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Acta Cryst. (2009). E65, m106    [ doi:10.1107/S1600536808042530 ]

Diaquabis(5-methylpyridine-2-carboxylato-[kappa]2N,O)zinc(II)

L.-C. Du

Abstract top

In the title compound, [Zn(C7H6NO2)2(H2O)2], the Zn atom (site symmetry \overline{1}) adopts a distorted trans-ZnN2O4 octahedral coordination arising from two N,O-bidentate 5-methylpyridine-2-carboxylate ligands and two water molecules. In the crystal structure, molecules form a layered network linked by O-H...O hydrogen bonds.

Comment top

As part of our efforts to achieve supramolecular transition metal complexes by self-assembly (Ranford, et al., 1998; Hagrman, et al., 1998), we now report on the synthesis and crystal structure of the title compound, (I), (Fig. 1).

The ZnII centre in (I) is six-coordinate with two O donors of H2O, and two N,O-bidentate ligands (Table 1). In the crystal packing, the molecules form a layers linked by O—H···O hydrogen bonds (Table 2).

Related literature top

For background, see: Hagrman et al. (1998); Ranford et al. (1998).

Experimental top

A solution of 1.0 mmol 5-methylpyridine-2-carboxylic acid and 1.0 mmol NaOH in 5 ml 95% ethanol was added to a solution of 0.5 mmol Zn(CH3COO)2.4H2O in 5 ml ethanol at room temperature. The mixture was refluxed for 2 h with stirring, then the resulting precipitate was filtered, washed, and dried in vacuo over P4O10 for 48 h. Colourless blocks of (I) were obtained by slowly evaporating from methanol at room temperature.

