Three-dimensional hydrogen-bonded assembly in 2,2'-disulfanyl­idene-5,5'-biimidazolidinyl­idene-4,4'-dione-di­methyl­formamide-water (3/2/4)

The title compound, 3C₆H₄N₄O₂S₂·2C₃H₇NO·4H₂O, com­prises three 2,2'-disulfanyl­idene-5,5'-biimidazolidinyl­idene-4,4'-di­one mol­ecules, two di­methyl­formamide mol­ecules and four water mol­ecules arranged around a crystallographic inversion centre. The non-H atoms within the 5,5'-bi­imida­zoli­din­yl­idene mol­ecule are coplanar and these mol­ecules aggregate through N-H...S hydrogen-bonding inter­actions with cyclic motifs [graph set R₂²(8)], giving two-dimensional ribbon structures which are close to being parallel. The two inde­pendent water mol­ecules associate to form centrosymmetric cyclic hydrogen-bonded (H₂O)₄ tetra­meric units [graph set R₄⁴(8)]. The ribbon structures extend along the a axis and are linked through the water tetra­mers and the di­methyl­formamide mol­ecules by a combination of two- and three-centre hydrogen bonds, giving an overall three-dimensional structure.

S1. Introduction

The common synthetic routes employed in the synthesis of di­hydro­pyrimidinone derivatives generally involve multi-step transformations that are essentially based on the Biginelli condensation methodology (Steele et al., 1998). 3,4-Di­hydro­pyrimidino­nes have drawn widespread attention due to their broad pharmaceutical applications. A variety of di­hydro­pyrimidinone derivatives have been screened for anti­hypertension (Atwal, 1990), anti­bacterial (Matsuda & Hirao, 1965) and calcium-channel-blocking activities (Manjula et al., 2004). The title compound, 2,2'-disulfanyl­idene-5,5'-biimidazolidinyl­idene-4,4'-dione–di­methyl­formamide–water (3/2/4), (I), was obtained as the reaction product in the attempted synthesis of 5-eth­oxy­carbonyl-6-methyl-2-sulfanyl­idene-1,2,3,4-tetra­hydro­pyrimidine-4-carb­oxy­lic acid and the structure is reported herein.

S2. Experimental

S2.1. Synthesis and crystallization

The title compound, (I), was prepared as an unexpected product. Glyoxylic acid (50% in water, 8 mmol), ethyl aceto­acetate (8 mmol), thio­urea (12 mmol) and CaF₂ (4 mmol) were mixed in a 50 ml flask. After the mixture had been stirred and refluxed at 373 K for 8 h, the reaction mixture was allowed to stand at room temperature and the crude product formed was filtered, washed with ethanol followed by water and dried. Further purification was done by recrystallization from di­methyl­formamide. Recrystallization of the crude product from DMF resulted in brown plate-like single crystals of (I) suitable for X-ray diffraction analysis after six weeks.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions (C—H = 0.93 and 0.96 Å for Csp² and Csp³ atoms, respectively), assigned fixed U_iso values [U_iso(H) = 1.2U_eq(Csp²) and 1.5U_eq(Csp³)] and allowed to ride. H atoms attached to O and N atoms were found in the difference electron-density map with O—H and N—H bond lengths in the range 0.78–0.86 Å. Water atoms H5C and H6C are disordered over two positions, with occupancies of 0.53 (4) and 0.47 (4), and all disordered atoms were subjected to a rigid-bond restraint.

S3. Results and discussion

The title compound, (I), crystallizes in the space group P1, with one and a half molecules of 2,2'-disulfanyl­idene-5,5'-biimidazolidinyl­idene-4,4'-dione, one di­methyl­formamide molecule and two water molecules in the asymmetric unit. The half molecule sits on a crystallographic inversion center situated at the mid-point of C9—C9(-x+2, -y+2, -z+1) bond (Fig. 1). The non-H atoms in the main organic component of (I) are coplanar, with maximum deviations from the least-squares planes of 0.0030 and 0.0109 Å, respectively, for the two independent molecules. The average C—S bond length of 1.644 (2) Å agrees well with similar bonds in related compounds, being inter­mediate between the value of 1.82 Å for a C—S single bond and 1.56 Å for a C═S double bond (Sutton, 1965). The corresponding average C—-N bond length of 1.373 (3) Å is indicative of some double-bond character, suggesting extensive electron delocalization over the whole 2,2'-disulfanyl­idene-5,5'-biimidazolidinyl­idene-4,4'-dione molecule.

