3-Cyano-6-hy­droxy-4-methyl-2-pyridone: two new pseudopolymorphs and two cocrystals with products of an in situ nucleophilic aromatic substitution

Four crystal structures of 3-cyano-6-hy­droxy-4-methyl-2-pyridone (CMP), viz. the dimethyl sulfoxide monosolvate, C₇H₆N₂O₂·C₂H₆OS, (1), the N,N-di­methyl­acetamide monosolvate, C₇H₆N₂O₂·C₄H₉NO, (2), a cocrystal with 2-amino-4-di­methyl­amino-6-methyl­pyrimidine (as the salt 2-amino-4-di­methyl­amino-6-methyl­pyrimidin-1-ium 5-cyano-4-methyl-6-oxo-1,6-di­hydro­pyridin-2-olate), C₇H₁₃N₄⁺·C₇H₅N₂O₂⁻, (3), and a cocrystal with N,N-di­methyl­acetamide and 4,6-di­amino-2-di­methyl­amino-1,3,5-triazine [as the solvated salt 2,6-di­amino-4-di­methyl­amino-1,3,5-triazin-1-ium 5-cyano-4-methyl-6-oxo-1,6-di­hydro­pyridin-2-olate–N,N-di­methyl­acet­am­ide (1/1)], C₅H₁₁N₆⁺·C₇H₅N₂O₂⁻·C₄H₉NO, (4), are re­ported. Solvates (1) and (2) both contain the hydroxy group in a para position with respect to the cyano group of CMP, acting as a hydrogen-bond donor and leading to rather similar packing motifs. In cocrystals (3) and (4), hydrolysis of the solvent mol­ecules occurs and an in situ nucleophilic aromatic substitution of a Cl atom with a di­methyl­amino group has taken place. Within all four structures, an R₂²(8) N—H...O hydrogen-bonding pattern is observed, connecting the CMP mol­ecules, but the pattern differs depending on which O atom participates in the motif, either the ortho or para O atom with respect to the cyano group. Solvents and coformers are attached to these arrangements via single-point O—H...O inter­actions in (1) and (2) or by additional R₄⁴(16) hydrogen-bonding patterns in (3) and (4). Since the in situ nucleophilic aromatic substitution of the coformers occurs, the possible Watson–Crick C–G base-pair-like arrangement is inhibited, yet the cyano group of the CMP mol­ecules participates in hydrogen bonds with their co­formers, influencing the crystal packing to form chains.

S1. Introduction

Due to their possible applications within chemistry to pharmacology, pyridin-2-one and nitrile derivatives have been part of various investigations in recent years (Zhu et al., 2003; Hutter & Benner, 2003; Wittman et al., 2005; Filipski et al., 2006). Their uses range from inter­mediates for many heterocyclic compounds to those with specific pharmacological activities. In particular, the 4,6-disubstituted pyridin-2-one derivatives can be used as bioisosteric substitutents for uracil derivatives (Karcı et al., 2013; Ahmed et al., 2009). 4,6-Disubstituted 3-cyano­pyridin-2-ones, as a combination of both pyridines and nitriles, are used as pigments, manufacturing dyes, and additives for fuels and oils, as well as stabilizers for oligomers (Alimmari et al., 2012). Thus, we decided to examine 3-cyano-6-hy­droxy-4-methyl-2-pyridone (CMP), which is a potent and noncompetetive human uridine phospho­rylase (hUP1) inhibitor (Renck et al., 2013). CMP is capable of forming three different tautomeric forms, viz. the 2-hy­droxy tautomer, the 6-hy­droxy tautomer and the 2,6-di­hydroxy tautomer, leading to hydrogen-bonding sites comprising either a donor–donor–acceptor (DDA1 and DDA2) or a donor–acceptor–donor (DAD) arrangement, with the hy­droxy group acting as hydrogen-bond donor (Fig. 1). Since DDA2 displays the higher dipole moment, it can be assumed that it is the most stable tautomer within the solid phase. However, the cyano group can inter­act as an additional hydrogen-bond acceptor of weaker strength. To confirm the DDA2 tautomer within the solid-state, cocrystallization attempts with 2,6-di­chloro­phenol (DCP) have been performed, yielding two new pseudopolymorphs of CMP.

Furthermore, CMP is capable of cocrystallizing with partners showing complementary binding sites, viz. AAD, leading to Watson–Crick C–G base-pair-like arrangements. On the basis of the crystallization attempts with DCP, we chose 2-amino-4-chloro-6-methyl­pyrimidine (ACM) and 2-chloro-4,6-di­amino-1,3,5-triazine (CDT) as complementary cocrystallization partners. Both coformers show a strong donor–acceptor site (DA) next to a Cl atom which is capable of forming weak hydrogen bonds, implicating an AAD binding site with one strong and one weak hydrogen-bond acceptor. Experiments involving CMP with CDT and ACM yielded two new cocrystals showing a distinct hydrogen-bonding pattern due to an in situ nucleophilic aromatic substitution.

S2. Experimental

S2.0.1. Synthesis and crystallization

All experiments were performed with commercially available substances in various hydrous [Should this be anhydrous?] solvents and at different temperatures. Isothermal solvent evaporation experiments of 3-cyano-6-hy­droxy-4-methyl-2-pyridone (CMP) with 2,6-di­chloro­phenol (DCP) at room temperature yielded crystals of the solvent-containing compounds (1) and (2). Crystals of (3) and (4) were obtained during solvent evaporation experiments of CMP with 2-amino-4-chloro-6-methyl­pyrimidine (ACM) at room temperature and with 2-chloro-4,6-di­amino-1,3,5-triazine (CDT) at 323 K, respectively. A detailed summary of the solvent evaporation experiments that were performed is presented in Table 2.

S2.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were initially located by difference Fourier synthesis. Subsequently, C-bound H atoms were refined using a riding model, with methyl C—H = 0.98 Å and aromatic C—H = 0.95 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) for aromatic H atoms. N- and O-bound H atoms were refined isotropically, with U_iso(H) = 1.2U_eq(N) and 1.5U_eq(O) for (1) and (4), and 1,2 distance restaints for N—H bonds in (1) and (2). Distance restraints were also applied to the 1,2 and 1,3 distances of the DMAC solvent molecule in (4). In (3), a rotational disorder for methyl groups C41B and C61B was refined, with site-occupancy factors of 0.634 (19) and 0.718 (20), respectively. For the methyl groups in (2) and (4), free rotation about their local threefold axis was allowed, as well as for C62B in (3). In (4), the DMAC molecule X is disordered across a pseudo-mirror plane, which passes through atoms O2X and C5X with a site-occupancy factor of 0.915 (5).

Since (1) is a nonmerohedral twin defined by the matrix (1 0.002 -0.002/ -0.25 -1 0/-0.25 0 -1), the reflection data file was prepared using PLATON (Spek, 2009). As a result, a file with 549 reflections that are considered to be overlaps from both domains was generated. Thus, the domain ratio could be refined to 0.32 (6):0.68 (6) via the HKLF5 command (SHELXL97; Sheldrick, 2008) and an additional variable (BASF command in SHELXL97).

S3. Results and discussion

The di­methyl sulfoxide (DMSO) monosolvate of CMP, (1), crystallizes with one molecule each of essentially planar CMP (r.m.s. deviation for non-H atoms = 0.018 Å) and DMSO within the asymmetric unit (Fig. 2). The two molecules are connected via an O—H···O hydrogen bond, and a dihedral angle of 88.55 (11)° is formed between the plane of the solvent molecule and that of the CMP molecule (Table 3). The crystal packing of (1) is characterized by dimers, which are built by inversion-symmetric CMP molecules providing an R₂²(8) hydrogen-bonding pattern via N—H···O inter­actions (Fig. 3; Bernstein et al., 1995). This particular inter­action includes the O atom, located in an ortho position with respect to the cyano group in CMP. The dimers are arranged parallel to (241) and show no further hydrogen-bonding inter­actions in the crystal.

The N,N-di­methyl­acetamide (DMAC) monosolvate of CMP, (2), was obtained during crystallization attempts of CMP with 2,6-di­chloro­phenol (DCP) in DMAC. It crystallizes in the space group P1 with one planar CMP molecule and one planar DMAC molecule (X) (r.m.s. deviations for non-H atoms of CMP = 0.011 Å and X = 0.019 Å) in the asymmetric unit (Fig. 4). Similar to (1), the solvent molecule is connected to CMP via an O—H···O hydrogen bond, wherein X is located at an dihedral angle of 69.47 (7) ° with respect to CMP (Table 4). Again, dimers of inversion-symmetric molecules of CMP that are located parallel to (210) are formed in the crystal packing via R₂²(8) N—H···O inter­actions (Fig. 5). Similar to (1), the R₂²(8) pattern includes the O atom in an ortho position with respect to the cyano group in CMP.

Crystallization attempts of CMP with 2-amino-4-chloro-6-methyl­pyrimidine (ACM) in di­methyl­formamide (DMF) yielded the solvent-free cocrystal CMP.DACM, (3). Due to an acidic hydrolysis of the DMF molecule, wherein di­methyl­amine is formed, and followed by an in situ nucleophilic aromatic substitution, the Cl atom in ACM is replaced by the di­methyl­amino group, leading to the molecule DACM (according to Petersen et al., 2013). The asymmetric unit of (3) comprises one deprotonated planar molecule of CMP (A) and, as a result of the two described reactions, one protonated planar molecule of DACM (B) (r.m.s. deviations for non-H atoms of A = 0.0.020 Å and B = 0.025 Å) (Fig. 6). A and B are connected by an N—H···N inter­action from the amino group in B to the cyano group in A. In the crystal structure, the A and B ions are linked to chains parallel to (522) by three different hydrogen-bonding patterns, viz. R₂¹(6) N—H···O hydrogen bonds connecting A and B ions, R₂²(8) N—H···O inter­actions between two CMP molecules, and R₄⁴(16) patterns of two N—H···O and two N—H···N hydrogen bonds between two molecules of CMP and DACM (Table 5 and Fig. 7). In contrast with the CMP solvates (1) and (2), the R₂²(8) hydrogen-bonding motif in (3) is built by the O atom located in the para position with respect to the cyano group of the CMP molecule.

The DMAC solvate of CMP, (4), was obtained during crystallization attempts of CMP with 2-chloro-4,6-di­amino-1,3,5-triazine (CDT) in DMAC. As in (3), an in situ nucleophilic aromatic substitution takes places after the partial acidic hydrolysis of DMAC, resulting in the replacement of the Cl atom of CDT by di­methyl­amine (again according to Petersen et al., 2013). The asymmetric unit contains one molecule of CMP (A), which is again deprotonated, one protonated molecule of DCDT (B) and one DMAC molecule (X). The planar molecules (r.m.s. deviations for non-H atoms of A = 0.007 Å, B = 0.029 Å and X = 0.152 Å) are located almost parallel to (533), whereby A is connected to B through R₂¹(6) N—H···O hydrogen bonds and X shows a single-point N—H···O hydrogen bond to B (Fig. 8). Also, a slight angle of 11.92 (8)° is formed between the DMAC molecule and B. Similar to (3), R₂²(8) N—H···O inter­actions between two CMP molecules, and R₄⁴(16) patterns of two N—H···O and two N—H···N hydrogen bonds between two molecules of CMP and DCDT are formed, leading to chains. Similar to (3), but in contrast with the CMP solvates (1) and (2), an R₂²(8) motif is formed via the O atom in the para position with respect to the cyano group in CMP. In addition to these three patterns, R₃²(10) N—H···O hydrogen bonds between two CMP molecules with one DCDT molecule support the packing (Table 6 and Fig. 9).

