Acta Cryst. (2008). E64, m1217 [ doi:10.1107/S1600536808027165 ]
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N1)dioxidohexa-![[mu]](/logos/entities/mu_rmgif.gif)
4-sulfido-hexacopper(I)divanadium(V)The title compound, [Cu6V2O2S6(C6H8N2)6], is constructed from six CuS3N and two VOS3 distorted tetrahedra, forming an octanuclear V/S/Cu cluster with Ci 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.
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.
The amino hydrogen atoms were found from Fourier difference maps and fixed with N—H bond lengths of 0.90 Å. The H atoms of the aromatic group were geometrically idealized. All the H atoms were refined isotropically with isotropic vibration parameters related to the atoms to which they are bonded with Uĩso~ = 1.2 U~eq~ (Uĩso~ = 1.5U~eq~ for methyl H atoms).
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).
![[Figure 1]](./bv2103fig1thm.gif)
| Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids. All H atoms have been omitted. |
![[Figure 2]](./bv2103fig2thm.gif)
| Fig. 2. Cubic arrangement of metal atoms. |
| [Cu6V2O2S6(C6H8N2)6] | Z = 3 |
| Mr = 1356.34 | F000 = 2040 |
| Hexagonal, R3 | Dx = 1.874 Mg m−3 |
| Hall symbol: -R 3 | Mo Kα radiation λ = 0.71073 Å |
| a = 14.139 (2) Å | Cell parameters from 6634 reflections |
| b = 14.139 (2) Å | θ = 1.9–27.5º |
| c = 20.830 (4) Å | µ = 3.28 mm−1 |
| α = 90º | T = 293 (2) K |
| β = 90º | Block, black |
| γ = 120º | 0.3 × 0.2 × 0.15 mm |
| V = 3606.2 (10) Å3 |
| Bruker APEXII CCD diffractometer | 1837 independent reflections |
| Radiation source: fine-focus sealed tube | 1092 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.054 |
| T = 293(2) K | θmax = 27.5º |
| φ and ω scans | θmin = 1.9º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −17→18 |
| Tmin = 0.465, Tmax = 0.611 | k = −12→18 |
| 6168 measured reflections | l = −26→27 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
| wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0525P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max = 0.001 |
| 1837 reflections | Δρmax = 0.58 e Å−3 |
| 97 parameters | Δρmin = −0.69 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Cu6V2O2S6(C6H8N2)6] | γ = 120º |
| Mr = 1356.34 | V = 3606.2 (10) Å3 |
| Hexagonal, R3 | Z = 3 |
| a = 14.139 (2) Å | Mo Kα |
| b = 14.139 (2) Å | µ = 3.28 mm−1 |
| c = 20.830 (4) Å | T = 293 (2) K |
| α = 90º | 0.3 × 0.2 × 0.15 mm |
| β = 90º |
| Bruker APEXII CCD diffractometer | 1837 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1092 reflections with I > 2σ(I) |
| Tmin = 0.465, Tmax = 0.611 | Rint = 0.054 |
| 6168 measured reflections |
| R[F2 > 2σ(F2)] = 0.050 | 97 parameters |
| wR(F2) = 0.128 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 0.58 e Å−3 |
| 1837 reflections | Δρmin = −0.69 e Å−3 |
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 | ||
| 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* |
| 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) |
| 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—Cu1iv | 2.6932 (11) | C5—H5A | 0.9300 |
| V1—Cu1v | 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) | Cu1iv—V1—Cu1 | 90.91 (4) |
| N1—Cu1—S1 | 104.52 (13) | Cu1v—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—Cu1iv | 124.62 (3) | C4—C5—H5A | 117.9 |
| S1ii—V1—Cu1iv | 54.36 (4) | C2—C3—C4 | 117.2 (5) |
| S1iii—V1—Cu1iv | 55.61 (4) | C2—C3—C6 | 121.0 (5) |
| S1i—V1—Cu1iv | 126.41 (7) | C4—C3—C6 | 121.8 (6) |
| O1—V1—Cu1v | 124.62 (3) | C3—C6—H6A | 109.5 |
| S1ii—V1—Cu1v | 126.41 (7) | C3—C6—H6B | 109.5 |
| S1iii—V1—Cu1v | 54.36 (4) | H6A—C6—H6B | 109.5 |
| S1i—V1—Cu1v | 55.61 (4) | C3—C6—H6C | 109.5 |
| Cu1iv—V1—Cu1v | 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. |
This project was supported by the Natural Science Foundation of Jiangsu Educational Office
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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)(Liuet 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.