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The structure of the title compound, [La(C5H6O4)(C5H7O4)-(H2O)]·H2O, consists of dense layers formed by chains of one-edge-sharing LaO9(H2O) polyhedra, linked together by the glutarate ligand. The three-dimensional polymeric structure, built up through connection of these layers by the hydrogen glutarate ligand, exhibits cavities accommodating a guest water mol­ecule. The lanthanum ion is tenfold coordinated by four glutarates, acting as bridging-chelating carboxyl­ate groups, by three hydrogen glutarates, three times monodentate, and by one water mol­ecule. Its coordination polyhedron is highly distorted and intermediate between a bicapped dodecahedron and a tetracapped trigonal prism. Hydro­gen bonding links the two water mol­ecules and the framework built up from this polynuclear coordination polymer. A very short hydrogen bond, D...A = 2.484 (3) Å, links the proton­ated with the deprotonated acid groups in the hydrogen glutarate.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010000500X/sk1364sup1.cif
Contains datablocks LaGLUT, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010000500X/sk1364Isup2.hkl
Contains datablock I

CCDC reference: 147623

Comment top

The aliphatic dicarboxylic acids, HOOC-(CH2)n-COOH, present interesting complexing properties. This is due to the flexibility of the ligand that may be completely or only partially deprotonated. It has a large variation in coordination behavior, even with large values of n, showing both polyunidentate and/or chelating modes. This allows for clusters, cage structures or open frameworks. Combined with metallic cations assuming high coordination numbers, e.g. the rare earths, these ligands often yield infinite frameworks built up by polynuclear coordination polymers. This is due to the small directionality of the mainly electrostatic bonding of these cations. Two structural studies have been published on lanthanide glutarates (Głowiak et al., 1986; Serpaggi et al., 1998). Both studies exclude the lanthanum glutarate, which has not been synthesized so far.

We report in this paper the structure of the first lanthanum(III) compound obtained with glutaric acid: [La(HL)(L)(H2O)].H2O, (I). It contains hydrogen glutarate (HL) and glutarate (L) groups. One interesting feature of the structure is the infinite helicoidal chains of one-edge sharing LaO9(H2O) polyhedra running along the [010] direction (Fig. 1). The repeat distance between two nearest-neighbor La3+ within the chain is 4.429 Å. The La3+ ions are slightly displaced, by 0.32 Å, off the helical axis. The structure can be regarded as dense layers parallel to the (100) plane located around x=1/4 and x=3/4. These are formed by the polyhedral chains described above, linked together by the glutarates running along the [001] direction. The layers are connected through the monodeprotonated glutarates building a three-dimensional polymeric structure. Their packing results in cavities accommodating one guest water molecule (Fig. 2). \sch

Fig. 3 shows the tenfold coordination of La3+. The coordination sphere consists of four glutarates, three hydrogen glutarates and one water molecule. Although the dispersion of the bond lengths of lanthanum to oxygen is high [2.488 (2)–2.774 (2) Å, see Table 1], the average value of these distances is the same as otherwise found for ten-coordinated lanthanum (Marrot et al., 1993, 1994). The glutarate ligand L is a bridging-chelating carboxylate group in that it is bidentate by its two functions and that one of the chelating oxygen atoms bridges an adjacent metal atom. The doubly ligating O atoms (O11 and O13) show one short and one long La—O distance. The long distance is as expected associated with the bidentate function. The geometry for the two carboxylate groups of L is almost the same [the differences between the bond lengths are La—O11ii—La—O13ishort = 0.000 (3), La—O11—La—O13iiilong = 0.055 (3) and La—O12—La—O14iiimonodentate = 0.017 (3) Å]. This coordination leads to the infinite chain of pairs along the [010] direction and makes up the dense layers mentioned above.

The hydrogen glutarate ligand, HL, is three times monodentate, coordinating with all its O atoms, except the oxygen which belongs to the hydroxyl function. The dispersion of distances La—O are smaller in this ligand [between 2.590 (2) and 2.699 (2) Å]. The distances within the acid group are somewhat different from what would be expected: they are almost the same in the two ends [C21—O21 1.293 (4), C25—O24 1.292 (4) and C21—O22 1.240 (4), C25—O23 1.242 (4) Å] despite the fact that one is deprotonated and the other is protonated. This is different from the expected values if we refer to the usual distances which are 1.214 Å for CO and 1.308 Å for C—OH (Allen et al., 1995). However, this bonding situation resembles that of salts of dicarboxylic acids (Speakman, 1972). In addition, the C—C distances adjacent to the acid groups fit exactly with expected values: C21—C22 is 1.520 (5) Å which is expected for the C—C distance in C—COO (Allen et al., 1995); C24—C25 is 1.504 (5) while the expected C—C distance in C—COOH is 1.502 Å.

