A synchrotron radiation study of the one-dimensional complex of sodium with (1S)-N-carboxyl­ato-1-(9-deaza­adenin-9-yl)-1,4-dide­oxy-1,4-imino-D-ribitol, a member of the 'immucillin' family

The sodium salt of [immucillin-A-CO₂H]^- (Imm-A), namely catena-poly[[[triaqua­disodium(I)]([mu]-aqua)[[mu]-(1S)-N-car­box­yl­ato-1-(9-deaza­adenin-9-yl)-1,4-dide­oxy-1,4-imino-D-ribi­tol][triaqua­disodium(I)][[mu]-(1S)-N-carboxyl­ato-1-(9-deaza­aden­in-9-yl)-1,4-dide­oxy-1,4-imino-D-ribitol]] tetra­hydrate], {[Na₂(C₁₂H₁₃N₄O₆)₂(H₂O)₇]·4H₂O}_n, (I), forms a polymeric chain via Na⁺-O inter­actions involving the carboxyl­ate and keto O atoms of two independent Imm-A mol­ecules. Extensive N,O-H...O hydrogen bonding utilizing all water H atoms, including four waters of crystallization, provides crystal packing. The structural definition of this novel compound was made possible through the use of synchrotron radiation utilizing a minute fragment (volume ~2.4 × 10^-5 mm^-3) on a beamline optimized for protein data collection. A summary of intra-ring conformations for immucillin structures indicates considerable flexibility while retaining similar intra-ring orientations.

S1. Comment

The title compound, (I), was prepared as part of continuing studies of the so-called 'immucillin' family of compounds which are potent aza-C-nucleoside inhibitors of purine nucleoside phosphorylase (Evans et al., 2003). The immucillin compounds do not usually form adequate-quality crystals, and only adducts protonated on the aza-ribitol sugar (N1) positions have been reported [MILMAV, Federov et al. (2001); MEFZOM, Evans et al. (2000)] [alphabetic codes used herein are those used in the Cambridge Structural Database, 2009]. A related compound, with oxygen replacing NH in the saturated five-membered ring, is VOVJIZ (Otter et al., 1992) while compound VILHON (Ikegami et al., 1990) has been re-assigned as a related 6'-amino compound by Otter et al. (1992). Some of these compounds have been successfully defined `in action' as inhibitors in sites within the enzymes (e.g. MT-Imm_A, Singh et al., 2004). The size of the crystal fragment used here meant that both the superb power and resolution of synchrotron radiation was essential even when used in the less than optimum settings at the end of a protein data collection. We are thus able to present the first anionic derivative of this family.

The asymmetric unit contents of the title compound, (I), are shown in Fig. 1; the polymer linking bonds (Na1*—O16, Na1—O16*) are shown at the top and bottom of the figure (see also Fig. 2 and scheme). The two independent ImmA-CO₂^- molecules, which are label-related by adding 10 to the number of the first (i.e. N1 and N11), are almost superimposable. The absolute configurations at C1' (S), C2' (S), C3' (R) and C4' (R) indicated by a Flack parameter of 0.0 (3) agree with the stereochemistry known from the synthesis. There is a slight difference in tilt angle ~10° between the two rings (see the dihedral angles around C1'—C9 and C11'—C19 in Table 1) and ring comparisons (Spek, 2009) give r.m.s. bond and angle fits of 0.016 Å and 1.25°. The 1,9-deazaadenin-9-yl nine-membered rings (e.g. N1, C2, N3, C4, C9, C8, N7, C5, C6) are made up of two rigidly planar five- and six-membered rings which are at an average of 1.8 (3)° to each other. The five-membered (imino-ribitol) rings (e.g. N1', C1'-C4') are puckered on C2' and C3' [Cremer & Pople (1975) parameters Q(2) 0.342 (6) Å, ϕ(2) 272.3 (9)°] in molecule 1 and twisted on C12'–C13' [Q(2) 0.307 (6) Å, ϕ(2) 268.2 (10)°] in the other. Such variations are normal as shown by the pyrrolidine-1-carboxylate adduct FISNUR (Zukerman-Schpector et al., 2005) which also twists along C2'–C3' [Q(2) 0.426 Å, ϕ(2) 266.4 (3)°].

For completeness we note that other pyrimidine-4-one structures have been reported: FOYWIZ (Girgis et al., 1987) and QINBOE (Jukic et al., 2000); the former has (fortuitously) similar relative orientations of the two rings to molecule 1 here.

One of the ImmA-CO₂^- molecules provides a bridging oxygen (O6) to the two independent cations while the other bonds to only Na2 through the carboxylate oxygen O7b' (Fig. 1). The Na cations are further bridged by one water molecule (O2W) and both have the usual approximate octahedral binding stereochemistry, with variation in Na—O distances depending on the trans donor atoms. Finally, the packing cohesion is provided by extensive hydrogen bonds involving all the waters of crystallization, the aqua molecules and the ImmA-CO₂^- nitrogen H atoms as donors (Table 2, scheme). Overall, the structure can be described as a polymeric chain parallel to the (1,-1,1) plane cross-linked by hydrogen bonds to the water molecules that lie between the chains (Fig. 2).

It is of interest to compare the relative conformations of the two independent ImmA-CO₂^- molecules here with the previously reported (free) ImmH cationic molecules and ImmH as found bound in a human purine nucleoside phosphorylase mutant (Table 3). There is quite a wide variation of relative conformations of the ten-membered 9-deazaadenin-9-yl and the 4-aza-ribitol rings with respect to the linking bond (e.g. C1–C9') with the two independent molecules here being closely related both in intra-ring orientations and in the 4-aza ribitol ring descriptions. This is rather remarkable given the variation that might be expected in the strongly hydrogen-bonded network and with each molecule involved in different interactions with the cations. Agreement between the two free ImmH studies (entries 4 and 6) is also notable. It is also apparent that the protein-bound molecule (entry 5) has been twisted about the link bond in response to close interactions, but still retained a similar intraplanar angle (between the two rings) to that in the free ligand structures. The linking factor in these determinations is that the variable conformations retain a similar intraplanar angle with only minor variations in the attachment angles [e.g. C1'–C9–C8, C11'–C19–C18 126.3 (5),129.1 (5)°, respectively, here compared with 130.2° in the bound molecule (Murkin et al., 2007)].

