Redetermination of di-aqua-tris-(4-oxo-pent-2-en-2-olato-κ(2) O,O')lanthanum(III).

The structure of the title compound, [La(C5H7O2)3(H2O)2], has been redetermined to modern standards with anisotropic displacement parameters for all non-H atoms and the hydrogen-bonding pattern unambiguously established [for the previous study, see Phillips et al. (1968 ▶). Inorg. Chem. 7, 2295-2299]. The La(3+) ion is coordinated by three O,O'-bidentate acetyl-acetate (acac(-)) ligands and two water mol-ecules, resulting in a fairly regular square-anti-prismatic LaO8 coordination geometry, with both aqua ligands part of the same square face. In the crystal, the neutral complex mol-ecules are linked into [110] chains by O-H⋯O hydrogen bonds.

Related literature

For the previous report on the title compound, see: Phillips et al. (1968 ▶). For related tris­(acetyl­acetonato)lanthanide complexes, see: Watkins et al. (1969 ▶); Kooijman et al. (2000 ▶). For other lanthanide complexes, see: Richardson et al. (1968 ▶); Lama et al. (2007 ▶).

Experimental

Crystal data

[La(C5H7O2)3(H2O)2]

M = 472.26

Triclinic,

a = 8.9245 (12) Å

b = 10.6597 (15) Å

c = 11.3727 (15) Å

α = 96.614 (2)°

β = 100.601 (2)°

γ = 114.325 (2)°

V = 946.8 (2) Å3

Z = 2

Mo Kα radiation

μ = 2.29 mm−1

T = 100 K

0.50 × 0.50 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.40, T max = 0.63

13810 measured reflections

5213 independent reflections

5068 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.058

S = 1.06

5213 reflections

240 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.04 e Å−3

Δρmin = −1.41 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814013336/hb7216sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013336/hb7216Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814013336/hb7216Isup3.cdx

CCDC reference: 1007160

Additional supporting information: crystallographic information; 3D view; checkCIF report

[La(C5H7O2)3(H2O)2]	Z = 2
Mr = 472.26	F(000) = 472
Triclinic, P1	Dx = 1.657 Mg m−3
a = 8.9245 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6597 (15) Å	Cell parameters from 9940 reflections
c = 11.3727 (15) Å	θ = 2.5–30.5°
α = 96.614 (2)°	µ = 2.29 mm−1
β = 100.601 (2)°	T = 100 K
γ = 114.325 (2)°	Block, colourless
V = 946.8 (2) Å3	0.50 × 0.50 × 0.22 mm

Bruker APEXII CCD diffractometer	5213 independent reflections
Radiation source: fine focus sealed tube	5068 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 8.3333 pixels mm-1	θmax = 29.6°, θmin = 1.9°
phi and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −14→14
Tmin = 0.40, Tmax = 0.63	l = −15→15
13810 measured reflections

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)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.058	w = 1/[σ2(Fo2) + (0.0344P)2 + 0.2713P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.003
5213 reflections	Δρmax = 1.04 e Å−3
240 parameters	Δρmin = −1.41 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0149 (8)

