supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m1931    [ doi:10.1107/S1600536807028875 ]

Bis[[mu]-diphenyl(2-pyridylmethyl)phosphine-[kappa]2N,P]bis[nitratosilver(I)](Ag-Ag)

K. K. Klausmeyer and F. Hung-Low

Abstract top

In the title molecular structure, [Ag2(NO3)2(C18H16NP)2], the AgI atoms are held in close proximity by the chelating effect of the diphenyl(2-pyridylmethyl)phosphine ligand, with an Ag-Ag bond distance of 2.9171 (7) Å. The angles around the metal centers describe a distorted tetrahedral geometry, with the NO3- ions bound to the AgI atoms in a monodentate fashion. The molecule is centrosymmetric.

Comment top

The study of silver coordinated complexes using P,N based ligands is a well established field of research, with reports that describe the formation of a large variety of coordination modes associated with variation in the ligand/metal ratio or by changes in the solvent or counterion in charged systems (Cingolani et al., 2006; Feazell et al., 2005). The well known 2-(phosphinomethyl)pyridyl family of ligands of the type PPhxCH2py3 − x (x = 0, 1, 2) have been widely used in coordination chemistry associated with transition metals and applications in the catalysis arena, due to the geometrical flexibility and electronic properties that these phosphine ligands exhibit (Murso & Stalke, 2004; Sandee & Reek, 2006). The diphenyl(2-pyridylmethyl)phosphine is of special interest because as a bidentate ligand it can connect two identical or different metal centers, allowing for a close proximity and direct metal-metal interactions. The use of silver starting materials and these P,N based ligands have received great attention lately because of the flexible coordination sphere of the silver centers, allowing it to take different structural motifs (Klausmeyer et al., 2004). Thus, following this research line we present in this study the synthesis of a silver-based dinuclear complex, obtained by the reaction of the diphenyl(2-pyridylmethyl)phosphine ligand with silver nitrate in a 1:1 ratio.

The title compound, (I), consists of two phosphine ligands coordinated head-to-tail to two silver atoms across the Ag—Ag axis, and the nitrate anions bound to the metal centers in a unidentate fashion. Accordingly, the AgI atom in (I) is four-coordinated by one P atom, one N atom, an O atom from the nitrate anion, and a Ag atom with which the metallophilic interaction occurs. The coordination sphere of the metal centers reveal a distorted tetrahedral environment with angles ranging between 87.23 (3) and 132.1 (9)°. The flexibility of the ligand is evidenced by a twisting angle of 77.4 (4)° for P1—C1—C2—N1. The Ag—P and Ag—N distances fall in the range of reported values. The NO3 anions coordinated to the corresponding silver atoms through one of the oxygen atoms, are bounded perpendicular to the Ag—Ag bond with an angle of 89.21 (11)° for O1—Ag1—Ag1i [symmetry code: (i) −x, −y, −z].

Related literature top

For related literature, see: Cingolani et al. (2006); Feazell et al. (2005); Klausmeyer et al. (2004); Murso & Stalke (2004); Sandee & Reek (2006).

Experimental top

The title compound was obtained by mixing AgNO3 (0.051 g, 0.3 mmol) and PPh2(2-CH2C5H4N) (0.083 g, 0.3 mmol) in 20 ml of acetonitrile. The mixture was stirred for 10 min and pulled dry under vacuum. Diffraction-quality crystals were obtained by slow diffusion of diethyl ether into a concentrated N,N-dimethylformamide solution of (I) in the presence of air.

