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Acta Cryst. (2009). E65, m682    [ doi:10.1107/S1600536809018194 ]

Poly[diaqua([mu]-oxalato)([mu]-2-oxidopyridinium-3-carboxylato)lanthanum(III)]

Z. Hu and Z.-B. Zhu

Abstract top

In the title complex, [La(C6H4NO3)(C2O4)(H2O)2]n, the LaIII ion is coordinated by eight O atoms from two 2-oxidopyridinium-3-carboxylate ligands, two oxalate ligands and two water molecules in a distorted bicapped square-antiprismatic geometry. The carboxylate groups link adjacent LaIII ions, forming two-dimensional layers that are further linked by N-H...O and O-H...O hydrogen bonds.

Comment top

Whereas a large number of metal derivatives of oxalic acid have been reported, there are few examples of metal derivatives of 2-oxynicotinic acid and oxalic acid: the crystal structures of praseodymium (Xu et al., 2009) and dysprosium (Huang et al., 2009) derivatives have been reported only. We report here a lanthanum(III) complex formed by reaction of lanthanum nitrate, 2-oxynicotinic acid and oxalic acid under hydrothermal conditions.

As illustrated in Fig. 1, each LaIII centre adopts a distorted bicapped square-antiprismatic geometry, defined by eight O atoms from two 2-oxynicotinate ligands, two oxalate ligands, and two water molecules. The 2-oxynicotinate ligands and oxalate ligands link the LaIII ions to form layers in the bc plane in which the shortest La···La separation is 4.429 (3) Å. These layers are connected through O—H···O and N—H···O hydrogen bonding (Table 1) involving 2-oxynicotinate ligands, oxalate ligands and the coordinating water molecules, forming a three-dimensional supramolecular network motif (Fig. 2).

Related literature top

For related structures, see: Huang et al. (2009); Xu et al. (2009).

Experimental top

A mixture of La2O3 (0.245 g, 0.75 mmol), 2-oxynicotinic acid (0.127 g, 1 mmol), oxalic acid (0.09 g, 1 mmol), water (10 ml) and HNO3 (0.024 g, 0.385 mmol) was stirred vigorously for 20 min then sealed in a Teflon-lined stainless-steel autoclave (20 ml capacity). The autoclave was heated and maintained at 433 K for 4 days, then cooled to room temperature at 5 K h-1 to yield colourless block crystals.

Refinement top

H atoms bound to C and N atoms were placed at calculated positions and refined as riding with N—H = 0.86 Å, C—H = 0.93 Å and with Uiso(H) = 1.2 Ueq(C/N). H atoms of the water molecules were tentatively located in difference Fourier maps and refined with distance restraints of O—H = 0.850 (1) Å and H···H = 1.350 (1) Å. In the final cycles of refinement, the O—H distances were normalized to 0.85 Å and the H atoms were refined as riding with Uiso(H) = 1.5 Ueq(O). Atom H4W forms a symmetrical H-bond about a centre of inversion and therefore is included with site occupancy factor 0.5. The alternative position H4W' points towards the centroid of an adjacent pyridyl ring.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 showing displacement ellipsoids at 30% probability for non-H atoms. Symmetry codes: (i) -x, -y, -z; (ii) -x, 1 - y, 1 - z; (iii) -x, -y, 1 - z. The H atoms on O2W are disordered.
[Figure 2] Fig. 2. Packing diagram showing part of the 2-D layers (horizontal).
Poly[diaqua(µ-oxalato)(µ-2-oxidopyridinium-3-carboxylato)lanthanum(III)] top
Crystal data top
[La(C6H4NO3)(C2O4)(H2O)2]Z = 2
Mr = 401.06F000 = 384
Triclinic, P1Dx = 2.424 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.0856 (18) ÅCell parameters from 2827 reflections
b = 8.5493 (19) Åθ = 2.5–28.3º
c = 9.388 (3) ŵ = 3.93 mm−1
α = 109.281 (3)ºT = 293 K
β = 104.702 (3)ºBlock, colourless
γ = 104.940 (2)º0.20 × 0.18 × 0.17 mm
V = 549.5 (2) Å3
Data collection top
Bruker APEXII CCD
diffractometer		1946 independent reflections
Radiation source: fine-focus sealed tube1870 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 293 Kθmax = 25.2º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −7→9
Tmin = 0.460, Tmax = 0.512k = −10→10
2843 measured reflectionsl = −11→11
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)] = 0.025H-atom parameters constrained
wR(F2) = 0.069  w = 1/[σ2(Fo2) + (0.0415P)2 + 0.4664P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
1946 reflectionsΔρmax = 0.92 e Å−3
172 parametersΔρmin = −1.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[La(C6H4NO3)(C2O4)(H2O)2]γ = 104.940 (2)º
Mr = 401.06V = 549.5 (2) Å3
Triclinic, P1Z = 2
a = 8.0856 (18) ÅMo Kα
b = 8.5493 (19) ŵ = 3.93 mm−1
c = 9.388 (3) ÅT = 293 K
α = 109.281 (3)º0.20 × 0.18 × 0.17 mm
β = 104.702 (3)º
Data collection top
Bruker APEXII CCD
diffractometer		1946 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1870 reflections with I > 2σ(I)
Tmin = 0.460, Tmax = 0.512Rint = 0.020
