2,2'-(Disulfanedi-yl)dibenzoic acid-2,9-dimethyl-phenanthroline-tetra-hydro-furan (1/2/1).

The asymmetric unit of the title co-crystal solvate, C(14)H(10)O(4)S(2)·2C(14)H(12)N(2)·C(4)H(8)O, comprises a 2,2'-(disulfanedi-yl)dibenzoic acid mol-ecule, two mol-ecules of 2,9-dimethyl-phenanthroline and a tetra-hydro-furan (THF) solvent mol-ecule. Each end of the twisted diacid [dihedral angle between the benzene rings = 74.33 (17)°] forms a strong O-H⋯N hydrogen bond with a 2,9-dimethyl-phenanthroline mol-ecule, forming a trimeric aggregate. The crystal structure comprises layers of acid and THF mol-ecules, and layers of 2,9-dimethyl-phenanthroline mol-ecules that alternate along the a axis, the main connections between them being of the type C-H⋯O.

Related literature

For related studies on co-crystal formation involving 2-[(2-carb­oxy­phen­yl)disulfan­yl]benzoic acid, see: Broker & Tiekink (2007 ▶, 2010 ▶); Broker et al. (2008 ▶). For a co-crystal involving 2,9-dimethyl­phenanthroline, see: Arman et al. (2010 ▶).

Experimental

Crystal data

C14H10O4S2·2C14H12N2·C4H8O

M = 794.96

Monoclinic,

a = 14.011 (4) Å

b = 8.516 (3) Å

c = 17.403 (5) Å

β = 109.637 (6)°

V = 1955.7 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.19 mm−1

T = 98 K

0.26 × 0.21 × 0.10 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer

13023 measured reflections

8637 independent reflections

7988 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.169

S = 1.05

8637 reflections

499 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.83 e Å−3

Δρmin = −0.85 e Å−3

Absolute structure: Flack (1983 ▶), 3550 Friedel pairs

Flack parameter: 0.01 (9)

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810037165/su2213sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037165/su2213Isup2.hkl

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

C14H10O4S2·2C14H12N2·C4H8O	F(000) = 836
Mr = 794.96	Dx = 1.350 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 8113 reflections
a = 14.011 (4) Å	θ = 2.3–40.2°
b = 8.516 (3) Å	µ = 0.19 mm−1
c = 17.403 (5) Å	T = 98 K
β = 109.637 (6)°	Block, gold
V = 1955.7 (10) Å3	0.26 × 0.21 × 0.10 mm
Z = 2

Rigaku AFC12K/SATURN724 diffractometer	7988 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
graphite	θmax = 27.5°, θmin = 2.3°
ω scans	h = −15→18
13023 measured reflections	k = −10→11
8637 independent reflections	l = −22→21

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)] = 0.068	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.169	w = 1/[σ2(Fo2) + (0.0751P)2 + 1.2802P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
8637 reflections	Δρmax = 0.83 e Å−3
499 parameters	Δρmin = −0.85 e Å−3
8 restraints	Absolute structure: Flack (1983), 3550 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (9)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.42365 (6)	0.42502 (11)	0.23785 (5)	0.02513 (19)
S2	0.57129 (6)	0.34896 (10)	0.26918 (6)	0.02557 (19)
O1	0.24189 (19)	0.5734 (3)	0.19397 (16)	0.0292 (6)
O2	0.2027 (2)	0.7481 (3)	0.27555 (17)	0.0333 (6)
H2o	0.154 (3)	0.776 (6)	0.234 (2)	0.050*
O3	0.76279 (19)	0.2507 (3)	0.29142 (16)	0.0289 (6)
O4	0.80075 (19)	0.0087 (3)	0.25967 (17)	0.0283 (6)
H4o	0.855 (2)	0.053 (5)	0.261 (3)	0.042*
C1	0.4064 (2)	0.4616 (4)	0.3339 (2)	0.0239 (7)
C2	0.3269 (2)	0.5589 (4)	0.3380 (2)	0.0230 (7)
C3	0.3127 (3)	0.5853 (5)	0.4125 (2)	0.0279 (8)
H3	0.2585	0.6502	0.4146	0.034*
C4	0.3771 (3)	0.5176 (5)	0.4835 (2)	0.0314 (8)
H4	0.3673	0.5359	0.5342	0.038*
C5	0.4560 (3)	0.4227 (5)	0.4797 (2)	0.0294 (8)
H5	0.4998	0.3750	0.5280	0.035*
C6	0.4715 (2)	0.3967 (4)	0.4064 (2)	0.0242 (7)
H6	0.5271	0.3340	0.4052	0.029*
C7	0.2529 (2)	0.6278 (4)	0.2614 (2)	0.0233 (7)
C8	0.5633 (3)	0.1399 (4)	0.2802 (2)	0.0243 (7)
C9	0.6461 (3)	0.0442 (4)	0.2825 (2)	0.0228 (7)
C10	0.6392 (3)	−0.1175 (4)	0.2914 (2)	0.0273 (8)
H10	0.6940	−0.1827	0.2909	0.033*
C11	0.5540 (3)	−0.1847 (5)	0.3008 (2)	0.0323 (8)
H11	0.5516	−0.2946	0.3094	0.039*
C12	0.4721 (3)	−0.0905 (5)	0.2977 (2)	0.0308 (8)
H12	0.4127	−0.1363	0.3028	0.037*
C13	0.4766 (3)	0.0702 (4)	0.2872 (2)	0.0272 (8)
H13	0.4199	0.1337	0.2847	0.033*
C14	0.7423 (3)	0.1115 (4)	0.2779 (2)	0.0236 (7)
N1	1.0745 (2)	0.8741 (3)	0.13399 (18)	0.0244 (6)
N2	0.9787 (3)	0.7029 (4)	0.21862 (19)	0.0282 (7)
C15	1.1222 (3)	0.9556 (4)	0.0924 (2)	0.0276 (8)
C16	1.0706 (3)	1.0298 (4)	0.0182 (2)	0.0280 (7)
H16	1.1070	1.0878	−0.0095	0.034*
C17	0.9668 (3)	1.0182 (4)	−0.0142 (2)	0.0289 (8)
H17	0.9311	1.0682	−0.0644	0.035*
C18	0.9138 (3)	0.9315 (4)	0.0276 (2)	0.0260 (7)
C19	0.8062 (3)	0.9126 (5)	−0.0028 (2)	0.0313 (8)
H19	0.7678	0.9592	−0.0533	0.038*
C20	0.7588 (3)	0.8293 (5)	0.0396 (2)	0.0323 (8)
H20	0.6873	0.8180	0.0182	0.039*
C21	0.8140 (3)	0.7573 (5)	0.1164 (2)	0.0311 (8)
C22	0.7672 (3)	0.6662 (5)	0.1615 (3)	0.0338 (9)
H22	0.6958	0.6518	0.1424	0.041*
C23	0.8265 (3)	0.5986 (5)	0.2336 (3)	0.0360 (9)
H23	0.7962	0.5384	0.2653	0.043*
C24	0.9327 (3)	0.6194 (4)	0.2602 (2)	0.0309 (8)
C25	0.9211 (3)	0.7715 (4)	0.1483 (2)	0.0239 (7)
C26	0.9722 (3)	0.8614 (4)	0.1026 (2)	0.0242 (7)
C27	1.2360 (3)	0.9665 (5)	0.1295 (3)	0.0362 (9)
H27A	1.2548	0.9921	0.1876	0.054*
H27B	1.2610	1.0488	0.1017	0.054*
H27C	1.2663	0.8656	0.1233	0.054*
C28	0.9995 (4)	0.5427 (5)	0.3367 (3)	0.0404 (10)
H28A	1.0702	0.5712	0.3459	0.061*
H28B	0.9919	0.4284	0.3313	0.061*
H28C	0.9801	0.5781	0.3829	0.061*
N3	1.0152 (2)	0.4436 (4)	0.59852 (18)	0.0247 (6)
N4	1.0154 (2)	0.6163 (4)	0.73176 (19)	0.0246 (6)
C29	1.0161 (3)	0.3580 (5)	0.5358 (2)	0.0269 (7)
C30	0.9254 (3)	0.3064 (4)	0.4751 (2)	0.0274 (7)
H30	0.9281	0.2410	0.4316	0.033*
C31	0.8345 (3)	0.3520 (5)	0.4802 (2)	0.0284 (7)
H31	0.7734	0.3204	0.4393	0.034*
C32	0.8309 (3)	0.4456 (4)	0.5455 (2)	0.0266 (7)
C33	0.7390 (3)	0.5060 (5)	0.5519 (3)	0.0345 (9)
H33	0.6766	0.4803	0.5109	0.041*
C34	0.7386 (3)	0.5989 (5)	0.6146 (2)	0.0306 (8)
H34	0.6761	0.6389	0.6166	0.037*
C35	0.8316 (3)	0.6379 (4)	0.6785 (2)	0.0256 (7)
C36	0.8348 (3)	0.7342 (4)	0.7439 (2)	0.0304 (8)
H36	0.7739	0.7763	0.7481	0.036*
C37	0.9266 (3)	0.7683 (5)	0.8025 (2)	0.0309 (8)
H37	0.9294	0.8323	0.8479	0.037*
C38	1.0165 (3)	0.7075 (4)	0.7948 (2)	0.0263 (7)
C39	0.9249 (3)	0.5806 (4)	0.6737 (2)	0.0234 (7)
C40	0.9247 (3)	0.4860 (4)	0.6051 (2)	0.0229 (7)
C41	1.1178 (3)	0.3183 (5)	0.5301 (3)	0.0333 (9)
H41A	1.1660	0.4023	0.5552	0.050*
H41B	1.1119	0.3074	0.4726	0.050*
H41C	1.1420	0.2192	0.5587	0.050*
C42	1.1181 (3)	0.7423 (5)	0.8571 (2)	0.0313 (8)
H42A	1.1562	0.6443	0.8734	0.047*
H42B	1.1088	0.7915	0.9050	0.047*
H42C	1.1557	0.8138	0.8336	0.047*
O5	0.5266 (4)	0.6646 (6)	0.0293 (3)	0.0881 (15)*
C43	0.4873 (6)	0.6959 (12)	−0.0568 (5)	0.106 (3)*
H43A	0.5205	0.7896	−0.0701	0.127*
H43B	0.4994	0.6053	−0.0879	0.127*
C44	0.3809 (5)	0.7227 (10)	−0.0764 (4)	0.089 (2)*
H44A	0.3429	0.6232	−0.0927	0.106*
H44B	0.3563	0.7982	−0.1221	0.106*
C45	0.3658 (5)	0.7886 (8)	−0.0006 (4)	0.0757 (18)*
H45A	0.3626	0.9047	−0.0023	0.091*
H45B	0.3034	0.7468	0.0064	0.091*
C46	0.4594 (5)	0.7317 (10)	0.0663 (4)	0.086 (2)*
H46A	0.4928	0.8205	0.1018	0.103*
H46B	0.4406	0.6521	0.1001	0.103*

