Conformational chirality of chemically symmetric mol­ecules and a superlattice through enantioselective self assembly: 1,1,1 tris­­[(4 cyano­phen­oxy)­methyl]­ethane

Acta Crystallographica Section E Structure Reports

Online ISSN 1600-5368

Conformational chirality of chemically symmetric

molecules and a superlattice through enantioselective

self-assembly:

1,1,1-tris[(4-cyanophenoxy)methyl]-ethane

Wei Xu,a,b_{* Zhen-Guang Zou,}b

Peng Guoa_{and Yin-Xiang Lu}a

a_{Department of Materials Science, Fudan}

University, Shanghai 200433, People's Republic of China, andb_{Department of Chemistry, Fudan}

University, Shanghai 200433, People's Republic of China

Correspondence e-mail: wexu@fudan.edu.cn

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.003 AÊ

Rfactor = 0.052

wRfactor = 0.134

Data-to-parameter ratio = 13.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C26H21N3O3, is a chemically symmetrical

molecule with one methyl group and three (4-cyanophenoxy)-methyl groups bonded to a tetracoordinate C atom. It crystallizes in the centrosymmetric space group P1. In the crystal structure, there are many non-covalent interactions, including O N short contacts and antiparallel dipole-dipole interactions. The tetracoordinate C atom of the molecule exhibits central chirality, while the three attached groups exhibit different axial chirality. The enantiomers form homochiral monolayers through enantioselective self-assembly, and the monolayers are packed in the formation of a superlattice based on alternating the two enantiomeric states. The physical image of molecular chirality as well as the concept of a superlattice with respect to chirality may provide a new insight into such a racemic crystal, which is very common in crystallography.

Comment

Molecules usually will not maintain their ideal shapes upon adsorption on solid surfaces or being packed into condensed phases, since they are soft materials. In recent years, much attention has been devoted to the recognition and measure-ment of chirality in molecules and molecular assemblies (Fasel

et al., 2004; Lopinskiet al., 1998; Casariniet al., 2001; Yuan & Liu, 2003; Borovkovet al., 2003). However, the understanding of the molecular packing arrangement and particularly the knowledge of the molecular geometry remains incomplete (Anthony et al., 1998; Pidcock & Motherwell, 2004). Very recently, we have shown that four chemically identical substituents attached to a central C atom have different conformations (Xu, Lu, Guo et al., 2004; Xu, Lu, Liu et al., 2004), indicating that the loss of ideal molecular symmetry does occur in the solid state. This paper continues our study of chemically symmetric molecules and focuses on the expression of molecular chirality and chiral structures in the solid state.

The title compound, (I), is a chemically symmetric molecule, with one methyl group and three (4-cyanophenoxy)methyl groups bonded to a tetracoordinate C atom. The molecular structure of (I), with the atom-labeling scheme, is shown in Fig. 1. Selected geometric parameters are given in Table 1.

In the crystal structure, there are CÐH N, CÐH O, CÐ H C, CÐH (C N) and edge-to-face aromatic interac-tions, similar to those observed in the crystal structure of tetrakis[(4-cyanophenoxy)methyl]methane (Xu et al., 2004). The short N Oi_{separation [3.268 (3) AÊ; symmetry code: (i)}

ÿ1ÿx, 1ÿy, 2ÿz] may partly be due to the dipole inter-action between the N atom and the Oi_{atom, since}

phenoxy)methyl groups are typical push±pull conjugated units.

In addition, the antiparallel dipole±dipole interactions between two push±pull conjugated units have been observed. For example, two conjugated units containing N3 are closely

packed in the formation of a dimer, as shown in Fig. 2; the N3 O3

ii _{separation is 3.478 (3) AÊ and the C26ÐN3 O3}ii

angle is 97.80 (15)_{[symmetry code: (ii) 1ÿx, 2ÿy, 1ÿz]. A}

relatively weak antiparallel dipole±dipole interaction exists between two conjugated units containing N2; the N2 O2i

separation is 4.242 (4) AÊ and the C18ÐN2 O2i _{angle is}

97.48 (19)_{. However, as for the conjugated units containing}

N1, the antiparallel dipole±dipole interaction can be neglected, since the separation between the two antiparallel units is larger than 5 AÊ. This discrimination suggests that the three (4-cyanophenoxy)methyl groups of the same molecule participate in different dipole interactions, and it also implies that such chemically identical groups are situated in different interaction environments.

