Crystal structure of 3,4-dimethyl 2-(tert-butyl-amino)-5-[2-oxo-4-(thio-morpholin-4-yl)-2H-chromen-3-yl]furan-3,4-di-carboxyl-ate ethyl acetate hemisolvate.

In the title hemisolvate, C25H28N2O7S·0.5C4H8O2, the thio-morpholine ring adopts a chair conformation, with the exocyclic N-C bond in an equatorial orientation. The dihedral angle between the coumarin ring system (r.m.s. deviation = 0.044 Å) and the furan ring is 64.84 (6)°. An intra-molecular N-H⋯O hydrogen bond closes an S(6) ring. The ethyl acetate solvent mol-ecule is disordered about a crystallographic inversion centre. In the crystal, the components are linked by C-H⋯O and C-H⋯S hydrogen bonds, generating a three-dimensional network.

Related literature

For the syntheses and properties of coumarins, see: Arango et al. (2010 ▸); Chodankar & Seshadri (1985 ▸); Khan & Kulkarni (1999 ▸); Kitamura et al. (2005 ▸); Luo et al. (2012 ▸); Sawa et al. (2006 ▸); Schiedel et al. (2001 ▸); Udaya Kumari et al. (2000 ▸); Zen et al. (2014 ▸).

Experimental

Crystal data

C25H28N2O7S·0.5C4H8O2

M = 544.61

Monoclinic,

a = 14.3733 (17) Å

b = 16.1159 (19) Å

c = 11.7019 (14) Å

β = 95.007 (1)°

V = 2700.3 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.17 mm−1

T = 90 K

0.50 × 0.40 × 0.25 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.853, T max = 0.958

25410 measured reflections

4757 independent reflections

4316 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.086

S = 1.02

4757 reflections

375 parameters

30 restraints

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015021970/hb7531sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021970/hb7531Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015021970/hb7531Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015021970/hb7531fig1.tif

Mol­ecular configuration and atom-numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for clarity.

Click here for additional data file.

. DOI: 10.1107/S2056989015021970/hb7531fig2.tif

Crystal packing diagram of the title compound.

Click here for additional data file.

. DOI: 10.1107/S2056989015021970/hb7531fig3.tif

Chemical scheme of title compound with solvent mol­ecule. In the cystal system the main mol­ecule and solvent mol­ecule was found in 1:0.5 ratio.

Click here for additional data file.

. DOI: 10.1107/S2056989015021970/hb7531fig4.tif

Synthesis of title compound (I).

CCDC reference: 1432824

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

C25H28N2O7S·0.5C4H8O2	F(000) = 1152
Mr = 544.61	Dx = 1.340 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25410 reflections
a = 14.3733 (17) Å	θ = 1.4–25.0°
b = 16.1159 (19) Å	µ = 0.17 mm−1
c = 11.7019 (14) Å	T = 90 K
β = 95.007 (1)°	Prism, yellow
V = 2700.3 (6) Å3	0.50 × 0.40 × 0.25 mm
Z = 4

Bruker APEXII diffractometer	4757 independent reflections
Radiation source: fine-focus sealed tube	4316 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 8.333 pixels mm-1	θmax = 25.0°, θmin = 1.4°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −19→19
Tmin = 0.853, Tmax = 0.958	l = −13→13
25410 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.040P)2 + 1.5222P] where P = (Fo2 + 2Fc2)/3
4757 reflections	(Δ/σ)max < 0.001
375 parameters	Δρmax = 0.26 e Å−3
30 restraints	Δρmin = −0.23 e Å−3

