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Acta Cryst. (2007). E63, m2326    [ doi:10.1107/S1600536807036896 ]

Diaquabis(2-oxidopyridinium-3-carboxylato-[kappa]2O2,O3)cobalt(II)

H.-Y. Yan and T.-Q. Hu

Abstract top

In the title mononuclear complex, [Co(C6H4NO3)2(H2O)2], the six-coordinate CoII atom assumes an octahedral geometry and is located on an inversion centre. There is a weak [pi]-[pi] stacking interaction between adjacent pyridyl rings [centroid-to-centroid distance = 3.8067 (17) Å and perpendicular distance = 3.533 Å]. O-H...O, N-H...O and C-H...O hydrogen bonds connect the mononuclear complexes and form a supramolecular three-dimensional structure.

Comment top

Metal complexes containing N-heterocyclic ligands play a pivotal role in the area of modern coordination chemistry, and it has been reported that complex containing 3-hydroxypicolinamide ligand displays strong fluorescent emission (Sakai et al., 2006). The interest in this area led us to synthesize the title complex, and here we report its crystal structure, (I).

Fig. 1 shows the molecular structure of (I), the CoII atom lies in an inversion centre and assumes a little distored octahedral geometry (Table 1). There is a weak π-π stacking interaction between adjacent pyridyl rings of the neighboring complexes; the relevant distances are Cg1···Cg1i = 3.8067 (17) Å and Cg1···Cg1iperp = 3.533 Å [symmetry codes: (i) X, 3/2-Y, −1/2+Z; Cg1 is the centroid of pyridyl ring; Cg1···Cg1perp is the perpendicular distance from ring Cg1 to ring Cg1i]. Table 2 and Fig. 2 show the information of O—H···O, N—H···O and C—H···O hydrogen bonds, and it is the hydrogen bonds that led to the connection of adjacent mononuclear complexes and to the formation of a super-molecular three-dimensional polymer.

Related literature top

For a related crystal structure, see: Sakai et al. (2006).

Experimental top

Diluted sodium hydroxide H2O solution was added in drops into 30 ml H2O solution containing Co(ClO4)2·6H2O (0.1830 g, 0.500 mmol) and 2-hydroxyl-3-carboxylpyridine (0.1390 g, 1.13 mmol) until the pH value reached 4, and the solution was stirred for another a few minutes. The red single crystals were obtained after the mixed solution had been allowed to stand at room temperature for one week.

