Purine 3′:5′-cyclic nucleotides with the nucleobase in a syn orientation: cAMP, cGMP and cIMP

Ślepokura, K.A.

doi:10.1107/S2053229616006999

Purine 3':5'-cyclic nucleotides with the nucleobase in a syn orientation: cAMP, cGMP and cIMP

Purine 3':5'-cyclic nucleotides are very well known for their role as the secondary messengers in hormone action and cellular signal transduction. Nonetheless, their solid-state conformational details still require investigation. Five crystals containing purine 3':5'-cyclic nucleotides have been obtained and structurally characterized, namely adenosine 3':5'-cyclic phosphate dihydrate, C₁₀H₁₂N₅O₆P·2H₂O or cAMP·2H₂O, (I), adenosine 3':5'-cyclic phosphate 0.3-hydrate, C₁₀H₁₂N₅O₆P·0.3H₂O or cAMP·0.3H₂O, (II), guanosine 3':5'-cyclic phosphate pentahydrate, C₁₀H₁₂N₅O₇P·5H₂O or cGMP·5H₂O, (III), sodium guanosine 3':5'-cyclic phosphate tetrahydrate, Na⁺·C₁₀H₁₁N₅O₇P^-·4H₂O or Na(cGMP)·4H₂O, (IV), and sodium inosine 3':5'-cyclic phosphate tetrahydrate, Na⁺·C₁₀H₁₀N₄O₇P^-·4H₂O or Na(cIMP)·4H₂O, (V). Most of the cyclic nucleotide zwitterions/anions [two from four cAMP present in total in (I) and (II), cGMP in (III), cGMP^- in (IV) and cIMP^- in (V)] are syn conformers about the N-glycosidic bond, and this nucleobase arrangement is accompanied by C_rib-H

N_pur hydrogen bonds (rib = ribose and pur = purine). The base orientation is tuned by the ribose pucker. An analysis of data obtained from the Cambridge Structural Database made in the context of syn-anti conformational preferences has revealed that among the syn conformers of various purine nucleotides, cyclic nucleotides and dinucleotides predominate significantly. The interactions stabilizing the syn conformation have been indicated. The inter-nucleotide contacts in (I)-(V) have been systematized in terms of the chemical groups involved. All five structures display three-dimensional hydrogen-bonded networks.

Keywords: 3':5'-cyclic nucleotides; adenosine 3':5'-cyclic phosphate; guanosine 3':5'-cyclic phosphate; inosine 3':5'-cyclic phosphate; cAMP; cGMP; cIMP; crystal structure; sodium salts; 1,3,2-dioxaphosphorinane; syn-anti nucleobase conformation; CSD data screening.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616006999/sk3622sup1.cif Contains datablocks I_camp, II_camp1ab, III_gmpdc, IV_gmpna, V_impna, I-V
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006999/sk3622I_campsup2.hkl Contains datablock I_camp
	MDL mol file https://doi.org/10.1107/S2053229616006999/sk3622I_campsup7.mol Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006999/sk3622II_camp1absup3.hkl Contains datablock II_camp1ab
	MDL mol file https://doi.org/10.1107/S2053229616006999/sk3622II_camp1absup8.mol Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006999/sk3622III_gmpdcsup4.hkl Contains datablock III_gmpdc
	MDL mol file https://doi.org/10.1107/S2053229616006999/sk3622III_gmpdcsup9.mol Supplementary material
	MDL mol file https://doi.org/10.1107/S2053229616006999/sk3622IV_gmpnasup10.mol Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006999/sk3622IV_gmpnasup5.hkl Contains datablock IV_gmpna
	MDL mol file https://doi.org/10.1107/S2053229616006999/sk3622V_impnasup11.mol Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006999/sk3622V_impnasup6.hkl Contains datablock V_impna

CCDC references: 1476482; 1476481; 1476480; 1476479; 1476478

Introduction top

3':5'-Cyclic nucleotides (cNMP), especially purine cyclic nucleotides have been known since the mid-20th century, when adenosine 3':5'-cyclic phosphate (cAMP) was discovered (Rall et al., 1957) and structurally characterized (Lipkin et al., 1959) and guanosine 3':5'-cyclic phosphate (cGMP) was isolated (Ashman et al., 1963). Today the role of both cAMP and cGMP as the second messengers in hormone action and cellular signal transduction under normal physiological conditions (as well as in a number of pathophysiological states, including cancer) is well known and documented (Rehmann et al., 2007; Fajardo et al., 2014). cNMP receptor proteins, for example, the protein kinases or cyclic-nucleotide-regulated ion channels, have conserved cyclic nucleotide binding domains (CNBD), which bind cAMP or cGMP (Rehmann et al., 2007; Schmidt et al., 2009). It should be mentioned that other cNMPs, including inosine 3':5'-cyclic phosphate (cIMP) have been identified in mammalian tissues (Newton et al., 1986). In addition, the utility of 3':5'-cyclic nucleotides analogues as prodrugs with anti-HCV efficacy has been reported (Reddy et al., 2010; Du et al., 2012).

From all structural aspects (in addition to sugar and phosphate O/P/O/C/C/C rings puckering), the syn–anti conformation about the N-glycosydic C1'—N bond is of great interest. It is known that in solution the distribution between the syn and anti conformers of cNMPs is ~30:70 for cAMP and 95:5 for cGMP (Francis et al., 2011). In the cyclic nucleotide-binding domain (CNBD) of cNMP-gated channels, cAMP and cGMP bind in different conformations about the glycosidic bond, i.e. cAMP in the anti and cGMP in the syn form (Schmidt et al., 2009). On the other hand, catalytic sites of some families of mammalian phosphodiesterases (PDEs) bind cyclic nucleotides in a syn conformation, while the other – in anti [not clear], regardless of the specificity of the enzyme towards cAMP or cGMP. Another issue to be taken into account is the conformation of the substrate (cNMP) versus the conformation of the product (5'-NMP), which is not always the same, as well as the role of the interactions of the purine nucleobase with the purine-binding pocket of the PDE catalytic site in the catalytic process and the substrate release.

Although, from a solid-state structure point of view, purine 3':5'-cyclic nucleotides are slightly better determined than their pyrimidine analogues, their structural details still need to be investigated. In the Cambridge Structural Database (CSD, Version 5.37; Groom & Allen, 2014) and the latest literature data (Ślepokura, 2016a), there are only 13 reported structures of cNMPs without covalent modification, eight of which are the structures of purine nucleotides: cAMP (two examples), cGMP (three structures) and cIMP (three structures). In spite of the general preference of the nucleobase in all types of nucleotides to adopt an anti (χ_CN 180±90°) rather than a syn (χ_CN 0±90°) orientation, it is known that guanosine and its nucleotides often adopt a syn conformation about the N-glycosidic C1'—N9 bond both in solution and in the solid state (Saenger, 1984; Blackburn & Gait, 1996). This uniqueness of guanosine compounds and their preference for a syn arrangement is believed to be related to van der Waals and electrostatic attractions between the amino group in position 2 of the base and the 5'-phosphate group (see the Scheme for the atom-numbering), which are associated with the change in electronic structure of the purine. The same effect was thought to stabilize the syn conformation of IMP nucleotides (Saenger, 1984). The intramolecular hydrogen bonds formed between the purine base and 5'-hydroxy group or the phosphate group, e.g. N2—H···O5' (for guanosine derivatives) or O5'—H···N3 (for nucleosides in general) are believed to play a role in the stabilization of the syn conformations (Govil & Hosur, 1982; Saenger, 1984). It has also been shown that in the RNAs with tertiary structure, including aptamers, riboswitches, ribozymes and ribosomal RNAs, the syn conformers are much more common among purine nucleotides (Sokoloski et al., 2011). Furthermore, a correlation between the conformation about the C1'—N9 bond and the sugar ring puckering has been revealed both by X-ray crystallography and NMR techniques for nucleotides, both free and in nucleic acids. Thus, syn conformers slightly favour ²E-like conformations, while anti conformers are associated with ³E-like sugar puckering modes, which, however, is not in line for cyclic nucleotides, which are known to have furanose ring fixed in a high-energy conformation ³T₄ [Saenger, 1984; definitions of puckering descriptors are given in IUPAC–IUB Joint Commission on Biochemical Nomenclature (1983) and IUPAC–IUBMB Joint Commission on Biochemical Nomenclature (1996)].

To gain insight into the structures of cyclic nucleotides, five crystals of purine cNMPs have been obtained and structurally characterized, namely cAMP·2H₂O, (I), cAMP·0.3H₂O, (II), cGMP·5H₂O, (III), Na(cGMP)·4H₂O, (IV), and Na(cIMP)·4H₂O, (V) (see Scheme). The syn–anti preference of various purine nucleotides was analysed statistically based on CSD data. In addition, inter-nucleotide interactions and nucleotide–Na interaction modes have been analysed.

Experimental top

Synthesis and crystallization top

To commercially available cAMP (Sigma; 60 mg, 0.182 mmol) dissolved in distilled water, KHCO₃ (9.1 mg, 0.091 mmol) was added and the solution was evaporated at room temperature for several days to give large plate-shaped crystals of (I), i.e. cAMP·2H₂O. Small plates of (II), i.e. cAMP·0.3H₂O, were obtained after a three-month room-temperature evaporation of an MeOH solution of a cAMP–KHCO₃ mixture (molar ratio 2:1). Crystals of (I) were also obtained in an analogous procedure from a water solution of a cAMP–CaCl₂·6H₂O mixture (molar ratio 1:1) or a cAMP–NaHCO₃ (molar ratio 2:1) or cAMP–CaCl₂·6H₂O–NaHCO₃ (molar ratio 3:1:1) mixture, or by slow room-temperature evaporation of water, MeOH, EtOH, i-PrOH or water–EtOH (2:1 v/v) solutions of cAMP, but then the crystallization took several weeks or months, and the crystals were of much worse quality. It should be noted that cAMP is slightly soluble in water and alcohols, thus its solutions need heating to about 320 K or decantation from the undissolved solid before crystallization.

A solution of commercially available Na(cGMP)·5.5H₂O (Sigma; 60 mg) in a minimal quantity of distilled water was passed through an ion-exchange column [Dowex 50-H⁺ × 2–100 (Serva) was regenerated after use by washing it with 3–4 M HCl and then with water until the pH was neutral]. The acidic solution of cGMP was evaporated slowly to give delicate plates of (III), i.e. cGMP·5H₂O. The same crystals were also obtained from water solution of cGMP–KaHCO₃ (molar ratio 2:1) or cGMP–CaCl₂·6H₂O (molar ratio 2:1). Crystals of (III) are slightly soluble in water or water–alcohol solutions, thus they appear even at low concentrations.

Commercially available Na(cGMP)·5.5H₂O (Sigma) was dissolved in distilled water and evaporated slowly at room temperature for several days to give large blocks of (IV), i.e. Na(cGMP)·4H₂O. In a similar way, by room-temperature evaporation of a water–i-PrOH (10:1 v/v) solution of commercially available Na(cIMP)·H₂O (Sigma), plates of (V), i.e. Na(cIMP)·4H₂O, were obtained.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The room-temperature crystal structure of (IV), i.e. Na(cGMP)·4H₂O, has been reported previously (CSD refcode SCGMPT10; Chwang & Sundaralingam, 1974). We report here the structure at 100 K in the standard cell setting. The structure of cAMP·0.3H₂O, (II), has also been reported in the literature (ADCPOP; Watenpaugh et al., 1968), but the atomic coordinates have not been deposited in the CSD.

The water molecule in (II) was found to be not fully occupied and was refined to a site-occupancy factor (SOF) of 0.630 (15).

The diffraction data for (III) were collected at 298 K, due to the low quality of the diffraction pattern or even breaking of the crystal at lower temperatures, which was difficult to avoid even using flash cooling or slow cooling from room temperature. The probable reason is a phase transition at 260–270 K, which is suggested by changes in the diffraction pattern obtained from the crystal during temperature changes; this will be the subject of further analyses. At room temperature, all the water molecules in (III) are highly disordered; O1W, O3W, O4W and O5W were refined isotropically and distributed over four positions each, and O2W over five [SOFs are: 0.30 (3)/0.25 (3)/0.24 (3)/0.21 (2) for O1W, 0.29 (4):0.21 (3):0.21 (3):0.16 (4):0.13 (3) for O2W, 0.35 (3):0.25 (3):0.25 (3):0.14 (2) for O3W, 0.44 (5):0.24 (5):0.19 (3):0.14 (4) for O4W and 0.46 (4):0.33 (2):0.14 (2):0.07 (4) for O5W]. The respective water positions were refined with linear restraints applied to their occupancies, with the SOFs summing to unity. The water H atoms in (III) were not found in the difference Fourier maps. The finally accepted formula for (III) is cGMP.5H₂O, although the number of solvent molecules should be treated as a rough approximation.

The O3W water molecules in (IV) and (V) were found to be slightly disordered and were refined with the O atoms in two positions each, with SOFs of 0.929 (11):0.071 (11) in (IV) and 0.861 (8):0.139 (8) in (V). The sites with lower occupancy were refined isotropically. Both O3W-bound H atoms in (IV) and one of them in (V) were modelled as common for two positions of the O atoms. The other H atom of O3W in (V) was refined over two positions.

Most of the C-bound H atoms and all O- or N-bound H atoms in (I)–(V) were found in difference Fourier maps. The remaining H atoms were included using geometrical considerations. In the final refinement cycles, all C-bound H atoms in (I)–(V) were repositioned in their calculated positions and refined using a riding model, with C—H = 0.93–1.00 Å, and with U_iso(H) = 1.2U_eq(C) for CH and CH₂ groups, and U_iso(H) = 1.5U_eq(C) for CH₃ groups. Purine N-bound, ribose O-bound and water H atoms were refined with the N—H and O—H bond lengths restrained to 0.880 (2) and 0.840 (2) Å, respectively, and with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O), and then they were constrained to ride on their parent atoms. Additionally, H···H distances in the water molecules in (I), (II), (IV) and (V) were set at 1.38 Å.

Data screening top

The statistical study concerning the conformation of purine nucleotides is based on the crystal structures deposited in the Cambridge Structural Database (CSD, Version 5.37; Groom & Allen, 2014). The ConQuest program (Version 1.18; Bruno et al., 2002) was used to retrieve structures satisfying the following criteria: (i) a phosphate group attached to the 5'-, 3'- and/or 2'-position of the nucleoside, (ii) no additional (to the glycosidic) covalent bonds between base and sugar, (iii) no powder structures and (iv) three-dimensional coordinates determined. Disordered and polymeric structures, both anions and zwitterions of (oligo)nucleotides, and nonsubstituted and covalently modified compounds were included. For the syn–anti analysis, the χ_CN torsion angles (O4'—C1'—N9—C4) were investigated. Since the absolute configuration in several structures is incorrect, the inverted models were used and the values of χ_CN were corrected accordingly (changed into opposite) before making the histograms.

Results and discussion top

Conformations of the cAMP and cGMP zwitterions, and the cGMP\\\\\\\^-\\\\\\\^ and cIMP\\\\\\\^-\\\\\\\^ anions top

The asymmetric units of (I)–(III), with the general formula cRMP·xH₂O [R is the purine nucleoside, i.e. adenosine (A) or guanosine (G)], consist of two cAMP zwitterions in (I) and (II), one cGMP zwitterion in (III), and four, 0.6 or five water molecules, respectively (Figs. 1 and 2, and Figs. S1–S3 in the Supporting information). The crystallographically independent zwitterions in (I) and (II), hereafter denoted as cAMP-A and cAMP-B, have the phosphate group deprotonated and the adenine N1 atom protonated. The zwitterion of cGMP in (III) has the guanine N7 atom protonated. As shown in Fig. S3 ( see the Supporting information), all water molecules in (III) are highly disordered and were refined over four (O1W, O3W, O4W and O5W) or five (O2W) positions each. The asymmetric units of the sodium salts (IV) and (V) comprise one cGMP^- or cIMP^- anion, one Na⁺ cation and four water molecules each (one of which is disordered as shown in Fig. 2).

As shown in Figs. 1 and 2, most of the cNMPs present in (I)–(V) exist with the purine nucleobase located above the ribose ring, i.e. in a syn conformation about the N-glycosidic bond. According to the general definition (IUPAC–IUB Joint Commission on Biochemical Nomenclature, 1983), nucleotides with χ_CN = 0±90° are called syn conformers, while those with χ_CN = 180±90° are anti conformers. It should be noted, however, that values of χ_CN lying just beyond the borderline of the syn and anti descriptors, i.e. in the +ac range (90 < χ_CN < ~120°) or in the -sc range (-90 < χ_CN < -60°), although formally referred to, respectively, as anti and syn conformers, in practice indicate that the nucleobase is located above the ribose ring or not, and therefore are denoted as high-syn or high-anti, respectively. The χ_CN torsion angles for the purine 3':5'-cyclic nucleotides (those reported to date and presented here) lie in two narrow ranges: (i) -175 < χ_CN < -122° (anti) and (ii) 59 < χ_CN < 91° (syn and high-syn). Obviously, cGMP prefers the syn arrangement (see Table 2 for details). In cGMP, cGMP^- and cIMP^-, stabilization of the syn conformation is provided by C_rib—H···N3_pur hydrogen-bond contacts (rib = ribose; pur = purine) formed mainly by atom C3', but also by atom C2', as well as by both C2' and C3' (Fig. 3), instead of N2—H···O5' (which may not be formed due to O5' being involved in the O/P/O/C/C/C ring; N2···O5' > 5.9 Å) or N2—H···O_phos (phos = phosphate; N2···O3 > 4.5 Å).

For cyclic purine nucleotides, the base orientation is slightly tuned by the ribose pucker (Figs. 3 and 4, and conformational parameters given in Table 2). The sugar rings in all the cAMP, cGMP and cIMP anions/zwitterions are locked in the N range (northern half; pseudorotation parameter P = 0±90°; Rao et al., 1981) and lie between envelope puckering ³E (P for ideal ³E = 18°) and E₄ (ideal P = 54°), with the intermediate twist form (ideal P = 36°) and its deformations (³T₄) being the most common. That is quite typical for 3':5'-cyclic nucleotides, which have been known to be restricted to the ³T₄ conformation (Saenger, 1984). However, based on the data from Table 2 (and visualised in Fig. S4 in the Supporting information), the general observation may be stated as follows: the syn and anti forms favour slightly different sugar conformations; anti nucleotides adopt a ribose puckering mode close to ³E and ³₄T, while (high-)syn-nucleotides prefer ribose puckering close to ³₄T and E₄.

Superposition of the syn and anti conformers (Fig. 4) reveals relatively large differences in the position of the phosphate P and O atoms (especially exocyclic O atoms), which play a dominant role in the formation of intermolecular contacts (e.g. within the protein active site). This is the cumulative effect of two different factors: (i) a sugar puckering mode and (ii) a chair-puckered six-membered 1,3,2-dioxaphosphorinane ring deformation. The puckering characteristics for the O/P/O/C/C/C ring, given in Table 3, confirm a chair conformation with significant flattening at the phosphate end. This distortion is reflected in both the Cremer–Pople parameters (Cremer & Pople, 1975) and in the values of the angle between the O/P/O and C/C/C planes (denoted herein as φ₃). In the chair-puckered-model compounds (monocyclic 1,3,2-dioxaphosphorinanes; Ślepokura, 2008, 2013, 2016b; Ślepokura & Lis, 2004; Ślepokura & Mitaszewska, 2011), the flattening is related to the ionization state of the phosphate group as follows: anions are more evenly puckered (ideal chair; φ₃ of a few degrees) than the free acids or triesters (φ₃ > 12°). Although the phosphate rings in all the 3':5'-cylic nucleotides reported to date (including the compounds presented here) are ionized, the values of φ₃ determined for them are relatively high and range from 7.2 to 25.6° [Table 3 and Groom & Allen (2014)]. That is clear evidence that the deformation of the O/P/O/C/C/C ring is much more marked in cyclic nucleotides (with fused furanose ring) than in monocyclic compounds. As noted previously (Ślepokura, 2016b), there is a correlation between the flattening of the ring at the P end (expressed by φ₁) and the puckering at the opposite C end (φ₂) and, consequently, the overall deformation of the ring (φ₃); with increased flattening, the puckering at the opposite C atom (φ₂) usually decreases, which means that the phosphate ring flattens on the one side and puckers on the other at the same time. (Definitions for φ₁ and φ₂ are given in the footnote of Table 3.) The influence of different deformations of the O/P/O/C/C/C ring on the overall conformation of the cyclic nucleotide is illustrated in Fig. 4(c), where the geometry of two cNMPs with the same sugar puckering and a different deformation of the phosphate ring [φ₃ for cAMP-B in (I) = 7.2 (5)°, and for cGMP^- in (IV) = 25.6 (2)°] is compared.

Finally, it should be noted that according to the present state of knowledge, the phosphate ring distortion (deformation from the ideal chair conformation) in both purine and pyrimidine 3':5'-cylic nucleotides is related neither to an overall ionization state of the nucleotide, nor to nucleobase type and its syn–anti conformation, nor to the furanose puckering. It seems that the deformation of the O/P/O/C/C/C ring is influenced mostly by different factors, e.g. the chemical environment and the intermolecular interactions made by the nucleotide.

As indicated in Table 4, the cyclic phosphate groups in (I)–(V) are deformed from the ideal tetrahedral shape. As in the other cyclic chair-puckered anionic dioxaphosphorinanes, both model compounds and the other 3':5'-cyclic nucleotides, endocyclic P—O bonds (of approximately 1.61 Å) are over 0.1 Å longer than the exocyclic P—O bonds (on average 1.49 Å). This is accompanied by a distribution of the values of the O—P—O angles in which the endo- and exocyclic angles (O3'—P1—O5' and O3—P1—O5, respectively) are the smallest and the largest, respectively (on average 103 and 118°), in which the strain in the phosphate group is mostly manifested.

CSD data analysis: the syn–anti preference of purine nucleotides top

By searching the CSD with the criteria described in Section 2.3, the following numbers of structures of purine nucleoside 5'-, 3'- or/and 2'-(oligo)phosphates (including 3':5'- and 2':3'-cyclic nucleotides) were found: 67 structures of various Ade nucleotides (103 fragments), 81 structures of Gua nucleotides (164 fragments) and 17 Hyp nucleotides (only IMPs; 24 fragments). Along with the structures presented here, there are 107 fragments of Ado–P, 166 fragments of Guo–P1and 25 fragments of IMPs (Ado–P and Guo–P stand for various mono- and oligophosphates of Ado and Guo nucleosides). In order to study the preference for the syn or anti conformation about the N-glycosidic bond, the distribution of the χ_CN torsion angle (O4'—C1'—N9—C4) was analysed (Fig. 5).

By comparing the Ade, Gua and Hyp nucleotides, some general features may be observed. (i) In the solid state, there is not a clear tendency of Gua nucleotides to adopt a syn conformation; about 11% of all Guo–P (18 fragments) and 12% of Ado–P (13 fragments) are syn conformers. (ii) There is a slight tendency for Guo–P to adopt a high-anti arrangement compared to Ado–P and IMPs. (iii) Among the syn conformers of various purine nucleotides, cyclic nucleotides and dinucleotides predominate significantly. From the 13 syn-Ado–P structures, there are six dinucleotides and six cAMP derivatives, from the 18 syn-Guo–P structures, there are five dinucleotides, eight cGMP derivatives and one 2':3'-cGMP, and both the syn-IMPs are the salts of cIMP. It should be noted here that two of six syn-arranged cAMP derivatives are substituted in the 8-position of the adenine base, thus their conformation is forced to lock in the syn region. (iv) Syn conformations are stabilized by C_rib—H···N3_pur (where C_rib = C2' or C3') or O5'—H···N3_pur hydrogen bonds. If there is a free hydroxy group at the C5' atom, it usually forms a hydrogen bond with the N3_pur atom (as in Ade dinucleotides A-3'-5'-A or A-2'-5'-A or Gua dinucleotides G-2'-5'-C), and this is accompanied by the smallest values of the χ_CN torsion angles (41–56°). However, if the OH group at the C5' atom is not available, C2'—H···N3_pur or C3'—H···N3_pur contacts are formed, depending on the value of χ_CN (i.e. the smaller values of χ_CN are associated with the C3'—H···N3_pur interaction), which has to be also related with the sugar ring puckering providing the H atoms accessible for hydrogen bonding. It should be stressed that intramolecular N2_Gua—H···O hydrogen bonds have not been observed. Instead, the C2-bonded NH₂ group of the guanine base is involved in water-mediated N2—H···H₂O···O_phos contacts in several structures. The preference for the formation of C_rib—H···N3_pur interactions is clearly manifested in the structure of the Et₃NH⁺ salt of 2':3'-cGMP [χ_CN = 65.2 (2)°; CSD refcode CELLOV; Sierosławski et al., 2006), the syn arrangement of which is accompanied by neither the N2—H···O5' nor the O5'—H···N3 contacts (both possible due to a free hydroxymethyl group), but by the C5'—H···N3_pur interaction (Fig. 6).

