(2,2′-Bipyridine)bis­(triphenyl­phosphine)copper(I) nitrate chloro­form solvate hemihydrate

Maribel Navarro; Oscar A Corona; Teresa González; Mario V Capparelli

doi:10.1107/S1600536808006260

. 2008 Mar 12;64(Pt 4):m533–m534. doi: 10.1107/S1600536808006260

(2,2′-Bipyridine)bis(triphenylphosphine)copper(I) nitrate chloroform solvate hemihydrate

Maribel Navarro ^a, Oscar A Corona ^a, Teresa González ^a, Mario V Capparelli ^b,^*

PMCID: PMC2960891 PMID: 21201995

Abstract

In the title compound, [Cu(C₁₀H₈N₂)(C₁₈H₁₅P)₂]NO₂·CHCl₃·0.5H₂O, the Cu atom is tetrahedrally coordinated by a bidentate 2,2′-bipyridine ligand and two PPh₃ ligands. The Cu—N and Cu—P distances are similar to those observed in similar compounds. The range of coordination angles shows a moderate distortion from ideal tetrahedral geometry. The bipyridine ligand is twisted [14.2 (4)°] about the ring–ring C—C bond. The nitrate anion and the water and chloroform molecules of solvation are disordered. In the crystal structure, there are O(water)—H⋯O(nitrate), C—H⋯O(water) and C—H⋯O(nitrate) hydrogen bonds.

Related literature

For related literature, see: Allen et al. (1987 ▶); Engelhardt et al. (1985 ▶); Hirshfeld (1976 ▶); Navarro et al. (2003 ▶).

Experimental

Crystal data

[Cu(C₁₀H₈N₂)(C₁₈H₁₅P)₂]NO₃·CHCl₃·0.5H₂O
M _r = 934.65
Triclinic,
a = 10.754 (2) Å
b = 12.672 (3) Å
c = 17.464 (4) Å
α = 99.100 (5)°
β = 99.279 (4)°
γ = 101.229 (5)°
V = 2259.4 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 296 (2) K
0.56 × 0.51 × 0.40 mm

Data collection

Rigaku AFC7S Mercury diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.584, T _max = 0.733
25842 measured reflections
8576 independent reflections
6719 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.136
S = 1.06
8576 reflections
549 parameters
20 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006260/bg2166sup1.cif

e-64-0m533-sup1.cif^{(34.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006260/bg2166Isup2.hkl

e-64-0m533-Isup2.hkl^{(411KB, hkl)}

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

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

Cu1—N1	2.070 (2)
Cu1—N12	2.103 (3)
Cu1—P2	2.2600 (9)
Cu1—P1	2.2659 (9)

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N1—Cu1—N12	79.71 (10)
N1—Cu1—P2	111.18 (8)
N12—Cu1—P2	111.86 (7)
N1—Cu1—P1	111.46 (8)
N12—Cu1—P1	108.68 (7)
P2—Cu1—P1	124.89 (3)

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N1—C6—C7—N12

14.2 (4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3Sⁱ	0.93	2.56	3.317 (9)	139
C5—H5⋯O1Wⁱ	0.93	2.34	3.182 (15)	151
C8—H8⋯O2Sⁱⁱ	0.93	2.38	3.242 (11)	155
C45—H45⋯O3S	0.93	2.59	3.493 (10)	163
C1S—H1S⋯O1Sⁱⁱⁱ	0.98	2.25	3.204 (7)	165
O1W⋯O2S^iv			2.663 (19)
O1W⋯O2S^v			2.667 (19)

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

Acknowledgments

Financial support from the Fondo Nacional de Ciencia, Tecnología e Investigación (FONACIT) of Venezuela, project Lab-199700821, is gratefully acknowledged.

supplementary crystallographic information

Comment

The title compound (I) was prepared within our program of studies of copper complexes containing N-bidentated aromatic ligands, focused on the search for drugs with biological activity, especially against parasitic diseases (Navarro et al., 2003).

The structure analysis showed that, in addition to the complex cation and the (partially disordered) nitrate anion the crystals contain disordered molecules of water and chloroform of solvation.

In the cation (Fig. 1), the metal atom is tetrahedrally coordinated to a bidentated 2,2'-bipyridine (bipy) ligand and to two PPh₃ moieties. The Cu—N and Cu—P (Table 1) distances are comparable to Cu—N, 2.056 (8), 2.113 (9) Å and Cu—P, 2.246 (3), 2.256 (3) Å observed in the same cation in [Cu(PPh₃)₂(bipy)]ClO₄ (Engelhardt et al., 1985). All bond lengths and angles in the organic ligands are within normal values (Allen et al., 1987).

The range of coordination angles (Table 1) shows a moderate distortion from the ideal tetrahedral geometry. As expected, the bite angle is the smaller one, while the P—Cu—P angle is the largest, due to the bulkiness of the PPh₃ moieties. The five-member metallacycle, Cu1—N1—C6—C7—N2, can be described as an envelope on C6, albeit a flat one [C6 is 0.148 (4) Å out of the plane]. The bipy ligand is twisted about C6—C7 (Table 1); the dihedral angle between both heterocycles is 17.0 (2)°.

Although the water's H atoms could not be located (see Refinement Section), short contacts with the nitrate anion [O1w···O2s(1 + x, y, z), 2.663 (19) Å; O1w···O2s(1 - x, 2 - y, -z), 2.667 (19) Å] indicate hydrogen bonds between these two groups. Further evidence of the feasibility of these links is given by the corresponding O2s···O1w···O2s angle [146.7 (5)°]. Several C—H···O bonds may also contribute to the crystal packing (Fig. 2 and Supplementary material).

Experimental

The title compound (I) was synthesized by the reaction of copper nitrate with bipyridine. To a solution of Cu(PPh₃)₂NO₃ (100 mg, 0.15 mmol) in dichloromethane (10 ml) was added 2,2'-bipyridine (24 mg, 0.15 mmol). The solution, initially transparent, became yellow. It was stirred for 1 h at room temperature and then was added to hexane (50 ml). The light yellow solid formed was filtered and dried (122 mg, 98%). All operations were carried out under inert atmosphere. Crystals suitable for X-ray analysis were obtained by slow evaporation of a chloroform solution.