1,N⁶-Etheno-2′-de­oxy­tubercidin hemihydrate

The title compound [systematic name: 7-(2-de­oxy-β-D-erythro-pentofuranos­yl)-7H-imidazo[1,2-c]pyrrolo­[2,3-d]py­rimi­dine hemihydrate], 2C₁₃H₁₄N₄O₃·H₂O or (I)·0.5H₂O, shows two similar conformations in the asymmetric unit. These two conformers are connected through one water mol­ecule by hydrogen bonds. The N-glycosylic bonds of both conformers show an almost identical anti conformation with χ = −107.7 (2)° for conformer (I-1) and −107.0 (2)° for conformer (I-2). The sugar moiety adopts an unusual N-type (C3′-endo) sugar pucker for 2′-de­oxy­ribonucleosides, with P = 36.8 (2)° and τ_m = 40.6 (1)° for conformer (I-1), and P = 34.5 (2)° and τ_m = 41.4 (1)° for conformer (I-2). Both conformers and the solvent mol­ecule participate in the formation of a three-dimensional pattern with a `chain'-like arrangement of the conformers. The structure is stabilized by inter­molecular O—H...O and O—H...N hydrogen bonds, together with weak C—H...O contacts.

S1. Comment

Etheno adducts have proved to be biomarkers for DNA damage arising from reactions of endogenous lipid peroxidation, chloroethylene oxide or chloroacetaldehyde (Bolt, 1994). They are also thought to initiate vinyl-chloride- and urethane-induced tumours because of their miscoding capability, leading to point mutations (Arab et al., 2009; Pandya & Moriya, 1996). 1,N⁶-Etheno-2'-deoxytubercidin, (I), and the corresponding congener 1,N⁶-ethenoadenosine, (III), can be considered as 7-deazapurine or purine pyrrole ring annelation products with a [1,2-c]-ring connectivity (purine numbering is used throughout this discussion). By enlarging the aromatic system, these tricyclic nucleosides show strong fluorescence with quantum yields higher than 0.5 (Seela et al., 2007). Their propensity to fluorescence makes these compounds valuable for probing the biochemical and biophysical properties of nucleosides, nucleotides and nucleic acids (Bielecki et al., 2000; Inoue et al., 1981; Paulsen & Wintermeyer, 1984; Secrist et al., 1972; Seela et al., 2007). The 7-deazapurine nucleoside, (I), shows extraordinary stability in acidic and in alkaline media compared to its `purine' counterpart, (III) (Seela et al., 2007). The synthesis of the title compound, (I), which was prepared from 2'-deoxytubercidin with chloroacetaldehyde, was reported earlier (Seela et al., 2007). The single-crystal structure of (I) is studied herein and is compared to the closely related crystal structures of 2'-deoxytubercidin, [(IIa) and (IIb)] (Zabel et al., 1987), 1,N⁶-ethenoadenosine, (III) (Jaskólski, 1982), and 7-deaza-2,8-diaza-1,N⁶-ethenoadenosine, (IV) (Lin et al., 2004).

In the asymmetric unit of (I)₂.H₂O, two conformational states with a slightly different sugar puckering exist which are connected through water molecules by hydrogen bonds. They are defined as types 1 and 2, and denoted (I-1) and (I-2), respectively. The three-dimensional structures of the molecules of (I-1) and (I-2) are shown in Figs. 1 and 2, [respectively?], and selected geometric parameters are summarized in Table 1.

Conformers (I-1) and (I-2) exhibit almost identical torsion angles χ (O4'—C1'—N9—C4) of -107.7 (2) and -107.0 (2)°, respectively; referring to conformations situated between anti and high-anti (IUPAC-IUB Joint Commission on Biochemical Nomenclature, 1983). These values are close to that of the water-free crystal of (IIa) [χ = -104 (2)°], whereas the torsion angle of dihydrate, (IIb) [χ = -115.5 (3)°], falls into the anti range (Zabel et al., 1987). The length of the glycosylic bond N9—C1' is 1.451 (2) Å for (I-1) and 1.449 (2) Å for (I-2), which is almost identical to the bond length observed for 2'-deoxytubercidin [(IIa): 1.449 (2) Å; (IIb): 1.446 (4) Å; Zabel et al., 1987]. The parent ribonucleoside, (III), adopts a slightly longer glycosylic bond [1.455 (4) Å] (Jaskólski, 1982).

The heterocyclic base moiety of 1,N⁶-ethenoadenosine, (III), forms a `U'-shaped structure when looking from the edge side with a maximum deviation of 0.064 (4) Å out of the plane (Jaskólski, 1982). In contrast, the 7-deazapurine moieties of (I-1) and (I-2) are nearly planar. The r.m.s. deviations of the ring atoms from their calculated least-squares planes are 0.0121 Å for (I-1) and 0.0206 Å for (I-2). Maximum deviations were found for atom C112 of (I-1) with -0.0185 (2) Å and for atom N29 (I-2) with -0.0365 (2) Å.

