(2,9-Dimeth­oxy-1,10-phenanthroline-κ²N,N′)nitratosilver(I)

In the crystal structure of the title compound, [Ag(NO₃)(C₁₄H₁₂N₂O₂)], the Ag^I 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 π 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.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.043
• wR factor = 0.122
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.33
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        300 Deg.
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 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

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S1. Comment

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 Ag^I 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

For related literature about Ag^I 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).

S2. Experimental

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%).

S3. Refinement

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 U_iso(H) values set at 1.2 times and 1.5 times U_eq(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

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

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)

Crystal data

[Ag(NO3)(C14H12N2O2)]	Z = 2
Mr = 410.14	F(000) = 408
Triclinic, P1	Dx = 1.867 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8510 (12) Å	Cell parameters from 1736 reflections
b = 10.3094 (17) Å	θ = 3.0–25.5°
c = 10.7294 (18) Å	µ = 1.41 mm^−1
α = 105.174 (3)°	T = 291 K
β = 92.224 (3)°	Needle, colourless
γ = 92.896 (3)°	0.50 × 0.30 × 0.11 mm
V = 729.4 (2) Å^3

Data collection

Bruker APEX-II CCD detector diffractometer	2659 independent reflections
Radiation source: fine-focus sealed tube	2271 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 25.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→7
Tmin = 0.539, Tmax = 0.860	k = −9→12
3810 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0759P)^2 + 0.3168P] where P = (Fo^2 + 2Fc^2)/3
2659 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 1.51 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ag1	0.21110 (6)	0.31461 (3)	0.64007 (3)	0.05986 (19)
O1	0.3742 (7)	0.2845 (5)	0.8828 (4)	0.0870 (13)
O2	0.1719 (7)	0.1546 (4)	0.7418 (4)	0.0807 (12)
O3	0.2569 (8)	0.0994 (4)	0.9147 (3)	0.0861 (14)
O4	0.1377 (5)	0.5804 (3)	0.8756 (3)	0.0524 (8)
O5	0.2725 (5)	0.1390 (3)	0.3440 (3)	0.0558 (8)
N1	0.2584 (5)	0.3565 (3)	0.4420 (3)	0.0381 (7)
N2	0.1984 (4)	0.5443 (3)	0.6671 (3)	0.0361 (7)
N3	0.2718 (6)	0.1797 (4)	0.8481 (3)	0.0550 (10)
C1	0.2876 (6)	0.2654 (4)	0.3324 (4)	0.0428 (9)
C2	0.3284 (6)	0.2990 (5)	0.2166 (4)	0.0462 (10)
