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

Abstract

In the title complex, [La(C₆H₄NO₃)(C₂O₄)(H₂O)₂]_n, the La^III 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 La^III ions, forming two-dimensional layers that are further linked by N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

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

Experimental

Crystal data

• [La(C₆H₄NO₃)(C₂O₄)(H₂O)₂]

• M _r = 401.06

• Triclinic,

• a = 8.0856 (18) Å

• b = 8.5493 (19) Å

• c = 9.388 (3) Å

• α = 109.281 (3)°

• β = 104.702 (3)°

• γ = 104.940 (2)°

• V = 549.5 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 3.93 mm⁻¹

• T = 293 K

• 0.20 × 0.18 × 0.17 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.460, T _max = 0.512

• 2843 measured reflections

• 1946 independent reflections

• 1870 reflections with I > 2σ(I)

• R _int = 0.020

Refinement

• R[F ² > 2σ(F ²)] = 0.025

• wR(F ²) = 0.069

• S = 1.10

• 1946 reflections

• 172 parameters

• H-atom parameters constrained

• Δρ_max = 0.92 e Å⁻³

• Δρ_min = −1.37 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4i	0.86	1.96	2.789 (5)	162
O1W—H1W⋯O6i	0.85	2.01	2.805 (5)	155
O2W—H4W⋯O2Wii	0.85	2.00	2.853 (7)	180
O2W—H3W⋯O7iii	0.85	1.97	2.753 (5)	152

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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 La^III 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 La^III 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).

Experimental

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

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 U_iso(H) = 1.2 U_eq(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 U_iso(H) = 1.5 U_eq(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.

Figures

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.

Fig. 2.

Packing diagram showing part of the 2-D layers (horizontal).

Crystal data

[La(C6H4NO3)(C2O4)(H2O)2]	Z = 2
Mr = 401.06	F(000) = 384
Triclinic, P1	Dx = 2.424 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0856 (18) Å	Cell parameters from 2827 reflections
b = 8.5493 (19) Å	θ = 2.5–28.3°
c = 9.388 (3) Å	µ = 3.93 mm−1
α = 109.281 (3)°	T = 293 K
β = 104.702 (3)°	Block, colourless
γ = 104.940 (2)°	0.20 × 0.18 × 0.17 mm
V = 549.5 (2) Å3

Data collection

Bruker APEXII CCD diffractometer	1946 independent reflections
Radiation source: fine-focus sealed tube	1870 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 25.2°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→9
Tmin = 0.460, Tmax = 0.512	k = −10→10
2843 measured reflections	l = −11→11

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0415P)2 + 0.4664P] where P = (Fo2 + 2Fc2)/3
1946 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.92 e Å−3
0 restraints	Δρmin = −1.37 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.5156 (6)	0.3528 (6)	0.7873 (5)	0.0193 (9)
C2	0.4448 (6)	0.2225 (6)	0.8439 (5)	0.0190 (9)
C3	0.5510 (7)	0.2276 (6)	0.9869 (5)	0.0278 (10)
H3A	0.5043	0.1411	1.0209	0.033*
C4	0.7265 (7)	0.3590 (7)	1.0820 (6)	0.0340 (12)
H4A	0.7963	0.3617	1.1788	0.041*
C5	0.7924 (6)	0.4829 (7)	1.0291 (6)	0.0310 (11)
H5A	0.9085	0.5728	1.0910	0.037*
C6	0.2549 (6)	0.0837 (6)	0.7555 (5)	0.0195 (9)
C7	0.0124 (6)	0.0944 (6)	0.0035 (5)	0.0209 (9)
C8	0.0714 (6)	0.5526 (5)	0.4754 (5)	0.0180 (8)
La1	0.14649 (3)	0.16626 (3)	0.39929 (2)	0.01432 (11)
N1	0.6911 (5)	0.4769 (5)	0.8873 (5)	0.0253 (8)
H1A	0.7393	0.5561	0.8570	0.030*
O1	0.1395 (4)	0.0964 (4)	0.6424 (3)	0.0215 (7)
O2	0.2093 (4)	−0.0404 (4)	0.7976 (4)	0.0285 (7)
O3	0.4372 (4)	0.3643 (4)	0.6604 (4)	0.0276 (7)
O4	0.1045 (5)	0.2240 (4)	0.1390 (4)	0.0258 (7)
O5	−0.0601 (5)	0.1020 (4)	−0.1273 (4)	0.0275 (7)
O6	0.1897 (4)	0.4906 (4)	0.4461 (4)	0.0238 (7)
O7	0.0581 (4)	0.6932 (4)	0.4686 (4)	0.0263 (7)
O1W	0.4501 (5)	0.2684 (5)	0.3496 (4)	0.0400 (9)
H1W	0.5512	0.3270	0.4309	0.060*
H2W	0.4721	0.1911	0.2808	0.060*
O2W	0.3055 (5)	−0.0633 (5)	0.4169 (4)	0.0329 (8)
H3W	0.2604	−0.1491	0.4396	0.049*
H4W	0.4214	−0.0254	0.4667	0.049*	0.50
H4W'	0.2871	−0.1202	0.3175	0.049*	0.50

