meso-Tetra­kis[4-(hept­yloxy)phen­yl]porphyrin

The core of the novel title centrosymmetric porphyrin derivative, C₇₂H₈₆N₄O₄, with long flexible hex­yloxy substituents, is almost planar, which is anti­cipated to facilitate π-electron delocalization and lead to a significant deviation between the planes of the benzene rings and the mol­ecular plane. The two N-bound H atoms on the pyrrole rings are disordered and the occupancy factors refined to a ratio of 0.28 (2):0.72 (2).

S1. Comment

Porphyrins and metalloporphyrins have been widely studied in many fields, such as catalysts (Gross & Ini, 1999), dye-sensitized solar cells (Barea et al., 2011) and liquid crystals (Kugimiya & Takemura, 1990). In most cases, the porphyrin macrocycle has been functionalized with carboxyphenyl, hydroxyphenyl or pyridyl groups, and they can be used as molecular scaffolds to construct two- or three-dimensional polymeric materials (Chung et al., 2009) through efficient hydrogen bonds, π–π interactions and metal–ligand interactions.

Owing to the flexibility of long hydrocarbon chains and similar substituents, porphyrin crystals with long flexible chains (such as alkyl and alkoxy) are not easy to obtain (Balaban et al. 2000; Bhyrappa et al., 2008). Recently, we reported the single-crystal structures of metal complexes of meso-tetrakis(4-alkoxyphenyl)porphyrins (Chen et al., 2010; Yang et al., 2011). In order to investigate the structures of porphyrins without the presence of a metal ion, we have now synthesized meso-tetrakis[4-(heptyloxy)phenyl]porphyrin, (I), which is an important intermediate in the synthesis of metalloporphyrins for liquid-crystal materials (Zhao et al., 2000). This type of discotic liquid crystal has been researched in several fields, such as electron-transfer (Jakob et al., 2009) and ferroelectric switching (Heppke et al., 2000).

The 24-membered porphyrin core of (I) (Fig. 1) is planar, with a mean deviation of 0.037 (1) Å; the angle between adjacent pyrrole ring planes (C1–C4/N1 and C6–C9/N2)is 2.20 (9)°, and other bond lengths and angles are close to those found for tetraphenylporphyrin (Silvers & Tulinsky, 1967). This suggests that the long alkoxy chains substituted on the phenyl rings have no significant effect on the geometry of the porphine molecular plane.

The redetermination of the structure of porphine (Chen & Tulinsky, 1972) indicates that there are two structurally different pairs of pyrrole rings. We found that the N-bound H atoms in (I) (Fig. 1) are disordered, which is similar to the situation of tautomerism in free-base porphyrins, such as meso-tetraphenylporphyrin (H₂TPP; Limbach et al., 1984) and meso-tetratolylporphyrin (H₂TTP; Butcher et al., 1985). The transannular N···N separations [N1···N1ⁱ = 4.055 (2) Å and N2···N2ⁱ = 4.175 (2) Å; symmetry code: (i) -x + 2, -y, -z] for (I) are comparable with the values found in H₂TTP [4.079 (6) and 4.154 (6) Å]. The N···N distances between adjacent N atoms in (I) [2.893 (2) and 2.927 (2) Å] are also similar to those in H₂TTP, where the values are 2.894 (4) and 2.940 (4) Å.

In the crystal structure of H₂TTP, the H atoms are disordered and it was thought that this disorder could be confirmed unequivocally by indirect means, since several bond angles in the porphyrin skeleton have been shown to be sensitive to imino versus amino N atoms in ordered structures. For example, the C—N—C angles of 107.9 (3) and 107.7 (3)° in H₂TTP are midway between the average values for imino and amino N atoms of 105.7 (4) and 109.9 (4)°, respectively (Jameson & Ibers, 1980). However, in (I), the C1—N1—C4 [106.02 (13)°] and C6—N2—C9 [109.58 (13)°] angles are different from those of H₂TTP and, in contrast, they are closer to the expected values for distinct imino and amino N atoms. We therefore believe that using the nitrogen angle is not a sufficiently comprehensive and accurate criterion to judge the presence or absence of H-atom disorder in porphyrins.

