μ-1,2-Bis(diethyl­phosphino)ethane-κ2 P:P′-bis­{[1,2-bis­(diethyl­phosphino)ethane-κ2 P,P′]trichloridonitrosyl­tungsten(II)}

Nataša Avramović; Olivier Blacque; Helmut W Schmalle; Heinz Berke

doi:10.1107/S1600536808001141

. 2008 Jan 16;64(Pt 2):m367–m368. doi: 10.1107/S1600536808001141

μ-1,2-Bis(diethylphosphino)ethane-κ² P:P′-bis{[1,2-bis(diethylphosphino)ethane-κ² P,P′]trichloridonitrosyltungsten(II)}

Nataša Avramović ^a, Olivier Blacque ^a,^*, Helmut W Schmalle ^a, Heinz Berke ^a

PMCID: PMC2960239 PMID: 21201325

Abstract

The title binuclear compound, [W₂Cl₆(NO)₂(C₁₀H₂₂P₂)₃], contains two W atoms which are bridged by a bis(diethylphosphino)ethane (depe) ligand. The seven-coordinated tungsten(II) centres display distorted pentagonal–bipyramidal geometries with trans nitrosyl and chloride ligands. The title molecule lies on a crystallographic inversion centre. The ethane group of the non-bridging depe ligand is positionally disordered, with site-occupancy factors of 0.63 and 0.37. In the crystal structure, the binuclear molecules are linked by weak intermolecular C—H⋯O and C—H⋯Cl interactions. In addition, weak intramolecular C—H⋯Cl interactions are also present.

Related literature

For related literature, see: Avramović et al. (2008 ▶); Bencze & Kohàn (1982 ▶); Campbell et al. (1985 ▶); Carmona et al. (1989 ▶); Desiraju & Steiner (1999 ▶); Han & Coucouvanis (2002 ▶); Hunter & Legzdins (1984 ▶); Landau et al. (1999 ▶); Zeng et al. (1994 ▶).

Experimental

Crystal data

[W₂Cl₆(NO)₂(C₁₀H₂₂P₂)₃]
M _r = 1259.10
Orthorhombic,
a = 12.6406 (14) Å
b = 17.6485 (14) Å
c = 20.5243 (17) Å
V = 4578.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 5.61 mm⁻¹
T = 183 (2) K
0.26 × 0.20 × 0.15 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: numerical (Coppens et al., 1965 ▶) T _min = 0.329, T _max = 0.499
52250 measured reflections
3982 independent reflections
3026 reflections with I > 2σ(I)
R _int = 0.079

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.056
S = 0.84
3982 reflections
224 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Data collection: IPDS Software (Stoe & Cie, 1999 ▶); cell refinement: IPDS Software; data reduction: X-RED (Stoe & Cie, 1999 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001141/su2041sup1.cif

e-64-0m367-sup1.cif^{(26.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001141/su2041Isup2.hkl

e-64-0m367-Isup2.hkl^{(191.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

W1—P1	2.5598 (13)
W1—P2	2.5675 (14)
W1—P3	2.6051 (12)
W1—Cl1	2.4750 (12)
W1—Cl2	2.4703 (11)
W1—Cl3	2.4905 (11)
W1—N1	1.783 (4)

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N1—W1—Cl1	98.06 (14)
N1—W1—Cl2	99.08 (13)
N1—W1—Cl3	177.72 (13)
Cl1—W1—Cl2	141.66 (4)
Cl2—W1—Cl3	82.27 (4)
Cl1—W1—Cl3	81.87 (4)
Cl1—W1—P2	71.30 (5)
Cl1—W1—P3	73.09 (4)
Cl2—W1—P1	70.77 (4)
Cl2—W1—P3	73.54 (4)
Cl3—W1—P1	90.21 (4)
P1—W1—P2	72.90 (5)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5B⋯Cl2	0.97	2.81	3.196 (7)	105
C11—H11A⋯Cl1	0.97	2.71	3.129 (7)	107
C13—H13B⋯Cl1	0.97	2.75	3.132 (5)	104
C14—H14A⋯Cl2	0.97	2.76	3.150 (5)	105
C13—H13A⋯Cl1ⁱ	0.97	2.80	3.425 (5)	123
C10—H10A⋯Cl3ⁱⁱ	0.96	2.81	3.726 (7)	161
C2—H2A⋯O1ⁱⁱⁱ	0.97	2.65	3.579 (10)	161
C4—H4B⋯O1ⁱⁱⁱ	0.97	2.56	3.470 (15)	156

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

Acknowledgments

The authors thank the University of Zürich and the Swiss National Science Foundation for financial support.

supplementary crystallographic information

Comment

The mononuclear compound [W(Cl)₂(NO)(dmpe)₂](Cl) was previously obtained by the reaction of [W(Cl)₃(NO)(NCCH₃)₂] with 2.5 equivalents of dmpe [1,2-bis(dimethylphosphino)ethane] at room temperature in tetrahydrofuran (Avramović et al., 2008). The synthesis of the analogous compound [W(Cl)₂(NO)(depe)₂](Cl) was also attempted by the same procedure using the bidentate ligand depe [1,2-bis(diethylphosphino)ethane]. Presumably because of steric factors, only the binuclear compound [W(Cl)₃(NO)(depe)]₂(µ-depe) was formed instead of the expected mononuclear compound.

The title compound consists of two metal units bridged by a depe ligand (see: Campbell et al., 1985; Han & Coucouvanis, 2002; Zeng et al., 1994; Landau et al., 1999). Both tungsten centers are crystallographically equivalent since the molecule lies on a crystallographic inversion center (Fig. 1). The geometry at tungsten(II) is very similar to that in [W(Cl)₂(NO)(dmpe)₂](Cl) with a distorted pentagonal bipyramidal coordination. A second chloride ligand takes the place of one phosphorus in [W(Cl)₂(NO)(dmpe)₂](Cl) to complete the equatorial plane of the polyhedron (P1, P2, P3, Cl1 and Cl2). The five equatorial bond angles, in the range 70.8 - 73.5°, are close to the theoretically average angle of 72°. It is worth noting that the five equatorial atoms are not completely coplanar. Atoms Cl1 and Cl2 deviate from the P1—P2—P3 plane, toward the third chloride atom Cl3, by 0.303 (2) and 0.543 (2) Å, respectively. Nevertheless, this geometry is clearly different to that observed for the related compound Mo(Cl)₃(NO)(PMe₃)₃, for which the coordination polyhedron is described as a capped-octahedron (Carmona et al., 1989).

All the chloride ligands are engaged in hydrogen bonding, with atoms Cl1 and Cl2 involved in ten intramolecular interactions with CH₂ hydrogen atoms within the dimer, and atom Cl3 (trans to the nitrosyl group) in one weak intermolecular interaction with the methyl hydrogen atom H10A (Fig. 2, Table 1). The C10···Cl3 donor-acceptor distance of 3.726 (7) Å represents a rather weak interaction of this type (Desiraju & Steiner, 1999). In addition, the binuclear complexes are linked by two weak intermolecular C—H···O hydrogen bonds between the nitrosyl oxygen atom and the hydrogen atoms of the disordered ethane bridge.

Experimental

[W(Cl)₃(NO)(depe)]₂(µ-depe) was prepared from the complex [W(Cl)₃(NO)(CH₃CN)₂]. The latter is easily synthesized by the reaction of W(Cl)₆ with NO gas in dichloromethane in the presence of acetonitrile at room temperature, according to a literature procedure (Bencze & Kohàn, 1982; Hunter & Legzdins, 1984). 5.00 g (12.6 mmol) of WCl₆ and 1.32 ml (25.2 mmol) of acetonitrile were dissolved in 180 ml of dichloromethane in a 500 ml three-necked flask. Nitric oxide was passed through the solution, which was stirred at room temperature until the dark purple colour of the solution turned to the light green precipitate after ca 1 h. The volume of the final mixture was reduced to 50 ml in vacuo and the mixture was then cooled to 0°C for 15 min. The precipitate was isolated by filtration and the collected solid was then washed first with cold dichloromethane (2 x 10 ml at 0°C) and then with hexane (4 x 20 ml) at room temperature. Final drying of the solid under vacuum for 18 h afforded the yellow-green [W(Cl)₃(NO)(CH₃CN)₂] compound. 0.200 g (0.497 mmol) of [W(Cl)₃(NO)(NCCH₃)₂] was dissolved in 20 ml of tetrahydrofurane in a Young tap Schlenk and the depe ligand (0.29 ml, 1.243 mmol) was syringed into the solution. The solution was stirred at room temperature for 24 h, then filtered and the solvent removed under vacuum. The resulting solid was crystallized from dichloromethane at room temperature and gave light-green crystals of the title compound.

Yield: 0.266 g (85%).

IR (cm^-1, CH₂Cl₂): 1520 (NO).

¹H NMR (200.0 MHz, CD₂Cl₂, 25°C): 2.69 (m, 4H, P(CH₂)₂P); 2.39 (m, 8H, PCH₂CH₃); 2.19 (16H, PCH₂CH₃), 2.06 (m, 8H, P(CH₂)₂P), 1.25 (m, 24H, PCH₂CH₃), 1.19 (m,12H, PCH₂CH₃).

³¹P{¹H} NMR (80.9 MHz, CD₂Cl₂, 25°C): 46.8 (m, P(CH₂)₂P), 45.8 (m, P(CH₂)₂P) and 21.4 (m, P(CH₂)₂P), ²J_PN = 15.6 Hz; ¹J_PW = 203 Hz.

¹³C{¹H} NMR (50.3 MHz, CD₂Cl₂, 25°C): 8.8 (m, PCH₂CH₃), 9.2 (s, PCH₂CH₃), 15.7 (m, PCH₂CH₃), 18.5 (m, PCH₂CH₃), 20.0 (m, P(CH₂)₂P).

Anal. Calcd for C₃₀H₇₂Cl₆N₂O₂P₆W₂: C, 28.60; H, 5.72; N, 2.22. Found: C, 28.87; H, 6.01; N, 1.98.