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Acta Cryst. (2009). E65, m1065-m1066    [ doi:10.1107/S1600536809031250 ]

Poly[diaqua([mu]2-oxalato-[kappa]4O1,O2:O1',O2')([mu]2-pyrazine-2-carboxylato-[kappa]4N1,O:O,O')neodymium(III)]

K.-C. Chen, H.-M. Luo, Q.-H. Meng, Y.-F. Luo and R.-H. Zeng

Abstract top

In the title complex, [Nd(C5H3N2O2)(C2O4)(H2O)2]n, the NdIII atom is ten-coordinated by one N atom and three O atoms from two pyrazine-2-carboxylate ligands, four O atoms from two oxalate ligands and two water molecules in a distorted bicapped square-antiprismatic geometry. The two crystallographically independent oxalate ligands, each lying on an inversion center, act as bridging ligands, linking Nd atoms into an extended zigzag chain. Neighboring chains are linked by the pyrazine-2-carboxylate ligands into a two-dimensional layerlike network in the (10\overline{1}) plane. The layers are further connected by O-H...O and O-H...N hydrogen bonds, forming a three-dimensional supramolecular network.

Comment top

In recent years, many research groups have devoted their work to the design and synthesis of lanthanide coordination frameworks with bridging multifunctional organic ligands, not only because of their fascinating topological networks, but also due to their potential applications in ion exchange, gas storage, catalysis and luminescence (Wang et al., 2006; Zhou et al., 2006). As a building block, pyrazine-2-carboxylic acid and oxalic acid are good ligands with multifunctional coordination sites providing a high likelihood for the generation of structures with high dimensions (Han et al., 2009; Li et al., 2006). Recently, we obtained the title coordination polymer under hydrothermal conditions.

In the title compound, the NdIII atom is coordinated by seven O atoms and one N atom from two pyrazine-2-carboxylate ligands and two oxalate ligands, and by two water molecules in a distorted bicapped square-antiprismatic geometry (Fig. 1). The NdIII atoms are linked by the oxalate ligands, forming an extended zigzag chain. These chains are linked by the pyrazine-2-carboxylate ligands into a two-dimensional layerlike network (Fig. 2). The Nd—O and Nd—N bond lengths range from 2.467 (4) to 2.885 (6) Å (Table 1). O—H···O and O—H···N hydrogen bonds (Table 2) involving the pyrazine-2-carboxylate ligands, coordinated water molecules and oxalate ligands assemble neighboring layers into a three-dimensional supramolecular network.

Related literature top

For general background to lanthanide coordination frameworks, see: Han et al. (2009); Li et al. (2006); Wang et al. (2006); Zhou et al. (2006).

Experimental top

A mixture of Nd2O3 (0.245 g, 0.75 mmol), pyrazine-2-carboxylic acid (0.186 g, 1.5 mmol), oxalic acid (0.135 g, 1.5 mmol), water (10 ml) in the presence of HNO3 (0.024 g, 0.385 mmol) was stirred vigorously for 20 min and then sealed in a Teflon-lined stainless-steel autoclave (20 ml capacity). The autoclave was heated and maintained at 433 K for 3 d, and then cooled to room temperature at 5 K h-1. Colorless block crystals of the title compound were obtained.