The 2,2'-disulfanyl­idene-5,5'-biimidazolidinyl­idene-4,4'-dione molecules aggregate into parallel layered ribbons of the type ···A···A···B···A···A···B stacked along the b axis (Fig. 2). The spacing between the layers A···A and A···B is ca 3.28 Å. In the A layer, these molecules associate through N5—H5A···S2^vii and N5^vii—H5A^vii···S2 hydrogen bonds (see Table 2 for geometric details and symmetry codes), forming a centrosymmetric cyclic motif [graph set R₂²(8); Bernstein et al., 1995]. Atoms N5 and N5^vii act as donors to atoms O3ⁱ and O3ⁱⁱ through intra­molecular N5—H5A···O3ⁱ and N5^vii—H5A^vii···O3ⁱⁱ [check codes against Table 2] hydrogen-bond inter­actions. Atom N6 acts as a donor to water molecule O6^viii through an inter­molecular N6—H6A···O6^viii hydrogen bond to afford a two-dimensional network. In the B layer, the dimeric R₂²(8) association is formed through N1—H1A···S3ⁱⁱⁱ and N4ⁱⁱ—H4Aⁱⁱ···S1 [check] hydrogen bonds, generating the ribbon structure, but through translation-related molecules. Atoms N1 and N4 act as donors to atoms O2 and O1 through intra­molecular N1—H1A···O2 and N4—H4A···O1 hydrogen bonds. Atoms N2 and N3 act as donors to atoms O4^iv and O5^v through N2—H2A···O4^iv and N3—H3A···O5^v hydrogen bonds to afford a second two-dimensional network.

In the crystal packing of (I), as indicated previously, there are ribbon structures or tapes which extend along the a axis (see Fig. 3) and which are linked peripherally by the water and DMF molecules into an overall three-dimensional structure. Although the inter­layer spacing is ca 3.28 Å, PLATON (Spek, 2009) indicates that there is no ring centroid separation that is less than 4.4020 (17) Å, which is beyond the extreme value for π–π inter­actions (ca 3.9 Å) because of the ring offsets in the layers (Fig. 3).

Of recent inter­est is the presence of water clusters of the type (H₂O)_n in structures and their possible role in the anomalous behaviour of bulk water in the stabilization and function of biomolecules and in the design of new materials (Atwood et al., 2001; Lu et al., 2005; Luo et al., 2012). In the crystal structure of (I), there are two crystallographically unique water molecules in the asymmetric unit (O5 and O6) which associate through hydrogen bonds to form a cyclic centrosymmetric (H₂O)₄ tetra­mer unit [graph set R₄⁴(8)] (Bernstein et al., 1995). Atoms H5C and H6C of the water molecules which hold this tetra­mer together are, not surprisingly, disordered over two positions with occupancies of 0.53 (4) and 0.47 (4) (Fig. 4 and Table 2). Within this cluster, the four O atoms are coplanar, with the remaining two H atoms being 0.20 and 0.12 Å above plane of the ring. Such an arrangement is described as an irregular uudd-type water tetra­mer (u = up and d = down; Chen et al., 2013; Gregory & Clary, 1996; Liu & Wu, 2013; Long et al., 2004). The two water molecules (O5 and O6) are involved in the formation of a number of hydrogen bonds in addition to the water–water inter­actions which hold the tetra­mer together. These include O6 which acts as a hydrogen-bond donor to DMF atom O4^ix and O5 which acts as a hydrogen-bond donor to imidazolidinone atom O2 (see Table 2 for geometric details and symmetry codes). The water molecules of the tetra­mer also act as hydrogen-bond acceptors; O5^v accepts a hydrogen bond from imidazolidinone atom N3, while O6^viii accepts a hydrogen bond from imidazolidinone atom N6. Thus, the water tetra­mer is involved in eight inter­molecular hydrogen bonds and clearly plays a pivotal role in the stabilization of the crystal packing in this complex. Each of di­methyl­formamide molecules acts as a double acceptor, viz to a water molecules in an O6—H6B···O4^ix hydrogen bond and to an imidazolidinone molecule in an N2—H2A···O4^iv. Thus, the (H₂O)₄(DMF)₂ moieties are anchored by abundant hydrogen bonds to the organic layered ribbon structures in (I) to construct the three-dimensional supra­molecular network (Fig. 5). The majority of these hydrogen bonds are of a two-centre-type and the minority of a three-centre-type of N1—H1A···O2/S3ⁱⁱⁱ, N4—H4A···O1/S1^vi and N5—H5A···O3ⁱ/S2^vii. These chains are linked across the c axis through water O5—H5B···O2 and the N4—H4A···O5^iv [not in Table 2] links, as well as through an N2—H2A···O5 [not in Table 2] link to a DMF O-atom acceptor.

In conclusion, the hydrated title compound has been crystallized and structurally characterized, showing abundant two-centre and three-centre hydrogen-bonding inter­actions in the solid state.

Related literature

For related literature, see: Atwal (1990); Atwood et al. (2001); Bernstein et al. (1995); Chen et al. (2013); Gregory & Clary (1996); Liu & Wu (2013); Long et al. (2004); Lu et al. (2005); Luo et al. (2012); Manjula et al. (2004); Matsuda & Hirao (1965); Steele et al. (1998); Sutton (1965).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The atom-numbering scheme for (I), showing 30% probability displacement ellipsoids. All disorder components are shown. Inversion-related A and B species are generated by the symmetry operations (-x+2, -y+2, -z+1) and (-x+1, -y+1, -z+2), respectively.
	Fig. 2. Intermolecular R2^2(8) hydrogen-bonding associations (shown as green dashed lines) between 2,2'-disulfanylidene-5,5'-biimidazolidinylidene-4,4'-dione molecules and peripheral hydrogen-bond extensions in the A and B ribbon structures of (I) with non-associated H atoms being omitted for clarity. For symmetry codes, see Table 2.
	Fig. 3. The one-dimensional layered ribbon structures in (I), with the water and DMF molecules and non-associated H atoms omitted. Green dashed lines indicate hydrogen bonds.
	Fig. 4. The hydrogen bonding (green dashed lines) involving the water tetramers and the DMF molecules in the structure of (I), with the 2,2'-disulfanylidene-5,5'-biimidazolidinylidene-4,4'-dione molecules omitted. For symmetry codes, see Table 2.
	Fig. 5. The three-dimensional structure of (I), viewed down the a axis, showing the inter-species hydrogen bonds as green dashed lines, with non-associated H atoms omitted for clarity.

2,2'-Disulfanylidene-5,5'-biimidazolidinylidene-4,4'-dione–dimethylformamide–water (3/2/4)

Crystal data

3C6H4N4O2S2·2C3H7NO·4H2O	Z = 1
Mr = 903.01	F(000) = 468
Triclinic, P1	Dx = 1.574 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0655 (16) Å	Cell parameters from 8524 reflections
b = 10.391 (2) Å	θ = 3.2–27.5°
c = 12.735 (3) Å	µ = 0.44 mm^−1
α = 105.60 (1)°	T = 298 K
β = 103.47 (1)°	Block, brown
γ = 102.81 (2)°	0.24 × 0.22 × 0.20 mm
V = 952.5 (3) Å^3

