The monoclinic cell of dicyclohexylammonium 2,4-dichlorophenoxyacetate contains four C
12H
24N
+·C
5H
8Cl
2O
3- ion pairs. The ammonium N atom is hydrogen bonded to the oxygen ends of two carboxyl groups to form a 12-membered O-C-O
HNH
O-C-O
HNH ring. In (2,4-dichlorophenoxylacetato)bis(triphenylphosphine)silver(I), [Ag(C
8H
5Cl
2O
3)(C
18H
15P)
2], the carboxyl CO
2 unit chelates to the Ag atom in an anisobidentate manner [Ag-O = 2.436 (2) and 2.517 (2) Å]; the Ag atom shows distorted tetrahedral geometry.
Supporting information
CCDC references: 147690; 147691
Dicyclohexylamine, dissolved in a small volume of ethanol, was added to an ethanol solution of 2,4-dichlorphenoxylacetic acid (1:1 molar ratio of reactants). Ethanol was added to dissolve the ammonium carboxylate that precipitated from solution, and the mixture was heated until most had dissolved completely; the filtered solution afforded long colourless crystals when it was cooled. Solid-state cross-polarization/magic-angle-spinning (CP/MAS) 13C NMR: δ = 172.3 (–CO2); 154.3, 129.8, 114.1 (–C6H3Cl2); 68.0 (–CH2—O–); 54.6, 51.4, 31.4, 29.8, 28.1, 26.2 p.p.m. (cyclo-C6H11). Equimolar quantities of aqueous sodium 2,4-dichlorophenoxyacetate and silver nitrate were mixed to afford an immediate white precipitate of silver 2,4-dichlorophenoxyacetate, which was collected, washed with water, and then air dried. The silver salt and triphenylphosphine (1:2 molar ratio) were heated in a small volume of ethanol until the reactants dissolved completely; slow cooling of the filtered solution yielded faint tan-colored crystals of the 1:2 complex. 13C NMR: δ = 173.9 (–CO2); 155.6, 135.4–130.1, 116.4 (–C6H3Cl2 overlapped with –C6H5); 70.3 p.p.m. (–CH2—O). CP/MAS 31P NMR for the ordered triphenylphosphine ligand: δ = 20.8±0.1 p.p.m., 1J(Ag–P) = 508±4 Hz, 2J(P–P) = 140±4 Hz. CP/MAS 31P NMR for the disordered triphenylphosphine ligand: δ = 15.9±0.1 p.p.m., 1J(Ag–P) = 383±4 Hz, 2J(P–P) = 140±4 Hz.
In (II), two of the phenyl rings of one of the triphenylphosphine ligands are disordered, and each was refined as two regular hexagons; an ISOR 0.02 instruction was used on all the disordered atoms. The P—Cipso distances were restrainted by a SADI 0.01 instruction, as were the four P—Cortho distances.
For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPII (Johnson, 1976) for (II). For both compounds, software used to prepare material for publication: SHELXL97.
(I) Dicyclohexylammonium) 2,4-dichlorophenoxyacetate
top
Crystal data top
C12H24N+·C8H5O3Cl2− | F(000) = 856 |
Mr = 402.34 | Dx = 1.260 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.3847 (1) Å | Cell parameters from 6107 reflections |
b = 18.2966 (3) Å | θ = 2.7–28.4° |
c = 8.9780 (1) Å | µ = 0.33 mm−1 |
β = 105.296 (1)° | T = 298 K |
V = 2120.78 (4) Å3 | Parallelepiped, colourless |
Z = 4 | 0.48 × 0.42 × 0.28 mm |
Data collection top
Siemens CCD area-detector diffractometer | 3737 independent reflections |
Radiation source: fine-focus sealed tube | 2447 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.7° |
w scans | h = −15→15 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −21→11 |
Tmin = 0.860, Tmax = 0.915 | l = −10→10 |
11531 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.063 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.198 | w = 1/[σ2(Fo2) + (0.0975P)2 + 0.5146P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
3737 reflections | Δρmax = 0.37 e Å−3 |
244 parameters | Δρmin = −0.44 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (2) |
Crystal data top
C12H24N+·C8H5O3Cl2− | V = 2120.78 (4) Å3 |
Mr = 402.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.3847 (1) Å | µ = 0.33 mm−1 |
b = 18.2966 (3) Å | T = 298 K |
c = 8.9780 (1) Å | 0.48 × 0.42 × 0.28 mm |
β = 105.296 (1)° | |
Data collection top
Siemens CCD area-detector diffractometer | 3737 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2447 reflections with I > 2σ(I) |
Tmin = 0.860, Tmax = 0.915 | Rint = 0.059 |
11531 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.198 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.37 e Å−3 |
3737 reflections | Δρmin = −0.44 e Å−3 |
244 parameters | |
Special details top
Refinement. For both structures, the refinements used only the reflections up to 2θ = 50°. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.4665 (1) | 0.4144 (1) | 0.3168 (1) | 0.124 (1) | |
Cl2 | 0.5334 (1) | 0.6977 (1) | 0.2262 (3) | 0.183 (1) | |
O1 | 0.0899 (2) | 0.4418 (1) | −0.2712 (2) | 0.061 (1) | |
O2 | 0.1316 (2) | 0.4660 (2) | −0.0237 (2) | 0.078 (1) | |
O3 | 0.3296 (2) | 0.4193 (1) | 0.0152 (3) | 0.070 (1) | |
N1 | −0.0964 (2) | 0.5062 (1) | −0.2593 (3) | 0.045 (1) | |
C1 | 0.1509 (2) | 0.4430 (2) | −0.1408 (3) | 0.044 (1) | |
C2 | 0.2572 (2) | 0.4121 (2) | −0.1317 (3) | 0.056 (1) | |
C3 | 0.3723 (2) | 0.4859 (2) | 0.0565 (3) | 0.060 (1) | |
C4 | 0.4422 (2) | 0.4910 (3) | 0.2021 (4) | 0.080 (1) | |
C5 | 0.4909 (3) | 0.5564 (4) | 0.2523 (5) | 0.102 (2) | |
C6 | 0.4721 (3) | 0.6167 (3) | 0.1582 (7) | 0.105 (2) | |
C7 | 0.4038 (3) | 0.6123 (2) | 0.0156 (5) | 0.087 (1) | |
C8 | 0.3542 (2) | 0.5478 (2) | −0.0341 (4) | 0.067 (1) | |
C9 | −0.0977 (2) | 0.5778 (2) | −0.3391 (3) | 0.045 (1) | |
C10 | −0.0086 (2) | 0.6243 (2) | −0.2492 (4) | 0.065 (1) | |
C11 | −0.0064 (3) | 0.6970 (2) | −0.3291 (5) | 0.082 (1) | |
C12 | −0.1074 (3) | 0.7380 (2) | −0.3492 (5) | 0.083 (1) | |
C13 | −0.1973 (3) | 0.6915 (2) | −0.4356 (5) | 0.078 (1) | |
C14 | −0.2001 (2) | 0.6172 (2) | −0.3606 (4) | 0.063 (1) | |
C15 | −0.1766 (2) | 0.4509 (2) | −0.3327 (3) | 0.045 (1) | |
C16 | −0.1667 (3) | 0.3852 (2) | −0.2288 (3) | 0.063 (1) | |
C17 | −0.2454 (3) | 0.3274 (2) | −0.3016 (4) | 0.079 (1) | |
