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Acta Cryst. (2009). E65, m732    [ doi:10.1107/S1600536809020479 ]

Poly[diaqua([mu]4-3,5-dicarboxylatopyrazol-1-ido-[kappa]6N1,O5:N2,O3:O3':O5,O5')lanthanum(III)]

J. Xia and J.-F. Wei

Abstract top

In the title coordination polymer, [La(C5HN2O4)(H2O)2]n, the lanthanum(III) metal centre is nine-coordinated, with a distorted tricapped trigonal prismatic geometry, by the O atoms of two water molecules and by two N and five O atoms of two N,O-bidentate, one O,O'-bidentate and one O-monodentate 3,5-dicarboxylatopyrazol-1-ide ligands. The polymeric three-dimensional structure is stabilized by intermolecular O-H...O hydrogen bonds.

Comment top

In the past decade, the design and synthesis of metal–organic frameworks have drawn great attention. Pyrazole-3,5-dicarboxylic acid (H3pdc) has been found to be a suitable ligand in this study for its various coordination modes and strong coordination ability. Some complexes of H3pdc have been reported recently (Sakagami et al., 1996; Wang et al., 2007; Yang et al., 2004; King et al., 2003; Pan et al., 2000). Herein, we report the synthesis and crystal structure of a new lanthanum complex with pdc3- anions.

The coordination environment of the lanthanum(III) metal centre (Fig. 1) is provided by two N atoms and seven O atoms, of which the N atoms are from two pyrazole rings, five O atoms are from four carboxyl groups, and two O atoms are from water molecules. These atoms define a distorted tricapped trigonal prism, as commonly observed for nine-coordinate lanthanides. In the title complex, the La—O and La—N bond lengths are in the range 2.424 (2)–2.739 (2) and 2.621 (2)–2.665 (2) Å, respectively. The pdc3- ligands link lanthanum(III) atoms to form a three-dimensional framework using a µ4 coordination mode (Fig. 2). The crystal structure is stabilized by O—H···O hydrogen bonds (Table 1).

Related literature top

For other coordination complexes with pyrazole-3,5-dicarboxylic acid ligands, see: Sakagami et al. (1996); Wang et al. (2007); Yang et al. (2004); King et al. (2003); Pan et al. (2000).

Experimental top

All chemicals used (reagent grade) were commercially avaiable. The compound was synthesized by heating a mixture of pyrazole-3,5-dicarboxylic acid (0.078 g, 0.5 mmol), lanthanum nitrate (0.129 g, 0.3 mmol) and water (10 ml) in a 20 ml acid digestion bomb at 180 °C for 3 d. Colourless single crystals suitable for X-ray analysis were obtained after cooling to room temperature.