Refinement top

H atoms of water molecule were located in a difference Fourier map and included in the refinements as riding in their as-found positions, with O—H = 0.886–0.889 Å, Uiso(H) = 1.5Ueq(O); the rest of the H atoms were placed in calculated positions with C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C); N—H = 0.86 Å, Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The coordination structure of (I) showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) −x, −y + 2, −z].
[Figure 2] Fig. 2. Unit cell and hydrogen bonds (line of dashes).
Diaquabis(2-oxidopyridinium-3-carboxylate)cobalt(II) top
Crystal data top
[Co(C6H4NO3)2(H2O)2]F000 = 378
Mr = 371.17Dx = 1.811 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1158 reflections
a = 7.4216 (19) Åθ = 2.8–26.7º
b = 12.330 (3) ŵ = 1.31 mm−1
c = 7.550 (2) ÅT = 298 (2) K
β = 99.921 (4)ºPrism, red
V = 680.6 (3) Å30.26 × 0.20 × 0.05 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		1331 independent reflections
Radiation source: fine-focus sealed tube1151 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 298(2) Kθmax = 26.0º
φ and ω scansθmin = 2.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→9
Tmin = 0.727, Tmax = 0.937k = −15→8
3627 measured reflectionsl = −9→8
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.083  w = 1/[σ2(Fo2) + (0.0376P)2 + 0.5342P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1331 reflectionsΔρmax = 0.39 e Å−3
106 parametersΔρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Co(C6H4NO3)2(H2O)2]V = 680.6 (3) Å3
Mr = 371.17Z = 2
Monoclinic, P21/cMo Kα
a = 7.4216 (19) ŵ = 1.31 mm−1
b = 12.330 (3) ÅT = 298 (2) K
c = 7.550 (2) Å0.26 × 0.20 × 0.05 mm
β = 99.921 (4)º
Data collection top
Bruker SMART APEX CCD
diffractometer		1331 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1151 reflections with I > 2σ(I)
Tmin = 0.727, Tmax = 0.937Rint = 0.035
3627 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034106 parameters
wR(F2) = 0.083H-atom parameters constrained
S = 1.02Δρmax = 0.39 e Å−3
1331 reflectionsΔρmin = −0.29 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1−0.0608 (2)0.84059 (13)−0.0153 (2)0.0183 (4)
C60.0373 (3)0.7569 (2)0.0071 (3)0.0153 (5)
Co10.00001.00000.00000.01392 (16)
O30.2707 (2)0.95557 (14)−0.0135 (2)0.0185 (4)
N10.5220 (3)0.86194 (17)0.1087 (3)0.0195 (5)
H10.58270.92110.10470.023*
O2−0.0295 (2)0.66277 (14)−0.0126 (2)0.0194 (4)
C10.2408 (3)0.7664 (2)0.0610 (3)0.0158 (5)
C50.3400 (4)0.6753 (2)0.1223 (3)0.0198 (6)
H40.27830.60980.12460.024*
O40.0769 (3)0.99441 (13)0.2817 (2)0.0239 (4)
H60.05451.05470.33800.036*
H50.03720.94110.34440.036*
C20.3378 (3)0.8659 (2)0.0496 (3)0.0157 (5)
C30.6169 (4)0.7728 (2)0.1729 (3)0.0235 (6)
H20.74270.77690.21150.028*
C40.5282 (4)0.6769 (2)0.1809 (4)0.0245 (6)
H30.59130.61450.22410.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0140 (9)0.0112 (9)0.0291 (10)0.0005 (7)0.0023 (7)−0.0004 (7)
C60.0171 (13)0.0169 (14)0.0124 (11)0.0000 (9)0.0041 (10)0.0001 (10)
Co10.0123 (3)0.0098 (3)0.0198 (3)0.00027 (18)0.00311 (18)0.00043 (19)
O30.0146 (9)0.0132 (9)0.0285 (10)0.0006 (7)0.0055 (7)0.0025 (8)
N10.0135 (11)0.0200 (12)0.0251 (12)−0.0025 (8)0.0031 (9)0.0012 (9)
O20.0194 (10)0.0111 (10)0.0269 (10)−0.0022 (7)0.0020 (8)−0.0005 (7)
C10.0171 (13)0.0153 (13)0.0152 (11)−0.0011 (10)0.0036 (10)0.0005 (10)
C50.0203 (14)0.0191 (14)0.0209 (13)−0.0001 (10)0.0056 (11)0.0030 (10)
O40.0371 (12)0.0128 (9)0.0223 (9)−0.0003 (8)0.0064 (8)0.0011 (7)
C20.0138 (13)0.0191 (14)0.0148 (12)−0.0004 (10)0.0041 (10)−0.0015 (10)
C30.0152 (13)0.0317 (16)0.0230 (13)0.0024 (11)0.0013 (11)0.0075 (12)
C40.0207 (15)0.0230 (15)0.0294 (14)0.0081 (11)0.0033 (11)0.0101 (11)
Geometric parameters (Å, °) top
O1—C61.257 (3)N1—C21.364 (3)
O1—Co12.0155 (17)N1—H10.8600
C6—O21.261 (3)C1—C51.379 (3)
C6—C11.500 (3)C1—C21.432 (3)
Co1—O1i2.0155 (17)C5—C41.390 (4)
Co1—O3i2.1016 (17)C5—H40.9300
Co1—O32.1016 (17)O4—H60.8862
Co1—O4i2.1065 (19)O4—H50.8893
Co1—O42.1065 (19)C3—C41.359 (4)
O3—C21.271 (3)C3—H20.9300
N1—C31.350 (3)C4—H30.9300
C6—O1—Co1132.40 (16)C3—N1—H1117.3
O1—C6—O2122.2 (2)C2—N1—H1117.3
O1—C6—C1120.3 (2)C5—C1—C2118.3 (2)
O2—C6—C1117.5 (2)C5—C1—C6118.8 (2)
O1i—Co1—O1180.0C2—C1—C6122.9 (2)
O1i—Co1—O3i87.10 (7)C1—C5—C4123.0 (2)
O1—Co1—O3i92.90 (7)C1—C5—H4118.5
O1i—Co1—O392.90 (7)C4—C5—H4118.5
O1—Co1—O387.10 (7)Co1—O4—H6114.6
O3i—Co1—O3180.0Co1—O4—H5120.3
O1i—Co1—O4i92.57 (7)H6—O4—H5105.0
O1—Co1—O4i87.43 (7)O3—C2—N1117.4 (2)
O3i—Co1—O4i86.87 (7)O3—C2—C1126.8 (2)
O3—Co1—O4i93.13 (7)N1—C2—C1115.8 (2)
O1i—Co1—O487.43 (7)N1—C3—C4119.8 (2)
O1—Co1—O492.57 (7)N1—C3—H2120.1
O3i—Co1—O493.13 (7)C4—C3—H2120.1
O3—Co1—O486.87 (7)C3—C4—C5117.8 (2)
O4i—Co1—O4180.00 (9)C3—C4—H3121.1
C2—O3—Co1121.63 (15)C5—C4—H3121.1
C3—N1—C2125.3 (2)
Co1—O1—C6—O2−178.61 (15)O2—C6—C1—C2165.8 (2)
Co1—O1—C6—C12.1 (3)C2—C1—C5—C43.0 (4)
C6—O1—Co1—O1i9(13)C6—C1—C5—C4−177.8 (2)
C6—O1—Co1—O3i−164.1 (2)Co1—O3—C2—N1−151.59 (17)
C6—O1—Co1—O315.9 (2)Co1—O3—C2—C130.4 (3)
C6—O1—Co1—O4i109.2 (2)C3—N1—C2—O3−177.3 (2)
C6—O1—Co1—O4−70.8 (2)C3—N1—C2—C11.0 (4)
O1i—Co1—O3—C2149.27 (18)C5—C1—C2—O3175.4 (2)
O1—Co1—O3—C2−30.73 (18)C6—C1—C2—O3−3.8 (4)
O3i—Co1—O3—C2−15 (93)C5—C1—C2—N1−2.6 (3)
O4i—Co1—O3—C2−117.99 (18)C6—C1—C2—N1178.2 (2)
O4—Co1—O3—C262.01 (18)C2—N1—C3—C40.5 (4)
O1—C6—C1—C5166.0 (2)N1—C3—C4—C5−0.3 (4)
O2—C6—C1—C5−13.3 (3)C1—C5—C4—C3−1.4 (4)
O1—C6—C1—C2−14.8 (3)
Symmetry codes: (i) −x, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H5···O2ii0.891.802.686 (2)175
O4—H6···O2iii0.891.912.772 (2)165
N1—H1···O3iv0.862.062.886 (3)162
C3—H2···O1v0.932.563.100 (3)118
C3—H2···O2vi0.932.563.318 (3)139
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x+1, −y+2, −z; (v) x+1, y, z; (vi) x+1, −y+3/2, z+1/2.
Table 1
Selected geometric parameters (Å) top
O1—Co12.0155 (17)Co1—O42.1065 (19)
Co1—O32.1016 (17)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H5···O2i0.891.802.686 (2)175
O4—H6···O2ii0.891.912.772 (2)165
N1—H1···O3iii0.862.062.886 (3)162
C3—H2···O1iv0.932.563.100 (3)118
C3—H2···O2v0.932.563.318 (3)139
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, −y+2, −z; (iv) x+1, y, z; (v) x+1, −y+3/2, z+1/2.
references
References top

Bruker (1997). SMART (Version 5.6) and SAINT (Version 5.06a), Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SHELXS and SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.

Sakai, K. I., Imakubo, T., Ichikawa, M. & Taniguchi, Y. (2006). Dalton Trans. 881–883.

Sheldrick, G. M. (1996). SADABS. (Version 2.10). University of Göttingen, Germany.