Hydrogen-bonded layers in the 1:2 cocrystal of 2,2'-dithio­dibenzoic acid with isonicotinohydrazide

Cocrystallization of 2,2'-dithio­dibenzoic acid with isonicotino­hydrazide from methanol solution yields the 1:2 cocrystal 2,2'-dithio­dibenzoic acid-isonicotinohydrazide (1/2), C₁₄H₁₀O₄S₂·2C₆H₇N₃O. The component mol­ecules are linked by inter­molecular O-H...N, N-H...O, N-H...N and C-H...O hydrogen bonds into layers running parallel to the (010) plane, and these layers are further linked into a three-dimensional framework structure by means of weak aromatic [pi]-[pi] stacking inter­actions. As a potential cocrystallization agent, isonico­tino­hydrazide may be used for effective and versatile synthetic supra­molecular strategies utilizing hydrogen bonding of specific mol­ecular building blocks.

S1. Comment

Molecular recognition, a central concept in supramolecular chemistry resulting from a delicate balance of shape, size and functional complementarity, may allow for the assembly of individual entities into complex multi-component aggregates with desirable connectivities and metrics (Steed & Atwood, 2000; Lehn, 1995; Lehn et al., 1996). Although there are a variety of supramolecular interactions from which to choose, the hydrogen-bonded synthon involved the carboxylic acid group remains the most widely used for designing purely organic-based architectures owing to its strength, directionality, specificity and potential for electronic/geometric fine-tuning (Aakeroÿ et al., 2002, 2005, 2006; Aakeroÿ & Salmon, 2005; Braga & Grepioni, 2005; Varaghese & Pedireddi, 2006). 2,2'-Dithiodibenzoic acid (DSDA), possessing two carboxylic acid groups, has been often employed as a bridge ligand in metal coordination chemistry (Murugavel et al., 2001); however, because of its insolubility in water, molecular adducts based on DSDA have been reported for only a few cases to date (Li et al., 2001; Cai et al., 2006; Kang et al., 2002; Hu et al., 2004). With the aim of investigating the structural diversity arising from two hydrogen-bonded R-COOH groups and an N-containing heterocycle in the solid state, we used isonicotinohydrazide (INAH) as the potential cocrystallization agent. We report here the crystal structure of the title compound, (I).

The asymmetric unit of (I) comprises one DSDA and two INAH molecules, which are joined together by the expected carboxylic acid–N(heterocycle) hydrogen bonds (Fig. 1). The dihedral angle between the two benzene rings [76.0 (1)°], the disulfide bridge [2.052 (1) Å] and the average S—C bonds distance [1.782 (3) Å] in DSDA are all comparable to those observed in some analogs [Cambridge Structural Database (Allen, 2002) refcodes ACEYEH, MIPVAI, MUFNIK, WUBHOQ, XEBDEO and XEXFOV {please provide original references for each of these structures}]. According to the definitions of a cocrystal proposed by Aakeröy et al. (2005) [and/or Aakeröy & Salmon, 2005?], (I) can be regarded as the first binary acyl hydrazine-containing cocrystal. In DSDA, the C—O bond lengths in both the carboxylic acid groups [C19—O3 = 1.211 (3) Å, C19—O4 = 1.309 (3) Å, C26—O5 = 1.209 (3) Å and C26—O6 = 1.316 (3) Å] agree well with those tabulated in the International Tables for Crystallography (1992, Vol. C, Table 9.5.1.1, pp. 685–706) for a carboxylic acid group attached to a phenyl ring [1.305 (20) and 1.226 (20) Å]. In the INAH molecules, the C3—N1—C4 and C9—N4—C10 bond angles [117.5 (3) and 116.6 (3)°, respectively] are also consistent with the unprotonated-conformation C—N—C angle of 116.3 (16)° in pyridine molecules (Allen, 2002), although the size of the s.u. values prevents any firm conclusions being drawn from this comparison. Owing to the difference of the basicity of N atoms in pyridine and that in the hydrazine group, INAH may be used as a linker agent in constructing binary or ternary cocrystals.

