Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108018404/em3015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108018404/em3015Isup2.hkl |
CCDC reference: 700009
The synthesis was carried out in an atmosphere of dry N2 using standard Schlenk and vacuum line techniques. A methanolic solution (5 ml) of Li2S (23 mg, 0.50 mmol) was added to a dichloromethane solution (10 ml) of [Cu2(Ph2PNHPPh2)2(MeCN)2](BF4)2 (148 mg, 0.13 mmol). After stirring the solution for 8 h at room temperature, the solvents were removed and the residue dissolved in dichloromethane (5 ml). Diethyl ether was layered onto this solution and the product, (I), was obtained after a few days as well shaped colourless crystals in a yield of about 48%.
All H atoms on C and N atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for phenyl H, C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for –CH3, and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N). Atom H1 on the O atom of MeOH was located and then refined with calculated geometry but allowed rotational freedom. All H atoms on S atoms were not included because of the poor diffraction of compound (I).
Data collection: SMART (Siemens, 1994); cell refinement: SMART (Siemens, 1994); data reduction: SMART (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cu4(SH)4(C24H21NP2)2]·2CH4O | F(000) = 2496 |
Mr = 1221.23 | Dx = 1.519 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3911 reflections |
a = 17.0144 (8) Å | θ = 2.0–25.1° |
b = 18.2738 (9) Å | µ = 1.89 mm−1 |
c = 17.1713 (9) Å | T = 298 K |
V = 5338.9 (5) Å3 | Block, yellow |
Z = 4 | 0.30 × 0.24 × 0.24 mm |
Siemens SMART CCD diffractometer | 4726 independent reflections |
Radiation source: fine-focus sealed tube | 2983 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
ω scans | θmax = 25.1°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2001) | h = −20→13 |
Tmin = 0.586, Tmax = 0.636 | k = −21→11 |
15623 measured reflections | l = −20→18 |
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)] = 0.086 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.174 | H-atom parameters constrained |
S = 1.21 | w = 1/[σ2(Fo2) + (0.0261P)2 + 28.2604P] where P = (Fo2 + 2Fc2)/3 |
4726 reflections | (Δ/σ)max < 0.001 |
300 parameters | Δρmax = 0.76 e Å−3 |
0 restraints | Δρmin = −0.99 e Å−3 |
[Cu4(SH)4(C24H21NP2)2]·2CH4O | V = 5338.9 (5) Å3 |
Mr = 1221.23 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 17.0144 (8) Å | µ = 1.89 mm−1 |
b = 18.2738 (9) Å | T = 298 K |
c = 17.1713 (9) Å | 0.30 × 0.24 × 0.24 mm |
Siemens SMART CCD diffractometer | 4726 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2001) | 2983 reflections with I > 2σ(I) |
Tmin = 0.586, Tmax = 0.636 | Rint = 0.071 |
15623 measured reflections |
R[F2 > 2σ(F2)] = 0.086 | 0 restraints |
wR(F2) = 0.174 | H-atom parameters constrained |
S = 1.21 | w = 1/[σ2(Fo2) + (0.0261P)2 + 28.2604P] where P = (Fo2 + 2Fc2)/3 |
4726 reflections | Δρmax = 0.76 e Å−3 |
300 parameters | Δρmin = −0.99 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.49263 (6) | 0.39757 (7) | 0.48675 (8) | 0.0788 (4) | |
Cu2 | 0.62310 (7) | 0.49213 (6) | 0.51180 (8) | 0.0748 (4) | |
S1 | 0.51610 (12) | 0.47084 (11) | 0.59688 (12) | 0.0492 (5) | |
S2 | 0.62503 (12) | 0.38210 (11) | 0.44708 (14) | 0.0546 (6) | |
P1 | 0.40520 (12) | 0.31447 (12) | 0.45799 (13) | 0.0509 (6) | |
P2 | 0.28274 (12) | 0.42741 (11) | 0.48215 (13) | 0.0493 (5) | |
O1 | 0.1912 (5) | 0.2333 (4) | 0.4333 (5) | 0.102 (3) | |
H1 | 0.1759 | 0.2089 | 0.4704 | 0.154* | |
N1 | 0.3114 (3) | 0.3424 (3) | 0.4609 (4) | 0.0557 (18) | |
H1A | 0.2755 | 0.3107 | 0.4506 | 0.067* | |
C1 | 0.1637 (8) | 0.2039 (8) | 0.3665 (8) | 0.150 (6) | |
H1B | 0.1078 | 0.2108 | 0.3638 | 0.225* | |
H1C | 0.1754 | 0.1525 | 0.3654 | 0.225* | |
H1D | 0.1882 | 0.2275 | 0.3229 | 0.225* | |
C11 | 0.4190 (5) | 0.2752 (4) | 0.3617 (5) | 0.052 (2) | |
C12 | 0.4734 (6) | 0.3038 (6) | 0.3121 (6) | 0.074 (3) | |
H12A | 0.5014 | 0.3450 | 0.3276 | 0.089* | |
C13 | 0.4886 (8) | 0.2743 (7) | 0.2404 (7) | 0.095 (4) | |
H13A | 0.5271 | 0.2944 | 0.2084 | 0.114* | |
C14 | 0.4467 (8) | 0.2157 (7) | 0.2169 (6) | 0.094 (4) | |
H14A | 0.4562 | 0.1956 | 0.1681 | 0.113* | |
C15 | 0.3916 (8) | 0.1859 (6) | 0.2631 (6) | 0.095 (4) | |
H15A | 0.3629 | 0.1457 | 0.2459 | 0.114* | |
C16 | 0.3773 (6) | 0.2153 (5) | 0.3368 (6) | 0.078 (3) | |
H16A | 0.3396 | 0.1943 | 0.3690 | 0.094* | |
C21 | 0.4054 (4) | 0.2323 (4) | 0.5183 (5) | 0.051 (2) | |
C22 | 0.4731 (6) | 0.1904 (6) | 0.5186 (6) | 0.076 (3) | |
H22A | 0.5164 | 0.2055 | 0.4897 | 0.091* | |
C23 | 0.4773 (7) | 0.1267 (7) | 0.5610 (7) | 0.094 (4) | |
H23A | 0.5232 | 0.0991 | 0.5609 | 0.113* | |
C24 | 0.4140 (8) | 0.1044 (6) | 0.6030 (7) | 0.095 (4) | |
H24A | 0.4166 | 0.0611 | 0.6314 | 0.114* | |
C25 | 0.3470 (7) | 0.1447 (6) | 0.6040 (6) | 0.083 (3) | |
H25A | 0.3040 | 0.1292 | 0.6331 | 0.100* | |
C26 | 0.3428 (5) | 0.2088 (5) | 0.5615 (6) | 0.072 (3) | |
H26A | 0.2968 | 0.2363 | 0.5623 | 0.087* | |
C31 | 0.2102 (5) | 0.4458 (4) | 0.4070 (5) | 0.052 (2) | |
C32 | 0.2072 (5) | 0.4078 (5) | 0.3375 (5) | 0.065 (2) | |
H32A | 0.2427 | 0.3701 | 0.3284 | 0.078* | |
C33 | 0.1516 (7) | 0.4252 (7) | 0.2806 (6) | 0.087 (3) | |
H33A | 0.1500 | 0.3993 | 0.2340 | 0.104* | |
C34 | 0.0994 (7) | 0.4809 (7) | 0.2941 (7) | 0.094 (4) | |
H34A | 0.0622 | 0.4930 | 0.2565 | 0.113* | |
C35 | 0.1020 (7) | 0.5187 (6) | 0.3625 (7) | 0.089 (3) | |
H35A | 0.0659 | 0.5560 | 0.3716 | 0.107* | |
C36 | 0.1571 (6) | 0.5026 (5) | 0.4180 (6) | 0.075 (3) | |
H36A | 0.1590 | 0.5299 | 0.4637 | 0.090* | |
C41 | 0.2233 (4) | 0.4189 (4) | 0.5699 (4) | 0.047 (2) | |
C42 | 0.2427 (6) | 0.4568 (5) | 0.6357 (5) | 0.066 (2) | |
H42A | 0.2870 | 0.4867 | 0.6355 | 0.079* | |
C43 | 0.1975 (6) | 0.4514 (6) | 0.7027 (5) | 0.081 (3) | |
H43A | 0.2116 | 0.4778 | 0.7468 | 0.097* | |
C44 | 0.1328 (6) | 0.4079 (6) | 0.7044 (6) | 0.075 (3) | |
H44A | 0.1021 | 0.4048 | 0.7491 | 0.090* | |
C45 | 0.1133 (5) | 0.3686 (6) | 0.6388 (6) | 0.083 (3) | |
H45A | 0.0696 | 0.3380 | 0.6394 | 0.099* | |
C46 | 0.1577 (5) | 0.3742 (6) | 0.5726 (5) | 0.075 (3) | |
H46A | 0.1436 | 0.3476 | 0.5286 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0480 (6) | 0.0842 (8) | 0.1042 (10) | −0.0197 (6) | 0.0062 (6) | −0.0318 (7) |
Cu2 | 0.0712 (8) | 0.0587 (7) | 0.0944 (9) | −0.0267 (6) | 0.0163 (7) | −0.0161 (7) |
S1 | 0.0575 (12) | 0.0496 (11) | 0.0406 (11) | −0.0008 (10) | 0.0026 (10) | 0.0001 (10) |
S2 | 0.0420 (11) | 0.0496 (12) | 0.0723 (15) | 0.0022 (9) | 0.0057 (11) | −0.0125 (11) |
P1 | 0.0416 (11) | 0.0535 (13) | 0.0577 (14) | −0.0043 (10) | 0.0016 (10) | −0.0092 (11) |
P2 | 0.0490 (12) | 0.0434 (11) | 0.0556 (13) | −0.0068 (10) | 0.0065 (11) | −0.0063 (11) |
O1 | 0.112 (6) | 0.098 (6) | 0.097 (6) | −0.055 (5) | −0.015 (5) | 0.000 (5) |
N1 | 0.034 (3) | 0.051 (4) | 0.082 (5) | −0.012 (3) | −0.003 (3) | −0.011 (4) |
C1 | 0.149 (13) | 0.184 (15) | 0.118 (11) | −0.069 (12) | −0.056 (10) | 0.010 (11) |
C11 | 0.055 (5) | 0.055 (5) | 0.048 (5) | 0.000 (4) | −0.001 (4) | 0.005 (4) |
C12 | 0.079 (7) | 0.084 (7) | 0.060 (6) | 0.002 (6) | 0.008 (5) | 0.003 (6) |
C13 | 0.123 (10) | 0.104 (9) | 0.060 (7) | −0.002 (8) | 0.008 (7) | 0.003 (7) |
C14 | 0.147 (12) | 0.094 (9) | 0.041 (6) | 0.039 (9) | −0.004 (7) | 0.001 (6) |
C15 | 0.155 (12) | 0.067 (7) | 0.061 (7) | −0.011 (7) | −0.011 (8) | −0.004 (6) |
C16 | 0.096 (8) | 0.073 (7) | 0.064 (7) | −0.018 (6) | −0.004 (6) | −0.003 (6) |
C21 | 0.043 (4) | 0.063 (5) | 0.045 (5) | −0.007 (4) | −0.010 (4) | −0.013 (4) |
C22 | 0.066 (6) | 0.092 (7) | 0.068 (7) | 0.010 (6) | 0.014 (5) | 0.013 (6) |
C23 | 0.098 (9) | 0.096 (9) | 0.088 (8) | 0.033 (7) | 0.000 (7) | 0.013 (7) |
C24 | 0.097 (9) | 0.081 (8) | 0.106 (10) | −0.007 (7) | −0.025 (8) | 0.023 (7) |
C25 | 0.074 (7) | 0.092 (8) | 0.083 (8) | −0.017 (6) | −0.006 (6) | 0.017 (7) |
C26 | 0.052 (5) | 0.087 (7) | 0.079 (7) | −0.005 (5) | −0.010 (5) | 0.012 (6) |
