Bis(2,2'-bipyridine)iodo­(oxo)tri-[mu]₃-sulfido-tricopper(I)tungsten(VI)

The title nest-shaped cluster, [Cu₃WIOS₃(C₁₀H₈N₂)₂], has been synthesized by the reaction of (NH₄)₂[WOS₃], CuI and 2,2'-bipyridine (bipy) in dimethyl­formamide under a purified nitro­gen atmosphere. The cluster has a neutral skeleton containing the bipy ligands, and the central W atom is tetra­hedrally coordinated by three S atoms and one O atom. The three Cu atoms are divided into two different kinds. Two Cu atoms adopt distorted tetra­hedral geometry, with each Cu atom coordinated by two S atoms and the two N atoms of a bipy ligand. The other Cu atom adopts a trigonal mode surrounded by two S atoms and one I atom.

S1. Comment

Research into chalcogenometallate anions [MO_nS_4-n]²⁻ (M = Mo and W; n = 0–2) and their related cluster compounds has been a comparatively active field in modern chemistry, physics and materials science because of the interesting electronic, biological, optical, structural and catalytic properties of these compounds (Marks et al., 1995; Gray & Lawson, 1999). Current research activity concerning the Mo(W)/Cu(Ag)/S clusters is aimed at properties such as catalysis, conductivity and strong nonlinear optical (NLO) characteristics (Fujita et al., 1994; Aumuller et al., 1986; Hou et al., 1996). The literature on this subject is exhaustive, but it mainly focuses on a narrow scope of structure types in which the ligands attached to the Cu (Ag) atoms are only halogen, pyridine, PPh₃ or their analogues showing strong affinities to Cu^I and so shows limitation in the advantage of easy structural modification. As far as we know, there are only a limited number of nest-shaped clusters with a 2,2'-bipy skeleton, and these were reported recently (Hu, Wang et al., 2003; Hu, Zheng et al., 2003; Li et al., 2004). In an attempt to search for better NLO materials, we report here the synthesis and crystal structure of the title compound, (I), [Cu₃WIOS₃(bipy)₂].

Fig. 1 shows the molecular structure of (I) with the atomic labelling scheme. Selected bond lengths and angles are listed in Table 1. Atom W1 is tetrahedrally coordinated by atom O1 and the three µ₃-S atoms, which, in turn, coordinate with the three Cu atoms. Within the core, the W—O bond length of 1.717 (4) Å is characteristic of a double bond, while the W—S bond distances 2.2531 (18)–2.2649 (17) Å indicate single bonds. The three Cu atoms are divided into two different kinds. Atom Cu3 adopts a trigonal mode, surrounded by two µ₃-S atoms and one I atom, to form the [CuS₂I] unit. Atoms Cu1 and Cu2 adopt distorted tetrahedral geometry, with each Cu atom coordinated by two µ₃-S atoms and two N atoms of the 2,2'-bipy ligand, forming a [CuS₂(bipy)] unit. Owing to their different coordination modes, atom Cu3 has a slightly shorter Cu—W distance than atoms Cu1 and Cu2. The bipy ligands act as bidentate ligands to atoms Cu1 and Cu2. As shown in Fig. 2, the complexes are linked via C—H···O interactions (Table 2), forming a chain structure along the a axis.

S2. Experimental

All reactions and manipulations were performed in oven-dried glassware under a purified nitrogen atmosphere using standard Schlenk techniques. The solvents and other chemicals were commercially available and used without further purification. The starting material [NH₄]₂[WOS₃] was prepared according to the literature (McDonald et al., 1983). A well ground mixture of CuI (0.191 g, 1.0 mmol), (NH₄)₂WOS₃ (0.174 g, 0.5 mmol), 2,2'-bipy (0.156 g, 1.0 mmol) and (n-Bu)₄NI (0.369 g, 1.0 mmol) was added to CH₂Cl₂ (15 ml) and stirred for 12 h under pure nitrogen. The red solution was filtered and i-PrOH (40 ml) was added to the filtrate. The filtrate was left to stand for several days and red–brown crystals were produced (yield 0.25 g, 27%). Analysis calculated for C₂₀H₁₆Cu₃IN₄OS₃W: C 25.94, H 1.74, N 6.05%; found: C 25.98, H 1.78, N 6.01%.

S3. Refinement

All H atoms were positioned geometrically, with C—H distances of 0.93 Å and U_iso(H) values of 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids.
	Fig. 2. The packing of (I), projected down the b axis. Dotted lines show C—H···O interactions. H atoms have been omitted.