Refinement top

All H atoms were included in calculated positions (C—H = 0.95–0.99 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C). The highest residual electron density peak is located 1.11 Å from atom Ag1.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2; 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 (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. The suffix A corresponds to symmetry code (−x, −y, −z).
Bis[µ-diphenyl(2-pyridylmethyl)phosphine- κ2N,P]bis[nitratosilver(I)](Ag—Ag) top
Crystal data top
[Ag2(NO3)2(C18H16NP)2]F000 = 1792
Mr = 894.34Dx = 1.673 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 7549 reflections
a = 13.7678 (19) Åθ = 2.9–27.9º
b = 12.7143 (17) ŵ = 1.25 mm−1
c = 20.364 (3) ÅT = 110 (2) K
β = 95.251 (5)ºBlock, colorless
V = 3549.7 (9) Å30.32 × 0.10 × 0.09 mm
Z = 4
Data collection top
Bruker APEX X8 CCD area-detector
diffractometer		3109 independent reflections
Radiation source: fine-focus sealed tube2726 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.044
T = 110(2) Kθmax = 25.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.70, Tmax = 0.89k = −11→15
17376 measured reflectionsl = −24→24
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)] = 0.038H-atom parameters constrained
wR(F2) = 0.099  w = 1/[σ2(Fo2) + (0.047P)2 + 24.9163P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3109 reflectionsΔρmax = 2.89 e Å−3
226 parametersΔρmin = −0.74 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ag2(NO3)2(C18H16NP)2]V = 3549.7 (9) Å3
Mr = 894.34Z = 4
Monoclinic, C2/cMo Kα
a = 13.7678 (19) ŵ = 1.25 mm−1
b = 12.7143 (17) ÅT = 110 (2) K
c = 20.364 (3) Å0.32 × 0.10 × 0.09 mm
β = 95.251 (5)º
Data collection top
Bruker APEX X8 CCD area-detector
diffractometer		3109 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2726 reflections with I > 2σ(I)
Tmin = 0.70, Tmax = 0.89Rint = 0.044
17376 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.099  w = 1/[σ2(Fo2) + (0.047P)2 + 24.9163P]
where P = (Fo2 + 2Fc2)/3
S = 1.03Δρmax = 2.89 e Å−3
3109 reflectionsΔρmin = −0.74 e Å−3
226 parameters
Special details top