The planes of the 4-(heptyloxy)phenyl groups in (I) are rotated at angles of 85.92 (5) (C11–C16) and 73.86 (4)° (C24–C29) with respect to the porphyrin mean plane, and these angles are larger than the corresponding dihedral angles in 2,3,12,13-tetrabromo-5,10,15,20-tetrakis(4-butoxyphenyl)porphyrin 1,2-dichloroethane solvate ([Values?]; Bhyrappa et al., 2008). This may be related to steric hindrance, because the heptyloxy group is longer than butoxy. By comparison, the two benzene rings (C11–C16) and (C24–C29) are almost perpendicular to one another, with an interplanar angle of 89.82 (6)°.

The unit-cell packing of (I) along the c axis is shown in Fig. 2. There are no significant π–π interactions between the porphyrins. The benzene groups with long chains around the porphyrin core may hinder interactions between the porphyrins.

Related literature

For related literature, see: Balaban et al. (2000); Barea et al. (2011); Bhyrappa et al. (2008); Butcher et al. (1985); Chen & Tulinsky (1972); Chen et al. (2010); Chung et al. (2009); Gross & Ini (1999); Heppke et al. (2000); Jakob et al. (2009); Jameson & Ibers (1980); Kugimiya & Takemura (1990); Limbach et al. (1984); Silvers & Tulinsky (1967); Yang et al. (2011); Zhao et al. (2000).

S2. Experimental

4-(Heptyloxy)benzaldehyde (0.02 mol, 4.4 g) was mixed with propionic acid (40 ml) in a 100 ml flask. The mixture was refluxed for 15 min and then freshly distilled pyrrole (0.02 mol, 1.45 ml) was added dropwise to the reaction mixture. The mixture was refluxed for 1.0 h and then stirred at room temperature, and methanol (40 ml) was added, keeping the temperature [constant?] overnight. The purple solid which formed was filtered off and washed with methanol to remove traces of propionic acid. The title compound, (I), was obtained after purification by column chromatography using neutral alumina and was recrystallized from chloroform–methanol [Solvent ratio?] as a purple solid (yield 12%, m.p. 527–528 K). Single crystals of (I) suitable for X-ray diffraction were obtained by vapour diffusion of hexane into a dichloromethane solution at room temperature.

S3. Refinement

C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 (aromatic), 0.99 (CH₂) or 0.98 Å (CH₃), and with U_iso(H) = xU_eq(C), where x = 1.5 for methyl and 1.2 for all other H atoms. Electron-density peaks near to atoms N1 and N2 and corresponding to H atoms were found in a difference Fourier map, which means disorder of these H atoms. Atoms H1A and H2A attached to atoms N1 and N2 were refined with a distance restraint of N—H = 0.86 (1) Å and with U_iso(H) = 1.2U_eq(N) (semi-free treatment). The occupancy factors of the disordered H atoms refined to 0.28 (2):0.72 (2) (H1A:H2A).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and with 50% probability displacement ellipsoids.
	Fig. 2. A view of the packing in (I), along the c axis. All H atoms and heptyl groups have been omitted for clarity.

meso-Tetrakis[4-(heptyloxy)phenyl]porphyrin

Crystal data

C72H86N4O4	F(000) = 1156
Mr = 1071.45	Dx = 1.146 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3478 reflections
a = 15.9611 (10) Å	θ = 2.3–25.2°
b = 19.1464 (12) Å	µ = 0.07 mm^−1
c = 10.1620 (6) Å	T = 185 K
β = 91.335 (1)°	Block, purple
V = 3104.6 (3) Å^3	0.25 × 0.12 × 0.09 mm
Z = 2