	U11	U22	U33	U12	U13	U23
S1	0.0238 (4)	0.0282 (4)	0.0225 (4)	0.0022 (3)	0.0066 (3)	0.0010 (3)
S2	0.0232 (4)	0.0245 (4)	0.0300 (5)	0.0000 (3)	0.0103 (3)	0.0003 (3)
O1	0.0279 (13)	0.0325 (14)	0.0231 (13)	0.0051 (11)	0.0031 (10)	0.0004 (11)
O2	0.0331 (14)	0.0318 (14)	0.0282 (14)	0.0131 (12)	0.0013 (10)	−0.0029 (12)
O3	0.0247 (13)	0.0295 (13)	0.0332 (14)	−0.0019 (11)	0.0105 (10)	−0.0017 (11)
O4	0.0208 (12)	0.0308 (14)	0.0338 (15)	0.0012 (10)	0.0100 (11)	−0.0037 (11)
C1	0.0205 (15)	0.0267 (17)	0.0247 (18)	0.0008 (13)	0.0078 (13)	−0.0005 (13)
C2	0.0181 (15)	0.0241 (17)	0.0249 (17)	0.0001 (12)	0.0049 (12)	−0.0004 (13)
C3	0.0241 (17)	0.0323 (19)	0.0251 (18)	0.0027 (15)	0.0053 (13)	−0.0032 (15)
C4	0.0263 (18)	0.044 (2)	0.0239 (19)	0.0037 (16)	0.0084 (14)	−0.0019 (16)
C5	0.0250 (17)	0.0366 (19)	0.0228 (17)	−0.0004 (15)	0.0029 (13)	0.0014 (16)
C6	0.0162 (14)	0.0308 (19)	0.0239 (17)	0.0011 (12)	0.0043 (12)	0.0010 (13)
C7	0.0193 (15)	0.0226 (16)	0.0272 (18)	−0.0007 (13)	0.0068 (13)	−0.0005 (14)
C8	0.0256 (17)	0.0248 (17)	0.0214 (17)	−0.0037 (13)	0.0063 (13)	−0.0030 (13)
C9	0.0228 (16)	0.0272 (17)	0.0168 (16)	−0.0022 (13)	0.0045 (12)	−0.0016 (13)
C10	0.0261 (17)	0.0273 (19)	0.0257 (18)	0.0025 (13)	0.0048 (13)	0.0003 (13)
C11	0.0299 (19)	0.0268 (19)	0.035 (2)	−0.0048 (14)	0.0034 (15)	−0.0009 (15)
C12	0.0277 (17)	0.0354 (19)	0.0283 (18)	−0.0086 (15)	0.0083 (14)	−0.0029 (16)
C13	0.0217 (16)	0.0313 (19)	0.0252 (18)	−0.0025 (14)	0.0035 (13)	0.0005 (14)
C14	0.0224 (16)	0.0287 (18)	0.0191 (16)	0.0014 (13)	0.0062 (12)	0.0014 (13)
N1	0.0277 (14)	0.0212 (14)	0.0230 (15)	0.0033 (11)	0.0067 (11)	−0.0009 (11)
N2	0.0391 (18)	0.0235 (15)	0.0240 (16)	0.0011 (13)	0.0134 (13)	0.0011 (12)
C15	0.0317 (19)	0.0226 (17)	0.0290 (19)	0.0001 (14)	0.0109 (14)	−0.0020 (14)
C16	0.0353 (19)	0.0247 (17)	0.0277 (18)	0.0009 (14)	0.0154 (15)	0.0027 (14)
C17	0.038 (2)	0.0249 (18)	0.0220 (18)	0.0016 (15)	0.0077 (15)	0.0010 (14)
C18	0.0264 (17)	0.0234 (17)	0.0243 (17)	0.0017 (14)	0.0035 (13)	−0.0030 (14)
C19	0.0314 (19)	0.0303 (18)	0.0266 (18)	0.0046 (16)	0.0026 (14)	−0.0062 (16)
C20	0.0268 (18)	0.033 (2)	0.033 (2)	0.0011 (15)	0.0049 (14)	−0.0031 (16)
C21	0.035 (2)	0.0244 (17)	0.036 (2)	0.0039 (15)	0.0147 (15)	−0.0015 (15)
C22	0.030 (2)	0.0266 (19)	0.048 (2)	−0.0044 (15)	0.0171 (17)	−0.0074 (17)
C23	0.050 (2)	0.029 (2)	0.039 (2)	−0.0038 (18)	0.0269 (19)	−0.0044 (17)
C24	0.044 (2)	0.0213 (17)	0.031 (2)	0.0006 (15)	0.0175 (16)	−0.0005 (15)
C25	0.0318 (18)	0.0192 (16)	0.0221 (17)	0.0008 (13)	0.0108 (13)	−0.0007 (13)
C26	0.0314 (17)	0.0207 (15)	0.0204 (16)	0.0041 (14)	0.0086 (13)	−0.0019 (13)
C27	0.0285 (19)	0.039 (2)	0.040 (2)	0.0000 (16)	0.0105 (16)	0.0030 (17)
C28	0.062 (3)	0.035 (2)	0.026 (2)	0.001 (2)	0.0163 (19)	0.0050 (17)
N3	0.0235 (14)	0.0261 (15)	0.0256 (15)	0.0019 (12)	0.0099 (11)	−0.0006 (12)
N4	0.0258 (14)	0.0224 (14)	0.0271 (15)	0.0008 (11)	0.0111 (11)	0.0022 (12)
C29	0.0271 (17)	0.0280 (17)	0.0263 (18)	0.0003 (15)	0.0097 (13)	0.0024 (15)
C30	0.0296 (18)	0.0293 (18)	0.0236 (18)	−0.0045 (14)	0.0092 (14)	−0.0013 (14)
C31	0.0284 (17)	0.0299 (17)	0.0253 (18)	−0.0022 (15)	0.0068 (13)	−0.0008 (15)
C32	0.0244 (16)	0.0262 (18)	0.0286 (18)	−0.0032 (14)	0.0081 (13)	0.0023 (14)
C33	0.0212 (18)	0.044 (2)	0.036 (2)	−0.0018 (16)	0.0069 (15)	0.0039 (18)
C34	0.0222 (17)	0.0341 (19)	0.035 (2)	−0.0004 (15)	0.0086 (14)	0.0037 (16)
C35	0.0261 (17)	0.0228 (16)	0.0296 (19)	0.0042 (13)	0.0118 (14)	0.0078 (14)
C36	0.0304 (19)	0.0273 (18)	0.036 (2)	0.0088 (15)	0.0144 (15)	0.0049 (16)
C37	0.037 (2)	0.0285 (19)	0.031 (2)	0.0044 (16)	0.0167 (15)	0.0021 (15)
C38	0.0301 (18)	0.0248 (17)	0.0248 (18)	−0.0017 (14)	0.0103 (14)	0.0029 (14)
C39	0.0242 (16)	0.0200 (16)	0.0285 (18)	0.0017 (13)	0.0120 (13)	0.0038 (13)
C40	0.0234 (16)	0.0211 (16)	0.0257 (18)	−0.0009 (13)	0.0101 (13)	0.0020 (13)
C41	0.0319 (19)	0.037 (2)	0.032 (2)	0.0035 (16)	0.0118 (15)	−0.0070 (16)
C42	0.034 (2)	0.0302 (18)	0.029 (2)	−0.0022 (16)	0.0102 (15)	−0.0015 (16)