The conformation of the two independent ligands L and HL is completely different as indicated by the dihedral angles in each ligand (Table 1). L adopts an extended conformation while HL is twisted (Fig. 3). All the C-COO groups are planar. In L, C13, C14 and C15 are the only co-planar carbon atoms. This plane forms an angle of 30.25 (20) and 17.45 (17)° to the C12—C11—O11—O12 and C14—C15—O13—O14 planes, respectively. In HL, C21, C22, C23 and C24 form a plane that has an angle of 71.5 (2)° to the C22—C21—O21—O22 plane and 73.3° to the C24—C25—O23—O24 plane. The angle between the two acid planes is 30.40 (11)° in L while in HL it is 40.49 (19)°.

The coordination polyhedron is very distorted and may be described as intermediate between a bicapped dodecahedron and a tetracapped trigonal prism (Kepert, 1965; Marrot et al., 1993).

Hydrogen-bonding geometries are given in Table 2. The protonated acid group of HL is donating the hydrogen to a very short hydrogen bond to the carboxylate end of HL, see Fig. 3. This strong hydrogen bond is probably stabilizing the coordination geometry. Similar hydrogen bonds are found in acid salts of dicarboxylic acids in which hydrogendicarboxylate ions are linked by short hydrogen bonds into infinite chains (Speakman, 1972).

Another framework stabilizing hydrogen bond is present between the coordinating water molecule and the deprotonated acid group of HL. The non-coordinating water molecule is kept in place by hydrogen bonding with the coordinating framework (Fig. 2). It is disordered (see experimental) but the disorder could not be resolved with the present data. Due to the disorder, there is a very short hydrogen-hydrogen contact, H2W1···H2W1iii = 1.90 Å [operation (iii) is −x, 2 − z, 1 − z] and the O2W···O2W hydrogen bond has a distorted geometry. It can reasonably be assumed that the non-coordinating water plays a templating role during crystallization.

The framework created by the packing is that of parallelepipeds formed by the La3+ ions. The shortest dimensions of the La-parallelepipeds are along the b axis (the helical axis). In the a,c plane the dimensions are 9.96 by 9.78 Å with a major angle of 124.6°.

This structure is closely related to the two isostructural compounds Nd2(C5H6O4)3(H2O)2.2H2O (Głowiak et al., 1986) and Nd2(C5H6O4)3(H2O)2.4H2O (Serpaggi et al., 1998). The heavier lanthanide structures (Nd and heavier) are all isostructural, at least when using the same synthesis path (Serpaggi et al., 1998). Nd is ninefold coordinated while here we find tenfold coordination. The Nd-structures crystallize in C2/c and show an almost square grid of Nd-ions. The Nd structures are related to the present by exchanging a and b. The solvent containing cavities are truly open in the Nd compound leading to open solvent channels. In the present structure they are collapsed into isolated cavities from which no easy solvent diffusion path is present.

The differences between the heavier lanthanides and the La structure point to the possibility of obtaining new phases by varying the synthesis temperature and pH and consequently, the number of water molecules of crystallization. The importance of this factor is underlined by the fact that the glutarate of all the lanthanoids have been obtained previously except the glutarate of lanthanum.

Experimental top

The compound was obtained by applying grown phase under reflux, the preparation process being comparable with that used by Marrot & Trombe (1994). After mixing appropriate amounts of glutaric acid and lanthanum oxide, with carefully controlled pH and temperature, single crystals were obtained from the mother liquor after 10 d.

Refinement top

H atoms on carbon atoms were generated (after having been observed in the difference map) and refined in the riding model with Uiso(H) = 1.2Ueq(C). The acid-group hydrogen was refined as a rotating riding atom. The water H atoms were picked from the difference map and included with restraints d(O—H) = 0.820 (5) Å and d(H···H) = 1.30 (1) Å to get an angle of \sim104.5°. These restraints are so hard that the internal water geometry is given by them and the data are determining only the orientation of the water molecules. For all H atoms bound to O atoms: Uiso(H) = 1.5Ueq(O).

