(Flavonolato)copper Isoindoline Complexes
Inorganic Chemistry, Vol. 39, No. 19, 2000 4225
Found: C, 65.84; H, 3.64; N, 11.46. Recrystallization from acetonitrile
gave green crystals of CuII(fla)(ind)‚CH3CN. The acetonitrile solution
produced crystals suitable for X-ray analysis upon standing at room
temperature for a few days.
here the preparation and characterization of several copper(I)
and copper(II) flavonolate complexes with the ligand 1,3-bis-
(2-pyridylimino)isoindoline and its deprotonated form and their
oxygenations to the corresponding copper depside (O-benzoyl-
salicylic acid, O-bs) complexes. The crystal structures of a
copper(II) flavonolate complex with indH and that of an (O-
benzoylsalicylato)copper(I) complex are also reported.
(d) CuI(indH)(O-bs) (7). [CuI(mes)]5 (0.183 g, 0.2 mmol), O-
benzoylsalicylic acid (0.242 g, 1 mmol), and indH (0.300 g, 1 mmol)
were dissolved in 60 mL of acetonitrile, and the mixture was stirred
under an atmosphere of Ar for 4 h. A small quantity of a brown
precipitate formed, which was filtered off, and the filtrate was allowed
to stand at room temperature for 2 days. Brown crystals formed, which
were filtered off, washed with ether, and dried under vacuum. The
product was identified as CuI(indH)(O-bs). Yield: 72%. The filtrate
produced crystals suitable for X-ray analysis upon standing at room
temperature for a few days. Mp: 275 °C dec. IR (Nujol): 1666, 1634,
1741, 1578, 1380, 1009 cm-1. UV-vis (DMF), λmax/nm (ꢀ/M-1 cm-1):
272 (10 965), 309 (10 471), 334 (10 471), 421 sh (10 965), 447 (9333).
Anal. Calcd for C32H22N5O4Cu: C, 63.62; H, 3.67; N, 11.59. Found:
C, 63.34; H, 3.54; N, 11.22.
(e) CuII(ind)(O-bs) (8). Method A. [CuI(mes)]5 (0.183 g, 0.2 mmol),
O-benzoylsalicylic acid (0.242 g, 1 mmol), and indH (0.300 g, 1 mmol)
were dissolved in 50 mL of acetonitrile, and the mixture was stirred
under an atmosphere of O2 for 3 h. A green precipitate formed, which
was filtered off, washed with ether, and dried under vacuum. It was
identified as CuII(ind)(O-bs). Yield: 85%. Mp: 253 °C. µ ) 1.87 µB.
IR (Nujol): 1742, 1636, 1581, 1387 cm-1. Anal. Calcd for C32H21N5O4-
Cu: C, 63.73; H, 3.51; N, 11.61. Found: C, 63.45; H, 3.57; N, 11.36.
UV-vis (DMF), λmax/nm (ꢀ/M-1 cm-1): 309 (912), 333 (955), 417
(1096), 440 (891.3), 816 (14). Attempts to obtain suitable single crystals
of CuII(ind)(O-bs) for X-ray analysis failed.
Method B. CuII(fla)(ind) (0.30 g, 0.5 mmol) in acetonitrile (30 mL)
was treated with dioxygen (0.1 MPa) at 80 °C for 30 h. The green
precipitate was filtered off, washed with acetonitrile, and dried under
vacuum (0.39 g, 65%).
Method C. CuI(fla)(indH) (0.30 g, 0.5 mmol) in acetonitrile (25
mL) was treated with dioxygen (0.1 MPa) at 80 °C for 25 h. The green
precipitate was filtered off, washed with acetonitrile, and dried under
vacuum (0.30 g, 50%).
Crystallographic Data Collections and Refinements of the
Structures. (a) CuII(fla)(ind)‚CH3CN (6‚CH3CN). The diffraction
intensities of an approximately 0.30 × 0.30 × 0.30 mm crystal were
collected with graphite-monochromatized Mo KR radiation using a
Siemens (Nicolet Syntex) R3m/V diffractometer and the ω-scan
technique. A total of 4378 reflections were collected, of which 4378
(Rint ) 0.000) were considered unique and 2397 were considered
observed (I > 2σ(I)). An experimental absorption correction was applied
(æ scan; ∆æ ) 10°), and the data were corrected for Lorentz and
polarization effects. The cell parameters were obtained from the least-
squares refinement of the setting angles of 25 carefully centered
reflections with 2θ in the range 4.4-47.6°.
The structure was solved by direct methods. Final cycles of
refinement converged with discrepancy indices of R ) 0.0878 and
Rw ) 0.1495. Form factors were taken from the usual sources.29 All
calculations were performed with SHELXL9330 and SHELXS8631
crystallographic software packages.
Experimental Section
Materials. Solvents used for the reactions were purified by literature
methods22 and stored under argon. 3-Hydroxyflavone,23 1,3-bis(2-
pyridylimino)isoindoline,24 O-benzoylsalicylic acid,25 mesitylcopper-
27
(I),26 and [CuI(CH3CN)4]ClO4 were prepared by literature methods.
