N-Cyclo­hexyl-2-[5-(4-pyridyl)-4-(p-tolyl)-4H-1,2,4-triazol-3-yl­sulfanyl]­acetamide dihydrate

In the title compound, C₂₂H₂₅N₅OS·2H₂O, the mol­ecules are stacked in columns running along the b axis. In this arrangemant, the mol­ecules are linked to each other by a combination of one two-centre N-H...O hydrogen bond and four two-centre O-H...O hydrogen bonds containing two types of ring motif, viz. R₄⁴(10) and R₃³(11). In the crystal structure, centrosymmetric [pi]-[pi] inter­actions between the triazole rings, with a distance of 3.691 (2) Å between the ring centroids, also affect the packing of the mol­ecules.

S1. Comment

1,2,4-Triazole and its derivatives represent one of the most biologically active classes of compounds, possessing a wide spectrum of activities including antibacterial, antifungal, antiviral, anti-inflammatory, anticonvulsant, antidepressant, antihypertensive, analgesic and hypoglycaemic properties (Abbas & Khalil, 2005; Holla et al., 1998; Hovsepian et al., 2004). In addition to these important biological applications, mercapto-1,2,4-triazoles are also of great utility in preparative organic chemistry, and triazolothiadiazines, for example, in the presence of various reagents, undergo different types of reaction to yield other heterocyclic compounds, e.g. thiazolotriazoles, triazolothiadizoles and triazolothiazepines. The amino and mercapto groups of these compounds serve as readily accessible nucleophilic centres for the preparation of N-bridged heterocycles (Shaker, 2006). Furthermore, there have been some studies of the electronic structures and thiol–thione tautomeric equilibrium of heterocyclic thione derivatives (Koparır, Çetin & Cansız, 2005; Coyanis et al., 2002). Substituted 1,2,4-triazoles have been actively studied as bridging ligands coordinating through their vicinal N atoms (Mills et al., 2002; Li et al., 2003, 2006; Zaleski et al., 2005). It is of interest that some complexes containing 1,2,4-triazole ligands have particular structures and specific magnetic properties (Vreugdenhil et al., 1987; van Albada et al., 1984; Vos et al., 1983; Kahn & Martinez, 1998). Taking into account these important properties, the present single-crystal X-ray diffraction study of the title compound, (III), was carried out and the results are presented here.

In the present study, the reaction of 4-(p-tolyl)-5-pyridin-4-yl-4H-1,2,4-triazole-3-thiol, (I), with 2-chloro-N-cyclohexylacetamide, (II), in a basic medium gave the corresponding N-cyclohexyl-2-[5-(pyridin-4-yl)-4-p-tolyl-4H-1,2,4-triazol-3-ylthio] acetamide dihydrate, (III), in close to quantitative yield (65%) (Hovsepian et al., 2004). The reaction sequences depicted in the scheme were followed to obtain the new compound. The structure of this compound has been confirmed by IR and ¹H NMR spectroscopies.

A view of the hydrogen-bonded structure of (III) and its atom-numbering scheme are shown in Fig. 1. Selected geometric parameters are listed in Table 1. The asymmetric unit of (III) is made up of just one organic moiety and two water molecules. The organic component is composed of a central 1,2,4-triazole ring, with an N-cyclohexyl-2-mercaptoacetamide group connected to the 3-position of the ring, a toluene group in the 4-position and a pyridine ring in the 5-position. As expected, the 1,2,4-triazole and pyridine rings are planar, as are all similar fragments reported in the Cambridge Structural Database (CSD, Version?; CONQUEST, Version 3.6; Allen, 2002), which can be attributed to a wide range of electron delocalization [maximum deviations of 0.0015 (11) and −0.0067 (17) Å for atoms N4 and N5, respectively]. The cyclohexane ring adopts a chair conformation, as is evident from the puckering parameters for the atom sequence C33–C38 [Q = 0.578 (3) Å, θ = 180 (3)° and ϕ = 360 (3)°; Cremer & Pople, 1975]. Atoms C33 and C36 are on opposite sides of the C34/C35/C37/C38 plane and displaced from it by −0.234 (2) and 0.243 (2) Å, respectively. The phenyl ring is essentially planar and twisted out of the plane of the triazole ring. The dihedral angle between these planes is 74.12 (7)°. The dihedral angle between the triazole and pyridine rings is 28.55 (10)°. A non-planar disposition of the three rings has been observed in similar 1,2,4-triazole derivatives (Zhu et al., 2000; Bruno et al., 2003; Yılmaz et al., 2005). The mercaptoacetamide bridge linking the triazole ring with the cyclohexane ring is not planar, and the Φ_CC torsion angle (S3—C31—C32—N3) is 164.05 (15)°, which shows that the conformation about the C31—C32 bond is (+)-antiperiplanar.

