Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012202/gd1054sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012202/gd1054Isup2.hkl |
CCDC reference: 140925
Silver(I) lactate and triphenylphosphine (1:1 molar ratio) were dissolved in a small volume of ethanol. Slow cooling of the filtered solution yielded the title adduct, (I), as large crystals. The solid state 31P NMR spectrum was interpreted in terms of two orientations of the anion. Spectroscopic data for orientation 1 (δ, p.p.m.): 18.5 [1JAg—P = 478 Hz, 2JP—P = 144 Hz]; 12.9 [1JAg—P = 390 Hz, 2JP—P = 144 Hz]; orientation 2 (δ, p.p.m.): 16.6 [1JAg—P = 471 Hz, 2JP—P = 144 Hz]; 13.6 [1JAg—P = 478 Hz, 2JP—P = 144 Hz].
The methyl and hydroxyl groups on the C38 atom are disordered over two positions and were refined as two (CH3)(OH)CH– groups sharing a common C38 atom, subject to C—C = 1.54 (1), C—O = 1.45 (1), C···C = 2.52 (2) and C···O = 2.44 (2) Å. The displacement parameters for the umprimed and primed atoms were set to be equal.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
[Ag(C3H5O3)(C18H15P)2] | Z = 2 |
Mr = 721.48 | F(000) = 740 |
Triclinic, P1 | Dx = 1.404 Mg m−3 |
a = 12.5745 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.8844 (1) Å | Cell parameters from 8418 reflections |
c = 13.0438 (1) Å | θ = 1.8–29.3° |
α = 73.967 (1)° | µ = 0.72 mm−1 |
β = 66.242 (1)° | T = 298 K |
γ = 62.598 (1)° | Block, colourless |
V = 1706.43 (2) Å3 | 0.43 × 0.38 × 0.15 mm |
Siemens CCD area-detector diffractometer | 5792 independent reflections |
Radiation source: fine-focus sealed tube | 5263 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
frames ω scan | θmax = 25°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | h = −10→14 |
Tmin = 0.727, Tmax = 0.875 | k = −15→15 |
8775 measured reflections | l = −15→15 |
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0553P)2 + 1.5612P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
5792 reflections | Δρmax = 0.59 e Å−3 |
413 parameters | Δρmin = −0.78 e Å−3 |
6 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (1) |
[Ag(C3H5O3)(C18H15P)2] | γ = 62.598 (1)° |
Mr = 721.48 | V = 1706.43 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.5745 (1) Å | Mo Kα radiation |
b = 12.8844 (1) Å | µ = 0.72 mm−1 |
c = 13.0438 (1) Å | T = 298 K |
α = 73.967 (1)° | 0.43 × 0.38 × 0.15 mm |
β = 66.242 (1)° |
Siemens CCD area-detector diffractometer | 5792 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | 5263 reflections with I > 2σ(I) |
Tmin = 0.727, Tmax = 0.875 | Rint = 0.015 |
