3-Benzyl-2-(4-fluoro­phen­yl)-1,3-thia­zolidin-4-one

The title compound, C₁₆H₁₄FNOS, crystallizes with Z' = 2 in the space group P2₁/c. In one of the two independent mol­ecules, the heterocyclic ring is effectively planar, but in the other mol­ecule this ring adopts an envelope conformation. The mol­ecules are weakly linked by two C-H...O hydrogen bonds to form C₂²(14) chains. Comparisons are made with some symmetrically substituted 2-aryl-3-benzyl-1,3-thia­zoli­din-4-ones.

S1. Comment

In our synthetic search for new bioactive compounds, we have recently focused on the preparation of thiazol-4-one derivatives, which have shown a wide range of pharmacological activities (Insuasty et al., 2010, and references therein), i.e. antibacterial, antifungal, antimicrobial, antiviral and anticonvulsant activity. We report here the structure of the title compound, (I) (Fig. 1), an asymmetrically substituted 2-aryl-3-benzyl-1,3-thiazolidin-4-one derivative, which we compare with the series of symmetrically substituted analogues (Cunico et al., 2007), compounds (II)–(VI) (see scheme). Compound (I) was prepared in excellent yield using a three-component cyclocondensation reaction between benzylamine, 4-fluorobenzaldehyde and mercaptoacetic acid. By contrast, compounds (II)–(VI) were all prepared using the reactions of aryl aldehydes with L-valine [(S)-2-amino-3-methylpropionic acid] and mercaptoacetic acid (Cunico et al., 2006). In all of (I)–(VI), atom C2 in the heterocyclic ring is a stereogenic centre, but all of the compounds are formed as racemic mixtures, despite the presence of an enantiomerically pure amino acid in the synthesis of (II)–(VI).

Compound (I) crystallizes with Z' = 2 in space group P2₁/c, and in the selected asymmetric unit molecule 1, containing atom S11 (Fig. 1), has the R-configuration at atom C12, while molecule 2, containing atom S21, has the S-configuration at atom C22. Compounds (II)–(VI) all crystallize with Z' = 1, either in space group C2/c [(V)], or in space groups P2₁/c or P2₁/n [(II)–(IV) and (VI)], but the cell dimensions of (I) bear no close resemblance to those in any of (II)–(VI).

In molecule 1 of (I), the heterocyclic ring is effectively planar, with a maximum deviation from the mean plane through the ring atoms of only 0.021 (3) Å for atom C15. However, the corresponding ring in molecule 2 adopts an envelope conformation, folded across the line C22···C25, with ring-puckering parameters (Cremer & Pople, 1975) for the atom sequence S21/C22/N23/C24/C25 of Q₂ = 0.220 (3) Å and ϕ₂ = 184.4 (8)°. Similar envelope conformations were observed in each of (III)–(VI), but in (II) the heterocyclic ring adopts a half-chair conformation, twisted about the S1—C5 bond (Cunico et al., 2007). It seems likely that the saturated heterocyclic rings in (I)–(VI) are all fairly flexible and that their detailed conformations may, to some extent, be a reflection of direction-specific intermolecular forces.

The molecules of (I) are weakly linked into chains by two C—H···O hydrogen bonds (Table 1), but C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent, despite the presence of four independent and relatively unencumbered aryl rings in the asymmetric unit. Within the selected asymmetric unit, the two molecules are linked by a hydrogen bond having atom O14 as the acceptor, and dimeric units of this type, related to one another by translation, are linked by a second hydrogen bond having atom O24 as the acceptor, so giving rise to a C²₂(14) (Bernstein et al., 1995) chain running parallel to the [100] direction (Fig. 2).

There is a reasonably short C—H···F contact in (I) involving atom F124, but no corresponding contact occurs involving atom F224. However, this contact should not be regarded either as a hydrogen bond or indeed as structurally significant, as it has been established that halogen atoms bonded to C atoms are extremely poor acceptors, even from O—H or N—H, and worse from C—H (Howard et al., 1996; Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001).

