	5925
No. of parameters	280	335	451
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.18	0.33, −0.29	0.32, −0.26

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SMART, SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cg1ⁱ	0.95	2.67	3.61	172
C11—H11···C16ⁱⁱ	0.95	2.74	3.6196 (18)	154

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

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···Cg2ⁱ	0.95	2.65	3.57	162
C29—H29···Cg3ⁱⁱ	0.95	2.63	3.56	163
C3—H3···C27	0.95	2.80	3.692 (5)	157
C28—H28···C22	0.95	2.84	3.658 (6)	147
C12—H12···C31ⁱⁱⁱ	0.95	2.87	3.783 (5)	161
C31—H31···C19^iv	0.95	2.80	3.708 (5)	159

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+2, −z; (iii) x−1, y, z; (iv) x+1, y, z.

Acknowledgements

The authors thank the EPSRC, UK, for funding the purchase of the diffractometer and the University of York for additional financial assistance.

References

Alcazar, V. & Diederich, F. (1992). Angew. Chem. Int. Ed. Engl. 31, 1521–1523. CrossRef Web of Science Google Scholar
Bruker (2000). SMART (Version 5.625), SAINT-Plus (Version 6.22) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Clarkson, R. G. & Gomberg, M. (1930). J. Am. Chem. Soc. 52, 2881–2896. CrossRef CAS Google Scholar
Lowden, L. J. & Chandler, D. (1974). J. Chem. Phys. 61, 5228–5241. CrossRef CAS Web of Science Google Scholar
Poriel, C., Ferrand, Y., le Maux, P., Paul, C., Rault-Berthelot, J. & Simonneaux, G. (2003). Chem. Commun. pp. 2308–2309. Web of Science CrossRef Google Scholar
Schenk, H. (1972). Acta Cryst. B28, 625–628. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Shi, X. Q. & Bartell, L. S. (1988). J. Phys. Chem. 92, 5667–5673. CrossRef CAS Web of Science Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar
Williams, J. H. (1993). Acc. Chem. Res. 26, 593–598. CrossRef CAS Web of Science Google Scholar
Wong, K. T., Chien, Y. Y., Chen, R. T., Wang, C. F., Lin, Y. T., Chiang, H. H., Hsieh, P. Y., Wu, C. C., Chou, C. H., Su, Y. O., Lee, G. H. & Peng, S. M. (2002). J. Am. Chem. Soc. 124, 11576–11577. Web of Science CSD CrossRef PubMed CAS Google Scholar

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ISSN: 2053-2296

Volume 61| Part 5| May 2005| Pages o328-o331

doi:10.1107/S0108270105009479