Data collection

Rigaku Mercury2 (2x2 bin mode) diffractometer	4359 independent reflections
Radiation source: fine-focus sealed tube	3164 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
Tmin = 0.903, Tmax = 0.918	l = −16→16
9925 measured 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0464P)^2 + 0.4062P] where P = (Fo^2 + 2Fc^2)/3
4359 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 0.41 e Å^−3
9 restraints	Δρmin = −0.21 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.4184 (3)	0.2934 (2)	0.41471 (16)	0.0289 (4)
C2	0.6914 (3)	0.2880 (2)	0.39488 (16)	0.0310 (4)
C3	0.7072 (3)	0.3421 (2)	0.51797 (16)	0.0289 (4)
C4	0.8596 (3)	0.3828 (2)	0.60573 (16)	0.0294 (4)
C5	0.8822 (3)	0.4365 (2)	0.72936 (16)	0.0312 (4)
C6	1.1511 (3)	0.4299 (2)	0.70438 (17)	0.0302 (4)
C7	0.6343 (3)	0.9291 (2)	0.35311 (17)	0.0306 (4)
C8	0.9043 (3)	0.9142 (2)	0.33321 (17)	0.0324 (5)
C9	0.9241 (3)	0.9789 (2)	0.45587 (16)	0.0305 (4)
C10	0.7671 (3)	−0.0194 (3)	0.90246 (18)	0.0392 (5)
H10A	0.8067	−0.0208	0.8393	0.047*
C11	0.9646 (4)	0.2181 (3)	0.9900 (2)	0.0567 (7)
H11A	0.9924	0.1952	0.9193	0.085*
H11B	1.0719	0.2457	1.0533	0.085*
H11C	0.9136	0.2940	0.9962	0.085*
C12	0.7797 (4)	0.1109 (3)	1.0936 (2)	0.0677 (9)
H12A	0.6957	0.0240	1.0845	0.102*
H12B	0.7238	0.1839	1.1039	0.102*
H12C	0.8817	0.1343	1.1596	0.102*
N1	0.5383 (2)	0.34206 (18)	0.52230 (14)	0.0316 (4)
H1A	0.5119	0.3691	0.5846	0.038*
N2	0.5133 (2)	0.26329 (19)	0.33965 (15)	0.0316 (4)
N3	1.0600 (2)	0.46253 (19)	0.78212 (15)	0.0331 (4)
N4	1.0288 (2)	0.38197 (19)	0.59895 (15)	0.0322 (4)
N5	0.7559 (2)	0.98398 (19)	0.46006 (15)	0.0328 (4)
N6	0.7271 (2)	0.8921 (2)	0.27791 (16)	0.0346 (4)
N7	0.8369 (2)	0.0963 (2)	0.99199 (15)	0.0405 (5)
O1	0.8073 (2)	0.26955 (19)	0.35280 (12)	0.0460 (4)
O2	0.76758 (19)	0.45526 (17)	0.77458 (12)	0.0420 (4)
O3	1.0169 (2)	0.88547 (18)	0.29070 (13)	0.0454 (4)
O4	0.6535 (2)	−0.12680 (18)	0.89406 (13)	0.0489 (4)
O5	0.7311 (2)	0.4853 (2)	0.99285 (14)	0.0437 (4)
O6	0.4087 (3)	0.2772 (2)	0.95776 (15)	0.0455 (4)
S1	0.20223 (7)	0.27339 (6)	0.37913 (5)	0.03975 (16)
S2	0.41841 (7)	0.90828 (7)	0.31867 (5)	0.04311 (16)
S3	1.36683 (7)	0.44883 (7)	0.73832 (5)	0.03996 (16)
H2A	0.471 (3)	0.228 (2)	0.273 (2)	0.034 (6)*
H3A	1.108 (3)	0.484 (3)	0.856 (2)	0.055 (8)*
H4A	1.052 (3)	0.359 (2)	0.5431 (18)	0.020 (5)*
H5A	0.731 (3)	1.016 (2)	0.518 (2)	0.042 (7)*
H6A	0.683 (3)	0.847 (2)	0.210 (2)	0.037 (7)*
H5B	0.746 (4)	0.476 (3)	0.9328 (17)	0.059 (9)*
H6B	0.401 (5)	0.236 (3)	1.002 (3)	0.093 (13)*
H5C	0.655 (5)	0.416 (3)	0.982 (4)	0.055 (16)*	0.53 (4)
H6C	0.372 (6)	0.342 (4)	0.977 (5)	0.07 (2)*	0.53 (4)
H5C'	0.512 (3)	0.308 (6)	0.966 (5)	0.064 (17)*	0.47 (4)
H6C'	0.696 (9)	0.551 (4)	1.010 (6)	0.10 (3)*	0.47 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0281 (10)	0.0306 (10)	0.0261 (10)	0.0074 (8)	0.0076 (8)	0.0086 (8)
C2	0.0317 (11)	0.0351 (11)	0.0231 (10)	0.0090 (9)	0.0070 (8)	0.0071 (8)
C3	0.0273 (10)	0.0344 (11)	0.0227 (9)	0.0093 (8)	0.0078 (8)	0.0062 (8)
C4	0.0269 (10)	0.0360 (11)	0.0233 (10)	0.0106 (8)	0.0073 (8)	0.0067 (8)
C5	0.0297 (10)	0.0374 (11)	0.0233 (10)	0.0099 (9)	0.0071 (8)	0.0066 (9)
C6	0.0288 (10)	0.0341 (11)	0.0254 (10)	0.0095 (8)	0.0076 (8)	0.0074 (8)
C7	0.0319 (10)	0.0311 (11)	0.0297 (10)	0.0107 (9)	0.0091 (8)	0.0113 (9)
C8	0.0315 (11)	0.0358 (11)	0.0261 (10)	0.0075 (9)	0.0077 (8)	0.0081 (9)
C9	0.0294 (10)	0.0355 (11)	0.0248 (10)	0.0086 (9)	0.0089 (8)	0.0079 (8)
C10	0.0408 (13)	0.0523 (14)	0.0259 (10)	0.0179 (11)	0.0094 (9)	0.0131 (10)
C11	0.0561 (16)	0.0481 (15)	0.0579 (17)	0.0089 (13)	0.0190 (13)	0.0099 (13)
C12	0.0684 (19)	0.082 (2)	0.0361 (14)	0.0074 (16)	0.0241 (13)	0.0000 (14)
N1	0.0263 (9)	0.0439 (10)	0.0229 (8)	0.0124 (7)	0.0083 (7)	0.0069 (7)
N2	0.0267 (9)	0.0419 (10)	0.0190 (8)	0.0067 (8)	0.0038 (7)	0.0051 (8)
N3	0.0272 (9)	0.0458 (11)	0.0212 (9)	0.0111 (8)	0.0053 (7)	0.0053 (8)
N4	0.0278 (9)	0.0450 (11)	0.0215 (9)	0.0118 (8)	0.0087 (7)	0.0061 (8)
N5	0.0281 (9)	0.0437 (11)	0.0239 (9)	0.0116 (8)	0.0075 (7)	0.0074 (8)
N6	0.0316 (10)	0.0433 (11)	0.0236 (9)	0.0094 (8)	0.0064 (8)	0.0064 (8)
N7	0.0372 (10)	0.0503 (12)	0.0293 (9)	0.0124 (9)	0.0108 (8)	0.0065 (9)
O1	0.0329 (8)	0.0742 (12)	0.0286 (8)	0.0195 (8)	0.0130 (7)	0.0082 (8)
O2	0.0313 (8)	0.0616 (10)	0.0295 (8)	0.0148 (7)	0.0127 (6)	0.0064 (7)
O3	0.0356 (8)	0.0634 (11)	0.0337 (8)	0.0153 (8)	0.0149 (7)	0.0070 (8)
O4	0.0520 (10)	0.0529 (10)	0.0280 (8)	0.0019 (8)	0.0057 (7)	0.0092 (7)
O5	0.0360 (9)	0.0644 (13)	0.0264 (9)	0.0118 (9)	0.0083 (7)	0.0124 (9)
O6	0.0423 (11)	0.0552 (12)	0.0312 (9)	0.0073 (9)	0.0079 (8)	0.0115 (9)
S1	0.0255 (3)	0.0557 (4)	0.0327 (3)	0.0113 (2)	0.0059 (2)	0.0101 (3)
S2	0.0288 (3)	0.0583 (4)	0.0400 (3)	0.0146 (3)	0.0067 (2)	0.0156 (3)
S3	0.0260 (3)	0.0591 (4)	0.0321 (3)	0.0140 (2)	0.0073 (2)	0.0118 (3)