Related literature

For related literature, see: Cambridge Structural Database (2009); Cremer & Pople (1975); Evans et al. (2000, 2003); Federov et al. (2001); Girgis et al. (1987); Ikegami et al. (1990); Jukic et al. (2000); Murkin et al. (2007); Otter et al. (1992); Singh et al. (2004); Spek (2009); Zukerman-Schpector, Caracelli, Teijido, Garcia, Costenaro & Correia (2005).

S2. Experimental

The title compound (immucillin-A—CO₂H) was made by incubation of the Imm-A-HCl salt (50 mg, 0.165 mmol) (Evans et al., 2003) dissolved in 2 ml of water. The compound was deprotonated with 0.165 mmol (6.6 mg) sodium hydroxide dissolved in 100 µl water, which caused precipitation, but an additional 0.165 mmol [?mg] sodium hydroxide dissolved in 100 µl caused the compound to redissolve. The aqueous mixture was left open to the atmosphere to allow for evaporation of solvent (and to pick up CO₂) and for crystallization. The described material crystallized after 1 week.

S3. Refinement

One low angle reflection (-1,1,0) and 8 high angle reflections (Δ(F²)/e.s.d. > 3.8) were omitted. A total of 44 non-H atoms were refined with isotropic displacement parameters (some being unstable to anisotropic refinement) thereby improving the data/parameter value. The number of Friedel pairs was 1161. All H atoms were constrained, with U_iso values of 1.2 times the U_eq of the parent atom for C, N and hydroxy O atoms, and with U_iso values of 1.2 times the U_eq of the parent atom for water O atoms. Most water H atoms were located on difference Fourier maps; other water H atoms were positioned from stereochemical considerations and confirmed by improved agreement factors and Fourier maps. The O10W water H atoms could not be resolved from difference Fourier maps and their placement lead to unacceptably close contacts with other water H atoms (< 1.5 Å); they were excluded from the final refinement. In final refinements, all water O—H distances were constrained to 0.82 (3) Å, with a minimum H···H distance of 1.35 (3) Å. In the final model, there are some close water H···H distances reflecting the model and data limitations. All other H atoms were geometrically constrained (riding model) to C–H,N–H and O–H bond lengths of 0.99,0.88 and 0.84 Å, respectively.

Computing details

Data collection: DENZO, (Otwinowski & Minor, 1997); cell refinement: DENZO, (Otwinowski & Minor, 1997); data reduction: DENZO & SCALEPACK, (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP in WinGX (Farrugia, 1997); PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008); PLATON (Spek, 2009) Mercury (Bruno et al., 2002).

Figures

	Fig. 1. Diagram of the asymmetric unit and two atoms of (I) with 50% displacement ellipsoids (Farrugia, 1997). Atoms Na1* (at x-1, y-1, z) and O16* (at x+1, y+1, z) are included and linked by 3-line bonds to show the polymeric linkages. H atoms have arbitrary radii. Identified hydrogen bonds within the asymmetric unit are shown as dashed lines.
	Fig. 2. Packing diagram of the cell of (I) (Bruno et al., 2002) viewed approximately down the c axis. Representative atom labels are given (see text and Table 2) and H atoms are omitted for clarity. Hydrogen bonds are shown as dashed lines. N, blue sticks; Na, purple balls; O, red sticks; C, grey wires.

catena-Poly[[[triaquadisodium(I)](µ-aqua)[µ-(1S)-N-carboxylato-1-(9-deazaadenin-9-yl)-1,4-dideoxy-1,4-imino-D-ribitol][triaquadisodium(I)][µ-(1S)-N-carboxylato-1-(9-deazaadenin-9-yl)-1,4-dideoxy-1,4-imino-D-ribitol]] tetrahydrate]

Crystal data

[Na2(C12H13N4O6)2(H2O)7]·4H2O	Z = 1
Mr = 862.68	F(000) = 454
Triclinic, P1	Dx = 1.571 Mg m^−3
Hall symbol: P 1	Synchrotron radiation, λ = 0.98000 Å
a = 7.6620 (15) Å	Cell parameters from 185 reflections
b = 10.488 (2) Å	θ = 3.8–26.5°
c = 11.606 (2) Å	µ = 0.16 mm^−1
α = 98.24 (3)°	T = 100 K
β = 91.07 (3)°	Plate, colourless
γ = 98.49 (3)°	0.08 × 0.06 × 0.01 mm
V = 912.1 (3) Å^3

Data collection

MAR CCD detector diffractometer	2330 reflections with I > 2σ(I)
Si111 monochromator	Rint = 0.034
Detector resolution: 4000 pixels mm^-1	θmax = 25.5°, θmin = 2.5°
ϕ scan	h = −6→6
2357 measured reflections	k = −9→9
2357 independent reflections	l = −9→9

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 1.0082P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2357 reflections	Δρmax = 0.22 e Å^−3
360 parameters	Δρmin = −0.21 e Å^−3
27 restraints	Absolute structure: Flack (1983), 1161 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.0 (3)

Special details

Experimental. Crystal decay was monitored and corrected by the inter-frame analysis (DENZO: Otwinowski & Minor (1997)).