Inter-nucleotide interactions in (I)–(V) top

Crystals of (cyclic) nucleotides may be useful models for understanding the noncovalent interactions involving nucleotides in biological systems. Therefore, all the intermolecular contacts present in (I)–(V) may be divided into two groups: (i) direct and indirect inter-nucleotide hydrogen bonds and other contacts [cNMP···cNMP and cNMP···(H₂O)_n···cNMP], and (ii) coordination interactions with the Na⁺ ions. Those from group (i) may be realized in several ways, e.g. edge-to-edge non-Watson–Crick base pairing, stacking interactions, base–sugar, base–phosphate, sugar–phosphate and sugar–sugar interactions.

In nucleotides (I) and (II), the vast majority of the types of direct inter-nucleotide contacts are present, but the crystal packings are dominated by base–phosphate and base–sugar interactions (Tables 5–7), which are realized in a syn-cAMP–anti-cAMP mode, and in which the protonated N1_Ade atom (along with the contribution of N6_Ade of anti conformer) is predominantly involved. Sugar–phosphate and sugar–sugar interactions, also formed between syn and anti conformers, are identical in (I) and (II), in terms of both atoms being involved and the geometry (strength) of the contacts. These give rise to layers parallel to (001) plane, almost identical in (I) and (II) (Fig. 7). The additional stabilization of the layer is provided by the Ade–Ade π–π stacking interactions along the a axis (Fig. 8). The interlayer contacts are realized via water-mediated inter-nucleotide cAMP···(H₂O)_n···cAMP interactions (Fig. 8), while in (II), with very few water molecules in the crystal lattice, additional direct cAMP···cAMP hydrogen bonds occur, in which N6_Ade atoms from syn conformers are used (N6A···N7Bⁱⁱⁱ, N6A···O3B^iv,O5B^iv; the symmetry codes are as in Table 7).

In nucleotides (III) and (IV), the direct inter-nucleotide contacts are realized mainly by base–phosphate hydrogen bonds and base–base stacking interactions, which play the most important role in the cGMP– self-assembly (Tables 5, 8 and 9). The bifurcated Gua–phosphate N1—H1···O5ⁱⁱ and N2—H2A···O5ⁱⁱ hydrogen bonds give rise to nucleotide ribbons running down the c axis (Fig. 9a). Adjacent ribbons (at y = 0, 1/2, ···) are crosslinked along the b axis by sugar–phosphate O2'—H2'···O3ⁱ hydrogen bonds [which in (IV) is additionally accompanied by a weaker O2'—H2'···O5ⁱ hydrogen bond], and stacked along the a axis via Gua–Gua π–π interactions. As a result, channels running down the a axis filled with water [in (III)] or water impregnated with Na⁺ ions, i.e. chains of edges-sharing Na(H₂O)₆ octahedra [in (IV)] are formed (Figs. 9b and 9c). Interestingly, the crystal architectures of (III) and (IV) are very similar, which is shown by the superposition of the ribbons presented in Fig. 9(a), and the main difference is related to the ionization state of the ribbons, which are neutral in (III) and anionic in (IV), due to the N7_Gua atom being protonated in (III).

Gua–Gua stacking π–π interactions in (III) and (IV) are shown in Fig. 10. Centroid–centroid distances marked for the six-membered rings of the guanines reveal that the protonated Gua bases in (III) are stacked much more tightly than the neutral Gua bases in (IV). In (III), two types of C—H···O contacts, involving the O6_Gua atom, provide additional stabilization of the stacking interactions, while only one of them affects the O6_Gua atom in (IV), which in turn acts as an acceptor of two additional hydrogen bonds from water molecules (Fig. 10b).

In (V), the direct inter-nucleotide contacts are few (Table 10), and the crystal packing is determined by cIMP^-···(H₂O)_n···cIMP^- hydrogen bonds and coordination interactions with Na⁺ cations. As shown in Fig. 11, cIMP^- anions and Na⁺ cations are arranged in layers parallel to the (001) plane. Each nucleotide is extended along the b axis, between two Na⁺ ions, to which it coordinates via exocyclic the phosphate O5 and hypoxanthine (Hyp) O6 atoms. Two other ribose O atoms (O2' and O4') are engaged in additional Na···O interactions (along the a axis), giving rise to the layers shown in Fig. 11(a). Thus, every cIMP^- anion, being a bridging ligand and acting as a monodentate ligand for the individual Na⁺ cations, is in fact coordinated by four different Na⁺ cations. This has not been hitherto observed in the Na–cNMP crystals; among the eleven different nucleotide anions present in Na(cdTMP)·7H₂O, Na(cdTMP)·3.7H₂O (Ślepokura, 2016a) and Na(cAMP)·4H₂O (Varughese et al., 1982) reported to date, the typical amount of Na⁺ bound to cNMP^- was one or two, and only once it was three. On the other hand, the coordination environment of the octahedral Na⁺ cation in (V) is also quite crowded, due to four different cIMP^- anions occupying four positions in the coordination sphere, leaving only two sites for water molecules. Selected Na—O and Na···Na distances are given in Table S1 in the Supporting information. The structure of the layer is additionally stabilized by the direct inter-nucleotide O2'—H2'···O5'ⁱ interactions of the sugar–sugar type, and by Hyp–Hyp stacking π–π interactions. The contacts between the adjacent layers (at z = 0, 1/2, ···) are provided mainly by the water-mediated hydrogen bonds, as well as by direct base–phosphate N1–H1···O3ⁱⁱ hydrogen bonds, accompanied by a C2—H2···O5ⁱⁱ hydrogen bond. Interestingly, when only the latter are taken into consideration, one can find a ribbon motif similar to that observed in (III) and (IV) (see the highlighted cIMP^- anions in Fig. 11b).

Structure description top

Synthesis and crystallization top

Refinement details top

The water molecule in (II) was found to be not fully occupied and was refined to a site-occupancy factor (SOF) of 0.630 (15).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012) for I_camp, II_camp1ab, IV_gmpna, V_impna; CrysAlis CCD (Oxford Diffraction, 2004) for III_gmpdc. Cell refinement: CrysAlis PRO (Agilent, 2012) for I_camp, II_camp1ab, IV_gmpna, V_impna; CrysAlis RED (Oxford Diffraction, 2004) for III_gmpdc. Data reduction: CrysAlis PRO (Agilent, 2012) for I_camp, II_camp1ab, IV_gmpna, V_impna; CrysAlis RED (Oxford Diffraction, 2004) for III_gmpdc. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2014); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric units of (a) cAMP·2H₂O, (I), and (b) cAMP·0.3H₂O, (II), showing the atom-numbering schemes (for P, O, N and selected C atoms) and symmetry-independent hydrogen bonds (dashed lines). Displacement ellipsoids are shown at the 50% probability level. For the full atom-numbering schemes, see Figs. S1 and S2 in the Supporting information.
	Fig. 2. The asymmetric units of (a) cGMP·5H₂O, (III), (b) Na(cGMP)·4H₂O, (IV) and (c) Na(cIMP)·4H₂O, (V), showing the atom-numbering schemes and symmetry-independent hydrogen bonds (dashed lines). Displacement ellipsoids are shown at the 30% probability level for (III) and 50% for (IV) and (V). Transparent spheres (and grey labels) in (III) represent selected positions (with the highest site-occupation factors) of partially occupied O atoms of disordered water molecules. In (IV) and (V), they represent water positions with lower site-occupation factors. For the details of (III), see Fig. S3 in the Supporting information.
	Fig. 3. Comparison of the geometry of all 3':5'-cyclic nucleotides with the nucleobase in the syn orientation [anions and/or zwitterions of cAMP, cGMP and cIMP of (I)–(V) and deposited in the CSD]. Most of the H atoms have been omitted for clarity. Intramolecular C—H···N hydrogen bonds are shown with dashed lines. The common reference points are the O4', C1' and C2' atoms. (The legend indicates the order of increasing χ_CN.)
	Fig. 4. Comparison of the geometry of the anions and zwitterions of (a) cAMP and (b) cIMP of (I), (II) and (V) and deposited in the CSD, along with (c) two cNMPs with the same sugar puckering and different deformation of the O/P/O/C/C/C ring. Most of the H atoms have been omitted for clarity. Intramolecular C—H···N hydrogen bonds are shown with dashed lines. The common reference points are the O4', C1' and C2' atoms. (For ZOXVOX, an inverted model has been used.)
	Fig. 5. Distributions of the χ_CN torsion angle for the Ade, Gua and Hyp nucleotides (Ado–P, Guo–P and IMPs). Conformational regions in histograms: anti (light grey), high-anti (dark grey), and syn (blue); based on CSD data and presented structures.
	Fig. 6. Comparison of the geometry of 3':5'-cGMP with 2':3'-cGMP [CSD refcode CELLOV; χ_CN = 65.2 (2)°; flattened ³T₂]. Most of the H atoms have been omitted for clarity. Intramolecular C—H···N hydrogen bonds are shown with dashed lines. The common reference points are the O4', C1' and C2' atoms.
	Fig. 7. The arrangement of the cAMP zwitterions within the layer [parallel to the (001) plane] in the crystal lattice of (II). Similar layers are also present in (I). H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity. The symmetry codes are as given in Table 7.
	Fig. 8. Ade–Ade π–π stacking interactions (dotted lines) formed within the layer and the nucleotide–water hydrogen bonds (dashed lines) providing inter-layer contacts in (I). C—H···O/N contacts formed between the syn and anti conformer are also shown as dashed lines.
	Fig. 9. (a) Superposition of the nucleotide ribbons present in (III) (transparent) and (IV), formed by Gua–phosphate hydrogen bonds [dashed lines; atoms for (IV) are labelled], and the crystal packing scheme in (b) (III) and (c) (IV). Hydrogen-bonded water molecules in (III) and the Na(H₂O)₆ polyhedra in (IV) are also shown. Disorder of atom O3W in (IV) has been omitted. [Symmetry code: (ii) -x+1/2, -y+1, z+1/2.]
	Fig. 10. Gua–Gua π–π interactions in (a) (III) and (b) (IV), shown with red dotted lines. The accompanied hydrogen bonds are shown with dashed lines. The symmetry codes are as given in Tables 8 and 9 for (III) and (IV), respectively, with the addition of (#) x, y+1, z.
	Fig. 11. (a) cIMP^-–Na layers in (V) stabilized by the π–π stacking interactions (dotted lines) and (b) the hydrogen bonds (dashed lines) formed between two layers (shown in yellow and grey). Nucleotide H atoms and noncoordinated water molecules in (a) have been omitted for clarity. H atoms not involved in hydrogen bonds in (b) are not shown. The symmetry codes are as given in Table 10 and Fig. S1 in the Supporting information.

(I_camp) Adenosine 3':5'-cyclic phosphate dihydrate top

Crystal data top

C₁₀H₁₂N₅O₆P·2H₂O	D_x = 1.673 Mg m⁻³
M_r = 365.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7087 reflections
a = 7.715 (2) Å	θ = 2.9–36.8°
b = 10.598 (3) Å	µ = 0.25 mm⁻¹
c = 35.481 (9) Å	T = 100 K
V = 2901.1 (13) Å³	Plate, colourless
Z = 8	0.36 × 0.16 × 0.01 mm
F(000) = 1520

Data collection top

Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire2 CCD camera	6322 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4907 reflections with I > 2σ(I)
Detector resolution: 8.3359 pixels mm^-1	R_int = 0.086
ω scan	θ_max = 27.0°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −9→9
T_min = 0.953, T_max = 1.000	k = −13→13
27238 measured reflections	l = −45→43

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0363P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
6322 reflections	Δρ_max = 0.34 e Å⁻³
433 parameters	Δρ_min = −0.33 e Å⁻³
20 restraints	Absolute structure: Flack x determined using 1672 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (7)

Crystal data top

C₁₀H₁₂N₅O₆P·2H₂O	V = 2901.1 (13) Å³
M_r = 365.25	Z = 8
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.715 (2) Å	µ = 0.25 mm⁻¹
b = 10.598 (3) Å	T = 100 K
c = 35.481 (9) Å	0.36 × 0.16 × 0.01 mm

Data collection top

Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire2 CCD camera	6322 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	4907 reflections with I > 2σ(I)
T_min = 0.953, T_max = 1.000	R_int = 0.086
27238 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.090	Δρ_max = 0.34 e Å⁻³
S = 1.01	Δρ_min = −0.33 e Å⁻³
6322 reflections	Absolute structure: Flack x determined using 1672 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
433 parameters	Absolute structure parameter: 0.03 (7)
20 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1A	0.14964 (12)	0.63706 (11)	0.79392 (3)	0.0133 (2)
O3A	0.0865 (4)	0.7405 (3)	0.76961 (8)	0.0168 (7)
O5A	0.0831 (3)	0.6264 (3)	0.83372 (8)	0.0155 (6)
O2'A	0.6983 (3)	0.5528 (3)	0.79650 (8)	0.0168 (7)
H2'A	0.7016	0.6077	0.8135	0.025*
O3'A	0.3591 (3)	0.6418 (3)	0.79712 (8)	0.0148 (6)
O4'A	0.5069 (4)	0.4547 (3)	0.71938 (7)	0.0162 (6)
O5'A	0.1134 (3)	0.5002 (3)	0.77556 (8)	0.0151 (7)
N1A	0.6172 (4)	0.8049 (3)	0.61977 (10)	0.0167 (8)
H1A	0.5702	0.8514	0.6019	0.020*
N3A	0.5968 (4)	0.7483 (3)	0.68416 (10)	0.0170 (8)
N6A	0.7555 (4)	0.6885 (3)	0.57300 (10)	0.0182 (8)
H6A	0.6920	0.7254	0.5556	0.022*
H6B	0.8098	0.6183	0.5670	0.022*
N7A	0.8714 (4)	0.5188 (3)	0.63917 (10)	0.0146 (8)
N9A	0.7529 (4)	0.5522 (3)	0.69645 (10)	0.0143 (8)
C1'A	0.6719 (5)	0.5065 (4)	0.73091 (11)	0.0133 (9)
H1'1	0.7446	0.4370	0.7416	0.016*
C2'A	0.6364 (5)	0.6050 (4)	0.76237 (12)	0.0144 (9)
H2'1	0.6908	0.6885	0.7567	0.017*
C3'A	0.4384 (5)	0.6113 (4)	0.76157 (12)	0.0134 (9)
H3'1	0.3990	0.6718	0.7417	0.016*
C4'A	0.3928 (5)	0.4774 (4)	0.75034 (12)	0.0144 (9)
H4'1	0.4212	0.4186	0.7715	0.017*
C5'A	0.2021 (5)	0.4674 (4)	0.74083 (12)	0.0146 (9)
H5'1	0.1708	0.5267	0.7204	0.018*
H5'2	0.1722	0.3806	0.7328	0.018*
C2A	0.5636 (5)	0.8231 (4)	0.65570 (13)	0.0173 (10)
H2A	0.4963	0.8963	0.6607	0.021*
C4A	0.6998 (5)	0.6501 (4)	0.67397 (12)	0.0140 (9)
C5A	0.7724 (5)	0.6285 (4)	0.63907 (12)	0.0135 (9)
C6A	0.7187 (5)	0.7052 (4)	0.60872 (13)	0.0160 (9)
C8A	0.8546 (5)	0.4778 (4)	0.67341 (12)	0.0141 (9)
H8A	0.9082	0.4023	0.6820	0.017*
P1B	0.49585 (14)	0.09412 (10)	0.56762 (3)	0.0154 (2)
O3B	0.4858 (4)	0.1583 (3)	0.53017 (8)	0.0173 (6)
O5B	0.4922 (4)	−0.0463 (2)	0.56819 (8)	0.0194 (6)
O2'B	0.2015 (3)	0.2681 (3)	0.66036 (8)	0.0177 (7)
H2'B	0.1034	0.2338	0.6613	0.027*
O3'B	0.3417 (3)	0.1440 (3)	0.59437 (8)	0.0160 (6)
O4'B	0.5057 (3)	0.4407 (2)	0.62712 (8)	0.0158 (6)
O5'B	0.6670 (3)	0.1393 (3)	0.58913 (8)	0.0167 (7)
N1B	0.0538 (4)	0.8890 (3)	0.65325 (10)	0.0157 (8)
H1B	0.0004	0.9573	0.6613	0.019*
N3B	0.1816 (4)	0.6959 (3)	0.67162 (10)	0.0153 (8)
N6B	0.0008 (5)	0.9559 (3)	0.59228 (10)	0.0184 (8)
H6C	−0.0568	1.0198	0.6020	0.022*
H6D	0.0162	0.9560	0.5677	0.022*
N7B	0.1835 (4)	0.7024 (3)	0.57042 (11)	0.0177 (8)
N9B	0.2680 (4)	0.5727 (3)	0.61741 (10)	0.0146 (8)
C1'B	0.3273 (5)	0.4593 (4)	0.63699 (12)	0.0145 (9)
H1'2	0.3186	0.4733	0.6648	0.017*
C2'B	0.2266 (5)	0.3372 (4)	0.62653 (12)	0.0142 (9)
H2'2	0.1151	0.3555	0.6132	0.017*
C3'B	0.3600 (5)	0.2762 (4)	0.60086 (12)	0.0145 (9)
H3'2	0.3593	0.3209	0.5760	0.017*
C4'B	0.5277 (5)	0.3073 (4)	0.62130 (13)	0.0148 (9)
H4'2	0.5329	0.2621	0.6460	0.018*
C5'B	0.6838 (5)	0.2748 (4)	0.59760 (13)	0.0183 (10)
H5'3	0.6847	0.3251	0.5741	0.022*
H5'4	0.7923	0.2916	0.6116	0.022*
C2B	0.1072 (5)	0.8032 (4)	0.67967 (13)	0.0182 (10)
H2B	0.0889	0.8230	0.7055	0.022*
C4B	0.2009 (5)	0.6782 (4)	0.63428 (12)	0.0137 (9)
C5B	0.1500 (5)	0.7575 (4)	0.60541 (12)	0.0142 (9)
C6B	0.0677 (5)	0.8718 (4)	0.61553 (13)	0.0165 (9)
C8B	0.2528 (5)	0.5925 (4)	0.57913 (12)	0.0187 (10)
H8B	0.2888	0.5326	0.5608	0.022*
O1W	0.8284 (4)	0.4878 (3)	0.52517 (10)	0.0381 (9)
H1W	0.9049	0.4537	0.5118	0.057*
H2W	0.7385	0.5013	0.5124	0.057*
O2W	0.5736 (4)	0.7834 (3)	0.50791 (9)	0.0266 (8)
H3W	0.6129	0.7961	0.4861	0.040*
H4W	0.5168	0.8464	0.5153	0.040*
O3W	0.0159 (4)	0.9611 (3)	0.51357 (8)	0.0262 (7)
H5W	−0.0724	1.0045	0.5086	0.039*
H6W	0.0103	0.8907	0.5028	0.039*
O4W	0.7863 (3)	0.1325 (3)	0.48819 (8)	0.0220 (7)
H7W	0.7050	0.1501	0.5030	0.033*
H8W	0.8537	0.1942	0.4859	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1A	0.0116 (5)	0.0105 (5)	0.0178 (6)	0.0002 (4)	0.0005 (4)	−0.0014 (5)
O3A	0.0172 (14)	0.0137 (16)	0.0194 (18)	0.0010 (12)	0.0019 (12)	0.0013 (13)
O5A	0.0150 (13)	0.0125 (16)	0.0189 (17)	0.0011 (12)	−0.0001 (11)	−0.0014 (13)
O2'A	0.0166 (14)	0.0185 (17)	0.0153 (17)	0.0004 (12)	−0.0025 (12)	−0.0028 (13)
O3'A	0.0122 (13)	0.0140 (15)	0.0182 (16)	0.0001 (12)	0.0028 (12)	−0.0014 (14)
O4'A	0.0132 (13)	0.0155 (16)	0.0199 (17)	−0.0022 (13)	0.0023 (12)	−0.0038 (12)
O5'A	0.0146 (14)	0.0099 (16)	0.0208 (18)	−0.0025 (11)	0.0025 (11)	−0.0042 (13)
N1A	0.0175 (17)	0.0116 (19)	0.021 (2)	0.0012 (14)	−0.0028 (15)	0.0029 (16)
N3A	0.0144 (17)	0.013 (2)	0.023 (2)	0.0003 (15)	0.0003 (15)	−0.0007 (17)
N6A	0.0212 (17)	0.0169 (19)	0.016 (2)	0.0044 (16)	−0.0032 (16)	0.0012 (16)
N7A	0.0113 (16)	0.0136 (19)	0.019 (2)	0.0010 (14)	−0.0001 (14)	−0.0013 (16)
N9A	0.0126 (15)	0.0122 (18)	0.018 (2)	0.0004 (15)	−0.0014 (14)	−0.0003 (15)
C1'A	0.0141 (19)	0.010 (2)	0.016 (2)	0.0001 (17)	−0.0022 (16)	0.0028 (17)
C2'A	0.0138 (19)	0.012 (2)	0.018 (2)	0.0023 (17)	0.0001 (17)	−0.0050 (18)
C3'A	0.0160 (19)	0.013 (2)	0.011 (2)	−0.0005 (17)	0.0008 (16)	0.0010 (18)
C4'A	0.014 (2)	0.012 (2)	0.017 (3)	0.0003 (16)	0.0019 (16)	−0.0008 (19)
C5'A	0.015 (2)	0.011 (2)	0.018 (2)	0.0014 (16)	0.0008 (17)	−0.0022 (19)
C2A	0.017 (2)	0.013 (2)	0.022 (3)	−0.0009 (17)	−0.0010 (18)	−0.001 (2)
C4A	0.0099 (18)	0.010 (2)	0.022 (3)	−0.0049 (16)	−0.0019 (16)	0.0024 (19)
C5A	0.0120 (18)	0.011 (2)	0.017 (2)	−0.0017 (17)	−0.0008 (16)	0.0000 (19)
C6A	0.0135 (19)	0.013 (2)	0.021 (3)	−0.0014 (17)	0.0030 (17)	−0.0017 (19)
C8A	0.0120 (18)	0.011 (2)	0.020 (2)	−0.0007 (17)	0.0022 (17)	−0.0029 (18)
P1B	0.0172 (5)	0.0112 (5)	0.0179 (6)	0.0017 (5)	−0.0014 (5)	−0.0007 (5)
O3B	0.0199 (14)	0.0160 (16)	0.0160 (16)	−0.0012 (13)	−0.0004 (12)	−0.0001 (12)
O5B	0.0278 (15)	0.0086 (14)	0.0217 (17)	0.0011 (14)	−0.0030 (14)	−0.0009 (13)
O2'B	0.0154 (14)	0.0164 (17)	0.0213 (18)	−0.0036 (12)	0.0043 (12)	0.0060 (14)
O3'B	0.0155 (14)	0.0093 (15)	0.0233 (18)	−0.0020 (12)	0.0004 (12)	−0.0018 (14)
O4'B	0.0121 (13)	0.0102 (15)	0.0250 (18)	0.0009 (12)	0.0002 (13)	−0.0029 (12)
O5'B	0.0176 (14)	0.0108 (15)	0.0215 (17)	0.0037 (13)	−0.0024 (12)	−0.0037 (14)
N1B	0.0176 (17)	0.011 (2)	0.019 (2)	0.0013 (14)	0.0011 (14)	−0.0033 (16)
N3B	0.0143 (16)	0.016 (2)	0.016 (2)	−0.0015 (14)	−0.0011 (14)	0.0004 (16)
N6B	0.0231 (17)	0.0130 (19)	0.019 (2)	0.0043 (17)	0.0013 (16)	0.0010 (15)
N7B	0.0188 (17)	0.0134 (19)	0.021 (2)	0.0012 (15)	0.0030 (15)	0.0000 (17)
N9B	0.0146 (16)	0.0120 (19)	0.017 (2)	−0.0004 (14)	0.0013 (14)	−0.0005 (15)
C1'B	0.0154 (19)	0.013 (2)	0.015 (2)	0.0031 (17)	0.0009 (16)	0.0003 (18)
C2'B	0.0116 (18)	0.015 (2)	0.016 (2)	0.0005 (16)	0.0001 (16)	−0.0002 (18)
C3'B	0.017 (2)	0.011 (2)	0.016 (2)	0.0002 (18)	0.0026 (17)	0.0016 (18)
C4'B	0.0140 (19)	0.009 (2)	0.021 (2)	0.0005 (16)	−0.0012 (17)	0.0008 (18)
C5'B	0.016 (2)	0.010 (2)	0.029 (3)	0.0000 (18)	−0.0003 (18)	−0.004 (2)
C2B	0.015 (2)	0.020 (2)	0.019 (3)	−0.0016 (18)	−0.0012 (17)	−0.002 (2)
C4B	0.0089 (18)	0.011 (2)	0.021 (3)	0.0005 (15)	−0.0001 (16)	0.0003 (19)
C5B	0.0117 (19)	0.014 (2)	0.017 (2)	0.0017 (17)	−0.0002 (17)	−0.0019 (18)
C6B	0.0125 (18)	0.014 (2)	0.023 (3)	−0.0021 (17)	0.0003 (17)	−0.001 (2)
C8B	0.021 (2)	0.015 (2)	0.020 (3)	0.002 (2)	0.0026 (18)	−0.0033 (19)
O1W	0.0332 (19)	0.043 (2)	0.038 (2)	0.0161 (17)	−0.0029 (16)	−0.0194 (19)
O2W	0.0362 (18)	0.0188 (19)	0.025 (2)	0.0044 (14)	0.0044 (14)	−0.0003 (15)
O3W	0.0298 (17)	0.0206 (17)	0.0283 (19)	0.0054 (15)	−0.0023 (15)	−0.0007 (15)
O4W	0.0223 (15)	0.0159 (16)	0.0278 (18)	−0.0027 (13)	0.0058 (13)	0.0024 (15)

Geometric parameters (Å, º) top

P1A—O3'A	1.621 (3)	O2'B—C2'B	1.420 (5)
P1A—O5'A	1.615 (3)	O2'B—H2'B	0.8401
P1A—O3A	1.478 (3)	O3'B—C3'B	1.427 (5)
P1A—O5A	1.507 (3)	O4'B—C1'B	1.433 (5)
O2'A—C2'A	1.414 (5)	O4'B—C4'B	1.439 (5)
O2'A—H2'A	0.8398	O5'B—C5'B	1.473 (5)
O3'A—C3'A	1.438 (5)	N1B—C6B	1.355 (5)
O4'A—C4'A	1.428 (5)	N1B—C2B	1.369 (5)
O4'A—C1'A	1.445 (5)	N1B—H1B	0.8800
O5'A—C5'A	1.452 (5)	N3B—C2B	1.305 (5)
N1A—C2A	1.354 (5)	N3B—C4B	1.346 (5)
N1A—C6A	1.372 (5)	N6B—C6B	1.320 (5)
N1A—H1A	0.8800	N6B—H6C	0.8802
N3A—C2A	1.309 (5)	N6B—H6D	0.8802
N3A—C4A	1.359 (5)	N7B—C8B	1.318 (5)
N6A—C6A	1.311 (5)	N7B—C5B	1.396 (5)
N6A—H6A	0.8799	N9B—C4B	1.371 (5)
N6A—H6B	0.8801	N9B—C8B	1.379 (5)
N7A—C8A	1.297 (5)	N9B—C1'B	1.462 (5)
N7A—C5A	1.391 (5)	C1'B—C2'B	1.554 (6)
N9A—C4A	1.371 (5)	C1'B—H1'2	1.0000
N9A—C8A	1.381 (5)	C2'B—C3'B	1.519 (5)
N9A—C1'A	1.456 (5)	C2'B—H2'2	1.0000
C1'A—C2'A	1.552 (6)	C3'B—C4'B	1.520 (6)
C1'A—H1'1	1.0000	C3'B—H3'2	1.0000
C2'A—C3'A	1.529 (5)	C4'B—C5'B	1.509 (6)
C2'A—H2'1	1.0000	C4'B—H4'2	1.0000
C3'A—C4'A	1.515 (6)	C5'B—H5'3	0.9900
C3'A—H3'1	1.0000	C5'B—H5'4	0.9900
C4'A—C5'A	1.514 (5)	C2B—H2B	0.9500
C4'A—H4'1	1.0000	C4B—C5B	1.381 (6)
C5'A—H5'1	0.9900	C5B—C6B	1.414 (6)
C5'A—H5'2	0.9900	C8B—H8B	0.9500
C2A—H2A	0.9500	O1W—H1W	0.8400
C4A—C5A	1.378 (6)	O1W—H2W	0.8401
C5A—C6A	1.412 (6)	O2W—H3W	0.8405
C8A—H8A	0.9500	O2W—H4W	0.8405
P1B—O3'B	1.611 (3)	O3W—H5W	0.8402
P1B—O5'B	1.598 (3)	O3W—H6W	0.8398
P1B—O3B	1.495 (3)	O4W—H7W	0.8400
P1B—O5B	1.489 (3)	O4W—H8W	0.8401

O5'A—P1A—O3'A	103.21 (15)	O5B—P1B—O3'B	107.80 (17)
O3A—P1A—O3'A	110.30 (17)	O3B—P1B—O5'B	109.32 (17)
O5A—P1A—O3'A	106.04 (15)	O5B—P1B—O5'B	107.97 (17)
O3A—P1A—O5'A	111.96 (17)	O5B—P1B—O3B	117.80 (17)
O5A—P1A—O5'A	104.60 (16)	C2'B—O2'B—H2'B	112.4
O3A—P1A—O5A	119.35 (17)	C3'B—O3'B—P1B	110.1 (2)
C2'A—O2'A—H2'A	110.9	C1'B—O4'B—C4'B	106.5 (3)
C3'A—O3'A—P1A	110.8 (2)	C5'B—O5'B—P1B	117.5 (2)
C4'A—O4'A—C1'A	105.1 (3)	C6B—N1B—C2B	124.3 (4)
C5'A—O5'A—P1A	118.4 (2)	C6B—N1B—H1B	117.8
C2A—N1A—C6A	123.6 (4)	C2B—N1B—H1B	117.8
C2A—N1A—H1A	118.1	C2B—N3B—C4B	112.7 (4)
C6A—N1A—H1A	117.4	C6B—N6B—H6C	118.1
C2A—N3A—C4A	111.9 (4)	C6B—N6B—H6D	124.5
C6A—N6A—H6A	119.9	H6C—N6B—H6D	117.2
C6A—N6A—H6B	116.7	C8B—N7B—C5B	103.7 (4)
H6A—N6A—H6B	118.2	C4B—N9B—C8B	105.9 (3)
C8A—N7A—C5A	103.2 (3)	C4B—N9B—C1'B	125.6 (4)
C4A—N9A—C8A	104.9 (3)	C8B—N9B—C1'B	128.3 (4)
C4A—N9A—C1'A	127.7 (3)	O4'B—C1'B—N9B	107.3 (3)
C8A—N9A—C1'A	123.4 (3)	O4'B—C1'B—C2'B	107.9 (3)
O4'A—C1'A—N9A	105.5 (3)	N9B—C1'B—C2'B	114.5 (3)
O4'A—C1'A—C2'A	107.7 (3)	O4'B—C1'B—H1'2	109.0
N9A—C1'A—C2'A	117.1 (3)	N9B—C1'B—H1'2	109.0
O4'A—C1'A—H1'1	108.8	C2'B—C1'B—H1'2	109.0
N9A—C1'A—H1'1	108.8	O2'B—C2'B—C3'B	112.3 (3)
C2'A—C1'A—H1'1	108.8	O2'B—C2'B—C1'B	107.2 (3)
O2'A—C2'A—C3'A	111.7 (3)	C3'B—C2'B—C1'B	99.1 (3)
O2'A—C2'A—C1'A	107.0 (3)	O2'B—C2'B—H2'2	112.4
C3'A—C2'A—C1'A	101.1 (3)	C3'B—C2'B—H2'2	112.4
O2'A—C2'A—H2'1	112.1	C1'B—C2'B—H2'2	112.4
C3'A—C2'A—H2'1	112.1	O3'B—C3'B—C2'B	116.6 (3)
C1'A—C2'A—H2'1	112.1	O3'B—C3'B—C4'B	112.0 (3)
O3'A—C3'A—C4'A	110.0 (3)	C2'B—C3'B—C4'B	101.4 (3)
O3'A—C3'A—C2'A	114.7 (3)	O3'B—C3'B—H3'2	108.8
C4'A—C3'A—C2'A	101.3 (3)	C2'B—C3'B—H3'2	108.8
O3'A—C3'A—H3'1	110.2	C4'B—C3'B—H3'2	108.8
C4'A—C3'A—H3'1	110.2	O4'B—C4'B—C5'B	113.5 (3)
C2'A—C3'A—H3'1	110.2	O4'B—C4'B—C3'B	100.4 (3)
O4'A—C4'A—C5'A	114.6 (3)	C5'B—C4'B—C3'B	111.4 (3)
O4'A—C4'A—C3'A	102.6 (3)	O4'B—C4'B—H4'2	110.4
C5'A—C4'A—C3'A	110.5 (3)	C5'B—C4'B—H4'2	110.4
O4'A—C4'A—H4'1	109.7	C3'B—C4'B—H4'2	110.4
C5'A—C4'A—H4'1	109.7	O5'B—C5'B—C4'B	105.4 (3)
C3'A—C4'A—H4'1	109.7	O5'B—C5'B—H5'3	110.7
O5'A—C5'A—C4'A	104.6 (3)	C4'B—C5'B—H5'3	110.7
O5'A—C5'A—H5'1	110.8	O5'B—C5'B—H5'4	110.7
C4'A—C5'A—H5'1	110.8	C4'B—C5'B—H5'4	110.7
O5'A—C5'A—H5'2	110.8	H5'3—C5'B—H5'4	108.8
C4'A—C5'A—H5'2	110.8	N3B—C2B—N1B	124.1 (4)
H5'1—C5'A—H5'2	108.9	N3B—C2B—H2B	117.9
N3A—C2A—N1A	125.5 (4)	N1B—C2B—H2B	117.9
N3A—C2A—H2A	117.2	N3B—C4B—N9B	125.8 (4)
N1A—C2A—H2A	117.2	N3B—C4B—C5B	127.8 (4)
N3A—C4A—N9A	126.9 (4)	N9B—C4B—C5B	106.2 (4)
N3A—C4A—C5A	127.2 (4)	C4B—C5B—N7B	110.6 (4)
N9A—C4A—C5A	106.0 (4)	C4B—C5B—C6B	117.4 (4)
C4A—C5A—N7A	111.1 (4)	N7B—C5B—C6B	131.8 (4)
C4A—C5A—C6A	118.0 (4)	N6B—C6B—N1B	119.7 (4)
N7A—C5A—C6A	130.1 (4)	N6B—C6B—C5B	126.6 (4)
N6A—C6A—N1A	120.3 (4)	N1B—C6B—C5B	113.7 (4)
N6A—C6A—C5A	126.6 (4)	N7B—C8B—N9B	113.6 (4)
N1A—C6A—C5A	113.1 (4)	N7B—C8B—H8B	123.2
N7A—C8A—N9A	114.8 (4)	N9B—C8B—H8B	123.2
N7A—C8A—H8A	122.6	H1W—O1W—H2W	110.4
N9A—C8A—H8A	122.6	H3W—O2W—H4W	110.3
O5'B—P1B—O3'B	103.32 (14)	H5W—O3W—H6W	110.4
O3B—P1B—O3'B	109.64 (17)	H7W—O4W—H8W	110.5

O3A—P1A—O3'A—C3'A	−68.0 (3)	O5B—P1B—O3'B—C3'B	168.5 (2)
O5A—P1A—O3'A—C3'A	161.5 (2)	O3B—P1B—O3'B—C3'B	−62.1 (3)
O5'A—P1A—O3'A—C3'A	51.8 (3)	O5'B—P1B—O3'B—C3'B	54.4 (3)
O3A—P1A—O5'A—C5'A	65.3 (3)	O5B—P1B—O5'B—C5'B	−170.1 (3)
O5A—P1A—O5'A—C5'A	−164.0 (3)	O3B—P1B—O5'B—C5'B	60.6 (3)
O3'A—P1A—O5'A—C5'A	−53.3 (3)	O3'B—P1B—O5'B—C5'B	−56.1 (3)
C4'A—O4'A—C1'A—N9A	−147.5 (3)	C4'B—O4'B—C1'B—N9B	−139.1 (3)
C4'A—O4'A—C1'A—C2'A	−21.7 (4)	C4'B—O4'B—C1'B—C2'B	−15.3 (4)
C4A—N9A—C1'A—O4'A	66.5 (5)	C4B—N9B—C1'B—O4'B	−121.7 (4)
C8A—N9A—C1'A—O4'A	−87.8 (4)	C8B—N9B—C1'B—O4'B	64.5 (5)
C4A—N9A—C1'A—C2'A	−53.2 (5)	C4B—N9B—C1'B—C2'B	118.6 (4)
C8A—N9A—C1'A—C2'A	152.5 (4)	C8B—N9B—C1'B—C2'B	−55.2 (5)
O4'A—C1'A—C2'A—O2'A	109.4 (3)	O4'B—C1'B—C2'B—O2'B	101.1 (3)
N9A—C1'A—C2'A—O2'A	−132.1 (3)	N9B—C1'B—C2'B—O2'B	−139.5 (3)
O4'A—C1'A—C2'A—C3'A	−7.7 (4)	O4'B—C1'B—C2'B—C3'B	−15.8 (4)
N9A—C1'A—C2'A—C3'A	110.8 (4)	N9B—C1'B—C2'B—C3'B	103.6 (4)
P1A—O3'A—C3'A—C4'A	−62.9 (4)	P1B—O3'B—C3'B—C2'B	−178.5 (3)
P1A—O3'A—C3'A—C2'A	−176.3 (3)	P1B—O3'B—C3'B—C4'B	−62.3 (4)
O2'A—C2'A—C3'A—O3'A	36.9 (5)	O2'B—C2'B—C3'B—O3'B	47.9 (5)
C1'A—C2'A—C3'A—O3'A	150.5 (3)	C1'B—C2'B—C3'B—O3'B	160.9 (3)
O2'A—C2'A—C3'A—C4'A	−81.5 (4)	O2'B—C2'B—C3'B—C4'B	−73.9 (4)
C1'A—C2'A—C3'A—C4'A	32.1 (4)	C1'B—C2'B—C3'B—C4'B	39.0 (4)
C1'A—O4'A—C4'A—C5'A	162.6 (3)	C1'B—O4'B—C4'B—C5'B	158.9 (3)
C1'A—O4'A—C4'A—C3'A	42.8 (4)	C1'B—O4'B—C4'B—C3'B	40.0 (4)
O3'A—C3'A—C4'A—O4'A	−168.9 (3)	O3'B—C3'B—C4'B—O4'B	−175.0 (3)
C2'A—C3'A—C4'A—O4'A	−47.1 (4)	C2'B—C3'B—C4'B—O4'B	−49.9 (4)
O3'A—C3'A—C4'A—C5'A	68.5 (4)	O3'B—C3'B—C4'B—C5'B	64.6 (4)
C2'A—C3'A—C4'A—C5'A	−169.7 (3)	C2'B—C3'B—C4'B—C5'B	−170.4 (4)
P1A—O5'A—C5'A—C4'A	58.7 (4)	P1B—O5'B—C5'B—C4'B	58.4 (4)
O4'A—C4'A—C5'A—O5'A	−177.2 (3)	O4'B—C4'B—C5'B—O5'B	−170.1 (3)
C3'A—C4'A—C5'A—O5'A	−61.9 (4)	C3'B—C4'B—C5'B—O5'B	−57.6 (4)
C4A—N3A—C2A—N1A	2.6 (6)	C4B—N3B—C2B—N1B	0.1 (5)
C6A—N1A—C2A—N3A	−1.7 (6)	C6B—N1B—C2B—N3B	1.7 (6)
C2A—N3A—C4A—N9A	−177.1 (4)	C2B—N3B—C4B—N9B	−177.2 (4)
C2A—N3A—C4A—C5A	3.0 (6)	C2B—N3B—C4B—C5B	−1.0 (6)
C8A—N9A—C4A—N3A	−179.9 (4)	C8B—N9B—C4B—N3B	176.2 (4)
C1'A—N9A—C4A—N3A	22.1 (6)	C1'B—N9B—C4B—N3B	1.3 (6)
C8A—N9A—C4A—C5A	0.0 (4)	C8B—N9B—C4B—C5B	−0.7 (4)
C1'A—N9A—C4A—C5A	−158.0 (4)	C1'B—N9B—C4B—C5B	−175.6 (4)
N3A—C4A—C5A—N7A	179.5 (3)	N3B—C4B—C5B—N7B	−176.4 (4)
N9A—C4A—C5A—N7A	−0.4 (4)	N9B—C4B—C5B—N7B	0.4 (4)
N3A—C4A—C5A—C6A	−9.2 (6)	N3B—C4B—C5B—C6B	0.1 (6)
N9A—C4A—C5A—C6A	170.9 (3)	N9B—C4B—C5B—C6B	176.9 (3)
C8A—N7A—C5A—C4A	0.5 (4)	C8B—N7B—C5B—C4B	0.0 (4)
C8A—N7A—C5A—C6A	−169.4 (4)	C8B—N7B—C5B—C6B	−175.8 (4)
C2A—N1A—C6A—N6A	175.1 (4)	C2B—N1B—C6B—N6B	175.0 (4)
C2A—N1A—C6A—C5A	−4.4 (5)	C2B—N1B—C6B—C5B	−2.4 (5)
C4A—C5A—C6A—N6A	−170.5 (4)	C4B—C5B—C6B—N6B	−175.7 (4)
N7A—C5A—C6A—N6A	−1.1 (7)	N7B—C5B—C6B—N6B	0.0 (7)
C4A—C5A—C6A—N1A	9.0 (5)	C4B—C5B—C6B—N1B	1.5 (5)
N7A—C5A—C6A—N1A	178.3 (4)	N7B—C5B—C6B—N1B	177.2 (4)
C5A—N7A—C8A—N9A	−0.5 (4)	C5B—N7B—C8B—N9B	−0.5 (4)
C4A—N9A—C8A—N7A	0.3 (5)	C4B—N9B—C8B—N7B	0.7 (5)
C1'A—N9A—C8A—N7A	159.6 (3)	C1'B—N9B—C8B—N7B	175.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2′A—H2′A···O2′Bⁱ	0.84	2.07	2.854 (4)	154
N1A—H1A···O5Bⁱⁱ	0.88	1.72	2.601 (5)	174
N6A—H6A···O2W	0.88	2.02	2.883 (5)	167
N6A—H6B···O1W	0.88	2.03	2.778 (5)	142
C1′A—H1′1···O3Aⁱⁱⁱ	1.00	2.49	3.379 (5)	148
C3′A—H3′1···N3A	1.00	2.68	3.339 (6)	124
C4′A—H4′1···N3Aⁱⁱⁱ	1.00	2.40	3.362 (6)	162
C5′A—H5′1···N3B	0.99	2.49	3.453 (6)	163
C5′A—H5′2···O3A^iv	0.99	2.49	3.298 (5)	139
C8A—H8A···O3Aⁱⁱⁱ	0.95	2.43	3.258 (5)	146
O2′B—H2′B···O5A^iv	0.84	1.84	2.668 (4)	167
N1B—H1B···O5A^v	0.88	1.91	2.768 (4)	163
N1B—H1B···O5′A^v	0.88	2.45	3.071 (4)	128
N6B—H6C···O5A^v	0.88	2.55	3.252 (5)	137
N6B—H6C···O5′B^vi	0.88	2.52	3.228 (4)	138
N6B—H6D···O3W	0.88	1.92	2.796 (5)	172
C1′B—H1′2···O4′A	1.00	2.43	3.235 (5)	137
C3′B—H3′2···O4W^vii	1.00	2.40	3.353 (5)	159
C4′B—H4′2···O3′Aⁱⁱⁱ	1.00	2.53	3.495 (5)	163
C2B—H2B···O3A	0.95	2.44	3.264 (6)	145
C2B—H2B···O5′A^v	0.95	2.53	3.127 (5)	121
C8B—H8B···O4W^vii	0.95	2.47	3.384 (5)	163
O1W—H1W···O3B^viii	0.84	2.00	2.781 (4)	153
O1W—H2W···O3W^ix	0.84	1.99	2.827 (5)	175
O2W—H3W···N7B^ix	0.84	2.08	2.910 (5)	169
O2W—H4W···O5Bⁱⁱ	0.84	2.20	2.868 (4)	136
O3W—H5W···O4W^vi	0.84	1.89	2.692 (4)	161
O3W—H6W···O2W^x	0.84	1.95	2.738 (4)	157
O4W—H7W···O3B	0.84	1.95	2.770 (4)	166
O4W—H8W···O3B^viii	0.84	1.95	2.776 (4)	167

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y+1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x, y−1/2, −z+3/2; (v) −x, y+1/2, −z+3/2; (vi) x−1, y+1, z; (vii) x−1/2, −y+1/2, −z+1; (viii) x+1/2, −y+1/2, −z+1; (ix) x+1/2, −y+3/2, −z+1; (x) x−1/2, −y+3/2, −z+1.

(II_camp1ab) Adenosine 3':5'-cyclic phosphate 0.3-hydrate top

Crystal data top

C₁₀H₁₂N₅O₆P·0.3H₂O	D_x = 1.796 Mg m⁻³
M_r = 334.62	Cu Kα radiation, λ = 1.5418 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 5879 reflections
a = 7.786 (2) Å	θ = 4.2–76.6°
b = 10.638 (3) Å	µ = 2.45 mm⁻¹
c = 29.887 (8) Å	T = 120 K
V = 2475.5 (12) Å³	Plate, colourless
Z = 8	0.19 × 0.08 × 0.02 mm
F(000) = 1384

Data collection top

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	4505 independent reflections
Radiation source: Enhance (Cu) X-ray Source	4090 reflections with I > 2σ(I)
Detector resolution: 8.1956 pixels mm^-1	R_int = 0.065
ω and phi scans	θ_max = 68.0°, θ_min = 4.4°
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]	h = −7→9
T_min = 0.678, T_max = 0.952	k = −12→10
22972 measured reflections	l = −35→35

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0922P)² + 0.926P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4505 reflections	Δρ_max = 0.90 e Å⁻³
407 parameters	Δρ_min = −0.45 e Å⁻³
11 restraints	Absolute structure: Flack x determined using 1568 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.020 (14)

Crystal data top

C₁₀H₁₂N₅O₆P·0.3H₂O	V = 2475.5 (12) Å³
M_r = 334.62	Z = 8
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 7.786 (2) Å	µ = 2.45 mm⁻¹
b = 10.638 (3) Å	T = 120 K
c = 29.887 (8) Å	0.19 × 0.08 × 0.02 mm

Data collection top

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	4505 independent reflections
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]	4090 reflections with I > 2σ(I)
T_min = 0.678, T_max = 0.952	R_int = 0.065
22972 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.134	Δρ_max = 0.90 e Å⁻³
S = 1.05	Δρ_min = −0.45 e Å⁻³
4505 reflections	Absolute structure: Flack x determined using 1568 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
407 parameters	Absolute structure parameter: −0.020 (14)
11 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
P1A	0.14444 (16)	0.59315 (12)	0.80164 (5)	0.0179 (3)
O3A	0.0830 (5)	0.6951 (3)	0.77175 (13)	0.0224 (8)
O5A	0.0738 (5)	0.5832 (4)	0.84843 (13)	0.0227 (8)
O2'A	0.6894 (5)	0.5122 (4)	0.80757 (13)	0.0233 (8)
H2'A	0.6776	0.5671	0.8276	0.035*
O3'A	0.3515 (4)	0.5985 (3)	0.80635 (12)	0.0196 (8)
O4'A	0.5050 (4)	0.4105 (3)	0.71528 (12)	0.0193 (7)
O5'A	0.1106 (4)	0.4567 (3)	0.78004 (13)	0.0195 (8)
N1A	0.6329 (6)	0.7584 (4)	0.59556 (15)	0.0206 (9)
H1A	0.6098	0.8130	0.5743	0.025*
N3A	0.5976 (6)	0.7008 (4)	0.67200 (16)	0.0214 (10)
N6A	0.7854 (6)	0.6426 (4)	0.54222 (16)	0.0223 (9)
H6A	0.7723	0.7035	0.5226	0.027*
H6B	0.8473	0.5768	0.5346	0.027*
N7A	0.8806 (5)	0.4733 (4)	0.62235 (15)	0.0203 (9)
N9A	0.7509 (5)	0.5076 (4)	0.68886 (15)	0.0181 (9)
C1'A	0.6678 (6)	0.4629 (5)	0.72927 (18)	0.0183 (10)
H1'1	0.7392	0.3942	0.7425	0.022*
C2'A	0.6296 (6)	0.5626 (5)	0.76636 (18)	0.0192 (11)
H2'1	0.6832	0.6458	0.7595	0.023*
C3'A	0.4331 (6)	0.5683 (5)	0.76492 (18)	0.0163 (10)
H3'1	0.3950	0.6281	0.7411	0.020*
C4'A	0.3894 (6)	0.4339 (4)	0.75140 (17)	0.0171 (10)
H4'1	0.4163	0.3758	0.7767	0.020*
C5'A	0.2011 (6)	0.4226 (5)	0.73936 (18)	0.0188 (10)
H5'1	0.1711	0.4805	0.7146	0.023*
H5'2	0.1727	0.3356	0.7303	0.023*
C2A	0.5694 (7)	0.7751 (5)	0.6376 (2)	0.0216 (11)
H2A	0.4986	0.8466	0.6425	0.026*
C4A	0.7018 (6)	0.6039 (5)	0.66160 (18)	0.0189 (10)
C5A	0.7803 (6)	0.5818 (5)	0.62041 (18)	0.0199 (11)
C6A	0.7378 (7)	0.6601 (5)	0.58445 (19)	0.0213 (11)
C8A	0.8564 (6)	0.4329 (5)	0.66263 (18)	0.0186 (10)
H8A	0.9072	0.3577	0.6735	0.022*
P1B	0.47995 (17)	0.04508 (12)	0.53870 (5)	0.0211 (3)
O3B	0.4643 (6)	0.0953 (4)	0.49283 (15)	0.0342 (10)
O5B	0.4682 (5)	−0.0930 (3)	0.54488 (13)	0.0243 (8)
O2'B	0.1996 (5)	0.2383 (4)	0.64563 (14)	0.0253 (9)
H2'B	0.1140	0.1931	0.6398	0.038*
O3'B	0.3321 (5)	0.1052 (3)	0.57029 (14)	0.0229 (8)
O4'B	0.5107 (5)	0.3989 (3)	0.60449 (15)	0.0266 (9)
O5'B	0.6529 (5)	0.0920 (4)	0.56184 (15)	0.0294 (9)
N1B	0.0562 (6)	0.8491 (4)	0.63471 (17)	0.0237 (10)
H1B	0.0159	0.9197	0.6459	0.028*
N3B	0.1782 (6)	0.6548 (4)	0.65761 (16)	0.0206 (10)
N6B	0.0216 (6)	0.9161 (5)	0.56120 (18)	0.0312 (11)
H6C	0.0045	0.9962	0.5671	0.037*
H6D	0.0387	0.9154	0.5321	0.037*
N7B	0.2229 (6)	0.6745 (4)	0.53792 (17)	0.0249 (10)
N9B	0.2835 (5)	0.5385 (4)	0.59331 (15)	0.0199 (9)
C1'B	0.3366 (6)	0.4236 (5)	0.61679 (19)	0.0186 (11)
H1'2	0.3309	0.4387	0.6498	0.022*
C2'B	0.2286 (7)	0.3044 (5)	0.60524 (19)	0.0201 (11)
H2'2	0.1196	0.3253	0.5892	0.024*
C3'B	0.3576 (6)	0.2374 (4)	0.57544 (19)	0.0191 (11)
H3'2	0.3584	0.2781	0.5453	0.023*
C4'B	0.5255 (7)	0.2648 (5)	0.5989 (2)	0.0253 (12)
H4'2	0.5285	0.2223	0.6287	0.030*
C5'B	0.6776 (7)	0.2260 (6)	0.5714 (3)	0.0336 (15)
H5'3	0.6827	0.2750	0.5432	0.040*
H5'4	0.7856	0.2396	0.5882	0.040*
C2B	0.1032 (7)	0.7639 (5)	0.6670 (2)	0.0231 (11)
H2B	0.0812	0.7839	0.6974	0.028*
C4B	0.2084 (6)	0.6403 (5)	0.61384 (18)	0.0187 (11)
C5B	0.1718 (6)	0.7229 (5)	0.57884 (19)	0.0198 (11)
C6B	0.0846 (7)	0.8334 (5)	0.5905 (2)	0.0235 (12)
C8B	0.2888 (7)	0.5634 (5)	0.54860 (19)	0.0243 (12)
H8B	0.3351	0.5068	0.5272	0.029*
O1W	0.0106 (8)	1.1474 (5)	0.5216 (2)	0.024 (2)	0.630 (15)
H1W	0.0013	1.2195	0.5104	0.036*	0.630 (15)
H2W	0.1053	1.1399	0.5349	0.024*	0.630 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1A	0.0119 (6)	0.0117 (6)	0.0301 (7)	0.0009 (5)	0.0012 (5)	−0.0007 (5)
O3A	0.0189 (18)	0.0121 (17)	0.036 (2)	0.0019 (14)	0.0023 (16)	0.0050 (15)
O5A	0.0178 (17)	0.0162 (18)	0.034 (2)	0.0005 (15)	0.0035 (15)	0.0006 (16)
O2'A	0.0168 (17)	0.0217 (19)	0.031 (2)	0.0026 (15)	−0.0025 (15)	−0.0010 (15)
O3'A	0.0113 (16)	0.0157 (17)	0.032 (2)	0.0010 (14)	0.0004 (14)	−0.0020 (15)
O4'A	0.0098 (16)	0.0170 (16)	0.0312 (19)	−0.0044 (15)	0.0029 (14)	−0.0057 (15)
O5'A	0.0138 (17)	0.0115 (16)	0.033 (2)	0.0013 (14)	0.0043 (15)	−0.0018 (14)
N1A	0.017 (2)	0.014 (2)	0.031 (2)	0.0026 (19)	0.0035 (18)	−0.0009 (18)
N3A	0.014 (2)	0.015 (2)	0.035 (3)	0.0008 (17)	0.0022 (18)	−0.0022 (19)
N6A	0.018 (2)	0.020 (2)	0.029 (2)	−0.0009 (18)	0.0040 (19)	−0.0017 (19)
N7A	0.013 (2)	0.015 (2)	0.033 (3)	0.0006 (17)	−0.0010 (18)	−0.0015 (18)
N9A	0.0119 (18)	0.0135 (19)	0.029 (2)	0.0022 (17)	0.0025 (17)	−0.0019 (16)
C1'A	0.009 (2)	0.014 (2)	0.031 (3)	−0.001 (2)	0.001 (2)	0.002 (2)
C2'A	0.007 (2)	0.017 (2)	0.033 (3)	−0.001 (2)	0.001 (2)	−0.002 (2)
C3'A	0.010 (2)	0.013 (2)	0.026 (3)	0.0005 (18)	0.0003 (18)	−0.002 (2)
C4'A	0.012 (2)	0.013 (2)	0.026 (3)	−0.0002 (19)	0.0022 (19)	−0.0030 (19)
C5'A	0.012 (2)	0.014 (2)	0.030 (3)	−0.0025 (19)	0.000 (2)	−0.002 (2)
C2A	0.016 (2)	0.012 (2)	0.036 (3)	0.000 (2)	0.003 (2)	0.003 (2)
C4A	0.013 (2)	0.013 (2)	0.030 (3)	−0.002 (2)	0.000 (2)	−0.001 (2)
C5A	0.010 (2)	0.013 (2)	0.037 (3)	−0.0014 (19)	0.003 (2)	−0.004 (2)
C6A	0.011 (2)	0.016 (2)	0.037 (3)	−0.007 (2)	−0.001 (2)	−0.002 (2)
C8A	0.008 (2)	0.015 (2)	0.033 (3)	0.000 (2)	−0.002 (2)	−0.002 (2)
P1B	0.0177 (6)	0.0122 (6)	0.0335 (7)	0.0025 (5)	−0.0019 (6)	−0.0016 (5)
O3B	0.043 (3)	0.0223 (19)	0.037 (2)	0.009 (2)	0.000 (2)	0.0026 (18)
O5B	0.0222 (19)	0.0128 (17)	0.038 (2)	0.0039 (15)	−0.0049 (16)	−0.0029 (16)
O2'B	0.0187 (19)	0.0186 (19)	0.038 (2)	−0.0018 (16)	0.0042 (16)	0.0007 (16)
O3'B	0.0164 (17)	0.0097 (17)	0.043 (2)	−0.0007 (14)	0.0011 (15)	−0.0022 (15)
O4'B	0.0100 (17)	0.0109 (17)	0.059 (3)	−0.0018 (15)	0.0023 (17)	−0.0106 (17)
O5'B	0.0155 (18)	0.0167 (19)	0.056 (3)	0.0021 (16)	0.0001 (18)	−0.0119 (18)
N1B	0.016 (2)	0.013 (2)	0.041 (3)	0.0031 (18)	−0.0002 (19)	−0.002 (2)
N3B	0.012 (2)	0.015 (2)	0.035 (3)	−0.0017 (17)	0.0000 (18)	−0.0008 (19)
N6B	0.029 (3)	0.020 (2)	0.045 (3)	0.004 (2)	−0.009 (2)	0.006 (2)
N7B	0.027 (2)	0.019 (2)	0.029 (2)	−0.0026 (19)	0.001 (2)	−0.0009 (19)
N9B	0.014 (2)	0.0110 (19)	0.035 (3)	0.0017 (17)	0.0005 (17)	−0.0010 (18)
C1'B	0.012 (2)	0.010 (2)	0.034 (3)	0.0002 (19)	0.0011 (19)	−0.001 (2)
C2'B	0.015 (3)	0.016 (2)	0.030 (3)	0.004 (2)	0.001 (2)	−0.001 (2)
C3'B	0.013 (2)	0.008 (2)	0.036 (3)	−0.001 (2)	0.002 (2)	−0.004 (2)
C4'B	0.015 (3)	0.013 (2)	0.047 (3)	0.003 (2)	−0.001 (2)	−0.008 (2)
C5'B	0.014 (3)	0.019 (3)	0.068 (5)	0.001 (2)	0.005 (3)	−0.014 (3)
C2B	0.013 (2)	0.016 (3)	0.040 (3)	0.003 (2)	0.001 (2)	−0.001 (2)
C4B	0.012 (2)	0.014 (2)	0.030 (3)	−0.003 (2)	0.001 (2)	−0.003 (2)
C5B	0.014 (2)	0.013 (2)	0.032 (3)	−0.002 (2)	−0.001 (2)	0.000 (2)
C6B	0.013 (2)	0.013 (3)	0.045 (4)	−0.002 (2)	−0.002 (2)	0.001 (2)
C8B	0.021 (3)	0.019 (3)	0.033 (3)	−0.003 (2)	0.005 (2)	0.001 (2)
O1W	0.020 (3)	0.013 (3)	0.040 (4)	−0.001 (2)	−0.006 (3)	0.003 (2)

Geometric parameters (Å, º) top

P1A—O3'A	1.619 (4)	P1B—O5'B	1.594 (4)
P1A—O5'A	1.610 (4)	P1B—O3B	1.476 (5)
P1A—O3A	1.484 (4)	P1B—O5B	1.484 (4)
P1A—O5A	1.507 (4)	O2'B—C2'B	1.415 (7)
O2'A—C2'A	1.421 (6)	O2'B—H2'B	0.8401
O2'A—H2'A	0.8400	O3'B—C3'B	1.429 (6)
O3'A—C3'A	1.429 (6)	O4'B—C1'B	1.429 (6)
O4'A—C4'A	1.427 (6)	O4'B—C4'B	1.440 (6)
O4'A—C1'A	1.446 (6)	O5'B—C5'B	1.467 (7)
O5'A—C5'A	1.451 (6)	N1B—C6B	1.350 (8)
N1A—C2A	1.361 (7)	N1B—C2B	1.374 (8)
N1A—C6A	1.368 (7)	N1B—H1B	0.8802
N1A—H1A	0.8804	N3B—C2B	1.329 (7)
N3A—C2A	1.316 (8)	N3B—C4B	1.338 (7)
N3A—C4A	1.348 (7)	N6B—C6B	1.335 (7)
N6A—C6A	1.329 (7)	N6B—H6C	0.8800
N6A—H6A	0.8800	N6B—H6D	0.8800
N6A—H6B	0.8799	N7B—C8B	1.327 (7)
N7A—C8A	1.292 (7)	N7B—C5B	1.385 (7)
N7A—C5A	1.394 (7)	N9B—C8B	1.363 (7)
N9A—C4A	1.364 (7)	N9B—C4B	1.375 (7)
N9A—C8A	1.385 (7)	N9B—C1'B	1.469 (6)
N9A—C1'A	1.451 (7)	C1'B—C2'B	1.560 (7)
C1'A—C2'A	1.563 (7)	C1'B—H1'2	1.0000
C1'A—H1'1	1.0000	C2'B—C3'B	1.520 (7)
C2'A—C3'A	1.532 (6)	C2'B—H2'2	1.0000
C2'A—H2'1	1.0000	C3'B—C4'B	1.511 (7)
C3'A—C4'A	1.523 (6)	C3'B—H3'2	1.0000
C3'A—H3'1	1.0000	C4'B—C5'B	1.499 (8)
C4'A—C5'A	1.515 (7)	C4'B—H4'2	1.0000
C4'A—H4'1	1.0000	C5'B—H5'3	0.9900
C5'A—H5'1	0.9900	C5'B—H5'4	0.9900
C5'A—H5'2	0.9900	C2B—H2B	0.9500
C2A—H2A	0.9500	C4B—C5B	1.396 (8)
C4A—C5A	1.394 (7)	C5B—C6B	1.401 (7)
C5A—C6A	1.400 (8)	C8B—H8B	0.9500
C8A—H8A	0.9500	O1W—H1W	0.8399
P1B—O3'B	1.620 (4)	O1W—H2W	0.8402

O5'A—P1A—O3'A	103.25 (19)	O3B—P1B—O3'B	109.9 (2)
O3A—P1A—O3'A	110.3 (2)	O5B—P1B—O3'B	105.9 (2)
O5A—P1A—O3'A	106.6 (2)	O3B—P1B—O5'B	111.1 (3)
O3A—P1A—O5'A	111.4 (2)	O5B—P1B—O5'B	107.9 (2)
O5A—P1A—O5'A	104.4 (2)	O3B—P1B—O5B	117.9 (2)
O3A—P1A—O5A	119.5 (2)	C2'B—O2'B—H2'B	103.6
C2'A—O2'A—H2'A	108.6	C3'B—O3'B—P1B	110.6 (3)
C3'A—O3'A—P1A	111.1 (3)	C1'B—O4'B—C4'B	106.8 (4)
C4'A—O4'A—C1'A	105.5 (4)	C5'B—O5'B—P1B	120.0 (4)
C5'A—O5'A—P1A	118.8 (3)	C6B—N1B—C2B	124.2 (5)
C2A—N1A—C6A	122.7 (5)	C6B—N1B—H1B	122.4
C2A—N1A—H1A	120.4	C2B—N1B—H1B	113.0
C6A—N1A—H1A	116.8	C2B—N3B—C4B	112.6 (5)
C2A—N3A—C4A	112.3 (5)	C6B—N6B—H6C	124.3
C6A—N6A—H6A	119.9	C6B—N6B—H6D	125.9
C6A—N6A—H6B	120.7	H6C—N6B—H6D	103.2
H6A—N6A—H6B	118.4	C8B—N7B—C5B	103.3 (5)
C8A—N7A—C5A	103.4 (4)	C8B—N9B—C4B	107.3 (4)
C4A—N9A—C8A	105.0 (4)	C8B—N9B—C1'B	128.5 (4)
C4A—N9A—C1'A	128.2 (4)	C4B—N9B—C1'B	124.2 (4)
C8A—N9A—C1'A	123.2 (4)	O4'B—C1'B—N9B	107.3 (4)
O4'A—C1'A—N9A	106.1 (4)	O4'B—C1'B—C2'B	107.7 (4)
O4'A—C1'A—C2'A	107.5 (4)	N9B—C1'B—C2'B	114.8 (4)
N9A—C1'A—C2'A	116.9 (4)	O4'B—C1'B—H1'2	109.0
O4'A—C1'A—H1'1	108.7	N9B—C1'B—H1'2	109.0
N9A—C1'A—H1'1	108.7	C2'B—C1'B—H1'2	109.0
C2'A—C1'A—H1'1	108.7	O2'B—C2'B—C3'B	111.9 (4)
O2'A—C2'A—C3'A	111.5 (4)	O2'B—C2'B—C1'B	107.5 (4)
O2'A—C2'A—C1'A	107.2 (4)	C3'B—C2'B—C1'B	98.9 (4)
C3'A—C2'A—C1'A	101.3 (4)	O2'B—C2'B—H2'2	112.6
O2'A—C2'A—H2'1	112.1	C3'B—C2'B—H2'2	112.6
C3'A—C2'A—H2'1	112.1	C1'B—C2'B—H2'2	112.6
C1'A—C2'A—H2'1	112.1	O3'B—C3'B—C4'B	111.1 (4)
O3'A—C3'A—C4'A	110.0 (4)	O3'B—C3'B—C2'B	115.6 (4)
O3'A—C3'A—C2'A	115.4 (4)	C4'B—C3'B—C2'B	102.1 (4)
C4'A—C3'A—C2'A	101.2 (4)	O3'B—C3'B—H3'2	109.2
O3'A—C3'A—H3'1	110.0	C4'B—C3'B—H3'2	109.2
C4'A—C3'A—H3'1	110.0	C2'B—C3'B—H3'2	109.2
C2'A—C3'A—H3'1	110.0	O4'B—C4'B—C5'B	113.6 (5)
O4'A—C4'A—C5'A	114.6 (4)	O4'B—C4'B—C3'B	100.1 (4)
O4'A—C4'A—C3'A	102.9 (4)	C5'B—C4'B—C3'B	112.1 (5)
C5'A—C4'A—C3'A	110.7 (4)	O4'B—C4'B—H4'2	110.2
O4'A—C4'A—H4'1	109.5	C5'B—C4'B—H4'2	110.2
C5'A—C4'A—H4'1	109.5	C3'B—C4'B—H4'2	110.2
C3'A—C4'A—H4'1	109.5	O5'B—C5'B—C4'B	105.7 (5)
O5'A—C5'A—C4'A	104.5 (4)	O5'B—C5'B—H5'3	110.6
O5'A—C5'A—H5'1	110.8	C4'B—C5'B—H5'3	110.6
C4'A—C5'A—H5'1	110.8	O5'B—C5'B—H5'4	110.6
O5'A—C5'A—H5'2	110.8	C4'B—C5'B—H5'4	110.6
C4'A—C5'A—H5'2	110.8	H5'3—C5'B—H5'4	108.7
H5'1—C5'A—H5'2	108.9	N3B—C2B—N1B	123.1 (6)
N3A—C2A—N1A	125.6 (5)	N3B—C2B—H2B	118.5
N3A—C2A—H2A	117.2	N1B—C2B—H2B	118.5
N1A—C2A—H2A	117.2	N3B—C4B—N9B	127.0 (5)
N3A—C4A—N9A	127.3 (5)	N3B—C4B—C5B	128.6 (5)
N3A—C4A—C5A	126.6 (5)	N9B—C4B—C5B	104.4 (5)
N9A—C4A—C5A	106.1 (4)	N7B—C5B—C4B	111.6 (5)
C4A—C5A—N7A	110.4 (5)	N7B—C5B—C6B	132.1 (5)
C4A—C5A—C6A	118.3 (5)	C4B—C5B—C6B	116.1 (5)
N7A—C5A—C6A	131.1 (5)	N6B—C6B—N1B	120.0 (5)
N6A—C6A—N1A	120.3 (5)	N6B—C6B—C5B	124.6 (6)
N6A—C6A—C5A	125.4 (5)	N1B—C6B—C5B	115.3 (5)
N1A—C6A—C5A	114.2 (5)	N7B—C8B—N9B	113.4 (5)
N7A—C8A—N9A	115.0 (4)	N7B—C8B—H8B	123.3
N7A—C8A—H8A	122.5	N9B—C8B—H8B	123.3
N9A—C8A—H8A	122.5	H1W—O1W—H2W	110.5
O5'B—P1B—O3'B	102.9 (2)

