Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010200848X/av1108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010200848X/av1108Isup2.hkl |
CCDC reference: 173459
The title compound was prepared and characterized using the method reported by Kannan, Venugopal, Pillai, Droege, Barnes & Schlember (1996). Crystals of (I) suitable for X-ray diffraction analysis were obtained from slow evaporation of a chloform-toluene solution.
The Friedel opposites were not merged and the choice of absolute structure was determined by the Flack parameter (Flack, 1983; Flack & Bernardinelli, 1999, 2000). All six phenyl groups were fitted as regular aromatic rings with C—C distances of 1.390 Å and were refined anistropically. All H atoms were geometrically fixed and allowed to ride on their attached parent C atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
[U(C15H11O2)2(C14H14OS)O2] | Dx = 1.607 Mg m−3 |
Mr = 946.82 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8192 reflections |
a = 12.3178 (1) Å | θ = 2.6–28.3° |
b = 15.5281 (1) Å | µ = 4.25 mm−1 |
c = 20.4617 (1) Å | T = 183 K |
V = 3913.75 (4) Å3 | Block, red |
Z = 4 | 0.34 × 0.16 × 0.16 mm |
F(000) = 1856 |
Siemens SMART CCD area-detector diffractometer | 9217 independent reflections |
Radiation source: fine-focus sealed tube | 7611 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.092 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.6° |
ω scans | h = −16→15 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −20→14 |
Tmin = 0.300, Tmax = 0.507 | l = −26→26 |
23363 measured reflections |
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)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0423P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
9217 reflections | Δρmax = 2.01 e Å−3 |
352 parameters | Δρmin = −3.10 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 3842 Friedel reflections |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.023 (10) |
[U(C15H11O2)2(C14H14OS)O2] | V = 3913.75 (4) Å3 |
Mr = 946.82 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.3178 (1) Å | µ = 4.25 mm−1 |
b = 15.5281 (1) Å | T = 183 K |
c = 20.4617 (1) Å | 0.34 × 0.16 × 0.16 mm |
Siemens SMART CCD area-detector diffractometer | 9217 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 7611 reflections with I > 2σ(I) |
Tmin = 0.300, Tmax = 0.507 | Rint = 0.092 |
