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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): m1606–m1607.
Published online 2010 November 20. doi:  10.1107/S1600536810047252
PMCID: PMC3011689

Hexaaqua­zinc(II) bis­[tris­(3-carb­oxy­pyridine-2-carboxyl­ato)zincate(II)]

Abstract

The title compound, [Zn(H2O)6][Zn(C7H4NO4)3]2, consists of two [Zn(py-2,3-dcH)3] anions (py-2,3-dcH is 3-carboxy­pyridine-2-carboxylate) and one [Zn(H2O)6]2+ cation. The anion is a six-coordinate complex located on a threefold rotation axis with a slightly distorted octa­hedral geometry around Zn2+ ion. The cation is also six-coordinate with an octa­hedral geometry around the Zn atom, located at a An external file that holds a picture, illustration, etc.
Object name is e-66-m1606-efi1.jpg axis. Non-covalent inter­actions such as π–π stacking [centroid–centroid distance = 3.828 (4)Å] and O—H(...)O hydrogen bonds play important roles in stabilizing the supra­molecular structure.

Related literature

For first-row transition metal complexes of pyridine-2,3-dicarb­oxy­lic acid and various bases and for Zn—O distances, see: Aghabozorg, Daneshvar et al. (2007 [triangle]); Aghabozorg, Sadr-khanlou et al. (2007) [triangle]; Goher et al. (1993 [triangle]); Kang et al. (2006 [triangle]); Li et al. (2006 [triangle]); Prior & Rosseinsky (2001 [triangle]); Swiegers & Malefetse (2000 [triangle]); Yin & Liu (2009 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1606-scheme1.jpg

Experimental

Crystal data

  • [Zn(H2O)6][Zn(C7H4NO4)3]2
  • M r = 1300.88
  • Trigonal, An external file that holds a picture, illustration, etc.
Object name is e-66-m1606-efi2.jpg
  • a = 14.470 (4) Å
  • c = 6.284 (2) Å
  • V = 1139.4 (6) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 1.68 mm−1
  • T = 153 K
  • 1.20 × 0.44 × 0.42 mm

Data collection

  • Siemens SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.237, T max = 0.538
  • 10776 measured reflections
  • 1356 independent reflections
  • 1009 reflections with I > 2σ(I)
  • R int = 0.154

Refinement

  • R[F 2 > 2σ(F 2)] = 0.061
  • wR(F 2) = 0.158
  • S = 1.00
  • 1356 reflections
  • 133 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.86 e Å−3
  • Δρmin = −0.82 e Å−3

Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2010 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810047252/om2373sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047252/om2373Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We acknowledge financial support of this work by the Nation Elite Foundation. We are also grateful to the Institute for Color Science and Technology.

supplementary crystallographic information

Comment

Metal-organic coordination complexes with one-, two- or three-dimensional structures have attracted attentions for their potential applications as photoelectric materials, catalysis, carriers, sensors, etc. (Prior & Rosseinsky, 2001; Swiegers & Malefetse, 2000). From a chemical point of view, L-lysine, a base, contains two amino groups and one carboxylic acid group, these amino groups often participate in hydrogen bonding and as a general base in catalysis. There are previously reported compounds containing pyridine-2,3-dicarboxylic acid, (py-2,3-dcH2), (Goher et al., 1993; Yin & Liu 2009; Aghabozorg, Daneshvar et al., 2007, Kang et al., 2006, Li et al., 2006).

