cis-Di­chloridobis(ethyl methyl sulfide-κS)oxidovanadium(IV)

The mononuclear title complex, [VCl₂O(C₃H₈S)₂], features a V^IV=O double bond [1.5845 (15) Å] in an overall trigonal–bipyramidal coordination environment defined by two Cl⁻ and the S atoms of two (CH₃CH₂)(CH₃)S ligands. In the crystal, pairs of mol­ecules form centrosymmetric dimers via C—H⋯O hydrogen bonds between the methyl C—H group and the oxidovanadium O atom of a neighbouring mol­ecule.

Related literature

For related structures, see: Azuma et al. (1994); Bristow et al. (1989); Hartung et al. (2005); Kakeya, Fujihara, Kasaya et al. (2006); Kakeya, Fujihara & Nagasawa (2006); Matsuura et al. (2012); Papoutsakis et al. (2004); Takano et al. (2009). For hydrogen-bonded motifs, see: Bernstein et al. (1995).

Experimental

Crystal data

• [VCl₂O(C₃H₈S)₂]

• M_r = 290.15

• Monoclinic, P 2₁ /n

• a = 10.503 (3) Å

• b = 10.386 (3) Å

• c = 11.890 (4) Å

• β = 93.484 (3)°

• V = 1294.6 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 1.46 mm⁻¹

• T = 150 K

• 0.15 × 0.13 × 0.11 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008) T_min = 0.811, T_max = 0.856

• 13449 measured reflections

• 2646 independent reflections

• 2125 reflections with I > 2σ(I)

• R_int = 0.059

Refinement

• R[F² > 2σ(F²)] = 0.031

• wR(F²) = 0.066

• S = 1.24

• 2646 reflections

• 113 parameters

• H-atom parameters constrained

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1^i	0.99	2.57	3.547 (3)	170
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); 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, 2012); software used to prepare material for publication: XCIF (Bruker, 2008).

Supporting information

S1. Comment

The chemistry of the higher oxidation states of vanadium with neutral thioether ligands in discrete complexes remains relatively unexplored due to the instability of such complexes. Our research group has already carried out X-ray crystallographic determinations of lower oxidation state niobium complexes of the general formula [Nb₂Cl₆L¹₂L²] (L¹= L²= tetrahydrothiophene C₄H₈S (THT) (Kakeya, Fujihara, Kasaya et al., 2006) and dimethyl sulfide C₂H₆S (Kakeya, Fujihara & Nagasawa, 2006)) and (L¹ = dimethyl selenide C₂H₆Se, L² = C₂H₆S) (Matsuura et al., 2012). We report here the structure of [VOCl₂(C₃H₈S)₂] (I, Scheme I). The molecule has two Cl^- and two EtMeS ligands (Fig. 1). Crystal structures have been reported for trigonal bipyramidal complexes formed when the water ligands in [VOCl₂(H₂O)₂] are replaced by 8-hydroxyquinolinium chloride (Takano et al., 2009), bis(2-(2-pyridylamino)pyridinium) dichloride (Hartung et al., 2005), diethyl ether (Papoutsakis et al., 2004) and benzo-15-crown-5 (Azuma et al., 1994). The only trigonal bipyramidal complex containing S^2- reported to date is [VOCl₂(thiourea)₂] (II, Bristow et al., 1989). In complex I, the O atom and two Cl^- ligands occupy the equatorial positions and the two EtMeS ligands the axial positions of a distorted trigonal bipyramid. The S2—V1—S1 angle of 166.66 (2) ^o deviates from the ideal value of 180 ^o. The steric bulkness of the EtMeS ligand may be responsible for controlling the structure. The V—S distances, 2.4803 (9) and 2.4858 (9) Å, in our complex are slightly longer than that of 2.424 (1) Å in II. The average V—Cl distance and other geometrical parameters fall within the range of those in II. In the crystal, pairs of molecules form centrosymmetric R₂²(10) dimers (Bernstein et al., 1995) via C—H···O hydrogen bonds between the methyl C—H group and the O atom of oxidovanadium in a neighboring molecule (Fig. 2).

Related literature

For related structures, see: Azuma et al. (1994); Bristow et al. (1989); Hartung et al. (2005); Kakeya, Fujihara, Kasaya et al. (2006); Kakeya, Fujihara & Nagasawa (2006); Matsuura et al. (2012); Papoutsakis et al. (2004); Takano et al. (2009). For hydrogen-bonded motifs, see: Bernstein et al. (1995).

S2. Experimental

All the reactions were carried out under a dry argon atmosphere by using standard Schlenk tube techniques. Vanadium trichloride, VCl₃ (1.0 g, 6.4 mmol), was suspended in CH₂Cl₂ (40 mL), and ethylmethyl sulfide (C₃H₈S, 1.7 mL, 19 mmol) added to the solution at room temperature. The mixture was stirred at room temperature for 2 d, during which time, a purple precipitate, probably of residual starting material, was generated gradually. This was removed by filtration. The resultant filtrate was concentrated to 5 mL before the addition of n-hexane (10 mL). The solution was then set aside in a freezer at 255 K. After several days, blue crystals grew in the solution. The product was too reactive with liquid water to exist at temperatures higher than 273 K even in solvent under an Ar atmosphere.

