[Ag2(L2)(NO3)2]N, 2. Prepared as described for 1, except that
L2 (0.15 g, 0.5 mmol) was used. Yield: 0.38 g (60%, based on Ag).
Anal calcd for C13H10Ag2ClN5O9 (MW ¼ 631.45): C 24.73, H
1.60, N 11.09%. Found: C 24.98, H 1.52, N 10.83%. FTIR
(cmꢀ1): 3317(m), 3033(m), 2952(m), 2360(m), 2343(m), 1724(s),
1676(s) 1575(s), 1561(m), 1540(m), 1509(m), 1493(s), 1431(s),
1362(s), 1272(s), 1245(m), 1194(m), 1153(m), 1113(s), 1015(m),
945(m), 908(w), 867(m), 825(m), 782(m), 724(m), 701(m), 638
(m), 539(w), 515(m), 460(w), 445(w), 418(m).
[Ag2(L4)4](PF6)2, 7. Prepared as described for 6, except that
AgPF6 (0.13 g, 0.5 mmol) was used. Yield: 0.32 g (63%, based on
Ag). Anal calcd for C26H20AgF6I2N6O6P (MW ¼ 1019.12): C
30.64, H 1.98, N 8.25%. Found: C 30.98, H 1.65, N 8.43%. FTIR
(cmꢀ1): 3302(m), 3061(m), 2962(m), 2360(m), 2343(m), 1708(s),
1690(s), 1672(s), 1577(s), 1509(m), 1485(s), 1423(s), 1375(m),
1335(m), 1294(m), 1280(s), 1241(m), 1195(m), 1170(m), 1112(s),
1018(m), 975(m), 937(m), 903(w), 875(m), 855(m), 831(m), 787
(m), 728(m), 661(s), 639(m), 535(m), 512(m), 492(w), 474(w), 458
(m), 420(w).
[Ag2(L3)(NO3)2]N, 3. Prepared as described for 1, except that
L3 (0.17 g, 0.5 mmol) was used. Yield: 0.44 g (65%, based on Ag).
Anal calcd for C13H10Ag2BrN5O9 (MW ¼ 675.91): C 23.10, H
1.49, N 10.36%. Found: C 23.57, H 1.21, N 10.58%. FTIR
(cmꢀ1): 3305(m), 3091(m), 3039(m), 2962(m), 2360(m), 2342(m),
1719(s), 1672(s) 1577(s), 1559(m), 1541(m), 1508(m), 1491(s),
1427(s), 1384(s), 1281(s), 1194(m), 1112(s), 1028(m), 938(m), 904
(w), 880(m), 825(m), 790(w), 774(m), 727(m), 697(m), 657(m),
537(w), 511(m), 460(w), 473(w), 418(m).
[Ag2(L4)4](SbF6), 8. Prepared as described for 6, except that
AgSbF6 (0.17 g, 0.5 mmol) was used. Yield: 0.31 g (56%, based
on Ag). Anal calcd for C26H20AgF6I2N6O6Sb (MW ¼ 1109.90):
C 28.14, H 1.82, N 7.57%. Found: C 28.33, H 2.15, N 7.14%.
FTIR (cmꢀ1): 3299(m), 3058(m), 2964(m), 2360(m), 2343(m),
1710(s), 1684(s), 1669(s), 1575(s), 1508(m), 1484(s), 1421(s), 1370
(m), 1336(m), 1296(m), 1279(s), 1243(m), 1197(m), 1171(s), 1114
(s), 1019(m), 978(m), 939(m), 903(w), 876(m), 858(m), 829(m),
788(m), 723(m), 659(s), 643(m), 539(m), 513(m), 492(w), 473(w),
459(m), 418(w).
[Ag(L4)(NO3)]N, 4. Prepared as described for 1, except that L4
(0.38 g, 1.0 mmol) was used. Yield: 0.38 g (69%, based on Ag).
Anal calcd for C13H10AgIN4O6 (MW ¼ 553.02): C 28.23, H 1.82,
N 10.13%. Found: C 28.45, H 1.68, N 10.35%. FTIR (cmꢀ1): 3278
(m), 3240(m), 3056(m), 2948(m), 2361(m), 2342(m), 1704(s), 1668
(s), 1637(m), 1578(s), 1532(m), 1483(s), 1421(s), 1386(s), 1329(s),
1293(s), 1278(s), 1247(s), 1192(m), 1113(s), 1015(m), 951(m), 937
(m), 903(m), 881(m), 862(w), 827(m), 787(m), 723(m), 669(w),
646(m), 535(w), 509(m), 472(w), 445(w), 419(w).
Colourless crystals of 1–4 and 6–8 suitable for X-ray crystal-
lography were obtained by layering the methanol solutions of the
complexes with diethyl ether, while colourless crystals of 5 were
crystallized from a THF solution.
Thermal gravimetric analyses
Thermal gravimetric analyses (TGA) were carried out to examine
the thermal stabilities of 1–8. The samples were heated up in
nitrogen gas at 1 atm pressure with the heating rate of 10 ꢁC
minꢀ1 and finished at 900 ꢁC, ESI Fig. S1.† Complex 1 was stable
up to 230 ꢁC. The first weight loss of 44.77% (calcd 46.16%) from
230 to 300 ꢁC is due to the removal of the methyl benzoate group
{[Ag(L3)](BF4)$0.5THF}N, 5. AgBF4 (0.20 g, 1.0 mmol) and L3
(0.34 g, 1.0 mmol) were placed in a flask containing 20 mL THF.
The mixture was then stirred at room temperature for 24 h to
produce a light brown solution. The volume of the solution was
reduced and diethyl ether added to induce precipitate. The
precipitate was then collected and dried under vacuum. Yield:
0.36 g (64%, based on Ag). Anal calcd for C15H14AgBBrF4N3O3.5
(MW ¼ 566.88): C 31.78, H 2.49, N 7.41%. Found: C 31.56, H
2.23, N 7.62%. FTIR (cmꢀ1): 3337(m), 3057(m), 2957(m), 2360
(m), 2342(m), 1708(s), 1679(s), 1636(m), 1578(s), 1508(s), 1496(s),
1428(s), 1375(m), 1336(m), 1279(s), 1244(m), 1192(m), 1099(s),
1062(s), 1018(m), 905(m), 873(m), 829(m), 782(m), 726(m), 668
(m), 653(m), 540(w), 519(m), 473(m), 459(m), 445(m), 418(m).
ꢀ
of the L1 ligands and the NO3 anions. The second weight loss
from 300 to 800 ꢁC corresponds to the removal the pyrimidyl-2-
carbamyl group of the L1 ligands. Complexes 2 and 3 were stable
up to 195 and 220 ꢁC, respectivelyꢁ. The first weight loss of 20.15%
(calcd 21.40%) from 195 to 220 C and 19.81% (calcd 19.99%)
from 220 to 245 ꢁC, for 2 and 3, respectively, are due to the
removal methyl benzoate group of the ligands. The second
weight loss of 18.83% (calcd 19.64%) from 220 to 290 ꢁC and
18.08% (calcd 18.34%) from 245 to 315 ꢁC corresponds to the
removal of two coordinated NO3ꢀ anions. The third weight loss
from 290 to 800 ꢁC and 315 to 800 ꢁC corresponds to the removal
5-halopyrimidin-2-ylcarbamyl group of the ligands. The TGA
curve of 4 shows the first weight loss of 23.81% (calcd 24.44%)
from 210 to 240 ꢁC, due to the removal methyl benzoate group of
the L4 ligands and the second weight loss 10.14% (calcd 11.21%)
from 240 to 280 ꢁC corresponds to the removal the coordinated
[Ag2(L4)4](BF4)2$2CH3OH, 6. AgBF4 (0.10 g, 0.5 mmol) and
L4 (0.38 g, 1.0 mmol) were placed in a flask containing 20 mL
MeOH. The mixture was then stirred at room temperature for 24
h to produce a white suspension. The suspension was filtered out
and the volume of the solution reduced. Diethyl ether was added
to induce precipitate, which was then collected and dried under
vacuum. Yield: 0.28 g (56%, based on Ag). Anal calcd for
C27H24AgBF4I2N6O7 (MW ¼ 993.00): C 32.66, H 2.44, N 8.46%.
Found: C 32.37, H 2.01, N 8.21%. FTIR (cmꢀ1): 3316(m), 3048
(m), 2952(m), 2360(m), 2343(m), 1724(s), 1707(s), 1685(s), 1671
(s), 1576(s), 1558(m), 1508(s), 1490(s), 1457(m), 1425(s), 1367(m),
1337(m), 1282(s), 1242(m), 1192(m), 1109(s), 1017(m), 967(m),
903(w), 872(m), 826(m), 787(m), 719(m), 668(w), 642(m), 507(m),
492(w), 473(w), 459(m), 444(m), 420(w).
ꢀ
ꢁ
NO3 anions. The third weight loss from 280 to 800 C corre-
sponds to the removal the 5-iodopyrimidin-2-ylcarbamyl group
of the L4 ligands. For 5, the first weight loss of 15.76% (calcd
16.35%) which occurred in the temperature range 233–280 ꢁC can
ꢀ
be ascribed to the removal of the uncoordinated BF4 anions.
ꢁ
The second weight loss from 330 to 800 C corresponds to the
removal the L3 ligands. The TGA curves of 6, 7 and 8 show the
first weight loss of 7.87% (calcd 9.03%) from 198 to 207 ꢁC,
13.94% (calcd 14.22%) from 212 to 245 ꢁC and 19.86% (calcd
This journal is ª The Royal Society of Chemistry 2011
CrystEngComm, 2011, 13, 4121–4130 | 4123