L-Phenyl­alanyl-L-tryptophan 0.75-hydrate

The title compound, C₂₀H₂₁N₃O₃·0.75H₂O, crystallizes as exceedingly thin fibers. The crystal packing arrangement is related to those of other hydro­phobic dipeptides with phenyl­alanine residues, but the structure has pseudo-tetra­gonal symmetry in an ortho­rhom­bic space group with four peptide mol­ecules and three water mol­ecules in the asymmetric unit.

S1. Comment

In a series of papers, it has been shown that dipeptides with two hydrophobic residues can form two different classes of nanoporous crystal structures (Görbitz, 2005, and references therein). The FF-class, named after L-phenylalanyl-L-phenylalanine, includes also L-phenylalanyl-L-leucine (FL), L-leucyl-L-phenylalanine (LF), L-leucyl-L-leucine (LL) (Görbitz, 2001), L-isoleucyl-L-leucine (Görbitz, 2004) and L-tryptophylglycine (WG) (Emge et al., 2000; Birkedal et al., 2002). The common characteristic of this group is aggregation of peptide molecules into hydrophobic tubes with a hydrophilic core that incorporates a central channel filled with solvent molecules.

As part of an investigation focused on the self-assembly of FF, Reches & Gazit (2003) reported that very thin hollow fibers with diameter less than 300 nm could be formed by dilution of a concentrated solution of the dipeptide in 1,1,1,3,3,3-hexafluoro-2-propanol with water. Furthermore, it was reported that fibers of similar dimensions could be formed by L-phenylalanyl-L-tryptophane (FW). Following continued research efforts on the nature of the FF fibers (Görbitz, 2006), we wondered what the nature of the FW fibers could be and decided to test if it was possible to grow them large enough for single-crystal structure determination. This proved to be a challenging task, but eventually needles with diameter up to 20 µm were grown by diffusion of acetonitrile into a saturated 1,1,1,3,3,3-hexafluoropropan-2-ol solution of FW (Görbitz, 2006). The structure of this peptide is presented in detail here.

The asymmetric unit of FW, shown in Fig. 1, contains four peptide molecules and three water molecules. The main chains of the peptide molecules have rather similar conformations, but the phenylalanine side chain of molecule A is in a gauche+ orientation, as opposed to the more common trans orientation for B, C and D. Furthermore, even if all thryptophane side chains have well defined gauche- χ¹ torsion angles (N2—C10—C11—C12), the χ^2,1 torsion angles (C10—C11—C12—C13) vary considerably (Table 1).

The crystal packing arrangement of FW is compared in Fig. 2 with the crystal structures of FF, FL (Görbitz, 2001) and WG (Emge et al., 2000; Birkedal et al., 2002). The hexagonal FF structure and the tetragonal WG structure both have one peptide molecule in the asymmetric unit, while Z' = 2 for the orthorhombic structure of FL as well as for the structures of LL, LF (Görbitz, 2001) and IL (Görbitz, 2004) (not shown). It follows that the water-filled channels of FW are the first to be devoid of crystallographic symmetry, and they also have a more irregular appearance than those of the other structures in the family.

In accordance with previous findings, each peptide amine group donates one of its H atoms to a water molecule located in the channel (Table 2). In WG the side-chain N^e—H donor manages to find a carboxylate acceptor. In the present structure the equivalent four H atoms are accepted by aromatic groups, two by phenylalanyl side chains and two by the six-membered ring of the tryptophane side chains.

S2. Experimental

The title compound was obtained from Bachem. Extremely thin fibers were grown by diffusion of acetonitrile into a saturated 1,1,1,3,3,3-hexafluoropropan-2-ol solution (50µl) of the peptide. A 20 × 18 µm cross section specimen was used for data collection.

S3. Refinement

Owing to the combination of a large unit cell and a small crystal, more than 80% of the reflections with 2θ between 40 and 50° are unobserved, resulting in a high value for R_int. In order not to further impair the rather poor reflection-to-parameter ratio, only O atoms, N atoms and side-chain C atoms that obtained large U_iso values in the initial isotropic refinement were refined anisotropically. Other C atoms were refined isotropically. Mild SHELXTLSAME restraints [preferably rephrase this so that readers who do not use this software can understand the method] were applied to link the geometries of the four peptide molecules. The tryptophane side chain of peptide molecule D is disordered over two nearby positions with occupancies 0.620 (14) and 0.380 (14), respectively. C– and N-bound H atoms were positioned with idealized geometry and fixed N—H and C—H distances in the range 0.88–1.00 Å. Six water H atoms were positioned by consideration of the local atomic environment, but three of them could also be detected in electron density maps. The intramolecular water geometries were restrained by tight DFIX commands and the s.u. values associated with these atoms are underestimated. U_iso(H) atoms were set at 1.2U_eq of the carrier atom or 1.5U_eq for amine groups and water molecules. In the absence of significant anomalous scattering effects, 5310 Friedel pairs were merged. The absolute configuration was known for the purchased material.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. : The molecular structure of FW. Displacement ellipsoids are shown at the 50% probability level and H atoms are shown as spheres of arbitrary size. The minor position for the disordered tryptophane side chain of peptide molecule D is shown as a stick drawing
	Fig. 2. : Molecular packing and unit cell of FW viewed along the a axis. The four independent peptide molecules in the asymmetric unit have been labeled A, B, C and D. For comparison, the structures of FF, FL (Görbitz, 2001) and WG (Emge et al., 2000; Birkedal et al.,2002) are shown on the same scale. Atoms in side chains are shown in a darker tone.

L-phenylalanyl-L-tryptophan 0.75-hydrate

Crystal data

C20H21N3O3·0.75H2O	Dx = 1.354 Mg m^−3
Mr = 364.91	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 1981 reflections
a = 5.6207 (6) Å	θ = 0.8–20.8°
b = 35.556 (4) Å	µ = 0.10 mm^−1
c = 35.835 (4) Å	T = 105 K
V = 7161.5 (15) Å^3	Needle, colourless
Z = 16	0.54 × 0.02 × 0.02 mm
F(000) = 3096

Data collection

Siemens SMART CCD diffractometer	7087 independent reflections
Radiation source: fine-focus sealed tube	3234 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.170
Detector resolution: 8.3 pixels mm^-1	θmax = 25.0°, θmin = 0.8°
Three sets of frames each taken over 0.3° ω rotation with 150 s exposure time. scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −42→32
Tmin = 0.876, Tmax = 0.998	l = −41→41
33425 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.079	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.182	w = 1/[σ^2(Fo^2) + (0.064P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.004
7087 reflections	Δρmax = 0.45 e Å^−3
726 parameters	Δρmin = −0.37 e Å^−3
529 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0127 (6)

