Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028607/br2046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028607/br2046Isup2.hkl |
CCDC reference: 654761
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.004 Å
- Disorder in solvent or counterion
- R factor = 0.025
- wR factor = 0.058
- Data-to-parameter ratio = 21.3
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT761_ALERT_1_A CIF Contains no X-H Bonds ...................... ? PLAT762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles .......... ?
Alert level C PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.27 From the CIF: _reflns_number_total 9243 Count of symmetry unique reflns 5072 Completeness (_total/calc) 182.24% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 4171 Fraction of Friedel pairs measured 0.822 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 9
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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).
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.
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.
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.
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).
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.
[Ag2(CN)2(C16H21P)2]·CH2Cl2 | F(000) = 900 |
Mr = 889.34 | Dx = 1.500 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2yb | Cell parameters from 7412 reflections |
a = 10.0007 (12) Å | θ = 2.5–28.3° |
b = 14.7062 (18) Å | µ = 1.24 mm−1 |
c = 13.5338 (17) Å | T = 120 K |
β = 98.285 (2)° | Needle, colourless |
V = 1969.7 (4) Å3 | 0.24 × 0.11 × 0.09 mm |
Z = 2 |
Bruker APEX diffractometer | 9243 independent reflections |
Radiation source: fine-focus sealed tube | 8980 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 836.6 pixels mm-1 | θmax = 28.3°, θmin = 2.1° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | k = −18→19 |
Tmin = 0.784, Tmax = 0.899 | l = −17→17 |
22828 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0222P)2 + 1.1832P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
9243 reflections | Δρmax = 0.87 e Å−3 |
434 parameters | Δρmin = −0.53 e Å−3 |
9 restraints | Absolute structure: Flack (1983), 4318 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.087 (16) |
[Ag2(CN)2(C16H21P)2]·CH2Cl2 | V = 1969.7 (4) Å3 |
Mr = 889.34 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.0007 (12) Å | µ = 1.24 mm−1 |
b = 14.7062 (18) Å | T = 120 K |
c = 13.5338 (17) Å | 0.24 × 0.11 × 0.09 mm |
β = 98.285 (2)° |
Bruker APEX diffractometer | 9243 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 8980 reflections with I > 2σ(I) |
Tmin = 0.784, Tmax = 0.899 | Rint = 0.021 |
22828 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.058 | Δρmax = 0.87 e Å−3 |
S = 1.07 | Δρmin = −0.53 e Å−3 |
9243 reflections | Absolute structure: Flack (1983), 4318 Friedel pairs |
434 parameters | Absolute structure parameter: 0.087 (16) |
9 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<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) | |
P2 | 0.03650 (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 | −0.1765 | 0.1357 | 1.3605 | 0.035* | |
H1B | −0.0712 | 0.1601 | 1.4575 | 0.035* | |
C2 | −0.2420 (3) | 0.0939 (2) | 1.4921 (3) | 0.0383 (8) | |
H2A | −0.2041 | 0.0319 | 1.4892 | 0.046* | |
H2B | −0.2277 | 0.1139 | 1.5627 | 0.046* | |
C3 | −0.3929 (3) | 0.0917 (2) | 1.4538 (3) | 0.0353 (7) | |
H3A | −0.4079 | 0.0668 | 1.3851 | 0.042* | |
H3B | −0.4391 | 0.0515 | 1.4968 | 0.042* | |
C4 | −0.4520 (3) | 0.1871 (2) | 1.4540 (3) | 0.0338 (7) | |
H4A | −0.4441 | 0.2094 | 1.5236 | 0.041* | |
H4B | −0.5492 | 0.1849 | 1.4265 | 0.041* | |
C5 | −0.3802 (3) | 0.2533 (2) | 1.3925 (2) | 0.0284 (6) | |
H5A | −0.4177 | 0.3151 | 1.3977 | 0.034* | |
H5B | −0.3964 | 0.2349 | 1.3213 | 0.034* | |
C6 | −0.2263 (3) | 0.2547 (2) | 1.4294 (2) | 0.0229 (6) | |
H6 | −0.2104 | 0.2796 | 1.4989 | 0.027* | |
C7 | −0.3316 (3) | 0.4613 (2) | 1.2994 (2) | 0.0259 (6) | |
H7 | −0.3734 | 0.4171 | 1.2538 | 0.031* | |
C8 | −0.3922 (3) | 0.5458 (2) | 1.3058 (2) | 0.0293 (7) | |
H8 | −0.4765 | 0.5583 | 1.2660 | 0.035* | |
C9 | −0.3306 (3) | 0.6116 (2) | 1.3697 (2) | 0.0268 (6) | |
H9 | −0.3717 | 0.6694 | 1.3736 | 0.032* | |
C10 | −0.2078 (3) | 0.5923 (2) | 1.4283 (2) | 0.0285 (6) | |
H10 | −0.1646 | 0.6376 | 1.4717 | 0.034* | |
C11 | −0.1483 (3) | 0.5080 (2) | 1.4240 (2) | 0.0243 (5) | |
H11 | −0.0651 | 0.4956 | 1.4651 | 0.029* | |
C12 | −0.2093 (3) | 0.44075 (19) | 1.3594 (2) | 0.0214 (5) | |
C13 | 0.0679 (3) | 0.3287 (2) | 1.5178 (2) | 0.0265 (6) | |
H13 | −0.0006 | 0.3168 | 1.5579 | 0.032* | |
C14 | 0.2023 (3) | 0.3373 (2) | 1.5623 (3) | 0.0332 (7) | |
H14 | 0.2248 | 0.3307 | 1.6325 | 0.040* | |
C15 | 0.3022 (3) | 0.3551 (2) | 1.5052 (3) | 0.0353 (8) | |
H15 | 0.3933 | 0.3608 | 1.5360 | 0.042* | |
C16 | 0.2703 (3) | 0.3647 (2) | 1.4030 (3) | 0.0364 (8) | |
H16 | 0.3393 | 0.3773 | 1.3635 | 0.044* | |
C17 | 0.1368 (3) | 0.3560 (2) | 1.3580 (2) | 0.0282 (6) | |
H17 | 0.1154 | 0.3626 | 1.2877 | 0.034* | |
C18 | 0.0341 (3) | 0.33775 (19) | 1.4142 (2) | 0.0225 (6) | |
C19 | 0.1764 (3) | 0.1125 (2) | 1.2704 (2) | 0.0253 (6) | |
H19A | 0.1028 | 0.1288 | 1.3089 | 0.030* | |
H19B | 0.2425 | 0.1630 | 1.2764 | 0.030* | |
C20 | 0.2459 (3) | 0.0248 (2) | 1.3127 (2) | 0.0295 (7) | |
H20A | 0.3219 | 0.0104 | 1.2759 | 0.035* | |