Water molecule 2 (O2W) shows some anisotropy in the ADPs, the ratio of the largest and smallest eigenvalues of the ADP tensor being 4.6. In addition, the equivalent isotropic displacement parameter of O2W is 2.33 (6) times larger than that of O1W. This, together with the rather small hydrogen bond angle between two symmetry-related water molecules (132°), points toward some residual disorder. Attempts to resolve this were not successful. It should be noted, that even with a split description of the oxygen, only one position for each hydrogen was visible in the difference map.

Computing details top

Data collection: KM4CCD (KUMA, 1999); cell refinement: KM4RED (KUMA, 1999); data reduction: KM4RED and XPREP (Siemens 1996a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens 1996b).

Figures top
[Figure 1] Fig. 1. Chains of lanthanum polyhedra running along [010].
[Figure 2] Fig. 2. : Perspective view of the packing seen along the b axis. Only H atoms bound to O atoms have been included. Hydrogen bonds are indicated by dashed lines. Note the water containing cavity in the center. Full displacement ellipsoids are used for the fully deprotonated ligand L while open ellipsoids are used for HL. Ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. Coordination around the lanthanum ion, including the numbering scheme and anisotropic displacement ellipsoids. Note the strong hydrogen bond O24—H24···O21iv. Only the unique chains have been labeled completely. The symmetry operations are as in Table 1 [(viii) is x, y − 1, z]. The view is along the b axis. Full displacement ellipsoids are used for the fully deprotonated ligand L while open ellipsoids are used for HL. Ellipsoids are drawn at the 50% probability level.
(I) top
Crystal data top
[Ln(C5H7O4)(C5H6O4)(H2O)]·H2ODx = 2.060 Mg m3
Mr = 436.15Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 10492 reflections
a = 16.4027 (6) Åθ = 3.6–27.7°
b = 8.76805 (19) ŵ = 3.09 mm1
c = 19.5576 (4) ÅT = 293 K
V = 2812.76 (13) Å3Needle, colourless
Z = 80.27 × 0.07 × 0.03 mm
F(000) = 1712
Data collection top
KUMA CCD
diffractometer
2992 independent reflections
Radiation source: fine-focus sealed tube2764 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
Detector resolution: 17.13 pixels mm-1θmax = 27.7°, θmin = 3.6°
Oscillation method, ϕ and ω scansh = 2018
Absorption correction: gaussian
XPREP (Siemens 1996a)
k = 1111
Tmin = 0.576, Tmax = 0.906l = 2525
25012 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: Difference map and geometry
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.049 w = 1/[σ2(Fo2) + 6.3345P]
where P = (Fo2 + 2Fc2)/3
S = 1.19(Δ/σ)max = 0.002
2992 reflectionsΔρmax = 1.28 e Å3
204 parametersΔρmin = 0.71 e Å3
6 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00071 (7)
Crystal data top
[Ln(C5H7O4)(C5H6O4)(H2O)]·H2OV = 2812.76 (13) Å3
Mr = 436.15Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 16.4027 (6) ŵ = 3.09 mm1
b = 8.76805 (19) ÅT = 293 K
c = 19.5576 (4) Å0.27 × 0.07 × 0.03 mm
Data collection top
KUMA CCD
diffractometer
2992 independent reflections
Absorption correction: gaussian
XPREP (Siemens 1996a)
2764 reflections with I > 2σ(I)
Tmin = 0.576, Tmax = 0.906Rint = 0.040
25012 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0286 restraints
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.19Δρmax = 1.28 e Å3
2992 reflectionsΔρmin = 0.71 e Å3
204 parameters
Special details top

Experimental. XPREP (Siemens 1996b) Data were collected with a CCD camera in about 27 h. Possible crystal decay was tested by comparing the intensity of two identical frames measured at the beginning and the end of the data collection. They show the same intensity showing that no decay took place.

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*/Ueq
La0.230754 (11)0.760514 (17)0.394496 (7)0.01376 (7)
O110.23399 (14)1.0345 (2)0.46554 (10)0.0195 (5)
O120.17251 (15)0.8376 (2)0.51232 (10)0.0239 (5)
C110.1999 (2)0.9710 (3)0.51675 (14)0.0166 (6)
C120.1943 (2)1.0581 (3)0.58343 (14)0.0248 (8)
H12A0.14891.12880.58070.030*
H12B0.24371.11770.58920.030*
C130.1829 (2)0.9571 (4)0.64600 (14)0.0246 (8)
H13A0.22530.87990.64670.030*
H13B0.13070.90540.64290.030*
C140.1862 (2)1.0485 (3)0.71220 (13)0.0195 (7)
H14A0.23331.11530.71080.023*
H14B0.13791.11230.71490.023*
C150.1910 (2)0.9516 (3)0.77637 (14)0.0164 (6)
O130.21474 (15)1.0148 (2)0.83168 (10)0.0230 (5)
O140.17286 (15)0.8126 (2)0.77513 (10)0.0253 (5)
O210.10546 (15)0.9467 (2)0.36388 (11)0.0270 (5)
O220.14444 (16)1.1725 (2)0.32364 (12)0.0328 (6)
C210.1013 (2)1.0567 (3)0.31993 (17)0.0247 (7)
C220.0426 (2)1.0397 (4)0.26031 (18)0.0363 (9)
H22A0.01011.13170.25610.044*
H22B0.00580.95530.26930.044*
C230.0878 (2)1.0109 (4)0.19306 (19)0.0365 (9)
H23A0.12471.09520.18450.044*
H23B0.12030.91910.19760.044*
C240.0307 (3)0.9933 (4)0.1318 (2)0.0440 (11)
H24A0.06320.96940.09170.053*
H24B0.00520.90740.14010.053*
C250.0206 (2)1.1311 (4)0.11615 (15)0.0240 (7)
O230.08612 (15)1.1213 (2)0.08452 (11)0.0270 (5)
O240.00798 (16)1.2592 (3)0.13830 (13)0.0321 (6)
H240.02781.32430.13680.048*
O1W0.36246 (15)0.8280 (3)0.46230 (13)0.0309 (6)
H1W10.4029 (13)0.773 (3)0.463 (2)0.046*
H1W20.3799 (19)0.9119 (18)0.451 (2)0.046*
O2W0.0009 (2)0.8518 (4)0.5362 (2)0.0719 (11)
H2W10.006 (3)0.9436 (14)0.541 (3)0.108*
H2W20.0500 (8)0.840 (6)0.531 (3)0.108*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La0.01960 (13)0.01158 (9)0.01010 (9)0.00031 (7)0.00017 (6)0.00052 (6)
O110.0274 (14)0.0184 (10)0.0129 (9)0.0008 (9)0.0037 (9)0.0018 (8)
O120.0360 (16)0.0189 (11)0.0169 (10)0.0071 (10)0.0054 (10)0.0032 (8)
C110.0184 (18)0.0178 (14)0.0135 (13)0.0027 (12)0.0019 (12)0.0015 (11)
C120.043 (2)0.0182 (15)0.0129 (13)0.0036 (15)0.0045 (14)0.0004 (11)
C130.039 (2)0.0204 (15)0.0142 (14)0.0044 (15)0.0001 (14)0.0002 (11)
C140.027 (2)0.0186 (14)0.0126 (13)0.0023 (13)0.0012 (13)0.0012 (11)
C150.0180 (18)0.0192 (14)0.0119 (12)0.0032 (12)0.0001 (12)0.0019 (11)
O130.0382 (15)0.0179 (10)0.0128 (10)0.0001 (10)0.0068 (9)0.0016 (8)
O140.0441 (16)0.0161 (10)0.0155 (10)0.0040 (10)0.0056 (10)0.0014 (8)
O210.0310 (16)0.0227 (11)0.0273 (12)0.0043 (10)0.0091 (10)0.0042 (9)
O220.0370 (17)0.0202 (11)0.0412 (14)0.0069 (11)0.0129 (12)0.0056 (10)
C210.026 (2)0.0206 (15)0.0275 (16)0.0021 (14)0.0046 (15)0.0010 (13)
C220.030 (2)0.039 (2)0.040 (2)0.0097 (17)0.0137 (17)0.0135 (16)
