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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): m279.
Published online 2008 January 4. doi:  10.1107/S1600536807067591
PMCID: PMC2960343

trans-Bis(4-methoxy­thio­phenolato-κS)bis­(trimethyl­phosphine-κP)nickel(II)

Abstract

The title compound, [Ni(C7H7OS)2(C3H9P)2], was obtained as a product of the reaction of [NiMe2(PMe3)3] with two molar equivalents of 4-methoxy­thio­phenol in diethyl ether. The compound is stable in the air for several hours, but rapidly decomposes at room temperature in solution. The Ni atom displays a square-planar coordination with two P-donor atoms lying in trans positions. The benzene rings of the thio­phenolate ligands are almost perpendicular to the square coordination plane, making dihedral angles of 80.43 (4) and 72.60 (4)°.

Related literature

For the crystal structures of related diphenolato-nickel compounds, see: Klein et al. (1998 [triangle]). For synthetic details, see: Klein & Karsch (1972 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m279-scheme1.jpg

Experimental

Crystal data

  • [Ni(C7H7OS)2(C3H9P)2]
  • M r = 489.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m279-efi1.jpg
  • a = 14.022 (3) Å
  • b = 15.983 (3) Å
  • c = 10.758 (2) Å
  • β = 100.93 (3)°
  • V = 2367.3 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.14 mm−1
  • T = 273 (2) K
  • 0.30 × 0.24 × 0.21 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.725, T max = 0.795
  • 14644 measured reflections
  • 5103 independent reflections
  • 4078 reflections with I > 2σ(I)
  • R int = 0.040
  • 14954 standard reflections every 6 reflections intensity decay: 30%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.085
  • S = 1.00
  • 5103 reflections
  • 372 parameters
  • All H-atom parameters refined
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.47 e Å−3

Data collection: XSCANS (Siemens, 1996 [triangle]); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2001 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067591/fi2053sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067591/fi2053Isup2.hkl

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

Acknowledgments

This work was supported by the NSFC (grant Nos. 20572062 and 20372042).

supplementary crystallographic information

Comment

In the title molecule (Fig.1) the nickel atom is coordinated in a square-planar geometry by two P atoms of trimethylphosphine groups and two S atoms of thiophenol groups. The phenyl rings of the thiophenlato ligands are almost perpendicular to the square coordination plane (angles 80.43 (4)° and 72.60 (4)°). Similar crystal structures have been reported in the literature, e.g. Bis(2-tert-butyl-4-methylphenolato)bis(trimethylphosphane)nickel and Bis(2-tert-butyl-6-methylphenolato)bis(trimethylphosphane)nickel (Klein et al.(1998)). The bond lengths and angles of these compounds are similar to those in the title compound.

Experimental

Dimethyltris(trimethylphosphine)nickel was prepared according to the literature (Klein & Karsch (1972)). Other chemicals were used by purchased. To the solution of NiMe2(PMe3)3 (1.0 g, 3.15 mmol) in 50 ml of diethyl ether was added 4-methoxythiophenol (0.884 g, 6.30 mmol) at -80 °C, a dark red suspension formed rapidly. After stirring at room temperature for 16 h the reaction solution was filtrated, then the red solid residue was extracted with THF (50 ml). Crystallization from ether and THF at 4 °C afforded dark red crystals suitable for X-ray diffraction analysis. (yield: 0.89 g, 57.8%, m. p.: 135 °C).

Refinement

All H atoms were positioned geometrically and were refined freely (C—H = 0.86–1.02 Å).

Figures

Fig. 1.
The molecular structure of (I), with a 30% probability displacement ellipsoids for non-H atoms.

