catena-Poly[[triaqua-chlorido-μ(3)-malonato-cerium(III)] hemihydrate].

The asymmetric unit of the title compound, {[Ce(C(3)H(2)O(4))Cl(H(2)O)(3)]·0.5H(2)O}(n), contains a Ce(3+) atom coordinated by a chloride anion, three water mol-ecules and a malonate ligand, and one water mol-ecule 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 supra-molecular 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 = 681.34

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.053

S = 1.17

2514 reflections

143 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.46 e Å−3

Δρmin = −1.77 e Å−3

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044727/cv2789Isup2.hkl

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

[Ce(C3H2O4)Cl(H2O)3]·0.5H2O	F(000) = 648
Mr = 681.34	Dx = 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

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

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(Fo2) + (0.0241P)2 + 1.2954P] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max = 0.001
2514 reflections	Δρmax = 1.46 e Å−3
143 parameters	Δρmin = −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)

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	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

	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)

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)

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···O2iv	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···O4Wv	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···O4vi	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···O4vii	0.95 (1)	2.26 (4)	3.083 (4)	144 (5)

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) ; (ii) .

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⋯O2iv	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⋯O4Wv	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⋯O4vi	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⋯O4vii	0.95 (1)	2.26 (4)	3.083 (4)	144 (5)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .