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Acta Cryst. (2007). E63, m2951    [ doi:10.1107/S1600536807055146 ]

(2,9-Dimethoxy-1,10-phenanthroline-[kappa]2N,N')nitratosilver(I)

X.-S. Wan, H.-Y. Zhang, C.-Y. Niu, C.-H. Kou and C.-L. Feng

Abstract top

In the crystal structure of the title compound, [Ag(NO3)(C14H12N2O2)], the AgI centre is three-coordinated by two N atoms from 2,9-dimethoxy-1,10-phenanthroline and one O atom of the nitrate anion. The Ag-N bond lengths are almost identical, and O-Ag-N bond angles are larger than the bite angle N-Ag-N. In the main ligand, the O and C atoms of the methoxy groups lie almost in the plane defined by the phenanthroline ring system. Based on the extended delocalized [pi] system of phenanthroline and the d10 electronic configuration of the metal centre, the title complex is expected to produce strong luminescent emission when properly excited.

Comment top

2,9-Dimethoxy-1,10-phenanthroline and 2,9-diethoxy-1,10-phenanthroline were synthesized at early time and they are known to possess antimycoplasmal activity in the presence of copper (Pijper et al., 1984). However, crystal structures of their coordination complexes with transition metal ions have not been reported so far.

The title compound, (I), is a mononuclear AgI complex of 2,9-dimethoxy-1,10-phenanthroline (Fig.1). The Ag metal centre is three coordinated by two N atoms from the 1,10-phenanthroline ring and one O atom from the nitrate anion. The Ag—O bond length is 2.214 (4) Å, and the Ag—N bond lengths are 2.309 (3) and 2.316 (3) Å. The O—Ag—N bond angles are 142.80 (13) and 144.53 (13)°, which are larger than N—Ag—N angle. Intermolecular interactions corresponding to π–π stacking contacts between phenanthroline rings are observed in the crystal structure, with separations of ca. 3.5 Å. Regarding the main ligand, it remains almost planar, with the O and C atoms of methoxy groups deviating from the phenanthroline plane by about 0.03 and 0.18 Å, respectively.

Because the ligand 1,10-phenanthroline was reported to be used in the preparation of some potentially strong luminescent materials with d10 metals, it can be expected that the title complex also has strong luminescent properties (Majumder et al., 2006; Bie et al., 2006).

Related literature top

For related literature about AgI luminescent complexes, see: Bie et al. (2006); Majumder et al. (2006); For the synthesis of 2,9-dimethoxy-1,10-phenanthroline, see: Pijper et al. (1984).

Experimental top

The organic ligand 2,9-dimethoxy-1,10-phenanthroline was prepared according to the literature procedure (Pijper et al., 1984). The slow evaporation of a mixture of the ligand (0.024 g, 0.1 mmol) and silver nitrate (0.017 g, 0.1 mmol) in methanol (30 ml) afforded colourless needles suitable for X-ray crystallography in about 7 days (yield: 40%).

