Poly[[tetra­aquadi-μ4-fumarato-μ2-oxalato-dierbium(III)] tetra­hydrate]

Yang, Q.-F.; Wang, X.-Z.; Xue, P.

doi:10.1107/S160053681205026X

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page m52

https://doi.org/10.1107/S160053681205026X

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Poly[[tetraaquadi-μ₄-fumarato-μ₂-oxalato-dierbium(III)] tetrahydrate]

Qing-Feng Yang,^a ^* Xiao-Zhong Wang ^b and Ping Xue ^a

^aKey Laboratory of Energy Resources and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, People's Republic of China
^*Correspondence e-mail: yangqf@nxu.edu.cn

(Received 14 November 2012; accepted 10 December 2012; online 15 December 2012)

The title compound, {[Er₂(C₄H₂O₄)₂(C₂O₄)(H₂O)₄]·4H₂O}_n, was synthesized by the reaction of erbium nitrate hexahydrate with fumaric acid and oxalic acid under hydrothermal conditions. The Er³⁺ cation (site symmetry ..2) is eight-coordinated by six O atoms from four fumarate anions (site symmetry ..2) and one bidentate oxalate anion (site symmetry 222), and by two water molecules. The complex exhibits a three-dimensional structure consisting of oxalate pillared Er–fumarate layers with channels occupied by coordinating and lattice water molecules. The three-dimensional structure features by O_water—H⋯O hydrogen bonds involving both the coordinating and lattice water molecules.

Related literature

For lanthanide–metal complexes containing fumarate ligands, see: Zhang et al. (2006 ). For lanthanide-containing structures with metal-organic frameworks and two different flexible carboxylate ligands, see: Zhang et al. (2008 ); Zhu et al. (2007 ).

Experimental

Crystal data

[Er₂(C₄H₂O₄)₂(C₂O₄)(H₂O)₄]·4H₂O
M_r = 794.78
Orthorhombic, F d d d
a = 9.6016 (19) Å
b = 15.701 (3) Å
c = 26.722 (5) Å
V = 4028.5 (14) Å³
Z = 8
Mo Kα radiation
μ = 8.38 mm⁻¹
T = 293 K
0.19 × 0.16 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.305, T_max = 0.402
9284 measured reflections
1162 independent reflections
1088 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.045
S = 1.11
1162 reflections
74 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O5ⁱ	0.85	2.35	3.045 (5)	139
O4—H4B⋯O3ⁱⁱ	0.85	1.91	2.750 (3)	168
O5—H5A⋯O4	0.85	1.99	2.836	180
O5—H5B⋯O2ⁱⁱⁱ	0.85	2.36	2.938 (4)	125
Symmetry codes: (i) $[-x+{\script{3\over 4}}, y, -z+{\script{3\over 4}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681205026X/hg5272sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681205026X/hg5272Isup2.hkl

checkCIF report

Comment top

In recent years, lanthanide metal-organic compounds have been of great interest due to their fascinating structures and potential applications in magnetism, luminescence, catalysis, gas storage and separation. Multitopic carboxylates have received considerable study due to their availability and potential for allowing for the tailored design of such frameworks. As we know, fumaric acid is a unique ligand with a relatively small, conjugated middle part and versatile coordination modes. A large number of lanthanide metal complexes containing fumarate ligands have been reported, see: Zhang et al. (2006). And lanthanide-containing MOFs with two different flexible carboxylate ligands are less developed, see: Zhang et al.(2008); Zhu et al.(2007). In this paper, we report the synthesis and structure of a new metal-organic compound constructed from fumarate ligands coordinated to Er atoms in the presence of oxalate ligands.

