(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene)nickel(II) bis­[O,O′-bis­(4-tert-butyl­phen­yl) dithio­phosphate]

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

doi:10.1107/S1600536810049615

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page m17

https://doi.org/10.1107/S1600536810049615

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(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) bis[O,O′-bis(4-tert-butylphenyl) dithiophosphate]

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

^aCollege of Material and Chemical 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 27 November 2010; online 4 December 2010)

The title salt, [Ni(C₁₆H₃₂N₄)](C₂₀H₂₆O₂PS₂)₂, comprises a centrosymmetric [Ni(Me₆[14]dieneN₄)]²⁺ dication (Me₆[14]dieneN₄ is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) and two O,O′-bis(4-tert-butylphenyl) dithiophosphate anions. The Ni^II ion lies on an inversion centre and displays a slightly distorted NiN₄ square-planar chelation arrangement with four N atoms from the Me₆[14]dieneN₄ macrocycle. Two S atoms from symmetry-related anions are located in pseudo-axial positions with respect to the Ni^II ion, with Ni⋯S distances of 3.2991 (7) Å. Intermolecular N—H⋯S and C—H⋯S hydrogen bonds link the complex cation and pair of anions into a 1:2 type salt.

Related literature

For synthetic procedures, see: Li & Xie (1997 ); Xie et al. (2009 ). For applications as mimetic enzymes of transition metal complexes of tetramine macrocycles, see: Aoki & Kimura (2002 ). For related structures, see: Feng et al. (2010 ); He et al. (2010 ); Zou et al. (2010 ).

Experimental

Crystal data

[Ni(C₁₆H₃₂N₄)](C₂₀H₂₆O₂PS₂)₂
M_r = 1126.16
Triclinic, $[P \overline 1]$
a = 9.445 (2) Å
b = 12.168 (3) Å
c = 12.740 (3) Å
α = 95.965 (4)°
β = 91.360 (3)°
γ = 99.787 (4)°
V = 1433.7 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 103 K
0.27 × 0.23 × 0.08 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.859, T_max = 0.955
14032 measured reflections
6434 independent reflections
4838 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.101
S = 1.00
6434 reflections
335 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S2ⁱ	0.88 (3)	2.70 (3)	3.542 (2)	162 (3)
C7—H7A⋯S2ⁱ	0.98	2.82	3.703 (3)	150
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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/S1600536810049615/pv2360sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049615/pv2360Isup2.hkl

checkCIF report

Comment top

The synthesis and structural investigation of tetramine macrocycle have attracted much attention due to their analogy to naturally occurring macrocyclic systems and the potential applications as mimetic enzymes of their transition metal complexes (Aoki et al., 2002). We have recently reported the crystal structures of tetramine macrocyclic transition metal adducts with O,O'-dialkyldithiophosphate (He et al., 2010; Feng et al., 2010; Zou et al., 2010). We report herein the synthesis and structure of an analogous adduct, [Ni(Me₆[14]dieneN₄)][S₂P(OC₆H₄Me-4)₂]₂, where Me₆[14]dieneN₄ is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene.

In the centrosymmetric structure of the title adduct, Ni^II ion lies on an inversion centre and is accommodated in the tetradentatic 14-membered tetramine macrocycle cavity in a slightly distorted mononuclear NiN₄ square-planar geometry (Fig. 1). The net charge on Ni^II ion is balanced by two symmetry related O,O'- bis(4-tert-butylphenyl)dithiophosphate anions, which are located in the pseudo-axial positions with respect to the inversion centre with Ni···S distances of 3.2991 (7) Å. The complex cations and anions interact with each other through intermolecular N—H···S and C—H···S hydrogen bonds (Table 1).

Related literature top

For synthetic procedures, see: Li & Xie (1997); Xie et al. (2009). For applications as mimetic enzymes of transition metal complexes of tetramine macrocycles, see: Aoki & Kimura (2002). For related structures, see: Feng et al. (2010); He et al. (2010); Zou et al. (2010).