Data collection

Bruker APEX CCD area-detector diffractometer	5897 independent reflections
Radiation source: fine-focus sealed tube	4393 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 25.7°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −17→19
Tmin = 0.983, Tmax = 0.994	k = −20→23
15401 measured reflections	l = −10→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0568P)^2 + 0.7417P] where P = (Fo^2 + 2Fc^2)/3
5897 reflections	(Δ/σ)max = 0.001
370 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Experimental. UV–Vis (λ, nm) in chloroform: 422.97, 519.82, 556.96,593.02, 650.91.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.51741 (7)	0.09266 (7)	0.42585 (12)	0.0410 (3)
O2	1.09423 (8)	0.46877 (6)	−0.07553 (11)	0.0349 (3)
N1	0.93494 (8)	0.08790 (7)	0.04215 (13)	0.0262 (3)
H1A	0.960 (4)	0.0484 (17)	0.031 (6)	0.031*	0.28 (2)
N2	1.09930 (9)	0.06192 (7)	−0.06170 (13)	0.0283 (3)
H2A	1.0594 (11)	0.0346 (11)	−0.039 (2)	0.034*	0.72 (2)
C1	0.85825 (10)	0.09096 (9)	0.10027 (15)	0.0269 (4)
C2	0.83418 (10)	0.16273 (9)	0.11867 (16)	0.0308 (4)
H2	0.7842	0.1789	0.1576	0.037*
C3	0.89564 (10)	0.20264 (9)	0.07042 (16)	0.0303 (4)
H3	0.8968	0.2522	0.0670	0.036*
C4	0.95948 (10)	0.15567 (8)	0.02476 (15)	0.0258 (4)
C5	1.03729 (10)	0.17813 (8)	−0.02219 (15)	0.0262 (4)
C6	1.10158 (10)	0.13348 (9)	−0.06101 (15)	0.0276 (4)
C7	1.18019 (10)	0.15404 (9)	−0.11416 (16)	0.0321 (4)
H7	1.1997	0.2006	−0.1239	0.039*
C8	1.22180 (11)	0.09537 (9)	−0.14801 (17)	0.0321 (4)
H8	1.2755	0.0936	−0.1863	0.039*
C9	1.17105 (10)	0.03643 (9)	−0.11615 (16)	0.0280 (4)
C10	0.80933 (10)	0.03361 (9)	0.13792 (16)	0.0275 (4)
C11	0.73178 (10)	0.04817 (8)	0.21401 (17)	0.0291 (4)
C12	0.73573 (11)	0.04892 (10)	0.34984 (18)	0.0389 (5)
H12	0.7877	0.0396	0.3937	0.047*
C13	0.66586 (12)	0.06295 (10)	0.42414 (18)	0.0407 (5)
H13	0.6704	0.0628	0.5175	0.049*
C14	0.58989 (11)	0.07708 (9)	0.36240 (18)	0.0331 (4)
C15	0.58460 (12)	0.07570 (10)	0.22576 (19)	0.0416 (5)
H15	0.5326	0.0849	0.1818	0.050*
C16	0.65470 (11)	0.06105 (10)	0.15357 (18)	0.0402 (5)
H16	0.6499	0.0598	0.0602	0.048*
C17	0.51999 (12)	0.09014 (10)	0.56676 (18)	0.0431 (5)
H17A	0.5666	0.1195	0.6015	0.052*
H17B	0.5295	0.0415	0.5968	0.052*
C18	0.43755 (12)	0.11673 (10)	0.6172 (2)	0.0456 (5)
H18A	0.4340	0.1052	0.7119	0.055*
H18B	0.3911	0.0923	0.5701	0.055*
C19	0.42644 (12)	0.19497 (10)	0.5995 (2)	0.0430 (5)
H19A	0.4172	0.2051	0.5048	0.052*
H19B	0.4789	0.2187	0.6283	0.052*