The interatomic distances within the triazole ring are not equal, ranging from 1.308 (2) to 1.388 (2) Å. The C—N bonds in the ring are classified into localized single (e.g. N4—C3 and N4—C5) and double bonds (e.g. N1═C5 and N2═C3). The N4—C5 single bond is associated with a larger endo angle, N4—C5—C51, whereas the N1═C5 double bond has a smaller exo angle, N1═C5—C51. The difference between the S3—C3 and S3—C31 bond distances [1.7319 (18) and 1.7880 (19) Å, respectively] can be attributed to the different hybridization of the Csp² and Csp³ atoms. The N1═C5 and N2═C3 bond distances are in a good agreement with those found for structures containing the 1,2,4-triazole ring (Wang et al., 1998; Özbey et al., 1999; Zhu et al., 2000; Bruno et al., 2003; Dinçer et al., 2005). The N—N bond length is 1.388 (2) Å, which is smaller than a pure single bond (1.41 Å; Burke-Laing & Laing, 1976). The fact that the C3—N4 and C5—N4 bond distances are shorter than the C41—N4 bond distance can be considered as possible evidence of conjugation over the whole of the triazole moiety. Furthermore, the C—N bond distances in the mercaptoacetamide linkage are quite different. The C32—N3 bond length [1.314 (2) Å] is significantly shorter than the C33—N3 bond [1.460 (2) Å], which is indicative of some multiple-bond character. The sum of the angles around atom N3 is 360°, indicating sp² hybridization. Scrutiny of the amide link shows that the delocalization of electron density in the planar H—N—C═O unit is due to n(N3) → π^*(C32═O3) donation. The remaining bond lengths in (III) show no unusual values.

In the crystal structure of (III), the molecules are packed in columns running along the b axis, and linked to each other by a combination of one two-centre N—H···O hydrogen bond and four two-centre O—H···O hydrogen bonds, in which the solvent water molecules lead to a number of intermolecular hydrogen bonds (Table 2). Taking these entities alone first, the water (O2W) molecule at (x, y, z) participates in O2W—H21W···N1 and O2W—H22W···N2ⁱ hydrogen bonds [symmetry code: (i) −x + 1, −y, −z + 1], forming a centrosymmetric R⁴₄(10) ring (Bernstein et al., 1995). Another ring forms from a combination of hydrogen bonds [N3—H3···O1W, O1W—H11W···O2Wⁱ and O2W—H22W···N2ⁱ]. Together, these form an R³₃(11) ring (Fig. 2).

In addition to these hydrogen bonds occurring between molecules in inversion-related columns, there are also O—H···O hydrogen bonds between the molecules in each column. In this interaction, the water molecule (O1W) at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O3 at (x, y − 1, z). This hydrogen bond, together with N3—H3···O1W, links the molecules in each column in a zigzag arrangement.

Water is potentially capable of participating in four hydrogen bonds but frequently shows a three-coordinate configuration (Jeffrey & Maluszynska, 1990). This is illustrated in the case of (III), where atoms O1W and O2W donate two hydrogen bonds but accept one. A centrosymmetric π–π stacking interaction also plays a role in the crystal packing, which takes the form of stacks of triazole rings. The triazole rings of the molecules at (x, y, z) and (−x + 1, −y + 1, −z + 1) are strictly parallel, with an interplanar spacing of 3.343 (2) Å. The ring-centroid separation is 3.691 (2) Å, corresponding to a near-ideal ring offset of 1.564 (2) Å (Fig. 3).

S2. Experimental

Compounds (I) and (II) were prepared according to our previously reported method (Çetin, 2004; Koparır, Cansız & Çetin, 2005). Triazole (I) (2 mmol, 0.536 g) was dissolved in a solution of KOH (2 mmol, 0.112 g) in methanol (15 ml) at 313 K. 2-Chloro-N-cyclohexylacetamide, (II) (0.002 mmol, 0.365 g), was added to the solution obtained and the mixture was refluxed for 2 h. After cooling, the precipitated product, (III), was filtered off and recrystallized from ethanol (yield 65%; m.p. 450–451 K). Spectroscopic anlaysis: IR (ν, cm⁻¹): 3446–3340 (s, N—H, O—H), 3160–3020 (b, Ar C—H), 2980–2930 (b, Alk C—H), 1680 (s, C═O), 1618 (m, C═N); ¹H NMR (400 MHz, DMSO-d₆, δ, p.p.m.): 1.25–1.89 (m, 10H, cyclohexyl CH₂), 2.47 (s, 3H, CH₃), 3.71–3.73 (m, 1H, cyclohexyl N—CH), 7.11–7.61 (m, 7H, Ar CH, NH), 7.78–7.80 (d, 2H, J = 6.23 Hz, pyridine N—CH).

S3. Refinement

The coordinates of the H atoms of the water molecules were determined from a difference map and were then allowed to refine isotropically, while the coordinates of atom H12W were refined isotropically subject to a DFIX restraint Of what?. All other H atoms were positioned geometrically and refined with a riding model, fixing the bond lengths at 0.98, 0.97, 0.96, 0.93 and 0.86 Å for CH, CH₂, CH₃, aromatic CH and NH groups, respectively. The displacement parameters of the H atoms were constrained to U_iso(H) = 1.2U_eq(parent), or 1.5U_eq(C) for methyl H atoms. Riding methyl H atoms were allowed to rotate freely during refinement using the AFIX 137 command of SHELXL97 (Sheldrick, 1997). Examination of the refined structure using PLATON (Spek, 2003) revealed the presence of void spaces having a total volume of 20.9 ų (0.9%) per unit cell.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecule of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as broken lines.
	Fig. 2. Part of the crystal structure of (III), showing the formation of R^44(10) and R^33(11) rings. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. For the sake of clarity, H atoms not involved in the motif shown have been omitted. [Symmetry code: (i) −x + 1, −y, −z + 1.]
	Fig. 3. A packing diagram for compound (III), showing the N—H···O, O—H···O, O—H···N and π–π interactions (dashed lines). For clarity, only H atoms involved in hydrogen bonding have been included.

N-Cyclohexyl-2-[5-(4-pyridyl)-4-(p-tolyl)-4H-1,2,4-triazol-3- ylsulfanyl]acetamide dihydrate

Crystal data

C22H25N5OS·2H2O	F(000) = 944
Mr = 443.56	Dx = 1.248 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 26172 reflections
a = 12.3634 (10) Å	θ = 1.5–25.0°
b = 6.8031 (4) Å	µ = 0.17 mm^−1
c = 28.077 (2) Å	T = 296 K
β = 90.306 (7)°	Prism, colourless
V = 2361.5 (3) Å^3	0.68 × 0.43 × 0.15 mm
Z = 4

Data collection

Stoe IPDS II diffractometer	4135 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2947 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.048
Detector resolution: 6.67 pixels mm^-1	θmax = 25.0°, θmin = 1.5°
ω scans	h = −14→14
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −7→8
Tmin = 0.921, Tmax = 0.979	l = −33→33
26676 measured reflections

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0634P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4135 reflections	Δρmax = 0.17 e Å^−3
298 parameters	Δρmin = −0.17 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0066 (10)

Special details

Experimental. Melting points were determined in open capillary tubes on a digital Gallenkamp melting-point apparatus and are uncorrected. The IR spectra were recorded for KBr disks with a Mattson 1000 F T–IR spectrometer. ¹H NMR spectra were recorded on a Varian Mercury Plus 400 MHz ¹H NMR spectrometer in DMSO-d₆ with TMS as an internal standard. Starting materials were obtained from Fluka or Aldrich.

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	0.23210 (5)	0.54135 (9)	0.550646 (18)	0.0722 (2)
O1W	0.3081 (2)	−0.0792 (3)	0.64499 (8)	0.0966 (6)
H11W	0.343 (3)	−0.064 (5)	0.6184 (12)	0.119 (11)*
H12W	0.260 (3)	−0.165 (6)	0.6411 (17)	0.20 (2)*
O2W	0.56974 (18)	0.0079 (3)	0.43530 (7)	0.1030 (7)
H21W	0.533 (3)	0.095 (6)	0.4479 (12)	0.143 (13)*
H22W	0.571 (2)	−0.095 (5)	0.4527 (10)	0.106 (9)*
O3	0.16757 (14)	0.5786 (2)	0.64496 (5)	0.0826 (5)
N1	0.43480 (13)	0.3257 (2)	0.45999 (5)	0.0593 (4)
N2	0.38925 (13)	0.3274 (2)	0.50506 (5)	0.0598 (4)
N3	0.21820 (13)	0.2839 (2)	0.67360 (5)	0.0598 (4)
H3	0.2510	0.1756	0.6672	0.072*
N4	0.31391 (11)	0.5604 (2)	0.46182 (5)	0.0503 (4)
N5	0.48340 (16)	0.5811 (3)	0.29153 (7)	0.0850 (6)
C3	0.31735 (15)	0.4685 (3)	0.50519 (6)	0.0536 (4)
C5	0.38915 (14)	0.4644 (3)	0.43469 (6)	0.0500 (4)
C31	0.27660 (16)	0.3733 (3)	0.59562 (6)	0.0622 (5)
H31A	0.2619	0.2391	0.5858	0.075*
H31B	0.3538	0.3871	0.6010	0.075*
