Regioisomeric 4-nitroindazole N¹- and N²-([beta]-D-ribonucleosides)

The structures of the isomeric nucleosides 4-nitro-1-([beta]-D-ribo­furan­osyl)-1H-indazole, C₁₂H₁₃N₃O₆, (I), and 4-nitro-2-([beta]-D-ribo­furan­osyl)-2H-indazole, C₁₂H₁₃N₃O₆, (II), have been determined. For compound (I), the conformation of the gly­cosylic bond is anti [[chi] = -93.6 (6)°] and the sugar puckering is C2'-exo-C3'-endo. Compound (II) shows two conformations in the crystalline state which differ mainly in the sugar pucker; type 1 adopts the C2'-endo-C3'-exo sugar puckering associated with a syn base orientation [[chi] = 43.7 (6)°] and type 2 shows C2'-exo-C3'-endo sugar puckering accompanied by a somewhat different syn base orientation [[chi] = 13.8 (6)°].

S1. Comment

Universal nucleosides, which base-pair equally well with the canonical four nucleic acid constituents - either ribonucleosides or 2'-deoxyribonucleosides - are categorized into two types, those forming base pairs by hydrogen-bonding and those whose stability depends mainly on stacking interactions. 5-Nitro-1H-indole 2'-deoxy-β-D-ribofuranoside, which has been incorporated in duplex DNA, shows such universal base-pairing properties. It belongs to the second category of universal nucleosides, which stabilize DNA by stacking interactions rather than by hydrogen-bonding (Loakes & Brown, 1994). Likewise, the regiosiomeric 4-nitroindazole 2'-deoxyribonucleosides have been shown to act as universal nucleosides, because they behave indiscriminately towards the four natural DNA constituents (Seela & Bourgeois, 1991; Seela & Jawalekar, 2002). Recently, the title regioisomeric 4-nitroindazole ribonucleosides, (I) and (II) have been prepared (Seela & Peng, 2003; Revankar & Townsend, 1970). Here, the single-crystal structure analyses of 4-nitroindazole N¹– and N²-(β-D-ribonucleosides), (I) and (II), are described. \sch

For the canonical ribonucleosides, the orientation of the base relative to the sugar (syn/anti) is defined by the torsion angle χ (O4'-C1'-N9—C4) (purine numbering; IUPAC-IUB Joint Commission on Biochemical Nomenclature, 1983). The preferred conformation at the N-glycosylic bond of the common purine nucleosides is usually anti (Saenger, 1989). By analogy, the torsion angle χ of compound (I) was defined as O4'-C1'-N1—C7a. For compound (II), the analogy is less straightforward, but the torsion angle related to χ is defined as O4'-C1'-N2—C3, as in the corresponding pyrazolo[3,4-d]pyrimidine (Seela & Debelak, 2000). The C2'-endo (S) and C3'-endo (N) puckerings are the most frequently observed sugar-ring conformations of nucleosides (Saenger, 1984a). Among these, ribonucleosides often show C3'-endo sugar puckering with a half-chair or envelope conformation.

The structure of (I) is shown in Fig. 1 and selected geometric parameters are summarized in Table 1 (systematic numbering is used throughout). For (I), the conformation of the glycosylic bond is between the anti and the high-anti range [χ = −93.6 (6)°], which was also observed for 1-(2-deoxy-β-D-erythropentofuranosyl)-4-nitro-1H-indazole [χ = −105.2 (5)°; Seela & Jawalekar, 2003], 2-(2'-deoxy-β-D-erythro-pentofuranosyl)-1H-pyrazolo[3,4-d]pyrimidine, (III) [χ = −100.4 (2)°; He et al., 2002] and pyrazolo[3,4-d]pyrimidine-4-amine 2'-deoxyribonucleoside [8-aza-7-deaza-2'-deoxyadenosine; χ = −106.3 (2)°; Seela et al., 1999]. The puckering of the ribose ring in (I) is C2'-exo-C3'-endo, showing an N-type sugar conformation (³T₂) with pseudorotation parameters (Saenger, 1984b) of P = 6.5 (4)° and τ_m = 38.3°. The torsion angle γ (O5'-C5'-C4'-C3') is 58.0 (7)°, which corresponds to +sc (Saenger, 1984b). In contrast, 4-nitro-1H-indazole 2'-deoxyribonucleoside displays S-type sugar puckering and the orientation of the exocyclic C4'-C5' bond is -sc (Seela & Jawalekar, 2003).

The base moiety of nucleoside (I) is nearly planar; the r.m.s. deviation of the ring atoms (N1/N2/C3—C7/C7a/C3a) from their calculated least-squares planes is 0.0218 Å, with a maximum deviation of 0.037 (4) Å for atom N1. However, the exocyclic substituents (nitro atom N4 and atom C1') show significant deviations from the plane [0.14 (1) and 0.052 (9) Å, respectively] and lie on the same side of the base.

The bases are strongly stacked in the crystal structure of (I). There are three intermolecular hydrogen bonds responsible for the packing of the molecules (Table 2). The O5'-H5'A···O2'(x − 1, y, z) bond connects molecules parallel to the a axis to form infinite chains in which the bases are stacked and parallel to each other (Fig. 2). Another two interchain hydrogen bonds, O3'-H3'A···O5'(1 − x, 1/2 + y, 1 − z) and O2'-H2'A···O4'(2 − x, 1/2 + y, 1 − z), are found linking two neighbouring chains.

Compound (II) differs from compound (I) only in the glycosylation position (N2 versus N1), yet it shows a significantly different structure in the crystalline state (Fig. 3). Slow crystallization of 4-nitro-2H-indazole N²-ribonucleoside from methanol gave crystals which consist of two forms of molecules, defined as type 1 and type 2, while nucleoside (I) displays only one structure. A comparison of these two different structures shows that both exhibit a syn conformation of the N-glycosylic bond, with different torsion angles: χ = 43.7 (6) for (II-1) and 13.8 (6)° for (II-2). 2-(2-Deoxy-β-D-erythropentofuranosyl)-2H-pyrazolo[3,4-d]pyrimidine, (IV), shows similar values (He et al., 2002). The structures of the nucleosides (II-1) and (II-2) are shown in Fig. 3.

The structures of (II-1) and (II-2) differ mainly in the sugar ring conformations (Table 3). For (II-2), the sugar shows N-type sugar puckering (P = 2.1°, C2'-exo-C3'-endo, ³T₂) with a puckering amplitude τ_m = 41.1°, which is very close to that of (I), whereas S-type sugar puckering (P = 185.4°, C2'-endo-C3'-exo, ₃T², τ_m = 40.6°) characterizes (II-1) (Saenger, 1984b). Both (II-1) and (II-2) display different conformations about the C4'-C5' bond: the former is -sc (-gauche) (Saenger, 1984b) with a torsion angle γ (O5'-C5'-C4'-C3') of −80.9 (5)°, whereas the latter is -ap (trans) (Saenger, 1984b) with γ = −176.1 (5)°.

The base moieties of compound (II) are nearly planar, showing maximum deviations of their C and N atoms from the least-squares plane in the range −0.007 (4)–0.005 (4) Å for (II-1) and −0.008 (4)–0.007 (3) Å for (II-2). The structure of nucleoside (II) is stabilized by several intermolecular hydrogen bonds between conformations (II-1) and (II-2) (Table 4 and Fig. 4), leading to the formation of layers. In every layer, each molecule links two neighbouring molecules of different conformations by four intermolecular hydrogen bonds, O12'-H12A···O22'(x, y − 1, z − 1), O13'-H13O···O23'(x − 1, y − 1, z), O22'-H22A···O13'(1 + x, 1 + y, 1 + z) and O23'-H23O···O15'(x, 1 + y, z). Two further hydrogen bonds between the sugar moieties and the adjacent nucleobase units are found linking molecules of identical conformation [O15'-H15A···N11(1 + x, y, 1 + z) for (II-1) and O25'-H25A···N21(x − 1, y, z − 1) for (II-2)].

Compounds (I) and (II) show different sugar conformations in the solid state; nucleoside (I) shows only the N conformation, but compound (II) displays two conformations, N and S. In solution, both regioisomers are observed to be a mixture of N– and S-conformers. The population of N– and S-conformers in D₂O solution is found to be 53% N and 47% S for nucleoside (I), and 51% N, 49% S for (II). This was shown by ¹H NMR spectroscopy using the vicinal [¹H,¹H] coupling constants and applying the PSEUROT 6.3 program (Van Wijk, et al., 1999).

S2. Experimental

The syntheses of compounds (I) and (II) has been published elsewhere (Seela & Peng, 2003). Both compounds were slowly crystallized from MeOH.

S3. Refinement

The known configuration of the sugar moiety was used to define the enantiomer employed in the refined model. All H atoms were initially found in a difference Fourier synthesis. In order to maximize the data/parameter ratio, H atoms bonded to C atoms were placed in geometrically idealized positions (C—H = 0.93–0.98 Å) and constrained to ride on their parent atoms, with U_iso(H) =?

Computing details

For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1999).

Figures

	Fig. 1. A perspective view of nucleoside (I) showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing in (I) viewed down the a axis, showing the intermolecular hydrogen bonding.
	Fig. 3. A perspective view of molecules 1 and 2 of nucleoside (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The hydrogen bonding within the double layers of the crystal structure of (II).

(I) 4-nitro-1-(β-D-ribofuranosyl)-1H-indazole

Crystal data

C12H13N3O6	F(000) = 308
Mr = 295.25	Dx = 1.525 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 30 reflections
a = 5.8912 (11) Å	θ = 6.1–12.5°
b = 10.0825 (12) Å	µ = 0.12 mm^−1
c = 11.0998 (17) Å	T = 293 K
β = 102.821 (15)°	Block, yellow
V = 642.87 (17) Å^3	0.6 × 0.4 × 0.3 mm
Z = 2