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. Data were collected by measuring three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F² against ALL reflections.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1A	−0.0577 (9)	0.41420 (15)	0.40838 (18)	0.0239 (17)
O2A	−0.1059 (10)	0.37911 (15)	0.33058 (16)	0.0231 (16)
O3A	−0.3932 (9)	0.34500 (15)	0.35613 (17)	0.0194 (15)
N1A	0.2911 (12)	0.46494 (16)	0.3991 (2)	0.024 (2)
H1A	0.3021	0.4673	0.3739	0.036*
H2A	0.3906	0.4818	0.4102	0.036*
H3A	0.1389	0.4696	0.4064	0.036*
N2A	0.1865 (11)	0.36649 (15)	0.39170 (19)	0.0197 (19)*
H4A	0.3347	0.3590	0.3888	0.024*
C1A	0.3598 (12)	0.42602 (18)	0.4103 (2)	0.016 (2)*
H11A	0.4917	0.4174	0.3936	0.019*
C2A	0.4475 (12)	0.4253 (2)	0.45007 (18)	0.019 (2)*
H21A	0.4877	0.3990	0.4565	0.023*
H22A	0.5966	0.4400	0.4514	0.023*
C3A	0.2803 (14)	0.4401 (2)	0.4793 (2)	0.019 (2)*
C4A	0.2967 (15)	0.4764 (2)	0.4926 (3)	0.024 (3)
H41A	0.4203	0.4924	0.4837	0.029*
C5A	0.1357 (16)	0.4901 (2)	0.5186 (3)	0.030 (3)
H51A	0.1498	0.5153	0.5272	0.036*
C6A	−0.0433 (16)	0.4678 (2)	0.5320 (3)	0.037 (3)
H61A	−0.1537	0.4772	0.5497	0.045*
C7A	−0.0601 (15)	0.4310 (2)	0.5190 (3)	0.037 (3)
H71A	−0.1832	0.4151	0.5280	0.044*
C8A	0.0997 (15)	0.4174 (2)	0.4933 (2)	0.027 (3)
H81A	0.0864	0.3922	0.4850	0.032*
C9A	0.1435 (12)	0.40118 (18)	0.4033 (2)	0.016 (2)*
C10A	−0.0081 (12)	0.34023 (19)	0.38349 (19)	0.015 (2)*
H10A	0.0662	0.3176	0.3718	0.018*
C11A	−0.1320 (13)	0.3267 (2)	0.41917 (19)	0.020 (2)*
H14A	−0.2127	0.3483	0.4311	0.024*
H15A	−0.2556	0.3080	0.4124	0.024*
C12A	0.0363 (13)	0.3090 (2)	0.44702 (19)	0.016 (2)*
C13A	0.2383 (13)	0.2892 (2)	0.4392 (2)	0.020 (2)*
H13A	0.2948	0.2834	0.4149	0.023*
N3A	0.3477 (11)	0.27892 (18)	0.47213 (17)	0.0204 (19)*
H5A	0.4810	0.2660	0.4737	0.025*
C14A	0.2190 (12)	0.2916 (2)	0.50192 (18)	0.015 (2)*
C15A	0.0153 (13)	0.3099 (2)	0.48647 (18)	0.019 (2)*
C16A	−0.1512 (13)	0.3252 (2)	0.5111 (2)	0.018 (2)*
H16A	−0.2882	0.3377	0.5018	0.021*
C17A	−0.1152 (14)	0.3219 (2)	0.5491 (2)	0.027 (3)
H17A	−0.2298	0.3320	0.5659	0.032*
C18A	0.0871 (14)	0.3041 (2)	0.5633 (2)	0.024 (3)
H18A	0.1076	0.3024	0.5896	0.029*
C19A	0.2592 (14)	0.2887 (2)	0.5399 (2)	0.023 (3)*
H19A	0.3976	0.2769	0.5495	0.028*
C20A	−0.1789 (13)	0.3566 (2)	0.3546 (2)	0.022 (2)*
O1B	−0.0902 (9)	0.51465 (15)	0.20447 (17)	0.0196 (15)
O2B	−0.1076 (9)	0.53399 (15)	0.28926 (17)	0.0247 (17)
O3B	−0.3905 (9)	0.57121 (15)	0.26697 (18)	0.0234 (17)
N1B	0.3056 (12)	0.46099 (16)	0.2138 (2)	0.023 (2)
H1B	0.3618	0.4624	0.2376	0.034*
H2B	0.1516	0.4531	0.2142	0.034*
H3B	0.3952	0.4444	0.2005	0.034*
N2B	0.1849 (11)	0.55343 (16)	0.22969 (18)	0.0181 (19)*
H4B	0.3376	0.5578	0.2330	0.022*
C1B	0.3190 (13)	0.49854 (19)	0.1961 (2)	0.022 (2)*
H11B	0.4753	0.5104	0.2024	0.026*
C2B	0.2986 (17)	0.49451 (19)	0.1539 (2)	0.028 (3)*
H21B	0.4400	0.4809	0.1444	0.034*
H22B	0.1564	0.4792	0.1479	0.034*
C3B	0.2798 (14)	0.5319 (2)	0.1344 (2)	0.024 (3)*
C4B	0.0802 (16)	0.5410 (3)	0.1141 (3)	0.051 (4)
H41B	−0.0455	0.5233	0.1119	0.061*
C5B	0.0606 (18)	0.5757 (3)	0.0968 (3)	0.060 (4)
H51B	−0.0760	0.5810	0.0821	0.072*
C6B	0.2329 (19)	0.6023 (2)	0.1005 (3)	0.051 (4)
H61B	0.2172	0.6261	0.0888	0.061*
C7B	0.4318 (19)	0.5938 (2)	0.1217 (3)	0.051 (4)
H71B	0.5537	0.6121	0.1247	0.062*
C8B	0.4543 (16)	0.5589 (2)	0.1385 (3)	0.045 (3)
H81B	0.5913	0.5535	0.1531	0.055*
C9B	0.1184 (12)	0.52302 (19)	0.2113 (2)	0.018 (2)*
C10B	0.0106 (12)	0.58022 (17)	0.2448 (2)	0.014 (2)*
H10B	0.1012	0.5960	0.2630	0.016*
C11B	−0.0797 (13)	0.60772 (19)	0.2151 (2)	0.024 (2)*
H14B	−0.1042	0.5939	0.1914	0.028*
H15B	−0.2357	0.6179	0.2231	0.028*
C12B	0.0894 (12)	0.64015 (18)	0.2083 (2)	0.015 (2)*
C13B	0.2962 (13)	0.6474 (2)	0.2270 (2)	0.021 (2)*
H13B	0.3602	0.6324	0.2465	0.025*
N3B	0.3977 (11)	0.67990 (17)	0.21335 (18)	0.0212 (19)*
H5B	0.5346	0.6894	0.2207	0.025*
C14B	0.2528 (13)	0.69515 (19)	0.1867 (2)	0.018 (2)*
C15B	0.0550 (12)	0.67051 (19)	0.1830 (2)	0.015 (2)*
C16B	−0.1209 (13)	0.6799 (2)	0.1570 (2)	0.020 (2)*
H16B	−0.2533	0.6637	0.1533	0.024*
C17B	−0.1011 (14)	0.7130 (2)	0.1367 (2)	0.022 (2)
H17B	−0.2228	0.7199	0.1196	0.027*
C18B	0.0965 (15)	0.7362 (2)	0.1412 (3)	0.028 (3)
H18B	0.1091	0.7583	0.1265	0.033*
C19B	0.2742 (14)	0.7281 (2)	0.1665 (2)	0.021 (2)*
H19B	0.4058	0.7446	0.1699	0.025*
C20B	−0.1761 (12)	0.5597 (2)	0.2679 (2)	0.021 (2)*
O1C	−0.0793 (9)	0.33831 (15)	0.25150 (16)	0.0199 (16)
O2C	−0.1135 (10)	0.42240 (15)	0.22414 (16)	0.0222 (16)
O3C	−0.4157 (9)	0.39970 (15)	0.19051 (17)	0.0209 (16)
N1C	0.3324 (12)	0.36912 (16)	0.29549 (19)	0.0181 (19)
H1C	0.3687	0.3921	0.2858	0.027*
H2C	0.4419	0.3628	0.3131	0.027*
H3C	0.1853	0.3699	0.3061	0.027*
N2C	0.1631 (10)	0.36191 (16)	0.20679 (16)	0.0125 (17)*
H4C	0.3116	0.3653	0.1998	0.015*
C1C	0.3344 (12)	0.34058 (17)	0.26523 (19)	0.011 (2)*
H11C	0.4829	0.3437	0.2502	0.014*
C2C	0.3354 (15)	0.30172 (16)	0.28296 (19)	0.019 (2)*
H21C	0.4725	0.2999	0.3002	0.022*
H22C	0.1886	0.2987	0.2979	0.022*
C3C	0.3503 (13)	0.27011 (19)	0.2552 (2)	0.017 (2)*
C4C	0.1678 (13)	0.2446 (2)	0.2516 (2)	0.018 (2)
H41C	0.0308	0.2468	0.2670	0.021*
C5C	0.1816 (14)	0.2156 (2)	0.2258 (2)	0.025 (3)
H51C	0.0546	0.1980	0.2239	0.031*
C6C	0.3741 (14)	0.2118 (2)	0.2029 (3)	0.027 (3)
H61C	0.3814	0.1920	0.1851	0.032*
C7C	0.5589 (14)	0.2374 (2)	0.2062 (2)	0.025 (3)
H71C	0.6943	0.2353	0.1905	0.030*
C8C	0.5466 (13)	0.2658 (2)	0.2323 (2)	0.018 (2)
H81C	0.6757	0.2829	0.2345	0.021*
C9C	0.1206 (12)	0.3471 (2)	0.24006 (19)	0.018 (2)*
C10C	−0.0287 (12)	0.37290 (19)	0.1812 (2)	0.015 (2)*
H10C	0.0482	0.3873	0.1605	0.018*
C11C	−0.1493 (12)	0.33882 (19)	0.1630 (2)	0.016 (2)*
H14C	−0.2098	0.3220	0.1829	0.019*
H15C	−0.2875	0.3476	0.1483	0.019*
C12C	0.0142 (13)	0.3167 (2)	0.13786 (19)	0.017 (2)*
C13C	0.2182 (13)	0.2981 (2)	0.1482 (2)	0.019 (2)*
H13C	0.2793	0.2966	0.1729	0.023*
N3C	0.3199 (11)	0.28188 (18)	0.11719 (17)	0.022 (2)*
H5C	0.4533	0.2689	0.1171	0.027*
C14C	0.1826 (13)	0.2889 (2)	0.08639 (19)	0.020 (2)*
C15C	−0.0139 (13)	0.3108 (2)	0.09889 (19)	0.020 (2)*
C16C	−0.1851 (14)	0.3212 (2)	0.0727 (2)	0.025 (3)
H16C	−0.3175	0.3360	0.0802	0.030*
C17C	−0.1625 (16)	0.3101 (2)	0.0358 (2)	0.034 (3)
H17C	−0.2809	0.3168	0.0181	0.040*
C18C	0.0346 (17)	0.2890 (3)	0.0247 (2)	0.037 (3)
H18C	0.0498	0.2821	−0.0008	0.045*
C19C	0.2082 (15)	0.2778 (2)	0.0497 (2)	0.033 (3)
H19C	0.3400	0.2630	0.0419	0.039*
C20C	−0.1994 (12)	0.4003 (2)	0.2008 (2)	0.015 (2)*
O1D	−0.1079 (9)	0.58450 (16)	0.36541 (17)	0.0219 (16)
O2D	−0.1373 (9)	0.50159 (15)	0.39652 (17)	0.0234 (16)
O3D	−0.4571 (9)	0.52678 (15)	0.42303 (18)	0.0231 (17)
N1D	0.3180 (12)	0.55271 (17)	0.32626 (19)	0.0211 (19)
H1D	0.3700	0.5308	0.3365	0.032*
H2D	0.4183	0.5597	0.3076	0.032*
H3D	0.1691	0.5494	0.3169	0.032*
N2D	0.1249 (11)	0.56465 (16)	0.41329 (17)	0.0174 (18)*
H4D	0.2710	0.5631	0.4220	0.021*
C1D	0.3126 (13)	0.58255 (18)	0.3554 (2)	0.018 (2)*
H11D	0.4558	0.5799	0.3718	0.022*
C2D	0.3175 (15)	0.62090 (16)	0.3366 (2)	0.016 (2)*
H21D	0.4643	0.6230	0.3215	0.020*
H22D	0.1799	0.6230	0.3195	0.020*
C3D	0.3093 (13)	0.65297 (19)	0.3642 (2)	0.015 (2)*
C4D	0.1142 (13)	0.6763 (2)	0.3655 (2)	0.024 (2)
H41D	−0.0153	0.6721	0.3490	0.028*
C5D	0.1046 (14)	0.7061 (2)	0.3907 (3)	0.030 (3)
H51D	−0.0281	0.7226	0.3906	0.037*
C6D	0.2862 (14)	0.7115 (2)	0.4157 (2)	0.024 (3)
H61D	0.2772	0.7312	0.4336	0.029*
C7D	0.4822 (14)	0.6881 (2)	0.4146 (2)	0.024 (3)
H71D	0.6112	0.6922	0.4312	0.029*
C8D	0.4916 (13)	0.6587 (2)	0.3893 (2)	0.020 (2)
H81D	0.6249	0.6423	0.3893	0.024*
C9D	0.0894 (12)	0.5773 (2)	0.37888 (19)	0.018 (2)*
C10D	−0.0748 (12)	0.55323 (18)	0.43719 (19)	0.013 (2)*	0.620 (14)
H10D	−0.0028	0.5387	0.4583	0.016*	0.620 (14)
C11D	−0.2050 (19)	0.5865 (3)	0.4551 (3)	0.020 (9)*	0.620 (14)
H14D	−0.2351	0.6060	0.4360	0.024*	0.620 (14)
H15D	−0.3607	0.5779	0.4649	0.024*	0.620 (14)
C12D	−0.062 (2)	0.6034 (3)	0.4866 (2)	0.020 (10)*	0.620 (14)
C13D	0.140 (3)	0.6248 (5)	0.4829 (3)	0.034 (5)*	0.620 (14)
H13D	0.1983	0.6349	0.4601	0.041*	0.620 (14)
N3D	0.2442 (19)	0.6293 (3)	0.5172 (3)	0.032 (4)*	0.620 (14)
H5D	0.3732	0.6427	0.5215	0.039*	0.620 (14)
C14D	0.118 (2)	0.6102 (4)	0.5437 (3)	0.022 (4)*	0.620 (14)
C15D	−0.075 (2)	0.5927 (4)	0.5246 (2)	0.017 (4)*	0.620 (14)
C16D	−0.238 (2)	0.5720 (4)	0.5455 (3)	0.031 (5)*	0.620 (14)
H16D	−0.3665	0.5595	0.5336	0.037*	0.620 (14)
C17D	−0.211 (3)	0.5699 (5)	0.5840 (3)	0.043 (6)*	0.620 (14)
H17D	−0.3278	0.5573	0.5985	0.052*	0.620 (14)
C18D	−0.015 (3)	0.5861 (5)	0.6014 (3)	0.040 (6)*	0.620 (14)
H18D	0.0064	0.5826	0.6275	0.048*	0.620 (14)
C19D	0.151 (2)	0.6072 (4)	0.5817 (3)	0.029 (5)*	0.620 (14)
H19D	0.2805	0.6190	0.5939	0.035*	0.620 (14)
C20D	−0.2352 (12)	0.5256 (2)	0.4166 (2)	0.022 (2)*
C10E	−0.0748 (12)	0.55323 (18)	0.43719 (19)	0.013 (2)*	0.380 (14)
H10E	−0.0048	0.5393	0.4588	0.016*	0.380 (14)
C11E	−0.176 (4)	0.5901 (4)	0.4528 (4)	0.033 (17)*	0.380 (14)
H14E	−0.1438	0.6107	0.4349	0.040*	0.380 (14)
H15E	−0.3501	0.5877	0.4556	0.040*	0.380 (14)
C12E	−0.067 (3)	0.5997 (4)	0.4900 (3)	0.020 (16)*	0.380 (14)
C13E	0.131 (4)	0.6213 (8)	0.4963 (5)	0.031 (8)*	0.380 (14)
H13E	0.2193	0.6343	0.4777	0.038*	0.380 (14)
N3E	0.182 (3)	0.6212 (6)	0.5338 (5)	0.023 (6)*	0.380 (14)
H5E	0.3034	0.6327	0.5442	0.027*	0.380 (14)
C14E	0.016 (3)	0.6004 (6)	0.5525 (4)	0.023 (7)*	0.380 (14)
C15E	−0.148 (3)	0.5872 (6)	0.5252 (3)	0.010*	0.380 (14)
C16E	−0.341 (3)	0.5655 (6)	0.5369 (4)	0.023 (7)*	0.380 (14)
H16E	−0.4529	0.5563	0.5193	0.028*	0.380 (14)
C17E	−0.367 (3)	0.5576 (5)	0.5746 (4)	0.017 (7)*	0.380 (14)
H17E	−0.4977	0.5429	0.5828	0.020*	0.380 (14)
C18E	−0.203 (4)	0.5710 (7)	0.6006 (4)	0.026 (8)*	0.380 (14)
H18E	−0.2233	0.5649	0.6262	0.032*	0.380 (14)
C19E	−0.010 (4)	0.5930 (8)	0.5901 (4)	0.035 (10)*	0.380 (14)
H19E	0.0985	0.6026	0.6080	0.042*	0.380 (14)
O1W	0.1128 (12)	0.4494 (2)	0.3242 (2)	0.046 (2)
H11W	0.035 (12)	0.4290 (12)	0.327 (3)	0.069*
H12W	0.003 (9)	0.4655 (18)	0.319 (3)	0.069*
O2W	0.5445 (11)	0.4391 (2)	0.2765 (2)	0.0304 (18)
H21W	0.673 (8)	0.437 (3)	0.264 (2)	0.046*
H22W	0.584 (12)	0.453 (2)	0.2947 (16)	0.046*
O3W	0.6223 (11)	0.49047 (17)	0.3334 (2)	0.0264 (17)
H31W	0.699 (12)	0.5071 (18)	0.3210 (18)	0.040*
H32W	0.703 (13)	0.489 (2)	0.3536 (13)	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.009 (3)	0.022 (3)	0.041 (4)	0.001 (3)	0.001 (3)	−0.007 (3)
O2A	0.014 (3)	0.025 (4)	0.030 (5)	0.001 (3)	−0.004 (3)	−0.007 (3)
O3A	0.010 (2)	0.026 (3)	0.023 (3)	0.000 (2)	0.001 (2)	−0.003 (2)
N1A	0.010 (4)	0.026 (5)	0.037 (6)	−0.005 (4)	0.005 (4)	−0.004 (4)
C4A	0.016 (5)	0.024 (6)	0.033 (8)	−0.002 (5)	0.002 (5)	0.000 (5)
C5A	0.039 (7)	0.025 (6)	0.027 (7)	0.014 (6)	−0.001 (6)	0.002 (5)
C6A	0.021 (6)	0.049 (8)	0.042 (9)	0.004 (6)	0.011 (6)	−0.005 (6)
C7A	0.018 (6)	0.046 (8)	0.046 (9)	−0.007 (6)	0.002 (6)	−0.012 (6)
C8A	0.031 (6)	0.021 (6)	0.028 (7)	−0.008 (5)	0.000 (6)	−0.002 (5)
C17A	0.012 (4)	0.029 (5)	0.039 (6)	−0.003 (4)	0.007 (4)	−0.001 (4)
C18A	0.037 (6)	0.018 (5)	0.017 (7)	−0.011 (5)	−0.003 (5)	0.005 (4)
O1B	0.011 (3)	0.020 (3)	0.028 (3)	−0.003 (2)	0.000 (3)	−0.005 (2)
O2B	0.010 (3)	0.026 (4)	0.038 (5)	−0.002 (3)	−0.003 (3)	0.009 (3)
O3B	0.010 (3)	0.026 (3)	0.035 (4)	0.002 (3)	0.004 (3)	−0.003 (3)
N1B	0.012 (4)	0.017 (4)	0.040 (6)	0.004 (4)	−0.006 (4)	−0.003 (4)
C4B	0.036 (7)	0.046 (8)	0.071 (11)	−0.003 (7)	−0.025 (7)	0.018 (7)
C5B	0.044 (8)	0.055 (9)	0.081 (12)	−0.006 (8)	−0.014 (8)	0.024 (8)
C6B	0.069 (9)	0.027 (7)	0.056 (10)	0.005 (7)	0.016 (8)	0.010 (6)
C7B	0.061 (9)	0.039 (8)	0.054 (10)	−0.022 (7)	0.007 (7)	0.003 (6)
C8B	0.036 (7)	0.046 (7)	0.055 (9)	−0.015 (7)	−0.008 (6)	0.025 (6)
C17B	0.020 (5)	0.021 (5)	0.026 (7)	0.007 (5)	−0.001 (5)	0.000 (4)
C18B	0.036 (6)	0.012 (5)	0.035 (8)	0.003 (5)	0.015 (6)	0.005 (5)
O1C	0.009 (3)	0.024 (3)	0.026 (4)	−0.001 (3)	0.003 (3)	−0.002 (3)
O2C	0.023 (4)	0.019 (3)	0.025 (4)	−0.002 (3)	0.001 (3)	−0.004 (3)
O3C	0.008 (3)	0.021 (4)	0.033 (5)	0.005 (3)	0.001 (3)	0.005 (3)
N1C	0.015 (4)	0.016 (4)	0.023 (5)	0.000 (4)	−0.003 (4)	−0.007 (3)
C4C	0.012 (3)	0.020 (4)	0.022 (4)	0.003 (3)	0.001 (3)	0.001 (3)
C5C	0.014 (5)	0.022 (5)	0.041 (6)	−0.005 (4)	−0.004 (4)	−0.001 (4)
C6C	0.025 (6)	0.019 (5)	0.036 (7)	0.007 (5)	−0.015 (6)	−0.011 (5)
C7C	0.017 (5)	0.025 (5)	0.034 (6)	0.009 (4)	0.000 (5)	0.000 (4)
C8C	0.011 (4)	0.022 (4)	0.021 (4)	−0.002 (3)	−0.003 (3)	0.002 (3)
C16C	0.021 (6)	0.017 (5)	0.039 (8)	0.005 (5)	−0.003 (5)	−0.003 (5)
C17C	0.043 (7)	0.026 (6)	0.032 (8)	0.004 (6)	−0.016 (6)	−0.002 (5)
C18C	0.071 (8)	0.022 (6)	0.020 (7)	0.001 (6)	−0.003 (7)	0.001 (5)
C19C	0.028 (6)	0.027 (6)	0.043 (9)	0.002 (6)	0.010 (6)	0.001 (5)
O1D	0.013 (3)	0.026 (4)	0.027 (5)	0.002 (3)	−0.009 (3)	−0.005 (3)
O2D	0.012 (3)	0.023 (3)	0.035 (4)	−0.001 (3)	0.002 (3)	−0.010 (3)
O3D	0.011 (3)	0.020 (3)	0.039 (4)	0.003 (3)	0.007 (3)	0.004 (3)
N1D	0.011 (3)	0.025 (4)	0.027 (4)	0.002 (3)	0.004 (3)	−0.001 (3)
C4D	0.017 (5)	0.021 (5)	0.032 (6)	−0.001 (4)	−0.002 (4)	0.001 (4)
C5D	0.017 (6)	0.023 (6)	0.051 (8)	0.006 (5)	0.007 (6)	−0.004 (5)
C6D	0.021 (6)	0.028 (6)	0.023 (7)	−0.012 (5)	0.002 (5)	−0.001 (5)
C7D	0.021 (6)	0.025 (6)	0.025 (7)	−0.004 (5)	−0.001 (5)	0.007 (5)
C8D	0.015 (4)	0.021 (5)	0.024 (5)	0.004 (4)	−0.003 (4)	0.004 (4)
O1W	0.029 (4)	0.050 (5)	0.058 (6)	0.009 (4)	0.000 (4)	−0.006 (5)
O2W	0.019 (4)	0.033 (4)	0.039 (6)	−0.003 (4)	−0.001 (4)	−0.004 (4)
O3W	0.021 (4)	0.029 (4)	0.030 (5)	0.005 (3)	−0.001 (4)	0.003 (3)

