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

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)°.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.085
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...         32

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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.

Related literature

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

S2. 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).

S3. Refinement

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

Computing details

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

Figures

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

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

Crystal data

[Ni(C7H7OS)2(C3H9P)2]	F(000) = 1032
Mr = 489.23	Dx = 1.373 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1843 reflections
a = 14.022 (3) Å	θ = 2.4–24.3°
b = 15.983 (3) Å	µ = 1.14 mm^−1
c = 10.758 (2) Å	T = 273 K
β = 100.93 (3)°	Cubic, dark red
V = 2367.3 (8) Å^3	0.30 × 0.24 × 0.21 mm
Z = 4

Data collection

Bruker P4 diffractometer	4078 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 27.1°, θmin = 1.5°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −20→20
Tmin = 0.725, Tmax = 0.795	l = −13→13
14644 measured reflections	14954 standard reflections every 6 reflections
5103 independent reflections	intensity decay: 30%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	All H-atom parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0526P)^2] where P = (Fo^2 + 2Fc^2)/3
5103 reflections	(Δ/σ)max = 0.001
372 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.257048 (17)	0.016260 (16)	0.74629 (2)	0.03027 (9)
P1	0.37880 (4)	0.08109 (3)	0.68296 (5)	0.03426 (13)
P2	0.13706 (4)	−0.05297 (3)	0.80892 (5)	0.03389 (13)
S1	0.17664 (4)	0.00061 (3)	0.54812 (5)	0.03656 (13)
S2	0.33803 (4)	0.03453 (3)	0.94334 (5)	0.03455 (12)
C1	0.24429 (14)	−0.07893 (12)	0.48988 (19)	0.0322 (4)
C2	0.30721 (15)	−0.13200 (13)	0.56961 (19)	0.0345 (4)
C3	0.35857 (15)	−0.19580 (13)	0.52267 (19)	0.0336 (4)
C4	0.34651 (14)	−0.20757 (12)	0.39280 (19)	0.0319 (4)
C5	0.28431 (15)	−0.15531 (13)	0.31149 (19)	0.0334 (4)
C6	0.23405 (15)	−0.09207 (13)	0.35826 (19)	0.0318 (4)
C7	0.4551 (2)	−0.32462 (15)	0.4172 (3)	0.0473 (6)
C8	0.25968 (14)	0.10267 (12)	1.00678 (18)	0.0317 (4)
C9	0.19724 (15)	0.15744 (13)	0.9314 (2)	0.0349 (4)
C10	0.13341 (16)	0.20890 (13)	0.9820 (2)	0.0352 (4)
C11	0.13282 (14)	0.20600 (12)	1.11072 (19)	0.0330 (4)
C12	0.19604 (15)	0.15232 (13)	1.18851 (19)	0.0344 (4)
C13	0.25869 (15)	0.10109 (13)	1.13772 (19)	0.0330 (4)
C14	0.00536 (19)	0.30705 (15)	1.0914 (3)	0.0465 (6)
C15	0.49677 (17)	0.03403 (16)	0.7405 (3)	0.0439 (5)
C16	0.3913 (2)	0.18866 (15)	0.7388 (3)	0.0465 (5)
C17	0.3817 (2)	0.0948 (2)	0.5153 (2)	0.0527 (6)
C18	0.01701 (18)	−0.00824 (17)	0.7602 (3)	0.0492 (6)
C19	0.1249 (2)	−0.15763 (16)	0.7437 (3)	0.0489 (6)
C20	0.1384 (3)	−0.0739 (2)	0.9760 (3)	0.0594 (7)
O1	0.39280 (12)	−0.26858 (9)	0.33592 (14)	0.0417 (4)
O2	0.07266 (11)	0.25359 (10)	1.16992 (14)	0.0409 (3)
H8	0.3030 (17)	0.0637 (14)	1.193 (2)	0.037 (6)*
H4	0.1928 (17)	−0.0562 (14)	0.305 (2)	0.036 (6)*
H2	0.4020 (17)	−0.2288 (14)	0.581 (2)	0.037 (6)*
H6	0.0932 (18)	0.2463 (15)	0.926 (2)	0.042 (6)*
H1	0.3157 (18)	−0.1256 (15)	0.658 (2)	0.045 (7)*
