Cocrystals of 6-chlorouracil and 6-chloro-3-methyl­uracil: exploring their hydrogen-bond-based synthon motifs with several triazine and pyrimidine derivatives

In order to obtain complexes held together by hydrogen as well as halogen bonds, 6-chlorouracil [6-chloropyrimidin-2,4(1H,3H)-dione; 6CU] and its 3-methyl derivative [6-chloro-3-methylpyrimidin-2,4(1H,3H)-dione; M6CU] were cocrystallized with 2,4,6-triaminopyrimidine and the three triazine derivatives 2,4,6-triamino-1,3,5-triazine (melamine), 2,4-diamino-6-methyl-1,3,5-triazine and 2-chloro-4,6-diamino-1,3,5-triazine, which all offer complementary hydrogen-bonding sites. Three of these compounds form cocrystals with 6CU; however, melamine yielded only a new pseudopolymorph with 6CU, but formed a cocrystal with M6CU. All six cocrystals contain solvent molecules (N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidin-2-one), whose intermolecular interactions contribute significantly to the stabilization of the crystal packing. Each of these structures comprises chains, which are primarily formed by strong hydrogen bonds with a basic framework built by R₂²(8) hydrogen bonds of either pure N—H...N or mixed patterns. Solvent molecules are aligned to the border of these chains via N—H...O hydrogen bonds. Two of the reported crystal structures containing 6CU show additional Cl...O halogen bonds, which connect the chains to two-dimensional layers, while one weak and one strong Cl...Cl interaction are observed in the two structures in which molecules of M6CU are present.

S1. Introduction

During the last years we have studied a number of cocrystals in which the components are held together by two or three hydrogen bonds (Tutughamiarso et al., 2012; Tutughamiarso & Egert, 2012; Ton & Egert, 2015a; Ton & Egert, 2015b; Hützler & Egert, 2015). The resulting patterns, of which some resemble the Watson-Crick base pairs adenine/thymine (or uracil) and guanine/cytosine, are simple models of molecular recognition, e.g. between a biologically active molecule and its receptor. We wondered if halogen-substituted coformers would give rise to extend patterns where, in addition to hydrogen bonds (HB), halogen bonds (XB) contribute significally to their stabilization.

XB, which are caused by the anisotropic distribution of electron density, have experienced a rising inter­est in various fields (metrangolo & Resnati, 2012; Metrangolo &Resnati, 2014), such as supra­molecular chemistry (Aakeröy et al., 2013; Sarwar et al., 2013), crystal engineering (Desiraju, 2013; Mukherjee et al., 2014), medicine (Heshmati et al., 2009), pharmaceutical chemistry (Baldrighi et al., 2013) and material sciences (Shin et al., 2014). Similar to HB, XB are non-covalent and highly directional inter­actions (Shields et al., 2010), wherein a covalently bonded halogen atom X inter­acts with a Lewis base or a second halogen atom (Troff et al., 2013; Desiraju et al., 2013). Their strength depends on the halogen-bond donor as well as on the type of halogen and ranges from 5 up to 180 kJ/mol (Metrangolo et al., 2007).

X···O contacts are of special inter­est in biological inter­actions (Auffinger et al., 2004; Parisini et al., 2011); for example, they have been shown to influence the binding selectivity and affinity in protein-ligand complexes (Hardegger et al., 2011). In crystal engineering, the combination of HB and XB is of increasing importance (Corradi et al., 2000; Saha et al., 2005) since they both obtain special geometrical properties and synthons, which are partially orthoghonal (Politzer et al., 2007; Aakeröy et al., 2011). However, the supra­molecular inter­actions based on HB and XB, especially single-point and multi-point inter­actions, are difficult to predict, therefore the development of new synthons is still a major task in crystal engineering (Aakeröy et al., 2011).

Due to their relevance as nucleobases and their role in important biological processes uracil derivatives are continually exposed to scientific investigations. For example, halogen-substituted uracil derivatives were examined as new inhibitors of the angiogenic actions of thymidine phospho­rylase and show significant better inhibitory characteristics compared with the corresponding methyl-substituted compounds (Klein et al., 2001). On the basis of these and related results, we have studied cocrystals of 6-chloro­uracil (6CU) and its derivative 6-chloro-3-methyl­uracil (M6CU) with several coformers. Since both uracil derivatives exhibit an ADA (A = acceptor and D = donor) hydrogen-bonding site with the the N—H group at position 1 as donor and the O and Cl atoms at positions 2 and 6 as acceptors (strong and weak, respectively), we chose coformers with complementary DAD sites and were successful with 2,4,6-tri­amino­pyrimidine (TAP) and three triazine derivatives [2,4,6-tri­amino-1,3,5-triazine (melamine, TAT), 2,4-di­amino-6-methyl-1,3,5-triazine (DMT) and 2-chloro-4,6-di­amino-1,3,5-triazine (CDT)] (Scheme 1).

S2. Experimental

S2.1. Crystallization

All experiments were performed with commercially available substances in various hydrous solvents and at various temperatures. Isothermal solvent evaporation experiments of 6CU with TAP in N-methyl­pyrrolidin-2-one (NMP) yielded cocrystal (I), which also contains NMP and H₂O, while experiments with TAT in NMP only led to a new pseudopolymorph of TAT with NMP and H₂O (II). Similar experiments with DMT in N,N- di­methyl­acetamide (DMAC) or N,N-di­methyl­formamide (DMF) yielded the cocrystal solvates (III) and (IV). Further experiments of 6CU with CDT in DMF led to the two DMF-containing cocrystals (Va) and (Vb). When M6CU was cocrystallized with iso­butyl 3,5-di­amino-4-chloro­benzoate in DMAC, a solvent-free crystal of M6CU (VI) was obtained, whereas cocrystallization experiments with TAT in DMAC under acidic conditions provided cocrystal (VII), which contains M6CU, TAT, DMAC, (CH₃)₂NH, and HCl. A detailled summary of the solvent evaporation experiments performed is presented in Table 10.

S2.2. Crystal Structure Analysis

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were initially located by difference Fourier synthesis. Subsequently, H atoms bonded to C atoms were refined using a riding model, with methyl C—H = 0.98 Å, secondary C—H = 0.99 Å and aromatic C—H = 0.95 Å, and U_iso(H) = 1.5 U_eq(C) for methyl H atoms or 1.2 U_eq(C) for the other H atoms, whereby ordered methyl groups were allowed to rotate about their local threefold axis. H atoms bonded to N atoms were refined isotropically with U_iso(H) = 1.2 U_eq(N), and with N—H distance restraints in (I), (Va), (Vb) and (VII). 1,2 and 1,3 distance restraints were applied for the H₂O molecules, as well as for the NMP solvent molecules in (I) and for the DMAC molecule in (VII).

In (I), one NMP molecule (X) is disordered across a pseudo-mirror plane, which passes approximately through atoms O2X and C5X with a site occupation factor of 0.816 (6) for the major occupied site, while this value amounts to 0.625 (19) for the disordered DMAC molecule in (VII). For the two positions of the disordered solvent molecule in (I), the 1,2 and 1,3 distances were restrained to be the same; also the dispacement parameters were constrained to the same values. In (VII), only the TAT molecule and one chloride ion occupy general positions, whereas the remaining atoms are located on a mirror plane or, in the case of the second chloride ion (Cl1D), on a twofold axis.

S3. Results

The crystal structures obtained from the various cocrystallization experiments exhibit repeatedly certain inter­action patterns which can be regarded as supra­molecular synthons (Desiraju, 1995). Especially important is the formation of two or three hydrogen bonds between the donor and acceptor groups of two molecules. If two HB are formed leading to an R₂²(8) pattern according to Bernstein et al. (1995), we will call this synthon 2 and distinguish if the pair of HB is formed between identical (2i) or different functional groups (2d). In order to clarify the participating donor/acceptor groups involved in synthon 2, they can be added in paranthesis [2i_D.A and 2d_D.A;D'A', respectively]. If three HB are formed there will either be a symmetric ADA-DAD (synthon 3s) or an unsymmetric AAD-DDA (synthon 3u) pattern (Fig. 1). The use of these synthons abbreviates the following discussion considerably.

S3.1. Co-crystallization experiments with 6-chloro­uracil

Cocrystallization attempts of 6CU with TAP in NMP yielded cocrystal (I) as a disolvate-monohydrate. The asymmetric unit of the triclinic crystal comprises one molecule of 6CU (A) deprotonated at N1A, one molecule of TAP (B) which is protonated at N3B, one H₂O molecule (W) and two planar NMP molecules (X, Y) (r.m.s. deviations for non-H atoms of X and Y = 0.044 and 0.021 Å, respectively), of which X is disordered (Fig. 2). 6CU and TAP are connected via synthon 2d_N.N;N.O (r.m.s. deviation for non-H atoms of 6CU and TAP = 0.040 Å). Furthermore, X is directly N—H···O hydrogen bonded to TAP, whereas Y is bridged to TAP via the H₂O molecule. In the crystal packing molecules of 6CU and TAP are connected to their respective inversion-symmetric equivalent via synthon 2i_N.O between 6CU and 2i_N.N inter­actions between TAP molecules (Fig. 3 and Table 2). Almost flat chains of alternating 6CU and TAP molecules, running parallel to (130), result in additional R₃²(8) and R₃²(10) HB inter­actions. In the first case two molecules of TAP are connected to one molecule of 6CU via one N—H···N and two N—H···O hydrogen bonds, and in the latter one two molecules of 6CU are linked with one molecule of TAP via three N—H···O hydrogen bonds. Additional O—H···O inter­actions from the water molecules connect chains which are situated on top of each other to a multi-storied two-dimensional network (Fig. 4).

The cocrystallization experiments of 6CU with TAT in DMAC yielded one cocrystal monosolvate of only minor quality (Gerhardt, 2014), wherein a proton transfer from 6CU to TAT, similar to that in (I), is observed. In the crystal, TAT molecules are connected to 6CU via synthon 2d_N.N;N.O hydrogen bonds forming chains. Attempts to cocrystallize 6CU with TAT in hydrous NMP we obtained the TAT-pseudopolymorph (II). (II) crystallizes in P2₁/n with one TAT molecule, two NMP (X, Y) molecules (r.m.s. deviations for non-H atoms of X and Y = 0.042 and 0.087 Å, respectively) and one H₂O (W) molecule in the asymmetric unit. The TAT molecule is bridged to the solvent molecule X via the H₂O molecule by one N—H···O and one O—H···O hydrogen bond, whereas the second NMP molecule (Y) is connected directly to TAT (Fig. 2). Synthon 2i_N.N patterns of TAT form almost planar chains (r.m.s. deviation for non-H atoms of TAT plus O1W = 0.041 Å) parallel to (101). These are strengthened by R₃²(8) inter­actions of TAT with the solvent molecule Y as well as with the water molecue, with two further N—H···O hydrogen bonds in each case (Fig. 5 and Table 3). Similar to (I), R₄²(8) O—H···O inter­actions of W with X connect the chains to two-dimensional layers (see supplementary material).

The cocrystallization of 6CU and DMT yielded two cocrystals, (III) and (IV). From DMAC we obtained the DMAC monosolvate of 6CU-DMT (III), which crystallizes in the triclinic space group P1 with one molecule of 6CU (A), DMT (B) and DMAC (X) within the asymmetric unit. Again a proton transfer from the 6CU to the DMT is observed. The resulting ions are connected by the planar synthon 3s (r.m.s. deviation for non-H atoms = 0.078 Å). One further N—H···O hydrogen bond links the solvent molecule with the DMT molecule, whereby X is oriented at an angle of 65.95 (5)° with respect to synthon 3s (Fig. 9). A one-dimensional framework of chains is built by alternating patterns of synthon 2d_N.N;N.O with synthon 3s parallel to (403); between these chains there are only van der Waals inter­actions (Fig. 6 and Table 4).

The second cocrystal, (IV), which is also triclinic, was obtained from DMF. The asymmetric unit of (IV) consists of one molecule of 6CU (A), DMT (B), DMF (X) and H₂O (W) each (Fig. 11). Similar to (I) and (III), a proton transfer from 6CU to DMT has taken place. As in (III), the planar synthon 3s (r.m.s. deviation for non-H atoms = 0.035 Å) is formed. The water molecule and the solvent molecule, which is located at an angle of 78.40 (14)° with respect to synthon 3s, are connected to 6CU and DMT, respectively, by one O—H···O and one N—H···O hydrogen bond. The crystal packing of (IV) shows chains parallel to (403) consisting of synthon 3s connected by 2d_N.N;N.O patterns. Additional R₄³(9) patterns including a very weak Cl···O inter­action between 6CU and water [d= 3.455 (4) Å] and three different (N,O)—H···(N,O) hydrogen bonds stabilize the chains further (Fig. 7 and Table 5). Two parallel chains, which are arranged one above the other, are connected by an additional O—H···O hydrogen bond from the water to the solvent molecule resulting in a two-dimensional network of tubes (Fig. 8).

During the cocrystallization experiments of 6CU with CDT in DMF at different temperatures two cocrystals, (Va) and (Vb), were formed as DMF monosolvates. At 277 K, compound (Va) crystallized in P1 with three coplanar molecules in the asymmetric unit, namely one 6CU (A), one CDT (B) and one DMF (X) molecule (r.m.s. deviation for all non-H atoms = 0.077 Å). Again synthon 3s is present, but unlike in (I), (III) and (IV) no proton transfer is observed. The solvent molecule is connected to 6CU by an R₂²(7) pattern with a strong N—H···O hydrogen bond and a weak C—H···O inter­action (Fig. 2). Chains parallel to (211) are built through two symmetry-independent synthon 2i_N.N patterns between CDT molecules solely. 6CU molecules are adjusted via synthon 3s in sort of a zig-zag arrangement to these chains, and the solvent molecules are oriented in an anti­parallel fashion. Due to this arrangement an R₄²(10) inter­action is formed by two inversion-symmetric Cl···O halogen bonds [d = 3.081 (2) Å] which fulfil the criteria of a halogen bond (Desiraju et al.,2013), extending the chains to two-dimensional layers (Fig. 9, and Table 6).

At 323 K, a second DMF monosolvate of 6CU-CDT, (Vb), was obtained. Compound (Vb) is also triclinic (P1), but comprises two molecules of 6CU (A and C), CDT (B and D) and DMF (X and Y), respectively, in the asymmetric unit (Fig. 2). Similar to (Va) the planar synthon 3s is formed between pairs of 6CU and CDT molecules (r.m.s. deviation for non-H atoms of A/B = 0.078 Å and C/D = 0.074 Å]. Also, R₂²(7) patterns with a strong N—H···O hydrogen bond and a weak C—H···O inter­action connect the solvent molecules to 6CU. The two 3s synthons are linked by a 2i_N.N pattern between the two independent CDT molecules, yielding chains parallel to (011) (Fig. 10 and Table 7). As in (Va), the 3s synthons within these chains are arranged in a zig-zag fashion, whereby the heterodimers (A/B and C/D) are related by a pseudo-2₁ screw axis parallel to the crystallograpic a axis. The parallel chains allow for Cl···O halogen bonds between Cl6A and O1Y [d = 3.031 (3) Å], thus forming relatively flat two-dimensional layers (r.m.s. deviation for all non-H atoms = 0.103 Å). In contrast to (Va), all solvent molecules within one layer are oriented in the same direction, but they are oriented oppositely in neighbouring layers, due to inversion centers located between them.

S3.2. Cocrystallization experiments with 6-chloro-3-methyl­uracil

During the cocrystallization experiments with 6CU we did not obtain cocrystals between 6CU and TAT with a good quality. After replacing 6CU with its 3-methyl derivative M6CU, we also used various coformers in various solvents at various temperatures. First we got a solvent-free structure of M6CU, (VI), but finally also the desired cocrystal with TAT, (VII).

The solvent-free structure crystallizes in the monoclinic space group P2₁/c with one planar molecule of M6CU (r.m.s. deviation for non-H atoms = 0.015 Å) in the asymmetric unit (Fig. 2). The crystal packing of (VI) is characterized by R₂²(8) patterns, with an N—H···O hydrogen bond supported by a weak C—H···O inter­action (synthon 2d_N.O;C.O), the translation of which leads to chains parallel to (102). These chains are further stabilized by Cl···Cl inter­actions [d = 3.353 (1) Å] between two inversion-symmetric chlorine atoms thus forming layers (Fig. 11, and Table 8).

The asymmetric unit of cocrystal (VII), which crystallizes in space group C2/m, contains five different entities: besides one molecule of M6CU (A), TAT (B) and DMAC (X), which had be expected, one molecule of (CH₃)₂NH (E), which had obviously been formed upon hydrolysis of DMAC, and two chloride ions (C and D) from HCl molecules, which have protonated the molecules of TAT and (CH₃)₂NH (Fig. 2). There are no synthon 3s heterodimers formed between the M6CU and TAT molecules, but the protonated TAT molecules are linked by synthon 2i_N.N to chains parallel to (001). These chains are further connected to two-dimensional layers via N—H···Cl hydrogen bonds (Fig. 12 and Table 9). An additional N—H···Cl hydrogen bond from the di­methyl­ammonium ion to the chloride ion Cl1C inter­links adjacent layers to a three-dimensional arrangement. The latter contains voids that are occupied by M6CU molecules, which are N—H···O hydrogen bonded to the DMAC molecules and form dimers via Cl···Cl inter­actions [d = 3.070 (4) Å] (Fig. 13).

S4. Discussion

In a Cambridge Structural Database (CSD, version 5.36 of November 2014, plus one update; Groom & Allen, 2014) search for melamine, which was restricted to organic compounds with known 3D coordinates and the exclusion of ions, 31 unique structures were found. One of the primary motifs within these structures is synthon 2i; it is present in 13 structures that form chains or dimers, either solely by melamine or with participation of the corresponding coformers, which are related to those observed in (II). Only four crystals contain synthon 2d connecting the melamine molecules with their coformer. Synthon 3s is also found in 15 structures but no predominant packing arrangement is observed therein. Inter­estingly, only the melamine-adipidic acid hydrate (CSD refcode: NUSHIT; Zhao et al., 2010) shows a 2i chain arrangement of melamine molecules and a three-dimensional network formed between the water molecules and the coformer, in a similar way to the inter­actions observed in (II).

A further CSD search for uracil (U), 6-methyl­uracil (6MU) and 6-chloro­uracil (6CU) yielded altogether seven structures, viz. one solvent-free structure of U (CSD refcode URACIL; Stewart & Jensen, 1967), one cocrystal of U with TAT (VIFKUR; Thomas & Kulkarni, 2007), two solvent-free structures of 6MU [(CEWVOP01 (Reck et al., 1988) and CEWVOP02 (Leonidow et al., 1993)], one structure of C5-substituted 6CU (NIYGIN; Al-Omary et al., 2014), one trihydrate cocrystal of 6CU with 4-(di­methyl­amino)­pyridine (QECNOB; Schmidt et al., 1999), and a structure of N1-substituted 6CU (VEXYUS, Ishikawa et al., 1990). URACIL crystallizes in space group P2₁/a; the packing shows two-dimensional layers, which are built by 2i_N.O and 2d_N.O;C.O patterns. Synthon 3s is observed in VIFKUR where each synthon is connected with its neighbour via 2i_N.N hydrogen bonds between two TAT molecules and via 2d_N.N;N.O hydrogen bonds between TAT and U, resulting in a three-dimensional network. Both solvent-free 6MU crystals contain 2i_(N.O) HB providing a two-dimensional network of dimers in CEWVOP01 and chains in CEWVOP02. Similar to (I), (III) and (IV), a proton transfer from 6CU to its counterpart 4-(2-meth­oxy­phenyl)­piperazine (MOP) is observed in NIYGIN. In this structure, chains are built by alternating 2i_N.O hydrogen bonds between 6CU molecules and R₄⁴(8) N—H···O inter­actions between 6CU and MOP. In QECNOB, again, 2i_N.O inter­actions connect deprotonated 6CU molecules; single N—H···O hydrogen bonds link 6CU molecules with their protonated counterpart 4-(di­methyl­amino)­pyridine to form tetra­mers. In VEXYUS, dimers are formed by 2i_N.O hydrogen bonds and, related to (Va) and (Vb), a Cl···O halogen bond expands those dimers to chains.

The structures (I)–(VII) are essentially dominated by hydrogen bonds, either by both synthon 2 types or synthon 3s patterns. In (VI) the packing is mainly stabilized by weak C—H···O inter­actions within the chains together with Cl···Cl inter­actions, which help to form two-dimensional layers, whereas only one N—H···O hydrogen bond is formed. In (I), (III), (IV) and (VI) synthon 2d is observed, as well as in the 6CU-TAT cocrystal monosolvate (Gerhardt, 2014). In contrast, synthon 2i is predominant in (II), (Va) and (Vb) and is also found in CEWVOP01, CEWVOP02, NIYGIN, QECNOB and VEXYUS. Only in URACIL both synthon 2 types are present for the main compounds. Five structures contain synthon 3s, viz. (III), (IV), (Va), (Vb) and VIFKUR. A proton transfer, which has taken place in the compounds (I), (III) and (IV) and the 6CU-TAT cocrystal monosolvate, is also present in NIYGIN.

In the crystal structures reported, chains are prevalent, either with alternating components, as in (I), (III) and (IV), or consisting of only one component, as in (Va) and (Vb); in (Va) an anti­parallel and in (Vb) a parallel arrangement of the solvent DMF molecules is displayed, which leads to different types of linkage in the packing. Surprisingly, a three-dimensional network is observed only in VIFKUR. In the structures CEWVOP02, NIYGIN, QECNOB and VEXYUS, there is a tendency of one-dimensional packing motifs, while only URACIL and CEWVOP01 show two-dimensional networks. In contrast to this trend, six of the structures reported by us show two-dimensional motifs, mainly in the form of layers [(II), (Va), (Vb) and (VI)], but tubes [(IV)] and stair-like [(I)] arrangements are also present.