Geometric parameters (Å, º)

O1A—C9A	1.235 (7)	C2C—C3C	1.502 (7)
O2A—C20A	1.245 (7)	C2C—H21C	0.9900
O3A—C20A	1.274 (7)	C2C—H22C	0.9900
N1A—C1A	1.492 (7)	C3C—C4C	1.376 (7)
N1A—H1A	0.9100	C3C—C8C	1.385 (8)
N1A—H2A	0.9100	C4C—C5C	1.389 (8)
N1A—H3A	0.9100	C4C—H41C	0.9500
N2A—C9A	1.324 (7)	C5C—C6C	1.363 (8)
N2A—C10A	1.468 (7)	C5C—H51C	0.9500
N2A—H4A	0.8800	C6C—C7C	1.385 (8)
C1A—C2A	1.509 (8)	C6C—H61C	0.9500
C1A—C9A	1.524 (8)	C7C—C8C	1.379 (8)
C1A—H11A	1.0000	C7C—H71C	0.9500
C2A—C3A	1.503 (8)	C8C—H81C	0.9500
C2A—H21A	0.9900	C10C—C11C	1.533 (7)
C2A—H22A	0.9900	C10C—C20C	1.538 (7)
C3A—C4A	1.381 (7)	C10C—H10C	1.0000
C3A—C8A	1.389 (8)	C11C—C12C	1.510 (7)
C4A—C5A	1.387 (8)	C11C—H14C	0.9900
C4A—H41A	0.9500	C11C—H15C	0.9900
C5A—C6A	1.369 (8)	C12C—C13C	1.374 (7)
C5A—H51A	0.9500	C12C—C15C	1.421 (7)
C6A—C7A	1.389 (8)	C13C—N3C	1.377 (7)
C6A—H61A	0.9500	C13C—H13C	0.9500
C7A—C8A	1.375 (8)	N3C—C14C	1.370 (7)
C7A—H71A	0.9500	N3C—H5C	0.8800
C8A—H81A	0.9500	C14C—C19C	1.382 (8)
C10A—C20A	1.527 (7)	C14C—C15C	1.422 (7)
C10A—C11A	1.534 (8)	C15C—C16C	1.395 (8)
C10A—H10A	1.0000	C16C—C17C	1.386 (8)
C11A—C12A	1.512 (7)	C16C—H16C	0.9500
C11A—H14A	0.9900	C17C—C18C	1.396 (9)
C11A—H15A	0.9900	C17C—H17C	0.9500
C12A—C13A	1.365 (7)	C18C—C19C	1.382 (9)
C12A—C15A	1.419 (7)	C18C—H18C	0.9500
C13A—N3A	1.379 (7)	C19C—H19C	0.9500
C13A—H13A	0.9500	O1D—C9D	1.237 (7)
N3A—C14A	1.366 (7)	O2D—C20D	1.246 (7)
N3A—H5A	0.8800	O3D—C20D	1.269 (7)
C14A—C19A	1.383 (8)	N1D—C1D	1.490 (7)
C14A—C15A	1.428 (7)	N1D—H1D	0.9100
C15A—C16A	1.396 (8)	N1D—H2D	0.9100
C16A—C17A	1.382 (8)	N1D—H3D	0.9100
C16A—H16A	0.9500	N2D—C9D	1.327 (7)
C17A—C18A	1.398 (8)	N2D—C10D	1.469 (7)
C17A—H17A	0.9500	N2D—H4D	0.8800
C18A—C19A	1.393 (8)	C1D—C9D	1.521 (8)
C18A—H18A	0.9500	C1D—C2D	1.522 (8)
C19A—H19A	0.9500	C1D—H11D	1.0000
O1B—C9B	1.234 (7)	C2D—C3D	1.511 (7)
O2B—C20B	1.255 (7)	C2D—H21D	0.9900
O3B—C20B	1.272 (7)	C2D—H22D	0.9900
N1B—C1B	1.479 (7)	C3D—C4D	1.376 (7)
N1B—H1B	0.9114	C3D—C8D	1.379 (8)
N1B—H2B	0.9103	C4D—C5D	1.393 (8)
N1B—H3B	0.9103	C4D—H41D	0.9500
N2B—C9B	1.320 (7)	C5D—C6D	1.373 (8)
N2B—C10B	1.469 (7)	C5D—H51D	0.9500
N2B—H4B	0.8800	C6D—C7D	1.382 (8)
C1B—C2B	1.525 (8)	C6D—H61D	0.9500
C1B—C9B	1.525 (8)	C7D—C8D	1.384 (8)
C1B—H11B	1.0000	C7D—H71D	0.9500
C2B—C3B	1.508 (8)	C8D—H81D	0.9500
C2B—H21B	0.9900	C10D—C20D	1.523 (7)
C2B—H22B	0.9900	C10D—C11D	1.533 (7)
C3B—C4B	1.375 (8)	C10D—H10D	1.0000
C3B—C8B	1.380 (8)	C11D—C12D	1.512 (8)
C4B—C5B	1.383 (8)	C11D—H14D	0.9900
C4B—H41B	0.9500	C11D—H15D	0.9900
C5B—C6B	1.360 (9)	C12D—C13D	1.371 (8)
C5B—H51B	0.9500	C12D—C15D	1.417 (8)
C6B—C7B	1.385 (9)	C13D—N3D	1.372 (8)
C6B—H61B	0.9500	C13D—H13D	0.9500
C7B—C8B	1.386 (8)	N3D—C14D	1.366 (9)
C7B—H71B	0.9500	N3D—H5D	0.8800
C8B—H81B	0.9500	C14D—C19D	1.380 (9)
C10B—C20B	1.522 (7)	C14D—C15D	1.425 (8)
C10B—C11B	1.531 (7)	C15D—C16D	1.393 (8)
C10B—H10B	1.0000	C16D—C17D	1.388 (9)
C11B—C12B	1.514 (7)	C16D—H16D	0.9500
C11B—H14B	0.9900	C17D—C18D	1.392 (10)
C11B—H15B	0.9900	C17D—H17D	0.9500
C12B—C13B	1.367 (8)	C18D—C19D	1.388 (10)
C12B—C15B	1.422 (7)	C18D—H18D	0.9500
C13B—N3B	1.377 (7)	C19D—H19D	0.9500
C13B—H13B	0.9500	C11E—C12E	1.508 (8)
N3B—C14B	1.368 (7)	C11E—H14E	0.9900
N3B—H5B	0.8800	C11E—H15E	0.9900
C14B—C19B	1.383 (8)	C12E—C13E	1.369 (9)
C14B—C15B	1.422 (7)	C12E—C15E	1.415 (9)
C15B—C16B	1.399 (8)	C13E—N3E	1.373 (9)
C16B—C17B	1.388 (8)	C13E—H13E	0.9500
C16B—H16B	0.9500	N3E—C14E	1.366 (10)
C17B—C18B	1.394 (8)	N3E—H5E	0.8800
C17B—H17B	0.9500	C14E—C19E	1.379 (9)
C18B—C19B	1.378 (8)	C14E—C15E	1.425 (9)
C18B—H18B	0.9500	C15E—C16E	1.393 (9)
C19B—H19B	0.9500	C16E—C17E	1.388 (10)
O1C—C9C	1.236 (7)	C16E—H16E	0.9500
O2C—C20C	1.245 (7)	C17E—C18E	1.393 (11)
O3C—C20C	1.271 (7)	C17E—H17E	0.9500
N1C—C1C	1.485 (7)	C18E—C19E	1.387 (11)
N1C—H1C	0.9100	C18E—H18E	0.9500
N1C—H2C	0.9100	C19E—H19E	0.9500
N1C—H3C	0.9100	O1W—H11W	0.852 (10)
N2C—C9C	1.325 (7)	O1W—H12W	0.859 (10)
N2C—C10C	1.469 (7)	O2W—H21W	0.854 (10)
N2C—H4C	0.8800	O2W—H22W	0.849 (10)
C1C—C9C	1.520 (8)	O3W—H31W	0.856 (10)
C1C—C2C	1.521 (7)	O3W—H32W	0.856 (10)
C1C—H11C	1.0000
C1A—N1A—H1A	109.5	C1C—C2C—H21C	108.8
C1A—N1A—H2A	109.5	C3C—C2C—H22C	108.8
H1A—N1A—H2A	109.5	C1C—C2C—H22C	108.8
C1A—N1A—H3A	109.5	H21C—C2C—H22C	107.7
H1A—N1A—H3A	109.5	C4C—C3C—C8C	117.7 (6)
H2A—N1A—H3A	109.5	C4C—C3C—C2C	121.0 (6)
C9A—N2A—C10A	121.3 (6)	C8C—C3C—C2C	121.3 (6)
C9A—N2A—H4A	119.4	C3C—C4C—C5C	120.7 (6)
C10A—N2A—H4A	119.4	C3C—C4C—H41C	119.6
N1A—C1A—C2A	110.8 (5)	C5C—C4C—H41C	119.6
N1A—C1A—C9A	106.7 (5)	C6C—C5C—C4C	121.2 (7)
C2A—C1A—C9A	113.9 (6)	C6C—C5C—H51C	119.4
N1A—C1A—H11A	108.4	C4C—C5C—H51C	119.4
C2A—C1A—H11A	108.4	C5C—C6C—C7C	118.7 (6)
C9A—C1A—H11A	108.4	C5C—C6C—H61C	120.7
C3A—C2A—C1A	116.6 (6)	C7C—C6C—H61C	120.7
C3A—C2A—H21A	108.1	C8C—C7C—C6C	120.1 (7)
C1A—C2A—H21A	108.1	C8C—C7C—H71C	120.0
C3A—C2A—H22A	108.1	C6C—C7C—H71C	120.0
C1A—C2A—H22A	108.1	C7C—C8C—C3C	121.6 (6)
H21A—C2A—H22A	107.3	C7C—C8C—H81C	119.2
C4A—C3A—C8A	117.9 (6)	C3C—C8C—H81C	119.2
C4A—C3A—C2A	121.8 (6)	O1C—C9C—N2C	124.2 (6)
C8A—C3A—C2A	120.4 (6)	O1C—C9C—C1C	118.9 (6)
C3A—C4A—C5A	121.0 (7)	N2C—C9C—C1C	116.9 (6)
C3A—C4A—H41A	119.5	N2C—C10C—C11C	112.3 (5)
C5A—C4A—H41A	119.5	N2C—C10C—C20C	109.9 (5)
C6A—C5A—C4A	120.8 (7)	C11C—C10C—C20C	114.8 (5)
C6A—C5A—H51A	119.6	N2C—C10C—H10C	106.4
C4A—C5A—H51A	119.6	C11C—C10C—H10C	106.4
C5A—C6A—C7A	118.6 (7)	C20C—C10C—H10C	106.4
C5A—C6A—H61A	120.7	C12C—C11C—C10C	113.4 (6)
C7A—C6A—H61A	120.7	C12C—C11C—H14C	108.9
C8A—C7A—C6A	120.6 (7)	C10C—C11C—H14C	108.9
C8A—C7A—H71A	119.7	C12C—C11C—H15C	108.9
C6A—C7A—H71A	119.7	C10C—C11C—H15C	108.9
C7A—C8A—C3A	121.1 (6)	H14C—C11C—H15C	107.7
C7A—C8A—H81A	119.5	C13C—C12C—C15C	106.7 (5)
C3A—C8A—H81A	119.5	C13C—C12C—C11C	126.7 (6)
O1A—C9A—N2A	124.2 (6)	C15C—C12C—C11C	126.6 (6)
O1A—C9A—C1A	119.3 (6)	C12C—C13C—N3C	109.2 (6)
N2A—C9A—C1A	116.5 (6)	C12C—C13C—H13C	125.4
N2A—C10A—C20A	111.2 (5)	N3C—C13C—H13C	125.4
N2A—C10A—C11A	111.8 (6)	C14C—N3C—C13C	109.9 (6)
C20A—C10A—C11A	113.5 (5)	C14C—N3C—H5C	125.0
N2A—C10A—H10A	106.6	C13C—N3C—H5C	125.0
C20A—C10A—H10A	106.6	N3C—C14C—C19C	131.0 (6)
C11A—C10A—H10A	106.6	N3C—C14C—C15C	106.5 (6)
C12A—C11A—C10A	113.4 (5)	C19C—C14C—C15C	122.5 (6)
C12A—C11A—H14A	108.9	C16C—C15C—C12C	134.3 (6)
C10A—C11A—H14A	108.9	C16C—C15C—C14C	118.0 (6)
C12A—C11A—H15A	108.9	C12C—C15C—C14C	107.7 (5)
C10A—C11A—H15A	108.9	C17C—C16C—C15C	120.2 (7)
H14A—C11A—H15A	107.7	C17C—C16C—H16C	119.9
C13A—C12A—C15A	106.5 (5)	C15C—C16C—H16C	119.9
C13A—C12A—C11A	126.9 (6)	C16C—C17C—C18C	119.9 (7)
C15A—C12A—C11A	126.6 (6)	C16C—C17C—H17C	120.1
C12A—C13A—N3A	109.4 (6)	C18C—C17C—H17C	120.1
C12A—C13A—H13A	125.3	C19C—C18C—C17C	122.1 (7)
N3A—C13A—H13A	125.3	C19C—C18C—H18C	119.0
C14A—N3A—C13A	110.1 (5)	C17C—C18C—H18C	119.0
C14A—N3A—H5A	124.9	C14C—C19C—C18C	117.4 (7)
C13A—N3A—H5A	124.9	C14C—C19C—H19C	121.3
N3A—C14A—C19A	131.1 (6)	C18C—C19C—H19C	121.3
N3A—C14A—C15A	105.8 (5)	O2C—C20C—O3C	125.2 (6)
C19A—C14A—C15A	123.1 (6)	O2C—C20C—C10C	117.7 (6)
C16A—C15A—C12A	134.0 (6)	O3C—C20C—C10C	117.0 (6)
C16A—C15A—C14A	118.0 (6)	C1D—N1D—H1D	109.5
C12A—C15A—C14A	108.0 (5)	C1D—N1D—H2D	109.5
C17A—C16A—C15A	119.5 (7)	H1D—N1D—H2D	109.5
C17A—C16A—H16A	120.2	C1D—N1D—H3D	109.5
C15A—C16A—H16A	120.2	H1D—N1D—H3D	109.5
C16A—C17A—C18A	121.1 (7)	H2D—N1D—H3D	109.5
C16A—C17A—H17A	119.4	C9D—N2D—C10D	121.4 (6)
C18A—C17A—H17A	119.4	C9D—N2D—H4D	119.3
C19A—C18A—C17A	121.5 (7)	C10D—N2D—H4D	119.3
C19A—C18A—H18A	119.3	N1D—C1D—C9D	108.5 (6)
C17A—C18A—H18A	119.3	N1D—C1D—C2D	109.0 (6)
C14A—C19A—C18A	116.8 (7)	C9D—C1D—C2D	111.8 (6)
C14A—C19A—H19A	121.6	N1D—C1D—H11D	109.2
C18A—C19A—H19A	121.6	C9D—C1D—H11D	109.2
O2A—C20A—O3A	123.3 (7)	C2D—C1D—H11D	109.2
O2A—C20A—C10A	120.4 (6)	C3D—C2D—C1D	112.6 (6)
O3A—C20A—C10A	116.2 (6)	C3D—C2D—H21D	109.1
C1B—N1B—H1B	109.5	C1D—C2D—H21D	109.1
C1B—N1B—H2B	109.5	C3D—C2D—H22D	109.1
H1B—N1B—H2B	109.3	C1D—C2D—H22D	109.1
C1B—N1B—H3B	109.5	H21D—C2D—H22D	107.8
H1B—N1B—H3B	109.5	C4D—C3D—C8D	118.8 (6)
H2B—N1B—H3B	109.5	C4D—C3D—C2D	120.1 (6)
C9B—N2B—C10B	121.7 (6)	C8D—C3D—C2D	121.1 (6)
C9B—N2B—H4B	119.2	C3D—C4D—C5D	120.7 (7)
C10B—N2B—H4B	119.2	C3D—C4D—H41D	119.6
N1B—C1B—C2B	109.6 (6)	C5D—C4D—H41D	119.6
N1B—C1B—C9B	108.9 (6)	C6D—C5D—C4D	120.2 (7)
C2B—C1B—C9B	110.7 (6)	C6D—C5D—H51D	119.9
N1B—C1B—H11B	109.2	C4D—C5D—H51D	119.9
C2B—C1B—H11B	109.2	C5D—C6D—C7D	119.2 (7)
C9B—C1B—H11B	109.2	C5D—C6D—H61D	120.4
C3B—C2B—C1B	112.5 (6)	C7D—C6D—H61D	120.4
C3B—C2B—H21B	109.1	C6D—C7D—C8D	120.4 (7)
C1B—C2B—H21B	109.1	C6D—C7D—H71D	119.8
C3B—C2B—H22B	109.1	C8D—C7D—H71D	119.8
C1B—C2B—H22B	109.1	C3D—C8D—C7D	120.7 (6)
H21B—C2B—H22B	107.8	C3D—C8D—H81D	119.7
C4B—C3B—C8B	118.3 (6)	C7D—C8D—H81D	119.7
C4B—C3B—C2B	120.6 (7)	O1D—C9D—N2D	124.6 (6)
C8B—C3B—C2B	120.9 (6)	O1D—C9D—C1D	119.9 (6)
C3B—C4B—C5B	120.7 (7)	N2D—C9D—C1D	115.5 (6)
C3B—C4B—H41B	119.7	N2D—C10D—C20D	110.4 (5)
C5B—C4B—H41B	119.7	N2D—C10D—C11D	113.3 (7)
C6B—C5B—C4B	121.3 (7)	C20D—C10D—C11D	114.7 (6)
C6B—C5B—H51B	119.4	N2D—C10D—H10D	105.9
C4B—C5B—H51B	119.4	C20D—C10D—H10D	105.9
C5B—C6B—C7B	118.5 (7)	C11D—C10D—H10D	105.9
C5B—C6B—H61B	120.7	C12D—C11D—C10D	111.4 (6)
C7B—C6B—H61B	120.7	C12D—C11D—H14D	109.3
C6B—C7B—C8B	120.4 (7)	C10D—C11D—H14D	109.3
C6B—C7B—H71B	119.8	C12D—C11D—H15D	109.3
C8B—C7B—H71B	119.8	C10D—C11D—H15D	109.3
C3B—C8B—C7B	120.7 (7)	H14D—C11D—H15D	108.0
C3B—C8B—H81B	119.6	C13D—C12D—C15D	106.8 (6)
C7B—C8B—H81B	119.6	C13D—C12D—C11D	126.0 (8)
O1B—C9B—N2B	124.5 (6)	C15D—C12D—C11D	125.6 (8)
O1B—C9B—C1B	119.6 (6)	C12D—C13D—N3D	109.2 (7)
N2B—C9B—C1B	115.9 (6)	C12D—C13D—H13D	125.4
N2B—C10B—C20B	110.5 (5)	N3D—C13D—H13D	125.4
N2B—C10B—C11B	112.3 (6)	C14D—N3D—C13D	110.0 (7)
C20B—C10B—C11B	117.0 (6)	C14D—N3D—H5D	125.0
N2B—C10B—H10B	105.3	C13D—N3D—H5D	125.0
C20B—C10B—H10B	105.3	N3D—C14D—C19D	131.0 (8)
C11B—C10B—H10B	105.3	N3D—C14D—C15D	106.3 (6)
C12B—C11B—C10B	113.0 (5)	C19D—C14D—C15D	122.6 (8)