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	0.99995 (10)	0.03172 (9)	0.34623 (12)	0.0231 (3)
C2	1.08898 (11)	0.03216 (10)	0.40315 (13)	0.0282 (3)
H1	1.1151	0.0815	0.4321	0.034*
C3	1.13819 (11)	−0.04082 (11)	0.41634 (14)	0.0316 (4)
H2	1.197	−0.0413	0.4563	0.038*
C4	1.09998 (11)	−0.11405 (11)	0.36986 (14)	0.0310 (4)
H3	1.1343	−0.163	0.3759	0.037*
C5	1.01118 (10)	−0.11389 (10)	0.31490 (13)	0.0257 (3)
H4	0.9864	−0.1631	0.2837	0.031*
C6	0.95710 (10)	−0.04105 (9)	0.30487 (12)	0.0208 (3)
C7	0.86234 (9)	−0.03596 (9)	0.24765 (11)	0.0190 (3)
C8	0.82094 (10)	0.04097 (9)	0.23612 (12)	0.0199 (3)
C9	0.87117 (10)	0.11639 (9)	0.27233 (13)	0.0239 (3)
C10	0.81001 (10)	−0.18053 (9)	0.27629 (12)	0.0215 (3)
H5	0.7459	−0.1825	0.2962	0.026*
H6	0.8502	−0.1745	0.3468	0.026*
C11	0.83315 (11)	−0.26140 (9)	0.21796 (12)	0.0242 (3)
H7	0.8264	−0.3073	0.2703	0.029*
H8	0.8976	−0.2601	0.1993	0.029*
C12	0.77517 (10)	−0.17887 (9)	0.02143 (12)	0.0238 (3)
H10	0.8391	−0.1757	0.0011	0.029*
H9	0.7342	−0.1748	−0.0488	0.029*
C13	0.75641 (10)	−0.10617 (9)	0.09892 (12)	0.0217 (3)
H11	0.7635	−0.0545	0.0581	0.026*
H12	0.6928	−0.1092	0.1205	0.026*
C14	0.72271 (10)	0.05441 (8)	0.19528 (12)	0.0201 (3)
C15	0.64058 (9)	0.03168 (8)	0.23338 (12)	0.0185 (3)
C16	0.56676 (10)	0.06269 (9)	0.15304 (12)	0.0194 (3)
C17	0.61162 (10)	0.10511 (9)	0.07106 (12)	0.0214 (3)
C18	0.62518 (11)	0.20817 (9)	−0.09030 (12)	0.0243 (3)
C19	0.68655 (12)	0.26826 (10)	−0.01648 (14)	0.0323 (4)
H14	0.6495	0.296	0.0363	0.048*
H16	0.7128	0.3086	−0.0648	0.048*
H15	0.736	0.2381	0.0255	0.048*
C20	0.54811 (12)	0.25574 (10)	−0.16032 (14)	0.0320 (4)
H17	0.5063	0.2172	−0.2007	0.048*
H18	0.5754	0.2911	−0.2144	0.048*
H19	0.5142	0.2889	−0.1099	0.048*
