Trans-diaqua-bis(nicotinamide-κN)bis-(salicylato-κO)cobalt(II)

Article abstract of DOI:10.1107/S0108270108029521

The title compound, [Co(C₇H₅O₃) ₂(C₆H₆N₂O)₂(H ₂O)₂], forms a three-dimensional hydrogen-bonded supra-molecular structure. The Co^II ion is in an octa-hedral coordination environment comprising two pyridyl N atoms, two carboxyl-ate O atoms and two O atoms from water mol-ecules. Inter-molecular N - H...O and O - H...O hydrogen bonds produce R ₂²(8), R ₂²(12) and R ₂²(14) rings, which lead to two-dimensional chains. An extensive three-dimensional supra-molecular network of C - H...O, N - H...O and O - H...O hydrogen bonds and C - H...π inter-actions is responsible for crystal structure stabilization. This study is an example of the construction of a supra-molecular assembly based on hydrogen bonds in mixed-ligand metal complexes.

Full text of DOI:10.1107/S0108270108029521

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
The molecular structure of (I) and the atom-labelling
scheme are shown in Fig. 1. The CoII ion is coordinated by two
O atoms from two identical carboxylate groups, two O atoms
from two water molecules and two pyridyl N atoms. The
ISSN 0108-2701
trans-Diaquabis(nicotinamide-jN)-
bis(salicylato-jO)cobalt(II)
Onur S¸ahin,a* Orhan Buyukgungor,a Dursun Ali Koseb and
¨
¨
¨ ¨
¨
Hacali Necefogluc
aDepartment of Physics, Ondokuz Mayıs University, TR-55139 Samsun, Turkey,
bDepartment of Chemistry, Hacettepe University, Beytepe Campus, TR-06800
Ankara, Turkey, and cDepartment of Chemistry, Kafkas University, Derei¸ci,
TR-36100 Kars, Turkey
geometry around the CoII ion (Table 1) is that of a slightly
distorted octahedron. The distortion arises from the N1—
Co1—N2 axis, which is not perfectly perpendicular to the
coordination plane (O1/O2/O3/O4/Co1). The significant
difference between the Co—O bond distances in the equa-
torial plane and the Co—N bond distances in the axial posi-
tions has also been observed in another cobalt complex (S¸ahin
et al., 2007).
Correspondence e-mail: onurs@omu.edu.tr
Received 5 August 2008
Accepted 15 September 2008
Online 20 September 2008
The molecules of (I) are linked by intermolecular hydrogen
bonding, and we employ graph-set notation (Bernstein et al.,
1995) to describe the patterns of hydrogen bonding. Molecules
of (I) are linked into sheets by a combination of C—Hꢀ ꢀ ꢀO,
O—Hꢀ ꢀ ꢀO and N—Hꢀ ꢀ ꢀO hydrogen bonds (Table 2). Within
the selected asymmetric unit, intramolecular O—Hꢀ ꢀ ꢀO
hydrogen bonds define S12(10) and S(6) motifs (Fig. 1). Water
atom O1 in the molecule at (x, y, z) acts as hydrogen-bond
donor, via atoms H1A and H1B, to atom O5 at (x + 1, y, z) and
O10 at (x + 1, y, z), respectively, so forming a C(6)C(8)[R22(12)]
chain of rings running parallel to the [100] direction. Similarly,
The title compound, [Co(C7H5O3)2(C6H6N2O)2(H2O)2],
forms a three-dimensional hydrogen-bonded supramolecular
structure. The CoII ion is in an octahedral coordination
environment comprising two pyridyl N atoms, two carboxylate
O atoms and two O atoms from water molecules. Inter-
molecular N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀO hydrogen bonds produce
R22(8), R22(12) and R22(14) rings, which lead to two-dimensional
chains. An extensive three-dimensional supramolecular
network of C—Hꢀ ꢀ ꢀO, N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀO hydrogen
bonds and C—Hꢀ ꢀ ꢀꢀ interactions is responsible for crystal
structure stabilization. This study is an example of the
construction of a supramolecular assembly based on hydrogen
bonds in mixed-ligand metal complexes.
Comment
Metal–organic supramolecular complexes with various fasci-
nating topologies have been studied widely for their versatile
chemical and physical properties and potential applications as
functional materials (Janiak, 2003; Kitagawa et al., 2004; Yaghi
et al., 2003). Self-assembly based on molecular building blocks
has become an effective approach for constructing these
functional materials. In the development of supramolecular
chemistry, hydrogen-bonding and ꢀ–ꢀ interactions, acting as
the two main driving forces, play an important role in the self-
assembly of multidimensional metal–organic supramolecular
frameworks or networks (Graham & Pike, 2000; Mitzi et al.,
1995). Some interesting coordination polymers assembled
with 4,40-bipyridine (bipy) have been reported, showing
various structural motifs, including two-dimensional layers
(Carlucci et al., 1997; Tong et al., 1998) and three-dimensional
nets (Lu et al., 1998; Hagrman et al., 1998; Kondo et al., 1999;
Greve et al., 2003; Zhang et al., 1999; S¸ahin et al., 2007). We
report here the structure of the title complex, (I), in which
hydrogen-bond interactions lead to a three-dimensional
supramolecular network.
Figure 1
A view of the molecule of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are
indicated by dashed lines.
Acta Cryst. (2008). C64, m317–m320
doi:10.1107/S0108270108029521
# 2008 International Union of Crystallography m317

metal-organic compounds
Figure 3
Part of the crystal structure of (I), showing the formation of an R22(8)
dimer. Hydrogen bonds are indicated by dashed lines. H atoms not
involved in these interactions have been omitted for clarity. (Symmetry
codes as in Table 2.)
ates a chain of edge-fused R44(40) rings parallel to the bc plane
(Fig. 4).
Compound (I) also contains two intermolecular C—Hꢀ ꢀ ꢀꢀ
interactions. In the first, atom C9 in the molecule at (x, y, z)
acts as hydrogen-bond donor to the C21–C26 benzene ring in
the molecule at (x, y, z ꢁ 1), so forming a chain running
parallel to the [001] direction. In the second, atom C3 in the
molecule at (x, y, z) acts as hydrogen-bond donor to the C14–
C19 benzene ring in the molecule at (x, y, z + 1), so forming a
chain running parallel to the [001] direction. Details of these
interactions are given in Table 2. The combination of C—
Hꢀ ꢀ ꢀꢀ interactions defines an R22(20) ring pattern (Fig. 5).
Figure 2
Part of the crystal structure of (I), showing the formation of R22(12) and
R22(14) rings. Hydrogen bonds are indicated by dashed lines. H atoms not
involved in these interactions have been omitted for clarity. (Symmetry
codes as in Table 2.)
water atom O2 in the reference molecule at (x, y, z) acts as
hydrogen-bond donor, via atom H2B, to atom O9 in the
molecule at (x ꢁ 1, y, z), so forming a C(8) chain running
parallel to the [100] direction. The combination of C(6) and
C(8) chains generates a chain of edge-fused R22(14) rings
running parallel to the [100] direction (Fig. 2). Amino atom N4
in the reference molecule at (x, y, z) acts as hydrogen-bond
donor, via atom H4A, to atom O10 in the molecule at (x + 1, y,
z ꢁ 1), so forming a C(12) chain running parallel to the [101]
direction (Fig. 3). Amino atom N3 in the molecule at (x, y, z)
acts as hydrogen-bond donor, via atom H3A, to atom O9 in
the molecule at (x ꢁ 1, y, z + 1), so forming a C(12) chain
running parallel to the [101] direction. The combination of
C(12) chains generates a chain of edge-fused R22(8) rings
running parallel to the [101] direction (Fig. 3).
Fig. 4 shows the way in which amino atom N4, hydroxyl
atom O6, atom C18 and carboxylate atom O5 enter into
intermolecular hydrogen-bonding interactions. As a result,
amino atom N4 in the reference molecule at (x, y, z) acts as
hydrogen-bond donor, via atom H4B, to atom O6 in the
molecule at (x, y, z ꢁ 1), so forming a C(12) chain running
parallel to the [001] direction. At the same time, atom C18 in
the reference molecule at (x, y, z) acts as hydrogen-bond
Figure 4
Part of the crystal structure of (I), showing the formation of a chain of
edge-fused R44(40) rings. Hydrogen bonds are indicated by dashed lines.
For the sake of clarity, H atoms not involved in the motif shown have
1
donor, via atom H18, to atom O5 in the molecule at (ꢁx, y ꢁ ,
2
1
2
ꢁz), so forming a C(10) chain running parallel to the [010]
direction. The combination of C(10) and C(12) chains gener-
been omitted. [Symmetry codes: (iii) x, y, z ꢁ 1; (vi) ꢁx, y ꢁ , ꢁz; (vii) x,
1
2
y, z + 1; (viii) ꢁx, y + , ꢁz.]
ꢂ
m318 ¸Sahin et al. [Co(C7H5O3)2(C6H6N2O)2(H2O)2]
Acta Cryst. (2008). C64, m317–m320

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
ꢃ
˚
N1—Co1
N2—Co1
O1—Co1
2.157 (3)
2.147 (3)
2.112 (3)
O2—Co1
O3—Co1
O4—Co1
2.121 (3)
2.079 (3)
2.076 (3)
C13—O3—Co1
C20—O4—Co1
O4—Co1—O3
130.1 (3)
134.1 (3)
174.58 (11)
O1—Co1—O2
N2—Co1—N1
174.40 (12)
178.26 (12)
Figure 5
Part of the crystal structure of (I), showing the formation of a chain along
[001] generated by the C—Hꢀ ꢀ ꢀꢀ interactions (dashed lines; see Table 2).
For the sake of clarity, H atoms not involved in the motif shown have
been omitted. [Symmetry codes: (iii) x, y, z ꢁ 1; (vii) x, y, z + 1.]
Table 2
Hydrogen-bond geometry (A, ).
ꢃ
˚
Cg1 and Cg2 are the centroids of the C14–C19 and C21–C26 benzene rings,
respectively.
The combination of the chains along [100], [101], [010] and
[001] suffices to generate a three-dimensional structure of
considerable complexity.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N3—H3Aꢀ ꢀ ꢀO9i
N4—H4Aꢀ ꢀ ꢀO10ii
N4—H4Bꢀ ꢀ ꢀO6iii
O6—H6ꢀ ꢀ ꢀO4
0.86
0.86
0.86
0.82
2.11
2.09
2.48
1.80
2.955 (4)
2.916 (5)
3.210 (6)
2.521 (4)
2.553 (5)
2.684 (4)
2.810 (4)
2.677 (5)
2.906 (4)
3.311 (6)
3.520 (4)
3.614 (4)
167
162
144
146
Experimental
O8—H8Aꢀ ꢀ ꢀO7
O1—H1Aꢀ ꢀ ꢀO5iv
O1—H1Bꢀ ꢀ ꢀO10iv
O2—H2Aꢀ ꢀ ꢀO7
O2—H2Bꢀ ꢀ ꢀO9v
C18—H18ꢀ ꢀ ꢀO5vi
C3—H3ꢀ ꢀ ꢀCg1vii
C9—H9ꢀ ꢀ ꢀCg2iii
0.82
1.83
147
As a first step, the sodium salt of salicylic acid (SA) was prepared and
cobalt salicylate was synthesized from the Na(SA) salt. A solution of
Co(SA)2ꢀnH2O in water was left for 15 d at room temperature for
crystallization. In a second step, a solution of nicotinamide (2 mmol)
in distilled water (30 ml) was added dropwise to a stirred solution of
Co(SA)2ꢀnH2O (1 mmol) in hot distilled water (50 ml). The resulting
solution was heated to 323 K in a temperature-controlled bath and
stirred for 4 h, then cooled to room temperature and left for 15–17 d
for crystallization. The brown crystals which formed were filtered off,
washed with cold water and acetone and dried in vacuo (yield 84%,
0.83 (5)
0.81 (4)
0.834 (19)
0.82 (4)
0.93
1.86 (5)
2.11 (4)
1.88 (2)
2.23 (4)
2.41
172 (5)
145 (5)
158 (5)
140 (5)
165
0.93
0.93
2.68
2.82
151
144
Symmetry codes: (i) x ꢁ 1; y; z þ 1; (ii) x þ 1; y; z ꢁ 1; (iii) x; y; z ꢁ 1; (iv) x þ 1; y; z; (v)
1
2
x ꢁ 1; y; z; (vi) ꢁx; y ꢁ ; ꢁz; (vii) x; y; z þ 1.
˚
were allowed for with a fixed O—H distance of 0.82 A [Uiso(H) =
1.5Ueq(O)].
0.51 g). Analysis found:
C26H28CoN4O10: C 50.86, H 4.57%.
C
50.38,
H
4.12%; calculated for
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement:
X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s)
used to solve structure: SHELXS97 (Sheldrick, 2008); program(s)
used to refine structure: SHELXL97 (Sheldrick, 2008); molecular
graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to
prepare material for publication: WinGX (Farrugia, 1999).
Crystal data
3
˚
[Co(C7H5O3)2(C6H6N2O)2(H2O)2]
Mr = 613.44
Monoclinic, P21
V = 1331.33 (11) A
Z = 2
Mo Kꢂ radiation
ꢃ = 0.71 mmꢁ1
T = 296 K
˚
a = 7.0484 (4) A
˚
b = 19.4249 (7) A
˚
c = 10.3331 (5) A
0.48 ꢄ 0.39 ꢄ 0.36 mm
The authors acknowledge the Faculty of Arts and Sciences,
Ondokuz Mayıs University, Turkey, for the use of the Stoe
IPDSII diffractometer (purchased under grant No. F279 of the
University Research Fund).
ꢁ = 109.774 (4)ꢃ
Data collection
Stoe IPDSII diffractometer
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
Tmin = 0.549, Tmax = 0.811
9880 measured reflections
5360 independent reflections
4725 reflections with I > 2ꢄ(I)
Rint = 0.061
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: HJ3085). Services for accessing these data are
described at the back of the journal.
Refinement
R[F2 > 2ꢄ(F2)] = 0.043
wR(F2) = 0.115
S = 1.05
5360 reflections
383 parameters
7 restraints
H atoms treated by a mixture of
independent and constrained
refinement
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Carlucci, L., Ciani, G., Proserpio, D. M. & Sironi, A. (1997). J. Chem. Soc.
Dalton Trans. pp. 1801–1803.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Graham, P. M. & Pike, R. D. (2000). Inorg. Chem. 39, 5121–5132.
ꢁ3
˚
Áꢅmax = 0.38 e A
ꢁ3
˚
Áꢅmin = ꢁ0.67 e A
Absolute structure: Flack (1983),
with 2533 Friedel pairs
Flack parameter: 0.012 (16)
H atoms bonded to C and N atoms were included in their expected
positions and allowed to ride, with C—H and N—H distances
¨
Greve, J., Jess, I. & Nather, C. (2003). J. Solid State Chem. 175, 328–340.
Hagrman, D., Hammond, R. P., Haushalter, R. & Zubieta, J. (1998). Chem.
Mater. 10, 2091–2094.
Janiak, C. (2003). Dalton Trans. pp. 2781–2804.
Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–
2375.
˚
restrained to 0.93 and 0.86 A, respectively, and with Uiso(H) =
1.2Ueq(C,N). Water H atoms were located in a difference map and
refined subject to a DFIX (SHELXL97; Sheldrick, 2008) restraint of
˚
O—H = 0.83 (2) A. The H atoms of the hydroxy groups (O6 and O8)
ꢂ
Acta Cryst. (2008). C64, m317–m320
¸Sahin et al.
[Co(C7H5O3)2(C6H6N2O)2(H2O)2] m319

