The inter­play of solvation, mol­ecular conformation and supra­molecular assembly in 1,1′-({[(ethane-1,2-diyl)dioxy](1,2-phenyl­ene)}bis­(methanylyl­idene))bis­(thio­semicarbazide) and its N,N-di­methyl­formamide disolvate

The wide diversity of applications of thio­semicarbazones and bis(thio­semi­carba­zones) has seen them used as anti­cancer and anti­tubercular agents, and as ligands in metal complexes designed to act as site-specific radiopharmaceuticals. Mol­e­cules of 1,1′-({[(ethane-1,2-diyl)di­oxy](1,2-phenyl­ene)}bis­(methanylyl­idene))bis­(thio­semicarbazide) {alternative name: 2,2′-[ethane-1,2-diylbis(oxy)]dibenz­aldehyde bis­(thio­semicarbazide)}, C₁₈H₂₀N₆O₂S₂, (I), lie across twofold rotation axes in the space group C2/c, with an O—C—C—O torsion angle of −59.62 (13)° and a trans-planar arrangement of the thio­semicarbazide fragments relative to the adjacent aryl rings. The mol­ecules of (I) are linked by N—H...S hydrogen bonds to form sheets containing R²₄(38) rings and two types of R²₂(8) ring. In the N,N-di­methyl­formamide disolvate, C₁₈H₂₀N₆O₂S₂·2C₃H₇NO, (II), the independent mol­ecular components all lie in general positions, but one of the solvent mol­ecules is disordered over two sets of atomic sites having occupancies of 0.839 (3) and 0.161 (3). The O—C—C—O torsion angle in the ArOCH₂CH₂OAr component is −75.91 (14)° and the independent thio­semicarbazide fragments both adopt a cis-planar arrangement relative to the adjacent aryl rings. The ArOCH₂CH₂OAr components in (II) are linked by N—H...S hydrogen bonds to form deeply puckered sheets containing R²₂(8), R²₄(8) and two types of R²₂(38) rings, and which contain cavities which accommodate all of the solvent mol­ecules in the inter­ior of the sheets. Comparisons are made with some related compounds.

S1. Introduction

Thio­semicarbazones are a class of small molecules that have been evaluated over a number of years as anti­cancer agents (Finch et al., 1999) and as anti­tubercular agents (Shucla et al., 1984; Desai et al., 1984), as well as for their parasiticidal action (Wilson et al., 1974; Du et al., 2002; Greenbaum et al., 2004) against Plasmodium falciparum and Trypanasoma cruzi which are the causative agents of malaria and Chagas' disease, respectively. On the other hand, bis­(thio­semicarbazone) derivatives have been used as ligands in metal complexes designed to act as site-specific radiopharmaceuticals (Holland et al., 2007). This very wide diversity of application has thus prompted the present study in which we report the synthesis and the molecular and supra­molecular structures of two bis­(thio­semicarbazones), namely 1,1'-({[(ethane-1,2-diyl)di­oxy](1,2-phenyl­ene)}bis­(methanylyl­idene))bis­(thio­semicarbazide), (I) (Fig. 1), and its N,N-di­methyl­formamide disolvate, (II) (Fig. 2).

S2. Experimental

S2.1. Synthesis and crystallization

For the synthesis of compound (I), a mixture of 2,2'-[ethane-1,2-diylbis(­oxy)]dibenzaldehyde (1 mmol) and thio­semicarbazide (2 mmol) in ethanol (15 ml) containing a catalytic qu­antity of acetic acid was heated under reflux for 4 h. The mixture was cooled to ambient temperature and then poured into ice/water. The resulting solid product, (I), was collected by filtration, washed with water and dried in air to give colourless crystals suitable for single-crystal X-ray diffraction. ¹³C NMR (δ, p.p.m.): 67.34 (CH₂), 112.91, 120.97, 122.65, 126.21, 131.27, 138.10, 157.04 (aryl and alkenyl), 178.77 (C═S). In an alternative synthesis, a similar mixture, in methanol rather than ethanol, was subjected to microwave irradiation at 80 W for 20 min, after which the product (I) was isolated as before. Recrystallization by slow evaporation, at ambient temperature and in the presence of air, of a solution in N,N-di­methyl­formamide gave the bis­(solvate), (II).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. It was apparent from an early stage in the refinement of (II) that one of the N,N-di­methyl­formamide molecules, that containing atom N41 (Fig. 2), was disordered over two sets of atomic sites having unequal occupancies. For the minor disorder component, the bonded distances and the one-angle non-bonded distances were restrained to be identical to the corresponding distances in the major disorder component, subject to uncertainties of 0.005 Å and 0.01 Å, respectively. In addition, the anisotropic displacement parameters for the atom sites N41 and N51 were constrained to be identical, as were those for the sites O41 and O51. Under these conditions, the refined site occupancies were 0.839 (3) and 0.161 (3). The H atoms, apart from those in the disordered solvent molecule, were all located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 Å (alkenyl, aromatic and formyl), 0.98 (CH₃) or 0.99 Å (CH₂) and N—H = 0.88 Å, and with U_iso(H) = kU_eq(carrier) where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. The H atoms of the disordered solvent molecule were included in calculated positions in a similar manner. For (II), the bad outlier reflection (−5, 3, 4) was omitted from the final refinements. Also for (II) there was a large value of K, 3.198, for the group of very weak reflections having F_c/F_c(max) in the range 0.000 < F_c/F_c(max) < 0.005.

S3. Comment

In the unsolvated form, (I), the molecules lie across a twofold rotation axis in space group C2/c, and the reference molecule was selected as one lying across the axis along (1/2, y, 1/4). The molecular components of the solvated form, (II), all lie in general positions and one of the two molecules of N,N-di­methyl­formamide is disordered over two sets of atomic sites having occupancies 0.839 (3) and 0.161 (3). For the following discussion, it is convenient to denote the molecule of (I) and that of the principal component in (II) in the form ArOCH₂CH₂OAr.