H20B | 0.2831 | 0.0342 | 1.3838 | 0.035* | |
C21 | 0.1478 (4) | −0.0542 (2) | 1.3039 (3) | 0.0370 (8) | |
H21A | 0.0756 | −0.0420 | 1.3451 | 0.044* | |
H21B | 0.1958 | −0.1102 | 1.3294 | 0.044* | |
C22 | 0.0849 (4) | −0.0682 (2) | 1.1950 (3) | 0.0343 (7) | |
H22A | 0.1562 | −0.0869 | 1.1554 | 0.041* | |
H22B | 0.0173 | −0.1177 | 1.1913 | 0.041* | |
C23 | 0.0167 (3) | 0.0185 (2) | 1.1501 (2) | 0.0290 (6) | |
H23A | −0.0610 | 0.0338 | 1.1849 | 0.035* | |
H23B | −0.0179 | 0.0085 | 1.0787 | 0.035* | |
C24 | 0.1184 (3) | 0.09822 (18) | 1.1606 (2) | 0.0206 (5) | |
H24 | 0.1947 | 0.0817 | 1.1237 | 0.025* | |
C25 | 0.0990 (4) | 0.1231 (3) | 0.9238 (2) | 0.0396 (8) | |
H25 | 0.1816 | 0.1047 | 0.9623 | 0.047* | |
C26 | 0.0742 (4) | 0.1020 (3) | 0.8223 (3) | 0.0461 (10) | |
H26 | 0.1388 | 0.0685 | 0.7921 | 0.055* | |
C27 | −0.0444 (4) | 0.1299 (3) | 0.7663 (3) | 0.0423 (9) | |
H27 | −0.0616 | 0.1156 | 0.6971 | 0.051* | |
C28 | −0.1379 (4) | 0.1781 (3) | 0.8097 (3) | 0.0391 (8) | |
H28 | −0.2186 | 0.1981 | 0.7699 | 0.047* | |
C29 | −0.1158 (3) | 0.1980 (2) | 0.9115 (2) | 0.0307 (7) | |
H29 | −0.1823 | 0.2299 | 0.9413 | 0.037* | |
C30 | 0.0041 (3) | 0.1710 (2) | 0.9694 (2) | 0.0237 (6) | |
C31 | 0.1320 (3) | 0.3762 (2) | 1.0905 (2) | 0.0247 (6) | |
H31 | 0.0388 | 0.3915 | 1.0792 | 0.030* | |
C32 | 0.2284 (3) | 0.4443 (2) | 1.0936 (2) | 0.0280 (6) | |
H32 | 0.2010 | 0.5060 | 1.0844 | 0.034* | |
C33 | 0.3647 (3) | 0.4227 (2) | 1.1101 (2) | 0.0287 (6) | |
H33 | 0.4306 | 0.4695 | 1.1133 | 0.034* | |
C34 | 0.4048 (3) | 0.3323 (2) | 1.1220 (2) | 0.0271 (6) | |
H34 | 0.4982 | 0.3173 | 1.1327 | 0.033* | |
C35 | 0.3083 (3) | 0.2643 (3) | 1.11829 (19) | 0.0238 (5) | |
H35 | 0.3362 | 0.2026 | 1.1256 | 0.029* | |
C36 | 0.1709 (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 | −0.6066 | 0.2109 | 0.8460 | 0.064* | 0.880 (2) |
H39B | −0.5223 | 0.2760 | 0.9273 | 0.064* | 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 | −0.6348 | 0.3350 | 0.9051 | 0.064* | 0.120 (2) |
H40B | −0.7044 | 0.2710 | 0.8154 | 0.064* | 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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.01662 (9) | 0.02012 (9) | 0.02306 (9) | 0.00090 (8) | 0.00141 (7) | −0.00285 (9) |
Ag2 | 0.02438 (11) | 0.02882 (12) | 0.04481 (14) | −0.00741 (10) | 0.00503 (9) | −0.01479 (11) |
P1 | 0.0181 (3) | 0.0182 (3) | 0.0219 (3) | 0.0007 (3) | 0.0024 (3) | −0.0020 (3) |
P2 | 0.0173 (3) | 0.0189 (3) | 0.0206 (3) | 0.0009 (3) | 0.0023 (3) | −0.0017 (3) |
N1 | 0.0286 (13) | 0.0287 (14) | 0.0344 (15) | 0.0065 (11) | 0.0046 (11) | 0.0035 (11) |
N2 | 0.0312 (15) | 0.0321 (15) | 0.0510 (18) | −0.0047 (12) | 0.0061 (13) | −0.0140 (13) |
C1 | 0.0214 (14) | 0.0214 (15) | 0.0439 (19) | 0.0008 (11) | 0.0015 (13) | 0.0074 (13) |
C2 | 0.0309 (17) | 0.0256 (16) | 0.055 (2) | −0.0002 (13) | −0.0031 (16) | 0.0122 (15) |
C3 | 0.0302 (16) | 0.0249 (16) | 0.051 (2) | −0.0053 (13) | 0.0062 (15) | 0.0072 (14) |
C4 | 0.0278 (16) | 0.0328 (18) | 0.0418 (19) | −0.0034 (13) | 0.0086 (14) | 0.0033 (14) |
C5 | 0.0229 (13) | 0.0264 (17) | 0.0363 (16) | 0.0023 (12) | 0.0062 (11) | 0.0048 (14) |
C6 | 0.0208 (12) | 0.0220 (15) | 0.0257 (13) | −0.0028 (11) | 0.0030 (10) | 0.0002 (12) |
C7 | 0.0247 (14) | 0.0227 (15) | 0.0293 (15) | −0.0014 (11) | 0.0004 (12) | −0.0034 (12) |
C8 | 0.0258 (15) | 0.0280 (16) | 0.0331 (16) | 0.0053 (12) | 0.0009 (12) | 0.0007 (12) |
C9 | 0.0314 (16) | 0.0196 (14) | 0.0308 (16) | 0.0053 (12) | 0.0089 (12) | −0.0004 (12) |
C10 | 0.0350 (17) | 0.0182 (14) | 0.0313 (16) | −0.0020 (12) | 0.0009 (13) | −0.0060 (12) |
C11 | 0.0253 (13) | 0.0229 (14) | 0.0243 (13) | 0.0019 (12) | 0.0021 (10) | 0.0002 (12) |
C12 | 0.0222 (14) | 0.0180 (13) | 0.0242 (13) | 0.0019 (11) | 0.0045 (11) | −0.0017 (11) |
C13 | 0.0285 (15) | 0.0236 (14) | 0.0263 (14) | −0.0006 (12) | 0.0000 (11) | −0.0019 (12) |
C14 | 0.0339 (17) | 0.0239 (16) | 0.0362 (17) | 0.0029 (13) | −0.0140 (14) | −0.0023 (13) |
C15 | 0.0233 (15) | 0.0263 (16) | 0.052 (2) | 0.0084 (12) | −0.0096 (14) | −0.0112 (15) |
C16 | 0.0225 (15) | 0.0380 (19) | 0.049 (2) | 0.0005 (13) | 0.0064 (14) | −0.0144 (16) |
C17 | 0.0232 (14) | 0.0330 (16) | 0.0283 (15) | 0.0004 (12) | 0.0032 (12) | −0.0105 (13) |
C18 | 0.0187 (13) | 0.0184 (13) | 0.0292 (14) | 0.0024 (10) | −0.0004 (11) | −0.0049 (11) |
C19 | 0.0258 (14) | 0.0258 (15) | 0.0238 (14) | 0.0030 (12) | 0.0025 (11) | −0.0005 (12) |
C20 | 0.0291 (15) | 0.0333 (18) | 0.0258 (15) | 0.0095 (14) | 0.0028 (12) | 0.0100 (13) |
C21 | 0.046 (2) | 0.0289 (17) | 0.0379 (18) | 0.0059 (15) | 0.0130 (15) | 0.0141 (14) |
C22 | 0.0392 (19) | 0.0207 (15) | 0.044 (2) | −0.0003 (13) | 0.0097 (15) | 0.0028 (13) |
C23 | 0.0297 (15) | 0.0231 (14) | 0.0337 (16) | −0.0010 (13) | 0.0027 (12) | −0.0002 (13) |
C24 | 0.0231 (13) | 0.0165 (13) | 0.0222 (13) | 0.0031 (10) | 0.0034 (11) | 0.0003 (10) |
C25 | 0.0312 (17) | 0.060 (2) | 0.0263 (16) | 0.0124 (16) | 0.0015 (13) | −0.0088 (16) |
C26 | 0.044 (2) | 0.068 (3) | 0.0253 (17) | 0.0154 (19) | 0.0015 (15) | −0.0127 (17) |
C27 | 0.048 (2) | 0.055 (2) | 0.0224 (16) | 0.0026 (18) | −0.0007 (15) | −0.0102 (16) |
C28 | 0.040 (2) | 0.0403 (19) | 0.0334 (18) | 0.0063 (15) | −0.0082 (15) | −0.0021 (15) |
C29 | 0.0298 (16) | 0.0277 (16) | 0.0327 (16) | 0.0033 (13) | −0.0014 (13) | −0.0025 (13) |
C30 | 0.0239 (14) | 0.0245 (14) | 0.0217 (13) | −0.0020 (11) | 0.0002 (11) | −0.0019 (11) |
