The title complex, {[Ag(C
2H
8N
2)](CF
3SO
3)}
n, is a mononuclear silver(I) compound. The Ag
I atom lies on a mirror plane and is bicoordinated in a linear configuration by two N atoms from two ethane-1,2-diamine ligands, giving zigzag polymeric chains with an [—Ag—N—C—C—N—]
n backbone running along the
b axis. These chains are interconnected by N—H

O hydrogen bonds involving the trifluoromethanesulfonate anions (which also lie on mirror planes), forming a three-dimensional network.
Supporting information
CCDC reference: 254907
Silver trifluoromethanesulfonate (0.1 mmol, 25.7 mg) and 1,2-diaminoethane (0.1 mmol, 6.0 mg) were dissolved in an ammonia solution (10 ml, 30%). The mixture was stirred for about 10 min at room temperature to obtain a clear colourless solution. The resulting solution was kept in the dark and, after slow evaporation of the solvent over a period of 5 d, crystals of (I) were isolated, washed three times with water and dried in a vacuum desiccator using anhydrous CaCl2 (yield 61%). Elemental analysis, calculated: C 11.4, H 2.5, N 8.8%; found: C 11.3, H 2.5, N 8.9%.
All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H = 0.90 and C—H = 0.96 Å, and with Uiso(H) = 0.08 Å2.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
catena-Poly[[silver(I)-µ-ethane-1,2-diamine-
κ2N:
N'] trifluoromethanesulfonate]
top
Crystal data top
[Ag(C2H8N2)](CF3SO3) | F(000) = 616 |
Mr = 317.04 | Dx = 2.353 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 2334 reflections |
a = 8.711 (11) Å | θ = 2.8–28.0° |
b = 10.050 (13) Å | µ = 2.51 mm−1 |
c = 10.224 (13) Å | T = 298 K |
V = 895 (2) Å3 | Block, colourless |
Z = 4 | 0.21 × 0.10 × 0.08 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1025 independent reflections |
Radiation source: fine-focus sealed tube | 972 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 27.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.621, Tmax = 0.824 | k = −12→10 |
4585 measured reflections | l = −8→13 |
Refinement top
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0314P)2 + 1.0534P] where P = (Fo2 + 2Fc2)/3 |
1025 reflections | (Δ/σ)max < 0.001 |
67 parameters | Δρmax = 0.88 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
Crystal data top
[Ag(C2H8N2)](CF3SO3) | V = 895 (2) Å3 |
Mr = 317.04 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 8.711 (11) Å | µ = 2.51 mm−1 |
b = 10.050 (13) Å | T = 298 K |
c = 10.224 (13) Å | 0.21 × 0.10 × 0.08 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1025 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 972 reflections with I > 2σ(I) |
Tmin = 0.621, Tmax = 0.824 | Rint = 0.029 |
4585 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.88 e Å−3 |
1025 reflections | Δρmin = −0.57 e Å−3 |
67 parameters | |
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 | x | y | z | Uiso*/Ueq | |
Ag1 | 0.04722 (5) | 0.7500 | 0.32019 (4) | 0.04027 (16) | |
S1 | 0.64497 (13) | 0.7500 | 0.56504 (11) | 0.0301 (3) | |
N1 | 0.0457 (3) | 0.5368 (3) | 0.3239 (3) | 0.0377 (7) | |
H1A | 0.1436 | 0.5082 | 0.3234 | 0.080* | |
H1B | 0.0011 | 0.5076 | 0.2498 | 0.080* | |
C2 | 0.4396 (6) | 0.7500 | 0.5307 (5) | 0.0379 (11) | |
C1 | −0.0337 (4) | 0.4751 (3) | 0.4367 (3) | 0.0357 (8) | |
H1C | −0.0282 | 0.3800 | 0.4296 | 0.080* | |
H1E | −0.1393 | 0.5025 | 0.4370 | 0.080* | |
O2 | 0.6658 (3) | 0.6296 (3) | 0.6389 (3) | 0.0488 (7) | |
F1 | 0.3989 (3) | 0.6442 (3) | 0.4631 (3) | 0.0720 (8) | |
O1 | 0.7145 (4) | 0.7500 | 0.4376 (4) | 0.0520 (10) | |
F2 | 0.3591 (4) | 0.7500 | 0.6396 (4) | 0.0689 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.0534 (3) | 0.0290 (2) | 0.0384 (3) | 0.000 | −0.00441 (17) | 0.000 |
S1 | 0.0275 (5) | 0.0282 (5) | 0.0348 (6) | 0.000 | −0.0001 (5) | 0.000 |
N1 | 0.0421 (16) | 0.0318 (15) | 0.0393 (17) | 0.0039 (12) | 0.0002 (13) | −0.0038 (12) |
C2 | 0.034 (2) | 0.041 (3) | 0.039 (3) | 0.000 | 0.001 (2) | 0.000 |
C1 | 0.0382 (18) | 0.0279 (16) | 0.041 (2) | −0.0018 (14) | −0.0020 (15) | −0.0005 (14) |
O2 | 0.0485 (15) | 0.0375 (14) | 0.0604 (17) | 0.0066 (12) | −0.0065 (14) | 0.0124 (12) |
F1 | 0.0506 (13) | 0.0715 (17) | 0.094 (2) | −0.0167 (13) | −0.0110 (14) | −0.0339 (15) |
O1 | 0.039 (2) | 0.068 (3) | 0.048 (2) | 0.000 | 0.0116 (17) | 0.000 |
F2 | 0.0445 (19) | 0.102 (3) | 0.060 (2) | 0.000 | 0.0247 (18) | 0.000 |
Geometric parameters (Å, º) top
Ag1—N1i | 2.143 (4) | N1—H1B | 0.8999 |
Ag1—N1 | 2.143 (4) | C2—F2 | 1.316 (6) |
S1—O1 | 1.437 (4) | C2—F1 | 1.317 (4) |
S1—O2i | 1.437 (3) | C2—F1i | 1.317 (4) |
S1—O2 | 1.437 (3) | C1—C1ii | 1.506 (7) |
S1—C2 | 1.823 (6) | C1—H1C | 0.9600 |
N1—C1 | 1.481 (5) | C1—H1E | 0.9601 |
N1—H1A | 0.9001 | | |
| | | |
N1i—Ag1—N1 | 177.86 (15) | F2—C2—F1 | 107.5 (3) |
O1—S1—O2i | 115.02 (15) | F2—C2—F1i | 107.5 (3) |
O1—S1—O2 | 115.02 (15) | F1—C2—F1i | 107.7 (5) |
O2i—S1—O2 | 114.6 (3) | F2—C2—S1 | 111.1 (4) |
O1—S1—C2 | 103.8 (3) | F1—C2—S1 | 111.5 (3) |
O2i—S1—C2 | 103.02 (15) | F1i—C2—S1 | 111.5 (3) |
O2—S1—C2 | 103.02 (15) | N1—C1—C1ii | 110.4 (4) |
C1—N1—Ag1 | 115.8 (2) | N1—C1—H1C | 109.5 |
C1—N1—H1A | 108.2 | C1ii—C1—H1C | 112.1 |
Ag1—N1—H1A | 108.3 | N1—C1—H1E | 109.3 |
C1—N1—H1B | 108.5 | C1ii—C1—H1E | 106.0 |
Ag1—N1—H1B | 108.3 | H1C—C1—H1E | 109.5 |
H1A—N1—H1B | 107.5 | | |
| | | |
N1—C1—C1ii—N1ii | −180.0 | O1—S1—C2—F1 | 60.2 (3) |
O2—S1—C2—F1 | −60.1 (4) | O2i—S1—C2—F1 | −179.6 (3) |
O2—S1—C2—F2 | 59.74 (14) | O1—S1—C2—F1i | −60.2 (3) |
O1—S1—C2—F2 | 180.0 | O2i—S1—C2—F1i | 60.1 (4) |
O2i—S1—C2—F2 | −59.74 (14) | O2—S1—C2—F1i | 179.6 (3) |
Symmetry codes: (i) x, −y+3/2, z; (ii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2iii | 0.90 | 2.30 | 3.126 (5) | 152 |
N1—H1A···O2iv | 0.90 | 2.20 | 3.043 (5) | 156 |
Symmetry codes: (iii) −x+1/2, −y+1, z−1/2; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Ag(C2H8N2)](CF3SO3) |
Mr | 317.04 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 298 |
a, b, c (Å) | 8.711 (11), 10.050 (13), 10.224 (13) |
V (Å3) | 895 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.51 |
Crystal size (mm) | 0.21 × 0.10 × 0.08 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.621, 0.824 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4585, 1025, 972 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.076, 1.19 |
No. of reflections | 1025 |
No. of parameters | 67 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.57 |
Selected geometric parameters (Å, º) topAg1—N1 | 2.143 (4) | | |
| | | |
N1i—Ag1—N1 | 177.86 (15) | | |
| | | |
N1—C1—C1ii—N1ii | −180.0 | O2—S1—C2—F2 | 59.74 (14) |
O2—S1—C2—F1 | −60.1 (4) | O1—S1—C2—F1 | 60.2 (3) |
Symmetry codes: (i) x, −y+3/2, z; (ii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2iii | 0.90 | 2.30 | 3.126 (5) | 152 |
N1—H1A···O2iv | 0.90 | 2.20 | 3.043 (5) | 156 |
Symmetry codes: (iii) −x+1/2, −y+1, z−1/2; (iv) −x+1, −y+1, −z+1. |
Inorganic supramolecular chemistry, and in particular the construction of polymeric coordination networks, is an extremely topical area of research (Xu et al., 2001; Yaghi & Li, 1996). The construction of a wide variety of network topologies has been achieved through ligand design and the use of different counteranions. The balance between the formation of different structures is often subtle. Factors which affect the topology of coordination polymers include not only the highly influential forces of metal and ligand coordination preferences, but also anion-based interactions. The latter factor is particularly notable in AgI coordination polymers (Blake et al., 2000; Melcer et al., 2001). Owing to the flexible coordination sphere of AgI, coordination numbers from 2 to 6 are all possible and, due to the relatively weak nature of many AgI-ligand interactions, such compounds are particularly susceptible to the influence of weaker supramolecular forces (Khlobystov et al., 2001).
Recently, we have reported a polynuclear AgI complex, (II), with 1,2-diaminoethane as the ligand and 3-fluorobenzoate as the counteranion, catena-poly[(silver(I)-µ-ethane-1,2-diamine-κ2N:N') 3-fluorobenzoate monohydrate] (You et al., 2004). In order to study the effects of the couteranion in the construction of silver(I) coordination polymers, the structure of the title compound, (I), is reported here. \sch
Complex (I) is a polymeric ethylenediamine-AgI compound (Fig. 1). The smallest repeat unit for the complex contains an ethylenediamine-AgI cation and a trifluoromethanesulfonate anion, where the Ag1 atom and the O1—S1—C2—F2 moiety of the anion lie on a mirror plane and the ethylenediamine ligand has a centre of symmetry. The AgI atom is in a linear coordination environment and is bicoordinated by two N atoms of ethylenediamine ligands, the N1—Ag1—N1i bond angle being 177.86 (15)° [symmetry code: (i) x, 3/2 − y, z; Table 1].
In the crystal packing of (I), the ethylenediamine-AgI polymer forms a zigzag chain along the b axis, and the trifluoromethanesulfonate anions are located between the chains. The sulfonate group ends connect the chains via N—H···O hydrogen bonds (Table 2), forming a three-dimensional structure (Fig. 2).
The Ag—N bond length in (I) [2.143 (4) Å] is comparable with the average value of 2.138 (2) Å in (II). The coordination geometry around the Ag atom in (II) is also linear but slightly distorted, with an N—Ag—N bond angle of 170.50 (11)°. This may be due to weak interactions between the solvate water molecule and the Ag atom in (II), with an Ag···OW distance of 2.610 (3) Å, which inclines the AgI atom towards the solvate water molecule.
In (I), two O atoms of the trifluoroacetate anion contribute to intermolecular N—H···O hydrogen bonds, which results in the two 1,2-diaminoethane ligands being located on the same side of the N—Ag—N axis and adopting the trans form to minimize steric effects (Fig. 2). However, in (II), the diaminoethane ligand shows the gauche form, with a C—N—N—C torsion angle of −74.1 (4)°. The 3-fluorobenzoate anion is located near the two N atoms of the diaminoethane ligand. In (II), a nine-membered ring is formed through N—H···O hydrogen bonds involving the carboxylate group of the anion.