Di-μ-chlorido-bis-[diacetonitrile-chlorido-oxidovanadium(IV)].

The title compound, [V(2)Cl(4)O(2)(CH(3)CN)(4)], is a centrosymmetric dinuclear V(IV) complex associated with four mol-ecules of acetonitrile. The coordination around both V(IV) atoms is essentially square-planar, involving three Cl atoms and one O atom [maximum deviation = 0.017 (3) Å for the O atom]. The augmented octahedral coordination of the metal atom is completed by the N atoms of acetonitrile ligands. The V(IV) atoms are linked by two Cl atoms, acting as bridging atoms. The crystal studied was a non-merohedral twin with a ratio of the two twin components of 0.8200 (3):0.1800 (3). Although Cl and O atoms are present as potential acceptors in the title compound, no hydrogen bonds were observed in the crystal structure.

Related literature

For the biological activity of vanadium(IV) compounds, see: D’Cruz et al. (2003 ▶); Lopez et al. (1976 ▶); Lu et al. (2001 ▶); Shi et al. (1996 ▶). For Ziegler–Natta catalysts, see: Hagen et al. (2002 ▶). For the synthesis of chloridooxidovanadium(IV) complexes, see: du Preez & Sadle (1967 ▶); Homden et al. (2009 ▶); Kern (1962 ▶); Papoutsakis et al. (2004 ▶); Priebsch & Rehder (1990 ▶).

Experimental

Crystal data

[V2Cl4O2(C2H3N)4]

M = 439.90

Triclinic,

a = 7.0242 (6) Å

b = 8.1388 (6) Å

c = 8.7118 (5) Å

α = 86.536 (6)°

β = 66.806 (7)°

γ = 74.374 (7)°

V = 440.28 (6) Å3

Z = 1

Mo Kα radiation

μ = 1.67 mm−1

T = 120 K

0.30 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T min = 0.804, T max = 1.000

1550 measured reflections

1550 independent reflections

1432 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.103

S = 1.25

1550 reflections

94 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811037184/ru2013sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037184/ru2013Isup2.hkl

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

[V2Cl4O2(C2H3N)4]	Z = 1
Mr = 439.90	F(000) = 218
Triclinic, P1	Dx = 1.659 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 7.0242 (6) Å	Cell parameters from 5307 reflections
b = 8.1388 (6) Å	θ = 3.3–25.0°
c = 8.7118 (5) Å	µ = 1.67 mm−1
α = 86.536 (6)°	T = 120 K
β = 66.806 (7)°	Block, blue
γ = 74.374 (7)°	0.30 × 0.20 × 0.15 mm
V = 440.28 (6) Å3

Oxford Diffraction Xcalibur Sapphire2 diffractometer	1550 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1432 reflections with I > 2σ(I)
graphite	Rint = 0.000
Detector resolution: 8.4 pixels mm-1	θmax = 25.0°, θmin = 3.3°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −9→9
Tmin = 0.804, Tmax = 1.000	l = −9→10
1550 measured reflections

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.25	w = 1/[σ2(Fo2) + (0.0397P)2 + 1.0484P] where P = (Fo2 + 2Fc2)/3
1550 reflections	(Δ/σ)max < 0.001
94 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.51 e Å−3

Experimental. 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
V1	0.58161 (10)	0.06353 (8)	0.67541 (8)	0.0141 (2)
Cl1	0.71230 (14)	−0.15703 (11)	0.46017 (11)	0.0172 (2)
Cl2	0.38000 (14)	0.30593 (12)	0.85537 (12)	0.0201 (2)
O1	0.7642 (4)	−0.0069 (3)	0.7454 (3)	0.0192 (6)
N2	0.7440 (5)	0.2175 (4)	0.5012 (4)	0.0197 (7)
C4	0.9873 (6)	0.3945 (5)	0.3008 (5)	0.0228 (8)
H4A	0.8981	0.5071	0.2916	0.034*
H4B	1.0645	0.3351	0.1901	0.034*
H4C	1.0911	0.4083	0.3448	0.034*
C2	0.1588 (7)	−0.2589 (5)	1.0454 (5)	0.0241 (9)
H2A	0.0118	−0.2274	1.0500	0.036*
H2B	0.1555	−0.2385	1.1563	0.036*
H2C	0.2258	−0.3801	1.0105	0.036*
N1	0.3766 (5)	−0.0747 (4)	0.8326 (4)	0.0190 (7)
C3	0.8514 (6)	0.2950 (5)	0.4132 (5)	0.0193 (8)
C1	0.2821 (6)	−0.1565 (5)	0.9263 (5)	0.0190 (8)

	U11	U22	U33	U12	U13	U23
V1	0.0142 (3)	0.0150 (3)	0.0125 (3)	−0.0029 (2)	−0.0051 (3)	−0.0007 (2)
Cl1	0.0173 (4)	0.0172 (5)	0.0155 (5)	−0.0002 (3)	−0.0071 (4)	−0.0039 (3)
Cl2	0.0191 (5)	0.0192 (5)	0.0197 (5)	−0.0014 (4)	−0.0066 (4)	−0.0054 (4)
O1	0.0197 (14)	0.0202 (14)	0.0188 (14)	−0.0028 (11)	−0.0100 (11)	−0.0016 (11)
N2	0.0180 (16)	0.0195 (17)	0.0177 (17)	−0.0033 (14)	−0.0039 (14)	−0.0002 (14)
C4	0.025 (2)	0.024 (2)	0.020 (2)	−0.0099 (17)	−0.0079 (17)	0.0039 (16)
C2	0.025 (2)	0.024 (2)	0.023 (2)	−0.0136 (17)	−0.0040 (17)	0.0005 (17)
N1	0.0219 (16)	0.0209 (17)	0.0135 (16)	−0.0070 (14)	−0.0051 (14)	−0.0010 (14)
C3	0.0182 (19)	0.019 (2)	0.020 (2)	0.0008 (16)	−0.0096 (17)	−0.0040 (16)
C1	0.0200 (19)	0.0182 (19)	0.019 (2)	−0.0030 (16)	−0.0087 (16)	−0.0028 (16)

V1—O1	1.588 (3)	C4—H4A	0.9800
V1—N1	2.085 (3)	C4—H4B	0.9800
V1—N2	2.086 (3)	C4—H4C	0.9800
V1—Cl2	2.3399 (10)	C2—C1	1.448 (6)
V1—Cl1	2.3969 (10)	C2—H2A	0.9800
V1—Cl1i	2.6836 (10)	C2—H2B	0.9800
Cl1—V1i	2.6836 (10)	C2—H2C	0.9800
N2—C3	1.139 (5)	N1—C1	1.138 (5)
C4—C3	1.453 (6)
O1—V1—N1	94.79 (14)	C3—N2—V1	171.8 (3)
O1—V1—N2	95.52 (14)	C3—C4—H4A	109.5
N1—V1—N2	169.69 (13)	C3—C4—H4B	109.5
O1—V1—Cl2	99.62 (10)	H4A—C4—H4B	109.5
N1—V1—Cl2	89.60 (9)	C3—C4—H4C	109.5
N2—V1—Cl2	88.90 (9)	H4A—C4—H4C	109.5
O1—V1—Cl1	96.44 (10)	H4B—C4—H4C	109.5
N1—V1—Cl1	89.01 (9)	C1—C2—H2A	109.5
N2—V1—Cl1	89.61 (9)	C1—C2—H2B	109.5
Cl2—V1—Cl1	163.95 (4)	H2A—C2—H2B	109.5
O1—V1—Cl1i	174.92 (10)	C1—C2—H2C	109.5
N1—V1—Cl1i	84.57 (9)	H2A—C2—H2C	109.5
N2—V1—Cl1i	85.15 (9)	H2B—C2—H2C	109.5
Cl2—V1—Cl1i	85.42 (3)	C1—N1—V1	172.0 (3)
Cl1—V1—Cl1i	78.53 (4)	N2—C3—C4	179.6 (4)
V1—Cl1—V1i	101.47 (4)	N1—C1—C2	179.1 (4)
O1—V1—Cl1—V1i	179.36 (11)	Cl2—V1—Cl1—V1i	−0.47 (16)
N1—V1—Cl1—V1i	84.66 (9)	Cl1i—V1—Cl1—V1i	0.0
N2—V1—Cl1—V1i	−85.13 (9)