Polysulfonylamines. CXXXII. A robust eight-membered ring motif in the hydrogen-bonded structure of 2-amino­pyridinium di­(benzene­sulfonyl)­amidate

The crystal structure of the title compound, C₅H₇N₂⁺·C₁₂H₁₀NO₄S₂⁻, consists of two independent cation–anion pairs, A and B. Within each pair, the H—N—C—N*—H grouping (N*—H is the pyridinium function) and one N—S—O moiety of the anion are linked by N*—H...N and N—H...O hydrogen bonds to form an antidromic ring motif of type R²₂(8). The remaining amino donors give rise to N—H...O hydrogen bonds, connecting the ion pairs into A–B–A–B– chains. The structure testifies to the persistence of the R²₂(8) motif in question, which was previously detected as a highly robust supramolecular synthon in a series of onium di(methane­sulfonyl)­amidates. The structure is pseudosymmetric; the anion positions correspond to space group P2₁/n, but those of the cations do not.

S1. Comment

The design process in crystal engineering depends crucially on the `robustness', or high probability of formation, of a limited number of supramolecular synthons (Desiraju, 1995; Aakeröy, 1997). Among these non-covalent interactions, bimolecular hydrogen-bonded ring motifs (Allen et al., 1999) are prominently utilized for controlling the assembly of complementary molecular building blocks into finite or infinite architectures (Subramanian & Zaworotko, 1994). Since the hydrogen bond is primarily electrostatic in nature, the strengths of such interactions involving charged species is enhanced and, as a result, acyclic or preferentially cyclic hydrogen-bonded motifs become a powerful tool for linking ions together in a predictable manner (Aakeröy, 1997; Aakeröy & Seddon, 1993; Mascal et al., 1995; Braga & Grepioni, 1999).

This laboratory has synthesized and characterized a series of onium di(methanesulfonyl)amidates, BH⁺·(MeSO₂)₂N^-, in which a novel and remarkably robust antidromic ring synthon of second-level graph set R²₂(8) (Bernstein et al., 1995) is systematically formed from a V-shaped O—S—N fragment of the conformationally rigid anion and syn,syn-[H—N—Csp²—N—H] sequences drawn from a variety of organic cations. In order to demonstrate its high probability of formation, the motif in question was successfully integrated into hydrogen-bonded assemblies of increasing complexity, i.e. prototypical ion pairs (Wijaya et al., 1999), cyclodimers and catemers of ion pairs (Moers, Wijaya et al., 2000) and three-dimensional networks (Wijaya et al., 2000). The 2-aminopyridinium salt, (I), represents an example for a catemeric structure composed of R²₂(8) bonded ion pairs, and the structure determination of the analogous title compound, (II), was carried out in order to evaluate the influence of a sterically more demanding disulfonylamidate anion on the robustness of the target motif. \scheme

The asymmetric unit of (II) consists of two crystallographically independent ion pairs, A (unprimed labels) and B (primed labels), as shown in Fig. 1. Important bond lengths, bond angles, torsion angles and intraionic non-bonded distances are summarized in Table 1. The two anions adopt extended conformations approximating to C₂ symmetry, in which each O₂S—N—S moiety displays an antiperiplanar and a synclinal O atom, denoted hereafter as O(ap) and O(sc), respectively. The molecular dimensions of the ions are normal and similar to those observed in (I) and other related structures [2-aminopyridinium: Henschel et al. (1999), and references therein; di(benzenesulfonyl)amidate (extended form): Henschel et al. (1997); di(benzenesulfonyl)amidate (folded form): Cotton & Stokely (1970); Bombicz et al. (1996)]. A combination of N—H···N, N—H···O and C—H···O hydrogen bonds (Table 2) links the ions into a three-dimensional framework. It is noteworthy that the weak C—H···O bonds exhaustively satisfy all acceptors that are not involved in classical H bonds.

As is apparent from Fig. 1, the antidromic R²₂(8) motif observed in structure (I) neatly persists in the ion pairs of (II). There is no change in the way in which the oppositely charged ions are held together. In both crystals, the ring-forming hydrogen bonds connect the pyridinium donor to the amidate N acceptor and one of the amino donors to an O(ap) acceptor. The near planarity of the D₂A₂ systems in A and B is testimony to the robustness of the motif [dihedral angles: N2—N1—O1—N3 - 3.55 (10) and N2'—N1'—O1'—N3' 8.13 (10)°; deviations of C and S ring atoms from the respective D₂A₂ mean plane: C3 0.055 (4), S1 - 0.113 (2), C3' -0.071 (4) and S1' -0.246 (2) Å]. The amino donors not involved in ring formation serve to link alternating A and B units into chains, which propagate parallel to the y direction and are generated by twofold screw axes (Fig. 2).

The structure is pseudosymmetric; the anions are related to a good approximation (mean deviation 0.09 Å) by an inversion centre at ca -0.257, 0.760, 0.252, but the cations are not. The pseudo-centre is automatically associated with a pseudo-glide plane and, accordingly, the reflections h0l with h+l odd are weak, but present. One clear topological difference between the two cations is shown by the NH₂ groups; that at N3 forms hydrogen bonds to two O(ap) atoms, but that at N3' to one O(ap) and one O(sc) (see Figs. 1 and 2). Associated with this, the environment at N3 is essentially planar (angle sum 360°), whereas that at N3' is pyramidalized (angle sum 346°).

On comparing the monoclinic crystal structures of (I) (space group P2₁/c, Z' = 1; Moers, Wijaya et al., 2000) and (II) (space group P2₁, Z' = 2), the following similarities and discrepancies become apparent: (i) both assemblies contain the R²₂(8) target synthon; (ii) the differing shapes and volumes of the disulfonylamidate building blocks do not interfere with the donor-acceptor selectivity within the ring motifs [common pattern: C₂N—H···N/CN(H)—H···O(ap)]; (iii) the independent ion pairs, one in (I) and two in (II), are linked via the second amino donors into chains generated by 2₁ transformation in the y direction, but the c-glide plane (and concomitant inversion centre) operative in (I) is not maintained in (II); (iv) a striking contrast arises in the supramolecular catenation modi, so far as in (I) the chain-forming H bond is accepted by the O(ap) atom already pertaining to the ring motif, whereas in the present structure (Fig. 2) the catenation relies upon an O(sc) atom and an O(ap) acceptor that is not involved in the cyclic synthon; (v) the latter, apparently disparate catenation mode clearly gives rise to a strongly meandering chain, which conveniently accommodates the bulky phenyl rings within spacious bays.

Related literature

For related literature, see: Aakeröy (1997); Aakeröy & Seddon (1993); Allen et al. (1999); Bernstein et al. (1995); Bombicz et al. (1996); Cotton & Stokely (1970); Desiraju (1995); Freytag & Jones (1999); Henschel et al. (1997, 1999); Mascal et al. (1995); Moers, Wijaya, Lange, Blaschette & Jones (2000); Subramanian & Zaworotko (1994); Wijaya et al. (1999, 2000).

S2. Experimental

Compound (II) was prepared by dissolving di(benzenesulfonyl)amine (0.60 g, 2.0 mmol) and 2-aminopyridine (0.19 g, 2.0 mmol) in acetonitrile (10 ml). Slow partial evaporation of the solvent at ambient temperature gave a yield of 0.68 g (86%) and crystals suitable for X-ray study (m.p. 403–408 K). A satisfactory elemental analysis was obtained.

S3. Refinement

The structure was refined as a racemic twin with components 0.62 (6) and 0.38 (6); 3930 Friedel pairs were available. H atoms bonded to N atoms were refined freely, but with chemically equivalent N—H and H···H distances of the NH₂ groups restrained to be approximately equal. The freely refined N—H distances were longer than expected but could not be satisfactorily restrained to standard values. We have observed this effect previously (Freytag & Jones, 1999). Other H atoms were refined using a riding model starting from calculated positions.

Computing details

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The asymmetric unit of the title compound. Hydrogen bonds are indicated by dashed lines. Radii are arbitrary.
	Fig. 2. Packing diagram of the title compound, showing the formation of a strongly curved chain. For clarity, all ions are shown reduced to the fragments directly involved in catenation. Hydrogen bonds are indicated by dashed lines.

2-aminopyridinium di(benzenesulfonyl)amidate

Crystal data

C5H7N2^+·C12H10NO4S2^−	F(000) = 816
Mr = 391.46	Dx = 1.471 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.643 (3) Å	Cell parameters from 52 reflections
b = 15.624 (3) Å	θ = 10–11.5°
c = 11.349 (3) Å	µ = 0.33 mm^−1
β = 110.500 (12)°	T = 143 K
V = 1767.5 (7) Å^3	Block, colourless
Z = 4	0.6 × 0.6 × 0.5 mm

Data collection

Stoe Stadi-4 four-circle diffractometer	Rint = 0.035
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 3.2°
Graphite monochromator	h = −13→13
ω/θ scans	k = −20→20
11932 measured reflections	l = −14→14
8139 independent reflections	3 standard reflections every 60 min
7516 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0499P)^2 + 0.7866P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
8139 reflections	Δρmax = 0.37 e Å^−3
494 parameters	Δρmin = −0.35 e Å^−3
9 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.62 (6)

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
N1	0.4417 (2)	0.10194 (15)	0.5530 (2)	0.0277 (5)
S1	0.38404 (6)	0.15964 (4)	0.63857 (6)	0.02908 (14)
S2	0.34889 (6)	0.03191 (4)	0.45918 (6)	0.02736 (14)
O1	0.4989 (2)	0.20080 (15)	0.72903 (19)	0.0423 (5)
O2	0.2977 (2)	0.11356 (15)	0.69011 (19)	0.0408 (5)
O3	0.4175 (2)	0.01182 (16)	0.3733 (2)	0.0444 (5)
O4	0.21066 (19)	0.05755 (15)	0.4045 (2)	0.0390 (5)
C11	0.2862 (2)	0.24109 (17)	0.5406 (2)	0.0267 (5)
C12	0.1775 (3)	0.2732 (2)	0.5669 (3)	0.0326 (6)
H12	0.1552	0.2509	0.6349	0.039*
C13	0.1018 (3)	0.3383 (2)	0.4926 (3)	0.0374 (7)
H13	0.0274	0.3612	0.5099	0.045*
C14	0.1345 (3)	0.3699 (2)	0.3937 (3)	0.0374 (6)
H14	0.0816	0.4140	0.3424	0.045*
C15	0.2432 (3)	0.3380 (2)	0.3684 (3)	0.0367 (7)
H15	0.2649	0.3602	0.2999	0.044*
C16	0.3204 (3)	0.2739 (2)	0.4426 (3)	0.0346 (6)
H16	0.3964	0.2524	0.4265	0.042*
C21	0.3551 (2)	−0.06113 (18)	0.5502 (2)	0.0250 (5)
C22	0.2515 (3)	−0.1198 (2)	0.5061 (3)	0.0360 (7)
H22	0.1773	−0.1087	0.4314	0.043*
C23	0.2578 (3)	−0.1945 (2)	0.5728 (3)	0.0397 (7)
H23	0.1872	−0.2351	0.5440	0.048*
C24	0.3664 (3)	−0.2109 (2)	0.6813 (3)	0.0349 (6)
H24	0.3703	−0.2627	0.7262	0.042*
C25	0.4690 (3)	−0.1518 (2)	0.7242 (3)	0.0329 (6)
H25	0.5433	−0.1628	0.7988	0.039*
C26	0.4634 (2)	−0.07673 (19)	0.6587 (2)	0.0298 (6)
H26	0.5337	−0.0359	0.6880	0.036*
N2	0.6999 (2)	0.09234 (18)	0.5228 (2)	0.0366 (5)
H01	0.617 (3)	0.094 (3)	0.525 (4)	0.055 (11)*
N3	0.7613 (3)	0.17743 (19)	0.7005 (3)	0.0478 (6)
H02	0.667 (3)	0.180 (3)	0.711 (5)	0.106 (17)*
H03	0.826 (5)	0.220 (4)	0.766 (5)	0.16 (3)*
C3	0.7949 (3)	0.1327 (2)	0.6167 (3)	0.0342 (6)
C4	0.9287 (3)	0.1282 (2)	0.6190 (3)	0.0407 (7)
H4	0.9997	0.1533	0.6861	0.049*
C5	0.9539 (3)	0.0870 (2)	0.5232 (4)	0.0493 (8)
H5	1.0431	0.0845	0.5232	0.059*
C6	0.8498 (4)	0.0485 (2)	0.4250 (4)	0.0521 (9)
H6	0.8671	0.0211	0.3575	0.063*
C7	0.7253 (4)	0.0513 (2)	0.4285 (3)	0.0468 (8)
H7	0.6540	0.0241	0.3640	0.056*
N1'	1.0369 (2)	0.41970 (16)	0.9614 (2)	0.0299 (5)
S1'	1.14071 (6)	0.48731 (4)	1.04803 (6)	0.02664 (14)
S2'	1.07918 (7)	0.35861 (4)	0.86922 (6)	0.03303 (15)
O1'	1.0826 (2)	0.51506 (16)	1.1388 (2)	0.0449 (5)
O2'	1.27585 (19)	0.45600 (15)	1.09909 (19)	0.0388 (5)
O3'	0.9568 (2)	0.31509 (16)	0.7966 (2)	0.0570 (7)
O4'	1.1511 (3)	0.40249 (15)	0.8001 (2)	0.0484 (6)
C11'	1.1421 (2)	0.57810 (17)	0.9549 (2)	0.0236 (5)
C12'	1.2466 (3)	0.63581 (19)	1.0023 (3)	0.0319 (6)
H12'	1.3181	0.6236	1.0786	0.038*
C13'	1.2463 (3)	0.7111 (2)	0.9385 (3)	0.0399 (7)
H13'	1.3177	0.7509	0.9708	0.048*
C14'	1.1407 (3)	0.7287 (2)	0.8261 (3)	0.0355 (6)
H14'	1.1391	0.7811	0.7830	0.043*
