4-(3-Methyl-anilino)-N-[N-(1-methyl-ethyl)carbamo-yl]pyridinium-3-sulfon-amidate (torasemide T-N): a low temperature redetermination.

The structure [Danilovski et al. (2001 ▶). Croat. Chim. Acta74, 103-120] of the T-N (non-solvated) polymorph of torasemide, C(16)H(20)N(4)O(3)S, a diuretic drug used in the treatment of hypertension, has been redetermined at low temperature. The zwitterionic form of the mol-ecule is confirmed, although GAUSSIAN03 calculations suggest that this form is less stable in the gas phase. The unit-cell contraction between 298 and 100 K is approximately isotropic and the largest structual change is in a C-N-C-C torsion angle, which differs by 11.4 (3)° between the room-temperature and low-temperature structures. There are two mol-ecules in the asymmetric unit, both of which contain an intra-molecular N-H⋯N hydrogen bond. In the crystal structure, both mol-ecules form inversion dimers linked by pairs of N-H⋯N hydrogen bonds. Further N-H⋯N and N-H⋯O hydrogen bonds lead to a three-dimensional network. The different hydrogen-bond arrangements and packing motifs in the polymorphs of torasemide are discussed in detail.

Related literature

For the crystal structures of polymorphs of torasemide, see: Dupont et al. (1978 ▶); Danilovski et al. (2001 ▶). For the structure of the water–methanol solvated T–II form of torasemide, see: Bartolucci et al. (2009 ▶).

Experimental

Crystal data

C16H20N4O3S

M = 348.42

Monoclinic,

a = 11.3378 (1) Å

b = 18.9055 (1) Å

c = 16.4958 (1) Å

β = 94.273 (1)°

V = 3525.99 (4) Å3

Z = 8

Cu Kα radiation

μ = 1.82 mm−1

T = 100 K

0.50 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur PX Ultra CCD diffractometer

Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006 ▶) T min = 0.541, T max = 1.000 (expected range = 0.412–0.761)

53231 measured reflections

6941 independent reflections

6840 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.117

S = 1.07

6941 reflections

458 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.36 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 ▶); software used to prepare material for publication: SHELXL97, WinGX (Farrugia, 1999 ▶), GAUSSIAN03 (Frisch et al., 2004 ▶) and PARST (Nardelli, 1995 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012069/hb2935sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012069/hb2935Isup2.hkl

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

C16H20N4O3S	F(000) = 1472
Mr = 348.42	Dx = 1.313 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ybc	Cell parameters from 43504 reflections
a = 11.3378 (1) Å	θ = 4.6–72.2°
b = 18.9055 (1) Å	µ = 1.82 mm−1
c = 16.4958 (1) Å	T = 100 K
β = 94.273 (1)°	Prism, colorless
V = 3525.99 (4) Å3	0.50 × 0.20 × 0.15 mm
Z = 8

Oxford Diffraction Xcalibur PX Ultra CCD diffractometer	6941 independent reflections
Radiation source: fine-focus sealed tube	6840 reflections with I > 2σ(I)
Oxford Diffraction, Enhance ULTRA assembly	Rint = 0.029
Detector resolution: 8.1241 pixels mm-1	θmax = 72.6°, θmin = 4.6°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006)	k = −19→23
Tmin = 0.541, Tmax = 1.000	l = −20→17
53231 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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0678P)2 + 1.9103P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
6941 reflections	Δρmax = 0.64 e Å−3
458 parameters	Δρmin = −0.36 e Å−3
0 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: 0.0029 (2)