In five structures [(IV), (Va), (Vb), (VI) and (VII)] the Cl atoms are involved in noticable inter­molecular inter­actions. In (IV) a very weak Cl···O contact between 6CU and the water molecule is observed, however, this inter­action seems only to support the packing, which is dominated by hydrogen bonds. In (VI) and (VII), on the other hand, Cl···Cl inter­actions are explicitly involved in the formation of layers [in (VI)] or dimers [in (VII)]. Similar characteristics to those observed in (VI) and (VII), but with Cl···O halogen bonds that act as linkers to form more complex packing motifs are found in (Va), (Vb) and VEXYUS.

In conclusion, our investigation showed that, for 6-chloro­uracil and 6-chloro-3-methyl­uracil in combination with several triazine and pyrimidine derivatives, distinct synthons are formed. Inter­molecular inter­actions of the Cl atoms are able to expand one-dimensional hydrogen-bonded networks to more complex packing motifs. These findings might help to design new two- and possibly three-dimensional networks of more complex molecules by using such synthons as building blocks.

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 (Version 3.1, Macrae et al., 2008) and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Synthons used for supramolecular patterns with two or three hydrogen bonds. In synthon 2 the D—H and D'—H bonds can be oriented either antiparallel (as shown above) or parallel.
	Fig. 2. The asymmetric units and atom numbering schemes of (I)-(VII). Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. In (I) and (VII), only the major occupied site of the disordered solvent molecule X is shown.
	Fig. 3. A partial packing diagram for (I). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. The minor occupied sites of the solvent molecule X are omitted. [symmetry codes: (i) -x + 1, -y, -z+2; (ii) -x + 1, -y, -z+1; (iii) x, y, z-1]
	Fig. 4. A partial packing diagram for (I), showing the two-dimensional networks parallel to (130). Dashed lines indicate hydrogen bonds.
	Fig. 5. A partial packing diagram for (II). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. [symmetry codes: (i) x + 1/2, -y + 1/2, z+1/2; (ii) x - 1/2, -y + 1/2, z-1/2]
	Fig. 6. A partial packing diagram for (III). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. [symmetry code: (i) x, y - 1, z]
	Fig. 7. A partial packing diagram for (IV). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds and solid lines represent halogen bonds. [symmetry codes: (i) x, y+1, z; (ii) -x + 1, -y + 1, -z+1; (iii) x, y - 1, z]
	Fig. 8. A partial packing diagram for (IV), showing the two-dimensional arrangement of tubes.
	Fig. 9. A partial packing diagram for (Va). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds and solid lines represent halogen bonds. [symmetry codes: (i) -x + 1, -y + 2, -z + 1; (ii) -x + 1, -y + 1, -z+2; (iii) -x, -y, -z + 1]
	Fig. 10. A partial packing diagram for (Vb). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds and solid lines represent halogen bonds. [symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z; (iii) x + 1, y + 1, z - 1]
	Fig. 11. A partial packing diagram for (VI). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds and solid lines represent halogen bonds. [symmetry codes: (i) x - 1, -y + 1/2, z - 1/2; (ii) x + 1, -y + 1/2, z + 1/2; (iii) -x, -y + 1, -z + 1]
	Fig. 12. A partial packing diagram for (VII) showing the layer built by melamine molecules and chloride ions. Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. [symmetry codes: (i) -x + 1/2, -y + 1/2, -z + 2; (ii) -x + 1/2, -y + 1/2, -z + 1; (iii) -x + 1, y, -z + 2]
	Fig. 13. A partial packing diagram for (VII) showing the M6CU homodimers and the dimethylammonium cations in between the melamine / chloride layers (see Fig. 12). Only hydrogen atoms which participate in hydrogen bonds are shown. Dashed lines indicate hydrogen bonds. Halogen bonds are emphasized by solid lines. [symmetry code: (iv) -x + 1, -y, -z]

(I)

Crystal data

C4H3ClN2O2·C4H7N5·2(C5H9NO)·H2O	Z = 2
Mr = 487.96	F(000) = 516
Triclinic, P1	Dx = 1.381 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4450 (6) Å	Cell parameters from 26327 reflections
b = 10.3974 (7) Å	θ = 4.2–25.9°
c = 13.3661 (8) Å	µ = 0.21 mm^−1
α = 77.188 (5)°	T = 173 K
β = 89.846 (5)°	Block, colourless
γ = 67.043 (5)°	0.63 × 0.18 × 0.13 mm
V = 1173.40 (13) Å^3

Data collection

STOE IPDS II two-circle diffractometer	4521 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	3965 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.050
ω scans	θmax = 25.9°, θmin = 3.4°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −11→11
Tmin = 0.879, Tmax = 0.972	k = −12→12
23834 measured reflections	l = −16→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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.244	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0843P)^2 + 4.5246P] where P = (Fo^2 + 2Fc^2)/3
4521 reflections	(Δ/σ)max < 0.001
350 parameters	Δρmax = 1.27 e Å^−3
102 restraints	Δρmin = −0.53 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	0.1098 (4)	0.1306 (4)	0.9239 (3)	0.0263 (7)
C2A	0.2646 (5)	0.0755 (4)	0.9510 (3)	0.0259 (8)
O2A	0.3610 (3)	0.0410 (3)	0.8867 (2)	0.0308 (7)
N3A	0.3144 (4)	0.0601 (4)	1.0506 (2)	0.0249 (7)
H3A	0.413 (3)	0.028 (5)	1.069 (4)	0.030*
C4A	0.2210 (5)	0.0921 (5)	1.1284 (3)	0.0295 (9)
O4A	0.2817 (3)	0.0728 (4)	1.2150 (2)	0.0391 (8)
C5A	0.0601 (5)	0.1465 (5)	1.0990 (3)	0.0296 (9)
H5A	−0.0148	0.1713	1.1467	0.036*
C6A	0.0200 (4)	0.1612 (4)	0.9977 (3)	0.0259 (8)
Cl6A	−0.17873 (11)	0.23212 (12)	0.95603 (8)	0.0334 (3)
N1B	0.2802 (4)	0.0736 (4)	0.5073 (2)	0.0253 (7)
C2B	0.3235 (4)	0.0573 (4)	0.6055 (3)	0.0240 (8)
N2B	0.4720 (4)	0.0062 (5)	0.6369 (3)	0.0333 (8)
H21B	0.507 (6)	−0.004 (6)	0.701 (2)	0.040*
H22B	0.540 (5)	−0.017 (5)	0.592 (3)	0.040*
N3B	0.2197 (4)	0.0894 (4)	0.6766 (3)	0.0257 (7)
H3B	0.258 (6)	0.073 (5)	0.734 (4)	0.031*
C4B	0.0647 (4)	0.1359 (4)	0.6500 (3)	0.0267 (8)
N4B	−0.0281 (4)	0.1631 (5)	0.7249 (3)	0.0386 (9)
H41B	−0.002 (5)	0.154 (6)	0.7884 (19)	0.046*
H42B	−0.127 (2)	0.194 (6)	0.713 (3)	0.046*
C5B	0.0162 (5)	0.1534 (5)	0.5497 (3)	0.0287 (9)
H5B	−0.0905	0.1866	0.5282	0.034*
C6B	0.1272 (4)	0.1212 (4)	0.4794 (3)	0.0244 (8)
N6B	0.0859 (4)	0.1381 (4)	0.3798 (3)	0.0320 (8)
H61B	0.158 (4)	0.117 (5)	0.338 (3)	0.038*
H62B	−0.003 (3)	0.173 (5)	0.347 (3)	0.038*
O1W	−0.3421 (4)	0.2228 (5)	0.6820 (4)	0.0656 (12)
H2W	−0.352 (8)	0.149 (4)	0.716 (6)	0.098*
H1W	−0.414 (6)	0.300 (4)	0.685 (6)	0.098*
O2X	−0.2254 (5)	0.2456 (8)	0.2848 (4)	0.0427 (13)	0.816 (6)
N1X	−0.4882 (5)	0.3345 (5)	0.2501 (4)	0.0387 (11)	0.816 (6)
C1X	−0.4877 (9)	0.3138 (9)	0.1477 (5)	0.0521 (17)	0.816 (6)
H1X1	−0.5943	0.3513	0.1167	0.078*	0.408 (3)
H1X2	−0.4369	0.2109	0.1500	0.078*	0.408 (3)
H1X3	−0.4316	0.3650	0.1061	0.078*	0.408 (3)
H1X4	−0.3809	0.2668	0.1319	0.078*	0.408 (3)
H1X5	−0.5383	0.4073	0.0985	0.078*	0.408 (3)
H1X6	−0.5436	0.2531	0.1425	0.078*	0.408 (3)
C2X	−0.3594 (6)	0.2952 (7)	0.3125 (4)	0.0364 (13)	0.816 (6)
C3X	−0.4070 (8)	0.3216 (8)	0.4163 (5)	0.0459 (14)	0.816 (6)
H3X1	−0.3610	0.3833	0.4375	0.055*	0.816 (6)
H3X2	−0.3729	0.2295	0.4692	0.055*	0.816 (6)
C4X	−0.5823 (8)	0.3964 (9)	0.4036 (6)	0.0597 (17)	0.816 (6)
H4X1	−0.6280	0.3479	0.4583	0.072*	0.816 (6)
H4X2	−0.6163	0.4983	0.4064	0.072*	0.816 (6)
C5X	−0.6292 (7)	0.3851 (14)	0.2982 (6)	0.0491 (16)	0.816 (6)
H5X1	−0.6797	0.3165	0.3052	0.059*	0.816 (6)
H5X2	−0.7016	0.4801	0.2571	0.059*	0.816 (6)
O2X'	−0.2292 (19)	0.231 (5)	0.3165 (19)	0.0427 (13)	0.184 (6)
N1X'	−0.4899 (18)	0.331 (2)	0.3294 (12)	0.0387 (11)	0.184 (6)
C1X'	−0.484 (3)	0.330 (4)	0.4367 (15)	0.0521 (17)	0.184 (6)
H1X7	−0.5886	0.3638	0.4581	0.078*	0.092 (3)
H1X8	−0.4344	0.3933	0.4482	0.078*	0.092 (3)
H1X9	−0.4234	0.2316	0.4771	0.078*	0.092 (3)
H1XX	−0.3757	0.2954	0.4642	0.078*	0.092 (3)
H1XY	−0.5299	0.2659	0.4740	0.078*	0.092 (3)
H1XZ	−0.5409	0.4275	0.4452	0.078*	0.092 (3)
C2X'	−0.3661 (17)	0.285 (4)	0.2766 (15)	0.0364 (13)	0.184 (6)
C3X'	−0.422 (3)	0.292 (4)	0.1689 (15)	0.0459 (14)	0.184 (6)
H3X3	−0.3799	0.1952	0.1551	0.055*	0.184 (6)
H3X4	−0.3878	0.3561	0.1173	0.055*	0.184 (6)
C4X'	−0.597 (3)	0.352 (4)	0.1645 (17)	0.0597 (17)	0.184 (6)
H4X3	−0.6439	0.4401	0.1084	0.072*	0.184 (6)
H4X4	−0.6356	0.2799	0.1528	0.072*	0.184 (6)
C5X'	−0.6353 (18)	0.385 (7)	0.269 (2)	0.0491 (16)	0.184 (6)
H5X3	−0.6898	0.4900	0.2611	0.059*	0.184 (6)
H5X4	−0.7019	0.3372	0.3013	0.059*	0.184 (6)
N1Y	−0.8861 (7)	0.4619 (6)	0.7251 (5)	0.0778 (17)
C1Y	−0.9714 (10)	0.4862 (9)	0.6341 (6)	0.088 (2)
H1Y1	−1.0817	0.5290	0.6433	0.132*
H1Y2	−0.9469	0.3949	0.6147	0.132*
H1Y3	−0.9463	0.5522	0.5797	0.132*
C2Y	−0.7319 (6)	0.4054 (6)	0.7362 (6)	0.072 (2)
O2Y	−0.6521 (6)	0.3656 (6)	0.6661 (5)	0.0887 (16)
C3Y	−0.6762 (10)	0.3906 (7)	0.8402 (6)	0.083 (2)
H3Y1	−0.6060	0.4407	0.8401	0.100*
H3Y2	−0.6192	0.2878	0.8749	0.100*
C4Y	−0.8173 (7)	0.4579 (7)	0.8956 (7)	0.080 (2)
H4Y1	−0.8169	0.5443	0.9149	0.096*
H4Y2	−0.8204	0.3884	0.9587	0.096*
C5Y	−0.9592 (7)	0.4993 (7)	0.8154 (5)	0.0645 (17)
H5Y1	−1.0219	0.4433	0.8400	0.077*
H5Y2	−1.0259	0.6032	0.8015	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0200 (16)	0.0351 (18)	0.0223 (16)	−0.0084 (14)	−0.0010 (13)	−0.0085 (14)
C2A	0.030 (2)	0.030 (2)	0.0195 (18)	−0.0132 (17)	0.0015 (15)	−0.0074 (15)
O2A	0.0227 (14)	0.0488 (18)	0.0223 (14)	−0.0128 (13)	0.0056 (11)	−0.0144 (13)
N3A	0.0156 (15)	0.0358 (18)	0.0216 (16)	−0.0072 (14)	−0.0010 (12)	−0.0091 (14)
C4A	0.027 (2)	0.039 (2)	0.022 (2)	−0.0113 (18)	0.0032 (16)	−0.0092 (17)
O4A	0.0283 (16)	0.066 (2)	0.0202 (15)	−0.0129 (15)	0.0046 (12)	−0.0159 (14)
C5A	0.025 (2)	0.037 (2)	0.025 (2)	−0.0090 (17)	0.0064 (16)	−0.0107 (17)
C6A	0.0186 (18)	0.031 (2)	0.028 (2)	−0.0095 (16)	0.0009 (15)	−0.0061 (16)
Cl6A	0.0200 (5)	0.0469 (6)	0.0285 (5)	−0.0079 (4)	−0.0005 (4)	−0.0098 (4)
N1B	0.0229 (16)	0.0352 (18)	0.0181 (16)	−0.0108 (14)	0.0011 (12)	−0.0082 (13)
C2B	0.0211 (19)	0.0273 (19)	0.0232 (19)	−0.0097 (15)	−0.0024 (15)	−0.0054 (15)
N2B	0.0191 (17)	0.057 (2)	0.0207 (17)	−0.0098 (16)	−0.0009 (13)	−0.0126 (16)
N3B	0.0254 (17)	0.0366 (19)	0.0167 (16)	−0.0131 (15)	−0.0002 (13)	−0.0079 (14)
C4B	0.0225 (19)	0.033 (2)	0.025 (2)	−0.0106 (16)	0.0037 (15)	−0.0075 (16)
N4B	0.0244 (18)	0.071 (3)	0.0219 (18)	−0.0183 (19)	0.0038 (14)	−0.0162 (18)
C5B	0.0210 (19)	0.043 (2)	0.0216 (19)	−0.0111 (17)	0.0016 (15)	−0.0095 (17)
C6B	0.0222 (19)	0.030 (2)	0.0198 (18)	−0.0092 (16)	−0.0010 (14)	−0.0053 (15)
N6B	0.0255 (18)	0.048 (2)	0.0189 (17)	−0.0110 (16)	0.0002 (13)	−0.0092 (15)
O1W	0.032 (2)	0.076 (3)	0.079 (3)	−0.019 (2)	−0.0037 (19)	−0.003 (3)
O2X	0.0283 (18)	0.051 (3)	0.040 (3)	−0.0108 (16)	−0.0014 (19)	−0.005 (3)
N1X	0.026 (2)	0.047 (3)	0.042 (2)	−0.0135 (19)	0.0006 (19)	−0.010 (2)
C1X	0.044 (4)	0.068 (4)	0.046 (4)	−0.021 (4)	0.003 (3)	−0.021 (3)
C2X	0.036 (3)	0.037 (3)	0.035 (3)	−0.015 (2)	−0.004 (2)	−0.004 (3)
C3X	0.044 (3)	0.053 (3)	0.041 (3)	−0.019 (3)	−0.001 (3)	−0.012 (3)
C4X	0.049 (4)	0.070 (4)	0.053 (4)	−0.016 (3)	0.009 (3)	−0.017 (3)
C5X	0.032 (2)	0.055 (3)	0.056 (4)	−0.013 (2)	0.005 (3)	−0.012 (4)
O2X'	0.0283 (18)	0.051 (3)	0.040 (3)	−0.0108 (16)	−0.0014 (19)	−0.005 (3)
N1X'	0.026 (2)	0.047 (3)	0.042 (2)	−0.0135 (19)	0.0006 (19)	−0.010 (2)
C1X'	0.044 (4)	0.068 (4)	0.046 (4)	−0.021 (4)	0.003 (3)	−0.021 (3)
C2X'	0.036 (3)	0.037 (3)	0.035 (3)	−0.015 (2)	−0.004 (2)	−0.004 (3)
C3X'	0.044 (3)	0.053 (3)	0.041 (3)	−0.019 (3)	−0.001 (3)	−0.012 (3)
C4X'	0.049 (4)	0.070 (4)	0.053 (4)	−0.016 (3)	0.009 (3)	−0.017 (3)
C5X'	0.032 (2)	0.055 (3)	0.056 (4)	−0.013 (2)	0.005 (3)	−0.012 (4)
N1Y	0.084 (4)	0.062 (3)	0.099 (5)	−0.037 (3)	0.014 (4)	−0.026 (3)
C1Y	0.081 (5)	0.081 (5)	0.101 (6)	−0.024 (4)	0.003 (5)	−0.032 (5)
C2Y	0.040 (3)	0.041 (3)	0.122 (6)	−0.006 (3)	0.038 (4)	−0.012 (4)
O2Y	0.063 (3)	0.093 (4)	0.099 (4)	−0.018 (3)	0.007 (3)	−0.024 (3)
C3Y	0.118 (7)	0.044 (4)	0.097 (6)	−0.044 (4)	0.004 (5)	−0.015 (4)
C4Y	0.054 (4)	0.048 (3)	0.139 (7)	−0.021 (3)	0.010 (4)	−0.024 (4)
C5Y	0.058 (4)	0.048 (3)	0.080 (5)	−0.018 (3)	0.017 (3)	−0.007 (3)

Geometric parameters (Å, º)