Data collection

Bruker P4 diffractometer	Rint = 0.043
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 1.9°
Graphite monochromator	h = −8→1
2θ/ω scans	k = −1→14
2712 measured reflections	l = −15→15
1960 independent reflections	3 standard reflections every 97 reflections
1659 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0654P)^2 + 0.0968P] where P = (Fo^2 + 2Fc^2)/3
1960 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.30 e Å^−3
4 restraints	Δρmin = −0.28 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	0.6080 (8)	0.6039 (5)	0.2903 (4)	0.0346 (10)
N2	0.4098 (9)	0.6777 (6)	0.2767 (5)	0.0397 (11)
C3	0.2652 (10)	0.6334 (7)	0.1758 (5)	0.0392 (12)
H3A	0.1166	0.6668	0.1448	0.047*
C3a	0.3671 (10)	0.5285 (6)	0.1216 (5)	0.0356 (11)
N4	0.0918 (12)	0.4695 (7)	−0.0746 (5)	0.0539 (16)
C4	0.3107 (12)	0.4470 (7)	0.0163 (6)	0.0444 (14)
C5	0.4584 (15)	0.3499 (9)	−0.0048 (8)	0.060 (2)
H5A	0.4169	0.2953	−0.0737	0.072*
C6	0.6748 (15)	0.3329 (9)	0.0791 (7)	0.062 (2)
H6A	0.7738	0.2660	0.0643	0.074*
C7	0.7440 (13)	0.4113 (7)	0.1813 (6)	0.0455 (15)
H7A	0.8872	0.3995	0.2358	0.055*
C7a	0.5883 (10)	0.5102 (6)	0.1997 (5)	0.0334 (11)
O41	0.0459 (12)	0.3977 (8)	−0.1664 (5)	0.081 (2)
O42	−0.0332 (11)	0.5603 (8)	−0.0565 (5)	0.0720 (17)
C1'	0.8022 (9)	0.6260 (5)	0.3942 (5)	0.0301 (10)
H1'A	0.9456	0.5946	0.3727	0.036*
O2'	1.0679 (7)	0.7948 (4)	0.4819 (5)	0.0402 (10)
H2'A	1.105 (15)	0.875 (12)	0.488 (9)	0.060*
C2'	0.8311 (9)	0.7726 (5)	0.4315 (5)	0.0302 (10)
H2'B	0.7707	0.8316	0.3617	0.036*
O3'	0.7413 (8)	0.8866 (4)	0.6129 (4)	0.0410 (10)
H3'A	0.703 (17)	0.953 (12)	0.575 (8)	0.061*
C3'	0.6872 (9)	0.7813 (5)	0.5308 (5)	0.0286 (10)
H3'B	0.5214	0.7847	0.4907	0.034*
O4'	0.7690 (7)	0.5565 (4)	0.5004 (3)	0.0349 (9)
C4'	0.7416 (9)	0.6481 (6)	0.5973 (5)	0.0306 (10)
H4'A	0.8900	0.6553	0.6578	0.037*
O5'	0.3376 (8)	0.5771 (5)	0.5793 (5)	0.0491 (11)
H5'A	0.274 (16)	0.648 (6)	0.556 (9)	0.074*
C5'	0.5591 (11)	0.5946 (7)	0.6609 (5)	0.0415 (13)
H5'B	0.6115	0.5101	0.6988	0.050*
H5'C	0.5426	0.6552	0.7263	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.035 (2)	0.034 (2)	0.033 (2)	0.005 (2)	0.0036 (17)	−0.0066 (19)
N2	0.035 (2)	0.042 (3)	0.038 (2)	0.009 (2)	0.0006 (18)	−0.004 (2)
C3	0.035 (3)	0.042 (3)	0.038 (3)	0.002 (3)	0.002 (2)	0.002 (2)
C3a	0.039 (3)	0.035 (3)	0.031 (2)	−0.005 (2)	0.005 (2)	0.001 (2)
N4	0.061 (4)	0.050 (3)	0.043 (3)	−0.020 (3)	−0.006 (3)	−0.001 (3)
C4	0.050 (3)	0.041 (3)	0.038 (3)	−0.011 (3)	0.000 (2)	−0.005 (3)
C5	0.073 (5)	0.050 (4)	0.050 (3)	−0.004 (4)	0.001 (3)	−0.022 (3)
C6	0.071 (5)	0.049 (4)	0.063 (4)	0.014 (4)	0.008 (4)	−0.020 (4)
C7	0.049 (3)	0.040 (3)	0.045 (3)	0.006 (3)	0.005 (3)	−0.007 (3)
C7a	0.039 (3)	0.029 (2)	0.032 (2)	−0.003 (2)	0.007 (2)	−0.003 (2)
O41	0.091 (4)	0.084 (5)	0.054 (3)	−0.017 (4)	−0.015 (3)	−0.023 (3)
O42	0.060 (3)	0.070 (4)	0.071 (3)	0.002 (3)	−0.019 (3)	−0.012 (3)
C1'	0.029 (2)	0.027 (2)	0.033 (2)	0.001 (2)	0.0041 (18)	−0.003 (2)
O2'	0.031 (2)	0.027 (2)	0.061 (3)	−0.0036 (16)	0.0071 (17)	−0.0017 (19)
C2'	0.031 (2)	0.023 (2)	0.035 (2)	0.001 (2)	0.0042 (19)	0.000 (2)
O3'	0.049 (2)	0.0283 (19)	0.041 (2)	0.0023 (19)	0.0009 (19)	−0.0101 (17)
C3'	0.028 (2)	0.025 (2)	0.029 (2)	0.001 (2)	0.0003 (17)	−0.0035 (19)
O4'	0.045 (2)	0.0225 (17)	0.0359 (18)	0.0030 (17)	0.0057 (16)	0.0002 (15)
C4'	0.030 (2)	0.027 (2)	0.031 (2)	0.001 (2)	−0.0006 (18)	−0.0018 (19)
O5'	0.034 (2)	0.035 (2)	0.073 (3)	−0.0031 (19)	0.004 (2)	0.004 (2)
C5'	0.042 (3)	0.042 (3)	0.038 (3)	−0.005 (3)	0.005 (2)	0.004 (2)

Geometric parameters (Å, º)

