Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037580/cs2045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037580/cs2045Isup2.hkl |
CCDC reference: 660080
A flask containing 1,10-phenanthroline hydrate (1.00 g, 5.04 mmol) and potassium bromide (5.95 g, 50.0 mmol) was placed in an ice bath. Concentrated sulfuric acid (20 cm3) was added in small portions, followed by drop wise addition of concentrated nitric acid (10 cm3). The resulting solution was heated for 2 h at 80–85° C and cooled to room temperature. The solution was then poured into 400 cm3 of water and neutralized with sodium bicarbonate, after which the phendione was extracted with dichloromethane, and recrystallized using a methanol-water mixture.
The title compound was synthesized in an atmosphere saturated with N2. To a solution of AgClO4 in 15 ml of CH3CN, was added drop-wise a solution (15 ml) of CH3CN containing 0.26 g of phendione. The final yellowish solution was filtered and allowed to slowly evaporate for about a week yielding reddish brown prismatic crystals of the title compound suitable for X-ray studies.
H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C).
Phendione (1,10-phenanthroline-5,6-dione) is an excellent ligand that incorporates two functional groups with different coordination properties. Since the stereochemical behavior of Cu+ and Ag+ are similar it is interesting to compare the behavior of these cations with phendione. Isomorphous and isostructural Cu+ and Ag+ derivatives {[M(L)2](ClO4)2, where M = Cu+ and Ag+} have recently been determined (Galet et al., 2005; McCann et al., 2004) as well as a Ag+ complex, with trifluoromethanesulfonate instead of perchlorate as counterion (Wen et al., 2006). In addition a polymeric Ag+ phendione complex where the ligand coordinates to Ag through N and O donors has been reported (Wen et al., 2006). In this paper we report the synthesis and characterization of the title compound, [AgL2]+(ClO4)- (I).
The structure of the title compound, shown in Figure 1, is made up of an [Ag(L)2]+ cation and a perchlorate anion. Each silver atom is coordinated to the two nitrogen atoms of both phendione ligands. In contrast to the previous structure determination of this complex where there is crystallographically imposed symmetry on both the anion and cation in the present case there is no such symmetry. Table 1 gives a listing of selected bond lengths and bond angles. The C=O bond lengths in the phendione ligands (1.220 (5) Å and 1.207 (5) Å) are comparable to those values found in other such complexes (Allen, 2002). The metrical parameters for the phendione ligand is in the normal ranges observed for complexes where only the N atoms are coordinated to a metal (Allen, 2002). The Ag—N bond lengths (2.261 (3), 2.331 (4) Å, 2.349 (3) Å, and 2.453 (4) Å) are similar to those found in related phenanthroline derivatives of silver (McCann et al., 2004; Wen et al., 2006; Leschke et al., 2002; Paramonov et al., 2003; Pallenberg et al., 1997; Titze et al., 1997). In I, silver is in a distorted tetrahedral environment. This is best illustrated by the dihedral angle between the planes of the coordinated ligands which would be 90° for tetrahedral and 0° for planar. In this case the angle is 36.7 (2)° which is intermediate between these extremes.
There are weak C—H···O hydrogen bonds between the hydrogen atoms on C1A, C1B, C2A, C6A, C6B, C8A, and C8B and either perchlorate O atoms or phendione O atoms from an adjoining cation. In addition, there are short contacts between the perchlorate anion and the phendione ligands (O14···C4B 2.845 (5) Å) as well as unusual and different torsion angles for O1—C4—C5—O2 for the two phendione ligands (-21.9 (7)° and -5.0 (7)°) which reflects the fact that in this polymorph there is no crystallographically imposed symmetry on the cation.
For related literature, see: Galet et al. (2005); McCann et al. (2004); Pallenberg et al. (1997); Paramonov et al. (2003); Ruiz et al. (1999); Titze et al. (1997); Wen et al. (2006);
For related literature, see: Allen (2002); Leschke et al. (2002); Whitesides et al. (1991).
