Crystal structure of 4-[(5-methyl-isoxazol-3-yl)amino-sulfon-yl]anilinium 3,5-di-nitro-salicylate.

The title mol-ecular salt, C10H12N3O3S(+)·C7H3N2O7 (-), protonation occurs at the amino N atom attached to the benzene ring of sulfamethoxazole. In the anion, there is an intra-molecular O-H⋯O hydrogen bond and the cation is linked to the anion by an N-H⋯O hydrogen bond. In the extended structure, the cations and anions are linked via N-H⋯O, N-H⋯N and C-H⋯O hydrogen bonds, forming a three-dimensional framework.

Chemical context

Sulfamethoxazole, {4-[(5-methyl­isoxazol-3-yl)amino­sulfon­yl]aniline} (SMZ) is a well-known anti­bacterial and anti­fungal sulfa drug (Ma et al., 2007 ▸; Hida et al., 2005 ▸). This drug prevents the formation of di­hydro­folic acid, a compound that bacteria must be able to make in order to endure. The structural resemblance of p-amino benzoic acid to the sulfanilamide group enables sulfanilamide block folic acid synthesis in bacteria (Bock et al.,1974 ▸). SMZ is also known to be effective against gram positive and gram negative bacteria and some protozoans. In clinical practice, SMZ is used as a combinatorial drug along with Trimethoprim (TMP) to treat a variety of bacterial infections. In the last three and half decades, multiple crystalline forms of SMZ (Bettinetti et al., 1982 ▸; Maury et al., 1985 ▸; Price et al., 2005 ▸), metal complexes (Marques et al., 2006 ▸; Nakai et al., 1984 ▸) and salt forms (Nakai et al., 1984 ▸; Subashini et al., 2007 ▸) have been reported. We report herein on the crystal structure and supra­molecular packing pattern of the title salt.

Structural commentary

The asymmetric unit of the title salt (SMZDNS), consists of a sulfamethoxazolium cation and a 3,5-di­nitro­salicylate anion (Fig. 1 ▸). The SMZ cation is L-shaped with the dihedral angle between the oxazole and anilinium rings being 81.86 (10)°. The geometry around the sulfur atom is slightly distorted tetra­hedral, which is evident from the O1—S1—O2 angle of 120.44 (8)°. Protonation occurs at the amino atom N1 of the benzene moiety of SMZ. In the cation there is an intra­molecular O—H⋯O hydrogen bond with an S(6) ring motif (Fig. 1 ▸ and Table 1 ▸). The cation is linked to the anion by an N—H⋯O hydrogen bond (Fig. 1 ▸ and Table 1 ▸), and the dihedral angle between the benzene rings of the cation and anion is 78.51 (8)°.

Figure 1

A view of the mol­ecular structure of the title mol­ecular salt, showing the atom labelling. The displacement ellipsoids are drawn at the 50% probability level. The hydrogen bonds are shown as dashed lines (see Table 1 ▸ for details).

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O6H6AO5	0.82	1.68	2.4296(19)	151
N2H2AO5	0.86	2.12	2.7852(18)	134
N1H1AO4i	0.89	1.77	2.661(2)	177
N1H1BN3i	0.89	2.24	3.041(2)	150
N1H1CO6ii	0.89	2.21	3.064(2)	160
C5H5O6ii	0.93	2.60	3.293(2)	132
C6H6O8iii	0.93	2.60	3.176(2)	121

Symmetry codes: (i) ; (ii) ; (iii) .

Supra­molecular features

In the crystal of the title salt, there are various hydrogen bonds present linking the anions and cations and forming a three-dimensional network (Figs. 2 ▸ and 3 ▸, and Table 1 ▸). The ammonium ion of the cation generates a C(3) chain and two (6) and (10) ring motifs (Bernstein et al., 1995 ▸). The primary inter­action between the cation and anion happens through an N—H⋯O hydrogen bond and it forms a chain of C(3) graph set. The (6) motif is formed via N—H⋯O and C—H⋯O hydrogen bonds that link the ammonium N1 phenyl C5 group of SMZ and the hy­droxy O6 group of the anion. The (10) ring motif is a result of the linking of two symmetry-related cations and one anion via a pair of N—H⋯O and N—H⋯N hydrogen bonds. This motif is formed by the inter­action of symmetry-related imino N2, oxazole N3, ammonium N1 atoms of the cation and the carboxyl­ate (O4 and O5) group of the anion. The (6) and (10) motifs are linked by another ring motif with an (8) graph set. This motif is formed by linking two symmetry-related cations with an anion via a pair of bifurcated N—H⋯O hydrogen bonds. The amalgamation of the above ring motifs leads to the formation of supra­molecular sheets along the a axis (Fig. 2 ▸). The sheets thus formed are linked to adjacent ones through (16) and (20) motifs. The (16) motif is formed by inter­action of ammonium atom N1 and atom O2 of the sulfate group of an inversion-related SMZ ion in an adjacent sheet via a pair of N—H⋯O hydrogen bonds. The other motif, an (20) ring, is formed by the linkage of two inversion-related cations along the b axis. Finally, through these arrangements a three-dimensional hydrogen-bonded architecture is formed.

