(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) bis[O,O′-bis(4-methylphenyl) dithiophosphate]

The title complex, [Ni(C24H32N4)](C14H14O2PS2)2, comprises a centrosymmetric [Ni(meso-diphenyl[14]dien)]2+ dication (meso-diphenyl[14]dien is C-meso-N-meso-5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) and two O,O′-bis(4-methylphenyl) dithiophosphate anions. The NiII ion lies on an inversion center and is chelated by a tetraamine macrocycle ligand in a slightly distorted NiN4 square-planar geometry. Two S atoms from symmetry-related anions are located in pseudo-axial positions with respect to the NiII ion, with Ni⋯S distances of 3.1869 (8) Å. In the crystal, bifurcated intermolecular N—H⋯S(S) hydrogen bonds connect cations and pairs of anions into three-component clusters. Weak intermolecular C—H⋯S hydrogen bonds link these clusters into chains along [100].


Comment
The significance of synthetic tetramine macrocycles is most obvious because of their strong chelating ability and analogy to naturally occurring macrocyclic systems, therefore the synthesis and potential use of their transition-metal complexes have been extensively studied (Aoki et al., 2002). At the same time, the transition-metal complexes of O,O'-dialkyldithiophosphate ligands (DDP) have attracted our attention due to their luxuriant variety of coordination bonding characteristics (Drew et al., 1987;Liaw et al., 2005) and potential application as mimetic hydrolases for carboxylic acid esters (Zou et al., 2009). For these reasons, we have recently reported several structures of tetramine macrocyclic transition-metal adducts with O,O'-dialkyldithiophosphate (Feng et al., 2009;Xie et al., 2009;He et al., 2010). Herein, we report the structure of dien)][S 2 P(OC 6 H 4 Me-4) 2 ] 2 , where meso-diphenyl [14]dien is C-meso- N-meso-5,12-dimethyl-7,14diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. The molecular of the title complex comprises a complex mononuclear dien)] 2+ cation and two O,O'-bis(4-methylphenyl) dithiophosphate anions. The Ni II atom lies on an inversion centre and is chelated by four N atoms from the macrocyclic tetramine meso-diphenyl [14]dien in a slightly distorted NiN 4 square-planar geometry (Fig.1). Two uncoordinated O,O'-bis(4-methylphenyl) dithiophosphate anions occupy pseudo-axial positions with Cu···S distances of 3.1869 (7) Å, forming a octahedral type arrangement. Intermolecular N-H···S and C-H···S hydrogen bonds are present between the anions and the cations. All bond lengths (Allen et al., 1987) and angles in the complex are within normal ranges.
The title complex was prepared by a modified method according to our previous work (Xie et al., 2009). A cellulose thimble containing 0.634 g (1 mmol) of mixed isomers of [Ni(diphenyl[14]dien)](ClO 4 ) 2 was placed in a Soxhlet apparatus.
The isomers were slowly extracted to a solution of 0.767 g (2 mmol) [(C 2 H 5 ) 2 NH 2 ][S 2 P(OC 6 H 4 Me-4) 2 ] in 70 mL methanol (extraction solvent) and the less soluble meso-isomer of the adduct, [Ni(diphenyl[14]dien)][S 2 P(OC 6 H 4 Me-4) 2 ] 2 , was slowly pricipitated out during the extraction procedure. The whole extraction process lasted about 36 hours and then refluxed for another 4 hours. After cooling to room temperature, the solid was filtered off and washed successively with methanol, acetone and diethyl ether. The crude product was dissolved in hot dimethylformamide and filtered, the filtrate was kept at room temperature and pale-violet block crystals suitable for X-ray diffraction studies were obtained after three months.

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.