2843 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025172 parameters
wR(F2) = 0.069H-atom parameters constrained
S = 1.10Δρmax = 0.92 e Å−3
1946 reflectionsΔρmin = −1.37 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*/UeqOcc. (<1)
C10.5156 (6)0.3528 (6)0.7873 (5)0.0193 (9)
C20.4448 (6)0.2225 (6)0.8439 (5)0.0190 (9)
C30.5510 (7)0.2276 (6)0.9869 (5)0.0278 (10)
H3A0.50430.14111.02090.033*
C40.7265 (7)0.3590 (7)1.0820 (6)0.0340 (12)
H4A0.79630.36171.17880.041*
C50.7924 (6)0.4829 (7)1.0291 (6)0.0310 (11)
H5A0.90850.57281.09100.037*
C60.2549 (6)0.0837 (6)0.7555 (5)0.0195 (9)
C70.0124 (6)0.0944 (6)0.0035 (5)0.0209 (9)
C80.0714 (6)0.5526 (5)0.4754 (5)0.0180 (8)
La10.14649 (3)0.16626 (3)0.39929 (2)0.01432 (11)
N10.6911 (5)0.4769 (5)0.8873 (5)0.0253 (8)
H1A0.73930.55610.85700.030*
O10.1395 (4)0.0964 (4)0.6424 (3)0.0215 (7)
O20.2093 (4)−0.0404 (4)0.7976 (4)0.0285 (7)
O30.4372 (4)0.3643 (4)0.6604 (4)0.0276 (7)
O40.1045 (5)0.2240 (4)0.1390 (4)0.0258 (7)
O5−0.0601 (5)0.1020 (4)−0.1273 (4)0.0275 (7)
O60.1897 (4)0.4906 (4)0.4461 (4)0.0238 (7)
O70.0581 (4)0.6932 (4)0.4686 (4)0.0263 (7)
O1W0.4501 (5)0.2684 (5)0.3496 (4)0.0400 (9)
H1W0.55120.32700.43090.060*
H2W0.47210.19110.28080.060*
O2W0.3055 (5)−0.0633 (5)0.4169 (4)0.0329 (8)
H3W0.2604−0.14910.43960.049*
H4W0.4214−0.02540.46670.049*0.50
H4W'0.2871−0.12020.31750.049*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.018 (2)0.016 (2)0.018 (2)0.0023 (17)0.0060 (17)0.0040 (17)
C20.017 (2)0.017 (2)0.0160 (19)0.0019 (17)0.0018 (17)0.0062 (17)
C30.027 (2)0.023 (2)0.024 (2)0.002 (2)0.000 (2)0.012 (2)
C40.024 (3)0.034 (3)0.024 (2)0.001 (2)−0.011 (2)0.012 (2)
C50.017 (2)0.029 (3)0.029 (2)0.001 (2)−0.0042 (19)0.006 (2)
C60.016 (2)0.020 (2)0.016 (2)−0.0004 (17)0.0025 (17)0.0074 (17)
C70.021 (2)0.024 (2)0.017 (2)0.0035 (18)0.0066 (18)0.0103 (18)
C80.014 (2)0.014 (2)0.017 (2)0.0005 (17)−0.0001 (16)0.0029 (17)
La10.01183 (15)0.01383 (16)0.01434 (15)0.00163 (11)0.00223 (11)0.00694 (11)
N10.0186 (19)0.022 (2)0.027 (2)−0.0013 (16)0.0045 (16)0.0110 (17)
O10.0154 (15)0.0253 (17)0.0172 (15)0.0003 (13)−0.0005 (12)0.0118 (13)
O20.0215 (17)0.0269 (18)0.0325 (18)0.0002 (14)0.0028 (14)0.0192 (15)
O30.0211 (17)0.0312 (18)0.0235 (16)−0.0002 (14)0.0014 (14)0.0163 (14)
O40.0326 (19)0.0190 (16)0.0157 (15)−0.0002 (14)0.0040 (14)0.0068 (13)
O50.0369 (19)0.0238 (16)0.0163 (15)0.0085 (15)0.0030 (14)0.0093 (13)
O60.0193 (16)0.0192 (16)0.0336 (17)0.0070 (13)0.0107 (14)0.0116 (14)
O70.0294 (18)0.0209 (16)0.0373 (18)0.0110 (14)0.0169 (15)0.0177 (14)
O1W0.0197 (18)0.057 (2)0.0307 (19)0.0001 (17)0.0090 (15)0.0158 (18)
O2W0.0285 (18)0.040 (2)0.043 (2)0.0178 (16)0.0155 (16)0.0276 (17)
Geometric parameters (Å, °) top
C1—O31.248 (5)La1—O62.574 (3)
C1—N11.382 (6)La1—O5i2.582 (3)
C1—C21.437 (6)La1—O32.585 (3)
C2—C31.377 (6)La1—O1W2.598 (3)
C2—C61.489 (6)La1—O42.606 (3)
C3—C41.395 (7)La1—O7ii2.608 (3)
C3—H3A0.930La1—O1iii2.612 (3)
C4—C51.357 (7)La1—O2W2.634 (3)
C4—H4A0.930La1—O2iii2.691 (3)
C5—N11.351 (6)N1—H1A0.860
C5—H5A0.930O1—La1iii2.612 (3)
C6—O21.252 (5)O2—La1iii2.691 (3)
C6—O11.279 (5)O5—La1i2.582 (3)
C7—O41.250 (5)O7—La1ii2.608 (3)
C7—O51.251 (5)O1W—H1W0.850
C7—C7i1.550 (9)O1W—H2W0.850
C8—O61.253 (5)O2W—H3W0.850
C8—O71.255 (5)O2W—H4W0.850
C8—C8ii1.537 (8)O2W—H4W'0.850
La1—O12.553 (3)
O3—C1—N1118.0 (4)O1—La1—O1iii61.92 (11)
O3—C1—C2127.4 (4)O6—La1—O1iii130.59 (10)
N1—C1—C2114.6 (4)O5i—La1—O1iii70.65 (10)
C3—C2—C1120.0 (4)O3—La1—O1iii127.57 (9)
C3—C2—C6118.0 (4)O1W—La1—O1iii148.31 (12)
C1—C2—C6121.9 (4)O4—La1—O1iii111.41 (10)
C2—C3—C4121.8 (4)O7ii—La1—O1iii72.58 (10)
C2—C3—H3A119.1O1—La1—O2W68.95 (10)
C4—C3—H3A119.1O6—La1—O2W147.03 (10)
C5—C4—C3118.1 (4)O5i—La1—O2W64.56 (10)
C5—C4—H4A121.0O3—La1—O2W78.73 (11)
C3—C4—H4A121.0O1W—La1—O2W72.87 (12)
N1—C5—C4120.6 (4)O4—La1—O2W115.38 (10)
N1—C5—H5A119.7O7ii—La1—O2W138.08 (10)
C4—C5—H5A119.7O1iii—La1—O2W81.33 (10)
O2—C6—O1121.1 (4)O1—La1—O2iii105.06 (9)
O2—C6—C2119.0 (4)O6—La1—O2iii92.61 (10)
O1—C6—C2119.8 (4)O5i—La1—O2iii66.21 (10)
O4—C7—O5126.4 (4)O3—La1—O2iii157.15 (11)
O4—C7—C7i116.9 (4)O1W—La1—O2iii131.48 (11)
O5—C7—C7i116.7 (5)O4—La1—O2iii67.14 (10)
O6—C8—O7126.1 (4)O7ii—La1—O2iii65.52 (10)
O6—C8—C8ii117.3 (4)O1iii—La1—O2iii49.08 (9)
O7—C8—C8ii116.6 (4)O2W—La1—O2iii118.71 (11)
O1—La1—O6115.01 (10)C5—N1—C1124.9 (4)
O1—La1—O5i116.73 (10)C5—N1—H1A117.6
O6—La1—O5i127.50 (10)C1—N1—H1A117.6
O1—La1—O365.68 (10)C6—O1—La1135.9 (3)
O6—La1—O374.38 (10)C6—O1—La1iii96.3 (3)
O5i—La1—O3136.55 (11)La1—O1—La1iii118.08 (11)
O1—La1—O1W121.99 (10)C6—O2—La1iii93.3 (2)
O6—La1—O1W78.71 (11)C1—O3—La1136.4 (3)
O5i—La1—O1W81.66 (11)C7—O4—La1118.5 (3)
O3—La1—O1W65.28 (11)C7—O5—La1i119.4 (3)
O1—La1—O4172.10 (10)C8—O6—La1120.7 (3)
O6—La1—O465.38 (10)C8—O7—La1ii119.8 (3)
O5i—La1—O462.14 (10)La1—O1W—H1W118.9
O3—La1—O4120.98 (10)La1—O1W—H2W118.3
O1W—La1—O465.90 (11)H1W—O1W—H2W105.2
O1—La1—O7ii69.92 (10)La1—O2W—H3W122.1
O6—La1—O7ii62.13 (9)La1—O2W—H4W119.6
O5i—La1—O7ii131.12 (11)H3W—O2W—H4W105.2
O3—La1—O7ii91.67 (11)La1—O2W—H4W'101.0
O1W—La1—O7ii139.07 (11)H3W—O2W—H4W'100.6
O4—La1—O7ii104.60 (10)H4W—O2W—H4W'105.2
O3—C1—C2—C3179.2 (4)N1—C1—O3—La1168.2 (3)