Refinement top

C-bound H atoms in phenanthroline ring and methyl groups were placed at calculated positions (C—H = 0.93 Å and 0.96 Å, respectively), and they were included in the refinement in the riding-model approximation, with Uiso(H) values set at 1.2 times and 1.5 times Ueq(C), respectively. The final difference map had a highest peak at 0.93 Å from atom Ag1 and a deepest hole at 0.85 Å from atom Ag1, but was otherwise featureless.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
(2,9-Dimethoxy-1,10-phenanthroline-κ2N,N')nitratosilver(I) top
Crystal data top
[Ag(NO3)(C14H12N2O2)]Z = 2
Mr = 410.14F000 = 408
Triclinic, P1Dx = 1.867 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.8510 (12) ÅCell parameters from 1736 reflections
b = 10.3094 (17) Åθ = 3.0–25.5º
c = 10.7294 (18) ŵ = 1.41 mm−1
α = 105.174 (3)ºT = 291 (2) K
β = 92.224 (3)ºNeedle, colourless
γ = 92.896 (3)º0.50 × 0.30 × 0.11 mm
V = 729.4 (2) Å3
Data collection top
Bruker APEX-II CCD detector
diffractometer		2659 independent reflections
Radiation source: fine-focus sealed tube2271 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→7
Tmin = 0.539, Tmax = 0.860k = −9→12
3810 measured reflectionsl = −12→12
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)] = 0.043H-atom parameters constrained
wR(F2) = 0.122  w = 1/[σ2(Fo2) + (0.0759P)2 + 0.3168P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2659 reflectionsΔρmax = 1.51 e Å−3
210 parametersΔρmin = −0.65 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ag(NO3)(C14H12N2O2)]γ = 92.896 (3)º
Mr = 410.14V = 729.4 (2) Å3
Triclinic, P1Z = 2
a = 6.8510 (12) ÅMo Kα
b = 10.3094 (17) ŵ = 1.41 mm−1
c = 10.7294 (18) ÅT = 291 (2) K
α = 105.174 (3)º0.50 × 0.30 × 0.11 mm
β = 92.224 (3)º
Data collection top
Bruker APEX-II CCD detector
diffractometer		2659 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2271 reflections with I > 2σ(I)
Tmin = 0.539, Tmax = 0.860Rint = 0.015
3810 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043210 parameters
wR(F2) = 0.122H-atom parameters constrained
S = 1.07Δρmax = 1.51 e Å−3
2659 reflectionsΔρmin = −0.65 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag10.21110 (6)0.31461 (3)0.64007 (3)0.05986 (19)
O10.3742 (7)0.2845 (5)0.8828 (4)0.0870 (13)
O20.1719 (7)0.1546 (4)0.7418 (4)0.0807 (12)
O30.2569 (8)0.0994 (4)0.9147 (3)0.0861 (14)
O40.1377 (5)0.5804 (3)0.8756 (3)0.0524 (8)
O50.2725 (5)0.1390 (3)0.3440 (3)0.0558 (8)
N10.2584 (5)0.3565 (3)0.4420 (3)0.0381 (7)
N20.1984 (4)0.5443 (3)0.6671 (3)0.0361 (7)
N30.2718 (6)0.1797 (4)0.8481 (3)0.0550 (10)
C10.2876 (6)0.2654 (4)0.3324 (4)0.0428 (9)
C20.3284 (6)0.2990 (5)0.2166 (4)0.0462 (10)
H20.34770.23270.14140.055*
C30.3388 (6)0.4321 (5)0.2181 (4)0.0492 (10)
H30.36690.45680.14300.059*
C40.3077 (6)0.5324 (5)0.3314 (4)0.0430 (9)
C50.3116 (7)0.6722 (5)0.3377 (4)0.0540 (11)
H50.33670.70050.26400.065*
C60.2793 (8)0.7641 (5)0.4488 (5)0.0558 (11)
H60.28280.85490.45060.067*
C70.2401 (6)0.7249 (4)0.5630 (4)0.0444 (9)
C80.2094 (6)0.8164 (4)0.6822 (5)0.0499 (10)
H80.21140.90800.68770.060*
C90.1771 (6)0.7737 (4)0.7882 (4)0.0476 (10)
H90.15900.83480.86700.057*
C100.1713 (6)0.6350 (4)0.7773 (4)0.0405 (9)
C110.2338 (5)0.5881 (4)0.5614 (4)0.0353 (8)
C120.2668 (5)0.4886 (4)0.4419 (4)0.0370 (8)
C130.2794 (9)0.0303 (5)0.2287 (5)0.0701 (15)
H13A0.17300.03420.16920.105*
H13B0.2686−0.05410.25080.105*
H13C0.40130.03830.18930.105*
C140.1242 (8)0.6691 (6)1.0025 (5)0.0644 (13)
H14A0.24730.71911.02990.097*
H14B0.09230.61711.06200.097*
H14C0.02390.73031.00020.097*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag10.0811 (3)0.0493 (3)0.0537 (3)0.00036 (19)−0.00120 (19)0.02297 (18)
O10.081 (3)0.101 (3)0.076 (3)−0.022 (2)−0.002 (2)0.024 (2)
O20.136 (4)0.051 (2)0.057 (2)−0.008 (2)−0.016 (2)0.0224 (17)
O30.164 (4)0.055 (2)0.0444 (19)0.020 (2)0.005 (2)0.0189 (17)
O40.0637 (19)0.0552 (19)0.0365 (15)0.0055 (15)0.0068 (13)0.0078 (13)
O50.075 (2)0.0411 (16)0.0458 (17)0.0042 (15)0.0011 (15)0.0020 (13)
N10.0361 (17)0.0416 (18)0.0326 (16)0.0007 (14)−0.0027 (13)0.0040 (13)
N20.0326 (16)0.0376 (17)0.0352 (16)0.0008 (13)−0.0004 (12)0.0049 (13)
N30.076 (3)0.046 (2)0.043 (2)0.016 (2)0.0104 (19)0.0083 (18)
C10.039 (2)0.045 (2)0.040 (2)0.0040 (17)−0.0024 (16)0.0044 (17)
C20.045 (2)0.055 (3)0.0325 (19)0.0038 (19)0.0004 (16)0.0006 (18)
C30.044 (2)0.067 (3)0.035 (2)−0.001 (2)−0.0003 (17)0.0120 (19)
C40.036 (2)0.053 (2)0.041 (2)−0.0004 (17)−0.0030 (16)0.0147 (18)
C50.060 (3)0.059 (3)0.046 (2)−0.007 (2)−0.004 (2)0.023 (2)
C60.071 (3)0.046 (3)0.055 (3)−0.001 (2)−0.002 (2)0.023 (2)
C70.040 (2)0.045 (2)0.048 (2)−0.0023 (17)−0.0054 (17)0.0138 (18)
C80.053 (3)0.037 (2)0.056 (2)0.0044 (19)0.000 (2)0.0050 (18)
C90.046 (2)0.044 (2)0.047 (2)0.0046 (18)0.0002 (18)0.0023 (18)
C100.035 (2)0.044 (2)0.041 (2)0.0010 (16)−0.0006 (16)0.0082 (17)
C110.0312 (18)0.038 (2)0.0363 (19)0.0019 (15)−0.0020 (14)0.0101 (15)
C120.0287 (18)0.045 (2)0.0371 (19)−0.0002 (15)−0.0043 (15)0.0106 (16)
C130.093 (4)0.048 (3)0.061 (3)0.007 (3)0.004 (3)0.000 (2)
C140.075 (3)0.071 (3)0.042 (2)0.005 (3)0.006 (2)0.005 (2)
Geometric parameters (Å, °) top
Ag1—N12.309 (3)C4—C121.407 (6)
Ag1—N22.316 (3)C4—C51.424 (6)
Ag1—O22.214 (4)C5—C61.349 (7)
O1—N31.221 (5)C5—H50.9300
O2—N31.266 (5)C6—C71.418 (7)
O3—N31.230 (5)C6—H60.9300
O4—C101.341 (5)C7—C111.404 (6)
O4—C141.437 (5)C7—C81.407 (6)
O5—C11.340 (6)C8—C91.345 (7)
O5—C131.440 (5)C8—H80.9300
N1—C11.328 (5)C9—C101.402 (6)
N1—C121.361 (5)C9—H90.9300
N2—C101.327 (5)C11—C121.451 (5)
N2—C111.353 (5)C13—H13A0.9600
C1—C21.409 (6)C13—H13B0.9600
C2—C31.366 (6)C13—H13C0.9600
C2—H20.9300C14—H14A0.9600
C3—C41.406 (6)C14—H14B0.9600
C3—H30.9300C14—H14C0.9600
O2—Ag1—N1144.53 (13)C7—C6—H6119.4
O2—Ag1—N2142.80 (13)C11—C7—C8116.4 (4)
N1—Ag1—N272.42 (11)C11—C7—C6119.9 (4)
N3—O2—Ag1113.0 (3)C8—C7—C6123.7 (4)
C10—O4—C14118.3 (4)C9—C8—C7121.1 (4)
C1—O5—C13118.1 (4)C9—C8—H8119.4
C1—N1—C12118.3 (3)C7—C8—H8119.4
C1—N1—Ag1126.2 (3)C8—C9—C10118.6 (4)
C12—N1—Ag1115.4 (2)C8—C9—H9120.7
C10—N2—C11118.4 (3)C10—C9—H9120.7
C10—N2—Ag1125.9 (3)N2—C10—O4113.3 (4)
C11—N2—Ag1115.6 (2)N2—C10—C9122.8 (4)
O1—N3—O3122.4 (5)O4—C10—C9124.0 (4)
O1—N3—O2119.0 (4)N2—C11—C7122.8 (4)
O3—N3—O2118.6 (4)N2—C11—C12118.0 (3)
N1—C1—O5112.8 (4)C7—C11—C12119.2 (4)
N1—C1—C2123.2 (4)N1—C12—C4122.8 (4)
O5—C1—C2124.0 (4)N1—C12—C11118.3 (3)
C3—C2—C1118.0 (4)C4—C12—C11118.9 (4)
C3—C2—H2121.0O5—C13—H13A109.5
C1—C2—H2121.0O5—C13—H13B109.5
C2—C3—C4121.0 (4)H13A—C13—H13B109.5
C2—C3—H3119.5O5—C13—H13C109.5
C4—C3—H3119.5H13A—C13—H13C109.5
C3—C4—C12116.7 (4)H13B—C13—H13C109.5
C3—C4—C5123.4 (4)O4—C14—H14A109.5
C12—C4—C5119.9 (4)O4—C14—H14B109.5
C6—C5—C4120.9 (4)H14A—C14—H14B109.5
C6—C5—H5119.5O4—C14—H14C109.5
C4—C5—H5119.5H14A—C14—H14C109.5
C5—C6—C7121.2 (4)H14B—C14—H14C109.5
C5—C6—H6119.4
N1—Ag1—O2—N3135.9 (3)C7—C8—C9—C10−1.1 (7)
N2—Ag1—O2—N3−52.8 (5)C11—N2—C10—O4−179.9 (3)
O2—Ag1—N1—C1−5.5 (5)Ag1—N2—C10—O4−4.2 (5)
N2—Ag1—N1—C1−180.0 (3)C11—N2—C10—C90.3 (6)
O2—Ag1—N1—C12178.2 (3)Ag1—N2—C10—C9176.0 (3)
N2—Ag1—N1—C123.7 (2)C14—O4—C10—N2174.3 (4)
O2—Ag1—N2—C106.1 (4)C14—O4—C10—C9−5.9 (6)
N1—Ag1—N2—C10−179.2 (3)C8—C9—C10—N20.7 (6)
O2—Ag1—N2—C11−178.0 (3)C8—C9—C10—O4−179.0 (4)
N1—Ag1—N2—C11−3.4 (2)C10—N2—C11—C7−1.0 (5)
Ag1—O2—N3—O10.3 (6)Ag1—N2—C11—C7−177.1 (3)
Ag1—O2—N3—O3177.9 (4)C10—N2—C11—C12178.9 (3)
C12—N1—C1—O5−179.0 (3)Ag1—N2—C11—C122.7 (4)
Ag1—N1—C1—O54.8 (5)C8—C7—C11—N20.6 (6)
C12—N1—C1—C20.6 (6)C6—C7—C11—N2179.6 (4)
Ag1—N1—C1—C2−175.6 (3)C8—C7—C11—C12−179.2 (4)
C13—O5—C1—N1173.2 (4)C6—C7—C11—C12−0.2 (6)
C13—O5—C1—C2−6.3 (7)C1—N1—C12—C4−0.9 (5)
N1—C1—C2—C30.2 (6)Ag1—N1—C12—C4175.7 (3)
O5—C1—C2—C3179.7 (4)C1—N1—C12—C11179.6 (3)
C1—C2—C3—C4−0.7 (6)Ag1—N1—C12—C11−3.8 (4)
C2—C3—C4—C120.3 (6)C3—C4—C12—N10.5 (6)
C2—C3—C4—C5−178.3 (4)C5—C4—C12—N1179.1 (4)
C3—C4—C5—C6179.5 (4)C3—C4—C12—C11179.9 (4)
C12—C4—C5—C60.9 (7)C5—C4—C12—C11−1.4 (5)
C4—C5—C6—C7−0.1 (8)N2—C11—C12—N10.7 (5)
C5—C6—C7—C11−0.2 (7)C7—C11—C12—N1−179.4 (3)
C5—C6—C7—C8178.6 (4)N2—C11—C12—C4−178.8 (3)
C11—C7—C8—C90.4 (6)C7—C11—C12—C41.1 (5)
C6—C7—C8—C9−178.5 (4)
Table 1
Selected geometric parameters (Å, °) top
Ag1—N12.309 (3)Ag1—O22.214 (4)
Ag1—N22.316 (3)
O2—Ag1—N1144.53 (13)N1—Ag1—N272.42 (11)
O2—Ag1—N2142.80 (13)
Acknowledgements top

We are grateful to Professor J, G. Wang and J. H. Qin for their assistance with the X-ray crystallographic analysis.

references
References top

Bie, H.-Y., Ji, W., Yu, J.-H., Wang, T.-G., Lu, J. & Xu, J.-Q. (2006). Mater. Lett. 60, 2475–2479.

Bruker (2001). SAINT (Version 6.02a), SMART (Version 5.625), SADABS (Version 2.03a) and SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.

Majumder, A., Westerhausen, M., Kneifel, A. N., Sutter, J.-P., Daro, N. & Mitra, S. (2006). Inorg. Chim. Acta, 359, 3841–3846.

Pijper, P. J., Van der Goot, H., Timmerman, H. & Nauta, W. T. (1984). Eur. J. Med. Chem. 19, 399–404.

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