Methyl 3-[(1,1-dioxo-1λ(6),2-benzothiazol-3-yl)amino]-5-nitrothiophene-2-carboxyl-ate.

The title nitro-thio-phene compound, C(13)H(9)N(3)O(6)S(2), crystallizes with two independent mol-ecules in the asymmetric unit; the mol-ecular structure of each is stabilized by an intra-molecular N-H⋯O hydrogen bond. The two mol-ecules adopt flattened but slightly different conformations, viz. the dihedral angle between the thio-phene ring and the essentailly planar 1,2-benzisothia-zole fragment (r.m.s. deviations = 0.0227 and 0.0108 Å, respectively) is 15.62 (11)° in one mol-ecule and 5.46 (11)° in the other. In the crystal, mol-ecules are arranged into layers parallel to (-111) with weak C(ar)-H⋯O inter-actions formed within the layer. N-H⋯O hydrogen bonds also occur. There are π-π stacking inter-actions between the mol-ecules in neighbouring layers, the distance between the centroids of the 1,2-benzisothia-zole benzene rings being 3.8660 (16) Å. Moreover, dipolar S=O⋯C=O inter-actions with an O⋯C distance of 2.893 (3) Å are observed between the symmetry-independent mol-ecules in different layers. The title compound showed weak inhibition of HLE (human leukocyte elastase).

Related literature

For general information on elastases, see: Bode et al. (1989 ▶); Edwards & Bernstein (1994 ▶). For biochemical assays of HLE inhibition, see: Rode et al. (2005 ▶, 2006 ▶). For information on the synthesis, see: Wade et al. (1979 ▶); Gupta et al. (1999 ▶).

Experimental

Crystal data

C13H9N3O6S2

M = 367.35

Triclinic,

a = 8.4462 (7) Å

b = 12.5495 (11) Å

c = 15.2557 (14) Å

α = 100.754 (7)°

β = 96.956 (7)°

γ = 105.287 (7)°

V = 1507.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.39 mm−1

T = 293 K

0.44 × 0.29 × 0.12 mm

Data collection

Kuma Diffraction KM4CCD Sapphire2 diffractometer

14750 measured reflections

8613 independent reflections

7242 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.165

S = 1.09

8613 reflections

443 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −0.32 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶), PLATON (Spek, 2003 ▶), WinGX (Farrugia, 1999 ▶) and Mercury (Macrae et al., 2006 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812038378/gk2503sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038378/gk2503Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812038378/gk2503Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H9N3O6S2	Z = 4
Mr = 367.35	F(000) = 752
Triclinic, P1	Dx = 1.619 Mg m−3
Hall symbol: -P 1	Melting point = 558–560 K
a = 8.4462 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.5495 (11) Å	Cell parameters from 4406 reflections
c = 15.2557 (14) Å	θ = 2–30°
α = 100.754 (7)°	µ = 0.39 mm−1
β = 96.956 (7)°	T = 293 K
γ = 105.287 (7)°	Plate, light yellow
V = 1507.5 (2) Å3	0.44 × 0.29 × 0.12 mm

Kuma Diffraction KM4CCD Sapphire2 diffractometer	7242 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 8.1883 pixels mm-1	θmax = 30°, θmin = 2.6°
ω scans	h = −11→11
14750 measured reflections	k = −17→17
8613 independent reflections	l = −21→20

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0822P)2 + 0.8507P] where P = (Fo2 + 2Fc2)/3
8613 reflections	(Δ/σ)max = 0.006
443 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Experimental. Column chromatography (CC) was performed by using Merck silica gel 60, Nr. 7734. Melting points (M.p.) were determined by MEL-TEMP (Mel-Temp laboratories Inc, USA) melting point apparatus and are uncorrected. Analytical TLC was performed on Merck TLC plates (Aluminium plates coated with silica gel 60 F254, No. 5554). Visualization of spots was carried out by using ultraviolet illumination (λ = 254 nm) and analytical data are reported as "ratio of front"-values (Rf -value). Infrared spectra were obtained by using an IR spectrophotometer, Perkin-Elmer 1600 series FTIR. Absorption is reported in relation to wavenumber (¯ν). 1H NMR spectra were measured with a Bruker DPX 200 (200 MHz) spectrometer, and 13C NMR spectra were measured with a Bruker DPX 200 (50 MHz), both at 25° C with tetramethylsilane (TMS) as an internal standard. Chemical shifts are reported as parts per million (p.p.m., δ units). Coupling constants are reported in Hz. The spectra were analysed by MESTREC NMR software. The following abbreviations were used -s: singlet, bs: broad singlet, d: doublet, m: multiplet. Analytical purity was assessed at 30° C by RP-HPLC using LaChrom apparatus series 7000, Merck Hitachi (Pump: L-7100, Diode-Array-Detector L-7450, Auto sampler L-7200, thermostat column L-7350, Solvent degasser L-7612, Interface D-7000). Column used was LiChrospher 250–4, RP-18, 5 µm. The measurement was carried out at λ max 220 nm unless otherwise stated. All solvents were used without further purification. 3-Aminothiophene-2-carboxylic acid methyl ester was purchased from Aldrich. PPE (EC 3.4.21.36, ≈200 U/mg) and HLE (EC 3.4.21.37, ≈34 U/mg) were purchased from Serva. Suc-(Ala)3-pNA, and N-methoxysuccinyl-(Ala)2 –Pro-Val-pNA were obtained from Bachem. compound 2 IR: ¯ν = 3446 (NH), 3090, 2990, 2944 (CH), 1683 (ester with intramolecular hydrogen bonds), 1616 (C=N), 1320, 1161 (SO2); 1H NMR [D6]DMSO: δ = 11.07 (bs, 1H, NH), 8.19–8.10, 8.04–7.90 (2 m, 4H, ar), 8.09 (d, J = 5.40 Hz, 1H, 5'-Hthiophene), 7.85 (d, J = 5.40 Hz, 1H, 4'-Hthiophene), 3.89 (s, 3H, OMe); 13C NMR [D6]DMSO: δ = 162.84, 156.30, 140.94, 140.83, 134.18, 133.72, 133.08, 127.12, 124.15, 122.63, 121.81, 116.71, 52.46; HPLC: k' = 4.57, t0 = 1.85 (RP-18, ACN/ H2O 1:1). compound 3 IR: ¯ν = 2958 (CH), 1707 (C=O), 1610 (C=N), 1344, 1174 (SO2); 1H NMR [D6]DMSO: δ = 11.20 (bs, 1H, NH), 8.55 (s, 1H, 4'-Hthiophene), 8.28–8.19, 8.18–8.10, 8.01–7.92 (3 m, 4H, ar), 3.93 (s, 3H, OMe); 13C NMR [D6]DMSO: δ = 160.98, 157.37, 152.00, 141.04, 137.58, 134.42, 133.79, 126.72, 125.50, 123.50, 123.11, 121.89, 53.37; HPLC: k' = 4.60, t0 = 1.77 (RP-18, ACN/ H2O 1:1).

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.

	x	y	z	Uiso*/Ueq
S1	0.78764 (6)	0.38838 (4)	0.14560 (4)	0.03408 (13)
S2	0.82812 (8)	0.09330 (5)	0.48592 (4)	0.04228 (15)
N1	0.7960 (2)	0.32182 (15)	0.22894 (13)	0.0378 (4)
N2	0.9528 (2)	0.35411 (15)	0.37411 (12)	0.0355 (4)
N3	0.5301 (3)	−0.00535 (17)	0.37232 (14)	0.0422 (4)
O1	0.6285 (2)	0.40847 (18)	0.12949 (14)	0.0516 (4)
O2	0.8372 (2)	0.32854 (15)	0.06896 (12)	0.0482 (4)
O3	0.4174 (2)	−0.00021 (18)	0.31698 (13)	0.0553 (5)
O4	0.5245 (3)	−0.08320 (18)	0.41086 (16)	0.0677 (6)
O5	1.1821 (2)	0.38075 (15)	0.52810 (12)	0.0465 (4)
O6	1.1375 (2)	0.23414 (16)	0.59779 (12)	0.0475 (4)
C1	0.9457 (3)	0.51416 (17)	0.20129 (15)	0.0328 (4)
C2	1.0033 (3)	0.6138 (2)	0.17343 (19)	0.0463 (5)
H2	0.9595	0.6231	0.1174	0.065*
C3	1.1305 (4)	0.6994 (2)	0.2336 (2)	0.0574 (7)
H3	1.1714	0.7683	0.2179	0.080*
C4	1.1979 (4)	0.6846 (2)	0.3168 (2)	0.0528 (6)
H4	1.2854	0.7426	0.3546	0.074*
C5	1.1361 (3)	0.58433 (19)	0.34400 (16)	0.0399 (5)
H5	1.1799	0.5748	0.4000	0.056*
C6	1.0071 (2)	0.49860 (16)	0.28539 (14)	0.0314 (4)
C7	0.9133 (2)	0.38550 (17)	0.29652 (14)	0.0310 (4)
C8	0.8755 (3)	0.25233 (17)	0.39677 (14)	0.0319 (4)
C9	0.7199 (3)	0.17426 (18)	0.35328 (15)	0.0361 (4)
H9	0.6530	0.1811	0.3028	0.050*
C10	0.6826 (3)	0.08730 (18)	0.39657 (15)	0.0369 (4)
C11	0.9476 (3)	0.21983 (18)	0.47066 (14)	0.0350 (4)
C12	1.1014 (3)	0.2871 (2)	0.53436 (15)	0.0375 (4)
C13	1.2858 (3)	0.2927 (3)	0.66588 (18)	0.0529 (6)
H13A	1.3808	0.3111	0.6367	0.074*
H13B	1.3026	0.2446	0.7060	0.074*
H13C	1.2723	0.3612	0.7000	0.074*
H2A	1.036 (4)	0.401 (3)	0.416 (2)	0.057 (9)*
S3	1.19939 (7)	0.08057 (5)	0.84081 (4)	0.03976 (14)
S4	0.55736 (7)	−0.42292 (5)	0.68575 (4)	0.03977 (14)
N4	1.0485 (2)	−0.04004 (16)	0.80561 (13)	0.0387 (4)
N5	0.9233 (2)	−0.19586 (15)	0.86273 (12)	0.0332 (3)
N6	0.5555 (3)	−0.2926 (2)	0.56298 (13)	0.0463 (5)
O7	1.3266 (3)	0.08190 (17)	0.78639 (13)	0.0556 (5)
O8	1.1299 (3)	0.17360 (16)	0.84891 (16)	0.0604 (5)
O9	0.6148 (3)	−0.2076 (2)	0.53579 (13)	0.0627 (6)
O10	0.4332 (3)	−0.3710 (2)	0.52161 (15)	0.0746 (7)
O11	0.7795 (2)	−0.38408 (16)	0.93357 (12)	0.0487 (4)
O12	0.6092 (2)	−0.53493 (14)	0.82870 (12)	0.0441 (4)
C14	1.2651 (3)	0.05876 (18)	0.94846 (14)	0.0352 (4)
C15	1.3942 (3)	0.1271 (2)	1.01748 (18)	0.0474 (6)
H15	1.4612	0.1963	1.0117	0.066*
C16	1.4187 (3)	0.0876 (3)	1.09528 (18)	0.0541 (7)
H16	1.5047	0.1307	1.1428	0.076*
C17	1.3169 (4)	−0.0153 (2)	1.10338 (17)	0.0516 (6)
H17	1.3359	−0.0397	1.1565	0.072*
C18	1.1866 (3)	−0.0831 (2)	1.03386 (15)	0.0394 (5)
H18	1.1185	−0.1519	1.0398	0.055*
C19	1.1628 (2)	−0.04395 (16)	0.95559 (13)	0.0302 (4)
C20	1.0386 (2)	−0.09623 (16)	0.86997 (13)	0.0302 (4)
C21	0.7995 (2)	−0.25694 (17)	0.78739 (13)	0.0301 (4)
C22	0.7594 (3)	−0.21886 (18)	0.70763 (14)	0.0337 (4)
H22	0.8117	−0.1487	0.6967	0.047*
C23	0.6318 (3)	−0.30199 (19)	0.64987 (14)	0.0355 (4)
C24	0.7004 (2)	−0.36494 (17)	0.78475 (13)	0.0317 (4)
C25	0.7026 (3)	−0.42710 (18)	0.85771 (15)	0.0351 (4)
C26	0.5853 (5)	−0.6019 (3)	0.8964 (2)	0.0609 (8)
H26A	0.6918	−0.5963	0.9303	0.085*
H26B	0.5291	−0.6797	0.8671	0.085*
H26C	0.5191	−0.5739	0.9368	0.085*
H5A	0.936 (4)	−0.233 (3)	0.902 (2)	0.052 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0325 (2)	0.0321 (2)	0.0353 (2)	0.00579 (18)	−0.00127 (19)	0.01206 (19)
S2	0.0439 (3)	0.0377 (3)	0.0409 (3)	0.0013 (2)	−0.0005 (2)	0.0190 (2)
N1	0.0393 (9)	0.0300 (8)	0.0371 (9)	−0.0008 (7)	−0.0044 (7)	0.0136 (7)
N2	0.0383 (9)	0.0300 (8)	0.0320 (8)	0.0002 (7)	−0.0011 (7)	0.0111 (7)
N3	0.0435 (10)	0.0370 (9)	0.0382 (9)	−0.0006 (8)	0.0040 (8)	0.0093 (8)
O1	0.0346 (8)	0.0658 (12)	0.0582 (11)	0.0152 (8)	0.0018 (8)	0.0270 (9)
O2	0.0598 (11)	0.0430 (9)	0.0405 (9)	0.0169 (8)	0.0036 (8)	0.0071 (7)
O3	0.0434 (10)	0.0597 (11)	0.0490 (10)	−0.0026 (8)	−0.0065 (8)	0.0141 (9)
O4	0.0666 (13)	0.0477 (11)	0.0740 (14)	−0.0122 (9)	−0.0064 (11)	0.0319 (10)
O5	0.0420 (9)	0.0400 (8)	0.0485 (9)	−0.0029 (7)	−0.0049 (7)	0.0181 (7)
O6	0.0429 (9)	0.0492 (9)	0.0435 (9)	−0.0013 (7)	−0.0057 (7)	0.0241 (8)
C1	0.0320 (9)	0.0275 (9)	0.0392 (10)	0.0077 (7)	0.0046 (8)	0.0111 (7)
C2	0.0520 (14)	0.0355 (11)	0.0557 (14)	0.0125 (10)	0.0100 (11)	0.0210 (10)
C3	0.0613 (16)	0.0294 (11)	0.0760 (19)	0.0017 (11)	0.0118 (14)	0.0160 (12)
C4	0.0490 (14)	0.0309 (11)	0.0650 (16)	−0.0022 (10)	0.0071 (12)	0.0001 (11)
C5	0.0362 (10)	0.0322 (10)	0.0421 (11)	0.0025 (8)	0.0002 (9)	0.0008 (8)
C6	0.0313 (9)	0.0246 (8)	0.0370 (10)	0.0069 (7)	0.0047 (7)	0.0066 (7)
C7	0.0313 (9)	0.0276 (9)	0.0336 (9)	0.0067 (7)	0.0039 (7)	0.0098 (7)