O3A—P1A—O3'A—C3'A	−67.2 (4)	O3B—P1B—O3'B—C3'B	−65.6 (4)
O5A—P1A—O3'A—C3'A	161.6 (3)	O5B—P1B—O3'B—C3'B	166.0 (3)
O5'A—P1A—O3'A—C3'A	51.9 (3)	O5'B—P1B—O3'B—C3'B	52.8 (4)
O3A—P1A—O5'A—C5'A	65.3 (4)	O3B—P1B—O5'B—C5'B	65.1 (5)
O5A—P1A—O5'A—C5'A	−164.4 (3)	O5B—P1B—O5'B—C5'B	−164.1 (5)
O3'A—P1A—O5'A—C5'A	−53.1 (4)	O3'B—P1B—O5'B—C5'B	−52.4 (5)
C4'A—O4'A—C1'A—N9A	−147.4 (4)	C4'B—O4'B—C1'B—N9B	−140.4 (4)
C4'A—O4'A—C1'A—C2'A	−21.6 (5)	C4'B—O4'B—C1'B—C2'B	−16.3 (6)
C4A—N9A—C1'A—O4'A	66.6 (6)	C8B—N9B—C1'B—O4'B	54.9 (6)
C8A—N9A—C1'A—O4'A	−88.8 (5)	C4B—N9B—C1'B—O4'B	−128.9 (5)
C4A—N9A—C1'A—C2'A	−53.2 (7)	C8B—N9B—C1'B—C2'B	−64.7 (7)
C8A—N9A—C1'A—C2'A	151.4 (5)	C4B—N9B—C1'B—C2'B	111.4 (5)
O4'A—C1'A—C2'A—O2'A	109.4 (4)	O4'B—C1'B—C2'B—O2'B	101.9 (5)
N9A—C1'A—C2'A—O2'A	−131.5 (4)	N9B—C1'B—C2'B—O2'B	−138.7 (4)
O4'A—C1'A—C2'A—C3'A	−7.5 (5)	O4'B—C1'B—C2'B—C3'B	−14.5 (5)
N9A—C1'A—C2'A—C3'A	111.5 (5)	N9B—C1'B—C2'B—C3'B	104.9 (5)
P1A—O3'A—C3'A—C4'A	−62.8 (4)	P1B—O3'B—C3'B—C4'B	−63.1 (5)
P1A—O3'A—C3'A—C2'A	−176.4 (3)	P1B—O3'B—C3'B—C2'B	−178.8 (4)
O2'A—C2'A—C3'A—O3'A	36.3 (6)	O2'B—C2'B—C3'B—O3'B	46.0 (6)
C1'A—C2'A—C3'A—O3'A	150.1 (4)	C1'B—C2'B—C3'B—O3'B	159.1 (4)
O2'A—C2'A—C3'A—C4'A	−82.3 (5)	O2'B—C2'B—C3'B—C4'B	−74.7 (5)
C1'A—C2'A—C3'A—C4'A	31.5 (5)	C1'B—C2'B—C3'B—C4'B	38.3 (5)
C1'A—O4'A—C4'A—C5'A	162.8 (4)	C1'B—O4'B—C4'B—C5'B	160.2 (5)
C1'A—O4'A—C4'A—C3'A	42.5 (5)	C1'B—O4'B—C4'B—C3'B	40.5 (6)
O3'A—C3'A—C4'A—O4'A	−169.0 (4)	O3'B—C3'B—C4'B—O4'B	−173.5 (4)
C2'A—C3'A—C4'A—O4'A	−46.5 (5)	C2'B—C3'B—C4'B—O4'B	−49.7 (5)
O3'A—C3'A—C4'A—C5'A	68.1 (5)	O3'B—C3'B—C4'B—C5'B	65.7 (6)
C2'A—C3'A—C4'A—C5'A	−169.4 (4)	C2'B—C3'B—C4'B—C5'B	−170.4 (5)
P1A—O5'A—C5'A—C4'A	58.3 (5)	P1B—O5'B—C5'B—C4'B	55.0 (7)
O4'A—C4'A—C5'A—O5'A	−177.0 (4)	O4'B—C4'B—C5'B—O5'B	−169.1 (5)
C3'A—C4'A—C5'A—O5'A	−61.1 (5)	C3'B—C4'B—C5'B—O5'B	−56.5 (6)
C4A—N3A—C2A—N1A	1.2 (8)	C4B—N3B—C2B—N1B	2.6 (7)
C6A—N1A—C2A—N3A	−0.8 (9)	C6B—N1B—C2B—N3B	−1.9 (8)
C2A—N3A—C4A—N9A	−177.2 (5)	C2B—N3B—C4B—N9B	−179.9 (5)
C2A—N3A—C4A—C5A	2.3 (8)	C2B—N3B—C4B—C5B	0.0 (8)
C8A—N9A—C4A—N3A	179.7 (5)	C8B—N9B—C4B—N3B	180.0 (5)
C1'A—N9A—C4A—N3A	20.8 (9)	C1'B—N9B—C4B—N3B	3.1 (8)
C8A—N9A—C4A—C5A	0.1 (5)	C8B—N9B—C4B—C5B	0.1 (5)
C1'A—N9A—C4A—C5A	−158.8 (5)	C1'B—N9B—C4B—C5B	−176.8 (4)
N3A—C4A—C5A—N7A	179.3 (5)	C8B—N7B—C5B—C4B	0.3 (6)
N9A—C4A—C5A—N7A	−1.2 (6)	C8B—N7B—C5B—C6B	−175.9 (6)
N3A—C4A—C5A—C6A	−5.9 (8)	N3B—C4B—C5B—N7B	179.9 (5)
N9A—C4A—C5A—C6A	173.6 (4)	N9B—C4B—C5B—N7B	−0.2 (6)
C8A—N7A—C5A—C4A	1.7 (5)	N3B—C4B—C5B—C6B	−3.3 (8)
C8A—N7A—C5A—C6A	−172.2 (5)	N9B—C4B—C5B—C6B	176.6 (4)
C2A—N1A—C6A—N6A	174.7 (5)	C2B—N1B—C6B—N6B	174.3 (5)
C2A—N1A—C6A—C5A	−2.7 (7)	C2B—N1B—C6B—C5B	−1.6 (8)
C4A—C5A—C6A—N6A	−171.7 (5)	N7B—C5B—C6B—N6B	4.1 (9)
N7A—C5A—C6A—N6A	1.8 (9)	C4B—C5B—C6B—N6B	−172.0 (5)
C4A—C5A—C6A—N1A	5.6 (7)	N7B—C5B—C6B—N1B	179.8 (5)
N7A—C5A—C6A—N1A	179.1 (5)	C4B—C5B—C6B—N1B	3.8 (7)
C5A—N7A—C8A—N9A	−1.7 (6)	C5B—N7B—C8B—N9B	−0.3 (6)
C4A—N9A—C8A—N7A	1.1 (6)	C4B—N9B—C8B—N7B	0.1 (6)
C1'A—N9A—C8A—N7A	161.3 (5)	C1'B—N9B—C8B—N7B	176.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2′A—H2′A···O2′Bⁱ	0.84	2.21	2.914 (6)	142
N1A—H1A···O5Bⁱⁱ	0.88	1.73	2.537 (6)	152
N6A—H6A···N7Bⁱⁱⁱ	0.88	2.26	3.124 (7)	168
N6A—H6B···O3B^iv	0.88	2.20	3.072 (6)	170
N6A—H6B···O5B^iv	0.88	2.56	3.013 (6)	113
C1′A—H1′1···O3A^v	1.00	2.57	3.447 (6)	147
C4′A—H4′1···N3A^v	1.00	2.41	3.376 (7)	162
C5′A—H5′1···N3B	0.99	2.52	3.479 (7)	163
C5′A—H5′2···O3A^vi	0.99	2.49	3.295 (6)	138
C8A—H8A···O3A^v	0.95	2.38	3.236 (7)	149
O2′B—H2′B···O5A^vi	0.84	1.90	2.699 (5)	157
N1B—H1B···O5A^vii	0.88	1.88	2.735 (6)	163
N1B—H1B···O5′A^vii	0.88	2.45	3.080 (6)	129
N6B—H6C···O1W	0.88	2.11	2.731 (7)	127
C1′B—H1′2···O4′A	1.00	2.40	3.225 (7)	139
C3′B—H3′2···O1Wⁱⁱⁱ	1.00	2.46	3.367 (8)	151
C4′B—H4′2···O3′A^v	1.00	2.53	3.475 (7)	158
C5′B—H5′3···O1Wⁱⁱⁱ	0.99	2.50	3.351 (10)	144
C2B—H2B···O3A	0.95	2.41	3.219 (7)	142
C2B—H2B···O5′A^vii	0.95	2.46	3.080 (7)	123
C8B—H8B···O1Wⁱⁱⁱ	0.95	2.59	3.524 (8)	169
O1W—H1W···O3B^viii	0.84	1.99	2.795 (7)	159
O1W—H2W···O3′Bⁱⁱ	0.84	2.09	2.930 (7)	175

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y+1, z; (iii) x+1/2, −y+3/2, −z+1; (iv) x+1/2, −y+1/2, −z+1; (v) −x+1, y−1/2, −z+3/2; (vi) −x, y−1/2, −z+3/2; (vii) −x, y+1/2, −z+3/2; (viii) x−1/2, −y+3/2, −z+1.

(III_gmpdc) Guanosine 3':5'-cyclic phosphate pentahydrate top

Crystal data top

C₁₀H₁₂N₅O₇P·5H₂O	D_x = 1.605 Mg m⁻³
M_r = 435.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 5000 reflections
a = 6.691 (2) Å	θ = 4.6–26.0°
b = 13.555 (3) Å	µ = 0.23 mm⁻¹
c = 19.863 (4) Å	T = 298 K
V = 1801.5 (8) Å³	Plate, colourless
Z = 4	0.20 × 0.10 × 0.02 mm
F(000) = 912

Data collection top

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	R_int = 0.063
Radiation source: Enhance (Mo) X-ray Source	θ_max = 26.0°, θ_min = 4.6°
ω and phi scans	h = −8→8
22088 measured reflections	k = −16→16
3526 independent reflections	l = −24→24
2999 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.062	H-atom parameters constrained
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.0811P)²] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
3526 reflections	Δρ_max = 0.21 e Å⁻³
313 parameters	Δρ_min = −0.22 e Å⁻³
10 restraints	Absolute structure: Flack x determined using 892 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.16 (9)

Crystal data top

C₁₀H₁₂N₅O₇P·5H₂O	V = 1801.5 (8) Å³
M_r = 435.29	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.691 (2) Å	µ = 0.23 mm⁻¹
b = 13.555 (3) Å	T = 298 K
c = 19.863 (4) Å	0.20 × 0.10 × 0.02 mm

Data collection top

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	2999 reflections with I > 2σ(I)
22088 measured reflections	R_int = 0.063
3526 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	H-atom parameters constrained
wR(F²) = 0.146	Δρ_max = 0.21 e Å⁻³
S = 1.12	Δρ_min = −0.22 e Å⁻³
3526 reflections	Absolute structure: Flack x determined using 892 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
313 parameters	Absolute structure parameter: −0.16 (9)
10 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
P1	0.2392 (2)	0.47825 (9)	0.21641 (6)	0.0458 (4)
O3	0.2552 (6)	0.4211 (2)	0.27981 (15)	0.0595 (9)
O5	0.2892 (6)	0.4284 (3)	0.15284 (16)	0.0595 (10)
O2'	0.5017 (7)	0.7642 (3)	0.21677 (17)	0.0728 (12)
H2'	0.6078	0.7967	0.2126	0.109*
O3'	0.3812 (5)	0.5739 (2)	0.22260 (17)	0.0471 (8)
O4'	0.0736 (5)	0.7601 (2)	0.29584 (18)	0.0539 (9)
O5'	0.0200 (5)	0.5234 (3)	0.21009 (18)	0.0590 (10)
O6	0.2501 (6)	0.8627 (3)	0.60380 (15)	0.0589 (9)
N1	0.2667 (6)	0.7127 (3)	0.55252 (17)	0.0425 (9)
H1	0.2718	0.6873	0.5933	0.051*
N2	0.2678 (8)	0.5556 (3)	0.5083 (2)	0.0578 (11)
H2A	0.2880	0.5206	0.4716	0.069*
H2B	0.2801	0.5362	0.5504	0.069*
N3	0.2694 (6)	0.6860 (3)	0.43435 (17)	0.0397 (9)
N7	0.2708 (7)	0.9447 (3)	0.45762 (18)	0.0469 (9)
H7	0.2557	0.9998	0.4805	0.056*
N9	0.2716 (6)	0.8412 (2)	0.37339 (17)	0.0391 (8)
C1'	0.2605 (9)	0.8083 (3)	0.3035 (2)	0.0460 (11)
H1'1	0.2619	0.8666	0.2743	0.055*
C2'	0.4281 (7)	0.7368 (3)	0.2799 (2)	0.0438 (11)
H2'1	0.5345	0.7298	0.3135	0.053*
C3'	0.3072 (7)	0.6429 (3)	0.2715 (2)	0.0397 (11)
H3'1	0.2958	0.6098	0.3152	0.048*
C4'	0.1035 (7)	0.6810 (4)	0.2506 (3)	0.0489 (12)
H4'1	0.1082	0.7056	0.2043	0.059*
C5'	−0.0481 (8)	0.5998 (5)	0.2564 (3)	0.0701 (17)
H5'1	−0.0535	0.5747	0.3021	0.084*
H5'2	−0.1798	0.6233	0.2438	0.084*
C2	0.2678 (7)	0.6523 (3)	0.4970 (2)	0.0402 (10)
C4	0.2704 (7)	0.7852 (3)	0.43152 (19)	0.0354 (9)
C5	0.2688 (8)	0.8496 (3)	0.4843 (2)	0.0407 (10)
C6	0.2601 (8)	0.8152 (4)	0.5517 (2)	0.0454 (11)
C8	0.2716 (9)	0.9374 (3)	0.3917 (2)	0.0480 (11)
H8	0.2721	0.9904	0.3620	0.058*
O1W	0.197 (5)	0.3992 (14)	0.4144 (9)	0.082 (9)*	0.30 (3)
O10W	0.096 (6)	0.408 (2)	0.4031 (12)	0.083 (11)*	0.25 (3)
O11W	0.088 (6)	0.332 (3)	0.3974 (18)	0.15 (2)*	0.24 (3)
O12W	−0.049 (6)	0.354 (3)	0.3644 (18)	0.135 (18)*	0.21 (2)
O2W	0.377 (6)	0.1597 (15)	0.4000 (10)	0.077 (11)*	0.29 (4)
O20W	0.508 (9)	0.150 (3)	0.4110 (15)	0.107 (17)*	0.21 (3)
O21W	0.272 (11)	0.173 (3)	0.3881 (19)	0.132 (18)*	0.21 (3)
O22W	0.559 (11)	0.228 (5)	0.419 (2)	0.12 (3)*	0.16 (4)
O23W	0.424 (11)	0.235 (4)	0.422 (2)	0.11 (3)*	0.13 (3)
O3W	0.189 (5)	0.1179 (19)	0.5152 (16)	0.136 (13)*	0.35 (3)
O30W	0.288 (3)	0.1061 (11)	0.5380 (10)	0.045 (8)*	0.25 (3)
O31W	0.191 (5)	0.077 (2)	0.5622 (19)	0.123 (15)*	0.25 (3)
O32W	0.362 (7)	0.116 (3)	0.507 (2)	0.079 (17)*	0.14 (2)
O4W	0.481 (13)	0.323 (4)	0.540 (3)	0.40 (4)*	0.44 (5)
O40W	0.272 (13)	0.325 (4)	0.559 (4)	0.20 (4)*	0.24 (5)
O41W	0.269 (9)	0.318 (3)	0.503 (3)	0.16 (3)*	0.19 (3)
O42W	0.141 (14)	0.336 (5)	0.579 (3)	0.11 (3)*	0.14 (4)
O5W	0.638 (7)	0.452 (2)	0.352 (2)	0.21 (2)*	0.46 (4)
O50W	0.496 (3)	0.4669 (11)	0.3917 (8)	0.084 (7)*	0.33 (2)
O51W	0.349 (9)	0.418 (3)	0.415 (2)	0.11 (2)*	0.14 (2)
O52W	0.603 (7)	0.458 (3)	0.362 (2)	0.02 (3)*	0.07 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0522 (7)	0.0445 (6)	0.0407 (6)	−0.0003 (6)	0.0032 (6)	−0.0133 (5)
O3	0.084 (2)	0.0472 (17)	0.0475 (18)	0.002 (2)	0.004 (2)	−0.0052 (15)
O5	0.071 (3)	0.060 (2)	0.0473 (19)	−0.001 (2)	0.0094 (17)	−0.0182 (17)
O2'	0.100 (3)	0.070 (2)	0.049 (2)	−0.032 (2)	0.028 (2)	−0.0110 (19)
O3'	0.0496 (18)	0.0468 (18)	0.0449 (18)	−0.0003 (15)	0.0070 (15)	−0.0134 (15)
O4'	0.0497 (19)	0.052 (2)	0.060 (2)	0.0134 (16)	−0.0168 (16)	−0.0177 (19)
O5'	0.050 (2)	0.063 (2)	0.063 (2)	0.0013 (17)	−0.0062 (18)	−0.031 (2)
O6	0.070 (2)	0.071 (2)	0.0352 (17)	0.006 (2)	0.0004 (19)	−0.0128 (16)
N1	0.045 (2)	0.051 (2)	0.0316 (17)	0.002 (2)	−0.0043 (18)	0.0050 (16)
N2	0.079 (3)	0.046 (2)	0.048 (2)	0.005 (3)	0.005 (2)	0.0093 (19)
N3	0.040 (2)	0.0387 (18)	0.0404 (19)	0.0014 (18)	0.0012 (18)	0.0010 (16)
N7	0.058 (2)	0.0400 (19)	0.043 (2)	0.003 (2)	−0.003 (2)	−0.0076 (17)
N9	0.045 (2)	0.0386 (18)	0.0343 (18)	0.0030 (18)	−0.0030 (18)	0.0012 (15)
C1'	0.064 (3)	0.041 (2)	0.032 (2)	0.002 (3)	−0.004 (2)	0.0015 (19)
C2'	0.051 (3)	0.045 (3)	0.036 (2)	0.003 (2)	0.006 (2)	−0.005 (2)
C3'	0.047 (3)	0.039 (2)	0.033 (2)	0.000 (2)	−0.0015 (19)	−0.0045 (19)
C4'	0.052 (3)	0.048 (3)	0.047 (3)	0.011 (2)	−0.009 (2)	−0.012 (2)
C5'	0.044 (3)	0.084 (4)	0.083 (4)	0.007 (3)	−0.005 (3)	−0.041 (3)
C2	0.036 (2)	0.044 (2)	0.040 (2)	0.007 (2)	0.002 (2)	0.0022 (19)
C4	0.035 (2)	0.041 (2)	0.030 (2)	0.000 (2)	−0.002 (2)	0.0010 (18)
C5	0.042 (3)	0.044 (2)	0.036 (2)	−0.001 (2)	0.001 (2)	−0.0012 (19)
C6	0.037 (2)	0.061 (3)	0.038 (2)	0.003 (3)	0.001 (2)	−0.006 (2)
C8	0.062 (3)	0.040 (2)	0.042 (2)	0.004 (3)	−0.008 (3)	−0.002 (2)

Geometric parameters (Å, º) top

P1—O3'	1.612 (3)	N7—C5	1.394 (6)
P1—O5'	1.594 (4)	N7—H7	0.8799
P1—O3	1.482 (3)	N9—C8	1.353 (6)
P1—O5	1.470 (3)	N9—C4	1.382 (5)
O2'—C2'	1.397 (5)	N9—C1'	1.459 (5)
O2'—H2'	0.8399	C1'—C2'	1.555 (7)
O3'—C3'	1.436 (5)	C1'—H1'1	0.9800
O4'—C4'	1.412 (6)	C2'—C3'	1.517 (7)
O4'—C1'	1.419 (7)	C2'—H2'1	0.9800
O5'—C5'	1.458 (6)	C3'—C4'	1.515 (7)
O6—C6	1.219 (5)	C3'—H3'1	0.9800
N1—C2	1.374 (6)	C4'—C5'	1.501 (8)
N1—C6	1.391 (6)	C4'—H4'1	0.9800
N1—H1	0.8801	C5'—H5'1	0.9700
N2—C2	1.330 (6)	C5'—H5'2	0.9700
N2—H2A	0.8799	C4—C5	1.365 (6)
N2—H2B	0.8798	C5—C6	1.419 (6)
N3—C2	1.325 (5)	C8—H8	0.9300
N3—C4	1.346 (5)	O22W—O42Wⁱ	1.03 (7)
N7—C8	1.313 (6)	O42W—O22Wⁱⁱ	1.03 (7)

O5'—P1—O3'	103.85 (19)	C1'—C2'—H2'1	112.3
O3—P1—O3'	108.2 (2)	O3'—C3'—C4'	110.3 (4)
O5—P1—O3'	107.49 (19)	O3'—C3'—C2'	116.0 (4)
O3—P1—O5'	109.5 (2)	C4'—C3'—C2'	103.0 (4)
O5—P1—O5'	108.5 (2)	O3'—C3'—H3'1	109.1
O5—P1—O3	118.2 (2)	C4'—C3'—H3'1	109.1
C2'—O2'—H2'	121.7	C2'—C3'—H3'1	109.1
C3'—O3'—P1	111.9 (3)	O4'—C4'—C5'	114.3 (4)
C4'—O4'—C1'	107.1 (3)	O4'—C4'—C3'	102.2 (3)
C5'—O5'—P1	120.7 (3)	C5'—C4'—C3'	109.7 (4)
C2—N1—C6	125.9 (4)	O4'—C4'—H4'1	110.1
C2—N1—H1	120.3	C5'—C4'—H4'1	110.1
C6—N1—H1	113.7	C3'—C4'—H4'1	110.1
C2—N2—H2A	113.0	O5'—C5'—C4'	105.1 (4)
C2—N2—H2B	117.0	O5'—C5'—H5'1	110.7
H2A—N2—H2B	127.7	C4'—C5'—H5'1	110.7
C2—N3—C4	112.5 (4)	O5'—C5'—H5'2	110.7
C8—N7—C5	108.0 (4)	C4'—C5'—H5'2	110.7
C8—N7—H7	125.5	H5'1—C5'—H5'2	108.8
C5—N7—H7	125.9	N3—C2—N2	119.9 (4)
C8—N9—C4	107.7 (3)	N3—C2—N1	123.3 (4)
C8—N9—C1'	123.3 (4)	N2—C2—N1	116.9 (4)
C4—N9—C1'	128.8 (3)	N3—C4—C5	127.4 (4)
O4'—C1'—N9	106.7 (4)	N3—C4—N9	125.7 (4)
O4'—C1'—C2'	108.4 (3)	C5—C4—N9	106.9 (4)
N9—C1'—C2'	116.1 (4)	C4—C5—N7	107.4 (4)
O4'—C1'—H1'1	108.5	C4—C5—C6	121.0 (4)
N9—C1'—H1'1	108.5	N7—C5—C6	131.6 (4)
C2'—C1'—H1'1	108.5	O6—C6—N1	121.3 (4)
O2'—C2'—C3'	108.1 (4)	O6—C6—C5	129.0 (5)
O2'—C2'—C1'	111.1 (4)	N1—C6—C5	109.7 (4)
C3'—C2'—C1'	99.9 (4)	N7—C8—N9	109.9 (4)
O2'—C2'—H2'1	112.4	N7—C8—H8	125.0
C3'—C2'—H2'1	112.4	N9—C8—H8	125.0

O5—P1—O3'—C3'	162.9 (3)	P1—O5'—C5'—C4'	55.7 (6)
O3—P1—O3'—C3'	−68.4 (3)	O4'—C4'—C5'—O5'	−175.3 (4)
O5'—P1—O3'—C3'	48.0 (3)	C3'—C4'—C5'—O5'	−61.1 (5)
O5—P1—O5'—C5'	−162.3 (4)	C4—N3—C2—N2	−179.6 (5)
O3—P1—O5'—C5'	67.3 (4)	C4—N3—C2—N1	0.2 (7)
O3'—P1—O5'—C5'	−48.1 (4)	C6—N1—C2—N3	2.4 (8)
C4'—O4'—C1'—N9	−144.4 (4)	C6—N1—C2—N2	−177.8 (5)
C4'—O4'—C1'—C2'	−18.6 (4)	C2—N3—C4—C5	−0.4 (7)
C8—N9—C1'—O4'	−113.2 (5)	C2—N3—C4—N9	−179.8 (4)
C4—N9—C1'—O4'	62.1 (6)	C8—N9—C4—N3	179.8 (5)
C8—N9—C1'—C2'	125.9 (5)	C1'—N9—C4—N3	3.9 (8)
C4—N9—C1'—C2'	−58.8 (7)	C8—N9—C4—C5	0.3 (5)
O4'—C1'—C2'—O2'	104.6 (4)	C1'—N9—C4—C5	−175.6 (5)
N9—C1'—C2'—O2'	−135.4 (4)	N3—C4—C5—N7	180.0 (5)
O4'—C1'—C2'—C3'	−9.4 (4)	N9—C4—C5—N7	−0.5 (5)
N9—C1'—C2'—C3'	110.7 (4)	N3—C4—C5—C6	−1.7 (8)
P1—O3'—C3'—C4'	−62.1 (4)	N9—C4—C5—C6	177.7 (5)
P1—O3'—C3'—C2'	−178.6 (3)	C8—N7—C5—C4	0.6 (6)
O2'—C2'—C3'—O3'	36.0 (5)	C8—N7—C5—C6	−177.4 (5)
C1'—C2'—C3'—O3'	152.2 (4)	C2—N1—C6—O6	176.5 (5)
O2'—C2'—C3'—C4'	−84.5 (4)	C2—N1—C6—C5	−4.1 (8)
C1'—C2'—C3'—C4'	31.6 (4)	C4—C5—C6—O6	−177.0 (5)
C1'—O4'—C4'—C5'	157.4 (4)	N7—C5—C6—O6	0.8 (10)
C1'—O4'—C4'—C3'	38.9 (4)	C4—C5—C6—N1	3.7 (7)
O3'—C3'—C4'—O4'	−168.9 (4)	N7—C5—C6—N1	−178.5 (5)
C2'—C3'—C4'—O4'	−44.5 (5)	C5—N7—C8—N9	−0.4 (7)
O3'—C3'—C4'—C5'	69.4 (5)	C4—N9—C8—N7	0.1 (6)
C2'—C3'—C4'—C5'	−166.2 (4)	C1'—N9—C8—N7	176.2 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2′···O3ⁱⁱⁱ	0.84	1.93	2.679 (5)	149
N1—H1···O5^iv	0.88	2.01	2.788 (5)	147
N2—H2A···O1W	0.88	2.09	2.86 (2)	146
N2—H2A···O10W	0.88	2.42	3.12 (3)	137
N2—H2A···O50W	0.88	2.23	3.023 (18)	149
N2—H2A···O51W	0.88	1.84	2.69 (5)	162
N2—H2B···O5^iv	0.88	2.14	2.905 (5)	145
N7—H7···O3W^v	0.88	1.80	2.67 (2)	169
N7—H7···O30W^v	0.88	1.85	2.711 (15)	165
N7—H7···O31W^v	0.88	1.98	2.80 (3)	154
N7—H7···O32W^v	0.88	1.81	2.59 (4)	148
C2′—H2′1···O6^vi	0.98	2.52	3.435 (6)	155
C3′—H3′1···N3	0.98	2.59	3.297 (6)	129
C4′—H4′1···O12W^vii	0.98	2.46	3.30 (4)	143
C5′—H5′1···O6^viii	0.97	2.44	3.129 (7)	128
C8—H8···O5′^vii	0.93	2.46	3.042 (6)	120
C8—H8···O2W^v	0.93	2.52	3.10 (2)	121
C8—H8···O21W^v	0.93	2.52	3.19 (4)	129

Symmetry codes: (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1/2, −y+1, z+1/2; (v) x, y+1, z; (vi) x+1/2, −y+3/2, −z+1; (vii) −x, y+1/2, −z+1/2; (viii) x−1/2, −y+3/2, −z+1.