C12B—C11B—H14B	109.0	C16D—C15D—C12D	134.0 (7)
C10B—C11B—H14B	109.0	C16D—C15D—C14D	118.4 (7)
C12B—C11B—H15B	109.0	C12D—C15D—C14D	107.5 (6)
C10B—C11B—H15B	109.0	C17D—C16D—C15D	119.3 (8)
H14B—C11B—H15B	107.8	C17D—C16D—H16D	120.3
C13B—C12B—C15B	106.5 (5)	C15D—C16D—H16D	120.3
C13B—C12B—C11B	126.8 (6)	C16D—C17D—C18D	120.7 (9)
C15B—C12B—C11B	126.6 (6)	C16D—C17D—H17D	119.7
C12B—C13B—N3B	109.7 (6)	C18D—C17D—H17D	119.7
C12B—C13B—H13B	125.2	C19D—C18D—C17D	121.7 (9)
N3B—C13B—H13B	125.2	C19D—C18D—H18D	119.1
C14B—N3B—C13B	109.5 (5)	C17D—C18D—H18D	119.1
C14B—N3B—H5B	125.2	C14D—C19D—C18D	117.1 (8)
C13B—N3B—H5B	125.2	C14D—C19D—H19D	121.4
N3B—C14B—C19B	130.5 (6)	C18D—C19D—H19D	121.4
N3B—C14B—C15B	106.6 (5)	O2D—C20D—O3D	124.1 (6)
C19B—C14B—C15B	122.8 (6)	O2D—C20D—C10D	117.4 (6)
C16B—C15B—C14B	117.9 (6)	O3D—C20D—C10D	118.3 (6)
C16B—C15B—C12B	134.5 (6)	C12E—C11E—H14E	109.3
C14B—C15B—C12B	107.6 (5)	C12E—C11E—H15E	109.3
C17B—C16B—C15B	119.7 (7)	H14E—C11E—H15E	108.0
C17B—C16B—H16B	120.2	C13E—C12E—C15E	107.0 (7)
C15B—C16B—H16B	120.2	C13E—C12E—C11E	127.1 (10)
C16B—C17B—C18B	120.3 (7)	C15E—C12E—C11E	125.9 (9)
C16B—C17B—H17B	119.8	C12E—C13E—N3E	109.2 (8)
C18B—C17B—H17B	119.8	C12E—C13E—H13E	125.4
C19B—C18B—C17B	122.1 (7)	N3E—C13E—H13E	125.4
C19B—C18B—H18B	119.0	C14E—N3E—C13E	110.0 (8)
C17B—C18B—H18B	119.0	C14E—N3E—H5E	125.0
C18B—C19B—C14B	117.2 (7)	C13E—N3E—H5E	125.0
C18B—C19B—H19B	121.4	N3E—C14E—C19E	131.0 (9)
C14B—C19B—H19B	121.4	N3E—C14E—C15E	106.4 (7)
O2B—C20B—O3B	122.7 (6)	C19E—C14E—C15E	122.5 (9)
O2B—C20B—C10B	118.0 (6)	C16E—C15E—C12E	133.9 (8)
O3B—C20B—C10B	119.1 (6)	C16E—C15E—C14E	118.6 (8)
C1C—N1C—H1C	109.5	C12E—C15E—C14E	107.4 (7)
C1C—N1C—H2C	109.5	C17E—C16E—C15E	119.1 (9)
H1C—N1C—H2C	109.5	C17E—C16E—H16E	120.4
C1C—N1C—H3C	109.5	C15E—C16E—H16E	120.4
H1C—N1C—H3C	109.5	C16E—C17E—C18E	120.7 (10)
H2C—N1C—H3C	109.5	C16E—C17E—H17E	119.6
C9C—N2C—C10C	122.4 (6)	C18E—C17E—H17E	119.6
C9C—N2C—H4C	118.8	C19E—C18E—C17E	121.9 (10)
C10C—N2C—H4C	118.8	C19E—C18E—H18E	119.1
N1C—C1C—C9C	108.9 (5)	C17E—C18E—H18E	119.1
N1C—C1C—C2C	108.4 (5)	C14E—C19E—C18E	117.1 (10)
C9C—C1C—C2C	112.9 (6)	C14E—C19E—H19E	121.5
N1C—C1C—H11C	108.9	C18E—C19E—H19E	121.5
C9C—C1C—H11C	108.9	H11W—O1W—H12W	103.2 (17)
C2C—C1C—H11C	108.9	H21W—O2W—H22W	104.0 (17)
C3C—C2C—C1C	113.8 (6)	H31W—O3W—H32W	102.9 (16)
C3C—C2C—H21C	108.8
N1A—C1A—C2A—C3A	56.7 (8)	C4C—C3C—C8C—C7C	0.9 (13)
C9A—C1A—C2A—C3A	−63.6 (8)	C2C—C3C—C8C—C7C	−178.6 (8)
C1A—C2A—C3A—C4A	−97.2 (10)	C10C—N2C—C9C—O1C	6.1 (12)
C1A—C2A—C3A—C8A	81.5 (10)	C10C—N2C—C9C—C1C	−174.2 (6)
C8A—C3A—C4A—C5A	−1.0 (14)	N1C—C1C—C9C—O1C	−73.7 (9)
C2A—C3A—C4A—C5A	177.7 (8)	C2C—C1C—C9C—O1C	46.7 (10)
C3A—C4A—C5A—C6A	0.4 (15)	N1C—C1C—C9C—N2C	106.6 (8)
C4A—C5A—C6A—C7A	0.2 (16)	C2C—C1C—C9C—N2C	−133.0 (7)
C5A—C6A—C7A—C8A	0.0 (17)	C9C—N2C—C10C—C11C	−74.0 (8)
C6A—C7A—C8A—C3A	−0.6 (16)	C9C—N2C—C10C—C20C	55.1 (9)
C4A—C3A—C8A—C7A	1.1 (15)	N2C—C10C—C11C—C12C	−64.7 (8)
C2A—C3A—C8A—C7A	−177.6 (9)	C20C—C10C—C11C—C12C	168.8 (7)
C10A—N2A—C9A—O1A	0.5 (13)	C10C—C11C—C12C—C13C	62.5 (11)
C10A—N2A—C9A—C1A	−179.0 (6)	C10C—C11C—C12C—C15C	−118.0 (9)
N1A—C1A—C9A—O1A	−34.9 (10)	C15C—C12C—C13C—N3C	1.6 (9)
C2A—C1A—C9A—O1A	87.7 (9)	C11C—C12C—C13C—N3C	−178.8 (7)
N1A—C1A—C9A—N2A	144.6 (7)	C12C—C13C—N3C—C14C	−1.2 (9)
C2A—C1A—C9A—N2A	−92.8 (8)	C13C—N3C—C14C—C19C	−178.1 (9)
C9A—N2A—C10A—C20A	56.0 (10)	C13C—N3C—C14C—C15C	0.3 (9)
C9A—N2A—C10A—C11A	−72.0 (9)	C13C—C12C—C15C—C16C	178.0 (10)
N2A—C10A—C11A—C12A	−55.5 (8)	C11C—C12C—C15C—C16C	−1.6 (16)
C20A—C10A—C11A—C12A	177.6 (7)	C13C—C12C—C15C—C14C	−1.4 (9)
C10A—C11A—C12A—C13A	−31.9 (11)	C11C—C12C—C15C—C14C	179.0 (7)
C10A—C11A—C12A—C15A	148.0 (8)	N3C—C14C—C15C—C16C	−178.8 (8)
C15A—C12A—C13A—N3A	−2.1 (9)	C19C—C14C—C15C—C16C	−0.3 (13)
C11A—C12A—C13A—N3A	177.8 (8)	N3C—C14C—C15C—C12C	0.7 (10)
C12A—C13A—N3A—C14A	0.3 (9)	C19C—C14C—C15C—C12C	179.2 (8)
C13A—N3A—C14A—C19A	−178.9 (9)	C12C—C15C—C16C—C17C	−178.7 (10)
C13A—N3A—C14A—C15A	1.7 (9)	C14C—C15C—C16C—C17C	0.7 (13)
C13A—C12A—C15A—C16A	−179.1 (9)	C15C—C16C—C17C—C18C	−1.3 (14)
C11A—C12A—C15A—C16A	1.0 (16)	C16C—C17C—C18C—C19C	1.6 (15)
C13A—C12A—C15A—C14A	3.1 (10)	N3C—C14C—C19C—C18C	178.7 (9)
C11A—C12A—C15A—C14A	−176.8 (8)	C15C—C14C—C19C—C18C	0.6 (14)
N3A—C14A—C15A—C16A	178.9 (7)	C17C—C18C—C19C—C14C	−1.3 (14)
C19A—C14A—C15A—C16A	−0.6 (13)	N2C—C10C—C20C—O2C	33.3 (10)
N3A—C14A—C15A—C12A	−2.9 (9)	C11C—C10C—C20C—O2C	161.0 (8)
C19A—C14A—C15A—C12A	177.6 (8)	N2C—C10C—C20C—O3C	−149.8 (7)
C12A—C15A—C16A—C17A	−178.1 (10)	C11C—C10C—C20C—O3C	−22.1 (11)
C14A—C15A—C16A—C17A	−0.5 (12)	N1D—C1D—C2D—C3D	179.3 (6)
C15A—C16A—C17A—C18A	1.0 (13)	C9D—C1D—C2D—C3D	59.4 (9)
C16A—C17A—C18A—C19A	−0.4 (13)	C1D—C2D—C3D—C4D	−113.4 (9)
N3A—C14A—C19A—C18A	−178.2 (8)	C1D—C2D—C3D—C8D	64.3 (10)
C15A—C14A—C19A—C18A	1.2 (13)	C8D—C3D—C4D—C5D	2.4 (14)
C17A—C18A—C19A—C14A	−0.7 (13)	C2D—C3D—C4D—C5D	−179.8 (8)
N2A—C10A—C20A—O2A	29.6 (11)	C3D—C4D—C5D—C6D	−2.7 (15)
C11A—C10A—C20A—O2A	156.7 (8)	C4D—C5D—C6D—C7D	2.5 (15)
N2A—C10A—C20A—O3A	−152.5 (7)	C5D—C6D—C7D—C8D	−2.1 (14)
C11A—C10A—C20A—O3A	−25.4 (11)	C4D—C3D—C8D—C7D	−2.1 (14)
N1B—C1B—C2B—C3B	172.8 (7)	C2D—C3D—C8D—C7D	−179.8 (8)
C9B—C1B—C2B—C3B	52.6 (9)	C6D—C7D—C8D—C3D	1.9 (14)
C1B—C2B—C3B—C4B	−117.6 (10)	C10D—N2D—C9D—O1D	8.4 (12)
C1B—C2B—C3B—C8B	57.7 (12)	C10D—N2D—C9D—C1D	−171.3 (6)
C8B—C3B—C4B—C5B	3.1 (18)	N1D—C1D—C9D—O1D	−71.2 (9)
C2B—C3B—C4B—C5B	178.5 (11)	C2D—C1D—C9D—O1D	49.0 (10)
C3B—C4B—C5B—C6B	−2 (2)	N1D—C1D—C9D—N2D	108.5 (8)
C4B—C5B—C6B—C7B	1 (2)	C2D—C1D—C9D—N2D	−131.3 (7)
C5B—C6B—C7B—C8B	0.4 (19)	C9D—N2D—C10D—C20D	51.2 (9)
C4B—C3B—C8B—C7B	−2.0 (17)	C9D—N2D—C10D—C11D	−79.0 (8)
C2B—C3B—C8B—C7B	−177.5 (10)	N2D—C10D—C11D—C12D	−74.6 (10)
C6B—C7B—C8B—C3B	0.3 (19)	C20D—C10D—C11D—C12D	157.4 (8)
C10B—N2B—C9B—O1B	1.6 (13)	C10D—C11D—C12D—C13D	72.9 (16)
C10B—N2B—C9B—C1B	177.9 (6)	C10D—C11D—C12D—C15D	−90.6 (14)
N1B—C1B—C9B—O1B	−65.5 (10)	C15D—C12D—C13D—N3D	−3.2 (18)
C2B—C1B—C9B—O1B	55.1 (10)	C11D—C12D—C13D—N3D	−169.1 (11)
N1B—C1B—C9B—N2B	117.9 (8)	C12D—C13D—N3D—C14D	1.9 (19)
C2B—C1B—C9B—N2B	−121.5 (8)	C13D—N3D—C14D—C19D	−178.2 (18)
C9B—N2B—C10B—C20B	51.2 (10)	C13D—N3D—C14D—C15D	0.1 (17)
C9B—N2B—C10B—C11B	−81.5 (9)	C13D—C12D—C15D—C16D	178.2 (19)
N2B—C10B—C11B—C12B	−81.0 (8)	C11D—C12D—C15D—C16D	−16 (3)
C20B—C10B—C11B—C12B	149.7 (7)	C13D—C12D—C15D—C14D	3.2 (17)
C10B—C11B—C12B—C13B	−4.1 (12)	C11D—C12D—C15D—C14D	169.2 (11)
C10B—C11B—C12B—C15B	−179.0 (8)	N3D—C14D—C15D—C16D	−178.0 (14)
C15B—C12B—C13B—N3B	−2.9 (10)	C19D—C14D—C15D—C16D	1 (2)
C11B—C12B—C13B—N3B	−178.6 (8)	N3D—C14D—C15D—C12D	−2.0 (17)
C12B—C13B—N3B—C14B	2.7 (10)	C19D—C14D—C15D—C12D	176.4 (15)
C13B—N3B—C14B—C19B	176.8 (10)	C12D—C15D—C16D—C17D	−173.0 (18)
C13B—N3B—C14B—C15B	−1.4 (10)	C14D—C15D—C16D—C17D	2 (2)
N3B—C14B—C15B—C16B	−179.8 (8)	C15D—C16D—C17D—C18D	−4 (3)
C19B—C14B—C15B—C16B	1.8 (13)	C16D—C17D—C18D—C19D	5 (3)
N3B—C14B—C15B—C12B	−0.4 (10)	N3D—C14D—C19D—C18D	178.1 (17)
C19B—C14B—C15B—C12B	−178.7 (9)	C15D—C14D—C19D—C18D	0 (2)
C13B—C12B—C15B—C16B	−178.7 (10)	C17D—C18D—C19D—C14D	−3 (3)
C11B—C12B—C15B—C16B	−3.0 (17)	N2D—C10D—C20D—O2D	39.2 (11)
C13B—C12B—C15B—C14B	2.0 (10)	C11D—C10D—C20D—O2D	168.6 (9)
C11B—C12B—C15B—C14B	177.7 (8)	N2D—C10D—C20D—O3D	−145.8 (8)
C14B—C15B—C16B—C17B	−1.9 (13)	C11D—C10D—C20D—O3D	−16.3 (12)
C12B—C15B—C16B—C17B	178.9 (10)	C15E—C12E—C13E—N3E	3 (3)
C15B—C16B—C17B—C18B	2.0 (14)	C11E—C12E—C13E—N3E	−175.8 (18)
C16B—C17B—C18B—C19B	−2.0 (14)	C12E—C13E—N3E—C14E	−1 (3)
C17B—C18B—C19B—C14B	1.9 (14)	C13E—N3E—C14E—C19E	−178 (3)
N3B—C14B—C19B—C18B	−179.7 (9)	C13E—N3E—C14E—C15E	−1 (3)
C15B—C14B—C19B—C18B	−1.8 (14)	C13E—C12E—C15E—C16E	178 (3)
N2B—C10B—C20B—O2B	41.7 (11)	C11E—C12E—C15E—C16E	−3 (4)
C11B—C10B—C20B—O2B	171.9 (8)	C13E—C12E—C15E—C14E	−3 (3)
N2B—C10B—C20B—O3B	−143.7 (8)	C11E—C12E—C15E—C14E	175.5 (17)
C11B—C10B—C20B—O3B	−13.5 (12)	N3E—C14E—C15E—C16E	−179 (2)
N1C—C1C—C2C—C3C	−177.0 (6)	C19E—C14E—C15E—C16E	−1 (4)
C9C—C1C—C2C—C3C	62.3 (9)	N3E—C14E—C15E—C12E	2 (3)
C1C—C2C—C3C—C4C	−116.5 (9)	C19E—C14E—C15E—C12E	−180 (3)
C1C—C2C—C3C—C8C	62.9 (11)	C12E—C15E—C16E—C17E	179 (3)
C8C—C3C—C4C—C5C	0.1 (13)	C14E—C15E—C16E—C17E	0 (4)
C2C—C3C—C4C—C5C	179.5 (8)	C15E—C16E—C17E—C18E	0 (4)
C3C—C4C—C5C—C6C	−0.8 (15)	C16E—C17E—C18E—C19E	1 (4)
C4C—C5C—C6C—C7C	0.7 (15)	N3E—C14E—C19E—C18E	179 (3)
C5C—C6C—C7C—C8C	0.3 (14)	C15E—C14E—C19E—C18E	2 (4)
C6C—C7C—C8C—C3C	−1.0 (14)	C17E—C18E—C19E—C14E	−2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1W	0.91	2.17	2.917 (11)	139
N1A—H1A···O3W	0.91	2.45	3.135 (10)	132
N1A—H2A···O3D^i	0.91	1.87	2.752 (9)	162
N1A—H3A···O2D	0.91	1.96	2.740 (9)	143
N2A—H4A···O3A^i	0.88	1.99	2.791 (8)	151
N3A—H5A···C19A^ii	0.88	2.55	3.365 (10)	155
C1A—H11A···O1A^i	1.00	2.59	3.302 (8)	128
N1B—H1B···O2W^i	0.91	1.92	2.731 (10)	147
N1B—H2B···O2C	0.91	1.88	2.751 (9)	159
N1B—H3B···O3C^i	0.91	1.95	2.811 (8)	158
N2B—H4B···O3B^i	0.88	2.01	2.807 (8)	150
N3B—H5B···C5C^iii	0.88	2.66	3.458 (11)	151
C1B—H11B···O1B^i	1.00	2.45	3.383 (9)	155
N1C—H1C···O2W	0.91	1.97	2.842 (9)	160
N1C—H2C···O3A^i	0.91	1.91	2.800 (9)	166
N1C—H3C···O2A	0.91	1.89	2.788 (9)	171
N2C—H4C···O3C^i	0.88	1.99	2.784 (8)	150
N3C—H5C···C6D^iv	0.88	2.77	3.542 (10)	147
C1C—H11C···O1C^i	1.00	2.47	3.333 (8)	144
N1D—H1D···O3W	0.91	2.02	2.809 (9)	144
N1D—H2D···O3B^i	0.91	1.85	2.763 (9)	175
N1D—H3D···O2B	0.91	1.92	2.815 (9)	166
N2D—H4D···O3D^i	0.88	2.00	2.730 (8)	139
N3D—H5D···C17C^v	0.88	2.39	3.257 (13)	167
C1D—H11D···O1D^i	1.00	2.47	3.278 (8)	138
O1W—H11W···O2A	0.85 (1)	1.95 (2)	2.793 (9)	172 (9)
O1W—H12W···O3W^vi	0.86 (1)	2.37 (4)	3.138 (9)	148 (6)
O2W—H21W···O2C^i	0.85 (1)	1.93 (2)	2.750 (9)	159 (7)
O2W—H22W···O3W	0.85 (1)	1.93 (2)	2.774 (9)	170 (9)
O3W—H31W···O2B^i	0.86 (1)	1.84 (2)	2.684 (8)	167 (9)
O3W—H32W···O2D^i	0.86 (1)	1.84 (3)	2.664 (9)	161 (7)

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