Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803006330/fl6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803006330/fl6025Isup2.hkl |
CCDC reference: 209898
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.011 Å
- R factor = 0.068
- wR factor = 0.169
- Data-to-parameter ratio = 14.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
A mixture of [Cu(MeCN)4](PF6)2 (Shriver, 1979) and dppm in 1:1 ratio in dichloromethane was stirred under inert atmosphere at room temperature overnight. Concentration of the solution and addition of diethyl ether resulted in the precipitation of an off-white solid. Well shaped colorless crystals suitable for X-ray diffraction measurement were grown by slow diffusion of diethyl ether into acetonitrile at room temperature.
The positions of the H atoms were genetared geometrically (C—H = 0.96 Å), assigned isotropic displacement parameters and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement.
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of the title complex with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
[Cu2(C25H22P2)2(C2H3N)4](PF6)2 | F(000) = 2752 |
Mr = 1349.97 | Dx = 1.476 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4793 reflections |
a = 22.5125 (3) Å | θ = 1.8–25.0° |
b = 13.1916 (2) Å | µ = 0.94 mm−1 |
c = 21.6096 (3) Å | T = 293 K |
β = 108.748 (1)° | Block, colorless |
V = 6077.02 (15) Å3 | 0.60 × 0.56 × 0.56 mm |
Z = 4 |
Siemens SMART 1K CCD diffractometer | 5273 independent reflections |
Radiation source: fine-focus sealed tube | 4180 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −26→23 |
Tmin = 0.561, Tmax = 0.592 | k = −15→13 |
8897 measured reflections | l = −10→25 |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + (0.0384P)2 + 40.8701P] where P = (Fo2 + 2Fc2)/3 |
5273 reflections | (Δ/σ)max < 0.001 |
368 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
[Cu2(C25H22P2)2(C2H3N)4](PF6)2 | V = 6077.02 (15) Å3 |
Mr = 1349.97 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 22.5125 (3) Å | µ = 0.94 mm−1 |
b = 13.1916 (2) Å | T = 293 K |
c = 21.6096 (3) Å | 0.60 × 0.56 × 0.56 mm |
β = 108.748 (1)° |
Siemens SMART 1K CCD diffractometer | 5273 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4180 reflections with I > 2σ(I) |
Tmin = 0.561, Tmax = 0.592 | Rint = 0.025 |
8897 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + (0.0384P)2 + 40.8701P] where P = (Fo2 + 2Fc2)/3 |
5273 reflections | Δρmax = 0.55 e Å−3 |
