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Acta Cryst. (2007). E63, m1902-m1903    [ doi:10.1107/S1600536807028607 ]

catena-Poly[[[bis(cyclohexyldiphenylphosphine-[kappa]P)silver(I)]-[mu]-cyano-[kappa]2N:C-silver(I)-[mu]-cyano-[kappa]2C:N] dichloromethane solvate]

X. Xie, B. Saparov and G. P. A. Yap

Abstract top

The 1:1 AgCN-cyclohexyldiphenylphosphine adduct was synthesized to explore the structural possibilities of C- or N-atom coordination available to the cyanide ligand in the presence of cyclohexyldiphenylphosphine (PCyPh2), which would exert a steric influence intermediate between PCy3 and PPh3. The title compound, {[Ag2(CN)2(C16H21P)2]·CH2Cl2}n, is an inorganic polymer with monomeric units consisting of a linear bis(cyano)silver complex (formally a -1 anion) coordinated via the C atoms alternating with a tetrahedral silver complex having two phosphine ligands (formally a +1 cation). The tetrahedral coordination of the bis(phosphine)silver fragment is completed by dative bonds through the N-atom lone pairs of two bis(cyano)silver fragments. For each disilver monomeric unit, one molecule of dichloromethane solvent is found, disordered over two positions with relative occupancies 0.88:0.12. The polymer is propagated by a twofold screw causing each polymer strand to be chiral. Crystallization in a noncentrosymmetric space group implies spontaneous resolution from the solution, which could be achiral if the solvated species is different from the solid state or racemic if the polymers persist in solution. Even at a twofold excess of the phosphine, only the 1:1 polymer is observed, suggesting that the PCyPh2 ligand has a structural behaviour more like PPh3 than PCy3.

Comment top

The 1:1 adduct of AgCN and triphenylphosphine (PPh3) is known to yield polymer chains (Bowmaker, Effendy, Reid et al., 1998) since the cyanide ligand can coordinate through either the C or N atoms. In comparison, the 1:1 adduct of AgCN and the more sterically demanding tricyclohexylphosphine (PCy3) can yield, in addition to the polymer (Bowmaker, Effendy, Junk & White, 1998), a di-silver bis-phosphine monomeric complex (Lin et al., 2005).

Indeed when the even bulkier tri(1-cyclohepta-2,4,6-trienyl)phosphine is used the N atom coordination of the cyanide ligand is blocked and only a linear, monomeric 1:1 silver phosphine cyanide is observed (Herberhold et al., 2006). In comparison, the mono-Ag phosphine cyano adducts reported are 1:2 AgCN:PCy3 (Bowmaker et al., 1996) and 1:3 AgCN:PPh3 (Bowmaker, Effendy, Reid et al., 1998).

In order to generate polymers with bigger phosphines, a second much smaller ligand may be employed to complete the tetrahedral coordination on the phosphine-bearing Ag as in the case of AgCN:P(o-tolyl)3:pyridine (2:1:1) (Bowmaker, Effendy, Reid et al., 1998) or using less phosphine and changing the coordination around the phosphine-bearing Ag to trigonal as in the case of the 2:1 AgCN:PCy3 polymer (Lin et al., 2005). Surprisingly, the reported synthesis of both the 2:1 and the 1:1 AgCN:PCy3 polymers require a 1:1 molar ratio of the reactants!

We have decided to use cyclohexyldiphenylphosphine (PCyPh2) in order to explore the structural chemistry in the steric regime intermediate between PCy3 and PPh3. We have been able to synthesize the title compound which is a polymer similar to that reported for the PPh3 case. The monomeric unit can be described as linear bis-cyano Ag complex (formally a −1 anion) coordinated via the C atoms, and a tetrahedral Ag complex with two phosphines (formally a +1 cation). The tetrahedral coordination sphere is completed by dative bonds through the N lone pairs of two bis-cyano Ag fragments. The polymer is propagated by a twofold screw causing each polymer strand to be chiral. Crystallization in a noncentrosymmetric space group implies spontaneous resolution from the solution which could be achiral if the solvated species is different from the solid-state or racemic if the polymers persist in solution. In contrast, the enantiomeric polymers with PPh3 crystallized in centrosymmetric, and therefore racemic, crystals. Even at a twofold excess of the phosphine, only the 1:1 polymer is observed suggesting that the PCyPh2 phosphine has structural behaviour more similar to PPh3 than to PCy3.

