catena-Poly[[triaqua­chlorido-μ3-malonato-cerium(III)] hemihydrate]

Silva, P.; Fernandes, J.A.; Almeida Paz, F.A.

doi:10.1107/S1600536810044727

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages m1514-m1515

https://doi.org/10.1107/S1600536810044727

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catena-Poly[[triaquachlorido-μ₃-malonato-cerium(III)] hemihydrate]

Patrícia Silva,^a José A. Fernandes ^a and Filipe A. Almeida Paz ^a ^*

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 30 October 2010; accepted 1 November 2010; online 6 November 2010)

The asymmetric unit of the title compound, {[Ce(C₃H₂O₄)Cl(H₂O)₃]·0.5H₂O}_n, contains a Ce³⁺ atom coordinated by a chloride anion, three water molecules and a malonate ligand, and one water molecule of crystallization with a factor of occupancy of 50%. The malonate ligand is bonded to three different symmetry-related metal atoms yielding a one-dimensional coordination polymer running parallel to the a axis. A supramolecular network composed of strong and highly directional O—H⋯O and O—H⋯Cl hydrogen bonds ensures a close and effective packing of adjacent polymeric chains.

Related literature

For general background to coordination compounds of malonates with lanthanides, see: Cañadillas-Delgado et al. (2006 ); Doreswamy et al. (2003 , 2005 ); Hernández-Molina et al. (2000 , 2002 , 2003 ). For previous research from our group on coordination compounds of phosphonates, see: Cunha-Silva et al. (2007 , 2009 ); Shi et al. (2008 ); Paz et al. (2004 , 2005 ). For general background to the synthesis of coordination polymers using microwave heating, see: Klinowski et al. (2010 ).

Experimental

Crystal data

[Ce(C₃H₂O₄)Cl(H₂O)₃]·0.5H₂O
M_r = 681.34
Monoclinic, P 2₁ /c
a = 7.6340 (2) Å
b = 14.3065 (3) Å
c = 8.7370 (2) Å
β = 99.949 (1)°
V = 939.87 (4) Å³
Z = 2
Mo Kα radiation
μ = 5.13 mm⁻¹
T = 150 K
0.26 × 0.16 × 0.16 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.349, T_max = 0.494
8271 measured reflections
2514 independent reflections
2481 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.053
S = 1.17
2514 reflections
143 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.46 e Å⁻³
Δρ_min = −1.77 e Å⁻³

Table 1
Selected bond lengths (Å)

Ce1—O1W	2.4580 (17)
Ce1—O3	2.4940 (16)
Ce1—O3W	2.5525 (18)
Ce1—O1	2.5683 (16)
Ce1—O2W	2.5895 (17)
Ce1—O2ⁱ	2.6083 (16)
Ce1—O3ⁱⁱ	2.6304 (17)
Ce1—O4ⁱⁱ	2.6487 (18)
Ce1—O1ⁱ	2.6793 (18)
Ce1—Cl1	2.9086 (6)
Symmetry codes: (i) -x+2, -y, -z+2; (ii) -x+1, -y, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1X⋯Cl1ⁱⁱⁱ	0.94 (1)	2.20 (2)	3.0967 (18)	159 (2)
O1W—H1Y⋯O2^iv	0.94 (1)	1.71 (1)	2.652 (2)	174 (3)
O2W—H2X⋯Cl1ⁱ	0.94 (1)	2.11 (1)	3.0416 (19)	171 (3)
O2W—H2Y⋯O4W^v	0.94 (1)	1.94 (2)	2.816 (4)	153 (3)
O2W—H2Y⋯O4W	0.94 (1)	2.00 (2)	2.793 (4)	141 (3)
O3W—H3X⋯O4^vi	0.95 (1)	1.86 (1)	2.798 (2)	173 (3)
O3W—H3Y⋯O2Wⁱⁱ	0.95 (3)	1.85 (3)	2.794 (3)	173 (3)
O4W—H4X⋯Cl1ⁱⁱ	0.95 (1)	2.38 (1)	3.326 (4)	176 (6)
O4W—H4Y⋯O4^vii	0.95 (1)	2.26 (4)	3.083 (4)	144 (5)
Symmetry codes: (i) -x+2, -y, -z+2; (ii) -x+1, -y, -z+2; (iii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (v) -x+1, -y, -z+1; (vi) $[-x+1, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (vii) x, y, z-1.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810044727/cv2789sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044727/cv2789Isup2.hkl

