Inclusion of HNEt₃⁺ in an acyclic tetraphenolate

The acyclic tetraphenolic derivative 2,2'-methyl­ene­bis[6-(3-tert-butyl-2-hydroxy-5-methyl­benzyl)-4-methyl­phenol] reacts with excess triethyl­amine in aceto­nitrile to form a molecular complex, i.e. triethyl­ammonium 2-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-6-[3-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-2-hydroxy-5-methylbenzyl]-4-methylphenolate aceto­nitrile sol­vate, C₆H₁₆N⁺·­C₃₉H₄₇O₄^-·­C₂H₃N, where the organic HNEt₃⁺ cation is included in the partial cone defined by the aromatic faces of the acyclic poly­phenolate.

S1. Comment

The separation of radioactive metal cations from waste solutions produced by the nuclear industry is an important goal for the environmental management and recycling of nuclear fuels. In this respect, the comparative study of various classes of complexing agents has been undertaken, in particular the calixarene and their acyclic counterparts. The latter are very flexible ligands which have the potential to fit the coordination requirements of actinide cations (Thuéry & Nierlich, 1997). Full characterization of the organic extractants including determination of their conformation in the solid state is important for the understanding of extraction processes. If there are now numerous examples of crystal structures of calix[4]arenes reported in the literature, those of their acyclic homologues are less common (Casiraghi et al., 1982; Paulus & Böhmer, 1984; Usui et al., 1991). All these reports concern the fully protonated ligands. Herein we present the crystal structure of the triethylammonium salt of [methylenebis-2,2'-(6,6'- (3-tert-butyl-2-hydroxy-5-methyl)benzyl-4,4'-methyl)phenol].(acetonitrile), (I), the first of an anionic derivative of an acyclic tetraphenol. \sch

The crystal structure of (I) (Fig. 1) reveals that the tetraphenolic derivative has been deprotonated once by reaction with excess triethylamine and that the anion formed is stabilized by strong intramolecular hydrogen bonds. The triethylammonium cation donates an hydrogen bond to the deprotonated phenolate group O3. Two other hydrogen bonds are donated to O3 by O2 and O4, while O2 receives one from O1. This arrangement is reminiscent of the hydrogen-bond pattern classically stabilizing the deprotonated calix[4]arene (Gutsche, 1998).

The conformation of (I) in the solid state can be described as syn-anti (Casiraghi et al., 1982; Perrin & Oehler, 1990). Consequently, three of its aromatic faces are organized into a partial cone. This cavity is occupied by one of the terminal methyl group of a triethylammonium cation hydrogen bound to an adjacent phenolate (Fig. 2). This methyl group is positioned 1.17 (2) Å below the plane defined by the lips of the partial cone (C28, C38 and C48) that can be considered as the limit of the cavity. Interestingly, the inclusion of cations in the aromatic cavity of calix[4]arenes is a well known feature of this class of macrocycles (Leverd et al., 2000). Conversely, the formation of host–guest complexes of acyclic oligomers (induced-fit inclusion) has only been evidenced for neutral organic molecules (Sone et al., 1989; Usui et al., 1991) and not for charged species. Compound (I) is, to the best of our knowledge, the first example of such an inclusion occurring with a cation.

The extended structure (Fig. 2) consists of residues organizing the solid into rods parallel to the [010] direction. In contrast to previously reported structures of polyphenolic oligomers which pack into hydrogen bound dimers or infinite chains, the arrangement of the solid in (I) results from the interactions due to both hydrogen bonds and inclusion phenomena.

S2. Experimental

The tetraphenol was synthesized according to the published method (Weber et al., 1999). Single crystals of the title compound suitable for structure determination were obtained by slow evaporation (298 K) of an acetonitrile solution containing a mixture of the tetraphenol and a twofold excess of triethylamine.

S3. Refinement

Hydrogen atoms of the ligand were included as riding atoms at calculated positions (U = 1.2 times that of corresponding carbon) with the exception of those involved in hydrogen bonding which were positioned from the Fourier difference map and refined.

