Full text of DOI:10.1107/S0108270101006229

metal-organic compounds
0
Acta Crystallographica Section C
Crystal Structure
Fig. 1 shows the structure of (I), which consists of [Ni1(4,4 -
0
bipy) O ], [V O ], [Ni2(H O) (4,4 -bipy) O ] units, and crys-
2
4
2
2
6
2
2
2
Communications
tallization water molecules (O8, O9 and O10). The [V O ] unit
2
6
ISSN 0108-2701
is made up of a pair of corner-sharing [VO ] tetrahedra. There
4
are three types of O atoms in the [V O ] group, viz. terminal
6
2
O2 and O6 atoms, bridging O5 and O7 atoms connected to
both V1 and V2 atoms, and bridging O1 and O4 atoms linking
A three-dimensional inorganic/organic
0
i
Ni and Vatoms. Ni1 is coordinated by O1 and O1 atoms from
ii
hybrid material, [Ni (4,4 -bipy) -
2
3
iii
iii
two [V O ] groups, and N1, N1 , N2 and N2 atoms from four
2
6
(
H O) V O ]Á2.5H O
2
2 4 12
2
0
4
coordinated by O4 and O4 atoms from two [V O ] groups,
,4 -bipy ligands to form an Ni1O N octahedron, while Ni2 is
2 4
iv
2
6
iv
N3 and N3 atoms from two 4,4 -bipy ligands, and O3 and O3
0
iv
Lan Yang, Changwen Hu, Haruo Naruke and Toshihiro
Yamase*
atoms, identi®ed as water molecules from the Ni2ÐO3 bond
valence of 0.29 (Brown & Altermatt, 1985; Brese & O'Keeffe,
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta,
Midori-ku, Yokohama 226-8503, Japan
1
bond angles in the Ni1O N and Ni2O N octahedra are
991), to form an Ni2O N octahedron. O(N)ÐNiÐO(N)
4 4
2
4
4
2
Correspondence e-mail: tyamase@res.titech.ac.jp
ꢀ
ꢀ
ꢀ
nearly 90 [88.7 (1)±91.3 (1) ] or ideally linear (180 ). The
vi
Received 19 January 2001
Accepted 11 April 2001
[V O ] group links Ni1 and Ni2 atoms, forming an
2 6
±[Ni2(H O) (4,4 -bipy) ]±[V O ]±[Ni1(4,4 -bipy) ]± bimetallic
0
0
2
2
2
2
6
4
0
chain. Two crystallographically different 4,4 -bipy groups are
0
The title compound, poly[[[diaqua(ꢀ-4,4 -bipyridyl)di-
0
nickel(II)]-bis(ꢀ-4,4 -bipyridyl)-di-ꢀ-hexaoxodivanadate(2� )]
2
.5-hydrate], [Ni (V O ) (C H N ) (H O) ]Á2.5H O, has
2
2
6 2 10
8
2 3
2
2
2
been prepared hydrothermally and characterized by elemental
analyses, IR spectroscopy and single-crystal X-ray diffraction.
0
The structure consists of [V O ], [Ni(4,4 -bipy) O ] and
2
6
4
2
0
Ni(H O) (4,4 -bipy) O ] polyhedra, and water of crystal-
2 2 2 2
[
lization. The Ni atoms and one bipyridyl group lie on centres
of symmetry.
Comment
There is increasing interest in the synthesis of organic/inor-
ganic hybrid compounds because of their novel structural
architectures (Hagrman et al., 1999) and unusual electro-
chemical and magnetic properties (Leroux et al., 1996; Lira-
Cant u & G o mez-Romero, 1998). Hydrothermal synthesis and
structural characterization of vanadium oxide lattices
containing Zn±, Cu± and Co±bipyridyl (bipy) complexes have
been intensively studied because of their large structural
diversity; for example, two-dimensional layered vanadium
0
0
oxide with interlayer zinc±2,2 -bipy complex, [Zn(2,2 -
bipy) ] V O (Zhang et al., 1996), discrete neutral hexa-
2
2
6
17
0
nuclear [Zn V ] clusters, [{Zn(2,2 -bipy) } V O ] (Zhang et
2
4
2 2
4
12
al., 1997), a one-dimensional vanadium oxide chain with
0
0
copper±2,2 -bipy complexes, [Cu(2,2 -bipy)V O ] and
2
6
0
Cu(2,2 -bipy) V O ] (DeBord et al., 1996), and a three-
2 2 6
[
0
dimensional
bipy) } V O ] (LaDuca et al., 2000). It should be noted that
bimetallic
oxide
network,
[{Co(3,3 -
2
2
4
12
0
0
all the bipy ligands in these complexes are of the 2,2 - and 3,3 -
0
isomers, and no 4,4 -bipy-containing compound has been
observed in the vanadate±M(bipy) system. We report here
n
Figure 1
ORTEPII (Johnson, 1976) drawing of the partial structure of (I).
