Catena-Poly[[bis(pentane-2,4-dionato-k2O,O′)cobalt(II)]- μ-4,4′-methylene-dianiline-k2N:N′]

Article abstract of DOI:10.1107/S0108270104022073

In the title compound, [Co(C₅H₇O₂) ₂(C₁₃H₁₄N₂)]_n or [Co(acac)₂(dadpm)]_n, where acac is acetylacetonate and dadpm is 4,4′-methylenedianiline, the Co atom is on a centre of symmetry and is octahedrally coordinated by four O atoms from two acac anions and by two N atoms from two dadpm ligands. Each dadpm ligand, which has a twofold axis passing through its methylene C atom, bridges two Co atoms to form a spiral polymeric chain. Neighbouring chains connect via hydrogen bonds to form a two-dimensional network.

Full text of DOI:10.1107/S0108270104022073

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
been widely used to coordinate with metals to create spiral
oligonuclear complexes and polymers (Hasenknopf et al.,
1996; Jung et al., 1998; Abrahams et al., 1999).
ISSN 0108-2701
Ligands containing amino groups are well known to coor-
dinate with various metals to give coordination polymers
(Dickman, 2000; Alcock et al., 1997; Lu et al., 1994). Among
these ligands, 4,40-methylenedianiline (dadpm) has frequently
been employed for the construction of coordination polymers,
e.g. the one-dimensional polymer [Cu2(dadpm)2(trans-
oxpy)](NO3)2Á6H2O [trans-oxpy is trans-N,N0-bis(2-pyridyl-
methyl)oxamide; Zhang, Kang et al., 2001], the one-dimen-
sional polymer {[Cu(dadpm)(C3H4O4)Cl]Cl}2 (C3H4O4 is
malonic acid; Zhang et al., 1999), the three-dimensional
polymer [Ni(dadpm)4(H2O)2](NO3)2Á2H2O (Zhang, Lei et al.,
2001) and the three-dimensional polymer [Cd(dadpm)2Cl]-
(dca) (dca is dicyanamide; Luo et al., 2003). We report here the
crystal structure of the title cobalt(II) acac±dadpm complex,
(I) (acac is acetylacetonate).
catena-Poly[[bis(pentane-2,4-dionato-
j2O,O0)cobalt(II)]-l-4,40-methylene-
dianiline-j2N:N0]
Xin-Lei Zhi,a Wen-Hua Zhang,a Yong Zhanga and Jian-Ping
Langa,b
*
aKey Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry and
Chemical Engineering, Suzhou Uinversity, Suzhou 215006, Jiangsu, People's
Republic of China, and bState Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032,
People's Republic of China
Correspondence e-mail: jplang@suda.edu.cn
Received 15 July 2004
Accepted 7 September 2004
Online 22 October 2004
In the title compound, [Co(C5H7O2)2(C13H14N2)]n or
[Co(acac)2(dadpm)]n, where acac is acetylacetonate and
dadpm is 4,40-methylenedianiline, the Co atom is on a centre
of symmetry and is octahedrally coordinated by four O atoms
from two acac anions and by two N atoms from two dadpm
ligands. Each dadpm ligand, which has a twofold axis passing
through its methylene C atom, bridges two Co atoms to form a
spiral polymeric chain. Neighbouring chains connect via
hydrogen bonds to form a two-dimensional network.
The polymer backbone of (I) is made up of Co(acac)2
fragments and bridging dadpm ligands. Each dadpm ligand
links two fragments through two CoÐN bonds, forming an
interesting one-dimensional spiral array of repeating
Co(acac)2(dadpm) units stacked along the crystallographic c
axis (Fig. 1). The Co atom in (I) lies on a centre of symmetry
and is coordinated by four O atoms from two chelated acac
anions and two N atoms from two different dadpm ligands,
forming a distorted octahedral coordination geometry. Four O
atoms (O1, O2, O1A and O2A) occupy the equatorial posi-
Comment
`Spirality' is an important structural feature of great interest in
inorganic and coordination chemistry (Constable, 1992;
Carina et al., 1993; Lehn, 1995). Much effort has been devoted
in recent decades to the design of metal complexes exhibiting
spiral, particularly helical, architectures (Constable, 1992;
Carina et al., 1993; Lehn, 1995; Zaworotko, 1998). Suitably
tailored polydentate ligands, particularly oligopyridines, have
Ê
tions, with bond lengths of 2.0672 (12) and 2.0319 (12) A
(Table 1), and two N atoms (N1 and N1A) are located in the
Ê
axial positions, with a Co1ÐN1 distance of 2.2201 (17) A.
Figure 1
A view of the polymeric structure of (I), with the atom-labelling scheme. Atoms related by the centre of symmetry at ( x; 1 y; 1 z) are indicated
with the suf®x A. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
m554 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270104022073
Acta Cryst. (2004). C60, m554±m556

metal-organic compounds
Crystal data
[Co(C5H7O2)2(C13H14N2)]
Mr = 455.40
Mo Kꢂ radiation
Cell parameters from 3781
re¯ections
Monoclinic, P2=c
a = 5.5805 (5) A
ꢃ = 3.6±25.3ꢀ
Ê
Ê
1
b = 8.9808 (9) A
ꢄ = 0.81 mm
T = 193 (2) K
Ê
c = 21.955 (2) A
ꢁ = 94.976 (3)ꢀ
V = 1096.20 (19) A
Plate, pink
0.36 Â 0.35 Â 0.07 mm
3
Ê
Z = 2
Dx = 1.380 Mg m
Figure 2
A packing diagram for (I), showing the two-dimensional network formed
by hydrogen bonds (dashed lines) between the polymeric chains.
3
Data collection
Rigaku Mercury CCD area-detector
diffractometer
! scans
Absorption correction: multi-scan
(Jacobson, 1998)
Tmin = 0.758, Tmax = 0.945
10 160 measured re¯ections
2005 independent re¯ections
1887 re¯ections with I > 2ꢅ(I)
Rint = 0.023
The Co1ÐO bond lengths in (I) are similar to those found
in related CoII±acac complexes, such as [Co(acac)2(pz)]
ꢃmax = 25.4ꢀ
h = 6 ! 6
0
Ê
(2.0382 A; pz is pyrazine; Ma et al., 2001), [Co(acac)2(4,4 -
k = 10 ! 10
0
0
Ê
bipy)] (2.032 A; 4,4 -bipy is 4,4 -bipyridine; Ma et al., 2001) and
l = 23 ! 26
Ê
[Co2(acac)4(H2O)2][Co(acac)(H2O)4](ClO4)ÁEtOH (2.051 A;
Re®nement
Re®nement on F2
R(F) = 0.031
Ê
McCann et al., 2001). The CoÐN bond length of 2.2201 (17) A
in (I) is comparable with that in compounds with similar
w = 1/[ꢅ2(Fo2) + (0.0316P)2
+ 0.6071P]
wR(F2) = 0.074
S = 1.11
where P = (Fo + 2Fc2)/3
2
Ê
motifs, such as [Co(hfac)2(opda)2] (2.2243 A; hfac is
(Á/ꢅ)max < 0.001
1,1,1,5,5,5-hexa¯uoropentane-2,4-dionate and opda is 1,2-
phenylenediamine; Dickman, 2000), but longer than those
3
Ê
2005 re¯ections
195 parameters
All H-atom parameters re®ned
Áꢆmax = 0.20 e A
3
Ê
0.29 e A
Áꢆmin
=
0
Ê
observed in [Co(azpy)(pht)(H2O)3] (2.188 A; azpy is 4,4 -azo-
pyridine and pht is o-phthalate; Zhu et al., 2003) and [Co-
0
3,30-azopyridine; Li et al., 2001).
0
0
Ê
Table 1
Selected geometric parameters (A, ).
(3,3 -azpy)(H2O)4](ClO4)2Á3(3,3 -azpy) (2.176 A; 3,3 -azpy is
ꢀ
Ê
There is a twofold axis passing through methylene atom C12
of the dadpm ligand in (I). The dadpm ligand adopts a trans±
gauche con®rmation. The dihedral angle between the two
phenyl rings in the dadpm ligand in (I) [75.78 (7)ꢀ] is smaller
than that in [Cd(dadpm)2Br](dca) [98.7 (5)ꢀ; Luo et al., 2003],
but larger than that in [Cd(dadpm)(dca)2] [55.3 (2)ꢀ; Luo et al.,
2003]. The C(Ph)ÐCÐC(Ph) bond angle between the two
phenyl groups of dadpm in (I) is 117.0 (2)ꢀ, which is slightly
larger than the values reported for [CdCl(dadpm)2](dca)
[115.8 (4)ꢀ; Luo et al., 2003], [CdBr(dadpm)2](dca) [115.9 (1)ꢀ;
Luo et al., 2003] and {[CuCl(dadpm)(C3H4O4)]Cl}2 [114.7 (7)ꢀ;
Zhang et al., 1999].
Co1ÐO2
Co1ÐO1
Co1ÐN1
2.0319 (12)
2.0672 (12)
2.2201 (17)
O1ÐC2
O2ÐC4
N1ÐC6
1.269 (2)
1.259 (2)
1.425 (2)
O2ÐCo1ÐO1
O2ÐCo1ÐN1
O1ÐCo1ÐN1
89.87 (5)
91.46 (6)
93.07 (6)
C6ÐN1ÐCo1
C9iÐC12ÐC9
118.35 (12)
117.0 (2)
Symmetry code: (i) x; y; 12 z.
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
N1ÐH1AÁ Á ÁO1ii
DÐH
HÁ Á ÁA
2.36 (2)
DÁ Á ÁA
DÐHÁ Á ÁA
The NH2 groups of the dadpm ligand of (I) interact with the
O atoms of acac anions from adjacent chains via atom H1A
(Table 2), thereby forming a two-dimensional hydrogen-
bonded network (Fig. 2). The second atom, H1B, is located
0.83 (2)
3.155 (2)
159 (2)
Symmetry code: (ii) 1 x; 1 y; 1 z.
Ê
2.51 (3) A above the Co(acac) group and in contact with an
All H atoms were placed in geometrically idealized positions and
re®ned with isotropic displacement parameters.
Ê
adjacent atom, H1E(1 x, 1 y, 1 z), at 2.37 (4) A.
Data collection: CrystalClear (Rigaku, 2001); cell re®nement:
CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004);
program(s) used to solve structure: SHELXS97 (Sheldrick, 1997);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: ORTEPII (Johnson, 1976); software used to
prepare material for publication: SHELXL97.
Experimental
An ethanol solution (3.5 ml) of 4,40-methylenedianiline (0.103 g,
0.1 mmol) was added to [Co(acac)2(CH3CO2)2]Á6H2O (0.035 g,
0.1 mmol) in N,N-dimethylformamide (1.5 ml) at room temperature
and the resulting mixture stirred for 1 h. The mixture was layered
with propan-2-ol and pink plates of (I) were formed (yield 0.023 g,
51% based on Co). The crystal used for the crystal structure deter-
mination was obtained directly from the above preparation. Analysis
found: C 60.85, H 6.18, N 6.22%; calculated for C23H28CoN2O4: C
60.66, H 6.20, N 6.15%. IR (KBr, ꢀ, cm 1): 3368 (w), 3271 (w), 1589
(s), 1512 (s), 1458 (s), 1408 (s), 1358 (w), 1253 (m), 972 (m), 760 (w),
555 (w).
The authors thank the National Natural Science Foundation
of China (grant No. 20271036), the Natural Science Founda-
tion of the Education Committee of Jiangsu Province (grant
No. 02KJB150001), the State Key Laboratory of Organo-
metallic Chemistry (grant No. 04-31) and the Key Laboratory
of Organic Synthesis of Jiangsu Province (grant No. JSK001)
for supporting this study.
ꢁ
Acta Cryst. (2004). C60, m554±m556
Xin-Lei Zhi et al.
[Co(C5H7O2)2(C13H14N2)] m555

metal-organic compounds
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m556 Xin-Lei Zhi et al.
[Co(C5H7O2)2(C13H14N2)]
Acta Cryst. (2004). C60, m554±m556