C18 | −0.2369 (3) | 0.3051 (2) | −0.4601 (4) | 0.069 (1) | |
C19 | −0.2421 (3) | 0.3705 (2) | −0.5636 (4) | 0.065 (1) | |
C20 | −0.1650 (2) | 0.4292 (2) | −0.4898 (3) | 0.053 (1) | |
H1a | −0.031 (3) | 0.483 (2) | −0.250 (4) | 0.07 (1)* | |
H1b | −0.102 (3) | 0.519 (2) | −0.169 (4) | 0.07 (1)* | |
H2a | 0.2500 | 0.3606 | −0.1584 | 0.084* | |
H2b | 0.2849 | 0.4364 | −0.2081 | 0.084* | |
H5 | 0.5366 | 0.5596 | 0.3501 | 0.152* | |
H7 | 0.3910 | 0.6533 | −0.0481 | 0.131* | |
H8 | 0.3073 | 0.5457 | −0.1311 | 0.101* | |
H9 | −0.0873 | 0.5685 | −0.4415 | 0.067* | |
H10a | 0.0562 | 0.5987 | −0.2403 | 0.098* | |
H10b | −0.0159 | 0.6326 | −0.1459 | 0.098* | |
H11a | 0.0059 | 0.6887 | −0.4295 | 0.123* | |
H11b | 0.0502 | 0.7264 | −0.2686 | 0.123* | |
H12a | −0.1164 | 0.7507 | −0.2487 | 0.124* | |
H12b | −0.1054 | 0.7829 | −0.4059 | 0.124* | |
H13a | −0.1925 | 0.6844 | −0.5406 | 0.118* | |
H13b | −0.2615 | 0.7171 | −0.4404 | 0.118* | |
H14a | −0.2145 | 0.6236 | −0.2610 | 0.095* | |
H14b | −0.2552 | 0.5879 | −0.4249 | 0.095* | |
H15 | −0.2454 | 0.4725 | −0.3454 | 0.068* | |
H16a | −0.1773 | 0.3998 | −0.1302 | 0.094* | |
H16b | −0.0974 | 0.3651 | −0.2101 | 0.094* | |
H17a | −0.2354 | 0.2847 | −0.2352 | 0.119* | |
H17b | −0.3145 | 0.3461 | −0.3101 | 0.119* | |
H18a | −0.1719 | 0.2796 | −0.4502 | 0.103* | |
H18b | −0.2928 | 0.2717 | −0.5064 | 0.103* | |
H19a | −0.3114 | 0.3908 | −0.5880 | 0.097* | |
H19b | −0.2282 | 0.3551 | −0.6596 | 0.097* | |
H20a | −0.0953 | 0.4113 | −0.4793 | 0.079* | |
H20b | −0.1754 | 0.4718 | −0.5564 | 0.079* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.061 (1) | 0.237 (2) | 0.068 (1) | 0.031 (1) | 0.005 (1) | 0.052 (1) |
Cl2 | 0.088 (1) | 0.191 (2) | 0.270 (2) | −0.043 (1) | 0.047 (1) | −0.158 (2) |
O1 | 0.047 (1) | 0.090 (2) | 0.042 (1) | 0.010 (1) | 0.005 (1) | −0.004 (1) |
O2 | 0.066 (1) | 0.131 (2) | 0.043 (1) | 0.017 (1) | 0.025 (1) | −0.013 (1) |
O3 | 0.045 (1) | 0.091 (2) | 0.064 () | 0.006 (1) | −0.003 (1) | 0.014 (1) |
N1 | 0.044 (1) | 0.059 (2) | 0.032 (1) | 0.006 (1) | 0.011 (1) | −0.002 (1) |
C1 | 0.039 (1) | 0.055 (2) | 0.039 (1) | 0.001 (1) | 0.013 (1) | −0.000 (1) |
C2 | 0.043 (2) | 0.067 (2) | 0.057 (2) | 0.006 (2) | 0.010 (1) | −0.005 (2) |
C3 | 0.034 (1) | 0.096 (3) | 0.047 (2) | 0.005 (2) | 0.006 (1) | −0.007 (2) |
C4 | 0.034 (2) | 0.155 (4) | 0.048 (2) | 0.010 (2) | 0.008 (1) | −0.011 (2) |
C5 | 0.042 (2) | 0.191 (6) | 0.071 (3) | −0.004 (3) | 0.013 (2) | −0.056 (3) |
C6 | 0.052 (2) | 0.142 (4) | 0.127 (4) | −0.014 (3) | 0.033 (3) | −0.077 (4) |
C7 | 0.058 (2) | 0.092 (3) | 0.114 (3) | −0.003 (2) | 0.027 (2) | −0.033 (3) |
C8 | 0.052 (2) | 0.085 (2) | 0.060 (2) | 0.002 (2) | 0.006 (2) | −0.012 (2) |
C9 | 0.046 (2) | 0.053 (2) | 0.038 (1) | 0.000 (1) | 0.015 (1) | −0.003 (1) |
C10 | 0.054 (2) | 0.067 (2) | 0.070 (2) | −0.002 (2) | 0.007 (2) | −0.013 (2) |
C11 | 0.070 (2) | 0.062 (2) | 0.115 (3) | −0.013 (2) | 0.027 (2) | −0.015 (2) |
C12 | 0.094 (3) | 0.054 (2) | 0.104 (3) | 0.006 (2) | 0.032 (2) | −0.011 (2) |
C13 | 0.075 (2) | 0.068 (2) | 0.087 (3) | 0.012 (2) | 0.014 (2) | 0.014 (2) |
C14 | 0.050 (2) | 0.066 (2) | 0.071 (2) | 0.007 (2) | 0.011 (2) | 0.009 (2) |
C15 | 0.038 (1) | 0.054 (2) | 0.046 (2) | 0.004 (1) | 0.014 (1) | 0.001 (1) |
C16 | 0.090 (2) | 0.062 (2) | 0.044 (2) | 0.000 (2) | 0.033 (2) | 0.006 (2) |
C17 | 0.103 (3) | 0.065 (2) | 0.088 (3) | −0.013 (2) | 0.056 (2) | 0.001 (2) |
C18 | 0.074 (2) | 0.062 (2) | 0.074 (2) | −0.013 (2) | 0.025 (2) | −0.009 (2) |
C19 | 0.060 (2) | 0.069 (2) | 0.057 (2) | −0.007 (2) | 0.001 (2) | −0.004 (2) |
C20 | 0.057 (2) | 0.061 (2) | 0.037 (2) | −0.008 (2) | 0.008 (1) | 0.001 (1) |
Geometric parameters (Å, º) top
Cl1—C4 | 1.720 (5) | N1—H1b | 0.86 (4) |
Cl2—C6 | 1.726 (5) | C2—H2a | 0.9700 |
O1—C1 | 1.239 (3) | C2—H2b | 0.9700 |
O2—C1 | 1.222 (3) | C5—H5 | 0.9300 |
O3—C3 | 1.356 (4) | C7—H7 | 0.9300 |
O3—C2 | 1.421 (4) | C8—H8 | 0.9300 |
N1—C9 | 1.491 (4) | C9—H9 | 0.9800 |
N1—C15 | 1.496 (4) | C10—H10a | 0.9700 |
C1—C2 | 1.514 (4) | C10—H10b | 0.9700 |
C3—C8 | 1.377 (5) | C11—H11a | 0.9700 |
C3—C4 | 1.395 (4) | C11—H11b | 0.9700 |
C4—C5 | 1.380 (7) | C12—H12a | 0.9700 |
C5—C6 | 1.372 (7) | C12—H12b | 0.9700 |
C6—C7 | 1.365 (7) | C13—H13a | 0.9700 |
C7—C8 | 1.371 (5) | C13—H13b | 0.9700 |
C9—C10 | 1.513 (4) | C14—H14a | 0.9700 |
C9—C14 | 1.514 (4) | C14—H14b | 0.9700 |
C10—C11 | 1.515 (5) | C15—H15 | 0.9800 |
C11—C12 | 1.515 (5) | C16—H16a | 0.9700 |
C12—C13 | 1.511 (5) | C16—H16b | 0.9700 |
C13—C14 | 1.522 (5) | C17—H17a | 0.9700 |
C15—C16 | 1.506 (4) | C17—H17b | 0.9700 |
C15—C20 | 1.512 (4) | C18—H18a | 0.9700 |
C16—C17 | 1.514 (5) | C18—H18b | 0.9700 |
C17—C18 | 1.513 (5) | C19—H19a | 0.9700 |
C18—C19 | 1.506 (5) | C19—H19b | 0.9700 |
C19—C20 | 1.514 (4) | C20—H20a | 0.9700 |
N1—H1a | 0.95 (4) | C20—H20b | 0.9700 |
| | | |
C3—O3—C2 | 118.2 (3) | C9—C10—H10a | 109.5 |
C9—N1—C15 | 117.8 (2) | C11—C10—H10a | 109.5 |
O2—C1—O1 | 125.7 (3) | C9—C10—H10b | 109.5 |
O2—C1—C2 | 119.5 (2) | C11—C10—H10b | 109.5 |
O1—C1—C2 | 114.8 (2) | H10a—C10—H10b | 108.1 |
O3—C2—C1 | 114.6 (2) | C10—C11—H11a | 109.4 |
O3—C3—C8 | 125.5 (3) | C12—C11—H11a | 109.4 |
O3—C3—C4 | 116.6 (4) | C10—C11—H11b | 109.4 |
C8—C3—C4 | 117.9 (4) | C12—C11—H11b | 109.4 |
C5—C4—C3 | 120.4 (4) | H11a—C11—H11b | 108.0 |
C5—C4—Cl1 | 120.8 (3) | C13—C12—H12a | 109.6 |
C3—C4—Cl1 | 118.7 (4) | C11—C12—H12a | 109.6 |
C6—C5—C4 | 120.1 (4) | C13—C12—H12b | 109.6 |
C7—C6—C5 | 119.9 (5) | C11—C12—H12b | 109.6 |
C7—C6—Cl2 | 121.4 (5) | H12a—C12—H12b | 108.1 |
C5—C6—Cl2 | 118.7 (4) | C12—C13—H13a | 109.1 |
C6—C7—C8 | 120.2 (5) | C14—C13—H13a | 109.1 |
C7—C8—C3 | 121.4 (4) | C12—C13—H13b | 109.1 |
N1—C9—C10 | 109.3 (2) | C14—C13—H13b | 109.1 |
N1—C9—C14 | 112.0 (2) | H13a—C13—H13b | 107.8 |
C10—C9—C14 | 111.1 (2) | C9—C14—H14a | 109.5 |
C9—C10—C11 | 110.6 (3) | C13—C14—H14a | 109.5 |
C10—C11—C12 | 111.3 (3) | C9—C14—H14b | 109.5 |
C13—C12—C11 | 110.3 (3) | C13—C14—H14b | 109.5 |
C12—C13—C14 | 112.6 (3) | H14a—C14—H14b | 108.1 |
C9—C14—C13 | 110.7 (3) | N1—C15—H15 | 108.7 |
N1—C15—C16 | 109.3 (2) | C16—C15—H15 | 108.7 |
N1—C15—C20 | 110.5 (2) | C20—C15—H15 | 108.7 |
C16—C15—C20 | 110.8 (2) | C15—C16—H16a | 109.5 |
C15—C16—C17 | 110.6 (3) | C17—C16—H16a | 109.5 |
C18—C17—C16 | 112.2 (3) | C15—C16—H16b | 109.5 |
C19—C18—C17 | 111.3 (3) | C17—C16—H16b | 109.5 |
C18—C19—C20 | 112.2 (3) | H16a—C16—H16b | 108.1 |
C15—C20—C19 | 111.6 (2) | C18—C17—H17a | 109.2 |
C9—N1—H1a | 109 (2) | C16—C17—H17a | 109.2 |
C15—N1—H1a | 106 (2) | C18—C17—H17b | 109.2 |
C9—N1—H1b | 103 (2) | C16—C17—H17b | 109.2 |
C15—N1—H1b | 111 (2) | H17a—C17—H17b | 107.9 |
H1a—N1—H1b | 109 (3) | C19—C18—H18a | 109.4 |
O3—C2—H2a | 108.6 | C17—C18—H18a | 109.4 |
C1—C2—H2a | 108.6 | C19—C18—H18b | 109.4 |
O3—C2—H2b | 108.6 | C17—C18—H18b | 109.4 |
C1—C2—H2b | 108.6 | H18a—C18—H18b | 108.0 |
H2a—C2—H2b | 107.6 | C18—C19—H19a | 109.2 |
C6—C5—H5 | 119.9 | C20—C19—H19a | 109.2 |
C4—C5—H5 | 119.9 | C18—C19—H19b | 109.2 |
C6—C7—H7 | 119.9 | C20—C19—H19b | 109.2 |
C8—C7—H7 | 119.9 | H19a—C19—H19b | 107.9 |
C7—C8—H8 | 119.3 | C15—C20—H20a | 109.3 |
C3—C8—H8 | 119.3 | C19—C20—H20a | 109.3 |
N1—C9—H9 | 108.1 | C15—C20—H20b | 109.3 |
C10—C9—H9 | 108.1 | C19—C20—H20b | 109.3 |
C14—C9—H9 | 108.1 | H20a—C20—H20b | 108.0 |
| | | |
C3—O3—C2—C1 | −75.9 (3) | C15—N1—C9—C14 | 58.4 (3) |
O2—C1—C2—O3 | −5.7 (4) | N1—C9—C10—C11 | 178.8 (3) |
O1—C1—C2—O3 | 174.9 (3) | C14—C9—C10—C11 | −57.1 (4) |
C2—O3—C3—C8 | −2.2 (4) | C9—C10—C11—C12 | 57.7 (4) |
C2—O3—C3—C4 | 179.4 (2) | C10—C11—C12—C13 | −55.9 (4) |
O3—C3—C4—C5 | 178.7 (3) | C11—C12—C13—C14 | 54.4 (5) |
C8—C3—C4—C5 | 0.2 (4) | N1—C9—C14—C13 | 177.4 (3) |
O3—C3—C4—Cl1 | −1.1 (4) | C10—C9—C14—C13 | 54.9 (4) |
C8—C3—C4—Cl1 | −179.6 (2) | C12—C13—C14—C9 | −54.2 (4) |
C3—C4—C5—C6 | −1.0 (5) | C9—N1—C15—C16 | −175.9 (2) |
Cl1—C4—C5—C6 | 178.8 (3) | C9—N1—C15—C20 | 62.0 (3) |
C4—C5—C6—C7 | 1.0 (6) | N1—C15—C16—C17 | −178.7 (2) |
C4—C5—C6—Cl2 | 179.3 (3) | C20—C15—C16—C17 | −56.7 (3) |
C5—C6—C7—C8 | −0.1 (6) | C15—C16—C17—C18 | 56.0 (4) |
Cl2—C6—C7—C8 | −178.4 (3) | C16—C17—C18—C19 | −53.5 (4) |
C6—C7—C8—C3 | −0.7 (5) | C17—C18—C19—C20 | 52.2 (4) |
O3—C3—C8—C7 | −177.7 (3) | N1—C15—C20—C19 | 177.3 (2) |
C4—C3—C8—C7 | 0.7 (5) | C16—C15—C20—C19 | 55.9 (3) |
C15—N1—C9—C10 | −178.1 (2) | C18—C19—C20—C15 | −53.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1a···O1 | 0.95 (4) | 1.85 (4) | 2.784 (3) | 169 (3) |
N1—H1b···O2i | 0.86 (4) | 1.90 (4) | 2.751 (3) | 171 (3) |
Symmetry code: (i) −x, −y+1, −z. |
(II) Bis(triphenylphosphine)(2,4-dichlorophenoxyacetato)silver(I)
top
Crystal data top
[Ag(C8H5Cl2O3)(C18H15P)2] | F(000) = 1736 |
Mr = 852.43 | Dx = 1.402 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.4500 (2) Å | Cell parameters from 7909 reflections |
b = 25.8202 (4) Å | θ = 2.8–28.4° |
c = 11.7071 (2) Å | µ = 0.75 mm−1 |
β = 96.790 (1)° | T = 298 K |
V = 4037.2 (1) Å3 | Parallelepiped, colourless |
Z = 4 | 0.42 × 0.38 × 0.28 mm |
Data collection top
Siemens CCD area-detector diffractometer | 7085 independent reflections |
Radiation source: fine-focus sealed tube | 5520 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.8° |
w scans | h = −15→15 |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | k = −26→30 |
Tmin = 0.744, Tmax = 0.818 | l = −13→13 |
22253 measured reflections | |
Refinement top
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.058P)2] where P = (Fo2 + 2Fc2)/3 |
7085 reflections | (Δ/σ)max = 0.001 |
531 parameters | Δρmax = 0.63 e Å−3 |
178 restraints | Δρmin = −0.63 e Å−3 |
Crystal data top
[Ag(C8H5Cl2O3)(C18H15P)2] | V = 4037.2 (1) Å3 |
Mr = 852.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.4500 (2) Å | µ = 0.75 mm−1 |
b = 25.8202 (4) Å | T = 298 K |
c = 11.7071 (2) Å | 0.42 × 0.38 × 0.28 mm |
β = 96.790 (1)° | |
Data collection top
Siemens CCD area-detector diffractometer | 7085 independent reflections |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | 5520 reflections with I > 2σ(I) |
Tmin = 0.744, Tmax = 0.818 | Rint = 0.066 |
22253 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 178 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.63 e Å−3 |
7085 reflections | Δρmin = −0.63 e Å−3 |
531 parameters | |
Special details top
Refinement. For both structures, the refinements used only the reflections up to 2θ = 50°. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ag1 | 0.83691 (2) | 0.09632 (1) | 0.79029 (2) | 0.0473 (1) | |
Cl1 | 0.45625 (9) | 0.11996 (6) | 0.26294 (9) | 0.0953 (4) | |
Cl2 | 0.3328 (2) | 0.25515 (8) | 0.56444 (19) | 0.172 (1) | |
P1 | 1.00941 (6) | 0.12158 (3) | 0.79246 (7) | 0.0433 (2) | |
P2 | 0.72360 (6) | 0.11832 (4) | 0.93503 (7) | 0.0422 (2) | |
O1 | 0.7450 (2) | 0.0265 (1) | 0.6853 (2) | 0.053 (1) | |
O2 | 0.7239 (2) | 0.1033 (1) | 0.6037 (2) | 0.070 (1) | |
O3 | 0.5565 (2) | 0.0692 (1) | 0.4617 (2) | 0.057 (1) | |
C1 | 1.0225 (4) | 0.1920 (1) | 0.7855 (6) | 0.049 (4) | 0.598 (14) |
C2 | 1.1064 (6) | 0.2153 (2) | 0.7488 (9) | 0.105 (4) | 0.598 (14) |
C3 | 1.1190 (8) | 0.2686 (2) | 0.758 (1) | 0.145 (6) | 0.598 (14) |
C4 | 1.0478 (7) | 0.2987 (1) | 0.804 (1) | 0.147 (6) | 0.598 (14) |
C5 | 0.9639 (6) | 0.2754 (2) | 0.841 (1) | 0.122 (5) | 0.598 (14) |
C6 | 0.9512 (5) | 0.2221 (2) | 0.831 (1) | 0.087 (4) | 0.598 (14) |
C1' | 1.0130 (8) | 0.1911 (2) | 0.7926 (7) | 0.072 (8) | 0.402 (14) |
C2' | 1.040 (1) | 0.2170 (3) | 0.6970 (9) | 0.111 (6) | 0.402 (14) |
C3' | 1.033 (2) | 0.2706 (3) | 0.690 (1) | 0.159 (9) | 0.402 (14) |