23363 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.121 | Δρmax = 2.01 e Å−3 |
S = 0.98 | Δρmin = −3.10 e Å−3 |
9217 reflections | Absolute structure: Flack (1983), 3842 Friedel reflections |
352 parameters | Absolute structure parameter: 0.023 (10) |
0 restraints |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
U1 | 0.37242 (2) | 0.429082 (18) | −0.016628 (13) | 0.01416 (8) | |
S1 | 0.13073 (19) | 0.37490 (12) | 0.05943 (9) | 0.0178 (4) | |
O1 | 0.2597 (5) | 0.4962 (4) | −0.0382 (3) | 0.0255 (15) | |
O2 | 0.4814 (5) | 0.3591 (4) | 0.0066 (3) | 0.0234 (14) | |
O3 | 0.4736 (5) | 0.5562 (4) | −0.0096 (3) | 0.0258 (14) | |
O4 | 0.3673 (5) | 0.4807 (4) | 0.0913 (3) | 0.0231 (12) | |
O5 | 0.3001 (5) | 0.3319 (4) | −0.0936 (3) | 0.0269 (15) | |
O6 | 0.4637 (6) | 0.4472 (5) | −0.1154 (3) | 0.0375 (19) | |
O7 | 0.2435 (4) | 0.3410 (4) | 0.0425 (3) | 0.0184 (12) | |
C1 | 0.1487 (5) | 0.2229 (4) | −0.1436 (2) | 0.026 (2) | |
H1 | 0.1640 | 0.2207 | −0.0991 | 0.031* | |
C2 | 0.0590 (5) | 0.1794 (4) | −0.1683 (3) | 0.038 (3) | |
H2 | 0.0143 | 0.1482 | −0.1404 | 0.046* | |
C3 | 0.0362 (4) | 0.1826 (4) | −0.2348 (3) | 0.033 (2) | |
H3 | −0.0238 | 0.1535 | −0.2514 | 0.039* | |
C4 | 0.1030 (5) | 0.2292 (4) | −0.2766 (2) | 0.044 (3) | |
H4 | 0.0877 | 0.2314 | −0.3210 | 0.053* | |
C5 | 0.1927 (5) | 0.2727 (4) | −0.2518 (2) | 0.0230 (19) | |
H5 | 0.2375 | 0.3039 | −0.2798 | 0.028* | |
C6 | 0.2156 (4) | 0.2695 (3) | −0.1854 (3) | 0.0140 (16) | |
C7 | 0.3007 (6) | 0.3221 (5) | −0.1558 (4) | 0.0164 (17) | |
C8 | 0.3774 (9) | 0.3580 (5) | −0.1955 (4) | 0.0268 (19) | |
H8 | 0.3763 | 0.3424 | −0.2394 | 0.032* | |
C9 | 0.4602 (7) | 0.4184 (6) | −0.1750 (4) | 0.0197 (18) | |
C10 | 0.5455 (4) | 0.4557 (4) | −0.2209 (3) | 0.023 (2) | |
C11 | 0.5379 (5) | 0.4442 (5) | −0.2882 (3) | 0.048 (2) | |
H11 | 0.4790 | 0.4148 | −0.3058 | 0.057* | |
C12 | 0.6182 (6) | 0.4768 (5) | −0.3290 (2) | 0.048 (2) | |
H12 | 0.6131 | 0.4691 | −0.3740 | 0.057* | |
C13 | 0.7062 (5) | 0.5208 (5) | −0.3026 (3) | 0.054 (4) | |
H13 | 0.7599 | 0.5426 | −0.3299 | 0.064* | |
C14 | 0.7138 (4) | 0.5322 (4) | −0.2354 (4) | 0.047 (3) | |
H14 | 0.7726 | 0.5617 | −0.2177 | 0.056* | |
C15 | 0.6335 (5) | 0.4997 (4) | −0.1945 (2) | 0.032 (2) | |
H15 | 0.6386 | 0.5073 | −0.1496 | 0.038* | |
C16 | 0.5828 (7) | 0.6955 (5) | −0.0592 (3) | 0.068 (2) | |