C31 | 0.057 (5) | 0.049 (5) | 0.052 (5) | −0.006 (4) | 0.008 (4) | 0.008 (4) |
C32 | 0.074 (6) | 0.070 (6) | 0.050 (6) | −0.009 (5) | 0.007 (5) | 0.005 (5) |
C33 | 0.113 (9) | 0.096 (8) | 0.050 (6) | −0.037 (8) | −0.013 (6) | 0.014 (6) |
C34 | 0.089 (8) | 0.107 (10) | 0.087 (9) | −0.022 (7) | −0.024 (7) | 0.056 (8) |
C35 | 0.093 (8) | 0.078 (7) | 0.097 (9) | 0.010 (6) | −0.017 (7) | 0.028 (7) |
C36 | 0.085 (7) | 0.065 (6) | 0.074 (7) | 0.001 (6) | 0.000 (6) | 0.005 (5) |
C41 | 0.048 (5) | 0.047 (5) | 0.046 (5) | −0.007 (4) | 0.001 (4) | 0.007 (4) |
C42 | 0.071 (6) | 0.069 (6) | 0.056 (6) | −0.012 (5) | −0.002 (5) | −0.003 (5) |
C43 | 0.103 (8) | 0.093 (8) | 0.047 (6) | −0.015 (7) | −0.002 (6) | −0.005 (6) |
C44 | 0.075 (7) | 0.100 (8) | 0.050 (6) | −0.003 (6) | 0.014 (5) | 0.012 (6) |
C45 | 0.060 (6) | 0.119 (9) | 0.069 (7) | −0.040 (6) | 0.012 (5) | −0.003 (7) |
C46 | 0.069 (6) | 0.098 (7) | 0.057 (6) | −0.025 (6) | 0.010 (5) | −0.013 (5) |
Cu1—P1 | 2.182 (2) | C21—C22 | 1.385 (12) |
Cu1—S1 | 2.351 (2) | C22—C23 | 1.376 (13) |
Cu1—S2 | 2.370 (2) | C22—H22A | 0.9300 |
Cu1—S1i | 2.805 (2) | C23—C24 | 1.360 (15) |
Cu1—Cu2i | 2.8179 (18) | C23—H23A | 0.9300 |
Cu1—Cu2 | 2.8456 (15) | C24—C25 | 1.357 (14) |
Cu2—P2i | 2.177 (2) | C24—H24A | 0.9300 |
Cu2—S2 | 2.298 (2) | C25—C26 | 1.380 (13) |
Cu2—S1 | 2.366 (2) | C25—H25A | 0.9300 |
P1—N1 | 1.675 (6) | C26—H26A | 0.9300 |
P1—C11 | 1.818 (8) | C31—C32 | 1.382 (11) |
P1—C21 | 1.825 (9) | C31—C36 | 1.389 (12) |
P2—N1 | 1.669 (7) | C32—C33 | 1.397 (13) |
P2—C31 | 1.818 (9) | C32—H32A | 0.9300 |
P2—C41 | 1.821 (8) | C33—C34 | 1.371 (15) |
O1—C1 | 1.353 (13) | C33—H33A | 0.9300 |
O1—H1 | 0.8200 | C34—C35 | 1.366 (15) |
N1—H1A | 0.8600 | C34—H34A | 0.9300 |
C1—H1B | 0.9600 | C35—C36 | 1.367 (13) |
C1—H1C | 0.9600 | C35—H35A | 0.9300 |
C1—H1D | 0.9600 | C36—H36A | 0.9300 |
C11—C12 | 1.362 (12) | C41—C42 | 1.364 (11) |
C11—C16 | 1.373 (11) | C41—C46 | 1.385 (11) |
C12—C13 | 1.368 (14) | C42—C43 | 1.389 (12) |
C12—H12A | 0.9300 | C42—H42A | 0.9300 |
C13—C14 | 1.347 (15) | C43—C44 | 1.358 (13) |
C13—H13A | 0.9300 | C43—H43A | 0.9300 |
C14—C15 | 1.343 (15) | C44—C45 | 1.377 (13) |
C14—H14A | 0.9300 | C44—H44A | 0.9300 |
C15—C16 | 1.397 (14) | C45—C46 | 1.368 (12) |
C15—H15A | 0.9300 | C45—H45A | 0.9300 |
C16—H16A | 0.9300 | C46—H46A | 0.9300 |
C21—C26 | 1.367 (11) | ||
P1—Cu1—S1 | 133.94 (10) | C13—C14—H14A | 119.5 |
P1—Cu1—S2 | 119.99 (9) | C14—C15—C16 | 120.0 (11) |
S1—Cu1—S2 | 97.92 (8) | C14—C15—H15A | 120.0 |
P1—Cu1—S1i | 116.40 (9) | C16—C15—H15A | 120.0 |
S1—Cu1—S1i | 86.14 (8) | C11—C16—C15 | 119.9 (10) |
S2—Cu1—S1i | 90.32 (8) | C11—C16—H16A | 120.1 |
