Hexakis(2-amino-4-methyl­pyridine-κN1)dioxidohexa-μ4-sulfido-hexa­copper(I)divanadium(V)

Yu, Z.; Tang, G.; Zhao, J.; Jiang, Z.

doi:10.1107/S1600536808027165

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page m1217

doi:10.1107/S1600536808027165

Open

access

Hexakis(2-amino-4-methylpyridine-κN¹)dioxidohexa-μ₄-sulfido-hexacopper(I)divanadium(V)

Zhang Yu,^a Guodong Tang,^a Jianying Zhao ^a and Zhengjing Jiang ^a ^*

^aDepartment of Chemistry, Huaiyin Teachers College, Huai'an 223300, Jiangsu, People's Republic of China
^*Correspondence e-mail: yuzhang@hytc.edu.cn

(Received 3 June 2008; accepted 23 August 2008; online 30 August 2008)

The title compound, [Cu₆V₂O₂S₆(C₆H₈N₂)₆], is constructed from six CuS₃N and two VOS₃ distorted tetrahedra, forming an octanuclear V/S/Cu cluster with C_i symmetry. The geometry around the V atoms is slightly distorted tetrahedral, while there are large distortions from ideal tetrahedral geometry for the Cu atoms. Adjacent metal–metal distances range from 2.693 (1) to 2.772 (10) Å, indicating weak metal–metal interactions in the cluster.

Related literature

The most relevant known analog of the title compound is hexakis(μ₄-sulfido)-dioxohexakis(triphenylphosphine) -hexacopper(I)divanadium(V) (Zheng et al., 2001 ), For related literature, see: Du et al. (1992 ); Holm (1992 ); Hou et al. (1996 ); Liu et al. (1995 ); Naruta et al. (1994 ); Zhang et al. (1996 , 2001 ).

Experimental

Crystal data

[Cu₆V₂O₂S₆(C₆H₈N₂)₆]
M_r = 1356.34
Hexagonal, $[R \overline 3]$
a = 14.139 (2) Å
c = 20.830 (4) Å
V = 3606.2 (10) Å³
Z = 3
Mo Kα radiation
μ = 3.28 mm⁻¹
T = 293 (2) K
0.3 × 0.2 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.465, T_max = 0.611
6168 measured reflections
1837 independent reflections
1092 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.128
S = 1.02
1837 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808027165/bv2103sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027165/bv2103Isup2.hkl

checkCIF report

Comment top

In the past two decades, considerable attention has been directed to the study of tetrathiometalate anions [MXS₃]^n- (X=O, S; M=V, Mo, W, Re) cluster compounds, since these complexes play a special role in catalysis reactions (Du et al., 1992), biological processes (Holm et al., 1992) and advanced materials (Naruta et al., 1994). These moieties can react as multidentate ligands with a wide variety of metal ions, such as Cu, Ag, Au, Zn, Cd, Hg, Fe, Co, Ni, Pd, Pt, Sn, and Ru to form a wide range of novel structures (Hou et al., 1996). More than 300 heterothiometallic cluster compounds containing these moieties have been synthesized and extensively studied (Zhang et al.,, 2001). However, crystal structures of these clusters containing 2-amino-4-methylpyridine ligands have not been reported until now.

In order to explore the chemistry of Mo(W)/S/Cu(Ag) clusters extensively, we have synthesized such a cluster by reaction in solution at normal temperatures. The solid-state molecular structure of the octanuclear neutral cluster 1 is shown in Fig. 1. It contains a cluster core [V₂Cu₆S₆O₂], of which the V₂Cu₆ atoms form a distorted cube, shown in Fig. 2. Each µ₄-S atom is bonded to three Cu atoms and one V atom constructing each face of the dodecahedron. The geometry around the V atoms is slightly distorted tetrahedral with S–V–S 109.97 (5)° and S–V–O 108.97 (5)°, and the V–S bonds, 2.2382 (15) Å, are somewhat longer than those of the free [VS₄]^3- anion as expected [2.17 Å in the ammonium salt]. The coordination geometry of every Cu atom, bonded to three µ₄-S atoms and one terminal ligand 2-amino-4-methylpyridine, is strongly distorted from an ideal tetrahedron with S—Cu—N angles varying from 104.52 (13)° to 121.11 (14)°. This phenomenon may arise from the steric effect of the bulky 2-amino-4-methylpyridine ligands. The Cu—N distance of 2.033 (4) Å is somewhat longer than the Cu—N distance found in [V₂S₄O₃(CuPPh₃)₄(CuMeCN)₂] complexes (Zhang et al.,, 1996). The Cu—S distances between 2.2886 (15) Å and 2.4701 (16) Å are comparable to those reported in (Et₄N)₃[(VS₄Cu₄(Et₂dtc)(PhS)₃] (Et₂dtc=diethyldithiocarbamate) complexes (mean Cu—S = 2.236 (5) Å)(Liu et al., 1995).

In the preparation of the title compound, one S atom of the [VS₄]^3- unit is replaced by an O atom and [VS₄]^3- becomes [VS₃O]^3-. The V—O distance 1.618 (6) Å is a typical double bond distance. The adjacent metal-metal distances range from 2.6932 (11) Å to 2.7725 (10) Å, and are slightly shorter than normal V—Cu and Cu—Cu distances, indicating that there are weak metal-metal interactions. The terminal 2-amino-4-methylpyridine ligand is present in the usual monodentate mode. The C1—N1, C5—N1 and C1—N2 distances of 1.344 (6) Å, 1.344 (7) Å and 1.350 (7) Å, respectively, are typical Csp²—Nsp² values.

Related literature top

The most relevant known analog of the title compound is hexakis(µ₄-sulfido)-dioxohexakis(triphenylphosphine) -hexacopper(I)divanadium(V) (Zheng et al., 2001), For related literature, see: Du et al. (1992); Holm (1992); Hou et al. (1996); Liu et al. (1995); Naruta et al. (1994); Zhang et al. (1996, 2001).

Experimental top

To a solution of 2-amino-4-methylpyridine (0.0230 g, 0.1 mmol) in dimethylformamide (DMF) (10 ml) were added a solution of CuI (0.0741 g, 0.2 mmol) and (NH₄)₃VS₄ suspended in DMF (5 ml). The reaction mixture was stirred at room temperature for about 8 h. The deep brown solution was filtered and slow diffution of i-PrOH/MeCN to the solution, resulted in black prismatic crystals suitable for X-ray analysis.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted.
	Fig. 2. Cubic arrangement of metal atoms.

Hexakis(2-amino-4-methylpyridine-κN¹)dioxidohexa-µ₄-sulfido-hexacopper(I)divanadium(V) top

Crystal data top

[Cu₆V₂O₂S₆(C₆H₈N₂)₆]	D_x = 1.874 Mg m⁻³
M_r = 1356.34	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, R3	Cell parameters from 6634 reflections
Hall symbol: -R 3	θ = 1.9–27.5°
a = 14.139 (2) Å	µ = 3.28 mm⁻¹
c = 20.830 (4) Å	T = 293 K
V = 3606.2 (10) Å³	Block, black
Z = 3	0.3 × 0.2 × 0.15 mm
F(000) = 2040

Data collection top

Bruker APEXII CCD diffractometer	1837 independent reflections
Radiation source: fine-focus sealed tube	1092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→18
T_min = 0.465, T_max = 0.611	k = −12→18
6168 measured reflections	l = −26→27

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0525P)²] where P = (F_o² + 2F_c²)/3
1837 reflections	(Δ/σ)_max = 0.001
97 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Cu₆V₂O₂S₆(C₆H₈N₂)₆]	Z = 3
M_r = 1356.34	Mo Kα radiation
Hexagonal, R3	µ = 3.28 mm⁻¹
a = 14.139 (2) Å	T = 293 K
c = 20.830 (4) Å	0.3 × 0.2 × 0.15 mm
V = 3606.2 (10) Å³

Data collection top

Bruker APEXII CCD diffractometer	1837 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1092 reflections with I > 2σ(I)
T_min = 0.465, T_max = 0.611	R_int = 0.054
6168 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.02	Δρ_max = 0.58 e Å⁻³
1837 reflections	Δρ_min = −0.69 e Å⁻³
97 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cu1	0.15031 (5)	0.98780 (5)	0.96002 (3)	0.0233 (3)
V1	0.0000	1.0000	0.88657 (7)	0.0207 (4)
S1	0.14481 (11)	0.99064 (11)	1.07850 (6)	0.0200 (4)
N1	0.2966 (4)	1.0004 (4)	0.9392 (2)	0.0247 (12)
N2	0.2279 (4)	0.8233 (4)	0.9034 (2)	0.0412 (14)
H2A	0.1631	0.8107	0.9120	0.049*
H2B	0.2373	0.7723	0.8878	0.049*
C2	0.4198 (5)	0.9427 (5)	0.9031 (3)	0.0269 (14)
H2C	0.4295	0.8870	0.8865	0.032*
O1	0.0000	1.0000	0.8089 (3)	0.0252 (16)
C1	0.3149 (5)	0.9230 (5)	0.9147 (2)	0.0227 (13)
C4	0.4909 (5)	1.1207 (5)	0.9417 (3)	0.0309 (15)
H4A	0.5492	1.1893	0.9518	0.037*
C5	0.3854 (5)	1.0969 (5)	0.9528 (3)	0.0296 (15)
H5A	0.3749	1.1511	0.9710	0.036*
C3	0.5092 (5)	1.0422 (5)	0.9155 (3)	0.0255 (14)
C6	0.6221 (5)	1.0633 (6)	0.9020 (3)	0.0424 (18)
H6A	0.6744	1.1371	0.9134	0.064*
H6B	0.6289	1.0522	0.8571	0.064*
H6C	0.6356	1.0139	0.9267	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0191 (4)	0.0213 (4)	0.0307 (4)	0.0111 (4)	0.0002 (3)	0.0007 (3)
V1	0.0197 (6)	0.0197 (6)	0.0226 (9)	0.0098 (3)	0.000	0.000
S1	0.0180 (8)	0.0194 (8)	0.0234 (7)	0.0099 (7)	−0.0012 (6)	0.0018 (6)
N1	0.027 (3)	0.030 (3)	0.020 (2)	0.016 (3)	−0.002 (2)	−0.003 (2)
N2	0.026 (3)	0.030 (3)	0.063 (4)	0.011 (3)	0.012 (3)	−0.007 (3)
C2	0.025 (4)	0.034 (4)	0.030 (3)	0.022 (3)	0.006 (3)	−0.002 (3)
O1	0.030 (2)	0.030 (2)	0.016 (3)	0.0150 (12)	0.000	0.000
C1	0.024 (4)	0.023 (3)	0.021 (3)	0.012 (3)	−0.002 (3)	−0.003 (3)
C4	0.022 (4)	0.029 (4)	0.039 (4)	0.010 (3)	−0.003 (3)	−0.003 (3)
C5	0.031 (4)	0.021 (4)	0.037 (4)	0.013 (3)	0.004 (3)	−0.004 (3)
C3	0.024 (4)	0.037 (4)	0.022 (3)	0.020 (3)	−0.001 (3)	0.003 (3)
C6	0.029 (4)	0.066 (5)	0.040 (4)	0.030 (4)	0.006 (3)	0.006 (4)

Geometric parameters (Å, º) top

Cu1—N1	2.033 (4)	N1—C5	1.344 (7)
Cu1—S1ⁱ	2.2886 (15)	N1—C1	1.344 (6)
Cu1—S1ⁱⁱ	2.3353 (15)	N2—C1	1.350 (7)
Cu1—S1	2.4701 (16)	N2—H2A	0.8600
Cu1—V1	2.6932 (11)	N2—H2B	0.8600
Cu1—Cu1ⁱⁱ	2.7725 (10)	C2—C3	1.366 (8)
Cu1—Cu1ⁱ	2.7725 (10)	C2—C1	1.387 (7)
V1—O1	1.618 (6)	C2—H2C	0.9300
V1—S1ⁱⁱ	2.2382 (15)	C4—C3	1.373 (8)
V1—S1ⁱⁱⁱ	2.2382 (15)	C4—C5	1.374 (7)
V1—S1ⁱ	2.2382 (15)	C4—H4A	0.9300
V1—Cu1^iv	2.6932 (11)	C5—H5A	0.9300
V1—Cu1^v	2.6932 (11)	C3—C6	1.498 (7)
S1—V1ⁱⁱⁱ	2.2382 (15)	C6—H6A	0.9600
S1—Cu1ⁱⁱ	2.2886 (15)	C6—H6B	0.9600
S1—Cu1ⁱ	2.3353 (15)	C6—H6C	0.9600

N1—Cu1—S1ⁱ	121.11 (14)	S1ⁱⁱⁱ—V1—Cu1	126.41 (7)
N1—Cu1—S1ⁱⁱ	107.71 (14)	S1ⁱ—V1—Cu1	54.36 (4)
S1ⁱ—Cu1—S1ⁱⁱ	104.91 (7)	Cu1^iv—V1—Cu1	90.91 (4)
N1—Cu1—S1	104.52 (13)	Cu1^v—V1—Cu1	90.91 (4)
S1ⁱ—Cu1—S1	109.83 (6)	V1ⁱⁱⁱ—S1—Cu1ⁱⁱ	73.01 (5)
S1ⁱⁱ—Cu1—S1	108.29 (5)	V1ⁱⁱⁱ—S1—Cu1ⁱ	72.12 (5)
N1—Cu1—V1	132.40 (12)	Cu1ⁱⁱ—S1—Cu1ⁱ	112.24 (6)
S1ⁱ—Cu1—V1	52.63 (4)	V1ⁱⁱⁱ—S1—Cu1	111.28 (7)
S1ⁱⁱ—Cu1—V1	52.27 (4)	Cu1ⁱⁱ—S1—Cu1	71.15 (4)
S1—Cu1—V1	122.30 (5)	Cu1ⁱ—S1—Cu1	70.41 (4)
N1—Cu1—Cu1ⁱⁱ	114.62 (14)	C5—N1—C1	116.4 (5)
S1ⁱ—Cu1—Cu1ⁱⁱ	124.25 (4)	C5—N1—Cu1	115.9 (4)
S1ⁱⁱ—Cu1—Cu1ⁱⁱ	57.07 (4)	C1—N1—Cu1	127.6 (4)
S1—Cu1—Cu1ⁱⁱ	51.37 (4)	C1—N2—H2A	120.0
V1—Cu1—Cu1ⁱⁱ	90.71 (3)	C1—N2—H2B	120.0
N1—Cu1—Cu1ⁱ	127.78 (13)	H2A—N2—H2B	120.0
S1ⁱ—Cu1—Cu1ⁱ	57.48 (4)	C3—C2—C1	121.3 (5)
S1ⁱⁱ—Cu1—Cu1ⁱ	123.48 (4)	C3—C2—H2C	119.4
S1—Cu1—Cu1ⁱ	52.52 (4)	C1—C2—H2C	119.4
V1—Cu1—Cu1ⁱ	90.71 (3)	N1—C1—N2	118.1 (5)
Cu1ⁱⁱ—Cu1—Cu1ⁱ	87.63 (4)	N1—C1—C2	121.6 (5)
O1—V1—S1ⁱⁱ	108.97 (5)	N2—C1—C2	120.2 (5)
O1—V1—S1ⁱⁱⁱ	108.97 (5)	C3—C4—C5	119.3 (5)
S1ⁱⁱ—V1—S1ⁱⁱⁱ	109.97 (5)	C3—C4—H4A	120.3
O1—V1—S1ⁱ	108.97 (5)	C5—C4—H4A	120.3
S1ⁱⁱ—V1—S1ⁱ	109.97 (5)	N1—C5—C4	124.1 (5)
S1ⁱⁱⁱ—V1—S1ⁱ	109.97 (5)	N1—C5—H5A	117.9
O1—V1—Cu1^iv	124.62 (3)	C4—C5—H5A	117.9
S1ⁱⁱ—V1—Cu1^iv	54.36 (4)	C2—C3—C4	117.2 (5)
S1ⁱⁱⁱ—V1—Cu1^iv	55.61 (4)	C2—C3—C6	121.0 (5)
S1ⁱ—V1—Cu1^iv	126.41 (7)	C4—C3—C6	121.8 (6)
O1—V1—Cu1^v	124.62 (3)	C3—C6—H6A	109.5
S1ⁱⁱ—V1—Cu1^v	126.41 (7)	C3—C6—H6B	109.5
S1ⁱⁱⁱ—V1—Cu1^v	54.36 (4)	H6A—C6—H6B	109.5
S1ⁱ—V1—Cu1^v	55.61 (4)	C3—C6—H6C	109.5
Cu1^iv—V1—Cu1^v	90.91 (4)	H6A—C6—H6C	109.5
O1—V1—Cu1	124.62 (3)	H6B—C6—H6C	109.5
S1ⁱⁱ—V1—Cu1	55.61 (4)

Symmetry codes: (i) y−1, −x+y, −z+2; (ii) x−y+1, x+1, −z+2; (iii) −x, −y+2, −z+2; (iv) −y+1, x−y+2, z; (v) −x+y−1, −x+1, z.

Experimental details

Crystal data
Chemical formula	[Cu₆V₂O₂S₆(C₆H₈N₂)₆]
M_r	1356.34
Crystal system, space group	Hexagonal, R3
Temperature (K)	293
a, c (Å)	14.139 (2), 20.830 (4)
V (Å³)	3606.2 (10)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	3.28
Crystal size (mm)	0.3 × 0.2 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.465, 0.611
No. of measured, independent and observed [I > 2σ(I)] reflections	6168, 1837, 1092
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.128, 1.02
No. of reflections	1837
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.69

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Acknowledgements

This project was supported by the Natural Science Foundation of Jiangsu Educational Office

References

Bruker (2000). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Du, S. W., Zhu, N. Y., Chen, P. C. & Wu, X. T. (1992). Angew. Chem. Int. Ed. Engl. 31, 1085–1089. CSD CrossRef Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Holm, R. H. (1992). Adv. Inorg. Chem. 38, 1–10. CrossRef CAS Google Scholar
Hou, H. W., Xin, X. Q. & Shi, S. (1996). Coord. Chem. Rev. 153, 25–56. CrossRef CAS Web of Science Google Scholar
Liu, Q. T., Yang, Y., Huang, L. R., Wu, D. X., Kang, B. S., Chen, C. N., Deng, Y. H. & Lu, J. X. (1995). Inorg. Chem. 34, 1884–1893. CSD CrossRef CAS Web of Science Google Scholar
Naruta, Y., Sasayama, M. & Sasaki, T. (1994). Angew. Chem. Int. Ed. Engl. 33, 1839–1843. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, C., Jin, G., Chen, J., Xin, X. & Qian, K. (2001). Coord. Chem. Rev. 213, 51–72. Web of Science CrossRef CAS Google Scholar
Zhang, H. H., Yu, X. F., Yang, R. S., Zheng, F. K., Huang, L. Y. & Zhou, R. P. (1996). Chin. J. Struct. Chem. 15, 353-357. CAS Google Scholar
Zheng, F. K., Guo, G. C., Zhou, G. W., Zhang, X. & Huang, J. S. (2001). Chin. J. Struct. Chem. 20, 489–493. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.