H16 | 0.5464 | 0.6575 | −0.0867 | 0.081* | |
C17 | 0.6447 (8) | 0.7618 (5) | −0.0855 (3) | 0.068 (2) | |
H17 | 0.6498 | 0.7682 | −0.1306 | 0.081* | |
C18 | 0.6990 (7) | 0.8187 (5) | −0.0444 (4) | 0.058 (4) | |
H18 | 0.7404 | 0.8630 | −0.0620 | 0.070* | |
C19 | 0.6913 (7) | 0.8092 (5) | 0.0230 (3) | 0.068 (2) | |
H19 | 0.7277 | 0.8472 | 0.0505 | 0.081* | |
C20 | 0.6294 (8) | 0.7428 (5) | 0.0493 (2) | 0.0678 (3) | |
H20 | 0.6243 | 0.7365 | 0.0944 | 0.081* | |
C21 | 0.5751 (7) | 0.6860 (5) | 0.0082 (3) | 0.068 (2) | |
C22 | 0.5089 (6) | 0.6089 (6) | 0.0325 (4) | 0.0176 (16) | |
C23 | 0.4930 (8) | 0.5974 (5) | 0.1000 (4) | 0.023 (2) | |
H23 | 0.5280 | 0.6349 | 0.1285 | 0.027* | |
C24 | 0.4281 (7) | 0.5332 (5) | 0.1264 (4) | 0.0191 (18) | |
C25 | 0.4162 (4) | 0.5231 (4) | 0.19876 (19) | 0.0204 (19) | |
C26 | 0.5006 (4) | 0.5468 (4) | 0.2401 (3) | 0.024 (2) | |
H26 | 0.5644 | 0.5694 | 0.2228 | 0.029* | |
C27 | 0.4898 (4) | 0.5367 (4) | 0.3073 (2) | 0.031 (2) | |
H27 | 0.5463 | 0.5525 | 0.3349 | 0.037* | |
C28 | 0.3945 (5) | 0.5029 (4) | 0.3331 (2) | 0.046 (3) | |
H28 | 0.3873 | 0.4961 | 0.3781 | 0.055* | |
C29 | 0.3101 (4) | 0.4792 (4) | 0.2918 (3) | 0.028 (2) | |
H29 | 0.2464 | 0.4566 | 0.3091 | 0.034* | |
C30 | 0.3209 (4) | 0.4893 (4) | 0.2246 (3) | 0.025 (2) | |
H30 | 0.2644 | 0.4735 | 0.1969 | 0.030* | |
C31 | 0.2081 (5) | 0.2365 (4) | 0.1874 (3) | 0.036 (2) | |
H31 | 0.2445 | 0.2093 | 0.1533 | 0.044* | |
C32 | 0.2473 (5) | 0.2299 (5) | 0.2509 (4) | 0.061 (4) | |
H32 | 0.3098 | 0.1983 | 0.2593 | 0.073* | |
C33 | 0.1930 (7) | 0.2707 (6) | 0.3018 (3) | 0.066 (3) | |
H33 | 0.2192 | 0.2663 | 0.3443 | 0.079* | |
C34 | 0.0995 (7) | 0.3180 (6) | 0.2891 (3) | 0.066 (3) | |
H34 | 0.0632 | 0.3453 | 0.3232 | 0.079* | |
C35 | 0.0604 (5) | 0.3246 (5) | 0.2256 (3) | 0.0657 (16) | |
H35 | −0.0022 | 0.3563 | 0.2172 | 0.079* | |
C36 | 0.1147 (5) | 0.2839 (4) | 0.1747 (2) | 0.0204 (16) | |
C37 | 0.0682 (8) | 0.2891 (7) | 0.1064 (4) | 0.029 (2) | |
H37A | −0.0094 | 0.2990 | 0.1091 | 0.035* | |
H37B | 0.0797 | 0.2346 | 0.0843 | 0.035* | |
C38 | 0.0515 (7) | 0.3604 (6) | −0.0155 (5) | 0.0234 (18) | |
H38A | 0.0941 | 0.3794 | −0.0527 | 0.028* | |
H38B | 0.0356 | 0.2997 | −0.0214 | 0.028* | |
C39 | −0.0535 (3) | 0.4105 (3) | −0.0132 (3) | 0.0217 (18) | |
C40 | −0.0537 (4) | 0.5000 (3) | −0.0150 (3) | 0.032 (2) | |
H40 | 0.0116 | 0.5301 | −0.0157 | 0.038* | |
