organic papers
Acta Cryst.(2005). E61, o659–o661 doi:10.1107/S1600536805004228 Aramakiet al. C
44H38N43C7H8
o659
Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
1,4:8,11:15,18:22,25-Tetraethano-29
H
,31
H
-tetra-benzo[
b
,
g
,
l
,
q
]porphine toluene trisolvate
Shinji Aramaki,aYoshimasa Sakai,aHiroyuki Yanagisawab and Jin Mizuguchib*
aMitsubishi Chemical Group Science and
Technology Research Centre, Kamoshida-cho 1000, Aoba-ku, Yokohama 227-8502, Japan, andbDepartment of Applied Physics, Graduate
School of Engineering, Yokohama National University, Tokiwadai 79-5, Hodogaya-ku, Yokohama 240-8501, Japan
Correspondence e-mail: mizu-j@ynu.ac.jp
Key indicators
Single-crystal X-ray study T= 93 K
Mean(C–C) = 0.009 A˚ Disorder in solvent or counterion Rfactor = 0.073
wRfactor = 0.197 Data-to-parameter ratio = 9.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
In the title compound, C44H38N43C7H8, the porphine (CP) is a
soluble precursor of metal-free porphyrin which exhibits an excellent field-effect transistor characteristic. The CP mol-ecule is not entirely flat in its crystal structure (i.e.notD2h),
but is slightly deformed, as characterized by crystallographic
Ci symmetry. The geometric isomer of CP could not be
identified due to orientational disorder.
Comment
Organic field-effect transistors (FET) are advantageous due to lower fabrication costs and larger-area devices compared with inorganic FETs. We have recently reported that metal-free porphyrin, so-called benzoporphyrin (BP), exhibits an
excel-lent FET characteristic (Aramaki et al., 2004). Our FET
[image:1.610.208.468.445.637.2]system is characterized by the use of a soluble BP precursor, CP, and its thermal transformation into BP directly on the substrate at about 473 K. In order to improve the FET performance further, it is crucial to study the correlation between structure and solid-state properties. The structure of BP has previously been reported (Aramaki & Mizuguchi, 2003). The present paper deals with the structure of the title compound, (I), which is the toluene trisolvate of CP.
Fig. 1 shows the structure of the CP molecule of (I). The centrosymmetric molecule is not entirely planar. The angle
between the plane of the four N atoms [N1/N1i/N2/N2i;
symmetry code: (i) 1x, 2y, 1z] and the C3/C4/C7/C8
plane is 2.9 (3), while the angle between the central plane and
that composed of atoms C14/C15/C16/C19 is 7.1 (3).
According to the scheme, there should be one single bond and one double bond in the bicyclic ring system at the periphery of
the molecule. However, the C5—C6, C9—C10, C17—C18 and C20—C21 bond lengths are in the range 1.426 (9)–1.436 (8) A˚ . These are intermediate between single and double bonds. This presumably occurs because the molecule and its inverse are arranged randomly in the crystal structure, giving a crystal-lographically averaged bond length.
It is also to be noted that we have successfully isolated two geometric isomers by column chromatography and confirmed that their NMR spectra are different. However, the crystals of the two isomers showed the same cell constants and similar disorder of the bicyclic ring system by X-ray analyses.
Fig. 2 shows the packing arrangement of CP with the toluene molecules. The solvent molecules are sandwiched between two CP molecules.
Experimental
CP was synthesized according to the method previously reported by Itoet al. (1998). The product was purified by column chromatography and recrystallization. Single crystals of (I) were then grown from a toluene solution. Since the crystal was found to include solvent molecules, X-ray intensity data were collected at 93 K.
Crystal data
C44H38N43C7H8
Mr= 899.18
Triclinic,P1
a= 9.986 (3) A˚
b= 11.682 (3) A˚
c= 12.222 (4) A˚ = 117.17 (2) = 103.69 (2) = 92.56 (2) V= 1213.0 (7) A˚3
Z= 1
Dx= 1.231 Mg m
3
CuKradiation Cell parameters from 8380
reflections = 4.2–56.9 = 0.54 mm1
T= 93.2 K Block, dark red 0.400.400.20 mm
Data collection
Rigaku R-AXIS RAPID imaging plate diffractometer
!scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)
Tmin= 0.471,Tmax= 0.897
8409 measured reflections
3020 independent reflections 1754 reflections withF2> 2(F2)
Rint= 0.067
max= 56.9
h=10!10
k=12!12
l=13!12
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.073
wR(F2) = 0.197
S= 1.26 3020 reflections 316 parameters
H-atom parameters constrained
w= 1/[2(F o2) +
{0.05[max(Fo2,0) + 2Fc2]/3}2]
(/)max< 0.001 max= 0.45 e A˚
3 min=0.46 e A˚
[image:2.610.316.565.71.291.2]3
Table 1
Selected geometric parameters (A˚ ,).
N1—C2 1.376 (7)
N1—C11 1.382 (7)
N2—C13 1.392 (7)
N2—C22 1.381 (7)
C1—C2 1.391 (8)
C1—C13 1.382 (8)
C2—C3 1.441 (8)
C3—C8 1.361 (8)
C5—C6 1.433 (9)
C8—C11 1.433 (7)
C9—C10 1.435 (10)
C11—C12 1.382 (8) C12—C22i
1.397 (8) C13—C14 1.446 (8) C14—C15 1.343 (8) C15—C22 1.452 (8) C17—C18 1.426 (9) C20—C21 1.436 (8)
C2—N1—C11 110.0 (4) C13—N2—C22 106.5 (4) C2—C1—C13 127.5 (5) N1—C2—C1 124.7 (5) N1—C2—C3 107.0 (5) C1—C2—C3 128.2 (5) C2—C3—C8 107.6 (5) C3—C8—C11 108.9 (5) N1—C11—C8 106.5 (5) N1—C11—C12 125.9 (5)
C8—C11—C12 127.6 (5) C11—C12—C22i
128.3 (5) N2—C13—C1 124.4 (5) N2—C13—C14 109.3 (5) C1—C13—C14 126.3 (5) C13—C14—C15 107.2 (5) C14—C15—C22 108.1 (5) N2—C22—C12i
125.8 (5) N2—C22—C15 108.8 (5) C12i
—C22—C15 125.3 (5)
Symmetry code: (i) 1x;2y;1z.
organic papers
o660
Aramakiet al. C44H38N43C7H8 Acta Cryst.(2005). E61, o659–o661
Figure 2
[image:2.610.50.294.74.320.2]The crystal structure of (I). H atoms and one of two possible positions of the methyl C33 atom of toluene have been omitted for clarity.
Figure 1
[image:2.610.314.566.541.725.2]All the H atoms were positioned geometrically and included in a riding-model approximation, with C—H and N—H distances of 0.95 A˚ and withUiso(H) = 1.2Ueq(C,N). A positive peak was found
near atom N1 in the difference density map. However, it deviated slightly from the plane composed of the four N atoms. Therefore, the H atom bonded to N1 was calculated by assumingsp2hybridation. Six H atoms attached to the bicyclic ring system at the periphery of the CP molecule were positioned in the following way. As described in theComment, one of the two C—C bonds is a single bond, whereas the other one is double. At one corner, since the C5—C6 bond is just slightly shorter than the C9—C10 one, two –CH were tentatively attached to the former, and two –CH2 to the latter. Similarly, at
another corner, two –CH were attached to the C17—C18 bond, and two –CH2to the C20—C21 bond. There are one and a half
inde-pendent toluene molecules in the asymmetric unit. The benzene ring of one of the three toluene molecules in the unit cell has a crystal-lographic centre of symmetry, and the methyl group (C33) is disor-dered over two sites of 50% occupancy each.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refine-ment: PROCESS-AUTO; data reduction: TEXSAN (Molecular
Structure Corporation, 2001); program(s) used to solve structure: SHELXS86(Sheldrick, 1985); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication:TEXSAN.
The authors express their sincere thanks to Mr I. Suzuki for experimental assistance.
References
Aramaki, S. & Mizuguchi, J. (2003).Acta Cryst. E,59, o1556–o1558. Aramaki, S., Sakai, Y. & Ono, N. (2004). Appl. Phys. Lett. 84, 2085–
2087.
Burnett, M. N. & Johnson, C. K. (1996).ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory. Tennessee, USA.
Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.
Ito, S., Ochi, N., Murashima, T., Uno, H. & Ono, N. (1998).Chem. Commun.
pp. 1661–1662.
Molecular Structure Corporation (2001).TEXSAN. Version 1.11. MSC, 9009 New Trails Drive, The Woodlands, TX 77381-5209, USA.
Rigaku (1998).PROCESS-AUTO.Rigaku Corporation, Tokyo, Japan. Sheldrick, G. M. (1985).SHELXS86. University of Go¨ttingen, Germany.
organic papers
Acta Cryst.(2005). E61, o659–o661 Aramakiet al. C
supporting information
sup-1
Acta Cryst. (2005). E61, o659–o661
supporting information
Acta Cryst. (2005). E61, o659–o661 [https://doi.org/10.1107/S1600536805004228]
1,4:8,11:15,18:22,25-Tetraethano-29
H
,31
H
-tetrabenzo[
b
,
g
,
l
,
q
]porphine toluene
trisolvate
Shinji Aramaki, Yoshimasa Sakai, Hiroyuki Yanagisawa and Jin Mizuguchi
1,4:8,11:15,18:22,25-Tetraethano-29H,31H-tetrabenzo[b,g,l,q]porphine toluene trisolvate
Crystal data
C44H38N4·3C7H8 Mr = 899.18
Triclinic, P1 Hall symbol: -P 1
a = 9.986 (3) Å
b = 11.682 (3) Å
c = 12.222 (4) Å
α = 117.17 (2)°
β = 103.69 (2)°
γ = 92.56 (2)°
V = 1213.0 (7) Å3
Z = 1
F(000) = 480
Dx = 1.231 Mg m−3
Cu Kα radiation, λ = 1.5418 Å Cell parameters from 8380 reflections
θ = 4.2–56.9°
µ = 0.54 mm−1 T = 93 K Block, dark red 0.40 × 0.40 × 0.20 mm
Data collection
Rigaku R-AXIS RAPID imaging plate diffractometer
Detector resolution: 10.00 pixels mm-1
48 frames, δω = 15° scans Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
Tmin = 0.471, Tmax = 0.897 8409 measured reflections
3020 independent reflections 1754 reflections with F2 > 2σ(F2) Rint = 0.067
θmax = 56.9°
h = 0→10
k = −12→12
l = −13→12
Refinement
Refinement on F2 R[F2 > 2σ(F2)] = 0.073 wR(F2) = 0.197 S = 1.26 3020 reflections 316 parameters
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.05(Max(Fo2,0) + 2Fc2)/3)2]
(Δ/σ)max < 0.001
Δρmax = 0.45 e Å−3
Δρmin = −0.46 e Å−3
Special details
Refinement. Refinement using reflections with F2 > -10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are
based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor
supporting information
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Acta Cryst. (2005). E61, o659–o661
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq Occ. (<1)
N1 0.4543 (4) 0.9085 (4) 0.2983 (4) 0.033 (1) N2 0.6729 (4) 0.9136 (4) 0.5039 (4) 0.033 (1) C1 0.6541 (5) 0.7942 (5) 0.2741 (5) 0.032 (2) C2 0.5308 (5) 0.8277 (5) 0.2251 (5) 0.030 (2) C3 0.4586 (5) 0.7868 (5) 0.0927 (5) 0.035 (2) C4 0.4760 (6) 0.7001 (6) −0.0366 (5) 0.038 (2) C5 0.3418 (6) 0.5977 (6) −0.1127 (5) 0.047 (2) C6 0.2184 (6) 0.6558 (6) −0.1131 (5) 0.045 (2) C7 0.2502 (6) 0.8047 (6) −0.0436 (5) 0.038 (2) C8 0.3417 (5) 0.8424 (5) 0.0906 (5) 0.034 (2) C9 0.4710 (6) 0.7846 (7) −0.1034 (6) 0.051 (2) C10 0.3463 (6) 0.8410 (6) −0.1070 (5) 0.046 (2) C11 0.3374 (5) 0.9207 (5) 0.2199 (5) 0.032 (2) C12 0.2361 (5) 0.9926 (5) 0.2604 (5) 0.031 (2) C13 0.7214 (5) 0.8334 (5) 0.4014 (5) 0.031 (2) C14 0.8531 (5) 0.8020 (5) 0.4501 (5) 0.032 (2) C15 0.8819 (6) 0.8603 (5) 0.5785 (5) 0.033 (2) C16 1.0209 (5) 0.8443 (5) 0.6475 (5) 0.034 (2) C17 1.1299 (6) 0.8963 (6) 0.6044 (6) 0.045 (2) C18 1.0998 (6) 0.8360 (6) 0.4682 (6) 0.043 (2) C19 0.9654 (5) 0.7335 (5) 0.3986 (5) 0.032 (2) C20 1.0197 (6) 0.6972 (5) 0.5873 (5) 0.041 (2) C21 0.9899 (6) 0.6352 (5) 0.4501 (5) 0.043 (2) C22 0.7697 (5) 0.9308 (5) 0.6141 (5) 0.035 (2) C23 0.1954 (5) 0.4492 (5) 0.1300 (5) 0.035 (2) C24 0.2206 (6) 0.3839 (6) 0.2015 (5) 0.042 (2) C25 0.1860 (6) 0.2495 (6) 0.1446 (6) 0.044 (2) C26 0.1232 (6) 0.1776 (6) 0.0137 (6) 0.047 (2) C27 0.0957 (6) 0.2413 (6) −0.0588 (5) 0.045 (2) C28 0.1313 (6) 0.3760 (6) −0.0006 (5) 0.040 (2) C29 0.2401 (7) 0.5962 (6) 0.1937 (6) 0.054 (2) C30 0.4276 (8) 0.4140 (9) 0.5241 (6) 0.066 (2) C31 0.5326 (8) 0.3776 (8) 0.4649 (6) 0.064 (2) C32 0.6027 (8) 0.4643 (9) 0.4404 (6) 0.069 (3)
C33 0.5583 (11) 0.2617 (13) 0.4296 (11) 0.035 (3) 0.50 H1 0.6969 0.7378 0.2129 0.0382*
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Acta Cryst. (2005). E61, o659–o661
H16 1.0387 0.8861 0.7382 0.0406* H17A 1.2187 0.8807 0.6386 0.0544* H17B 1.1328 0.9877 0.6372 0.0544* H18A 1.1758 0.7947 0.4442 0.0520* H18B 1.0897 0.9015 0.4428 0.0520* H19 0.9433 0.6937 0.3077 0.0390* H20 1.0368 0.6517 0.6354 0.0497* H21 0.9858 0.5444 0.3971 0.0511* H24 0.2627 0.4328 0.2917 0.0500* H25 0.2052 0.2067 0.1951 0.0524* H26 0.0990 0.0851 −0.0263 0.0559* H27 0.0521 0.1923 −0.1488 0.0541* H28 0.1115 0.4187 −0.0512 0.0474* H29A 0.3386 0.6186 0.2320 0.0646* H29B 0.2153 0.6243 0.1310 0.0646* H29C 0.1943 0.6378 0.2578 0.0646* H30 0.3775 0.3545 0.5396 0.0797*
H31 0.5565 0.2934 0.4413 0.0507* 0.50 H32 0.6730 0.4381 0.3980 0.0824*
H33A 0.5852 0.2485 0.5024 0.0417* 0.50 H33B 0.6321 0.2503 0.3908 0.0417* 0.50 H33C 0.4766 0.2003 0.3695 0.0417* 0.50 H34 0.4783 0.9500 0.3894 0.0395*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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Acta Cryst. (2005). E61, o659–o661
C20 0.049 (4) 0.028 (3) 0.039 (4) 0.004 (3) −0.005 (3) 0.018 (3) C21 0.058 (4) 0.029 (3) 0.039 (4) 0.008 (3) 0.011 (3) 0.016 (3) C22 0.032 (3) 0.033 (3) 0.037 (4) 0.004 (3) 0.007 (3) 0.016 (3) C23 0.026 (3) 0.040 (4) 0.036 (3) 0.004 (3) 0.007 (3) 0.017 (3) C24 0.035 (3) 0.050 (4) 0.029 (3) 0.003 (3) 0.005 (3) 0.012 (3) C25 0.037 (3) 0.045 (4) 0.051 (4) 0.006 (3) 0.008 (3) 0.028 (3) C26 0.036 (3) 0.041 (4) 0.049 (4) −0.000 (3) 0.007 (3) 0.014 (3) C27 0.043 (4) 0.043 (4) 0.034 (3) −0.004 (3) 0.003 (3) 0.011 (3) C28 0.037 (3) 0.046 (4) 0.033 (3) 0.004 (3) 0.006 (3) 0.020 (3) C29 0.057 (4) 0.045 (4) 0.050 (4) 0.007 (3) 0.011 (3) 0.017 (3) C30 0.065 (5) 0.080 (6) 0.028 (4) −0.042 (5) −0.003 (4) 0.017 (4) C31 0.072 (5) 0.067 (5) 0.025 (4) −0.032 (5) −0.006 (4) 0.013 (4) C32 0.066 (5) 0.087 (6) 0.029 (4) −0.031 (5) 0.003 (4) 0.018 (4) C33 0.032 (6) 0.050 (8) 0.030 (6) 0.008 (6) 0.013 (5) 0.024 (6)
Geometric parameters (Å, º)
N1—C2 1.376 (7) C16—H16 0.950
N1—C11 1.382 (7) C17—C18 1.426 (9)
N1—H34 0.950 C17—H17A 0.950
N2—C13 1.392 (7) C17—H17B 0.950
N2—C22 1.381 (7) C18—C19 1.531 (7)
C1—C2 1.391 (8) C18—H18A 0.950
C1—C13 1.382 (8) C18—H18B 0.950
C1—H1 0.950 C19—C21 1.54 (1)
C2—C3 1.441 (8) C19—H19 0.950
C3—C4 1.496 (8) C20—C21 1.436 (8)
C3—C8 1.361 (8) C20—H20 0.950
C4—C5 1.530 (7) C21—H21 0.950
C4—C9 1.54 (1) C23—C24 1.39 (1)
C4—H4 0.950 C23—C28 1.382 (7)
C5—C6 1.433 (9) C23—C29 1.516 (9)
C5—H5A 0.950 C24—C25 1.382 (9)
C5—H5B 0.950 C24—H24 0.950
C6—C7 1.524 (9) C25—C26 1.382 (8)
C6—H6A 0.950 C25—H25 0.950
C6—H6B 0.950 C26—C27 1.38 (1)
C7—C8 1.522 (8) C26—H26 0.950
C7—C10 1.52 (1) C27—C28 1.385 (9)
C7—H7 0.950 C27—H27 0.950
C8—C11 1.433 (7) C28—H28 0.950
C9—C10 1.435 (10) C29—H29A 0.950
C9—H9 0.950 C29—H29B 0.950
C10—H10 0.950 C29—H29C 0.950
C11—C12 1.382 (8) C30—C31 1.39 (1)
C12—C22i 1.397 (8) C30—C32ii 1.36 (1)
C12—H12 0.950 C30—H30 0.950
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Acta Cryst. (2005). E61, o659–o661
C14—C15 1.343 (8) C31—C33 1.28 (2)
C14—C19 1.500 (8) C31—H31 0.950
C15—C16 1.512 (8) C32—H32 0.950
C15—C22 1.452 (8) C33—H33A 0.950
C16—C17 1.53 (1) C33—H33B 0.950
C16—C20 1.527 (8) C33—H33C 0.950
N2···C18iii 3.458 (7) C9···C25iv 3.592 (8)
N2···C33ii 3.49 (1) C13···C17iii 3.467 (8)
C1···C17iii 3.580 (8) C18···C22iii 3.596 (8)
