Diaqua-bis(N,N-diethyl-nicotinamide-κN)bis-(4-methyl-benzoato-κO)cobalt(II).

Abstract

In the centrosymmetric mononuclear title complex, [Co(C(8)H(7)O(2))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], the Co(II) ion is located on an inversion center. The asymmetric unit contains one 4-methyl-benzoate (PMB) anion, one N,N-diethyl-nicotinamide (DENA) ligand and one coordinated water mol-ecule. The four O atoms in the equatorial plane around the Co(II) ion form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two pyridine N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the attached benzene ring is 3.73 (14)°, while the pyridine and benzene rings are oriented at a dihedral angle of 77.28 (6)°. In the crystal structure, inter-molecular O-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a two-dimensional network parallel to (001). The structure is further stabilized by π-π contacts between the pyridine rings [centroid-centroid distance = 3.544 (1) Å] and weak C-H⋯π inter-actions involving the benzene ring.

Full text

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Diaquabis(N,N-diethylnicotinamide-
jN1)bis(4-methylbenzoato-jO)cobalt(II)
Hacali Necefog ˘lu,aEfdal C ¸imen,aBarıs ¸ Tercan,bEmel
Ermis ¸cand Tuncer Ho ¨kelekd*
aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey,bDepartment of
Physics, Karabu ¨k University, 78050 Karabu ¨k, Turkey,cDepartment of Chemistry,
Faculty of Science, Anadolu University, 26470 Yenibag ˘lar, Eskis ¸ehir, Turkey, and
dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
Correspondence e-mail: merzifon@hacettepe.edu.tr
Received 4 April 2010; accepted 15 April 2010
Key indicators: single-crystal X-ray study; T = 100 K; mean ?(C–C) = 0.003 A ˚;
R factor = 0.038; wR factor = 0.090; data-to-parameter ratio = 19.2.
In
[Co(C8H7O2)2(C10H14N2O)2(H2O)2], the CoIIion is located
on an inversion center. The asymmetric unit contains one 4-
methylbenzoate (PMB) anion, one N,N-diethylnicotinamide
(DENA) ligand and one coordinated watermolecule. The four
O atoms in the equatorial plane around the CoIIion form a
slightly distorted square-planar arrangement, while the
slightly distorted octahedral coordination is completed by
the two pyridine N atoms of the DENA ligands in the axial
positions. The dihedral angle between the carboxylate group
and the attached benzene ring is 3.73 (14)?, while the pyridine
and benzene rings are oriented at a dihedral angle of
77.28 (6)?. In the crystal structure, intermolecular O—H???O
and C—H???O hydrogen bonds link the molecules into a two-
dimensional network parallel to (001). The structure is further
stabilized by ?–? contacts between the pyridine rings
[centroid–centroid distance = 3.544 (1) A˚] and weak C—
H???? interactions involving the benzene ring.
the centrosymmetric mononucleartitlecomplex,
Related literature
For niacin, see: Krishnamachari (1974), and for the nicotinic
acid derivative N,N-diethylnicotinamide, see: Bigoli et al.
(1972). For related structures, see: Ho ¨kelek et al. (1996,
2009a,b,c); Ho ¨kelek & Necefog ˘lu (1998); Necefog ˘lu et al.
(2010).
Experimental
Crystal data
[Co(C8H7O2)2(C10H14N2O)2-
(H2O)2]
Mr= 721.70
Triclinic, P1
a = 7.2791 (2) A˚
b = 8.5453 (2) A˚
c = 16.0438 (4) A˚
? = 84.090 (3)?
? = 77.583 (3)?
? = 67.271 (2)?
V = 898.71 (4) A˚3
Z = 1
Mo K? radiation
? = 0.53 mm?1
T = 100 K
0.35 ? 0.25 ? 0.15 mm
Data collection
Bruker Kappa APEXII CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
Tmin= 0.852, Tmax= 0.922
15243 measured reflections
4484 independent reflections
3821 reflections with I > 2?(I)
Rint= 0.025
Refinement
R[F2> 2?(F2)] = 0.038
wR(F2) = 0.090
S = 1.04
4484 reflections
234 parameters
3 restraints
H atoms treated by a mixture of
independent and constrained
refinement
??max= 0.86 e A˚?3
??min= ?0.55 e A˚?3
Table 1
Selected bond lengths (A˚).
Co1—O2
Co1—O4
2.0885 (12)
2.1209 (12)
Co1—N1 2.1439 (14)
Table 2
Hydrogen-bond geometry (A˚,?).
Cg1 is the centroid of the C2–C7 ring.
D—H???A
O4—H41???O1i
O4—H42???O3ii
C6—H6???O1
C11—H11???O1
C17—H17A???Cg1iii
Symmetry codes: (i) ?x;?y;?z; (ii) ?x þ 1;?y;?z; (iii) x ? 1;y þ 1;z.
D—HH???AD???AD—H???A
1.00 (2)
0.89 (2)
0.93
0.93
0.97
1.69 (2)
1.88 (2)
2.40
2.42
2.95
2.6443 (18)
2.7557 (18)
3.249 (3)
3.339 (2)
3.594 (2)
160 (3)
170 (2)
152
168
125
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure:SHELXL97(Sheldrick,
Mercury (Macrae et al., 2006); software used to prepare material for
publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
2008);molecular graphics:
The authors are indebted to Anadolu University and the
Medicinal Plants and Medicine Research Centre of Anadolu
University, Eskis ¸ehir, Turkey, for the use of X-ray diffract-
ometer. This work was supported financially by the Scientific
and Technological Research Council of Turkey (grant No. 108
T657).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: CI5076).
metal-organic compounds
m556
Necefog ˘lu et al.
doi:10.1107/S1600536810013954
Acta Cryst. (2010). E66, m556–m557
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111.
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R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
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Cryst. E66, m361–m362.
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metal-organic compounds
Acta Cryst. (2010). E66, m556–m557Necefog ˘lu et al.
? [Co(C8H7O2)2(C10H14N2O)2(H2O)2]
m557