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.018 (2)	0.016 (2)	0.018 (2)	0.0023 (17)	0.0060 (17)	0.0040 (17)
C2	0.017 (2)	0.017 (2)	0.0160 (19)	0.0019 (17)	0.0018 (17)	0.0062 (17)
C3	0.027 (2)	0.023 (2)	0.024 (2)	0.002 (2)	0.000 (2)	0.012 (2)
C4	0.024 (3)	0.034 (3)	0.024 (2)	0.001 (2)	−0.011 (2)	0.012 (2)
C5	0.017 (2)	0.029 (3)	0.029 (2)	0.001 (2)	−0.0042 (19)	0.006 (2)
C6	0.016 (2)	0.020 (2)	0.016 (2)	−0.0004 (17)	0.0025 (17)	0.0074 (17)
C7	0.021 (2)	0.024 (2)	0.017 (2)	0.0035 (18)	0.0066 (18)	0.0103 (18)
C8	0.014 (2)	0.014 (2)	0.017 (2)	0.0005 (17)	−0.0001 (16)	0.0029 (17)
La1	0.01183 (15)	0.01383 (16)	0.01434 (15)	0.00163 (11)	0.00223 (11)	0.00694 (11)
N1	0.0186 (19)	0.022 (2)	0.027 (2)	−0.0013 (16)	0.0045 (16)	0.0110 (17)
O1	0.0154 (15)	0.0253 (17)	0.0172 (15)	0.0003 (13)	−0.0005 (12)	0.0118 (13)
O2	0.0215 (17)	0.0269 (18)	0.0325 (18)	0.0002 (14)	0.0028 (14)	0.0192 (15)
O3	0.0211 (17)	0.0312 (18)	0.0235 (16)	−0.0002 (14)	0.0014 (14)	0.0163 (14)
O4	0.0326 (19)	0.0190 (16)	0.0157 (15)	−0.0002 (14)	0.0040 (14)	0.0068 (13)
O5	0.0369 (19)	0.0238 (16)	0.0163 (15)	0.0085 (15)	0.0030 (14)	0.0093 (13)
O6	0.0193 (16)	0.0192 (16)	0.0336 (17)	0.0070 (13)	0.0107 (14)	0.0116 (14)
O7	0.0294 (18)	0.0209 (16)	0.0373 (18)	0.0110 (14)	0.0169 (15)	0.0177 (14)
O1W	0.0197 (18)	0.057 (2)	0.0307 (19)	0.0001 (17)	0.0090 (15)	0.0158 (18)
O2W	0.0285 (18)	0.040 (2)	0.043 (2)	0.0178 (16)	0.0155 (16)	0.0276 (17)

Geometric parameters (Å, °)