A Cambridge Structural Database substructure search (CSD; Version 5.35; Allen, 2002) for CMP, limited to organic structures and excluding one peroxo salt (CSD refcode EYUBIJ; Albov et al., 2004a), revealed ten independent results. Within these, two aspects were analysed, the first addressing the preferred crystal packing and the second being dedicated to the involvement of the cyano group in the hydrogen-bonding pattern. In ERISIH (Rybakov et al., 2004) and YIBZAL (Eyduran et al., 2007), dimers are observed, which are connected via R₂²(8) hydrogen-bonding patterns of N—H···O in ERISIH and N—H···S in YIBZAL, similar to crystals (1) and (2). In addition, the cyano group is not involved in any hydrogen-bonding inter­actions. The second observed packing arrangement contains two-dimensional networks in IHAGUU (Tewari & Dubey, 2009), XIMSOC (Valerga & Puerta, 2007a), PAVQIO (Al-Said et al., 2012) and KILZEM (El-Essawy et al., 2012). Each of these four structures shows weak C—H···N≡C hydrogen bonds within the packing. The third packing arrangement, observed within some structures, namely ELOJEV (Valerga & Puerta, 2009), IXAQAZ (Albov et al., 2004b), SABDUW (Wang et al., 2010) and XIMTOD (Valerga & Puerta, 2007b), consists of chains mainly built by weak C—H···O inter­actions. Only in XIMTOD are additional C—H···N≡C hydrogen bonds present, also supporting the crystal packing. In contrast with these results, cocrystals (3) and (4) both present N—H···N≡C hydrogen bonds that are essential building blocks for the overall packing motif of the chains.

In summary, CMP provides the predicted binding site DDA2. Thus, it possesses the ability to be cocrystallized with molecules providing the complementary acceptor–acceptor–donor sites, resulting in inter­actions related to the Watson–Crick C–G base pair. Since hydrolysis of the solvent molecules DMF and DMAC takes place in (3) and (4), followed by in situ nucleophilic aromatic substitutions with the coformers, the hydrogen-bonding patterns of the reported crystal structures differ from this possible DDA2 arrangement. In (1)–(4), as well as in one structure of the CSD search, which was restricted to organic molecules (CSD refcode ERISIH), R₂²(8) N—H···O hydrogen bonds are present, linking pairs of molecules of CMP. These are further connected to their coformers in (3) and (4) via additional R₄⁴(16) patterns of two N—H···O and two N—H···N hydrogen bonds involving the cyano group, contributing to the presented crystal-packing arrangement. Inter­estingly, the R₂²(8) patterns observed in (1)–(4) differ regarding their origin of the participating O atom. While in (1) and (2) the ortho-O atom relative to the cyano group inter­acts within the hydrogen-bonding motif, in (3) and (4) the para-O atom is involved in the inter­action, possibly facilitating the hydrogen bond with the weak cyano-group acceptor.

Related literature

For related literature, see: Ahmed et al. (2009); Al-Said, Ghorab, Ghabbour, Arshad & Fun (2012); Albov et al. (2004a, 2004b); Alimmari et al. (2012); Allen (2002); Bernstein et al. (1995); El-Essawy, El-Sayed, El-Etrawy & El-Bayaa (2012); Eyduran et al. (2007); Filipski et al. (2006); Hutter & Benner (2003); Karcı, Karcı, Demirçalı & Yamaç (2013); Petersen et al. (2013); Renck et al. (2013); Rybakov et al. (2004); Sheldrick (2008); Spek (2009); Tewari & Dubey (2009); Valerga & Puerta (2007a, 2007b, 2009); Wang et al. (2010); Wittman (2005); Zhu et al. (2003).

Structure description

Due to their possible applications within chemistry to pharmacology, pyridin-2-one and nitrile derivatives have been part of various investigations in recent years (Zhu et al., 2003; Hutter & Benner, 2003; Wittman et al., 2005; Filipski et al., 2006). Their uses range from inter­mediates for many heterocyclic compounds to those with specific pharmacological activities. In particular, the 4,6-disubstituted pyridin-2-one derivatives can be used as bioisosteric substitutents for uracil derivatives (Karcı et al., 2013; Ahmed et al., 2009). 4,6-Disubstituted 3-cyano­pyridin-2-ones, as a combination of both pyridines and nitriles, are used as pigments, manufacturing dyes, and additives for fuels and oils, as well as stabilizers for oligomers (Alimmari et al., 2012). Thus, we decided to examine 3-cyano-6-hy­droxy-4-methyl-2-pyridone (CMP), which is a potent and noncompetetive human uridine phospho­rylase (hUP1) inhibitor (Renck et al., 2013). CMP is capable of forming three different tautomeric forms, viz. the 2-hy­droxy tautomer, the 6-hy­droxy tautomer and the 2,6-di­hydroxy tautomer, leading to hydrogen-bonding sites comprising either a donor–donor–acceptor (DDA1 and DDA2) or a donor–acceptor–donor (DAD) arrangement, with the hy­droxy group acting as hydrogen-bond donor (Fig. 1). Since DDA2 displays the higher dipole moment, it can be assumed that it is the most stable tautomer within the solid phase. However, the cyano group can inter­act as an additional hydrogen-bond acceptor of weaker strength. To confirm the DDA2 tautomer within the solid-state, cocrystallization attempts with 2,6-di­chloro­phenol (DCP) have been performed, yielding two new pseudopolymorphs of CMP.

Furthermore, CMP is capable of cocrystallizing with partners showing complementary binding sites, viz. AAD, leading to Watson–Crick C–G base-pair-like arrangements. On the basis of the crystallization attempts with DCP, we chose 2-amino-4-chloro-6-methyl­pyrimidine (ACM) and 2-chloro-4,6-di­amino-1,3,5-triazine (CDT) as complementary cocrystallization partners. Both coformers show a strong donor–acceptor site (DA) next to a Cl atom which is capable of forming weak hydrogen bonds, implicating an AAD binding site with one strong and one weak hydrogen-bond acceptor. Experiments involving CMP with CDT and ACM yielded two new cocrystals showing a distinct hydrogen-bonding pattern due to an in situ nucleophilic aromatic substitution.

The di­methyl sulfoxide (DMSO) monosolvate of CMP, (1), crystallizes with one molecule each of essentially planar CMP (r.m.s. deviation for non-H atoms = 0.018 Å) and DMSO within the asymmetric unit (Fig. 2). The two molecules are connected via an O—H···O hydrogen bond, and a dihedral angle of 88.55 (11)° is formed between the plane of the solvent molecule and that of the CMP molecule (Table 3). The crystal packing of (1) is characterized by dimers, which are built by inversion-symmetric CMP molecules providing an R₂²(8) hydrogen-bonding pattern via N—H···O inter­actions (Fig. 3; Bernstein et al., 1995). This particular inter­action includes the O atom, located in an ortho position with respect to the cyano group in CMP. The dimers are arranged parallel to (241) and show no further hydrogen-bonding inter­actions in the crystal.

The N,N-di­methyl­acetamide (DMAC) monosolvate of CMP, (2), was obtained during crystallization attempts of CMP with 2,6-di­chloro­phenol (DCP) in DMAC. It crystallizes in the space group P1 with one planar CMP molecule and one planar DMAC molecule (X) (r.m.s. deviations for non-H atoms of CMP = 0.011 Å and X = 0.019 Å) in the asymmetric unit (Fig. 4). Similar to (1), the solvent molecule is connected to CMP via an O—H···O hydrogen bond, wherein X is located at an dihedral angle of 69.47 (7) ° with respect to CMP (Table 4). Again, dimers of inversion-symmetric molecules of CMP that are located parallel to (210) are formed in the crystal packing via R₂²(8) N—H···O inter­actions (Fig. 5). Similar to (1), the R₂²(8) pattern includes the O atom in an ortho position with respect to the cyano group in CMP.

Crystallization attempts of CMP with 2-amino-4-chloro-6-methyl­pyrimidine (ACM) in di­methyl­formamide (DMF) yielded the solvent-free cocrystal CMP.DACM, (3). Due to an acidic hydrolysis of the DMF molecule, wherein di­methyl­amine is formed, and followed by an in situ nucleophilic aromatic substitution, the Cl atom in ACM is replaced by the di­methyl­amino group, leading to the molecule DACM (according to Petersen et al., 2013). The asymmetric unit of (3) comprises one deprotonated planar molecule of CMP (A) and, as a result of the two described reactions, one protonated planar molecule of DACM (B) (r.m.s. deviations for non-H atoms of A = 0.0.020 Å and B = 0.025 Å) (Fig. 6). A and B are connected by an N—H···N inter­action from the amino group in B to the cyano group in A. In the crystal structure, the A and B ions are linked to chains parallel to (522) by three different hydrogen-bonding patterns, viz. R₂¹(6) N—H···O hydrogen bonds connecting A and B ions, R₂²(8) N—H···O inter­actions between two CMP molecules, and R₄⁴(16) patterns of two N—H···O and two N—H···N hydrogen bonds between two molecules of CMP and DACM (Table 5 and Fig. 7). In contrast with the CMP solvates (1) and (2), the R₂²(8) hydrogen-bonding motif in (3) is built by the O atom located in the para position with respect to the cyano group of the CMP molecule.

The DMAC solvate of CMP, (4), was obtained during crystallization attempts of CMP with 2-chloro-4,6-di­amino-1,3,5-triazine (CDT) in DMAC. As in (3), an in situ nucleophilic aromatic substitution takes places after the partial acidic hydrolysis of DMAC, resulting in the replacement of the Cl atom of CDT by di­methyl­amine (again according to Petersen et al., 2013). The asymmetric unit contains one molecule of CMP (A), which is again deprotonated, one protonated molecule of DCDT (B) and one DMAC molecule (X). The planar molecules (r.m.s. deviations for non-H atoms of A = 0.007 Å, B = 0.029 Å and X = 0.152 Å) are located almost parallel to (533), whereby A is connected to B through R₂¹(6) N—H···O hydrogen bonds and X shows a single-point N—H···O hydrogen bond to B (Fig. 8). Also, a slight angle of 11.92 (8)° is formed between the DMAC molecule and B. Similar to (3), R₂²(8) N—H···O inter­actions between two CMP molecules, and R₄⁴(16) patterns of two N—H···O and two N—H···N hydrogen bonds between two molecules of CMP and DCDT are formed, leading to chains. Similar to (3), but in contrast with the CMP solvates (1) and (2), an R₂²(8) motif is formed via the O atom in the para position with respect to the cyano group in CMP. In addition to these three patterns, R₃²(10) N—H···O hydrogen bonds between two CMP molecules with one DCDT molecule support the packing (Table 6 and Fig. 9).