H7	0.1979 (17)	0.1481 (13)	1.278 (2)	0.038 (6)*
H3	0.2763 (18)	−0.1623 (15)	0.226 (2)	0.043 (6)*
H30	0.083 (2)	−0.1094 (17)	0.983 (3)	0.060 (8)*
H21	0.444 (2)	0.1243 (17)	0.506 (3)	0.064 (8)*
H5	0.2010 (18)	0.1621 (15)	0.843 (2)	0.047 (7)*
H22	0.3789 (19)	0.0424 (18)	0.477 (3)	0.047 (7)*
H24	−0.028 (2)	−0.0478 (17)	0.788 (3)	0.061 (8)*
H15	0.506 (2)	0.0290 (18)	0.822 (3)	0.064 (9)*
H27	0.065 (2)	−0.1831 (17)	0.755 (3)	0.061 (8)*
H16	0.544 (2)	0.0681 (17)	0.715 (3)	0.059 (8)*
H12	−0.031 (2)	0.3322 (17)	1.149 (3)	0.059 (8)*
H9	0.5112 (18)	−0.2937 (15)	0.477 (2)	0.045 (6)*
H25	0.004 (2)	−0.0024 (19)	0.673 (3)	0.072 (10)*
H18	0.387 (2)	0.1897 (17)	0.826 (3)	0.059 (8)*
H13	−0.0356 (19)	0.2742 (16)	1.023 (3)	0.046 (7)*
H28	0.123 (2)	−0.1555 (17)	0.655 (3)	0.061 (8)*
H19	0.341 (2)	0.2181 (19)	0.694 (3)	0.070 (9)*
H14	0.038 (2)	0.3483 (18)	1.049 (3)	0.060 (8)*
H31	0.130 (2)	−0.021 (2)	1.020 (3)	0.078 (10)*
H29	0.183 (2)	−0.1915 (19)	0.785 (3)	0.076 (9)*
H32	0.190 (2)	−0.1022 (19)	1.005 (3)	0.066 (10)*
H20	0.455 (2)	0.2127 (17)	0.728 (3)	0.062 (8)*
H17	0.500 (2)	−0.0226 (18)	0.701 (3)	0.059 (8)*
H10	0.4198 (19)	−0.3535 (16)	0.469 (3)	0.051 (7)*
H11	0.480 (2)	−0.3626 (17)	0.361 (3)	0.062 (8)*
H26	0.010 (2)	0.047 (2)	0.799 (3)	0.066 (9)*
H23	0.327 (2)	0.125 (2)	0.477 (3)	0.073 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02676 (14)	0.03814 (15)	0.02594 (14)	0.00280 (10)	0.00507 (11)	−0.00110 (9)
P1	0.0296 (3)	0.0426 (3)	0.0310 (3)	0.0011 (2)	0.0065 (2)	0.0020 (2)
P2	0.0300 (3)	0.0403 (3)	0.0314 (3)	−0.0006 (2)	0.0058 (2)	0.0005 (2)
S1	0.0313 (3)	0.0491 (3)	0.0280 (3)	0.0076 (2)	0.0023 (2)	−0.0026 (2)
S2	0.0304 (3)	0.0442 (3)	0.0280 (2)	0.0055 (2)	0.0028 (2)	−0.0019 (2)
C1	0.0274 (9)	0.0401 (10)	0.0288 (10)	−0.0031 (8)	0.0045 (8)	−0.0007 (8)
C2	0.0355 (11)	0.0437 (11)	0.0241 (9)	0.0010 (8)	0.0048 (9)	−0.0020 (8)
C3	0.0340 (10)	0.0375 (10)	0.0287 (10)	−0.0003 (8)	0.0046 (9)	0.0015 (8)
C4	0.0340 (10)	0.0319 (9)	0.0305 (10)	−0.0039 (8)	0.0079 (9)	−0.0022 (7)
C5	0.0357 (11)	0.0401 (10)	0.0243 (10)	−0.0054 (8)	0.0055 (9)	−0.0017 (8)
C6	0.0303 (10)	0.0370 (10)	0.0273 (10)	−0.0026 (8)	0.0033 (8)	0.0034 (8)
C7	0.0602 (16)	0.0377 (11)	0.0441 (13)	0.0093 (11)	0.0102 (13)	−0.0008 (10)
C8	0.0311 (10)	0.0364 (10)	0.0278 (10)	−0.0005 (8)	0.0057 (8)	−0.0015 (8)
C9	0.0369 (11)	0.0408 (11)	0.0277 (10)	0.0021 (8)	0.0076 (9)	0.0013 (8)
C10	0.0374 (11)	0.0354 (10)	0.0326 (11)	0.0038 (8)	0.0060 (9)	0.0022 (8)
C11	0.0315 (10)	0.0344 (9)	0.0342 (11)	−0.0038 (8)	0.0090 (9)	−0.0078 (8)
C12	0.0364 (11)	0.0413 (11)	0.0257 (10)	−0.0048 (8)	0.0066 (9)	−0.0030 (8)
C13	0.0329 (10)	0.0361 (10)	0.0286 (10)	−0.0010 (8)	0.0021 (9)	0.0011 (8)
C14	0.0482 (14)	0.0390 (12)	0.0538 (15)	0.0080 (10)	0.0136 (12)	−0.0038 (11)
C15	0.0336 (11)	0.0498 (13)	0.0508 (15)	0.0038 (10)	0.0144 (11)	0.0081 (11)
C16	0.0448 (14)	0.0432 (12)	0.0521 (15)	0.0023 (10)	0.0106 (12)	0.0040 (11)
C17	0.0517 (16)	0.0705 (18)	0.0376 (13)	−0.0125 (14)	0.0124 (12)	0.0036 (12)
C18	0.0362 (12)	0.0544 (14)	0.0597 (17)	0.0063 (10)	0.0161 (12)	0.0100 (12)
C19	0.0460 (14)	0.0430 (12)	0.0597 (17)	−0.0040 (11)	0.0148 (13)	−0.0049 (11)
C20	0.0605 (18)	0.075 (2)	0.0420 (14)	−0.0214 (16)	0.0091 (14)	0.0093 (13)
O1	0.0503 (9)	0.0424 (8)	0.0319 (8)	0.0087 (7)	0.0061 (7)	−0.0055 (6)
O2	0.0388 (8)	0.0495 (8)	0.0353 (8)	0.0066 (7)	0.0091 (7)	−0.0084 (6)

