Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803016635/su6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803016635/su6025Isup2.hkl |
CCDC reference: 222788
Ethylenediamine and 2,4,6-trinitrophenolate are available commercially and were used without further purification. Ag2O (0.5 mmol, 116 mg) and 2,4,6-trinitrophenol (1 mmol, 229 mg) were dissolved in an aqueous solution of ammonia (10 ml). The mixture was stirred for ca 10 min to obtain a clear solution. To this solution was added ethylenediamine (2 mmol, 120 mg) in an ammonium solution (2 ml). After keeping the resulting solution in air for one month, large brown single crystals were formed on slow evaporation. The crystals were isolated, washed with water three times and dried in a vacuum desiccator using CaCl2 (yield = 42%).
All H atoms were placed in idealized positions and constrained to ride on their parent atoms, with N—H and C—H distances of 0.90 and 0.96 Å, respectively, and Uiso(H) values of 0.08 Å2.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).
[Ag(C2H8)](C6H2N3O7) | F(000) = 784 |
Mr = 396.08 | Dx = 2.068 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.844 (2) Å | Cell parameters from 5661 reflections |
b = 19.406 (4) Å | θ = 2.5–25.4° |
c = 8.376 (2) Å | µ = 1.63 mm−1 |
β = 93.72 (3)° | T = 293 K |
V = 1272.3 (5) Å3 | Prism, brown |
Z = 4 | 0.54 × 0.25 × 0.16 mm |
Siemens SMART CCD area-detector diffractometer | 2492 independent reflections |
Radiation source: fine-focus sealed tube | 2031 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −9→6 |
Tmin = 0.575, Tmax = 0.787 | k = −20→23 |
5663 measured reflections | l = −10→9 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.20 | w = 1/[σ2(Fo2) + (0.0337P)2] where P = (Fo2 + 2Fc2)/3 |
2492 reflections | (Δ/σ)max = 0.009 |
191 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
[Ag(C2H8)](C6H2N3O7) | V = 1272.3 (5) Å3 |
Mr = 396.08 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.844 (2) Å | µ = 1.63 mm−1 |
b = 19.406 (4) Å | T = 293 K |
c = 8.376 (2) Å | 0.54 × 0.25 × 0.16 mm |
β = 93.72 (3)° |
Siemens SMART CCD area-detector diffractometer | 2492 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2031 reflections with I > 2σ(I) |
Tmin = 0.575, Tmax = 0.787 | Rint = 0.033 |
5663 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.20 | Δρmax = 0.61 e Å−3 |
2492 reflections | Δρmin = −0.64 e Å−3 |
191 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 | 0.05122 (6) | 0.72871 (2) | 0.74301 (6) | 0.0481 (2) | |
O1 | 0.0840 (5) | 1.1431 (2) | 0.9180 (5) | 0.0533 (11) | |
O2 | 0.3732 (5) | 1.0845 (2) | 0.8259 (6) | 0.0605 (13) | |
O3 | 0.3305 (5) | 1.0283 (3) | 0.6063 (6) | 0.0776 (16) | |
O4 | −0.1221 (6) | 0.8615 (2) | 0.6094 (6) | 0.0734 (15) | |
O5 | −0.3491 (6) | 0.8848 (2) | 0.7299 (5) | 0.0646 (13) | |
O6 | −0.3450 (5) | 1.0816 (2) | 1.0866 (5) | 0.0573 (12) | |
O7 | −0.2443 (5) | 1.1725 (2) | 0.9808 (5) | 0.0602 (12) | |
N1 | −0.0169 (6) | 0.7164 (2) | 0.9826 (6) | 0.0443 (12) | |
H1C | −0.0294 | 0.7586 | 1.0251 | 0.080* | |
H1D | 0.0704 | 0.6956 | 1.0385 | 0.080* | |
N2 | −0.3833 (6) | 0.7729 (3) | 1.0006 (6) | 0.0500 (13) | |
H2C | −0.4739 | 0.7901 | 0.9423 | 0.080* | |
H2D | −0.2978 | 0.8035 | 0.9947 | 0.080* | |
N3 | 0.2808 (6) | 1.0529 (2) | 0.7288 (7) | 0.0449 (13) | |
N4 | −0.2058 (7) | 0.8995 (2) | 0.6915 (6) | 0.0489 (13) | |