C41 | −0.1516 (5) | 0.5446 (3) | −0.0159 (4) | 0.062 (4) | |
H41 | −0.1517 | 0.6044 | −0.0171 | 0.074* | |
C42 | −0.2492 (4) | 0.4997 (4) | −0.0149 (4) | 0.0501 (18) | |
H42 | −0.3146 | 0.5295 | −0.0155 | 0.060* | |
C43 | −0.2489 (3) | 0.4102 (4) | −0.0131 (4) | 0.0501 (18) | |
H43 | −0.3142 | 0.3801 | −0.0125 | 0.060* | |
C44 | −0.1511 (4) | 0.3656 (3) | −0.0123 (4) | 0.0501 (18) | |
H44 | −0.1509 | 0.3057 | −0.0111 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.01510 (13) | 0.01480 (12) | 0.01259 (12) | −0.00337 (13) | −0.00159 (13) | −0.00205 (13) |
S1 | 0.0176 (9) | 0.0194 (9) | 0.0163 (9) | 0.0005 (9) | −0.0004 (9) | −0.0012 (7) |
O1 | 0.016 (3) | 0.024 (3) | 0.037 (4) | −0.008 (3) | −0.012 (3) | 0.014 (3) |
O2 | 0.021 (3) | 0.021 (3) | 0.029 (4) | −0.001 (2) | −0.007 (3) | 0.000 (3) |
O3 | 0.030 (3) | 0.026 (3) | 0.022 (3) | −0.018 (3) | −0.001 (3) | −0.010 (3) |
O4 | 0.025 (3) | 0.026 (3) | 0.018 (3) | −0.007 (3) | −0.002 (3) | −0.003 (2) |
O5 | 0.027 (4) | 0.035 (4) | 0.019 (3) | −0.018 (3) | 0.004 (3) | −0.001 (3) |
O6 | 0.048 (4) | 0.046 (5) | 0.019 (3) | −0.028 (4) | 0.010 (3) | −0.009 (3) |
O7 | 0.005 (3) | 0.025 (3) | 0.025 (3) | −0.001 (2) | 0.001 (2) | 0.000 (3) |
C1 | 0.035 (6) | 0.019 (4) | 0.025 (4) | −0.013 (4) | 0.005 (4) | −0.012 (4) |
C2 | 0.051 (7) | 0.031 (6) | 0.032 (6) | −0.017 (5) | 0.012 (5) | −0.004 (5) |
C3 | 0.031 (6) | 0.027 (5) | 0.041 (6) | −0.012 (4) | −0.013 (5) | −0.006 (5) |
C4 | 0.089 (10) | 0.018 (5) | 0.025 (5) | −0.007 (5) | −0.019 (6) | −0.001 (4) |
C5 | 0.025 (5) | 0.019 (5) | 0.025 (5) | −0.006 (4) | −0.002 (4) | −0.001 (4) |
C6 | 0.011 (4) | 0.012 (4) | 0.018 (4) | 0.000 (3) | −0.002 (3) | −0.003 (3) |
C7 | 0.013 (4) | 0.017 (4) | 0.019 (4) | 0.002 (3) | −0.002 (3) | −0.002 (3) |
C8 | 0.038 (5) | 0.027 (5) | 0.015 (4) | −0.009 (5) | 0.002 (5) | −0.008 (3) |
C9 | 0.021 (4) | 0.015 (4) | 0.022 (4) | 0.004 (4) | −0.001 (3) | −0.001 (4) |
C10 | 0.017 (4) | 0.025 (5) | 0.026 (5) | 0.004 (3) | 0.001 (4) | 0.000 (4) |
C11 | 0.064 (6) | 0.058 (6) | 0.021 (4) | −0.005 (5) | 0.010 (4) | 0.008 (4) |
C12 | 0.064 (6) | 0.058 (6) | 0.021 (4) | −0.005 (5) | 0.010 (4) | 0.008 (4) |
C13 | 0.014 (5) | 0.071 (9) | 0.077 (9) | −0.001 (5) | 0.016 (6) | 0.019 (8) |
C14 | 0.020 (6) | 0.059 (8) | 0.061 (8) | −0.015 (5) | 0.014 (5) | −0.004 (7) |
