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In the title compound, [Ni(C6H14O2PS2)2(C5H6N2)2], the coordination around the Ni atom, which lies on a crystallographic centre of symmetry, is octahedral with the S atoms from the di­thio­phosphate ligands occupying the equatorial positions, while the axial positions are occupied by the ring N atoms of the 2-amino­pyridine ligands. The mol­ecules form layers in the bc plane which are stacked in the direction of the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100016073/ln1110sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100016073/ln1110Isup2.hkl
Contains datablock I

CCDC reference: 159983

Comment top

Nickel(II) dialkyldithiophosphates and their derivatives find wide applications in rubber chemistry and technology, and as lubrication oil additives (Jones & Symes, 1971). Metal chelates in which the metal ion is coordinatively unsaturated can act as electron acceptors and yield adducts with neutral molecules which are electron donors (Harrison et al., 1986). Adducts and their formation reactions have also been found useful in a wide variety of ways. In recent years, adducts of nickel(II) dialkyl dithiophosphate with neutral nitrogen bases have received increasing attention, partly because of the reactivity of a variety of nitrogen bases with nickel(II) dialkyl dithiophosphate in solution (Liu et al., 1991; You et al., 1994; Xiong et al., 1995). The antioxidant effectiveness for diisopropyl dithiophosphates decreases in the order: Co > Ni > Zn > Cu > Cd > Ba = Ca. For Ni dialkyl dithiophosphates, the effectiveness decreases in the order iso-Pr > cyclohexyl > tert-Bu (Kovtun et al., 1992). Furthermore, the amines in lubricating oil have a great influence on the properties of metal dialkyl dithiophosphate additives (Shiomi et al., 1989).

The Ni atom in the title compound, (I), lies on a crystallographic centre of symmetry with the dithiophosphato (dtp) ligands coordinated to it by their two S atoms, forming four-membered chelate rings. The two 2-aminopyridine molecules are coordinated to the central Ni atom through the two ring N atoms. This coordination forms a distorted octahedral environment around Ni with S1, S1(2 - x, 1 - y, -z), S2, S2(2 - x, 1 - y, -z) at the equatorial positions, while the axial positions are occupied by the 2-aminopyridine moieties. The ideal octahedral geometry is distorted by the minor steric constraints imposed by the restricted bite angles of the dithiophosphate ligand. \sch

The S1—Ni1—S2, S1—P1—S2 bond angles and Ni—S bond lengths are comparable with those of Ni[(C2H5O)2PS2]2py2 [81.7 (1), 110.4 (3)° and 2.49 (1)–2.50 (1) Å, respectively] (Ooi & Fernando, 1967) and Ni[(C4H9O)2PS2]2py2 [81.5 (1), 111.7 (1)° and 2.486 (1)–2.511 (1) Å, respectively] (Liu et al., 1987), whereas the Ni—N bond lengths are about 0.11 Å longer than those in these two related compounds [2.11 (1) and 2.116 (4) Å, respectively]. However, the S1—Ni1—S2 and S1—P1—S2 bond angles are slightly smaller than those found in Ni(Bu-dtp)2(4-aminopy)2 [81.91 (5) and 112.46 (5)°, respectively] (You et al., 1994). The mean Ni—S bond length in the title compound is substantially longer than the value of 2.222 (1) Å reported for Ni[(C3H7O2)2PS2]2 (Hoskins & Tiekink, 1985). This is a direct consequence of the six- versus four-coordinate electronic environments of the metal centres in the two compounds. The mean Ni—S—P angle in the title complex is larger than those of Ni(Bu-dtp)2(4-aminopy)2 [82.83 (5)°] (You et al., 1994) and Ni[(C4H9O)2PS2]2py2 [82.57°] (Liu et al., 1987). However, this angle is comparable to the mean value of 85.08 (6)° reported by Hoskins & Tiekink (1985).

The P—S bond lengths are comparable to those in Ni[(C3H7O2)2PS2]2 [1.991 (2) and 1.993 (2) Å] (Hoskins & Tiekink, 1985), but different from those in Zn[(iPrO)2PS2]2(bipy) [2.005 (6), 1.925 (6), 1.997 (8) and 1.926 (9) Å] (Harrison et al., 1986) where the S atoms of the shorter bonds are not bonded to or are only very weakly interacting with the central atom. The P—O, O—C and C—C bond lengths of the bis(O,O'-disopropyldithiophosphate) are comparable with the reported values (Hoskins & Tiekink, 1985).

In the crystal, the molecules are arranged in layers in the bc plane. Layers are stacked in the a axis direction by S2···S2(1 - x, 1 - y, -z) interactions [3.5475 (6) Å].

Related literature top

For related literature, see: Harrison et al. (1986); Hoskins & Tiekink (1985); Jones & Symes (1971); Kovtun et al. (1992); Liu et al. (1987, 1991); Ooi & Fernando (1967); Shiomi et al. (1989); Xiong et al. (1995); You et al. (1994).

Experimental top

The title compound was prepared by adding nickel(II) bis(O,O'-diisopropyl dithiophosphate) (0.01 mmol) in EtOH (80 ml) followed by the addition of 2-aminopyridine (0.02 mmol). The mixture was heated until the solids dissolved and then filtered. The filtrate was allowed to stand at room temperature. Dark green crystals formed upon slow evaporation of the solvent.

Refinement top

After checking their presence in the difference map, the positions of all H atoms were geometrically calculated and allowed to ride on their attached atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PARST (Nardelli, 1995).

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms were omitted for clarity.
Trans-bis(aminopyridine)-bis(O,O'-diisopropyl dithiophosphato-S,S')nickel(II) top
Crystal data top
[Ni(C6H14O2PS2)2(C5H6N2)2]F(000) = 708
Mr = 673.47Dx = 1.430 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.6296 (1) ÅCell parameters from 8192 reflections
b = 16.3605 (2) Åθ = 2.5–28.3°
c = 14.6386 (2) ŵ = 1.02 mm1
β = 99.938 (1)°T = 293 K
V = 1563.93 (4) Å3Slab, dark green
Z = 20.40 × 0.24 × 0.14 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
3823 independent reflections
Radiation source: fine-focus sealed tube3246 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.058
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 2.5°
ω scansh = 88
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 2120
Tmin = 0.685, Tmax = 0.870l = 1910
10833 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087See text
S = 0.97 w = 1/[σ2(Fo2) + (0.041P)2]
where P = (Fo2 + 2Fc2)/3
3823 reflections(Δ/σ)max < 0.001
169 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.71 e Å3
Crystal data top
[Ni(C6H14O2PS2)2(C5H6N2)2]V = 1563.93 (4) Å3
Mr = 673.47Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.6296 (1) ŵ = 1.02 mm1
b = 16.3605 (2) ÅT = 293 K
c = 14.6386 (2) Å0.40 × 0.24 × 0.14 mm
β = 99.938 (1)°
Data collection top
Siemens SMART CCD area detector
diffractometer
3823 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
3246 reflections with I > 2σ(I)
Tmin = 0.685, Tmax = 0.870Rint = 0.058
10833 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.087See text
S = 0.97Δρmax = 0.43 e Å3
3823 reflectionsΔρmin = 0.71 e Å3
169 parameters
Special details top

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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
xyzUiso*/Ueq
Ni11.00000.50000.00000.02178 (9)
P10.91563 (7)0.37889 (3)0.14719 (3)0.02491 (11)
S11.19032 (6)0.40239 (3)0.11659 (3)0.02979 (11)
S20.70622 (6)0.44565 (3)0.06641 (3)0.02791 (11)
O10.9068 (2)0.38744 (7)0.25437 (9)0.0345 (3)
O20.8653 (2)0.28386 (7)0.14268 (9)0.0338 (3)
N11.0261 (2)0.60077 (8)0.10370 (10)0.0263 (3)
N21.3746 (2)0.59021 (11)0.16186 (12)0.0438 (4)
H2A1.37950.54640.12990.053*
H2B1.48380.60840.19620.053*
C11.1957 (3)0.63046 (11)0.15812 (12)0.0309 (4)
C21.1896 (3)0.70225 (13)0.21090 (15)0.0454 (5)
H2C1.30930.72290.24580.055*
C31.0081 (4)0.74135 (14)0.21067 (17)0.0534 (6)
H3A1.00240.78830.24590.064*
C40.8315 (3)0.71005 (13)0.15704 (15)0.0433 (5)
H4A0.70520.73500.15650.052*
C50.8482 (3)0.64201 (10)0.10541 (13)0.0310 (4)
H5A0.72980.62220.06860.037*
C60.9090 (4)0.46761 (12)0.29897 (14)0.0422 (5)
H6A0.87380.50990.25150.051*
C70.7457 (5)0.4639 (2)0.3587 (2)0.0786 (9)
H7A0.61550.45330.32050.118*
H7B0.74030.51520.39010.118*
H7C0.77720.42090.40350.118*
C81.1183 (5)0.48395 (18)0.3529 (2)0.0699 (8)
H8A1.21540.48570.31130.105*
H8B1.15520.44120.39760.105*
H8C1.11840.53550.38430.105*
C90.8272 (4)0.24303 (11)0.05237 (14)0.0432 (5)
H9A0.84220.28270.00380.052*
C100.6097 (4)0.21280 (18)0.0378 (2)0.0836 (10)
H10A0.51850.25830.03790.125*
H10B0.59290.17580.08680.125*
H10C0.57900.18490.02070.125*
C110.9838 (4)0.17673 (15)0.0533 (2)0.0648 (7)
H11A1.11830.20040.06280.097*
H11B0.95960.14830.00490.097*
H11C0.97370.13910.10260.097*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01822 (16)0.02211 (16)0.02495 (17)0.00007 (10)0.00359 (11)0.00248 (10)
P10.0262 (2)0.0222 (2)0.0264 (2)0.00074 (15)0.00482 (17)0.00325 (15)
S10.0225 (2)0.0320 (2)0.0342 (2)0.00169 (16)0.00279 (17)0.00615 (17)
S20.0206 (2)0.0295 (2)0.0336 (2)0.00070 (15)0.00472 (16)0.00493 (16)
O10.0483 (8)0.0293 (6)0.0266 (7)0.0005 (5)0.0088 (6)0.0033 (5)
O20.0429 (8)0.0236 (6)0.0350 (7)0.0053 (5)0.0072 (6)0.0032 (5)
N10.0244 (7)0.0269 (7)0.0281 (8)0.0041 (5)0.0057 (6)0.0013 (5)
N20.0255 (8)0.0526 (10)0.0500 (11)0.0044 (7)0.0026 (7)0.0106 (8)
C10.0305 (9)0.0341 (9)0.0275 (9)0.0063 (7)0.0030 (7)0.0006 (7)
C20.0466 (12)0.0447 (12)0.0412 (12)0.0102 (9)0.0031 (9)0.0123 (9)
C30.0673 (16)0.0417 (12)0.0504 (14)0.0003 (11)0.0081 (11)0.0198 (10)
C40.0431 (11)0.0404 (11)0.0474 (12)0.0076 (9)0.0108 (9)0.0086 (9)
C50.0292 (9)0.0302 (9)0.0338 (10)0.0007 (7)0.0063 (7)0.0015 (7)
C60.0638 (14)0.0300 (9)0.0324 (10)0.0041 (9)0.0067 (9)0.0002 (8)
C70.080 (2)0.081 (2)0.081 (2)0.0141 (17)0.0339 (17)0.0246 (17)
C80.080 (2)0.0699 (17)0.0564 (17)0.0188 (15)0.0014 (14)0.0150 (13)
C90.0611 (14)0.0277 (9)0.0388 (12)0.0070 (9)0.0030 (10)0.0025 (8)
C100.0525 (16)0.0640 (18)0.122 (3)0.0019 (13)0.0197 (17)0.0339 (17)
C110.0645 (17)0.0536 (14)0.0784 (19)0.0002 (12)0.0185 (14)0.0247 (13)
Geometric parameters (Å, º) top
Ni1—N12.2275 (14)N1—C51.362 (2)
Ni1—S22.4865 (4)N2—C11.350 (2)
Ni1—S12.5123 (4)C1—C21.410 (3)
P1—O11.5863 (14)C2—C31.362 (3)
P1—O21.5892 (12)C3—C41.390 (3)
P1—S11.9866 (6)C4—C51.361 (3)
P1—S21.9879 (6)C6—C81.497 (4)
O1—C61.464 (2)C6—C71.505 (4)
O2—C91.464 (2)C9—C111.500 (3)
N1—C11.351 (2)C9—C101.504 (3)
N1—Ni1—N1i180.0C9—O2—P1119.09 (11)
N1—Ni1—S2i91.59 (4)C1—N1—C5116.48 (15)
N1—Ni1—S288.41 (4)C1—N1—Ni1128.81 (12)
S2i—Ni1—S2180.0C5—N1—Ni1114.42 (11)
N1—Ni1—S1i87.90 (4)N2—C1—N1118.99 (16)
S2—Ni1—S1i99.060 (14)N2—C1—C2119.47 (17)
N1—Ni1—S192.10 (4)N1—C1—C2121.54 (18)
S2—Ni1—S180.940 (14)C3—C2—C1119.89 (19)
S1i—Ni1—S1180.0C2—C3—C4119.08 (19)
O1—P1—O294.82 (7)C5—C4—C3118.26 (19)
O1—P1—S1113.44 (6)C4—C5—N1124.69 (18)
O2—P1—S1111.97 (6)O1—C6—C8109.39 (19)
O1—P1—S2113.49 (6)O1—C6—C7105.67 (19)
O2—P1—S2113.12 (6)C8—C6—C7113.3 (2)
S1—P1—S2109.44 (3)O2—C9—C11108.08 (19)
P1—S1—Ni184.476 (19)O2—C9—C10106.85 (19)
P1—S2—Ni185.142 (19)C11—C9—C10114.11 (19)
C6—O1—P1121.39 (11)
O1—P1—S1—Ni1127.36 (5)S1i—Ni1—N1—C1126.60 (14)
O2—P1—S1—Ni1126.76 (6)S1—Ni1—N1—C153.40 (14)
S2—P1—S1—Ni10.50 (3)S2i—Ni1—N1—C5127.76 (11)
N1—Ni1—S1—P187.67 (4)S2—Ni1—N1—C552.24 (11)
N1i—Ni1—S1—P192.33 (4)S1i—Ni1—N1—C546.89 (11)
S2i—Ni1—S1—P1179.617 (19)S1—Ni1—N1—C5133.11 (11)
S2—Ni1—S1—P10.383 (19)C5—N1—C1—N2177.49 (17)
O1—P1—S2—Ni1127.33 (6)Ni1—N1—C1—N29.1 (2)
O2—P1—S2—Ni1126.11 (6)C5—N1—C1—C22.5 (3)
S1—P1—S2—Ni10.51 (3)Ni1—N1—C1—C2170.90 (14)
N1—Ni1—S2—P192.00 (4)N2—C1—C2—C3177.2 (2)
N1i—Ni1—S2—P188.00 (4)N1—C1—C2—C32.8 (3)
S1i—Ni1—S2—P1179.618 (19)C1—C2—C3—C40.8 (4)
S1—Ni1—S2—P10.382 (19)C2—C3—C4—C51.1 (4)
O2—P1—O1—C6169.77 (15)C3—C4—C5—N11.4 (3)
S1—P1—O1—C673.75 (15)C1—N1—C5—C40.4 (3)
S2—P1—O1—C651.98 (16)Ni1—N1—C5—C4173.95 (16)
O1—P1—O2—C9172.19 (14)P1—O1—C6—C8102.5 (2)
S1—P1—O2—C970.14 (15)P1—O1—C6—C7135.20 (18)
S2—P1—O2—C954.09 (15)P1—O2—C9—C11120.07 (17)
S2i—Ni1—N1—C145.73 (14)P1—O2—C9—C10116.72 (18)
S2—Ni1—N1—C1134.27 (14)
Symmetry code: (i) x+2, y+1, z.

Experimental details

Crystal data
Chemical formula[Ni(C6H14O2PS2)2(C5H6N2)2]
Mr673.47
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.6296 (1), 16.3605 (2), 14.6386 (2)
β (°) 99.938 (1)
V3)1563.93 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.02
Crystal size (mm)0.40 × 0.24 × 0.14
Data collection
DiffractometerSiemens SMART CCD area detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.685, 0.870
No. of measured, independent and
observed [I > 2σ(I)] reflections
10833, 3823, 3246
Rint0.058
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.087, 0.97
No. of reflections3823
No. of parameters169
H-atom treatmentSee text
Δρmax, Δρmin (e Å3)0.43, 0.71

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PARST (Nardelli, 1995).

Selected geometric parameters (Å, º) top
Ni1—N12.2275 (14)P1—S11.9866 (6)
Ni1—S22.4865 (4)P1—S21.9879 (6)
Ni1—S12.5123 (4)O1—C61.464 (2)
P1—O11.5863 (14)O2—C91.464 (2)
P1—O21.5892 (12)
N1—Ni1—N1i180.0S1i—Ni1—S1180.0
N1—Ni1—S288.41 (4)S1—P1—S2109.44 (3)
N1—Ni1—S192.10 (4)P1—S1—Ni184.476 (19)
S2—Ni1—S180.940 (14)P1—S2—Ni185.142 (19)
Symmetry code: (i) x+2, y+1, z.
 

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