C32	0.21543 (15)	0.4212 (3)	0.64068 (7)	0.0578 (5)
C33	0.16869 (16)	0.3053 (3)	0.72039 (6)	0.0582 (5)
H33	0.0953	0.3567	0.7158	0.070*
C34	0.1600 (2)	0.1054 (4)	0.74345 (8)	0.0859 (7)
H34A	0.2315	0.0485	0.7468	0.103*
H34B	0.1172	0.0192	0.7233	0.103*
C35	0.1071 (3)	0.1219 (4)	0.79251 (9)	0.1012 (9)
H35A	0.0332	0.1677	0.7889	0.121*
H35B	0.1053	−0.0065	0.8075	0.121*
C36	0.1691 (2)	0.2624 (5)	0.82340 (9)	0.1010 (9)
H36A	0.2413	0.2112	0.8290	0.121*
H36B	0.1335	0.2741	0.8540	0.121*
C37	0.1770 (3)	0.4637 (5)	0.80047 (9)	0.0998 (9)
H37A	0.2196	0.5502	0.8206	0.120*
H37B	0.1052	0.5198	0.7971	0.120*
C38	0.2299 (2)	0.4475 (4)	0.75134 (8)	0.0863 (7)
H38A	0.2309	0.5757	0.7363	0.104*
H38B	0.3040	0.4032	0.7550	0.104*
C41	0.23171 (14)	0.7009 (3)	0.44848 (6)	0.0488 (4)
C42	0.23571 (17)	0.8886 (3)	0.46582 (8)	0.0664 (5)
H42	0.2946	0.9311	0.4838	0.080*
C43	0.1500 (2)	1.0144 (3)	0.45603 (9)	0.0781 (6)
H43	0.1521	1.1421	0.4678	0.094*
C44	0.06237 (17)	0.9557 (4)	0.42949 (8)	0.0755 (7)
C45	0.06281 (18)	0.7683 (4)	0.41153 (9)	0.0842 (7)
H45	0.0056	0.7274	0.3923	0.101*
C46	0.14583 (17)	0.6392 (3)	0.42120 (8)	0.0692 (5)
H46	0.1437	0.5116	0.4094	0.083*
C47	−0.0318 (2)	1.0943 (5)	0.42092 (12)	0.1224 (12)
H47A	−0.0267	1.2036	0.4425	0.184*
H47B	−0.0985	1.0257	0.4262	0.184*
H47C	−0.0298	1.1413	0.3887	0.184*
C51	0.41822 (14)	0.5090 (3)	0.38515 (6)	0.0523 (4)
C52	0.41153 (17)	0.6946 (3)	0.36565 (8)	0.0697 (6)
H52	0.3849	0.7992	0.3834	0.084*
C53	0.4450 (2)	0.7223 (4)	0.31934 (9)	0.0837 (7)
H53	0.4404	0.8485	0.3068	0.100*
C54	0.49046 (18)	0.4045 (4)	0.31104 (8)	0.0777 (6)
H54	0.5182	0.3030	0.2926	0.093*
C55	0.45952 (16)	0.3614 (3)	0.35676 (7)	0.0638 (5)
H55	0.4663	0.2341	0.3685	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S3	0.0900 (4)	0.0747 (4)	0.0521 (3)	0.0413 (3)	0.0181 (2)	0.0127 (2)
O1W	0.1272 (17)	0.0709 (12)	0.0921 (13)	0.0259 (12)	0.0321 (12)	−0.0005 (10)
O2W	0.1429 (17)	0.0830 (12)	0.0836 (12)	0.0603 (12)	0.0421 (11)	0.0241 (10)
O3	0.1085 (11)	0.0711 (10)	0.0685 (9)	0.0399 (9)	0.0309 (8)	0.0157 (8)