A Cambridge Structural Database substructure search (CSD; Version 5.35; Allen, 2002) for CMP, limited to organic structures and excluding one peroxo salt (CSD refcode EYUBIJ; Albov et al., 2004a), revealed ten independent results. Within these, two aspects were analysed, the first addressing the preferred crystal packing and the second being dedicated to the involvement of the cyano group in the hydrogen-bonding pattern. In ERISIH (Rybakov et al., 2004) and YIBZAL (Eyduran et al., 2007), dimers are observed, which are connected via R₂²(8) hydrogen-bonding patterns of N—H···O in ERISIH and N—H···S in YIBZAL, similar to crystals (1) and (2). In addition, the cyano group is not involved in any hydrogen-bonding inter­actions. The second observed packing arrangement contains two-dimensional networks in IHAGUU (Tewari & Dubey, 2009), XIMSOC (Valerga & Puerta, 2007a), PAVQIO (Al-Said et al., 2012) and KILZEM (El-Essawy et al., 2012). Each of these four structures shows weak C—H···N≡C hydrogen bonds within the packing. The third packing arrangement, observed within some structures, namely ELOJEV (Valerga & Puerta, 2009), IXAQAZ (Albov et al., 2004b), SABDUW (Wang et al., 2010) and XIMTOD (Valerga & Puerta, 2007b), consists of chains mainly built by weak C—H···O inter­actions. Only in XIMTOD are additional C—H···N≡C hydrogen bonds present, also supporting the crystal packing. In contrast with these results, cocrystals (3) and (4) both present N—H···N≡C hydrogen bonds that are essential building blocks for the overall packing motif of the chains.

In summary, CMP provides the predicted binding site DDA2. Thus, it possesses the ability to be cocrystallized with molecules providing the complementary acceptor–acceptor–donor sites, resulting in inter­actions related to the Watson–Crick C–G base pair. Since hydrolysis of the solvent molecules DMF and DMAC takes place in (3) and (4), followed by in situ nucleophilic aromatic substitutions with the coformers, the hydrogen-bonding patterns of the reported crystal structures differ from this possible DDA2 arrangement. In (1)–(4), as well as in one structure of the CSD search, which was restricted to organic molecules (CSD refcode ERISIH), R₂²(8) N—H···O hydrogen bonds are present, linking pairs of molecules of CMP. These are further connected to their coformers in (3) and (4) via additional R₄⁴(16) patterns of two N—H···O and two N—H···N hydrogen bonds involving the cyano group, contributing to the presented crystal-packing arrangement. Inter­estingly, the R₂²(8) patterns observed in (1)–(4) differ regarding their origin of the participating O atom. While in (1) and (2) the ortho-O atom relative to the cyano group inter­acts within the hydrogen-bonding motif, in (3) and (4) the para-O atom is involved in the inter­action, possibly facilitating the hydrogen bond with the weak cyano-group acceptor.

For related literature, see: Ahmed et al. (2009); Al-Said, Ghorab, Ghabbour, Arshad & Fun (2012); Albov et al. (2004a, 2004b); Alimmari et al. (2012); Allen (2002); Bernstein et al. (1995); El-Essawy, El-Sayed, El-Etrawy & El-Bayaa (2012); Eyduran et al. (2007); Filipski et al. (2006); Hutter & Benner (2003); Karcı, Karcı, Demirçalı & Yamaç (2013); Petersen et al. (2013); Renck et al. (2013); Rybakov et al. (2004); Sheldrick (2008); Spek (2009); Tewari & Dubey (2009); Valerga & Puerta (2007a, 2007b, 2009); Wang et al. (2010); Wittman (2005); Zhu et al. (2003).

Synthesis and crystallization

All experiments were performed with commercially available substances in various hydrous [Should this be anhydrous?] solvents and at different temperatures. Isothermal solvent evaporation experiments of 3-cyano-6-hy­droxy-4-methyl-2-pyridone (CMP) with 2,6-di­chloro­phenol (DCP) at room temperature yielded crystals of the solvent-containing compounds (1) and (2). Crystals of (3) and (4) were obtained during solvent evaporation experiments of CMP with 2-amino-4-chloro-6-methyl­pyrimidine (ACM) at room temperature and with 2-chloro-4,6-di­amino-1,3,5-triazine (CDT) at 323 K, respectively. A detailed summary of the solvent evaporation experiments that were performed is presented in Table 2.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were initially located by difference Fourier synthesis. Subsequently, C-bound H atoms were refined using a riding model, with methyl C—H = 0.98 Å and aromatic C—H = 0.95 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) for aromatic H atoms. N- and O-bound H atoms were refined isotropically, with U_iso(H) = 1.2U_eq(N) and 1.5U_eq(O) for (1) and (4), and 1,2 distance restaints for N—H bonds in (1) and (2). Distance restraints were also applied to the 1,2 and 1,3 distances of the DMAC solvent molecule in (4). In (3), a rotational disorder for methyl groups C41B and C61B was refined, with site-occupancy factors of 0.634 (19) and 0.718 (20), respectively. For the methyl groups in (2) and (4), free rotation about their local threefold axis was allowed, as well as for C62B in (3). In (4), the DMAC molecule X is disordered across a pseudo-mirror plane, which passes through atoms O2X and C5X with a site-occupancy factor of 0.915 (5).

Since (1) is a nonmerohedral twin defined by the matrix (1 0.002 -0.002/ -0.25 -1 0/-0.25 0 -1), the reflection data file was prepared using PLATON (Spek, 2009). As a result, a file with 549 reflections that are considered to be overlaps from both domains was generated. Thus, the domain ratio could be refined to 0.32 (6):0.68 (6) via the HKLF5 command (SHELXL97; Sheldrick, 2008) and an additional variable (BASF command in SHELXL97).

Computing details

For all compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008) and XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Selected hydrogen-bonding sites of CMP are presented within the three tautomeric forms, including the hydroxy groups acting as hydrogen-bond donors. In addition, possible forms of deprotonated CMP are shown below.
	Fig. 2. A perspective view of (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is indicated by a dashed line.
	Fig. 3. A partial packing diagram for (1). Only H atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) -x, -y + 2, -z + 1.]
	Fig. 4. A perspective view of (2), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is indicated by a dashed line.
	Fig. 5. A partial packing diagram for (2). Only H atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) -x + 1, -y + 2, -z + 1.]
	Fig. 6. A perspective view of (3), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is indicated by a dashed line and only the major occupied sites of the H atoms of the methyl groups are displayed.
	Fig. 7. A partial packing diagram for (3). Only H atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. The minor occupied site of the H atoms of the methyl group has been omitted. [Symmetry codes: (i) -x + 2, -y + 1, -z; (ii) -x + 2, -y + 2, -z + 1.]
	Fig. 8. A perspective view of (4), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines and only the major occupied sites of the solvent molecule are displayed.
	Fig. 9. A partial packing diagram for (4). Only H atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. The minor occupied site of the solvent molecule has been omitted. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, -y + 2, -z + 1.]

(1) 3-Cyano-6-hydroxy-4-methyl-2-pyridone dimethyl sulfoxide monosolvate

Crystal data

C7H6N2O2·C2H6OS	Z = 2
Mr = 228.27	F(000) = 240
Triclinic, P1	Dx = 1.400 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3065 (8) Å	Cell parameters from 5034 reflections
b = 8.4460 (14) Å	θ = 3.4–26.4°
c = 12.1459 (19) Å	µ = 0.29 mm^−1
α = 91.810 (13)°	T = 173 K
β = 92.977 (13)°	Needle, colourless
γ = 94.585 (13)°	0.18 × 0.08 × 0.06 mm
V = 541.54 (15) Å^3

Data collection

Stoe IPDS II two-circle diffractometer	2684 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	1675 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.066
ω scans	θmax = 26.1°, θmin = 3.9°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −6→6
Tmin = 0.951, Tmax = 0.984	k = −10→10
2135 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.232	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.1558P)^2 + 0.029P] where P = (Fo^2 + 2Fc^2)/3
2135 reflections	(Δ/σ)max < 0.001
143 parameters	Δρmax = 0.50 e Å^−3
2 restraints	Δρmin = −0.57 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.2622 (5)	0.8692 (4)	0.5172 (2)	0.0287 (7)
H1	0.172 (7)	0.930 (4)	0.559 (3)	0.034*
C2	0.2163 (6)	0.8713 (4)	0.4038 (3)	0.0292 (8)
O2	0.0435 (4)	0.9471 (3)	0.36488 (19)	0.0330 (6)
C3	0.3759 (6)	0.7798 (4)	0.3406 (3)	0.0299 (8)
C31	0.3383 (7)	0.7777 (5)	0.2241 (3)	0.0374 (9)
N32	0.3093 (7)	0.7741 (5)	0.1293 (3)	0.0508 (10)
C4	0.5665 (6)	0.6957 (4)	0.3904 (3)	0.0297 (8)
C41	0.7261 (7)	0.6006 (5)	0.3212 (3)	0.0346 (8)
H41A	0.8478	0.5493	0.3688	0.052*
H41B	0.8176	0.6706	0.2712	0.052*
H41C	0.6181	0.5192	0.2779	0.052*
C5	0.6029 (6)	0.7046 (4)	0.5053 (3)	0.0300 (8)
H5	0.7336	0.6510	0.5407	0.036*
C6	0.4491 (6)	0.7910 (4)	0.5665 (3)	0.0277 (7)
O6	0.4661 (5)	0.8104 (3)	0.6751 (2)	0.0340 (6)
H6	0.598 (6)	0.773 (6)	0.701 (4)	0.051*
C1X	1.0785 (9)	0.8898 (6)	0.8705 (3)	0.0476 (11)
H1X1	1.2044	0.9212	0.8173	0.071*
H1X2	1.1509	0.9136	0.9456	0.071*
H1X3	0.9286	0.9489	0.8579	0.071*
S2X	0.99094 (18)	0.68346 (12)	0.85345 (7)	0.0392 (4)
O2X	0.8323 (6)	0.6588 (4)	0.7463 (2)	0.0461 (8)
C3X	0.7715 (10)	0.6634 (7)	0.9587 (4)	0.0588 (13)
H3X1	0.7030	0.5524	0.9605	0.088*
H3X2	0.6330	0.7311	0.9435	0.088*
H3X3	0.8574	0.6958	1.0302	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0222 (14)	0.0401 (17)	0.0251 (14)	0.0103 (13)	0.0011 (11)	0.0013 (12)
C2	0.0181 (15)	0.039 (2)	0.0300 (16)	0.0030 (14)	−0.0016 (13)	0.0016 (14)
O2	0.0232 (13)	0.0451 (16)	0.0321 (13)	0.0141 (11)	−0.0026 (9)	0.0023 (11)
C3	0.0221 (16)	0.039 (2)	0.0291 (16)	0.0085 (14)	0.0000 (13)	0.0005 (14)
C31	0.0264 (18)	0.053 (2)	0.0347 (19)	0.0135 (17)	0.0011 (14)	0.0000 (16)
N32	0.046 (2)	0.078 (3)	0.0318 (17)	0.026 (2)	0.0003 (15)	−0.0015 (16)
C4	0.0189 (15)	0.0361 (19)	0.0344 (17)	0.0039 (14)	0.0017 (14)	0.0006 (14)
C41	0.0261 (17)	0.044 (2)	0.0345 (17)	0.0128 (15)	0.0000 (14)	−0.0070 (15)
C5	0.0234 (16)	0.0360 (19)	0.0313 (17)	0.0097 (15)	−0.0035 (13)	0.0005 (14)
C6	0.0183 (15)	0.0350 (18)	0.0301 (16)	0.0049 (13)	0.0002 (12)	0.0016 (13)
O6	0.0255 (13)	0.0479 (16)	0.0292 (12)	0.0101 (11)	−0.0043 (10)	0.0014 (10)
C1X	0.056 (3)	0.056 (3)	0.0321 (19)	0.014 (2)	0.0015 (17)	0.0008 (17)
S2X	0.0322 (6)	0.0548 (7)	0.0325 (5)	0.0206 (5)	−0.0062 (4)	0.0012 (4)
O2X	0.0445 (17)	0.0602 (19)	0.0348 (14)	0.0247 (14)	−0.0128 (12)	−0.0058 (12)
C3X	0.048 (3)	0.090 (4)	0.039 (2)	0.007 (3)	0.002 (2)	0.003 (2)

