Triclinic modification of tetra­kis­(triethyl­ammonium) dihydrogeno­deca­vanadate(V)

Seik Weng Ng

doi:10.1107/S1600536811019696

. 2011 May 28;67(Pt 6):m811–m812. doi: 10.1107/S1600536811019696

Triclinic modification of tetrakis(triethylammonium) dihydrogenodecavanadate(V)

Seik Weng Ng ^a,^*

PMCID: PMC3120463 PMID: 21754685

Abstract

In the title ammonium polyoxometallate salt, (C₆H₁₆N)₄[H₂V₁₀O₂₈], the anion features O atoms engaged in μ₆-, μ₃- and μ₂-bridging of adjacent V^V atoms, confering an octahedral coordination at each of the twenty unique metal atoms. Two anions are linked by μ₃- and μ₂-bridged OH units across a center of inversion, forming a dimer which is linked to the cations by N—H⋯O hydrogen bonds. The cation is disordered over two positions in a 0.776 (4):0.224 (4) ratio in one of the two independent ion pairs in the asymmetric unit, and 0.627 (10):0.373 (10) in the other.

Related literature

For the monoclinic modification, see: Correia et al. (2004 ▶); Sarkar & Pal (2008 ▶).

Experimental

Crystal data

(C₆H₁₆N)₄[H₂V₁₀O₂₈]
M _r = 1368.21
Triclinic,
a = 13.1735 (4) Å
b = 20.0061 (7) Å
c = 20.2427 (7) Å
α = 62.669 (3)°
β = 86.263 (3)°
γ = 76.979 (3)°
V = 4613.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.688, T _max = 0.824
38533 measured reflections
20465 independent reflections
13087 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.133
S = 1.04
20465 reflections
1230 parameters
132 restraints
H-atom parameters constrained
Δρ_max = 1.47 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811019696/zs2113sup1.cif

e-67-0m811-sup1.cif^{(114.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811019696/zs2113Isup2.hkl

e-67-0m811-Isup2.hkl^{(1,000KB, 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—H1⋯O3	0.88	2.06	2.937 (4)	175
N2—H2⋯O14	0.88	1.89	2.765 (4)	176
N3—H3⋯O41	0.88	1.82	2.699 (4)	175
N4—H4⋯O9	0.88	2.13	2.968 (9)	160
N4′—H4′⋯O9	0.88	1.99	2.830 (16)	158
N5—H5⋯O26	0.88	2.39	2.981 (5)	125
N5—H5⋯O28	0.88	2.38	3.187 (5)	153
N6—H6⋯O51	0.88	1.96	2.823 (4)	167
N7—H7⋯O34	0.88	2.33	3.061 (4)	141
N7—H7⋯O45	0.88	2.44	3.156 (5)	139
N7—H7⋯O46	0.88	2.40	3.139 (4)	142
N8—H8⋯O52	0.88	1.91	2.766 (4)	162
O15—H15⋯O18ⁱ	0.84	1.99	2.819 (4)	171
O17—H17⋯O16ⁱ	0.84	1.90	2.715 (4)	162
O54—H54⋯O55ⁱⁱ	0.84	1.88	2.686 (4)	159
O56—H56⋯O53ⁱⁱ	0.84	1.94	2.775 (4)	177

Open in a new tab

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

Acknowledgments

I thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The polyoxometallate, 4(C₂H₅)₃NH⁺ [H₂O₂₈V₁₀]^4-, tetrakis(triethylammonium) bis(µ₆-oxo)-(µ₃-hydroxo)-tris(µ₃-oxo)-(µ₂-hydroxo)-trideca(µ₂-oxo)-octaoxo-decavanadate(V) (Scheme I) was the product obtained by reacting triethylammonium D,L-aminopropionate, salicylaldehyde and vanadyl(IV) sulfate in methanol (Correia et al., 2004). The POM can also be synthesized from the reaction of triethylamine and vanadium(V) oxide in water (Sarkar & Pal, 2008). The compound, which belongs to the monoclinic P2₁/c space group, features the dihydrogenodecavanadate tetraanion surrounded by the cations; two tetraanions are linked by a pair of O–H···O hydrogen bonds to generate a dimer. In the present triclinic modification, the ion similarly features oxygen atoms engaged in µ₆–, µ₃– and µ₂-bridging of adjacent vanadium(V) atoms to confer octahedral coordination at the metal centers (Figs. 1 & 2). Two ions are linked by µ₃-bridged and µ₂-bridged OH units across a center-of-inversion to form a dimer (Fig. 3). The dimers are linked to the cations by N–H···O hydrogen bonds (Table 1).

Experimental

Vanadyl(IV) sulfate (0.25 g, 1 mmol), 4-oxo-1,4-pyran-2,6-dicarboxylic acid (chelidonic acid) (0.18 g, 1 mmol) and triethylamine (0.4 ml, 3 mmol) were heated in water (100 ml) for an hour. The solution was filtered and upon slow evaporation of the filtrate afforded orange prisms of the title compound as a side product in low yield.