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
C1	0.06628 (14)	0.35277 (8)	0.09441 (9)	0.0240 (3)
C2	0.05152 (15)	0.28496 (9)	0.12963 (10)	0.0292 (3)
H2	−0.0181	0.2749	0.1562	0.035*
C3	0.13599 (15)	0.23451 (9)	0.12564 (11)	0.0308 (4)
H3	0.1238	0.1893	0.1487	0.037*
N2	0.23689 (12)	0.24714 (7)	0.08976 (9)	0.0281 (3)
H2N	0.2975 (19)	0.2144 (11)	0.0880 (13)	0.034*
C4	0.25680 (14)	0.31069 (8)	0.05726 (9)	0.0253 (3)
H4	0.3287	0.3186	0.0326	0.030*
C5	0.17588 (13)	0.36451 (8)	0.05876 (9)	0.0232 (3)
S1	0.20832 (3)	0.446859 (19)	0.01391 (2)	0.02230 (12)
O1	0.19638 (10)	0.49999 (6)	0.07600 (7)	0.0259 (2)
O2	0.32755 (10)	0.44000 (6)	−0.01170 (7)	0.0259 (2)
N3	0.10577 (12)	0.45781 (7)	−0.05325 (8)	0.0242 (3)
C6	0.09635 (14)	0.41075 (8)	−0.11840 (9)	0.0253 (3)
O3	0.17766 (10)	0.37454 (6)	−0.14317 (7)	0.0285 (3)
N4	−0.01530 (13)	0.40839 (8)	−0.15352 (9)	0.0319 (3)
H4N	−0.069 (2)	0.4363 (12)	−0.1341 (14)	0.038*
C7	−0.04833 (16)	0.36875 (10)	−0.22750 (10)	0.0330 (4)
H7	0.0095	0.3292	−0.2316	0.040*
C8	−0.1707 (2)	0.33682 (15)	−0.22238 (16)	0.0605 (7)
H81	−0.1694	0.3039	−0.1764	0.091*
H82	−0.1936	0.3113	−0.2728	0.091*
H83	−0.2279	0.3746	−0.2146	0.091*
C9	−0.0425 (2)	0.41555 (12)	−0.30182 (12)	0.0474 (5)
H91	0.0377	0.4345	−0.3035	0.071*
H92	−0.0987	0.4547	−0.2989	0.071*
H93	−0.0627	0.3877	−0.3510	0.071*
N1	−0.01871 (12)	0.40159 (7)	0.09416 (8)	0.0252 (3)
H1N	−0.0117 (18)	0.4407 (12)	0.0675 (13)	0.030*
C10	−0.11809 (14)	0.39528 (8)	0.14235 (10)	0.0247 (3)
C11	−0.22992 (14)	0.38155 (8)	0.10547 (10)	0.0279 (3)
H11	−0.2402	0.3758	0.0482	0.033*
C12	−0.32729 (15)	0.37622 (9)	0.15230 (11)	0.0306 (4)
C13	−0.30887 (15)	0.38601 (9)	0.23606 (11)	0.0327 (4)
H13	−0.3740	0.3823	0.2689	0.039*
C14	−0.19782 (16)	0.40100 (10)	0.27239 (11)	0.0338 (4)
H14	−0.1876	0.4084	0.3294	0.041*
C15	−0.10120 (15)	0.40520 (9)	0.22556 (10)	0.0300 (3)
H15	−0.0245	0.4148	0.2503	0.036*
C16	−0.44868 (16)	0.36000 (11)	0.11375 (14)	0.0426 (5)
H161	−0.4641	0.3092	0.1178	0.064*
H162	−0.4532	0.3739	0.0564	0.064*
H163	−0.5079	0.3863	0.1419	0.064*
C17	0.53049 (14)	0.00721 (8)	0.20469 (10)	0.0255 (3)
C18	0.57906 (15)	0.00421 (9)	0.28673 (10)	0.0287 (3)
H18	0.6541	−0.0171	0.2990	0.034*
C19	0.51868 (16)	0.03167 (9)	0.34779 (10)	0.0303 (3)
H19	0.5517	0.0286	0.4023	0.036*
N6	0.41244 (13)	0.06327 (8)	0.33205 (9)	0.0295 (3)
H6N	0.3709 (19)	0.0776 (12)	0.3695 (14)	0.035*
C20	0.36491 (15)	0.07020 (9)	0.25530 (10)	0.0267 (3)
H20	0.2912	0.0938	0.2455	0.032*
C21	0.42078 (14)	0.04394 (8)	0.19141 (10)	0.0246 (3)
S2	0.34526 (3)	0.048572 (19)	0.09286 (2)	0.02303 (12)
O4	0.24685 (10)	0.09590 (6)	0.10138 (7)	0.0273 (2)
O5	0.31276 (10)	−0.02365 (6)	0.07219 (7)	0.0267 (2)
N7	0.43996 (12)	0.07155 (7)	0.03378 (8)	0.0241 (3)
C22	0.48491 (14)	0.13952 (8)	0.03857 (9)	0.0247 (3)
O6	0.44602 (10)	0.18959 (6)	0.07821 (7)	0.0297 (3)
N8	0.57991 (14)	0.14797 (8)	−0.00463 (10)	0.0335 (3)
H8N	0.611 (2)	0.1105 (12)	−0.0284 (14)	0.040*
C23	0.64106 (16)	0.21554 (9)	−0.00994 (12)	0.0337 (4)
H23	0.6350	0.2413	0.0425	0.040*
C24	0.5836 (2)	0.26095 (11)	−0.07816 (14)	0.0468 (5)
H241	0.5935	0.2382	−0.1306	0.070*
H242	0.6211	0.3077	−0.0771	0.070*
H243	0.4991	0.2662	−0.0707	0.070*
C25	0.77101 (18)	0.20277 (11)	−0.02102 (15)	0.0462 (5)
H251	0.8055	0.1739	0.0241	0.069*
H252	0.8125	0.2482	−0.0218	0.069*
H253	0.7790	0.1779	−0.0725	0.069*
N5	0.58380 (12)	−0.02241 (8)	0.14337 (8)	0.0278 (3)
H5N	0.5523 (18)	−0.0126 (11)	0.0923 (13)	0.033*
C26	0.67680 (15)	−0.07370 (10)	0.15013 (10)	0.0303 (4)
C27	0.77484 (16)	−0.06222 (12)	0.10718 (11)	0.0383 (4)
H27	0.7847	−0.0182	0.0808	0.046*
C28	0.86000 (18)	−0.11553 (17)	0.10247 (13)	0.0596 (7)
C29	0.8433 (3)	−0.17915 (16)	0.14258 (17)	0.0703 (9)
H29	0.9001	−0.2158	0.1398	0.084*
C30	0.7461 (3)	−0.18997 (14)	0.18613 (17)	0.0644 (7)
H30	0.7368	−0.2336	0.2135	0.077*
C31	0.66150 (19)	−0.13720 (11)	0.19027 (13)	0.0449 (5)
H31	0.5941	−0.1445	0.2202	0.054*
C32	0.9641 (2)	−0.1025 (2)	0.05306 (16)	0.0944 (14)
H321	1.0160	−0.1440	0.0560	0.142*
H322	1.0082	−0.0611	0.0746	0.142*
H323	0.9361	−0.0938	−0.0037	0.142*

