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Acta Cryst. (2009). E65, m1083-m1084    [ doi:10.1107/S1600536809031778 ]

Aquabis(5-methylpyrazine-2-carboxylato)zinc(II) trihydrate

Y.-M. Cui, J. Li, X. Zhang and Q.-F. Zeng

Abstract top

In the title compound, [Zn(C6H5N2O2)2(H2O)]·3H2O, the ZnII centre is five-coordinated by two O,N-bidentate Schiff base ligands and one O atom from a water molecule in a slightly distorted square-pyramidal geometry. In the crystal, the complex and uncoordinated water molecules are linked by O-H...O, O-H...N and C-H...O hydrogen bonds, forming a three-dimensional network.

Comment top

There has been much research interest in benzoic acid metal complexes due to their molecular architectures and biological activities (Cheng et al., 2006; Yang et al., 2004). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The ZnII atom is five-coordinated by two O and two N atoms from the two Schiff base ligands and one O from the water molecule, forming a slightly distorted square pyramid coordination (Table 1). The mononuclear complex interacts with the solvent water molecules to form a three-dimensional network (Table 2).

Related literature top

For background to the molecular architecture and biological activity of benzoic acid–metal complexes, see: Cheng et al. (2006); Yang et al. (2004). For reference structural data, see: Allen et al. (1987);

Experimental top

A mixture of 5-methylpyrazine-2-carboxylic acid (276 mg, 2 mmol) and Zn(NO3)2.6H2O (1 mmol, 271 mg) in methanol (10 ml) was stirred for 3 h. After keeping the filtrate in air for 7 d, colourless blocks of (I) were formed.