N1	0.0678 (9)	0.0585 (9)	0.0519 (9)	0.0213 (8)	0.0113 (7)	0.0051 (7)
N2	0.0722 (10)	0.0570 (10)	0.0502 (9)	0.0227 (8)	0.0097 (7)	0.0074 (7)
N3	0.0764 (10)	0.0551 (9)	0.0479 (9)	0.0157 (8)	0.0086 (7)	0.0041 (7)
N4	0.0579 (8)	0.0476 (8)	0.0454 (8)	0.0159 (7)	0.0038 (6)	0.0038 (7)
N5	0.0883 (13)	0.1053 (16)	0.0614 (11)	0.0187 (11)	0.0202 (9)	0.0151 (11)
C3	0.0639 (11)	0.0504 (10)	0.0466 (10)	0.0163 (9)	0.0047 (8)	0.0049 (8)
C5	0.0526 (9)	0.0484 (10)	0.0490 (9)	0.0119 (8)	0.0042 (7)	−0.0005 (8)
C31	0.0699 (12)	0.0645 (12)	0.0522 (11)	0.0218 (10)	0.0097 (9)	0.0070 (9)
C32	0.0638 (11)	0.0576 (12)	0.0520 (10)	0.0146 (9)	0.0073 (8)	0.0032 (9)
C33	0.0631 (11)	0.0642 (12)	0.0474 (10)	0.0086 (9)	0.0072 (8)	0.0038 (9)
C34	0.1135 (19)	0.0751 (15)	0.0691 (14)	−0.0035 (14)	0.0177 (13)	0.0096 (12)
C35	0.125 (2)	0.1004 (19)	0.0788 (17)	−0.0112 (17)	0.0302 (16)	0.0179 (15)
C36	0.1034 (19)	0.143 (3)	0.0563 (14)	0.0077 (18)	0.0104 (13)	0.0158 (16)
C37	0.115 (2)	0.120 (2)	0.0649 (14)	−0.0232 (17)	0.0205 (14)	−0.0215 (15)
C38	0.1011 (17)	0.0981 (18)	0.0600 (13)	−0.0266 (14)	0.0177 (12)	−0.0114 (12)
C41	0.0530 (10)	0.0505 (10)	0.0429 (9)	0.0134 (8)	0.0040 (8)	0.0048 (8)
C42	0.0733 (13)	0.0554 (12)	0.0704 (13)	0.0155 (10)	−0.0095 (10)	−0.0003 (10)
C43	0.0992 (17)	0.0546 (12)	0.0807 (15)	0.0277 (12)	0.0066 (13)	0.0058 (11)
C44	0.0624 (13)	0.0886 (17)	0.0757 (14)	0.0314 (12)	0.0153 (11)	0.0305 (13)
C45	0.0599 (12)	0.104 (2)	0.0889 (17)	0.0109 (13)	−0.0148 (11)	0.0166 (15)
C46	0.0705 (13)	0.0678 (13)	0.0692 (13)	0.0084 (11)	−0.0077 (10)	−0.0029 (11)
C47	0.0813 (16)	0.138 (3)	0.148 (3)	0.0593 (18)	0.0254 (17)	0.062 (2)
C51	0.0468 (9)	0.0608 (11)	0.0494 (10)	0.0080 (8)	0.0035 (7)	0.0036 (8)
C52	0.0781 (13)	0.0647 (13)	0.0665 (13)	0.0145 (10)	0.0161 (10)	0.0100 (11)
C53	0.0938 (16)	0.0847 (16)	0.0728 (15)	0.0173 (13)	0.0200 (12)	0.0276 (13)
C54	0.0854 (15)	0.0906 (17)	0.0572 (12)	0.0189 (12)	0.0160 (11)	−0.0012 (12)
C55	0.0720 (12)	0.0647 (12)	0.0549 (11)	0.0142 (10)	0.0090 (9)	0.0000 (10)