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Na1	0.9839 (3)	1.3128 (2)	0.4851 (2)	0.0262 (6)
Na2	0.6910 (3)	1.23034 (19)	0.7169 (2)	0.0273 (6)
O1W	0.4963 (5)	1.2928 (4)	0.8598 (4)	0.0330 (12)
H1W1	0.474 (9)	1.365 (4)	0.887 (6)	0.049*
H1W2	0.405 (6)	1.250 (6)	0.863 (7)	0.049*
O2W	0.7781 (5)	1.4180 (4)	0.6201 (4)	0.0290 (11)
H2W1	0.710 (8)	1.432 (5)	0.568 (4)	0.044*
H2W2	0.781 (8)	1.481 (5)	0.673 (4)	0.044*
O3W	0.9204 (5)	1.3167 (4)	0.8678 (4)	0.0264 (11)
H3W1	0.982 (7)	1.386 (4)	0.883 (6)	0.040*
H3W2	0.854 (8)	1.299 (6)	0.922 (4)	0.040*
O4W	0.4326 (5)	1.1534 (4)	0.5740 (4)	0.0289 (11)
H4W1	0.457 (8)	1.160 (5)	0.504 (3)	0.043*
H4W2	0.369 (7)	1.083 (4)	0.571 (5)	0.043*
O5W	1.2008 (5)	1.3340 (4)	0.6402 (4)	0.0291 (12)
H5W1	1.286 (7)	1.303 (6)	0.607 (5)	0.044*
H5W2	1.159 (9)	1.304 (6)	0.695 (4)	0.044*
O6W	0.4746 (6)	1.1225 (4)	0.3375 (4)	0.0315 (11)
H6W1	0.473 (9)	1.055 (5)	0.290 (5)	0.047*
H6W2	0.557 (7)	1.176 (5)	0.322 (6)	0.047*
O7W	0.7809 (5)	0.2924 (4)	0.0848 (4)	0.0261 (11)
H7W1	0.734 (8)	0.221 (4)	0.055 (6)	0.039*
H7W2	0.699 (6)	0.332 (6)	0.108 (6)	0.039*
O8W	1.1404 (5)	1.2039 (4)	0.3334 (4)	0.0256 (11)
H8W1	1.137 (7)	1.256 (5)	0.285 (5)	0.038*
H8W2	1.239 (5)	1.185 (5)	0.335 (5)	0.038*
O9W	0.7699 (5)	1.3102 (4)	0.3328 (4)	0.0286 (11)
H9W1	0.686 (6)	1.348 (6)	0.359 (5)	0.043*
H9W2	0.786 (8)	1.329 (6)	0.266 (3)	0.043*
O10W	0.5397 (5)	0.4641 (3)	0.4447 (3)	0.0280 (11)
O11W	0.1833 (5)	0.3381 (4)	0.1420 (4)	0.0279 (11)
H11A	0.131 (8)	0.279 (5)	0.094 (5)	0.042*
H11B	0.124 (8)	0.399 (5)	0.156 (6)	0.042*
N1'	0.8358 (6)	0.6307 (4)	0.0682 (4)	0.0213 (12)*
C1'	0.7459 (7)	0.6338 (6)	0.1812 (5)	0.0227 (15)*
H1'	0.7942	0.5716	0.2265	0.027*
C2'	0.5563 (8)	0.5816 (5)	0.1489 (5)	0.0198 (15)*
H2'	0.4754	0.6226	0.2045	0.024*
O2'	0.5336 (5)	0.4434 (3)	0.1453 (4)	0.0231 (10)*
H2'O	0.4261	0.4127	0.1337	0.028*
C3'	0.5332 (7)	0.6162 (5)	0.0276 (5)	0.0190 (15)*
H3'	0.5123	0.7088	0.0334	0.023*
O3'	0.3980 (5)	0.5334 (3)	−0.0465 (3)	0.0209 (10)*
H3'O	0.3006	0.5596	−0.0344	0.025*
C4'	0.7074 (7)	0.6011 (5)	−0.0323 (5)	0.0176 (15)*
H4'	0.7034	0.5078	−0.0673	0.021*
C5'	0.7362 (7)	0.6847 (5)	−0.1277 (5)	0.0214 (15)*
H5'A	0.6217	0.6812	−0.1700	0.026*
H5'B	0.7745	0.7761	−0.0913	0.026*
O5'	0.8628 (5)	0.6490 (4)	−0.2104 (4)	0.0250 (10)*
H5'O	0.9509	0.6310	−0.1753	0.030*
C7'	1.0041 (8)	0.6007 (5)	0.0601 (6)	0.0212 (15)*
O7'A	1.0922 (5)	0.5926 (3)	0.1502 (3)	0.0212 (10)*
O7'B	1.0623 (5)	0.5786 (3)	−0.0429 (4)	0.0211 (10)*
N1	0.7170 (5)	0.9150 (4)	0.5883 (4)	0.0209 (13)*
H1N	0.7040	0.9468	0.6615	0.025*
C2	0.6629 (7)	0.7864 (5)	0.5547 (6)	0.0242 (16)*
H2	0.6148	0.7366	0.6119	0.029*
N3	0.6719 (6)	0.7249 (4)	0.4478 (4)	0.0231 (13)*
C4	0.7457 (7)	0.8033 (5)	0.3708 (5)	0.0198 (15)*
C5	0.8032 (7)	0.9355 (5)	0.4015 (6)	0.0199 (15)*