C21	0.68273 (12)	0.15921 (10)	−0.17061 (14)	0.0323 (4)
H20	0.727	0.1249	−0.1262	0.048*
H22	0.7154	0.197	−0.2163	0.048*
H21	0.642	0.1249	−0.2198	0.048*
C22	0.46747 (10)	0.06935 (9)	0.16008 (12)	0.0204 (3)
C23	0.34095 (10)	0.05062 (10)	0.27252 (14)	0.0297 (4)
H23	0.3276	0.1089	0.2747	0.045*
H24	0.3263	0.0253	0.343	0.045*
H25	0.3039	0.0256	0.2095	0.045*
C24	0.62849 (9)	−0.01445 (9)	0.34073 (12)	0.0200 (3)
C25	0.55129 (12)	−0.12568 (10)	0.42109 (13)	0.0298 (4)
H26	0.605	−0.1357	0.4739	0.045*
H27	0.522	−0.1775	0.3994	0.045*
H28	0.5078	−0.0912	0.457	0.045*
C1S	1.0683 (9)	−0.1031 (8)	1.0236 (11)	0.059 (3)	0.5
H1SA	1.1073	−0.0784	1.0852	0.088*	0.5
H1SB	1.1057	−0.1181	0.9628	0.088*	0.5
H1SC	1.0388	−0.1517	1.0511	0.088*	0.5
C2S	0.994 (2)	−0.041 (2)	0.979 (2)	0.0624 (17)	0.5
C3S	0.9217 (9)	0.0898 (7)	0.9635 (11)	0.0506 (17)	0.5
H3SA	0.8679	0.0739	1.0031	0.061*	0.5
H3SB	0.9073	0.0815	0.8817	0.061*	0.5
C4S	0.9519 (2)	0.1897 (2)	0.9924 (3)	0.0399 (9)	0.5
H4SA	0.9024	0.2257	0.9627	0.06*	0.5
H4SB	1.0079	0.2028	0.9569	0.06*	0.5
H4SC	0.9627	0.1971	1.0738	0.06*	0.5
N1	0.82204 (8)	−0.10814 (7)	0.20229 (10)	0.0197 (3)
N2	0.57584 (9)	0.15043 (8)	−0.01773 (11)	0.0286 (3)
H13	0.5167	0.1455	−0.0349	0.034*
O1	0.95818 (7)	0.10811 (6)	0.32980 (9)	0.0263 (2)
O2	0.84156 (8)	0.18618 (7)	0.25827 (10)	0.0324 (3)
O3	0.70539 (7)	0.09935 (6)	0.09266 (8)	0.0223 (2)
O4	0.41429 (7)	0.10217 (7)	0.08665 (9)	0.0299 (3)
O5	0.43880 (7)	0.03856 (6)	0.25799 (8)	0.0226 (2)
O6	0.65724 (8)	0.00853 (8)	0.43480 (9)	0.0370 (3)
O7	0.57991 (7)	−0.08439 (6)	0.32009 (8)	0.0235 (2)
O1S	0.9264 (3)	−0.0628 (3)	0.9137 (4)	0.1025 (13)	0.5
O2S	1.0034 (13)	0.0428 (14)	1.0052 (12)	0.0550 (15)	0.5
S1	0.75716 (3)	−0.27772 (2)	0.08816 (3)	0.02791 (11)