N1—C1—C2—C3−0.4 (6)C2—C1—O3—La1−11.5 (7)
O3—C1—C2—C6−3.1 (7)O1—La1—O3—C122.7 (4)
N1—C1—C2—C6177.2 (4)O6—La1—O3—C1150.2 (4)
C1—C2—C3—C41.3 (7)O5i—La1—O3—C1−81.2 (4)
C6—C2—C3—C4−176.5 (4)O1W—La1—O3—C1−125.3 (4)
C2—C3—C4—C5−0.6 (8)O4—La1—O3—C1−162.1 (4)
C3—C4—C5—N1−0.8 (8)O7ii—La1—O3—C189.7 (4)
C3—C2—C6—O2−11.8 (6)O1iii—La1—O3—C120.6 (5)
C1—C2—C6—O2170.5 (4)O2W—La1—O3—C1−49.1 (4)
C3—C2—C6—O1165.6 (4)O2iii—La1—O3—C192.9 (5)
C1—C2—C6—O1−12.0 (6)O5—C7—O4—La1160.6 (4)
C4—C5—N1—C11.7 (7)C7i—C7—O4—La1−20.2 (6)
O3—C1—N1—C5179.3 (4)O6—La1—O4—C7−157.7 (3)
C2—C1—N1—C5−1.0 (6)O5i—La1—O4—C720.9 (3)
O2—C6—O1—La1−137.1 (4)O3—La1—O4—C7150.7 (3)
C2—C6—O1—La145.4 (6)O1W—La1—O4—C7114.1 (3)
O2—C6—O1—La1iii5.4 (4)O7ii—La1—O4—C7−108.3 (3)
C2—C6—O1—La1iii−172.0 (3)O1iii—La1—O4—C7−31.6 (4)
O6—La1—O1—C6−98.9 (4)O2W—La1—O4—C758.8 (3)
O5i—La1—O1—C690.3 (4)O2iii—La1—O4—C7−53.3 (3)
O3—La1—O1—C6−41.3 (4)O4—C7—O5—La1i159.7 (4)
O1W—La1—O1—C6−6.8 (4)C7i—C7—O5—La1i−19.6 (6)
O7ii—La1—O1—C6−142.8 (4)O7—C8—O6—La1−165.0 (3)
O1iii—La1—O1—C6136.7 (5)C8ii—C8—O6—La115.1 (6)
O2W—La1—O1—C645.5 (4)O1—La1—O6—C8−63.1 (3)
O2iii—La1—O1—C6160.9 (4)O5i—La1—O6—C8106.6 (3)
O6—La1—O1—La1iii124.39 (13)O3—La1—O6—C8−116.0 (3)
O5i—La1—O1—La1iii−46.43 (16)O1W—La1—O6—C8176.7 (3)
O3—La1—O1—La1iii−178.07 (17)O4—La1—O6—C8108.2 (3)
O1W—La1—O1—La1iii−143.50 (14)O7ii—La1—O6—C8−15.6 (3)
O7ii—La1—O1—La1iii80.43 (14)O1iii—La1—O6—C810.4 (4)
O1iii—La1—O1—La1iii0.0O2W—La1—O6—C8−152.6 (3)
O2W—La1—O1—La1iii−91.27 (15)O2iii—La1—O6—C844.9 (3)
O2iii—La1—O1—La1iii24.16 (15)O6—C8—O7—La1ii−165.3 (3)
O1—C6—O2—La1iii−5.2 (4)C8ii—C8—O7—La1ii14.7 (6)
C2—C6—O2—La1iii172.2 (3)
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4iv0.861.962.789 (5)162
O1W—H1W···O6iv0.852.012.805 (5)155
O2W—H4W···O2Wv0.852.002.853 (7)180
O2W—H3W···O7vi0.851.972.753 (5)152
Symmetry codes: (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.861.962.789 (5)162
O1W—H1W···O6i0.852.012.805 (5)155
O2W—H4W···O2Wii0.852.002.853 (7)180
O2W—H3W···O7iii0.851.972.753 (5)152
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x, y−1, z.
Acknowledgements top

The authors acknowledge Southern Medical University for supporting this work.

references
References top

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Huang, C.-D., Huang, J.-X., Wu, Y.-Y., Lian, Y.-Y. & Zeng, R.-H. (2009). Acta Cryst. E65, m177–m178.

Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.

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

Xu, Y.-J., Yang, X.-X. & Zhao, H.-B. (2009). Acta Cryst. E65, m310.