(IV_gmpna) Guanosine 3':5'-cyclic phosphate sodium salt tetrahydrate top

Crystal data top

Na⁺·C₁₀H₁₁N₅O₇P⁻·4H₂O	D_x = 1.704 Mg m⁻³
M_r = 439.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 22354 reflections
a = 7.206 (2) Å	θ = 4.8–38.5°
b = 12.669 (3) Å	µ = 0.26 mm⁻¹
c = 18.754 (3) Å	T = 100 K
V = 1712.1 (7) Å³	Block, colourless
Z = 4	0.40 × 0.12 × 0.12 mm
F(000) = 912

Data collection top

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	7524 independent reflections
Radiation source: Enhance (Mo) X-ray Source	7142 reflections with I > 2σ(I)
Detector resolution: 8.1956 pixels mm^-1	R_int = 0.026
ω and phi scans	θ_max = 35.0°, θ_min = 4.8°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −11→11
T_min = 0.949, T_max = 1.000	k = −15→20
32323 measured reflections	l = −30→30

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0402P)² + 0.2589P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
7524 reflections	Δρ_max = 0.42 e Å⁻³
258 parameters	Δρ_min = −0.43 e Å⁻³
18 restraints	Absolute structure: Flack x determined using 3048 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.031 (18)

Crystal data top

Na⁺·C₁₀H₁₁N₅O₇P⁻·4H₂O	V = 1712.1 (7) Å³
M_r = 439.26	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.206 (2) Å	µ = 0.26 mm⁻¹
b = 12.669 (3) Å	T = 100 K
c = 18.754 (3) Å	0.40 × 0.12 × 0.12 mm

Data collection top

Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	7524 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	7142 reflections with I > 2σ(I)
T_min = 0.949, T_max = 1.000	R_int = 0.026
32323 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.075	Δρ_max = 0.42 e Å⁻³
S = 1.10	Δρ_min = −0.43 e Å⁻³
7524 reflections	Absolute structure: Flack x determined using 3048 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
258 parameters	Absolute structure parameter: −0.031 (18)
18 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Na1	0.37779 (8)	0.26984 (4)	0.51191 (3)	0.01258 (10)
P1	0.20996 (4)	0.41025 (2)	0.24538 (2)	0.00854 (6)
O3	0.20916 (15)	0.35833 (8)	0.31757 (5)	0.01272 (16)
O5	0.25330 (15)	0.34269 (8)	0.18320 (5)	0.01334 (17)
O2'	0.53051 (14)	0.68959 (8)	0.20882 (5)	0.01253 (17)
H2'	0.6107	0.7376	0.2104	0.019*
O3'	0.36526 (13)	0.50242 (7)	0.24555 (5)	0.01044 (15)
O4'	0.12534 (14)	0.74416 (7)	0.27850 (6)	0.01228 (17)
O5'	0.01884 (14)	0.47096 (7)	0.23123 (6)	0.01222 (17)
O6	0.23094 (16)	0.93840 (7)	0.58672 (5)	0.01359 (18)
N1	0.26431 (17)	0.76469 (8)	0.55677 (6)	0.01143 (18)
H1	0.2564	0.7475	0.6021	0.014*
N2	0.27738 (19)	0.58504 (9)	0.53627 (6)	0.0149 (2)
H2A	0.2768	0.5764	0.5828	0.018*
H2B	0.3047	0.5315	0.5083	0.018*
N3	0.29292 (17)	0.69673 (8)	0.43900 (6)	0.01094 (18)
N7	0.29982 (18)	0.98010 (8)	0.42553 (6)	0.01088 (18)
N9	0.31909 (15)	0.83913 (8)	0.35331 (6)	0.00947 (17)
C1'	0.31107 (18)	0.78330 (9)	0.28604 (6)	0.00961 (19)
H1'1	0.3357	0.8347	0.2467	0.012*
C2'	0.44602 (18)	0.68773 (9)	0.27749 (7)	0.00964 (19)
H2'1	0.5400	0.6847	0.3167	0.012*
C3'	0.30999 (17)	0.59684 (9)	0.28116 (6)	0.00908 (18)
H3'1	0.2828	0.5804	0.3323	0.011*
C4'	0.13810 (17)	0.64281 (9)	0.24668 (7)	0.00961 (18)
H4'1	0.1560	0.6494	0.1940	0.012*
C5'	−0.02526 (18)	0.57253 (10)	0.26287 (7)	0.0123 (2)
H5'1	−0.0428	0.5655	0.3150	0.015*
H5'2	−0.1402	0.6018	0.2418	0.015*
C2	0.27949 (18)	0.68287 (9)	0.50894 (7)	0.01056 (19)
C4	0.29697 (19)	0.79966 (9)	0.42120 (6)	0.00960 (19)
C5	0.28404 (19)	0.88745 (9)	0.46514 (6)	0.00977 (19)
C6	0.25799 (18)	0.87123 (10)	0.53910 (7)	0.0104 (2)
C8	0.32045 (18)	0.94708 (9)	0.35961 (7)	0.0103 (2)
H8	0.3349	0.9934	0.3202	0.012*
O1W	0.41210 (15)	0.41977 (8)	0.43714 (5)	0.01479 (18)
H1W	0.3530	0.4030	0.4002	0.022*
H2W	0.5028	0.4584	0.4266	0.022*
O2W	0.15792 (15)	0.18866 (8)	0.42961 (6)	0.01390 (18)
H3W	0.1706	0.2210	0.3908	0.021*
H4W	0.2004	0.1271	0.4263	0.021*
O3W	0.3659 (3)	0.14447 (13)	0.60332 (11)	0.0233 (6)	0.929 (11)
O30W	0.4161 (14)	0.1286 (3)	0.5877 (7)	0.016 (5)*	0.071 (11)
H5W	0.4629	0.1404	0.6280	0.024*
H6W	0.3306	0.0838	0.5912	0.024*
O4W	0.10246 (15)	0.34446 (8)	0.56450 (6)	0.01539 (18)
H7W	0.0943	0.3275	0.6077	0.023*
H8W	0.0488	0.4024	0.5572	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0126 (2)	0.0119 (2)	0.0133 (2)	0.0002 (2)	−0.00116 (19)	0.00045 (19)
P1	0.00953 (12)	0.00727 (11)	0.00883 (12)	0.00061 (10)	−0.00006 (10)	−0.00066 (9)
O3	0.0161 (4)	0.0125 (4)	0.0096 (4)	−0.0011 (4)	−0.0014 (3)	0.0021 (3)
O5	0.0161 (4)	0.0118 (4)	0.0121 (4)	−0.0005 (3)	0.0014 (3)	−0.0045 (3)
O2'	0.0132 (4)	0.0118 (4)	0.0126 (4)	−0.0026 (3)	0.0040 (3)	−0.0034 (3)
O3'	0.0097 (3)	0.0071 (3)	0.0145 (4)	0.0004 (3)	0.0013 (3)	−0.0028 (3)
O4'	0.0108 (4)	0.0087 (3)	0.0173 (4)	0.0014 (3)	−0.0011 (3)	−0.0036 (3)
O5'	0.0100 (4)	0.0084 (3)	0.0182 (4)	0.0013 (3)	−0.0024 (3)	−0.0018 (3)
O6	0.0198 (5)	0.0106 (3)	0.0103 (4)	0.0011 (3)	0.0009 (3)	−0.0026 (3)
N1	0.0172 (5)	0.0086 (4)	0.0086 (4)	0.0009 (4)	0.0016 (4)	−0.0002 (3)
N2	0.0256 (6)	0.0084 (4)	0.0107 (4)	0.0011 (4)	0.0026 (4)	0.0010 (3)
N3	0.0157 (5)	0.0074 (4)	0.0098 (4)	0.0001 (4)	0.0013 (4)	0.0001 (3)
N7	0.0148 (5)	0.0080 (4)	0.0098 (4)	0.0005 (4)	0.0003 (4)	0.0001 (3)
N9	0.0132 (4)	0.0064 (4)	0.0088 (4)	0.0003 (3)	0.0010 (3)	−0.0003 (3)
C1'	0.0120 (5)	0.0086 (4)	0.0083 (4)	0.0002 (4)	−0.0006 (4)	−0.0011 (3)
C2'	0.0104 (5)	0.0083 (4)	0.0102 (5)	−0.0003 (4)	0.0003 (4)	−0.0016 (4)
C3'	0.0101 (4)	0.0071 (4)	0.0101 (4)	0.0012 (4)	0.0001 (4)	−0.0014 (3)
C4'	0.0102 (4)	0.0073 (4)	0.0114 (5)	0.0006 (4)	−0.0006 (4)	−0.0015 (4)
C5'	0.0103 (5)	0.0097 (4)	0.0167 (5)	0.0002 (4)	−0.0002 (4)	−0.0016 (4)
C2	0.0125 (5)	0.0086 (4)	0.0106 (5)	0.0001 (4)	0.0014 (4)	0.0000 (4)
C4	0.0117 (5)	0.0087 (4)	0.0084 (4)	−0.0001 (4)	0.0009 (4)	−0.0001 (3)
C5	0.0134 (5)	0.0074 (4)	0.0085 (4)	0.0006 (4)	0.0007 (4)	−0.0006 (3)
C6	0.0118 (5)	0.0092 (4)	0.0104 (5)	0.0008 (4)	0.0003 (4)	−0.0009 (4)
C8	0.0137 (5)	0.0072 (4)	0.0100 (5)	0.0000 (4)	0.0004 (4)	−0.0001 (4)
O1W	0.0177 (4)	0.0144 (4)	0.0123 (4)	−0.0021 (4)	−0.0007 (3)	0.0001 (3)
O2W	0.0158 (4)	0.0116 (4)	0.0143 (4)	0.0020 (3)	0.0022 (3)	−0.0002 (3)
O3W	0.0237 (9)	0.0160 (6)	0.0303 (8)	−0.0066 (6)	−0.0130 (7)	0.0086 (5)
O4W	0.0171 (5)	0.0149 (4)	0.0141 (4)	0.0029 (4)	0.0020 (4)	0.0011 (3)

Geometric parameters (Å, º) top

Na1—O1W	2.3739 (12)	N7—C5	1.3937 (16)
Na1—O2W	2.4394 (13)	N9—C8	1.3727 (16)
Na1—O2Wⁱ	2.3567 (13)	N9—C4	1.3771 (16)
Na1—O3W	2.3387 (14)	N9—C1'	1.4475 (16)
Na1—O30W	2.301 (8)	C1'—C2'	1.5612 (17)
Na1—O4W	2.4089 (13)	C1'—H1'1	1.0000
Na1—O4Wⁱ	2.6021 (13)	C2'—C3'	1.5137 (17)
Na1—Na1ⁱⁱ	3.6652 (10)	C2'—H2'1	1.0000
Na1—Na1ⁱ	3.6652 (10)	C3'—C4'	1.5137 (17)
P1—O3'	1.6174 (10)	C3'—H3'1	1.0000
P1—O5'	1.5996 (11)	C4'—C5'	1.5069 (18)
P1—O3	1.5052 (10)	C4'—H4'1	1.0000
P1—O5	1.4800 (10)	C5'—H5'1	0.9900
O2'—C2'	1.4247 (16)	C5'—H5'2	0.9900
O2'—H2'	0.8397	C4—C5	1.3874 (16)
O3'—C3'	1.4268 (15)	C5—C6	1.4147 (18)
O4'—C4'	1.4189 (15)	C8—H8	0.9500
O4'—C1'	1.4342 (17)	O1W—H1W	0.8403
O5'—C5'	1.4522 (16)	O1W—H2W	0.8400
O6—C6	1.2489 (15)	O2W—Na1ⁱⁱ	2.3567 (13)
N1—C2	1.3752 (16)	O2W—H3W	0.8396
N1—C6	1.3907 (17)	O2W—H4W	0.8403
N1—H1	0.8803	O3W—H5W	0.8401
N2—C2	1.3412 (16)	O3W—H6W	0.8410
N2—H2A	0.8795	O30W—H5W	0.8417
N2—H2B	0.8800	O30W—H6W	0.8405
N3—C2	1.3268 (16)	O4W—Na1ⁱⁱ	2.6021 (13)
N3—C4	1.3464 (16)	O4W—H7W	0.8403
N7—C8	1.3135 (17)	O4W—H8W	0.8403

O30W—Na1—O2Wⁱ	77.48 (12)	C2'—C1'—H1'1	108.5
O3W—Na1—O2Wⁱ	80.90 (5)	O2'—C2'—C3'	109.30 (10)
O30W—Na1—O1W	167.0 (2)	O2'—C2'—C1'	110.26 (10)
O3W—Na1—O1W	168.60 (6)	C3'—C2'—C1'	100.48 (10)
O2Wⁱ—Na1—O1W	90.41 (4)	O2'—C2'—H2'1	112.1
O30W—Na1—O4W	98.7 (4)	C3'—C2'—H2'1	112.1
O3W—Na1—O4W	86.34 (8)	C1'—C2'—H2'1	112.1
O2Wⁱ—Na1—O4W	115.30 (5)	O3'—C3'—C2'	115.83 (10)
O1W—Na1—O4W	90.78 (4)	O3'—C3'—C4'	110.55 (10)
O30W—Na1—O2W	98.10 (8)	C2'—C3'—C4'	102.58 (10)
O3W—Na1—O2W	98.84 (5)	O3'—C3'—H3'1	109.2
O2Wⁱ—Na1—O2W	160.89 (4)	C2'—C3'—H3'1	109.2
O1W—Na1—O2W	91.79 (4)	C4'—C3'—H3'1	109.2
O4W—Na1—O2W	83.66 (4)	O4'—C4'—C5'	113.54 (10)
O30W—Na1—O4Wⁱ	80.4 (4)	O4'—C4'—C3'	102.80 (10)
O3W—Na1—O4Wⁱ	92.79 (8)	C5'—C4'—C3'	109.02 (10)
O2Wⁱ—Na1—O4Wⁱ	81.23 (4)	O4'—C4'—H4'1	110.4
O1W—Na1—O4Wⁱ	93.16 (4)	C5'—C4'—H4'1	110.4
O4W—Na1—O4Wⁱ	163.00 (4)	C3'—C4'—H4'1	110.4
O2W—Na1—O4Wⁱ	79.69 (4)	O5'—C5'—C4'	105.68 (10)
O30W—Na1—Na1ⁱⁱ	95.0 (2)	O5'—C5'—H5'1	110.6
O3W—Na1—Na1ⁱⁱ	87.71 (5)	C4'—C5'—H5'1	110.6
O2Wⁱ—Na1—Na1ⁱⁱ	158.32 (4)	O5'—C5'—H5'2	110.6
O1W—Na1—Na1ⁱⁱ	98.05 (4)	C4'—C5'—H5'2	110.6
O4W—Na1—Na1ⁱⁱ	45.10 (3)	H5'1—C5'—H5'2	108.7
O2W—Na1—Na1ⁱⁱ	39.34 (3)	N3—C2—N2	120.06 (11)
O4Wⁱ—Na1—Na1ⁱⁱ	117.92 (4)	N3—C2—N1	123.42 (11)
O30W—Na1—Na1ⁱ	81.4 (3)	N2—C2—N1	116.51 (11)
O3W—Na1—Na1ⁱ	91.85 (7)	N3—C4—N9	125.70 (11)
O2Wⁱ—Na1—Na1ⁱ	41.01 (3)	N3—C4—C5	128.88 (11)
O1W—Na1—Na1ⁱ	86.29 (4)	N9—C4—C5	105.41 (10)
O4W—Na1—Na1ⁱ	155.97 (4)	C4—C5—N7	110.68 (11)
O2W—Na1—Na1ⁱ	120.24 (4)	C4—C5—C6	118.35 (11)
O4Wⁱ—Na1—Na1ⁱ	40.97 (3)	N7—C5—C6	130.98 (11)
Na1ⁱⁱ—Na1—Na1ⁱ	158.86 (4)	O6—C6—N1	119.74 (11)
O5'—P1—O3'	104.41 (5)	O6—C6—C5	128.52 (12)
O3—P1—O3'	108.45 (6)	N1—C6—C5	111.73 (11)
O5—P1—O3'	105.85 (6)	N7—C8—N9	113.43 (11)
O3—P1—O5'	110.86 (6)	N7—C8—H8	123.3
O5—P1—O5'	109.21 (6)	N9—C8—H8	123.3
O5—P1—O3	117.19 (6)	Na1—O1W—H1W	103.4
C2'—O2'—H2'	106.0	Na1—O1W—H2W	133.3
C3'—O3'—P1	114.40 (8)	H1W—O1W—H2W	110.4
C4'—O4'—C1'	107.09 (9)	Na1ⁱⁱ—O2W—Na1	99.66 (4)
C5'—O5'—P1	123.13 (8)	Na1ⁱⁱ—O2W—H3W	112.8
C2—N1—C6	125.37 (11)	Na1—O2W—H3W	105.8
C2—N1—H1	116.7	Na1ⁱⁱ—O2W—H4W	123.6
C6—N1—H1	117.9	Na1—O2W—H4W	101.6
C2—N2—H2A	119.6	H3W—O2W—H4W	110.4
C2—N2—H2B	118.8	Na1—O3W—H5W	114.5
H2A—N2—H2B	119.8	Na1—O3W—H6W	115.7
C2—N3—C4	112.02 (11)	H5W—O3W—H6W	110.2
C8—N7—C5	104.04 (10)	Na1—O30W—H5W	117.7
C8—N9—C4	106.44 (10)	Na1—O30W—H6W	119.1
C8—N9—C1'	124.21 (11)	H5W—O30W—H6W	110.1
C4—N9—C1'	128.58 (10)	Na1—O4W—Na1ⁱⁱ	93.93 (4)
O4'—C1'—N9	106.98 (10)	Na1—O4W—H7W	110.6
O4'—C1'—C2'	107.64 (9)	Na1ⁱⁱ—O4W—H7W	110.2
N9—C1'—C2'	116.34 (10)	Na1—O4W—H8W	130.9
O4'—C1'—H1'1	108.5	Na1ⁱⁱ—O4W—H8W	96.3
N9—C1'—H1'1	108.5	H7W—O4W—H8W	110.3

O5—P1—O3'—C3'	155.93 (9)	P1—O5'—C5'—C4'	51.42 (13)
O3—P1—O3'—C3'	−77.54 (10)	O4'—C4'—C5'—O5'	−175.50 (10)
O5'—P1—O3'—C3'	40.71 (10)	C3'—C4'—C5'—O5'	−61.56 (13)
O5—P1—O5'—C5'	−152.41 (10)	C4—N3—C2—N2	−178.68 (13)
O3—P1—O5'—C5'	77.01 (11)	C4—N3—C2—N1	2.4 (2)
O3'—P1—O5'—C5'	−39.58 (11)	C6—N1—C2—N3	1.1 (2)
C4'—O4'—C1'—N9	−142.00 (10)	C6—N1—C2—N2	−177.93 (13)
C4'—O4'—C1'—C2'	−16.27 (12)	C2—N3—C4—N9	176.71 (12)
C8—N9—C1'—O4'	−104.30 (13)	C2—N3—C4—C5	−1.9 (2)
C4—N9—C1'—O4'	64.27 (15)	C8—N9—C4—N3	−178.28 (14)
C8—N9—C1'—C2'	135.38 (13)	C1'—N9—C4—N3	11.6 (2)
C4—N9—C1'—C2'	−56.05 (17)	C8—N9—C4—C5	0.64 (14)
O4'—C1'—C2'—O2'	103.62 (11)	C1'—N9—C4—C5	−169.52 (12)
N9—C1'—C2'—O2'	−136.42 (11)	N3—C4—C5—N7	178.24 (14)
O4'—C1'—C2'—C3'	−11.63 (12)	N9—C4—C5—N7	−0.64 (15)
N9—C1'—C2'—C3'	108.34 (12)	N3—C4—C5—C6	−1.9 (2)
P1—O3'—C3'—C2'	−175.48 (8)	N9—C4—C5—C6	179.25 (12)
P1—O3'—C3'—C4'	−59.39 (12)	C8—N7—C5—C4	0.36 (16)
O2'—C2'—C3'—O3'	37.66 (14)	C8—N7—C5—C6	−179.51 (14)
C1'—C2'—C3'—O3'	153.63 (10)	C2—N1—C6—O6	174.99 (13)
O2'—C2'—C3'—C4'	−82.85 (11)	C2—N1—C6—C5	−4.71 (19)
C1'—C2'—C3'—C4'	33.12 (11)	C4—C5—C6—O6	−174.84 (14)
C1'—O4'—C4'—C5'	155.28 (11)	N7—C5—C6—O6	5.0 (3)
C1'—O4'—C4'—C3'	37.67 (12)	C4—C5—C6—N1	4.83 (18)
O3'—C3'—C4'—O4'	−168.87 (9)	N7—C5—C6—N1	−175.31 (14)
C2'—C3'—C4'—O4'	−44.78 (11)	C5—N7—C8—N9	0.06 (16)
O3'—C3'—C4'—C5'	70.37 (13)	C4—N9—C8—N7	−0.46 (16)
C2'—C3'—C4'—C5'	−165.55 (10)	C1'—N9—C8—N7	170.25 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2′···O3ⁱⁱⁱ	0.84	2.07	2.8869 (15)	163
O2′—H2′···O5ⁱⁱⁱ	0.84	2.59	3.2079 (15)	131
N1—H1···O5^iv	0.88	1.90	2.7365 (15)	157
N2—H2A···O5^iv	0.88	2.15	2.9120 (16)	144
N2—H2B···O1W	0.88	2.09	2.9635 (16)	170
C2′—H2′1···O5ⁱⁱⁱ	1.00	2.50	3.0154 (17)	112
C3′—H3′1···N3	1.00	2.49	3.2216 (17)	130
C5′—H5′1···O6^v	0.99	2.46	3.3260 (18)	146
C8—H8···O3′ⁱⁱⁱ	0.95	2.49	3.0839 (17)	121
O1W—H1W···O3	0.84	1.95	2.7879 (15)	177
O1W—H2W···O6^vi	0.84	2.12	2.9509 (16)	173
O2W—H3W···O3	0.84	2.23	3.0285 (15)	158
O2W—H4W···N7^vii	0.84	2.00	2.8342 (16)	176
O3W—H5W···O3ⁱ	0.84	2.05	2.885 (2)	175
O30W—H5W···O3ⁱ	0.84	2.05	2.765 (3)	143
O3W—H6W···O6^vii	0.84	1.98	2.8032 (18)	166
O30W—H6W···O6^vii	0.84	1.98	2.755 (5)	153
O4W—H7W···O2′^iv	0.84	2.11	2.9034 (16)	157
O4W—H8W···N7^v	0.84	2.35	3.1195 (17)	152

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1/2, −y+1, z+1/2; (v) x−1/2, −y+3/2, −z+1; (vi) x+1/2, −y+3/2, −z+1; (vii) x, y−1, z.