C6	0.7918 (7)	1.0008 (5)	0.5156 (5)	0.0207 (15)*
O6	0.8372 (5)	1.1186 (4)	0.5543 (3)	0.0245 (10)*
N7	0.8716 (6)	0.9840 (4)	0.3065 (4)	0.0190 (12)*
H7N	0.9166	1.0657	0.3038	0.023*
C8	0.8579 (7)	0.8830 (5)	0.2156 (6)	0.0212 (15)*
H8	0.8953	0.8901	0.1388	0.025*
C9	0.7809 (7)	0.7694 (5)	0.2535 (5)	0.0211 (15)*
C11'	0.3086 (7)	0.9684 (5)	0.7875 (5)	0.0227 (16)*
H11'	0.3760	1.0289	0.7392	0.027*
N11'	0.4092 (5)	0.9768 (4)	0.8984 (4)	0.0165 (12)*
C12'	0.1380 (8)	1.0204 (6)	0.8215 (6)	0.0218 (15)*
H12'	0.0357	0.9738	0.7697	0.026*
O12'	0.1631 (5)	1.1565 (3)	0.8168 (3)	0.0229 (10)*
H2O'	0.0782	1.1890	0.8474	0.027*
C13'	0.1162 (7)	0.9941 (5)	0.9456 (5)	0.0211 (15)*
H13'	0.0555	0.9026	0.9441	0.025*
O13'	0.0200 (5)	1.0800 (3)	1.0168 (3)	0.0219 (10)*
H3O'	−0.0886	1.0517	1.0080	0.026*
C14'	0.3006 (7)	1.0062 (5)	1.0009 (5)	0.0192 (15)*
H14'	0.3397	1.0976	1.0401	0.023*
C15'	0.3003 (7)	0.9131 (5)	1.0885 (5)	0.0211 (15)*
H5A'	0.2039	0.9268	1.1424	0.025*
H5B'	0.2731	0.8230	1.0466	0.025*
C17'	0.5883 (7)	1.0141 (5)	0.9013 (5)	0.0193 (15)*
O7A'	0.6680 (5)	1.0309 (3)	1.0035 (3)	0.0241 (10)*
O7B'	0.6689 (5)	1.0272 (3)	0.8106 (3)	0.0209 (10)*
O15'	0.4637 (5)	0.9248 (4)	1.1570 (4)	0.0278 (10)*
H5O'	0.5472	0.9617	1.1221	0.033*
N11	0.1676 (6)	0.6995 (4)	0.3774 (4)	0.0237 (13)*
H11N	0.1414	0.6694	0.3035	0.028*
C12	0.1920 (7)	0.8325 (5)	0.4112 (6)	0.0236 (16)*
H12	0.1825	0.8864	0.3529	0.028*
N13	0.2276 (6)	0.8893 (4)	0.5194 (4)	0.0212 (12)*
C14	0.2396 (7)	0.8053 (5)	0.5985 (5)	0.0198 (15)*
C15	0.2189 (7)	0.6706 (5)	0.5691 (5)	0.0204 (15)*
C16	0.1821 (7)	0.6103 (5)	0.4531 (5)	0.0176 (15)*
O16	0.1628 (5)	0.4905 (3)	0.4148 (3)	0.0244 (10)*
N17	0.2487 (6)	0.6181 (4)	0.6665 (4)	0.0190 (12)*
H17N	0.2451	0.5346	0.6702	0.023*
C18	0.2852 (7)	0.7169 (5)	0.7577 (6)	0.0193 (15)*
H18	0.3101	0.7061	0.8359	0.023*
C19	0.2804 (7)	0.8343 (5)	0.7194 (5)	0.0198 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0263 (14)	0.0240 (13)	0.0279 (17)	0.0038 (10)	0.0009 (11)	0.0029 (10)
Na2	0.0295 (13)	0.0230 (13)	0.0288 (17)	0.0057 (10)	0.0019 (11)	−0.0007 (11)
O1W	0.026 (3)	0.021 (3)	0.047 (3)	0.001 (2)	0.003 (2)	−0.010 (2)
O2W	0.036 (3)	0.025 (3)	0.026 (3)	0.010 (2)	0.001 (2)	−0.001 (2)
O3W	0.022 (3)	0.023 (2)	0.033 (4)	0.001 (2)	0.005 (2)	0.002 (2)
O4W	0.034 (3)	0.027 (3)	0.026 (3)	−0.0010 (19)	0.005 (2)	0.007 (2)
O5W	0.026 (3)	0.033 (3)	0.030 (4)	0.008 (2)	0.006 (2)	0.006 (2)
O6W	0.028 (3)	0.032 (3)	0.035 (3)	0.004 (2)	0.002 (3)	0.006 (2)
O7W	0.022 (3)	0.026 (3)	0.032 (3)	0.010 (2)	−0.001 (2)	0.001 (2)
O8W	0.026 (3)	0.026 (3)	0.029 (3)	0.011 (2)	0.003 (2)	0.009 (2)
O9W	0.028 (2)	0.032 (3)	0.027 (3)	0.007 (2)	0.001 (2)	0.005 (2)
O10W	0.030 (3)	0.025 (2)	0.029 (3)	0.0097 (19)	0.000 (2)	−0.003 (2)
O11W	0.023 (3)	0.029 (3)	0.029 (3)	0.005 (2)	0.001 (2)	−0.005 (2)

Geometric parameters (Å, º)

Na1—O9W	2.382 (5)	C7'—O7'B	1.286 (7)
Na1—O5W	2.391 (5)	N1—C2	1.349 (7)
Na1—O16^i	2.396 (4)	N1—C6	1.391 (7)
Na1—O8W	2.398 (5)	N1—H1N	0.8800
Na1—O6	2.426 (4)	C2—N3	1.321 (7)
Na1—O2W	2.504 (5)	C2—H2	0.9500
Na1—H8W1	2.65 (6)	N3—C4	1.374 (8)
Na2—O1W	2.340 (5)	C4—C5	1.384 (8)
Na2—O2W	2.419 (5)	C4—C9	1.398 (8)
Na2—O3W	2.436 (5)	C5—N7	1.361 (7)
Na2—O6	2.454 (4)	C5—C6	1.412 (8)
Na2—O7B'	2.513 (4)	C6—O6	1.247 (6)
Na2—O4W	2.518 (5)	N7—C8	1.375 (7)
Na2—H3W2	2.62 (7)	N7—H7N	0.8800
O1W—H1W1	0.82 (3)	C8—C9	1.384 (8)
O1W—H1W2	0.78 (3)	C8—H8	0.9500
O2W—H2W1	0.84 (3)	C11'—N11'	1.473 (7)
O2W—H2W2	0.83 (3)	C11'—C19	1.495 (8)
O3W—H3W1	0.80 (3)	C11'—C12'	1.527 (8)
O3W—H3W2	0.84 (3)	C11'—H11'	1.0000
O4W—H4W1	0.85 (3)	N11'—C17'	1.369 (7)
O4W—H4W2	0.81 (3)	N11'—C14'	1.487 (7)
O5W—H5W1	0.85 (3)	C12'—O12'	1.421 (7)
O5W—H5W2	0.80 (3)	C12'—C13'	1.513 (9)
O6W—H6W1	0.83 (3)	C12'—H12'	1.0000
O6W—H6W2	0.82 (3)	O12'—H2O'	0.8400
O7W—H7W1	0.81 (3)	C13'—O13'	1.429 (7)
O7W—H7W2	0.83 (3)	C13'—C14'	1.521 (8)
O8W—H8W1	0.84 (3)	C13'—H13'	1.0000
O8W—H8W2	0.81 (3)	O13'—H3O'	0.8400
O9W—H9W1	0.84 (3)	C14'—C15'	1.506 (8)
O9W—H9W2	0.83 (3)	C14'—H14'	1.0000
O11W—H11A	0.82 (3)	C15'—O15'	1.450 (7)
O11W—H11B	0.84 (3)	C15'—H5A'	0.9900
N1'—C7'	1.373 (7)	C15'—H5B'	0.9900
N1'—C4'	1.479 (7)	C17'—O7B'	1.245 (6)
N1'—C1'	1.491 (8)	C17'—O7A'	1.300 (7)
C1'—C2'	1.496 (9)	O15'—H5O'	0.8400
C1'—C9	1.528 (8)	N11—C12	1.378 (7)
C1'—H1'	1.0000	N11—C16	1.386 (7)
C2'—O2'	1.428 (7)	N11—H11N	0.8800
C2'—C3'	1.517 (8)	C12—N13	1.316 (7)
C2'—H2'	1.0000	C12—H12	0.9500
O2'—H2'O	0.8400	N13—C14	1.371 (7)
C3'—O3'	1.433 (7)	C14—C15	1.389 (8)
C3'—C4'	1.535 (8)	C14—C19	1.412 (8)
C3'—H3'	1.0000	C15—N17	1.356 (7)
O3'—H3'O	0.8400	C15—C16	1.407 (8)
C4'—C5'	1.507 (8)	C16—O16	1.257 (6)
C4'—H4'	1.0000	O16—Na1^ii	2.396 (4)
C5'—O5'	1.429 (7)	N17—C18	1.365 (7)
C5'—H5'A	0.9900	N17—H17N	0.8800
C5'—H5'B	0.9900	C18—C19	1.373 (8)
O5'—H5'O	0.8400	C18—H18	0.9500
C7'—O7'A	1.254 (7)
O9W—Na1—O5W	175.42 (18)	C4'—C5'—H5'B	108.5
O9W—Na1—O16^i	89.10 (16)	H5'A—C5'—H5'B	107.5
O5W—Na1—O16^i	87.54 (16)	C5'—O5'—H5'O	109.5
O9W—Na1—O8W	84.02 (16)	O7'A—C7'—O7'B	122.8 (5)
O5W—Na1—O8W	98.27 (16)	O7'A—C7'—N1'	120.3 (6)
O16^i—Na1—O8W	77.40 (15)	O7'B—C7'—N1'	116.8 (5)
O9W—Na1—O6	95.41 (16)	C2—N1—C6	124.7 (5)
O5W—Na1—O6	88.27 (16)	C2—N1—H1N	117.7
O16^i—Na1—O6	172.39 (15)	C6—N1—H1N	117.7
O8W—Na1—O6	96.94 (14)	N3—C2—N1	124.7 (6)
O9W—Na1—O2W	86.85 (16)	N3—C2—H2	117.6
O5W—Na1—O2W	90.99 (17)	N1—C2—H2	117.6
O16^i—Na1—O2W	104.75 (16)	C2—N3—C4	114.1 (5)
O8W—Na1—O2W	170.60 (16)	N3—C4—C5	123.2 (5)
O6—Na1—O2W	81.67 (15)	N3—C4—C9	129.0 (5)
O9W—Na1—H8W1	72.7 (10)	C5—C4—C9	107.8 (5)
O5W—Na1—H8W1	108.4 (10)	N7—C5—C4	108.7 (5)
O16^i—Na1—H8W1	63.6 (11)	N7—C5—C6	128.9 (5)
O8W—Na1—H8W1	18.4 (7)	C4—C5—C6	122.4 (5)
O6—Na1—H8W1	111.9 (11)	O6—C6—N1	120.2 (5)
O2W—Na1—H8W1	156.1 (7)	O6—C6—C5	128.8 (5)
O1W—Na2—O2W	106.58 (16)	N1—C6—C5	110.9 (5)