C230.038 (3)0.0313 (19)0.040 (2)0.0143 (17)0.0185 (18)0.0067 (15)
C240.057 (3)0.032 (2)0.044 (2)0.017 (2)0.024 (2)0.0126 (16)
C250.028 (2)0.0243 (16)0.0196 (15)0.0017 (14)0.0024 (14)0.0003 (12)
O230.0268 (15)0.0258 (12)0.0285 (12)0.0013 (10)0.0062 (11)0.0027 (9)
O240.0279 (15)0.0225 (12)0.0460 (15)0.0018 (11)0.0131 (12)0.0037 (11)
O1W0.0264 (15)0.0246 (12)0.0416 (14)0.0018 (10)0.0033 (12)0.0069 (11)
O2W0.037 (2)0.0488 (19)0.129 (3)0.0110 (16)0.019 (2)0.015 (2)
Geometric parameters (Å, º) top
La—O112.776 (2)C15—Lav3.037 (3)
La—O122.584 (2)O13—Lavi2.488 (2)
La—O11i2.4884 (19)O13—Lav2.721 (2)
La—O13ii2.721 (2)O14—Lav2.601 (2)
La—O14ii2.601 (2)C21—O211.293 (4)
La—O13iii2.488 (2)C21—O221.240 (4)
La—O212.692 (2)O22—Lavii2.590 (2)
La—O22i2.590 (2)C21—C221.520 (5)
La—O23iv2.699 (2)C22—C231.531 (5)
La—O1W2.603 (3)C22—H22A0.9700
La—C15ii3.037 (3)C22—H22B0.9700
La—C113.063 (3)C23—C241.528 (5)
C11—O111.275 (3)C23—H23A0.9700
C11—O121.256 (3)C23—H23B0.9700
C11—C121.514 (4)C24—C251.504 (5)
C12—C131.522 (4)C24—H24A0.9700
C12—H12A0.9700C24—H24B0.9700
C12—H12B0.9700C25—O231.242 (4)
C13—C141.524 (4)C25—O241.292 (4)
C13—H13A0.9700O23—Laviii2.699 (2)
C13—H13B0.9700O24—H240.8200
C14—C151.517 (4)O1W—H1W10.821 (5)
C14—H14A0.9700O1W—H1W20.820 (5)
C14—H14B0.9700O2W—H2W10.818 (5)
C15—O131.276 (3)O2W—H2W20.819 (5)
C15—O141.255 (3)
O11—La—O1248.27 (6)C11—O11—Lavii152.65 (18)
O11—La—O11i113.91 (7)C11—O11—La90.41 (16)
O11i—La—O1278.25 (7)C11—O12—La99.96 (17)
O11—La—O13ii174.60 (7)O12—C11—La56.22 (14)
O11—La—O14ii132.05 (6)O11—C11—La65.00 (14)
O11—La—O13iii63.57 (6)C12—C11—La170.6 (2)
O11—La—O2166.49 (7)O12—C11—O11120.6 (3)
O11—La—O22i120.71 (7)O12—C11—C12120.5 (3)
O11—La—O23iv109.40 (7)O11—C11—C12118.9 (3)
O11—La—O1W62.12 (7)C11—C12—C13114.0 (2)
O11i—La—O13ii64.42 (6)C11—C12—H12A108.8
O11i—La—O14ii112.94 (6)C13—C12—H12A108.8
O11i—La—O13iii145.37 (8)C11—C12—H12B108.8
O11i—La—O21141.68 (7)C13—C12—H12B108.8
O11i—La—O22i82.98 (7)H12A—C12—H12B107.7
O11i—La—O23iv76.07 (7)C12—C13—C14111.9 (2)
O11i—La—O1W72.76 (7)C12—C13—H13A109.2
O12—La—O13ii126.79 (6)C14—C13—H13A109.2
O12—La—O14ii136.88 (8)C12—C13—H13B109.2
O12—La—O13iii111.46 (6)C14—C13—H13B109.2
O12—La—O2175.97 (7)H13A—C13—H13B107.9
O12—La—O22i147.91 (8)C13—C14—C15114.2 (2)
O12—La—O23iv70.00 (7)C15—C14—H14A108.7
O12—La—O1W78.06 (8)C13—C14—H14A108.7
O13ii—La—O14ii48.76 (6)C15—C14—H14B108.7
O13ii—La—O21111.34 (7)C13—C14—H14B108.7
O13ii—La—O22i64.56 (7)H14A—C14—H14B107.6
O13ii—La—O23iv65.33 (7)O14—C15—O13120.7 (3)
O13ii—La—O1W120.79 (7)O14—C15—C14121.0 (2)
O13ii—La—O13iii120.95 (8)O13—C15—C14118.3 (2)
O13iii—La—O14ii83.29 (7)O14—C15—Lav58.04 (14)
O13iii—La—O2171.59 (7)O13—C15—Lav63.59 (14)
O13iii—La—O22i71.80 (7)C14—C15—Lav169.5 (2)
O13iii—La—O23iv138.50 (7)C15—O13—Lavi150.68 (19)
O13iii—La—O1W76.90 (7)C15—O13—Lav91.57 (16)
O14ii—La—O2170.80 (7)C15—O14—Lav97.79 (17)
O14ii—La—O22i74.62 (8)C21—O21—La129.8 (2)
O14ii—La—O23iv72.78 (7)C21—O22—Lavii136.6 (2)
O14ii—La—O1W144.73 (8)O22—C21—O21122.8 (3)
O21—La—O22i131.69 (7)O22—C21—C22119.1 (3)
O21—La—O23iv68.73 (7)O21—C21—C22118.0 (3)
O21—La—O1W127.51 (7)C21—C22—C23111.6 (3)
O22i—La—O23iv129.89 (7)C21—C22—H22A109.3
O22i—La—O1W71.60 (8)C23—C22—H22A109.3
O1W—La—O23iv139.01 (7)C21—C22—H22B109.3
Lavii—O11—La114.47 (7)C23—C22—H22B109.3
Lavi—O13—Lav116.41 (7)H22A—C22—H22B108.0
O13iii—La—C15ii100.76 (7)C22—C23—C24113.2 (3)
O11i—La—C15ii89.26 (7)C24—C23—H23A108.9
O12—La—C15ii139.38 (8)C22—C23—H23A108.9
O22i—La—C15ii65.19 (8)C24—C23—H23B108.9
O14ii—La—C15ii24.16 (7)C22—C23—H23B108.9
O1W—La—C15ii134.84 (8)H23A—C23—H23B107.7
O21—La—C15ii92.19 (8)C23—C24—C25114.9 (3)
O23iv—La—C15ii69.50 (8)C25—C24—H24A108.5
O13ii—La—C15ii24.84 (7)C23—C24—H24A108.5
O11—La—C15ii156.20 (7)C25—C24—H24B108.5
O13iii—La—C1188.14 (7)C23—C24—H24B108.5
O11i—La—C1194.73 (7)H24A—C24—H24B107.5
O12—La—C1123.83 (7)O23—C25—O24122.8 (3)
O22i—La—C11136.71 (8)O23—C25—C24122.0 (3)
O14ii—La—C11142.10 (8)O24—C25—C24115.2 (3)
O1W—La—C1166.57 (8)C25—O23—Laviii130.8 (2)
O21—La—C1171.46 (7)C25—O24—H24109.5
O23iv—La—C1190.50 (8)La—O1W—H1W1123 (3)
O13ii—La—C11150.59 (7)La—O1W—H1W2111 (3)
O11—La—C1124.60 (7)H1W1—O1W—H1W2104.5 (13)
C15ii—La—C11158.05 (9)H2W1—O2W—H2W2105.3 (14)
O11—C11—C12—C13158.3 (3)O21—C21—C22—C23107.7 (4)
O12—C11—C12—C1320.7 (5)O22—C21—C22—C2370.5 (4)
C11—C12—C13—C14174.3 (3)C21—C22—C23—C24179.9 (3)
C12—C13—C14—C15169.2 (3)C22—C23—C24—C2561.7 (5)
O13—C15—C14—C13162.2 (3)O23—C25—C24—C23156.1 (4)
O14—C15—C14—C1317.1 (5)O24—C25—C24—C2323.4 (5)
O11—C11—C15—O139.9 (5)O21—C21—C25—O2349.8 (5)
O11—C11—C15—O14148.3 (4)O21—C21—C25—O24169.5 (4)
O12—C11—C15—O13165.5 (4)O22—C21—C25—O23138.5 (4)
O12—C11—C15—O147.4 (3)O22—C21—C25—O2418.8 (3)
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x, y+3/2, z1/2; (iii) x+1/2, y+2, z1/2; (iv) x, y1/2, z+1/2; (v) x, y+3/2, z+1/2; (vi) x+1/2, y+2, z+1/2; (vii) x+1/2, y+1/2, z; (viii) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W2···O23ix0.82 (1)2.04 (1)2.857 (3)174 (4)
O1W—H1W1···O2Wx0.82 (1)1.94 (1)2.764 (4)178 (3)
O2W—H2W1···O2Wxi0.82 (1)2.35 (4)2.960 (8)132 (5)
O2W—H2W2···O120.82 (1)2.04 (1)2.856 (4)173 (6)
O24—H24···O21viii0.821.672.484 (3)176
Symmetry codes: (viii) x, y+1/2, z+1/2; (ix) x+1/2, y, z+1/2; (x) x+1/2, y+3/2, z+1; (xi) x, y+2, z+1.

Experimental details

Crystal data
Chemical formula[Ln(C5H7O4)(C5H6O4)(H2O)]·H2O
Mr436.15
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)16.4027 (6), 8.76805 (19), 19.5576 (4)
V3)2812.76 (13)
Z8
Radiation typeMo Kα
µ (mm1)3.09
Crystal size (mm)0.27 × 0.07 × 0.03
Data collection
DiffractometerKUMA CCD
diffractometer
Absorption correctionGaussian
XPREP (Siemens 1996a)
Tmin, Tmax0.576, 0.906
No. of measured, independent and
observed [I > 2σ(I)] reflections
25012, 2992, 2764
Rint0.040
(sin θ/λ)max1)0.654
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.049, 1.19
No. of reflections2992
No. of parameters204
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.28, 0.71

Computer programs: KM4CCD (KUMA, 1999), KM4RED (KUMA, 1999), KM4RED and XPREP (Siemens 1996a), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens 1996b).

Selected geometric parameters (Å, º) top
La—O112.776 (2)C12—C131.522 (4)
La—O122.584 (2)C13—C141.524 (4)
La—O11i2.4884 (19)C14—C151.517 (4)
La—O13ii2.721 (2)C15—O131.276 (3)
La—O14ii2.601 (2)C15—O141.255 (3)
La—O13iii2.488 (2)C21—O211.293 (4)
La—O212.692 (2)C21—O221.240 (4)
La—O22i2.590 (2)C21—C221.520 (5)
La—O23iv2.699 (2)C22—C231.531 (5)
La—O1W2.603 (3)C23—C241.528 (5)
C11—O111.275 (3)C24—C251.504 (5)
C11—O121.256 (3)C25—O231.242 (4)
C11—C121.514 (4)C25—O241.292 (4)
O11—La—O1248.27 (6)Lav—O11—La114.47 (7)
O11—La—O11i113.91 (7)Lavi—O13—Lavii116.41 (7)
O11i—La—O1278.25 (7)O12—C11—O11120.6 (3)
O13ii—La—O14ii48.76 (6)O14—C15—O13120.7 (3)
O13ii—La—O13iii120.95 (8)O22—C21—O21122.8 (3)
O13iii—La—O14ii83.29 (7)O23—C25—O24122.8 (3)
O21—La—O22i131.69 (7)
O11—C11—C12—C13158.3 (3)O21—C21—C22—C23107.7 (4)
O12—C11—C12—C1320.7 (5)O22—C21—C22—C2370.5 (4)
C11—C12—C13—C14174.3 (3)C21—C22—C23—C24179.9 (3)
C12—C13—C14—C15169.2 (3)C22—C23—C24—C2561.7 (5)
O13—C15—C14—C13162.2 (3)O23—C25—C24—C23156.1 (4)
O14—C15—C14—C1317.1 (5)O24—C25—C24—C2323.4 (5)
O11—C11—C15—O139.9 (5)O21—C21—C25—O2349.8 (5)
O11—C11—C15—O14148.3 (4)O21—C21—C25—O24169.5 (4)
O12—C11—C15—O13165.5 (4)O22—C21—C25—O23138.5 (4)
O12—C11—C15—O147.4 (3)O22—C21—C25—O2418.8 (3)
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x, y+3/2, z1/2; (iii) x+1/2, y+2, z1/2; (iv) x, y1/2, z+1/2; (v) x+1/2, y+1/2, z; (vi) x+1/2, y+2, z+1/2; (vii) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W2···O23viii0.820 (5)2.040 (7)2.857 (3)174 (4)
O1W—H1W1···O2Wix0.821 (5)1.944 (7)2.764 (4)178 (3)
O2W—H2W1···O2Wx0.818 (5)2.35 (4)2.960 (8)132 (5)
O2W—H2W2···O120.819 (5)2.042 (11)2.856 (4)173 (6)
O24—H24···O21xi0.821.672.484 (3)175.7
Symmetry codes: (viii) x+1/2, y, z+1/2; (ix) x+1/2, y+3/2, z+1; (x) x, y+2, z+1; (xi) x, y+1/2, z+1/2.
 

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