P1—Cu1—Cu2i | 91.34 (7) | C15—C16—H16A | 120.1 |
S1—Cu1—Cu2i | 72.80 (7) | C26—C21—C22 | 118.2 (8) |
S2—Cu1—Cu2i | 138.77 (8) | C26—C21—P1 | 124.5 (7) |
S1i—Cu1—Cu2i | 49.78 (5) | C22—C21—P1 | 117.3 (7) |
P1—Cu1—Cu2 | 171.27 (8) | C23—C22—C21 | 120.8 (10) |
S1—Cu1—Cu2 | 53.14 (6) | C23—C22—H22A | 119.6 |
S2—Cu1—Cu2 | 51.29 (6) | C21—C22—H22A | 119.6 |
S1i—Cu1—Cu2 | 66.31 (6) | C24—C23—C22 | 119.7 (11) |
Cu2i—Cu1—Cu2 | 96.28 (5) | C24—C23—H23A | 120.1 |
P2i—Cu2—S2 | 127.12 (9) | C22—C23—H23A | 120.1 |
P2i—Cu2—S1 | 130.38 (9) | C25—C24—C23 | 120.5 (11) |
S2—Cu2—S1 | 99.54 (8) | C25—C24—H24A | 119.7 |
P2i—Cu2—Cu1i | 91.76 (7) | C23—C24—H24A | 119.7 |
S2—Cu2—Cu1i | 129.81 (8) | C24—C25—C26 | 119.8 (11) |
S1—Cu2—Cu1i | 64.82 (6) | C24—C25—H25A | 120.1 |
P2i—Cu2—Cu1 | 172.45 (9) | C26—C25—H25A | 120.1 |
S2—Cu2—Cu1 | 53.60 (6) | C21—C26—C25 | 120.9 (9) |
S1—Cu2—Cu1 | 52.66 (6) | C21—C26—H26A | 119.5 |
Cu1i—Cu2—Cu1 | 83.72 (5) | C25—C26—H26A | 119.5 |
Cu1—S1—Cu2 | 74.20 (7) | C32—C31—C36 | 118.0 (9) |
Cu1—S1—Cu1i | 93.86 (8) | C32—C31—P2 | 123.1 (7) |
Cu2—S1—Cu1i | 65.40 (6) | C36—C31—P2 | 118.9 (7) |
Cu2—S2—Cu1 | 75.11 (7) | C31—C32—C33 | 121.0 (10) |
N1—P1—C11 | 105.7 (4) | C31—C32—H32A | 119.5 |
N1—P1—C21 | 103.6 (4) | C33—C32—H32A | 119.5 |
C11—P1—C21 | 101.0 (4) | C34—C33—C32 | 119.2 (11) |
N1—P1—Cu1 | 115.5 (2) | C34—C33—H33A | 120.4 |
C11—P1—Cu1 | 113.1 (3) | C32—C33—H33A | 120.4 |
C21—P1—Cu1 | 116.3 (3) | C35—C34—C33 | 120.1 (11) |
N1—P2—C31 | 102.5 (4) | C35—C34—H34A | 119.9 |
N1—P2—C41 | 105.3 (4) | C33—C34—H34A | 119.9 |
C31—P2—C41 | 103.1 (4) | C34—C35—C36 | 120.8 (11) |
N1—P2—Cu2i | 115.1 (2) | C34—C35—H35A | 119.6 |
C31—P2—Cu2i | 114.1 (3) | C36—C35—H35A | 119.6 |
C41—P2—Cu2i | 115.3 (3) | C35—C36—C31 | 120.8 (10) |
C1—O1—H1 | 109.5 | C35—C36—H36A | 119.6 |
P2—N1—P1 | 124.7 (4) | C31—C36—H36A | 119.6 |
P2—N1—H1A | 117.7 | C42—C41—C46 | 117.9 (8) |
P1—N1—H1A | 117.7 | C42—C41—P2 | 120.4 (6) |
O1—C1—H1B | 109.5 | C46—C41—P2 | 121.7 (6) |
O1—C1—H1C | 109.5 | C41—C42—C43 | 121.0 (9) |
H1B—C1—H1C | 109.5 | C41—C42—H42A | 119.5 |
O1—C1—H1D | 109.5 | C43—C42—H42A | 119.5 |
H1B—C1—H1D | 109.5 | C44—C43—C42 | 120.6 (9) |
H1C—C1—H1D | 109.5 | C44—C43—H43A | 119.7 |
C12—C11—C16 | 117.6 (9) | C42—C43—H43A | 119.7 |
C12—C11—P1 | 120.4 (7) | C43—C44—C45 | 118.8 (9) |
C16—C11—P1 | 122.1 (7) | C43—C44—H44A | 120.6 |
C11—C12—C13 | 122.7 (10) | C45—C44—H44A | 120.6 |
C11—C12—H12A | 118.6 | C46—C45—C44 | 120.6 (9) |
C13—C12—H12A | 118.6 | C46—C45—H45A | 119.7 |
C14—C13—C12 | 118.8 (12) | C44—C45—H45A | 119.7 |
C14—C13—H13A | 120.6 | C45—C46—C41 | 121.0 (9) |
C12—C13—H13A | 120.6 | C45—C46—H46A | 119.5 |