O1W—Na2—O3W	84.76 (16)	C6—O6—Na1	137.8 (4)
O2W—Na2—O3W	89.45 (16)	C6—O6—Na2	122.3 (3)
O1W—Na2—O6	165.81 (16)	Na1—O6—Na2	96.92 (15)
O2W—Na2—O6	82.83 (15)	C5—N7—C8	108.0 (5)
O3W—Na2—O6	106.30 (15)	C5—N7—H7N	126.0
O1W—Na2—O7B'	83.68 (16)	C8—N7—H7N	126.0
O2W—Na2—O7B'	167.45 (16)	N7—C8—C9	109.2 (6)
O3W—Na2—O7B'	84.24 (15)	N7—C8—H8	125.4
O6—Na2—O7B'	88.54 (14)	C9—C8—H8	125.4
O1W—Na2—O4W	89.51 (16)	C8—C9—C4	106.4 (5)
O2W—Na2—O4W	90.70 (16)	C8—C9—C1'	126.3 (6)
O3W—Na2—O4W	174.07 (16)	C4—C9—C1'	127.3 (5)
O6—Na2—O4W	79.60 (14)	N11'—C11'—C19	113.0 (4)
O7B'—Na2—O4W	96.70 (15)	N11'—C11'—C12'	104.8 (5)
O1W—Na2—H3W2	68.6 (10)	C19—C11'—C12'	114.0 (5)
O2W—Na2—H3W2	102.9 (11)	N11'—C11'—H11'	108.3
O3W—Na2—H3W2	18.7 (8)	C19—C11'—H11'	108.3
O6—Na2—H3W2	120.4 (11)	C12'—C11'—H11'	108.3
O7B'—Na2—H3W2	73.7 (12)	C17'—N11'—C11'	118.7 (5)
O4W—Na2—H3W2	156.7 (9)	C17'—N11'—C14'	122.5 (4)
H1W1—O1W—H1W2	101 (8)	C11'—N11'—C14'	112.1 (4)
Na2—O2W—Na1	95.78 (15)	O12'—C12'—C13'	110.8 (5)
Na2—O2W—H2W1	118 (5)	O12'—C12'—C11'	108.4 (5)
Na1—O2W—H2W1	96 (4)	C13'—C12'—C11'	103.4 (5)
Na2—O2W—H2W2	104 (5)	O12'—C12'—H12'	111.3
Na1—O2W—H2W2	139 (5)	C13'—C12'—H12'	111.3
H2W1—O2W—H2W2	105 (4)	C11'—C12'—H12'	111.3
Na2—O3W—H3W1	133 (5)	C12'—O12'—H2O'	109.5
Na2—O3W—H3W2	93 (5)	O13'—C13'—C12'	115.3 (4)
H3W1—O3W—H3W2	112 (7)	O13'—C13'—C14'	108.3 (5)
Na2—O4W—H4W1	114 (4)	C12'—C13'—C14'	107.1 (4)
Na2—O4W—H4W2	124 (4)	O13'—C13'—H13'	108.6
H4W1—O4W—H4W2	105 (4)	C12'—C13'—H13'	108.6
Na1—O5W—H5W1	103 (5)	C14'—C13'—H13'	108.6
Na1—O5W—H5W2	111 (5)	C13'—O13'—H3O'	109.5
H5W1—O5W—H5W2	120 (8)	N11'—C14'—C15'	114.5 (4)
H6W1—O6W—H6W2	107 (8)	N11'—C14'—C13'	102.6 (4)
H7W1—O7W—H7W2	105 (7)	C15'—C14'—C13'	109.7 (4)
Na1—O8W—H8W1	98 (4)	N11'—C14'—H14'	109.9
Na1—O8W—H8W2	130 (4)	C15'—C14'—H14'	109.9
H8W1—O8W—H8W2	108 (4)	C13'—C14'—H14'	109.9
Na1—O9W—H9W1	110 (4)	O15'—C15'—C14'	115.4 (5)
Na1—O9W—H9W2	129 (4)	O15'—C15'—H5A'	108.4
H9W1—O9W—H9W2	107 (4)	C14'—C15'—H5A'	108.4
H11A—O11W—H11B	110 (7)	O15'—C15'—H5B'	108.4
C7'—N1'—C4'	122.1 (5)	C14'—C15'—H5B'	108.4
C7'—N1'—C1'	120.3 (5)	H5A'—C15'—H5B'	107.5
C4'—N1'—C1'	111.7 (4)	O7B'—C17'—O7A'	122.7 (5)
N1'—C1'—C2'	105.0 (5)	O7B'—C17'—N11'	121.4 (5)
N1'—C1'—C9	111.6 (4)	O7A'—C17'—N11'	115.9 (5)
C2'—C1'—C9	115.6 (5)	C17'—O7B'—Na2	123.0 (3)
N1'—C1'—H1'	108.1	C15'—O15'—H5O'	109.5
C2'—C1'—H1'	108.1	C12—N11—C16	123.9 (5)
C9—C1'—H1'	108.1	C12—N11—H11N	118.1
O2'—C2'—C1'	107.8 (4)	C16—N11—H11N	118.1
O2'—C2'—C3'	110.5 (5)	N13—C12—N11	123.9 (6)
C1'—C2'—C3'	103.2 (5)	N13—C12—H12	118.0
O2'—C2'—H2'	111.6	N11—C12—H12	118.0
C1'—C2'—H2'	111.6	C12—N13—C14	114.6 (5)
C3'—C2'—H2'	111.6	N13—C14—C15	123.9 (5)
C2'—O2'—H2'O	109.5	N13—C14—C19	128.8 (5)
O3'—C3'—C2'	115.9 (4)	C15—C14—C19	107.2 (5)
O3'—C3'—C4'	105.8 (4)	N17—C15—C14	108.5 (5)
C2'—C3'—C4'	106.1 (5)	N17—C15—C16	130.2 (5)
O3'—C3'—H3'	109.6	C14—C15—C16	121.3 (5)
C2'—C3'—H3'	109.6	O16—C16—N11	120.0 (5)
C4'—C3'—H3'	109.6	O16—C16—C15	127.7 (5)