C4' | 0.998 (2) | 0.2983 (2) | 0.779 (1) | 0.16 (1) | 0.402 (14) |
C5' | 0.971 (1) | 0.2724 (3) | 0.875 (1) | 0.16 (1) | 0.402 (14) |
C6' | 0.9782 (9) | 0.2188 (3) | 0.8816 (9) | 0.074 (4) | 0.402 (14) |
C7 | 1.0766 (4) | 0.0960 (3) | 0.6786 (4) | 0.055 (5) | 0.64 (2) |
C8 | 1.0227 (4) | 0.0696 (4) | 0.5880 (6) | 0.069 (3) | 0.64 (2) |
C9 | 1.0709 (6) | 0.0514 (5) | 0.4973 (5) | 0.086 (3) | 0.64 (2) |
C10 | 1.1731 (7) | 0.0595 (3) | 0.4973 (6) | 0.092 (5) | 0.64 (2) |
C11 | 1.2270 (6) | 0.0858 (4) | 0.588 (1) | 0.095 (4) | 0.64 (2) |
C12 | 1.1788 (5) | 0.1040 (4) | 0.6786 (9) | 0.076 (3) | 0.64 (2) |
C7' | 1.0798 (6) | 0.1018 (5) | 0.6771 (5) | 0.047 (7) | 0.36 (2) |
C8' | 1.0316 (7) | 0.101 (1) | 0.5653 (6) | 0.082 (6) | 0.36 (2) |
C9' | 1.0828 (9) | 0.084 (1) | 0.4755 (7) | 0.099 (6) | 0.36 (2) |
C10' | 1.182 (1) | 0.0689 (7) | 0.497 (1) | 0.080 (8) | 0.36 (2) |
C11' | 1.2304 (9) | 0.0699 (7) | 0.609 (1) | 0.070 (5) | 0.36 (2) |
C12' | 1.1792 (7) | 0.0863 (6) | 0.6990 (7) | 0.054 (4) | 0.36 (2) |
C13 | 1.0880 (2) | 0.1027 (1) | 0.9232 (3) | 0.038 (1) | |
C14 | 1.0915 (3) | 0.0511 (2) | 0.9536 (4) | 0.076 (1) | |
C15 | 1.1466 (3) | 0.0345 (2) | 1.0540 (4) | 0.087 (2) | |
C16 | 1.1985 (3) | 0.0685 (2) | 1.1259 (3) | 0.066 (1) | |
C17 | 1.1980 (3) | 0.1193 (2) | 1.0964 (4) | 0.077 (1) | |
C18 | 1.1426 (3) | 0.1366 (2) | 0.9953 (3) | 0.062 (1) | |
C19 | 0.5954 (2) | 0.0938 (1) | 0.9137 (3) | 0.048 (1) | |
C20 | 0.5796 (3) | 0.0441 (2) | 0.8705 (3) | 0.055 (1) | |
C21 | 0.4839 (3) | 0.023 (3) | 0.8555 (4) | 0.073 (1) | |
C22 | 0.4049 (3) | 0.0517 (2) | 0.8832 (4) | 0.084 (1) | |
C23 | 0.4184 (3) | 0.1005 (2) | 0.9260 (4) | 0.084 (2) | |
C24 | 0.5138 (3) | 0.1227 (2) | 0.9407 (3) | 0.065 (1) | |
C25 | 0.7103 (2) | 0.1882 (1) | 0.9414 (3) | 0.049 (1) | |
C26 | 0.6724 (3) | 0.2136 (2) | 0.8413 (3) | 0.066 (1) | |
C27 | 0.6635 (4) | 0.2670 (2) | 0.8391 (4) | 0.083 (1) | |
C28 | 0.6950 (4) | 0.2956 (2) | 0.9353 (5) | 0.085 (1) | |
C29 | 0.7337 (4) | 0.2716 (2) | 1.0328 (4) | 0.089 (2) | |
C30 | 0.7423 (3) | 0.2178 (2) | 1.0371 (3) | 0.072 (1) | |
C31 | 0.7682 (2) | 0.0984 (1) | 1.0818 (3) | 0.045 (1) | |
C32 | 0.7042 (3) | 0.0928 (2) | 1.1659 (3) | 0.064 (1) | |
C33 | 0.7401 (3) | 0.0772 (2) | 1.2747 (3) | 0.077 (1) | |
C34 | 0.8397 (3) | 0.0662 (2) | 1.3024 (4) | 0.083 (1) | |
C35 | 0.9049 (3) | 0.0723 (2) | 1.2209 (4) | 0.086 (1) | |
C36 | 0.8686 (3) | 0.0884 (2) | 1.1105 (3) | 0.068 (1) | |
C37 | 0.7001 (2) | 0.0578 (2) | 0.6166 (3) | 0.044 (1) | |
C38 | 0.6054 (3) | 0.0359 (1) | 0.5484 (3) | 0.055 (1) | |
C39 | 0.5037 (2) | 0.1109 (1) | 0.4932 (3) | 0.050 (1) | |
C40 | 0.4522 (3) | 0.1390 (2) | 0.4033 (3) | 0.062 (1) | |
C41 | 0.4000 (3) | 0.1833 (2) | 0.4254 (4) | 0.082 (1) | |
C42 | 0.3970 (4) | 0.1984 (2) | 0.5366 (5) | 0.093 (2) | |
C43 | 0.4450 (3) | 0.1709 (2) | 0.6270 (4) | 0.083 (1) | |
C44 | 0.4977 (3) | 0.1267 (2) | 0.6050 (3) | 0.062 (1) | |
H2 | 1.1541 | 0.1951 | 0.7182 | 0.158* | 0.60 (1) |
H3 | 1.1751 | 0.2841 | 0.7335 | 0.217* | 0.60 (1) |
H4 | 1.0562 | 0.3343 | 0.8101 | 0.220* | 0.60 (1) |
H5 | 0.9162 | 0.2955 | 0.8713 | 0.183* | 0.60 (1) |
H6 | 0.8951 | 0.2065 | 0.8559 | 0.130* | 0.60 (1) |
H2' | 1.0635 | 0.1985 | 0.6375 | 0.167* | 0.40 (1) |
H3' | 1.0508 | 0.2880 | 0.6264 | 0.239* | 0.40 (1) |
H4' | 0.9927 | 0.3342 | 0.7749 | 0.241* | 0.40 (1) |
H5' | 0.9473 | 0.2910 | 0.9345 | 0.236* | 0.40 (1) |
H6' | 0.9600 | 0.2015 | 0.9456 | 0.111* | 0.40 (1) |
H8 | 0.9543 | 0.0642 | 0.5880 | 0.103* | 0.64 (2) |
H9 | 1.0348 | 0.0338 | 0.4367 | 0.129* | 0.64 (2) |
H10 | 1.2054 | 0.0473 | 0.4366 | 0.139* | 0.64 (2) |
H11 | 1.2954 | 0.0912 | 0.5879 | 0.142* | 0.64 (2) |
H12 | 1.2149 | 0.1216 | 0.7392 | 0.113* | 0.64 (2) |
H8' | 0.9651 | 0.1112 | 0.5507 | 0.124* | 0.36 (2) |
H9' | 1.0505 | 0.0837 | 0.4007 | 0.148* | 0.36 (2) |
H10' | 1.2165 | 0.0579 | 0.4373 | 0.119* | 0.36 (2) |
H11' | 1.2969 | 0.0596 | 0.6238 | 0.105* | 0.36 (2) |
H12' | 1.2115 | 0.0870 | 0.7738 | 0.081* | 0.36 (2) |
H14 | 1.0561 | 0.0270 | 0.9056 | 0.114* | |
H15 | 1.1480 | −0.0006 | 1.0724 | 0.131* | |
H16 | 1.2340 | 0.0572 | 1.1944 | 0.099* | |
H17 | 1.2350 | 0.1429 | 1.1441 | 0.115* | |
H18 | 1.1428 | 0.1716 | 0.9767 | 0.093* | |
H20 | 0.6336 | 0.0247 | 0.8513 | 0.082* | |
H21 | 0.4738 | −0.0104 | 0.8269 | 0.109* | |
H22 | 0.3409 | 0.0376 | 0.8727 | 0.126* | |
H23 | 0.3638 | 0.1192 | 0.9456 | 0.127* | |
H24 | 0.5228 | 0.1564 | 0.9683 | 0.098* | |
H26 | 0.6528 | 0.1945 | 0.7751 | 0.100* | |
H27 | 0.6361 | 0.2835 | 0.7721 | 0.125* | |
H28 | 0.6897 | 0.3315 | 0.9332 | 0.127* | |
H29 | 0.7550 | 0.2911 | 1.0979 | 0.133* | |
H30 | 0.7697 | 0.2017 | 1.1047 | 0.108* | |
H32 | 0.6363 | 0.0997 | 1.1481 | 0.096* | |
H33 | 0.6965 | 0.0740 | 1.3304 | 0.115* | |
H34 | 0.8633 | 0.0547 | 1.3759 | 0.125* | |
H35 | 0.9728 | 0.0657 | 1.2397 | 0.129* | |
H36 | 0.9125 | 0.0924 | 1.0555 | 0.102* | |
H38a | 0.6227 | 0.0039 | 0.5121 | 0.083* | |
H38b | 0.5581 | 0.0274 | 0.6021 | 0.083* | |
H41 | 0.3673 | 0.2026 | 0.3652 | 0.123* | |
H43 | 0.4423 | 0.1818 | 0.7022 | 0.124* | |
H44 | 0.5293 | 0.1074 | 0.6659 | 0.093* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag1 | 0.0325 (2) | 0.0608 (2) | 0.0478 (2) | 0.0008 (1) | 0.0011 (1) | −0.0085 (1) |
Cl1 | 0.0807 (8) | 0.147 (1) | 0.0527 (6) | 0.0326 (8) | −0.0156 (5) | 0.0007 (7) |
Cl2 | 0.199 (2) | 0.152 (2) | 0.164 (2) | 0.111 (2) | 0.018 (2) | −0.015 (1) |
P1 | 0.0306 (4) | 0.0539 (5) | 0.0444 (5) | 0.0022 (4) | 0.0005 (3) | −0.0006 (4) |
P2 | 0.0382 (4) | 0.0495 (5) | 0.0395 (4) | 0.0023 (4) | 0.0073 (3) | −0.0020 (4) |
O1 | 0.051 (1) | 0.053 (1) | 0.052 (1) | 0.008 (1) | −0.007 (1) | −0.001 (1) |
O2 | 0.063 (2) | 0.059 (2) | 0.080 (2) | −0.019 (1) | −0.022 (1) | 0.018 (1) |
O3 | 0.049 (1) | 0.068 (2) | 0.050 (1) | 0.005 (1) | −0.008 (1) | −0.001 (1) |
C1 | 0.041 (5) | 0.044 (6) | 0.063 (8) | 0.019 (4) | 0.006 (5) | 0.015 (6) |
C2 | 0.082 (6) | 0.063 (5) | 0.18 (1) | 0.017 (4) | 0.060 (7) | 0.049 (6) |
C3 | 0.123 (9) | 0.077 (7) | 0.25 (1) | 0.004 (6) | 0.08 (1) | 0.052 (8) |
C4 | 0.16 (1) | 0.052 (6) | 0.23 (1) | 0.016 (6) | 0.05 (1) | 0.046 (8) |
C5 | 0.090 (8) | 0.056 (7) | 0.23 (1) | 0.010 (6) | 0.058 (8) | −0.016 (7) |
C6 | 0.048 (5) | 0.059 (5) | 0.16 (1) | −0.002 (4) | 0.024 (7) | −0.021 (5) |
C1' | 0.07 (1) | 0.08 (2) | 0.07 (1) | −0.01 (1) | 0.01 (1) | 0.03 (1) |
C2' | 0.16 (2) | 0.086 (9) | 0.094 (9) | 0.026 (9) | 0.037 (9) | 0.053 (8) |
C3' | 0.23 (2) | 0.10 (1) | 0.14 (1) | 0.00 (1) | 0.03 (1) | 0.08 (1) |
C4' | 0.19 (2) | 0.11 (1) | 0.18 (2) | 0.04 (1) | 0.01 (2) | 0.05 (1) |
C5' | 0.16 (2) | 0.10 (2) | 0.21 (2) | 0.03 (1) | 0.03 (1) | 0.01 (1) |
C6' | 0.052 (7) | 0.062 (8) | 0.103 (9) | 0.004 (5) | −0.012 (7) | −0.012 (6) |
C7 | 0.044 (7) | 0.069 (7) | 0.054 (8) | 0.013 (5) | 0.015 (6) | 0.003 (5) |
C8 | 0.057 (4) | 0.102 (7) | 0.044 (4) | 0.020 (4) | −0.008 (3) | −0.018 (4) |
C9 | 0.092 (6) | 0.115 (8) | 0.048 (4) | 0.040 (6) | −0.007 (4) | −0.011 (5) |
C10 | 0.11 (1) | 0.112 (8) | 0.059 (8) | 0.047 (7) | 0.025 (7) | 0.007 (6) |
C11 | 0.082 (7) | 0.118 (9) | 0.091 (7) | −0.004 (5) | 0.040 (6) | −0.015 (7) |
C12 | 0.051 (5) | 0.106 (9) | 0.073 (5) | −0.013 (4) | 0.020 (4) | −0.016 (5) |
C7' | 0.05 (1) | 0.05 (1) | 0.04 (1) | −0.010 (8) | −0.022 (8) | −0.002 (7) |
C8' | 0.059 (7) | 0.13 (2) | 0.052 (7) | 0.025 (8) | −0.004 (6) | −0.007 (8) |
C9' | 0.10 (1) | 0.14 (2) | 0.051 (7) | 0.01 (1) | −0.004 (7) | −0.019 (9) |
C10' | 0.06 (1) | 0.12 (1) | 0.07 (1) | 0.00 (1) | 0.03 (1) | −0.02 (1) |
C11' | 0.059 (8) | 0.08 (1) | 0.077 (9) | 0.017 (6) | 0.029 (7) | 0.004 (8) |
C12' | 0.055 (7) | 0.056 (8) | 0.053 (7) | 0.012 (5) | 0.013 (6) | 0.007 (6) |
C13 | 0.033 (2) | 0.039 (2) | 0.044 (2) | 0.001 (1) | 0.005 (1) | 0.001 (1) |
C14 | 0.079 (3) | 0.049 (2) | 0.093 (3) | −0.005 (2) | −0.023 (2) | 0.004 (2) |
C15 | 0.091 (3) | 0.055 (3) | 0.109 (4) | 0.002 (2) | −0.016 (3) | 0.035 (3) |
C16 | 0.060 (2) | 0.082 (3) | 0.055 (2) | 0.018 (2) | −0.001 (2) | 0.016 (2) |
C17 | 0.082 (3) | 0.076 (3) | 0.064 (2) | 0.008 (2) | −0.028 (2) | −0.013 (2) |
C18 | 0.065 (2) | 0.051 (2) | 0.064 (2) | −0.004 (2) | −0.014 (2) | 0.001 (2) |
C19 | 0.040 (2) | 0.066 (2) | 0.038 (2) | 0.003 (2) | 0.007 (1) | 0.004 (2) |
C20 | 0.048 (2) | 0.060 (2) | 0.056 (2) | −0.004 (2) | 0.006 (2) | 0.006 (2) |
C21 | 0.063 (3) | 0.079 (3) | 0.075 (3) | −0.022 (2) | 0.005 (2) | 0.012 (2) |
C22 | 0.047 (2) | 0.116 (4) | 0.088 (3) | −0.017 (3) | 0.006 (2) | 0.018 (3) |
C23 | 0.039 (2) | 0.129 (5) | 0.087 (3) | 0.016 (2) | 0.015 (2) | 0.002 (3) |
C24 | 0.046 (2) | 0.085 (3) | 0.065 (2) | 0.009 (2) | 0.012 (2) | −0.003 (2) |
C25 | 0.046 (2) | 0.057 (2) | 0.047 (2) | 0.006 (2) | 0.017 (2) | 0.000 (2) |
C26 | 0.074 (3) | 0.063 (3) | 0.063 (2) | 0.010 (2) | 0.011 (2) | 0.007 (2) |
C27 | 0.095 (3) | 0.069 (3) | 0.088 (3) | 0.020 (3) | 0.020 (3) | 0.024 (3) |
C28 | 0.115 (4) | 0.051 (3) | 0.097 (4) | 0.016 (3) | 0.046 (3) | 0.003 (3) |
C29 | 0.137 (4) | 0.058 (3) | 0.076 (3) | 0.000 (3) | 0.036 (3) | −0.016 (2) |
C30 | 0.106 (3) | 0.058 (3) | 0.054 (2) | 0.002 (2) | 0.017 (2) | −0.008 (2) |
C31 | 0.045 (2) | 0.046 (2) | 0.044 (2) | −0.001 (1) | 0.002 (1) | −0.002 (2) |
C32 | 0.058 (2) | 0.085 (3) | 0.050 (2) | 0.003 (2) | 0.010 (2) | 0.010 (2) |
C33 | 0.083 (3) | 0.097 (3) | 0.052 (2) | −0.005 (3) | 0.016 (2) | 0.013 (2) |
C34 | 0.085 (3) | 0.104 (4) | 0.056 (3) | −0.011 (3) | −0.009 (2) | 0.024 (2) |
C35 | 0.066 (3) | 0.126 (4) | 0.063 (3) | 0.000 (3) | −0.013 (2) | 0.018 (3) |
C36 | 0.048 (2) | 0.101 (3) | 0.055 (2) | −0.001 (2) | 0.003 (2) | 0.008 (2) |
C37 | 0.042 (2) | 0.046 (2) | 0.044 (2) | 0.002 (2) | 0.003 (1) | −0.004 (2) |
C38 | 0.050 (2) | 0.049 (2) | 0.062 (2) | −0.003 (2) | −0.012 (2) | 0.003 (2) |
C39 | 0.034 (2) | 0.060 (2) | 0.054 (2) | −0.004 (2) | −0.002 (2) | 0.006 (2) |
C40 | 0.042 (2) | 0.087 (3) | 0.054 (2) | 0.004 (2) | −0.003 (2) | 0.010 (2) |
C41 | 0.072 (3) | 0.094 (4) | 0.078 (3) | 0.023 (3) | 0.002 (2) | 0.018 (3) |
C42 | 0.086 (3) | 0.099 (4) | 0.095 (4) | 0.036 (3) | 0.018 (3) | −0.004 (3) |
C43 | 0.079 (3) | 0.096 (4) | 0.075 (3) | 0.021 (3) | 0.013 (2) | −0.006 (3) |
C44 | 0.055 (2) | 0.078 (3) | 0.052 (2) | 0.007 (2) | 0.000 (2) | 0.006 (2) |
Geometric parameters (Å, º) top
Ag1—O1 | 2.435 (2) | C29—C30 | 1.394 (6) |
Ag1—O2 | 2.516 (2) | C31—C36 | 1.377 (5) |
Ag1—P1 | 2.4073 (8) | C31—C32 | 1.390 (5) |
Ag1—P2 | 2.4753 (8) | C32—C33 | 1.368 (5) |
Cl1—C40 | 1.722 (4) | C33—C34 | 1.371 (6) |
Cl2—C42 | 1.752 (5) | C34—C35 | 1.379 (6) |
P1—C1' | 1.795 (5) | C35—C36 | 1.390 (6) |
P1—C7' | 1.812 (4) | C37—C38 | 1.530 (4) |
P1—C7 | 1.821 (3) | C39—C44 | 1.382 (5) |
P1—C13 | 1.821 (3) | C39—C40 | 1.394 (5) |
P1—C1 | 1.830 (3) | C40—C41 | 1.383 (6) |
P2—C25 | 1.816 (4) | C41—C42 | 1.363 (6) |
P2—C31 | 1.825 (3) | C42—C43 | 1.371 (7) |
P2—C19 | 1.826 (3) | C43—C44 | 1.383 (6) |
O1—C37 | 1.244 (4) | C2—H2 | 0.9300 |
O2—C37 | 1.233 (4) | C3—H3 | 0.9300 |
O3—C39 | 1.365 (4) | C4—H4 | 0.9300 |
O3—C38 | 1.429 (4) | C5—H5 | 0.9300 |
C1—C2 | 1.3900 | C6—H6 | 0.9300 |
C1—C6 | 1.3900 | C2'—H2' | 0.9300 |
C2—C3 | 1.3900 | C3'—H3' | 0.9300 |
C3—C4 | 1.3900 | C4'—H4' | 0.9300 |
C4—C5 | 1.3900 | C5'—H5' | 0.9300 |
C5—C6 | 1.3900 | C6'—H6' | 0.9300 |
C1'—C2' | 1.3900 | C8—H8 | 0.9300 |
C1'—C6' | 1.3900 | C9—H9 | 0.9300 |
C2'—C3' | 1.3900 | C10—H10 | 0.9300 |
C3'—C4' | 1.3900 | C11—H11 | 0.9300 |
C4'—C5' | 1.3900 | C12—H12 | 0.9300 |
C5'—C6' | 1.3900 | C8'—H8' | 0.9300 |
C7—C8 | 1.3900 | C9'—H9' | 0.9300 |
C7—C12 | 1.3900 | C10'—H10' | 0.9300 |