Refinement top

Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O—H = 0.84 (1) and H···H = 1.34 (1) Å , and with a fixed Uiso(H). C-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms, with C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq(C). The highest residual electron density was found 0.96 Å from Nd1 and the deepest hole 0.87 Å from Nd1.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) 2-x, 2-y, 2-z; (iii) 2-x, 1-y, 2-z.]
[Figure 2] Fig. 2. View of the layered network in the title compound.
Poly[diaqua(µ2-oxalato- κ4O1,O2:O1',O2')(µ2-pyrazine- 2-carboxylato-κ4N1,O:O,O')neodymium(III)] top
Crystal data top
[Nd(C5H3N2O2)(C2O4)(H2O)2]Z = 2
Mr = 391.39F(000) = 374
Triclinic, P1Dx = 2.514 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.948 (3) ÅCell parameters from 2522 reflections
b = 8.6512 (18) Åθ = 2.7–28.3°
c = 8.7425 (18) ŵ = 5.06 mm−1
α = 115.525 (2)°T = 296 K
β = 101.970 (3)°Block, colorless
γ = 96.306 (3)°0.23 × 0.19 × 0.17 mm
V = 517.0 (2) Å3
Data collection top
Bruker APEXII CCD
diffractometer		1824 independent reflections
Radiation source: fine-focus sealed tube1756 reflections with I > 2σ(I)
graphiteRint = 0.065
φ and ω scansθmax = 25.2°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→9
Tmin = 0.320, Tmax = 0.420k = −8→10
2533 measured reflectionsl = −10→10
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0478P)2 + 0.0313P]
where P = (Fo2 + 2Fc2)/3
1824 reflections(Δ/σ)max = 0.002
175 parametersΔρmax = 1.95 e Å−3
6 restraintsΔρmin = −2.98 e Å−3
Crystal data top
[Nd(C5H3N2O2)(C2O4)(H2O)2]γ = 96.306 (3)°
Mr = 391.39V = 517.0 (2) Å3
Triclinic, P1Z = 2
a = 7.948 (3) ÅMo Kα radiation
b = 8.6512 (18) ŵ = 5.06 mm−1
c = 8.7425 (18) ÅT = 296 K
α = 115.525 (2)°0.23 × 0.19 × 0.17 mm
β = 101.970 (3)°
Data collection top
Bruker APEXII CCD
diffractometer		1824 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1756 reflections with I > 2σ(I)
Tmin = 0.320, Tmax = 0.420Rint = 0.065
2533 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.132Δρmax = 1.95 e Å−3
S = 1.08Δρmin = −2.98 e Å−3
1824 reflectionsAbsolute structure: ?
175 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C11.1008 (9)0.3421 (10)0.7510 (9)0.0146 (15)
C21.2220 (10)0.2213 (10)0.7476 (10)0.0175 (15)
C31.2449 (13)0.0959 (12)0.5928 (12)0.0246 (19)
H31.18820.09200.48650.030*
C41.4345 (11)0.0053 (11)0.7489 (11)0.0227 (17)
H41.5126−0.06600.75430.027*
C51.4166 (11)0.1312 (11)0.9049 (11)0.0235 (17)
H51.48180.14151.01160.028*
C60.9283 (8)1.0062 (9)0.9289 (9)0.0114 (14)
C70.4413 (9)0.5252 (9)0.5645 (9)0.0156 (15)
H1W1.058 (11)0.745 (10)0.649 (9)0.023*
H2W1.143 (10)0.630 (10)0.676 (10)0.023*