C15—C14—C13 | 121.1 (11) | C41—C46—H46A | 119.5 |
C15—C14—H14A | 119.5 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.86 | 2.04 | 2.895 (9) | 177 |
O1—H1···S2ii | 0.82 | 2.35 | 3.152 (7) | 166 |
Symmetry code: (ii) x−1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu4(SH)4(C24H21NP2)2]·2CH4O |
Mr | 1221.23 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 17.0144 (8), 18.2738 (9), 17.1713 (9) |
V (Å3) | 5338.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.89 |
Crystal size (mm) | 0.30 × 0.24 × 0.24 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.586, 0.636 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15623, 4726, 2983 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.086, 0.174, 1.21 |
No. of reflections | 4726 |
No. of parameters | 300 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0261P)2 + 28.2604P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.76, −0.99 |
Computer programs: SMART (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
P1—Cu1—S1 | 133.94 (10) | P2i—Cu2—S2 | 127.12 (9) |
P1—Cu1—S2 | 119.99 (9) | P2i—Cu2—S1 | 130.38 (9) |
S1—Cu1—S2 | 97.92 (8) | S2—Cu2—S1 | 99.54 (8) |
P1—Cu1—S1i | 116.40 (9) | Cu1—S1—Cu2 | 74.20 (7) |
S1—Cu1—S1i | 86.14 (8) | Cu1—S1—Cu1i | 93.86 (8) |
S2—Cu1—S1i | 90.32 (8) | Cu2—S1—Cu1i | 65.40 (6) |
Cu2i—Cu1—Cu2 | 96.28 (5) | Cu2—S2—Cu1 | 75.11 (7) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.86 | 2.04 | 2.895 (9) | 176.5 |
O1—H1···S2ii | 0.82 | 2.35 | 3.152 (7) | 166.0 |
Symmetry code: (ii) x−1/2, −y+1/2, −z+1. |
The design of luminescent polynuclear d10 metal complexes with various molecular motifs has attracted increasing attention in recent years due to their potential applications in materials science, such as photoactive reagents, optical sensors, light-emitting devices and photovoltaic fabrication (Yam et al., 2003; Chen et al., 2008; Henkel & Krebs, 2004). This stems from the tendency of these metal ions to form clusters and aggregates as a result of weak metal–metal interactions. In this area, polynuclear CuI–chalcogenide species are attracting considerable interest because of their rich photophysical properties and structural diversity (Henkel & Krebs, 2004; Brown et al., 2005; Lee et al., 2006). Many novel structures have been discovered in the synthesis of CuI aggregates of high nuclearity based on metal diphosphine building blocks and using the S2- ion, monothiolates, 1,1-dithiolates or 1,2-dithiolates as the bridging ligands (Yam et al., 2003). However, in only a few cases were they derived from self-assembly with a capped SH- ion (Han et al., 2003; Chen et al., 2004).