C8—C9 | 1.3900 | C11'—H11' | 0.9300 |
C9—C10 | 1.3900 | C12'—H12' | 0.9300 |
C10—C11 | 1.3900 | C14—H14 | 0.9300 |
C11—C12 | 1.3900 | C15—H15 | 0.9300 |
C7'—C8' | 1.3900 | C16—H16 | 0.9300 |
C7'—C12' | 1.3900 | C17—H17 | 0.9300 |
C8'—C9' | 1.3900 | C18—H18 | 0.9300 |
C9'—C10' | 1.3900 | C20—H20 | 0.9300 |
C10'—C11' | 1.3900 | C21—H21 | 0.9300 |
C11'—C12' | 1.3900 | C22—H22 | 0.9300 |
C13—C18 | 1.369 (5) | C23—H23 | 0.9300 |
C13—C14 | 1.379 (5) | C24—H24 | 0.9300 |
C14—C15 | 1.382 (6) | C26—H26 | 0.9300 |
C15—C16 | 1.352 (6) | C27—H27 | 0.9300 |
C16—C17 | 1.358 (6) | C28—H28 | 0.9300 |
C17—C18 | 1.395 (5) | C29—H29 | 0.9300 |
C19—C20 | 1.387 (5) | C30—H30 | 0.9300 |
C19—C24 | 1.394 (5) | C32—H32 | 0.9300 |
C20—C21 | 1.389 (5) | C33—H33 | 0.9300 |
C21—C22 | 1.365 (6) | C34—H34 | 0.9300 |
C22—C23 | 1.361 (7) | C35—H35 | 0.9300 |
C23—C24 | 1.397 (6) | C36—H36 | 0.9300 |
C25—C30 | 1.382 (5) | C38—H38a | 0.9700 |
C25—C26 | 1.385 (5) | C38—H38b | 0.9700 |
C26—C27 | 1.384 (6) | C41—H41 | 0.9300 |
C27—C28 | 1.371 (7) | C43—H43 | 0.9300 |
C28—C29 | 1.349 (7) | C44—H44 | 0.9300 |
| | | |
O1—Ag1—O2 | 52.9 (1) | C18—C13—C14 | 117.4 (3) |
O1—Ag1—O1 | 129.6 (1) | C18—C13—P1 | 124.2 (3) |
O1—Ag1—P2 | 101.5 (1) | C14—C13—P1 | 118.3 (3) |
O2—Ag1—P1 | 118.2 (1) | C13—C14—C15 | 121.2 (4) |
O2—Ag1—P2 | 102.7 (1) | C13—C14—H14 | 119.4 |
P1—Ag1—P2 | 127.0 (1) | C15—C14—H14 | 119.4 |
C1—P1—C7 | 105.6 (3) | C16—C15—C14 | 120.9 (4) |
C1—P1—C7' | 100.7 (5) | C16—C15—H15 | 119.5 |
C1—P1—C13 | 104.7 (2) | C14—C15—H15 | 119.5 |
C1'—P1—C7' | 105.4 (5) | C15—C16—C17 | 118.9 (4) |
C1'—P1—C7 | 110.4 (3) | C15—C16—H16 | 120.6 |
C1'—P1—C13 | 104.7 (3) | C17—C16—H16 | 120.6 |
C7'—P1—C13 | 104.4 (3) | C16—C17—C18 | 120.8 (4) |
C7—P1—C13 | 103.2 (2) | C16—C17—H17 | 119.6 |
C1—P1—Ag1 | 111.5 (2) | C18—C17—H17 | 119.6 |
C1'—P1—Ag1 | 107.3 (3) | C13—C18—C17 | 120.8 (4) |
C7—P1—Ag1 | 117.1 (2) | C13—C18—H18 | 119.6 |
C7'—P1—Ag1 | 120.2 (3) | C17—C18—H18 | 119.6 |
C13—P1—Ag1 | 113.5 (1) | C20—C19—C24 | 119.2 (3) |
C25—P2—C31 | 105.4 (2) | C20—C19—P2 | 118.1 (3) |
C25—P2—C19 | 104.7 (2) | C24—C19—P2 | 122.7 (3) |
C31—P2—C19 | 103.3 (2) | C19—C20—C21 | 120.5 (4) |
C25—P2—Ag1 | 109.1 (1) | C19—C20—H20 | 119.7 |
C31—P2—Ag1 | 114.8 (1) | C21—C20—H20 | 119.7 |
C19—P2—Ag1 | 118.3 (1) | C22—C21—C20 | 119.5 (4) |
C37—O1—Ag1 | 91.4 (2) | C22—C21—H21 | 120.2 |
C37—O2—Ag1 | 87.9 (2) | C20—C21—H21 | 120.2 |
C39—O3—C38 | 119.5 (3) | C23—C22—C21 | 121.1 (4) |
C2—C1—C6 | 120.0 | C23—C22—H22 | 119.4 |
C2—C1—P1 | 121.9 (3) | C21—C22—H22 | 119.4 |
C6—C1—P1 | 117.6 (3) | C22—C23—C24 | 120.3 (4) |
C3—C2—C1 | 120.0 | C22—C23—H23 | 119.8 |
C3—C2—H2 | 120.0 | C24—C23—H23 | 119.8 |
C1—C2—H2 | 120.0 | C19—C24—C23 | 119.3 (4) |
C4—C3—C2 | 120.0 | C19—C24—H24 | 120.4 |
C4—C3—H3 | 120.0 | C23—C24—H24 | 120.4 |
C2—C3—H3 | 120.0 | C30—C25—C26 | 118.2 (4) |
C3—C4—C5 | 120.0 | C30—C25—P2 | 124.0 (3) |
C3—C4—H4 | 120.0 | C26—C25—P2 | 117.6 (3) |
C5—C4—H4 | 120.0 | C27—C26—C25 | 120.6 (4) |
C6—C5—C4 | 120.0 | C27—C26—H26 | 119.7 |
C6—C5—H5 | 120.0 | C25—C26—H26 | 119.7 |
C4—C5—H5 | 120.0 | C28—C27—C26 | 120.3 (4) |
C5—C6—C1 | 120.0 | C28—C27—H27 | 119.9 |
C5—C6—H6 | 120.0 | C26—C27—H27 | 119.9 |
C1—C6—H6 | 120.0 | C29—C28—C27 | 119.9 (4) |
C2'—C1'—C6' | 120.0 | C29—C28—H28 | 120.0 |
C2'—C1'—P1 | 119.3 (3) | C27—C28—H28 | 120.0 |
C6'—C1'—P1 | 120.3 (4) | C28—C29—C30 | 120.7 (4) |
C1'—C2'—C3' | 120.0 | C28—C29—H29 | 119.7 |
C1'—C2'—H2' | 120.0 | C30—C29—H29 | 119.7 |
C3'—C2'—H2' | 120.0 | C25—C30—C29 | 120.3 (4) |
C2'—C3'—C4' | 120.0 | C25—C30—H30 | 119.9 |
C2'—C3'—H3' | 120.0 | C29—C30—H30 | 119.9 |
C4'—C3'—H3' | 120.0 | C36—C31—C32 | 118.6 (3) |
C3'—C4'—C5' | 120.0 | C36—C31—P2 | 119.1 (3) |
C3'—C4'—H4' | 120.0 | C32—C31—P2 | 122.3 (3) |
C5'—C4'—H4' | 120.0 | C33—C32—C31 | 120.7 (4) |
C6'—C5'—C4' | 120.0 | C33—C32—H32 | 119.7 |
C6'—C5'—H5' | 120.0 | C31—C32—H32 | 119.7 |
C4'—C5'—H5' | 120.0 | C32—C33—C34 | 120.6 (4) |
C5'—C6'—C1' | 120.0 | C32—C33—H33 | 119.7 |
C5'—C6'—H6' | 120.0 | C34—C33—H33 | 119.7 |
C1'—C6'—H6' | 120.0 | C33—C34—C35 | 119.7 (4) |
C8—C7—C12 | 120.0 | C33—C34—H34 | 120.1 |
C8—C7—P1 | 118.5 (2) | C35—C34—H34 | 120.1 |
C12—C7—P1 | 121.5 (3) | C34—C35—C36 | 119.8 (4) |
C7—C8—C9 | 120.0 | C34—C35—H35 | 120.1 |
C7—C8—H8 | 120.0 | C36—C35—H35 | 120.1 |
C9—C8—H8 | 120.0 | C31—C36—C35 | 120.6 (4) |
C8—C9—C10 | 120.0 | C31—C36—H36 | 119.7 |
C8—C9—H9 | 120.0 | C35—C36—H36 | 119.7 |
C10—C9—H9 | 120.0 | O2—C37—O1 | 125.8 (3) |
C11—C10—C9 | 120.0 | O2—C37—C38 | 120.0 (3) |
C11—C10—H10 | 120.0 | O1—C37—C38 | 114.1 (3) |
C9—C10—H10 | 120.0 | O3—C38—C37 | 115.7 (3) |
C10—C11—C12 | 120.0 | O3—C38—H38a | 108.4 |
C10—C11—H11 | 120.0 | C37—C38—H38a | 108.4 |
C12—C11—H11 | 120.0 | O3—C38—H38b | 108.4 |
C11—C12—C7 | 120.0 | C37—C38—H38b | 108.4 |
C11—C12—H12 | 120.0 | H38a—C38—H38b | 107.4 |
C7—C12—H12 | 120.0 | O3—C39—C44 | 125.4 (3) |
C8'—C7'—C12' | 120.0 | O3—C39—C40 | 115.8 (3) |
C8'—C7'—P1 | 118.7 (3) | C44—C39—C40 | 118.8 (4) |
C12'—C7'—P1 | 121.3 (3) | C41—C40—C39 | 120.5 (4) |
C7'—C8'—C9' | 120.0 | C41—C40—Cl1 | 119.3 (3) |
C7'—C8'—H8' | 120.0 | C39—C40—Cl1 | 120.2 (3) |
C9'—C8'—H8' | 120.0 | C42—C41—C40 | 119.2 (4) |
C10'—C9'—C8' | 120.0 | C42—C41—H41 | 120.4 |
C10'—C9'—H9' | 120.0 | C40—C41—H41 | 120.4 |
C8'—C9'—H9' | 120.0 | C41—C42—C43 | 121.7 (4) |
C9'—C10'—C11' | 120.0 | C41—C42—Cl2 | 119.2 (4) |
C9'—C10'—H10' | 120.0 | C43—C42—Cl2 | 119.1 (4) |
C11'—C10'—H10' | 120.0 | C42—C43—C44 | 119.2 (4) |
C10'—C11'—C12' | 120.0 | C42—C43—H43 | 120.4 |
C10'—C11'—H11' | 120.0 | C44—C43—H43 | 120.4 |
C12'—C11'—H11' | 120.0 | C39—C44—C43 | 120.6 (4) |
C11'—C12'—C7' | 120.0 | C39—C44—H44 | 119.7 |
C11'—C12'—H12' | 120.0 | C43—C44—H44 | 119.7 |
C7'—C12'—H12' | 120.0 | | |
| | | |