H3W0.599 (5)0.229 (10)0.680 (9)0.023*
H4W0.731 (9)0.226 (9)0.802 (10)0.023*
N11.3077 (9)0.2389 (9)0.9065 (8)0.0175 (13)
N21.3439 (9)−0.0191 (9)0.5892 (9)0.0240 (15)
Nd10.83941 (4)0.58653 (4)0.82456 (4)0.0124 (2)
O11.0011 (8)0.3228 (8)0.6106 (7)0.0244 (13)
O21.1050 (7)0.4616 (7)0.9021 (7)0.0182 (11)
O30.8094 (7)0.8693 (7)0.8272 (7)0.0185 (11)
O40.9419 (7)1.1485 (7)0.9251 (7)0.0192 (11)
O50.5149 (7)0.5678 (8)0.7214 (7)0.0230 (12)
O60.2843 (7)0.5193 (8)0.4984 (6)0.0210 (11)
O1W1.0754 (9)0.6971 (9)0.7148 (8)0.0240 (13)
O2W0.7008 (7)0.2834 (7)0.7480 (7)0.0204 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.019 (4)0.013 (4)0.016 (4)0.002 (3)0.009 (3)0.009 (3)
C20.024 (4)0.013 (4)0.016 (4)0.001 (3)0.005 (3)0.007 (3)
C30.034 (5)0.016 (5)0.020 (4)0.005 (4)0.007 (4)0.006 (4)
C40.028 (4)0.016 (4)0.028 (4)0.010 (3)0.016 (4)0.010 (4)
C50.025 (4)0.024 (4)0.030 (4)0.011 (3)0.009 (3)0.018 (4)
C60.008 (3)0.006 (3)0.014 (3)−0.001 (2)−0.001 (3)0.001 (3)
C70.018 (4)0.006 (4)0.016 (4)0.000 (3)0.007 (3)−0.001 (3)
N10.023 (3)0.015 (3)0.018 (3)0.008 (3)0.007 (3)0.009 (3)
N20.029 (4)0.013 (3)0.027 (4)0.003 (3)0.014 (3)0.004 (3)
Nd10.0159 (3)0.0065 (3)0.0146 (3)0.00016 (19)0.0035 (2)0.0058 (2)
O10.032 (3)0.027 (3)0.021 (3)0.010 (3)0.009 (2)0.016 (3)
O20.022 (3)0.014 (3)0.024 (3)0.006 (2)0.011 (2)0.012 (2)
O30.016 (3)0.013 (3)0.024 (3)0.000 (2)0.000 (2)0.010 (2)
O40.025 (3)0.010 (3)0.024 (3)0.002 (2)0.003 (2)0.011 (2)
O50.022 (3)0.033 (3)0.019 (3)0.009 (2)0.008 (2)0.014 (3)
O60.019 (3)0.024 (3)0.015 (3)0.004 (2)0.003 (2)0.006 (2)
O1W0.033 (3)0.022 (3)0.022 (3)0.008 (3)0.013 (3)0.012 (3)
O2W0.029 (3)0.007 (3)0.022 (3)−0.003 (2)0.006 (2)0.006 (2)
Geometric parameters (Å, °) top
C1—O11.246 (9)Nd1—O2W2.467 (5)
C1—O21.270 (9)Nd1—O32.474 (5)
C1—C21.492 (10)Nd1—O6ii2.490 (5)
C2—N11.350 (10)Nd1—O4i2.508 (5)
C2—C31.386 (11)Nd1—O52.512 (5)
C3—N21.328 (11)Nd1—O1W2.549 (6)
C3—H30.9300Nd1—O2iii2.557 (5)
C4—N21.345 (11)Nd1—O22.573 (5)
C4—C51.379 (11)Nd1—N1iii2.765 (6)
C4—H40.9300Nd1—O12.885 (6)
C5—N11.337 (10)O2—Nd1iii2.557 (5)
C5—H50.9300O4—Nd1i2.508 (5)
C6—O41.239 (9)O6—Nd1ii2.490 (5)
C6—O31.259 (9)O1W—H1W0.84 (9)
C6—C6i1.553 (13)O1W—H2W0.85 (8)
C7—O51.243 (9)O2W—H3W0.84 (5)
C7—O61.247 (9)O2W—H4W0.84 (8)
C7—C7ii1.560 (13)
O1—C1—O2123.1 (7)O6ii—Nd1—O2iii151.94 (19)
O1—C1—C2120.3 (6)O4i—Nd1—O2iii72.00 (17)
O2—C1—C2116.6 (6)O5—Nd1—O2iii107.89 (16)
N1—C2—C3121.0 (7)O1W—Nd1—O2iii125.89 (18)
N1—C2—C1115.7 (6)O2W—Nd1—O276.93 (18)
C3—C2—C1123.3 (7)O3—Nd1—O2133.80 (17)
N2—C3—C2123.2 (8)O6ii—Nd1—O2113.72 (16)
N2—C3—H3118.4O4i—Nd1—O276.60 (17)
C2—C3—H3118.4O5—Nd1—O2153.11 (18)
N2—C4—C5122.9 (7)O1W—Nd1—O274.92 (18)
