Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103022078/ln1179sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103022078/ln1179Isup2.hkl |
CCDC reference: 226104
(NH4)2[WS4] was prepared according to the literature method (McDonald et al., 1983). To a suspension produced by combining CuCN (0.89 g, 10 mmol) and KCN (0.70 g, 10.77 mmol) in water (20 ml) was added solid (NH4)2[WS4] (1.74 g, 5 mmol). The mixture was stirred for 1 h and filtered. The addition of a solution of PPh4Br (4.19 g, 10 mmol) in water (10 ml) produced a yellow precipitate, which was filtered off, washed with water and dissolved in acetonitril (60 ml). Evaporation of the solvent produced yellow platelets of (I), which were collected by filtration, washed with methanol and diethyl ether, and dried in vacuo (yield 5.29 g, 86%). IR (KBr disk, cm-1): υ(C—N) 2123 (m); υ(W—S) 457 (m), 417 (w). The crystal used for the structure determination was obtained directly from the above preparation.
The positions of the H atoms of the water molecule were located from a difference Fourier map and were refined freely, along with the isotropic displacement parameters. The acetonitrile H atoms were constrained to an ideal geometry [C—H = 0.96 Å, with Uiso(H) = 1.5Ueq(C)]. All other H atoms were placed in idealized positions (C—H = 0.93 Å) and constrained to ride on their parent atoms [Uiso(H) = 1.2Ueq(C)].
In the past decade, the third-order non-linear optical (NLO) properties of group IB–VIB chalcogenide clusters derived from tetrathiometallate ([MS4]2-; M = Mo and W) anions have been studied extensively (Shi et al., 1994; Shi, 1998; Yu et al., 2001). However, only a few Mo(W)/Cu(Ag)/S clusters containing cyanides have been prepared and confirmed to exhibit good NLO properties in solution (Hou et al., 1999; Zhang et al., 2000). To find clusters with better NLO properties, we carried out the reaction of CuCN and KCN with (NH4)2[WS4]. We report here the structure of the title trinuclear W/Cu/S cluster, (I).
The asymmetric unit of (I) contains one discrete cluster anion, two [PPh4]+ cations, one acetonitrile molecule and one water molecule (Fig. 1). Being isostructural with its molybdenum analogue (Gheller, et al., 1984), the dianion of (I) consists of a central WS4 moiety and two CuCN groups, which are connected via µ-S atoms. However, the dianion is slightly distorted from D2 d symmetry by small bends of 6–8° at all three metal atoms along the NC—Cu—W—Cu—CN axis (Table 1). The two Cu—C—N angles also deviate from linearity (by 2–4°). The two WCuS2 rhombuses are not quite planar but are essentially perpendicularly disposed to one another.
Each of the two Cu atoms adopts an approximately trigonal-planar coordination geometry. The WS4 moiety is a slightly distorted tetrahedron, with S—W—S bond angles ranging from 107.34 (4) to 112.17 (5)°. The mean W—µ-S bond length shows an apparent elongation of 0.052 (11) Å compared with that in free [WS4]2- [2.165 (3) Å] (Sasvari, 1963) as a result of binding two CuCN groups. The mean W—Cu distance [2.6504 (6) Å] is comparable to those found in three-coordinate Cu clusters, such as [PPh4]2[(η5-C5Me5)WS3Cu3Br3]2 [2.661 (1) Å] (Lang et al., 1997) and [PPh4][{(η5-C5Me5) WS3Cu2}2S2]2 [2.677 (3) Å] (Lang & Tatsumi, 1998). The mean Cu—µ-S and Cu—C distances are similar to those in the corresponding molybdenum analogue [Cu—µ-S = 2.210 (2) Å and Cu—C = 1.886 (9) Å; Gheller et al., 1984].
Each water molecule acts as a donor for two intermolecular hydrogen bonds (Table 2). The acceptor atoms are the cyano N atoms from opposite ends of two adjacent anions. These interactions link an alternating sequence of anions and water molecules into extended chains that run in the [1–10] direction.
Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).
Fig. 1. View of the asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. |
(C24H20P)2[Cu2WS4(CN)2]·C2H3N·H2O | Z = 2 |
Mr = 1229.07 | F(000) = 1224 |
Triclinic, P1 | Dx = 1.586 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6193 (2) Å | Cell parameters from 6823 reflections |
b = 12.7441 (10) Å | θ = 3.0–27.5° |
