Poly[tetra­aqua­bis­(μ₄-thio­phene-2,5-dicarboxyl­ato)(μ₂-thio­phene-2,5-dicarboxyl­ato)dieuropium(III)]

Abstract

The three-dimensional coordination polymer, [Eu₂(C₆H₂O₄S)₃(H₂O)₄]_n, has been synthesized under hydro­thermal conditions. The asymmetric unit comprises one Eu³⁺ cation, two aqua ligands and one and a half thiophene-2,5-dicarboxylate anions (the half-anion being completed by a twofold rotation axis). The Eu³⁺ cation is eight-coordinated in a distorted dodeca­hedral geometry. The crystal structure features O—H⋯O hydrogen bonds.

Related literature  

For the structures and potential applications of metal hybrid compounds, see: Bo et al. (2008 ▶). For a number of lanthanide coordination polymers based on pyridine­dicarb­oxy­lic acid, see: Xu et al. (2011 ▶). For metal-organic framework structures formed by 4f metals and thiophene-2,5-dicarboxylate anions, see: Huang et al. (2009 ▶).

Experimental  

Crystal data  

• [Eu₂(C₆H₂O₄S)₃(H₂O)₄]

• M _r = 886.44

• Monoclinic,

• a = 25.366 (8) Å

• b = 5.8326 (14) Å

• c = 19.008 (6) Å

• β = 124.136 (4)°

• V = 2327.7 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 5.69 mm⁻¹

• T = 295 K

• 0.22 × 0.12 × 0.11 mm

Data collection  

• Bruker SMART APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.445, T _max = 0.535

• 8572 measured reflections

• 2634 independent reflections

• 2290 reflections with I > 2σ(I)

• R _int = 0.061

Refinement  

• R[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 0.090

• S = 1.00

• 2634 reflections

• 180 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.97 e Å⁻³

• Δρ_min = −1.74 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: enCIFer (Allen et al., 2004) ▶ and PLATON (Spek, 2009 ▶).

Supplementary Material

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
O7—H7A⋯O4i	0.85	2.11	2.915 (6)	158
O7—H7A⋯O3ii	0.85	2.53	3.073 (5)	123
O7—H7B⋯O5ii	0.85	2.03	2.833 (5)	158
O8—H8B⋯O6iii	0.85	2.10	2.846 (5)	147
O8—H8A⋯O5iv	0.85	2.46	2.919 (5)	115

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

The design and synthesis of metal-hybrid compounds have attracted considerable interest due to their intriguing topological structures and potential applications as functional materials in luminescence, magnetism, host-guest chemistry, catalysis and gas adsorption and separation (Bo et al., 2008). In recent years, a number of lanthanide coordination polymers based on pyridinedicarboxylic acid have been synthesized under hydrothermal conditions (Xu et al., 2011). By contrast with these lanthanide complexes containing only rigid pyridinedicarboxylic ligands, the high-dimensional coordination complexes of 4f metal-organic frameworks formed by H₂tdc (thiophene-2,5-dicarboxylic acid) are still scarce (Huang et al., 2009). Herein, we report a new structure derived from thiophene-2,5-dicarboxylic acid (Scheme 1), namely [Eu₂(tdc)₃(H₂O)₄]_n.

A view of the coordination environment of the Eu³⁺ with atom labeling is illustrated in Fig. 1. The Hydrogen-bond are listed in Table 1. The Eu—O bond lengths range from 2.336 (2)Å to 2.493 (1)Å, and the bond angles of O—Eu—O are in the range of 51.87 (11)° to 156.27 (13)°. In structure, tdc ligand adopt two different coordination modes, constructing an ordered three-dimensional lanthanide framework (Fig. 2).

Experimental

All chemicals and solvents except Eu(NO₃)₃ were purchased and used as received without further purification. Eu(NO₃)₃ was prepared by dissolving Eu₂O₃ with concentrated HNO₃ and then evaporating at 373 K until crystal film formed. A mixture of Eu(NO₃)₃ (0.3 mmol), KSCN (0.15 mmol), H₂tdc (0.3 mmol) and deionized water (8.0 ml) in a 23 ml teflon-lined autoclave and kept under autogenous pressure at 443 K for 5 days and then cooling to room temperature at a rate of 5 K h^-1. Colourless crystals were isolated by filtration.

Refinement

All hydrogen atoms were positioned geometrically and treated as riding, with C–H = 0.93Å (CH) and U_iso(H) = 1.2U_eq(C), with C–H = 0.97Å (CH₂) and U_iso(H) = 1.2U_eq(C), and with C–H = 0.96Å (CH₃) and U_iso(H) = 1.5U_eq(C)

Figures

Fig. 1.

The coordination environment of the Eu3+ with the atom numbering scheme. Displacement ellipsoids are presented at 30% probability level. Symmetry codes: (i) x, 1-y, 1/2+z; (ii) x, -y, 1/2+z; (iii) 3/2-x, 1/2+y, 3/2-z; (iv) 2-x, y, 1/2-z;

Fig. 2.

Three-dimensional architecture in the crystal structure of title compound. All the hydrogen atoms are omitted for clarity.

Crystal data

[Eu2(C6H2O4S)3(H2O)4]	F(000) = 1696
Mr = 886.44	Dx = 2.530 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8572 reflections
a = 25.366 (8) Å	θ = 2.6–27.5°
b = 5.8326 (14) Å	µ = 5.69 mm−1
c = 19.008 (6) Å	T = 295 K
β = 124.136 (4)°	Block, colourless
V = 2327.7 (12) Å3	0.22 × 0.12 × 0.11 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer	2634 independent reflections
Radiation source: fine-focus sealed tube	2290 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
φ and ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −32→32
Tmin = 0.445, Tmax = 0.535	k = −7→7
8572 measured reflections	l = −24→24

Refinement

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0272P)2] where P = (Fo2 + 2Fc2)/3
2634 reflections	(Δ/σ)max = 0.026
180 parameters	Δρmax = 1.97 e Å−3
0 restraints	Δρmin = −1.74 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 (Ų)

	x	y	z	Uiso*/Ueq
Eu1	0.866707 (10)	0.33845 (4)	0.887181 (14)	0.01268 (11)
S1	0.80798 (6)	0.0059 (2)	0.56308 (7)	0.0174 (3)
S2	1.0000	0.3059 (3)	0.7500	0.0186 (4)
O1	0.89384 (19)	0.3300 (5)	0.4736 (2)	0.0174 (8)
O2	0.84987 (18)	−0.0175 (6)	0.4448 (2)	0.0222 (8)
O3	0.73304 (15)	−0.0491 (6)	0.6396 (2)	0.0183 (7)
O4	0.79280 (18)	0.1905 (6)	0.7483 (2)	0.0197 (8)
O5	0.92823 (17)	0.0273 (6)	0.8657 (2)	0.0188 (7)
O6	0.94444 (17)	0.3894 (6)	0.8480 (2)	0.0186 (7)
O7	0.83645 (19)	0.6714 (5)	0.7928 (2)	0.0175 (8)
H7A	0.7974	0.7025	0.7705	0.026*
H7B	0.8592	0.7858	0.8214	0.026*
O8	0.96903 (18)	0.2934 (7)	1.0254 (2)	0.0254 (9)
H8B	0.9831	0.4248	1.0475	0.038*
H8A	0.9956	0.2279	1.0181	0.038*
C1	0.8071 (2)	0.1795 (8)	0.6351 (3)	0.0144 (10)
C2	0.8346 (2)	0.3894 (9)	0.6426 (3)	0.0185 (10)
H2	0.8382	0.5055	0.6786	0.022*
C3	0.8565 (2)	0.4072 (9)	0.5900 (3)	0.0171 (10)
H3	0.8758	0.5383	0.5866	0.021*
C4	0.8467 (2)	0.2123 (9)	0.5438 (3)	0.0154 (10)
C5	0.8649 (2)	0.1712 (7)	0.4835 (3)	0.0135 (10)
C6	0.7759 (2)	0.1015 (8)	0.6773 (3)	0.0139 (9)
C7	0.9866 (3)	−0.1143 (10)	0.7733 (4)	0.0283 (13)
C8	0.9766 (2)	0.1034 (9)	0.7912 (3)	0.0172 (10)
C9	0.9486 (2)	0.1754 (8)	0.8384 (3)	0.0153 (11)
H7	0.976 (3)	−0.227 (10)	0.794 (3)	0.018*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Eu1	0.01266 (17)	0.01346 (19)	0.01289 (17)	0.00158 (7)	0.00776 (14)	0.00075 (7)
S1	0.0208 (6)	0.0165 (6)	0.0195 (6)	−0.0051 (5)	0.0142 (5)	−0.0040 (5)
S2	0.0227 (9)	0.0160 (8)	0.0265 (9)	0.000	0.0195 (8)	0.000
O1	0.020 (2)	0.020 (2)	0.0183 (19)	−0.0001 (13)	0.0144 (18)	0.0045 (13)
O2	0.0246 (19)	0.0203 (19)	0.0277 (18)	−0.0023 (15)	0.0183 (17)	−0.0077 (15)
O3	0.0154 (16)	0.0226 (18)	0.0193 (16)	−0.0090 (14)	0.0112 (15)	−0.0068 (15)
O4	0.023 (2)	0.026 (2)	0.0136 (17)	−0.0048 (14)	0.0122 (17)	−0.0045 (14)
O5	0.0225 (18)	0.0167 (18)	0.0263 (18)	0.0018 (14)	0.0193 (16)	0.0025 (15)
O6	0.0195 (18)	0.0171 (18)	0.0240 (18)	0.0007 (14)	0.0150 (16)	−0.0003 (15)
O7	0.019 (2)	0.016 (2)	0.0163 (18)	0.0006 (12)	0.0093 (17)	0.0015 (12)
O8	0.0196 (19)	0.0235 (18)	0.0209 (19)	0.0019 (15)	0.0039 (17)	−0.0051 (16)
C1	0.012 (2)	0.018 (3)	0.014 (2)	−0.0042 (17)	0.007 (2)	−0.0008 (17)
C2	0.020 (3)	0.019 (2)	0.018 (2)	−0.002 (2)	0.011 (2)	−0.003 (2)
C3	0.022 (3)	0.013 (2)	0.020 (2)	−0.0036 (19)	0.013 (2)	0.000 (2)
C4	0.012 (2)	0.020 (2)	0.016 (2)	−0.0009 (19)	0.009 (2)	−0.001 (2)
C5	0.010 (2)	0.015 (3)	0.014 (2)	0.0018 (16)	0.006 (2)	0.0016 (17)
C6	0.012 (2)	0.016 (2)	0.013 (2)	0.0052 (19)	0.0073 (19)	0.0038 (19)
C7	0.050 (4)	0.016 (2)	0.044 (3)	−0.008 (3)	0.042 (3)	−0.002 (3)
C8	0.018 (2)	0.020 (2)	0.022 (2)	0.001 (2)	0.016 (2)	0.000 (2)
C9	0.010 (2)	0.020 (3)	0.015 (2)	−0.0005 (17)	0.006 (2)	−0.0012 (18)

Geometric parameters (Å, º)

Eu1—O2i	2.326 (3)	O4—C6	1.275 (6)
Eu1—O1ii	2.375 (3)	O5—C9	1.259 (6)
Eu1—O3iii	2.376 (3)	O6—C9	1.274 (5)
Eu1—O4	2.382 (4)	O7—H7A	0.8500
Eu1—O7	2.456 (3)	O7—H7B	0.8500
Eu1—O8	2.461 (4)	O8—H8B	0.8500
Eu1—O6	2.486 (4)	O8—H8A	0.8501
Eu1—O5	2.572 (3)	C1—C2	1.376 (7)
S1—C1	1.713 (5)	C1—C6	1.480 (7)
S1—C4	1.718 (5)	C2—C3	1.392 (7)
S2—C8iv	1.697 (5)	C2—H2	0.9300
S2—C8	1.697 (5)	C3—C4	1.372 (7)
O1—C5	1.260 (6)	C3—H3	0.9300
O1—Eu1v	2.375 (3)	C4—C5	1.476 (7)
O2—C5	1.258 (5)	C7—C8	1.373 (8)
O2—Eu1vi	2.326 (3)	C7—C7iv	1.389 (11)
O3—C6	1.262 (6)	C7—H7	0.87 (6)
O3—Eu1vii	2.376 (3)	C8—C9	1.484 (7)
O2i—Eu1—O1ii	112.82 (13)	C9—O6—Eu1	94.0 (3)
O2i—Eu1—O3iii	82.43 (12)	Eu1—O7—H7A	109.4
O1ii—Eu1—O3iii	77.54 (13)	Eu1—O7—H7B	109.4
O2i—Eu1—O4	89.55 (13)	H7A—O7—H7B	109.5
O1ii—Eu1—O4	143.48 (13)	Eu1—O8—H8B	109.3
O3iii—Eu1—O4	77.34 (13)	Eu1—O8—H8A	109.3
O2i—Eu1—O7	156.27 (13)	H8B—O8—H8A	109.5
O1ii—Eu1—O7	73.27 (14)	C2—C1—C6	127.7 (5)
O3iii—Eu1—O7	76.49 (12)	C2—C1—S1	112.1 (4)
O4—Eu1—O7	75.39 (12)	C6—C1—S1	120.2 (3)
O2i—Eu1—O8	76.92 (13)	C1—C2—C3	112.0 (5)
O1ii—Eu1—O8	68.02 (13)	C1—C2—H2	124.0
O3iii—Eu1—O8	128.08 (13)	C3—C2—H2	124.0
O4—Eu1—O8	147.93 (13)	C4—C3—C2	113.4 (5)
O7—Eu1—O8	125.05 (13)	C4—C3—H3	123.3
O2i—Eu1—O6	128.58 (12)	C2—C3—H3	123.3
O1ii—Eu1—O6	98.00 (13)	C3—C4—C5	127.6 (5)
O3iii—Eu1—O6	146.20 (12)	C3—C4—S1	111.3 (4)
O4—Eu1—O6	88.55 (12)	C5—C4—S1	121.1 (4)
O7—Eu1—O6	70.23 (13)	O2—C5—O1	124.5 (5)
O8—Eu1—O6	78.11 (13)	O2—C5—C4	118.1 (4)
O2i—Eu1—O5	78.18 (12)	O1—C5—C4	117.3 (4)
O1ii—Eu1—O5	135.91 (12)	O3—C6—O4	123.7 (5)
O3iii—Eu1—O5	145.99 (12)	O3—C6—C1	117.3 (4)
O4—Eu1—O5	74.85 (12)	O4—C6—C1	119.0 (4)
O7—Eu1—O5	114.24 (12)	C8—C7—C7iv	112.4 (3)
O8—Eu1—O5	73.97 (12)	C8—C7—H7	116 (4)
O6—Eu1—O5	51.87 (11)	C7iv—C7—H7	131 (4)
C1—S1—C4	91.2 (2)	C7—C8—C9	128.9 (5)
C8iv—S2—C8	91.8 (4)	C7—C8—S2	111.7 (4)
C5—O1—Eu1v	137.3 (3)	C9—C8—S2	119.4 (4)