It is of interest briefly to compare the structure of asymmetrically substituted (I) with those of symmetrically disubstituted (II)–(VI) (Cunico et al., 2007), all of which, as noted earlier, crystallize with Z' = 1. In the difluoro compound, (II), where the 2-aryl ring, but not the benzyl ring, exhibits orientational disorder over two sets of sites, a combination of C—H···O and C—H···π(arene) hydrogen bonds links the molecules into sheets, which are themselves linked in pairs by an aromatic π–π stacking interaction. Thus, the direction-specific intermolecular forces which are manifest in the structure of the difluoro compound, (II), differ significantly from those in the monofluoro compound, (I). The two isomeric dimethoxy compounds, (III) and (IV), present very different patterns of behaviour. There are no direction-specific intermolecular interactions of any type in the crystal structure of (III), but in (IV), a combination of C—H···O and C—H···π(arene) hydrogen bonds links the molecules into sheets. In a somewhat similar way, the isomeric dinitro compounds, (V) and (VI), again show different modes of molecular aggregation. In (V), a C—H···π(arene) hydrogen bond combines with three independent C—H···O hydrogen bonds to link the molecules into sheets, while in (VI), the molecules are linked into chains of fused rings by the action of four independent C—H···O hydrogen bonds. Thus, the supramolecular aggregation is significantly different in each member of this series of rather similar compounds, (I)–(VI).

Related literature

For related literature, see: Aakeröy et al. (1999); Bernstein et al. (1995); Brammer et al. (2001); Cremer & Pople (1975); Cunico et al. (2006, 2007); Howard et al. (1996); Insuasty et al. (2010); Thallapally & Nangia (2001).

S2. Experimental

A solution of equimolar amounts (9.4 mmol of each component) of benzylamine, 4-fluorobenzaldehyde and mercaptoacetic acid in anhydrous benzene (10 ml) was heated under reflux for 8 h. The reaction mixture was then allowed to cool to ambient temperature, after which it was washed with aqueous sodium hydrogencarbonate solution (10 ml of a 2% solution). The organic phase was dried over anhydrous magnesium sulfate and the solvent removed under reduced pressure. The solid residue was purified by crystallization from ethanol to give colourless crystals of (I) which were suitable for single-crystal X-ray diffraction (yield 96%, m.p. 367–368 K). MS (EI, 70 eV) m/z (% abundance): 287 (4, M⁺), 212 (23), 196 (32), 147 (52), 104 (38), 91 (100), 28 (28).

S3. Refinement

The merging R index is fairly high (0.1238), indicative of rather modest crystal quality. This is also reflected in the final R indices and the overall precision of the molecular geometry. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.99 (CH₂) or 1.00 Å (aliphatic CH), and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The independent molecules of (I), showing the atom-labelling scheme. (a) A type 1 molecule having the R-configuration at atom C12. (b) A type 2 molecule having the S-configuration at atom C22. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded C^22(14) chain parallel to [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

3-Benzyl-2-(4-fluorophenyl)-1,3-thiazolidin-4-one

Crystal data

C16H14FNOS	F(000) = 1200
Mr = 287.34	Dx = 1.425 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4986 reflections
a = 9.6931 (9) Å	θ = 3.1–25.5°
b = 16.8888 (16) Å	µ = 0.25 mm^−1
c = 16.4202 (18) Å	T = 120 K
β = 94.706 (12)°	Plate, colourless
V = 2679.0 (5) Å^3	0.45 × 0.40 × 0.14 mm
Z = 8

