Redetermination of bis-(O,O'-diethyl dithio-phosphato-κS,S')nickel(II).

The centrosymmetric title complex, [Ni{S(2)P(OC(2)H(5))(2)}(2)], has been redetermined using area-detector data. The central Ni(S(2)P)(2) core is essentially planar and confirms the early results of McConnell & Kastalsky [Acta Cryst. (1967), 22, 853-859] based on multiple film technique data. In the title structure, the standard uncertainty values are approximately seven times lower and all H-atom positions are calculated. A pair of short symmetry-related H⋯H contacts with distances of 2.33 Å is observed in the crystal structure.

Related literature

For the syntheses and structure of a series of homologous Ni(S2P{OR}2)2 complexes, see: R = Me: Kastalsky & McConnell (1969 ▶); R = Et: Fernando & Green (1967 ▶); McConnell & Kastalsky (1967 ▶); R = Pr and R = Bu: Ivanov et al. (2004 ▶); R = Pr: Tkachev & Atovmyan (1976 ▶); Hoskins & Tiekink (1985 ▶). For complexes with sulfur-rich kernel-bearing silanethiol­ato and dithio­carbamato ligands, see: Kropidłowska et al. (2008 ▶). For hydrogen bonds, see: Steiner & Desiraju (1998 ▶).

Experimental

Crystal data

[Ni(C4H10O2PS2)2]

M = 429.13

Monoclinic,

a = 10.4810 (4) Å

b = 10.2777 (3) Å

c = 8.7541 (3) Å

β = 102.820 (3)°

V = 919.49 (6) Å3

Z = 2

Mo Kα radiation

μ = 1.69 mm−1

T = 295 K

0.41 × 0.34 × 0.09 mm

Data collection

Oxford Diffraction KM-4-CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.530, T max = 0.853

7073 measured reflections

2012 independent reflections

1768 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.083

S = 1.09

2012 reflections

91 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.32 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901767X/si2169sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901767X/si2169Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C4H10O2PS2)2]	F(000) = 444
Mr = 429.13	Dx = 1.55 Mg m−3
Monoclinic, P21/c	Melting point: 378 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.4810 (4) Å	Cell parameters from 5670 reflections
b = 10.2777 (3) Å	θ = 2.0–32.3°
c = 8.7541 (3) Å	µ = 1.69 mm−1
β = 102.820 (3)°	T = 295 K
V = 919.49 (6) Å3	Prism, violet
Z = 2	0.41 × 0.34 × 0.09 mm

Oxford Diffraction KM-4-CCD diffractometer	2012 independent reflections
graphite	1768 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1	Rint = 0.016
ω (0.75° width) scans	θmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	h = −13→13
Tmin = 0.530, Tmax = 0.853	k = −7→13
7073 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031	H-atom parameters constrained
wR(F2) = 0.083	w = 1/[σ2(Fo2) + (0.0441P)2 + 0.3217P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
2012 reflections	Δρmax = 0.30 e Å−3
91 parameters	Δρmin = −0.32 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (2)

Experimental. Oxford Diffraction Ltd., 2008. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
Ni1	0	1	0	0.04253 (14)
P1	−0.23354 (5)	0.94137 (6)	0.09934 (7)	0.04844 (17)
S1	−0.07705 (6)	0.82989 (6)	0.10854 (9)	0.0633 (2)
S2	−0.18740 (6)	1.10251 (6)	−0.00212 (8)	0.06062 (19)
O1	−0.36674 (16)	0.87744 (19)	0.01719 (18)	0.0621 (4)
O2	−0.26962 (16)	0.96353 (18)	0.26213 (18)	0.0583 (4)
C1	−0.3979 (3)	0.8474 (3)	−0.1498 (3)	0.0745 (8)
H1A	−0.3223	0.8095	−0.1799	0.089*
H1B	−0.4217	0.9263	−0.2102	0.089*
C2	−0.5078 (3)	0.7549 (3)	−0.1810 (4)	0.0786 (8)
H2A	−0.4839	0.6779	−0.1192	0.118*
H2B	−0.5282	0.7322	−0.2901	0.118*
H2C	−0.5829	0.7942	−0.1539	0.118*
C3	−0.1754 (3)	1.0198 (4)	0.3917 (4)	0.0835 (9)
H3A	−0.1529	1.1071	0.3648	0.1*
H3B	−0.0962	0.9678	0.4135	0.1*
C4	−0.2321 (4)	1.0239 (3)	0.5302 (3)	0.0873 (9)
H4A	−0.3118	1.0732	0.507	0.131*
H4B	−0.1713	1.0642	0.6153	0.131*
H4C	−0.2503	0.9369	0.5592	0.131*

	U11	U22	U33	U12	U13	U23
Ni1	0.0394 (2)	0.0400 (2)	0.0513 (2)	−0.00037 (13)	0.01666 (15)	0.00300 (14)
P1	0.0433 (3)	0.0526 (3)	0.0531 (3)	−0.0052 (2)	0.0188 (2)	0.0003 (2)
S1	0.0587 (4)	0.0458 (3)	0.0936 (5)	0.0031 (2)	0.0342 (3)	0.0150 (3)
S2	0.0514 (3)	0.0525 (3)	0.0849 (4)	0.0098 (2)	0.0300 (3)	0.0166 (3)
O1	0.0524 (9)	0.0873 (12)	0.0500 (8)	−0.0183 (8)	0.0184 (7)	−0.0112 (8)
O2	0.0519 (9)	0.0756 (10)	0.0502 (8)	−0.0125 (8)	0.0171 (7)	−0.0067 (8)
C1	0.0777 (18)	0.097 (2)	0.0518 (13)	−0.0140 (16)	0.0204 (12)	−0.0100 (13)
C2	0.0576 (15)	0.100 (2)	0.0758 (17)	−0.0038 (15)	0.0089 (12)	−0.0278 (16)
C3	0.0717 (18)	0.113 (2)	0.0635 (16)	−0.0253 (17)	0.0093 (13)	−0.0236 (16)
C4	0.108 (3)	0.093 (2)	0.0587 (16)	−0.0009 (19)	0.0146 (16)	−0.0152 (15)

Ni1—S2	2.2253 (6)	C1—C2	1.472 (4)
Ni1—S2i	2.2253 (6)	C1—H1A	0.97
Ni1—S1	2.2254 (6)	C1—H1B	0.97
Ni1—S1i	2.2254 (6)	C2—H2A	0.96
Ni1—P1	2.8382 (5)	C2—H2B	0.96
Ni1—P1i	2.8382 (5)	C2—H2C	0.96
P1—O1	1.5660 (17)	C3—C4	1.464 (4)
P1—O2	1.5700 (16)	C3—H3A	0.97
P1—S1	1.9876 (8)	C3—H3B	0.97
P1—S2	1.9890 (8)	C4—H4A	0.96
O1—C1	1.459 (3)	C4—H4B	0.96
O2—C3	1.449 (3)	C4—H4C	0.96
S2—Ni1—S2i	180	C1—O1—P1	121.83 (15)
S2—Ni1—S1	88.41 (2)	C3—O2—P1	120.60 (17)
S2i—Ni1—S1	91.59 (2)	O1—C1—C2	108.3 (2)
S2—Ni1—S1i	91.59 (2)	O1—C1—H1A	110
S2i—Ni1—S1i	88.41 (2)	C2—C1—H1A	110
S1—Ni1—S1i	180	O1—C1—H1B	110
S2—Ni1—P1	44.230 (19)	C2—C1—H1B	110
S2i—Ni1—P1	135.770 (19)	H1A—C1—H1B	108.4
S1—Ni1—P1	44.194 (19)	C1—C2—H2A	109.5
S1i—Ni1—P1	135.81 (2)	C1—C2—H2B	109.5
S2—Ni1—P1i	135.770 (19)	H2A—C2—H2B	109.5
S2i—Ni1—P1i	44.230 (19)	C1—C2—H2C	109.5
S1—Ni1—P1i	135.81 (2)	H2A—C2—H2C	109.5
S1i—Ni1—P1i	44.194 (19)	H2B—C2—H2C	109.5
P1—Ni1—P1i	180	O2—C3—C4	109.2 (3)
O1—P1—O2	96.20 (9)	O2—C3—H3A	109.8
O1—P1—S1	114.85 (8)	C4—C3—H3A	109.8
O2—P1—S1	114.18 (8)	O2—C3—H3B	109.8
O1—P1—S2	115.13 (8)	C4—C3—H3B	109.8
O2—P1—S2	114.58 (8)	H3A—C3—H3B	108.3
S1—P1—S2	102.58 (3)	C3—C4—H4A	109.5
O1—P1—Ni1	133.63 (6)	C3—C4—H4B	109.5
O2—P1—Ni1	130.17 (6)	H4A—C4—H4B	109.5
S1—P1—Ni1	51.30 (2)	C3—C4—H4C	109.5
S2—P1—Ni1	51.30 (2)	H4A—C4—H4C	109.5
P1—S1—Ni1	84.50 (3)	H4B—C4—H4C	109.5
P1—S2—Ni1	84.47 (3)

Ni1—S2	2.2253 (6)
Ni1—S1	2.2254 (6)
P1—S1	1.9876 (8)
P1—S2	1.9890 (8)

S2—Ni1—S1	88.41 (2)
S1—P1—S2	102.58 (3)
P1—S1—Ni1	84.50 (3)
P1—S2—Ni1	84.47 (3)