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

Du, X.-G.; Zhang, J.; Li, J.-J.

doi:10.1107/S1600536812029546

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page m1024

https://doi.org/10.1107/S1600536812029546

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

Xi-Gang Du,^a ^* Jun Zhang ^a and Jia-Jia Li ^b

^aSchool of Chemical Engineering and Pharmaceutics, Henan University of Science and Technology, Luoyang 471003, People's Republic of China, and ^bDepartment of Chemistry, Zhengzhou University, Zhengzhou 450001, People's Republic of China
^*Correspondence e-mail: yyduxigang@yahoo.com.cn

(Received 23 May 2012; accepted 28 June 2012; online 4 July 2012)

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, C 2/c
a = 25.366 (8) Å
b = 5.8326 (14) Å
c = 19.008 (6) Å
β = 124.136 (4)°
V = 2327.7 (12) Å³
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[F² > 2σ(F²)] = 0.035
wR(F²) = 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

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⋯O5^iv	0.85	2.46	2.919 (5)	115
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z; (iii) -x+2, -y+1, -z+2; (iv) -x+2, -y, -z+2.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812029546/rk2364sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029546/rk2364Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For the topological 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 4f metal-organic frameworks formed by thiophene-2,5-dicarboxylic acid, see: Huang et al. (2009).

Experimental top

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.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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).

Figures top

	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.

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

Crystal data top

[Eu₂(C₆H₂O₄S)₃(H₂O)₄]	F(000) = 1696
M_r = 886.44	D_x = 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 top

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

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)] = 0.035	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(F_o²) + (0.0272P)²] where P = (F_o² + 2F_c²)/3
2634 reflections	(Δ/σ)_max = 0.026
180 parameters	Δρ_max = 1.97 e Å⁻³
0 restraints	Δρ_min = −1.74 e Å⁻³

Crystal data top

[Eu₂(C₆H₂O₄S)₃(H₂O)₄]	V = 2327.7 (12) Å³
M_r = 886.44	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 25.366 (8) Å	µ = 5.69 mm⁻¹
b = 5.8326 (14) Å	T = 295 K
c = 19.008 (6) Å	0.22 × 0.12 × 0.11 mm
β = 124.136 (4)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2634 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2290 reflections with I > 2σ(I)
T_min = 0.445, T_max = 0.535	R_int = 0.061
8572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 1.97 e Å⁻³
2634 reflections	Δρ_min = −1.74 e Å⁻³
180 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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—C8^iv	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—Eu1^v	2.375 (3)	C4—C5	1.476 (7)
O2—C5	1.258 (5)	C7—C8	1.373 (8)
O2—Eu1^vi	2.326 (3)	C7—C7^iv	1.389 (11)
O3—C6	1.262 (6)	C7—H7	0.87 (6)
O3—Eu1^vii	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—C7^iv	112.4 (3)
O8—Eu1—O5	73.97 (12)	C8—C7—H7	116 (4)
O6—Eu1—O5	51.87 (11)	C7^iv—C7—H7	131 (4)
C1—S1—C4	91.2 (2)	C7—C8—C9	128.9 (5)
C8^iv—S2—C8	91.8 (4)	C7—C8—S2	111.7 (4)
C5—O1—Eu1^v	137.3 (3)	C9—C8—S2	119.4 (4)
C5—O2—Eu1^vi	154.6 (3)	O5—C9—O6	121.7 (5)
C6—O3—Eu1^vii	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)	Eu1^vi—O2—C5—O1	40.7 (11)
O3ⁱⁱⁱ—Eu1—O4—C6	168.6 (8)	Eu1^vi—O2—C5—C4	−140.3 (6)
O7—Eu1—O4—C6	89.5 (8)	Eu1^v—O1—C5—O2	91.7 (6)
O8—Eu1—O4—C6	−45.1 (9)	Eu1^v—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)	Eu1^vii—O3—C6—O4	36.1 (8)
O4—Eu1—O5—C9	92.6 (3)	Eu1^vii—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)	C7^iv—C7—C8—C9	179.4 (7)
O7—Eu1—O6—C9	−139.1 (3)	C7^iv—C7—C8—S2	0.3 (9)
O8—Eu1—O6—C9	86.5 (3)	C8^iv—S2—C8—C7	−0.1 (3)
O5—Eu1—O6—C9	7.7 (3)	C8^iv—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) top

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···O3^viii	0.85	2.53	3.073 (5)	123
O7—H7B···O5^viii	0.85	2.03	2.833 (5)	158
O8—H8B···O6^ix	0.85	2.10	2.846 (5)	147
O8—H8A···O5^x	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.

Experimental details

Crystal data
Chemical formula	[Eu₂(C₆H₂O₄S)₃(H₂O)₄]
M_r	886.44
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	25.366 (8), 5.8326 (14), 19.008 (6)
β (°)	124.136 (4)
V (Å³)	2327.7 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.69
Crystal size (mm)	0.22 × 0.12 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.445, 0.535
No. of measured, independent and observed [I > 2σ(I)] reflections	8572, 2634, 2290
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 1.00
No. of reflections	2634
No. of parameters	180
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.97, −1.74

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), enCIFer (Allen et al., 2004) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4ⁱ	0.85	2.11	2.915 (6)	158.0
O7—H7A···O3ⁱⁱ	0.85	2.53	3.073 (5)	122.8
O7—H7B···O5ⁱⁱ	0.85	2.03	2.833 (5)	158.4
O8—H8B···O6ⁱⁱⁱ	0.85	2.10	2.846 (5)	146.6
O8—H8A···O5^iv	0.85	2.46	2.919 (5)	114.9

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

Acknowledgements

This work was supported financially by the Doctoral Fund Project of Shandong Province (BS2009SF019) and the National Natural Science Foundation of China (grants Nos. 21076063 and 20963007).

References

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