368 parameters | Δρmin = −0.66 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 | 0.44474 (3) | 0.64257 (5) | 0.79918 (3) | 0.0433 (2) | |
P1 | 0.38179 (6) | 0.70275 (11) | 0.70157 (6) | 0.0372 (3) | |
P2 | 0.51986 (6) | 0.74477 (11) | 0.86682 (6) | 0.0369 (3) | |
P3 | 0.12445 (10) | 0.37859 (16) | 0.37166 (10) | 0.0678 (5) | |
F1 | 0.0778 (4) | 0.4279 (7) | 0.3144 (4) | 0.192 (4) | |
F2 | 0.1679 (5) | 0.3197 (6) | 0.4271 (4) | 0.195 (4) | |
F3 | 0.1111 (4) | 0.2824 (8) | 0.3281 (4) | 0.195 (4) | |
F4 | 0.0766 (5) | 0.3449 (8) | 0.4021 (5) | 0.215 (5) | |
F5 | 0.1805 (4) | 0.3977 (7) | 0.3503 (5) | 0.205 (4) | |
F6 | 0.1347 (4) | 0.4777 (5) | 0.4096 (4) | 0.151 (2) | |
N1 | 0.4595 (2) | 0.4906 (4) | 0.8079 (2) | 0.0552 (13) | |
N2 | 0.3827 (3) | 0.6485 (4) | 0.8580 (3) | 0.0595 (14) | |
C1 | 0.4631 (3) | 0.4063 (5) | 0.8172 (3) | 0.0591 (16) | |
C01 | 0.5831 (2) | 0.7964 (4) | 0.8396 (3) | 0.0382 (12) | |
H01A | 0.6156 | 0.8233 | 0.8772 | 0.046* | |
H01B | 0.5665 | 0.8523 | 0.8098 | 0.046* | |
C2 | 0.4661 (6) | 0.2965 (6) | 0.8286 (7) | 0.107 (3) | |
HC2A | 0.5044 | 0.2800 | 0.8625 | 0.19 (6)* | |
HC2B | 0.4648 | 0.2619 | 0.7891 | 0.19 (6)* | |
HC2C | 0.4310 | 0.2757 | 0.8417 | 0.22 (7)* | |
C3 | 0.3533 (3) | 0.6836 (6) | 0.8851 (3) | 0.0654 (18) | |
C4 | 0.3146 (5) | 0.7325 (8) | 0.9196 (5) | 0.108 (3)* | |
H4A | 0.3287 | 0.7120 | 0.9646 | 0.162* | |
H4B | 0.2716 | 0.7127 | 0.8998 | 0.162* | |
H4C | 0.3181 | 0.8047 | 0.9169 | 0.162* | |
C111 | 0.3414 (3) | 0.6132 (4) | 0.6372 (3) | 0.0443 (13) | |
C112 | 0.3575 (3) | 0.5117 (5) | 0.6433 (3) | 0.0554 (15) | |
H11A | 0.3900 | 0.4894 | 0.6794 | 0.066* | |
C113 | 0.3253 (4) | 0.4426 (6) | 0.5957 (4) | 0.077 (2) | |
H11C | 0.3368 | 0.3746 | 0.5997 | 0.092* | |
C114 | 0.2765 (4) | 0.4746 (7) | 0.5429 (4) | 0.078 (2) | |
H11D | 0.2539 | 0.4280 | 0.5120 | 0.093* | |
C115 | 0.2611 (3) | 0.5749 (6) | 0.5356 (3) | 0.075 (2) | |
H11E | 0.2288 | 0.5965 | 0.4990 | 0.090* | |
C116 | 0.2931 (3) | 0.6445 (5) | 0.5822 (3) | 0.0623 (17) | |
H11B | 0.2822 | 0.7127 | 0.5768 | 0.075* | |
C121 | 0.3159 (3) | 0.7721 (5) | 0.7137 (3) | 0.0454 (13) | |
C122 | 0.3127 (3) | 0.8763 (6) | 0.7142 (4) | 0.072 (2) | |
H12B | 0.3434 | 0.9147 | 0.7048 | 0.087* | |
C123 | 0.2636 (4) | 0.9246 (8) | 0.7287 (5) | 0.103 (3) | |
H12E | 0.2611 | 0.9949 | 0.7281 | 0.123* | |
C124 | 0.2189 (4) | 0.8675 (10) | 0.7439 (4) | 0.101 (4) | |
H12C | 0.1872 | 0.8997 | 0.7555 | 0.122* | |
C125 | 0.2207 (4) | 0.7638 (10) | 0.7420 (4) | 0.095 (3) | |
H12D | 0.1896 | 0.7256 | 0.7509 | 0.114* | |
C126 | 0.2687 (3) | 0.7165 (6) | 0.7268 (3) | 0.0671 (19) | |
H12A | 0.2697 | 0.6461 | 0.7253 | 0.080* | |
C211 | 0.5619 (2) | 0.6938 (4) | 0.9477 (2) | 0.0430 (13) | |
C212 | 0.6053 (3) | 0.7506 (6) | 0.9957 (3) | 0.0611 (17) | |
H21D | 0.6124 | 0.8181 | 0.9879 | 0.073* | |
C213 | 0.6377 (3) | 0.7063 (7) | 1.0550 (3) | 0.073 (2) | |
H21B | 0.6664 | 0.7447 | 1.0870 | 0.088* | |
C214 | 0.6282 (4) | 0.6065 (7) | 1.0673 (3) | 0.080 (2) | |
H21C | 0.6505 | 0.5776 | 1.1073 | 0.097* | |
C215 | 0.5858 (4) | 0.5499 (6) | 1.0206 (3) | 0.081 (2) | |
H21E | 0.5790 | 0.4824 | 1.0287 | 0.097* | |
C216 | 0.5526 (3) | 0.5936 (5) | 0.9608 (3) | 0.0616 (17) | |
H21A | 0.5239 | 0.5547 | 0.9292 | 0.074* | |
C221 | 0.4813 (2) | 0.8582 (4) | 0.8845 (3) | 0.0425 (12) | |
C222 | 0.4621 (3) | 0.9350 (5) | 0.8384 (3) | 0.0555 (15) | |
H22A | 0.4744 | 0.9328 | 0.8012 | 0.067* | |
C223 | 0.4252 (4) | 1.0146 (5) | 0.8464 (4) | 0.077 (2) | |
H22E | 0.4128 | 1.0651 | 0.8148 | 0.093* | |
C224 | 0.4072 (4) | 1.0188 (6) | 0.9006 (4) | 0.083 (2) | |
H22D | 0.3818 | 1.0715 | 0.9057 | 0.100* | |
C225 | 0.4263 (4) | 0.9457 (7) | 0.9479 (4) | 0.083 (2) | |
H22C | 0.4149 | 0.9502 | 0.9855 | 0.100* | |
C226 | 0.4628 (3) | 0.8647 (6) | 0.9401 (3) | 0.0641 (18) | |
H22B | 0.4750 | 0.8147 | 0.9720 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0446 (4) | 0.0405 (4) | 0.0385 (4) | −0.0039 (3) | 0.0046 (3) | 0.0024 (3) |
P1 | 0.0368 (7) | 0.0385 (7) | 0.0346 (7) | −0.0011 (6) | 0.0088 (6) | 0.0013 (6) |
P2 | 0.0394 (7) | 0.0386 (7) | 0.0321 (6) | −0.0028 (6) | 0.0107 (6) | −0.0020 (6) |
P3 | 0.0643 (12) | 0.0669 (12) | 0.0676 (12) | 0.0085 (9) | 0.0150 (10) | 0.0060 (10) |
F1 | 0.179 (7) | 0.235 (9) | 0.130 (6) | 0.069 (7) | 0.004 (5) | 0.009 (6) |
F2 | 0.240 (10) | 0.138 (6) | 0.164 (7) | 0.016 (6) | 0.006 (7) | 0.005 (5) |
F3 | 0.197 (8) | 0.225 (9) | 0.155 (7) | 0.013 (7) | 0.044 (6) | −0.047 (7) |
F4 | 0.229 (10) | 0.259 (11) | 0.186 (8) | −0.120 (9) | 0.107 (8) | −0.081 (8) |
F5 | 0.175 (8) | 0.182 (8) | 0.292 (12) | 0.025 (7) | 0.122 (8) | 0.024 (8) |
F6 | 0.193 (7) | 0.096 (4) | 0.156 (6) | 0.003 (4) | 0.046 (5) | −0.005 (4) |
N1 | 0.058 (3) | 0.047 (3) | 0.052 (3) | −0.001 (2) | 0.006 (2) | 0.004 (2) |
N2 | 0.052 (3) | 0.079 (4) | 0.047 (3) | −0.006 (3) | 0.016 (3) | 0.012 (3) |
C1 | 0.061 (4) | 0.050 (4) | 0.063 (4) | 0.009 (3) | 0.016 (3) | 0.007 (3) |
C01 | 0.043 (3) | 0.029 (3) | 0.041 (3) | 0.000 (2) | 0.011 (2) | −0.003 (2) |
C2 | 0.125 (9) | 0.053 (5) | 0.155 (10) | 0.019 (5) | 0.061 (8) | 0.027 (6) |
C3 | 0.055 (4) | 0.092 (5) | 0.055 (4) | −0.007 (4) | 0.025 (3) | 0.007 (4) |
C111 | 0.044 (3) | 0.047 (3) | 0.040 (3) | −0.008 (3) | 0.010 (2) | −0.003 (2) |
C112 | 0.068 (4) | 0.044 (3) | 0.051 (3) | −0.006 (3) | 0.014 (3) | −0.002 (3) |
C113 | 0.102 (6) | 0.050 (4) | 0.077 (5) | −0.013 (4) | 0.028 (5) | −0.015 (4) |
C114 | 0.077 (5) | 0.087 (6) | 0.062 (4) | −0.029 (4) | 0.014 (4) | −0.025 (4) |
C115 | 0.059 (4) | 0.089 (6) | 0.061 (4) | −0.007 (4) | −0.004 (3) | −0.010 (4) |
C116 | 0.063 (4) | 0.055 (4) | 0.056 (4) | 0.003 (3) | 0.001 (3) | −0.005 (3) |
C121 | 0.039 (3) | 0.062 (4) | 0.035 (3) | 0.004 (3) | 0.012 (2) | −0.001 (3) |
C122 | 0.057 (4) | 0.069 (5) | 0.096 (5) | −0.002 (3) | 0.031 (4) | −0.028 (4) |
C123 | 0.067 (5) | 0.108 (7) | 0.131 (8) | 0.017 (5) | 0.030 (5) | −0.059 (6) |
C124 | 0.050 (5) | 0.189 (11) | 0.064 (5) | 0.037 (6) | 0.018 (4) | −0.027 (6) |
C125 | 0.053 (5) | 0.172 (10) | 0.066 (5) | 0.023 (6) | 0.028 (4) | 0.030 (6) |
C126 | 0.048 (4) | 0.091 (5) | 0.065 (4) | 0.008 (4) | 0.023 (3) | 0.030 (4) |
C211 | 0.040 (3) | 0.054 (3) | 0.035 (3) | −0.003 (3) | 0.011 (2) | 0.000 (2) |
C212 | 0.062 (4) | 0.070 (4) | 0.043 (3) | −0.012 (3) | 0.005 (3) | −0.007 (3) |
C213 | 0.061 (4) | 0.110 (7) | 0.039 (3) | −0.007 (4) | 0.002 (3) | −0.012 (4) |
C214 | 0.082 (5) | 0.108 (7) | 0.040 (4) | 0.016 (5) | 0.004 (4) | 0.015 (4) |
C215 | 0.095 (6) | 0.077 (5) | 0.056 (4) | −0.004 (4) | 0.005 (4) | 0.026 (4) |
C216 | 0.073 (4) | 0.061 (4) | 0.043 (3) | −0.008 (3) | 0.008 (3) | 0.008 (3) |
C221 | 0.041 (3) | 0.040 (3) | 0.047 (3) | −0.008 (2) | 0.014 (2) | −0.013 (2) |
C222 | 0.068 (4) | 0.045 (3) | 0.057 (4) | 0.004 (3) | 0.025 (3) | −0.006 (3) |
C223 | 0.094 (6) | 0.054 (4) | 0.084 (5) | 0.021 (4) | 0.028 (5) | −0.006 (4) |
C224 | 0.083 (5) | 0.074 (5) | 0.096 (6) | 0.020 (4) | 0.034 (5) | −0.028 (5) |
C225 | 0.091 (6) | 0.100 (6) | 0.070 (5) | 0.012 (5) | 0.041 (4) | −0.024 (5) |
C226 | 0.070 (4) | 0.075 (5) | 0.055 (4) | 0.009 (4) | 0.032 (3) | −0.007 (3) |
Cu1—N1 | 2.031 (5) | C115—C116 | 1.383 (9) |
Cu1—N2 | 2.172 (6) | C115—H11E | 0.9300 |
Cu1—P1 | 2.2730 (14) | C116—H11B | 0.9300 |
Cu1—P2 | 2.2859 (15) | C121—C122 | 1.376 (9) |
P1—C111 | 1.829 (5) | C121—C126 | 1.394 (8) |
P1—C121 | 1.832 (6) | C122—C123 | 1.396 (10) |
P1—C01i | 1.843 (5) | C122—H12B | 0.9300 |
P2—C211 | 1.828 (5) | C123—C124 | 1.380 (14) |
P2—C221 | 1.831 (6) | C123—H12E | 0.9300 |
P2—C01 | 1.837 (5) | C124—C125 | 1.369 (14) |
P3—F1 | 1.490 (7) | C124—H12C | 0.9300 |
P3—F2 | 1.497 (8) | C125—C126 | 1.377 (11) |
P3—F5 | 1.498 (9) | C125—H12D | 0.9300 |
P3—F4 | 1.499 (8) | C126—H12A | 0.9300 |
P3—F6 | 1.521 (7) | C211—C216 | 1.381 (8) |
P3—F3 | 1.551 (9) | C211—C212 | 1.393 (8) |
N1—C1 | 1.128 (8) | C212—C213 | 1.383 (9) |
N2—C3 | 1.115 (8) | C212—H21D | 0.9300 |
C1—C2 | 1.468 (10) | C213—C214 | 1.374 (11) |
C01—P1i | 1.843 (5) | C213—H21B | 0.9300 |
C01—H01A | 0.9700 | C214—C215 | 1.368 (11) |
C01—H01B | 0.9700 | C214—H21C | 0.9300 |
C2—HC2A | 0.9600 | C215—C216 | 1.392 (9) |
C2—HC2B | 0.9600 | C215—H21E | 0.9300 |
C2—HC2C | 0.9600 | C216—H21A | 0.9300 |
C3—C4 | 1.465 (11) | C221—C222 | 1.389 (8) |
C4—H4A | 0.9600 | C221—C226 | 1.393 (8) |
C4—H4B | 0.9600 | C222—C223 | 1.385 (9) |
C4—H4C | 0.9600 | C222—H22A | 0.9300 |
C111—C112 | 1.382 (8) | C223—C224 | 1.359 (11) |
C111—C116 | 1.391 (8) | C223—H22E | 0.9300 |
C112—C113 | 1.391 (9) | C224—C225 | 1.370 (11) |
C112—H11A | 0.9300 | C224—H22D | 0.9300 |
C113—C114 | 1.372 (11) | C225—C226 | 1.391 (10) |
C113—H11C | 0.9300 | C225—H22C | 0.9300 |
C114—C115 | 1.363 (11) | C226—H22B | 0.9300 |
C114—H11D | 0.9300 | ||
N1—Cu1—N2 | 95.6 (2) | C115—C114—C113 | 120.1 (7) |
N1—Cu1—P1 | 117.74 (14) | C115—C114—H11D | 120.0 |
N2—Cu1—P1 | 101.79 (14) | C113—C114—H11D | 120.0 |
N1—Cu1—P2 | 117.24 (15) | C114—C115—C116 | 120.4 (7) |
N2—Cu1—P2 | 95.01 (15) | C114—C115—H11E | 119.8 |
P1—Cu1—P2 | 119.99 (6) | C116—C115—H11E | 119.8 |
C111—P1—C121 | 101.7 (3) | C115—C116—C111 | 120.5 (6) |
C111—P1—C01i | 104.6 (2) | C115—C116—H11B | 119.8 |
C121—P1—C01i | 103.1 (3) | C111—C116—H11B | 119.8 |
C111—P1—Cu1 | 119.29 (19) | C122—C121—C126 | 118.6 (6) |
C121—P1—Cu1 | 109.52 (17) | C122—C121—P1 | 123.2 (5) |
C01i—P1—Cu1 | 116.46 (18) | C126—C121—P1 | 118.1 (5) |
C211—P2—C221 | 103.6 (3) | C121—C122—C123 | 120.3 (8) |
C211—P2—C01 | 103.1 (2) | C121—C122—H12B | 119.8 |
C221—P2—C01 | 103.4 (2) | C123—C122—H12B | 119.8 |
C211—P2—Cu1 | 116.35 (19) | C124—C123—C122 | 119.7 (9) |
C221—P2—Cu1 | 108.21 (17) | C124—C123—H12E | 120.1 |
C01—P2—Cu1 | 120.26 (17) | C122—C123—H12E | 120.1 |
F1—P3—F2 | 174.5 (5) | C125—C124—C123 | 120.5 (8) |
F1—P3—F5 | 96.2 (6) | C125—C124—H12C | 119.8 |
F2—P3—F5 | 86.3 (6) | C123—C124—H12C | 119.8 |
F1—P3—F4 | 94.6 (6) | C124—C125—C126 | 119.5 (9) |
F2—P3—F4 | 82.7 (6) | C124—C125—H12D | 120.2 |
F5—P3—F4 | 168.8 (6) | C126—C125—H12D | 120.2 |
F1—P3—F6 | 91.0 (5) | C125—C126—C121 | 121.2 (8) |
F2—P3—F6 | 93.9 (4) | C125—C126—H12A | 119.4 |
F5—P3—F6 | 91.5 (5) | C121—C126—H12A | 119.4 |
F4—P3—F6 | 91.3 (5) | C216—C211—C212 | 118.6 (6) |
F1—P3—F3 | 84.6 (5) | C216—C211—P2 | 118.8 (4) |
F2—P3—F3 | 90.6 (5) | C212—C211—P2 | 122.6 (5) |
F5—P3—F3 | 88.2 (5) | C213—C212—C211 | 119.9 (7) |
F4—P3—F3 | 89.9 (5) | C213—C212—H21D | 120.1 |
F6—P3—F3 | 175.5 (5) | C211—C212—H21D | 120.1 |
C1—N1—Cu1 | 171.8 (6) | C214—C213—C212 | 121.0 (7) |
C3—N2—Cu1 | 157.5 (6) | C214—C213—H21B | 119.5 |
N1—C1—C2 | 178.5 (9) | C212—C213—H21B | 119.5 |
P2—C01—P1i | 113.8 (3) | C215—C214—C213 | 119.7 (7) |
P2—C01—H01A | 108.8 | C215—C214—H21C | 120.2 |
P1i—C01—H01A | 108.8 | C213—C214—H21C | 120.2 |
P2—C01—H01B | 108.8 | C214—C215—C216 | 119.9 (7) |
P1i—C01—H01B | 108.8 | C214—C215—H21E | 120.1 |
H01A—C01—H01B | 107.7 | C216—C215—H21E | 120.1 |
C1—C2—HC2A | 109.5 | C211—C216—C215 | 121.0 (6) |
C1—C2—HC2B | 109.5 | C211—C216—H21A | 119.5 |
HC2A—C2—HC2B | 109.5 | C215—C216—H21A | 119.5 |
C1—C2—HC2C | 109.5 | C222—C221—C226 | 117.7 (6) |
HC2A—C2—HC2C | 109.5 | C222—C221—P2 | 120.3 (4) |
HC2B—C2—HC2C | 109.5 | C226—C221—P2 | 121.5 (5) |
N2—C3—C4 | 178.3 (9) | C223—C222—C221 | 121.6 (6) |
C3—C4—H4A | 109.5 | C223—C222—H22A | 119.2 |
C3—C4—H4B | 109.5 | C221—C222—H22A | 119.2 |
H4A—C4—H4B | 109.5 | C224—C223—C222 | 119.7 (7) |
C3—C4—H4C | 109.5 | C224—C223—H22E | 120.1 |
H4A—C4—H4C | 109.5 | C222—C223—H22E | 120.1 |
H4B—C4—H4C | 109.5 | C223—C224—C225 | 120.4 (7) |
C112—C111—C116 | 118.5 (5) | C223—C224—H22D | 119.8 |
C112—C111—P1 | 120.2 (4) | C225—C224—H22D | 119.8 |
C116—C111—P1 | 121.3 (5) | C224—C225—C226 | 120.3 (7) |
C111—C112—C113 | 120.5 (6) | C224—C225—H22C | 119.8 |
C111—C112—H11A | 119.8 | C226—C225—H22C | 119.8 |
C113—C112—H11A | 119.8 | C225—C226—C221 | 120.3 (7) |
C114—C113—C112 | 120.0 (7) | C225—C226—H22B | 119.9 |
C114—C113—H11C | 120.0 | C221—C226—H22B | 119.9 |
C112—C113—H11C | 120.0 |
Symmetry code: (i) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C25H22P2)2(C2H3N)4](PF6)2 |
Mr | 1349.97 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 22.5125 (3), 13.1916 (2), 21.6096 (3) |
β (°) | 108.748 (1) |
V (Å3) | 6077.02 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.94 |
Crystal size (mm) | 0.60 × 0.56 × 0.56 |
Data collection | |
Diffractometer | Siemens SMART 1K CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.561, 0.592 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8897, 5273, 4180 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.169, 1.23 |