To investigate new structural and functional motifs, we are currently interested in developing luminescent molecular materials formed by self-assembly occurring between metal diphosphine and chalcogenide components, where the former possesses labile solvate sites while the latter show versatile bridging characteristics. Recently, the first example of a copper(I)–thiolate complex with a diphosphine as co-ligand, namely [Cu3(µ2-Ph2PNHPPh2)3(µ3-SH)2]+, which displays an unprecedented trigonal bipyramid comprising a triangular CuI3 core dicapped with µ3-SH, has been isolated via the disruption of a C—S bond from the reaction between [Cu2(Ph2PNHPPh2)2(MeCN)2](BF4)2 and the sodium salt of mercaptoacetic acid (HSCH2COONa) (Han et al., 2003). Here, we report the synthesis and crystal structure of the title novel neutral tetranuclear copper(I)–thiolate complex, [Cu4(µ2-SH)2(µ3-SH)2(µ2-Ph2PNHPPh2)2](CH3OH)2, (I), which is considerably different from the complex mentioned above in structural and functional motifs. To our knowledge, (I) is the first example of a coinage tetranuclear metal complex with mixed µ2-SH-bridged and µ3-SH-bridged chromophores.
Complex (I) is composed of two [Cu2(Ph2PNHPPh2)] units linked together by two µ2-SH and two µ3-SH chromophores. The complex is located on a crystallographic centre of inversion (Fig.1; selected bond angles in Table 1). In (I), the Cu and S atoms are alternately bonded to form an eight-membered ring in which two S atoms further bridge two Cu atoms to form a distorted stepladder arrangement or a distorted chair-like conformation. Each Cu atom is bonded to one P atom of a bis(phosphine) ligand in such a way that two Cu atoms have approximate CuPS2 trigonal planar geometry and the other two have CuPS3 tetrahedral coordination geometry. There are two types of bridging –SH groups present, namely µ2-SH and µ3-SH. This structural feature is similar to the tetramer [(µ2-X)2(µ3-X)2(CuPPh3)4] (X is Cl, Br, I or SPh) reported in the literature (Camus et al., 1975; Fu et al., 2004; Ganesamoorthy et al., 2007; Dance et al., 1985). The Cu—S bond distances at the trigonal Cu1 centre [2.298 (2) and 2.366 (2) Å)] are slightly shorter than the corresponding distances at the tetrahedral Cu2 centre [2.351 (2), 2.370 (2) and 2.805 (2) Å]. The Cu—S bond distances observed here are comparable with the corresponding distances observed in the copper thiolate tetramer (Dance et al., 1985). The Cu—P bond distances are normal. The distances between the two Cu centres are Cu1···Cu2 = 2.8456 (15) Å and Cu1···Cu2i = 2.8179 (18) Å [symmetry code: (i) 1-x, 1-y, 1-z], which indicates the presence of weak ligand-supported Cu···Cu interactions in complex (I). Such metallophilic interactions between formally closed-shell metal centres are well documented and are due to the combination of correlation and relativistic effects with added ionic contributions (Pyykko, 1997).
There are two unique hydrogen-bond interactions between the neutral tetranuclear cluster [Cu4(µ2-SH)2(µ3-SH)2(µ2-Ph2PNHPPh2)2] and the solvent MeOH molecules. As shown in Fig. 2, each tetranuclear cluster molecule links to four MeOH molecules through two N—H···O and two O—H···S hydrogen bonds. Each of these four MeOH molecules further links to another tetranuclear cluster unit through N—H···O or O—H···S hydrogen bonds. Details of the hydrogen-bond geometry are listed in Table 2. Consequently, a two-dimensional hydrogen-bonded supramolecular network of (I) is formed in the ab plane.
In conclusion, a novel tetranuclear copper(I)–thiolate complex supported by Ph2PNHPPh2 ligands has been successfully prepared. The molecular structure has an interesting Cu4(µ2-SH)2(µ3-SH)2 core with a distorted stepladder motif and exhibits ligand-supported Cu···Cu interactions.