	U11	U22	U33	U12	U13	U23
C1	0.0205 (7)	0.0277 (8)	0.0213 (7)	−0.0025 (6)	0.0037 (6)	0.0008 (6)
C2	0.0218 (8)	0.0373 (9)	0.0252 (8)	−0.0098 (7)	−0.0001 (6)	−0.0009 (7)
C3	0.0166 (7)	0.0500 (10)	0.0272 (8)	−0.0029 (7)	−0.0034 (6)	0.0055 (7)
C4	0.0216 (8)	0.0390 (9)	0.0317 (9)	0.0058 (7)	−0.0020 (6)	0.0040 (7)
C5	0.0219 (7)	0.0290 (8)	0.0256 (8)	0.0008 (6)	−0.0010 (6)	0.0000 (6)
C6	0.0177 (7)	0.0277 (8)	0.0171 (7)	−0.0014 (6)	0.0015 (5)	0.0016 (6)
C7	0.0177 (7)	0.0236 (7)	0.0159 (7)	−0.0013 (6)	0.0026 (5)	0.0023 (5)
C8	0.0178 (7)	0.0231 (7)	0.0191 (7)	−0.0012 (6)	0.0031 (5)	0.0015 (6)
C9	0.0219 (7)	0.0257 (8)	0.0245 (8)	−0.0017 (6)	0.0043 (6)	0.0002 (6)
C10	0.0219 (7)	0.0227 (7)	0.0194 (7)	−0.0020 (6)	−0.0001 (6)	0.0041 (6)
C11	0.0270 (8)	0.0221 (7)	0.0229 (7)	−0.0015 (6)	−0.0020 (6)	0.0043 (6)
C12	0.0228 (7)	0.0283 (8)	0.0194 (7)	0.0022 (6)	−0.0035 (6)	0.0008 (6)
C13	0.0210 (7)	0.0228 (7)	0.0202 (7)	0.0006 (6)	−0.0046 (6)	0.0018 (6)
C14	0.0224 (7)	0.0175 (7)	0.0200 (7)	0.0018 (6)	0.0002 (6)	0.0034 (5)
C15	0.0191 (7)	0.0168 (7)	0.0194 (7)	0.0016 (5)	0.0004 (5)	−0.0004 (5)
C16	0.0189 (7)	0.0200 (7)	0.0187 (7)	0.0018 (5)	−0.0008 (5)	0.0010 (5)
C17	0.0195 (7)	0.0226 (7)	0.0218 (7)	0.0028 (6)	−0.0004 (6)	0.0019 (6)
C18	0.0309 (8)	0.0213 (7)	0.0209 (7)	0.0007 (6)	0.0030 (6)	0.0039 (6)
C19	0.0402 (9)	0.0246 (8)	0.0314 (9)	−0.0006 (7)	−0.0010 (7)	0.0005 (7)
C20	0.0425 (10)	0.0277 (8)	0.0251 (8)	0.0061 (7)	−0.0007 (7)	0.0049 (6)
C21	0.0378 (9)	0.0299 (8)	0.0300 (8)	0.0010 (7)	0.0075 (7)	−0.0007 (7)
C22	0.0203 (7)	0.0194 (7)	0.0209 (7)	0.0005 (6)	−0.0003 (6)	−0.0014 (6)
C23	0.0207 (8)	0.0340 (9)	0.0353 (9)	0.0037 (6)	0.0082 (6)	0.0009 (7)
C24	0.0148 (6)	0.0229 (7)	0.0219 (7)	0.0010 (5)	−0.0006 (5)	0.0021 (6)
C25	0.0328 (9)	0.0313 (8)	0.0249 (8)	−0.0065 (7)	0.0008 (6)	0.0099 (7)
C1S	0.036 (4)	0.090 (5)	0.055 (4)	−0.004 (3)	0.028 (3)	−0.002 (3)
C2S	0.049 (3)	0.082 (3)	0.060 (4)	−0.003 (2)	0.026 (3)	0.013 (3)
C3S	0.036 (3)	0.070 (3)	0.047 (3)	0.013 (3)	0.007 (2)	0.020 (3)
C4S	0.0258 (17)	0.052 (2)	0.044 (2)	0.0120 (15)	0.0153 (15)	0.0192 (17)
N1	0.0199 (6)	0.0199 (6)	0.0185 (6)	−0.0012 (5)	−0.0039 (5)	0.0028 (5)
N2	0.0200 (6)	0.0372 (8)	0.0280 (7)	0.0004 (5)	−0.0007 (5)	0.0136 (6)
O1	0.0223 (5)	0.0244 (5)	0.0319 (6)	−0.0049 (4)	0.0000 (4)	−0.0021 (4)
O2	0.0326 (6)	0.0207 (6)	0.0437 (7)	0.0006 (5)	0.0019 (5)	−0.0024 (5)
O3	0.0185 (5)	0.0251 (5)	0.0232 (5)	0.0016 (4)	0.0023 (4)	0.0073 (4)
O4	0.0204 (5)	0.0408 (7)	0.0277 (6)	0.0047 (5)	−0.0027 (4)	0.0086 (5)
O5	0.0175 (5)	0.0271 (5)	0.0236 (5)	0.0021 (4)	0.0035 (4)	0.0028 (4)
O6	0.0417 (7)	0.0463 (7)	0.0214 (6)	−0.0190 (6)	−0.0069 (5)	0.0048 (5)
O7	0.0284 (5)	0.0218 (5)	0.0202 (5)	−0.0045 (4)	0.0014 (4)	0.0039 (4)
O1S	0.104 (3)	0.113 (3)	0.094 (3)	−0.019 (3)	0.029 (2)	0.021 (3)
O2S	0.0419 (18)	0.0739 (19)	0.052 (4)	0.0088 (17)	0.017 (3)	0.014 (3)
S1	0.0304 (2)	0.0225 (2)	0.0294 (2)	−0.00151 (15)	−0.00565 (16)	−0.00288 (15)

C1—O1	1.3759 (18)	C18—N2	1.4817 (19)
C1—C2	1.390 (2)	C18—C21	1.525 (2)
C1—C6	1.392 (2)	C18—C20	1.526 (2)
C2—C3	1.374 (2)	C18—C19	1.526 (2)
C2—H1	0.93	C19—H14	0.96
C3—C4	1.392 (2)	C19—H16	0.96
C3—H2	0.93	C19—H15	0.96
C4—C5	1.378 (2)	C20—H17	0.96
C4—H3	0.93	C20—H18	0.96
C5—C6	1.407 (2)	C20—H19	0.96
C5—H4	0.93	C21—H20	0.96
C6—C7	1.4667 (19)	C21—H22	0.96
C7—C8	1.377 (2)	C21—H21	0.96
C7—N1	1.3844 (18)	C22—O4	1.2197 (17)
C8—C9	1.458 (2)	C22—O5	1.3457 (17)
C8—C14	1.467 (2)	C23—O5	1.4444 (17)
C9—O2	1.2088 (19)	C23—H23	0.96
C9—O1	1.3737 (18)	C23—H24	0.96
C10—N1	1.4721 (18)	C23—H25	0.96
C10—C11	1.521 (2)	C24—O6	1.2001 (18)
C10—H5	0.97	C24—O7	1.3367 (17)
C10—H6	0.97	C25—O7	1.4469 (18)
C11—S1	1.8110 (15)	C25—H26	0.96
C11—H7	0.97	C25—H27	0.96
C11—H8	0.97	C25—H28	0.96
C12—C13	1.520 (2)	C1S—C2S	1.51 (3)
C12—S1	1.8027 (15)	C1S—H1SA	0.96
C12—H10	0.97	C1S—H1SB	0.96
C12—H9	0.97	C1S—H1SC	0.96
C13—N1	1.4680 (17)	C2S—O1S	1.23 (3)
C13—H11	0.97	C2S—O2S	1.396 (16)
C13—H12	0.97	C3S—O2S	1.446 (19)
C14—C15	1.348 (2)	C3S—C4S	1.693 (13)
C14—O3	1.4058 (17)	C3S—H3SA	0.97
C15—C16	1.4440 (19)	C3S—H3SB	0.97
C15—C24	1.4830 (19)	C4S—H4SA	0.96
C16—C17	1.383 (2)	C4S—H4SB	0.96
C16—C22	1.441 (2)	C4S—H4SC	0.96
C17—N2	1.3357 (19)	N2—H13	0.86
C17—O3	1.3527 (17)
O1—C1—C2	115.75 (13)	C18—C19—H14	109.5
O1—C1—C6	122.08 (13)	C18—C19—H16	109.5
C2—C1—C6	122.13 (14)	H14—C19—H16	109.5
C3—C2—C1	119.52 (15)	C18—C19—H15	109.5
C3—C2—H1	120.2	H14—C19—H15	109.5
C1—C2—H1	120.2	H16—C19—H15	109.5
C2—C3—C4	120.00 (14)	C18—C20—H17	109.5
C2—C3—H2	120.0	C18—C20—H18	109.5
C4—C3—H2	120.0	H17—C20—H18	109.5
C5—C4—C3	119.90 (15)	C18—C20—H19	109.5
C5—C4—H3	120.1	H17—C20—H19	109.5
C3—C4—H3	120.1	H18—C20—H19	109.5
C4—C5—C6	121.52 (15)	C18—C21—H20	109.5
C4—C5—H4	119.2	C18—C21—H22	109.5
C6—C5—H4	119.2	H20—C21—H22	109.5
C1—C6—C5	116.71 (13)	C18—C21—H21	109.5
C1—C6—C7	118.48 (13)	H20—C21—H21	109.5
C5—C6—C7	124.67 (13)	H22—C21—H21	109.5
C8—C7—N1	123.80 (12)	O4—C22—O5	122.69 (13)
C8—C7—C6	118.12 (13)	O4—C22—C16	123.71 (13)
N1—C7—C6	117.96 (12)	O5—C22—C16	113.56 (12)
C7—C8—C9	121.56 (13)	O5—C23—H23	109.5
C7—C8—C14	124.09 (13)	O5—C23—H24	109.5
C9—C8—C14	114.21 (12)	H23—C23—H24	109.5
O2—C9—O1	116.85 (13)	O5—C23—H25	109.5
