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Acta Cryst. (2007). E63, m1769    [ doi:10.1107/S1600536807025032 ]

Diaquabis(3-carboxypyridine-2-carboxylato-[kappa]2N,O2)zinc(II)

H. Aghabozorg, E. Sadr-khanlou, J. Soleimannejad and H. Adams

Abstract top

The centrosymmetric title compound, [Zn(C14H8N2O8)2(H2O)2], shows a distorted octahedral coordination. The four donor atoms of the two coplanar 3-carboxypyridine-2-carboxylate or (2,3-pydcH)- anions form a square-planar arrangement around the ZnII centre. This crystal structure has an infinite three-dimensional framework. The stabilizing interactions existing in the crystal structure are intermolecular O-H...O and very strong intramolecular O-H...O hydrogen bonds. H atoms of coordinated water molecules participate in hydrogen-bonded chains described by C22(12) and C11(8) graph-set descriptors.

Comment top

The lattice consists of [Zn(2,3-pydcH)2(H2O)2] complexes resulted by a doubly monoprotonated (2,3-pydcH)- as a bidentate ligand. The presence of this bidentate ligand leads to a neutral complex and does not allow the 2,9-dimethyl-1,10-phenanthroline Lewis base to crystallize in the produced network. The asymmetric unit of compound, [Zn(2,3-pydcH)2(H2O)2] is presented in Figure 1. The metal center is hexacoordinated by two (2,3-pydcH)- bidentate ligand and two water molecules. The geometry around ZnII center is distorted octahedral. The four donor atoms of the two (2,3-pydcH)- anions form a square planar arrangement around ZnII center. The rings are almost coplanar (RMS deviation 0.0057 Å). In construction of this crystal which has an infinite three dimensional framework based on [100], [001] and [010] vectors, the hydrogen bonding intermolecular interactions play the essential role. The stabilizing interactions existing in the crystal lattice are intermolecular O–H···O and very strong intramolecular O–H···O type hydrogen bonds.

Hydrogen atoms of coordinated water molecules participate in hydrogen bonded chains described by C22(12) and C11(8) graph set descriptors. Thus, the three-dimensional supramolecule structure for [Zn(2,3-pydcH)2(H2O)2] is confirmed.

Related literature top

Several complexes of zinc with pyridine-2,6-dicarboxylic acid have been reported (Aghajani et al., 2006, and references therein). There is also a report of a similar copper compound with pyridine-2,3-dicarboxylic acid in the literature (Xiang et al., 2006).