Experimental top

[Et₂NH₂][S₂P(OC₆H₄(Bu-t)-4)₂] was synthesized according to the procedure described by Li & Xie (1997). [Ni(Me₆[14]dieneN₄)](ClO₄)₂ was prepared by the method reported by Xie et al. (2009). The title adduct was obtained by the reaction of [Ni(Me₆[14]dieneN₄)](ClO₄)₂ (0.541 g, 1 mmol) and [Et₂NH₂][S₂P(OC₆H₄(Bu-t)-4)₂] (0.936 g, 2 mmol) in refluxing methanol for 3 h. After cooling to room temperature, the precipitate was filtered off, washed with diethyl ether and recrystallized from benzene. The obtained solid was dissolved in hot methanol and filtered, the filtrate was slowly evaporated at room temperature for several days until the formation of orange platelet crystals of the title adduct.

Structure description top

For synthetic procedures, see: Li & Xie (1997); Xie et al. (2009). For applications as mimetic enzymes of transition metal complexes of tetramine macrocycles, see: Aoki & Kimura (2002). For related structures, see: Feng et al. (2010); He et al. (2010); Zou et al. (2010).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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 at 50% 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. Atoms with the superscript i are generated by the symmetry operation (-x, -y + 1,-z + 1).

(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) bis[O,O'-bis(4-tert-butylphenyl) dithiophosphate] top

Crystal data top

[Ni(C₁₆H₃₂N₄)](C₂₀H₂₆O₂PS₂)₂	Z = 1
M_r = 1126.16	F(000) = 602
Triclinic, P1	D_x = 1.304 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.445 (2) Å	Cell parameters from 3818 reflections
b = 12.168 (3) Å	θ = 3.0–27.5°
c = 12.740 (3) Å	µ = 0.59 mm⁻¹
α = 95.965 (4)°	T = 103 K
β = 91.360 (3)°	Plate, orange
γ = 99.787 (4)°	0.27 × 0.23 × 0.08 mm
V = 1433.7 (5) Å³

Data collection top

Rigaku SPIDER diffractometer	6434 independent reflections
Radiation source: Rotating Anode	4838 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→12
T_min = 0.859, T_max = 0.955	k = −15→14
14032 measured reflections	l = −16→16

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0451P)² + 0.698P] where P = (F_o² + 2F_c²)/3
6434 reflections	(Δ/σ)_max = 0.001
335 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Ni(C₁₆H₃₂N₄)](C₂₀H₂₆O₂PS₂)₂	γ = 99.787 (4)°
M_r = 1126.16	V = 1433.7 (5) Å³
Triclinic, P1	Z = 1
a = 9.445 (2) Å	Mo Kα radiation
b = 12.168 (3) Å	µ = 0.59 mm⁻¹
c = 12.740 (3) Å	T = 103 K
α = 95.965 (4)°	0.27 × 0.23 × 0.08 mm
β = 91.360 (3)°

Data collection top

Rigaku SPIDER diffractometer	6434 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4838 reflections with I > 2σ(I)
T_min = 0.859, T_max = 0.955	R_int = 0.036
14032 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.36 e Å⁻³
6434 reflections	Δρ_min = −0.35 e Å⁻³
335 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.0000	0.5000	0.5000	0.01467 (11)
P1	0.38240 (6)	0.74491 (5)	0.59769 (5)	0.01291 (13)
S1	0.18719 (6)	0.75534 (5)	0.55415 (5)	0.01884 (14)
S2	0.41409 (6)	0.65477 (5)	0.71245 (4)	0.01634 (13)
O1	0.47162 (17)	0.69494 (13)	0.50147 (12)	0.0163 (3)
O2	0.46883 (16)	0.87255 (13)	0.62254 (12)	0.0161 (3)
N1	−0.11781 (19)	0.56640 (16)	0.59937 (15)	0.0147 (4)
N2	−0.1166 (2)	0.54850 (17)	0.39160 (15)	0.0147 (4)
C1	−0.2353 (2)	0.6077 (2)	0.54470 (19)	0.0186 (5)
H1A	−0.2638	0.6718	0.5885	0.022*
H1B	−0.3203	0.5474	0.5312	0.022*
C2	−0.1784 (2)	0.6437 (2)	0.44242 (18)	0.0180 (5)
H2A	−0.2568	0.6602	0.3969	0.022*
H2B	−0.1036	0.7118	0.4555	0.022*
C3	−0.0567 (2)	0.56507 (19)	0.28493 (18)	0.0158 (5)
C4	−0.0187 (2)	0.4525 (2)	0.24158 (18)	0.0180 (5)
H4A	−0.1058	0.3944	0.2416	0.022*
H4B	0.0075	0.4569	0.1672	0.022*
C5	0.1014 (2)	0.41448 (19)	0.29968 (19)	0.0168 (5)
C6	0.0743 (2)	0.6583 (2)	0.29262 (18)	0.0172 (5)
H6A	0.0457	0.7298	0.3179	0.021*
H6B	0.1147	0.6633	0.2228	0.021*
H6C	0.1468	0.6417	0.3421	0.021*
C7	−0.1720 (2)	0.5932 (2)	0.20931 (18)	0.0176 (5)
H7A	−0.2588	0.5359	0.2077	0.021*
H7B	−0.1351	0.5950	0.1381	0.021*
H7C	−0.1954	0.6668	0.2341	0.021*
C8	0.1938 (3)	0.3504 (2)	0.2313 (2)	0.0233 (5)
H8A	0.2953	0.3819	0.2480	0.028*
H8B	0.1710	0.3562	0.1568	0.028*
H8C	0.1753	0.2714	0.2444	0.028*
C9	0.4542 (2)	0.70913 (19)	0.39500 (17)	0.0135 (4)
C10	0.4612 (2)	0.61550 (19)	0.32408 (18)	0.0148 (5)
H10	0.4730	0.5466	0.3492	0.018*
C11	0.4510 (2)	0.62328 (19)	0.21665 (18)	0.0153 (5)
H11	0.4557	0.5590	0.1685	0.018*
C12	0.4338 (2)	0.72341 (19)	0.17723 (18)	0.0155 (5)
C13	0.4277 (2)	0.81515 (19)	0.25037 (18)	0.0167 (5)
H13	0.4161	0.8842	0.2256	0.020*
C14	0.4379 (2)	0.80954 (19)	0.35900 (18)	0.0165 (5)
H14	0.4337	0.8737	0.4074	0.020*
C15	0.4216 (3)	0.7279 (2)	0.05768 (18)	0.0190 (5)
C16	0.5521 (3)	0.6889 (2)	0.00546 (19)	0.0248 (6)
H16A	0.5442	0.6924	−0.0709	0.030*
H16B	0.5550	0.6115	0.0192	0.030*
H16C	0.6404	0.7379	0.0348	0.030*
C17	0.4152 (3)	0.8452 (2)	0.0292 (2)	0.0342 (7)
H17A	0.4071	0.8437	−0.0478	0.041*
H17B	0.5030	0.8962	0.0564	0.041*
H17C	0.3315	0.8712	0.0606	0.041*
C18	0.2848 (3)	0.6490 (3)	0.0122 (2)	0.0341 (7)
H18A	0.2004	0.6748	0.0428	0.041*
H18B	0.2877	0.5728	0.0295	0.041*
H18C	0.2790	0.6491	−0.0647	0.041*
C19	0.6129 (2)	0.89734 (18)	0.65979 (18)	0.0155 (5)
C20	0.6442 (2)	0.90526 (19)	0.76688 (18)	0.0151 (5)
H20	0.5700	0.8875	0.8145	0.018*
C21	0.7862 (2)	0.93967 (19)	0.80414 (18)	0.0162 (5)
H21	0.8080	0.9446	0.8778	0.019*
C22	0.8978 (2)	0.96726 (19)	0.73619 (18)	0.0167 (5)
C23	0.8612 (3)	0.9561 (2)	0.62884 (19)	0.0220 (5)
H23	0.9349	0.9724	0.5804	0.026*
C24	0.7195 (3)	0.9215 (2)	0.59016 (19)	0.0208 (5)
H24	0.6970	0.9148	0.5164	0.025*
C25	1.0515 (2)	1.0085 (2)	0.78141 (19)	0.0192 (5)
C26	1.1533 (3)	1.0529 (2)	0.6975 (2)	0.0265 (6)
H26A	1.1627	0.9913	0.6436	0.032*
H26B	1.2479	1.0848	0.7308	0.032*
H26C	1.1142	1.1111	0.6643	0.032*
C27	1.0506 (3)	1.1031 (2)	0.8708 (2)	0.0261 (6)
H27A	1.0100	1.1640	0.8436	0.031*
H27B	1.1492	1.1317	0.8984	0.031*
H27C	0.9919	1.0741	0.9276	0.031*
C28	1.1095 (3)	0.9114 (2)	0.8255 (2)	0.0258 (6)
H28A	1.0468	0.8826	0.8803	0.031*
H28B	1.2070	0.9383	0.8560	0.031*
H28C	1.1117	0.8513	0.7684	0.031*
H2N	−0.185 (3)	0.490 (3)	0.379 (2)	0.046 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0110 (2)	0.0202 (2)	0.0153 (2)	0.00699 (16)	0.00251 (16)	0.00626 (17)
P1	0.0122 (3)	0.0134 (3)	0.0131 (3)	0.0027 (2)	0.0002 (2)	0.0005 (2)
S1	0.0125 (3)	0.0244 (3)	0.0195 (3)	0.0046 (2)	−0.0016 (2)	0.0007 (2)
S2	0.0169 (3)	0.0166 (3)	0.0154 (3)	0.0011 (2)	−0.0002 (2)	0.0047 (2)
O1	0.0179 (8)	0.0211 (9)	0.0119 (8)	0.0091 (6)	0.0002 (6)	0.0024 (7)
O2	0.0155 (8)	0.0124 (8)	0.0199 (9)	0.0017 (6)	−0.0031 (7)	0.0018 (7)
N1	0.0100 (9)	0.0168 (10)	0.0182 (10)	0.0036 (7)	0.0015 (7)	0.0045 (8)
N2	0.0113 (9)	0.0162 (10)	0.0185 (10)	0.0045 (7)	0.0029 (8)	0.0064 (8)
C1	0.0118 (11)	0.0243 (13)	0.0225 (13)	0.0089 (9)	0.0019 (9)	0.0062 (10)
C2	0.0159 (11)	0.0198 (12)	0.0204 (12)	0.0089 (9)	0.0018 (9)	0.0033 (10)
C3	0.0126 (11)	0.0187 (12)	0.0169 (12)	0.0027 (8)	0.0019 (9)	0.0059 (9)
C4	0.0148 (11)	0.0220 (12)	0.0167 (12)	0.0028 (9)	−0.0010 (9)	0.0012 (10)
C5	0.0113 (11)	0.0167 (12)	0.0217 (12)	0.0002 (8)	0.0015 (9)	0.0031 (10)
C6	0.0137 (11)	0.0225 (12)	0.0157 (12)	0.0017 (9)	0.0006 (9)	0.0055 (10)
C7	0.0144 (11)	0.0211 (12)	0.0184 (12)	0.0038 (9)	−0.0025 (9)	0.0074 (10)
C8	0.0204 (13)	0.0244 (13)	0.0251 (13)	0.0080 (10)	−0.0006 (10)	−0.0040 (11)
C9	0.0095 (10)	0.0197 (12)	0.0111 (11)	0.0022 (8)	0.0003 (8)	0.0016 (9)
C10	0.0122 (11)	0.0139 (11)	0.0185 (12)	0.0031 (8)	0.0022 (9)	0.0020 (9)
C11	0.0131 (11)	0.0153 (11)	0.0174 (12)	0.0034 (8)	0.0014 (9)	−0.0009 (9)
C12	0.0099 (10)	0.0211 (12)	0.0153 (11)	0.0026 (8)	0.0005 (8)	0.0011 (9)
C13	0.0186 (12)	0.0150 (11)	0.0168 (12)	0.0028 (9)	0.0005 (9)	0.0026 (9)
C14	0.0154 (11)	0.0167 (12)	0.0167 (12)	0.0023 (9)	−0.0008 (9)	−0.0005 (9)
C15	0.0185 (12)	0.0232 (13)	0.0157 (12)	0.0047 (9)	0.0004 (9)	0.0029 (10)
C16	0.0221 (13)	0.0367 (16)	0.0158 (12)	0.0057 (11)	0.0045 (10)	0.0017 (11)
C17	0.056 (2)	0.0365 (17)	0.0163 (13)	0.0209 (14)	0.0063 (13)	0.0094 (12)
C18	0.0226 (14)	0.060 (2)	0.0152 (13)	−0.0037 (13)	−0.0026 (11)	0.0036 (13)
C19	0.0134 (11)	0.0118 (11)	0.0208 (12)	0.0013 (8)	−0.0024 (9)	0.0013 (9)
C20	0.0175 (11)	0.0139 (11)	0.0141 (11)	0.0016 (8)	0.0041 (9)	0.0026 (9)
C21	0.0201 (12)	0.0180 (12)	0.0093 (11)	0.0007 (9)	0.0002 (9)	0.0004 (9)
C22	0.0162 (11)	0.0143 (11)	0.0189 (12)	−0.0003 (8)	0.0008 (9)	0.0036 (9)
C23	0.0187 (12)	0.0285 (14)	0.0164 (12)	−0.0029 (10)	0.0044 (10)	0.0019 (10)
C24	0.0231 (13)	0.0241 (13)	0.0135 (12)	−0.0012 (10)	−0.0013 (10)	0.0027 (10)
C25	0.0142 (11)	0.0217 (13)	0.0203 (12)	−0.0019 (9)	−0.0006 (9)	0.0039 (10)
C26	0.0156 (12)	0.0319 (15)	0.0289 (14)	−0.0044 (10)	0.0004 (10)	0.0033 (12)
C27	0.0246 (13)	0.0222 (14)	0.0261 (14)	−0.0069 (10)	−0.0025 (11)	−0.0036 (11)
C28	0.0201 (13)	0.0314 (15)	0.0266 (14)	0.0054 (10)	−0.0015 (11)	0.0061 (11)

Geometric parameters (Å, º) top

Ni1—N1	1.9114 (19)	C11—C12	1.398 (3)
Ni1—N1ⁱ	1.9114 (19)	C11—H11	0.9500
Ni1—N2	1.9457 (19)	C12—C13	1.388 (3)
Ni1—N2ⁱ	1.9457 (19)	C12—C15	1.532 (3)
Ni1—S1	3.2990 (9)	C13—C14	1.394 (3)
P1—O2	1.6226 (16)	C13—H13	0.9500
P1—O1	1.6281 (17)	C14—H14	0.9500
P1—S1	1.9413 (9)	C15—C17	1.519 (4)
P1—S2	1.9632 (9)	C15—C18	1.534 (3)
O1—C9	1.394 (3)	C15—C16	1.536 (3)
O2—C19	1.403 (3)	C16—H16A	0.9800
N1—C5ⁱ	1.284 (3)	C16—H16B	0.9800
N1—C1	1.481 (3)	C16—H16C	0.9800
N2—C2	1.481 (3)	C17—H17A	0.9800
N2—C3	1.504 (3)	C17—H17B	0.9800
N2—H2N	0.88 (3)	C17—H17C	0.9800
C1—C2	1.500 (3)	C18—H18A	0.9800
C1—H1A	0.9900	C18—H18B	0.9800
C1—H1B	0.9900	C18—H18C	0.9800
C2—H2A	0.9900	C19—C24	1.372 (3)
C2—H2B	0.9900	C19—C20	1.379 (3)
C3—C6	1.524 (3)	C20—C21	1.392 (3)
C3—C4	1.526 (3)	C20—H20	0.9500
C3—C7	1.542 (3)	C21—C22	1.399 (3)
C4—C5	1.503 (3)	C21—H21	0.9500
C4—H4A	0.9900	C22—C23	1.390 (3)
C4—H4B	0.9900	C22—C25	1.531 (3)
C5—N1ⁱ	1.284 (3)	C23—C24	1.395 (3)
C5—C8	1.501 (3)	C23—H23	0.9500
C6—H6A	0.9800	C24—H24	0.9500
C6—H6B	0.9800	C25—C26	1.534 (3)
C6—H6C	0.9800	C25—C28	1.534 (4)
C7—H7A	0.9800	C25—C27	1.535 (3)
C7—H7B	0.9800	C26—H26A	0.9800
C7—H7C	0.9800	C26—H26B	0.9800
C8—H8A	0.9800	C26—H26C	0.9800
C8—H8B	0.9800	C27—H27A	0.9800
C8—H8C	0.9800	C27—H27B	0.9800
C9—C14	1.380 (3)	C27—H27C	0.9800
C9—C10	1.390 (3)	C28—H28A	0.9800
C10—C11	1.384 (3)	C28—H28B	0.9800
C10—H10	0.9500	C28—H28C	0.9800

