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Acta Cryst. (2007). E63, m1662-m1663    [ doi:10.1107/S1600536807022544 ]

Bis([mu]-pyridazine-3-carboxylato)-[kappa]3N,O:O;[kappa]3O:N,O-bis[triaquacalcium(II)]

W. Starosta and J. Leciejewicz

Abstract top

The structure of the title compound, [Ca2(C5H3N2O2)2(H2O)6], is composed of centrosymmetric dimeric molecules, in which the CaII ions are bridged by two carboxylate O atoms of bidentate ligands. Each CaII ion is coordinated by two carboxylate O atoms, a hetero-ring N atom and three water O atoms. The coordination number of each CaII ion is eight, forming a distorted decahedron. Coordinated water molecules act as donors linking adjacent dimers into a three-dimensional hydrogen-bonded network. Intra-dimer hydrogen bonds are also present.

Comment top

The structure of compound (1) is composed of discrete, dinuclear centrosymmetric units consisting of two CaII ions bridged by two carboxylate oxygen atoms each donated by the ligand molecule coordinated to a different CaII ion. Figure 1 shows the molecular structure of a dimer with atom labelling scheme; Figure 2 illustrates the way the dimers are packed in the crystal. The CaII ion is coordinated by two pyridazine-3-carboxylate ligands via their N,O bonding groups. In both, only one carboxylate O atom participates in coordination. Pyridazine rings are planar with r.m.s. of 0.0074 Å and 0.0050Å for the two symmetry unique ligand molecules. The planes of the rings make an angle of 84.0° each to the other. The planes of the carboxylate groups make the angles of 11.6° and 0.2° with the two pyridazine rings to which they are bonded. Bond distances and bond angles within the ligand molecules agree well with those reported earlier for the parent acid (Gryz et al., 2003). The coordinated carboxylate oxygen atom of one ligand molecule acts as bidentate being coordinated to the symmetry related CaII ion, thus forming two bridges Ca – O11 – Cai and Ca – O11i – Cai [symmetry code as in Table 1]. Apart from the two N,O bonding groups and the bridging carboxylate O atom, each CaII ion is also coordinated by three O atoms of water molecules. The coordination number of each CaII ion is eight and the coordination geometry is represented by a severely distorted decahedron, similar to that observed in a Ca complex with pyrazine-2-carboxylate and water ligands (Ptasiewicz-Bąk & et al., 1998). One of the strongly distorted tetragonal bases (r.m.s 0.2715 Å) is composed of O11, N12, O21 and N22 atoms, the other base (r.m.s. 0.2990 Å) is formed by three water oxygen O (O1, O2, O3) and the bridging carboxylate O atom O11i. The bases are almost parallel making an angle of 6.1° but the tetragons are rotated by ca 45°, one in respect to the other. The observed Ca—O bond distances and angles are typical for calcium complexes with carboxylate ligands (Einspahr & Bugg, 1981). Coordinated water molecules act as donors in hydrogen bonds to the carboxylate oxygen atoms and hetero-ring nitrogen atoms in adjacent dimers (Fig. 2). Intradimeric hydrogen bonds are also observed. For details – see Table 2.

Related literature top

We have recently determined the structure of the free ligand (Gryz et al., 2003) and a related structure has also been reported (Ptasiewicz-Bąk et al., 1998). The bond lengths and angles in the title compound are typical (Einspahr & Bugg, 1981).

Experimental top

Hot aqueous solutions containing 2 mmol s of pyridazine-3-carboxylic acid and 1 mmol of calcium(II) acetate tetrahydrate, respectively, were mixed and boiled for one hour with constant stirring. After cooling to room temperature, 5 ml of 3 N acetic acid were added. The solution when evaporated to dryness at room temperature, over several days, provided rectangular blocks as single crystals. They were washed with cold ethanol and dried in air.

Refinement top

H atoms were refined independently with isotropic displacement parameters.