C31 | 0.0227 (14) | 0.0253 (15) | 0.0260 (15) | 0.0001 (12) | 0.0039 (11) | 0.0012 (12) |
C32 | 0.0302 (16) | 0.0220 (14) | 0.0322 (16) | −0.0003 (12) | 0.0061 (13) | 0.0051 (12) |
C33 | 0.0288 (16) | 0.0299 (16) | 0.0268 (15) | −0.0081 (13) | 0.0024 (12) | 0.0016 (12) |
C34 | 0.0207 (14) | 0.0325 (16) | 0.0279 (15) | −0.0018 (12) | 0.0026 (11) | 0.0009 (13) |
C35 | 0.0214 (12) | 0.0251 (12) | 0.0248 (12) | 0.0002 (13) | 0.0024 (10) | −0.0015 (14) |
C36 | 0.0189 (12) | 0.0222 (15) | 0.0184 (12) | −0.0018 (10) | 0.0033 (10) | −0.0008 (10) |
C37 | 0.0245 (15) | 0.0281 (16) | 0.0335 (16) | 0.0029 (12) | 0.0081 (13) | 0.0041 (13) |
C38 | 0.0234 (15) | 0.0338 (18) | 0.049 (2) | −0.0013 (13) | 0.0062 (14) | −0.0148 (15) |
C39 | 0.072 (4) | 0.042 (3) | 0.047 (2) | 0.005 (3) | 0.011 (3) | −0.001 (2) |
Cl1 | 0.0404 (7) | 0.0945 (11) | 0.0531 (7) | −0.0046 (7) | 0.0097 (6) | −0.0245 (7) |
Cl2 | 0.0573 (8) | 0.1012 (12) | 0.0411 (6) | 0.0117 (7) | 0.0108 (5) | −0.0066 (7) |
C40 | 0.072 (4) | 0.042 (3) | 0.047 (2) | 0.005 (3) | 0.011 (3) | −0.001 (2) |
Cl3 | 0.0404 (7) | 0.0945 (11) | 0.0531 (7) | −0.0046 (7) | 0.0097 (6) | −0.0245 (7) |
Cl4 | 0.0573 (8) | 0.1012 (12) | 0.0411 (6) | 0.0117 (7) | 0.0108 (5) | −0.0066 (7) |
Ag1—N2 | 2.317 (3) | C14—C15 | 1.372 (5) |
Ag1—N1 | 2.345 (3) | C15—C16 | 1.382 (5) |
Ag1—P1 | 2.4532 (8) | C16—C17 | 1.391 (4) |
Ag1—P2 | 2.4623 (7) | C17—C18 | 1.389 (4) |
Ag2—C38 | 2.044 (3) | C19—C24 | 1.529 (4) |
Ag2—C37i | 2.052 (3) | C19—C20 | 1.536 (4) |
P1—C18 | 1.826 (3) | C20—C21 | 1.514 (5) |
P1—C12 | 1.831 (3) | C21—C22 | 1.531 (5) |
P1—C6 | 1.854 (3) | C22—C23 | 1.531 (5) |
P2—C36 | 1.823 (3) | C23—C24 | 1.545 (4) |
P2—C30 | 1.833 (3) | C25—C30 | 1.395 (4) |
P2—C24 | 1.844 (3) | C25—C26 | 1.395 (5) |
N1—C37 | 1.146 (4) | C26—C27 | 1.375 (5) |
N2—C38 | 1.155 (4) | C27—C28 | 1.371 (5) |
C1—C2 | 1.528 (4) | C28—C29 | 1.395 (5) |
C1—C6 | 1.529 (4) | C29—C30 | 1.393 (4) |
C2—C3 | 1.524 (5) | C31—C32 | 1.387 (4) |
C3—C4 | 1.523 (5) | C31—C36 | 1.399 (4) |
C4—C5 | 1.525 (4) | C32—C33 | 1.386 (4) |
C5—C6 | 1.548 (4) | C33—C34 | 1.391 (5) |
C7—C8 | 1.391 (4) | C34—C35 | 1.386 (4) |
C7—C12 | 1.400 (4) | C35—C36 | 1.394 (4) |
C8—C9 | 1.383 (4) | C37—Ag2ii | 2.052 (3) |
C9—C10 | 1.391 (4) | C39—Cl2 | 1.740 (5) |
C10—C11 | 1.380 (4) | C39—Cl1 | 1.784 (5) |
C11—C12 | 1.401 (4) | C40—Cl4 | 1.779 (18) |
C13—C14 | 1.397 (4) | C40—Cl3 | 1.779 (18) |
C13—C18 | 1.401 (4) | ||
N2—Ag1—N1 | 94.59 (11) | C14—C13—C18 | 120.1 (3) |
N2—Ag1—P1 | 110.09 (8) | C15—C14—C13 | 120.5 (3) |
N1—Ag1—P1 | 109.41 (7) | C14—C15—C16 | 120.1 (3) |
N2—Ag1—P2 | 106.97 (8) | C15—C16—C17 | 119.8 (3) |
N1—Ag1—P2 | 105.12 (7) | C18—C17—C16 | 121.2 (3) |