C15 | 0.032 (5) | 0.028 (5) | 0.036 (5) | −0.013 (5) | 0.013 (5) | 0.001 (4) |
C16 | 0.120 (6) | 0.052 (4) | 0.031 (3) | −0.049 (4) | −0.001 (4) | 0.004 (3) |
C17 | 0.120 (6) | 0.052 (4) | 0.031 (3) | −0.049 (4) | −0.001 (4) | 0.004 (3) |
C18 | 0.081 (9) | 0.038 (7) | 0.056 (8) | −0.040 (6) | 0.006 (7) | −0.002 (6) |
C19 | 0.120 (6) | 0.052 (4) | 0.031 (3) | −0.049 (4) | −0.001 (4) | 0.004 (3) |
C20 | 0.1198 (6) | 0.0524 (6) | 0.0313 (4) | −0.049 (4) | −0.001 (4) | 0.004 (3) |
C21 | 0.120 (6) | 0.052 (4) | 0.031 (3) | −0.049 (4) | −0.001 (4) | 0.004 (3) |
C22 | 0.015 (3) | 0.021 (4) | 0.017 (4) | 0.001 (3) | 0.001 (3) | 0.001 (3) |
C23 | 0.033 (5) | 0.017 (4) | 0.019 (4) | −0.012 (4) | 0.000 (4) | −0.004 (3) |
C24 | 0.025 (5) | 0.011 (4) | 0.021 (4) | −0.001 (3) | −0.001 (4) | −0.003 (3) |
C25 | 0.028 (5) | 0.016 (4) | 0.017 (4) | 0.003 (3) | −0.003 (3) | −0.003 (4) |
C26 | 0.014 (4) | 0.034 (6) | 0.024 (5) | −0.007 (3) | −0.001 (3) | −0.003 (4) |
C27 | 0.033 (6) | 0.041 (6) | 0.019 (5) | 0.002 (4) | −0.008 (4) | −0.005 (4) |
C28 | 0.090 (10) | 0.026 (5) | 0.021 (5) | 0.005 (6) | 0.027 (6) | −0.008 (4) |
C29 | 0.029 (5) | 0.027 (5) | 0.028 (5) | 0.001 (4) | 0.011 (4) | −0.001 (4) |
C30 | 0.031 (5) | 0.019 (5) | 0.026 (5) | −0.003 (4) | 0.005 (4) | −0.004 (4) |
C31 | 0.025 (5) | 0.039 (6) | 0.045 (6) | 0.002 (4) | −0.007 (5) | −0.003 (5) |
C32 | 0.039 (7) | 0.065 (9) | 0.078 (9) | 0.002 (7) | −0.027 (7) | 0.017 (8) |
C33 | 0.080 (8) | 0.082 (8) | 0.035 (5) | −0.025 (6) | −0.001 (5) | 0.000 (5) |
C34 | 0.080 (8) | 0.082 (8) | 0.035 (5) | −0.025 (6) | −0.001 (5) | 0.000 (5) |
C35 | 0.080 (4) | 0.082 (4) | 0.035 (3) | −0.025 (4) | −0.001 (3) | 0.000 (3) |
C36 | 0.028 (4) | 0.019 (4) | 0.015 (3) | −0.010 (4) | 0.000 (3) | 0.006 (3) |
C37 | 0.031 (5) | 0.035 (6) | 0.020 (5) | −0.019 (4) | −0.002 (4) | 0.009 (4) |
C38 | 0.028 (5) | 0.026 (5) | 0.016 (4) | −0.004 (3) | 0.000 (4) | −0.006 (4) |
C39 | 0.015 (4) | 0.031 (5) | 0.019 (4) | 0.004 (3) | −0.005 (4) | 0.000 (4) |
C40 | 0.044 (6) | 0.026 (5) | 0.025 (5) | −0.001 (4) | 0.008 (5) | 0.004 (5) |
C41 | 0.100 (11) | 0.048 (7) | 0.037 (6) | 0.038 (7) | 0.000 (8) | 0.002 (6) |
C42 | 0.015 (3) | 0.075 (5) | 0.060 (4) | 0.002 (3) | −0.003 (3) | 0.004 (4) |
C43 | 0.015 (3) | 0.075 (5) | 0.060 (4) | 0.002 (3) | −0.003 (3) | 0.004 (4) |
C44 | 0.015 (3) | 0.075 (5) | 0.060 (4) | 0.002 (3) | −0.003 (3) | 0.004 (4) |