Refinement top

The H atoms were geometrically placed (C—H = 0.93-0.96Å, O—H = 0.85Å) and refined as riding with Uiso(H) = 1.2Ueq(C, O) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids for the non-hydrogen atoms. Symmetry code: (i) 1–x, 1–y, 1–z.
Diaquabis(5-methylpyridine-2-carboxylato-κ2N,O)zinc(II) top
Crystal data top
[Zn(C7H6NO2)2(H2O)2]Z = 1
Mr = 373.66F(000) = 192
Triclinic, P1Dx = 1.668 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.1703 (6) ÅCell parameters from 1975 reflections
b = 6.462 (1) Åθ = 3.4–27.9°
c = 12.2781 (14) ŵ = 1.68 mm−1
α = 104.678 (2)°T = 298 K
β = 90.646 (1)°Block, colourless
γ = 109.493 (2)°0.49 × 0.46 × 0.27 mm
V = 372.01 (8) Å3
Data collection top
Bruker SMART CCD
diffractometer		1275 independent reflections
Radiation source: fine-focus sealed tube1260 reflections with I > 2σ(I)
graphiteRint = 0.013
ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −6→3
Tmin = 0.493, Tmax = 0.659k = −6→7
1917 measured reflectionsl = −14→14
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) = 0.097 w = 1/[σ2(Fo2) + (0.0603P)2 + 0.3083P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
1275 reflectionsΔρmax = 0.63 e Å−3
108 parametersΔρmin = −0.60 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.094 (11)
Crystal data top
[Zn(C7H6NO2)2(H2O)2]γ = 109.493 (2)°
Mr = 373.66V = 372.01 (8) Å3
Triclinic, P1Z = 1
a = 5.1703 (6) ÅMo Kα radiation
b = 6.462 (1) ŵ = 1.68 mm−1
c = 12.2781 (14) ÅT = 298 K
α = 104.678 (2)°0.49 × 0.46 × 0.27 mm
β = 90.646 (1)°
Data collection top
Bruker SMART CCD
diffractometer		1275 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1260 reflections with I > 2σ(I)
Tmin = 0.493, Tmax = 0.659Rint = 0.013
1917 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.097Δρmax = 0.63 e Å−3
S = 1.15Δρmin = −0.60 e Å−3
1275 reflectionsAbsolute structure: ?
108 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
Zn10.50000.50000.50000.0269 (2)
N10.4060 (5)0.5257 (4)0.6691 (2)0.0265 (5)
C40.3260 (7)0.5138 (6)0.8903 (2)0.0351 (7)
H40.29790.50790.96430.042*
O10.6819 (4)0.2811 (3)0.54326 (17)0.0298 (5)
O20.7442 (5)0.1369 (4)0.6842 (2)0.0399 (6)
O30.1258 (4)0.2198 (4)0.4350 (2)0.0368 (5)
H3A0.14100.09050.40680.044*
H3B−0.01990.20480.46830.044*
C10.6533 (6)0.2552 (5)0.6414 (2)0.0266 (6)
C20.4953 (6)0.3907 (5)0.7150 (2)0.0269 (6)
C30.4520 (8)0.3852 (6)0.8251 (3)0.0417 (8)
H30.51240.28870.85500.050*
C60.2809 (6)0.6541 (5)0.7341 (3)0.0309 (6)
H60.21750.74900.70400.037*
C50.2430 (6)0.6500 (6)0.8452 (3)0.0351 (7)
C70.1086 (8)0.8011 (7)0.9188 (3)0.0500 (9)
H7A−0.00930.71860.96500.075*
H7B0.00100.84730.87180.075*
H7C0.24830.93370.96640.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0346 (3)0.0309 (3)0.0229 (3)0.0191 (2)0.00841 (19)0.01007 (19)
N10.0300 (12)0.0281 (12)0.0253 (12)0.0143 (10)0.0049 (10)0.0083 (10)
C40.0477 (18)0.0513 (19)0.0163 (13)0.0286 (15)0.0102 (12)0.0108 (13)
O10.0357 (11)0.0321 (11)0.0293 (11)0.0209 (9)0.0098 (8)0.0089 (9)
O20.0559 (14)0.0394 (12)0.0369 (12)0.0323 (11)0.0035 (10)0.0111 (10)
O30.0337 (11)0.0298 (11)0.0486 (13)0.0161 (9)0.0117 (10)0.0067 (10)
