Tris(2-meth­oxy­ethanaminium) dodeca­molybdophosphate trihydrate

Akbar Raissi Shabari; Sara Kharaghani; Mehrdad Pourayoubi

doi:10.1107/S1600536810028801

. 2010 Jul 24;66(Pt 8):m1000. doi: 10.1107/S1600536810028801

Tris(2-methoxyethanaminium) dodecamolybdophosphate trihydrate

Akbar Raissi Shabari ^a,^*, Sara Kharaghani ^a, Mehrdad Pourayoubi ^b

PMCID: PMC3007375 PMID: 21588083

Abstract

The asymmetric unit of the polyoxidometalate-based organic–inorganic hybrid title compound, (C₃H₁₀NO)₃[PMo₁₂O₄₀]·3H₂O, consists of one α-Keggin-type [PMo₁₂O₄₀]³⁻ polyoxidoanion, three independent [CH₃–O–CH₂–CH₂–NH₃]⁺ cations and three solvent water molecules. The polyoxidoanion shows characteristic features with respect to bond lengths and angles. In the crystal structure, extensive intermolecular N—H⋯O and O—H⋯O hydrogen bonding between the organic cations, inorganic anions and solvent water molecules leads to a three-dimensional supramolecular network.

Related literature

For background information on polyoxometalate-based organic–inorganic hybrid materials, see: Pourayoubi & Mahjoub (2007 ▶, 2010 ▶); Raissi Shabari et al. (2009 ▶). For related structures, see: Gong et al. (2006 ▶); Han et al. (2005 ▶).

Experimental

Crystal data

(C₃H₁₀NO)₃[PMo₁₂O₄₀]·3H₂O
M _r = 2104.66
Monoclinic,
a = 12.7806 (2) Å
b = 27.0489 (4) Å
c = 14.6360 (2) Å
β = 114.876 (1)°
V = 4590.24 (12) Å³
Z = 4
Mo Kα radiation
μ = 3.32 mm⁻¹
T = 100 K
0.10 × 0.05 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.820, T _max = 0.907
100492 measured reflections
12174 independent reflections
10404 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.052
S = 1.00
12174 reflections
646 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028801/lh5078sup1.cif

e-66-m1000-sup1.cif^{(53KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028801/lh5078Isup2.hkl

e-66-m1000-Isup2.hkl^{(595.2KB, 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
O1W—H1WA⋯O2W	0.75	2.00	2.726 (5)	161
O1W—H1WB⋯O31ⁱ	0.85	2.14	2.936 (4)	157
O2W—H2WB⋯O15	0.83	1.99	2.807 (3)	167
O2W—H2WA⋯O22ⁱⁱ	0.90	2.03	2.780 (3)	140
O3W—H3WA⋯O40ⁱⁱⁱ	0.88	2.05	2.904 (3)	162
O3W—H3WB⋯O10^iv	0.84	1.97	2.772 (3)	159
N1S—H1NA⋯O3W	0.91	1.93	2.812 (4)	164
N1S—H1NB⋯O2S^v	0.91	2.59	3.182 (4)	123
N1S—H1NB⋯O9^v	0.91	2.24	2.949 (4)	134
N1S—H1NC⋯O1S	0.91	2.31	2.731 (4)	108
N1S—H1NC⋯O31^v	0.91	2.48	3.110 (4)	127
N1S—H1NC⋯O35ⁱⁱ	0.91	2.28	2.887 (3)	124
N2S—H2NA⋯O2S	0.91	2.42	2.814 (5)	106
N2S—H2NA⋯O8	0.91	1.94	2.811 (3)	159
N2S—H2NB⋯O1W	0.91	1.83	2.629 (5)	145
N2S—H2NC⋯O3S	0.91	1.93	2.798 (5)	158
N3S—H3NA⋯O23ⁱⁱ	0.91	2.31	3.110 (4)	146
N3S—H3NB⋯O34^iv	0.91	2.08	2.955 (4)	161
N3S—H3NC⋯O2W	0.91	1.96	2.822 (4)	158

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

Acknowledgments

Support of this investigation by the Islamic Azad University-North Tehran Branch is gratefully acknowledged.

supplementary crystallographic information

Comment

Keggin-type polyoxoanions have been used as the inorganic building blocks to construct polyoxometalate-based organic-inorganic hybrid materials containing the organic cations such as protonated-amino acid (Raissi Shabari et al., 2009), heterocyclic base (Pourayoubi & Mahjoub, 2007) and amide (Pourayoubi & Mahjoub, 2010).

We report here on the synthesis and crystal structure of a new POM-based hybrid material containing a protonated aminoether.

The title polyoxometalate-based organic-inorganic hybrid compound consists of one [PMo₁₂O₄₀]^3- polyoxoanion, three symmetrically independent CH₃–O–CH₂–CH₂–NH₃⁺ cations and three solvent water molecules. The inorganic anion shows a classical α-Keggin structure (Fig. 1) with 4 different types of O atoms. This includes 12 terminal O atoms, 4 O atoms which are bonded to P and Mo, 12 MoO₆ octahedra corner-shared and 12 MoO₆ octahedra edge-shared oxygen atoms.

The central PO₄ tetrahedron is slightly distorted and is surrounded by 12 distorted MoO₆ octahedra. The P—O bond lengths range from 1.534 (2) to 1.539 (2) Å, and the O—P—O angles are in the range of 109.20 (11)–109.66 (11)°.

All three organic cations (Fig. 2) show slight differences in bond lengths, angles and torsion angles. They are involved in an extensive hydrogen bonding. Several N–H···O (N···O distances are in the range of 2.629 (5) to 3.182 (4) Å) and O–H···O (O···O distances are in the range from 2.726 (5) to 2.936 (4) Å) hydrogen bonds between the organic cations, inorganic anions and crystal water molecules lead to a 3-D supramolecular network.

In the title hybrid compound, the position of organic cations and water molecules allows to direct interaction of one polyoxoanion with four neighboring polyoxoanions via O···O contacts [2.80-3.018 Å]. Two important O···O contacts are the O36···O6 (2.800 Å) and O32···O17 (2.814 Å) interactions, O36 and O32 are the terminal and O6 and O17 are the bridged oxygen atoms of the polyoxoanions. The less important O···O contacts are O31···O35 (3.018 Å), O29···O34 (3.012 Å), O27···O28 (2.981 Å) and O24···O40 (2.915 Å) [O31, O35, O29, O34 and O40 are terminal and O24, O27 and O28 are bridging oxygen atoms]. Similar interactions have been observed in the structure of (C₅N₂H₇)₅H[P₂Mo₅O₂₃] (C₅N₂H₇ = protonated 2-aminopyridine) reported by Gong et al. (2006) [O_terminal···O_terminal = 2.398 Å] and in the structure of (H_3/4pbpy)₄[PMo₁₂O₄₀].1.25H₂O (pbpy = 5-phenyl-2-(4-pyridinyl)pyridine) reported by Han et al. (2005) [O_terminal···O_terminal and O_terminal···O_bridge in the range of 2.931 to 3.001 Å].

Experimental

The title hybrid compound was obtained from mixing H₃PMo₁₂O₄₀ and SrCl₂.2H₂O and then the treatment with CH₃OCH₂CH₂NH₂ in a mixture of H₂O and CH₃CN. ³¹P-NMR (DMSO-d₆, p.p.m.): -4.11. IR (KBr, cm^-1): 3371.4 m, 2908.7 w, 1611.7 m, 1501.6 m, 1208.2 w, 1062.1 s, 957.9 vs, 878.8 s, 783.6 vs.