The title compound consists of two [Zn(py-2,3-dcH)3]¯ anions and one Zn(H2O)62+ cation. The anion is a six-coordinate complex located at a 3-fold crystallographic axis around Zn1 atom by three chelating (py-2,3-dcH)¯ ligands via one N and one O atom from carboxylate groups (Fig. 1). The cation is also six-coordinate with an octahedral geometry around Zn2 atom, located at a 3-bar axis. L-lysine, even it was included during the synthesis, is not part of this crystal structure and we were surprised that the product material contains Zn atoms in both form of cation and anion units. In anionic complex the three O—Zn1—N angles indicate that there is a distorted octahedral geometry around Zn1 atoms (for selected bond distances and angles see Table 1), but in cationic unit there are three O—Zn2—O angles exactly 180° as imposed by the crystallographic symmetry and good octahedral geometry environment around Zn2 atom (Table 1). The anionic Zn—O distances (Table 1) fall within the range of those found in related Zn complexes, 2.031- 2.117 Å (Aghabozorg, Daneshvar et al., 2007; Aghabozorg, Sadr-khanlou et al., 2007; Kang, et al., 2006; Li, et al., 2006;Yin, et al., 2009).

There are three principal hydrogen bonds of O—H···O type (see Table 2) forming a complicated and extensive hydrogen bonding pattern. Graph-set analysis (Bernstein et al., 1995) on the first level is indicating chains with symbols C22(20) and C22(16) for hydrogen bond with donor atoms O3 and O5, respectively, as well as ring R22(20) for hydrogen bond with O3 as a donor. On second level graph-set, most important are ring R12(6) and chains C22(14) and C22(16) between hexaaqua zinc cations, as well as rings R33(15) formed between anions and cations.

There are π-π stacking interactions between anions proved by short distance Cg4···Cg4 3.828 (4)Å [Cg4 is centroid of N1/C2—C6 ring. Symmetry code: 1 - x,1 - y,1 - z]. These π-π stacking interactions and O—H···O hydrogen bonds have important roles in stabilizing the structure. Crystal packing is depicted in Fig. 2.

Experimental

The title compound was prepared by the reaction of pyridine-2,3-dicarboxylic acid (py-2,3-dcH2) (167 mg, 1 mmol), L-Lysine (L-Lys) (164 mg, 1 mmol) and with zinc(II) nitrate hexahydrate Zn(NO3)2. 6H2O (148.7 mg, 0.5 mmol), which were dissolved in distilled water (30 ml) as solvent in 2:2:1 molar ratio. The crystals were obtained by slow evaporation of solvent at room temperature.

Refinement

Aromatic hydrogen atoms were refined isotropically with Uiso(H) = 1.2Ueq(C) and their positions were constrained to ideal geometry using an appropriate riding model, with C—H = 0.95. The carboxylate and water H atoms were located at the difference Fourier map and refined isotropically with Uiso(H) = 1.5Ueq(O), and restrained to ideal geometry with O—H distances 0.84 (2)Å and H···H distance 1.34 (2) Å for the water molecule.

Figures

Fig. 1.
The molecular structure of the title compound, with the displacement ellipsoids drawn at 50% probability level.
Fig. 2.
A view of along the a axis of the crystal packing in the title compounds. Layers perpendicular to c-directions are connected via hydrogen bonds.

Crystal data

[Zn(H2O)6][Zn(C7H4NO4)3]2Dx = 1.896 Mg m3
Mr = 1300.88Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3Cell parameters from 1491 reflections
Hall symbol: -P 3θ = 2.8–22.5°
a = 14.470 (4) ŵ = 1.68 mm1
c = 6.284 (2) ÅT = 153 K
V = 1139.4 (6) Å3Block, colourless
Z = 11.20 × 0.44 × 0.42 mm
F(000) = 660

Data collection

Siemens SMART CCD area-detector diffractometer1356 independent reflections
Radiation source: fine-focus sealed tube1009 reflections with I > 2σ(I)
graphiteRint = 0.154
ω scansθmax = 25.1°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −17→17
Tmin = 0.237, Tmax = 0.538k = −17→17
10776 measured reflectionsl = −7→7

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.158w = 1/[σ2(Fo2) + (0.0993P)2 + 0.9035P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1356 reflectionsΔρmax = 0.86 e Å3
133 parametersΔρmin = −0.82 e Å3
4 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.035 (5)