H2	0.3477	0.2327	0.1414	0.055*
C3	0.3388 (6)	0.4321 (5)	0.2181 (4)	0.0492 (10)
H3	0.3669	0.4568	0.1430	0.059*
C4	0.3077 (6)	0.5324 (5)	0.3314 (4)	0.0430 (9)
C5	0.3116 (7)	0.6722 (5)	0.3377 (4)	0.0540 (11)
H5	0.3367	0.7005	0.2640	0.065*
C6	0.2793 (8)	0.7641 (5)	0.4488 (5)	0.0558 (11)
H6	0.2828	0.8549	0.4506	0.067*
C7	0.2401 (6)	0.7249 (4)	0.5630 (4)	0.0444 (9)
C8	0.2094 (6)	0.8164 (4)	0.6822 (5)	0.0499 (10)
H8	0.2114	0.9080	0.6877	0.060*
C9	0.1771 (6)	0.7737 (4)	0.7882 (4)	0.0476 (10)
H9	0.1590	0.8348	0.8670	0.057*
C10	0.1713 (6)	0.6350 (4)	0.7773 (4)	0.0405 (9)
C11	0.2338 (5)	0.5881 (4)	0.5614 (4)	0.0353 (8)
C12	0.2668 (5)	0.4886 (4)	0.4419 (4)	0.0370 (8)
C13	0.2794 (9)	0.0303 (5)	0.2287 (5)	0.0701 (15)
H13A	0.1730	0.0342	0.1692	0.105*
H13B	0.2686	−0.0541	0.2508	0.105*
H13C	0.4013	0.0383	0.1893	0.105*
C14	0.1242 (8)	0.6691 (6)	1.0025 (5)	0.0644 (13)
H14A	0.2473	0.7191	1.0299	0.097*
H14B	0.0923	0.6171	1.0620	0.097*
H14C	0.0239	0.7303	1.0002	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0811 (3)	0.0493 (3)	0.0537 (3)	0.00036 (19)	−0.00120 (19)	0.02297 (18)
O1	0.081 (3)	0.101 (3)	0.076 (3)	−0.022 (2)	−0.002 (2)	0.024 (2)
O2	0.136 (4)	0.051 (2)	0.057 (2)	−0.008 (2)	−0.016 (2)	0.0224 (17)
O3	0.164 (4)	0.055 (2)	0.0444 (19)	0.020 (2)	0.005 (2)	0.0189 (17)
O4	0.0637 (19)	0.0552 (19)	0.0365 (15)	0.0055 (15)	0.0068 (13)	0.0078 (13)
O5	0.075 (2)	0.0411 (16)	0.0458 (17)	0.0042 (15)	0.0011 (15)	0.0020 (13)
N1	0.0361 (17)	0.0416 (18)	0.0326 (16)	0.0007 (14)	−0.0027 (13)	0.0040 (13)
N2	0.0326 (16)	0.0376 (17)	0.0352 (16)	0.0008 (13)	−0.0004 (12)	0.0049 (13)
N3	0.076 (3)	0.046 (2)	0.043 (2)	0.016 (2)	0.0104 (19)	0.0083 (18)
C1	0.039 (2)	0.045 (2)	0.040 (2)	0.0040 (17)	−0.0024 (16)	0.0044 (17)
C2	0.045 (2)	0.055 (3)	0.0325 (19)	0.0038 (19)	0.0004 (16)	0.0006 (18)
C3	0.044 (2)	0.067 (3)	0.035 (2)	−0.001 (2)	−0.0003 (17)	0.0120 (19)
C4	0.036 (2)	0.053 (2)	0.041 (2)	−0.0004 (17)	−0.0030 (16)	0.0147 (18)
C5	0.060 (3)	0.059 (3)	0.046 (2)	−0.007 (2)	−0.004 (2)	0.023 (2)
C6	0.071 (3)	0.046 (3)	0.055 (3)	−0.001 (2)	−0.002 (2)	0.023 (2)
C7	0.040 (2)	0.045 (2)	0.048 (2)	−0.0023 (17)	−0.0054 (17)	0.0138 (18)
C8	0.053 (3)	0.037 (2)	0.056 (2)	0.0044 (19)	0.000 (2)	0.0050 (18)
C9	0.046 (2)	0.044 (2)	0.047 (2)	0.0046 (18)	0.0002 (18)	0.0023 (18)
C10	0.035 (2)	0.044 (2)	0.041 (2)	0.0010 (16)	−0.0006 (16)	0.0082 (17)
C11	0.0312 (18)	0.038 (2)	0.0363 (19)	0.0019 (15)	−0.0020 (14)	0.0101 (15)
C12	0.0287 (18)	0.045 (2)	0.0371 (19)	−0.0002 (15)	−0.0043 (15)	0.0106 (16)
C13	0.093 (4)	0.048 (3)	0.061 (3)	0.007 (3)	0.004 (3)	0.000 (2)
C14	0.075 (3)	0.071 (3)	0.042 (2)	0.005 (3)	0.006 (2)	0.005 (2)