Computing details top

Data collection: KM-4 Software (Kuma Diffraction, 1996); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma Diffraction, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1992) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (1) with atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabeled atoms are related by the symmetry operator (-x + 1, -y + 2, -z + 1).
[Figure 2] Fig. 2. The packing of (1) with hydrogen bonds shown as dashed lines.
Bis(µ-pyridazine-3-carboxylato)-κ3N,O:O;κ3O:N,O-bis[triaquacalcium(II)] top
Crystal data top
[Ca2(C5H3N2O2)2(H2O)6]F(000) = 704
Mr = 680.63Dx = 1.582 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 9.1730 (18) Åθ = 6–15°
b = 10.539 (2) ŵ = 0.48 mm−1
c = 14.984 (3) ÅT = 293 K
β = 99.43 (3)°Rectangular block, colourless
V = 1429.0 (5) Å30.54 × 0.22 × 0.18 mm
Z = 2
Data collection top
Kuma KM4 four-circle
diffractometer		3154 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
graphiteθmax = 30.1°, θmin = 2.4°
profile data from θ/2θ scansh = 0→12
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2000)		k = −14→0
Tmin = 0.877, Tmax = 0.901l = −21→20
4432 measured reflections3 standard reflections every 200 reflections
4182 independent reflections intensity decay: 2.5%
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102Only H-atom coordinates refined
S = 0.98 w = 1/[σ2(Fo2) + (0.0631P)2 + 0.4166P]
where P = (Fo2 + 2Fc2)/3
4182 reflections(Δ/σ)max = 0.001
247 parametersΔρmax = 0.35 e Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Ca2(C5H3N2O2)2(H2O)6]V = 1429.0 (5) Å3
Mr = 680.63Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.1730 (18) ŵ = 0.48 mm−1
b = 10.539 (2) ÅT = 293 K
c = 14.984 (3) Å0.54 × 0.22 × 0.18 mm
β = 99.43 (3)°
Data collection top
Kuma KM4 four-circle
diffractometer		3154 reflections with I > 2σ(I)
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2000)		Rint = 0.017
Tmin = 0.877, Tmax = 0.901θmax = 30.1°
4432 measured reflections3 standard reflections every 200 reflections
4182 independent reflections intensity decay: 2.5%
Refinement top
R[F2 > 2σ(F2)] = 0.033Only H-atom coordinates refined
wR(F2) = 0.102Δρmax = 0.35 e Å−3
S = 0.98Δρmin = −0.47 e Å−3
4182 reflectionsAbsolute structure: ?
247 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
Ca10.65075 (3)0.88232 (3)0.575164 (18)0.02345 (8)
O110.39476 (11)0.95185 (10)0.55635 (7)0.0282 (2)
