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Acta Cryst. (2009). E65, m640    [ doi:10.1107/S1600536809017115 ]

trans-Diaquabis(6-methoxycarbonylpyridazine-3-carboxylato-[kappa]2N,O)zinc(II) dihydrate

W. Starosta and J. Leciejewicz

Abstract top

In the title centrosymmetric complex, [Zn(C7H5N2O4)2(H2O)2]·2H2O, the ZnII ion is coordinated in a trans mode by two symmetry-related bis-chelating 6-methoxycarbonylpyridazine-3-carboxylate ligands via N and O atoms, and by two aqua ligand O atoms in axial positions, in a slightly distorted octahedral environment. In the crystal structure, complex molecules are linked by intermolecular O-H...O hydrogen bonds between coordinated and solvent water molecules and carboxylate O atoms, forming molecular ribbons propagating along the a axis.

Comment top

In the molecluar structure of the title compound (I) (Fig.1) the ZnII ion, which is located on a center of symmetry, is coordinated in trans mode by two, symmetry related, bis chelating ligand molecules through their N,O bonding atoms. Two water O atoms in axial positions complete the number of coordinated atoms to six. The coordination geometry is slightly distorted octahedral. Bond distances and bond angles are close to those reported for two zinc complexes with pyridazine-3-carboxylate and water ligands (Gryz et al., 2003, 2004), a complex with pyridazine-3,6-dicarboxylate and water ligands (Gryz et al., 2006) and for both modifications of pyridazine-3,6-dicarboxylic acid (Sueur et al., 1987; Starosta & Leciejewicz, 2004). The ligand molecules and the ZnII ion are almost coplanar [r.m.s. 0.0074 Å]. The carboxylic C12/O11/O12 and the carboxymethyl C18/O21/O22/C19 groups make dihedral angles with the pyridazine ring of 3.0 (2) and 6.8 (1)°, respectively. In the crystal structure complex molecules are linked by hydrogen bonds to form molecular ribbons (Fig. 2). The relevant hydrogen-bond parameters are listed in Table 1.

Related literature top

For the crystal structures of two zinc complexes with pyridazine-3-carboxylate and water ligands, see: Gryz et al. (2003, 2004). For a centrosymmetric dimeric zinc(II) complex with pyridazine-3,6-dicarboxylate and water ligands, see: Gryz et al. (2006). For modifications of pyridazine-3,6-dicarboxylic acid, see: Starosta & Leciejewicz (2004); Sueur et al. (1987).

Experimental top

Hot aqueous solutions containing 2 mmol of 6-carboxymethylpyridazine-3-carboxylic acid and 1 mmol of zinc(II) acetate tetrahydrate, respectively, were mixed and boiled for two hours with constant stirring and then left to crystallize at room temperature. After few days, well formed colorless single crystals were found in the mother liquid in the mass of polycrystalline material. The crystals were washed with cold ethanol and dried in air.

Refinement top

H atoms bonded to C atoms were placed in calculated positions with C—H = 0.93 and 0.96 Å and included in a riding-model approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl atoms. Water H atoms were located in difference Fourier maps and were refined isotropically.

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); data reduction: DATAPROC (Kuma, 2001); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code:(i) -x + 1, -y + 1, -z + 1. The symmetry related solvent water molecule is not shown.
[Figure 2] Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.
trans-Diaquabis(6-methoxycarbonylpyridazine-3-carboxylato- κ2N,O)zinc(II) dihydrate top
Crystal data top
[Zn(C7H5N2O4)2(H2O)2]·2H2OZ = 1
Mr = 499.69F000 = 256
Triclinic, P1Dx = 1.766 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.3678 (13) ÅCell parameters from 25 reflections
b = 8.3178 (17) Åθ = 6–15º
c = 9.7717 (19) ŵ = 1.38 mm−1
α = 102.99 (3)ºT = 293 K
β = 108.90 (3)ºPlate, colourless
γ = 94.97 (3)º0.31 × 0.25 × 0.05 mm
V = 469.93 (17) Å3
Data collection top
Kuma KM4 four-circle
diffractometer		Rint = 0.022
Radiation source: fine-focus sealed tubeθmax = 30.1º
Monochromator: graphiteθmin = 2.3º
T = 293 Kh = 0→8
profile data from ω/2θ scansk = −8→11
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)		l = −13→13
Tmin = 0.699, Tmax = 0.9423 standard reflections
2787 measured reflections every 200 reflections
2595 independent reflections intensity decay: 0.0%
2235 reflections with I > 2σ(I)
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)] = 0.035H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0761P)2 + 0.0253P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
2595 reflectionsΔρmax = 0.65 e Å−3
159 parametersΔρmin = −0.75 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C7H5N2O4)2(H2O)2]·2H2Oγ = 94.97 (3)º
Mr = 499.69V = 469.93 (17) Å3
Triclinic, P1Z = 1
a = 6.3678 (13) ÅMo Kα
b = 8.3178 (17) ŵ = 1.38 mm−1
c = 9.7717 (19) ÅT = 293 K
α = 102.99 (3)º0.31 × 0.25 × 0.05 mm
β = 108.90 (3)º
Data collection top
Kuma KM4 four-circle
diffractometer		2235 reflections with I > 2σ(I)
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)		Rint = 0.022
Tmin = 0.699, Tmax = 0.9423 standard reflections
2787 measured reflections every 200 reflections
2595 independent reflections intensity decay: 0.0%
Refinement top
R[F2 > 2σ(F2)] = 0.035159 parameters
wR(F2) = 0.101H atoms treated by a mixture of
independent and constrained refinement
S = 1.07Δρmax = 0.65 e Å−3
2595 reflectionsΔρmin = −0.75 e Å−3
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
Zn10.50000.50000.50000.02700 (11)
O110.8125 (2)0.43757 (16)0.58939 (15)0.0313 (3)
O121.0055 (2)0.22915 (17)0.57098 (18)0.0371 (3)
N110.2403 (2)0.15325 (19)0.29574 (15)0.0255 (3)
N120.4382 (2)0.24189 (17)0.39017 (15)0.0235 (3)
C170.8332 (3)0.2900 (2)0.53776 (18)0.0253 (3)
C130.6217 (3)0.1734 (2)0.42383 (17)0.0226 (3)
C140.6202 (3)0.0068 (2)0.36089 (19)0.0278 (3)
H140.7511−0.03930.38320.033*
O10.4013 (2)0.44171 (18)0.67752 (15)0.0326 (3)
H110.382 (6)0.535 (5)0.738 (4)0.060 (9)*
O21−0.1599 (2)−0.0300 (2)0.10069 (19)0.0436 (3)
C160.2308 (3)−0.0079 (2)0.23612 (17)0.0242 (3)
C18−0.0011 (3)−0.0981 (2)0.13509 (17)0.0272 (3)
C150.4172 (3)−0.0876 (2)0.26422 (19)0.0297 (3)
H150.4048−0.20080.21910.036*
O22−0.0035 (2)−0.25921 (17)0.09206 (16)0.0378 (3)
C19−0.2178 (4)−0.3623 (3)−0.0046 (3)0.0479 (5)
H191−0.3354−0.2966−0.00890.072*
H192−0.2459−0.45460.03460.072*
H193−0.2146−0.4041−0.10360.072*
O20.1965 (3)0.6755 (3)0.8035 (2)0.0493 (4)
H120.274 (5)0.379 (4)0.639 (3)0.043 (7)*
H210.207 (6)0.765 (5)0.830 (4)0.061 (11)*
H220.054 (7)0.622 (6)0.738 (4)0.074 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01928 (14)0.01626 (16)0.03827 (16)0.00521 (9)0.00402 (10)0.00167 (10)
O110.0207 (5)0.0216 (6)0.0435 (6)0.0055 (4)0.0047 (5)0.0023 (5)
O120.0205 (5)0.0257 (7)0.0593 (8)0.0086 (5)0.0064 (5)0.0095 (6)
N110.0200 (6)0.0217 (6)0.0317 (6)0.0038 (5)0.0065 (5)0.0048 (5)
N120.0199 (6)0.0177 (6)0.0308 (6)0.0042 (5)0.0073 (5)0.0045 (5)
C170.0190 (6)0.0219 (7)0.0346 (7)0.0040 (5)0.0080 (5)0.0088 (6)
C130.0206 (6)0.0193 (7)0.0288 (6)0.0045 (5)0.0092 (5)0.0071 (5)
C140.0230 (7)0.0223 (8)0.0373 (8)0.0080 (6)0.0098 (6)0.0065 (6)
O10.0249 (6)0.0286 (6)0.0404 (6)0.0026 (5)0.0095 (5)0.0053 (5)
O210.0268 (6)0.0339 (8)0.0563 (8)0.0047 (5)0.0021 (6)0.0040 (6)
C160.0237 (7)0.0200 (7)0.0265 (6)0.0024 (5)0.0072 (5)0.0043 (5)
C180.0271 (7)0.0233 (8)0.0271 (6)0.0004 (6)0.0072 (6)0.0038 (5)
C150.0312 (8)0.0181 (7)0.0369 (8)0.0060 (6)0.0113 (6)0.0022 (6)
O220.0329 (6)0.0231 (6)0.0429 (7)−0.0004 (5)0.0017 (5)−0.0002 (5)
C190.0403 (10)0.0297 (10)0.0535 (11)−0.0072 (9)0.0010 (9)−0.0003 (8)
O20.0391 (8)0.0403 (10)0.0611 (10)0.0129 (7)0.0139 (7)0.0023 (8)
Geometric parameters (Å, °) top
Zn1—O112.0617 (13)C14—H140.9300
Zn1—O11i2.0617 (13)O1—H110.90 (4)
Zn1—N12i2.1118 (15)O1—H120.84 (3)
Zn1—N122.1118 (15)O21—C181.192 (2)
Zn1—O1i2.1612 (14)C16—C151.390 (2)
Zn1—O12.1612 (14)C16—C181.500 (2)
O11—C171.253 (2)C18—O221.309 (2)
O12—C171.227 (2)C15—H150.9300
N11—C161.324 (2)O22—C191.445 (2)
N11—N121.3277 (19)C19—H1910.9600
N12—C131.323 (2)C19—H1920.9600
C17—C131.520 (2)C19—H1930.9600
C13—C141.382 (2)O2—H210.72 (4)
C14—C151.371 (2)O2—H220.93 (4)
O11—Zn1—O11i180.0C14—C13—C17122.46 (14)
O11—Zn1—N12i101.21 (6)C15—C14—C13117.11 (16)
O11i—Zn1—N12i78.79 (6)C15—C14—H14121.4
O11—Zn1—N1278.79 (6)C13—C14—H14121.4
O11i—Zn1—N12101.21 (6)Zn1—O1—H11111 (2)
N12i—Zn1—N12180.0Zn1—O1—H12108.5 (18)
O11—Zn1—O1i89.08 (6)H11—O1—H12106 (3)
O11i—Zn1—O1i90.91 (6)N11—C16—C15123.58 (15)
N12i—Zn1—O1i89.79 (6)N11—C16—C18113.77 (15)
N12—Zn1—O1i90.20 (6)C15—C16—C18122.66 (15)
O11—Zn1—O190.92 (6)O21—C18—O22125.50 (16)
O11i—Zn1—O189.08 (6)O21—C18—C16123.73 (16)
N12i—Zn1—O190.21 (6)O22—C18—C16110.77 (15)
N12—Zn1—O189.80 (6)C14—C15—C16117.52 (16)
O1i—Zn1—O1180.00 (6)C14—C15—H15121.2
C17—O11—Zn1116.33 (11)C16—C15—H15121.2
C16—N11—N12117.85 (14)C18—O22—C19116.76 (16)
C13—N12—N11121.74 (14)O22—C19—H191109.5
C13—N12—Zn1112.69 (11)O22—C19—H192109.5
N11—N12—Zn1125.56 (11)H191—C19—H192109.5
O12—C17—O11126.85 (16)O22—C19—H193109.5
O12—C17—C13116.54 (15)H191—C19—H193109.5
O11—C17—C13116.61 (14)H192—C19—H193109.5
N12—C13—C14122.16 (15)H21—O2—H22114 (4)
N12—C13—C17115.37 (14)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H22···O11ii0.93 (4)1.99 (4)2.874 (3)158 (4)
O2—H21···O21iii0.72 (4)2.23 (4)2.940 (3)168 (4)
O1—H12···O12ii0.84 (3)1.86 (3)2.695 (2)174 (3)
O1—H11···O20.90 (4)1.89 (4)2.720 (2)152 (3)
Symmetry codes: (ii) x−1, y, z; (iii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H22···O11i0.93 (4)1.99 (4)2.874 (3)158 (4)
O2—H21···O21ii0.72 (4)2.23 (4)2.940 (3)168 (4)
O1—H12···O12i0.84 (3)1.86 (3)2.695 (2)174 (3)
O1—H11···O20.90 (4)1.89 (4)2.720 (2)152 (3)
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1.
references
References top

Gryz, M., Starosta, W. & Leciejewicz, J. (2004). Acta Cryst. E60, m1481–m1483.

Gryz, M., Starosta, initials? & Leciejewicz, J. (2006). Acta Cryst. E62, m3470–m3472.

Gryz, M., Starosta, W., Ptasiewicz-Bąk, H. & Leciejewicz, J. (2003). J. Coord. Chem. 56, 1505–1511.

Kuma (1996). KM-4 Software. Kuma Diffraction Ltd. Wrocław, Poland.

Kuma (2001). DATAPROC. Kuma Diffraction Ltd. Wrocł aw, Poland.

Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England

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

Starosta, W. & Leciejewicz, J. (2004). Acta Cryst. E60, o2219–o2220.

Sueur, S., Lagrenee, M., Abraham, F. & Bremard, C. (1987). J. Heterocycl. Chem. 24, 1285–1289.