Bis[μ-methylenebis(diphenylphosphine)-κ2P:P′]disilver(I) diperchlorate acetonitrile disolvate
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007244/ci6210sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007244/ci6210Isup2.hkl |
CCDC reference: 214558
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.013 Å
- R factor = 0.066
- wR factor = 0.131
- Data-to-parameter ratio = 14.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was synthesized by a modification of a literature procedure (Lusser & Peringer, 1985). The complex was obtained by the reaction between [Cu2(µ2-dppm)2](ClO4)2 and AgCCC(CH3)3 in a 1:2 ratio in acetonitrile solution under anaerobic conditions for 24 h. Well formed colorless crystals suitable for X-ray diffraction measurements were grown by the slow diffusion of diethyl ether into a solution of acetonitrile at room temperature.
The H atoms were positioned geometrically (C—H bond lengths were fixed in the range 0.93–0.97 Å), assigned isotropic displacement parameters and allowed to ride on their respective parent C atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of the dication of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted. |
[Ag2(C50H44P4)2](ClO4)2·2C2H3N | F(000) = 1280 |
Mr = 1265.48 | Dx = 1.538 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2900 reflections |
a = 11.4553 (3) Å | θ = 2.3–25.0° |
b = 15.1766 (1) Å | µ = 0.99 mm−1 |
c = 16.0597 (5) Å | T = 293 K |
β = 101.826 (2)° | Prism, colorless |
V = 2732.76 (11) Å3 | 0.32 × 0.30 × 0.28 mm |
Z = 2 |
Siemens SMART CCD diffractometer | 4806 independent reflections |
Radiation source: fine-focus sealed tube | 2920 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→9 |
Tmin = 0.723, Tmax = 0.759 | k = −18→15 |
9485 measured reflections | l = −14→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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0246P)2 + 7.4956P] where P = (Fo2 + 2Fc2)/3 |
4806 reflections | (Δ/σ)max = 0.001 |
326 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[Ag2(C50H44P4)2](ClO4)2·2C2H3N | V = 2732.76 (11) Å3 |
Mr = 1265.48 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.4553 (3) Å | µ = 0.99 mm−1 |
b = 15.1766 (1) Å | T = 293 K |
c = 16.0597 (5) Å | 0.32 × 0.30 × 0.28 mm |
β = 101.826 (2)° |
Siemens SMART CCD diffractometer | 4806 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2920 reflections with I > 2σ(I) |
Tmin = 0.723, Tmax = 0.759 | Rint = 0.060 |
9485 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.63 e Å−3 |
4806 reflections | Δρmin = −0.53 e Å−3 |
326 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 | ||
Ag1 | −0.09335 (5) | 0.51188 (4) | 0.05485 (4) | 0.0507 (2) | |
P1 | −0.01338 (14) | 0.38672 (12) | 0.13986 (11) | 0.0382 (4) | |
C11 | −0.0293 (6) | 0.3960 (4) | 0.2500 (4) | 0.0414 (17) | |
C12 | 0.0567 (7) | 0.4305 (6) | 0.3128 (6) | 0.074 (3) | |
H12 | 0.1290 | 0.4483 | 0.3004 | 0.089* | |
C13 | 0.0378 (9) | 0.4395 (7) | 0.3946 (6) | 0.094 (3) | |
H13 | 0.0965 | 0.4646 | 0.4365 | 0.113* | |
C14 | −0.0674 (11) | 0.4114 (7) | 0.4143 (7) | 0.092 (3) | |
H14 | −0.0784 | 0.4146 | 0.4700 | 0.110* | |
C15 | −0.1539 (10) | 0.3794 (7) | 0.3529 (7) | 0.094 (3) | |
H15 | −0.2265 | 0.3625 | 0.3653 | 0.112* | |
C16 | −0.1347 (7) | 0.3715 (6) | 0.2707 (6) | 0.073 (3) | |
H16 | −0.1953 | 0.3490 | 0.2285 | 0.088* | |
C21 | −0.0812 (6) | 0.2810 (4) | 0.1095 (4) | 0.0393 (16) | |
C22 | −0.0554 (6) | 0.2084 (5) | 0.1630 (5) | 0.056 (2) | |
H22 | 0.0000 | 0.2139 | 0.2139 | 0.067* | |
C23 | −0.1106 (8) | 0.1286 (5) | 0.1416 (6) | 0.068 (2) | |
H23 | −0.0926 | 0.0801 | 0.1773 | 0.082* | |
C24 | −0.1933 (8) | 0.1219 (6) | 0.0662 (7) | 0.075 (3) | |
H24 | −0.2323 | 0.0686 | 0.0519 | 0.090* | |
C25 | −0.2191 (7) | 0.1915 (6) | 0.0124 (6) | 0.069 (2) | |
H25 | −0.2743 | 0.1856 | −0.0386 | 0.082* | |
C26 | −0.1628 (6) | 0.2712 (5) | 0.0340 (5) | 0.0516 (19) | |
H26 | −0.1802 | 0.3189 | −0.0028 | 0.062* | |
P2 | 0.18296 (15) | 0.37193 (12) | 0.03915 (12) | 0.0398 (5) | |
C20 | 0.1470 (5) | 0.3723 (4) | 0.1448 (4) | 0.0363 (16) | |
H20A | 0.1903 | 0.4197 | 0.1782 | 0.044* | |
H20B | 0.1728 | 0.3171 | 0.1732 | 0.044* | |
C31 | 0.1413 (6) | 0.2630 (4) | −0.0019 (4) | 0.0426 (17) | |
C32 | 0.0596 (6) | 0.2537 (5) | −0.0773 (5) | 0.055 (2) | |
H32 | 0.0309 | 0.3034 | −0.1087 | 0.066* | |
C33 | 0.0193 (7) | 0.1704 (6) | −0.1069 (6) | 0.067 (2) | |
H33 | −0.0346 | 0.1645 | −0.1584 | 0.080* | |
C34 | 0.0596 (8) | 0.0977 (6) | −0.0595 (7) | 0.079 (3) | |
H34 | 0.0313 | 0.0421 | −0.0781 | 0.094* | |
C35 | 0.1414 (8) | 0.1061 (5) | 0.0150 (6) | 0.067 (2) | |
H35 | 0.1693 | 0.0561 | 0.0463 | 0.081* | |
C36 | 0.1826 (7) | 0.1876 (5) | 0.0440 (5) | 0.057 (2) | |
H36 | 0.2386 | 0.1925 | 0.0947 | 0.068* | |
C41 | 0.3452 (6) | 0.3769 (5) | 0.0576 (5) | 0.0462 (18) | |
C42 | 0.4018 (7) | 0.3437 (6) | −0.0027 (5) | 0.069 (2) | |
H42 | 0.3591 | 0.3116 | −0.0482 | 0.082* | |
C43 | 0.5233 (7) | 0.3579 (7) | 0.0043 (7) | 0.087 (3) | |
H43 | 0.5609 | 0.3348 | −0.0370 | 0.104* | |
C44 | 0.5869 (8) | 0.4034 (7) | 0.0683 (8) | 0.090 (3) | |
H44 | 0.6678 | 0.4131 | 0.0712 | 0.108* | |
C45 | 0.5324 (7) | 0.4361 (7) | 0.1300 (8) | 0.098 (4) | |
H45 | 0.5768 | 0.4669 | 0.1758 | 0.117* | |
C46 | 0.4111 (7) | 0.4233 (6) | 0.1246 (6) | 0.077 (3) | |
H46 | 0.3742 | 0.4461 | 0.1663 | 0.092* | |
N1 | −0.1897 (9) | 0.5868 (6) | 0.1907 (6) | 0.104 (3) | |
C1 | −0.0815 (10) | 0.6813 (8) | 0.3134 (8) | 0.127 (4) | |
H1A | −0.0443 | 0.7302 | 0.2911 | 0.153* | |
H1B | −0.0216 | 0.6462 | 0.3490 | 0.153* | |
H1C | −0.1367 | 0.7028 | 0.3462 | 0.153* | |
C2 | −0.1434 (10) | 0.6290 (7) | 0.2450 (7) | 0.084 (3) | |
Cl1 | 0.23319 (18) | 0.62567 (14) | 0.20439 (13) | 0.0609 (6) | |
O11 | 0.2947 (6) | 0.5654 (4) | 0.2641 (4) | 0.098 (2) | |
O12 | 0.1535 (6) | 0.5837 (4) | 0.1384 (4) | 0.111 (3) | |
O13 | 0.1764 (8) | 0.6882 (6) | 0.2446 (5) | 0.159 (4) | |
O14 | 0.3154 (7) | 0.6731 (7) | 0.1683 (5) | 0.174 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0438 (3) | 0.0460 (4) | 0.0622 (4) | 0.0067 (3) | 0.0109 (2) | 0.0124 (3) |
P1 | 0.0333 (9) | 0.0398 (11) | 0.0420 (11) | 0.0036 (8) | 0.0090 (8) | 0.0018 (9) |
C11 | 0.048 (4) | 0.036 (4) | 0.041 (4) | 0.006 (3) | 0.012 (3) | −0.004 (3) |
C12 | 0.059 (5) | 0.099 (7) | 0.064 (6) | 0.012 (5) | 0.012 (5) | −0.019 (5) |
C13 | 0.089 (7) | 0.141 (10) | 0.045 (6) | 0.030 (7) | −0.003 (5) | −0.034 (6) |
C14 | 0.136 (10) | 0.082 (8) | 0.065 (7) | 0.021 (7) | 0.040 (7) | −0.001 (6) |
C15 | 0.104 (8) | 0.103 (8) | 0.093 (8) | −0.021 (7) | 0.064 (7) | −0.026 (7) |
C16 | 0.063 (5) | 0.093 (7) | 0.072 (6) | −0.011 (5) | 0.035 (5) | −0.014 (5) |
C21 | 0.041 (4) | 0.039 (4) | 0.039 (4) | 0.002 (3) | 0.011 (3) | −0.003 (3) |
C22 | 0.054 (5) | 0.051 (5) | 0.060 (5) | 0.008 (4) | 0.008 (4) | 0.002 (4) |
C23 | 0.081 (6) | 0.038 (5) | 0.087 (7) | 0.006 (5) | 0.021 (5) | 0.005 (5) |
C24 | 0.070 (6) | 0.051 (6) | 0.108 (8) | −0.010 (5) | 0.024 (6) | −0.018 (6) |
C25 | 0.062 (5) | 0.064 (6) | 0.076 (6) | −0.014 (5) | 0.005 (5) | −0.015 (5) |
C26 | 0.048 (4) | 0.053 (5) | 0.055 (5) | 0.000 (4) | 0.013 (4) | −0.001 (4) |
P2 | 0.0347 (9) | 0.0381 (11) | 0.0482 (12) | 0.0058 (8) | 0.0121 (8) | 0.0023 (9) |
C20 | 0.031 (3) | 0.029 (4) | 0.048 (4) | 0.002 (3) | 0.008 (3) | −0.002 (3) |
C31 | 0.041 (4) | 0.041 (4) | 0.050 (5) | 0.004 (3) | 0.019 (3) | −0.001 (4) |
C32 | 0.049 (4) | 0.051 (5) | 0.066 (6) | 0.002 (4) | 0.014 (4) | −0.002 (4) |
C33 | 0.064 (5) | 0.067 (6) | 0.071 (6) | −0.012 (5) | 0.018 (5) | −0.020 (5) |
C34 | 0.089 (7) | 0.050 (6) | 0.110 (9) | −0.012 (5) | 0.053 (7) | −0.021 (6) |
C35 | 0.090 (7) | 0.036 (5) | 0.083 (7) | 0.008 (5) | 0.036 (6) | 0.003 (5) |
C36 | 0.072 (5) | 0.050 (5) | 0.053 (5) | 0.008 (4) | 0.022 (4) | −0.004 (4) |
C41 | 0.040 (4) | 0.040 (4) | 0.060 (5) | 0.008 (3) | 0.014 (4) | 0.006 (4) |
C42 | 0.056 (5) | 0.088 (7) | 0.066 (6) | 0.016 (5) | 0.024 (4) | −0.001 (5) |
C43 | 0.050 (6) | 0.125 (9) | 0.093 (8) | 0.022 (6) | 0.031 (5) | 0.019 (7) |
C44 | 0.040 (5) | 0.092 (8) | 0.139 (11) | 0.004 (5) | 0.020 (6) | 0.021 (7) |
C45 | 0.042 (5) | 0.099 (8) | 0.146 (10) | −0.006 (5) | 0.006 (6) | −0.032 (7) |
C46 | 0.050 (5) | 0.081 (7) | 0.100 (8) | 0.002 (5) | 0.019 (5) | −0.026 (6) |
N1 | 0.117 (8) | 0.100 (8) | 0.100 (8) | 0.009 (6) | 0.030 (6) | −0.002 (6) |
C1 | 0.124 (10) | 0.134 (11) | 0.137 (12) | −0.020 (8) | 0.058 (9) | −0.025 (9) |
C2 | 0.101 (8) | 0.075 (8) | 0.082 (8) | 0.013 (6) | 0.034 (7) | −0.002 (6) |
Cl1 | 0.0605 (12) | 0.0630 (14) | 0.0560 (13) | −0.0011 (11) | 0.0042 (10) | −0.0068 (11) |
O11 | 0.117 (5) | 0.078 (5) | 0.078 (5) | 0.005 (4) | −0.025 (4) | 0.003 (4) |
O12 | 0.128 (6) | 0.070 (4) | 0.101 (5) | −0.009 (4) | −0.055 (4) | −0.021 (4) |
O13 | 0.185 (8) | 0.166 (8) | 0.104 (6) | 0.096 (7) | −0.026 (6) | −0.057 (6) |
O14 | 0.117 (6) | 0.265 (12) | 0.129 (7) | −0.083 (7) | −0.002 (5) | 0.066 (8) |
Ag1—P1 | 2.4081 (18) | C20—H20B | 0.97 |
Ag1—P2i | 2.4097 (18) | C31—C32 | 1.377 (10) |
Ag1—Ag1i | 3.0581 (12) | C31—C36 | 1.392 (10) |
P1—C21 | 1.806 (7) | C32—C33 | 1.395 (10) |
P1—C11 | 1.820 (7) | C32—H32 | 0.93 |
P1—C20 | 1.836 (6) | C33—C34 | 1.367 (12) |
C11—C12 | 1.362 (10) | C33—H33 | 0.93 |
C11—C16 | 1.368 (9) | C34—C35 | 1.366 (12) |
C12—C13 | 1.381 (11) | C34—H34 | 0.93 |
C12—H12 | 0.93 | C35—C36 | 1.371 (11) |
C13—C14 | 1.376 (13) | C35—H35 | 0.93 |
C13—H13 | 0.93 | C36—H36 | 0.93 |
C14—C15 | 1.337 (13) | C41—C42 | 1.367 (10) |
C14—H14 | 0.93 | C41—C46 | 1.374 (10) |
C15—C16 | 1.387 (12) | C42—C43 | 1.390 (11) |
C15—H15 | 0.93 | C42—H42 | 0.93 |
C16—H16 | 0.93 | C43—C44 | 1.326 (13) |
C21—C26 | 1.378 (9) | C43—H43 | 0.93 |
C21—C22 | 1.391 (9) | C44—C45 | 1.368 (13) |
C22—C23 | 1.377 (10) | C44—H44 | 0.93 |
C22—H22 | 0.93 | C45—C46 | 1.388 (11) |
C23—C24 | 1.380 (11) | C45—H45 | 0.93 |
C23—H23 | 0.93 | C46—H46 | 0.93 |
C24—C25 | 1.359 (11) | N1—C2 | 1.123 (12) |
C24—H24 | 0.93 | C1—C2 | 1.422 (14) |
C25—C26 | 1.381 (10) | C1—H1A | 0.96 |
C25—H25 | 0.93 | C1—H1B | 0.96 |
C26—H26 | 0.93 | C1—H1C | 0.96 |
P2—C31 | 1.808 (7) | Cl1—O13 | 1.383 (7) |
P2—C41 | 1.823 (7) | Cl1—O12 | 1.402 (6) |
P2—C20 | 1.826 (6) | Cl1—O14 | 1.402 (8) |
P2—Ag1i | 2.4097 (18) | Cl1—O11 | 1.406 (6) |
C20—H20A | 0.97 | ||
P1—Ag1—P2i | 174.95 (7) | P1—C20—H20A | 109.2 |