Crystal data

[Ni(C7H7OS)2(C3H9P)2]F000 = 1032
Mr = 489.23Dx = 1.373 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1843 reflections
a = 14.022 (3) Åθ = 2.4–24.3º
b = 15.983 (3) ŵ = 1.14 mm1
c = 10.758 (2) ÅT = 273 (2) K
β = 100.93 (3)ºCubic, dark red
V = 2367.3 (8) Å30.30 × 0.24 × 0.21 mm
Z = 4

Data collection

Bruker P4 diffractometerRint = 0.040
Radiation source: fine-focus sealed tubeθmax = 27.1º
Monochromator: graphiteθmin = 1.5º
T = 423(2) Kh = −17→17
ω scansk = −20→20
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)l = −13→13
Tmin = 0.725, Tmax = 0.79514954 standard reflections
14644 measured reflections every 6 reflections
5103 independent reflections intensity decay: 30%
4078 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032All H-atom parameters refined
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.0526P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
5103 reflectionsΔρmax = 0.34 e Å3
372 parametersΔρmin = −0.47 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Ni10.257048 (17)0.016260 (16)0.74629 (2)0.03027 (9)
P10.37880 (4)0.08109 (3)0.68296 (5)0.03426 (13)
P20.13706 (4)−0.05297 (3)0.80892 (5)0.03389 (13)
S10.17664 (4)0.00061 (3)0.54812 (5)0.03656 (13)
S20.33803 (4)0.03453 (3)0.94334 (5)0.03455 (12)
C10.24429 (14)−0.07893 (12)0.48988 (19)0.0322 (4)
C20.30721 (15)−0.13200 (13)0.56961 (19)0.0345 (4)
C30.35857 (15)−0.19580 (13)0.52267 (19)0.0336 (4)
C40.34651 (14)−0.20757 (12)0.39280 (19)0.0319 (4)
C50.28431 (15)−0.15531 (13)0.31149 (19)0.0334 (4)
C60.23405 (15)−0.09207 (13)0.35826 (19)0.0318 (4)
C70.4551 (2)−0.32462 (15)0.4172 (3)0.0473 (6)
C80.25968 (14)0.10267 (12)1.00678 (18)0.0317 (4)
C90.19724 (15)0.15744 (13)0.9314 (2)0.0349 (4)
C100.13341 (16)0.20890 (13)0.9820 (2)0.0352 (4)
C110.13282 (14)0.20600 (12)1.11072 (19)0.0330 (4)
C120.19604 (15)0.15232 (13)1.18851 (19)0.0344 (4)
C130.25869 (15)0.10109 (13)1.13772 (19)0.0330 (4)
C140.00536 (19)0.30705 (15)1.0914 (3)0.0465 (6)
C150.49677 (17)0.03403 (16)0.7405 (3)0.0439 (5)
C160.3913 (2)0.18866 (15)0.7388 (3)0.0465 (5)
C170.3817 (2)0.0948 (2)0.5153 (2)0.0527 (6)
C180.01701 (18)−0.00824 (17)0.7602 (3)0.0492 (6)
C190.1249 (2)−0.15763 (16)0.7437 (3)0.0489 (6)
C200.1384 (3)−0.0739 (2)0.9760 (3)0.0594 (7)
O10.39280 (12)−0.26858 (9)0.33592 (14)0.0417 (4)
O20.07266 (11)0.25359 (10)1.16992 (14)0.0409 (3)
H80.3030 (17)0.0637 (14)1.193 (2)0.037 (6)*
H40.1928 (17)−0.0562 (14)0.305 (2)0.036 (6)*
H20.4020 (17)−0.2288 (14)0.581 (2)0.037 (6)*
H60.0932 (18)0.2463 (15)0.926 (2)0.042 (6)*
H10.3157 (18)−0.1256 (15)0.658 (2)0.045 (7)*
H70.1979 (17)0.1481 (13)1.278 (2)0.038 (6)*
H30.2763 (18)−0.1623 (15)0.226 (2)0.043 (6)*
H300.083 (2)−0.1094 (17)0.983 (3)0.060 (8)*
H210.444 (2)0.1243 (17)0.506 (3)0.064 (8)*
H50.2010 (18)0.1621 (15)0.843 (2)0.047 (7)*
H220.3789 (19)0.0424 (18)0.477 (3)0.047 (7)*