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
Ag10.04440 (2)−0.01171 (2)0.067423 (15)0.02050 (13)
P1−0.08720 (8)0.09272 (8)0.10130 (5)0.0171 (2)
N10.1901 (2)0.0319 (3)0.03379 (16)0.0177 (7)
C10.1915 (3)−0.1181 (3)−0.04038 (18)0.0179 (8)
H1A0.1696−0.1612−0.00410.021*
H1B0.2414−0.1589−0.06160.021*
C20.2369 (3)−0.0183 (3)−0.01233 (19)0.0170 (9)
C30.3233 (3)0.0199 (3)−0.0336 (2)0.0227 (9)
H30.3542−0.0157−0.06700.027*
C40.3636 (3)0.1110 (4)−0.0050 (2)0.0280 (10)
H40.42280.1383−0.01870.034*
C50.3172 (3)0.1616 (3)0.0433 (2)0.0234 (9)
H50.34410.22330.06410.028*
C60.2310 (3)0.1200 (3)0.0604 (2)0.0219 (9)
H60.19830.15560.09300.026*
C7−0.1431 (3)0.0425 (3)0.17266 (19)0.0199 (9)
C8−0.1145 (3)−0.0544 (4)0.1985 (2)0.0268 (10)
H8−0.0682−0.09520.17770.032*
C9−0.1528 (3)−0.0925 (4)0.2546 (2)0.0316 (11)
H9−0.1318−0.15840.27260.038*
C10−0.2218 (3)−0.0344 (4)0.2844 (2)0.0306 (11)
H10−0.2477−0.06010.32300.037*
C11−0.2527 (3)0.0612 (4)0.2576 (2)0.0284 (10)
H11−0.30100.10040.27740.034*
C12−0.2140 (3)0.1003 (4)0.2022 (2)0.0230 (9)
H12−0.23540.16610.18420.028*
C13−0.0448 (3)0.2231 (3)0.12690 (18)0.0166 (8)
C140.0418 (3)0.2276 (3)0.1691 (2)0.0225 (9)
H140.07360.16440.18380.027*
C150.0809 (3)0.3234 (4)0.1895 (2)0.0272 (10)
H150.13930.32550.21820.033*
C160.0364 (3)0.4161 (4)0.1687 (2)0.0260 (10)
H160.06410.48170.18260.031*
C17−0.0494 (3)0.4128 (3)0.1271 (2)0.0258 (10)
H17−0.08070.47650.11270.031*
C18−0.0896 (3)0.3170 (3)0.1064 (2)0.0234 (9)
H18−0.14820.31560.07790.028*
N20.0698 (3)−0.2472 (3)0.0958 (2)0.0291 (9)
O10.0043 (3)−0.1936 (3)0.0628 (2)0.0543 (12)
O20.1523 (2)−0.2084 (3)0.10666 (15)0.0378 (8)
O30.0526 (3)−0.3363 (3)0.1142 (2)0.0573 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0186 (2)0.0202 (2)0.0234 (2)0.00012 (12)0.00551 (13)−0.00150 (13)
P10.0180 (5)0.0182 (5)0.0153 (5)−0.0019 (4)0.0028 (4)0.0005 (4)
N10.0172 (18)0.0183 (18)0.0178 (17)−0.0016 (14)0.0034 (14)0.0005 (14)
C10.020 (2)0.021 (2)0.0127 (19)−0.0006 (17)0.0026 (16)−0.0003 (16)
C20.017 (2)0.020 (2)0.014 (2)0.0001 (16)0.0010 (16)0.0046 (16)
C30.017 (2)0.034 (2)0.017 (2)−0.0004 (18)0.0047 (17)0.0016 (18)
C40.019 (2)0.034 (3)0.032 (2)−0.0074 (19)0.0040 (19)0.005 (2)
C50.023 (2)0.022 (2)0.024 (2)−0.0072 (18)−0.0028 (18)−0.0006 (18)
C60.024 (2)0.019 (2)0.022 (2)0.0002 (18)0.0007 (18)0.0003 (17)
C70.021 (2)0.024 (2)0.015 (2)−0.0066 (18)−0.0007 (17)0.0004 (17)
C80.026 (2)0.029 (2)0.025 (2)0.0004 (19)0.0032 (19)0.0058 (19)
C90.032 (3)0.037 (3)0.025 (2)−0.003 (2)0.003 (2)0.012 (2)
C100.031 (3)0.043 (3)0.017 (2)−0.015 (2)0.0010 (19)0.008 (2)
C110.019 (2)0.046 (3)0.021 (2)−0.006 (2)0.0048 (18)−0.004 (2)
C120.023 (2)0.029 (2)0.017 (2)−0.0048 (18)−0.0002 (18)−0.0008 (18)
C130.018 (2)0.017 (2)0.015 (2)−0.0018 (16)0.0059 (16)−0.0002 (16)
C140.019 (2)0.025 (2)0.023 (2)0.0014 (17)0.0031 (18)−0.0035 (18)
C150.024 (2)0.034 (3)0.024 (2)−0.006 (2)0.0004 (19)−0.008 (2)
C160.032 (3)0.025 (2)0.023 (2)−0.0107 (19)0.011 (2)−0.0064 (18)
C170.035 (3)0.016 (2)0.027 (2)−0.0011 (18)0.008 (2)0.0001 (18)
C180.022 (2)0.025 (2)0.024 (2)−0.0018 (18)0.0022 (18)−0.0014 (18)
N20.030 (2)0.017 (2)0.042 (2)−0.0030 (17)0.0130 (18)−0.0056 (17)
O10.0246 (19)0.0224 (18)0.114 (4)−0.0011 (15)−0.001 (2)0.017 (2)
O20.038 (2)0.049 (2)0.0263 (17)−0.0196 (17)−0.0024 (15)0.0013 (15)