C1—O3	1.248 (5)	La1—O6	2.574 (3)
C1—N1	1.382 (6)	La1—O5i	2.582 (3)
C1—C2	1.437 (6)	La1—O3	2.585 (3)
C2—C3	1.377 (6)	La1—O1W	2.598 (3)
C2—C6	1.489 (6)	La1—O4	2.606 (3)
C3—C4	1.395 (7)	La1—O7ii	2.608 (3)
C3—H3A	0.930	La1—O1iii	2.612 (3)
C4—C5	1.357 (7)	La1—O2W	2.634 (3)
C4—H4A	0.930	La1—O2iii	2.691 (3)
C5—N1	1.351 (6)	N1—H1A	0.860
C5—H5A	0.930	O1—La1iii	2.612 (3)
C6—O2	1.252 (5)	O2—La1iii	2.691 (3)
C6—O1	1.279 (5)	O5—La1i	2.582 (3)
C7—O4	1.250 (5)	O7—La1ii	2.608 (3)
C7—O5	1.251 (5)	O1W—H1W	0.850
C7—C7i	1.550 (9)	O1W—H2W	0.850
C8—O6	1.253 (5)	O2W—H3W	0.850
C8—O7	1.255 (5)	O2W—H4W	0.850
C8—C8ii	1.537 (8)	O2W—H4W'	0.850
La1—O1	2.553 (3)
O3—C1—N1	118.0 (4)	O1—La1—O1iii	61.92 (11)
O3—C1—C2	127.4 (4)	O6—La1—O1iii	130.59 (10)
N1—C1—C2	114.6 (4)	O5i—La1—O1iii	70.65 (10)
C3—C2—C1	120.0 (4)	O3—La1—O1iii	127.57 (9)
C3—C2—C6	118.0 (4)	O1W—La1—O1iii	148.31 (12)
C1—C2—C6	121.9 (4)	O4—La1—O1iii	111.41 (10)
C2—C3—C4	121.8 (4)	O7ii—La1—O1iii	72.58 (10)
C2—C3—H3A	119.1	O1—La1—O2W	68.95 (10)
C4—C3—H3A	119.1	O6—La1—O2W	147.03 (10)
C5—C4—C3	118.1 (4)	O5i—La1—O2W	64.56 (10)
C5—C4—H4A	121.0	O3—La1—O2W	78.73 (11)
C3—C4—H4A	121.0	O1W—La1—O2W	72.87 (12)
N1—C5—C4	120.6 (4)	O4—La1—O2W	115.38 (10)
N1—C5—H5A	119.7	O7ii—La1—O2W	138.08 (10)
C4—C5—H5A	119.7	O1iii—La1—O2W	81.33 (10)
O2—C6—O1	121.1 (4)	O1—La1—O2iii	105.06 (9)
O2—C6—C2	119.0 (4)	O6—La1—O2iii	92.61 (10)
O1—C6—C2	119.8 (4)	O5i—La1—O2iii	66.21 (10)
O4—C7—O5	126.4 (4)	O3—La1—O2iii	157.15 (11)
O4—C7—C7i	116.9 (4)	O1W—La1—O2iii	131.48 (11)
O5—C7—C7i	116.7 (5)	O4—La1—O2iii	67.14 (10)
O6—C8—O7	126.1 (4)	O7ii—La1—O2iii	65.52 (10)
O6—C8—C8ii	117.3 (4)	O1iii—La1—O2iii	49.08 (9)
O7—C8—C8ii	116.6 (4)	O2W—La1—O2iii	118.71 (11)
O1—La1—O6	115.01 (10)	C5—N1—C1	124.9 (4)
O1—La1—O5i	116.73 (10)	C5—N1—H1A	117.6
O6—La1—O5i	127.50 (10)	C1—N1—H1A	117.6
O1—La1—O3	65.68 (10)	C6—O1—La1	135.9 (3)
O6—La1—O3	74.38 (10)	C6—O1—La1iii	96.3 (3)
O5i—La1—O3	136.55 (11)	La1—O1—La1iii	118.08 (11)
O1—La1—O1W	121.99 (10)	C6—O2—La1iii	93.3 (2)
O6—La1—O1W	78.71 (11)	C1—O3—La1	136.4 (3)
O5i—La1—O1W	81.66 (11)	C7—O4—La1	118.5 (3)
O3—La1—O1W	65.28 (11)	C7—O5—La1i	119.4 (3)
O1—La1—O4	172.10 (10)	C8—O6—La1	120.7 (3)
O6—La1—O4	65.38 (10)	C8—O7—La1ii	119.8 (3)