C20	0.35393 (12)	0.22543 (10)	0.6756 (2)	0.0433 (5)
H20A	0.3006	0.2068	0.6384	0.052*
H20B	0.3589	0.2101	0.7685	0.052*
C21	0.35147 (13)	0.30456 (10)	0.6711 (2)	0.0490 (5)
H21A	0.3428	0.3195	0.5785	0.059*
H21B	0.4065	0.3228	0.7020	0.059*
C22	0.28363 (13)	0.33698 (11)	0.7534 (2)	0.0564 (6)
H22A	0.2282	0.3211	0.7194	0.068*
H22B	0.2903	0.3202	0.8453	0.068*
C23	0.28581 (18)	0.41588 (13)	0.7529 (3)	0.0809 (8)
H23A	0.3408	0.4320	0.7854	0.097*
H23B	0.2421	0.4339	0.8100	0.097*
H23C	0.2759	0.4329	0.6629	0.097*
C24	1.05164 (10)	0.25488 (8)	−0.03540 (15)	0.0268 (4)
C25	1.00965 (12)	0.29237 (9)	−0.13296 (17)	0.0362 (4)
H25	0.9715	0.2685	−0.1903	0.043*
C26	1.02143 (11)	0.36351 (9)	−0.14985 (17)	0.0357 (4)
H26	0.9914	0.3878	−0.2174	0.043*
C27	1.07736 (10)	0.39885 (9)	−0.06746 (16)	0.0285 (4)
C28	1.11947 (11)	0.36240 (9)	0.03157 (17)	0.0357 (4)
H28	1.1575	0.3863	0.0890	0.043*
C29	1.10656 (11)	0.29164 (9)	0.04748 (17)	0.0344 (4)
H29	1.1357	0.2676	0.1163	0.041*
C30	1.04834 (11)	0.50883 (9)	−0.17326 (18)	0.0348 (4)
H30A	0.9882	0.5107	−0.1515	0.042*
H30B	1.0535	0.4870	−0.2610	0.042*
C31	1.08495 (11)	0.58145 (9)	−0.17379 (18)	0.0352 (4)
H31A	1.0868	0.5998	−0.0827	0.042*
H31B	1.0480	0.6124	−0.2274	0.042*
C32	1.17261 (11)	0.58327 (9)	−0.22846 (18)	0.0339 (4)
H32A	1.1706	0.5634	−0.3184	0.041*
H32B	1.2093	0.5528	−0.1734	0.041*
C33	1.21197 (11)	0.65554 (9)	−0.23443 (18)	0.0358 (4)
H33A	1.1715	0.6883	−0.2766	0.043*
H33B	1.2238	0.6723	−0.1437	0.043*
C34	1.29262 (11)	0.65618 (10)	−0.31055 (18)	0.0383 (4)
H34A	1.3314	0.6212	−0.2712	0.046*
H34B	1.2798	0.6415	−0.4022	0.046*
C35	1.33689 (13)	0.72612 (11)	−0.3134 (2)	0.0527 (6)
H35A	1.3525	0.7399	−0.2222	0.063*
H35B	1.2977	0.7618	−0.3495	0.063*
C36	1.41502 (15)	0.72523 (13)	−0.3954 (2)	0.0642 (7)
H36A	1.4533	0.6890	−0.3622	0.077*
H36B	1.4427	0.7708	−0.3897	0.077*
H36C	1.3995	0.7153	−0.4874	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0299 (7)	0.0454 (8)	0.0483 (8)	0.0039 (6)	0.0156 (6)	−0.0035 (6)
O2	0.0421 (8)	0.0235 (6)	0.0388 (7)	−0.0047 (5)	−0.0028 (6)	0.0033 (5)
N1	0.0242 (8)	0.0248 (8)	0.0298 (7)	−0.0014 (6)	0.0058 (6)	−0.0002 (6)
N2	0.0257 (8)	0.0240 (8)	0.0354 (8)	−0.0016 (6)	0.0072 (6)	0.0006 (6)
C1	0.0247 (9)	0.0279 (9)	0.0283 (8)	0.0008 (7)	0.0023 (7)	−0.0011 (7)
C2	0.0259 (9)	0.0304 (10)	0.0363 (9)	0.0038 (7)	0.0056 (7)	−0.0023 (7)
C3	0.0310 (9)	0.0239 (9)	0.0364 (9)	0.0022 (7)	0.0049 (7)	−0.0009 (7)
