Tetra­aqua­bis(biuret-κ2 O,O′)yttrium(III) trichloride

William T A Harrison

doi:10.1107/S1600536808008659

. 2008 Apr 2;64(Pt 5):m619. doi: 10.1107/S1600536808008659

Tetraaquabis(biuret-κ² O,O′)yttrium(III) trichloride

William T A Harrison ^a,^*

PMCID: PMC2961277 PMID: 21202174

Abstract

In the title compound, [Y(C₂H₅N₃O₂)₂(H₂O)₄]Cl₃, the Y³⁺ ion (site symmetry 2) is bonded to eight O atoms (arising from two O,O′-bidentate biuret molecules and four water molecules) in a distorted square-antiprismatic arrangement. A network of N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds help to establish the packing, leading to a three-dimensional network. One of the chloride ions has site symmetry 2.

Related literature

For related structures, see: Carugo et al. (1992 ▶); Haddad (1987 ▶, 1988 ▶). For related literature, see: Bernstein et al. (1995 ▶). For valence-sum calculations, see: Brese & O’Keeffe (1991 ▶).

Experimental

Crystal data

[Y(C₂H₅N₃O₂)₂(H₂O)₄]Cl₃
M _r = 473.50
Monoclinic,
a = 7.6510 (4) Å
b = 13.2534 (7) Å
c = 17.2547 (9) Å
β = 100.817 (1)°
V = 1718.57 (16) Å³
Z = 4
Mo Kα radiation
μ = 3.90 mm⁻¹
T = 293 (2) K
0.36 × 0.24 × 0.14 mm

Data collection

Bruker SMART1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.340, T _max = 0.611 (expected range = 0.322–0.579)
8075 measured reflections
3105 independent reflections
2464 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.059
S = 0.98
3105 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808008659/tk2260sup1.cif

e-64-0m619-sup1.cif^{(14.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008659/tk2260Isup2.hkl

e-64-0m619-Isup2.hkl^{(152.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Y1—O1	2.3157 (11)
Y1—O2	2.3349 (11)
Y1—O4	2.3536 (12)
Y1—O3	2.3660 (10)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.10	2.9111 (18)	157
N1—H2⋯Cl1ⁱⁱ	0.86	2.39	3.1897 (17)	155
N2—H3⋯Cl1ⁱⁱ	0.86	2.53	3.3184 (14)	153
N3—H4⋯Cl1ⁱⁱⁱ	0.86	2.54	3.3633 (15)	161
N3—H5⋯Cl1^iv	0.86	2.54	3.3232 (15)	151
O3—H6⋯Cl1^v	0.80	2.39	3.1607 (12)	161
O3—H7⋯Cl2^vi	0.79	2.27	3.0504 (12)	168
O4—H8⋯Cl1	0.75	2.45	3.2028 (13)	177
O4—H9⋯Cl2	0.80	2.40	3.1238 (12)	150

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

Comment

No complexes of yttrium(III) with biuret (biur), H₂N—CO—NH—CO—NH₂ (or C₂H₅N₃O₂) have been structurally characterized. The structures of two samarium-biuret complexes, Sm(biur)₄.(NO₃)₃ (Haddad, 1987) and Sm(biur)₄.(ClO₄)₃ (Haddad, 1988) have been described. In both cases, an SmO₈ square antiprismatic coordination arises for the metal ion. Based on X-ray photographs, it was suggested that all the Ln(biur)₄.(NO₃)₃ and Ln(biur)₄.(ClO₄)₃ compounds are isostructural with their samarium prototypes. In this paper, we describe the synthesis and structure of the title compound, (I).

Compound (I) is an ionic salt containing a new [Y(biur)₂(H₂O)₄]³⁺ complex ion. The complete complex ion is generated by crystallographic 2-fold symmetry, with the Y atom lying on the rotation axis. Two uncoordinated chloride ions, one of which has crystallographic site symmetry 2, complete the structure of (I), Fig. 1.

The resulting YO₈ polyhedral geometry in (I) (Table 1) is a distorted square antiprism (Fig. 2). The nominal square face formed by atoms O1, O2, O1ⁱ and O2ⁱ (i = -x, y, 3/2 - z) is reasonably regular, but the second face formed by the four water molecules (O3, O4, O3ⁱ and O4ⁱ) is much more distorted, and the diagonal O3···O3ⁱ and O4···O4ⁱ distances of 4.223 (2)Å and 3.5197 (19) Å, respectively, are very different. The Y1 atom deviates from the mean planes of O1/O2/O1ⁱ/O2ⁱ and O3/O4/O3ⁱ/O4ⁱ by 1.1616 (8) Å and 1.3151 (9) Å, respectively. The two O atom mean planes are constrained to be parallel by symmetry. The bond valence sum (Brese & O'Keeffe, 1991) for Y1 of 3.34 in (I) indicates that its valence requirement is easily satisfied by this geometry.

The O,O-bidenate coordination of the biuret molecule to the yttrium ion in (I) results in a six-membered chelate ring that is non-planar. As noted previously (Carugo et al., 1992), the biuret molecule can be regarded as two planar amide fragments linked by the NH bridge. Here, the dihedral angle betwen the N1/C1/O1/N2 and N2/C2/O2/N3 units is 5.06 (10)°. The yttrium cation deviates from the N1/C1/O1/N2 and N2/C2/O2/N3 mean planes by 0.894 (4) Å and 0.606 (4) Å, respectively.

The component species in (I) are linked by a dense array of N—H···O, N—H···Cl and O—H···Cl hydrogen bonds (Table 2) resulting in a three-dimensional network. Of note is the N—H···O hydrogen bond, which results in [100] chains (Fig. 3) of cations, in which R²₂(8) loops (Bernstein et al., 1995) linking the molecules are apparent.

Experimental

0.1 M Aqueous solutions of YCl₃ (10 ml) and biuret (10 ml) were mixed and a small quantity of dilute hydrochloric acid was added, to result in a colourless solution. Colourless blocks of (I) grew over several days as the water slowly evaporated.