Inter­molecular π-stacking and F...F inter­actions of fluorine-substituted meso-alkynylporphyrin

Two C2-symmetric meso-alkynylporphyrins, namely 5,15-bis­[(4-butyl-2,3,5,6-tetra­fluoro­phen­yl)ethyn­yl]-10,20-dipropyl­porphyrin, C₅₀H₄₂F₈N₄, (I), and 5,15-bis­[(4-butyl­phen­yl)ethyn­yl]-10,20-dipropyl­porphyrin, C₅₀H₅₀N₄, (II), show remarkable π–π stacking that forms columns of porphyrin centers. The tetra­fluoro­phenyl­ene moieties in (I) show inter­molecular inter­actions with each other through the F atoms, forming one-dimensional ribbons. No significant π–π inter­actions are observed in the plane of the phenyl­ene and tetra­fluoro­phenyl­ene moieties in either (I) or (II). The molecules of both compounds lie about inversion centers.

S1. Comment

Porphyrin assemblies allow chemists to create mechanical architectures and to understand biological systems (Drain et al., 2009; Beletskaya et al., 2009; Nakamura et al., 2007). For the past few decades, porphyrin derivatives with acetylene connections at the meso-positions have found great utility as the motifs of self-assembling systems and electronic materials (Huang et al., 2006; Anderson et al., 1998). In particular, substitutions for the meso-alkynylporphyrins, while maintaining the coplanar molecule, are important in the development of intermolecular arrays in crystals and on surfaces (Kato et al., 2004). While many kinds of alkynyl, aryl and mono-halogeno derivatives have been investigated, few examples of fluorine-substituted meso-alkynylporphyrins have been reported, such as those exhibiting mono-substitution by –F or –CF₃ groups (Kuo et al., 2007; Doerksen & Thakkar, 1999). We have been interested in the crystal packing of fully fluorinated aromatic compounds, because fluorine substitution would control the distance, direction and strength of the π-stacking based on the high electronegativity of the F atoms. Actually, the unique interactions induced by fluorine are demonstrated as the arene–perfluoroarene (Williams, 1993; Hori et al., 2007), C—H···F (Thalladi et al., 1998) and anion···π (Quiñonero et al., 2002) and other interactions. This prompted us to design the perfluorophenylene-attached meso-alkynylporphyrin (I) and to compare it with (II), which hopefully will provide a good basis for understanding the intermolecular interactions and for designing further reactions of self-assembling motifs. The butyl and propyl groups were attached in order to increase the solubility of the compounds.

The two porphyrin derivatives were synthesized in two steps using the Linsey reaction (see Experimental). Crystallization by diffusion of MeOH into a CH₂Cl₂ solution of the compounds yielded pure products. The UV–visible spectra of (I) and (II) in CH₂Cl₂ solution are very similar – both soret bands are observed at 442 nm for (I) and (II); the Q bands are observed at 603 and 698 nm for (I) and at 601 and 698 nm for (II). However, the diffuse reflection spectra of the powder samples with KBr of (I) and (II) are slightly but significantly different from the spectra in a CH₂Cl₂ solution. The peak tops of the broad bands are observed around 429–450, 626 and 716 nm for (I) and 448, 618 and 710 nm for (II), which means that, except for the soret band of (I), the bands are red-shifted compared with a solution, as usual for the solid state. The small blue shift in the broad soret band of (I) is attributed to the effects of intermolecular interactions.

Molecules of (I) and (II) lie across crystallographic inversion centers, with the porphyrin ring and the phenylene moieties almost coplanar (Fig. 1). However, the dihedral angle between them, N1/N2/C1–C10 (12 porphyrin atoms) and C13–C18 (six phenylene atoms), in (I) is 10.72 (7)°, which is greater than that of (II) [2.29 (8)°]. The acetylene linkers in (I) are slightly sigmoidal in a plane perpendicular to the plane of the porphyrin moiety. Accordingly, the entire framework without protons, fluorines and aliphatic groups of the molecules of (I) is less flat than that of (II): the r.m.s deviation of the aromatic atoms from their mean planes is 0.1076(s.u.??) Å in (I) and 0.0432(s.u.??) Å in (II) <— Please check these r.m.s.deviations: we cannot reproduce them. In (II), the sigmoidal form is also observed in the plane of the porphyrin moiety (Fig. 1). Bifurcated intramolecular N—H···N hydrogen bonds link the amino atom N2 via H1 to the imino atoms N1 and N1ⁱ (see Tables 1 and 2). The C5—C11, C11—C12 and C12—C13 distances around the acetylene linkage clearly indicate the localization of the triple bonds of the acetylene linkers in (I) and (II).

The crystal packing arrangements in (I) and (II) are shown in Figs. 2 and 3, respectively. In (I), the molecules are aligned in a flattened ribbon along the c axis, and an intermolecular F1···F1ⁱⁱⁱ interaction [symmetry code: (iii) - x + 2, - y, - z] of 2.7808 (15) Å is observed between the tetrafluorophenylene moieties. The ribbons are aligned parallel with the overlapping of half of the porphyrin moiety through intermolecular π–π stacking along the a axis, producing molecular columns. The corresponding intermolecular atom···atom distance of the molecules through the π–π stacking is 4.7936 (8) Å, the length of the a axis. The closest distance between the two pyrrole rings in the porphyrin center, CgA···CgB^iv [symmetry code: (iv) x - 1, y, z] is 3.7176 (12) Å, where CgA and CgB are the centroids of the five-membered N1/C1–C4 and N2/C6–C9 rings, respectively. The corresponding perpendicular distance from the ring centroids to the adjacent planes is 3.2399 (7) Å. In the column, the tetrafluorophenylene moieties are positioned close to each other and electrostatic π–π interactions are dominant. The intermolecular distances between the two tetrafluorophenylene rings, CgC···CgC^iv and CgC···CgC^v [symmetry code: (v) - x + 1, - y, - z], are 4.7936 (8) and 5.1995 (13) Å, respectively, where CgC is the centroid of the tetrafluorophenylene ring C13–C18. The short C—F···CgC distances involving C14—F1···CgC^vi [symmetry code: (vi) x + 1, y, z] and C17—F3···CgC^iv are 3.3590 (13) and 3.3599 (13) Å, respectively. Finally, the columns are arranged in a zigzag fashion along the b axis and the dihedral angle between the two planes of porphyrins is 87.85 (14)°, with alternation of the aligned butyl and propyl chains.

In (II) the molecules also show π–π stacking to produce columns of molecules along the b axis. The corresponding intermolecular atom···atom distance of the molecules through the π–π stacking is 5.2845 (5) Å, the length of the b axis and greater than that in (I). The closest intermolecular distance between the two pyrrole rings in the porphyrin center, CgA···CgB^vii [symmetry code: (vii) x, y + 1, z] is 3.5863 (10) Å and the perpendicular distance from the ring centroids to the adjacent planes is 3.3016 (7) Å. The lateral interaction along [1 0 2] between the columns is much weaker than that in (I). The phenylene ring is close to a butyl group and the acetylene linker of the other molecules; the short distances H15···H20A^viii [symmetry code: (viii) x, y - 1, z] and C12···H17^ix [symmetry code: (ix) - x + 1/2, y - 1/2, - z + 1/2] being 2.31 and 2.83 Å, respectively. No remarkable π–π intermolecular interactions are observed for the phenylene moiety and the closest intermolecular distance between the two phenylene rings, CgC···CgC^ix is 4.9821 (10) Å. Along the c axis, the columns are arranged in a zigzag arrangement and the inclination of the two planes of the porphyrins is 78.2 (13)°.

In conclusion, both C2-symmetric porphyrins show intermolecular π–π stacking between the porphyrin centers, and no unusual stackings were observed between the phenylene moieties in (I) and (II). On the other hand, the tetrafluorophenylene moieties in (I) interact with each other through F···F interactions to give planar porphyrin ribbons. Accordingly, the π–π overlap is more significant in (I) than in (II), which probably increases the H-aggregate character of porphyrin (I) to produce small blue shifts in the solid state.

Related literature

For related literature, see: Anderson et al. (1998); Beletskaya et al. (2009); Doerksen & Thakkar (1999); Drain et al. (2009); Hori et al. (2007); Huang et al. (2006); Kato et al. (2004); Kuo et al. (2007); Nakamura et al. (2007); Quiñonero, Garay, Rotger, Frontera, Ballester, Costa & Deyà (2002); Thalladi et al. (1998); Williams (1993).

S2. Experimental

The porphyrins (I) and (II) were prepared in two steps using the general Linsey method (Anderson et al., 1998). Typically, BF₃.Et₂O (0.40 mmol) was added to a solution of 4-butyl-2,3,5,6-tetrafluorophenylpropiolaldehyde (1.35 mmol) in CH₂Cl₂ (35 ml) and an excess amount of pyrrole (68 mmol) at 248 K. The reaction mixture was stirred for 30 min, the solution was washed with 10% aqueous NaOH and water, dried over MgSO₄, and purified by column chromatography to give the meso-4-butyl-2,3,5,6-tetrafluorophenyl-2,2'-dipyrrylmethane in 86% yield. The product (1.17 mmol) was further reacted with n-butylaldehyde (1.17 mmol), BF₃.Et₂O (0.40 mmol) and DDQ (1.17 mmol) under the Linsey conditions to produce the porphyrin (I) as a dark blue powder in 6% yield. The porphyrin (I) was also obtained in the same yield from 4-butyl-2,3,5,6-tetrafluorophenylpropiolaldehyde and meso-propyl-2,2'-dipyrrylmethane, which was prepared from n-butylaldehyde and an excess amount of pyrrole, under the same conditions as the first method. The porphyrin (II) was prepared from 4-butylphenylpropiolaldehyde and meso-propyl-2,2'-dipyrrylmethane as a dark blue powder in 1% yield.

For (I), UV–visible spectra in a solution (MeCN): 442 nm (ε = 410000 M^-1cm^-1), 603 nm (ε = 54400 M^-1cm^-1), 698 nm (ε = 37000 M^-1cm^-1); in solid (KBr): 429–450, 626 and 716 nm. Elemental analysis: Calculated for C₅₀H₄₂F₈N₄ (%): C, 70.58; H, 4.98; N, 6.58. Found: C, 70.23; H, 4.98; N, 6.53. For (II), UV–visible spectra in a solution (MeCN): 442 nm (ε = 413000 M^-1cm^-1), 601 nm (ε = 60000 M^-1cm^-1), 698 nm (ε = 48300 M^-1cm^-1); in solid (KBr): 448, 618 and 710 nm. Elemental analysis: Calculated for C₅₀H₅₀N₄ (%): C, 84.95; H, 7.13; N, 7.92. Found: C, 84.91; H,7.01; N, 7.95.

S3. Refinement

H atoms attached to C atoms were placed in geometrically idealized positions and refined riding on their carrier atoms, with aromatic, methyl and methylene C—H distances of 0.95, 0.98 and 0.99 Å, respectively, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and U_iso(H) = 1.2U_eq(C) for others. Atom H1 (attached to N2) was located in a difference Fourier density map and refined freely to give N—H distances of 0.85 (3) and 0.906 (18) Å for (I) and (II), respectively.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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 structures of (a) (I) and (b) (II) at 100 K, showing the atom-labeling schemes. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of part of the crystal structure of (I) along the a axis.
	Fig. 3. A view of part of the crystal structure of (II) along the b axis.

(I) 5,15-bis[(4-butyl-2,3,5,6-tetrafluorophenyl)ethynyl]-10,20-dipropylporphyrin

Crystal data

C50H42F8N4	F(000) = 884
Mr = 850.88	Dx = 1.425 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2297 reflections
a = 4.7936 (8) Å	θ = 2.5–26.6°
b = 23.483 (4) Å	µ = 0.11 mm^−1
c = 17.628 (3) Å	T = 100 K
β = 91.824 (2)°	Prismatic, dark blue
V = 1983.4 (6) Å^3	0.28 × 0.08 × 0.06 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer	4444 independent reflections
Radiation source: fine-focus sealed tube	3019 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 8.333 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −6→5
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −30→28
Tmin = 0.970, Tmax = 0.993	l = −22→16
10839 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0484P)^2 + 0.259P] where P = (Fo^2 + 2Fc^2)/3
4444 reflections	(Δ/σ)max < 0.001
286 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.7231 (3)	0.05805 (6)	0.45808 (8)	0.0181 (3)
N2	1.1486 (3)	−0.01859 (6)	0.39257 (9)	0.0176 (3)
C1	0.5313 (3)	0.09036 (7)	0.49578 (10)	0.0177 (4)
C2	0.3769 (4)	0.12542 (8)	0.44186 (10)	0.0213 (4)
H2	0.2339	0.1518	0.4531	0.026*
C3	0.4733 (4)	0.11374 (8)	0.37283 (10)	0.0210 (4)
H3	0.4117	0.1303	0.3261	0.025*
C4	0.6872 (3)	0.07136 (7)	0.38311 (10)	0.0174 (4)
C5	0.8296 (3)	0.04661 (7)	0.32281 (10)	0.0173 (4)
C6	1.0383 (4)	0.00462 (7)	0.32744 (10)	0.0173 (4)
C7	1.1731 (4)	−0.02054 (8)	0.26464 (10)	0.0202 (4)
H7	1.1356	−0.0123	0.2125	0.024*
C8	1.3640 (4)	−0.05820 (8)	0.29265 (10)	0.0197 (4)
H8	1.4850	−0.0810	0.2637	0.024*
C9	1.3507 (3)	−0.05737 (7)	0.37386 (10)	0.0176 (4)
C10	1.5082 (4)	−0.09036 (7)	0.42555 (10)	0.0182 (4)
C11	0.7440 (4)	0.06466 (7)	0.24792 (10)	0.0197 (4)
C12	0.6599 (4)	0.07884 (8)	0.18624 (10)	0.0198 (4)
C13	0.5474 (4)	0.09299 (7)	0.11293 (9)	0.0175 (4)
C14	0.6410 (4)	0.06667 (7)	0.04753 (10)	0.0191 (4)
C15	0.5263 (4)	0.07866 (7)	−0.02279 (10)	0.0200 (4)
C16	0.3110 (4)	0.11773 (8)	−0.03378 (10)	0.0201 (4)
C17	0.2229 (4)	0.14469 (7)	0.03123 (10)	0.0195 (4)
C18	0.3335 (4)	0.13268 (7)	0.10226 (10)	0.0186 (4)
C19	0.1800 (4)	0.12897 (8)	−0.11140 (10)	0.0250 (4)
H19A	−0.0129	0.1429	−0.1052	0.030*
H19B	0.1685	0.0926	−0.1397	0.030*
C20	0.3375 (4)	0.17225 (8)	−0.15856 (10)	0.0244 (4)
H20A	0.5304	0.1583	−0.1646	0.029*
H20B	0.2470	0.1743	−0.2098	0.029*
C21	0.3507 (4)	0.23186 (8)	−0.12539 (11)	0.0282 (5)
H21A	0.4605	0.2310	−0.0769	0.034*
H21B	0.1594	0.2447	−0.1144	0.034*
C22	0.4825 (5)	0.27430 (9)	−0.17876 (12)	0.0352 (5)
H22A	0.6758	0.2631	−0.1874	0.053*
H22B	0.4799	0.3124	−0.1560	0.053*
H22C	0.3767	0.2748	−0.2272	0.053*
C23	1.7267 (4)	−0.13026 (7)	0.39568 (10)	0.0189 (4)
H23A	1.8904	−0.1304	0.4313	0.023*
H23B	1.7888	−0.1157	0.3463	0.023*
C24	1.6221 (4)	−0.19151 (7)	0.38523 (11)	0.0213 (4)
H24A	1.5248	−0.2034	0.4313	0.026*
H24B	1.4856	−0.1928	0.3419	0.026*
C25	1.8570 (4)	−0.23293 (8)	0.37087 (11)	0.0250 (4)
H25A	1.9589	−0.2205	0.3265	0.038*
H25B	1.7794	−0.2710	0.3615	0.038*
H25C	1.9847	−0.2341	0.4154	0.038*
F1	0.8467 (2)	0.02776 (4)	0.05451 (6)	0.0254 (3)
F2	0.6238 (2)	0.05077 (4)	−0.08358 (6)	0.0273 (3)
F3	0.0145 (2)	0.18338 (4)	0.02522 (6)	0.0280 (3)
F4	0.2343 (2)	0.15987 (4)	0.16276 (6)	0.0256 (3)
H1	1.100 (6)	−0.0115 (13)	0.4377 (18)	0.089 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0205 (8)	0.0192 (8)	0.0144 (8)	−0.0016 (6)	0.0004 (6)	−0.0024 (6)
N2	0.0200 (8)	0.0182 (8)	0.0145 (8)	0.0002 (6)	−0.0008 (7)	−0.0006 (6)
C1	0.0180 (9)	0.0168 (9)	0.0181 (9)	0.0001 (7)	−0.0019 (7)	0.0000 (7)
C2	0.0225 (10)	0.0208 (10)	0.0205 (10)	0.0045 (8)	−0.0013 (8)	0.0011 (8)
C3	0.0238 (10)	0.0219 (10)	0.0171 (9)	0.0032 (8)	−0.0033 (8)	0.0026 (7)
C4	0.0187 (9)	0.0177 (9)	0.0156 (9)	−0.0018 (7)	−0.0017 (7)	0.0011 (7)
C5	0.0194 (9)	0.0186 (9)	0.0136 (9)	−0.0018 (8)	−0.0029 (7)	0.0003 (7)
C6	0.0192 (9)	0.0184 (9)	0.0141 (9)	−0.0036 (7)	−0.0021 (7)	0.0010 (7)
C7	0.0237 (9)	0.0230 (10)	0.0138 (9)	−0.0022 (8)	−0.0014 (7)	0.0002 (7)
C8	0.0215 (9)	0.0216 (10)	0.0161 (9)	−0.0003 (8)	0.0019 (7)	−0.0025 (8)
C9	0.0176 (9)	0.0188 (9)	0.0163 (9)	−0.0027 (7)	0.0003 (7)	−0.0009 (7)
C10	0.0175 (9)	0.0177 (9)	0.0193 (9)	−0.0034 (7)	−0.0005 (7)	−0.0019 (7)
C11	0.0212 (9)	0.0172 (9)	0.0208 (10)	−0.0010 (8)	0.0010 (8)	−0.0008 (7)
C12	0.0215 (9)	0.0201 (9)	0.0180 (10)	−0.0012 (8)	0.0017 (8)	0.0003 (7)
C13	0.0216 (9)	0.0168 (9)	0.0139 (9)	−0.0053 (7)	−0.0007 (7)	0.0016 (7)
C14	0.0200 (9)	0.0163 (9)	0.0210 (10)	0.0007 (7)	0.0004 (8)	0.0025 (7)
C15	0.0267 (10)	0.0187 (9)	0.0149 (9)	−0.0044 (8)	0.0032 (8)	−0.0042 (7)
C16	0.0248 (10)	0.0190 (9)	0.0164 (9)	−0.0060 (8)	−0.0028 (8)	0.0024 (7)
C17	0.0197 (9)	0.0171 (9)	0.0216 (10)	0.0015 (8)	−0.0014 (8)	0.0027 (7)
C18	0.0240 (10)	0.0174 (9)	0.0145 (9)	−0.0027 (8)	0.0031 (8)	−0.0021 (7)
C19	0.0306 (11)	0.0265 (11)	0.0175 (10)	−0.0047 (9)	−0.0066 (8)	0.0020 (8)
C20	0.0316 (11)	0.0256 (10)	0.0156 (9)	−0.0021 (9)	−0.0047 (8)	0.0018 (8)
C21	0.0365 (11)	0.0268 (11)	0.0209 (10)	−0.0020 (9)	−0.0040 (9)	0.0015 (8)
C22	0.0467 (13)	0.0309 (11)	0.0276 (12)	−0.0117 (10)	−0.0072 (10)	0.0020 (9)
C23	0.0179 (9)	0.0213 (10)	0.0174 (9)	−0.0002 (8)	0.0000 (7)	0.0001 (7)
C24	0.0213 (9)	0.0210 (10)	0.0217 (10)	0.0003 (8)	0.0013 (8)	−0.0005 (8)
C25	0.0276 (10)	0.0229 (10)	0.0245 (11)	0.0033 (8)	−0.0007 (8)	0.0000 (8)
F1	0.0277 (6)	0.0249 (6)	0.0237 (6)	0.0066 (5)	0.0011 (5)	0.0012 (5)
F2	0.0378 (6)	0.0273 (6)	0.0169 (6)	−0.0011 (5)	0.0054 (5)	−0.0053 (5)
F3	0.0277 (6)	0.0270 (6)	0.0290 (6)	0.0075 (5)	−0.0033 (5)	0.0030 (5)
F4	0.0306 (6)	0.0280 (6)	0.0183 (6)	0.0025 (5)	0.0047 (5)	−0.0038 (4)

Geometric parameters (Å, º)

N1—C4	1.364 (2)	C14—C15	1.369 (2)
N1—C1	1.379 (2)	C15—F2	1.3521 (19)
N2—C6	1.362 (2)	C15—C16	1.390 (2)
N2—C9	1.377 (2)	C16—C17	1.387 (3)
N2—H1	0.85 (3)	C16—C19	1.510 (2)
C1—N1	1.379 (2)	C17—F3	1.352 (2)
C1—C10^i	1.406 (2)	C17—C18	1.373 (2)
C1—C2	1.444 (2)	C18—F4	1.3429 (19)
C2—C3	1.344 (2)	C19—C20	1.528 (3)
C2—H2	0.9500	C19—H19A	0.9900
C3—C4	1.436 (2)	C19—H19B	0.9900
C3—H3	0.9500	C20—C21	1.517 (3)
C4—N1	1.364 (2)	C20—H20A	0.9900
C4—C5	1.407 (2)	C20—H20B	0.9900
C5—C6	1.405 (2)	C21—C22	1.522 (3)
C5—C11	1.434 (2)	C21—H21A	0.9900
C6—C7	1.427 (2)	C21—H21B	0.9900
C7—C8	1.355 (2)	C22—H22A	0.9800
C7—H7	0.9500	C22—H22B	0.9800
C8—C9	1.435 (2)	C22—H22C	0.9800
C8—H8	0.9500	C23—C24	1.532 (2)
C9—C10	1.399 (2)	C23—H23A	0.9900
C10—C1^i	1.406 (2)	C23—H23B	0.9900
C10—C23	1.512 (2)	C24—C25	1.515 (2)
C11—C12	1.195 (2)	C24—H24A	0.9900
C12—C13	1.424 (2)	C24—H24B	0.9900
C13—C18	1.394 (2)	C25—H25A	0.9800
C13—C14	1.395 (2)	C25—H25B	0.9800
C14—F1	1.3472 (19)	C25—H25C	0.9800
C4—N1—C1	106.00 (14)	C17—C16—C19	122.68 (17)
C6—N2—C9	108.65 (15)	C15—C16—C19	121.82 (16)
C6—N2—H1	127 (2)	F3—C17—C18	118.18 (16)
C9—N2—H1	125 (2)	F3—C17—C16	119.07 (15)
N1—C1—C10^i	126.03 (15)	C18—C17—C16	122.73 (16)
N1—C1—C10^i	126.03 (15)	F4—C18—C17	119.35 (16)
N1—C1—C2	109.40 (15)	F4—C18—C13	119.23 (15)
N1—C1—C2	109.40 (15)	C17—C18—C13	121.41 (16)
C10^i—C1—C2	124.57 (16)	C16—C19—C20	114.26 (15)
C3—C2—C1	107.21 (16)	C16—C19—H19A	108.7
C3—C2—H2	126.4	C20—C19—H19A	108.7
C1—C2—H2	126.4	C16—C19—H19B	108.7
C2—C3—C4	106.98 (16)	C20—C19—H19B	108.7
C2—C3—H3	126.5	H19A—C19—H19B	107.6
C4—C3—H3	126.5	C21—C20—C19	114.79 (16)
N1—C4—C5	126.04 (15)	C21—C20—H20A	108.6
N1—C4—C5	126.04 (15)	C19—C20—H20A	108.6
N1—C4—C3	110.39 (15)	C21—C20—H20B	108.6
N1—C4—C3	110.39 (15)	C19—C20—H20B	108.6
C5—C4—C3	123.54 (16)	H20A—C20—H20B	107.5
C6—C5—C4	127.41 (16)	C20—C21—C22	112.27 (17)
C6—C5—C11	116.30 (16)	C20—C21—H21A	109.2
C4—C5—C11	116.24 (15)	C22—C21—H21A	109.2
N2—C6—C5	125.89 (16)	C20—C21—H21B	109.2
N2—C6—C7	108.35 (15)	C22—C21—H21B	109.2
C5—C6—C7	125.76 (16)	H21A—C21—H21B	107.9
C8—C7—C6	107.75 (15)	C21—C22—H22A	109.5
C8—C7—H7	126.1	C21—C22—H22B	109.5
C6—C7—H7	126.1	H22A—C22—H22B	109.5
C7—C8—C9	107.68 (16)	C21—C22—H22C	109.5
C7—C8—H8	126.2	H22A—C22—H22C	109.5
C9—C8—H8	126.2	H22B—C22—H22C	109.5
N2—C9—C10	125.41 (16)	C10—C23—C24	113.33 (14)
N2—C9—C8	107.57 (15)	C10—C23—H23A	108.9
C10—C9—C8	127.02 (16)	C24—C23—H23A	108.9
C9—C10—C1^i	123.78 (16)	C10—C23—H23B	108.9
C9—C10—C23	118.80 (16)	C24—C23—H23B	108.9
C1^i—C10—C23	117.38 (15)	H23A—C23—H23B	107.7
C12—C11—C5	176.83 (19)	C25—C24—C23	112.38 (14)
C11—C12—C13	176.46 (19)	C25—C24—H24A	109.1
C18—C13—C14	116.06 (15)	C23—C24—H24A	109.1
C18—C13—C12	122.29 (16)	C25—C24—H24B	109.1
C14—C13—C12	121.62 (16)	C23—C24—H24B	109.1
F1—C14—C15	119.59 (16)	H24A—C24—H24B	107.9
F1—C14—C13	118.61 (15)	C24—C25—H25A	109.5
C15—C14—C13	121.79 (16)	C24—C25—H25B	109.5
F2—C15—C14	118.62 (16)	H25A—C25—H25B	109.5
F2—C15—C16	118.89 (15)	C24—C25—H25C	109.5
C14—C15—C16	122.48 (16)	H25A—C25—H25C	109.5
C17—C16—C15	115.50 (16)	H25B—C25—H25C	109.5
C4—N1—C1—C10^i	179.68 (16)	C8—C9—C10—C23	2.5 (3)
C4—N1—C1—C2	−1.15 (18)	C18—C13—C14—F1	−179.73 (14)
N1—C1—C2—C3	0.6 (2)	C12—C13—C14—F1	−1.3 (2)
N1—C1—C2—C3	0.6 (2)	C18—C13—C14—C15	−0.9 (2)
C10^i—C1—C2—C3	179.81 (16)	C12—C13—C14—C15	177.60 (17)
C1—C2—C3—C4	0.1 (2)	F1—C14—C15—F2	0.1 (2)
C1—N1—C4—C5	−176.85 (16)	C13—C14—C15—F2	−178.79 (15)
C1—N1—C4—C3	1.25 (18)	F1—C14—C15—C16	179.07 (15)
C2—C3—C4—N1	−0.9 (2)	C13—C14—C15—C16	0.2 (3)
C2—C3—C4—N1	−0.9 (2)	F2—C15—C16—C17	−179.84 (15)
C2—C3—C4—C5	177.27 (16)	C14—C15—C16—C17	1.2 (3)
N1—C4—C5—C6	−1.3 (3)	F2—C15—C16—C19	1.2 (3)
N1—C4—C5—C6	−1.3 (3)	C14—C15—C16—C19	−177.84 (16)
C3—C4—C5—C6	−179.20 (17)	C15—C16—C17—F3	179.87 (15)
N1—C4—C5—C11	175.94 (16)	C19—C16—C17—F3	−1.1 (3)
N1—C4—C5—C11	175.94 (16)	C15—C16—C17—C18	−1.9 (3)
C3—C4—C5—C11	−1.9 (2)	C19—C16—C17—C18	177.06 (17)
C9—N2—C6—C5	−178.90 (16)	F3—C17—C18—F4	−0.7 (2)
C9—N2—C6—C7	0.45 (19)	C16—C17—C18—F4	−178.91 (16)
C4—C5—C6—N2	−2.5 (3)	F3—C17—C18—C13	179.56 (15)
C11—C5—C6—N2	−179.74 (16)	C16—C17—C18—C13	1.3 (3)
C4—C5—C6—C7	178.29 (17)	C14—C13—C18—F4	−179.64 (15)
C11—C5—C6—C7	1.0 (3)	C12—C13—C18—F4	1.9 (2)
N2—C6—C7—C8	−0.4 (2)	C14—C13—C18—C17	0.1 (2)
C5—C6—C7—C8	178.91 (17)	C12—C13—C18—C17	−178.34 (17)
C6—C7—C8—C9	0.25 (19)	C17—C16—C19—C20	96.9 (2)
C6—N2—C9—C10	−179.17 (16)	C15—C16—C19—C20	−84.1 (2)
C6—N2—C9—C8	−0.30 (19)	C16—C19—C20—C21	−63.4 (2)
C7—C8—C9—N2	0.02 (19)	C19—C20—C21—C22	−173.90 (16)
C7—C8—C9—C10	178.87 (17)	C9—C10—C23—C24	−95.93 (19)
N2—C9—C10—C1^i	3.7 (3)	C1^i—C10—C23—C24	81.73 (19)
C8—C9—C10—C1^i	−174.95 (17)	C10—C23—C24—C25	−168.34 (15)
N2—C9—C10—C23	−178.80 (15)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N1	0.85 (3)	2.47 (3)	2.980 (2)	119 (2)
N2—H1···N1^i	0.85 (3)	2.28 (3)	2.840 (2)	124 (3)

Symmetry code: (i) −x+2, −y, −z+1.

(II) 5,15-bis[(4-butylphenyl)ethynyl]-10,20-dipropylporphyrin

Crystal data

C50H50N4	F(000) = 1512
Mr = 706.94	Dx = 1.225 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2683 reflections
a = 33.613 (3) Å	θ = 2.6–27.2°
b = 5.2845 (5) Å	µ = 0.07 mm^−1
c = 23.152 (2) Å	T = 100 K
β = 111.252 (1)°	Prismatic, dark blue
V = 3832.7 (6) Å^3	0.28 × 0.14 × 0.06 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	4292 independent reflections
Radiation source: sealed tube	3128 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 8.333 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
ϕ and ω scans	h = −36→42
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −6→6
Tmin = 0.980, Tmax = 0.996	l = −26→29
10125 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0477P)^2 + 1.9292P] where P = (Fo^2 + 2Fc^2)/3
4292 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.04748 (4)	0.7578 (2)	0.01432 (5)	0.0202 (3)
N2	0.02993 (4)	0.3394 (2)	0.08792 (5)	0.0195 (3)
C1	0.05081 (4)	0.9507 (3)	−0.02369 (6)	0.0204 (3)
C2	0.08937 (5)	1.0980 (3)	0.00689 (7)	0.0237 (3)
H2	0.0990	1.2396	−0.0097	0.028*
C3	0.10870 (4)	0.9937 (3)	0.06334 (7)	0.0233 (3)
H3	0.1347	1.0474	0.0942	0.028*
C4	0.08223 (4)	0.7844 (3)	0.06778 (6)	0.0207 (3)
C5	0.09127 (4)	0.6358 (3)	0.12180 (6)	0.0198 (3)
C6	0.06712 (4)	0.4330 (3)	0.13039 (6)	0.0196 (3)
C7	0.07656 (5)	0.2848 (3)	0.18515 (7)	0.0229 (3)
H7	0.1005	0.3062	0.2225	0.028*
C8	0.04548 (5)	0.1079 (3)	0.17489 (6)	0.0227 (3)
H8	0.0439	−0.0159	0.2037	0.027*
C9	0.01550 (4)	0.1402 (3)	0.11302 (6)	0.0200 (3)
C10	−0.02150 (4)	−0.0029 (3)	0.08350 (6)	0.0197 (3)
C11	0.12819 (4)	0.7034 (3)	0.17452 (6)	0.0216 (3)
C12	0.15816 (4)	0.7621 (3)	0.21982 (7)	0.0222 (3)
C13	0.19470 (4)	0.8152 (3)	0.27460 (6)	0.0217 (3)
C14	0.20357 (5)	0.6575 (3)	0.32616 (7)	0.0274 (4)
H14	0.1846	0.5235	0.3255	0.033*
C15	0.23992 (5)	0.6954 (3)	0.37827 (7)	0.0283 (4)
H15	0.2454	0.5867	0.4130	0.034*
C16	0.26840 (4)	0.8889 (3)	0.38082 (7)	0.0225 (3)
C17	0.25905 (5)	1.0491 (3)	0.32999 (7)	0.0257 (3)
H17	0.2779	1.1847	0.3312	0.031*
C18	0.22252 (5)	1.0147 (3)	0.27728 (7)	0.0259 (3)
H18	0.2166	1.1270	0.2431	0.031*
C19	0.30802 (4)	0.9266 (3)	0.43841 (7)	0.0254 (3)
H19A	0.3315	0.9901	0.4260	0.031*
H19B	0.3170	0.7613	0.4592	0.031*
C20	0.30077 (5)	1.1123 (3)	0.48413 (7)	0.0271 (4)
H20A	0.2948	1.2816	0.4645	0.033*
H20B	0.2752	1.0585	0.4925	0.033*
C21	0.33820 (5)	1.1349 (3)	0.54565 (7)	0.0260 (3)
H21A	0.3431	0.9691	0.5670	0.031*
H21B	0.3643	1.1797	0.5375	0.031*
C22	0.33023 (5)	1.3342 (3)	0.58772 (7)	0.0298 (4)
H22A	0.3285	1.5016	0.5687	0.045*
H22B	0.3537	1.3322	0.6280	0.045*
H22C	0.3034	1.2970	0.5935	0.045*
C23	−0.03103 (4)	−0.2186 (3)	0.11947 (7)	0.0226 (3)
H23A	−0.0038	−0.2838	0.1497	0.027*
H23B	−0.0448	−0.3577	0.0905	0.027*
C24	−0.06012 (5)	−0.1403 (3)	0.15405 (7)	0.0275 (4)
H24A	−0.0462	−0.0030	0.1835	0.033*
H24B	−0.0871	−0.0727	0.1239	0.033*
C25	−0.07016 (5)	−0.3585 (3)	0.18939 (7)	0.0326 (4)
H25A	−0.0832	−0.4972	0.1607	0.049*
H25B	−0.0900	−0.3009	0.2089	0.049*
H25C	−0.0437	−0.4179	0.2214	0.049*
H1	0.0177 (6)	0.394 (4)	0.0483 (8)	0.043 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0150 (6)	0.0278 (7)	0.0161 (6)	0.0011 (5)	0.0035 (5)	−0.0022 (5)
N2	0.0145 (6)	0.0271 (7)	0.0145 (6)	−0.0002 (5)	0.0025 (5)	−0.0008 (5)
C1	0.0156 (7)	0.0264 (8)	0.0197 (7)	0.0008 (6)	0.0070 (6)	−0.0015 (6)
C2	0.0174 (7)	0.0288 (8)	0.0238 (8)	−0.0036 (6)	0.0063 (6)	−0.0014 (6)
C3	0.0155 (7)	0.0311 (8)	0.0213 (7)	−0.0021 (6)	0.0040 (6)	−0.0037 (6)
C4	0.0134 (7)	0.0277 (8)	0.0188 (7)	0.0010 (6)	0.0033 (6)	−0.0037 (6)
C5	0.0128 (6)	0.0268 (8)	0.0175 (7)	0.0016 (6)	0.0028 (5)	−0.0041 (6)
C6	0.0142 (6)	0.0265 (8)	0.0156 (7)	0.0029 (6)	0.0023 (5)	−0.0029 (6)
C7	0.0192 (7)	0.0287 (8)	0.0176 (7)	0.0037 (6)	0.0028 (6)	−0.0013 (6)
C8	0.0210 (7)	0.0276 (8)	0.0170 (7)	0.0020 (6)	0.0041 (6)	0.0005 (6)
C9	0.0170 (7)	0.0242 (8)	0.0192 (7)	0.0026 (6)	0.0070 (6)	−0.0011 (6)
C10	0.0155 (6)	0.0248 (7)	0.0190 (7)	0.0022 (6)	0.0064 (5)	−0.0015 (6)
C11	0.0175 (7)	0.0257 (8)	0.0204 (7)	0.0000 (6)	0.0055 (6)	−0.0005 (6)
C12	0.0174 (7)	0.0259 (8)	0.0214 (7)	0.0003 (6)	0.0046 (6)	−0.0005 (6)
C13	0.0154 (7)	0.0267 (8)	0.0201 (7)	0.0019 (6)	0.0030 (6)	−0.0031 (6)
C14	0.0220 (8)	0.0268 (8)	0.0275 (8)	−0.0035 (7)	0.0018 (6)	0.0026 (7)
C15	0.0259 (8)	0.0287 (8)	0.0232 (8)	0.0005 (7)	0.0002 (6)	0.0052 (7)
C16	0.0166 (7)	0.0268 (8)	0.0217 (7)	0.0034 (6)	0.0038 (6)	−0.0028 (6)
C17	0.0206 (7)	0.0309 (8)	0.0238 (8)	−0.0051 (7)	0.0061 (6)	−0.0019 (7)
C18	0.0243 (8)	0.0318 (8)	0.0189 (7)	−0.0024 (7)	0.0047 (6)	0.0018 (7)
C19	0.0157 (7)	0.0317 (8)	0.0232 (8)	0.0004 (6)	0.0001 (6)	−0.0010 (7)
C20	0.0207 (7)	0.0299 (8)	0.0234 (8)	0.0015 (7)	−0.0009 (6)	−0.0018 (7)
C21	0.0190 (7)	0.0298 (8)	0.0229 (8)	−0.0027 (6)	0.0001 (6)	0.0002 (7)
C22	0.0254 (8)	0.0330 (9)	0.0266 (8)	−0.0064 (7)	0.0042 (7)	−0.0027 (7)
C23	0.0183 (7)	0.0251 (8)	0.0213 (7)	0.0012 (6)	0.0033 (6)	0.0006 (6)
C24	0.0269 (8)	0.0314 (9)	0.0258 (8)	0.0001 (7)	0.0114 (7)	0.0017 (7)
C25	0.0327 (9)	0.0375 (10)	0.0271 (8)	−0.0075 (8)	0.0103 (7)	0.0012 (7)

Geometric parameters (Å, º)

N1—C4	1.3668 (17)	C14—H14	0.9500
N1—C1	1.3775 (18)	C15—C16	1.387 (2)
N2—C6	1.3723 (17)	C15—H15	0.9500
N2—C9	1.3733 (19)	C16—C17	1.390 (2)
N2—H1	0.906 (18)	C16—C19	1.5178 (19)
C1—N1	1.3775 (18)	C17—C18	1.394 (2)
C1—C10^i	1.4053 (19)	C17—H17	0.9500
C1—C2	1.456 (2)	C18—H18	0.9500
C2—C3	1.348 (2)	C19—C20	1.527 (2)
C2—H2	0.9500	C19—H19A	0.9900
C3—C4	1.446 (2)	C19—H19B	0.9900
C3—H3	0.9500	C20—C21	1.5254 (19)
C4—N1	1.3668 (17)	C20—H20A	0.9900
C4—C5	1.413 (2)	C20—H20B	0.9900
C5—C6	1.401 (2)	C21—C22	1.523 (2)
C5—C11	1.4350 (19)	C21—H21A	0.9900
C6—C7	1.425 (2)	C21—H21B	0.9900
C7—C8	1.357 (2)	C22—H22A	0.9800
C7—H7	0.9500	C22—H22B	0.9800
C8—C9	1.4317 (19)	C22—H22C	0.9800
C8—H8	0.9500	C23—C24	1.528 (2)
C9—C10	1.403 (2)	C23—H23A	0.9900
C10—C1^i	1.4054 (19)	C23—H23B	0.9900
C10—C23	1.513 (2)	C24—C25	1.521 (2)
C11—C12	1.202 (2)	C24—H24A	0.9900
C12—C13	1.4375 (19)	C24—H24B	0.9900
C13—C18	1.395 (2)	C25—H25A	0.9800
C13—C14	1.397 (2)	C25—H25B	0.9800
C14—C15	1.386 (2)	C25—H25C	0.9800
C4—N1—C1	105.17 (12)	C15—C16—C19	120.41 (14)
C6—N2—C9	110.06 (12)	C17—C16—C19	121.40 (14)
C6—N2—H1	124.8 (12)	C16—C17—C18	121.24 (14)
C9—N2—H1	125.0 (12)	C16—C17—H17	119.4
N1—C1—C10^i	125.75 (13)	C18—C17—H17	119.4
N1—C1—C10^i	125.75 (13)	C17—C18—C13	120.06 (14)
N1—C1—C2	110.43 (12)	C17—C18—H18	120.0
N1—C1—C2	110.43 (12)	C13—C18—H18	120.0
C10^i—C1—C2	123.82 (13)	C16—C19—C20	112.56 (12)
C3—C2—C1	106.51 (13)	C16—C19—H19A	109.1
C3—C2—H2	126.7	C20—C19—H19A	109.1
C1—C2—H2	126.7	C16—C19—H19B	109.1
C2—C3—C4	106.77 (13)	C20—C19—H19B	109.1
C2—C3—H3	126.6	H19A—C19—H19B	107.8
C4—C3—H3	126.6	C21—C20—C19	114.37 (12)
N1—C4—C5	125.68 (13)	C21—C20—H20A	108.7
N1—C4—C5	125.68 (13)	C19—C20—H20A	108.7
N1—C4—C3	111.11 (13)	C21—C20—H20B	108.7
N1—C4—C3	111.11 (13)	C19—C20—H20B	108.7
C5—C4—C3	123.18 (12)	H20A—C20—H20B	107.6
C6—C5—C4	126.91 (12)	C22—C21—C20	111.99 (13)
C6—C5—C11	115.87 (13)	C22—C21—H21A	109.2
C4—C5—C11	117.18 (13)	C20—C21—H21A	109.2
N2—C6—C5	126.74 (13)	C22—C21—H21B	109.2
N2—C6—C7	106.89 (13)	C20—C21—H21B	109.2
C5—C6—C7	126.37 (13)	H21A—C21—H21B	107.9
C8—C7—C6	108.30 (13)	C21—C22—H22A	109.5
C8—C7—H7	125.9	C21—C22—H22B	109.5
C6—C7—H7	125.9	H22A—C22—H22B	109.5
C7—C8—C9	108.12 (13)	C21—C22—H22C	109.5
C7—C8—H8	125.9	H22A—C22—H22C	109.5
C9—C8—H8	125.9	H22B—C22—H22C	109.5
N2—C9—C10	126.40 (13)	C10—C23—C24	112.79 (12)
N2—C9—C8	106.64 (12)	C10—C23—H23A	109.0
C10—C9—C8	126.96 (13)	C24—C23—H23A	109.0
C9—C10—C1^i	123.73 (13)	C10—C23—H23B	109.0
C9—C10—C23	117.70 (12)	C24—C23—H23B	109.0
C1^i—C10—C23	118.53 (12)	H23A—C23—H23B	107.8
C12—C11—C5	177.62 (15)	C25—C24—C23	112.67 (13)
C11—C12—C13	176.30 (17)	C25—C24—H24A	109.1
C18—C13—C14	118.74 (13)	C23—C24—H24A	109.1
C18—C13—C12	122.10 (13)	C25—C24—H24B	109.1
C14—C13—C12	119.12 (14)	C23—C24—H24B	109.1
C15—C14—C13	120.36 (14)	H24A—C24—H24B	107.8
C15—C14—H14	119.8	C24—C25—H25A	109.5
C13—C14—H14	119.8	C24—C25—H25B	109.5
C14—C15—C16	121.39 (15)	H25A—C25—H25B	109.5
C14—C15—H15	119.3	C24—C25—H25C	109.5
C16—C15—H15	119.3	H25A—C25—H25C	109.5
C15—C16—C17	118.17 (13)	H25B—C25—H25C	109.5
C4—N1—C1—C10^i	−178.47 (14)	C6—N2—C9—C10	180.00 (14)
C4—N1—C1—C2	1.20 (15)	C6—N2—C9—C8	0.06 (15)
N1—C1—C2—C3	−0.59 (16)	C7—C8—C9—N2	−0.06 (16)
N1—C1—C2—C3	−0.59 (16)	C7—C8—C9—C10	180.00 (14)
C10^i—C1—C2—C3	179.08 (14)	N2—C9—C10—C1^i	−3.7 (2)
C1—C2—C3—C4	−0.25 (16)	C8—C9—C10—C1^i	176.18 (14)
C1—N1—C4—C5	176.60 (13)	N2—C9—C10—C23	178.81 (13)
C1—N1—C4—C3	−1.36 (15)	C8—C9—C10—C23	−1.3 (2)
C2—C3—C4—N1	1.03 (17)	C18—C13—C14—C15	−1.6 (2)
C2—C3—C4—N1	1.03 (17)	C12—C13—C14—C15	176.26 (15)
C2—C3—C4—C5	−176.99 (13)	C13—C14—C15—C16	−0.1 (2)
N1—C4—C5—C6	1.2 (2)	C14—C15—C16—C17	1.5 (2)
N1—C4—C5—C6	1.2 (2)	C14—C15—C16—C19	−179.96 (15)
C3—C4—C5—C6	178.96 (14)	C15—C16—C17—C18	−1.2 (2)
N1—C4—C5—C11	−176.41 (13)	C19—C16—C17—C18	−179.69 (14)
N1—C4—C5—C11	−176.41 (13)	C16—C17—C18—C13	−0.5 (2)
C3—C4—C5—C11	1.3 (2)	C14—C13—C18—C17	1.9 (2)
C9—N2—C6—C5	−179.94 (13)	C12—C13—C18—C17	−175.87 (14)
C9—N2—C6—C7	−0.04 (15)	C15—C16—C19—C20	−92.00 (18)
C4—C5—C6—N2	0.0 (2)	C17—C16—C19—C20	86.47 (17)
C11—C5—C6—N2	177.62 (13)	C16—C19—C20—C21	173.83 (13)
C4—C5—C6—C7	−179.92 (14)	C19—C20—C21—C22	176.50 (13)
C11—C5—C6—C7	−2.3 (2)	C9—C10—C23—C24	92.90 (16)
N2—C6—C7—C8	0.00 (16)	C1^i—C10—C23—C24	−84.67 (16)
C5—C6—C7—C8	179.90 (14)	C10—C23—C24—C25	179.15 (13)
C6—C7—C8—C9	0.03 (16)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N1^i	0.906 (18)	2.290 (18)	2.8586 (16)	120.5 (15)
N2—H1···N1	0.906 (18)	2.425 (19)	2.9779 (17)	119.5 (14)

Symmetry code: (i) −x, −y+1, −z.