C5—O2—Eu1vi	154.6 (3)	O5—C9—O6	121.7 (5)
C6—O3—Eu1vii	142.1 (3)	O5—C9—C8	120.1 (4)
C6—O4—Eu1	155.3 (3)	O6—C9—C8	118.1 (4)
C9—O5—Eu1	90.4 (3)
O2i—Eu1—O4—C6	−109.1 (8)	C1—S1—C4—C5	179.0 (4)
O1ii—Eu1—O4—C6	121.1 (8)	Eu1vi—O2—C5—O1	40.7 (11)
O3iii—Eu1—O4—C6	168.6 (8)	Eu1vi—O2—C5—C4	−140.3 (6)
O7—Eu1—O4—C6	89.5 (8)	Eu1v—O1—C5—O2	91.7 (6)
O8—Eu1—O4—C6	−45.1 (9)	Eu1v—O1—C5—C4	−87.3 (6)
O6—Eu1—O4—C6	19.5 (8)	C3—C4—C5—O2	−177.7 (5)
O5—Eu1—O4—C6	−31.2 (8)	S1—C4—C5—O2	1.7 (7)
O2i—Eu1—O5—C9	−174.6 (3)	C3—C4—C5—O1	1.4 (8)
O1ii—Eu1—O5—C9	−63.9 (3)	S1—C4—C5—O1	−179.2 (4)
O3iii—Eu1—O5—C9	128.8 (3)	Eu1vii—O3—C6—O4	36.1 (8)
O4—Eu1—O5—C9	92.6 (3)	Eu1vii—O3—C6—C1	−142.9 (4)
O7—Eu1—O5—C9	26.7 (3)	Eu1—O4—C6—O3	140.6 (6)
O8—Eu1—O5—C9	−95.0 (3)	Eu1—O4—C6—C1	−40.4 (10)
O6—Eu1—O5—C9	−7.7 (3)	C2—C1—C6—O3	152.4 (5)
O2i—Eu1—O6—C9	24.1 (3)	S1—C1—C6—O3	−24.0 (6)
O1ii—Eu1—O6—C9	151.9 (3)	C2—C1—C6—O4	−26.7 (8)
O3iii—Eu1—O6—C9	−128.6 (3)	S1—C1—C6—O4	156.9 (4)
O4—Eu1—O6—C9	−64.1 (3)	C7iv—C7—C8—C9	179.4 (7)
O7—Eu1—O6—C9	−139.1 (3)	C7iv—C7—C8—S2	0.3 (9)
O8—Eu1—O6—C9	86.5 (3)	C8iv—S2—C8—C7	−0.1 (3)
O5—Eu1—O6—C9	7.7 (3)	C8iv—S2—C8—C9	−179.3 (5)
C4—S1—C1—C2	1.0 (4)	Eu1—O5—C9—O6	14.0 (5)
C4—S1—C1—C6	177.9 (4)	Eu1—O5—C9—C8	−164.0 (4)
C6—C1—C2—C3	−176.9 (5)	Eu1—O6—C9—O5	−14.6 (5)
S1—C1—C2—C3	−0.2 (6)	Eu1—O6—C9—C8	163.5 (4)
C1—C2—C3—C4	−1.0 (7)	C7—C8—C9—O5	−2.5 (8)
C2—C3—C4—C5	−178.9 (5)	S2—C8—C9—O5	176.5 (4)
C2—C3—C4—S1	1.7 (6)	C7—C8—C9—O6	179.4 (6)
C1—S1—C4—C3	−1.5 (4)	S2—C8—C9—O6	−1.6 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4iii	0.85	2.11	2.915 (6)	158
O7—H7A···O3viii	0.85	2.53	3.073 (5)	123
O7—H7B···O5viii	0.85	2.03	2.833 (5)	158
O8—H8B···O6ix	0.85	2.10	2.846 (5)	147
O8—H8A···O5x	0.85	2.46	2.919 (5)	115

Symmetry codes: (iii) −x+3/2, y+1/2, −z+3/2; (viii) x, y+1, z; (ix) −x+2, −y+1, −z+2; (x) −x+2, −y, −z+2.