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

Xiang, Y.-G.; Xie, B.; Zou, L.-K.; Feng, J.-S.; Lai, C.

doi:10.1107/S1600536810051184

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page m59

https://doi.org/10.1107/S1600536810051184

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(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 and Chuan Lai ^a

^aCollege of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, 643000 Zigong, Sichuan, People's Republic of China, and ^bResearch Institute of Functional Material, Sichuan University of Science and Engineering, 643000 Zigong, Sichuan, People's Republic of China
^*Correspondence e-mail: xiebinqhg@sina.com

(Received 21 November 2010; accepted 6 December 2010; online 11 December 2010)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.053
wR(F²) = 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

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)
Symmetry code: (i) -x+1, -y+1, -z+1.

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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051184/nc2207Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title complex, showing the atom-numbering scheme with displacement ellipsoids drawn at 30% probability level. H atoms on N are represented as small spheres of arbitary radii and H atoms on C have been omitted for the sake of clarity. Hydrogen-bonds are shown as dashed lines. [Symmetry code: (i) -x + 1, -y + 1, -z + 1].

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

Crystal data top

[Ni(C₁₆H₃₆N₄)](C₁₄H₁₄O₃PS)₂	F(000) = 988
M_r = 929.76	D_x = 1.352 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7232 reflections
a = 10.977 (2) Å	θ = 2.2–27.9°
b = 16.360 (3) Å	µ = 0.64 mm⁻¹
c = 12.767 (3) Å	T = 113 K
β = 94.85 (3)°	Block, orange
V = 2284.6 (8) Å³	0.24 × 0.23 × 0.22 mm
Z = 2

Data collection top

Rigaku Saturn CCD area-detector diffractometer	5376 independent reflections
Radiation source: rotating anode	2665 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.101
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 2.2°
φ and ω scans	h = −14→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −21→19
T_min = 0.862, T_max = 0.873	l = −16→16
18654 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: mixed
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0244P)²] where P = (F_o² + 2F_c²)/3
5376 reflections	(Δ/σ)_max < 0.001
281 parameters	Δρ_max = 0.97 e Å⁻³
0 restraints	Δρ_min = −0.91 e Å⁻³

Crystal data top

[Ni(C₁₆H₃₆N₄)](C₁₄H₁₄O₃PS)₂	V = 2284.6 (8) Å³
M_r = 929.76	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.977 (2) Å	µ = 0.64 mm⁻¹
b = 16.360 (3) Å	T = 113 K
c = 12.767 (3) Å	0.24 × 0.23 × 0.22 mm
β = 94.85 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	5376 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2665 reflections with I > 2σ(I)
T_min = 0.862, T_max = 0.873	R_int = 0.101
18654 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.97 e Å⁻³
5376 reflections	Δρ_min = −0.91 e Å⁻³
281 parameters

Special details top

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 F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.5000	0.02073 (17)
P1	0.49238 (7)	0.69655 (5)	0.59137 (7)	0.0216 (2)
S1	0.57082 (7)	0.69510 (5)	0.73310 (7)	0.0288 (2)
O1	0.38094 (17)	0.76174 (13)	0.58832 (18)	0.0236 (6)
O2	0.58179 (16)	0.73444 (12)	0.50834 (17)	0.0214 (5)
O3	0.44815 (16)	0.61948 (12)	0.53863 (17)	0.0223 (5)
N1	0.3899 (2)	0.50845 (17)	0.3600 (2)	0.0219 (6)
H1	0.395 (3)	0.4578 (19)	0.329 (3)	0.035 (10)*
N2	0.6334 (2)	0.55494 (16)	0.4156 (2)	0.0215 (7)
H2	0.616 (3)	0.6087 (18)	0.441 (3)	0.030 (9)*
C1	0.2889 (3)	0.76449 (19)	0.5047 (3)	0.0223 (8)
C2	0.3144 (3)	0.76956 (19)	0.4017 (3)	0.0246 (8)
H2A	0.3966	0.7682	0.3837	0.030*
C3	0.2189 (3)	0.7767 (2)	0.3242 (3)	0.0275 (8)
H3	0.2366	0.7805	0.2528	0.033*
C4	0.0970 (3)	0.77851 (19)	0.3485 (3)	0.0250 (8)
C5	0.0746 (3)	0.7723 (2)	0.4531 (3)	0.0278 (9)
H5	−0.0073	0.7727	0.4719	0.033*
C6	0.1699 (3)	0.7656 (2)	0.5310 (3)	0.0296 (9)
H6	0.1531	0.7617	0.6026	0.035*
C7	−0.0083 (3)	0.7901 (2)	0.2647 (3)	0.0389 (10)
H7A	−0.0184	0.7405	0.2218	0.058*
H7C	0.0093	0.8365	0.2198	0.058*
H7B	−0.0837	0.8009	0.2984	0.058*
C8	0.6458 (3)	0.80740 (19)	0.5269 (3)	0.0217 (8)
C9	0.7636 (3)	0.8040 (2)	0.5759 (3)	0.0267 (8)
H9	0.7978	0.7536	0.6008	0.032*
C10	0.8303 (3)	0.8763 (2)	0.5877 (3)	0.0307 (9)
H10	0.9115	0.8743	0.6199	0.037*
C11	0.7829 (3)	0.9500 (2)	0.5545 (3)	0.0295 (9)
C12	0.6644 (3)	0.9517 (2)	0.5073 (3)	0.0341 (9)
H12	0.6292	1.0023	0.4843	0.041*
C13	0.5966 (3)	0.8805 (2)	0.4934 (3)	0.0301 (9)
H13	0.5157	0.8826	0.4605	0.036*
C14	0.8567 (3)	1.0273 (2)	0.5677 (3)	0.0458 (11)
H14A	0.8793	1.0458	0.4989	0.069*
H14B	0.9310	1.0169	0.6139	0.069*
H14C	0.8080	1.0697	0.5989	0.069*
C15	0.8417 (3)	0.6094 (2)	0.3973 (3)	0.0361 (10)
H15A	0.8263	0.6104	0.3206	0.054*
H15C	0.9291	0.6010	0.4164	0.054*
H15B	0.8161	0.6615	0.4264	0.054*
C16	0.8058 (3)	0.45790 (19)	0.3946 (3)	0.0322 (9)
H16A	0.7479	0.4153	0.4115	0.048*
H16C	0.8882	0.4429	0.4239	0.048*
H16B	0.8050	0.4635	0.3182	0.048*
C17	0.7688 (3)	0.5393 (2)	0.4421 (3)	0.0264 (8)
C18	0.5894 (3)	0.5475 (2)	0.3036 (3)	0.0292 (9)
H18A	0.6039	0.4914	0.2783	0.035*
H18B	0.6335	0.5864	0.2610	0.035*
C19	0.4532 (3)	0.5665 (2)	0.2936 (3)	0.0286 (9)
H19B	0.4395	0.6233	0.3167	0.034*
H19A	0.4202	0.5612	0.2193	0.034*
C20	0.2599 (3)	0.5272 (2)	0.3719 (3)	0.0271 (8)
H20	0.2554	0.5804	0.4102	0.033*
C21	0.2064 (3)	0.4599 (2)	0.4382 (3)	0.0284 (9)
H21B	0.1166	0.4606	0.4221	0.034*
H21A	0.2360	0.4069	0.4129	0.034*
C22	0.1847 (3)	0.5349 (2)	0.2649 (3)	0.0393 (10)
H22C	0.2188	0.5788	0.2240	0.059*
H22B	0.0996	0.5477	0.2762	0.059*
H22A	0.1880	0.4832	0.2266	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0054 (3)	0.0286 (3)	0.0277 (4)	−0.0020 (2)	−0.0018 (2)	0.0003 (3)
P1	0.0101 (4)	0.0288 (5)	0.0254 (6)	0.0011 (4)	−0.0012 (4)	0.0002 (4)
S1	0.0183 (5)	0.0418 (6)	0.0253 (6)	0.0041 (4)	−0.0039 (4)	0.0001 (4)
O1	0.0097 (11)	0.0319 (13)	0.0286 (16)	0.0078 (10)	−0.0013 (10)	−0.0016 (10)
O2	0.0102 (11)	0.0251 (12)	0.0287 (15)	−0.0035 (9)	−0.0003 (10)	0.0007 (10)
O3	0.0090 (11)	0.0259 (12)	0.0311 (16)	−0.0025 (9)	−0.0037 (10)	−0.0022 (10)
N1	0.0093 (14)	0.0271 (16)	0.0282 (19)	−0.0002 (12)	−0.0046 (12)	0.0010 (13)
N2	0.0068 (13)	0.0291 (17)	0.0287 (19)	−0.0005 (12)	0.0022 (12)	0.0010 (13)
C1	0.0087 (16)	0.0267 (18)	0.030 (2)	0.0015 (14)	−0.0059 (15)	−0.0003 (15)
C2	0.0074 (16)	0.037 (2)	0.028 (2)	−0.0006 (15)	−0.0028 (15)	−0.0053 (16)
C3	0.0164 (18)	0.041 (2)	0.025 (2)	0.0003 (16)	0.0000 (16)	−0.0053 (16)
C4	0.0109 (17)	0.0274 (19)	0.035 (2)	−0.0008 (14)	−0.0083 (15)	−0.0062 (15)
C5	0.0088 (17)	0.037 (2)	0.037 (3)	−0.0005 (15)	0.0000 (16)	0.0045 (17)
C6	0.0208 (19)	0.037 (2)	0.031 (2)	0.0005 (16)	0.0033 (17)	0.0057 (17)
C7	0.0173 (19)	0.053 (3)	0.044 (3)	0.0011 (18)	−0.0110 (18)	−0.005 (2)
C8	0.0154 (17)	0.0243 (18)	0.025 (2)	−0.0019 (14)	−0.0005 (15)	−0.0022 (14)
C9	0.0120 (17)	0.0276 (19)	0.039 (3)	0.0033 (14)	−0.0042 (15)	−0.0014 (16)
C10	0.0104 (17)	0.035 (2)	0.045 (3)	0.0011 (15)	−0.0036 (16)	−0.0060 (18)
C11	0.0216 (19)	0.0244 (19)	0.042 (3)	−0.0039 (15)	0.0015 (17)	−0.0068 (17)
C12	0.028 (2)	0.0241 (19)	0.049 (3)	0.0052 (16)	−0.0078 (18)	0.0010 (17)
C13	0.0134 (17)	0.034 (2)	0.041 (3)	0.0020 (16)	−0.0046 (16)	0.0004 (17)
C14	0.033 (2)	0.032 (2)	0.071 (4)	−0.0046 (18)	0.002 (2)	−0.007 (2)
C15	0.0163 (18)	0.040 (2)	0.052 (3)	−0.0080 (17)	0.0056 (18)	−0.0021 (19)
C16	0.0117 (17)	0.039 (2)	0.046 (3)	−0.0004 (16)	0.0041 (16)	−0.0026 (18)
C17	0.0038 (15)	0.032 (2)	0.043 (3)	−0.0026 (14)	0.0005 (15)	−0.0032 (17)
C18	0.0139 (17)	0.037 (2)	0.038 (3)	−0.0031 (15)	0.0064 (16)	0.0042 (17)
C19	0.0194 (18)	0.035 (2)	0.030 (2)	0.0013 (16)	−0.0020 (16)	0.0037 (16)
C20	0.0071 (16)	0.038 (2)	0.036 (2)	0.0036 (15)	−0.0035 (15)	0.0000 (17)
C21	0.0051 (16)	0.037 (2)	0.043 (3)	−0.0018 (15)	−0.0024 (15)	−0.0024 (17)
C22	0.0195 (19)	0.051 (3)	0.045 (3)	0.0058 (18)	−0.0129 (17)	0.004 (2)