For both conformers, the torsion angle about the exocyclic C4'—C5' bond, which is defined as γ (O5'—C5'—C4'—C3'), adopts an -antiperiplanar (gauche, trans) conformation with γ = -168.7 (2)° for (I-1) and γ = -167.1 (2)° for (I-2). In the crystal structures of (IIa) and (IIb), the torsion angles γ are also within the antiperiplanar range [-179.6 (2)°, -173.6 (3)°; trans] (Zabel et al., 1987).

Usually, the sugar conformation of ribonucleosides adopts the N-type pucker whereas 2'-deoxyribonucleosides prefer the S conformation. In solution, the predominant conformation of compound (I) shows the S-type conformation (75% S). The sugar conformation of compound (I) was determined from the vicinal ³J(H,H) coupling constants of the ¹H NMR spectra measured in D₂O, applying the program PSEUROT6.3 (Van Wijk et al., 1999). It has to be noted that both conformers exhibit sugar moieties with the N conformation in the crystalline state. For conformer (I-1), the sugar pucker is ³T₄ (C3'-endo-C4'-exo) (Altona & Sundaralingam, 1972) with a phase angle of pseudorotation of P = 36.8° and a maximum amplitude of puckering of τ_m = 40.6°. In conformer (I-2), the sugar moiety adopts a slightly different N-type sugar pucker with P = 34.5° and τ_m = 41.4°. In contrast, the parent 2'-deoxytubercidins, (IIa) and (IIb), adopt S conformations with P = 186.6° and 215.1°, respectively (C2'-endo-C1'-exo, ²T₁). A similar influence on the sugar conformation was also found for the ribonucleoside 1,N⁶-etheno derivatives, (III) and (IV), which adopt the S conformation (C2'-endo-C3'-exo; ₃T²) instead of the usual N-type conformation of ribonucleosides. The ribose ring of nucleoside (III) is characterized by P = 163.5° with τ_m = 44.3° (Jaskólski, 1982), and P = 183.4° with τ_m = 42.4° for compound (IV) (Lin et al., 2004).

The title compound forms a three-dimensional network, which is generated by numerous hydrogen bonds involving the two conformers (I-1) and (I-2) and the water molecule (Fig. 3 and Table 2). Within the ac plane, the conformers (I-1) and (I-2) are located in a `chain'- like arrangement. Each chain is composed of molecules of identical conformation, either (I-1) or (I-2), and the chains are ordered in an alternating fashion. Furthermore, within the chains, the individual molecules are arranged in a head-to-tail fashion. The different chains are connected to each other via hydrogen bonding of the two conformers. The individual chains are also stabilized by hydrogen bonds. In both cases, the water molecule participates in hydrogen bonding. Conformers (I-1) and (I-2) show a different hydrogen-bonding pattern. Hydrogen bonds are formed to neighbouring molecules of identical conformation (O13'—H13'···O15'ⁱ, O15'—H15'···N112ⁱⁱ, O23'—H23'···O25'ⁱⁱⁱ, O25'—H25'···N212^iv; for symmetry codes and geometry see Table 2), while those to the water molecule employ different atoms as acceptors. For (I-1), atom O15' functions as acceptor (O100—H102···O15'ⁱ), whereas atom O23' is the acceptor for (I-2) (O100—H101···O23'). Additional weak contacts (Steiner, 2002) were observed for both conformers, including that of conformer (I-2) to oxygen O100 of the water molecule (C210—H210···O100^vi, C12—H12···O13'^v, C22—H22···O23'^vi).

Related literature

For related literature, see: Altona & Sundaralingam (1972); Arab et al. (2009); Bielecki et al. (2000); Bolt (1994); IUPAC-IUB Joint Commission on Biochemical Nomenclature (1983); Inoue et al. (1981); Jaskólski (1982); Lin et al. (2004); Pandya & Moriya (1996); Paulsen & Wintermeyer (1984); Secrist et al. (1972); Seela et al. (2007); Steiner (2002); Van Wijk, Haasnoot, de Leeuw, Huckriede, Westra Hoekzema & Altona (1999); Zabel et al. (1987).

S2. Experimental

Compound (I) was synthesized as reported previously (Seela et al., 2007). Slow crystallization from aqueous methanol afforded (I).H₂O as colourless crystals (m.p. 442 K). For the diffraction experiment, a single crystal was mounted on a MiTeGen MicroMountsfibre in a thin smear of oil.