H24−0.028 (2)−0.0478 (17)0.788 (3)0.061 (8)*
H150.506 (2)0.0290 (18)0.822 (3)0.064 (9)*
H270.065 (2)−0.1831 (17)0.755 (3)0.061 (8)*
H160.544 (2)0.0681 (17)0.715 (3)0.059 (8)*
H12−0.031 (2)0.3322 (17)1.149 (3)0.059 (8)*
H90.5112 (18)−0.2937 (15)0.477 (2)0.045 (6)*
H250.004 (2)−0.0024 (19)0.673 (3)0.072 (10)*
H180.387 (2)0.1897 (17)0.826 (3)0.059 (8)*
H13−0.0356 (19)0.2742 (16)1.023 (3)0.046 (7)*
H280.123 (2)−0.1555 (17)0.655 (3)0.061 (8)*
H190.341 (2)0.2181 (19)0.694 (3)0.070 (9)*
H140.038 (2)0.3483 (18)1.049 (3)0.060 (8)*
H310.130 (2)−0.021 (2)1.020 (3)0.078 (10)*
H290.183 (2)−0.1915 (19)0.785 (3)0.076 (9)*
H320.190 (2)−0.1022 (19)1.005 (3)0.066 (10)*
H200.455 (2)0.2127 (17)0.728 (3)0.062 (8)*
H170.500 (2)−0.0226 (18)0.701 (3)0.059 (8)*
H100.4198 (19)−0.3535 (16)0.469 (3)0.051 (7)*
H110.480 (2)−0.3626 (17)0.361 (3)0.062 (8)*
H260.010 (2)0.047 (2)0.799 (3)0.066 (9)*
H230.327 (2)0.125 (2)0.477 (3)0.073 (10)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.02676 (14)0.03814 (15)0.02594 (14)0.00280 (10)0.00507 (11)−0.00110 (9)
P10.0296 (3)0.0426 (3)0.0310 (3)0.0011 (2)0.0065 (2)0.0020 (2)
P20.0300 (3)0.0403 (3)0.0314 (3)−0.0006 (2)0.0058 (2)0.0005 (2)
S10.0313 (3)0.0491 (3)0.0280 (3)0.0076 (2)0.0023 (2)−0.0026 (2)
S20.0304 (3)0.0442 (3)0.0280 (2)0.0055 (2)0.0028 (2)−0.0019 (2)
C10.0274 (9)0.0401 (10)0.0288 (10)−0.0031 (8)0.0045 (8)−0.0007 (8)
C20.0355 (11)0.0437 (11)0.0241 (9)0.0010 (8)0.0048 (9)−0.0020 (8)
C30.0340 (10)0.0375 (10)0.0287 (10)−0.0003 (8)0.0046 (9)0.0015 (8)
C40.0340 (10)0.0319 (9)0.0305 (10)−0.0039 (8)0.0079 (9)−0.0022 (7)
C50.0357 (11)0.0401 (10)0.0243 (10)−0.0054 (8)0.0055 (9)−0.0017 (8)
C60.0303 (10)0.0370 (10)0.0273 (10)−0.0026 (8)0.0033 (8)0.0034 (8)
C70.0602 (16)0.0377 (11)0.0441 (13)0.0093 (11)0.0102 (13)−0.0008 (10)
C80.0311 (10)0.0364 (10)0.0278 (10)−0.0005 (8)0.0057 (8)−0.0015 (8)
C90.0369 (11)0.0408 (11)0.0277 (10)0.0021 (8)0.0076 (9)0.0013 (8)
C100.0374 (11)0.0354 (10)0.0326 (11)0.0038 (8)0.0060 (9)0.0022 (8)
C110.0315 (10)0.0344 (9)0.0342 (11)−0.0038 (8)0.0090 (9)−0.0078 (8)
C120.0364 (11)0.0413 (11)0.0257 (10)−0.0048 (8)0.0066 (9)−0.0030 (8)
C130.0329 (10)0.0361 (10)0.0286 (10)−0.0010 (8)0.0021 (9)0.0011 (8)
C140.0482 (14)0.0390 (12)0.0538 (15)0.0080 (10)0.0136 (12)−0.0038 (11)
C150.0336 (11)0.0498 (13)0.0508 (15)0.0038 (10)0.0144 (11)0.0081 (11)
C160.0448 (14)0.0432 (12)0.0521 (15)0.0023 (10)0.0106 (12)0.0040 (11)
C170.0517 (16)0.0705 (18)0.0376 (13)−0.0125 (14)0.0124 (12)0.0036 (12)
C180.0362 (12)0.0544 (14)0.0597 (17)0.0063 (10)0.0161 (12)0.0100 (12)
C190.0460 (14)0.0430 (12)0.0597 (17)−0.0040 (11)0.0148 (13)−0.0049 (11)
C200.0605 (18)0.075 (2)0.0420 (14)−0.0214 (16)0.0091 (14)0.0093 (13)
O10.0503 (9)0.0424 (8)0.0319 (8)0.0087 (7)0.0061 (7)−0.0055 (6)
O20.0388 (8)0.0495 (8)0.0353 (8)0.0066 (7)0.0091 (7)−0.0084 (6)

Geometric parameters (Å, °)

Ni1—P12.2121 (7)C9—H50.96 (2)
Ni1—P22.2224 (7)C10—C111.387 (3)
Ni1—S22.2261 (9)C10—H60.96 (3)
Ni1—S12.2288 (9)C11—O21.378 (2)
P1—C151.816 (2)C11—C121.393 (3)
P1—C161.819 (3)C12—C131.387 (3)
P1—C171.825 (3)C12—H70.96 (2)
P2—C191.809 (3)C13—H80.98 (2)
P2—C181.812 (3)C14—O21.425 (3)
P2—C201.825 (3)C14—H120.97 (3)
S1—C11.770 (2)C14—H130.99 (3)
S2—C81.7729 (19)C14—H140.97 (3)
C1—C21.395 (3)C15—H150.86 (3)
C1—C61.412 (3)C15—H160.94 (3)
C2—C31.397 (3)C15—H171.01 (3)
C2—H10.94 (3)C16—H180.95 (3)
C3—C41.388 (3)C16—H190.91 (3)
C3—H20.95 (2)C16—H201.00 (3)
C4—O11.377 (2)C17—H211.02 (3)
C4—C51.391 (3)C17—H220.93 (3)
C5—C61.381 (3)C17—H230.93 (3)
C5—H30.91 (3)C18—H240.98 (3)
C6—H40.93 (2)C18—H250.92 (4)
C7—O11.428 (3)C18—H260.99 (3)
C7—H91.04 (3)C19—H270.96 (3)
C7—H100.94 (3)C19—H280.95 (3)
C7—H110.97 (3)C19—H291.01 (3)
C8—C91.386 (3)C20—H300.97 (3)
C8—C131.412 (3)C20—H310.99 (4)
C9—C101.400 (3)C20—H320.86 (3)
P1—Ni1—P2178.07 (2)O2—C11—C10124.26 (19)
P1—Ni1—S287.01 (3)O2—C11—C12115.96 (18)
P2—Ni1—S293.17 (3)C10—C11—C12119.78 (18)
P1—Ni1—S192.17 (3)C13—C12—C11120.36 (18)
P2—Ni1—S187.67 (3)C13—C12—H7117.0 (14)
S2—Ni1—S1178.85 (2)C11—C12—H7122.6 (14)
C15—P1—C16104.76 (13)C12—C13—C8120.63 (19)
C15—P1—C17101.37 (14)C12—C13—H8120.1 (13)
C16—P1—C17101.21 (14)C8—C13—H8119.2 (13)
C15—P1—Ni1114.04 (8)O2—C14—H12104.1 (17)
C16—P1—Ni1111.87 (8)O2—C14—H13110.3 (14)
C17—P1—Ni1121.57 (10)H12—C14—H13113 (2)
C19—P2—C18103.82 (14)O2—C14—H14111.5 (18)
C19—P2—C20101.25 (15)H12—C14—H14112 (2)
C18—P2—C20101.07 (16)H13—C14—H14106 (2)
C19—P2—Ni1111.32 (9)P1—C15—H15110 (2)
C18—P2—Ni1115.54 (9)P1—C15—H16108.0 (17)
C20—P2—Ni1121.54 (10)H15—C15—H16112 (3)
C1—S1—Ni1102.20 (7)P1—C15—H17109.9 (17)
C8—S2—Ni1101.87 (7)H15—C15—H17110 (3)
C2—C1—C6117.29 (18)H16—C15—H17107 (2)
