3744 Inorganic Chemistry, Vol. 39, No. 17, 2000
Zhou et al.
mL). The mixture was heated overnight at 60 °C, then EtOH (60 mL)
was added. The mixture was placed in a fume hood for 12 h during
which time a crystalline solid formed (2.08 g, 45.9%). Anal. Found:
C, 58.48; H, 4.32; N, 4.71; Zn, 7.33%. Calcd for Zn2C86H78Cl4N6O18:
C, 58.82; H, 4.48; N, 4.79; Zn, 7.45%. H NMR (in DMSO-d6): δ
(ppm) 7.74(H-13,14), 7.72(15,16), 7.12(H-3), 7.01(H-4), 6.78(H-6),
H, 3.95; N, 3.04; Zn, 8.38%. Calcd for ZnC38H34Cl2N2O10: C, 56.00;
H, 4.20; N, 3.44; Zn, 8.02%. H NMR (in DMSO-d6): δ (ppm) 7.73-
(H-13,14), 7.71(15,16), 7.11(H-3), 6.99(H-4), 6.76(H-6), 3.81(H-9),
3.44(H-18), 2.25(H-19).
1
1
Aqua(methylamine)bis(η2-O,O′-Indo)zinc(II)‚1.25H2O, [Zn(Indo)2-
(NH2Me)(OH2)]‚1.25H2O, 11. [Zn(Indo)2(OH2)2] was slowly added
to a THF solution of methylamine (2.0 M, 15 mL) until a saturated
solution was formed. The mixture was stirred for 1.5 h at 45 °C, then
set aside in a fume hood overnight. The white precipitate was collected
by filtration, washed with a small amount of EtOH, and air-dried. Anal.
Found: C, 54.75; H, 4.19; N, 4.95; Zn, 7.73%. Calcd for ZnC39H37-
3.82(H-9), 3.51(H-18), 2.27(H-19).
cis-Bis(ethanol)bis(η2-O,O′-Indo)zinc(II), cis-[Zn(Indo)2(EtOH)2],
4. A solution of Zn(OAc)2‚2H2O (2.16 g, 9.84 mmol) in DMA (10
mL) was added slowly to a solution of IndoH (7.26 g, 20.29 mmol) in
DMA (10 mL). The mixture was stirred and heated at 50 °C overnight.
The resultant yellow solution was cooled to room temperature, at which
time ethanol (100 mL) was added. When the solution stood for a few
days, a pale-yellow crystalline solid formed, which was collected by
filtration under vacuum, washed with absolute ethanol (ca. 50 mL),
and air-dried (7.43 g, 87%). Anal. Found: C, 57.49; H, 4.34; N, 3.29;
Zn, 7.93%. Calcd for ZnC42H42Cl2N2O10: C, 57.91; H, 4.86; N, 3.22;
1
Cl2N3O9‚1.25H2O: C, 55.07; H, 4.68; N, 4.94; Zn, 7.69%. H NMR
(in DMSO-d6): δ (ppm) 7.7(H-13,14), 7.71(15,16), 7.12(H-3), 7.03-
(H-4), 6.75(H-6), 3.82(H-9), 3.43(H-18), 2.26(H-19).
Aquaimidazolebis(η2-O,O′-Indo)zinc(II)‚1.25H2O, [Zn(Indo)2-
(Im)(OH2)]‚1.25H2O, 12. [Zn(Indo)2(OH2)2] (0.40 g, 0.49 mmol) was
slowly added to a solution of imidazole (0.034 g, 0.50 mmol) in MeOH
(10 mL). The resultant mixture was stirred for 2 h, then filtered and
washed with a small amount of MeOH, and air-dried. Anal. Found:
C, 55.20; H, 4.30; N, 6.16; Zn, 6.89%. Calcd for ZnC41H36Cl2N4O9‚
1.25H2O: C, 55.48; H, 4.37; N, 6.31; Zn, 7.37%. 1H NMR (in DMSO-
d6): δ (ppm) 7.75(H-13,14), 7.73(15,16), 7.14(H-3), 7.04(H-4), 6.78(H-
6), 3.80(H-9), 3.41(H-18), 2.28(H-19).
