(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)nickel(II) bis­[O,O′-bis­(4-methyl­phen­yl) thio­phosphate]

Yang-Guang Xiang; Bin Xie; Li-Ke Zou; Jian-Shen Feng; Chuan Lai

doi:10.1107/S1600536810051184

. 2010 Dec 11;67(Pt 1):m59. doi: 10.1107/S1600536810051184

(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) bis[O,O′-bis(4-methylphenyl) thiophosphate]

Yang-Guang Xiang ^a, Bin Xie ^b,^*, Li-Ke Zou ^b, Jian-Shen Feng ^a, Chuan Lai ^a

PMCID: PMC3050336 PMID: 21522577

Abstract

In the centrosymmetric title complex, [Ni(C₁₆H₃₆N₄)](C₁₄H₁₄O₃PS)₂, the Ni^II ion is coordinated by four N atoms and two O atoms within a slightly distorted NiN₄O₂ octahedral geometry. The asymmetric unit consits of one Ni^II ion that is located on a center of inversion, half of the macrocylic ligand and one anion occupying general positions. Intramolecular N—H⋯O and N—H⋯S hydrogen bonding is found between the macrocyclic ligand and the monothiophosphate anion.

Related literature

For the synthesis of O,O′-bis(4-methylphenyl) monothiophosphate, see: Pesin & Khaletakii (1961 ▶). For related structures, see: Feng et al. (2010 ▶); He et al. (2010 ▶); Zou et al. (2010 ▶).

Experimental

Crystal data

[Ni(C₁₆H₃₆N₄)](C₁₄H₁₄O₃PS)₂
M _r = 929.76
Monoclinic,
a = 10.977 (2) Å
b = 16.360 (3) Å
c = 12.767 (3) Å
β = 94.85 (3)°
V = 2284.6 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 113 K
0.24 × 0.23 × 0.22 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.862, T _max = 0.873
18654 measured reflections
5376 independent reflections
2665 reflections with I > 2σ(I)
R _int = 0.101

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.122
S = 0.99
5376 reflections
281 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.91 e Å⁻³

Data collection: CrystalClear (Rigaku, 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 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051184/nc2207sup1.cif

e-67-00m59-sup1.cif^{(25.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051184/nc2207Isup2.hkl

e-67-00m59-Isup2.hkl^{(263.3KB, 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
N1—H1⋯S1ⁱ	0.92 (3)	2.66 (3)	3.574 (3)	171 (3)
N2—H2⋯O2	0.96 (3)	2.27 (3)	3.234 (3)	178 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Education Committee (No. 09ZA057) and the Science and Technology Committee (No. 2010GZ0130) of Sichuan Province, the Science and Technology Office of Zigong City (Nos. 08X01 and 10X05) and the Graduate Student Innovation Fund of Sichuan University of Science & Engineering (No. Y2009023).

supplementary crystallographic information

Comment

In our research on tetramine macrocycles transition metal complexes as mimetic hydrolases, we have recently reported several structures of their adducts with O,O'-dialkyldithiophosphate (He et al., 2010; Feng et al., 2010; Zou et al., 2010). Herein, we report the structure of an analogous O,O'-dialkylmonothiophosphate adducts, [Ni(meso-hmta)][OP(S)(OC₆H₄Me-4)₂]₂, where meso-hmta is meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane and (4-MeC₆H₄O)₂(S)PO^- is O,O'-bis(4-methylphenyl) monothiophosphate.

In the crystal structure of the title complex, the Ni^II ion is located on a center of inversion and possesses a slightly distorted NiN₄O₂ octahedral geometry (Fig. 1). The tetraamine macrocycle meso-hmta folds around the Ni^II centre at equatorial position and two O atoms from symmetry related O,O'-bis(4-methylphenyl) monothiophosphates are located in axial positions (Fig. 1). Intramolecular N—H···O and N—H···S hydrogen bonds are present between meso-hmta and monothiophosphates ligands (table 1). Furthermore, there exists a pair of symmetry related weak intermolecular C—H···π interactions for (C14—H14C)···C3(phenyl) between each couple of adjacent monothiophosphate ligands, which link the molecules into one-dimensional chains along [010]. The P1—O3 and P1—S1 bond lengths are 1.491 (2) and 1.9372 (14) Å respectively, corresponding to a delocalization of the negative charge over the O3—P1—S1 fragment.

Experimental

The ammonium O,O'-bis(4-methylphenyl)monothiophosphate was prepared according to the procedure described by Pesin (1961).

A solution of meso-5,5,7,12,12,14- hexamethyl-1,4,8,11- tetraazacyclotetradecane dihydrate (0.64 g, 2 mmol) and Ni(OAc)₂.4H₂O (0.50 g, 2 mmol) in 20 mL methanol was added to a solution of ammonium O,O'-bis(4-methylphenyl)monothiophosphate (4 mmol, 1.24 g) in 60 mL methanol. The mixture was refluxed for 6 h at 353 K and then filtered after cooling to room temperature. The filtrate was kept at room temperature and orange block crystals were obtained after 4 weeks.