5,10,15,20-Tetrakis­[(4-ethyl­carbonyl)­oxy]­phenyl­porphyrin

The crystal structure of the title compound, C₅₆H₄₆N₄O₈, shows the porphyrin core to be composed of four pyrrole rings linked through methene carbon bridges. Each mol­ecule lies across a crystallographic inversion center. The porphyrin core is planar, which facilitates π-electron delocalization. The inner nitro­gen H atoms are found localized on opposite pyrrole rings and these rings differ structurally from the other two pyrrole rings.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.065
• wR factor = 0.161
• Data-to-parameter ratio = 18.1

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry

---

S1. Comment

Porphyrins are receiving attention as photosensitizers in prospective photochemical electron-transfer systems for solar energy conversion (Morstyn & Kaye, 1990; Zanelli & Kaelin, 1990; Mehta et al., 1993). In addition, porphyrins are important prosthetic groups for a number of metalloproteins and enzymes, and their function depends on the metal ion and the nature of the axial ligand, as well as on the specific environment provided by the polypeptide chain (Dolphin, 1978; Conn et al., 1996). In the present study, the synthesis and X-ray crystal structure of the title compound is reported.

The porphyrin macrocycle is composed of four pyrrole rings alternately linked through methene carbon bridges. Each molecule possesses a crystallographic inversion center. The porphyrin core is planar which, facilitates the π-electron delocalization·The re-determination of the structure of porphine was reported by Chen & Tulinsky (1972), and it suggests that there are two structurally different pairs of pyrrole rings. Similarly, the title compound has two localized imino hydrogen atoms on opposite pyrrole rings and these rings differ structurally from the other two pyrrole rings. The imino H atoms cannot occupy adjacent pyrrole rings due to steric and electronic interactions which would increase potential energy of this configuration. Hence they should be present on diametrically opposed rings. Two dominant resonance structures of tetraphenylporphyrin (TPP), each with 18π electrons, have been reported by Silvers & Tulinsky (1967). The title porphyrin structure corresponds approximately to a structure expected of a hybrid of the two predominant classic resonance forms of the macrocyclic ring system. The pyrrolyl protons are equivalent in the NMR spectra, appearing as a singlet at lower field. The pyrrole N—H protons apparently undergo fast exchange in deuterochloroform solution, since their resonances are not visible in the NMR spectra.

The structure of the porphyrin core is very similar to other free base porphyrins (Silvers & Tulinsky, 1967, Chen & Tulinsky, 1972, Codding & Tulinsky, 1972, Little & Ibers, 1975). The chemically equivalent bonds around the 24 atom core have similar bond lengths. The 24 atom core is planar with an r.m.s. deviation from the the plane of 0.021 (3) Å, and the two independent pyrrole ring planes are tilted slightly at an angle of 2.1 (3)°. The imino H atoms are displaced on opposite sides with respect to the porphyrin macrocycle. The distance between the two imino H atoms is 2.33 (4) Å, which is slightly shorter than those values found in porphine (2.41 Å), and comparable with those in TPP (2.36 Å) and octaethylporphyrin (OEP) [2.36 (4) Å] (Codding & Tulinsky, 1972, Silvers & Tulinsky, 1967, Lauher & Ibers, 1973). The imino H atoms form bifurcated intramolecular hydrogen bonds with the adjacent unprotonted N atoms (Table 2). Owing to the steric effect of the bulky phenyl group, the four planes of the phenyl groups are almost perpendicular to the porphyrin macrocycle. Therefore, the angles between the planes of the first pyrrole ring containing N1 and its neighboring two phenyl rings containing C10 and C20 are 86.1 (2)° and 84.0 (1)°, respectively, while those between the planes of the second pyrrole ring containing N2 and its neighboring two phenyl rings containing C10 and C20ⁱ are 84.0 (2)° and 84.1 (2)°, respectively.

Each individual porphyrin molecule is linked to four molecules by four C8—H8···O2 weak hydrogen bonds, in two of them acting as donor and two as acceptor. This interaction generates a R⁴₄(54) graph-set ring (Etter et al., 1990) as shown in Fig. 2. These rings are joined in a sheet, extended along all the crystal, by C(12) chains.

S2. Experimental

A 250 ml three-necked round-bottomed flask equipped with a magnetic stirring bar and a reflux condenser was charged with 4-hydroxybenzaldehyde (2.46 g, 20.2 mmol), acetic anhydride (12 ml), and propionic acid (100 ml) and stirred for 15 min at 383 K. Pyrrole (1.36 g, 20.6 mmol) was added slowly, and the mixture was refluxed for 1.0 h. The resulting solution was then cooled to room temperature and kept overnight. The purple crystals were filtered, washed with hot water and ethanol to remove traced of propionic acid, and dried in a vacuum oven to give a 12% yield (547 mg, 0.606 mmol): TLC R_f 0.95 (dichloromethane); ¹H-NMR (CDCl₃, 400 MHz) δ −2.77 (s, 2 H, NH), 1.45 (t, J = 8.0 Hz, 12 H, CH₃), 2.80 (q, J = 7.2 Hz, 8 H, CH₂), 7.54 (d, J = 8.4 Hz, 8 H, ArH), 8.26 (d, J = 8.8 Hz, 8 H, ArH), 8.92 (s, 8 H, β-pyrrole-H); ¹³C-NMR (CDCl₃, 75 Hz) δ 9.18, 27.97, 119.27, 119.86, 131.17, 135.27, 139.44, 150.76, 173.05; FT—IR (KBr) 3318 (br, NH), 3037 (w), 2979 (w), 1760 (s, C=O), 1594 (s, C=C), 1503 (m), 1198 (s), 1139 (s), 968 (s), 799 (s) cm⁻¹; UV-vis (CH₂Cl₂) λ_maxnm (ε, dm³mol⁻¹cm⁻¹): 418 (4.72 x 10⁵), 446 (1.95 x 10⁴), 514 (1.85 x 10⁵), 548 (8.42 x 10³), 590 (5.75 x 10²), 646 (5.21 x 10²); MS (FAB) m/z (relative intensity) 903 (M⁺).

S3. Refinement

The H atoms bonded to C atoms were placed in geometrically calculated positions and refined as riding, with U_iso(H) = 1.2U_eq(C) [1.5U_eq(C) for the methyl H atoms]. The imino H atom (H2) was located from a difference Fourier synthesis and refined by constraining the distance H2—N2 to 0.96 (2) Å. The C26—C27, C27—C28 bond lengths were restrained to 1.500 (3) Å in the refinement. SADI restraints were used for the bonds involving O1 and O3 atoms. During anisotropic refinement, the atomic displacement parameters of the end chain atoms were poorly defined and the temperature factors of atoms C18 and C28 were higher than those of atoms C17 and C27, because of the easily vibrating ends of the chains far away from the porphyrin ring. Attempts to refine a disordered model for these groups were unsuccessful, and SIMU/DELU restraints [instructions in the SHELX97 Manual (Sheldrick, 1997)] were used to get the final structure. As a result, the geometric parameters involving the end chain atoms are only a rough approximation to reality. The poor data to parameter ratio is due to the contribution of the floppy ester group in the low angle data only.

Computing details

Data collection: Bruker (1998) SMART; cell refinement: Bruker (1998) SMART; data reduction: Bruker (2000) SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: NRCVAX (Gabe et al., 1989); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. Structure chemical diagram Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids. Fig. 2. A part of the crystal structure, showing the formation of a sheet through C—H···O interactions and the R^44(54) motif. The ester group (c20 → c28) and H atoms not taken part in the interactions are omitted. Dotted lines reperesent H-bonds.

(I)

Crystal data

C56H46N4O8	F(000) = 948
Mr = 902.97	Dx = 1.283 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4045 (10) Å	Cell parameters from all reflections
b = 10.9423 (11) Å	θ = 1.8–28.3°
c = 23.4260 (19) Å	µ = 0.09 mm^−1
β = 104.187 (4)°	T = 293 K
V = 2337.2 (4) Å^3	Pillar, violet
Z = 2	0.25 × 0.20 × 0.15 mm

Data collection

Bruker CCD area detector diffractometer	5626 independent reflections
Radiation source: fine-focus sealed tube	928 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
phi and ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: ψ scan (North, Phillips & Mathews, 1968)	h = −12→12
Tmin = 0.969, Tmax = 0.990	k = −11→14
14839 measured reflections	l = −28→30

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	w = 1/[σ^2(Fo^2) + (0.049P)^2] where P = (Fo^2 + 2Fc^2)/3
5626 reflections	(Δ/σ)max < 0.001
311 parameters	Δρmax = 0.26 e Å^−3
318 restraints	Δρmin = −0.31 e Å^−3

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 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
N1	0.4521 (4)	0.1475 (3)	0.04429 (15)	0.0797 (10)
N2	0.3839 (5)	0.0737 (4)	−0.07914 (19)	0.0844 (10)
O1	0.0224 (4)	0.7161 (3)	−0.10525 (16)	0.1313 (11)
O2	−0.0466 (5)	0.6733 (3)	−0.19746 (18)	0.1795 (18)
O3	0.7002 (4)	0.2078 (4)	0.38940 (17)	0.1551 (13)
O4	0.7145 (6)	0.4020 (4)	0.37414 (18)	0.1947 (19)
C1	0.4916 (5)	0.1678 (4)	0.1051 (2)	0.0837 (11)
C2	0.4308 (5)	0.2814 (4)	0.1192 (2)	0.0910 (12)
H2A	0.4396	0.3136	0.1567	0.109*
C3	0.3587 (5)	0.3319 (4)	0.0680 (2)	0.0888 (12)
H3	0.3102	0.4067	0.0635	0.107*
C4	0.3704 (5)	0.2483 (4)	0.0205 (2)	0.0814 (11)
C5	0.3073 (5)	0.2665 (4)	−0.0379 (2)	0.0825 (10)
C6	0.3117 (5)	0.1861 (4)	−0.0826 (2)	0.0830 (11)
C7	0.2453 (5)	0.2010 (4)	−0.14587 (19)	0.0955 (13)
H7	0.1906	0.2682	−0.1629	0.115*
C8	0.2757 (5)	0.1031 (4)	−0.1753 (2)	0.0973 (13)
H8	0.2436	0.0908	−0.2157	0.117*
C9	0.3649 (5)	0.0213 (4)	−0.1347 (2)	0.0881 (12)
C10	0.2323 (6)	0.3847 (4)	−0.0569 (2)	0.0902 (12)
C11	0.3070 (6)	0.4849 (4)	−0.0657 (2)	0.1014 (13)
H11	0.4086	0.4815	−0.0590	0.122*
C12	0.2347 (6)	0.5925 (4)	−0.0844 (2)	0.1099 (13)
H12	0.2886	0.6596	−0.0915	0.132*
C13	0.0874 (7)	0.6037 (4)	−0.0929 (2)	0.1098 (13)
C14	0.0099 (6)	0.5038 (5)	−0.0853 (2)	0.1195 (13)
H14	−0.0917	0.5080	−0.0924	0.143*
C15	0.0827 (6)	0.3939 (4)	−0.0665 (2)	0.1103 (13)
H15	0.0288	0.3261	−0.0604	0.132*
C16	−0.0449 (7)	0.7466 (6)	−0.1619 (3)	0.1470 (17)
C17	−0.0982 (7)	0.8742 (5)	−0.1654 (3)	0.1648 (19)
H17A	−0.0286	0.9241	−0.1376	0.198*
H17B	−0.1911	0.8770	−0.1544	0.198*
C18	−0.1181 (8)	0.9264 (6)	−0.2271 (3)	0.240 (3)
H18A	−0.1535	1.0088	−0.2280	0.359*
H18B	−0.1876	0.8776	−0.2546	0.359*
H18C	−0.0257	0.9257	−0.2377	0.359*
C19	0.5777 (5)	0.0892 (4)	0.1465 (2)	0.0859 (11)
C20	0.6120 (6)	0.1265 (4)	0.2090 (2)	0.1020 (12)
C21	0.7268 (6)	0.1993 (5)	0.2331 (2)	0.1238 (14)
H21	0.7881	0.2263	0.2100	0.149*
C22	0.7554 (6)	0.2351 (5)	0.2923 (2)	0.1365 (15)
H22	0.8324	0.2887	0.3069	0.164*
C23	0.6740 (8)	0.1939 (6)	0.3292 (2)	0.1360 (14)
C24	0.5582 (6)	0.1157 (5)	0.3049 (2)	0.1256 (14)
H24	0.5005	0.0851	0.3286	0.151*
C25	0.5271 (6)	0.0824 (4)	0.2458 (2)	0.1164 (13)
H25	0.4490	0.0301	0.2306	0.140*
C26	0.7346 (8)	0.3237 (6)	0.4075 (2)	0.1565 (18)
C27	0.7571 (7)	0.3233 (5)	0.4723 (2)	0.1578 (19)
H27A	0.6646	0.3326	0.4832	0.189*
H27B	0.8035	0.2481	0.4892	0.189*
C28	0.8536 (8)	0.4293 (5)	0.4922 (3)	0.243 (3)
H28A	0.8712	0.4373	0.5341	0.365*
H28B	0.8073	0.5021	0.4736	0.365*
H28C	0.9452	0.4173	0.4817	0.365*
H2	0.426 (4)	0.038 (3)	−0.0437 (12)	0.119 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.085 (2)	0.076 (2)	0.0752 (18)	0.0067 (17)	0.0143 (19)	0.0026 (18)
N2	0.095 (3)	0.081 (2)	0.075 (2)	0.0121 (19)	0.016 (2)	0.009 (2)
O1	0.140 (3)	0.1029 (19)	0.135 (2)	0.0427 (19)	0.004 (2)	−0.005 (2)
O2	0.212 (4)	0.137 (3)	0.142 (3)	0.045 (3)	−0.048 (3)	−0.020 (2)
O3	0.154 (3)	0.195 (3)	0.106 (2)	0.037 (3)	0.012 (2)	−0.021 (2)
O4	0.240 (5)	0.221 (3)	0.121 (3)	0.051 (4)	0.040 (3)	0.010 (3)
C1	0.091 (3)	0.082 (2)	0.080 (2)	0.0051 (19)	0.025 (2)	0.000 (2)
C2	0.101 (3)	0.086 (2)	0.086 (2)	0.006 (2)	0.024 (2)	−0.006 (2)
C3	0.094 (3)	0.083 (2)	0.090 (2)	0.009 (2)	0.024 (2)	−0.001 (2)
C4	0.086 (3)	0.076 (2)	0.0831 (19)	0.0036 (19)	0.022 (2)	0.0031 (19)
C5	0.083 (2)	0.081 (2)	0.0848 (19)	0.0101 (19)	0.022 (2)	0.0068 (18)
C6	0.089 (3)	0.079 (2)	0.0792 (19)	0.011 (2)	0.018 (2)	0.011 (2)
C7	0.103 (3)	0.092 (3)	0.084 (2)	0.018 (2)	0.010 (2)	0.011 (2)
C8	0.110 (3)	0.097 (3)	0.076 (2)	0.019 (3)	0.006 (2)	0.004 (2)
C9	0.101 (3)	0.087 (3)	0.071 (3)	0.012 (2)	0.012 (2)	0.006 (2)
C10	0.083 (2)	0.082 (2)	0.107 (2)	0.014 (2)	0.025 (2)	0.009 (2)
C11	0.093 (3)	0.083 (2)	0.129 (3)	0.013 (2)	0.027 (3)	0.018 (3)
C12	0.109 (3)	0.082 (2)	0.135 (3)	0.013 (2)	0.023 (3)	0.013 (2)
C13	0.111 (3)	0.085 (2)	0.128 (3)	0.027 (2)	0.017 (3)	0.002 (2)
C14	0.091 (3)	0.107 (3)	0.154 (3)	0.025 (2)	0.019 (3)	0.011 (3)
C15	0.087 (3)	0.096 (2)	0.146 (3)	0.015 (2)	0.024 (3)	0.018 (3)
C16	0.152 (3)	0.123 (3)	0.146 (3)	0.048 (3)	−0.003 (3)	−0.001 (3)
C17	0.168 (4)	0.133 (3)	0.169 (4)	0.065 (3)	−0.004 (4)	0.014 (3)
C18	0.282 (7)	0.197 (5)	0.215 (5)	0.058 (5)	0.013 (6)	0.057 (4)
C19	0.093 (3)	0.091 (3)	0.073 (2)	0.001 (2)	0.020 (2)	0.005 (2)
C20	0.110 (3)	0.118 (3)	0.077 (2)	0.000 (2)	0.022 (2)	−0.004 (2)
C21	0.125 (3)	0.151 (3)	0.091 (3)	−0.016 (2)	0.017 (3)	−0.018 (3)
C22	0.135 (3)	0.165 (3)	0.098 (3)	−0.014 (3)	0.007 (3)	−0.022 (3)
C23	0.137 (3)	0.173 (3)	0.093 (2)	0.015 (2)	0.020 (2)	−0.009 (3)
C24	0.135 (3)	0.165 (3)	0.080 (2)	0.014 (2)	0.032 (3)	−0.002 (3)
C25	0.126 (3)	0.142 (3)	0.083 (2)	0.004 (2)	0.029 (2)	0.002 (3)
C26	0.168 (3)	0.190 (4)	0.104 (3)	0.041 (3)	0.019 (3)	−0.010 (3)
C27	0.172 (4)	0.193 (4)	0.101 (3)	0.030 (3)	0.020 (4)	−0.008 (3)
C28	0.274 (8)	0.254 (7)	0.163 (5)	−0.016 (5)	−0.021 (5)	−0.020 (5)

Geometric parameters (Å, º)

N1—C4	1.381 (5)	C12—H12	0.9300
N1—C1	1.399 (5)	C13—C14	1.350 (6)
N2—C9	1.393 (5)	C14—C15	1.400 (5)
N2—C6	1.398 (5)	C14—H14	0.9300
N2—H2	0.92 (2)	C15—H15	0.9300
O1—C16	1.363 (4)	C16—C17	1.478 (7)
O1—C13	1.373 (3)	C17—C18	1.524 (6)
O2—C16	1.154 (6)	C17—H17A	0.9700
O3—C26	1.352 (4)	C17—H17B	0.9700
O3—C23	1.378 (4)	C18—H18A	0.9600
O4—C26	1.143 (6)	C18—H18B	0.9600
C1—C19	1.396 (5)	C18—H18C	0.9600
C1—C2	1.440 (5)	C19—C9^i	1.379 (5)
C2—C3	1.344 (5)	C19—C20	1.479 (6)
C2—H2A	0.9300	C20—C21	1.349 (6)
C3—C4	1.465 (5)	C20—C25	1.397 (6)
C3—H3	0.9300	C21—C22	1.401 (6)
C4—C5	1.366 (5)	C21—H21	0.9300
C5—C6	1.376 (5)	C22—C23	1.364 (6)
C5—C10	1.488 (5)	C22—H22	0.9300
C6—C7	1.470 (5)	C23—C24	1.392 (7)
C7—C8	1.343 (5)	C24—C25	1.391 (6)
C7—H7	0.9300	C24—H24	0.9300
C8—C9	1.421 (5)	C25—H25	0.9300
C8—H8	0.9300	C26—C27	1.481 (3)
C9—C19^i	1.379 (5)	C27—C28	1.476 (9)
C10—C11	1.346 (5)	C27—H27A	0.9700
C10—C15	1.373 (6)	C27—H27B	0.9700
C11—C12	1.376 (5)	C28—H28A	0.9600
C11—H11	0.9300	C28—H28B	0.9600
C12—C13	1.356 (6)	C28—H28C	0.9600
C4—N1—C1	105.5 (4)	O2—C16—O1	117.0 (6)
C9—N2—C6	111.0 (4)	O2—C16—C17	132.2 (6)
C9—N2—H2	127 (3)	O1—C16—C17	110.8 (6)
C6—N2—H2	122 (3)	C16—C17—C18	111.6 (5)
C16—O1—C13	120.1 (5)	C16—C17—H17A	109.3
C26—O3—C23	113.2 (5)	C18—C17—H17A	109.3
C19—C1—N1	125.0 (4)	C16—C17—H17B	109.3
C19—C1—C2	124.6 (5)	C18—C17—H17B	109.3
N1—C1—C2	110.4 (4)	H17A—C17—H17B	108.0
C3—C2—C1	107.0 (4)	C17—C18—H18A	109.5
C3—C2—H2A	126.5	C17—C18—H18B	109.5
C1—C2—H2A	126.5	H18A—C18—H18B	109.5
C2—C3—C4	107.8 (4)	C17—C18—H18C	109.5
C2—C3—H3	126.1	H18A—C18—H18C	109.5
C4—C3—H3	126.1	H18B—C18—H18C	109.5
C5—C4—N1	125.6 (5)	C9^i—C19—C1	126.2 (5)
C5—C4—C3	125.0 (5)	C9^i—C19—C20	116.0 (5)
N1—C4—C3	109.3 (4)	C1—C19—C20	117.8 (4)
C4—C5—C6	125.6 (5)	C21—C20—C25	117.8 (5)
C4—C5—C10	118.9 (5)	C21—C20—C19	122.4 (5)
C6—C5—C10	115.3 (4)	C25—C20—C19	119.8 (5)
C5—C6—N2	128.5 (4)	C20—C21—C22	121.2 (6)
C5—C6—C7	127.8 (4)	C20—C21—H21	119.4
N2—C6—C7	103.7 (4)	C22—C21—H21	119.4
C8—C7—C6	109.8 (4)	C23—C22—C21	122.3 (6)
C8—C7—H7	125.1	C23—C22—H22	118.9
C6—C7—H7	125.1	C21—C22—H22	118.9
C7—C8—C9	108.8 (5)	C22—C23—O3	128.6 (7)
C7—C8—H8	125.6	C22—C23—C24	116.5 (5)
C9—C8—H8	125.6	O3—C23—C24	114.4 (6)
C19^i—C9—N2	125.5 (5)	C25—C24—C23	121.4 (5)
C19^i—C9—C8	127.9 (5)	C25—C24—H24	119.3
N2—C9—C8	106.6 (4)	C23—C24—H24	119.3
C11—C10—C15	117.9 (5)	C24—C25—C20	120.7 (5)
C11—C10—C5	121.8 (5)	C24—C25—H25	119.7
C15—C10—C5	120.3 (5)	C20—C25—H25	119.7
C10—C11—C12	120.7 (5)	O4—C26—O3	120.1 (5)
C10—C11—H11	119.7	O4—C26—C27	131.4 (6)
C12—C11—H11	119.7	O3—C26—C27	106.4 (5)
C13—C12—C11	122.1 (5)	C28—C27—C26	104.1 (5)
C13—C12—H12	119.0	C28—C27—H27A	110.9
C11—C12—H12	119.0	C26—C27—H27A	110.9
C14—C13—C12	118.3 (5)	C28—C27—H27B	110.9
C14—C13—O1	121.7 (6)	C26—C27—H27B	110.9
C12—C13—O1	119.9 (6)	H27A—C27—H27B	109.0
C13—C14—C15	119.9 (5)	C27—C28—H28A	109.5
C13—C14—H14	120.0	C27—C28—H28B	109.5
C15—C14—H14	120.0	H28A—C28—H28B	109.5
C10—C15—C14	121.2 (5)	C27—C28—H28C	109.5
C10—C15—H15	119.4	H28A—C28—H28C	109.5
C14—C15—H15	119.4	H28B—C28—H28C	109.5
C4—N1—C1—C19	−178.9 (4)	C16—O1—C13—C14	−84.3 (7)
C4—N1—C1—C2	1.3 (5)	C16—O1—C13—C12	99.9 (7)
C19—C1—C2—C3	178.4 (4)	C12—C13—C14—C15	2.8 (8)
N1—C1—C2—C3	−1.8 (5)	O1—C13—C14—C15	−173.0 (4)
C1—C2—C3—C4	1.5 (5)	C11—C10—C15—C14	0.5 (7)
C1—N1—C4—C5	−179.1 (4)	C5—C10—C15—C14	−179.0 (4)
C1—N1—C4—C3	−0.4 (5)	C13—C14—C15—C10	−1.5 (8)
C2—C3—C4—C5	178.0 (4)	C13—O1—C16—O2	1.7 (10)
C2—C3—C4—N1	−0.7 (5)	C13—O1—C16—C17	−176.1 (5)
N1—C4—C5—C6	1.7 (8)	O2—C16—C17—C18	−19.6 (12)
C3—C4—C5—C6	−176.8 (4)	O1—C16—C17—C18	157.7 (6)
N1—C4—C5—C10	−175.3 (4)	N1—C1—C19—C9^i	−1.3 (8)
C3—C4—C5—C10	6.2 (7)	C2—C1—C19—C9^i	178.5 (4)
C4—C5—C6—N2	−2.8 (8)	N1—C1—C19—C20	178.5 (4)
C10—C5—C6—N2	174.3 (4)	C2—C1—C19—C20	−1.7 (7)
C4—C5—C6—C7	179.7 (4)	C9^i—C19—C20—C21	94.0 (6)
C10—C5—C6—C7	−3.2 (7)	C1—C19—C20—C21	−85.8 (6)
C9—N2—C6—C5	−178.3 (4)	C9^i—C19—C20—C25	−83.6 (6)
C9—N2—C6—C7	−0.4 (5)	C1—C19—C20—C25	96.6 (6)
C5—C6—C7—C8	179.2 (4)	C25—C20—C21—C22	−3.4 (8)
N2—C6—C7—C8	1.2 (5)	C19—C20—C21—C22	178.9 (5)
C6—C7—C8—C9	−1.6 (6)	C20—C21—C22—C23	3.3 (9)
C6—N2—C9—C19^i	179.8 (4)	C21—C22—C23—O3	170.7 (5)
C6—N2—C9—C8	−0.5 (5)	C21—C22—C23—C24	−1.2 (9)
C7—C8—C9—C19^i	−179.1 (5)	C26—O3—C23—C22	47.5 (9)
C7—C8—C9—N2	1.3 (6)	C26—O3—C23—C24	−140.5 (6)
C4—C5—C10—C11	82.5 (6)	C22—C23—C24—C25	−0.4 (9)
C6—C5—C10—C11	−94.8 (6)	O3—C23—C24—C25	−173.5 (4)
C4—C5—C10—C15	−98.1 (6)	C23—C24—C25—C20	0.1 (8)
C6—C5—C10—C15	84.6 (6)	C21—C20—C25—C24	1.8 (8)
C15—C10—C11—C12	−0.8 (7)	C19—C20—C25—C24	179.5 (5)
C5—C10—C11—C12	178.6 (4)	C23—O3—C26—O4	13.9 (11)
C10—C11—C12—C13	2.3 (8)	C23—O3—C26—C27	179.2 (5)
C11—C12—C13—C14	−3.2 (8)	O4—C26—C27—C28	−41.2 (12)
C11—C12—C13—O1	172.7 (4)	O3—C26—C27—C28	155.8 (6)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.92 (3)	2.34 (3)	2.918 (6)	121 (3)
N2—H2···N1^i	0.92 (3)	2.33 (3)	2.879 (6)	118 (3)
C8—H8···O2^ii	0.93	2.56	3.312 (6)	139

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