C10.0274 (13)0.0224 (13)0.0306 (15)0.0109 (11)0.0018 (11)0.0052 (11)
C20.0304 (14)0.0264 (13)0.0252 (14)0.0119 (11)0.0036 (11)0.0066 (11)
C30.054 (2)0.051 (2)0.0337 (17)0.0306 (17)0.0084 (15)0.0194 (15)
C60.0349 (15)0.0321 (15)0.0313 (15)0.0196 (12)0.0078 (12)0.0076 (12)
C50.0341 (15)0.0399 (17)0.0289 (15)0.0146 (13)0.0065 (12)0.0029 (13)
C70.054 (2)0.059 (2)0.0395 (19)0.0315 (19)0.0155 (16)0.0005 (17)
Geometric parameters (Å, °) top
Zn1—O12.104 (2)O2—C11.232 (4)
Zn1—O32.134 (2)O3—H3A0.8499
Zn1—O1i2.104 (2)O3—H3B0.8499
Zn1—N1i2.116 (2)C1—C21.531 (4)
Zn1—N12.116 (2)C2—C31.380 (4)
Zn1—O3i2.134 (2)C3—H30.9300
N1—C61.334 (4)C6—C51.387 (5)
N1—C21.343 (4)C6—H60.9300
C4—C51.327 (5)C5—C71.507 (4)
C4—C31.338 (5)C7—H7A0.9600
C4—H40.9300C7—H7B0.9600
O1—C11.262 (4)C7—H7C0.9600
O1—Zn1—O1i180.0Zn1—O3—H3B121.9
O1—Zn1—N1i100.78 (8)H3A—O3—H3B110.5
O1i—Zn1—N1i79.22 (8)O2—C1—O1126.8 (3)
O1—Zn1—N179.22 (8)O2—C1—C2117.3 (3)
O1i—Zn1—N1100.78 (8)O1—C1—C2115.9 (2)
N1i—Zn1—N1180.0N1—C2—C3120.1 (3)
O1—Zn1—O3i89.38 (9)N1—C2—C1116.9 (2)
O1i—Zn1—O3i90.62 (9)C3—C2—C1123.0 (3)
N1i—Zn1—O3i92.23 (9)C4—C3—C2122.3 (3)
N1—Zn1—O3i87.77 (9)C4—C3—H3118.8
O1—Zn1—O390.62 (9)C2—C3—H3118.8
O1i—Zn1—O389.38 (9)N1—C6—C5121.7 (3)
N1i—Zn1—O387.77 (9)N1—C6—H6119.1
N1—Zn1—O392.23 (9)C5—C6—H6119.1
O3i—Zn1—O3180.0C4—C5—C6120.9 (3)
C6—N1—C2117.7 (2)C4—C5—C7117.9 (3)
C6—N1—Zn1130.4 (2)C6—C5—C7121.2 (3)
C2—N1—Zn1111.95 (18)C5—C7—H7A109.5
C5—C4—C3117.3 (3)C5—C7—H7B109.5
C5—C4—H4121.3H7A—C7—H7B109.5
C3—C4—H4121.3C5—C7—H7C109.5
C1—O1—Zn1115.99 (17)H7A—C7—H7C109.5
Zn1—O3—H3A116.6H7B—C7—H7C109.5
O1—Zn1—N1—C6176.5 (3)C6—N1—C2—C1−176.5 (2)
O1i—Zn1—N1—C6−3.5 (3)Zn1—N1—C2—C12.3 (3)
O3i—Zn1—N1—C686.7 (3)O2—C1—C2—N1177.6 (3)
O3—Zn1—N1—C6−93.3 (3)O1—C1—C2—N1−0.9 (4)
O1—Zn1—N1—C2−2.21 (19)O2—C1—C2—C30.0 (4)
O1i—Zn1—N1—C2177.79 (19)O1—C1—C2—C3−178.5 (3)
O3i—Zn1—N1—C2−92.0 (2)C5—C4—C3—C2−0.2 (6)
O3—Zn1—N1—C288.0 (2)N1—C2—C3—C4−1.1 (5)
N1i—Zn1—O1—C1−178.1 (2)C1—C2—C3—C4176.4 (3)
N1—Zn1—O1—C11.9 (2)C2—N1—C6—C50.0 (4)
O3i—Zn1—O1—C189.7 (2)Zn1—N1—C6—C5−178.6 (2)
O3—Zn1—O1—C1−90.3 (2)C3—C4—C5—C61.3 (5)
Zn1—O1—C1—O2−179.4 (2)C3—C4—C5—C7−178.2 (3)
Zn1—O1—C1—C2−1.2 (3)N1—C6—C5—C4−1.3 (5)
C6—N1—C2—C31.2 (4)N1—C6—C5—C7178.2 (3)
Zn1—N1—C2—C3−180.0 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2ii0.851.882.693 (4)160
O3—H3B···O1iii0.851.942.757 (3)160
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y, z.
Table 1
Selected geometric parameters (Å) top
Zn1—O12.104 (2)Zn1—N12.116 (2)
Zn1—O32.134 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2i0.851.882.693 (4)160
O3—H3B···O1ii0.851.942.757 (3)160
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z.
Acknowledgements top

The author thanks the Science and Technology Foundation of Weifang (2008–19) for a research grant.

references
References top

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Hagrman, D., Hammond, R. P. & Haushalter, R. (1998). Chem. Mater. 10, 2091–2096.

Ranford, J. D., Vittal, J. J. & Wang, Y. M. (1998). Inorg. Chem. 37, 1226–1231.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.