S1—C1	1.795 (4)	C23—H23	0.9500
S1—S2	2.0586 (13)	C24—C28	1.496 (6)
S2—C8	1.798 (4)	C25—C26	1.455 (5)
O1—C7	1.222 (4)	C27—H27A	0.9800
O2—C7	1.312 (4)	C27—H27B	0.9800
O2—H2o	0.85 (4)	C27—H27C	0.9800
O3—C14	1.224 (5)	C28—H28A	0.9800
O4—C14	1.309 (4)	C28—H28B	0.9800
O4—H4o	0.84 (4)	C28—H28C	0.9800
C1—C6	1.398 (5)	N3—C29	1.316 (5)
C1—C2	1.409 (5)	N3—C40	1.360 (4)
C2—C3	1.395 (5)	N4—C38	1.340 (5)
C2—C7	1.506 (5)	N4—C39	1.365 (4)
C3—C4	1.387 (5)	C29—C30	1.423 (5)
C3—H3	0.9500	C29—C41	1.500 (5)
C4—C5	1.389 (5)	C30—C31	1.362 (5)
C4—H4	0.9500	C30—H30	0.9500
C5—C6	1.382 (5)	C31—C32	1.404 (5)
C5—H5	0.9500	C31—H31	0.9500
C6—H6	0.9500	C32—C40	1.417 (5)
C8—C13	1.393 (5)	C32—C33	1.424 (5)
C8—C9	1.408 (5)	C33—C34	1.351 (6)
C9—C10	1.392 (5)	C33—H33	0.9500
C9—C14	1.490 (5)	C34—C35	1.439 (5)
C10—C11	1.383 (5)	C34—H34	0.9500
C10—H10	0.9500	C35—C36	1.391 (5)
C11—C12	1.386 (6)	C35—C39	1.425 (5)
C11—H11	0.9500	C36—C37	1.378 (6)
C12—C13	1.385 (6)	C36—H36	0.9500
C12—H12	0.9500	C37—C38	1.409 (5)
C13—H13	0.9500	C37—H37	0.9500
N1—C15	1.333 (5)	C38—C42	1.502 (5)
N1—C26	1.357 (4)	C39—C40	1.439 (5)
N2—C24	1.326 (5)	C41—H41A	0.9800
N2—C25	1.351 (5)	C41—H41B	0.9800
C15—C16	1.401 (5)	C41—H41C	0.9800
C15—C27	1.509 (5)	C42—H42A	0.9800
C16—C17	1.375 (5)	C42—H42B	0.9800
C16—H16	0.9500	C42—H42C	0.9800
C17—C18	1.411 (5)	O5—C46	1.426 (7)
C17—H17	0.9500	O5—C43	1.436 (7)
C18—C26	1.417 (5)	C43—C44	1.432 (7)
C18—C19	1.429 (5)	C43—H43A	0.9900
C19—C20	1.348 (6)	C43—H43B	0.9900
C19—H19	0.9500	C44—C45	1.512 (7)
C20—C21	1.437 (5)	C44—H44A	0.9900
C20—H20	0.9500	C44—H44B	0.9900
C21—C22	1.413 (6)	C45—C46	1.511 (7)
C21—C25	1.419 (5)	C45—H45A	0.9900
C22—C23	1.377 (6)	C45—H45B	0.9900
C22—H22	0.9500	C46—H46A	0.9900
C23—C24	1.413 (6)	C46—H46B	0.9900
C1—S1—S2	104.22 (12)	H27A—C27—H27B	109.5
C8—S2—S1	104.28 (13)	C15—C27—H27C	109.5
C7—O2—H2O	113 (4)	H27A—C27—H27C	109.5
C14—O4—H4O	109 (3)	H27B—C27—H27C	109.5
C6—C1—C2	118.3 (3)	C24—C28—H28A	109.5
C6—C1—S1	121.3 (3)	C24—C28—H28B	109.5
C2—C1—S1	120.3 (3)	H28A—C28—H28B	109.5
C3—C2—C1	120.3 (3)	C24—C28—H28C	109.5
C3—C2—C7	119.3 (3)	H28A—C28—H28C	109.5
C1—C2—C7	120.4 (3)	H28B—C28—H28C	109.5
