Poly[diaqua-(μ(4)-3,5-dicarb-oxyl-ato-pyra-zol-1-ido-κN,O:N,O:O:O,O)lanthanum(III)].

In the title coordination polymer, [La(C(5)HN(2)O(4))(H(2)O)(2)](n), the lanthanum(III) metal centre is nine-coordinated, with a distorted tricapped trigonal prismatic geometry, by the O atoms of two water mol-ecules and by two N and five O atoms of two N,O-bidentate, one O,O'-bidentate and one O-mono-dentate 3,5-dicarb-oxyl-ato-pyra-zol-1-ide ligands. The polymeric three-dimensional structure is stabilized by inter-molecular O-H⋯O hydrogen bonds.

Related literature

For other coordination complexes with pan class="Chemical">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

Crystal data

pan class="Chemical">[La(C5HN2O4)(H2O)2]

M = 328.02

Orthorhombic,

a = 12.5712 (8) Å

b = 8.4350 (6) Å

c = 16.0070 (10) Å

V = 1697.35 (19) Å3

Z = 8

Mo Kα radiation

μ = 5.04 mm−1

T = 293 K

0.32 × 0.24 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.239, T max = 0.365

8554 measured reflections

1496 independent reflections

1316 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.041

S = 1.06

1496 reflections

128 parameters

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.50 e Å−3

Data collection: pan class="Gene">APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020479/rz2328sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020479/rz2328Isup2.hkl

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

[La(C5HN2O4)(H2O)2]	F(000) = 1232
Mr = 328.02	Dx = 2.567 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3962 reflections
a = 12.5712 (8) Å	θ = 2.5–27.8°
b = 8.4350 (6) Å	µ = 5.04 mm−1
c = 16.007 (1) Å	T = 293 K
V = 1697.35 (19) Å3	Block, colourless
Z = 8	0.32 × 0.24 × 0.20 mm

Bruker APEXII CCD diffractometer	1496 independent reflections
Radiation source: fine-focus sealed tube	1316 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.239, Tmax = 0.365	k = −10→10
8554 measured reflections	l = −19→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.016	H-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 reflections	Δρmax = 0.52 e Å−3
128 parameters	Δρmin = −0.50 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00271 (13)

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.

	x	y	z	Uiso*/Ueq
La1	0.968426 (12)	0.009678 (17)	0.662201 (9)	0.01104 (9)
O1	0.80247 (17)	0.1816 (2)	0.67873 (12)	0.0212 (5)
O2	0.68279 (17)	0.3455 (3)	0.62560 (14)	0.0274 (5)
O3	0.9060 (2)	0.5049 (2)	0.31256 (13)	0.0222 (5)
O4	0.98606 (16)	0.2761 (2)	0.29004 (12)	0.0170 (4)
O5	1.0936 (2)	0.2221 (3)	0.60343 (15)	0.0325 (6)
H5A	1.0942	0.1442	0.6371	0.049*
H5B	1.0973	0.3066	0.6322	0.049*
O6	1.15184 (19)	−0.0151 (2)	0.73037 (16)	0.0338 (6)
H6A	1.1780	−0.1047	0.7434	0.051*
H6B	1.1851	0.0664	0.7475	0.051*
N1	0.89277 (19)	0.1436 (3)	0.52362 (14)	0.0162 (5)
N2	0.93750 (19)	0.1715 (3)	0.44839 (14)	0.0165 (5)
C1	0.7644 (2)	0.2632 (3)	0.61947 (19)	0.0153 (6)
C2	0.8238 (2)	0.2624 (3)	0.53938 (17)	0.0155 (6)
C3	0.8237 (2)	0.3719 (3)	0.47460 (18)	0.0190 (7)
H3	0.7841	0.4646	0.4698	0.023*
C4	0.8967 (2)	0.3099 (3)	0.41903 (17)	0.0160 (6)
C5	0.9322 (2)	0.3675 (3)	0.33671 (17)	0.0154 (6)

	U11	U22	U33	U12	U13	U23
La1	0.01164 (12)	0.01181 (12)	0.00967 (12)	0.00021 (6)	0.00036 (6)	−0.00053 (6)
O1	0.0230 (12)	0.0285 (11)	0.0122 (11)	0.0074 (9)	0.0021 (9)	0.0032 (9)
O2	0.0223 (12)	0.0311 (12)	0.0287 (13)	0.0141 (10)	0.0086 (10)	0.0075 (10)
O3	0.0358 (13)	0.0158 (11)	0.0150 (10)	0.0056 (9)	0.0055 (10)	0.0026 (8)
O4	0.0217 (11)	0.0158 (10)	0.0134 (11)	0.0024 (8)	0.0033 (8)	−0.0008 (8)
O5	0.0410 (15)	0.0214 (11)	0.0351 (13)	−0.0112 (11)	0.0097 (12)	−0.0019 (10)
O6	0.0253 (13)	0.0264 (12)	0.0496 (16)	−0.0030 (10)	−0.0187 (12)	0.0042 (10)
N1	0.0190 (13)	0.0176 (12)	0.0120 (12)	0.0019 (10)	0.0034 (10)	0.0015 (9)
N2	0.0201 (13)	0.0186 (12)	0.0108 (12)	0.0022 (10)	0.0041 (10)	0.0027 (10)
C1	0.0151 (16)	0.0149 (14)	0.0159 (15)	−0.0019 (12)	0.0012 (11)	−0.0016 (11)
C2	0.0159 (15)	0.0169 (14)	0.0137 (15)	0.0016 (12)	0.0000 (12)	0.0006 (11)
C3	0.0235 (17)	0.0163 (14)	0.0173 (16)	0.0060 (12)	0.0011 (12)	0.0011 (12)
C4	0.0190 (16)	0.0153 (13)	0.0137 (15)	0.0014 (12)	0.0004 (12)	0.0016 (11)
C5	0.0159 (15)	0.0153 (14)	0.0149 (16)	−0.0021 (11)	−0.0020 (11)	0.0005 (12)

La1—O2i	2.424 (2)	O4—La1iii	2.5929 (19)
La1—O3ii	2.535 (2)	O4—La1v	2.7388 (19)
La1—O1	2.554 (2)	O5—H5A	0.8500
La1—O6	2.559 (2)	O5—H5B	0.8500
La1—O5	2.564 (2)	O6—H6A	0.8500
La1—O4iii	2.5929 (19)	O6—H6B	0.8499
La1—N2iii	2.620 (2)	N1—C2	1.349 (4)
La1—N1	2.665 (2)	N1—N2	1.350 (3)
La1—O4ii	2.7388 (19)	N2—C4	1.360 (4)
La1—C5ii	3.014 (3)	N2—La1iii	2.620 (2)
La1—H5A	1.9874	C1—C2	1.483 (4)
O1—C1	1.266 (4)	C2—C3	1.389 (4)
O2—C1	1.242 (3)	C3—C4	1.380 (4)
O2—La1iv	2.424 (2)	C3—H3	0.9300
O3—C5	1.266 (3)	C4—C5	1.474 (4)
O3—La1v	2.535 (2)	C5—La1v	3.014 (3)
O4—C5	1.269 (3)
O2i—La1—O3ii	87.64 (7)	O2i—La1—H5A	154.3
O2i—La1—O1	73.08 (8)	O3ii—La1—H5A	117.8
O3ii—La1—O1	71.11 (7)	O1—La1—H5A	110.3
O2i—La1—O6	139.71 (7)	O6—La1—H5A	54.3
O3ii—La1—O6	82.55 (8)	O5—La1—H5A	15.9
O1—La1—O6	137.56 (7)	O4iii—La1—H5A	114.5
O2i—La1—O5	142.39 (7)	N2iii—La1—H5A	80.6
O3ii—La1—O5	124.93 (7)	N1—La1—H5A	82.7
O1—La1—O5	98.20 (7)	O4ii—La1—H5A	73.1
O6—La1—O5	70.16 (8)	C5ii—La1—H5A	96.4
O2i—La1—O4iii	73.32 (7)	C1—O1—La1	122.68 (18)
O3ii—La1—O4iii	75.12 (6)	C1—O2—La1iv	170.3 (2)
O1—La1—O4iii	132.65 (6)	C5—O3—La1v	99.48 (17)
O6—La1—O4iii	66.39 (6)	C5—O4—La1iii	120.58 (17)
O5—La1—O4iii	128.50 (7)	C5—O4—La1v	89.78 (16)
O2i—La1—N2iii	81.81 (8)	La1iii—O4—La1v	148.37 (8)
O3ii—La1—N2iii	138.85 (7)	La1—O5—H5B	114.9
O1—La1—N2iii	140.31 (7)	H5A—O5—H5B	107.7
O6—La1—N2iii	80.43 (8)	La1—O6—H6A	121.7
O5—La1—N2iii	83.25 (7)	La1—O6—H6B	120.9
O4iii—La1—N2iii	63.74 (7)	H6A—O6—H6B	116.7
O2i—La1—N1	76.18 (7)	C2—N1—N2	107.8 (2)
O3ii—La1—N1	134.47 (7)	C2—N1—La1	112.86 (17)
O1—La1—N1	63.52 (7)	N2—N1—La1	131.91 (17)
O6—La1—N1	135.32 (8)	N1—N2—C4	107.5 (2)
O5—La1—N1	67.51 (8)	N1—N2—La1iii	133.56 (17)
O4iii—La1—N1	135.91 (6)	C4—N2—La1iii	115.97 (17)
N2iii—La1—N1	81.13 (7)	O2—C1—O1	123.8 (3)
O2i—La1—O4ii	128.39 (7)	O2—C1—C2	119.1 (3)
O3ii—La1—O4ii	49.28 (6)	O1—C1—C2	117.0 (2)
O1—La1—O4ii	67.31 (6)	N1—C2—C3	110.8 (3)
O6—La1—O4ii	70.28 (7)	N1—C2—C1	119.2 (2)
O5—La1—O4ii	76.32 (6)	C3—C2—C1	129.9 (3)
O4iii—La1—O4ii	112.04 (2)	C4—C3—C2	103.2 (2)
N2iii—La1—O4ii	148.53 (7)	C4—C3—H3	128.4
N1—La1—O4ii	111.79 (6)	C2—C3—H3	128.4
O2i—La1—C5ii	107.57 (8)	N2—C4—C3	110.7 (2)
O3ii—La1—C5ii	24.47 (7)	N2—C4—C5	118.5 (2)
O1—La1—C5ii	65.50 (7)	C3—C4—C5	130.8 (3)
O6—La1—C5ii	76.66 (8)	O3—C5—O4	121.0 (3)
O5—La1—C5ii	101.11 (7)	O3—C5—C4	119.7 (3)
O4iii—La1—C5ii	94.58 (7)	O4—C5—C4	119.2 (2)
N2iii—La1—C5ii	153.48 (8)	O3—C5—La1v	56.04 (14)
N1—La1—C5ii	124.88 (7)	O4—C5—La1v	65.32 (14)
O4ii—La1—C5ii	24.90 (7)	C4—C5—La1v	171.1 (2)
O2i—La1—O1—C1	−89.3 (2)	La1—N1—N2—La1iii	55.4 (3)
O3ii—La1—O1—C1	177.3 (2)	La1—O1—C1—O2	178.7 (2)
O6—La1—O1—C1	122.6 (2)	La1—O1—C1—C2	−3.1 (3)
O5—La1—O1—C1	53.1 (2)	N2—N1—C2—C3	−0.9 (3)
O4iii—La1—O1—C1	−135.8 (2)	La1—N1—C2—C3	152.7 (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—C1	124.5 (2)	O2—C1—C2—N1	−161.5 (3)
C5ii—La1—O1—C1	151.7 (2)	O1—C1—C2—N1	20.3 (4)
O2i—La1—N1—C2	93.7 (2)	O2—C1—C2—C3	21.1 (5)
O3ii—La1—N1—C2	21.3 (2)	O1—C1—C2—C3	−157.2 (3)
O1—La1—N1—C2	15.99 (18)	N1—C2—C3—C4	0.4 (3)
O6—La1—N1—C2	−115.99 (19)	C1—C2—C3—C4	178.0 (3)
O5—La1—N1—C2	−96.26 (19)	N1—N2—C4—C3	−0.9 (3)
O4iii—La1—N1—C2	141.00 (17)	La1iii—N2—C4—C3	162.30 (19)
N2iii—La1—N1—C2	177.4 (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—N2	0.3 (3)
O2i—La1—N1—N2	−120.8 (2)	C2—C3—C4—C5	178.8 (3)
O3ii—La1—N1—N2	166.70 (19)	La1v—O3—C5—O4	7.1 (3)
O1—La1—N1—N2	161.4 (2)	La1v—O3—C5—C4	−170.7 (2)
O6—La1—N1—N2	29.5 (3)	La1iii—O4—C5—O3	−177.2 (2)
O5—La1—N1—N2	49.2 (2)	La1v—O4—C5—O3	−6.5 (3)
O4iii—La1—N1—N2	−73.6 (2)	La1iii—O4—C5—C4	0.7 (3)
N2iii—La1—N1—N2	−37.1 (2)	La1v—O4—C5—C4	171.4 (2)
O4ii—La1—N1—N2	113.0 (2)	La1iii—O4—C5—La1v	−170.65 (16)
C5ii—La1—N1—N2	137.2 (2)	N2—C4—C5—O3	−171.1 (3)
C2—N1—N2—C4	1.1 (3)	C3—C4—C5—O3	10.5 (5)
La1—N1—N2—C4	−145.6 (2)	N2—C4—C5—O4	11.0 (4)
C2—N1—N2—La1iii	−157.9 (2)	C3—C4—C5—O4	−167.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6	0.85	2.14	2.944 (3)	159
O5—H5B···O3vi	0.85	1.82	2.667 (3)	174
O6—H6A···O1vii	0.85	2.20	2.999 (3)	155
O6—H6B···O1viii	0.85	2.12	2.908 (3)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6	0.85	2.14	2.944 (3)	159
O5—H5B⋯O3i	0.85	1.82	2.667 (3)	174
O6—H6A⋯O1ii	0.85	2.20	2.999 (3)	155
O6—H6B⋯O1iii	0.85	2.12	2.908 (3)	153

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