Article
Crystal Growth & Design, Vol. 10, No. 12, 2010 5035
and the chemical shifts were reported in ppm with respect to the
reference standards. High resolution mass spectra were measured
on a Finnigan GC-MS-4021 spectrometer. X-ray photoelectron
spectroscopy (XPS) analysis was performed on a Kratos Axis Ultra
DLD multi-technique spectrometer with a monochromated Al-Ka
X-ray source. Variable-temperature magnetic susceptibilities were
measured by using a MPMS-7 SQUID magnetometer. Diamagnetic
corrections were made with Pascal’s constants for all constituent
atoms. Abbreviations: DMF=N,N-dimethylformamide, DMSO =
dimethyl sulfoxide, HL4 =3,5-bis(2-pyrazinyl)-1,2,4-triazole-4-yl-
N-pyrazinamide, H3TMA = trimesic acid.
room temperature at a rate of 5 °C/h. The resulting crystalline
products were isolated by filtration, washed with a small amount of
water, and dried in air.
[CoIII2(L3)3](H2O)7.5 (4). Starting reagents: L2 (24 mg, 0.1 mmol)
and Co(NO3)2 6H2O (29 mg, 0.1 mmol). Dark-red lamellar crystals
were obtained in 21% yield (7 mg, based on L2). Anal. Calcd for
3
C
30H33Co2N18O13.5: C, 36.78; H, 3.40; N, 25.74%. Found: C, 36.56;
H, 3.72; N, 25.87%. IR (cm-1): 3425bs, 3063s, 1638vs, 1586s,
1470w, 1426m, 1353s, 1285m, 1169m, 1055m, 949w, 864m, 777w,
595w, 502w.
[Co(L1)2(SCN)2(H2O)2](L1)2(H2O)6 (5). Starting reagents: L2
General Synthetic Procedure for Condition I. A mixture of the
starting reagents in H2O-DMF (v/v = 1:1, 10 mL) was placed into
a Parr Teflon-lined stainless steel vessel (20 mL) under autogenous
pressure, which was heated at 60 °C for 48 h and then cooled to room
temperature at a rate of 5 °C/h. The resulting crystalline products
were isolated by filtration, washed with a small amount of water,
and dried in air.
(24 mg, 0.1 mmol), NH4SCN (8 mg, 0.1 mmol), and Co(NO3)2
3
6H2O (29 mg, 0.1 mmol). Red block crystals were obtained in 39%
yield (12 mg, based on L2). Anal. Calcd for C42H40CoN26O12S2: C,
41.21; H, 3.29; N, 29.75%. Found: C, 41.03; H, 3.19; N, 29.92%. IR
(cm-1): 3431m, 2083m, 2050vs, 1669vs, 1569m, 1503w, 1473w,
1417m, 1384m, 1311s, 1277s, 1188m, 1142vs, 1094m, 1059s, 933m,
855m, 775w, 754w, 727w, 702w, 655w, 500m, 458w.
L2. Starting reagents: L1 (23 mg, 0.1 mmol) and Zn(NO3)2 6H2O
[CuICuII(L1)(L3)(SCN)]2(DMF)2 (6a). Starting reagents: L2
(24 mg, 0.1 mmol), NH4SCN (8 mg, 0.1 mmol), and Cu(NO3)2
3
(30 mg, 0.1 mmol). Dark-brown lamellar crystals were collected in
42% yield (5 mg, based on L1). Anal. Calcd for C10H8N8: C, 50.00;
H, 3.36; N, 46.64%. Found: C, 49.86; H, 3.30; N, 46.43%. IR
(cm-1): 3319m, 3232m, 1573s, 1543m, 1464w, 1407s, 1386s, 1316w,
1291w, 1145s, 1087s, 1018vs, 971s, 863s, 754m, 702w, 583w, 489w.
1H NMR (DMSO, ppm): δ = 7.03 (s, 2H), 8.84 (s, 4H), 9.39 (s, 2H).
EI-MS: m/z 240 [M]þ.
3
3H2O (24 mg, 0.1 mmol). Red block crystals were obtained in 17%
yield (12 mg, based on L2). Anal. Calcd for C48H38Cu4N28O8S2: C,
39.67; H, 2.64; N, 26.99%. Found: C, 39.82; H, 2.46; N, 27.09%. IR
(cm-1): 3059w, 2924m, 2067s, 1657vs, 1536s, 1426w, 1427w, 1383s,
1285w, 1239w, 1157m, 1037m, 856w, 767w, 578w, 497w, 460w.
[CuICuII(L1)(L3)(SCN)]2(DMF)2(H2O)2 (6b). Starting reagents:
HL4 H2O. Starting reagents: L1 (23 mg, 0.1 mmol) and ZnSO4
7H2O (29 mg, 0.1 mmol). Colorless block crystals were collected in
38% yield (7 mg, based on L1). Anal. Calcd for C15H12
10O2: C, 49.45; H, 3.32; N, 38.45%. Found: C, 49.76; H, 3.43;
L2 (24 mg, 0.1 mmol), NH4SCN (8 mg, 0.1 mmol), and CuCl2 2H2O
3
3
3
(17 mg, 0.1 mmol). Red block crystals were obtained in 19% yield
(14 mg, based on L2). Anal. Calcd for C48H42Cu4N28O10S2: C,
38.71; H, 2.84; N, 26.33%. Found: C, 38.51; H, 2.71; N, 26.49%. IR
(cm-1): 3439s, 2921m, 2067s, 1657vs, 1538s, 1465w, 1385s, 1278w,
1193m, 1154s, 1041m, 759w, 617w, 556w, 516w, 464w.
-
N
N, 38.25%. IR (cm-1): 3509s, 3323m, 3237m, 1701vs, 1652w,
1581w, 1510s, 1462m, 1405s, 1320w, 1297w, 1163s, 1126m, 1079w,
1049w, 1017s, 975w, 921w, 858w, 815w, 751w, 699m, 637w, 570w,
488w. 1H NMR (DMSO, ppm): δ = 4.59 (s, 2H), 8.65 (s, 4H),
8.77 (s, 2H), 9.21 (s, 1H), 9.38 (s, 2H), 13.53 (s, 1H). EI-MS: m/z 346
[M]þ (HL4).
General Synthetic Procedure for Condition III. A mixture of the
starting reagents in H2O-DMF (v/v = 1:1, 10 mL) was stirred and
heated at 60 °C for 30 min. The resulting solution was cooled to
room temperature and filtered. The filtrate was allowed to stand at
room temperature, affording well-shaped single crystals suitable for
X-ray diffraction analysis upon slow solvent evaporation. The
products were isolated by filtration, washed with a small amount
of water, and dried in air.
[(H3TMA) (L2)] (1). Starting reagents: H3TMA (21 mg, 0.1
3
mmol), L1 (23 mg, 0.1 mmol), and Zn(NO3)2 6H2O (30 mg, 0.1
3
mmol). Colorless block crystals were obtained in 27% yield (6 mg,
based on L1). Anal. Calcd for C19H14N8O6: C, 50.67; H, 3.13; N,
24.88%. Found: C, 50.82; H, 3.34; N, 24.65%. IR (cm-1): 3332m,
3240w, 2801s, 2526s, 1872w, 1701vs, 1592w, 1554m, 1450m, 1412m,
1388m, 1320w, 1238vs, 1179s, 1143vs, 1095m, 1045m, 1020s, 982s,
928m, 860m, 743s, 676s, 653m, 586w, 503w. 1H NMR (DMSO,
ppm): δ=7.56 (s, 2H), 8.65 (s, 3H), 8.87 (s, 4H), 9.34 (s, 2H), 12.77 (s,
3H).
[Co(L2)2(SCN)2] (7). Starting reagents: L2 (24 mg, 0.1 mmol),
NH4SCN (8 mg, 0.1 mmol), and CoCl2 6H2O (24 mg, 0.1 mmol).
3
Red block single crystals were collected in 43% yield (14 mg, based
on L2). Anal. Calcd for C22H16CoN18S2: C, 40.31; H, 2.46; N,
38.46%. Found: C, 40.11; H, 2.59; N, 38.56%. IR (cm-1): 3273m,
3197m, 3056w, 2084vs, 1683w, 1590w, 1481w, 1442m, 1400m, 1378m,
1292w, 1183m, 1140w, 1027s, 859w, 774w, 703w, 668w, 489w.
[Mn(L2)(SCN)2(H2O)]2(H2O)2 (8). Starting reagents: L2 (24 mg,
[(H3TMA) (HL4)] H2O (2). Starting reagents: H3TMA (21 mg,
3
3
0.1 mmol), L1 (23 mg, 0.1 mmol), and ZnSO4 7H2O (29 mg,
3
0.1 mmol). Pale-red lamellar single crystals were obtained in 38%
yield (11 mg, based on L1). Anal. Calcd for C24H18N10O8: C, 50.18;
H, 3.16; N, 24.38%. Found: C, 50.36; H, 3.35; N, 24.57%. IR
(cm-1): 3257s, 3078m, 2892s, 2524m, 1710vs, 1489m, 1406s, 1258s,
1235s, 1163s, 1101s, 1051m, 1018s, 981w, 927w, 861w, 740w, 699w,
0.1 mmol), NH4SCN (8 mg, 0.1 mmol), and MnCl2 4H2O (20 mg,
3
0.1 mmol). Yellow block crystals were collected in 49% yield (11 mg,
based on L2). Anal. Calcd for C24H24Mn2N20O4S4: C, 32.22; H,
2.70; N, 31.31%. Found: C, 32.31; H, 2.55; N, 31.45%. IR (cm-1):
3456b, 3215m, 3153m, 2066vs, 1607w, 1548w, 1500m, 1478m,
1408m, 1276m, 1198m, 1133w, 1029s, 808w, 769w, 699w, 656w.
X-ray Crystallography. Single-crystal X-ray diffraction data for
all compounds were collected on a Bruker Apex II CCD diffrac-
1
672m, 584w, 522w, 479w. H NMR (DMSO, ppm): δ = 4.68 (s,
2H), 8.62 (s, 3H), 8.73 (s, 4H), 8.82 (s, 2H), 9.25 (s, 1H), 9.35 (s, 2H),
12.82 (s, 3H), 13.57 (s, 1H).
{[Cu3(L4)2(SO4)2(H2O)3](H2O)9}n (3). Starting reagents: L1 (23
˚
tometer at room temperature with Mo KR radiation (λ=0.71073 A).
mg, 0.1 mmol) and CuSO4 5H2O (25 mg, 0.1 mmol). Green block
In each case, there was no evidence of crystal decay during data
collection. A semiempirical absorption correction was applied (SADABS),
and the program SAINT was used for integration of the diffraction
profiles.15 All structures were solved by direct methods using the
SHELXS program of the SHELXTL package and refined with
SHELXL.16 The non-H atoms were modeled with anisotropic
thermal parameters and refined by full-matrix least-squares meth-
ods on F2. In general, C-bound H atoms were placed geometrically
and refined as riding, whereas O- and N-bound H atoms were first
located in difference Fourier maps, and then fixed at the calculated
sites. For 3, the hydrogen atoms for all water molecules were not
located (O22 was refined isotropically). For 4, all lattice water
moieties are located at the special positions and disordered over
two sites (see CIF for details) with pseudoisotropic restraint (ISOR)
used in the refinement. Thus, the affiliated H atoms were not
determined. For 6b, both pseudoisotropic and standard geometry
constraints were used for the lattice DMF. In addition, the lattice
3
crystals were obtained in 25% yield (8 mg, based on L1). Anal. Calcd
for C30H42Cu3N20O22S2: C, 27.94; H, 3.28; N, 21.72%. Found: C,
28.13; H, 3.15; N, 21.91%. IR (cm-1): 3435bs, 3081w, 1672s, 1624vs,
1483w, 1449w, 1418w, 1386w, 1314m, 1153m, 1044m, 992w, 858w,
756w, 717w, 619w, 512w, 464w.
[CoIII2(L3)3](H2O)7.5 (4). Starting reagents: L1 (23 mg, 0.1 mmol)
and Co(NO3)2 6H2O (29 mg, 0.1 mmol). Dark-red lamellar crystals
were obtained in 28% yield (9 mg, based on L1). Anal. Calcd for
3
C
30H33Co2N18O13.5: C, 36.78; H, 3.40; N, 25.74%. Found: C, 36.69;
H, 3.55; N, 25.89%. IR (cm-1): 3431bs, 3067m, 1638vs, 1587s,
1472w, 1426w, 1352s, 1286m, 1168s, 1055m, 952w, 862w, 777w,
594w, 504w.
General Synthetic Procedure for Condition II. A mixture of the
starting reagents in H2O-DMF (v/v = 1:1, 10 mL) was placed into
a Parr Teflon-lined stainless steel vessel (20 mL) under autogenous
pressure, which was heated at 140 °C at 72 h and then cooled to