T. S. Lobana, I. Kinoshita, K. Kimura, T. Nishioka, D. Shiomi, K. Isobe
FULL PAPER
5 mL of degassed water was added dropwise to the metal-contain-
ing solution by a syringe. The mixture was allowed to stand for 2
days, yielding yellow crystals of 4, stable in air and moisture. Yield
0.069 g (20%). C12H16FeN2O8S2 (436.23): calcd. C 33.01, H 3.67,
N 6.42; found C 33.04, H 3.68, N 6.46. IR: ν˜ ϭ ν(OϪH) 3417 (br.
vs), 3349 (br. vs), 3253 (br. s) cmϪ1; ν(PyCϪH) 3092 (w), 3064 (w);
ν(MeCϪH) 3020Ϫ2881 (w); δ(OϪH) 1658 (s); ν(CϪN) ϩ ν(CϪC)
1581 (m); δ(CϪH) 1456 (m), 1416 (w), 1391 (w); ν(SϪO) 1238 (vs),
1217 (w), 1194 (s), 1154 (s), 1125 (w), 1076 (m); ν(CϪS) 1027 (s);
δ(CϪCH3) 840 (m), 804 (s).
1376 (m); ν(SϪO) 1240 (vs), 1188 (vs), 1141 (s), 1113 (s), 1036 (s);
ν(CϪS) 1018 (vs); δ(CϪCH3) 847 (s).
[Ni(3-mpSO3)2(H2O)2].H2O
(10):
Yield
0.12 g
(66%).
C12H18N2NiO9S2 (457.10): calcd. C 31.50, H 3.94, N 6.13; found
C 31.78, H 3.90, N 6.23. IR: ν˜ ϭ ν(OϪH) 3453 (br. vs), 3366 (br.
vs), 3266 (br. s) cmϪ1; ν(PyCϪH) 3094 (m), 3066 (m); ν(MeCϪH)
3000Ϫ2800 (vw); δ(OϪH) 1655 (s); ν(CϪN) ϩ ν(CϪC) 1588 (m);
δ(CϪH) 1457 (s), 1391 (m); ν(SϪO) 1243 (vs), 1186 (vs), 1155 (vs),
1077 (s); ν(CϪS) 1026 (vs); δ(CϪCH3) 843 (s), 807 (s).
[VO(acac)(3-mpSO3)(H2O)] (11): A solution of bis(acetylacetona-
to)vanadium() oxide (0.11 g, 0.40 mmol) in 2 mL of methanol
was added to a solution of 3-mpSO3H (0.14 g, 0.80 mmol) in 5 mL
of water. The navy blue mixture was stirred for 5 minutes and left
at room temperature for 2 days to afford navy blue crystals of 11.
Yield 0.098 g (68%). C11H15NO7SV (356.24): calcd. C 37.05, H
4.24, N 3.93; found C 37.17, H 4.27, N 3.96. IR: ν˜ ϭ ν(OϪH)
3324 (br. vs), 3222 (br. vs) cmϪ1; ν(PyCϪH) 3092 (w); ν(MeCϪH)
3001Ϫ2884 (w); δ(OϪH) 1648 (s); ν(CϪN) ϩ ν(CϪC) ϩ ν(CϪO)
1578 (vs), 1525 (vs); δ(CϪH) ϩ ν(CHϭC) 1452 (m), 1430 (m), 1366
(vs); ν(SϪO) 1284 (s), 1259 (vs), 1192 (vs), 1156 (s), 1077 (m);
ν(CϪS) 1031 (vs); ν(VϪO) 974 (vs); δ(CϪCH3) 841 (m), 811 (s).
[Co(3-mpSO3)2(H2O)2] (5): A solution of cobalt() bromide hexa-
hydrate (0.10 g, 0.31 mmol) in 2 mL of water was added to a solu-
tion of 3-mpSO3H (0.11 g, 0.62 mmol) in 5 mL of water and the
mixture was stirred for 10 minutes. The solution was concentrated
slowly to ca. 3 mL in a dessicator under water vapor pressure, yield-
ing reddish purple crystals of 5. Yield 0.049 g (36%).