P1—Ag1—Ag1i | 90.22 (5) | P2—C20—H20B | 109.2 |
P2i—Ag1—Ag1i | 89.07 (5) | P1—C20—H20B | 109.2 |
C21—P1—C11 | 102.0 (3) | H20A—C20—H20B | 107.9 |
C21—P1—C20 | 106.1 (3) | C32—C31—C36 | 118.5 (7) |
C11—P1—C20 | 105.4 (3) | C32—C31—P2 | 119.7 (6) |
C21—P1—Ag1 | 117.1 (2) | C36—C31—P2 | 121.5 (6) |
C11—P1—Ag1 | 112.8 (2) | C31—C32—C33 | 120.7 (8) |
C20—P1—Ag1 | 112.3 (2) | C31—C32—H32 | 119.6 |
C12—C11—C16 | 117.7 (7) | C33—C32—H32 | 119.6 |
C12—C11—P1 | 123.2 (6) | C34—C33—C32 | 119.4 (8) |
C16—C11—P1 | 119.0 (6) | C34—C33—H33 | 120.3 |
C11—C12—C13 | 120.7 (9) | C32—C33—H33 | 120.3 |
C11—C12—H12 | 119.6 | C35—C34—C33 | 120.3 (8) |
C13—C12—H12 | 119.6 | C35—C34—H34 | 119.8 |
C14—C13—C12 | 120.3 (9) | C33—C34—H34 | 119.8 |
C14—C13—H13 | 119.9 | C34—C35—C36 | 120.6 (8) |
C12—C13—H13 | 119.9 | C34—C35—H35 | 119.7 |
C15—C14—C13 | 119.6 (9) | C36—C35—H35 | 119.7 |
C15—C14—H14 | 120.2 | C35—C36—C31 | 120.4 (8) |
C13—C14—H14 | 120.2 | C35—C36—H36 | 119.8 |
C14—C15—C16 | 119.7 (9) | C31—C36—H36 | 119.8 |
C14—C15—H15 | 120.2 | C42—C41—C46 | 118.7 (7) |
C16—C15—H15 | 120.2 | C42—C41—P2 | 119.0 (6) |
C11—C16—C15 | 121.9 (9) | C46—C41—P2 | 121.7 (6) |
C11—C16—H16 | 119.1 | C41—C42—C43 | 119.9 (9) |
C15—C16—H16 | 119.1 | C41—C42—H42 | 120.1 |
C26—C21—C22 | 118.6 (7) | C43—C42—H42 | 120.1 |
C26—C21—P1 | 120.6 (5) | C44—C43—C42 | 121.6 (10) |
C22—C21—P1 | 120.7 (5) | C44—C43—H43 | 119.2 |
C23—C22—C21 | 120.9 (7) | C42—C43—H43 | 119.2 |
C23—C22—H22 | 119.6 | C43—C44—C45 | 119.4 (9) |
C21—C22—H22 | 119.6 | C43—C44—H44 | 120.3 |
C22—C23—C24 | 118.8 (8) | C45—C44—H44 | 120.3 |
C22—C23—H23 | 120.6 | C44—C45—C46 | 120.2 (10) |
C24—C23—H23 | 120.6 | C44—C45—H45 | 119.9 |
C25—C24—C23 | 121.5 (8) | C46—C45—H45 | 119.9 |
C25—C24—H24 | 119.3 | C41—C46—C45 | 120.2 (9) |
C23—C24—H24 | 119.3 | C41—C46—H46 | 119.9 |
C24—C25—C26 | 119.4 (8) | C45—C46—H46 | 119.9 |
C24—C25—H25 | 120.3 | C2—C1—H1A | 109.5 |
C26—C25—H25 | 120.3 | C2—C1—H1B | 109.5 |
C21—C26—C25 | 120.9 (7) | H1A—C1—H1B | 109.5 |
C21—C26—H26 | 119.6 | C2—C1—H1C | 109.5 |
C25—C26—H26 | 119.6 | H1A—C1—H1C | 109.5 |
C31—P2—C41 | 106.4 (3) | H1B—C1—H1C | 109.5 |
C31—P2—C20 | 104.4 (3) | N1—C2—C1 | 178.3 (13) |
C41—P2—C20 | 105.4 (3) | O13—Cl1—O12 | 111.6 (5) |
C31—P2—Ag1i | 113.2 (2) | O13—Cl1—O14 | 105.1 (7) |
C41—P2—Ag1i | 111.1 (2) | O12—Cl1—O14 | 108.1 (5) |
C20—P2—Ag1i | 115.6 (2) | O13—Cl1—O11 | 110.2 (5) |
P2—C20—P1 | 112.0 (3) | O12—Cl1—O11 | 112.2 (4) |
P2—C20—H20A | 109.2 | O14—Cl1—O11 | 109.3 (5) |
Ag1i—Ag1—P1—C21 | −93.2 (2) | Ag1i—P2—C20—P1 | 47.0 (4) |