O1—Ag1—P1—C1' | 140.0 (3) | C7'—C8'—C9'—C10' | 0.0 |
P2—Ag1—P1—C1' | −59.3 (3) | C8'—C9'—C10'—C11' | 0.0 |
O2—Ag1—P1—C1' | 76.4 (3) | C9'—C10'—C11'—C12' | 0.0 |
O1—Ag1—P1—C7' | 19.7 (5) | C10'—C11'—C12'—C7' | 0.0 |
P2—Ag1—P1—C7' | −179.5 (5) | C8'—C7'—C12'—C11' | 0.0 |
O2—Ag1—P1—C7' | −43.8 (5) | P1—C7'—C12'—C11' | 178 (1) |
O1—Ag1—P1—C7 | 15.3 (3) | C1'—P1—C13—C18 | −5.3 (4) |
P2—Ag1—P1—C7 | 176.1 (3) | C7'—P1—C13—C18 | 105.3 (5) |
O2—Ag1—P1—C7 | −48.2 (3) | C7—P1—C13—C18 | 110.3 (4) |
O1—Ag1—P1—C13 | −104.9 (1) | C1—P1—C13—C18 | −0.1 (4) |
P2—Ag1—P1—C13 | 55.9 (1) | Ag1—P1—C13—C18 | −122.0 (3) |
O2—Ag1—P1—C13 | −168.4 (1) | C1'—P1—C13—C14 | 173.2 (4) |
O1—Ag1—P1—C1 | 137.1 (2) | C7'—P1—C13—C14 | −76.2 (6) |
P2—Ag1—P1—C1 | −62.1 (2) | C7—P1—C13—C14 | −71.3 (4) |
O2—Ag1—P1—C1 | 73.6 (2) | C1—P1—C13—C14 | 178.4 (3) |
P1—Ag1—P2—C25 | 60.9 (1) | Ag1—P1—C13—C14 | 56.5 (3) |
O1—Ag1—P2—C25 | −134.1 (1) | C18—C13—C14—C15 | 1.1 (6) |
O2—Ag1—P2—C25 | −80.0 (1) | P1—C13—C14—C15 | −177.5 (4) |
P1—Ag1—P2—C31 | −57.1 (1) | C13—C14—C15—C16 | 0.3 (7) |
O1—Ag1—P2—C31 | 107.9 (1) | C14—C15—C16—C17 | −1.8 (7) |
O2—Ag1—P2—C31 | 162.1 (1) | C15—C16—C17—C18 | 1.8 (7) |
P1—Ag1—P2—C19 | −179.6 (1) | C14—C13—C18—C17 | −1.0 (6) |
O1—Ag1—P2—C19 | −14.6 (1) | P1—C13—C18—C17 | 177.4 (3) |
O2—Ag1—P2—C19 | 39.5 (2) | C16—C17—C18—C13 | −0.4 (7) |
P1—Ag1—O1—C37 | −105.7 (2) | C25—P2—C19—C20 | 160.4 (3) |
P2—Ag1—O1—C37 | 89.9 (2) | C31—P2—C19—C20 | −89.5 (3) |
O2—Ag1—O1—C37 | −7.5 (2) | Ag1—P2—C19—C20 | 38.6 (3) |
P1—Ag1—O2—C37 | 127.6 (2) | C25—P2—C19—C24 | −20.6 (3) |
O1—Ag1—O2—C37 | 7.6 (2) | C31—P2—C19—C24 | 89.5 (3) |
P2—Ag1—O2—C37 | −87.3 (2) | Ag1—P2—C19—C24 | −142.4 (3) |
C7'—P1—C1—C2 | −30.2 (7) | C24—C19—C20—C21 | −0.8 (5) |
C7—P1—C1—C2 | −30.6 (7) | P2—C19—C20—C21 | 178.2 (3) |
C13—P1—C1—C2 | 78.0 (7) | C19—C20—C21—C22 | 0.3 (6) |
Ag1—P1—C1—C2 | −158.8 (6) | C20—C21—C22—C23 | −0.4 (7) |
C7'—P1—C1—C6 | 157.5 (6) | C21—C22—C23—C24 | 1.1 (7) |
C7—P1—C1—C6 | 157.0 (5) | C20—C19—C24—C23 | 1.4 (6) |
C13—P1—C1—C6 | −94.4 (5) | P2—C19—C24—C23 | −177.6 (3) |
Ag1—P1—C1—C6 | 28.8 (5) | C22—C23—C24—C19 | −1.5 (7) |
C6—C1—C2—C3 | 0.0 | C31—P2—C25—C30 | 8.0 (4) |
P1—C1—C2—C3 | −172.2 (6) | C19—P2—C25—C30 | 116.6 (3) |
C1—C2—C3—C4 | 0.0 | Ag1—P2—C25—C30 | −115.8 (3) |
C2—C3—C4—C5 | 0.0 | C31—P2—C25—C26 | −177.0 (3) |
C3—C4—C5—C6 | 0.0 | C19—P2—C25—C26 | −68.3 (3) |
C4—C5—C6—C1 | 0.0 | Ag1—P2—C25—C26 | 59.3 (3) |
C2—C1—C6—C5 | 0.0 | C30—C25—C26—C27 | −2.4 (6) |
P1—C1—C6—C5 | 172.5 (6) | P2—C25—C26—C27 | −177.8 (3) |
C7'—P1—C1'—C2' | 16.5 (9) | C25—C26—C27—C28 | 2.0 (7) |
C7—P1—C1'—C2' | 15.9 (9) | C26—C27—C28—C29 | −0.8 (7) |
C13—P1—C1'—C2' | 126.3 (8) | C27—C28—C29—C30 | 0.1 (8) |
Ag1—P1—C1'—C2' | −112.7 (8) | C26—C25—C30—C29 | 1.7 (6) |
C7'—P1—C1'—C6' | −170.7 (8) | P2—C25—C30—C29 | 176.8 (3) |
C7—P1—C1'—C6' | −171.4 (8) | C28—C29—C30—C25 | −0.6 (7) |
C13—P1—C1'—C6' | −60.9 (9) | C25—P2—C31—C36 | −100.0 (3) |
Ag1—P1—C1'—C6' | 60.0 (8) | C19—P2—C31—C36 | 150.4 (3) |
C6'—C1'—C2'—C3' | 0.0 | Ag1—P2—C31—C36 | 20.1 (3) |
P1—C1'—C2'—C3' | 172.8 (9) | C25—P2—C31—C32 | 80.2 (3) |
C1'—C2'—C3'—C4' | 0.0 | C19—P2—C31—C32 | −29.5 (3) |
C2'—C3'—C4'—C5' | 0.0 | Ag1—P2—C31—C32 | −159.8 (3) |
C3'—C4'—C5'—C6' | 0.0 | C36—C31—C32—C33 | −0.6 (6) |
C4'—C5'—C6'—C1' | 0.0 | P2—C31—C32—C33 | 179.2 (3) |
C2'—C1'—C6'—C5' | 0.0 | C31—C32—C33—C34 | −0.7 (7) |
P1—C1'—C6'—C5' | −172.7 (9) | C32—C33—C34—C35 | 1.8 (8) |
C1'—P1—C7—C8 | −114.0 (7) | C33—C34—C35—C36 | −1.5 (8) |
C13—P1—C7—C8 | 134.5 (6) | C32—C31—C36—C35 | 0.8 (6) |
C1—P1—C7—C8 | −115.8 (6) | P2—C31—C36—C35 | −179.0 (4) |
Ag1—P1—C7—C8 | 9.0 (7) | C34—C35—C36—C31 | 0.2 (8) |
C1'—P1—C7—C12 | 63.4 (7) | Ag1—O2—C37—O1 | −14.7 (4) |
C13—P1—C7—C12 | −48.1 (7) | Ag1—O2—C37—C38 | 162.5 (3) |
C1—P1—C7—C12 | 61.6 (6) | Ag1—O1—C37—O2 | 15.2 (4) |
Ag1—P1—C7—C12 | −173.6 (6) | Ag1—O1—C37—C38 | −162.2 (3) |
C12—C7—C8—C9 | 0.0 | C39—O3—C38—C37 | −73.9 (4) |
P1—C7—C8—C9 | 177.4 (5) | O2—C37—C38—O3 | 7.6 (5) |
C7—C8—C9—C10 | 0.0 | O1—C37—C38—O3 | −174.8 (3) |
C8—C9—C10—C11 | 0.0 | C38—O3—C39—C44 | 4.5 (5) |
C9—C10—C11—C12 | 0.0 | C38—O3—C39—C40 | −175.3 (3) |
C10—C11—C12—C7 | 0.0 | O3—C39—C40—C41 | −177.1 (4) |
C8—C7—C12—C11 | 0.0 | C44—C39—C40—C41 | 3.0 (6) |
P1—C7—C12—C11 | −177.3 (5) | O3—C39—C40—Cl1 | 0.9 (5) |
C1'—P1—C7'—C8' | −83 (1) | C44—C39—C40—Cl1 | −179.0 (3) |
C13—P1—C7'—C8' | 167 (1) | C39—C40—C41—C42 | −1.9 (7) |
C1—P1—C7'—C8' | −85 (1) | Cl1—C40—C41—C42 | −179.9 (4) |
Ag1—P1—C7'—C8' | 38 (1) | C40—C41—C42—C43 | 0.4 (8) |
C1'—P1—C7'—C12' | 99 (1) | C40—C41—C42—Cl2 | 178.8 (4) |
C13—P1—C7'—C12' | −12 (1) | C41—C42—C43—C44 | −0.1 (8) |
C1—P1—C7'—C12' | 97 (1) | Cl2—C42—C43—C44 | −178.5 (4) |
Ag1—P1—C7'—C12' | −140 (1) | O3—C39—C44—C43 | 177.4 (4) |
C12'—C7'—C8'—C9' | 0.0 | C40—C39—C44—C43 | −2.7 (6) |
P1—C7'—C8'—C9' | −178 (1) | C42—C43—C44—C39 | 1.3 (7) |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C12H24N+·C8H5O3Cl2− | [Ag(C8H5Cl2O3)(C18H15P)2] |
Mr | 402.34 | 852.43 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 13.3847 (1), 18.2966 (3), 8.9780 (1) | 13.4500 (2), 25.8202 (4), 11.7071 (2) |
β (°) | 105.296 (1) | 96.790 (1) |
V (Å3) | 2120.78 (4) | 4037.2 (1) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.75 |
Crystal size (mm) | 0.48 × 0.42 × 0.28 | 0.42 × 0.38 × 0.28 |
|
Data collection |
Diffractometer | Siemens CCD area-detector diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.860, 0.915 | 0.744, 0.818 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11531, 3737, 2447 | 22253, 7085, 5520 |
Rint | 0.059 | 0.066 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.198, 1.06 | 0.042, 0.110, 0.97 |
No. of reflections | 3737 | 7085 |
No. of parameters | 244 | 531 |
