metal-organic compounds
Bis[O-propan-2-yl (4-ethoxyphenyl)dithiophosphonato-κ2S,S′]nickel(II)
aSchool of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
*Correspondence e-mail: vanzylw@ukzn.ac.za
The title compound, [Ni(C11H16O2PS2)2], is a neutral four-coordinate mononuclear complex with a square-planar geometry. The complex lies on an inversion center. The metal atom is surrounded by two chelating isobidentate O-propan-2-yl (4-ethoxyphenyl)dithiophosphonate ligands in a trans configuration binding through the S-donor atoms. The Ni—S bond lengths are 2.2328 (5) and 2.2369 (5) Å, an insignificant difference to be considered anisobidentate. The Ni⋯P separation is 2.8224 (5) Å and the S—P bond lengths are 2.0035 (7) and 2.0053 (7) Å. The S—Ni—S (chelating) and S—Ni—S (trans) bond angles are 88.321 (18) and 180°. The Ni—S—P bond angles are 83.26 (2) and 83.33 (2)°, indicating a very minor distortion from ideal square-planar geometry for the Ni atom. The P atom, however, is distorted quite significantly from an ideal tetrahedral geometry, as reflected by the S—P—S and O—P—C bond angles of 101.93 (3) and 100.70 (7)°, respectively.
Related literature
For information on dithiophosphonate compounds, see: Van Zyl & Fackler (2000); Van Zyl (2010). For examples of nickel(II) dithiophosphonate complexes, see: Liu et al. (2004); Gray et al. (2004); Aragoni et al. (2007); Arca et al. (1997); Malatesta & Pizzotti (1945); Hartung (1967).
Experimental
Crystal data
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Data collection: COLLECT (Nonius, 2000); cell DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812045114/bh2460sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812045114/bh2460Isup2.hkl
A colorless methanol (40 ml) solution of NH4[S2P(OiPr)(4-C6H4OEt)] (982 mg, 3.347 mmol) was prepared. A second green solution of NiCl2.6H20 (399 mg, 1.679 mmol) in deionized water (20 ml) was prepared, and added to the colorless solution with stirring over a period of 5 min. This resulted in a purple precipitate indicating the formation of the title complex. The precipitate was collected by vacuum filtration, washed with water (3 × 10 ml) and allowed to dry under vacuum for a period of 3 hrs, yielding a dry, free-flowing purple powder. Purple crystals suitable for X-ray analysis were grown by the slow diffusion of hexane into a dichloromethane solution of the title complex. Yield: 761 mg, 75%. M.p. 168–169°C.
31P NMR (CDCl3): δ (p.p.m.): 97.96. 1H NMR (CDCl3): δ (p.p.m.): 7.96 (2H, dd, o-ArH), 6.95 (2H, dd, m-ArH), 5.19 (1H, d quart, OCH), 4.06 (2H, quart, ArOCH2), 1.42 (3H, t, ArOCH2CH3), 1.38 (6H, d, CH3). 13C NMR (CDCl3): δ (p.p.m.): 162.22 (p-ArC), 131.71 (m-ArC), 128.04 (Ar—C1), 114.44 (o-ArC), 72.10 (CH), 63.76(ArOCH2), 24.30 (CH3), 14.67 (ArOCH2CH3).
All hydrogen atoms were found in the difference electron density maps and were placed in idealized positions and refined with geometrical constraints, with C—H bond lengths in the range 0.95-1.00 Å. The structure was refined to
factor of 0.0303.Data collection: COLLECT (Nonius, 2000); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title complex, shown with 50% probability displacement ellipsoids. |
[Ni(C11H16O2PS2)2] | Z = 1 |
Mr = 609.37 | F(000) = 318 |
Triclinic, P1 | Dx = 1.455 Mg m−3 |
Hall symbol: -P 1 | Melting point: 441 K |
a = 7.8893 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.4178 (7) Å | Cell parameters from 14410 reflections |
c = 11.4825 (10) Å | θ = 2.6–27.5° |
α = 109.530 (4)° | µ = 1.14 mm−1 |
β = 101.959 (4)° | T = 173 K |
γ = 93.913 (5)° | Block, purple |
V = 695.22 (10) Å3 | 0.39 × 0.26 × 0.14 mm |
Nonius KappaCCD diffractometer | 3062 independent reflections |
Radiation source: fine-focus sealed tube | 2381 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
1.2° ϕ scans and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = 0→10 |
Tmin = 0.665, Tmax = 0.857 | k = −10→10 |
14410 measured reflections | l = −14→14 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.028P)2 + 0.2462P] where P = (Fo2 + 2Fc2)/3 |
3062 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
0 constraints |
[Ni(C11H16O2PS2)2] | γ = 93.913 (5)° |
Mr = 609.37 | V = 695.22 (10) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.8893 (6) Å | Mo Kα radiation |
b = 8.4178 (7) Å | µ = 1.14 mm−1 |
c = 11.4825 (10) Å | T = 173 K |
α = 109.530 (4)° | 0.39 × 0.26 × 0.14 mm |
β = 101.959 (4)° |
Nonius KappaCCD diffractometer | 3062 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2381 reflections with I > 2σ(I) |
Tmin = 0.665, Tmax = 0.857 | Rint = 0.035 |
14410 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.27 e Å−3 |
3062 reflections | Δρmin = −0.31 e Å−3 |
154 parameters |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.5000 | 0.5000 | 0.0000 | 0.02229 (10) | |
S1 | 0.64099 (6) | 0.75272 (6) | 0.02356 (5) | 0.02729 (13) | |
S2 | 0.58144 (7) | 0.38847 (6) | −0.18193 (5) | 0.02842 (13) | |
P1 | 0.64598 (6) | 0.63370 (6) | −0.15849 (5) | 0.02271 (12) | |
O1 | 0.19743 (19) | 0.8621 (2) | −0.53641 (14) | 0.0416 (4) | |
O2 | 0.82744 (15) | 0.67472 (17) | −0.18857 (12) | 0.0266 (3) | |
C1 | 0.5013 (2) | 0.7025 (2) | −0.26799 (17) | 0.0231 (4) | |
C2 | 0.4982 (3) | 0.8752 (3) | −0.2422 (2) | 0.0317 (5) | |
H2 | 0.5664 | 0.9551 | −0.1634 | 0.038* | |
C3 | 0.3977 (3) | 0.9335 (3) | −0.3289 (2) | 0.0336 (5) | |
H3 | 0.3976 | 1.0523 | −0.3099 | 0.040* | |
C4 | 0.2974 (2) | 0.8179 (3) | −0.44330 (19) | 0.0308 (5) | |
C5 | 0.2947 (3) | 0.6447 (3) | −0.4682 (2) | 0.0405 (6) | |
H5 | 0.2227 | 0.5647 | −0.5455 | 0.049* | |
C6 | 0.3960 (3) | 0.5880 (3) | −0.3815 (2) | 0.0360 (5) | |