Geometric parameters (Å, º)

N1—C6	1.358 (4)	C5—C6	1.370 (5)
N1—C2	1.388 (4)	C5—H5	0.9500
N1—H1	0.891 (19)	C6—O6	1.321 (4)
C2—O2	1.242 (4)	O6—H6	0.840 (10)
C2—C3	1.427 (5)	C1X—S2X	1.770 (5)
C3—C4	1.405 (5)	C1X—H1X1	0.9800
C3—C31	1.418 (5)	C1X—H1X2	0.9800
C31—N32	1.153 (5)	C1X—H1X3	0.9800
C4—C5	1.397 (5)	S2X—O2X	1.512 (3)
C4—C41	1.486 (5)	S2X—C3X	1.777 (5)
C41—H41A	0.9800	C3X—H3X1	0.9800
C41—H41B	0.9800	C3X—H3X2	0.9800
C41—H41C	0.9800	C3X—H3X3	0.9800
C6—N1—C2	123.6 (3)	C4—C5—H5	120.2
C6—N1—H1	119 (3)	O6—C6—N1	113.5 (3)
C2—N1—H1	117 (3)	O6—C6—C5	125.5 (3)
O2—C2—N1	119.8 (3)	N1—C6—C5	121.0 (3)
O2—C2—C3	125.2 (3)	C6—O6—H6	110 (3)
N1—C2—C3	115.0 (3)	S2X—C1X—H1X1	109.5
C4—C3—C31	120.3 (3)	S2X—C1X—H1X2	109.5
C4—C3—C2	122.0 (3)	H1X1—C1X—H1X2	109.5
C31—C3—C2	117.6 (3)	S2X—C1X—H1X3	109.5
N32—C31—C3	179.1 (4)	H1X1—C1X—H1X3	109.5
C5—C4—C3	118.7 (3)	H1X2—C1X—H1X3	109.5
C5—C4—C41	121.3 (3)	O2X—S2X—C1X	107.04 (19)
C3—C4—C41	120.0 (3)	O2X—S2X—C3X	105.1 (2)
C4—C41—H41A	109.5	C1X—S2X—C3X	99.0 (2)
C4—C41—H41B	109.5	S2X—C3X—H3X1	109.5
H41A—C41—H41B	109.5	S2X—C3X—H3X2	109.5
C4—C41—H41C	109.5	H3X1—C3X—H3X2	109.5
H41A—C41—H41C	109.5	S2X—C3X—H3X3	109.5
H41B—C41—H41C	109.5	H3X1—C3X—H3X3	109.5
C6—C5—C4	119.6 (3)	H3X2—C3X—H3X3	109.5
C6—C5—H5	120.2
C6—N1—C2—O2	−179.2 (3)	C31—C3—C4—C41	−1.5 (6)
C6—N1—C2—C3	2.1 (5)	C2—C3—C4—C41	179.3 (3)
O2—C2—C3—C4	−179.4 (4)	C3—C4—C5—C6	1.7 (6)
N1—C2—C3—C4	−0.7 (5)	C41—C4—C5—C6	−178.8 (4)
O2—C2—C3—C31	1.4 (6)	C2—N1—C6—O6	177.2 (3)
N1—C2—C3—C31	−179.9 (3)	C2—N1—C6—C5	−1.6 (6)
C31—C3—C4—C5	178.1 (3)	C4—C5—C6—O6	−179.1 (3)
C2—C3—C4—C5	−1.1 (6)	C4—C5—C6—N1	−0.4 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.89 (2)	1.87 (2)	2.755 (4)	175 (4)
O6—H6···O2X	0.84 (1)	1.72 (2)	2.541 (3)	167 (5)

Symmetry code: (i) −x, −y+2, −z+1.

(2) 3-Cyano-6-hydroxy-4-methyl-2-pyridone N,N-dimethylacetamide monosolvate

Crystal data

C7H6N2O2·C4H9NO	Z = 2
Mr = 237.26	F(000) = 252
Triclinic, P1	Dx = 1.306 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1268 (14) Å	Cell parameters from 3553 reflections
b = 7.5481 (13) Å	θ = 3.3–25.9°
c = 12.774 (2) Å	µ = 0.10 mm^−1
α = 89.486 (13)°	T = 173 K
β = 75.620 (14)°	Needle, colourless
γ = 65.679 (13)°	0.31 × 0.08 × 0.04 mm
V = 603.18 (19) Å^3

Data collection

Stoe IPDS II two-circle diffractometer	2246 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	1481 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.065
ω scans	θmax = 25.6°, θmin = 3.3°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −8→8
Tmin = 0.971, Tmax = 0.996	k = −9→9
5011 measured reflections	l = −13→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0629P)^2] where P = (Fo^2 + 2Fc^2)/3
2246 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.23 e Å^−3
1 restraint	Δρmin = −0.24 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.5960 (3)	0.8203 (2)	0.59197 (14)	0.0266 (4)
H1	0.524 (4)	0.954 (4)	0.591 (2)	0.039 (7)*
C2	0.6453 (3)	0.7037 (3)	0.49770 (17)	0.0250 (5)
O2	0.6033 (3)	0.7806 (2)	0.41476 (12)	0.0328 (4)
C3	0.7438 (3)	0.4978 (3)	0.50460 (17)	0.0240 (5)
C31	0.7985 (3)	0.3716 (3)	0.40937 (18)	0.0286 (5)
N32	0.8411 (3)	0.2687 (3)	0.33250 (16)	0.0394 (5)
C4	0.7834 (3)	0.4241 (3)	0.60130 (17)	0.0253 (5)
C41	0.8861 (4)	0.2071 (3)	0.60763 (19)	0.0323 (5)
H41A	0.9330	0.1818	0.6744	0.048*
H41B	1.0098	0.1452	0.5445	0.048*
H41C	0.7824	0.1528	0.6082	0.048*
C5	0.7261 (3)	0.5531 (3)	0.69227 (17)	0.0272 (5)
H5	0.7529	0.5049	0.7585	0.033*
C6	0.6296 (3)	0.7522 (3)	0.68625 (17)	0.0262 (5)
O6	0.5655 (3)	0.8891 (2)	0.76657 (13)	0.0365 (4)
H6	0.589 (6)	0.837 (5)	0.826 (2)	0.086 (12)*
C1X	0.8758 (4)	0.8642 (4)	0.9370 (2)	0.0467 (6)
H1X1	0.8890	0.8594	0.8588	0.070*
H1X2	1.0175	0.7946	0.9493	0.070*
H1X3	0.8137	1.0007	0.9682	0.070*
C2X	0.7336 (4)	0.7690 (3)	0.99046 (19)	0.0358 (6)
O2X	0.6044 (3)	0.7496 (2)	0.94471 (13)	0.0393 (4)
N3X	0.7438 (3)	0.7067 (3)	1.08666 (16)	0.0398 (5)
C4X	0.8830 (4)	0.7331 (4)	1.1462 (2)	0.0526 (7)
H4X1	1.0327	0.6582	1.1057	0.079*
H4X2	0.8572	0.6868	1.2180	0.079*
H4X3	0.8522	0.8720	1.1547	0.079*
C5X	0.5960 (5)	0.6241 (4)	1.1419 (2)	0.0499 (7)
H5X1	0.4590	0.7303	1.1803	0.075*
H5X2	0.6571	0.5382	1.1942	0.075*
H5X3	0.5732	0.5488	1.0881	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0336 (10)	0.0207 (8)	0.0267 (10)	−0.0098 (8)	−0.0131 (8)	0.0046 (7)
C2	0.0282 (11)	0.0264 (10)	0.0233 (11)	−0.0145 (9)	−0.0067 (9)	0.0045 (8)
O2	0.0492 (10)	0.0273 (7)	0.0234 (8)	−0.0152 (7)	−0.0141 (7)	0.0070 (6)
C3	0.0233 (10)	0.0240 (9)	0.0235 (11)	−0.0098 (8)	−0.0044 (8)	0.0017 (8)
C31	0.0276 (11)	0.0273 (10)	0.0278 (12)	−0.0099 (9)	−0.0049 (9)	0.0052 (9)
N32	0.0464 (13)	0.0371 (10)	0.0295 (11)	−0.0139 (9)	−0.0075 (9)	−0.0035 (9)
C4	0.0230 (10)	0.0249 (9)	0.0285 (12)	−0.0099 (8)	−0.0083 (9)	0.0045 (8)
C41	0.0392 (13)	0.0235 (10)	0.0322 (13)	−0.0094 (9)	−0.0127 (10)	0.0027 (9)
C5	0.0312 (12)	0.0267 (9)	0.0254 (11)	−0.0105 (9)	−0.0135 (9)	0.0064 (8)
C6	0.0300 (11)	0.0250 (9)	0.0245 (11)	−0.0110 (9)	−0.0097 (9)	0.0028 (8)
O6	0.0559 (11)	0.0244 (7)	0.0276 (9)	−0.0111 (7)	−0.0188 (8)	−0.0007 (7)
C1X	0.0465 (15)	0.0632 (16)	0.0305 (14)	−0.0254 (13)	−0.0067 (11)	0.0051 (12)
C2X	0.0386 (14)	0.0331 (11)	0.0255 (13)	−0.0075 (10)	−0.0047 (10)	−0.0033 (9)
O2X	0.0527 (11)	0.0401 (9)	0.0272 (9)	−0.0184 (8)	−0.0164 (8)	0.0026 (7)
N3X	0.0405 (12)	0.0442 (11)	0.0261 (11)	−0.0096 (9)	−0.0091 (8)	0.0029 (8)
C4X	0.0408 (15)	0.0705 (18)	0.0357 (15)	−0.0089 (13)	−0.0174 (12)	0.0004 (13)
C5X	0.0625 (18)	0.0471 (14)	0.0359 (15)	−0.0216 (13)	−0.0092 (13)	0.0150 (11)

Geometric parameters (Å, º)