For (I), the 14 non-H atoms forming the asymmetric unit (Fig. 1) are very nearly co-planar; the r.m.s. deviation from the mean plane through these atoms is 0.0508 Å and the maximum deviation from this plane, for atom C1, is 0.0891 (10) Å. In the analogous component of (II), the non-H atoms in the fragment from C1 to N13 and S1 have an r.m.s. deviation from their mean plane of 0.0631 Å with a maximum deviation, for atom N13, of 0.1643 (10) Å; the corresponding values for the fragment from C2 to N23 and S2 are 0.0467 Å and 0.1106 (7) Å, for atom S2. In both compounds the two ArO fragments adopt a synplanar conformation relative to the central C—C bond, as confirmed by the O—C—C—O torsion angles (Tables 2 and 4). Although the molecule of (I), and the corresponding component in (II), could both, in principle, lie across centres of inversion with maximum molecular symmetry 2/m (C_2h), neither in fact does so, with just a twofold rotation axis present in (I) and no inter­nal symmetry in (II).

Despite the conformational similarities noted above, there is one significant conformational difference between the two compounds, namely the orientation of the thio­semicarbazide fragments relative to the adjacent aryl rings, which are trans-planar in (I) but cis-planar in (II), as indicated by the relevant C—C—C—N torsion angles (Tables 2 and 3) which are close to zero in (I) but almost 180° in (II). The bond distances in (I) and (II) show no significant deviations from the normal values (Allen et al., 1987), but we note that the inter-bond angles at atoms O1 and O2 (Tables 2 and 3) are significantly larger than the usual values for such C—O—C angles.

In each of (I) and (II) there are short N—H···N contacts (Tables 4 and 5) within the thio­semicarbazide units, but these have very small N—H···N angles and so must be regarded as adventitious contacts rather than structurally significant hydrogen bonds. A combination of two independent N—H···S hydrogen bonds (Table 4) links the molecules of (I) into complex sheets, but the formation of these sheets can readily be analysed in terms of two simple sub-structures (Ferguson et al., 1998a,b; Gregson et al., 2000). In the first of these two sub-structures, the N—H···S hydrogen bond having atom N2 as the donor links molecules lying across the twofold rotation axes along (1/2, y, n + 1/4), where n represents an integer, to form a chain of rings running parallel to the [001] direction and consisting of R²₂(8) (Bernstein et al., 1995) rings, which lie across the twofold axes along (1/2, y, n − 1/4), where n again represents an integer (Fig. 3). In the second sub-structure, the N—H···S hydrogen bond having atom N3 as the donor links molecules lying across the twofold rotation axes along (-n/2 + 1/2, y, n/2 + 1/4) into a chain of centrosymmetric R²₂(8) rings running parallel to the [101] direction, in which the hydrogen-bonded rings are centred at (-n/2 + 3/4, 1/4, n/2), where n represents an integer in each case (Fig. 4). The combination of these two chain-of-rings motifs gives rise to a sheet lying parallel to (010), in the domain 0 < y < 1/2, which contains R²₄(38) rings as well as two types of R²₂(8) rings (Fig. 5). A second sheet of this type, related to the first by inversion, lies in the domain 0.5 < y < 1.0, but there are no significant direction-specific inter­actions between adjacent sheets.

The solvent components of (II) are linked to the ArOCH₂CH₂OAr component by two independent N—H···O hydrogen bonds (Table 5, Fig. 2), but neither of the N—H bonds involved in these inter­actions, nor the solvent molecules themselves, play any further direct role in the supra­molecular assembly. The ArOCH₂CH₂OAr components of (II) are linked by two independent three-centre N—H···(S)₂ hydrogen bonds (Table 5), both of which are effectively planar, to form complex sheets which can, like those in (I), be readily analysed in terms of two simpler sub-structures. In one sub-structure, the ArOCH₂CH₂OAr components which are related by translation along the [001] direction are linked by two N—H···S hydrogen bonds to form a C(19)C(19)[R²₂(8)] chain of rings. In the second sub-structure, molecules related by inversion are again linked by two independent N—H···S hydrogen bonds to form a chain of edge-fused R²₂(38) rings running parallel to the [100] direction, in which the rings involving atoms of type N13 as the hydrogen-bond donors are centred at (n, 1/2, 1/2), while those involving atoms of type N23 as the donors are centred at (n + 1/2, 1/2, 1/2), where n represents an integer in each case. The combination of these two motifs generates a sheet lying parallel to (010) and containing four types of ring, namely R²₂(8), R²₄(8) and two types of R²₂(38) rings, all of which, apart from the R²₂(8) rings, are centrosymmetric (Fig. 6). Because of the conformation of the ArOCH₂CH₂OAr components discussed above, the hydrogen-bonded sheets in the structure of (II) are deeply puckered and they enclose substantial voids, each of which accommodates four solvent molecules in two inversion-related pairs, one ordered and one disordered (Fig. 7). Two such sheets, related to one another by the translational symmetry elements of the space group, pass through each unit cell, and they are arranged such that the wide parts of one sheet are adjacent to the narrow parts of the two adjacent sheets (Fig. 7), although there are no significant direction-specific inter­actions between adjacent sheets.

It is of inter­est to compare the structure of the N,N-di­methyl­formamide disolvate, (II), reported here with that of the di­methyl­sulfoxide disolvate, (III), which was briefly reported a number of years ago (Zhu et al., 1999), although with no description or discussion whatever of the supra­molecular assembly; indeed, the presence in the structure of hydrogen bonds was not mentioned. In (III), the ArOCH₂CH₂OAr component lies across a twofold rotation axis in space group C2/c with an O—C—C—O torsion angle of −69.5 (3)°, very similar to those found in (I) and (II), and the overall conformation of this component corresponds to that observed in disolvate (II) rather than that found in unsolvated form (I). The unique solvent molecule in (III) is disordered over two sets of atomic sites having occupancies 0.708 (2) and 0.292 (2), and the molecular components within the selected asymmetric unit are linked by N—H···O hydrogen bonds. Examination of the deposited atomic coordinates for (III) shows, in fact, that the ArOCH₂CH₂OAr components in (III) are linked into sheets by N—H···S hydrogen bonds which contain a similar range of hydrogen-bonded rings to those in (II). Overall, however, the puckering of the sheets in (III) is far less that that found in (II) such that there are no cavities within the sheets, so that the solvent molecules are attached to the faces of the sheets, rather than being located in the inter­ior of deeply puckered sheets as in (II). The two solvent species, N,N-di­methyl­formamide in (II) and di­methyl­sulfoxide in (III), have fairly similar steric requirements, and both act as excellent acceptors of hydrogen bonds but poor donors. It is thus of inter­est that (II) and (III) crystallize in different space groups, P2₁/c and C2/c, respectively, with the non-solvent component lying in a general position in (II) and across a twofold rotation axis in (III), and thus also with different numbers of independent solvent molecules.

Closely related to the bis­(thio­semicarbazide) components in (I)–(III) is that in (IV) (see Scheme 2), which differs from the previous compounds in having a three-carbon spacer unit, –(CH₂)₃–, as opposed to a two-carbon spacer, –CH₂—CH₂–. Compound (IV) crystallizes from N,N-di­methyl­formamide as a partial solvate, but the solvent component was so badly disordered that no chemically sensible model could be developed (Mague et al., 2015). The non-solvent molecules in (IV) lie across twofold rotation axes in space group C2/c, and the conformation of the thio­semicarbazide fragment closely resembles that found in (II) and (III). Thus, the torsion angle corresponding to the angle C11—C12—C17—N1 in (I) and to Cx1—Cx2—Cx7—Nx1 (x = 1 or 2) in (II) has a value of 177.76 (17) Å in (IV), close to the values in (II) (Table 4) and (III) [−161.3 (3); Zhu et al., 1999] but very different from that in unsolvated (I) (Table 2). The conformation in (IV) is thus also consistent with the view that the orientation of the thio­semicarbazide fragments in this series of compounds takes one or the other of only two possible forms, depending upon whether or not the compound is solvated.

Computing details

For both compounds, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the unsolvated form, (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and atoms marked `a' are at the symmetry position (1 − x, y, −1/2 − z).
	Fig. 2. The independent molecular components of the solvated form, (II), showing the atom-labelling scheme and the hydrogen bonds within the selected asymmetric unit (dashed lines). Displacement ellipsoids are drawn at the 30% probability level and the two components of the disordered solvent molecule have occupancies of 0.839 (3) and 0.161 (3).
	Fig. 3. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain of R^22(8) rings running parallel to the [001] direction. For the sake of clarity, H atoms bonded to C atoms have been omitted. [Dashed lines indicate hydrogen bonds.] Atoms marked with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (1 − x, y, 1/2 − z), (x, y, 1 + z) and (1 − x, y, −1/2 − z), respectively.
	Fig. 4. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain of R^22(8) rings running parallel to the [101] direction. For the sake of clarity, H atoms bonded to C atoms have been omitted. [Dashed lines indicate hydrogen bonds.] Atoms marked with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (1 − x, y, 1/2 − z), (1/2 + x, 1/2 − y, −1/2 + z) and (1/2 − x, 1/2 − y, 1 − z), respectively.
	Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet lying parallel to (010). For the sake of clarity, H atoms bonded to C atoms have been omitted. [Dashed lines indicate hydrogen bonds.]
	Fig. 6. A projection, down [010], of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (010) and containing four types of ring. For the sake of clarity, the solvent components and H atoms bonded to C atoms have been omitted. [Dashed lines indicate hydrogen bonds.]
	Fig. 7. A projection, down [100], of part of the crystal structure of (II), showing both the arrangement of adjacent (010) sheets and the solvent molecules accommodated in the cavities. For the sake of clarity, H atoms bonded to C atoms have been omitted. [Dashed lines indicate hydrogen bonds.]

(I) 1,1'-({[(ethane-1,2-diyl)dioxy](1,2-phenylene)}-bis(methanylylidene))bis(thiosemicarbazide)

Crystal data

C18H20N6O2S2	F(000) = 872
Mr = 416.52	Dx = 1.421 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.063 (2) Å	Cell parameters from 2599 reflections
b = 17.869 (3) Å	θ = 1.9–29.2°
c = 7.8770 (12) Å	µ = 0.30 mm^−1
β = 100.296 (2)°	T = 150 K
V = 1947.6 (5) Å^3	Plate, colourless
Z = 4	0.14 × 0.13 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2238 independent reflections
Radiation source: fine-focus sealed tube	2028 reflections with I > 2σ(I)
Detector resolution: 0.3660 pixels mm^-1	Rint = 0.040
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −18→18
Tmin = 0.842, Tmax = 0.982	k = −23→23
16331 measured reflections	l = −10→10

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 1.5017P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2238 reflections	Δρmax = 0.42 e Å^−3
127 parameters	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.

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

	x	y	z	Uiso*/Ueq
C1	0.44565 (10)	0.51048 (8)	0.23979 (18)	0.0211 (3)
H1A	0.4260	0.5108	0.3544	0.025*
H1B	0.4185	0.5555	0.1755	0.025*
O1	0.41093 (7)	0.44423 (5)	0.14692 (12)	0.0198 (2)
C11	0.31327 (9)	0.43693 (7)	0.08975 (17)	0.0174 (3)
C12	0.28319 (9)	0.37372 (7)	−0.01346 (16)	0.0166 (3)
C13	0.18428 (10)	0.36537 (8)	−0.07851 (18)	0.0204 (3)
H13	0.1631	0.3237	−0.1504	0.025*
C14	0.11654 (10)	0.41618 (8)	−0.04077 (19)	0.0247 (3)
H14	0.0497	0.4092	−0.0851	0.030*
C15	0.14763 (11)	0.47719 (9)	0.0623 (2)	0.0277 (3)
H15	0.1017	0.5122	0.0891	0.033*
C16	0.24544 (10)	0.48801 (8)	0.12731 (19)	0.0242 (3)
H16	0.2658	0.5304	0.1974	0.029*
C17	0.34716 (10)	0.31550 (7)	−0.05783 (17)	0.0185 (3)
H17	0.3195	0.2773	−0.1352	0.022*
N1	0.43828 (8)	0.31236 (6)	0.00061 (15)	0.0193 (2)
N2	0.48436 (8)	0.25064 (6)	−0.05148 (15)	0.0212 (3)
H2	0.4508	0.2147	−0.1108	0.025*
C18	0.58142 (10)	0.24608 (8)	−0.01045 (17)	0.0195 (3)
S1	0.63697 (2)	0.17213 (2)	−0.08613 (5)	0.02270 (13)
N3	0.62690 (9)	0.29966 (8)	0.08909 (17)	0.0277 (3)
H3A	0.5937	0.3362	0.1255	0.033*
H3B	0.6903	0.2986	0.1187	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0250 (7)	0.0173 (6)	0.0188 (6)	0.0025 (5)	−0.0021 (5)	−0.0034 (5)
O1	0.0181 (5)	0.0183 (5)	0.0219 (5)	0.0017 (4)	0.0005 (4)	−0.0057 (4)
C11	0.0183 (6)	0.0188 (6)	0.0148 (6)	0.0021 (5)	0.0024 (5)	0.0016 (5)
C12	0.0180 (6)	0.0174 (6)	0.0151 (6)	0.0020 (5)	0.0048 (5)	0.0023 (5)
C13	0.0193 (6)	0.0206 (7)	0.0209 (7)	−0.0002 (5)	0.0021 (5)	0.0032 (5)
C14	0.0169 (6)	0.0287 (7)	0.0277 (7)	0.0039 (5)	0.0019 (5)	0.0044 (6)
C15	0.0239 (7)	0.0296 (8)	0.0298 (8)	0.0114 (6)	0.0054 (6)	−0.0002 (6)
C16	0.0253 (7)	0.0236 (7)	0.0228 (7)	0.0066 (6)	0.0024 (5)	−0.0040 (5)
C17	0.0199 (6)	0.0170 (6)	0.0191 (6)	−0.0005 (5)	0.0050 (5)	−0.0013 (5)
N1	0.0198 (5)	0.0185 (5)	0.0203 (6)	0.0031 (4)	0.0057 (4)	−0.0028 (4)
N2	0.0178 (5)	0.0185 (6)	0.0275 (6)	0.0013 (4)	0.0047 (4)	−0.0068 (5)
C18	0.0196 (6)	0.0206 (6)	0.0190 (6)	0.0022 (5)	0.0055 (5)	0.0015 (5)
S1	0.02035 (19)	0.0197 (2)	0.0286 (2)	0.00532 (12)	0.00597 (14)	−0.00086 (13)
N3	0.0180 (6)	0.0311 (7)	0.0331 (7)	0.0029 (5)	0.0017 (5)	−0.0117 (5)

Geometric parameters (Å, º)

C1—O1	1.4309 (16)	C15—C16	1.393 (2)
C1—C1^i	1.508 (3)	C15—H15	0.9500
C1—H1A	0.9900	C16—H16	0.9500
C1—H1B	0.9900	C17—N1	1.2831 (18)
O1—C11	1.3730 (16)	C17—H17	0.9500
C11—C16	1.3898 (19)	N1—N2	1.3783 (15)
C11—C12	1.4116 (18)	N2—C18	1.3478 (18)
C12—C13	1.4017 (18)	N2—H2	0.8800
C12—C17	1.4581 (18)	C18—N3	1.3271 (18)
C13—C14	1.386 (2)	C18—S1	1.6966 (14)
C13—H13	0.9500	N3—H3A	0.8800
C14—C15	1.383 (2)	N3—H3B	0.8800
C14—H14	0.9500
O1—C1—C1^i	107.54 (9)	C14—C15—C16	120.89 (13)
O1—C1—H1A	110.2	C14—C15—H15	119.6
C1^i—C1—H1A	110.2	C16—C15—H15	119.6
O1—C1—H1B	110.2	C11—C16—C15	120.05 (13)
C1^i—C1—H1B	110.2	C11—C16—H16	120.0
H1A—C1—H1B	108.5	C15—C16—H16	120.0
C1—O1—C11	118.45 (10)	N1—C17—C12	124.38 (12)
O1—C11—C16	123.51 (12)	N1—C17—H17	117.8
O1—C11—C12	116.37 (11)	C12—C17—H17	117.8
C16—C11—C12	120.12 (12)	C17—N1—N2	114.88 (11)
C13—C12—C11	118.12 (12)	C18—N2—N1	119.13 (11)
C13—C12—C17	116.80 (12)	C18—N2—H2	120.4
C11—C12—C17	125.08 (12)	N1—N2—H2	120.4
C14—C13—C12	121.80 (13)	N3—C18—N2	117.30 (12)
C14—C13—H13	119.1	N3—C18—S1	124.46 (11)
C12—C13—H13	119.1	N2—C18—S1	118.23 (10)
C15—C14—C13	119.01 (13)	C18—N3—H3A	120.0
C15—C14—H14	120.5	C18—N3—H3B	120.0
C13—C14—H14	120.5	H3A—N3—H3B	120.0
O1^i—C1^i—C1—O1	−59.62 (13)	C13—C14—C15—C16	0.2 (2)
C1^i—C1—O1—C11	−170.48 (12)	O1—C11—C16—C15	179.07 (13)
C1—O1—C11—C16	−4.60 (19)	C12—C11—C16—C15	−0.4 (2)
C1—O1—C11—C12	174.88 (11)	C14—C15—C16—C11	−0.4 (2)
O1—C11—C12—C13	−178.20 (11)	C13—C12—C17—N1	−175.18 (13)
C16—C11—C12—C13	1.29 (19)	C11—C12—C17—N1	4.5 (2)
O1—C11—C12—C17	2.13 (19)	C12—C17—N1—N2	177.03 (12)
C16—C11—C12—C17	−178.38 (13)	C17—N1—N2—C18	173.65 (12)
C11—C12—C13—C14	−1.48 (19)	N1—N2—C18—N3	4.51 (19)
C17—C12—C13—C14	178.22 (13)	N1—N2—C18—S1	−176.42 (9)
C12—C13—C14—C15	0.7 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C11–C16 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^ii	0.88	2.60	3.3596 (13)	145
N3—H3A···N1	0.88	2.27	2.6292 (18)	104
N3—H3B···S1^iii	0.88	2.54	3.3629 (14)	155
C1—H1B···O1^iv	0.99	2.48	3.4260 (18)	159
C16—H16···Cg1^iv	0.95	2.90	3.5769 (17)	129

Symmetry codes: (ii) −x+1, y, −z−1/2; (iii) −x+3/2, −y+1/2, −z; (iv) x, −y+1, z+1/2.

(II) 1,1'-({[(ethane-1,2-diyl)dioxy](1,2- phenylene)}bis(methanylylidene))bis(thiosemicarbazide) bis(N,N-dimethylformamide) solvate

Crystal data

C18H20N6O2S2·2C3H7NO	F(000) = 1192
Mr = 562.71	Dx = 1.278 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.6081 (16) Å	Cell parameters from 7514 reflections
b = 18.136 (3) Å	θ = 1.8–28.7°
c = 14.186 (2) Å	µ = 0.23 mm^−1
β = 101.801 (2)°	T = 150 K
V = 2923.4 (8) Å^3	Plate, colourless
Z = 4	0.26 × 0.20 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5575 reflections with I > 2σ(I)
Detector resolution: 0.3660 pixels mm^-1	Rint = 0.047
φ and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −15→15
Tmin = 0.822, Tmax = 0.982	k = −22→23
49268 measured reflections	l = −18→18
6697 independent reflections

Refinement

Refinement on F^2	8 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0593P)^2 + 0.4701P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
6697 reflections	Δρmax = 0.39 e Å^−3
383 parameters	Δρmin = −0.27 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.85899 (10)	0.24709 (6)	0.44770 (8)	0.0374 (3)
C1	0.85412 (16)	0.18343 (8)	0.50688 (11)	0.0371 (4)
H1A	0.9103	0.1890	0.5691	0.045*
H1B	0.8759	0.1388	0.4744	0.045*
C2	0.73189 (16)	0.17599 (8)	0.52358 (11)	0.0363 (4)
H2A	0.6743	0.1839	0.4625	0.044*
H12B	0.7199	0.1259	0.5475	0.044*
O2	0.71502 (10)	0.22985 (5)	0.59320 (7)	0.0340 (2)
C11	0.96302 (14)	0.26073 (8)	0.41976 (10)	0.0327 (3)
C12	0.96271 (13)	0.31932 (8)	0.35439 (10)	0.0298 (3)
C13	1.06747 (14)	0.33593 (9)	0.32491 (11)	0.0361 (3)
H13	1.0688	0.3756	0.2814	0.043*
C14	1.16912 (15)	0.29601 (10)	0.35768 (12)	0.0428 (4)
H14	1.2395	0.3082	0.3369	0.051*
C15	1.16770 (16)	0.23817 (10)	0.42100 (12)	0.0469 (4)
H15	1.2373	0.2104	0.4433	0.056*
C16	1.06595 (16)	0.22055 (9)	0.45199 (11)	0.0425 (4)
H16	1.0660	0.1808	0.4956	0.051*
C17	0.85570 (13)	0.36211 (8)	0.31858 (10)	0.0290 (3)
H17	0.7858	0.3530	0.3417	0.035*
N11	0.85868 (10)	0.41231 (6)	0.25519 (8)	0.0272 (2)
N12	0.75795 (10)	0.45316 (6)	0.22535 (8)	0.0266 (2)
H12	0.6944	0.4445	0.2485	0.032*
C18	0.75916 (11)	0.50678 (7)	0.15978 (9)	0.0235 (3)
S1	0.63846 (3)	0.56058 (2)	0.12321 (3)	0.02861 (10)
N13	0.85679 (10)	0.51483 (7)	0.12566 (8)	0.0289 (3)
H13A	0.9174	0.4857	0.1460	0.035*
H13B	0.8608	0.5493	0.0827	0.035*
C21	0.61113 (13)	0.22865 (7)	0.62434 (10)	0.0298 (3)
C22	0.59782 (13)	0.28345 (7)	0.69180 (10)	0.0281 (3)
C23	0.49286 (14)	0.28640 (9)	0.72506 (11)	0.0367 (3)
H23	0.4828	0.3232	0.7704	0.044*
C24	0.40334 (15)	0.23658 (10)	0.69305 (13)	0.0456 (4)
H24	0.3321	0.2392	0.7161	0.055*
C25	0.41793 (15)	0.18277 (9)	0.62724 (13)	0.0445 (4)
H25	0.3563	0.1485	0.6053	0.053*
C26	0.52082 (15)	0.17821 (8)	0.59301 (11)	0.0392 (4)
H26	0.5300	0.1408	0.5482	0.047*
C27	0.69081 (12)	0.33792 (7)	0.72159 (10)	0.0274 (3)
H27	0.7606	0.3359	0.6965	0.033*
N21	0.67777 (10)	0.38848 (6)	0.78175 (8)	0.0260 (2)
N22	0.76780 (10)	0.43899 (6)	0.80416 (8)	0.0265 (2)
H22	0.8301	0.4359	0.7779	0.032*
C28	0.75845 (11)	0.49324 (7)	0.86715 (9)	0.0217 (3)
S2	0.86573 (3)	0.55753 (2)	0.89315 (2)	0.02724 (10)
N23	0.66310 (10)	0.49286 (6)	0.90542 (8)	0.0261 (2)
H23A	0.6096	0.4582	0.8893	0.031*
H23B	0.6534	0.5273	0.9469	0.031*
N31	0.44284 (12)	0.43093 (8)	0.41013 (10)	0.0408 (3)
C31	0.50736 (14)	0.44984 (10)	0.34677 (12)	0.0417 (4)
H31	0.4783	0.4882	0.3027	0.050*
O31	0.60092 (11)	0.42186 (8)	0.34074 (10)	0.0549 (3)
C32	0.48081 (17)	0.37110 (12)	0.47756 (15)	0.0614 (6)
H32A	0.5577	0.3530	0.4694	0.092*
H32B	0.4233	0.3309	0.4652	0.092*
H32C	0.4870	0.3891	0.5436	0.092*
C33	0.33580 (15)	0.46992 (12)	0.41613 (14)	0.0503 (4)
H33A	0.3216	0.5089	0.3673	0.076*
H33B	0.3438	0.4918	0.4803	0.076*
H33C	0.2695	0.4354	0.4048	0.076*
N41	1.0758 (5)	0.4003 (5)	0.6358 (5)	0.0402 (7)	0.839 (3)
C41	0.99151 (16)	0.45030 (11)	0.63041 (14)	0.0365 (5)	0.839 (3)
H41	1.0028	0.4958	0.6003	0.044*	0.839 (3)
O41	0.90127 (17)	0.44357 (13)	0.66020 (15)	0.0476 (5)	0.839 (3)
C42	1.0695 (3)	0.33192 (15)	0.6838 (2)	0.0808 (10)	0.839 (3)
H42A	0.9875	0.3217	0.6871	0.121*	0.839 (3)