H6 | 0.3937 | 0.4690 | −0.3996 | 0.043* | |
C7 | 0.2176 (3) | 1.0381 (3) | −0.5253 (2) | 0.0463 (6) | |
H7A | 0.3430 | 1.0834 | −0.5079 | 0.056* | |
H7B | 0.1696 | 1.1073 | −0.4548 | 0.056* | |
C8 | 0.1178 (3) | 1.0441 (4) | −0.6510 (3) | 0.0654 (8) | |
H8A | 0.1653 | 0.9734 | −0.7200 | 0.098* | |
H8B | 0.1299 | 1.1621 | −0.6482 | 0.098* | |
H8C | −0.0063 | 1.0008 | −0.6662 | 0.098* | |
C9 | 0.9927 (2) | 0.6387 (3) | −0.11992 (19) | 0.0302 (5) | |
H9 | 0.9693 | 0.6009 | −0.0502 | 0.036* | |
C10 | 1.1185 (3) | 0.8017 (3) | −0.0629 (3) | 0.0646 (8) | |
H10A | 1.1334 | 0.8447 | −0.1302 | 0.097* | |
H10B | 1.2319 | 0.7811 | −0.0211 | 0.097* | |
H10C | 1.0725 | 0.8863 | 0.0001 | 0.097* | |
C11 | 1.0541 (3) | 0.4983 (3) | −0.2128 (2) | 0.0567 (7) | |
H11A | 0.9642 | 0.3971 | −0.2481 | 0.085* | |
H11B | 1.1628 | 0.4711 | −0.1695 | 0.085* | |
H11C | 1.0758 | 0.5343 | −0.2819 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02098 (18) | 0.0252 (2) | 0.0246 (2) | 0.00292 (14) | 0.00633 (14) | 0.01367 (16) |
S1 | 0.0299 (3) | 0.0276 (3) | 0.0257 (3) | 0.0000 (2) | 0.0069 (2) | 0.0119 (2) |
S2 | 0.0343 (3) | 0.0258 (3) | 0.0305 (3) | 0.0050 (2) | 0.0128 (2) | 0.0138 (2) |
P1 | 0.0197 (2) | 0.0268 (3) | 0.0260 (3) | 0.00378 (19) | 0.0065 (2) | 0.0145 (2) |
O1 | 0.0440 (9) | 0.0502 (10) | 0.0364 (9) | 0.0170 (7) | 0.0024 (7) | 0.0253 (8) |
O2 | 0.0170 (6) | 0.0397 (8) | 0.0333 (8) | 0.0077 (6) | 0.0074 (6) | 0.0248 (7) |
C1 | 0.0184 (9) | 0.0282 (11) | 0.0257 (10) | 0.0047 (8) | 0.0065 (8) | 0.0125 (9) |
C2 | 0.0288 (11) | 0.0299 (12) | 0.0315 (12) | 0.0026 (9) | −0.0009 (9) | 0.0100 (10) |
C3 | 0.0329 (11) | 0.0284 (11) | 0.0413 (13) | 0.0073 (9) | 0.0041 (10) | 0.0170 (10) |
C4 | 0.0259 (10) | 0.0406 (13) | 0.0323 (12) | 0.0111 (9) | 0.0076 (9) | 0.0198 (10) |
C5 | 0.0466 (14) | 0.0352 (13) | 0.0292 (12) | 0.0069 (10) | −0.0062 (10) | 0.0073 (10) |
C6 | 0.0407 (12) | 0.0283 (11) | 0.0355 (12) | 0.0090 (9) | 0.0008 (10) | 0.0112 (10) |
C7 | 0.0392 (13) | 0.0601 (16) | 0.0630 (16) | 0.0159 (11) | 0.0154 (12) | 0.0483 (14) |
C8 | 0.0461 (15) | 0.107 (2) | 0.082 (2) | 0.0262 (15) | 0.0198 (14) | 0.0779 (19) |
C9 | 0.0194 (10) | 0.0415 (12) | 0.0363 (12) | 0.0080 (9) | 0.0029 (8) | 0.0240 (10) |
C10 | 0.0313 (13) | 0.0465 (15) | 0.097 (2) | 0.0041 (11) | −0.0166 (14) | 0.0217 (16) |
C11 | 0.0352 (13) | 0.0701 (18) | 0.0548 (17) | 0.0292 (12) | −0.0002 (12) | 0.0123 (14) |
Ni1—S2 | 2.2328 (5) | C4—C5 | 1.387 (3) |
Ni1—S2i | 2.2328 (5) | C5—C6 | 1.378 (3) |
Ni1—S1i | 2.2369 (5) | C5—H5 | 0.9500 |
Ni1—S1 | 2.2369 (5) | C6—H6 | 0.9500 |
Ni1—P1 | 2.8224 (5) | C7—C8 | 1.513 (3) |
Ni1—P1i | 2.8224 (5) | C7—H7A | 0.9900 |
S1—P1 | 2.0035 (7) | C7—H7B | 0.9900 |
S2—P1 | 2.0053 (7) | C8—H8A | 0.9800 |
P1—O2 | 1.5828 (12) | C8—H8B | 0.9800 |
P1—C1 | 1.7894 (18) | C8—H8C | 0.9800 |
O1—C4 | 1.364 (2) | C9—C11 | 1.489 (3) |
O1—C7 | 1.438 (3) | C9—C10 | 1.497 (3) |
O2—C9 | 1.484 (2) | C9—H9 | 1.0000 |
C1—C6 | 1.385 (3) | C10—H10A | 0.9800 |
C1—C2 | 1.386 (3) | C10—H10B | 0.9800 |
C2—C3 | 1.383 (3) | C10—H10C | 0.9800 |
C2—H2 | 0.9500 | C11—H11A | 0.9800 |
C3—C4 | 1.381 (3) | C11—H11B | 0.9800 |
C3—H3 | 0.9500 | C11—H11C | 0.9800 |
S2—Ni1—S2i | 180.0 | O1—C4—C5 | 116.20 (19) |
S2—Ni1—S1i | 91.679 (18) | C3—C4—C5 | 119.59 (18) |
S2i—Ni1—S1i | 88.321 (18) | C6—C5—C4 | 120.3 (2) |
S2—Ni1—S1 | 88.321 (18) | C6—C5—H5 | 119.8 |
S2i—Ni1—S1 | 91.679 (18) | C4—C5—H5 | 119.8 |
S1i—Ni1—S1 | 180.0 | C5—C6—C1 | 120.7 (2) |
S2—Ni1—P1 | 44.885 (16) | C5—C6—H6 | 119.6 |
S2i—Ni1—P1 | 135.115 (17) | C1—C6—H6 | 119.6 |
S1i—Ni1—P1 | 135.174 (16) | O1—C7—C8 | 106.7 (2) |
S1—Ni1—P1 | 44.827 (16) | O1—C7—H7A | 110.4 |
S2—Ni1—P1i | 135.115 (16) | C8—C7—H7A | 110.4 |
S2i—Ni1—P1i | 44.885 (16) | O1—C7—H7B | 110.4 |
S1i—Ni1—P1i | 44.827 (16) | C8—C7—H7B | 110.4 |
S1—Ni1—P1i | 135.173 (16) | H7A—C7—H7B | 108.6 |
P1—Ni1—P1i | 180.0 | C7—C8—H8A | 109.5 |
P1—S1—Ni1 | 83.26 (2) | C7—C8—H8B | 109.5 |
P1—S2—Ni1 | 83.33 (2) | H8A—C8—H8B | 109.5 |
O2—P1—C1 | 100.70 (7) | C7—C8—H8C | 109.5 |
O2—P1—S1 | 113.76 (6) | H8A—C8—H8C | 109.5 |
C1—P1—S1 | 113.38 (7) | H8B—C8—H8C | 109.5 |
O2—P1—S2 | 114.16 (6) | O2—C9—C11 | 107.84 (16) |
C1—P1—S2 | 113.47 (7) | O2—C9—C10 | 107.22 (17) |
S1—P1—S2 | 101.93 (3) | C11—C9—C10 | 113.9 (2) |
O2—P1—Ni1 | 141.40 (5) | O2—C9—H9 | 109.3 |
C1—P1—Ni1 | 117.90 (6) | C11—C9—H9 | 109.3 |
S1—P1—Ni1 | 51.913 (17) | C10—C9—H9 | 109.3 |
S2—P1—Ni1 | 51.790 (18) | C9—C10—H10A | 109.5 |
C4—O1—C7 | 118.46 (17) | C9—C10—H10B | 109.5 |
C9—O2—P1 | 121.36 (11) | H10A—C10—H10B | 109.5 |
C6—C1—C2 | 118.40 (18) | C9—C10—H10C | 109.5 |
C6—C1—P1 | 121.83 (15) | H10A—C10—H10C | 109.5 |
C2—C1—P1 | 119.72 (15) | H10B—C10—H10C | 109.5 |
C3—C2—C1 | 121.31 (19) | C9—C11—H11A | 109.5 |
C3—C2—H2 | 119.3 | C9—C11—H11B | 109.5 |
C1—C2—H2 | 119.3 | H11A—C11—H11B | 109.5 |
C4—C3—C2 | 119.60 (19) | C9—C11—H11C | 109.5 |
C4—C3—H3 | 120.2 | H11A—C11—H11C | 109.5 |
C2—C3—H3 | 120.2 | H11B—C11—H11C | 109.5 |
O1—C4—C3 | 124.21 (19) | ||
S2—Ni1—S1—P1 | 12.58 (2) | S1—P1—O2—C9 | 58.46 (15) |
S2i—Ni1—S1—P1 | −167.42 (2) | S2—P1—O2—C9 | −57.97 (15) |
P1i—Ni1—S1—P1 | 180.0 | Ni1—P1—O2—C9 | 0.38 (19) |
S1i—Ni1—S2—P1 | 167.43 (2) | O2—P1—C1—C6 | 101.89 (17) |
S1—Ni1—S2—P1 | −12.57 (2) | S1—P1—C1—C6 | −136.21 (15) |
P1i—Ni1—S2—P1 | 180.0 | S2—P1—C1—C6 | −20.53 (18) |
Ni1—S1—P1—O2 | −137.71 (6) | Ni1—P1—C1—C6 | −78.31 (17) |
Ni1—S1—P1—C1 | 107.99 (7) | O2—P1—C1—C2 | −75.50 (16) |
Ni1—S1—P1—S2 | −14.35 (3) | S1—P1—C1—C2 | 46.41 (17) |
Ni1—S2—P1—O2 | 137.47 (6) | S2—P1—C1—C2 | 162.08 (14) |
Ni1—S2—P1—C1 | −107.90 (7) | Ni1—P1—C1—C2 | 104.30 (15) |
Ni1—S2—P1—S1 | 14.37 (3) | C6—C1—C2—C3 | −2.3 (3) |
S2—Ni1—P1—O2 | −81.30 (9) | P1—C1—C2—C3 | 175.20 (15) |
S2i—Ni1—P1—O2 | 98.70 (9) | C1—C2—C3—C4 | 0.4 (3) |
