Heterobimetallic Na–Mo and Cs–Mo 2D Networks
FULL PAPER
MoO2(C9H9ON)2]. 1H, 13C, 23Na, and 95Mo NMR spectra were
recorded in CDCl3, CD3OD, or [D6]DMSO on a Bruker AC-200
instrument. The IR spectra were recorded on a Perkin–Elmer
model 883 spectrometer. UV/vis spectra were recorded in solution
with a Shimadzu model UV-1601 spectrophotometer. For the mass
spectral measurements a methanolic solution of the compounds
was prepared and the spectra recorded on a Waters LCT mass spec-
trometer using the electrospray ionization (ES+ mode) technique.
s, 1 H), 6.85 (br. m, 1 H), 7.10 (br. m, 1 H) ppm. 13C NMR ([D6]
DMSO): δ = 29.6, 29.9, 30.1, 31.5, 31.7, 33.7, 34.4, 34.5, 51.3, 51.6,
52.7, 53.1, 121.5, 121.9, 122.5, 122.7, 123.0, 124.1, 124.3, 136.7,
136.8, 137.9, 138.3, 159.8, 159.9, 175.2, 175.3 ppm. ESI HRMS:
m/z = 936.3138 [Na2(Mo2O5L2)(H2O)2].
Reaction of 1 with CsCl. Synthesis of [Cs2(Mo2O5L2)·H2O]n (2):
Compound 1 (0.048 g, 0.025 mmol) was dissolved in methanol
(20 mL), an aqueous solution (5 mL) of CsCl (0.037 g, 0.2 mmol)
was added, and the reaction solution was stirred for 5 h. On stand-
ing for about 20 days orange crystals of 2 were obtained in 50%
yield. C34H52Cs2Mo2N2O12 (1138.5): calcd. C 35.87, H 4.60, Mo
16.85, N 2.46; found C 36.05, H 4.34, Mo 17.15, N 2.54. IR (KBr
Synthesis of {(3,5-Di-tert-butyl-2-hydroxybenzyl)amino}acetic Acid
(L): Glycine (3.00 g, 40 mmol) was dissolved in water (20 mL), a
40% aqueous formaldehyde (30 mL, 400 mmol) solution was
added, and the mixture was stirred for 20 min. An ethanolic solu-
tion (30 mL) of 2,4-di-tert-butylphenol (2.06 g, 10 mmol) was then
added dropwise and the reaction mixture was stirred for 30 min
and allowed to stand overnight. The precipitated ligand was fil-
tered, washed with water, dried, and finally recrystallized from a
mixture of methanol and dichloromethane. Yield: 2.53 g (86.5%).
C17H27NO3 (293.4): calcd. C 69.59, H 9.28, N 4.77; found C 69.25,
pellet): ν = 2960 cm–1, 1580, 1475, 1260, 906, 870, 790. UV/Vis:
˜
λmax (ε) = 356 nm (6460), 213 (27590). ESI HRMS: m/z =
1138.2913 [Cs2(Mo2O5L2)(H2O)]. 1H NMR ([D6]DMSO): δ = 1.27
(br. s, 9 H), 1.39 (br. s, 9 H), 3.28 (br. m, 2 H), 4.64 (br. s, 1 H),
6.95 (br. m, 1 H), 7.20 (br. m, 1 H) ppm.
H 9.10, N 4.46. IR (KBr pellet): ν = 2960 cm–1, 1710, 1630, 1230,
Independent Synthesis of [Cs2(Mo2O5L2)•H2O]n (2): An aqueous
solution (5 mL) of Na2MoO4·2H2O (0.061 g, 0.25 mmol) was
added to a methanolic solution (25 mL) of the ligand (0.073 g,
0.25 mmol). The solution immediately turned orange. The reaction
solution was stirred for 6 h and then CsCl (0.2524 g; 1.5 mmol) was
added and solution was stirred for a further hour. On standing for
10 days crystals of compound 2 were obtained in 60% yield.