C4—C3—C2	120.5 (3)	C29—N3—C40	119.1 (3)
C4—C3—H3	119.7	C38—N4—C39	119.2 (3)
C2—C3—H3	119.7	N3—C29—C30	122.1 (3)
C3—C4—C5	119.3 (4)	N3—C29—C41	117.0 (3)
C3—C4—H4	120.4	C30—C29—C41	120.8 (3)
C5—C4—H4	120.4	C31—C30—C29	119.0 (4)
C6—C5—C4	120.8 (3)	C31—C30—H30	120.5
C6—C5—H5	119.6	C29—C30—H30	120.5
C4—C5—H5	119.6	C30—C31—C32	120.3 (3)
C5—C6—C1	120.8 (3)	C30—C31—H31	119.9
C5—C6—H6	119.6	C32—C31—H31	119.9
C1—C6—H6	119.6	C31—C32—C40	116.9 (3)
O1—C7—O2	125.0 (3)	C31—C32—C33	123.2 (3)
O1—C7—C2	122.0 (3)	C40—C32—C33	119.8 (4)
O2—C7—C2	113.0 (3)	C34—C33—C32	121.6 (4)
C13—C8—C9	119.1 (3)	C34—C33—H33	119.2
C13—C8—S2	121.2 (3)	C32—C33—H33	119.2
C9—C8—S2	119.7 (3)	C33—C34—C35	120.7 (4)
C10—C9—C8	119.2 (3)	C33—C34—H34	119.6
C10—C9—C14	118.9 (3)	C35—C34—H34	119.6
C8—C9—C14	121.9 (3)	C36—C35—C39	118.2 (3)
C11—C10—C9	121.2 (3)	C36—C35—C34	122.7 (3)
C11—C10—H10	119.4	C39—C35—C34	119.0 (4)
C9—C10—H10	119.4	C37—C36—C35	119.7 (4)
C10—C11—C12	119.5 (4)	C37—C36—H36	120.2
C10—C11—H11	120.3	C35—C36—H36	120.2
C12—C11—H11	120.3	C36—C37—C38	119.6 (4)
C13—C12—C11	120.2 (4)	C36—C37—H37	120.2
C13—C12—H12	119.9	C38—C37—H37	120.2
C11—C12—H12	119.9	N4—C38—C37	121.8 (3)
C12—C13—C8	120.8 (3)	N4—C38—C42	116.9 (3)
C12—C13—H13	119.6	C37—C38—C42	121.3 (4)
C8—C13—H13	119.6	N4—C39—C35	121.5 (3)
O3—C14—O4	124.6 (3)	N4—C39—C40	118.8 (3)
O3—C14—C9	121.3 (3)	C35—C39—C40	119.7 (3)
O4—C14—C9	114.0 (3)	N3—C40—C32	122.4 (3)
C15—N1—C26	118.5 (3)	N3—C40—C39	118.5 (3)
C24—N2—C25	118.3 (3)	C32—C40—C39	119.0 (3)
N1—C15—C16	122.5 (3)	C29—C41—H41A	109.5
N1—C15—C27	116.8 (3)	C29—C41—H41B	109.5
C16—C15—C27	120.8 (4)	H41A—C41—H41B	109.5
C17—C16—C15	119.6 (4)	C29—C41—H41C	109.5
C17—C16—H16	120.2	H41A—C41—H41C	109.5
C15—C16—H16	120.2	H41B—C41—H41C	109.5
C16—C17—C18	119.6 (3)	C38—C42—H42A	109.5
C16—C17—H17	120.2	C38—C42—H42B	109.5
C18—C17—H17	120.2	H42A—C42—H42B	109.5
C17—C18—C26	117.0 (3)	C38—C42—H42C	109.5
C17—C18—C19	122.7 (3)	H42A—C42—H42C	109.5
C26—C18—C19	120.3 (3)	H42B—C42—H42C	109.5
C20—C19—C18	120.6 (4)	C46—O5—C43	108.4 (6)
C20—C19—H19	119.7	C44—C43—O5	106.4 (6)
C18—C19—H19	119.7	C44—C43—H43A	110.5