N1—Ni1—N1ⁱ	180.0	C10—C11—C12	121.6 (2)
N1—Ni1—N2	86.13 (8)	C10—C11—H11	119.2
N1ⁱ—Ni1—N2	93.87 (8)	C12—C11—H11	119.2
N1—Ni1—N2ⁱ	93.87 (8)	C13—C12—C11	117.2 (2)
N1ⁱ—Ni1—N2ⁱ	86.13 (8)	C13—C12—C15	123.0 (2)
N2—Ni1—N2ⁱ	180.0	C11—C12—C15	119.8 (2)
N1—Ni1—S1	78.48 (6)	C12—C13—C14	122.3 (2)
N1ⁱ—Ni1—S1	101.52 (6)	C12—C13—H13	118.8
N2—Ni1—S1	91.63 (6)	C14—C13—H13	118.8
N2ⁱ—Ni1—S1	88.37 (6)	C9—C14—C13	118.8 (2)
O2—P1—O1	101.95 (9)	C9—C14—H14	120.6
O2—P1—S1	106.69 (7)	C13—C14—H14	120.6
O1—P1—S1	112.73 (6)	C17—C15—C12	112.5 (2)
O2—P1—S2	111.23 (6)	C17—C15—C18	108.5 (2)
O1—P1—S2	103.62 (7)	C12—C15—C18	109.3 (2)
S1—P1—S2	119.33 (4)	C17—C15—C16	108.0 (2)
P1—S1—Ni1	109.04 (3)	C12—C15—C16	109.77 (19)
C9—O1—P1	126.04 (15)	C18—C15—C16	108.7 (2)
C19—O2—P1	122.48 (14)	C15—C16—H16A	109.5
C5ⁱ—N1—C1	119.43 (19)	C15—C16—H16B	109.5
C5ⁱ—N1—Ni1	129.37 (16)	H16A—C16—H16B	109.5
C1—N1—Ni1	110.98 (14)	C15—C16—H16C	109.5
C2—N2—C3	115.10 (18)	H16A—C16—H16C	109.5
C2—N2—Ni1	106.77 (14)	H16B—C16—H16C	109.5
C3—N2—Ni1	119.71 (14)	C15—C17—H17A	109.5
C2—N2—H2N	109 (2)	C15—C17—H17B	109.5
C3—N2—H2N	104 (2)	H17A—C17—H17B	109.5
Ni1—N2—H2N	101 (2)	C15—C17—H17C	109.5
N1—C1—C2	106.80 (18)	H17A—C17—H17C	109.5
N1—C1—H1A	110.4	H17B—C17—H17C	109.5
C2—C1—H1A	110.4	C15—C18—H18A	109.5
N1—C1—H1B	110.4	C15—C18—H18B	109.5
C2—C1—H1B	110.4	H18A—C18—H18B	109.5
H1A—C1—H1B	108.6	C15—C18—H18C	109.5
N2—C2—C1	105.96 (19)	H18A—C18—H18C	109.5
N2—C2—H2A	110.5	H18B—C18—H18C	109.5
C1—C2—H2A	110.5	C24—C19—C20	121.0 (2)
N2—C2—H2B	110.5	C24—C19—O2	119.5 (2)
C1—C2—H2B	110.5	C20—C19—O2	119.3 (2)
H2A—C2—H2B	108.7	C19—C20—C21	119.0 (2)
N2—C3—C6	111.51 (19)	C19—C20—H20	120.5
N2—C3—C4	106.03 (19)	C21—C20—H20	120.5
C6—C3—C4	111.42 (19)	C20—C21—C22	121.9 (2)
N2—C3—C7	110.55 (18)	C20—C21—H21	119.1
C6—C3—C7	109.24 (19)	C22—C21—H21	119.1
C4—C3—C7	107.99 (18)	C23—C22—C21	116.9 (2)
C5—C4—C3	116.19 (19)	C23—C22—C25	123.1 (2)
C5—C4—H4A	108.2	C21—C22—C25	119.9 (2)
C3—C4—H4A	108.2	C22—C23—C24	121.9 (2)
C5—C4—H4B	108.2	C22—C23—H23	119.1
C3—C4—H4B	108.2	C24—C23—H23	119.1
H4A—C4—H4B	107.4	C19—C24—C23	119.3 (2)
N1ⁱ—C5—C8	124.0 (2)	C19—C24—H24	120.4
N1ⁱ—C5—C4	121.0 (2)	C23—C24—H24	120.4
C8—C5—C4	114.9 (2)	C22—C25—C26	112.07 (19)
C3—C6—H6A	109.5	C22—C25—C28	109.5 (2)
C3—C6—H6B	109.5	C26—C25—C28	108.1 (2)
H6A—C6—H6B	109.5	C22—C25—C27	109.1 (2)
C3—C6—H6C	109.5	C26—C25—C27	108.7 (2)
H6A—C6—H6C	109.5	C28—C25—C27	109.3 (2)
H6B—C6—H6C	109.5	C25—C26—H26A	109.5
C3—C7—H7A	109.5	C25—C26—H26B	109.5
C3—C7—H7B	109.5	H26A—C26—H26B	109.5
H7A—C7—H7B	109.5	C25—C26—H26C	109.5
C3—C7—H7C	109.5	H26A—C26—H26C	109.5
H7A—C7—H7C	109.5	H26B—C26—H26C	109.5
H7B—C7—H7C	109.5	C25—C27—H27A	109.5
C5—C8—H8A	109.5	C25—C27—H27B	109.5
C5—C8—H8B	109.5	H27A—C27—H27B	109.5
H8A—C8—H8B	109.5	C25—C27—H27C	109.5
C5—C8—H8C	109.5	H27A—C27—H27C	109.5
H8A—C8—H8C	109.5	H27B—C27—H27C	109.5
H8B—C8—H8C	109.5	C25—C28—H28A	109.5
C14—C9—C10	120.5 (2)	C25—C28—H28B	109.5
C14—C9—O1	123.8 (2)	H28A—C28—H28B	109.5
C10—C9—O1	115.6 (2)	C25—C28—H28C	109.5
C11—C10—C9	119.6 (2)	H28A—C28—H28C	109.5
C11—C10—H10	120.2	H28B—C28—H28C	109.5
C9—C10—H10	120.2