As can be seen in Table 1, the bond length C2ÐC3 is larger than C2ÐC11 and C2ÐC19. Although C2ÐC11 and C2ÐC19 are the same, C11ÐO2 and C19ÐO3 are different. Such differences are further con®rmed by the torsion angles (see Table 1). For example, the torsion angles C2ÐC3ÐO1ÐC4, C2ÐC11ÐO2ÐC17 and C2ÐC19ÐO3ÐC20 are different, and the differences are far larger than their uncertainties [174.6 (2), 163.7 (2) and 172.8 (2)_{, respectively]. This}

indi-cates that the three chemically identical groups are different, and accordingly the tetracoordinated C2 can be regarded as an asymmetric center.

Considering each molecule in the unit cell, the spatial arrangement of the central C2 and the four neighboring atoms (C1, C3, C11 and C19) can be displayed by usingORTEP-3 (Farrugia, 1999). The con®gurations (Z = 2) are depicted in Fig. 3 and show that the tetracoordinate C2 is the mirror image of C2iii_{[symmetry code: (iii) 1ÿx,ÿy, 1ÿz].}

Furthermore, the corresponding torsion angles from one attached group are found to be different. For example, the

organic papers

Acta Cryst.(2004). E60, o2434±o2437 Xu, Zou, Guo and Lu C₂₆H₂₁N₃O₃

o2435

Figure 1

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2

torsion angles C11ÐO2ÐC17ÐC12 and C11ÐO2ÐC17Ð C16 are 14.6 (3) and ÿ166.65 (18)_{, respectively, suggesting}

that the arrangement of the bond C11ÐO2 and the benzene ring exhibits axial chirality. According to the space group, if one (4-cyanophenoxy)methyl group of the C2-molecule has a right-handed twist, the corresponding group of the C2iii

-mol-ecule has a left-handed one, orvice-versa.

The chiral feature of such a symmetric molecule is actually a combination of central and axial chirality: the tetracoordinate center exhibits central chirality, whereas the attached groups have axial chirality with left-handed or right-handed twist. For its convenience, if the molecule of C2 is de®ned as left-handed (L0_{), the molecule of C2}iii_{is right-handed (R}0_).

Inspection of the molecular packing arrangement of (I) reveals that the two enantiomers self-assemble into homo-chiral monolayers (all-L0 _{or all-R}0_{) parallel to (001). Each}

monolayer contains just one type of enantiomer. The mono-layers repeat in an . . .L0_R0_L0_R0_{. . . stacking sequence,}

forming a superlattice based on alternating the two enantio-meric layers, as shown in Fig. 4. Such a superlattice is very different from any ordinary superlattice (Noh et al., 1995; Gido, 1999), since the latter usually is based on alternating two different entities such asA-layer andB-layer.

Similar features have been seen in the crystal structures of tetrakis[(4-cyanophenoxy)methyl]methane (Xu et al., 2004).

In that case, the tetracoordinate C1 and C1iv_{have the same}

con®guration, while C1v _{and C1}vi _{exist in the enantiomeric}

state of C1 and C1iv_{[symmetry codes: (iv) 1ÿx,yÿ}1 2,12+z;

(v) 1ÿx, 1ÿy, 1ÿz; (vi) x, 3

2ÿy, 12+z]. It has also been

seen that the enantiomers self-assemble into homochiral monolayers, and further form a superlattice with respect to chirality.

The alternate packing of enantiomeric layers may be very common in many crystal structures; however, the concept of such a superlattice has never been mentioned. It may be helpful in the study of the physical and functional properties of a crystal, if we have a clear concept that the crystal is actually a low-dimensional system with respect to chirality. The fact that symmetric molecules exist in enantiomeric states may be the reason why high molecular symmetry does not necessarily lead to high crystal symmetry (Anthony et al., 1998). It also suggests that enantioselective self-organization should be taken into consideration in the description of the crystal packing of symmetric molecules (Pidcock & Mother-well, 2004).

Experimental

Compound (I) was synthesized by reacting 1,1,1-tris(bromomethyl)-ethane and potassium 4-cyanophenoxide, analogous to the procedure for the preparation of tetrakis[(4-cyanophenoxy)methyl]methane (Xuet al., 2004). Work-up gave the desired product (yield 76.8%), which was puri®ed by recrystallization from dimethylformamide and ethanol (m.p. 387±389 K); IR (KBr):2944, 2877, 2223, 1605, 1509, 1470, 1302, 1254, 1172, 1021, 829, 713 cmÿ1_. 1_{H NMR (CDCl}

3,

500 MHz):1.36 (s, 3H), 4.14 (s, 6H), 6.97 (d, J= 8.85 Hz, 6 H), 7.58 (d, J= 8.82 Hz, 6H).

Crystal data C26H21N3O3 Mr= 423.46 Triclinic,P1

a= 8.248 (3) AÊ

b= 10.097 (3) AÊ

c= 14.786 (5) AÊ

= 79.404 (5) = 74.292 (5) = 75.089 (4) V= 1136.8 (6) AÊ3

Z= 2

Dx= 1.237 Mg mÿ3 MoKradiation Cell parameters from 828

re¯ections

= 2.7±27.1 = 0.08 mmÿ1 T= 293 (2) K

Parallelepiped, colorless 0.450.400.35 mm Data collection

Bruker SMART CCD area-detector diffractometer

'and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.964,Tmax= 0.972

4780 measured re¯ections

3936 independent re¯ections 3350 re¯ections withI> 2(I)

Rint= 0.015 max= 25.0 h=ÿ9!9

k=ÿ11!11

l=ÿ12!17 Refinement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.052} wR(F2_{) = 0.134} S= 1.05 3936 re¯ections 289 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0533P)2 + 0.3456P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.22 e AÊÿ3

min=ÿ0.16 e AÊÿ3 Figure 3

The con®gurations of the two tetracoordinate centers (Z= 2).

Figure 4

Table 1

Selected geometric parameters (AÊ,_).

O1ÐC3 1.428 (2) O2ÐC11 1.437 (2) O3ÐC19 1.426 (2)

C2ÐC11 1.519 (3) C2ÐC19 1.519 (3) C2ÐC3 1.532 (3)

C1ÐC2ÐC3ÐO1 ÿ59.9 (2) C1ÐC2ÐC11ÐO2 ÿ59.3 (2) C1ÐC2ÐC19ÐO3 172.34 (15) C2ÐC3ÐO1ÐC4 174.57 (16) C2ÐC11ÐO2ÐC17 163.67 (16) C2ÐC19ÐO3ÐC20 172.76 (15)

C3ÐO1ÐC4ÐC5 ÿ0.6 (3) C3ÐO1ÐC4ÐC9 ÿ179.73 (18) C11ÐO2ÐC17ÐC12 14.6 (3) C11ÐO2ÐC17ÐC16 ÿ166.65 (18) C19ÐO3ÐC20ÐC21 ÿ4.9 (3) C19ÐO3ÐC20ÐC25 175.73 (17)

H atoms were included using a riding model, with CÐH = 0.95 AÊ andUiso= 1.2Ueq(C).

Data collection:SMART(Bruker, 1999); cell re®nement:SAINT (Bruker, 1999); data reduction:SAINT(Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.

The authors gratefully acknowledge ®nancial support from the Ministry of Education, China, and through project No. 0214nm005 supported by the Shanghai Science and Tech-nology Committee.

References

Anthony, A., Desiraju, G. R., Jetti, R. K. R., Kuduva, S. S., Madhavi, N. N. L., Nangia, A., Thaimattam, R. & Thalladi, V. R. (1998).Mater. Res. Bull.1, 1±18.

Borovkov, V. V., Harada, T., Hembury, G. A., Inoue, Y. & Kuroda, R. (2003).

Angew. Chem. Int. Ed.42, 1746±1749.

Bruker (1999).SMARTandSAINT.Bruker AXS Inc., Madison, Wisconsin, USA.

Casarini, D., Lunazzi, L. & Mazzanti, A. (2001).Angew. Chem. Int. Ed.40, 2536±2540.

Farrugia, L. J. (1999).ORTEP-3 for Windows. Version 1.05. University of Glasgow, Scotland.

Fasel, R., Wider, J., Quitmann, C., Ernst, K.-H. & Greber, T. (2004).Angew. Chem. Int. Ed.43, 2853±2856.

Gido, S. P. (1999).Nature (London),398, 107±108.

Lopinski, G. P., Moffatt, D. J., Wayner, D. D. & Wolkow, R. A. (1998).Nature (London),392, 909±911.

Noh, M., Thiel, J. & Johnson, D. C. (1995).Science,270, 1181±1184. Pidcock, E. & Motherwell, W. D. S. (2004).Cryst.Growth Des.4, 611±620. Sheldrick, G. M. (1996).SADABS.University of GoÈttingen, Germany. Sheldrick, G. M. (1997a).SHELXS97 &SHELXL97. University of GoÈttingen,

Germany.

Sheldrick, G. M. (1997b).SHELXTL.Bruker AXS Inc., Madison, Wisconsin, USA.

Xu, W., Lu, Y.-X., Guo, P., Zhou, H. & Lan, B.-J. (2004).Acta Cryst.E60, o428± o430.

Xu, W., Lu, Y.-X., Liu, C.-M., Guo, P., Lan, B.-J. & Zhou, H. (2004).Acta Cryst.

E60, o1049±o1050.

Yuan, J. & Liu, M.-H. (2003).J. Am. Chem. Soc.125, 5051±5056.

organic papers

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Acta Cryst. (2004). E60, o2434–o2437

supporting information

Acta Cryst. (2004). E60, o2434–o2437 [https://doi.org/10.1107/S1600536804029939]

Conformational chirality of chemically symmetric molecules and a superlattice

through enantioselective self-assembly:

1,1,1-tris[(4-cyanophenoxy)methyl]-ethane

Wei Xu, Zhen-Guang Zou, Peng Guo and Yin-Xiang Lu

1,1,1-tris[(4-cyanophenoxy)methyl]ethane

Crystal data C26H21N3O3

Mr = 423.46

Triclinic, P1 a = 8.248 (3) Å b = 10.097 (3) Å c = 14.786 (5) Å α = 79.404 (5)° β = 74.292 (5)° γ = 75.089 (4)° V = 1136.8 (6) Å3

Z = 2 F(000) = 444 Dx = 1.237 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 828 reflections θ = 2.7–27.1°

µ = 0.08 mm−1

T = 293 K

Parallelepiped, colourless 0.45 × 0.40 × 0.35 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.964, Tmax = 0.972

4780 measured reflections 3936 independent reflections 3350 reflections with I > 2σ(I) Rint = 0.015

θmax = 25.0°, θmin = 2.1°

h = −9→9 k = −11→11 l = −12→17

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.052}

wR(F2_{) = 0.134}

S = 1.05 3936 reflections 289 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0533P)2 + 0.3456P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.22 e Å−3

supporting information

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Acta Cryst. (2004). E60, o2434–o2437 Special details

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

N1 0.9279 (3) −0.0993 (2) 0.86727 (19) 0.0883 (7) N2 −0.9152 (3) 0.7360 (3) 1.09970 (18) 0.0960 (8) N3 0.4091 (3) 1.3621 (2) 0.43431 (15) 0.0698 (6) O1 0.24958 (16) 0.36296 (14) 0.75397 (11) 0.0560 (4) O2 −0.19828 (17) 0.66364 (15) 0.74973 (10) 0.0579 (4) O3 0.1547 (2) 0.78080 (14) 0.64707 (10) 0.0576 (4) C1 0.0183 (3) 0.4640 (2) 0.63121 (17) 0.0565 (5)

H1A −0.0938 0.5104 0.6213 0.085*

H1B 0.0098 0.3808 0.6739 0.085*

H1C 0.0950 0.4416 0.5718 0.085*

C2 0.0884 (2) 0.55825 (19) 0.67348 (14) 0.0443 (5) C3 0.2673 (2) 0.48579 (19) 0.69009 (15) 0.0466 (5)

H3A 0.3470 0.4629 0.6307 0.056*

H3B 0.3117 0.5459 0.7169 0.056*

C4 0.3945 (2) 0.2748 (2) 0.77336 (15) 0.0465 (5) C5 0.5600 (3) 0.2951 (2) 0.73465 (16) 0.0538 (5)

H5A 0.5788 0.3737 0.6930 0.065*

C6 0.6968 (3) 0.1964 (2) 0.75896 (17) 0.0594 (6)

H6A 0.8087 0.2088 0.7332 0.071*

C7 0.6700 (3) 0.0795 (2) 0.82093 (16) 0.0555 (5) C8 0.5035 (3) 0.0606 (2) 0.85917 (17) 0.0566 (5)

H8A 0.4847 −0.0181 0.9008 0.068*

C9 0.3664 (3) 0.1578 (2) 0.83564 (16) 0.0543 (5)

H9A 0.2545 0.1452 0.8614 0.065*

C10 0.8139 (3) −0.0204 (2) 0.84715 (18) 0.0652 (6) C11 −0.0320 (2) 0.5954 (2) 0.76736 (14) 0.0474 (5)

H11A −0.0409 0.5126 0.8119 0.057*

H11B 0.0119 0.6561 0.7940 0.057*

C12 −0.3288 (3) 0.6546 (2) 0.91831 (15) 0.0531 (5)

H12A −0.2221 0.6295 0.9339 0.064*

C13 −0.4788 (3) 0.6708 (2) 0.98840 (16) 0.0568 (5)

H13A −0.4729 0.6561 1.0515 0.068*

C14 −0.6374 (3) 0.7086 (2) 0.96607 (16) 0.0526 (5) C15 −0.6463 (3) 0.7314 (2) 0.87184 (17) 0.0588 (6)

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C16 −0.4965 (3) 0.7147 (2) 0.80180 (16) 0.0581 (6)

H16A −0.5021 0.7298 0.7386 0.070*

C17 −0.3376 (2) 0.6758 (2) 0.82461 (15) 0.0474 (5) C18 −0.7936 (3) 0.7242 (2) 1.04004 (18) 0.0658 (6) C19 0.1116 (3) 0.6853 (2) 0.60234 (15) 0.0493 (5)

H19A 0.2029 0.6597 0.5473 0.059*

H19B 0.0057 0.7269 0.5817 0.059*

C20 0.2010 (2) 0.89694 (19) 0.59648 (14) 0.0470 (5) C21 0.2234 (3) 0.9298 (2) 0.49932 (15) 0.0505 (5)

H21A 0.2025 0.8718 0.4637 0.061*

C22 0.2770 (3) 1.0495 (2) 0.45589 (15) 0.0521 (5)

H22A 0.2934 1.0714 0.3906 0.062*

C23 0.3066 (2) 1.1372 (2) 0.50814 (15) 0.0481 (5) C24 0.2804 (3) 1.1041 (2) 0.60568 (16) 0.0563 (5)

H24A 0.2986 1.1630 0.6416 0.068*

C25 0.2280 (3) 0.9855 (2) 0.64909 (15) 0.0570 (6)

H25A 0.2104 0.9642 0.7145 0.068*

C26 0.3646 (3) 1.2616 (2) 0.46505 (16) 0.0541 (5)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

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Acta Cryst. (2004). E60, o2434–o2437

C21 0.0513 (12) 0.0469 (11) 0.0498 (12) −0.0059 (9) −0.0118 (10) −0.0040 (9) C22 0.0507 (12) 0.0520 (12) 0.0446 (11) −0.0017 (9) −0.0099 (9) 0.0006 (9) C23 0.0386 (10) 0.0416 (11) 0.0542 (12) 0.0012 (8) −0.0074 (9) −0.0007 (9) C24 0.0671 (14) 0.0452 (12) 0.0544 (13) −0.0065 (10) −0.0152 (11) −0.0078 (10) C25 0.0728 (14) 0.0480 (12) 0.0437 (12) −0.0064 (10) −0.0131 (11) −0.0001 (10) C26 0.0452 (11) 0.0506 (12) 0.0568 (13) −0.0022 (10) −0.0054 (10) −0.0042 (10)

Geometric parameters (Å, º)

N1—C10 1.134 (3) C9—H9A 0.9300

N2—C18 1.139 (3) C11—H11A 0.9700

N3—C26 1.142 (3) C11—H11B 0.9700

O1—C4 1.359 (2) C12—C13 1.377 (3)

O1—C3 1.428 (2) C12—C17 1.381 (3)

O2—C17 1.360 (2) C12—H12A 0.9300

O2—C11 1.437 (2) C13—C14 1.378 (3)

O3—C20 1.354 (2) C13—H13A 0.9300

O3—C19 1.426 (2) C14—C15 1.388 (3)

C1—C2 1.525 (3) C14—C18 1.441 (3)

C1—H1A 0.9600 C15—C16 1.375 (3)

C1—H1B 0.9600 C15—H15A 0.9300

C1—H1C 0.9600 C16—C17 1.382 (3)

