Poly[μ2-aqua-μ4-[1-(4-chloro­phen­yl)-4,4,4-tri­fluoro­butane-1,3-dionato]-potassium]

João P Martins; Cláudia C Arranja; Abílio J F N Sobral; Manuela Ramos Silva

doi:10.1107/S1600536813017388

. 2013 Jun 29;69(Pt 7):m422–m423. doi: 10.1107/S1600536813017388

Poly[μ₂-aqua-μ₄-[1-(4-chlorophenyl)-4,4,4-trifluorobutane-1,3-dionato]-potassium]

João P Martins ^a, Cláudia C Arranja ^b, Abílio J F N Sobral ^b, Manuela Ramos Silva ^a,^*

PMCID: PMC3772444 PMID: 24046587

Abstract

In the title compound, [K(C₁₀H₅ClO₂F₃)(H₂O)]_n, the two independent K⁺ ions are located on a twofold rotation axis. For each of the cations, the distorted cubic coordination environment is defined by two F and four O atoms of symmetry-related 1,4-chlorophenyl-4,4,4-trifluorobutane-1,3-dionate anions and by two O atoms of water molecules. The μ₄-bridging character of the anion and the μ₂-bridging of the water molecule lead to the formation of layers parallel to (100). The coordinating water molecules are also involved in O—H⋯O hydrogen bonds that reinforce the molecular cohesion within the layers, which are stacked along [100]. The β-diketonate anion is not planar, with an angle of 31.78 (10)° between the mean planes of the diketonate group and the chlorophenyl ring.

Related literature

For background to lanthanide complexes with diketonate ligands, see: Martín-Ramos et al. (2013a ▶,b ▶).

Experimental

Crystal data

[K(C₁₀H₅ClF₃O₂)(H₂O)]
M _r = 306.71
Monoclinic,
a = 30.164 (2) Å
b = 8.0739 (4) Å
c = 10.2696 (5) Å
β = 98.752 (2)°
V = 2471.9 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 293 K
0.20 × 0.11 × 0.08 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.830, T _max = 0.999
11396 measured reflections
2182 independent reflections
1559 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.097
S = 1.01
2182 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813017388/wm2752sup1.cif

e-69-0m422-sup1.cif^{(27.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813017388/wm2752Isup2.hkl

e-69-0m422-Isup2.hkl^{(107.4KB, hkl)}

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
O3—H1W⋯O2	0.82 (3)	1.90 (3)	2.709 (2)	173 (3)
O3—H2W⋯O1ⁱ	0.87 (3)	2.06 (3)	2.843 (3)	150 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Fundo Europeu de Desenvolvimento Regional-QREN-COMPETE through projects PEst-C/FIS/UI0036/2011, PTDC/FIS/102284/2008, PTDC/AAC-CLI/098308/2008 and PTDC/AAC-CLI/118092/2010-Fundação para a Ciência e a Tecnologia (FCT).

supplementary crystallographic information

Comment

The title compound, [K(C₁₀H₅ClO₂F₃)(H₂O)], Fig. 1, was obtained serendipitously as part of a project to synthesize new lanthanide coordination complexes as potential emissive layers in organic light emitting diodes (OLEDs) (Martín-Ramos, 2013a,b).

The title compound contains two potassium ions, one 1,4-chlorophenyl-4,4,4-trifluoro-1,3-butanedionate anion and one coordinating water molecule in the asymmetric unit. Both potassium ions are situated on twofold rotation axes and are in the centres of distorted cubes, that are formed by two F and six O atoms. The cations are arranged in alternating chains along [010], Fig. 2, with K···K distances of 3.6379 (11) and 4.4360 (11) Å, respectively. The cations are bridged by two water molecules and one bis-monodentate CF₃ group, as well as by four oxygen atoms of two β-diketonate groups. The chains are joined into layers parallel to (100) since each diketonate coordinates potassium ions from two adjacent chains. The β-diketonate ligand is not planar with an angle of 31.78 (10)° between the mean planes of the diketonate group and the chlorophenyl ring. Within the layers, there are hydrogen bonds between the coordinating water molecules and adjacent diketonate O atoms (Table 1, Fig. 3). The unit cell does not contain any residual solvent acessible voids.

Experimental

Firstly, 0.5 mmol of europium(III) nitrate pentahydrate were dissolved in 20 ml of methanol followed by the addition of 0.9 ml of potassium methoxide. This solution was left to reflux at 353 K for 15 min. Secondly, 1.5 mmol of 1,14 chlorophenyl-4,4,4-trifluoro-1,3-butanedionate were dissolved in 15 ml of methanol and added to the main solution. After decanting the resulting solution, 0.5 mmol of bathophenanthroline were dissolved in 10 ml of methanol and added to the main solution. The main solution was then transferred from a volumetric balloon to a beaker covered with paraffin film and placed on a water bath at 303 K until complete evaporation was verified. Since from the evaporation process no crystals were obtained, all the material from this batch was dissolved in 25 ml of chloroform. A light orange powder was formed alongside with some transparent crystals. The powder was studied by X-ray powder diffraction and was proven to be amorphous; the transparent crystals were studied by single-crystal X-ray diffraction, and as a result, the title compound was revealed.