Coordination interactions in the crystalline lattice of alkaline
ions with the polyoxometalate [V
12
B
18
O
60
H
6
]
10−
ligand
PATRICIO HERMOSILLA-IBÁÑEZ†‡, JUAN COSTAMAGNA†, ANDRÉS VEGA‡§,
VERÓNICA PAREDES-GARCÍA‡§, ERIC LE FUR¶‖, EVGENIA SPODINE*‡†† and
DIEGO VENEGAS-YAZIGI*†‡
†Facultad de Química y Biología, Universidad de Santiago de Chile, Santiago, Chile
‡CEDENNA, Santiago, Chile
§Facultad de Ciencias Exactas, Departamento de Ciencias Químicas, Universidad Andres Bello,
Santiago, Chile
¶ENSCR, CNRS, UMR 6226, Rennes, France
‖Université Européenne de Bretagne, France
††Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Chile
(Received 6 June 2014; accepted 24 July 2014)
In the present work, the synthesis and structural characterization of two new polyoxovanadoborate
(BVO) frameworks, based on the [V
12
B
18
O
60
H
6
]
10−
polyanion, are reported, K(H
3
O)
(enH
2
)
4
[V
12
B
18
O
60
H
6
]·9.60H
2
O(1) and Li
8
(NH
4
)
2
[V
12
B
18
O
60
H
6
]·8.02H
2
O(2). Both compounds
are obtained in a mixed valence ratio of 10V
IV
/2V
V
. Framework 1 is characterized by potassium
ions coordinated by the BVO cluster and ethylenediammonium and hydronium ions as charge-
compensating agents. In framework 2, the BVO clusters are coordinating lithium ions and the charge
is compensated by ammonium ions. Using the SHAPE 2.1 program, it was possible to calculate the
best geometry for the existing lithium and potassium ions. For 2, the lithium ions are five-
coordinate, best described by a square pyramid (SPY-5), while the coordination sphere around the
potassium ions in 1 are six-coordinate. For 1, the coordination sphere of the existing potassium ions
in the framework can be described as trigonal prism (TPR-6). Calculations were also done for a
previously reported cluster [Na
10
[(H
2
O)V
12
B
18
O
60
H
6
]·18H
2
O] (3), in which the sodium ions are
*Corresponding authors. Email: espodine@ciq.uchile.cl (E. Spodine); diego.venegas@usach.cl (D. Venegas-Yazigi)
© 2014 Taylor & Francis
Journal of Coordination Chemistry , 2014
Vol. 67, Nos. 23–24, 3940–3952, http://dx.doi.org/10.1080/00958972.2014.960407
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