Computing details

Data collection: DENZO (Otwinowski & Minor, 1997); cell refinement: DENZO; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Drawing of the title compound with atom labelling. Displacement ellipsoids are drawn at the 20% probability level except for the H atoms which are represented as spheres of arbitrary radii. H atoms which do not participate in hydrogen bonding have been omitted for clarity. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. View of the extended structure.

(I)

Crystal data

C6H16N^+·C39H47O4^−·C2H3N	F(000) = 1576
Mr = 723.02	Dx = 1.141 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 16.024 (3) Å	Cell parameters from all reflections
b = 17.073 (3) Å	θ = 2.7–26.4°
c = 16.067 (3) Å	µ = 0.07 mm^−1
β = 106.75 (3)°	T = 100 K
V = 4209.1 (15) Å^3	Block, colourless
Z = 4	0.2 × 0.2 × 0.15 mm

Data collection

Nonius CCD diffractometer	5631 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 26.4°, θmin = 2.7°
ω–scans	h = 0→19
15352 measured reflections	k = −21→21
8472 independent reflections	l = −20→18

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)] = 0.051	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) + (0.0501P)^2 + 0.8636P] where P = (Fo^2 + 2Fc^2)/3
8472 reflections	(Δ/σ)max < 0.001
508 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.19 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. Hydrogen atoms of the ligand were included as riding atoms at calculated positions (U=1.2 times that of corresponding carbon) with the exception of those involved in hydrogen bonding which were positionned from the molecules were introduced Fourier difference map and refined.

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

	x	y	z	Uiso*/Ueq
O1	0.32625 (10)	0.12633 (7)	0.55719 (8)	0.0313 (3)
O2	0.28551 (8)	0.20731 (7)	0.40769 (8)	0.0257 (3)
O3	0.28826 (8)	0.19770 (6)	0.25329 (7)	0.0211 (3)
O4	0.43541 (9)	0.28074 (7)	0.29659 (8)	0.0275 (3)
C11	0.32510 (12)	0.16343 (10)	0.63245 (11)	0.0222 (4)
C12	0.32054 (11)	0.11636 (10)	0.70262 (11)	0.0223 (4)
C13	0.32214 (13)	0.15443 (11)	0.77964 (12)	0.0285 (4)
H13A	0.3196	0.1243	0.8271	0.034*
C14	0.32738 (14)	0.23598 (11)	0.78903 (12)	0.0323 (5)
C15	0.33020 (13)	0.27982 (11)	0.71751 (12)	0.0303 (4)
H15A	0.3336	0.3341	0.7225	0.036*
C16	0.32821 (12)	0.24578 (10)	0.63875 (11)	0.0231 (4)
C17	0.32661 (12)	0.29687 (10)	0.56090 (11)	0.0249 (4)
H17A	0.3439	0.3497	0.5809	0.030*
H17B	0.3690	0.2770	0.5335	0.030*
C18	0.33149 (19)	0.27309 (14)	0.87532 (14)	0.0539 (7)
H18A	0.3609	0.2385	0.9215	0.081*
H18B	0.2734	0.2827	0.8784	0.081*
H18C	0.3627	0.3217	0.8809	0.081*
C19	0.31458 (13)	0.02651 (11)	0.69526 (12)	0.0285 (4)
C19A	0.30778 (15)	−0.01189 (12)	0.77920 (13)	0.0383 (5)
H19A	0.2562	0.0064	0.7920	0.057*
H19B	0.3581	0.0015	0.8262	0.057*
H19C	0.3048	−0.0677	0.7720	0.057*
C19B	0.39693 (16)	−0.00555 (12)	0.67726 (15)	0.0432 (6)
H19D	0.4010	0.0145	0.6227	0.065*
H19E	0.3942	−0.0617	0.6748	0.065*
H19F	0.4472	0.0104	0.7229	0.065*
C19C	0.23348 (16)	0.00258 (13)	0.62246 (15)	0.0494 (6)
H19G	0.1822	0.0194	0.6368	0.074*
H19H	0.2324	−0.0533	0.6160	0.074*
H19I	0.2351	0.0267	0.5690	0.074*
C21	0.21966 (12)	0.25387 (10)	0.41832 (11)	0.0219 (4)
C22	0.23800 (12)	0.29970 (10)	0.49399 (11)	0.0226 (4)
C23	0.17275 (13)	0.34865 (10)	0.50564 (12)	0.0258 (4)
H23A	0.1843	0.3797	0.5552	0.031*
C24	0.09038 (13)	0.35234 (11)	0.44490 (12)	0.0282 (4)
C25	0.07421 (13)	0.30441 (10)	0.37202 (12)	0.0264 (4)
H25A	0.0194	0.3058	0.3315	0.032*
C26	0.13730 (12)	0.25436 (10)	0.35764 (11)	0.0212 (4)
C27	0.11637 (12)	0.20294 (10)	0.27688 (11)	0.0245 (4)
H27A	0.1481	0.1541	0.2913	0.029*
H27B	0.0547	0.1907	0.2599	0.029*
C28	0.02158 (14)	0.40659 (13)	0.45894 (14)	0.0402 (5)
H28A	0.0426	0.4311	0.5149	0.060*
H28B	−0.0302	0.3772	0.4564	0.060*
H28C	0.0085	0.4461	0.4145	0.060*
C31	0.22443 (12)	0.23644 (9)	0.19300 (11)	0.0199 (4)
C32	0.13873 (12)	0.23980 (10)	0.19998 (11)	0.0212 (4)
C33	0.07487 (12)	0.27958 (10)	0.13676 (11)	0.0247 (4)
