Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104023066/sq1176sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104023066/sq1176Isup2.hkl |
CCDC reference: 256990
N,N'-Bis(2-fluorobenzylidene)butane-1,4-diamine (0.1 mmol, 30.0 mg) and silver(I) benzoate (0.2 mmol, 45.8 mg) were dissolved in a 30% ammonia solution (10 ml) with stirring. The mixture was stirred at room temperature for 20 min and then filtered. The filtrate was allowed to stand in air for 17 d, during which time about three-quarters of the original solvent volume evaporated and colourless block-shaped crystals formed at the bottom of the vessel. The crystals were isolated, washed three times with water and dried in a vacuum desiccator using anhydrous CaCl2 (pure product yield 68.7%). Analysis found: C 50.5, H 3.7, N 3.8%; calculated for C16H14AgFNO2: C 50.7, H 3.7, N 3.7%.
All H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H distances of 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.
[Ag2(C7H5O2)2(C18H18F2N2)] | Z = 1 |
Mr = 758.30 | F(000) = 378 |
Triclinic, p1 | Dx = 1.724 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.703 (3) Å | Cell parameters from 1624 reflections |
b = 10.313 (5) Å | θ = 2.6–23.5° |
c = 12.805 (6) Å | µ = 1.39 mm−1 |
α = 86.978 (6)° | T = 293 K |
β = 84.452 (7)° | Block, colourless |
γ = 77.115 (7)° | 0.27 × 0.22 × 0.15 mm |
V = 730.4 (6) Å3 |
Bruker SMART CCD area-detector diffractometer | 2524 independent reflections |
Radiation source: fine-focus sealed tube | 1952 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→4 |
Tmin = 0.705, Tmax = 0.818 | k = −10→12 |
3880 measured reflections | l = −14→15 |
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)] = 0.080 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.1604P)2] where P = (Fo2 + 2Fc2)/3 |
2524 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 1.86 e Å−3 |
0 restraints | Δρmin = −1.84 e Å−3 |
[Ag2(C7H5O2)2(C18H18F2N2)] | γ = 77.115 (7)° |
Mr = 758.30 | V = 730.4 (6) Å3 |
Triclinic, p1 | Z = 1 |
a = 5.703 (3) Å | Mo Kα radiation |
b = 10.313 (5) Å | µ = 1.39 mm−1 |
c = 12.805 (6) Å | T = 293 K |
α = 86.978 (6)° | 0.27 × 0.22 × 0.15 mm |
β = 84.452 (7)° |
Bruker SMART CCD area-detector diffractometer | 2524 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1952 reflections with I > 2σ(I) |
Tmin = 0.705, Tmax = 0.818 | Rint = 0.047 |
3880 measured reflections |
R[F2 > 2σ(F2)] = 0.080 | 0 restraints |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.86 e Å−3 |
2524 reflections | Δρmin = −1.84 e Å−3 |
190 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 | 0.75137 (11) | 0.91168 (6) | 0.50699 (4) | 0.0652 (4) | |
F1 | 0.8616 (16) | 0.7128 (9) | 0.9210 (5) | 0.116 (2) | |
N1 | 0.9338 (12) | 0.7175 (7) | 0.6085 (5) | 0.0612 (16) | |
O1 | 0.8060 (10) | 1.0757 (6) | 0.6018 (5) | 0.0657 (14) | |
O2 | 0.4124 (10) | 1.1708 (7) | 0.6162 (5) | 0.0757 (17) | |
C1 | 0.8822 (17) | 0.6933 (9) | 0.7067 (7) | 0.067 (2) | |
H1 | 0.9872 | 0.6262 | 0.7411 | 0.080* | |
C2 | 0.6675 (18) | 0.7660 (9) | 0.7664 (7) | 0.068 (2) | |