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	0.770906 (10)	0.782106 (9)	0.614919 (8)	0.01085 (5)
O7	1.00237 (17)	0.85834 (14)	0.50120 (13)	0.0153 (2)
O6	0.67267 (17)	0.56182 (14)	0.69763 (12)	0.0162 (2)
O4	0.45916 (16)	0.69885 (14)	0.55190 (12)	0.0159 (2)
O1	0.95280 (17)	1.03835 (14)	0.70708 (12)	0.0180 (3)
O2	0.72212 (18)	0.84749 (15)	0.81177 (13)	0.0209 (3)
O3	0.68870 (16)	0.90080 (14)	0.45213 (12)	0.0161 (2)
O8	0.66186 (18)	0.58124 (15)	0.42448 (13)	0.0170 (3)
C3	0.9035 (3)	1.0876 (2)	0.90089 (18)	0.0193 (4)
H3	0.9367	1.1593	0.9716	0.023*
C2	0.9814 (2)	1.1236 (2)	0.80637 (17)	0.0170 (3)
C4	0.7789 (2)	0.9524 (2)	0.89890 (17)	0.0175 (3)
C5	0.7027 (3)	0.9307 (2)	1.00763 (19)	0.0239 (4)
H5A	0.6022	0.9485	0.9939	0.036*
H5B	0.7869	0.9961	1.0817	0.036*
H5C	0.6697	0.8336	1.0177	0.036*
C1	1.1092 (3)	1.2747 (2)	0.8198 (2)	0.0281 (4)
H1A	1.2086	1.2767	0.7937	0.042*
H1B	1.1445	1.3239	0.9057	0.042*
H1C	1.0571	1.3216	0.7688	0.042*
C9	0.3503 (2)	0.71969 (18)	0.47772 (17)	0.0142 (3)
C7	0.5536 (2)	0.89906 (19)	0.39080 (17)	0.0146 (3)
C10	0.1669 (2)	0.6312 (2)	0.47366 (19)	0.0188 (4)
H10A	0.1324	0.5336	0.4336	0.028*
H10B	0.0959	0.6679	0.4275	0.028*
H10C	0.1529	0.6344	0.5573	0.028*
C8	0.3893 (2)	0.8151 (2)	0.40103 (18)	0.0174 (3)
H8	0.2974	0.824	0.3518	0.021*
C6	0.5706 (2)	0.9907 (2)	0.29805 (18)	0.0198 (4)
H6A	0.6826	1.0725	0.3242	0.03*
H6B	0.4817	1.0229	0.2913	0.03*
H6C	0.5586	0.9366	0.2183	0.03*
O5	1.01440 (17)	0.74506 (15)	0.72219 (13)	0.0189 (3)
C14	0.7368 (3)	0.5254 (2)	0.78893 (17)	0.0179 (4)
C12	1.0387 (3)	0.6712 (2)	0.79565 (17)	0.0183 (3)
C13	0.9103 (3)	0.5708 (2)	0.83696 (18)	0.0209 (4)
H13	0.9441	0.5314	0.9017	0.025*
C15	0.6127 (3)	0.4243 (3)	0.8472 (2)	0.0299 (5)
H15A	0.5659	0.4746	0.8951	0.045*
H15B	0.6714	0.3842	0.9011	0.045*
H15C	0.52	0.3484	0.7831	0.045*
C11	1.2197 (3)	0.6933 (3)	0.8430 (2)	0.0279 (4)
H11A	1.2719	0.6932	0.7743	0.042*
H11B	1.2194	0.6171	0.8838	0.042*
H11C	1.285	0.7839	0.9014	0.042*
H2W	0.985 (4)	0.867 (3)	0.435 (3)	0.035 (8)*
H1W	1.104 (4)	0.932 (3)	0.536 (3)	0.034 (8)*
H4W	0.659 (4)	0.514 (3)	0.441 (3)	0.027 (7)*
H3W	0.569 (4)	0.561 (3)	0.381 (3)	0.040 (9)*

	U11	U22	U33	U12	U13	U23
La1	0.01059 (7)	0.00983 (7)	0.01199 (7)	0.00403 (4)	0.00295 (4)	0.00369 (4)
O7	0.0140 (6)	0.0156 (6)	0.0167 (6)	0.0058 (5)	0.0048 (5)	0.0062 (5)
O6	0.0164 (6)	0.0141 (6)	0.0163 (6)	0.0052 (5)	0.0030 (5)	0.0052 (5)
O4	0.0127 (6)	0.0154 (6)	0.0204 (6)	0.0062 (5)	0.0046 (5)	0.0061 (5)
O1	0.0221 (7)	0.0138 (6)	0.0152 (6)	0.0051 (5)	0.0057 (5)	0.0021 (5)
O2	0.0226 (7)	0.0193 (7)	0.0175 (6)	0.0055 (6)	0.0082 (5)	0.0020 (5)
O3	0.0127 (6)	0.0168 (6)	0.0198 (6)	0.0068 (5)	0.0037 (5)	0.0077 (5)
O8	0.0178 (7)	0.0128 (6)	0.0177 (6)	0.0047 (5)	0.0035 (5)	0.0029 (5)
C3	0.0209 (9)	0.0185 (9)	0.0148 (8)	0.0068 (7)	0.0036 (7)	−0.0013 (7)
C2	0.0174 (8)	0.0154 (8)	0.0159 (8)	0.0065 (7)	0.0016 (7)	0.0022 (6)
C4	0.0173 (8)	0.0237 (9)	0.0145 (8)	0.0114 (8)	0.0046 (7)	0.0047 (7)
C5	0.0226 (10)	0.0329 (11)	0.0169 (9)	0.0120 (9)	0.0081 (8)	0.0041 (8)
C1	0.0319 (11)	0.0154 (9)	0.0251 (10)	0.0010 (8)	0.0047 (9)	0.0015 (8)
C9	0.0124 (7)	0.0128 (7)	0.0180 (8)	0.0061 (6)	0.0052 (6)	0.0014 (6)
C7	0.0156 (8)	0.0129 (8)	0.0160 (8)	0.0074 (7)	0.0031 (6)	0.0033 (6)
C10	0.0128 (8)	0.0176 (8)	0.0265 (10)	0.0065 (7)	0.0069 (7)	0.0050 (7)
C8	0.0120 (8)	0.0185 (8)	0.0220 (9)	0.0071 (7)	0.0028 (7)	0.0066 (7)
C6	0.0192 (9)	0.0215 (9)	0.0211 (9)	0.0094 (7)	0.0055 (7)	0.0107 (7)
O5	0.0165 (6)	0.0195 (6)	0.0222 (7)	0.0084 (5)	0.0035 (5)	0.0107 (5)
C14	0.0239 (9)	0.0164 (8)	0.0130 (8)	0.0075 (7)	0.0059 (7)	0.0051 (7)
C12	0.0194 (9)	0.0184 (8)	0.0152 (8)	0.0087 (7)	−0.0011 (7)	0.0037 (7)
C13	0.0226 (9)	0.0220 (9)	0.0152 (8)	0.0081 (8)	−0.0005 (7)	0.0088 (7)
C15	0.0289 (11)	0.0321 (12)	0.0229 (10)	0.0052 (9)	0.0078 (9)	0.0146 (9)
C11	0.0203 (10)	0.0310 (11)	0.0335 (12)	0.0130 (9)	0.0002 (8)	0.0151 (9)