N1—C6	1.343 (3)	O6—H6	0.875 (19)
N1—C2	1.380 (3)	C1X—C2X	1.502 (4)
N1—H1	0.92 (3)	C1X—H1X1	0.9800
C2—O2	1.246 (3)	C1X—H1X2	0.9800
C2—C3	1.430 (3)	C1X—H1X3	0.9800
C3—C4	1.395 (3)	C2X—O2X	1.262 (3)
C3—C31	1.421 (3)	C2X—N3X	1.320 (3)
C31—N32	1.154 (3)	N3X—C4X	1.464 (4)
C4—C5	1.386 (3)	N3X—C5X	1.470 (4)
C4—C41	1.505 (3)	C4X—H4X1	0.9800
C41—H41A	0.9800	C4X—H4X2	0.9800
C41—H41B	0.9800	C4X—H4X3	0.9800
C41—H41C	0.9800	C5X—H5X1	0.9800
C5—C6	1.382 (3)	C5X—H5X2	0.9800
C5—H5	0.9500	C5X—H5X3	0.9800
C6—O6	1.314 (3)
C6—N1—C2	124.35 (17)	C6—O6—H6	111 (2)
C6—N1—H1	118.5 (16)	C2X—C1X—H1X1	109.5
C2—N1—H1	116.9 (16)	C2X—C1X—H1X2	109.5
O2—C2—N1	119.66 (17)	H1X1—C1X—H1X2	109.5
O2—C2—C3	125.03 (18)	C2X—C1X—H1X3	109.5
N1—C2—C3	115.31 (18)	H1X1—C1X—H1X3	109.5
C4—C3—C31	121.43 (18)	H1X2—C1X—H1X3	109.5
C4—C3—C2	121.20 (18)	O2X—C2X—N3X	120.0 (2)
C31—C3—C2	117.37 (19)	O2X—C2X—C1X	120.7 (2)
N32—C31—C3	179.3 (2)	N3X—C2X—C1X	119.3 (2)
C5—C4—C3	119.29 (18)	C2X—N3X—C4X	122.6 (2)
C5—C4—C41	120.05 (19)	C2X—N3X—C5X	119.4 (2)
C3—C4—C41	120.67 (18)	C4X—N3X—C5X	117.8 (2)
C4—C41—H41A	109.5	N3X—C4X—H4X1	109.5
C4—C41—H41B	109.5	N3X—C4X—H4X2	109.5
H41A—C41—H41B	109.5	H4X1—C4X—H4X2	109.5
C4—C41—H41C	109.5	N3X—C4X—H4X3	109.5
H41A—C41—H41C	109.5	H4X1—C4X—H4X3	109.5
H41B—C41—H41C	109.5	H4X2—C4X—H4X3	109.5
C6—C5—C4	119.8 (2)	N3X—C5X—H5X1	109.5
C6—C5—H5	120.1	N3X—C5X—H5X2	109.5
C4—C5—H5	120.1	H5X1—C5X—H5X2	109.5
O6—C6—N1	114.26 (17)	N3X—C5X—H5X3	109.5
O6—C6—C5	125.7 (2)	H5X1—C5X—H5X3	109.5
N1—C6—C5	120.06 (18)	H5X2—C5X—H5X3	109.5
C6—N1—C2—O2	178.2 (2)	C3—C4—C5—C6	0.4 (3)
C6—N1—C2—C3	−1.8 (3)	C41—C4—C5—C6	−179.3 (2)
O2—C2—C3—C4	−179.4 (2)	C2—N1—C6—O6	−178.3 (2)
N1—C2—C3—C4	0.6 (3)	C2—N1—C6—C5	2.3 (3)
O2—C2—C3—C31	0.2 (3)	C4—C5—C6—O6	179.1 (2)
N1—C2—C3—C31	−179.7 (2)	C4—C5—C6—N1	−1.5 (3)
C31—C3—C4—C5	−179.6 (2)	O2X—C2X—N3X—C4X	−177.1 (2)
C2—C3—C4—C5	0.0 (3)	C1X—C2X—N3X—C4X	2.4 (3)
C31—C3—C4—C41	0.0 (3)	O2X—C2X—N3X—C5X	−3.1 (3)
C2—C3—C4—C41	179.7 (2)	C1X—C2X—N3X—C5X	176.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.92 (3)	1.84 (3)	2.762 (2)	177 (2)
O6—H6···O2X	0.88 (2)	1.66 (2)	2.528 (2)	174 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

(3) 2-Amino-4-dimethylamino-6-methylpyrimidin-1-ium 5-cyano-4-methyl-6-oxo-1,6-dihydropyridin-2-olate

Crystal data

C7H13N4^+·C7H5N2O2^−	Z = 2
Mr = 302.34	F(000) = 320
Triclinic, P1	Dx = 1.356 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1928 (6) Å	Cell parameters from 16835 reflections
b = 8.1316 (7) Å	θ = 3.2–26.4°
c = 13.6009 (11) Å	µ = 0.10 mm^−1
α = 93.219 (7)°	T = 173 K
β = 99.114 (7)°	Block, light brown
γ = 108.395 (6)°	0.21 × 0.18 × 0.15 mm
V = 740.53 (11) Å^3

Data collection

Stoe IPDS II two-circle diffractometer	2922 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	2450 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.046
ω scans	θmax = 26.1°, θmin = 3.2°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −8→8
Tmin = 0.980, Tmax = 0.986	k = −10→10
18362 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.2111P] where P = (Fo^2 + 2Fc^2)/3
2922 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1B	0.72412 (18)	0.61456 (15)	0.68255 (8)	0.0255 (3)
C2B	0.7932 (2)	0.78383 (17)	0.71155 (10)	0.0243 (3)
N2B	0.8649 (2)	0.89491 (16)	0.64799 (10)	0.0324 (3)
H21B	0.873 (3)	0.850 (2)	0.5876 (15)	0.040 (5)*
H22B	0.919 (3)	1.009 (2)	0.6724 (13)	0.038 (5)*
N3B	0.79176 (18)	0.85237 (15)	0.80525 (8)	0.0256 (3)
H3B	0.849 (3)	0.966 (2)	0.8245 (12)	0.033 (4)*
C4B	0.7153 (2)	0.74642 (18)	0.87363 (10)	0.0244 (3)
C41B	0.7129 (2)	0.83464 (19)	0.97289 (11)	0.0317 (3)
H41A	0.5936	0.7687	0.9978	0.048*	0.634 (19)
H41B	0.7113	0.9533	0.9650	0.048*	0.634 (19)
H41C	0.8322	0.8397	1.0208	0.048*	0.634 (19)
H411	0.7082	0.7580	1.0208	0.048*	0.366 (19)
H412	0.5642	0.8456	0.9636	0.048*	0.366 (19)
H413	0.8136	0.9447	0.9899	0.048*	0.366 (19)
C5B	0.6461 (2)	0.57194 (18)	0.84805 (10)	0.0267 (3)
H5B	0.5925	0.4947	0.8941	0.032*
C6B	0.6559 (2)	0.50648 (17)	0.74967 (10)	0.0247 (3)
N6B	0.59755 (18)	0.33566 (15)	0.72042 (9)	0.0288 (3)
C61B	0.6019 (2)	0.26945 (19)	0.61885 (12)	0.0344 (3)
H61A	0.4651	0.2123	0.5824	0.052*	0.72 (2)
H61B	0.6738	0.1851	0.6222	0.052*	0.72 (2)
H61C	0.6696	0.3666	0.5839	0.052*	0.72 (2)
H611	0.7178	0.2877	0.6031	0.052*	0.28 (2)
H612	0.5287	0.3386	0.5675	0.052*	0.28 (2)
H613	0.4962	0.1445	0.6046	0.052*	0.28 (2)
C62B	0.5220 (2)	0.20669 (19)	0.78727 (12)	0.0351 (4)
H62A	0.6085	0.2400	0.8535	0.053*
H62B	0.5205	0.0921	0.7599	0.053*
H62C	0.3863	0.2013	0.7934	0.053*
N1A	0.92610 (18)	0.54039 (14)	0.11809 (8)	0.0242 (3)
H1A	0.981 (3)	0.589 (2)	0.0716 (15)	0.044 (5)*
C2A	0.9359 (2)	0.64251 (17)	0.20408 (10)	0.0234 (3)
O2A	1.00640 (16)	0.80541 (12)	0.20788 (7)	0.0301 (2)
C3A	0.8629 (2)	0.55140 (17)	0.28319 (10)	0.0234 (3)
C31A	0.8725 (2)	0.65553 (18)	0.37253 (10)	0.0261 (3)
N32A	0.8826 (2)	0.74419 (17)	0.44345 (9)	0.0350 (3)
C4A	0.7924 (2)	0.36751 (17)	0.27413 (10)	0.0242 (3)
C41A	0.7278 (2)	0.2783 (2)	0.36280 (11)	0.0324 (3)
H41D	0.6783	0.1517	0.3446	0.049*
H41E	0.6215	0.3161	0.3830	0.049*
H41F	0.8416	0.3090	0.4186	0.049*
C5A	0.7868 (2)	0.27515 (17)	0.18580 (10)	0.0251 (3)
H5A	0.7364	0.1513	0.1794	0.030*
C6A	0.8547 (2)	0.36014 (17)	0.10357 (10)	0.0236 (3)
O6A	0.85508 (16)	0.28481 (12)	0.02075 (7)	0.0305 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1B	0.0286 (6)	0.0235 (6)	0.0237 (6)	0.0083 (5)	0.0044 (5)	−0.0010 (4)
C2B	0.0276 (7)	0.0241 (7)	0.0225 (6)	0.0108 (5)	0.0043 (5)	0.0004 (5)
N2B	0.0507 (8)	0.0222 (6)	0.0236 (6)	0.0090 (6)	0.0119 (6)	−0.0008 (5)
N3B	0.0322 (6)	0.0204 (6)	0.0236 (6)	0.0084 (5)	0.0060 (5)	−0.0018 (4)
C4B	0.0246 (7)	0.0269 (7)	0.0227 (7)	0.0098 (5)	0.0049 (5)	0.0014 (5)
C41B	0.0423 (9)	0.0286 (7)	0.0235 (7)	0.0099 (6)	0.0093 (6)	−0.0007 (5)
C5B	0.0294 (7)	0.0260 (7)	0.0248 (7)	0.0084 (6)	0.0068 (6)	0.0026 (5)
C6B	0.0230 (7)	0.0236 (7)	0.0270 (7)	0.0080 (5)	0.0036 (5)	0.0000 (5)
N6B	0.0336 (7)	0.0212 (6)	0.0295 (6)	0.0059 (5)	0.0081 (5)	−0.0022 (5)
C61B	0.0389 (9)	0.0271 (7)	0.0339 (8)	0.0073 (6)	0.0081 (7)	−0.0070 (6)
C62B	0.0404 (9)	0.0217 (7)	0.0407 (9)	0.0048 (6)	0.0118 (7)	0.0017 (6)
N1A	0.0332 (7)	0.0203 (6)	0.0186 (5)	0.0067 (5)	0.0082 (5)	0.0005 (4)
C2A	0.0265 (7)	0.0218 (6)	0.0223 (7)	0.0092 (5)	0.0042 (5)	−0.0014 (5)
O2A	0.0448 (6)	0.0193 (5)	0.0258 (5)	0.0081 (4)	0.0111 (4)	−0.0007 (4)
C3A	0.0249 (7)	0.0262 (7)	0.0189 (6)	0.0087 (5)	0.0039 (5)	−0.0012 (5)
C31A	0.0267 (7)	0.0275 (7)	0.0238 (7)	0.0080 (5)	0.0057 (5)	0.0023 (5)
N32A	0.0420 (8)	0.0382 (7)	0.0240 (6)	0.0123 (6)	0.0085 (5)	−0.0042 (5)
C4A	0.0220 (7)	0.0264 (7)	0.0224 (7)	0.0066 (5)	0.0023 (5)	0.0015 (5)
C41A	0.0398 (8)	0.0302 (7)	0.0247 (7)	0.0067 (6)	0.0083 (6)	0.0037 (6)
C5A	0.0279 (7)	0.0201 (6)	0.0250 (7)	0.0054 (5)	0.0046 (5)	0.0001 (5)
C6A	0.0254 (7)	0.0213 (6)	0.0225 (7)	0.0071 (5)	0.0030 (5)	−0.0022 (5)
O6A	0.0428 (6)	0.0229 (5)	0.0228 (5)	0.0057 (4)	0.0099 (4)	−0.0044 (4)