8775 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 6 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.59 e Å−3 |
5792 reflections | Δρmin = −0.78 e Å−3 |
413 parameters |
Experimental. 30 initial frames were recollected at the end of the data collection and the intensity decay was found to be negligible. |
Refinement. H atoms were treated as riding, with U(H) = 1.5Ueq(C) |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ag1 | 0.78510 (2) | 0.38529 (2) | 0.27978 (2) | 0.0436 (1) | |
P1 | 0.61037 (8) | 0.57128 (8) | 0.25834 (7) | 0.0396 (2) | |
P2 | 0.88000 (9) | 0.21779 (8) | 0.17013 (7) | 0.0400 (2) | |
O1 | 0.9543 (5) | 0.4029 (5) | 0.3208 (5) | 0.139 (2) | |
O2 | 0.8539 (3) | 0.3029 (3) | 0.4444 (3) | 0.074 (1) | |
O3 | 1.059 (1) | 0.3943 (9) | 0.479 (1) | 0.145 (3) | 0.50 |
O3' | 0.976 (1) | 0.275 (1) | 0.5859 (8) | 0.145 (3) | 0.50 |
C1 | 0.4779 (3) | 0.5492 (3) | 0.2553 (3) | 0.045 (1) | |
C2 | 0.4424 (4) | 0.5817 (4) | 0.1592 (4) | 0.059 (1) | |
C3 | 0.3474 (5) | 0.5546 (5) | 0.1587 (5) | 0.077 (1) | |
C4 | 0.2862 (5) | 0.4992 (5) | 0.2530 (5) | 0.076 (1) | |
C5 | 0.3200 (5) | 0.4667 (4) | 0.3491 (5) | 0.075 (1) | |
C6 | 0.4173 (4) | 0.4903 (4) | 0.3488 (4) | 0.061 (1) | |
C7 | 0.6506 (3) | 0.6616 (3) | 0.1248 (3) | 0.045 (1) | |
C8 | 0.6047 (4) | 0.7830 (3) | 0.1154 (4) | 0.057 (1) | |
C9 | 0.6397 (5) | 0.8473 (4) | 0.0116 (4) | 0.071 (1) | |
C10 | 0.7192 (5) | 0.7895 (5) | −0.0825 (4) | 0.069 (1) | |
C11 | 0.7647 (4) | 0.6684 (4) | −0.0750 (4) | 0.063 (1) | |
C12 | 0.7315 (4) | 0.6051 (4) | 0.0286 (3) | 0.054 (1) | |
C13 | 0.5428 (3) | 0.6725 (3) | 0.3640 (3) | 0.042 (1) | |
C14 | 0.6266 (4) | 0.7040 (4) | 0.3796 (4) | 0.061 (1) | |
C15 | 0.5832 (5) | 0.7847 (5) | 0.4532 (4) | 0.074 (1) | |
C16 | 0.4559 (5) | 0.8337 (4) | 0.5125 (4) | 0.073 (1) | |
C17 | 0.3742 (4) | 0.8009 (4) | 0.4988 (4) | 0.065 (1) | |
C18 | 0.4154 (4) | 0.7209 (3) | 0.4249 (3) | 0.050 (1) | |
C19 | 1.0181 (3) | 0.0903 (3) | 0.1946 (3) | 0.042 (1) | |
C20 | 1.0246 (4) | 0.0575 (4) | 0.3028 (4) | 0.066 (1) | |
C21 | 1.1275 (5) | −0.0413 (5) | 0.3241 (4) | 0.087 (2) | |
C22 | 1.2233 (5) | −0.1041 (4) | 0.2392 (4) | 0.073 (1) | |
C23 | 1.2196 (4) | −0.0697 (4) | 0.1315 (4) | 0.060 (1) | |
C24 | 1.1166 (4) | 0.0267 (3) | 0.1092 (3) | 0.051 (1) | |
C25 | 0.7685 (3) | 0.1572 (3) | 0.1833 (3) | 0.043 (1) | |
C26 | 0.7960 (4) | 0.0374 (4) | 0.2022 (4) | 0.057 (1) | |
C27 | 0.7075 (5) | −0.0035 (4) | 0.2100 (4) | 0.071 (1) | |
C28 | 0.5917 (5) | 0.0750 (5) | 0.1999 (4) | 0.075 (1) | |
C29 | 0.5624 (4) | 0.1945 (5) | 0.1815 (5) | 0.074 (1) | |