O5i—La1—O4	62.14 (10)	La1—O1W—H1W	118.9
O3—La1—O4	120.98 (10)	La1—O1W—H2W	118.3
O1W—La1—O4	65.90 (11)	H1W—O1W—H2W	105.2
O1—La1—O7ii	69.92 (10)	La1—O2W—H3W	122.1
O6—La1—O7ii	62.13 (9)	La1—O2W—H4W	119.6
O5i—La1—O7ii	131.12 (11)	H3W—O2W—H4W	105.2
O3—La1—O7ii	91.67 (11)	La1—O2W—H4W'	101.0
O1W—La1—O7ii	139.07 (11)	H3W—O2W—H4W'	100.6
O4—La1—O7ii	104.60 (10)	H4W—O2W—H4W'	105.2
O3—C1—C2—C3	179.2 (4)	N1—C1—O3—La1	168.2 (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—C1	22.7 (4)
N1—C1—C2—C6	177.2 (4)	O6—La1—O3—C1	150.2 (4)
C1—C2—C3—C4	1.3 (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—C1	89.7 (4)
C3—C2—C6—O2	−11.8 (6)	O1iii—La1—O3—C1	20.6 (5)
C1—C2—C6—O2	170.5 (4)	O2W—La1—O3—C1	−49.1 (4)
C3—C2—C6—O1	165.6 (4)	O2iii—La1—O3—C1	92.9 (5)
C1—C2—C6—O1	−12.0 (6)	O5—C7—O4—La1	160.6 (4)
C4—C5—N1—C1	1.7 (7)	C7i—C7—O4—La1	−20.2 (6)
O3—C1—N1—C5	179.3 (4)	O6—La1—O4—C7	−157.7 (3)
C2—C1—N1—C5	−1.0 (6)	O5i—La1—O4—C7	20.9 (3)
O2—C6—O1—La1	−137.1 (4)	O3—La1—O4—C7	150.7 (3)
C2—C6—O1—La1	45.4 (6)	O1W—La1—O4—C7	114.1 (3)
O2—C6—O1—La1iii	5.4 (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—C7	58.8 (3)
O5i—La1—O1—C6	90.3 (4)	O2iii—La1—O4—C7	−53.3 (3)
O3—La1—O1—C6	−41.3 (4)	O4—C7—O5—La1i	159.7 (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—C6	136.7 (5)	C8ii—C8—O6—La1	15.1 (6)
O2W—La1—O1—C6	45.5 (4)	O1—La1—O6—C8	−63.1 (3)
O2iii—La1—O1—C6	160.9 (4)	O5i—La1—O6—C8	106.6 (3)
O6—La1—O1—La1iii	124.39 (13)	O3—La1—O6—C8	−116.0 (3)
O5i—La1—O1—La1iii	−46.43 (16)	O1W—La1—O6—C8	176.7 (3)
O3—La1—O1—La1iii	−178.07 (17)	O4—La1—O6—C8	108.2 (3)
O1W—La1—O1—La1iii	−143.50 (14)	O7ii—La1—O6—C8	−15.6 (3)
O7ii—La1—O1—La1iii	80.43 (14)	O1iii—La1—O6—C8	10.4 (4)
O1iii—La1—O1—La1iii	0.0	O2W—La1—O6—C8	−152.6 (3)
O2W—La1—O1—La1iii	−91.27 (15)	O2iii—La1—O6—C8	44.9 (3)
O2iii—La1—O1—La1iii	24.16 (15)	O6—C8—O7—La1ii	−165.3 (3)
O1—C6—O2—La1iii	−5.2 (4)	C8ii—C8—O7—La1ii	14.7 (6)
C2—C6—O2—La1iii	172.2 (3)

Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4iv	0.86	1.96	2.789 (5)	162
O1W—H1W···O6iv	0.85	2.01	2.805 (5)	155
O2W—H4W···O2Wv	0.85	2.00	2.853 (7)	180
O2W—H3W···O7vi	0.85	1.97	2.753 (5)	152

Symmetry codes: (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) x, y−1, z.