C2—C11 1.519 (3) C16—H16A 0.9300

C2—C19 1.519 (3) C19—H19A 0.9700

C2—C3 1.532 (3) C19—H19B 0.9700

C3—H3A 0.9700 C20—C25 1.381 (3)

C3—H3B 0.9700 C20—C21 1.386 (3)

C4—C5 1.382 (3) C21—C22 1.380 (3)

C4—C9 1.387 (3) C21—H21A 0.9300

C5—C6 1.379 (3) C22—C23 1.380 (3)

C5—H5A 0.9300 C22—H22A 0.9300

C6—C7 1.381 (3) C23—C24 1.389 (3)

C6—H6A 0.9300 C23—C26 1.436 (3)

C7—C8 1.385 (3) C24—C25 1.366 (3)

C7—C10 1.437 (3) C24—H24A 0.9300

C8—C9 1.371 (3) C25—H25A 0.9300

C8—H8A 0.9300

C4—O1—C3 118.51 (14) H11A—C11—H11B 108.5

C17—O2—C11 118.39 (15) C13—C12—C17 119.59 (19) C20—O3—C19 120.52 (16) C13—C12—H12A 120.2

C2—C1—H1A 109.5 C17—C12—H12A 120.2

C2—C1—H1B 109.5 C12—C13—C14 120.7 (2)

H1A—C1—H1B 109.5 C12—C13—H13A 119.6

C2—C1—H1C 109.5 C14—C13—H13A 119.6

H1A—C1—H1C 109.5 C13—C14—C15 119.67 (19)

H1B—C1—H1C 109.5 C13—C14—C18 120.2 (2)

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Acta Cryst. (2004). E60, o2434–o2437

C11—C2—C1 110.15 (16) C16—C15—C14 119.6 (2)

C19—C2—C1 108.66 (17) C16—C15—H15A 120.2

C11—C2—C3 108.82 (16) C14—C15—H15A 120.2

C19—C2—C3 106.78 (15) C15—C16—C17 120.5 (2)

C1—C2—C3 110.27 (16) C15—C16—H16A 119.8

O1—C3—C2 107.68 (15) C17—C16—H16A 119.8

O1—C3—H3A 110.2 O2—C17—C12 124.64 (18)

C2—C3—H3A 110.2 O2—C17—C16 115.43 (18)

O1—C3—H3B 110.2 C12—C17—C16 119.92 (19)

C2—C3—H3B 110.2 N2—C18—C14 178.8 (3)

H3A—C3—H3B 108.5 O3—C19—C2 108.19 (16)

O1—C4—C5 124.37 (18) O3—C19—H19A 110.1

O1—C4—C9 114.95 (17) C2—C19—H19A 110.1

C5—C4—C9 120.67 (18) O3—C19—H19B 110.1

C6—C5—C4 118.7 (2) C2—C19—H19B 110.1

C6—C5—H5A 120.6 H19A—C19—H19B 108.4

C4—C5—H5A 120.6 O3—C20—C25 114.88 (18)

C5—C6—C7 121.04 (19) O3—C20—C21 125.20 (19)

C5—C6—H6A 119.5 C25—C20—C21 119.92 (19)

C7—C6—H6A 119.5 C22—C21—C20 119.4 (2)

C6—C7—C8 119.62 (18) C22—C21—H21A 120.3

C6—C7—C10 120.2 (2) C20—C21—H21A 120.3

C8—C7—C10 120.2 (2) C21—C22—C23 120.8 (2)

C9—C8—C7 120.0 (2) C21—C22—H22A 119.6

C9—C8—H8A 120.0 C23—C22—H22A 119.6

C7—C8—H8A 120.0 C22—C23—C24 119.12 (19)

C8—C9—C4 119.99 (19) C22—C23—C26 122.2 (2)

C8—C9—H9A 120.0 C24—C23—C26 118.7 (2)

C4—C9—H9A 120.0 C25—C24—C23 120.4 (2)

N1—C10—C7 179.6 (3) C25—C24—H24A 119.8

O2—C11—C2 107.68 (15) C23—C24—H24A 119.8

O2—C11—H11A 110.2 C24—C25—C20 120.4 (2)

C2—C11—H11A 110.2 C24—C25—H25A 119.8

O2—C11—H11B 110.2 C20—C25—H25A 119.8

C2—C11—H11B 110.2 N3—C26—C23 177.3 (2)