Catena-Poly[copper(II)-di-μ-acetyl-acetonato-copper(II) -bis(μ-4-hydroxy-3-methoxybenzaldehyde picoloyl-hydrazonato)] and (acetyl-acetonato)(4-meth-oxy-benzaldehyde picoloyl-hydrazonato)copper(II)

Article abstract of DOI:10.1107/S0108270110044343

In the two title copper(II) complexes, [CuL(C₅H ₇O₂)]_n , (I), and [CuL′(C ₅H₇O₂)], (II), respectively, where HL is 4-hy - droxy-3-meth-oxy-benzaldehyde picoloylhydrazone, C₁₄H ₁₂N₃O₃, and HL′ is 4-meth-oxy- benzaldehyde picoloylhydrazone, C₁₄H₁₂N₃O ₂, the Cu^II ions display a highly Jahn-Teller-distorted octa-hedral and a square-planar coordination geom-etry, respectively. In complex (I), two neighbouring Cu^II atoms are bridged by L^- and acetyl-acetonate, alternately, giving rise to a one-dimensional chain of CuN₂O₄ octa-hedra inter-connected by these two ligands along the a axis. In addition, the hydroxy H atom of the vanillin group connects to the carboxyl O atom of the adjacent chain via an O - H...O hydrogen bond, giving rise to a three-dimensional supra-molecular assembly. Complex (II) displays a discrete structure.

Full text of DOI:10.1107/S0108270110044343

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
catena-poly[copper(II)-di-ꢀ-acetylacetonato-copper(II)-bis(ꢀ-
4-hydroxy-3-methoxybenzaldehyde picoloylhydrazonato)],
[CuL(C5H7O2)]n, (I), and acetylacetonato(4-methoxybenz-
aldehyde picoloylhydrazonato)copper(II), [CuL0(C5H7O2)],
(II), where HL and HL0 are 4-hydroxy-3-methoxybenz-
aldehyde picoloylhydrazone and 4-methoxybenzaldehyde
ISSN 0108-2701
catena-Poly[copper(II)-di-l-acetyl-
acetonato-copper(II)-bis(l-4-hydroxy-
3-methoxybenzaldehyde picoloyl-
hydrazonato)] and (acetylacetonato)-
(4-methoxybenzaldehyde picoloyl-
hydrazonato)copper(II)
Li-Fang Jiang
picoloylhydrazone, respectively. To the best of our knowledge,
the title complexes represent the first examples of structurally
characterized CuL and CuL0 complexes.
Department of Chemistry and Chemical Engineering, Minjiang University, Fuzhou,
Fujian 350108, People’s Republic of China
Correspondence e-mail: fanhue@gmail.com
Received 10 September 2010
Accepted 29 October 2010
Online 10 November 2010
In the two title copper(II) complexes, [CuL(C5H7O2)]n, (I),
and [CuL0(C5H7O2)], (II), respectively, where HL is 4-hy-
droxy-3-methoxybenzaldehyde picoloylhydrazone, C14H12N3-
O3, and HL0 is 4-methoxybenzaldehyde picoloylhydrazone,
C14H12N3O2, the CuII ions display a highly Jahn–Teller-
distorted octahedral and a square-planar coordination geom-
etry, respectively. In complex (I), two neighbouring CuII atoms
are bridged by Lꢀ and acetylacetonate, alternately, giving rise
to a one-dimensional chain of CuN2O4 octahedra inter-
connected by these two ligands along the a axis. In addition,
the hydroxy H atom of the vanillin group connects to the
carboxyl O atom of the adjacent chain via an O—Hꢁ ꢁ ꢁO
hydrogen bond, giving rise to a three-dimensional supra-
molecular assembly. Complex (II) displays a discrete structure.
Figure 1
The molecular structure of (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level.
[Symmetry codes: (ii) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z; (iii) ꢀx, 1 ꢀ y, 1 ꢀ z.]
Comment
Studies of acylhydrazone Schiff bases and the construction of
complexes with transition metals are of great interest, not only
because of their intriguing structural motifs, but also because
of their important potential applications (Pickart et al., 1983;
Sreekanth et al., 2004) such as catalytic materials (Duda et al.,
2003) and magnetochemistry (Lin et al., 2008). The use of
carefully selected multidentate ligands and metal ions has
allowed the construction of polymers with defined geometries
and special properties. From the structural point of view,
picoloylhydrazone and its derivatives have been used exten-
sively as versatile ligands for building extended structures as
they have potential N,O-donor sites, which give rise to
different coordination modes (Domiano et al., 1980; Wu & Liu,
2003). As part of continuing investigations of these types of
Schiff base ligands, this work presents the syntheses and
structural characterization of two copper(II) complexes,
Figure 2
The molecular structure of (II), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level.
Acta Cryst. (2010). C66, m375–m378
doi:10.1107/S0108270110044343
# 2010 International Union of Crystallography m375

metal-organic compounds
Figure 3
The one-dimensional chain structure in (I). [Symmetry codes: (ii) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z; (iii) ꢀ x, 1 ꢀ y, 1 ꢀ z.]
Structural views of (I) and (II) are shown in Figs. 1 and 2,
respectively, and selected bond lengths and angles are given in
Tables 1 and 3. In complex (I), the CuII ion displays a highly
Jahn–Teller-distorted CuN2O4 octahedron, with the equatorial
plane defined by the two N atoms (pyridyl N1 and hydrazine
N2) of the Lꢀ ligand and atoms O4 and O5 of the acetyl-
acetonate ligand. The Cu1—N1 and Cu1—N2 distances are
similar to the values reported for other copper complexes
involving N-donor ligands (Table 4). The Cu1—O4 and
Cu1—O5 bond lengths correspond to the distances observed
in other Cu–acetylacetonate complexes (Heinze & Reinhart,
2006). There is no significant deviation of the metal centre
from the N2O2 equatorial plane, which shows a small but
significant tetrahedral distortion. The maximum displace-
ments from the least-squares plane through atoms N1, N2, O4
and carboxyl atom O1iii of an Lꢀ ligand [symmetry code: (iii)
ꢀx, 1 ꢀ y, 1 ꢀ z], with two weak coordination bonds of
˚
2.847 (3) and 2.894 (3) A, respectively (Das & Pal, 2005;
Heinze & Reinhart, 2006).
The tridentate hydrazone ligand Lꢀ is a bridging ligand to
coordinating to two neighbouring CuII ions through its donors
carboxyl atom O2, hydrazine atom N2 and phenolic atom O1.
In addition, acetylacetonate atom O5 acts as a bridging atom
linking Cu1 and Cu1ii. Therefore, a one-dimensional chain is
built up, consisting of CuN2O4 octahedra connected alter-
nately by pairs of the different ligands along the a axis, shown
in Fig. 3.
The planes through the acetylacetonate (O4/C15–C19/O5)
and picoloylhydrazone (C1–C5/N1/C6/O1/N2/N3) groups
make dihedral angles of 17.40 (18) and 8.60 (18)ꢂ, respectively,
with the equatorial N2O2 plane. More buckling of acetyl-
acetonate than picoloylhydrazone allows for a closer approach
of atom O5 towards Cu1ii and simultaneously reduces the
steric interaction between the two ligands (Bhadbhade &
Srinivas, 1993) (Fig. 3). The O—H function of the vanillin
group connects to the carboxyl O atom of the adjacent chain
via an O3—H3Bꢁ ꢁ ꢁO1i hydrogen bond [symmetry code: (i) x,
˚
and O5 are ꢀ0.0798 (15) and 0.0824 (15) A for atoms N2 and
˚
N1, respectively; Cu1 is 0.0339 (16) A below this plane. The
two axial positions are occupied by carbonyl atom O5ii of an
acetylacetonate ligand [symmetry code: (ii) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z]
1
2
1
2
ꢀ y, ꢀ + z], giving rise to a three-dimensional supra-
molecular assembly, as shown in Fig. 4.
In complex (II), atom Cu1 displays a square-planar coor-
dination geometry (Fig. 2). The Cu1—N and Cu1—O bond
lengths in the N2O4 plane are comparable with those found in
(I) (Table 3). However, unlike (I), (II) does not form chains
but is rather a simple discrete complex. The closest distance
between a CuII ion and an O atom from a neighbouring
iii
˚
molecule is 3.334 (4) A for Cu1ꢁ ꢁ ꢁO3 , indicating that no
intermolecular interactions are present. Just as in (I), there is
no significant deviation of the metal centre from the N2O2
coordination plane and the distortion of this plane is even
smaller. The maximum displacements from the least-squares
plane through atoms N1, N2, O3 and O4 are ꢀ0.042 (2) and
Figure 4
The three-dimensional supramolecular structure of (I). [Symmetry code:
˚
1
2
1
2
0.043 (2) A for atoms N2 and N1, respectively; Cu1 is
(i) x, ꢀ y, ꢀ + z.]
ꢃ
m376 Li-Fang Jiang [Cu(C14H12N3O3)(C5H7O2)] and [Cu(C14H12N3O2)(C5H7O2)]
Acta Cryst. (2010). C66, m375–m378

metal-organic compounds
˚
0.0054 (19) A below this plane. It is worth noting that the
Table 1
Selected geometric parameters (A, ) for (I).
ꢂ
˚
acetylacetonate (C15–C19/O3/O4) and picoloylhydrazone
(C1–C5/N1/C6/O1/N2/N3) planes make dihedral angles of
7.97 (18) and 6.43 (15)ꢂ, respectively, with the N2O2 plane. The
approximately planar conformation of the CuII ion in complex
(II) could be due to the absence of the Cu1ꢁ ꢁ ꢁO3iii interaction,
which reduces the steric interaction between the ligands and a
second molecule compared with (I).
Cu1—O4
Cu1—O5
1.902 (3)
1.931 (3)
Cu1—N1
Cu1—N2
1.979 (3)
1.996 (3)
O4—Cu1—O5
O4—Cu1—N1
O5—Cu1—N1
92.40 (12)
172.69 (14)
90.77 (12)
O4—Cu1—N2
O5—Cu1—N2
N1—Cu1—N2
95.14 (12)
172.15 (12)
81.99 (12)
Table 2
Hydrogen-bond geometry (A, ) for (I).
Experimental
ꢂ
˚
Ligand HL was prepared by the reaction of picolinohydrazide and
4-hydroxy-3-methoxybenzaldehyde in a 1:1 molar ratio under reflux
in ethanol for 3 h. The yellow product obtained on cooling was
washed with anhydrous ethanol. Ligand HL0 was obtained by a
similar procedure to that for HL, using 4-methoxybenzaldehyde in
place of 4-hydroxy-3-methoxybenzaldehyde. Both complexes were
prepared using the same method. Complex (I) was synthesized by
adding Cu(acac)2 (acac is acetylacetonate; 16.2 mg, 0.10 mmol) to a
solution of HL (27.1 mg, 0.10 mmol) in methanol (15 ml). The
resulting mixture was stirred for 3 h at room temperature to afford a
green solution. The solution was allowed to stand at room tempera-
ture for about two weeks, during which time dark-green crystals of (I)
were produced at the bottom of the vessel on slow evaporation of the
methanol (yield 56.0%, based on Cu). Complex (II) was obtained by
using HL0 in place of HL. After two weeks, dark-green crystals of
complex (II) appeared (yield 49.0%, based on Cu).
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
O3—H3Bꢁ ꢁ ꢁO1i
Symmetry code: (i) x; ꢀy þ ; z ꢀ .
0.79 (3)
1.93 (4)
2.636 (4)
149 (6)
1
2
1
2
Table 3
Selected geometric parameters (A, ) for (II).
ꢂ
˚
Cu1—O4
Cu1—O3
1.892 (3)
1.914 (3)
Cu1—N2
Cu1—N1
1.962 (4)
1.982 (4)
O4—Cu1—O3
O4—Cu1—N2
O3—Cu1—N2
91.81 (14)
95.25 (15)
172.67 (16)
O4—Cu1—N1
O3—Cu1—N1
N2—Cu1—N1
176.03 (16)
91.08 (15)
81.97 (15)
Compound (I)
Table 4
Comparative geometric parameters (A) for Cu—N in copper complexes.
˚
Crystal data
Complex
Cu—N(pyridyl)
Cu—N(hydrazine)
3
˚
[Cu(C14H12N3O3)(C5H7O2)]
Mr = 432.91
V = 1915.0 (5) A
Z = 4
(I)†
(II)†
1.979 (3)
1.982 (4)
1.989 (2)
1.980 (4), 1.996 (3)
1.996 (3)
1.962 (4)
1.921 (2)
2.008 (4), 1.919 (3)
Monoclinic, P21=c
Mo Kꢂ radiation
ꢀ = 1.18 mmꢀ1
T = 293 K
0.42 ꢄ 0.31 ꢄ 0.18 mm
˚
a = 8.4719 (15) A
[Cu(C15H13N4O2)Cl]‡
[Cu2(C12H8N4O2)(H2O)3]-
(NO3)2ꢁ2H2O§
[Cu4(C13H9N3O2)2Cl4]n}
˚
b = 23.586 (3) A
˚
c = 9.8635 (14) A
ꢁ = 103.683 (6)ꢂ
2.013 (6)
1.984 (6)
´
† This work. ‡ Grove et al. (2004). § Lagrenee et al. (1991). } Bai et al. (2006).
Data collection
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.652, Tmax = 0.809
18642 measured reflections
4358 independent reflections
2831 reflections with I > 2ꢃ(I)
Rint = 0.089
Data collection
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.680, Tmax = 0.806
16505 measured reflections
4005 independent reflections
1904 reflections with I > 2ꢃ(I)
Rint = 0.125
Refinement
R[F2 > 2ꢃ(F2)] = 0.060
wR(F2) = 0.138
S = 1.04
4358 reflections
259 parameters
1 restraint
H atoms treated by a mixture of
independent and constrained
refinement
Refinement
ꢀ3
˚
Áꢄmax = 0.47 e A
R[F2 > 2ꢃ(F2)] = 0.051
wR(F2) = 0.154
S = 0.91
247 parameters
H-atom parameteꢀrs3 constrained
ꢀ3
˚
Áꢄmin = ꢀ0.63 e A
˚
Áꢄmax = 0.39 e A
Áꢄmin = ꢀ0.51 e A
ꢀ3
˚
4005 reflections
Compound (II)
Crystal data
In both complexes, H atoms bonded to C atoms were positioned
geometrically and refined using a riding model, with Csp2—H =
3
˚
V = 1763.4 (6) A
Z = 4
[Cu(C14H12N3O2)(C5H7O2)]
Mr = 416.91
Monoclinic, P21=c
˚
a = 7.4198 (15) A
˚
˚
0.93 A, with Uiso(H) = 1.2Ueq(C), and methyl C—H = 0.96 A, with
Uiso(H) = 1.5Ueq(C). The H atom bonded to the phenol O atom in (I)
was located in a difference Fourier map and subesquently refined
Mo Kꢂ radiation
ꢀ = 1.27 mmꢀ1
T = 293 K
0.39 ꢄ 0.26 ꢄ 0.17 mm
˚
b = 14.969 (3) A
˚
with the help of an O—H distance restraint of 0.82 (3) A, and with
Uiso(H) = 1.2Ueq(O).
˚
c = 15.885 (3) A
ꢁ = 91.78 (3)ꢂ
ꢃ
Acta Cryst. (2010). C66, m375–m378
Li-Fang Jiang
[Cu(C14H12N3O3)(C5H7O2)] and [Cu(C14H12N3O2)(C5H7O2)] m377

metal-organic compounds
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For both compounds, data collection: APEX2 (Bruker, 2007); cell
refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-
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2008); program(s) used to refine structure: SHELXL97 (Sheldrick,
2008); molecular graphics: SHELXTL (Sheldrick, 2008); software
used to prepare material for publication: SHELXTL.
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The author thanks Minjiang University for financial
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´
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described at the back of the journal.
´
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ꢃ
m378 Li-Fang Jiang [Cu(C14H12N3O3)(C5H7O2)] and [Cu(C14H12N3O2)(C5H7O2)]
Acta Cryst. (2010). C66, m375–m378