N1—N2	1.364 (7)	C1'—O4'	1.422 (6)
N1—C7a	1.366 (7)	C1'—C2'	1.534 (8)
N1—C1'	1.450 (6)	C1'—H1'A	0.9800
N2—C3	1.325 (7)	O2'—C2'	1.401 (7)
C3—C3a	1.415 (9)	O2'—H2'A	0.84 (12)
C3—H3A	0.9300	C2'—C3'	1.534 (7)
C3a—C4	1.407 (8)	C2'—H2'B	0.9800
C3a—C7a	1.408 (8)	O3'—C3'	1.390 (6)
N4—O42	1.220 (10)	O3'—H3'A	0.80 (12)
N4—O41	1.230 (8)	C3'—C4'	1.532 (8)
N4—C4	1.468 (9)	C3'—H3'B	0.9800
C4—C5	1.364 (11)	O4'—C4'	1.453 (7)
C5—C6	1.412 (12)	C4'—C5'	1.511 (9)
C5—H5A	0.9300	C4'—H4'A	0.9800
C6—C7	1.369 (10)	O5'—C5'	1.425 (7)
C6—H6A	0.9300	O5'—H5'A	0.82 (4)
C7—C7a	1.400 (9)	C5'—H5'B	0.9700
C7—H7A	0.9300	C5'—H5'C	0.9700
N2—N1—C7a	111.4 (5)	O4'—C1'—H1'A	109.1
N2—N1—C1'	120.6 (4)	N1—C1'—H1'A	109.1
C7a—N1—C1'	127.9 (5)	C2'—C1'—H1'A	109.1
C3—N2—N1	106.5 (5)	C2'—O2'—H2'A	114 (6)
N2—C3—C3a	110.9 (5)	O2'—C2'—C3'	111.4 (4)
N2—C3—H3A	124.5	O2'—C2'—C1'	107.6 (4)
C3a—C3—H3A	124.5	C3'—C2'—C1'	101.7 (4)
C4—C3a—C7a	116.8 (6)	O2'—C2'—H2'B	111.9
C4—C3a—C3	138.2 (6)	C3'—C2'—H2'B	111.9
C7a—C3a—C3	105.0 (5)	C1'—C2'—H2'B	111.9
O42—N4—O41	123.3 (7)	C3'—O3'—H3'A	108 (7)
O42—N4—C4	118.2 (6)	O3'—C3'—C4'	111.1 (4)
O41—N4—C4	118.5 (7)	O3'—C3'—C2'	115.6 (4)
C5—C4—C3a	121.3 (6)	C4'—C3'—C2'	101.9 (4)
C5—C4—N4	119.3 (6)	O3'—C3'—H3'B	109.3
C3a—C4—N4	119.4 (6)	C4'—C3'—H3'B	109.3
C4—C5—C6	119.4 (6)	C2'—C3'—H3'B	109.3
C4—C5—H5A	120.3	C1'—O4'—C4'	111.0 (4)
C6—C5—H5A	120.3	O4'—C4'—C5'	109.1 (5)
C7—C6—C5	122.4 (7)	O4'—C4'—C3'	104.3 (4)
C7—C6—H6A	118.8	C5'—C4'—C3'	116.3 (5)
C5—C6—H6A	118.8	O4'—C4'—H4'A	109.0
C6—C7—C7a	116.6 (6)	C5'—C4'—H4'A	109.0
C6—C7—H7A	121.7	C3'—C4'—H4'A	109.0
C7a—C7—H7A	121.7	C5'—O5'—H5'A	112 (7)
N1—C7a—C7	130.4 (5)	O5'—C5'—C4'	113.1 (5)
N1—C7a—C3a	106.2 (5)	O5'—C5'—H5'B	108.9
C7—C7a—C3a	123.4 (5)	C4'—C5'—H5'B	108.9
O4'—C1'—N1	110.8 (4)	O5'—C5'—H5'C	108.9
O4'—C1'—C2'	106.1 (4)	C4'—C5'—H5'C	108.9
N1—C1'—C2'	112.5 (4)	H5'B—C5'—H5'C	107.8
C7a—N1—N2—C3	−1.4 (7)	C4—C3a—C7a—C7	−4.0 (9)
C1'—N1—N2—C3	−179.0 (5)	C3—C3a—C7a—C7	177.5 (6)
N1—N2—C3—C3a	0.3 (7)	N2—N1—C1'—O4'	83.5 (6)
N2—C3—C3a—C4	−177.0 (7)	C7a—N1—C1'—O4'	−93.6 (6)
N2—C3—C3a—C7a	0.9 (7)	N2—N1—C1'—C2'	−35.2 (7)
C7a—C3a—C4—C5	3.7 (10)	C7a—N1—C1'—C2'	147.7 (5)
C3—C3a—C4—C5	−178.5 (8)	O4'—C1'—C2'—O2'	88.2 (5)
C7a—C3a—C4—N4	−174.4 (6)	N1—C1'—C2'—O2'	−150.4 (4)
C3—C3a—C4—N4	3.3 (12)	O4'—C1'—C2'—C3'	−28.9 (5)
O42—N4—C4—C5	−177.1 (8)	N1—C1'—C2'—C3'	92.4 (5)
O41—N4—C4—C5	1.5 (10)	O2'—C2'—C3'—O3'	44.0 (6)
O42—N4—C4—C3a	1.1 (10)	C1'—C2'—C3'—O3'	158.4 (4)
O41—N4—C4—C3a	179.7 (7)	O2'—C2'—C3'—C4'	−76.6 (5)
C3a—C4—C5—C6	−1.6 (12)	C1'—C2'—C3'—C4'	37.8 (5)
N4—C4—C5—C6	176.5 (8)	N1—C1'—O4'—C4'	−114.4 (5)
C4—C5—C6—C7	−0.5 (14)	C2'—C1'—O4'—C4'	8.0 (5)
C5—C6—C7—C7a	0.3 (13)	C1'—O4'—C4'—C5'	141.4 (5)
N2—N1—C7a—C7	−177.2 (7)	C1'—O4'—C4'—C3'	16.5 (5)
C1'—N1—C7a—C7	0.1 (10)	O3'—C3'—C4'—O4'	−157.5 (4)
N2—N1—C7a—C3a	2.0 (6)	C2'—C3'—C4'—O4'	−33.8 (5)
C1'—N1—C7a—C3a	179.3 (5)	O3'—C3'—C4'—C5'	82.4 (6)
C6—C7—C7a—N1	−178.9 (7)	C2'—C3'—C4'—C5'	−153.9 (5)
C6—C7—C7a—C3a	2.1 (10)	O4'—C4'—C5'—O5'	−59.5 (7)
C4—C3a—C7a—N1	176.7 (5)	C3'—C4'—C5'—O5'	58.0 (7)
C3—C3a—C7a—N1	−1.7 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2′A···O4′^i	0.84 (12)	1.96 (12)	2.800 (6)	173 (9)
O3′—H3′A···O5′^ii	0.80 (12)	2.09 (11)	2.832 (7)	154 (10)
O5′—H5′A···O2′^iii	0.82 (4)	1.97 (5)	2.784 (7)	168 (10)

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

(II) 4-nitro-2-(β-D-ribofuranosyl)-2H-indazole

Crystal data

C12H13N3O6	F(000) = 616
Mr = 295.25	Dx = 1.560 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 44 reflections
a = 4.9355 (13) Å	θ = 4.5–12.4°
b = 35.936 (5) Å	µ = 0.13 mm^−1
c = 7.1833 (9) Å	T = 293 K
β = 99.311 (18)°	Block, yellow
V = 1257.2 (4) Å^3	0.4 × 0.3 × 0.2 mm
Z = 4