C4	0.0272 (9)	0.0243 (9)	0.0259 (8)	0.0000 (7)	0.0013 (7)	0.0000 (7)
C5	0.0275 (9)	0.0240 (9)	0.0271 (8)	−0.0013 (7)	0.0009 (7)	−0.0009 (7)
C6	0.0285 (9)	0.0254 (9)	0.0289 (9)	−0.0032 (7)	0.0030 (7)	0.0015 (7)
C7	0.0309 (9)	0.0260 (9)	0.0397 (10)	−0.0042 (7)	0.0076 (8)	0.0021 (8)
C8	0.0259 (9)	0.0310 (10)	0.0399 (10)	−0.0028 (7)	0.0097 (7)	0.0011 (8)
C9	0.0241 (9)	0.0288 (9)	0.0314 (9)	−0.0003 (7)	0.0057 (7)	0.0006 (7)
C10	0.0231 (9)	0.0299 (9)	0.0297 (9)	−0.0002 (7)	0.0039 (7)	0.0002 (7)
C11	0.0265 (9)	0.0235 (9)	0.0377 (10)	−0.0005 (7)	0.0083 (7)	0.0007 (7)
C12	0.0263 (10)	0.0486 (12)	0.0420 (11)	0.0055 (8)	0.0036 (8)	−0.0035 (9)
C13	0.0352 (11)	0.0533 (13)	0.0339 (10)	0.0050 (9)	0.0084 (8)	−0.0056 (9)
C14	0.0257 (9)	0.0276 (9)	0.0465 (11)	0.0000 (7)	0.0129 (8)	−0.0016 (8)
C15	0.0280 (10)	0.0512 (12)	0.0457 (11)	0.0075 (9)	0.0034 (8)	0.0035 (9)
C16	0.0321 (10)	0.0533 (13)	0.0356 (10)	0.0038 (9)	0.0078 (8)	0.0034 (9)
C17	0.0439 (12)	0.0392 (11)	0.0469 (11)	0.0029 (9)	0.0153 (9)	−0.0036 (9)
C18	0.0426 (12)	0.0406 (12)	0.0546 (12)	−0.0007 (9)	0.0246 (10)	−0.0038 (9)
C19	0.0362 (11)	0.0407 (12)	0.0528 (12)	−0.0001 (9)	0.0168 (9)	−0.0018 (9)
C20	0.0340 (11)	0.0387 (11)	0.0578 (12)	−0.0002 (8)	0.0159 (9)	−0.0054 (9)
C21	0.0459 (12)	0.0386 (12)	0.0630 (13)	0.0012 (9)	0.0131 (10)	−0.0022 (10)
C22	0.0452 (13)	0.0394 (12)	0.0850 (16)	0.0042 (10)	0.0124 (11)	−0.0120 (11)
C23	0.084 (2)	0.0461 (15)	0.114 (2)	0.0120 (13)	0.0280 (17)	−0.0107 (15)
C24	0.0249 (9)	0.0255 (9)	0.0302 (9)	−0.0007 (7)	0.0062 (7)	−0.0005 (7)
C25	0.0415 (11)	0.0308 (10)	0.0360 (10)	−0.0078 (8)	−0.0051 (8)	−0.0002 (8)
C26	0.0431 (11)	0.0299 (10)	0.0338 (10)	−0.0021 (8)	−0.0051 (8)	0.0050 (8)
C27	0.0305 (9)	0.0226 (9)	0.0327 (9)	−0.0028 (7)	0.0062 (7)	−0.0002 (7)
C28	0.0371 (10)	0.0301 (10)	0.0395 (10)	−0.0058 (8)	−0.0079 (8)	0.0005 (8)
C29	0.0336 (10)	0.0297 (10)	0.0396 (10)	−0.0011 (8)	−0.0060 (8)	0.0059 (8)
C30	0.0380 (10)	0.0285 (10)	0.0380 (10)	0.0003 (8)	0.0026 (8)	0.0055 (8)
C31	0.0393 (11)	0.0258 (9)	0.0409 (10)	0.0017 (8)	0.0054 (8)	0.0039 (8)
C32	0.0382 (11)	0.0255 (9)	0.0383 (10)	0.0026 (8)	0.0046 (8)	0.0002 (8)
C33	0.0364 (10)	0.0291 (10)	0.0420 (10)	0.0014 (8)	0.0059 (8)	0.0020 (8)
C34	0.0384 (11)	0.0361 (11)	0.0405 (10)	0.0012 (8)	0.0066 (8)	0.0008 (8)
C35	0.0521 (13)	0.0412 (12)	0.0656 (14)	−0.0072 (10)	0.0207 (11)	0.0011 (10)
C36	0.0607 (15)	0.0595 (15)	0.0735 (16)	−0.0156 (12)	0.0266 (12)	0.0018 (12)