	U11	U22	U33	U12	U13	U23
C1	0.0236 (7)	0.0249 (8)	0.0240 (7)	0.0036 (6)	0.0044 (6)	0.0007 (6)
C2	0.0273 (8)	0.0261 (8)	0.0355 (9)	0.0035 (6)	0.0113 (6)	0.0048 (7)
C3	0.0320 (9)	0.0259 (8)	0.0359 (9)	0.0042 (6)	0.0122 (7)	0.0056 (7)
N2	0.0283 (7)	0.0238 (7)	0.0333 (7)	0.0073 (5)	0.0089 (6)	0.0037 (5)
C4	0.0239 (7)	0.0269 (8)	0.0256 (7)	0.0032 (6)	0.0050 (6)	0.0012 (6)
C5	0.0218 (7)	0.0261 (7)	0.0221 (7)	0.0033 (6)	0.0044 (6)	0.0014 (6)
S1	0.0216 (2)	0.0232 (2)	0.0225 (2)	0.00266 (13)	0.00451 (14)	0.00186 (13)
O1	0.0261 (6)	0.0259 (5)	0.0259 (5)	0.0018 (4)	0.0036 (4)	−0.0026 (4)
O2	0.0214 (5)	0.0303 (6)	0.0266 (6)	0.0024 (4)	0.0063 (4)	0.0031 (4)
N3	0.0247 (7)	0.0253 (6)	0.0229 (6)	0.0046 (5)	0.0030 (5)	0.0020 (5)
C6	0.0271 (8)	0.0247 (7)	0.0245 (7)	0.0027 (6)	0.0057 (6)	0.0033 (6)
O3	0.0264 (6)	0.0274 (6)	0.0326 (6)	0.0037 (4)	0.0083 (5)	−0.0015 (5)
N4	0.0269 (7)	0.0400 (8)	0.0285 (7)	0.0082 (6)	0.0003 (6)	−0.0081 (6)
C7	0.0321 (9)	0.0366 (9)	0.0305 (8)	0.0023 (7)	0.0022 (7)	−0.0072 (7)
C8	0.0474 (13)	0.0741 (17)	0.0611 (14)	−0.0202 (12)	0.0124 (11)	−0.0272 (13)
C9	0.0630 (13)	0.0464 (12)	0.0317 (10)	0.0050 (10)	−0.0029 (9)	−0.0017 (8)
N1	0.0226 (6)	0.0245 (7)	0.0295 (7)	0.0049 (5)	0.0084 (5)	0.0059 (5)
C10	0.0230 (7)	0.0219 (7)	0.0297 (8)	0.0043 (6)	0.0063 (6)	0.0020 (6)
C11	0.0263 (8)	0.0242 (8)	0.0333 (8)	0.0030 (6)	0.0040 (6)	−0.0036 (6)
C12	0.0248 (8)	0.0231 (8)	0.0447 (10)	0.0011 (6)	0.0076 (7)	−0.0053 (7)
C13	0.0287 (8)	0.0307 (8)	0.0405 (9)	0.0026 (7)	0.0142 (7)	0.0015 (7)
C14	0.0339 (9)	0.0391 (9)	0.0294 (8)	0.0062 (7)	0.0083 (7)	0.0017 (7)
C15	0.0251 (8)	0.0345 (9)	0.0306 (8)	0.0044 (6)	0.0038 (6)	0.0015 (7)
C16	0.0264 (9)	0.0416 (10)	0.0606 (12)	−0.0022 (7)	0.0077 (8)	−0.0177 (9)