Geometric parameters (Å, º)

N1B—C2B	1.3199 (17)	C61B—H61C	0.9800
N1B—C6B	1.3441 (18)	C61B—H611	0.8634
C2B—N2B	1.3281 (18)	C61B—H612	1.0936
C2B—N3B	1.3649 (17)	C61B—H613	1.0449
N2B—H21B	0.898 (19)	C62B—H62A	0.9800
N2B—H22B	0.906 (19)	C62B—H62B	0.9800
N3B—C4B	1.3649 (18)	C62B—H62C	0.9800
N3B—H3B	0.890 (18)	N1A—C2A	1.3749 (17)
C4B—C5B	1.3513 (19)	N1A—C6A	1.3825 (17)
C4B—C41B	1.4979 (18)	N1A—H1A	0.85 (2)
C41B—H41A	0.9800	C2A—O2A	1.2548 (16)
C41B—H41B	0.9800	C2A—C3A	1.4160 (18)
C41B—H41C	0.9800	C3A—C4A	1.4104 (19)
C41B—H411	0.9236	C3A—C31A	1.4211 (18)
C41B—H412	1.0893	C31A—N32A	1.1498 (18)
C41B—H413	0.9450	C4A—C5A	1.3688 (18)
C5B—C6B	1.4324 (19)	C4A—C41A	1.5030 (18)
C5B—H5B	0.9500	C41A—H41D	0.9800
C6B—N6B	1.3345 (17)	C41A—H41E	0.9800
N6B—C62B	1.4579 (19)	C41A—H41F	0.9800
N6B—C61B	1.4628 (18)	C5A—C6A	1.4190 (18)
C61B—H61A	0.9800	C5A—H5A	0.9500
C61B—H61B	0.9800	C6A—O6A	1.2524 (16)
C2B—N1B—C6B	118.07 (11)	H61A—C61B—H61C	109.5
N1B—C2B—N2B	119.96 (12)	H61B—C61B—H61C	109.5
N1B—C2B—N3B	122.62 (12)	N6B—C61B—H611	116.9
N2B—C2B—N3B	117.40 (12)	H61A—C61B—H611	133.6
C2B—N2B—H21B	117.7 (12)	H61B—C61B—H611	55.5
C2B—N2B—H22B	116.9 (11)	H61C—C61B—H611	54.8
H21B—N2B—H22B	124.8 (17)	N6B—C61B—H612	106.8
C4B—N3B—C2B	120.66 (12)	H61A—C61B—H612	59.3
C4B—N3B—H3B	118.6 (11)	H61B—C61B—H612	143.7
C2B—N3B—H3B	120.5 (11)	H61C—C61B—H612	54.3
C5B—C4B—N3B	118.89 (12)	H611—C61B—H612	104.9
C5B—C4B—C41B	124.53 (13)	N6B—C61B—H613	106.0
N3B—C4B—C41B	116.58 (12)	H61B—C61B—H613	72.2
C4B—C41B—H41A	109.5	H61C—C61B—H613	141.0
C4B—C41B—H41B	109.5	H611—C61B—H613	120.0
H41A—C41B—H41B	109.5	H612—C61B—H613	100.3
C4B—C41B—H41C	109.5	N6B—C62B—H62A	109.5
H41A—C41B—H41C	109.5	N6B—C62B—H62B	109.5
H41B—C41B—H41C	109.5	H62A—C62B—H62B	109.5
C4B—C41B—H411	109.7	N6B—C62B—H62C	109.5
H41A—C41B—H411	54.1	H62A—C62B—H62C	109.5
H41B—C41B—H411	140.8	H62B—C62B—H62C	109.5
H41C—C41B—H411	58.3	C2A—N1A—C6A	125.89 (12)
C4B—C41B—H412	103.5	C2A—N1A—H1A	118.5 (13)
H41A—C41B—H412	48.7	C6A—N1A—H1A	115.2 (13)
H41B—C41B—H412	66.5	O2A—C2A—N1A	119.51 (12)
H41C—C41B—H412	145.8	O2A—C2A—C3A	124.80 (12)
H411—C41B—H412	102.0	N1A—C2A—C3A	115.69 (12)
C4B—C41B—H413	112.9	C4A—C3A—C2A	121.27 (12)
H41A—C41B—H413	136.9	C4A—C3A—C31A	122.46 (12)
H41B—C41B—H413	48.1	C2A—C3A—C31A	116.22 (12)
H41C—C41B—H413	63.2	N32A—C31A—C3A	177.94 (15)
H411—C41B—H413	115.7	C5A—C4A—C3A	119.44 (12)
H412—C41B—H413	111.9	C5A—C4A—C41A	121.78 (12)
C4B—C5B—C6B	118.22 (13)	C3A—C4A—C41A	118.78 (12)
C4B—C5B—H5B	120.9	C4A—C41A—H41D	109.5
C6B—C5B—H5B	120.9	C4A—C41A—H41E	109.5
N6B—C6B—N1B	116.96 (12)	H41D—C41A—H41E	109.5
N6B—C6B—C5B	121.60 (13)	C4A—C41A—H41F	109.5
N1B—C6B—C5B	121.43 (12)	H41D—C41A—H41F	109.5
C6B—N6B—C62B	121.60 (12)	H41E—C41A—H41F	109.5
C6B—N6B—C61B	121.40 (12)	C4A—C5A—C6A	121.50 (12)
C62B—N6B—C61B	116.98 (12)	C4A—C5A—H5A	119.3
N6B—C61B—H61A	109.5	C6A—C5A—H5A	119.3
N6B—C61B—H61B	109.5	O6A—C6A—N1A	118.64 (12)
H61A—C61B—H61B	109.5	O6A—C6A—C5A	125.20 (12)
N6B—C61B—H61C	109.5	N1A—C6A—C5A	116.17 (11)
C6B—N1B—C2B—N2B	178.98 (13)	C6A—N1A—C2A—O2A	179.18 (13)
C6B—N1B—C2B—N3B	−2.2 (2)	C6A—N1A—C2A—C3A	−0.9 (2)
N1B—C2B—N3B—C4B	−0.7 (2)	O2A—C2A—C3A—C4A	−177.75 (13)
N2B—C2B—N3B—C4B	178.18 (13)	N1A—C2A—C3A—C4A	2.28 (19)
C2B—N3B—C4B—C5B	1.9 (2)	O2A—C2A—C3A—C31A	−0.1 (2)
C2B—N3B—C4B—C41B	−177.58 (13)	N1A—C2A—C3A—C31A	179.93 (12)
N3B—C4B—C5B—C6B	−0.2 (2)	C2A—C3A—C4A—C5A	−2.6 (2)
C41B—C4B—C5B—C6B	179.17 (13)	C31A—C3A—C4A—C5A	179.90 (13)
C2B—N1B—C6B—N6B	−176.22 (13)	C2A—C3A—C4A—C41A	176.51 (13)
C2B—N1B—C6B—C5B	3.83 (19)	C31A—C3A—C4A—C41A	−1.0 (2)
C4B—C5B—C6B—N6B	177.39 (13)	C3A—C4A—C5A—C6A	1.4 (2)
C4B—C5B—C6B—N1B	−2.7 (2)	C41A—C4A—C5A—C6A	−177.69 (13)
N1B—C6B—N6B—C62B	179.66 (13)	C2A—N1A—C6A—O6A	179.99 (13)
C5B—C6B—N6B—C62B	−0.4 (2)	C2A—N1A—C6A—C5A	−0.3 (2)
N1B—C6B—N6B—C61B	−1.9 (2)	C4A—C5A—C6A—O6A	179.73 (13)
C5B—C6B—N6B—C61B	178.05 (13)	C4A—C5A—C6A—N1A	0.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O6A^i	0.85 (2)	1.97 (2)	2.8097 (15)	171.3 (18)
N2B—H21B···N32A	0.898 (19)	2.12 (2)	3.0142 (18)	177.9 (17)
N2B—H22B···O2A^ii	0.906 (19)	2.037 (19)	2.8466 (16)	148.1 (16)
N3B—H3B···O2A^ii	0.890 (18)	1.934 (18)	2.7335 (15)	148.5 (15)

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

(4) 2,6-Diamino-4-dimethylamino-1,3,5-triazin-1-ium 5-cyano-4-methyl-6-oxo-1,6-dihydropyridin-2-olate–N,N-dimethylacetamide (1/1)

Crystal data

C5H11N6^+·C7H5N2O2^−·C4H9NO	Z = 2
Mr = 391.45	F(000) = 416
Triclinic, P1	Dx = 1.306 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6590 (6) Å	Cell parameters from 27839 reflections
b = 10.2703 (8) Å	θ = 3.2–26.3°
c = 13.9231 (11) Å	µ = 0.10 mm^−1
α = 105.134 (6)°	T = 173 K
β = 104.921 (6)°	Plate, colourless
γ = 98.267 (6)°	0.48 × 0.41 × 0.17 mm
V = 995.08 (14) Å^3

Data collection

Stoe IPDS II two-circle diffractometer	3836 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	3352 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.052
ω scans	θmax = 25.9°, θmin = 3.4°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −9→9
Tmin = 0.956, Tmax = 0.984	k = −12→12
23600 measured reflections	l = −16→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0642P)^2 + 0.3174P] where P = (Fo^2 + 2Fc^2)/3
3836 reflections	(Δ/σ)max < 0.001
289 parameters	Δρmax = 0.27 e Å^−3
16 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1A	0.54398 (19)	0.66486 (13)	0.09229 (10)	0.0296 (3)
H1A	0.501 (3)	0.571 (2)	0.0790 (16)	0.045 (5)*
C2A	0.5518 (2)	0.74794 (16)	0.18862 (12)	0.0281 (3)
O2A	0.50539 (18)	0.69277 (11)	0.25174 (9)	0.0378 (3)
C3A	0.6129 (2)	0.89160 (15)	0.20919 (12)	0.0291 (3)
C31A	0.6188 (2)	0.97749 (16)	0.30837 (13)	0.0345 (4)
N32A	0.6224 (2)	1.04332 (16)	0.38949 (13)	0.0495 (4)
C4A	0.6639 (2)	0.94424 (16)	0.13385 (13)	0.0320 (4)
C41A	0.7305 (3)	1.09811 (17)	0.16005 (15)	0.0458 (5)
H41A	0.7397	1.1202	0.0969	0.069*
H41B	0.8527	1.1290	0.2133	0.069*
H41C	0.6425	1.1454	0.1870	0.069*
C5A	0.6538 (2)	0.85493 (17)	0.03933 (13)	0.0347 (4)
H5A	0.6886	0.8908	−0.0111	0.042*
C6A	0.5924 (2)	0.70993 (16)	0.01539 (12)	0.0314 (3)
O6A	0.57947 (19)	0.61975 (12)	−0.06893 (9)	0.0417 (3)
N1B	0.22188 (18)	0.33194 (13)	0.38320 (10)	0.0307 (3)
C2B	0.2323 (2)	0.43049 (16)	0.47172 (12)	0.0283 (3)
N2B	0.16943 (19)	0.38958 (15)	0.54316 (11)	0.0347 (3)
C21B	0.1783 (3)	0.4865 (2)	0.64232 (13)	0.0388 (4)
H21A	0.2255	0.5812	0.6438	0.058*
H21B	0.2614	0.4656	0.6999	0.058*
H21C	0.0539	0.4781	0.6501	0.058*
C22B	0.0878 (3)	0.24494 (19)	0.52504 (15)	0.0439 (4)
H22A	0.0923	0.1888	0.4573	0.066*
H22B	−0.0414	0.2352	0.5248	0.066*
H22C	0.1577	0.2134	0.5808	0.066*
N3B	0.29940 (18)	0.56850 (13)	0.49655 (10)	0.0296 (3)
C4B	0.3595 (2)	0.60768 (15)	0.42533 (11)	0.0269 (3)
N4B	0.4227 (2)	0.74041 (14)	0.43921 (11)	0.0326 (3)
H4B1	0.463 (3)	0.760 (2)	0.3859 (18)	0.052 (6)*
H4B2	0.419 (3)	0.804 (2)	0.4972 (16)	0.036 (5)*
N5B	0.35657 (18)	0.51455 (13)	0.33445 (10)	0.0279 (3)
H5B	0.399 (3)	0.544 (2)	0.2890 (17)	0.045 (6)*
C6B	0.2897 (2)	0.37689 (15)	0.31600 (12)	0.0276 (3)
N6B	0.2929 (2)	0.29076 (14)	0.22793 (11)	0.0352 (3)
H6B1	0.252 (3)	0.196 (2)	0.2118 (16)	0.044 (5)*
H6B2	0.340 (3)	0.320 (2)	0.1821 (18)	0.052 (6)*
C1X	0.1344 (3)	−0.0500 (2)	0.29990 (15)	0.0488 (5)
H4XA	0.1164	−0.0840	0.3570	0.073*	0.085 (5)
H4XB	0.0492	0.0102	0.2860	0.073*	0.085 (5)
H4XC	0.2626	0.0025	0.3198	0.073*	0.085 (5)
H1X1	0.0106	−0.0859	0.3025	0.073*	0.915 (5)
H1X2	0.1673	0.0511	0.3301	0.073*	0.915 (5)
H1X3	0.2251	−0.0896	0.3400	0.073*	0.915 (5)
O2X	0.1782 (2)	0.00152 (12)	0.14671 (11)	0.0488 (3)
C4X	0.0805 (4)	−0.2578 (2)	0.02152 (17)	0.0625 (6)
H1XA	0.0345	−0.3432	0.0350	0.094*	0.085 (5)
H1XB	0.1959	−0.2629	0.0041	0.094*	0.085 (5)
H1XC	−0.0124	−0.2465	−0.0371	0.094*	0.085 (5)
H4X1	0.1756	−0.3095	0.0109	0.094*	0.915 (5)
H4X2	0.1038	−0.1728	0.0027	0.094*	0.915 (5)
H4X3	−0.0421	−0.3149	−0.0227	0.094*	0.915 (5)
C5X	0.0366 (3)	−0.3327 (2)	0.1733 (2)	0.0651 (7)
H5XA	0.0221	−0.3565	0.2350	0.098*	0.085 (5)
H5XB	0.1321	−0.3749	0.1507	0.098*	0.085 (5)
H5XC	−0.0814	−0.3674	0.1166	0.098*	0.085 (5)
H5X1	−0.0857	−0.3904	0.1292	0.098*	0.915 (5)
H5X2	0.0328	−0.2921	0.2445	0.098*	0.915 (5)
H5X3	0.1290	−0.3897	0.1748	0.098*	0.915 (5)
C2X	0.1348 (3)	−0.08964 (19)	0.18689 (16)	0.0408 (6)	0.915 (5)
N3X	0.0870 (3)	−0.22227 (17)	0.13081 (14)	0.0468 (6)	0.915 (5)
C2X'	0.118 (3)	−0.1314 (5)	0.1212 (6)	0.034 (6)*	0.085 (5)
N3X'	0.095 (3)	−0.1731 (5)	0.2012 (6)	0.047 (6)*	0.085 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0402 (7)	0.0249 (6)	0.0253 (7)	0.0041 (5)	0.0147 (5)	0.0080 (5)
C2A	0.0312 (8)	0.0292 (7)	0.0256 (7)	0.0055 (6)	0.0119 (6)	0.0089 (6)
O2A	0.0576 (8)	0.0301 (6)	0.0291 (6)	0.0022 (5)	0.0227 (5)	0.0096 (5)
C3A	0.0312 (8)	0.0283 (8)	0.0279 (8)	0.0049 (6)	0.0116 (6)	0.0072 (6)
C31A	0.0382 (9)	0.0285 (8)	0.0372 (9)	0.0018 (6)	0.0172 (7)	0.0086 (7)
N32A	0.0645 (11)	0.0369 (8)	0.0423 (9)	0.0004 (7)	0.0286 (8)	−0.0018 (7)
C4A	0.0351 (8)	0.0289 (8)	0.0335 (8)	0.0054 (6)	0.0124 (7)	0.0113 (6)
C41A	0.0681 (12)	0.0282 (8)	0.0439 (10)	0.0050 (8)	0.0242 (9)	0.0120 (7)
C5A	0.0463 (9)	0.0324 (8)	0.0310 (8)	0.0058 (7)	0.0183 (7)	0.0145 (7)
C6A	0.0398 (9)	0.0311 (8)	0.0260 (8)	0.0059 (6)	0.0146 (6)	0.0100 (6)
O6A	0.0681 (8)	0.0307 (6)	0.0279 (6)	0.0022 (5)	0.0251 (6)	0.0064 (5)
N1B	0.0331 (7)	0.0328 (7)	0.0285 (7)	0.0042 (5)	0.0120 (5)	0.0130 (6)
C2B	0.0253 (7)	0.0363 (8)	0.0272 (8)	0.0082 (6)	0.0096 (6)	0.0143 (6)
N2B	0.0381 (8)	0.0408 (8)	0.0315 (7)	0.0060 (6)	0.0175 (6)	0.0167 (6)
C21B	0.0413 (9)	0.0517 (10)	0.0315 (8)	0.0121 (8)	0.0193 (7)	0.0178 (8)
C22B	0.0492 (10)	0.0448 (10)	0.0436 (10)	0.0005 (8)	0.0232 (8)	0.0202 (8)
N3B	0.0323 (7)	0.0335 (7)	0.0265 (7)	0.0078 (5)	0.0124 (5)	0.0115 (5)
C4B	0.0270 (7)	0.0317 (7)	0.0240 (7)	0.0087 (6)	0.0089 (6)	0.0097 (6)
N4B	0.0468 (8)	0.0272 (7)	0.0274 (7)	0.0078 (6)	0.0181 (6)	0.0081 (6)
N5B	0.0350 (7)	0.0280 (6)	0.0243 (6)	0.0064 (5)	0.0132 (5)	0.0105 (5)
C6B	0.0285 (7)	0.0297 (7)	0.0258 (7)	0.0054 (6)	0.0085 (6)	0.0111 (6)
N6B	0.0508 (9)	0.0279 (7)	0.0282 (7)	0.0028 (6)	0.0177 (6)	0.0089 (6)
C1X	0.0501 (11)	0.0533 (11)	0.0478 (11)	0.0119 (9)	0.0159 (9)	0.0231 (9)
O2X	0.0638 (9)	0.0327 (6)	0.0524 (8)	0.0028 (6)	0.0217 (7)	0.0178 (6)
C4X	0.0737 (15)	0.0512 (12)	0.0589 (13)	0.0047 (10)	0.0270 (12)	0.0100 (10)
C5X	0.0547 (13)	0.0509 (12)	0.0963 (19)	0.0029 (10)	0.0138 (12)	0.0480 (13)
C2X	0.0361 (10)	0.0372 (10)	0.0523 (13)	0.0088 (8)	0.0137 (9)	0.0187 (9)
N3X	0.0530 (11)	0.0362 (10)	0.0546 (12)	0.0042 (7)	0.0182 (8)	0.0213 (8)

Geometric parameters (Å, º)