Ag1i—Ag1—P1—C11 | 148.8 (2) | C21—P1—C20—P2 | 77.6 (4) |
Ag1i—Ag1—P1—C20 | 29.8 (2) | C11—P1—C20—P2 | −174.7 (3) |
C21—P1—C11—C12 | 140.8 (7) | Ag1—P1—C20—P2 | −51.5 (4) |
C20—P1—C11—C12 | 30.1 (7) | C41—P2—C31—C32 | −126.4 (6) |
Ag1—P1—C11—C12 | −92.8 (6) | C20—P2—C31—C32 | 122.4 (6) |
C21—P1—C11—C16 | −42.8 (7) | Ag1i—P2—C31—C32 | −4.1 (6) |
C20—P1—C11—C16 | −153.4 (6) | C41—P2—C31—C36 | 58.8 (6) |
Ag1—P1—C11—C16 | 83.7 (6) | C20—P2—C31—C36 | −52.4 (6) |
C16—C11—C12—C13 | 0.6 (13) | Ag1i—P2—C31—C36 | −178.9 (5) |
P1—C11—C12—C13 | 177.2 (7) | C36—C31—C32—C33 | −0.1 (11) |
C11—C12—C13—C14 | 1.7 (15) | P2—C31—C32—C33 | −175.1 (6) |
C12—C13—C14—C15 | −3.4 (16) | C31—C32—C33—C34 | 1.4 (12) |
C13—C14—C15—C16 | 2.6 (16) | C32—C33—C34—C35 | −1.9 (13) |
C12—C11—C16—C15 | −1.4 (13) | C33—C34—C35—C36 | 1.1 (13) |
P1—C11—C16—C15 | −178.1 (7) | C34—C35—C36—C31 | 0.3 (12) |
C14—C15—C16—C11 | −0.2 (16) | C32—C31—C36—C35 | −0.8 (11) |
C11—P1—C21—C26 | 132.7 (6) | P2—C31—C36—C35 | 174.1 (6) |
C20—P1—C21—C26 | −117.1 (6) | C31—P2—C41—C42 | 43.8 (7) |
Ag1—P1—C21—C26 | 9.1 (7) | C20—P2—C41—C42 | 154.3 (6) |
C11—P1—C21—C22 | −45.0 (6) | Ag1i—P2—C41—C42 | −79.8 (6) |
C20—P1—C21—C22 | 65.2 (6) | C31—P2—C41—C46 | −144.9 (7) |
Ag1—P1—C21—C22 | −168.6 (5) | C20—P2—C41—C46 | −34.4 (8) |
C26—C21—C22—C23 | −0.5 (11) | Ag1i—P2—C41—C46 | 91.5 (7) |
P1—C21—C22—C23 | 177.3 (6) | C46—C41—C42—C43 | −0.7 (12) |
C21—C22—C23—C24 | −0.6 (12) | P2—C41—C42—C43 | 170.9 (7) |
C22—C23—C24—C25 | 1.3 (13) | C41—C42—C43—C44 | −0.1 (15) |
C23—C24—C25—C26 | −1.0 (13) | C42—C43—C44—C45 | 1.2 (16) |
C22—C21—C26—C25 | 0.9 (11) | C43—C44—C45—C46 | −1.5 (17) |
P1—C21—C26—C25 | −176.9 (6) | C42—C41—C46—C45 | 0.4 (13) |
C24—C25—C26—C21 | −0.2 (12) | P2—C41—C46—C45 | −170.9 (7) |
C31—P2—C20—P1 | −78.0 (4) | C44—C45—C46—C41 | 0.7 (16) |
C41—P2—C20—P1 | 170.2 (3) |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ag2(C50H44P4)2](ClO4)2·2C2H3N |
Mr | 1265.48 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.4553 (3), 15.1766 (1), 16.0597 (5) |
β (°) | 101.826 (2) |
V (Å3) | 2732.76 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.99 |
Crystal size (mm) | 0.32 × 0.30 × 0.28 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.723, 0.759 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9485, 4806, 2920 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.131, 1.14 |
No. of reflections | 4806 |
No. of parameters | 326 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.53 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SAINT, SHELXTL (Siemens, 1994), SHELXTL.