No. of restraints | 0 | 178 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.44 | 0.63, −0.63 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1a···O1 | 0.95 (4) | 1.85 (4) | 2.784 (3) | 169 (3) |
N1—H1b···O2i | 0.86 (4) | 1.90 (4) | 2.751 (3) | 171 (3) |
Symmetry code: (i) −x, −y+1, −z. |
Selected geometric parameters (Å, º) for (II) topAg1—O1 | 2.435 (2) | Ag1—P1 | 2.4073 (8) |
Ag1—O2 | 2.516 (2) | Ag1—P2 | 2.4753 (8) |
| | | |
O1—Ag1—O2 | 52.9 (1) | O2—Ag1—P1 | 118.2 (1) |
O1—Ag1—O1 | 129.6 (1) | O2—Ag1—P2 | 102.7 (1) |
O1—Ag1—P2 | 101.5 (1) | P1—Ag1—P2 | 127.0 (1) |
Dimeric 2,4-dichlorophenoxyacetic acid [O···O = 2.632 (6) Å; Smith et al., 1976] is a potent herbicide (Que Hee & Sutherland, 1981). The acid cocrystallizes with 4-aminobenzoic acid (Lynch et al., 1992) and with 2-aminopyrimidine (Lynch et al., 1994), and its anion has been characterized as the zinc (Kennard et al., 1982), potassium (Kennard et al., 1983), silver (Mak et al., 1988) and copper (Dendrinou-Samara et al., 1996) salts. The only ammonium salt of the acid that has been examined appears to be the 3-hydroxypyridinium derivative, which adopts a chain structure in which the anions are linked by hydrogen bonds (N···O = 2.60 and O···O = 2.55 Å; Byriel et al., 1992). The study on the present dicyclohexylammonium salt, (I), continues on studies of dicyclohexylammonium salts of monocarboxylic acids. Dicyclohexylammonium trifluoroacetate crystallizes as linear hydrogen-bonded chains [N···O = 2.785 (2) and 2.794 (2) Å; Ng et al., 1999], but this architecture is not common as several other dicyclohexylammonium monocarboxylates pack as dimeric ion-pairs across a centre of symmetry. Such an architecture is observed for the O-(N,N-dimethylmonothiocarbamoyl)acetate [N···O = 2.706 (4) and 2.750 (3) Å], N-phthaloylglycinate [N···O = 2.733 (5) and 2.783 (5) Å; Ng, 1995], bis(N,N-dimethyldithiocarbamoyl)acetate [N···O = 2.701 (3) and 2.796 (3) Å; 2.698 (3) and 2.837 (3) Å; Ng, 1996], N,N-dicyclohexyldithiocarbamoylacetate [N···O = 2.706 (2) and 2.757 (2) Å; Ng, 1997] and 3-oxapentamethylenedithiocarbamoylacetate [N···O = 2.732 (4) and 2.738 (4) Å; Ng & Hook, 1999]. As the substituted acetate group carries bulky substituents, steric effects probably contribute to this type of dimer formation. This arrangment is also found in the 2,4-dichlorophenoxyacetate [N···O = 2.751 (3) and 2.784 (3) Å]. the carbon–oxygen distances in the carboxyl –CO2 end [C—O = 1.224 (2) and 1.238 (2) Å] indicate delocalization of the negative charge. At the ether linkage, the Calkyl—O distance [C—O = 1.421 (4) Å] exceeds the Caryl—O distance [C—O = 1.356 (4) Å]. Bond dimensions in the anion are not much different from those found in the parent acid [C—Ocarboxyl = 1.217 (6) and 1.304 (5) Å; Calkyl—O = 1.423 (5), Caryl = 1.365 (5) Å; Smith et al., 1976]. In the parent acid as well as in the dicyclohexylammonium salt, the angle at the ether linkage is nearly 120°. The bond dimensions of the ether linkage in the acid and in the salt are in agreement with the results (Calkyl—O = 1.407, Caryl—O = 1.371 Å, C—O—C = 119.4°) of molecular mechanics calculations on the monomeric acid computed with the MM3+ basis set (Hypercube Inc., 1995). The computations suggest a planar structure as the most stable conformation; on the other hand, the carboxyl unit is twisted by 85.2° with respect to the aromatic ring in the acid and by 80.8 (3)° in the salt. The synclinal conformation of 2,4-dichlorophenoxyacetic acid appears to be a feature that is not usually found in other phenoxyacetic acids or in metal phenoxyacetates (Mak et al., 1988) such as zinc 2,4-dichlorophenoxyacetate (Kennard et al., 1982) and potassium 2,4-dichlorophenoxyacetate (Kennard et al., 1983).
The silver 2,4-dichlorophenoxyacetate dimer, for which only partial structural details are reported, displays a zigzag motif that is derived through carboxylate bridging of the two independent molecules, and both Ag atoms are two-coordinate. The compound is isomorphous and isostructural with silver 2-methyl-4-chlorophenoxyacetate [Ag—O = 2.185 (3)–2.217 (3) Å], whose full structural details are reported. As the dihedral angles between the carboxyl and the aromatic planes in the latter compound are 15 and 18°, both invidual monomers are almost planar (Mak et al., 1988). Bis(triphenylphosphine)(2,4-dichlorophenoxyacetato)silver, (II), shows a twist [dihedral angle = 65.1 (1)°] that is comparable with that found in the dicyclohexylammonium salt. The chain motif of the silver salt is disrupted upon coordination by the two phosphine-donor ligands, and two weaker silver–oxygen bonds are formed instead [Ag—O = 2.435 (2) and 2.516 (2) Å]. The distorted tetrahedral geometry of silver in this adduct is similar to those found in a number of 1:2 adducts of silver carboxylates with triphenylphosphine such as the acetate (Ng & Othman, 1997), trifluoroacetate (Ng, 1998) and lactate (Hanna & Ng, 2000).
Of the two triphenylphosphine ligands, one is disordered in two of phenyl rings. The C1–C6/C1'–C7' pair of rings are twisted by 42 (1)°, and the C7–C12/C7'–C12' pair by 33 (1)°. The disorder is corroborated by the CP/MAS spectral values: the 1J(Ag–P) coupling constants of the ordered and disordered phosphorus sites are significantly different. The linewidths of the NMR signals constitute the basis for assigning the ordered/disordered sites; the ordered phosphorus signal yields 1J(107Ag–31P) and 1J(109Ag–31P) couplings that are clearly resolved, whereas the disordered phosphorus signal is Lorentzian broaden so that these couplings cannot be resolved. The silver–phosphorusdisordered distance [2.4073 (8) Å] is statistically shorter than the silver–phosphorusordered distance [2.4753 (8) Å].