Polymeric structure of (ethyl­ene­diamine)silver(I) 3-nitro­benzoate monohydrate

In the ternary title compound, catena-poly­[[silver(I)-μ-ethylenedi­amine-κ²N:N′] 3-nitro­benzoate monohydrate], {[Ag(C₂H₈N₂)](C₇H₄NO₄)·H₂O}_n, the Ag atom is bicoordinated in a linear configuration by two different N atoms from two symmetry-related ethyl­enedi­amine ligands, thus giving linear polymeric chains with an [–Ag—N—C—C—N–]_n backbone running parallel to the a axis. In the crystal packing, these linear chains are interconnected by N—H...O and O—H...O hydrogen bonds to form layers parallel to the ab plane.

S1. Comment

The synthesis or construction of supramolecular coordination polymeric architecture is currently receiving considerable attention. Ethylenediamine and its analogues are a family of organic ligands of this type. The analogues can also interact with almost all transition metal ions, thus giving a wide variety of supramolecular coordination possibilities. Furthermore, the coinage metals, especially silver, have been a subject of investigation for the construction of supramolecular complexes for decades. Interest in this area grew out of the diverse structural motifs displayed by these superficially similar monovalent cations. Some interesting ethylenediamine complexes with Ag^I atoms have been reported, such as silver ethylenediamine perchlorate (Bang, 1978) and silver ethylenediamine thiocyanates (Ren, 2001). Our interest in silver complexes has led us to the title complex, (I), a hydrate of ethylenediamine-silver(I)-3-nitrobenzoate, whose structure is reported here.

The bond lengths in (I) (Table 1) are within the normal ranges (Allen et al., 1987). The Ag—N bond lengths are slightly shorter than those in the silver ethylenediamine perchlorate [2.17 (1) Å] or the silver thiocyanates [2.172 (2)–2.313 (3) Å]. The C—O bond distances of the 3-nitrobenzoate anion are intermediate between C—O single and double bonds, implying that the negative charge located on the anion is delocalized over the two C—O bonds. This assumption is supported by the geometry of the anion and the unambiguous location of H atoms attached to N and O atoms. Within the 3-nitrobenzoate anion, the carboxylate group (O1/O2/C7) and the nitro group (N3/O3/O4) are twisted out of the plane of the aromatic ring by 8.9 (1)° about the C1—C7 bond and 13.1 (2)° about the N3—C3 bond, respectively.

The Ag1 atom is bi-coordinated in an essentially linear configuration by two different N atoms (N1 and N2) from two symmetry-related ethylenediamine ligands from different asymmetric units, with an N1—Ag1—N2(x + 1,y,z) angle of 177.1 (1)°. This gives rise to a linear polymeric chain of (I) running parallel to the x axis, with a [–Ag1—N1—C8—C9—N2–]_n backbone.

In one asymmetric unit, the three components, viz. the ethylenediamine-coordinated silver cation, the 3-nitrobenzoate anion, and the water molecule, are linked together by N—H···O and O—H···O hydrogen bonds (Fig. 1), namely N1—H11···O1, N2—H12···O1, N2—H12···O2, N1—H21···O1W, and O1W—H2W···O2 (Table 2). The ethylenediamine ligand acts as a multiple hydrogen-bond donor via its amino groups, whereas the water molecule acts as both a hydrogen donor and a hydrogen acceptor. The donor function N2—H12 is involved in a three-centered hydrogen bond to the carboxylate O atoms, with an O1···H21···O2 angle of 52.1 (1)°. Within the cation, Ag1, N1, C8, and C9 are coplanar, and N2 is displaced by 1.226 (2) Å because C9 is sp³ hybridized.

The packing structure comprises layers parallel to the xy plane (Fig. 2), in which the polymeric chains are interconnected symmetrically by O1W—H1W···O2ⁱ and N2—H22···O1ⁱⁱ hydrogen bonds (Table 2). The layers are further linked by C4—H4···O1Wⁱⁱⁱ contacts and four short Ag···O contacts (Table 3) into a three-dimensional network.

S2. Experimental

Ethylenediamine and 3-nitrobenzoic acid were available commercially and were used without further purification. Ag₂O (0.5 mmol, 116 mg) and 3-nitrobenzoic acid (1 mmol, 167 mg) were dissolved in ammonium solution (10 ml). The mixture was stirred for ca 10 min to obtain a clear solution. To this solution, ethylenediamine (2 mmol, 120 mg) in ammonium solution (2 ml) was added. After keeping the resulting solution in air for 2 d with ammonium gas escaping, large colourless single crystals formed. These were isolated, washed with water three times, and dried in a vacuum desiccator using drying CaCl₂ (yield = 42%).

S3. Refinement

H atoms attached to N and O atoms were located from Fourier maps, taking O—H (water) distances of 0.78 (3)–0.84 (4) Å and N—H distances of 0.79 (3)–0.87 (3) Å, and were isotropically refined. H atoms attached to C atoms were geometrically fixed and treated as riding atoms, with C—H distances of 0.93–0.97 Å and U_iso(H) equal to 1.2 U_eq(C).

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, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of one monomeric unit of the polymeric complex (I), showing displacement ellipsoids at the 50% probability level and the atom-numbering scheme.
	Fig. 2. A part of the packing structure of (I), showing the formations of layers parallel to the xy plane. Hydrogen bonds are indicated by dashed lines.

catena-poly[[silver(I)-µ-ethylenediamine-κ²N:N'] 3-nitrobenzoate monohydrate]

Crystal data

[Ag(C2H8N2)](C7H4NO4)·H2O	Z = 2
Mr = 352.10	F(000) = 352
Triclinic, P1	Dx = 1.885 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1816 (4) Å	Cell parameters from 3342 reflections
b = 9.6857 (5) Å	θ = 2.6–28.3°
c = 10.1259 (5) Å	µ = 1.64 mm^−1
α = 67.825 (1)°	T = 293 K
β = 72.047 (1)°	Block, colorless
γ = 83.078 (1)°	0.40 × 0.24 × 0.12 mm
V = 620.48 (6) Å^3

Data collection

Siemens SMART CCD area detector diffractometer	2920 independent reflections
Radiation source: fine-focus sealed tube	2776 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.6°
ω scans	h = −9→9
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996)	k = −7→12
Tmin = 0.560, Tmax = 0.827	l = −12→13
3951 measured reflections

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0162P)^2 + 0.384P] where P = (Fo^2 + 2Fc^2)/3
2920 reflections	(Δ/σ)max = 0.002
187 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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
O1	1.0173 (3)	0.79324 (19)	0.1878 (2)	0.0510 (4)
O2	0.9479 (3)	0.5942 (2)	0.15512 (18)	0.0477 (4)
O3	0.6816 (4)	0.1587 (2)	0.5923 (3)	0.0718 (6)
O4	0.5037 (3)	0.1868 (3)	0.7928 (2)	0.0695 (6)
N3	0.6161 (3)	0.2351 (2)	0.6678 (2)	0.0469 (5)
C1	0.8313 (3)	0.6013 (2)	0.3973 (2)	0.0300 (4)
C2	0.7702 (3)	0.4546 (2)	0.4563 (2)	0.0319 (4)
H2	0.7928	0.3987	0.3957	0.038*
C3	0.6751 (3)	0.3922 (2)	0.6068 (2)	0.0346 (4)
C4	0.6355 (3)	0.4710 (3)	0.7008 (2)	0.0413 (5)
H4	0.5694	0.4272	0.8013	0.050*
C5	0.6974 (4)	0.6174 (3)	0.6410 (3)	0.0448 (6)
H5	0.6732	0.6733	0.7018	0.054*
C6	0.7954 (4)	0.6817 (3)	0.4907 (3)	0.0389 (5)
H6	0.8375	0.7799	0.4521	0.047*
C7	0.9406 (3)	0.6694 (2)	0.2335 (2)	0.0342 (4)
Ag1	1.62372 (2)	0.852457 (19)	−0.113660 (19)	0.03799 (6)
N1	1.3384 (3)	0.8053 (2)	−0.1105 (2)	0.0345 (4)
N2	0.9152 (3)	0.8944 (2)	−0.1251 (2)	0.0342 (4)
C8	1.2769 (3)	0.8924 (3)	−0.2444 (3)	0.0400 (5)
H8A	1.3707	0.8760	−0.3295	0.048*
H8B	1.2803	0.9975	−0.2605	0.048*
C9	1.0733 (3)	0.8553 (3)	−0.2378 (3)	0.0390 (5)
H9A	1.0520	0.9078	−0.3346	0.047*
H9B	1.0674	0.7493	−0.2166	0.047*
H11	1.258 (4)	0.812 (3)	−0.035 (3)	0.039 (7)*
H21	1.328 (4)	0.712 (4)	−0.097 (3)	0.051 (8)*
H12	0.928 (4)	0.846 (3)	−0.046 (3)	0.044 (8)*
H22	0.928 (4)	0.982 (3)	−0.138 (3)	0.045 (8)*
O1W	1.2671 (3)	0.4702 (2)	−0.0027 (3)	0.0528 (5)
H1W	1.212 (5)	0.454 (4)	−0.057 (4)	0.065 (10)*
H2W	1.176 (5)	0.487 (3)	0.056 (4)	0.053 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0621 (12)	0.0373 (9)	0.0424 (9)	−0.0089 (8)	−0.0043 (8)	−0.0082 (7)
O2	0.0519 (10)	0.0627 (11)	0.0319 (8)	−0.0087 (8)	−0.0068 (7)	−0.0223 (8)
O3	0.1001 (18)	0.0447 (11)	0.0606 (13)	−0.0163 (11)	−0.0057 (12)	−0.0172 (10)
O4	0.0726 (15)	0.0661 (13)	0.0458 (11)	−0.0228 (11)	0.0017 (10)	−0.0021 (10)
N3	0.0450 (12)	0.0450 (11)	0.0422 (11)	−0.0081 (9)	−0.0119 (9)	−0.0045 (9)
C1	0.0267 (9)	0.0357 (10)	0.0276 (9)	0.0040 (8)	−0.0097 (7)	−0.0112 (8)
C2	0.0294 (10)	0.0374 (11)	0.0315 (10)	0.0019 (8)	−0.0104 (8)	−0.0145 (8)
C3	0.0289 (10)	0.0385 (11)	0.0327 (10)	0.0017 (8)	−0.0104 (8)	−0.0079 (8)
C4	0.0349 (11)	0.0548 (14)	0.0289 (10)	0.0069 (10)	−0.0068 (8)	−0.0134 (10)
C5	0.0500 (14)	0.0523 (14)	0.0377 (12)	0.0130 (11)	−0.0132 (10)	−0.0259 (11)
C6	0.0438 (12)	0.0364 (11)	0.0403 (12)	0.0079 (9)	−0.0160 (10)	−0.0173 (9)
C7	0.0317 (10)	0.0397 (11)	0.0287 (10)	0.0026 (8)	−0.0095 (8)	−0.0098 (8)
Ag1	0.02415 (9)	0.04587 (11)	0.04422 (10)	−0.00267 (6)	−0.01187 (7)	−0.01412 (7)
N1	0.0244 (9)	0.0373 (10)	0.0396 (10)	−0.0020 (7)	−0.0085 (7)	−0.0114 (8)
N2	0.0283 (9)	0.0366 (10)	0.0383 (10)	−0.0017 (7)	−0.0128 (7)	−0.0111 (8)
C8	0.0267 (10)	0.0484 (13)	0.0387 (11)	−0.0043 (9)	−0.0085 (9)	−0.0084 (10)
C9	0.0294 (11)	0.0508 (13)	0.0409 (12)	−0.0026 (9)	−0.0126 (9)	−0.0182 (10)
O1W	0.0419 (11)	0.0617 (12)	0.0655 (13)	−0.0013 (9)	−0.0163 (10)	−0.0333 (10)

Geometric parameters (Å, º)

O1—C7	1.240 (3)	Ag1—N2^i	2.1403 (19)
O2—C7	1.250 (3)	Ag1—N1	2.1409 (18)
O3—N3	1.214 (3)	N1—C8	1.470 (3)
O4—N3	1.220 (3)	N1—H11	0.82 (3)
N3—C3	1.470 (3)	N1—H21	0.87 (3)
C1—C2	1.384 (3)	N2—C9	1.470 (3)
C1—C6	1.387 (3)	N2—Ag1^ii	2.1403 (18)
C1—C7	1.516 (3)	N2—H12	0.79 (3)
C2—C3	1.384 (3)	N2—H22	0.82 (3)
C2—H2	0.9300	C8—C9	1.522 (3)
C3—C4	1.379 (3)	C8—H8A	0.9700
C4—C5	1.383 (4)	C8—H8B	0.9700
C4—H4	0.9300	C9—H9A	0.9700
C5—C6	1.389 (3)	C9—H9B	0.9700
C5—H5	0.9300	O1W—H1W	0.84 (4)
C6—H6	0.9300	O1W—H2W	0.78 (3)
O3—N3—O4	122.8 (2)	C8—N1—Ag1	116.20 (14)
O3—N3—C3	118.9 (2)	C8—N1—H11	111.4 (19)
O4—N3—C3	118.4 (2)	Ag1—N1—H11	108.9 (19)
C2—C1—C6	119.05 (19)	C8—N1—H21	106 (2)
C2—C1—C7	119.55 (18)	Ag1—N1—H21	111 (2)
C6—C1—C7	121.4 (2)	H11—N1—H21	102 (3)
C1—C2—C3	119.2 (2)	C9—N2—Ag1^ii	116.02 (14)
C1—C2—H2	120.4	C9—N2—H12	109 (2)
C3—C2—H2	120.4	Ag1^ii—N2—H12	105 (2)
C4—C3—C2	122.6 (2)	C9—N2—H22	108 (2)
C4—C3—N3	119.2 (2)	Ag1^ii—N2—H22	111 (2)
C2—C3—N3	118.2 (2)	H12—N2—H22	107 (3)
C3—C4—C5	117.9 (2)	N1—C8—C9	114.51 (18)
C3—C4—H4	121.1	N1—C8—H8A	108.6
C5—C4—H4	121.1	C9—C8—H8A	108.6
C4—C5—C6	120.5 (2)	N1—C8—H8B	108.6
C4—C5—H5	119.8	C9—C8—H8B	108.6
C6—C5—H5	119.8	H8A—C8—H8B	107.6
C1—C6—C5	120.8 (2)	N2—C9—C8	113.71 (19)
C1—C6—H6	119.6	N2—C9—H9A	108.8
C5—C6—H6	119.6	C8—C9—H9A	108.8
O1—C7—O2	125.1 (2)	N2—C9—H9B	108.8
O1—C7—C1	118.2 (2)	C8—C9—H9B	108.8
O2—C7—C1	116.7 (2)	H9A—C9—H9B	107.7
N2^i—Ag1—N1	177.09 (8)	H1W—O1W—H2W	101 (3)
C6—C1—C2—C3	0.0 (3)	C2—C1—C6—C5	−0.9 (3)
C7—C1—C2—C3	178.30 (19)	C7—C1—C6—C5	−179.1 (2)
C1—C2—C3—C4	1.0 (3)	C4—C5—C6—C1	0.7 (4)
C1—C2—C3—N3	−178.43 (19)	C2—C1—C7—O1	−170.1 (2)
O3—N3—C3—C4	−166.6 (2)	C6—C1—C7—O1	8.2 (3)
O4—N3—C3—C4	13.1 (3)	C2—C1—C7—O2	9.0 (3)
O3—N3—C3—C2	12.9 (3)	C6—C1—C7—O2	−172.7 (2)
O4—N3—C3—C2	−167.5 (2)	Ag1—N1—C8—C9	179.88 (16)
C2—C3—C4—C5	−1.1 (3)	Ag1^ii—N2—C9—C8	178.01 (15)
N3—C3—C4—C5	178.3 (2)	N1—C8—C9—N2	66.0 (3)
C3—C4—C5—C6	0.2 (4)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2^iii	0.84 (4)	1.93 (4)	2.754 (3)	171 (4)
O1W—H2W···O2	0.78 (4)	2.03 (4)	2.789 (3)	162 (3)
N1—H11···O1	0.82 (3)	2.34 (3)	3.156 (3)	171 (3)
N2—H12···O1	0.79 (3)	2.49 (3)	3.233 (3)	157 (3)
N2—H12···O2	0.79 (3)	2.54 (3)	3.253 (3)	151 (3)
N1—H21···O1W	0.87 (4)	2.21 (4)	3.061 (3)	165 (3)
N2—H22···O1^iv	0.82 (3)	2.10 (3)	2.916 (3)	175 (3)
C4—H4···O1W^v	0.93	2.56	3.332 (3)	140

Symmetry codes: (iii) −x+2, −y+1, −z; (iv) −x+2, −y+2, −z; (v) x−1, y, z+1.