Hydrogen-bonded zigzag chains in 2,2′-dithio­dibenzoic acid–1,3-di-4-pyridylpropane (1/1)

The title 1:1 cocrystal, C₁₄H₁₀O₄S₂·C₁₃H₁₄N₂ or H₂L·bpp, has the two components connected by O—H...N hydrogen bonds to generate a one-dimensional zigzag chain running along the crystallographic a direction. These chains are further stacked into a three-dimensional supra­molecular network by weak C—H...O and C—H...π contacts. Comparison of the structural differences with previous findings suggests that deprotonated forms, hydrogen-bonding sites and flexible ligand conformations become significant factors that influence the topological arrangement and binding stoichiometry of the resulting cocrystals.

S1. Comment

Recently, the design and preparation of cocrystals with desired structures has attracted considerable interest in supramolecular chemistry and crystal engineering fields, due to their potential application in materials science (Zaworotko, 2001; Beatty et al., 2002), molecular recognition (Ghosh et al., 2006) and pharmaceutical chemistry (Remenar et al., 2003). To date, the most extensively observed cocrystals are those prepared from carboxylic acid and pyridine-type molecules. In this regard, since it possesses multiple hydrogen-bonding sites, a relatively flexible conformation and a variable degree of deprotonation, 2,2'-dithiodibenzoic acid (H₂L) is a promising candidate for binary or tertiary cocrystals. Several H₂L-based cocrystals with 4,4-bipyridine-type bases (Bi et al., 2002; Hu et al., 2004; Broker & Tiekink, 2007), isonicotinohydrazide (Meng et al., 2008), isomeric n-pyridinealdazines (n = 2, 3, 4) (Broker et al., 2008), 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (Basiuk et al., 1999) or hexamethylenetetramine (Li et al., 2001), and/or common solvent molecules (Murugavel et al., 2001; Kang et al., 2002; Kresinski & Fackler, 1994; Cai et al., 2006), have been well documented, with the acid and base components forming chain-based polymer topologies via classical O—H···N hydrogen bonds.

To investigate further the influence of framework flexibility on the resulting topology of H₂L-based cocrystals, 1,3-bis(4-pyridyl)propane (bpp) was selected to cocrystallize with H₂L in a mixed solvent, to give the title 1:1 cocrystal, (I). In addition to offering two hydrogen-bonding acceptor sites, bpp can also exhibit anti–anti, anti–gauche and gauche–gauche conformations (Niu et al., 2006), resulting from free rotation about the C—C single bonds, which may potentially induce novel supramolecular aggregation patterns.

The asymmetric unit of (I) is shown in Fig. 1. When viewed along the central S—S bond, the H₂L molecule adopts a characteristic L-shaped conformation [torsion angle C15—S1—S2—C22 = 95.43 (10)°]. A search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) yielded a mean value over 40 hits for H₂L type structures of ±86° for this C—S—S—C torsion angle. The carboxylic acid residues are almost coplanar with their respective benzene rings, and the carbonyl O atoms are adjacent to the S atoms, with S···O separations of 2.628 (2) and 2.665 (2) Å. In the neutral bpp molecule, the torsion angles C1—C2—C3—C11 [179.41 (18)°] and C6—C1—C2—C3 [62.0 (2)°] are consistent with an anti–gauche conformation.

In the crystal structure of (I), the neutral H₂L and bpp molecules are linked alternately by O1—H1···N1 and O4—H4'···N2 hydrogen bonds (Table 1) which generate a twisted zigzag chain extending along the crystallographic a-axis direction. These chains are further linked into a two-dimensional layer parallel to the (010) plane by weak C—H···O interactions (Table 2 and Fig. 2). Weak C—H···π contacts involving C10—H10 of bpp and an adjacent C21–C26 ring of H₂L are observed between the layers, leading to a three-dimensional network [H10···Cg1 = 2.75 Å, C10···Cg1 = 3.556 (3) Å and C10—H10···Cg1 = 145°, where Cg1 is the centroid of the C21–C26 ring at (1 - x, 1 - y, 1 - z)].