La1—O2	2.4365 (14)	C1—H1B	0.98
La1—O4	2.4754 (13)	C1—H1C	0.98
La1—O5	2.4917 (14)	C9—C8	1.393 (3)
La1—O1	2.5013 (14)	C9—C10	1.504 (2)
La1—O6	2.5067 (13)	C7—C8	1.404 (2)
La1—O3	2.5241 (13)	C7—C6	1.505 (3)
La1—O7	2.5381 (13)	C10—H10A	0.98
La1—O8	2.5811 (14)	C10—H10B	0.98
O7—H2W	0.76 (3)	C10—H10C	0.98
O7—H1W	0.90 (3)	C8—H8	0.95
O6—C14	1.270 (2)	C6—H6A	0.98
O4—C9	1.274 (2)	C6—H6B	0.98
O1—C2	1.278 (2)	C6—H6C	0.98
O2—C4	1.258 (2)	O5—C12	1.261 (2)
O3—C7	1.269 (2)	C14—C13	1.393 (3)
O8—H4W	0.75 (3)	C14—C15	1.509 (3)
O8—H3W	0.81 (4)	C12—C13	1.408 (3)
C3—C2	1.392 (3)	C12—C11	1.514 (3)
C3—C4	1.406 (3)	C13—H13	0.95
C3—H3	0.95	C15—H15A	0.98
C2—C1	1.511 (3)	C15—H15B	0.98
C4—C5	1.513 (3)	C15—H15C	0.98
C5—H5A	0.98	C11—H11A	0.98
C5—H5B	0.98	C11—H11B	0.98
C5—H5C	0.98	C11—H11C	0.98
C1—H1A	0.98
O2—La1—O4	80.43 (5)	H5A—C5—H5C	109.5
O2—La1—O5	89.79 (5)	H5B—C5—H5C	109.5
O4—La1—O5	147.90 (4)	C2—C1—H1A	109.5
O2—La1—O1	68.90 (5)	C2—C1—H1B	109.5
O4—La1—O1	117.77 (4)	H1A—C1—H1B	109.5
O5—La1—O1	86.07 (5)	C2—C1—H1C	109.5
O2—La1—O6	74.35 (5)	H1A—C1—H1C	109.5
O4—La1—O6	79.74 (4)	H1B—C1—H1C	109.5
O5—La1—O6	68.17 (4)	O4—C9—C8	125.02 (16)
O1—La1—O6	134.81 (4)	O4—C9—C10	115.96 (16)
O2—La1—O3	114.29 (5)	C8—C9—C10	119.01 (16)
O4—La1—O3	68.42 (4)	O3—C7—C8	124.70 (17)
O5—La1—O3	142.08 (4)	O3—C7—C6	117.55 (16)
O1—La1—O3	76.92 (4)	C8—C7—C6	117.74 (16)
O6—La1—O3	144.19 (4)	C9—C10—H10A	109.5
O2—La1—O7	139.98 (5)	C9—C10—H10B	109.5
O4—La1—O7	133.31 (5)	H10A—C10—H10B	109.5
O5—La1—O7	70.81 (5)	C9—C10—H10C	109.5
O1—La1—O7	74.97 (4)	H10A—C10—H10C	109.5
O6—La1—O7	124.99 (4)	H10B—C10—H10C	109.5
O3—La1—O7	72.12 (4)	C9—C8—C7	125.12 (17)
O2—La1—O8	143.70 (5)	C9—C8—H8	117.4
O4—La1—O8	74.43 (5)	C7—C8—H8	117.4
O5—La1—O8	97.74 (5)	C7—C6—H6A	109.5
O1—La1—O8	146.72 (4)	C7—C6—H6B	109.5
O6—La1—O8	75.73 (5)	H6A—C6—H6B	109.5
O3—La1—O8	80.19 (5)	C7—C6—H6C	109.5
O7—La1—O8	75.20 (5)	H6A—C6—H6C	109.5
La1—O7—H2W	122 (2)	H6B—C6—H6C	109.5
La1—O7—H1W	120.9 (19)	C12—O5—La1	137.23 (13)
H2W—O7—H1W	103 (3)	O6—C14—C13	124.89 (18)
C14—O6—La1	133.49 (12)	O6—C14—C15	116.30 (19)
C9—O4—La1	139.02 (12)	C13—C14—C15	118.80 (18)
C2—O1—La1	136.92 (12)	O5—C12—C13	124.82 (18)
C4—O2—La1	139.63 (13)	O5—C12—C11	117.21 (18)
C7—O3—La1	137.69 (12)	C13—C12—C11	117.97 (17)
La1—O8—H4W	112 (2)	C14—C13—C12	124.17 (17)
La1—O8—H3W	117 (2)	C14—C13—H13	117.9
H4W—O8—H3W	106 (3)	C12—C13—H13	117.9
C2—C3—C4	124.49 (18)	C14—C15—H15A	109.5
C2—C3—H3	117.8	C14—C15—H15B	109.5
C4—C3—H3	117.8	H15A—C15—H15B	109.5
O1—C2—C3	124.97 (18)	C14—C15—H15C	109.5
O1—C2—C1	116.52 (17)	H15A—C15—H15C	109.5
C3—C2—C1	118.51 (18)	H15B—C15—H15C	109.5
O2—C4—C3	124.92 (18)	C12—C11—H11A	109.5
O2—C4—C5	116.86 (18)	C12—C11—H11B	109.5
C3—C4—C5	118.19 (18)	H11A—C11—H11B	109.5
C4—C5—H5A	109.5	C12—C11—H11C	109.5
C4—C5—H5B	109.5	H11A—C11—H11C	109.5
H5A—C5—H5B	109.5	H11B—C11—H11C	109.5
C4—C5—H5C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O7—H2W···O1i	0.76 (3)	2.05 (3)	2.7514 (19)	153 (3)
O7—H1W···O3i	0.90 (3)	1.94 (3)	2.7912 (19)	158 (3)
O8—H4W···O4ii	0.75 (3)	2.09 (3)	2.7907 (19)	155 (3)
O8—H3W···O6ii	0.81 (4)	1.96 (4)	2.721 (2)	155 (3)

Table 1

Selected bond lengths (Å)

La1—O2	2.4365 (14)
La1—O4	2.4754 (13)
La1—O5	2.4917 (14)
La1—O1	2.5013 (14)
La1—O6	2.5067 (13)
La1—O3	2.5241 (13)
La1—O7	2.5381 (13)
La1—O8	2.5811 (14)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H2W⋯O1i	0.76 (3)	2.05 (3)	2.7514 (19)	153 (3)
O7—H1W⋯O3i	0.90 (3)	1.94 (3)	2.7912 (19)	158 (3)
O8—H4W⋯O4ii	0.75 (3)	2.09 (3)	2.7907 (19)	155 (3)
O8—H3W⋯O6ii	0.81 (4)	1.96 (4)	2.721 (2)	155 (3)

Symmetry codes: (i) ; (ii) .