Bis[tris­(phenanthroline-κ2 N,N′)cobalt(II)] undeca­tungsto(VI)vanado(V)phosphate dihydrate

Assia Hajsalem; Sameh Aoun; Aurelien Planchat; Mohamed Rzaigui; Samah Akriche Toumi

doi:10.1107/S160053681400484X

. 2014 Mar 8;70(Pt 4):m125–m126. doi: 10.1107/S160053681400484X

Bis[tris(phenanthroline-κ² N,N′)cobalt(II)] undecatungsto(VI)vanado(V)phosphate dihydrate

Assia Hajsalem ^a, Sameh Aoun ^b, Aurelien Planchat ^b, Mohamed Rzaigui ^a, Samah Akriche Toumi ^a,^*

PMCID: PMC3998553 PMID: 24826091

Abstract

In the title hydrated salt, [Co(C₁₂H₈N₂)₃]₂[PVW₁₁O₄₀]·2H₂O, the complete Kegggin ion is generated by crystallographic inversion symmetry, which imposes statistical disorder on the O atoms of its central PO₄ group. The V atom is statistically disordered over all the metal sites of the anion. In the cation, the Co²⁺ ion is coordinated by three bidentate 1,10-phenanthroline (phen) ligands, generating a distorted CoN₆ octahedron. Possible very weak intramolecular C—H⋯π interactions occur in the cation. In the crystal, the components are linked by O—H⋯O and C—H⋯O interactions, building a three-dimensional network featuring one-dimensional voids along the c-axis direction.

Related literature

For related vanadium-substituted Keggin-ion structures, see: Glinskaya et al. (1989 ▶); Klevtsova et al. (1990 ▶, 1991 ▶); Li et al. (2008 ▶); Radkov & Beer (1995 ▶). For IR spectroscopy investigations of Keggin ions, see: Lee & Misono (1997 ▶); Deltcheff et al. (1983 ▶); Watras & Teplyakov (2005 ▶). For bond-valence calculations, see: Brown & Altermatt (1985 ▶). For background to polyoxidometalate chemistry, see: Pope & Müller (1991 ▶, 1994 ▶). graphic file with name e-70-0m125-scheme1.jpg

Experimental

Crystal data

[Co(C₁₂H₈N₂)₃][PVW₁₁O₄₀]·2H₂O
M _r = 3979.38
Monoclinic,
a = 19.487 (2) Å
b = 18.049 (3) Å
c = 25.216 (2) Å
β = 100.22 (3)°
V = 8728.4 (18) Å³
Z = 4
Mo Kα radiation
μ = 15.02 mm⁻¹
T = 295 K
0.13 × 0.08 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.202, T _max = 0.421
62427 measured reflections
11235 independent reflections
8172 reflections with I > 2σ(I)
R _int = 0.070

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.095
S = 1.16
11235 reflections
688 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.39 e Å⁻³
Δρ_min = −1.51 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681400484X/hb7203sup1.cif

e-70-0m125-sup1.cif^{(42KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400484X/hb7203Isup2.hkl

e-70-0m125-Isup2.hkl^{(538.4KB, hkl)}

CCDC reference: 989480

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Co—N3	2.053 (9)
Co—N6	2.060 (8)
Co—N1	2.066 (10)
Co—N4	2.066 (11)
Co—N2	2.078 (10)
Co—N5	2.085 (8)

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Table 2. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the N1/C1–C4/C12 and N3/C13–C16/C24 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1E	0.85 (1)	2.17 (11)	2.928 (14)	149 (20)
O1W—H2W1⋯O3E ⁱ	0.85 (1)	1.99 (3)	2.836 (13)	173 (17)
C9—H9⋯O5E ⁱⁱ	0.93	2.55	3.208 (15)	128
C26—H26⋯O12ⁱⁱⁱ	0.93	2.46	2.973 (15)	114
C33—H33⋯O5^iv	0.93	2.53	3.345 (13)	147
C34—H34⋯O8	0.93	2.43	3.114 (13)	130
C34—H34⋯Cg1	0.93	3.04	3.811 (12)	142
C25—H25⋯Cg2	0.93	2.99	3.777 (13)	143

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

Acknowledgments

The authors express their appreciation to the CNRS 6230 UFR Sciences and Techniques of Nantes in France for supporting this work.

supplementary crystallographic information

1. Comment

A bibliographic survey shows only a few examples of substituted vanadium keggin-type [XV₁W₁₁O₄₀]^p^- clusters associated to organometallic or organic moieties: such as (C₂N₂H₁₀)₂[VV₁W₁₁O₄₀]·6H₂O (Glinskaya et al., 1989), [N(CH₃)₄]₄[VV₁W₁₁O₄₀]·4.5H₂O (Klevtsova et al., 1991),[(CH₃)₂NCHO]₄H₄[VV₁W₁₁O₄₀].2[(CH₃)₂NCHO]·2H₂O (Klevtsova et al., 1990), [Cu(phen)₂]₂[PVW₁₁O₄₀] (phen = phenanthroline)(Li et al., 2008),(n-Bu₄N)₄[PMW₁₁O₄₀] (n-Bu = n-Butyl and M = V, Nb, Ta) (Radkov & Beer, 1995). Here, we report a new monosubstituted vanadium tungstophosphate Keggin-type cluster decorated by mononuclear metal-organic complex [Co(phen)₃]₂[PVW₁₁O₄₀]·2H₂O (phen = phenanthroline) (I).

The asymmetric unit of of I consists of a mononuclear complex [Co(phen)₃]²⁺ cation and a half of Keggin-type [PVW₁₁O₄₀]^4- anion and one water molecule. As P atom is located on centre of inversion symmetry, the whole [PVW₁₁O₄₀]^4- polyoxidoanion is generated by this element and so is composed of a disordered PO₄ tetrahedron surrounded by four vertex-sharing M₃O₁₃ (with M = W/V) subunits which result from the association of three edge-sharing MO₆ octahedra enwrapping a PO₈ cube with oxygen atom site occupancy of 0.5. In the MO₆ (with M = W/V) octahedra, the position of metal atom is crystallographically disordered and constrained as 11/12 W and 1/12 V, with occupancies of 0.083 and 0.917 for W and V respectively.

The contents of W and V revealed by X-ray analysis are consistent with the results from elemental analyses and scanning electronic microscopy (Fig. 2) as well as the IR spectroscopy wich shows that the streching vibration of (P—O) splits into two absoption bands at 1095 cm^-1 and 1068 cm^-1 because of the lower symmetry so as well confirm the presence of monosubstituted vanadium keggin-type clusters in I (Lee et al., 1997; Deltcheff et al., 1983; Watras et al., 2005).

The assignment of oxidation states for the tungsten and vanadium atoms is confirmed by bond valence sum calculations (Brown & Altermatt, 1985)) which show that vanadium atom has +V oxidation state (average 4.98 valence units) while tungsten atoms have +VI oxidation state (average 6.23 valence units). These oxidation states are identical with the charge balance considerations and so consistent with the expected [PV^+VW^+VI₁₁O₄₀]^4- subunits.

The P—O bond distances range 1.481 (11)—1.582 (11) Å and O—P—O bond angles interval 105.5 (6)—112.6 (6) °. Commonly, the M—O bond distances are grouped into three sets: M—Ot, M—Ob and M—Oc (with Ot: terminal oxygen atoms, Oc: central oxygen atoms, Ob: bridging oxygen atoms) which are respectively ranged between 1.667 (8)—1.677 (7) Å, 2.396 (11)—2.526 (12) Å and 1.750 (18)—2.085 (14) Å. With regard to the mononuclear complex,the Co²⁺ metal is also coordinated by six nitrogen atoms from three chelating 1,10-phenanthroline ligands to form a slightly distorted MN₆ octahedron with bond lenghts around Co, are 2.053 (9)—2.085 (8) Å (Co—N) and 80.0 (4)—173.9 (4)° (N—Co—N) (Table 1).

The crystal packing of I shows that the discrete polyoxidoanion subunits are interconnected through water molecules via O—H···O hydrogen bonding interactions with O···O separation ranging from 2.836 (13) to 2.928 (14) Å (Table 2), to perform alternating [PVW₁₁O₄₀(H₂O)₂]^4n- ribbons extending along [110] and [110] crystallographic directions. The so-obtained one-dimensional-subnetworks stack together by the metal-organic moieties thanks to weak C–H···O (mean C···O = 3.144 Å) (Table 1) and electrostatic interactions so as to build three-dimensional-supramolecular network generating vacant one-dimensional-channels along c axis as can be seen in Fig. 3. Very weak intramolecular C—H···π interactions of phen rings (Fig. 4) with mean distances of 3 Å (Table 2) are also observed.

2. Experimental

A reaction mixture of Na₂WO₄·2H₂O (2 g, 6.064 mmol), NaH₂PO₄·2H₂O (0.1034 g, 0.6628 mmol), CoCl₂·6H₂O (0.1951 g, 0.8196 mmol), V₂O₅ (0,0455 g; 0.25 mmol) and phen·H₂O (0.3196 g, 1.7758 mmol) were added to water (10 ml). The mixture was adjusted to pH = 5.5 by the addition of 4M HCl aqueous solution then stirred for 30 min in air. The mixture solution was transferred into a 23 ml Teflon-lined autoclave and crystallized at 180°C for 4 days. Then the autoclave was cooled at 10°C.h^-1 to room temperature. The resulting dark yellow block crystals of I were filtered off, washed with water, and dried at ambient temperature to give yields of 68% based on W. Anal. Calc. For C₇₂H₅₂N₁₂Co₂O₄₂PVW₁₁ (%): C 21.79, H 1.27, N 4.20, W 50.92, V 1.28, P 0.78, Co 2.96; Found C 21.71, H 1.31, N 4.25, W 50.80, V 1.31, P 3/4, Co 2.98; IR (KBr, cm^-1): 966 ν(M=Ot), 887 ν(M—Ob—M), 799 ν(M—Oc—M) with M=W/V and 1095 and 1068 ν(P—O).