Related literature top

Background information on monodentate phosphine–AgCN adducts can be found in Bowmaker, Effendy, Reid et al. (1998), Bowmaker, Effendy, Junk & White (1998), Bowmaker et al. (1996), Lin et al. (2005) and Herberhold et al. (2006).

Experimental top

The title compound can be synthesized quantitatively using literature methods (Herberhold et al., 2006) modified with the appropriate phosphine and with tetrahydrofuran reaction solvent. X-ray quality crystals were generated from a saturated solution in methylene chloride layered with hexanes.

Refinement top

The cocrystallized methylene chloride molecule was located disordered in two positions. The C—Cl and Cl···Cl distances were restrained to be similar in the disordered contributions. Atomic displacement parameters were constrained to be equal in the chemically equivalent atomic positions. The solvent molecule was restrained from close contact to the polymer. The site occupancies refined to 88:12. 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 a monomeric unit of the title compound with ellipsoids at 30% probability. Cocrystallized solvent molecule, and hydrogen atoms omitted for clarity.
[Figure 2] Fig. 2. Packing diagram and strand segment of the title compound along the b axis. Minor disordered contribution of the solvent molecule omitted for clarity.
catena-Poly[[[bis(cyclohexyldiphenylphosphine-κP)silver(I)]-µ-cyano- κ2N:C-silver(I)-µ-cyano-κ2C:N] dichloromethane solvate] top
Crystal data top
[Ag2(CN)2(C16H21P1)2]·CH2Cl2F000 = 900
Mr = 889.34Dx = 1.500 Mg m−3
Monoclinic, P21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: p 2ybCell parameters from 7412 reflections
a = 10.0007 (12) Åθ = 2.5–28.3º
b = 14.7062 (18) ŵ = 1.24 mm−1
c = 13.5338 (17) ÅT = 120 (2) K
β = 98.285 (2)ºNeedle, colourless
V = 1969.7 (4) Å30.24 × 0.11 × 0.09 mm
Z = 2
Data collection top
Bruker APEX
diffractometer		9243 independent reflections
Radiation source: fine-focus sealed tube8980 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
Detector resolution: 836.6 pixels mm-1θmax = 28.3º
T = 120(2) Kθmin = 2.1º
ω scansh = −13→13
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		k = −18→19
Tmin = 0.784, Tmax = 0.899l = −17→17
22828 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025  w = 1/[σ2(Fo2) + (0.0222P)2 + 1.1832P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.058(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.87 e Å−3
9243 reflectionsΔρmin = −0.53 e Å−3
434 parametersExtinction correction: none
9 restraintsAbsolute structure: Flack (1983), 4318 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.087 (16)
