Thio­acetanilide at 120 K

The title compound, C₈H₉NS, has four symmetry-independent molecules in the asymmetric unit. These mol­ecules link into two independent infinite N-H...S hydrogen-bonded chains in the a-axis direction with graph-set notation C₂²(8). The NH-CS group adopts a trans conformation and forms a dihedral angle of about 50° with the phenyl ring. The inter­molecular hydrogen-bond energy calculated by the density functional theory (DFT) method is -14.95 kJ mol^-1. The correlation between the IR spectrum of this compound and the hydrogen-bond energy is also discussed. This mol­ecular system is of inter­est because of its biological function.

S1. Comment

The title compound, (I), belongs to the thioamides, which have a thiol and a carbonyl group capable of forming hydrogen bonds. The objects of our research are the IR spectra of thioamide crystals in the frequency range of the proton and deuteron stretching vibrations in hydrogen bonds. Characteristic isotopic and spectroscopic effects, called self-organization effects, are observed in this vibration frequency range (Flakus, 1989, 2003; Flakus & Bańczyk, 1999). As a result of structural and polarized IR spectroscopic investigations of hydrogen-bonded molecular systems, an even richer set of data concerning the complexity of ν_X—H band-generation mechanisms could be obtained. Measurements of the polarized IR spectra of diverse spatially oriented hydrogen-bond systems present in the lattices of molecular crystals allow us to estimate the polarization properties of the transitions, found in the excited states of proton vibrations in the crystal structures, which contribute to the ν_X—H band-generation mechanisms in the crystalline spectra. Thus, for a reliable interpretation of the reasons for the self-organization mechanism, the crystal structure of the hydrogen-bonded system must be known. In the case of (I), a crystallographic study has not been reported until now.

In this article, the result of our structural studies of the hydrogen bonds of (I) is presented. This molecular system is of central interest for researchers, as (I) is one of the smaller molecules with a thiopeptide group, capable of associating with other thiopeptide groups to form hydrogen bonds. The biological function of (I) has attracted interest in recent years. Thus, the metabolism and acute toxicity of (I) have been studied in the rat (Trennery & Warning, 1983). The proton magnetic resonance and IR spectra of solutions of (I) have been reported (Birchall & Gillespie, 1963; Galabov et al., 2003). The conformational stability of the thioamide group in (I) has been discussed using density functional theory (DFT) (Galabov et al., 2003).

Compound (I) crystallizes with four molecules in the asymmetric unit (Fig. 1). All four molecules adopt the trans conformation of the –NH—CS– group with comparable bond lengths and angles. The N—C(═S) and C═S bond lengths are in the region of 1.329 and 1.675 Å, respectively, and compare well with those of related compounds in the literature [References and examples?]. These lengths are also in good agreement with those calculated at the B3LYP/6–31G** level of theory (Galabov et al., 2003). The CS—NH group is almost planar in each molecule and the dihedral angles with the phenyl ring plane are in the range 45–53°. The calculated dihedral angle between the aromatic ring and the NH—CS group is in the region of 0 (180)°. This is a very surprising fact, because in the literature the trans isomer is reported to be almost planar with deviations from planarity smaller than 3° (Galabov et al., 2003). A search of the Cambridge Structural Database (CSD, Version 5.28; Conquest Version 1.9; Allen, 2002) was carried out to check the reported angle. This angle varies in related compounds, such as formanilide (Omondi et al., 2008), acetanilide (Brown, 1966) and larger molecules with a thioacetamide group such as (Z)-N-(2-t-butylphenyl)propanethioamide (Dantale et al., 2002), in which this dihedral angle could adopt a larger value.

For a comparison of the bond lengths and angles with other thioacetanilide derivatives, a search of the CSD yielded only one structure, thioacetanilide-S-oxide [CSD refcode SACANO (Jarchow, 1969) and SACANO01 (Kraeft, 1967)]. In that compound, the thioacetanilide is found in the cis form of the –NH—CS– group. A comparison of the bond lengths and angles indicates that the N1—C1 and C1—S1 bond lengths and N1—C7—S1 and N1—C7—C8 angles are mostly affected by the atom type bound to the S atom: H in (I) by hydrogen bonding, and O in thioacetanilide-S-oxide.

In the crystal structure of (I), the molecules interact via N—H···S hydrogen bonds to form four different infinite zigzag chains parallel to the a axis with graph-set notation C¹₁(4) and C²₂(8) (Fig. 2) (Bernstein et al., 1990; Grell et al., 1999). The values of the hydrogen-bond distances are in the range 3.0–4.0 Å and therefore they can be treated as weak hydrogen bonds (Desiraju & Steiner, 1999). The strength of the hydrogen bonds in this compound was also investigated by IR spectroscopy. The band of the isolated N—H stretching vibration, ν_N—H, is located at a frequency of 3400 cm^-1. In the case of (I), we observed this band in the frequency range 3200–2800 cm^-1 with the shift of about 400 cm^-1 (Fig. 3). This relative shift is larger than 5% and is characteristic for a strong hydrogen bond (Desiraju & Steiner, 1999). Thus, the energy of the intermolecular hydrogen bonds was also calculated.

The initial geometry of (I) was optimized using the MM+ molecular modelling method implemented in HYPERCHEM (Hypercube, 1998). In the next step, the DFT calculations were performed using the GAUSSIAN03 software package (Frisch et al., 2003) with the B3LYP hybrid function. The theoretical investigation of the hydrogen bonds was performed using GAUSSIAN03 at the B3LYP/6–31G** level of theory. A cluster (57 atoms) consisted of three neighbouring molecules of (I) with two intermolecular hydrogen bonds, N1—H···S2 and N2—H···S3. The energy of the intermolecular hydrogen bonds was calculated and corrected to basis set superposition error (BSSE) using a standard procedure (Boys & Bernardi, 1970). The total energy of the two hydrogen bonds was estimated at -29.9 kJ mol^-1. This value indicates that the hydrogen bonds are strong (Desiraju & Steiner, 1999). Calculated hydrogen-bond distances for these two intermolecular hydrogen bonds (N1—H···S2 and N2—H···S3) were N—H = 1.019 and 1.018 Å, H···S = 2.692 and 2.746 Å, and N···S = 3.677 and 3.764 Å, respectively. The calculated N—H···S angles for these hydrogen bonds were 162.2 and 177.1°, respectively. The obtained values of the hydrogen-bond geometry correspond well with the experimental data.

Our knowledge of the hydrogen-bond geometry enables us to recognize the type of self-organization mechanism. Therefore, we plan to carry out further studies on the polarized IR spectra of this compound and its isotopic derivatives.

S2. Experimental

Thioacetanilide was purchased from Sigma–Aldrich and used without further purification. It was dissolved in a water–acetone mixture (1:1 v/v). After several days, yellow single crystals of (I) had formed, which proved to be suitable for single-crystal X-ray diffraction analysis. The crystals were mounted on a quartz glass capillary and cooled to 120 K with a cold dry nitrogen gas stream (Oxford Cryosystems equipment); the temperature stability was ±0.1 K. The IR spectrum of a polycrystalline sample of (I) was measured in transmission at room temperature using the KBr pellet technique on a Nicolet Magna 560 FT–IR spectrometer with 4 cm^-1 resolution.

S3. Refinement

The H atoms of the phenyl rings and of the methyl group were treated as riding on their parent atoms, with C—H = 0.95 or 0.98 Å, respectively, and with U_iso(H) = 1.2 or 1.5 times U_eq(C), respectively. H atoms involved in hydrogen bonding were located in a difference Fourier map (ΔF) and refined freely with isotropic temperature factors.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures

	Fig. 1. The four symmetry-independent molecules of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitary radii.
	Fig. 2. A view of hydrogen-bonded chains of (I) along the a axis. Only H atoms involved in hydrogen bonding are shown.
	Fig. 3. The IR spectrum of (I) measured by the KBr pellet technique at room temperature presented in the νN—H frequency range.

N-phenylthioacetamide

Crystal data

C8H9NS	F(000) = 1280
Mr = 151.22	Dx = 1.276 Mg m^−3
Monoclinic, P21/n	Melting point: 350 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.8858 (4) Å	Cell parameters from 10000 reflections
b = 10.5330 (4) Å	θ = 2.9–32.9°
c = 30.3073 (13) Å	µ = 0.33 mm^−1
β = 94.050 (4)°	T = 120 K
V = 3147.9 (2) Å^3	Needle, yellow
Z = 16	0.3 × 0.12 × 0.06 mm

Data collection

Oxford Diffraction KM4 CCD with Sapphire3 detector diffractometer	3903 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.1°, θmin = 2.9°
Detector resolution: 16.0328 pixels mm^-1	h = −6→11
ε scans	k = −12→12
19399 measured reflections	l = −36→36
5572 independent 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0544P)^2] where P = (Fo^2 + 2Fc^2)/3
5572 reflections	(Δ/σ)max = 0.001
381 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
S41	0.63020 (5)	0.89094 (5)	−0.001632 (17)	0.02050 (14)
H41N	0.944 (2)	0.756 (2)	0.0141 (8)	0.039 (7)*
S11	0.63255 (5)	0.39037 (5)	0.248576 (17)	0.02101 (14)
N11	0.87765 (17)	0.28578 (17)	0.26086 (6)	0.0181 (4)
C11	0.9249 (2)	0.35763 (18)	0.29896 (6)	0.0178 (4)
C12	1.0563 (2)	0.40594 (18)	0.30056 (7)	0.0213 (5)
H12	1.1100	0.3953	0.2760	0.026*
C13	1.1087 (2)	0.4694 (2)	0.33796 (7)	0.0249 (5)
H13	1.1986	0.5016	0.3392	0.030*
C14	1.0298 (2)	0.4862 (2)	0.37360 (7)	0.0257 (5)
H14	1.0655	0.5300	0.3992	0.031*
C15	0.8987 (2)	0.4388 (2)	0.37171 (7)	0.0248 (5)
H15	0.8445	0.4513	0.3960	0.030*
C16	0.8460 (2)	0.3735 (2)	0.33479 (7)	0.0220 (5)
H16	0.7567	0.3398	0.3339	0.026*
C17	0.75708 (19)	0.28934 (18)	0.23844 (6)	0.0178 (4)
C18	0.7407 (2)	0.19660 (19)	0.20075 (7)	0.0233 (5)
H118	0.6482	0.1625	0.1989	0.035*
H218	0.8057	0.1270	0.2058	0.035*
H318	0.7574	0.2399	0.1730	0.035*
H11N	0.933 (2)	0.234 (2)	0.2516 (7)	0.032 (7)*
S21	0.13246 (5)	0.08707 (5)	0.242693 (17)	0.01909 (13)
N21	0.37322 (17)	0.19453 (17)	0.26196 (5)	0.0182 (4)
C21	0.4090 (2)	0.12174 (19)	0.30094 (7)	0.0189 (4)
C22	0.5372 (2)	0.0676 (2)	0.30543 (7)	0.0239 (5)
H22	0.5971	0.0751	0.2824	0.029*
C23	0.5771 (2)	0.0021 (2)	0.34407 (7)	0.0282 (5)
H23	0.6644	−0.0357	0.3473	0.034*
C24	0.4913 (2)	−0.0084 (2)	0.37770 (7)	0.0286 (5)
H24	0.5195	−0.0525	0.4041	0.034*
C25	0.3632 (2)	0.0460 (2)	0.37278 (7)	0.0254 (5)
H25	0.3033	0.0374	0.3958	0.031*
C26	0.3217 (2)	0.11249 (19)	0.33477 (6)	0.0209 (5)
H26	0.2347	0.1512	0.3319	0.025*
C27	0.2593 (2)	0.18918 (18)	0.23598 (7)	0.0186 (4)
