supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

Acta Cryst. (2009). E65, m76    [ doi:10.1107/S1600536808041664 ]

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

L. Han, Q.-H. Meng, J.-D. Hao, Y.-F. Luo and R.-H. Zeng

Abstract top

In the title complex, [La(C5H3N2O2)(C2O4)(H2O)2]n, the LaIII ion is coordinated by one N and three O atoms from two pyrazine-2-carboxylate ligands, by four O atoms from two oxalate ligands and by two O atoms of two water molecules, displaying a distorted bicapped square-antiprismatic geometry. The carboxylate groups of pyrazine-2-carboxylate and oxalate ligands link the lanthanum metal centres, forming layers parallel to (10\overline{1}). The layers are further connected by intermolecular O-H...O and N-H...O hydrogen-bonding interactions, forming a three-dimensional supramolecular network.

Comment top

The design, synthesis, characterization, and properties of supramolecular networks formed by using functionalized organic molecules as bridges between metal centers are of great interest(Eddaoudi et al., 2001; Rizk et al., 2005; Zeng et al.,2007). As a building block, pyrazine-2-carboxylic acid and oxalic acid are excellent candidates for the construction of supramolecular complexes. Herein, we reported the new coordination polymer, (I).

In (I), each LaIII centre is coordinated by seven oxygen atoms and one nitrogen atom from two pyrazine-2-carboxylate ligands, two oxalate ligands and two water molecules (Fig. 1), and represents a distorted bicapped square antiprismatic geometry. The LaIII ions are linked by pyrazine-2-carboxylate ligands and oxalate ligands to form layers parallel to the (1 0 -1) plane (Fig.2), and the adjacent La···La separations are 6.570 (4) and 4.506 (5) Å, respectively. O—H···O and N—H···O hydrogen bonds (Table 1), involving the pyrazine-2-carboxylate ligands, coordinating water molecules and oxalate ligands assemble neighboring layers into a three-dimensional supramolecular network motif .

Related literature top

For general background, see: Eddaoudi et al. (2001); Rizk et al. (2005); Zeng et al. (2007).

Experimental top

A mixture of La2O3 (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 433K for 3 days, and then cooled to room temperature at 5 K h-1 and obtained the colorless block crystals.

Refinement top

Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.84 Å and H···H = 1.35 Å, and with Uiso(H) = 1.5 Ueq(O). In the last cycles of refinement they were treated as riding on the O atoms. Carbon-bound H atoms were placed at calculated positions and were treated as riding on their parent C atoms with C—H = 0.93 Å, and with Uiso(H) = 1.2 Ueq(C).