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	4986 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2857 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.124
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 3.1°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −20→20
Tmin = 0.868, Tmax = 0.966	l = −19→19
58245 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0436P)^2 + 2.3474P] where P = (Fo^2 + 2Fc^2)/3
4986 reflections	(Δ/σ)max = 0.001
361 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S11	0.79958 (9)	0.63084 (5)	0.52984 (5)	0.0225 (2)
C12	0.7586 (3)	0.61105 (18)	0.63504 (19)	0.0195 (7)
H12	0.8461	0.6147	0.6716	0.023*
N13	0.6675 (3)	0.67494 (15)	0.65566 (15)	0.0190 (6)
C14	0.6320 (3)	0.73163 (19)	0.59987 (19)	0.0201 (7)
C15	0.6914 (3)	0.71789 (19)	0.51968 (19)	0.0244 (8)
H15A	0.7468	0.7643	0.5052	0.029*
H15B	0.6160	0.7099	0.4760	0.029*
O14	0.5591 (2)	0.78937 (13)	0.61217 (14)	0.0274 (6)
C121	0.6970 (3)	0.53010 (18)	0.64497 (18)	0.0179 (7)
C122	0.5642 (3)	0.5130 (2)	0.61141 (19)	0.0224 (8)
H122	0.5104	0.5533	0.5837	0.027*
C123	0.5098 (3)	0.4382 (2)	0.6178 (2)	0.0255 (8)
H123	0.4188	0.4263	0.5952	0.031*
C124	0.5906 (4)	0.38163 (19)	0.6579 (2)	0.0260 (8)
C125	0.7225 (4)	0.3957 (2)	0.6918 (2)	0.0267 (8)
H125	0.7759	0.3548	0.7187	0.032*
C126	0.7750 (3)	0.47128 (19)	0.68535 (19)	0.0225 (8)
H126	0.8655	0.4830	0.7089	0.027*
F124	0.5379 (2)	0.30715 (11)	0.66378 (12)	0.0379 (5)
C137	0.6281 (3)	0.6807 (2)	0.73977 (19)	0.0234 (8)
H13A	0.5942	0.6286	0.7572	0.028*
H13B	0.5515	0.7193	0.7419	0.028*
C131	0.7480 (3)	0.70644 (19)	0.79791 (19)	0.0198 (7)
C132	0.8243 (3)	0.6516 (2)	0.84623 (19)	0.0237 (8)
H132	0.7974	0.5975	0.8455	0.028*
C133	0.9400 (3)	0.6760 (2)	0.8955 (2)	0.0260 (8)
H133	0.9920	0.6384	0.9284	0.031*
C134	0.9796 (4)	0.7546 (2)	0.8970 (2)	0.0294 (9)
H134	1.0591	0.7709	0.9305	0.035*
C135	0.9033 (3)	0.8096 (2)	0.8498 (2)	0.0264 (8)
H135	0.9294	0.8638	0.8511	0.032*
C136	0.7890 (3)	0.7849 (2)	0.8006 (2)	0.0246 (8)
H136	0.7373	0.8227	0.7680	0.029*
S21	0.30057 (9)	0.66988 (5)	0.52727 (5)	0.0229 (2)
C22	0.2483 (3)	0.70331 (19)	0.62657 (19)	0.0220 (8)
H22	0.3338	0.7139	0.6633	0.026*
N23	0.1771 (3)	0.63621 (15)	0.65876 (15)	0.0198 (6)
