10
R. Křikavová et al. / Journal of Inorganic Biochemistry 163 (2016) 8–17
427m, 409w, 389w, 331w, 307m, 272m, 258m, 249m. UV–Vis (metha-
nol, 10−5 M): λmax (nm) (εmax × 104 M−1 cm−1) 272 (31.00), 294
(18.70), 340 (16.00), 431 (7.60). UV–Vis (nujol): λmax (nm) 275, 309,
363, 458.
(methanol, 10−5 M): λmax (nm) (εmax × 104 M−1 cm−1) 272 (30.00),
294 (17.60), 358 (19.00), 420sh (11.00). UV–Vis (nujol): λmax (nm)
280, 368, 450sh.
[Cu(L8)(phen)]NO3 (8): Yield: 83%, Anal. calc. for C29H24N4O5Cu
(Mr = 572.07): C, 60.89; H, 4.23; N, 9.79%. Found: C, 60.54; H, 4.26; N,
[Cu(L2)(phen)]NO3 (2): Yield: 56%, Anal. calcd. for C29H23N3O7Cu
(Mr = 589.05): C, 59.13; H, 3.93; N, 7.13%. Found: C, 58.81; H, 4.17; N,
9.59%. ESI+ MS (methanol, m/z): 243.0 (calc 243.0) [Cu(phen)]+
,
6.86%. ESI+ MS (methanol, m/z): 243.0 (calc 243.0) [Cu(phen)]+
,
509.1 (calc. 509.1) [M-NO3]+. Λm (Acetonitrile, 25 °C, S cm2 mol−1):
128 (electrolyte 1:1). IR (νATR/cm−1): 3061m, 2901m, 2821m, 2644m,
1590s, 1526s, 1486s, 1433m, 1364m, 1333s, 1307s, 1178m, 1150s,
1030m, 976m, 842m, 815m, 774m, 716m, 654w, 574s, 516m, 501m,
477m, 453m, 433m, 397m, 301m, 275m, 245m, 226m, 202m. UV–Vis
(methanol, 10−5 M): λmax (nm) (εmax × 104 M−1 cm−1) 272 (38.80),
294sh (18.70), 483 (31.80). UV–Vis (nujol): λmax (nm) 273, 429, 533.
526.1 (calc. 526.1) [M-NO3]+. Λm (Acetonitrile, 25 °C, S cm2 mol−1):
139 (electrolyte 1:1). IR (νATR/cm−1): 3445m, 3069m, 2981m, 2941m,
2842m, 1595s, 1541s, 1486s, 1425m, 1374s, 1319s, 1286s, 1256m,
1205s, 1172s, 1135s, 1105m, 1014m, 969m, 840m, 801m, 719m,
603w, 518s, 494m, 486m, 463w, 429m, 401m, 373m, 309m,
273m, 265m, 248m. UV–Vis (methanol, 10−5 M): λmax (nm)
(εmax × 104 M−1 cm−1) 272 (37.00), 294 (23.00), 362 (24.00), 412sh
(14.00). UV–Vis (nujol): λmax (nm) 273, 300, 368, 450sh.
