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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028875/is2178sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028875/is2178Isup2.hkl
Contains datablock I

CCDC reference: 654778

Key indicators

  • Single-crystal X-ray study
  • T = 110 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.038
  • wR factor = 0.099
  • Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 3.89 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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.

Structure description 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].

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

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]F(000) = 1792
Mr = 894.34Dx = 1.673 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 7549 reflections
a = 13.7678 (19) Åθ = 2.9–27.9°
b = 12.7143 (17) ŵ = 1.25 mm1
c = 20.364 (3) ÅT = 110 K
β = 95.251 (5)°Block, 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)
Graphite monochromatorRint = 0.044
φ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1616
Tmin = 0.70, Tmax = 0.89k = 1115
17376 measured reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.047P)2 + 24.9163P]
where P = (Fo2 + 2Fc2)/3
3109 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 2.89 e Å3
0 restraintsΔρmin = 0.74 e Å3
Crystal data top
[Ag2(NO3)2(C18H16NP)2]V = 3549.7 (9) Å3
Mr = 894.34Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.7678 (19) ŵ = 1.25 mm1
b = 12.7143 (17) ÅT = 110 K
c = 20.364 (3) Å0.32 × 0.10 × 0.09 mm
β = 95.251 (5)°
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)] = 0.0380 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.047P)2 + 24.9163P]
where P = (Fo2 + 2Fc2)/3
3109 reflectionsΔρmax = 2.89 e Å3
226 parametersΔρmin = 0.74 e Å3
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)
P10.08720 (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)
H1A0.16960.16120.00410.021*
H1B0.24140.15890.06160.021*
C20.2369 (3)0.0183 (3)0.01233 (19)0.0170 (9)
C30.3233 (3)0.0199 (3)0.0336 (2)0.0227 (9)
H30.35420.01570.06700.027*
C40.3636 (3)0.1110 (4)0.0050 (2)0.0280 (10)
H40.42280.13830.01870.034*
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*
C70.1431 (3)0.0425 (3)0.17266 (19)0.0199 (9)
C80.1145 (3)0.0544 (4)0.1985 (2)0.0268 (10)
H80.06820.09520.17770.032*
C90.1528 (3)0.0925 (4)0.2546 (2)0.0316 (11)
H90.13180.15840.27260.038*
C100.2218 (3)0.0344 (4)0.2844 (2)0.0306 (11)
H100.24770.06010.32300.037*
C110.2527 (3)0.0612 (4)0.2576 (2)0.0284 (10)
H110.30100.10040.27740.034*
C120.2140 (3)0.1003 (4)0.2022 (2)0.0230 (9)
H120.23540.16610.18420.028*
C130.0448 (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*
C170.0494 (3)0.4128 (3)0.1271 (2)0.0258 (10)
H170.08070.47650.11270.031*
C180.0896 (3)0.3170 (3)0.1064 (2)0.0234 (9)
H180.14820.31560.07790.028*
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, º) 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 code: (i) x, y, z.

Experimental details

Crystal data
Chemical formula[Ag2(NO3)2(C18H16NP)2]
Mr894.34
Crystal system, space groupMonoclinic, C2/c
Temperature (K)110
a, b, c (Å)13.7678 (19), 12.7143 (17), 20.364 (3)
β (°) 95.251 (5)
V3)3549.7 (9)
Z4
Radiation typeMo Kα
µ (mm1)1.25
Crystal size (mm)0.32 × 0.10 × 0.09
Data collection
DiffractometerBruker APEX X8 CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.70, 0.89
No. of measured, independent and
observed [I > 2σ(I)] reflections
17376, 3109, 2726
Rint0.044
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.099, 1.03
No. of reflections3109
No. of parameters226
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.047P)2 + 24.9163P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)2.89, 0.74

Computer programs: APEX2 (Bruker, 2003), APEX2, SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000), SHELXTL.

Selected geometric parameters (Å, º) 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 code: (i) x, y, z.
 

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