c = 20.7526 (3) Å | µ = 3.31 mm−1 |
α = 72.922 (9)° | T = 193 K |
β = 76.449 (9)° | Prism, orange |
γ = 77.159 (10)° | 0.40 × 0.35 × 0.30 mm |
V = 2574.1 (3) Å3 |
Rigaku Mercury CCD area-detector diffractometer | 11796 independent reflections |
Radiation source: fine-focus sealed tube | 10551 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −16→16 |
Tmin = 0.260, Tmax = 0.370 | l = −26→26 |
25798 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0435P)2 + 3.3249P] where P = (Fo2 + 2Fc2)/3 |
11567 reflections | (Δ/σ)max = 0.001 |
594 parameters | Δρmax = 1.02 e Å−3 |
0 restraints | Δρmin = −0.84 e Å−3 |
(C24H20P)2[Cu2WS4(CN)2]·C2H3N·H2O | γ = 77.159 (10)° |
Mr = 1229.07 | V = 2574.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.6193 (2) Å | Mo Kα radiation |
b = 12.7441 (10) Å | µ = 3.31 mm−1 |
c = 20.7526 (3) Å | T = 193 K |
α = 72.922 (9)° | 0.40 × 0.35 × 0.30 mm |
β = 76.449 (9)° |
Rigaku Mercury CCD area-detector diffractometer | 11796 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 10551 reflections with I > 2σ(I) |
Tmin = 0.260, Tmax = 0.370 | Rint = 0.030 |
25798 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 1.02 e Å−3 |
11567 reflections | Δρmin = −0.84 e Å−3 |
594 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 | 0.191801 (14) | 0.456795 (13) | 0.213625 (7) | 0.03355 (6) | |
Cu1 | 0.04607 (5) | 0.65710 (4) | 0.18518 (2) | 0.03762 (11) | |
Cu2 | 0.33923 (5) | 0.26156 (4) | 0.25402 (3) | 0.04664 (13) | |
S1 | 0.02834 (10) | 0.52665 (11) | 0.28493 (5) | 0.0517 (3) | |
S2 | 0.20355 (11) | 0.58110 (10) | 0.11241 (5) | 0.0446 (2) | |
S3 | 0.37574 (9) | 0.42850 (9) | 0.25390 (5) | 0.0383 (2) | |
S4 | 0.16032 (13) | 0.29406 (11) | 0.20766 (8) | 0.0643 (4) | |
P1 | 0.70803 (8) | 0.30988 (7) | 0.55733 (4) | 0.02707 (17) | |
P2 | 0.36721 (8) | 0.27464 (8) | 0.95461 (4) | 0.02791 (18) | |
O1 | 0.7771 (4) | 0.0719 (3) | 0.2394 (2) | 0.0641 (10) | |
N1 | −0.1291 (4) | 0.8821 (3) | 0.17698 (19) | 0.0457 (8) | |
N2 | 0.5008 (5) | 0.0438 (4) | 0.3165 (3) | 0.0809 (15) | |
N3 | 0.8447 (15) | 0.8912 (8) | 0.5232 (5) | 0.189 (5) | |
C1 | −0.0620 (4) | 0.7988 (3) | 0.17763 (19) | 0.0377 (8) | |
C2 | 0.4387 (4) | 0.1246 (4) | 0.2924 (3) | 0.0560 (12) | |
C3 | 0.7686 (3) | 0.4398 (3) | 0.53309 (17) | 0.0289 (7) | |
C4 | 0.7743 (3) | 0.4905 (3) | 0.58379 (18) | 0.0320 (7) | |
H4A | 0.7477 | 0.4569 | 0.6299 | 0.038* | |
C5 | 0.8201 (4) | 0.5911 (3) | 0.5645 (2) | 0.0368 (8) | |
H5A | 0.8231 | 0.6256 | 0.5978 | 0.044* | |
C6 | 0.8613 (4) | 0.6403 (3) | 0.4960 (2) | 0.0416 (9) | |
H6A | 0.8943 | 0.7066 | 0.4836 | 0.050* | |
C7 | 0.8538 (4) | 0.5915 (4) | 0.4460 (2) | 0.0433 (9) | |
H7A | 0.8792 | 0.6262 | 0.4000 | 0.052* | |
C8 | 0.8083 (4) | 0.4906 (3) | 0.46432 (18) | 0.0358 (8) | |
H8A | 0.8044 | 0.4573 | 0.4307 | 0.043* | |
C9 | 0.6921 (4) | 0.2761 (3) | 0.48143 (18) | 0.0324 (7) | |
C10 | 0.5690 (4) | 0.2879 (3) | 0.46541 (19) | 0.0361 (8) | |
H10A | 0.4934 | 0.3087 | 0.4951 | 0.043* | |
C11 | 0.5604 (5) | 0.2678 (3) | 0.4037 (2) | 0.0473 (10) | |
H11A | 0.4785 | 0.2746 | 0.3927 | 0.057* | |
C12 | 0.6718 (5) | 0.2383 (4) | 0.3598 (2) | 0.0540 (12) | |
H12A | 0.6652 | 0.2268 | 0.3186 | 0.065* | |
C13 | 0.7933 (6) | 0.2254 (4) | 0.3762 (2) | 0.0598 (13) | |
H13A | 0.8681 | 0.2039 | 0.3462 | 0.072* | |
C14 | 0.8058 (4) | 0.2442 (4) | 0.4369 (2) | 0.0487 (10) | |
H14A | 0.8882 | 0.2356 | 0.4477 | 0.058* | |
C15 | 0.8181 (3) | 0.1984 (3) | 0.60206 (17) | 0.0298 (7) | |
C16 | 0.8126 (4) | 0.0885 (3) | 0.6040 (2) | 0.0416 (9) | |
H16A | 0.7591 | 0.0745 | 0.5788 | 0.050* | |
C17 | 0.8872 (4) | 0.0008 (4) | 0.6435 (2) | 0.0486 (10) | |
H17A | 0.8822 | −0.0722 | 0.6457 | 0.058* | |
C18 | 0.9698 (4) | 0.0218 (4) | 0.6798 (2) | 0.0480 (10) | |
H18A | 1.0207 | −0.0371 | 0.7058 | 0.058* | |
C19 | 0.9762 (4) | 0.1301 (4) | 0.6773 (2) | 0.0442 (9) | |
H19A | 1.0318 | 0.1439 | 0.7014 | 0.053* | |
C20 | 0.9002 (3) | 0.2182 (3) | 0.63916 (18) | 0.0331 (7) | |
H20A | 0.9038 | 0.2909 | 0.6382 | 0.040* | |
C21 | 0.5502 (3) | 0.3230 (3) | 0.61230 (17) | 0.0275 (7) | |
C22 | 0.4858 (4) | 0.4245 (3) | 0.62475 (19) | 0.0360 (8) | |