Geometric parameters (Å, º)

Ag1—N1	2.309 (3)	C4—C12	1.407 (6)
Ag1—N2	2.316 (3)	C4—C5	1.424 (6)
Ag1—O2	2.214 (4)	C5—C6	1.349 (7)
O1—N3	1.221 (5)	C5—H5	0.9300
O2—N3	1.266 (5)	C6—C7	1.418 (7)
O3—N3	1.230 (5)	C6—H6	0.9300
O4—C10	1.341 (5)	C7—C11	1.404 (6)
O4—C14	1.437 (5)	C7—C8	1.407 (6)
O5—C1	1.340 (6)	C8—C9	1.345 (7)
O5—C13	1.440 (5)	C8—H8	0.9300
N1—C1	1.328 (5)	C9—C10	1.402 (6)
N1—C12	1.361 (5)	C9—H9	0.9300
N2—C10	1.327 (5)	C11—C12	1.451 (5)
N2—C11	1.353 (5)	C13—H13A	0.9600
C1—C2	1.409 (6)	C13—H13B	0.9600
C2—C3	1.366 (6)	C13—H13C	0.9600
C2—H2	0.9300	C14—H14A	0.9600
C3—C4	1.406 (6)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
O2—Ag1—N1	144.53 (13)	C7—C6—H6	119.4
O2—Ag1—N2	142.80 (13)	C11—C7—C8	116.4 (4)
N1—Ag1—N2	72.42 (11)	C11—C7—C6	119.9 (4)
N3—O2—Ag1	113.0 (3)	C8—C7—C6	123.7 (4)
C10—O4—C14	118.3 (4)	C9—C8—C7	121.1 (4)
C1—O5—C13	118.1 (4)	C9—C8—H8	119.4
C1—N1—C12	118.3 (3)	C7—C8—H8	119.4
C1—N1—Ag1	126.2 (3)	C8—C9—C10	118.6 (4)
C12—N1—Ag1	115.4 (2)	C8—C9—H9	120.7
C10—N2—C11	118.4 (3)	C10—C9—H9	120.7
C10—N2—Ag1	125.9 (3)	N2—C10—O4	113.3 (4)
C11—N2—Ag1	115.6 (2)	N2—C10—C9	122.8 (4)
O1—N3—O3	122.4 (5)	O4—C10—C9	124.0 (4)
O1—N3—O2	119.0 (4)	N2—C11—C7	122.8 (4)
O3—N3—O2	118.6 (4)	N2—C11—C12	118.0 (3)
N1—C1—O5	112.8 (4)	C7—C11—C12	119.2 (4)
N1—C1—C2	123.2 (4)	N1—C12—C4	122.8 (4)
O5—C1—C2	124.0 (4)	N1—C12—C11	118.3 (3)
C3—C2—C1	118.0 (4)	C4—C12—C11	118.9 (4)
C3—C2—H2	121.0	O5—C13—H13A	109.5
C1—C2—H2	121.0	O5—C13—H13B	109.5
C2—C3—C4	121.0 (4)	H13A—C13—H13B	109.5
C2—C3—H3	119.5	O5—C13—H13C	109.5
C4—C3—H3	119.5	H13A—C13—H13C	109.5
C3—C4—C12	116.7 (4)	H13B—C13—H13C	109.5
C3—C4—C5	123.4 (4)	O4—C14—H14A	109.5
C12—C4—C5	119.9 (4)	O4—C14—H14B	109.5
C6—C5—C4	120.9 (4)	H14A—C14—H14B	109.5
C6—C5—H5	119.5	O4—C14—H14C	109.5
C4—C5—H5	119.5	H14A—C14—H14C	109.5
C5—C6—C7	121.2 (4)	H14B—C14—H14C	109.5
C5—C6—H6	119.4
N1—Ag1—O2—N3	135.9 (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—C9	0.3 (6)
O2—Ag1—N1—C12	178.2 (3)	Ag1—N2—C10—C9	176.0 (3)
N2—Ag1—N1—C12	3.7 (2)	C14—O4—C10—N2	174.3 (4)
O2—Ag1—N2—C10	6.1 (4)	C14—O4—C10—C9	−5.9 (6)
N1—Ag1—N2—C10	−179.2 (3)	C8—C9—C10—N2	0.7 (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—O1	0.3 (6)	Ag1—N2—C11—C7	−177.1 (3)
Ag1—O2—N3—O3	177.9 (4)	C10—N2—C11—C12	178.9 (3)
C12—N1—C1—O5	−179.0 (3)	Ag1—N2—C11—C12	2.7 (4)
Ag1—N1—C1—O5	4.8 (5)	C8—C7—C11—N2	0.6 (6)
C12—N1—C1—C2	0.6 (6)	C6—C7—C11—N2	179.6 (4)
Ag1—N1—C1—C2	−175.6 (3)	C8—C7—C11—C12	−179.2 (4)
C13—O5—C1—N1	173.2 (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—C3	0.2 (6)	Ag1—N1—C12—C4	175.7 (3)
O5—C1—C2—C3	179.7 (4)	C1—N1—C12—C11	179.6 (3)
C1—C2—C3—C4	−0.7 (6)	Ag1—N1—C12—C11	−3.8 (4)
C2—C3—C4—C12	0.3 (6)	C3—C4—C12—N1	0.5 (6)
C2—C3—C4—C5	−178.3 (4)	C5—C4—C12—N1	179.1 (4)
C3—C4—C5—C6	179.5 (4)	C3—C4—C12—C11	179.9 (4)
C12—C4—C5—C6	0.9 (7)	C5—C4—C12—C11	−1.4 (5)
C4—C5—C6—C7	−0.1 (8)	N2—C11—C12—N1	0.7 (5)
C5—C6—C7—C11	−0.2 (7)	C7—C11—C12—N1	−179.4 (3)
C5—C6—C7—C8	178.6 (4)	N2—C11—C12—C4	−178.8 (3)
C11—C7—C8—C9	0.4 (6)	C7—C11—C12—C4	1.1 (5)
C6—C7—C8—C9	−178.5 (4)