C24	0.1359 (3)	0.5761 (2)	0.6078 (2)	0.0221 (8)
C25	0.1800 (3)	0.58839 (19)	0.52250 (19)	0.0242 (8)
H25A	0.0987	0.6007	0.4842	0.029*
H25B	0.2247	0.5399	0.5033	0.029*
O24	0.0707 (2)	0.51840 (13)	0.62763 (13)	0.0291 (6)
C221	0.1633 (3)	0.77903 (19)	0.61890 (19)	0.0197 (7)
C222	0.0255 (3)	0.78243 (19)	0.6341 (2)	0.0239 (8)
H222	−0.0196	0.7359	0.6506	0.029*
C223	−0.0483 (3)	0.8531 (2)	0.6258 (2)	0.0265 (8)
H223	−0.1430	0.8555	0.6366	0.032*
C224	0.0198 (4)	0.91894 (19)	0.6017 (2)	0.0266 (8)
C225	0.1550 (3)	0.9181 (2)	0.5851 (2)	0.0285 (9)
H225	0.1987	0.9646	0.5672	0.034*
C226	0.2271 (3)	0.84754 (19)	0.5948 (2)	0.0254 (8)
H226	0.3222	0.8461	0.5848	0.030*
F224	−0.0522 (2)	0.98835 (11)	0.59266 (13)	0.0421 (6)
C237	0.1556 (3)	0.63268 (19)	0.74639 (19)	0.0236 (8)
H23A	0.0730	0.5997	0.7537	0.028*
H23B	0.1361	0.6868	0.7657	0.028*
C231	0.2768 (3)	0.59943 (19)	0.79866 (19)	0.0209 (7)
C232	0.3327 (3)	0.6402 (2)	0.8667 (2)	0.0278 (8)
H232	0.2965	0.6906	0.8793	0.033*
C233	0.4412 (4)	0.6081 (2)	0.9167 (2)	0.0356 (9)
H233	0.4788	0.6367	0.9632	0.043*
C234	0.4940 (4)	0.5355 (2)	0.8990 (2)	0.0359 (10)
H234	0.5681	0.5136	0.9332	0.043*
C235	0.4394 (4)	0.4940 (2)	0.8313 (2)	0.0378 (10)
H235	0.4758	0.4435	0.8191	0.045*
C236	0.3317 (4)	0.5258 (2)	0.7813 (2)	0.0293 (9)
H236	0.2948	0.4972	0.7347	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S11	0.0242 (5)	0.0216 (5)	0.0224 (5)	0.0005 (4)	0.0059 (4)	0.0006 (4)
C12	0.0175 (17)	0.0207 (18)	0.0205 (18)	−0.0003 (14)	0.0028 (14)	−0.0031 (15)
N13	0.0207 (15)	0.0200 (15)	0.0165 (14)	−0.0013 (12)	0.0032 (12)	−0.0014 (12)
C14	0.0160 (17)	0.0194 (19)	0.0249 (19)	−0.0008 (15)	0.0011 (14)	−0.0029 (16)
C15	0.0252 (19)	0.0248 (19)	0.0233 (19)	0.0011 (15)	0.0029 (15)	0.0012 (16)
O14	0.0232 (13)	0.0235 (14)	0.0357 (14)	0.0037 (11)	0.0031 (11)	−0.0005 (11)
C121	0.0224 (19)	0.0184 (18)	0.0140 (17)	−0.0001 (14)	0.0078 (14)	−0.0010 (14)
C122	0.0227 (19)	0.0244 (19)	0.0197 (18)	0.0011 (15)	0.0001 (15)	−0.0003 (15)
C123	0.0237 (19)	0.024 (2)	0.029 (2)	−0.0018 (16)	0.0063 (16)	−0.0025 (16)
C124	0.035 (2)	0.0145 (18)	0.030 (2)	−0.0066 (16)	0.0115 (17)	−0.0023 (16)
C125	0.034 (2)	0.024 (2)	0.0231 (19)	0.0046 (16)	0.0068 (16)	0.0044 (16)
C126	0.0231 (18)	0.026 (2)	0.0187 (18)	−0.0015 (15)	0.0021 (14)	0.0033 (15)
F124	0.0464 (13)	0.0242 (12)	0.0449 (13)	−0.0083 (10)	0.0146 (10)	0.0027 (10)
C137	0.0261 (19)	0.0227 (19)	0.0220 (18)	−0.0029 (15)	0.0060 (15)	−0.0028 (15)
C131	0.0229 (18)	0.0213 (19)	0.0157 (17)	−0.0027 (15)	0.0042 (14)	−0.0043 (15)
C132	0.027 (2)	0.0221 (19)	0.0222 (18)	0.0000 (15)	0.0072 (16)	0.0004 (16)
C133	0.025 (2)	0.032 (2)	0.0208 (19)	0.0095 (17)	0.0008 (15)	−0.0015 (16)
C134	0.0228 (19)	0.041 (2)	0.025 (2)	−0.0011 (17)	0.0028 (16)	−0.0115 (18)
C135	0.028 (2)	0.029 (2)	0.0229 (19)	−0.0073 (17)	0.0060 (16)	−0.0074 (17)
C136	0.028 (2)	0.026 (2)	0.0201 (18)	−0.0034 (16)	0.0043 (15)	−0.0004 (16)
S21	0.0226 (5)	0.0244 (5)	0.0222 (5)	0.0013 (4)	0.0053 (4)	−0.0005 (4)
C22	0.0213 (18)	0.0231 (19)	0.0216 (18)	−0.0010 (15)	0.0028 (15)	−0.0001 (15)
N23	0.0245 (15)	0.0181 (15)	0.0171 (14)	0.0012 (12)	0.0032 (12)	−0.0009 (12)
C24	0.0204 (18)	0.0214 (19)	0.0249 (19)	0.0038 (16)	0.0037 (15)	0.0003 (16)
C25	0.028 (2)	0.0206 (19)	0.0242 (19)	−0.0006 (15)	0.0011 (15)	−0.0018 (15)
O24	0.0296 (14)	0.0257 (14)	0.0326 (14)	−0.0026 (11)	0.0067 (11)	0.0039 (11)
C221	0.0234 (19)	0.0168 (18)	0.0193 (17)	−0.0020 (14)	0.0038 (14)	−0.0030 (14)
C222	0.025 (2)	0.0182 (18)	0.029 (2)	−0.0048 (15)	0.0007 (15)	0.0005 (15)
C223	0.0206 (19)	0.029 (2)	0.030 (2)	0.0051 (16)	0.0052 (15)	0.0011 (16)
C224	0.032 (2)	0.0190 (19)	0.029 (2)	0.0081 (16)	0.0077 (16)	0.0018 (16)
C225	0.033 (2)	0.0210 (19)	0.033 (2)	−0.0058 (16)	0.0092 (17)	−0.0003 (16)
C226	0.0231 (19)	0.026 (2)	0.028 (2)	−0.0010 (15)	0.0043 (15)	0.0017 (16)
F224	0.0442 (13)	0.0227 (11)	0.0610 (15)	0.0103 (10)	0.0139 (11)	0.0047 (11)
C237	0.0284 (19)	0.0215 (19)	0.0215 (18)	0.0055 (15)	0.0061 (15)	−0.0013 (15)
C231	0.0210 (18)	0.0247 (19)	0.0176 (18)	−0.0016 (15)	0.0060 (14)	0.0029 (15)
C232	0.026 (2)	0.032 (2)	0.026 (2)	−0.0016 (16)	0.0077 (16)	−0.0028 (17)
C233	0.029 (2)	0.054 (3)	0.024 (2)	−0.005 (2)	0.0029 (17)	−0.0010 (19)
C234	0.029 (2)	0.057 (3)	0.022 (2)	0.007 (2)	0.0063 (17)	0.011 (2)
C235	0.043 (2)	0.038 (2)	0.034 (2)	0.0163 (19)	0.0091 (19)	0.0093 (19)
C236	0.037 (2)	0.027 (2)	0.023 (2)	0.0042 (17)	0.0030 (17)	0.0010 (16)