C28	0.2533 (2)	0.28128 (19)	0.19788 (7)	0.0231 (5)
H128	0.3122	0.3541	0.2055	0.035*
H228	0.1598	0.3107	0.1918	0.035*
H328	0.2841	0.2390	0.1716	0.035*
H21N	0.432 (2)	0.245 (2)	0.2530 (7)	0.025 (6)*
S31	0.12939 (5)	0.60924 (5)	0.000385 (17)	0.02044 (14)
N31	0.37382 (17)	0.68827 (16)	−0.01835 (6)	0.0185 (4)
C31	0.3899 (2)	0.60325 (19)	−0.05435 (7)	0.0184 (4)
C32	0.4317 (2)	0.6530 (2)	−0.09354 (7)	0.0241 (5)
H32	0.4421	0.7421	−0.0969	0.029*
C33	0.4580 (2)	0.5711 (2)	−0.12787 (7)	0.0285 (5)
H33	0.4873	0.6045	−0.1547	0.034*
C34	0.4421 (2)	0.4421 (2)	−0.12328 (7)	0.0291 (5)
H34	0.4605	0.3867	−0.1469	0.035*
C35	0.3992 (2)	0.3932 (2)	−0.08414 (7)	0.0280 (5)
H35	0.3871	0.3042	−0.0811	0.034*
C36	0.3740 (2)	0.4733 (2)	−0.04953 (7)	0.0228 (5)
H36	0.3458	0.4395	−0.0226	0.027*
C37	0.27183 (19)	0.69516 (19)	0.00769 (6)	0.0176 (4)
C38	0.2937 (2)	0.78651 (19)	0.04564 (7)	0.0223 (5)
H138	0.2072	0.8262	0.0516	0.033*
H238	0.3583	0.8522	0.0381	0.033*
H338	0.3298	0.7406	0.0720	0.033*
H31N	0.441 (2)	0.739 (2)	−0.0123 (7)	0.022 (6)*
N41	0.88224 (17)	0.81196 (17)	0.01892 (6)	0.0193 (4)
C41	0.90954 (19)	0.89769 (18)	0.05500 (6)	0.0178 (4)
C42	0.9598 (2)	0.8488 (2)	0.09555 (7)	0.0230 (5)
H42	0.9700	0.7597	0.0994	0.028*
C43	0.9947 (2)	0.9306 (2)	0.13022 (7)	0.0264 (5)
H43	1.0296	0.8977	0.1579	0.032*
C44	0.9788 (2)	1.0602 (2)	0.12461 (7)	0.0259 (5)
H44	1.0026	1.1163	0.1485	0.031*
C45	0.9282 (2)	1.1081 (2)	0.08421 (7)	0.0258 (5)
H45	0.9164	1.1971	0.0805	0.031*
C46	0.89463 (19)	1.02708 (19)	0.04915 (7)	0.0210 (5)
H46	0.8616	1.0602	0.0213	0.025*
C47	0.77047 (19)	0.80441 (18)	−0.00803 (6)	0.0171 (4)
C48	0.7781 (2)	0.7140 (2)	−0.04585 (7)	0.0232 (5)
H148	0.6888	0.6756	−0.0528	0.035*
H248	0.8444	0.6473	−0.0378	0.035*
H348	0.8061	0.7600	−0.0718	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S41	0.0142 (3)	0.0188 (3)	0.0283 (3)	0.0007 (2)	0.0004 (2)	−0.0011 (2)
S11	0.0158 (3)	0.0192 (3)	0.0278 (3)	0.0018 (2)	0.0001 (2)	−0.0042 (2)
N11	0.0159 (9)	0.0170 (9)	0.0217 (10)	0.0040 (8)	0.0037 (7)	−0.0017 (7)
C11	0.0197 (11)	0.0144 (10)	0.0192 (11)	0.0035 (8)	0.0013 (8)	0.0019 (8)
C12	0.0200 (11)	0.0220 (12)	0.0221 (12)	0.0025 (9)	0.0031 (9)	0.0022 (9)
C13	0.0238 (11)	0.0217 (12)	0.0285 (13)	−0.0024 (9)	−0.0024 (9)	0.0020 (9)
C14	0.0353 (13)	0.0203 (12)	0.0204 (12)	0.0031 (10)	−0.0052 (10)	0.0011 (9)
C15	0.0311 (13)	0.0256 (12)	0.0182 (11)	0.0075 (10)	0.0048 (9)	0.0037 (9)