C3 | 0.662 (2) | 0.7753 (11) | 0.8737 (8) | 0.088 (3) | |
C4 | 0.462 (3) | 0.8432 (16) | 0.9346 (11) | 0.119 (5) | |
H4 | 0.4675 | 0.8514 | 1.0062 | 0.143* | |
C5 | 0.261 (3) | 0.8967 (14) | 0.8869 (12) | 0.116 (5) | |
H5 | 0.1226 | 0.9381 | 0.9271 | 0.139* | |
C6 | 0.256 (2) | 0.8913 (11) | 0.7785 (11) | 0.097 (3) | |
H6 | 0.1186 | 0.9326 | 0.7457 | 0.116* | |
C7 | 0.4581 (17) | 0.8236 (9) | 0.7213 (7) | 0.070 (2) | |
H7 | 0.4534 | 0.8163 | 0.6495 | 0.084* | |
C8 | 1.1502 (16) | 0.6318 (8) | 0.5563 (7) | 0.065 (2) | |
H8A | 1.2391 | 0.5734 | 0.6078 | 0.078* | |
H8B | 1.2550 | 0.6860 | 0.5213 | 0.078* | |
C9 | 1.0707 (17) | 0.5497 (8) | 0.4766 (6) | 0.065 (2) | |
H9A | 0.9725 | 0.6098 | 0.4290 | 0.078* | |
H9B | 1.2130 | 0.5024 | 0.4356 | 0.078* | |
C10 | 0.6218 (13) | 1.1569 (7) | 0.6407 (6) | 0.0528 (17) | |
C11 | 0.6576 (13) | 1.2485 (7) | 0.7235 (5) | 0.0484 (16) | |
C12 | 0.8733 (17) | 1.2292 (9) | 0.7694 (7) | 0.066 (2) | |
H12 | 1.0031 | 1.1616 | 0.7472 | 0.079* | |
C13 | 0.8947 (19) | 1.3119 (11) | 0.8492 (7) | 0.080 (3) | |
H13 | 1.0382 | 1.2980 | 0.8813 | 0.096* | |
C14 | 0.708 (2) | 1.4121 (10) | 0.8802 (8) | 0.082 (3) | |
H14 | 0.7223 | 1.4653 | 0.9346 | 0.098* | |
C15 | 0.502 (2) | 1.4354 (10) | 0.8334 (8) | 0.080 (3) | |
H15 | 0.3781 | 1.5078 | 0.8525 | 0.096* | |
C16 | 0.4713 (16) | 1.3516 (9) | 0.7562 (7) | 0.066 (2) | |
H16 | 0.3246 | 1.3654 | 0.7268 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0608 (5) | 0.0685 (5) | 0.0709 (5) | −0.0200 (3) | −0.0106 (3) | −0.0098 (3) |
F1 | 0.130 (6) | 0.168 (7) | 0.064 (3) | −0.065 (5) | −0.019 (4) | 0.007 (4) |
N1 | 0.058 (4) | 0.058 (4) | 0.067 (4) | −0.010 (3) | −0.006 (3) | −0.001 (3) |
O1 | 0.051 (3) | 0.068 (3) | 0.081 (4) | −0.016 (3) | 0.000 (3) | −0.023 (3) |
O2 | 0.050 (3) | 0.102 (5) | 0.078 (4) | −0.013 (3) | −0.013 (3) | −0.030 (3) |
C1 | 0.063 (5) | 0.072 (5) | 0.067 (5) | −0.021 (4) | −0.008 (4) | 0.004 (4) |
C2 | 0.070 (6) | 0.071 (5) | 0.066 (5) | −0.028 (4) | −0.001 (4) | 0.000 (4) |
C3 | 0.098 (8) | 0.103 (8) | 0.077 (6) | −0.051 (7) | −0.005 (6) | −0.005 (6) |
C4 | 0.143 (13) | 0.143 (12) | 0.093 (8) | −0.087 (11) | 0.037 (9) | −0.047 (8) |
C5 | 0.107 (11) | 0.119 (11) | 0.129 (12) | −0.059 (9) | 0.053 (10) | −0.041 (9) |
C6 | 0.071 (7) | 0.084 (7) | 0.134 (10) | −0.020 (6) | 0.010 (7) | −0.007 (7) |
C7 | 0.066 (6) | 0.074 (6) | 0.074 (5) | −0.025 (4) | 0.000 (5) | −0.001 (4) |
C8 | 0.055 (5) | 0.063 (5) | 0.075 (5) | −0.011 (4) | −0.005 (4) | 0.004 (4) |
C9 | 0.069 (5) | 0.052 (4) | 0.067 (5) | −0.007 (4) | 0.014 (4) | −0.008 (3) |
C10 | 0.044 (4) | 0.063 (4) | 0.055 (4) | −0.018 (3) | −0.003 (3) | −0.001 (3) |
C11 | 0.041 (4) | 0.058 (4) | 0.051 (4) | −0.020 (3) | −0.001 (3) | −0.004 (3) |
C12 | 0.058 (5) | 0.083 (6) | 0.062 (5) | −0.026 (4) | −0.006 (4) | −0.008 (4) |
C13 | 0.071 (6) | 0.115 (8) | 0.070 (5) | −0.047 (6) | −0.024 (5) | −0.005 (5) |
C14 | 0.091 (7) | 0.088 (7) | 0.076 (6) | −0.038 (6) | 0.001 (5) | −0.027 (5) |
C15 | 0.080 (7) | 0.079 (6) | 0.085 (6) | −0.023 (5) | 0.001 (5) | −0.024 (5) |
C16 | 0.060 (5) | 0.068 (5) | 0.070 (5) | −0.010 (4) | −0.011 (4) | −0.014 (4) |
Ag1—O2i | 2.206 (6) | C6—H6 | 0.9300 |
Ag1—O1 | 2.227 (5) | C7—H7 | 0.9300 |
Ag1—N1 | 2.417 (7) | C8—C9 | 1.522 (12) |
Ag1—Ag1i | 3.051 (2) | C8—H8A | 0.9700 |
F1—C3 | 1.357 (14) | C8—H8B | 0.9700 |
N1—C1 | 1.287 (10) | C9—C9ii | 1.507 (17) |
N1—C8 | 1.472 (10) | C9—H9A | 0.9700 |
O1—C10 | 1.266 (9) | C9—H9B | 0.9700 |
O2—C10 | 1.240 (9) | C10—C11 | 1.514 (10) |
O2—Ag1i | 2.206 (6) | C11—C16 | 1.376 (11) |
C1—C2 | 1.455 (13) | C11—C12 | 1.384 (11) |
C1—H1 | 0.9300 | C12—C13 | 1.396 (12) |
C2—C7 | 1.376 (13) | C12—H12 | 0.9300 |
C2—C3 | 1.378 (14) | C13—C14 | 1.355 (14) |
C3—C4 | 1.387 (19) | C13—H13 | 0.9300 |
C4—C5 | 1.35 (2) | C14—C15 | 1.339 (14) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.396 (18) | C15—C16 | 1.394 (13) |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—C7 | 1.373 (14) | C16—H16 | 0.9300 |
O2i—Ag1—O1 | 153.9 (3) | N1—C8—H8A | 110.0 |
O2i—Ag1—N1 | 103.8 (2) | C9—C8—H8A | 110.0 |
O1—Ag1—N1 | 101.6 (2) | N1—C8—H8B | 110.0 |
O2i—Ag1—Ag1i | 73.73 (16) | C9—C8—H8B | 110.0 |
O1—Ag1—Ag1i | 83.45 (15) | H8A—C8—H8B | 108.4 |
N1—Ag1—Ag1i | 137.03 (17) | C9ii—C9—C8 | 114.7 (9) |
C1—N1—C8 | 117.5 (7) | C9ii—C9—H9A | 108.6 |
C1—N1—Ag1 | 126.3 (6) | C8—C9—H9A | 108.6 |
C8—N1—Ag1 | 115.4 (5) | C9ii—C9—H9B | 108.6 |
C10—O1—Ag1 | 118.5 (5) | C8—C9—H9B | 108.6 |
C10—O2—Ag1i | 134.0 (5) | H9A—C9—H9B | 107.6 |
N1—C1—C2 | 123.1 (8) | O2—C10—O1 | 126.2 (7) |
N1—C1—H1 | 118.5 | O2—C10—C11 | 116.0 (7) |
C2—C1—H1 | 118.5 | O1—C10—C11 | 117.8 (7) |
C7—C2—C3 | 116.5 (10) | C16—C11—C12 | 118.7 (7) |
C7—C2—C1 | 122.8 (8) | C16—C11—C10 | 119.8 (7) |
C3—C2—C1 | 120.7 (10) | C12—C11—C10 | 121.4 (7) |
F1—C3—C2 | 117.7 (10) | C11—C12—C13 | 119.6 (9) |
F1—C3—C4 | 119.2 (12) | C11—C12—H12 | 120.2 |
C2—C3—C4 | 123.1 (13) | C13—C12—H12 | 120.2 |
C5—C4—C3 | 118.1 (13) | C14—C13—C12 | 120.3 (9) |
C5—C4—H4 | 121.0 | C14—C13—H13 | 119.8 |
C3—C4—H4 | 121.0 | C12—C13—H13 | 119.8 |
C4—C5—C6 | 121.4 (13) | C15—C14—C13 | 120.7 (9) |
C4—C5—H5 | 119.3 | C15—C14—H14 | 119.7 |
C6—C5—H5 | 119.3 | C13—C14—H14 | 119.7 |
C7—C6—C5 | 118.4 (13) | C14—C15—C16 | 120.3 (10) |
C7—C6—H6 | 120.8 | C14—C15—H15 | 119.8 |
C5—C6—H6 | 120.8 | C16—C15—H15 | 119.8 |
C6—C7—C2 | 122.4 (10) | C11—C16—C15 | 120.2 (9) |
C6—C7—H7 | 118.8 | C11—C16—H16 | 119.9 |
C2—C7—H7 | 118.8 | C15—C16—H16 | 119.9 |
N1—C8—C9 | 108.5 (7) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag2(C7H5O2)2(C18H18F2N2)] |
Mr | 758.30 |
Crystal system, space group | Triclinic, p1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.703 (3), 10.313 (5), 12.805 (6) |
α, β, γ (°) | 86.978 (6), 84.452 (7), 77.115 (7) |
V (Å3) | 730.4 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.39 |
Crystal size (mm) | 0.27 × 0.22 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.705, 0.818 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3880, 2524, 1952 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.080, 0.215, 0.98 |
No. of reflections | 2524 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.86, −1.84 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1997), SHELXTL.
Ag1—O2i | 2.206 (6) | Ag1—Ag1i | 3.051 (2) |
Ag1—O1 | 2.227 (5) | N1—C1 | 1.287 (10) |
Ag1—N1 | 2.417 (7) | N1—C8 | 1.472 (10) |
O2i—Ag1—O1 | 153.9 (3) | O1—Ag1—N1 | 101.6 (2) |
O2i—Ag1—N1 | 103.8 (2) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Transition metal compounds containing Schiff base ligands have been of great interest for many years (Yamada, 1999; Chang et al., 1998; Chaturvedl, 1977; Archer & Wang, 1990). These compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures (Costamagna et al., 1992; Bhatia et al., 1981). Inorganic supramolecular chemistry and in particular the construction of polymeric coordination networks is an extremely topical area of research (Xu et al., 2001; Yaghi & Li, 1996). The construction of a wide variety of network topologies has been achieved through ligand design and the use of different counter-anions. Owing to the flexible coordination sphere of AgI, coordination numbers from two to six are all possible, and because of the relatively weak nature of many AgI-ligand interactions such compounds are particularly susceptible to the influence of weaker supramolecular forces (Khlobystov et al., 2001).
Our work is aimed at obtaining multidimensional metal complexes. On the basis of the above considerations, we designed and synthesized a flexible bidentate ligand, N,N'-bis(2-fluorophenylmethylidene)butane-1,4-diamine (BFBD). The flexible BFBD ligand offers advantages over rigid ligands in that it can adopt a different coordination mode according to the geometric needs of the coordination environment of the transition metal ion. Silver(I) is a good candidate for a trigonal coordination geometry. We report here an interesting one-dimensional infinite chain structure formed by the reaction of the BFBD ligand with silver(I) benzoate.
The title complex, (I), is a polymeric compound with an inversion center (Fig. 1). The smallest repeat unit of the complex contains a BFBD–AgI2 cation and two benzoate anions. Each AgI ion is three-coordinated in a trigonal configuration by two O atoms belonging to two benzoate anions and one N atom of a Schiff base ligand. Atom Ag1 lies 0.100 (6) Å out of the plane defined by the three donor atoms [O1/N1/O2i; symmetry code: (i) 1 − x, 2 − y, 1 − z]. The benzoate anion bridges two silver(I) ions related by the inversion center. The distance [3.051 (2) Å] between the two silver ions is shorter than the van der Waals radii of two Ag atoms (3.44 Å) and comparable to the value of 3.035 (2) Å observed in a silver complex with weak Ag···Ag interactions (Zhu, Shao et al., 2003), indicating the existence of similar interactions in (I).
The Ag1—N1 bond length [2.417 (7) Å; Table 1] is comparable to the value of 2.397 (3) Å observed in another Schiff base–silver(I) complex (Fei et al., 2000). The average Ag—O bond length in (I) [2.216 (6) Å] is essentially the same as the value of 2.210 (4) Å observed in a silver(I)–carboxylate complex (Zhu, Zhang et al., 2003). The O1—Ag1—O2i bond angle [153.9 (3) °] is larger than the other two bond angles about atom Ag1, viz. N1—Ag1—O2i [103.8 (2) °] and N1—Ag1—O1 [101.6 (2) °], apparently as a result of the Ag···Ag interactions. The Ag···Ag interactions also flatten the eight-membered Ag1/O1/C10/O2/Ag1i/O1i/C10i/O2i ring. The diagonal distance between atoms C10 and C10i [5.439 (9) Å] is much longer than the diagonal distance [3.051 (2) Å] between Ag1 and Ag1i. The mean deviation of the eight-membered ring from the combined mean plane is 0.109 (7) Å.
The bridging BFBD ligand adopts a trans configuration and coordinates to two Ag atoms belonging to two different repeat units. The C1=N1 bond length [1.287 (10) Å] conforms to the value for a double bond, while the C8—N1 bond length [1.472 (10) Å] conforms to the value for a single bond.
In the crystal structure, the linking of the dibenzoatodisilver(I) moieties by the bridging Schiff base ligand results in zigzag polymeric chains with an [–Ag—Ag—N—C—C—C—C—N–]n backbone running along the b axis. The molecules stack along the a axis with no short intermolecular contacts (<3.2 Å; see Fig. 2).