Geometric parameters (Å, º)

S11—C15	1.806 (3)	S21—C25	1.803 (3)
S11—C12	1.835 (3)	S21—C22	1.836 (3)
C12—N13	1.452 (4)	C22—N23	1.449 (4)
C12—C121	1.506 (4)	C22—C221	1.521 (4)
C12—H12	1.0000	C22—H22	1.0000
N13—C14	1.350 (4)	N23—C24	1.355 (4)
N13—C137	1.466 (4)	N23—C237	1.472 (4)
C14—O14	1.230 (4)	C24—O24	1.220 (4)
C14—C15	1.498 (4)	C24—C25	1.511 (4)
C15—H15A	0.9900	C25—H25A	0.9900
C15—H15B	0.9900	C25—H25B	0.9900
C121—C126	1.384 (4)	C221—C222	1.380 (4)
C121—C122	1.388 (4)	C221—C226	1.385 (4)
C122—C123	1.375 (4)	C222—C223	1.392 (4)
C122—H122	0.9500	C222—H222	0.9500
C123—C124	1.370 (5)	C223—C224	1.368 (5)
C123—H123	0.9500	C223—H223	0.9500
C124—F124	1.364 (4)	C224—C225	1.361 (5)
C124—C125	1.372 (5)	C224—F224	1.366 (4)
C125—C126	1.382 (4)	C225—C226	1.384 (4)
C125—H125	0.9500	C225—H225	0.9500
C126—H126	0.9500	C226—H226	0.9500
C137—C131	1.507 (4)	C237—C231	1.506 (4)
C137—H13A	0.9900	C237—H23A	0.9900
C137—H13B	0.9900	C237—H23B	0.9900
C131—C136	1.383 (4)	C231—C232	1.384 (4)
C131—C132	1.392 (4)	C231—C236	1.391 (4)
C132—C133	1.391 (5)	C232—C233	1.390 (5)
C132—H132	0.9500	C232—H232	0.9500
C133—C134	1.381 (5)	C233—C234	1.370 (5)
C133—H133	0.9500	C233—H233	0.9500
C134—C135	1.385 (5)	C234—C235	1.382 (5)
C134—H134	0.9500	C234—H234	0.9500
C135—C136	1.380 (5)	C235—C236	1.383 (5)
C135—H135	0.9500	C235—H235	0.9500
C136—H136	0.9500	C236—H236	0.9500
C15—S11—C12	93.80 (14)	C25—S21—C22	92.78 (15)
N13—C12—C121	113.3 (3)	N23—C22—C221	114.6 (3)
N13—C12—S11	105.5 (2)	N23—C22—S21	104.9 (2)
C121—C12—S11	112.7 (2)	C221—C22—S21	111.9 (2)
N13—C12—H12	108.4	N23—C22—H22	108.4
C121—C12—H12	108.4	C221—C22—H22	108.4
S11—C12—H12	108.4	S21—C22—H22	108.4
C14—N13—C12	119.7 (3)	C24—N23—C22	119.0 (3)
C14—N13—C137	121.4 (3)	C24—N23—C237	121.0 (3)
C12—N13—C137	118.7 (3)	C22—N23—C237	119.9 (3)
O14—C14—N13	124.6 (3)	O24—C24—N23	124.5 (3)
O14—C14—C15	122.3 (3)	O24—C24—C25	123.3 (3)
N13—C14—C15	113.1 (3)	N23—C24—C25	112.2 (3)
C14—C15—S11	107.9 (2)	C24—C25—S21	107.2 (2)
C14—C15—H15A	110.1	C24—C25—H25A	110.3
S11—C15—H15A	110.1	S21—C25—H25A	110.3
C14—C15—H15B	110.1	C24—C25—H25B	110.3
S11—C15—H15B	110.1	S21—C25—H25B	110.3
H15A—C15—H15B	108.4	H25A—C25—H25B	108.5
C126—C121—C122	119.5 (3)	C222—C221—C226	118.6 (3)
C126—C121—C12	119.8 (3)	C222—C221—C22	123.1 (3)
C122—C121—C12	120.6 (3)	C226—C221—C22	118.3 (3)
C123—C122—C121	120.7 (3)	C221—C222—C223	121.0 (3)
C123—C122—H122	119.7	C221—C222—H222	119.5
C121—C122—H122	119.7	C223—C222—H222	119.5
C124—C123—C122	118.0 (3)	C224—C223—C222	117.9 (3)
C124—C123—H123	121.0	C224—C223—H223	121.0
C122—C123—H123	121.0	C222—C223—H223	121.0
F124—C124—C123	118.3 (3)	C225—C224—F224	118.6 (3)
F124—C124—C125	118.2 (3)	C225—C224—C223	123.0 (3)
C123—C124—C125	123.5 (3)	F224—C224—C223	118.3 (3)
C124—C125—C126	117.7 (3)	C224—C225—C226	118.2 (3)
C124—C125—H125	121.1	C224—C225—H225	120.9
C126—C125—H125	121.1	C226—C225—H225	120.9
C125—C126—C121	120.7 (3)	C225—C226—C221	121.2 (3)
C125—C126—H126	119.7	C225—C226—H226	119.4
C121—C126—H126	119.7	C221—C226—H226	119.4
N13—C137—C131	111.6 (3)	N23—C237—C231	113.9 (3)
N13—C137—H13A	109.3	N23—C237—H23A	108.8
C131—C137—H13A	109.3	C231—C237—H23A	108.8
N13—C137—H13B	109.3	N23—C237—H23B	108.8
C131—C137—H13B	109.3	C231—C237—H23B	108.8
H13A—C137—H13B	108.0	H23A—C237—H23B	107.7