H33A	0.0186	0.2820	0.1420	0.030*
C34	0.09231 (12)	0.31590 (10)	0.06603 (12)	0.0260 (4)
C35	0.17751 (12)	0.31242 (10)	0.06109 (11)	0.0242 (4)
H35A	0.1906	0.3366	0.0145	0.029*
C36	0.24386 (12)	0.27420 (9)	0.12298 (11)	0.0207 (4)
C37	0.33612 (12)	0.27597 (10)	0.11588 (11)	0.0229 (4)
H37A	0.3336	0.2752	0.0548	0.027*
H37B	0.3659	0.2287	0.1422	0.027*
C38	0.02127 (13)	0.35581 (12)	−0.00416 (13)	0.0361 (5)
H38A	−0.0172	0.3832	0.0219	0.054*
H38B	−0.0111	0.3172	−0.0440	0.054*
H38C	0.0470	0.3924	−0.0349	0.054*
C41	0.43774 (12)	0.34478 (10)	0.24627 (11)	0.0225 (4)
C42	0.38952 (11)	0.34635 (10)	0.15836 (11)	0.0220 (4)
C43	0.39326 (12)	0.41272 (10)	0.10948 (12)	0.0251 (4)
H43A	0.3607	0.4139	0.0513	0.030*
C44	0.44384 (13)	0.47724 (10)	0.14446 (12)	0.0276 (4)
C45	0.49240 (12)	0.47294 (10)	0.23148 (12)	0.0266 (4)
H45A	0.5271	0.5155	0.2557	0.032*
C46	0.49189 (12)	0.40814 (11)	0.28446 (12)	0.0247 (4)
C47	0.55121 (13)	0.40428 (12)	0.37861 (12)	0.0304 (4)
C47A	0.49863 (15)	0.38958 (13)	0.44372 (13)	0.0397 (5)
H47A	0.5377	0.3865	0.5015	0.060*
H47B	0.4671	0.3412	0.4296	0.060*
H47C	0.4583	0.4318	0.4406	0.060*
C47B	0.60091 (15)	0.48141 (13)	0.40571 (14)	0.0411 (5)
H47D	0.6352	0.4781	0.4654	0.062*
H47E	0.5601	0.5238	0.3989	0.062*
H47F	0.6385	0.4906	0.3697	0.062*
C47C	0.61828 (14)	0.33849 (13)	0.38518 (14)	0.0399 (5)
H47G	0.6549	0.3347	0.4440	0.060*
H47H	0.6534	0.3500	0.3474	0.060*
H47I	0.5884	0.2897	0.3683	0.060*
C48	0.44711 (15)	0.54927 (12)	0.09064 (14)	0.0386 (5)
H48A	0.4953	0.5816	0.1209	0.058*
H48B	0.3938	0.5782	0.0811	0.058*
H48C	0.4543	0.5337	0.0357	0.058*
N1	0.18773 (10)	0.54503 (9)	0.26795 (10)	0.0233 (3)
C1	0.27162 (12)	0.50116 (10)	0.30186 (12)	0.0263 (4)
H1AA	0.3043	0.5237	0.3571	0.032*
H1AB	0.3060	0.5075	0.2616	0.032*
C2	0.25848 (14)	0.41482 (11)	0.31432 (14)	0.0335 (5)
H2A1	0.3141	0.3899	0.3369	0.050*
H2A2	0.2281	0.3917	0.2595	0.050*
H2A3	0.2248	0.4081	0.3545	0.050*
C3	0.13098 (13)	0.54373 (11)	0.32795 (12)	0.0279 (4)
H1BA	0.1073	0.4915	0.3279	0.033*
H1BB	0.0825	0.5793	0.3057	0.033*
C4	0.17847 (14)	0.56660 (12)	0.42072 (13)	0.0338 (5)
H2B1	0.2150	0.5241	0.4488	0.051*
H2B2	0.1368	0.5781	0.4516	0.051*
H2B3	0.2137	0.6121	0.4205	0.051*
C5	0.13507 (13)	0.51849 (11)	0.17922 (12)	0.0292 (4)
H1CA	0.0863	0.5540	0.1579	0.035*
H1CB	0.1116	0.4669	0.1841	0.035*