P1—Ag1—P2 | 126.04 (2) | C17—C18—C13 | 118.4 (3) |
C38—Ag2—C37i | 173.26 (15) | C17—C18—P1 | 117.6 (2) |
C18—P1—C12 | 103.51 (13) | C13—C18—P1 | 124.1 (2) |
C18—P1—C6 | 104.52 (13) | C24—C19—C20 | 109.5 (2) |
C12—P1—C6 | 104.20 (13) | C21—C20—C19 | 111.2 (3) |
C18—P1—Ag1 | 114.59 (10) | C20—C21—C22 | 110.5 (3) |
C12—P1—Ag1 | 116.63 (10) | C23—C22—C21 | 111.5 (3) |
C6—P1—Ag1 | 112.09 (10) | C22—C23—C24 | 110.2 (2) |
C36—P2—C30 | 101.66 (13) | C19—C24—C23 | 110.2 (2) |
C36—P2—C24 | 105.62 (13) | C19—C24—P2 | 112.76 (19) |
C30—P2—C24 | 103.15 (13) | C23—C24—P2 | 109.7 (2) |
C36—P2—Ag1 | 109.90 (9) | C30—C25—C26 | 120.9 (3) |
C30—P2—Ag1 | 117.68 (10) | C27—C26—C25 | 119.5 (3) |
C24—P2—Ag1 | 117.14 (9) | C28—C27—C26 | 120.4 (3) |
C37—N1—Ag1 | 168.8 (3) | C27—C28—C29 | 120.7 (3) |
C38—N2—Ag1 | 169.7 (3) | C30—C29—C28 | 119.8 (3) |
C2—C1—C6 | 111.4 (3) | C29—C30—C25 | 118.7 (3) |
C3—C2—C1 | 111.0 (3) | C29—C30—P2 | 119.9 (2) |
C4—C3—C2 | 110.2 (3) | C25—C30—P2 | 121.4 (2) |
C3—C4—C5 | 111.9 (3) | C32—C31—C36 | 120.6 (3) |
C4—C5—C6 | 110.9 (3) | C33—C32—C31 | 120.1 (3) |
C1—C6—C5 | 110.3 (2) | C32—C33—C34 | 119.9 (3) |
C1—C6—P1 | 108.8 (2) | C35—C34—C33 | 119.9 (3) |
C5—C6—P1 | 110.75 (19) | C34—C35—C36 | 120.9 (3) |
C8—C7—C12 | 120.6 (3) | C35—C36—C31 | 118.6 (3) |
C9—C8—C7 | 120.3 (3) | C35—C36—P2 | 124.3 (2) |
C8—C9—C10 | 119.4 (3) | C31—C36—P2 | 117.2 (2) |
C11—C10—C9 | 120.6 (3) | N1—C37—Ag2ii | 173.3 (3) |
C10—C11—C12 | 120.6 (3) | N2—C38—Ag2 | 174.1 (4) |
C7—C12—C11 | 118.4 (3) | Cl2—C39—Cl1 | 110.8 (3) |
C7—C12—P1 | 117.8 (2) | Cl4—C40—Cl3 | 102.7 (13) |
C11—C12—P1 | 123.8 (2) |
Symmetry codes: (i) −x−1, y−1/2, −z+2; (ii) −x−1, y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Ag2(CN)2(C16H21P)2]·CH2Cl2 |
Mr | 889.34 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 10.0007 (12), 14.7062 (18), 13.5338 (17) |
β (°) | 98.285 (2) |
V (Å3) | 1969.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.24 |
Crystal size (mm) | 0.24 × 0.11 × 0.09 |
Data collection | |
Diffractometer | Bruker APEX |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.784, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22828, 9243, 8980 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.058, 1.07 |
No. of reflections | 9243 |
No. of parameters | 434 |
No. of restraints | 9 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.87, −0.53 |
Absolute structure | Flack (1983), 4318 Friedel pairs |
Absolute structure parameter | 0.087 (16) |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 2002), SHELXTL.
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
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.