Data collection: APEX2 (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
[Ag(C12H6N2O2)2]ClO4 | Z = 2 |
Mr = 627.70 | F(000) = 624 |
Triclinic, P1 | Dx = 1.899 Mg m−3 |
a = 8.493 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.260 (3) Å | Cell parameters from 6560 reflections |
c = 13.190 (4) Å | θ = 2.6–29.9° |
α = 112.525 (3)° | µ = 1.10 mm−1 |
β = 103.682 (4)° | T = 93 K |
γ = 97.378 (4)° | Prism, red-brown |
V = 1097.8 (5) Å3 | 0.38 × 0.32 × 0.12 mm |
Bruker APEX II CCD area-detector diffractometer | 6019 independent reflections |
Radiation source: fine-focus sealed tube | 4791 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
φ and ω scans | θmax = 30.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→12 |
Tmin = 0.679, Tmax = 0.879 | k = −15→15 |
11431 measured reflections | l = −18→17 |
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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.107P)2] where P = (Fo2 + 2Fc2)/3 |
6019 reflections | (Δ/σ)max = 0.001 |
343 parameters | Δρmax = 2.36 e Å−3 |
0 restraints | Δρmin = −1.63 e Å−3 |
[Ag(C12H6N2O2)2]ClO4 | γ = 97.378 (4)° |
Mr = 627.70 | V = 1097.8 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.493 (2) Å | Mo Kα radiation |
b = 11.260 (3) Å | µ = 1.10 mm−1 |
c = 13.190 (4) Å | T = 93 K |
α = 112.525 (3)° | 0.38 × 0.32 × 0.12 mm |
β = 103.682 (4)° |
Bruker APEX II CCD area-detector diffractometer | 6019 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 4791 reflections with I > 2σ(I) |
Tmin = 0.679, Tmax = 0.879 | Rint = 0.067 |
11431 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.07 | Δρmax = 2.36 e Å−3 |
6019 reflections | Δρmin = −1.63 e Å−3 |
343 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. |
x | y | z | Uiso*/Ueq | ||
Ag | 0.13352 (4) | 0.50994 (3) | 0.25677 (2) | 0.02407 (14) | |
Cl | −0.44552 (14) | 0.71466 (11) | 0.77901 (11) | 0.0285 (3) | |
O1A | 0.2299 (5) | 0.2746 (3) | −0.2772 (3) | 0.0303 (7) | |
C9BB | 0.1294 (5) | 0.7156 (4) | 0.5018 (3) | 0.0169 (7) | |
N2B | 0.3438 (5) | 0.6887 (3) | 0.4071 (3) | 0.0193 (7) | |
N1B | 0.0294 (4) | 0.6065 (3) | 0.4095 (3) | 0.0197 (7) | |
C9AA | 0.1678 (5) | 0.4269 (4) | 0.0013 (3) | 0.0160 (7) | |
O14 | −0.6087 (4) | 0.7408 (3) | 0.7568 (3) | 0.0302 (7) | |
O2B | 0.4469 (5) | 1.0657 (3) | 0.7624 (3) | 0.0358 (8) | |
N2A | 0.0182 (4) | 0.3212 (3) | 0.0921 (3) | 0.0174 (6) | |
O1B | 0.1547 (5) | 0.9601 (3) | 0.7828 (3) | 0.0308 (7) | |
C8A | −0.0858 (5) | 0.2175 (4) | 0.0876 (4) | 0.0215 (8) | |
H8AA | −0.1122 | 0.2253 | 0.1541 | 0.026* | |
C1B | −0.1214 (5) | 0.5583 (4) | 0.4135 (4) | 0.0232 (8) | |
H1BA | −0.1916 | 0.4830 | 0.3500 | 0.028* | |
C5AA | −0.0150 (5) | 0.1964 (4) | −0.1072 (3) | 0.0176 (7) | |
C8BB | 0.2980 (5) | 0.7637 (4) | 0.4973 (3) | 0.0169 (7) | |
C6B | 0.5636 (5) | 0.9226 (4) | 0.5775 (3) | 0.0215 (8) | |
H6BA | 0.6364 | 1.0019 | 0.6341 | 0.026* | |