Geometric parameters (Å, º) top

Ni1—N1	2.076 (3)	C9—H9	0.9500
Ni1—N1ⁱ	2.076 (3)	C10—C11	1.367 (4)
Ni1—N2	2.093 (2)	C10—H10	0.9500
Ni1—N2ⁱ	2.093 (2)	C11—C12	1.388 (4)
Ni1—O3ⁱ	2.106 (2)	C11—C14	1.504 (4)
Ni1—O3	2.106 (2)	C12—C13	1.385 (4)
P1—O3	1.491 (2)	C12—H12	0.9500
P1—O1	1.621 (2)	C13—H13	0.9500
P1—O2	1.627 (2)	C14—H14A	0.9800
P1—S1	1.9372 (14)	C14—H14B	0.9800
O1—C1	1.407 (4)	C14—H14C	0.9800
O2—C8	1.395 (3)	C15—C17	1.535 (4)
N1—C20	1.480 (4)	C15—H15A	0.9800
N1—C19	1.485 (4)	C15—H15C	0.9800
N1—H1	0.92 (3)	C15—H15B	0.9800
N2—C18	1.474 (4)	C16—C17	1.533 (4)
N2—C17	1.518 (4)	C16—H16A	0.9800
N2—H2	0.96 (3)	C16—H16C	0.9800
C1—C2	1.370 (4)	C16—H16B	0.9800
C1—C6	1.376 (4)	C17—C21ⁱ	1.529 (5)
C2—C3	1.384 (4)	C18—C19	1.522 (4)
C2—H2A	0.9500	C18—H18A	0.9900
C3—C4	1.399 (4)	C18—H18B	0.9900
C3—H3	0.9500	C19—H19B	0.9900
C4—C5	1.382 (5)	C19—H19A	0.9900
C4—C7	1.519 (4)	C20—C21	1.536 (4)
C5—C6	1.385 (4)	C20—C22	1.540 (4)
C5—H5	0.9500	C20—H20	1.0000
C6—H6	0.9500	C21—C17ⁱ	1.529 (5)
C7—H7A	0.9800	C21—H21B	0.9900
C7—H7C	0.9800	C21—H21A	0.9900
C7—H7B	0.9800	C22—H22C	0.9800
C8—C13	1.366 (4)	C22—H22B	0.9800
C8—C9	1.390 (4)	C22—H22A	0.9800
C9—C10	1.392 (4)

N1—Ni1—N1ⁱ	180.0	C11—C10—C9	122.2 (3)
N1—Ni1—N2	84.83 (11)	C11—C10—H10	118.9
N1ⁱ—Ni1—N2	95.17 (11)	C9—C10—H10	118.9
N1—Ni1—N2ⁱ	95.17 (11)	C10—C11—C12	118.1 (3)
N1ⁱ—Ni1—N2ⁱ	84.83 (11)	C10—C11—C14	121.4 (3)
N2—Ni1—N2ⁱ	180.0	C12—C11—C14	120.6 (3)
N1—Ni1—O3ⁱ	90.54 (10)	C13—C12—C11	120.8 (3)
N1ⁱ—Ni1—O3ⁱ	89.46 (10)	C13—C12—H12	119.6
N2—Ni1—O3ⁱ	93.63 (9)	C11—C12—H12	119.6
N2ⁱ—Ni1—O3ⁱ	86.37 (9)	C8—C13—C12	120.2 (3)
N1—Ni1—O3	89.46 (10)	C8—C13—H13	119.9
N1ⁱ—Ni1—O3	90.54 (10)	C12—C13—H13	119.9
N2—Ni1—O3	86.37 (9)	C11—C14—H14A	109.5
N2ⁱ—Ni1—O3	93.63 (9)	C11—C14—H14B	109.5
O3ⁱ—Ni1—O3	179.999 (1)	H14A—C14—H14B	109.5
O3—P1—O1	109.22 (12)	C11—C14—H14C	109.5
O3—P1—O2	102.67 (12)	H14A—C14—H14C	109.5
O1—P1—O2	103.25 (11)	H14B—C14—H14C	109.5
O3—P1—S1	120.90 (10)	C17—C15—H15A	109.5
O1—P1—S1	107.79 (10)	C17—C15—H15C	109.5
O2—P1—S1	111.61 (9)	H15A—C15—H15C	109.5
C1—O1—P1	122.1 (2)	C17—C15—H15B	109.5
C8—O2—P1	122.6 (2)	H15A—C15—H15B	109.5
P1—O3—Ni1	143.74 (12)	H15C—C15—H15B	109.5
C20—N1—C19	115.3 (2)	C17—C16—H16A	109.5
C20—N1—Ni1	115.0 (2)	C17—C16—H16C	109.5
C19—N1—Ni1	105.51 (19)	H16A—C16—H16C	109.5
C20—N1—H1	108.7 (19)	C17—C16—H16B	109.5
C19—N1—H1	106 (2)	H16A—C16—H16B	109.5
Ni1—N1—H1	105 (2)	H16C—C16—H16B	109.5
C18—N2—C17	115.9 (2)	N2—C17—C21ⁱ	108.1 (2)
C18—N2—Ni1	106.15 (18)	N2—C17—C16	110.2 (3)
C17—N2—Ni1	121.8 (2)	C21ⁱ—C17—C16	111.8 (3)
C18—N2—H2	110 (2)	N2—C17—C15	108.8 (3)
C17—N2—H2	107.0 (18)	C21ⁱ—C17—C15	108.2 (3)
Ni1—N2—H2	93.0 (17)	C16—C17—C15	109.7 (3)
C2—C1—C6	120.6 (3)	N2—C18—C19	107.6 (3)
C2—C1—O1	122.5 (3)	N2—C18—H18A	110.2
C6—C1—O1	116.8 (3)	C19—C18—H18A	110.2
C1—C2—C3	119.2 (3)	N2—C18—H18B	110.2
C1—C2—H2A	120.4	C19—C18—H18B	110.2
C3—C2—H2A	120.4	H18A—C18—H18B	108.5
C2—C3—C4	121.6 (3)	N1—C19—C18	109.0 (3)
C2—C3—H3	119.2	N1—C19—H19B	109.9
C4—C3—H3	119.2	C18—C19—H19B	109.9
C5—C4—C3	117.6 (3)	N1—C19—H19A	109.9
C5—C4—C7	120.2 (3)	C18—C19—H19A	109.9
C3—C4—C7	122.1 (3)	H19B—C19—H19A	108.3
C4—C5—C6	121.0 (3)	N1—C20—C21	108.9 (3)
C4—C5—H5	119.5	N1—C20—C22	112.0 (3)
C6—C5—H5	119.5	C21—C20—C22	110.3 (3)
C1—C6—C5	120.0 (3)	N1—C20—H20	108.5
C1—C6—H6	120.0	C21—C20—H20	108.5
C5—C6—H6	120.0	C22—C20—H20	108.5
C4—C7—H7A	109.5	C17ⁱ—C21—C20	120.1 (3)
C4—C7—H7C	109.5	C17ⁱ—C21—H21B	107.3
H7A—C7—H7C	109.5	C20—C21—H21B	107.3
C4—C7—H7B	109.5	C17ⁱ—C21—H21A	107.3
H7A—C7—H7B	109.5	C20—C21—H21A	107.3
H7C—C7—H7B	109.5	H21B—C21—H21A	106.9
C13—C8—C9	120.3 (3)	C20—C22—H22C	109.5
C13—C8—O2	121.1 (3)	C20—C22—H22B	109.5
C9—C8—O2	118.6 (3)	H22C—C22—H22B	109.5
C8—C9—C10	118.4 (3)	C20—C22—H22A	109.5
C8—C9—H9	120.8	H22C—C22—H22A	109.5
C10—C9—H9	120.8	H22B—C22—H22A	109.5

O3—P1—O1—C1	−32.3 (3)	C2—C3—C4—C7	177.2 (3)
O2—P1—O1—C1	76.4 (2)	C3—C4—C5—C6	0.8 (5)
S1—P1—O1—C1	−165.4 (2)	C7—C4—C5—C6	−176.9 (3)
O3—P1—O2—C8	−179.0 (2)	C2—C1—C6—C5	−0.4 (5)
O1—P1—O2—C8	67.5 (2)	O1—C1—C6—C5	176.8 (3)
S1—P1—O2—C8	−48.0 (2)	C4—C5—C6—C1	−0.3 (5)
O1—P1—O3—Ni1	−177.58 (19)	P1—O2—C8—C13	−91.2 (4)
O2—P1—O3—Ni1	73.3 (2)	P1—O2—C8—C9	91.8 (3)
S1—P1—O3—Ni1	−51.7 (2)	C13—C8—C9—C10	−1.4 (5)
N1—Ni1—O3—P1	−144.9 (2)	O2—C8—C9—C10	175.6 (3)
N1ⁱ—Ni1—O3—P1	35.1 (2)	C8—C9—C10—C11	1.2 (5)
N2—Ni1—O3—P1	−60.0 (2)	C9—C10—C11—C12	−0.3 (5)
N2ⁱ—Ni1—O3—P1	120.0 (2)	C9—C10—C11—C14	−179.8 (3)
N2—Ni1—N1—C20	−143.3 (2)	C10—C11—C12—C13	−0.6 (6)
N2ⁱ—Ni1—N1—C20	36.7 (2)	C14—C11—C12—C13	178.9 (3)
O3ⁱ—Ni1—N1—C20	123.1 (2)	C9—C8—C13—C12	0.6 (5)
O3—Ni1—N1—C20	−56.9 (2)	O2—C8—C13—C12	−176.3 (3)
N2—Ni1—N1—C19	−15.08 (19)	C11—C12—C13—C8	0.5 (5)
N2ⁱ—Ni1—N1—C19	164.92 (19)	C18—N2—C17—C21ⁱ	−173.6 (3)
O3ⁱ—Ni1—N1—C19	−108.67 (19)	Ni1—N2—C17—C21ⁱ	−41.9 (3)
O3—Ni1—N1—C19	71.33 (19)	C18—N2—C17—C16	−51.1 (4)
N1—Ni1—N2—C18	−15.2 (2)	Ni1—N2—C17—C16	80.6 (3)
N1ⁱ—Ni1—N2—C18	164.8 (2)	C18—N2—C17—C15	69.2 (4)
O3ⁱ—Ni1—N2—C18	75.0 (2)	Ni1—N2—C17—C15	−159.1 (2)
O3—Ni1—N2—C18	−105.0 (2)	C17—N2—C18—C19	−179.2 (3)
N1—Ni1—N2—C17	−150.8 (2)	Ni1—N2—C18—C19	42.2 (3)
N1ⁱ—Ni1—N2—C17	29.2 (2)	C20—N1—C19—C18	170.7 (3)
O3ⁱ—Ni1—N2—C17	−60.6 (2)	Ni1—N1—C19—C18	42.7 (3)
O3—Ni1—N2—C17	119.4 (2)	N2—C18—C19—N1	−58.6 (3)
P1—O1—C1—C2	−52.2 (4)	C19—N1—C20—C21	177.5 (3)
P1—O1—C1—C6	130.7 (3)	Ni1—N1—C20—C21	−59.3 (3)
C6—C1—C2—C3	0.7 (5)	C19—N1—C20—C22	55.2 (4)
O1—C1—C2—C3	−176.3 (3)	Ni1—N1—C20—C22	178.4 (2)
C1—C2—C3—C4	−0.3 (5)	N1—C20—C21—C17ⁱ	79.5 (4)
C2—C3—C4—C5	−0.4 (5)	C22—C20—C21—C17ⁱ	−157.2 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₆H₃₆N₄)](C₁₄H₁₄O₃PS)₂
M_r	929.76
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	10.977 (2), 16.360 (3), 12.767 (3)
β (°)	94.85 (3)
V (Å³)	2284.6 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.24 × 0.23 × 0.22

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.862, 0.873
No. of measured, independent and observed [I > 2σ(I)] reflections	18654, 5376, 2665
R_int	0.101
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.122, 0.99
No. of reflections	5376
No. of parameters	281
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.97, −0.91

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

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)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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).

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Feng, J.-S., Zou, L.-K., Xie, B., Xiang, Y.-G. & Lai, C. (2010). Acta Cryst. E66, m1593. Web of Science CSD CrossRef IUCr Journals Google Scholar
He, L.-X., Zou, L.-K., Xie, B., Xiang, Y.-G. & Feng, J.-S. (2010). Acta Cryst. E66, m428. Web of Science CrossRef IUCr Journals Google Scholar
Pesin, V. G. & Khaletakii, A. M. (1961). J. Gen. Chem. USSR, 31, 2337–2343. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zou, L.-K., Xie, B., Feng, J.-S. & Lai, C. (2010). Acta Cryst. E66, m1592. Web of Science CSD CrossRef IUCr Journals Google Scholar

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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