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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028607/br2046sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028607/br2046Isup2.hkl
Contains datablock I

CCDC reference: 654761

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](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

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.

Structure description 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.

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).

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(C16H21P)2]·CH2Cl2F(000) = 900
Mr = 889.34Dx = 1.500 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: p 2ybCell parameters from 7412 reflections
a = 10.0007 (12) Åθ = 2.5–28.3°
b = 14.7062 (18) ŵ = 1.24 mm1
c = 13.5338 (17) ÅT = 120 K
β = 98.285 (2)°Needle, 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)
Graphite monochromatorRint = 0.021
Detector resolution: 836.6 pixels mm-1θmax = 28.3°, θmin = 2.1°
ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
k = 1819
Tmin = 0.784, Tmax = 0.899l = 1717
22828 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)] = 0.025H-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 reflectionsΔρmax = 0.87 e Å3
434 parametersΔρmin = 0.53 e Å3
9 restraintsAbsolute structure: Flack (1983), 4318 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.087 (16)
Crystal data top
[Ag2(CN)2(C16H21P)2]·CH2Cl2V = 1969.7 (4) Å3
Mr = 889.34Z = 2
Monoclinic, P21Mo Kα radiation
a = 10.0007 (12) ŵ = 1.24 mm1
b = 14.7062 (18) ÅT = 120 K
c = 13.5338 (17) Å0.24 × 0.11 × 0.09 mm
β = 98.285 (2)°
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 Å3
S = 1.07Δρmin = 0.53 e Å3
9243 reflectionsAbsolute structure: Flack (1983), 4318 Friedel pairs
434 parametersAbsolute structure 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)
Ag10.151855 (18)0.265568 (13)1.178117 (14)0.02008 (5)
Ag20.54560 (2)0.012640 (17)1.06267 (2)0.03267 (6)
P10.13755 (7)0.32740 (5)1.34766 (5)0.01945 (14)
P20.03650 (7)0.20108 (5)1.10216 (5)0.01898 (14)
N10.2515 (3)0.37361 (19)1.0630 (2)0.0306 (6)
N20.3297 (3)0.1636 (2)1.1481 (2)0.0381 (7)
C10.1683 (3)0.1585 (2)1.4299 (3)0.0292 (7)
H1A0.17650.13571.36050.035*
H1B0.07120.16011.45750.035*
C20.2420 (3)0.0939 (2)1.4921 (3)0.0383 (8)
H2A0.20410.03191.48920.046*
H2B0.22770.11391.56270.046*
C30.3929 (3)0.0917 (2)1.4538 (3)0.0353 (7)
H3A0.40790.06681.38510.042*
H3B0.43910.05151.49680.042*
C40.4520 (3)0.1871 (2)1.4540 (3)0.0338 (7)
H4A0.44410.20941.52360.041*
H4B0.54920.18491.42650.041*
C50.3802 (3)0.2533 (2)1.3925 (2)0.0284 (6)
H5A0.41770.31511.39770.034*
H5B0.39640.23491.32130.034*
C60.2263 (3)0.2547 (2)1.4294 (2)0.0229 (6)
H60.21040.27961.49890.027*
C70.3316 (3)0.4613 (2)1.2994 (2)0.0259 (6)
H70.37340.41711.25380.031*
C80.3922 (3)0.5458 (2)1.3058 (2)0.0293 (7)
H80.47650.55831.26600.035*
C90.3306 (3)0.6116 (2)1.3697 (2)0.0268 (6)
H90.37170.66941.37360.032*
C100.2078 (3)0.5923 (2)1.4283 (2)0.0285 (6)
H100.16460.63761.47170.034*
C110.1483 (3)0.5080 (2)1.4240 (2)0.0243 (5)
H110.06510.49561.46510.029*
C120.2093 (3)0.44075 (19)1.3594 (2)0.0214 (5)
C130.0679 (3)0.3287 (2)1.5178 (2)0.0265 (6)
H130.00060.31681.55790.032*
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)
H21A0.07560.04201.34510.044*
H21B0.19580.11021.32940.044*
C220.0849 (4)0.0682 (2)1.1950 (3)0.0343 (7)
H22A0.15620.08691.15540.041*
H22B0.01730.11771.19130.041*
C230.0167 (3)0.0185 (2)1.1501 (2)0.0290 (6)
H23A0.06100.03381.18490.035*
H23B0.01790.00851.07870.035*
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*
C270.0444 (4)0.1299 (3)0.7663 (3)0.0423 (9)
H270.06160.11560.69710.051*
C280.1379 (4)0.1781 (3)0.8097 (3)0.0391 (8)
H280.21860.19810.76990.047*
C290.1158 (3)0.1980 (2)0.9115 (2)0.0307 (7)
H290.18230.22990.94130.037*
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)
C370.3189 (3)0.4236 (2)1.0136 (2)0.0283 (6)
C380.4078 (3)0.1074 (2)1.1226 (3)0.0354 (8)
C390.5746 (6)0.2741 (4)0.8594 (5)0.0537 (12)0.880 (2)
H39A0.60660.21090.84600.064*0.880 (2)
H39B0.52230.27600.92730.064*0.880 (2)
Cl10.46825 (14)0.30626 (12)0.77027 (10)0.0624 (4)0.880 (2)
Cl20.71293 (14)0.34665 (12)0.85379 (9)0.0662 (4)0.880 (2)
C400.617 (4)0.292 (3)0.852 (4)0.0537 (12)0.120 (2)
H40A0.63480.33500.90510.064*0.120 (2)
H40B0.70440.27100.81540.064*0.120 (2)
Cl30.5162 (11)0.3441 (9)0.7695 (8)0.0624 (4)0.120 (2)
Cl40.5150 (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, º) 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) x1, y1/2, z+2; (ii) x1, y+1/2, z+2.

Experimental details

Crystal data
Chemical formula[Ag2(CN)2(C16H21P)2]·CH2Cl2
Mr889.34
Crystal system, space groupMonoclinic, P21
Temperature (K)120
a, b, c (Å)10.0007 (12), 14.7062 (18), 13.5338 (17)
β (°) 98.285 (2)
V3)1969.7 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.24
Crystal size (mm)0.24 × 0.11 × 0.09
Data collection
DiffractometerBruker APEX
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.784, 0.899
No. of measured, independent and
observed [I > 2σ(I)] reflections
22828, 9243, 8980
Rint0.021
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.058, 1.07
No. of reflections9243
No. of parameters434
No. of restraints9
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.87, 0.53
Absolute structureFlack (1983), 4318 Friedel pairs
Absolute structure parameter0.087 (16)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 2002), SHELXTL.

 

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