C2—C1—S1122.53 (15)P1—C16—H18108.8 (17)
C6—C1—S1120.16 (16)P1—C16—H19107 (2)
C1—C2—C3122.05 (19)H18—C16—H19109 (3)
C1—C2—H1119.9 (15)P1—C16—H20111.0 (16)
C3—C2—H1118.0 (15)H18—C16—H20109 (2)
C4—C3—C2119.3 (2)H19—C16—H20111 (2)
C4—C3—H2121.8 (14)P1—C17—H21109.3 (17)
C2—C3—H2118.8 (14)P1—C17—H22108.9 (17)
O1—C4—C3124.43 (19)H21—C17—H22110 (2)
O1—C4—C5115.97 (17)P1—C17—H23109.3 (19)
C3—C4—C5119.60 (18)H21—C17—H23112 (3)
C6—C5—C4120.87 (18)H22—C17—H23108 (3)
C6—C5—H3118.9 (15)P2—C18—H24106.1 (17)
C4—C5—H3120.2 (15)P2—C18—H25109 (2)
C5—C6—C1120.84 (19)H24—C18—H25111 (3)
C5—C6—H4121.8 (14)P2—C18—H26113.3 (18)
C1—C6—H4117.3 (14)H24—C18—H26108 (2)
O1—C7—H9112.5 (14)H25—C18—H26109 (3)
O1—C7—H10110.2 (16)P2—C19—H27111.2 (16)
H9—C7—H10107 (2)P2—C19—H28109.9 (17)
O1—C7—H11105.1 (17)H27—C19—H28106 (3)
H9—C7—H11111 (2)P2—C19—H29108.5 (18)
H10—C7—H11111 (2)H27—C19—H29112 (2)
C9—C8—C13118.05 (18)H28—C19—H29109 (2)
C9—C8—S2122.12 (15)P2—C20—H30108.9 (17)
C13—C8—S2119.82 (16)P2—C20—H31110 (2)
C8—C9—C10121.55 (19)H30—C20—H31107 (2)
C8—C9—H5118.6 (15)P2—C20—H32107 (2)
C10—C9—H5119.8 (15)H30—C20—H32107 (3)
C11—C10—C9119.6 (2)H31—C20—H32117 (3)
C11—C10—H6122.6 (14)C4—O1—C7117.19 (17)
C9—C10—H6117.8 (14)C11—O2—C14116.84 (17)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FI2053).

References

  • Klein, H.-F., Dal, A., Jung, T., Braun, S., Roehr, C., Floerke, U. & Haupt, H.-J. (1998). Eur. J. Inorg. Chem. pp. 621–627.
  • Klein, H.-F. & Karsch, H. H. (1972). Chem. Ber.105, 2628–2636.
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.
  • Sheldrick, G. M. (2001). SHELXTL Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Siemens (1996). XSCANS Version 2.2. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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