C16	0.0196 (11)	0.0240 (11)	0.0228 (12)	0.0022 (9)	0.0034 (9)	0.0042 (9)
C17	0.0184 (11)	0.0178 (11)	0.0178 (11)	−0.0010 (9)	0.0040 (8)	0.0034 (8)
C18	0.0240 (11)	0.0203 (11)	0.0254 (12)	0.0018 (9)	0.0002 (9)	−0.0035 (9)
S21	0.0148 (3)	0.0183 (3)	0.0239 (3)	−0.0016 (2)	−0.0011 (2)	0.0011 (2)
N21	0.0153 (9)	0.0194 (10)	0.0199 (10)	−0.0034 (8)	0.0022 (7)	0.0044 (7)
C21	0.0198 (11)	0.0163 (10)	0.0202 (11)	−0.0017 (9)	−0.0023 (8)	−0.0001 (9)
C22	0.0183 (11)	0.0253 (12)	0.0280 (12)	−0.0010 (9)	0.0006 (9)	−0.0011 (10)
C23	0.0264 (12)	0.0232 (12)	0.0336 (14)	0.0024 (10)	−0.0083 (10)	0.0000 (10)
C24	0.0384 (14)	0.0219 (12)	0.0237 (13)	−0.0017 (10)	−0.0091 (10)	0.0015 (9)
C25	0.0340 (13)	0.0240 (12)	0.0182 (11)	−0.0037 (10)	0.0014 (9)	−0.0017 (9)
C26	0.0225 (11)	0.0207 (11)	0.0193 (11)	0.0001 (9)	−0.0002 (9)	−0.0021 (9)
C27	0.0202 (11)	0.0162 (10)	0.0196 (11)	0.0031 (9)	0.0027 (9)	−0.0032 (9)
C28	0.0265 (12)	0.0203 (11)	0.0220 (12)	−0.0023 (9)	−0.0013 (9)	0.0028 (9)
S31	0.0139 (3)	0.0201 (3)	0.0273 (3)	−0.0014 (2)	0.0013 (2)	−0.0027 (2)
N31	0.0142 (9)	0.0192 (10)	0.0223 (10)	−0.0040 (8)	0.0016 (7)	−0.0016 (7)
C31	0.0126 (10)	0.0225 (12)	0.0197 (11)	0.0006 (8)	−0.0012 (8)	−0.0020 (9)
C32	0.0203 (11)	0.0259 (12)	0.0261 (12)	−0.0061 (9)	0.0018 (9)	0.0033 (9)
C33	0.0232 (12)	0.0427 (14)	0.0196 (12)	−0.0053 (10)	0.0019 (9)	0.0005 (10)
C34	0.0220 (12)	0.0382 (14)	0.0273 (13)	0.0024 (10)	0.0024 (10)	−0.0084 (11)
C35	0.0282 (12)	0.0217 (12)	0.0340 (13)	0.0042 (10)	0.0022 (10)	−0.0034 (10)
C36	0.0229 (11)	0.0237 (12)	0.0222 (12)	0.0029 (9)	0.0046 (9)	0.0025 (9)
C37	0.0183 (11)	0.0160 (10)	0.0181 (11)	0.0032 (8)	−0.0006 (8)	0.0048 (8)
C38	0.0208 (11)	0.0221 (12)	0.0240 (12)	−0.0023 (9)	0.0016 (9)	−0.0024 (9)
N41	0.0165 (9)	0.0191 (9)	0.0223 (10)	0.0033 (8)	0.0005 (7)	−0.0027 (8)
C41	0.0125 (10)	0.0222 (11)	0.0191 (11)	−0.0004 (8)	0.0029 (8)	−0.0023 (8)
C42	0.0194 (11)	0.0242 (12)	0.0254 (12)	0.0029 (9)	0.0013 (9)	0.0037 (9)
C43	0.0201 (11)	0.0401 (14)	0.0186 (11)	0.0011 (10)	−0.0004 (9)	0.0024 (10)
C44	0.0214 (11)	0.0353 (13)	0.0213 (12)	−0.0058 (10)	0.0028 (9)	−0.0091 (10)
C45	0.0247 (12)	0.0218 (12)	0.0311 (13)	−0.0035 (9)	0.0030 (10)	−0.0025 (10)
C46	0.0185 (11)	0.0250 (12)	0.0194 (11)	−0.0019 (9)	−0.0003 (9)	0.0033 (9)
C47	0.0175 (10)	0.0144 (10)	0.0199 (11)	−0.0007 (8)	0.0039 (8)	0.0020 (8)
C48	0.0183 (11)	0.0251 (12)	0.0261 (12)	−0.0002 (9)	0.0009 (9)	−0.0050 (9)