To explore the structural features of H₂L in cocrystals, various kinds of multifunctional N-heterocycles have already been used as cocrystallization agents `B' with H₂L (see Fig. 3). The stoichiometric ratios of the components in the known cocrystals are 1:2, 1:1, 2:1, 2:3 and 3:1 (see Fig. 3). What can be obtained depends in part on the molar ratio of the materials used, as well as on the steric congestion of the secondary cocrystal agents. Various 1:1 and 2:1 cocrystals can be isolated by controlling the molar ratio of the raw materials for the H₂L and B components, but only a 2:3 H₂L–2-pyridinealdazine (SODKIG; Broker et al., 2008) cocrystal can be reproducibly obtained despite the use of different molar ratios of the reactants. The O—H_acid···N synthon is always present in these systems. In addition, as a binary organic acid, H₂L can potentially act as a neutral molecule or as a singly or a doubly deprotonated anion in cocrystals. Only eight examples are currently known (see Fig. 3) involving deprotonated HL^- and/or L^2- anions, and here the O—H_acid···N hydrogen-bond synthon is replaced by charge-assisted O—H···O^- and N—H···N⁺ hydrogen bonds. The crystal structures all have a chain-based polymer topology, despite the variable binding stoichiometry. These hydrogen-bonded chains exhibit twisted-linear, zigzag and/or helical topologies. In addition, C—H···O and C—H···π contacts also contribute to the supramolecular aggregate patterns.

The H₂L and B components can sometimes cocrystallize with solvent molecules such as H₂O, CH₂Cl₂, dimethylformamide, tetrahydrofuran or EtOH, leading to ternary hydrogen-bonded compounds (see Fig. 3). Here, solvent interference in the cocrystallization process can significantly direct the crystallization towards a particular crystal structure. In the case of 2HL–trans-1,2-bis(4-pyridyl)ethane.2EtOH (SIQCEB; Broker & Tiekink, 2007), the solvent ethanol molecules are found in the rectangular columns formed by the HL^- anions and bipyridinium dications. In contrast, the water molecules in H₂L–hexamethylenetetramine.0.5H₂O (MIPVAI; Li et al., 2001) act as a bridges in the formation of a ladder-like double-chain.

Thus, the degree of deprotonation, the available hydrogen-bonding sites and the flexible conformation of the components, together with any solvent molecule intervention, are all important factors in governing supramolecular structures.

S2. Experimental

To an acetone–water solution (1:1, 2.0 ml) of H₂L (15.3 mg, 0.05 mmol) was added dropwise an ethanol–water solution (1:1, 3.0 ml) of bpp (30.8 mg, 0.1 mmol) with constant stirring. The mixture was further stirred for 1 h at room temperature and then filtered. The resulting yellow filtrate was allowed to evaporate at room temperature. Pale-yellow block-shaped crystals of (I) suitable for X-ray diffraction were obtained within one week in 62% yield. Elemental analysis calculated for C₂₇H₂₄N₂O₄S₂: C 64.27, H 4.79, N 5.55%; found: C 64.27, H 4.55, N 5.63%.

S3. Refinement

H atoms were located in difference maps, but were subsequently placed in calculated positions and treated as riding, with C—H = 0.93 Å and O—H = 0.82 Å, and with U_iso(H) = 1.2U_eq(C,O).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I),showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates the intermolecular O—H···N hydrogen bond.
	Fig. 2. The two-dimensional supramolecular network in (I), linked by O—H···N and C—H···O contacts (dashed lines).
	Fig. 3. The structure of 2,2'-dithiodibenzoic acid upon the formation of various co-crystals. The references for the CSD refcodes are: ACEYEN (Hu et al., 2004); ACEYEN01 (Broker & Tiekink, 2007); BIZMAZ (Meng et al., 2008); MIPVAI (Li et al., 2001); MUFNIK (Bi et al., 2002); MUFNIK01 (Broker & Tiekink, 2007); NIDDIN (Murugavel et al., 2001); SIQBOK, SIQBIE, SIQBUQ, SIQCAX, SIQCEB and SITGAE (Broker & Tiekink, 2007); SODKIG, SODKOM and SODKUS (Broker et al., 2008); WIKNOT (Kresinski & Fackler, 1994); WUBHOQ (Kang et al., 2002); XEBDEO (Cai et al., 2006); and XEXFOV (Basiuk et al., 1999).

2,2'-dithiodibenzoic acid–1,3-di-4-pyridylpropane (1/1)

Crystal data

C14H10O4S2·C13H14N2	F(000) = 1056
Mr = 504.60	Dx = 1.306 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.9613 (13) Å	Cell parameters from 5139 reflections
b = 9.3021 (5) Å	θ = 2.7–27.4°
c = 13.3790 (8) Å	µ = 0.24 mm^−1
β = 100.399 (1)°	T = 296 K
V = 2565.8 (3) Å^3	Block, pale-yellow
Z = 4	0.24 × 0.23 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4508 independent reflections
Radiation source: fine-focus sealed tube	3399 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 25.0°, θmin = 1.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −24→24
Tmin = 0.944, Tmax = 0.967	k = −11→6
12563 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0608P)^2 + 0.4257P] where P = (Fo^2 + 2Fc^2)/3
4508 reflections	(Δ/σ)max < 0.001
318 parameters	Δρmax = 0.23 e Å^−3
0 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
S1	0.79794 (3)	0.50222 (6)	0.43112 (4)	0.05352 (18)
S2	0.69963 (3)	0.52406 (7)	0.41760 (5)	0.05959 (19)
O1	0.97759 (7)	0.25743 (17)	0.48239 (12)	0.0593 (4)
H1	1.0009	0.2826	0.4425	0.089*
O2	0.92221 (7)	0.45284 (17)	0.42348 (12)	0.0597 (4)
O3	0.57347 (9)	0.5632 (2)	0.37477 (19)	0.1046 (7)
O4	0.52542 (9)	0.7740 (2)	0.3773 (2)	0.1032 (7)
H4'	0.4955	0.7319	0.3411	0.155*
N1	0.04598 (8)	0.32215 (19)	0.34271 (12)	0.0481 (4)
N2	0.42580 (10)	0.6473 (3)	0.26945 (19)	0.0853 (7)
C1	0.12821 (10)	0.4185 (2)	0.07801 (15)	0.0506 (5)
H1A	0.0963	0.4699	0.0295	0.061*
H1B	0.1380	0.3292	0.0465	0.061*
C2	0.19002 (10)	0.5090 (2)	0.10170 (15)	0.0483 (5)
H2A	0.2047	0.5316	0.0387	0.058*
H2B	0.1804	0.5988	0.1327	0.058*
C3	0.24366 (10)	0.4326 (2)	0.17221 (16)	0.0527 (5)
H3A	0.2280	0.4102	0.2343	0.063*
H3B	0.2517	0.3419	0.1409	0.063*
C4	0.03926 (10)	0.4510 (2)	0.29882 (16)	0.0491 (5)
H4	0.0158	0.5208	0.3264	0.059*
C5	0.06527 (10)	0.4862 (2)	0.21468 (16)	0.0485 (5)
H5	0.0598	0.5783	0.1875	0.058*
C6	0.09958 (9)	0.3845 (2)	0.17048 (14)	0.0426 (5)
C7	0.10602 (10)	0.2502 (2)	0.21587 (16)	0.0513 (5)
H7	0.1282	0.1776	0.1889	0.062*
C8	0.07943 (10)	0.2245 (2)	0.30104 (17)	0.0548 (5)
H8	0.0852	0.1341	0.3310	0.066*
C9	0.41408 (13)	0.5147 (3)	0.2988 (3)	0.0933 (10)
H9	0.4468	0.4670	0.3427	0.112*
C10	0.35668 (12)	0.4449 (3)	0.2680 (2)	0.0745 (7)
H10	0.3508	0.3532	0.2925	0.089*
C11	0.30750 (10)	0.5092 (2)	0.20091 (16)	0.0503 (5)
C12	0.32103 (11)	0.6430 (3)	0.16628 (19)	0.0634 (6)
H12	0.2903	0.6898	0.1185	0.076*
C13	0.37976 (12)	0.7081 (3)	0.2018 (2)	0.0790 (8)
H13	0.3874	0.7987	0.1771	0.095*
C14	0.88198 (9)	0.3087 (2)	0.54383 (14)	0.0416 (4)
C15	0.82086 (9)	0.3749 (2)	0.53162 (14)	0.0420 (4)
C16	0.77903 (11)	0.3373 (2)	0.59685 (16)	0.0516 (5)
H16	0.7383	0.3801	0.5896	0.062*
C17	0.79756 (11)	0.2367 (2)	0.67258 (16)	0.0558 (6)
H17	0.7690	0.2121	0.7155	0.067*
C18	0.85734 (11)	0.1725 (2)	0.68548 (16)	0.0539 (5)
H18	0.8696	0.1059	0.7372	0.065*
C19	0.89902 (10)	0.2081 (2)	0.62092 (14)	0.0471 (5)
H19	0.9394	0.1640	0.6290	0.057*
C20	0.92901 (9)	0.3468 (2)	0.47711 (14)	0.0436 (5)
C21	0.62873 (10)	0.7470 (2)	0.47683 (18)	0.0570 (6)
C22	0.68896 (10)	0.6785 (2)	0.49235 (16)	0.0492 (5)
C23	0.73932 (10)	0.7353 (2)	0.56369 (16)	0.0547 (6)
H23	0.7797	0.6908	0.5748	0.066*
C24	0.72980 (13)	0.8566 (3)	0.61777 (19)	0.0680 (7)
H24	0.7637	0.8927	0.6656	0.082*
C25	0.67106 (14)	0.9249 (3)	0.6021 (2)	0.0822 (8)
H25	0.6651	1.0074	0.6386	0.099*
C26	0.62084 (13)	0.8701 (3)	0.5317 (2)	0.0772 (8)
H26	0.5809	0.9165	0.5208	0.093*
C27	0.57309 (11)	0.6861 (3)	0.4040 (2)	0.0703 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0477 (3)	0.0638 (4)	0.0493 (3)	0.0061 (2)	0.0092 (2)	0.0104 (3)
S2	0.0445 (3)	0.0669 (4)	0.0624 (4)	0.0006 (3)	−0.0039 (3)	−0.0068 (3)
O1	0.0488 (9)	0.0664 (10)	0.0666 (10)	0.0105 (7)	0.0209 (7)	0.0134 (8)
O2	0.0561 (9)	0.0667 (10)	0.0605 (9)	0.0086 (7)	0.0220 (7)	0.0180 (8)
O3	0.0548 (11)	0.0892 (15)	0.151 (2)	0.0041 (10)	−0.0310 (12)	−0.0230 (14)
O4	0.0528 (11)	0.0819 (14)	0.158 (2)	0.0061 (9)	−0.0258 (12)	0.0129 (13)
N1	0.0417 (9)	0.0539 (11)	0.0491 (10)	−0.0026 (8)	0.0090 (7)	−0.0023 (8)
N2	0.0461 (12)	0.0859 (17)	0.1156 (19)	−0.0028 (11)	−0.0076 (12)	0.0264 (14)
C1	0.0512 (12)	0.0580 (13)	0.0417 (11)	−0.0022 (10)	0.0062 (9)	−0.0024 (10)
C2	0.0448 (11)	0.0578 (13)	0.0428 (11)	0.0000 (9)	0.0091 (9)	0.0038 (10)
C3	0.0521 (13)	0.0531 (13)	0.0524 (12)	0.0008 (10)	0.0080 (10)	0.0008 (10)
C4	0.0436 (11)	0.0511 (13)	0.0534 (12)	−0.0025 (9)	0.0104 (9)	−0.0127 (10)
C5	0.0447 (11)	0.0451 (12)	0.0553 (12)	0.0003 (9)	0.0078 (10)	−0.0001 (10)
C6	0.0353 (10)	0.0499 (12)	0.0405 (10)	−0.0048 (8)	0.0011 (8)	−0.0052 (9)
C7	0.0498 (12)	0.0484 (13)	0.0584 (13)	0.0031 (9)	0.0165 (10)	−0.0044 (10)
C8	0.0529 (13)	0.0488 (13)	0.0646 (14)	0.0019 (10)	0.0156 (11)	0.0074 (11)
C9	0.0456 (15)	0.105 (2)	0.119 (3)	−0.0019 (14)	−0.0118 (15)	0.0431 (19)
C10	0.0514 (14)	0.0774 (18)	0.0902 (19)	−0.0014 (12)	0.0004 (13)	0.0281 (15)
C11	0.0408 (11)	0.0574 (13)	0.0539 (12)	0.0065 (9)	0.0115 (9)	0.0028 (10)
C12	0.0430 (13)	0.0647 (15)	0.0783 (16)	0.0011 (10)	−0.0006 (11)	0.0150 (12)
C13	0.0490 (14)	0.0683 (17)	0.114 (2)	−0.0002 (12)	0.0007 (14)	0.0251 (16)
C14	0.0446 (11)	0.0433 (11)	0.0356 (10)	−0.0057 (9)	0.0039 (8)	−0.0056 (9)
C15	0.0456 (11)	0.0424 (11)	0.0371 (10)	−0.0049 (9)	0.0051 (8)	−0.0038 (8)
C16	0.0498 (12)	0.0555 (13)	0.0518 (12)	−0.0011 (10)	0.0155 (10)	−0.0035 (10)
C17	0.0673 (15)	0.0551 (14)	0.0498 (13)	−0.0112 (11)	0.0234 (11)	−0.0017 (11)
C18	0.0727 (16)	0.0477 (12)	0.0422 (11)	−0.0015 (11)	0.0127 (10)	0.0026 (10)
C19	0.0523 (12)	0.0471 (12)	0.0403 (11)	0.0016 (9)	0.0036 (9)	−0.0018 (9)
C20	0.0408 (11)	0.0515 (13)	0.0373 (10)	−0.0033 (9)	0.0037 (8)	−0.0037 (9)
C21	0.0432 (12)	0.0558 (14)	0.0701 (14)	−0.0009 (10)	0.0048 (10)	0.0088 (12)
C22	0.0429 (11)	0.0502 (12)	0.0532 (12)	−0.0049 (9)	0.0051 (9)	0.0084 (10)
C23	0.0449 (12)	0.0628 (15)	0.0544 (13)	−0.0038 (10)	0.0037 (10)	0.0023 (11)
C24	0.0678 (16)	0.0638 (16)	0.0688 (16)	−0.0091 (13)	0.0025 (13)	−0.0053 (13)
C25	0.082 (2)	0.0646 (17)	0.096 (2)	0.0035 (15)	0.0065 (16)	−0.0124 (15)
C26	0.0615 (16)	0.0653 (17)	0.103 (2)	0.0126 (13)	0.0105 (15)	0.0037 (16)
C27	0.0412 (13)	0.0676 (17)	0.0968 (19)	0.0018 (12)	−0.0022 (12)	0.0140 (15)