In the supramolecular structure of (I) (Fig. 2), N—H···N hydrogen bonds link the INAH molecules to form two types of dimers, (IIa) and (IIb). The molecular components are further linked by N—H···O and C—H···O hydrogen bonds into two-dimensional layers, and these adjacent layers are then linked by weak π–π stacking interactions into a three-dimensional framework that can be analyzed in terms of several substructures.

Firstly, INAH molecules are linked by intermolecular N2···O2ⁱ, N3···N3ⁱⁱ, N5···N6^iv and N6···O1^vii hydrogen bonds (symmetry codes as in Table 1) into two-dimensional layers (layers A) running parallel to the (010) plane. These layers comprise four types of centrosymmetric hydrogen-bond motifs, namely R²₂(4), R²₂(6), R⁴₄(18) and R⁸₈(18) (Fig. 2); the reference layer is in the domain -0.380 < y < 0.380. Although the R²₂(4) motif exists frequently in nature, it has only been discussed in detail in a few reports (Glidewell et al., 1996; Eppel & Bernstein, 2008); the other three motifs are all commonly observed in hydrogen-bonded supramolecular complexes (Bernstein et al., 1995). The two-dimensional layers are further augmented by weak C9—H9···O1^vi hydrogen bonds [C···O = 3.292 (4) Å, C—H···O = 140°] and strong π–π stacking interactions between inversion-related N4-containing pyridine fragments. The face-to-face pyridine rings are strictly parallel, with an inter-planar spacing of 3.612 (1) Å, and the ring-centroid separation is 3.707 (1) Å, corresponding to a ring offset of 0.832 (1) Å.

Secondly, DSDA molecules are linked to the INAH molecules by the remaining two strong (O4···N1 and O6···N4) and two weak (N3···O3ⁱⁱ and N6···O5^v) hydrogen bonds, expanding the above-mentioned two-dimensional layers into the domain -0.811 < y < 0.811 (denoted layer B); this layer is about two times thicker than layer A (Fig.3). Finally, neighbouring B layers are linked by rather weak π–π stacking interactions between parallel symmetry-related C20–C25 benzene rings, with a centroid-to-centroid distance of 4.298 (2) Å, an interplanar spacing of 3.584 (2) Å and a larger ring offset of 2.372 (1) Å.

In summary, this study provides a foundation for effective and versatile synthetic supramolecular strategies by using INAH molecules as a molecular building block. It should be possible to construct a wide variety of heteromolecular architectures with predetermined connectivities and dimensions.

Related literature

For related literature, see: Aakeröy & Salmon (2005); Aakeroÿ et al. (2002, 2005); Allen (2002); Allen et al. (1992); Bernstein et al. (1995); Braga & Grepioni (2005); Cai et al. (2006); Eppel & Bernstein (2008); Glidewell et al. (1996); Hu et al. (2004); Kang et al. (2002); Lehn (1995); Lehn et al. (1996); Li et al. (2001); Murugavel et al. (2001); Steed & Atwood (2000); Varaghese & Pedireddi (2006).

S2. Experimental

All the reagents and solvents were used as obtained without further purification. Equivalent molar amounts of 2,2'-dithiodibenzoic acid (0.1 mmol, 0.0306 g) and isonicotinohydrazide (0.2 mmol, 0.0274 g) were dissolved in 95% methanol (10 ml). The mixture was stirred for 10 min at ambient temperature and then filtered. The resulting light-brown solution was kept in air for two weeks. Plate-like pale-yellow [red according to CIF] crystals of (I) suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solution at the bottom of the vessel (yield 6.8.2 mg, 10%, based on 1:2 cocrystal).

S3. Refinement

H atoms bonded to C atoms were positioned geometrically (C–H = 0.93 Å) and treated as riding [U_iso(H) = 1.2U_eq(C)]. H atoms bonded to N and O atoms were found in difference maps and the N—H and O—H distances were refined freely [the refined distances are given in Table 1; U_iso(H) = 1.2U_eq(N) and 1.5U_eq(O), respectively].

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
	Fig. 2. Part of the crystal structure of (I), showing the two-dimensional layer formed only by INAH molecules running parallel to the (010) plane. Hydrogen bonds are shown as dashed lines. For clarity, the DSDA molecules and H atoms not involved in the motif have been omitted.
	Fig. 3. Part of the crystal structure of (I), showing the formation of the (010) two-dimensional layer built up by hydrogen bonds involving both DSDA and INAH molecules. Hydrogen bonds are shown as dashed lines. For clarity, H atoms not involved in the motif have been omitted.

2,2'-dithiodibenzoic acid–isonicotinohydrazide (1/2)

Crystal data

C14H10O4S2·2C6H7N3O	Z = 2
Mr = 580.63	F(000) = 604
Triclinic, P1	Dx = 1.462 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8821 (8) Å	Cell parameters from 2241 reflections
b = 11.0170 (9) Å	θ = 2.4–21.4°
c = 12.2592 (10) Å	µ = 0.26 mm^−1
α = 83.444 (1)°	T = 298 K
β = 88.054 (1)°	Plate, red
γ = 84.345 (1)°	0.10 × 0.06 × 0.04 mm
V = 1319.14 (19) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5145 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	3619 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
0.3° wide ω exposures scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −12→12
Tmin = 0.886, Tmax = 0.990	k = −13→13
12845 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.062P)^2 + 0.1314P] where P = (Fo^2 + 2Fc^2)/3
5145 reflections	(Δ/σ)max < 0.001
385 parameters	Δρmax = 0.30 e Å^−3
0 restraints	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
C1	−0.1097 (3)	0.1583 (2)	0.5380 (2)	0.0353 (6)
C2	−0.0377 (3)	0.1620 (3)	0.4392 (2)	0.0421 (7)
H2	−0.0531	0.1083	0.3886	0.051*
C3	0.0569 (3)	0.2458 (3)	0.4161 (2)	0.0475 (8)
H3	0.1051	0.2467	0.3496	0.057*
C4	0.0106 (3)	0.3232 (3)	0.5793 (3)	0.0483 (8)
H4	0.0256	0.3798	0.6273	0.058*
C5	−0.0837 (3)	0.2418 (3)	0.6090 (2)	0.0426 (7)
H5	−0.1298	0.2426	0.6763	0.051*
C6	−0.2102 (3)	0.0675 (3)	0.5739 (2)	0.0409 (7)
N1	0.0821 (2)	0.3255 (2)	0.4850 (2)	0.0475 (7)
N2	−0.2642 (3)	0.0154 (3)	0.4958 (2)	0.0514 (7)
H2A	−0.244 (3)	0.037 (3)	0.431 (3)	0.062*
N3	−0.3597 (3)	−0.0714 (3)	0.5175 (3)	0.0628 (9)
H3A	−0.326 (4)	−0.135 (2)	0.555 (3)	0.075*
H3B	−0.421 (3)	−0.046 (3)	0.555 (2)	0.075*
O1	−0.2380 (2)	0.0435 (2)	0.67213 (17)	0.0621 (7)
C7	1.6566 (3)	0.0793 (2)	0.1208 (2)	0.0372 (7)
C8	1.5404 (3)	0.0694 (3)	0.1846 (3)	0.0493 (8)
H8	1.5454	0.0298	0.2558	0.059*
C9	1.4171 (3)	0.1179 (3)	0.1434 (3)	0.0543 (9)
H9	1.3402	0.1112	0.1887	0.065*
C10	1.5144 (3)	0.1830 (3)	−0.0202 (3)	0.0535 (9)
H10	1.5063	0.2220	−0.0914	0.064*
C11	1.6411 (3)	0.1381 (3)	0.0153 (2)	0.0475 (8)
H11	1.7167	0.1469	−0.0312	0.057*
N4	1.4015 (2)	0.1739 (2)	0.0422 (2)	0.0503 (7)
C12	1.7903 (3)	0.0284 (3)	0.1687 (2)	0.0399 (7)
N5	1.8966 (3)	0.0221 (2)	0.0996 (2)	0.0465 (7)
H5A	1.886 (3)	0.038 (3)	0.029 (3)	0.056*
N6	2.0265 (3)	−0.0290 (3)	0.1353 (2)	0.0567 (7)
H6A	2.055 (3)	−0.073 (2)	0.1978 (16)	0.068*
H6B	2.063 (3)	0.0379 (13)	0.139 (2)	0.068*
O2	1.8005 (2)	−0.0061 (2)	0.26723 (16)	0.0554 (6)
C13	0.4765 (3)	0.5258 (2)	0.3540 (2)	0.0332 (6)
C14	0.5966 (3)	0.4930 (2)	0.2951 (2)	0.0341 (6)
C15	0.6845 (3)	0.5827 (3)	0.2644 (2)	0.0422 (7)
H15	0.7643	0.5626	0.2253	0.051*
C16	0.6554 (3)	0.7004 (3)	0.2908 (3)	0.0494 (8)
H16	0.7150	0.7593	0.2688	0.059*
C17	0.5384 (3)	0.7318 (3)	0.3498 (3)	0.0523 (8)
H17	0.5193	0.8112	0.3686	0.063*
C18	0.4507 (3)	0.6443 (3)	0.3803 (2)	0.0431 (7)
H18	0.3716	0.6655	0.4199	0.052*
C19	0.3751 (3)	0.4353 (3)	0.3851 (2)	0.0370 (7)
C20	0.9415 (3)	0.3499 (3)	−0.0036 (2)	0.0362 (7)
C21	0.8277 (3)	0.3781 (2)	0.0644 (2)	0.0354 (7)
C22	0.7142 (3)	0.4466 (3)	0.0174 (2)	0.0461 (8)
H22	0.6381	0.4651	0.0614	0.055*
C23	0.7128 (3)	0.4875 (3)	−0.0929 (3)	0.0539 (9)
H23	0.6369	0.5351	−0.1224	0.065*
C24	0.8230 (4)	0.4582 (3)	−0.1597 (3)	0.0596 (9)
H24	0.8211	0.4842	−0.2346	0.072*
C25	0.9349 (3)	0.3908 (3)	−0.1152 (2)	0.0493 (8)
H25	1.0092	0.3716	−0.1608	0.059*
C26	1.0681 (3)	0.2813 (3)	0.0411 (2)	0.0400 (7)
O3	0.3859 (2)	0.3334 (2)	0.35568 (18)	0.0527 (6)
O4	0.2723 (2)	0.4780 (2)	0.44413 (17)	0.0497 (6)
H4A	0.206 (4)	0.418 (3)	0.464 (3)	0.075*
O5	1.0847 (2)	0.2491 (2)	0.13772 (17)	0.0538 (6)
O6	1.1615 (2)	0.2591 (2)	−0.03501 (18)	0.0580 (6)
H6	1.243 (4)	0.233 (4)	−0.001 (3)	0.087*
S1	0.63294 (8)	0.33963 (7)	0.26177 (6)	0.0447 (2)
S2	0.83205 (8)	0.32746 (7)	0.20758 (6)	0.0448 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0281 (15)	0.0398 (16)	0.0363 (15)	0.0000 (13)	−0.0009 (12)	0.0003 (12)
C2	0.0394 (17)	0.0509 (19)	0.0362 (16)	−0.0047 (15)	0.0025 (13)	−0.0059 (13)
C3	0.0419 (18)	0.066 (2)	0.0331 (16)	−0.0054 (16)	0.0065 (13)	−0.0033 (15)
C4	0.0398 (18)	0.057 (2)	0.0508 (19)	−0.0085 (15)	0.0020 (15)	−0.0138 (15)
C5	0.0348 (17)	0.059 (2)	0.0350 (16)	−0.0063 (15)	0.0063 (12)	−0.0091 (14)
C6	0.0379 (17)	0.0455 (18)	0.0373 (17)	0.0010 (14)	0.0015 (13)	−0.0013 (14)
N1	0.0345 (15)	0.0600 (17)	0.0476 (16)	−0.0091 (13)	0.0039 (12)	−0.0011 (13)
