Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106007438/ob1248sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106007438/ob1248Isup2.hkl |
CCDC reference: 238241
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%.
All H atoms were positioned geometrically, with C—H distances of 0.93 Å and Uiso(H) values of 1.2Ueq(C).
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.
[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) Å3 |
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 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.03P)2] where P = (Fo2 + 2Fc2)/3 |
4503 reflections | (Δ/σ)max = 0.002 |
298 parameters | Δρmax = 1.33 e Å−3 |
0 restraints | Δρmin = −1.35 e Å−3 |
[Cu3WIOS3(C10H8N2)2] | γ = 67.38 (1)° |
Mr = 925.97 | V = 1296.4 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.895 (1) Å | Mo Kα radiation |
b = 9.828 (1) Å | µ = 8.30 mm−1 |
c = 16.331 (2) Å | T = 293 K |
α = 79.66 (1)° | 0.30 × 0.20 × 0.20 mm |
β = 85.90 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 4503 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2000) | 3824 reflections with I > 2σ(I) |
Tmin = 0.148, Tmax = 0.191 | Rint = 0.026 |
6494 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.33 e Å−3 |
4503 reflections | Δρmin = −1.35 e Å−3 |
298 parameters |
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 | ||
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.93 | 2.57 | 3.202 (9) | 126 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu3WIOS3(C10H8N2)2] |
Mr | 925.97 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.895 (1), 9.828 (1), 16.331 (2) |
α, β, γ (°) | 79.66 (1), 85.90 (1), 67.38 (1) |
V (Å3) | 1296.4 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 8.30 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.148, 0.191 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6494, 4503, 3824 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.079, 1.05 |
No. of reflections | 4503 |
No. of parameters | 298 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.33, −1.35 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
W1—O1 | 1.717 (4) | Cu1—S1 | 2.2517 (17) |
W1—S1 | 2.2531 (18) | Cu1—S3 | 2.2810 (19) |
W1—S3 | 2.2556 (15) | Cu2—N4 | 2.037 (5) |
W1—S2 | 2.2649 (17) | Cu2—N3 | 2.099 (5) |
W1—Cu3 | 2.6551 (8) | Cu2—S1 | 2.2741 (18) |
W1—Cu2 | 2.6662 (8) | Cu2—S2 | 2.2818 (19) |
W1—Cu1 | 2.6680 (9) | Cu3—S2 | 2.2650 (17) |
Cu1—N1 | 2.057 (5) | Cu3—S3 | 2.2658 (18) |
Cu1—N2 | 2.076 (5) | Cu3—I1 | 2.4435 (9) |
O1—W1—S1 | 110.80 (18) | N2—Cu1—S3 | 108.65 (14) |
O1—W1—S3 | 110.76 (16) | S1—Cu1—S3 | 107.24 (7) |
S1—W1—S3 | 108.07 (6) | N4—Cu2—S1 | 129.03 (16) |
O1—W1—S2 | 110.50 (18) | N3—Cu2—S1 | 107.22 (14) |
S1—W1—S2 | 108.58 (6) | N4—Cu2—S2 | 116.21 (16) |
S3—W1—S2 | 108.03 (6) | N3—Cu2—S2 | 113.02 (15) |
N1—Cu1—N2 | 79.5 (2) | S1—Cu2—S2 | 107.27 (6) |
N1—Cu1—S1 | 121.81 (15) | S2—Cu3—S3 | 107.67 (6) |
N2—Cu1—S1 | 124.53 (15) | S2—Cu3—I1 | 127.99 (5) |
N1—Cu1—S3 | 112.81 (16) | S3—Cu3—I1 | 124.34 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.93 | 2.57 | 3.202 (9) | 126 |
Symmetry code: (i) x−1, y, z. |
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Research into chalcogenometallate anions [MOnS4-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 CuI 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.