Data collection

Bruker P4 diffractometer	Rint = 0.048
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 2.3°
Graphite monochromator	h = −1→6
2θ/ω scans	k = −1→50
4996 measured reflections	l = −10→10
3706 independent reflections	3 standard reflections every 97 reflections
2657 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0767P)^2 + 0.5939P] where = P = (Fo^2 + 2Fc^2)/3
3706 reflections	(Δ/σ)max < 0.001
397 parameters	Δρmax = 0.30 e Å^−3
13 restraints	Δρmin = −0.36 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
N11	0.1287 (8)	0.04844 (12)	−0.1019 (5)	0.0307 (8)
N12	0.2705 (7)	0.04215 (11)	0.0735 (5)	0.0277 (8)
C13	0.4826 (9)	0.06543 (15)	0.1242 (6)	0.0320 (10)
H13A	0.6023	0.0656	0.2384	0.038*
C13a	0.4872 (9)	0.08891 (13)	−0.0265 (6)	0.0299 (9)
C14	0.6476 (10)	0.11968 (14)	−0.0715 (7)	0.0338 (10)
N14	0.8820 (9)	0.13200 (14)	0.0645 (7)	0.0440 (11)
O141	1.0196 (10)	0.15791 (14)	0.0239 (8)	0.0624 (12)
O142	0.9295 (10)	0.11460 (15)	0.2138 (7)	0.0669 (14)
C15	0.5860 (12)	0.13696 (15)	−0.2421 (8)	0.0405 (12)
H15D	0.6931	0.1568	−0.2708	0.049*
C16	0.3612 (12)	0.12499 (17)	−0.3753 (7)	0.0457 (13)
H16C	0.3227	0.1373	−0.4903	0.055*
C17	0.1982 (11)	0.09591 (16)	−0.3414 (7)	0.0401 (12)
H17B	0.0506	0.0884	−0.4307	0.048*
C17a	0.2623 (9)	0.07767 (14)	−0.1649 (6)	0.0297 (9)
C11'	0.1828 (8)	0.01156 (13)	0.1843 (6)	0.0263 (9)
H11A	−0.0051	0.0044	0.1308	0.032*
O12'	0.2859 (7)	−0.04550 (11)	0.0358 (4)	0.0363 (8)
H12A	0.422 (4)	−0.0552 (15)	0.004 (6)	0.054*
C12'	0.3690 (8)	−0.02250 (13)	0.1931 (5)	0.0249 (8)
H12C	0.5597	−0.0146	0.1957	0.030*
O13'	0.0729 (7)	−0.05681 (11)	0.3563 (4)	0.0372 (8)
H13O	0.062 (7)	−0.0692 (15)	0.451 (5)	0.056*
C13'	0.3344 (8)	−0.03872 (14)	0.3849 (6)	0.0286 (9)
H13B	0.4844	−0.0556	0.4356	0.034*
O14'	0.1892 (6)	0.02362 (10)	0.3708 (4)	0.0317 (7)
C14'	0.3305 (8)	−0.00384 (14)	0.5020 (6)	0.0278 (9)
H14A	0.2243	−0.0083	0.6038	0.033*
O15'	0.7219 (8)	−0.00780 (12)	0.7486 (5)	0.0447 (9)
H15A	0.841 (11)	0.0049 (10)	0.812 (5)	0.067*
C15'	0.6117 (9)	0.01193 (14)	0.5841 (6)	0.0327 (10)
H15B	0.7343	0.0099	0.4918	0.039*
H15C	0.5941	0.0381	0.6140	0.039*
N21	1.1154 (8)	0.80507 (12)	1.1277 (5)	0.0340 (9)
N22	0.9196 (7)	0.81226 (11)	0.9763 (5)	0.0268 (8)
C23	0.9253 (10)	0.78854 (14)	0.8319 (6)	0.0322 (9)
H23A	0.8084	0.7887	0.7165	0.039*
C23a	1.1395 (10)	0.76383 (14)	0.8883 (6)	0.0318 (10)
C24	1.2616 (11)	0.73328 (16)	0.8120 (7)	0.0387 (11)
N24	1.1518 (13)	0.72039 (17)	0.6225 (8)	0.0620 (15)
O241	1.2554 (14)	0.6934 (2)	0.5598 (9)	0.103 (2)
O242	0.9577 (16)	0.7366 (2)	0.5374 (8)	0.115 (3)
C25	1.4811 (12)	0.71482 (17)	0.9150 (8)	0.0460 (13)
H25D	1.5581	0.6944	0.8638	0.055*
C26	1.5884 (11)	0.72722 (17)	1.0990 (9)	0.0467 (13)
H26C	1.7395	0.7151	1.1665	0.056*
C27	1.4763 (11)	0.75648 (17)	1.1799 (8)	0.0454 (13)
H27B	1.5471	0.7639	1.3021	0.054*
C27a	1.2508 (10)	0.77532 (13)	1.0752 (6)	0.0313 (9)
C21'	0.7426 (9)	0.84488 (13)	0.9856 (5)	0.0265 (8)
H21A	0.6699	0.8448	1.1048	0.032*
O22'	0.7675 (6)	0.91074 (10)	1.0459 (4)	0.0309 (7)
H22A	0.882 (4)	0.9220 (11)	1.121 (7)	0.046*
C22'	0.9010 (8)	0.88093 (13)	0.9679 (6)	0.0243 (8)
H22C	1.0950	0.8789	1.0242	0.029*
O23'	0.9200 (7)	0.91993 (10)	0.6844 (4)	0.0338 (7)
H23O	0.865 (12)	0.9361 (3)	0.749 (6)	0.051*
C23'	0.8612 (8)	0.88460 (13)	0.7526 (6)	0.0251 (8)
H23B	0.9788	0.8662	0.7040	0.030*
O24'	0.5244 (6)	0.84386 (10)	0.8324 (4)	0.0294 (7)
C24'	0.5626 (8)	0.87262 (13)	0.6954 (5)	0.0257 (8)
H24A	0.4409	0.8937	0.7080	0.031*
O25'	0.2127 (8)	0.84913 (17)	0.4553 (6)	0.0644 (15)
H25A	0.187 (4)	0.834 (2)	0.367 (9)	0.097*
C25'	0.4981 (10)	0.85686 (15)	0.4971 (6)	0.0337 (10)
H25B	0.5484	0.8747	0.4072	0.040*
H25C	0.6024	0.8342	0.4883	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0287 (17)	0.039 (2)	0.0223 (16)	0.0028 (17)	−0.0020 (13)	0.0041 (16)
N12	0.0247 (16)	0.036 (2)	0.0201 (15)	0.0004 (15)	−0.0035 (12)	0.0016 (14)
C13	0.029 (2)	0.041 (3)	0.0238 (19)	−0.0022 (19)	−0.0041 (16)	0.0035 (18)
C13a	0.029 (2)	0.035 (3)	0.025 (2)	0.0012 (18)	0.0006 (16)	0.0020 (17)
C14	0.034 (2)	0.033 (3)	0.033 (2)	−0.0044 (19)	0.0029 (18)	0.0017 (19)
N14	0.038 (2)	0.043 (3)	0.050 (3)	−0.012 (2)	0.0047 (19)	−0.001 (2)
O141	0.049 (2)	0.057 (3)	0.080 (3)	−0.018 (2)	0.007 (2)	0.004 (2)
O142	0.061 (3)	0.080 (4)	0.051 (2)	−0.027 (2)	−0.018 (2)	0.016 (2)
C15	0.048 (3)	0.034 (3)	0.041 (3)	−0.003 (2)	0.010 (2)	0.011 (2)
C16	0.057 (3)	0.046 (3)	0.032 (2)	0.007 (3)	0.003 (2)	0.018 (2)
C17	0.050 (3)	0.040 (3)	0.027 (2)	0.005 (2)	−0.004 (2)	0.004 (2)
C17a	0.029 (2)	0.037 (3)	0.0217 (18)	0.0013 (19)	0.0011 (15)	0.0024 (18)
C11'	0.0232 (18)	0.033 (2)	0.0221 (18)	−0.0004 (17)	0.0029 (14)	−0.0009 (17)
O12'	0.0368 (17)	0.045 (2)	0.0277 (15)	−0.0016 (16)	0.0079 (13)	−0.0099 (14)
C12'	0.0217 (18)	0.032 (2)	0.0217 (17)	−0.0064 (16)	0.0047 (14)	−0.0017 (16)
O13'	0.0357 (17)	0.053 (2)	0.0216 (14)	−0.0188 (16)	0.0018 (12)	0.0039 (14)
C13'	0.0225 (19)	0.038 (3)	0.0240 (18)	−0.0048 (18)	0.0012 (15)	0.0008 (18)
O14'	0.0323 (16)	0.0404 (19)	0.0223 (14)	0.0092 (14)	0.0040 (12)	−0.0001 (13)
C14'	0.0224 (18)	0.040 (3)	0.0203 (17)	−0.0034 (18)	0.0028 (14)	0.0035 (18)
O15'	0.0404 (19)	0.056 (3)	0.0318 (17)	−0.0054 (17)	−0.0121 (14)	−0.0022 (17)
C15'	0.029 (2)	0.038 (3)	0.030 (2)	−0.0058 (19)	−0.0002 (16)	−0.0048 (19)
N21	0.038 (2)	0.038 (2)	0.0224 (16)	0.0033 (18)	−0.0055 (15)	−0.0031 (16)
N22	0.0299 (18)	0.029 (2)	0.0200 (15)	−0.0012 (15)	0.0005 (13)	−0.0016 (14)
C23	0.037 (2)	0.032 (2)	0.0246 (19)	0.0023 (19)	−0.0031 (17)	−0.0018 (17)
C23a	0.036 (2)	0.034 (2)	0.0243 (19)	−0.0006 (19)	0.0012 (17)	0.0008 (18)
C24	0.047 (3)	0.036 (3)	0.031 (2)	0.002 (2)	0.000 (2)	−0.005 (2)
N24	0.075 (4)	0.062 (4)	0.046 (3)	0.014 (3)	0.001 (3)	−0.026 (3)
O241	0.121 (5)	0.110 (5)	0.071 (3)	0.050 (4)	−0.008 (3)	−0.059 (4)
O242	0.135 (5)	0.130 (6)	0.058 (3)	0.076 (5)	−0.050 (4)	−0.048 (4)
C25	0.048 (3)	0.040 (3)	0.049 (3)	0.014 (3)	0.006 (2)	0.001 (3)
C26	0.041 (3)	0.042 (3)	0.053 (3)	0.008 (2)	−0.005 (2)	0.006 (3)
C27	0.043 (3)	0.052 (3)	0.035 (3)	0.002 (3)	−0.011 (2)	0.001 (2)
C27a	0.038 (2)	0.029 (2)	0.0255 (19)	−0.0031 (19)	0.0007 (17)	0.0024 (17)
C21'	0.0295 (19)	0.030 (2)	0.0205 (17)	0.0002 (18)	0.0044 (15)	0.0023 (17)
O22'	0.0288 (15)	0.0390 (19)	0.0238 (14)	0.0011 (14)	0.0011 (11)	−0.0108 (14)
C22'	0.0216 (18)	0.027 (2)	0.0232 (18)	−0.0006 (16)	0.0016 (14)	−0.0004 (16)
O23'	0.0416 (18)	0.0348 (19)	0.0269 (15)	−0.0026 (15)	0.0115 (13)	0.0016 (13)
C23'	0.0222 (18)	0.033 (2)	0.0202 (17)	0.0008 (16)	0.0052 (14)	−0.0022 (16)
O24'	0.0230 (13)	0.0384 (18)	0.0254 (13)	−0.0049 (13)	−0.0003 (11)	−0.0013 (14)
C24'	0.0243 (18)	0.033 (2)	0.0193 (17)	−0.0013 (17)	0.0026 (14)	−0.0037 (17)
O25'	0.0302 (17)	0.112 (4)	0.048 (2)	−0.002 (2)	−0.0014 (15)	−0.050 (3)
C25'	0.031 (2)	0.048 (3)	0.0217 (18)	0.003 (2)	0.0017 (15)	−0.0069 (19)