O2—P1—S1—Ni1	179.72 (6)	C3—C4—C5—N1ⁱ	36.6 (3)
O1—P1—S1—Ni1	68.62 (7)	C3—C4—C5—C8	−145.5 (2)
S2—P1—S1—Ni1	−53.26 (5)	P1—O1—C9—C14	42.9 (3)
N1—Ni1—S1—P1	126.44 (7)	P1—O1—C9—C10	−140.20 (18)
N1ⁱ—Ni1—S1—P1	−53.56 (7)	C14—C9—C10—C11	−0.3 (3)
N2—Ni1—S1—P1	−147.85 (6)	O1—C9—C10—C11	−177.36 (19)
N2ⁱ—Ni1—S1—P1	32.15 (6)	C9—C10—C11—C12	0.1 (3)
O2—P1—O1—C9	−82.29 (18)	C10—C11—C12—C13	0.1 (3)
S1—P1—O1—C9	31.73 (19)	C10—C11—C12—C15	−179.4 (2)
S2—P1—O1—C9	162.11 (15)	C11—C12—C13—C14	0.0 (3)
O1—P1—O2—C19	−63.81 (18)	C15—C12—C13—C14	179.5 (2)
S1—P1—O2—C19	177.78 (15)	C10—C9—C14—C13	0.4 (3)
S2—P1—O2—C19	46.09 (18)	O1—C9—C14—C13	177.2 (2)
N2—Ni1—N1—C5ⁱ	−169.7 (2)	C12—C13—C14—C9	−0.2 (3)
N2ⁱ—Ni1—N1—C5ⁱ	10.3 (2)	C13—C12—C15—C17	4.9 (3)
S1—Ni1—N1—C5ⁱ	−77.3 (2)	C11—C12—C15—C17	−175.5 (2)
N2—Ni1—N1—C1	4.72 (15)	C13—C12—C15—C18	−115.6 (3)
N2ⁱ—Ni1—N1—C1	−175.28 (15)	C11—C12—C15—C18	63.9 (3)
S1—Ni1—N1—C1	97.18 (14)	C13—C12—C15—C16	125.3 (2)
N1—Ni1—N2—C2	23.67 (14)	C11—C12—C15—C16	−55.2 (3)
N1ⁱ—Ni1—N2—C2	−156.33 (14)	P1—O2—C19—C24	98.6 (2)
S1—Ni1—N2—C2	−54.67 (14)	P1—O2—C19—C20	−86.2 (2)
N1—Ni1—N2—C3	156.67 (17)	C24—C19—C20—C21	0.8 (4)
N1ⁱ—Ni1—N2—C3	−23.33 (17)	O2—C19—C20—C21	−174.3 (2)
S1—Ni1—N2—C3	78.33 (16)	C19—C20—C21—C22	0.5 (4)
C5ⁱ—N1—C1—C2	143.3 (2)	C20—C21—C22—C23	−1.6 (4)
Ni1—N1—C1—C2	−31.7 (2)	C20—C21—C22—C25	177.9 (2)
C3—N2—C2—C1	178.12 (18)	C21—C22—C23—C24	1.5 (4)
Ni1—N2—C2—C1	−46.42 (19)	C25—C22—C23—C24	−178.0 (2)
N1—C1—C2—N2	50.7 (2)	C20—C19—C24—C23	−0.9 (4)
C2—N2—C3—C6	66.1 (2)	O2—C19—C24—C23	174.2 (2)
Ni1—N2—C3—C6	−63.2 (2)	C22—C23—C24—C19	−0.3 (4)
C2—N2—C3—C4	−172.42 (17)	C23—C22—C25—C26	9.1 (3)
Ni1—N2—C3—C4	58.2 (2)	C21—C22—C25—C26	−170.4 (2)
C2—N2—C3—C7	−55.6 (2)	C23—C22—C25—C28	−110.9 (3)
Ni1—N2—C3—C7	175.03 (14)	C21—C22—C25—C28	69.6 (3)
N2—C3—C4—C5	−66.3 (2)	C23—C22—C25—C27	129.5 (3)
C6—C3—C4—C5	55.2 (3)	C21—C22—C25—C27	−50.0 (3)
C7—C3—C4—C5	175.17 (19)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S2ⁱ	0.88 (3)	2.70 (3)	3.542 (2)	162 (3)
C7—H7A···S2ⁱ	0.98	2.82	3.703 (3)	150