Refinement top

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93, O—H = 0.85 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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 coordination environment of the lanthanum(III) atom, with the atom-numbering scheme, showing displacement ellipsoids drawn at the 30% probability level. H atoms are omitted for clarity. Symmetry codes: (A) 3/2-x, -1/2+y, z; (B) x, 1/2-y, 1/2+z; (C) 2-x, -y, 1-z.
[Figure 2] Fig. 2. Crystal packing of the title compound viewed along the a axis. H atoms are omitted for clarity.
Poly[diaqua(µ4-3,5-dicarboxylatopyrazol-1-ido- κ6N1,O5:N2,O3:O3': O5,O5')lanthanum(III)] top
Crystal data top
[La(C5HN2O4)(H2O)2]F(000) = 1232
Mr = 328.02Dx = 2.567 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3962 reflections
a = 12.5712 (8) Åθ = 2.5–27.8°
b = 8.4350 (6) ŵ = 5.04 mm−1
c = 16.007 (1) ÅT = 293 K
V = 1697.35 (19) Å3Block, colourless
Z = 80.32 × 0.24 × 0.20 mm
Data collection top
Bruker APEXII CCD
diffractometer		1496 independent reflections
Radiation source: fine-focus sealed tube1316 reflections with I > 2σ(I)
graphiteRint = 0.023
φ and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→13
Tmin = 0.239, Tmax = 0.365k = −10→10
8554 measured reflectionsl = −19→15
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)] = 0.016H-atom parameters constrained
wR(F2) = 0.041 w = 1/[σ2(Fo2) + (0.0185P)2 + 2.3502P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.003
1496 reflectionsΔρmax = 0.52 e Å−3
128 parametersΔρmin = −0.50 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: 0.00271 (13)
Crystal data top
[La(C5HN2O4)(H2O)2]V = 1697.35 (19) Å3
Mr = 328.02Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.5712 (8) ŵ = 5.04 mm−1
b = 8.4350 (6) ÅT = 293 K
c = 16.007 (1) Å0.32 × 0.24 × 0.20 mm
Data collection top
Bruker APEXII CCD
diffractometer		1496 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1316 reflections with I > 2σ(I)
Tmin = 0.239, Tmax = 0.365Rint = 0.023
8554 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.016H-atom parameters constrained
wR(F2) = 0.041Δρmax = 0.52 e Å−3
S = 1.06Δρmin = −0.50 e Å−3
1496 reflectionsAbsolute structure: ?
128 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
La10.968426 (12)0.009678 (17)0.662201 (9)0.01104 (9)
O10.80247 (17)0.1816 (2)0.67873 (12)0.0212 (5)
O20.68279 (17)0.3455 (3)0.62560 (14)0.0274 (5)
O30.9060 (2)0.5049 (2)0.31256 (13)0.0222 (5)
O40.98606 (16)0.2761 (2)0.29004 (12)0.0170 (4)
O51.0936 (2)0.2221 (3)0.60343 (15)0.0325 (6)
H5A1.09420.14420.63710.049*
H5B1.09730.30660.63220.049*
O61.15184 (19)−0.0151 (2)0.73037 (16)0.0338 (6)
H6A1.1780−0.10470.74340.051*
H6B1.18510.06640.74750.051*
N10.89277 (19)0.1436 (3)0.52362 (14)0.0162 (5)
N20.93750 (19)0.1715 (3)0.44839 (14)0.0165 (5)
C10.7644 (2)0.2632 (3)0.61947 (19)0.0153 (6)
C20.8238 (2)0.2624 (3)0.53938 (17)0.0155 (6)
C30.8237 (2)0.3719 (3)0.47460 (18)0.0190 (7)
H30.78410.46460.46980.023*
C40.8967 (2)0.3099 (3)0.41903 (17)0.0160 (6)
C50.9322 (2)0.3675 (3)0.33671 (17)0.0154 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La10.01164 (12)0.01181 (12)0.00967 (12)0.00021 (6)0.00036 (6)−0.00053 (6)
O10.0230 (12)0.0285 (11)0.0122 (11)0.0074 (9)0.0021 (9)0.0032 (9)
O20.0223 (12)0.0311 (12)0.0287 (13)0.0141 (10)0.0086 (10)0.0075 (10)
O30.0358 (13)0.0158 (11)0.0150 (10)0.0056 (9)0.0055 (10)0.0026 (8)
O40.0217 (11)0.0158 (10)0.0134 (11)0.0024 (8)0.0033 (8)−0.0008 (8)
O50.0410 (15)0.0214 (11)0.0351 (13)−0.0112 (11)0.0097 (12)−0.0019 (10)
O60.0253 (13)0.0264 (12)0.0496 (16)−0.0030 (10)−0.0187 (12)0.0042 (10)
N10.0190 (13)0.0176 (12)0.0120 (12)0.0019 (10)0.0034 (10)0.0015 (9)
N20.0201 (13)0.0186 (12)0.0108 (12)0.0022 (10)0.0041 (10)0.0027 (10)
C10.0151 (16)0.0149 (14)0.0159 (15)−0.0019 (12)0.0012 (11)−0.0016 (11)
C20.0159 (15)0.0169 (14)0.0137 (15)0.0016 (12)0.0000 (12)0.0006 (11)
C30.0235 (17)0.0163 (14)0.0173 (16)0.0060 (12)0.0011 (12)0.0011 (12)
C40.0190 (16)0.0153 (13)0.0137 (15)0.0014 (12)0.0004 (12)0.0016 (11)
C50.0159 (15)0.0153 (14)0.0149 (16)−0.0021 (11)−0.0020 (11)0.0005 (12)
Geometric parameters (Å, °) top
La1—O2i2.424 (2)O4—La1iii2.5929 (19)
La1—O3ii2.535 (2)O4—La1v2.7388 (19)
La1—O12.554 (2)O5—H5A0.8500
La1—O62.559 (2)O5—H5B0.8500
La1—O52.564 (2)O6—H6A0.8500
La1—O4iii2.5929 (19)O6—H6B0.8499
La1—N2iii2.620 (2)N1—C21.349 (4)
La1—N12.665 (2)N1—N21.350 (3)
La1—O4ii2.7388 (19)N2—C41.360 (4)
La1—C5ii3.014 (3)N2—La1iii2.620 (2)
La1—H5A1.9874C1—C21.483 (4)
O1—C11.266 (4)C2—C31.389 (4)
O2—C11.242 (3)C3—C41.380 (4)
O2—La1iv2.424 (2)C3—H30.9300
O3—C51.266 (3)C4—C51.474 (4)
O3—La1v2.535 (2)C5—La1v3.014 (3)
O4—C51.269 (3)
O2i—La1—O3ii87.64 (7)O2i—La1—H5A154.3
O2i—La1—O173.08 (8)O3ii—La1—H5A117.8
O3ii—La1—O171.11 (7)O1—La1—H5A110.3
O2i—La1—O6139.71 (7)O6—La1—H5A54.3
O3ii—La1—O682.55 (8)O5—La1—H5A15.9
O1—La1—O6137.56 (7)O4iii—La1—H5A114.5
O2i—La1—O5142.39 (7)N2iii—La1—H5A80.6
O3ii—La1—O5124.93 (7)N1—La1—H5A82.7
O1—La1—O598.20 (7)O4ii—La1—H5A73.1
O6—La1—O570.16 (8)C5ii—La1—H5A96.4
O2i—La1—O4iii73.32 (7)C1—O1—La1122.68 (18)
O3ii—La1—O4iii75.12 (6)C1—O2—La1iv170.3 (2)
O1—La1—O4iii132.65 (6)C5—O3—La1v99.48 (17)
O6—La1—O4iii66.39 (6)C5—O4—La1iii120.58 (17)
O5—La1—O4iii128.50 (7)C5—O4—La1v89.78 (16)
O2i—La1—N2iii81.81 (8)La1iii—O4—La1v148.37 (8)
O3ii—La1—N2iii138.85 (7)La1—O5—H5B114.9
O1—La1—N2iii140.31 (7)H5A—O5—H5B107.7
O6—La1—N2iii80.43 (8)La1—O6—H6A121.7
O5—La1—N2iii83.25 (7)La1—O6—H6B120.9
O4iii—La1—N2iii63.74 (7)H6A—O6—H6B116.7
O2i—La1—N176.18 (7)C2—N1—N2107.8 (2)
O3ii—La1—N1134.47 (7)C2—N1—La1112.86 (17)
O1—La1—N163.52 (7)N2—N1—La1131.91 (17)
O6—La1—N1135.32 (8)N1—N2—C4107.5 (2)
O5—La1—N167.51 (8)N1—N2—La1iii133.56 (17)
O4iii—La1—N1135.91 (6)C4—N2—La1iii115.97 (17)
N2iii—La1—N181.13 (7)O2—C1—O1123.8 (3)
O2i—La1—O4ii128.39 (7)O2—C1—C2119.1 (3)
O3ii—La1—O4ii49.28 (6)O1—C1—C2117.0 (2)
O1—La1—O4ii67.31 (6)N1—C2—C3110.8 (3)
O6—La1—O4ii70.28 (7)N1—C2—C1119.2 (2)
O5—La1—O4ii76.32 (6)C3—C2—C1129.9 (3)
O4iii—La1—O4ii112.04 (2)C4—C3—C2103.2 (2)
N2iii—La1—O4ii148.53 (7)C4—C3—H3128.4
N1—La1—O4ii111.79 (6)C2—C3—H3128.4
O2i—La1—C5ii107.57 (8)N2—C4—C3110.7 (2)
O3ii—La1—C5ii24.47 (7)N2—C4—C5118.5 (2)
O1—La1—C5ii65.50 (7)C3—C4—C5130.8 (3)
O6—La1—C5ii76.66 (8)O3—C5—O4121.0 (3)
O5—La1—C5ii101.11 (7)O3—C5—C4119.7 (3)
O4iii—La1—C5ii94.58 (7)O4—C5—C4119.2 (2)
N2iii—La1—C5ii153.48 (8)O3—C5—La1v56.04 (14)
N1—La1—C5ii124.88 (7)O4—C5—La1v65.32 (14)
O4ii—La1—C5ii24.90 (7)C4—C5—La1v171.1 (2)
O2i—La1—O1—C1−89.3 (2)La1—N1—N2—La1iii55.4 (3)
O3ii—La1—O1—C1177.3 (2)La1—O1—C1—O2178.7 (2)
O6—La1—O1—C1122.6 (2)La1—O1—C1—C2−3.1 (3)
O5—La1—O1—C153.1 (2)N2—N1—C2—C3−0.9 (3)
O4iii—La1—O1—C1−135.8 (2)La1—N1—C2—C3152.7 (2)
N2iii—La1—O1—C1−36.2 (3)N2—N1—C2—C1−178.8 (2)
N1—La1—O1—C1−6.6 (2)La1—N1—C2—C1−25.2 (3)
O4ii—La1—O1—C1124.5 (2)O2—C1—C2—N1−161.5 (3)
C5ii—La1—O1—C1151.7 (2)O1—C1—C2—N120.3 (4)
O2i—La1—N1—C293.7 (2)O2—C1—C2—C321.1 (5)
O3ii—La1—N1—C221.3 (2)O1—C1—C2—C3−157.2 (3)
O1—La1—N1—C215.99 (18)N1—C2—C3—C40.4 (3)
O6—La1—N1—C2−115.99 (19)C1—C2—C3—C4178.0 (3)
O5—La1—N1—C2−96.26 (19)N1—N2—C4—C3−0.9 (3)
O4iii—La1—N1—C2141.00 (17)La1iii—N2—C4—C3162.30 (19)
N2iii—La1—N1—C2177.4 (2)N1—N2—C4—C5−179.6 (2)
O4ii—La1—N1—C2−32.5 (2)La1iii—N2—C4—C5−16.4 (3)
C5ii—La1—N1—C2−8.2 (2)C2—C3—C4—N20.3 (3)
O2i—La1—N1—N2−120.8 (2)C2—C3—C4—C5178.8 (3)
O3ii—La1—N1—N2166.70 (19)La1v—O3—C5—O47.1 (3)
O1—La1—N1—N2161.4 (2)La1v—O3—C5—C4−170.7 (2)
O6—La1—N1—N229.5 (3)La1iii—O4—C5—O3−177.2 (2)
O5—La1—N1—N249.2 (2)La1v—O4—C5—O3−6.5 (3)
O4iii—La1—N1—N2−73.6 (2)La1iii—O4—C5—C40.7 (3)
N2iii—La1—N1—N2−37.1 (2)La1v—O4—C5—C4171.4 (2)
O4ii—La1—N1—N2113.0 (2)La1iii—O4—C5—La1v−170.65 (16)
C5ii—La1—N1—N2137.2 (2)N2—C4—C5—O3−171.1 (3)
C2—N1—N2—C41.1 (3)C3—C4—C5—O310.5 (5)
La1—N1—N2—C4−145.6 (2)N2—C4—C5—O411.0 (4)
C2—N1—N2—La1iii−157.9 (2)C3—C4—C5—O4−167.4 (3)
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y, −z+1; (iv) −x+3/2, y+1/2, z; (v) x, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O60.852.142.944 (3)159
O5—H5B···O3vi0.851.822.667 (3)174
O6—H6A···O1vii0.852.202.999 (3)155
O6—H6B···O1viii0.852.122.908 (3)153
Symmetry codes: (vi) −x+2, −y+1, −z+1; (vii) −x+2, y−1/2, −z+3/2; (viii) x+1/2, y, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O60.852.142.944 (3)159
O5—H5B···O3i0.851.822.667 (3)174
O6—H6A···O1ii0.852.202.999 (3)155
O6—H6B···O1iii0.852.122.908 (3)153
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y−1/2, −z+3/2; (iii) x+1/2, y, −z+3/2.
Acknowledgements top

The authors acknowledge financial support from the Young Teachers' Starting Fund of Tianjin Polytechnic University.

references
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