catena-Poly­[[silver(I)-μ-ethane-1,2-diamine-κ²N:N′] 3-fluorobenzoate monohydrate]

The title compound, {[Ag(C₂H₈N₂)](C₇H₄FO₂)·H₂O}_n, has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Ag atom is bicoordinated in a linear configuration by two N atoms from two symmetry-related ethyl­enedi­amine ligands, giving linear polymeric chains with [–Ag—N—C—C—N–]_n backbones running parallel to the b axis. In the crystal packing, these linear chains are interconnected by N—H...O and O—H...O hydrogen bonds, and by weak Ag...OW interactions, forming layers parallel to the ab plane.

S1. Comment

Silver(I) complexes with carboxylate anions as counterions or ligands are a group of metal compounds which, due to their wide usage in many fields, have been structurally characterized for 30 years (Graham et al., 1996; Kristiansson, 2001; Nomiya et al., 2000; Pingrong et al., 1998). Recently, we have reported a few dozens of silver(I)-carboxylate complexes with various amines and imines, all of which have been structurally characterized (Usman et al., 2003; Zhu et al., 1999, 2000; Zhu, Usman et al., 2003; Zhu, Zhang et al., 2003; Zheng Tong Zhu & Chen, 2001; Zheng Tong Zhu Fang & Chen, 2001). As an extension of our work on the structural characterization of these silver(I) carboxylates, the title novel complex, (I), is reported here. \sch

Complex (I) is a polymeric ethylenediaminesilver(I) complex. The smallest repeat unit for the complex contains an ethylenediaminesilver(I) cation, a 3-fluorobenzoate anion and a lattice water molecule. In the cation, the Ag^I atom is in a linear coordination environment and is bi-coordianted by two N atoms from different ethylenediamine ligands. The N1—Ag1—N2 angle is 170.50 (11)°, indicating a significantly distorted linear geometry for atom Ag1, which is comparable with the value of 172.37 (8)° observed in a similar silver complex (Zhu Liu et al., 2003). The average Ag—N bond length is 2.148 (3) Å, which is a little longer than the value of 2.138 (2) Å observed in the same complex described above. In the anion, the dihedral angle between the benzene ring and the plane constructed by the carboxylic group (O1/C7/O2) is 9.4 (5)°. The torsion C6—C5—C7—O2 and C4—C5—C7—O1 angles are −171.1 (4) and −170.2 (4)°, respectively. Atom F1 lies in the plane of the phenyl moiety.

The Ag—N bonds link the amine molecules and the Ag^I atoms to form a chain along the b axis. The O atoms of the water molecules join neighbouring chains by bridging Ag atoms [Ag1···O1w(1/2 − x, 1/2 − y, 1 − z) 2.993 (4) Å] (Fig.1), forming a number of Ag₂O₂ tetragons, which are well defined planes with no deviation. These Ag₂O₂ tetragons link the chains to form layers along the ab direction (Fig. 2).

The 3-fluorobenzoate anions in (I) are located among the chains, their carboxylic acid group ends linking to the chains by forming N1—H1A···O1ⁱ and N1—H1B···O2ⁱⁱ hydrogen bonds. In addition, there are O1W—H1WA···O1ⁱ and O1W—H1WB···O2ⁱ hydrogen bonds between the water molecules and the carboxylic acid groups (see Table 1 for symmetry codes).

S2. Experimental

All reagents and solvents were used as obtained without further purification. The CHN elemental analyses were performed on a Perkin-Elmer elemental analyzer. Silver 3-fluorobenzoate (0.5 mmol, 124 mg) and 1,2-diaminoethane (0.5 mmol, 30 mg) were dissolved in an ammonia solution (10 ml, Concentration?). The mixture was stirred for about 10 min at room temperature to give a clear colourless solution. The resulting solution was kept in air and, after slow evaporation of the solvent for 2 d, large colourless crystals of (I) formed at the bottom of the vessel. The crystals were isolated, washed three times with water and dried in a vacuum desiccator using CaCl₂ (yield 85.2%). Analysis found: C 33.21, H 4.39, N 8.55%; calculated for C₉H₁₄AgFN₂O₃: C 33.25, H 4.34, N 8.62%.

S3. Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H = 0.90 Å, C—H = 0.96 Å and O—H = 0.85 Å, and with U_iso(H) values fixed at 0.08 Ų. The U_eq value for the F atom is a little large, but we did not attempt to split it.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); 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.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of (I), viewed along the c axis. H atoms have been omitted for clarity.

catena-Poly[[silver(I)-µ-ethane-1,2-diamine-κ²N:N'] 3-fluorobenzoate monohydrate]

Crystal data

[Ag(C2H8N2)](C7H4FO2)·H2O	F(000) = 1296
Mr = 325.09	Dx = 1.847 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4521 reflections
a = 23.721 (5) Å	θ = 2.6–25.8°
b = 7.180 (1) Å	µ = 1.73 mm^−1
c = 13.961 (3) Å	T = 293 K
β = 100.45 (3)°	Prism, colourless
V = 2338.4 (8) Å^3	0.40 × 0.31 × 0.16 mm
Z = 8

Data collection

Siemens SMART CCD area-detector diffractometer	2372 independent reflections
Radiation source: fine-focus sealed tube	1973 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 26.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→29
Tmin = 0.530, Tmax = 0.758	k = −8→8
5175 measured reflections	l = −17→16

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0446P)^2] where P = (Fo^2 + 2Fc^2)/3
2372 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.56 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	0.210141 (14)	0.21391 (4)	0.37163 (2)	0.05367 (15)
F1	0.52579 (13)	0.3821 (6)	0.3696 (3)	0.1135 (11)
O1	0.32941 (11)	0.5878 (4)	0.4021 (2)	0.0609 (8)
O2	0.33092 (11)	0.8914 (4)	0.3819 (2)	0.0557 (7)
O1W	0.16714 (17)	0.2686 (4)	0.5287 (2)	0.0772 (10)
H1WA	0.1582	0.3780	0.5437	0.080*
H1WB	0.1621	0.1771	0.5649	0.080*
N1	0.20777 (12)	0.9180 (4)	0.3943 (2)	0.0442 (7)
H1A	0.2425	0.8706	0.3909	0.080*
H1B	0.2014	0.8978	0.4550	0.080*
N2	0.20890 (13)	0.4980 (4)	0.3239 (2)	0.0467 (7)
H2A	0.2066	0.4995	0.2588	0.080*
H2C	0.2422	0.5523	0.3508	0.080*
C1	0.5006 (2)	0.5516 (8)	0.3759 (3)	0.0677 (13)
C2	0.5327 (2)	0.7094 (9)	0.3778 (4)	0.0818 (18)
H2B	0.5728	0.7003	0.3755	0.080*
C3	0.5067 (2)	0.8789 (9)	0.3818 (4)	0.0830 (16)
H3A	0.5288	0.9914	0.3837	0.080*
C4	0.4497 (2)	0.8861 (7)	0.3848 (3)	0.0632 (12)
H4A	0.4311	1.0046	0.3864	0.080*
C5	0.41715 (18)	0.7253 (5)	0.3837 (3)	0.0442 (9)
C6	0.44348 (17)	0.5549 (6)	0.3786 (3)	0.0535 (10)
H6A	0.4218	0.4416	0.3769	0.080*
C7	0.35481 (18)	0.7356 (5)	0.3897 (3)	0.0440 (9)
C8	0.16115 (16)	0.6104 (5)	0.3484 (3)	0.0502 (9)
H8A	0.1608	0.5962	0.4166	0.080*
H8B	0.1257	0.5616	0.3132	0.080*
C9	0.16419 (18)	0.8147 (5)	0.3264 (3)	0.0496 (10)
H9A	0.1726	0.8282	0.2620	0.080*
H9B	0.1274	0.8704	0.3265	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0618 (2)	0.02830 (19)	0.0736 (3)	0.00095 (13)	0.01958 (17)	0.00067 (14)
F1	0.084 (2)	0.118 (3)	0.144 (3)	0.040 (2)	0.036 (2)	0.008 (2)
O1	0.0504 (16)	0.0456 (17)	0.090 (2)	−0.0037 (13)	0.0206 (15)	0.0036 (15)
O2	0.0582 (17)	0.0430 (17)	0.0667 (17)	0.0070 (14)	0.0136 (14)	0.0004 (14)
O1W	0.124 (3)	0.0460 (19)	0.071 (2)	0.0017 (17)	0.042 (2)	0.0036 (14)
N1	0.0517 (19)	0.0253 (16)	0.0579 (19)	0.0009 (13)	0.0159 (16)	0.0000 (13)
N2	0.059 (2)	0.0308 (17)	0.0511 (18)	−0.0009 (14)	0.0128 (15)	−0.0041 (14)
C1	0.056 (3)	0.086 (4)	0.062 (3)	0.024 (3)	0.014 (2)	0.002 (2)
C2	0.040 (3)	0.127 (6)	0.080 (4)	−0.013 (3)	0.016 (3)	−0.007 (3)
C3	0.062 (3)	0.092 (4)	0.100 (4)	−0.022 (3)	0.029 (3)	−0.018 (3)
C4	0.058 (3)	0.059 (3)	0.077 (3)	−0.009 (2)	0.022 (2)	−0.009 (2)
C5	0.048 (2)	0.048 (2)	0.0361 (19)	−0.0026 (18)	0.0084 (17)	−0.0015 (16)
C6	0.049 (2)	0.056 (3)	0.056 (2)	0.0077 (19)	0.0109 (19)	0.001 (2)
C7	0.047 (2)	0.047 (2)	0.038 (2)	−0.0032 (18)	0.0087 (17)	0.0026 (17)
C8	0.052 (2)	0.034 (2)	0.066 (2)	−0.0033 (17)	0.015 (2)	0.0015 (18)
C9	0.053 (2)	0.033 (2)	0.064 (2)	0.0034 (17)	0.012 (2)	0.0023 (18)

Geometric parameters (Å, º)

Ag1—N2	2.145 (3)	C1—C6	1.363 (6)
Ag1—N1^i	2.150 (3)	C2—C3	1.370 (8)
F1—C1	1.366 (6)	C2—H2B	0.9601
O1—C7	1.248 (4)	C3—C4	1.362 (6)
O2—C7	1.249 (5)	C3—H3A	0.9601
O1W—H1WA	0.8500	C4—C5	1.387 (6)
O1W—H1WB	0.8500	C4—H4A	0.9600
N1—C9	1.471 (5)	C5—C6	1.381 (5)
N1—Ag1^ii	2.150 (3)	C5—C7	1.498 (6)
N1—H1A	0.9000	C6—H6A	0.9600
N1—H1B	0.9000	C8—C9	1.503 (5)
N2—C8	1.481 (5)	C8—H8A	0.9600
N2—H2A	0.9000	C8—H8B	0.9600
N2—H2C	0.9001	C9—H9A	0.9600
C1—C2	1.362 (7)	C9—H9B	0.9600
N2—Ag1—N1^i	170.51 (11)	C3—C4—H4A	119.8
H1WA—O1W—H1WB	120.0	C5—C4—H4A	118.7
C9—N1—Ag1^ii	115.9 (2)	C6—C5—C4	118.8 (4)
C9—N1—H1A	108.5	C6—C5—C7	120.4 (4)
Ag1^ii—N1—H1A	108.5	C4—C5—C7	120.8 (4)
C9—N1—H1B	107.9	C1—C6—C5	118.6 (4)
Ag1^ii—N1—H1B	108.1	C1—C6—H6A	121.0
H1A—N1—H1B	107.6	C5—C6—H6A	120.5
C8—N2—Ag1	114.5 (2)	O1—C7—O2	123.4 (4)
C8—N2—H2A	108.6	O1—C7—C5	118.2 (4)
Ag1—N2—H2A	108.6	O2—C7—C5	118.4 (3)
C8—N2—H2C	108.5	N2—C8—C9	114.7 (3)
Ag1—N2—H2C	108.7	N2—C8—H8A	108.5
H2A—N2—H2C	107.7	C9—C8—H8A	108.4
C2—C1—C6	122.7 (5)	N2—C8—H8B	108.6
C2—C1—F1	119.5 (5)	C9—C8—H8B	108.8
C6—C1—F1	117.8 (5)	H8A—C8—H8B	107.7
C1—C2—C3	119.0 (5)	N1—C9—C8	114.5 (3)
C1—C2—H2B	119.8	N1—C9—H9A	108.2
C3—C2—H2B	121.1	C8—C9—H9A	108.4
C4—C3—C2	119.5 (5)	N1—C9—H9B	108.7
C4—C3—H3A	120.4	C8—C9—H9B	109.2
C2—C3—H3A	120.1	H9A—C9—H9B	107.7
C3—C4—C5	121.5 (5)
C6—C1—C2—C3	−0.5 (8)	C7—C5—C6—C1	−178.3 (4)
F1—C1—C2—C3	178.4 (4)	C6—C5—C7—O1	8.8 (6)
C1—C2—C3—C4	0.7 (8)	C4—C5—C7—O1	−170.2 (4)
C2—C3—C4—C5	−0.1 (8)	C6—C5—C7—O2	−171.2 (4)
C3—C4—C5—C6	−0.6 (7)	C4—C5—C7—O2	9.8 (6)
C3—C4—C5—C7	178.4 (4)	Ag1—N2—C8—C9	172.7 (2)
C2—C1—C6—C5	−0.2 (7)	Ag1^ii—N1—C9—C8	−176.1 (2)
F1—C1—C6—C5	−179.2 (4)	N2—C8—C9—N1	−74.1 (4)
C4—C5—C6—C1	0.8 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2^iii	0.85	1.95	2.739 (4)	154
O1W—H1WB···O1^iv	0.85	1.96	2.731 (4)	150
N1—H1B···O1^iii	0.90	2.25	3.126 (4)	165
N2—H2A···O2^v	0.90	2.15	2.958 (4)	149
N1—H1A···O2	0.90	2.13	2.964 (4)	154
N2—H2C···O1	0.90	2.08	2.941 (4)	160

Symmetry codes: (iii) −x+1/2, −y+3/2, −z+1; (iv) −x+1/2, −y+1/2, −z+1; (v) −x+1/2, y−1/2, −z+1/2.