O2—C9—C8	125.21 (14)	H23—C23—H25	109.5
O1—C9—C8	117.91 (12)	H24—C23—H25	109.5
N1—C10—C11	111.94 (11)	O6—C24—O7	123.96 (13)
N1—C10—H5	109.2	O6—C24—C15	124.46 (13)
C11—C10—H5	109.2	O7—C24—C15	111.57 (12)
N1—C10—H6	109.2	O7—C25—H26	109.5
C11—C10—H6	109.2	O7—C25—H27	109.5
H5—C10—H6	107.9	H26—C25—H27	109.5
C10—C11—S1	111.17 (10)	O7—C25—H28	109.5
C10—C11—H7	109.4	H26—C25—H28	109.5
S1—C11—H7	109.4	H27—C25—H28	109.5
C10—C11—H8	109.4	C2S—C1S—H1SA	109.5
S1—C11—H8	109.4	C2S—C1S—H1SB	109.5
H7—C11—H8	108.0	H1SA—C1S—H1SB	109.5
C13—C12—S1	112.52 (10)	C2S—C1S—H1SC	109.5
C13—C12—H10	109.1	H1SA—C1S—H1SC	109.5
S1—C12—H10	109.1	H1SB—C1S—H1SC	109.5
C13—C12—H9	109.1	O1S—C2S—O2S	117 (2)
S1—C12—H9	109.1	O1S—C2S—C1S	122 (3)
H10—C12—H9	107.8	O2S—C2S—C1S	120.8 (16)
N1—C13—C12	109.89 (11)	O2S—C3S—C4S	104.1 (11)
N1—C13—H11	109.7	O2S—C3S—H3SA	110.9
C12—C13—H11	109.7	C4S—C3S—H3SA	110.9
N1—C13—H12	109.7	O2S—C3S—H3SB	110.9
C12—C13—H12	109.7	C4S—C3S—H3SB	110.9
H11—C13—H12	108.2	H3SA—C3S—H3SB	109.0
C15—C14—O3	109.12 (12)	C3S—C4S—H4SA	109.5
C15—C14—C8	134.25 (13)	C3S—C4S—H4SB	109.5
O3—C14—C8	116.62 (12)	H4SA—C4S—H4SB	109.5
C14—C15—C16	107.78 (12)	C3S—C4S—H4SC	109.5
C14—C15—C24	125.94 (13)	H4SA—C4S—H4SC	109.5
C16—C15—C24	126.25 (12)	H4SB—C4S—H4SC	109.5
C17—C16—C22	121.81 (13)	C7—N1—C13	121.00 (11)
C17—C16—C15	105.20 (12)	C7—N1—C10	120.47 (11)
C22—C16—C15	131.59 (13)	C13—N1—C10	113.69 (11)
N2—C17—O3	119.51 (13)	C17—N2—C18	128.18 (13)
N2—C17—C16	129.71 (13)	C17—N2—H13	115.9
O3—C17—C16	110.72 (12)	C18—N2—H13	115.9
N2—C18—C21	109.92 (13)	C9—O1—C1	121.51 (11)
N2—C18—C20	105.19 (12)	C17—O3—C14	107.11 (11)
C21—C18—C20	109.66 (13)	C22—O5—C23	115.10 (11)
N2—C18—C19	110.86 (12)	C24—O7—C25	114.92 (11)
C21—C18—C19	111.06 (13)	C2S—O2S—C3S	112.1 (10)
C20—C18—C19	109.99 (13)	C12—S1—C11	97.82 (7)
O1—C1—C2—C3	−175.67 (13)	C15—C16—C17—O3	2.48 (16)
C6—C1—C2—C3	2.1 (2)	C17—C16—C22—O4	10.8 (2)
C1—C2—C3—C4	1.9 (2)	C15—C16—C22—O4	175.22 (15)
C2—C3—C4—C5	−2.8 (2)	C17—C16—C22—O5	−166.81 (13)
C3—C4—C5—C6	−0.4 (2)	C15—C16—C22—O5	−2.4 (2)
O1—C1—C6—C5	172.56 (13)	C14—C15—C24—O6	58.0 (2)
C2—C1—C6—C5	−5.1 (2)	C16—C15—C24—O6	−119.79 (17)
O1—C1—C6—C7	−3.4 (2)	C14—C15—C24—O7	−123.19 (15)
C2—C1—C6—C7	178.92 (13)	C16—C15—C24—O7	59.05 (18)
