Bipodal 1,1'-acyl-3,3,3',3'-tetra­alkyl­bis(thio­urea) ligands with flexible C₃, C₄ and C₆ spacer groups

In the structures of 3,3,3',3'-tetra­ethyl-1,1'-(propane-1,3-diyl­dicarbon­yl)bis­(thio­urea), C₁₅H₂₈N₄O₂S₂, (I), 3,3,3',3'-tetra­ethyl-1,1'-(butane-1,4-diyldicarbon­yl)bis­(thio­urea), C₁₆H₃₀N₄O₂S₂, (II), and 3,3,3',3'-tetra­butyl-1,1'-(hexane-1,6-diyl­di­car­bon­yl)bis­(thio­urea), C₂₆H₅₀N₄O₂S₂, (III), compound (I) displays resonance-assisted hydrogen bonding, (II) exhibits an inversion centre, and both (II) and (III) are characterized by inter­molecular hydrogen bonds between the carbonyl O atoms and thio­amide H atoms, leading to chains of hydrogen-bonded mol­ecules throughout the structures. The accurate structural data for these molecules is expected to assist in molecular modelling and other studies currently in progress.

S1. Comment

N,N-dialkyl-N'-aryl(aroyl)thioureas coordinate to a diverse array of transition metal ions, usually in an S,O-bidentate manner, although several examples of coordination through the S atom and an S,N-donor-atom set have been reported (Koch et al., 2001). In view of the interesting practical applications of metal complexes of this class of ligands, a considerable number of both ligands and metal complexes have been studied, and several have been structurally characterized (Sacht et al., 2000; Hernandez et al., 2005). Potentially `bipodal' derivatives of N,N-dialkyl-N'-aroylthioureas in which two potentially S,O-chelating acylthiourea motifs are linked through a `spacer' R (see scheme) were reported as early as 1965 (Goerdeler & Stadelbauer, 1965). More recently, work on bipodal derivatives based on para-substituted phenyl ring spacers [as in 3,3,3',3'-tetraethyl-1,1'-terephthaloylbis(thiourea) or 3,3,3',3'-tetra-n-butyl-1,1'-terephthaloylbis(thiourea)] has shown that with d⁸ metal ions, such ligands form almost exclusively 3:3 metallamacrocycles of Ni^II (Köhler et al., 1986), Pt^II (Koch et al., 1999) and Pd^II (Koch et al., 2001). In this context, we showed that the corresponding meta-substituted phenyl ligands [3,3,3',3'-tetra-n-ethyl-1,1'-isophthaloylbis(thiourea)] undergo `self-assembly' with d⁸ metal ions to form exclusively the corresponding 2:2 metallamacrocycles, largely as a result of the strong tendency of these ligands to form cis-coordinated metal complexes (Koch et al., 1999). The pyridine adducts of 2:2 and 3:3 nickel(II) complexes of 3,3,3',3'-tetraethyl-1,1'-terephthaloylbis(thiourea) show some interesting host–guest chemistry in the solid state (Hallale et al., 2005). Recently, the corresponding diiodoplatinum(IV) adducts were prepared and characterized after electrochemically induced oxidative addition of I₂ to the corresponding 2:2 and 3:3 Pt^II complexes of 3,3,3',3'-tetraethyl-1,1'-isophthaloylbis(thiourea) and 3,3,3',3'-tetraethyl-1,1'-terephthaloylbis(thiourea) (Westra et al., 2005). A similar bipodal ligand with a 2,6-substituted pyridine ring as spacer and its Ag^I coordination polymer have been described (Schröder et al., 2000). In all these bipodal ligands the spacer moiety was a planar, 'rigid' phenyl or pyridyl ring.

As part of our continuing interest in such bipodal ligands, we have prepared a series of N,N-dialkyl-N'-(acyl)thioureas with flexible C₃, C₄ and C₆ spacers and report here the crystal and molecular structures of 3,3,3',3'-tetraethyl-1,1'-glutaroylbis(thiourea) (I), 3,3,3',3'-tetraethyl-1,1'-adipoylbis(thiourea) (II) and 3,3,3',3'-tetrabutyl-1,1'-suberoylbis(thiourea) (III). König et al.(1987) reported the synthesis of a variety of 3,3,3',3'-tetraalkyl-1,1'-alkanedioylbis(thioureas) and the Ni^II, Cu^II, Pd^II and Pt^II metal complexes of 3,3,3',3'-tetraethyl-1,1'-adipoylbis(thiourea), although no structural characterization was carried out.

In view of the nomenclature and atom-numbering schemes of compounds of this type reported in the literature historically being inconsistent, we here follow an atom-numbering scheme for molecules (I)–(III) to correspond to the bipodal molecules with rigid `spacers' as reported by Westra et al. (2005), as this method offers the most clarity.

Compound (I) crystallizes in the space group P2₁/n and the molecule adopts a conformation such that the two acylthiourea motifs are at an approximate right angle to one another, owing to the flexible nature of the spacer group (Fig. 1). The donor O and S atoms in each acylthiourea unit assume opposing orientations indicated by the O—C(O)—N—C(O)—C(S) and S—C(S)—N—C(S)—C(O) torsion angles (Table 1). Table 1 shows that the N—C bond lengths are all shorter than the average C—N single bond length of 1.472 (5) Å (Allen et al., 1987), but follow the expected order in which the thioamide N1—C12 bond length is relatively the longest, followed by the amide N1—C11 bond; the second thioamide N2—C12 bond is the shortest. This trend is consistent with that generally observed for a variety of related simple N,N-dialkyl-N'-benzoylthioureas (Koch et al., 1995; Dillen et al., 2006).

In the crystal structure, molecules of (I) are linked by two intermolecular hydrogen bonds (Table 2) between the S atom of one molecule and the thioamide H atom of a neighbouring molecule (Fig. 2). The acylthiourea unit consists of a donor–acceptor pair connected by a `resonant π system', evident from the shortening of the amide and thioamide C—N bonds. This leads to one molecule being hydrogen bonded to two others, as shown in Fig. 2, and this type of hydrogen-bond formation represents an example of π-bond cooperativity or resonance-assisted hydrogen bonding (Steiner, 2002). This, to the best of our knowledge, is the first time that hydrogen bonding of this type has been reported for these compounds. Similar observations have been made for the closely related N,N-diethyl-N'-benzoylselenourea (Bruce et al., 2007).

The relative orientations of the acylthiourea units are exchanged, such that, if a plane is defined by C11/C1–C3/C31 along the length of the spacer group, the O atom of one acylthiourea unit is above the plane and the corresponding S atom below, while in the second acylthiourea unit, the O atom is below the plane while the corresponding S atom lies above the plane.

Compound (II) crystallizes in the space group P1, exhibiting an inversion centre located midway between atoms C2 and C2', resulting in only half the molecule appearing in the asymmetric unit. The remainder of the molecule can be generated with the symmetry operator (-x, -y, 1 - z) and the whole molecule is shown in Fig. 3. The C—N bond lengths of (II) are similar to those in (I) in that the C—N bond lengths in the acylthiourea unit are all shorter than the average C—N single bond length of 1.472 (5) Å and are consistent with the trend described previously for (I). It is noteworthy that the molecule of (II) with the C₄ flexible spacer assumes an approximately linear conformation in the solid state, in contrast to that of (I) in which the molecule with the C₃ spacer is significantly `bent'. Moreover, the relative anti orientations of the S and O donor atoms in (I) are not observed in (II), for which the torsion angles O1—C11—N1—C12 [7.1 (4)°] and S1—C12—N1—C11 [45.5 (3)°] are substantially different from the corresponding angles [12.6 (4)° and 125.7 (2)°] in (I). This is most likely due to the involvement of the O-atom donor in the intramolecular hydrogen bond exhibited by (II) (see below).