Refinement top

All H atoms were positioned geometrically (C—H = 0.93 Å for the aromatic H atoms and C—H = 0.96 Å for the aliphatic H atoms) and were refined as riding, with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 30% probability displacement ellipsoids.
Aquabis(5-methylpyrazine-2-carboxylato)zinc(II) trihydrate top
Crystal data top
[Zn(C6H5N2O2)2(H2O)]·3H2OZ = 2
Mr = 411.67F(000) = 424
Triclinic, P1Dx = 1.627 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.134 (4) ÅCell parameters from 25 reflections
b = 10.492 (5) Åθ = 9–12°
c = 10.982 (5) ŵ = 1.51 mm−1
α = 66.61 (2)°T = 296 K
β = 81.85 (2)°Block, colourless
γ = 78.33 (2)°0.32 × 0.28 × 0.23 mm
V = 840.3 (7) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer		2539 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
graphiteθmax = 25.0°, θmin = 2.0°
ω/2θ scansh = −9→9
Absorption correction: ψ scan
(North et al., 1968)		k = −12→12
Tmin = 0.644, Tmax = 0.723l = −13→13
4392 measured reflections3 standard reflections every 200 reflections
2923 independent reflections intensity decay: 1%
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0629P)2 + 0.6023P]
where P = (Fo2 + 2Fc2)/3
2923 reflections(Δ/σ)max = 0.016
260 parametersΔρmax = 0.43 e Å−3
12 restraintsΔρmin = −0.68 e Å−3
Crystal data top
[Zn(C6H5N2O2)2(H2O)]·3H2Oγ = 78.33 (2)°
Mr = 411.67V = 840.3 (7) Å3
Triclinic, P1Z = 2
a = 8.134 (4) ÅMo Kα radiation
b = 10.492 (5) ŵ = 1.51 mm−1
c = 10.982 (5) ÅT = 296 K
α = 66.61 (2)°0.32 × 0.28 × 0.23 mm
β = 81.85 (2)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		2539 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.018
Tmin = 0.644, Tmax = 0.723θmax = 25.0°
4392 measured reflections3 standard reflections every 200 reflections
2923 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.43 e Å−3
S = 1.05Δρmin = −0.68 e Å−3
2923 reflectionsAbsolute structure: ?
260 parametersFlack parameter: ?
12 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
C10.6126 (4)0.8388 (3)0.6598 (3)0.0398 (8)
C20.7345 (4)0.8625 (3)0.5379 (3)0.0328 (7)
C30.7920 (4)0.9875 (3)0.4653 (3)0.0402 (8)
H30.75511.06350.49120.048*
C40.9502 (4)0.8932 (3)0.3229 (3)0.0371 (7)
C50.8939 (4)0.7652 (3)0.3960 (3)0.0358 (7)
H50.93100.68910.37030.043*
C61.0683 (5)0.9107 (4)0.2018 (4)0.0555 (10)
H6A1.01630.98320.12570.083*
H6B1.09470.82370.18810.083*
H6C1.16990.93630.21390.083*
C70.6723 (4)0.3717 (3)0.5483 (3)0.0350 (7)
C80.5573 (4)0.3445 (3)0.6745 (3)0.0315 (7)
C90.4702 (4)0.2334 (3)0.7297 (3)0.0387 (7)
H90.48460.16730.69080.046*
C100.3477 (4)0.3130 (4)0.8926 (3)0.0381 (7)
C110.4392 (4)0.4242 (3)0.8389 (3)0.0362 (7)
H110.42810.48860.87930.043*
C120.2293 (5)0.2978 (4)1.0126 (4)0.0533 (10)
H12A0.11580.31460.98830.080*
H12B0.24210.36471.04870.080*
H12C0.25390.20421.07810.080*
H5A0.964 (4)0.540 (3)0.750 (3)0.040 (10)*
H7A0.070 (5)0.7757 (14)0.720 (4)0.056 (12)*
H8A0.406 (6)0.908 (4)0.855 (3)0.090 (18)*
H5B0.875 (4)0.438 (3)0.8366 (14)0.048 (11)*