Conventional Schlenk-type inert gas techniques were used.28
Physical Measurements. Electronic spectra were recorded with a
Shimadzu UV-160 spectrometer. Infrared spectra were obtained for
Nujol mulls using a Specord IR-75 (Carl Zeiss) spectrometer. Magnetic
susceptibilities were determined at room temperature on a Bruker B-E
10B8 magnetic balance. EPR spectra were obtained with a JEOL JES-
FE3X spectrometer. Microanalyses were carried out by the Microana-
lytical Service of the University of Veszpre´m. GC analyses were
performed on an HP 5830A gas chromatograph equipped with a flame
ionization detector and a CP SIL8CB column. GC-MS measurements
were recorded on an HP 5890 II, 5971 GC-MSD gas chromatograph
at 75 eV.
Syntheses of the Complexes. (a) [CuII(fla)(indH)]ClO4 (4).
[CuI(CH3CN)4]ClO4 (0.328 g, 1 mmol), flavonol (0.238 g, 1 mmol),
and indH (0.300 g, 1 mmol) were dissolved in 60 mL of acetonitrile,
and the mixture was stirred under an atmosphere of O2 for 4 h. A green
precipitate formed, which was filtered off, washed with ether, and dried
under vacuum. It was identified as [CuII(fla)(indH)]ClO4. Yield: 90%.
Mp: 265-267 °C. IR (Nujol): 3276, 3209, 1661, 1632, 1562, 1107,
611 cm-1. UV-vis (MeCN), λmax/nm: 240, 306, 334, 417, 440, 631,
797. Anal. Calcd for C33H22N5O7CuCl: C, 56.65; H, 3.17; N, 10.01.
Found: C, 56.24; H, 3.06; N, 9.62. µ ) 2.10 µB. Recrystallization of
[CuII(fla)(indH)]ClO4 from acetonitrile gave green crystals of CuII(fla)-
(ind).
(b) CuI(fla)(indH) (5). [CuI(mes)]5 (0.183 g, 0.2 mmol), flavonol
(0.238 g, 1 mmol), and indH (0.300 g, 1 mmol) were dissolved in 60
mL of acetonitrile, and the mixture was stirred under an atmosphere
of argon for 8 h. A brown precipitate formed, which was filtered off,
washed with ether, and dried under vacuum. It was identified as CuI-
(fla)(indH). Yield: 88%. Mp: >300 °C. IR (Nujol): 1654, 1627, 1580,
1009 cm-1. UV-vis (DMF), λmax/nm (ꢀ/M-1 cm-1): 277 (5754), 418
(5248), 447 (9333). Anal. Calcd for C33H22N5O3Cu: C, 66.04; H, 3.69;
N, 11.67. Found: C, 65.82; H, 3.59; N, 11.48.
(c) CuII(fla)(ind) (6). [CuI(mes)]5 (0.183 g, 0.2 mmol), flavonol
(0.238 g, 1 mmol), and indH (0.300 g, 1 mmol) were dissolved in 60
mL of dichloromethane, and the mixture was stirred under an
atmosphere of O2 for 4 h. The solution was initially brown, but it
became green after approximately 5 min and a green solid deposited.
The solid was filtered off, washed with ether, and dried under vacuum.
Yield: 85%. The filtrate gave a small quantity of green crystals of
CuII(fla)(ind) on standing overnight, which were, however, unsuitable
for crystallographic characterization. Mp: 306-308 °C. µ ) 1.86 µB.
IR (Nujol): 1636, 1574, 1001 cm-1. UV-vis (MeCN), λmax/nm (ꢀ/
M-1 cm-1): 307 (16 785), 334 (17 103), 415 (14 698), 444 sh (9073),
631 (152). Anal. Calcd for C33H21N5O3Cu: C, 66.16; H, 3.53; N, 11.69.
A summary of the crystal data and X-ray experimental details is
given in Table 1.
(b) CuI(indH)(O-bs) (7). The diffraction intensities of an ap-
proximately 0.20 × 0.40 × 0.40 mm crystal were collected with
graphite-monochromatized Mo KR radiation using a Siemens (Nicolet
Syntex) R3m/V diffractometer and the ω-scan technique. A total of
4530 reflections were collected, of which 4171 (Rint ) 0.0335) were
considered unique and 3207 were considered observed (I > 2σ(I)). An
experimental absorption correction was applied (æ scan), and the data
were corrected for Lorentz and polarization effects. The cell parameters
(22) Perrin, D. D.; Armarego, W. L.; Perrin, W. L. Purification of
Laboratory Chemicals, 2nd ed.; Pergamon: New York, 1990.
(23) Nishinaga, A.; Tojo, T.; Tomita, H.; Matsuura, T. J. Chem. Soc., Perkin
Trans. 1 1979, 2511.
(24) Siegl, W. O. J. Org. Chem. 1977, 42, 1872.
(25) Einhorn, A.; Rothlauf, L.; Seuffert, R. Chem. Ber. 1911, 44, 3309.
(26) Tsuda, T.; Yazawa, T.; Watanabe, K.; Fujii, T.; Saegusa, T. J. Org.
Chem. 1981, 46, 192.
(27) Hathaway, B. J.; Holah, D. G.; Postlethwaite, J. D. J. Chem. Soc.
1961, 3215.
(29) International Tables for X-ray Crystallography; Kynoch Press: Bir-
mingham, U.K., 1974; Vol. 4.
(30) Sheldrick, G. M. SHELXL93: Program for Crystal Structure Refine-
ment. University of Go¨ttingen, 1993.
(28) Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air-sensitiVe
(31) Sheldrick, G. M. SHELXS86: Program for Crystal Structure Solution.
University of Go¨ttingen, 1990.
Compounds; John Wiley & Sons: New York, 1986.