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Acta Cryst. (2009). E65, m1087    [ doi:10.1107/S160053680903178X ]

{4-[(Diphenylphosphino)methylamino]pyridinium-[kappa]P}bis(nitrato-[kappa]O)silver(I)

J. Shang, L.-C. Gui, Q.-L. Ni, M. Zhong and H.-C. Lian

Abstract top

In the title mononuclear complex, [Ag(C18H18N2P)(NO3)2], the metal centre is coordinated in a slightly distorted trigonal-planar geometry by the P atom of the phosphine ligand and the O atoms of the two monodentate nitrate anions. In the crystal structure, complex molecules are connected by intermolecular N-H...O hydrogen bonds, forming chains running parallel to the b axis.

Comment top

Silver(I) metal complexes with pyridine-phosphine ligands which contain a soft Lewis base (P) and a hard Lewis acid (N) had been extensively studied so far (Song et al., 2002; Durran et al., 2006; Jiang et al., 2009; Wang et al. 2008). Herein, we report the crystal structure of the title complex.

In the title complex (Fig. 1), the silver(I) metal centre adopts a slightly distorted trigonal-planar geometry provided by the P atom of the phosphine ligand and by the O atoms of two monodentate nitrate anions. The metal is displaced by 0.0629 (3) Å from the plane of the donor atoms. In the crystal structure, the complex molecules are linked by intermolecular N—H···O hydrogen bonds (Table 1, Fig. 2) to form chains running parallel to the b axis.

Related literature top

For related structures, see: Song et al. (2002); Durran et al. (2006); Jiang et al. (2009); Wang et al. (2008).

For related literature, see: .

Experimental top

Silver nitrate (0.0168 g, 1 mmol) was dissolved in CH3CN (2 ml) and a solution of N-diphenylphosphinomethyl-4-aminopyridinium (0.0292 g, 1 mmol) in CH3OH (4 ml) was added with stirring for three hours at room temperature. Subsequent diethyl ether diffusion into the solution afforded colourless crystal of the title compound suitable for X-ray analysis.

