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Acta Cryst. (2007). E63, m1943    [ doi:10.1107/S1600536807029042 ]

Di-[mu]-iodido-bis[bis(cyclohexyldiphenylphosphine-[kappa]P)silver(I)]

J. F. Young and G. P. A. Yap

Abstract top

The title compound, [Ag2I2(C18H21P)4], has a dimeric structure located on a twofold rotation axis with each tetrahedral AgI ion coordinated by two terminal phosphines and bridged by iodide ligands. Although this structural motif has been reported in bromide- and chloride-silver complexes, this is the first reported dimeric iodide-silver complex with monodentate phosphine.

Comment top

The 1:2 AgI:PCyPh2 dimeric complex is similar to the reported triphenyphosphine complexes with chlorine or bromine (Cassel, 1979; Bowmaker et al.,1993; Teo & Calabrese, 1976) and the 5-phenyldibenzophosphine complex with chloride (Attar et al., 1991). The 1:2 AgI:PCyPh2 dimeric complex is the first reported complex of this type with bridging iodine and monodentate phosphine. The molecule is located on a twofold axis.

Related literature top

Background information on monodentate phosphine–AgX (X=Br, Cl) adducts can be found in Attar et al. (1991), Bowmaker et al. (1993), Cassel (1979) and Teo & Calabrese (1976).

Experimental top

Synthesis of [Ag(PCyPh2)2I]2: 1 equivalent of AgI and 2.1 equivalents of diphenylcyclohexylphosphine were added in a vial containing anhydrous methylenechloride·The mixture was allowed to stir for 3 h at room temperature in darkness. Colorless crystals were grown by slow cooling of a saturated methylenechloride solution from ambient to 273 K in the dark. (yield 54%).

Refinement top

H atoms were assigned calculated positions with Uiso restrained to be 0.2Ueq of the bonded C atom and a C—H distance of 0.95–0.99 Å.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular diagram of the 1:2 AgI:PCyPh2 dimeric complex with ellipsoids at 30% probability. Hydrogen atoms are omitted for clarity.
Di-µ-iodido-bis[bis(cyclohexyldiphenylphosphine-κP)silver(I)] top
Crystal data top
[Ag2I2(C18H21P)4]F000 = 3104
Mr = 1542.81Dx = 1.574 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 934 reflections
a = 27.805 (4) Åθ = 2.7–22.1º
b = 13.3327 (17) ŵ = 1.69 mm−1
c = 17.598 (4) ÅT = 120 (2) K
β = 93.474 (13)ºTabular, colourless
V = 6511.8 (19) Å30.38 × 0.24 × 0.16 mm
Z = 4
Data collection top
Bruker APEX
diffractometer		5724 independent reflections
Radiation source: fine-focus sealed tube4448 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.099
Detector resolution: 836.6 pixels mm-1θmax = 25.0º
T = 120(2) Kθmin = 2.0º
ω scansh = −32→32
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		k = −15→15
Tmin = 0.556, Tmax = 0.763l = −20→20
30202 measured reflections
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)] = 0.039H-atom parameters constrained
wR(F2) = 0.090  w = 1/[σ2(Fo2) + (0.0207P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.005
5724 reflectionsΔρmax = 0.94 e Å−3
361 parametersΔρmin = −0.50 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ag2I2(C18H21P)4]V = 6511.8 (19) Å3
Mr = 1542.81Z = 4
Monoclinic, C2/cMo Kα
a = 27.805 (4) ŵ = 1.69 mm−1
b = 13.3327 (17) ÅT = 120 (2) K
c = 17.598 (4) Å0.38 × 0.24 × 0.16 mm
β = 93.474 (13)º
Data collection top
Bruker APEX
diffractometer		5724 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		4448 reflections with I > 2σ(I)
Tmin = 0.556, Tmax = 0.763Rint = 0.099
30202 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039361 parameters
wR(F2) = 0.090H-atom parameters constrained
S = 1.05Δρmax = 0.94 e Å−3
5724 reflectionsΔρmin = −0.50 e Å−3
Special details top

Experimental. Data collection is performed with four batch runs at φ = 0.00 ° (600 frames), at φ = 90.00 ° (600 frames), at φ = 180 ° (600 frames) and at φ = 270 ° (600 frames). Frame width = 0.30 ° in ω. Data is merged, corrected for decay, and treated with multi-scan absorption corrections.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.936332 (13)0.23521 (3)0.22857 (2)0.02529 (11)
I11.011583 (11)0.21772 (2)0.122587 (17)0.02443 (10)
P10.87855 (4)0.08676 (9)0.22706 (7)0.0218 (3)
P20.89485 (4)0.40206 (9)0.21388 (7)0.0238 (3)
C10.86182 (16)−0.0960 (3)0.3073 (3)0.0258 (11)
H1A0.8616−0.13520.25950.031*
H1B0.8286−0.07190.31370.031*
C20.87775 (17)−0.1632 (4)0.3743 (3)0.0345 (13)
H2A0.8736−0.12650.42230.041*
H2B0.8567−0.22310.37390.041*
C30.92953 (17)−0.1967 (3)0.3723 (3)0.0347 (13)
H3A0.9325−0.24420.32960.042*
H3B0.9391−0.23240.42020.042*
C40.96339 (17)−0.1084 (3)0.3626 (3)0.0314 (12)
H4A0.9652−0.06790.40990.038*
H4B0.9961−0.13400.35470.038*
C50.94707 (15)−0.0418 (3)0.2958 (3)0.0241 (11)
H5A0.9496−0.07930.24770.029*
H5B0.96850.01750.29450.029*
C60.89525 (15)−0.0071 (3)0.3020 (3)0.0236 (11)
H6A0.89450.02910.35170.028*
C70.82980 (17)−0.0480 (4)0.1225 (3)0.0313 (12)
H7A0.8026−0.04380.15260.038*
C80.82872 (19)−0.1112 (4)0.0600 (3)0.0399 (14)
H8A0.8002−0.14790.04620.048*
C90.86880 (19)−0.1215 (4)0.0171 (3)0.0345 (13)
H9A0.8681−0.1672−0.02440.041*
C100.90939 (19)−0.0653 (4)0.0349 (3)0.0331 (12)
H10A0.9367−0.07120.00520.040*
C110.91036 (17)0.0005 (3)0.0967 (3)0.0264 (11)
H11A0.93840.03950.10860.032*
C120.87082 (17)0.0097 (3)0.1414 (3)0.0257 (11)
C130.80198 (16)0.1262 (3)0.3217 (3)0.0258 (11)
H13A0.82230.10060.36250.031*
C140.75725 (17)0.1661 (3)0.3368 (3)0.0322 (12)
H14A0.74720.16750.38750.039*
C150.72758 (18)0.2036 (4)0.2778 (3)0.0385 (14)
H15A0.69730.23230.28790.046*
C160.74172 (18)0.1995 (4)0.2052 (3)0.0398 (14)
H16A0.72070.22320.16460.048*
C170.78624 (16)0.1612 (4)0.1898 (3)0.0325 (12)
H17A0.79580.16070.13880.039*
C180.81737 (15)0.1233 (3)0.2479 (3)0.0248 (11)
C190.83838 (17)0.3677 (3)0.3350 (3)0.0268 (11)
H19A0.85840.30710.34470.032*
H19B0.81140.34960.29820.032*
C200.81820 (17)0.4027 (4)0.4094 (3)0.0324 (12)
H20A0.79390.45580.39820.039*
H20B0.80190.34570.43310.039*
C210.85711 (19)0.4429 (4)0.4649 (3)0.0354 (13)
H21A0.84200.47150.50960.042*
H21B0.87830.38700.48300.042*
C220.88707 (18)0.5224 (4)0.4294 (3)0.0355 (13)
H22A0.86680.58220.41800.043*
H22B0.91360.54250.46620.043*
C230.90791 (16)0.4870 (3)0.3574 (3)0.0274 (11)
H23A0.93130.43250.36950.033*
H23B0.92540.54300.33440.033*
C240.86880 (16)0.4490 (3)0.3005 (3)0.0270 (11)
H24A0.84720.50660.28580.032*
C250.85027 (17)0.3252 (3)0.0829 (3)0.0277 (11)
H25A0.87970.28950.08000.033*
C260.81439 (19)0.3152 (4)0.0253 (3)0.0346 (13)
H26A0.81920.2722−0.01660.042*
C270.77145 (18)0.3678 (4)0.0283 (3)0.0341 (13)
H27A0.74710.3621−0.01170.041*
C280.76458 (17)0.4282 (4)0.0900 (3)0.0302 (12)
H28A0.73510.46370.09300.036*
C290.80011 (17)0.4378 (3)0.1477 (3)0.0281 (12)
H29A0.79480.47980.19000.034*
C300.84357 (16)0.3867 (3)0.1447 (3)0.0241 (11)
C310.95789 (16)0.5014 (3)0.1230 (3)0.0276 (11)
H31A0.97050.43640.11450.033*
C320.97607 (17)0.5842 (4)0.0841 (3)0.0335 (12)
H32A1.00200.57570.05190.040*
C330.95618 (17)0.6771 (4)0.0929 (3)0.0306 (12)
H33A0.96660.73200.06360.037*
C340.92163 (19)0.6915 (4)0.1434 (3)0.0402 (14)
H34A0.91000.75730.15210.048*
C350.90309 (17)0.6105 (3)0.1825 (3)0.0327 (12)
H35A0.87770.62070.21530.039*
C360.92213 (16)0.5132 (3)0.1732 (3)0.0263 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0247 (2)0.0233 (2)0.0284 (2)−0.00002 (15)0.00537 (16)0.00078 (16)
I10.02476 (19)0.02417 (18)0.02487 (19)0.00026 (13)0.00564 (14)−0.00068 (13)
P10.0205 (6)0.0209 (7)0.0238 (7)−0.0006 (5)0.0011 (5)0.0009 (5)
P20.0269 (7)0.0186 (6)0.0265 (7)0.0007 (5)0.0061 (6)−0.0029 (5)
C10.020 (3)0.025 (3)0.032 (3)0.000 (2)−0.002 (2)0.005 (2)
C20.030 (3)0.029 (3)0.044 (3)−0.003 (2)0.004 (2)0.011 (2)
C30.030 (3)0.026 (3)0.048 (3)0.002 (2)0.002 (3)0.011 (2)
C40.029 (3)0.022 (3)0.044 (3)0.001 (2)0.002 (2)0.004 (2)
C50.023 (3)0.018 (2)0.031 (3)−0.002 (2)0.004 (2)0.000 (2)
C60.019 (2)0.023 (3)0.029 (3)−0.001 (2)0.002 (2)0.003 (2)
C70.030 (3)0.034 (3)0.030 (3)−0.001 (2)0.002 (2)−0.001 (2)
C80.037 (3)0.044 (3)0.038 (3)−0.013 (3)−0.010 (3)−0.002 (3)
C90.054 (4)0.028 (3)0.019 (3)0.002 (3)−0.007 (3)−0.005 (2)
C100.043 (3)0.030 (3)0.027 (3)0.008 (2)0.009 (2)0.004 (2)
C110.027 (3)0.027 (3)0.026 (3)−0.005 (2)−0.001 (2)−0.005 (2)
C120.031 (3)0.021 (3)0.025 (3)−0.002 (2)−0.002 (2)0.000 (2)
C130.023 (3)0.025 (3)0.029 (3)−0.001 (2)0.002 (2)−0.002 (2)
C140.031 (3)0.024 (3)0.043 (3)−0.004 (2)0.013 (3)−0.004 (2)
C150.019 (3)0.027 (3)0.069 (4)0.005 (2)0.006 (3)0.005 (3)
C160.024 (3)0.036 (3)0.058 (4)−0.001 (2)−0.007 (3)0.018 (3)
C170.024 (3)0.033 (3)0.040 (3)−0.006 (2)−0.002 (2)0.009 (2)
C180.017 (2)0.019 (2)0.038 (3)−0.0030 (19)−0.002 (2)0.003 (2)
C190.030 (3)0.024 (3)0.026 (3)0.000 (2)0.005 (2)0.001 (2)
C200.029 (3)0.037 (3)0.032 (3)0.002 (2)0.008 (2)−0.002 (2)
C210.048 (3)0.036 (3)0.023 (3)0.010 (3)0.005 (2)−0.002 (2)
C220.034 (3)0.042 (3)0.030 (3)0.003 (3)0.000 (2)−0.011 (2)
C230.024 (3)0.028 (3)0.029 (3)0.006 (2)−0.001 (2)−0.004 (2)
C240.027 (3)0.025 (3)0.030 (3)0.003 (2)0.004 (2)−0.004 (2)
C250.036 (3)0.023 (3)0.026 (3)−0.004 (2)0.010 (2)−0.002 (2)
C260.047 (3)0.027 (3)0.030 (3)−0.010 (3)0.009 (3)−0.008 (2)
C270.035 (3)0.037 (3)0.030 (3)−0.015 (3)0.002 (2)−0.005 (2)
C280.029 (3)0.030 (3)0.032 (3)0.001 (2)0.005 (2)0.001 (2)
C290.036 (3)0.029 (3)0.021 (3)−0.001 (2)0.009 (2)0.000 (2)
C300.027 (3)0.021 (3)0.025 (3)−0.002 (2)0.008 (2)0.003 (2)