C17	0.0261 (8)	0.0252 (8)	0.0256 (8)	0.0003 (6)	0.0053 (6)	0.0020 (6)
C18	0.0290 (8)	0.0304 (8)	0.0263 (8)	−0.0007 (6)	−0.0002 (6)	0.0033 (6)
C19	0.0357 (9)	0.0318 (8)	0.0233 (8)	−0.0049 (7)	0.0016 (6)	0.0017 (6)
N6	0.0338 (8)	0.0320 (7)	0.0236 (7)	−0.0029 (6)	0.0088 (6)	−0.0025 (6)
C20	0.0287 (8)	0.0260 (8)	0.0261 (8)	−0.0001 (6)	0.0058 (6)	−0.0013 (6)
C21	0.0270 (8)	0.0238 (7)	0.0236 (7)	0.0017 (6)	0.0050 (6)	0.0009 (6)
S2	0.0245 (2)	0.0222 (2)	0.0226 (2)	0.00471 (13)	0.00328 (14)	−0.00076 (13)
O4	0.0248 (6)	0.0261 (6)	0.0314 (6)	0.0077 (4)	0.0044 (4)	−0.0015 (4)
O5	0.0298 (6)	0.0226 (5)	0.0282 (6)	0.0024 (4)	0.0047 (4)	−0.0023 (4)
N7	0.0280 (7)	0.0227 (6)	0.0221 (6)	0.0047 (5)	0.0055 (5)	0.0001 (5)
C22	0.0259 (7)	0.0247 (7)	0.0236 (7)	0.0052 (6)	0.0024 (6)	0.0006 (6)
O6	0.0260 (6)	0.0259 (6)	0.0379 (6)	0.0040 (4)	0.0077 (5)	−0.0065 (5)
N8	0.0347 (8)	0.0243 (7)	0.0438 (8)	0.0011 (6)	0.0176 (6)	−0.0062 (6)
C23	0.0319 (9)	0.0294 (9)	0.0413 (9)	−0.0001 (7)	0.0121 (7)	−0.0068 (7)
C24	0.0486 (12)	0.0396 (11)	0.0533 (12)	−0.0040 (9)	0.0116 (9)	0.0056 (9)
C25	0.0343 (10)	0.0426 (11)	0.0636 (13)	−0.0012 (8)	0.0152 (9)	−0.0112 (10)
N5	0.0269 (7)	0.0334 (7)	0.0231 (7)	0.0092 (6)	0.0030 (5)	0.0018 (5)
C26	0.0269 (8)	0.0358 (9)	0.0278 (8)	0.0099 (7)	−0.0024 (6)	−0.0032 (7)
C27	0.0264 (9)	0.0600 (12)	0.0278 (9)	0.0069 (8)	−0.0019 (7)	−0.0106 (8)
C28	0.0317 (10)	0.107 (2)	0.0382 (11)	0.0312 (12)	−0.0102 (8)	−0.0284 (12)
C29	0.0653 (17)	0.0767 (18)	0.0643 (15)	0.0491 (15)	−0.0254 (13)	−0.0237 (14)
C30	0.0738 (17)	0.0438 (13)	0.0712 (16)	0.0247 (12)	−0.0234 (14)	−0.0020 (11)
C31	0.0448 (11)	0.0383 (10)	0.0502 (12)	0.0078 (8)	−0.0062 (9)	0.0068 (9)
C32	0.0323 (12)	0.200 (4)	0.0498 (14)	0.0384 (18)	−0.0021 (10)	−0.037 (2)