Geometric parameters (Å, º)

Ni1—P1	2.2121 (7)	C9—H5	0.96 (2)
Ni1—P2	2.2224 (7)	C10—C11	1.387 (3)
Ni1—S2	2.2261 (9)	C10—H6	0.96 (3)
Ni1—S1	2.2288 (9)	C11—O2	1.378 (2)
P1—C15	1.816 (2)	C11—C12	1.393 (3)
P1—C16	1.819 (3)	C12—C13	1.387 (3)
P1—C17	1.825 (3)	C12—H7	0.96 (2)
P2—C19	1.809 (3)	C13—H8	0.98 (2)
P2—C18	1.812 (3)	C14—O2	1.425 (3)
P2—C20	1.825 (3)	C14—H12	0.97 (3)
S1—C1	1.770 (2)	C14—H13	0.99 (3)
S2—C8	1.7729 (19)	C14—H14	0.97 (3)
C1—C2	1.395 (3)	C15—H15	0.86 (3)
C1—C6	1.412 (3)	C15—H16	0.94 (3)
C2—C3	1.397 (3)	C15—H17	1.01 (3)
C2—H1	0.94 (3)	C16—H18	0.95 (3)
C3—C4	1.388 (3)	C16—H19	0.91 (3)
C3—H2	0.95 (2)	C16—H20	1.00 (3)
C4—O1	1.377 (2)	C17—H21	1.02 (3)
C4—C5	1.391 (3)	C17—H22	0.93 (3)
C5—C6	1.381 (3)	C17—H23	0.93 (3)
C5—H3	0.91 (3)	C18—H24	0.98 (3)
C6—H4	0.93 (2)	C18—H25	0.92 (4)
C7—O1	1.428 (3)	C18—H26	0.99 (3)
C7—H9	1.04 (3)	C19—H27	0.96 (3)
C7—H10	0.94 (3)	C19—H28	0.95 (3)
C7—H11	0.97 (3)	C19—H29	1.01 (3)
C8—C9	1.386 (3)	C20—H30	0.97 (3)
C8—C13	1.412 (3)	C20—H31	0.99 (4)
C9—C10	1.400 (3)	C20—H32	0.86 (3)
P1—Ni1—P2	178.07 (2)	O2—C11—C10	124.26 (19)
P1—Ni1—S2	87.01 (3)	O2—C11—C12	115.96 (18)
P2—Ni1—S2	93.17 (3)	C10—C11—C12	119.78 (18)
P1—Ni1—S1	92.17 (3)	C13—C12—C11	120.36 (18)
P2—Ni1—S1	87.67 (3)	C13—C12—H7	117.0 (14)
S2—Ni1—S1	178.85 (2)	C11—C12—H7	122.6 (14)
C15—P1—C16	104.76 (13)	C12—C13—C8	120.63 (19)
C15—P1—C17	101.37 (14)	C12—C13—H8	120.1 (13)
C16—P1—C17	101.21 (14)	C8—C13—H8	119.2 (13)
C15—P1—Ni1	114.04 (8)	O2—C14—H12	104.1 (17)
C16—P1—Ni1	111.87 (8)	O2—C14—H13	110.3 (14)
C17—P1—Ni1	121.57 (10)	H12—C14—H13	113 (2)
C19—P2—C18	103.82 (14)	O2—C14—H14	111.5 (18)
C19—P2—C20	101.25 (15)	H12—C14—H14	112 (2)
