Poly[hexa­aqua­tri-μ-malonato-didysprosium(III)]

Fang, Z.-Q.; Zeng, R.-H.; Song, Z.-F.; Yang, M.

doi:10.1107/S1600536808015961

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m877

doi:10.1107/S1600536808015961

Open

access

Poly[hexaaquatri-μ-malonato-didysprosium(III)]

Zhan-Qiang Fang,^a ^* Rong-Hua Zeng,^a Zhao-Feng Song ^a and Mei Yang ^a

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: zhqfang77@yahoo.com.cn

(Received 24 April 2008; accepted 27 May 2008; online 7 June 2008)

The title compound, [Dy₂(C₃H₂O₄)₃(H₂O)₆]_n, forms a coordination polymeric structure comprising hydrated dysprosium ions and malonate ligands. In the asymmetric unit, there are one dysprosium ion, one and a half malonate ligands, and three water molecules. Each Dy^III atom is coordinated by six O atoms from four malonate ligands and by three water molecules, and displays a tricapped trigonal–prismatic coordination geometry. The malonate ligands adopt two types of coordination mode, linking dysprosium centres to form a three-dimensional coordination polymer. The extensive network of hydrogen bonds in this polymer enhances the structural stability.

Related literature

For related literature, see: Iglesias et al. (2003 ); Kim et al. (2003 ); Moulton & Zaworotko (2001 ).

Experimental

Crystal data

[Dy₂(C₃H₂O₄)₃(H₂O)₆]
M_r = 739.23
Monoclinic, C 2/c
a = 17.1805 (2) Å
b = 12.3124 (1) Å
c = 11.1541 (1) Å
β = 127.52 (2)°
V = 1871.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 8.02 mm⁻¹
T = 296 (2) K
0.11 × 0.10 × 0.08 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2004 ) T_min = 0.435, T_max = 0.529
10051 measured reflections
2136 independent reflections
2001 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.053
S = 1.07
2136 reflections
132 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O5ⁱ	0.82	2.04	2.854 (4)	172
O1W—H2W⋯O3ⁱⁱ	0.81	1.94	2.729 (4)	165
O2W—H3W⋯O3ⁱⁱⁱ	0.82	1.95	2.761 (4)	170
O3W—H6W⋯O4ⁱⁱⁱ	0.81	2.02	2.802 (4)	160
O3W—H6W⋯O3ⁱⁱⁱ	0.81	2.59	3.291 (4)	144
O3W—H5W⋯O2^iv	0.81	1.96	2.738 (4)	161
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[x, -y, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015961/dn2344sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015961/dn2344Isup2.hkl

checkCIF report

Comment top

Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Kim et al., 2003; Iglesias et al., 2003; Moulton & Zaworotko, 2001). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metals ions and bridging building blocks as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. Recently, we obtained the title compound, (I), by the hydrothermal reaction of Dy(NO₃)₃ with malonic acid in alkaline aqueous solution.

As illustrated in Fig. 1, in the asymmetric unit of complex (I), each Dy^III centre is coordinated by six carboxyl O atoms from four malonate ligands, and three water molecules. The two unique malonate ligands act as two types of chelating and bridging modes: one lies on an inversion centre and uses each carboxylate group to bond to two Dy^III ions; one uses three carboxyl O atoms to coordinate to two Dy^III ions involving a six-membered chelate ring. The adjacent Dy···Dy separations are 4.303 (3), 6.600 (1) and 6.982 (2) Å respectively. The ligands link dysprosium centres to form a three-dimensional coordination polymer which is also stabilized by the extensive network of hydrogen bonding interactions (Fig. 2; Table 1).

Related literature top

For related literature, see: Iglesias et al. (2003); Kim et al. (2003); Moulton & Zaworotko (2001).

Experimental top

A mixture of Dy(NO₃)₃ (0.1 mmol), malonato acid (0.15 mmol), NaOH (0.1 mmol), water (10 ml) was stirred vigorously for 20 min and then sealed in a Teflon-lined stainless-steel autoclave (20 ml, capacity). The autoclave was heated to and maintained at 433 K for 7 days, and then cooled to room temperature at 5 K h^-1 to obtain the colorless block crystals.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure showing the atomic-numbering scheme. Displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1-x, y, 3/2-y; (ii) 1/2-x, y-1/2, 1/2-z; (iii) 1/2-x, 1/2-y, 1-z]
	Fig. 2. The molecular packing showing the intra/intermolecular hydrogen bonding interactions as broken lines.