C4—C5—C6—C1	4.2 (2)	C8—C7—N1—C13	28.2 (2)
C4—C5—C6—C7	179.92 (14)	C6—C7—N1—C13	−147.75 (13)
C1—C6—C7—C8	0.98 (19)	C8—C7—N1—C10	−125.64 (15)
C5—C6—C7—C8	−174.66 (13)	C6—C7—N1—C10	58.43 (17)
C1—C6—C7—N1	177.15 (12)	C12—C13—N1—C7	139.30 (13)
C5—C6—C7—N1	1.5 (2)	C12—C13—N1—C10	−65.24 (15)
N1—C7—C8—C9	−171.86 (13)	C11—C10—N1—C7	−138.82 (13)
C6—C7—C8—C9	4.1 (2)	C11—C10—N1—C13	65.57 (15)
N1—C7—C8—C14	12.7 (2)	O3—C17—N2—C18	−10.2 (2)
C6—C7—C8—C14	−171.36 (12)	C16—C17—N2—C18	166.87 (15)
C7—C8—C9—O2	175.03 (15)	C21—C18—N2—C17	73.7 (2)
C14—C8—C9—O2	−9.1 (2)	C20—C18—N2—C17	−168.28 (15)
C7—C8—C9—O1	−6.8 (2)	C19—C18—N2—C17	−49.4 (2)
C14—C8—C9—O1	169.05 (12)	O2—C9—O1—C1	−177.30 (13)
N1—C10—C11—S1	−60.96 (14)	C8—C9—O1—C1	4.37 (19)
S1—C12—C13—N1	62.57 (14)	C2—C1—O1—C9	178.43 (13)
C7—C8—C14—C15	61.3 (2)	C6—C1—O1—C9	0.6 (2)
C9—C8—C14—C15	−114.41 (18)	N2—C17—O3—C14	175.06 (13)
C7—C8—C14—O3	−117.28 (15)	C16—C17—O3—C14	−2.50 (16)
C9—C8—C14—O3	66.99 (16)	C15—C14—O3—C17	1.49 (15)
O3—C14—C15—C16	0.03 (16)	C8—C14—O3—C17	−179.57 (12)
C8—C14—C15—C16	−178.64 (15)	O4—C22—O5—C23	−2.8 (2)
O3—C14—C15—C24	−178.07 (12)	C16—C22—O5—C23	174.87 (12)
C8—C14—C15—C24	3.3 (3)	O6—C24—O7—C25	9.0 (2)
C14—C15—C16—C17	−1.50 (16)	C15—C24—O7—C25	−169.88 (12)
C24—C15—C16—C17	176.60 (13)	O1S—C2S—O2S—C3S	9.0 (14)
C14—C15—C16—C22	−167.79 (15)	C1S—C2S—O2S—C3S	−175 (2)
C24—C15—C16—C22	10.3 (2)	C4S—C3S—O2S—C2S	−174.6 (5)
C22—C16—C17—N2	−6.8 (2)	C13—C12—S1—C11	−53.91 (11)
C15—C16—C17—N2	−174.76 (15)	C10—C11—S1—C12	52.18 (11)
C22—C16—C17—O3	170.45 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H13···O4	0.86	2.25	2.8255 (17)	125
C3—H2···O6i	0.93	2.41	3.325 (2)	167
C12—H9···O4ii	0.97	2.44	3.1531 (18)	130
C12—H10···O1Siii	0.97	2.48	3.208 (5)	132
C19—H15···O3	0.96	2.42	3.0090 (19)	119
C23—H23···S1iv	0.96	2.78	3.5639 (17)	139
C25—H26···S1v	0.96	2.83	3.7406 (18)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H13⋯O4	0.86	2.25	2.8255 (17)	125
C3—H2⋯O6i	0.93	2.41	3.325 (2)	167
C12—H9⋯O4ii	0.97	2.44	3.1531 (18)	130
C12—H10⋯O1S iii	0.97	2.48	3.208 (5)	132
C19—H15⋯O3	0.96	2.42	3.0090 (19)	119
C23—H23⋯S1iv	0.96	2.78	3.5639 (17)	139
C25—H26⋯S1v	0.96	2.83	3.7406 (18)	159

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