0
the synthesis and crystal structure of [Ni (4,4 -bipy) (H O) -
2
3
2
2
Displacement ellipsoids are drawn at the 50% probability level. H atoms
0
V O ]Á2.5H O, (I), which is constructed from a three-
4
12
2
in 4,4 -bipy groups have been omitted for clarity. [Symmetry codes: (i) x,
1
dimensional network containing [V O ] and Ni/V-bimetallic
2
3
1
5
6 1
1 + y, z; (ii) � x, � y, 1 � z; (iii) � x, � y, 1 � z; (iv) 1 � x, 1 � y,
2
2
2
2
0
1
oxide chains linked by 4,4 -bipy ligands.
1 � z; (v) x, 1 � y, + z; (vi) x, � 1 + y, z.]
2
ꢁ
Acta Cryst. (2001). C57, 799±801
# 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved 799

metal-organic compounds
0
present: 4,4 -bipy(I) comprises the N1, N3 and C1±C10 atoms,
0
Experimental
and 4,4 -bipy(II) comprises N2, C11±C15 and their symmetry-
0
All reagents were of analytical grade and were used without further
puri®cation. A mixture of NiCl
related atoms. In the 4,4 -bipy(I) group, the dihedral angle
between the two pyridyl rings N1/C1±C5 and N3/C6±C10 is
2
Á6H
2
O (0.0880 g), NaVO
3
(0.0904 g),
0
4
,4 -bipyridyl (0.1157 g), (CH
3
)
4
NOH (0.0338 g) and H
2
O (10 ml) in a
ꢀ
35.8 (1) . This is in contrast to the conformation between the
0
two rings in the 4,4 -bipy(II) group which are constrained to be
molar ratio 1:2:2:1:1500 was placed in a 20 ml Te¯on-lined steel
autoclave, and heated at 453 K for 72 h. After cooling to room
temperature, green needle-like crystals were obtained in ca 70% yield
based on vanadium (found: H 3.18, C 35.09, N 8.20, V 18.9, Ni
0
planar by a centre of symmetry. The 4,4 -bipy(I) links Ni1 and
Ni2 atoms in two adjacent bimetallic chains to give a two-
dimensional in®nite network sheet parallel to the ab plane
Fig. 1). Fig. 2 shows the crystal structure of (I) viewed down
the b axis. There exist two crystallographically equivalent two-
dimensional network sheets, denoted by sheet A and sheet B
in Fig. 2, which are stacked alternately (...ABAB...) along the c
axis with an interval of 5.53 A. Each of the 4,4 -bipy(II) groups
lying in the c direction links two Ni1 atoms in two different A
sheets, or equivalently B sheets. Also, the [V O ] groups in
10.48%; calculated for C30
33 6 2 16.5 4
H N Ni O V : H 3.13, C 33.9, N 7.93, V
19.17, Ni 11.04%). The IR spectrum exhibits absorption bands in the
range 950±500 cm attributed to V O or VÐOÐV stretching and
(
�
1
�
1
0
additional bands in the range 1600±1000 cm assigned to 4,4 -bipy
groups. Thermal gravimetric analysis shows a weight loss of 5.8%
between 293 and 533 K corresponding to water of crystallization, and
a further loss of 34.9% occurred between 533 and 705 K due to
Ê
0
0
elemination of the O3 water molecule and the decomposition of 4,4 -
bipy.
2
6
two adjacent A and B sheets are connected through the O7
atom, to form an in®nite [V O ] chain running along the c
axis.
Crystal data
2
6 1
�
3
[Ni
2
(V O
2 6
2
) (C10
H
8
N
2 3
) -
D
x
= 1.864 Mg m
0
(H O) ]Á2:5H O
Mo Kꢂ radiation
Cell parameters from 14338
re¯ections
2
2
2
In conclusion, it is the characteristic geometry of 4,4 -bipy,
where N donors are located in two opposite ends of the ligand,
that leads to the highly interlinked three-dimensional network
structure. The successful preparation of the new three-
dimensional network vanadium oxide cluster with a nickel
M
r
= 1062.79
Monoclinic, C2/c
Ê
Ê
ꢀ
a = 30.3799 (9) A
b = 11.2402 (3) A
Ê
c = 11.5366 (3) A
ꢃ = 1.9±30.0
ꢀ = 2.00 mm
T = 173.2 K
� 1
ꢀ
ꢁ
= 105.961 (1)
Prism, green
0.30 Â 0.12 Â 0.03 mm
0
Ê
3
complex of the 4,4 -bipy ligand will extend the variety of
network structures in the organic/inorganic hybrid system.
V = 3787.6 (2) A
Z = 4
Data collection
Rigaku R-AXIS RAPID Imaging
Plate diffractometer
5509 independent re¯ections
R
ꢃmax = 30.0
int = 0.027
ꢀ
!
scans
Absorption correction: multi-scan
ABSCOR; Higashi, 1995)
min = 0.515, Tmax = 0.869
4250 measured re¯ections
h = � 42 ! 42
(
T
k = � 15 ! 15
l = � 16 ! 16
1
Intensity decay: none
Re®nement
2
Re®nement on F
R(F) = 0.042
H atoms treated by a mixture of
independent and constrained
re®nement
2
wR(F ) = 0.114
S = 1.40
2
2
2
w = 1/[ꢄ (F
where P = (F
(Á/ꢄ)max = 0.002
Áꢅmax = 0.90 e A
Áꢅmin = � 0.50 e AÊ
o
) + (0.05P) ]
+ 2F )/3
o c
2 2
4
3
634 re¯ections
12 parameters
Ê
� 3
� 3
Table 1
Selected bond lengths (A).
Ê
i
Ni1ÐO1
Ni1ÐN1
Ni1ÐN2
Ni2ÐO4
Ni2ÐN3
Ni2ÐO3
V1ÐO6
2.017 (2)
V1ÐO4
V1ÐO7
V1ÐO5
V2ÐO2
V2ÐO1
1.663 (2)
1.788 (2)
1.791 (3)
1.615 (3)
1.661 (2)
1.781 (3)
1.793 (3)
2.162 (3)
2.231 (2)
2.034 (2)
2.099 (3)
2.103 (3)
1.612 (3)
ii
V2ÐO7
V2ÐO5
1
2
Symmetry codes: (i) x; 1 ‡ y; z; (ii) x; 1 � y; ‡ z.
0
H atoms were de®ned and re®ned only for the 4,4 -bipy groups
Ê
CÐH = 0.81 (5)±1.04 (5) A]. Positional and Uiso parameters for H14
[
Figure 2
Packing diagram of (I) viewed along the b axis. H atoms in 4,4 -bipy
0
were ®xed because of their gradual divergence during the re®nement.
Crystallization water molecules O8, O9 and O10 were re®ned with
occupancies of 0.5, 0.5 and 0.25, respectively, because of too large Uiso
parameters when re®ned on full occupancies.
groups have been omitted. The primed atoms are located at symmetry-
5
1
0
related ( � x, � y, � z) positions from unprimed atoms. Atoms in 4,4 -
2
bipy(II) groups and [V
2
O
2 6
]
1
chains are denoted by grey circles.
ꢁ
800 Lan Yang et al.
[Ni (V (H O)
2
2
O
6
)
2
(C10
H
8
N
2
)
3
2
2
]Á2.5H
2
O
Acta Cryst. (2001). C57, 799±801

metal-organic compounds
Data collection: PROCESS-AUTO (Rigaku Corporation, 1998);
cell re®nement: PROCESS-AUTO; data reduction: TEXSAN
DeBord, J. R. D., Zhang, Y., Haushalter, R. C., Zubieta, J. & O'Connor, C. J.
(
1996). J. Solid State Chem. 122, 251±258.
Hagrman, P. J., Hagrman, D. & Zubieta, J. (1999). Angew. Chem. Int. Ed. 38,
638±2684.
(Molecular Structure Corporation, 1999); program(s) used to solve
2
structure: SIR92 (Altomare et al., 1994); program(s) used to re®ne
structure: TEXSAN.
Higashi, T. (1995). ABSCOR. Program for Absorption Correction. Rigaku
Corporation, Tokyo, Japan.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
LaDuca, R. L. Jr, Brodkin, C., Finn, R. C. & Zubieta, J. (2000). Inorg. Chem.
Commun. 3, 248±250.
Leroux, F., Koene, B. E. & Nazar, L. F. (1996). J. Electrochem. Soc. 143, L181±
183.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: BR1320). Services for accessing these data are
described at the back of the journal.
Lira-Cant u , M. & G o mez-Romero, P. (1998). Chem. Mater. 10, 698±704.
Molecular Structure Corporation (1999). TEXSAN. MSC, 3200 Research
Forest Drive, The Woodlands, TX 77381, USA.
Rigaku Corporation (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo,
Japan.
Zhang, Y., DeBord, J. R. D., O'Connor, C. J., Haushalter, R. C., Clear®eld, A.
& Zubieta, J. (1996). Angew. Chem. Int. Ed. Engl. 35, 989.
Zhang, Y., Zapf, P. J., Meyer, L. M., Haushalter, R. C. & Zubieta, J. (1997).
References
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C.,
Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.
Altermatt, D. & Brown, I. D. (1985). Acta Cryst. B41, 240±244.
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192±197.
Inorg. Chem. 36, 2159±2165.
ꢁ
Acta Cryst. (2001). C57, 799±801
Lan Yang et al.
2 2
[Ni (V O
6
)
2 8 2
(C10H N )
3 2
(H O)
2
2
]Á2.5H O
801