[{C6H5NNN(O)C6H5}V(O)2(C5H5N)] and [{O2NC6H4NNN(O)C6H5}V(O)2(C5H5N)]
˚
Experimental Section
Table 3 Hydrogen-bonding geometric parameters /A, ° for com-
plexes 1 and 2
A single crystal fixed on a glass fiber was used for the X-ray data
collection. Data were collected with a Bruker APEX II CCD area-
detector diffractometer and graphite-monochromatized Mo-Kα
radiation using COSMO program [13]. Cell refinement, data re-
duction and the absorption correction were performed using
SAINT and SADABS programs, respectively [13]. The structure of
complexes 1 and 2 were solved by direct methods [14] and refined
on F2 with anisotropic temperature parameters for all non H atoms
[15]. H atoms of the aromatic groups were positioned geometrically
(CϪH ϭ 0.93 A for Csp atoms) and treated as riding on their
respective C atoms, with Uiso(H) values set at 1.2UeqCsp2. The crys-
tallographic parameters and details of data collection and refine-
ment are given in Table 1.
DϪH···A
DϪH
H···A
D···A
DϪH···A
Complex 1
C32ϪH32···O2Ј
C35ϪH35···O3Љ
0.93
0.93
2.54
2.60
3.293(3)
3.290(3)
138
132
Complex 2
C36ϪH36···O11Љ
C14ϪH14···O2Ј
0.93
0.93
2.56
2.44
3.294(5)
3.350(4)
136
166
2
˚
(D ϭ donor atom, A ϭ acceptor atom)
Symmetry codes: (Ј) x, 1ϩy, z, (Љ) Ϫx, Ϫy, Ϫz for complex (1)
Symmetry codes: (Ј) 1ϩx, y, z, (Љ) Ϫx, Ϫy, Ϫz for complex (2)
Crystallographic data for the structural analyses have been de-
posited with the Cambridge Crystallographic Data Centre CCDC
no. 638028 and 638029. Further details of the crystal structures
conts/retrieving.html (or from the CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: ϩ44 1223 336033; e-mail:
In complex 1 the [{C6H5NNN(O)C6H5}V(O)2(C5H5N)]
molecules are associated to [{C6H5NNN(O)C6H5}V(O)2-
(C5H5N)]2 dimeric units through centrosymmetric non-
classical CϪH···O hydrogen bonds [C35···O3Љ
ϭ
˚
3.290(3) A; symmetry code: (Љ) Ϫx, Ϫy, Ϫz] (Table 3). The
dimers compose a twelve-membered ring with a chair con-
formation in which the V and VЉ atoms are distanced at
˚
6.2523(7) A. The dimeric units Ϫ related to each other by
Preparation of [{C6H5NNN(O)C6H5}V(O)2(C5H5N)],
[1,3-Bis(phenyl)triazenide 1-oxide-κ2N3,O]pyridine-
cis-dioxovanadium(V) (1)
translation Ϫ associate to one-dimensional chains along to
the crystallographic direction[010] via additional centro-
symmetric non-classical CϪH···O hydrogen bonds
Pale-yellow 1,3-bis(phenyl)triazene 1-oxide (50 mg, 0.23 mmol) was
dissolved in 15 mL of ethanol at 35 °C, and treated with one KOH
pellet. Stirring was maintained for 10 min, while the reaction mix-
˚
[C32···O2Ј ϭ 3.293(3) A; symmetry code: (Ј) x, 1ϩy, z]
(Table 3). In the 1-D supramolecular arrangement of com-
plex 1, two pyridine molecules related to each other by an
inversion centre, acts as bridges between two [VO2]ϩ frag-
ments Ϫ equivalent by an inversion centre Ϫ via non-classi-
cal CϪH···O hydrogen bonds involving terminal oxo-li-
gands attached to the vanadium centres.
ture turns dark-yellow.
A solution of VOSO4 ·5H2O (60 mg
0.24 mmol) in water (5 mL) was added under continuous stirring.
After 10 min an olive-green solid was formed. The precipitation
was completed after keeping the reaction system at 5 °C. This solid
was filtered-off, washed with small portions of cool water, and
vacuum dried over P2O5. Yellow crystals of complex 1, suitable for
X-ray analysis, were obtained within 60 days at room temperature
by recrystallization from a acetone (15 mL)/pyridine (2 mL) mix-
ture.
Complex 2 attains a supramolecular arrangement similar
to 1. [{O2NC6H4NNN(O)C6H5}V(O)2(C5H5N)]2 dimeric
units results from [{O2NC6H4NNN(O)C6H5}V(O)2-
(C5H5N)] complex molecules associated through centro-
symmetric non-classical CϪH···O hydrogen bonds
Properties: yellow block-shaped with vitreous brilliancy crystals.
C17H15N4O3V (374.27). Yield: 70 mg (0.19 mmol), 80 % based on
VOSO4 ·5H2O. Melting point: 139 °C.
˚
[C36···O11Љ ϭ 3.294(5) A; Symmetry code: (Љ) Ϫx, Ϫy, Ϫz]
(Table 3). Compared with 1, the distance between the va-
˚
nadium atoms at 7.797(1) A is significantly longer. The di-
Solid free ligand C6H5N(H)ϪNϭN(ǞO)C6H5 (213.23). IR (KBr),
bands as a whole: 3146 [s, ν(NϪH)], 1605 [vs, ν(CϭC)], 1517
[vs, δ(NϪH)], 1444 [s, νs(NϭN)], 1293 [w, ν(NǞO)], 1215 [vs,
νs(NϪN)], 1180 cmϪ1 [s, νas(NǞO)].
meric units associate by translation to one-dimensional
chains along to the crystallographic direction [100] via ad-
ditional centrosymmetric non-classical CϪH···O hydrogen
˚
bonds [C14···O2Ј ϭ 3.350(4) A; symmetry code: (Ј)1ϩx, y, z]
(Table 3). In the case of complex 2, the 1-D supramolecular
arrangement includes NC6H4NO moieties belonging to a
centrosymmetric pair of [O2NC6H4NNN(O)C6H5]Ϫ li-
gands, acting as bridges between two [VO2]ϩ fragments
equivalent by inversion. The resulting dimeric units are then
connected via non-classical CϪH···O hydrogen bonds in-
volving terminal oxo-ligands attached to the vanadium
centres.
The single-crystal X-ray structural analysis of the title
compounds are the first reported in the literature related to
triazenido 1-oxide anions stabilizing cis-dioxovanadium(V)
fragments.
C17H14N5O5V (419.27). IR (KBr), bands as a whole: the νNϪH
band is absent. 1244 [s, ν(NϪO)], 1181 [w, νs(NϪN)], 1069 [m,
νas(NϪO)], 937 cmϪ1 [vs, ν(VϭO)].
Preparation of
[{O2NC6H4NNN(O)C6H5}V(O)2(C5H5N)], [1-phenyl-
3-(4-nitrophenyl)triazenide 1-oxide-κ2N3,O]pyridine-
cis-dioxovanadium(V)
Yellow
1-phenyl-3-(4-nitrophenyl)triazene
1-oxide
(0.05 g,
0.19 mmol) was dissolved in 10 mL of ethanol at 35 °C, and treated
with one KOH pellet. Stirring was continued for 10 min, while the
Z. Anorg. Allg. Chem. 2008, 1058Ϫ1062
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1061
Hoerner, Manfredo