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₆H₃₂N₄)](C₂₀H₂₆O₂PS₂)₂
M_r	1126.16
Crystal system, space group	Triclinic, P1
Temperature (K)	103
a, b, c (Å)	9.445 (2), 12.168 (3), 12.740 (3)
α, β, γ (°)	95.965 (4), 91.360 (3), 99.787 (4)
V (Å³)	1433.7 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.27 × 0.23 × 0.08

Data collection
Diffractometer	Rigaku SPIDER
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.859, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	14032, 6434, 4838
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.101, 1.00
No. of reflections	6434
No. of parameters	335
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.35

Computer programs: RAPID-AUTO (Rigaku, 2004), 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
N2—H2N···S2ⁱ	0.88 (3)	2.70 (3)	3.542 (2)	162 (3)
C7—H7A···S2ⁱ	0.98	2.82	3.703 (3)	150

Symmetry code: (i) −x, −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, and the Science and Technology Office of Zigong City (Nos. 08X01 and 10X05).

References

Aoki, S. & Kimura, E. (2002). Rev. Mol. Biotechnol. 90, 129–155. CrossRef CAS Google Scholar
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
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, J.-S. & Xie, B. (1997). Acta Chim. Sin. 55, 892–896. CAS Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, B., Zhang, X.-L., Zou, L.-K., Wang, J., Lai, C., Wu, Y. & Feng, J.-S. (2009). Chem J Chin. Univ. 30, 2337–2343. CAS 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\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(5,7,7,12,14,14-Hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene)nickel(II) bis­­[O,O′-bis­­(4-tert-butyl­phen­yl) di­thio­phosphate]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) bis[O,O′-bis(4-tert-butylphenyl) dithiophosphate]