Secondary atom site location: difference Fourier map
Crystal data top
[Ag2(CN)2(C16H21P1)2]·CH2Cl2V = 1969.7 (4) Å3
Mr = 889.34Z = 2
Monoclinic, P21Mo Kα
a = 10.0007 (12) ŵ = 1.24 mm−1
b = 14.7062 (18) ÅT = 120 (2) K
c = 13.5338 (17) Å0.24 × 0.11 × 0.09 mm
β = 98.285 (2)º
Data collection top
Bruker APEX
diffractometer		9243 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		8980 reflections with I > 2σ(I)
Tmin = 0.784, Tmax = 0.899Rint = 0.021
22828 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.058Δρmax = 0.87 e Å−3
S = 1.07Δρmin = −0.53 e Å−3
9243 reflectionsAbsolute structure: Flack (1983), 4318 Friedel pairs
434 parametersFlack parameter: 0.087 (16)
9 restraints
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*/UeqOcc. (<1)
Ag1−0.151855 (18)0.265568 (13)1.178117 (14)0.02008 (5)
Ag2−0.54560 (2)0.012640 (17)1.06267 (2)0.03267 (6)
P1−0.13755 (7)0.32740 (5)1.34766 (5)0.01945 (14)
P20.03650 (7)0.20108 (5)1.10216 (5)0.01898 (14)
N1−0.2515 (3)0.37361 (19)1.0630 (2)0.0306 (6)
N2−0.3297 (3)0.1636 (2)1.1481 (2)0.0381 (7)
C1−0.1683 (3)0.1585 (2)1.4299 (3)0.0292 (7)
H1A−0.17650.13571.36050.035*
H1B−0.07120.16011.45750.035*
C2−0.2420 (3)0.0939 (2)1.4921 (3)0.0383 (8)
H2A−0.20410.03191.48920.046*
H2B−0.22770.11391.56270.046*
C3−0.3929 (3)0.0917 (2)1.4538 (3)0.0353 (7)
H3A−0.40790.06681.38510.042*
H3B−0.43910.05151.49680.042*
C4−0.4520 (3)0.1871 (2)1.4540 (3)0.0338 (7)
H4A−0.44410.20941.52360.041*
H4B−0.54920.18491.42650.041*
C5−0.3802 (3)0.2533 (2)1.3925 (2)0.0284 (6)
H5A−0.41770.31511.39770.034*
H5B−0.39640.23491.32130.034*
C6−0.2263 (3)0.2547 (2)1.4294 (2)0.0229 (6)
H6−0.21040.27961.49890.027*
C7−0.3316 (3)0.4613 (2)1.2994 (2)0.0259 (6)
H7−0.37340.41711.25380.031*
C8−0.3922 (3)0.5458 (2)1.3058 (2)0.0293 (7)
H8−0.47650.55831.26600.035*
C9−0.3306 (3)0.6116 (2)1.3697 (2)0.0268 (6)
H9−0.37170.66941.37360.032*
C10−0.2078 (3)0.5923 (2)1.4283 (2)0.0285 (6)
H10−0.16460.63761.47170.034*
C11−0.1483 (3)0.5080 (2)1.4240 (2)0.0243 (5)
H11−0.06510.49561.46510.029*
C12−0.2093 (3)0.44075 (19)1.3594 (2)0.0214 (5)
C130.0679 (3)0.3287 (2)1.5178 (2)0.0265 (6)
H13−0.00060.31681.55790.032*
C140.2023 (3)0.3373 (2)1.5623 (3)0.0332 (7)
H140.22480.33071.63250.040*
C150.3022 (3)0.3551 (2)1.5052 (3)0.0353 (8)
H150.39330.36081.53600.042*
C160.2703 (3)0.3647 (2)1.4030 (3)0.0364 (8)
H160.33930.37731.36350.044*
C170.1368 (3)0.3560 (2)1.3580 (2)0.0282 (6)
H170.11540.36261.28770.034*
C180.0341 (3)0.33775 (19)1.4142 (2)0.0225 (6)
C190.1764 (3)0.1125 (2)1.2704 (2)0.0253 (6)
H19A0.10280.12881.30890.030*
H19B0.24250.16301.27640.030*
C200.2459 (3)0.0248 (2)1.3127 (2)0.0295 (7)
H20A0.32190.01041.27590.035*