S3. Refinement

The H atoms were placed in calculated positions, with C—H = 0.98 (methyl) and 0.99 (methylene) Å , and refined using a riding model, with U_iso(H) = 1.5.(methyl) and 1.2 U_eq (methylene).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); 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, 2012); software used to prepare material for publication: XCIF (Bruker, 2008).

Figures

	Fig. 1. The molecular structure of the complex (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Centrosymmetric dimer of two molecules of the title compound (I) connected by mutual C—H···O hydrogen bonds (symmetry code = 1 - x, -y, 2 - z).

cis-Dichloridobis(ethyl methyl sulfide-κS)oxidovanadium(IV)

Crystal data

[VCl2O(C3H8S)2]	F(000) = 596
Mr = 290.15	Dx = 1.489 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3238 reflections
a = 10.503 (3) Å	θ = 2.5–27.0°
b = 10.386 (3) Å	µ = 1.46 mm^−1
c = 11.890 (4) Å	T = 150 K
β = 93.484 (3)°	Block, blue
V = 1294.6 (7) Å^3	0.15 × 0.13 × 0.11 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2646 independent reflections
Radiation source: Bruker TXS fine-focus rotating anode	2125 reflections with I > 2σ(I)
Bruker Helios multilayer confocal mirror monochromator	Rint = 0.059
Detector resolution: 8.333 pixels mm^-1	θmax = 26.4°, θmin = 2.5°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −12→12
Tmin = 0.811, Tmax = 0.856	l = −14→14
13449 measured reflections

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H-atom parameters constrained
S = 1.24	w = 1/[σ^2(Fo^2) + (0.P)^2] where P = (Fo^2 + 2Fc^2)/3
2646 reflections	(Δ/σ)max < 0.001
113 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
V1	0.29967 (3)	0.19666 (4)	0.98439 (3)	0.02823 (12)
Cl1	0.08892 (5)	0.14880 (7)	0.95318 (5)	0.0513 (2)
Cl2	0.38968 (6)	0.37705 (6)	1.06207 (5)	0.04726 (18)
S1	0.27796 (5)	0.11532 (6)	1.17891 (4)	0.03144 (15)
S2	0.28225 (5)	0.31343 (6)	0.80213 (5)	0.03179 (15)
C1	0.4391 (2)	0.1050 (2)	1.24240 (17)	0.0361 (6)
H1A	0.4932	0.0586	1.1905	0.043*
H1B	0.4740	0.1931	1.2527	0.043*
C2	0.4459 (2)	0.0369 (3)	1.35491 (17)	0.0464 (7)
H2A	0.3901	0.0805	1.4059	0.070*
H2B	0.5339	0.0386	1.3874	0.070*
H2C	0.4182	−0.0526	1.3444	0.070*
C3	0.2416 (2)	−0.0523 (2)	1.15743 (19)	0.0467 (6)
H3A	0.3105	−0.0935	1.1186	0.070*
H3B	0.1613	−0.0607	1.1115	0.070*
H3C	0.2332	−0.0941	1.2305	0.070*
C4	0.4450 (2)	0.3479 (3)	0.7720 (2)	0.0492 (7)
H4A	0.4942	0.2677	0.7732	0.074*
H4B	0.4826	0.4070	0.8291	0.074*
H4C	0.4468	0.3878	0.6974	0.074*
C5	0.2422 (2)	0.1881 (2)	0.70034 (18)	0.0392 (6)
H5A	0.3071	0.1190	0.7085	0.047*
H5B	0.1588	0.1503	0.7169	0.047*
C6	0.2351 (3)	0.2359 (3)	0.5799 (2)	0.0544 (7)
H6A	0.1737	0.3068	0.5718	0.082*
H6B	0.2075	0.1655	0.5292	0.082*
H6C	0.3194	0.2662	0.5606	0.082*
O1	0.39676 (14)	0.09120 (15)	0.94548 (12)	0.0415 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.02533 (19)	0.0281 (2)	0.0312 (2)	−0.00192 (16)	0.00131 (15)	0.00101 (16)
Cl1	0.0309 (3)	0.0701 (5)	0.0518 (4)	−0.0170 (3)	−0.0072 (3)	0.0221 (3)
Cl2	0.0595 (4)	0.0392 (4)	0.0433 (3)	−0.0187 (3)	0.0047 (3)	−0.0057 (3)
S1	0.0290 (3)	0.0353 (4)	0.0302 (3)	−0.0030 (3)	0.0034 (2)	−0.0008 (2)
S2	0.0319 (3)	0.0292 (4)	0.0345 (3)	−0.0001 (3)	0.0044 (2)	0.0039 (2)
C1	0.0298 (11)	0.0464 (16)	0.0317 (12)	−0.0050 (11)	−0.0007 (9)	−0.0011 (11)
C2	0.0441 (14)	0.0599 (19)	0.0344 (13)	0.0017 (13)	−0.0029 (11)	0.0058 (12)
C3	0.0614 (16)	0.0385 (16)	0.0391 (14)	−0.0180 (13)	−0.0068 (12)	0.0046 (12)
C4	0.0378 (14)	0.0590 (19)	0.0517 (15)	−0.0153 (13)	0.0097 (12)	0.0001 (13)
C5	0.0410 (13)	0.0388 (16)	0.0376 (13)	−0.0033 (11)	0.0019 (11)	−0.0036 (11)
C6	0.0561 (16)	0.070 (2)	0.0371 (14)	−0.0027 (15)	0.0041 (12)	−0.0044 (13)
O1	0.0471 (9)	0.0402 (11)	0.0374 (9)	0.0140 (8)	0.0031 (7)	0.0023 (7)