C19—C20—C21	121.5 (4)	O5—C43—H43A	110.5
C19—C20—H20	119.2	C44—C43—H43B	110.5
C21—C20—H20	119.2	O5—C43—H43B	110.5
C22—C21—C25	117.1 (4)	H43A—C43—H43B	108.6
C22—C21—C20	123.1 (4)	C43—C44—C45	106.8 (6)
C25—C21—C20	119.7 (4)	C43—C44—H44A	110.4
C23—C22—C21	119.1 (4)	C45—C44—H44A	110.4
C23—C22—H22	120.5	C43—C44—H44B	110.4
C21—C22—H22	120.5	C45—C44—H44B	110.4
C22—C23—C24	119.4 (4)	H44A—C44—H44B	108.6
C22—C23—H23	120.3	C46—C45—C44	102.4 (6)
C24—C23—H23	120.3	C46—C45—H45A	111.3
N2—C24—C23	122.7 (4)	C44—C45—H45A	111.3
N2—C24—C28	116.5 (4)	C46—C45—H45B	111.3
C23—C24—C28	120.7 (4)	C44—C45—H45B	111.3
N2—C25—C21	123.4 (3)	H45A—C45—H45B	109.2
N2—C25—C26	118.0 (3)	O5—C46—C45	108.3 (6)
C21—C25—C26	118.7 (3)	O5—C46—H46A	110.0
N1—C26—C18	122.8 (3)	C45—C46—H46A	110.0
N1—C26—C25	118.0 (3)	O5—C46—H46B	110.0
C18—C26—C25	119.2 (3)	C45—C46—H46B	110.0
C15—C27—H27A	109.5	H46A—C46—H46B	108.4
C15—C27—H27B	109.5
C1—S1—S2—C8	88.74 (17)	C24—N2—C25—C26	−179.3 (3)
S2—S1—C1—C6	−18.7 (3)	C22—C21—C25—N2	−0.1 (5)
S2—S1—C1—C2	160.5 (2)	C20—C21—C25—N2	−177.7 (3)
C6—C1—C2—C3	−1.8 (5)	C22—C21—C25—C26	178.6 (3)
S1—C1—C2—C3	179.0 (3)	C20—C21—C25—C26	1.0 (5)
C6—C1—C2—C7	−178.2 (3)	C15—N1—C26—C18	−0.2 (5)
S1—C1—C2—C7	2.6 (4)	C15—N1—C26—C25	179.7 (3)
C1—C2—C3—C4	0.7 (6)	C17—C18—C26—N1	−0.5 (5)
C7—C2—C3—C4	177.1 (3)	C19—C18—C26—N1	179.3 (3)
C2—C3—C4—C5	−0.1 (6)	C17—C18—C26—C25	179.7 (3)
C3—C4—C5—C6	0.7 (6)	C19—C18—C26—C25	−0.5 (5)
C4—C5—C6—C1	−1.9 (6)	N2—C25—C26—N1	−1.4 (5)
C2—C1—C6—C5	2.4 (5)	C21—C25—C26—N1	179.9 (3)
S1—C1—C6—C5	−178.4 (3)	N2—C25—C26—C18	178.5 (3)
C3—C2—C7—O1	−157.5 (4)	C21—C25—C26—C18	−0.2 (5)
C1—C2—C7—O1	19.0 (5)	C40—N3—C29—C30	−0.9 (5)
C3—C2—C7—O2	21.9 (5)	C40—N3—C29—C41	178.2 (3)
C1—C2—C7—O2	−161.7 (3)	N3—C29—C30—C31	2.7 (6)
S1—S2—C8—C13	−15.5 (3)	C41—C29—C30—C31	−176.5 (4)
S1—S2—C8—C9	165.0 (2)	C29—C30—C31—C32	−1.5 (6)
C13—C8—C9—C10	0.2 (5)	C30—C31—C32—C40	−1.1 (5)
S2—C8—C9—C10	179.7 (3)	C30—C31—C32—C33	175.7 (4)
C13—C8—C9—C14	−178.0 (3)	C31—C32—C33—C34	−178.3 (4)
S2—C8—C9—C14	1.4 (4)	C40—C32—C33—C34	−1.5 (6)
C8—C9—C10—C11	−2.3 (5)	C32—C33—C34—C35	−1.1 (6)
C14—C9—C10—C11	176.0 (3)	C33—C34—C35—C36	179.4 (4)
