Binary and ternary cocrystals of sulfa drug acetazolamide with pyridine carboxamides and cyclic amides

A novel design strategy for cocrystals of a sulfonamide drug with pyridine carboxamides and cyclic amides is developed based on synthon identification as well as size and shape match of coformers. Binary adducts of acetazolamide (ACZ) with lactams (valerolactam and caprolactam, VLM, CPR), cyclic amides (2-pyridone, labeled as 2HP and its derivatives MeHP, OMeHP) and pyridine amides (nicotinamide and picolinamide, NAM, PAM) were obtained by manual grinding, and their single crystals by solution crystallization. The heterosynthons in the binary cocrystals of ACZ with these coformers suggested a ternary combination for ACZ with pyridone and nicotinamide. Novel supramolecular synthons of ACZ with lactams and pyridine carboxamides are reported together with binary and ternary cocrystals for a sulfonamide drug. This crystal engineering study resulted in the first ternary cocrystal of acetazolamide with amide coformers, ACZ–NAM–2HP (1:1:1).

1. Introduction

Hydrogen bonding is the key adhesive to construct supramolecular synthons for the design of crystalline architectures by using multiple functional groups (Desiraju, 1995). From a crystal engineering perspective, binary and ternary adducts are formed due to robust heterosynthons in the cocrystal, compared with homosynthons in the constituent molecules (Walsh et al., 2003). It has been shown over more than a decade that crystal engineering of multi-component phases offers rational approaches to systematically tune the physicochemical and pharmacokinetic properties of active pharmaceutical ingredients (APIs, Fig. 1). The matching of functional groups and supramolecular synthons together with size and shape factors of molecules offers an approach to assemble three different molecules in the same crystal lattice (Tothadi & Desiraju, 2013, 2014; Chakraborty et al., 2014; Aakeröy et al., 2001, 2005; Seaton et al., 2013; Aitipamula et al., 2013). Ternary cocrystals are relatively less studied and the sulfonamide group is a `structural gap', even as SO₂NH₂ is the key functional group in the most populated sulfa drugs category. These considerations encouraged us to systematically study binary and ternary cocrystals of the sulfonamide group (Bolla et al., 2015). The assembly of three different molecular components in the same crystal lattice is challenging because it hinges on a balance of intermolecular interaction strengths, chemical recognition, geometric fit and overall shape complementarity (Tothadi & Desiraju, 2013). There is more than one possible outcome of a three-component cocrystallization; it may result in one of the components, its solvates or hydrate, a new polymorph of the molecule, binary systems, starting materials, or the ternary product (Fig. 1).

Figure 1 Multiple possibilities of solid forms during cocrystallization to give single, binary and ternary products.

Recent success in the deliberate construction of ternary cocrystals (Bolla & Nangia, 2015) and our work on binary sulfonamide cocrystals (Bolla et al., 2014, 2015) served as the background for the present study. The Cambridge Structural Database (CSD version 5.36, May 2105 update) contains about 75 X-ray crystal structures of ternary systems. Recently, we reported the assembly of ternary components using amides and the sulfonamide group along with a carboxylic acid (Bolla & Nangia, 2015). In the present work, the sulfonamide and acetamide groups of acetazolamide are the starting point to demonstrate the sulfonamide–lactam supramolecular synthon for the assembly of ternary systems.

Acetazolamide, 5-acetamido-1,3,4-thiadiazole-2-sulfon­amide (Fig. 2), is an antiepileptic, diuretic drug for respiratory diseases (Arenas-García et al., 2010, 2012; Grecu et al., 2014). It is also used to prevent the symptoms of altitude sickness as this medication decreases headache, tiredness, nausea, dizziness and shortness of breath at high altitudes. This drug is also used to treat open-angle glaucoma by reducing the amount of fluid that can build up in the eye. The aqueous solubility of ACZ (0.72 mg ml⁻¹ in water at 25°C) is low, has poor permeability and, according to the Biopharmaceutics Drug Disposition Classification System (BDDCS), ACZ belongs to the low solubility and poor permeability Class IV category (Granero et al., 2008; Benet, 2010). ACZ is administered as a 250 mg dose according to the World Health Organization's list (WHO) of essential medicines, a list of the most important medications needed in a basic healthcare system (WHO list dated April 2013, https://apps.who.Int/iris/bitstream/10665/93142/1/EML_18_eng.pdf?ua = 1, accessed 15 Nov. 2015). Two polymorphs of ACZ, forms (I) and (II), and cocrystals with 4-hydroxybenzoic acid, nicotinamide, 4-hydroxybenzamide, picolinamide, 2,3-dihydroxy benzoic acid, and a few inorganic coordination complexes with Ni, Cu, Zn are reported (Umeda et al., 1985; Baraldi et al., 2009; Arenas-García et al., 2010, 2012; Ferrer et al., 1989, 1990; Hartmann & Vahrenkamp, 1991).

Figure 2 Chemical structures of ACZ as A, coformers pyridine carboxamides and syn-amides, aromatic COOH compounds as B and C used in cocrystallization.

The work plan described in this paper was to first prepare binary cocrystals of ACZ with nicotinamide (ACZ–NAM, 1:1), valerolactam (ACZ–VLM, 1:2), caprolactam (ACZ–CPR hydrate, 1:1:1), 2-pyridone (ACZ–2HP, 1:1 and 1:2), 6-methyl-2-pyridone (ACZ–MeHP, 1:1) and 3-methoxy-2-pyridone (ACZ–OMeHP, 1:2), with the idea of assessing the hydrogen bond synthons and recognition modes. By using the moderate to weak association between pyridine amide and cyclic lactam coformers (Bolla & Nangia, 2015), a successful ternary combination of ACZ, NAM and 2HP (ACZ–NAM–2HP, 1:1:1) was then derived from an analysis of the binary cocrystals. The molecules are classified as: A = ACZ; B = pyridine carboxamides, NAM, PAM; and C = cyclic lactams: VLM, CPR; syn amides: 2HP, MeHP, OMeHP (see Fig. 2).

2. Experimental

All the coformers used in this study were purchased from Sigma-Aldrich, India. All chemicals are of analytical and chromatographic grade. Acetazolamide was purchased from Yarrow Chemicals, Mumbai, India, and its purity was confirmed by NMR and DSC.

2.1. ACZ–NAM (1:1)

ACZ (100 mg, 0.45 mmol) and NAM (54 mg, 0.45 mmol) were ground well in a mortar and pestle for 20–30 min by adding 4–5 drops of EtOAc. The ground material was kept for crystallization from a solvent mixture of EtOAc and THF (5 ml) as well as in individual solvents in a 25 ml conical flask at room temperature. Good quality crystals were harvested at ambient condition after a week; m.p. 180°C.

2.2. ACZ–VLM (1:2)

ACZ (100 mg, 0.45 mmol) and VLM (45 mg, 0.45 mmol) were taken in a 1:1 ratio and ground well in a mortar and pestle for 20–30 min by adding 4–5 drops of EtOAc. The ground material was kept for crystallization in EtOAc (5 ml) at room temperature. Good quality crystals were harvested at ambient conditions after a week. Even though the components were taken in an equal molar ratio, the product crystallized in a 1:2 ratio from solution; m.p. 93°C.

2.3. ACZ–CPR hydrate (1:1:1)

ACZ (100 mg, 0.45 mmol) and CPR (50 mg, 0.45 mmol) were taken in a 1:1 ratio and ground well in a mortar and pestle for 20–30 min by adding 4–7 drops of EtOAc. The ground material was kept for crystallization from a solvent mixture of EtOAc and THF (5 ml) as well as individual solvents at room temperature. The ground material crystallized from solution as a hydrate after one week; m.p. 80°C. Solvents used here are analytically pure and crystallization was carried out at room temperature (ca 30°C) in an open evaporation flask, which gave the cocrystal hydrate product.

2.4. ACZ–2HP (1:2)

ACZ (100 mg, 0.45 mmol) and 2HP (42 mg, 0.45 mmol) were taken in a 1:1 ratio and ground well in a mortar and pestle for 20–30 min by adding 4–7 drops of EtOAc. The ground material was kept for crystallization from a solvent mixture of EtOAc and THF (5 ml) as well as individual solvents at room temperature. Good quality crystals were harvested at ambient conditions after a week. The ground material crystallized from solution in a 1:2 ratio; m.p. 160°C.

2.5. ACZ–2HP (1:1)

ACZ (100 mg, 0.45 mmol) and 2HP (42 mg, 0.45 mmol) were ground well in a mortar and pestle for 20–30 min by adding 4–7 drops of EtOAc in the presence of NAM or INA to obtain a ternary system. Even though the attempts to obtain an ACZ binary cocrystal with isonicotinamide (INA) were not successful, experiments were carried out to obtain a ternary ACZ–INA–2HP adduct in a trial attempt. A binary product ACZ–2HP (1:1) was obtained. A unit cell check of randomly selected crystals showed that the majority are ACZ–2HP (1:1), while a few crystals had 1:2 stoichiometry. The ground material of 1:1 stoichiometry was kept for crystallization from a solvent mixture of EtOAc and THF (5 ml) as well as individual solvents at room temperature. Good quality crystals were harvested at ambient condition after a week; m.p. 180°C.

2.6. ACZ–MeHP (1:1)

ACZ (100 mg, 0.45 mmol) and MeHP (49 mg, 0.45 mmol) were ground well in a mortar and pestle for 20–30 min. The ground material was kept for crystallization in 5 ml of EtOAc at room temperature to obtain good quality single crystals at ambient conditions after 1 week; m.p. 130°C.

2.7. ACZ–OMeHP hydrate (1:1:1)

ACZ (100 mg, 0.45 mmol) and OMeHP (56 mg, 0.45 mmol) were ground well in a mortar and pestle for 25 min with a few drops of EtOAc added. The ground material was kept for crystallization in 5 ml of EtOAc and THF mixture or in the individual solvents at room temperature to give good quality single crystals after 4–5 d. The product crystallized as a monohydrate; m.p. 90°C.

2.8. ACZ–NAM–2HP (1:1:1)

ACZ (100 mg, 0.45 mmol), NAM (54 mg, 0.45 mmol) and 2HP (42 mg, 0.45 mmol) were ground well in a mortar and pestle for 20–30 min by adding 4–7 drops of EtOAc. The ground material was kept for crystallization from a solvent mixture of 5 ml EtOAc and THF as well as the individual solvents at room temperature to give good quality single crystals of the ternary adduct after 5–6 days. A few crystals of binary products ACZ−NAM and ACZ−2HP (1:1, 1:2) were also observed in the crystallization flask concomitantly based on a unit cell check. Single crystal data were collected of the ternary product by manual separation of their different morphology crystals as a plate and a block; m.p. 125°C.

2.9. Single-crystal X-ray diffraction

A single crystal was mounted on the goniometer of an Oxford Diffraction Gemini X-ray diffractometer equipped with Cu Kα radiation source (λ = 1.54184 Å) at 298 K. Data reduction was performed using CrysAlisPro 171.33.55 software (Oxford Diffraction, 2008). The crystal structure was solved and refined using Olex2-1.0 (Dolomanov et al., 2009) with anisotropic displacement parameters for non-H atoms. H atoms were experimentally located through the difference-Fourier electron density maps in all crystal structures. Data were reduced by SAINT-Plus (Bruker, 1998) and further continued with SHELXTL (Sheldrick, 2008). A check of the final CIF file with PLATON (Spek, 2009) did not show any missed symmetry. X-Seed (Barbour, 2001) was used to prepare the figures and packing diagrams. The crystallographic parameters of all the cocrystals are summarized in Table 1 and hydrogen-bond distances are listed in Table S1 . CIF files are deposited at CCDC Nos. 1436978–1436985. Single-crystal X-ray diffraction data were also collected at 298 K on a Bruker SMART APEX-1 CCD area-detector system equipped with a graphite monochromator Mo Kα fine-focus sealed tube (λ = 0.71073 Å) operating at 1500 power, 40 kV, 30 mA. The frames were integrated by SAINT (Bruker, 1998) software using a narrow-frame integration algorithm. Data were corrected for absorption effects using the multi-scan method (SADABS; Bruker, 1998). The structures were solved and refined using SHELXTL (Sheldrick, 2008).

Table 1
Crystallographic parameters of cocrystals

	ACZ–NAM (1:1)	ACZ–VLM (1:2)	ACZ–CPR hydrate (1:1:1)	ACZ–2HP (1:2)	ACZ–2HP (1:1)	ACZ–MeHP (1:1)	ACZ–OMeHP hydrate (1:1:1)	ACZ–NAM–2HP (1:1:1)
Empirical formula	C4H6N4O3S2·C6H6N2O	C4H6N4O3S2·2C5H9NO	C4H6N4O3S2·C6H11NO·H2O	C4H6N4O3S2·2C5H5NO	C4H6N4O3S2·C5H5NO	C4H6N4O3S2·C6H7NO	C4H6N4O3S2·C6H7NO2·H2O	C4H6N4O3S2·C6H6N2O·C5H5NO
Formula weight	344.38	420.51	353.42	412.45	317.35	994.12	775.22 (9)	439.48
Crystal system	Triclinic	Monoclinic	Triclinic	Triclinic	Monoclinic	Monoclinic	Triclinic	Triclinic
Space group		P21/c			P21/n	Pc
T (K)	298	298	298	298	298	298	298	298
a (Å)	5.1477 (8)	9.66166 (19)	4.9969 (2)	6.8501 (3)	4.9138 (4)	11.3972 (7)	7.7872 (6)	7.0347 (3)
b (Å)	10.8147 (14)	23.4685 (4)	11.6983 (6)	11.3563 (6)	33.192 (3)	18.1641 (3)	10.2130 (7)	10.2539 (7)
c (Å)	14.2604 (16)	8.84352 (17)	14.6244 (8)	12.3387 (8)	8.3659 (7)	10.338 (3)	10.2464 (7)	13.7934 (9)
α (°)	69.797 (11)	90	70.868 (5)	82.288 (5)	90	90	88.192 (5)	81.685 (6)
β (°)	85.463 (12)	100.773 (1)	81.892 (4)	81.856 (4)	99.520 (1)	97.046 (16)	76.587 (6)	83.028 (5)
γ (°)	81.889 (12)	90	80.262 (4)	75.804 (4)	90	90	88.192 (5)	88.283 (5)
V (Å^3)	737.20 (18)	1969.88 (6)	792.65 (7)	916.19 (9)	1345.7 (2)	2124.0 (6)	775.22 (10)	977.14 (5)
Dx (g cm^−3)	1.55	1.42	1.48	1.49	1.56	1.55	1.56	1.49
Z	2	4	2	2	4	6	2	2
R1 [I > 2σ(I)]	0.0631	0.0427	0.0378	0.0647	0.0378	0.0397	0.0492	0.0612
wR2 (all)	0.1944	3507	2792	0.1710	0.0984	4590	0.1408	0.1789
Goodness-of-fit	1.005	1.064	1.078	1.061	1.000	1.020	1.057	1.083
X-ray diffracto­meter	Oxford CCD	Oxford CCD	Oxford CCD	Oxford CCD	Bruker APEX	Oxford CCD	Oxford CCD	Oxford CCD

2.10. X-ray powder diffraction

Bulk samples were analyzed by X-ray powder diffraction on a Bruker AXS D8 diffractometer (Bruker-AXS, Karlsruhe, Germany). Experimental conditions: Cu Kα radiation (λ = 1.54056 Å), 40 kV, 30 mA, scanning interval 5–50° 2θ at a scan rate of 1° min⁻¹, time per step 0.5 s.

3. Results and discussion

3.1. ACZ polymorphs and reported binary adducts

Acetazolamide (ACZ, Fig. 2) consists of a primary sulfonamide group, thiadiazole heterocycle and acetamide groups. Both the sulfonamide and acetamido groups are sites for hydrogen bonding with complementary coformers listed under B and C. Crystal structures of two polymorphs (I) and (II) of ACZ are reported (Umeda et al., 1985). Form (I) exhibits multiple ring synthons such as N—H⋯N homodimers R₂²(8), sulfonamide dimer R₂²(8), sulfon­amide–amide macrocycle ring R₂²(20) (Fig. 3a) (Etter, 1990; Bernstein et al., 1995). Form (II) comprises sulfonamide catemer chains C(4) as well as amide–thiadiazole N—H⋯N ring motif R₂²(8) (Fig. 3b). The hydrogen-bond motifs present in the reported cocrystals of ACZ (Baraldi et al., 2009; Arenas-García et al., 2010, 2012; Ferrer et al., 1989, 1990; Hartmann & Vahrenkamp, 1991) with 4-hydroxybenzoic acid (ACZ–4HBA; 1:1), a hydrate with nicotinamide (ACZ–NAM hydrate; 1:1:1), picolinamide (ACZ–PAM; 1:2) and 2,3-dihydroxy benzoic acid (ACZ–2,3DHBA; 3:1) are displayed in Figs. 3(c)–(f). The fact that the synthons in cocrystal structures are quite different from those in the two polymorphs of ACZ means that the coformer functional groups are able to disrupt the self-association to give stronger and newer motifs in the binary complexes. This is a positive indication for successful cocrystallization.

Figure 3 (a), (b) Supramolecular synthons in ACZ polymorphs Form (I) and (II). (c), (d), (e), (f) Binary cocrystals of ACZ with picolinamide, nicotinamide, 4-hydroxybenzoic acid and 2,3-dihydroxybenzoic acid.

The crystal structures and supramolecular synthons of binary systems with a few pharmaceutically acceptable coformers are discussed to understand the hydrogen bonding and stoichiometry in self-assembly: ACZ–NAM (1:1), ACZ–VLM (1:2), ACZ–CPR hydrate (1:1:1), ACZ–2HP (1:1 and 1:2), ACZ–MeHP (1:1) ACZ–OMeHP hydrate (1:1:1). The designed assembly of a ternary cocrystal ACZ–NAM–2HP (1:1:1) is as such rare for drug molecules.

3.2. Crystal structures of binary cocrystals

The crystal structure parameters are summarized in Table 1 and hydrogen-bond parameters in Table S1 of the supporting information . The synthons and molecular packing of binary cocrystals is presented first and then the build up to the ternary system is described.

3.2.1. ACZ–NAM (1:1)

The cocrystal structure (space group ) contains N—H⋯N homodimers R₂²(8) of ACZ, similar to those observed in polymorph (II). However, the sulfonamide dimer of ACZ is replaced by N—H⋯O and N—H⋯N hydrogen bonds to nicotinamide. Two ACZ and two NAM molecules form a tetramer ring motif R₄⁴(16) via N—H⋯O and N—H⋯N hydrogen bonds (Fig. 4a). The overall structure has a layered two-dimensional pattern (Fig. 4b).