Poly[hexaaquatri-µ-malonato-didysprosium(III)] top

Crystal data top

[Dy₂(C₃H₂O₄)₃(H₂O)₆]	F(000) = 1392
M_r = 739.23	D_x = 2.624 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6377 reflections
a = 17.1805 (2) Å	θ = 1.7–28.0°
b = 12.3124 (1) Å	µ = 8.02 mm⁻¹
c = 11.1541 (1) Å	T = 296 K
β = 127.52 (2)°	Block, colorless
V = 1871.4 (5) Å³	0.11 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	2136 independent reflections
Radiation source: fine-focus sealed tube	2001 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (APEX2; Bruker, 2004)	h = −22→20
T_min = 0.435, T_max = 0.529	k = −15→15
10051 measured reflections	l = −12→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0241P)² + 12.727P] where P = (F_o² + 2F_c²)/3
2136 reflections	(Δ/σ)_max = 0.001
132 parameters	Δρ_max = 0.91 e Å⁻³
10 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

[Dy₂(C₃H₂O₄)₃(H₂O)₆]	V = 1871.4 (5) Å³
M_r = 739.23	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.1805 (2) Å	µ = 8.02 mm⁻¹
b = 12.3124 (1) Å	T = 296 K
c = 11.1541 (1) Å	0.11 × 0.10 × 0.08 mm
β = 127.52 (2)°

Data collection top

Bruker APEXII area-detector diffractometer	2136 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2004)	2001 reflections with I > 2σ(I)
T_min = 0.435, T_max = 0.529	R_int = 0.023
10051 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	10 restraints
wR(F²) = 0.053	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0241P)² + 12.727P] where P = (F_o² + 2F_c²)/3
2136 reflections	Δρ_max = 0.91 e Å⁻³
132 parameters	Δρ_min = −0.51 e Å⁻³

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)
C1	0.3116 (3)	0.3839 (3)	0.2419 (4)	0.0139 (7)
C2	0.3805 (3)	0.3285 (3)	0.2198 (5)	0.0174 (7)
H2A	0.4462	0.3325	0.3148	0.021*
H2B	0.3808	0.3704	0.1464	0.021*
C3	0.3607 (3)	0.2110 (3)	0.1686 (4)	0.0137 (7)
C4	0.4246 (2)	0.2993 (3)	0.6243 (4)	0.0119 (7)
C5	0.5000	0.3747 (4)	0.7500	0.0135 (10)
H5A	0.4703	0.4205	0.7829	0.016*	0.50
H5B	0.5297	0.4205	0.7171	0.016*	0.50
Dy1	0.283235 (12)	0.148077 (13)	0.379865 (19)	0.01461 (7)
O1	0.2989 (2)	0.4832 (2)	0.2144 (4)	0.0268 (6)
O2	0.2741 (2)	0.3315 (2)	0.2918 (3)	0.0165 (5)
O3	0.3717 (2)	0.1844 (2)	0.0723 (3)	0.0256 (6)
O4	0.3355 (2)	0.14437 (19)	0.2259 (3)	0.0200 (6)
O5	0.44917 (18)	0.2424 (2)	0.5591 (3)	0.0192 (5)
O6	0.34060 (17)	0.2909 (2)	0.5918 (3)	0.0144 (5)
O1W	0.1257 (2)	0.1789 (2)	0.1179 (3)	0.0226 (6)
H1W	0.0785	0.2029	0.1100	0.034*
H2W	0.1369	0.2230	0.0756	0.034*
O2W	0.4141 (3)	0.0048 (3)	0.4897 (5)	0.0435 (10)
H3W	0.4088	−0.0512	0.5238	0.065*
H4W	0.4700	0.0253	0.5538	0.065*
O3W	0.3194 (2)	0.0640 (2)	0.6116 (4)	0.0322 (7)
H6W	0.3294	−0.0003	0.6333	0.048*
H5W	0.3019	0.0889	0.6593	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0179 (17)	0.0087 (15)	0.0121 (17)	0.0002 (13)	0.0077 (15)	−0.0012 (13)
C2	0.0267 (19)	0.0119 (16)	0.024 (2)	−0.0038 (14)	0.0211 (18)	−0.0010 (14)
C3	0.0166 (17)	0.0121 (16)	0.0163 (18)	−0.0007 (13)	0.0119 (15)	−0.0004 (13)
C4	0.0099 (15)	0.0139 (16)	0.0082 (16)	−0.0002 (12)	0.0037 (14)	0.0026 (13)
C5	0.010 (2)	0.011 (2)	0.014 (2)	0.000	0.005 (2)	0.000
Dy1	0.01901 (10)	0.01230 (10)	0.01759 (11)	−0.00036 (6)	0.01376 (8)	−0.00016 (6)
O1	0.0366 (17)	0.0102 (12)	0.0372 (18)	0.0042 (11)	0.0244 (15)	0.0062 (12)
O2	0.0249 (14)	0.0116 (12)	0.0203 (14)	0.0034 (10)	0.0175 (12)	0.0027 (10)
O3	0.0474 (18)	0.0187 (14)	0.0288 (16)	−0.0005 (13)	0.0326 (16)	−0.0014 (12)
O4	0.0366 (16)	0.0100 (12)	0.0276 (16)	−0.0013 (10)	0.0270 (14)	−0.0012 (10)
O5	0.0137 (12)	0.0264 (14)	0.0183 (13)	−0.0008 (10)	0.0102 (11)	−0.0068 (11)
O6	0.0104 (11)	0.0196 (13)	0.0131 (12)	−0.0015 (9)	0.0072 (10)	−0.0016 (10)
O1W	0.0206 (14)	0.0300 (15)	0.0198 (15)	−0.0003 (12)	0.0137 (12)	0.0065 (12)
O2W	0.0431 (19)	0.0277 (17)	0.085 (3)	0.0166 (15)	0.052 (2)	0.0281 (18)
O3W	0.063 (2)	0.0176 (14)	0.0415 (19)	0.0177 (14)	0.0450 (18)	0.0154 (13)

Geometric parameters (Å, º) top

C1—O1	1.247 (4)	Dy1—O4	2.375 (3)
C1—O2	1.256 (4)	Dy1—O2	2.430 (2)
C1—C2	1.512 (5)	Dy1—O6ⁱⁱⁱ	2.452 (2)
C2—C3	1.516 (5)	Dy1—O3W	2.487 (3)
C2—H2A	0.9700	Dy1—O2W	2.513 (3)
C2—H2B	0.9700	Dy1—O1W	2.524 (3)
C3—O3	1.243 (4)	Dy1—O5	2.555 (3)
C3—O4	1.266 (4)	Dy1—O6	2.610 (2)
C4—O5	1.254 (4)	O1W—H1W	0.8155
C4—O6	1.260 (4)	O1W—H2W	0.8146
C4—C5	1.514 (4)	O2W—H3W	0.8184
C5—C4ⁱ	1.514 (4)	O2W—H4W	0.8133
C5—H5A	0.9700	O3W—H6W	0.8149
C5—H5B	0.9700	O3W—H5W	0.8144
Dy1—O1ⁱⁱ	2.326 (3)

O1—C1—O2	123.5 (3)	O4—Dy1—O1W	77.10 (10)
O1—C1—C2	116.0 (3)	O2—Dy1—O1W	68.42 (9)
O2—C1—C2	120.4 (3)	O6ⁱⁱⁱ—Dy1—O1W	72.58 (9)
C1—C2—C3	118.3 (3)	O3W—Dy1—O1W	132.74 (10)
C1—C2—H2A	107.7	O2W—Dy1—O1W	132.85 (12)
C3—C2—H2A	107.7	O1ⁱⁱ—Dy1—O5	146.20 (10)
C1—C2—H2B	107.7	O4—Dy1—O5	80.87 (9)
C3—C2—H2B	107.7	O2—Dy1—O5	70.15 (9)
H2A—C2—H2B	107.1	O6ⁱⁱⁱ—Dy1—O5	113.70 (8)
O3—C3—O4	123.0 (3)	O3W—Dy1—O5	85.58 (10)
O3—C3—C2	117.3 (3)	O2W—Dy1—O5	72.37 (10)
O4—C3—C2	119.7 (3)	O1W—Dy1—O5	137.36 (9)
O5—C4—O6	121.2 (3)	O1ⁱⁱ—Dy1—O6	141.99 (9)
O5—C4—C5	118.7 (3)	O4—Dy1—O6	124.57 (8)
O6—C4—C5	120.1 (3)	O2—Dy1—O6	68.62 (8)
C4—C5—C4ⁱ	104.4 (4)	O6ⁱⁱⁱ—Dy1—O6	63.60 (9)
C4—C5—H5A	110.9	O3W—Dy1—O6	67.78 (9)
C4ⁱ—C5—H5A	110.9	O2W—Dy1—O6	107.42 (11)
C4—C5—H5B	110.9	O1W—Dy1—O6	119.61 (9)
C4ⁱ—C5—H5B	110.9	O5—Dy1—O6	50.15 (8)
H5A—C5—H5B	108.9	C1—O1—Dy1^iv	159.0 (3)
O1ⁱⁱ—Dy1—O4	92.80 (10)	C1—O2—Dy1	137.0 (2)
O1ⁱⁱ—Dy1—O2	139.15 (10)	C3—O4—Dy1	138.4 (2)
O4—Dy1—O2	71.67 (8)	C4—O5—Dy1	95.7 (2)
O1ⁱⁱ—Dy1—O6ⁱⁱⁱ	89.46 (9)	C4—O6—Dy1ⁱⁱⁱ	150.4 (2)
O4—Dy1—O6ⁱⁱⁱ	147.09 (9)	C4—O6—Dy1	92.9 (2)
O2—Dy1—O6ⁱⁱⁱ	85.38 (8)	Dy1ⁱⁱⁱ—O6—Dy1	116.40 (9)
O1ⁱⁱ—Dy1—O3W	78.76 (11)	Dy1—O1W—H1W	118.3
O4—Dy1—O3W	141.16 (9)	Dy1—O1W—H2W	107.9
O2—Dy1—O3W	136.14 (9)	H1W—O1W—H2W	105.4
O6ⁱⁱⁱ—Dy1—O3W	71.36 (9)	Dy1—O2W—H3W	119.8
O1ⁱⁱ—Dy1—O2W	73.98 (11)	Dy1—O2W—H4W	115.9
O4—Dy1—O2W	73.66 (10)	H3W—O2W—H4W	105.1
O2—Dy1—O2W	131.94 (9)	Dy1—O3W—H6W	126.0
O6ⁱⁱⁱ—Dy1—O2W	137.86 (9)	Dy1—O3W—H5W	124.4
O3W—Dy1—O2W	67.55 (10)	H6W—O3W—H5W	105.5
O1ⁱⁱ—Dy1—O1W	71.37 (10)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, −y+1/2, −z+1; (iv) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O5^v	0.82	2.04	2.854 (4)	172
O1W—H2W···O3^vi	0.81	1.94	2.729 (4)	165
O2W—H3W···O3^vii	0.82	1.95	2.761 (4)	170
O3W—H6W···O4^vii	0.81	2.02	2.802 (4)	160
O3W—H6W···O3^vii	0.81	2.59	3.291 (4)	144
O3W—H5W···O2ⁱⁱⁱ	0.81	1.96	2.738 (4)	161

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

Experimental details

Crystal data
Chemical formula	[Dy₂(C₃H₂O₄)₃(H₂O)₆]
M_r	739.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	17.1805 (2), 12.3124 (1), 11.1541 (1)
β (°)	127.52 (2)
V (Å³)	1871.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.02
Crystal size (mm)	0.11 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2004)
T_min, T_max	0.435, 0.529
No. of measured, independent and observed [I > 2σ(I)] reflections	10051, 2136, 2001
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.053, 1.07
No. of reflections	2136
No. of parameters	132
No. of restraints	10
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0241P)² + 12.727P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.51

Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O5ⁱ	0.82	2.04	2.854 (4)	172.1
O1W—H2W···O3ⁱⁱ	0.81	1.94	2.729 (4)	164.5
O2W—H3W···O3ⁱⁱⁱ	0.82	1.95	2.761 (4)	169.7
O3W—H6W···O4ⁱⁱⁱ	0.81	2.02	2.802 (4)	160.0
O3W—H6W···O3ⁱⁱⁱ	0.81	2.59	3.291 (4)	144.4
O3W—H5W···O2^iv	0.81	1.96	2.738 (4)	161.0

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

Acknowledgements

The authors acknowledge South China Normal University for supporting this work.

References

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Iglesias, S., Castillo, O., Luque, A. & Romaan, P. (2003). Inorg. Chim. Acta, 349, 273–278. Web of Science CSD CrossRef CAS Google Scholar
Kim, J. C., Jo, H., Lough, A. J., Cho, J., Lee, U. & Pyun, S. Y. (2003). Inorg. Chem. Commun. 6, 474–477. Web of Science CSD CrossRef CAS Google Scholar
Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar