Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108033180/gg3175sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108033180/gg3175Isup2.hkl |
CCDC reference: 710748
A sample of Eu2O3 (0.354 g, 1 mmol) was suspended in water (10 ml), and ethanesulfonic acid (0.5 ml, 6 mmol) was added carefully to avoid uncontrolled local heating. The mixture was heated slowly to ca 343 K and stirred until dissolution of the rare earth oxide after a few minutes. Colourless needles of [Eu(C2H5SO3)3(H2O)3] were obtained by evaporation of the solvent at room temperature. To isolate crystals suitable for X-ray structure analysis and single-crystal attenuated total reflection IR recrystallization of the raw product from a mixture of ca 4 ml of water, 4 ml of methanol, 1 ml of ethanol and a few drops of glycerol proved to be necessary. IR (ν, cm-1): 3387 (m, br), 2980 (m, sh), 2943 (m, sh), 2884 (w, sh), 1716 (w, br), 1660 (w), 1618 (w, sh), 1458 (w), 1429 (w, sh), 1421 (w), 1302 (w), 1254 (m), 1200 (m, sh), 1139 (vs), 1073 (s, sh), 1052 (s, sh), 1038 (vs), 983 (m, sh), 787 (w), 746 (m), 575 (m); CHN analysis (533.41), found: C 13.60, H 3.95%; calculated; C 13.51, H 3.97 %.
As the difference of atom displacement of Eu1 and O11 along the corresponding bond direction was somewhat too high, one `rigid bond' restraint was applied. All H-atom positions of the water molecules, including the partial occupancy positions H6 and H6A (Fig. 1), could be located in difference Fourier maps. The water molecules were treated as rigid groups with idealized geometry but with freedom of rotation and translation. Isotropic displacement parameters for their H atoms were refined, except for H5, H6 and H6A, for which the Uiso values were fixed at 150% of the Ueq value of the parent atom O12. As the partial occupancy positions of the disordered atoms H6 and H6A were not stable during refinement, their principal orientation found in the difference map was stabilized by restraining the intermolecular distances between H6 and H6Av and H6A and H6v [symmetry code: (v) -x + 1/2, y, -z] to 2.70 Å with an estimated standard deviation of 0.01 Å. The H atoms of the CH2 groups were treated as riding on the C atoms with idealized bond lengths and angles. Those of the CH3 groups were allowed to ride on the C atoms likewise, but were additionally free to rotate about the C—C bond. Uiso values were fixed at 120% of the Ueq value of the respective parent C atom, whereas the Uiso values of H atoms of the CH3 groups were fixed at 150% of the Ueq value of the carrier atom. Three significant electron-density maxima (1.16 e Å-3 at 0.90 Å, 1.04 e Å-3 at 0.93 Å and 1.04 e Å-3 at 0.90 Å from Eu1) were found in the final difference Fourier map.
Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004).
[Eu(C2H5SO3)3(H2O)3] | F(000) = 2112 |
Mr = 533.41 | Dx = 2.124 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I 2ya | Cell parameters from 7998 reflections |
a = 24.323 (2) Å | θ = 2.8–26.1° |
b = 5.4408 (4) Å | µ = 4.19 mm−1 |
c = 27.066 (2) Å | T = 233 K |
β = 111.328 (9)° | Needle, colourless |
V = 3336.5 (5) Å3 | 0.57 × 0.10 × 0.10 mm |
Z = 8 |
Stoe IPDS diffractometer | 3282 independent reflections |
Radiation source: fine-focus sealed tube | 2788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.1°, θmin = 2.8° |
ϕ scans | h = −29→29 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | k = −6→6 |
Tmin = 0.578, Tmax = 0.672 | l = −33→33 |
22872 measured reflections |
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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 1.22 | w = 1/[σ2(Fo2) + (0.0275P)2] where P = (Fo2 + 2Fc2)/3 |
3282 reflections | (Δ/σ)max = 0.001 |
216 parameters | Δρmax = 1.16 e Å−3 |
3 restraints | Δρmin = −1.19 e Å−3 |
[Eu(C2H5SO3)3(H2O)3] | V = 3336.5 (5) Å3 |
Mr = 533.41 | Z = 8 |
Monoclinic, I2/a | Mo Kα radiation |
a = 24.323 (2) Å | µ = 4.19 mm−1 |
b = 5.4408 (4) Å | T = 233 K |
c = 27.066 (2) Å | 0.57 × 0.10 × 0.10 mm |
β = 111.328 (9)° |
Stoe IPDS diffractometer | 3282 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 2788 reflections with I > 2σ(I) |
Tmin = 0.578, Tmax = 0.672 | Rint = 0.085 |
22872 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 3 restraints |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 1.22 | Δρmax = 1.16 e Å−3 |
3282 reflections | Δρmin = −1.19 e Å−3 |
216 parameters |
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. The non-standard space group setting was preferred to the standard setting because of a significant smaller monoclinic angle of 111.33 ° compared to 119.87 °. It was necessary to refine one of the water molecules containing O(12) as disordered: otherwise the structure model is not plausible because neighbouring atoms are too close to each other. In spite of a careful search no superstructure reflections could be found, i. e. a split site for this aqua ligand is given or the related noncentrosymmetric space group Ia has to be chosen. Based on the distribution of E-values and arguments given by Marsh [Acta Cryst. (1986), B42, 193–198) concerning the choice of centrosymmetric and noncentrosymmetric space groups a statistic treatment in a centrosymmetric space group deemed more sensible than the use of the noncentrosymmetric subgroup. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Eu1 | 0.350369 (6) | 0.37896 (3) | 0.124278 (6) | 0.01568 (6) | |
S1 | 0.28461 (3) | 0.87040 (13) | 0.17595 (3) | 0.01754 (15) | |
S2 | 0.35168 (3) | −0.12394 (13) | 0.02760 (3) | 0.01897 (15) | |
S3 | 0.50656 (3) | 0.19178 (14) | 0.16842 (3) | 0.02174 (16) | |
O1 | 0.29347 (11) | 0.6213 (4) | 0.15977 (11) | 0.0314 (6) | |
O2 | 0.29488 (10) | 1.0538 (4) | 0.14085 (9) | 0.0246 (5) | |
O3 | 0.31854 (10) | 0.9206 (4) | 0.23147 (9) | 0.0296 (5) | |
O4 | 0.34044 (10) | 0.0900 (4) | 0.05461 (10) | 0.0279 (5) | |
O5 | 0.30774 (11) | −0.1525 (5) | −0.02521 (10) | 0.0385 (6) | |
O6 | 0.35952 (13) | −0.3469 (4) | 0.05927 (10) | 0.0358 (6) | |
O7 | 0.44884 (9) | 0.2802 (4) | 0.13132 (9) | 0.0266 (5) | |
O8 | 0.51312 (11) | 0.2367 (5) | 0.22303 (10) | 0.0376 (6) | |
O9 | 0.51577 (12) | −0.0621 (4) | 0.15713 (12) | 0.0380 (6) | |
O10 | 0.41375 (10) | 0.7201 (4) | 0.17091 (10) | 0.0252 (5) | |
H1 | 0.4260 | 0.7184 | 0.2038 | 0.035 (11)* | |
H2 | 0.4436 | 0.7465 | 0.1637 | 0.032 (10)* | |
O11 | 0.39591 (10) | 0.2747 (4) | 0.21706 (9) | 0.0261 (5) | |
H3 | 0.4318 | 0.2644 | 0.2349 | 0.038 (11)* | |
H4 | 0.3803 | 0.1735 | 0.2309 | 0.035 (11)* | |
O12 | 0.25025 (11) | 0.4005 (5) | 0.05719 (11) | 0.0401 (6) | |
H5 | 0.2324 | 0.5318 | 0.0469 | 0.060* | |
H6 | 0.2390 | 0.3102 | 0.0307 | 0.060* | 0.50 |
H6A | 0.2238 | 0.2962 | 0.0519 | 0.060* | 0.50 |
C1 | 0.20846 (14) | 0.8823 (6) | 0.16530 (14) | 0.0262 (7) | |
H11 | 0.1860 | 0.8411 | 0.1286 | 0.031* | |
H12 | 0.1998 | 0.7595 | 0.1874 | 0.031* | |
C2 | 0.18868 (19) | 1.1317 (7) | 0.1775 (2) | 0.0504 (11) | |
H21 | 0.1467 | 1.1309 | 0.1684 | 0.076* | |
H22 | 0.1990 | 1.2555 | 0.1571 | 0.076* | |
H23 | 0.2078 | 1.1666 | 0.2146 | 0.076* | |
C3 | 0.42025 (15) | −0.0709 (6) | 0.02031 (14) | 0.0259 (7) | |
H31 | 0.4511 | −0.0565 | 0.0551 | 0.031* | |
H32 | 0.4297 | −0.2098 | 0.0023 | 0.031* | |
C4 | 0.41839 (18) | 0.1611 (6) | −0.01112 (17) | 0.0380 (9) | |
H41 | 0.4552 | 0.1801 | −0.0163 | 0.057* | |
H42 | 0.4121 | 0.3003 | 0.0080 | 0.057* | |
H43 | 0.3868 | 0.1500 | −0.0450 | 0.057* | |
C5 | 0.56084 (15) | 0.3712 (6) | 0.15678 (14) | 0.0276 (7) | |
H51 | 0.5558 | 0.5415 | 0.1648 | 0.033* | |
H52 | 0.5995 | 0.3183 | 0.1806 | 0.033* | |
C6 | 0.55857 (18) | 0.3542 (8) | 0.10026 (16) | 0.0433 (10) | |
H61 | 0.5910 | 0.4444 | 0.0970 | 0.065* | |
H62 | 0.5220 | 0.4223 | 0.0767 | 0.065* | |
H63 | 0.5612 | 0.1850 | 0.0913 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Eu1 | 0.01554 (9) | 0.01393 (8) | 0.01771 (9) | 0.00028 (6) | 0.00620 (6) | 0.00126 (6) |
S1 | 0.0176 (4) | 0.0167 (3) | 0.0206 (4) | −0.0004 (3) | 0.0096 (3) | −0.0001 (3) |
S2 | 0.0234 (4) | 0.0180 (3) | 0.0155 (4) | −0.0045 (3) | 0.0070 (3) | −0.0010 (3) |
S3 | 0.0178 (4) | 0.0228 (3) | 0.0239 (4) | 0.0025 (3) | 0.0068 (3) | 0.0005 (3) |
O1 | 0.0294 (13) | 0.0184 (10) | 0.0538 (17) | −0.0011 (10) | 0.0238 (12) | −0.0038 (11) |
O2 | 0.0252 (12) | 0.0261 (11) | 0.0214 (12) | −0.0063 (9) | 0.0071 (10) | 0.0031 (9) |
O3 | 0.0281 (12) | 0.0387 (13) | 0.0202 (12) | −0.0037 (10) | 0.0068 (10) | 0.0040 (10) |
O4 | 0.0282 (12) | 0.0262 (12) | 0.0326 (13) | −0.0033 (10) | 0.0150 (11) | −0.0077 (10) |
O5 | 0.0326 (14) | 0.0567 (16) | 0.0209 (13) | −0.0128 (12) | 0.0034 (10) | −0.0066 (12) |
O6 | 0.0554 (17) | 0.0224 (11) | 0.0337 (14) | −0.0038 (11) | 0.0210 (13) | 0.0081 (10) |
O7 | 0.0175 (11) | 0.0372 (12) | 0.0231 (12) | 0.0051 (10) | 0.0049 (9) | −0.0015 (10) |
O8 | 0.0273 (13) | 0.0621 (17) | 0.0216 (13) | 0.0094 (13) | 0.0067 (10) | 0.0003 (12) |
O9 | 0.0366 (14) | 0.0200 (11) | 0.0603 (19) | 0.0029 (10) | 0.0212 (13) | 0.0004 (11) |
O10 | 0.0222 (11) | 0.0271 (11) | 0.0260 (13) | −0.0064 (10) | 0.0084 (10) | −0.0037 (10) |
O11 | 0.0231 (12) | 0.0307 (12) | 0.0219 (9) | −0.0057 (10) | 0.0052 (9) | 0.0043 (10) |
O12 | 0.0266 (13) | 0.0459 (15) | 0.0390 (16) | 0.0081 (12) | 0.0014 (11) | 0.0075 (12) |
C1 | 0.0198 (16) | 0.0283 (16) | 0.0328 (18) | −0.0016 (14) | 0.0126 (14) | 0.0001 (15) |
C2 | 0.032 (2) | 0.043 (2) | 0.078 (3) | 0.0078 (18) | 0.022 (2) | −0.017 (2) |
C3 | 0.0251 (17) | 0.0283 (16) | 0.0275 (18) | 0.0011 (14) | 0.0133 (14) | −0.0017 (14) |
C4 | 0.043 (2) | 0.035 (2) | 0.046 (2) | −0.0076 (17) | 0.0276 (19) | 0.0022 (17) |
C5 | 0.0214 (16) | 0.0238 (15) | 0.0362 (19) | −0.0044 (14) | 0.0087 (14) | −0.0023 (15) |
C6 | 0.036 (2) | 0.059 (2) | 0.037 (2) | −0.008 (2) | 0.0168 (18) | 0.0086 (19) |
Eu1—O1 | 2.354 (2) | O11—H3 | 0.8320 |
Eu1—O2i | 2.365 (2) | O11—H4 | 0.8311 |
Eu1—O4 | 2.399 (2) | O12—H5 | 0.8299 |
Eu1—O6ii | 2.378 (2) | O12—H6 | 0.8301 |
Eu1—O7 | 2.394 (2) | O12—H6A | 0.8300 |
Eu1—O11 | 2.415 (2) | C1—C2 | 1.515 (5) |
Eu1—O10 | 2.449 (2) | C1—H11 | 0.9700 |
Eu1—O12 | 2.454 (3) | C1—H12 | 0.9700 |
S1—O1 | 1.464 (2) | C2—H21 | 0.9600 |
S1—O2 | 1.460 (2) | C2—H22 | 0.9600 |
S1—O3 | 1.453 (2) | C2—H23 | 0.9600 |
S1—C1 | 1.769 (3) | C3—C4 | 1.514 (5) |
S2—O4 | 1.452 (2) | C3—H31 | 0.9700 |
S2—O5 | 1.449 (3) | C3—H32 | 0.9700 |
S2—O6 | 1.457 (2) | C4—H41 | 0.9600 |
S2—C3 | 1.773 (3) | C4—H42 | 0.9600 |
S3—O7 | 1.479 (2) | C4—H43 | 0.9600 |
S3—O8 | 1.449 (3) | C5—C6 | 1.513 (5) |
S3—O9 | 1.449 (2) | C5—H51 | 0.9700 |
S3—C5 | 1.760 (3) | C5—H52 | 0.9700 |
O2—Eu1ii | 2.365 (2) | C6—H61 | 0.9600 |
O6—Eu1i | 2.378 (2) | C6—H62 | 0.9600 |
O10—H1 | 0.8290 | C6—H63 | 0.9600 |
O10—H2 | 0.8311 | ||
O1—Eu1—O2i | 83.16 (8) | S2—O6—Eu1i | 158.40 (16) |
O1—Eu1—O6ii | 100.24 (8) | S3—O7—Eu1 | 143.38 (14) |
O2i—Eu1—O6ii | 145.38 (9) | Eu1—O10—H1 | 117.3 |
O1—Eu1—O7 | 144.37 (8) | Eu1—O10—H2 | 116.8 |
O2i—Eu1—O7 | 116.14 (8) | H1—O10—H2 | 104.4 |
O6ii—Eu1—O7 | 80.76 (9) | Eu1—O11—H3 | 127.4 |
O1—Eu1—O4 | 141.41 (9) | Eu1—O11—H4 | 120.8 |
O2i—Eu1—O4 | 75.97 (8) | H3—O11—H4 | 104.4 |
O6ii—Eu1—O4 | 80.74 (8) | Eu1—O12—H5 | 123.2 |
O7—Eu1—O4 | 74.17 (8) | Eu1—O12—H6 | 122.6 |
O1—Eu1—O11 | 79.79 (9) | H5—O12—H6 | 104.6 |
O2i—Eu1—O11 | 72.82 (8) | Eu1—O12—H6A | 126.4 |
O6ii—Eu1—O11 | 141.80 (9) | H5—O12—H6A | 104.6 |
O7—Eu1—O11 | 78.30 (8) | C2—C1—S1 | 113.2 (2) |
O4—Eu1—O11 | 122.71 (8) | C2—C1—H11 | 108.9 |
O1—Eu1—O10 | 73.66 (8) | S1—C1—H11 | 108.9 |
O2i—Eu1—O10 | 139.89 (8) | C2—C1—H12 | 108.9 |
O6ii—Eu1—O10 | 72.26 (9) | S1—C1—H12 | 108.9 |
O7—Eu1—O10 | 72.84 (8) | H11—C1—H12 | 107.8 |
O4—Eu1—O10 | 140.02 (8) | C1—C2—H21 | 109.5 |
O11—Eu1—O10 | 71.18 (8) | C1—C2—H22 | 109.5 |
O1—Eu1—O12 | 72.71 (9) | H21—C2—H22 | 109.5 |
O2i—Eu1—O12 | 72.24 (8) | C1—C2—H23 | 109.5 |
O6ii—Eu1—O12 | 75.96 (10) | H21—C2—H23 | 109.5 |
O7—Eu1—O12 | 139.86 (9) | H22—C2—H23 | 109.5 |
O4—Eu1—O12 | 70.17 (9) | C4—C3—S2 | 111.2 (2) |
O11—Eu1—O12 | 137.47 (9) | C4—C3—H31 | 109.4 |
O10—Eu1—O12 | 127.89 (8) | S2—C3—H31 | 109.4 |
O3—S1—O2 | 112.15 (13) | C4—C3—H32 | 109.4 |
O3—S1—O1 | 113.15 (15) | S2—C3—H32 | 109.4 |
O2—S1—O1 | 111.05 (13) | H31—C3—H32 | 108.0 |
O3—S1—C1 | 109.20 (15) | C3—C4—H41 | 109.5 |
O2—S1—C1 | 106.60 (15) | C3—C4—H42 | 109.5 |
O1—S1—C1 | 104.15 (14) | H41—C4—H42 | 109.5 |
O5—S2—O4 | 112.10 (15) | C3—C4—H43 | 109.5 |
O5—S2—O6 | 112.51 (16) | H41—C4—H43 | 109.5 |
O4—S2—O6 | 112.32 (14) | H42—C4—H43 | 109.5 |
O5—S2—C3 | 107.09 (16) | C6—C5—S3 | 113.2 (2) |
O4—S2—C3 | 106.40 (14) | C6—C5—H51 | 108.9 |
O6—S2—C3 | 105.88 (16) | S3—C5—H51 | 108.9 |
O8—S3—O9 | 114.06 (17) | C6—C5—H52 | 108.9 |
O8—S3—O7 | 111.30 (14) | S3—C5—H52 | 108.9 |
O9—S3—O7 | 110.38 (15) | H51—C5—H52 | 107.8 |
O8—S3—C5 | 106.13 (16) | C5—C6—H61 | 109.5 |
O9—S3—C5 | 107.89 (15) | C5—C6—H62 | 109.5 |
O7—S3—C5 | 106.66 (15) | H61—C6—H62 | 109.5 |
S1—O1—Eu1 | 144.36 (13) | C5—C6—H63 | 109.5 |
S1—O2—Eu1ii | 151.51 (14) | H61—C6—H63 | 109.5 |
S2—O4—Eu1 | 159.61 (16) | H62—C6—H63 | 109.5 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H1···O8iii | 0.83 | 2.00 | 2.774 (3) | 156 |
O10—H2···O9ii | 0.83 | 2.10 | 2.894 (3) | 159 |
O11—H3···O8 | 0.83 | 2.12 | 2.804 (3) | 139 |
O11—H4···O3i | 0.83 | 2.04 | 2.818 (3) | 155 |
O12—H5···O5iv | 0.83 | 1.96 | 2.787 (4) | 178 |
O12—H6···O12v | 0.83 | 2.53 | 3.092 | 126 |
O12—H6A···O5v | 0.83 | 2.58 | 3.302 (4) | 146 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1/2, y+1, −z; (v) −x+1/2, y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Eu(C2H5SO3)3(H2O)3] |
Mr | 533.41 |
Crystal system, space group | Monoclinic, I2/a |
Temperature (K) | 233 |
a, b, c (Å) | 24.323 (2), 5.4408 (4), 27.066 (2) |
β (°) | 111.328 (9) |
V (Å3) | 3336.5 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 4.19 |
Crystal size (mm) | 0.57 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.578, 0.672 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22872, 3282, 2788 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.620 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.050, 1.22 |
No. of reflections | 3282 |
No. of parameters | 216 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.16, −1.19 |
Computer programs: IPDS Software (Stoe & Cie, 2000), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), SHELXL97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H1···O8i | 0.83 | 2.00 | 2.774 (3) | 156 |
O10—H2···O9ii | 0.83 | 2.10 | 2.894 (3) | 159 |
O11—H3···O8 | 0.83 | 2.12 | 2.804 (3) | 139 |
O11—H4···O3iii | 0.83 | 2.04 | 2.818 (3) | 155 |
O12—H5···O5iv | 0.83 | 1.96 | 2.787 (4) | 178 |
O12—H6···O12v | 0.83 | 2.53 | 3.092 | 126 |
O12—H6A···O5v | 0.83 | 2.58 | 3.302 (4) | 146 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, y+1, z; (iii) x, y−1, z; (iv) −x+1/2, y+1, −z; (v) −x+1/2, y, −z. |
From the beginning of the 20th century, some alkanesulfonates of the rare earth elements, such as samarium and neodymium methane-, ethane-, propane- and isobutansulfonate, have been known and characterized by elemental analysis (James et al., 1912). Crystal structure analyses have only, thus far, been performed on methanesulfonates of the lanthanoids and their hydrates (Arico et al., 1997, 2001; Wickleder, 2001, 2002; Wickleder & Müller, 2004). The first crystallographically characterized rare earth ethanesulfonate is presented here. catena-poly[[triaquabis(ethanesulfonato-κO)europium(III)]-µ-ethanesulfonato-κ2O:O'], (I), is obtained from a solution of europium(III) oxide and ethanesulfonic acid in water after slow evaporation of the solvent at room temperature. After recrystallization of the raw product from a mixture of water and selected alcohols, thin colourless needles suitable for single-crystal diffraction experiments are isolated. [Eu(C2H5SO3)3(H2O)3] crystallizes in the monoclinic space group I2/a and in the chosen asymmetric unit the central Eu atom is surrounded by three sulfonate anions and three water molecules, all in general positions. The primary coordination is completed by two additional O atoms from two further ethanesulfonate anions (Fig. 1). In total the Eu atom is eightfold coordinated by O atoms. The coordination polyhedron is a bicapped trigonal prism. The Eu—O distances are in the range 2.354 (2) to 2.454 (3) Å. Bond lengths and angles of the sulfonate groups are as expected, with S—O distances of 1.449 (3)–1.479 (2) Å, S—C distances of 1.760 (3)–1.773 (3) Å and C—C distances of 1.513 (5)–1.515 (5) Å.
The ethanesulfonate anions containing atoms S1 and S2 operate as bidentate ligands; they link the metal atoms in a µ-κO:κO' mode and thus connect the building blocks into infinite chains along [010] (Fig. 2). In contrast, the anion containing S3 only acts as a monodentate ligand. Some µ-κO:κO'-bridging ethanesulfonate ligands are also found in dinuclear chloro–sulfonato–antimony(V) complexes (Burchardt et al., 1998; Lang et al., 1998) and in polymeric chains of the dioxouranium(VI) complex [(UO2)(H2O)(C2H5SO3)2] (Alcock et al., 1993) and the ethanesulfonato–hydrogenmethanephosphonato–diorganyltin(IV) compound [(C4H9)2Sn{OP(O)(OH)CH3}OS(O)2C2H5] (Shankar et al., 2006). In contrast to this bridging mode, the ethanesulfonate group in the polymeric chain structure of [Cu(CO)C2H5SO3] is 1κO:2κO',κO''-bridging (Doyle et al., 1983).
The structural assembly of (I) in the solid state is determined by a hierarchical system of supramolecular interactions with a pronounced gradation in bond strength with respect to each of the three dimensions. Firstly, strong Eu—O bonds are responsible for the formation of a one-dimensional chain structure. Secondly, hydrogen bonding occurs between water molecules of one chain and sulfonate anions and water molecules of adjacent chains, and thus provides an association of the one-dimensional supramolecular system in a second direction, resulting in a layered assembly of chains. Atoms H3 and H4 take part in hydrogen bonding to O atoms of the same chain exclusively. Although the bond strength can be classified as only weak to medium, proved by the O···O distances of 2.774 (3)–3.302 (4) Å, the contribution of hydrogen bonding to the composition of the solid is essential. In the third direction, van der Waals forces between ethyl groups are the only interactions of note. Fig. 3 shows the connection of the chains in the solid state packing.