N5 | −0.2528 (6) | 1.1101 (3) | 0.9942 (6) | 0.0415 (12) | |
C1 | −0.1749 (8) | 0.6776 (3) | 1.0051 (8) | 0.0559 (18) | |
H1A | −0.1936 | 0.6748 | 1.1171 | 0.080* | |
H1B | −0.1601 | 0.6315 | 0.9665 | 0.080* | |
C2 | −0.3287 (8) | 0.7098 (3) | 0.9203 (8) | 0.0567 (18) | |
H2A | −0.3031 | 0.7204 | 0.8125 | 0.080* | |
H2B | −0.4212 | 0.6773 | 0.9160 | 0.080* | |
C3 | 0.0189 (7) | 1.0894 (3) | 0.8637 (6) | 0.0349 (13) | |
C4 | 0.1030 (6) | 1.0405 (3) | 0.7657 (6) | 0.0329 (13) | |
C5 | 0.0314 (6) | 0.9807 (3) | 0.7055 (6) | 0.0356 (13) | |
H5A | 0.0928 | 0.9513 | 0.6372 | 0.080* | |
C6 | −0.1316 (7) | 0.9633 (3) | 0.7462 (6) | 0.0354 (13) | |
C7 | −0.2238 (7) | 1.0059 (3) | 0.8410 (7) | 0.0361 (13) | |
H7A | −0.3366 | 0.9933 | 0.8685 | 0.080* | |
C8 | −0.1522 (6) | 1.0664 (3) | 0.8941 (6) | 0.0328 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0463 (3) | 0.0510 (3) | 0.0484 (3) | 0.0019 (2) | 0.0142 (2) | 0.0046 (2) |
O1 | 0.037 (2) | 0.043 (2) | 0.080 (3) | 0.0007 (19) | 0.004 (2) | −0.020 (2) |
O2 | 0.037 (3) | 0.055 (3) | 0.090 (4) | −0.003 (2) | 0.010 (2) | −0.013 (3) |
O3 | 0.054 (3) | 0.126 (4) | 0.056 (3) | 0.005 (3) | 0.025 (2) | −0.008 (3) |
O4 | 0.074 (3) | 0.052 (3) | 0.096 (4) | −0.004 (2) | 0.021 (3) | −0.029 (3) |
O5 | 0.062 (3) | 0.061 (3) | 0.073 (3) | −0.027 (2) | 0.019 (3) | −0.016 (2) |
O6 | 0.052 (3) | 0.064 (3) | 0.059 (3) | 0.009 (2) | 0.026 (2) | 0.006 (2) |
O7 | 0.058 (3) | 0.039 (3) | 0.086 (4) | 0.011 (2) | 0.023 (2) | −0.005 (2) |
N1 | 0.051 (3) | 0.039 (3) | 0.043 (3) | 0.008 (2) | 0.004 (2) | 0.000 (2) |
N2 | 0.033 (3) | 0.069 (4) | 0.049 (3) | 0.000 (3) | 0.012 (2) | 0.004 (3) |
N3 | 0.039 (3) | 0.043 (3) | 0.053 (4) | 0.004 (2) | 0.007 (3) | 0.005 (3) |
N4 | 0.058 (4) | 0.042 (3) | 0.047 (3) | −0.005 (3) | 0.005 (3) | −0.005 (2) |
N5 | 0.037 (3) | 0.045 (3) | 0.042 (3) | 0.010 (2) | 0.001 (2) | −0.003 (2) |
C1 | 0.072 (5) | 0.045 (4) | 0.053 (4) | −0.001 (3) | 0.025 (4) | −0.001 (3) |
C2 | 0.053 (4) | 0.073 (5) | 0.046 (4) | −0.021 (3) | 0.017 (3) | −0.009 (3) |
C3 | 0.035 (3) | 0.035 (3) | 0.034 (3) | 0.005 (3) | −0.001 (2) | 0.001 (3) |
C4 | 0.029 (3) | 0.039 (3) | 0.032 (3) | 0.004 (2) | 0.003 (2) | 0.004 (2) |
C5 | 0.039 (3) | 0.042 (3) | 0.026 (3) | 0.004 (3) | 0.002 (3) | 0.002 (2) |
C6 | 0.042 (3) | 0.035 (3) | 0.030 (3) | −0.002 (3) | 0.002 (2) | −0.003 (2) |
C7 | 0.034 (3) | 0.038 (3) | 0.036 (3) | 0.001 (3) | −0.001 (2) | 0.002 (3) |
C8 | 0.029 (3) | 0.036 (3) | 0.033 (3) | 0.010 (2) | 0.008 (2) | 0.001 (2) |
Ag1—N1 | 2.123 (5) | N2—Ag1ii | 2.126 (5) |
Ag1—N2i | 2.126 (5) | N3—C4 | 1.468 (6) |
O1—C3 | 1.234 (6) | N4—C6 | 1.431 (7) |
O2—N3 | 1.219 (6) | N5—C8 | 1.461 (6) |
O3—N3 | 1.218 (6) | C1—C2 | 1.496 (8) |
O4—N4 | 1.228 (5) | C3—C4 | 1.441 (7) |
O5—N4 | 1.223 (6) | C3—C8 | 1.453 (7) |
O6—N5 | 1.225 (5) | C4—C5 | 1.371 (7) |
O7—N5 | 1.218 (5) | C5—C6 | 1.386 (7) |
N1—C1 | 1.473 (7) | C6—C7 | 1.383 (7) |
N2—C2 | 1.474 (7) | C7—C8 | 1.362 (7) |
N1—Ag1—N2i | 172.70 (18) | O1—C3—C4 | 124.9 (5) |
C1—N1—Ag1 | 116.3 (4) | O1—C3—C8 | 124.0 (5) |
C2—N2—Ag1ii | 121.3 (4) | C4—C3—C8 | 111.1 (5) |
O3—N3—O2 | 123.4 (5) | C5—C4—C3 | 125.1 (5) |
O3—N3—C4 | 118.3 (5) | C5—C4—N3 | 115.7 (5) |
O2—N3—C4 | 118.3 (5) | C3—C4—N3 | 119.3 (5) |
O5—N4—O4 | 122.7 (5) | C4—C5—C6 | 118.6 (5) |
O5—N4—C6 | 118.6 (5) | C7—C6—C5 | 121.4 (5) |
O4—N4—C6 | 118.6 (5) | C7—C6—N4 | 119.0 (5) |
O7—N5—O6 | 123.0 (5) | C5—C6—N4 | 119.6 (5) |
O7—N5—C8 | 119.3 (5) | C8—C7—C6 | 118.8 (5) |
O6—N5—C8 | 117.6 (5) | C7—C8—C3 | 125.0 (5) |
N1—C1—C2 | 112.6 (5) | C7—C8—N5 | 117.4 (5) |
N2—C2—C1 | 112.3 (5) | C3—C8—N5 | 117.5 (5) |
Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x−1/2, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O1iii | 0.90 | 2.02 | 2.908 (6) | 169 |
N1—H1C···O7iii | 0.90 | 2.53 | 2.976 (6) | 111 |
N1—H1D···O5iv | 0.90 | 2.30 | 3.087 (6) | 147 |
N2—H2C···O7v | 0.90 | 2.45 | 3.121 (6) | 131 |
N2—H2D···O1iii | 0.90 | 2.06 | 2.904 (6) | 155 |
Symmetry codes: (iii) −x, −y+2, −z+2; (iv) x+1/2, −y+3/2, z+1/2; (v) −x−1, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C2H8)](C6H2N3O7) |
Mr | 396.08 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.844 (2), 19.406 (4), 8.376 (2) |
β (°) | 93.72 (3) |
V (Å3) | 1272.3 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.63 |
Crystal size (mm) | 0.54 × 0.25 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.575, 0.787 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5663, 2492, 2031 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.102, 1.20 |
No. of reflections | 2492 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.64 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O1i | 0.90 | 2.02 | 2.908 (6) | 169 |
N1—H1C···O7i | 0.90 | 2.53 | 2.976 (6) | 111 |
N1—H1D···O5ii | 0.90 | 2.30 | 3.087 (6) | 147 |
N2—H2C···O7iii | 0.90 | 2.45 | 3.121 (6) | 131 |
N2—H2D···O1i | 0.90 | 2.06 | 2.904 (6) | 155 |
Symmetry codes: (i) −x, −y+2, −z+2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x−1, −y+2, −z+2. |
The title complex, (I), is an analogue of the compound we reported on recently, that is, silver ethylenediamine 3-nitrobenzoate (Usman et al., 2003).
In (I), atom Ag1 is bicoordinated in a slightly distorted linear configuration by two different N atoms [N1 and N2i; symmetry code: (i) x + 1/2, −y + 3/2, z − 1/2] from two symmetry-related ethylenediamnie ligands (Fig. 1). The Ag1—N1 and Ag—N2i bond lengths are 2.123 (5) and 2.126 (5) Å, respectively, which are slightly shorter than those observed in the silver ethylenediamine 3-nitrobenzoate analogue [2.140 (2) and 2.141 (2) Å]. The N1—Ag1—N2i angle is 172.70 (18)°, which is less than that [177.1 (1)°] observed in the 3-nitrobenzoate analogue. This configuration gives rise to a linear polymeric chain in (I), with an [–Ag—N—C—C—N–]n backbone (Fig. 2).
The remainder of the bond lengths in (I) are within the normal ranges (Allen et al., 1987). The C—O bond length of the phenolate is typical for a double bond, implying that the negative charge located on the phenolate O atom is delocalized over the whole C—O bond. The N—O bond distances of the nitro groups of the trinitrophenolate anion are typical double bonds.
In each repeat unit, the two components, viz. the ethylenediamine-coordinated silver cation and the 2,4,6-trinitrophenolate anion, are linked by weak Ag···O interactions [2.927 (6)–3.643 (6) Å]. Hydrogen bonds between the NH2 H atoms and some of the O atoms of the anions result in the formation of a three-dimensional network (Fig. 2 and Table 1). The distance between the centroids of the neighbouring parallel aromatic rings of the 2,4,6-trinitrophenolate anions is 3.504 (3) Å (symmetry code: −x, 2 − y, 2 − z). The π–π stacking of the benzene planes also contributes to the three-dimensional structure of the complex.