C30 | 0.6504 (4) | 0.2347 (4) | 0.1751 (4) | 0.059 (1) | |
C31 | 0.9364 (3) | 0.2616 (3) | 0.0196 (3) | 0.041 (1) | |
C32 | 0.9976 (4) | 0.3381 (4) | −0.0169 (3) | 0.053 (1) | |
C33 | 1.0413 (4) | 0.3744 (4) | −0.1303 (4) | 0.062 (1) | |
C34 | 1.0248 (4) | 0.3349 (4) | −0.2093 (3) | 0.060 (1) | |
C35 | 0.9652 (4) | 0.2593 (4) | −0.1743 (3) | 0.057 (1) | |
C36 | 0.9209 (4) | 0.2222 (3) | −0.0601 (3) | 0.051 (1) | |
C37 | 0.9356 (4) | 0.3421 (4) | 0.4098 (4) | 0.060 (1) | |
C38 | 1.0197 (6) | 0.3108 (5) | 0.4777 (6) | 0.094 (2) | 0.50 |
C39 | 1.112 (2) | 0.1841 (8) | 0.485 (2) | 0.117 (4) | 0.50 |
C38' | 1.0197 (6) | 0.3108 (5) | 0.4777 (6) | 0.094 (2) | 0.50 |
C39' | 1.156 (1) | 0.225 (1) | 0.418 (1) | 0.117 (4) | 0.50 |
H2 | 0.4820 | 0.6214 | 0.0955 | 0.088* | |
H3 | 0.3254 | 0.5743 | 0.0938 | 0.116* | |
H4 | 0.2214 | 0.4834 | 0.2524 | 0.114* | |
H5 | 0.2781 | 0.4295 | 0.4133 | 0.112* | |
H6 | 0.4422 | 0.4661 | 0.4126 | 0.091* | |
H8 | 0.5501 | 0.8222 | 0.1788 | 0.086* | |
H9 | 0.6092 | 0.9288 | 0.0061 | 0.106* | |
H10 | 0.7426 | 0.8323 | −0.1516 | 0.103* | |
H11 | 0.8171 | 0.6297 | −0.1390 | 0.095* | |
H12 | 0.7638 | 0.5235 | 0.0340 | 0.081* | |
H14 | 0.7126 | 0.6706 | 0.3401 | 0.092* | |
H15 | 0.6398 | 0.8059 | 0.4628 | 0.111* | |
H16 | 0.4260 | 0.8889 | 0.5614 | 0.110* | |
H17 | 0.2886 | 0.8329 | 0.5402 | 0.097* | |
H18 | 0.3582 | 0.7000 | 0.4162 | 0.074* | |
H20 | 0.9609 | 0.1009 | 0.3611 | 0.099* | |
H21 | 1.1305 | −0.0646 | 0.3973 | 0.131* | |
H22 | 1.2910 | −0.1701 | 0.2546 | 0.109* | |
H23 | 1.2860 | −0.1110 | 0.0730 | 0.090* | |
H24 | 1.1140 | 0.0487 | 0.0358 | 0.076* | |
H26 | 0.8741 | −0.0160 | 0.2098 | 0.085* | |
H27 | 0.7269 | −0.0839 | 0.2220 | 0.107* | |
H28 | 0.5327 | 0.0475 | 0.2054 | 0.113* | |
H29 | 0.4845 | 0.2475 | 0.1735 | 0.111* | |
H30 | 0.6296 | 0.3152 | 0.1651 | 0.088* | |
H32 | 1.0091 | 0.3651 | 0.0354 | 0.080* | |
H33 | 1.0821 | 0.4256 | −0.1538 | 0.093* | |
H34 | 1.0540 | 0.3597 | −0.2855 | 0.090* | |
H35 | 0.9543 | 0.2324 | −0.2271 | 0.085* | |
H36 | 0.8807 | 0.1707 | −0.0372 | 0.076* | |
H38 | 0.9585 | 0.3124 | 0.5538 | 0.142* | 0.50 |
H3A | 1.1089 | 0.3641 | 0.5275 | 0.218* | 0.00 |
H3B | 0.9859 | 0.4639 | 0.5050 | 0.218* | 0.50 |
H3C | 1.1082 | 0.4132 | 0.4035 | 0.218* | 0.00 |
H39A | 1.1566 | 0.1726 | 0.5349 | 0.176* | 0.50 |
H39B | 1.1715 | 0.1656 | 0.4114 | 0.176* | 0.50 |
H39C | 1.0668 | 0.1337 | 0.5135 | 0.176* | 0.50 |
H38' | 1.0272 | 0.3838 | 0.4758 | 0.142* | 0.50 |
H3'1 | 1.0349 | 0.2603 | 0.6225 | 0.218* | 0.00 |
H3'2 | 0.9648 | 0.2042 | 0.5931 | 0.218* | 0.50 |
H3'3 | 0.8959 | 0.3350 | 0.6204 | 0.218* | 0.00 |