C3AA | 0.2244 (5) | 0.4194 (4) | −0.0913 (3) | 0.0179 (7) | |
C7B | 0.6096 (5) | 0.8460 (4) | 0.4850 (4) | 0.0230 (8) | |
H7BA | 0.7138 | 0.8712 | 0.4781 | 0.028* | |
O2A | −0.0645 (5) | 0.1084 (4) | −0.3101 (3) | 0.0352 (8) | |
C4B | 0.1929 (6) | 0.9039 (4) | 0.6977 (4) | 0.0223 (8) | |
C3B | −0.0743 (6) | 0.7283 (5) | 0.6016 (4) | 0.0248 (9) | |
H3BA | −0.1084 | 0.7688 | 0.6659 | 0.030* | |
C6A | −0.1213 (6) | 0.0888 (4) | −0.1098 (4) | 0.0239 (8) | |
H6AA | −0.1679 | 0.0112 | −0.1777 | 0.029* | |
N1A | 0.2144 (4) | 0.5387 (3) | 0.0994 (3) | 0.0199 (7) | |
C8AA | 0.0549 (5) | 0.3108 (4) | −0.0038 (3) | 0.0166 (7) | |
C5A | 0.0205 (6) | 0.1890 (4) | −0.2137 (4) | 0.0209 (8) | |
C4A | 0.1674 (6) | 0.2938 (4) | −0.1997 (4) | 0.0226 (8) | |
C8B | 0.4943 (6) | 0.7290 (4) | 0.4016 (4) | 0.0229 (8) | |
H8BA | 0.5245 | 0.6765 | 0.3388 | 0.027* | |
C5BB | 0.4073 (5) | 0.8811 (4) | 0.5863 (3) | 0.0174 (7) | |
C3BB | 0.0804 (5) | 0.7798 (4) | 0.5979 (3) | 0.0196 (8) | |
C2A | 0.3813 (6) | 0.6438 (4) | 0.0180 (4) | 0.0243 (9) | |
H2AA | 0.4543 | 0.7186 | 0.0267 | 0.029* | |
C2B | −0.1769 (6) | 0.6150 (4) | 0.5072 (4) | 0.0271 (9) | |
H2BA | −0.2814 | 0.5778 | 0.5069 | 0.033* | |
C3A | 0.3321 (5) | 0.5288 (4) | −0.0830 (4) | 0.0232 (8) | |
H3AA | 0.3704 | 0.5246 | −0.1444 | 0.028* | |
O13 | −0.3380 (5) | 0.7847 (4) | 0.7458 (4) | 0.0480 (11) | |
C7A | −0.1556 (6) | 0.0998 (4) | −0.0107 (4) | 0.0247 (9) | |
H7AA | −0.2245 | 0.0293 | −0.0097 | 0.030* | |
C5B | 0.3604 (6) | 0.9603 (4) | 0.6878 (4) | 0.0220 (8) | |
C1A | 0.3188 (5) | 0.6445 (4) | 0.1060 (4) | 0.0201 (8) | |
H1AA | 0.3505 | 0.7224 | 0.1737 | 0.024* | |
O12 | −0.3734 (6) | 0.7661 (5) | 0.9063 (4) | 0.0550 (12) | |
O11 | −0.4590 (6) | 0.5775 (4) | 0.7348 (5) | 0.0566 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag | 0.0258 (2) | 0.01959 (18) | 0.01995 (18) | 0.00118 (13) | 0.00769 (12) | 0.00246 (13) |
Cl | 0.0157 (5) | 0.0261 (5) | 0.0515 (7) | 0.0045 (4) | 0.0112 (4) | 0.0243 (5) |
O1A | 0.0285 (18) | 0.0360 (18) | 0.0269 (15) | 0.0071 (15) | 0.0155 (13) | 0.0100 (14) |
C9BB | 0.0136 (18) | 0.0170 (16) | 0.0230 (17) | 0.0055 (14) | 0.0091 (13) | 0.0090 (14) |
N2B | 0.0152 (17) | 0.0213 (15) | 0.0199 (15) | 0.0058 (13) | 0.0082 (12) | 0.0053 (13) |
N1B | 0.0159 (17) | 0.0212 (16) | 0.0218 (15) | 0.0051 (13) | 0.0059 (12) | 0.0089 (13) |
C9AA | 0.0108 (17) | 0.0171 (16) | 0.0227 (17) | 0.0063 (13) | 0.0061 (13) | 0.0097 (14) |
O14 | 0.0171 (16) | 0.0337 (17) | 0.0419 (18) | 0.0067 (14) | 0.0090 (13) | 0.0183 (15) |
O2B | 0.044 (2) | 0.0232 (15) | 0.0261 (16) | −0.0054 (15) | 0.0121 (14) | 0.0001 (13) |
N2A | 0.0143 (16) | 0.0183 (15) | 0.0204 (15) | 0.0036 (13) | 0.0079 (12) | 0.0078 (13) |
O1B | 0.041 (2) | 0.0267 (16) | 0.0269 (16) | 0.0122 (15) | 0.0188 (14) | 0.0082 (13) |
C8A | 0.018 (2) | 0.0217 (18) | 0.0253 (19) | 0.0010 (15) | 0.0075 (14) | 0.0110 (16) |
C1B | 0.0146 (19) | 0.027 (2) | 0.0265 (19) | 0.0001 (16) | 0.0046 (15) | 0.0126 (17) |