O30.046 (2)0.025 (2)0.099 (3)−0.0062 (17)−0.004 (2)0.017 (2)
Geometric parameters (Å, °) top
Ag1—N12.247 (3)C8—C91.389 (6)
Ag1—O12.378 (3)C8—H80.9500
Ag1—P12.3980 (11)C9—C101.386 (7)
Ag1—Ag1i2.9171 (7)C9—H90.9500
P1—C131.818 (4)C10—C111.383 (7)
P1—C71.821 (4)C10—H100.9500
P1—C1i1.839 (4)C11—C121.384 (6)
N1—C61.346 (5)C11—H110.9500
N1—C21.348 (5)C12—H120.9500
C1—C21.504 (6)C13—C181.391 (6)
C1—P1i1.839 (4)C13—C141.406 (6)
C1—H1A0.9900C14—C151.380 (6)
C1—H1B0.9900C14—H140.9500
C2—C31.390 (6)C15—C161.376 (7)
C3—C41.389 (6)C15—H150.9500
C3—H30.9500C16—C171.390 (7)
C4—C51.380 (6)C16—H160.9500
C4—H40.9500C17—C181.387 (6)
C5—C61.374 (6)C17—H170.9500
C5—H50.9500C18—H180.9500
C6—H60.9500N2—O31.222 (5)
C7—C81.383 (6)N2—O21.239 (5)
C7—C121.399 (6)N2—O11.273 (5)
N1—Ag1—O1116.02 (13)C12—C7—P1121.4 (3)
N1—Ag1—P1132.06 (9)C7—C8—C9120.4 (4)
O1—Ag1—P1111.77 (10)C7—C8—H8119.8
N1—Ag1—Ag1i89.81 (9)C9—C8—H8119.8
O1—Ag1—Ag1i89.21 (11)C10—C9—C8120.1 (5)
P1—Ag1—Ag1i87.23 (3)C10—C9—H9119.9
C13—P1—C7103.83 (18)C8—C9—H9119.9
C13—P1—C1i104.12 (18)C11—C10—C9119.6 (4)
C7—P1—C1i103.81 (19)C11—C10—H10120.2
C13—P1—Ag1110.85 (13)C9—C10—H10120.2
C7—P1—Ag1114.91 (15)C10—C11—C12120.7 (4)
C1i—P1—Ag1117.87 (13)C10—C11—H11119.7
C6—N1—C2117.8 (3)C12—C11—H11119.7
C6—N1—Ag1115.8 (3)C11—C12—C7119.8 (4)
C2—N1—Ag1126.3 (3)C11—C12—H12120.1
C2—C1—P1i112.3 (3)C7—C12—H12120.1
C2—C1—H1A109.1C18—C13—C14118.5 (4)
P1i—C1—H1A109.1C18—C13—P1125.1 (3)
C2—C1—H1B109.1C14—C13—P1116.4 (3)
P1i—C1—H1B109.1C15—C14—C13120.4 (4)
H1A—C1—H1B107.9C15—C14—H14119.8
N1—C2—C3121.9 (4)C13—C14—H14119.8
N1—C2—C1117.2 (3)C16—C15—C14120.9 (4)
C3—C2—C1120.9 (4)C16—C15—H15119.6
C4—C3—C2118.8 (4)C14—C15—H15119.6
C4—C3—H3120.6C15—C16—C17119.4 (4)
C2—C3—H3120.6C15—C16—H16120.3
C5—C4—C3119.6 (4)C17—C16—H16120.3
C5—C4—H4120.2C18—C17—C16120.3 (4)
C3—C4—H4120.2C18—C17—H17119.9
C6—C5—C4118.0 (4)C16—C17—H17119.9
C6—C5—H5121.0C17—C18—C13120.6 (4)
C4—C5—H5121.0C17—C18—H18119.7
N1—C6—C5123.9 (4)C13—C18—H18119.7
N1—C6—H6118.1O3—N2—O2121.0 (4)
C5—C6—H6118.1O3—N2—O1120.6 (4)
C8—C7—C12119.3 (4)O2—N2—O1118.3 (4)
C8—C7—P1119.3 (3)N2—O1—Ag1110.4 (3)
Symmetry codes: (i) −x, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Ag1—N12.247 (3)Ag1—Ag1i2.9171 (7)
Ag1—P12.3980 (11)
N1—Ag1—O1116.02 (13)O1—Ag1—Ag1i89.21 (11)
N1—Ag1—P1132.06 (9)P1—Ag1—Ag1i87.23 (3)
O1—Ag1—P1111.77 (10)C13—P1—C7103.83 (18)
N1—Ag1—Ag1i89.81 (9)
Symmetry codes: (i) −x, −y, −z.
Acknowledgements top

The diffractometer was purchased with funds received from the National Science Foundation Major Research Instrumentation Program Grant CHE-0321214. K K thanks the Robert A. Welch Foundation for support (AA-1508).

references
References top

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

Cingolani, A., Effendy, initials?, Martini, D., Pettinari, C., Skelton, B. W. & White, A. H. (2006). Inorg. Chim. Acta, 359, 2183–2193.

Feazell, R. P., Carson, C. E. & Klausmeyer, K. K. (2005). Inorg. Chem. 44, 996–1005.

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

Murso, A. & Stalke, D. (2004). Dalton Trans. pp. 2563–2569.

Sandee, A. J. & Reek, J. N. H. (2006). Dalton Trans. pp. 3385–3391.

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

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

Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.