H39D | 1.2081 | 0.2038 | 0.4635 | 0.176* | 0.50 |
H39E | 1.1901 | 0.2625 | 0.3459 | 0.176* | 0.50 |
H39F | 1.1525 | 0.1554 | 0.4081 | 0.176* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0456 (2) | 0.0409 (2) | 0.0435 (2) | −0.0108 (1) | −0.0196 (1) | −0.0069 (1) |
P1 | 0.0387 (5) | 0.0385 (5) | 0.0389 (5) | −0.0108 (4) | −0.0144 (4) | −0.0055 (3) |
P2 | 0.0440 (5) | 0.0356 (4) | 0.0393 (5) | −0.0100 (4) | −0.0176 (4) | −0.0068 (3) |
O1 | 0.143 (4) | 0.167 (5) | 0.148 (4) | −0.115 (4) | −0.106 (4) | 0.106 (4) |
O2 | 0.061 (2) | 0.111 (3) | 0.055 (2) | −0.042 (2) | −0.022 (2) | 0.000 (2) |
O3 | 0.147 (7) | 0.201 (9) | 0.135 (7) | −0.079 (6) | −0.082 (6) | −0.013 (6) |
O3' | 0.147 (7) | 0.201 (9) | 0.135 (7) | −0.079 (6) | −0.082 (6) | −0.013 (6) |
C1 | 0.043 (2) | 0.036 (2) | 0.057 (2) | −0.009 (2) | −0.024 (2) | −0.006 (2) |
C2 | 0.053 (2) | 0.065 (3) | 0.059 (2) | −0.015 (2) | −0.027 (2) | −0.009 (2) |
C3 | 0.067 (3) | 0.090 (4) | 0.088 (4) | −0.022 (3) | −0.047 (3) | −0.015 (3) |
C4 | 0.058 (3) | 0.077 (3) | 0.109 (4) | −0.025 (2) | −0.040 (3) | −0.016 (3) |
C5 | 0.064 (3) | 0.071 (3) | 0.097 (4) | −0.036 (2) | −0.031 (3) | 0.003 (3) |
C6 | 0.064 (3) | 0.059 (2) | 0.069 (3) | −0.031 (2) | −0.033 (2) | 0.008 (2) |
C7 | 0.044 (2) | 0.045 (2) | 0.045 (2) | −0.015 (2) | −0.017 (2) | −0.005 (2) |
C8 | 0.060 (2) | 0.045 (2) | 0.056 (2) | −0.015 (2) | −0.014 (2) | −0.005 (2) |
C9 | 0.081 (3) | 0.057 (3) | 0.066 (3) | −0.029 (2) | −0.025 (2) | 0.009 (2) |
C10 | 0.075 (3) | 0.087 (3) | 0.052 (2) | −0.046 (3) | −0.025 (2) | 0.012 (2) |
C11 | 0.069 (3) | 0.082 (3) | 0.044 (2) | −0.038 (2) | −0.014 (2) | −0.009 (2) |
C12 | 0.056 (2) | 0.057 (2) | 0.046 (2) | −0.020 (2) | −0.014 (2) | −0.011 (2) |
C13 | 0.044 (2) | 0.044 (2) | 0.036 (2) | −0.016 (2) | −0.013 (1) | −0.004 (1) |
C14 | 0.053 (2) | 0.083 (3) | 0.055 (2) | −0.034 (2) | −0.006 (2) | −0.025 (2) |
C15 | 0.089 (3) | 0.094 (4) | 0.062 (3) | −0.056 (3) | −0.016 (2) | −0.021 (2) |
C16 | 0.091 (4) | 0.074 (3) | 0.052 (2) | −0.032 (3) | −0.010 (2) | −0.024 (2) |
C17 | 0.059 (2) | 0.069 (3) | 0.048 (2) | −0.013 (2) | −0.007 (2) | −0.018 (2) |
C18 | 0.045 (2) | 0.054 (2) | 0.041 (2) | −0.014 (2) | −0.013 (2) | −0.005 (2) |
C19 | 0.045 (2) | 0.035 (2) | 0.046 (2) | −0.011 (2) | −0.021 (2) | −0.004 (1) |
C20 | 0.068 (3) | 0.066 (3) | 0.047 (2) | −0.009 (2) | −0.026 (2) | −0.003 (2) |
C21 | 0.087 (4) | 0.086 (4) | 0.059 (3) | 0.001 (3) | −0.044 (3) | 0.003 (3) |
C22 | 0.067 (3) | 0.056 (3) | 0.081 (3) | 0.002 (2) | −0.043 (3) | −0.006 (2) |
C23 | 0.053 (2) | 0.048 (2) | 0.074 (3) | −0.004 (2) | −0.026 (2) | −0.017 (2) |