H22A | 0.5223 | 0.4887 | 0.6029 | 0.043* | |
C23 | 0.3671 (4) | 0.4297 (3) | 0.6699 (2) | 0.0426 (9) | |
H23A | 0.3241 | 0.4975 | 0.6786 | 0.051* | |
C24 | 0.3127 (4) | 0.3355 (4) | 0.7018 (2) | 0.0421 (9) | |
H24A | 0.2337 | 0.3396 | 0.7326 | 0.051* | |
C25 | 0.3737 (4) | 0.2349 (4) | 0.6885 (2) | 0.0452 (10) | |
H25A | 0.3347 | 0.1719 | 0.7095 | 0.054* | |
C26 | 0.4928 (4) | 0.2275 (3) | 0.6442 (2) | 0.0364 (8) | |
H26A | 0.5346 | 0.1594 | 0.6356 | 0.044* | |
C27 | 0.4636 (3) | 0.2145 (3) | 0.88705 (18) | 0.0330 (7) | |
C28 | 0.5792 (4) | 0.2544 (4) | 0.8513 (2) | 0.0494 (10) | |
H28A | 0.6017 | 0.3140 | 0.8610 | 0.059* | |
C29 | 0.6598 (4) | 0.2061 (5) | 0.8020 (2) | 0.0562 (12) | |
H29A | 0.7364 | 0.2333 | 0.7779 | 0.067* | |
C30 | 0.6268 (4) | 0.1170 (4) | 0.7882 (2) | 0.0495 (10) | |
H30A | 0.6824 | 0.0835 | 0.7554 | 0.059* | |
C31 | 0.5127 (4) | 0.0774 (4) | 0.8225 (2) | 0.0465 (10) | |
H31A | 0.4908 | 0.0180 | 0.8123 | 0.056* | |
C32 | 0.4297 (4) | 0.1260 (3) | 0.87241 (18) | 0.0354 (8) | |
H32A | 0.3524 | 0.0994 | 0.8957 | 0.043* | |
C33 | 0.2878 (3) | 0.4134 (3) | 0.92062 (18) | 0.0315 (7) | |
C34 | 0.1981 (4) | 0.4692 (3) | 0.9655 (2) | 0.0392 (8) | |
H34A | 0.1858 | 0.4370 | 1.0125 | 0.047* | |
C35 | 0.1275 (4) | 0.5731 (4) | 0.9397 (3) | 0.0510 (11) | |
H35A | 0.0696 | 0.6114 | 0.9695 | 0.061* | |
C36 | 0.1431 (5) | 0.6193 (4) | 0.8700 (3) | 0.0572 (12) | |
H36A | 0.0941 | 0.6880 | 0.8529 | 0.069* | |
C37 | 0.2310 (6) | 0.5644 (4) | 0.8255 (3) | 0.0597 (13) | |
H37A | 0.2408 | 0.5966 | 0.7785 | 0.072* | |
C38 | 0.3055 (5) | 0.4612 (3) | 0.8498 (2) | 0.0446 (9) | |
H38A | 0.3657 | 0.4249 | 0.8196 | 0.053* | |
C39 | 0.4767 (3) | 0.2679 (3) | 1.01048 (18) | 0.0321 (7) | |
C40 | 0.4670 (4) | 0.3528 (4) | 1.04186 (19) | 0.0385 (8) | |
H40A | 0.4073 | 0.4182 | 1.0316 | 0.046* | |
C41 | 0.5479 (4) | 0.3386 (4) | 1.0890 (2) | 0.0477 (10) | |
H41A | 0.5421 | 0.3948 | 1.1102 | 0.057* | |
C42 | 0.6363 (4) | 0.2420 (4) | 1.1041 (2) | 0.0525 (12) | |
H42A | 0.6880 | 0.2322 | 1.1366 | 0.063* | |
C43 | 0.6485 (4) | 0.1597 (4) | 1.0716 (3) | 0.0534 (12) | |
H43A | 0.7102 | 0.0955 | 1.0811 | 0.064* | |
C44 | 0.5694 (4) | 0.1720 (4) | 1.0247 (2) | 0.0453 (10) | |
H44A | 0.5781 | 0.1162 | 1.0027 | 0.054* | |
C45 | 0.2376 (3) | 0.1970 (3) | 1.00156 (18) | 0.0312 (7) | |
C46 | 0.1272 (4) | 0.2128 (4) | 0.97261 (19) | 0.0403 (9) | |
H46A | 0.1213 | 0.2641 | 0.9306 | 0.048* | |
C47 | 0.0266 (4) | 0.1535 (4) | 1.0053 (2) | 0.0473 (10) | |
H47A | −0.0455 | 0.1628 | 0.9847 | 0.057* | |
C48 | 0.0330 (4) | 0.0807 (4) | 1.0684 (3) | 0.0569 (12) | |
H48A | −0.0357 | 0.0417 | 1.0912 | 0.068* | |
C49 | 0.1404 (5) | 0.0655 (5) | 1.0980 (3) | 0.0709 (16) | |
H49A | 0.1442 | 0.0153 | 1.1406 | 0.085* | |
C50 | 0.2441 (4) | 0.1239 (4) | 1.0654 (2) | 0.0547 (12) | |
H50A | 0.3161 | 0.1141 | 1.0862 | 0.066* | |
C51 | 0.7660 (14) | 0.9164 (7) | 0.4880 (6) | 0.130 (4) | |
C52 | 0.6797 (10) | 0.9403 (8) | 0.4412 (8) | 0.190 (7) | |
H52A | 0.5995 | 0.9850 | 0.4571 | 0.285* | |
H52B | 0.6610 | 0.8721 | 0.4378 | 0.285* | |
H52C | 0.7200 | 0.9802 | 0.3970 | 0.285* | |
H1WA | 0.805 (5) | 0.017 (5) | 0.218 (3) | 0.065 (16)* | |
H1WB | 0.701 (8) | 0.064 (6) | 0.261 (4) | 0.10 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.02836 (8) | 0.04182 (9) | 0.03259 (8) | −0.00316 (6) | −0.00754 (5) | −0.01305 (6) |
Cu1 | 0.0354 (2) | 0.0434 (3) | 0.0349 (2) | −0.0008 (2) | −0.01073 (19) | −0.0122 (2) |
Cu2 | 0.0390 (3) | 0.0419 (3) | 0.0617 (3) | 0.0011 (2) | −0.0152 (2) | −0.0181 (2) |
S1 | 0.0364 (5) | 0.0674 (7) | 0.0327 (5) | 0.0110 (5) | −0.0010 (4) | −0.0032 (5) |
S2 | 0.0478 (6) | 0.0567 (6) | 0.0279 (4) | −0.0040 (5) | −0.0047 (4) | −0.0140 (4) |
S3 | 0.0313 (4) | 0.0471 (5) | 0.0423 (5) | −0.0011 (4) | −0.0115 (4) | −0.0206 (4) |
S4 | 0.0581 (7) | 0.0515 (7) | 0.0996 (10) | −0.0112 (6) | −0.0402 (7) | −0.0219 (7) |
P1 | 0.0270 (4) | 0.0299 (4) | 0.0250 (4) | −0.0001 (3) | −0.0073 (3) | −0.0093 (3) |
P2 | 0.0277 (4) | 0.0321 (5) | 0.0267 (4) | −0.0095 (3) | −0.0046 (3) | −0.0086 (4) |
O1 | 0.058 (2) | 0.063 (2) | 0.081 (3) | 0.0097 (19) | −0.030 (2) | −0.035 (2) |
N1 | 0.047 (2) | 0.040 (2) | 0.049 (2) | −0.0071 (16) | −0.0067 (16) | −0.0101 (16) |
N2 | 0.066 (3) | 0.037 (2) | 0.145 (5) | 0.006 (2) | −0.037 (3) | −0.028 (3) |
N3 | 0.340 (17) | 0.122 (7) | 0.159 (9) | −0.026 (8) | −0.095 (10) | −0.088 (7) |
C1 | 0.040 (2) | 0.044 (2) | 0.0321 (19) | −0.0153 (18) | −0.0055 (15) | −0.0072 (16) |
C2 | 0.043 (2) | 0.042 (2) | 0.092 (4) | −0.005 (2) | −0.015 (2) | −0.028 (2) |
C3 | 0.0261 (16) | 0.0331 (18) | 0.0268 (16) | −0.0029 (13) | −0.0051 (13) | −0.0080 (14) |
C4 | 0.0333 (17) | 0.0380 (19) | 0.0246 (16) | −0.0050 (15) | −0.0045 (13) | −0.0092 (14) |
C5 | 0.0371 (19) | 0.039 (2) | 0.039 (2) | −0.0062 (16) | −0.0097 (16) | −0.0147 (16) |
C6 | 0.036 (2) | 0.040 (2) | 0.049 (2) | −0.0128 (17) | −0.0039 (17) | −0.0091 (18) |
C7 | 0.047 (2) | 0.050 (2) | 0.0298 (19) | −0.0176 (19) | −0.0003 (16) | −0.0038 (17) |
C8 | 0.0386 (19) | 0.044 (2) | 0.0261 (17) | −0.0080 (16) | −0.0025 (14) | −0.0132 (16) |
C9 | 0.0410 (19) | 0.0282 (17) | 0.0311 (17) | 0.0016 (15) | −0.0154 (15) | −0.0110 (14) |
C10 | 0.045 (2) | 0.0303 (18) | 0.0352 (19) | −0.0062 (16) | −0.0171 (16) | −0.0046 (15) |
C11 | 0.070 (3) | 0.038 (2) | 0.044 (2) | −0.011 (2) | −0.031 (2) | −0.0082 (18) |
C12 | 0.090 (4) | 0.041 (2) | 0.042 (2) | −0.002 (2) | −0.031 (2) | −0.0186 (19) |
C13 | 0.081 (3) | 0.054 (3) | 0.043 (2) | 0.018 (2) | −0.014 (2) | −0.030 (2) |
C14 | 0.049 (2) | 0.056 (3) | 0.045 (2) | 0.011 (2) | −0.0161 (19) | −0.028 (2) |
C15 | 0.0268 (16) | 0.0339 (18) | 0.0274 (16) | 0.0020 (14) | −0.0061 (13) | −0.0102 (14) |
C16 | 0.044 (2) | 0.037 (2) | 0.048 (2) | 0.0090 (17) | −0.0226 (18) | −0.0163 (18) |
C17 | 0.052 (2) | 0.036 (2) | 0.057 (3) | 0.0123 (19) | −0.022 (2) | −0.018 (2) |
C18 | 0.047 (2) | 0.047 (2) | 0.048 (2) | 0.0162 (19) | −0.0223 (19) | −0.0157 (19) |
C19 | 0.036 (2) | 0.060 (3) | 0.040 (2) | 0.0034 (18) | −0.0163 (17) | −0.0186 (19) |
C20 | 0.0295 (17) | 0.040 (2) | 0.0283 (17) | −0.0008 (15) | −0.0062 (14) | −0.0086 (15) |
C21 | 0.0239 (15) | 0.0303 (17) | 0.0266 (16) | −0.0011 (13) | −0.0076 (12) | −0.0049 (13) |
C22 | 0.0320 (18) | 0.0333 (19) | 0.039 (2) | −0.0025 (15) | −0.0043 (15) | −0.0074 (16) |
C23 | 0.0324 (19) | 0.040 (2) | 0.049 (2) | 0.0038 (16) | −0.0048 (17) | −0.0126 (18) |
C24 | 0.0264 (17) | 0.053 (2) | 0.038 (2) | −0.0004 (17) | −0.0024 (15) | −0.0058 (18) |
C25 | 0.035 (2) | 0.045 (2) | 0.047 (2) | −0.0127 (18) | −0.0040 (17) | 0.0035 (18) |
C26 | 0.0339 (18) | 0.0274 (18) | 0.045 (2) | −0.0007 (15) | −0.0097 (16) | −0.0057 (16) |
C27 | 0.0322 (17) | 0.040 (2) | 0.0281 (17) | −0.0084 (15) | −0.0015 (14) | −0.0114 (15) |
C28 | 0.044 (2) | 0.064 (3) | 0.046 (2) | −0.023 (2) | 0.0053 (18) | −0.021 (2) |
C29 | 0.044 (2) | 0.081 (3) | 0.043 (2) | −0.020 (2) | 0.0119 (19) | −0.022 (2) |
C30 | 0.047 (2) | 0.065 (3) | 0.033 (2) | 0.003 (2) | −0.0015 (18) | −0.020 (2) |
C31 | 0.058 (3) | 0.045 (2) | 0.041 (2) | −0.003 (2) | −0.0121 (19) | −0.0192 (19) |
C32 | 0.041 (2) | 0.036 (2) | 0.0318 (18) | −0.0081 (16) | −0.0068 (15) | −0.0113 (15) |
C33 | 0.0300 (17) | 0.0326 (18) | 0.0352 (18) | −0.0122 (14) | −0.0079 (14) | −0.0069 (15) |
C34 | 0.0336 (19) | 0.035 (2) | 0.047 (2) | −0.0098 (16) | −0.0032 (16) | −0.0080 (17) |
C35 | 0.0299 (19) | 0.044 (2) | 0.081 (3) | −0.0038 (17) | −0.012 (2) | −0.019 (2) |
C36 | 0.055 (3) | 0.040 (2) | 0.085 (4) | −0.006 (2) | −0.037 (3) | −0.011 (2) |
C37 | 0.089 (4) | 0.044 (3) | 0.049 (3) | −0.011 (2) | −0.035 (3) | 0.003 (2) |
C38 | 0.061 (3) | 0.042 (2) | 0.034 (2) | −0.0099 (19) | −0.0155 (18) | −0.0071 (17) |
C39 | 0.0297 (17) | 0.039 (2) | 0.0310 (17) | −0.0132 (15) | −0.0064 (14) | −0.0076 (15) |
C40 | 0.0367 (19) | 0.049 (2) | 0.0342 (19) | −0.0125 (17) | −0.0038 (15) | −0.0150 (17) |
C41 | 0.048 (2) | 0.068 (3) | 0.037 (2) | −0.027 (2) | −0.0058 (18) | −0.018 (2) |
C42 | 0.051 (2) | 0.067 (3) | 0.045 (2) | −0.030 (2) | −0.024 (2) | 0.003 (2) |
C43 | 0.043 (2) | 0.050 (3) | 0.072 (3) | −0.016 (2) | −0.031 (2) | 0.000 (2) |
C44 | 0.041 (2) | 0.041 (2) | 0.060 (3) | −0.0106 (18) | −0.0193 (19) | −0.011 (2) |
C45 | 0.0307 (17) | 0.0329 (18) | 0.0307 (17) | −0.0108 (14) | −0.0011 (14) | −0.0086 (14) |
C46 | 0.042 (2) | 0.051 (2) | 0.0313 (19) | −0.0195 (18) | −0.0119 (16) | −0.0028 (17) |
C47 | 0.039 (2) | 0.058 (3) | 0.050 (2) | −0.024 (2) | −0.0099 (18) | −0.008 (2) |
C48 | 0.039 (2) | 0.057 (3) | 0.064 (3) | −0.025 (2) | 0.001 (2) | 0.006 (2) |
C49 | 0.049 (3) | 0.085 (4) | 0.057 (3) | −0.029 (3) | −0.010 (2) | 0.030 (3) |
C50 | 0.040 (2) | 0.062 (3) | 0.050 (3) | −0.015 (2) | −0.0145 (19) | 0.013 (2) |
C51 | 0.207 (13) | 0.060 (5) | 0.126 (8) | −0.019 (6) | −0.017 (8) | −0.043 (5) |
C52 | 0.101 (7) | 0.095 (7) | 0.338 (19) | −0.018 (5) | −0.086 (10) | 0.038 (9) |
W1—S1 | 2.2087 (11) | C21—C26 | 1.399 (5) |
W1—S4 | 2.2151 (12) | C22—C23 | 1.385 (5) |
W1—S3 | 2.2178 (9) | C22—H22A | 0.9300 |
W1—S2 | 2.2243 (11) | C23—C24 | 1.369 (6) |
W1—Cu2 | 2.6463 (6) | C23—H23A | 0.9300 |
W1—Cu1 | 2.6545 (6) | C24—C25 | 1.376 (6) |
Cu1—C1 | 1.897 (4) | C24—H24A | 0.9300 |
Cu1—S2 | 2.2295 (11) | C25—C26 | 1.382 (5) |
Cu1—S1 | 2.2404 (12) | C25—H25A | 0.9300 |
Cu2—C2 | 1.885 (5) | C26—H26A | 0.9300 |
Cu2—S4 | 2.2316 (13) | C27—C32 | 1.388 (5) |
Cu2—S3 | 2.2449 (11) | C27—C28 | 1.395 (5) |
P1—C21 | 1.798 (3) | C28—C29 | 1.373 (6) |
P1—C15 | 1.800 (4) | C28—H28A | 0.9300 |
P1—C3 | 1.800 (4) | C29—C30 | 1.382 (7) |
P1—C9 | 1.803 (3) | C29—H29A | 0.9300 |
P2—C27 | 1.792 (4) | C30—C31 | 1.373 (6) |
P2—C33 | 1.794 (4) | C30—H30A | 0.9300 |
P2—C45 | 1.798 (3) | C31—C32 | 1.393 (5) |
P2—C39 | 1.798 (3) | C31—H31A | 0.9300 |
O1—H1WA | 0.91 (6) | C32—H32A | 0.9300 |
O1—H1WB | 0.84 (7) | C33—C34 | 1.397 (5) |
N1—C1 | 1.138 (5) | C33—C38 | 1.401 (5) |
N2—C2 | 1.138 (6) | C34—C35 | 1.390 (6) |
N3—C51 | 1.168 (15) | C34—H34A | 0.9300 |
C3—C8 | 1.389 (5) | C35—C36 | 1.376 (7) |
C3—C4 | 1.405 (5) | C35—H35A | 0.9300 |
C4—C5 | 1.387 (5) | C36—C37 | 1.380 (7) |
C4—H4A | 0.9300 | C36—H36A | 0.9300 |
C5—C6 | 1.383 (6) | C37—C38 | 1.395 (6) |
C5—H5A | 0.9300 | C37—H37A | 0.9300 |
C6—C7 | 1.383 (6) | C38—H38A | 0.9300 |
C6—H6A | 0.9300 | C39—C44 | 1.392 (6) |
C7—C8 | 1.390 (5) | C39—C40 | 1.393 (5) |
C7—H7A | 0.9300 | C40—C41 | 1.396 (5) |
C8—H8A | 0.9300 | C40—H40A | 0.9300 |
C9—C10 | 1.389 (5) | C41—C42 | 1.376 (7) |
C9—C14 | 1.399 (6) | C41—H41A | 0.9300 |
C10—C11 | 1.404 (5) | C42—C43 | 1.374 (7) |
C10—H10A | 0.9300 | C42—H42A | 0.9300 |
C11—C12 | 1.367 (7) | C43—C44 | 1.381 (6) |
C11—H11A | 0.9300 | C43—H43A | 0.9300 |
C12—C13 | 1.373 (7) | C44—H44A | 0.9300 |
C12—H12A | 0.9300 | C45—C50 | 1.385 (6) |
C13—C14 | 1.390 (6) | C45—C46 | 1.390 (5) |
C13—H13A | 0.9300 | C46—C47 | 1.375 (5) |
C14—H14A | 0.9300 | C46—H46A | 0.9300 |
C15—C20 | 1.394 (5) | C47—C48 | 1.372 (6) |
C15—C16 | 1.403 (5) | C47—H47A | 0.9300 |
C16—C17 | 1.386 (5) | C48—C49 | 1.370 (7) |
C16—H16A | 0.9300 | C48—H48A | 0.9300 |
C17—C18 | 1.395 (6) | C49—C50 | 1.395 (6) |
C17—H17A | 0.9300 | C49—H49A | 0.9300 |
C18—C19 | 1.382 (6) | C50—H50A | 0.9300 |
C18—H18A | 0.9300 | C51—C52 | 1.411 (15) |
C19—C20 | 1.384 (5) | C52—H52A | 0.9600 |
C19—H19A | 0.9300 | C52—H52B | 0.9600 |
C20—H20A | 0.9300 | C52—H52C | 0.9600 |
C21—C22 | 1.389 (5) | ||
S1—W1—S4 | 110.51 (5) | C15—C20—H20A | 119.9 |
S1—W1—S3 | 108.45 (4) | C22—C21—C26 | 119.7 (3) |
S4—W1—S3 | 107.78 (4) | C22—C21—P1 | 121.7 (3) |
S1—W1—S2 | 107.34 (4) | C26—C21—P1 | 118.6 (3) |
S4—W1—S2 | 112.17 (5) | C23—C22—C21 | 119.6 (4) |
S3—W1—S2 | 110.54 (4) | C23—C22—H22A | 120.2 |
S1—W1—Cu2 | 121.83 (3) | C21—C22—H22A | 120.2 |
S4—W1—Cu2 | 53.77 (3) | C24—C23—C22 | 120.3 (4) |
S3—W1—Cu2 | 54.10 (3) | C24—C23—H23A | 119.8 |
S2—W1—Cu2 | 130.80 (3) | C22—C23—H23A | 119.8 |
S1—W1—Cu1 | 53.92 (3) | C23—C24—C25 | 120.6 (4) |
S4—W1—Cu1 | 130.54 (3) | C23—C24—H24A | 119.7 |
S3—W1—Cu1 | 121.64 (3) | C25—C24—H24A | 119.7 |
S2—W1—Cu1 | 53.51 (3) | C24—C25—C26 | 120.1 (4) |
Cu2—W1—Cu1 | 173.961 (16) | C24—C25—H25A | 120.0 |
C1—Cu1—S2 | 133.75 (12) | C26—C25—H25A | 120.0 |
C1—Cu1—S1 | 120.18 (12) | C25—C26—C21 | 119.6 (4) |
S2—Cu1—S1 | 106.06 (4) | C25—C26—H26A | 120.2 |
C1—Cu1—W1 | 172.31 (11) | C21—C26—H26A | 120.2 |
S2—Cu1—W1 | 53.32 (3) | C32—C27—C28 | 119.8 (3) |
S1—Cu1—W1 | 52.82 (3) | C32—C27—P2 | 121.7 (3) |