Special details

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)

xyzUiso*/Ueq
Zn10.33330.66670.29441 (18)0.0155 (4)
O10.2510 (3)0.5298 (3)0.1090 (6)0.0193 (9)
O20.1958 (3)0.3552 (3)0.0954 (6)0.0194 (10)
O30.3623 (3)0.2972 (3)0.1662 (6)0.0213 (10)
H30.352 (5)0.247 (4)0.086 (9)0.032*
O40.2312 (4)0.1865 (3)0.3858 (7)0.0322 (11)
N10.3482 (4)0.5491 (4)0.4789 (7)0.0161 (11)
C20.3119 (4)0.4565 (4)0.3746 (8)0.0155 (12)
C30.3237 (4)0.3729 (4)0.4533 (9)0.0167 (13)
C40.3667 (5)0.3851 (5)0.6543 (10)0.0216 (14)
H40.37250.32830.71640.026*
C50.4011 (4)0.4781 (5)0.7648 (9)0.0200 (13)
H50.42940.48630.90440.024*
C60.3935 (4)0.5601 (5)0.6677 (9)0.0183 (13)
H60.42190.62670.73910.022*
C70.2490 (4)0.4467 (4)0.1750 (9)0.0168 (13)
C80.2983 (5)0.2751 (4)0.3263 (9)0.0187 (13)
Zn20.00000.00000.00000.0226 (5)
O50.0098 (3)0.1271 (4)0.1776 (7)0.0305 (11)
H51−0.038 (3)0.109 (5)0.267 (8)0.046*
H520.069 (2)0.161 (5)0.238 (9)0.046*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0124 (5)0.0124 (5)0.0217 (7)0.0062 (2)0.0000.000
O10.017 (2)0.016 (2)0.024 (2)0.0074 (18)−0.0023 (17)−0.0024 (17)
O20.016 (2)0.011 (2)0.031 (2)0.0056 (18)−0.0076 (17)−0.0055 (17)
O30.019 (2)0.016 (2)0.029 (3)0.0096 (19)0.0048 (19)−0.0047 (18)
O40.040 (3)0.013 (2)0.035 (3)0.007 (2)0.012 (2)0.0014 (19)
N10.012 (2)0.012 (2)0.020 (3)0.003 (2)0.0024 (19)−0.003 (2)
C20.013 (3)0.013 (3)0.018 (3)0.005 (2)0.001 (2)0.002 (2)
C30.011 (3)0.013 (3)0.025 (3)0.005 (2)0.003 (2)0.000 (2)
C40.021 (3)0.021 (3)0.027 (3)0.014 (3)0.003 (3)0.001 (3)
C50.015 (3)0.027 (3)0.021 (3)0.013 (3)−0.002 (2)−0.002 (3)
C60.014 (3)0.025 (3)0.018 (3)0.012 (3)−0.002 (2)−0.005 (2)
C70.009 (3)0.022 (3)0.022 (3)0.010 (3)0.003 (2)0.000 (3)
C80.020 (3)0.015 (3)0.026 (3)0.012 (3)−0.001 (3)0.001 (2)
Zn20.0185 (6)0.0185 (6)0.0307 (11)0.0092 (3)0.0000.000
O50.018 (2)0.029 (3)0.038 (3)0.008 (2)0.001 (2)−0.004 (2)

Geometric parameters (Å, °)