C15'	1.0388 (3)	0.66972 (19)	0.7781 (2)	0.0306 (6)
H15'	0.9683	0.6810	0.7008	0.037*
C16'	1.0391 (3)	0.59362 (18)	0.8426 (2)	0.0276 (5)
H16'	0.9692	0.5530	0.8096	0.033*
C21'	1.1900 (3)	0.27961 (18)	0.9619 (2)	0.0289 (5)
C22'	1.2974 (3)	0.25334 (19)	0.9301 (3)	0.0333 (6)
H22'	1.3142	0.2788	0.8610	0.040*
C23'	1.3810 (3)	0.1894 (2)	0.9999 (3)	0.0389 (7)
H23'	1.4543	0.1702	0.9774	0.047*
C24'	1.3583 (3)	0.1531 (2)	1.1026 (3)	0.0362 (6)
H24'	1.4175	0.1107	1.1519	0.043*
C25'	1.2491 (3)	0.1792 (2)	1.1321 (3)	0.0383 (7)
H25'	1.2318	0.1537	1.2008	0.046*
C26'	1.1642 (3)	0.2428 (2)	1.0614 (3)	0.0361 (6)
H26'	1.0889	0.2608	1.0817	0.043*
N2'	0.7674 (3)	0.43261 (16)	0.9693 (2)	0.0349 (5)
H04	0.852 (3)	0.429 (3)	0.979 (3)	0.045 (10)*
N3'	0.8229 (3)	0.5026 (2)	1.1608 (3)	0.0531 (7)
H05	0.912 (4)	0.524 (3)	1.155 (4)	0.094 (16)*
H06	0.782 (5)	0.542 (3)	1.210 (5)	0.13 (2)*
C3'	0.7305 (3)	0.4691 (2)	1.0597 (3)	0.0409 (7)
C4'	0.5929 (3)	0.4684 (2)	1.0443 (3)	0.0460 (8)
H4'	0.5640	0.4925	1.1074	0.055*
C5'	0.5025 (3)	0.4335 (2)	0.9406 (4)	0.0475 (8)
H5'	0.4101	0.4337	0.9304	0.057*
C6'	0.5439 (3)	0.3973 (2)	0.8484 (4)	0.0487 (8)
H6'	0.4804	0.3729	0.7750	0.058*
C7'	0.6787 (3)	0.3975 (2)	0.8651 (3)	0.0403 (7)
H7'	0.7088	0.3729	0.8032	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0244 (10)	0.0273 (11)	0.0292 (11)	−0.0004 (8)	0.0065 (8)	0.0014 (9)
S1	0.0314 (3)	0.0319 (3)	0.0201 (3)	0.0002 (3)	0.0043 (2)	0.0022 (2)
S2	0.0258 (3)	0.0335 (4)	0.0194 (3)	−0.0004 (2)	0.0037 (2)	0.0016 (3)
O1	0.0421 (11)	0.0412 (12)	0.0288 (9)	−0.0006 (9)	−0.0060 (8)	−0.0051 (9)
O2	0.0545 (12)	0.0414 (12)	0.0325 (10)	0.0011 (10)	0.0227 (9)	0.0085 (9)
O3	0.0599 (13)	0.0492 (14)	0.0326 (10)	−0.0025 (11)	0.0270 (10)	−0.0026 (10)
O4	0.0293 (9)	0.0440 (12)	0.0308 (10)	0.0018 (9)	−0.0055 (8)	0.0061 (9)
C11	0.0275 (12)	0.0266 (13)	0.0222 (12)	−0.0014 (10)	0.0041 (9)	0.0012 (10)
C12	0.0330 (13)	0.0352 (15)	0.0320 (13)	−0.0048 (11)	0.0144 (11)	−0.0019 (12)
C13	0.0311 (13)	0.0351 (16)	0.0453 (17)	0.0047 (11)	0.0126 (12)	−0.0031 (13)
C14	0.0392 (14)	0.0321 (16)	0.0331 (14)	0.0036 (12)	0.0029 (12)	0.0000 (13)
C15	0.0466 (16)	0.0341 (18)	0.0286 (14)	0.0016 (12)	0.0121 (12)	0.0060 (12)
C16	0.0382 (14)	0.0367 (16)	0.0325 (14)	0.0080 (12)	0.0168 (11)	0.0071 (12)
C21	0.0242 (11)	0.0269 (13)	0.0227 (12)	0.0015 (9)	0.0067 (9)	−0.0010 (10)
C22	0.0270 (12)	0.0440 (19)	0.0323 (14)	−0.0067 (11)	0.0045 (10)	−0.0037 (13)
C23	0.0363 (15)	0.0336 (17)	0.0472 (17)	−0.0127 (12)	0.0120 (13)	−0.0057 (13)
C24	0.0391 (14)	0.0297 (15)	0.0398 (15)	0.0008 (12)	0.0186 (12)	0.0004 (12)
C25	0.0337 (13)	0.0331 (16)	0.0294 (13)	0.0032 (11)	0.0079 (10)	0.0048 (12)
C26	0.0248 (11)	0.0310 (14)	0.0278 (13)	−0.0026 (10)	0.0022 (10)	−0.0005 (11)
N2	0.0325 (12)	0.0382 (14)	0.0387 (13)	−0.0067 (10)	0.0122 (10)	0.0004 (11)
N3	0.0403 (13)	0.0531 (17)	0.0497 (15)	−0.0027 (12)	0.0155 (12)	−0.0046 (13)
C3	0.0311 (13)	0.0353 (15)	0.0382 (15)	−0.0039 (11)	0.0144 (11)	0.0037 (12)
C4	0.0276 (13)	0.0398 (16)	0.0552 (19)	−0.0037 (11)	0.0150 (13)	0.0047 (14)
C5	0.0459 (17)	0.0445 (18)	0.072 (2)	0.0079 (14)	0.0390 (17)	0.0168 (17)
C6	0.080 (2)	0.0369 (17)	0.054 (2)	0.0042 (17)	0.0415 (19)	0.0038 (15)
C7	0.063 (2)	0.0389 (17)	0.0376 (16)	−0.0062 (15)	0.0167 (15)	−0.0025 (13)
N1'	0.0249 (10)	0.0320 (12)	0.0296 (11)	−0.0026 (9)	0.0056 (8)	0.0035 (10)
S1'	0.0267 (3)	0.0316 (3)	0.0193 (3)	0.0024 (2)	0.0051 (2)	0.0020 (2)
S2'	0.0429 (3)	0.0277 (3)	0.0212 (3)	−0.0004 (3)	0.0020 (2)	0.0015 (3)
O1'	0.0638 (13)	0.0458 (13)	0.0347 (11)	0.0017 (11)	0.0293 (10)	0.0005 (10)
O2'	0.0286 (9)	0.0410 (12)	0.0340 (10)	0.0053 (8)	−0.0050 (8)	0.0060 (9)
O3'	0.0580 (14)	0.0386 (12)	0.0447 (13)	−0.0046 (11)	−0.0194 (11)	−0.0056 (10)
O4'	0.0816 (16)	0.0376 (12)	0.0333 (11)	0.0091 (11)	0.0293 (11)	0.0101 (9)
C11'	0.0192 (10)	0.0303 (14)	0.0206 (11)	0.0005 (9)	0.0062 (8)	−0.0004 (10)
C12'	0.0254 (12)	0.0396 (17)	0.0259 (13)	−0.0027 (10)	0.0030 (10)	−0.0015 (11)
C13'	0.0301 (13)	0.0405 (18)	0.0487 (17)	−0.0101 (12)	0.0134 (12)	−0.0082 (15)
C14'	0.0418 (15)	0.0296 (15)	0.0410 (16)	0.0021 (12)	0.0219 (13)	0.0043 (13)
C15'	0.0324 (12)	0.0325 (15)	0.0252 (12)	0.0035 (11)	0.0080 (10)	0.0024 (11)
C16'	0.0270 (12)	0.0276 (13)	0.0241 (12)	0.0004 (10)	0.0038 (10)	−0.0006 (11)
C21'	0.0319 (13)	0.0275 (13)	0.0244 (12)	−0.0016 (10)	0.0064 (10)	−0.0007 (11)
C22'	0.0395 (14)	0.0349 (15)	0.0271 (13)	−0.0077 (12)	0.0136 (11)	−0.0047 (11)
C23'	0.0340 (13)	0.0396 (16)	0.0454 (16)	−0.0001 (12)	0.0169 (12)	−0.0078 (13)
C24'	0.0380 (14)	0.0280 (15)	0.0375 (15)	0.0028 (12)	0.0067 (12)	−0.0018 (13)
C25'	0.0426 (15)	0.0382 (18)	0.0346 (14)	0.0056 (12)	0.0140 (12)	0.0080 (13)
C26'	0.0395 (14)	0.0372 (17)	0.0366 (15)	0.0052 (12)	0.0195 (12)	0.0079 (13)
N2'	0.0370 (12)	0.0321 (12)	0.0404 (13)	0.0011 (10)	0.0194 (10)	0.0038 (11)
N3'	0.0543 (16)	0.0592 (18)	0.0447 (15)	0.0034 (14)	0.0161 (13)	−0.0096 (14)
C3'	0.0521 (17)	0.0313 (16)	0.0399 (16)	0.0004 (13)	0.0169 (14)	0.0063 (12)
C4'	0.0552 (18)	0.0371 (16)	0.061 (2)	0.0083 (14)	0.0390 (16)	0.0090 (15)
C5'	0.0431 (16)	0.0349 (16)	0.074 (2)	−0.0042 (13)	0.0332 (16)	0.0031 (16)
C6'	0.0429 (16)	0.0421 (17)	0.061 (2)	−0.0076 (14)	0.0182 (15)	0.0015 (16)
C7'	0.0453 (16)	0.0363 (15)	0.0413 (16)	−0.0017 (13)	0.0179 (13)	−0.0008 (13)

Geometric parameters (Å, º)

N2—C3	1.342 (4)	N2'—C3'	1.347 (4)
N2—C7	1.353 (4)	N2'—C7'	1.345 (4)
N3—C3	1.326 (4)	N3'—C3'	1.329 (4)
N1—S1	1.597 (2)	N1'—S1'	1.595 (2)
S1—O1	1.443 (2)	S1'—O1'	1.442 (2)
N2—N3	2.311 (4)	N2'—N3'	2.316 (4)
N1—O1	2.428 (3)	N1'—O1'	2.413 (3)
N1—S2	1.603 (2)	N1'—S2'	1.593 (2)
S1—O2	1.442 (2)	S1'—O2'	1.435 (2)
S1—C11	1.769 (3)	S1'—C11'	1.772 (3)
S2—O4	1.439 (2)	S2'—O3'	1.444 (2)
S2—O3	1.442 (2)	S2'—O4'	1.447 (2)
S2—C21	1.771 (3)	S2'—C21'	1.775 (3)
C11—C16	1.384 (4)	C11'—C16'	1.381 (3)
C11—C12	1.387 (4)	C11'—C12'	1.385 (4)
C12—C13	1.384 (4)	C12'—C13'	1.381 (4)
C13—C14	1.378 (4)	C13'—C14'	1.401 (4)
C14—C15	1.379 (4)	C14'—C15'	1.381 (4)
C15—C16	1.380 (4)	C15'—C16'	1.396 (4)
C21—C26	1.382 (3)	C21'—C22'	1.377 (4)
C21—C22	1.386 (4)	C21'—C26'	1.378 (4)
C22—C23	1.380 (5)	C22'—C23'	1.387 (4)
C23—C24	1.386 (4)	C23'—C24'	1.391 (4)
C24—C25	1.382 (4)	C24'—C25'	1.378 (4)
C25—C26	1.378 (4)	C25'—C26'	1.394 (4)
C3—C4	1.416 (4)	C3'—C4'	1.413 (4)
C4—C5	1.369 (5)	C4'—C5'	1.347 (5)
C5—C6	1.403 (5)	C5'—C6'	1.390 (5)
C6—C7	1.340 (5)	C6'—C7'	1.380 (4)
O2—S1—O1	115.79 (14)	O2'—S1'—O1'	115.73 (14)
O2—S1—N1	113.57 (13)	O2'—S1'—N1'	113.78 (13)
O2—S1—C11	107.21 (13)	O2'—S1'—C11'	107.28 (12)
O1—S1—C11	106.98 (13)	O1'—S1'—C11'	106.32 (13)
N1—S1—C11	106.90 (12)	N1'—S1'—C11'	108.14 (12)
O4—S2—O3	116.88 (14)	O3'—S2'—O4'	117.16 (16)
O4—S2—N1	113.30 (13)	O3'—S2'—N1'	104.53 (15)
O3—S2—N1	104.92 (13)	O4'—S2'—N1'	113.41 (13)
O4—S2—C21	107.69 (13)	O3'—S2'—C21'	106.84 (14)
O3—S2—C21	106.92 (13)	O4'—S2'—C21'	106.45 (14)
N1—S2—C21	106.52 (12)	N1'—S2'—C21'	108.00 (12)
C16—C11—C12	120.9 (3)	C16'—C11'—C12'	121.0 (2)
C16—C11—S1	120.6 (2)	C16'—C11'—S1'	121.4 (2)
C12—C11—S1	118.5 (2)	C12'—C11'—S1'	117.52 (19)
C13—C12—C11	119.1 (3)	C13'—C12'—C11'	119.8 (2)
C14—C13—C12	120.0 (3)	C12'—C13'—C14'	119.9 (3)
C13—C14—C15	120.7 (3)	C15'—C14'—C13'	119.8 (3)
C14—C15—C16	119.9 (3)	C14'—C15'—C16'	120.3 (2)
C15—C16—C11	119.4 (3)	C11'—C16'—C15'	119.3 (2)
C26—C21—C22	121.0 (3)	C22'—C21'—C26'	120.9 (3)
C26—C21—S2	120.9 (2)	C22'—C21'—S2'	119.5 (2)
C22—C21—S2	118.0 (2)	C26'—C21'—S2'	119.6 (2)
C23—C22—C21	118.8 (3)	C21'—C22'—C23'	119.4 (3)
C22—C23—C24	120.6 (3)	C22'—C23'—C24'	120.5 (3)
C25—C24—C23	120.0 (3)	C25'—C24'—C23'	119.5 (3)
C26—C25—C24	119.9 (3)	C24'—C25'—C26'	120.2 (3)
C25—C26—C21	119.7 (3)	C21'—C26'—C25'	119.6 (3)
C3—N2—C7	123.2 (3)	C3'—N2'—C7'	122.7 (3)
H01—N2—C3	116 (3)	H04—N2'—C3'	119 (2)
H01—N2—C7	120 (3)	H04—N2'—C7'	118 (2)
H02—N3—C3	127 (3)	H05—N3'—C3'	119 (3)
H03—N3—C3	124 (3)	H06—N3'—C3'	112 (3)
H02—N3—H03	109 (3)	H05—N3'—H06	115 (3)
N2—C3—N3	120.0 (3)	N2'—C3'—N3'	119.9 (3)
N1—S1—O1	105.90 (13)	N1'—S1'—O1'	105.14 (13)
S1—N1—S2	120.70 (13)	S2'—N1'—S1'	120.48 (14)
N3—C3—C4	122.3 (3)	N3'—C3'—C4'	122.1 (3)
N2—C3—C4	117.7 (3)	N2'—C3'—C4'	118.0 (3)
C5—C4—C3	119.0 (3)	C5'—C4'—C3'	120.2 (3)
C4—C5—C6	120.8 (3)	C4'—C5'—C6'	120.4 (3)
C7—C6—C5	118.5 (3)	C7'—C6'—C5'	118.9 (3)
C6—C7—N2	120.8 (3)	N2'—C7'—C6'	119.9 (3)
S2—N1—S1—O1	167.75 (15)	S2'—N1'—S1'—O1'	−166.13 (16)
S2—N1—S1—O2	39.6 (2)	S2'—N1'—S1'—O2'	−38.5 (2)
S1—N1—S2—O3	163.29 (16)	S1'—N1'—S2'—O3'	−173.12 (16)
S1—N1—S2—O4	34.7 (2)	S1'—N1'—S2'—O4'	−44.4 (2)
C11—S1—S2—C21	−147.86 (12)	C11'—S1'—S2'—C21'	139.69 (12)
S2—N1—S1—C11	−78.42 (18)	S2'—N1'—S1'—C11'	80.60 (17)
S1—N1—S2—C21	−83.56 (17)	S1'—N1'—S2'—C21'	73.36 (19)
O2—S1—C11—C16	−154.8 (2)	O2'—S1'—C11'—C16'	141.5 (2)
O1—S1—C11—C16	80.4 (3)	O1'—S1'—C11'—C16'	−94.1 (2)
N1—S1—C11—C16	−32.7 (3)	N1'—S1'—C11'—C16'	18.3 (2)
O2—S1—C11—C12	27.3 (3)	O2'—S1'—C11'—C12'	−42.3 (2)
O1—S1—C11—C12	−97.5 (2)	O1'—S1'—C11'—C12'	82.1 (2)
N1—S1—C11—C12	149.4 (2)	N1'—S1'—C11'—C12'	−165.4 (2)
C16—C11—C12—C13	0.7 (4)	C16'—C11'—C12'—C13'	1.7 (4)
S1—C11—C12—C13	178.6 (2)	S1'—C11'—C12'—C13'	−174.6 (2)
C11—C12—C13—C14	0.4 (4)	C11'—C12'—C13'—C14'	−0.1 (4)
C12—C13—C14—C15	−0.8 (5)	C12'—C13'—C14'—C15'	−1.5 (4)
C13—C14—C15—C16	0.0 (5)	C13'—C14'—C15'—C16'	1.5 (4)
C14—C15—C16—C11	1.1 (5)	C12'—C11'—C16'—C15'	−1.7 (4)
C12—C11—C16—C15	−1.5 (5)	S1'—C11'—C16'—C15'	174.4 (2)
S1—C11—C16—C15	−179.3 (2)	C14'—C15'—C16'—C11'	0.1 (4)
O4—S2—C21—C26	−146.9 (2)	O3'—S2'—C21'—C22'	106.3 (3)
O3—S2—C21—C26	86.7 (2)	O4'—S2'—C21'—C22'	−19.7 (3)
N1—S2—C21—C26	−25.1 (2)	N1'—S2'—C21'—C22'	−141.8 (2)
O4—S2—C21—C22	36.2 (2)	O3'—S2'—C21'—C26'	−71.0 (3)
O3—S2—C21—C22	−90.2 (2)	O4'—S2'—C21'—C26'	163.1 (2)
N1—S2—C21—C22	158.0 (2)	N1'—S2'—C21'—C26'	41.0 (3)
C26—C21—C22—C23	0.1 (4)	C26'—C21'—C22'—C23'	−0.4 (4)
S2—C21—C22—C23	177.0 (2)	S2'—C21'—C22'—C23'	−177.6 (2)
C21—C22—C23—C24	−0.4 (4)	C21'—C22'—C23'—C24'	−1.2 (4)
C22—C23—C24—C25	0.5 (5)	C22'—C23'—C24'—C25'	2.2 (5)
C23—C24—C25—C26	−0.3 (4)	C23'—C24'—C25'—C26'	−1.5 (5)
C24—C25—C26—C21	−0.1 (4)	C22'—C21'—C26'—C25'	1.1 (5)
C22—C21—C26—C25	0.2 (4)	S2'—C21'—C26'—C25'	178.3 (2)
S2—C21—C26—C25	−176.6 (2)	C24'—C25'—C26'—C21'	−0.1 (5)
C7—N2—C3—N3	174.6 (3)	C7'—N2'—C3'—N3'	179.8 (3)
C7—N2—C3—C4	−3.0 (5)	C7'—N2'—C3'—C4'	1.4 (5)
N3—C3—C4—C5	−174.3 (3)	N3'—C3'—C4'—C5'	−179.7 (3)
N2—C3—C4—C5	3.3 (5)	N2'—C3'—C4'—C5'	−1.4 (5)
C3—C4—C5—C6	−1.1 (5)	C3'—C4'—C5'—C6'	0.6 (5)
C4—C5—C6—C7	−1.4 (5)	C4'—C5'—C6'—C7'	0.2 (5)
C5—C6—C7—N2	1.8 (5)	C3'—N2'—C7'—C6'	−0.6 (5)
C3—N2—C7—C6	0.5 (5)	C5'—C6'—C7'—N2'	−0.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H01···N1	0.89 (3)	2.01 (3)	2.890 (3)	172 (4)
N3—H02···O1	1.05 (3)	1.90 (3)	2.945 (4)	172 (5)
N3—H03···O3′	1.05 (3)	1.98 (4)	2.925 (4)	148 (5)
N2′—H04···N1′	0.87 (3)	2.05 (3)	2.907 (3)	168 (3)
N3′—H05···O1′	1.03 (3)	1.89 (3)	2.868 (4)	157 (4)
N3′—H06···O2^i	1.03 (3)	1.98 (3)	3.006 (4)	178 (5)
C25—H25···O2′^ii	0.95	2.63	3.227 (4)	121
C26—H26···O2′^ii	0.95	2.56	3.190 (3)	124
C5—H5···O4^iii	0.95	2.62	3.474 (4)	150
C6—H6···O4′^iv	0.95	2.53	3.422 (4)	155
C7—H7···O3	0.95	2.56	3.173 (4)	122
C12′—H12′···O1^v	0.95	2.65	3.447 (3)	141
C15′—H15′···O4^vi	0.95	2.68	3.250 (3)	119
C16′—H16′···O4^vi	0.95	2.51	3.166 (3)	126
C5′—H5′···O4′^vii	0.95	2.68	3.548 (4)	153

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