H42B	1.1174	0.3346	0.7491	0.121*	0.839 (3)
H42C	1.0991	0.2924	0.6481	0.121*	0.839 (3)
C43	1.1793 (2)	0.41538 (17)	0.59595 (18)	0.0589 (7)	0.839 (3)
H43A	1.1741	0.4654	0.5693	0.088*	0.839 (3)
H43B	1.1835	0.3797	0.5449	0.088*	0.839 (3)
H43C	1.2501	0.4112	0.6469	0.088*	0.839 (3)
N51	1.091 (3)	0.403 (3)	0.635 (3)	0.0402 (7)	0.161 (3)
C51	1.0150 (8)	0.3948 (7)	0.6915 (7)	0.065 (4)	0.161 (3)
H51	1.0375	0.3620	0.7443	0.079*	0.161 (3)
O51	0.9197 (9)	0.4242 (8)	0.6841 (9)	0.0476 (5)	0.161 (3)
C52	1.0712 (13)	0.4539 (9)	0.5564 (9)	0.079 (5)	0.161 (3)
H52A	1.0699	0.4274	0.4960	0.118*	0.161 (3)
H52B	1.1345	0.4906	0.5660	0.118*	0.161 (3)
H52C	0.9956	0.4788	0.5534	0.118*	0.161 (3)
C53	1.2003 (9)	0.3610 (9)	0.6513 (9)	0.074 (5)	0.161 (3)
H53A	1.2033	0.3309	0.5945	0.110*	0.161 (3)
H53B	1.2037	0.3289	0.7073	0.110*	0.161 (3)
H53C	1.2674	0.3950	0.6635	0.110*	0.161 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0516 (7)	0.0297 (5)	0.0355 (6)	0.0109 (5)	0.0199 (5)	0.0116 (4)
C1	0.0667 (11)	0.0207 (7)	0.0275 (7)	0.0081 (7)	0.0178 (7)	0.0042 (5)
C2	0.0660 (10)	0.0198 (7)	0.0264 (7)	−0.0028 (7)	0.0169 (7)	−0.0042 (5)
O2	0.0506 (6)	0.0249 (5)	0.0304 (5)	−0.0076 (4)	0.0173 (5)	−0.0099 (4)
C11	0.0457 (9)	0.0296 (7)	0.0258 (7)	0.0111 (6)	0.0141 (6)	0.0018 (6)
C12	0.0366 (7)	0.0302 (7)	0.0241 (7)	0.0078 (6)	0.0095 (6)	0.0018 (5)
C13	0.0384 (8)	0.0423 (9)	0.0297 (8)	0.0086 (7)	0.0118 (6)	0.0046 (6)
C14	0.0380 (8)	0.0547 (10)	0.0374 (9)	0.0132 (8)	0.0119 (7)	−0.0019 (7)
C15	0.0500 (10)	0.0542 (10)	0.0359 (9)	0.0279 (8)	0.0078 (7)	0.0008 (7)
C16	0.0587 (10)	0.0393 (9)	0.0311 (8)	0.0219 (8)	0.0129 (7)	0.0072 (6)
C17	0.0322 (7)	0.0295 (7)	0.0271 (7)	0.0030 (6)	0.0102 (6)	0.0044 (5)
N11	0.0278 (6)	0.0282 (6)	0.0263 (6)	0.0045 (5)	0.0072 (5)	0.0030 (5)
N12	0.0247 (6)	0.0297 (6)	0.0277 (6)	0.0029 (5)	0.0105 (5)	0.0057 (5)
C18	0.0251 (6)	0.0257 (6)	0.0204 (6)	0.0006 (5)	0.0059 (5)	−0.0009 (5)
S1	0.02542 (18)	0.03206 (19)	0.02971 (19)	0.00731 (13)	0.00883 (14)	0.00404 (13)
N13	0.0242 (6)	0.0343 (6)	0.0298 (6)	0.0050 (5)	0.0094 (5)	0.0113 (5)
C21	0.0426 (8)	0.0226 (7)	0.0244 (7)	−0.0065 (6)	0.0073 (6)	0.0008 (5)
C22	0.0369 (7)	0.0231 (6)	0.0249 (7)	−0.0057 (6)	0.0074 (6)	−0.0002 (5)
C23	0.0404 (8)	0.0342 (8)	0.0387 (8)	−0.0069 (6)	0.0157 (7)	−0.0040 (6)
C24	0.0410 (9)	0.0435 (9)	0.0550 (11)	−0.0139 (7)	0.0158 (8)	0.0006 (8)
C25	0.0469 (9)	0.0336 (8)	0.0511 (10)	−0.0182 (7)	0.0056 (8)	0.0003 (7)
C26	0.0554 (10)	0.0254 (7)	0.0348 (8)	−0.0118 (7)	0.0047 (7)	−0.0036 (6)
C27	0.0325 (7)	0.0257 (7)	0.0257 (7)	−0.0028 (5)	0.0098 (5)	−0.0045 (5)
N21	0.0312 (6)	0.0234 (5)	0.0245 (6)	−0.0040 (5)	0.0078 (5)	−0.0025 (4)
N22	0.0280 (6)	0.0262 (6)	0.0277 (6)	−0.0046 (5)	0.0114 (5)	−0.0080 (4)
C28	0.0242 (6)	0.0218 (6)	0.0195 (6)	0.0012 (5)	0.0054 (5)	0.0002 (5)
S2	0.02784 (18)	0.02690 (18)	0.02888 (19)	−0.00679 (13)	0.01024 (14)	−0.00706 (13)
N23	0.0278 (6)	0.0251 (6)	0.0279 (6)	−0.0044 (5)	0.0111 (5)	−0.0062 (4)
N31	0.0310 (7)	0.0566 (9)	0.0369 (7)	0.0058 (6)	0.0125 (6)	0.0185 (6)
C31	0.0345 (8)	0.0581 (11)	0.0339 (8)	0.0041 (7)	0.0107 (7)	0.0177 (7)
O31	0.0406 (7)	0.0758 (9)	0.0551 (8)	0.0120 (6)	0.0255 (6)	0.0252 (7)
C32	0.0431 (10)	0.0771 (14)	0.0663 (13)	0.0054 (9)	0.0167 (9)	0.0437 (11)
C33	0.0344 (9)	0.0687 (12)	0.0499 (10)	0.0065 (8)	0.0135 (8)	0.0093 (9)
N41	0.0373 (18)	0.0547 (12)	0.0321 (7)	0.0027 (18)	0.0152 (12)	−0.0042 (6)
C41	0.0370 (10)	0.0436 (11)	0.0319 (10)	−0.0017 (8)	0.0145 (8)	−0.0062 (8)
O41	0.0368 (9)	0.0675 (16)	0.0441 (12)	0.0008 (7)	0.0210 (8)	−0.0079 (8)
C42	0.125 (3)	0.0616 (17)	0.0681 (18)	0.0312 (17)	0.0485 (18)	0.0192 (13)
C43	0.0372 (12)	0.091 (2)	0.0545 (15)	−0.0041 (12)	0.0237 (11)	−0.0256 (14)
N51	0.0373 (18)	0.0547 (12)	0.0321 (7)	0.0027 (18)	0.0152 (12)	−0.0042 (6)
C51	0.044 (7)	0.105 (12)	0.047 (7)	−0.020 (7)	0.007 (5)	−0.030 (7)
O51	0.0368 (9)	0.0675 (16)	0.0441 (12)	0.0008 (7)	0.0210 (8)	−0.0079 (8)
C52	0.074 (10)	0.115 (13)	0.057 (9)	0.021 (9)	0.037 (7)	0.014 (8)
C53	0.042 (7)	0.116 (13)	0.064 (9)	0.022 (8)	0.014 (6)	−0.032 (9)

Geometric parameters (Å, º)

O1—C11	1.3684 (18)	C27—H27	0.9500
O1—C1	1.4353 (16)	N21—N22	1.3771 (15)
C1—C2	1.492 (2)	N22—C28	1.3483 (16)
C1—H1A	0.9900	N22—H22	0.8800
C1—H1B	0.9900	C28—N23	1.3288 (16)
C2—O2	1.4308 (16)	C28—S2	1.6907 (13)
C2—H2A	0.9900	N23—H23A	0.8800
C2—H12B	0.9900	N23—H23B	0.8800
O2—C21	1.3666 (18)	N31—C31	1.327 (2)
C11—C16	1.394 (2)	N31—C33	1.447 (2)
C11—C12	1.4099 (19)	N31—C32	1.454 (2)
C12—C13	1.397 (2)	C31—O31	1.218 (2)
C12—C17	1.4646 (19)	C31—H31	0.9500
C13—C14	1.381 (2)	C32—H32A	0.9800
C13—H13	0.9500	C32—H32B	0.9800
C14—C15	1.383 (2)	C32—H32C	0.9800
C14—H14	0.9500	C33—H33A	0.9800
C15—C16	1.379 (2)	C33—H33B	0.9800
C15—H15	0.9500	C33—H33C	0.9800
C16—H16	0.9500	N41—C41	1.324 (5)
C17—N11	1.2850 (17)	N41—C42	1.424 (7)
C17—H17	0.9500	N41—C43	1.455 (4)
N11—N12	1.3759 (16)	C41—O41	1.213 (2)
N12—C18	1.3478 (17)	C41—H41	0.9500
N12—H12	0.8800	C42—H42A	0.9800
C18—N13	1.3283 (17)	C42—H42B	0.9800
C18—S1	1.6991 (13)	C42—H42C	0.9800
N13—H13A	0.8800	C43—H43A	0.9800
N13—H13B	0.8800	C43—H43B	0.9800
C21—C26	1.394 (2)	C43—H43C	0.9800
C21—C22	1.4099 (19)	N51—C51	1.323 (6)
C22—C23	1.395 (2)	N51—C52	1.424 (9)
C22—C27	1.4605 (19)	N51—C53	1.456 (6)
C23—C24	1.382 (2)	C51—O51	1.213 (5)
C23—H23	0.9500	C51—H51	0.9500
C24—C25	1.385 (2)	C52—H52A	0.9800
C24—H24	0.9500	C52—H52B	0.9800
C25—C26	1.381 (2)	C52—H52C	0.9800
C25—H25	0.9500	C53—H53A	0.9800
C26—H26	0.9500	C53—H53B	0.9800
C27—N21	1.2825 (17)	C53—H53C	0.9800
C1—O1—C11	117.23 (11)	C22—C27—H27	120.2
O1—C1—C2	108.55 (12)	C27—N21—N22	116.22 (11)
O1—C1—H1A	110.0	C28—N22—N21	118.57 (11)
C2—C1—H1A	110.0	C28—N22—H22	120.7
O1—C1—H1B	110.0	N21—N22—H22	120.7
C2—C1—H1B	110.0	N23—C28—N22	116.98 (11)
H1A—C1—H1B	108.4	N23—C28—S2	123.52 (10)
O2—C2—C1	108.47 (12)	N22—C28—S2	119.49 (10)
O2—C2—H2A	110.0	C28—N23—H23A	120.0
C1—C2—H2A	110.0	C28—N23—H23B	120.0
O2—C2—H12B	110.0	H23A—N23—H23B	120.0
C1—C2—H12B	110.0	C31—N31—C33	121.58 (14)
H2A—C2—H12B	108.4	C31—N31—C32	120.09 (14)
C2—O2—C21	117.82 (11)	C33—N31—C32	118.31 (14)
O1—C11—C16	123.94 (13)	O31—C31—N31	125.08 (15)
O1—C11—C12	116.30 (12)	O31—C31—H31	117.5
C16—C11—C12	119.76 (14)	N31—C31—H31	117.5
C13—C12—C11	118.29 (13)	N31—C32—H32A	109.5
C13—C12—C17	120.68 (13)	N31—C32—H32B	109.5
C11—C12—C17	121.02 (13)	H32A—C32—H32B	109.5
C14—C13—C12	121.47 (15)	N31—C32—H32C	109.5
C14—C13—H13	119.3	H32A—C32—H32C	109.5
C12—C13—H13	119.3	H32B—C32—H32C	109.5
C13—C14—C15	119.55 (16)	N31—C33—H33A	109.5
C13—C14—H14	120.2	N31—C33—H33B	109.5
C15—C14—H14	120.2	H33A—C33—H33B	109.5
C16—C15—C14	120.49 (15)	N31—C33—H33C	109.5
C16—C15—H15	119.8	H33A—C33—H33C	109.5
C14—C15—H15	119.8	H33B—C33—H33C	109.5
C15—C16—C11	120.44 (15)	C41—N41—C42	120.9 (3)
C15—C16—H16	119.8	C41—N41—C43	120.6 (5)
C11—C16—H16	119.8	C42—N41—C43	118.5 (3)
N11—C17—C12	118.41 (13)	O41—C41—N41	126.2 (3)
N11—C17—H17	120.8	O41—C41—H41	116.9
C12—C17—H17	120.8	N41—C41—H41	116.9
C17—N11—N12	116.99 (11)	N41—C42—H42A	109.5
C18—N12—N11	118.21 (11)	N41—C42—H42B	109.5