C12H16CoN2O8S2 (439.32): calcd. C 32.78, H 3.64, N 6.37; found
C 32.73, H 3.64, N 6.37. IR: ν˜ ϭ ν(OϪH) 3433 (br. vs), 3358 (br.
vs), 3260 (br. s) cmϪ1; ν(PyCϪH) 3092 (w), 3065 (w); ν(MeCϪH)
3000Ϫ2827 (vw); δ(OϪH) 1657 (s); ν(CϪN) ϩ ν(CϪC) 1586 (m);
δ(CϪH) 1458 (s), 1391 (w); ν(SϪO) 1241 (vs), 1219 (m), 1186 (vs),
1152 (s), 1127 (m), 1076 (m); ν(CϪS) 1027 (vs);); δ(CϪCH3) 841
(m), 805 (s).
X-ray Crystallography: For all crystals intensity data were collected
on a Rigaku AFC-7S diffractometer with a graphite-monochrom-
ated Mo-Kα radiation (λ ϭ 0.71069 A) at 296 K using the ωϪ2θ
[Zn(3-mpSO3)2(H2O)2] (6): A solution of zinc() bromide (0.091 g,
0.40 mmol) in 2 mL of water was added to a solution of 3-mpSO3H
(0.14 g, 0.80 mmol) in 5 mL of water, and the mixture was stirred
for 10 minutes. The solution was left for two weeks to yield color-
less crystals of 6. Yield 0.040 g (22%). C12H16N2O8S2Zn (445.77):
calcd. C 32.30, H 3.59, N 6.28; found C 32.30, H 3.58, N 6.26. IR:
ν˜ ϭ ν(OϪH) 3424 (br. vs), 3356 (vs), 3255 (vs) cmϪ1; ν(PyCϪH)
3093 (m), 3066 (m); ν(MeCϪH) 3025Ϫ2856 (w); δ(OϪH) 1655 (s);
ν(CϪN) 1587 (s); ν(CϪC) 1541 (w); δ(CϪH) 1454 (s), 1419 (w),
1391 (m); ν(SϪO) 1282 (m), 1237 (vs), 1197 (vs), 1157 (vs), 1127
(s), 1078 (s); ν(CϪS) 1031 (vs); δ(CϪCH3) 842 (m), 806 (s). 1H
˚
scan technique to a maximum 2θ value of 60.° Three standard re-
flections monitored after every 150 reflections were used for the
crystal decay corrections. The observed reflections [I Ͼ 3σ(I)] were
extracted from the unique reflections, and the data were corrected
for Lorentz and polarization effects. An absorption correction was
applied using the empirical ψ-scan method. All crystallographic
calculations were carried out using teXsan programs.[23] The struc-
ture was solved by the direct methods (SIR92),[24] and refined with
full-matrix least-squares techniques,[25] with anisotropic displace-
ment parameters for the non-hydrogen atoms. Some hydrogen
atoms were located on difference Fourier maps and refined iso-
tropically, the rest were located in calculated positions and included
in the refinement. Table 3 contains crystal data for complexes
1Ϫ11. CCDC-205227 to -205236 for complexes 1Ϫ5, 7Ϫ11, respec-
tively, and -116650 for complex 6 contain the supplementary crys-
tallographic data for this paper. These data can be obtained free
of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk]
NMR (400 MHz, [D4]methanol, 22 °C): δ ϭ 8.60 (d, JH,H
ϭ
4.9 Hz, 1 H, 6-H), 7.99 (d, JH,H ϭ 7.7 Hz, 1 H, 4-H); 7.59 (dd,
JH,H ϭ 4.9, 7.7 Hz, 1 H, 5-H), 3.41 (s, 3 H, CH3) ppm.
[Zn(5-mpSO3)2(H2O)2] (7): Yield 0.068 g (34%). C12H16N2O8S2Zn
(445.77): calcd. C 32.30, H 3.59, N 6.28; found C 32.43, H 3.58,
N 6.20. IR: ν˜ ϭ ν(OϪH) 3359 (vs), 3245 (s) cmϪ1; ν(PyCϪH) ϩ
ν(MeCϪH) 3100Ϫ2900 (vw); δ(OϪH) 1649 (s); ν(CϪN) 1598(m);
ν(CϪC) 1577 (w); δ(CϪH) 1473 (m), 1378 (m); ν(SϪO) 1298 (m),
1233 (vs), 1207 (vs), 1157 (s), 1125 (s); ν(CϪS) 1030 (vs);
δ(CϪCH3) 835 (s). 1H NMR (400 MHz, [D4]methanol, 22 °C): δ ϭ
8.58 (s, 1 H, 6-H), 8.02 (d, JH,H ϭ 8.2 Hz, 1 H, 4-H), 7.95 (d,
JH,H ϭ 8.2 Hz, 1 H, 3-H); 3.05 (s, 3 H, CH3) ppm.
Acknowledgments
[Zn(PySO3)2(H2O)2] (8): Yield 0.016 g (31%). C10H12N2O8S2Zn
(417.71): calcd. C 28.73, H 2.87, N 6.70; found C 28.84, H 2.82, N
6.70. IR: ν˜ ϭ ν(OϪH) 3335 (br. vs), 3240 (s) cmϪ1; ν(PyCϪH)
3107(m); δ(OϪH) 1650 (s); ν(CϪN) 1596 (s); ν(CϪC) 1568 (w);
δ(CϪH) 1470 (m), 1436 (s); ν(SϪO) 1300 (m), 1235 (vs), 1205 (vs),
1170 (s), 1159 (s), 1101 (m), 1056 (m); ν(CϪS) 1032 (vs). 1H NMR
(400 MHz, [D4]methanol, 22 °C): δ ϭ 8.72 (d, JH,H ϭ 5.1 Hz, 1 H,
6-H), 8.18 (t, JH,H ϭ 7.8 Hz, 1 H, 4-H), 8.08 (d, JH,H ϭ 7.8 Hz, 1
H, 3-H), 7.69 (t, JH,H ϭ 6.2 Hz, 1 H, 5-H) ppm.
T. S. L. thanks the Japan Society for Promotion of Science for
Invitation Fellowship. He also thanks the Guru Nanak Dev
University, Amritsar, India for leave. Financial assistance from
Ministry of Education, Science and Culture, Japan. Elemental
analysis services rendered by the Analytical Center of Osaka City
University are gratefully acknowledged. The authors are grateful
to the referees for useful comments.
[1]
J. M. Lehn, Supramolecular Chemistry: Concepts and Perspec-
tives; Wiley-VCH, Weinheim, 1995, p. 89 and 139.
[Co(4-mpSO3)2(H2O)2] (9): Yield 0.130 g (38%). C12H16CoN2O8S2
(439.32): calcd. C 32.78, H 3.64, N 6.37; found C 32.94, H 3.64, N
6.42. IR: ν˜ ϭ ν(OϪH) 3375 (br. vs), 3260 (br. s) cmϪ1; ν(PyCϪH)
3081 (m); ν(MeCϪH) 2964Ϫ2834 (w); δ(OϪH) 1654 (s); ν(CϪN)
1611 (s); ν(CϪC) 1555 (w); δ(CϪH) 1473 (m), 1438 (m), 1405 (m),
[2]
G. R. Desiraju, Angew. Chem. Int. Ed. Engl. 1995, 34,
2311Ϫ2327.
[3]
V. Baron, B. Gillon, A. Cousson, C. Mathoniere, O. Kahn, A.
Grand, L. Ohrstrom, B. Delley, M. Bonnet, J. X. Boucherle, J.
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2004, 356Ϫ367