(V_impna) Inosine 3':5'-cyclic phosphate sodium salt tetrahydrate top

Crystal data top

Na⁺·C₁₀H₁₀N₄O₇P⁻·4H₂O	D_x = 1.672 Mg m⁻³
M_r = 424.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 6269 reflections
a = 6.652 (2) Å	θ = 3.0–36.6°
b = 14.726 (3) Å	µ = 0.26 mm⁻¹
c = 17.208 (4) Å	T = 100 K
V = 1685.7 (7) Å³	Plate, colourless
Z = 4	0.60 × 0.19 × 0.05 mm
F(000) = 880

Data collection top

Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire2 CCD camera	5098 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.042
ω scan	θ_max = 36.7°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −9→7
T_min = 0.681, T_max = 1.000	k = −24→19
16251 measured reflections	l = −22→26
5851 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0422P)² + 0.4883P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
5851 reflections	Δρ_max = 0.67 e Å⁻³
249 parameters	Δρ_min = −0.46 e Å⁻³
17 restraints	Absolute structure: Flack x determined using 1605 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (6)

Crystal data top

Na⁺·C₁₀H₁₀N₄O₇P⁻·4H₂O	V = 1685.7 (7) Å³
M_r = 424.24	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.652 (2) Å	µ = 0.26 mm⁻¹
b = 14.726 (3) Å	T = 100 K
c = 17.208 (4) Å	0.60 × 0.19 × 0.05 mm

Data collection top

Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire2 CCD camera	5851 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	5098 reflections with I > 2σ(I)
T_min = 0.681, T_max = 1.000	R_int = 0.042
16251 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.103	Δρ_max = 0.67 e Å⁻³
S = 1.06	Δρ_min = −0.46 e Å⁻³
5851 reflections	Absolute structure: Flack x determined using 1605 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
249 parameters	Absolute structure parameter: 0.03 (6)
17 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Na1	1.04887 (15)	0.47040 (6)	0.35974 (6)	0.0141 (2)
P1	0.50817 (10)	0.28271 (4)	0.63663 (3)	0.01117 (12)
O3	0.4683 (3)	0.34258 (11)	0.70488 (9)	0.0146 (3)
O5	0.5940 (3)	0.19105 (11)	0.64898 (10)	0.0143 (3)
O2'	0.7999 (3)	0.41743 (11)	0.44161 (11)	0.0181 (4)
H2'	0.7749	0.3619	0.4471	0.027*
O3'	0.6518 (3)	0.33532 (11)	0.57633 (9)	0.0121 (3)
O4'	0.3215 (3)	0.47015 (11)	0.45894 (10)	0.0137 (3)
O5'	0.3006 (3)	0.27104 (11)	0.58782 (10)	0.0127 (3)
O6	0.4757 (3)	0.89263 (11)	0.57602 (11)	0.0181 (4)
N1	0.4747 (3)	0.76238 (13)	0.64817 (11)	0.0151 (4)
H1	0.4817	0.7908	0.6930	0.018*
N3	0.4754 (4)	0.61254 (13)	0.59865 (12)	0.0166 (4)
N7	0.4713 (3)	0.76281 (13)	0.43412 (12)	0.0139 (4)
N9	0.4808 (3)	0.61297 (12)	0.45756 (11)	0.0119 (4)
C1'	0.5073 (4)	0.51706 (13)	0.44159 (13)	0.0116 (4)
H1'1	0.5386	0.5091	0.3852	0.014*
C2'	0.6768 (4)	0.47120 (16)	0.49054 (13)	0.0119 (4)
H2'1	0.7584	0.5177	0.5189	0.014*
C3'	0.5533 (4)	0.41507 (15)	0.54634 (14)	0.0111 (4)
H3'1	0.5079	0.4541	0.5906	0.013*
C4'	0.3733 (4)	0.38771 (16)	0.49794 (14)	0.0124 (4)
H4'1	0.4140	0.3408	0.4590	0.015*
C5'	0.2101 (4)	0.35015 (16)	0.54986 (14)	0.0141 (5)
H5'1	0.1682	0.3958	0.5888	0.017*
H5'2	0.0912	0.3321	0.5189	0.017*
C2	0.4767 (4)	0.67059 (15)	0.65602 (14)	0.0173 (5)
H2	0.4793	0.6467	0.7073	0.021*
C4	0.4731 (4)	0.65526 (15)	0.52854 (13)	0.0123 (4)
C5	0.4682 (4)	0.74713 (15)	0.51348 (13)	0.0119 (4)
C6	0.4724 (4)	0.80948 (15)	0.57739 (14)	0.0131 (4)
C8	0.4780 (4)	0.68141 (15)	0.40317 (14)	0.0131 (4)
H8	0.4807	0.6708	0.3487	0.016*
O1W	0.8110 (4)	0.50601 (15)	0.26239 (12)	0.0274 (5)
H1W	0.8643	0.5506	0.2400	0.041*
H2W	0.7187	0.4842	0.2348	0.041*
O2W	1.2887 (3)	0.52640 (14)	0.27033 (11)	0.0233 (4)
H3W	1.2215	0.5654	0.2460	0.035*
H4W	1.3392	0.4887	0.2393	0.035*
O3W	0.4729 (4)	0.90567 (14)	0.31821 (13)	0.0192 (7)	0.861 (8)
H6W	0.4947	0.8671	0.2832	0.029*	0.861 (8)
H5W	0.4627	0.8798	0.3616	0.029*
O30W	0.484 (3)	0.9353 (4)	0.3548 (7)	0.044 (6)*	0.139 (8)
H60W	0.5438	0.9578	0.3932	0.066*	0.139 (8)
O4W	0.9803 (4)	0.22871 (17)	0.71053 (14)	0.0409 (6)
H7W	1.0645	0.2346	0.6744	0.061*
H8W	0.8692	0.2112	0.6926	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0194 (5)	0.0105 (4)	0.0125 (4)	0.0000 (4)	0.0008 (4)	0.0001 (4)
P1	0.0158 (3)	0.0084 (2)	0.0092 (2)	0.0000 (2)	−0.0006 (2)	−0.00010 (19)
O3	0.0231 (10)	0.0115 (7)	0.0094 (7)	0.0016 (7)	0.0010 (7)	−0.0015 (6)
O5	0.0198 (9)	0.0093 (7)	0.0138 (8)	0.0008 (6)	−0.0014 (7)	0.0004 (6)
O2'	0.0251 (10)	0.0087 (7)	0.0206 (9)	0.0035 (7)	0.0106 (8)	0.0006 (7)
O3'	0.0149 (9)	0.0096 (7)	0.0119 (8)	0.0013 (6)	0.0002 (6)	0.0025 (6)
O4'	0.0162 (9)	0.0096 (7)	0.0153 (8)	−0.0008 (7)	−0.0027 (7)	0.0039 (7)
O5'	0.0140 (9)	0.0100 (7)	0.0142 (8)	−0.0009 (6)	−0.0033 (6)	0.0034 (6)
O6	0.0234 (10)	0.0091 (7)	0.0217 (9)	0.0010 (7)	−0.0022 (8)	−0.0026 (6)
N1	0.0215 (11)	0.0129 (8)	0.0110 (9)	0.0008 (8)	−0.0003 (8)	−0.0022 (7)
N3	0.0267 (13)	0.0126 (8)	0.0106 (9)	0.0009 (9)	0.0016 (9)	−0.0004 (7)
N7	0.0162 (11)	0.0114 (8)	0.0142 (9)	0.0002 (8)	−0.0021 (8)	0.0012 (7)
N9	0.0168 (11)	0.0091 (7)	0.0098 (8)	0.0000 (8)	0.0019 (8)	0.0008 (6)
C1'	0.0163 (12)	0.0081 (8)	0.0103 (10)	−0.0003 (9)	0.0005 (9)	−0.0006 (7)
C2'	0.0154 (12)	0.0082 (9)	0.0121 (11)	0.0008 (9)	0.0020 (8)	−0.0001 (8)
C3'	0.0141 (12)	0.0086 (8)	0.0107 (10)	0.0006 (8)	−0.0006 (8)	0.0018 (8)
C4'	0.0163 (13)	0.0090 (9)	0.0119 (11)	−0.0002 (9)	−0.0015 (9)	0.0014 (8)
C5'	0.0162 (12)	0.0123 (10)	0.0140 (11)	−0.0005 (9)	−0.0023 (9)	0.0031 (9)
C2	0.0271 (15)	0.0126 (9)	0.0121 (10)	0.0018 (10)	−0.0003 (10)	0.0010 (8)
C4	0.0130 (12)	0.0106 (8)	0.0134 (10)	0.0010 (9)	0.0006 (9)	−0.0018 (8)
C5	0.0116 (12)	0.0111 (8)	0.0130 (11)	0.0004 (9)	−0.0006 (8)	−0.0005 (8)
C6	0.0121 (12)	0.0131 (9)	0.0141 (10)	0.0004 (9)	0.0007 (9)	−0.0017 (8)
C8	0.0154 (12)	0.0109 (9)	0.0131 (10)	−0.0003 (9)	−0.0003 (9)	0.0016 (8)
O1W	0.0348 (13)	0.0253 (11)	0.0221 (10)	−0.0102 (10)	−0.0061 (9)	0.0066 (8)
O2W	0.0258 (11)	0.0255 (10)	0.0187 (9)	0.0100 (9)	0.0042 (8)	0.0059 (8)
O3W	0.0264 (14)	0.0170 (10)	0.0143 (11)	0.0016 (10)	0.0011 (9)	0.0053 (8)
O4W	0.0315 (13)	0.0570 (15)	0.0341 (12)	−0.0041 (13)	−0.0007 (11)	0.0116 (11)

Geometric parameters (Å, º) top

Na1—O2'	2.310 (2)	N7—C5	1.385 (3)
Na1—O4'ⁱ	2.491 (2)	N9—C4	1.372 (3)
Na1—O5ⁱⁱ	2.401 (2)	N9—C8	1.375 (3)
Na1—O6ⁱⁱⁱ	2.3510 (19)	N9—C1'	1.450 (3)
Na1—O1W	2.363 (2)	C1'—C2'	1.561 (3)
Na1—O2W	2.365 (2)	C1'—H1'1	1.0000
Na1—H1W	2.6739	C2'—C3'	1.510 (3)
Na1—H3W	2.6662	C2'—H2'1	1.0000
P1—O3'	1.6093 (18)	C3'—C4'	1.513 (3)
P1—O5'	1.6253 (19)	C3'—H3'1	1.0000
P1—O3	1.4924 (17)	C4'—C5'	1.511 (4)
P1—O5	1.4809 (18)	C4'—H4'1	1.0000
O5—Na1^iv	2.401 (2)	C5'—H5'1	0.9900
O2'—C2'	1.416 (3)	C5'—H5'2	0.9900
O2'—H2'	0.8396	C2—H2	0.9500
O3'—C3'	1.440 (3)	C4—C5	1.378 (3)
O4'—C4'	1.429 (3)	C5—C6	1.433 (3)
O4'—C1'	1.447 (3)	C8—H8	0.9500
O4'—Na1^v	2.491 (2)	O1W—H1W	0.8400
O5'—C5'	1.465 (3)	O1W—H2W	0.8401
O6—C6	1.225 (3)	O2W—H3W	0.8401
O6—Na1^vi	2.3510 (19)	O2W—H4W	0.8405
N1—C2	1.359 (3)	O3W—H6W	0.8406
N1—C6	1.402 (3)	O3W—H5W	0.8417
N1—H1	0.8797	O30W—H5W	0.8385
N3—C2	1.306 (3)	O30W—H60W	0.8401
N3—C4	1.361 (3)	O4W—H7W	0.8415
N7—C8	1.313 (3)	O4W—H8W	0.8413

O2'—Na1—O6ⁱⁱⁱ	81.63 (7)	O4'—C1'—C2'	107.41 (17)
O2'—Na1—O1W	91.56 (8)	N9—C1'—C2'	114.00 (19)
O6ⁱⁱⁱ—Na1—O1W	90.25 (8)	O4'—C1'—H1'1	108.8
O2'—Na1—O2W	176.58 (8)	N9—C1'—H1'1	108.8
O6ⁱⁱⁱ—Na1—O2W	98.42 (8)	C2'—C1'—H1'1	108.8
O1W—Na1—O2W	85.02 (8)	O2'—C2'—C3'	112.74 (19)
O2'—Na1—O5ⁱⁱ	78.07 (7)	O2'—C2'—C1'	109.79 (18)
O6ⁱⁱⁱ—Na1—O5ⁱⁱ	154.79 (7)	C3'—C2'—C1'	100.74 (19)
O1W—Na1—O5ⁱⁱ	105.02 (8)	O2'—C2'—H2'1	111.1
O2W—Na1—O5ⁱⁱ	102.73 (7)	C3'—C2'—H2'1	111.1
O2'—Na1—O4'ⁱ	95.94 (7)	C1'—C2'—H2'1	111.1
O6ⁱⁱⁱ—Na1—O4'ⁱ	80.19 (7)	O3'—C3'—C2'	115.2 (2)
O1W—Na1—O4'ⁱ	166.83 (8)	O3'—C3'—C4'	109.88 (18)
O2W—Na1—O4'ⁱ	87.43 (7)	C2'—C3'—C4'	103.09 (19)
O5ⁱⁱ—Na1—O4'ⁱ	87.16 (7)	O3'—C3'—H3'1	109.5
O2'—Na1—H1W	106.9	C2'—C3'—H3'1	109.5
O6ⁱⁱⁱ—Na1—H1W	83.6	C4'—C3'—H3'1	109.5
O1W—Na1—H1W	17.9	O4'—C4'—C5'	114.6 (2)
O2W—Na1—H1W	69.8	O4'—C4'—C3'	102.88 (18)
O5ⁱⁱ—Na1—H1W	116.5	C5'—C4'—C3'	109.91 (19)
O4'ⁱ—Na1—H1W	149.7	O4'—C4'—H4'1	109.8
O2'—Na1—H3W	159.0	C5'—C4'—H4'1	109.8
O6ⁱⁱⁱ—Na1—H3W	89.1	C3'—C4'—H4'1	109.8
O1W—Na1—H3W	69.6	O5'—C5'—C4'	105.0 (2)
O2W—Na1—H3W	18.0	O5'—C5'—H5'1	110.7
O5ⁱⁱ—Na1—H3W	114.8	C4'—C5'—H5'1	110.7
O4'ⁱ—Na1—H3W	101.0	O5'—C5'—H5'2	110.7
H1W—Na1—H3W	53.1	C4'—C5'—H5'2	110.7
O3'—P1—O5'	102.82 (9)	H5'1—C5'—H5'2	108.8
O3—P1—O3'	109.18 (10)	N3—C2—N1	125.2 (2)
O5—P1—O3'	107.61 (10)	N3—C2—H2	117.4
O3—P1—O5'	108.55 (10)	N1—C2—H2	117.4
O5—P1—O5'	107.78 (10)	N3—C4—N9	125.4 (2)
O5—P1—O3	119.61 (10)	N3—C4—C5	128.4 (2)
P1—O5—Na1^iv	147.72 (11)	N9—C4—C5	106.21 (19)
C2'—O2'—Na1	126.02 (14)	C4—C5—N7	110.4 (2)
C2'—O2'—H2'	111.3	C4—C5—C6	119.0 (2)
Na1—O2'—H2'	122.6	N7—C5—C6	130.5 (2)
C3'—O3'—P1	110.70 (15)	O6—C6—N1	120.7 (2)
C4'—O4'—C1'	107.26 (17)	O6—C6—C5	128.8 (2)
C4'—O4'—Na1^v	119.90 (14)	N1—C6—C5	110.48 (19)
C1'—O4'—Na1^v	118.67 (13)	N7—C8—N9	113.2 (2)
C5'—O5'—P1	119.70 (15)	N7—C8—H8	123.4
C6—O6—Na1^vi	148.46 (18)	N9—C8—H8	123.4
C2—N1—C6	125.4 (2)	Na1—O1W—H1W	102.5
C2—N1—H1	112.7	Na1—O1W—H2W	143.6
C6—N1—H1	121.8	H1W—O1W—H2W	110.4
C2—N3—C4	111.6 (2)	Na1—O2W—H3W	101.8
C8—N7—C5	104.37 (19)	Na1—O2W—H4W	116.9
C4—N9—C8	105.82 (18)	H3W—O2W—H4W	110.3
C4—N9—C1'	127.99 (18)	H6W—O3W—H5W	110.1
C8—N9—C1'	125.92 (19)	H5W—O30W—H60W	110.7
O4'—C1'—N9	108.81 (19)	H7W—O4W—H8W	110.1

O3—P1—O5—Na1^iv	114.7 (2)	O3'—C3'—C4'—O4'	−167.36 (18)
O3'—P1—O5—Na1^iv	−120.0 (2)	C2'—C3'—C4'—O4'	−44.0 (2)
O5'—P1—O5—Na1^iv	−9.8 (2)	O3'—C3'—C4'—C5'	70.2 (2)
O5—P1—O3'—C3'	165.44 (14)	C2'—C3'—C4'—C5'	−166.44 (19)
O3—P1—O3'—C3'	−63.31 (16)	P1—O5'—C5'—C4'	55.8 (2)
O5'—P1—O3'—C3'	51.82 (16)	O4'—C4'—C5'—O5'	−175.71 (18)
O5—P1—O5'—C5'	−164.21 (17)	C3'—C4'—C5'—O5'	−60.5 (2)
O3—P1—O5'—C5'	64.87 (19)	C4—N3—C2—N1	0.4 (4)
O3'—P1—O5'—C5'	−50.71 (19)	C6—N1—C2—N3	−0.5 (5)
C4'—O4'—C1'—N9	−138.04 (18)	C2—N3—C4—N9	176.8 (3)
Na1^v—O4'—C1'—N9	82.08 (19)	C2—N3—C4—C5	−1.4 (4)
C4'—O4'—C1'—C2'	−14.2 (2)	C8—N9—C4—N3	−179.1 (3)
Na1^v—O4'—C1'—C2'	−154.07 (13)	C1'—N9—C4—N3	−4.8 (4)
C4—N9—C1'—O4'	74.7 (3)	C8—N9—C4—C5	−0.6 (3)
C8—N9—C1'—O4'	−112.2 (3)	C1'—N9—C4—C5	173.6 (2)
C4—N9—C1'—C2'	−45.2 (3)	N3—C4—C5—N7	178.8 (3)
C8—N9—C1'—C2'	128.0 (3)	N9—C4—C5—N7	0.4 (3)
Na1—O2'—C2'—C3'	−170.40 (16)	N3—C4—C5—C6	2.3 (4)
Na1—O2'—C2'—C1'	78.2 (2)	N9—C4—C5—C6	−176.1 (2)
O4'—C1'—C2'—O2'	106.0 (2)	C8—N7—C5—C4	0.0 (3)
N9—C1'—C2'—O2'	−133.3 (2)	C8—N7—C5—C6	176.0 (3)
O4'—C1'—C2'—C3'	−13.1 (2)	Na1^vi—O6—C6—N1	20.2 (5)
N9—C1'—C2'—C3'	107.6 (2)	Na1^vi—O6—C6—C5	−159.1 (2)
P1—O3'—C3'—C2'	178.49 (16)	C2—N1—C6—O6	−178.2 (3)
P1—O3'—C3'—C4'	−65.6 (2)	C2—N1—C6—C5	1.2 (4)
O2'—C2'—C3'—O3'	36.5 (3)	C4—C5—C6—O6	177.4 (3)
C1'—C2'—C3'—O3'	153.45 (18)	N7—C5—C6—O6	1.7 (5)
O2'—C2'—C3'—C4'	−83.2 (2)	C4—C5—C6—N1	−2.0 (3)
C1'—C2'—C3'—C4'	33.7 (2)	N7—C5—C6—N1	−177.7 (3)
C1'—O4'—C4'—C5'	155.00 (19)	C5—N7—C8—N9	−0.4 (3)
Na1^v—O4'—C4'—C5'	−65.7 (2)	C4—N9—C8—N7	0.7 (3)
C1'—O4'—C4'—C3'	35.8 (2)	C1'—N9—C8—N7	−173.7 (2)
Na1^v—O4'—C4'—C3'	175.05 (13)

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, −z+1; (iii) x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+1/2, −z+1; (v) x−1, y, z; (vi) x−1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2′···O5′ⁱⁱ	0.84	2.05	2.821 (2)	152
N1—H1···O3^vii	0.88	1.94	2.817 (3)	172
C1′—H1′1···O2W^v	1.00	2.59	3.289 (3)	127
C2′—H2′1···O6ⁱⁱⁱ	1.00	2.55	3.047 (3)	110
C3′—H3′1···N3	1.00	2.35	3.088 (3)	130
C2—H2···O5^vii	0.95	2.60	3.402 (3)	142
O1W—H1W···O3^viii	0.84	2.02	2.847 (3)	168
O1W—H2W···O3W^ix	0.84	1.95	2.770 (3)	166
O1W—H2W···O30W^ix	0.84	2.17	3.000 (10)	169
O2W—H3W···O3^viii	0.84	1.98	2.813 (3)	170
O2W—H4W···O3W^x	0.84	2.01	2.828 (3)	165
O2W—H4W···O30W^x	0.84	2.15	2.953 (15)	160
O3W—H6W···O4W^viii	0.84	1.89	2.729 (3)	173
O3W—H5W···N7	0.84	2.13	2.899 (3)	152
O30W—H5W···N7	0.84	2.13	2.885 (5)	150
O4W—H7W···O5′ⁱ	0.84	2.23	3.064 (3)	171
O4W—H8W···O5	0.84	2.00	2.834 (3)	171

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, −z+1; (iii) x+1/2, −y+3/2, −z+1; (v) x−1, y, z; (vii) −x+1, y+1/2, −z+3/2; (viii) −x+3/2, −y+1, z−1/2; (ix) −x+1, y−1/2, −z+1/2; (x) −x+2, y−1/2, −z+1/2.