C310.027 (3)0.023 (3)0.034 (3)0.002 (2)0.009 (2)−0.001 (2)
C320.027 (3)0.032 (3)0.043 (3)−0.001 (2)0.011 (2)0.004 (2)
C330.036 (3)0.026 (3)0.030 (3)−0.009 (2)0.000 (2)0.005 (2)
C340.048 (4)0.018 (3)0.055 (4)0.001 (2)0.012 (3)0.000 (3)
C350.034 (3)0.025 (3)0.041 (3)0.004 (2)0.012 (2)0.001 (2)
C360.023 (3)0.021 (3)0.035 (3)−0.001 (2)0.006 (2)−0.002 (2)
Geometric parameters (Å, °) top
Ag1—P22.5120 (12)C13—C141.393 (6)
Ag1—P12.5485 (12)C14—C151.380 (7)
Ag1—I12.8955 (6)C15—C161.360 (7)
Ag1—I1i2.9245 (7)C16—C171.381 (6)
P1—C121.826 (5)C17—C181.395 (6)
P1—C181.828 (4)C19—C241.523 (6)
P1—C61.856 (4)C19—C201.529 (6)
P2—C361.830 (5)C20—C211.511 (6)
P2—C301.829 (5)C21—C221.508 (7)
P2—C241.837 (5)C22—C231.501 (6)
C1—C61.513 (6)C23—C241.520 (6)
C1—C21.525 (6)C25—C301.384 (6)
C2—C31.510 (6)C25—C261.385 (7)
C3—C41.524 (6)C26—C271.388 (7)
C4—C51.520 (6)C27—C281.375 (6)
C5—C61.524 (6)C28—C291.379 (6)
C7—C81.384 (7)C29—C301.391 (6)
C7—C121.399 (6)C31—C361.379 (6)
C8—C91.391 (7)C31—C321.409 (6)
C9—C101.374 (7)C32—C331.369 (6)
C10—C111.397 (6)C33—C341.361 (7)
C11—C121.396 (6)C34—C351.396 (6)
C13—C181.392 (6)C35—C361.414 (6)
P2—Ag1—P1113.67 (4)C7—C12—P1124.0 (4)
P2—Ag1—I1110.50 (3)C18—C13—C14121.1 (5)
P1—Ag1—I1114.23 (3)C15—C14—C13119.7 (5)
P2—Ag1—I1i111.24 (3)C16—C15—C14119.9 (5)
P1—Ag1—I1i103.01 (3)C15—C16—C17120.9 (5)
I1—Ag1—I1i103.45 (2)C16—C17—C18120.9 (5)
Ag1—I1—Ag1i75.796 (19)C13—C18—C17117.6 (4)
C12—P1—C18104.6 (2)C13—C18—P1122.5 (3)
C12—P1—C6102.7 (2)C17—C18—P1119.5 (4)
C18—P1—C6103.4 (2)C24—C19—C20111.5 (4)
C12—P1—Ag1119.22 (15)C21—C20—C19112.1 (4)
C18—P1—Ag1112.61 (15)C22—C21—C20111.9 (4)
C6—P1—Ag1112.67 (14)C23—C22—C21112.4 (4)
C36—P2—C3098.9 (2)C22—C23—C24111.3 (4)
C36—P2—C24104.0 (2)C23—C24—C19111.6 (4)
C30—P2—C24105.1 (2)C23—C24—P2111.0 (3)
C36—P2—Ag1123.97 (15)C19—C24—P2110.1 (3)
C30—P2—Ag1107.71 (15)C30—C25—C26120.4 (5)
C24—P2—Ag1114.71 (16)C25—C26—C27120.4 (5)
C6—C1—C2111.0 (4)C28—C27—C26119.2 (5)
C3—C2—C1112.9 (4)C27—C28—C29120.5 (5)
C2—C3—C4111.8 (4)C28—C29—C30120.8 (4)
C5—C4—C3112.3 (4)C25—C30—C29118.6 (4)
C4—C5—C6111.2 (4)C25—C30—P2116.9 (4)
C1—C6—C5110.7 (4)C29—C30—P2124.3 (4)
C1—C6—P1116.4 (3)C36—C31—C32121.1 (4)
C5—C6—P1110.5 (3)C33—C32—C31119.6 (5)
C8—C7—C12120.1 (5)C34—C33—C32120.5 (5)
C7—C8—C9120.8 (5)C33—C34—C35120.6 (5)
C10—C9—C8119.8 (5)C34—C35—C36120.1 (5)
C9—C10—C11119.8 (5)C31—C36—C35117.9 (4)
C12—C11—C10121.1 (4)C31—C36—P2119.4 (3)
C11—C12—C7118.4 (4)C35—C36—P2122.1 (4)
C11—C12—P1117.2 (3)
Symmetry codes: (i) −x+2, y, −z+1/2.
Acknowledgements top

We wish to thank Professor and Director Klaus H. Theopold of the Center for Catalytic Science and Technology for synthetic assistance and the Department of Chemistry and Biochemistry for the purchase of reagents.

references
References top

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