[NH3 (liq.)]: 325, 289. UV (EtOH) lmax/nm (log e): 458 (3.24), 324 (3.45),
273 (3.95), 214 (4.07).
Compound 2. To a solution of 100 mg (5 3 1024 mol) of 1 in 0.6 cm3 of
pyridine was added 36 mg (2 3 1023 mol) of H2O. After 24 h the precipitate
(which consisted of a mixture of 2 and pyridinium sulfate, according to the
MS and IR data) was filtered off, washed with pyridine and recrystallized
from toluene. Compound 2, 5 %, colorless crystals, mp 215–217 °C. MS m/z
309.9729 (M+; calculated for C12H10N2S4 309.9727). IR n/cm21 (KBr):
3274s, 3050w, 1585m, 1470s, 1443m, 1269s, 901m, 757s, 612s, 575m,
448s. Evaporation of the filtrate under reduced pressure affords viscous oil
assumed to be (GC-MS, 1H and 13C NMR) a mixture of 2,2A-diaminodiphe-
nyl disulfide and related polysulfanes.
Scheme 2
Compound 13. To a solution of 105 mg (5.25 3 1024 mol) of 1 in 4 cm3
of CH2Cl2 was added 228 mg (2.1 3 1023 mol) of Me3SiCl. After 21 d the
precipitate was filtered off and recrystallized from SOCl2–CCl4 (3+1).
Compound 13, 10%, yellow crystals, mp 194–196 °C (decomp.) MS m/z
amounts of pyridine facilitate the hydrolysis in THF insignif-
icantly.
According to the X-ray diffraction data (Fig. 3) the molecule
2 possesses an inversion center. The macrocycle conformation
can be described as a chair featuring two transannular N–H…S
hydrogen bonds with a H…S distance of 2.60 Å.
153.9775 (M+
2
35Cl; calculated for C6H4NS2 153.9785). NMR d
(CF3CO2H): 1H: 9.09, 9.00, 8.65, 8.46; 13C: 164.0, 156.2, 139.1, 133.9,
128.1, 123.4; 14N [NH3 (liq.)]: 406. UV lmax/nm (log e) (CF3CO2H): 426
(3.25), 347 (4.38).
After evaporation of the filtrate under reduced pressure unreacted 1 was
recovered in 80% yield.
‡ X-ray crystallography and ab initio calculations. X-ray structure data for
2 and 11. Compound 2: C12H10N2S4, M = 310.46, monoclinic, a =
8.101(2), b = 4.7156(9), c = 16.905(5) Å, b = 95.57(2)°, U = 642.7(3)
Å3, space group P21/c, Z = 2, dc = 1.604 g cm23, m(MoKa) = 0.719
mm21, 875 reflections measured, 807 unique (Rint = 0.037) which were
used in all calculations. The final R was 0.0873 (for 505 observed
reflections).
Compound 11: C6H3IN2S3, M = 326.18, monoclinic, a = 4.117(2), b =
11.048(7), c = 20.63(1) Å, b = 91.74(5)°, U = 938.2(9) Å3, space group
P21/c, Z = 4, dc = 2.309 g cm23, m(MoKa) = 4.023 mm21, 1859
reflections measure, 1616 unique (Rint = 0.040) which were used in all
calculations. The final R was 0.0831 (for 943 observed reflections).
b1/b105001j/ for electronic files in .cif or other electronic format.
The MP2/6-31G* calculations were performed using the GAMESS
program.14
Fig. 3 The X-ray structure of molecule 2. Selected bond lengths (Å), bond
and torsion angles (°): S(1)-S(2) 2.082(5), S(2)-N(3) 1.66(1), N(3)-C(4)
1.42(2), C(4)-C(5) 1.37(2), C(5)-S(6) 1.80(1), S(6)-S(7) 2.082(5); S(1)-
S(2)-N(3) 107.1(5), S(2)-N(3)-C(4) 124(1), N(3)-C(4)-C(5) 121(1), C(4)-
C(5)-S(6) 121.2(9), C(5)-S(6)-S(7) 100.9(4), C(10)-S(1)-S(2)-N(3)
268.3(7), S(1)-S(2)-N(3)- C(4) 269(1), S(2)-N(3)-C(4)-C(5) 144(1), C(4)-
C(5)-S(6)-S(7) 297(1). The dotted lines show N-H…S hydrogen bonds.
1 C. W. Rees, J. Heterocycl. Chem., 1992, 29, 639; X.-G. Duan, X.-L.
Duan, C. W. Rees and T.-Y. Yue, J. Heterocycl. Chem., 1996, 33,
1419.
2 J. M. Rawson, A. J. Banister and I. Lavender, Adv. Heterocycl. Chem.,
1995, 62, 137; J. M. Rawson and G. D. McManus, Coord. Chem. Rev.,
1999, 189, 135; T. M. Barclay, A. W. Cordes, R. C. Haddon, M. E. Itkis,
R. T. Oakley, R. W. Reed and H. Zhang, J. Am. Chem. Soc., 1999, 121,
969.
Thus, two novel polysulfur–nitrogen heterocyclic systems
have been prepared by original approaches and structurally
characterized.
The authors are grateful to the Russian Foundation for Basic
Research for financial support of their work (project
99-03-33115 and grant 01-03-06190) and access to the
Cambridge Structural Database (grant 99-07-90133) and to the
STN International databases via STN Center at their Institute
(grant 00-03-32721).
3 T. Torroba, J. Prakt. Chem., 1999, 341, 99.
4 I. V. Vlasyuk, V. A. Bagryansky, N. P. Gritsan, Yu. N. Molin, A. Yu.
Makarov, Yu. V. Gatilov, V. V. Shcherbukhin and A. V. Zibarev, Phys.
Chem. Chem. Phys., 2001, 3, 409.
5 (a) J. L. Morris, C. W. Rees and J. D. Rigg, J. Chem. Soc., Chem.
Commun., 1985, 55; (b) S. T. A. K. Daley, C. W. Rees and D. J.
Williams, J. Chem. Soc., Chem. Commun., 1985, 57.
6 A. W. Cordes, M. Hojo, H. Koenig, M. C. Noble, R. T. Oakley and W.
T. Pennington, Inorg. Chem., 1986, 25, 1137.
7 J. L. Morris and C. W. Rees, J. Chem. Soc., Perkin Trans. 1, 1987, 211;
J. L. Morris and C. W. Rees, J. Chem. Soc., Perkin Trans. 1, 1987,
217.
Notes and references
† Syntheses. Compounds 1–6, 9–11. In an argon atmosphere, solutions of
1.35 g (0.01 mol) of S2Cl2 and 0.01 mol of Ar-NNSNN-SiMe3 (Ar = C6H5,
4-BrC6H4, 3-CH3C6H4 and 3-IC6H4),6,9 each in 30 cm3 of CH2Cl2, were
slowly mixed by adding them dropwise to 300 cm3 of CH2Cl2 at 20 °C, over
a period of 1 h, with stirring. After a further 1 h, the reaction solution was
filtered, the solvent distilled off under reduced pressure, and the residue was
chromatographed on silica (CCl4).
8 M. J. Plater and C. W. Rees, J. Chem. Soc., Perkin Trans. 1, 1991,
317.
Compound 1, 10%, red oil. MS m/z 199.9534 (M+; calculated for
C6H4N2S3 199.9537). NMR (Bruker DRX-500 throughout the work) d
(CDCl3): 1H: 7.59, 7.34, 6.98; 13C: 151.1, 146.0, 132.7, 130.6, 130.4, 124.9;
15N [NH3 (liq.)]: 318.9 (s), 292.0 (d, J 3.3 Hz). UV (heptane) lmax/nm (log
e): 457 (3.39), 322 (3.53), 272 (3.85), 267 (3.83), 258 (3.75).
9 I. Yu. Bagryanskaya, Yu. V. Gatilov, A. Yu. Makarov, A. M.
Maksimov, A. O. Miller, M. M. Shakirov and A. V. Zibarev, Heteroat.
Chem., 1999, 10, 113; A. Yu. Makarov, I. Yu. Bagryanskaya, Yu. V.
Gatilov, T. V. Mikhalina, M. M. Shakirov, L. N. Shchegoleva and A. V.
Zibarev, Heteroat. Chem., 2001, 12, in the press.
10 F. Feher and B. Engelen, Z. Anorg. Allg. Chem., 1979, 452, 37.
11 I. Yu. Bagryanskaya, H. Bock, Yu. V. Gatilov, A. Haas, M. M.
Shakirov, B. Solouki and A. V. Zibarev, Chem. Ber./Recueil, 1997, 130,
247.
12 F. Blockhuys, S. L. Hinchley, A. Yu. Makarov, Yu. V. Gatilov, A. V.
Zibarev, J. D. Woollins and D. W. H. Rankin, Chem. Eur. J., 2001, 7,
3592.
13 A. V. Zibarev, A. V. Rogoza, S. N. Konchenko, M. A. Fedotov and G.
G. Furin, Zh. Obshch. Khim., 1991, 61, 441 (Chem. Abstr., 115,
92167).
Compound 6, 4%, orange–red crystals, mp 80–81 °C (hexane). MS m/z
277.8642 (M+; calculated for C6H3BrN2S3 277.8642, 79Br). NMR
d
(CDCl3): 1H: 7.78, 7.46, 7.19; 13C: 150.0, 147.6, 134.5, 133.0, 131.0, 117.1;
14N [NH3 (liq.)]: 319, 292. UV (heptane) lmax/nm (log e): 464 (3.51), 325
(3.60), 277 (3.98), 229 (4.32), 208 (4.32).
Compounds 9 and 10 ( ~ 2+1 mixture, 1H NMR), 7%, red oil. MS m/z
213.9697 (M+; calculated for C7H6N2S3 213.9693). NMR d (CDCl3): 1H: 9,
7.48, 7.14, 6.80, 2.34; 10, 7.22, 7.17, 6.91, 2.49; 13C: 9, 150.9, 142.8, 140.4,
131.9, 130.1, 125.2, 20.8; 10, 152.1, 145.2, 140.4, 129.7, 128.0, 125.5,
21.3; 15N [NH3 (liq.)]: 9, 319.2 (s), 292.1 (d, J 3.3 Hz); 10, 319.8 (s), 292.3
(d, J 3.3 Hz).
14 M. V. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon,
J. J. Jensen, S. Koseki, N. Matsunaga, K. A. Nguen, S. Su, T. L. Windus,
M. Dupuis and J. A. Montgomery, J. Comput. Chem., 1993, 14,
1347.
Compound 11, 3%, red crystals, mp 100–101 °C (hexane). MS m/z
325.8505 (M+; calculated for C6H3IN2S3 325.8505). NMR d (CDCl3): 1H:
7.70, 7.30, 7.29; 13C: 151.9, 145.5, 138.5, 133.2, 132.7, 95.5; 14N
Chem. Commun., 2001, 1774–1775
1775