Experimental details

	(I_camp)	(II_camp1ab)	(III_gmpdc)
Crystal data
Chemical formula	C₁₀H₁₂N₅O₆P·2H₂O	C₁₀H₁₂N₅O₆P·0.3H₂O	C₁₀H₁₂N₅O₇P·5H₂O
M_r	365.25	334.62	435.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Orthorhombic, P2₁2₁2₁	Orthorhombic, P2₁2₁2₁
Temperature (K)	100	120	298
a, b, c (Å)	7.715 (2), 10.598 (3), 35.481 (9)	7.786 (2), 10.638 (3), 29.887 (8)	6.691 (2), 13.555 (3), 19.863 (4)
V (Å³)	2901.1 (13)	2475.5 (12)	1801.5 (8)
Z	8	8	4
Radiation type	Mo Kα	Cu Kα	Mo Kα
µ (mm⁻¹)	0.25	2.45	0.23
Crystal size (mm)	0.36 × 0.16 × 0.01	0.19 × 0.08 × 0.02	0.20 × 0.10 × 0.02

Data collection
Diffractometer	Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire2 CCD camera	Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)	Analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]	–
T_min, T_max	0.953, 1.000	0.678, 0.952	–
No. of measured, independent and observed [I > 2σ(I)] reflections	27238, 6322, 4907	22972, 4505, 4090	22088, 3526, 2999
R_int	0.086	0.065	0.063
(sin θ/λ)_max (Å⁻¹)	0.639	0.601	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.090, 1.01	0.052, 0.134, 1.05	0.062, 0.146, 1.12
No. of reflections	6322	4505	3526
No. of parameters	433	407	313
No. of restraints	20	11	10
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.33	0.90, −0.45	0.21, −0.22
Absolute structure	Flack x determined using 1672 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)	Flack x determined using 1568 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)	Flack x determined using 892 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Absolute structure parameter	0.03 (7)	−0.020 (14)	−0.16 (9)

	(IV_gmpna)	(V_impna)
Crystal data
Chemical formula	Na⁺·C₁₀H₁₁N₅O₇P⁻·4H₂O	Na⁺·C₁₀H₁₀N₄O₇P⁻·4H₂O
M_r	439.26	424.24
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Orthorhombic, P2₁2₁2₁
Temperature (K)	100	100
a, b, c (Å)	7.206 (2), 12.669 (3), 18.754 (3)	6.652 (2), 14.726 (3), 17.208 (4)
V (Å³)	1712.1 (7)	1685.7 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.26	0.26
Crystal size (mm)	0.40 × 0.12 × 0.12	0.60 × 0.19 × 0.05

Data collection
Diffractometer	Oxford Diffraction Xcalibur PX κ-geometry diffractometer with an Onyx CCD camera	Kuma KM-4 CCD κ-geometry diffractometer with a Sapphire2 CCD camera
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.949, 1.000	0.681, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	32323, 7524, 7142	16251, 5851, 5098
R_int	0.026	0.042
(sin θ/λ)_max (Å⁻¹)	0.807	0.840

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.075, 1.10	0.049, 0.103, 1.06
No. of reflections	7524	5851
No. of parameters	258	249
No. of restraints	18	17
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.43	0.67, −0.46
Absolute structure	Flack x determined using 3048 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)	Flack x determined using 1605 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Absolute structure parameter	−0.031 (18)	0.03 (6)

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis CCD (Oxford Diffraction, 2004), CrysAlis RED (Oxford Diffraction, 2004), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 2014), PLATON (Spek, 2009).

Conformation of purine 3':5'-cyclic nucleotides: nucleobase and sugar ring conformational parameters for the cAMP and cGMP zwitterions and cGMP^- and cIMP^- anions in (I)–(V), together with the relevant values for the literature data. Bold text indicates uncommon conformations top

(I)–(V) (this work) or CSD refcode	Nucleobase conformation		Sugar conformation
			Pseudorotation parameters (Rao et al., 1981); for C2'–C3' bond		Cremer–Pople parameters (Cremer & Pople, 1975)		Nearest pucker descriptor
	χ_CN (°)^a	syn/anti orientation	P (°)	τ_m (°)	Q₂ (Å)	Φ₂ (°)
cAMP^b/cAMP^-^c
(I)-A^b	66.5 (5)	syn	45.6 (3)	47.4 (3)	0.447 (4)	313.1 (5)	E₄↔³₄T
(II)-A^b	66.6 (6)	syn	45.8 (4)	46.8 (3)	0.442 (5)	313.1 (7)	E₄↔³₄T
(I)-B^b	-121.7 (4)	anti	36.1 (3)	49.4 (3)	0.476 (4)	303.7 (5)	³₄T
(II)-B^b	-128.9 (5)	anti	37.5 (4)	49.3 (3)	0.472 (6)	305.0 (7)	³₄T
NAAMPH10-A ^c^,^d	-148.6	anti	33.1	48.8	0.472	300.9	³T₄
ZOXVOX ^c^,^e	-159.7	anti	29.6	42.6	0.402	297.7	³T₄
NAAMPH10-B ^c^,^d	-173.7	anti	14.8	46.9	0.460	283.4	³E

cGMP^b/cGMP^-^c
(III)^b	62.1 (6)	syn	42.8 (3)	44.5 (3)	0.418 (5)	309.7 (7)	³T₄→E₄
(IV)^c	64.27 (15)	syn	39.7 (1)	44.4 (1)	0.4178 (13)	306.95 (17)	³T₄
CATTIA-A^c^,^f	58.7	syn	38.6	47.8	0.452	306.6	³T₄
SCGMPT10^c^,^g	68.6	syn	42.7	44.2	0.413	310.2	³T₄→E₄
CATTIA-B^c^,^f	78.3	syn	40.6	49.9	0.472	307.8	³T₄
BIVJEV^c^,^h	81.7	syn	47.4	48.3	0.448	314.9	E₄

cIMP^b/cIMP^-^c
(V)^c	74.7 (3)	syn	37.2 (2)	43.5 (1)	0.411 (3)	304.7 (3)	³₄T
CATTEW^c^,^f	90.8	high-syn	38.6	48.6	0.463	306.2	³T₄
BEPRAP^b,i	-151.6	anti	27.6	43.4	0.420	295.0	³E↔³₄T
MEDNUG ^c^,^j	-174.66 (12)	anti	14.7 (1)	46.5 (1)	0.4561 (15)	283.22 (17)	³E

Notes and references: (a) χCN is the O4'—C1'—N9—C4 torsion angle; (b) cAMP is a zwitterion with the adenine N1 atom protonated, cGMP is a zwitterion with the guanine N7 atom protonated and cIMP is a zwitterion with the hypoxanthine N7 atom protonated; (c) cAMP^-, cGMP^- and cIMP^- stand for anionic forms of the respective cNMP with the phosphate group deprotonated; (d) Varughese et al. (1982); (e) Iverson et al. (1996) (the inverted model has been used); (f) Sheldrick (1983); (g) Chwang & Sundaralingam (1974) [room-temperature structure of (IV)] (h) Sheldrick (1982); (i) Sundaralingam et al. (1982); (j) Ślepokura (2012).

Values of φ₁, φ₂ and φ₃ (°), and the Cremer–Pople puckering parameters (Å,°) (Cremer & Pople, 1975) Q, Θ and Φ for the O/P/O/C/C/C rings in the cAMP and cGMP zwitterions, and the cGMP^- and cIMP^- anions in (I)–(V), together with the relevant values for the literature data top

(I)–(V) (this work) or CSD refcode	φ₁†	φ₂‡	φ₃§	Cremer–Pople parameters
				Q	Θ	Φ
cAMP^b/cAMP^-^c
(I)-A^b	46.2 (2)	60.0 (4)	13.8 (3)	0.613 (4)	173.5 (4)	338 (3)
(II)-A^b	46.0 (3)	59.5 (4)	13.5 (4)	0.609 (5)	173.2 (4)	335 (4)
(I)-B^b	48.7 (3)	55.9 (4)	7.2 (5)	0.602 (4)	180.0 (4)	301 (8)
(II)-B^b	45.9 (3)	55.9 (6)	10.1 (8)	0.586 (5)	174.1 (5)	300 (5)
NAAMPH10-A^c^,^d	41.1	58.6	17.6	0.577	169.8	356
ZOXVOX^c^,^e	39.0	58.8	19.8	0.566	167.4	344
NAAMPH10-B^c^,^d	43.0	59.2	16.2	0.592	170.8	339

cGMP^b/cGMP^-^c
(III)^b	41.9 (3)	59.8 (4)	17.9 (3)	0.592 (5)	168.9 (4)	338 (2)
(IV)^c	34.49 (5)	60.07 (2)	25.6 (2)	0.5661 (12)	161.10 (11)	344.8 (4)
CATTIA-A^c^,^f	44.5	63.2	18.7	0.605	171.9	6
SCGMPT10^c^,^g	38.2	58.9	20.7	0.566	166.4	344
CATTIA-B ^c^,^f	44.7	59.1	14.4	0.589	174.0	358
BIVJEV^c^,^h	45.5	56.4	10.9	0.589	175.9	358

cIMP^b/cIMP^-^c
(V)^c	45.0 (2)	59.9 (3)	15.0 (2)	0.611 (2)	170.97 (19)	322.2 (13)
CATTEW^c^,^f	43.0	57.8	14.8	0.574	173.2	350
BEPRAP^b,i	43.3	61.5	18.2	0.606	169.4	2
MEDNUG^c^,^j	44.5 (1)	59.4 (1)	14.9 (2)	0.5959 (13)	172.88 (12)	346.0 (11)

Notes: † φ₁ is the angle between the reference plane (O3'/O5'/C5'/C3') and the plane defined by O/P/O. ‡ φ₂ is the angle between the reference plane and the plane defined by C/C/C. § φ₃ is the angle between the O/P/O and C/C/C planes (for chair-puckered rings φ₃ = |φ₂ - φ₁|). (b)–(j) are the same as in Table 2.

Selected geometric parameters (Å, °) for the cAMP and cGMP zwitterions, and the cGMP^- and cIMP^- anions in (I)–(V) top

	(I)		(II)		(III)	(IV)	(V)
	cAMP-A	cAMP-B	cAMP-A	cAMP-B	cGMP	cGMP^-	cIMP^-
P1—O3'	1.621 (3)	1.611 (3)	1.619 (4)	1.620 (4)	1.612 (3)	1.6174 (10)	1.6093 (18)
P1—O5'	1.615 (3)	1.598 (3)	1.610 (4)	1.594 (4)	1.594 (4)	1.5996 (11)	1.6253 (19)
P1—O3	1.478 (3)	1.495 (3)	1.484 (4)	1.476 (5)	1.482 (3)	1.5052 (10)	1.4924 (17)
P1—O5	1.507 (3)	1.489 (3)	1.507 (4)	1.484 (4)	1.470 (3)	1.4800 (10)	1.4809 (18)
O3'—P1—O5'	103.21 (15)	103.32 (14)	103.25 (19)	102.9 (2)	103.85 (19)	104.41 (5)	102.82 (9)
O3'—P1—O3	110.30 (17)	109.64 (17)	110.3 (2)	109.9 (2)	108.2 (2)	108.45 (6)	109.18 (10)
O3'—P1—O5	106.04 (15)	107.80 (17)	106.6 (2)	105.9 (2)	107.49 (19)	105.85 (6)	107.61 (10)
O5'—P1—O3	111.96 (17)	109.32 (17)	111.4 (2)	111.1 (3)	109.5 (2)	110.86 (6)	108.55 (10)
O5'—P1—O5	104.60 (16)	107.97 (17)	104.4 (2)	107.9 (2)	108.5 (2)	109.21 (6)	107.78 (10)
O3—P1—O5	119.35 (17)	117.80 (17)	119.5 (2)	117.9 (2)	118.2 (2)	117.19 (6)	119.61 (10)
P1—O3'—C3'—C2'	-176.3 (3)	-178.5 (3)	-176.4 (3)	-178.8 (4)	-178.6 (3)	-175.48 (8)	178.49 (16)
O4'—C4'—C5'—O5'	-177.2 (3)	-170.1 (3)	-177.0 (4)	-169.1 (5)	-175.3 (4)	-175.50 (10)	-175.71 (18)

Types of direct inter-nucleotide and nucleotide–water contacts in (I)–(V).
Bold text indicates (atoms of) syn-cNMP. Atoms involved in hydrogen bonds more than once are underlined top

	cNMP present	Base–base interactions (B–B)		Base–sugar (B–S)	Base–phosphate (B–P)	Sugar–phosphate (S–P)	Sugar–sugar (S–S)	Atoms involved in hydrogen bonds with water
		Edge-to-edge non-Watson–Crick	π–π
(I)	cAMP^±		A···A	N1···O5'	N1···O5	O2'···O5	O2'···O2'	B: N6, N6, N7
	cAMP^±			N6···O5'	N1···O5			P: O3, O5
					N6···O5
(II)	cAMP^±	N6···N7	A···A	N1···O5'	N1···O5	O2'···O5	O2'···O2'	B: N6
	cAMP^±				N1···O5			S: O3'
					N6···O3,O5			P: O3
(III)	cGMP^±		G···G		N1···O5	O2'···O3		B: N2, N7, O6
					N2···O5			P: O3
(IV)	cGMP^-		G···G		N1···O5	O2'···O3		B: N2, N7, O6
					N2···O5	O2'···O5		S: O2'
								P: O3
(V)	cIMP^-		I···I		N1···O3		O2'···O5'	B: N7
								S: O5'
								P: O3, O5

Hydrogen-bond geometry (Å, º) for (I_camp) top

D—H···A	D—H	H···A	D···A	D—H···A
O2'A—H2'A···O2'Bⁱ	0.84	2.07	2.854 (4)	154
N1A—H1A···O5Bⁱⁱ	0.88	1.72	2.601 (5)	174
N6A—H6A···O2W	0.88	2.02	2.883 (5)	167
N6A—H6B···O1W	0.88	2.03	2.778 (5)	142
C1'A—H1'1···O3Aⁱⁱⁱ	1.00	2.49	3.379 (5)	148
C3'A—H3'1···N3A	1.00	2.68	3.339 (6)	124
C4'A—H4'1···N3Aⁱⁱⁱ	1.00	2.40	3.362 (6)	162
C5'A—H5'1···N3B	0.99	2.49	3.453 (6)	163
C5'A—H5'2···O3A^iv	0.99	2.49	3.298 (5)	139
C8A—H8A···O3Aⁱⁱⁱ	0.95	2.43	3.258 (5)	146
O2'B—H2'B···O5A^iv	0.84	1.84	2.668 (4)	167
N1B—H1B···O5A^v	0.88	1.91	2.768 (4)	163
N1B—H1B···O5'A^v	0.88	2.45	3.071 (4)	128
N6B—H6C···O5A^v	0.88	2.55	3.252 (5)	137
N6B—H6C···O5'B^vi	0.88	2.52	3.228 (4)	138
N6B—H6D···O3W	0.88	1.92	2.796 (5)	172
C1'B—H1'2···O4'A	1.00	2.43	3.235 (5)	137
C3'B—H3'2···O4W^vii	1.00	2.40	3.353 (5)	159
C4'B—H4'2···O3'Aⁱⁱⁱ	1.00	2.53	3.495 (5)	163
C2B—H2B···O3A	0.95	2.44	3.264 (6)	145
C2B—H2B···O5'A^v	0.95	2.53	3.127 (5)	121
C8B—H8B···O4W^vii	0.95	2.47	3.384 (5)	163
O1W—H1W···O3B^viii	0.84	2.00	2.781 (4)	153
O1W—H2W···O3W^ix	0.84	1.99	2.827 (5)	175
O2W—H3W···N7B^ix	0.84	2.08	2.910 (5)	169
O2W—H4W···O5Bⁱⁱ	0.84	2.20	2.868 (4)	136
O3W—H5W···O4W^vi	0.84	1.89	2.692 (4)	161
O3W—H6W···O2W^x	0.84	1.95	2.738 (4)	157
O4W—H7W···O3B	0.84	1.95	2.770 (4)	166
O4W—H8W···O3B^viii	0.84	1.95	2.776 (4)	167

Hydrogen-bond geometry (Å, º) for (II_camp1ab) top

D—H···A	D—H	H···A	D···A	D—H···A
O2'A—H2'A···O2'Bⁱ	0.84	2.21	2.914 (6)	142
N1A—H1A···O5Bⁱⁱ	0.88	1.73	2.537 (6)	152
N6A—H6A···N7Bⁱⁱⁱ	0.88	2.26	3.124 (7)	168
N6A—H6B···O3B^iv	0.88	2.20	3.072 (6)	170
N6A—H6B···O5B^iv	0.88	2.56	3.013 (6)	113
C1'A—H1'1···O3A^v	1.00	2.57	3.447 (6)	147
C4'A—H4'1···N3A^v	1.00	2.41	3.376 (7)	162
C5'A—H5'1···N3B	0.99	2.52	3.479 (7)	163
C5'A—H5'2···O3A^vi	0.99	2.49	3.295 (6)	138
C8A—H8A···O3A^v	0.95	2.38	3.236 (7)	149
O2'B—H2'B···O5A^vi	0.84	1.90	2.699 (5)	157
N1B—H1B···O5A^vii	0.88	1.88	2.735 (6)	163
N1B—H1B···O5'A^vii	0.88	2.45	3.080 (6)	129
N6B—H6C···O1W	0.88	2.11	2.731 (7)	127
C1'B—H1'2···O4'A	1.00	2.40	3.225 (7)	139
C3'B—H3'2···O1Wⁱⁱⁱ	1.00	2.46	3.367 (8)	151
C4'B—H4'2···O3'A^v	1.00	2.53	3.475 (7)	158
C5'B—H5'3···O1Wⁱⁱⁱ	0.99	2.50	3.351 (10)	144
C2B—H2B···O3A	0.95	2.41	3.219 (7)	142
C2B—H2B···O5'A^vii	0.95	2.46	3.080 (7)	123
C8B—H8B···O1Wⁱⁱⁱ	0.95	2.59	3.524 (8)	169
O1W—H1W···O3B^viii	0.84	1.99	2.795 (7)	159
O1W—H2W···O3'Bⁱⁱ	0.84	2.09	2.930 (7)	175

Hydrogen-bond geometry (Å, º) for (III_gmpdc) top

D—H···A	D—H	H···A	D···A	D—H···A
O2'—H2'···O3ⁱ	0.84	1.93	2.679 (5)	149
N1—H1···O5ⁱⁱ	0.88	2.01	2.788 (5)	147
N2—H2A···O1W	0.88	2.09	2.86 (2)	146
N2—H2A···O10W	0.88	2.42	3.12 (3)	137
N2—H2A···O50W	0.88	2.23	3.023 (18)	149
N2—H2A···O51W	0.88	1.84	2.69 (5)	162
N2—H2B···O5ⁱⁱ	0.88	2.14	2.905 (5)	145
N7—H7···O3Wⁱⁱⁱ	0.88	1.80	2.67 (2)	169
N7—H7···O30Wⁱⁱⁱ	0.88	1.85	2.711 (15)	165
N7—H7···O31Wⁱⁱⁱ	0.88	1.98	2.80 (3)	154
N7—H7···O32Wⁱⁱⁱ	0.88	1.81	2.59 (4)	148
C2'—H2'1···O6^iv	0.98	2.52	3.435 (6)	155
C3'—H3'1···N3	0.98	2.59	3.297 (6)	129
C4'—H4'1···O12W^v	0.98	2.46	3.30 (4)	143
C5'—H5'1···O6^vi	0.97	2.44	3.129 (7)	128
C8—H8···O5'^v	0.93	2.46	3.042 (6)	120
C8—H8···O2Wⁱⁱⁱ	0.93	2.52	3.10 (2)	121
C8—H8···O21Wⁱⁱⁱ	0.93	2.52	3.19 (4)	129

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1/2, −y+1, z+1/2; (iii) x, y+1, z; (iv) x+1/2, −y+3/2, −z+1; (v) −x, y+1/2, −z+1/2; (vi) x−1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) for (IV_gmpna) top

D—H···A	D—H	H···A	D···A	D—H···A
O2'—H2'···O3ⁱⁱⁱ	0.84	2.07	2.8869 (15)	163
O2'—H2'···O5ⁱⁱⁱ	0.84	2.59	3.2079 (15)	131
N1—H1···O5^iv	0.88	1.90	2.7365 (15)	157
N2—H2A···O5^iv	0.88	2.15	2.9120 (16)	144
N2—H2B···O1W	0.88	2.09	2.9635 (16)	170
C2'—H2'1···O5ⁱⁱⁱ	1.00	2.50	3.0154 (17)	112
C3'—H3'1···N3	1.00	2.49	3.2216 (17)	130
C5'—H5'1···O6^v	0.99	2.46	3.3260 (18)	146
C8—H8···O3'ⁱⁱⁱ	0.95	2.49	3.0839 (17)	121
O1W—H1W···O3	0.84	1.95	2.7879 (15)	177
O1W—H2W···O6^vi	0.84	2.12	2.9509 (16)	173
O2W—H3W···O3	0.84	2.23	3.0285 (15)	158
O2W—H4W···N7^vii	0.84	2.00	2.8342 (16)	176
O3W—H5W···O3ⁱ	0.84	2.05	2.885 (2)	175
O30W—H5W···O3ⁱ	0.84	2.05	2.765 (3)	143
O3W—H6W···O6^vii	0.84	1.98	2.8032 (18)	166
O30W—H6W···O6^vii	0.84	1.98	2.755 (5)	153
O4W—H7W···O2'^iv	0.84	2.11	2.9034 (16)	157
O4W—H8W···N7^v	0.84	2.35	3.1195 (17)	152

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1/2, −y+1, z+1/2; (v) x−1/2, −y+3/2, −z+1; (vi) x+1/2, −y+3/2, −z+1; (vii) x, y−1, z.

Hydrogen-bond geometry (Å, º) for (V_impna) top

D—H···A	D—H	H···A	D···A	D—H···A
O2'—H2'···O5'ⁱⁱ	0.84	2.05	2.821 (2)	152
N1—H1···O3^iv	0.88	1.94	2.817 (3)	172
C1'—H1'1···O2W^v	1.00	2.59	3.289 (3)	127
C2'—H2'1···O6ⁱⁱⁱ	1.00	2.55	3.047 (3)	110
C3'—H3'1···N3	1.00	2.35	3.088 (3)	130
C2—H2···O5^iv	0.95	2.60	3.402 (3)	142
O1W—H1W···O3^vi	0.84	2.02	2.847 (3)	168
O1W—H2W···O3W^vii	0.84	1.95	2.770 (3)	166
O1W—H2W···O30W^vii	0.84	2.17	3.000 (10)	169
O2W—H3W···O3^vi	0.84	1.98	2.813 (3)	170
O2W—H4W···O3W^viii	0.84	2.01	2.828 (3)	165
O2W—H4W···O30W^viii	0.84	2.15	2.953 (15)	160
O3W—H6W···O4W^vi	0.84	1.89	2.729 (3)	173
O3W—H5W···N7	0.84	2.13	2.899 (3)	152
O30W—H5W···N7	0.84	2.13	2.885 (5)	150
O4W—H7W···O5'ⁱ	0.84	2.23	3.064 (3)	171
O4W—H8W···O5	0.84	2.00	2.834 (3)	171

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, −z+1; (iii) x+1/2, −y+3/2, −z+1; (iv) −x+1, y+1/2, −z+3/2; (v) x−1, y, z; (vi) −x+3/2, −y+1, z−1/2; (vii) −x+1, y−1/2, −z+1/2; (viii) −x+2, y−1/2, −z+1/2.

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Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text