C6	0.18634 (15)	0.51513 (11)	0.11391 (13)	0.0364 (5)
H2C1	0.1473	0.5064	0.0569	0.055*
H2C2	0.2277	0.4731	0.1286	0.055*
H2C3	0.2166	0.5638	0.1146	0.055*
N2	0.03583 (14)	0.32827 (12)	0.66329 (16)	0.0591 (6)
C7	0.09630 (15)	0.19802 (12)	0.62241 (17)	0.0457 (6)
H1A	0.0637	0.1550	0.6358	0.069*
H1B	0.1566	0.1926	0.6547	0.069*
H1C	0.0908	0.1980	0.5613	0.069*
C8	0.06287 (15)	0.27073 (13)	0.64570 (15)	0.0414 (5)
H3	0.2028 (14)	0.5996 (13)	0.2598 (14)	0.046 (6)*
H1	0.3161 (19)	0.1622 (17)	0.5088 (19)	0.086 (10)*
H4	0.3804 (17)	0.2501 (14)	0.2718 (15)	0.058 (7)*
H2	0.2845 (16)	0.2030 (14)	0.3426 (17)	0.062 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0520 (9)	0.0244 (7)	0.0188 (7)	0.0055 (6)	0.0123 (6)	−0.0007 (6)
O2	0.0291 (8)	0.0289 (7)	0.0210 (7)	0.0093 (5)	0.0102 (6)	0.0019 (6)
O3	0.0247 (7)	0.0201 (6)	0.0186 (6)	0.0032 (5)	0.0062 (5)	0.0015 (5)
O4	0.0287 (8)	0.0296 (7)	0.0224 (7)	−0.0043 (6)	0.0043 (6)	0.0053 (6)
C11	0.0214 (10)	0.0260 (9)	0.0191 (9)	0.0031 (7)	0.0056 (7)	−0.0026 (8)
C12	0.0181 (9)	0.0266 (9)	0.0215 (9)	0.0028 (7)	0.0048 (7)	0.0002 (8)
C13	0.0314 (11)	0.0350 (10)	0.0198 (9)	0.0054 (8)	0.0088 (8)	0.0050 (8)
C14	0.0425 (13)	0.0341 (10)	0.0207 (10)	0.0064 (9)	0.0097 (9)	−0.0034 (8)
C15	0.0376 (12)	0.0281 (10)	0.0249 (10)	0.0015 (8)	0.0084 (9)	−0.0050 (8)
C16	0.0207 (10)	0.0272 (9)	0.0216 (9)	0.0000 (7)	0.0065 (8)	−0.0009 (8)
C17	0.0271 (11)	0.0236 (9)	0.0246 (10)	−0.0018 (8)	0.0086 (8)	−0.0004 (8)
C18	0.093 (2)	0.0430 (13)	0.0291 (12)	0.0112 (13)	0.0235 (13)	−0.0037 (10)
C19	0.0322 (11)	0.0260 (10)	0.0254 (10)	0.0015 (8)	0.0052 (8)	0.0036 (8)
C19A	0.0463 (14)	0.0321 (11)	0.0396 (12)	0.0005 (10)	0.0173 (11)	0.0092 (10)
C19B	0.0614 (16)	0.0332 (11)	0.0424 (13)	0.0181 (11)	0.0268 (12)	0.0117 (10)
C19C	0.0564 (16)	0.0328 (11)	0.0461 (14)	−0.0129 (11)	−0.0055 (12)	0.0051 (11)
C21	0.0265 (10)	0.0184 (8)	0.0234 (9)	0.0046 (7)	0.0112 (8)	0.0043 (7)
C22	0.0290 (10)	0.0185 (8)	0.0220 (9)	−0.0007 (7)	0.0100 (8)	0.0033 (7)
C23	0.0366 (12)	0.0210 (9)	0.0231 (9)	0.0039 (8)	0.0138 (9)	−0.0006 (8)
C24	0.0326 (11)	0.0271 (9)	0.0278 (10)	0.0074 (8)	0.0135 (9)	0.0047 (8)
C25	0.0251 (10)	0.0298 (10)	0.0253 (10)	0.0031 (8)	0.0088 (8)	0.0040 (8)
C26	0.0254 (10)	0.0207 (8)	0.0204 (9)	−0.0008 (7)	0.0110 (8)	0.0015 (7)
C27	0.0237 (10)	0.0246 (9)	0.0261 (10)	−0.0026 (8)	0.0088 (8)	0.0006 (8)
C28	0.0413 (13)	0.0436 (12)	0.0383 (12)	0.0153 (10)	0.0155 (10)	−0.0022 (10)
C31	0.0231 (10)	0.0175 (8)	0.0178 (9)	0.0001 (7)	0.0039 (7)	−0.0035 (7)
C32	0.0253 (10)	0.0199 (8)	0.0191 (9)	−0.0039 (7)	0.0078 (8)	−0.0038 (7)
C33	0.0220 (10)	0.0256 (9)	0.0255 (9)	−0.0025 (7)	0.0055 (8)	−0.0030 (8)
C34	0.0259 (11)	0.0252 (9)	0.0243 (10)	−0.0003 (8)	0.0030 (8)	−0.0005 (8)
C35	0.0289 (11)	0.0235 (9)	0.0200 (9)	−0.0027 (8)	0.0066 (8)	−0.0003 (7)
C36	0.0255 (10)	0.0190 (8)	0.0180 (9)	−0.0013 (7)	0.0068 (7)	−0.0049 (7)
C37	0.0265 (10)	0.0252 (9)	0.0185 (9)	−0.0007 (7)	0.0089 (8)	−0.0015 (7)
C38	0.0287 (12)	0.0439 (12)	0.0331 (11)	0.0022 (9)	0.0049 (9)	0.0100 (10)
C41	0.0239 (10)	0.0235 (9)	0.0229 (9)	0.0011 (7)	0.0111 (8)	0.0021 (8)
C42	0.0198 (9)	0.0264 (9)	0.0214 (9)	0.0004 (7)	0.0085 (8)	−0.0017 (7)
C43	0.0263 (10)	0.0285 (9)	0.0213 (9)	0.0016 (8)	0.0080 (8)	0.0016 (8)
C44	0.0307 (11)	0.0256 (9)	0.0292 (10)	0.0019 (8)	0.0128 (9)	0.0034 (8)
C45	0.0277 (11)	0.0252 (9)	0.0287 (10)	−0.0051 (8)	0.0108 (8)	−0.0034 (8)
C46	0.0230 (10)	0.0299 (10)	0.0219 (9)	−0.0008 (8)	0.0077 (8)	−0.0049 (8)
C47	0.0279 (11)	0.0379 (11)	0.0233 (10)	−0.0066 (9)	0.0042 (8)	−0.0030 (8)
C47A	0.0428 (13)	0.0534 (13)	0.0219 (10)	−0.0100 (11)	0.0076 (9)	−0.0048 (10)
C47B	0.0393 (13)	0.0492 (13)	0.0314 (11)	−0.0115 (10)	0.0050 (10)	−0.0095 (10)
C47C	0.0327 (12)	0.0469 (12)	0.0344 (12)	0.0012 (10)	0.0005 (10)	0.0016 (10)
C48	0.0484 (14)	0.0330 (11)	0.0362 (12)	−0.0035 (10)	0.0151 (10)	0.0045 (10)
N1	0.0226 (9)	0.0210 (7)	0.0251 (8)	−0.0004 (6)	0.0051 (7)	0.0016 (7)
C1	0.0244 (10)	0.0266 (9)	0.0287 (10)	0.0019 (8)	0.0087 (8)	0.0030 (8)
C2	0.0378 (12)	0.0278 (10)	0.0391 (12)	0.0080 (9)	0.0178 (10)	0.0067 (9)
C3	0.0250 (11)	0.0274 (9)	0.0332 (11)	0.0026 (8)	0.0116 (9)	−0.0004 (8)
C4	0.0382 (12)	0.0347 (11)	0.0305 (11)	0.0011 (9)	0.0132 (9)	−0.0008 (9)
C5	0.0322 (11)	0.0265 (9)	0.0249 (10)	0.0006 (8)	0.0016 (8)	−0.0006 (8)
C6	0.0546 (15)	0.0267 (10)	0.0276 (11)	−0.0017 (9)	0.0114 (10)	−0.0013 (9)
N2	0.0545 (14)	0.0483 (12)	0.0863 (17)	−0.0048 (10)	0.0390 (13)	−0.0082 (12)
C7	0.0359 (13)	0.0406 (12)	0.0664 (16)	0.0033 (10)	0.0241 (12)	0.0072 (12)
C8	0.0317 (13)	0.0416 (12)	0.0556 (15)	−0.0057 (10)	0.0201 (11)	0.0012 (11)