Bis(2,2'-bipyridine)iodo(oxo)tri-µ₃-sulfido-tricopper(I)tungsten(VI)

Crystal data

[Cu3WIOS3(C10H8N2)2]	Z = 2
Mr = 925.97	F(000) = 868
Triclinic, P1	Dx = 2.372 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.895 (1) Å	Cell parameters from 3064 reflections
b = 9.828 (1) Å	θ = 2.4–26.8°
c = 16.331 (2) Å	µ = 8.30 mm^−1
α = 79.66 (1)°	T = 293 K
β = 85.90 (1)°	Block, brown
γ = 67.38 (1)°	0.30 × 0.20 × 0.20 mm
V = 1296.4 (3) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4503 independent reflections
Radiation source: sealed tube	3824 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2000)	h = −10→6
Tmin = 0.148, Tmax = 0.191	k = −11→11
6494 measured reflections	l = −19→19

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.03P)^2] where P = (Fo^2 + 2Fc^2)/3
4503 reflections	(Δ/σ)max = 0.002
298 parameters	Δρmax = 1.33 e Å^−3
0 restraints	Δρmin = −1.35 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
W1	0.47708 (3)	0.61446 (3)	0.221255 (14)	0.03868 (10)
Cu1	0.24673 (10)	0.70810 (9)	0.33506 (5)	0.0487 (2)
Cu2	0.24730 (10)	0.70558 (9)	0.10520 (5)	0.0480 (2)
Cu3	0.41980 (10)	0.36417 (9)	0.25406 (5)	0.0492 (2)
S1	0.2598 (2)	0.83236 (18)	0.20645 (10)	0.0487 (4)
S2	0.4595 (2)	0.47961 (19)	0.12609 (10)	0.0488 (4)
S3	0.4649 (2)	0.48618 (18)	0.34909 (9)	0.0443 (4)
I1	0.34111 (7)	0.14822 (6)	0.28889 (3)	0.06171 (15)
O1	0.6552 (6)	0.6454 (6)	0.2085 (3)	0.0643 (14)
C1	−0.0540 (9)	0.6287 (9)	0.3468 (4)	0.067 (2)
H1	−0.0258	0.6054	0.2937	0.081*
C2	−0.1858 (9)	0.6023 (9)	0.3858 (5)	0.070 (2)
H2	−0.2446	0.5615	0.3601	0.084*
C3	−0.2264 (9)	0.6385 (9)	0.4633 (5)	0.069 (2)
H3	−0.3134	0.6211	0.4916	0.083*
C4	−0.1396 (8)	0.7005 (8)	0.5000 (5)	0.0594 (19)
H4	−0.1688	0.7282	0.5522	0.071*
C5	−0.0068 (7)	0.7210 (7)	0.4573 (4)	0.0450 (15)
C6	0.0983 (8)	0.7820 (7)	0.4931 (4)	0.0439 (15)
C7	0.0741 (10)	0.8223 (8)	0.5722 (4)	0.063 (2)
H7	−0.0113	0.8121	0.6056	0.076*
C8	0.1781 (12)	0.8769 (9)	0.5998 (5)	0.079 (3)
H8	0.1641	0.9043	0.6523	0.095*
C9	0.3031 (10)	0.8908 (8)	0.5493 (5)	0.068 (2)
H9	0.3754	0.9268	0.5673	0.082*
C10	0.3201 (9)	0.8507 (7)	0.4714 (4)	0.0555 (18)
H10	0.4040	0.8618	0.4370	0.067*
N1	0.0348 (6)	0.6858 (6)	0.3817 (3)	0.0490 (14)
N2	0.2209 (6)	0.7969 (5)	0.4438 (3)	0.0428 (12)
C11	0.3648 (9)	0.9037 (8)	−0.0339 (4)	0.0567 (18)
H11	0.4431	0.8934	0.0040	0.068*
C12	0.3647 (9)	0.9844 (8)	−0.1091 (5)	0.063 (2)
H12	0.4400	1.0296	−0.1222	0.075*
C13	0.2522 (10)	0.9995 (9)	−0.1666 (5)	0.070 (2)
H13	0.2502	1.0540	−0.2196	0.085*
C14	0.1421 (8)	0.9320 (8)	−0.1439 (4)	0.0559 (18)
H14	0.0648	0.9404	−0.1820	0.067*
C15	0.1460 (7)	0.8514 (7)	−0.0645 (3)	0.0407 (14)
C16	0.0321 (7)	0.7779 (7)	−0.0329 (4)	0.0426 (15)
C17	−0.0862 (8)	0.7766 (8)	−0.0836 (4)	0.0543 (17)
H17	−0.0949	0.8209	−0.1393	0.065*
C18	−0.1903 (9)	0.7080 (8)	−0.0493 (5)	0.061 (2)
H18	−0.2712	0.7065	−0.0818	0.074*
C19	−0.1752 (8)	0.6428 (8)	0.0315 (5)	0.0573 (18)
H19	−0.2446	0.5959	0.0552	0.069*
C20	−0.0537 (8)	0.6474 (8)	0.0783 (4)	0.0527 (17)
H20	−0.0432	0.6024	0.1339	0.063*
N3	0.2600 (6)	0.8367 (6)	−0.0097 (3)	0.0439 (12)
N4	0.0481 (6)	0.7130 (6)	0.0475 (3)	0.0427 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.04201 (16)	0.05145 (18)	0.03022 (14)	−0.02765 (13)	−0.00218 (10)	−0.00227 (11)
Cu1	0.0528 (5)	0.0556 (5)	0.0388 (4)	−0.0223 (4)	0.0032 (4)	−0.0074 (4)
Cu2	0.0566 (5)	0.0563 (5)	0.0360 (4)	−0.0268 (4)	−0.0124 (4)	−0.0030 (4)
Cu3	0.0561 (5)	0.0440 (5)	0.0516 (5)	−0.0244 (4)	−0.0020 (4)	−0.0051 (4)
S1	0.0697 (11)	0.0397 (9)	0.0373 (8)	−0.0219 (9)	−0.0098 (8)	−0.0015 (7)
S2	0.0565 (10)	0.0523 (10)	0.0390 (9)	−0.0208 (9)	−0.0025 (7)	−0.0096 (7)
S3	0.0509 (9)	0.0484 (10)	0.0339 (8)	−0.0215 (8)	−0.0042 (7)	0.0001 (7)
I1	0.0897 (4)	0.0651 (3)	0.0493 (3)	−0.0499 (3)	0.0082 (2)	−0.0130 (2)
O1	0.062 (3)	0.091 (4)	0.057 (3)	−0.052 (3)	0.004 (2)	−0.005 (3)
C1	0.076 (5)	0.096 (6)	0.041 (4)	−0.048 (5)	−0.017 (4)	0.001 (4)
C2	0.059 (5)	0.099 (6)	0.065 (5)	−0.051 (5)	−0.024 (4)	0.014 (5)
C3	0.040 (4)	0.088 (6)	0.072 (5)	−0.026 (4)	−0.004 (4)	0.013 (5)
C4	0.051 (4)	0.056 (5)	0.057 (4)	−0.010 (4)	0.001 (3)	0.000 (4)
C5	0.040 (4)	0.045 (4)	0.042 (4)	−0.013 (3)	−0.005 (3)	0.006 (3)
C6	0.051 (4)	0.038 (4)	0.035 (3)	−0.008 (3)	−0.004 (3)	−0.003 (3)
C7	0.075 (5)	0.059 (5)	0.048 (4)	−0.019 (4)	−0.006 (4)	−0.004 (4)
C8	0.104 (7)	0.072 (6)	0.054 (5)	−0.018 (5)	−0.020 (5)	−0.022 (4)
C9	0.077 (6)	0.053 (5)	0.070 (5)	−0.013 (4)	−0.028 (5)	−0.016 (4)
C10	0.063 (5)	0.046 (4)	0.058 (4)	−0.021 (4)	−0.018 (4)	−0.002 (3)
N1	0.048 (3)	0.066 (4)	0.038 (3)	−0.028 (3)	−0.005 (2)	−0.005 (3)
N2	0.045 (3)	0.038 (3)	0.041 (3)	−0.011 (2)	−0.008 (2)	−0.003 (2)
C11	0.064 (5)	0.073 (5)	0.049 (4)	−0.043 (4)	−0.002 (3)	−0.009 (4)
C12	0.070 (5)	0.068 (5)	0.062 (5)	−0.038 (4)	0.013 (4)	−0.016 (4)
C13	0.079 (6)	0.068 (5)	0.054 (5)	−0.026 (5)	0.013 (4)	0.008 (4)
C14	0.052 (4)	0.069 (5)	0.041 (4)	−0.019 (4)	−0.014 (3)	0.001 (3)
C15	0.042 (3)	0.045 (4)	0.035 (3)	−0.016 (3)	−0.002 (3)	−0.006 (3)
C16	0.047 (4)	0.041 (4)	0.040 (4)	−0.014 (3)	−0.008 (3)	−0.009 (3)
C17	0.052 (4)	0.063 (5)	0.052 (4)	−0.025 (4)	−0.016 (3)	−0.009 (3)
C18	0.050 (4)	0.074 (5)	0.071 (5)	−0.028 (4)	−0.016 (4)	−0.023 (4)
C19	0.046 (4)	0.067 (5)	0.072 (5)	−0.031 (4)	0.006 (4)	−0.025 (4)
C20	0.049 (4)	0.070 (5)	0.050 (4)	−0.032 (4)	0.005 (3)	−0.016 (4)
N3	0.048 (3)	0.052 (3)	0.039 (3)	−0.026 (3)	−0.003 (2)	−0.009 (2)
N4	0.045 (3)	0.054 (3)	0.037 (3)	−0.026 (3)	−0.001 (2)	−0.009 (2)

Geometric parameters (Å, º)

W1—O1	1.717 (4)	C6—C7	1.396 (9)
W1—S1	2.2531 (18)	C7—C8	1.369 (11)
W1—S3	2.2556 (15)	C7—H7	0.9300
W1—S2	2.2649 (17)	C8—C9	1.372 (11)
W1—Cu3	2.6551 (8)	C8—H8	0.9300
W1—Cu2	2.6662 (8)	C9—C10	1.379 (10)
W1—Cu1	2.6680 (9)	C9—H9	0.9300
Cu1—N1	2.057 (5)	C10—N2	1.328 (8)
Cu1—N2	2.076 (5)	C10—H10	0.9300
Cu1—S1	2.2517 (17)	C11—N3	1.336 (8)
Cu1—S3	2.2810 (19)	C11—C12	1.337 (9)
Cu2—N4	2.037 (5)	C11—H11	0.9300
Cu2—N3	2.099 (5)	C12—C13	1.369 (10)
Cu2—S1	2.2741 (18)	C12—H12	0.9300
Cu2—S2	2.2818 (19)	C13—C14	1.377 (10)
Cu3—S2	2.2650 (17)	C13—H13	0.9300
Cu3—S3	2.2658 (18)	C14—C15	1.388 (8)
Cu3—I1	2.4435 (9)	C14—H14	0.9300
C1—N1	1.336 (8)	C15—N3	1.350 (7)
C1—C2	1.384 (10)	C15—C16	1.473 (8)
C1—H1	0.9300	C16—N4	1.345 (7)
C2—C3	1.363 (11)	C16—C17	1.390 (8)
C2—H2	0.9300	C17—C18	1.377 (9)
C3—C4	1.373 (10)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.350 (10)
C4—C5	1.391 (9)	C18—H18	0.9300
C4—H4	0.9300	C19—C20	1.386 (9)
C5—N1	1.331 (8)	C19—H19	0.9300
C5—C6	1.487 (9)	C20—N4	1.326 (8)
C6—N2	1.347 (8)	C20—H20	0.9300
O1—W1—S1	110.80 (18)	C4—C3—H3	119.8
O1—W1—S3	110.76 (16)	C3—C4—C5	118.4 (7)
S1—W1—S3	108.07 (6)	C3—C4—H4	120.8
O1—W1—S2	110.50 (18)	C5—C4—H4	120.8
S1—W1—S2	108.58 (6)	N1—C5—C4	121.8 (6)
S3—W1—S2	108.03 (6)	N1—C5—C6	115.7 (5)
O1—W1—Cu3	131.77 (18)	C4—C5—C6	122.5 (6)
S1—W1—Cu3	117.43 (5)	N2—C6—C7	121.2 (6)
S3—W1—Cu3	54.22 (5)	N2—C6—C5	115.5 (5)
S2—W1—Cu3	54.12 (4)	C7—C6—C5	123.3 (6)
O1—W1—Cu2	124.40 (16)	C8—C7—C6	119.0 (7)
S1—W1—Cu2	54.28 (5)	C8—C7—H7	120.5
S3—W1—Cu2	124.84 (5)	C6—C7—H7	120.5
S2—W1—Cu2	54.39 (5)	C7—C8—C9	119.3 (8)
Cu3—W1—Cu2	85.99 (3)	C7—C8—H8	120.3
O1—W1—Cu1	126.51 (17)	C9—C8—H8	120.3
S1—W1—Cu1	53.66 (5)	C8—C9—C10	119.1 (8)
S3—W1—Cu1	54.42 (5)	C8—C9—H9	120.4
S2—W1—Cu1	122.99 (5)	C10—C9—H9	120.4
Cu3—W1—Cu1	84.69 (3)	N2—C10—C9	122.4 (7)
Cu2—W1—Cu1	89.58 (3)	N2—C10—H10	118.8
N1—Cu1—N2	79.5 (2)	C9—C10—H10	118.8
N1—Cu1—S1	121.81 (15)	C5—N1—C1	118.4 (6)
N2—Cu1—S1	124.53 (15)	C5—N1—Cu1	114.9 (4)
N1—Cu1—S3	112.81 (16)	C1—N1—Cu1	126.4 (5)
N2—Cu1—S3	108.65 (14)	C10—N2—C6	119.0 (6)
S1—Cu1—S3	107.24 (7)	C10—N2—Cu1	126.9 (5)
N1—Cu1—W1	141.09 (16)	C6—N2—Cu1	113.8 (4)
N2—Cu1—W1	137.72 (15)	N3—C11—C12	124.4 (7)
S1—Cu1—W1	53.71 (5)	N3—C11—H11	117.8
S3—Cu1—W1	53.54 (4)	C12—C11—H11	117.8
N4—Cu2—N3	79.56 (19)	C11—C12—C13	119.0 (7)
N4—Cu2—S1	129.03 (16)	C11—C12—H12	120.5
N3—Cu2—S1	107.22 (14)	C13—C12—H12	120.5
N4—Cu2—S2	116.21 (16)	C12—C13—C14	118.3 (7)
N3—Cu2—S2	113.02 (15)	C12—C13—H13	120.8
S1—Cu2—S2	107.27 (6)	C14—C13—H13	120.8
N4—Cu2—W1	157.25 (14)	C13—C14—C15	120.3 (6)
N3—Cu2—W1	122.70 (13)	C13—C14—H14	119.9
S1—Cu2—W1	53.56 (5)	C15—C14—H14	119.9
S2—Cu2—W1	53.80 (4)	N3—C15—C14	120.0 (5)
S2—Cu3—S3	107.67 (6)	N3—C15—C16	115.1 (5)
S2—Cu3—I1	127.99 (5)	C14—C15—C16	124.9 (6)
S3—Cu3—I1	124.34 (5)	N4—C16—C17	121.9 (6)
S2—Cu3—W1	54.11 (5)	N4—C16—C15	116.5 (5)
S3—Cu3—W1	53.86 (4)	C17—C16—C15	121.6 (6)
I1—Cu3—W1	174.48 (4)	C18—C17—C16	118.3 (6)
Cu1—S1—W1	72.64 (5)	C18—C17—H17	120.8
Cu1—S1—Cu2	112.27 (7)	C16—C17—H17	120.8
W1—S1—Cu2	72.16 (6)	C19—C18—C17	120.1 (6)
W1—S2—Cu3	71.76 (5)	C19—C18—H18	119.9
W1—S2—Cu2	71.80 (6)	C17—C18—H18	119.9
Cu3—S2—Cu2	105.89 (7)	C18—C19—C20	118.5 (6)
W1—S3—Cu3	71.92 (5)	C18—C19—H19	120.7
W1—S3—Cu1	72.04 (5)	C20—C19—H19	120.7
Cu3—S3—Cu1	104.11 (7)	N4—C20—C19	123.0 (6)
N1—C1—C2	123.3 (7)	N4—C20—H20	118.5
N1—C1—H1	118.3	C19—C20—H20	118.5
C2—C1—H1	118.3	C11—N3—C15	118.0 (5)
C3—C2—C1	117.6 (7)	C11—N3—Cu2	128.5 (4)
C3—C2—H2	121.2	C15—N3—Cu2	113.5 (4)
C1—C2—H2	121.2	C20—N4—C16	118.2 (5)
C2—C3—C4	120.5 (7)	C20—N4—Cu2	126.6 (4)
C2—C3—H3	119.8	C16—N4—Cu2	114.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^i	0.93	2.57	3.202 (9)	126

Symmetry code: (i) x−1, y, z.