HAMOUD et al.
124
diffractometer (Research Center for X-ray Diffraction
Studies, St. Petersburg State University) using
CrysAlisPro software package [8]. The structure was
initially solved by the direct method using SIR2011
[9]. Hydrogen atoms in molecule 3 were placed into
calculated positions which were refined in the rigid
body approximation. However, at this step solvent
atoms were not revealed by the Fourier difference
syntheses, and the R-factor was too large (12–13%).
Therefore, the structure was solved by the SQUEEZE
procedure [10] included in SHELXL [11], and then
chloroform and water molecules were detected by the
Fourier difference syntheses; nevertheless, refinement
of the coordinates of atoms therein and their thermal
parameters was not reliable. For that reason, the coor-
dinates of atoms in the solvent molecules and their
populations were not included in the deposited crys-
tallographic information file (CIF) but are available
from the authors.
kept for 1 h at 0°C, and the solidified material was
ground to obtain a white powder which was dried
under reduced pressure. Yield 50.0 g (85%), mp 90–
92°C; published data [13]: mp 86–88°C. IR spectrum,
ν, cm–1: 3280 (NH), 2996, 2960 (CH2), 1567 (C–N,
δ N–H), 1340 (C–N), 1301 (C=S), 1014 (C–O).
1H NMR spectrum (DMSO-d6), δ, ppm: 4.83 s (4H,
CH2), 5.48 s (2H, OH), 8.03 s (2H, NH). Found:
m/z 159.0199 [M + Na]+. C3H8N2NaO2S. Calculated:
M + Na 159.0198.
1,3,5,7,11,13,15,17-Octaazatricyclo[15.3.1.17,11]-
docosane-4,14-dithione (3). a. Modified procedure
[5]. A suspension of 5.45 g (40 mmol) of compound 2
in 22 mL of isopropyl alcohol was cooled to 3°C,
3.35 mL (2.96 g, 40 mmol) of propane-1,3-diamine
was added under vigorous stirring, and the mixture
was stirred for 10 min at 3°C, heated for 2 h at 68–
75°C, and left overnight at room temperature. The
precipitate was filtered off, washed with 10 mL of
isopropyl alcohol, and dried under reduced pressure.
Yield 0.795 g (16%), mp 203–204°C (from CHCl3–
i-PrOH, 2:1). IR spectrum, ν, cm–1: 3443 (OH), 3238,
3160 (NH), 3007, 2969, 2937, 2925, 2857, 2826, 2801,
2757 (CH2), 1578, 1574 (C–N, δNH), 1300 (C=S).
1H NMR spectrum (CDCl3), δ, ppm: 1.75 d.m (2H,
Compound 3 crystallized in tetragonal crystal sys-
tem, space group I41/a. C14H28N8S2. Unit cell param-
eters: a = 17.7648(7), c = 20.0444(13) Å; V =
6325.8(6) Å3; dcalc = 0.787 g/cm3 (without solvent
molecules); Z = 8; F(000) = 1600. Final divergence
factors R = 0.071 [F2 > 2σ(F2)], wR = 0.196 (F2);
goodness of fit 1.01; number of variables 109; absorp-
tion coefficient 1.59 mm–1. Intensities of 7093 reflec-
tions, including 2763 independent nonequivalent
reflections, were measured at 100 K (micro-focused
2
9-HB, 19-HB,* J = 12.9 Hz), 1.85 pseudo-q.t (2H,
2
3
3
9-HA, 19-HA, J = 12.9, JAB = 12.6, JAA = 4.3 Hz),
2
2.32 pseudo-t.d (4H, 8-HB, 10-HB, 18-HB, 20-HB, J =
11.8, JBA = 11.8, JBB = 2.6 Hz), 2.86 d (2H, 21-HB,
3
3
2
monochromatized CuKα radiation, λ 1.54184Å; θmin
=
22-HB, J = 10.3 Hz), 2.90 d.m (4H, 8-HA, 10-HA,
18-HA, 20-HA, 2J = 11.2 Hz), 3.62 d.d (4H, 2-HB, 6-HB,
3.3°, θmax = 67.5°) from a 0.15×0.13×0.17-mm single
crystal of 3, which was grown at room temperature by
slow evaporation of the mother liquor obtained by re-
crystallization of a crude sample of 3 from chloro-
form–isopropyl alcohol (2:1). The molecular structure
of 3 was plotted using Mercury 3.5.1 [12]. The crystal-
lographic data were deposited to the Cambridge crys-
tallographic Data Centre (entry no. CCDC 1433826).
2
3
12-HB, 16-HB, J = 11.9, JNH,B = 2.7 Hz), 4.23 d (2H,
21-HA, 22-HA, 2J = 10.0 Hz), 5.29 d.d (4H, 2-HA, 6-HA,
12-HA, 16-HA, 2J = 11.6, 3JNH,A = 9.8 Hz), 9.85 d.d (4H,
3
3
NH, JNH,A = 9.8, JNH,B = 2.7 Hz); the spectrum also
contained signals of water (δ 1.64 ppm) and weak sig-
nals of solvate propan-2-ol. 13C–{1H} NMR spectrum,
δC, ppm: 185.01 (C4, C14), 70.72 (C21, C22), 63.08 (C2,
C6, C12, C16), 50.46 (C8, C10, C18, C20), 24.33 (C9, C19);
the spectrum also contained a weak signal of solvate
propan-2-ol (δC 25.37 ppm). Found: m/z 373.1951
[M + H]+. C14H29N8S2. Calculated: M + H 373.1951.
The melting points were determined on a PTP-M
melting point apparatus and are uncorrected. Com-
mercial solvents used for the recrystallization of 3
were preliminarily purified by distillation, the first 5%
and the last 10% of the distillate being discarded.
b. A solution of 2.96 g (40 mmol, 3.35 mL) of
propane-1,3-diamine in 7 mL of isopropyl alcohol was
cooled to 5°C, a mixture of 3.25 g (40 mmol) of 37%
formaldehyde solution and 8 mL of isopropyl alcohol
was added dropwise over a period of 10 min under
vigorous stirring, and 5.45 g (40 mmol) of compound 2
N,N′-Bis(hydroxymethyl)thiourea (2) was syn-
thesized according to a simplified procedure [13].
Thiourea (1), 32.7 g (0.43 mol), was dissolved on
heating in 74.5 g (0.87 mol) of a 35% formaldehyde
solution, and the mixture was stirred for 15 min at 45–
50°C and kept for 10–12 h in a crystallizer (according
to [13], water was distilled off). The syrupy liquid was
* Hereinafter, HA stands for pseudoequatorial, and HB, for pseudo-
axial protons.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016