C24 | 0.058 (2) | 0.042 (2) | 0.050 (2) | −0.011 (2) | −0.025 (2) | −0.007 (2) |
C25 | 0.048 (2) | 0.044 (2) | 0.037 (2) | −0.018 (2) | −0.011 (2) | −0.009 (1) |
C26 | 0.058 (2) | 0.051 (2) | 0.059 (2) | −0.023 (2) | −0.014 (2) | −0.008 (2) |
C27 | 0.077 (3) | 0.061 (3) | 0.079 (3) | −0.036 (3) | −0.013 (2) | −0.015 (2) |
C28 | 0.067 (3) | 0.096 (4) | 0.079 (3) | −0.043 (3) | −0.011 (2) | −0.031 (3) |
C29 | 0.055 (3) | 0.080 (3) | 0.094 (4) | −0.021 (2) | −0.025 (2) | −0.028 (3) |
C30 | 0.048 (2) | 0.053 (2) | 0.076 (3) | −0.013 (2) | −0.023 (2) | −0.016 (2) |
C31 | 0.042 (2) | 0.036 (2) | 0.042 (2) | −0.009 (1) | −0.018 (2) | −0.004 (1) |
C32 | 0.050 (2) | 0.056 (2) | 0.057 (2) | −0.023 (2) | −0.016 (2) | −0.010 (2) |
C33 | 0.053 (2) | 0.061 (3) | 0.068 (3) | −0.028 (2) | −0.015 (2) | 0.003 (2) |
C34 | 0.047 (2) | 0.065 (3) | 0.045 (2) | −0.011 (2) | −0.013 (2) | 0.004 (2) |
C35 | 0.064 (2) | 0.061 (2) | 0.045 (2) | −0.021 (2) | −0.024 (2) | −0.004 (2) |
C36 | 0.064 (2) | 0.047 (2) | 0.045 (2) | −0.023 (2) | −0.022 (2) | −0.003 (2) |
C37 | 0.070 (3) | 0.061 (3) | 0.061 (3) | −0.029 (2) | −0.034 (2) | 0.000 (2) |
C38 | 0.109 (5) | 0.096 (4) | 0.121 (5) | −0.048 (4) | −0.079 (4) | 0.003 (4) |
C39 | 0.14 (1) | 0.102 (9) | 0.15 (1) | −0.036 (7) | −0.11 (1) | 0.015 (7) |
C38' | 0.109 (5) | 0.096 (4) | 0.121 (5) | −0.048 (4) | −0.079 (4) | 0.003 (4) |
C39' | 0.14 (1) | 0.102 (9) | 0.15 (1) | −0.036 (7) | −0.11 (1) | 0.015 (7) |
Ag1—P1 | 2.4345 (9) | C13—C14 | 1.389 (5) |
Ag1—P2 | 2.4671 (9) | C14—C15 | 1.382 (6) |
Ag1—O1 | 2.508 (4) | C15—C16 | 1.379 (7) |
Ag1—O2 | 2.425 (3) | C16—C17 | 1.363 (7) |
P1—C1 | 1.832 (4) | C17—C18 | 1.383 (6) |
P1—C7 | 1.832 (4) | C19—C24 | 1.380 (5) |
P1—C13 | 1.830 (4) | C19—C20 | 1.382 (5) |
P2—C19 | 1.830 (3) | C20—C21 | 1.395 (6) |
P2—C25 | 1.829 (4) | C21—C22 | 1.362 (7) |
P2—C31 | 1.819 (4) | C22—C23 | 1.365 (7) |
O1—C37 | 1.210 (6) | C23—C24 | 1.389 (5) |
O2—C37 | 1.222 (5) | C25—C30 | 1.385 (5) |
C37—C38 | 1.493 (6) | C25—C26 | 1.389 (5) |
C1—C6 | 1.384 (6) | C26—C27 | 1.395 (6) |
C1—C2 | 1.390 (5) | C27—C28 | 1.373 (7) |
C2—C3 | 1.394 (6) | C28—C29 | 1.382 (7) |
C3—C4 | 1.368 (8) | C29—C30 | 1.389 (6) |
C4—C5 | 1.379 (7) | C31—C32 | 1.390 (5) |
C5—C6 | 1.388 (6) | C31—C36 | 1.386 (5) |
C7—C8 | 1.384 (5) | C32—C33 | 1.381 (6) |
C7—C12 | 1.391 (5) | C33—C34 | 1.386 (6) |
C8—C9 | 1.395 (6) | C34—C35 | 1.367 (6) |
C9—C10 | 1.374 (7) | C35—C36 | 1.393 (6) |
C10—C11 | 1.383 (7) | C38—O3 | 1.375 (8) |
C11—C12 | 1.384 (6) | C38—C39 | 1.510 (9) |
C13—C18 | 1.384 (5) | ||
P1—Ag1—P2 | 126.15 (3) | C12—C11—C10 | 119.5 (4) |
P1—Ag1—O1 | 114.6 (1) | C7—C12—C11 | 121.1 (4) |
P1—Ag1—O2 | 126.5 (1) | C18—C13—C14 | 119.2 (3) |
P2—Ag1—O1 | 109.7 (2) | C18—C13—P1 | 124.3 (3) |
P2—Ag1—O2 | 104.7 (1) | C14—C13—P1 | 116.4 (3) |
O1—Ag1—O2 | 51.3 (1) | C15—C14—C13 | 120.5 (4) |
C1—P1—C7 | 103.4 (2) | C16—C15—C14 | 119.8 (4) |
C1—P1—C13 | 106.2 (2) | C17—C16—C15 | 119.6 (4) |
C13—P1—C7 | 103.3 (2) | C16—C17—C18 | 121.5 (4) |
C13—P1—Ag1 | 117.2 (1) | C17—C18—C13 | 119.3 (4) |
C1—P1—Ag1 | 111.8 (1) | C24—C19—C20 | 118.8 (3) |
C7—P1—Ag1 | 113.6 (1) | C24—C19—P2 | 122.6 (3) |
C19—P2—C25 | 105.1 (2) | C20—C19—P2 | 118.6 (3) |
C19—P2—C31 | 103.0 (2) | C19—C20—C21 | 119.6 (4) |
C25—P2—C31 | 103.6 (2) | C22—C21—C20 | 121.0 (4) |
C19—P2—Ag1 | 118.4 (1) | C21—C22—C23 | 119.6 (4) |
C25—P2—Ag1 | 113.9 (1) | C22—C23—C24 | 120.1 (4) |
C31—P2—Ag1 | 111.4 (1) | C19—C24—C23 | 120.8 (4) |
C37—O1—Ag1 | 91.0 (3) | C30—C25—C26 | 118.4 (4) |
C37—O2—Ag1 | 94.7 (3) | C30—C25—P2 | 118.3 (3) |
O1—C37—O2 | 122.9 (4) | C26—C25—P2 | 123.2 (3) |
O1—C37—C38 | 118.0 (5) | C27—C26—C25 | 120.5 (4) |
O2—C37—C38 | 119.1 (4) | C28—C27—C26 | 120.0 (4) |
C6—C1—C2 | 118.9 (4) | C27—C28—C29 | 120.4 (4) |
C6—C1—P1 | 118.9 (3) | C28—C29—C30 | 119.4 (5) |
C2—C1—P1 | 122.1 (3) | C25—C30—C29 | 121.3 (4) |
C1—C2—C3 | 119.7 (4) | C32—C31—C36 | 118.6 (3) |
C4—C3—C2 | 120.6 (4) | C32—C31—P2 | 118.5 (3) |
C3—C4—C5 | 120.4 (4) | C36—C31—P2 | 122.9 (3) |
C4—C5—C6 | 119.2 (5) | C33—C32—C31 | 120.5 (4) |
C1—C6—C5 | 121.2 (4) | C32—C33—C34 | 120.4 (4) |
C8—C7—C12 | 118.6 (4) | C35—C34—C33 | 119.6 (4) |
C8—C7—P1 | 123.1 (3) | C34—C35—C36 | 120.4 (4) |
C12—C7—P1 | 118.3 (3) | C35—C36—C31 | 120.5 (4) |
C7—C8—C9 | 120.7 (4) | O3—C38—C37 | 118.1 (6) |
C10—C9—C8 | 119.7 (4) | O3—C38—C39 | 116.7 (8) |
C9—C10—C11 | 120.5 (4) | C37—C38—C39 | 116.5 (7) |
Experimental details
Crystal data | |
Chemical formula | [Ag(C3H5O3)(C18H15P)2] |
Mr | 721.48 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 12.5745 (1), 12.8844 (1), 13.0438 (1) |
α, β, γ (°) | 73.967 (1), 66.242 (1), 62.598 (1) |
V (Å3) | 1706.43 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.43 × 0.38 × 0.15 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.727, 0.875 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8775, 5792, 5263 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.107, 1.09 |
No. of reflections | 5792 |
No. of parameters | 413 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.78 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997a), ORTEPII (Johnson, 1976), SHELXL97.
Ag1—P1 | 2.4345 (9) | Ag1—O1 | 2.508 (4) |
Ag1—P2 | 2.4671 (9) | Ag1—O2 | 2.425 (3) |
P1—Ag1—P2 | 126.15 (3) | P2—Ag1—O1 | 109.7 (2) |
P1—Ag1—O1 | 114.6 (1) | P2—Ag1—O2 | 104.7 (1) |
P1—Ag1—O2 | 126.5 (1) | O1—Ag1—O2 | 51.3 (1) |
The reaction of silver acetate and triphenylphosphine in ethanol produces 1:1 and 1:2 adducts, and both adducts crystallize with one or more water/ethanol molecules (Hanna & Ng, 1999; Ng & Othman, 1995, 1997). Silver trifluoroacetate yields only the anhydrous 1:2 adduct (Ng, 1998), as does the present lactate, (lactato-O,O')bis(triphenylphosphine-P)silver(I), (I). In (I), the Ag atom shows tetrahedral coordination [Ag—P = 2.4345 (9) and 2.4671 (9) Å, and Ag—O = 2.425 (3) and 2.508 (4) Å] but the geometry is distorted owing to the small bite of the carboxyl group [O—Ag—O = 51.3 (1)°]. The geometry is similar to those found in the analogous bis(triphenylphosphine) complexes of the acetate and trifluoroacetate.
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The solid-state NMR spectral characterization of the compound was undertaken with 13C CPMAS, one-dimensional 31P CPMAS and two-dimensional 31P CPCOSY techniques (CPMAS = ???; CPCOSY = CP??? correlated spectroscopy). The 13C CPMAS NMR confirmed the lactate coordination, with resonances being observed at 24.2, 70.3 and 183.1 p.p.m. These resonances are assigned to the –CH3, –CH(OH) and –CO2 groups, respectively. The unit cell has only one independent molecule, but the molecule exhibits disorder with respect to the positioning of the –CH3 and –OH groups. The 13C NMR chemical shifts are insensitive to this disorder, however, so that only one methyl signal is observed. On the other hand, the 31P NMR chemical shifts are much more sensitive to such structural differences. In the 31P CPMAS spectrum, both orientations of the CH3/OH groups are clearly resolved to be (approximately) equally distributed (i.e. 1:1) between the two orientations. The much larger 31P chemical shift anisotropy and the greater sensitivity of the σ11, σ22 and σ33 shift tensorial elements with respect to long-range metal coordination and geometry make this nucleus more diagnostic in the study of such disorder than its 13C counterparts. The one-dimensional 31P CPMAS spectrum is a complex overlap of four doublet-of-doublets (i.e. 16 resonances) that can only be properly analyzed in a two-dimensional 31P CPCOSY experiment. The one-bond 1JAg—P coupling constants exhibit virtually no variation (within experimental error) from this disorder, with orientation 1 yielding 478 Hz and 390 Hz, and orientation 2 yielding 471 Hz and 389 Hz (see Experimental).
The structure of [silver bis(triphenylphosphine)actate]·0.5H2O·0.75CH3CH2OH is disordered (Hanna & Ng, 1999), but the disorder concerns only the lattice ethanol, which is hydrogen bonded to the lattice water molecule. The disorder is not noted in its 31P CPMAS.
The invariate behaviour of the 1JAg—P coupling constants of the lactate in (I) suggests that the bond angles and distances of the P2AgO2 core, and the phenyl ring twist of each triphenylphosphine entity, are largely unperturbed by the different orientations defining this disorder. However, the spread of 31P chemical shifts from the two P sites in each molecule is unambiguously different for each orientation adopted by the lactate group. Orientation 1 yields a greater dispersion of 31P chemical shifts, with values of 18.5 p.p.m. and 12.9 p.p.m. being obtained, whereas the shifts defining orientation 2 (16.6 pm and 13.6 p.p.m.) are much closer.