N1A—C6A	1.310 (5)	C3X—H3X1	0.9900
N1A—C2A	1.362 (5)	C3X—H3X2	0.9900
C2A—O2A	1.255 (5)	C4X—C5X	1.520 (9)
C2A—N3A	1.367 (5)	C4X—H4X1	0.9900
N3A—C4A	1.375 (5)	C4X—H4X2	0.9900
N3A—H3A	0.869 (19)	C5X—H5X1	0.9900
C4A—O4A	1.233 (5)	C5X—H5X2	0.9900
C4A—C5A	1.420 (6)	O2X'—C2X'	1.256 (10)
C5A—C6A	1.366 (6)	N1X'—C2X'	1.341 (10)
C5A—H5A	0.9500	N1X'—C1X'	1.433 (11)
C6A—Cl6A	1.766 (4)	N1X'—C5X'	1.437 (11)
N1B—C2B	1.331 (5)	C1X'—H1X7	0.9800
N1B—C6B	1.355 (5)	C1X'—H1X8	0.9800
C2B—N2B	1.322 (5)	C1X'—H1X9	0.9800
C2B—N3B	1.362 (5)	C1X'—H1XX	0.9800
N2B—H21B	0.88 (2)	C1X'—H1XY	0.9800
N2B—H22B	0.88 (2)	C1X'—H1XZ	0.9800
N3B—C4B	1.371 (5)	C2X'—C3X'	1.510 (12)
N3B—H3B	0.80 (5)	C3X'—C4X'	1.523 (13)
C4B—N4B	1.333 (5)	C3X'—H3X3	0.9900
C4B—C5B	1.368 (6)	C3X'—H3X4	0.9900
N4B—H41B	0.860 (19)	C4X'—C5X'	1.516 (14)
N4B—H42B	0.865 (19)	C4X'—H4X3	0.9900
C5B—C6B	1.398 (6)	C4X'—H4X4	0.9900
C5B—H5B	0.9500	C5X'—H5X3	0.9900
C6B—N6B	1.342 (5)	C5X'—H5X4	0.9900
N6B—H61B	0.870 (19)	N1Y—C2Y	1.335 (7)
N6B—H62B	0.853 (19)	N1Y—C1Y	1.379 (7)
O1W—H2W	0.838 (10)	N1Y—C5Y	1.442 (7)
O1W—H1W	0.837 (10)	C1Y—H1Y1	0.9800
O2X—C2X	1.256 (6)	C1Y—H1Y2	0.9800
N1X—C2X	1.345 (6)	C1Y—H1Y3	0.9800
N1X—C1X	1.432 (8)	C2Y—O2Y	1.242 (8)
N1X—C5X	1.436 (7)	C2Y—C3Y	1.442 (10)
C1X—H1X1	0.9800	C3Y—C4Y	1.520 (10)
C1X—H1X2	0.9800	C3Y—H3Y1	0.9900
C1X—H1X3	0.9800	C3Y—H3Y2	0.9900
C1X—H1X4	0.9800	C4Y—C5Y	1.577 (9)
C1X—H1X5	0.9800	C4Y—H4Y1	0.9900
C1X—H1X6	0.9800	C4Y—H4Y2	0.9900
C2X—C3X	1.508 (8)	C5Y—H5Y1	0.9900
C3X—C4X	1.521 (9)	C5Y—H5Y2	0.9900
C6A—N1A—C2A	116.3 (3)	N1X—C5X—C4X	105.5 (5)
O2A—C2A—N1A	121.6 (4)	N1X—C5X—H5X1	110.6
O2A—C2A—N3A	119.9 (4)	C4X—C5X—H5X1	110.6
N1A—C2A—N3A	118.5 (3)	N1X—C5X—H5X2	110.6
C2A—N3A—C4A	125.5 (3)	C4X—C5X—H5X2	110.6
C2A—N3A—H3A	120 (3)	H5X1—C5X—H5X2	108.8
C4A—N3A—H3A	115 (3)	C2X'—N1X'—C1X'	124.8 (13)
O4A—C4A—N3A	118.6 (4)	C2X'—N1X'—C5X'	114.2 (10)
O4A—C4A—C5A	126.3 (4)	C1X'—N1X'—C5X'	121.0 (13)
N3A—C4A—C5A	115.1 (3)	N1X'—C1X'—H1X7	109.5
C6A—C5A—C4A	115.7 (4)	N1X'—C1X'—H1X8	109.5
C6A—C5A—H5A	122.1	H1X7—C1X'—H1X8	109.5
C4A—C5A—H5A	122.1	N1X'—C1X'—H1X9	109.5
N1A—C6A—C5A	128.8 (4)	H1X7—C1X'—H1X9	109.5
N1A—C6A—Cl6A	113.4 (3)	H1X8—C1X'—H1X9	109.5
C5A—C6A—Cl6A	117.8 (3)	N1X'—C1X'—H1XX	109.5
C2B—N1B—C6B	117.7 (3)	H1X7—C1X'—H1XX	141.1
N2B—C2B—N1B	119.7 (4)	H1X8—C1X'—H1XX	56.3
N2B—C2B—N3B	118.1 (4)	H1X9—C1X'—H1XX	56.3
N1B—C2B—N3B	122.2 (3)	N1X'—C1X'—H1XY	109.5
C2B—N2B—H21B	123 (3)	H1X7—C1X'—H1XY	56.3
C2B—N2B—H22B	119 (4)	H1X8—C1X'—H1XY	141.1
H21B—N2B—H22B	118 (5)	H1X9—C1X'—H1XY	56.3
C2B—N3B—C4B	120.8 (3)	H1XX—C1X'—H1XY	109.5
C2B—N3B—H3B	114 (4)	N1X'—C1X'—H1XZ	109.5
C4B—N3B—H3B	125 (4)	H1X7—C1X'—H1XZ	56.3
N4B—C4B—C5B	124.9 (4)	H1X8—C1X'—H1XZ	56.3
N4B—C4B—N3B	116.6 (4)	H1X9—C1X'—H1XZ	141.1
C5B—C4B—N3B	118.4 (4)	H1XX—C1X'—H1XZ	109.5
C4B—N4B—H41B	127 (3)	H1XY—C1X'—H1XZ	109.5
C4B—N4B—H42B	121 (3)	O2X'—C2X'—N1X'	123.9 (14)
H41B—N4B—H42B	112 (3)	O2X'—C2X'—C3X'	127.3 (15)
C4B—C5B—C6B	118.5 (4)	N1X'—C2X'—C3X'	108.3 (9)
C4B—C5B—H5B	120.8	C2X'—C3X'—C4X'	106.0 (9)
C6B—C5B—H5B	120.8	C2X'—C3X'—H3X3	110.5
N6B—C6B—N1B	116.7 (4)	C4X'—C3X'—H3X3	110.5
N6B—C6B—C5B	121.0 (4)	C2X'—C3X'—H3X4	110.5
N1B—C6B—C5B	122.3 (3)	C4X'—C3X'—H3X4	110.5
C6B—N6B—H61B	119 (3)	H3X3—C3X'—H3X4	108.7
C6B—N6B—H62B	130 (3)	C5X'—C4X'—C3X'	105.0 (10)
H61B—N6B—H62B	111 (3)	C5X'—C4X'—H4X3	110.7
H2W—O1W—H1W	115 (3)	C3X'—C4X'—H4X3	110.7
C2X—N1X—C1X	123.8 (5)	C5X'—C4X'—H4X4	110.7
C2X—N1X—C5X	114.4 (5)	C3X'—C4X'—H4X4	110.7
C1X—N1X—C5X	121.4 (5)	H4X3—C4X'—H4X4	108.8
N1X—C1X—H1X1	109.5	N1X'—C5X'—C4X'	105.9 (10)
N1X—C1X—H1X2	109.5	N1X'—C5X'—H5X3	110.6
H1X1—C1X—H1X2	109.5	C4X'—C5X'—H5X3	110.6
N1X—C1X—H1X3	109.5	N1X'—C5X'—H5X4	110.6
H1X1—C1X—H1X3	109.5	C4X'—C5X'—H5X4	110.6
H1X2—C1X—H1X3	109.5	H5X3—C5X'—H5X4	108.7
N1X—C1X—H1X4	109.5	C2Y—N1Y—C1Y	123.4 (7)
H1X1—C1X—H1X4	141.1	C2Y—N1Y—C5Y	115.1 (6)
H1X2—C1X—H1X4	56.3	C1Y—N1Y—C5Y	121.5 (6)
H1X3—C1X—H1X4	56.3	N1Y—C1Y—H1Y1	109.5
N1X—C1X—H1X5	109.5	N1Y—C1Y—H1Y2	109.5
H1X1—C1X—H1X5	56.3	H1Y1—C1Y—H1Y2	109.5
H1X2—C1X—H1X5	141.1	N1Y—C1Y—H1Y3	109.5
H1X3—C1X—H1X5	56.3	H1Y1—C1Y—H1Y3	109.5
H1X4—C1X—H1X5	109.5	H1Y2—C1Y—H1Y3	109.5
N1X—C1X—H1X6	109.5	O2Y—C2Y—N1Y	122.8 (8)
H1X1—C1X—H1X6	56.3	O2Y—C2Y—C3Y	126.6 (6)
H1X2—C1X—H1X6	56.3	N1Y—C2Y—C3Y	110.5 (6)
H1X3—C1X—H1X6	141.1	C2Y—C3Y—C4Y	106.7 (7)
H1X4—C1X—H1X6	109.5	C2Y—C3Y—H3Y1	110.4
H1X5—C1X—H1X6	109.5	C4Y—C3Y—H3Y1	110.4
O2X—C2X—N1X	123.6 (6)	C2Y—C3Y—H3Y2	110.4
O2X—C2X—C3X	128.3 (5)	C4Y—C3Y—H3Y2	110.4
N1X—C2X—C3X	108.0 (5)	H3Y1—C3Y—H3Y2	108.6
C2X—C3X—C4X	106.0 (5)	C3Y—C4Y—C5Y	104.7 (6)
C2X—C3X—H3X1	110.5	C3Y—C4Y—H4Y1	110.8
C4X—C3X—H3X1	110.5	C5Y—C4Y—H4Y1	110.8
C2X—C3X—H3X2	110.5	C3Y—C4Y—H4Y2	110.8
C4X—C3X—H3X2	110.5	C5Y—C4Y—H4Y2	110.8
H3X1—C3X—H3X2	108.7	H4Y1—C4Y—H4Y2	108.9
C5X—C4X—C3X	104.8 (5)	N1Y—C5Y—C4Y	102.7 (5)
C5X—C4X—H4X1	110.8	N1Y—C5Y—H5Y1	111.2
C3X—C4X—H4X1	110.8	C4Y—C5Y—H5Y1	111.2
C5X—C4X—H4X2	110.8	N1Y—C5Y—H5Y2	111.2
C3X—C4X—H4X2	110.8	C4Y—C5Y—H5Y2	111.2
H4X1—C4X—H4X2	108.9	H5Y1—C5Y—H5Y2	109.1
C6A—N1A—C2A—O2A	179.2 (4)	C5X—N1X—C2X—C3X	−1.4 (9)
C6A—N1A—C2A—N3A	−1.8 (6)	O2X—C2X—C3X—C4X	174.3 (8)
O2A—C2A—N3A—C4A	−179.1 (4)	N1X—C2X—C3X—C4X	−5.7 (8)
N1A—C2A—N3A—C4A	1.9 (6)	C2X—C3X—C4X—C5X	10.0 (9)
C2A—N3A—C4A—O4A	180.0 (4)	C2X—N1X—C5X—C4X	7.9 (11)
C2A—N3A—C4A—C5A	−0.6 (6)	C1X—N1X—C5X—C4X	−178.6 (7)
O4A—C4A—C5A—C6A	178.7 (5)	C3X—C4X—C5X—N1X	−10.7 (11)
N3A—C4A—C5A—C6A	−0.6 (6)	C1X'—N1X'—C2X'—O2X'	3 (6)
C2A—N1A—C6A—C5A	0.6 (7)	C5X'—N1X'—C2X'—O2X'	−178 (5)
C2A—N1A—C6A—Cl6A	180.0 (3)	C1X'—N1X'—C2X'—C3X'	175 (3)
C4A—C5A—C6A—N1A	0.7 (7)	C5X'—N1X'—C2X'—C3X'	−6 (5)
C4A—C5A—C6A—Cl6A	−178.7 (3)	O2X'—C2X'—C3X'—C4X'	173 (4)
C6B—N1B—C2B—N2B	177.6 (4)	N1X'—C2X'—C3X'—C4X'	1 (4)
C6B—N1B—C2B—N3B	−1.3 (6)	C2X'—C3X'—C4X'—C5X'	3 (5)
N2B—C2B—N3B—C4B	−176.7 (4)	C2X'—N1X'—C5X'—C4X'	8 (6)
N1B—C2B—N3B—C4B	2.2 (6)	C1X'—N1X'—C5X'—C4X'	−173 (3)
C2B—N3B—C4B—N4B	179.2 (4)	C3X'—C4X'—C5X'—N1X'	−6 (5)
C2B—N3B—C4B—C5B	−1.9 (6)	C1Y—N1Y—C2Y—O2Y	−2.5 (11)
N4B—C4B—C5B—C6B	179.6 (4)	C5Y—N1Y—C2Y—O2Y	178.8 (6)
N3B—C4B—C5B—C6B	0.9 (6)	C1Y—N1Y—C2Y—C3Y	−178.9 (7)
C2B—N1B—C6B—N6B	179.4 (4)	C5Y—N1Y—C2Y—C3Y	2.3 (8)
C2B—N1B—C6B—C5B	0.2 (6)	O2Y—C2Y—C3Y—C4Y	179.0 (7)
C4B—C5B—C6B—N6B	−179.2 (4)	N1Y—C2Y—C3Y—C4Y	−4.7 (7)
C4B—C5B—C6B—N1B	0.0 (6)	C2Y—C3Y—C4Y—C5Y	5.1 (7)
C1X—N1X—C2X—O2X	5.2 (11)	C2Y—N1Y—C5Y—C4Y	1.0 (7)
C5X—N1X—C2X—O2X	178.6 (9)	C1Y—N1Y—C5Y—C4Y	−177.7 (6)
C1X—N1X—C2X—C3X	−174.8 (6)	C3Y—C4Y—C5Y—N1Y	−3.7 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3A···O2A^i	0.87 (2)	2.02 (2)	2.884 (4)	178 (5)
N2B—H21B···O4A^i	0.88 (2)	2.08 (4)	2.796 (5)	138 (5)
N2B—H22B···N1B^ii	0.88 (2)	2.13 (2)	3.008 (5)	175 (5)
N3B—H3B···O2A	0.80 (5)	2.17 (5)	2.964 (4)	177 (5)
N4B—H41B···N1A	0.86 (2)	2.01 (2)	2.857 (5)	166 (4)
N4B—H42B···O1W	0.87 (2)	1.96 (2)	2.815 (5)	168 (5)
N6B—H61B···O4A^iii	0.87 (2)	2.05 (2)	2.898 (5)	165 (4)
N6B—H62B···O2X	0.85 (2)	2.04 (2)	2.887 (6)	173 (4)
O1W—H1W···O2Y	0.84 (1)	2.08 (6)	2.701 (6)	131 (7)
O1W—H2W···O4A^iv	0.84 (1)	2.12 (3)	2.903 (6)	156 (6)

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

(II) ;

Crystal data

C3H6N6·2(C5H9NO)·H2O	F(000) = 736
Mr = 342.42	Dx = 1.309 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 42744 reflections
a = 7.6291 (4) Å	θ = 2.9–26.4°
b = 21.0118 (8) Å	µ = 0.10 mm^−1
c = 10.9690 (6) Å	T = 173 K
β = 98.950 (4)°	Plate, colourless
V = 1736.93 (15) Å^3	0.32 × 0.20 × 0.07 mm
Z = 4

Data collection

STOE IPDS II two-circle diffractometer	3394 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	2914 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.058
ω scans	θmax = 26.0°, θmin = 3.0°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −9→9
Tmin = 0.970, Tmax = 0.993	k = −25→25
50506 measured reflections	l = −13→13

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) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 0.8452P] where P = (Fo^2 + 2Fc^2)/3
3394 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.18 e Å^−3
3 restraints	Δρmin = −0.18 e Å^−3

Special details

Experimental. ;

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	0.57216 (18)	0.23511 (6)	0.32536 (12)	0.0253 (3)
C2	0.5679 (2)	0.29920 (7)	0.31483 (15)	0.0242 (3)
N2	0.6625 (2)	0.33208 (7)	0.40692 (14)	0.0302 (3)
H21	0.723 (3)	0.3118 (10)	0.471 (2)	0.036*
H22	0.663 (3)	0.3720 (11)	0.4023 (19)	0.036*
N3	0.47915 (18)	0.33242 (6)	0.22077 (12)	0.0264 (3)
C4	0.3856 (2)	0.29598 (7)	0.13273 (15)	0.0245 (3)
N4	0.2952 (2)	0.32570 (7)	0.03575 (14)	0.0338 (4)
H41	0.237 (3)	0.3030 (10)	−0.027 (2)	0.041*
H42	0.299 (3)	0.3676 (11)	0.0322 (19)	0.041*
N5	0.37670 (18)	0.23186 (6)	0.13293 (12)	0.0252 (3)
C6	0.4748 (2)	0.20421 (7)	0.23057 (14)	0.0234 (3)
N6	0.4749 (2)	0.14032 (7)	0.23526 (14)	0.0303 (3)
H61	0.420 (3)	0.1182 (10)	0.168 (2)	0.036*
H62	0.549 (3)	0.1209 (10)	0.292 (2)	0.036*
O1W	0.82290 (19)	0.44772 (6)	0.52417 (13)	0.0388 (3)
H1W1	0.817 (3)	0.4877 (5)	0.534 (2)	0.058*
H1W2	0.916 (2)	0.4418 (10)	0.492 (2)	0.058*
N1X	0.7549 (2)	0.67951 (7)	0.49912 (14)	0.0335 (3)
C1X	0.8635 (3)	0.71339 (9)	0.59756 (19)	0.0403 (4)
H1X1	0.9330	0.6829	0.6529	0.060*
H1X2	0.7874	0.7382	0.6439	0.060*
H1X3	0.9440	0.7421	0.5627	0.060*
C2X	0.7504 (2)	0.61649 (8)	0.48894 (17)	0.0321 (4)
O2X	0.84431 (18)	0.57929 (6)	0.55929 (13)	0.0415 (3)
C3X	0.6158 (3)	0.59790 (9)	0.38030 (19)	0.0405 (4)
H3X1	0.5146	0.5755	0.4077	0.049*
H3X2	0.6696	0.5696	0.3241	0.049*
C4X	0.5551 (3)	0.66021 (10)	0.3161 (2)	0.0452 (5)
H4X1	0.4240	0.6631	0.3020	0.054*
H4X2	0.5980	0.6635	0.2357	0.054*
C5X	0.6357 (3)	0.71267 (9)	0.40343 (19)	0.0392 (4)
H5X1	0.7017	0.7436	0.3597	0.047*
H5X2	0.5423	0.7356	0.4391	0.047*
N1Y	0.7454 (2)	−0.03784 (7)	0.51588 (15)	0.0377 (4)
C1Y	0.8290 (3)	−0.01487 (12)	0.6341 (2)	0.0579 (6)
H1Y1	0.9546	−0.0269	0.6473	0.087*
H1Y2	0.7707	−0.0336	0.6991	0.087*
H1Y3	0.8186	0.0316	0.6365	0.087*
C2Y	0.6946 (2)	−0.00107 (8)	0.41834 (17)	0.0330 (4)
O2Y	0.7016 (2)	0.05755 (6)	0.41793 (12)	0.0452 (4)
C3Y	0.6352 (3)	−0.04271 (9)	0.3087 (2)	0.0472 (5)
H3Y1	0.7240	−0.0427	0.2518	0.057*
H3Y2	0.5200	−0.0279	0.2633	0.057*
C4Y	0.6175 (3)	−0.10836 (9)	0.3620 (2)	0.0506 (6)
H4Y1	0.4925	−0.1175	0.3700	0.061*
H4Y2	0.6604	−0.1414	0.3094	0.061*
C5Y	0.7321 (3)	−0.10592 (9)	0.4871 (2)	0.0503 (6)
H5Y1	0.6759	−0.1292	0.5493	0.060*
H5Y2	0.8506	−0.1244	0.4839	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0294 (7)	0.0224 (7)	0.0224 (7)	−0.0005 (5)	−0.0013 (6)	−0.0003 (5)
C2	0.0249 (8)	0.0236 (8)	0.0239 (8)	−0.0017 (6)	0.0031 (6)	−0.0009 (6)
N2	0.0377 (8)	0.0213 (7)	0.0281 (8)	−0.0037 (6)	−0.0062 (6)	−0.0003 (6)
N3	0.0307 (7)	0.0217 (6)	0.0251 (7)	−0.0011 (5)	−0.0009 (6)	0.0006 (5)
C4	0.0257 (8)	0.0220 (7)	0.0250 (8)	0.0006 (6)	0.0014 (6)	0.0003 (6)
N4	0.0458 (9)	0.0205 (7)	0.0299 (8)	−0.0001 (6)	−0.0104 (7)	0.0015 (6)
N5	0.0281 (7)	0.0224 (7)	0.0235 (7)	0.0002 (5)	−0.0013 (6)	0.0005 (5)
C6	0.0252 (8)	0.0227 (7)	0.0221 (8)	−0.0001 (6)	0.0029 (6)	−0.0001 (6)
N6	0.0403 (8)	0.0199 (7)	0.0267 (8)	0.0005 (6)	−0.0075 (6)	0.0010 (6)
O1W	0.0442 (7)	0.0233 (6)	0.0469 (8)	−0.0033 (5)	0.0010 (6)	0.0007 (6)
N1X	0.0349 (8)	0.0250 (7)	0.0405 (9)	0.0021 (6)	0.0057 (7)	−0.0022 (6)
C1X	0.0424 (10)	0.0321 (9)	0.0473 (11)	−0.0045 (8)	0.0096 (9)	−0.0110 (8)
C2X	0.0331 (9)	0.0265 (8)	0.0365 (10)	0.0032 (7)	0.0054 (7)	−0.0025 (7)
O2X	0.0461 (8)	0.0277 (6)	0.0470 (8)	0.0076 (6)	−0.0040 (6)	−0.0010 (6)
C3X	0.0409 (10)	0.0352 (10)	0.0433 (11)	0.0001 (8)	0.0001 (9)	−0.0065 (8)
C4X	0.0402 (11)	0.0506 (12)	0.0427 (11)	0.0084 (9)	0.0001 (9)	0.0021 (9)
C5X	0.0413 (10)	0.0309 (9)	0.0478 (11)	0.0082 (8)	0.0147 (9)	0.0099 (8)
N1Y	0.0446 (9)	0.0275 (8)	0.0399 (9)	0.0053 (6)	0.0033 (7)	0.0085 (6)
C1Y	0.0668 (15)	0.0599 (14)	0.0417 (12)	−0.0007 (11)	−0.0085 (11)	0.0145 (10)
C2Y	0.0367 (9)	0.0267 (9)	0.0336 (9)	0.0014 (7)	−0.0012 (7)	−0.0003 (7)
O2Y	0.0697 (10)	0.0193 (6)	0.0392 (8)	−0.0004 (6)	−0.0145 (7)	0.0009 (5)
C3Y	0.0655 (14)	0.0315 (10)	0.0429 (12)	−0.0085 (9)	0.0032 (10)	−0.0083 (8)
C4Y	0.0602 (13)	0.0262 (9)	0.0709 (15)	−0.0085 (9)	0.0277 (12)	−0.0108 (9)
C5Y	0.0674 (14)	0.0244 (9)	0.0654 (14)	0.0097 (9)	0.0296 (12)	0.0107 (9)

Geometric parameters (Å, º)

N1—C6	1.347 (2)	C3X—C4X	1.524 (3)
N1—C2	1.352 (2)	C3X—H3X1	0.9900
C2—N2	1.338 (2)	C3X—H3X2	0.9900
C2—N3	1.339 (2)	C4X—C5X	1.525 (3)
N2—H21	0.89 (2)	C4X—H4X1	0.9900
N2—H22	0.84 (2)	C4X—H4X2	0.9900
N3—C4	1.347 (2)	C5X—H5X1	0.9900
C4—N4	1.330 (2)	C5X—H5X2	0.9900
C4—N5	1.349 (2)	N1Y—C2Y	1.328 (2)
N4—H41	0.89 (2)	N1Y—C1Y	1.436 (3)
N4—H42	0.88 (2)	N1Y—C5Y	1.465 (2)
N5—C6	1.340 (2)	C1Y—H1Y1	0.9800
C6—N6	1.343 (2)	C1Y—H1Y2	0.9800
N6—H61	0.91 (2)	C1Y—H1Y3	0.9800
N6—H62	0.87 (2)	C2Y—O2Y	1.233 (2)
O1W—H1W1	0.850 (9)	C2Y—C3Y	1.499 (3)
O1W—H1W2	0.852 (9)	C3Y—C4Y	1.513 (3)
N1X—C2X	1.329 (2)	C3Y—H3Y1	0.9900
N1X—C1X	1.443 (2)	C3Y—H3Y2	0.9900
N1X—C5X	1.455 (2)	C4Y—C5Y	1.508 (4)
C1X—H1X1	0.9800	C4Y—H4Y1	0.9900
C1X—H1X2	0.9800	C4Y—H4Y2	0.9900
C1X—H1X3	0.9800	C5Y—H5Y1	0.9900
C2X—O2X	1.244 (2)	C5Y—H5Y2	0.9900
C2X—C3X	1.499 (3)
C6—N1—C2	114.29 (13)	C3X—C4X—H4X1	110.6
N2—C2—N3	117.46 (14)	C5X—C4X—H4X1	110.6
N2—C2—N1	116.54 (14)	C3X—C4X—H4X2	110.6
N3—C2—N1	126.00 (14)	C5X—C4X—H4X2	110.6
C2—N2—H21	120.1 (13)	H4X1—C4X—H4X2	108.8
C2—N2—H22	118.5 (14)	N1X—C5X—C4X	104.62 (15)
H21—N2—H22	121.5 (19)	N1X—C5X—H5X1	110.8
C2—N3—C4	113.85 (13)	C4X—C5X—H5X1	110.8
N4—C4—N3	117.23 (14)	N1X—C5X—H5X2	110.8
N4—C4—N5	116.77 (14)	C4X—C5X—H5X2	110.8
N3—C4—N5	125.99 (14)	H5X1—C5X—H5X2	108.9
C4—N4—H41	119.7 (14)	C2Y—N1Y—C1Y	124.38 (17)
C4—N4—H42	119.2 (14)	C2Y—N1Y—C5Y	113.13 (17)
H41—N4—H42	121 (2)	C1Y—N1Y—C5Y	121.93 (17)
C6—N5—C4	114.37 (13)	N1Y—C1Y—H1Y1	109.5
N5—C6—N6	117.46 (14)	N1Y—C1Y—H1Y2	109.5
N5—C6—N1	125.47 (14)	H1Y1—C1Y—H1Y2	109.5
N6—C6—N1	117.07 (14)	N1Y—C1Y—H1Y3	109.5
C6—N6—H61	118.7 (13)	H1Y1—C1Y—H1Y3	109.5
C6—N6—H62	119.4 (13)	H1Y2—C1Y—H1Y3	109.5
H61—N6—H62	120.0 (18)	O2Y—C2Y—N1Y	125.24 (17)
H1W1—O1W—H1W2	105.1 (17)	O2Y—C2Y—C3Y	126.01 (17)
C2X—N1X—C1X	123.98 (16)	N1Y—C2Y—C3Y	108.70 (16)
C2X—N1X—C5X	114.30 (15)	C2Y—C3Y—C4Y	104.84 (17)
C1X—N1X—C5X	121.69 (15)	C2Y—C3Y—H3Y1	110.8
N1X—C1X—H1X1	109.5	C4Y—C3Y—H3Y1	110.8
N1X—C1X—H1X2	109.5	C2Y—C3Y—H3Y2	110.8
H1X1—C1X—H1X2	109.5	C4Y—C3Y—H3Y2	110.8
N1X—C1X—H1X3	109.5	H3Y1—C3Y—H3Y2	108.9
H1X1—C1X—H1X3	109.5	C5Y—C4Y—C3Y	104.28 (16)
H1X2—C1X—H1X3	109.5	C5Y—C4Y—H4Y1	110.9
O2X—C2X—N1X	124.68 (17)	C3Y—C4Y—H4Y1	110.9
O2X—C2X—C3X	125.93 (16)	C5Y—C4Y—H4Y2	110.9
N1X—C2X—C3X	109.39 (15)	C3Y—C4Y—H4Y2	110.9
C2X—C3X—C4X	105.36 (15)	H4Y1—C4Y—H4Y2	108.9
C2X—C3X—H3X1	110.7	N1Y—C5Y—C4Y	103.90 (16)
C4X—C3X—H3X1	110.7	N1Y—C5Y—H5Y1	111.0
C2X—C3X—H3X2	110.7	C4Y—C5Y—H5Y1	111.0
C4X—C3X—H3X2	110.7	N1Y—C5Y—H5Y2	111.0
H3X1—C3X—H3X2	108.8	C4Y—C5Y—H5Y2	111.0
C3X—C4X—C5X	105.48 (16)	H5Y1—C5Y—H5Y2	109.0
C6—N1—C2—N2	179.89 (14)	O2X—C2X—C3X—C4X	−173.06 (18)
C6—N1—C2—N3	−0.6 (2)	N1X—C2X—C3X—C4X	6.8 (2)
N2—C2—N3—C4	−179.18 (14)	C2X—C3X—C4X—C5X	−9.1 (2)
N1—C2—N3—C4	1.3 (2)	C2X—N1X—C5X—C4X	−4.4 (2)
C2—N3—C4—N4	−179.40 (15)	C1X—N1X—C5X—C4X	177.27 (16)
C2—N3—C4—N5	−0.3 (2)	C3X—C4X—C5X—N1X	8.2 (2)
N4—C4—N5—C6	177.86 (15)	C1Y—N1Y—C2Y—O2Y	−4.9 (3)
N3—C4—N5—C6	−1.2 (2)	C5Y—N1Y—C2Y—O2Y	−176.41 (19)
C4—N5—C6—N6	−178.64 (15)	C1Y—N1Y—C2Y—C3Y	172.7 (2)
C4—N5—C6—N1	2.1 (2)	C5Y—N1Y—C2Y—C3Y	1.2 (2)
C2—N1—C6—N5	−1.3 (2)	O2Y—C2Y—C3Y—C4Y	−169.4 (2)
C2—N1—C6—N6	179.46 (14)	N1Y—C2Y—C3Y—C4Y	13.0 (2)
C1X—N1X—C2X—O2X	−3.4 (3)	C2Y—C3Y—C4Y—C5Y	−21.3 (2)
C5X—N1X—C2X—O2X	178.34 (17)	C2Y—N1Y—C5Y—C4Y	−14.9 (2)
C1X—N1X—C2X—C3X	176.74 (17)	C1Y—N1Y—C5Y—C4Y	173.32 (19)
C5X—N1X—C2X—C3X	−1.6 (2)	C3Y—C4Y—C5Y—N1Y	21.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···N5^i	0.89 (2)	2.18 (2)	3.060 (2)	176.1 (18)
N2—H22···O1W	0.84 (2)	2.30 (2)	2.9268 (19)	131.4 (18)
N4—H41···N1^ii	0.89 (2)	2.06 (2)	2.938 (2)	169.6 (19)
N4—H42···O2Y^ii	0.88 (2)	2.08 (2)	2.8126 (19)	140.6 (19)
N6—H61···O1W^ii	0.91 (2)	2.15 (2)	3.048 (2)	169.3 (18)
N6—H62···O2Y	0.87 (2)	2.13 (2)	2.992 (2)	168.9 (19)
O1W—H1W1···O2X	0.85 (1)	1.95 (1)	2.7926 (17)	171 (2)
O1W—H1W2···O2X^iii	0.85 (1)	2.04 (1)	2.886 (2)	171 (2)

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

(III) ;

Crystal data

C4H3ClN2O2·C4H7N5·C4H9NO	Z = 2
Mr = 358.80	F(000) = 376
Triclinic, P1	Dx = 1.483 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9970 (5) Å	Cell parameters from 33416 reflections
b = 8.6140 (5) Å	θ = 3.3–26.3°
c = 13.8513 (9) Å	µ = 0.27 mm^−1
α = 85.725 (5)°	T = 173 K
β = 84.516 (5)°	Plate, colourless
γ = 75.572 (5)°	0.44 × 0.31 × 0.05 mm
V = 803.70 (9) Å^3

Data collection

STOE IPDS II two-circle diffractometer	3103 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	2815 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.045
ω scans	θmax = 25.9°, θmin = 3.3°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −8→8
Tmin = 0.890, Tmax = 0.986	k = −10→10
27171 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ^2(Fo^2) + (0.042P)^2 + 0.5034P] where P = (Fo^2 + 2Fc^2)/3
3103 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. ;

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
N1A	0.3519 (2)	0.82955 (17)	0.35115 (11)	0.0232 (3)
C2A	0.3130 (3)	0.7147 (2)	0.41647 (13)	0.0205 (3)
O2A	0.2482 (2)	0.74520 (14)	0.50291 (9)	0.0262 (3)
N3A	0.3438 (2)	0.56102 (17)	0.38803 (11)	0.0217 (3)
H3A	0.314 (3)	0.490 (3)	0.4316 (16)	0.026*
C4A	0.4099 (3)	0.5120 (2)	0.29560 (13)	0.0227 (4)
O4A	0.4297 (2)	0.37024 (15)	0.27664 (10)	0.0313 (3)
C5A	0.4491 (3)	0.6352 (2)	0.22779 (13)	0.0250 (4)
H5A	0.4964	0.6140	0.1623	0.030*
C6A	0.4156 (3)	0.7840 (2)	0.26146 (13)	0.0225 (4)
Cl6A	0.45510 (8)	0.94166 (5)	0.18076 (3)	0.03276 (15)
N1B	0.2060 (2)	0.05636 (18)	0.55784 (11)	0.0228 (3)
H1B	0.224 (3)	−0.042 (3)	0.5365 (16)	0.027*
C2B	0.2423 (3)	0.1777 (2)	0.49481 (13)	0.0218 (4)
N2B	0.3016 (3)	0.1458 (2)	0.40461 (12)	0.0300 (4)
H2B1	0.338 (3)	0.220 (3)	0.3674 (18)	0.036*
H2B2	0.320 (3)	0.047 (3)	0.3850 (17)	0.036*
N3B	0.2183 (2)	0.32494 (17)	0.52511 (11)	0.0217 (3)
C4B	0.1553 (2)	0.3465 (2)	0.61899 (13)	0.0206 (3)
N4B	0.1285 (2)	0.49194 (18)	0.65006 (12)	0.0247 (3)
H4B1	0.100 (3)	0.509 (3)	0.7112 (18)	0.030*
H4B2	0.153 (3)	0.569 (3)	0.6094 (17)	0.030*
N5B	0.1172 (2)	0.22898 (18)	0.68548 (11)	0.0233 (3)
C6B	0.1460 (3)	0.0866 (2)	0.65163 (13)	0.0221 (4)
C61B	0.1165 (3)	−0.0530 (2)	0.71617 (14)	0.0283 (4)
H61A	0.0729	−0.0180	0.7821	0.043*
H61B	0.2416	−0.1354	0.7172	0.043*
H61C	0.0158	−0.0976	0.6916	0.043*
C1X	−0.2197 (3)	0.6746 (3)	0.93637 (17)	0.0389 (5)
H1X1	−0.2738	0.6405	0.8810	0.058*
H1X2	−0.2901	0.7852	0.9499	0.058*
H1X3	−0.2365	0.6037	0.9936	0.058*
C2X	−0.0028 (3)	0.6659 (2)	0.91266 (14)	0.0282 (4)
O2X	0.0892 (2)	0.5991 (2)	0.84235 (11)	0.0412 (4)
N3X	0.0863 (2)	0.7354 (2)	0.97338 (12)	0.0307 (4)
C4X	−0.0034 (4)	0.7936 (3)	1.06727 (17)	0.0443 (6)
H4X1	−0.1465	0.8043	1.0705	0.067*
H4X2	0.0224	0.8984	1.0754	0.067*
H4X3	0.0538	0.7173	1.1191	0.067*
C5X	0.2953 (3)	0.7296 (3)	0.95317 (16)	0.0351 (5)
H5X1	0.3726	0.6461	0.9956	0.053*
H5X2	0.3189	0.8338	0.9650	0.053*
H5X3	0.3356	0.7050	0.8852	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0308 (8)	0.0162 (7)	0.0230 (8)	−0.0073 (6)	−0.0009 (6)	−0.0010 (6)
C2A	0.0242 (8)	0.0174 (8)	0.0212 (9)	−0.0066 (6)	−0.0024 (7)	−0.0029 (6)
O2A	0.0400 (7)	0.0186 (6)	0.0209 (7)	−0.0098 (5)	0.0027 (5)	−0.0045 (5)
N3A	0.0307 (8)	0.0147 (7)	0.0203 (8)	−0.0077 (6)	0.0004 (6)	−0.0005 (6)
C4A	0.0279 (9)	0.0187 (8)	0.0219 (9)	−0.0064 (7)	−0.0006 (7)	−0.0034 (7)
O4A	0.0500 (8)	0.0188 (6)	0.0261 (7)	−0.0126 (6)	0.0067 (6)	−0.0064 (5)
C5A	0.0327 (10)	0.0216 (9)	0.0206 (9)	−0.0073 (7)	0.0007 (7)	−0.0019 (7)
C6A	0.0259 (9)	0.0186 (8)	0.0234 (9)	−0.0071 (7)	−0.0029 (7)	0.0029 (7)
Cl6A	0.0481 (3)	0.0222 (2)	0.0278 (3)	−0.0121 (2)	0.0019 (2)	0.00586 (17)
N1B	0.0315 (8)	0.0150 (7)	0.0225 (8)	−0.0070 (6)	−0.0014 (6)	−0.0015 (6)
C2B	0.0265 (9)	0.0173 (8)	0.0224 (9)	−0.0069 (7)	−0.0022 (7)	−0.0018 (7)
N2B	0.0536 (11)	0.0164 (7)	0.0217 (8)	−0.0142 (7)	0.0064 (7)	−0.0037 (6)
N3B	0.0297 (8)	0.0156 (7)	0.0208 (7)	−0.0075 (6)	−0.0016 (6)	−0.0022 (5)
C4B	0.0221 (8)	0.0187 (8)	0.0218 (8)	−0.0051 (6)	−0.0041 (6)	−0.0018 (6)
N4B	0.0370 (9)	0.0189 (7)	0.0191 (8)	−0.0081 (6)	−0.0010 (6)	−0.0042 (6)
N5B	0.0290 (8)	0.0201 (7)	0.0216 (7)	−0.0071 (6)	−0.0020 (6)	−0.0022 (6)
C6B	0.0240 (8)	0.0199 (8)	0.0227 (9)	−0.0058 (7)	−0.0037 (7)	−0.0002 (7)
C61B	0.0402 (11)	0.0216 (9)	0.0234 (9)	−0.0098 (8)	0.0003 (8)	0.0011 (7)
C1X	0.0322 (11)	0.0403 (12)	0.0455 (13)	−0.0122 (9)	−0.0087 (9)	0.0083 (10)
C2X	0.0345 (10)	0.0252 (9)	0.0248 (10)	−0.0079 (8)	−0.0036 (8)	0.0025 (7)
O2X	0.0472 (9)	0.0481 (9)	0.0321 (8)	−0.0173 (7)	0.0028 (7)	−0.0151 (7)
N3X	0.0302 (8)	0.0343 (9)	0.0274 (9)	−0.0071 (7)	0.0004 (7)	−0.0072 (7)
C4X	0.0471 (13)	0.0539 (14)	0.0329 (12)	−0.0128 (11)	0.0059 (10)	−0.0183 (10)
C5X	0.0305 (10)	0.0387 (11)	0.0379 (11)	−0.0119 (9)	−0.0019 (8)	−0.0029 (9)

Geometric parameters (Å, º)

N1A—C6A	1.333 (2)	N4B—H4B1	0.87 (2)
N1A—C2A	1.351 (2)	N4B—H4B2	0.88 (2)
C2A—O2A	1.262 (2)	N5B—C6B	1.307 (2)
C2A—N3A	1.369 (2)	C6B—C61B	1.489 (2)
N3A—C4A	1.379 (2)	C61B—H61A	0.9800
N3A—H3A	0.88 (2)	C61B—H61B	0.9800
C4A—O4A	1.239 (2)	C61B—H61C	0.9800
C4A—C5A	1.425 (2)	C1X—C2X	1.506 (3)
C5A—C6A	1.355 (2)	C1X—H1X1	0.9800
C5A—H5A	0.9500	C1X—H1X2	0.9800
C6A—Cl6A	1.7524 (17)	C1X—H1X3	0.9800
N1B—C6B	1.350 (2)	C2X—O2X	1.214 (2)
N1B—C2B	1.369 (2)	C2X—N3X	1.347 (3)
N1B—H1B	0.89 (2)	N3X—C5X	1.452 (3)
C2B—N2B	1.305 (2)	N3X—C4X	1.456 (3)
C2B—N3B	1.331 (2)	C4X—H4X1	0.9800
N2B—H2B1	0.87 (3)	C4X—H4X2	0.9800
N2B—H2B2	0.89 (3)	C4X—H4X3	0.9800
N3B—C4B	1.344 (2)	C5X—H5X1	0.9800
C4B—N4B	1.318 (2)	C5X—H5X2	0.9800
C4B—N5B	1.376 (2)	C5X—H5X3	0.9800
C6A—N1A—C2A	116.56 (15)	N5B—C6B—N1B	122.80 (16)
O2A—C2A—N1A	121.86 (15)	N5B—C6B—C61B	121.05 (16)
O2A—C2A—N3A	119.02 (15)	N1B—C6B—C61B	116.15 (15)
N1A—C2A—N3A	119.12 (15)	C6B—C61B—H61A	109.5
C2A—N3A—C4A	125.01 (15)	C6B—C61B—H61B	109.5
C2A—N3A—H3A	117.0 (14)	H61A—C61B—H61B	109.5
C4A—N3A—H3A	117.9 (14)	C6B—C61B—H61C	109.5
O4A—C4A—N3A	120.09 (16)	H61A—C61B—H61C	109.5
O4A—C4A—C5A	124.99 (16)	H61B—C61B—H61C	109.5
N3A—C4A—C5A	114.92 (15)	C2X—C1X—H1X1	109.5
C6A—C5A—C4A	116.60 (16)	C2X—C1X—H1X2	109.5
C6A—C5A—H5A	121.7	H1X1—C1X—H1X2	109.5
C4A—C5A—H5A	121.7	C2X—C1X—H1X3	109.5
N1A—C6A—C5A	127.78 (16)	H1X1—C1X—H1X3	109.5
N1A—C6A—Cl6A	113.47 (13)	H1X2—C1X—H1X3	109.5
C5A—C6A—Cl6A	118.74 (14)	O2X—C2X—N3X	120.98 (19)
C6B—N1B—C2B	119.49 (15)	O2X—C2X—C1X	121.97 (19)
C6B—N1B—H1B	121.0 (14)	N3X—C2X—C1X	117.05 (18)
C2B—N1B—H1B	119.5 (14)	C2X—N3X—C5X	118.77 (17)
N2B—C2B—N3B	120.81 (16)	C2X—N3X—C4X	124.24 (18)
N2B—C2B—N1B	118.59 (16)	C5X—N3X—C4X	116.18 (17)
N3B—C2B—N1B	120.60 (16)	N3X—C4X—H4X1	109.5
C2B—N2B—H2B1	117.5 (16)	N3X—C4X—H4X2	109.5
C2B—N2B—H2B2	120.5 (16)	H4X1—C4X—H4X2	109.5
H2B1—N2B—H2B2	121 (2)	N3X—C4X—H4X3	109.5
C2B—N3B—C4B	116.52 (15)	H4X1—C4X—H4X3	109.5
N4B—C4B—N3B	117.38 (16)	H4X2—C4X—H4X3	109.5
N4B—C4B—N5B	117.31 (16)	N3X—C5X—H5X1	109.5
N3B—C4B—N5B	125.31 (15)	N3X—C5X—H5X2	109.5
C4B—N4B—H4B1	120.1 (15)	H5X1—C5X—H5X2	109.5
C4B—N4B—H4B2	119.4 (15)	N3X—C5X—H5X3	109.5
H4B1—N4B—H4B2	120 (2)	H5X1—C5X—H5X3	109.5
C6B—N5B—C4B	115.26 (15)	H5X2—C5X—H5X3	109.5
C6A—N1A—C2A—O2A	−178.58 (16)	N2B—C2B—N3B—C4B	179.48 (17)
C6A—N1A—C2A—N3A	1.1 (2)	N1B—C2B—N3B—C4B	−0.8 (2)
O2A—C2A—N3A—C4A	178.55 (16)	C2B—N3B—C4B—N4B	−179.25 (16)
N1A—C2A—N3A—C4A	−1.1 (3)	C2B—N3B—C4B—N5B	1.1 (3)
C2A—N3A—C4A—O4A	−178.68 (17)	N4B—C4B—N5B—C6B	−179.88 (16)
C2A—N3A—C4A—C5A	0.8 (3)	N3B—C4B—N5B—C6B	−0.2 (3)
O4A—C4A—C5A—C6A	178.91 (18)	C4B—N5B—C6B—N1B	−1.0 (3)
N3A—C4A—C5A—C6A	−0.6 (3)	C4B—N5B—C6B—C61B	178.14 (16)
C2A—N1A—C6A—C5A	−1.0 (3)	C2B—N1B—C6B—N5B	1.2 (3)
C2A—N1A—C6A—Cl6A	178.17 (13)	C2B—N1B—C6B—C61B	−177.92 (16)
C4A—C5A—C6A—N1A	0.8 (3)	O2X—C2X—N3X—C5X	0.2 (3)
C4A—C5A—C6A—Cl6A	−178.38 (13)	C1X—C2X—N3X—C5X	179.92 (17)
C6B—N1B—C2B—N2B	179.47 (17)	O2X—C2X—N3X—C4X	−169.1 (2)
C6B—N1B—C2B—N3B	−0.3 (3)	C1X—C2X—N3X—C4X	10.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3A···N3B	0.88 (2)	2.04 (2)	2.917 (2)	174 (2)
N1B—H1B···O2A^i	0.89 (2)	1.89 (2)	2.7779 (19)	174 (2)
N2B—H2B1···O4A	0.87 (3)	1.92 (3)	2.780 (2)	175 (2)
N2B—H2B2···N1A^i	0.89 (3)	1.92 (3)	2.805 (2)	176 (2)
N4B—H4B1···O2X	0.87 (2)	2.02 (3)	2.850 (2)	161 (2)
N4B—H4B2···O2A	0.88 (2)	2.21 (2)	3.088 (2)	173 (2)

Symmetry code: (i) x, y−1, z.

(IV) ;

Crystal data

C4H3ClN2O2·C4H7N5·C3H7NO·H2O	Z = 2
Mr = 362.79	F(000) = 380
Triclinic, P1	Dx = 1.472 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1719 (11) Å	Cell parameters from 12063 reflections
b = 8.6197 (11) Å	θ = 3.3–26.2°
c = 13.5029 (19) Å	µ = 0.27 mm^−1
α = 94.574 (11)°	T = 173 K
β = 92.707 (12)°	Block, colourless
γ = 99.840 (11)°	0.16 × 0.14 × 0.11 mm
V = 818.3 (2) Å^3

Data collection

STOE IPDS II two-circle diffractometer	3149 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	2270 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.117
ω scans	θmax = 25.9°, θmin = 3.4°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −8→8
Tmin = 0.958, Tmax = 0.972	k = −10→10
13964 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0926P)^2 + 0.0699P] where P = (Fo^2 + 2Fc^2)/3
3149 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.32 e Å^−3
3 restraints	Δρmin = −0.42 e Å^−3

Special details

Experimental. ;

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
N1A	0.3252 (4)	0.1427 (3)	0.37736 (17)	0.0314 (6)
C2A	0.2869 (4)	0.2611 (4)	0.4408 (2)	0.0306 (6)
O2A	0.2276 (3)	0.2352 (3)	0.52532 (14)	0.0348 (5)
N3A	0.3137 (4)	0.4116 (3)	0.41226 (17)	0.0308 (6)
H3A	0.281 (5)	0.486 (5)	0.451 (3)	0.037*
C4A	0.3711 (4)	0.4551 (4)	0.3213 (2)	0.0317 (7)
O4A	0.3851 (3)	0.5947 (3)	0.30202 (16)	0.0407 (6)
C5A	0.4091 (4)	0.3284 (4)	0.2552 (2)	0.0324 (7)
H5A	0.4509	0.3454	0.1906	0.039*
C6A	0.3829 (4)	0.1837 (4)	0.2885 (2)	0.0313 (6)
Cl6A	0.42203 (12)	0.02266 (9)	0.20984 (5)	0.0398 (3)
N1B	0.1959 (4)	0.9265 (3)	0.58219 (17)	0.0313 (6)
H1B	0.211 (5)	1.021 (5)	0.564 (3)	0.038*
C2B	0.2342 (4)	0.8050 (4)	0.5196 (2)	0.0330 (7)
N2B	0.2951 (5)	0.8361 (4)	0.4329 (2)	0.0398 (7)
H21B	0.309 (5)	0.925 (5)	0.414 (3)	0.048*
H22B	0.323 (5)	0.768 (5)	0.398 (3)	0.048*
N3B	0.2124 (4)	0.6585 (3)	0.54793 (17)	0.0316 (6)
C4B	0.1470 (4)	0.6369 (4)	0.6383 (2)	0.0302 (6)
N4B	0.1223 (4)	0.4930 (3)	0.6668 (2)	0.0360 (6)
H41B	0.090 (5)	0.471 (5)	0.722 (3)	0.043*
H42B	0.153 (5)	0.421 (5)	0.628 (3)	0.043*
N5B	0.1044 (4)	0.7548 (3)	0.70368 (17)	0.0338 (6)
C6B	0.1321 (4)	0.8961 (4)	0.6727 (2)	0.0317 (7)
C61B	0.0943 (5)	1.0341 (4)	0.7371 (2)	0.0390 (7)
H61A	0.0356	0.9974	0.7970	0.059*
H61B	0.0085	1.0895	0.7005	0.059*
H61C	0.2139	1.1063	0.7561	0.059*
O1W	0.5689 (4)	0.6740 (5)	0.1317 (2)	0.0703 (9)
H1W	0.530 (6)	0.654 (7)	0.189 (2)	0.105*
H2W	0.679 (4)	0.651 (7)	0.126 (4)	0.105*
C1X	−0.0839 (5)	0.3389 (4)	0.9020 (2)	0.0434 (8)
H1X	−0.2027	0.3470	0.8705	0.052*
O1X	0.0606 (4)	0.3911 (3)	0.86028 (17)	0.0486 (6)
N2X	−0.0855 (4)	0.2729 (4)	0.98674 (19)	0.0460 (7)
C3X	−0.2618 (6)	0.2178 (6)	1.0324 (3)	0.0595 (11)
H3X1	−0.3677	0.2487	0.9947	0.089*
H3X2	−0.2547	0.2652	1.1012	0.089*
H3X3	−0.2818	0.1024	1.0320	0.089*
C4X	0.0891 (6)	0.2543 (6)	1.0402 (3)	0.0616 (11)
H4X1	0.1070	0.1441	1.0298	0.092*
H4X2	0.0814	0.2827	1.1114	0.092*
H4X3	0.1964	0.3235	1.0154	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0405 (14)	0.0257 (13)	0.0287 (12)	0.0091 (11)	0.0022 (10)	−0.0011 (10)
C2A	0.0359 (16)	0.0307 (16)	0.0264 (14)	0.0094 (13)	−0.0001 (11)	0.0030 (11)
O2A	0.0485 (13)	0.0313 (12)	0.0262 (10)	0.0096 (9)	0.0067 (9)	0.0040 (8)
N3A	0.0420 (15)	0.0265 (14)	0.0248 (12)	0.0096 (11)	0.0045 (10)	−0.0002 (10)
C4A	0.0340 (16)	0.0298 (17)	0.0311 (14)	0.0054 (13)	0.0028 (12)	0.0010 (12)
O4A	0.0586 (15)	0.0286 (12)	0.0371 (12)	0.0103 (10)	0.0139 (10)	0.0046 (9)
C5A	0.0364 (17)	0.0328 (17)	0.0277 (13)	0.0051 (13)	0.0050 (12)	0.0009 (12)
C6A	0.0345 (16)	0.0291 (16)	0.0294 (14)	0.0058 (12)	0.0008 (12)	−0.0024 (12)
Cl6A	0.0503 (5)	0.0328 (4)	0.0358 (4)	0.0084 (3)	0.0089 (3)	−0.0064 (3)
N1B	0.0430 (15)	0.0228 (13)	0.0293 (12)	0.0097 (11)	0.0034 (10)	0.0006 (10)
C2B	0.0411 (17)	0.0328 (17)	0.0260 (14)	0.0108 (13)	0.0006 (12)	−0.0011 (12)
N2B	0.0652 (19)	0.0268 (15)	0.0300 (13)	0.0122 (14)	0.0136 (13)	0.0036 (11)
N3B	0.0426 (14)	0.0281 (14)	0.0250 (11)	0.0081 (11)	0.0046 (10)	0.0028 (10)
C4B	0.0352 (16)	0.0301 (16)	0.0257 (13)	0.0083 (12)	−0.0003 (11)	0.0016 (11)
N4B	0.0497 (17)	0.0335 (16)	0.0255 (12)	0.0079 (12)	0.0069 (11)	0.0040 (11)
N5B	0.0416 (15)	0.0350 (15)	0.0248 (11)	0.0085 (12)	0.0015 (10)	−0.0010 (10)
C6B	0.0364 (16)	0.0321 (17)	0.0264 (13)	0.0082 (13)	−0.0016 (12)	−0.0014 (12)
C61B	0.054 (2)	0.0332 (17)	0.0312 (15)	0.0135 (15)	0.0068 (14)	−0.0033 (12)
O1W	0.0632 (19)	0.103 (3)	0.0505 (16)	0.0207 (18)	0.0112 (14)	0.0241 (16)
C1X	0.050 (2)	0.051 (2)	0.0298 (15)	0.0111 (16)	0.0046 (14)	0.0007 (14)
O1X	0.0525 (15)	0.0624 (17)	0.0344 (12)	0.0153 (12)	0.0090 (10)	0.0122 (11)
N2X	0.0500 (18)	0.0576 (19)	0.0305 (13)	0.0080 (14)	0.0074 (12)	0.0052 (13)
C3X	0.058 (2)	0.079 (3)	0.0396 (19)	0.002 (2)	0.0097 (17)	0.0121 (19)
C4X	0.058 (2)	0.089 (3)	0.0418 (19)	0.018 (2)	0.0038 (17)	0.022 (2)

Geometric parameters (Å, º)

N1A—C6A	1.342 (4)	N4B—H41B	0.82 (4)
N1A—C2A	1.352 (4)	N4B—H42B	0.84 (4)
C2A—O2A	1.259 (3)	N5B—C6B	1.306 (4)
C2A—N3A	1.368 (4)	C6B—C61B	1.487 (4)
N3A—C4A	1.374 (4)	C61B—H61A	0.9800
N3A—H3A	0.87 (4)	C61B—H61B	0.9800
C4A—O4A	1.240 (4)	C61B—H61C	0.9800
C4A—C5A	1.426 (4)	O1W—H1W	0.852 (10)
C5A—C6A	1.346 (4)	O1W—H2W	0.855 (10)
C5A—H5A	0.9500	C1X—O1X	1.237 (4)
C6A—Cl6A	1.749 (3)	C1X—N2X	1.318 (4)
N1B—C6B	1.354 (4)	C1X—H1X	0.9500
N1B—C2B	1.366 (4)	N2X—C4X	1.455 (5)
N1B—H1B	0.86 (4)	N2X—C3X	1.456 (5)
C2B—N2B	1.301 (4)	C3X—H3X1	0.9800
C2B—N3B	1.335 (4)	C3X—H3X2	0.9800
N2B—H21B	0.81 (4)	C3X—H3X3	0.9800
N2B—H22B	0.78 (4)	C4X—H4X1	0.9800
N3B—C4B	1.343 (4)	C4X—H4X2	0.9800
C4B—N4B	1.314 (4)	C4X—H4X3	0.9800
C4B—N5B	1.376 (4)
C6A—N1A—C2A	116.1 (3)	H41B—N4B—H42B	118 (4)
O2A—C2A—N1A	121.3 (3)	C6B—N5B—C4B	115.4 (2)
O2A—C2A—N3A	119.7 (3)	N5B—C6B—N1B	123.1 (3)
N1A—C2A—N3A	119.0 (3)	N5B—C6B—C61B	120.6 (3)
C2A—N3A—C4A	125.6 (3)	N1B—C6B—C61B	116.3 (3)
C2A—N3A—H3A	119 (2)	C6B—C61B—H61A	109.5
C4A—N3A—H3A	115 (2)	C6B—C61B—H61B	109.5
O4A—C4A—N3A	120.2 (3)	H61A—C61B—H61B	109.5
O4A—C4A—C5A	125.3 (3)	C6B—C61B—H61C	109.5
N3A—C4A—C5A	114.5 (3)	H61A—C61B—H61C	109.5
C6A—C5A—C4A	117.0 (3)	H61B—C61B—H61C	109.5
C6A—C5A—H5A	121.5	H1W—O1W—H2W	110 (3)
C4A—C5A—H5A	121.5	O1X—C1X—N2X	125.0 (3)
N1A—C6A—C5A	127.9 (3)	O1X—C1X—H1X	117.5
N1A—C6A—Cl6A	113.0 (2)	N2X—C1X—H1X	117.5
C5A—C6A—Cl6A	119.1 (2)	C1X—N2X—C4X	121.6 (3)
C6B—N1B—C2B	119.2 (3)	C1X—N2X—C3X	121.6 (3)
C6B—N1B—H1B	121 (2)	C4X—N2X—C3X	116.8 (3)
C2B—N1B—H1B	120 (2)	N2X—C3X—H3X1	109.5
N2B—C2B—N3B	121.1 (3)	N2X—C3X—H3X2	109.5
N2B—C2B—N1B	118.5 (3)	H3X1—C3X—H3X2	109.5
N3B—C2B—N1B	120.5 (3)	N2X—C3X—H3X3	109.5
C2B—N2B—H21B	123 (3)	H3X1—C3X—H3X3	109.5
C2B—N2B—H22B	119 (3)	H3X2—C3X—H3X3	109.5
H21B—N2B—H22B	118 (4)	N2X—C4X—H4X1	109.5
C2B—N3B—C4B	117.0 (3)	N2X—C4X—H4X2	109.5
N4B—C4B—N3B	117.8 (3)	H4X1—C4X—H4X2	109.5
N4B—C4B—N5B	117.4 (3)	N2X—C4X—H4X3	109.5
N3B—C4B—N5B	124.8 (3)	H4X1—C4X—H4X3	109.5
C4B—N4B—H41B	124 (3)	H4X2—C4X—H4X3	109.5
C4B—N4B—H42B	118 (3)
C6A—N1A—C2A—O2A	178.3 (3)	C6B—N1B—C2B—N3B	−1.2 (4)
C6A—N1A—C2A—N3A	−1.8 (4)	N2B—C2B—N3B—C4B	−179.4 (3)
O2A—C2A—N3A—C4A	−177.6 (3)	N1B—C2B—N3B—C4B	1.8 (4)
N1A—C2A—N3A—C4A	2.6 (4)	C2B—N3B—C4B—N4B	179.1 (3)
C2A—N3A—C4A—O4A	177.7 (3)	C2B—N3B—C4B—N5B	−1.1 (4)
C2A—N3A—C4A—C5A	−1.9 (4)	N4B—C4B—N5B—C6B	179.6 (3)
O4A—C4A—C5A—C6A	−178.9 (3)	N3B—C4B—N5B—C6B	−0.2 (4)
N3A—C4A—C5A—C6A	0.7 (4)	C4B—N5B—C6B—N1B	0.8 (4)
C2A—N1A—C6A—C5A	0.7 (5)	C4B—N5B—C6B—C61B	−179.0 (3)
C2A—N1A—C6A—Cl6A	−178.1 (2)	C2B—N1B—C6B—N5B	−0.2 (5)
C4A—C5A—C6A—N1A	−0.2 (5)	C2B—N1B—C6B—C61B	179.7 (3)
C4A—C5A—C6A—Cl6A	178.6 (2)	O1X—C1X—N2X—C4X	−0.4 (6)
C6B—N1B—C2B—N2B	179.9 (3)	O1X—C1X—N2X—C3X	178.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3A···N3B	0.87 (4)	2.04 (4)	2.906 (4)	177 (3)
N1B—H1B···O2A^i	0.86 (4)	1.94 (4)	2.803 (3)	176 (3)
N2B—H21B···N1A^i	0.81 (4)	1.97 (4)	2.781 (4)	175 (4)
N2B—H22B···O4A	0.78 (4)	2.02 (4)	2.802 (4)	177 (4)
N4B—H41B···O1X	0.82 (4)	2.05 (4)	2.852 (4)	167 (4)
N4B—H42B···O2A	0.84 (4)	2.19 (4)	3.031 (4)	179 (3)
O1W—H1W···O4A	0.85 (1)	1.94 (2)	2.779 (4)	167 (5)
O1W—H2W···O1X^ii	0.86 (1)	1.96 (2)	2.807 (4)	169 (5)

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

(Va) ;

Crystal data

C4H3ClN2O2·C3H4ClN5·C3H7NO	Z = 2
Mr = 365.19	F(000) = 376
Triclinic, P1	Dx = 1.543 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4573 (10) Å	Cell parameters from 11913 reflections
b = 9.3488 (10) Å	θ = 3.4–26.3°
c = 10.8269 (11) Å	µ = 0.44 mm^−1
α = 72.144 (8)°	T = 173 K
β = 77.879 (9)°	Plate, colourless
γ = 77.444 (9)°	0.38 × 0.10 × 0.04 mm
V = 785.79 (15) Å^3

Data collection

STOE IPDS II two-circle diffractometer	3027 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	2270 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.065
ω scans	θmax = 25.9°, θmin = 3.4°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −10→10
Tmin = 0.849, Tmax = 0.983	k = −11→10
17138 measured reflections	l = −13→13

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0418P)^2] where P = (Fo^2 + 2Fc^2)/3
3027 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.45 e Å^−3
6 restraints	Δρmin = −0.18 e Å^−3

Special details

Experimental. ;

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
N3A	0.2679 (2)	0.4575 (2)	0.56294 (16)	0.0262 (4)
H3A	0.312 (3)	0.509 (3)	0.597 (2)	0.031*
C2A	0.2306 (3)	0.3210 (3)	0.6430 (2)	0.0279 (5)
O2A	0.2557 (2)	0.27378 (19)	0.75712 (14)	0.0359 (4)
N1A	0.1619 (2)	0.2407 (2)	0.58756 (16)	0.0281 (4)
H1A	0.139 (3)	0.150 (2)	0.636 (2)	0.034*
C6A	0.1313 (2)	0.2963 (3)	0.46136 (19)	0.0265 (5)
Cl6A	0.04350 (7)	0.18198 (7)	0.40860 (5)	0.03486 (16)
C5A	0.1659 (3)	0.4313 (3)	0.3832 (2)	0.0274 (5)
H5A	0.1424	0.4661	0.2958	0.033*
C4A	0.2394 (3)	0.5228 (3)	0.43389 (19)	0.0262 (5)
O4A	0.2749 (2)	0.64760 (18)	0.37309 (13)	0.0332 (4)
N1B	0.5019 (2)	0.6631 (2)	0.85823 (15)	0.0255 (4)
C2B	0.5252 (2)	0.7981 (3)	0.78126 (19)	0.0258 (5)
Cl2B	0.60189 (8)	0.90762 (7)	0.85200 (5)	0.03968 (17)
N3B	0.4988 (2)	0.8646 (2)	0.66009 (16)	0.0243 (4)
C4B	0.4341 (2)	0.7766 (2)	0.60976 (18)	0.0234 (4)
N4B	0.4060 (2)	0.8327 (2)	0.48765 (17)	0.0287 (4)
H4B1	0.430 (3)	0.920 (2)	0.440 (2)	0.034*
H4B2	0.365 (3)	0.781 (3)	0.452 (2)	0.034*
N5B	0.3993 (2)	0.6372 (2)	0.67718 (15)	0.0239 (4)
C6B	0.4350 (2)	0.5850 (2)	0.79993 (19)	0.0235 (4)
N6B	0.4042 (2)	0.4484 (2)	0.87209 (17)	0.0297 (4)
H6B1	0.366 (3)	0.391 (3)	0.838 (2)	0.036*
H6B2	0.431 (3)	0.414 (3)	0.9517 (18)	0.036*
C1X	0.1418 (3)	−0.0607 (3)	0.8601 (2)	0.0331 (5)
H1X	0.2044	0.0067	0.8703	0.040*
O1X	0.0903 (2)	−0.02903 (19)	0.75371 (14)	0.0365 (4)
N2X	0.1159 (2)	−0.1815 (2)	0.96019 (17)	0.0331 (4)
C3X	0.1854 (3)	−0.2139 (3)	1.0795 (2)	0.0468 (7)
H3X1	0.2430	−0.1312	1.0737	0.070*
H3X2	0.2627	−0.3100	1.0903	0.070*
H3X3	0.0973	−0.2224	1.1551	0.070*
C4X	0.0232 (3)	−0.2910 (3)	0.9521 (2)	0.0453 (6)
H4X1	−0.0185	−0.2557	0.8681	0.068*
H4X2	−0.0690	−0.3013	1.0245	0.068*
H4X3	0.0945	−0.3899	0.9583	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N3A	0.0361 (10)	0.0259 (10)	0.0216 (8)	−0.0125 (8)	−0.0097 (7)	−0.0050 (7)
C2A	0.0324 (11)	0.0288 (12)	0.0247 (10)	−0.0129 (9)	−0.0055 (8)	−0.0043 (9)
O2A	0.0538 (10)	0.0385 (10)	0.0204 (7)	−0.0228 (8)	−0.0120 (7)	−0.0004 (7)
N1A	0.0385 (11)	0.0265 (11)	0.0218 (8)	−0.0157 (9)	−0.0069 (7)	−0.0017 (7)
C6A	0.0288 (11)	0.0328 (13)	0.0223 (10)	−0.0079 (9)	−0.0062 (8)	−0.0104 (9)
Cl6A	0.0477 (3)	0.0345 (3)	0.0314 (3)	−0.0186 (3)	−0.0119 (2)	−0.0099 (2)
C5A	0.0364 (11)	0.0271 (13)	0.0219 (10)	−0.0069 (9)	−0.0092 (8)	−0.0068 (9)
C4A	0.0315 (11)	0.0284 (12)	0.0200 (9)	−0.0072 (9)	−0.0067 (8)	−0.0051 (8)
O4A	0.0521 (10)	0.0256 (9)	0.0246 (7)	−0.0154 (7)	−0.0133 (7)	0.0003 (6)
N1B	0.0343 (10)	0.0270 (10)	0.0180 (8)	−0.0114 (8)	−0.0082 (7)	−0.0028 (7)
C2B	0.0296 (11)	0.0279 (12)	0.0243 (10)	−0.0086 (9)	−0.0062 (8)	−0.0095 (9)
Cl2B	0.0608 (4)	0.0371 (4)	0.0317 (3)	−0.0213 (3)	−0.0181 (3)	−0.0082 (2)
N3B	0.0322 (9)	0.0219 (10)	0.0207 (8)	−0.0081 (7)	−0.0081 (7)	−0.0033 (7)
C4B	0.0256 (11)	0.0243 (11)	0.0213 (9)	−0.0052 (9)	−0.0066 (8)	−0.0051 (8)
N4B	0.0457 (11)	0.0234 (10)	0.0207 (8)	−0.0163 (8)	−0.0146 (8)	0.0023 (7)
N5B	0.0305 (9)	0.0234 (10)	0.0187 (8)	−0.0080 (7)	−0.0076 (7)	−0.0020 (7)
C6B	0.0244 (10)	0.0252 (12)	0.0205 (9)	−0.0057 (9)	−0.0043 (8)	−0.0040 (8)
N6B	0.0452 (11)	0.0270 (11)	0.0204 (8)	−0.0150 (9)	−0.0127 (7)	−0.0001 (8)
C1X	0.0370 (13)	0.0312 (13)	0.0331 (12)	−0.0092 (10)	−0.0072 (9)	−0.0078 (10)
O1X	0.0470 (10)	0.0343 (10)	0.0293 (8)	−0.0144 (8)	−0.0112 (7)	−0.0016 (7)
N2X	0.0380 (11)	0.0320 (11)	0.0281 (9)	−0.0076 (9)	−0.0073 (8)	−0.0036 (8)
C3X	0.0499 (15)	0.0548 (18)	0.0300 (12)	−0.0027 (13)	−0.0137 (11)	−0.0026 (11)
C4X	0.0560 (16)	0.0398 (16)	0.0391 (13)	−0.0190 (13)	−0.0046 (11)	−0.0033 (11)