C3'—O3'—H3'O	109.5	N11—C16—C15	112.4 (5)
N1'—C4'—C5'	117.3 (5)	C16—O16—Na1^ii	129.2 (4)
N1'—C4'—C3'	101.6 (5)	C15—N17—C18	108.4 (5)
C5'—C4'—C3'	111.6 (4)	C15—N17—H17N	125.8
N1'—C4'—H4'	108.7	C18—N17—H17N	125.8
C5'—C4'—H4'	108.7	N17—C18—C19	109.7 (6)
C3'—C4'—H4'	108.7	N17—C18—H18	125.2
O5'—C5'—C4'	115.3 (4)	C19—C18—H18	125.2
O5'—C5'—H5'A	108.5	C18—C19—C14	106.2 (5)
C4'—C5'—H5'A	108.5	C18—C19—C11'	129.0 (6)
O5'—C5'—H5'B	108.5	C14—C19—C11'	124.8 (5)
O1W—Na2—O2W—Na1	178.36 (15)	C5—N7—C8—C9	−0.3 (6)
O3W—Na2—O2W—Na1	93.99 (16)	N7—C8—C9—C4	0.5 (6)
O6—Na2—O2W—Na1	−12.51 (14)	N7—C8—C9—C1'	−178.2 (5)
O7B'—Na2—O2W—Na1	34.4 (8)	N3—C4—C9—C8	−179.1 (5)
O4W—Na2—O2W—Na1	−91.94 (16)	C5—C4—C9—C8	−0.5 (6)
O9W—Na1—O2W—Na2	108.63 (17)	N3—C4—C9—C1'	−0.4 (9)
O5W—Na1—O2W—Na2	−75.41 (17)	C5—C4—C9—C1'	178.2 (5)
O16^i—Na1—O2W—Na2	−163.12 (14)	N1'—C1'—C9—C8	11.0 (7)
O6—Na1—O2W—Na2	12.70 (15)	C2'—C1'—C9—C8	−109.0 (6)
C7'—N1'—C1'—C2'	−143.6 (5)	N1'—C1'—C9—C4	−167.6 (5)
C4'—N1'—C1'—C2'	9.8 (6)	C2'—C1'—C9—C4	72.5 (8)
C7'—N1'—C1'—C9	90.5 (6)	C19—C11'—N11'—C17'	94.2 (6)
C4'—N1'—C1'—C9	−116.2 (5)	C12'—C11'—N11'—C17'	−141.1 (5)
N1'—C1'—C2'—O2'	89.4 (5)	C19—C11'—N11'—C14'	−113.7 (5)
C9—C1'—C2'—O2'	−147.2 (5)	C12'—C11'—N11'—C14'	11.0 (6)
N1'—C1'—C2'—C3'	−27.6 (5)	N11'—C11'—C12'—O12'	91.7 (5)
C9—C1'—C2'—C3'	95.8 (6)	C19—C11'—C12'—O12'	−144.2 (5)
O2'—C2'—C3'—O3'	38.1 (6)	N11'—C11'—C12'—C13'	−26.0 (5)
C1'—C2'—C3'—O3'	153.1 (4)	C19—C11'—C12'—C13'	98.1 (6)
O2'—C2'—C3'—C4'	−79.0 (5)	O12'—C12'—C13'—O13'	36.9 (6)
C1'—C2'—C3'—C4'	36.0 (5)	C11'—C12'—C13'—O13'	152.9 (5)
C7'—N1'—C4'—C5'	−73.3 (6)	O12'—C12'—C13'—C14'	−83.7 (5)
C1'—N1'—C4'—C5'	133.9 (5)	C11'—C12'—C13'—C14'	32.3 (5)
C7'—N1'—C4'—C3'	164.8 (5)	C17'—N11'—C14'—C15'	−81.7 (6)
C1'—N1'—C4'—C3'	12.0 (5)	C11'—N11'—C14'—C15'	127.5 (5)
O3'—C3'—C4'—N1'	−153.0 (4)	C17'—N11'—C14'—C13'	159.5 (5)
C2'—C3'—C4'—N1'	−29.3 (5)	C11'—N11'—C14'—C13'	8.7 (5)
O3'—C3'—C4'—C5'	81.3 (5)	O13'—C13'—C14'—N11'	−150.3 (4)
C2'—C3'—C4'—C5'	−155.0 (5)	C12'—C13'—C14'—N11'	−25.4 (5)
N1'—C4'—C5'—O5'	81.7 (6)	O13'—C13'—C14'—C15'	87.6 (6)
C3'—C4'—C5'—O5'	−161.7 (4)	C12'—C13'—C14'—C15'	−147.5 (5)
C4'—N1'—C7'—O7'A	−160.1 (5)	N11'—C14'—C15'—O15'	71.8 (6)
C1'—N1'—C7'—O7'A	−9.5 (7)	C13'—C14'—C15'—O15'	−173.5 (5)
C4'—N1'—C7'—O7'B	18.2 (7)	C11'—N11'—C17'—O7B'	−7.8 (7)
C1'—N1'—C7'—O7'B	168.8 (4)	C14'—N11'—C17'—O7B'	−156.8 (5)
C6—N1—C2—N3	−0.7 (8)	C11'—N11'—C17'—O7A'	174.2 (4)
N1—C2—N3—C4	1.1 (7)	C14'—N11'—C17'—O7A'	25.1 (7)
C2—N3—C4—C5	−1.0 (7)	O7A'—C17'—O7B'—Na2	−99.3 (5)
C2—N3—C4—C9	177.4 (5)	N11'—C17'—O7B'—Na2	82.8 (5)
N3—C4—C5—N7	179.1 (5)	O1W—Na2—O7B'—C17'	−6.0 (4)
C9—C4—C5—N7	0.4 (6)	O2W—Na2—O7B'—C17'	139.5 (7)
N3—C4—C5—C6	0.5 (8)	O3W—Na2—O7B'—C17'	79.3 (4)
C9—C4—C5—C6	−178.1 (5)	O6—Na2—O7B'—C17'	−174.1 (4)
C2—N1—C6—O6	179.6 (5)	O4W—Na2—O7B'—C17'	−94.8 (4)
C2—N1—C6—C5	0.2 (7)	C16—N11—C12—N13	−1.6 (8)
N7—C5—C6—O6	2.3 (9)	N11—C12—N13—C14	0.2 (8)
C4—C5—C6—O6	−179.5 (5)	C12—N13—C14—C15	0.8 (8)