No. of reflections | 5273 |
No. of parameters | 368 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0384P)2 + 40.8701P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.55, −0.66 |
Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1994), XPREP in SHELXTL (Siemens, 1994), SHELXTL.
Cu1—N1 | 2.031 (5) | Cu1—P1 | 2.2730 (14) |
Cu1—N2 | 2.172 (6) | Cu1—P2 | 2.2859 (15) |
N1—Cu1—N2 | 95.6 (2) | C121—P1—Cu1 | 109.52 (17) |
N1—Cu1—P1 | 117.74 (14) | C01i—P1—Cu1 | 116.46 (18) |
N2—Cu1—P1 | 101.79 (14) | C211—P2—Cu1 | 116.35 (19) |
N1—Cu1—P2 | 117.24 (15) | C01—P2—Cu1 | 120.26 (17) |
N2—Cu1—P2 | 95.01 (15) | C1—N1—Cu1 | 171.8 (6) |
P1—Cu1—P2 | 119.99 (6) | C3—N2—Cu1 | 157.5 (6) |
Symmetry code: (i) −x+1, y, −z+3/2. |
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The diphosphine bis(diphenylphosphino)methane (dppm) is widely used to design coinage metal complexes due to its good bridging properties (Diez et al., 1987). The binuclear compounds [M2(µ2-dppm)2] usually display eight-membered rings (Yang et al., 1997), such as [Au2(µ2-dppm)2][Au(GeCl3)2]2 (Bauer et al., 1997), [Ag2(µ2-dppm)2](ClO4)2 (Ahrens & Jones, 1998) and [Cu2(µ2-dppm)2(MeCN)4](ClO4)2 (Diez et al., 1997). This paper describes the crystal structure of a copper-based system with PF6− as the anion, (I).
The complex consists of the dication [Cu2(µ2-dppm)2(MeCN)4]2+, situated about a twofold axis, and two PF6− anions. A perspective drawing of the complex with the atomic numbering scheme is depicted in Fig. 1. Selected bond lengths and angles are presented in Table 1. The two Cu atoms are doubly bridged by dppm ligands to give an eight-membered ring, [M2(µ2-dppm)2]. The Cu centers adopt a distorted tetrahedral geometry in which the four coordination sites around the copper are occupied by two P atoms of dppm and two N atoms from acetonitrile. The Cu—Cu distance of 3.756 Å, which is longer than that in [Cu2(µ2-dppm)2(MeCN)4](ClO4)2, may be due to the Cu–anion interaction. The Cu—P distances are 2.2730 (14) and 2.2859 (15) Å, which are close to those in the above-mentioned compound. The acetonitrile ligands, on the other hand, are quite different, with one being nearly linear [C1—N1—Cu1 = 171.8 (6)°] and the other bent [C3—N2—Cu1 = 157.5 (6)°). The corresponding Cu—N bond lengths are also different, with N1—Cu1 [2.031 (5) Å] being shorter than N2—Cu1 [2.172 (5) Å].