C2—Cu2—S4 | 129.30 (14) | C28—C27—P2 | 118.4 (3) |
C2—Cu2—S3 | 124.32 (14) | C29—C28—C27 | 120.2 (4) |
S4—Cu2—S3 | 106.27 (5) | C29—C28—H28A | 119.9 |
C2—Cu2—W1 | 173.86 (17) | C27—C28—H28A | 119.9 |
S4—Cu2—W1 | 53.19 (3) | C28—C29—C30 | 119.8 (4) |
S3—Cu2—W1 | 53.16 (3) | C28—C29—H29A | 120.1 |
W1—S1—Cu1 | 73.26 (3) | C30—C29—H29A | 120.1 |
W1—S2—Cu1 | 73.17 (3) | C31—C30—C29 | 120.7 (4) |
W1—S3—Cu2 | 72.74 (3) | C31—C30—H30A | 119.7 |
W1—S4—Cu2 | 73.04 (4) | C29—C30—H30A | 119.7 |
C21—P1—C15 | 108.88 (16) | C30—C31—C32 | 120.0 (4) |
C21—P1—C3 | 109.30 (16) | C30—C31—H31A | 120.0 |
C15—P1—C3 | 111.30 (16) | C32—C31—H31A | 120.0 |
C21—P1—C9 | 109.45 (16) | C27—C32—C31 | 119.4 (4) |
C15—P1—C9 | 108.58 (16) | C27—C32—H32A | 120.3 |
C3—P1—C9 | 109.31 (16) | C31—C32—H32A | 120.3 |
C27—P2—C33 | 110.86 (17) | C34—C33—C38 | 120.2 (4) |
C27—P2—C45 | 110.58 (16) | C34—C33—P2 | 118.7 (3) |
C33—P2—C45 | 105.95 (17) | C38—C33—P2 | 120.7 (3) |
C27—P2—C39 | 106.53 (17) | C35—C34—C33 | 119.8 (4) |
C33—P2—C39 | 113.36 (17) | C35—C34—H34A | 120.1 |
C45—P2—C39 | 109.60 (16) | C33—C34—H34A | 120.1 |
H1WA—O1—H1WB | 107 (6) | C36—C35—C34 | 120.1 (4) |
N1—C1—Cu1 | 176.2 (4) | C36—C35—H35A | 120.0 |
N2—C2—Cu2 | 177.7 (5) | C34—C35—H35A | 120.0 |
C8—C3—C4 | 120.0 (3) | C35—C36—C37 | 120.4 (4) |
C8—C3—P1 | 120.1 (3) | C35—C36—H36A | 119.8 |
C4—C3—P1 | 119.9 (3) | C37—C36—H36A | 119.8 |
C5—C4—C3 | 119.5 (3) | C36—C37—C38 | 120.9 (4) |
C5—C4—H4A | 120.3 | C36—C37—H37A | 119.5 |
C3—C4—H4A | 120.3 | C38—C37—H37A | 119.5 |
C6—C5—H5A | 119.9 | C37—C38—C33 | 118.6 (4) |
C4—C5—H5A | 119.9 | C37—C38—H38A | 120.7 |
C5—C6—H6A | 119.8 | C33—C38—H38A | 120.7 |
C7—C6—H6A | 119.8 | C44—C39—C40 | 119.8 (3) |
C6—C7—H7A | 119.9 | C44—C39—P2 | 118.2 (3) |
C8—C7—H7A | 119.9 | C40—C39—P2 | 121.9 (3) |
C6—C5—C4 | 120.2 (3) | C39—C40—C41 | 119.1 (4) |
C5—C6—C7 | 120.4 (4) | C39—C40—H40A | 120.4 |
C6—C7—C8 | 120.1 (4) | C41—C40—H40A | 120.4 |
C3—C8—C7 | 119.8 (3) | C42—C41—C40 | 120.4 (4) |
C3—C8—H8A | 120.1 | C42—C41—H41A | 119.8 |
C7—C8—H8A | 120.1 | C40—C41—H41A | 119.8 |
C10—C9—C14 | 120.5 (3) | C43—C42—C41 | 120.4 (4) |
C10—C9—P1 | 120.4 (3) | C43—C42—H42A | 119.8 |
C14—C9—P1 | 119.0 (3) | C41—C42—H42A | 119.8 |
C9—C10—C11 | 119.0 (4) | C42—C43—C44 | 120.2 (4) |
C9—C10—H10A | 120.5 | C42—C43—H43A | 119.9 |
C11—C10—H10A | 120.5 | C44—C43—H43A | 119.9 |
C12—C11—C10 | 120.4 (4) | C43—C44—C39 | 120.1 (4) |
C12—C11—H11A | 119.8 | C43—C44—H44A | 120.0 |
C10—C11—H11A | 119.8 | C39—C44—H44A | 120.0 |
C11—C12—C13 | 120.5 (4) | C50—C45—C46 | 119.6 (3) |
C11—C12—H12A | 119.8 | C50—C45—P2 | 122.1 (3) |
C13—C12—H12A | 119.8 | C46—C45—P2 | 118.3 (3) |
C12—C13—C14 | 120.8 (4) | C47—C46—C45 | 120.9 (4) |
C12—C13—H13A | 119.6 | C47—C46—H46A | 119.6 |
C14—C13—H13A | 119.6 | C45—C46—H46A | 119.6 |
C13—C14—C9 | 118.8 (4) | C48—C47—C46 | 119.6 (4) |
C13—C14—H14A | 120.6 | C48—C47—H47A | 120.2 |
C9—C14—H14A | 120.6 | C46—C47—H47A | 120.2 |
C20—C15—C16 | 119.6 (3) | C49—C48—C47 | 120.1 (4) |
C20—C15—P1 | 121.5 (3) | C49—C48—H48A | 119.9 |
C16—C15—P1 | 118.7 (3) | C47—C48—H48A | 119.9 |
C17—C16—C15 | 119.8 (4) | C48—C49—C50 | 121.1 (4) |
C17—C16—H16A | 120.1 | C48—C49—H49A | 119.4 |
C15—C16—H16A | 120.1 | C50—C49—H49A | 119.4 |
C16—C17—C18 | 120.1 (4) | C45—C50—C49 | 118.6 (4) |
C16—C17—H17A | 120.0 | C45—C50—H50A | 120.7 |
C18—C17—H17A | 120.0 | C49—C50—H50A | 120.7 |
C19—C18—C17 | 120.1 (4) | N3—C51—C52 | 174.2 (13) |
C19—C18—H18A | 119.9 | C51—C52—H52A | 109.5 |
C17—C18—H18A | 119.9 | C51—C52—H52B | 109.5 |
C18—C19—C20 | 120.3 (4) | H52A—C52—H52B | 109.5 |
C18—C19—H19A | 119.9 | C51—C52—H52C | 109.5 |
C20—C19—H19A | 119.9 | H52A—C52—H52C | 109.5 |
C19—C20—C15 | 120.2 (4) | H52B—C52—H52C | 109.5 |
C19—C20—H20A | 119.9 | ||
S1—W1—Cu1—S2 | −176.12 (6) | C17—C18—C19—C20 | 0.4 (6) |
S4—W1—Cu1—S2 | −89.14 (7) | C18—C19—C20—C15 | −1.0 (6) |
S3—W1—Cu1—S2 | 93.25 (5) | C16—C15—C20—C19 | 0.3 (5) |
S4—W1—Cu1—S1 | 86.98 (7) | P1—C15—C20—C19 | 175.0 (3) |
S3—W1—Cu1—S1 | −90.63 (5) | C15—P1—C21—C22 | 128.5 (3) |
S2—W1—Cu1—S1 | 176.12 (6) | C3—P1—C21—C22 | 6.7 (3) |
S1—W1—Cu2—S4 | 93.23 (7) | C9—P1—C21—C22 | −112.9 (3) |
S3—W1—Cu2—S4 | −176.16 (6) | C15—P1—C21—C26 | −50.2 (3) |
S2—W1—Cu2—S4 | −89.17 (7) | C3—P1—C21—C26 | −172.0 (3) |
S1—W1—Cu2—S3 | −90.60 (5) | C9—P1—C21—C26 | 68.4 (3) |
S4—W1—Cu2—S3 | 176.16 (6) | C26—C21—C22—C23 | 1.6 (5) |
S2—W1—Cu2—S3 | 86.99 (5) | P1—C21—C22—C23 | −177.1 (3) |
S4—W1—S1—Cu1 | −125.88 (4) | C21—C22—C23—C24 | −0.5 (6) |
S3—W1—S1—Cu1 | 116.18 (4) | C22—C23—C24—C25 | −1.2 (6) |
S2—W1—S1—Cu1 | −3.27 (5) | C23—C24—C25—C26 | 1.8 (6) |
Cu2—W1—S1—Cu1 | 174.822 (19) | C24—C25—C26—C21 | −0.7 (6) |
C1—Cu1—S1—W1 | −176.15 (13) | C22—C21—C26—C25 | −1.0 (5) |
S2—Cu1—S1—W1 | 3.24 (5) | P1—C21—C26—C25 | 177.7 (3) |
S1—W1—S2—Cu1 | 3.29 (5) | C33—P2—C27—C32 | −112.1 (3) |
S4—W1—S2—Cu1 | 124.86 (4) | C45—P2—C27—C32 | 5.1 (4) |
S3—W1—S2—Cu1 | −114.82 (4) | C39—P2—C27—C32 | 124.1 (3) |
Cu2—W1—S2—Cu1 | −174.57 (2) | C33—P2—C27—C28 | 71.5 (4) |
C1—Cu1—S2—W1 | 176.06 (16) | C45—P2—C27—C28 | −171.3 (3) |
S1—Cu1—S2—W1 | −3.22 (5) | C39—P2—C27—C28 | −52.2 (4) |
S1—W1—S3—Cu2 | 116.41 (4) | C32—C27—C28—C29 | −0.3 (7) |
S4—W1—S3—Cu2 | −3.25 (5) | P2—C27—C28—C29 | 176.1 (4) |
S2—W1—S3—Cu2 | −126.17 (4) | C27—C28—C29—C30 | −0.6 (7) |
Cu1—W1—S3—Cu2 | 174.84 (2) | C28—C29—C30—C31 | 1.3 (7) |
C2—Cu2—S3—W1 | −173.1 (2) | C29—C30—C31—C32 | −0.9 (7) |
S4—Cu2—S3—W1 | 3.20 (5) | C28—C27—C32—C31 | 0.6 (6) |
S1—W1—S4—Cu2 | −115.09 (4) | P2—C27—C32—C31 | −175.7 (3) |
S3—W1—S4—Cu2 | 3.26 (5) | C30—C31—C32—C27 | 0.0 (6) |
S2—W1—S4—Cu2 | 125.18 (4) | C27—P2—C33—C34 | 173.7 (3) |
Cu1—W1—S4—Cu2 | −174.60 (2) | C45—P2—C33—C34 | 53.7 (3) |
C2—Cu2—S4—W1 | 172.9 (2) | C39—P2—C33—C34 | −66.5 (3) |
S3—Cu2—S4—W1 | −3.20 (5) | C27—P2—C33—C38 | −0.3 (3) |
C21—P1—C3—C8 | −126.7 (3) | C45—P2—C33—C38 | −120.3 (3) |
C15—P1—C3—C8 | 113.0 (3) | C39—P2—C33—C38 | 119.5 (3) |
C9—P1—C3—C8 | −6.9 (3) | C38—C33—C34—C35 | −0.8 (5) |
C21—P1—C3—C4 | 52.6 (3) | P2—C33—C34—C35 | −174.8 (3) |
C15—P1—C3—C4 | −67.7 (3) | C33—C34—C35—C36 | 1.9 (6) |
C9—P1—C3—C4 | 172.4 (3) | C34—C35—C36—C37 | −1.6 (7) |
C8—C3—C4—C5 | −0.2 (5) | C35—C36—C37—C38 | 0.1 (7) |
P1—C3—C4—C5 | −179.4 (3) | C36—C37—C38—C33 | 1.0 (7) |
C3—C4—C5—C6 | −0.8 (6) | C34—C33—C38—C37 | −0.6 (6) |
C4—C5—C6—C7 | 1.9 (6) | P2—C33—C38—C37 | 173.2 (3) |
C5—C6—C7—C8 | −2.0 (6) | C27—P2—C39—C44 | −40.5 (3) |
C4—C3—C8—C7 | 0.1 (6) | C33—P2—C39—C44 | −162.7 (3) |
P1—C3—C8—C7 | 179.4 (3) | C45—P2—C39—C44 | 79.2 (3) |
C6—C7—C8—C3 | 0.9 (6) | C27—P2—C39—C40 | 142.5 (3) |
C21—P1—C9—C10 | 14.1 (3) | C33—P2—C39—C40 | 20.3 (4) |
C15—P1—C9—C10 | 132.8 (3) | C45—P2—C39—C40 | −97.8 (3) |
C3—P1—C9—C10 | −105.6 (3) | C44—C39—C40—C41 | −2.1 (6) |
C21—P1—C9—C14 | −169.6 (3) | P2—C39—C40—C41 | 174.8 (3) |
C15—P1—C9—C14 | −50.9 (4) | C39—C40—C41—C42 | 0.1 (6) |
C3—P1—C9—C14 | 70.7 (4) | C40—C41—C42—C43 | 1.9 (6) |
C14—C9—C10—C11 | −0.3 (6) | C41—C42—C43—C44 | −1.9 (7) |
P1—C9—C10—C11 | 175.9 (3) | C42—C43—C44—C39 | −0.1 (7) |
C9—C10—C11—C12 | −0.7 (6) | C40—C39—C44—C43 | 2.1 (6) |
C10—C11—C12—C13 | 1.5 (7) | P2—C39—C44—C43 | −174.9 (3) |
C11—C12—C13—C14 | −1.2 (7) | C27—P2—C45—C50 | 103.4 (4) |
C12—C13—C14—C9 | 0.2 (7) | C33—P2—C45—C50 | −136.5 (4) |
C10—C9—C14—C13 | 0.5 (6) | C39—P2—C45—C50 | −13.8 (4) |
P1—C9—C14—C13 | −175.7 (4) | C27—P2—C45—C46 | −77.6 (3) |
C21—P1—C15—C20 | −93.6 (3) | C33—P2—C45—C46 | 42.6 (3) |
C3—P1—C15—C20 | 27.0 (3) | C39—P2—C45—C46 | 165.3 (3) |
C9—P1—C15—C20 | 147.3 (3) | C50—C45—C46—C47 | −2.6 (6) |
C21—P1—C15—C16 | 81.1 (3) | P2—C45—C46—C47 | 178.3 (3) |
C3—P1—C15—C16 | −158.3 (3) | C45—C46—C47—C48 | 2.3 (7) |
C9—P1—C15—C16 | −37.9 (3) | C46—C47—C48—C49 | −1.4 (8) |
C20—C15—C16—C17 | 1.0 (6) | C47—C48—C49—C50 | 0.8 (9) |
P1—C15—C16—C17 | −173.9 (3) | C46—C45—C50—C49 | 2.0 (7) |
C15—C16—C17—C18 | −1.5 (7) | P2—C45—C50—C49 | −179.0 (4) |
C16—C17—C18—C19 | 0.8 (7) | C48—C49—C50—C45 | −1.1 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1WA···N1i | 0.90 (6) | 2.05 (6) | 2.947 (5) | 175 (5) |
O1—H1WB···N2 | 0.84 (9) | 2.20 (9) | 3.038 (7) | 179 (10) |
Symmetry code: (i) x+1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (C24H20P)2[Cu2WS4(CN)2]·C2H3N·H2O |
Mr | 1229.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 193 |