C18—N12—H12	120.9	H42A—C42—H42B	109.5
N11—N12—H12	120.9	N41—C42—H42C	109.5
N13—C18—N12	117.44 (11)	H42A—C42—H42C	109.5
N13—C18—S1	122.50 (10)	H42B—C42—H42C	109.5
N12—C18—S1	120.05 (10)	N41—C43—H43A	109.5
C18—N13—H13A	120.0	N41—C43—H43B	109.5
C18—N13—H13B	120.0	H43A—C43—H43B	109.5
H13A—N13—H13B	120.0	N41—C43—H43C	109.5
O2—C21—C26	124.28 (13)	H43A—C43—H43C	109.5
O2—C21—C22	115.76 (12)	H43B—C43—H43C	109.5
C26—C21—C22	119.96 (14)	C51—N51—C52	121.8 (7)
C23—C22—C21	118.76 (13)	C51—N51—C53	120.6 (8)
C23—C22—C27	121.42 (13)	C52—N51—C53	117.6 (7)
C21—C22—C27	119.74 (13)	O51—C51—N51	127.6 (9)
C24—C23—C22	120.94 (15)	O51—C51—H51	116.2
C24—C23—H23	119.5	N51—C51—H51	116.2
C22—C23—H23	119.5	N51—C52—H52A	109.5
C23—C24—C25	119.66 (16)	N51—C52—H52B	109.5
C23—C24—H24	120.2	H52A—C52—H52B	109.5
C25—C24—H24	120.2	N51—C52—H52C	109.5
C26—C25—C24	120.88 (14)	H52A—C52—H52C	109.5
C26—C25—H25	119.6	H52B—C52—H52C	109.5
C24—C25—H25	119.6	N51—C53—H53A	109.5
C25—C26—C21	119.79 (15)	N51—C53—H53B	109.5
C25—C26—H26	120.1	H53A—C53—H53B	109.5
C21—C26—H26	120.1	N51—C53—H53C	109.5
N21—C27—C22	119.69 (13)	H53A—C53—H53C	109.5
N21—C27—H27	120.2	H53B—C53—H53C	109.5
C2—C1—O1—C11	−176.33 (12)	O2—C21—C22—C23	178.65 (12)
C1—O1—C11—C16	−5.8 (2)	C26—C21—C22—C23	−0.7 (2)
C1—O1—C11—C12	174.21 (12)	O2—C21—C22—C27	1.75 (19)
O1—C11—C12—C13	179.10 (13)	C26—C21—C22—C27	−177.64 (13)
C16—C11—C12—C13	−0.9 (2)	C21—C22—C23—C24	0.2 (2)
O1—C11—C12—C17	−0.5 (2)	C27—C22—C23—C24	177.05 (15)
C16—C11—C12—C17	179.45 (14)	C22—C23—C24—C25	0.2 (3)
C11—C12—C13—C14	0.6 (2)	C23—C24—C25—C26	−0.1 (3)
C17—C12—C13—C14	−179.77 (15)	C24—C25—C26—C21	−0.5 (3)
C12—C13—C14—C15	0.1 (2)	O2—C21—C26—C25	−178.45 (14)
C13—C14—C15—C16	−0.5 (3)	C22—C21—C26—C25	0.9 (2)
C14—C15—C16—C11	0.1 (3)	C23—C22—C27—N21	2.0 (2)
O1—C11—C16—C15	−179.44 (15)	C21—C22—C27—N21	178.86 (13)
C12—C11—C16—C15	0.6 (2)	C22—C27—N21—N22	−178.21 (12)
C13—C12—C17—N11	4.1 (2)	C27—N21—N22—C28	−179.94 (12)
C11—C12—C17—N11	−176.32 (13)	N21—N22—C28—N23	1.71 (17)
C12—C17—N11—N12	−177.92 (12)	N21—N22—C28—S2	−178.05 (9)
C17—N11—N12—C18	179.20 (12)	C33—N31—C31—O31	176.36 (19)
N11—N12—C18—N13	2.38 (18)	C32—N31—C31—O31	−1.9 (3)
N11—N12—C18—S1	−178.06 (9)	C42—N41—C41—O41	−3.1 (12)
O1—C1—C2—O2	−75.91 (14)	C43—N41—C41—O41	179.3 (5)
C1—C2—O2—C21	−175.10 (11)	C52—N51—C51—O51	4 (8)
C2—O2—C21—C26	0.3 (2)	C53—N51—C51—O51	−177 (3)
C2—O2—C21—C22	−179.07 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12···O31	0.88	1.91	2.7468 (18)	159
N13—H13A···N11	0.88	2.25	2.6110 (17)	104
N13—H13A···S2^i	0.88	2.80	3.5383 (14)	143
N13—H13B···S2^ii	0.88	2.71	3.4103 (13)	138
N22—H22···O41	0.88	2.01	2.806 (2)	149
N22—H22···O51	0.88	1.86	2.704 (12)	160
N23—H23A···N21	0.88	2.25	2.6101 (16)	105
N23—H23A···S1^iii	0.88	2.87	3.5744 (14)	138
N23—H23B···S1^iv	0.88	2.61	3.3907 (13)	148
C17—H17···O31	0.95	2.48	3.225 (2)	135
C27—H27···O51	0.95	2.48	3.220 (12)	135

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