Ag1—P1 | 2.4081 (18) | P1—C21 | 1.806 (7) |
Ag1—P2i | 2.4097 (18) | P1—C11 | 1.820 (7) |
Ag1—Ag1i | 3.0581 (12) | P1—C20 | 1.836 (6) |
P1—Ag1—P2i | 174.95 (7) | C11—P1—C20 | 105.4 (3) |
P1—Ag1—Ag1i | 90.22 (5) | C21—P1—Ag1 | 117.1 (2) |
P2i—Ag1—Ag1i | 89.07 (5) | C11—P1—Ag1 | 112.8 (2) |
C21—P1—C11 | 102.0 (3) | C20—P1—Ag1 | 112.3 (2) |
C21—P1—C20 | 106.1 (3) |
Symmetry code: (i) −x, −y+1, −z. |
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Binuclear complexes of silver with certain bidentate ligands are of great interest due to their rich luminescence and bonding properties. Several compounds of binuclear [Ag2(µ2-dppm)2]2+ dications, counterbalanced by various anionic species have been reported previously (Ahrens & Jones, 1998; Lusser & Peringer, 1985; Ho & Bau, 1983). Herein we report the crystal structure of the title compound, [Ag2(µ2-dppm)2](ClO4)2·2CH3CN, (I).
The asymmetric unit of (I) consists of one-half of an [Ag2(µ2-dppm)2]2+ dication, situated across a crystallographic inversion centre, an independent ClO4− anion and a acetonitrile solvent molecule. The structure of the dication with atomic numbering scheme is shown in Fig. 1. In the dication, the Ag atoms are doubly bridged by two dppm ligands, forming an eight-membered Ag2P4C2 ring. The formation of M2P4C2 ring (M = Cu, Ag, Au, Pt and Pd) has been reported previously (Ho & Bau, 1983; Neo et al., 1995; Van der Ploeg et al., 1979; Yam et al., 1997). The eight-membered ring displays a pseudo-chair conformation, as observed in [Ag2(µ2-dppm)2](ClO4)2·2CH2Cl2 (Ahrens & Jones, 1998). In the ring, the Ag centers are two-coordinated to exhibit an approximately linear coordination geometry with a P1—Ag1—P2i [symmetry code: (i) −x, 1 − y, −z] angle of 174.95 (7)°. The intramolecular Ag···Ag contact is 3.0581 (12) Å, which is longer than that observed in other silver systems; 2.9532 (7) Å in [Ag2(µ2-dppm)2](ClO4)2·2CH2Cl2 (Ahrens & Jones, 1998) and 2.987 (2) Å in [Ag2(µ2-dppm)3](NO3)2·2H2O (Hong et al., 1997). The Ag—P distances of 2.408 (2) and 2.410 (2) Å are comparable to those observed in the above two complexes.
The Ag1···N1 contact distance of 2.874 (10) Å is shorter than that observed [3.160 (6) Å] in [Ag3{HC(PPh2)3}2](ClO4)3·2CH3CN (Che et al., 1992) but longer than that observed [2.552 (2) Å] in [Ag3(dppm)2(CH3CN)2](ClO4)2·(CH3CH2)2O (Che et al., 1991). The Ag···O contact distances in (I) [Ag1···O12 = 3.071 (7) Å and Ag1···O12i = 3.367 (6) Å] lie in the range 2.959 (3)–3.514 (2) Å reported for [Ag2(µ2-dppm)2](ClO4)2·2CH2Cl2 (Ahrens et al., 1998) but lie outside the range of 2.418 (5)–2.689 (6) Å reported for [Ag2(dppm)2(NO3)2] (Ho et al., 1983).