Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103028683/na1632sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103028683/na1632Isup2.hkl |
CCDC reference: 235316
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%.
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 Uiso(H) values fixed at 0.08 Å2. The Ueq value for the F atom is a little large, but we did not attempt to split it.
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.
[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) Å3 | 0.40 × 0.31 × 0.16 mm |
Z = 8 |
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 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0446P)2] where P = (Fo2 + 2Fc2)/3 |
2372 reflections | (Δ/σ)max = 0.001 |
145 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[Ag(C2H8N2)](C7H4FO2)·H2O | V = 2338.4 (8) Å3 |
Mr = 325.09 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.721 (5) Å | µ = 1.73 mm−1 |
b = 7.180 (1) Å | T = 293 K |
c = 13.961 (3) Å | 0.40 × 0.31 × 0.16 mm |
β = 100.45 (3)° |
Siemens SMART CCD area-detector diffractometer | 2372 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1973 reflections with I > 2σ(I) |
Tmin = 0.530, Tmax = 0.758 | Rint = 0.023 |
5175 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.54 e Å−3 |
2372 reflections | Δρmin = −0.56 e Å−3 |
145 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 | 0.210141 (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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ag1—N2 | 2.145 (3) | C1—C6 | 1.363 (6) |
Ag1—N1i | 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—Ag1ii | 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—N1i | 170.51 (11) | C3—C4—H4A | 119.8 |
H1WA—O1W—H1WB | 120.0 | C5—C4—H4A | 118.7 |
C9—N1—Ag1ii | 115.9 (2) | C6—C5—C4 | 118.8 (4) |
C9—N1—H1A | 108.5 | C6—C5—C7 | 120.4 (4) |
Ag1ii—N1—H1A | 108.5 | C4—C5—C7 | 120.8 (4) |
C9—N1—H1B | 107.9 | C1—C6—C5 | 118.6 (4) |
Ag1ii—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) | Ag1ii—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2iii | 0.85 | 1.95 | 2.739 (4) | 154 |
O1W—H1WB···O1iv | 0.85 | 1.96 | 2.731 (4) | 150 |
N1—H1B···O1iii | 0.90 | 2.25 | 3.126 (4) | 165 |
N2—H2A···O2v | 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. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C2H8N2)](C7H4FO2)·H2O |
Mr | 325.09 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 23.721 (5), 7.180 (1), 13.961 (3) |
β (°) | 100.45 (3) |
V (Å3) | 2338.4 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.73 |
Crystal size (mm) | 0.40 × 0.31 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.530, 0.758 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5175, 2372, 1973 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.091, 1.07 |
No. of reflections | 2372 |
No. of parameters | 145 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.54, −0.56 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2i | 0.85 | 1.95 | 2.739 (4) | 154 |
O1W—H1WB···O1ii | 0.85 | 1.96 | 2.731 (4) | 150 |
N1—H1B···O1i | 0.90 | 2.25 | 3.126 (4) | 165 |
N2—H2A···O2iii | 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: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1/2, y−1/2, −z+1/2. |
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 AgI 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 AgI 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).