C8	0.0326 (9)	0.0311 (9)	0.0312 (9)	0.0056 (7)	0.0045 (7)	0.0111 (7)
C9	0.0360 (10)	0.0347 (10)	0.0349 (10)	0.0059 (8)	0.0023 (8)	0.0108 (8)
C10	0.0375 (10)	0.0322 (10)	0.0350 (10)	0.0012 (8)	0.0023 (8)	0.0091 (8)
C11	0.0352 (10)	0.0326 (9)	0.0346 (10)	0.0036 (8)	0.0026 (8)	0.0127 (8)
C12	0.0363 (10)	0.0397 (11)	0.0328 (10)	0.0042 (8)	0.0019 (8)	0.0121 (8)
C13	0.0490 (14)	0.0580 (15)	0.0436 (13)	0.0027 (11)	−0.0078 (11)	0.0210 (11)
S3	0.0438 (3)	0.0320 (3)	0.0403 (3)	0.0034 (2)	0.0067 (2)	0.0123 (2)
S4	0.0376 (3)	0.0380 (3)	0.0345 (3)	0.0007 (2)	−0.0030 (2)	0.0068 (2)
N4	0.0412 (10)	0.0360 (9)	0.0343 (9)	0.0026 (7)	−0.0003 (7)	0.0137 (7)
N5	0.0322 (8)	0.0319 (8)	0.0314 (8)	0.0028 (6)	−0.0027 (6)	0.0118 (7)
N6	0.0504 (12)	0.0574 (12)	0.0307 (9)	0.0198 (10)	−0.0020 (8)	0.0094 (8)
O7	0.0558 (11)	0.0549 (11)	0.0510 (10)	0.0011 (9)	0.0198 (9)	0.0150 (9)
O8	0.0725 (14)	0.0395 (9)	0.0751 (14)	0.0190 (9)	0.0133 (11)	0.0238 (9)
O9	0.0863 (16)	0.0675 (13)	0.0424 (10)	0.0283 (12)	0.0063 (10)	0.0274 (9)
O10	0.0654 (14)	0.0885 (17)	0.0489 (11)	0.0051 (12)	−0.0229 (10)	0.0113 (11)
O11	0.0500 (10)	0.0497 (10)	0.0387 (8)	0.0017 (8)	−0.0034 (7)	0.0169 (7)
O12	0.0536 (10)	0.0334 (8)	0.0416 (8)	0.0048 (7)	0.0038 (7)	0.0141 (6)
C14	0.0335 (10)	0.0330 (10)	0.0346 (10)	0.0047 (8)	0.0045 (8)	0.0049 (8)
C15	0.0419 (12)	0.0394 (12)	0.0480 (13)	0.0006 (9)	0.0031 (10)	−0.0017 (10)
C16	0.0460 (13)	0.0580 (16)	0.0401 (12)	0.0037 (11)	−0.0090 (10)	−0.0058 (11)
C17	0.0580 (15)	0.0550 (15)	0.0334 (11)	0.0133 (12)	−0.0073 (10)	0.0040 (10)
C18	0.0435 (11)	0.0386 (11)	0.0342 (10)	0.0101 (9)	0.0018 (9)	0.0101 (8)
C19	0.0295 (9)	0.0292 (9)	0.0291 (9)	0.0067 (7)	0.0025 (7)	0.0043 (7)
C20	0.0292 (8)	0.0275 (8)	0.0314 (9)	0.0061 (7)	0.0013 (7)	0.0062 (7)
C21	0.0280 (8)	0.0303 (9)	0.0302 (9)	0.0071 (7)	0.0011 (7)	0.0075 (7)
C22	0.0347 (10)	0.0341 (9)	0.0322 (9)	0.0096 (8)	0.0021 (7)	0.0110 (8)
C23	0.0360 (10)	0.0404 (10)	0.0294 (9)	0.0111 (8)	0.0018 (8)	0.0091 (8)
C24	0.0308 (9)	0.0338 (9)	0.0287 (9)	0.0061 (7)	0.0016 (7)	0.0103 (7)
C25	0.0339 (10)	0.0354 (10)	0.0359 (10)	0.0063 (8)	0.0072 (8)	0.0132 (8)
C26	0.081 (2)	0.0467 (14)	0.0545 (16)	0.0060 (14)	0.0123 (14)	0.0285 (12)

S1—O1	1.4323 (18)	S3—O8	1.431 (2)
S1—O2	1.4361 (18)	S3—O7	1.4338 (19)
S1—N1	1.6507 (19)	S3—N4	1.649 (2)
S1—C1	1.763 (2)	S3—C14	1.763 (2)
S2—C10	1.697 (2)	S4—C23	1.700 (2)
S2—C11	1.716 (2)	S4—C24	1.719 (2)
N1—C7	1.308 (3)	N4—C20	1.310 (3)
N2—C7	1.347 (3)	N5—C20	1.343 (3)
N2—C8	1.399 (3)	N5—C21	1.400 (2)
N2—H2A	0.88 (3)	N5—H5A	0.84 (3)
N3—O3	1.217 (3)	N6—O9	1.222 (3)
N3—O4	1.224 (3)	N6—O10	1.228 (3)
N3—C10	1.443 (3)	N6—C23	1.442 (3)
O5—C12	1.221 (3)	O11—C25	1.205 (3)
O6—C12	1.322 (3)	O12—C25	1.334 (3)
O6—C13	1.450 (3)	O12—C26	1.449 (3)
C1—C2	1.381 (3)	C14—C19	1.381 (3)
C1—C6	1.392 (3)	C14—C15	1.388 (3)
C2—C3	1.391 (4)	C15—C16	1.383 (4)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.392 (5)	C16—C17	1.386 (4)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.389 (4)	C17—C18	1.395 (3)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.389 (3)	C18—C19	1.386 (3)
C5—H5	0.9300	C18—H18	0.9300
C6—C7	1.484 (3)	C19—C20	1.490 (3)
C8—C11	1.394 (3)	C21—C24	1.383 (3)
C8—C9	1.412 (3)	C21—C22	1.423 (3)
C9—C10	1.365 (3)	C22—C23	1.364 (3)
C9—H9	0.9300	C22—H22	0.9300
C11—C12	1.467 (3)	C24—C25	1.475 (3)
C13—H13A	0.9600	C26—H26A	0.9600
C13—H13B	0.9600	C26—H26B	0.9600
C13—H13C	0.9600	C26—H26C	0.9600
O1···C25i	2.893 (3)	C12···O9ii	3.063 (3)
O1—S1—O2	116.41 (12)	O8—S3—O7	117.16 (13)
O1—S1—N1	109.99 (11)	O8—S3—N4	109.67 (12)
O2—S1—N1	109.26 (11)	O7—S3—N4	109.93 (11)
O1—S1—C1	111.45 (11)	O8—S3—C14	110.86 (12)
O2—S1—C1	111.32 (11)	O7—S3—C14	110.92 (12)
N1—S1—C1	96.60 (9)	N4—S3—C14	96.31 (10)
C10—S2—C11	89.52 (10)	C23—S4—C24	89.12 (10)
C7—N1—S1	109.66 (14)	C20—N4—S3	109.72 (15)
C7—N2—C8	126.69 (18)	C20—N5—C21	126.90 (18)
C7—N2—H2A	119 (2)	C20—N5—H5A	118 (2)
C8—N2—H2A	115 (2)	C21—N5—H5A	114 (2)
O3—N3—O4	125.1 (2)	O9—N6—O10	124.5 (2)
O3—N3—C10	118.6 (2)	O9—N6—C23	118.5 (2)
O4—N3—C10	116.3 (2)	O10—N6—C23	117.1 (2)
C12—O6—C13	117.00 (19)	C25—O12—C26	116.8 (2)
C2—C1—C6	123.0 (2)	C19—C14—C15	122.7 (2)
C2—C1—S1	129.99 (19)	C19—C14—S3	107.78 (15)
C6—C1—S1	107.04 (14)	C15—C14—S3	129.52 (19)
C1—C2—C3	116.5 (2)	C16—C15—C14	117.0 (2)
C1—C2—H2	121.8	C16—C15—H15	121.5
C3—C2—H2	121.8	C14—C15—H15	121.5
C2—C3—C4	121.7 (2)	C15—C16—C17	120.9 (2)
C2—C3—H3	119.2	C15—C16—H16	119.5
C4—C3—H3	119.2	C17—C16—H16	119.5
C5—C4—C3	120.8 (2)	C16—C17—C18	121.7 (2)
C5—C4—H4	119.6	C16—C17—H17	119.2
C3—C4—H4	119.6	C18—C17—H17	119.2
C4—C5—C6	118.3 (2)	C19—C18—C17	117.4 (2)
C4—C5—H5	120.9	C19—C18—H18	121.3
C6—C5—H5	120.9	C17—C18—H18	121.3
C5—C6—C1	119.77 (19)	C14—C19—C18	120.26 (19)
C5—C6—C7	130.5 (2)	C14—C19—C20	109.28 (18)
C1—C6—C7	109.67 (17)	C18—C19—C20	130.45 (19)
N1—C7—N2	123.96 (18)	N4—C20—N5	123.65 (18)
N1—C7—C6	116.99 (18)	N4—C20—C19	116.87 (18)
N2—C7—C6	119.05 (18)	N5—C20—C19	119.48 (18)
C11—C8—N2	121.07 (19)	C24—C21—N5	121.09 (18)
C11—C8—C9	112.35 (18)	C24—C21—C22	112.71 (18)
N2—C8—C9	126.54 (19)	N5—C21—C22	126.20 (18)
C10—C9—C8	109.73 (19)	C23—C22—C21	108.87 (19)
C10—C9—H9	125.1	C23—C22—H22	125.6
C8—C9—H9	125.1	C21—C22—H22	125.6
C9—C10—N3	124.6 (2)	C22—C23—N6	124.6 (2)
C9—C10—S2	115.90 (17)	C22—C23—S4	116.54 (16)
N3—C10—S2	119.44 (16)	N6—C23—S4	118.88 (17)
C8—C11—C12	125.68 (19)	C21—C24—C25	126.73 (18)
C8—C11—S2	112.46 (16)	C21—C24—S4	112.76 (15)
C12—C11—S2	121.70 (16)	C25—C24—S4	120.43 (15)
O5—C12—O6	125.7 (2)	O11—C25—O12	125.3 (2)
O5—C12—C11	122.7 (2)	O11—C25—C24	123.3 (2)
O6—C12—C11	111.63 (19)	O12—C25—C24	111.37 (18)
O6—C13—H13A	109.5	O12—C26—H26A	109.5
O6—C13—H13B	109.5	O12—C26—H26B	109.5
H13A—C13—H13B	109.5	H26A—C26—H26B	109.5
O6—C13—H13C	109.5	O12—C26—H26C	109.5
H13A—C13—H13C	109.5	H26A—C26—H26C	109.5
H13B—C13—H13C	109.5	H26B—C26—H26C	109.5
O1—S1—N1—C7	−117.46 (18)	O8—S3—N4—C20	−113.04 (18)
O2—S1—N1—C7	113.60 (17)	O7—S3—N4—C20	116.77 (18)
C1—S1—N1—C7	−1.75 (18)	C14—S3—N4—C20	1.79 (18)
O1—S1—C1—C2	−61.9 (2)	O8—S3—C14—C19	112.61 (17)
O2—S1—C1—C2	69.9 (2)	O7—S3—C14—C19	−115.43 (16)
N1—S1—C1—C2	−176.5 (2)	N4—S3—C14—C19	−1.26 (17)
O1—S1—C1—C6	116.68 (16)	O8—S3—C14—C15	−67.5 (3)
O2—S1—C1—C6	−111.53 (16)	O7—S3—C14—C15	64.5 (3)
N1—S1—C1—C6	2.15 (16)	N4—S3—C14—C15	178.6 (2)
C6—C1—C2—C3	1.1 (4)	C19—C14—C15—C16	0.6 (4)
S1—C1—C2—C3	179.5 (2)	S3—C14—C15—C16	−179.3 (2)
C1—C2—C3—C4	1.1 (4)	C14—C15—C16—C17	−0.6 (4)
C2—C3—C4—C5	−2.2 (5)	C15—C16—C17—C18	0.2 (4)
C3—C4—C5—C6	1.0 (4)	C16—C17—C18—C19	0.3 (4)
C4—C5—C6—C1	1.1 (3)	C15—C14—C19—C18	−0.1 (3)
C4—C5—C6—C7	−177.8 (2)	S3—C14—C19—C18	179.79 (17)
C2—C1—C6—C5	−2.3 (3)	C15—C14—C19—C20	−179.5 (2)
S1—C1—C6—C5	179.00 (17)	S3—C14—C19—C20	0.4 (2)
C2—C1—C6—C7	176.9 (2)	C17—C18—C19—C14	−0.3 (3)
S1—C1—C6—C7	−1.9 (2)	C17—C18—C19—C20	178.9 (2)
S1—N1—C7—N2	−178.88 (17)	S3—N4—C20—N5	177.40 (17)
S1—N1—C7—C6	0.9 (2)	S3—N4—C20—C19	−1.9 (2)
C8—N2—C7—N1	−1.7 (4)	C21—N5—C20—N4	1.5 (3)
C8—N2—C7—C6	178.53 (19)	C21—N5—C20—C19	−179.26 (18)
C5—C6—C7—N1	179.8 (2)	C14—C19—C20—N4	0.9 (3)
C1—C6—C7—N1	0.8 (3)	C18—C19—C20—N4	−178.4 (2)
C5—C6—C7—N2	−0.5 (3)	C14—C19—C20—N5	−178.37 (19)
C1—C6—C7—N2	−179.47 (19)	C18—C19—C20—N5	2.3 (3)
C7—N2—C8—C11	167.2 (2)	C20—N5—C21—C24	172.4 (2)
C7—N2—C8—C9	−15.3 (4)	C20—N5—C21—C22	−7.9 (3)
C11—C8—C9—C10	0.1 (3)	C24—C21—C22—C23	−0.2 (3)
N2—C8—C9—C10	−177.6 (2)	N5—C21—C22—C23	−179.8 (2)
C8—C9—C10—N3	177.6 (2)	C21—C22—C23—N6	178.6 (2)
C8—C9—C10—S2	−1.4 (3)	C21—C22—C23—S4	0.0 (2)
O3—N3—C10—C9	−9.3 (4)	O9—N6—C23—C22	4.9 (4)
O4—N3—C10—C9	171.6 (2)	O10—N6—C23—C22	−174.4 (2)
O3—N3—C10—S2	169.59 (19)	O9—N6—C23—S4	−176.59 (19)
O4—N3—C10—S2	−9.5 (3)	O10—N6—C23—S4	4.1 (3)
C11—S2—C10—C9	1.7 (2)	C24—S4—C23—C22	0.10 (18)
C11—S2—C10—N3	−177.3 (2)	C24—S4—C23—N6	−178.52 (18)
N2—C8—C11—C12	3.4 (3)	N5—C21—C24—C25	3.2 (3)
C9—C8—C11—C12	−174.5 (2)	C22—C21—C24—C25	−176.52 (19)
N2—C8—C11—S2	178.97 (16)	N5—C21—C24—S4	179.92 (15)
C9—C8—C11—S2	1.1 (2)	C22—C21—C24—S4	0.2 (2)
C10—S2—C11—C8	−1.53 (18)	C23—S4—C24—C21	−0.20 (17)
C10—S2—C11—C12	174.2 (2)	C23—S4—C24—C25	176.80 (18)
C13—O6—C12—O5	0.1 (4)	C26—O12—C25—O11	6.7 (4)
C13—O6—C12—C11	−179.2 (2)	C26—O12—C25—C24	−173.1 (2)
C8—C11—C12—O5	0.2 (4)	C21—C24—C25—O11	9.4 (4)
S2—C11—C12—O5	−175.0 (2)	S4—C24—C25—O11	−167.15 (19)
C8—C11—C12—O6	179.5 (2)	C21—C24—C25—O12	−170.9 (2)
S2—C11—C12—O6	4.3 (3)	S4—C24—C25—O12	12.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5	0.88 (3)	2.08 (3)	2.765 (2)	134 (3)
N5—H5A···O11	0.84 (3)	2.17 (3)	2.825 (3)	134 (3)
N5—H5A···O2ii	0.84 (3)	2.55 (3)	3.141 (3)	128 (3)
C4—H4···O4iii	0.93	2.48	3.376 (3)	162
C5—H5···O10iii	0.93	2.51	3.316 (3)	146
C17—H17···O3iv	0.93	2.38	3.223 (3)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O5	0.88 (3)	2.08 (3)	2.765 (2)	134 (3)
N5—H5A⋯O11	0.84 (3)	2.17 (3)	2.825 (3)	134 (3)
N5—H5A⋯O2i	0.84 (3)	2.55 (3)	3.141 (3)	128 (3)
C4—H4⋯O4ii	0.93	2.48	3.376 (3)	162
C5—H5⋯O10ii	0.93	2.51	3.316 (3)	146
C17—H17⋯O3iii	0.93	2.38	3.223 (3)	151

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