Experimental top

To a 10 ml of a stirring aqueous solution of 2,9-dimethyl-1,10-phenathroline (0.104 g, 0.5 mmol) and pyridine-2,3-dicarboxylic acid (0.0836 g, 0.5 mmol), was added a 0.5 molar equivalent of ZnSO4 . 7H2O (0.0727 g, 0.25 mmol) at room temperature. A neutral zinc(II) complex, [Zn(2,3-pydcH)2(H2O)2], was isolated at pH 3.0 as a colorless crystals. Slow evaporation of the solvent during 10 days resulted in product complexes. Recrystallization of resultants for several times leads to X-ray quality crystals.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level. The intramolecular hydrogen bonds are shown by dashed lines.
[Figure 2] Fig. 2. Packing diagram of (I) with H-bonds with dashed lines. H atoms not involved in H-bonds omitter for clarity.
Diaquabis(3-carboxypyridine-2-carboxylato-κ2N,O2)zinc(II) top
Crystal data top
[Zn(C14H8N2O8)(H2O)2]F(000) = 440
Mr = 433.63Dx = 1.913 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.304 (3) ÅCell parameters from 5661 reflections
b = 7.909 (3) Åθ = 2.8–27.5°
c = 10.276 (4) ŵ = 1.70 mm−1
β = 95.317 (6)°T = 150 K
V = 752.9 (5) Å3Block, colourless
Z = 20.38 × 0.38 × 0.35 mm
Data collection top
Bruker SMART
diffractometer		1706 independent reflections
Radiation source: fine-focus sealed tube1575 reflections with I > 2σ(I)
graphiteRint = 0.023
Detector resolution: 100 pixels mm-1θmax = 27.5°, θmin = 2.8°
ω scansh = −11→11
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)		k = −10→10
Tmin = 0.565, Tmax = 0.588l = −13→13
8225 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0383P)2 + 0.3534P]
where P = (Fo2 + 2Fc2)/3
1706 reflections(Δ/σ)max = 0.001
124 parametersΔρmax = 0.40 e Å−3
0 restraintsΔρmin = −0.40 e Å−3
Crystal data top
[Zn(C14H8N2O8)(H2O)2]V = 752.9 (5) Å3
Mr = 433.63Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.304 (3) ŵ = 1.70 mm−1
b = 7.909 (3) ÅT = 150 K
c = 10.276 (4) Å0.38 × 0.38 × 0.35 mm
β = 95.317 (6)°
Data collection top
Bruker SMART
diffractometer		1706 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)		1575 reflections with I > 2σ(I)
Tmin = 0.565, Tmax = 0.588Rint = 0.023
8225 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.069Δρmax = 0.40 e Å−3
S = 1.12Δρmin = −0.40 e Å−3
1706 reflectionsAbsolute structure: ?
124 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Zn10.50000.50001.00000.01651 (11)
N10.66631 (13)0.66168 (17)0.96316 (12)0.0159 (3)
C10.77906 (16)0.59130 (19)0.90988 (14)0.0147 (3)
C20.89688 (16)0.6908 (2)0.88011 (14)0.0156 (3)
C30.88952 (17)0.8644 (2)0.90586 (15)0.0189 (3)
H30.96650.93560.88550.023*
C40.77323 (18)0.9340 (2)0.96005 (16)0.0206 (3)
H40.76881.05190.97710.025*
C50.66301 (17)0.8268 (2)0.98885 (15)0.0187 (3)
H50.58280.87211.02800.022*
C60.75688 (16)0.39930 (19)0.89076 (14)0.0158 (3)
C71.03467 (16)0.6349 (2)0.82239 (15)0.0179 (3)
O10.63949 (11)0.33806 (14)0.91765 (11)0.0181 (2)
O20.85601 (12)0.31061 (14)0.85009 (11)0.0203 (2)
O31.13066 (12)0.74039 (15)0.81237 (12)0.0218 (3)
O41.05136 (14)0.48120 (15)0.78668 (14)0.0261 (3)
H4A0.98610.41620.81340.031*
O50.60695 (12)0.44082 (15)1.19303 (11)0.0201 (2)
H5A0.63250.54291.23810.024*
H5B0.69200.37411.19550.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01293 (15)0.01436 (16)0.02298 (16)−0.00098 (8)0.00569 (10)−0.00054 (9)