S1i—Ni1—P1—O2 | −99.27 (9) | C7—O1—C4—C3 | 10.4 (3) |
S1—Ni1—P1—O2 | 80.73 (9) | C7—O1—C4—C5 | −169.75 (19) |
S2—Ni1—P1—C1 | 99.02 (8) | C2—C3—C4—O1 | −178.27 (18) |
S2i—Ni1—P1—C1 | −80.98 (8) | C2—C3—C4—C5 | 1.9 (3) |
S1i—Ni1—P1—C1 | 81.05 (8) | O1—C4—C5—C6 | 177.9 (2) |
S1—Ni1—P1—C1 | −98.95 (8) | C3—C4—C5—C6 | −2.2 (3) |
S2—Ni1—P1—S1 | −162.03 (3) | C4—C5—C6—C1 | 0.3 (3) |
S2i—Ni1—P1—S1 | 17.97 (3) | C2—C1—C6—C5 | 1.9 (3) |
S1i—Ni1—P1—S1 | 180.000 (1) | P1—C1—C6—C5 | −175.49 (17) |
S2i—Ni1—P1—S2 | 180.0 | C4—O1—C7—C8 | 169.83 (18) |
S1i—Ni1—P1—S2 | −17.97 (3) | P1—O2—C9—C11 | 112.06 (18) |
S1—Ni1—P1—S2 | 162.03 (3) | P1—O2—C9—C10 | −124.87 (18) |
C1—P1—O2—C9 | −179.91 (14) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C11H16O2PS2)2] |
Mr | 609.37 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 7.8893 (6), 8.4178 (7), 11.4825 (10) |
α, β, γ (°) | 109.530 (4), 101.959 (4), 93.913 (5) |
V (Å3) | 695.22 (10) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.14 |
Crystal size (mm) | 0.39 × 0.26 × 0.14 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.665, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14410, 3062, 2381 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.065, 1.02 |
No. of reflections | 3062 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.31 |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank the National Research Foundation (NRF) and UKZN for financial support.
References
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The phosphor-1,1,-dithiolate class of compounds is the heavier and softer congener of the more popular phosphonate derivatives. It contains the S2P functionality as a common feature and several sub-categories are known which include the dithiophosphato [S2P(OR')2]¯, (typically, R' = alkyl), dithiophosphinato [S2PR2]¯ (R = alkyl or aryl), and dithiophosphonato [S2PR(OR')]¯, (typically, R = aryl or ferrocenyl, R' = alkyl) monoanionic ligands. The latter may be described as a hybrid of the former two, and are also much less developed. Amongst all metals involved in the coordination chemistry of dithiophosphonato ligands, however, nickel(II) is by far the best represented (Aragoni et al., 2007; Arca et al., 1997; Liu et al., 2004; Gray et al., 2004), with the first example dating back to 1945 (Malatesta & Pizzotti, 1945) whilst the first X-ray structural report of a nickel(II) dithiophosphonate complex reported more than 2 decades later (Hartung, 1967). The complex in the present study was formed from the reaction between NiCl2.6H20 and the ammonium salt of [S2P(OiPr)(4-C6H4OEt)] (molar ratio 1:2) in an aqueous/methanolic solution, the NH4Cl by-product was dissolved and the precipitated product filtered off and washed with water. General and convenient methods to prepare dithiophosphonate salt derivatives have been reported (Van Zyl & Fackler, 2000; Van Zyl, 2010).