N120.49408 (13)0.77300 (12)0.68154 (8)0.0277 (2)
O30.67401 (17)1.08313 (13)0.64699 (10)0.0474 (3)
O20.87173 (14)0.87577 (15)0.51303 (10)0.0434 (3)
O10.83709 (16)0.83982 (14)0.70706 (9)0.0473 (3)
O210.53629 (13)0.76031 (11)0.44708 (8)0.0391 (3)
C170.30113 (15)0.89606 (14)0.59370 (10)0.0279 (3)
O120.16530 (13)0.90909 (17)0.57563 (12)0.0590 (4)
N220.73182 (16)0.64577 (12)0.57056 (9)0.0327 (3)
N110.54731 (15)0.68921 (14)0.74637 (10)0.0362 (3)
C130.35352 (16)0.80508 (14)0.66984 (9)0.0270 (3)
C230.68131 (18)0.58150 (14)0.49646 (10)0.0317 (3)
O220.5225 (2)0.59002 (14)0.35821 (10)0.0611 (4)
N210.8315 (2)0.59353 (15)0.63436 (11)0.0501 (4)
C270.56975 (18)0.64986 (15)0.42743 (11)0.0341 (3)
C140.2554 (2)0.7596 (2)0.72419 (13)0.0436 (4)
C160.4569 (2)0.6429 (2)0.79794 (14)0.0474 (4)
C240.7276 (3)0.45936 (19)0.48169 (15)0.0575 (6)
C150.3101 (2)0.6764 (2)0.79061 (15)0.0544 (5)
C260.8765 (3)0.4766 (2)0.62310 (16)0.0648 (7)
C250.8276 (4)0.4049 (2)0.54776 (18)0.0713 (8)
H310.610 (3)1.141 (3)0.6249 (19)0.062 (7)*
H110.885 (3)0.862 (2)0.7526 (18)0.049 (6)*
H140.152 (3)0.789 (2)0.7140 (16)0.056 (7)*
H150.253 (3)0.649 (3)0.830 (2)0.073 (8)*
H160.504 (3)0.586 (2)0.8425 (17)0.057 (7)*
H230.687 (3)0.418 (3)0.427 (2)0.078 (9)*
H250.955 (4)0.446 (3)0.674 (2)0.090 (10)*
H240.870 (3)0.324 (3)0.5399 (19)0.070 (8)*
H120.853 (3)0.755 (3)0.706 (2)0.090 (10)*
H320.734 (3)1.108 (2)0.6894 (18)0.056 (7)*
H210.949 (3)0.873 (3)0.546 (2)0.071 (9)*
H220.869 (3)0.949 (3)0.4853 (17)0.056 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ca10.02048 (13)0.02388 (13)0.02488 (13)−0.00055 (9)0.00039 (9)−0.00032 (9)
O110.0232 (4)0.0304 (5)0.0308 (5)0.0006 (4)0.0035 (4)0.0058 (4)
N120.0272 (6)0.0278 (6)0.0273 (6)0.0009 (4)0.0023 (4)0.0029 (4)
O30.0530 (8)0.0348 (6)0.0445 (7)0.0109 (6)−0.0219 (6)−0.0133 (5)
O20.0257 (5)0.0553 (8)0.0487 (7)0.0012 (5)0.0045 (5)0.0161 (6)
O10.0538 (8)0.0407 (7)0.0384 (6)−0.0004 (6)−0.0195 (6)−0.0027 (5)
O210.0415 (6)0.0282 (5)0.0409 (6)0.0060 (5)−0.0129 (5)−0.0040 (5)
C170.0230 (6)0.0284 (6)0.0315 (7)0.0002 (5)0.0018 (5)0.0024 (5)
O120.0218 (5)0.0739 (10)0.0796 (11)0.0013 (6)0.0035 (6)0.0423 (8)
N220.0407 (7)0.0270 (6)0.0273 (6)0.0034 (5)−0.0042 (5)0.0013 (5)
N110.0355 (7)0.0360 (7)0.0360 (7)0.0059 (5)0.0023 (5)0.0098 (5)
C130.0284 (6)0.0258 (6)0.0266 (6)0.0005 (5)0.0044 (5)0.0010 (5)
C230.0396 (8)0.0247 (6)0.0284 (7)0.0011 (6)−0.0013 (6)−0.0006 (5)