H7B0.175 (4)0.675 (4)0.683 (3)0.076 (15)*
H8B0.329 (5)0.985 (2)0.929 (3)0.049 (12)*
H6D0.259 (6)0.734 (3)0.977 (4)0.088 (18)*
H6E0.183 (5)0.674 (4)0.915 (2)0.065 (14)*
N10.7865 (3)0.7518 (3)0.5033 (2)0.0317 (6)
N20.9005 (4)1.0029 (3)0.3579 (3)0.0417 (7)
N30.5426 (3)0.4391 (3)0.7298 (2)0.0318 (6)
N40.3644 (4)0.2175 (3)0.8390 (3)0.0405 (7)
O10.5584 (4)0.9371 (3)0.6954 (3)0.0624 (8)
O20.5775 (3)0.7154 (2)0.7156 (2)0.0423 (6)
O30.6850 (4)0.2940 (2)0.4880 (2)0.0514 (7)
O40.7438 (3)0.4786 (2)0.5142 (2)0.0394 (5)
O50.9020 (3)0.4833 (3)0.7568 (2)0.0449 (6)
O60.2178 (4)0.6625 (3)0.9876 (3)0.0635 (8)
O70.0982 (4)0.6891 (3)0.7377 (3)0.0494 (6)
O80.3459 (4)0.9068 (3)0.9238 (3)0.0654 (8)
Zn10.68363 (5)0.58672 (4)0.62838 (4)0.03747 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0472 (19)0.0338 (17)0.0442 (18)−0.0088 (14)0.0072 (15)−0.0233 (15)
C20.0402 (17)0.0294 (15)0.0330 (15)−0.0068 (13)−0.0022 (13)−0.0157 (13)
C30.051 (2)0.0308 (16)0.0444 (18)−0.0087 (14)0.0016 (15)−0.0211 (15)
C40.0361 (17)0.0369 (17)0.0363 (16)−0.0046 (13)−0.0006 (13)−0.0131 (14)
C50.0402 (18)0.0325 (16)0.0380 (17)−0.0037 (13)−0.0005 (14)−0.0187 (14)
C60.059 (2)0.048 (2)0.050 (2)−0.0061 (18)0.0150 (18)−0.0161 (18)
C70.0468 (18)0.0249 (15)0.0339 (16)−0.0017 (13)−0.0005 (14)−0.0146 (13)
C80.0359 (16)0.0247 (14)0.0368 (16)−0.0031 (12)−0.0015 (13)−0.0158 (13)
C90.0465 (19)0.0318 (16)0.0431 (18)−0.0077 (14)−0.0030 (15)−0.0190 (15)
C100.0327 (17)0.0417 (18)0.0410 (17)−0.0068 (13)0.0010 (13)−0.0178 (15)
C110.0392 (17)0.0352 (16)0.0406 (17)−0.0054 (13)0.0015 (14)−0.0226 (14)
C120.053 (2)0.062 (2)0.050 (2)−0.0182 (18)0.0151 (17)−0.0278 (19)
N10.0369 (14)0.0270 (12)0.0339 (13)−0.0041 (10)−0.0003 (11)−0.0158 (11)
N20.0494 (17)0.0327 (14)0.0427 (15)−0.0095 (12)0.0032 (13)−0.0147 (12)
N30.0352 (14)0.0287 (13)0.0349 (13)−0.0047 (10)0.0007 (11)−0.0169 (11)
N40.0444 (16)0.0356 (14)0.0450 (16)−0.0121 (12)0.0025 (13)−0.0181 (13)
O10.092 (2)0.0378 (13)0.0634 (17)−0.0178 (13)0.0312 (15)−0.0344 (13)
O20.0563 (14)0.0331 (12)0.0444 (13)−0.0164 (10)0.0166 (11)−0.0243 (10)
O30.0831 (19)0.0376 (13)0.0436 (13)−0.0201 (12)0.0148 (13)−0.0273 (11)
O40.0550 (14)0.0322 (12)0.0372 (12)−0.0144 (10)0.0103 (10)−0.0205 (10)
O50.0494 (15)0.0442 (14)0.0403 (14)−0.0148 (11)0.0000 (11)−0.0127 (12)
O60.079 (2)0.071 (2)0.0412 (15)−0.0360 (17)0.0014 (14)−0.0121 (14)
O70.0609 (17)0.0442 (15)0.0444 (14)−0.0189 (12)0.0128 (12)−0.0185 (12)
O80.080 (2)0.0525 (18)0.0684 (19)−0.0268 (15)0.0282 (16)−0.0311 (15)
Zn10.0488 (3)0.0304 (2)0.0392 (2)−0.01200 (16)0.00646 (16)−0.01988 (17)
Geometric parameters (Å, °) top
C1—O11.224 (4)C10—N41.327 (4)
C1—O21.266 (4)C10—C111.394 (5)
C1—C21.516 (4)C10—C121.492 (5)
C2—N11.334 (4)C11—N31.336 (4)
C2—C31.373 (4)C11—H110.9300
C3—N21.345 (4)C12—H12A0.9600
C3—H30.9300C12—H12B0.9600
C4—N21.325 (4)C12—H12C0.9600
C4—C51.395 (5)Zn1—N11.989 (2)
C4—C61.497 (5)Zn1—N31.985 (2)
C5—N11.341 (4)Zn1—O21.951 (2)
C5—H50.9300Zn1—O41.957 (2)
C6—H6A0.9600Zn1—O52.245 (3)
C6—H6B0.9600O5—H5A0.830 (10)
C6—H6C0.9600O5—H5B0.835 (10)
C7—O31.221 (4)O6—H6D0.839 (10)
C7—O41.267 (4)O6—H6E0.841 (10)
C7—C81.518 (4)O7—H7A0.839 (10)
C8—N31.334 (4)O7—H7B0.836 (10)
C8—C91.370 (4)O8—H8A0.835 (10)
C9—N41.347 (4)O8—H8B0.832 (10)
C9—H90.9300
O1—C1—O2126.4 (3)N3—C11—H11119.7
O1—C1—C2118.7 (3)C10—C11—H11119.7
O2—C1—C2115.0 (3)C10—C12—H12A109.5
N1—C2—C3120.3 (3)C10—C12—H12B109.5
N1—C2—C1115.6 (3)H12A—C12—H12B109.5
C3—C2—C1124.1 (3)C10—C12—H12C109.5
N2—C3—C2121.7 (3)H12A—C12—H12C109.5
N2—C3—H3119.2H12B—C12—H12C109.5
C2—C3—H3119.2C2—N1—C5118.9 (3)
N2—C4—C5121.2 (3)C2—N1—Zn1110.7 (2)
N2—C4—C6118.0 (3)C5—N1—Zn1130.3 (2)
C5—C4—C6120.8 (3)C4—N2—C3117.8 (3)
N1—C5—C4120.0 (3)C8—N3—C11118.4 (3)
N1—C5—H5120.0C8—N3—Zn1111.5 (2)
C4—C5—H5120.0C11—N3—Zn1130.1 (2)
C4—C6—H6A109.5C10—N4—C9117.6 (3)
C4—C6—H6B109.5C1—O2—Zn1115.0 (2)
H6A—C6—H6B109.5C7—O4—Zn1115.3 (2)
C4—C6—H6C109.5Zn1—O5—H5A112 (2)
H6A—C6—H6C109.5Zn1—O5—H5B114 (2)
H6B—C6—H6C109.5H5A—O5—H5B110.6 (17)
O3—C7—O4126.2 (3)H6D—O6—H6E108.5 (17)
O3—C7—C8119.0 (3)H7A—O7—H7B109.8 (17)
O4—C7—C8114.8 (3)H8A—O8—H8B110.3 (18)
N3—C8—C9120.6 (3)O2—Zn1—O4166.16 (10)
N3—C8—C7115.2 (3)O2—Zn1—N395.36 (10)
C9—C8—C7124.2 (3)O4—Zn1—N383.22 (9)
N4—C9—C8121.7 (3)O2—Zn1—N183.64 (9)
N4—C9—H9119.2O4—Zn1—N195.00 (10)
C8—C9—H9119.2N3—Zn1—N1168.45 (10)
N4—C10—C11121.0 (3)O2—Zn1—O597.35 (10)
N4—C10—C12118.2 (3)O4—Zn1—O596.49 (10)
C11—C10—C12120.8 (3)N3—Zn1—O594.98 (10)
N3—C11—C10120.6 (3)N1—Zn1—O596.55 (10)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O1i0.932.353.204 (4)153
C3—H3···O3ii0.932.363.255 (4)162
O8—H8B···N4ii0.83 (1)2.30 (2)3.044 (4)150 (3)
O6—H6E···O70.84 (1)2.09 (1)2.932 (4)177 (4)
O6—H6D···O80.84 (1)1.92 (1)2.755 (4)171 (4)
O8—H8A···O10.84 (1)1.95 (1)2.781 (4)171 (4)
O7—H7B···O3iii0.84 (1)2.00 (2)2.797 (3)160 (4)
O7—H7A···N2iv0.84 (1)2.19 (2)2.977 (4)157 (3)
O5—H5B···O6v0.84 (1)1.92 (1)2.754 (4)172 (3)
O5—H5A···O7vi0.83 (1)2.03 (1)2.861 (4)175 (4)
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+2; (vi) x+1, y, z.
Table 1
Selected geometric parameters (Å) top
Zn1—N11.989 (2)Zn1—O41.957 (2)
Zn1—N31.985 (2)Zn1—O52.245 (3)
Zn1—O21.951 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O1i0.932.353.204 (4)153
C3—H3···O3ii0.932.363.255 (4)162
O8—H8B···N4ii0.83 (1)2.30 (2)3.044 (4)150 (3)
O6—H6E···O70.84 (1)2.09 (1)2.932 (4)177 (4)
O6—H6D···O80.84 (1)1.92 (1)2.755 (4)171 (4)
O8—H8A···O10.84 (1)1.95 (1)2.781 (4)171 (4)
O7—H7B···O3iii0.84 (1)2.00 (2)2.797 (3)160 (4)
O7—H7A···N2iv0.84 (1)2.19 (2)2.977 (4)157 (3)
O5—H5B···O6v0.84 (1)1.92 (1)2.754 (4)172 (3)
O5—H5A···O7vi0.83 (1)2.03 (1)2.861 (4)175 (4)
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+2, −z+1; (v) −x+1, −y+1, −z+2; (vi) x+1, y, z.
references
References top

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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

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

Yang, H.-L., You, Z.-L. & Zhu, H.-L. (2004). Acta Cryst. E60, m1213–m1214.