C5AA | 0.0125 (18) | 0.0186 (16) | 0.0216 (17) | 0.0048 (14) | 0.0054 (13) | 0.0084 (14) |
C8BB | 0.0135 (18) | 0.0170 (16) | 0.0200 (17) | 0.0054 (14) | 0.0059 (13) | 0.0071 (14) |
C6B | 0.018 (2) | 0.0215 (18) | 0.0217 (18) | −0.0018 (15) | 0.0029 (14) | 0.0101 (15) |
C3AA | 0.0131 (18) | 0.0191 (17) | 0.0221 (17) | 0.0052 (14) | 0.0071 (13) | 0.0081 (15) |
C7B | 0.0141 (19) | 0.027 (2) | 0.032 (2) | 0.0036 (16) | 0.0082 (15) | 0.0167 (18) |
O2A | 0.0292 (19) | 0.0374 (18) | 0.0263 (16) | −0.0060 (15) | 0.0049 (13) | 0.0072 (14) |
C4B | 0.030 (2) | 0.0157 (16) | 0.0217 (18) | 0.0058 (16) | 0.0103 (15) | 0.0074 (15) |
C3B | 0.022 (2) | 0.034 (2) | 0.029 (2) | 0.0143 (18) | 0.0161 (16) | 0.0173 (18) |
C6A | 0.021 (2) | 0.0190 (17) | 0.028 (2) | 0.0041 (16) | 0.0067 (16) | 0.0072 (16) |
N1A | 0.0147 (16) | 0.0157 (14) | 0.0283 (17) | 0.0022 (13) | 0.0067 (13) | 0.0088 (13) |
C8AA | 0.0115 (17) | 0.0159 (16) | 0.0230 (17) | 0.0058 (14) | 0.0053 (13) | 0.0082 (14) |
C5A | 0.020 (2) | 0.0210 (17) | 0.0225 (18) | 0.0056 (16) | 0.0096 (14) | 0.0079 (15) |
C4A | 0.019 (2) | 0.0229 (18) | 0.0253 (19) | 0.0061 (16) | 0.0080 (15) | 0.0092 (16) |
C8B | 0.019 (2) | 0.0259 (19) | 0.0256 (19) | 0.0088 (17) | 0.0120 (15) | 0.0093 (17) |
C5BB | 0.0178 (19) | 0.0158 (16) | 0.0190 (16) | 0.0041 (14) | 0.0067 (13) | 0.0072 (14) |
C3BB | 0.017 (2) | 0.0208 (17) | 0.0221 (18) | 0.0069 (15) | 0.0078 (14) | 0.0089 (15) |
C2A | 0.019 (2) | 0.0214 (18) | 0.032 (2) | 0.0022 (16) | 0.0058 (16) | 0.0133 (17) |
C2B | 0.014 (2) | 0.034 (2) | 0.038 (2) | 0.0055 (18) | 0.0094 (16) | 0.020 (2) |
C3A | 0.016 (2) | 0.028 (2) | 0.031 (2) | 0.0050 (16) | 0.0104 (15) | 0.0172 (18) |
O13 | 0.027 (2) | 0.047 (2) | 0.090 (4) | 0.0095 (18) | 0.030 (2) | 0.043 (2) |
C7A | 0.023 (2) | 0.0181 (18) | 0.032 (2) | 0.0001 (16) | 0.0096 (16) | 0.0109 (17) |
C5B | 0.026 (2) | 0.0156 (16) | 0.0233 (19) | 0.0044 (16) | 0.0083 (15) | 0.0067 (15) |
C1A | 0.0139 (18) | 0.0171 (17) | 0.030 (2) | 0.0028 (14) | 0.0060 (14) | 0.0114 (15) |
O12 | 0.043 (3) | 0.073 (3) | 0.043 (2) | 0.004 (2) | 0.0069 (18) | 0.026 (2) |
O11 | 0.047 (3) | 0.0230 (18) | 0.099 (4) | 0.0105 (18) | 0.026 (3) | 0.023 (2) |
Ag—N2A | 2.261 (3) | C5AA—C5A | 1.478 (6) |
Ag—N1B | 2.331 (4) | C8BB—C5BB | 1.403 (5) |
Ag—N2B | 2.349 (3) | C6B—C7B | 1.375 (6) |
Ag—N1A | 2.453 (4) | C6B—C5BB | 1.397 (6) |
Cl—O13 | 1.385 (4) | C6B—H6BA | 0.9300 |
Cl—O11 | 1.404 (4) | C3AA—C3A | 1.388 (5) |
Cl—O14 | 1.439 (4) | C3AA—C4A | 1.492 (6) |
Cl—O12 | 1.485 (5) | C7B—C8B | 1.398 (6) |
O1A—C4A | 1.220 (5) | C7B—H7BA | 0.9300 |
C9BB—N1B | 1.345 (5) | O2A—C5A | 1.215 (5) |
C9BB—C3BB | 1.389 (6) | C4B—C3BB | 1.500 (6) |
C9BB—C8BB | 1.487 (6) | C4B—C5B | 1.537 (7) |
N2B—C8B | 1.329 (6) | C3B—C3BB | 1.386 (6) |
N2B—C8BB | 1.346 (5) | C3B—C2B | 1.387 (6) |
N1B—C1B | 1.347 (6) | C3B—H3BA | 0.9300 |
C9AA—N1A | 1.341 (5) | C6A—C7A | 1.369 (6) |
C9AA—C3AA | 1.392 (5) | C6A—H6AA | 0.9300 |
C9AA—C8AA | 1.488 (5) | N1A—C1A | 1.351 (5) |
O2B—C5B | 1.207 (5) | C5A—C4A | 1.527 (6) |
N2A—C8AA | 1.339 (5) | C8B—H8BA | 0.9300 |
N2A—C8A | 1.344 (5) | C5BB—C5B | 1.475 (6) |
O1B—C4B | 1.204 (5) | C2A—C3A | 1.379 (6) |
C8A—C7A | 1.381 (6) | C2A—C1A | 1.383 (6) |
C8A—H8AA | 0.9300 | C2A—H2AA | 0.9300 |
C1B—C2B | 1.380 (6) | C2B—H2BA | 0.9300 |
C1B—H1BA | 0.9300 | C3A—H3AA | 0.9300 |
C5AA—C8AA | 1.396 (5) | C7A—H7AA | 0.9300 |
C5AA—C6A | 1.399 (6) | C1A—H1AA | 0.9300 |
N2A—Ag—N1B | 129.69 (12) | O1B—C4B—C3BB | 122.1 (4) |
N2A—Ag—N2B | 158.05 (13) | O1B—C4B—C5B | 120.0 (4) |
N1B—Ag—N2B | 71.16 (12) | C3BB—C4B—C5B | 117.9 (4) |
N2A—Ag—N1A | 70.77 (11) | C3BB—C3B—C2B | 118.4 (4) |
N1B—Ag—N1A | 144.28 (12) | C3BB—C3B—H3BA | 120.8 |
N2B—Ag—N1A | 95.79 (12) | C2B—C3B—H3BA | 120.8 |
O13—Cl—O11 | 115.7 (3) | C7A—C6A—C5AA | 118.8 (4) |
O13—Cl—O14 | 111.8 (2) | C7A—C6A—H6AA | 120.6 |
O11—Cl—O14 | 110.3 (3) | C5AA—C6A—H6AA | 120.6 |
O13—Cl—O12 | 105.8 (3) | C9AA—N1A—C1A | 117.8 (4) |
O11—Cl—O12 | 105.6 (3) | C9AA—N1A—Ag | 113.5 (2) |
O14—Cl—O12 | 106.9 (3) | C1A—N1A—Ag | 127.8 (3) |
N1B—C9BB—C3BB | 122.2 (4) | N2A—C8AA—C5AA | 121.3 (4) |
N1B—C9BB—C8BB | 116.7 (4) | N2A—C8AA—C9AA | 118.2 (3) |
C3BB—C9BB—C8BB | 121.1 (4) | C5AA—C8AA—C9AA | 120.4 (4) |
C8B—N2B—C8BB | 119.0 (4) | O2A—C5A—C5AA | 123.5 (4) |
C8B—N2B—Ag | 124.3 (3) | O2A—C5A—C4A | 119.2 (4) |
C8BB—N2B—Ag | 116.1 (3) | C5AA—C5A—C4A | 117.1 (3) |
C9BB—N1B—C1B | 117.7 (4) | O1A—C4A—C3AA | 122.7 (4) |
C9BB—N1B—Ag | 117.6 (3) | O1A—C4A—C5A | 119.9 (4) |
C1B—N1B—Ag | 124.6 (3) | C3AA—C4A—C5A | 117.3 (4) |
N1A—C9AA—C3AA | 121.4 (3) | N2B—C8B—C7B | 123.5 (4) |
N1A—C9AA—C8AA | 117.1 (4) | N2B—C8B—H8BA | 118.2 |
C3AA—C9AA—C8AA | 121.5 (4) | C7B—C8B—H8BA | 118.2 |
C8AA—N2A—C8A | 118.5 (3) | C6B—C5BB—C8BB | 118.6 (4) |
C8AA—N2A—Ag | 119.7 (2) | C6B—C5BB—C5B | 119.9 (4) |
C8A—N2A—Ag | 121.8 (3) | C8BB—C5BB—C5B | 121.5 (4) |
N2A—C8A—C7A | 123.3 (4) | C3B—C3BB—C9BB | 119.5 (4) |
N2A—C8A—H8AA | 118.4 | C3B—C3BB—C4B | 119.7 (4) |
C7A—C8A—H8AA | 118.4 | C9BB—C3BB—C4B | 120.8 (4) |
N1B—C1B—C2B | 123.2 (4) | C3A—C2A—C1A | 118.0 (4) |
N1B—C1B—H1BA | 118.4 | C3A—C2A—H2AA | 121.0 |
C2B—C1B—H1BA | 118.4 | C1A—C2A—H2AA | 121.0 |
C8AA—C5AA—C6A | 119.3 (4) | C1B—C2B—C3B | 118.9 (4) |
C8AA—C5AA—C5A | 120.6 (4) | C1B—C2B—H2BA | 120.6 |
C6A—C5AA—C5A | 120.1 (4) | C3B—C2B—H2BA | 120.6 |
N2B—C8BB—C5BB | 121.3 (4) | C2A—C3A—C3AA | 118.8 (4) |
N2B—C8BB—C9BB | 117.8 (3) | C2A—C3A—H3AA | 120.6 |
C5BB—C8BB—C9BB | 120.8 (4) | C3AA—C3A—H3AA | 120.6 |
C7B—C6B—C5BB | 119.8 (4) | C6A—C7A—C8A | 118.7 (4) |
C7B—C6B—H6BA | 120.1 | C6A—C7A—H7AA | 120.6 |
C5BB—C6B—H6BA | 120.1 | C8A—C7A—H7AA | 120.6 |
C3A—C3AA—C9AA | 120.0 (4) | O2B—C5B—C5BB | 123.2 (4) |
C3A—C3AA—C4A | 120.2 (4) | O2B—C5B—C4B | 119.2 (4) |
C9AA—C3AA—C4A | 119.8 (4) | C5BB—C5B—C4B | 117.5 (3) |
C6B—C7B—C8B | 117.7 (4) | N1A—C1A—C2A | 123.9 (4) |
C6B—C7B—H7BA | 121.1 | N1A—C1A—H1AA | 118.0 |
C8B—C7B—H7BA | 121.1 | C2A—C1A—H1AA | 118.0 |
N2A—Ag—N2B—C8B | 19.0 (5) | C5A—C5AA—C8AA—N2A | 177.0 (4) |
N1B—Ag—N2B—C8B | −177.5 (4) | C6A—C5AA—C8AA—C9AA | −179.7 (4) |
N1A—Ag—N2B—C8B | −31.7 (4) | C5A—C5AA—C8AA—C9AA | −0.6 (6) |
N2A—Ag—N2B—C8BB | −170.1 (3) | N1A—C9AA—C8AA—N2A | −5.4 (5) |
N1B—Ag—N2B—C8BB | −6.6 (3) | C3AA—C9AA—C8AA—N2A | 173.7 (4) |
N1A—Ag—N2B—C8BB | 139.2 (3) | N1A—C9AA—C8AA—C5AA | 172.3 (4) |
C3BB—C9BB—N1B—C1B | −1.3 (6) | C3AA—C9AA—C8AA—C5AA | −8.5 (6) |
C8BB—C9BB—N1B—C1B | 177.5 (3) | C8AA—C5AA—C5A—O2A | −161.6 (4) |
C3BB—C9BB—N1B—Ag | −179.1 (3) | C6A—C5AA—C5A—O2A | 17.5 (7) |
C8BB—C9BB—N1B—Ag | −0.3 (4) | C8AA—C5AA—C5A—C4A | 15.2 (6) |
N2A—Ag—N1B—C9BB | 175.6 (3) | C6A—C5AA—C5A—C4A | −165.7 (4) |
N2B—Ag—N1B—C9BB | 3.5 (3) | C3A—C3AA—C4A—O1A | 11.3 (6) |
N1A—Ag—N1B—C9BB | −69.5 (4) | C9AA—C3AA—C4A—O1A | −169.4 (4) |
N2A—Ag—N1B—C1B | −2.0 (4) | C3A—C3AA—C4A—C5A | −166.4 (4) |
N2B—Ag—N1B—C1B | −174.1 (4) | C9AA—C3AA—C4A—C5A | 12.9 (6) |
N1A—Ag—N1B—C1B | 112.9 (3) | O2A—C5A—C4A—O1A | −21.9 (7) |
N1B—Ag—N2A—C8AA | 150.5 (3) | C5AA—C5A—C4A—O1A | 161.0 (4) |
N2B—Ag—N2A—C8AA | −50.0 (5) | O2A—C5A—C4A—C3AA | 155.9 (4) |
N1A—Ag—N2A—C8AA | 4.6 (3) | C5AA—C5A—C4A—C3AA | −21.2 (5) |
N1B—Ag—N2A—C8A | −30.2 (4) | C8BB—N2B—C8B—C7B | 0.2 (6) |
N2B—Ag—N2A—C8A | 129.3 (4) | Ag—N2B—C8B—C7B | 170.8 (3) |
N1A—Ag—N2A—C8A | −176.1 (3) | C6B—C7B—C8B—N2B | 0.1 (7) |
C8AA—N2A—C8A—C7A | 0.7 (6) | C7B—C6B—C5BB—C8BB | −2.4 (6) |
Ag—N2A—C8A—C7A | −178.5 (3) | C7B—C6B—C5BB—C5B | 177.6 (4) |
C9BB—N1B—C1B—C2B | −0.2 (6) | N2B—C8BB—C5BB—C6B | 2.8 (6) |
Ag—N1B—C1B—C2B | 177.4 (3) | C9BB—C8BB—C5BB—C6B | −179.4 (4) |
C8B—N2B—C8BB—C5BB | −1.7 (6) | N2B—C8BB—C5BB—C5B | −177.2 (4) |
Ag—N2B—C8BB—C5BB | −173.1 (3) | C9BB—C8BB—C5BB—C5B | 0.6 (6) |
C8B—N2B—C8BB—C9BB | −179.5 (4) | C2B—C3B—C3BB—C9BB | −1.3 (6) |
Ag—N2B—C8BB—C9BB | 9.1 (4) | C2B—C3B—C3BB—C4B | 178.7 (4) |
N1B—C9BB—C8BB—N2B | −6.0 (5) | N1B—C9BB—C3BB—C3B | 2.1 (6) |
C3BB—C9BB—C8BB—N2B | 172.9 (4) | C8BB—C9BB—C3BB—C3B | −176.7 (4) |
N1B—C9BB—C8BB—C5BB | 176.2 (3) | N1B—C9BB—C3BB—C4B | −177.9 (4) |
C3BB—C9BB—C8BB—C5BB | −5.0 (6) | C8BB—C9BB—C3BB—C4B | 3.3 (6) |
N1A—C9AA—C3AA—C3A | 0.3 (6) | O1B—C4B—C3BB—C3B | 1.3 (7) |
C8AA—C9AA—C3AA—C3A | −178.8 (4) | C5B—C4B—C3BB—C3B | −177.7 (4) |
N1A—C9AA—C3AA—C4A | −179.0 (4) | O1B—C4B—C3BB—C9BB | −178.7 (4) |
C8AA—C9AA—C3AA—C4A | 1.9 (6) | C5B—C4B—C3BB—C9BB | 2.3 (6) |
C5BB—C6B—C7B—C8B | 1.0 (6) | N1B—C1B—C2B—C3B | 0.9 (7) |
C8AA—C5AA—C6A—C7A | 0.9 (6) | C3BB—C3B—C2B—C1B | −0.1 (6) |
C5A—C5AA—C6A—C7A | −178.2 (4) | C1A—C2A—C3A—C3AA | −0.7 (6) |
C3AA—C9AA—N1A—C1A | −0.1 (6) | C9AA—C3AA—C3A—C2A | 0.1 (6) |
C8AA—C9AA—N1A—C1A | 179.1 (3) | C4A—C3AA—C3A—C2A | 179.4 (4) |
C3AA—C9AA—N1A—Ag | −170.2 (3) | C5AA—C6A—C7A—C8A | 1.0 (6) |
C8AA—C9AA—N1A—Ag | 9.0 (4) | N2A—C8A—C7A—C6A | −1.9 (7) |