Refinement top

All H atoms were located geometrically and treated as riding atoms, with N—H= 0.88 Å, C—H = 0.95–0.98 Å, and with Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of title complex with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Partial packing diagram of the title compound, showing the intermlecular N—H···O hydrogen bonds as dashed lines. H atoms not involved in hydrogen bonding are omitted for clarity.
{4-[(Diphenylphosphino)methylamino]pyridinium-κP}bis(nitrato- κO)silver(I) top
Crystal data top
[Ag(C18H18N2P)(NO3)2]Z = 2
Mr = 525.20F(000) = 528
Triclinic, P1Dx = 1.711 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.9760 (9) ÅCell parameters from 5807 reflections
b = 9.6895 (11) Åθ = 2.7–27.0°
c = 14.1207 (16) ŵ = 1.11 mm−1
α = 86.170 (2)°T = 173 K
β = 89.170 (2)°Block, colourless
γ = 69.439 (2)°0.47 × 0.33 × 0.16 mm
V = 1019.5 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		4367 independent reflections
Radiation source: fine-focus sealed tube3802 reflections with I > 2σ(I)
graphiteRint = 0.018
ω scansθmax = 27.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −10→9
Tmin = 0.699, Tmax = 0.838k = −12→12
8623 measured reflectionsl = −18→17
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0737P)2 + 0.0727P]
where P = (Fo2 + 2Fc2)/3
4367 reflections(Δ/σ)max = 0.001
271 parametersΔρmax = 0.66 e Å−3
0 restraintsΔρmin = −0.46 e Å−3
Crystal data top
[Ag(C18H18N2P)(NO3)2]γ = 69.439 (2)°
Mr = 525.20V = 1019.5 (2) Å3
Triclinic, P1Z = 2
a = 7.9760 (9) ÅMo Kα radiation
b = 9.6895 (11) ŵ = 1.11 mm−1
c = 14.1207 (16) ÅT = 173 K
α = 86.170 (2)°0.47 × 0.33 × 0.16 mm
β = 89.170 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		4367 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		3802 reflections with I > 2σ(I)
Tmin = 0.699, Tmax = 0.838Rint = 0.018
8623 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.109Δρmax = 0.66 e Å−3
S = 1.15Δρmin = −0.46 e Å−3
4367 reflectionsAbsolute structure: ?
271 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Ag10.46577 (3)0.46190 (2)0.297716 (16)0.03069 (11)
P10.20209 (10)0.64942 (8)0.24168 (5)0.02155 (16)
O10.6827 (3)0.2456 (3)0.24276 (18)0.0391 (5)
O20.4738 (3)0.1861 (3)0.31211 (19)0.0429 (6)
O30.6975 (3)0.0183 (2)0.25015 (18)0.0428 (6)
O40.6546 (3)0.4154 (2)0.43169 (15)0.0311 (5)
O50.7902 (3)0.5171 (2)0.52073 (17)0.0381 (6)
O60.6328 (4)0.6441 (3)0.39968 (18)0.0481 (7)
N10.1753 (3)1.2090 (3)0.45460 (18)0.0283 (5)
H1A0.17741.29630.46670.034*
N20.1655 (3)0.7994 (2)0.40482 (16)0.0219 (5)
H2A0.23570.72710.44280.026*
N30.6180 (4)0.1481 (3)0.26837 (18)0.0288 (5)
N40.6919 (3)0.5284 (3)0.44974 (17)0.0265 (5)
C10.2731 (4)1.0885 (3)0.5089 (2)0.0269 (6)
H1B0.34421.09910.55940.032*
C20.2720 (4)0.9528 (3)0.4930 (2)0.0256 (6)
H2B0.34200.86930.53210.031*
C30.1658 (3)0.9348 (3)0.41738 (19)0.0204 (5)
C40.0664 (4)1.0632 (3)0.3620 (2)0.0231 (6)
H4A−0.00591.05670.31080.028*
C50.0740 (4)1.1971 (3)0.3818 (2)0.0284 (6)
H5A0.00701.28310.34380.034*
C60.0617 (4)0.7590 (3)0.33523 (19)0.0230 (5)
H6A−0.02720.85000.30510.028*
H6B−0.00490.70100.36800.028*
C70.0424 (4)0.5829 (3)0.18720 (19)0.0229 (5)
C80.0942 (4)0.4339 (3)0.1700 (2)0.0325 (7)
H8A0.21350.36970.18350.039*
C9−0.0290 (5)0.3790 (3)0.1330 (3)0.0394 (8)
H9A0.00680.27720.12170.047*
C10−0.1997 (5)0.4697 (4)0.1129 (2)0.0375 (8)
H10A−0.28310.43100.08840.045*
C11−0.2522 (4)0.6186 (4)0.1281 (2)0.0378 (8)
H11A−0.37110.68220.11290.045*
C12−0.1322 (4)0.6748 (3)0.1652 (2)0.0335 (7)
H12A−0.16920.77700.17580.040*
C130.2342 (4)0.7867 (3)0.15637 (19)0.0227 (5)
C140.1854 (4)0.7949 (4)0.0613 (2)0.0339 (7)
H14A0.13030.72970.04040.041*
C150.2167 (5)0.8975 (4)−0.0029 (2)0.0424 (8)
H15A0.18580.9011−0.06800.051*
C160.2934 (5)0.9955 (4)0.0282 (3)0.0414 (8)
H16A0.31041.0689−0.01500.050*
C170.3444 (5)0.9857 (4)0.1215 (3)0.0378 (8)
H17A0.39771.05190.14250.045*
C180.3189 (4)0.8801 (3)0.1855 (2)0.0285 (6)
H18A0.35930.87160.24930.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.03087 (16)0.02167 (15)0.03252 (16)0.00010 (10)−0.00920 (10)−0.00312 (9)
P10.0243 (4)0.0165 (3)0.0215 (3)−0.0036 (3)−0.0032 (3)−0.0036 (3)
O10.0364 (13)0.0254 (12)0.0523 (15)−0.0074 (10)0.0050 (11)−0.0014 (10)
O20.0350 (13)0.0333 (13)0.0535 (15)−0.0049 (10)0.0092 (11)0.0023 (11)
O30.0476 (14)0.0205 (11)0.0509 (15)0.0013 (10)−0.0151 (11)−0.0095 (10)
O40.0377 (12)0.0186 (10)0.0362 (12)−0.0080 (9)−0.0105 (9)−0.0035 (8)
O50.0479 (14)0.0260 (12)0.0433 (13)−0.0169 (11)−0.0224 (11)0.0037 (10)
O60.0708 (18)0.0321 (13)0.0454 (15)−0.0250 (13)−0.0217 (13)0.0142 (11)
N10.0319 (13)0.0239 (13)0.0343 (14)−0.0151 (11)0.0092 (11)−0.0096 (10)
N20.0283 (12)0.0136 (11)0.0207 (11)−0.0034 (9)−0.0046 (9)−0.0004 (8)
N30.0320 (14)0.0225 (13)0.0275 (13)−0.0035 (11)−0.0083 (10)−0.0036 (10)
N40.0292 (13)0.0214 (12)0.0271 (12)−0.0068 (10)−0.0038 (10)0.0000 (10)
C10.0248 (14)0.0313 (16)0.0276 (15)−0.0123 (12)0.0047 (11)−0.0092 (12)
C20.0234 (14)0.0331 (16)0.0205 (13)−0.0096 (12)0.0016 (10)−0.0042 (11)
C30.0171 (12)0.0223 (14)0.0205 (13)−0.0049 (10)0.0035 (10)−0.0043 (10)
C40.0230 (13)0.0214 (14)0.0240 (14)−0.0064 (11)−0.0002 (10)−0.0025 (11)
C50.0286 (15)0.0275 (16)0.0277 (15)−0.0085 (12)0.0053 (11)−0.0001 (11)
C60.0243 (13)0.0240 (14)0.0202 (13)−0.0074 (11)−0.0008 (10)−0.0039 (10)
C70.0267 (14)0.0198 (13)0.0229 (13)−0.0086 (11)−0.0025 (11)−0.0024 (10)
C80.0340 (17)0.0243 (16)0.0362 (17)−0.0058 (13)−0.0082 (13)−0.0045 (12)
C90.053 (2)0.0170 (15)0.049 (2)−0.0121 (15)−0.0120 (16)−0.0056 (13)
C100.0388 (18)0.0405 (19)0.0408 (18)−0.0222 (16)−0.0018 (14)−0.0082 (14)
C110.0276 (16)0.043 (2)0.0406 (19)−0.0075 (14)0.0001 (13)−0.0133 (15)
C120.0316 (16)0.0225 (16)0.0429 (18)−0.0033 (13)−0.0039 (13)−0.0111 (13)
C130.0206 (13)0.0209 (13)0.0233 (13)−0.0030 (11)0.0012 (10)−0.0025 (10)
C140.0360 (17)0.0389 (18)0.0293 (16)−0.0166 (15)−0.0054 (13)0.0011 (13)
C150.0381 (19)0.063 (2)0.0269 (16)−0.0213 (18)−0.0099 (13)0.0133 (15)
C160.0333 (17)0.0385 (19)0.049 (2)−0.0107 (15)0.0033 (15)0.0135 (15)
C170.0393 (19)0.0294 (17)0.048 (2)−0.0156 (15)0.0118 (15)−0.0065 (14)
C180.0282 (15)0.0315 (16)0.0276 (15)−0.0118 (13)0.0031 (12)−0.0081 (12)
Geometric parameters (Å, °) top
Ag1—P12.3500 (8)C5—H5A0.9500
Ag1—O42.354 (2)C6—H6A0.9900
Ag1—O12.370 (2)C6—H6B0.9900
P1—C71.817 (3)C7—C121.391 (4)
P1—C131.817 (3)C7—C81.393 (4)
P1—C61.854 (3)C8—C91.393 (4)
O1—N31.257 (3)C8—H8A0.9500
O2—N31.246 (3)C9—C101.358 (5)
O3—N31.236 (3)C9—H9A0.9500
O4—N41.273 (3)C10—C111.385 (5)
O5—N41.256 (3)C10—H10A0.9500
O6—N41.229 (3)C11—C121.381 (5)
N1—C11.349 (4)C11—H11A0.9500
N1—C51.352 (4)C12—H12A0.9500
N1—H1A0.8800C13—C181.390 (4)
N2—C31.336 (3)C13—C141.393 (4)
N2—C61.452 (3)C14—C151.387 (5)
N2—H2A0.8800C14—H14A0.9500
C1—C21.351 (4)C15—C161.394 (5)
C1—H1B0.9500C15—H15A0.9500
C2—C31.430 (4)C16—C171.371 (5)
