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Acta Cryst. (2008). E64, i35    [ doi:10.1107/S1600536808014359 ]

Hexaaquadibromidoeuropium(III) bromide, [EuBr2(H2O)6]Br

C. Hoch and A. Simon

Abstract top

The title compound crystallizes with the GdCl3·6H2O structure type, exhibiting discrete [EuBr2(H2O)6]+ cations as the main building blocks, linked with isolated bromide anions via H...Br hydrogen bonds to form a complex framework. The Eu atom and one Br atom each lie on a twofold rotation axis.

Comment top

[EuBr2(H2O)6]Br crystallizes in the monoclinic space group P2/c (No. 13) and is isotypic with the GdCl3.6H2O structure type (Marezio et al., 1961), like many chloride hexahydrates MCl3.6H2O with M = Y (Bell & Smith, 1990), Ce (Reuter et al., 1994), Nd (Habenschuss & Spedding, 1980), Sm - Tm (Graeber et al., 1966), Am, Bk (Burns & Peterson, 1971), and two bromide hexahydrates MBr3.6H2O (M = Pr, Dy, Junk et al., 1999).

The Eu atoms in [EuBr2(H2O)6]Br are coordinated by six water molecules and two bromine atoms forming a distorted square antiprism (Fig. 1). Hydrogen bonds H—Br connect the [EuBr2(H2O)6]+ cations with the Br- counter-anions to a network. The bromine atom Br1 belonging to the cationic complex is surrounded by four, the isolated bromine atom Br2 by six hydrogen bonds (Fig. 2). A view of the unit cell of [EuBr2(H2O)6]Br is given in Fig. 3.

The H—Br distances (2.46–2.63 Å) are in good agreement with those in other bromide hydrates (e.g. 2.38–2.54 Å in [Sc(H2O)5(OH)]Br2, Kolitsch, 2006; 2.32–2.80 Å in [Ca(H2O)6]2[CdBr6], Duhlev et al., 1988; 2.40–2.83 A in NaBr.2H2O, Tegenfeldt et al., 1979). The EuIII—O distances in [EuBr2(H2O)6]Br range from 2.39 to 2.42 Å and thus are very similar to those in EuCl3.3H2O (2.39–2.40 Å, Reuter et al., 1994), EuCl3.6H2O (2.39–2.43 Å, Graeber et al., 1966), or EuCl(OH)2 (2.35–2.44 Å, Demyanets et al., 1974). The same holds for the EuIII—Br distances in [EuBr2(H2O)6]Br (2.94 Å) which lie between those in Na3EuBr6 (2.83 Å, Wickleder & Meyer, 1995) and those in EuOBr (3.19 Å, Bärnighausen et al., 1965).

Related literature top

For related literature, see: Bärnighausen et al. (1965); Bell & Smith (1990); Burns & Peterson (1971); Demyanets et al. (1974); Duhlev et al. (1988); Graeber et al. (1966); Habenschuss & Spedding (1980); Junk et al. (1999); Kolitsch (2006); Marezio et al. (1961); Reuter et al. (1994); Tegenfeldt et al. (1979); Wickleder & Meyer (1995).

Experimental top

Colourless single crystals of [EuBr2(H2O)6]Br were obtained by recrystallizing the commercially available product ("EuBr3.X H2O", Alfa Aesar, 99.99%) under argon from degassed aqueous HBr solution by slow cooling of a solution saturated at ca 60 °C to room temperature.

Refinement top

The positions of all hydrogen atoms were identified from the difference Fourier map, close to their ideal positions. Their refinement was performed applying a DFIX command (Sheldrick, 2008), restricting the O—H bond lengths to 0.82 ± 0.02 Å.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2006); cell refinement: X-AREA (Stoe & Cie, 2006); data reduction: X-AREA (Stoe & Cie, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DRAWXTL (Finger et al., 2007); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. View of the cationic [Eu(H2O)6Br2]+ unit in [Eu(H2O)6Br2]Br, with displacement ellipsoids drawn at the 90% propability level. H atoms are shown as black spheres of arbitrary radii. [Symmetry code: (i) -x, y, 1/2 - z.]
[Figure 2] Fig. 2. View of the H—Br contacts in [Eu(H2O)6Br(2)2]Br(1), left: four hydrogen bonds link Br1 to water molecules, right: six hydrogen bonds link Br2 to water molecules. All displacement ellipsoids are drawn at the 90% propability level. [Symmetry codes: (i) -x, y, 1/2 - z; (ii) -x, -y, -z; (iii) x, -y, 1/2 + z.]
[Figure 3] Fig. 3. View along (010) on the crystal structure of [Eu(H2O)6Br2]Br. Small black spheres represent H atoms, large black spheres represent Eu atoms, grey spheres represent Br atoms, light grey spheres represent O atoms. Grey polyhedra represent the coordination of H atoms around Br atoms.
Hexaaquadibromidoeuropium(III) bromide top
Crystal data top
[EuBr2(H2O)6]BrF000 = 456
Mr = 499.79Dx = 3.006 Mg m−3
Monoclinic, P2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 10367 reflections
a = 8.1672 (7) Åθ = 3.0–32.1º
b = 6.7538 (4) ŵ = 16.52 mm−1
c = 12.5451 (10) ÅT = 293 (2) K
β = 127.077 (5)ºIrregular polyhedron, clear colourless
V = 552.08 (8) Å30.25 × 0.24 × 0.18 mm
Z = 2
Data collection top
Stoe IPDSII
diffractometer		1613 independent reflections
Radiation source: fine-focus sealed tube1397 reflections with I > 2s(I)
Monochromator: graphiteRint = 0.067
T = 293(2) Kθmax = 30.0º
ω scans (in two runs with φ1 = 0° and φ2 = 90°)θmin = 3.0º
Absorption correction: numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]		h = −11→11
Tmin = 0.065, Tmax = 0.155k = −9→9
10921 measured reflectionsl = −17→17
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.028  w = 1/[σ2(Fo2) + (0.0169P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.049(Δ/σ)max < 0.001
S = 1.11Δρmax = 1.14 e Å−3
1613 reflectionsΔρmin = −1.10 e Å−3
72 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0409 (10)
Secondary atom site location: difference Fourier map
Crystal data top
[EuBr2(H2O)6]BrV = 552.08 (8) Å3
Mr = 499.79Z = 2
Monoclinic, P2/cMo Kα
a = 8.1672 (7) ŵ = 16.52 mm−1
b = 6.7538 (4) ÅT = 293 (2) K
c = 12.5451 (10) Å0.25 × 0.24 × 0.18 mm
β = 127.077 (5)º
Data collection top
Stoe IPDSII
diffractometer		1613 independent reflections
Absorption correction: numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]		1397 reflections with I > 2s(I)
Tmin = 0.065, Tmax = 0.155Rint = 0.067
10921 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02872 parameters
wR(F2) = 0.049All H-atom parameters refined
S = 1.11Δρmax = 1.14 e Å−3
1613 reflectionsΔρmin = −1.10 e Å−3
Special details top

Experimental. The title compoud is a commercially available chemical (Alfa Aesar) and was recrystallized under argon from degassed aqueous HBr solution. A suitable single-crystal was sealed with mother liquor in a thin-walled glass capillary.

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
xyzUiso*/Ueq
Eu10.500000.16454 (4)0.250000.0170 (1)
Br10.70613 (6)−0.15845 (7)0.44669 (4)0.0295 (1)
Br20.000000.63151 (9)0.250000.0318 (2)
O10.1772 (5)0.3097 (5)0.0676 (3)0.0320 (7)
O20.2413 (5)0.0620 (5)0.2757 (4)0.0313 (7)
O30.4434 (5)0.4262 (5)0.3524 (4)0.0335 (7)
H110.148 (11)0.336 (10)−0.006 (4)0.06 (2)*
H120.072 (9)0.258 (14)0.050 (10)0.10 (3)*
H210.253 (12)0.098 (11)0.342 (5)0.07 (2)*
H220.183 (11)−0.046 (6)0.253 (9)0.09 (3)*
H310.518 (10)0.526 (7)0.376 (8)0.08 (2)*
H320.321 (5)0.456 (12)0.315 (8)0.09 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Eu10.0168 (1)0.0180 (1)0.0172 (1)0.0000.0109 (1)0.000
Br10.0295 (2)0.0293 (2)0.0266 (3)0.0027 (2)0.0152 (2)0.0066 (2)
Br20.0294 (3)0.0360 (3)0.0327 (4)0.0000.0202 (3)0.000
O10.0233 (13)0.0385 (17)0.0256 (18)0.0036 (12)0.0102 (13)0.0084 (14)
O20.0316 (15)0.0367 (17)0.0355 (19)−0.0076 (13)0.0254 (15)−0.0055 (14)
O30.0308 (15)0.0302 (15)0.042 (2)−0.0035 (13)0.0229 (16)−0.0106 (14)
Geometric parameters (Å, °) top
Eu1—Br12.9449 (5)Eu1—O3i2.388 (3)
Eu1—Br1i2.9449 (5)O1—H110.82 (2)
Eu1—O12.424 (3)O1—H120.83 (2)
Eu1—O1i2.424 (3)O2—H210.82 (2)
Eu1—O22.422 (3)O2—H220.82 (2)
Eu1—O2i2.422 (3)O3—H310.83 (2)
Eu1—O32.388 (3)O3—H320.83 (2)
Br1—Eu1—O1146.89 (8)O1—Eu1—O272.6 (1)
Br1i—Eu1—O1i146.89 (8)O1i—Eu1—O2i72.6 (1)
Br1—Eu1—O1i76.21 (9)O1—Eu1—O2i122.0 (1)
Br1i—Eu1—O176.21 (9)O1i—Eu1—O2122.0 (1)
Br1—Eu1—O277.33 (8)O1—Eu1—O375.8 (1)
Br1i—Eu1—O2i77.33 (8)O1i—Eu1—O3i75.8 (1)
Br1—Eu1—O2i78.22 (8)O1—Eu1—O3i69.3 (1)
Br1i—Eu1—O278.22 (8)O1i—Eu1—O369.3 (1)
Br1—Eu1—O3107.21 (9)O2—Eu1—O370.9 (1)
Br1i—Eu1—O3i107.21 (9)O2i—Eu1—O3i70.9 (1)
Br1—Eu1—O3i143.18 (8)O2—Eu1—O3i138.6 (1)
Br1i—Eu1—O3143.18 (8)O2i—Eu1—O3138.6 (1)
Br1—Eu1—Br1i84.41 (2)H11—O1—H12104 (8)
O1—Eu1—O1i132.3 (2)H21—O2—H22107 (8)
O2—Eu1—O2i146.8 (2)H31—O3—H32112 (8)
O3—Eu1—O3i84.5 (2)
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H11···Br2ii0.83 (2)2.53 (8)3.343 (4)168 (6)
O1—H12···Br1iii0.83 (2)2.52 (13)3.333 (4)165 (6)
O2—H21···Br1iv0.82 (2)2.49 (10)3.307 (4)172 (6)
O2—H22···Br2v0.83 (2)2.63 (11)3.417 (4)161 (6)
O3—H31···Br1vi0.83 (2)2.46 (8)3.288 (4)173 (6)
O3—H32···Br20.83 (2)2.52 (11)3.328 (5)163 (6)
Symmetry codes: (ii) −x, −y+1, −z; (iii) x−1, −y, z−1/2; (iv) −x+1, −y, −z+1; (v) x, y−1, z; (vi) x, y+1, z.
Table 1
Selected geometric parameters (Å, °) top
Eu1—Br12.9449 (5)Eu1—O3i2.388 (3)
Eu1—Br1i2.9449 (5)O1—H110.82 (2)
Eu1—O12.424 (3)O1—H120.83 (2)
Eu1—O1i2.424 (3)O2—H210.82 (2)
Eu1—O22.422 (3)O2—H220.82 (2)
Eu1—O2i2.422 (3)O3—H310.83 (2)
Eu1—O32.388 (3)O3—H320.83 (2)
Br1—Eu1—O1146.89 (8)O1—Eu1—O272.6 (1)
Br1i—Eu1—O1i146.89 (8)O1i—Eu1—O2i72.6 (1)
Br1—Eu1—O1i76.21 (9)O1—Eu1—O2i122.0 (1)
Br1i—Eu1—O176.21 (9)O1i—Eu1—O2122.0 (1)
Br1—Eu1—O277.33 (8)O1—Eu1—O375.8 (1)
Br1i—Eu1—O2i77.33 (8)O1i—Eu1—O3i75.8 (1)
Br1—Eu1—O2i78.22 (8)O1—Eu1—O3i69.3 (1)
Br1i—Eu1—O278.22 (8)O1i—Eu1—O369.3 (1)
Br1—Eu1—O3107.21 (9)O2—Eu1—O370.9 (1)
Br1i—Eu1—O3i107.21 (9)O2i—Eu1—O3i70.9 (1)
Br1—Eu1—O3i143.18 (8)O2—Eu1—O3i138.6 (1)
Br1i—Eu1—O3143.18 (8)O2i—Eu1—O3138.6 (1)
Br1—Eu1—Br1i84.41 (2)H11—O1—H12104 (8)
O1—Eu1—O1i132.3 (2)H21—O2—H22107 (8)
O2—Eu1—O2i146.8 (2)H31—O3—H32112 (8)
O3—Eu1—O3i84.5 (2)
Symmetry codes: (i) −x+1, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H11···Br2ii0.83 (2)2.53 (8)3.343 (4)168 (6)
O1—H12···Br1iii0.83 (2)2.52 (13)3.333 (4)165 (6)
O2—H21···Br1iv0.82 (2)2.49 (10)3.307 (4)172 (6)
O2—H22···Br2v0.83 (2)2.63 (11)3.417 (4)161 (6)
O3—H31···Br1vi0.83 (2)2.46 (8)3.288 (4)173 (6)
O3—H32···Br20.83 (2)2.52 (11)3.328 (5)163 (6)
Symmetry codes: (ii) −x, −y+1, −z; (iii) x−1, −y, z−1/2; (iv) −x+1, −y, −z+1; (v) x, y−1, z; (vi) x, y+1, z.
references
References top

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