metal-organic compounds
Kondo, M., Shimamura, M., Noro, S. I., Yoshitomi, T., Minakoshi, S. &
Kitagawa, S. (1999). Chem. Lett. pp. 285–286.
Lu, J., Yu, C., Niu, T. Y., Paliwala, T., Crisci, G., Somosa, F. & Jacobson, A. J.
(1998). Inorg. Chem. 37, 4637–4640.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Stoe & Cie (2002). X-RED and X-AREA. Stoe & Cie, Darmstadt, Germany.
Tong, M. L., Cai, J. W., Yu, X. L., Che, X. M., Ng, S. W. & Mak, T. C. W. (1998).
Aust. J. Chem. 51, 637–641.
Mitzi, D. B., Wang, S., Feild, C. A., Chess, C. A. & Guloy, A. M. (1995). Science,
267, 1473–1476.
Yaghi, O. M., O’Keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim,
J. (2003). Nature (London), 423, 705–714.
¨
¨
¨
¨
¨
S¸ahin, O., Buyukgungor, O., Kose, D. A., Ozturkkan, E. F. & Necefoglu, H.
(2007). Acta Cryst. C63, m243–m245.
Zhang, Y. S., Enright, G. D., Breeze, S. R. & Wang, S. (1999). New J. Chem. 23,
625–628.
ꢂ
m320 ¸Sahin et al. [Co(C7H5O3)2(C6H6N2O)2(H2O)2]
Acta Cryst. (2008). C64, m317–m320