C1—N1	1.334 (2)	C17—N5	1.339 (2)
C1—C2	1.422 (2)	C17—C18	1.424 (2)
C1—C5	1.431 (2)	C17—C21	1.427 (2)
C2—C3	1.357 (2)	C18—C19	1.362 (2)
C2—H2	0.9500	C18—H18	0.9500
C3—N2	1.348 (2)	C19—N6	1.352 (2)
C3—H3	0.9500	C19—H19	0.9500
N2—C4	1.342 (2)	N6—C20	1.345 (2)
N2—H2N	0.93 (2)	N6—H6N	0.85 (2)
C4—C5	1.372 (2)	C20—C21	1.363 (2)
C4—H4	0.9500	C20—H20	0.9500
C5—S1	1.7740 (16)	C21—S2	1.7823 (16)
S1—O1	1.4481 (11)	S2—O4	1.4452 (11)
S1—O2	1.4518 (11)	S2—O5	1.4483 (12)
S1—N3	1.5589 (13)	S2—N7	1.5643 (13)
N3—C6	1.393 (2)	N7—C22	1.382 (2)
C6—O3	1.2416 (19)	C22—O6	1.2495 (19)
C6—N4	1.353 (2)	C22—N8	1.345 (2)
N4—C7	1.457 (2)	N8—C23	1.459 (2)
N4—H4N	0.89 (2)	N8—H8N	0.90 (2)
C7—C9	1.517 (3)	C23—C25	1.517 (2)
C7—C8	1.521 (3)	C23—C24	1.523 (3)
C7—H7	1.0000	C23—H23	1.0000
C8—H81	0.9800	C24—H241	0.9800
C8—H82	0.9800	C24—H242	0.9800
C8—H83	0.9800	C24—H243	0.9800
C9—H91	0.9800	C25—H251	0.9800
C9—H92	0.9800	C25—H252	0.9800
C9—H93	0.9800	C25—H253	0.9800
N1—C10	1.4316 (19)	N5—C26	1.431 (2)
N1—H1N	0.87 (2)	N5—H5N	0.91 (2)
C10—C15	1.384 (2)	C26—C27	1.379 (3)
C10—C11	1.389 (2)	C26—C31	1.388 (3)
C11—C12	1.397 (2)	C27—C28	1.402 (3)
C11—H11	0.9500	C27—H27	0.9500
C12—C13	1.394 (3)	C28—C29	1.393 (4)
C12—C16	1.504 (2)	C28—C32	1.504 (4)
C13—C14	1.383 (3)	C29—C30	1.375 (4)
C13—H13	0.9500	C29—H29	0.9500
C14—C15	1.389 (2)	C30—C31	1.389 (3)
C14—H14	0.9500	C30—H30	0.9500
C15—H15	0.9500	C31—H31	0.9500
C16—H161	0.9800	C32—H321	0.9800
C16—H162	0.9800	C32—H322	0.9800
C16—H163	0.9800	C32—H323	0.9800
N1—C1—C2	121.19 (14)	N5—C17—C18	122.48 (15)
N1—C1—C5	122.72 (14)	N5—C17—C21	121.66 (14)
C2—C1—C5	116.09 (14)	C18—C17—C21	115.86 (14)
C3—C2—C1	120.58 (15)	C19—C18—C17	120.50 (15)
C3—C2—H2	119.7	C19—C18—H18	119.7
C1—C2—H2	119.7	C17—C18—H18	119.7
N2—C3—C2	121.47 (15)	N6—C19—C18	121.06 (15)
N2—C3—H3	119.3	N6—C19—H19	119.5
C2—C3—H3	119.3	C18—C19—H19	119.5
C4—N2—C3	120.51 (14)	C20—N6—C19	120.83 (15)
C4—N2—H2N	116.0 (13)	C20—N6—H6N	116.7 (15)
C3—N2—H2N	123.4 (13)	C19—N6—H6N	122.4 (15)
N2—C4—C5	121.63 (15)	N6—C20—C21	121.05 (15)
N2—C4—H4	119.2	N6—C20—H20	119.5
C5—C4—H4	119.2	C21—C20—H20	119.5
C4—C5—C1	119.66 (14)	C20—C21—C17	120.57 (15)
C4—C5—S1	118.93 (12)	C20—C21—S2	117.91 (12)
C1—C5—S1	121.39 (11)	C17—C21—S2	121.19 (12)
O1—S1—O2	113.94 (7)	O4—S2—O5	114.95 (7)
O1—S1—N3	107.85 (7)	O4—S2—N7	117.35 (7)
O2—S1—N3	117.80 (7)	O5—S2—N7	106.83 (7)
O1—S1—C5	106.29 (7)	O4—S2—C21	105.28 (7)
O2—S1—C5	105.64 (7)	O5—S2—C21	105.36 (7)
N3—S1—C5	104.25 (7)	N7—S2—C21	106.05 (7)
C6—N3—S1	118.27 (11)	C22—N7—S2	119.33 (11)
O3—C6—N4	122.33 (15)	O6—C22—N8	121.01 (15)
O3—C6—N3	126.15 (15)	O6—C22—N7	126.24 (15)
N4—C6—N3	111.52 (14)	N8—C22—N7	112.75 (14)
C6—N4—C7	123.33 (14)	C22—N8—C23	122.60 (14)
C6—N4—H4N	118.5 (15)	C22—N8—H8N	119.8 (14)
C7—N4—H4N	117.8 (15)	C23—N8—H8N	117.4 (14)
N4—C7—C9	110.66 (16)	N8—C23—C25	109.75 (15)
N4—C7—C8	109.64 (15)	N8—C23—C24	111.02 (16)
C9—C7—C8	111.79 (19)	C25—C23—C24	111.51 (17)
N4—C7—H7	108.2	N8—C23—H23	108.1
C9—C7—H7	108.2	C25—C23—H23	108.1
C8—C7—H7	108.2	C24—C23—H23	108.1
C7—C8—H81	109.5	C23—C24—H241	109.5
C7—C8—H82	109.5	C23—C24—H242	109.5
H81—C8—H82	109.5	H241—C24—H242	109.5
C7—C8—H83	109.5	C23—C24—H243	109.5
H81—C8—H83	109.5	H241—C24—H243	109.5
H82—C8—H83	109.5	H242—C24—H243	109.5
C7—C9—H91	109.5	C23—C25—H251	109.5
C7—C9—H92	109.5	C23—C25—H252	109.5
H91—C9—H92	109.5	H251—C25—H252	109.5
C7—C9—H93	109.5	C23—C25—H253	109.5
H91—C9—H93	109.5	H251—C25—H253	109.5
H92—C9—H93	109.5	H252—C25—H253	109.5
C1—N1—C10	122.61 (13)	C17—N5—C26	126.59 (14)
C1—N1—H1N	119.9 (14)	C17—N5—H5N	116.5 (13)
C10—N1—H1N	117.3 (14)	C26—N5—H5N	116.5 (13)
C15—C10—C11	120.92 (15)	C27—C26—C31	121.01 (17)
C15—C10—N1	118.87 (14)	C27—C26—N5	118.10 (16)
C11—C10—N1	120.19 (14)	C31—C26—N5	120.38 (17)
C10—C11—C12	120.28 (16)	C26—C27—C28	120.0 (2)
C10—C11—H11	119.9	C26—C27—H27	120.0
C12—C11—H11	119.9	C28—C27—H27	120.0
C13—C12—C11	118.17 (16)	C29—C28—C27	118.4 (2)
C13—C12—C16	120.72 (16)	C29—C28—C32	122.7 (3)
C11—C12—C16	121.11 (17)	C27—C28—C32	118.9 (3)
C14—C13—C12	121.40 (15)	C30—C29—C28	121.3 (2)
C14—C13—H13	119.3	C30—C29—H29	119.3
C12—C13—H13	119.3	C28—C29—H29	119.3
C13—C14—C15	120.07 (16)	C29—C30—C31	120.1 (3)
C13—C14—H14	120.0	C29—C30—H30	119.9
C15—C14—H14	120.0	C31—C30—H30	119.9
C10—C15—C14	119.15 (16)	C26—C31—C30	119.1 (2)
C10—C15—H15	120.4	C26—C31—H31	120.4
C14—C15—H15	120.4	C30—C31—H31	120.4
C12—C16—H161	109.5	C28—C32—H321	109.5
C12—C16—H162	109.5	C28—C32—H322	109.5
H161—C16—H162	109.5	H321—C32—H322	109.5
C12—C16—H163	109.5	C28—C32—H323	109.5
H161—C16—H163	109.5	H321—C32—H323	109.5
H162—C16—H163	109.5	H322—C32—H323	109.5
N1—C1—C2—C3	176.46 (16)	N5—C17—C18—C19	−176.36 (16)
C5—C1—C2—C3	−2.6 (2)	C21—C17—C18—C19	3.7 (2)
C1—C2—C3—N2	1.2 (3)	C17—C18—C19—N6	−1.0 (3)
C2—C3—N2—C4	0.4 (3)	C18—C19—N6—C20	−1.9 (3)
C3—N2—C4—C5	−0.4 (2)	C19—N6—C20—C21	1.8 (2)
N2—C4—C5—C1	−1.2 (2)	N6—C20—C21—C17	1.1 (2)
N2—C4—C5—S1	−179.61 (12)	N6—C20—C21—S2	174.53 (12)
N1—C1—C5—C4	−176.47 (15)	N5—C17—C21—C20	176.28 (16)
C2—C1—C5—C4	2.6 (2)	C18—C17—C21—C20	−3.7 (2)
N1—C1—C5—S1	1.9 (2)	N5—C17—C21—S2	3.1 (2)
C2—C1—C5—S1	−178.98 (12)	C18—C17—C21—S2	−176.91 (12)
C4—C5—S1—O1	−125.64 (13)	C20—C21—S2—O4	12.97 (15)
