Polymeric (ethyl­enedi­amine)silver(I) 2,4,6-tri­nitro­phenolate

In the title compound, catena-poly­[[silver(I)-μ-ethyl­enedi­amine] 2,4,6-tri­nitro­phenolate], {[Ag(C₂H₈)](C₆H₂N₃O₇)}_n, the Ag atom is bicoordinated, in a linear configuration, by two different N atoms from two symmetry-related ethyl­enedi­amine ligands, resulting in a linear polymeric helical chain with an [–Ag—N—C—C—N–]_n backbone. In the crystal structure, the components are connected by weak interactions between Ag and O atoms from the phenolate anion and the nitro groups. There are also weak hydrogen-bonding interactions between the NH₂ groups and some of the O atoms of the anions, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.061
• wR factor = 0.102
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT761_ALERT_1_A CIF Contains no X-H Bonds ....................          ?
PLAT762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles ........          ?

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ...................       0.98
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .....          ?

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

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.

S2. Experimental

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%).

S3. Refinement

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 U_iso(H) values of 0.08 Ų.

Computing details

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).

Figures

	Fig. 1. The structure of the title compound, (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of (I), showing the hydrogen-bonding interactions as dashed lines.

(I)

Crystal data

[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) Å^3	Prism, brown
Z = 4	0.54 × 0.25 × 0.16 mm

Data collection

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

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0337P)^2] where P = (Fo^2 + 2Fc^2)/3
2492 reflections	(Δ/σ)max = 0.009
191 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Ag1—N1	2.123 (5)	N2—Ag1^ii	2.126 (5)
Ag1—N2^i	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—N2^i	172.70 (18)	O1—C3—C4	124.9 (5)
C1—N1—Ag1	116.3 (4)	O1—C3—C8	124.0 (5)
C2—N2—Ag1^ii	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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1^iii	0.90	2.02	2.908 (6)	169
N1—H1C···O7^iii	0.90	2.53	2.976 (6)	111
N1—H1D···O5^iv	0.90	2.30	3.087 (6)	147
N2—H2C···O7^v	0.90	2.45	3.121 (6)	131
N2—H2D···O1^iii	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.