Yttrium ethyl­enediammonium squarate tetra­hydrate

Louiza Zenkhri; Nathalie Audebrand; Thierry Bataille

doi:10.1107/S1600536811011251

. 2011 Apr 7;67(Pt 5):m529–m530. doi: 10.1107/S1600536811011251

Yttrium ethylenediammonium squarate tetrahydrate

Louiza Zenkhri ^a,^*, Nathalie Audebrand ^b, Thierry Bataille ^b

PMCID: PMC3089218 PMID: 21754270

Abstract

The title compound, {(C₂H₁₀N₂)_1.5[Y(C₄O₄)₃(H₂O)₄]}_n {systematic name: catena-poly[sesqui(ethylenediammonium) [[tetraaquabis(squarato-κO)yttrium(III)]-μ-squarato-κ² O:O′]]}, was synthesized by slow evaporation of an acid solution. The asymetric unit contains one yttrium cation in an antiprismatic environnement, three squarate groups, one and a half protonated ethylenediamine molecules and four water molecules. YO₈ polyhedra are connected through bis(monodentate) squarates, leading to infinite zigzag chains, in between which are located ammonium groups. A framework of hydrogen bonds between protonated amine N atoms, water molecules and squarate anions ensures the cohesion of the structure.

Related literature

For a related structure, see: Kazerouni et al. (1994) ▶. The title compound was obtained together with two polymorphs of (C₂H₁₀N₂)(HC₄O₄)₂(H₂O) (Mathew et al., 2002 ▶; Zenkhri et al., 2011) ▶. For related yttrium squarates with potassium, see: Mahé & Bataille (2004 ▶).

Experimental

Crystal data

(C₂H₁₀N₂)_1.5[Y(C₄O₄)₃(H₂O)₄]
M _r = 590.27
Monoclinic,
a = 8.9780 (2) Å
b = 13.2864 (3) Å
c = 18.3970 (4) Å
β = 90.935 (1)°
V = 2194.20 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.75 mm⁻¹
T = 293 K
0.22 × 0.14 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965) ▶ T _min = 0.583, T _max = 0.734
23285 measured reflections
5016 independent reflections
4140 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.103
S = 1.10
5016 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 1.77 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DIRAX/LSQ (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011251/ru2003sup1.cif

e-67-0m529-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011251/ru2003Isup2.hkl

e-67-0m529-Isup2.hkl^{(240.7KB, hkl)}

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
N1—H12⋯O3ⁱ	0.87	2.21	3.027 (4)	157
N1—H12⋯O9ⁱⁱ	0.87	2.36	2.929 (4)	123
N1—H11⋯O4ⁱ	0.87	2.36	2.995 (4)	131
N1—H11⋯O7ⁱⁱ	0.87	2.28	2.987 (4)	138
N1—H13⋯O6ⁱⁱ	0.87	2.36	2.970 (4)	127
N1—H13⋯O12ⁱⁱ	0.87	2.26	3.032 (4)	148
N2—H23⋯O2	0.85	1.87	2.707 (4)	167
N2—H21⋯O4ⁱ	0.96	1.92	2.832 (4)	159
N2—H21⋯O7ⁱⁱ	0.96	2.46	2.952 (4)	112
N2—H22⋯O5ⁱⁱⁱ	0.95	2.01	2.929 (4)	163
N3—H31⋯O4	0.87	2.22	2.843 (4)	129
N3—H32⋯O8^iv	0.87	2.18	2.788 (4)	127
N3—H33⋯OW1^v	0.87	2.40	2.997 (4)	126
OW1—H911⋯O11^v	0.94	1.74	2.676 (3)	175
OW1—H912⋯O5	0.93	1.78	2.687 (3)	166
OW2—H922⋯O11	0.94	1.95	2.885 (4)	173
OW2—H921⋯O10^v	0.94	1.79	2.726 (3)	179
OW3—H931⋯O8^vi	0.93	1.94	2.857 (4)	172
OW3—H932⋯O1ⁱ	0.94	2.04	2.954 (5)	163
OW4—H942⋯O5^vi	0.92	1.86	2.779 (3)	172
OW4—H941⋯O10^vii	0.93	1.86	2.761 (4)	163

Open in a new tab

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

Acknowledgments

Grateful thanks are expressed to Dr T. Roisnel (Centre de Diffractométrie X, UMR CNRS 6226) for his assistance with the data collection.

supplementary crystallographic information

Comment

In the course of a study on mixed squarate of amines and metals, the role of the amine group has been investigated in the topology of the organic-inorganic framework. The synthesis led to a new mixed squarate of yttrium and ethylenediamine.

Yttrium is eightfold coordinated in the shape of a square antiprism. YO₈ polyhedra are connected along the b axis through bis(monodentate) squarates in the form of zigzag chains (Figures 1, 2). Amine groups are located between the chains (Figure 2) and are connected to them through hydrogen bonds involving oxygen atoms from squarate groups (Table 1). Other hydrogen bonds between water molecules and squarate groups contribute also to the formation of a three-dimensional molecular framework (Table 1). One ethylenediammonium possesses a gauche conformation as already reported for this molecule (Kazerouni et al., 1994).

Experimental

The title compound, Y(C₄O₄)₃(C₂H₁₀N₂)_1.54H₂O was prepared from an aquous solution (20 ml) of dissolved yttrium nitrate (0.5 mmol), ethylenediamine (0.1 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione, also named squaric acid (0.1 mmol). The slow evaporation at room temperature leads after some hours to the formation of the title compound together with two polymorphs of (HC₄O₄)₂(C₂H₁₀N₂)(H₂O) (Mathew et al., 2002; Zenkhri et al.., 2011).