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: ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP view showing the atomic-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i)1-x, 1-y, 1-z; (ii)1-x, -y, -z; (iii)1-x, -y, 1-z]
[Figure 2] Fig. 2. View of the layered network of the title structure.
Poly[diaqua-µ-oxalato-µ-pyrazine-2-carboxylato-lanthanum(III)] top
Crystal data top
[La(C5H3N2O2)(C2O4)(H2O)2]Z = 2
Mr = 386.06F(000) = 368
Triclinic, P1Dx = 2.391 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.040 (3) ÅCell parameters from 6377 reflections
b = 8.7343 (18) Åθ = 1.7–28.0°
c = 8.8329 (18) ŵ = 4.02 mm−1
α = 115.552 (2)°T = 296 K
β = 101.447 (3)°Block, colourless
γ = 95.789 (3)°0.17 × 0.16 × 0.14 mm
V = 536.1 (3) Å3
Data collection top
Bruker APEXII area-detector
diffractometer		1898 independent reflections
Radiation source: fine-focus sealed tube1787 reflections with I > 2σ(I)
graphiteRint = 0.020
φ and ω scansθmax = 25.2°, θmin = 2.6°
Absorption correction: multi-scan
(APEX2; Bruker, 2004)		h = −5→9
Tmin = 0.548, Tmax = 0.603k = −10→10
2761 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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0533P)2]
where P = (Fo2 + 2Fc2)/3
1898 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 1.61 e Å−3
6 restraintsΔρmin = −1.22 e Å−3
Crystal data top
[La(C5H3N2O2)(C2O4)(H2O)2]γ = 95.789 (3)°
Mr = 386.06V = 536.1 (3) Å3
Triclinic, P1Z = 2
a = 8.040 (3) ÅMo Kα radiation
b = 8.7343 (18) ŵ = 4.02 mm−1
c = 8.8329 (18) ÅT = 296 K
α = 115.552 (2)°0.17 × 0.16 × 0.14 mm
β = 101.447 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer		1898 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2004)		1787 reflections with I > 2σ(I)
Tmin = 0.548, Tmax = 0.603Rint = 0.020
2761 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.078Δρmax = 1.61 e Å−3
S = 1.07Δρmin = −1.22 e Å−3
1898 reflectionsAbsolute structure: ?
163 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C10.2750 (6)0.2794 (6)0.7523 (6)0.0218 (10)
C20.2577 (7)0.4053 (7)0.9066 (7)0.0285 (11)
H20.31910.41221.01110.034*
C30.0676 (7)0.4974 (7)0.7564 (7)0.0304 (12)
H3−0.00790.57060.75290.036*
C40.0849 (7)0.3716 (7)0.6014 (7)0.0289 (11)
H40.02020.36210.49680.035*
C50.5718 (6)0.4928 (6)0.5701 (6)0.0204 (10)
C60.0553 (6)−0.0282 (6)−0.0653 (6)0.0218 (10)
C70.3936 (6)0.1564 (7)0.7458 (6)0.0238 (10)
La10.33941 (3)0.08521 (3)0.32247 (3)0.01745 (13)
N10.1560 (6)0.5173 (6)0.9109 (6)0.0284 (10)
N80.1914 (5)0.2634 (5)0.5974 (5)0.0235 (9)
O10.3920 (5)0.0398 (4)0.5980 (4)0.0248 (8)
O20.4933 (5)0.1760 (5)0.8841 (5)0.0314 (8)
O30.5571 (5)0.3495 (4)0.5715 (4)0.0246 (7)
O40.6879 (4)0.6241 (4)0.6678 (4)0.0264 (8)
O5−0.0155 (4)−0.0721 (5)−0.2201 (4)0.0299 (8)
O60.2119 (4)−0.0240 (5)−0.0025 (4)0.0292 (8)
O1W0.2022 (5)−0.2208 (4)0.2499 (4)0.0271 (8)
O2W0.5746 (5)0.1980 (5)0.2097 (4)0.0300 (8)
H1W0.1827−0.29130.14410.045*
H3W0.52930.20790.12100.045*
H2W0.2583−0.26300.30710.045*
H4W0.66110.15340.19000.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.018 (2)0.027 (2)0.021 (2)0.007 (2)0.005 (2)0.012 (2)
C20.024 (3)0.033 (3)0.026 (3)0.008 (2)0.004 (2)0.012 (2)
C30.030 (3)0.030 (3)0.033 (3)0.012 (2)0.010 (2)0.014 (2)
C40.031 (3)0.033 (3)0.029 (3)0.017 (2)0.007 (2)0.018 (2)
C50.015 (2)0.025 (2)0.021 (2)0.0083 (19)0.005 (2)0.009 (2)
C60.017 (2)0.023 (2)0.024 (2)0.0043 (19)0.004 (2)0.010 (2)
C70.018 (2)0.033 (3)0.025 (3)0.005 (2)0.007 (2)0.016 (2)
La10.01352 (18)0.01999 (18)0.01806 (18)0.00464 (11)0.00163 (12)0.00898 (13)
N10.022 (2)0.027 (2)0.031 (2)0.0072 (18)0.0067 (19)0.0093 (19)
N80.022 (2)0.027 (2)0.023 (2)0.0084 (17)0.0035 (17)0.0132 (18)
O10.0267 (19)0.0270 (18)0.0238 (18)0.0104 (15)0.0089 (15)0.0126 (15)
O20.028 (2)0.046 (2)0.0244 (18)0.0153 (17)0.0049 (16)0.0195 (17)
O30.0261 (19)0.0225 (17)0.0260 (18)0.0047 (14)0.0020 (15)0.0143 (15)
O40.0196 (18)0.0241 (18)0.0316 (19)0.0037 (15)−0.0015 (15)0.0131 (16)
O50.0172 (18)0.049 (2)0.0197 (18)0.0097 (16)0.0016 (15)0.0132 (16)
O60.0147 (18)0.046 (2)0.0220 (17)0.0100 (16)0.0020 (14)0.0123 (16)
O1W0.0262 (19)0.0239 (18)0.0263 (18)0.0031 (15)0.0015 (15)0.0100 (15)
O2W0.027 (2)0.039 (2)0.0272 (19)0.0109 (17)0.0114 (16)0.0166 (17)
Geometric parameters (Å, °) top
C1—N81.340 (6)C7—O11.259 (6)
C1—C21.378 (7)La1—O1W2.533 (3)
C1—C71.497 (7)La1—O4i2.536 (3)
C2—N11.330 (7)La1—O62.544 (3)
C2—H20.9300La1—O32.551 (3)
C3—N11.336 (7)La1—O5ii2.555 (4)
C3—C41.382 (7)La1—O12.592 (3)
C3—H30.9300La1—O2W2.600 (4)
C4—N81.332 (7)La1—O1iii2.623 (3)
C4—H40.9300La1—N82.828 (4)
C5—O41.242 (6)La1—O2iii2.889 (4)
C5—O31.250 (6)La1—C7iii3.124 (5)
C5—C5i1.574 (9)O1W—H1W0.8385
C6—O51.239 (6)O1W—H2W0.8353
C6—O61.261 (6)O2W—H3W0.8400
C6—C6ii1.539 (9)O2W—H4W0.8421
C7—O21.252 (6)
N8—C1—C2122.0 (5)O5ii—La1—O1iii154.21 (12)
N8—C1—C7115.3 (4)O1—La1—O1iii60.45 (13)
C2—C1—C7122.7 (5)O2W—La1—O1iii75.58 (11)
N1—C2—C1122.1 (5)O1W—La1—N897.55 (12)
N1—C2—H2118.9O4i—La1—N872.37 (12)
C1—C2—H2118.9O6—La1—N8128.17 (11)
N1—C3—C4122.0 (5)O3—La1—N868.57 (12)
N1—C3—H3119.0O5ii—La1—N866.44 (11)
C4—C3—H3119.0O1—La1—N858.52 (11)
N8—C4—C3121.9 (5)O2W—La1—N8131.02 (12)
N8—C4—H4119.0O1iii—La1—N8115.86 (11)
C3—C4—H4119.0O1W—La1—O2iii66.41 (11)
O4—C5—O3126.6 (4)O4i—La1—O2iii129.49 (11)
O4—C5—C5i117.0 (5)O6—La1—O2iii68.05 (11)
O3—C5—C5i116.4 (5)O3—La1—O2iii112.40 (11)
O5—C6—O6126.1 (4)O5ii—La1—O2iii121.50 (11)
O5—C6—C6ii118.0 (5)O1—La1—O2iii99.45 (10)
O6—C6—C6ii115.9 (5)O2W—La1—O2iii65.10 (11)
O2—C7—O1122.7 (5)O1iii—La1—O2iii46.83 (10)
O2—C7—C1119.7 (5)N8—La1—O2iii157.23 (11)
O1—C7—C1117.5 (4)O1W—La1—C7iii68.77 (12)
O2—C7—La1iii67.6 (3)O4i—La1—C7iii137.10 (12)
O1—C7—La1iii55.5 (3)O6—La1—C7iii91.66 (12)
C1—C7—La1iii169.0 (3)O3—La1—C7iii95.00 (12)
O1W—La1—O4i150.33 (12)O5ii—La1—C7iii139.98 (12)
O1W—La1—O682.82 (11)O1—La1—C7iii78.74 (11)
O4i—La1—O682.26 (12)O2W—La1—C7iii70.04 (12)
O1W—La1—O3139.37 (10)O1iii—La1—C7iii23.29 (11)
O4i—La1—O363.95 (11)N8—La1—C7iii136.97 (12)
O6—La1—O3136.33 (11)O2iii—La1—C7iii23.62 (11)
O1W—La1—O5ii77.14 (12)C2—N1—C3116.0 (5)
O4i—La1—O5ii73.25 (12)C4—N8—C1115.9 (4)
O6—La1—O5ii63.19 (11)C4—N8—La1126.3 (3)
O3—La1—O5ii124.85 (11)C1—N8—La1114.8 (3)
O1W—La1—O168.69 (11)C7—O1—La1122.9 (3)
O4i—La1—O1122.78 (11)C7—O1—La1iii101.2 (3)
O6—La1—O1151.51 (12)La1—O1—La1iii119.55 (13)
O3—La1—O171.74 (11)C7—O2—La1iii88.8 (3)
O5ii—La1—O1108.11 (11)C5—O3—La1120.1 (3)
O1W—La1—O2W130.93 (11)C5—O4—La1i120.6 (3)
O4i—La1—O2W67.57 (12)C6—O5—La1ii121.0 (3)
O6—La1—O2W72.86 (11)C6—O6—La1121.8 (3)
O3—La1—O2W69.18 (11)La1—O1W—H1W113.1
O5ii—La1—O2W123.82 (12)La1—O1W—H2W115.0
O1—La1—O2W126.58 (11)H1W—O1W—H2W107.3
O1W—La1—O1iii77.11 (11)La1—O2W—H3W111.1
O4i—La1—O1iii132.53 (11)La1—O2W—H4W123.8
O6—La1—O1iii114.65 (11)H3W—O2W—H4W106.5
O3—La1—O1iii75.79 (11)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z; (iii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···N1iv0.841.972.796 (6)170
O2W—H3W···O2v0.841.942.737 (5)157
O1W—H2W···O3iii0.842.052.874 (5)167
O2W—H4W···O6vi0.842.092.825 (5)146
Symmetry codes: (iv) x, y−1, z−1; (v) x, y, z−1; (iii) −x+1, −y, −z+1; (vi) −x+1, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···N1i0.841.972.796 (6)170
O2W—H3W···O2ii0.841.942.737 (5)157
O1W—H2W···O3iii0.842.052.874 (5)167
O2W—H4W···O6iv0.842.092.825 (5)146
Symmetry codes: (i) x, y−1, z−1; (ii) x, y, z−1; (iii) −x+1, −y, −z+1; (iv) −x+1, −y, −z.
Acknowledgements top

The authors acknowledge South China Normal University for supporting this work.

references
References top

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

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Eddaoudi, M., Moler, D. B., Li, H. L., Chen, B. L., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.

Rizk, A. T., Kizk, A., ilner, C. A. & Halcrow, M. A. (2005). CrystEngCommun, 7, 359–362.

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

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Zeng, R.-H., Qiu, Y.-C., Cai, Y.-P., Wu, J.-Z. & Deng, H. (2007). Acta Cryst. E63, m1666.