C18—P2—C20	101.07 (16)	H13—C14—H14	106 (2)
C19—P2—Ni1	111.32 (9)	P1—C15—H15	110 (2)
C18—P2—Ni1	115.54 (9)	P1—C15—H16	108.0 (17)
C20—P2—Ni1	121.54 (10)	H15—C15—H16	112 (3)
C1—S1—Ni1	102.20 (7)	P1—C15—H17	109.9 (17)
C8—S2—Ni1	101.87 (7)	H15—C15—H17	110 (3)
C2—C1—C6	117.29 (18)	H16—C15—H17	107 (2)
C2—C1—S1	122.53 (15)	P1—C16—H18	108.8 (17)
C6—C1—S1	120.16 (16)	P1—C16—H19	107 (2)
C1—C2—C3	122.05 (19)	H18—C16—H19	109 (3)
C1—C2—H1	119.9 (15)	P1—C16—H20	111.0 (16)
C3—C2—H1	118.0 (15)	H18—C16—H20	109 (2)
C4—C3—C2	119.3 (2)	H19—C16—H20	111 (2)
C4—C3—H2	121.8 (14)	P1—C17—H21	109.3 (17)
C2—C3—H2	118.8 (14)	P1—C17—H22	108.9 (17)
O1—C4—C3	124.43 (19)	H21—C17—H22	110 (2)
O1—C4—C5	115.97 (17)	P1—C17—H23	109.3 (19)
C3—C4—C5	119.60 (18)	H21—C17—H23	112 (3)
C6—C5—C4	120.87 (18)	H22—C17—H23	108 (3)
C6—C5—H3	118.9 (15)	P2—C18—H24	106.1 (17)
C4—C5—H3	120.2 (15)	P2—C18—H25	109 (2)
C5—C6—C1	120.84 (19)	H24—C18—H25	111 (3)
C5—C6—H4	121.8 (14)	P2—C18—H26	113.3 (18)
C1—C6—H4	117.3 (14)	H24—C18—H26	108 (2)
O1—C7—H9	112.5 (14)	H25—C18—H26	109 (3)
O1—C7—H10	110.2 (16)	P2—C19—H27	111.2 (16)
H9—C7—H10	107 (2)	P2—C19—H28	109.9 (17)
O1—C7—H11	105.1 (17)	H27—C19—H28	106 (3)
H9—C7—H11	111 (2)	P2—C19—H29	108.5 (18)
H10—C7—H11	111 (2)	H27—C19—H29	112 (2)
C9—C8—C13	118.05 (18)	H28—C19—H29	109 (2)
C9—C8—S2	122.12 (15)	P2—C20—H30	108.9 (17)
C13—C8—S2	119.82 (16)	P2—C20—H31	110 (2)
C8—C9—C10	121.55 (19)	H30—C20—H31	107 (2)
C8—C9—H5	118.6 (15)	P2—C20—H32	107 (2)
C10—C9—H5	119.8 (15)	H30—C20—H32	107 (3)
C11—C10—C9	119.6 (2)	H31—C20—H32	117 (3)
C11—C10—H6	122.6 (14)	C4—O1—C7	117.19 (17)
C9—C10—H6	117.8 (14)	C11—O2—C14	116.84 (17)