N7—C5—C6—N1	−178.3 (5)	C12—N13—C14—C19	178.1 (5)
C4—C5—C6—N1	−0.1 (7)	N13—C14—C15—N17	176.7 (5)
N1—C6—O6—Na1	175.7 (3)	C19—C14—C15—N17	−1.1 (6)
C5—C6—O6—Na1	−4.9 (9)	N13—C14—C15—C16	−0.4 (8)
N1—C6—O6—Na2	−28.6 (6)	C19—C14—C15—C16	−178.2 (5)
C5—C6—O6—Na2	150.7 (5)	C12—N11—C16—O16	−178.0 (5)
O9W—Na1—O6—C6	60.9 (5)	C12—N11—C16—C15	1.9 (7)
O5W—Na1—O6—C6	−121.8 (5)	N17—C15—C16—O16	2.5 (10)
O8W—Na1—O6—C6	−23.7 (5)	C14—C15—C16—O16	178.9 (5)
O2W—Na1—O6—C6	146.9 (5)	N17—C15—C16—N11	−177.3 (5)
O9W—Na1—O6—Na2	−98.55 (16)	C14—C15—C16—N11	−0.9 (7)
O5W—Na1—O6—Na2	78.71 (16)	N11—C16—O16—Na1^ii	−131.1 (4)
O8W—Na1—O6—Na2	176.83 (14)	C15—C16—O16—Na1^ii	49.1 (7)
O2W—Na1—O6—Na2	−12.54 (15)	C14—C15—N17—C18	1.0 (6)
O1W—Na2—O6—C6	−18.4 (9)	C16—C15—N17—C18	177.7 (6)
O2W—Na2—O6—C6	−150.9 (4)	C15—N17—C18—C19	−0.4 (6)
O3W—Na2—O6—C6	121.8 (4)	N17—C18—C19—C14	−0.3 (6)
O7B'—Na2—O6—C6	38.2 (4)	N17—C18—C19—C11'	178.9 (5)
O4W—Na2—O6—C6	−58.9 (4)	N13—C14—C19—C18	−176.8 (5)
O1W—Na2—O6—Na1	145.4 (7)	C15—C14—C19—C18	0.8 (6)
O2W—Na2—O6—Na1	12.95 (15)	N13—C14—C19—C11'	4.0 (9)
O3W—Na2—O6—Na1	−74.36 (17)	C15—C14—C19—C11'	−178.4 (5)
O7B'—Na2—O6—Na1	−157.92 (14)	N11'—C11'—C19—C18	21.7 (8)
O4W—Na2—O6—Na1	104.99 (15)	C12'—C11'—C19—C18	−97.8 (7)
C4—C5—N7—C8	0.0 (6)	N11'—C11'—C19—C14	−159.3 (5)
C6—C5—N7—C8	178.4 (5)	C12'—C11'—C19—C14	81.2 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3′^iii	0.82 (5)	2.00 (5)	2.815 (5)	175 (7)
O1W—H1W2···O12′	0.78 (5)	1.99 (5)	2.735 (5)	160 (8)
O2′—H2′O···O11W	0.84	1.92	2.745 (5)	168
O2W—H2W1···O10W^iv	0.83 (5)	2.02 (5)	2.849 (6)	178 (7)
O3′—H3′O···O7′B^v	0.84	1.87	2.683 (4)	163
O2W—H2W2···O5′^iii	0.83 (5)	2.07 (5)	2.878 (6)	163 (6)
O3W—H3W1···O7′B^iii	0.80 (5)	2.08 (5)	2.839 (5)	159 (5)
O5′—H5′O···O7′B	0.84	1.93	2.701 (6)	152
O3W—H3W2···O7W^iii	0.84 (5)	1.99 (5)	2.785 (6)	158 (5)
O4W—H4W1···O6W	0.85 (4)	1.93 (4)	2.748 (7)	163 (5)
N7—H7N···O8W	0.88	2.06	2.833 (6)	145
O4W—H4W2···N13	0.82 (4)	2.15 (5)	2.952 (6)	165 (5)
O5W—H5W1···O4W^vi	0.85 (6)	2.06 (6)	2.821 (6)	150 (6)
O5W—H5W2···O12′^vi	0.80 (5)	2.24 (6)	2.951 (6)	148 (6)
O6W—H6W1···O15′^vii	0.84 (5)	1.89 (6)	2.717 (6)	168 (6)
O11W—H11A···O13′^viii	0.82 (5)	2.19 (5)	2.968 (5)	158 (5)
O11W—H11B···O7′A^v	0.84 (6)	2.09 (5)	2.846 (5)	150 (6)
N11—H11N···O7′A^v	0.88	1.85	2.729 (6)	175
O6W—H6W2···O9W	0.82 (6)	1.98 (5)	2.778 (6)	164 (7)
O12′—H2O′···O3W^v	0.84	1.93	2.704 (5)	153
O7W—H7W1···O7A′^viii	0.81 (4)	1.98 (5)	2.773 (5)	165 (5)
O13′—H3O′···O7A′^v	0.84	1.84	2.667 (5)	166
O7W—H7W2···O2′	0.83 (5)	1.86 (5)	2.685 (6)	170 (7)
O8W—H8W1···O11W^i	0.84 (5)	1.99 (6)	2.795 (6)	160 (5)
O15′—H5O′···O7A′	0.84	1.85	2.650 (6)	159
O8W—H8W2···O6W^vi	0.81 (4)	2.01 (4)	2.818 (6)	175 (6)
O9W—H9W1···O10W^iv	0.84 (5)	1.96 (5)	2.780 (6)	165 (5)
N17—H17N···O5W^ii	0.88	2.06	2.919 (6)	166
O9W—H9W2···O7W^iv	0.83 (4)	2.08 (3)	2.861 (7)	156 (6)
N1—H1N···O7B′	0.88	1.86	2.733 (6)	175

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