Geometric parameters (Å, º)

O1—C14	1.370 (2)	C19—H19B	0.9900
O1—C17	1.432 (2)	C20—C21	1.516 (3)
O2—C27	1.3683 (19)	C20—H20A	0.9900
O2—C30	1.441 (2)	C20—H20B	0.9900
N1—C4	1.368 (2)	C21—C22	1.516 (3)
N1—C1	1.373 (2)	C21—H21A	0.9900
N1—H1A	0.863 (10)	C21—H21B	0.9900
N2—C6	1.371 (2)	C22—C23	1.511 (3)
N2—C9	1.373 (2)	C22—H22A	0.9900
N2—H2A	0.860 (10)	C22—H22B	0.9900
C1—C10	1.405 (2)	C23—H23A	0.9800
C1—C2	1.440 (2)	C23—H23B	0.9800
C2—C3	1.345 (2)	C23—H23C	0.9800
C2—H2	0.9500	C24—C25	1.384 (2)
C3—C4	1.444 (2)	C24—C29	1.392 (2)
C3—H3	0.9500	C25—C26	1.386 (2)
C4—C5	1.408 (2)	C25—H25	0.9500
C5—C6	1.399 (2)	C26—C27	1.386 (2)
C5—C24	1.494 (2)	C26—H26	0.9500
C6—C7	1.433 (2)	C27—C28	1.386 (2)
C7—C8	1.354 (2)	C28—C29	1.380 (2)
C7—H7	0.9500	C28—H28	0.9500
C8—C9	1.431 (2)	C29—H29	0.9500
C8—H8	0.9500	C30—C31	1.508 (2)
C9—C10^i	1.396 (2)	C30—H30A	0.9900
C10—C9^i	1.396 (2)	C30—H30B	0.9900
C10—C11	1.501 (2)	C31—C32	1.518 (2)
C11—C12	1.380 (2)	C31—H31A	0.9900
C11—C16	1.384 (2)	C31—H31B	0.9900
C12—C13	1.387 (2)	C32—C33	1.521 (2)
C12—H12	0.9500	C32—H32A	0.9900
C13—C14	1.379 (3)	C32—H32B	0.9900
C13—H13	0.9500	C33—C34	1.517 (2)
C14—C15	1.389 (3)	C33—H33A	0.9900
C15—C16	1.381 (2)	C33—H33B	0.9900
C15—H15	0.9500	C34—C35	1.515 (3)
C16—H16	0.9500	C34—H34A	0.9900
C17—C18	1.511 (2)	C34—H34B	0.9900
C17—H17A	0.9900	C35—C36	1.516 (3)
C17—H17B	0.9900	C35—H35A	0.9900
C18—C19	1.519 (3)	C35—H35B	0.9900
C18—H18A	0.9900	C36—H36A	0.9800
C18—H18B	0.9900	C36—H36B	0.9800
C19—C20	1.523 (2)	C36—H36C	0.9800
C19—H19A	0.9900
C14—O1—C17	117.27 (14)	H20A—C20—H20B	107.8
C27—O2—C30	117.67 (13)	C20—C21—C22	114.25 (17)
C4—N1—C1	106.02 (13)	C20—C21—H21A	108.7
C4—N1—H1A	133 (4)	C22—C21—H21A	108.7
C1—N1—H1A	121 (4)	C20—C21—H21B	108.7
C6—N2—C9	109.58 (13)	C22—C21—H21B	108.7
C6—N2—H2A	128.8 (17)	H21A—C21—H21B	107.6
C9—N2—H2A	121.4 (17)	C23—C22—C21	112.98 (19)
N1—C1—C10	126.18 (15)	C23—C22—H22A	109.0
N1—C1—C2	109.86 (14)	C21—C22—H22A	109.0
C10—C1—C2	123.95 (15)	C23—C22—H22B	109.0
C3—C2—C1	107.20 (15)	C21—C22—H22B	109.0
C3—C2—H2	126.4	H22A—C22—H22B	107.8
C1—C2—H2	126.4	C22—C23—H23A	109.5
C2—C3—C4	106.83 (15)	C22—C23—H23B	109.5
C2—C3—H3	126.6	H23A—C23—H23B	109.5
C4—C3—H3	126.6	C22—C23—H23C	109.5
N1—C4—C5	126.23 (14)	H23A—C23—H23C	109.5
N1—C4—C3	110.05 (14)	H23B—C23—H23C	109.5
C5—C4—C3	123.60 (15)	C25—C24—C29	117.28 (16)
C6—C5—C4	124.56 (15)	C25—C24—C5	120.12 (15)
C6—C5—C24	117.42 (14)	C29—C24—C5	122.60 (15)
C4—C5—C24	117.99 (14)	C24—C25—C26	122.24 (16)