S3. Refinement

In the absence of suitable anomalous scattering, Friedel equivalents could not be used to determine the absolute structure. Refinement of the Flack parameter led to inconclusive values for this parameter [0.2 (7)]. Therefore, Friedel equivalents (2881) were merged before the final refinement. The known configuration of the parent molecule was used to define the enantiomer employed in the refined model.

All H atoms were found in a difference Fourier synthesis. In order to maximize the data/parameter ratio, the H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C). The OH groups were refined as rigid groups, allowed to rotate but not tip (AFIX 147) with O—H = 0.84 Å and U(H) = 1.5U_eq(O). The water H atoms were located from difference maps, and the parameters of the water H atoms were first refined freely. Owing to the low reflection/refined parameter ratio, the O—H distances were constrained [AFIX 3 (m = 0)] to 0.96 Å and U_iso(H) = 1.5U_eq(O) in the final cycles of refinement.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. Perspective views of (a) molecule (I-1) and (b) molecule (I-2), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary size
	Fig. 2. Overlay of molecules (I-1) and (I-2).
	Fig. 3. The crystal packing showing the intermolecular hydrogen-bonding network (parallel to ac plane).

7-(2-deoxy-β-D-erythro-pentofuranosyl)-7H-imidazo[1,2-c]pyrrolo[2,3-d]pyrimidine hemihydrate (1,N⁶-etheno-2'-deoxytubercidin hemihydrate

Crystal data

2C13H14N4O3·H2O	F(000) = 1192
Mr = 566.58	Dx = 1.434 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 9960 reflections
a = 19.6476 (12) Å	θ = 3.1–30.2°
b = 5.2979 (3) Å	µ = 0.11 mm^−1
c = 26.3354 (16) Å	T = 130 K
β = 106.865 (3)°	Block, colourless
V = 2623.4 (3) Å^3	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	4214 independent reflections
Radiation source: fine-focus sealed tube	3987 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 30.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −27→27
Tmin = 0.969, Tmax = 0.989	k = −6→7
46138 measured reflections	l = −37→37

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)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0528P)^2 + 2.1726P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
4214 reflections	Δρmax = 0.33 e Å^−3
374 parameters	Δρmin = −0.33 e Å^−3
1 restraint	Absolute structure: established by known chemical absolute configuration
Primary atom site location: structure-invariant direct methods