Geometric parameters (Å, º)

S1—C15	1.791 (2)	C9—C10	1.364 (4)
S1—S2	2.0459 (8)	C9—H9	0.9300
S2—C22	1.788 (2)	C10—C11	1.375 (3)
O1—C20	1.307 (2)	C10—H10	0.9300
O1—H1	0.8200	C11—C12	1.375 (3)
O2—C20	1.213 (2)	C12—C13	1.377 (3)
O3—C27	1.209 (3)	C12—H12	0.9300
O4—C27	1.290 (3)	C13—H13	0.9300
O4—H4'	0.8200	C14—C19	1.390 (3)
N1—C8	1.330 (3)	C14—C15	1.404 (3)
N1—C4	1.331 (3)	C14—C20	1.487 (3)
N2—C13	1.325 (3)	C15—C16	1.389 (3)
N2—C9	1.331 (3)	C16—C17	1.383 (3)
C1—C6	1.503 (3)	C16—H16	0.9300
C1—C2	1.530 (3)	C17—C18	1.370 (3)
C1—H1A	0.9700	C17—H17	0.9300
C1—H1B	0.9700	C18—C19	1.375 (3)
C2—C3	1.509 (3)	C18—H18	0.9300
C2—H2A	0.9700	C19—H19	0.9300
C2—H2B	0.9700	C21—C26	1.386 (3)
C3—C11	1.503 (3)	C21—C22	1.396 (3)
C3—H3A	0.9700	C21—C27	1.490 (3)
C3—H3B	0.9700	C22—C23	1.393 (3)
C4—C5	1.376 (3)	C23—C24	1.374 (3)
C4—H4	0.9300	C23—H23	0.9300
C5—C6	1.383 (3)	C24—C25	1.367 (4)
C5—H5	0.9300	C24—H24	0.9300
C6—C7	1.385 (3)	C25—C26	1.378 (4)
C7—C8	1.377 (3)	C25—H25	0.9300
C7—H7	0.9300	C26—H26	0.9300
C8—H8	0.9300
C15—S1—S2	105.16 (7)	C11—C12—C13	120.5 (2)
C22—S2—S1	104.84 (7)	C11—C12—H12	119.7
C20—O1—H1	109.5	C13—C12—H12	119.7
C27—O4—H4'	109.5	N2—C13—C12	122.9 (2)
C8—N1—C4	116.86 (18)	N2—C13—H13	118.5
C13—N2—C9	116.5 (2)	C12—C13—H13	118.5
C6—C1—C2	113.23 (16)	C19—C14—C15	119.23 (18)
C6—C1—H1A	108.9	C19—C14—C20	119.76 (18)
C2—C1—H1A	108.9	C15—C14—C20	121.00 (17)
C6—C1—H1B	108.9	C16—C15—C14	118.86 (18)
C2—C1—H1B	108.9	C16—C15—S1	121.59 (16)
H1A—C1—H1B	107.7	C14—C15—S1	119.54 (14)
C3—C2—C1	112.21 (18)	C17—C16—C15	120.3 (2)
C3—C2—H2A	109.2	C17—C16—H16	119.8
C1—C2—H2A	109.2	C15—C16—H16	119.8
C3—C2—H2B	109.2	C18—C17—C16	121.1 (2)
C1—C2—H2B	109.2	C18—C17—H17	119.4
H2A—C2—H2B	107.9	C16—C17—H17	119.4
C11—C3—C2	117.71 (18)	C17—C18—C19	119.1 (2)
C11—C3—H3A	107.9	C17—C18—H18	120.5
C2—C3—H3A	107.9	C19—C18—H18	120.5
C11—C3—H3B	107.9	C18—C19—C14	121.4 (2)
C2—C3—H3B	107.9	C18—C19—H19	119.3
H3A—C3—H3B	107.2	C14—C19—H19	119.3
N1—C4—C5	123.31 (19)	O2—C20—O1	123.83 (18)
N1—C4—H4	118.3	O2—C20—C14	121.95 (18)
C5—C4—H4	118.3	O1—C20—C14	114.23 (18)
C4—C5—C6	120.0 (2)	C26—C21—C22	119.3 (2)
C4—C5—H5	120.0	C26—C21—C27	120.4 (2)
C6—C5—H5	120.0	C22—C21—C27	120.3 (2)
C5—C6—C7	116.49 (18)	C23—C22—C21	118.8 (2)
C5—C6—C1	121.57 (19)	C23—C22—S2	122.15 (17)