Figure 4 Supramolecular synthons and molecular packing in ACZ binary systems. (a), (b) ACZ–NAM (1:1) displays ACZ sulfonamide N—H⋯O and N—H⋯N hydrogen bonds with NAM amide dimers and pyridine N motifs. (c), (d) ACZ–VLM (1:2) where one VLM forms a hydrogen bond with the amidediazole–amide synthon and the second VLM connects such heterodimer units. (e), (f) CPR homodimers interact with sulfonamide hydrate dimer motifs via N—H⋯O and O—H⋯O hydrogen bonds. (g), (h) ACZ–2HP (1:2) shows one equivalent of 2HP to make the heterodimer which is connected by the second 2HP homodimers and sulfonamide N—H⋯O chain. (i), (j) Two-dimensional packing in ACZ–2HP (1:1) makes the binary heterosynthon similar to the previous structure as well as the sulfonamide C(4) catemer. (k), (l) ACZ–MeHP (1:1) is similar to that of ACZ–2HP (1:1). (m), (n) Water molecules are present in the crystal lattice of ACZ–OMeHP hydrate (1:1:1) which connect the binary components of aminodiazole–amide. H atoms are removed in a few diagrams for clarity.

3.2.2. ACZ–VLM (1:2)

In the crystal structure (P2₁/c) VLM forms a R₂²(9) motif of sulfonamide, thiadiazole and amide groups (Fig. 4c). A second equivalent of VLM connects such heterosynthon units via N—H⋯O hydrogen bonds. Such one-dimensional chains extended parallel to the c-axis via N—H⋯O hydrogen bonds in a two-dimensional array (Fig. 4d). The inclusion of a second VLM in the cocrystal structure suggested that if this latter molecule could be replaced by a different amide, then a ternary system will result. In other words, the binary system has a tendency to include a third partner from solution. The same phenomenon is observed in the next structure.

3.2.3. ACZ–CPR hydrate (1:1:1)

The ground material of ACZ and CPR in a 1:1 ratio was crystallized as a hydrate (1:1:1) in space group . CPR homodimers R₂²(8) are sandwiched between the SO₂NH₂ and water molecules in a R₄⁴(12) ring motif (Fig. 4e). Such discrete clusters extend via the water O—H donor (Fig. 4f). Even though the water is serendipitously included, it makes three components in the crystal lattice.

3.2.4. ACZ–2HP (1:2)

The ground product of ACZ–2HP (1:2) was solved in space group . One equivalent of 2HP breaks the strong N—H⋯N homodimer R₂²(8) between ACZ molecules and forms an amide(2HP)–imino (ACZ) heterosynthon. The sulfonamide–carboxamide dimer motif R₂²(20) previously noted in ACZ Form (I) (Fig. 3a) is present in this binary system (Fig. 4g). The second equivalent of 2HP homodimers connect ACZ−2HP units via N—H⋯O hydrogen bonds to give the 1:2 composition (Fig. 4h). Again, the 2HP dimers could be replaced by a structural mimic to give a ternary system.

3.2.5. ACZ–2HP (1:1)

The cyclic ring motifs, such as the N—H⋯N dimer of ACZ polymorphs (Figs. 3a and b), are interrupted in the presence of 2HP to give an amide–iminodiazole R₂²(8) motif (Fig. 4i), similar to the previous structure. The extended motifs via N—H⋯O catemer chain C(4) in this structure (Fig. 4j) obviate the need for the 2HP dimer noted in the 1:2 structure (Fig. 4g). This binary structure suggests that 2HP should be a good partner for ternary assembly because the crystal structure is heavily disturbed compared with the ACZ structure, as well as other cocrystals. Moreover, both 1:1 and 1:2 combinations were routinely observed. A strong heterodimer between the two components is a prerequisite for ternary assembly (Aakeröy et al., 2001; Aakeröy & Salmon, 2005). The presence of the symmetry-independent 2HP dimer in the 1:2 structure appears to be optional and it could be replaced by another component of similar size, shape and hydrogen-bonding groups to yield a ternary cocrystal. We note that there is a similar NAM amide dimer in the ACZ–NAM (1:1) structure (Fig. 4a) and this gives a logical lead towards the ternary combination.

3.2.6. ACZ–MeHP (1:1)

The centrosymmetric R₂²(8) dimers of ACZ−MeHP are formed with N—H⋯O and N—H⋯N bonds between aminodiazole–amide groups (Fig. 4k), which is similar to the heterosynthon in ACZ–2HP. The sulfonamide N—H donors connect molecules to make extended arrays (Fig. 4l).

3.2.7. ACZ–OMeHP hydrate (1:1:1)

The ground product of ACZ and OMeHP in a 1:1 ratio crystallized as a hydrate (1:1:1) in space group . The dimer of ACZ diazole and OMeHP amide in ring motif R₂²(8) (Fig. 3a) and water molecules connect such units (Fig. 4m) in the inter-layer region (Fig. 4n). It appears that the inclusion of water was mandated as a spacer between the ACZ−OMeHP dimer units to accommodate the OMe group. This means that the bonding between ACZ and 2HP is strong enough to override steric groups which were overcome by the inclusion of a water molecule in the binary cocrystal.

The above crystal structures are described in the natural sequence of crystallization being carried out and the experimental results analyzed.

3.3. Crystal structure of ternary cocrystal ACZ–NAM–2HP (1:1:1)

After screening several binary combinations and their crystal structures, we have decided to replace the second equivalent of the coformer in ACZ−2HP (1:2) with NAM, given that nicotinamide can form an amide R₂²(8) dimer similar to 2HP. Moreover such dimers are present in ACZ–NAM (1:1). Grinding of ACZ, NAM and 2HP in an equimolar ratio and recrystallization of the crystalline product gave the ternary cocrystal ACZ–NAM–2HP, as confirmed by single-crystal X-ray diffraction (1:1:1 stoichiometry). The ternary cocrystal structure has resemblances with the binary structure ACZ–2HP (1:2) as expected. Hydrogen bonds between the sulfonamide NH and acetamide C=O groups of ACZ result in dimer pairs R₂²(20) (Fig. 5a), which were noted previously in polymorph (I) of ACZ as well as in ACZ−2HP (1:2). The R₂²(8) dimers of 2HP are also present here. The link between these ring motifs is that the amide NH of ACZ bonds to the pyridine N of NAM and the NH of NAM is bonded to the 2HP amide dimer. Thus, while the A and C dimers are repeating motifs, the linkage through the B molecule is somewhat different in the ternary structure compared with the previous binary cocrystals. Propagation of the centrosymmetric motifs via N—H⋯O and N—H⋯N hydrogen bonds is shown in Fig. 5(b). There is considerable `carry over' of synthons from the binary to the ternary cocrystal, yet there are unexpected motifs as well. Overall, the element of design and crystal engineering appears to be a consistent thread in this family of structures.

Figure 5 (a) Synthons in ternary cocrystal ACZ–NAM–2HP (1:1:1). The macrocycle ring motif R2^2(20) of ACZ are novel to the ternary structure and NAM further extends these units with hydrogen bonding to the dimers of 2HP. (b) Two-dimensional packing of the ternary cocrystal shows that ACZ molecules (green) are separated by NAM and 2HP (blue, red).

3.4. Supramoleculer synthons in this study

The three hydrogen bonding sites in ACZ are acetamide (donor–acceptor), sulfonamide group (donor–acceptor) and thiadiazole ring (acceptor only) (Fig. 6a). The sulfonamide is flexible (Arenas-García et al., 2010, 2012) while the other two moieties, acetamide and thiadiazole, are rigid functional groups for hydrogen bonding. The main synthons observed in different cocrystals are displayed in Figs. 6(b)–(d).

Figure 6 Hydrogen-bonding synthons of ACZ observed in this study. (a) Molecular diagram showing the hydrogen bonding groups as rigid or flexible (according to Arenas-García et al., 2010, 2012). (b) Synthon 1 between the acetamide and thiadiazole ring of ACZ with carboxylic acid, carboxamide, syn-amide, respectively. (c) Synthon 2 between the sulfonamide group of ACZ and pyridine carboxamides, e.g. NAM, PAM, to give large ring motifs. (d) Synthon 3 connects sulfonamide, thiadiazole N and lactam conformer C. The graph-set notations of ring motifs are given for identification.

The main stream of our approach and objective was to understand the long-range synthon Aufbau modules (LSAM; Ganguly & Desiraju, 2010; Mukherjee et al., 2014a,b) in the ternary cocrystals (Bolla & Nangia, 2015). However, because we were successful in crystallizing only a single ternary structure in this family, a supramolecular build-up or LSAM model for the ternary assembly of ACZ is difficult to analyze due to insufficient data. The ternary cocrystal suggests the ACZ amide bonds with NAM pyridine via N—H⋯N and the CONH₂ donor of NAM connects to the pyridone via N—H⋯O to give the ternary adduct (Fig. 7).

Figure 7 LSAM in the ternary assembly ACZ–NAM–2HP.

3.5. CSD analysis of heterosynthons in this study

A search of the Cambridge Structural Database (CSD Version 5.36, May 2015 update) was carried out to tabulate the reported supramolecular synthons of the sulfonamide functional group observed in this study (after eliminating hydrates, solvates, salts and duplicates) with those reported in previous structures. Relatively few hits are obtained on the sulfonamide functional group bonding to amide (25 hits), pyridine (4 hits) and carboxylic acids (3 hits); see Table 2 and Table S2 . The present study therefore is an early result on cocrystals of a sulfonamide drug with pyridine amide and lactam conformers (GRAS-type molecules; Bolla & Nangia, 2015). The synthons extracted from the CSD for a sulfonamide bonding to an amide or pyridine group are displayed in Fig. 8. Analogous to the carboxamide group (Nangia, 2010), the occurrence of SO₂NH₂ bonding with an amide group is much more likely than to a pyridine (six times) due to the stronger amide acceptor nature.

Table 2
Frequency of sulfonamide synthons in the CSD

Supramolecular synthons of SO2NH2 group in crystal structure adducts	Number of hits
Sulfonamide–amide	25
Sulfonamide–pyridine	4
Sulfonamide–acid	3

Figure 8 Different types of (a) sulfonamide–amide, (b) sulfonamide−pyridine and (c) sulfonamide−acid supramolecular synthons.

4. Conclusions

The first study of sulfonamide drug cocrystals with amide coformers is described leading to a ternary drug cocrystal. A library of supramolecular synthons was derived from binary adducts of ACZ with pyridine amide and lactam coformers (A–B and A–C cocrystals). There is competition and interplay of the hydrogen bonding functional groups during binary cocrystallization. The binary results suggest that the syn amides form reliable synthons to afford cocrystals with a sulfonamide drug. Using ACZ–NAM and ACZ–2HP cocrystals as leads, a ternary assembly was designed to give the 3-component cocrystal ACZ–NAM–2HP (1:1:1). Mechanochemistry, or grinding with solvent added, is necessary to hydrogen bond the components in the ternary adduct, which was then recrystallized to produce single crystals for X-ray diffraction. This is the first crystal structure report of a sulfa drug ternary cocrystal.

Supporting information

Computing details

For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

(ACZ2HP11)

Crystal data

C4H6N4O3S2·C5H5NO	Dx = 1.566 Mg m^−3
Mr = 317.35	Melting point: 453 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.9138 (4) Å	Cell parameters from 6192 reflections
b = 33.192 (3) Å	θ = 2.5–25.9°
c = 8.3659 (7) Å	µ = 0.42 mm^−1
β = 99.520 (1)°	T = 298 K
V = 1345.7 (2) Å^3	Needle, colorles
Z = 4	0.21 × 0.19 × 0.18 mm
F(000) = 656

Data collection

CCD area detector diffractometer	2176 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 26.0°, θmin = 1.2°
phi and ω scans	h = −6→6
13846 measured reflections	k = −40→40
2640 independent 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0591P)^2 + 0.2415P] where P = (Fo^2 + 2Fc^2)/3
2640 reflections	(Δ/σ)max < 0.001
198 parameters	Δρmax = 0.35 e Å^−3
1 restraint	Δρmin = −0.22 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
S1	−0.15925 (10)	0.228595 (15)	0.67680 (6)	0.03577 (16)
S2	−0.07309 (10)	0.137123 (16)	0.65477 (6)	0.04162 (17)
N1	0.2548 (3)	0.18467 (5)	0.8351 (2)	0.0383 (4)
N3	0.3114 (4)	0.08084 (5)	0.7764 (2)	0.0448 (4)
N4	−0.2949 (4)	0.24391 (6)	0.8236 (2)	0.0385 (4)
C1	0.0263 (4)	0.18371 (6)	0.7336 (2)	0.0339 (4)
O2	−0.3746 (3)	0.21585 (5)	0.55101 (18)	0.0548 (4)
C2	0.2258 (4)	0.11980 (6)	0.7721 (2)	0.0367 (4)
N2	0.3729 (3)	0.14739 (5)	0.8588 (2)	0.0402 (4)
O3	0.0387 (3)	0.25754 (5)	0.64635 (19)	0.0518 (4)
O1	−0.0546 (4)	0.05834 (5)	0.6013 (2)	0.0689 (5)
O4	−0.2082 (3)	0.06497 (5)	−0.0152 (2)	0.0612 (5)
C5	−0.0597 (4)	0.08755 (7)	0.0815 (3)	0.0478 (5)
N5	−0.1277 (4)	0.12714 (6)	0.0950 (2)	0.0467 (5)
C4	0.2896 (7)	0.01022 (8)	0.7138 (4)	0.0812 (9)
H4A	0.2667	0.0000	0.8180	0.122*
H4B	0.4827	0.0120	0.7079	0.122*
H4C	0.2011	−0.0076	0.6306	0.122*
C6	0.1882 (5)	0.07568 (8)	0.1854 (3)	0.0597 (7)
H6	0.2478	0.0491	0.1834	0.072*
C3	0.1627 (5)	0.05098 (7)	0.6901 (3)	0.0538 (6)
C8	0.2571 (6)	0.14215 (9)	0.2911 (3)	0.0648 (7)
H8	0.3630	0.1604	0.3591	0.078*
C9	0.0223 (5)	0.15392 (8)	0.1954 (3)	0.0565 (6)
H9	−0.0367	0.1805	0.1983	0.068*
C7	0.3371 (5)	0.10210 (9)	0.2859 (3)	0.0648 (7)
H7	0.4962	0.0934	0.3531	0.078*
H4D	−0.186 (5)	0.2539 (6)	0.899 (3)	0.038 (6)*
H4E	−0.432 (5)	0.2307 (7)	0.842 (3)	0.049 (7)*
H3A	0.470 (6)	0.0766 (8)	0.845 (3)	0.061 (7)*
H5A	−0.274 (4)	0.1352 (7)	0.034 (3)	0.056 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0334 (3)	0.0423 (3)	0.0300 (3)	0.0064 (2)	0.00046 (19)	0.0022 (2)
S2	0.0339 (3)	0.0442 (3)	0.0426 (3)	0.0019 (2)	−0.0061 (2)	−0.0087 (2)
N1	0.0317 (8)	0.0365 (9)	0.0435 (10)	0.0013 (7)	−0.0031 (7)	0.0006 (7)
N3	0.0363 (10)	0.0374 (10)	0.0568 (11)	0.0015 (8)	−0.0042 (9)	−0.0055 (8)
N4	0.0299 (9)	0.0454 (10)	0.0398 (10)	−0.0050 (8)	0.0046 (8)	−0.0078 (8)
C1	0.0298 (10)	0.0383 (11)	0.0328 (10)	0.0017 (8)	0.0028 (8)	−0.0007 (8)
O2	0.0542 (10)	0.0625 (10)	0.0398 (8)	0.0179 (8)	−0.0152 (7)	−0.0094 (7)
C2	0.0301 (10)	0.0390 (11)	0.0401 (11)	0.0003 (8)	0.0030 (8)	−0.0019 (9)
N2	0.0308 (9)	0.0350 (9)	0.0512 (10)	0.0011 (7)	−0.0040 (7)	−0.0012 (7)
O3	0.0510 (9)	0.0525 (10)	0.0552 (9)	0.0040 (7)	0.0187 (7)	0.0173 (7)
O1	0.0629 (11)	0.0560 (11)	0.0777 (12)	0.0010 (9)	−0.0180 (9)	−0.0198 (9)
O4	0.0505 (9)	0.0490 (9)	0.0770 (12)	0.0052 (8)	−0.0104 (9)	−0.0027 (8)
C5	0.0386 (12)	0.0516 (14)	0.0517 (13)	0.0007 (10)	0.0034 (10)	0.0047 (10)
N5	0.0366 (10)	0.0481 (11)	0.0525 (11)	0.0022 (8)	−0.0008 (9)	0.0055 (9)
C4	0.084 (2)	0.0406 (14)	0.108 (2)	0.0017 (13)	−0.0140 (18)	−0.0138 (15)
C6	0.0455 (13)	0.0599 (16)	0.0703 (16)	0.0113 (12)	−0.0007 (12)	0.0125 (13)
C3	0.0535 (14)	0.0426 (13)	0.0624 (15)	−0.0022 (11)	0.0014 (12)	−0.0095 (11)
C8	0.0540 (15)	0.0794 (19)	0.0569 (15)	−0.0074 (14)	−0.0032 (12)	−0.0052 (13)
C9	0.0548 (15)	0.0549 (15)	0.0582 (14)	−0.0046 (12)	0.0049 (12)	−0.0029 (12)
C7	0.0461 (14)	0.085 (2)	0.0580 (16)	0.0007 (13)	−0.0086 (12)	0.0100 (14)

Geometric parameters (Å, º)

S1—O3	1.4199 (16)	C5—N5	1.365 (3)
S1—O2	1.4274 (15)	C5—C6	1.430 (3)
S1—N4	1.5753 (18)	N5—C9	1.354 (3)
S1—C1	1.7701 (19)	N5—H5A	0.853 (16)
S2—C1	1.7197 (19)	C4—C3	1.489 (3)
S2—C2	1.725 (2)	C4—H4A	0.9600
N1—C1	1.291 (2)	C4—H4B	0.9600
N1—N2	1.367 (2)	C4—H4C	0.9600
N3—C2	1.359 (3)	C6—C7	1.345 (4)
N3—C3	1.365 (3)	C6—H6	0.9300
N3—H3A	0.90 (3)	C8—C9	1.349 (4)
N4—H4D	0.83 (2)	C8—C7	1.389 (4)
N4—H4E	0.84 (3)	C8—H8	0.9300
C2—N2	1.309 (2)	C9—H9	0.9300
O1—C3	1.221 (3)	C7—H7	0.9300
O4—C5	1.246 (3)
O3—S1—O2	120.96 (10)	C9—N5—C5	124.6 (2)
O3—S1—N4	108.20 (10)	C9—N5—H5A	118.8 (17)
O2—S1—N4	108.22 (10)	C5—N5—H5A	116.6 (17)
O3—S1—C1	106.26 (9)	C3—C4—H4A	109.5
O2—S1—C1	103.56 (9)	C3—C4—H4B	109.5
N4—S1—C1	109.15 (9)	H4A—C4—H4B	109.5
C1—S2—C2	85.44 (9)	C3—C4—H4C	109.5
C1—N1—N2	112.04 (16)	H4A—C4—H4C	109.5
C2—N3—C3	122.72 (19)	H4B—C4—H4C	109.5
C2—N3—H3A	113.5 (17)	C7—C6—C5	121.4 (2)
C3—N3—H3A	123.7 (17)	C7—C6—H6	119.3
S1—N4—H4D	115.1 (15)	C5—C6—H6	119.3
S1—N4—H4E	115.2 (16)	O1—C3—N3	121.0 (2)
H4D—N4—H4E	121 (2)	O1—C3—C4	124.6 (2)
N1—C1—S2	115.80 (14)	N3—C3—C4	114.4 (2)
N1—C1—S1	120.59 (15)	C9—C8—C7	118.5 (2)
S2—C1—S1	123.57 (11)	C9—C8—H8	120.7
N2—C2—N3	120.73 (18)	C7—C8—H8	120.7
N2—C2—S2	114.98 (15)	C8—C9—N5	120.2 (2)
N3—C2—S2	124.29 (15)	C8—C9—H9	119.9
C2—N2—N1	111.74 (16)	N5—C9—H9	119.9
O4—C5—N5	120.5 (2)	C6—C7—C8	121.1 (2)
O4—C5—C6	125.3 (2)	C6—C7—H7	119.5
N5—C5—C6	114.2 (2)	C8—C7—H7	119.5

(ACZ2HP12)

Crystal data

C4H6N4O3S2·2(C5H5NO)	F(000) = 428
Mr = 412.45	Dx = 1.495 Mg m^−3
Triclinic, P1	Melting point: 433 K
a = 6.8501 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.3563 (6) Å	Cell parameters from 3198 reflections
c = 12.3387 (8) Å	θ = 5.1–71.9°
α = 82.288 (5)°	µ = 3.01 mm^−1
β = 81.856 (4)°	T = 298 K
γ = 75.804 (4)°	Block, colorles
V = 916.20 (8) Å^3	0.23 × 0.22 × 0.22 mm
Z = 2

Data collection

Xcalibur, Eos, Gemini diffractometer	3268 independent reflections
Radiation source: fine-focus sealed tube	3035 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 67.1°, θmin = 3.6°
Absorption correction: multi-scan	h = −6→8
Tmin = 0.137, Tmax = 1.000	k = −12→13
5007 measured reflections	l = −13→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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1265P)^2 + 0.4073P] where P = (Fo^2 + 2Fc^2)/3
3268 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.80 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
S1	0.24089 (9)	0.05772 (5)	0.95947 (5)	0.0335 (2)
S2	0.30061 (10)	0.06609 (5)	0.70910 (5)	0.0379 (2)
O1	0.1813 (3)	0.01581 (17)	1.18019 (17)	0.0462 (5)
O4	0.0236 (3)	0.64656 (18)	0.43750 (17)	0.0493 (5)
O5	0.1665 (4)	0.43570 (19)	0.17745 (18)	0.0543 (6)
N6	0.2348 (3)	0.5258 (2)	0.00544 (18)	0.0368 (5)
N3	0.2022 (3)	0.2086 (2)	1.12119 (19)	0.0360 (5)
N1	0.2786 (3)	0.2507 (2)	0.83158 (19)	0.0383 (5)
N2	0.2504 (3)	0.28428 (19)	0.93644 (19)	0.0376 (5)
O2	0.3320 (4)	−0.06083 (18)	0.74606 (18)	0.0517 (5)
C11	0.2201 (4)	0.6368 (2)	0.1559 (2)	0.0398 (6)
H11	0.2011	0.6435	0.2312	0.048*
N5	0.1912 (4)	0.5326 (2)	0.57629 (18)	0.0393 (5)
C5	0.1597 (4)	0.6322 (2)	0.4996 (2)	0.0363 (6)
N4	0.0888 (4)	0.1104 (2)	0.6619 (2)	0.0445 (6)
O3	0.4477 (3)	0.1111 (2)	0.63316 (19)	0.0592 (6)
C10	0.2042 (4)	0.5270 (2)	0.1168 (2)	0.0360 (5)
C3	0.1763 (4)	0.1184 (2)	1.2020 (2)	0.0376 (6)
C2	0.2298 (3)	0.1931 (2)	1.0117 (2)	0.0311 (5)
C6	0.2904 (4)	0.7128 (3)	0.4969 (3)	0.0450 (6)
H6	0.2762	0.7825	0.4470	0.054*
C1	0.2781 (4)	0.1371 (2)	0.8312 (2)	0.0325 (5)
C13	0.2904 (4)	0.7245 (2)	−0.0287 (3)	0.0428 (6)
H13	0.3188	0.7897	−0.0775	0.051*
C14	0.2752 (4)	0.6207 (3)	−0.0661 (2)	0.0418 (6)
H14	0.2925	0.6144	−0.1414	0.050*
C8	0.4615 (5)	0.5844 (3)	0.6420 (2)	0.0499 (7)
H8	0.5612	0.5681	0.6894	0.060*
C12	0.2625 (4)	0.7313 (2)	0.0845 (3)	0.0415 (6)
H12	0.2732	0.8017	0.1116	0.050*
C7	0.4350 (5)	0.6892 (3)	0.5661 (3)	0.0489 (7)
H7	0.5183	0.7433	0.5633	0.059*
C4	0.1405 (5)	0.1532 (3)	1.3167 (3)	0.0536 (8)
H4C	0.0082	0.1445	1.3493	0.080*
H4D	0.1489	0.2365	1.3154	0.080*
H4E	0.2412	0.1010	1.3593	0.080*
C9	0.3372 (5)	0.5079 (3)	0.6441 (2)	0.0483 (7)
H9	0.3528	0.4372	0.6929	0.058*
H5A	0.118 (5)	0.483 (3)	0.580 (3)	0.046 (9)*
H4A	0.058 (5)	0.183 (4)	0.638 (3)	0.058 (10)*
H4B	−0.001 (6)	0.078 (4)	0.706 (4)	0.066 (11)*
H6A	0.229 (5)	0.457 (4)	−0.022 (3)	0.057 (10)*
H3A	0.191 (5)	0.281 (3)	1.138 (3)	0.039 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0420 (4)	0.0222 (3)	0.0378 (4)	−0.0110 (2)	−0.0054 (3)	−0.0009 (2)
S2	0.0474 (4)	0.0313 (4)	0.0352 (4)	−0.0129 (3)	−0.0011 (3)	−0.0009 (3)
O1	0.0681 (13)	0.0304 (10)	0.0434 (10)	−0.0213 (9)	0.0001 (9)	−0.0038 (8)
O4	0.0629 (12)	0.0402 (11)	0.0526 (12)	−0.0252 (9)	−0.0240 (10)	0.0106 (9)
O5	0.0881 (16)	0.0351 (11)	0.0444 (11)	−0.0256 (10)	−0.0035 (10)	−0.0036 (8)
N6	0.0469 (12)	0.0279 (11)	0.0395 (11)	−0.0118 (9)	−0.0082 (9)	−0.0074 (9)
N3	0.0426 (11)	0.0251 (11)	0.0437 (12)	−0.0115 (8)	−0.0086 (9)	−0.0046 (9)
N1	0.0475 (12)	0.0304 (11)	0.0410 (12)	−0.0175 (9)	−0.0103 (9)	0.0035 (9)
N2	0.0475 (12)	0.0263 (10)	0.0436 (12)	−0.0159 (9)	−0.0113 (9)	0.0005 (8)
O2	0.0728 (13)	0.0297 (10)	0.0496 (11)	−0.0069 (9)	−0.0059 (10)	−0.0035 (8)
C11	0.0491 (14)	0.0316 (13)	0.0415 (14)	−0.0079 (11)	−0.0100 (11)	−0.0113 (11)
N5	0.0505 (13)	0.0363 (12)	0.0343 (11)	−0.0189 (10)	−0.0057 (9)	0.0019 (9)
C5	0.0456 (14)	0.0327 (13)	0.0331 (12)	−0.0151 (11)	−0.0032 (10)	−0.0023 (10)
N4	0.0606 (15)	0.0363 (13)	0.0419 (13)	−0.0206 (11)	−0.0148 (11)	0.0039 (10)
O3	0.0605 (13)	0.0655 (15)	0.0512 (13)	−0.0273 (11)	0.0125 (10)	−0.0013 (11)
C10	0.0410 (13)	0.0298 (12)	0.0395 (13)	−0.0089 (10)	−0.0093 (10)	−0.0054 (10)
C3	0.0378 (12)	0.0328 (13)	0.0437 (14)	−0.0107 (10)	−0.0030 (10)	−0.0062 (10)
C2	0.0297 (11)	0.0230 (11)	0.0432 (13)	−0.0093 (8)	−0.0099 (9)	−0.0006 (9)
C6	0.0529 (15)	0.0373 (14)	0.0485 (15)	−0.0203 (12)	−0.0088 (12)	0.0048 (11)
C1	0.0344 (11)	0.0282 (12)	0.0375 (13)	−0.0116 (9)	−0.0082 (9)	0.0004 (9)
C13	0.0458 (14)	0.0281 (13)	0.0536 (16)	−0.0109 (11)	−0.0054 (12)	0.0033 (11)
C14	0.0489 (15)	0.0369 (14)	0.0388 (14)	−0.0071 (11)	−0.0058 (11)	−0.0055 (11)
C8	0.0549 (17)	0.0600 (19)	0.0384 (14)	−0.0180 (14)	−0.0130 (12)	−0.0015 (13)
C12	0.0415 (13)	0.0264 (12)	0.0601 (17)	−0.0078 (10)	−0.0113 (12)	−0.0106 (11)
C7	0.0516 (16)	0.0532 (17)	0.0495 (16)	−0.0262 (13)	−0.0084 (13)	−0.0025 (13)
C4	0.071 (2)	0.0458 (16)	0.0443 (17)	−0.0181 (14)	0.0043 (14)	−0.0100 (13)
C9	0.0625 (17)	0.0483 (16)	0.0348 (14)	−0.0157 (13)	−0.0103 (12)	0.0041 (12)

Geometric parameters (Å, º)

S1—C2	1.726 (2)	N5—C5	1.368 (3)
S1—C1	1.731 (3)	N5—H5A	0.84 (4)
S2—O3	1.418 (2)	C5—C6	1.423 (4)
S2—O2	1.425 (2)	N4—H4A	0.83 (4)
S2—N4	1.581 (3)	N4—H4B	0.88 (4)
S2—C1	1.773 (3)	C3—C4	1.491 (4)
O1—C3	1.222 (3)	C6—C7	1.352 (4)
O4—C5	1.256 (3)	C6—H6	0.9300
O5—C10	1.253 (3)	C13—C14	1.354 (4)
N6—C14	1.356 (4)	C13—C12	1.393 (4)
N6—C10	1.361 (4)	C13—H13	0.9300
N6—H6A	0.90 (4)	C14—H14	0.9300
N3—C3	1.356 (4)	C8—C9	1.353 (5)
N3—C2	1.366 (4)	C8—C7	1.403 (4)
N3—H3A	0.85 (3)	C8—H8	0.9300
N1—C1	1.292 (3)	C12—H12	0.9300
N1—N2	1.372 (3)	C7—H7	0.9300
N2—C2	1.316 (3)	C4—H4C	0.9600
C11—C12	1.356 (4)	C4—H4D	0.9600
C11—C10	1.429 (4)	C4—H4E	0.9600
C11—H11	0.9300	C9—H9	0.9300
N5—C9	1.347 (4)
C2—S1—C1	85.81 (12)	N2—C2—N3	120.9 (2)
O3—S2—O2	120.57 (14)	N2—C2—S1	114.39 (19)
O3—S2—N4	108.47 (15)	N3—C2—S1	124.73 (18)
O2—S2—N4	108.92 (14)	C7—C6—C5	120.8 (3)
O3—S2—C1	107.07 (13)	C7—C6—H6	119.6
O2—S2—C1	104.15 (12)	C5—C6—H6	119.6
N4—S2—C1	106.84 (13)	N1—C1—S1	115.6 (2)
C14—N6—C10	124.0 (2)	N1—C1—S2	123.4 (2)
C14—N6—H6A	119 (2)	S1—C1—S2	120.98 (14)
C10—N6—H6A	117 (2)	C14—C13—C12	118.3 (3)
C3—N3—C2	123.3 (2)	C14—C13—H13	120.8
C3—N3—H3A	120 (2)	C12—C13—H13	120.8
C2—N3—H3A	117 (2)	N6—C14—C13	120.5 (3)
C1—N1—N2	111.9 (2)	N6—C14—H14	119.7
C2—N2—N1	112.4 (2)	C13—C14—H14	119.7
C12—C11—C10	120.7 (3)	C9—C8—C7	117.9 (3)
C12—C11—H11	119.7	C9—C8—H8	121.1
C10—C11—H11	119.7	C7—C8—H8	121.1
C9—N5—C5	124.0 (2)	C11—C12—C13	121.1 (2)
C9—N5—H5A	118 (2)	C11—C12—H12	119.4
C5—N5—H5A	118 (2)	C13—C12—H12	119.4
O4—C5—N5	119.9 (2)	C6—C7—C8	121.1 (3)
O4—C5—C6	124.9 (2)	C6—C7—H7	119.4
N5—C5—C6	115.3 (2)	C8—C7—H7	119.4
S2—N4—H4A	116 (3)	C3—C4—H4C	109.5
S2—N4—H4B	109 (3)	C3—C4—H4D	109.5
H4A—N4—H4B	119 (4)	H4C—C4—H4D	109.5
O5—C10—N6	120.2 (2)	C3—C4—H4E	109.5
O5—C10—C11	124.5 (2)	H4C—C4—H4E	109.5
N6—C10—C11	115.3 (2)	H4D—C4—H4E	109.5
O1—C3—N3	121.0 (3)	N5—C9—C8	120.9 (3)
O1—C3—C4	123.1 (3)	N5—C9—H9	119.6
N3—C3—C4	115.9 (2)	C8—C9—H9	119.6

(ACZCPRH111)

Crystal data

C4H6N4O3S2·C6H11NO·H2O	F(000) = 372
Mr = 353.42	Dx = 1.481 Mg m^−3
Triclinic, P1	Melting point: 353 K
a = 4.9969 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.6983 (6) Å	Cell parameters from 2588 reflections
c = 14.6244 (8) Å	θ = 4.3–71.6°
α = 70.868 (5)°	µ = 3.34 mm^−1
β = 81.892 (4)°	T = 298 K
γ = 80.262 (4)°	Block, colorles
V = 792.64 (7) Å^3	0.22 × 0.20 × 0.18 mm
Z = 2

Data collection

Xcalibur, Eos, Gemini diffractometer	2792 independent reflections
Radiation source: fine-focus sealed tube	2633 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.012
ω scans	θmax = 67.1°, θmin = 3.2°
Absorption correction: multi-scan	h = −3→5
Tmin = 0.344, Tmax = 1.000	k = −13→13
4238 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0732P)^2 + 0.2015P] where P = (Fo^2 + 2Fc^2)/3
2792 reflections	(Δ/σ)max = 0.001
224 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.34 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
S1	0.46604 (9)	0.66085 (4)	0.81893 (3)	0.03689 (17)
S2	0.13348 (9)	0.88093 (4)	0.86580 (3)	0.03464 (16)
N1	0.5296 (3)	0.72165 (15)	0.96732 (11)	0.0366 (4)
O3	−0.0206 (3)	0.85828 (14)	0.80014 (11)	0.0457 (4)
O2	0.0081 (3)	0.89119 (14)	0.95736 (10)	0.0466 (4)
N3	0.8821 (4)	0.48098 (15)	0.88493 (12)	0.0368 (4)
N2	0.7199 (3)	0.62081 (14)	0.96965 (12)	0.0371 (4)
N4	0.2778 (4)	0.99761 (15)	0.81091 (14)	0.0429 (4)
O1	0.6895 (4)	0.47394 (14)	0.75737 (12)	0.0539 (4)
C2	0.7098 (4)	0.58016 (16)	0.89711 (13)	0.0328 (4)
C1	0.3890 (4)	0.75179 (16)	0.89379 (13)	0.0324 (4)
C3	0.8640 (4)	0.43117 (17)	0.81336 (14)	0.0390 (4)
C4	1.0735 (5)	0.3246 (2)	0.81105 (18)	0.0528 (5)
H4A	1.0230	0.2843	0.7697	0.079*
H4B	1.0847	0.2685	0.8756	0.079*
H4C	1.2474	0.3523	0.7864	0.079*
O5	0.4198 (4)	0.88908 (18)	0.10029 (14)	0.0568 (4)
O4	0.5211 (4)	0.97154 (16)	0.38384 (11)	0.0561 (4)
N5	0.2630 (4)	0.88580 (17)	0.51860 (14)	0.0481 (4)
C5	0.3483 (4)	0.90157 (19)	0.42601 (15)	0.0427 (5)
C9	0.1699 (7)	0.6720 (3)	0.5939 (2)	0.0746 (8)
H9A	0.3564	0.6564	0.6108	0.089*
H9B	0.0608	0.6243	0.6489	0.089*
C6	0.2383 (5)	0.8302 (2)	0.37460 (17)	0.0534 (6)
H6A	0.3010	0.8579	0.3061	0.064*
H6B	0.0407	0.8460	0.3805	0.064*
C7	0.3268 (6)	0.6928 (2)	0.4155 (2)	0.0677 (7)
H7A	0.3143	0.6554	0.3663	0.081*
H7B	0.5166	0.6795	0.4284	0.081*
C10	0.0673 (6)	0.8057 (2)	0.57692 (19)	0.0590 (6)
H10A	−0.0990	0.8260	0.5446	0.071*
H10B	0.0231	0.8202	0.6393	0.071*
C8	0.1611 (7)	0.6293 (2)	0.5076 (3)	0.0772 (9)
H8A	−0.0274	0.6402	0.4937	0.093*
H8B	0.2252	0.5425	0.5255	0.093*
H4E	0.367 (6)	1.022 (3)	0.850 (2)	0.058 (7)*
H3A	0.998 (5)	0.455 (2)	0.9228 (18)	0.039 (6)*
H5A	0.329 (6)	0.923 (2)	0.5448 (19)	0.050 (7)*
H4D	0.349 (5)	1.006 (2)	0.751 (2)	0.050 (7)*
H5B	0.287 (8)	0.934 (3)	0.076 (2)	0.079 (10)*
H5C	0.469 (10)	0.853 (4)	0.068 (3)	0.127 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0384 (3)	0.0384 (3)	0.0366 (3)	0.00291 (19)	−0.01233 (19)	−0.0158 (2)
S2	0.0302 (3)	0.0381 (3)	0.0352 (3)	0.00124 (18)	−0.00382 (18)	−0.01345 (19)
N1	0.0373 (8)	0.0387 (8)	0.0349 (8)	−0.0013 (6)	−0.0063 (6)	−0.0136 (7)
O3	0.0389 (8)	0.0512 (8)	0.0501 (8)	−0.0014 (6)	−0.0124 (6)	−0.0186 (7)
O2	0.0409 (8)	0.0547 (8)	0.0426 (8)	0.0022 (6)	0.0022 (6)	−0.0197 (7)
N3	0.0365 (9)	0.0349 (8)	0.0396 (9)	0.0027 (6)	−0.0127 (7)	−0.0123 (7)
N2	0.0387 (9)	0.0371 (8)	0.0362 (8)	0.0006 (6)	−0.0093 (6)	−0.0127 (6)
N4	0.0493 (10)	0.0381 (9)	0.0410 (10)	−0.0035 (7)	−0.0069 (8)	−0.0122 (7)
O1	0.0611 (10)	0.0526 (9)	0.0560 (9)	0.0082 (7)	−0.0247 (8)	−0.0277 (7)
C2	0.0309 (9)	0.0341 (9)	0.0326 (9)	−0.0045 (7)	−0.0062 (7)	−0.0078 (7)
C1	0.0309 (9)	0.0325 (9)	0.0340 (9)	−0.0018 (7)	−0.0029 (7)	−0.0119 (7)
C3	0.0416 (11)	0.0344 (9)	0.0409 (10)	−0.0035 (8)	−0.0059 (8)	−0.0114 (8)
C4	0.0578 (14)	0.0464 (12)	0.0569 (13)	0.0064 (10)	−0.0091 (11)	−0.0245 (10)
O5	0.0546 (11)	0.0621 (10)	0.0618 (11)	0.0095 (8)	−0.0177 (8)	−0.0334 (9)
O4	0.0656 (11)	0.0634 (10)	0.0453 (8)	−0.0290 (8)	0.0041 (7)	−0.0186 (7)
N5	0.0575 (12)	0.0494 (10)	0.0454 (10)	−0.0205 (9)	0.0012 (8)	−0.0212 (8)
C5	0.0447 (11)	0.0414 (10)	0.0435 (11)	−0.0061 (8)	−0.0062 (9)	−0.0141 (8)
C9	0.094 (2)	0.0565 (15)	0.0684 (17)	−0.0294 (15)	−0.0192 (16)	0.0009 (13)
C6	0.0556 (14)	0.0651 (14)	0.0475 (12)	−0.0154 (11)	−0.0106 (10)	−0.0221 (11)
C7	0.0662 (16)	0.0645 (16)	0.093 (2)	−0.0017 (13)	−0.0225 (15)	−0.0497 (15)
C10	0.0631 (15)	0.0655 (15)	0.0523 (13)	−0.0263 (12)	0.0078 (11)	−0.0202 (11)
C8	0.085 (2)	0.0432 (13)	0.111 (2)	−0.0118 (13)	−0.0362 (18)	−0.0211 (14)

Geometric parameters (Å, º)

S1—C2	1.7259 (18)	O1—C3	1.211 (3)
S1—C1	1.7276 (18)	C3—C4	1.493 (3)
S2—O3	1.4247 (15)	O4—C5	1.247 (3)
S2—O2	1.4295 (15)	N5—C5	1.323 (3)
S2—N4	1.5745 (18)	N5—C10	1.453 (3)
S2—C1	1.7804 (18)	C5—C6	1.499 (3)
N1—C1	1.287 (2)	C9—C8	1.510 (4)
N1—N2	1.378 (2)	C9—C10	1.511 (4)
N3—C2	1.369 (3)	C6—C7	1.530 (4)
N3—C3	1.374 (3)	C7—C8	1.513 (4)
N2—C2	1.307 (2)
C2—S1—C1	85.27 (9)	N1—C1—S2	123.64 (14)
O3—S2—O2	120.63 (9)	S1—C1—S2	120.19 (11)
O3—S2—N4	108.90 (10)	O1—C3—N3	120.60 (19)
O2—S2—N4	108.60 (10)	O1—C3—C4	124.51 (19)
O3—S2—C1	104.01 (9)	N3—C3—C4	114.88 (18)
O2—S2—C1	105.71 (9)	C5—N5—C10	126.3 (2)
N4—S2—C1	108.33 (9)	O4—C5—N5	120.5 (2)
C1—N1—N2	111.55 (15)	O4—C5—C6	121.2 (2)
C2—N3—C3	123.01 (17)	N5—C5—C6	118.22 (19)
C2—N2—N1	111.94 (15)	C8—C9—C10	114.0 (2)
N2—C2—N3	121.76 (17)	C5—C6—C7	112.5 (2)
N2—C2—S1	115.08 (14)	C8—C7—C6	114.5 (2)
N3—C2—S1	123.16 (14)	N5—C10—C9	113.3 (2)
N1—C1—S1	116.16 (14)	C9—C8—C7	115.7 (2)

(ACZDMSO)

Crystal data

2(C4H6N4O3S2)·C2H6OS	Dx = 1.607 Mg m^−3
Mr = 522.62	Melting point: 423 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 52.62 (3) Å	Cell parameters from 8298 reflections
b = 4.816 (2) Å	θ = 2.4–27.7°
c = 17.814 (9) Å	µ = 0.59 mm^−1
β = 106.785 (13)°	T = 298 K
V = 4322 (4) Å^3	Plate, colorles
Z = 8	0.20 × 0.18 × 0.18 mm
F(000) = 2160

Data collection

CCD area detector diffractometer	3834 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 26.5°, θmin = 1.6°
phi and ω scans	h = −64→64
21342 measured reflections	k = −6→6
4378 independent reflections	l = −22→22

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) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 4.6734P] where P = (Fo^2 + 2Fc^2)/3
4378 reflections	(Δ/σ)max = 0.002
299 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.25 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
S3	0.006883 (10)	−0.05456 (11)	0.15916 (3)	0.03631 (14)
S4	0.063213 (11)	−0.27631 (11)	0.21613 (3)	0.03644 (14)
O4	−0.04452 (3)	0.0799 (3)	0.12430 (9)	0.0474 (4)
N7	−0.02235 (3)	0.3259 (4)	0.05622 (10)	0.0355 (4)
O6	0.04826 (3)	−0.4541 (3)	0.25137 (10)	0.0513 (4)
C6	0.00128 (4)	0.1927 (4)	0.08639 (11)	0.0317 (4)
N5	0.04358 (3)	0.0927 (4)	0.09867 (10)	0.0369 (4)
N8	0.08079 (4)	−0.0763 (4)	0.28187 (12)	0.0416 (4)
O5	0.07982 (3)	−0.3869 (4)	0.17311 (10)	0.0516 (4)
N6	0.02160 (3)	0.2467 (4)	0.06040 (10)	0.0374 (4)
C7	−0.04479 (4)	0.2645 (5)	0.07735 (12)	0.0368 (5)
C5	0.03872 (4)	−0.0674 (4)	0.15096 (11)	0.0328 (4)
C8	−0.06839 (5)	0.4366 (6)	0.03851 (15)	0.0510 (6)
H8A	−0.0841	0.3476	0.0437	0.077*
H8B	−0.0697	0.4570	−0.0161	0.077*
H8C	−0.0666	0.6163	0.0628	0.077*
S2	0.145927 (11)	0.33975 (11)	0.45615 (3)	0.03771 (14)
S1	0.193875 (12)	0.26355 (14)	0.39428 (4)	0.04959 (17)
N4	0.12674 (4)	0.4870 (5)	0.38253 (13)	0.0435 (5)
O3	0.14239 (4)	0.4519 (4)	0.52612 (9)	0.0549 (4)
N2	0.21778 (4)	0.6305 (5)	0.49380 (12)	0.0495 (5)
C2	0.22078 (4)	0.4699 (5)	0.43775 (13)	0.0423 (5)
C1	0.17893 (4)	0.4219 (5)	0.45742 (12)	0.0383 (5)
N1	0.19316 (4)	0.6020 (4)	0.50505 (12)	0.0467 (5)
O2	0.14364 (4)	0.0484 (3)	0.44237 (11)	0.0542 (4)
N3	0.24391 (4)	0.4683 (5)	0.41755 (13)	0.0484 (5)
C3	0.24843 (5)	0.3005 (6)	0.36117 (15)	0.0576 (7)
O1	0.23177 (4)	0.1342 (6)	0.32735 (14)	0.0918 (8)
C4	0.27461 (6)	0.3372 (8)	0.34596 (17)	0.0676 (8)
H4A	0.2827	0.1589	0.3449	0.101*
H4B	0.2859	0.4485	0.3868	0.101*
H4C	0.2721	0.4279	0.2964	0.101*
S5	0.134755 (13)	0.27251 (13)	0.18180 (4)	0.04840 (17)
O7	0.13023 (4)	0.1643 (4)	0.25691 (9)	0.0564 (5)
C9	0.11184 (5)	0.0939 (6)	0.10491 (13)	0.0504 (6)
H9A	0.1137	−0.1024	0.1142	0.076*
H9B	0.1152	0.1371	0.0561	0.076*
H9C	0.0941	0.1500	0.1026	0.076*
C10	0.16389 (5)	0.1016 (8)	0.17402 (17)	0.0722 (9)
H10A	0.1790	0.1680	0.2144	0.108*
H10B	0.1663	0.1397	0.1236	0.108*
H10C	0.1621	−0.0949	0.1799	0.108*
H4D	0.1278 (5)	0.415 (6)	0.3405 (17)	0.056 (8)*
H7A	−0.0230 (4)	0.441 (5)	0.0219 (12)	0.029 (6)*
H4E	0.1260 (5)	0.634 (6)	0.3891 (15)	0.039 (8)*
H8D	0.0928 (6)	0.013 (6)	0.2678 (15)	0.052 (8)*
H8E	0.0721 (6)	−0.010 (6)	0.3084 (16)	0.060 (9)*
H3A	0.2545 (5)	0.567 (6)	0.4397 (15)	0.050 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S3	0.0381 (3)	0.0379 (3)	0.0362 (3)	0.0009 (2)	0.0160 (2)	0.0080 (2)
S4	0.0398 (3)	0.0301 (3)	0.0407 (3)	0.0057 (2)	0.0136 (2)	0.0033 (2)
O4	0.0456 (9)	0.0491 (10)	0.0541 (9)	−0.0005 (7)	0.0249 (7)	0.0120 (8)
N7	0.0342 (9)	0.0389 (10)	0.0337 (9)	−0.0011 (7)	0.0104 (7)	0.0089 (8)
O6	0.0545 (10)	0.0421 (9)	0.0588 (10)	0.0005 (8)	0.0189 (8)	0.0157 (8)
C6	0.0350 (10)	0.0327 (10)	0.0280 (9)	−0.0048 (8)	0.0098 (8)	−0.0006 (8)
N5	0.0348 (9)	0.0411 (10)	0.0358 (9)	0.0002 (8)	0.0116 (7)	0.0044 (8)
N8	0.0397 (10)	0.0453 (11)	0.0394 (10)	0.0043 (9)	0.0109 (8)	0.0006 (9)
O5	0.0557 (10)	0.0444 (9)	0.0600 (10)	0.0119 (8)	0.0250 (8)	−0.0057 (8)
N6	0.0340 (9)	0.0435 (10)	0.0350 (9)	−0.0016 (7)	0.0105 (7)	0.0083 (7)
C7	0.0348 (11)	0.0405 (12)	0.0359 (11)	−0.0037 (9)	0.0114 (9)	−0.0025 (9)
C5	0.0356 (10)	0.0325 (10)	0.0309 (10)	0.0010 (8)	0.0106 (8)	−0.0007 (8)
C8	0.0364 (12)	0.0612 (16)	0.0547 (14)	0.0043 (11)	0.0119 (10)	0.0067 (12)
S2	0.0394 (3)	0.0343 (3)	0.0405 (3)	−0.0055 (2)	0.0131 (2)	−0.0010 (2)
S1	0.0421 (3)	0.0571 (4)	0.0507 (4)	−0.0143 (3)	0.0152 (3)	−0.0174 (3)
N4	0.0423 (11)	0.0383 (12)	0.0485 (13)	0.0014 (9)	0.0109 (9)	−0.0056 (10)
O3	0.0643 (11)	0.0617 (11)	0.0448 (9)	−0.0113 (9)	0.0254 (8)	−0.0059 (8)
N2	0.0350 (10)	0.0523 (12)	0.0563 (12)	−0.0047 (9)	0.0055 (9)	−0.0129 (10)
C2	0.0349 (11)	0.0426 (12)	0.0443 (12)	−0.0049 (9)	0.0034 (9)	−0.0007 (10)
C1	0.0362 (11)	0.0378 (12)	0.0386 (11)	−0.0016 (9)	0.0071 (9)	−0.0003 (9)
N1	0.0347 (10)	0.0490 (12)	0.0515 (11)	−0.0018 (8)	0.0047 (8)	−0.0095 (9)
O2	0.0596 (10)	0.0334 (9)	0.0693 (11)	−0.0064 (8)	0.0184 (9)	0.0019 (8)
N3	0.0354 (10)	0.0558 (13)	0.0515 (12)	−0.0096 (9)	0.0085 (9)	−0.0068 (10)
C3	0.0494 (15)	0.0767 (19)	0.0479 (14)	−0.0093 (13)	0.0157 (12)	−0.0072 (13)
O1	0.0690 (14)	0.130 (2)	0.0859 (15)	−0.0363 (14)	0.0367 (12)	−0.0586 (16)
C4	0.0557 (16)	0.098 (2)	0.0542 (16)	−0.0054 (16)	0.0240 (13)	0.0036 (16)
S5	0.0511 (4)	0.0509 (4)	0.0475 (3)	−0.0027 (3)	0.0210 (3)	−0.0054 (3)
O7	0.0606 (11)	0.0700 (12)	0.0417 (9)	−0.0001 (9)	0.0195 (8)	−0.0046 (8)
C9	0.0455 (13)	0.0634 (16)	0.0425 (13)	0.0000 (12)	0.0131 (10)	0.0031 (11)
C10	0.0413 (14)	0.118 (3)	0.0572 (16)	0.0113 (16)	0.0136 (12)	−0.0061 (17)

Geometric parameters (Å, º)

S3—C6	1.722 (2)	S2—N4	1.574 (2)
S3—C5	1.724 (2)	S2—C1	1.775 (2)
S4—O5	1.4217 (17)	S1—C2	1.720 (2)
S4—O6	1.4252 (17)	S1—C1	1.725 (2)
S4—N8	1.590 (2)	N2—C2	1.308 (3)
S4—C5	1.777 (2)	N2—N1	1.374 (3)
O4—C7	1.218 (3)	C2—N3	1.365 (3)
N7—C6	1.364 (3)	C1—N1	1.291 (3)
N7—C7	1.371 (3)	N3—C3	1.363 (3)
C6—N6	1.308 (3)	C3—O1	1.211 (3)
N5—C5	1.290 (3)	C3—C4	1.489 (4)
N5—N6	1.378 (2)	S5—O7	1.5172 (19)
C7—C8	1.487 (3)	S5—C9	1.765 (3)
S2—O3	1.4192 (18)	S5—C10	1.780 (3)
S2—O2	1.4235 (19)
C6—S3—C5	85.43 (10)	O2—S2—N4	107.36 (12)
O5—S4—O6	121.06 (11)	O3—S2—C1	106.27 (11)
O5—S4—N8	107.84 (12)	O2—S2—C1	104.81 (11)
O6—S4—N8	108.49 (12)	N4—S2—C1	107.46 (11)
O5—S4—C5	107.61 (10)	C2—S1—C1	85.53 (11)
O6—S4—C5	103.86 (10)	C2—N2—N1	112.29 (19)
N8—S4—C5	107.22 (11)	N2—C2—N3	121.2 (2)
C6—N7—C7	123.36 (19)	N2—C2—S1	114.83 (18)
N6—C6—N7	120.83 (18)	N3—C2—S1	123.97 (19)
N6—C6—S3	115.10 (16)	N1—C1—S1	116.01 (17)
N7—C6—S3	124.07 (15)	N1—C1—S2	122.54 (18)
C5—N5—N6	111.46 (17)	S1—C1—S2	121.45 (13)
C6—N6—N5	111.91 (17)	C1—N1—N2	111.32 (19)
O4—C7—N7	120.4 (2)	C3—N3—C2	123.8 (2)
O4—C7—C8	124.7 (2)	O1—C3—N3	120.2 (3)
N7—C7—C8	114.93 (19)	O1—C3—C4	124.2 (3)
N5—C5—S3	116.08 (15)	N3—C3—C4	115.5 (2)
N5—C5—S4	123.54 (16)	O7—S5—C9	105.72 (12)
S3—C5—S4	120.27 (12)	O7—S5—C10	105.53 (13)
O3—S2—O2	120.03 (11)	C9—S5—C10	97.18 (14)
O3—S2—N4	110.19 (13)

(ACZMeHP11)

Crystal data

C4H6N4O3S2·C6H7NO	Dx = 1.554 Mg m^−3
Mr = 331.37	Melting point: 403 K
Monoclinic, p_1_c_1	Cu Kα radiation, λ = 1.54184 Å
a = 11.3972 (7) Å	Cell parameters from 3599 reflections
b = 18.1641 (3) Å	θ = 4.6–71.4°
c = 10.338 (3) Å	µ = 3.65 mm^−1
β = 97.046 (16)°	T = 298 K
V = 2124.0 (6) Å^3	BLOCK, colorles
Z = 6	0.22 × 0.20 × 0.20 mm
F(000) = 1032

Data collection

Xcalibur, Eos, Gemini diffractometer	4590 independent reflections
Radiation source: fine-focus sealed tube	4295 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 67.1°, θmin = 3.9°
Absorption correction: multi-scan	h = −13→13
Tmin = 0.732, Tmax = 1.000	k = −21→20
7371 measured reflections	l = −8→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0757P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
4590 reflections	Δρmax = 0.41 e Å^−3
583 parameters	Δρmin = −0.29 e Å^−3
4 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.19 (2)

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
S4	0.28049 (9)	0.44599 (6)	−0.01359 (11)	0.0376 (3)
S3	0.30014 (9)	0.27942 (6)	0.02210 (11)	0.0382 (3)
O4	0.2805 (3)	0.13407 (19)	0.0506 (4)	0.0573 (10)
O6	0.1619 (3)	0.4225 (2)	−0.0057 (4)	0.0549 (9)
O5	0.3345 (3)	0.50038 (19)	0.0722 (4)	0.0590 (9)
N5	0.4796 (3)	0.3647 (2)	0.0308 (4)	0.0409 (9)
N6	0.5258 (3)	0.2955 (2)	0.0511 (4)	0.0411 (8)
N7	0.4699 (3)	0.1731 (2)	0.0715 (4)	0.0449 (9)
H41	0.5431	0.1606	0.0858	0.054*
N8	0.2915 (3)	0.4716 (2)	−0.1575 (4)	0.0424 (8)
H6A	0.3718	0.4911	−0.1596	0.051*
H6B	0.2570	0.4484	−0.2139	0.051*
C8	0.4348 (6)	0.0452 (3)	0.0997 (8)	0.0729 (19)
H8A	0.4006	0.0246	0.1720	0.109*
H8B	0.5191	0.0484	0.1212	0.109*
H8C	0.4167	0.0143	0.0246	0.109*
C6	0.4428 (3)	0.2445 (3)	0.0508 (4)	0.0350 (9)
C7	0.3858 (4)	0.1197 (3)	0.0710 (5)	0.0488 (12)
C5	0.3653 (4)	0.3649 (2)	0.0142 (4)	0.0335 (9)
S5	0.10227 (8)	0.22150 (6)	0.72588 (10)	0.0358 (2)
S6	0.12122 (10)	0.05538 (6)	0.75917 (11)	0.0400 (3)
O7	0.1220 (3)	0.36760 (19)	0.6924 (4)	0.0535 (9)
O9	0.0660 (4)	0.00099 (19)	0.6728 (4)	0.0605 (10)
O8	0.2374 (3)	0.0809 (2)	0.7441 (4)	0.0630 (11)
N9	−0.0787 (4)	0.1382 (2)	0.7396 (4)	0.0446 (10)
N11	−0.0653 (3)	0.3308 (2)	0.7024 (4)	0.0396 (8)
H11A	−0.1380	0.3441	0.7005	0.047*
N12	0.1148 (4)	0.0280 (2)	0.9023 (4)	0.0497 (10)
H12D	0.0681	−0.0158	0.9096	0.060*
H12E	0.1412	0.0525	0.9528	0.060*
N10	−0.1225 (3)	0.2087 (2)	0.7257 (4)	0.0436 (9)
C10	−0.0376 (4)	0.2574 (2)	0.7178 (4)	0.0344 (9)
C12	−0.0299 (5)	0.4598 (3)	0.6730 (7)	0.0649 (17)
H12A	−0.0753	0.4713	0.7427	0.097*
H12B	−0.0796	0.4632	0.5912	0.097*
H12C	0.0344	0.4940	0.6738	0.097*
C11	0.0178 (4)	0.3835 (3)	0.6906 (5)	0.0431 (11)
C9	0.0359 (4)	0.1375 (2)	0.7408 (4)	0.0347 (9)
S1	0.63545 (9)	0.27176 (6)	0.37991 (11)	0.0397 (3)
S2	0.61804 (10)	0.43922 (6)	0.34541 (11)	0.0385 (2)
O3	0.4989 (3)	0.41432 (19)	0.3455 (4)	0.0573 (9)
O1	0.6167 (3)	0.1249 (2)	0.4129 (5)	0.0682 (12)
O2	0.6675 (4)	0.48895 (19)	0.4430 (4)	0.0617 (10)
N1	0.8152 (3)	0.3555 (2)	0.3680 (4)	0.0420 (9)
N2	0.8596 (3)	0.2849 (2)	0.3864 (4)	0.0418 (8)
N4	0.6389 (4)	0.4712 (2)	0.2079 (4)	0.0446 (9)
H4D	0.5983	0.4581	0.1403	0.054*
N3	0.8042 (3)	0.1637 (2)	0.4104 (4)	0.0394 (8)
C2	0.7768 (4)	0.2354 (2)	0.3929 (4)	0.0309 (9)
C4	0.7705 (6)	0.0349 (3)	0.4338 (8)	0.080 (2)
H4A	0.7213	0.0056	0.4826	0.119*
H4B	0.8491	0.0369	0.4793	0.119*
H4C	0.7727	0.0133	0.3494	0.119*
C3	0.7218 (4)	0.1102 (3)	0.4186 (6)	0.0511 (12)
C1	0.7018 (4)	0.3562 (2)	0.3629 (4)	0.0353 (9)
O12	0.7022 (3)	0.37071 (18)	0.6965 (4)	0.0497 (8)
N14	0.6329 (3)	0.2555 (2)	0.7260 (4)	0.0393 (8)
H8	0.7047	0.2402	0.7387	0.047*
C20	0.4947 (4)	0.3514 (3)	0.6817 (5)	0.0454 (11)
H20	0.4757	0.4006	0.6650	0.054*
C19	0.6146 (4)	0.3287 (2)	0.7012 (4)	0.0378 (9)
C22	0.4318 (5)	0.2274 (3)	0.7137 (5)	0.0492 (12)
H22	0.3706	0.1940	0.7185	0.059*
C21	0.4078 (4)	0.3010 (3)	0.6876 (5)	0.0502 (12)
H21	0.3294	0.3163	0.6737	0.060*
C24	0.5861 (6)	0.1268 (3)	0.7586 (6)	0.0631 (15)
H24A	0.5198	0.0971	0.7749	0.095*
H24B	0.6449	0.1256	0.8335	0.095*
H24C	0.6192	0.1078	0.6843	0.095*
C23	0.5461 (4)	0.2048 (3)	0.7322 (5)	0.0430 (11)
O11	0.0398 (3)	0.12277 (16)	0.4260 (3)	0.0455 (7)
N15	0.1045 (3)	0.2370 (2)	0.3838 (4)	0.0389 (9)
H18	0.0326	0.2519	0.3805	0.047*
C28	0.3019 (5)	0.2660 (3)	0.3663 (6)	0.0554 (14)
H28	0.3608	0.2995	0.3526	0.067*
C30	0.1456 (6)	0.3648 (3)	0.3433 (7)	0.0648 (16)
H30A	0.1424	0.3882	0.4261	0.097*
H30B	0.0680	0.3644	0.2951	0.097*
H30C	0.1986	0.3915	0.2952	0.097*
C25	0.1252 (4)	0.1634 (2)	0.4082 (4)	0.0391 (9)
C29	0.1883 (4)	0.2883 (3)	0.3641 (5)	0.0458 (11)
C26	0.2446 (5)	0.1411 (3)	0.4093 (6)	0.0521 (13)
H26	0.2650	0.0919	0.4235	0.063*
C27	0.3292 (4)	0.1909 (3)	0.3897 (5)	0.0597 (14)
H27	0.4072	0.1753	0.3918	0.072*
O10	0.6983 (3)	0.86477 (19)	0.6009 (4)	0.0580 (9)
N13	0.7772 (3)	0.7540 (2)	0.5595 (4)	0.0402 (8)
H13A	0.7070	0.7359	0.5512	0.048*
C16	0.9796 (4)	0.7358 (3)	0.5538 (5)	0.0500 (12)
H16	1.0436	0.7058	0.5424	0.060*
C13	0.7879 (4)	0.8275 (3)	0.5867 (5)	0.0436 (10)
C14	0.9056 (5)	0.8560 (3)	0.5969 (5)	0.0515 (13)
H14	0.9192	0.9057	0.6142	0.062*
C18	0.8373 (5)	0.6291 (3)	0.5169 (6)	0.0533 (12)
H18A	0.9042	0.6039	0.4898	0.080*
H18B	0.7720	0.6263	0.4489	0.080*
H18C	0.8157	0.6065	0.5945	0.080*
C17	0.8680 (4)	0.7066 (3)	0.5436 (5)	0.0434 (10)
C15	0.9974 (4)	0.8109 (3)	0.5814 (5)	0.0549 (13)
H15	1.0737	0.8300	0.5893	0.066*
H4E	0.656 (5)	0.5161 (13)	0.204 (5)	0.063 (16)*
H53A	0.875 (4)	0.155 (3)	0.423 (5)	0.048 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S4	0.0373 (5)	0.0325 (5)	0.0446 (6)	0.0043 (4)	0.0116 (4)	0.0000 (4)
S3	0.0266 (5)	0.0347 (5)	0.0532 (6)	−0.0019 (4)	0.0046 (4)	0.0010 (5)
O4	0.0358 (19)	0.042 (2)	0.092 (3)	−0.0081 (14)	0.0000 (17)	−0.0007 (19)
O6	0.0408 (17)	0.054 (2)	0.074 (2)	0.0074 (15)	0.0234 (16)	0.0140 (18)
O5	0.075 (2)	0.0427 (19)	0.059 (2)	0.0038 (17)	0.0064 (18)	−0.0133 (17)
N5	0.0361 (19)	0.031 (2)	0.055 (2)	−0.0055 (14)	0.0023 (16)	0.0009 (16)
N6	0.0303 (17)	0.0358 (19)	0.056 (2)	−0.0024 (14)	0.0005 (15)	0.0000 (16)
N7	0.0289 (17)	0.035 (2)	0.069 (3)	−0.0006 (14)	0.0018 (16)	0.0047 (18)
N8	0.0440 (19)	0.0385 (19)	0.044 (2)	0.0000 (16)	0.0040 (16)	0.0018 (16)
C8	0.057 (3)	0.037 (3)	0.122 (6)	−0.002 (2)	0.002 (3)	0.012 (3)
C6	0.0224 (19)	0.046 (3)	0.036 (2)	−0.0001 (18)	0.0010 (15)	−0.0080 (19)
C7	0.043 (3)	0.038 (2)	0.065 (3)	−0.006 (2)	0.007 (2)	0.006 (2)
C5	0.030 (2)	0.034 (2)	0.036 (2)	−0.0008 (16)	0.0018 (16)	0.0020 (17)
S5	0.0318 (5)	0.0285 (5)	0.0478 (6)	−0.0017 (4)	0.0078 (4)	−0.0019 (4)
S6	0.0446 (6)	0.0259 (5)	0.0518 (7)	0.0001 (4)	0.0144 (5)	−0.0006 (4)
O7	0.0367 (19)	0.0381 (19)	0.086 (3)	−0.0040 (14)	0.0102 (17)	0.0014 (17)
O9	0.092 (3)	0.0371 (18)	0.054 (2)	−0.0016 (18)	0.0126 (19)	−0.0094 (16)
O8	0.0479 (19)	0.042 (2)	0.105 (3)	0.0074 (15)	0.034 (2)	0.010 (2)
N9	0.038 (2)	0.035 (2)	0.062 (3)	−0.0059 (15)	0.0093 (18)	0.0023 (17)
N11	0.0310 (18)	0.0321 (19)	0.055 (2)	0.0022 (15)	0.0045 (16)	0.0029 (16)
N12	0.065 (3)	0.0335 (19)	0.050 (2)	−0.0082 (19)	0.0066 (19)	0.0047 (18)
N10	0.0339 (19)	0.0344 (19)	0.062 (3)	−0.0035 (16)	0.0051 (17)	0.0040 (17)
C10	0.032 (2)	0.032 (2)	0.038 (2)	−0.0014 (18)	0.0008 (17)	−0.0012 (18)
C12	0.050 (3)	0.039 (3)	0.107 (5)	0.002 (2)	0.015 (3)	0.013 (3)
C11	0.040 (3)	0.035 (2)	0.053 (3)	−0.0039 (19)	0.001 (2)	0.000 (2)
C9	0.035 (2)	0.026 (2)	0.044 (2)	−0.0026 (16)	0.0049 (18)	−0.0001 (17)
S1	0.0337 (5)	0.0321 (5)	0.0541 (7)	0.0011 (4)	0.0081 (5)	0.0012 (5)
S2	0.0454 (6)	0.0291 (5)	0.0428 (6)	0.0050 (4)	0.0128 (4)	0.0003 (4)
O3	0.0479 (19)	0.0468 (19)	0.083 (3)	0.0108 (15)	0.0301 (17)	0.0156 (18)
O1	0.040 (2)	0.050 (2)	0.117 (4)	−0.0044 (16)	0.018 (2)	0.008 (2)
O2	0.092 (3)	0.0418 (18)	0.051 (2)	0.0106 (18)	0.0070 (18)	−0.0111 (15)
N1	0.041 (2)	0.0315 (19)	0.055 (2)	0.0009 (14)	0.0085 (16)	0.0015 (16)
N2	0.0341 (17)	0.0330 (18)	0.058 (2)	0.0013 (15)	0.0047 (16)	0.0040 (17)
N4	0.058 (2)	0.0321 (19)	0.043 (2)	−0.0051 (17)	0.0035 (17)	0.0032 (16)
N3	0.0329 (19)	0.0300 (18)	0.055 (2)	0.0013 (15)	0.0048 (15)	0.0030 (16)
C2	0.031 (2)	0.031 (2)	0.032 (2)	0.0027 (16)	0.0071 (16)	0.0037 (16)
C4	0.056 (3)	0.034 (3)	0.148 (7)	0.002 (3)	0.010 (4)	0.000 (4)
C3	0.046 (3)	0.034 (2)	0.075 (4)	−0.001 (2)	0.013 (2)	0.002 (2)
C1	0.039 (2)	0.031 (2)	0.037 (2)	0.0026 (17)	0.0046 (17)	−0.0007 (17)
O12	0.0361 (16)	0.0369 (17)	0.076 (2)	−0.0010 (13)	0.0081 (15)	0.0028 (15)
N14	0.0323 (17)	0.0343 (19)	0.051 (2)	0.0030 (15)	0.0045 (15)	0.0038 (17)
C20	0.037 (2)	0.042 (2)	0.056 (3)	0.0099 (19)	0.002 (2)	−0.001 (2)
C19	0.034 (2)	0.034 (2)	0.045 (2)	−0.0009 (17)	0.0058 (17)	−0.0029 (18)
C22	0.039 (3)	0.057 (3)	0.053 (3)	−0.013 (2)	0.009 (2)	−0.007 (2)
C21	0.033 (2)	0.058 (3)	0.059 (3)	0.002 (2)	0.0041 (19)	−0.006 (2)
C24	0.077 (4)	0.039 (3)	0.076 (4)	−0.010 (3)	0.020 (3)	0.006 (3)
C23	0.044 (2)	0.041 (2)	0.046 (3)	−0.009 (2)	0.0126 (19)	−0.004 (2)
O11	0.0391 (15)	0.0318 (14)	0.066 (2)	−0.0012 (13)	0.0090 (14)	0.0051 (14)
N15	0.0346 (19)	0.0341 (19)	0.047 (2)	−0.0055 (15)	0.0035 (16)	0.0007 (16)
C28	0.050 (3)	0.057 (3)	0.060 (3)	−0.018 (2)	0.010 (2)	−0.002 (3)
C30	0.076 (4)	0.040 (3)	0.079 (4)	−0.012 (3)	0.010 (3)	0.007 (3)
C25	0.039 (2)	0.034 (2)	0.044 (2)	−0.0032 (18)	0.0058 (18)	−0.0021 (18)
C29	0.054 (3)	0.040 (2)	0.042 (2)	−0.013 (2)	0.002 (2)	0.0014 (19)
C26	0.044 (3)	0.039 (3)	0.072 (4)	−0.001 (2)	0.004 (2)	−0.003 (2)
C27	0.035 (2)	0.072 (4)	0.073 (4)	−0.007 (2)	0.008 (2)	−0.003 (3)
O10	0.0357 (16)	0.0432 (19)	0.094 (3)	−0.0010 (13)	0.0013 (16)	−0.0068 (17)
N13	0.0284 (17)	0.044 (2)	0.047 (2)	−0.0040 (15)	0.0031 (14)	0.0029 (17)
C16	0.033 (2)	0.058 (3)	0.059 (3)	0.000 (2)	0.010 (2)	0.009 (2)
C13	0.035 (2)	0.044 (2)	0.050 (3)	−0.0046 (19)	0.0002 (18)	0.0042 (19)
C14	0.043 (3)	0.045 (3)	0.064 (3)	−0.015 (2)	0.001 (2)	0.007 (2)
C18	0.052 (3)	0.044 (3)	0.064 (3)	0.000 (2)	0.011 (2)	0.000 (2)
C17	0.039 (2)	0.048 (3)	0.044 (2)	0.0016 (19)	0.0090 (18)	0.007 (2)
C15	0.033 (2)	0.068 (3)	0.064 (3)	−0.009 (2)	0.008 (2)	0.014 (3)

Geometric parameters (Å, º)

S4—O5	1.417 (4)	N3—C3	1.361 (6)
S4—O6	1.429 (3)	N3—H53A	0.82 (5)
S4—N8	1.579 (4)	C4—C3	1.477 (7)
S4—C5	1.767 (4)	C4—H4A	0.9600
S3—C5	1.727 (4)	C4—H4B	0.9600
S3—C6	1.736 (4)	C4—H4C	0.9600
O4—C7	1.222 (6)	O12—C19	1.262 (5)
N5—C5	1.293 (6)	N14—C23	1.359 (6)
N5—N6	1.370 (5)	N14—C19	1.365 (6)
N6—C6	1.324 (6)	N14—H8	0.8598
N7—C6	1.344 (6)	C20—C21	1.356 (7)
N7—C7	1.364 (6)	C20—C19	1.419 (6)
N7—H41	0.8600	C20—H20	0.9300
N8—H6A	0.9839	C22—C23	1.356 (7)
N8—H6B	0.7845	C22—C21	1.385 (7)
C8—C7	1.479 (7)	C22—H22	0.9300
C8—H8A	0.9600	C21—H21	0.9300
C8—H8B	0.9600	C24—C23	1.504 (7)
C8—H8C	0.9600	C24—H24A	0.9600
S5—C10	1.715 (5)	C24—H24B	0.9600
S5—C9	1.718 (4)	C24—H24C	0.9600
S6—O9	1.425 (4)	O11—C25	1.253 (5)
S6—O8	1.429 (4)	N15—C29	1.367 (6)
S6—N12	1.571 (4)	N15—C25	1.376 (6)
S6—C9	1.778 (4)	N15—H18	0.8601
O7—C11	1.220 (6)	C28—C29	1.355 (8)
N9—C9	1.305 (6)	C28—C27	1.413 (8)
N9—N10	1.375 (5)	C28—H28	0.9300
N11—C11	1.363 (6)	C30—C29	1.480 (7)
N11—C10	1.375 (6)	C30—H30A	0.9600
N11—H11A	0.8600	C30—H30B	0.9600
N12—H12D	0.9651	C30—H30C	0.9600
N12—H12E	0.7225	C25—C26	1.419 (7)
N10—C10	1.321 (6)	C26—C27	1.356 (7)
C12—C11	1.492 (7)	C26—H26	0.9300
C12—H12A	0.9600	C27—H27	0.9300
C12—H12B	0.9600	O10—C13	1.249 (5)
C12—H12C	0.9600	N13—C13	1.366 (6)
S1—C1	1.729 (4)	N13—C17	1.371 (6)
S1—C2	1.731 (4)	N13—H13A	0.8600
S2—O2	1.418 (4)	C16—C17	1.370 (7)
S2—O3	1.431 (3)	C16—C15	1.403 (8)
S2—N4	1.581 (4)	C16—H16	0.9300
S2—C1	1.782 (4)	C13—C14	1.430 (6)
O1—C3	1.222 (6)	C14—C15	1.354 (8)
N1—C1	1.287 (6)	C14—H14	0.9300
N1—N2	1.382 (5)	C18—C17	1.469 (7)
N2—C2	1.311 (6)	C18—H18A	0.9600
N4—H4D	0.8244	C18—H18B	0.9600
N4—H4E	0.84 (2)	C18—H18C	0.9600
N3—C2	1.347 (6)	C15—H15	0.9300
O5—S4—O6	120.9 (2)	C3—C4—H4C	109.5
O5—S4—N8	107.8 (2)	H4A—C4—H4C	109.5
O6—S4—N8	109.1 (2)	H4B—C4—H4C	109.5
O5—S4—C5	107.0 (2)	O1—C3—N3	121.4 (4)
O6—S4—C5	104.1 (2)	O1—C3—C4	124.1 (5)
N8—S4—C5	107.1 (2)	N3—C3—C4	114.5 (5)
C5—S3—C6	86.4 (2)	N1—C1—S1	115.8 (3)
C5—N5—N6	112.6 (4)	N1—C1—S2	122.4 (3)
C6—N6—N5	112.4 (4)	S1—C1—S2	121.7 (3)
C6—N7—C7	122.6 (4)	C23—N14—C19	125.0 (4)
C6—N7—H41	118.7	C23—N14—H8	117.3
C7—N7—H41	118.6	C19—N14—H8	117.6
S4—N8—H6A	107.9	C21—C20—C19	119.5 (4)
S4—N8—H6B	116.9	C21—C20—H20	120.2
H6A—N8—H6B	124.0	C19—C20—H20	120.2
C7—C8—H8A	109.5	O12—C19—N14	119.6 (4)
C7—C8—H8B	109.5	O12—C19—C20	124.8 (4)
H8A—C8—H8B	109.5	N14—C19—C20	115.6 (4)
C7—C8—H8C	109.5	C23—C22—C21	118.9 (5)
H8A—C8—H8C	109.5	C23—C22—H22	120.6
H8B—C8—H8C	109.5	C21—C22—H22	120.6
N6—C6—N7	121.6 (4)	C20—C21—C22	122.2 (5)
N6—C6—S3	113.5 (4)	C20—C21—H21	118.9
N7—C6—S3	124.9 (3)	C22—C21—H21	118.9
O4—C7—N7	121.5 (5)	C23—C24—H24A	109.5
O4—C7—C8	124.7 (5)	C23—C24—H24B	109.5
N7—C7—C8	113.7 (5)	H24A—C24—H24B	109.5
N5—C5—S3	115.1 (3)	C23—C24—H24C	109.5
N5—C5—S4	123.0 (3)	H24A—C24—H24C	109.5
S3—C5—S4	121.8 (2)	H24B—C24—H24C	109.5
C10—S5—C9	85.7 (2)	C22—C23—N14	118.7 (5)
O9—S6—O8	120.0 (3)	C22—C23—C24	125.1 (5)
O9—S6—N12	107.6 (2)	N14—C23—C24	116.2 (4)
O8—S6—N12	110.9 (2)	C29—N15—C25	125.7 (4)
O9—S6—C9	108.7 (2)	C29—N15—H18	117.3
O8—S6—C9	102.6 (2)	C25—N15—H18	117.1
N12—S6—C9	106.1 (2)	C29—C28—C27	118.8 (5)
C9—N9—N10	111.1 (4)	C29—C28—H28	120.6
C11—N11—C10	122.6 (4)	C27—C28—H28	120.6
C11—N11—H11A	118.7	C29—C30—H30A	109.5
C10—N11—H11A	118.7	C29—C30—H30B	109.5
S6—N12—H12D	115.1	H30A—C30—H30B	109.5
S6—N12—H12E	114.9	C29—C30—H30C	109.5
H12D—N12—H12E	129.5	H30A—C30—H30C	109.5
C10—N10—N9	111.8 (4)	H30B—C30—H30C	109.5
N10—C10—N11	119.8 (4)	O11—C25—N15	118.7 (4)
N10—C10—S5	115.2 (3)	O11—C25—C26	126.3 (4)
N11—C10—S5	125.0 (3)	N15—C25—C26	115.0 (4)
C11—C12—H12A	109.5	C28—C29—N15	118.5 (5)
C11—C12—H12B	109.5	C28—C29—C30	125.4 (5)
H12A—C12—H12B	109.5	N15—C29—C30	116.0 (5)
C11—C12—H12C	109.5	C27—C26—C25	120.5 (5)
H12A—C12—H12C	109.5	C27—C26—H26	119.8
H12B—C12—H12C	109.5	C25—C26—H26	119.8
O7—C11—N11	121.2 (4)	C26—C27—C28	121.6 (5)
O7—C11—C12	124.2 (4)	C26—C27—H27	119.2
N11—C11—C12	114.6 (4)	C28—C27—H27	119.2
N9—C9—S5	116.2 (3)	C13—N13—C17	126.1 (4)
N9—C9—S6	122.9 (3)	C13—N13—H13A	117.0
S5—C9—S6	120.9 (3)	C17—N13—H13A	117.0
C1—S1—C2	86.1 (2)	C17—C16—C15	120.1 (5)
O2—S2—O3	119.7 (2)	C17—C16—H16	119.9
O2—S2—N4	108.4 (2)	C15—C16—H16	119.9
O3—S2—N4	111.3 (2)	O10—C13—N13	120.0 (4)
O2—S2—C1	107.8 (2)	O10—C13—C14	124.6 (4)
O3—S2—C1	103.2 (2)	N13—C13—C14	115.4 (4)
N4—S2—C1	105.3 (2)	C15—C14—C13	120.2 (5)
C1—N1—N2	111.4 (4)	C15—C14—H14	119.9
C2—N2—N1	112.9 (3)	C13—C14—H14	119.9
S2—N4—H4D	121.6	C17—C18—H18A	109.5
S2—N4—H4E	117 (4)	C17—C18—H18B	109.5
H4D—N4—H4E	110.6	H18A—C18—H18B	109.5
C2—N3—C3	123.2 (4)	C17—C18—H18C	109.5
C2—N3—H53A	115 (4)	H18A—C18—H18C	109.5
C3—N3—H53A	121 (4)	H18B—C18—H18C	109.5
N2—C2—N3	120.9 (4)	C16—C17—N13	117.1 (5)
N2—C2—S1	113.8 (3)	C16—C17—C18	125.6 (5)
N3—C2—S1	125.3 (3)	N13—C17—C18	117.3 (4)
C3—C4—H4A	109.5	C14—C15—C16	121.2 (4)
C3—C4—H4B	109.5	C14—C15—H15	119.4
H4A—C4—H4B	109.5	C16—C15—H15	119.4
C5—N5—N6—C6	−0.8 (6)	C1—S1—C2—N3	179.9 (4)
N5—N6—C6—N7	−178.8 (4)	C2—N3—C3—O1	−1.5 (9)
N5—N6—C6—S3	1.0 (5)	C2—N3—C3—C4	178.2 (6)
C7—N7—C6—N6	−179.7 (4)	N2—N1—C1—S1	0.1 (5)
C7—N7—C6—S3	0.5 (7)	N2—N1—C1—S2	177.8 (3)
C5—S3—C6—N6	−0.8 (4)	C2—S1—C1—N1	−0.6 (4)
C5—S3—C6—N7	179.0 (4)	C2—S1—C1—S2	−178.3 (3)
C6—N7—C7—O4	0.5 (8)	O2—S2—C1—N1	−51.9 (5)
C6—N7—C7—C8	−178.3 (5)	O3—S2—C1—N1	−179.5 (4)
N6—N5—C5—S3	0.2 (5)	N4—S2—C1—N1	63.6 (4)
N6—N5—C5—S4	179.8 (3)	O2—S2—C1—S1	125.7 (3)
C6—S3—C5—N5	0.3 (4)	O3—S2—C1—S1	−1.9 (3)
C6—S3—C5—S4	−179.3 (3)	N4—S2—C1—S1	−118.8 (3)
O5—S4—C5—N5	−42.1 (5)	C23—N14—C19—O12	−179.3 (4)
O6—S4—C5—N5	−171.2 (4)	C23—N14—C19—C20	0.4 (7)
N8—S4—C5—N5	73.3 (4)	C21—C20—C19—O12	179.2 (5)
O5—S4—C5—S3	137.5 (3)	C21—C20—C19—N14	−0.5 (7)
O6—S4—C5—S3	8.4 (3)	C19—C20—C21—C22	0.8 (8)
N8—S4—C5—S3	−107.1 (3)	C23—C22—C21—C20	−0.9 (8)
C9—N9—N10—C10	−0.2 (6)	C21—C22—C23—N14	0.8 (8)
N9—N10—C10—N11	179.4 (4)	C21—C22—C23—C24	−178.7 (5)
N9—N10—C10—S5	0.2 (6)	C19—N14—C23—C22	−0.6 (7)
C11—N11—C10—N10	−178.4 (4)	C19—N14—C23—C24	179.0 (5)
C11—N11—C10—S5	0.7 (7)	C29—N15—C25—O11	179.1 (4)
C9—S5—C10—N10	−0.1 (4)	C29—N15—C25—C26	−1.5 (7)
C9—S5—C10—N11	−179.3 (4)	C27—C28—C29—N15	−0.5 (8)
C10—N11—C11—O7	0.4 (8)	C27—C28—C29—C30	178.8 (5)
C10—N11—C11—C12	179.2 (5)	C25—N15—C29—C28	1.2 (8)
N10—N9—C9—S5	0.1 (5)	C25—N15—C29—C30	−178.2 (5)
N10—N9—C9—S6	179.3 (3)	O11—C25—C26—C27	−179.4 (5)
C10—S5—C9—N9	0.0 (4)	N15—C25—C26—C27	1.3 (8)
C10—S5—C9—S6	−179.2 (3)	C25—C26—C27—C28	−0.8 (9)
O9—S6—C9—N9	47.4 (5)	C29—C28—C27—C26	0.3 (9)
O8—S6—C9—N9	175.5 (4)	C17—N13—C13—O10	−178.9 (5)
N12—S6—C9—N9	−68.1 (4)	C17—N13—C13—C14	1.1 (7)
O9—S6—C9—S5	−133.5 (3)	O10—C13—C14—C15	179.2 (5)
O8—S6—C9—S5	−5.4 (4)	N13—C13—C14—C15	−0.8 (7)
N12—S6—C9—S5	111.0 (3)	C15—C16—C17—N13	1.0 (8)
C1—N1—N2—C2	0.7 (6)	C15—C16—C17—C18	−179.1 (5)
N1—N2—C2—N3	179.9 (4)	C13—N13—C17—C16	−1.1 (8)
N1—N2—C2—S1	−1.2 (5)	C13—N13—C17—C18	178.9 (5)
C3—N3—C2—N2	179.6 (5)	C13—C14—C15—C16	0.8 (8)
C3—N3—C2—S1	0.8 (7)	C17—C16—C15—C14	−0.8 (8)
C1—S1—C2—N2	1.0 (4)

(ACZNAM11)

Crystal data

C4H6N4O3S2·C6H6N2O	F(000) = 356
Mr = 344.38	Dx = 1.551 Mg m^−3
Triclinic, P1	Melting point: 453 K
a = 5.1477 (8) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.8147 (14) Å	Cell parameters from 1270 reflections
c = 14.2604 (16) Å	θ = 4.4–71.7°
α = 69.797 (11)°	µ = 3.55 mm^−1
β = 85.463 (12)°	T = 298 K
γ = 81.889 (12)°	BLOCK, colorles
V = 737.20 (17) Å^3	0.22 × 0.21 × 0.20 mm
Z = 2

Data collection

Xcalibur, Eos, Gemini diffractometer	1906 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 67.1°, θmin = 3.3°
Detector resolution: ω scans pixels mm^-1	h = −3→6
multi–scan	k = −12→12
4027 measured reflections	l = −16→16
2607 independent reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.1157P)^2] where P = (Fo^2 + 2Fc^2)/3
2607 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.41 e Å^−3
2 restraints	Δρmin = −0.59 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
S1	0.1492 (2)	0.93431 (10)	0.78260 (8)	0.0528 (4)
S2	0.5163 (2)	0.78104 (10)	0.67044 (7)	0.0515 (3)
N2	0.7184 (7)	0.9964 (3)	0.5809 (2)	0.0533 (9)
N3	0.9226 (8)	0.8215 (4)	0.5326 (3)	0.0529 (9)
N1	0.5204 (7)	1.0284 (3)	0.6423 (3)	0.0543 (9)
O1	0.8030 (8)	0.6179 (3)	0.5851 (3)	0.0872 (12)
O3	0.0075 (6)	1.0630 (3)	0.7454 (3)	0.0690 (9)
O2	0.0271 (6)	0.8176 (3)	0.7988 (2)	0.0673 (9)
N4	0.2823 (9)	0.9208 (5)	0.8817 (3)	0.0592 (10)
C2	0.7357 (8)	0.8725 (4)	0.5871 (3)	0.0479 (10)
C3	0.9479 (10)	0.6950 (5)	0.5328 (4)	0.0637 (12)
C1	0.4034 (8)	0.9263 (4)	0.6926 (3)	0.0487 (10)
C4	1.1615 (13)	0.6621 (5)	0.4648 (5)	0.0875 (19)
H4A	1.2521	0.5757	0.4980	0.131*
H4B	1.2829	0.7269	0.4477	0.131*
H4C	1.0867	0.6627	0.4051	0.131*
O4	1.3130 (6)	0.6472 (3)	0.0123 (2)	0.0590 (8)
N6	1.2270 (8)	0.4391 (4)	0.0931 (3)	0.0561 (10)
C5	0.9382 (8)	0.6198 (4)	0.1226 (3)	0.0479 (9)
C10	1.1739 (8)	0.5686 (4)	0.0720 (3)	0.0481 (10)
N5	0.6488 (8)	0.8116 (4)	0.1285 (3)	0.0655 (11)
C6	0.8526 (9)	0.7547 (4)	0.0894 (4)	0.0623 (12)
H6	0.9449	0.8090	0.0360	0.075*
C9	0.8006 (9)	0.5412 (5)	0.2017 (3)	0.0628 (12)
H9	0.8511	0.4501	0.2270	0.075*
C7	0.5195 (10)	0.7322 (5)	0.2058 (4)	0.0676 (13)
H7	0.3773	0.7703	0.2351	0.081*
C8	0.5864 (11)	0.5979 (5)	0.2438 (4)	0.0727 (15)
H8	0.4897	0.5457	0.2969	0.087*
H6B	1.360 (6)	0.411 (4)	0.066 (3)	0.052 (13)*
H3A	1.028 (9)	0.870 (4)	0.506 (3)	0.053 (13)*
H6A	1.125 (7)	0.384 (4)	0.128 (3)	0.058 (13)*
H4F	0.328 (8)	0.986 (5)	0.885 (3)	0.046 (13)*
H4E	0.320 (10)	0.845 (5)	0.918 (4)	0.071 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0489 (6)	0.0520 (6)	0.0493 (6)	−0.0077 (4)	0.0116 (4)	−0.0090 (5)
S2	0.0566 (7)	0.0445 (6)	0.0463 (6)	−0.0127 (4)	0.0127 (4)	−0.0071 (4)
N2	0.061 (2)	0.047 (2)	0.0454 (18)	−0.0128 (16)	0.0146 (16)	−0.0083 (15)
N3	0.062 (2)	0.045 (2)	0.0479 (19)	−0.0186 (17)	0.0178 (17)	−0.0105 (15)
N1	0.059 (2)	0.048 (2)	0.0508 (19)	−0.0099 (16)	0.0117 (16)	−0.0122 (16)
O1	0.113 (3)	0.054 (2)	0.094 (3)	−0.032 (2)	0.051 (2)	−0.0278 (19)
O3	0.059 (2)	0.065 (2)	0.070 (2)	0.0068 (16)	0.0079 (16)	−0.0145 (16)
O2	0.064 (2)	0.069 (2)	0.066 (2)	−0.0228 (16)	0.0129 (16)	−0.0170 (16)
N4	0.080 (3)	0.048 (2)	0.046 (2)	−0.014 (2)	0.0039 (18)	−0.0100 (18)
C2	0.054 (2)	0.048 (2)	0.0348 (18)	−0.0124 (18)	0.0054 (17)	−0.0042 (16)
C3	0.074 (3)	0.053 (3)	0.061 (3)	−0.018 (2)	0.021 (2)	−0.017 (2)
C1	0.051 (2)	0.047 (2)	0.043 (2)	−0.0118 (18)	0.0073 (17)	−0.0088 (17)
C4	0.106 (4)	0.063 (3)	0.094 (4)	−0.024 (3)	0.049 (4)	−0.033 (3)
O4	0.0586 (18)	0.0482 (17)	0.0567 (17)	−0.0069 (14)	0.0210 (14)	−0.0054 (14)
N6	0.053 (2)	0.045 (2)	0.059 (2)	−0.0030 (17)	0.0180 (18)	−0.0087 (17)
C5	0.050 (2)	0.046 (2)	0.044 (2)	−0.0077 (18)	0.0063 (17)	−0.0108 (17)
C10	0.047 (2)	0.048 (2)	0.043 (2)	−0.0064 (18)	0.0040 (17)	−0.0081 (17)
N5	0.064 (3)	0.055 (2)	0.070 (3)	−0.0044 (19)	0.022 (2)	−0.0183 (19)
C6	0.066 (3)	0.052 (3)	0.061 (3)	−0.009 (2)	0.023 (2)	−0.014 (2)
C9	0.064 (3)	0.057 (3)	0.053 (2)	−0.003 (2)	0.017 (2)	−0.007 (2)
C7	0.065 (3)	0.071 (3)	0.063 (3)	−0.009 (2)	0.025 (2)	−0.024 (2)
C8	0.074 (3)	0.067 (3)	0.064 (3)	−0.008 (2)	0.033 (3)	−0.013 (2)

Geometric parameters (Å, º)

S1—O3	1.419 (3)	C4—H4B	0.9600
S1—O2	1.429 (3)	C4—H4C	0.9600
S1—N4	1.572 (4)	O4—C10	1.239 (5)
S1—C1	1.774 (4)	N6—C10	1.319 (5)
S2—C2	1.719 (4)	N6—H6B	0.832 (19)
S2—C1	1.721 (4)	N6—H6A	0.846 (19)
N2—C2	1.302 (5)	C5—C9	1.370 (6)
N2—N1	1.377 (5)	C5—C6	1.386 (6)
N3—C3	1.355 (6)	C5—C10	1.499 (6)
N3—C2	1.364 (5)	N5—C6	1.323 (6)
N3—H3A	0.79 (5)	N5—C7	1.337 (6)
N1—C1	1.292 (5)	C6—H6	0.9300
O1—C3	1.211 (6)	C9—C8	1.382 (6)
N4—H4F	0.79 (4)	C9—H9	0.9300
N4—H4E	0.81 (5)	C7—C8	1.366 (7)
C3—C4	1.495 (7)	C7—H7	0.9300
C4—H4A	0.9600	C8—H8	0.9300
O3—S1—O2	121.4 (2)	H4A—C4—H4B	109.5
O3—S1—N4	108.5 (2)	C3—C4—H4C	109.5
O2—S1—N4	108.5 (2)	H4A—C4—H4C	109.5
O3—S1—C1	106.4 (2)	H4B—C4—H4C	109.5
O2—S1—C1	103.6 (2)	C10—N6—H6B	118 (3)
N4—S1—C1	107.6 (2)	C10—N6—H6A	124 (3)
C2—S2—C1	85.42 (19)	H6B—N6—H6A	118 (4)
C2—N2—N1	112.2 (3)	C9—C5—C6	116.9 (4)
C3—N3—C2	124.2 (4)	C9—C5—C10	124.0 (4)
C3—N3—H3A	122 (3)	C6—C5—C10	119.1 (4)
C2—N3—H3A	113 (3)	O4—C10—N6	121.8 (4)
C1—N1—N2	111.1 (3)	O4—C10—C5	120.1 (4)
S1—N4—H4F	117 (3)	N6—C10—C5	118.2 (3)
S1—N4—H4E	114 (4)	C6—N5—C7	117.0 (4)
H4F—N4—H4E	128 (5)	N5—C6—C5	124.6 (4)
N2—C2—N3	120.8 (4)	N5—C6—H6	117.7
N2—C2—S2	115.1 (3)	C5—C6—H6	117.7
N3—C2—S2	124.0 (3)	C5—C9—C8	119.7 (4)
O1—C3—N3	120.3 (4)	C5—C9—H9	120.2
O1—C3—C4	124.7 (5)	C8—C9—H9	120.2
N3—C3—C4	115.0 (4)	N5—C7—C8	123.1 (4)
N1—C1—S2	116.2 (3)	N5—C7—H7	118.5
N1—C1—S1	121.7 (3)	C8—C7—H7	118.5
S2—C1—S1	122.0 (2)	C7—C8—C9	118.7 (4)
C3—C4—H4A	109.5	C7—C8—H8	120.6
C3—C4—H4B	109.5	C9—C8—H8	120.6

(ACZNAM2HP111)

Crystal data

C4H6N4O3S2·C6H6N2O·C5H5NO	F(000) = 456
Mr = 439.48	Dx = 1.494 Mg m^−3
Triclinic, P1	Melting point: 398 K
a = 7.0347 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.2539 (7) Å	Cell parameters from 3059 reflections
c = 13.7934 (9) Å	θ = 4.3–71.8°
α = 81.685 (6)°	µ = 2.87 mm^−1
β = 83.028 (5)°	T = 298 K
γ = 88.283 (5)°	PLATE, colorles
V = 977.13 (10) Å^3	0.20 × 0.18 × 0.18 mm
Z = 2

Data collection

Xcalibur, Eos, Gemini diffractometer	3493 independent reflections
Radiation source: fine-focus sealed tube	3085 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ω scans	θmax = 67.1°, θmin = 3.3°
Absorption correction: multi-scan	h = −8→5
Tmin = 0.374, Tmax = 1.000	k = −12→12
5696 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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.1265P)^2 + 0.1831P] where P = (Fo^2 + 2Fc^2)/3
3493 reflections	(Δ/σ)max < 0.001
269 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.44 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
S1	0.22992 (10)	0.58018 (6)	0.91819 (4)	0.0443 (2)
S2	0.10956 (11)	0.86219 (6)	0.84318 (5)	0.0509 (3)
N3	0.3772 (3)	0.3583 (2)	0.84479 (15)	0.0432 (5)
H3A	0.4276	0.3208	0.7958	0.052*
N4	−0.1101 (4)	0.8589 (3)	0.83042 (18)	0.0542 (6)
H4D	−0.135 (5)	0.874 (4)	0.765 (3)	0.065*
H4E	−0.169 (5)	0.809 (4)	0.875 (3)	0.065*
O4	0.2932 (3)	0.3349 (2)	1.00854 (14)	0.0579 (6)
N1	0.2665 (4)	0.6787 (2)	0.73554 (17)	0.0532 (6)
O2	0.1267 (4)	0.8680 (2)	0.94448 (18)	0.0756 (7)
N2	0.3323 (4)	0.5504 (2)	0.73756 (17)	0.0529 (6)
C2	0.3203 (4)	0.4885 (3)	0.82671 (17)	0.0398 (5)
O3	0.1975 (4)	0.9579 (2)	0.7666 (2)	0.0748 (7)
C3	0.3579 (4)	0.2863 (3)	0.93588 (19)	0.0449 (6)
C1	0.2122 (4)	0.7064 (3)	0.82222 (19)	0.0432 (6)
C4	0.4247 (6)	0.1463 (3)	0.9399 (2)	0.0640 (9)
H4A	0.5228	0.1301	0.9831	0.096*
H4B	0.4755	0.1299	0.8750	0.096*
H4C	0.3190	0.0889	0.9644	0.096*
O5	0.2092 (4)	1.1295 (2)	0.36200 (15)	0.0630 (6)
N7	0.0777 (4)	0.4994 (2)	0.36778 (17)	0.0498 (6)
H7A	0.0756	0.4481	0.4231	0.060*
N6	0.2013 (3)	1.0862 (2)	0.52532 (17)	0.0502 (6)
H6B	0.1589	1.1642	0.5325	0.060*
H6A	0.2210	1.0307	0.5762	0.060*
O1	−0.0862 (4)	0.6521 (2)	0.44814 (15)	0.0629 (6)
C6	0.3112 (4)	0.9151 (3)	0.42818 (18)	0.0398 (5)
N5	0.4717 (3)	0.7672 (2)	0.32463 (16)	0.0477 (5)
C12	0.0046 (5)	0.7021 (3)	0.2751 (2)	0.0540 (7)
H12	−0.0488	0.7866	0.2708	0.065*
C10	0.2361 (4)	1.0519 (3)	0.43622 (19)	0.0424 (6)
C11	−0.0067 (4)	0.6203 (3)	0.3685 (2)	0.0491 (6)
C5	0.3970 (4)	0.8856 (3)	0.33832 (18)	0.0444 (6)
H5	0.4032	0.9518	0.2843	0.053*
C14	0.1743 (5)	0.5306 (3)	0.1967 (2)	0.0579 (7)
H14	0.2330	0.5000	0.1400	0.069*
C15	0.1651 (4)	0.4540 (3)	0.2854 (2)	0.0521 (7)
H15	0.2189	0.3697	0.2902	0.063*
C13	0.0925 (5)	0.6582 (3)	0.1922 (2)	0.0575 (7)
H13	0.0986	0.7129	0.1320	0.069*
C7	0.3000 (5)	0.8162 (3)	0.5076 (2)	0.0555 (7)
H7	0.2422	0.8318	0.5692	0.067*
C8	0.3758 (6)	0.6939 (3)	0.4942 (2)	0.0658 (9)
H8	0.3688	0.6255	0.5466	0.079*
C9	0.4616 (5)	0.6739 (3)	0.4030 (2)	0.0547 (7)
H9	0.5153	0.5915	0.3954	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0696 (5)	0.0335 (4)	0.0282 (4)	0.0075 (3)	−0.0027 (3)	−0.0030 (2)
S2	0.0774 (5)	0.0294 (4)	0.0448 (4)	0.0050 (3)	−0.0058 (3)	−0.0038 (3)
N3	0.0577 (12)	0.0366 (11)	0.0318 (11)	0.0107 (9)	0.0030 (8)	−0.0025 (8)
N4	0.0779 (17)	0.0439 (13)	0.0353 (12)	0.0137 (11)	0.0025 (11)	0.0029 (10)
O4	0.0930 (15)	0.0422 (11)	0.0336 (10)	0.0111 (10)	0.0032 (9)	−0.0007 (8)
N1	0.0773 (16)	0.0404 (12)	0.0358 (12)	0.0141 (11)	0.0048 (10)	0.0026 (9)
O2	0.122 (2)	0.0509 (13)	0.0616 (15)	0.0163 (13)	−0.0293 (14)	−0.0222 (11)
N2	0.0769 (16)	0.0417 (13)	0.0336 (11)	0.0163 (11)	0.0063 (10)	0.0028 (9)
C2	0.0487 (13)	0.0381 (13)	0.0299 (12)	0.0063 (10)	0.0010 (9)	−0.0022 (9)
O3	0.0926 (17)	0.0371 (11)	0.0856 (18)	−0.0042 (11)	0.0049 (13)	0.0099 (11)
C3	0.0578 (15)	0.0377 (13)	0.0368 (13)	0.0057 (11)	−0.0016 (11)	−0.0020 (10)
C1	0.0598 (15)	0.0319 (12)	0.0353 (13)	0.0042 (10)	−0.0018 (10)	−0.0001 (10)
C4	0.099 (2)	0.0414 (17)	0.0458 (16)	0.0157 (16)	0.0004 (15)	0.0013 (12)
O5	0.1071 (17)	0.0416 (11)	0.0384 (11)	0.0224 (11)	−0.0126 (10)	−0.0005 (9)
N7	0.0734 (15)	0.0398 (12)	0.0368 (11)	0.0072 (10)	−0.0077 (10)	−0.0080 (9)
N6	0.0714 (15)	0.0380 (12)	0.0418 (12)	0.0150 (10)	−0.0086 (10)	−0.0091 (9)
O1	0.0994 (16)	0.0466 (12)	0.0427 (11)	0.0234 (11)	−0.0076 (10)	−0.0127 (9)
C6	0.0465 (13)	0.0368 (13)	0.0347 (12)	0.0067 (10)	−0.0020 (9)	−0.0041 (10)
N5	0.0618 (13)	0.0444 (12)	0.0349 (11)	0.0118 (10)	0.0023 (9)	−0.0080 (9)
C12	0.0746 (18)	0.0397 (14)	0.0487 (16)	0.0032 (13)	−0.0145 (13)	−0.0040 (12)
C10	0.0512 (13)	0.0365 (13)	0.0388 (13)	0.0057 (10)	−0.0058 (10)	−0.0036 (10)
C11	0.0672 (16)	0.0400 (14)	0.0430 (15)	0.0075 (12)	−0.0126 (12)	−0.0125 (11)
C5	0.0578 (15)	0.0414 (14)	0.0318 (12)	0.0078 (11)	−0.0024 (10)	−0.0021 (10)
C14	0.0686 (18)	0.0632 (19)	0.0425 (15)	−0.0006 (14)	0.0004 (13)	−0.0159 (13)
C15	0.0656 (17)	0.0440 (15)	0.0483 (15)	0.0063 (12)	−0.0040 (12)	−0.0154 (12)
C13	0.0710 (18)	0.0577 (18)	0.0420 (15)	−0.0062 (14)	−0.0086 (13)	0.0013 (13)
C7	0.085 (2)	0.0436 (15)	0.0316 (13)	0.0167 (13)	0.0092 (12)	−0.0008 (11)
C8	0.105 (3)	0.0426 (17)	0.0405 (16)	0.0237 (16)	0.0094 (15)	0.0050 (12)
C9	0.0780 (19)	0.0385 (14)	0.0438 (15)	0.0180 (13)	0.0020 (13)	−0.0049 (12)

Geometric parameters (Å, º)

S1—C1	1.726 (2)	N7—C15	1.361 (4)
S1—C2	1.730 (2)	N6—C10	1.320 (3)
S2—O2	1.427 (2)	O1—C11	1.253 (3)
S2—O3	1.428 (2)	C6—C7	1.377 (4)
S2—N4	1.578 (3)	C6—C5	1.381 (3)
S2—C1	1.781 (3)	C6—C10	1.499 (3)
N3—C3	1.356 (3)	N5—C9	1.332 (4)
N3—C2	1.379 (3)	N5—C5	1.338 (3)
O4—C3	1.216 (3)	C12—C13	1.361 (4)
N1—C1	1.279 (3)	C12—C11	1.427 (4)
N1—N2	1.379 (3)	C14—C15	1.351 (4)
N2—C2	1.294 (3)	C14—C13	1.409 (5)
C3—C4	1.493 (4)	C7—C8	1.376 (4)
O5—C10	1.233 (3)	C8—C9	1.368 (4)
N7—C11	1.359 (4)
C1—S1—C2	84.93 (12)	C11—N7—C15	124.4 (3)
O2—S2—O3	121.32 (18)	C7—C6—C5	117.9 (2)
O2—S2—N4	108.37 (16)	C7—C6—C10	122.6 (2)
O3—S2—N4	107.68 (15)	C5—C6—C10	119.5 (2)
O2—S2—C1	104.20 (13)	C9—N5—C5	117.2 (2)
O3—S2—C1	106.83 (14)	C13—C12—C11	120.8 (3)
N4—S2—C1	107.75 (14)	O5—C10—N6	121.4 (3)
C3—N3—C2	123.4 (2)	O5—C10—C6	121.0 (2)
C1—N1—N2	111.9 (2)	N6—C10—C6	117.6 (2)
C2—N2—N1	111.6 (2)	O1—C11—N7	119.5 (3)
N2—C2—N3	120.8 (2)	O1—C11—C12	125.1 (3)
N2—C2—S1	115.5 (2)	N7—C11—C12	115.4 (3)
N3—C2—S1	123.76 (18)	N5—C5—C6	123.6 (2)
O4—C3—N3	121.4 (2)	C15—C14—C13	118.2 (3)
O4—C3—C4	123.2 (2)	C14—C15—N7	120.5 (3)
N3—C3—C4	115.3 (2)	C12—C13—C14	120.8 (3)
N1—C1—S1	116.1 (2)	C8—C7—C6	118.8 (3)
N1—C1—S2	122.40 (19)	C9—C8—C7	119.4 (3)
S1—C1—S2	121.40 (15)	N5—C9—C8	122.9 (3)

(ACZOMeHPH111)

Crystal data

C4H6N4O3S2·C6H7NO2·H2O	F(000) = 380
Mr = 365.39	Dx = 1.565 Mg m^−3
Triclinic, P1	Melting point: 363 K
a = 7.7872 (6) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.2130 (7) Å	Cell parameters from 2221 reflections
c = 10.2464 (7) Å	θ = 4.4–71.6°
α = 88.192 (5)°	µ = 3.49 mm^−1
β = 76.587 (6)°	T = 298 K
γ = 77.996 (6)°	PLATE, colorles
V = 775.22 (9) Å^3	0.22 × 0.20 × 0.18 mm
Z = 2

Data collection

Xcalibur, Eos, Gemini diffractometer	2734 independent reflections
Radiation source: fine-focus sealed tube	2406 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 67.1°, θmin = 4.4°
Absorption correction: multi-scan	h = −7→9
Tmin = 0.530, Tmax = 1.000	k = −12→12
4182 measured reflections	l = −12→11

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) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1021P)^2] where P = (Fo^2 + 2Fc^2)/3
2734 reflections	(Δ/σ)max < 0.001
234 parameters	Δρmax = 0.41 e Å^−3
3 restraints	Δρmin = −0.48 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
S2	0.74682 (8)	0.29948 (6)	0.41441 (5)	0.0401 (2)
S1	0.89362 (8)	0.29672 (6)	0.11297 (5)	0.0375 (2)
O3	0.6751 (3)	0.42953 (19)	0.3709 (2)	0.0599 (6)
O5	0.5802 (2)	0.08098 (17)	0.15601 (17)	0.0447 (4)
O4	0.3422 (2)	0.29976 (16)	0.26201 (16)	0.0444 (4)
N4	0.5914 (3)	0.2185 (3)	0.4532 (2)	0.0460 (5)
N3	1.1399 (3)	0.1432 (2)	−0.08603 (19)	0.0364 (4)
N5	0.5962 (3)	0.16290 (19)	−0.0548 (2)	0.0378 (4)
O6	0.3340 (3)	0.0077 (2)	0.3844 (2)	0.0602 (6)
C7	0.3504 (3)	0.3883 (2)	0.0383 (2)	0.0375 (5)
H7	0.2658	0.4658	0.0697	0.045*
O1	0.9721 (3)	0.3295 (2)	−0.1467 (2)	0.0653 (6)
O2	0.8426 (3)	0.2846 (2)	0.51861 (19)	0.0592 (5)
N2	1.1116 (3)	0.0757 (2)	0.1363 (2)	0.0398 (5)
C5	0.4011 (3)	0.2938 (2)	0.1270 (2)	0.0336 (5)
C1	0.8998 (3)	0.2235 (2)	0.2664 (2)	0.0365 (5)
N1	1.0156 (3)	0.1136 (2)	0.2650 (2)	0.0414 (5)
C3	1.0888 (3)	0.2312 (3)	−0.1803 (2)	0.0436 (6)
C2	1.0616 (3)	0.1613 (2)	0.0475 (2)	0.0322 (5)
C8	0.4252 (4)	0.3693 (2)	−0.1000 (3)	0.0437 (6)
H8	0.3893	0.4333	−0.1603	0.052*
C6	0.5303 (3)	0.1729 (2)	0.0796 (2)	0.0338 (5)
C4	1.1868 (5)	0.1965 (4)	−0.3222 (3)	0.0627 (8)
H4A	1.1012	0.1972	−0.3764	0.094*
H4B	1.2627	0.1089	−0.3263	0.094*
H4C	1.2596	0.2609	−0.3553	0.094*
C9	0.5493 (4)	0.2576 (3)	−0.1445 (2)	0.0418 (5)
H9	0.6026	0.2450	−0.2355	0.050*
C13	0.2285 (4)	0.4222 (3)	0.3220 (3)	0.0506 (7)
H13A	0.2920	0.4941	0.3008	0.076*
H13B	0.1960	0.4130	0.4176	0.076*
H13C	0.1213	0.4415	0.2878	0.076*
H4D	0.620 (5)	0.149 (4)	0.489 (4)	0.057 (9)*
H4E	0.529 (5)	0.211 (4)	0.390 (4)	0.078 (11)*
H5A	0.683 (4)	0.087 (3)	−0.081 (3)	0.048 (8)*
H3A	1.217 (4)	0.076 (3)	−0.109 (3)	0.042 (7)*
H6B	0.220 (3)	0.043 (4)	0.379 (4)	0.080 (12)*
H6A	0.405 (4)	0.045 (3)	0.314 (3)	0.060 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0419 (4)	0.0430 (4)	0.0311 (3)	−0.0038 (3)	−0.0039 (2)	−0.0028 (2)
S1	0.0348 (4)	0.0377 (3)	0.0338 (3)	0.0016 (2)	−0.0040 (2)	0.0020 (2)
O3	0.0725 (14)	0.0416 (10)	0.0502 (11)	0.0010 (9)	0.0055 (10)	0.0007 (8)
O5	0.0497 (10)	0.0350 (9)	0.0407 (9)	0.0050 (7)	−0.0057 (8)	0.0038 (7)
O4	0.0552 (11)	0.0357 (9)	0.0347 (9)	0.0039 (8)	−0.0071 (8)	−0.0008 (7)
N4	0.0402 (12)	0.0567 (14)	0.0375 (11)	−0.0061 (10)	−0.0063 (9)	0.0079 (10)
N3	0.0340 (11)	0.0374 (10)	0.0326 (10)	−0.0006 (9)	−0.0031 (8)	−0.0007 (8)
N5	0.0427 (11)	0.0302 (10)	0.0378 (10)	−0.0029 (8)	−0.0076 (8)	−0.0028 (8)
O6	0.0564 (13)	0.0674 (13)	0.0529 (11)	−0.0058 (10)	−0.0136 (10)	0.0228 (10)
C7	0.0392 (13)	0.0285 (11)	0.0445 (12)	−0.0046 (9)	−0.0115 (10)	0.0018 (9)
O1	0.0630 (13)	0.0660 (13)	0.0457 (10)	0.0249 (11)	−0.0053 (9)	0.0097 (9)
O2	0.0592 (12)	0.0803 (14)	0.0407 (10)	−0.0134 (10)	−0.0160 (9)	−0.0114 (9)
N2	0.0410 (11)	0.0374 (10)	0.0356 (10)	−0.0006 (8)	−0.0047 (8)	0.0018 (8)
C5	0.0352 (12)	0.0299 (11)	0.0367 (11)	−0.0079 (9)	−0.0086 (9)	−0.0022 (9)
C1	0.0333 (12)	0.0406 (12)	0.0342 (11)	−0.0062 (9)	−0.0064 (9)	0.0007 (9)
N1	0.0395 (11)	0.0433 (11)	0.0359 (10)	−0.0025 (9)	−0.0033 (8)	0.0020 (8)
C3	0.0379 (13)	0.0531 (15)	0.0359 (12)	−0.0022 (11)	−0.0075 (10)	0.0041 (10)
C2	0.0293 (11)	0.0314 (11)	0.0355 (11)	−0.0068 (8)	−0.0063 (9)	0.0008 (9)
C8	0.0546 (16)	0.0366 (13)	0.0418 (13)	−0.0086 (11)	−0.0163 (11)	0.0090 (10)
C6	0.0353 (12)	0.0309 (11)	0.0364 (11)	−0.0083 (9)	−0.0094 (9)	0.0014 (9)
C4	0.0592 (18)	0.081 (2)	0.0347 (14)	0.0094 (15)	−0.0069 (12)	0.0058 (13)
C9	0.0492 (15)	0.0418 (13)	0.0344 (11)	−0.0111 (10)	−0.0081 (10)	0.0007 (10)
C13	0.0557 (17)	0.0435 (14)	0.0423 (13)	0.0030 (12)	−0.0019 (12)	−0.0061 (11)

Geometric parameters (Å, º)

S2—O2	1.4252 (19)	C7—C5	1.366 (3)
S2—O3	1.430 (2)	C7—C8	1.404 (3)
S2—N4	1.575 (2)	C7—H7	0.9300
S2—C1	1.781 (2)	O1—C3	1.204 (3)
S1—C2	1.724 (2)	N2—C2	1.310 (3)
S1—C1	1.726 (2)	N2—N1	1.380 (3)
O5—C6	1.260 (3)	C5—C6	1.438 (3)
O4—C5	1.352 (3)	C1—N1	1.284 (3)
O4—C13	1.436 (3)	C3—C4	1.493 (4)
N4—H4D	0.80 (4)	C8—C9	1.347 (4)
N4—H4E	0.91 (4)	C8—H8	0.9300
N3—C2	1.363 (3)	C4—H4A	0.9600
N3—C3	1.369 (3)	C4—H4B	0.9600
N3—H3A	0.81 (3)	C4—H4C	0.9600
N5—C6	1.352 (3)	C9—H9	0.9300
N5—C9	1.366 (3)	C13—H13A	0.9600
N5—H5A	0.92 (3)	C13—H13B	0.9600
O6—H6B	0.902 (18)	C13—H13C	0.9600
O6—H6A	0.923 (18)
O2—S2—O3	120.66 (13)	C1—N1—N2	111.50 (19)
O2—S2—N4	108.27 (13)	O1—C3—N3	120.2 (2)
O3—S2—N4	109.07 (14)	O1—C3—C4	124.0 (2)
O2—S2—C1	107.37 (12)	N3—C3—C4	115.7 (2)
O3—S2—C1	103.16 (11)	N2—C2—N3	121.5 (2)
N4—S2—C1	107.58 (12)	N2—C2—S1	114.94 (17)
C2—S1—C1	85.36 (11)	N3—C2—S1	123.57 (17)
C5—O4—C13	117.92 (18)	C9—C8—C7	119.4 (2)
S2—N4—H4D	114 (2)	C9—C8—H8	120.3
S2—N4—H4E	117 (2)	C7—C8—H8	120.3
H4D—N4—H4E	112 (3)	O5—C6—N5	121.3 (2)
C2—N3—C3	122.3 (2)	O5—C6—C5	123.3 (2)
C2—N3—H3A	118 (2)	N5—C6—C5	115.4 (2)
C3—N3—H3A	120 (2)	C3—C4—H4A	109.5
C6—N5—C9	125.0 (2)	C3—C4—H4B	109.5
C6—N5—H5A	113.3 (19)	H4A—C4—H4B	109.5
C9—N5—H5A	121.7 (19)	C3—C4—H4C	109.5
H6B—O6—H6A	105 (3)	H4A—C4—H4C	109.5
C5—C7—C8	120.5 (2)	H4B—C4—H4C	109.5
C5—C7—H7	119.8	C8—C9—N5	119.5 (2)
C8—C7—H7	119.8	C8—C9—H9	120.3
C2—N2—N1	111.88 (19)	N5—C9—H9	120.3
O4—C5—C7	126.7 (2)	O4—C13—H13A	109.5
O4—C5—C6	112.98 (19)	O4—C13—H13B	109.5
C7—C5—C6	120.3 (2)	H13A—C13—H13B	109.5
N1—C1—S1	116.32 (18)	O4—C13—H13C	109.5
N1—C1—S2	123.92 (18)	H13A—C13—H13C	109.5
S1—C1—S2	119.75 (14)	H13B—C13—H13C	109.5

(ACZVLM12)

Crystal data

C4H6N4O3S2·2(C5H9NO)	Dx = 1.418 Mg m^−3
Mr = 420.51	Melting point: 366 K
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 9.66166 (19) Å	Cell parameters from 3314 reflections
b = 23.4685 (4) Å	θ = 4.7–71.6°
c = 8.84352 (17) Å	µ = 2.80 mm^−1
β = 100.7730 (19)°	T = 298 K
V = 1969.88 (7) Å^3	Needle, colorles
Z = 4	0.22 × 0.20 × 0.20 mm
F(000) = 888

Data collection

Xcalibur, Eos, Gemini diffractometer	3507 independent reflections
Radiation source: fine-focus sealed tube	3068 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 67.1°, θmin = 3.8°
Absorption correction: multi-scan	h = −10→11
Tmin = 0.702, Tmax = 1.000	k = −28→24
6492 measured reflections	l = −10→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0736P)^2 + 0.4712P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3507 reflections	Δρmax = 0.37 e Å^−3
266 parameters	Δρmin = −0.40 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0017 (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
S1	0.05603 (6)	0.70069 (2)	0.86906 (7)	0.04789 (19)
S2	0.10589 (6)	0.57207 (2)	0.85192 (7)	0.04876 (19)
N1	0.1709 (2)	0.80103 (8)	0.7959 (2)	0.0458 (4)
O5	0.47643 (18)	0.51554 (7)	0.8041 (2)	0.0573 (4)
O1	−0.00847 (19)	0.80761 (8)	0.9245 (2)	0.0648 (5)
C3	0.0787 (2)	0.83161 (10)	0.8649 (3)	0.0477 (5)
N6	0.4989 (2)	0.59455 (9)	0.6701 (3)	0.0540 (5)
O2	0.00146 (19)	0.57761 (8)	0.9450 (3)	0.0687 (5)
N4	0.2449 (2)	0.54589 (8)	0.9520 (3)	0.0490 (5)
N2	0.2659 (2)	0.71498 (8)	0.7328 (3)	0.0545 (5)
C2	0.1729 (2)	0.74257 (9)	0.7927 (2)	0.0422 (5)
N3	0.2489 (2)	0.65681 (8)	0.7445 (3)	0.0547 (5)
C10	0.5413 (2)	0.54307 (9)	0.7199 (3)	0.0437 (5)
O3	0.0768 (2)	0.54194 (8)	0.7106 (2)	0.0722 (5)
C12	0.7225 (3)	0.55117 (12)	0.5462 (3)	0.0606 (6)
H12A	0.8188	0.5403	0.5430	0.073*
H12B	0.6642	0.5417	0.4478	0.073*
C4	0.0960 (3)	0.89508 (11)	0.8610 (3)	0.0607 (6)
H4A	0.0285	0.9129	0.9127	0.091*
H4B	0.0812	0.9078	0.7560	0.091*
H4C	0.1895	0.9052	0.9118	0.091*
C1	0.1459 (2)	0.64398 (9)	0.8114 (3)	0.0449 (5)
C11	0.6716 (3)	0.51911 (10)	0.6736 (3)	0.0543 (6)
H11A	0.6529	0.4799	0.6410	0.065*
H11B	0.7466	0.5186	0.7634	0.065*
C13	0.7154 (3)	0.61411 (12)	0.5745 (4)	0.0677 (7)
H13A	0.7516	0.6348	0.4952	0.081*
H13B	0.7733	0.6235	0.6732	0.081*
C14	0.5652 (3)	0.63159 (11)	0.5733 (4)	0.0691 (8)
H14A	0.5634	0.6705	0.6097	0.083*
H14B	0.5124	0.6302	0.4687	0.083*
O4	0.36338 (16)	0.63381 (7)	0.1712 (2)	0.0548 (4)
N5	0.5710 (2)	0.60207 (8)	0.1312 (2)	0.0488 (5)
C9	0.4827 (2)	0.64362 (9)	0.1412 (3)	0.0439 (5)
C5	0.7137 (3)	0.60708 (11)	0.1001 (4)	0.0620 (7)
H5A	0.7244	0.5811	0.0178	0.074*
H5B	0.7806	0.5960	0.1913	0.074*
C8	0.5261 (3)	0.70361 (10)	0.1132 (4)	0.0650 (7)
H8A	0.4698	0.7170	0.0174	0.078*
H8B	0.5053	0.7277	0.1952	0.078*
C7	0.6773 (4)	0.71018 (14)	0.1049 (9)	0.152 (3)
H7A	0.6853	0.7421	0.0375	0.182*
H7B	0.7272	0.7206	0.2067	0.182*
C6	0.7463 (4)	0.66532 (14)	0.0560 (6)	0.0999 (13)
H6A	0.8463	0.6714	0.0919	0.120*
H6B	0.7298	0.6668	−0.0556	0.120*
H5C	0.541 (3)	0.5676 (11)	0.145 (3)	0.050 (7)*
H4E	0.274 (3)	0.5665 (12)	1.040 (3)	0.075 (9)*
H4D	0.303 (3)	0.5368 (11)	0.902 (3)	0.052 (7)*
H1A	0.232 (3)	0.8176 (12)	0.753 (3)	0.055 (7)*
H6C	0.427 (3)	0.6059 (13)	0.700 (3)	0.061 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0429 (3)	0.0456 (3)	0.0613 (4)	−0.0024 (2)	0.0257 (3)	0.0037 (2)
S2	0.0439 (3)	0.0428 (3)	0.0609 (4)	−0.0060 (2)	0.0131 (2)	0.0042 (2)
N1	0.0430 (10)	0.0423 (10)	0.0571 (11)	−0.0013 (8)	0.0218 (9)	0.0047 (8)
O5	0.0625 (10)	0.0437 (8)	0.0732 (11)	−0.0004 (7)	0.0320 (9)	0.0080 (8)
O1	0.0583 (10)	0.0609 (11)	0.0858 (13)	−0.0025 (8)	0.0405 (10)	−0.0046 (9)
C3	0.0439 (11)	0.0491 (12)	0.0526 (12)	−0.0007 (10)	0.0156 (10)	−0.0021 (10)
N6	0.0535 (11)	0.0445 (11)	0.0701 (13)	0.0081 (9)	0.0271 (10)	0.0085 (9)
O2	0.0521 (9)	0.0591 (10)	0.1037 (15)	−0.0033 (8)	0.0370 (10)	0.0153 (10)
N4	0.0519 (11)	0.0432 (10)	0.0545 (12)	0.0000 (8)	0.0164 (10)	0.0044 (9)
N2	0.0507 (11)	0.0444 (10)	0.0761 (14)	0.0022 (8)	0.0319 (10)	0.0094 (10)
C2	0.0362 (10)	0.0463 (11)	0.0473 (11)	−0.0004 (9)	0.0159 (8)	0.0067 (9)
N3	0.0521 (11)	0.0446 (10)	0.0748 (13)	0.0036 (8)	0.0308 (10)	0.0066 (9)
C10	0.0449 (11)	0.0395 (11)	0.0485 (12)	−0.0021 (9)	0.0133 (9)	−0.0017 (9)
O3	0.0820 (13)	0.0607 (11)	0.0677 (12)	−0.0143 (10)	−0.0017 (10)	−0.0040 (9)
C12	0.0527 (13)	0.0741 (17)	0.0592 (15)	0.0016 (12)	0.0212 (12)	−0.0026 (13)
C4	0.0641 (15)	0.0484 (13)	0.0748 (17)	−0.0006 (11)	0.0266 (13)	−0.0063 (12)
C1	0.0399 (10)	0.0424 (11)	0.0543 (12)	0.0013 (9)	0.0142 (9)	0.0053 (9)
C11	0.0525 (13)	0.0471 (12)	0.0668 (15)	0.0077 (10)	0.0203 (11)	0.0010 (11)
C13	0.0672 (16)	0.0663 (17)	0.0769 (18)	−0.0137 (13)	0.0324 (14)	0.0068 (14)
C14	0.0805 (18)	0.0532 (14)	0.0818 (19)	0.0091 (13)	0.0360 (15)	0.0218 (13)
O4	0.0429 (8)	0.0503 (9)	0.0762 (11)	−0.0031 (7)	0.0242 (8)	−0.0110 (8)
N5	0.0435 (10)	0.0383 (10)	0.0685 (13)	0.0012 (8)	0.0208 (9)	0.0014 (9)
C9	0.0420 (10)	0.0425 (11)	0.0495 (12)	0.0002 (9)	0.0145 (9)	−0.0046 (9)
C5	0.0473 (13)	0.0534 (14)	0.093 (2)	0.0055 (11)	0.0319 (13)	0.0005 (13)
C8	0.0570 (15)	0.0399 (12)	0.103 (2)	0.0026 (10)	0.0289 (15)	0.0015 (13)
C7	0.095 (3)	0.0478 (17)	0.345 (9)	0.0019 (18)	0.125 (4)	0.022 (3)
C6	0.074 (2)	0.0688 (19)	0.178 (4)	−0.0040 (16)	0.078 (2)	0.010 (2)

Geometric parameters (Å, º)

S1—C1	1.718 (2)	C4—H4B	0.9600
S1—C2	1.727 (2)	C4—H4C	0.9600
S2—O3	1.418 (2)	C11—H11A	0.9700
S2—O2	1.4223 (19)	C11—H11B	0.9700
S2—N4	1.587 (2)	C13—C14	1.506 (4)
S2—C1	1.782 (2)	C13—H13A	0.9700
N1—C2	1.373 (3)	C13—H13B	0.9700
N1—C3	1.373 (3)	C14—H14A	0.9700
N1—H1A	0.85 (3)	C14—H14B	0.9700
O5—C10	1.240 (3)	O4—C9	1.251 (3)
O1—C3	1.212 (3)	N5—C9	1.309 (3)
C3—C4	1.500 (3)	N5—C5	1.460 (3)
N6—C10	1.324 (3)	N5—H5C	0.87 (3)
N6—C14	1.451 (3)	C9—C8	1.503 (3)
N6—H6C	0.83 (3)	C5—C6	1.471 (4)
N4—H4E	0.913 (18)	C5—H5A	0.9700
N4—H4D	0.81 (3)	C5—H5B	0.9700
N2—C2	1.297 (3)	C8—C7	1.484 (4)
N2—N3	1.381 (3)	C8—H8A	0.9700
N3—C1	1.285 (3)	C8—H8B	0.9700
C10—C11	1.503 (3)	C7—C6	1.359 (5)
C12—C13	1.502 (4)	C7—H7A	0.9700
C12—C11	1.512 (4)	C7—H7B	0.9700
C12—H12A	0.9700	C6—H6A	0.9700
C12—H12B	0.9700	C6—H6B	0.9700
C4—H4A	0.9600
C1—S1—C2	85.48 (10)	C10—C11—H11B	108.5
O3—S2—O2	120.72 (13)	C12—C11—H11B	108.5
O3—S2—N4	107.82 (13)	H11A—C11—H11B	107.5
O2—S2—N4	109.29 (13)	C12—C13—C14	109.9 (2)
O3—S2—C1	108.04 (11)	C12—C13—H13A	109.7
O2—S2—C1	103.50 (10)	C14—C13—H13A	109.7
N4—S2—C1	106.61 (10)	C12—C13—H13B	109.7
C2—N1—C3	123.02 (19)	C14—C13—H13B	109.7
C2—N1—H1A	115.7 (19)	H13A—C13—H13B	108.2
C3—N1—H1A	121.3 (19)	N6—C14—C13	111.3 (2)
O1—C3—N1	120.8 (2)	N6—C14—H14A	109.4
O1—C3—C4	124.1 (2)	C13—C14—H14A	109.4
N1—C3—C4	115.1 (2)	N6—C14—H14B	109.4
C10—N6—C14	126.8 (2)	C13—C14—H14B	109.4
C10—N6—H6C	114 (2)	H14A—C14—H14B	108.0
C14—N6—H6C	119 (2)	C9—N5—C5	127.1 (2)
S2—N4—H4E	111.5 (19)	C9—N5—H5C	116.5 (17)
S2—N4—H4D	113.4 (19)	C5—N5—H5C	116.4 (17)
H4E—N4—H4D	118 (3)	O4—C9—N5	121.0 (2)
C2—N2—N3	111.20 (18)	O4—C9—C8	120.3 (2)
N2—C2—N1	121.41 (19)	N5—C9—C8	118.7 (2)
N2—C2—S1	115.38 (17)	N5—C5—C6	112.4 (2)
N1—C2—S1	123.20 (16)	N5—C5—H5A	109.1
C1—N3—N2	112.29 (18)	C6—C5—H5A	109.1
O5—C10—N6	121.0 (2)	N5—C5—H5B	109.1
O5—C10—C11	120.7 (2)	C6—C5—H5B	109.1
N6—C10—C11	118.3 (2)	H5A—C5—H5B	107.9
C13—C12—C11	109.5 (2)	C7—C8—C9	114.4 (2)
C13—C12—H12A	109.8	C7—C8—H8A	108.7
C11—C12—H12A	109.8	C9—C8—H8A	108.7
C13—C12—H12B	109.8	C7—C8—H8B	108.7
C11—C12—H12B	109.8	C9—C8—H8B	108.7
H12A—C12—H12B	108.2	H8A—C8—H8B	107.6
C3—C4—H4A	109.5	C6—C7—C8	118.7 (3)
C3—C4—H4B	109.5	C6—C7—H7A	107.6
H4A—C4—H4B	109.5	C8—C7—H7A	107.6
C3—C4—H4C	109.5	C6—C7—H7B	107.6
H4A—C4—H4C	109.5	C8—C7—H7B	107.6
H4B—C4—H4C	109.5	H7A—C7—H7B	107.1
N3—C1—S1	115.65 (17)	C7—C6—C5	119.5 (3)
N3—C1—S2	122.00 (17)	C7—C6—H6A	107.4
S1—C1—S2	122.25 (12)	C5—C6—H6A	107.4
C10—C11—C12	115.0 (2)	C7—C6—H6B	107.4
C10—C11—H11A	108.5	C5—C6—H6B	107.4
C12—C11—H11A	108.5	H6A—C6—H6B	107.0