N2—C6—C5	126.33 (15)	C24—C25—H25	118.9
N2—C6—C7	107.23 (14)	C26—C25—H25	118.9
C5—C6—C7	126.36 (15)	C27—C26—C25	119.49 (16)
C8—C7—C6	107.87 (15)	C27—C26—H26	120.3
C8—C7—H7	126.1	C25—C26—H26	120.3
C6—C7—H7	126.1	O2—C27—C28	116.33 (15)
C7—C8—C9	108.27 (15)	O2—C27—C26	124.49 (15)
C7—C8—H8	125.9	C28—C27—C26	119.17 (16)
C9—C8—H8	125.9	C29—C28—C27	120.55 (16)
N2—C9—C10^i	126.70 (15)	C29—C28—H28	119.7
N2—C9—C8	107.02 (14)	C27—C28—H28	119.7
C10^i—C9—C8	126.27 (15)	C28—C29—C24	121.26 (16)
C9^i—C10—C1	125.40 (15)	C28—C29—H29	119.4
C9^i—C10—C11	116.80 (14)	C24—C29—H29	119.4
C1—C10—C11	117.73 (14)	O2—C30—C31	107.60 (14)
C12—C11—C16	117.46 (15)	O2—C30—H30A	110.2
C12—C11—C10	119.88 (15)	C31—C30—H30A	110.2
C16—C11—C10	122.66 (15)	O2—C30—H30B	110.2
C11—C12—C13	121.85 (17)	C31—C30—H30B	110.2
C11—C12—H12	119.1	H30A—C30—H30B	108.5
C13—C12—H12	119.1	C30—C31—C32	112.52 (14)
C14—C13—C12	119.98 (17)	C30—C31—H31A	109.1
C14—C13—H13	120.0	C32—C31—H31A	109.1
C12—C13—H13	120.0	C30—C31—H31B	109.1
O1—C14—C13	124.86 (16)	C32—C31—H31B	109.1
O1—C14—C15	116.24 (16)	H31A—C31—H31B	107.8
C13—C14—C15	118.90 (16)	C31—C32—C33	114.87 (14)
C16—C15—C14	120.24 (17)	C31—C32—H32A	108.5
C16—C15—H15	119.9	C33—C32—H32A	108.5
C14—C15—H15	119.9	C31—C32—H32B	108.5
C15—C16—C11	121.55 (17)	C33—C32—H32B	108.5
C15—C16—H16	119.2	H32A—C32—H32B	107.5
C11—C16—H16	119.2	C34—C33—C32	112.57 (14)
O1—C17—C18	108.82 (16)	C34—C33—H33A	109.1
O1—C17—H17A	109.9	C32—C33—H33A	109.1
C18—C17—H17A	109.9	C34—C33—H33B	109.1
O1—C17—H17B	109.9	C32—C33—H33B	109.1
C18—C17—H17B	109.9	H33A—C33—H33B	107.8
H17A—C17—H17B	108.3	C35—C34—C33	114.75 (15)
C17—C18—C19	113.11 (16)	C35—C34—H34A	108.6
C17—C18—H18A	109.0	C33—C34—H34A	108.6
C19—C18—H18A	109.0	C35—C34—H34B	108.6
C17—C18—H18B	109.0	C33—C34—H34B	108.6
C19—C18—H18B	109.0	H34A—C34—H34B	107.6
H18A—C18—H18B	107.8	C34—C35—C36	113.00 (17)
C18—C19—C20	113.96 (15)	C34—C35—H35A	109.0
C18—C19—H19A	108.8	C36—C35—H35A	109.0
C20—C19—H19A	108.8	C34—C35—H35B	109.0
C18—C19—H19B	108.8	C36—C35—H35B	109.0
C20—C19—H19B	108.8	H35A—C35—H35B	107.8
H19A—C19—H19B	107.7	C35—C36—H36A	109.5
C21—C20—C19	112.77 (16)	C35—C36—H36B	109.5
C21—C20—H20A	109.0	H36A—C36—H36B	109.5
C19—C20—H20A	109.0	C35—C36—H36C	109.5
C21—C20—H20B	109.0	H36A—C36—H36C	109.5
C19—C20—H20B	109.0	H36B—C36—H36C	109.5

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2	0.86 (1)	2.45 (6)	2.8935 (19)	113 (5)
N2—H2A···N1^i	0.86 (1)	2.35 (2)	2.928 (2)	125 (2)

Symmetry code: (i) −x+2, −y, −z.