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
N11	0.30649 (9)	−0.2198 (4)	−0.14311 (6)	0.0187 (3)
C12	0.37027 (11)	−0.2977 (5)	−0.10879 (8)	0.0211 (4)
H12	0.3969	−0.4236	−0.1203	0.025*
N13	0.39545 (9)	−0.2056 (4)	−0.06125 (7)	0.0199 (3)
C14	0.35434 (10)	−0.0236 (4)	−0.04813 (7)	0.0164 (4)
C15	0.28979 (10)	0.0733 (4)	−0.07974 (8)	0.0170 (4)
C16	0.26376 (10)	−0.0329 (4)	−0.13084 (8)	0.0174 (4)
C17	0.26837 (11)	0.2648 (4)	−0.04969 (8)	0.0204 (4)
H17	0.2266	0.3650	−0.0607	0.024*
C18	0.31983 (11)	0.2761 (5)	−0.00191 (8)	0.0212 (4)
H18	0.3194	0.3878	0.0262	0.025*
N19	0.37253 (9)	0.1013 (4)	−0.00059 (7)	0.0176 (3)
C110	0.27289 (11)	−0.2997 (5)	−0.19499 (8)	0.0224 (4)
H110	0.2886	−0.4257	−0.2147	0.027*
C111	0.21312 (11)	−0.1577 (5)	−0.21093 (8)	0.0224 (4)
H111	0.1795	−0.1692	−0.2451	0.027*
N112	0.20674 (9)	0.0069 (4)	−0.17148 (7)	0.0209 (4)
C11'	0.43588 (10)	0.0517 (4)	0.04298 (7)	0.0163 (4)
H11C	0.4684	−0.0612	0.0304	0.020*
C12'	0.47629 (11)	0.2920 (5)	0.06714 (8)	0.0204 (4)
H12B	0.5280	0.2732	0.0723	0.024*
H12C	0.4587	0.4406	0.0443	0.024*
O13'	0.51496 (8)	0.4410 (3)	0.15925 (6)	0.0222 (3)
H13'	0.4970	0.5362	0.1774	0.033*
C13'	0.46005 (10)	0.3168 (4)	0.12039 (8)	0.0176 (4)
H13C	0.4138	0.4064	0.1155	0.021*
C14'	0.45317 (10)	0.0405 (4)	0.13421 (7)	0.0166 (4)
H14A	0.5016	−0.0368	0.1472	0.020*
O14'	0.41504 (8)	−0.0729 (3)	0.08456 (5)	0.0197 (3)
C15'	0.41325 (11)	−0.0018 (4)	0.17449 (8)	0.0197 (4)
H15B	0.4317	0.1148	0.2048	0.024*
H15C	0.3623	0.0369	0.1581	0.024*
O15'	0.42026 (8)	−0.2549 (3)	0.19342 (6)	0.0209 (3)
H15'	0.3802	−0.3252	0.1846	0.031*
N21	0.41692 (9)	1.0061 (4)	0.64906 (6)	0.0190 (3)
C22	0.45326 (11)	1.0822 (5)	0.61436 (8)	0.0227 (4)
H22	0.4877	1.2123	0.6251	0.027*
N23	0.44254 (9)	0.9838 (4)	0.56751 (7)	0.0217 (4)
C24	0.39205 (10)	0.7990 (4)	0.55514 (7)	0.0171 (4)
C25	0.35263 (10)	0.7033 (4)	0.58726 (8)	0.0167 (4)
C26	0.36720 (10)	0.8110 (4)	0.63846 (8)	0.0178 (4)
C27	0.30727 (11)	0.5113 (5)	0.55762 (8)	0.0206 (4)
H27	0.2740	0.4126	0.5689	0.025*
C28	0.32117 (10)	0.4973 (5)	0.50961 (8)	0.0208 (4)
H28	0.2986	0.3851	0.4816	0.025*
N29	0.37295 (9)	0.6710 (4)	0.50806 (7)	0.0181 (3)
C210	0.42418 (11)	1.0875 (5)	0.70082 (8)	0.0235 (4)
H210	0.4540	1.2186	0.7197	0.028*
C211	0.37954 (11)	0.9389 (5)	0.71828 (8)	0.0241 (4)
H211	0.3735	0.9507	0.7527	0.029*
N212	0.34363 (9)	0.7673 (4)	0.67997 (7)	0.0211 (4)
C21'	0.40203 (10)	0.7148 (4)	0.46418 (7)	0.0169 (4)
H21B	0.4450	0.8251	0.4764	0.020*
C22'	0.42207 (10)	0.4712 (4)	0.44016 (8)	0.0193 (4)
H22B	0.4690	0.4876	0.4336	0.023*
H22C	0.4231	0.3248	0.4637	0.023*
O23'	0.38386 (8)	0.3114 (3)	0.34860 (6)	0.0193 (3)
H23'	0.3514	0.2116	0.3328	0.029*
C23'	0.36256 (10)	0.4444 (4)	0.38811 (7)	0.0163 (4)
H23C	0.3201	0.3616	0.3946	0.020*
C24'	0.34657 (10)	0.7205 (4)	0.37314 (8)	0.0152 (3)
H24A	0.3850	0.7908	0.3593	0.018*
O24'	0.34914 (7)	0.8411 (3)	0.42234 (5)	0.0182 (3)
C25'	0.27543 (10)	0.7644 (4)	0.33290 (8)	0.0173 (4)
H25B	0.2688	0.6414	0.3036	0.021*
H25C	0.2371	0.7375	0.3498	0.021*
O25'	0.27071 (7)	1.0146 (3)	0.31212 (6)	0.0190 (3)
H25'	0.2332	1.0832	0.3146	0.029*
O100	0.47493 (10)	0.5675 (5)	0.30043 (8)	0.0422 (5)
H101	0.4363	0.5204	0.3139	0.063*
H102	0.4536	0.6441	0.2665	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0186 (7)	0.0210 (9)	0.0177 (7)	0.0020 (7)	0.0071 (6)	−0.0021 (7)
C12	0.0192 (9)	0.0215 (10)	0.0227 (9)	0.0044 (8)	0.0065 (7)	−0.0026 (8)
N13	0.0179 (7)	0.0214 (9)	0.0211 (8)	0.0043 (7)	0.0067 (6)	−0.0015 (7)
C14	0.0165 (8)	0.0176 (9)	0.0163 (8)	0.0003 (8)	0.0067 (6)	0.0006 (7)
C15	0.0168 (8)	0.0165 (9)	0.0192 (8)	0.0008 (7)	0.0077 (7)	−0.0008 (7)
C16	0.0174 (8)	0.0167 (9)	0.0197 (8)	0.0029 (7)	0.0080 (7)	0.0012 (8)
C17	0.0213 (9)	0.0201 (10)	0.0211 (9)	0.0051 (8)	0.0084 (7)	0.0000 (8)
C18	0.0229 (9)	0.0207 (10)	0.0219 (9)	0.0042 (8)	0.0097 (7)	−0.0018 (8)
N19	0.0179 (7)	0.0192 (8)	0.0165 (7)	0.0024 (7)	0.0060 (6)	−0.0009 (7)
C110	0.0254 (9)	0.0267 (11)	0.0156 (8)	−0.0002 (9)	0.0067 (7)	−0.0031 (8)
C111	0.0225 (9)	0.0286 (12)	0.0168 (8)	0.0000 (9)	0.0067 (7)	−0.0002 (8)
N112	0.0189 (7)	0.0254 (9)	0.0178 (7)	0.0025 (7)	0.0047 (6)	−0.0007 (7)
C11'	0.0164 (8)	0.0170 (9)	0.0161 (8)	−0.0009 (7)	0.0058 (6)	−0.0004 (7)
C12'	0.0229 (9)	0.0198 (10)	0.0202 (9)	−0.0067 (8)	0.0089 (7)	−0.0011 (8)
O13'	0.0228 (7)	0.0216 (8)	0.0216 (7)	−0.0056 (6)	0.0058 (5)	−0.0057 (6)
C13'	0.0182 (8)	0.0171 (9)	0.0183 (8)	−0.0033 (7)	0.0065 (7)	−0.0016 (8)
C14'	0.0185 (8)	0.0158 (9)	0.0159 (8)	−0.0036 (7)	0.0056 (7)	−0.0018 (7)
O14'	0.0252 (7)	0.0186 (7)	0.0158 (6)	−0.0081 (6)	0.0065 (5)	−0.0019 (6)
C15'	0.0238 (9)	0.0186 (10)	0.0187 (8)	−0.0033 (8)	0.0092 (7)	−0.0024 (8)
O15'	0.0215 (7)	0.0215 (8)	0.0199 (7)	−0.0053 (6)	0.0064 (5)	0.0021 (6)
N21	0.0189 (7)	0.0209 (9)	0.0170 (7)	−0.0038 (7)	0.0049 (6)	−0.0021 (7)
C22	0.0216 (9)	0.0254 (11)	0.0223 (9)	−0.0087 (9)	0.0085 (7)	−0.0035 (9)
N23	0.0198 (7)	0.0244 (10)	0.0215 (8)	−0.0069 (8)	0.0069 (6)	−0.0030 (8)
C24	0.0145 (7)	0.0188 (9)	0.0176 (8)	−0.0005 (8)	0.0042 (6)	0.0007 (8)
C25	0.0125 (7)	0.0192 (9)	0.0180 (8)	−0.0012 (7)	0.0037 (6)	0.0014 (8)
C26	0.0142 (7)	0.0190 (9)	0.0201 (8)	−0.0001 (7)	0.0046 (7)	0.0004 (8)
C27	0.0189 (8)	0.0214 (10)	0.0211 (9)	−0.0061 (8)	0.0049 (7)	−0.0005 (8)
C28	0.0189 (8)	0.0216 (10)	0.0206 (9)	−0.0071 (8)	0.0039 (7)	−0.0021 (8)
N29	0.0155 (7)	0.0206 (8)	0.0178 (7)	−0.0040 (7)	0.0045 (6)	−0.0004 (7)
C210	0.0233 (9)	0.0291 (11)	0.0175 (9)	−0.0048 (9)	0.0052 (7)	−0.0058 (9)
C211	0.0230 (9)	0.0308 (12)	0.0186 (9)	−0.0010 (9)	0.0064 (7)	−0.0024 (9)
N212	0.0196 (7)	0.0257 (10)	0.0189 (7)	−0.0027 (7)	0.0070 (6)	−0.0004 (7)
C21'	0.0147 (8)	0.0199 (9)	0.0155 (8)	−0.0011 (7)	0.0036 (6)	0.0006 (7)
C22'	0.0183 (8)	0.0188 (10)	0.0192 (8)	0.0042 (8)	0.0030 (7)	0.0006 (8)
O23'	0.0223 (6)	0.0169 (7)	0.0211 (7)	0.0019 (6)	0.0098 (5)	−0.0021 (6)
C23'	0.0178 (8)	0.0149 (9)	0.0167 (8)	0.0018 (7)	0.0058 (7)	0.0005 (7)
C24'	0.0166 (8)	0.0137 (9)	0.0158 (8)	0.0015 (7)	0.0052 (6)	−0.0009 (7)
O24'	0.0203 (6)	0.0176 (7)	0.0150 (6)	0.0040 (6)	0.0024 (5)	−0.0010 (5)
C25'	0.0174 (8)	0.0162 (9)	0.0176 (8)	0.0015 (7)	0.0042 (7)	0.0000 (7)
O25'	0.0185 (6)	0.0192 (7)	0.0197 (6)	0.0044 (6)	0.0060 (5)	0.0034 (6)
O100	0.0315 (9)	0.0542 (14)	0.0414 (10)	0.0025 (10)	0.0114 (8)	0.0174 (10)

Geometric parameters (Å, º)

N11—C12	1.379 (3)	N21—C26	1.394 (3)
N11—C16	1.396 (3)	N21—C210	1.397 (3)
N11—C110	1.399 (3)	C22—N23	1.299 (3)
C12—N13	1.300 (3)	C22—H22	0.9500
C12—H12	0.9500	N23—C24	1.364 (3)
N13—C14	1.365 (3)	C24—N29	1.367 (3)
C14—N19	1.369 (3)	C24—C25	1.397 (3)
C14—C15	1.397 (3)	C25—C26	1.415 (3)
C15—C16	1.410 (3)	C25—C27	1.426 (3)
C15—C17	1.423 (3)	C26—N212	1.325 (2)
C16—N112	1.322 (2)	C27—C28	1.371 (3)
C17—C18	1.368 (3)	C27—H27	0.9500
C17—H17	0.9500	C28—N29	1.381 (3)
C18—N19	1.382 (3)	C28—H28	0.9500
C18—H18	0.9500	N29—C21'	1.449 (2)
N19—C11'	1.451 (2)	C210—C211	1.354 (3)
C110—C111	1.355 (3)	C210—H210	0.9500
C110—H110	0.9500	C211—N212	1.389 (3)
C111—N112	1.390 (3)	C211—H211	0.9500
C111—H111	0.9500	C21'—O24'	1.441 (2)
C11'—O14'	1.436 (2)	C21'—C22'	1.538 (3)
C11'—C12'	1.537 (3)	C21'—H21B	1.0000
C11'—H11C	1.0000	C22'—C23'	1.529 (3)
C12'—C13'	1.531 (3)	C22'—H22B	0.9900
C12'—H12B	0.9900	C22'—H22C	0.9900
C12'—H12C	0.9900	O23'—C23'	1.417 (2)
O13'—C13'	1.416 (2)	O23'—H23'	0.8400
O13'—H13'	0.8400	C23'—C24'	1.524 (3)
C13'—C14'	1.524 (3)	C23'—H23C	1.0000
C13'—H13C	1.0000	C24'—O24'	1.432 (2)
C14'—O14'	1.437 (2)	C24'—C25'	1.507 (3)
C14'—C15'	1.508 (3)	C24'—H24A	1.0000
C14'—H14A	1.0000	C25'—O25'	1.427 (3)
C15'—O15'	1.423 (3)	C25'—H25B	0.9900
C15'—H15B	0.9900	C25'—H25C	0.9900
C15'—H15C	0.9900	O25'—H25'	0.8400
O15'—H15'	0.8400	O100—H101	0.9601
N21—C22	1.373 (3)	O100—H102	0.9602
C12—N11—C16	123.65 (17)	C22—N21—C210	129.30 (19)
C12—N11—C110	129.14 (19)	C26—N21—C210	106.95 (17)
C16—N11—C110	107.19 (17)	N23—C22—N21	122.8 (2)
N13—C12—N11	122.59 (19)	N23—C22—H22	118.6
N13—C12—H12	118.7	N21—C22—H22	118.6
N11—C12—H12	118.7	C22—N23—C24	114.90 (18)
C12—N13—C14	114.89 (18)	N23—C24—N29	124.18 (18)
N13—C14—N19	123.81 (17)	N23—C24—C25	127.47 (19)
N13—C14—C15	127.61 (18)	N29—C24—C25	108.33 (18)
N19—C14—C15	108.55 (18)	C24—C25—C26	115.85 (18)
C14—C15—C16	115.92 (18)	C24—C25—C27	107.20 (17)
C14—C15—C17	107.12 (17)	C26—C25—C27	136.94 (19)
C16—C15—C17	136.95 (19)	N212—C26—N21	110.89 (18)
N112—C16—N11	110.55 (18)	N212—C26—C25	133.9 (2)
N112—C16—C15	134.1 (2)	N21—C26—C25	115.23 (17)
N11—C16—C15	115.33 (17)	C28—C27—C25	106.45 (18)
C18—C17—C15	106.49 (18)	C28—C27—H27	126.8
C18—C17—H17	126.8	C25—C27—H27	126.8
C15—C17—H17	126.8	C27—C28—N29	109.68 (19)
C17—C18—N19	110.01 (19)	C27—C28—H28	125.2
C17—C18—H18	125.0	N29—C28—H28	125.2
N19—C18—H18	125.0	C24—N29—C28	108.33 (17)
C14—N19—C18	107.82 (17)	C24—N29—C21'	125.18 (17)
C14—N19—C11'	124.89 (17)	C28—N29—C21'	126.48 (18)
C18—N19—C11'	127.28 (17)	C211—C210—N21	105.0 (2)
C111—C110—N11	104.81 (19)	C211—C210—H210	127.5
C111—C110—H110	127.6	N21—C210—H210	127.5
N11—C110—H110	127.6	C210—C211—N212	112.09 (19)
C110—C111—N112	112.01 (19)	C210—C211—H211	124.0
C110—C111—H111	124.0	N212—C211—H211	124.0
N112—C111—H111	124.0	C26—N212—C211	105.04 (18)
C16—N112—C111	105.44 (18)	O24'—C21'—N29	108.68 (15)
O14'—C11'—N19	108.50 (15)	O24'—C21'—C22'	106.79 (15)
O14'—C11'—C12'	107.01 (15)	N29—C21'—C22'	113.64 (18)
N19—C11'—C12'	113.50 (18)	O24'—C21'—H21B	109.2
O14'—C11'—H11C	109.2	N29—C21'—H21B	109.2
N19—C11'—H11C	109.2	C22'—C21'—H21B	109.2
C12'—C11'—H11C	109.2	C23'—C22'—C21'	103.08 (16)
C13'—C12'—C11'	103.30 (16)	C23'—C22'—H22B	111.1
C13'—C12'—H12B	111.1	C21'—C22'—H22B	111.1
C11'—C12'—H12B	111.1	C23'—C22'—H22C	111.1
C13'—C12'—H12C	111.1	C21'—C22'—H22C	111.1
C11'—C12'—H12C	111.1	H22B—C22'—H22C	109.1
H12B—C12'—H12C	109.1	C23'—O23'—H23'	109.5
C13'—O13'—H13'	109.5	O23'—C23'—C24'	111.71 (16)
O13'—C13'—C14'	112.06 (17)	O23'—C23'—C22'	113.13 (16)
O13'—C13'—C12'	112.60 (16)	C24'—C23'—C22'	100.92 (16)
C14'—C13'—C12'	101.13 (17)	O23'—C23'—H23C	110.3
O13'—C13'—H13C	110.3	C24'—C23'—H23C	110.3
C14'—C13'—H13C	110.3	C22'—C23'—H23C	110.3
C12'—C13'—H13C	110.3	O24'—C24'—C25'	110.45 (15)
O14'—C14'—C15'	109.74 (16)	O24'—C24'—C23'	104.08 (15)
O14'—C14'—C13'	104.09 (15)	C25'—C24'—C23'	114.18 (17)
C15'—C14'—C13'	114.29 (17)	O24'—C24'—H24A	109.3
O14'—C14'—H14A	109.5	C25'—C24'—H24A	109.3
C15'—C14'—H14A	109.5	C23'—C24'—H24A	109.3
C13'—C14'—H14A	109.5	C24'—O24'—C21'	108.25 (15)
C11'—O14'—C14'	108.23 (15)	O25'—C25'—C24'	110.91 (17)
O15'—C15'—C14'	111.68 (18)	O25'—C25'—H25B	109.5
O15'—C15'—H15B	109.3	C24'—C25'—H25B	109.5
C14'—C15'—H15B	109.3	O25'—C25'—H25C	109.5
O15'—C15'—H15C	109.3	C24'—C25'—H25C	109.5
C14'—C15'—H15C	109.3	H25B—C25'—H25C	108.0
H15B—C15'—H15C	107.9	C25'—O25'—H25'	109.5
C15'—O15'—H15'	109.5	H101—O100—H102	106.0
C22—N21—C26	123.62 (18)
C16—N11—C12—N13	1.4 (3)	C26—N21—C22—N23	2.5 (4)
C110—N11—C12—N13	179.8 (2)	C210—N21—C22—N23	177.7 (2)
N11—C12—N13—C14	−0.8 (3)	N21—C22—N23—C24	0.3 (3)
C12—N13—C14—N19	−178.1 (2)	C22—N23—C24—N29	−179.7 (2)
C12—N13—C14—C15	−0.5 (3)	C22—N23—C24—C25	−1.4 (3)
N13—C14—C15—C16	1.1 (3)	N23—C24—C25—C26	−0.2 (3)
N19—C14—C15—C16	179.03 (18)	N29—C24—C25—C26	178.42 (18)
N13—C14—C15—C17	−178.0 (2)	N23—C24—C25—C27	−179.3 (2)
N19—C14—C15—C17	−0.1 (2)	N29—C24—C25—C27	−0.7 (2)
C12—N11—C16—N112	178.6 (2)	C22—N21—C26—N212	176.1 (2)
C110—N11—C16—N112	−0.1 (2)	C210—N21—C26—N212	0.0 (2)
C12—N11—C16—C15	−0.6 (3)	C22—N21—C26—C25	−3.9 (3)
C110—N11—C16—C15	−179.33 (18)	C210—N21—C26—C25	179.98 (19)
C14—C15—C16—N112	−179.5 (2)	C24—C25—C26—N212	−177.3 (2)
C17—C15—C16—N112	−0.7 (4)	C27—C25—C26—N212	1.5 (4)
C14—C15—C16—N11	−0.5 (3)	C24—C25—C26—N21	2.6 (3)
C17—C15—C16—N11	178.3 (2)	C27—C25—C26—N21	−178.5 (2)
C14—C15—C17—C18	0.0 (2)	C24—C25—C27—C28	0.4 (2)
C16—C15—C17—C18	−178.8 (2)	C26—C25—C27—C28	−178.5 (2)
C15—C17—C18—N19	0.1 (3)	C25—C27—C28—N29	0.0 (3)
N13—C14—N19—C18	178.2 (2)	N23—C24—N29—C28	179.4 (2)
C15—C14—N19—C18	0.1 (2)	C25—C24—N29—C28	0.8 (2)
N13—C14—N19—C11'	−2.7 (3)	N23—C24—N29—C21'	−1.3 (3)
C15—C14—N19—C11'	179.31 (18)	C25—C24—N29—C21'	−179.90 (19)
C17—C18—N19—C14	−0.1 (3)	C27—C28—N29—C24	−0.5 (3)
C17—C18—N19—C11'	−179.3 (2)	C27—C28—N29—C21'	−179.8 (2)
C12—N11—C110—C111	−178.2 (2)	C22—N21—C210—C211	−175.6 (2)
C16—N11—C110—C111	0.4 (2)	C26—N21—C210—C211	0.3 (3)
N11—C110—C111—N112	−0.6 (3)	N21—C210—C211—N212	−0.4 (3)
N11—C16—N112—C111	−0.3 (2)	N21—C26—N212—C211	−0.2 (2)
C15—C16—N112—C111	178.8 (2)	C25—C26—N212—C211	179.8 (2)
C110—C111—N112—C16	0.6 (3)	C210—C211—N212—C26	0.4 (3)
C14—N19—C11'—O14'	−107.7 (2)	C24—N29—C21'—O24'	−107.0 (2)
C18—N19—C11'—O14'	71.3 (3)	C28—N29—C21'—O24'	72.2 (3)
C14—N19—C11'—C12'	133.5 (2)	C24—N29—C21'—C22'	134.3 (2)
C18—N19—C11'—C12'	−47.5 (3)	C28—N29—C21'—C22'	−46.5 (3)
O14'—C11'—C12'—C13'	−12.9 (2)	O24'—C21'—C22'—C23'	−14.6 (2)
N19—C11'—C12'—C13'	106.80 (18)	N29—C21'—C22'—C23'	105.17 (18)
C11'—C12'—C13'—O13'	151.50 (17)	C21'—C22'—C23'—O23'	152.70 (17)
C11'—C12'—C13'—C14'	31.74 (19)	C21'—C22'—C23'—C24'	33.22 (19)
O13'—C13'—C14'—O14'	−160.61 (15)	O23'—C23'—C24'—O24'	−161.76 (15)
C12'—C13'—C14'—O14'	−40.46 (18)	C22'—C23'—C24'—O24'	−41.27 (18)
O13'—C13'—C14'—C15'	79.7 (2)	O23'—C23'—C24'—C25'	77.7 (2)
C12'—C13'—C14'—C15'	−160.16 (16)	C22'—C23'—C24'—C25'	−161.76 (16)
N19—C11'—O14'—C14'	−135.80 (17)	C25'—C24'—O24'—C21'	156.46 (16)
C12'—C11'—O14'—C14'	−13.0 (2)	C23'—C24'—O24'—C21'	33.49 (19)
C15'—C14'—O14'—C11'	156.64 (17)	N29—C21'—O24'—C24'	−134.58 (17)
C13'—C14'—O14'—C11'	33.9 (2)	C22'—C21'—O24'—C24'	−11.6 (2)
O14'—C14'—C15'—O15'	74.9 (2)	O24'—C24'—C25'—O25'	76.1 (2)
C13'—C14'—C15'—O15'	−168.66 (16)	C23'—C24'—C25'—O25'	−167.05 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13′—H13′···O15′^i	0.84	2.01	2.800 (2)	156
O15′—H15′···N112^ii	0.84	1.87	2.705 (2)	175
O23′—H23′···O25′^iii	0.84	1.84	2.665 (2)	165
O25′—H25′···N212^iv	0.84	1.84	2.675 (2)	174
O100—H101···O23′	0.96	1.91	2.823 (3)	157
O100—H102···O15′^i	0.96	1.92	2.868 (2)	169
C12—H12···O13′^v	0.95	2.37	3.241 (3)	153
C22—H22···O23′^vi	0.95	2.47	3.295 (3)	145
C210—H210···O100^vi	0.95	2.47	3.230 (4)	138

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