Geometric parameters (Å, º)

N3A—C2A	1.364 (3)	C4B—N5B	1.346 (3)
N3A—C4A	1.392 (3)	N4B—H4B1	0.868 (17)
N3A—H3A	0.869 (16)	N4B—H4B2	0.865 (17)
C2A—O2A	1.225 (3)	N5B—C6B	1.342 (3)
C2A—N1A	1.369 (3)	C6B—N6B	1.326 (3)
N1A—C6A	1.363 (3)	N6B—H6B1	0.885 (17)
N1A—H1A	0.892 (17)	N6B—H6B2	0.883 (16)
C6A—C5A	1.340 (3)	C1X—O1X	1.245 (3)
C6A—Cl6A	1.708 (2)	C1X—N2X	1.325 (3)
C5A—C4A	1.443 (3)	C1X—H1X	0.9500
C5A—H5A	0.9500	N2X—C4X	1.450 (3)
C4A—O4A	1.218 (3)	N2X—C3X	1.452 (3)
N1B—C2B	1.311 (3)	C3X—H3X1	0.9800
N1B—C6B	1.365 (3)	C3X—H3X2	0.9800
C2B—N3B	1.311 (3)	C3X—H3X3	0.9800
C2B—Cl2B	1.742 (2)	C4X—H4X1	0.9800
N3B—C4B	1.367 (3)	C4X—H4X2	0.9800
C4B—N4B	1.316 (3)	C4X—H4X3	0.9800
C2A—N3A—C4A	126.62 (18)	C4B—N4B—H4B2	120.1 (17)
C2A—N3A—H3A	116.3 (16)	H4B1—N4B—H4B2	118 (2)
C4A—N3A—H3A	117.0 (16)	C6B—N5B—C4B	115.78 (18)
O2A—C2A—N3A	122.4 (2)	N6B—C6B—N5B	119.10 (19)
O2A—C2A—N1A	122.2 (2)	N6B—C6B—N1B	116.20 (17)
N3A—C2A—N1A	115.43 (18)	N5B—C6B—N1B	124.69 (19)
C6A—N1A—C2A	121.52 (19)	C6B—N6B—H6B1	120.0 (17)
C6A—N1A—H1A	120.5 (16)	C6B—N6B—H6B2	118.1 (17)
C2A—N1A—H1A	118.0 (16)	H6B1—N6B—H6B2	122 (2)
C5A—C6A—N1A	123.08 (19)	O1X—C1X—N2X	124.9 (2)
C5A—C6A—Cl6A	121.64 (16)	O1X—C1X—H1X	117.6
N1A—C6A—Cl6A	115.28 (17)	N2X—C1X—H1X	117.6
C6A—C5A—C4A	118.94 (19)	C1X—N2X—C4X	121.0 (2)
C6A—C5A—H5A	120.5	C1X—N2X—C3X	121.7 (2)
C4A—C5A—H5A	120.5	C4X—N2X—C3X	117.2 (2)
O4A—C4A—N3A	120.54 (19)	N2X—C3X—H3X1	109.5
O4A—C4A—C5A	125.06 (18)	N2X—C3X—H3X2	109.5
N3A—C4A—C5A	114.40 (19)	H3X1—C3X—H3X2	109.5
C2B—N1B—C6B	112.24 (16)	N2X—C3X—H3X3	109.5
N3B—C2B—N1B	130.55 (19)	H3X1—C3X—H3X3	109.5
N3B—C2B—Cl2B	114.70 (16)	H3X2—C3X—H3X3	109.5
N1B—C2B—Cl2B	114.74 (14)	N2X—C4X—H4X1	109.5
C2B—N3B—C4B	112.79 (17)	N2X—C4X—H4X2	109.5
N4B—C4B—N5B	118.78 (18)	H4X1—C4X—H4X2	109.5
N4B—C4B—N3B	117.29 (19)	N2X—C4X—H4X3	109.5
N5B—C4B—N3B	123.92 (17)	H4X1—C4X—H4X3	109.5
C4B—N4B—H4B1	121.8 (16)	H4X2—C4X—H4X3	109.5
C4A—N3A—C2A—O2A	−177.8 (2)	C6B—N1B—C2B—Cl2B	177.26 (15)
C4A—N3A—C2A—N1A	1.6 (3)	N1B—C2B—N3B—C4B	1.2 (3)
O2A—C2A—N1A—C6A	178.5 (2)	Cl2B—C2B—N3B—C4B	−178.15 (15)
N3A—C2A—N1A—C6A	−0.9 (3)	C2B—N3B—C4B—N4B	−178.85 (19)
C2A—N1A—C6A—C5A	0.1 (3)	C2B—N3B—C4B—N5B	0.6 (3)
C2A—N1A—C6A—Cl6A	−179.43 (16)	N4B—C4B—N5B—C6B	178.27 (19)
N1A—C6A—C5A—C4A	0.2 (3)	N3B—C4B—N5B—C6B	−1.2 (3)
Cl6A—C6A—C5A—C4A	179.70 (17)	C4B—N5B—C6B—N6B	−179.89 (18)
C2A—N3A—C4A—O4A	178.3 (2)	C4B—N5B—C6B—N1B	0.2 (3)
C2A—N3A—C4A—C5A	−1.4 (3)	C2B—N1B—C6B—N6B	−178.67 (19)
C6A—C5A—C4A—O4A	−179.3 (2)	C2B—N1B—C6B—N5B	1.3 (3)
C6A—C5A—C4A—N3A	0.4 (3)	O1X—C1X—N2X—C4X	0.7 (4)
C6B—N1B—C2B—N3B	−2.1 (3)	O1X—C1X—N2X—C3X	177.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1X	0.89 (2)	1.83 (2)	2.718 (2)	173 (2)
N3A—H3A···N5B	0.87 (2)	2.01 (2)	2.873 (2)	176 (2)
N4B—H4B1···N3B^i	0.87 (2)	2.12 (2)	2.981 (3)	174 (2)
N4B—H4B2···O4A	0.87 (2)	2.05 (2)	2.914 (2)	177 (2)
N6B—H6B1···O2A	0.89 (2)	2.05 (2)	2.930 (3)	174 (2)
N6B—H6B2···N1B^ii	0.88 (2)	2.12 (2)	2.998 (2)	179 (2)
C1X—H1X···O2A	0.95	2.51	3.267 (3)	137

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

(Vb) ;

Crystal data

C4H3ClN2O2·C3H4ClN5·C3H7NO	Z = 4
Mr = 365.19	F(000) = 752
Triclinic, P1	Dx = 1.556 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.9691 (7) Å	Cell parameters from 49386 reflections
b = 12.3455 (7) Å	θ = 3.3–26.2°
c = 12.4618 (7) Å	µ = 0.45 mm^−1
α = 109.385 (4)°	T = 173 K
β = 96.199 (5)°	Block, colourless
γ = 111.598 (4)°	0.33 × 0.23 × 0.12 mm
V = 1558.46 (15) Å^3

Data collection

STOE IPDS II two-circle diffractometer	6006 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	5104 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.113
ω scans	θmax = 25.9°, θmin = 3.3°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −14→14
Tmin = 0.867, Tmax = 0.949	k = −15→15
43838 measured reflections	l = −15→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) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0884P)^2 + 0.2231P] where P = (Fo^2 + 2Fc^2)/3
6006 reflections	(Δ/σ)max = 0.001
455 parameters	Δρmax = 0.53 e Å^−3
12 restraints	Δρmin = −0.55 e Å^−3

Special details

Experimental. ;

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
N1A	1.10387 (17)	0.71445 (18)	0.01328 (16)	0.0332 (4)
H1A	1.0418 (17)	0.731 (2)	−0.006 (2)	0.040*
C2A	1.0893 (2)	0.6518 (2)	0.08711 (18)	0.0322 (5)
O2A	0.99504 (14)	0.62269 (17)	0.12223 (14)	0.0393 (4)
N3A	1.18501 (16)	0.62431 (18)	0.11771 (16)	0.0319 (4)
H3A	1.178 (2)	0.588 (2)	0.167 (2)	0.038*
C4A	1.2915 (2)	0.6491 (2)	0.07770 (19)	0.0337 (5)
O4A	1.37070 (15)	0.61858 (18)	0.11124 (15)	0.0434 (4)
C5A	1.2991 (2)	0.7135 (2)	−0.00107 (19)	0.0340 (5)
H5A	1.3689	0.7344	−0.0328	0.041*
C6A	1.2065 (2)	0.7431 (2)	−0.02845 (18)	0.0321 (4)
Cl6A	1.20924 (5)	0.82486 (6)	−0.11633 (5)	0.03922 (16)
N1B	1.03171 (16)	0.39213 (18)	0.37766 (15)	0.0311 (4)
C2B	1.12287 (19)	0.3634 (2)	0.40395 (17)	0.0288 (4)
Cl2B	1.09762 (5)	0.27155 (5)	0.48701 (5)	0.03683 (16)
N3B	1.23014 (16)	0.39184 (18)	0.37696 (15)	0.0306 (4)
C4B	1.24436 (18)	0.4624 (2)	0.31082 (17)	0.0284 (4)
N4B	1.35034 (17)	0.4953 (2)	0.27861 (16)	0.0336 (4)
H41B	1.405 (2)	0.469 (2)	0.300 (2)	0.040*
H42B	1.359 (2)	0.540 (2)	0.236 (2)	0.040*
N5B	1.16003 (16)	0.50033 (17)	0.27749 (15)	0.0298 (4)
C6B	1.05566 (18)	0.4642 (2)	0.31321 (17)	0.0287 (4)
N6B	0.96892 (17)	0.4990 (2)	0.28446 (17)	0.0346 (4)
H61B	0.9022 (16)	0.469 (2)	0.308 (2)	0.042*
H62B	0.977 (2)	0.544 (2)	0.243 (2)	0.042*
N1C	0.44441 (18)	0.06150 (19)	0.70656 (17)	0.0367 (4)
H1C	0.3725 (18)	0.040 (3)	0.724 (2)	0.044*
C2C	0.4598 (2)	0.1297 (2)	0.6364 (2)	0.0366 (5)
O2C	0.38156 (15)	0.16306 (19)	0.60756 (16)	0.0466 (4)
N3C	0.56785 (17)	0.15543 (19)	0.60167 (16)	0.0351 (4)
H3C	0.576 (2)	0.198 (2)	0.557 (2)	0.042*
C4C	0.6608 (2)	0.1208 (2)	0.62992 (19)	0.0345 (5)
O4C	0.75319 (16)	0.14906 (18)	0.59262 (16)	0.0450 (4)
C5C	0.6387 (2)	0.0516 (2)	0.7046 (2)	0.0362 (5)
H5C	0.6977	0.0241	0.7287	0.043*
C6C	0.5335 (2)	0.0269 (2)	0.73910 (19)	0.0344 (5)
Cl6C	0.50222 (6)	−0.05056 (6)	0.83176 (5)	0.04304 (17)
N1D	0.52898 (16)	0.39743 (18)	0.34964 (15)	0.0316 (4)
C2D	0.63648 (19)	0.4272 (2)	0.32350 (17)	0.0300 (4)
Cl2D	0.66167 (5)	0.52286 (6)	0.24403 (5)	0.04027 (17)
N3D	0.72737 (16)	0.39691 (17)	0.34702 (15)	0.0309 (4)
C4D	0.70355 (18)	0.3238 (2)	0.41140 (17)	0.0283 (4)
N4D	0.78999 (17)	0.28810 (19)	0.43875 (16)	0.0329 (4)
H41D	0.8587 (15)	0.318 (2)	0.418 (2)	0.039*
H42D	0.780 (2)	0.246 (2)	0.4840 (19)	0.039*
N5D	0.59895 (15)	0.28691 (17)	0.44660 (15)	0.0293 (4)
C6D	0.51435 (19)	0.3249 (2)	0.41448 (18)	0.0298 (4)
N6D	0.40816 (17)	0.2905 (2)	0.44504 (18)	0.0376 (4)
H61D	0.357 (2)	0.322 (2)	0.429 (2)	0.045*
H62D	0.400 (2)	0.252 (2)	0.4942 (19)	0.045*
C1X	0.8254 (2)	0.7195 (2)	−0.0061 (2)	0.0375 (5)
H1X	0.8305	0.6627	0.0283	0.045*
O1X	0.91428 (14)	0.76902 (17)	−0.04360 (15)	0.0429 (4)
N2X	0.72423 (18)	0.73971 (19)	−0.01031 (17)	0.0384 (4)
C3X	0.7081 (3)	0.8212 (3)	−0.0654 (2)	0.0500 (6)
H3X1	0.7841	0.8613	−0.0873	0.075*
H3X2	0.6911	0.8872	−0.0099	0.075*
H3X3	0.6380	0.7703	−0.1361	0.075*
C4X	0.6234 (2)	0.6752 (3)	0.0321 (3)	0.0519 (6)
H4X1	0.6425	0.6165	0.0592	0.078*
H4X2	0.5464	0.6275	−0.0317	0.078*
H4X3	0.6127	0.7380	0.0978	0.078*
C1Y	0.1566 (2)	0.0425 (2)	0.7171 (2)	0.0438 (6)
H1Y	0.1892	0.0854	0.6689	0.053*
O1Y	0.22262 (16)	0.00372 (18)	0.76253 (15)	0.0458 (4)
N2Y	0.04442 (19)	0.0293 (2)	0.72996 (18)	0.0418 (5)
C3Y	−0.0267 (3)	0.0768 (3)	0.6730 (3)	0.0629 (8)
H3Y1	0.0237	0.1238	0.6323	0.094*
H3Y2	−0.0499	0.1337	0.7323	0.094*
H3Y3	−0.1021	0.0053	0.6157	0.094*
C4Y	−0.0136 (3)	−0.0392 (3)	0.7995 (2)	0.0498 (6)
H4Y1	0.0360	−0.0811	0.8195	0.075*
H4Y2	−0.0979	−0.1034	0.7535	0.075*
H4Y3	−0.0176	0.0208	0.8720	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0338 (9)	0.0421 (10)	0.0362 (9)	0.0193 (8)	0.0134 (8)	0.0259 (8)
C2A	0.0361 (11)	0.0364 (12)	0.0302 (10)	0.0167 (9)	0.0111 (8)	0.0186 (9)
O2A	0.0362 (8)	0.0571 (10)	0.0445 (9)	0.0244 (7)	0.0190 (7)	0.0360 (8)
N3A	0.0332 (9)	0.0417 (10)	0.0324 (9)	0.0179 (8)	0.0123 (7)	0.0254 (8)
C4A	0.0353 (11)	0.0381 (12)	0.0332 (11)	0.0164 (9)	0.0121 (9)	0.0190 (9)
O4A	0.0399 (9)	0.0640 (11)	0.0522 (10)	0.0312 (8)	0.0227 (7)	0.0402 (9)
C5A	0.0336 (10)	0.0423 (12)	0.0345 (11)	0.0178 (9)	0.0153 (9)	0.0218 (10)
C6A	0.0381 (11)	0.0343 (11)	0.0278 (10)	0.0140 (9)	0.0106 (8)	0.0184 (9)
Cl6A	0.0444 (3)	0.0474 (3)	0.0395 (3)	0.0207 (2)	0.0164 (2)	0.0307 (3)
N1B	0.0314 (9)	0.0392 (10)	0.0304 (9)	0.0166 (8)	0.0103 (7)	0.0207 (8)
C2B	0.0337 (10)	0.0324 (11)	0.0245 (9)	0.0145 (8)	0.0082 (8)	0.0158 (8)
Cl2B	0.0426 (3)	0.0442 (3)	0.0360 (3)	0.0202 (2)	0.0137 (2)	0.0279 (2)
N3B	0.0321 (9)	0.0383 (10)	0.0281 (8)	0.0177 (8)	0.0093 (7)	0.0180 (8)
C4B	0.0295 (10)	0.0339 (11)	0.0250 (9)	0.0153 (8)	0.0081 (8)	0.0134 (8)
N4B	0.0326 (9)	0.0495 (11)	0.0353 (9)	0.0231 (8)	0.0154 (7)	0.0280 (9)
N5B	0.0308 (8)	0.0379 (10)	0.0294 (9)	0.0176 (7)	0.0114 (7)	0.0195 (8)
C6B	0.0296 (9)	0.0349 (11)	0.0261 (9)	0.0148 (8)	0.0090 (8)	0.0158 (8)
N6B	0.0319 (9)	0.0490 (11)	0.0405 (10)	0.0220 (8)	0.0163 (8)	0.0313 (9)
N1C	0.0362 (10)	0.0455 (11)	0.0400 (10)	0.0187 (9)	0.0149 (8)	0.0281 (9)
C2C	0.0372 (11)	0.0415 (13)	0.0397 (12)	0.0176 (10)	0.0140 (9)	0.0243 (10)
O2C	0.0428 (9)	0.0658 (12)	0.0600 (11)	0.0311 (9)	0.0246 (8)	0.0468 (10)
N3C	0.0379 (10)	0.0446 (11)	0.0377 (10)	0.0213 (8)	0.0158 (8)	0.0280 (9)
C4C	0.0365 (11)	0.0404 (12)	0.0344 (11)	0.0189 (9)	0.0120 (9)	0.0208 (10)
O4C	0.0440 (9)	0.0638 (11)	0.0544 (10)	0.0313 (8)	0.0255 (8)	0.0422 (9)
C5C	0.0377 (11)	0.0427 (13)	0.0372 (11)	0.0191 (10)	0.0110 (9)	0.0243 (10)
C6C	0.0409 (11)	0.0345 (11)	0.0295 (10)	0.0140 (9)	0.0065 (9)	0.0184 (9)
Cl6C	0.0489 (3)	0.0493 (4)	0.0402 (3)	0.0179 (3)	0.0136 (2)	0.0317 (3)
N1D	0.0323 (9)	0.0396 (10)	0.0325 (9)	0.0185 (8)	0.0107 (7)	0.0214 (8)
C2D	0.0342 (10)	0.0361 (11)	0.0251 (9)	0.0156 (9)	0.0083 (8)	0.0178 (9)
Cl2D	0.0419 (3)	0.0536 (4)	0.0414 (3)	0.0223 (3)	0.0139 (2)	0.0349 (3)
N3D	0.0336 (9)	0.0383 (10)	0.0281 (9)	0.0168 (8)	0.0113 (7)	0.0195 (8)
C4D	0.0312 (10)	0.0316 (10)	0.0250 (9)	0.0137 (8)	0.0081 (8)	0.0144 (8)
N4D	0.0307 (9)	0.0449 (11)	0.0382 (10)	0.0204 (8)	0.0161 (7)	0.0276 (9)
N5D	0.0297 (8)	0.0368 (10)	0.0290 (8)	0.0162 (7)	0.0101 (7)	0.0190 (8)
C6D	0.0311 (10)	0.0348 (11)	0.0282 (10)	0.0146 (8)	0.0091 (8)	0.0171 (9)
N6D	0.0337 (9)	0.0522 (12)	0.0482 (11)	0.0252 (9)	0.0183 (8)	0.0351 (10)
C1X	0.0407 (12)	0.0425 (13)	0.0346 (11)	0.0199 (10)	0.0094 (9)	0.0195 (10)
O1X	0.0386 (9)	0.0548 (11)	0.0475 (9)	0.0247 (8)	0.0153 (7)	0.0284 (8)
N2X	0.0379 (10)	0.0442 (11)	0.0371 (10)	0.0188 (8)	0.0090 (8)	0.0202 (9)
C3X	0.0495 (14)	0.0599 (17)	0.0538 (15)	0.0308 (13)	0.0114 (12)	0.0307 (13)
C4X	0.0409 (13)	0.0606 (17)	0.0547 (15)	0.0184 (12)	0.0147 (11)	0.0271 (14)
C1Y	0.0470 (13)	0.0489 (14)	0.0438 (13)	0.0206 (11)	0.0170 (10)	0.0267 (11)
O1Y	0.0440 (9)	0.0601 (11)	0.0495 (10)	0.0256 (8)	0.0191 (8)	0.0351 (9)
N2Y	0.0455 (11)	0.0456 (11)	0.0432 (11)	0.0219 (9)	0.0148 (9)	0.0249 (9)
C3Y	0.0655 (18)	0.075 (2)	0.074 (2)	0.0434 (16)	0.0224 (15)	0.0444 (17)
C4Y	0.0507 (14)	0.0561 (16)	0.0471 (14)	0.0202 (12)	0.0227 (12)	0.0263 (13)

Geometric parameters (Å, º)

N1A—C6A	1.358 (3)	C6C—Cl6C	1.718 (2)
N1A—C2A	1.372 (3)	N1D—C2D	1.311 (3)
N1A—H1A	0.872 (10)	N1D—C6D	1.372 (3)
C2A—O2A	1.227 (3)	C2D—N3D	1.309 (3)
C2A—N3A	1.361 (3)	C2D—Cl2D	1.745 (2)
N3A—C4A	1.385 (3)	N3D—C4D	1.371 (3)
N3A—H3A	0.869 (17)	C4D—N4D	1.319 (3)
C4A—O4A	1.224 (3)	C4D—N5D	1.341 (3)
C4A—C5A	1.445 (3)	N4D—H41D	0.873 (10)
C5A—C6A	1.333 (3)	N4D—H42D	0.877 (10)
C5A—H5A	0.9500	N5D—C6D	1.338 (3)
C6A—Cl6A	1.714 (2)	C6D—N6D	1.325 (3)
N1B—C2B	1.307 (3)	N6D—H61D	0.874 (10)
N1B—C6B	1.362 (3)	N6D—H62D	0.885 (10)
C2B—N3B	1.313 (3)	C1X—O1X	1.242 (3)
C2B—Cl2B	1.745 (2)	C1X—N2X	1.323 (3)
N3B—C4B	1.365 (3)	C1X—H1X	0.9500
C4B—N4B	1.332 (3)	N2X—C4X	1.442 (3)
C4B—N5B	1.341 (3)	N2X—C3X	1.447 (3)
N4B—H41B	0.879 (10)	C3X—H3X1	0.9800
N4B—H42B	0.878 (10)	C3X—H3X2	0.9800
N5B—C6B	1.341 (3)	C3X—H3X3	0.9800
C6B—N6B	1.319 (3)	C4X—H4X1	0.9800
N6B—H61B	0.878 (10)	C4X—H4X2	0.9800
N6B—H62B	0.872 (10)	C4X—H4X3	0.9800
N1C—C6C	1.357 (3)	C1Y—O1Y	1.240 (3)
N1C—C2C	1.384 (3)	C1Y—N2Y	1.326 (3)
N1C—H1C	0.876 (17)	C1Y—H1Y	0.9500
C2C—O2C	1.219 (3)	N2Y—C3Y	1.445 (3)
C2C—N3C	1.367 (3)	N2Y—C4Y	1.460 (3)
N3C—C4C	1.383 (3)	C3Y—H3Y1	0.9800
N3C—H3C	0.883 (17)	C3Y—H3Y2	0.9800
C4C—O4C	1.223 (3)	C3Y—H3Y3	0.9800
C4C—C5C	1.442 (3)	C4Y—H4Y1	0.9800
C5C—C6C	1.336 (3)	C4Y—H4Y2	0.9800
C5C—H5C	0.9500	C4Y—H4Y3	0.9800
C6A—N1A—C2A	121.27 (18)	C2D—N1D—C6D	112.34 (17)
C6A—N1A—H1A	123.6 (18)	N3D—C2D—N1D	130.68 (19)
C2A—N1A—H1A	115.1 (18)	N3D—C2D—Cl2D	115.04 (15)
O2A—C2A—N3A	122.84 (19)	N1D—C2D—Cl2D	114.29 (15)
O2A—C2A—N1A	121.37 (19)	C2D—N3D—C4D	112.50 (18)
N3A—C2A—N1A	115.79 (18)	N4D—C4D—N5D	119.15 (18)
C2A—N3A—C4A	126.10 (18)	N4D—C4D—N3D	116.75 (18)
C2A—N3A—H3A	116.2 (17)	N5D—C4D—N3D	124.10 (18)
C4A—N3A—H3A	117.7 (17)	C4D—N4D—H41D	116.7 (17)
O4A—C4A—N3A	119.82 (19)	C4D—N4D—H42D	118.9 (17)
O4A—C4A—C5A	125.4 (2)	H41D—N4D—H42D	124 (2)
N3A—C4A—C5A	114.73 (18)	C6D—N5D—C4D	116.11 (18)
C6A—C5A—C4A	118.93 (19)	N6D—C6D—N5D	119.33 (19)
C6A—C5A—H5A	120.5	N6D—C6D—N1D	116.42 (18)
C4A—C5A—H5A	120.5	N5D—C6D—N1D	124.25 (18)
C5A—C6A—N1A	123.13 (19)	C6D—N6D—H61D	118.2 (19)
C5A—C6A—Cl6A	122.60 (17)	C6D—N6D—H62D	118.2 (18)
N1A—C6A—Cl6A	114.24 (16)	H61D—N6D—H62D	122 (3)
C2B—N1B—C6B	112.89 (17)	O1X—C1X—N2X	124.9 (2)
N1B—C2B—N3B	130.28 (19)	O1X—C1X—H1X	117.5
N1B—C2B—Cl2B	114.93 (15)	N2X—C1X—H1X	117.5
N3B—C2B—Cl2B	114.79 (15)	C1X—N2X—C4X	121.5 (2)
C2B—N3B—C4B	112.33 (17)	C1X—N2X—C3X	120.5 (2)
N4B—C4B—N5B	118.77 (18)	C4X—N2X—C3X	117.9 (2)
N4B—C4B—N3B	116.66 (18)	N2X—C3X—H3X1	109.5
N5B—C4B—N3B	124.57 (18)	N2X—C3X—H3X2	109.5
C4B—N4B—H41B	118.4 (18)	H3X1—C3X—H3X2	109.5
C4B—N4B—H42B	116.7 (17)	N2X—C3X—H3X3	109.5
H41B—N4B—H42B	125 (2)	H3X1—C3X—H3X3	109.5
C4B—N5B—C6B	115.66 (17)	H3X2—C3X—H3X3	109.5
N6B—C6B—N5B	119.02 (19)	N2X—C4X—H4X1	109.5
N6B—C6B—N1B	116.73 (18)	N2X—C4X—H4X2	109.5
N5B—C6B—N1B	124.26 (18)	H4X1—C4X—H4X2	109.5
C6B—N6B—H61B	113.4 (18)	N2X—C4X—H4X3	109.5
C6B—N6B—H62B	122.1 (18)	H4X1—C4X—H4X3	109.5
H61B—N6B—H62B	124 (3)	H4X2—C4X—H4X3	109.5
C6C—N1C—C2C	120.84 (19)	O1Y—C1Y—N2Y	125.6 (2)
C6C—N1C—H1C	124.4 (18)	O1Y—C1Y—H1Y	117.2
C2C—N1C—H1C	114.7 (18)	N2Y—C1Y—H1Y	117.2
O2C—C2C—N3C	123.0 (2)	C1Y—N2Y—C3Y	122.0 (2)
O2C—C2C—N1C	121.8 (2)	C1Y—N2Y—C4Y	120.4 (2)
N3C—C2C—N1C	115.21 (19)	C3Y—N2Y—C4Y	117.6 (2)
C2C—N3C—C4C	126.65 (19)	N2Y—C3Y—H3Y1	109.5
C2C—N3C—H3C	114.0 (17)	N2Y—C3Y—H3Y2	109.5
C4C—N3C—H3C	119.3 (17)	H3Y1—C3Y—H3Y2	109.5
O4C—C4C—N3C	120.4 (2)	N2Y—C3Y—H3Y3	109.5
O4C—C4C—C5C	124.8 (2)	H3Y1—C3Y—H3Y3	109.5
N3C—C4C—C5C	114.83 (19)	H3Y2—C3Y—H3Y3	109.5
C6C—C5C—C4C	118.6 (2)	N2Y—C4Y—H4Y1	109.5
C6C—C5C—H5C	120.7	N2Y—C4Y—H4Y2	109.5
C4C—C5C—H5C	120.7	H4Y1—C4Y—H4Y2	109.5
C5C—C6C—N1C	123.8 (2)	N2Y—C4Y—H4Y3	109.5
C5C—C6C—Cl6C	121.58 (17)	H4Y1—C4Y—H4Y3	109.5
N1C—C6C—Cl6C	114.57 (16)	H4Y2—C4Y—H4Y3	109.5
C6A—N1A—C2A—O2A	−177.9 (2)	O2C—C2C—N3C—C4C	−179.7 (2)
C6A—N1A—C2A—N3A	1.8 (3)	N1C—C2C—N3C—C4C	−0.3 (3)
O2A—C2A—N3A—C4A	177.0 (2)	C2C—N3C—C4C—O4C	179.6 (2)
N1A—C2A—N3A—C4A	−2.7 (3)	C2C—N3C—C4C—C5C	−0.6 (3)
C2A—N3A—C4A—O4A	−179.4 (2)	O4C—C4C—C5C—C6C	180.0 (2)
C2A—N3A—C4A—C5A	1.8 (3)	N3C—C4C—C5C—C6C	0.2 (3)
O4A—C4A—C5A—C6A	−178.8 (2)	C4C—C5C—C6C—N1C	1.1 (4)
N3A—C4A—C5A—C6A	0.0 (3)	C4C—C5C—C6C—Cl6C	−177.92 (17)
C4A—C5A—C6A—N1A	−0.7 (3)	C2C—N1C—C6C—C5C	−2.0 (4)
C4A—C5A—C6A—Cl6A	177.37 (17)	C2C—N1C—C6C—Cl6C	177.05 (17)
C2A—N1A—C6A—C5A	−0.2 (3)	C6D—N1D—C2D—N3D	1.6 (3)
C2A—N1A—C6A—Cl6A	−178.45 (16)	C6D—N1D—C2D—Cl2D	−178.51 (15)
C6B—N1B—C2B—N3B	−0.9 (3)	N1D—C2D—N3D—C4D	−1.2 (3)
C6B—N1B—C2B—Cl2B	179.78 (14)	Cl2D—C2D—N3D—C4D	178.84 (14)
N1B—C2B—N3B—C4B	−0.1 (3)	C2D—N3D—C4D—N4D	179.65 (18)
Cl2B—C2B—N3B—C4B	179.25 (14)	C2D—N3D—C4D—N5D	0.1 (3)
C2B—N3B—C4B—N4B	−179.67 (19)	N4D—C4D—N5D—C6D	−179.07 (19)
C2B—N3B—C4B—N5B	0.7 (3)	N3D—C4D—N5D—C6D	0.5 (3)
N4B—C4B—N5B—C6B	−179.81 (19)	C4D—N5D—C6D—N6D	179.19 (19)
N3B—C4B—N5B—C6B	−0.2 (3)	C4D—N5D—C6D—N1D	−0.1 (3)
C4B—N5B—C6B—N6B	179.48 (19)	C2D—N1D—C6D—N6D	179.90 (19)
C4B—N5B—C6B—N1B	−1.0 (3)	C2D—N1D—C6D—N5D	−0.8 (3)
C2B—N1B—C6B—N6B	−179.02 (19)	O1X—C1X—N2X—C4X	178.1 (2)
C2B—N1B—C6B—N5B	1.4 (3)	O1X—C1X—N2X—C3X	2.3 (4)
C6C—N1C—C2C—O2C	−179.0 (2)	O1Y—C1Y—N2Y—C3Y	−179.6 (3)
C6C—N1C—C2C—N3C	1.5 (3)	O1Y—C1Y—N2Y—C4Y	−2.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1X	0.87 (1)	1.81 (1)	2.683 (2)	179 (3)
N3A—H3A···N5B	0.87 (2)	2.00 (2)	2.866 (2)	179 (2)
N4B—H41B···N1D^i	0.88 (1)	2.13 (1)	3.003 (3)	177 (2)
N4B—H42B···O4A	0.88 (1)	2.07 (1)	2.944 (2)	171 (2)
N6B—H61B···N3D	0.88 (1)	2.13 (1)	3.002 (3)	172 (2)
N6B—H62B···O2A	0.87 (1)	2.03 (1)	2.890 (2)	170 (2)
N1C—H1C···O1Y	0.88 (2)	1.84 (2)	2.716 (3)	177 (3)
N3C—H3C···N5D	0.88 (2)	2.00 (2)	2.881 (3)	176 (2)
N6D—H61D···N3B^ii	0.87 (1)	2.14 (1)	3.017 (3)	176 (3)
N6D—H62D···O2C	0.89 (1)	2.04 (1)	2.927 (2)	180 (3)
N4D—H41D···N1B	0.87 (1)	2.13 (1)	2.998 (3)	177 (2)
N4D—H42D···O4C	0.88 (1)	2.06 (1)	2.937 (2)	178 (2)
C1X—H1X···O2A	0.95	2.47	3.234 (3)	138
C1Y—H1Y···O2C	0.95	2.46	3.244 (3)	140

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

(VI) ;

Crystal data

C5H5ClN2O2	F(000) = 328
Mr = 160.56	Dx = 1.690 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5122 reflections
a = 4.4135 (6) Å	θ = 3.4–25.9°
b = 15.780 (3) Å	µ = 0.53 mm^−1
c = 9.0645 (14) Å	T = 173 K
β = 92.025 (12)°	Plate, colourless
V = 630.91 (17) Å^3	0.11 × 0.09 × 0.08 mm
Z = 4

Data collection

STOE IPDS II two-circle diffractometer	1179 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	970 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.044
ω scans	θmax = 25.6°, θmin = 3.4°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −5→5
Tmin = 0.943, Tmax = 0.959	k = −19→19
4810 measured reflections	l = −10→10

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0367P)^2 + 0.1541P] where P = (Fo^2 + 2Fc^2)/3
1179 reflections	(Δ/σ)max < 0.001
96 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Experimental. ;

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	0.0809 (3)	0.26316 (10)	0.53362 (17)	0.0228 (3)
H1	−0.050 (6)	0.2800 (17)	0.467 (3)	0.039 (6)*
C2	0.1005 (4)	0.17687 (11)	0.54497 (19)	0.0214 (4)
O2	−0.0581 (3)	0.13002 (9)	0.46897 (15)	0.0295 (3)
N3	0.3132 (3)	0.14704 (9)	0.64970 (16)	0.0211 (3)
C3	0.3435 (5)	0.05577 (12)	0.6677 (2)	0.0291 (4)
H3A	0.5476	0.0383	0.6413	0.044*
H3B	0.1931	0.0270	0.6033	0.044*
H3C	0.3103	0.0405	0.7707	0.044*
C4	0.4967 (4)	0.19943 (12)	0.7379 (2)	0.0209 (4)
O4	0.6823 (3)	0.16599 (9)	0.82585 (15)	0.0286 (3)
C5	0.4570 (4)	0.28859 (12)	0.72132 (18)	0.0224 (4)
H5	0.5733	0.3273	0.7803	0.027*
C6	0.2515 (4)	0.31643 (11)	0.62035 (19)	0.0223 (4)
Cl6	0.18286 (12)	0.42189 (3)	0.59132 (5)	0.03316 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0215 (8)	0.0250 (8)	0.0214 (7)	0.0002 (6)	−0.0074 (6)	0.0007 (6)
C2	0.0199 (9)	0.0255 (10)	0.0186 (9)	−0.0014 (7)	−0.0022 (7)	0.0003 (7)
O2	0.0312 (7)	0.0280 (7)	0.0283 (7)	−0.0068 (6)	−0.0128 (6)	0.0000 (6)
N3	0.0207 (8)	0.0212 (8)	0.0210 (8)	−0.0002 (6)	−0.0044 (6)	−0.0011 (6)
C3	0.0365 (11)	0.0198 (9)	0.0304 (10)	−0.0011 (8)	−0.0084 (8)	0.0001 (7)
C4	0.0186 (8)	0.0265 (9)	0.0173 (8)	−0.0003 (7)	−0.0015 (6)	−0.0017 (7)
O4	0.0280 (7)	0.0298 (7)	0.0270 (7)	0.0033 (6)	−0.0129 (6)	−0.0012 (6)
C5	0.0213 (9)	0.0251 (9)	0.0204 (9)	−0.0007 (7)	−0.0036 (7)	−0.0036 (7)
C6	0.0229 (10)	0.0222 (9)	0.0217 (9)	0.0004 (7)	0.0000 (7)	−0.0003 (7)
Cl6	0.0425 (3)	0.0208 (2)	0.0352 (3)	0.0037 (2)	−0.0119 (2)	−0.00035 (19)

Geometric parameters (Å, º)

N1—C6	1.360 (2)	C3—H3B	0.9800
N1—C2	1.368 (2)	C3—H3C	0.9800
N1—H1	0.86 (3)	C4—O4	1.241 (2)
C2—O2	1.215 (2)	C4—C5	1.425 (3)
C2—N3	1.393 (2)	C5—C6	1.340 (2)
N3—C4	1.390 (2)	C5—H5	0.9500
N3—C3	1.455 (2)	C6—Cl6	1.7103 (19)
C3—H3A	0.9800
C6—N1—C2	122.65 (16)	N3—C3—H3C	109.5
C6—N1—H1	123.9 (18)	H3A—C3—H3C	109.5
C2—N1—H1	113.4 (18)	H3B—C3—H3C	109.5
O2—C2—N1	121.96 (17)	O4—C4—N3	118.33 (17)
O2—C2—N3	122.77 (17)	O4—C4—C5	124.30 (17)
N1—C2—N3	115.27 (15)	N3—C4—C5	117.37 (16)
C4—N3—C2	123.75 (16)	C6—C5—C4	118.26 (16)
C4—N3—C3	118.34 (15)	C6—C5—H5	120.9
C2—N3—C3	117.91 (15)	C4—C5—H5	120.9
N3—C3—H3A	109.5	C5—C6—N1	122.67 (17)
N3—C3—H3B	109.5	C5—C6—Cl6	122.42 (14)
H3A—C3—H3B	109.5	N1—C6—Cl6	114.91 (13)
C6—N1—C2—O2	178.34 (18)	C2—N3—C4—C5	1.5 (3)
C6—N1—C2—N3	−1.4 (3)	C3—N3—C4—C5	−178.26 (16)
O2—C2—N3—C4	−179.92 (18)	O4—C4—C5—C6	178.94 (19)
N1—C2—N3—C4	−0.2 (3)	N3—C4—C5—C6	−1.4 (3)
O2—C2—N3—C3	−0.1 (3)	C4—C5—C6—N1	−0.1 (3)
N1—C2—N3—C3	179.62 (16)	C4—C5—C6—Cl6	179.65 (14)
C2—N3—C4—O4	−178.75 (16)	C2—N1—C6—C5	1.6 (3)
C3—N3—C4—O4	1.5 (3)	C2—N1—C6—Cl6	−178.18 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^i	0.86 (3)	1.91 (3)	2.767 (2)	171 (3)
C5—H5···O2^ii	0.95	2.41	3.306 (2)	156

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

(VII)

Crystal data

C5H5ClN2O2·2(C3H6N6)·C4H9NO·C2H7N·3(HCl)	F(000) = 1368
Mr = 654.42	Dx = 1.480 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 29644 reflections
a = 18.6341 (15) Å	θ = 3.4–26.3°
b = 13.0507 (10) Å	µ = 0.46 mm^−1
c = 12.3166 (10) Å	T = 173 K
β = 101.365 (7)°	Plate, colourless
V = 2936.5 (4) Å^3	0.15 × 0.14 × 0.07 mm
Z = 4

Data collection

STOE IPDS II two-circle- diffractometer	2960 independent reflections
Radiation source: Genix 3D IµS microfocus X-ray source	2332 reflections with I > 2σ(I)
Genix 3D multilayer optics monochromator	Rint = 0.056
ω scans	θmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan X-AREA (Stoe & Cie, 2001)	h = −22→22
Tmin = 0.935, Tmax = 0.969	k = −15→15
25210 measured reflections	l = −15→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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0738P)^2 + 7.4826P] where P = (Fo^2 + 2Fc^2)/3
2960 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 0.34 e Å^−3
25 restraints	Δρmin = −0.62 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	0.2794 (3)	0.0000	−0.0591 (4)	0.0497 (13)
H1A	0.291 (4)	0.0000	−0.126 (3)	0.060*
C2A	0.2082 (3)	0.0000	−0.0565 (5)	0.0428 (14)
O2A	0.1602 (2)	0.0000	−0.1410 (4)	0.0648 (14)
N3A	0.1896 (3)	0.0000	0.0481 (4)	0.0435 (12)
C3A	0.1114 (3)	0.0000	0.0516 (5)	0.0484 (15)
H3A1	0.0840	−0.0345	−0.0144	0.073*	0.50
H3A2	0.0942	0.0708	0.0536	0.073*	0.50
H3A3	0.1038	−0.0363	0.1181	0.073*	0.50
C4A	0.2410 (3)	0.0000	0.1459 (5)	0.0455 (15)
O4A	0.2202 (2)	0.0000	0.2347 (3)	0.0565 (12)
C5A	0.3166 (3)	0.0000	0.1360 (5)	0.0535 (17)
H5A	0.3546	0.0000	0.2000	0.064*
C6A	0.3322 (4)	0.0000	0.0361 (6)	0.0594 (19)
Cl6A	0.42010 (10)	0.0000	0.0147 (2)	0.0930 (8)
N1B	0.23525 (18)	0.2494 (3)	0.8426 (3)	0.0448 (9)
C2B	0.2018 (2)	0.2539 (3)	0.7342 (3)	0.0407 (10)
N2B	0.12996 (19)	0.2587 (3)	0.7133 (3)	0.0488 (10)
H2B1	0.103 (2)	0.250 (4)	0.763 (3)	0.059*
H2B2	0.106 (2)	0.259 (4)	0.645 (2)	0.059*
N3B	0.23541 (17)	0.2543 (3)	0.6472 (3)	0.0360 (7)
C4B	0.3076 (2)	0.2531 (3)	0.6710 (3)	0.0353 (9)
N4B	0.34571 (19)	0.2542 (3)	0.5913 (3)	0.0401 (8)
H4B1	0.3940 (11)	0.251 (4)	0.604 (4)	0.048*
H4B2	0.320 (2)	0.253 (3)	0.524 (2)	0.048*
N5B	0.34509 (18)	0.2511 (3)	0.7776 (3)	0.0394 (8)
H5B	0.3927 (11)	0.257 (3)	0.790 (4)	0.047*
C6B	0.3076 (2)	0.2488 (3)	0.8611 (3)	0.0422 (10)
N6B	0.3454 (2)	0.2465 (3)	0.9644 (3)	0.0513 (11)
H6B1	0.3914 (13)	0.252 (4)	0.965 (4)	0.062*
H6B2	0.323 (3)	0.251 (4)	1.021 (3)	0.062*
Cl1C	0.49320 (5)	0.29003 (8)	1.15072 (7)	0.0399 (3)
Cl1D	0.0000	0.24959 (11)	0.5000	0.0393 (4)
C1E	0.4320 (4)	0.5000	1.3603 (5)	0.0516 (16)
H1E1	0.3815	0.5000	1.3185	0.077*
H1E2	0.4404	0.5613	1.4070	0.077*	0.50
H1E3	0.4404	0.4387	1.4070	0.077*	0.50
N2E	0.4833 (3)	0.5000	1.2819 (4)	0.0443 (12)
H2E1	0.474 (2)	0.448 (3)	1.236 (3)	0.053*
C3E	0.5599 (3)	0.5000	1.3414 (5)	0.0479 (15)
H3E1	0.5925	0.5000	1.2878	0.072*
H3E2	0.5692	0.4387	1.3880	0.072*	0.50
H3E3	0.5692	0.5613	1.3880	0.072*	0.50
C2X	0.3534 (7)	0.0000	−0.3328 (8)	0.046 (4)	0.626 (19)
N3X	0.3273 (5)	0.0000	−0.4391 (7)	0.040 (3)	0.626 (19)
C2X'	0.3129 (7)	0.0000	−0.3732 (11)	0.034 (5)	0.374 (19)
N3X'	0.3783 (7)	0.0000	−0.4019 (9)	0.039 (5)	0.374 (19)
C1X	0.4389 (5)	0.0000	−0.3022 (8)	0.084 (3)
H1X1	0.4587	0.0000	−0.3702	0.126*	0.626 (19)
H1X2	0.4557	−0.0613	−0.2587	0.126*	0.313 (9)
H1X3	0.4557	0.0613	−0.2587	0.126*	0.313 (9)
H4XA	0.4861	0.0000	−0.3258	0.126*	0.374 (19)
H4XB	0.4351	−0.0613	−0.2578	0.126*	0.187 (9)
H4XC	0.4351	0.0613	−0.2578	0.126*	0.187 (9)
O2X	0.3105 (3)	0.0000	−0.2688 (4)	0.0646 (14)
C4X	0.2471 (3)	0.0000	−0.4732 (5)	0.0476 (15)
H4X1	0.2336	0.0000	−0.5542	0.071*	0.626 (19)
H4X2	0.2271	0.0613	−0.4440	0.071*	0.313 (9)
H4X3	0.2271	−0.0613	−0.4440	0.071*	0.313 (9)
H1XA	0.2654	0.0000	−0.5425	0.071*	0.374 (19)
H1XB	0.2172	0.0613	−0.4700	0.071*	0.187 (9)
H1XC	0.2172	−0.0613	−0.4700	0.071*	0.187 (9)
C5X	0.3786 (4)	0.0000	−0.5218 (5)	0.0601 (19)
H5X1	0.3496	0.0000	−0.5974	0.090*	0.626 (19)
H5X2	0.4095	−0.0613	−0.5105	0.090*	0.313 (9)
H5X3	0.4095	0.0613	−0.5105	0.090*	0.313 (9)
H5XA	0.4292	0.0000	−0.5330	0.090*	0.374 (19)
H5XB	0.3533	0.0613	−0.5560	0.090*	0.187 (9)
H5XC	0.3533	−0.0613	−0.5560	0.090*	0.187 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.045 (3)	0.067 (4)	0.036 (3)	0.000	0.006 (2)	0.000
C2A	0.040 (3)	0.047 (4)	0.038 (3)	0.000	0.002 (2)	0.000
O2A	0.046 (3)	0.097 (4)	0.048 (3)	0.000	0.000 (2)	0.000
N3A	0.041 (3)	0.049 (3)	0.040 (3)	0.000	0.008 (2)	0.000
C3A	0.039 (3)	0.062 (4)	0.045 (3)	0.000	0.010 (3)	0.000
C4A	0.051 (4)	0.048 (4)	0.037 (3)	0.000	0.008 (3)	0.000
O4A	0.056 (3)	0.080 (4)	0.034 (2)	0.000	0.009 (2)	0.000
C5A	0.040 (3)	0.078 (5)	0.039 (3)	0.000	0.001 (3)	0.000
C6A	0.037 (3)	0.079 (5)	0.059 (4)	0.000	0.001 (3)	0.000
Cl6A	0.0386 (10)	0.156 (3)	0.0842 (15)	0.000	0.0117 (9)	0.000
N1B	0.0450 (19)	0.053 (2)	0.0284 (16)	−0.0272 (17)	−0.0117 (14)	0.0168 (15)
C2B	0.045 (2)	0.039 (2)	0.032 (2)	−0.0195 (18)	−0.0103 (16)	0.0122 (16)
N2B	0.0408 (19)	0.074 (3)	0.0258 (16)	−0.0241 (18)	−0.0080 (14)	0.0149 (17)
N3B	0.0380 (17)	0.0332 (18)	0.0310 (16)	−0.0099 (14)	−0.0074 (13)	0.0070 (13)
C4B	0.044 (2)	0.0216 (18)	0.0339 (19)	−0.0089 (16)	−0.0083 (16)	0.0074 (15)
N4B	0.0368 (17)	0.0364 (19)	0.0409 (19)	0.0012 (15)	−0.0072 (15)	−0.0019 (15)
N5B	0.0360 (17)	0.0343 (19)	0.0399 (18)	−0.0118 (15)	−0.0124 (14)	0.0074 (14)
C6B	0.047 (2)	0.035 (2)	0.037 (2)	−0.0242 (18)	−0.0124 (18)	0.0155 (17)
N6B	0.049 (2)	0.059 (2)	0.0354 (18)	−0.0272 (19)	−0.0166 (16)	0.0186 (18)
Cl1C	0.0323 (5)	0.0509 (6)	0.0321 (5)	−0.0078 (4)	−0.0042 (3)	0.0039 (4)
Cl1D	0.0380 (7)	0.0437 (8)	0.0295 (6)	0.000	−0.0093 (5)	0.000
C1E	0.050 (4)	0.059 (4)	0.045 (3)	0.000	0.009 (3)	0.000
N2E	0.050 (3)	0.045 (3)	0.033 (3)	0.000	−0.003 (2)	0.000
C3E	0.040 (3)	0.060 (4)	0.041 (3)	0.000	0.002 (3)	0.000
C2X	0.073 (9)	0.026 (6)	0.035 (6)	0.000	0.002 (6)	0.000
N3X	0.062 (7)	0.029 (4)	0.029 (5)	0.000	0.007 (4)	0.000
C2X'	0.057 (11)	0.019 (8)	0.024 (11)	0.000	0.004 (8)	0.000
N3X'	0.040 (9)	0.030 (8)	0.042 (10)	0.000	−0.008 (7)	0.000
C1X	0.073 (5)	0.064 (6)	0.096 (6)	0.000	−0.027 (5)	0.000
O2X	0.091 (4)	0.069 (4)	0.038 (2)	0.000	0.022 (3)	0.000
C4X	0.057 (4)	0.042 (4)	0.043 (3)	0.000	0.008 (3)	0.000
C5X	0.092 (6)	0.047 (4)	0.048 (4)	0.000	0.030 (4)	0.000

Geometric parameters (Å, º)

N1A—C2A	1.332 (8)	C1E—H1E3	0.9800
N1A—C6A	1.375 (8)	N2E—C3E	1.471 (8)
N1A—H1A	0.89 (2)	N2E—H2E1	0.877 (19)
C2A—O2A	1.231 (7)	C3E—H3E1	0.9800
C2A—N3A	1.399 (7)	C3E—H3E2	0.9800
N3A—C4A	1.384 (8)	C3E—H3E3	0.9800
N3A—C3A	1.466 (7)	C2X—O2X	1.227 (11)
C3A—H3A1	0.9800	C2X—N3X	1.304 (12)
C3A—H3A2	0.9800	C2X—C1X	1.563 (15)
C3A—H3A3	0.9800	N3X—C4X	1.470 (10)
C4A—O4A	1.230 (7)	N3X—C5X	1.528 (10)
C4A—C5A	1.438 (9)	C2X'—O2X	1.295 (13)
C5A—C6A	1.319 (9)	C2X'—N3X'	1.334 (16)
C5A—H5A	0.9500	C2X'—C4X	1.558 (13)
C6A—Cl6A	1.709 (7)	N3X'—C5X	1.478 (12)
N1B—C6B	1.322 (5)	N3X'—C1X	1.495 (12)
N1B—C2B	1.359 (5)	C1X—H1X1	0.9800
C2B—N2B	1.314 (6)	C1X—H1X2	0.9800
C2B—N3B	1.344 (5)	C1X—H1X3	0.9800
N2B—H2B1	0.882 (19)	C1X—H4XA	0.9800
N2B—H2B2	0.87 (2)	C1X—H4XB	0.9800
N3B—C4B	1.320 (5)	C1X—H4XC	0.9800
C4B—N4B	1.319 (5)	C4X—H4X1	0.9800
C4B—N5B	1.361 (5)	C4X—H4X2	0.9800
N4B—H4B1	0.884 (19)	C4X—H4X3	0.9800
N4B—H4B2	0.874 (19)	C4X—H1XA	0.9800
N5B—C6B	1.352 (6)	C4X—H1XB	0.9800
N5B—H5B	0.874 (19)	C4X—H1XC	0.9800
C6B—N6B	1.327 (5)	C5X—H5X1	0.9800
N6B—H6B1	0.86 (2)	C5X—H5X2	0.9800
N6B—H6B2	0.879 (19)	C5X—H5X3	0.9800
C1E—N2E	1.486 (8)	C5X—H5XA	0.9800
C1E—H1E1	0.9800	C5X—H5XB	0.9800
C1E—H1E2	0.9800	C5X—H5XC	0.9800
C2A—N1A—C6A	121.9 (5)	C2X—C1X—H1X1	109.5
C2A—N1A—H1A	116 (5)	N3X'—C1X—H1X2	123.9
C6A—N1A—H1A	122 (5)	C2X—C1X—H1X2	109.5
O2A—C2A—N1A	122.7 (6)	H1X1—C1X—H1X2	109.5
O2A—C2A—N3A	120.5 (5)	N3X'—C1X—H1X3	123.9
N1A—C2A—N3A	116.8 (5)	C2X—C1X—H1X3	109.5
C4A—N3A—C2A	123.2 (5)	H1X1—C1X—H1X3	109.5
C4A—N3A—C3A	119.7 (5)	H1X2—C1X—H1X3	109.5
C2A—N3A—C3A	117.1 (5)	N3X'—C1X—H4XA	109.5
N3A—C3A—H3A1	109.5	C2X—C1X—H4XA	149.5
N3A—C3A—H3A2	109.5	H1X2—C1X—H4XA	87.3
H3A1—C3A—H3A2	109.5	H1X3—C1X—H4XA	87.3
N3A—C3A—H3A3	109.5	N3X'—C1X—H4XB	109.5
H3A1—C3A—H3A3	109.5	C2X—C1X—H4XB	87.3
H3A2—C3A—H3A3	109.5	H1X1—C1X—H4XB	123.9
O4A—C4A—N3A	119.2 (6)	H1X3—C1X—H4XB	114.3
O4A—C4A—C5A	124.2 (6)	H4XA—C1X—H4XB	109.5
N3A—C4A—C5A	116.6 (5)	N3X'—C1X—H4XC	109.5
C6A—C5A—C4A	118.6 (6)	C2X—C1X—H4XC	87.3
C6A—C5A—H5A	120.7	H1X1—C1X—H4XC	123.9
C4A—C5A—H5A	120.7	H1X2—C1X—H4XC	114.3
C5A—C6A—N1A	122.9 (6)	H4XA—C1X—H4XC	109.5
C5A—C6A—Cl6A	122.5 (5)	H4XB—C1X—H4XC	109.5
N1A—C6A—Cl6A	114.6 (5)	N3X—C4X—H4X1	109.5
C6B—N1B—C2B	115.1 (4)	C2X'—C4X—H4X1	144.0
N2B—C2B—N3B	117.4 (3)	N3X—C4X—H4X2	109.5
N2B—C2B—N1B	116.6 (4)	C2X'—C4X—H4X2	90.4
N3B—C2B—N1B	126.0 (4)	H4X1—C4X—H4X2	109.5
C2B—N2B—H2B1	124 (3)	N3X—C4X—H4X3	109.5
C2B—N2B—H2B2	120 (3)	C2X'—C4X—H4X3	90.4
H2B1—N2B—H2B2	115 (5)	H4X1—C4X—H4X3	109.5
C4B—N3B—C2B	116.0 (3)	H4X2—C4X—H4X3	109.5
N4B—C4B—N3B	120.6 (3)	N3X—C4X—H1XA	74.9
N4B—C4B—N5B	118.0 (4)	C2X'—C4X—H1XA	109.5
N3B—C4B—N5B	121.4 (4)	H4X2—C4X—H1XA	122.8
C4B—N4B—H4B1	123 (3)	H4X3—C4X—H1XA	122.8
C4B—N4B—H4B2	115 (3)	N3X—C4X—H1XB	122.8
H4B1—N4B—H4B2	122 (4)	C2X'—C4X—H1XB	109.5
C6B—N5B—C4B	119.4 (3)	H4X1—C4X—H1XB	90.4
C6B—N5B—H5B	122 (3)	H4X3—C4X—H1XB	113.1
C4B—N5B—H5B	118 (3)	H1XA—C4X—H1XB	109.5
N1B—C6B—N6B	119.7 (4)	N3X—C4X—H1XC	122.8
N1B—C6B—N5B	122.1 (3)	C2X'—C4X—H1XC	109.5
N6B—C6B—N5B	118.2 (4)	H4X1—C4X—H1XC	90.4
C6B—N6B—H6B1	111 (4)	H4X2—C4X—H1XC	113.1
C6B—N6B—H6B2	121 (4)	H1XA—C4X—H1XC	109.5
H6B1—N6B—H6B2	128 (5)	H1XB—C4X—H1XC	109.5
N2E—C1E—H1E1	109.5	N3X'—C5X—H5X1	147.1
N2E—C1E—H1E2	109.5	N3X—C5X—H5X1	109.5
H1E1—C1E—H1E2	109.5	N3X'—C5X—H5X2	88.6
N2E—C1E—H1E3	109.5	N3X—C5X—H5X2	109.5
H1E1—C1E—H1E3	109.5	H5X1—C5X—H5X2	109.5
H1E2—C1E—H1E3	109.5	N3X'—C5X—H5X3	88.6
C3E—N2E—C1E	111.2 (5)	N3X—C5X—H5X3	109.5
C3E—N2E—H2E1	111 (3)	H5X1—C5X—H5X3	109.5
C1E—N2E—H2E1	111 (3)	H5X2—C5X—H5X3	109.5
N2E—C3E—H3E1	109.5	N3X'—C5X—H5XA	109.5
N2E—C3E—H3E2	109.5	N3X—C5X—H5XA	147.1
H3E1—C3E—H3E2	109.5	H5X1—C5X—H5XA	103.4
N2E—C3E—H3E3	109.5	H5X2—C5X—H5XA	57.6
H3E1—C3E—H3E3	109.5	H5X3—C5X—H5XA	57.6
H3E2—C3E—H3E3	109.5	N3X'—C5X—H5XB	109.5
O2X—C2X—N3X	118.9 (11)	N3X—C5X—H5XB	88.6
O2X—C2X—C1X	127.4 (9)	H5X1—C5X—H5XB	57.6
N3X—C2X—C1X	113.7 (9)	H5X2—C5X—H5XB	161.2
C2X—N3X—C4X	116.3 (9)	H5X3—C5X—H5XB	67.2
C2X—N3X—C5X	120.7 (9)	H5XA—C5X—H5XB	109.5
C4X—N3X—C5X	122.9 (7)	N3X'—C5X—H5XC	109.5
O2X—C2X'—N3X'	118.4 (12)	N3X—C5X—H5XC	88.6
O2X—C2X'—C4X	127.5 (10)	H5X1—C5X—H5XC	57.6
N3X'—C2X'—C4X	114.1 (11)	H5X2—C5X—H5XC	67.2
C2X'—N3X'—C5X	116.6 (11)	H5X3—C5X—H5XC	161.2
C2X'—N3X'—C1X	111.3 (11)	H5XA—C5X—H5XC	109.5
C5X—N3X'—C1X	132.1 (10)	H5XB—C5X—H5XC	109.5
N3X'—C1X—H1X1	69.5
C6A—N1A—C2A—O2A	180.0	C4B—N5B—C6B—N1B	−0.6 (6)
C6A—N1A—C2A—N3A	0.0	C4B—N5B—C6B—N6B	179.7 (4)
O2A—C2A—N3A—C4A	180.0	O2X—C2X—N3X—C4X	0.000 (1)
N1A—C2A—N3A—C4A	0.0	C1X—C2X—N3X—C4X	180.0
O2A—C2A—N3A—C3A	0.0	O2X—C2X—N3X—C5X	180.000 (1)
N1A—C2A—N3A—C3A	180.0	C1X—C2X—N3X—C5X	0.000 (1)
C2A—N3A—C4A—O4A	180.0	O2X—C2X'—N3X'—C5X	180.000 (1)
C3A—N3A—C4A—O4A	0.0	C4X—C2X'—N3X'—C5X	0.000 (2)
C2A—N3A—C4A—C5A	0.0	O2X—C2X'—N3X'—C1X	0.000 (2)
C3A—N3A—C4A—C5A	180.0	C4X—C2X'—N3X'—C1X	180.000 (2)
O4A—C4A—C5A—C6A	180.0	C2X'—N3X'—C1X—C2X	0.000 (2)
N3A—C4A—C5A—C6A	0.0	C5X—N3X'—C1X—C2X	180.000 (2)
C4A—C5A—C6A—N1A	0.0	O2X—C2X—C1X—N3X'	180.000 (2)
C4A—C5A—C6A—Cl6A	180.0	N3X—C2X—C1X—N3X'	0.000 (2)
C2A—N1A—C6A—C5A	0.0	N3X—C2X—O2X—C2X'	0.000 (3)
C2A—N1A—C6A—Cl6A	180.0	C1X—C2X—O2X—C2X'	180.000 (2)
C6B—N1B—C2B—N2B	−177.4 (4)	N3X'—C2X'—O2X—C2X	0.000 (3)
C6B—N1B—C2B—N3B	2.3 (6)	C4X—C2X'—O2X—C2X	180.000 (2)
N2B—C2B—N3B—C4B	177.6 (4)	C2X—N3X—C4X—C2X'	0.000 (2)
N1B—C2B—N3B—C4B	−2.0 (6)	C5X—N3X—C4X—C2X'	180.000 (2)
C2B—N3B—C4B—N4B	−179.4 (4)	O2X—C2X'—C4X—N3X	180.000 (2)
C2B—N3B—C4B—N5B	0.3 (6)	N3X'—C2X'—C4X—N3X	0.000 (2)
N4B—C4B—N5B—C6B	−179.3 (4)	C2X'—N3X'—C5X—N3X	0.000 (2)
N3B—C4B—N5B—C6B	0.9 (6)	C1X—N3X'—C5X—N3X	180.000 (2)
C2B—N1B—C6B—N6B	178.8 (4)	C2X—N3X—C5X—N3X'	0.000 (2)
C2B—N1B—C6B—N5B	−0.9 (6)	C4X—N3X—C5X—N3X'	180.000 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2X	0.89 (2)	1.87 (2)	2.757 (7)	178 (7)
N2B—H2B1···Cl1C^i	0.88 (2)	2.31 (2)	3.161 (4)	163 (5)
N2B—H2B2···Cl1D	0.87 (2)	2.39 (3)	3.205 (3)	156 (4)
N4B—H4B1···Cl1D^ii	0.88 (2)	2.56 (3)	3.288 (4)	140 (4)
N4B—H4B2···N3B^ii	0.87 (2)	2.16 (2)	3.029 (5)	175 (4)
N5B—H5B···Cl1C^iii	0.87 (2)	2.15 (2)	3.012 (3)	168 (4)
N6B—H6B1···Cl1C	0.86 (2)	2.71 (5)	3.269 (3)	124 (4)
N6B—H6B1···Cl1C^iii	0.86 (2)	2.85 (3)	3.614 (4)	149 (5)
N6B—H6B2···N1B^i	0.88 (2)	2.18 (2)	3.053 (6)	175 (5)
N2E—H2E1···Cl1C	0.88 (2)	2.37 (3)	3.205 (3)	158 (4)

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

Geometries of halogen bonds (see Fig. 1 for the definition of geometrical parameters)

crystal no.	D [Å]	d [Å]	θ1 [°]	θ2 [°]
IV	5.133 (5)	3.455 (4)	160.0 (1)	/
Va	4.755 (3)	3.081 (2)	165.8 (1)	/
Vb	4.732 (4)	3.031 (3)	171.3 (1)	/
VI	4.914 (2)	3.352 (1)	150.6 (1)	150.6 (1)
VII	4.777 (7)	3.070 (4)	178.0 (3)	178.0 (3)