Geometric parameters (Å, º)

S3—C3	1.7319 (18)	C36—C37	1.517 (4)
S3—C31	1.7880 (19)	C36—H36A	0.9700
O1W—H11W	0.87 (3)	C36—H36B	0.9700
O1W—H12W	0.84 (2)	C37—C38	1.534 (3)
O2W—H21W	0.83 (4)	C37—H37A	0.9700
O2W—H22W	0.86 (3)	C37—H37B	0.9700
O3—C32	1.230 (2)	C38—H38A	0.9700
N1—C5	1.308 (2)	C38—H38B	0.9700
N1—N2	1.388 (2)	C41—C42	1.368 (3)
N2—C3	1.308 (2)	C41—C46	1.372 (3)
N3—C32	1.314 (2)	C42—C43	1.389 (3)
N3—C33	1.460 (2)	C42—H42	0.9300
N3—H3	0.8600	C43—C44	1.371 (4)
N4—C3	1.369 (2)	C43—H43	0.9300
N4—C5	1.371 (2)	C44—C45	1.371 (4)
N4—C41	1.443 (2)	C44—C47	1.516 (3)
N5—C54	1.323 (3)	C45—C46	1.377 (3)
N5—C53	1.328 (3)	C45—H45	0.9300
C5—C51	1.470 (2)	C46—H46	0.9300
C31—C32	1.513 (2)	C47—H47A	0.9600
C31—H31A	0.9700	C47—H47B	0.9600
C31—H31B	0.9700	C47—H47C	0.9600
C33—C38	1.502 (3)	C51—C52	1.378 (3)
C33—C34	1.510 (3)	C51—C55	1.382 (3)
C33—H33	0.9800	C52—C53	1.380 (3)
C34—C35	1.532 (3)	C52—H52	0.9300
C34—H34A	0.9700	C53—H53	0.9300
C34—H34B	0.9700	C54—C55	1.373 (3)
C35—C36	1.499 (4)	C54—H54	0.9300
C35—H35A	0.9700	C55—H55	0.9300
C35—H35B	0.9700
C3—S3—C31	98.69 (8)	C36—C37—C38	110.2 (2)
H11W—O1W—H12W	109 (4)	C36—C37—H37A	109.6
H21W—O2W—H22W	111 (3)	C38—C37—H37A	109.6
C5—N1—N2	108.27 (13)	C36—C37—H37B	109.6
C3—N2—N1	106.72 (14)	C38—C37—H37B	109.6
C32—N3—C33	123.56 (16)	H37A—C37—H37B	108.1
C32—N3—H3	118.2	C33—C38—C37	110.54 (19)
C33—N3—H3	118.2	C33—C38—H38A	109.5
C3—N4—C5	104.98 (14)	C37—C38—H38A	109.5
C3—N4—C41	123.50 (14)	C33—C38—H38B	109.5
C5—N4—C41	130.55 (14)	C37—C38—H38B	109.5
C54—N5—C53	115.89 (19)	H38A—C38—H38B	108.1
N2—C3—N4	110.52 (15)	C42—C41—C46	120.73 (17)
N2—C3—S3	128.92 (14)	C42—C41—N4	120.11 (16)
N4—C3—S3	120.55 (12)	C46—C41—N4	118.98 (16)
N1—C5—N4	109.51 (15)	C41—C42—C43	118.6 (2)
N1—C5—C51	123.79 (15)	C41—C42—H42	120.7
N4—C5—C51	126.68 (15)	C43—C42—H42	120.7
C32—C31—S3	107.43 (13)	C44—C43—C42	121.9 (2)
C32—C31—H31A	110.2	C44—C43—H43	119.1
S3—C31—H31A	110.2	C42—C43—H43	119.1
C32—C31—H31B	110.2	C43—C44—C45	117.78 (19)
S3—C31—H31B	110.2	C43—C44—C47	120.6 (3)
H31A—C31—H31B	108.5	C45—C44—C47	121.6 (3)
O3—C32—N3	124.11 (17)	C44—C45—C46	121.7 (2)
O3—C32—C31	120.80 (17)	C44—C45—H45	119.2
N3—C32—C31	115.09 (16)	C46—C45—H45	119.2
N3—C33—C38	111.88 (16)	C41—C46—C45	119.3 (2)
N3—C33—C34	109.10 (16)	C41—C46—H46	120.4
C38—C33—C34	111.63 (19)	C45—C46—H46	120.4
N3—C33—H33	108.0	C44—C47—H47A	109.5
C38—C33—H33	108.0	C44—C47—H47B	109.5
C34—C33—H33	108.0	H47A—C47—H47B	109.5