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supplementary materials

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supplementary materials
sup-1
Acta Cryst. (2010). E66, m556-m557 [ doi:10.1107/S1600536810013954 ]
Diaquabis(N,N-diethylnicotinamide- N1)bis(4-methylbenzoato- O)cobalt(II)
H. Necefoglu, E. Çimen, B. Tercan, E. Ermis and T. Hökelek
Comment
As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krish-
namachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant
(Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.
The title complex, (I), is a crystallographically centrosymmetric mononuclear complex, consisting of two N,N-diethyl-
nicotinamide (DENA) and two 4-methylbenzoate (PMB) ligands and two coordinated water molecules; the CoII ion
lies on the centre of inversion (Fig. 1). The crystal structures of similar complexes of CuII, CoII, NiII, MnII and ZnII
ions, [Cu(C7H5O2)2(C10H14N2O)2], (II) (Hökelek et al., 1996), [Co(C6H6N2O)2(C7H4NO4)2(H2O)2], (III) (Hökelek &
Necefoğlu, 1998), [Ni(C7H4ClO2)2(C6H6N2O)2(H2O)2], (IV) (Hökelek et al., 2009a), [Ni(C8H7O2)2(C6H6N2O)2(H2O)2],
(V) (Necefoğlu et al., 2010), [Mn(C7H4ClO2)2(C10H14N2O)2(H2O)2], (VI) (Hökelek et al., 2009b) and
[Zn(C7H4BrO2)2(C6H6N2O)2(H2O)2], (VII) (Hökelek et al., 2009c) have also been reported. In (II), the two benzoate ions
are coordinated to the CuII atom as bidentate ligands, while in the other structures all ligands are monodentate.
All ligands are monodentate in (I). The four O atoms (O2, O4, and the symmetry-related atoms O2', O4') in the equat-
orial plane around the CoII ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral
coordination is completed by the pyridine N atoms of two DENA ligands (N1, N1') in the axial positions (Fig. 1). The near
equality of the C1—O1 [1.257 (2) Å] and C1—O2 [1.266 (2) Å] bonds in the carboxylate group indicates a delocalized
bonding arrangement, rather than localized single and double bonds. The average Co—O bond length is 2.1047 (12) Å
(Table 1), and the Co1 atom is displaced out of the least-squares plane of the carboxylate group (O1/C1/O2) by 0.8823 (1)
Å. The dihedral angle between the planar carboxylate group and the benzene ring A (C2—C7) is 3.73 (14)°, while that
between rings A and B (N1/C9—C13) is 77.28 (6)°.
In the crystal structure, intermolecular O—H···O and C—H···O hydrogen bonds (Table 2) link the molecules into a
two-dimensional network parallel to the (001). The π–π contact between the pyridine rings (N1/C9—C13) at (x, y, z) and
(1-x, -1-y, -z) [centroid-centroid distance = 3.544 (1) Å] further stabilize the structure. A weak C—H···π interaction involving
the benzene ring is also observed (Table 2).
Experimental
The title compound was prepared by the reaction of CoSO4.7H2O (1.41 g, 5 mmol) in H2O (40 ml) and DENA (1.78 g, 10
mmol) in H2O (10 ml) with sodium 4-methylbenzoate (1.58 g, 10 mmol) in H2O (300 ml). The mixture was filtered and set
aside to crystallize at ambient temperature for one week, giving pink single crystals.

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supplementary materials
sup-2
Refinement
Water H atoms (H41 and H42) were located in a difference Fourier map and refined with O–H and H···H distance restraints
of 0.95 (2) Å and 1.46 (4) Å, respectively. The remaining H atoms were positioned geometrically with C-H = 0.93, 0.97
and 0.96 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with
Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
Figures
Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Dis-
placement ellipsoids are drawn at the 30% probability level. Primed atoms are generated by
the symmetry operator:(') -x, -y, -z.
Diaquabis(N,N-diethylnicotinamide-κN1)bis(4- methylbenzoato-κO)cobalt(II)
Crystal data
[Co(C8H7O2)2(C10H14N2O)2(H2O)2]
Mr = 721.70
Z = 1
F(000) = 381
Dx = 1.334 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7347 reflections
θ = 2.6–28.3°
µ = 0.53 mm−1
T = 100 K
Block, pink
0.35 × 0.25 × 0.15 mm
Triclinic, P1
Hall symbol: -P 1
a = 7.2791 (2) Å
b = 8.5453 (2) Å
c = 16.0438 (4) Å
α = 84.090 (3)°
β = 77.583 (3)°
γ = 67.271 (2)°
V = 898.71 (4) Å3
Data collection
Bruker Kappa APEXII CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
graphite
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
Tmin = 0.852, Tmax = 0.922
15243 measured reflections
4484 independent reflections
3821 reflections with I > 2σ(I)
Rint = 0.025
θmax = 28.5°, θmin = 1.3°
h = −9→9
k = −11→11
l = −21→21
Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods