Poly[4,4′-imino­dipyridinium [tetra-μ3-oxido-tetra­oxido-di-μ4-phosphato-κ4 O:O′:O′′:O′′′-tetra­vanadium(V)]]

Gregory A Farnum; Robert L LaDuca

doi:10.1107/S1600536808038348

. 2008 Nov 22;64(Pt 12):m1602. doi: 10.1107/S1600536808038348

Poly[4,4′-iminodipyridinium [tetra-μ₃-oxido-tetraoxido-di-μ₄-phosphato-κ⁴ O:O′:O′′:O′′′-tetravanadium(V)]]

Gregory A Farnum ^a, Robert L LaDuca ^a,^*

PMCID: PMC2959979 PMID: 21581199

Abstract

In the title salt, {(C₁₀H₁₁N₃)[V₄O₈(PO₄)₂]}_n, cubane-like [V₄O₈]⁴⁺ clusters are connected by phosphate anions into anionic [V₄P₂O₁₆]_n ²ⁿ⁻ layers. These aggregate into the three-dimensional structure via N—H⋯O hydrogen-bonding mechanisms imparted by 4,4′-iminodipyridinium dications situated between the layers.

Related literature

For a nickel vanadate phase incorporating 4,4′-dipyridylamine, see: LaDuca et al. (2001 ▶). For a related layered vanadium phosphate solid containing doubly protonated 4,4′-bipyridine cations, see: Shi et al. (2004 ▶).

Experimental

Crystal data

(C₁₀H₁₁N₃)[V₄O₈(PO₄)₂]
M _r = 694.92
Monoclinic,
a = 7.4431 (10) Å
b = 14.524 (2) Å
c = 18.825 (3) Å
β = 94.363 (2)°
V = 2029.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.04 mm⁻¹
T = 173 (2) K
0.20 × 0.20 × 0.04 mm

Data collection

Bruker SMART 1K diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.786, T _max = 0.922
21687 measured reflections
4652 independent reflections
3678 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.101
S = 1.09
4652 reflections
325 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2007 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808038348/tk2326sup1.cif

e-64-m1602-sup1.cif^{(27.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038348/tk2326Isup2.hkl

e-64-m1602-Isup2.hkl^{(227.9KB, 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—H1N⋯O10	0.93 (4)	2.14 (4)	2.885 (4)	136 (4)
N1—H1N⋯O9ⁱ	0.93 (4)	2.45 (4)	3.018 (5)	119 (4)
N2—H2N⋯O2ⁱⁱ	0.862 (19)	2.35 (2)	3.195 (4)	166 (4)
N3—H3N⋯O8ⁱⁱⁱ	0.90 (5)	2.02 (5)	2.902 (4)	164 (4)

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

Acknowledgments

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

supplementary crystallographic information

Comment

The kinked and hydrogen-bonding capable imine 4,4'-dipyridylamine has proven useful in the construction of novel mixed metal oxide phases (LaDuca et al., 2001). In an attempt to extend this chemistry into a metal phosphate oxide system, yellow plate-like crystals of the title compound (I) were obtained.

The asymmetric unit of (I) comprises a cluster of four pentavalent V atoms, four terminal O atoms, four triply bridging O atoms, two phosphate anions and an unligated 4,4'-iminodipyridinium dication (Fig. 1). Each V atom is octahedrally coordinated, with three µ₃O atom donors, two O atoms from two different phosphate anions, and one terminal O atom with a formal V=O double bond. The four V=O groups and four µ₃ O atoms form a cubane-type [V₄O₈]⁴⁺ cluster.

Quadruply bridging phosphate anions bridge these cationic clusters into anionic [V₄O₈(PO₄)₂]_n^2n- layers that are situated parallel to the bc-planes (Fig. 2). The phosphate groups bracket rhomboid apertures within the layers, with through-space P···P contact distances of 7.2685 (2) and 7.4431 (2) Å. Adjacent [V₄O₈(PO₄)₂]_n^2n- layers stack in an AB pattern into the 3-D structure by N—H···O hydrogen bonding mediated by the protonated pyridyl-N atoms and the central amine groups of the 4,4'-iminodipyridinium cations situated in the interlamellar regions (Fig. 3).

The overall structure of (I) is very similar to a related phase incorporating doubly protonated 4,4'-bipyridine cations (Shi et al., 2004).

Experimental

All chemicals were obtained commercially. Vanadium(V) oxide (140 mg, 0.77 mmol) and 4,4'-dipyridylamine (132 mg, 0.77 mmol) and phosphoric acid (526 mg of an 85.5% aqueous solution, 4.56 mmol) were placed into H₂O (10 ml ) in a 23 ml Teflon-lined Parr acid digestion bomb. The bomb was heated at 393 K for 72 h and was then allowed to cool to room temperature. Yellow plates of (I) were obtained along with a reddish-brown amorphous solid.