checkCIF report

Comment top

The hydro-ionothermal reaction between tetraethyl-p-xylylenebisphosphonate (texbp) and CeCl₃^.6H₂O in pre-prepared homogeneous eutectic mixtures of choline chloride and malonic acid is known to lead to the phase-pure crystalline material [Ce(Hpmd)(H₂O)] [where H₄pmd is 1,4-phenylenebis(methylene)diphosphonic acid, the hydrolysis product of texbp] (Shi et al., 2008). Following our continuous interest in the preparation and study of the properties of metal-organic frameworks based on phosphonates (Cunha-Silva et al., 2009; Cunha-Silva et al., 2007; Paz et al., 2005; Paz et al., 2004), and our recent motivation to employ microwaves as an alternative heating source (Klinowski et al., 2010), we decided to test the aforementioned synthetic conditions inside a microwave reactor. The use of microwave heating instead of hydro-ionothermal conditions resulted instead in the isolation of the title compound as a by-product, being composed of a one-dimensional polymer of Ce³⁺ with malonate residues. Noteworthy, this organic ligand can be found in a number of structures comprising lanthanide centres (Cañadillas-Delgado et al., 2006; Hernández-Molina et al., 2000; Hernández-Molina et al., 2002; Hernández -Molina et al., 2003; Doreswamy et al., 2003; Doreswamy et al. 2005) exhibiting several types of coordination modes such as unidentate, chelating and bridging.

The asymmetric unit of the title compound (see Scheme) comprises a chlorido, three water and one malonato (mal^2-) entities coordinated to Ce³⁺, and one half-occupied water molecule of crystallization located in a generic crystallographic position: [CeCl(mal)(H₂O)₃]^.0.5(H₂O). The coordination geometry of the metallic centre can be described as a highly distorted dodecahedron (Figure 1). For example, while the Ce1—O_water distances range from 2.4580 (17) to 2.5895 (17) Å (see Table 1), the Ce1—Cl1 bond is considerably longer [2.9086 (6) Å]. The malonate ligand is, on the one hand, bound to the central Ce³⁺ via distal Ce—O bonds [distances of 2.5683 (16) and 2.4940 (16) Å], leading to the formation of a six-membered chelate ring. On the other, each carboxylate establishes a physical connection with a neighbouring metallic centre via proximal chelations [Ce—O distances in the 2.6083 (16) to 2.6793 (18) Å range - see Table 1], thus forming the four-membered chelate rings depicted in the chemical diagram. These two different coordination modes of the malonate ligand lead to the formation of a one-dimensional coordination polymer running parallel to the [100] direction (Figure 2). The intermetallic distances within the polymer are of 4.3832 (2) and 4.5091 (2) Å.

Due to the large number of donors and acceptors, the crystal structure of the title compound is rich in strong [D···A distances in the 2.652 (2)–3.326 (4) Å range] and highly directional [〈 D—H···A larger than ca 141 (3)°] hydrogen bonds (see Table 2). The hydrogen bonding interactions can be divided in three different types concerning the connectivity in relation to the polymeric chain. Intra-chain hydrogen bonds add stability to the coordination polymer by connecting three adjacent metal centres through a O3W···O2W···Cl chain (blue dashed lines in Figure 2). The other two types of hydrogen bonds involve the crystal packing of adjacent coordination polymers: inter-chain interactions (green dashed lines in Figures 2 and 3) connect coordinated water molecules (O1W and O3W) of one polymer to the oxygen atoms of malonato ligands (O2 and O4, respectively) of an adjacent polymer; the second type of inter-chain interactions occur via the half-occupied crystallization water molecule (O4W) forming O4···O4W···Cl1 chains (pink dashed lines in Figures 2 and 3). The extensive hydrogen bonding network described above leads to a series of strong connections among adjacent coordination polymers as depicted in Figure 3.

Related literature top

For general background to coordination compounds of malonates with lanthanides, see: Cañadillas-Delgado et al. (2006); Doreswamy et al. (2003, 2005); Hernández-Molina et al. (2000, 2002, 2003). For previous research from our group on coordination compounds of phosphonates, see: Cunha-Silva et al. (2007, 2009); Shi et al. (2008); Paz et al. (2004, 2005). For general background to the synthesis of coordination polymers using microwave heating, see: Klinowski et al. (2010).

Experimental top

The title compound was prepared following the procedure described elsewhere (Shi et al., 2008), while replacing hydrothermal heating by microwave heating (Klinowski et al., 2010). The reactive homogeneous suspension was transferred to a 10 ml IntelliVent reactor which was placed inside a CEM Focused Microwave^TM Synthesis System Discover S-Class equipment. The reaction took place with constant magnetic stirring (controlled by the microwave equipment) and by monitoring the temperature and pressure inside the vessel. Experimental conditions: i) temperature of 120 °C; ii) power of 50 W; iii) reaction time of 45 minutes of microwave irradiation. A constant flow of air (ca 10 psi) ensured a close control of the temperature inside the vessel. After reacting a colourless solution was obtained. The resulting solution was then left to stand at ambient temperature until large block crystals grew by slow evaporation of the solvent over a period of six months.

Structure description top

For general background to coordination compounds of malonates with lanthanides, see: Cañadillas-Delgado et al. (2006); Doreswamy et al. (2003, 2005); Hernández-Molina et al. (2000, 2002, 2003). For previous research from our group on coordination compounds of phosphonates, see: Cunha-Silva et al. (2007, 2009); Shi et al. (2008); Paz et al. (2004, 2005). For general background to the synthesis of coordination polymers using microwave heating, see: Klinowski et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title compound showing all non-hydrogen atoms as displacement ellipsoids drawn at the 50% probability level and hydrogen atoms as small spheres with arbitrary radius [symmetry codes: (i)2 - x, -y, 2 - z; (ii)1 - x, -y, 2 - z]. The water molecule of crystallization, with fractional occupancy, is also depicted. For clarity, the coordination sphere of Ce1 was completed by generating by symmetry the remaining oxygen atoms.
	Fig. 2. Schematic representation of the one-dimensional chain coordination polymer composing the crystal structure of the title compound. Hydrogen bonds are represented as dashed lines: blue - intra-chain interactions; pink - hydrogen bonds with the water molecule of crystallization O4W; green - inter-chain interactions establishing direct supramolecular connections between adjacent polymers.
	Fig. 3. Crystal packing viewed in perspective along the (a) [100] and (b) [001] directions of the unit cell. Hydrogen bonds represented as in Figure 2.

catena-Poly[[triaquachlorido-µ₃-malonato-cerium(III)] hemihydrate] top

Crystal data top

[Ce(C₃H₂O₄)Cl(H₂O)₃]·0.5H₂O	F(000) = 648
M_r = 681.34	D_x = 2.408 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6974 reflections
a = 7.6340 (2) Å	θ = 3.1–29.1°
b = 14.3065 (3) Å	µ = 5.13 mm⁻¹
c = 8.7370 (2) Å	T = 150 K
β = 99.949 (1)°	Block, colourless
V = 939.87 (4) Å³	0.26 × 0.16 × 0.16 mm
Z = 2

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	2514 independent reflections
Radiation source: fine-focus sealed tube	2481 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and φ scans	θ_max = 29.1°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −7→10
T_min = 0.349, T_max = 0.494	k = −19→18
8271 measured reflections	l = −11→11

Refinement top

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)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.053	w = 1/[σ²(F_o²) + (0.0241P)² + 1.2954P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.001
2514 reflections	Δρ_max = 1.46 e Å⁻³
143 parameters	Δρ_min = −1.77 e Å⁻³
12 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0139 (5)

Crystal data top

[Ce(C₃H₂O₄)Cl(H₂O)₃]·0.5H₂O	V = 939.87 (4) Å³
M_r = 681.34	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6340 (2) Å	µ = 5.13 mm⁻¹
b = 14.3065 (3) Å	T = 150 K
c = 8.7370 (2) Å	0.26 × 0.16 × 0.16 mm
β = 99.949 (1)°

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	2514 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	2481 reflections with I > 2σ(I)
T_min = 0.349, T_max = 0.494	R_int = 0.028
8271 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	12 restraints
wR(F²) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 1.46 e Å⁻³
2514 reflections	Δρ_min = −1.77 e Å⁻³
143 parameters

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ce1	0.742523 (15)	−0.079259 (8)	0.986480 (14)	0.00713 (7)
Cl1	0.93077 (9)	−0.10017 (4)	1.30370 (7)	0.01792 (13)
O1	0.9184 (2)	0.07240 (11)	1.0558 (2)	0.0110 (3)
O2	1.1044 (2)	0.14538 (12)	1.23544 (19)	0.0126 (3)
O3	0.5892 (2)	0.03721 (11)	1.12981 (19)	0.0100 (3)
O4	0.4894 (2)	0.16117 (13)	1.2331 (2)	0.0187 (4)
C1	0.9494 (3)	0.11752 (15)	1.1829 (3)	0.0089 (4)
C2	0.8055 (3)	0.14023 (19)	1.2763 (3)	0.0166 (5)
H2A	0.8375	0.1100	1.3793	0.020*
H2B	0.8066	0.2086	1.2938	0.020*
C3	0.6181 (3)	0.11199 (16)	1.2087 (3)	0.0113 (4)
O1W	0.8161 (3)	−0.24629 (12)	1.0159 (2)	0.0186 (4)
H1X	0.844 (5)	−0.2811 (19)	0.932 (2)	0.028*
H1Y	0.844 (5)	−0.2812 (19)	1.1084 (19)	0.028*
O2W	0.7066 (2)	0.03997 (12)	0.7602 (2)	0.0139 (3)
H2X	0.815 (2)	0.065 (2)	0.740 (3)	0.021*
H2Y	0.635 (3)	0.021 (2)	0.667 (2)	0.021*
O3W	0.5195 (3)	−0.16461 (12)	1.1230 (2)	0.0185 (4)
H3X	0.518 (5)	−0.2259 (10)	1.164 (4)	0.028*
H3Y	0.439 (4)	−0.1266 (17)	1.167 (4)	0.028*
O4W	0.4133 (5)	0.0545 (3)	0.5211 (4)	0.0186 (7)	0.50
H4X	0.318 (7)	0.066 (4)	0.576 (8)	0.028*	0.50
H4Y	0.435 (9)	0.109 (3)	0.465 (7)	0.028*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.00713 (9)	0.00740 (9)	0.00779 (9)	−0.00056 (4)	0.00394 (5)	−0.00129 (3)
Cl1	0.0202 (3)	0.0217 (3)	0.0116 (3)	−0.0073 (2)	0.0020 (2)	0.0043 (2)
O1	0.0114 (8)	0.0119 (7)	0.0108 (8)	−0.0008 (6)	0.0051 (6)	−0.0046 (6)
O2	0.0086 (8)	0.0182 (8)	0.0116 (7)	−0.0021 (6)	0.0034 (6)	−0.0050 (6)
O3	0.0094 (8)	0.0096 (7)	0.0118 (7)	−0.0012 (6)	0.0040 (6)	−0.0031 (6)
O4	0.0094 (8)	0.0192 (8)	0.0285 (10)	0.0005 (7)	0.0062 (7)	−0.0146 (7)
C1	0.0091 (10)	0.0076 (9)	0.0108 (9)	0.0003 (7)	0.0038 (8)	0.0005 (7)
C2	0.0078 (11)	0.0253 (12)	0.0180 (11)	−0.0024 (9)	0.0061 (9)	−0.0128 (10)
C3	0.0095 (10)	0.0140 (10)	0.0118 (10)	−0.0024 (8)	0.0062 (8)	−0.0034 (8)
O1W	0.0330 (11)	0.0132 (8)	0.0111 (8)	0.0097 (8)	0.0078 (7)	0.0013 (6)
O2W	0.0112 (8)	0.0178 (8)	0.0133 (8)	−0.0016 (6)	0.0036 (6)	0.0001 (6)
O3W	0.0198 (9)	0.0112 (7)	0.0288 (10)	0.0021 (7)	0.0159 (8)	0.0049 (7)
O4W	0.0189 (19)	0.0240 (18)	0.0134 (16)	0.0028 (16)	0.0043 (14)	0.0011 (14)

Geometric parameters (Å, º) top

Ce1—O1W	2.4580 (17)	O3—Ce1ⁱⁱ	2.6304 (17)
Ce1—O3	2.4940 (16)	O4—C3	1.256 (3)
Ce1—O3W	2.5525 (18)	O4—Ce1ⁱⁱ	2.6487 (18)
Ce1—O1	2.5683 (16)	C1—C2	1.512 (3)
Ce1—O2W	2.5895 (17)	C1—Ce1ⁱ	3.038 (2)
Ce1—O2ⁱ	2.6083 (16)	C2—C3	1.505 (3)
Ce1—O3ⁱⁱ	2.6304 (17)	C2—H2A	0.9900
Ce1—O4ⁱⁱ	2.6487 (18)	C2—H2B	0.9900
Ce1—O1ⁱ	2.6793 (18)	C3—Ce1ⁱⁱ	3.014 (2)
Ce1—Cl1	2.9086 (6)	O1W—H1X	0.943 (10)
Ce1—C3ⁱⁱ	3.014 (2)	O1W—H1Y	0.943 (10)
Ce1—C1ⁱ	3.038 (2)	O2W—H2X	0.944 (10)
O1—C1	1.271 (3)	O2W—H2Y	0.941 (10)
O1—Ce1ⁱ	2.6793 (18)	O3W—H3X	0.947 (10)
O2—C1	1.258 (3)	O3W—H3Y	0.95 (3)
O2—Ce1ⁱ	2.6083 (16)	O4W—H4X	0.947 (10)
O3—C3	1.271 (3)	O4W—H4Y	0.947 (10)

O1W—Ce1—O3	135.69 (6)	O3ⁱⁱ—Ce1—C3ⁱⁱ	24.86 (5)
O1W—Ce1—O3W	69.19 (6)	O4ⁱⁱ—Ce1—C3ⁱⁱ	24.56 (6)
O3—Ce1—O3W	71.11 (5)	O1ⁱ—Ce1—C3ⁱⁱ	137.52 (6)
O1W—Ce1—O1	134.11 (7)	Cl1—Ce1—C3ⁱⁱ	140.88 (5)
O3—Ce1—O1	65.71 (5)	O1W—Ce1—C1ⁱ	72.16 (6)
O3W—Ce1—O1	131.12 (6)	O3—Ce1—C1ⁱ	146.63 (6)
O1W—Ce1—O2W	135.43 (6)	O3W—Ce1—C1ⁱ	140.97 (6)
O3—Ce1—O2W	86.92 (5)	O1—Ce1—C1ⁱ	81.37 (6)
O3W—Ce1—O2W	132.90 (6)	O2W—Ce1—C1ⁱ	74.66 (6)
O1—Ce1—O2W	66.78 (6)	O2ⁱ—Ce1—C1ⁱ	24.25 (6)
O1W—Ce1—O2ⁱ	66.52 (6)	O3ⁱⁱ—Ce1—C1ⁱ	128.90 (6)
O3—Ce1—O2ⁱ	157.66 (5)	O4ⁱⁱ—Ce1—C1ⁱ	92.55 (6)
O3W—Ce1—O2ⁱ	126.49 (6)	O1ⁱ—Ce1—C1ⁱ	24.68 (6)
O1—Ce1—O2ⁱ	101.46 (5)	Cl1—Ce1—C1ⁱ	98.57 (4)
O2W—Ce1—O2ⁱ	70.93 (5)	C3ⁱⁱ—Ce1—C1ⁱ	113.88 (6)
O1W—Ce1—O3ⁱⁱ	116.75 (6)	C1—O1—Ce1	130.24 (15)
O3—Ce1—O3ⁱⁱ	62.43 (6)	C1—O1—Ce1ⁱ	93.64 (14)
O3W—Ce1—O3ⁱⁱ	67.32 (6)	Ce1—O1—Ce1ⁱ	118.46 (6)
O1—Ce1—O3ⁱⁱ	109.09 (5)	C1—O2—Ce1ⁱ	97.36 (13)
O2W—Ce1—O3ⁱⁱ	65.58 (5)	C3—O3—Ce1	141.45 (15)
O2ⁱ—Ce1—O3ⁱⁱ	108.72 (5)	C3—O3—Ce1ⁱⁱ	94.72 (14)
O1W—Ce1—O4ⁱⁱ	75.98 (6)	Ce1—O3—Ce1ⁱⁱ	117.57 (6)
O3—Ce1—O4ⁱⁱ	110.26 (5)	C3—O4—Ce1ⁱⁱ	94.24 (14)
O3W—Ce1—O4ⁱⁱ	73.16 (6)	O2—C1—O1	120.1 (2)
O1—Ce1—O4ⁱⁱ	143.27 (6)	O2—C1—C2	117.4 (2)
O2W—Ce1—O4ⁱⁱ	76.65 (6)	O1—C1—C2	122.5 (2)
O2ⁱ—Ce1—O4ⁱⁱ	68.32 (5)	O2—C1—Ce1ⁱ	58.39 (12)
O3ⁱⁱ—Ce1—O4ⁱⁱ	48.92 (5)	O1—C1—Ce1ⁱ	61.67 (12)
O1W—Ce1—O1ⁱ	80.87 (6)	C2—C1—Ce1ⁱ	175.81 (16)
O3—Ce1—O1ⁱ	126.38 (5)	C3—C2—C1	117.41 (19)
O3W—Ce1—O1ⁱ	145.13 (6)	C3—C2—H2A	107.9
O1—Ce1—O1ⁱ	61.54 (6)	C1—C2—H2A	107.9
O2W—Ce1—O1ⁱ	81.26 (6)	C3—C2—H2B	107.9
O2ⁱ—Ce1—O1ⁱ	48.93 (5)	C1—C2—H2B	107.9
O3ⁱⁱ—Ce1—O1ⁱ	145.80 (5)	H2A—C2—H2B	107.2
O4ⁱⁱ—Ce1—O1ⁱ	117.21 (5)	O4—C3—O3	119.7 (2)
O1W—Ce1—Cl1	74.57 (5)	O4—C3—C2	120.1 (2)
O3—Ce1—Cl1	77.74 (4)	O3—C3—C2	120.2 (2)
O3W—Ce1—Cl1	76.42 (5)	O4—C3—Ce1ⁱⁱ	61.20 (12)
O1—Ce1—Cl1	73.15 (4)	O3—C3—Ce1ⁱⁱ	60.43 (12)
O2W—Ce1—Cl1	139.90 (4)	C2—C3—Ce1ⁱⁱ	167.62 (17)
O2ⁱ—Ce1—Cl1	117.38 (4)	Ce1—O1W—H1X	120.7 (18)
O3ⁱⁱ—Ce1—Cl1	132.52 (4)	Ce1—O1W—H1Y	128.3 (18)
O4ⁱⁱ—Ce1—Cl1	143.42 (5)	H1X—O1W—H1Y	109.8 (14)
O1ⁱ—Ce1—Cl1	78.76 (4)	Ce1—O2W—H2X	114 (2)
O1W—Ce1—C3ⁱⁱ	94.47 (7)	Ce1—O2W—H2Y	116.0 (19)
O3—Ce1—C3ⁱⁱ	85.75 (6)	H2X—O2W—H2Y	110.2 (15)
O3W—Ce1—C3ⁱⁱ	64.67 (6)	Ce1—O3W—H3X	132.1 (19)
O1—Ce1—C3ⁱⁱ	130.83 (6)	Ce1—O3W—H3Y	116.4 (19)
O2W—Ce1—C3ⁱⁱ	72.81 (6)	H3X—O3W—H3Y	109 (3)
O2ⁱ—Ce1—C3ⁱⁱ	90.33 (6)	H4X—O4W—H4Y	110.0 (16)

O1W—Ce1—O1—C1	−84.6 (2)	C1ⁱ—Ce1—O3—C3	−23.8 (3)
O3—Ce1—O1—C1	46.42 (19)	O1W—Ce1—O3—Ce1ⁱⁱ	−101.07 (10)
O3W—Ce1—O1—C1	16.4 (2)	O3W—Ce1—O3—Ce1ⁱⁱ	−73.68 (8)
O2W—Ce1—O1—C1	143.9 (2)	O1—Ce1—O3—Ce1ⁱⁱ	129.82 (8)
O2ⁱ—Ce1—O1—C1	−152.87 (19)	O2W—Ce1—O3—Ce1ⁱⁱ	63.96 (7)
O3ⁱⁱ—Ce1—O1—C1	92.5 (2)	O2ⁱ—Ce1—O3—Ce1ⁱⁱ	71.47 (16)
O4ⁱⁱ—Ce1—O1—C1	138.16 (18)	O3ⁱⁱ—Ce1—O3—Ce1ⁱⁱ	0.0
O1ⁱ—Ce1—O1—C1	−123.6 (2)	O4ⁱⁱ—Ce1—O3—Ce1ⁱⁱ	−10.60 (9)
Cl1—Ce1—O1—C1	−37.46 (19)	O1ⁱ—Ce1—O3—Ce1ⁱⁱ	140.74 (6)
C3ⁱⁱ—Ce1—O1—C1	106.6 (2)	Cl1—Ce1—O3—Ce1ⁱⁱ	−153.33 (7)
C1ⁱ—Ce1—O1—C1	−139.21 (18)	C3ⁱⁱ—Ce1—O3—Ce1ⁱⁱ	−9.01 (7)
O1W—Ce1—O1—Ce1ⁱ	39.03 (11)	C1ⁱ—Ce1—O3—Ce1ⁱⁱ	119.68 (10)
O3—Ce1—O1—Ce1ⁱ	170.01 (9)	Ce1ⁱ—O2—C1—O1	−0.2 (2)
O3W—Ce1—O1—Ce1ⁱ	139.96 (7)	Ce1ⁱ—O2—C1—C2	179.99 (18)
O2W—Ce1—O1—Ce1ⁱ	−92.54 (8)	Ce1—O1—C1—O2	133.00 (19)
O2ⁱ—Ce1—O1—Ce1ⁱ	−29.27 (8)	Ce1ⁱ—O1—C1—O2	0.2 (2)
O3ⁱⁱ—Ce1—O1—Ce1ⁱ	−143.90 (7)	Ce1—O1—C1—C2	−47.2 (3)
O4ⁱⁱ—Ce1—O1—Ce1ⁱ	−98.25 (10)	Ce1ⁱ—O1—C1—C2	180.0 (2)
O1ⁱ—Ce1—O1—Ce1ⁱ	0.0	Ce1—O1—C1—Ce1ⁱ	132.79 (18)
Cl1—Ce1—O1—Ce1ⁱ	86.13 (7)	O2—C1—C2—C3	176.4 (2)
C3ⁱⁱ—Ce1—O1—Ce1ⁱ	−129.82 (8)	O1—C1—C2—C3	−3.4 (4)
C1ⁱ—Ce1—O1—Ce1ⁱ	−15.61 (7)	Ce1ⁱⁱ—O4—C3—O3	−15.7 (2)
O1W—Ce1—O3—C3	115.4 (2)	Ce1ⁱⁱ—O4—C3—C2	165.9 (2)
O3W—Ce1—O3—C3	142.8 (3)	Ce1—O3—C3—O4	163.95 (17)
O1—Ce1—O3—C3	−13.7 (2)	Ce1ⁱⁱ—O3—C3—O4	15.9 (2)
O2W—Ce1—O3—C3	−79.6 (2)	Ce1—O3—C3—C2	−17.7 (4)
O2ⁱ—Ce1—O3—C3	−72.1 (3)	Ce1ⁱⁱ—O3—C3—C2	−165.7 (2)
O3ⁱⁱ—Ce1—O3—C3	−143.5 (3)	Ce1—O3—C3—Ce1ⁱⁱ	148.1 (2)
O4ⁱⁱ—Ce1—O3—C3	−154.1 (2)	C1—C2—C3—O4	−146.9 (2)
O1ⁱ—Ce1—O3—C3	−2.8 (3)	C1—C2—C3—O3	34.7 (3)
Cl1—Ce1—O3—C3	63.1 (2)	C1—C2—C3—Ce1ⁱⁱ	−54.5 (8)
C3ⁱⁱ—Ce1—O3—C3	−152.5 (2)

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1X···Cl1ⁱⁱⁱ	0.94 (1)	2.20 (2)	3.0967 (18)	159 (2)
O1W—H1Y···O2^iv	0.94 (1)	1.71 (1)	2.652 (2)	174 (3)
O2W—H2X···Cl1ⁱ	0.94 (1)	2.11 (1)	3.0416 (19)	171 (3)
O2W—H2Y···O4W^v	0.94 (1)	1.94 (2)	2.816 (4)	153 (3)
O2W—H2Y···O4W	0.94 (1)	2.00 (2)	2.793 (4)	141 (3)
O3W—H3X···O4^vi	0.95 (1)	1.86 (1)	2.798 (2)	173 (3)
O3W—H3Y···O2Wⁱⁱ	0.95 (3)	1.85 (3)	2.794 (3)	173 (3)
O4W—H4X···Cl1ⁱⁱ	0.95 (1)	2.38 (1)	3.326 (4)	176 (6)
O4W—H4Y···O4^vii	0.95 (1)	2.26 (4)	3.083 (4)	144 (5)

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y, −z+2; (iii) x, −y−1/2, z−1/2; (iv) −x+2, y−1/2, −z+5/2; (v) −x+1, −y, −z+1; (vi) −x+1, y−1/2, −z+5/2; (vii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[Ce(C₃H₂O₄)Cl(H₂O)₃]·0.5H₂O
M_r	681.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.6340 (2), 14.3065 (3), 8.7370 (2)
β (°)	99.949 (1)
V (Å³)	939.87 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.13
Crystal size (mm)	0.26 × 0.16 × 0.16

Data collection
Diffractometer	Bruker X8 Kappa CCD APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.349, 0.494
No. of measured, independent and observed [I > 2σ(I)] reflections	8271, 2514, 2481
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.053, 1.17
No. of reflections	2514
No. of parameters	143
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.46, −1.77

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Selected bond lengths (Å) top

Ce1—O1W	2.4580 (17)	Ce1—O2ⁱ	2.6083 (16)
Ce1—O3	2.4940 (16)	Ce1—O3ⁱⁱ	2.6304 (17)
Ce1—O3W	2.5525 (18)	Ce1—O4ⁱⁱ	2.6487 (18)
Ce1—O1	2.5683 (16)	Ce1—O1ⁱ	2.6793 (18)
Ce1—O2W	2.5895 (17)	Ce1—Cl1	2.9086 (6)

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1X···Cl1ⁱⁱⁱ	0.943 (10)	2.197 (15)	3.0967 (18)	159 (2)
O1W—H1Y···O2^iv	0.943 (10)	1.712 (11)	2.652 (2)	174 (3)
O2W—H2X···Cl1ⁱ	0.944 (10)	2.106 (11)	3.0416 (19)	171 (3)
O2W—H2Y···O4W^v	0.941 (10)	1.944 (18)	2.816 (4)	153 (3)
O2W—H2Y···O4W	0.941 (10)	2.00 (2)	2.793 (4)	141 (3)
O3W—H3X···O4^vi	0.947 (10)	1.856 (11)	2.798 (2)	173 (3)
O3W—H3Y···O2Wⁱⁱ	0.95 (3)	1.85 (3)	2.794 (3)	173 (3)
O4W—H4X···Cl1ⁱⁱ	0.947 (10)	2.380 (12)	3.326 (4)	176 (6)
O4W—H4Y···O4^vii	0.947 (10)	2.26 (4)	3.083 (4)	144 (5)

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their financial support through the R&D project PTDC/QUI-QUI/098098/2008 (FCOMP-01–0124-FEDER-010785), the PhD and post-doctoral research grants Nos. SFRH/BD/46601/2008 (to PS) and SFRH/BPD/63736/2009 (to JAF), respectively, and also for specific funding for the purchase of the single-crystal diffractometer.

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