Geometric parameters (Å, º)

C1—N1	1.364 (2)	C10—O4	1.238 (3)
C1—N2	1.372 (3)	C10—N7	1.314 (3)
C1—S1	1.646 (2)	C10—H10A	0.9300
C2—O1	1.207 (2)	C11—N7	1.454 (3)
C2—N2	1.376 (3)	C11—H11A	0.9600
C2—C3	1.480 (3)	C11—H11B	0.9600
C3—C4	1.347 (3)	C11—H11C	0.9600
C3—N1	1.376 (2)	C12—N7	1.455 (3)
C4—N4	1.389 (3)	C12—H12A	0.9600
C4—C5	1.474 (3)	C12—H12B	0.9600
C5—O2	1.221 (2)	C12—H12C	0.9600
C5—N3	1.365 (3)	N1—H1A	0.8600
C6—N4	1.353 (3)	N2—H2A	0.78 (2)
C6—N3	1.380 (3)	N3—H3A	0.87 (3)
C6—S3	1.644 (2)	N4—H4A	0.76 (2)
C7—N5	1.361 (3)	N5—H5A	0.81 (2)
C7—N6	1.374 (3)	N6—H6A	0.81 (2)
C7—S2	1.643 (2)	O5—H5B	0.787 (17)
C8—O3	1.212 (2)	O5—H5C	0.788 (17)
C8—N6	1.374 (3)	O5—H6C'	0.788 (17)
C8—C9	1.479 (3)	O6—H6B	0.796 (19)
C9—C9^i	1.346 (4)	O6—H6C	0.796 (19)
C9—N5	1.382 (3)	O6—H5C'	0.796 (19)
N1—C1—N2	106.45 (17)	H11B—C11—H11C	109.5
N1—C1—S1	127.77 (15)	N7—C12—H12A	109.5
N2—C1—S1	125.78 (15)	N7—C12—H12B	109.5
O1—C2—N2	128.10 (19)	H12A—C12—H12B	109.5
O1—C2—C3	128.15 (19)	N7—C12—H12C	109.5
N2—C2—C3	103.75 (17)	H12A—C12—H12C	109.5
C4—C3—N1	128.45 (18)	H12B—C12—H12C	109.5
C4—C3—C2	125.31 (18)	C1—N1—C3	111.05 (16)
N1—C3—C2	106.24 (16)	C1—N1—H1A	124.5
C3—C4—N4	127.29 (18)	C3—N1—H1A	124.5
C3—C4—C5	127.39 (18)	C1—N2—C2	112.49 (17)
N4—C4—C5	105.32 (16)	C1—N2—H2A	124.6 (17)
O2—C5—N3	127.62 (19)	C2—N2—H2A	122.6 (17)
O2—C5—C4	127.65 (19)	C5—N3—C6	112.15 (17)
N3—C5—C4	104.73 (17)	C5—N3—H3A	124.4 (17)
N4—C6—N3	106.40 (17)	C6—N3—H3A	122.7 (18)
N4—C6—S3	128.59 (16)	C6—N4—C4	111.39 (17)
N3—C6—S3	125.01 (15)	C6—N4—H4A	123.6 (15)
N5—C7—N6	106.53 (18)	C4—N4—H4A	125.0 (16)
N5—C7—S2	127.50 (16)	C7—N5—C9	111.07 (18)
N6—C7—S2	125.97 (16)	C7—N5—H5A	123.5 (17)
O3—C8—N6	127.64 (19)	C9—N5—H5A	125.5 (17)
O3—C8—C9	128.35 (19)	C8—N6—C7	112.34 (18)
N6—C8—C9	104.01 (17)	C8—N6—H6A	120.7 (17)
C9^i—C9—N5	127.9 (2)	C7—N6—H6A	125.8 (17)
C9^i—C9—C8	126.1 (2)	C10—N7—C11	121.3 (2)
N5—C9—C8	105.95 (17)	C10—N7—C12	121.2 (2)
O4—C10—N7	126.3 (2)	C11—N7—C12	117.4 (2)
O4—C10—H10A	116.9	H5B—O5—H5C	104 (4)
N7—C10—H10A	116.9	H5B—O5—H6C'	109 (5)
N7—C11—H11A	109.5	H5C—O5—H6C'	110 (5)
N7—C11—H11B	109.5	H6B—O6—H6C	106 (5)
H11A—C11—H11B	109.5	H6B—O6—H5C'	107 (4)
N7—C11—H11C	109.5	H6C—O6—H5C'	108 (5)
H11A—C11—H11C	109.5
O1—C2—C3—C4	1.1 (4)	S1—C1—N2—C2	−178.67 (16)
N2—C2—C3—C4	−179.1 (2)	O1—C2—N2—C1	178.6 (2)
O1—C2—C3—N1	−179.1 (2)	C3—C2—N2—C1	−1.1 (2)
N2—C2—C3—N1	0.6 (2)	O2—C5—N3—C6	−179.5 (2)
N1—C3—C4—N4	−179.9 (2)	C4—C5—N3—C6	−0.3 (2)
C2—C3—C4—N4	−0.2 (4)	N4—C6—N3—C5	0.1 (2)
N1—C3—C4—C5	0.7 (4)	S3—C6—N3—C5	179.78 (16)
C2—C3—C4—C5	−179.7 (2)	N3—C6—N4—C4	0.2 (2)
C3—C4—C5—O2	−0.8 (4)	S3—C6—N4—C4	−179.47 (16)
N4—C4—C5—O2	179.6 (2)	C3—C4—N4—C6	−180.0 (2)
C3—C4—C5—N3	180.0 (2)	C5—C4—N4—C6	−0.4 (2)
N4—C4—C5—N3	0.4 (2)	N6—C7—N5—C9	−2.1 (2)
O3—C8—C9—C9^i	1.5 (4)	S2—C7—N5—C9	177.30 (16)
N6—C8—C9—C9^i	−179.2 (3)	C9^i—C9—N5—C7	−178.8 (3)
O3—C8—C9—N5	−177.4 (2)	C8—C9—N5—C7	0.1 (2)
N6—C8—C9—N5	1.8 (2)	O3—C8—N6—C7	176.1 (2)
N2—C1—N1—C3	−0.8 (2)	C9—C8—N6—C7	−3.2 (2)
S1—C1—N1—C3	179.13 (16)	N5—C7—N6—C8	3.4 (2)
C4—C3—N1—C1	179.8 (2)	S2—C7—N6—C8	−175.98 (16)
C2—C3—N1—C1	0.1 (2)	O4—C10—N7—C11	−177.5 (2)
N1—C1—N2—C2	1.2 (2)	O4—C10—N7—C12	−2.1 (4)

