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Acta Cryst. (2007). E63, m2395    [ doi:10.1107/S1600536807040597 ]

catena-Poly[[(acetonitrile-[kappa]N)silver(I)]-di-[mu]-trifluoromethanesulfonato-[kappa]4O:O'-[(acetonitrile-[kappa]N)silver(I)]-[mu]-tetraphenyldiphosphine-[kappa]2P:P']

C. E. Carson, R. P. Feazell and K. K. Klausmeyer

Abstract top

The silver(I)-based title polymer, [Ag2(CF3SO3)2(C28H26N2P2)]n, has been synthesized and structurally characterized. The compound shows the formation of a centrosymmetric eight-membered Ag/O/S/O/Ag/O/S/O ring situated around an inversion center, with the AgI ions bridged by two trifluoromethanesulfonate ions in a staggered conformation. The rings are then linked by tetraphenyldiphosphine ligands into a one-dimensional polymer. The rings have an Ag...Ag separation of 5.419 (5) Å and are linked by a 2.2206 (15) Å P-P bond. All AgI ions have pseudo-tetrahedral geometry, with a coordination environment consisting of two O atoms from two symmetry-related trifluoromethanesulfonate ions, a P atom from a phosphine ligand and an N atom from an acetonitrile ligand.

Comment top

The title polymer contains AgI ions in pseudo tetrahedral geometry bridged by a rigid bidentate diphosphine (DPP) ligand (Klausmeyer et al., 2004). The distorted tetrahedral angles range from 140.60 (10) to 86.61 (13)°. The AgI ion is stabilized by the soft donor phosphorus, from DPP, and 2 hard oxo ligands, from trifluoromethanesulfonate. The structure contains an 8-membered ring containing the silvers and the anions (Fig. 1). This ring is situated on an inversion center. The rings are then linked by the diphosphine ligand through the silvers into a one-dimensional polymer which boasts a 'Ring—P—P—Ring' design resembling a staircase (Fig. 2). The extended packing structure indicates that F atoms on the trifluoromethanesulfonate ion form a 3.186 (4) Å interaction with a C—H group on a neighboring 'staircase' polymer.

Related literature top

For the preparation of the diphosphine ligand, see: Klausmeyer et al. (2004).

Experimental top

The DPP ligand is an impurity formed in the synthesis of PCP-31 (Klausmeyer et al., 2004). Then combined with an equivalent of Ag(I)OTF in 10 ml CH3CN, a clear colorless solution results. Colorless blocks of the title compound were obtained by the slow diffusion of ether into a CH3CN solution containing the complex at 278 K.

Refinement top

H atoms were included in calculated positions and refined as riding on their parent atoms, with C—H bond lengths fixed to 0.95 (aromatic CH), or 0.98 Å (methyl CH3). Isotropic displacement parameters were fixed for H atoms: Uiso(H) = 1.5Ueq(C15) for the methyl group and Uiso(H) = 1.2Ueq(carrier C) for phenyl groups. In the last difference map, the highest residual peak, 1.47 e.Å−3, is found at 1.03 Å from Ag1.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of the monomer unit of the title compound. Displacement ellipsoids are shown at the 30% probability level and the labeling scheme is given for the asymmetric unit. Non-labeled atoms are generated by symmetry code 1 − x, 2 − y, −z.
[Figure 2] Fig. 2. Ball-and-Stick diagram displaying the 'Ring-P—P-Ring' pattern observed in the extended structure of the title polymer. H atoms have been omitted for clarity.
catena-Poly[[(acetonitrile-κN)silver(I)]-di-µ- trifluoromethanesulfonato-κ4O:O'-[(acetonitrile-κN)silver(I)]-µ- tetraphenyldiphosphine-κ2P:P'] top
Crystal data top
[Ag2(CF3SO3)2(C28H26N2P2)]F000 = 956
Mr = 483.16Dx = 1.771 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8448 reflections
a = 10.1128 (2) Åθ = 2.3–28.0º
b = 17.4753 (3) ŵ = 1.36 mm−1
c = 10.5053 (2) ÅT = 105 (2) K
β = 102.599 (1)ºRod, colourless
V = 1811.84 (6) Å30.21 × 0.17 × 0.10 mm
Z = 4
Data collection top
Bruker X8 APEX
diffractometer		4502 independent reflections
Radiation source: fine-focus sealed tube3588 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 105(2) Kθmax = 28.3º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→13
Tmin = 0.760, Tmax = 0.873k = −23→23
28681 measured reflectionsl = −14→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.112  w = 1/[σ2(Fo2) + (0.0619P)2 + 1.0373P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
4502 reflectionsΔρmax = 1.47 e Å−3
227 parametersΔρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ag2(CF3SO3)2(C28H26N2P2)]V = 1811.84 (6) Å3
Mr = 483.16Z = 4
Monoclinic, P21/nMo Kα
a = 10.1128 (2) ŵ = 1.36 mm−1
b = 17.4753 (3) ÅT = 105 (2) K
c = 10.5053 (2) Å0.21 × 0.17 × 0.10 mm
β = 102.599 (1)º
Data collection top
Bruker X8 APEX
diffractometer		4502 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3588 reflections with I > 2σ(I)
Tmin = 0.760, Tmax = 0.873Rint = 0.030
28681 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040227 parameters
wR(F2) = 0.112H-atom parameters constrained
S = 1.04Δρmax = 1.47 e Å−3
4502 reflectionsΔρmin = −0.23 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.61713 (3)1.022971 (14)0.25471 (3)0.05425 (11)
P10.50042 (7)0.96768 (4)0.40910 (7)0.03942 (17)
S30.57444 (9)0.87763 (4)0.03092 (8)0.05077 (19)
C70.3200 (3)0.95576 (16)0.3394 (3)0.0439 (6)
C80.2762 (4)0.9755 (2)0.2101 (4)0.0623 (9)
H80.33930.99410.16240.075*
C10.5731 (3)0.87625 (16)0.4756 (3)0.0442 (6)
C20.6818 (4)0.8485 (2)0.4273 (4)0.0607 (8)
H20.71380.87650.36270.073*
C60.5306 (4)0.83521 (19)0.5713 (4)0.0590 (8)
H60.45710.85350.60570.071*
C40.6990 (4)0.7402 (2)0.5701 (5)0.0736 (11)
H40.74250.69380.60280.088*
C50.5950 (4)0.7669 (2)0.6178 (4)0.0667 (10)
H50.56490.73900.68380.080*
C120.2260 (4)0.9294 (3)0.4062 (4)0.0729 (11)
H120.25480.91450.49490.087*
C130.6961 (5)0.8024 (3)0.0321 (4)0.0731 (11)
C90.1401 (5)0.9684 (3)0.1490 (5)0.0819 (13)
H90.11120.98120.05930.098*
C110.0889 (4)0.9245 (3)0.3452 (5)0.0830 (13)
H110.02450.90810.39320.100*
C30.7430 (4)0.7802 (3)0.4734 (5)0.0757 (11)
H30.81540.76070.43870.091*
C100.0478 (4)0.9433 (2)0.2168 (5)0.0735 (12)
H10−0.04500.93880.17450.088*
F20.7758 (4)0.8166 (3)−0.0462 (4)0.1362 (14)
F30.6357 (4)0.73743 (16)−0.0037 (4)0.1363 (15)
F10.7723 (3)0.7912 (2)0.1497 (3)0.1225 (12)
O20.4961 (3)0.85106 (17)0.1200 (3)0.0738 (7)
O10.6587 (3)0.94232 (16)0.0761 (3)0.0799 (8)
N10.8058 (3)1.0888 (2)0.2480 (4)0.0730 (9)
C140.8980 (4)1.1225 (2)0.2413 (4)0.0650 (9)
O30.5061 (4)0.88004 (19)−0.1030 (3)0.0885 (10)
C151.0188 (5)1.1660 (3)0.2352 (6)0.0971 (16)
H15A1.00591.21960.25720.146*
H15B1.03531.16300.14680.146*
H15C1.09661.14470.29740.146*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.05592 (17)0.05287 (16)0.05747 (17)−0.00550 (10)0.02006 (12)0.00355 (10)
P10.0370 (4)0.0361 (3)0.0438 (4)−0.0028 (3)0.0059 (3)0.0003 (3)
S30.0570 (4)0.0431 (4)0.0537 (4)0.0051 (3)0.0155 (4)0.0008 (3)
C70.0388 (14)0.0346 (13)0.0553 (17)−0.0022 (11)0.0039 (12)−0.0029 (12)
C80.0480 (18)0.073 (2)0.062 (2)0.0061 (16)0.0032 (16)0.0082 (17)
C10.0421 (14)0.0360 (13)0.0508 (16)0.0020 (11)0.0018 (12)0.0001 (12)
C20.0521 (18)0.063 (2)0.066 (2)0.0107 (16)0.0090 (16)0.0091 (17)
C60.064 (2)0.0435 (16)0.073 (2)0.0015 (14)0.0228 (18)0.0042 (15)
C40.063 (2)0.0495 (19)0.097 (3)0.0097 (17)−0.007 (2)0.016 (2)
C50.075 (2)0.0462 (18)0.077 (2)−0.0031 (17)0.011 (2)0.0162 (17)
C120.056 (2)0.096 (3)0.063 (2)−0.024 (2)0.0046 (17)0.011 (2)
C130.079 (3)0.073 (3)0.072 (2)0.023 (2)0.027 (2)0.002 (2)
C90.056 (2)0.102 (4)0.073 (3)0.009 (2)−0.016 (2)0.010 (2)
C110.049 (2)0.094 (3)0.104 (3)−0.023 (2)0.013 (2)0.012 (3)
C30.059 (2)0.073 (3)0.094 (3)0.0232 (19)0.014 (2)0.009 (2)
C100.0448 (19)0.062 (2)0.098 (3)0.0001 (16)−0.017 (2)−0.002 (2)
F20.122 (3)0.182 (4)0.134 (3)0.054 (2)0.090 (2)0.022 (3)
F30.177 (4)0.0536 (17)0.182 (4)0.0202 (19)0.046 (3)−0.0193 (19)
F10.102 (2)0.163 (3)0.099 (2)0.071 (2)0.0145 (17)0.024 (2)
O20.0638 (16)0.0796 (18)0.0868 (19)−0.0078 (14)0.0355 (15)−0.0007 (15)
O10.102 (2)0.0586 (15)0.090 (2)−0.0251 (15)0.0457 (18)−0.0175 (14)
N10.0616 (19)0.071 (2)0.089 (2)−0.0154 (16)0.0215 (17)−0.0050 (18)
C140.059 (2)0.068 (2)0.069 (2)−0.0121 (17)0.0172 (18)−0.0080 (18)
O30.111 (2)0.081 (2)0.0627 (17)0.0280 (18)−0.0042 (16)0.0076 (14)
C150.068 (3)0.105 (4)0.123 (4)−0.028 (3)0.031 (3)−0.007 (3)
Geometric parameters (Å, °) top
Ag1—N12.242 (3)C4—C51.344 (6)
Ag1—P12.4068 (8)C4—C31.383 (6)
Ag1—O12.455 (3)C4—H40.9500
Ag1—O3i2.470 (3)C5—H50.9500
P1—C71.824 (3)C12—C111.398 (5)
P1—C11.832 (3)C12—H120.9500
P1—P1ii2.2206 (15)C13—F21.295 (5)
S3—O31.427 (3)C13—F31.305 (5)
S3—O21.429 (3)C13—F11.320 (5)
S3—O11.433 (3)C9—C101.365 (7)
S3—C131.799 (4)C9—H90.9500
C7—C81.378 (5)C11—C101.362 (7)
C7—C121.378 (5)C11—H110.9500
C8—C91.392 (6)C3—H30.9500
C8—H80.9500C10—H100.9500
C1—C61.378 (5)N1—C141.118 (5)
C1—C21.394 (5)C14—C151.452 (6)
C2—C31.383 (5)O3—Ag1i2.470 (3)
C2—H20.9500C15—H15A0.9800
C6—C51.396 (5)C15—H15B0.9800
C6—H60.9500C15—H15C0.9800
N1—Ag1—P1140.60 (10)C3—C4—H4119.9
N1—Ag1—O188.97 (11)C4—C5—C6120.6 (4)
P1—Ag1—O1118.38 (7)C4—C5—H5119.7
N1—Ag1—O3i86.61 (13)C6—C5—H5119.7
P1—Ag1—O3i117.23 (9)C7—C12—C11120.8 (4)
O1—Ag1—O3i92.72 (11)C7—C12—H12119.6
C7—P1—C1109.67 (13)C11—C12—H12119.6
C7—P1—P1ii102.26 (11)F2—C13—F3107.5 (4)
C1—P1—P1ii101.08 (11)F2—C13—F1107.8 (4)
C7—P1—Ag1111.71 (11)F3—C13—F1106.4 (4)
C1—P1—Ag1113.08 (11)F2—C13—S3112.0 (3)
P1ii—P1—Ag1118.02 (5)F3—C13—S3110.9 (3)
O3—S3—O2115.9 (2)F1—C13—S3111.9 (3)
O3—S3—O1115.4 (2)C10—C9—C8120.6 (4)
O2—S3—O1114.45 (17)C10—C9—H9119.7
O3—S3—C13102.2 (2)C8—C9—H9119.7
O2—S3—C13103.52 (19)C10—C11—C12119.8 (4)
O1—S3—C13102.6 (2)C10—C11—H11120.1
C8—C7—C12118.5 (3)C12—C11—H11120.1
C8—C7—P1116.4 (3)C4—C3—C2120.1 (4)
C12—C7—P1125.0 (3)C4—C3—H3119.9
C7—C8—C9120.3 (4)C2—C3—H3119.9
C7—C8—H8119.8C11—C10—C9119.9 (4)
C9—C8—H8119.8C11—C10—H10120.0
C6—C1—C2118.7 (3)C9—C10—H10120.0
C6—C1—P1124.7 (2)S3—O1—Ag1121.18 (17)
C2—C1—P1116.6 (3)C14—N1—Ag1177.9 (4)
C3—C2—C1120.1 (4)N1—C14—C15178.9 (5)
C3—C2—H2120.0S3—O3—Ag1i136.42 (19)
C1—C2—H2120.0C14—C15—H15A109.5
C1—C6—C5120.3 (3)C14—C15—H15B109.5
C1—C6—H6119.9H15A—C15—H15B109.5
C5—C6—H6119.9C14—C15—H15C109.5
C5—C4—C3120.1 (3)H15A—C15—H15C109.5
C5—C4—H4119.9H15B—C15—H15C109.5
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1.
Acknowledgements top

The Bruker X8 APEX diffractometer was purchased with funds received from the National Science Foundation Major Research Instrumentation Program, grant No. CHE-0321214. K K thanks the Robert A. Welch Foundation for support (grant No. AA-1508).

references
References top

Bruker (2003). APEX2 (Version 1.0-28), SAINT-Plus (Version 6.25) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Klausmeyer, K. K., Feazell, R. P. & Reibenspies, J. H. (2004). Inorg. Chem. 43, 1130–1136.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany