cis-Diaqua­bis­[dimethyl (phenyl­sulfonyl­imino)­phospho­nato]cobalt(II)

Elizaveta A Trush; Victor A Trush; Tetyana Yu Sliva; Irina S Konovalova; Volodymyr M Amirkhanov

doi:10.1107/S1600536811006027

. 2011 Feb 23;67(Pt 3):m369–m370. doi: 10.1107/S1600536811006027

cis-Diaquabis[dimethyl (phenylsulfonylimino)phosphonato]cobalt(II)

Elizaveta A Trush ^a,^*, Victor A Trush ^a, Tetyana Yu Sliva ^a, Irina S Konovalova ^b, Volodymyr M Amirkhanov ^a

PMCID: PMC3051992 PMID: 21522293

Abstract

In the title diaquacobalt complex, [Co(C₈H₁₁NO₅PS)₂(H₂O)₂], the Co^II atom is surrounded by six O atoms belonging to the phosphoryl and sulfonyl groups of two deprotonated chelate ligands and two additional O atoms from water molecules which are in cis positions with respect to one another. The coordination environment of cobalt can be described as a distorted octahedron. O—H⋯O hydrogen bonds between the water and sulfonyl O atoms of neighboring molecules form chains running parallel to [010]. Two methoxy groups attached to one phosphorus are disordered over two sets of sites in a 0.6:0.4 ratio.

Related literature

For the coordination chemistry of β-diketone derivatives and their structural analogues, see Skopenko et al. (2004 ▶). For details of the pharmacological and biological properties of sulfonylamide derivatives, see: Kishino & Saito (1979 ▶); Xu & Angell (2000 ▶). For structural discussion, see: Cremer & Pople (1975 ▶); Zefirov et al. (1990 ▶). For related structures, see: Moroz et al. (2009 ▶); Shatrava et al. (2010 ▶).

Experimental

Crystal data

[Co(C₈H₁₁NO₅PS)₂(H₂O)₂]
M _r = 623.38
Triclinic,
a = 9.875 (1) Å
b = 10.207 (1) Å
c = 13.345 (2) Å
α = 91.60 (1)°
β = 110.59 (1)°
γ = 92.84 (1)°
V = 1256.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 294 K
0.40 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.681, T _max = 0.903
9231 measured reflections
5612 independent reflections
4025 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.066
S = 0.90
5612 reflections
354 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006027/dn2630sup1.cif

e-67-0m369-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006027/dn2630Isup2.hkl

e-67-0m369-Isup2.hkl^{(269.2KB, 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
O11—H11A⋯O3ⁱ	0.88	1.93	2.7898 (19)	167
O11—H11B⋯O6ⁱ	0.90	1.92	2.811 (2)	167
O12—H12A⋯O1ⁱⁱ	0.92	1.98	2.855 (2)	157
O12—H12B⋯O8ⁱⁱ	0.88	1.96	2.8035 (18)	163

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

Acknowledgments

The authors gratefully acknowledge the Ukrainian State Fund for Fundamental Researchers (SFFR) for financial support of the Research Program (Chemistry).

supplementary crystallographic information

Comment

Many efforts are devoted to the coordination chemistry of β- diketones derivatives and their structural analogues (Skopenko et al., 2004). The phosphorylated sulfonylamides, RSO₂NHP(O)(R')₂ (SAPh), present such type of heterosubstituted structural analogues with different substituents at sulfur and phosphorus atoms. In the past few decades SAPh have been intensively used as bactericidal agents in medicine and toxicology (Xu & Angell, 2000). Some of them are effective pesticides (Kishino & Saito, 1979). So a variety of new s-, d-, and f- metals based coordination compounds containing this type of phosphoramides have been synthesized. Structural investigation of compounds with phosphorylated sulfonylamide ligands have already been reported (Moroz et al., 2009, Shatrava et al., 2010). Herein we report the structure of the title compound containing one of the simplest representative of this class of ligands: the dimethyl(phenylsulfonyl)amidophosphate.

The crystal structure of CoL₂2H₂O (I) is built up from non-centrosymmetric molecular species with the two water molecules in cis- position to each other. The CoO₆ fragment is formed by two oxygen atoms of water molecules and four oxygen atoms of phosphoryl and sulfonyl groups from two ligands which are coordinated in bidentate chelating mode (Fig. 1). The coordination environment of cobalt can be described as a distorted octahedron.

The six-membered chelate rings have a twist–boat conformation (the puckering parameters (Cremer & Pople,1975) are θ=81.19,ψ=25.33, S=0.60 for CoO₂SNPO₃ fragment and θ=67.91, ψ=17.44, S=0.57 for the CoO₇S₂N₂P₂O₈ (Zefirov et al., 1990). The O4 and O5 atoms of methoxy groups are disordered over two positions due to the rotation around P1—O4 and P1—O5 bonds with populations 40:60%.

O—H···O intermolecular hydrogen bonds between the water and non-coordinated sulfonyl oxygen atoms and coordinated phosphoryl groups of neighboring SAPh molecules (Table 1) build up chains parallel to the [0 1 0] direction (Fig.2).

Experimental

The sodium salt (NaL) was prepared by the reaction between equimolar amounts of sodium isopropylate (0,023 g, 1 mmol of Na was solved in 2-propanol) and HL (0,2652 g, 1 mmol) in an 2-propanol medium and was used for preparation of complexes without isolation from the reaction mixture.

The solution of NaL (1 mmol) was added to the solution of CoCl₂6H₂O (0,124 2 g, 0,5 mmol) in 2-propanol (10 ml). The resulting mixture was filtrated off and mother liquor was left on air at room temperature for several days. Precipitated from the solution purple crystals were filtered and washed with cool 2-propanol. Single crystals of [Co(L)₂2H₂O] were prepared by slow recrystallization in 2-propanol-chloroform (3:1) mixture (yield - 80–90%). This complex as prepared is less soluble in non-polar aprotic solvents and H₂O. Analysis found: IR (KBr pellet, cm^-1): 1220, 1060 (s, SO₂) and 1190 (s, PO).