H20B0.28310.03421.38380.035*
C210.1478 (4)−0.0542 (2)1.3039 (3)0.0370 (8)
H21A0.0756−0.04201.34510.044*
H21B0.1958−0.11021.32940.044*
C220.0849 (4)−0.0682 (2)1.1950 (3)0.0343 (7)
H22A0.1562−0.08691.15540.041*
H22B0.0173−0.11771.19130.041*
C230.0167 (3)0.0185 (2)1.1501 (2)0.0290 (6)
H23A−0.06100.03381.18490.035*
H23B−0.01790.00851.07870.035*
C240.1184 (3)0.09822 (18)1.1606 (2)0.0206 (5)
H240.19470.08171.12370.025*
C250.0990 (4)0.1231 (3)0.9238 (2)0.0396 (8)
H250.18160.10470.96230.047*
C260.0742 (4)0.1020 (3)0.8223 (3)0.0461 (10)
H260.13880.06850.79210.055*
C27−0.0444 (4)0.1299 (3)0.7663 (3)0.0423 (9)
H27−0.06160.11560.69710.051*
C28−0.1379 (4)0.1781 (3)0.8097 (3)0.0391 (8)
H28−0.21860.19810.76990.047*
C29−0.1158 (3)0.1980 (2)0.9115 (2)0.0307 (7)
H29−0.18230.22990.94130.037*
C300.0041 (3)0.1710 (2)0.9694 (2)0.0237 (6)
C310.1320 (3)0.3762 (2)1.0905 (2)0.0247 (6)
H310.03880.39151.07920.030*
C320.2284 (3)0.4443 (2)1.0936 (2)0.0280 (6)
H320.20100.50601.08440.034*
C330.3647 (3)0.4227 (2)1.1101 (2)0.0287 (6)
H330.43060.46951.11330.034*
C340.4048 (3)0.3323 (2)1.1220 (2)0.0271 (6)
H340.49820.31731.13270.033*
C350.3083 (3)0.2643 (3)1.11829 (19)0.0238 (5)
H350.33620.20261.12560.029*
C360.1709 (3)0.28510 (18)1.1039 (2)0.0198 (5)
C37−0.3189 (3)0.4236 (2)1.0136 (2)0.0283 (6)
C38−0.4078 (3)0.1074 (2)1.1226 (3)0.0354 (8)
C39−0.5746 (6)0.2741 (4)0.8594 (5)0.0537 (12)0.880 (2)
H39A−0.60660.21090.84600.064*0.880 (2)
H39B−0.52230.27600.92730.064*0.880 (2)
Cl1−0.46825 (14)0.30626 (12)0.77027 (10)0.0624 (4)0.880 (2)
Cl2−0.71293 (14)0.34665 (12)0.85379 (9)0.0662 (4)0.880 (2)
C40−0.617 (4)0.292 (3)0.852 (4)0.0537 (12)0.120 (2)
H40A−0.63480.33500.90510.064*0.120 (2)
H40B−0.70440.27100.81540.064*0.120 (2)
Cl3−0.5162 (11)0.3441 (9)0.7695 (8)0.0624 (4)0.120 (2)
Cl4−0.5150 (10)0.1996 (8)0.9019 (6)0.0662 (4)0.120 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.01662 (9)0.02012 (9)0.02306 (9)0.00090 (8)0.00141 (7)−0.00285 (9)
Ag20.02438 (11)0.02882 (12)0.04481 (14)−0.00741 (10)0.00503 (9)−0.01479 (11)
P10.0181 (3)0.0182 (3)0.0219 (3)0.0007 (3)0.0024 (3)−0.0020 (3)
P20.0173 (3)0.0189 (3)0.0206 (3)0.0009 (3)0.0023 (3)−0.0017 (3)
N10.0286 (13)0.0287 (14)0.0344 (15)0.0065 (11)0.0046 (11)0.0035 (11)
N20.0312 (15)0.0321 (15)0.0510 (18)−0.0047 (12)0.0061 (13)−0.0140 (13)
C10.0214 (14)0.0214 (15)0.0439 (19)0.0008 (11)0.0015 (13)0.0074 (13)
C20.0309 (17)0.0256 (16)0.055 (2)−0.0002 (13)−0.0031 (16)0.0122 (15)
C30.0302 (16)0.0249 (16)0.051 (2)−0.0053 (13)0.0062 (15)0.0072 (14)
C40.0278 (16)0.0328 (18)0.0418 (19)−0.0034 (13)0.0086 (14)0.0033 (14)
C50.0229 (13)0.0264 (17)0.0363 (16)0.0023 (12)0.0062 (11)0.0048 (14)
C60.0208 (12)0.0220 (15)0.0257 (13)−0.0028 (11)0.0030 (10)0.0002 (12)
C70.0247 (14)0.0227 (15)0.0293 (15)−0.0014 (11)0.0004 (12)−0.0034 (12)
C80.0258 (15)0.0280 (16)0.0331 (16)0.0053 (12)0.0009 (12)0.0007 (12)
C90.0314 (16)0.0196 (14)0.0308 (16)0.0053 (12)0.0089 (12)−0.0004 (12)
C100.0350 (17)0.0182 (14)0.0313 (16)−0.0020 (12)0.0009 (13)−0.0060 (12)
C110.0253 (13)0.0229 (14)0.0243 (13)0.0019 (12)0.0021 (10)0.0002 (12)
C120.0222 (14)0.0180 (13)0.0242 (13)0.0019 (11)0.0045 (11)−0.0017 (11)
C130.0285 (15)0.0236 (14)0.0263 (14)−0.0006 (12)0.0000 (11)−0.0019 (12)
C140.0339 (17)0.0239 (16)0.0362 (17)0.0029 (13)−0.0140 (14)−0.0023 (13)
C150.0233 (15)0.0263 (16)0.052 (2)0.0084 (12)−0.0096 (14)−0.0112 (15)
C160.0225 (15)0.0380 (19)0.049 (2)0.0005 (13)0.0064 (14)−0.0144 (16)
C170.0232 (14)0.0330 (16)0.0283 (15)0.0004 (12)0.0032 (12)−0.0105 (13)
C180.0187 (13)0.0184 (13)0.0292 (14)0.0024 (10)−0.0004 (11)−0.0049 (11)
C190.0258 (14)0.0258 (15)0.0238 (14)0.0030 (12)0.0025 (11)−0.0005 (12)
C200.0291 (15)0.0333 (18)0.0258 (15)0.0095 (14)0.0028 (12)0.0100 (13)
C210.046 (2)0.0289 (17)0.0379 (18)0.0059 (15)0.0130 (15)0.0141 (14)
C220.0392 (19)0.0207 (15)0.044 (2)−0.0003 (13)0.0097 (15)0.0028 (13)
C230.0297 (15)0.0231 (14)0.0337 (16)−0.0010 (13)0.0027 (12)−0.0002 (13)
C240.0231 (13)0.0165 (13)0.0222 (13)0.0031 (10)0.0034 (11)0.0003 (10)
C250.0312 (17)0.060 (2)0.0263 (16)0.0124 (16)0.0015 (13)−0.0088 (16)
C260.044 (2)0.068 (3)0.0253 (17)0.0154 (19)0.0015 (15)−0.0127 (17)
C270.048 (2)0.055 (2)0.0224 (16)0.0026 (18)−0.0007 (15)−0.0102 (16)
C280.040 (2)0.0403 (19)0.0334 (18)0.0063 (15)−0.0082 (15)−0.0021 (15)
C290.0298 (16)0.0277 (16)0.0327 (16)0.0033 (13)−0.0014 (13)−0.0025 (13)
C300.0239 (14)0.0245 (14)0.0217 (13)−0.0020 (11)0.0002 (11)−0.0019 (11)
C310.0227 (14)0.0253 (15)0.0260 (15)0.0001 (12)0.0039 (11)0.0012 (12)
C320.0302 (16)0.0220 (14)0.0322 (16)−0.0003 (12)0.0061 (13)0.0051 (12)
C330.0288 (16)0.0299 (16)0.0268 (15)−0.0081 (13)0.0024 (12)0.0016 (12)
C340.0207 (14)0.0325 (16)0.0279 (15)−0.0018 (12)0.0026 (11)0.0009 (13)
C350.0214 (12)0.0251 (12)0.0248 (12)0.0002 (13)0.0024 (10)−0.0015 (14)
C360.0189 (12)0.0222 (15)0.0184 (12)−0.0018 (10)0.0033 (10)−0.0008 (10)
C370.0245 (15)0.0281 (16)0.0335 (16)0.0029 (12)0.0081 (13)0.0041 (13)
C380.0234 (15)0.0338 (18)0.049 (2)−0.0013 (13)0.0062 (14)−0.0148 (15)
C390.072 (4)0.042 (3)0.047 (2)0.005 (3)0.011 (3)−0.001 (2)
Cl10.0404 (7)0.0945 (11)0.0531 (7)−0.0046 (7)0.0097 (6)−0.0245 (7)
Cl20.0573 (8)0.1012 (12)0.0411 (6)0.0117 (7)0.0108 (5)−0.0066 (7)
C400.072 (4)0.042 (3)0.047 (2)0.005 (3)0.011 (3)−0.001 (2)
Cl30.0404 (7)0.0945 (11)0.0531 (7)−0.0046 (7)0.0097 (6)−0.0245 (7)
Cl40.0573 (8)0.1012 (12)0.0411 (6)0.0117 (7)0.0108 (5)−0.0066 (7)
Geometric parameters (Å, °) top
Ag1—N22.317 (3)C14—C151.372 (5)
Ag1—N12.345 (3)C15—C161.382 (5)
Ag1—P12.4532 (8)C16—C171.391 (4)
Ag1—P22.4623 (7)C17—C181.389 (4)
Ag2—C382.044 (3)C19—C241.529 (4)
Ag2—C37i2.052 (3)C19—C201.536 (4)
P1—C181.826 (3)C20—C211.514 (5)
P1—C121.831 (3)C21—C221.531 (5)
P1—C61.854 (3)C22—C231.531 (5)
P2—C361.823 (3)C23—C241.545 (4)
P2—C301.833 (3)C25—C301.395 (4)
P2—C241.844 (3)C25—C261.395 (5)
N1—C371.146 (4)C26—C271.375 (5)
N2—C381.155 (4)C27—C281.371 (5)
C1—C21.528 (4)C28—C291.395 (5)
C1—C61.529 (4)C29—C301.393 (4)
C2—C31.524 (5)C31—C321.387 (4)
C3—C41.523 (5)C31—C361.399 (4)
C4—C51.525 (4)C32—C331.386 (4)
C5—C61.548 (4)C33—C341.391 (5)
C7—C81.391 (4)C34—C351.386 (4)
C7—C121.400 (4)C35—C361.394 (4)
C8—C91.383 (4)C37—Ag2ii2.052 (3)
C9—C101.391 (4)C39—Cl21.740 (5)
C10—C111.380 (4)C39—Cl11.784 (5)
C11—C121.401 (4)C40—Cl41.779 (18)
C13—C141.397 (4)C40—Cl31.779 (18)
C13—C181.401 (4)
N2—Ag1—N194.59 (11)C14—C13—C18120.1 (3)
N2—Ag1—P1110.09 (8)C15—C14—C13120.5 (3)
N1—Ag1—P1109.41 (7)C14—C15—C16120.1 (3)
N2—Ag1—P2106.97 (8)C15—C16—C17119.8 (3)
N1—Ag1—P2105.12 (7)C18—C17—C16121.2 (3)
P1—Ag1—P2126.04 (2)C17—C18—C13118.4 (3)
C38—Ag2—C37i173.26 (15)C17—C18—P1117.6 (2)
C18—P1—C12103.51 (13)C13—C18—P1124.1 (2)
C18—P1—C6104.52 (13)C24—C19—C20109.5 (2)
C12—P1—C6104.20 (13)C21—C20—C19111.2 (3)
C18—P1—Ag1114.59 (10)C20—C21—C22110.5 (3)
C12—P1—Ag1116.63 (10)C23—C22—C21111.5 (3)
C6—P1—Ag1112.09 (10)C22—C23—C24110.2 (2)
C36—P2—C30101.66 (13)C19—C24—C23110.2 (2)
C36—P2—C24105.62 (13)C19—C24—P2112.76 (19)
C30—P2—C24103.15 (13)C23—C24—P2109.7 (2)
C36—P2—Ag1109.90 (9)C30—C25—C26120.9 (3)
C30—P2—Ag1117.68 (10)C27—C26—C25119.5 (3)
C24—P2—Ag1117.14 (9)C28—C27—C26120.4 (3)
C37—N1—Ag1168.8 (3)C27—C28—C29120.7 (3)
C38—N2—Ag1169.7 (3)C30—C29—C28119.8 (3)
C2—C1—C6111.4 (3)C29—C30—C25118.7 (3)
C3—C2—C1111.0 (3)C29—C30—P2119.9 (2)
C4—C3—C2110.2 (3)C25—C30—P2121.4 (2)
C3—C4—C5111.9 (3)C32—C31—C36120.6 (3)
C4—C5—C6110.9 (3)C33—C32—C31120.1 (3)
C1—C6—C5110.3 (2)C32—C33—C34119.9 (3)
C1—C6—P1108.8 (2)C35—C34—C33119.9 (3)
C5—C6—P1110.75 (19)C34—C35—C36120.9 (3)
C8—C7—C12120.6 (3)C35—C36—C31118.6 (3)
C9—C8—C7120.3 (3)C35—C36—P2124.3 (2)
C8—C9—C10119.4 (3)C31—C36—P2117.2 (2)
C11—C10—C9120.6 (3)N1—C37—Ag2ii173.3 (3)
C10—C11—C12120.6 (3)N2—C38—Ag2174.1 (4)
C7—C12—C11118.4 (3)Cl2—C39—Cl1110.8 (3)
C7—C12—P1117.8 (2)Cl4—C40—Cl3102.7 (13)
C11—C12—P1123.8 (2)
Symmetry codes: (i) −x−1, y−1/2, −z+2; (ii) −x−1, y+1/2, −z+2.
Acknowledgements top

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

references
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