Figure 2

A view of the graph set motifs formed in the crystal of the title salt, via N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds (dashed lines; see Table 1 ▸ for details). The cations are drawn in wire mode and the anions in ball-and-stick mode.

Figure 3

A view along the a axis of the crystal packing of the title salt. The hydrogen bonds are drawn as dashed lines (see Table 1 ▸ for details). H atoms not involved in hydrogen bonding have been omitted for clarity.

Database survey

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014 ▸) for 4-[(5-methyl­isoxazol-3-yl)amino­sulfon­yl]aniline revealed the presence of only two structures of the protonated form. These include, catena-[bis­(sulfa­methoxazolium)(μ2-chlorido)­tri­chlorido­cadmium(II) monohydrate] [RISZAV; Subashini et al., 2008 ▸] and 4-[(5-methyl­isoxazol-3-yl)amino­sulfon­yl]anilinium chloride (also known as sulfamethoxazole chloride; SIMJEE; Subashini et al., 2007 ▸). The dihedral angles between the oxazole ring and anilinium ring is found to be ca 88° in RISZAV, similar to the value of 81.86 (10)° in the title salt, and ca 58° in SIMJEE.

Synthesis and crystallization

20 ml of a hot ethano­lic solution of sulfamethoxazole (63 mg) and 3.5 di­nitro­salicylic acid (57 mg) were mixed and warmed at 323 K for 30 min over a water bath. The mixture was then allowed to cool slowly at room temperature. Three weeks later, light-yellow prismatic crystals were obtained.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were positioned geometrically and refined using a riding model: O—H = 0.82 Å, N—H = 0.86–0.89 Å, and C—H = 0.93–0.96 Å with U iso(H) = 1.5U eq(C,O,N) for methyl, hy­droxy and ammonium H atoms and 1.2U eq(C,N) for aromatic and other H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	C10H12N3O3S+C7H3N2O7
M r	481.41
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c ()	8.5551(1), 10.5000(2), 12.7576(3)
, , ()	106.463(1), 100.913(1), 108.272(1)
V (3)	993.72(3)
Z	2
Radiation type	Mo K
(mm1)	0.23
Crystal size (mm)	0.20 0.20 0.16
Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 ▸)
T min, T max	0.955, 0.964
No. of measured, independent and observed [I > 2(I)] reflections	24261, 6718, 4911
R int	0.030
(sin /)max (1)	0.758
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.048, 0.139, 1.05
No. of reflections	6718
No. of parameters	301
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.40, 0.40

Computer programs: APEX2 and SAINT (Bruker, 2004 ▸), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▸), PLATON (Spek, 2009 ▸), Mercury (Macrae et al., 2008 ▸), POVRay (Cason, 2004 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015008701/su5130sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008701/su5130Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015008701/su5130Isup3.cml

CCDC reference: 1063245

Additional supporting information: crystallographic information; 3D view; checkCIF report

C10H12N3O3S+·C7H3N2O7−	Z = 2
Mr = 481.41	F(000) = 496
Triclinic, P1	Dx = 1.609 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5551 (1) Å	Cell parameters from 6718 reflections
b = 10.5000 (2) Å	θ = 1.8–32.6°
c = 12.7576 (3) Å	µ = 0.23 mm−1
α = 106.463 (1)°	T = 296 K
β = 100.913 (1)°	Prism, yellow
γ = 108.272 (1)°	0.20 × 0.20 × 0.16 mm
V = 993.72 (3) Å3

Bruker Kappa APEXII CCD diffractometer	6718 independent reflections
Radiation source: fine-focus sealed tube	4911 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω and φ scan	θmax = 32.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→12
Tmin = 0.955, Tmax = 0.964	k = −15→15
24261 measured reflections	l = −19→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0667P)2 + 0.2293P] where P = (Fo2 + 2Fc2)/3
6718 reflections	(Δ/σ)max < 0.001
301 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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.

	x	y	z	Uiso*/Ueq
S1	−0.02011 (5)	0.65153 (4)	0.38510 (3)	0.0339 (1)
O1	−0.12139 (15)	0.56291 (12)	0.26954 (11)	0.0467 (4)
O2	−0.09563 (16)	0.65425 (13)	0.47595 (11)	0.0464 (4)
O3	0.47464 (18)	0.55503 (17)	0.32047 (14)	0.0620 (5)
N1	0.29162 (18)	1.24424 (14)	0.38400 (13)	0.0425 (4)
N2	0.13876 (17)	0.60279 (14)	0.42019 (12)	0.0379 (4)
N3	0.3923 (2)	0.57678 (19)	0.40572 (15)	0.0531 (5)
C1	0.07470 (18)	0.82911 (15)	0.38933 (13)	0.0317 (4)
C2	0.2170 (2)	0.93167 (19)	0.47915 (16)	0.0503 (5)
C3	0.2877 (2)	1.06900 (19)	0.47852 (16)	0.0512 (5)
C4	0.21460 (19)	1.10143 (15)	0.38930 (14)	0.0346 (4)
C5	0.0702 (2)	1.00106 (18)	0.30178 (15)	0.0436 (5)
C6	0.0001 (2)	0.86347 (18)	0.30136 (15)	0.0419 (5)
C7	0.24792 (19)	0.58288 (15)	0.35500 (14)	0.0351 (4)
C8	0.2303 (2)	0.5656 (2)	0.23927 (16)	0.0473 (6)
C9	0.3764 (3)	0.55030 (19)	0.22403 (18)	0.0508 (6)
C10	0.4458 (3)	0.5285 (3)	0.1246 (2)	0.0749 (10)
O4	0.51673 (18)	0.76879 (19)	0.75742 (13)	0.0650 (5)
O5	0.24957 (17)	0.72400 (14)	0.65907 (10)	0.0492 (4)
O6	0.03386 (14)	0.74389 (13)	0.75511 (10)	0.0423 (3)
O7	−0.1353 (2)	0.8493 (3)	0.89565 (18)	0.0976 (9)
O8	−0.1205 (2)	0.7661 (3)	1.02988 (15)	0.0952 (8)
O9	0.4658 (2)	0.9039 (2)	1.25864 (12)	0.0710 (6)
O10	0.66328 (19)	0.9064 (2)	1.17615 (14)	0.0731 (6)
N4	−0.06166 (19)	0.8072 (2)	0.96064 (14)	0.0581 (6)
N5	0.51517 (19)	0.88887 (16)	1.17389 (13)	0.0476 (5)
C11	0.31809 (18)	0.78573 (15)	0.85972 (13)	0.0322 (4)
C12	0.14695 (18)	0.77861 (15)	0.85294 (13)	0.0326 (4)
C13	0.10795 (19)	0.80780 (18)	0.95755 (14)	0.0386 (4)
C14	0.2252 (2)	0.84029 (18)	1.06109 (14)	0.0398 (4)
C15	0.38950 (19)	0.84785 (16)	1.06265 (13)	0.0361 (4)
C16	0.43768 (18)	0.82182 (16)	0.96381 (14)	0.0352 (4)
C17	0.3688 (2)	0.75745 (17)	0.75231 (14)	0.0391 (4)
H1A	0.35880	1.24140	0.33870	0.0640*
H1B	0.35470	1.30800	0.45420	0.0640*
H1C	0.20820	1.27010	0.35590	0.0640*
H2	0.26480	0.90860	0.53940	0.0600*
H2A	0.15640	0.58830	0.48370	0.0450*
H3	0.38410	1.13910	0.53810	0.0610*
H5	0.02000	1.02560	0.24320	0.0520*
H6	−0.09710	0.79410	0.24200	0.0500*
H8	0.13930	0.56490	0.18580	0.0570*
H10A	0.55580	0.60560	0.14430	0.1120*
H10B	0.36680	0.52770	0.05980	0.1120*
H10C	0.45950	0.43820	0.10560	0.1120*
H6A	0.07860	0.73090	0.70370	0.0630*
H14	0.19440	0.85670	1.12830	0.0480*
H16	0.54970	0.82850	0.96720	0.0420*

	U11	U22	U33	U12	U13	U23
S1	0.0360 (2)	0.0322 (2)	0.0349 (2)	0.0131 (1)	0.0121 (1)	0.0137 (2)
O1	0.0460 (6)	0.0366 (6)	0.0424 (7)	0.0088 (5)	0.0010 (5)	0.0093 (5)
O2	0.0511 (6)	0.0500 (7)	0.0531 (8)	0.0239 (5)	0.0301 (6)	0.0265 (6)
O3	0.0505 (7)	0.0712 (9)	0.0659 (10)	0.0312 (7)	0.0241 (7)	0.0152 (8)
N1	0.0506 (7)	0.0353 (7)	0.0509 (9)	0.0180 (6)	0.0277 (7)	0.0199 (6)
N2	0.0475 (7)	0.0421 (7)	0.0347 (7)	0.0238 (6)	0.0164 (6)	0.0198 (6)
N3	0.0485 (8)	0.0614 (10)	0.0492 (9)	0.0275 (7)	0.0145 (7)	0.0134 (8)
C1	0.0344 (6)	0.0310 (6)	0.0310 (7)	0.0136 (5)	0.0102 (5)	0.0120 (6)
C2	0.0576 (10)	0.0412 (9)	0.0381 (9)	0.0092 (7)	−0.0054 (7)	0.0189 (8)
C3	0.0529 (9)	0.0367 (8)	0.0428 (10)	0.0026 (7)	−0.0037 (8)	0.0132 (8)
C4	0.0397 (7)	0.0318 (7)	0.0399 (8)	0.0169 (6)	0.0203 (6)	0.0156 (6)
C5	0.0465 (8)	0.0430 (8)	0.0434 (9)	0.0185 (7)	0.0060 (7)	0.0228 (8)
C6	0.0393 (7)	0.0390 (8)	0.0403 (9)	0.0115 (6)	0.0000 (6)	0.0165 (7)
C7	0.0409 (7)	0.0272 (6)	0.0368 (8)	0.0132 (5)	0.0132 (6)	0.0106 (6)
C8	0.0559 (10)	0.0513 (10)	0.0423 (10)	0.0243 (8)	0.0220 (8)	0.0198 (8)
C9	0.0598 (10)	0.0385 (8)	0.0567 (12)	0.0173 (8)	0.0324 (9)	0.0136 (8)
C10	0.0892 (17)	0.0710 (15)	0.0808 (18)	0.0340 (13)	0.0583 (15)	0.0270 (13)
O4	0.0475 (7)	0.0968 (12)	0.0513 (8)	0.0267 (7)	0.0256 (6)	0.0230 (8)
O5	0.0571 (7)	0.0597 (8)	0.0306 (6)	0.0233 (6)	0.0132 (5)	0.0160 (6)
O6	0.0395 (5)	0.0529 (7)	0.0314 (6)	0.0198 (5)	0.0039 (4)	0.0138 (5)
O7	0.0692 (10)	0.171 (2)	0.0830 (13)	0.0813 (13)	0.0218 (9)	0.0526 (13)
O8	0.0515 (8)	0.167 (2)	0.0550 (10)	0.0286 (11)	0.0271 (8)	0.0321 (12)
O9	0.0746 (10)	0.0941 (12)	0.0313 (7)	0.0259 (9)	0.0026 (7)	0.0211 (8)
O10	0.0468 (7)	0.0981 (12)	0.0612 (10)	0.0296 (8)	−0.0061 (7)	0.0238 (9)
N4	0.0382 (7)	0.0850 (12)	0.0393 (9)	0.0244 (8)	0.0082 (6)	0.0079 (8)
N5	0.0474 (8)	0.0447 (8)	0.0376 (8)	0.0141 (6)	−0.0053 (6)	0.0128 (7)
C11	0.0333 (6)	0.0298 (6)	0.0305 (7)	0.0109 (5)	0.0073 (5)	0.0098 (6)
C12	0.0348 (6)	0.0304 (6)	0.0288 (7)	0.0116 (5)	0.0041 (5)	0.0102 (6)
C13	0.0327 (7)	0.0451 (8)	0.0349 (8)	0.0158 (6)	0.0079 (6)	0.0114 (7)
C14	0.0407 (7)	0.0452 (8)	0.0294 (8)	0.0154 (6)	0.0084 (6)	0.0109 (7)
C15	0.0361 (7)	0.0346 (7)	0.0299 (7)	0.0112 (6)	−0.0004 (6)	0.0105 (6)
C16	0.0321 (6)	0.0336 (7)	0.0369 (8)	0.0124 (5)	0.0057 (6)	0.0122 (6)
C17	0.0403 (7)	0.0394 (8)	0.0365 (8)	0.0134 (6)	0.0128 (6)	0.0140 (7)

S1—O1	1.4224 (13)	C2—C3	1.381 (3)
S1—O2	1.4276 (14)	C3—C4	1.373 (3)
S1—N2	1.6264 (16)	C4—C5	1.370 (2)
S1—C1	1.7651 (17)	C5—C6	1.378 (3)
O3—N3	1.408 (2)	C7—C8	1.408 (2)
O3—C9	1.331 (3)	C8—C9	1.351 (3)
O4—C17	1.221 (2)	C9—C10	1.490 (3)
O5—C17	1.288 (2)	C2—H2	0.9300
O6—C12	1.300 (2)	C3—H3	0.9300
O7—N4	1.210 (3)	C5—H5	0.9300
O8—N4	1.212 (3)	C6—H6	0.9300
O9—N5	1.221 (2)	C8—H8	0.9300
O10—N5	1.215 (2)	C10—H10A	0.9600
O6—H6A	0.8200	C10—H10B	0.9600
N1—C4	1.464 (2)	C10—H10C	0.9600
N2—C7	1.388 (2)	C11—C16	1.382 (2)
N3—C7	1.311 (3)	C11—C17	1.493 (2)
N1—H1B	0.8900	C11—C12	1.427 (2)
N1—H1C	0.8900	C12—C13	1.410 (2)
N1—H1A	0.8900	C13—C14	1.377 (2)
N2—H2A	0.8600	C14—C15	1.379 (3)
N4—C13	1.457 (3)	C15—C16	1.381 (2)
N5—C15	1.463 (2)	C14—H14	0.9300
C1—C2	1.380 (2)	C16—H16	0.9300
C1—C6	1.378 (2)
O1—S1—O2	120.44 (8)	C8—C9—C10	133.9 (2)
O1—S1—N2	108.84 (8)	O3—C9—C8	110.33 (19)
O1—S1—C1	107.28 (8)	C1—C2—H2	120.00
O2—S1—N2	104.18 (8)	C3—C2—H2	120.00
O2—S1—C1	109.04 (8)	C2—C3—H3	120.00
N2—S1—C1	106.25 (8)	C4—C3—H3	120.00
N3—O3—C9	108.82 (18)	C6—C5—H5	120.00
C12—O6—H6A	109.00	C4—C5—H5	120.00
S1—N2—C7	124.67 (12)	C5—C6—H6	120.00
O3—N3—C7	104.87 (15)	C1—C6—H6	120.00
H1B—N1—H1C	109.00	C9—C8—H8	128.00
C4—N1—H1A	109.00	C7—C8—H8	128.00
C4—N1—H1B	109.00	H10B—C10—H10C	109.00
C4—N1—H1C	109.00	C9—C10—H10B	109.00
H1A—N1—H1B	109.00	C9—C10—H10C	110.00
H1A—N1—H1C	110.00	H10A—C10—H10B	109.00
S1—N2—H2A	118.00	H10A—C10—H10C	109.00
C7—N2—H2A	118.00	C9—C10—H10A	109.00
O7—N4—O8	123.4 (2)	C12—C11—C16	121.17 (14)
O7—N4—C13	118.79 (19)	C12—C11—C17	118.90 (14)
O8—N4—C13	117.80 (18)	C16—C11—C17	119.92 (15)
O10—N5—C15	117.66 (15)	O6—C12—C13	122.61 (15)
O9—N5—O10	123.92 (17)	C11—C12—C13	116.05 (14)
O9—N5—C15	118.42 (17)	O6—C12—C11	121.32 (14)
S1—C1—C2	121.18 (13)	N4—C13—C12	120.47 (15)
C2—C1—C6	120.80 (16)	C12—C13—C14	123.04 (16)
S1—C1—C6	118.00 (13)	N4—C13—C14	116.48 (15)
C1—C2—C3	119.21 (17)	C13—C14—C15	118.34 (15)
C2—C3—C4	119.55 (17)	N5—C15—C16	120.25 (15)
C3—C4—C5	121.35 (16)	C14—C15—C16	121.92 (15)
N1—C4—C5	118.03 (15)	N5—C15—C14	117.80 (14)
N1—C4—C3	120.61 (16)	C11—C16—C15	119.46 (15)
C4—C5—C6	119.34 (17)	O4—C17—C11	119.62 (16)
C1—C6—C5	119.70 (16)	O5—C17—C11	115.95 (16)
N3—C7—C8	112.03 (16)	O4—C17—O5	124.43 (17)
N2—C7—C8	130.75 (16)	C13—C14—H14	121.00
N2—C7—N3	117.21 (15)	C15—C14—H14	121.00
C7—C8—C9	103.93 (17)	C11—C16—H16	120.00
O3—C9—C10	115.7 (2)	C15—C16—H16	120.00
O1—S1—N2—C7	49.04 (16)	C2—C3—C4—N1	−177.26 (16)
O2—S1—N2—C7	178.71 (14)	C2—C3—C4—C5	1.5 (3)
C1—S1—N2—C7	−66.19 (15)	C3—C4—C5—C6	−2.1 (3)
O1—S1—C1—C2	−161.03 (14)	N1—C4—C5—C6	176.66 (16)
O1—S1—C1—C6	20.36 (16)	C4—C5—C6—C1	0.7 (3)
O2—S1—C1—C2	67.01 (16)	N2—C7—C8—C9	−179.86 (19)
O2—S1—C1—C6	−111.60 (14)	N3—C7—C8—C9	−0.7 (2)
N2—S1—C1—C2	−44.74 (16)	C7—C8—C9—O3	1.0 (2)
N2—S1—C1—C6	136.65 (14)	C7—C8—C9—C10	−179.8 (3)
N3—O3—C9—C8	−0.9 (2)	C16—C11—C12—O6	−179.60 (16)
C9—O3—N3—C7	0.4 (2)	C16—C11—C12—C13	−1.1 (2)
N3—O3—C9—C10	179.7 (2)	C17—C11—C12—O6	2.1 (2)
S1—N2—C7—N3	164.49 (14)	C17—C11—C12—C13	−179.40 (15)
S1—N2—C7—C8	−16.4 (3)	C12—C11—C16—C15	1.7 (3)
O3—N3—C7—N2	179.46 (15)	C17—C11—C16—C15	179.96 (16)
O3—N3—C7—C8	0.2 (2)	C12—C11—C17—O4	177.09 (18)
O7—N4—C13—C14	144.2 (2)	C12—C11—C17—O5	−1.9 (2)
O8—N4—C13—C12	146.3 (2)	C16—C11—C17—O4	−1.2 (3)
O7—N4—C13—C12	−34.7 (3)	C16—C11—C17—O5	179.75 (16)
O8—N4—C13—C14	−34.7 (3)	O6—C12—C13—N4	−3.2 (3)
O9—N5—C15—C14	5.4 (3)	O6—C12—C13—C14	177.93 (17)
O9—N5—C15—C16	−176.34 (18)	C11—C12—C13—N4	178.36 (17)
O10—N5—C15—C16	3.9 (3)	C11—C12—C13—C14	−0.5 (3)
O10—N5—C15—C14	−174.40 (19)	N4—C13—C14—C15	−177.38 (17)
C6—C1—C2—C3	−1.9 (3)	C12—C13—C14—C15	1.6 (3)
S1—C1—C6—C5	179.87 (14)	C13—C14—C15—N5	177.28 (17)
S1—C1—C2—C3	179.55 (14)	C13—C14—C15—C16	−1.0 (3)
C2—C1—C6—C5	1.3 (3)	N5—C15—C16—C11	−178.83 (16)
C1—C2—C3—C4	0.5 (3)	C14—C15—C16—C11	−0.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O5	0.82	1.68	2.4296 (19)	151
N2—H2A···O5	0.86	2.12	2.7852 (18)	134
N1—H1A···O4i	0.89	1.77	2.661 (2)	177
N1—H1B···N3i	0.89	2.24	3.041 (2)	150
N1—H1C···O6ii	0.89	2.21	3.064 (2)	160
C5—H5···O6ii	0.93	2.60	3.293 (2)	132
C6—H6···O8iii	0.93	2.60	3.176 (2)	121