4-(3-Methyl-anilino)-N-[N-(1-methyl-ethyl)carbamo-yl]pyridinium-3-sulfon-amidate (torasemide) methanol 0.25-solvate 0.25-hydrate.

The title compound, C(16)H(20)N(4)O(3)S·0.25CH(4)O·0.25H(2)O, is a hydrate/methanol solvate of torasemide, a diuretic drug used in the treatment of hypertension. The asymmetric unit contains two torasemide mol-ecules and half-occupied methanol and water mol-ecules. It is isomorphous with the previously reported nonsolvated T-II form of torasemide. The water mol-ecules contribute to the stability of the structure by participating in an extensive system of O-H⋯O hydrogen bonds; N-H⋯N and N-H⋯O hydrogen bonds are also present. Both asymmetric mol-ecules of torasemide form inversion dimers in the crystal.

Related literature

For background on the medicinal properties and polymorphism of torasemide, see: Uchida et al. (1991 ▶); Broekhuysen et al. (1986 ▶); Ghys et al. (1985 ▶); Ishido & Senzaki (2008 ▶); Cosin & Diez (2002 ▶); Murray et al. (2001 ▶); Dupont et al. (1978 ▶); Danilovski et al. (2001 ▶).

Experimental

Crystal data

C16H20N4O3S·0.25CH4O·0.25H2O

M = 360.94

Monoclinic,

a = 16.8477 (2) Å

b = 11.5951 (1) Å

c = 20.3256 (2) Å

β = 108.646 (1)°

V = 3762.21 (7) Å3

Z = 8

Cu Kα radiation

μ = 1.74 mm−1

T = 200 K

0.45 × 0.38 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur PX Ultra CCD diffractometer

Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006 ▶) T min = 0.502, T max = 1.000 (expected range = 0.407–0.811)

50677 measured reflections

7402 independent reflections

6976 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.156

S = 1.04

7402 reflections

496 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.95 e Å−3

Δρmin = −0.57 e Å−3

Data collection: CrysAlisPro CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlisPro CCD; data reduction: CrysAlisPro RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶), WinGX (Farrugia, 1999 ▶) and PARST (Nardelli, 1995 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901160X/hb2934sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901160X/hb2934Isup2.hkl

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

C16H20N4O3S·0.25CH4O·0.25H2O	F(000) = 1528
Mr = 360.94	Dx = 1.274 Mg m−3
Monoclinic, P2/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yac	Cell parameters from 37208 reflections
a = 16.8477 (2) Å	θ = 4.1–72.4°
b = 11.5951 (1) Å	µ = 1.74 mm−1
c = 20.3256 (2) Å	T = 200 K
β = 108.646 (1)°	Prism, colorless
V = 3762.21 (7) Å3	0.45 × 0.38 × 0.12 mm
Z = 8

Oxford Diffraction Xcalibur PX Ultra CCD diffractometer	7402 independent reflections
Radiation source: fine-focus sealed tube	6976 reflections with I > 2σ(I)
Oxford Diffraction Enhance ULTRA assembly	Rint = 0.031
Detector resolution: 8.1241 pixels mm-1	θmax = 72.9°, θmin = 4.1°
ω scans	h = −17→20
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006)	k = −13→13
Tmin = 0.502, Tmax = 1.000	l = −25→25
50677 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.156	w = 1/[σ2(Fo2) + (0.0978P)2 + 2.03P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
7402 reflections	Δρmax = 0.95 e Å−3
496 parameters	Δρmin = −0.57 e Å−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00135 (17)

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	Occ. (<1)
C1	0.19533 (12)	0.48508 (17)	−0.00966 (10)	0.0373 (4)
C2	0.27341 (13)	0.43982 (19)	−0.01066 (12)	0.0437 (5)
H2	0.2910	0.3659	0.0087	0.052*
C3	0.32285 (14)	0.5010 (2)	−0.03890 (12)	0.0485 (5)
H3	0.3756	0.4706	−0.0379	0.058*
N2	0.29823 (12)	0.60467 (17)	−0.06847 (10)	0.0459 (4)
H2N	0.3334 (18)	0.643 (2)	−0.0811 (15)	0.055*
C4	0.22400 (13)	0.64928 (19)	−0.07146 (11)	0.0420 (4)
H4	0.2076	0.7215	−0.0937	0.050*
C5	0.17111 (12)	0.59364 (17)	−0.04330 (10)	0.0369 (4)
S1	0.07610 (3)	0.66425 (4)	−0.04649 (2)	0.03510 (15)
O1	0.08434 (9)	0.69312 (13)	0.02476 (7)	0.0404 (3)
O2	0.06917 (10)	0.76225 (12)	−0.09190 (8)	0.0426 (3)
N3	0.00665 (10)	0.56968 (14)	−0.07018 (8)	0.0357 (3)
C6	−0.00564 (12)	0.51828 (17)	−0.13380 (10)	0.0365 (4)
O3	0.02024 (10)	0.55425 (13)	−0.18126 (8)	0.0460 (4)
N4	−0.04911 (12)	0.41930 (16)	−0.14092 (9)	0.0445 (4)
H4N	−0.0622 (17)	0.389 (2)	−0.1047 (15)	0.053*
C7	−0.05800 (17)	0.3402 (2)	−0.19833 (12)	0.0533 (6)
H7	−0.0722	0.3856	−0.2424	0.064*
C8	−0.1274 (2)	0.2567 (3)	−0.20331 (17)	0.0795 (10)
H81	−0.1136	0.2106	−0.1607	0.119*
H82	−0.1346	0.2058	−0.2433	0.119*
H83	−0.1795	0.2992	−0.2092	0.119*
C9	0.0240 (2)	0.2749 (3)	−0.1887 (2)	0.0837 (10)
H91	0.0699	0.3303	−0.1823	0.126*
H92	0.0186	0.2277	−0.2299	0.126*
H93	0.0361	0.2251	−0.1477	0.126*
N1	0.14707 (11)	0.42831 (15)	0.02100 (10)	0.0403 (4)
H1N	0.0987 (18)	0.452 (2)	0.0161 (14)	0.048*
C10	0.17350 (13)	0.32972 (18)	0.06475 (11)	0.0404 (4)
C11	0.12689 (15)	0.23004 (18)	0.04998 (12)	0.0445 (5)
H11	0.0792	0.2260	0.0095	0.053*
C12	0.14906 (17)	0.1347 (2)	0.09404 (14)	0.0527 (6)
C13	0.21970 (18)	0.1432 (2)	0.15223 (14)	0.0602 (7)
H13	0.2363	0.0787	0.1824	0.072*
C14	0.26604 (18)	0.2426 (3)	0.16715 (15)	0.0632 (7)
H14	0.3140	0.2464	0.2074	0.076*
C15	0.24336 (16)	0.3373 (2)	0.12404 (13)	0.0542 (6)
H15	0.2750	0.4066	0.1347	0.065*
C16	0.0971 (2)	0.0273 (2)	0.07844 (19)	0.0770 (9)
H161	0.1053	−0.0119	0.0384	0.116*
H162	0.0378	0.0474	0.0679	0.116*
H163	0.1141	−0.0241	0.1188	0.116*
C17	0.46551 (12)	0.07450 (16)	0.14989 (10)	0.0361 (4)
C18	0.45704 (14)	0.05823 (19)	0.21650 (10)	0.0427 (5)
H18	0.4363	−0.0129	0.2275	0.051*
C19	0.47838 (14)	0.14364 (19)	0.26474 (11)	0.0437 (5)
H19	0.4733	0.1307	0.3094	0.052*
N6	0.50654 (12)	0.24638 (16)	0.25054 (9)	0.0418 (4)
H6N	0.5204 (16)	0.304 (2)	0.2829 (14)	0.050*
C20	0.51362 (13)	0.26759 (17)	0.18762 (11)	0.0381 (4)
H20	0.5332	0.3408	0.1785	0.046*
C21	0.49306 (12)	0.18543 (16)	0.13642 (10)	0.0344 (4)
S2	0.50042 (3)	0.21861 (4)	0.05304 (2)	0.03520 (15)
O5	0.53461 (10)	0.33358 (12)	0.05809 (8)	0.0430 (3)
O4	0.41666 (9)	0.20622 (13)	0.00468 (8)	0.0438 (3)
N7	0.55423 (10)	0.11763 (14)	0.03788 (8)	0.0360 (3)
C22	0.63508 (13)	0.10566 (17)	0.08225 (10)	0.0373 (4)
O6	0.67497 (9)	0.18090 (13)	0.12360 (7)	0.0432 (3)
N8	0.66900 (14)	0.00256 (19)	0.07774 (11)	0.0555 (5)
H8N	0.636 (2)	−0.047 (3)	0.0531 (17)	0.067*
C23	0.75356 (18)	−0.0308 (3)	0.11811 (16)	0.0696 (8)
H23	0.7776	0.0268	0.1559	0.084*
C24	0.7492 (3)	−0.1528 (5)	0.1507 (3)	0.134 (2)
H241	0.7311	−0.1440	0.1917	0.201*
H242	0.8046	−0.1890	0.1642	0.201*
H243	0.7089	−0.2015	0.1164	0.201*
C25	0.8076 (3)	−0.0405 (5)	0.0741 (3)	0.128 (2)
H251	0.7865	−0.1020	0.0398	0.192*
H252	0.8649	−0.0588	0.1031	0.192*
H253	0.8074	0.0328	0.0500	0.192*
N5	0.45039 (12)	−0.01004 (14)	0.10282 (9)	0.0404 (4)
H5N	0.4718 (16)	−0.004 (2)	0.0697 (14)	0.048*
C26	0.41125 (13)	−0.11707 (16)	0.10831 (10)	0.0370 (4)
C27	0.45708 (15)	−0.21778 (18)	0.11739 (11)	0.0426 (5)
H27	0.5151	−0.2154	0.1226	0.051*
C28	0.41752 (17)	−0.32354 (19)	0.11896 (11)	0.0497 (5)
C29	0.33272 (17)	−0.3224 (2)	0.11144 (12)	0.0525 (6)
H29	0.3052	−0.3934	0.1131	0.063*
C30	0.28749 (16)	−0.2224 (2)	0.10169 (13)	0.0521 (6)
H30	0.2293	−0.2246	0.0959	0.063*
C31	0.32645 (14)	−0.11830 (19)	0.10030 (11)	0.0440 (5)
H31	0.2956	−0.0483	0.0939	0.053*
C32	0.4664 (2)	−0.4336 (2)	0.12887 (16)	0.0704 (8)
H321	0.4287	−0.4990	0.1264	0.106*
H322	0.5100	−0.4328	0.1744	0.106*
H323	0.4925	−0.4410	0.0923	0.106*
O8	0.7099 (4)	0.2571 (5)	0.2572 (2)	0.0972 (18)	0.50
H81O	0.740 (6)	0.221 (10)	0.284 (4)	0.146*	0.50
H82O	0.706 (7)	0.228 (10)	0.223 (4)	0.146*	0.50
O7	0.6701 (3)	0.4556 (5)	0.2137 (3)	0.0920 (14)	0.50
H7O	0.679 (6)	0.397 (2)	0.2459 (11)	0.138*	0.50
C33	0.7049 (4)	0.5514 (6)	0.2484 (5)	0.087 (2)	0.50
H331	0.6809	0.5664	0.2856	0.131*	0.50
H332	0.6935	0.6171	0.2164	0.131*	0.50
H333	0.7656	0.5405	0.2685	0.131*	0.50

	U11	U22	U33	U12	U13	U23
C1	0.0406 (10)	0.0365 (10)	0.0361 (9)	−0.0021 (8)	0.0140 (8)	0.0001 (8)
C2	0.0443 (11)	0.0418 (11)	0.0480 (11)	0.0013 (8)	0.0192 (9)	−0.0009 (9)
C3	0.0451 (11)	0.0534 (13)	0.0518 (12)	−0.0019 (10)	0.0221 (10)	−0.0072 (10)
N2	0.0467 (10)	0.0478 (10)	0.0502 (10)	−0.0092 (8)	0.0254 (8)	−0.0023 (8)
C4	0.0476 (11)	0.0412 (11)	0.0407 (10)	−0.0066 (9)	0.0188 (9)	−0.0011 (8)
C5	0.0421 (10)	0.0360 (10)	0.0341 (9)	−0.0047 (8)	0.0142 (8)	0.0008 (7)
S1	0.0427 (3)	0.0318 (3)	0.0331 (3)	−0.00044 (17)	0.01538 (19)	0.00419 (17)
O1	0.0506 (8)	0.0383 (7)	0.0344 (7)	−0.0024 (6)	0.0165 (6)	0.0000 (6)
O2	0.0553 (8)	0.0328 (7)	0.0412 (8)	−0.0009 (6)	0.0174 (6)	0.0084 (6)
N3	0.0400 (8)	0.0349 (8)	0.0341 (8)	−0.0001 (6)	0.0146 (6)	0.0034 (6)
C6	0.0414 (10)	0.0349 (9)	0.0343 (9)	0.0022 (8)	0.0139 (8)	0.0068 (7)
O3	0.0672 (10)	0.0375 (8)	0.0396 (7)	−0.0043 (7)	0.0258 (7)	0.0047 (6)
N4	0.0593 (11)	0.0420 (10)	0.0351 (9)	−0.0114 (8)	0.0191 (8)	0.0007 (7)
C7	0.0709 (15)	0.0504 (13)	0.0381 (11)	−0.0137 (11)	0.0166 (10)	−0.0022 (9)
C8	0.102 (2)	0.077 (2)	0.0585 (16)	−0.0408 (19)	0.0252 (16)	−0.0156 (15)
C9	0.093 (2)	0.074 (2)	0.081 (2)	0.0160 (17)	0.0221 (18)	−0.0136 (17)
N1	0.0387 (9)	0.0367 (9)	0.0487 (10)	0.0042 (7)	0.0183 (7)	0.0114 (7)
C10	0.0435 (10)	0.0377 (10)	0.0435 (11)	0.0053 (8)	0.0185 (9)	0.0081 (8)
C11	0.0512 (12)	0.0373 (11)	0.0488 (12)	0.0033 (9)	0.0212 (10)	0.0044 (9)
C12	0.0706 (15)	0.0356 (11)	0.0616 (14)	0.0065 (10)	0.0345 (12)	0.0070 (10)
C13	0.0782 (17)	0.0478 (13)	0.0590 (15)	0.0194 (12)	0.0279 (13)	0.0203 (11)
C14	0.0624 (15)	0.0654 (16)	0.0553 (14)	0.0104 (13)	0.0098 (12)	0.0166 (12)
C15	0.0526 (13)	0.0508 (14)	0.0545 (14)	−0.0008 (10)	0.0103 (10)	0.0092 (10)
C16	0.107 (2)	0.0411 (14)	0.089 (2)	−0.0082 (14)	0.0399 (19)	0.0062 (14)
C17	0.0435 (10)	0.0321 (9)	0.0348 (9)	−0.0025 (8)	0.0156 (8)	−0.0036 (7)
C18	0.0576 (12)	0.0384 (10)	0.0365 (10)	−0.0092 (9)	0.0214 (9)	−0.0039 (8)
C19	0.0543 (12)	0.0451 (11)	0.0353 (10)	−0.0058 (9)	0.0192 (9)	−0.0050 (8)
N6	0.0520 (10)	0.0380 (9)	0.0374 (9)	−0.0038 (8)	0.0172 (7)	−0.0111 (7)
C20	0.0434 (10)	0.0323 (9)	0.0404 (10)	−0.0012 (8)	0.0159 (8)	−0.0047 (8)
C21	0.0401 (9)	0.0297 (9)	0.0359 (9)	−0.0021 (7)	0.0159 (8)	−0.0042 (7)
S2	0.0431 (3)	0.0301 (3)	0.0348 (3)	−0.00235 (17)	0.0158 (2)	−0.00089 (16)
O5	0.0552 (8)	0.0292 (7)	0.0493 (8)	−0.0046 (6)	0.0234 (7)	0.0004 (6)
O4	0.0443 (8)	0.0432 (8)	0.0416 (8)	−0.0003 (6)	0.0104 (6)	0.0008 (6)
N7	0.0446 (9)	0.0332 (8)	0.0332 (8)	−0.0022 (7)	0.0166 (7)	−0.0046 (6)
C22	0.0461 (10)	0.0366 (10)	0.0335 (9)	−0.0023 (8)	0.0187 (8)	−0.0019 (7)
O6	0.0512 (8)	0.0379 (7)	0.0385 (7)	−0.0064 (6)	0.0113 (6)	−0.0033 (6)
N8	0.0555 (12)	0.0475 (11)	0.0560 (12)	0.0099 (9)	0.0071 (9)	−0.0164 (9)
C23	0.0596 (15)	0.0695 (18)	0.0684 (17)	0.0205 (13)	0.0045 (13)	−0.0180 (14)
C24	0.101 (3)	0.176 (5)	0.126 (4)	0.047 (3)	0.037 (3)	0.084 (4)
C25	0.087 (3)	0.182 (5)	0.128 (4)	0.060 (3)	0.054 (3)	0.057 (4)
N5	0.0600 (11)	0.0299 (8)	0.0378 (9)	−0.0102 (7)	0.0250 (8)	−0.0059 (7)
C26	0.0514 (11)	0.0313 (9)	0.0307 (9)	−0.0070 (8)	0.0163 (8)	−0.0040 (7)
C27	0.0544 (12)	0.0383 (11)	0.0369 (10)	0.0019 (9)	0.0172 (9)	−0.0022 (8)
C28	0.0794 (16)	0.0329 (11)	0.0373 (11)	0.0006 (10)	0.0192 (10)	−0.0040 (8)
C29	0.0742 (16)	0.0402 (12)	0.0450 (12)	−0.0181 (11)	0.0218 (11)	−0.0050 (9)
C30	0.0544 (13)	0.0528 (14)	0.0514 (13)	−0.0147 (10)	0.0201 (10)	−0.0059 (10)
C31	0.0507 (12)	0.0417 (11)	0.0412 (11)	−0.0013 (9)	0.0168 (9)	−0.0015 (8)
C32	0.103 (2)	0.0414 (13)	0.0661 (17)	0.0128 (14)	0.0255 (16)	0.0007 (12)
O8	0.109 (4)	0.119 (4)	0.042 (2)	0.056 (3)	−0.006 (2)	−0.015 (3)
O7	0.080 (3)	0.090 (3)	0.100 (4)	−0.010 (3)	0.020 (3)	−0.007 (3)
C33	0.049 (3)	0.066 (4)	0.134 (6)	0.007 (3)	0.013 (3)	−0.012 (4)

C1—N1	1.344 (3)	C18—H18	0.9500
C1—C2	1.422 (3)	C19—N6	1.347 (3)
C1—C5	1.428 (3)	C19—H19	0.9500
C2—C3	1.354 (3)	N6—C20	1.345 (3)
C2—H2	0.9500	N6—H6N	0.92 (3)
C3—N2	1.348 (3)	C20—C21	1.371 (3)
C3—H3	0.9500	C20—H20	0.9500
N2—C4	1.337 (3)	C21—S2	1.781 (2)
N2—H2N	0.84 (3)	S2—O5	1.4428 (14)
C4—C5	1.365 (3)	S2—O4	1.4462 (15)
C4—H4	0.9500	S2—N7	1.5704 (16)
C5—S1	1.781 (2)	N7—C22	1.379 (3)
S1—O2	1.4449 (14)	C22—O6	1.248 (2)
S1—O1	1.4491 (14)	C22—N8	1.341 (3)
S1—N3	1.5630 (17)	N8—C23	1.451 (3)
N3—C6	1.378 (3)	N8—H8N	0.85 (3)
C6—O3	1.250 (2)	C23—C25	1.471 (5)
C6—N4	1.344 (3)	C23—C24	1.574 (6)
N4—C7	1.454 (3)	C23—H23	1.0000
N4—H4N	0.90 (3)	C24—H241	0.9800
C7—C8	1.496 (4)	C24—H242	0.9800
C7—C9	1.533 (4)	C24—H243	0.9800
C7—H7	1.0000	C25—H251	0.9800
C8—H81	0.9800	C25—H252	0.9800
C8—H82	0.9800	C25—H253	0.9800
C8—H83	0.9800	N5—C26	1.426 (2)
C9—H91	0.9800	N5—H5N	0.86 (3)
C9—H92	0.9800	C26—C27	1.379 (3)
C9—H93	0.9800	C26—C31	1.385 (3)
N1—C10	1.429 (3)	C27—C28	1.401 (3)
N1—H1N	0.83 (3)	C27—H27	0.9500
C10—C11	1.375 (3)	C28—C29	1.387 (4)
C10—C15	1.392 (3)	C28—C32	1.497 (3)
C11—C12	1.396 (3)	C29—C30	1.367 (4)
C11—H11	0.9500	C29—H29	0.9500
C12—C13	1.387 (4)	C30—C31	1.379 (3)
C12—C16	1.498 (4)	C30—H30	0.9500
C13—C14	1.371 (4)	C31—H31	0.9500
C13—H13	0.9500	C32—H321	0.9800
C14—C15	1.380 (4)	C32—H322	0.9800
C14—H14	0.9500	C32—H323	0.9800
C15—H15	0.9500	O8—H81O	0.75 (5)
C16—H161	0.9800	O8—H82O	0.75 (5)
C16—H162	0.9800	O7—C33	1.346 (8)
C16—H163	0.9800	O7—H7O	0.923 (8)
C17—N5	1.336 (2)	C33—H331	0.9800
C17—C18	1.419 (3)	C33—H332	0.9800
C17—C21	1.423 (3)	C33—H333	0.9800
C18—C19	1.359 (3)
N1—C1—C2	121.69 (19)	C19—C18—H18	119.7
N1—C1—C5	122.07 (18)	C17—C18—H18	119.7
C2—C1—C5	116.25 (18)	N6—C19—C18	121.33 (19)
C3—C2—C1	120.7 (2)	N6—C19—H19	119.3
C3—C2—H2	119.7	C18—C19—H19	119.3
C1—C2—H2	119.7	C20—N6—C19	120.66 (18)
N2—C3—C2	120.9 (2)	C20—N6—H6N	117.9 (17)
N2—C3—H3	119.6	C19—N6—H6N	121.4 (17)
C2—C3—H3	119.6	N6—C20—C21	121.13 (19)
C4—N2—C3	121.00 (19)	N6—C20—H20	119.4
C4—N2—H2N	121 (2)	C21—C20—H20	119.4
C3—N2—H2N	117.2 (19)	C20—C21—C17	120.05 (18)
N2—C4—C5	121.6 (2)	C20—C21—S2	119.65 (15)
N2—C4—H4	119.2	C17—C21—S2	120.30 (14)
C5—C4—H4	119.2	O5—S2—O4	114.89 (9)
C4—C5—C1	119.49 (19)	O5—S2—N7	117.42 (9)
C4—C5—S1	117.85 (16)	O4—S2—N7	106.96 (9)
C1—C5—S1	122.59 (15)	O5—S2—C21	106.24 (9)
O2—S1—O1	114.78 (9)	O4—S2—C21	106.00 (9)
O2—S1—N3	117.08 (9)	N7—S2—C21	104.24 (9)
O1—S1—N3	107.04 (9)	C22—N7—S2	117.27 (13)
O2—S1—C5	105.84 (9)	O6—C22—N8	121.3 (2)
O1—S1—C5	105.79 (9)	O6—C22—N7	125.21 (18)
N3—S1—C5	105.32 (9)	N8—C22—N7	113.48 (18)
C6—N3—S1	117.75 (14)	C22—N8—C23	124.2 (2)
O3—C6—N4	120.94 (19)	C22—N8—H8N	116 (2)
O3—C6—N3	126.50 (19)	C23—N8—H8N	119 (2)
N4—C6—N3	112.55 (17)	N8—C23—C25	111.3 (3)
C6—N4—C7	122.53 (18)	N8—C23—C24	107.9 (3)
C6—N4—H4N	120.4 (18)	C25—C23—C24	108.0 (4)
C7—N4—H4N	115.1 (18)	N8—C23—H23	109.9
N4—C7—C8	109.9 (2)	C25—C23—H23	109.9
N4—C7—C9	110.6 (2)	C24—C23—H23	109.9
C8—C7—C9	110.0 (3)	C23—C24—H241	109.5
N4—C7—H7	108.8	C23—C24—H242	109.5
C8—C7—H7	108.8	H241—C24—H242	109.5
C9—C7—H7	108.8	C23—C24—H243	109.5
C7—C8—H81	109.5	H241—C24—H243	109.5
C7—C8—H82	109.5	H242—C24—H243	109.5
H81—C8—H82	109.5	C23—C25—H251	109.5
C7—C8—H83	109.5	C23—C25—H252	109.5
H81—C8—H83	109.5	H251—C25—H252	109.5
H82—C8—H83	109.5	C23—C25—H253	109.5
C7—C9—H91	109.5	H251—C25—H253	109.5
C7—C9—H92	109.5	H252—C25—H253	109.5
H91—C9—H92	109.5	C17—N5—C26	124.70 (17)
C7—C9—H93	109.5	C17—N5—H5N	117.8 (18)
H91—C9—H93	109.5	C26—N5—H5N	116.9 (18)
H92—C9—H93	109.5	C27—C26—C31	121.27 (19)
C1—N1—C10	124.46 (18)	C27—C26—N5	119.60 (19)
C1—N1—H1N	119.7 (19)	C31—C26—N5	119.01 (19)
C10—N1—H1N	115.8 (19)	C26—C27—C28	119.6 (2)
C11—C10—C15	120.5 (2)	C26—C27—H27	120.2
C11—C10—N1	119.59 (19)	C28—C27—H27	120.2
C15—C10—N1	119.82 (19)	C29—C28—C27	118.0 (2)
C10—C11—C12	120.5 (2)	C29—C28—C32	121.7 (2)
C10—C11—H11	119.7	C27—C28—C32	120.3 (2)
C12—C11—H11	119.7	C30—C29—C28	122.0 (2)
C13—C12—C11	118.2 (2)	C30—C29—H29	119.0
C13—C12—C16	121.5 (2)	C28—C29—H29	119.0
C11—C12—C16	120.3 (3)	C29—C30—C31	119.9 (2)
C14—C13—C12	121.4 (2)	C29—C30—H30	120.0
C14—C13—H13	119.3	C31—C30—H30	120.0
C12—C13—H13	119.3	C30—C31—C26	119.1 (2)
C13—C14—C15	120.4 (3)	C30—C31—H31	120.4
C13—C14—H14	119.8	C26—C31—H31	120.4
C15—C14—H14	119.8	C28—C32—H321	109.5
C14—C15—C10	119.1 (2)	C28—C32—H322	109.5
C14—C15—H15	120.5	H321—C32—H322	109.5
C10—C15—H15	120.5	C28—C32—H323	109.5
C12—C16—H161	109.5	H321—C32—H323	109.5
C12—C16—H162	109.5	H322—C32—H323	109.5
H161—C16—H162	109.5	H81O—O8—H82O	105.0 (10)
C12—C16—H163	109.5	C33—O7—H7O	107.0 (7)
H161—C16—H163	109.5	O7—C33—H331	109.5
H162—C16—H163	109.5	O7—C33—H332	109.5
N5—C17—C18	122.11 (18)	H331—C33—H332	109.5
N5—C17—C21	121.63 (17)	O7—C33—H333	109.5
C18—C17—C21	116.25 (17)	H331—C33—H333	109.5
C19—C18—C17	120.50 (19)	H332—C33—H333	109.5
N1—C1—C2—C3	−176.8 (2)	N5—C17—C18—C19	175.5 (2)
C5—C1—C2—C3	3.5 (3)	C21—C17—C18—C19	−3.0 (3)
C1—C2—C3—N2	−1.9 (3)	C17—C18—C19—N6	1.2 (4)
C2—C3—N2—C4	−0.8 (3)	C18—C19—N6—C20	0.6 (3)
C3—N2—C4—C5	1.7 (3)	C19—N6—C20—C21	−0.5 (3)
N2—C4—C5—C1	0.1 (3)	N6—C20—C21—C17	−1.5 (3)
N2—C4—C5—S1	176.95 (16)	N6—C20—C21—S2	178.14 (16)
N1—C1—C5—C4	177.7 (2)	N5—C17—C21—C20	−175.4 (2)
C2—C1—C5—C4	−2.6 (3)	C18—C17—C21—C20	3.1 (3)
N1—C1—C5—S1	1.0 (3)	N5—C17—C21—S2	5.0 (3)
C2—C1—C5—S1	−179.31 (15)	C18—C17—C21—S2	−176.49 (16)
C4—C5—S1—O2	10.41 (19)	C20—C21—S2—O5	3.78 (19)
C1—C5—S1—O2	−172.81 (16)	C17—C21—S2—O5	−176.60 (16)
C4—C5—S1—O1	−111.79 (17)	C20—C21—S2—O4	−118.87 (17)
C1—C5—S1—O1	64.99 (18)	C17—C21—S2—O4	60.75 (18)
C4—C5—S1—N3	135.05 (17)	C20—C21—S2—N7	128.44 (17)
C1—C5—S1—N3	−48.17 (18)	C17—C21—S2—N7	−51.94 (18)
O2—S1—N3—C6	57.06 (17)	O5—S2—N7—C22	54.98 (17)
O1—S1—N3—C6	−172.47 (14)	O4—S2—N7—C22	−174.19 (14)
C5—S1—N3—C6	−60.20 (16)	C21—S2—N7—C22	−62.19 (16)
S1—N3—C6—O3	−15.8 (3)	S2—N7—C22—O6	−16.3 (3)
S1—N3—C6—N4	163.11 (15)	S2—N7—C22—N8	163.34 (16)
O3—C6—N4—C7	9.4 (3)	O6—C22—N8—C23	−1.3 (4)
N3—C6—N4—C7	−169.6 (2)	N7—C22—N8—C23	179.1 (2)
C6—N4—C7—C8	−164.5 (2)	C22—N8—C23—C25	−110.2 (4)
C6—N4—C7—C9	73.9 (3)	C22—N8—C23—C24	131.5 (3)
C2—C1—N1—C10	10.9 (3)	C18—C17—N5—C26	11.2 (3)
C5—C1—N1—C10	−169.43 (19)	C21—C17—N5—C26	−170.33 (19)
C1—N1—C10—C11	−125.7 (2)	C17—N5—C26—C27	−112.5 (2)
C1—N1—C10—C15	57.9 (3)	C17—N5—C26—C31	71.3 (3)
C15—C10—C11—C12	−0.2 (3)	C31—C26—C27—C28	−0.4 (3)
N1—C10—C11—C12	−176.6 (2)	N5—C26—C27—C28	−176.50 (18)
C10—C11—C12—C13	−0.9 (3)	C26—C27—C28—C29	−0.2 (3)
C10—C11—C12—C16	178.8 (2)	C26—C27—C28—C32	−179.9 (2)
C11—C12—C13—C14	1.1 (4)	C27—C28—C29—C30	1.0 (3)
C16—C12—C13—C14	−178.5 (3)	C32—C28—C29—C30	−179.3 (2)
C12—C13—C14—C15	−0.3 (4)	C28—C29—C30—C31	−1.1 (4)
C13—C14—C15—C10	−0.9 (4)	C29—C30—C31—C26	0.5 (3)
C11—C10—C15—C14	1.1 (4)	C27—C26—C31—C30	0.2 (3)
N1—C10—C15—C14	177.5 (2)	N5—C26—C31—C30	176.38 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.83 (3)	2.37 (3)	2.986 (2)	131 (2)
N1—H1N···N3i	0.83 (3)	2.38 (3)	3.060 (2)	139 (2)
N2—H2N···O5ii	0.84 (3)	2.14 (3)	2.847 (2)	142 (3)
N2—H2N···O6ii	0.84 (3)	2.21 (3)	2.822 (2)	130 (2)
N4—H4N···O1i	0.90 (3)	2.02 (3)	2.919 (2)	174 (3)
N5—H5N···N7	0.86 (3)	2.21 (3)	2.910 (2)	138 (2)
N5—H5N···N7iii	0.86 (3)	2.47 (3)	3.098 (2)	130 (2)
N6—H6N···O2iv	0.92 (3)	2.53 (3)	3.036 (2)	115 (2)
N6—H6N···O3iv	0.92 (3)	1.79 (3)	2.667 (2)	158 (2)
N8—H8N···O4iii	0.85 (3)	2.21 (3)	3.034 (3)	164 (3)
O7—H7O···O8	0.92 (1)	1.70 (5)	2.480 (8)	140 (7)
O7—H7O···O8v	0.92 (1)	2.50 (10)	2.995 (9)	114 (8)
O8—H82O···O6	0.75 (5)	2.00 (6)	2.735 (5)	166 (11)
O8—H81O···O6v	0.75 (5)	2.02 (6)	2.721 (5)	158 (12)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3	0.83 (3)	2.37 (3)	2.986 (2)	131 (2)
N1—H1N⋯N3i	0.83 (3)	2.38 (3)	3.060 (2)	139 (2)
N2—H2N⋯O5ii	0.84 (3)	2.14 (3)	2.847 (2)	142 (3)
N2—H2N⋯O6ii	0.84 (3)	2.21 (3)	2.822 (2)	130 (2)
N4—H4N⋯O1i	0.90 (3)	2.02 (3)	2.919 (2)	174 (3)
N5—H5N⋯N7	0.86 (3)	2.21 (3)	2.910 (2)	138 (2)
N5—H5N⋯N7iii	0.86 (3)	2.47 (3)	3.098 (2)	130 (2)
N6—H6N⋯O2iv	0.92 (3)	2.53 (3)	3.036 (2)	115 (2)
N6—H6N⋯O3iv	0.92 (3)	1.79 (3)	2.667 (2)	158 (2)
N8—H8N⋯O4iii	0.85 (3)	2.21 (3)	3.034 (3)	164 (3)
O7—H7O⋯O8	0.923 (8)	1.70 (5)	2.480 (8)	140 (7)
O7—H7O⋯O8v	0.923 (8)	2.50 (10)	2.995 (9)	114 (8)
O8—H82O⋯O6	0.75 (5)	2.00 (6)	2.735 (5)	166 (11)
O8—H81O⋯O6v	0.75 (5)	2.02 (6)	2.721 (5)	158 (12)

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