O220.0825 (11)0.0446 (7)0.0432 (7)0.0131 (7)−0.0288 (7)−0.0143 (6)
N210.0691 (11)0.0380 (8)0.0348 (7)0.0142 (7)−0.0166 (7)0.0015 (6)
C270.0384 (8)0.0281 (7)0.0315 (7)0.0013 (6)−0.0068 (6)−0.0013 (6)
C140.0347 (8)0.0509 (10)0.0488 (10)0.0073 (7)0.0172 (7)0.0159 (8)
C160.0504 (10)0.0490 (10)0.0437 (9)0.0084 (8)0.0104 (8)0.0213 (8)
C240.0833 (15)0.0335 (9)0.0472 (10)0.0159 (10)−0.0143 (10)−0.0117 (8)
C150.0524 (11)0.0641 (13)0.0522 (11)0.0086 (10)0.0250 (9)0.0265 (10)
C260.0882 (17)0.0422 (10)0.0527 (12)0.0239 (11)−0.0219 (12)0.0050 (9)
C250.103 (2)0.0350 (10)0.0650 (14)0.0299 (12)−0.0179 (13)−0.0060 (9)
Geometric parameters (Å, °) top
Ca1—O22.3662 (14)C17—O121.2385 (19)
Ca1—O32.3680 (13)C17—C131.508 (2)
Ca1—O212.4040 (13)N22—C231.3183 (19)
Ca1—O112.4318 (11)N22—N211.3294 (19)
Ca1—O12.4334 (15)N11—C161.317 (2)
Ca1—N122.5853 (14)C13—C141.394 (2)
Ca1—N222.6057 (14)C23—C241.385 (2)
Ca1—O11i2.6158 (11)C23—C271.513 (2)
Ca1—Ca1i4.1029 (11)O22—C271.230 (2)
Ca1—H222.68 (3)N21—C261.319 (3)
O11—C171.2466 (17)C14—C151.359 (3)
O11—Ca1i2.6158 (11)C14—H140.99 (3)
N12—C131.3166 (19)C16—C151.379 (3)
N12—N111.3440 (18)C16—H160.95 (3)
O3—H310.87 (3)C24—C251.361 (3)
O3—H320.81 (3)C24—H230.95 (3)
O2—H210.79 (3)C15—H150.90 (3)
O2—H220.87 (3)C26—C251.371 (3)
O1—H110.78 (3)C26—H251.01 (3)
O1—H120.91 (4)C25—H240.96 (3)
O21—C271.251 (2)
O2—Ca1—O3100.70 (6)C13—N12—N11119.79 (13)
O2—Ca1—O2187.74 (5)C13—N12—Ca1115.76 (9)
O3—Ca1—O21146.71 (4)N11—N12—Ca1124.45 (10)
O2—Ca1—O11146.76 (4)Ca1—O3—H31116.4 (18)
O3—Ca1—O1178.27 (5)Ca1—O3—H32129.8 (18)
O21—Ca1—O1177.38 (5)H31—O3—H32114 (2)
O2—Ca1—O177.35 (6)Ca1—O2—H21119 (2)
O3—Ca1—O178.25 (5)Ca1—O2—H22101.5 (17)
O21—Ca1—O1134.97 (5)H21—O2—H22107 (3)
O11—Ca1—O1133.32 (5)Ca1—O1—H11150.3 (18)
O2—Ca1—N12145.91 (5)Ca1—O1—H12105 (2)
O3—Ca1—N1297.81 (5)H11—O1—H12104 (3)
O21—Ca1—N1292.27 (5)C27—O21—Ca1126.41 (10)
O11—Ca1—N1265.29 (4)O12—C17—O11126.30 (14)
O1—Ca1—N1278.74 (5)O12—C17—C13114.87 (13)
O2—Ca1—N2272.25 (5)O11—C17—C13118.82 (12)
O3—Ca1—N22149.57 (5)C23—N22—N21119.89 (14)
O21—Ca1—N2263.66 (4)C23—N22—Ca1116.83 (10)
O11—Ca1—N22124.03 (4)N21—N22—Ca1122.89 (10)
O1—Ca1—N2271.33 (5)C16—N11—N12118.60 (14)
N12—Ca1—N2277.28 (5)N12—C13—C14123.08 (14)
O2—Ca1—O11i76.37 (5)N12—C13—C17116.61 (12)
O3—Ca1—O11i74.73 (5)C14—C13—C17120.31 (13)
O21—Ca1—O11i76.17 (4)N22—C23—C24122.52 (15)
O11—Ca1—O11i71.30 (4)N22—C23—C27115.86 (13)
O1—Ca1—O11i137.64 (5)C24—C23—C27121.62 (15)
N12—Ca1—O11i136.55 (4)C26—N21—N22119.19 (16)
N22—Ca1—O11i129.07 (4)O22—C27—O21127.52 (15)
O2—Ca1—Ca1i110.21 (4)O22—C27—C23115.95 (15)
O3—Ca1—Ca1i73.24 (4)O21—C27—C23116.53 (13)
O21—Ca1—Ca1i73.63 (3)C15—C14—C13116.98 (16)
O11—Ca1—Ca1i37.15 (3)C15—C14—H14123.2 (14)
O1—Ca1—Ca1i151.38 (4)C13—C14—H14119.8 (14)
N12—Ca1—Ca1i102.42 (3)N11—C16—C15123.98 (17)
N22—Ca1—Ca1i137.18 (3)N11—C16—H16112.9 (15)
O11i—Ca1—Ca1i34.15 (2)C15—C16—H16123.1 (15)
O2—Ca1—H2218.6 (6)C25—C24—C23117.60 (18)
O3—Ca1—H2288.6 (6)C25—C24—H23123.5 (19)
O21—Ca1—H2290.2 (6)C23—C24—H23118.9 (19)
O11—Ca1—H22130.5 (6)C14—C15—C16117.52 (17)
O1—Ca1—H2288.5 (6)C14—C15—H15120.4 (19)
N12—Ca1—H22164.1 (6)C16—C15—H15122.0 (18)
N22—Ca1—H2289.8 (6)N21—C26—C25123.58 (19)
O11i—Ca1—H2259.1 (6)N21—C26—H25113.6 (19)
Ca1i—Ca1—H2293.3 (6)C25—C26—H25122.7 (19)
C17—O11—Ca1121.94 (9)C24—C25—C26117.19 (19)
C17—O11—Ca1i128.07 (9)C24—C25—H24121.8 (17)
Ca1—O11—Ca1i108.70 (4)C26—C25—H24120.7 (17)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H31···O21i0.87 (3)1.89 (3)2.7458 (18)166 (3)
O1—H11···O22ii0.78 (3)1.92 (3)2.703 (2)173 (2)
O1—H12···N210.91 (4)2.00 (4)2.812 (2)148 (3)
O1—H12···N220.91 (4)2.43 (3)2.941 (2)116 (2)
O3—H32···N11iii0.81 (3)2.25 (3)3.000 (2)154 (2)
O2—H21···O12iv0.79 (3)2.00 (3)2.725 (2)152 (3)
O2—H22···O12i0.87 (3)1.76 (3)2.622 (2)171 (3)
O2—H22···O11i0.87 (3)2.61 (3)3.0861 (18)115 (2)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x+1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Ca1—O22.3662 (14)Ca1—O12.4334 (15)
Ca1—O32.3680 (13)Ca1—N122.5853 (14)
Ca1—O212.4040 (13)Ca1—N222.6057 (14)
Ca1—O112.4318 (11)Ca1—O11i2.6158 (11)
O21—Ca1—O1177.38 (5)O21—Ca1—N2263.66 (4)
O2—Ca1—O177.35 (6)N12—Ca1—N2277.28 (5)
O3—Ca1—O178.25 (5)O2—Ca1—O11i76.37 (5)
O11—Ca1—N1265.29 (4)O3—Ca1—O11i74.73 (5)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H31···O21i0.87 (3)1.89 (3)2.7458 (18)166 (3)
O1—H11···O22ii0.78 (3)1.92 (3)2.703 (2)173 (2)
O1—H12···N210.91 (4)2.00 (4)2.812 (2)148 (3)
O1—H12···N220.91 (4)2.43 (3)2.941 (2)116 (2)
O3—H32···N11iii0.81 (3)2.25 (3)3.000 (2)154 (2)
O2—H21···O12iv0.79 (3)2.00 (3)2.725 (2)152 (3)
O2—H22···O12i0.87 (3)1.76 (3)2.622 (2)171 (3)
O2—H22···O11i0.87 (3)2.61 (3)3.0861 (18)115 (2)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x+1, y, z.
references
References top

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