C2—H2B0.9500C16—H16A0.9500
C3—C41.408 (4)C17—C181.386 (4)
C4—C51.368 (4)C17—H17A0.9500
C4—H4A0.9500C18—H18A0.9500
P1—Ag1—O4136.46 (5)P1—C6—H6A109.0
P1—Ag1—O1138.31 (7)N2—C6—H6B109.0
O4—Ag1—O184.99 (8)P1—C6—H6B109.0
C7—P1—C13105.94 (13)H6A—C6—H6B107.8
C7—P1—C6100.58 (13)C12—C7—C8118.8 (3)
C13—P1—C6104.39 (13)C12—C7—P1122.2 (2)
C7—P1—Ag1114.33 (10)C8—C7—P1119.0 (2)
C13—P1—Ag1115.36 (9)C7—C8—C9120.0 (3)
C6—P1—Ag1114.65 (9)C7—C8—H8A120.0
N3—O1—Ag1102.13 (18)C9—C8—H8A120.0
N4—O4—Ag1111.82 (16)C10—C9—C8120.7 (3)
C1—N1—C5120.7 (3)C10—C9—H9A119.7
C1—N1—H1A119.7C8—C9—H9A119.7
C5—N1—H1A119.7C9—C10—C11120.0 (3)
C3—N2—C6126.9 (2)C9—C10—H10A120.0
C3—N2—H2A116.5C11—C10—H10A120.0
C6—N2—H2A116.5C12—C11—C10120.2 (3)
O3—N3—O2121.7 (3)C12—C11—H11A119.9
O3—N3—O1120.0 (3)C10—C11—H11A119.9
O2—N3—O1118.3 (3)C11—C12—C7120.4 (3)
O6—N4—O5121.6 (2)C11—C12—H12A119.8
O6—N4—O4121.0 (2)C7—C12—H12A119.8
O5—N4—O4117.5 (2)C18—C13—C14119.1 (3)
N1—C1—C2121.3 (3)C18—C13—P1119.2 (2)
N1—C1—H1B119.3C14—C13—P1121.5 (2)
C2—C1—H1B119.3C15—C14—C13120.4 (3)
C1—C2—C3120.1 (3)C15—C14—H14A119.8
C1—C2—H2B120.0C13—C14—H14A119.8
C3—C2—H2B120.0C14—C15—C16119.8 (3)
N2—C3—C4124.7 (2)C14—C15—H15A120.1
N2—C3—C2118.4 (3)C16—C15—H15A120.1
C4—C3—C2116.9 (3)C17—C16—C15119.7 (3)
C5—C4—C3120.0 (3)C17—C16—H16A120.1
C5—C4—H4A120.0C15—C16—H16A120.1
C3—C4—H4A120.0C16—C17—C18120.8 (3)
N1—C5—C4121.0 (3)C16—C17—H17A119.6
N1—C5—H5A119.5C18—C17—H17A119.6
C4—C5—H5A119.5C17—C18—C13120.1 (3)
N2—C6—P1112.86 (19)C17—C18—H18A120.0
N2—C6—H6A109.0C13—C18—H18A120.0
O4—Ag1—P1—C7−139.96 (13)C13—P1—C7—C12−63.3 (3)
O1—Ag1—P1—C747.87 (14)C6—P1—C7—C1245.2 (3)
O4—Ag1—P1—C1396.81 (13)Ag1—P1—C7—C12168.5 (2)
O1—Ag1—P1—C13−75.36 (13)C13—P1—C7—C8119.1 (2)
O4—Ag1—P1—C6−24.55 (14)C6—P1—C7—C8−132.4 (2)
O1—Ag1—P1—C6163.29 (13)Ag1—P1—C7—C8−9.1 (3)
P1—Ag1—O1—N3−89.92 (19)C12—C7—C8—C9−1.1 (5)
O4—Ag1—O1—N395.49 (19)P1—C7—C8—C9176.6 (3)
P1—Ag1—O4—N4−46.8 (2)C7—C8—C9—C100.3 (5)
O1—Ag1—O4—N4128.01 (19)C8—C9—C10—C110.8 (6)
Ag1—O1—N3—O3179.4 (2)C9—C10—C11—C12−1.1 (5)
Ag1—O1—N3—O2−0.7 (3)C10—C11—C12—C70.3 (5)
Ag1—O4—N4—O6−0.5 (4)C8—C7—C12—C110.7 (5)
Ag1—O4—N4—O5179.1 (2)P1—C7—C12—C11−176.9 (3)
C5—N1—C1—C2−0.5 (4)C7—P1—C13—C18166.2 (2)
N1—C1—C2—C30.0 (4)C6—P1—C13—C1860.5 (3)
C6—N2—C3—C4−1.9 (4)Ag1—P1—C13—C18−66.2 (2)
C6—N2—C3—C2177.3 (2)C7—P1—C13—C14−17.5 (3)
C1—C2—C3—N2−178.8 (3)C6—P1—C13—C14−123.2 (3)
C1—C2—C3—C40.4 (4)Ag1—P1—C13—C14110.0 (2)
N2—C3—C4—C5178.9 (3)C18—C13—C14—C15−1.7 (5)
C2—C3—C4—C5−0.2 (4)P1—C13—C14—C15−177.9 (3)
C1—N1—C5—C40.7 (4)C13—C14—C15—C16−1.6 (5)
C3—C4—C5—N1−0.3 (4)C14—C15—C16—C172.7 (6)
C3—N2—C6—P1111.1 (3)C15—C16—C17—C18−0.6 (5)
C7—P1—C6—N2167.0 (2)C16—C17—C18—C13−2.7 (5)
C13—P1—C6—N2−83.4 (2)C14—C13—C18—C173.8 (4)
Ag1—P1—C6—N243.8 (2)P1—C13—C18—C17−179.9 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O5i0.881.932.807 (3)172
N2—H2A···O4ii0.882.163.013 (3)162
N2—H2A···O5ii0.882.473.075 (3)127
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O5i0.881.932.807 (3)172
N2—H2A···O4ii0.882.163.013 (3)162
N2—H2A···O5ii0.882.473.075 (3)127
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1.
Acknowledgements top

This work was supported by the Natural Science Foundation of Guangxi Province (grant No. 0832100) and the Programme for Excellent Talents in Guangxi Higher Education Institutions.

references
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