Job/Unit: I42736
/KAP1
Date: 05-11-14 15:16:59
Pages: 12
FULL PAPER
0.53 mmol) and NiCl2·6H2O (132 mg, 0.56 mmol). Yield: 209 mg stirring, aqueous ammonia (5 mL, 25% in water) was added, and
(86%), pale blue powder. C12H16N2NiO9S2 (455.10): calcd. C stirring was continued overnight. The resulting light blue-violet
31.67, H 3.54, N 6.16, S 14.09; found C 31.66, H 3.53, N 6.15, S
solution was layered with ethanol to yield a precipitate of 7/8 after
14.81. IR (neat): ν = 3456 (m), 3391 (br, m), 3101 (w), 2982 (w), several days. The mother liquor was almost completely decanted,
˜
2922 (w), 1632 (w), 1599 (m), 1575 (m), 1477 (m), 1469 (m), 1435
and the precipitate was allowed to stand without drying overnight,
(m), 1402 (w), 1340 (w), 1324 (w), 1302 (m), 1241 (s), 1195 (vs), after which time the primary precipitate had redissolved to allow
1139 (vs), 1123 (sh), 1045 (s), 1033 (vs), 1018 (sh), 946 (w), 926 (w),
891 (w), 827 (m), 806 (s), 783 (s), 737 (w), 666 (s) cm–1. UV/Vis
(H2O): λ = 622, 914 nm.
the crystallization of 9. The resulting product was dried in vacuo.
Yield: 65 mg (53%), blue-green solid.
Method B: A mixture of 4 (49 mg, 0.11 mmol) and NH4Cl (168 mg,
3.14 mmol) was treated with water (5 mL). Aqueous ammonia
(0.8 mL, 1.6 mmol, 2 molL–1) was added to afford a pale violet
solution, which was layered with ethanol to afford blue-green crys-
tals after a couple of days. The mother liquor was decanted, and
Diaqua-6,6Ј-bis(sulfonatomethyl)-2,2Ј-bipyridinezinc(II)
Hydrate
{[Zn(smbipy)(H2O)2]·H2O, 5}: Prepared from Na2(smbipy)
(215 mg, 0.55 mmol) and Zn(NO3)2·4H2O (145 mg, 0.55 mmol).
Yield: 196 mg (77%), colourless powder. C12H16N2O9S2Zn
(461.79): calcd. C 31.21, H 3.49, N 6.07, S 13.89; found C 30.52, the product was washed with ethanol and dried in vacuo. Yield:
H 3.40, N 6.07, S 13.67. 1H NMR (400 MHz, D2O): δ = 4.66 (4 36 mg (77 %), blue-green crystalline powder. C12H16N4NiO6S2
H, CH ), 7.75 (2 H), 8.25 (2 H), 8.47 (2 H) ppm. IR (neat): ν =
(435.10): calcd. C 33.13, H 3.71, N 12.88, S 14.74; found C 32.88,
H 3.77, N 12.76, S 14.61. IR (neat): ν˜ = 3364 (m), 3349 (m), 3284
(w), 3206 (w), 3078 (w), 2969 (w), 2924 (w), 1596 (m), 1574 (m),
1476 (w), 1468 (w), 1432 (m), 1406 (w), 1335 (w), 1317 (w), 1296
(m), 1235 (s), 1195 (vs), 1143 (vs), 1126 (s), 1036 (vs), 1019 (s), 947
(w), 927 (w), 889 (m), 829 (w), 812 (s), 797 (s), 784 (m), 749 (w),
740 (w), 676 (s), 656 (s) cm–1.
˜
2
3487 (m), 3392 (br, m), 3102 (w), 2986 (w), 2923 (w), 1739 (w),
1634 (w), 1597 (m), 1576 (m), 1467 (w), 1437 (m), 1403 (w), 1337
(w), 1323 (w), 1299 (w), 1243 (s), 1195 (vs), 1139 (vs), 1123 (s),
1044 (s), 1029 (vs), 946 (w), 931 (w), 891 (w), 827 (w), 806 (s), 783
(s), 753 (w), 738 (w), 675 (m) cm–1.
Aqua-6,6Ј-bis(sulfonatomethyl)-2,2Ј-bipyridinecopper(II) {[Cu(smbipy)-
(H2O)], 6}: Prepared from Na2(smbipy) (201 mg, 0.52 mmol) and
CuSO4·5H2O (134 mg, 0.54 mmol). Yield: 173 mg (79%), green
powder. C12H12CuN2O7S2 (423.92): calcd. C 34.00, H 2.85, N 6.61,
Tetraamminecopper(II) 6,6Ј-Bis(sulfonatomethyl)-2,2Ј-bipyridine Di-
hydrate {[Cu(NH3)4](smbipy)·2H2O, 10}: Complex 6 (43 mg,
0.10 mmol) was suspended in a mixture of aqueous ammonia
(5 mL, 25% in water) and water (15 mL). The mixture was heated
briefly to ca. 80 °C until all of the solid dissolved. The mixture was
cooled to room temperature, and the resulting blue solution was
treated with ethanol (20 mL). To isolate the precipitated product,
the mother liquor was decanted, and the solid was dried in vacuo.
Yield: 26 mg (50 %), violet powder. C12H26CuN6O8S2 (510.07):
calcd. C 28.26, H 5.14, N 16.48, S 12.57; found C 28.52, H 4.93,
S 15.13; found C 33.87, H 2.89, N 6.54, S 15.09. IR (neat): ν =
˜
3344 (br, m), 3085 (w), 3059 (w), 3019 (w), 2997 (w), 1653 (w), 1600
(m), 1573 (m), 1485 (m), 1472 (m), 1433 (m), 1394 (w), 1342 (w),
1315 (sh), 1302 (m), 1274 (s), 1251 (s), 1221 (s), 1209 (s), 1194 (s),
1167 (s), 1135 (vs), 1119 (s), 1031 (sh), 1022 (s), 1006 (vs), 918 (w),
888 (m), 854 (w), 827 (m), 810 (s), 789 (s), 749 (s), 717 (w), 655 (s)
cm–1. UV/Vis (H2O): λ = 715 nm.
N 16.34, S 12.86. IR (neat): ν = 3564 (w), 3335 (m), 3267 (w), 3187
˜
Hexaamminenickel(II)
6,6Ј-Bis(sulfonatomethyl)-2,2Ј-bipyridine
(w), 1611 (w), 1576 (m), 1563 (m), 1439 (m), 1413 (w), 1394 (w),
1259 (s), 1225 (w), 1180 (vs), 1138 (s), 1094 (w), 1077 (w), 1035
(vs), 993 (m), 822 (s), 770 (w), 741 (s), 723 (s) cm–1.
{[Ni(NH3)6](smbipy), 7}: To a suspension of 4 (46 mg, 0.10 mmol)
in water (5 mL) was added aqueous ammonia (15 mL, 25% in
water). The resulting pale violet solution was layered with ethanol
and allowed to stand for several days to afford light violet crystals.
The mother liquor was decanted, and the product was briefly dried
in vacuo. Yield: 41 mg (80%), light violet crystalline powder.
C12H28N8NiO6S2 (503.22): calcd. C 28.64, H 5.61, N 22.27, S 12.74;
Triammine-6,6Ј-bis(sulfonatomethyl)-2,2Ј-bipyridinecopper(II) Di-
hydrate {[Cu(smbipy)(NH3)3]·2H2O, 11}: A mixture of 6 (43 mg,
0.10 mmol) and NH4Cl (162 mg, 3.03 mmol) was treated with
water (5 mL). Aqueous ammonia (0.4 mL, 0.8 mmol, 2 mol L–1
)
was added to afford a blue-green solution, which was layered with
ethanol to afford blue needles after a couple of days. The mother
liquor was decanted, and the product was washed with ethanol
and dried in vacuo. Yield: 25 mg (50%), blue crystalline powder.
found C 28.59, H 5.49, N 21.97, S 12.46. IR (neat): ν = 3356 (m),
˜
3285 (br, w), 3077 (w), 2932 (w), 1637 (m), 1619 (m), 1594 (w),
1565 (m), 1434 (m), 1403 (w), 1393 (w), 1272 (m), 1245 (m), 1224
(m), 1195 (s), 1175 (vs), 1128 (s), 1079 (m), 1035 (vs), 991 (m), 892
(w), 840 (w), 813 (s), 769 (w), 743 (s) cm–1.
C
12H23CuN5O8S2 (493.02): calcd. C 29.23, H 4.70, N 14.21, S
13.01; found C 29.18, H 4.44, N 14.03, S 12.92. IR (neat): ν = 3465
˜
Pentaamminemonoaquanickel(II) 6,6Ј-Bis(sulfonatomethyl)-2,2Ј-bi-
pyridine {[Ni(NH3)5(H2O)](smbipy), 8}: Prepared from 4 (50 mg,
0.11 mmol) in water (20 mL) and ammonia (3 mL, 25% in water)
according to the abovementioned procedure. Yield: 11 mg (20%),
light blue crystals. C12H27N7NiO7S2 (504.21): calcd. C 28.59, H
5.40, N 19.45, S 12.72; found C 28.59, H 5.33, N 19.25, S 12.90.
(br, w), 3316 (m), 3248 (w), 3180 (w), 3084 (w), 2975 (w), 2936 (w),
1601 (m), 1574 (m), 1476 (w), 1462 (m), 1436 (m), 1305 (sh), 1274
(s), 1260 (s), 1235 (s), 1182 (vs), 1137 (vs), 1113 (s), 1092 (m), 1031
(vs), 1008 (s), 927 (w), 889 (w), 814 (vs), 765 (m), 751 (sh), 736 (s)
cm–1.
Triammine-6,6Ј-bis(sulfonatomethyl)-2,2Ј-bipyridine(dihydroxido)di-
copper(II) Hydrate {[Cu2(smbipy)(μ-OH)2(NH3)3]·H2O, 12}: Com-
plex 6 (45 mg, 0.11 mmol) was suspended in water (5 mL). The ad-
dition of ammonia (0.5 mL, 1.0 mmol, 2 molL–1) led to a blue-
green solution, which was layered with ethanol. After several days,
the resulting crystalline product was dried in vacuo and manually
separated into three fractions according to crystal colour. Com-
bined yield: ca. 20 mg blue-green plates (12), blue needles (11) and
violet blocks (10; ratio 12/11/10 ≈ 3:1:2). C12H23Cu2N5O9S2
IR (neat): ν = 3346 (s), 3282 (m), 3208 (m), 3069 (w), 2938 (w),
˜
1625 (m), 1610 (m), 1576 (m), 1562 (m), 1440 (m), 1403 (w), 1395
(w), 1228 (s), 1195 (s), 1181 (vs), 1158 (s), 1128 (s), 1081 (m), 1036
(vs), 991 (m), 889 (w), 818 (s), 773 (m), 743 (s) cm–1.
Both 7 and 8 are unstable in the solid state at room temperature
and slowly lose ammonia.
Diammine-6,6Ј-bis(sulfonatomethyl)-2,2Ј-bipyridinenickel(II) {[Ni-
(smbipy)(NH3)2], 9}: Method A: A solution of NiCl2·6H2O (69 mg,
0.29 mmol) in water (5 mL) was added to a solution of 1 (109 mg, (572.56): calcd. C 25.17, H 4.05, N 12.23, S 11.20; found C 25.23,
0.28 mmol) in water (10 mL) at room temperature. After 15 min of
H 4.09, N 12.29, S 11.19. IR (neat): ν = 3552 (sh), 3494 (w), 3445
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Eur. J. Inorg. Chem. 0000, 0–0
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