2.3. General methods for characterization
[Cu(L3)(phen)]NO3 (3): Yield: 68%, Anal. calcd. for C28H21N3O6Cu
(Mr = 559.03): C, 60.16; H, 3.79; N, 7.52%. Found: C, 60.35; H, 3.79; N,
Elemental analysis (C, H, N) was performed on a Flash 2000 CHNS El-
emental Analyser (Thermo Scientific). Infrared spectra were measured
using a Nexus 670 FT-IR (Thermo Nicolet) spectrometer using an ATR
technique in the region 400–4000 cm−1. The intensities of bands are
defined as s = strong, m = medium and w = weak. Electrospray ioni-
zation mass spectrometry (ESI+ MS) was performed for methanol solu-
tions of complexes 1–8 using an LCQ Fleet Ion Trap mass spectrometer
(Thermo Scientific) in the positive ionization mode. 1H NMR spectra of
the chalcone ligands in CDCl3 were measured at 298 K on a Varian
400 MHz NMR spectrometer using tetramethylsilane (SiMe4) as a refer-
ence standard. Thermogravimetric (TG) and differential thermal (DTA)
analyses were performed on a thermal analyser Exstar TG/DTA 6200
7.24%. ESI+ MS (methanol, m/z): 243.0 (calc. 243.0) [Cu(phen)]+
,
496.1 (calc. 496.1) [M-NO3]+. Λm (Acetonitrile, 25 °C, S cm2 mol−1):
129 (electrolyte 1:1). IR (νATR/cm−1): 3057m, 3008m, 2971m, 2932m,
2838w, 1621m, 1600m, 1542m, 1505s, 1425m, 1391m, 1358m, 1298s,
1278s, 1248s, 1156m, 1028m, 969m, 847m, 833m, 810w, 756m,
717m, 654w, 575s, 561m, 533m, 521s, 496m, 487m, 462m, 430m,
375m, 325w, 307m, 266m. UV–Vis (methanol, 10−5 M): λmax (nm)
(εmax × 104 M−1 cm−1) 272 (34.00), 294 (18.00), 367 (23.30), 434
(10.00). UV–Vis (nujol): λmax (nm) 274, 356, 460sh.
[Cu(L4)(phen)]NO3 (4): Yield: 52%, Anal. calcd. for C28H20N4O9Cu
(Mr = 620.03): C, 54.24; H, 3.25; N, 9.04%. Found: C, 53.97; H, 3.65; N,
8.72%. ESI+ MS (methanol, m/z): 243.0 (calc 243.0) [Cu(phen)]+
,
(Seiko instruments Inc.) in a dynamic air atmosphere (100 mL min−1
)
557.0 (calc. 557.1) [M-NO3]+. Λm (Acetonitrile, 25 °C, S cm2 mol−1):
132 (electrolyte 1:1). IR (νATR/cm−1): 3065m, 2940w, 2838w, 2734w,
1609m, 1543m, 1488m, 1380m, 1338m, 1274m, 1224s, 1142m,
1107m, 1082m, 1016m, 973w, 848m, 825w, 741w, 719m, 602w,
577m, 561m, 497m, 488m, 460s, 433s, 417m, 371w, 344m, 311s,
277m, 192m. UV–Vis (methanol, 10−5 M): λmax (nm) (εmax × 104 M−1-
cm−1) 272 (32.00), 294 (25.00), 392 (18.70), 451 (21.60). UV–Vis
(nujol): λmax (nm) 276, 380.
between room temperature (ca. 25 °C) and 600 °C with a gradient of
2.5 °C min−1. Electronic and diffuse-reflectance spectra were recorded
on a Perkin-Elmer Lambda 40 spectrometer. Conductivity measure-
ments of
1 mM acetonitrile, nitromethane, methanol, N,N-
dimethylformamide (DMF) and dimethyl sulphoxide (DMSO) solutions
of 1–8 were measured on a Cond 340i/SET conductometer (WTW) at
25 °C.
[Cu(L5)(phen)]NO3 (5): Yield: 78%, Anal. calcd. for C30H25N3O8Cu
(Mr = 619.05): C, 58.20; H, 4.07; N, 6.79%. Found: C, 57.93; H, 3.95; N,
2.4. X-ray crystallography
6.48%. ESI+ MS (methanol, m/z): 243.0 (calc 243.0) [Cu(phen)]+
,
Single crystal X-ray data of the first pseudopolymorph of complex 5,
obtained by the recrystallization from methanol (5a), was collected on a
Rigaku HighFlux HomeLab™ universal dual wavelength (Mo–Kα and
Cu–Kα) single crystal diffractometer with a Rigaku Saturn724+
(2 × 2 bin mode) detector. The diffractometer was equipped with a
Eulerian 3 circle goniometer and measurements were performed at
120(2) K using Mo–Kα radiation. Data collection, data reduction and
cell parameters refinements were performed by the XDS software pack-
age [37,38]. X-ray data of the second pseudopolymorph of complex 5,
recrystallized from DMF (5b), was obtained on a Bruker D8 Quest dif-
fractometer equipped with Photon 100 CMOS detector, using Mo-Kα
radiation at 120(2) K. Data collection, data reduction, and cell parame-
ters refinements were performed by the Bruker Apex III software pack-
age [39]. The molecular structures were solved by direct methods
(SHELXS) and all non-hydrogen atoms were refined anisotropically on
F2 using full-matrix least-squares procedure in SHELXL-2014 [40]. Hy-
drogen atoms were found in differential Fourier maps and their param-
eters were refined using a riding model. Molecular graphics were
prepared and some structural parameters were interpreted in DIA-
MOND, release 3.2i [41] and Mercury, ver. 3.3. [42] The crystal data
and structure refinement are given in Table 1.
556.1 (calc. 556.1) [M-NO3]+. Λm (Acetonitrile, 25 °C, S cm2 mol−1):
135 (electrolyte 1:1). IR (νATR/cm−1): 3056w, 3001w, 2940m, 2834m,
2639w, 1621m, 1603m, 1578m, 1545m, 1499s, 1460m, 1418m, 1317s,
1244m, 1203m, 1186m, 1119s, 1023m, 999m, 969m, 823m, 765m,
717m, 570s, 523s, 503m, 486m, 431m, 327w, 308m, 272m, 196m.
UV–Vis (methanol, 10−5 M): λmax (nm) (εmax × 104 M−1 cm−1) 272
(36.60), 294 (19.90), 361 (22.00), 430 (8.80). UV–Vis (nujol): λmax
(nm) 275, 376, 470sh.
[Cu(L6)(phen)]NO3 (6): Yield: 64%, Anal. calcd. for C27H19N3O6Cu
(Mr = 545.00): C, 59.50; H, 3.51; N, 7.71%. Found: C, 59.27; H, 3.35; N,
7.44%. ESI+ MS (methanol, m/z): 243.0 (calc 243.0) [Cu(phen)]+
,
482.0 (calc. 482.0) [M-NO3]+. Λm (Acetonitrile, 25 °C, S cm2 mol−1):
135 (electrolyte 1:1). IR (νATR/cm−1): 3061m, 2943m, 2717m, 1614m,
1540s, 1505s, 1457m, 1301s, 1258m, 1196s, 1152s, 1022m, 981m,
906w, 843m, 751m, 717m, 579s, 560w, 538m, 591m, 464m, 432m,
391w, 325m, 308m, 271m, 211m. UV–Vis (methanol, 10−5 M): λmax
(nm) (εmax × 104 M−1 cm−1) 272 (27.00), 294 (16.20), 340 (15.00).
UV–Vis (nujol): λmax (nm) 280, 300sh, 378, 460sh.
[Cu(L7)(phen)]NO3 (7): Yield: 51%, Anal. calcd. for C31H27N3O9Cu
(Mr = 649.10): C, 57.36; H, 4.19; N, 6.47%. Found: C, 57.12; H, 4.28; N,
6.36%. ESI+ MS (methanol, m/z): 243.0 (calc 243.0) [Cu(phen)]+
,
586.1 (calc. 586.1) [M-NO3]+. Λm (Acetonitrile, 25 °C, S cm2 mol−1):
142 (electrolyte 1:1). IR (νATR/cm−1): 3418w, 3050w, 2985m, 2943m,
2839m, 1603m, 1580m, 1543m, 1488m, 1453m, 1417m, 1336s,
1274m, 1220s, 1122m, 1041w, 970m, 848m, 720m, 586s, 522m, 484s,
462m, 432m, 413m, 388m, 309m, 275m, 245m, 197m. UV–Vis
2.5. In vitro cytotoxicity (MTT test)
In vitro cytotoxicity was studied by the MTT assay (MTT = 3-(4,5-di-
methylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) on human oste-
osarcoma (HOS; ECACC No. 87070202), human breast adenocarcinoma