Zn1—O12.083 (4)C3—C41.380 (8)
Zn1—N12.157 (5)C3—C81.502 (8)
O1—C71.259 (7)C4—C51.369 (8)
O2—C71.256 (7)C4—H40.9500
O3—C81.294 (7)C5—C61.386 (8)
O3—H30.83 (5)C5—H50.9500
O4—C81.217 (7)C6—H60.9500
N1—C61.327 (7)Zn2—O52.095 (5)
N1—C21.340 (7)O5—H510.82 (5)
C2—C31.393 (8)O5—H520.83 (6)
C2—C71.514 (8)
O1—Zn1—O1i91.76 (15)C5—C4—H4119.7
O1—Zn1—N1i165.35 (16)C6—C5—C4118.2 (5)
O1—Zn1—N177.62 (16)C6—C5—H5120.9
O1i—Zn1—N198.55 (15)C4—C5—H5120.9
N1i—Zn1—N193.83 (16)N1—C6—C5122.5 (5)
C7—O1—Zn1116.9 (4)N1—C6—H6118.8
C8—O3—H3117 (5)C5—C6—H6118.8
C6—N1—C2118.7 (5)O2—C7—O1125.8 (5)
C6—N1—Zn1128.6 (4)O2—C7—C2116.8 (5)
C2—N1—Zn1112.5 (3)O1—C7—C2117.3 (5)
N1—C2—C3122.5 (5)O4—C8—O3126.5 (5)
N1—C2—C7114.5 (5)O4—C8—C3121.3 (5)
C3—C2—C7122.8 (5)O3—C8—C3111.9 (5)
C4—C3—C2117.2 (5)O5—Zn2—O5ii180.0
C4—C3—C8119.2 (5)O5—Zn2—O5iii85.74 (18)
C2—C3—C8123.5 (5)Zn2—O5—H51114 (5)
C3—C4—C5120.6 (5)Zn2—O5—H52111 (5)
C3—C4—H4119.7H51—O5—H52109 (3)
O1iv—Zn1—O1—C7−172.0 (4)C7—C2—C3—C4−169.1 (5)
O1i—Zn1—O1—C796.2 (4)N1—C2—C3—C8−170.8 (5)
N1iv—Zn1—O1—C7−94.3 (4)C7—C2—C3—C814.7 (9)
N1i—Zn1—O1—C753.1 (8)C2—C3—C4—C5−3.3 (9)
N1—Zn1—O1—C7−2.2 (4)C8—C3—C4—C5173.0 (5)
O1iv—Zn1—N1—C6−132.6 (6)C3—C4—C5—C6−1.3 (9)
O1—Zn1—N1—C6−176.9 (5)C2—N1—C6—C5−2.6 (8)
O1i—Zn1—N1—C693.2 (5)Zn1—N1—C6—C5−177.4 (4)
N1iv—Zn1—N1—C6−79.0 (4)C4—C5—C6—N14.5 (9)
N1i—Zn1—N1—C615.1 (5)Zn1—O1—C7—O2173.2 (4)
O1iv—Zn1—N1—C252.4 (8)Zn1—O1—C7—C2−3.5 (6)
O1—Zn1—N1—C28.0 (4)N1—C2—C7—O2−166.2 (5)
O1i—Zn1—N1—C2−81.9 (4)C3—C2—C7—O28.7 (8)
N1iv—Zn1—N1—C2105.9 (4)N1—C2—C7—O110.8 (7)
N1i—Zn1—N1—C2−159.9 (4)C3—C2—C7—O1−174.3 (5)
C6—N1—C2—C3−2.5 (8)C4—C3—C8—O463.8 (8)
Zn1—N1—C2—C3173.1 (4)C2—C3—C8—O4−120.1 (7)
C6—N1—C2—C7172.4 (5)C4—C3—C8—O3−110.0 (6)
Zn1—N1—C2—C7−12.0 (6)C2—C3—C8—O366.1 (7)
N1—C2—C3—C45.4 (8)

Symmetry codes: (i) −y+1, xy+1, z; (ii) −x, −y, −z; (iii) xy, x, −z; (iv) −x+y, −x+1, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O2v0.83 (5)1.72 (2)2.547 (5)169 (7)
O5—H52···O40.83 (5)2.38 (4)3.157 (7)156 (7)
O5—H51···O4vi0.82 (6)2.02 (3)2.795 (6)158 (6)

Symmetry codes: (v) y, −x+y, −z; (vi) −y, xy, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2373).

References

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