In the title compound I, Er1 is eight-coordinated with four O atoms from four fumarate ligands (O2ⁱⁱⁱ, O1^iv, O2, O1^v, (iii), 1.25 - x, 0.25 - y, z; (iv) 1.5 - x, 0.5 - y, 1 - z; (v) -0.25 + x, -0.25 + y, 1 - z), two O atoms from one oxalate ligand (O3 and O3ⁱⁱⁱ) and two water molecules (O4 and O4ⁱⁱⁱ) (Fig. 1). The Er—O bond lengths are between 2.273 (3)–2.428 (3) Å. The Er atoms are linked through bridging carboxyl groups of fumarate ligands to form two-dimensional Er–fum layers in the ab plane (Fig. 2). Along the c direction, the Er-fum layers are pillared by the oxalic acid resulting in a three-dimensional structure. The framework contains approximately 6.2 Å×11.1 Å rectangular channels along the [100] direction. These channels are occupied by coordinated and free water molecules (Fig. 3). The three-dimensional structure is stabilized by O_water—H···O hydrogen bonds involving both the coordinated and free water molecules.

Related literature top

For lanthanide–metal complexes containing fumarate ligands, see: Zhang et al. (2006). For lanthanide-containing structures with metal-organic frameworks and two different flexible carboxylate ligands, see: Zhang et al. (2008); Zhu et al. (2007).

Experimental top

A mixture of fumaric acid (0.058 g, 0.50 mmol), oxalic acid (0.063 g, 0.50 mmol) and erbium nitrate hexahydrate (0.230 g, 0.50 mmol) in distilled water (15 ml) was stirred fully in air, and then sealed in 25 ml Teflon-lined stainless steel container, which was heated firstly at 403 K for 2 days and then at 443 K for 1 day. The pink block product, I, was crystallized upon cooling to 273 K.

Structure description top

For lanthanide–metal complexes containing fumarate ligands, see: Zhang et al. (2006). For lanthanide-containing structures with metal-organic frameworks and two different flexible carboxylate ligands, see: Zhang et al. (2008); Zhu et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Coordination environment of Er1 in compound I with labelling and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (i) 2.25 - x, 0.25 - y, z; (ii) 1.25 - x, y, 1.25 - z; (iii) 1.25 - x, 0.25 - y, z; (iv) 1.5 - x, 0.5 - y, 1 - z; (v) -0.25 + x, -0.25 + y, 1 - z; (vi) 1 + x, y, z; (vii) 2 - x, -y, 1 - z; (viii) x, 0.25 - y, 1.25 - z; (ix) -1 + x, y, z; (x) -0.75 + x, 0.25 + y, 1 - z.
	Fig. 2. The two-dimensional Er-fum layer extends in the ab plane.
	Fig. 3. The three-dimensional network with rectangular channels along the [100] direction.

Poly[[tetraaquadi-µ₄-fumarato-µ₂-oxalato-dierbium(III)] tetrahydrate] top

Crystal data top

[Er₂(C₄H₂O₄)₂(C₂O₄)(H₂O)₄]·4H₂O	D_x = 2.621 Mg m⁻³
M_r = 794.78	Melting point: not measured K
Orthorhombic, Fddd	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -F 2uv 2vw	Cell parameters from 9875 reflections
a = 9.6016 (19) Å	θ = 3.0–27.5°
b = 15.701 (3) Å	µ = 8.38 mm⁻¹
c = 26.722 (5) Å	T = 293 K
V = 4028.5 (14) Å³	Block, pink
Z = 8	0.19 × 0.16 × 0.13 mm
F(000) = 3008

Data collection top

Bruker SMART APEX CCD diffractometer	1162 independent reflections
Radiation source: fine-focus sealed tube	1088 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 9.00cm pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −20→20
T_min = 0.305, T_max = 0.402	l = −34→31
9284 measured reflections

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)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.045	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0186P)² + 60.2587P] where P = (F_o² + 2F_c²)/3
1162 reflections	(Δ/σ)_max = 0.003
74 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³

Crystal data top

[Er₂(C₄H₂O₄)₂(C₂O₄)(H₂O)₄]·4H₂O	V = 4028.5 (14) Å³
M_r = 794.78	Z = 8
Orthorhombic, Fddd	Mo Kα radiation
a = 9.6016 (19) Å	µ = 8.38 mm⁻¹
b = 15.701 (3) Å	T = 293 K
c = 26.722 (5) Å	0.19 × 0.16 × 0.13 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1162 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1088 reflections with I > 2σ(I)
T_min = 0.305, T_max = 0.402	R_int = 0.022
9284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.045	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0186P)² + 60.2587P] where P = (F_o² + 2F_c²)/3
1162 reflections	Δρ_max = 0.51 e Å⁻³
74 parameters	Δρ_min = −1.04 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
C1	0.9358 (4)	0.1660 (2)	0.52974 (13)	0.0167 (6)
C2	1.0906 (4)	0.1604 (3)	0.53278 (16)	0.0268 (8)
H2	1.1407	0.2110	0.5348	0.032*
C3	0.6250	0.0756 (3)	0.6250	0.0150 (8)
Er1	0.6250	0.1250	0.508677 (7)	0.01528 (8)
O1	0.8868 (3)	0.23742 (16)	0.51740 (10)	0.0237 (5)
O2	0.8597 (3)	0.10210 (16)	0.53731 (11)	0.0239 (5)
O3	0.6164 (3)	0.04009 (15)	0.58332 (9)	0.0190 (5)
O4	0.4757 (3)	0.12267 (15)	0.43533 (9)	0.0256 (5)
H4A	0.3985	0.1447	0.4440	0.031*
H4B	0.4595	0.0706	0.4288	0.031*
O5	0.5533 (3)	0.20049 (15)	0.34370 (9)	0.0859 (16)
H5A	0.5298	0.1769	0.3711	0.103*
H5B	0.5661	0.2534	0.3485	0.129*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0141 (15)	0.0186 (16)	0.0173 (16)	0.0032 (13)	−0.0010 (13)	0.0001 (13)
C2	0.0159 (17)	0.0232 (18)	0.041 (2)	−0.0021 (14)	0.0015 (15)	−0.0025 (17)
C3	0.0133 (19)	0.013 (2)	0.019 (2)	0.000	−0.0012 (19)	0.000
Er1	0.01765 (12)	0.01422 (11)	0.01396 (11)	0.00560 (8)	0.000	0.000
O1	0.0239 (13)	0.0200 (12)	0.0270 (13)	0.0067 (10)	0.0003 (11)	0.0045 (10)
O2	0.0168 (12)	0.0205 (12)	0.0344 (14)	0.0009 (10)	0.0001 (11)	0.0027 (11)
O3	0.0269 (13)	0.0139 (11)	0.0161 (11)	−0.0003 (10)	−0.0015 (10)	−0.0010 (9)
O4	0.0296 (13)	0.0215 (12)	0.0256 (13)	−0.0017 (11)	−0.0040 (11)	0.0002 (11)
O5	0.099 (4)	0.076 (3)	0.082 (3)	−0.011 (3)	0.012 (3)	0.037 (3)

Geometric parameters (Å, º) top

C1—O2	1.258 (4)	Er1—O3	2.401 (2)
C1—O1	1.260 (4)	Er1—O2	2.407 (3)
C1—C2	1.491 (5)	Er1—O2ⁱⁱⁱ	2.407 (3)
C2—C2ⁱ	1.294 (8)	Er1—O4	2.428 (2)
C2—H2	0.9300	Er1—O4ⁱⁱⁱ	2.428 (2)
C3—O3	1.249 (3)	O1—Er1^iv	2.273 (3)
C3—O3ⁱⁱ	1.249 (3)	O4—H4A	0.8500
C3—C3ⁱⁱⁱ	1.550 (9)	O4—H4B	0.8499
Er1—O1^iv	2.273 (3)	O5—H5A	0.8500
Er1—O1^v	2.273 (3)	O5—H5B	0.8500
Er1—O3ⁱⁱⁱ	2.401 (2)

O2—C1—O1	122.4 (3)	O3—Er1—O2ⁱⁱⁱ	77.67 (9)
O2—C1—C2	121.5 (3)	O2—Er1—O2ⁱⁱⁱ	142.93 (13)
O1—C1—C2	116.0 (3)	O1^iv—Er1—O4	74.78 (9)
C2ⁱ—C2—C1	124.0 (5)	O1^v—Er1—O4	76.55 (9)
C2ⁱ—C2—H2	118.0	O3ⁱⁱⁱ—Er1—O4	134.38 (9)
C1—C2—H2	118.0	O3—Er1—O4	129.93 (8)
O3—C3—O3ⁱⁱ	126.9 (4)	O2—Er1—O4	143.80 (9)
O3—C3—C3ⁱⁱⁱ	116.6 (2)	O2ⁱⁱⁱ—Er1—O4	72.91 (9)
O3ⁱⁱ—C3—C3ⁱⁱⁱ	116.6 (2)	O1^iv—Er1—O4ⁱⁱⁱ	76.55 (9)
O1^iv—Er1—O1^v	144.28 (13)	O1^v—Er1—O4ⁱⁱⁱ	74.78 (9)
O1^iv—Er1—O3ⁱⁱⁱ	74.25 (9)	O3ⁱⁱⁱ—Er1—O4ⁱⁱⁱ	129.93 (8)
O1^v—Er1—O3ⁱⁱⁱ	141.35 (9)	O3—Er1—O4ⁱⁱⁱ	134.38 (9)
O1^iv—Er1—O3	141.35 (9)	O2—Er1—O4ⁱⁱⁱ	72.91 (9)
O1^v—Er1—O3	74.25 (9)	O2ⁱⁱⁱ—Er1—O4ⁱⁱⁱ	143.80 (9)
O3ⁱⁱⁱ—Er1—O3	67.62 (11)	O4—Er1—O4ⁱⁱⁱ	72.38 (12)
O1^iv—Er1—O2	106.62 (9)	C1—O1—Er1^iv	160.8 (3)
O1^v—Er1—O2	84.78 (9)	C1—O2—Er1	111.9 (2)
O3ⁱⁱⁱ—Er1—O2	77.67 (9)	C3—O3—Er1	119.4 (2)
O3—Er1—O2	71.66 (9)	Er1—O4—H4A	106.7
O1^iv—Er1—O2ⁱⁱⁱ	84.78 (9)	Er1—O4—H4B	106.7
O1^v—Er1—O2ⁱⁱⁱ	106.62 (9)	H4A—O4—H4B	106.7
O3ⁱⁱⁱ—Er1—O2ⁱⁱⁱ	71.66 (9)	H5A—O5—H5B	109.5

Symmetry codes: (i) −x+9/4, −y+1/4, z; (ii) −x+5/4, y, −z+5/4; (iii) −x+5/4, −y+1/4, z; (iv) −x+3/2, −y+1/2, −z+1; (v) x−1/4, y−1/4, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5^vi	0.85	2.35	3.045 (5)	139
O4—H4B···O3^vii	0.85	1.91	2.750 (3)	168
O5—H5A···O4	0.85	1.99	2.836	180
O5—H5B···O2^viii	0.85	2.36	2.938 (4)	125

Symmetry codes: (vi) −x+3/4, y, −z+3/4; (vii) −x+1, −y, −z+1; (viii) −x+3/2, y+1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	[Er₂(C₄H₂O₄)₂(C₂O₄)(H₂O)₄]·4H₂O
M_r	794.78
Crystal system, space group	Orthorhombic, Fddd
Temperature (K)	293
a, b, c (Å)	9.6016 (19), 15.701 (3), 26.722 (5)
V (Å³)	4028.5 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	8.38
Crystal size (mm)	0.19 × 0.16 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.305, 0.402
No. of measured, independent and observed [I > 2σ(I)] reflections	9284, 1162, 1088
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.045, 1.11
No. of reflections	1162
No. of parameters	74
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0186P)² + 60.2587P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.51, −1.04

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5ⁱ	0.85	2.35	3.045 (5)	138.8
O4—H4B···O3ⁱⁱ	0.85	1.91	2.750 (3)	168.1
O5—H5A···O4	0.85	1.99	2.836	179.5
O5—H5B···O2ⁱⁱⁱ	0.85	2.36	2.938 (4)	125.4

Symmetry codes: (i) −x+3/4, y, −z+3/4; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y+1/4, z−1/4.

Acknowledgements

This work was supported by the Natural Science Foundation of Ningxia Hui Autonomous Region (No. NZ1150).

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