N2	0.0495 (17)	0.0640 (19)	0.0430 (15)	−0.0209 (14)	−0.0018 (13)	−0.0023 (14)
N3	0.053 (2)	0.059 (2)	0.078 (2)	−0.0191 (16)	−0.0011 (16)	−0.0041 (16)
O1	0.0717 (17)	0.0755 (17)	0.0407 (13)	−0.0269 (13)	0.0135 (11)	−0.0011 (11)
C7	0.0401 (17)	0.0372 (16)	0.0360 (16)	−0.0070 (13)	0.0037 (13)	−0.0097 (12)
C8	0.046 (2)	0.058 (2)	0.0437 (18)	−0.0086 (16)	0.0073 (15)	−0.0014 (15)
C9	0.043 (2)	0.069 (2)	0.052 (2)	−0.0119 (17)	0.0127 (16)	−0.0071 (17)
C10	0.0402 (19)	0.072 (2)	0.0449 (19)	−0.0004 (17)	0.0037 (15)	0.0007 (16)
C11	0.0349 (18)	0.067 (2)	0.0397 (17)	−0.0026 (15)	0.0062 (13)	−0.0047 (15)
N4	0.0317 (15)	0.0610 (18)	0.0584 (17)	−0.0032 (13)	0.0022 (12)	−0.0097 (14)
C12	0.0436 (18)	0.0412 (17)	0.0358 (17)	−0.0046 (14)	−0.0005 (14)	−0.0076 (13)
N5	0.0383 (15)	0.0621 (18)	0.0368 (14)	0.0059 (13)	−0.0048 (12)	−0.0034 (13)
N6	0.0417 (17)	0.076 (2)	0.0469 (16)	0.0155 (15)	−0.0081 (13)	0.0024 (14)
O2	0.0623 (15)	0.0667 (15)	0.0353 (12)	−0.0039 (12)	−0.0011 (10)	0.0013 (10)
C13	0.0322 (16)	0.0379 (16)	0.0290 (14)	−0.0030 (12)	−0.0035 (11)	−0.0016 (12)
C14	0.0336 (16)	0.0399 (16)	0.0289 (14)	−0.0066 (13)	0.0004 (12)	−0.0021 (12)
C15	0.0408 (18)	0.0468 (19)	0.0399 (17)	−0.0126 (14)	0.0033 (13)	−0.0025 (14)
C16	0.050 (2)	0.044 (2)	0.055 (2)	−0.0193 (16)	−0.0050 (16)	−0.0002 (15)
C17	0.056 (2)	0.0419 (19)	0.061 (2)	−0.0073 (16)	−0.0038 (17)	−0.0120 (16)
C18	0.0399 (18)	0.0451 (19)	0.0445 (17)	−0.0010 (14)	−0.0032 (13)	−0.0081 (14)
C19	0.0305 (16)	0.0481 (19)	0.0313 (15)	−0.0035 (14)	−0.0018 (12)	0.0002 (13)
C20	0.0315 (16)	0.0415 (17)	0.0363 (16)	−0.0061 (13)	0.0021 (12)	−0.0060 (12)
C21	0.0317 (16)	0.0378 (16)	0.0374 (16)	−0.0050 (13)	−0.0003 (12)	−0.0066 (12)
C22	0.0375 (18)	0.0520 (19)	0.0467 (19)	0.0040 (15)	0.0014 (14)	−0.0041 (15)
C23	0.046 (2)	0.066 (2)	0.047 (2)	0.0090 (17)	−0.0104 (16)	−0.0024 (16)
C24	0.058 (2)	0.089 (3)	0.0292 (17)	0.001 (2)	−0.0051 (15)	0.0017 (17)
C25	0.0390 (18)	0.072 (2)	0.0373 (17)	−0.0065 (16)	0.0071 (14)	−0.0084 (15)
C26	0.0323 (17)	0.0470 (18)	0.0428 (18)	−0.0099 (14)	0.0032 (13)	−0.0100 (14)
O3	0.0491 (14)	0.0483 (14)	0.0633 (14)	−0.0171 (11)	0.0181 (11)	−0.0129 (11)
O4	0.0364 (12)	0.0570 (14)	0.0558 (14)	−0.0081 (10)	0.0146 (10)	−0.0075 (11)
O5	0.0403 (13)	0.0760 (16)	0.0409 (13)	0.0067 (11)	0.0023 (10)	0.0002 (11)
O6	0.0344 (13)	0.0898 (18)	0.0473 (13)	0.0066 (12)	0.0070 (10)	−0.0099 (12)
S1	0.0433 (5)	0.0398 (5)	0.0507 (5)	−0.0061 (3)	0.0142 (4)	−0.0066 (3)
S2	0.0388 (4)	0.0557 (5)	0.0359 (4)	0.0054 (4)	0.0052 (3)	0.0019 (3)

Geometric parameters (Å, º)

C1—C2	1.382 (4)	N6—H6B	0.86 (2)
C1—C5	1.384 (4)	C13—C18	1.378 (4)
C1—C6	1.498 (4)	C13—C14	1.407 (4)
C2—C3	1.377 (4)	C13—C19	1.493 (4)
C2—H2	0.9300	C14—C15	1.390 (4)
C3—N1	1.332 (4)	C14—S1	1.783 (3)
C3—H3	0.9300	C15—C16	1.373 (4)
C4—N1	1.332 (4)	C15—H15	0.9300
C4—C5	1.368 (4)	C16—C17	1.378 (4)
C4—H4	0.9300	C16—H16	0.9300
C5—H5	0.9300	C17—C18	1.372 (4)
C6—O1	1.231 (3)	C17—H17	0.9300
C6—N2	1.323 (4)	C18—H18	0.9300
N2—N3	1.407 (4)	C19—O3	1.211 (3)
N2—H2A	0.82 (3)	C19—O4	1.309 (3)
N3—H3A	0.843 (18)	C20—C25	1.393 (4)
N3—H3B	0.80 (3)	C20—C21	1.408 (4)
C7—C8	1.374 (4)	C20—C26	1.484 (4)
C7—C11	1.384 (4)	C21—C22	1.392 (4)
C7—C12	1.496 (4)	C21—S2	1.781 (3)
C8—C9	1.370 (4)	C22—C23	1.376 (4)
C8—H8	0.9300	C22—H22	0.9300
C9—N4	1.327 (4)	C23—C24	1.376 (4)
C9—H9	0.9300	C23—H23	0.9300
C10—N4	1.337 (4)	C24—C25	1.364 (4)
C10—C11	1.367 (4)	C24—H24	0.9300
C10—H10	0.9300	C25—H25	0.9300
C11—H11	0.9300	C26—O5	1.209 (3)
C12—O2	1.229 (3)	C26—O6	1.316 (3)
C12—N5	1.328 (4)	O4—H4A	0.98 (4)
N5—N6	1.413 (4)	O6—H6	0.93 (4)
N5—H5A	0.87 (3)	S1—S2	2.0519 (11)
N6—H6A	0.90 (2)
C2—C1—C5	117.4 (3)	N5—N6—H6B	99 (2)
C2—C1—C6	124.2 (3)	H6A—N6—H6B	101.2 (13)
C5—C1—C6	118.4 (2)	C18—C13—C14	119.3 (2)
C1—C2—C3	119.6 (3)	C18—C13—C19	119.8 (3)
C1—C2—H2	120.2	C14—C13—C19	120.9 (2)
C3—C2—H2	120.2	C15—C14—C13	118.3 (3)
N1—C3—C2	122.8 (3)	C15—C14—S1	121.7 (2)
N1—C3—H3	118.6	C13—C14—S1	119.9 (2)
C2—C3—H3	118.6	C16—C15—C14	121.1 (3)
N1—C4—C5	123.3 (3)	C16—C15—H15	119.5
N1—C4—H4	118.3	C14—C15—H15	119.5
C5—C4—H4	118.3	C15—C16—C17	120.4 (3)
C4—C5—C1	119.4 (3)	C15—C16—H16	119.8
C4—C5—H5	120.3	C17—C16—H16	119.8
C1—C5—H5	120.3	C18—C17—C16	119.1 (3)
O1—C6—N2	123.0 (3)	C18—C17—H17	120.5
O1—C6—C1	120.1 (3)	C16—C17—H17	120.5
N2—C6—C1	116.9 (3)	C17—C18—C13	121.8 (3)
C3—N1—C4	117.5 (3)	C17—C18—H18	119.1
C6—N2—N3	123.0 (3)	C13—C18—H18	119.1
C6—N2—H2A	119 (2)	O3—C19—O4	123.6 (3)
N3—N2—H2A	118 (2)	O3—C19—C13	122.9 (3)
N2—N3—H3A	111 (3)	O4—C19—C13	113.4 (3)
N2—N3—H3B	111 (3)	C25—C20—C21	118.5 (3)
H3A—N3—H3B	104 (3)	C25—C20—C26	119.7 (3)
C8—C7—C11	116.8 (3)	C21—C20—C26	121.8 (2)
C8—C7—C12	118.9 (3)	C22—C21—C20	118.6 (3)
C11—C7—C12	124.3 (3)	C22—C21—S2	121.5 (2)
C9—C8—C7	119.9 (3)	C20—C21—S2	119.9 (2)
C9—C8—H8	120.0	C23—C22—C21	121.1 (3)
C7—C8—H8	120.0	C23—C22—H22	119.4
N4—C9—C8	123.6 (3)	C21—C22—H22	119.4
N4—C9—H9	118.2	C22—C23—C24	120.3 (3)
C8—C9—H9	118.2	C22—C23—H23	119.9
N4—C10—C11	123.3 (3)	C24—C23—H23	119.9
N4—C10—H10	118.3	C25—C24—C23	119.4 (3)
C11—C10—H10	118.3	C25—C24—H24	120.3
C10—C11—C7	119.8 (3)	C23—C24—H24	120.3
C10—C11—H11	120.1	C24—C25—C20	122.0 (3)
C7—C11—H11	120.1	C24—C25—H25	119.0
C9—N4—C10	116.6 (3)	C20—C25—H25	119.0
O2—C12—N5	122.0 (3)	O5—C26—O6	123.0 (3)
O2—C12—C7	121.2 (3)	O5—C26—C20	123.7 (3)
N5—C12—C7	116.8 (3)	O6—C26—C20	113.3 (3)
C12—N5—N6	121.5 (3)	C19—O4—H4A	113 (2)
C12—N5—H5A	121 (2)	C26—O6—H6	109 (2)
N6—N5—H5A	117 (2)	C14—S1—S2	105.38 (9)
N5—N6—H6A	133 (2)	C21—S2—S1	105.62 (10)
C5—C1—C2—C3	1.0 (4)	C13—C14—C15—C16	0.1 (4)
C6—C1—C2—C3	−177.1 (3)	S1—C14—C15—C16	−179.8 (2)
C1—C2—C3—N1	−0.6 (5)	C14—C15—C16—C17	0.7 (5)
N1—C4—C5—C1	−1.3 (5)	C15—C16—C17—C18	−0.9 (5)
C2—C1—C5—C4	−0.1 (4)	C16—C17—C18—C13	0.2 (5)
C6—C1—C5—C4	178.1 (3)	C14—C13—C18—C17	0.6 (4)
C2—C1—C6—O1	157.2 (3)	C19—C13—C18—C17	−177.5 (3)
C5—C1—C6—O1	−20.9 (4)	C18—C13—C19—O3	173.1 (3)
C2—C1—C6—N2	−22.0 (4)	C14—C13—C19—O3	−5.0 (4)
C5—C1—C6—N2	160.0 (3)	C18—C13—C19—O4	−5.1 (4)
C2—C3—N1—C4	−0.7 (5)	C14—C13—C19—O4	176.8 (2)
C5—C4—N1—C3	1.7 (5)	C25—C20—C21—C22	−0.6 (4)
O1—C6—N2—N3	0.8 (5)	C26—C20—C21—C22	177.7 (3)
C1—C6—N2—N3	180.0 (3)	C25—C20—C21—S2	180.0 (2)
C11—C7—C8—C9	−0.8 (4)	C26—C20—C21—S2	−1.7 (4)
C12—C7—C8—C9	178.5 (3)	C20—C21—C22—C23	−0.7 (4)
C7—C8—C9—N4	1.1 (5)	S2—C21—C22—C23	178.7 (2)
N4—C10—C11—C7	0.1 (5)	C21—C22—C23—C24	1.8 (5)
C8—C7—C11—C10	0.2 (4)	C22—C23—C24—C25	−1.6 (5)
C12—C7—C11—C10	−179.1 (3)	C23—C24—C25—C20	0.2 (5)
C8—C9—N4—C10	−0.8 (5)	C21—C20—C25—C24	0.9 (5)
C11—C10—N4—C9	0.1 (5)	C26—C20—C25—C24	−177.5 (3)
C8—C7—C12—O2	−10.3 (4)	C25—C20—C26—O5	175.4 (3)
C11—C7—C12—O2	169.0 (3)	C21—C20—C26—O5	−2.9 (4)
C8—C7—C12—N5	169.5 (3)	C25—C20—C26—O6	−4.3 (4)
C11—C7—C12—N5	−11.2 (4)	C21—C20—C26—O6	177.4 (2)
O2—C12—N5—N6	2.3 (5)	C15—C14—S1—S2	11.8 (2)
C7—C12—N5—N6	−177.4 (2)	C13—C14—S1—S2	−168.14 (19)
C18—C13—C14—C15	−0.8 (4)	C22—C21—S2—S1	18.2 (3)
C19—C13—C14—C15	177.3 (2)	C20—C21—S2—S1	−162.45 (19)
C18—C13—C14—S1	179.1 (2)	C14—S1—S2—C21	−87.08 (13)
C19—C13—C14—S1	−2.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2^i	0.82 (3)	2.14 (3)	2.884 (3)	150 (3)
N3—H3A···O3^ii	0.84 (2)	2.44 (3)	3.148 (4)	142 (3)
N3—H3B···N3^iii	0.80 (3)	2.55 (2)	3.068 (7)	125 (2)
N5—H5A···N6^iv	0.87 (3)	2.18 (3)	2.947 (4)	148 (3)
N6—H6B···O5^v	0.86 (2)	2.36 (1)	3.177 (4)	160 (3)
C9—H9···O1^vi	0.93	2.53	3.292 (4)	140
N6—H6A···O1^vii	0.90 (2)	2.52 (2)	3.187 (3)	131 (2)
O4—H4A···N1	0.98 (4)	1.66 (4)	2.642 (3)	174 (3)
O6—H6···N4	0.93 (4)	1.71 (4)	2.629 (3)	171 (4)
C15—H15···S2	0.93	2.64	3.176 (3)	117
C22—H22···S1	0.93	2.68	3.197 (3)	116

Symmetry codes: (i) x−2, y, z; (ii) −x, −y, −z+1; (iii) −x−1, −y, −z+1; (iv) −x+4, −y, −z; (v) x+1, y, z; (vi) −x+1, −y, −z+1; (vii) −x+2, −y, −z+1.