Geometric parameters (Å, º)

O1—C11	1.370 (2)	C31—C32	1.411 (2)
O2—C21	1.371 (2)	C32—C33	1.393 (3)
O3—C31	1.360 (2)	C33—C34	1.392 (3)
O4—C41	1.367 (2)	C34—C35	1.392 (3)
C11—C12	1.403 (2)	C34—C38	1.514 (3)
C11—C16	1.410 (2)	C35—C36	1.391 (3)
C12—C13	1.391 (2)	C36—C37	1.516 (3)
C12—C19	1.540 (2)	C37—C42	1.518 (2)
C13—C14	1.400 (3)	C41—C42	1.401 (3)
C14—C15	1.383 (3)	C41—C46	1.412 (2)
C14—C18	1.508 (3)	C42—C43	1.390 (2)
C15—C16	1.384 (2)	C43—C44	1.387 (3)
C16—C17	1.519 (2)	C44—C45	1.392 (3)
C17—C22	1.515 (3)	C44—C48	1.513 (3)
C19—C19B	1.531 (3)	C45—C46	1.397 (3)
C19—C19A	1.531 (3)	C46—C47	1.539 (3)
C19—C19C	1.532 (3)	C47—C47B	1.536 (3)
C21—C26	1.397 (3)	C47—C47C	1.537 (3)
C21—C22	1.404 (2)	C47—C47A	1.541 (3)
C22—C23	1.393 (2)	N1—C1	1.498 (2)
C23—C24	1.399 (3)	N1—C5	1.502 (2)
C24—C25	1.390 (3)	N1—C3	1.504 (2)
C24—C28	1.506 (3)	C1—C2	1.510 (3)
C25—C26	1.393 (2)	C3—C4	1.516 (3)
C26—C27	1.522 (2)	C5—C6	1.509 (3)
C27—C32	1.519 (2)	N2—C8	1.142 (3)
C31—C36	1.407 (2)	C7—C8	1.443 (3)
O1—C11—C12	117.48 (15)	C33—C32—C31	119.28 (16)
O1—C11—C16	121.02 (16)	C33—C32—C27	119.95 (16)
C12—C11—C16	121.49 (16)	C31—C32—C27	120.74 (16)
C13—C12—C11	117.08 (16)	C34—C33—C32	122.30 (17)
C13—C12—C19	121.23 (16)	C35—C34—C33	117.31 (17)
C11—C12—C19	121.69 (15)	C35—C34—C38	121.08 (17)
C12—C13—C14	123.04 (17)	C33—C34—C38	121.59 (17)
C15—C14—C13	117.64 (17)	C36—C35—C34	122.65 (17)
C15—C14—C18	122.22 (18)	C35—C36—C31	119.13 (17)
C13—C14—C18	120.13 (18)	C35—C36—C37	119.86 (15)
C14—C15—C16	122.33 (18)	C31—C36—C37	120.98 (16)
C15—C16—C11	118.38 (17)	C36—C37—C42	114.67 (14)
C15—C16—C17	120.14 (16)	O4—C41—C42	120.70 (16)
C11—C16—C17	121.45 (16)	O4—C41—C46	118.30 (16)
C22—C17—C16	113.12 (15)	C42—C41—C46	120.98 (16)
C19B—C19—C19A	107.29 (16)	C43—C42—C41	118.96 (16)
C19B—C19—C19C	110.36 (18)	C43—C42—C37	120.11 (16)
C19A—C19—C19C	107.35 (17)	C41—C42—C37	120.90 (16)
C19B—C19—C12	109.44 (16)	C44—C43—C42	122.27 (17)
C19A—C19—C12	112.18 (16)	C43—C44—C45	117.21 (17)
C19C—C19—C12	110.16 (16)	C43—C44—C48	121.76 (18)
O2—C21—C26	121.53 (16)	C45—C44—C48	121.03 (17)
O2—C21—C22	117.04 (16)	C44—C45—C46	123.63 (17)
C26—C21—C22	121.41 (16)	C45—C46—C41	116.92 (17)
C23—C22—C21	118.23 (17)	C45—C46—C47	121.49 (16)
C23—C22—C17	120.68 (16)	C41—C46—C47	121.51 (16)
C21—C22—C17	121.09 (16)	C47B—C47—C47C	108.18 (17)
C22—C23—C24	121.83 (17)	C47B—C47—C46	111.41 (16)
C25—C24—C23	118.06 (17)	C47C—C47—C46	108.69 (16)
C25—C24—C28	121.43 (18)	C47B—C47—C47A	106.71 (16)
C23—C24—C28	120.51 (18)	C47C—C47—C47A	110.03 (17)
C24—C25—C26	122.20 (18)	C46—C47—C47A	111.76 (16)
C25—C26—C21	118.22 (16)	C1—N1—C5	113.21 (14)
C25—C26—C27	120.21 (17)	C1—N1—C3	113.87 (14)
C21—C26—C27	121.57 (16)	C5—N1—C3	109.02 (14)
C32—C27—C26	114.15 (14)	N1—C1—C2	113.05 (16)
O3—C31—C36	119.85 (16)	N1—C3—C4	113.66 (16)
O3—C31—C32	120.83 (15)	N1—C5—C6	113.71 (16)
C36—C31—C32	119.32 (16)	N2—C8—C7	179.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.96 (3)	1.74 (3)	2.684 (2)	166 (2)
O2—H2···O3	1.04 (3)	1.46 (3)	2.499 (2)	177 (2)
O4—H4···O3	1.00 (3)	1.68 (3)	2.666 (2)	167 (2)
N1—H3···O3^i	0.98 (3)	1.70 (3)	2.671 (3)	170 (2)

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.