Symmetry code: (i) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O3^ii	0.96	2.56	3.495 (3)	166
N1—H1A···O2	0.86	2.57	3.059 (2)	117
N1—H1A···S3^iii	0.86	2.55	3.3948 (18)	167
N2—H2A···O4^iv	0.78 (2)	1.99 (2)	2.774 (2)	175 (2)
N3—H3A···O5^v	0.87 (3)	1.96 (3)	2.803 (2)	164 (2)
N4—H4A···O1	0.76 (2)	2.52 (2)	2.980 (2)	119.9 (18)
N4—H4A···S1^vi	0.76 (2)	2.70 (2)	3.448 (2)	166.3 (19)
N5—H5A···O3^i	0.81 (2)	2.56 (2)	3.024 (2)	118 (2)
N5—H5A···S2^vii	0.81 (2)	2.67 (3)	3.466 (2)	168 (2)
N6—H6A···O6^viii	0.81 (2)	2.04 (2)	2.842 (3)	174 (2)
O5—H5B···O2	0.79 (2)	2.02 (2)	2.805 (2)	176 (3)
O6—H6B···O4^ix	0.80 (2)	2.03 (2)	2.817 (3)	173 (3)
O5—H5C···O6	0.79 (2)	2.08 (2)	2.843 (3)	162 (5)
O6—H6C···O5^x	0.80 (2)	2.12 (2)	2.913 (3)	172 (6)
O6—H5C′···O5	0.80 (2)	2.14 (3)	2.843 (3)	148 (5)
O5—H6C′···O6^x	0.79 (2)	2.13 (2)	2.913 (3)	175 (7)

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