˜
1122. UV/Vis: λmax (ε) = 280 nm (2290), 220 (7470). 1H NMR
(CDCl3): δ = 1.28 (s, 9 H), 1.37 (s, 9 H), 3.62 (s, 2 H), 4.10 (s, 2
H), 4.86 (s, 1 H), 6.79 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.4 Hz, 1
H) ppm. 13C NMR (CDCl3): δ = 29.6, 31.4, 34.2, 34.8, 52.0, 53.3,
116.8, 121.9, 122.8, 137.3, 143.5, 149.4, 172.6 ppm. MS: m/z = 293
[M+] (C17H27NO3).
Synthesis of [{Na4(H2O)4(µ-H2O)2}ʚ(Mo2O5L2)2] (1): An aqueous
solution (5 mL) of Na2MoO4·2H2O (0.121 g, 0.5 mmol) was added
to a methanolic solution (25 mL) of the ligand (0.147 g, 0.5 mmol).
The solution immediately turned orange. The solution was stirred
for 3 h and was then allowed to stand overnight. The precipitated
crystalline compound was filtered, washed 3–4 times with water,
dried in vacuo, and finally recrystallized from a mixture of meth-
anol and acetonitrile. Yield: 0.13 g (54%). C68H112Mo4N4Na4O28
(1909.3): calcd. C 42.78, H 5.91, Mo 20.10, N 2.93, Na 4.82; found
X-ray Crystallographic Study: Suitable crystals of 1 and 2 were
grown from dilute acetonitrile/MeOH and MeOH/water solutions,
respectively, at room temperature over a period of 5 to 20 days.
The single crystal data were collected on Bruker–Nonius Mach3
CAD4 X-ray diffractometer that uses graphite monochromated
Mo-Kα radiation (λ = 0.71073 Å) by the ω-scan method. No ab-
sorption correction was used. The structure was solved by direct
methods and refined by least-squares methods on F2 using
SHELX-97.[10] Non-hydrogen atoms were refined anisotropically
C 43.25, H 6.10, Mo 19.45, N 2.40, Na 4.20 (by flame photometry). and hydrogen atoms on C atoms were fixed at calculated positions
IR (KBr pellet): ν = 3433 cm–1, 2960, 1600, 1470, 1250, 1170, 920,
and refined using a riding model. The H atoms of the water mole-
cules in 1 and 2 and N atoms in 1 and 2 could not be located. The
details of crystal data are given in Table 1; selected bond lengths
are summarized in Table 2.
˜
880, 780. UV/Vis: λmax (ε) = 355 nm (11830), 270 (22950), 230
(24440). 95Mo NMR ([D6]DMSO) [reference Na2MoO4 (δ =
0 ppm)]: δ = 0.3 ppm. 23Na NMR ([D6]DMSO) [reference NaCl (δ
1
= 0 ppm)]: δ = 2.0 ppm. H NMR ([D6]DMSO): δ = 1.20 (br. s, 9
CCDC-269980 (for 1) and -269981 (for 2) contain the supplemen-
H), 1.34 (br. s, 9 H), 3.36 (br. m, 2 H), 4.25 (br. m, 2 H), 4.78 (br. tary crystallographic data for this paper. These data can be ob-
Table 1. Crystal data for [{Na4(H2O)4(µ-H2O)2}ʚ(Mo2O5L2)2] (1) and [Cs2(Mo2O5L2)·H2O]n (2).
1
2
Empirical formula
Formula mass
C68H112Mo4N4Na4O28
1909.34
C34H52Cs2Mo2N2O12
1138.47
Temperature [K]
Wavelength [Å]
293(2)
0.71073
293(2)
0.71073
Crystal system
Space group
triclinic
P1
monoclinic
C2/c
¯
a [Å]
b [Å]
c [Å]
10.746(2)
11.517(2)
18.427(4)
38.280(8)
10.961(2)
10.391(2)
α [°]
β
104.26(3)
94.19(3)
103.41(3)
γ
90.62(3)
2203.4(8)
Volume [Å3]
4241.1(15)
4
1.783
2.340
Z
1
Dcalcd. [Mg/m3]
1.439
0.649
984
Absorption coefficient [mm–1]
F(000)
2240
Final R indices [I Ͼ 2σ(I)]
R1 = 0.0751, wR2 = 0.1834
R1 = 0.0550; wR2 = 0.1343
Eur. J. Inorg. Chem. 2005, 5005–5010
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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