N2—C4—H4118.6O2iii—Nd1—O260.11 (19)
C5—C4—H4118.6O2W—Nd1—N1iii97.86 (19)
N1—C5—C4121.6 (7)O3—Nd1—N1iii72.90 (18)
N1—C5—H5119.2O6ii—Nd1—N1iii128.29 (18)
C4—C5—H5119.2O4i—Nd1—N1iii68.70 (19)
O4—C6—O3126.2 (6)O5—Nd1—N1iii65.79 (18)
O4—C6—C6i117.3 (8)O1W—Nd1—N1iii131.7 (2)
O3—C6—C6i116.4 (8)O2iii—Nd1—N1iii59.62 (17)
O5—C7—O6127.3 (6)O2—Nd1—N1iii116.80 (17)
O5—C7—C7ii116.5 (8)O2W—Nd1—O166.01 (18)
O6—C7—C7ii116.2 (8)O3—Nd1—O1128.48 (16)
C5—N1—C2116.2 (7)O6ii—Nd1—O166.65 (16)
C5—N1—Nd1iii126.3 (5)O4i—Nd1—O1113.54 (17)
C2—N1—Nd1iii114.6 (5)O5—Nd1—O1120.34 (17)
C3—N2—C4114.9 (7)O1W—Nd1—O164.46 (19)
O2W—Nd1—O3149.08 (18)O2iii—Nd1—O199.62 (15)
O2W—Nd1—O6ii83.06 (18)O2—Nd1—O147.38 (16)
O3—Nd1—O6ii80.47 (18)N1iii—Nd1—O1158.20 (17)
O2W—Nd1—O4i139.97 (17)C1—O1—Nd187.4 (4)
O3—Nd1—O4i65.15 (16)C1—O2—Nd1iii122.1 (4)
O6ii—Nd1—O4i135.42 (18)C1—O2—Nd1101.6 (4)
O2W—Nd1—O576.22 (19)Nd1iii—O2—Nd1119.89 (19)
O3—Nd1—O573.09 (18)C6—O3—Nd1120.1 (4)
O6ii—Nd1—O564.36 (16)C6—O4—Nd1i119.1 (4)
O4i—Nd1—O5124.93 (17)C7—O5—Nd1121.0 (4)
O2W—Nd1—O1W130.01 (19)C7—O6—Nd1ii121.8 (4)
O3—Nd1—O1W68.27 (19)Nd1—O1W—H1W125 (5)
O6ii—Nd1—O1W71.92 (19)Nd1—O1W—H2W117 (6)
O4i—Nd1—O1W69.52 (19)H1W—O1W—H2W105 (8)
O5—Nd1—O1W125.09 (18)Nd1—O2W—H3W124 (5)
O2W—Nd1—O2iii68.90 (17)Nd1—O2W—H4W128 (5)
O3—Nd1—O2iii124.64 (16)H3W—O2W—H4W106 (8)
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1iv0.84 (9)2.02 (6)2.707 (8)139 (7)
O1W—H2W···O6v0.85 (8)2.07 (4)2.838 (8)152 (6)
O2W—H3W···N2vi0.84 (5)2.50 (5)3.229 (9)145 (6)
O2W—H4W···O4vii0.84 (8)2.13 (4)2.872 (8)147 (7)
Symmetry codes: (iv) −x+2, −y+1, −z+1; (v) x+1, y, z; (vi) x−1, y, z; (vii) x, y−1, z.
Table 1
Selected geometric parameters (Å) top
Nd1—O2W2.467 (5)Nd1—O1W2.549 (6)
Nd1—O32.474 (5)Nd1—O2iii2.557 (5)
Nd1—O6i2.490 (5)Nd1—O22.573 (5)
Nd1—O4ii2.508 (5)Nd1—N1iii2.765 (6)
Nd1—O52.512 (5)Nd1—O12.885 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+2, −z+2; (iii) −x+2, −y+1, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1iv0.84 (9)2.02 (6)2.707 (8)139 (7)
O1W—H2W···O6v0.85 (8)2.07 (4)2.838 (8)152 (6)
O2W—H3W···N2vi0.84 (5)2.50 (5)3.229 (9)145 (6)
O2W—H4W···O4vii0.84 (8)2.13 (4)2.872 (8)147 (7)
Symmetry codes: (iv) −x+2, −y+1, −z+1; (v) x+1, y, z; (vi) x−1, y, z; (vii) x, y−1, z.
Acknowledgements top

The authors acknowledge the Chan Xue Yan Cooperative Special Project of Guangdong Province and the Ministry of Science and Technology of PRC (project No. 2007A090302046) and the Project of Science and Technology of Guangdong Province (project No. 2007A020200002-4) for supporting this work.

references
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