Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017422/su6040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017422/su6040Isup2.hkl |
CCDC reference: 222799
Silvertrifluoromethene sulfate and 4-aminopyridine were available commercially and were used without further purification. CF3SO3Ag (1.0 mmol, 257 mg) and 4-aminopyridine (1 mmol, 94 mg) were dissolved in an aqueous solution of ammonia (10 ml). The mixture was stirred for ca 10 min to obtain a clear solution. After keeping the resulting solution in air for 2 d, large colorless crystals were formed on slow evaporation of the solvents. The crystals were isolated, washed with water three times, and dried in a vacuum desiccator using CaCl2 (yield: 69%).
All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H distances of 0.86 Å, C—H distances of 0.97 Å and Uiso(H) = 1.2Ueq of the parent atom. The F-atom displacement parameters were quite large, presumably because these atoms were slightly disordered; however, no attempt was made to correct for this.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Ag(C5H6N2)2](CF3O2) | Z = 2 |
Mr = 409.13 | F(000) = 404 |
Triclinic, P1 | Dx = 1.736 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.492 (7) Å | Cell parameters from 2092 reflections |
b = 9.803 (7) Å | θ = 2.3–25.1° |
c = 10.002 (7) Å | µ = 1.33 mm−1 |
α = 115.206 (9)° | T = 298 K |
β = 108.078 (8)° | Prism, colorless |
γ = 92.793 (10)° | 0.32 × 0.27 × 0.15 mm |
V = 782.6 (10) Å3 |
Siemens SMART CCD area-detector diffractometer | 2720 independent reflections |
Radiation source: fine-focus sealed tube | 2200 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.676, Tmax = 0.826 | k = −7→11 |
3984 measured reflections | l = −11→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0848P)2 + 0.1491P] where P = (Fo2 + 2Fc2)/3 |
2720 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.94 e Å−3 |
6 restraints | Δρmin = −0.67 e Å−3 |
[Ag(C5H6N2)2](CF3O2) | γ = 92.793 (10)° |
Mr = 409.13 | V = 782.6 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.492 (7) Å | Mo Kα radiation |
b = 9.803 (7) Å | µ = 1.33 mm−1 |
c = 10.002 (7) Å | T = 298 K |
α = 115.206 (9)° | 0.32 × 0.27 × 0.15 mm |
β = 108.078 (8)° |
Siemens SMART CCD area-detector diffractometer | 2720 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2200 reflections with I > 2σ(I) |
Tmin = 0.676, Tmax = 0.826 | Rint = 0.015 |
3984 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 6 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.94 e Å−3 |
2720 reflections | Δρmin = −0.67 e Å−3 |
199 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ag1 | 0.85785 (4) | 0.81146 (4) | 0.13823 (5) | 0.0720 (2) | |
F1 | 0.8563 (10) | 0.9584 (8) | 0.5144 (7) | 0.233 (5) | |
F2 | 0.8111 (10) | 0.8823 (9) | 0.6519 (5) | 0.220 (4) | |
F3 | 0.6613 (10) | 0.9677 (10) | 0.5485 (13) | 0.338 (8) | |
N1 | 1.0028 (4) | 0.6663 (4) | 0.1821 (5) | 0.0576 (9) | |
N2 | 1.3307 (5) | 0.4377 (6) | 0.3243 (6) | 0.0788 (13) | |
H2A | 1.3129 | 0.3791 | 0.3638 | 0.095* | |
H2B | 1.4164 | 0.4493 | 0.3139 | 0.095* | |
N3 | 0.7608 (5) | 0.9921 (5) | 0.1097 (5) | 0.0608 (10) | |
N4 | 0.5651 (5) | 1.3482 (5) | 0.0635 (5) | 0.0659 (10) | |
H4A | 0.5164 | 1.3381 | −0.0295 | 0.079* | |
H4B | 0.5724 | 1.4313 | 0.1465 | 0.079* | |
O1 | 0.6433 (5) | 0.7312 (5) | 0.2514 (4) | 0.0777 (10) | |
O2 | 0.6495 (5) | 0.6200 (4) | 0.4028 (5) | 0.0740 (10) | |
C1 | 0.9802 (6) | 0.5731 (6) | 0.2444 (7) | 0.0656 (13) | |
H1 | 0.8873 | 0.5601 | 0.2550 | 0.079* | |
C2 | 1.0833 (5) | 0.4973 (6) | 0.2925 (6) | 0.0606 (12) | |
H2 | 1.0600 | 0.4353 | 0.3350 | 0.073* | |
C3 | 1.2246 (5) | 0.5112 (5) | 0.2788 (5) | 0.0546 (10) | |
C4 | 1.2474 (5) | 0.6056 (6) | 0.2104 (6) | 0.0614 (12) | |
H4 | 1.3382 | 0.6182 | 0.1954 | 0.074* | |
C5 | 1.1387 (6) | 0.6774 (6) | 0.1668 (6) | 0.0617 (12) | |
H5 | 1.1585 | 0.7393 | 0.1228 | 0.074* | |
C6 | 0.6847 (6) | 0.9820 (6) | −0.0329 (6) | 0.0568 (11) | |
H6 | 0.6752 | 0.8917 | −0.1229 | 0.068* | |
C7 | 0.6196 (5) | 1.0978 (5) | −0.0537 (5) | 0.0557 (11) | |
H7 | 0.5694 | 1.0855 | −0.1554 | 0.067* | |
C8 | 0.6299 (5) | 1.2340 (5) | 0.0793 (5) | 0.0501 (10) | |
C9 | 0.7108 (5) | 1.2446 (6) | 0.2283 (5) | 0.0601 (12) | |
H9 | 0.7231 | 1.3334 | 0.3208 | 0.072* | |
C10 | 0.7711 (6) | 1.1240 (6) | 0.2364 (6) | 0.0647 (12) | |
H10 | 0.8230 | 1.1336 | 0.3366 | 0.078* | |
C11 | 0.6726 (5) | 0.7286 (5) | 0.3786 (5) | 0.0522 (10) | |
C12 | 0.7508 (9) | 0.8820 (7) | 0.5228 (7) | 0.0909 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0709 (3) | 0.0625 (3) | 0.0866 (3) | 0.0243 (2) | 0.0234 (2) | 0.0409 (2) |
F1 | 0.316 (10) | 0.170 (6) | 0.116 (4) | −0.144 (7) | 0.050 (5) | 0.022 (4) |
F2 | 0.314 (9) | 0.179 (6) | 0.066 (3) | −0.102 (6) | 0.004 (4) | 0.031 (3) |
F3 | 0.216 (8) | 0.193 (8) | 0.290 (11) | 0.100 (7) | 0.013 (8) | −0.114 (8) |
N1 | 0.053 (2) | 0.052 (2) | 0.068 (2) | 0.0136 (17) | 0.0181 (18) | 0.030 (2) |
N2 | 0.065 (3) | 0.101 (4) | 0.111 (4) | 0.036 (3) | 0.042 (3) | 0.076 (3) |
N3 | 0.064 (2) | 0.057 (2) | 0.066 (2) | 0.0166 (19) | 0.0238 (19) | 0.033 (2) |
N4 | 0.080 (3) | 0.053 (2) | 0.062 (2) | 0.021 (2) | 0.021 (2) | 0.026 (2) |
O1 | 0.084 (2) | 0.092 (3) | 0.052 (2) | 0.010 (2) | 0.0174 (17) | 0.035 (2) |
O2 | 0.090 (3) | 0.061 (2) | 0.077 (2) | 0.0154 (19) | 0.032 (2) | 0.0357 (19) |
C1 | 0.052 (3) | 0.071 (3) | 0.084 (3) | 0.013 (2) | 0.029 (2) | 0.042 (3) |
C2 | 0.060 (3) | 0.060 (3) | 0.080 (3) | 0.013 (2) | 0.033 (2) | 0.043 (3) |
C3 | 0.053 (2) | 0.057 (3) | 0.053 (2) | 0.011 (2) | 0.019 (2) | 0.026 (2) |
C4 | 0.055 (3) | 0.073 (3) | 0.070 (3) | 0.014 (2) | 0.028 (2) | 0.042 (3) |
C5 | 0.066 (3) | 0.060 (3) | 0.065 (3) | 0.010 (2) | 0.024 (2) | 0.036 (2) |
C6 | 0.067 (3) | 0.052 (3) | 0.059 (3) | 0.016 (2) | 0.032 (2) | 0.026 (2) |
C7 | 0.064 (3) | 0.057 (3) | 0.049 (2) | 0.009 (2) | 0.023 (2) | 0.026 (2) |
C8 | 0.050 (2) | 0.048 (2) | 0.055 (2) | 0.0069 (19) | 0.0200 (19) | 0.026 (2) |
C9 | 0.065 (3) | 0.053 (3) | 0.051 (2) | 0.013 (2) | 0.014 (2) | 0.019 (2) |
C10 | 0.066 (3) | 0.065 (3) | 0.055 (3) | 0.012 (2) | 0.011 (2) | 0.029 (3) |
C11 | 0.049 (2) | 0.052 (3) | 0.055 (3) | 0.013 (2) | 0.021 (2) | 0.023 (2) |
C12 | 0.129 (6) | 0.070 (4) | 0.067 (4) | 0.003 (4) | 0.041 (4) | 0.023 (3) |
Ag1—N1 | 2.111 (4) | O1—C11 | 1.227 (6) |
Ag1—N3 | 2.119 (4) | O2—C11 | 1.212 (6) |
F1—C12 | 1.266 (8) | C1—C2 | 1.351 (7) |
F2—C12 | 1.238 (8) | C2—C3 | 1.395 (6) |
F3—C12 | 1.231 (9) | C3—C4 | 1.408 (7) |
N1—C1 | 1.348 (7) | C4—C5 | 1.344 (7) |
N1—C5 | 1.350 (6) | C6—C7 | 1.380 (7) |
N2—C3 | 1.344 (6) | C7—C8 | 1.398 (6) |
N3—C6 | 1.342 (7) | C8—C9 | 1.405 (6) |
N3—C10 | 1.343 (7) | C9—C10 | 1.360 (7) |
N4—C8 | 1.347 (6) | C11—C12 | 1.507 (8) |
N1—Ag1—N3 | 166.51 (15) | C6—C7—C8 | 119.5 (4) |
C1—N1—C5 | 114.7 (4) | N4—C8—C7 | 121.1 (4) |
C1—N1—Ag1 | 125.1 (3) | N4—C8—C9 | 122.3 (4) |
C5—N1—Ag1 | 119.7 (3) | C7—C8—C9 | 116.6 (4) |
C6—N3—C10 | 116.2 (4) | C10—C9—C8 | 119.5 (4) |
C6—N3—Ag1 | 123.0 (3) | N3—C10—C9 | 124.5 (5) |
C10—N3—Ag1 | 120.9 (3) | O2—C11—O1 | 128.9 (5) |
N1—C1—C2 | 124.5 (4) | O2—C11—C12 | 116.6 (5) |
C1—C2—C3 | 120.5 (4) | O1—C11—C12 | 114.5 (5) |
N2—C3—C2 | 122.8 (4) | F3—C12—F2 | 103.0 (8) |
N2—C3—C4 | 122.0 (4) | F3—C12—F1 | 105.1 (8) |
C2—C3—C4 | 115.2 (4) | F2—C12—F1 | 102.9 (7) |
C5—C4—C3 | 120.2 (4) | F3—C12—C11 | 111.4 (7) |
C4—C5—N1 | 124.8 (5) | F2—C12—C11 | 117.7 (6) |
N3—C6—C7 | 123.8 (4) | F1—C12—C11 | 115.2 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.86 | 2.25 | 2.969 (6) | 142 |
N2—H2B···O2ii | 0.86 | 2.37 | 3.126 (7) | 146 |
N4—H4A···O1iii | 0.86 | 2.05 | 2.887 (6) | 164 |
N4—H4B···O2iv | 0.86 | 2.28 | 3.108 (6) | 162 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+2, −z; (iv) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C5H6N2)2](CF3O2) |
Mr | 409.13 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 9.492 (7), 9.803 (7), 10.002 (7) |
α, β, γ (°) | 115.206 (9), 108.078 (8), 92.793 (10) |
V (Å3) | 782.6 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.33 |
Crystal size (mm) | 0.32 × 0.27 × 0.15 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.676, 0.826 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3984, 2720, 2200 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.133, 1.06 |
No. of reflections | 2720 |
No. of parameters | 199 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.94, −0.67 |
Computer programs: SMART (Siemens, 1996), SMART, SHELXTL (Sheldrick, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.86 | 2.25 | 2.969 (6) | 142 |
N2—H2B···O2ii | 0.86 | 2.37 | 3.126 (7) | 146 |
N4—H4A···O1iii | 0.86 | 2.05 | 2.887 (6) | 164 |
N4—H4B···O2iv | 0.86 | 2.28 | 3.108 (6) | 162 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+2, −z; (iv) x, y+1, z. |
The coinage metals, especially silver, have been the subject of investigation for preparing novel complexes for decades. Interest in this area grew out of the diverse structural motifs displayed by these superficially similar monovalent cations. Recently, we reported several 2-aminopyrimidine complexes (Zhu, Usman et al., 2003; Zhu, Wang et al., 2003) with AgI atoms, which exhibit interesting bioactivities (to be reported elsewhere). We report here the crystal structure of a new 4-aminopyridinesilver(I) trifluoroacetate complex, (I).
As shown in Fig. 1, the Ag1 atom is coordinated to the pyridine N atoms of two independent 4-aminopyridine ligands. One O atom from the trifluoroacetate anion weakly ligates to the Ag atom [Ag1—O1 = 2.843 (4) Å]. The Ag—N distances [Ag1—N1 = 2.111 (4) Å and Ag1—N3 = 2.119 (4) Å] are within acceptable values but are shorter than those in the silver(I) complexes of 2-aminopyridines [2.230 (3) and 2.205 (4) Å (Zhu, Usman et al., 2003), and 2.137 (2) Å (Zhu, Wang et al., 2003)]. The bond angles [N1—Ag1—N3 = 166.5 (15)°, N1—Ag1—O1 = 94.8 (2)° and N3—Ag1—O1 = 96.2 (2)°], indicate a distorted T-shape coordination environment of atom Ag1. To reduce the steric effects the two pyridine rings connected by Ag1 are nearly perpendicular to one another, with a dihedral angle of 78.4 (2)°. All the other bond lengths and angles are in the normal ranges.
In the crystal structure of (I) (Fig. 2), discrete cations are interconnected by N—H···O hydrogen bonds to form a one-dimensional chain (see Table 1 for details). These chains are further linked by three short Ag···F contacts [Ag1—F1 = 3.414 (4) Å, Ag1—F1i = 3.376 (4) Å and Ag1—F2i = 3.593 (4) Å; symmetry code: (i) 2 − x, 2 − y, 1 − z], forming a layer-like structure (Fig. 3).