Geometric parameters (Å, º)

S41—C47	1.682 (2)	C28—H328	0.9800
S11—C17	1.672 (2)	S31—C37	1.675 (2)
N11—C17	1.330 (3)	N31—C37	1.326 (2)
N11—C11	1.431 (3)	N31—C31	1.429 (3)
N11—H11N	0.84 (2)	N31—H31N	0.86 (2)
C11—C16	1.392 (3)	C31—C36	1.387 (3)
C11—C12	1.393 (3)	C31—C32	1.388 (3)
C12—C13	1.385 (3)	C32—C33	1.390 (3)
C12—H12	0.9500	C32—H32	0.9500
C13—C14	1.388 (3)	C33—C34	1.376 (3)
C13—H13	0.9500	C33—H33	0.9500
C14—C15	1.386 (3)	C34—C35	1.387 (3)
C14—H14	0.9500	C34—H34	0.9500
C15—C16	1.384 (3)	C35—C36	1.383 (3)
C15—H15	0.9500	C35—H35	0.9500
C16—H16	0.9500	C36—H36	0.9500
C17—C18	1.503 (3)	C37—C38	1.503 (3)
C18—H118	0.9800	C38—H138	0.9800
C18—H218	0.9800	C38—H238	0.9800
C18—H318	0.9800	C38—H338	0.9800
S21—C27	1.675 (2)	N41—C47	1.329 (2)
N21—C27	1.329 (2)	N41—C41	1.429 (3)
N21—C21	1.432 (2)	N41—H41N	0.87 (2)
N21—H21N	0.85 (2)	C41—C46	1.381 (3)
C21—C22	1.388 (3)	C41—C42	1.391 (3)
C21—C26	1.389 (3)	C42—C43	1.384 (3)
C22—C23	1.392 (3)	C42—H42	0.9500
C22—H22	0.9500	C43—C44	1.384 (3)
C23—C24	1.375 (3)	C43—H43	0.9500
C23—H23	0.9500	C44—C45	1.385 (3)
C24—C25	1.388 (3)	C44—H44	0.9500
C24—H24	0.9500	C45—C46	1.385 (3)
C25—C26	1.386 (3)	C45—H45	0.9500
C25—H25	0.9500	C46—H46	0.9500
C26—H26	0.9500	C47—C48	1.496 (3)
C27—C28	1.506 (3)	C48—H148	0.9800
C28—H128	0.9800	C48—H248	0.9800
C28—H228	0.9800	C48—H348	0.9800
C17—N11—C11	128.83 (18)	C37—N31—C31	128.26 (18)
C17—N11—H11N	115.9 (16)	C37—N31—H31N	116.6 (14)
C11—N11—H11N	115.3 (16)	C31—N31—H31N	115.1 (14)
C16—C11—C12	120.14 (19)	C36—C31—C32	120.39 (19)
C16—C11—N11	121.60 (18)	C36—C31—N31	121.24 (18)
C12—C11—N11	118.16 (18)	C32—C31—N31	118.21 (18)
C13—C12—C11	119.91 (19)	C31—C32—C33	119.3 (2)
C13—C12—H12	120.0	C31—C32—H32	120.4
C11—C12—H12	120.0	C33—C32—H32	120.4
C12—C13—C14	120.0 (2)	C34—C33—C32	120.6 (2)
C12—C13—H13	120.0	C34—C33—H33	119.7
C14—C13—H13	120.0	C32—C33—H33	119.7
C15—C14—C13	119.8 (2)	C33—C34—C35	119.9 (2)
C15—C14—H14	120.1	C33—C34—H34	120.1
C13—C14—H14	120.1	C35—C34—H34	120.1
C16—C15—C14	120.7 (2)	C36—C35—C34	120.3 (2)
C16—C15—H15	119.7	C36—C35—H35	119.9
C14—C15—H15	119.7	C34—C35—H35	119.9
C15—C16—C11	119.38 (19)	C35—C36—C31	119.7 (2)
C15—C16—H16	120.3	C35—C36—H36	120.2
C11—C16—H16	120.3	C31—C36—H36	120.2
N11—C17—C18	114.50 (17)	N31—C37—C38	114.61 (17)
N11—C17—S11	124.67 (16)	N31—C37—S31	124.00 (16)
C18—C17—S11	120.79 (15)	C38—C37—S31	121.39 (15)
C17—C18—H118	109.5	C37—C38—H138	109.5
C17—C18—H218	109.5	C37—C38—H238	109.5
H118—C18—H218	109.5	H138—C38—H238	109.5
C17—C18—H318	109.5	C37—C38—H338	109.5
H118—C18—H318	109.5	H138—C38—H338	109.5
H218—C18—H318	109.5	H238—C38—H338	109.5
C27—N21—C21	128.00 (18)	C47—N41—C41	127.73 (18)
C27—N21—H21N	114.2 (15)	C47—N41—H41N	114.8 (16)
C21—N21—H21N	117.8 (15)	C41—N41—H41N	117.5 (16)
C22—C21—C26	120.63 (19)	C46—C41—C42	120.47 (19)
C22—C21—N21	118.13 (18)	C46—C41—N41	120.84 (18)
C26—C21—N21	121.10 (18)	C42—C41—N41	118.57 (18)
C21—C22—C23	119.2 (2)	C43—C42—C41	119.7 (2)
C21—C22—H22	120.4	C43—C42—H42	120.2
C23—C22—H22	120.4	C41—C42—H42	120.2
C24—C23—C22	120.7 (2)	C42—C43—C44	120.1 (2)
C24—C23—H23	119.6	C42—C43—H43	120.0
C22—C23—H23	119.6	C44—C43—H43	120.0
C23—C24—C25	119.5 (2)	C43—C44—C45	119.9 (2)
C23—C24—H24	120.2	C43—C44—H44	120.0
C25—C24—H24	120.2	C45—C44—H44	120.0
C26—C25—C24	120.8 (2)	C46—C45—C44	120.4 (2)
C26—C25—H25	119.6	C46—C45—H45	119.8
C24—C25—H25	119.6	C44—C45—H45	119.8
C25—C26—C21	119.07 (19)	C41—C46—C45	119.48 (19)
C25—C26—H26	120.5	C41—C46—H46	120.3
C21—C26—H26	120.5	C45—C46—H46	120.3
N21—C27—C28	114.38 (17)	N41—C47—C48	115.11 (17)
N21—C27—S21	124.44 (16)	N41—C47—S41	123.57 (16)
C28—C27—S21	121.15 (15)	C48—C47—S41	121.31 (15)
C27—C28—H128	109.5	C47—C48—H148	109.5
C27—C28—H228	109.5	C47—C48—H248	109.5
H128—C28—H228	109.5	H148—C48—H248	109.5
C27—C28—H328	109.5	C47—C48—H348	109.5
H128—C28—H328	109.5	H148—C48—H348	109.5
H228—C28—H328	109.5	H248—C48—H348	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11N···S21^i	0.84 (2)	2.53 (2)	3.3504 (18)	166 (2)
N21—H21N···S11	0.85 (2)	2.51 (2)	3.3375 (18)	164.0 (19)
N31—H31N···S41	0.86 (2)	2.47 (2)	3.3251 (18)	174.8 (19)
N41—H41N···S31^i	0.87 (2)	2.45 (2)	3.3224 (18)	176 (2)

Symmetry code: (i) x+1, y, z.