C33—C34—C35	110.6 (2)	C44—C47—H47C	109.5
C33—C34—H34A	109.5	H47A—C47—H47C	109.5
C35—C34—H34A	109.5	H47B—C47—H47C	109.5
C33—C34—H34B	109.5	C52—C51—C55	117.27 (18)
C35—C34—H34B	109.5	C52—C51—C5	123.40 (17)
H34A—C34—H34B	108.1	C55—C51—C5	119.26 (17)
C36—C35—C34	110.3 (2)	C51—C52—C53	118.8 (2)
C36—C35—H35A	109.6	C51—C52—H52	120.6
C34—C35—H35A	109.6	C53—C52—H52	120.6
C36—C35—H35B	109.6	N5—C53—C52	124.4 (2)
C34—C35—H35B	109.6	N5—C53—H53	117.8
H35A—C35—H35B	108.1	C52—C53—H53	117.8
C35—C36—C37	111.3 (2)	N5—C54—C55	124.3 (2)
C35—C36—H36A	109.4	N5—C54—H54	117.9
C37—C36—H36A	109.4	C55—C54—H54	117.9
C35—C36—H36B	109.4	C54—C55—C51	119.3 (2)
C37—C36—H36B	109.4	C54—C55—H55	120.3
H36A—C36—H36B	108.0	C51—C55—H55	120.3
C5—N1—N2—C3	−0.1 (2)	C34—C33—C38—C37	−56.4 (3)
N1—N2—C3—N4	−0.1 (2)	C36—C37—C38—C33	56.1 (3)
N1—N2—C3—S3	178.86 (15)	C3—N4—C41—C42	76.5 (2)
C5—N4—C3—N2	0.3 (2)	C5—N4—C41—C42	−116.5 (2)
C41—N4—C3—N2	170.03 (16)	C3—N4—C41—C46	−98.6 (2)
C5—N4—C3—S3	−178.82 (14)	C5—N4—C41—C46	68.3 (3)
C41—N4—C3—S3	−9.0 (3)	C46—C41—C42—C43	1.2 (3)
C31—S3—C3—N2	1.9 (2)	N4—C41—C42—C43	−173.85 (18)
C31—S3—C3—N4	−179.24 (16)	C41—C42—C43—C44	−0.2 (3)
N2—N1—C5—N4	0.2 (2)	C42—C43—C44—C45	−1.7 (3)
N2—N1—C5—C51	178.91 (17)	C42—C43—C44—C47	177.8 (2)
C3—N4—C5—N1	−0.3 (2)	C43—C44—C45—C46	2.7 (4)
C41—N4—C5—N1	−169.07 (17)	C47—C44—C45—C46	−176.8 (2)
C3—N4—C5—C51	−178.93 (17)	C42—C41—C46—C45	−0.3 (3)
C41—N4—C5—C51	12.3 (3)	N4—C41—C46—C45	174.84 (19)
C3—S3—C31—C32	176.56 (15)	C44—C45—C46—C41	−1.7 (4)
C33—N3—C32—O3	−2.9 (3)	N1—C5—C51—C52	−149.1 (2)
C33—N3—C32—C31	177.03 (17)	N4—C5—C51—C52	29.3 (3)
S3—C31—C32—O3	−16.0 (3)	N1—C5—C51—C55	27.6 (3)
S3—C31—C32—N3	164.05 (15)	N4—C5—C51—C55	−153.98 (19)
C32—N3—C33—C38	−71.5 (3)	C55—C51—C52—C53	0.6 (3)
C32—N3—C33—C34	164.5 (2)	C5—C51—C52—C53	177.4 (2)
N3—C33—C34—C35	−179.4 (2)	C54—N5—C53—C52	−1.2 (4)
C38—C33—C34—C35	56.5 (3)	C51—C52—C53—N5	0.4 (4)
C33—C34—C35—C36	−56.4 (3)	C53—N5—C54—C55	1.0 (4)
C34—C35—C36—C37	57.4 (3)	N5—C54—C55—C51	−0.1 (4)
C35—C36—C37—C38	−57.3 (3)	C52—C51—C55—C54	−0.7 (3)
N3—C33—C38—C37	−179.0 (2)	C5—C51—C55—C54	−177.60 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2W^i	0.87 (3)	1.90 (3)	2.763 (3)	172 (3)
N3—H3···O1W	0.86	1.97	2.827 (2)	171
O2W—H22W···N2^i	0.86 (3)	2.03 (3)	2.873 (2)	167 (3)
O2W—H21W···N1	0.83 (4)	2.01 (4)	2.819 (2)	165 (3)
O1W—H12W···O3^ii	0.84 (2)	2.09 (2)	2.905 (3)	164 (5)

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