N2A—Ag—N1A—C9AA | −7.3 (3) | C6B—C5BB—C5B—O2B | 4.6 (6) |
N1B—Ag—N1A—C9AA | −139.6 (3) | C8BB—C5BB—C5B—O2B | −175.4 (4) |
N2B—Ag—N1A—C9AA | 154.9 (3) | C6B—C5BB—C5B—C4B | −175.1 (4) |
N2A—Ag—N1A—C1A | −176.1 (4) | C8BB—C5BB—C5B—C4B | 4.9 (6) |
N1B—Ag—N1A—C1A | 51.5 (4) | O1B—C4B—C5B—O2B | −5.0 (7) |
N2B—Ag—N1A—C1A | −14.0 (3) | C3BB—C4B—C5B—O2B | 173.9 (4) |
C8A—N2A—C8AA—C5AA | 1.3 (6) | O1B—C4B—C5B—C5BB | 174.7 (4) |
Ag—N2A—C8AA—C5AA | −179.4 (3) | C3BB—C4B—C5B—C5BB | −6.4 (6) |
C8A—N2A—C8AA—C9AA | 179.0 (3) | C9AA—N1A—C1A—C2A | −0.6 (6) |
Ag—N2A—C8AA—C9AA | −1.7 (5) | Ag—N1A—C1A—C2A | 167.9 (3) |
C6A—C5AA—C8AA—N2A | −2.1 (6) | C3A—C2A—C1A—N1A | 1.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8A—H8AA···O1Bi | 0.93 | 2.54 | 3.170 (5) | 125 |
C1B—H1BA···O14ii | 0.93 | 2.50 | 3.380 (5) | 157 |
C8B—H8BA···O11i | 0.93 | 2.58 | 3.155 (6) | 121 |
C1A—H1AA···O2Biii | 0.93 | 2.47 | 3.159 (5) | 131 |
C6B—H6BA···O2Aiv | 0.93 | 2.47 | 3.203 (5) | 136 |
C6A—H6AA···O13v | 0.93 | 2.45 | 3.235 (6) | 142 |
C8B—H8BA···O1Avi | 0.93 | 2.48 | 3.158 (6) | 130 |
C2A—H2AA···O12vii | 0.93 | 2.55 | 3.268 (6) | 134 |
C3A—H3AA···O11vii | 0.93 | 2.57 | 3.464 (7) | 162 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x−1, −y+1, −z+1; (iii) −x+1, −y+2, −z+1; (iv) x+1, y+1, z+1; (v) x, y−1, z−1; (vi) −x+1, −y+1, −z; (vii) x+1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Ag(C12H6N2O2)2]ClO4 |
Mr | 627.70 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 93 |
a, b, c (Å) | 8.493 (2), 11.260 (3), 13.190 (4) |
α, β, γ (°) | 112.525 (3), 103.682 (4), 97.378 (4) |
V (Å3) | 1097.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.10 |
Crystal size (mm) | 0.38 × 0.32 × 0.12 |
Data collection | |
Diffractometer | Bruker APEX II CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.679, 0.879 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11431, 6019, 4791 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.711 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.184, 1.07 |
No. of reflections | 6019 |
No. of parameters | 343 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.36, −1.63 |
Computer programs: APEX2 (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
Ag—N2A | 2.261 (3) | Ag—N2B | 2.349 (3) |
Ag—N1B | 2.331 (4) | Ag—N1A | 2.453 (4) |
N2A—Ag—N1B | 129.69 (12) | N2A—Ag—N1A | 70.77 (11) |
N2A—Ag—N2B | 158.05 (13) | N1B—Ag—N1A | 144.28 (12) |
N1B—Ag—N2B | 71.16 (12) | N2B—Ag—N1A | 95.79 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8A—H8AA···O1Bi | 0.93 | 2.54 | 3.170 (5) | 125.2 |
C1B—H1BA···O14ii | 0.93 | 2.50 | 3.380 (5) | 157.4 |
C8B—H8BA···O11i | 0.93 | 2.58 | 3.155 (6) | 120.8 |
C1A—H1AA···O2Biii | 0.93 | 2.47 | 3.159 (5) | 131.4 |
C6B—H6BA···O2Aiv | 0.93 | 2.47 | 3.203 (5) | 136.1 |
C6A—H6AA···O13v | 0.93 | 2.45 | 3.235 (6) | 142.1 |
C8B—H8BA···O1Avi | 0.93 | 2.48 | 3.158 (6) | 129.6 |
C2A—H2AA···O12vii | 0.93 | 2.55 | 3.268 (6) | 134.3 |
C3A—H3AA···O11vii | 0.93 | 2.57 | 3.464 (7) | 162.4 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x−1, −y+1, −z+1; (iii) −x+1, −y+2, −z+1; (iv) x+1, y+1, z+1; (v) x, y−1, z−1; (vi) −x+1, −y+1, −z; (vii) x+1, y, z−1. |
Phendione (1,10-phenanthroline-5,6-dione) is an excellent ligand that incorporates two functional groups with different coordination properties. Since the stereochemical behavior of Cu+ and Ag+ are similar it is interesting to compare the behavior of these cations with phendione. Isomorphous and isostructural Cu+ and Ag+ derivatives {[M(L)2](ClO4)2, where M = Cu+ and Ag+} have recently been determined (Galet et al., 2005; McCann et al., 2004) as well as a Ag+ complex, with trifluoromethanesulfonate instead of perchlorate as counterion (Wen et al., 2006). In addition a polymeric Ag+ phendione complex where the ligand coordinates to Ag through N and O donors has been reported (Wen et al., 2006). In this paper we report the synthesis and characterization of the title compound, [AgL2]+(ClO4)- (I).
The structure of the title compound, shown in Figure 1, is made up of an [Ag(L)2]+ cation and a perchlorate anion. Each silver atom is coordinated to the two nitrogen atoms of both phendione ligands. In contrast to the previous structure determination of this complex where there is crystallographically imposed symmetry on both the anion and cation in the present case there is no such symmetry. Table 1 gives a listing of selected bond lengths and bond angles. The C=O bond lengths in the phendione ligands (1.220 (5) Å and 1.207 (5) Å) are comparable to those values found in other such complexes (Allen, 2002). The metrical parameters for the phendione ligand is in the normal ranges observed for complexes where only the N atoms are coordinated to a metal (Allen, 2002). The Ag—N bond lengths (2.261 (3), 2.331 (4) Å, 2.349 (3) Å, and 2.453 (4) Å) are similar to those found in related phenanthroline derivatives of silver (McCann et al., 2004; Wen et al., 2006; Leschke et al., 2002; Paramonov et al., 2003; Pallenberg et al., 1997; Titze et al., 1997). In I, silver is in a distorted tetrahedral environment. This is best illustrated by the dihedral angle between the planes of the coordinated ligands which would be 90° for tetrahedral and 0° for planar. In this case the angle is 36.7 (2)° which is intermediate between these extremes.
There are weak C—H···O hydrogen bonds between the hydrogen atoms on C1A, C1B, C2A, C6A, C6B, C8A, and C8B and either perchlorate O atoms or phendione O atoms from an adjoining cation. In addition, there are short contacts between the perchlorate anion and the phendione ligands (O14···C4B 2.845 (5) Å) as well as unusual and different torsion angles for O1—C4—C5—O2 for the two phendione ligands (-21.9 (7)° and -5.0 (7)°) which reflects the fact that in this polymorph there is no crystallographically imposed symmetry on the cation.