Crystal structure of cis bis(4-benzoyl-3-methyl-1-phenyl pyrazol-5-one)-
cis bis(methanol)-cobalt(II), C
36
H
34
CoN
4
O
6
Omoruyi G. Idemudia
*, I
, Alexander P. Sadimenko
I
and Eric C. Hosten
II
I
Department of Chemistry, University of Fort Hare, Private Bag X1314, Alice 5700, South Africa
II
Department of Chemistry, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth 6031, South Africa
Received July 02, 2014, accepted March 05, 2015, available online March 10, 2015, CCDC no. 1267/4260
Abstract
C
36
H
34
CoN
4
O
6
, monoclinic, P2
1
/n (no. 14), a = 13.9021(5) Å,
b = 13.9557(5) Å, c = 17.3379(6) Å, b = 101.254(2)°,
V = 3299.1 Å
3
, Z = 4, R
gt
(F) = 0.0316, wR
ref
(F
2
) = 0.0869,
T = 200 K.
Source of material
To a solution of Bmpp-Ph (3-methyl-1-phenyl-4-[(phenyl)(2-
phenylhydrazin-1-yl)methylidene]-1H-pyrazol-5(4H)-one, 2
mmol, 0.74 g) in hot ethanol (40 mL) was added in drops aqueous
solution of CoCl
2
×4H
2
O (1 mmol, 0.20 g) while stirring under re-
flux. After 4 h of reflux, the pink precipitate was filtered, washed
with ethanol/water (1:1), dried at room temperature and stored
over fused CaCl
2
. Slow evaporation of a solution of the resultant
pink solid in methanol afforded orange crystals of an unprece-
dented Co(Bmpp)
2
(MeOH)
2
suitable for x-ray crystallography.
Experimental details
Carbon-bound H atoms were placed in calculated positions and
were included in the refinement in the riding model approxima-
tion, with U
iso
(H) set to 1.2 U
eq
(C). The H atoms of the methyl
groups were allowed to rotate with a fixed angle around the C–C
bond to best fit the experimental electron density (HFIX 137 in
the SHELX program suite [11]), with U
iso
(H) set to 1.5 U
eq
(C).
The oxygen-bound H atoms were located on a difference Fourier
map and refined freely.
Discussion
As an analytical reagent acylpyrazolones have been employed as
good spectroscopic chelating ligand for the determination of met-
als in trace amounts [1], they have also been used as excellent cat-
alysts [2]. They are bioactive di-ketone heterocycles [3] and are
capable of forming Schiff bases with amino groups [4, 5]. Suc-
cessful coordination of acylpyrazolone diketones with transition
metals have been reported to increase their catalytic properties
[6]. We have already reported a bioactive cobalt complex of acyl-
pyrazolone [7]. In view of our interest in metal complexes of
Schiff bases, presented herein is the molecular and crystal struc-
ture of a new cobalt complex. The studies on the bioactive and
catalytic activities of the title compound are presently ongoing. In
the crystal structure the title complex has an octahedral coordina-
tion geometry consisting of two Bmpp ligands and two coordinat-
ing methanol molecules. Each 4-benzoyl-3-methyl-1-phenyl
pyrazol-5-one (Bmpp) ligand is deprotonated with the negative
charge delocalized. The Bmpp ligands occur cis to each other sim-
ilarly to the cis complex reported by Wu et al. [8] which has one
methanol and one ethanol ligand. In contrast the complex we re-
ported earlier [7] with two coordinating ethanol ligands has two
Bmpp ligands trans to each other. The average Bmpp Co–O bond
length here is 2.070(33) Å which is very similar to the mixed etha-
nol methanol complex [8] where the average bond length is
2.071(29) Å. In the complex with the two trans ethanols [7] the
average Co–O bond length is only slightly shorter at 2.038(36) Å.
The title complex is obviously non-centrosym-metrical therefore
the two Bmpp ligands having different geometrical configura-
tions. In the first ligand the dihedral angle between the least
square planes through the phenyl rings is 20.76(9)°, while in the
second ligand the dihedral angle is larger at 86.25(10)°. There are
a number of potential intramolecular hydrogen bonds with the
shortest being the C216–H216×××O21 interaction with length 2.24
Å. There is also an intramolecular C–H×××p ring interaction
C222–H222 with the pyrazole ring N11, N12, C11–C13 of length
2.55 Å to the ring centroid. In the crystal structure adjacent com-
plexes are linked together with two intermolecular O3–H3×××O22
interactions with length 1.94(2) Å which in terms of graph-set
162 Z. Kristallogr. NCS 230 (2015) 162-164 / DOI 10.1515/ncrs-2014-0239
© 2015 Walter de Gruyter GmbH, Berlin/Munich/Boston
Crystal: orange blocks, size 0.365´0.396´0.444 mm
Wavelength: Mo K
a
radiation (0.71073 Å)
m: 5.72 cm
-1
Diffractometer, scan mode: Bruker APEX-II CCD, j and w
2q
max
: 56.77°
N(hkl)
measured
, N(hkl)
unique
: 48511, 8246
Criterion for I
obs
, N(hkl)
gt
: I
obs
>2 s(I
obs
), 6934
N(param)
refined
: 436
Programs: SHELX, SADABS, SAINT, ShelXLe,
ORTEP-3, PLATON, MERCURY [11–16]
Table 1. Data collection and handling.
_____________
* Correspondence author (e-mail: oidemudia@ufh.ac.za)