C9—C10—C11—C12	2.9 (6)	C33—C34—C35—C39	1.6 (6)
C10—C11—C12—C13	−1.6 (6)	C39—C35—C36—C37	−1.5 (5)
C11—C12—C13—C8	−0.5 (6)	C34—C35—C36—C37	−179.3 (4)
C9—C8—C13—C12	1.1 (5)	C35—C36—C37—C38	1.2 (6)
S2—C8—C13—C12	−178.4 (3)	C39—N4—C38—C37	−0.4 (5)
C10—C9—C14—O3	−160.7 (3)	C39—N4—C38—C42	179.7 (3)
C8—C9—C14—O3	17.6 (5)	C36—C37—C38—N4	−0.2 (6)
C10—C9—C14—O4	18.5 (5)	C36—C37—C38—C42	179.7 (4)
C8—C9—C14—O4	−163.2 (3)	C38—N4—C39—C35	0.0 (5)
C26—N1—C15—C16	0.7 (5)	C38—N4—C39—C40	178.4 (3)
C26—N1—C15—C27	−179.9 (3)	C36—C35—C39—N4	0.9 (5)
N1—C15—C16—C17	−0.6 (6)	C34—C35—C39—N4	178.8 (3)
C27—C15—C16—C17	−179.9 (4)	C36—C35—C39—C40	−177.4 (3)
C15—C16—C17—C18	−0.1 (5)	C34—C35—C39—C40	0.4 (5)
C16—C17—C18—C26	0.6 (5)	C29—N3—C40—C32	−1.9 (5)
C16—C17—C18—C19	−179.2 (4)	C29—N3—C40—C39	−179.5 (3)
C17—C18—C19—C20	−179.6 (4)	C31—C32—C40—N3	3.0 (5)
C26—C18—C19—C20	0.6 (6)	C33—C32—C40—N3	−174.0 (3)
C18—C19—C20—C21	0.2 (6)	C31—C32—C40—C39	−179.4 (3)
C19—C20—C21—C22	−178.5 (4)	C33—C32—C40—C39	3.6 (5)
C19—C20—C21—C25	−1.0 (6)	N4—C39—C40—N3	−3.7 (5)
C25—C21—C22—C23	0.9 (6)	C35—C39—C40—N3	174.7 (3)
C20—C21—C22—C23	178.5 (4)	N4—C39—C40—C32	178.6 (3)
C21—C22—C23—C24	−1.1 (6)	C35—C39—C40—C32	−3.0 (5)
C25—N2—C24—C23	0.4 (5)	C46—O5—C43—C44	−23.0 (9)
C25—N2—C24—C28	178.7 (3)	O5—C43—C44—C45	28.7 (9)
C22—C23—C24—N2	0.4 (6)	C43—C44—C45—C46	−22.9 (9)
C22—C23—C24—C28	−177.8 (4)	C43—O5—C46—C45	8.1 (9)
C24—N2—C25—C21	−0.6 (5)	C44—C45—C46—O5	8.9 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···N1i	0.85 (4)	1.91 (4)	2.734 (4)	163 (4)
O2—H2o···N2i	0.85 (4)	2.46 (4)	2.982 (5)	121 (4)
O4—H4o···N4ii	0.84 (4)	1.86 (3)	2.691 (4)	170 (4)
C19—H19···O1iii	0.95	2.59	3.448 (5)	150
C22—H22···O5	0.95	2.52	3.383 (7)	150
C23—H23···O3	0.95	2.56	3.345 (5)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2o⋯N1i	0.85 (4)	1.91 (4)	2.734 (4)	163 (4)
O2—H2o⋯N2i	0.85 (4)	2.46 (4)	2.982 (5)	121 (4)
O4—H4o⋯N4ii	0.84 (4)	1.86 (3)	2.691 (4)	170 (4)
C19—H19⋯O1iii	0.95	2.59	3.448 (5)	150
C22—H22⋯O5	0.95	2.52	3.383 (7)	150
C23—H23⋯O3	0.95	2.56	3.345 (5)	140

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