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Acta Cryst. (2007). E63, m2325    [ doi:10.1107/S1600536807037750 ]

Diaquabis(2-oxidopyridinium-3-carboxylate-[kappa]2O2,O3)zinc(II)

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

Abstract top

In the title mononuclear complex, [Zn(C6H4NO3)2(H2O)2], the six-coordinate ZnII atom adopts an octahedral coordination geometry and is located on an inversion centre. There is a weak [pi]-[pi] stacking interaction between adjacent pyridyl rings [the separation between the centroids of the pyridyl rings is 3.840 (2) Å and the perpendicular distance is 3.582 Å]. The crystal packing is stabilized by O-H...O and N-H...O hydrogen bonds.

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 complexes containing 3-hydroxypicolinamide ligand display strong fluorescent emission (Sakai et al. 2006). The interest in this area prompted us to synthesize the title complex, (I), which crystal structure we report herein.

Fig. 1 shows the asymmetric unit and symmetry-related fragment of (I). The ZnII atom lies at an inversion centre and adopts a slightly distored octahedral geometry (Table 1). Between neighboring complexes there is a weak π-π stacking interaction, which links adjacent pyridyl rings; the relevant distances are Cg1···Cg1i = 3.840 (2) Å and Cg1···Cg1iperp = 3.582 Å [symmetry codes: (i) X, 1/2-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 and N—H···O hydrogen bonds, which consolidate the crystal structure.

Related literature top

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

Experimental top

A diluted sodium hydroxide H2O solution was added dropwise into 30 ml of a, aqueous solution containing Zn(ClO4)2·6H2O (0.1862 g, 0.500 mmol) and 2-hydroxyl-3-carboxylpyridine (0.1232 g, 1.00 mmol) until the pH value reached 4, and the solution was stirred for another a few minutes. Colorless single crystals were obtained after the mixed solutions were allowed to stand at room temperature for one week.

Refinement top

H atoms of water molecule and N—H bond were located in a difference Fourier map and refined as riding in their as-found positions, with O—H = 0.842–0.844 Å, Uiso(H) = 1.5 Ueq(O), N—H = 0.86 Å, Uiso(H) = 1.2 Ueq(N). other H atoms were placed in calculated positions, and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; 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 + 1, −y + 1, −z].
[Figure 2] Fig. 2. Unit cell and hydrogen bonds (in broken lines).
Diaquabis(2-oxidopyridinium-3-carboxylate-κ2O2,O3)zinc(II) top
Crystal data top
[Zn(C6H4NO3)2(H2O)2]F000 = 384
Mr = 377.61Dx = 1.814 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 899 reflections
a = 7.491 (3) Åθ = 2.8–23.7º
b = 12.316 (4) ŵ = 1.82 mm−1
c = 7.621 (3) ÅT = 298 (2) K
β = 100.437 (5)ºBlock, colourless
V = 691.5 (4) Å30.24 × 0.18 × 0.10 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		1352 independent reflections
Radiation source: fine-focus sealed tube1069 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
T = 298(2) Kθmax = 26.0º
φ and ω scansθmin = 2.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→7
Tmin = 0.669, Tmax = 0.839k = −15→15
3479 measured reflectionsl = −9→6
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)] = 0.042H-atom parameters constrained
wR(F2) = 0.093  w = 1/[σ2(Fo2) + (0.0397P)2 + 0.1015P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1352 reflectionsΔρmax = 0.57 e Å−3
106 parametersΔρmin = −0.40 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Zn(C6H4NO3)2(H2O)2]V = 691.5 (4) Å3
Mr = 377.61Z = 2
Monoclinic, P21/cMo Kα
a = 7.491 (3) ŵ = 1.82 mm−1
b = 12.316 (4) ÅT = 298 (2) K
c = 7.621 (3) Å0.24 × 0.18 × 0.10 mm
β = 100.437 (5)º
Data collection top
Bruker SMART APEX CCD
diffractometer		1352 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1069 reflections with I > 2σ(I)
Tmin = 0.669, Tmax = 0.839Rint = 0.048
3479 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0423 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.04Δρmax = 0.57 e Å−3
1352 reflectionsΔρmin = −0.40 e Å−3
106 parameters
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
Zn10.50000.50000.00000.02360 (19)
O30.7719 (3)0.45670 (17)−0.0125 (3)0.0286 (6)
O20.4399 (3)0.34197 (17)−0.0143 (3)0.0292 (6)
N11.0205 (4)0.3608 (2)0.1060 (4)0.0311 (7)
H41.08150.41960.10180.037*
O10.4702 (3)0.16478 (17)−0.0133 (3)0.0311 (6)
O40.5772 (4)0.49450 (16)0.2831 (3)0.0380 (7)
H60.56800.55300.33790.057*
H50.53820.44130.33500.057*
C50.5381 (4)0.2586 (3)0.0077 (4)0.0228 (8)
C40.7405 (5)0.2668 (2)0.0606 (4)0.0223 (7)
C30.8381 (5)0.1755 (3)0.1208 (5)0.0314 (8)
H10.77600.11030.12410.038*
C60.8375 (4)0.3666 (2)0.0498 (4)0.0227 (7)
C11.1143 (5)0.2713 (3)0.1673 (5)0.0364 (9)
H31.23960.27460.20300.044*
C21.0253 (5)0.1758 (3)0.1770 (5)0.0394 (10)
H21.08740.11300.21970.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0219 (3)0.0139 (3)0.0354 (4)−0.0001 (2)0.0063 (2)0.0005 (2)
O30.0201 (12)0.0185 (12)0.0485 (16)0.0002 (10)0.0099 (11)0.0047 (11)
O20.0235 (13)0.0132 (12)0.0500 (17)−0.0005 (9)0.0040 (11)−0.0004 (10)
N10.0239 (17)0.0284 (16)0.041 (2)−0.0038 (12)0.0047 (13)0.0047 (13)
O10.0294 (15)0.0143 (12)0.0481 (17)−0.0043 (9)0.0030 (12)−0.0012 (10)
O40.0605 (19)0.0224 (13)0.0321 (15)−0.0024 (12)0.0107 (13)−0.0018 (11)
C50.025 (2)0.0215 (18)0.0217 (18)0.0005 (13)0.0047 (15)0.0018 (13)
C40.0251 (18)0.0194 (16)0.0229 (18)0.0008 (14)0.0057 (14)0.0011 (13)
C30.034 (2)0.0257 (19)0.035 (2)0.0005 (15)0.0062 (16)0.0052 (15)
C60.0184 (17)0.0271 (18)0.0235 (18)0.0024 (13)0.0059 (14)−0.0004 (14)
C10.0199 (19)0.047 (2)0.042 (2)0.0052 (16)0.0042 (16)0.0102 (18)
C20.032 (2)0.036 (2)0.049 (3)0.0134 (17)0.0055 (18)0.0166 (17)
Geometric parameters (Å, °) top
Zn1—O21.996 (2)O1—C51.261 (4)
Zn1—O2i1.996 (2)O4—H60.8415
Zn1—O3i2.124 (2)O4—H50.8440
Zn1—O32.124 (2)C5—C41.500 (4)
Zn1—O42.131 (3)C4—C31.374 (4)
Zn1—O4i2.131 (3)C4—C61.438 (4)
O3—C61.270 (4)C3—C21.390 (5)
O2—C51.256 (4)C3—H10.9300
N1—C11.345 (4)C1—C21.361 (5)
N1—C61.362 (4)C1—H30.9300
N1—H40.8600C2—H20.9300
O2—Zn1—O2i180.0Zn1—O4—H5116.4
O2—Zn1—O3i92.22 (9)H6—O4—H5111.5
O2i—Zn1—O3i87.78 (9)O2—C5—O1121.3 (3)
O2—Zn1—O387.78 (9)O2—C5—C4121.3 (3)
O2i—Zn1—O392.22 (9)O1—C5—C4117.4 (3)
O3i—Zn1—O3180.00 (13)C3—C4—C6118.4 (3)
O2—Zn1—O492.38 (8)C3—C4—C5119.1 (3)
O2i—Zn1—O487.62 (8)C6—C4—C5122.6 (3)
O3i—Zn1—O492.82 (9)C4—C3—C2123.1 (3)
O3—Zn1—O487.18 (9)C4—C3—H1118.4
O2—Zn1—O4i87.62 (8)C2—C3—H1118.4
O2i—Zn1—O4i92.38 (8)O3—C6—N1117.6 (3)
O3i—Zn1—O4i87.18 (9)O3—C6—C4127.1 (3)
O3—Zn1—O4i92.82 (9)N1—C6—C4115.3 (3)
O4—Zn1—O4i180.0N1—C1—C2119.8 (3)
C6—O3—Zn1120.79 (19)N1—C1—H3120.1
C5—O2—Zn1132.0 (2)C2—C1—H3120.1
C1—N1—C6125.8 (3)C1—C2—C3117.6 (3)
C1—N1—H4117.1C1—C2—H2121.2
C6—N1—H4117.1C3—C2—H2121.2
Zn1—O4—H6116.3
O2—Zn1—O3—C6−30.0 (2)C6—C4—C3—C22.1 (5)
O2i—Zn1—O3—C6150.0 (2)C5—C4—C3—C2−178.3 (3)
O4—Zn1—O3—C662.5 (2)Zn1—O3—C6—N1−153.4 (2)
O4i—Zn1—O3—C6−117.5 (2)Zn1—O3—C6—C429.8 (4)
O3i—Zn1—O2—C5−164.5 (3)C1—N1—C6—O3−176.6 (3)
O3—Zn1—O2—C515.5 (3)C1—N1—C6—C40.6 (5)
O4—Zn1—O2—C5−71.6 (3)C3—C4—C6—O3175.3 (3)
O4i—Zn1—O2—C5108.4 (3)C5—C4—C6—O3−4.3 (5)
Zn1—O2—C5—O1−177.9 (2)C3—C4—C6—N1−1.6 (4)
Zn1—O2—C5—C42.3 (4)C5—C4—C6—N1178.8 (3)
O2—C5—C4—C3165.9 (3)C6—N1—C1—C20.0 (6)
O1—C5—C4—C3−13.9 (4)N1—C1—C2—C30.4 (6)
O2—C5—C4—C6−14.5 (5)C4—C3—C2—C1−1.5 (6)
O1—C5—C4—C6165.6 (3)
Symmetry codes: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H4···O3ii0.862.062.895 (4)162
O4—H5···O1iii0.841.882.711 (3)170
O4—H6···O1iv0.841.982.798 (3)165
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) x, −y+1/2, z+1/2; (iv) −x+1, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H4···O3i0.862.062.895 (4)162
O4—H5···O1ii0.841.882.711 (3)170
O4—H6···O1iii0.841.982.798 (3)165
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2.
references
References top

Bruker (1997). SMART (Version 5.6) and SAINT (Version 5.A06). Bruker AXS Inc., Madison, Wisconsin, USA.

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

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

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