N1A—C2A	1.370 (2)	N5B—C6B	1.3644 (19)
N1A—C6A	1.383 (2)	N5B—H5B	0.88 (2)
N1A—H1A	0.92 (2)	C6B—N6B	1.320 (2)
C2A—O2A	1.2581 (19)	N6B—H6B1	0.93 (2)
C2A—C3A	1.411 (2)	N6B—H6B2	0.91 (2)
C3A—C4A	1.411 (2)	C1X—C2X	1.520 (3)
C3A—C31A	1.417 (2)	C1X—N3X'	1.533 (5)
C31A—N32A	1.146 (2)	C1X—H4XA	0.9800
C4A—C5A	1.370 (2)	C1X—H4XB	0.9800
C4A—C41A	1.504 (2)	C1X—H4XC	0.9800
C41A—H41A	0.9800	C1X—H1X1	0.9800
C41A—H41B	0.9800	C1X—H1X2	0.9800
C41A—H41C	0.9800	C1X—H1X3	0.9800
C5A—C6A	1.417 (2)	O2X—C2X	1.257 (2)
C5A—H5A	0.9500	O2X—C2X'	1.298 (4)
C6A—O6A	1.2618 (19)	C4X—N3X	1.455 (3)
N1B—C6B	1.328 (2)	C4X—C2X'	1.562 (4)
N1B—C2B	1.351 (2)	C4X—H1XA	0.9800
C2B—N2B	1.343 (2)	C4X—H1XB	0.9800
C2B—N3B	1.355 (2)	C4X—H1XC	0.9800
N2B—C21B	1.455 (2)	C4X—H4X1	0.9800
N2B—C22B	1.455 (2)	C4X—H4X2	0.9800
C21B—H21A	0.9800	C4X—H4X3	0.9800
C21B—H21B	0.9800	C5X—N3X	1.458 (2)
C21B—H21C	0.9800	C5X—N3X'	1.551 (4)
C22B—H22A	0.9800	C5X—H5XA	0.9800
C22B—H22B	0.9800	C5X—H5XB	0.9800
C22B—H22C	0.9800	C5X—H5XC	0.9800
N3B—C4B	1.322 (2)	C5X—H5X1	0.9800
C4B—N4B	1.324 (2)	C5X—H5X2	0.9800
C4B—N5B	1.3652 (19)	C5X—H5X3	0.9800
N4B—H4B1	0.93 (2)	C2X—N3X	1.324 (3)
N4B—H4B2	0.91 (2)	C2X'—N3X'	1.335 (5)
C2A—N1A—C6A	125.62 (13)	N3X'—C1X—H1X2	145.8
C2A—N1A—H1A	115.5 (13)	H4XA—C1X—H1X2	104.7
C6A—N1A—H1A	118.8 (13)	H4XB—C1X—H1X2	55.8
O2A—C2A—N1A	118.95 (13)	H4XC—C1X—H1X2	58.7
O2A—C2A—C3A	124.80 (14)	H1X1—C1X—H1X2	109.5
N1A—C2A—C3A	116.25 (13)	C2X—C1X—H1X3	109.5
C2A—C3A—C4A	120.89 (14)	N3X'—C1X—H1X3	90.9
C2A—C3A—C31A	116.18 (14)	H4XA—C1X—H1X3	56.5
C4A—C3A—C31A	122.93 (14)	H4XB—C1X—H1X3	158.9
N32A—C31A—C3A	177.86 (18)	H4XC—C1X—H1X3	66.6
C5A—C4A—C3A	119.71 (14)	H1X1—C1X—H1X3	109.5
C5A—C4A—C41A	121.41 (15)	H1X2—C1X—H1X3	109.5
C3A—C4A—C41A	118.88 (15)	N3X—C4X—H1XA	72.0
C4A—C41A—H41A	109.5	C2X'—C4X—H1XA	109.5
C4A—C41A—H41B	109.5	N3X—C4X—H1XB	119.0
H41A—C41A—H41B	109.5	C2X'—C4X—H1XB	109.5
C4A—C41A—H41C	109.5	H1XA—C4X—H1XB	109.5
H41A—C41A—H41C	109.5	N3X—C4X—H1XC	128.0
H41B—C41A—H41C	109.5	C2X'—C4X—H1XC	109.5
C4A—C5A—C6A	121.18 (14)	H1XA—C4X—H1XC	109.5
C4A—C5A—H5A	119.4	H1XB—C4X—H1XC	109.5
C6A—C5A—H5A	119.4	N3X—C4X—H4X1	109.5
O6A—C6A—N1A	117.86 (14)	C2X'—C4X—H4X1	121.7
O6A—C6A—C5A	125.78 (14)	H1XA—C4X—H4X1	78.6
N1A—C6A—C5A	116.35 (14)	H1XC—C4X—H4X1	122.0
C6B—N1B—C2B	115.48 (13)	N3X—C4X—H4X2	109.5
N2B—C2B—N1B	117.64 (14)	C2X'—C4X—H4X2	71.8
N2B—C2B—N3B	115.67 (14)	H1XA—C4X—H4X2	170.0
N1B—C2B—N3B	126.68 (13)	H1XB—C4X—H4X2	78.7
C2B—N2B—C21B	122.23 (14)	H1XC—C4X—H4X2	61.5
C2B—N2B—C22B	121.47 (14)	H4X1—C4X—H4X2	109.5
C21B—N2B—C22B	116.30 (14)	N3X—C4X—H4X3	109.5
N2B—C21B—H21A	109.5	C2X'—C4X—H4X3	125.3
N2B—C21B—H21B	109.5	H1XA—C4X—H4X3	61.4
H21A—C21B—H21B	109.5	H1XB—C4X—H4X3	124.7
N2B—C21B—H21C	109.5	H1XC—C4X—H4X3	48.1
H21A—C21B—H21C	109.5	H4X1—C4X—H4X3	109.5
H21B—C21B—H21C	109.5	H4X2—C4X—H4X3	109.5
N2B—C22B—H22A	109.5	N3X—C5X—H5XA	146.4
N2B—C22B—H22B	109.5	N3X'—C5X—H5XA	109.5
H22A—C22B—H22B	109.5	N3X—C5X—H5XB	88.0
N2B—C22B—H22C	109.5	N3X'—C5X—H5XB	109.5
H22A—C22B—H22C	109.5	H5XA—C5X—H5XB	109.5
H22B—C22B—H22C	109.5	N3X—C5X—H5XC	90.0
C4B—N3B—C2B	115.15 (13)	N3X'—C5X—H5XC	109.5
N3B—C4B—N4B	120.73 (14)	H5XA—C5X—H5XC	109.5
N3B—C4B—N5B	121.90 (14)	H5XB—C5X—H5XC	109.5
N4B—C4B—N5B	117.37 (13)	N3X—C5X—H5X1	109.5
C4B—N4B—H4B1	116.1 (14)	N3X'—C5X—H5X1	125.6
C4B—N4B—H4B2	118.8 (12)	H5XA—C5X—H5X1	92.2
H4B1—N4B—H4B2	125.1 (19)	H5XB—C5X—H5X1	108.8
C6B—N5B—C4B	119.39 (13)	N3X—C5X—H5X2	109.5
C6B—N5B—H5B	121.2 (13)	N3X'—C5X—H5X2	72.5
C4B—N5B—H5B	119.4 (13)	H5XB—C5X—H5X2	128.8
N6B—C6B—N1B	121.56 (14)	H5XC—C5X—H5X2	117.9
N6B—C6B—N5B	117.11 (14)	H5X1—C5X—H5X2	109.5
N1B—C6B—N5B	121.33 (14)	N3X—C5X—H5X3	109.5
C6B—N6B—H6B1	121.2 (13)	N3X'—C5X—H5X3	121.1
C6B—N6B—H6B2	122.3 (14)	H5XA—C5X—H5X3	85.6
H6B1—N6B—H6B2	116.5 (19)	H5XC—C5X—H5X3	118.4
C2X—C1X—H4XA	145.9	H5X1—C5X—H5X3	109.5
N3X'—C1X—H4XA	109.5	H5X2—C5X—H5X3	109.5
C2X—C1X—H4XB	90.7	O2X—C2X—N3X	120.31 (19)
N3X'—C1X—H4XB	109.5	O2X—C2X—C1X	120.84 (17)
H4XA—C1X—H4XB	109.5	N3X—C2X—C1X	118.85 (17)
C2X—C1X—H4XC	88.0	C2X—N3X—C4X	118.02 (17)
N3X'—C1X—H4XC	109.5	C2X—N3X—C5X	122.80 (19)
H4XA—C1X—H4XC	109.5	C4X—N3X—C5X	119.16 (18)
H4XB—C1X—H4XC	109.5	O2X—C2X'—N3X'	113.1 (4)
C2X—C1X—H1X1	109.5	O2X—C2X'—C4X	135.6 (5)
N3X'—C1X—H1X1	87.8	N3X'—C2X'—C4X	111.0 (4)
H4XA—C1X—H1X1	58.1	C2X'—N3X'—C1X	111.5 (4)
H4XB—C1X—H1X1	67.5	C2X'—N3X'—C5X	113.4 (4)
H4XC—C1X—H1X1	162.0	C1X—N3X'—C5X	135.1 (4)
C2X—C1X—H1X2	109.5
C6A—N1A—C2A—O2A	−179.21 (15)	C2B—N1B—C6B—N6B	177.98 (14)
C6A—N1A—C2A—C3A	0.8 (2)	C2B—N1B—C6B—N5B	−3.0 (2)
O2A—C2A—C3A—C4A	179.43 (15)	C4B—N5B—C6B—N6B	−178.80 (14)
N1A—C2A—C3A—C4A	−0.5 (2)	C4B—N5B—C6B—N1B	2.1 (2)
O2A—C2A—C3A—C31A	−0.8 (2)	C2X'—O2X—C2X—N3X	4.0 (13)
N1A—C2A—C3A—C31A	179.25 (14)	C2X'—O2X—C2X—C1X	−175.5 (14)
C2A—C3A—C4A—C5A	0.1 (2)	N3X'—C1X—C2X—O2X	178.7 (13)
C31A—C3A—C4A—C5A	−179.68 (16)	N3X'—C1X—C2X—N3X	−0.8 (13)
C2A—C3A—C4A—C41A	−179.20 (16)	O2X—C2X—N3X—C4X	−2.0 (3)
C31A—C3A—C4A—C41A	1.0 (2)	C1X—C2X—N3X—C4X	177.42 (19)
C3A—C4A—C5A—C6A	0.2 (3)	O2X—C2X—N3X—C5X	179.51 (19)
C41A—C4A—C5A—C6A	179.47 (16)	C1X—C2X—N3X—C5X	−1.0 (3)
C2A—N1A—C6A—O6A	179.09 (15)	C2X'—C4X—N3X—C2X	−2.1 (12)
C2A—N1A—C6A—C5A	−0.5 (2)	C2X'—C4X—N3X—C5X	176.4 (12)
C4A—C5A—C6A—O6A	−179.56 (17)	N3X'—C5X—N3X—C2X	1.5 (12)
C4A—C5A—C6A—N1A	0.0 (2)	N3X'—C5X—N3X—C4X	−176.9 (13)
C6B—N1B—C2B—N2B	−178.49 (14)	C2X—O2X—C2X'—N3X'	0.2 (10)
C6B—N1B—C2B—N3B	1.9 (2)	C2X—O2X—C2X'—C4X	−174 (3)
N1B—C2B—N2B—C21B	178.44 (14)	N3X—C4X—C2X'—O2X	172 (3)
N3B—C2B—N2B—C21B	−2.0 (2)	N3X—C4X—C2X'—N3X'	−1.6 (10)
N1B—C2B—N2B—C22B	−1.7 (2)	O2X—C2X'—N3X'—C1X	4 (2)
N3B—C2B—N2B—C22B	177.87 (15)	C4X—C2X'—N3X'—C1X	179.3 (11)
N2B—C2B—N3B—C4B	−179.47 (13)	O2X—C2X'—N3X'—C5X	−176.0 (12)
N1B—C2B—N3B—C4B	0.1 (2)	C4X—C2X'—N3X'—C5X	−1 (2)
C2B—N3B—C4B—N4B	177.81 (14)	C2X—C1X—N3X'—C2X'	−2.8 (9)
C2B—N3B—C4B—N5B	−1.1 (2)	C2X—C1X—N3X'—C5X	177 (3)
N3B—C4B—N5B—C6B	0.1 (2)	N3X—C5X—N3X'—C2X'	2.1 (10)
N4B—C4B—N5B—C6B	−178.89 (13)	N3X—C5X—N3X'—C1X	−178 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O6A^i	0.92 (2)	1.93 (2)	2.8451 (18)	173.2 (19)
N4B—H4B1···O2A	0.93 (2)	1.94 (2)	2.7800 (18)	148.3 (19)
N4B—H4B2···N32A^ii	0.91 (2)	2.04 (2)	2.936 (2)	170.4 (17)
N5B—H5B···O2A	0.88 (2)	1.88 (2)	2.6744 (17)	149.1 (19)
N6B—H6B1···O2X	0.93 (2)	1.89 (2)	2.8033 (19)	165.8 (19)
N6B—H6B2···O6A^i	0.91 (2)	2.03 (2)	2.9359 (18)	174.3 (19)

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