N10.0137 (6)0.0160 (6)0.0182 (6)0.0004 (5)0.0023 (5)0.0006 (5)
C10.0146 (7)0.0143 (8)0.0150 (7)0.0005 (5)0.0007 (5)0.0006 (5)
C20.0137 (7)0.0184 (8)0.0148 (7)0.0000 (6)0.0017 (5)0.0008 (6)
C30.0172 (7)0.0186 (8)0.0208 (7)−0.0038 (6)0.0022 (6)0.0011 (6)
C40.0224 (8)0.0144 (8)0.0251 (8)−0.0011 (6)0.0027 (6)−0.0009 (6)
C50.0173 (7)0.0169 (8)0.0224 (7)0.0019 (6)0.0045 (6)−0.0002 (6)
C60.0163 (7)0.0151 (8)0.0159 (7)−0.0005 (6)0.0017 (6)0.0010 (5)
C70.0149 (7)0.0211 (8)0.0179 (7)0.0003 (6)0.0021 (6)0.0031 (6)
O10.0151 (5)0.0158 (5)0.0243 (5)−0.0010 (4)0.0054 (4)−0.0009 (4)
O20.0171 (5)0.0159 (5)0.0290 (6)0.0014 (4)0.0073 (4)−0.0010 (5)
O30.0149 (5)0.0225 (6)0.0286 (6)−0.0013 (4)0.0047 (4)0.0033 (5)
O40.0192 (6)0.0209 (6)0.0405 (8)−0.0022 (4)0.0140 (5)−0.0025 (5)
O50.0167 (5)0.0196 (6)0.0243 (6)0.0018 (4)0.0030 (4)−0.0011 (5)
Geometric parameters (Å, °) top
Zn1—O12.0602 (12)C3—C41.377 (2)
Zn1—O1i2.0602 (12)C3—H30.9500
Zn1—N1i2.0691 (14)C4—C51.384 (2)
Zn1—N12.0691 (14)C4—H40.9500
Zn1—O52.1858 (13)C5—H50.9500
Zn1—O5i2.1858 (13)C6—O11.2489 (19)
N1—C51.334 (2)C6—O21.2604 (19)
N1—C11.3478 (19)C7—O31.2333 (19)
C1—C21.406 (2)C7—O41.283 (2)
C1—C61.543 (2)O4—H4A0.8600
C2—C31.401 (2)O5—H5A0.9500
C2—C71.527 (2)O5—H5B0.9500
O1—Zn1—O1i180.0C3—C2—C7114.50 (13)
O1—Zn1—N1i101.61 (6)C1—C2—C7128.45 (14)
O1i—Zn1—N1i78.39 (5)C4—C3—C2121.50 (15)
O1—Zn1—N178.39 (6)C4—C3—H3119.2
O1i—Zn1—N1101.61 (6)C2—C3—H3119.2
N1i—Zn1—N1180.0C3—C4—C5117.84 (15)
O1—Zn1—O589.34 (5)C3—C4—H4121.1
O1i—Zn1—O590.66 (5)C5—C4—H4121.1
N1i—Zn1—O589.25 (5)N1—C5—C4121.79 (14)
N1—Zn1—O590.75 (5)N1—C5—H5119.1
O1—Zn1—O5i90.66 (5)C4—C5—H5119.1
O1i—Zn1—O5i89.34 (5)O1—C6—O2122.63 (14)
N1i—Zn1—O5i90.75 (5)O1—C6—C1117.58 (13)
N1—Zn1—O5i89.25 (5)O2—C6—C1119.78 (13)
O5—Zn1—O5i180.0O3—C7—O4120.60 (15)
C5—N1—C1121.20 (13)O3—C7—C2118.49 (14)
C5—N1—Zn1122.53 (10)O4—C7—C2120.90 (14)
C1—N1—Zn1116.26 (10)C6—O1—Zn1116.54 (10)
N1—C1—C2120.60 (14)C7—O4—H4A111.6
N1—C1—C6111.00 (12)Zn1—O5—H5A109.4
C2—C1—C6128.40 (13)Zn1—O5—H5B116.8
C3—C2—C1117.05 (14)H5A—O5—H5B106.8
Symmetry codes: (i) −x+1, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O3ii0.951.882.8035 (19)164
O5—H5B···O3iii0.951.892.8358 (18)174
O5—H5B···O4iii0.952.643.226 (2)121
O4—H4A···O20.861.552.4017 (17)173
Symmetry codes: (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+2, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O12.0602 (12)Zn1—O52.1858 (13)
Zn1—N12.0691 (14)
O1—Zn1—N1i101.61 (6)O1—Zn1—N178.39 (6)
Symmetry codes: (i) −x+1, −y+1, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O3ii0.951.882.8035 (19)164
O5—H5B···O3iii0.951.892.8358 (18)174
O5—H5B···O4iii0.952.643.226 (2)121
O4—H4A···O20.861.552.4017 (17)173
Symmetry codes: (ii) x−1/2, −y+3/2, z+1/2; (iii) −x+2, −y+1, −z+2.
Acknowledgements top

The authors gratefully acknowledge the Teacher Training and Ilam Universities.

references
References top

Aghajani, Z., Sharif, M. A., Aghabozorg, H. & Naderpour, A. (2006). Acta Cryst. E62, m830–m832.

Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1998). SMART (Version 5.059) and SAINT-Plus (Version 6.01). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1998). SADABS. Version 2.01. University of Göttingen, Germany.

Xiang, J.-F., Li, M., Wu, S.-M., Yuan, L.-J. & Sun, J.-T. (2006). Acta Cryst. E62, m1122–m1123.