Geometric parameters (Å, º)

N11—C17a	1.356 (6)	N21—C27a	1.346 (6)
N11—N12	1.357 (5)	N21—N22	1.358 (5)
N12—C13	1.344 (6)	N22—C23	1.347 (6)
N12—C11'	1.463 (6)	N22—C21'	1.470 (6)
C13—C13a	1.376 (7)	C23—C23a	1.390 (7)
C13—H13A	0.9300	C23—H23A	0.9300
C13a—C17a	1.424 (6)	C23a—C24	1.406 (7)
C13a—C14	1.427 (7)	C23a—C27a	1.427 (6)
C14—C15	1.364 (7)	C24—C25	1.379 (8)
C14—N14	1.457 (6)	C24—N24	1.457 (7)
N14—O141	1.215 (6)	N24—O242	1.200 (8)
N14—O142	1.231 (7)	N24—O241	1.217 (7)
C15—C16	1.410 (8)	C25—C26	1.414 (8)
C15—H15D	0.9300	C25—H25D	0.9300
C16—C17	1.365 (9)	C26—C27	1.361 (9)
C16—H16C	0.9300	C26—H26C	0.9300
C17—C17a	1.417 (6)	C27—C27a	1.411 (7)
C17—H17B	0.9300	C27—H27B	0.9300
C11'—O14'	1.404 (5)	C21'—O24'	1.410 (5)
C11'—C12'	1.526 (6)	C21'—C22'	1.529 (6)
C11'—H11A	0.9800	C21'—H21A	0.9800
O12'—C12'	1.406 (5)	O22'—C22'	1.419 (5)
O12'—H12A	0.82 (3)	O22'—H22A	0.82 (4)
C12'—C13'	1.531 (6)	C22'—C23'	1.533 (5)
C12'—H12C	0.9800	C22'—H22C	0.9800
O13'—C13'	1.430 (5)	O23'—C23'	1.408 (6)
O13'—H13O	0.82 (4)	O23'—H23O	0.82 (3)
C13'—C14'	1.511 (7)	C23'—C24'	1.526 (6)
C13'—H13B	0.9800	C23'—H23B	0.9800
O14'—C14'	1.461 (5)	O24'—C24'	1.460 (5)
C14'—C15'	1.526 (6)	C24'—C25'	1.518 (6)
C14'—H14A	0.9800	C24'—H24A	0.9800
O15'—C15'	1.410 (6)	O25'—C25'	1.419 (6)
O15'—H15A	0.82 (5)	O25'—H25A	0.83 (7)
C15'—H15B	0.9700	C25'—H25B	0.9700
C15'—H15C	0.9700	C25'—H25C	0.9700
C17a—N11—N12	103.5 (4)	C27a—N21—N22	104.3 (4)
C13—N12—N11	114.2 (4)	C23—N22—N21	113.3 (4)
C13—N12—C11'	127.3 (4)	C23—N22—C21'	128.8 (4)
N11—N12—C11'	118.5 (4)	N21—N22—C21'	117.8 (3)
N12—C13—C13a	106.3 (4)	N22—C23—C23a	106.8 (4)
N12—C13—H13A	126.9	N22—C23—H23A	126.6
C13a—C13—H13A	126.9	C23a—C23—H23A	126.6
C13—C13a—C17a	105.4 (4)	C23—C23a—C24	137.7 (4)
C13—C13a—C14	137.2 (4)	C23—C23a—C27a	104.4 (4)
C17a—C13a—C14	117.4 (4)	C24—C23a—C27a	118.0 (4)
C15—C14—C13a	120.4 (4)	C25—C24—C23a	121.1 (5)
C15—C14—N14	120.1 (5)	C25—C24—N24	119.3 (5)
C13a—C14—N14	119.5 (4)	C23a—C24—N24	119.6 (5)
O141—N14—O142	124.3 (5)	O242—N24—O241	123.2 (6)
O141—N14—C14	119.1 (5)	O242—N24—C24	117.9 (5)
O142—N14—C14	116.6 (4)	O241—N24—C24	119.0 (6)
C14—C15—C16	120.5 (5)	C24—C25—C26	119.5 (5)
C14—C15—H15D	119.7	C24—C25—H25D	120.2
C16—C15—H15D	119.7	C26—C25—H25D	120.2
C17—C16—C15	122.3 (5)	C27—C26—C25	121.7 (5)
C17—C16—H16C	118.9	C27—C26—H26C	119.1
C15—C16—H16C	118.9	C25—C26—H26C	119.1
C16—C17—C17a	117.5 (5)	C26—C27—C27a	118.9 (5)
C16—C17—H17B	121.3	C26—C27—H27B	120.6
C17a—C17—H17B	121.3	C27a—C27—H27B	120.6
N11—C17a—C17	127.4 (4)	N21—C27a—C27	128.0 (4)
N11—C17a—C13a	110.6 (4)	N21—C27a—C23a	111.1 (4)
C17—C17a—C13a	122.0 (5)	C27—C27a—C23a	120.9 (5)
O14'—C11'—N12	108.9 (4)	O24'—C21'—N22	109.2 (4)
O14'—C11'—C12'	106.7 (3)	O24'—C21'—C22'	107.0 (3)
N12—C11'—C12'	113.3 (3)	N22—C21'—C22'	110.9 (3)
O14'—C11'—H11A	109.2	O24'—C21'—H21A	109.9
N12—C11'—H11A	109.2	N22—C21'—H21A	109.9
C12'—C11'—H11A	109.2	C22'—C21'—H21A	109.9
C12'—O12'—H12A	109 (3)	C22'—O22'—H22A	108.5 (13)
O12'—C12'—C11'	110.1 (3)	O22'—C22'—C21'	109.3 (3)
O12'—C12'—C13'	116.0 (4)	O22'—C22'—C23'	110.0 (3)
C11'—C12'—C13'	100.9 (3)	C21'—C22'—C23'	100.0 (3)
O12'—C12'—H12C	109.8	O22'—C22'—H22C	112.3
C11'—C12'—H12C	109.8	C21'—C22'—H22C	112.3
C13'—C12'—H12C	109.8	C23'—C22'—H22C	112.3
C13'—O13'—H13O	108 (3)	C23'—O23'—H23O	110 (3)
O13'—C13'—C14'	111.4 (4)	O23'—C23'—C24'	113.9 (4)
O13'—C13'—C12'	105.9 (3)	O23'—C23'—C22'	115.4 (4)
C14'—C13'—C12'	101.4 (4)	C24'—C23'—C22'	102.0 (3)
O13'—C13'—H13B	112.5	O23'—C23'—H23B	108.4
C14'—C13'—H13B	112.5	C24'—C23'—H23B	108.4
C12'—C13'—H13B	112.5	C22'—C23'—H23B	108.4
C11'—O14'—C14'	110.0 (3)	C21'—O24'—C24'	110.0 (3)
O14'—C14'—C13'	104.4 (3)	O24'—C24'—C25'	109.8 (4)
O14'—C14'—C15'	107.9 (4)	O24'—C24'—C23'	104.0 (3)
C13'—C14'—C15'	115.5 (4)	C25'—C24'—C23'	113.9 (3)
O14'—C14'—H14A	109.6	O24'—C24'—H24A	109.7
C13'—C14'—H14A	109.6	C25'—C24'—H24A	109.7
C15'—C14'—H14A	109.6	C23'—C24'—H24A	109.7
C15'—O15'—H15A	109.3 (13)	C25'—O25'—H25A	108.3 (14)
O15'—C15'—C14'	109.9 (4)	O25'—C25'—C24'	108.8 (4)
O15'—C15'—H15B	109.7	O25'—C25'—H25B	109.9
C14'—C15'—H15B	109.7	C24'—C25'—H25B	109.9
O15'—C15'—H15C	109.7	O25'—C25'—H25C	109.9
C14'—C15'—H15C	109.7	C24'—C25'—H25C	109.9
H15B—C15'—H15C	108.2	H25B—C25'—H25C	108.3
C17a—N11—N12—C13	0.1 (5)	C27a—N21—N22—C23	0.1 (5)
C17a—N11—N12—C11'	−179.3 (4)	C27a—N21—N22—C21'	−177.0 (4)
N11—N12—C13—C13a	−0.5 (6)	N21—N22—C23—C23a	−0.4 (6)
C11'—N12—C13—C13a	178.8 (4)	C21'—N22—C23—C23a	176.3 (4)
N12—C13—C13a—C17a	0.6 (5)	N22—C23—C23a—C24	−179.1 (6)
N12—C13—C13a—C14	179.3 (6)	N22—C23—C23a—C27a	0.5 (5)
C13—C13a—C14—C15	−179.2 (6)	C23—C23a—C24—C25	180.0 (6)
C17a—C13a—C14—C15	−0.7 (7)	C27a—C23a—C24—C25	0.4 (8)
C13—C13a—C14—N14	2.2 (9)	C23—C23a—C24—N24	−1.2 (10)
C17a—C13a—C14—N14	−179.3 (4)	C27a—C23a—C24—N24	179.2 (5)
C15—C14—N14—O141	0.5 (8)	C25—C24—N24—O242	178.7 (8)
C13a—C14—N14—O141	179.0 (5)	C23a—C24—N24—O242	−0.1 (10)
C15—C14—N14—O142	−178.3 (6)	C25—C24—N24—O241	0.5 (10)
C13a—C14—N14—O142	0.2 (8)	C23a—C24—N24—O241	−178.3 (7)
C13a—C14—C15—C16	0.8 (8)	C23a—C24—C25—C26	−1.2 (9)
N14—C14—C15—C16	179.4 (5)	N24—C24—C25—C26	−180.0 (6)
C14—C15—C16—C17	−0.4 (9)	C24—C25—C26—C27	1.7 (10)
C15—C16—C17—C17a	0.0 (9)	C25—C26—C27—C27a	−1.4 (9)
N12—N11—C17a—C17	−179.5 (5)	N22—N21—C27a—C27	179.5 (5)
N12—N11—C17a—C13a	0.3 (5)	N22—N21—C27a—C23a	0.3 (5)
C16—C17—C17a—N11	179.9 (5)	C26—C27—C27a—N21	−178.6 (5)
C16—C17—C17a—C13a	0.1 (8)	C26—C27—C27a—C23a	0.6 (8)
C13—C13a—C17a—N11	−0.6 (6)	C23—C23a—C27a—N21	−0.5 (6)
C14—C13a—C17a—N11	−179.6 (4)	C24—C23a—C27a—N21	179.2 (4)
C13—C13a—C17a—C17	179.2 (5)	C23—C23a—C27a—C27	−179.8 (5)
C14—C13a—C17a—C17	0.3 (7)	C24—C23a—C27a—C27	−0.1 (7)
C13—N12—C11'—O14'	43.7 (6)	C23—N22—C21'—O24'	13.8 (6)
N11—N12—C11'—O14'	−137.0 (4)	N21—N22—C21'—O24'	−169.6 (4)
C13—N12—C11'—C12'	−75.0 (6)	C23—N22—C21'—C22'	−103.9 (5)
N11—N12—C11'—C12'	104.3 (4)	N21—N22—C21'—C22'	72.7 (5)
O14'—C11'—C12'—O12'	153.9 (3)	O24'—C21'—C22'—O22'	82.8 (4)
N12—C11'—C12'—O12'	−86.2 (4)	N22—C21'—C22'—O22'	−158.3 (3)
O14'—C11'—C12'—C13'	30.9 (4)	O24'—C21'—C22'—C23'	−32.6 (4)
N12—C11'—C12'—C13'	150.8 (3)	N22—C21'—C22'—C23'	86.3 (4)
O12'—C12'—C13'—O13'	−42.1 (5)	O22'—C22'—C23'—O23'	49.2 (5)
C11'—C12'—C13'—O13'	76.8 (4)	C21'—C22'—C23'—O23'	164.1 (3)
O12'—C12'—C13'—C14'	−158.4 (4)	O22'—C22'—C23'—C24'	−74.8 (4)
C11'—C12'—C13'—C14'	−39.6 (4)	C21'—C22'—C23'—C24'	40.1 (4)
N12—C11'—O14'—C14'	−132.0 (3)	N22—C21'—O24'—C24'	−108.3 (4)
C12'—C11'—O14'—C14'	−9.3 (4)	C22'—C21'—O24'—C24'	11.8 (4)
C11'—O14'—C14'—C13'	−16.7 (4)	C21'—O24'—C24'—C25'	136.8 (4)
C11'—O14'—C14'—C15'	106.7 (4)	C21'—O24'—C24'—C23'	14.5 (4)
O13'—C13'—C14'—O14'	−77.1 (4)	O23'—C23'—C24'—O24'	−159.5 (3)
C12'—C13'—C14'—O14'	35.2 (4)	C22'—C23'—C24'—O24'	−34.5 (4)
O13'—C13'—C14'—C15'	164.6 (4)	O23'—C23'—C24'—C25'	81.0 (5)
C12'—C13'—C14'—C15'	−83.1 (4)	C22'—C23'—C24'—C25'	−154.0 (4)
O14'—C14'—C15'—O15'	162.8 (4)	O24'—C24'—C25'—O25'	67.8 (5)
C13'—C14'—C15'—O15'	−80.9 (5)	C23'—C24'—C25'—O25'	−176.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12′—H12A···O22′^i	0.82 (5)	2.08 (3)	2.841 (5)	154 (6)
O13′—H13O···O23′^ii	0.83 (7)	1.96 (3)	2.720 (4)	154 (6)
O15′—H15A···N11^iii	0.82 (5)	2.14 (4)	2.928 (6)	162 (2)
O22′—H22A···O13′^iv	0.82 (2)	1.95 (5)	2.741 (4)	161 (6)
O23′—H23O···O15′^v	0.82 (2)	2.14 (2)	2.839 (6)	144 (3)
O25′—H25A···N21^vi	0.83 (7)	1.99 (7)	2.812 (5)	172 (2)

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