Geometric parameters (Å, º)

V1—O1	1.5845 (15)	C2—H2C	0.9800
V1—Cl2	2.2695 (9)	C3—H3A	0.9800
V1—Cl1	2.2769 (9)	C3—H3B	0.9800
V1—S2	2.4803 (9)	C3—H3C	0.9800
V1—S1	2.4858 (9)	C4—H4A	0.9800
S1—C3	1.797 (3)	C4—H4B	0.9800
S1—C1	1.814 (2)	C4—H4C	0.9800
S2—C4	1.804 (2)	C5—C6	1.513 (3)
S2—C5	1.810 (2)	C5—H5A	0.9900
C1—C2	1.511 (3)	C5—H5B	0.9900
C1—H1A	0.9900	C6—H6A	0.9800
C1—H1B	0.9900	C6—H6B	0.9800
C2—H2A	0.9800	C6—H6C	0.9800
C2—H2B	0.9800
O1—V1—Cl2	115.47 (7)	H2A—C2—H2C	109.5
O1—V1—Cl1	115.97 (7)	H2B—C2—H2C	109.5
Cl2—V1—Cl1	128.56 (3)	S1—C3—H3A	109.5
O1—V1—S2	95.60 (6)	S1—C3—H3B	109.5
Cl2—V1—S2	87.64 (3)	H3A—C3—H3B	109.5
Cl1—V1—S2	86.85 (2)	S1—C3—H3C	109.5
O1—V1—S1	97.69 (6)	H3A—C3—H3C	109.5
Cl2—V1—S1	87.79 (3)	H3B—C3—H3C	109.5
Cl1—V1—S1	86.23 (2)	S2—C4—H4A	109.5
S2—V1—S1	166.66 (2)	S2—C4—H4B	109.5
C3—S1—C1	100.77 (12)	H4A—C4—H4B	109.5
C3—S1—V1	103.16 (8)	S2—C4—H4C	109.5
C1—S1—V1	105.74 (7)	H4A—C4—H4C	109.5
C4—S2—C5	101.24 (11)	H4B—C4—H4C	109.5
C4—S2—V1	104.47 (9)	C6—C5—S2	113.16 (18)
C5—S2—V1	103.56 (8)	C6—C5—H5A	108.9
C2—C1—S1	112.89 (15)	S2—C5—H5A	108.9
C2—C1—H1A	109.0	C6—C5—H5B	108.9
S1—C1—H1A	109.0	S2—C5—H5B	108.9
C2—C1—H1B	109.0	H5A—C5—H5B	107.8
S1—C1—H1B	109.0	C5—C6—H6A	109.5
H1A—C1—H1B	107.8	C5—C6—H6B	109.5
C1—C2—H2A	109.5	H6A—C6—H6B	109.5
C1—C2—H2B	109.5	C5—C6—H6C	109.5
H2A—C2—H2B	109.5	H6A—C6—H6C	109.5
C1—C2—H2C	109.5	H6B—C6—H6C	109.5
O1—V1—S1—C3	−51.05 (11)	Cl1—V1—S2—C4	−168.84 (9)
Cl2—V1—S1—C3	−166.45 (9)	S1—V1—S2—C4	132.35 (13)
Cl1—V1—S1—C3	64.67 (9)	O1—V1—S2—C5	52.59 (10)
S2—V1—S1—C3	123.54 (13)	Cl2—V1—S2—C5	167.95 (8)
O1—V1—S1—C1	54.33 (10)	Cl1—V1—S2—C5	−63.22 (8)
Cl2—V1—S1—C1	−61.07 (9)	S1—V1—S2—C5	−122.02 (13)
Cl1—V1—S1—C1	170.05 (9)	C3—S1—C1—C2	−63.62 (19)
S2—V1—S1—C1	−131.08 (13)	V1—S1—C1—C2	−170.74 (16)
O1—V1—S2—C4	−53.04 (11)	C4—S2—C5—C6	−68.07 (19)
Cl2—V1—S2—C4	62.33 (9)	V1—S2—C5—C6	−176.14 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1^i	0.99	2.57	3.547 (3)	170

Symmetry code: (i) −x+1, −y, −z+2.