a, b, c (Å) | 10.6193 (2), 12.7441 (10), 20.7526 (3) |
α, β, γ (°) | 72.922 (9), 76.449 (9), 77.159 (10) |
V (Å3) | 2574.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.31 |
Crystal size (mm) | 0.40 × 0.35 × 0.30 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.260, 0.370 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25798, 11796, 10551 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.089, 1.02 |
No. of reflections | 11567 |
No. of parameters | 594 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.02, −0.84 |
Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalClear, CrystalStructure (Rigaku/MSC, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2000).
W1—S1 | 2.2087 (11) | Cu1—S1 | 2.2404 (12) |
W1—S4 | 2.2151 (12) | Cu2—C2 | 1.885 (5) |
W1—S3 | 2.2178 (9) | Cu2—S4 | 2.2316 (13) |
W1—S2 | 2.2243 (11) | Cu2—S3 | 2.2449 (11) |
W1—Cu2 | 2.6463 (6) | N1—C1 | 1.138 (5) |
W1—Cu1 | 2.6545 (6) | N2—C2 | 1.138 (6) |
Cu1—C1 | 1.897 (4) | N3—C51 | 1.168 (15) |
Cu1—S2 | 2.2295 (11) | ||
S1—W1—S4 | 110.51 (5) | C2—Cu2—S4 | 129.30 (14) |
S1—W1—S3 | 108.45 (4) | C2—Cu2—S3 | 124.32 (14) |
S4—W1—S3 | 107.78 (4) | S4—Cu2—S3 | 106.27 (5) |
S1—W1—S2 | 107.34 (4) | C2—Cu2—W1 | 173.86 (17) |
S4—W1—S2 | 112.17 (5) | W1—S1—Cu1 | 73.26 (3) |
S3—W1—S2 | 110.54 (4) | W1—S2—Cu1 | 73.17 (3) |
Cu2—W1—Cu1 | 173.961 (16) | W1—S3—Cu2 | 72.74 (3) |
C1—Cu1—S2 | 133.75 (12) | W1—S4—Cu2 | 73.04 (4) |
C1—Cu1—S1 | 120.18 (12) | N1—C1—Cu1 | 176.2 (4) |
S2—Cu1—S1 | 106.06 (4) | N2—C2—Cu2 | 177.7 (5) |
C1—Cu1—W1 | 172.31 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1WA···N1i | 0.90 (6) | 2.05 (6) | 2.947 (5) | 175 (5) |
O1—H1WB···N2 | 0.84 (9) | 2.20 (9) | 3.038 (7) | 179 (10) |
Symmetry code: (i) x+1, y−1, z. |
In the past decade, the third-order non-linear optical (NLO) properties of group IB–VIB chalcogenide clusters derived from tetrathiometallate ([MS4]2-; M = Mo and W) anions have been studied extensively (Shi et al., 1994; Shi, 1998; Yu et al., 2001). However, only a few Mo(W)/Cu(Ag)/S clusters containing cyanides have been prepared and confirmed to exhibit good NLO properties in solution (Hou et al., 1999; Zhang et al., 2000). To find clusters with better NLO properties, we carried out the reaction of CuCN and KCN with (NH4)2[WS4]. We report here the structure of the title trinuclear W/Cu/S cluster, (I).
The asymmetric unit of (I) contains one discrete cluster anion, two [PPh4]+ cations, one acetonitrile molecule and one water molecule (Fig. 1). Being isostructural with its molybdenum analogue (Gheller, et al., 1984), the dianion of (I) consists of a central WS4 moiety and two CuCN groups, which are connected via µ-S atoms. However, the dianion is slightly distorted from D2 d symmetry by small bends of 6–8° at all three metal atoms along the NC—Cu—W—Cu—CN axis (Table 1). The two Cu—C—N angles also deviate from linearity (by 2–4°). The two WCuS2 rhombuses are not quite planar but are essentially perpendicularly disposed to one another.
Each of the two Cu atoms adopts an approximately trigonal-planar coordination geometry. The WS4 moiety is a slightly distorted tetrahedron, with S—W—S bond angles ranging from 107.34 (4) to 112.17 (5)°. The mean W—µ-S bond length shows an apparent elongation of 0.052 (11) Å compared with that in free [WS4]2- [2.165 (3) Å] (Sasvari, 1963) as a result of binding two CuCN groups. The mean W—Cu distance [2.6504 (6) Å] is comparable to those found in three-coordinate Cu clusters, such as [PPh4]2[(η5-C5Me5)WS3Cu3Br3]2 [2.661 (1) Å] (Lang et al., 1997) and [PPh4][{(η5-C5Me5) WS3Cu2}2S2]2 [2.677 (3) Å] (Lang & Tatsumi, 1998). The mean Cu—µ-S and Cu—C distances are similar to those in the corresponding molybdenum analogue [Cu—µ-S = 2.210 (2) Å and Cu—C = 1.886 (9) Å; Gheller et al., 1984].
Each water molecule acts as a donor for two intermolecular hydrogen bonds (Table 2). The acceptor atoms are the cyano N atoms from opposite ends of two adjacent anions. These interactions link an alternating sequence of anions and water molecules into extended chains that run in the [1–10] direction.