The intermolecular hydrogen-bonding pattern observed for (II) is quite different to that seen in (I). In (II) the thioamide H atoms (H1 and H1') hydrogen bond to the carbonyl O atoms (O1 and O1') of a neighbouring molecule (Table 4), as shown in Fig. 4, thus precluding the formation of resonance-assisted hydrogen bonding as observed in the crystal structure of (I).

Despite crystallizing in the same space group as (II), the molecule (III) with the C₆ spacer does not exhibit an inversion centre, the whole molecule being contained in the asymmetric unit and shown in Fig. 5. The overall conformation that molecule (III) adopts differs from both (I) and (II); while the C₆ spacer of the molecule remains reasonably linear, the molecule assumes an overall U shape with the dibutyl groups of the terminal thioamide units extending above and below this conformation (Fig. 5). As for the previous compounds, the relative orientations of the S and O donor atoms of the acylthiourea groups on either side of the C₆ spacer differ in that the carbonyl O atom of one acylthiourea residue is situated above the C11/C1–C6/C61 plane, while the other carbonyl O atom is below the plane. In each case, the S atom of the thiocarbonyl group has an anti orientation relative to that of the carbonyl O atom, as indicated by the torsion angles in Table 5. This is reminiscent of (I) and different from (II), which interestingly exhibits similar hydrogen bonding.

Similarly to (I), the C—N bond lengths in each chelate ring are not identical to the corresponding C—N bonds in the second ring; however, they are all shorter than the average single C—N bond length of 1.472 (5) Å, and the trend described for (I) is maintained here. Intermolecular hydrogen bonding (Table 6) between the carbonyl O atom of one molecule and thioamide H atom of a neighbouring molecule is evident, and the molecular arrangement in this compound is similar to that in (II), in that each molecule has two hydrogen bonds to each neighbour on either side of the central molecule, as shown in Fig. 6.

Related literature

For related literature, see: Allen et al. (1987); Bruce et al. (2007); Dillen et al. (2006); Goerdeler & Stadelbauer (1965); Hallale et al. (2005); Hernandez et al. (2005); Köhler et al. (1986); König et al. (1987); Koch et al. (1995, 1999, 2001); Sacht et al. (2000); Schröder et al. (2000); Steiner (2002); Westra et al. (2005).

S2. Experimental

All reactions were carried out under an inert N₂ atmosphere. All reagents and solvents used were commercially available and used without further purification, except for the acetone which was distilled prior to use. One molar equivalent of the appropriate acid dichloride in acetone was added dropwise to two molar equivalents of KSCN in acetone. The mixture was heated to reflux for 45 min, after which it was cooled to room temperature and the dropwise addition of two molar equivalents of the appropriate secondary amine in acetone followed. The mixture was heated to reflux for a further 45 min and cooled to room temperature followed by the addition of water. Slow evaporation of the acetone afforded a crystalline product and recrystallization from acetone/water solutions yielded crystals suitable for analysis.

Analysis for (I) (yield 53%, m.p. 392.6–393.4 K). ¹H NMR (400 MHz, CDCl₃, p.p.m.): 9.58 (s, 2H, –NH–), 3.96 [br s, 4H, –N(CH₂CH₃)₂], 3.61 [br s, 4H, –N(CH₂CH₃)₂], 2.39 (t, 4H, –CH₂—CH₂—CH₂–), 2.19 (m, 2H, –CH₂—CH₂—CH₂–), 1.30 [m, 12H, –N(CH₂CH₃)₂]. ¹³C NMR (100 MHz, CDCl₃, p.p.m.): 179.4 (CS), 170.6 (CO), 47.6 [–N(CH₂CH₃)₂], 47.3 [–N(CH₂CH₃)₂], 34.7 [CH₂—CH₂—CH₂], 24.0 (–CH₂—CH₂—CH₂–), 13.4 [–N(CH₂CH₃)₂], 11,2 [–N(CH₂CH₃)₂].

Compound (II) (yield 58%, m.p. 394.7–395.5 K). ¹H NMR (400 MHz, CDCl₃, p.p.m.): 7.96 (s, 2H, –NH–), 3.94 [br s, 4H, –N(CH₂CH₃)₂], 3.53 [br s, 4H, –N(CH₂CH₃)₂], 2.40 [t, 4H, –CH₂—(CH₂)₂—CH₂–], 1.74 [q, 4H, –CH₂—(CH₂)₂—CH₂–], 1.29 [s, 12H, –N(CH₂CH₃)₂]. ¹³C NMR (100 MHz, CDCl₃, p.p.m.): 178.9 (CS), 169.8 (CO), 47.6 [N(CH₂CH₃)₂], 36.3 [CH₂—(CH₂)₂—CH₂], 24.2 [CH₂—(CH₂)₂—CH₂], 13.2 [N(CH₂CH₃)₂], 11.6 [N(CH₂CH₃)₂].

Compound (III) (yield 76.1%, m.p. 353.2–355.2 K. ¹H NMR (400 MHz, CDCl₃, p.p.m.): 8.82 (s, 2H, –NH–), 3.88 [br t, 4H, –N(CH₂CH₂CH₂CH₃)₂], 3.44 [br t, 4H, –N(CH₂CH₂CH₂CH₃)₂], 2.34 [t, 4H, –CH₂—(CH₂)₄—CH₂–],1.67 [m, 12H, –CH₂—(CH₂)₄—CH₂– and –N(CH₂CH₂CH₂CH₃)₂], 1.36 [m, 12H, –CH₂—(CH₂)₄—CH₂– and –N(CH₂CH₂CH₂CH₃)₂], 0.92 [m, 12H, –N(CH₂CH₂CH₂CH₃)₂]. ¹³C NMR (100 MHz, CDCl₃, p.p.m.): 179.5 (CS), 169.9 (CO), 53.1 [–N(CH₂CH₂CH₂CH₃)₂], 52.9 [–N(CH₂CH₂CH₂CH₃)₂], 36.1 [–CH₂—(CH₂)₄—CH₂–], 30.0 [–N(CH₂CH₂CH₂CH₃)_2], 28.4 [–N(CH₂CH₂CH₂CH₃)_2], 28.0 [–CH₂—(CH₂)₄—CH₂–), 24.8 [–CH₂—(CH₂)₄—CH₂–), 20.0 [–N(CH₂CH₂CH₂CH₃)₂], 13.8 [–N(CH₂CH₂CH₂CH₃)₂],13.7 [–N(CH₂CH₂CH₂CH₃)₂].

S3. Refinement

H atoms involved in hydrogen bonding were located from a difference electron-density map and all other H atoms were placed in geometrically calculated positions. N-bound H atoms in (I) and (III) were refined freely (refined distances are given in Tables 2, 4 and 6). All other H atoms were treated as riding [C—H = 0.99 Å (for –CH₂), 0.98 Å (for –CH₃), N—H = 0.88 Å, and U_iso (H) = 1.2U_eq (C,N) for –CH₂ and amine or U_iso(H) = 1.5U_eq(C) for –CH₃]. Please check changes to text.

Computing details

For all compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Version 2.0; Barbour, 2001); software used to prepare material for publication: X-SEED (Version 2.0; Barbour, 2001).

Figures

	Fig. 1. The molecular structure of (I), with the atomic numbering shown. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the structure of (I), showing the intermolecular N—H···S hydrogen bonds (dashed lines). Displacement ellipsoids are drawn at the 50% probability level. H atoms, except H1 and H3, have been omitted for clarity. [Symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z.]
	Fig. 3. The molecular structure of (II), with the atomic numbering shown. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x, -y, -z + 1.]
	Fig. 4. The structure of (II), showing intermolecular N—H···O hydrogen bonds (dashed lines). Displacement ellipsoids are drawn at the 50% probability level. H atoms, except H1, have been omitted for clarity. [Symmetry codes: (i) -x, -y, -z + 1; (ii) x + 1, y, z; (iii) -x + 1, -y, -z + 1; (iv) x - 1, y, z; (v) -x - 1, -y, 1 - z.]
	Fig. 5. The molecular structure of (III), with the atomic numbering shown. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 6. The structure of (III), showing intermolecular N—H···O hydrogen bonds (dashed lines). Displacement ellipsoids are drawn at the 50% probability level. H atoms, except H1, have been omitted for clarity. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 2, -y + 1, -z.]

(I) 3,3,3',3'-Tetraethyl-1,1'-(propane-1,3-diyldicarbonyl)bis(thiourea)

Crystal data

C15H28N4O2S2	F(000) = 776
Mr = 360.53	Dx = 1.277 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1566 reflections
a = 7.1475 (18) Å	θ = 2.3–23.0°
b = 27.999 (7) Å	µ = 0.30 mm^−1
c = 9.387 (2) Å	T = 100 K
β = 93.026 (5)°	Block, colourless
V = 1875.9 (8) Å^3	0.22 × 0.21 × 0.18 mm
Z = 4

Data collection

Bruker APEX I CCD area-detector diffractometer	3685 independent reflections
Radiation source: fine-focus sealed tube	2845 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
\w scans	θmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
Tmin = 0.937, Tmax = 0.948	k = −34→32
10628 measured reflections	l = −11→11

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[\s^2^(Fo^2^) + (0.0666P)^2^] where P = (Fo^2^ + 2Fc^2^)/3
3685 reflections	(Δ/σ)max = 0.011
220 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

Special details

Experimental. Proton chemical shifts are quoted relative to the residual CHCl3 solvent resonance at 7.26 p.p.m.., and 13 C chemical shifts relative to the CDCl3 triplet at 77.0 p.p.m.. (centre peak). J values are given in Hz.

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
S1	0.29349 (9)	0.86228 (3)	0.69586 (7)	0.0248 (2)
O1	0.6668 (2)	0.97690 (6)	0.60062 (17)	0.0180 (4)
N1	0.5780 (3)	0.89967 (8)	0.5646 (2)	0.0174 (5)
C1	0.6717 (3)	0.94653 (9)	0.3616 (3)	0.0173 (5)
H1A	0.5785	0.9685	0.3151	0.021*
H1B	0.6544	0.9146	0.3176	0.021*
H1	0.545 (4)	0.8809 (10)	0.501 (3)	0.023 (8)*
S2	1.48544 (8)	0.82024 (2)	0.29718 (7)	0.01825 (18)
O2	0.9727 (2)	0.88464 (6)	0.17027 (18)	0.0219 (4)
N2	0.6099 (3)	0.89814 (7)	0.8145 (2)	0.0148 (4)
C2	0.8686 (3)	0.96459 (9)	0.3373 (3)	0.0185 (6)
H2A	0.8794	0.9708	0.2342	0.022*
H2B	0.8883	0.9953	0.3882	0.022*
N3	1.1458 (3)	0.85024 (8)	0.3537 (2)	0.0177 (5)
C3	1.0215 (3)	0.92982 (9)	0.3877 (3)	0.0188 (6)
H3A	1.1430	0.9469	0.3937	0.023*
H3B	0.9958	0.9187	0.4848	0.023*
H3	1.195 (4)	0.8563 (9)	0.426 (3)	0.012 (7)*
N4	1.1578 (3)	0.78830 (7)	0.1870 (2)	0.0174 (5)
C11	0.6392 (3)	0.94339 (9)	0.5200 (3)	0.0149 (5)
C12	0.5056 (3)	0.88878 (9)	0.6977 (3)	0.0171 (6)
C13	0.5350 (3)	0.88874 (9)	0.9555 (3)	0.0185 (6)
H13A	0.6409	0.8855	1.0272	0.022*
H13B	0.4664	0.8580	0.9518	0.022*
C14	0.4047 (4)	0.92781 (10)	1.0027 (3)	0.0270 (6)
H14A	0.3022	0.9321	0.9302	0.041*
H14B	0.4746	0.9578	1.0147	0.041*
H14C	0.3531	0.9188	1.0935	0.041*
C15	0.8116 (3)	0.91021 (9)	0.8186 (3)	0.0185 (6)
H15A	0.8527	0.9124	0.7197	0.022*
H15B	0.8837	0.8842	0.8673	0.022*
C16	0.8551 (4)	0.95695 (9)	0.8952 (3)	0.0234 (6)
H16A	0.8114	0.9553	0.9923	0.035*
H16B	0.7915	0.9832	0.8434	0.035*
H16C	0.9907	0.9625	0.8994	0.035*
C31	1.0378 (3)	0.88675 (9)	0.2915 (3)	0.0161 (5)
C32	1.2506 (3)	0.81819 (9)	0.2746 (3)	0.0163 (5)
C33	0.9561 (3)	0.77708 (10)	0.1956 (3)	0.0226 (6)
H33A	0.9015	0.7991	0.2647	0.027*
H33B	0.9437	0.7442	0.2326	0.027*
C34	0.8459 (4)	0.78091 (11)	0.0562 (3)	0.0307 (7)
H34A	0.8818	0.7550	−0.0069	0.046*
H34B	0.8718	0.8117	0.0118	0.046*
H34C	0.7119	0.7786	0.0724	0.046*
C35	1.2618 (4)	0.75827 (9)	0.0876 (3)	0.0222 (6)
H35A	1.3725	0.7762	0.0577	0.027*
H35B	1.1803	0.7519	0.0012	0.027*
C36	1.3261 (4)	0.71136 (10)	0.1520 (3)	0.0313 (7)
H36A	1.2187	0.6945	0.1889	0.047*
H36B	1.4196	0.7173	0.2302	0.047*
H36C	1.3820	0.6918	0.0789	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0203 (4)	0.0358 (4)	0.0179 (4)	−0.0092 (3)	−0.0014 (3)	0.0001 (3)
O1	0.0228 (10)	0.0151 (9)	0.0156 (9)	0.0017 (7)	−0.0022 (7)	−0.0028 (7)
N1	0.0210 (12)	0.0170 (11)	0.0140 (11)	−0.0024 (9)	−0.0014 (9)	−0.0029 (9)
C1	0.0199 (13)	0.0177 (13)	0.0140 (13)	0.0044 (10)	−0.0025 (10)	−0.0002 (10)
S2	0.0152 (3)	0.0186 (4)	0.0208 (4)	−0.0010 (2)	−0.0010 (3)	−0.0031 (3)
O2	0.0267 (10)	0.0221 (10)	0.0163 (10)	0.0055 (8)	−0.0046 (8)	−0.0047 (8)
N2	0.0149 (10)	0.0159 (11)	0.0135 (10)	0.0003 (8)	−0.0004 (8)	0.0006 (8)
C2	0.0261 (14)	0.0139 (13)	0.0156 (13)	−0.0024 (11)	0.0028 (11)	−0.0022 (10)
N3	0.0183 (12)	0.0223 (13)	0.0122 (12)	0.0004 (9)	−0.0035 (10)	−0.0040 (9)
C3	0.0175 (13)	0.0205 (14)	0.0188 (13)	−0.0004 (11)	0.0031 (10)	−0.0057 (11)
N4	0.0142 (11)	0.0183 (11)	0.0198 (12)	0.0001 (9)	0.0008 (9)	−0.0019 (9)
C11	0.0116 (12)	0.0164 (13)	0.0163 (13)	0.0032 (10)	−0.0014 (10)	0.0014 (10)
C12	0.0175 (13)	0.0156 (13)	0.0183 (13)	0.0034 (10)	0.0011 (10)	−0.0005 (10)
C13	0.0195 (14)	0.0213 (14)	0.0146 (13)	−0.0024 (11)	−0.0001 (10)	0.0020 (11)
C14	0.0269 (15)	0.0311 (16)	0.0236 (15)	0.0049 (12)	0.0064 (12)	0.0009 (12)
C15	0.0145 (13)	0.0215 (14)	0.0192 (14)	0.0005 (10)	−0.0015 (10)	0.0015 (11)
C16	0.0227 (14)	0.0265 (15)	0.0204 (14)	−0.0087 (11)	−0.0044 (11)	0.0023 (11)
C31	0.0135 (12)	0.0175 (13)	0.0176 (13)	−0.0009 (10)	0.0019 (10)	0.0007 (10)
C32	0.0211 (13)	0.0152 (13)	0.0125 (12)	0.0019 (10)	0.0010 (10)	0.0048 (10)
C33	0.0135 (13)	0.0251 (15)	0.0292 (15)	−0.0037 (11)	0.0015 (11)	−0.0069 (12)
C34	0.0203 (15)	0.0368 (18)	0.0348 (17)	−0.0002 (12)	−0.0013 (12)	−0.0120 (14)
C35	0.0175 (14)	0.0248 (15)	0.0241 (15)	0.0002 (11)	0.0005 (11)	−0.0100 (12)
C36	0.0297 (16)	0.0215 (16)	0.0431 (19)	0.0007 (12)	0.0059 (13)	−0.0061 (13)

Geometric parameters (Å, º)

S1—C12	1.687 (3)	N4—C35	1.485 (3)
O1—C11	1.215 (3)	C13—C14	1.518 (3)
N1—C11	1.373 (3)	C13—H13A	0.9900
N1—C12	1.411 (3)	C13—H13B	0.9900
N1—H1	0.82 (3)	C14—H14A	0.9800
C1—C11	1.520 (3)	C14—H14B	0.9800
C1—C2	1.524 (3)	C14—H14C	0.9800
C1—H1A	0.9900	C15—C16	1.518 (4)
C1—H1B	0.9900	C15—H15A	0.9900
S2—C32	1.682 (3)	C15—H15B	0.9900
O2—C31	1.208 (3)	C16—H16A	0.9800
N2—C12	1.319 (3)	C16—H16B	0.9800
N2—C13	1.477 (3)	C16—H16C	0.9800
N2—C15	1.480 (3)	C33—C34	1.495 (4)
C2—C3	1.520 (3)	C33—H33A	0.9900
C2—H2A	0.9900	C33—H33B	0.9900
C2—H2B	0.9900	C34—H34A	0.9800
N3—C31	1.390 (3)	C34—H34B	0.9800
N3—C32	1.406 (3)	C34—H34C	0.9800
N3—H3	0.77 (3)	C35—C36	1.508 (4)
C3—C31	1.515 (3)	C35—H35A	0.9900
C3—H3A	0.9900	C35—H35B	0.9900
C3—H3B	0.9900	C36—H36A	0.9800
N4—C32	1.326 (3)	C36—H36B	0.9800
N4—C33	1.482 (3)	C36—H36C	0.9800
C11—N1—C12	126.9 (2)	C13—C14—H14C	109.5
C11—N1—H1	116 (2)	H14A—C14—H14C	109.5
C12—N1—H1	114 (2)	H14B—C14—H14C	109.5
C11—C1—C2	110.83 (19)	N2—C15—C16	112.6 (2)
C11—C1—H1A	109.5	N2—C15—H15A	109.1
C2—C1—H1A	109.5	C16—C15—H15A	109.1
C11—C1—H1B	109.5	N2—C15—H15B	109.1
C2—C1—H1B	109.5	C16—C15—H15B	109.1
H1A—C1—H1B	108.1	H15A—C15—H15B	107.8
C12—N2—C13	119.6 (2)	C15—C16—H16A	109.5
C12—N2—C15	125.0 (2)	C15—C16—H16B	109.5
C13—N2—C15	114.59 (19)	H16A—C16—H16B	109.5
C3—C2—C1	113.3 (2)	C15—C16—H16C	109.5
C3—C2—H2A	108.9	H16A—C16—H16C	109.5
C1—C2—H2A	108.9	H16B—C16—H16C	109.5
C3—C2—H2B	108.9	O2—C31—N3	122.5 (2)
C1—C2—H2B	108.9	O2—C31—C3	124.2 (2)
H2A—C2—H2B	107.7	N3—C31—C3	113.2 (2)
C31—N3—C32	123.1 (2)	N4—C32—N3	117.9 (2)
C31—N3—H3	115 (2)	N4—C32—S2	124.26 (19)
C32—N3—H3	112 (2)	N3—C32—S2	117.87 (19)
C31—C3—C2	113.7 (2)	N4—C33—C34	114.0 (2)
C31—C3—H3A	108.8	N4—C33—H33A	108.8
C2—C3—H3A	108.8	C34—C33—H33A	108.8
C31—C3—H3B	108.8	N4—C33—H33B	108.8
C2—C3—H3B	108.8	C34—C33—H33B	108.8
H3A—C3—H3B	107.7	H33A—C33—H33B	107.7
C32—N4—C33	123.8 (2)	C33—C34—H34A	109.5
C32—N4—C35	119.7 (2)	C33—C34—H34B	109.5
C33—N4—C35	115.80 (19)	H34A—C34—H34B	109.5
O1—C11—N1	122.9 (2)	C33—C34—H34C	109.5
O1—C11—C1	122.5 (2)	H34A—C34—H34C	109.5
N1—C11—C1	114.7 (2)	H34B—C34—H34C	109.5
N2—C12—N1	118.4 (2)	N4—C35—C36	113.2 (2)
N2—C12—S1	124.31 (19)	N4—C35—H35A	108.9
N1—C12—S1	117.21 (18)	C36—C35—H35A	108.9
N2—C13—C14	112.9 (2)	N4—C35—H35B	108.9
N2—C13—H13A	109.0	C36—C35—H35B	108.9
C14—C13—H13A	109.0	H35A—C35—H35B	107.8
N2—C13—H13B	109.0	C35—C36—H36A	109.5
C14—C13—H13B	109.0	C35—C36—H36B	109.5
H13A—C13—H13B	107.8	H36A—C36—H36B	109.5
C13—C14—H14A	109.5	C35—C36—H36C	109.5
C13—C14—H14B	109.5	H36A—C36—H36C	109.5
H14A—C14—H14B	109.5	H36B—C36—H36C	109.5
C11—C1—C2—C3	66.8 (3)	C13—N2—C15—C16	−64.9 (3)
C1—C2—C3—C31	73.9 (3)	C32—N3—C31—O2	26.3 (4)
C12—N1—C11—O1	12.6 (4)	C32—N3—C31—C3	−150.2 (2)
C12—N1—C11—C1	−167.9 (2)	C2—C3—C31—O2	17.5 (4)
C2—C1—C11—O1	53.0 (3)	C2—C3—C31—N3	−166.1 (2)
C2—C1—C11—N1	−126.5 (2)	C33—N4—C32—N3	−17.6 (3)
C13—N2—C12—N1	177.8 (2)	C35—N4—C32—N3	172.0 (2)
C15—N2—C12—N1	−12.9 (4)	C33—N4—C32—S2	162.39 (19)
C13—N2—C12—S1	−5.0 (3)	C35—N4—C32—S2	−8.0 (3)
C15—N2—C12—S1	164.31 (19)	C31—N3—C32—N4	−66.1 (3)
C11—N1—C12—N2	−56.9 (3)	C31—N3—C32—S2	113.9 (2)
C11—N1—C12—S1	125.7 (2)	C32—N4—C33—C34	130.6 (3)
C12—N2—C13—C14	−80.3 (3)	C35—N4—C33—C34	−58.7 (3)
C15—N2—C13—C14	109.4 (2)	C32—N4—C35—C36	88.1 (3)
C12—N2—C15—C16	125.3 (3)	C33—N4—C35—C36	−83.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2^i	0.82 (3)	2.58 (3)	3.393 (2)	173 (3)
N3—H3···S1^ii	0.77 (3)	2.60 (3)	3.344 (2)	165 (2)

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

(II) 3,3,3',3'-tetraethyl-1,1'-(butane-1,4-diyldicarbonyl)bis(thiourea)

Crystal data

C16H30N4O2S2	Z = 1
Mr = 374.56	F(000) = 202
Triclinic, P1	Dx = 1.304 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8287 (9) Å	Cell parameters from 1762 reflections
b = 6.3977 (12) Å	θ = 2.6–27.1°
c = 15.661 (3) Å	µ = 0.30 mm^−1
α = 85.532 (3)°	T = 100 K
β = 86.985 (3)°	Needle, colourless
γ = 81.894 (3)°	0.47 × 0.21 × 0.05 mm
V = 477.09 (16) Å^3

Data collection

Bruker APEX I CCD area-detector diffractometer	1847 independent reflections
Radiation source: fine-focus sealed tube	1611 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
\w scans	θmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −5→5
Tmin = 0.874, Tmax = 0.985	k = −7→7
4902 measured reflections	l = −19→19

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.156	H-atom parameters constrained
S = 1.16	w = 1/[\s^2^(Fo^2^) + (0.0857P)^2^] where P = (Fo^2^ + 2Fc^2^)/3
1847 reflections	(Δ/σ)max = 0.010
111 parameters	Δρmax = 0.90 e Å^−3
0 restraints	Δρmin = −0.30 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
S1	0.11309 (15)	0.28285 (11)	0.17784 (4)	0.0182 (3)
O1	0.1802 (4)	0.3544 (3)	0.37327 (12)	0.0195 (5)
N1	−0.2414 (5)	0.3744 (3)	0.31216 (14)	0.0135 (5)
H1	−0.4206	0.3699	0.3243	0.016*
C1	−0.2095 (6)	0.2747 (4)	0.46408 (17)	0.0168 (6)
H1A	−0.3852	0.2192	0.4538	0.020*
H1B	−0.2590	0.4030	0.4962	0.020*
N2	−0.3359 (5)	0.5793 (3)	0.18682 (14)	0.0132 (5)
C2	−0.0228 (6)	0.1082 (4)	0.51824 (17)	0.0152 (6)
H2A	0.1612	0.1571	0.5227	0.018*
H2B	−0.1089	0.0946	0.5768	0.018*
C11	−0.0684 (6)	0.3347 (4)	0.37849 (17)	0.0137 (6)
C12	−0.1625 (6)	0.4225 (4)	0.22492 (17)	0.0134 (6)
C13	−0.5374 (6)	0.7262 (4)	0.23549 (17)	0.0154 (6)
H13A	−0.6542	0.6433	0.2750	0.018*
H13B	−0.6628	0.8154	0.1950	0.018*
C14	−0.3930 (6)	0.8680 (4)	0.28672 (18)	0.0193 (6)
H14A	−0.2842	0.7814	0.3310	0.029*
H14B	−0.5339	0.9704	0.3138	0.029*
H14C	−0.2676	0.9436	0.2484	0.029*
C15	−0.3247 (6)	0.6223 (5)	0.09346 (17)	0.0190 (6)
H15A	−0.5162	0.6331	0.0724	0.023*
H15B	−0.2090	0.5019	0.0671	0.023*
C16	−0.2042 (7)	0.8243 (5)	0.06495 (19)	0.0260 (7)
H16A	−0.3239	0.9454	0.0880	0.039*
H16B	−0.1955	0.8424	0.0022	0.039*
H16C	−0.0153	0.8156	0.0862	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0184 (4)	0.0168 (4)	0.0183 (4)	0.0005 (3)	0.0031 (3)	−0.0027 (3)
O1	0.0126 (11)	0.0283 (12)	0.0174 (11)	−0.0050 (8)	−0.0009 (8)	0.0035 (8)
N1	0.0096 (11)	0.0143 (12)	0.0160 (12)	−0.0017 (9)	0.0012 (9)	0.0015 (9)
C1	0.0131 (15)	0.0200 (15)	0.0161 (14)	−0.0002 (11)	0.0005 (11)	0.0027 (11)
N2	0.0155 (12)	0.0117 (11)	0.0122 (11)	−0.0016 (9)	0.0008 (9)	−0.0016 (9)
C2	0.0135 (14)	0.0206 (15)	0.0112 (13)	−0.0024 (11)	−0.0002 (10)	0.0016 (11)
C11	0.0150 (15)	0.0113 (13)	0.0139 (14)	0.0006 (11)	−0.0007 (11)	−0.0003 (10)
C12	0.0127 (14)	0.0128 (13)	0.0162 (14)	−0.0068 (10)	−0.0013 (11)	−0.0003 (11)
C13	0.0125 (14)	0.0160 (14)	0.0170 (14)	−0.0005 (11)	0.0003 (11)	−0.0015 (11)
C14	0.0224 (16)	0.0172 (14)	0.0185 (15)	−0.0009 (12)	−0.0005 (12)	−0.0048 (11)
C15	0.0241 (16)	0.0219 (15)	0.0109 (14)	−0.0020 (12)	−0.0031 (11)	−0.0010 (11)
C16	0.0313 (19)	0.0316 (18)	0.0155 (15)	−0.0090 (14)	−0.0020 (13)	0.0049 (13)

Geometric parameters (Å, º)

S1—C12	1.666 (3)	C2—H2B	0.9900
O1—C11	1.223 (3)	C13—C14	1.517 (4)
N1—C11	1.353 (3)	C13—H13A	0.9900
N1—C12	1.421 (3)	C13—H13B	0.9900
N1—H1	0.8800	C14—H14A	0.9800
C1—C11	1.518 (4)	C14—H14B	0.9800
C1—C2	1.528 (4)	C14—H14C	0.9800
C1—H1A	0.9900	C15—C16	1.517 (4)
C1—H1B	0.9900	C15—H15A	0.9900
N2—C12	1.336 (4)	C15—H15B	0.9900
N2—C15	1.466 (3)	C16—H16A	0.9800
N2—C13	1.479 (3)	C16—H16B	0.9800
C2—C2^i	1.522 (5)	C16—H16C	0.9800
C2—H2A	0.9900
C11—N1—C12	126.5 (2)	N2—C13—C14	112.3 (2)
C11—N1—H1	116.7	N2—C13—H13A	109.1
C12—N1—H1	116.7	C14—C13—H13A	109.1
C11—C1—C2	112.3 (2)	N2—C13—H13B	109.1
C11—C1—H1A	109.1	C14—C13—H13B	109.1
C2—C1—H1A	109.1	H13A—C13—H13B	107.9
C11—C1—H1B	109.1	C13—C14—H14A	109.5
C2—C1—H1B	109.1	C13—C14—H14B	109.5
H1A—C1—H1B	107.9	H14A—C14—H14B	109.5
C12—N2—C15	121.2 (2)	C13—C14—H14C	109.5
C12—N2—C13	122.7 (2)	H14A—C14—H14C	109.5
C15—N2—C13	116.1 (2)	H14B—C14—H14C	109.5
C2^i—C2—C1	113.2 (3)	N2—C15—C16	113.0 (2)
C2^i—C2—H2A	108.9	N2—C15—H15A	109.0
C1—C2—H2A	108.9	C16—C15—H15A	109.0
C2^i—C2—H2B	108.9	N2—C15—H15B	109.0
C1—C2—H2B	108.9	C16—C15—H15B	109.0
H2A—C2—H2B	107.7	H15A—C15—H15B	107.8
O1—C11—N1	124.3 (2)	C15—C16—H16A	109.5
O1—C11—C1	120.8 (2)	C15—C16—H16B	109.5
N1—C11—C1	114.9 (2)	H16A—C16—H16B	109.5
N2—C12—N1	113.3 (2)	C15—C16—H16C	109.5
N2—C12—S1	125.8 (2)	H16A—C16—H16C	109.5
N1—C12—S1	120.89 (19)	H16B—C16—H16C	109.5
C11—C1—C2—C2^i	−69.1 (4)	C13—N2—C12—S1	−166.40 (19)
C12—N1—C11—O1	7.1 (4)	C11—N1—C12—N2	−137.2 (3)
C12—N1—C11—C1	−176.4 (2)	C11—N1—C12—S1	45.5 (3)
C2—C1—C11—O1	−39.7 (3)	C12—N2—C13—C14	67.1 (3)
C2—C1—C11—N1	143.7 (2)	C15—N2—C13—C14	−109.5 (3)
C15—N2—C12—N1	−167.2 (2)	C12—N2—C15—C16	−108.3 (3)
C13—N2—C12—N1	16.4 (3)	C13—N2—C15—C16	68.4 (3)
C15—N2—C12—S1	10.0 (4)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^ii	0.88	2.05	2.921 (3)	171

Symmetry code: (ii) x−1, y, z.