C2—N1—C11 110.0 (4) C16—C17—H17A 108.6 C2—N1—H34 125.0 C16—C17—H17B 108.6 C11—N1—H34 125.0 C18—C17—H17A 108.6 C13—N2—C22 106.5 (4) C18—C17—H17B 108.6 C2—C1—C13 127.5 (5) H17A—C17—H17B 109.5 C2—C1—H1 116.2 C17—C18—C19 112.4 (6) C13—C1—H1 116.2 C17—C18—H18A 108.7 N1—C2—C1 124.7 (5) C17—C18—H18B 108.7 N1—C2—C3 107.0 (5) C19—C18—H18A 108.7 C1—C2—C3 128.2 (5) C19—C18—H18B 108.7 C2—C3—C4 137.6 (5) H18A—C18—H18B 109.5 C2—C3—C8 107.6 (5) C14—C19—C18 105.9 (4) C4—C3—C8 114.8 (5) C14—C19—C21 105.9 (6) C3—C4—C5 106.3 (5) C14—C19—H19 113.2 C3—C4—C9 105.7 (5) C18—C19—C21 104.8 (5)
C3—C4—H4 113.2 C18—C19—H19 113.2
C5—C4—C9 104.6 (5) C21—C19—H19 113.2 C5—C4—H4 113.2 C16—C20—C21 112.6 (6)
C9—C4—H4 113.2 C16—C20—H20 123.7
C4—C5—C6 112.3 (5) C21—C20—H20 123.7 C4—C5—H5A 108.8 C19—C21—C20 112.1 (5)
C4—C5—H5B 108.8 C19—C21—H21 124.0
C6—C5—H5A 108.8 C20—C21—H21 124.0
C6—C5—H5B 108.8 N2—C22—C12i 125.8 (5)
H5A—C5—H5B 109.5 N2—C22—C15 108.8 (5) C5—C6—C7 113.2 (5) C12i—C22—C15 125.3 (5)
C5—C6—H6A 108.5 C24—C23—C28 118.0 (6) C5—C6—H6B 108.5 C24—C23—C29 120.7 (5) C7—C6—H6A 108.5 C28—C23—C29 121.3 (7) C7—C6—H6B 108.5 C23—C24—C25 121.6 (5) H6A—C6—H6B 109.5 C23—C24—H24 119.2 C6—C7—C8 104.7 (6) C25—C24—H24 119.2 C6—C7—C10 105.5 (5) C24—C25—C26 119.6 (7)
C6—C7—H7 113.5 C24—C25—H25 120.2
C8—C7—C10 105.3 (4) C26—C25—H25 120.2 C8—C7—H7 113.5 C25—C26—C27 119.5 (6)
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Acta Cryst. (2005). E61, o659–o661
C3—C8—C7 114.2 (5) C27—C26—H26 120.2 C3—C8—C11 108.9 (5) C26—C27—C28 120.3 (5) C7—C8—C11 136.9 (5) C26—C27—H27 119.9 C4—C9—C10 112.0 (6) C28—C27—H27 119.9 C4—C9—H9 124.0 C23—C28—C27 120.9 (7)
C10—C9—H9 124.0 C23—C28—H28 119.6
C7—C10—C9 113.3 (7) C27—C28—H28 119.6 C7—C10—H10 123.3 C23—C29—H29A 109.5 C9—C10—H10 123.3 C23—C29—H29B 109.5 N1—C11—C8 106.5 (5) C23—C29—H29C 109.5 N1—C11—C12 125.9 (5) H29A—C29—H29B 109.5 C8—C11—C12 127.6 (5) H29A—C29—H29C 109.5 C11—C12—C22i 128.3 (5) H29B—C29—H29C 109.5
C11—C12—H12 115.9 C31—C30—C32ii 119.0 (9)
C22i—C12—H12 115.9 C31—C30—H30 120.5
N2—C13—C1 124.4 (5) C32ii—C30—H30 120.5
N2—C13—C14 109.3 (5) C30—C31—C32 119.9 (8) C1—C13—C14 126.3 (5) C30—C31—C33 118 (1) C13—C14—C15 107.2 (5) C30—C31—H31 120.1 C13—C14—C19 138.0 (5) C32—C31—C33 121.6 (10) C15—C14—C19 114.6 (5) C32—C31—H31 120.1 C14—C15—C16 114.9 (5) C33—C31—H31 2.9 C14—C15—C22 108.1 (5) C30ii—C32—C31 121.1 (8)
C16—C15—C22 136.9 (5) C30ii—C32—H32 119.5
C15—C16—C17 105.1 (6) C31—C32—H32 119.5 C15—C16—C20 105.9 (4) C31—C33—H33A 109.5 C15—C16—H16 113.3 C31—C33—H33B 109.5 C17—C16—C20 105.0 (5) C31—C33—H33C 109.5 C17—C16—H16 113.3 H33A—C33—H33B 109.5 C20—C16—H16 113.3 H33A—C33—H33C 109.5 C16—C17—C18 112.9 (4) H33B—C33—H33C 109.5