C1—C5—S1—O1	55.93 (14)	C17—C21—S2—O4	−173.67 (13)
C4—C5—S1—O2	−4.25 (15)	C20—C21—S2—O5	−108.94 (13)
C1—C5—S1—O2	177.32 (12)	C17—C21—S2—O5	64.42 (14)
C4—C5—S1—N3	120.55 (13)	C20—C21—S2—N7	138.01 (13)
C1—C5—S1—N3	−57.88 (14)	C17—C21—S2—N7	−48.63 (15)
O1—S1—N3—C6	−177.62 (11)	O4—S2—N7—C22	47.61 (14)
O2—S1—N3—C6	51.70 (14)	O5—S2—N7—C22	178.36 (11)
C5—S1—N3—C6	−64.93 (13)	C21—S2—N7—C22	−69.62 (13)
S1—N3—C6—O3	−23.6 (2)	S2—N7—C22—O6	−10.9 (2)
S1—N3—C6—N4	156.37 (12)	S2—N7—C22—N8	168.51 (12)
O3—C6—N4—C7	−5.9 (3)	O6—C22—N8—C23	−1.7 (3)
N3—C6—N4—C7	174.09 (15)	N7—C22—N8—C23	178.84 (15)
C6—N4—C7—C9	−92.7 (2)	C22—N8—C23—C25	149.93 (18)
C6—N4—C7—C8	143.5 (2)	C22—N8—C23—C24	−86.3 (2)
C2—C1—N1—C10	12.9 (2)	C18—C17—N5—C26	15.8 (3)
C5—C1—N1—C10	−168.03 (15)	C21—C17—N5—C26	−164.23 (16)
C1—N1—C10—C15	73.0 (2)	C17—N5—C26—C27	−131.35 (18)
C1—N1—C10—C11	−108.95 (18)	C17—N5—C26—C31	56.8 (3)
C15—C10—C11—C12	−1.2 (2)	C31—C26—C27—C28	1.0 (3)
N1—C10—C11—C12	−179.23 (14)	N5—C26—C27—C28	−170.78 (16)
C10—C11—C12—C13	0.9 (2)	C26—C27—C28—C29	−0.6 (3)
C10—C11—C12—C16	−178.81 (16)	C26—C27—C28—C32	178.09 (19)
C11—C12—C13—C14	0.4 (3)	C27—C28—C29—C30	−0.2 (3)
C16—C12—C13—C14	−179.96 (17)	C32—C28—C29—C30	−178.8 (2)
C12—C13—C14—C15	−1.3 (3)	C28—C29—C30—C31	0.6 (4)
C11—C10—C15—C14	0.2 (2)	C27—C26—C31—C30	−0.6 (3)
N1—C10—C15—C14	178.32 (15)	N5—C26—C31—C30	171.00 (19)
C13—C14—C15—C10	1.0 (3)	C29—C30—C31—C26	−0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.87 (2)	2.50 (2)	3.0897 (18)	126.1 (17)
N5—H5N···N7	0.91 (2)	2.21 (2)	2.9399 (19)	136.4 (18)
N4—H4N···O1i	0.89 (2)	2.16 (2)	3.0400 (18)	175 (2)
N8—H8N···O5ii	0.90 (2)	2.01 (2)	2.9067 (18)	175 (2)
N1—H1N···N3i	0.87 (2)	2.20 (2)	2.8977 (19)	137.4 (18)
N5—H5N···N7ii	0.91 (2)	2.37 (2)	3.0591 (19)	132.9 (17)
N2—H2N···O4	0.93 (2)	2.33 (2)	2.8674 (18)	116.8 (16)
N6—H6N···O2iii	0.85 (2)	2.08 (2)	2.8184 (18)	145 (2)
N2—H2N···O6	0.93 (2)	1.77 (2)	2.6286 (17)	153.4 (19)
N6—H6N···O3iii	0.85 (2)	2.37 (2)	2.9660 (19)	128.2 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3	0.87 (2)	2.50 (2)	3.0897 (18)	126.1 (17)
N5—H5N⋯N7	0.91 (2)	2.21 (2)	2.9399 (19)	136.4 (18)
N4—H4N⋯O1i	0.89 (2)	2.16 (2)	3.0400 (18)	175 (2)
N8—H8N⋯O5ii	0.90 (2)	2.01 (2)	2.9067 (18)	175 (2)
N1—H1N⋯N3i	0.87 (2)	2.20 (2)	2.8977 (19)	137.4 (18)
N5—H5N⋯N7ii	0.91 (2)	2.37 (2)	3.0591 (19)	132.9 (17)
N2—H2N⋯O4	0.93 (2)	2.33 (2)	2.8674 (18)	116.8 (16)
N6—H6N⋯O2iii	0.85 (2)	2.08 (2)	2.8184 (18)	145 (2)
N2—H2N⋯O6	0.93 (2)	1.77 (2)	2.6286 (17)	153.4 (19)
N6—H6N⋯O3iii	0.85 (2)	2.37 (2)	2.9660 (19)	128.2 (18)

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