C136—C131—C132	118.8 (3)	C232—C231—C236	118.6 (3)
C136—C131—C137	120.1 (3)	C232—C231—C237	120.6 (3)
C132—C131—C137	121.0 (3)	C236—C231—C237	120.7 (3)
C133—C132—C131	120.0 (3)	C231—C232—C233	120.7 (3)
C133—C132—H132	120.0	C231—C232—H232	119.7
C131—C132—H132	120.0	C233—C232—H232	119.7
C134—C133—C132	120.3 (3)	C234—C233—C232	120.1 (4)
C134—C133—H133	119.8	C234—C233—H233	120.0
C132—C133—H133	119.8	C232—C233—H233	120.0
C133—C134—C135	120.0 (3)	C233—C234—C235	120.0 (4)
C133—C134—H134	120.0	C233—C234—H234	120.0
C135—C134—H134	120.0	C235—C234—H234	120.0
C136—C135—C134	119.4 (3)	C234—C235—C236	120.1 (4)
C136—C135—H135	120.3	C234—C235—H235	120.0
C134—C135—H135	120.3	C236—C235—H235	120.0
C135—C136—C131	121.5 (3)	C235—C236—C231	120.6 (3)
C135—C136—H136	119.2	C235—C236—H236	119.7
C131—C136—H136	119.2	C231—C236—H236	119.7
C15—S11—C12—N13	−1.8 (2)	C25—S21—C22—N23	17.6 (2)
C15—S11—C12—C121	122.2 (2)	C25—S21—C22—C221	−107.3 (2)
C121—C12—N13—C14	−123.5 (3)	C221—C22—N23—C24	108.0 (3)
S11—C12—N13—C14	0.2 (3)	S21—C22—N23—C24	−15.1 (3)
C121—C12—N13—C137	62.9 (3)	C221—C22—N23—C237	−74.4 (4)
S11—C12—N13—C137	−173.4 (2)	S21—C22—N23—C237	162.5 (2)
C12—N13—C14—O14	−177.6 (3)	C22—N23—C24—O24	−177.1 (3)
C137—N13—C14—O14	−4.2 (5)	C237—N23—C24—O24	5.4 (5)
C12—N13—C14—C15	2.0 (4)	C22—N23—C24—C25	3.0 (4)
C137—N13—C14—C15	175.5 (3)	C237—N23—C24—C25	−174.6 (3)
O14—C14—C15—S11	176.4 (3)	O24—C24—C25—S21	−168.9 (3)
N13—C14—C15—S11	−3.2 (3)	N23—C24—C25—S21	11.1 (3)
C12—S11—C15—C14	2.9 (2)	C22—S21—C25—C24	−16.5 (2)
N13—C12—C121—C126	−133.1 (3)	N23—C22—C221—C222	−5.6 (4)
S11—C12—C121—C126	107.3 (3)	S21—C22—C221—C222	113.7 (3)
N13—C12—C121—C122	49.3 (4)	N23—C22—C221—C226	174.9 (3)
S11—C12—C121—C122	−70.4 (3)	S21—C22—C221—C226	−65.8 (3)
C126—C121—C122—C123	−0.1 (5)	C226—C221—C222—C223	−0.2 (5)
C12—C121—C122—C123	177.6 (3)	C22—C221—C222—C223	−179.6 (3)
C121—C122—C123—C124	−0.2 (5)	C221—C222—C223—C224	0.3 (5)
C122—C123—C124—F124	−179.3 (3)	C222—C223—C224—C225	0.6 (5)
C122—C123—C124—C125	0.0 (5)	C222—C223—C224—F224	179.4 (3)
F124—C124—C125—C126	179.9 (3)	F224—C224—C225—C226	179.7 (3)
C123—C124—C125—C126	0.6 (5)	C223—C224—C225—C226	−1.5 (5)
C124—C125—C126—C121	−0.9 (5)	C224—C225—C226—C221	1.6 (5)
C122—C121—C126—C125	0.7 (5)	C222—C221—C226—C225	−0.8 (5)
C12—C121—C126—C125	−177.0 (3)	C22—C221—C226—C225	178.7 (3)
C14—N13—C137—C131	−102.7 (3)	C24—N23—C237—C231	93.0 (3)
C12—N13—C137—C131	70.8 (4)	C22—N23—C237—C231	−84.5 (3)
N13—C137—C131—C136	76.6 (4)	N23—C237—C231—C232	128.0 (3)
N13—C137—C131—C132	−99.8 (3)	N23—C237—C231—C236	−54.4 (4)
C136—C131—C132—C133	−0.5 (5)	C236—C231—C232—C233	−0.1 (5)
C137—C131—C132—C133	175.9 (3)	C237—C231—C232—C233	177.5 (3)
C131—C132—C133—C134	0.1 (5)	C231—C232—C233—C234	0.0 (5)
C132—C133—C134—C135	0.5 (5)	C232—C233—C234—C235	0.0 (5)
C133—C134—C135—C136	−0.8 (5)	C233—C234—C235—C236	0.2 (5)
C134—C135—C136—C131	0.5 (5)	C234—C235—C236—C231	−0.3 (5)
C132—C131—C136—C135	0.2 (5)	C232—C231—C236—C235	0.3 (5)
C137—C131—C136—C135	−176.2 (3)	C237—C231—C236—C235	−177.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C126—H126···O24^i	0.95	2.56	3.193 (4)	125
C226—H226···O14	0.95	2.49	3.354 (4)	151
C137—H13B···F124^ii	0.99	2.36	3.175 (4)	139

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+3/2.