1
Zn, 7.51%. H NMR (in DMSO-d6): δ (ppm) 7.74(H-13,14), 7.72-
(15,16), 7.13(H-3), 7.02(H-4), 6.78(H-6), 3.83(H-9), 3.43(H-18), 2.27-
(H-19).
cis-Bis(methanol)bis(η2-O,O′-Indo)zinc(II), cis-[Zn(Indo)2(MeOH)2],
5. To a solution of IndoH (3.61 g, 10.09 mmol) in DMF (10 mL), a
solution of Zn(OAc)2‚2H2O (1.24 g, 5.65 mmol) in DMF (10 mL) was
added slowly. The mixture was stirred and heated at ca. 50 °C for 6 h
and cooled to room temperature. Then methanol (50 mL) was added.
When the solution stood overnight, colorless crystals were formed that
were collected through filtration and air-dried (3.04 g, 71.5%). Anal.
Found: C, 57.18; H, 4.26; N, 3.45; Zn 7.74%. Calcd for ZnC40H38-
Cl2N2O10: C, 56.99; H, 4.54; N, 3.32; Zn, 7.76%. 1H NMR (in DMSO-
d6): δ (ppm) 7.75(H-13,14), 7.73(15,16), 7.13(H-3), 7.02(H-4), 6.78(H-
6), 3.83(H-9), 3.44(H-18), 2.27(H-19).
Physical Methods. Infrared spectra were recorded using a KBr
matrix on a BIO-Rad Win-IR FTS-40 infrared spectrometer. Elemental
microanalyses were performed by the Department of Chemical
Engineering, University of Sydney. A Varian AA-800 air-acetylene
flame atomic absorption spectrophotometer was used for the Zn
analyses. 1H and 13C NMR spectra were recorded at room temperature
in DMF-d7, DMSO-d6, or pyridine-d5 on a Bruker AM400 spectrometer
using the solvents as internal standards but with shifts cited versus
tetramethylsilane (TMS).
X-ray Crystallographic Analyses. Crystal data and processing
parameters of complexes 1-5 are listed in Table 1. Diffraction data
were collected at 21 ( 1 °C on a Rigaku AFC7R diffractometer
employing graphite monochromated Cu KR radiation (λ ) 1.541 78
Å) from a rotating anode generator. There were no significant changes
in the intensities of three representative reflections measured every 150
reflections during the data collections for complexes 1, 2, and 4. A
generator anomaly during the data collection for complex 3 resulted in
a 30.0% increase in the reference reflections intensities, whereas the
intensities of the complex 5 standards decreased by 23.0% during the
data collection. A polynomial correction factor was accordingly applied
to the data for complexes 3 and 5. An empirical absorption correction
based on azimuthal scans of three reflections was applied to the data
for complexes 1, 3, and 5, and an analytical correction was applied to
the complex 2 and 4 data. The diffraction data were also corrected for
Lorentz and polarization effects.
Bis(1-butanol)bis(η2-O,O′-Indo)zinc(II)‚2.25H2O, [Zn(Indo)2(1-
butanol)2]‚2.25H2O, 6; Bis(2-butanol)bis(η2-O,O′-Indo)zinc(II)‚
3.25H2O, [Zn(Indo)2(2-butanol)2]‚3.25H2O, 7; and Bis(2-methyl-2-
propanol)bis(η2-O,O′-Indo)zinc(II)‚2.5H2O, [Zn(Indo)2(t-butanol)2]‚
2.5H2O, 8. Zn(OAc)2‚2H2O (0.58 g, 2.64 mmol) in the appropriate
warm butanol (20 mL) was slowly added to a warm solution of IndoH
(1.85 g, 5.17 mmol) in butanol (20 mL). The mixture was heated at
ca. 60 °C for 3 h, during which time a precipitate rapidly formed. Upon
cooling to room temperature, the mixture was then filtered and the
isolated solid was washed with a small amount of EtOH and finally
air-dried. For 6, yield 88.4%. Anal. Found: C, 56.71; H, 4.99; N, 2.85;
Zn 7.11%. Calcd for ZnC46H50Cl2N2O10‚2.25H2O: C, 57.09; H, 5.68;
N, 2.89; Zn, 7.05%. 1H NMR (in DMSO-d6): δ (ppm) 7.76(H-13,14),
7.73(15,16), 7.13(H-3), 7.02(H-4), 6.78(H-6), 3.83(H-9), 3.46(H-18),
2.27(H-19). For 7, yield 80.0%. Anal. Found: C, 55.57; H, 5.43; N,
2.71; Zn 7.52%. Calcd for ZnC46H50Cl2N2O10‚3.25H2O: C, 56.05; H,
1
5.78; N, 2.84; Zn, 7.05%. H NMR (in DMSO-d6): δ (ppm) 7.75(H-
All calculations were undertaken with the teXsan20 crystallographic
software package. Neutral atom scattering factors were taken from
Cromer and Waber.21 Anomalous dispersion effects were included in
Fc,22 and the values for ∆f ′ and ∆f ′′ were those of Creagh and
McAuley.23 The values for the mass attenuation coefficients were those
of Creagh and Hubbell.24 The structures were solved by direct methods25
and expanded using Fourier techniques.26 The least-squares planes were
13,14), 7.74(15,16), 7.13(H-3), 7.01(H-4), 6.78(H-6), 3.83(H-9), 3.49-
(H-18), 2.27(H-19). For 8, yield 68.6%. Anal. Found: C, 56.49; H,
5.05; N, 2.81; Zn 7.12%. Calcd for ZnC46H50Cl2N2O10‚2.5H2O: C,
56.83; H, 5.70; N, 2.88; Zn, 7.05%. 1H NMR (in DMSO-d6): δ (ppm)
7.75(H-13,14), 7.73(15,16), 7.13(H-3), 7.01(H-4), 6.78(H-6), 3.82(H-
9), 3.46(H-18), 2.27(H-19).
Bis(dimethyl sulfoxide)bis(η2-O,O′-Indo)zinc(II), [Zn(Indo)2-
(DMSO)2], 9. This complex was prepared in a manner similar to that
of 1 except that dimethyl sulfoxide was used as the solvent. The mixture
was heated with stirring for 7 h, then cooled to room temperature. The
precipitate that formed after a few weeks was collected by filtration
and washed with ethanol, then air-dried (0.95 g, 21.1%). Anal. Found:
C, 53.48; H, 4.49; N, 3.09; Zn, 6.84%. Calcd for ZnC42H42-
Cl2N2O10S2: C, 53.94; H, 4.53; N, 3.00; Zn, 6.99%. 1H NMR (in
DMSO-d6): δ (ppm) 7.71(H-13,14), 7.69(15,16), 7.09(H-3), 6.97(H-
4), 6.74(H-6), 3.79(H-9), 3.45(H-18), 2.23(H-19).
Diaquabis(η2-O,O′-Indo)zinc(II), [Zn(Indo)2(OH2)2], 10. To a
solution of IndoH (3.00 g, 8.38 mmol) in NaOH (0.1 M, 50 mL) a
solution of Zn(OAc)2‚2H2O (0.90 g, 4.10 mmol) in water (10 mL) was
slowly added. The mixture was stirred and heated at 60 °C for 3 h,
during which time a pale-yellow precipitate formed. After the mixture
was cooled, the precipitate was collected by filtration, washed with
water and EtOH, and air-dried (2.91 g, 89.3%). Anal. Found: C, 55.64;
(20) TEXSAN: Crystal Structure Analysis Package, Molecular Structure
Corporation; The Woodlands, TX, 1985-1992.
(21) Cromer, D. T.; Waber, J. T. International Tables for X-ray Crystal-
lography; The Kynoch Press: Birmingham, England, 1974; Vol. 4.
(22) Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, 781-782.
(23) Creagh, D. C.; McAuley, W. J. International Tables for Crystal-
lography; Wilson, A. J. C., Ed.; Kluwer Academic Publishers: Boston,
1992; Vol. C, Table 4.2.6.8, pp 219-222.
(24) Creagh, D. C.; Hubbell, J. H. International Tables for Crystallography;
Wilson, A. J. C., Ed.; Kluwer Academic Publishers: Boston, 1992;
Vol. C, Table 4.2.4.3, pp 200-206.
(25) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl.
Crystallogr. 1993, 26, 343-350.
(26) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; de
Gelder, R.; Israel, R.; Smits, J. M. M. The DIRDIF-94 program system;
Technical Report; Crystallography Laboratory, University of
Nijmegen: The Netherlands, 1994.