Tris[4,4′-(ethene-1,2-di­yl)dipyridinium] deca­vanadate dihydrate

Roberto Fernandez de Luis; M Karmele Urtiaga; José Luis Mesa; María I Arriortua

doi:10.1107/S1600536810006215

. 2010 Feb 24;66(Pt 3):m323–m324. doi: 10.1107/S1600536810006215

Tris[4,4′-(ethene-1,2-diyl)dipyridinium] decavanadate dihydrate

Roberto Fernandez de Luis ^a, M Karmele Urtiaga ^a,^*, José Luis Mesa ^b, María I Arriortua ^a

PMCID: PMC2983728 PMID: 21580261

Abstract

The asymmetric unit of the title compound, (C₁₂H₁₂N₂)₃[V₁₀O₂₈]·2H₂O, contains one half of a decavanadate anion, one and a half trans-1,2-bis(4-pyridinio)ethene cations and one water molecule. The V₁₀O₂₈ groups are involved in a three-dimensional hydrogen-bonding network through Ow—H⋯O, N—H⋯O and C—H⋯O interactions.

Related literature

For general background to inorganic–organic vanadates, see: Zavalij & Whittingham (1999 ▶); Fernández de Luis et al. (2009a ▶). For inorganic–organic vanadates constructed from pyridyl ligands, see: Fernández de Luis et al. (2009b ▶); Khan et al. (2004 ▶); Zheng et al. (2001 ▶). For general background to decavanadates, see: Pope & Müller (1991 ▶, 1994 ▶); Rhule et al. (1998 ▶). For hydrogen bonding, see: Steiner (2002 ▶).

Experimental

Crystal data

(C₁₂H₁₂N₂)₃[V₁₀O₂₈]·2H₂O
M _r = 1546.14
Triclinic,
a = 9.7343 (4) Å
b = 11.7754 (5) Å
c = 12.2311 (5) Å
α = 113.072 (4)°
β = 105.396 (4)°
γ = 93.171 (3)°
V = 1223.33 (9) Å³
Z = 1
Mo Kα radiation
μ = 1.92 mm⁻¹
T = 293 K
0.18 × 0.14 × 0.08 mm

Data collection

Oxford Xcalibur2 diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.780, T _max = 0.887
10137 measured reflections
5498 independent reflections
3829 reflections with I > 2σ(I)
R _int = 0.029
3 standard reflections every 50 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.076
S = 0.90
5498 reflections
378 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: TOPOS (Blatov, 2006 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006215/bg2319sup1.cif

e-66-0m323-sup1.cif^{(53.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810006215/bg2319Isup2.hkl

e-66-0m323-Isup2.hkl^{(263.7KB, 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
O1w—H19⋯O11ⁱ	0.92 (3)	2.01 (4)	2.919 (3)	168 (4)
O1w—H20⋯O12	0.92 (3)	2.15 (3)	3.028 (3)	160 (3)
N1—H21⋯O9	0.86	1.88	2.721 (3)	164
N2—H22⋯O2ⁱⁱ	0.86	1.75	2.568 (3)	159
N3—H23⋯O5	0.86	1.71	2.564 (3)	172
C2—H2⋯O1ⁱⁱⁱ	0.93	2.50	3.126 (4)	124
C4—H4⋯O1^iv	0.93	2.32	3.107 (4)	143
C8—H8⋯O10	0.93	2.57	3.162 (4)	122
C11—H11⋯O3^iv	0.93	2.33	3.254 (4)	173
C12—H12⋯O1w	0.93	2.57	3.230 (4)	128
C14—H14⋯O6^v	0.93	2.54	3.202 (3)	128
C14—H14⋯O12^v	0.93	2.39	3.293 (3)	162
C16—H16⋯O13^iv	0.93	2.58	3.401 (4)	147
C17—H17⋯O13	0.93	2.60	3.187 (4)	122

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

Acknowledgments

We gratefully acknowledge financial support of this work by the Ministerio de Educación y Ciencia (MAT2007–60400/66737-C02–01) and the Gobierno Vasco (IT-177–07 and GI07/126-IT-312–07). The authors also thank the technicians of SGIker, Drs J. Sangüesa, I. Orue, P. Vitoria and A. Larrañaga, financed by the National Program for the Promotion of Human Resources within the National Plan of Scientific Research, Development and Innovation, Ministerio de Ciencia y Tecnología and Fondo Social Europeo (FSE), for the X-ray diffraction and magnetic measurements, respectively. RFdeL thanks the MEC (Madrid, España) for funding (BES-2005–10322).

supplementary crystallographic information

Comment

The title compound was synthesized as part of our studies focused on the construction of new inorganic-organic vanadates (Zavalij & Whittingham, 1999) with first row transition metal centres (Fernández et al., 2009b). The pyridyl ligands have very often used since they have two nitrogen atoms that can bridge metal atoms to form polymeric compounds (Fernández et al., 2009a), (Khan et al., 2004), (Zheng et al., 2001). However, the hydrothermal synthesis of the Co/Bpe/V_xO_y system give rise to the crystallization of the title compound as a minor product of the reaction.

The polyoxovanadates exhibit interesting physical and chemical properties with relevance to catalysis, biochemical processes (enzyme inhibitor or activator), medicine, and material science (Pope & Muller, 1991, 1994; Rhule et al., 1998).

The asymmetric unit of (I) consists of one-half decavanadate anion, one and a half pyridinium cations and one water molecule. The decavanadate anion is composed of ten VO₆ octahedra combined via shared edges and corners. Six octahedra are arranged in a 2 x 3 equatorial plane sharing edges; the other four octahedra are distributed above and below the equatorial plane, connected by shared sloping edges with the central six octahedra (Fig. 1).

The V—O bond lengths are classified according to the coordinative conditions of the oxygen atoms: terminal O atoms (V═O, 1.597 (2) - 1.608 (2) Å); double-bridging O atoms (V—O, 1.684 (2) - 2.083 (2) Å), triply bridging O atoms located on the surface of the [V₁₀O₂₈]^6- cluster (V—O, 1.968 (2) - 2.061 (2) Å), and one six-coordinate O atom (V—O 2.085 (2) - 2.344 (2) Å).

The supramolecular structure is formed by Ow—H···O, N—H···O and C—H···O hydrogen bonds, between the anion and the water molecules, between the cation and the anion, and between cation and water molecule (Steiner, 2002).

The decavanadate anions are hydrogen bonded through two water molecules (Fig.2) forming chains in the [010] direction (Fig. 1). The N—H groups of the organic cations interact with the surface oxygen atoms of the decavanadate anion (N1—H21···O9, N2—H22···O2, N3—H23···O5). Each V₁₀O₂₈ anion is linked trough three organic cations to other two V₁₀O₂₈ anion (Fig. 2). The hydrogen bonding trough the water molecules (O—H···O) and organic cations (N—H···O) of the [V₁₀O₂₈] clusters, generates the layers shown in the figure 2. The layers are stacked along the [101] direction via C—H···O hydrogen bonds, establishing the three dimensional supramolecular network (Fig. 3).

Experimental

A mixture consisting of NaVO₃ (0.135 mmol), 1,2-di(4-pyridyl)ethylene (0.135 mmol), Co(NO₃)₂.6H₂O (0.135 mmol), and H₂O (30 ml) in the molar ratio 1:1:1 was placed in a 50-ml Parr Teflon-lined autoclave. The initial pH value was adjusted to 4.0 with a 1M HNO₃ solution under a vigorous stirring. The autoclave was sealed and heated for 3 days at 120°C. After the reaction a mixture of dark brown polycrystalline powder with a minor percentage of the title compound orange single crystals were obtained. In order to obtain the title compound as a single phase, the Co(NO₃)₂.6H₂O was suppressed from the initial reactants. However, all attempts to obtain the title compound as a single phase after the hydrothermal reaction have been unsuccessful.