(III) 3,3,3',3'-tetrabutyl-1,1'-(hexane-1,6–diyldicarbonyl)bis(thiourea),

Crystal data

C26H50N4O2S2	Z = 2
Mr = 514.82	F(000) = 564
Triclinic, P1	Dx = 1.160 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3206 (15) Å	Cell parameters from 1708 reflections
b = 10.6717 (17) Å	θ = 2.2–24.6°
c = 15.537 (2) Å	µ = 0.21 mm^−1
α = 105.164 (3)°	T = 100 K
β = 97.767 (3)°	Plate, colourless
γ = 92.111 (3)°	0.41 × 0.37 × 0.05 mm
V = 1473.7 (4) Å^3

Data collection

Bruker APEX I CCD area-detector diffractometer	5709 independent reflections
Radiation source: fine-focus sealed tube	3751 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
\w scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→11
Tmin = 0.961, Tmax = 0.990	k = −13→13
10961 measured reflections	l = −19→19

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	w = 1/[\s^2^(Fo^2^) + (0.0094P)^2^] where P = (Fo^2^ + 2Fc^2^)/3
5709 reflections	(Δ/σ)max = 0.002
319 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.28 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
S1	0.97260 (7)	0.28605 (6)	−0.37644 (4)	0.01970 (17)
O1	0.65384 (18)	0.48298 (15)	−0.24412 (11)	0.0170 (4)
N1	0.8933 (2)	0.4434 (2)	−0.23178 (14)	0.0150 (5)
C1	0.8264 (3)	0.6587 (2)	−0.15792 (15)	0.0159 (6)
H1A	0.7630	0.7208	−0.1784	0.019*
H1B	0.9275	0.6825	−0.1641	0.019*
H1	0.973 (3)	0.483 (2)	−0.2247 (16)	0.024 (8)*
S2	0.52714 (7)	0.15048 (6)	0.21415 (4)	0.01873 (17)
O2	0.84460 (17)	0.40659 (15)	0.21968 (10)	0.0177 (4)
N2	0.7861 (2)	0.23140 (19)	−0.27240 (13)	0.0161 (5)
C2	0.8167 (3)	0.6677 (2)	−0.05852 (16)	0.0186 (6)
H2A	0.8773	0.6026	−0.0395	0.022*
H2B	0.8572	0.7550	−0.0211	0.022*
N3	0.6214 (2)	0.40051 (19)	0.26145 (13)	0.0133 (5)
C3	0.6622 (3)	0.6448 (2)	−0.04072 (15)	0.0189 (6)
H3A	0.6007	0.7065	−0.0634	0.023*
H3B	0.6241	0.5556	−0.0758	0.023*
H3	0.535 (3)	0.417 (2)	0.2467 (15)	0.020 (7)*
N4	0.7269 (2)	0.27971 (18)	0.35380 (12)	0.0129 (5)
C4	0.6475 (3)	0.6605 (2)	0.05798 (15)	0.0183 (6)
H4A	0.6962	0.7455	0.0943	0.022*
H4B	0.5433	0.6619	0.0643	0.022*
C5	0.7114 (3)	0.5541 (2)	0.09602 (15)	0.0175 (6)
H5A	0.8168	0.5553	0.0929	0.021*
H5B	0.6659	0.4685	0.0585	0.021*
C6	0.6882 (3)	0.5702 (2)	0.19342 (15)	0.0142 (6)
H6A	0.7487	0.6474	0.2327	0.017*
H6B	0.5852	0.5856	0.1987	0.017*
C11	0.7806 (3)	0.5230 (2)	−0.21573 (16)	0.0148 (6)
C12	0.8754 (3)	0.3173 (2)	−0.29128 (16)	0.0146 (6)
C13	0.7389 (3)	0.1060 (2)	−0.33921 (16)	0.0197 (6)
H13A	0.7799	0.0347	−0.3162	0.024*
H13B	0.7774	0.1045	−0.3958	0.024*
C14	0.5742 (3)	0.0825 (2)	−0.35937 (16)	0.0190 (6)
H14A	0.5486	−0.0036	−0.4034	0.023*
H14B	0.5369	0.0796	−0.3032	0.023*
C15	0.4990 (3)	0.1850 (2)	−0.39667 (17)	0.0207 (6)
H15A	0.5343	0.1871	−0.4536	0.025*
H15B	0.5250	0.2715	−0.3532	0.025*
C16	0.3349 (3)	0.1593 (2)	−0.41452 (17)	0.0240 (7)
H16A	0.3083	0.0762	−0.4603	0.036*
H16B	0.2910	0.2296	−0.4361	0.036*
H16C	0.2995	0.1555	−0.3586	0.036*
C17	0.7336 (3)	0.2505 (2)	−0.18479 (16)	0.0184 (6)
H17A	0.6269	0.2546	−0.1939	0.022*
H17B	0.7768	0.3348	−0.1440	0.022*
C18	0.7713 (3)	0.1423 (2)	−0.14014 (16)	0.0206 (6)
H18A	0.7214	0.0589	−0.1785	0.025*
H18B	0.8772	0.1334	−0.1353	0.025*
C19	0.7270 (3)	0.1691 (3)	−0.04664 (17)	0.0320 (8)
H19A	0.6208	0.1767	−0.0519	0.038*
H19B	0.7753	0.2535	−0.0089	0.038*
C20	0.7660 (3)	0.0634 (3)	0.00020 (18)	0.0374 (8)
H20A	0.7185	−0.0205	−0.0367	0.056*
H20B	0.7332	0.0847	0.0593	0.056*
H20C	0.8715	0.0581	0.0081	0.056*
C61	0.7263 (3)	0.4529 (2)	0.22522 (15)	0.0141 (6)
C62	0.6321 (2)	0.2780 (2)	0.28123 (15)	0.0129 (6)
C63	0.7990 (3)	0.4011 (2)	0.41696 (15)	0.0156 (6)
H63A	0.8335	0.4582	0.3818	0.019*
H63B	0.8850	0.3795	0.4537	0.019*
C64	0.7005 (3)	0.4747 (2)	0.47937 (16)	0.0164 (6)
H64A	0.6579	0.4157	0.5104	0.020*
H64B	0.6201	0.5055	0.4436	0.020*
C65	0.7845 (3)	0.5904 (2)	0.54892 (16)	0.0179 (6)
H65A	0.8385	0.6418	0.5174	0.022*
H65B	0.8566	0.5579	0.5892	0.022*
C66	0.6890 (3)	0.6795 (2)	0.60614 (16)	0.0204 (6)
H66A	0.6199	0.7152	0.5671	0.031*
H66B	0.7499	0.7510	0.6500	0.031*
H66C	0.6357	0.6297	0.6381	0.031*
C67	0.7603 (3)	0.1598 (2)	0.37981 (16)	0.0179 (6)
H67A	0.6878	0.0883	0.3447	0.021*
H67B	0.7529	0.1732	0.4445	0.021*
C68	0.9123 (3)	0.1204 (2)	0.36342 (16)	0.0186 (6)
H68A	0.9839	0.1930	0.3976	0.022*
H68B	0.9330	0.0446	0.3874	0.022*
C69	0.9330 (3)	0.0855 (2)	0.26471 (16)	0.0195 (6)
H69A	0.8935	0.1532	0.2371	0.023*
H69B	1.0382	0.0852	0.2610	0.023*
C70	0.8593 (3)	−0.0461 (2)	0.21132 (16)	0.0241 (7)
H70A	0.8977	−0.1136	0.2383	0.036*
H70B	0.8780	−0.0645	0.1488	0.036*
H70C	0.7544	−0.0452	0.2123	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0183 (4)	0.0257 (4)	0.0174 (4)	0.0043 (3)	0.0085 (3)	0.0065 (3)
O1	0.0113 (10)	0.0188 (10)	0.0210 (10)	0.0025 (8)	0.0021 (8)	0.0053 (8)
N1	0.0092 (13)	0.0171 (13)	0.0186 (13)	0.0005 (10)	0.0027 (10)	0.0043 (10)
C1	0.0133 (15)	0.0169 (14)	0.0187 (15)	0.0020 (11)	0.0049 (11)	0.0059 (12)
S2	0.0173 (4)	0.0186 (4)	0.0194 (4)	0.0001 (3)	−0.0003 (3)	0.0054 (3)
O2	0.0129 (10)	0.0223 (10)	0.0211 (10)	0.0055 (8)	0.0066 (8)	0.0088 (8)
N2	0.0147 (13)	0.0179 (12)	0.0173 (12)	0.0027 (10)	0.0064 (10)	0.0054 (10)
C2	0.0186 (16)	0.0209 (15)	0.0156 (15)	0.0029 (12)	0.0016 (12)	0.0037 (12)
N3	0.0083 (13)	0.0188 (12)	0.0154 (12)	0.0043 (10)	0.0027 (10)	0.0083 (10)
C3	0.0192 (16)	0.0234 (15)	0.0161 (15)	0.0042 (12)	0.0027 (12)	0.0085 (12)
N4	0.0116 (12)	0.0141 (11)	0.0132 (11)	0.0006 (9)	0.0033 (9)	0.0035 (9)
C4	0.0201 (16)	0.0175 (15)	0.0181 (15)	0.0055 (12)	0.0049 (12)	0.0048 (12)
C5	0.0170 (15)	0.0200 (15)	0.0164 (14)	0.0022 (12)	0.0056 (12)	0.0048 (12)
C6	0.0108 (15)	0.0179 (14)	0.0143 (14)	0.0019 (11)	0.0037 (11)	0.0040 (11)
C11	0.0186 (16)	0.0183 (15)	0.0118 (14)	0.0033 (12)	0.0050 (12)	0.0100 (12)
C12	0.0111 (14)	0.0190 (15)	0.0150 (14)	0.0063 (11)	−0.0002 (11)	0.0075 (12)
C13	0.0195 (16)	0.0198 (15)	0.0192 (15)	0.0039 (12)	0.0027 (12)	0.0042 (12)
C14	0.0196 (16)	0.0179 (15)	0.0185 (15)	−0.0009 (12)	0.0044 (12)	0.0023 (12)
C15	0.0207 (16)	0.0220 (15)	0.0210 (15)	0.0022 (12)	0.0049 (12)	0.0079 (13)
C16	0.0186 (16)	0.0301 (17)	0.0277 (16)	0.0035 (13)	0.0049 (13)	0.0144 (13)
C17	0.0177 (16)	0.0187 (15)	0.0221 (15)	0.0045 (12)	0.0103 (12)	0.0068 (12)
C18	0.0193 (16)	0.0243 (16)	0.0202 (15)	0.0086 (12)	0.0070 (12)	0.0067 (12)
C19	0.043 (2)	0.0340 (18)	0.0298 (18)	0.0196 (15)	0.0187 (15)	0.0176 (15)
C20	0.051 (2)	0.0404 (19)	0.0312 (18)	0.0209 (16)	0.0171 (16)	0.0208 (15)
C61	0.0169 (16)	0.0137 (14)	0.0104 (14)	0.0003 (12)	0.0011 (11)	0.0018 (11)
C62	0.0075 (14)	0.0181 (14)	0.0160 (14)	0.0044 (11)	0.0089 (11)	0.0056 (12)
C63	0.0150 (15)	0.0164 (14)	0.0139 (14)	0.0009 (11)	−0.0013 (11)	0.0034 (12)
C64	0.0136 (15)	0.0177 (14)	0.0198 (15)	0.0022 (11)	0.0059 (12)	0.0065 (12)
C65	0.0166 (15)	0.0194 (15)	0.0181 (15)	0.0023 (12)	0.0032 (12)	0.0050 (12)
C66	0.0192 (16)	0.0227 (15)	0.0175 (15)	−0.0011 (12)	0.0032 (12)	0.0026 (12)
C67	0.0217 (16)	0.0180 (15)	0.0148 (14)	0.0015 (12)	0.0017 (12)	0.0065 (12)
C68	0.0170 (15)	0.0153 (14)	0.0230 (15)	0.0022 (12)	0.0000 (12)	0.0059 (12)
C69	0.0147 (15)	0.0206 (15)	0.0246 (16)	0.0052 (12)	0.0045 (12)	0.0071 (13)
C70	0.0236 (17)	0.0248 (16)	0.0236 (16)	0.0066 (13)	0.0074 (13)	0.0032 (13)

Geometric parameters (Å, º)

S1—C12	1.673 (2)	C15—H15A	0.9900
O1—C11	1.223 (3)	C15—H15B	0.9900
N1—C11	1.383 (3)	C16—H16A	0.9800
N1—C12	1.408 (3)	C16—H16B	0.9800
N1—H1	0.82 (2)	C16—H16C	0.9800
C1—C11	1.502 (3)	C17—C18	1.523 (3)
C1—C2	1.537 (3)	C17—H17A	0.9900
C1—H1A	0.9900	C17—H17B	0.9900
C1—H1B	0.9900	C18—C19	1.522 (3)
S2—C62	1.667 (2)	C18—H18A	0.9900
O2—C61	1.229 (3)	C18—H18B	0.9900
N2—C12	1.330 (3)	C19—C20	1.524 (3)
N2—C13	1.473 (3)	C19—H19A	0.9900
N2—C17	1.475 (3)	C19—H19B	0.9900
C2—C3	1.525 (3)	C20—H20A	0.9800
C2—H2A	0.9900	C20—H20B	0.9800
C2—H2B	0.9900	C20—H20C	0.9800
N3—C61	1.363 (3)	C63—C64	1.515 (3)
N3—C62	1.423 (3)	C63—H63A	0.9900
N3—H3	0.85 (2)	C63—H63B	0.9900
C3—C4	1.524 (3)	C64—C65	1.519 (3)
C3—H3A	0.9900	C64—H64A	0.9900
C3—H3B	0.9900	C64—H64B	0.9900
N4—C62	1.331 (3)	C65—C66	1.524 (3)
N4—C67	1.471 (3)	C65—H65A	0.9900
N4—C63	1.478 (3)	C65—H65B	0.9900
C4—C5	1.516 (3)	C66—H66A	0.9800
C4—H4A	0.9900	C66—H66B	0.9800
C4—H4B	0.9900	C66—H66C	0.9800
C5—C6	1.524 (3)	C67—C68	1.527 (3)
C5—H5A	0.9900	C67—H67A	0.9900
C5—H5B	0.9900	C67—H67B	0.9900
C6—C61	1.499 (3)	C68—C69	1.521 (3)
C6—H6A	0.9900	C68—H68A	0.9900
C6—H6B	0.9900	C68—H68B	0.9900
C13—C14	1.523 (3)	C69—C70	1.516 (3)
C13—H13A	0.9900	C69—H69A	0.9900
C13—H13B	0.9900	C69—H69B	0.9900
C14—C15	1.517 (3)	C70—H70A	0.9800
C14—H14A	0.9900	C70—H70B	0.9800
C14—H14B	0.9900	C70—H70C	0.9800
C15—C16	1.519 (3)
C11—N1—C12	123.6 (2)	N2—C17—C18	112.8 (2)
C11—N1—H1	114.3 (17)	N2—C17—H17A	109.0
C12—N1—H1	116.5 (18)	C18—C17—H17A	109.0
C11—C1—C2	110.42 (19)	N2—C17—H17B	109.0
C11—C1—H1A	109.6	C18—C17—H17B	109.0
C2—C1—H1A	109.6	H17A—C17—H17B	107.8
C11—C1—H1B	109.6	C19—C18—C17	112.0 (2)
C2—C1—H1B	109.6	C19—C18—H18A	109.2
H1A—C1—H1B	108.1	C17—C18—H18A	109.2
C12—N2—C13	120.3 (2)	C19—C18—H18B	109.2
C12—N2—C17	123.9 (2)	C17—C18—H18B	109.2
C13—N2—C17	115.84 (19)	H18A—C18—H18B	107.9
C3—C2—C1	113.5 (2)	C18—C19—C20	113.0 (2)
C3—C2—H2A	108.9	C18—C19—H19A	109.0
C1—C2—H2A	108.9	C20—C19—H19A	109.0
C3—C2—H2B	108.9	C18—C19—H19B	109.0
C1—C2—H2B	108.9	C20—C19—H19B	109.0
H2A—C2—H2B	107.7	H19A—C19—H19B	107.8
C61—N3—C62	122.1 (2)	C19—C20—H20A	109.5
C61—N3—H3	116.8 (16)	C19—C20—H20B	109.5
C62—N3—H3	113.5 (16)	H20A—C20—H20B	109.5
C4—C3—C2	114.9 (2)	C19—C20—H20C	109.5
C4—C3—H3A	108.6	H20A—C20—H20C	109.5
C2—C3—H3A	108.6	H20B—C20—H20C	109.5
C4—C3—H3B	108.6	O2—C61—N3	121.7 (2)
C2—C3—H3B	108.6	O2—C61—C6	122.5 (2)
H3A—C3—H3B	107.5	N3—C61—C6	115.7 (2)
C62—N4—C67	121.7 (2)	N4—C62—N3	114.5 (2)
C62—N4—C63	123.13 (19)	N4—C62—S2	127.16 (18)
C67—N4—C63	115.07 (18)	N3—C62—S2	118.33 (17)
C5—C4—C3	114.1 (2)	N4—C63—C64	113.1 (2)
C5—C4—H4A	108.7	N4—C63—H63A	109.0
C3—C4—H4A	108.7	C64—C63—H63A	109.0
C5—C4—H4B	108.7	N4—C63—H63B	109.0
C3—C4—H4B	108.7	C64—C63—H63B	109.0
H4A—C4—H4B	107.6	H63A—C63—H63B	107.8
C4—C5—C6	112.3 (2)	C63—C64—C65	110.7 (2)
C4—C5—H5A	109.1	C63—C64—H64A	109.5
C6—C5—H5A	109.1	C65—C64—H64A	109.5
C4—C5—H5B	109.1	C63—C64—H64B	109.5
C6—C5—H5B	109.1	C65—C64—H64B	109.5
H5A—C5—H5B	107.9	H64A—C64—H64B	108.1
C61—C6—C5	112.1 (2)	C64—C65—C66	113.7 (2)
C61—C6—H6A	109.2	C64—C65—H65A	108.8
C5—C6—H6A	109.2	C66—C65—H65A	108.8
C61—C6—H6B	109.2	C64—C65—H65B	108.8
C5—C6—H6B	109.2	C66—C65—H65B	108.8
H6A—C6—H6B	107.9	H65A—C65—H65B	107.7
O1—C11—N1	121.8 (2)	C65—C66—H66A	109.5
O1—C11—C1	123.5 (2)	C65—C66—H66B	109.5
N1—C11—C1	114.7 (2)	H66A—C66—H66B	109.5
N2—C12—N1	116.6 (2)	C65—C66—H66C	109.5
N2—C12—S1	125.50 (19)	H66A—C66—H66C	109.5
N1—C12—S1	117.85 (18)	H66B—C66—H66C	109.5
N2—C13—C14	112.1 (2)	N4—C67—C68	111.98 (19)
N2—C13—H13A	109.2	N4—C67—H67A	109.2
C14—C13—H13A	109.2	C68—C67—H67A	109.2
N2—C13—H13B	109.2	N4—C67—H67B	109.2
C14—C13—H13B	109.2	C68—C67—H67B	109.2
H13A—C13—H13B	107.9	H67A—C67—H67B	107.9
C15—C14—C13	114.0 (2)	C69—C68—C67	114.1 (2)
C15—C14—H14A	108.7	C69—C68—H68A	108.7
C13—C14—H14A	108.7	C67—C68—H68A	108.7
C15—C14—H14B	108.7	C69—C68—H68B	108.7
C13—C14—H14B	108.7	C67—C68—H68B	108.7
H14A—C14—H14B	107.6	H68A—C68—H68B	107.6
C14—C15—C16	112.4 (2)	C70—C69—C68	112.9 (2)
C14—C15—H15A	109.1	C70—C69—H69A	109.0
C16—C15—H15A	109.1	C68—C69—H69A	109.0
C14—C15—H15B	109.1	C70—C69—H69B	109.0
C16—C15—H15B	109.1	C68—C69—H69B	109.0
H15A—C15—H15B	107.9	H69A—C69—H69B	107.8
C15—C16—H16A	109.5	C69—C70—H70A	109.5
C15—C16—H16B	109.5	C69—C70—H70B	109.5
H16A—C16—H16B	109.5	H70A—C70—H70B	109.5
C15—C16—H16C	109.5	C69—C70—H70C	109.5
H16A—C16—H16C	109.5	H70A—C70—H70C	109.5
H16B—C16—H16C	109.5	H70B—C70—H70C	109.5
C11—C1—C2—C3	−64.5 (3)	N2—C17—C18—C19	175.4 (2)
C1—C2—C3—C4	−176.74 (19)	C17—C18—C19—C20	−178.9 (2)
C2—C3—C4—C5	−70.0 (3)	C62—N3—C61—O2	−10.6 (4)
C3—C4—C5—C6	−177.4 (2)	C62—N3—C61—C6	169.8 (2)
C4—C5—C6—C61	169.5 (2)	C5—C6—C61—O2	53.4 (3)
C12—N1—C11—O1	9.0 (4)	C5—C6—C61—N3	−126.9 (2)
C12—N1—C11—C1	−173.5 (2)	C67—N4—C62—N3	−175.01 (19)
C2—C1—C11—O1	83.2 (3)	C63—N4—C62—N3	8.9 (3)
C2—C1—C11—N1	−94.2 (2)	C67—N4—C62—S2	5.6 (3)
C13—N2—C12—N1	168.26 (19)	C63—N4—C62—S2	−170.47 (18)
C17—N2—C12—N1	−14.5 (3)	C61—N3—C62—N4	74.4 (3)
C13—N2—C12—S1	−14.6 (3)	C61—N3—C62—S2	−106.2 (2)
C17—N2—C12—S1	162.59 (17)	C62—N4—C63—C64	76.1 (3)
C11—N1—C12—N2	−60.3 (3)	C67—N4—C63—C64	−100.2 (2)
C11—N1—C12—S1	122.3 (2)	N4—C63—C64—C65	174.03 (18)
C12—N2—C13—C14	−125.5 (2)	C63—C64—C65—C66	172.30 (19)
C17—N2—C13—C14	57.1 (3)	C62—N4—C67—C68	108.5 (2)
N2—C13—C14—C15	59.8 (3)	C63—N4—C67—C68	−75.1 (3)
C13—C14—C15—C16	−179.1 (2)	N4—C67—C68—C69	−63.9 (3)
C12—N2—C17—C18	−122.3 (2)	C67—C68—C69—C70	−74.3 (3)
C13—N2—C17—C18	55.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^i	0.85 (2)	2.09 (2)	2.902 (3)	160 (2)
N1—H1···O2^ii	0.82 (2)	2.01 (2)	2.828 (3)	172 (2)

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