C7—C6—C1	121.94 (18)	C21—C22—S2	118.99 (17)
C8—C7—C6	119.85 (19)	C24—C23—C22	120.5 (2)
C8—C7—H7	120.1	C24—C23—H23	119.7
C6—C7—H7	120.1	C22—C23—H23	119.7
N1—C8—C7	123.4 (2)	C25—C24—C23	120.9 (2)
N1—C8—H8	118.3	C25—C24—H24	119.6
C7—C8—H8	118.3	C23—C24—H24	119.6
N2—C9—C10	123.5 (2)	C24—C25—C26	119.3 (3)
N2—C9—H9	118.3	C24—C25—H25	120.4
C10—C9—H9	118.3	C26—C25—H25	120.4
C9—C10—C11	120.5 (2)	C25—C26—C21	121.2 (2)
C9—C10—H10	119.8	C25—C26—H26	119.4
C11—C10—H10	119.8	C21—C26—H26	119.4
C12—C11—C10	115.9 (2)	O3—C27—O4	124.0 (2)
C12—C11—C3	124.81 (19)	O3—C27—C21	121.4 (2)
C10—C11—C3	119.2 (2)	O4—C27—C21	114.6 (3)
C15—S1—S2—C22	95.43 (10)	C14—C15—C16—C17	0.2 (3)
C6—C1—C2—C3	62.0 (2)	S1—C15—C16—C17	178.77 (15)
C1—C2—C3—C11	179.41 (18)	C15—C16—C17—C18	0.4 (3)
C8—N1—C4—C5	−0.4 (3)	C16—C17—C18—C19	−0.8 (3)
N1—C4—C5—C6	1.0 (3)	C17—C18—C19—C14	0.7 (3)
C4—C5—C6—C7	−0.5 (3)	C15—C14—C19—C18	−0.2 (3)
C4—C5—C6—C1	179.47 (18)	C20—C14—C19—C18	178.56 (18)
C2—C1—C6—C5	76.3 (2)	C19—C14—C20—O2	−164.63 (19)
C2—C1—C6—C7	−103.7 (2)	C15—C14—C20—O2	14.1 (3)
C5—C6—C7—C8	−0.6 (3)	C19—C14—C20—O1	14.9 (3)
C1—C6—C7—C8	179.43 (19)	C15—C14—C20—O1	−166.44 (18)
C4—N1—C8—C7	−0.8 (3)	C26—C21—C22—C23	0.7 (3)
C6—C7—C8—N1	1.3 (3)	C27—C21—C22—C23	−177.7 (2)
C13—N2—C9—C10	−4.4 (5)	C26—C21—C22—S2	−177.50 (18)
N2—C9—C10—C11	1.8 (5)	C27—C21—C22—S2	4.1 (3)
C9—C10—C11—C12	1.8 (4)	S1—S2—C22—C23	−16.22 (19)
C9—C10—C11—C3	−177.1 (3)	S1—S2—C22—C21	161.97 (16)
C2—C3—C11—C12	−1.2 (3)	C21—C22—C23—C24	0.0 (3)
C2—C3—C11—C10	177.6 (2)	S2—C22—C23—C24	178.19 (17)
C10—C11—C12—C13	−2.8 (4)	C22—C23—C24—C25	−0.7 (4)
C3—C11—C12—C13	176.0 (2)	C23—C24—C25—C26	0.5 (4)
C9—N2—C13—C12	3.3 (5)	C24—C25—C26—C21	0.2 (4)
C11—C12—C13—N2	0.2 (4)	C22—C21—C26—C25	−0.9 (4)
C19—C14—C15—C16	−0.3 (3)	C27—C21—C26—C25	177.6 (3)
C20—C14—C15—C16	−178.98 (18)	C26—C21—C27—O3	−161.3 (3)
C19—C14—C15—S1	−178.90 (14)	C22—C21—C27—O3	17.1 (4)
C20—C14—C15—S1	2.4 (2)	C26—C21—C27—O4	17.6 (4)
S2—S1—C15—C16	−14.37 (18)	C22—C21—C27—O4	−164.0 (2)
S2—S1—C15—C14	164.22 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^i	0.82	1.81	2.622 (2)	172
O4—H4′···N2	0.82	1.78	2.597 (3)	175
C18—H18···O2^ii	0.93	2.59	3.433 (3)	150

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