U1—O1 | 1.791 (6) | C19—C20 | 1.3900 |
U1—O2 | 1.792 (6) | C19—H19 | 0.9300 |
U1—O6 | 2.330 (6) | C20—C21 | 1.3900 |
U1—O3 | 2.339 (5) | C20—H20 | 0.9300 |
U1—O4 | 2.351 (5) | C21—C22 | 1.532 (9) |
U1—O5 | 2.357 (6) | C22—C23 | 1.405 (11) |
U1—O7 | 2.420 (6) | C23—C24 | 1.387 (11) |
S1—O7 | 1.525 (6) | C23—H23 | 0.9300 |
S1—C37 | 1.815 (9) | C24—C25 | 1.495 (9) |
S1—C38 | 1.832 (9) | C25—C26 | 1.3900 |
O3—C22 | 1.265 (9) | C25—C30 | 1.3900 |
O4—C24 | 1.320 (9) | C26—C27 | 1.3900 |
O5—C7 | 1.280 (10) | C26—H26 | 0.9300 |
O6—C9 | 1.300 (10) | C27—C28 | 1.3900 |
C1—C2 | 1.3900 | C27—H27 | 0.9300 |
C1—C6 | 1.3900 | C28—C29 | 1.3900 |
C1—H1 | 0.9300 | C28—H28 | 0.9300 |
C2—C3 | 1.3900 | C29—C30 | 1.3900 |
C2—H2 | 0.9300 | C29—H29 | 0.9300 |
C3—C4 | 1.3900 | C30—H30 | 0.9300 |
C3—H3 | 0.9300 | C31—C32 | 1.3900 |
C4—C5 | 1.3900 | C31—C36 | 1.3900 |
C4—H4 | 0.9300 | C31—H31 | 0.9300 |
C5—C6 | 1.3900 | C32—C33 | 1.3900 |
C5—H5 | 0.9300 | C32—H32 | 0.9300 |
C6—C7 | 1.461 (9) | C33—C34 | 1.3900 |
C7—C8 | 1.365 (12) | C33—H33 | 0.9300 |
C8—C9 | 1.447 (12) | C34—C35 | 1.3900 |
C8—H8 | 0.9300 | C34—H34 | 0.9300 |
C9—C10 | 1.524 (9) | C35—C36 | 1.3900 |
C10—C11 | 1.3900 | C35—H35 | 0.9300 |
C10—C15 | 1.3900 | C36—C37 | 1.512 (9) |
C11—C12 | 1.3900 | C37—H37A | 0.9700 |
C11—H11 | 0.9300 | C37—H37B | 0.9700 |
C12—C13 | 1.3900 | C38—C39 | 1.510 (9) |
C12—H12 | 0.9300 | C38—H38A | 0.9700 |
C13—C14 | 1.3900 | C38—H38B | 0.9700 |
C13—H13 | 0.9300 | C39—C40 | 1.3900 |
C14—C15 | 1.3900 | C39—C44 | 1.3900 |
C14—H14 | 0.9300 | C40—C41 | 1.3900 |
C15—H15 | 0.9300 | C40—H40 | 0.9300 |
C16—C17 | 1.3900 | C41—C42 | 1.3900 |
C16—C21 | 1.3900 | C41—H41 | 0.9300 |
C16—H16 | 0.9300 | C42—C43 | 1.3900 |
C17—C18 | 1.3900 | C42—H42 | 0.9300 |
C17—H17 | 0.9300 | C43—C44 | 1.3900 |
C18—C19 | 1.3900 | C43—H43 | 0.9300 |
C18—H18 | 0.9300 | C44—H44 | 0.9300 |
O1—U1—O2 | 177.7 (3) | C18—C19—H19 | 120.0 |
O1—U1—O6 | 95.1 (3) | C20—C19—H19 | 120.0 |
O2—U1—O6 | 86.7 (3) | C21—C20—C19 | 120.0 |
O1—U1—O3 | 86.4 (2) | C21—C20—H20 | 120.0 |
O2—U1—O3 | 95.5 (2) | C19—C20—H20 | 120.0 |
O6—U1—O3 | 72.2 (2) | C20—C21—C16 | 120.0 |
O1—U1—O4 | 90.7 (3) | C20—C21—C22 | 123.8 (6) |
O2—U1—O4 | 88.7 (3) | C16—C21—C22 | 116.2 (6) |
O6—U1—O4 | 141.9 (2) | O3—C22—C23 | 122.6 (8) |
O3—U1—O4 | 70.6 (2) | O3—C22—C21 | 117.9 (7) |
O1—U1—O5 | 85.1 (3) | C23—C22—C21 | 119.5 (7) |
O2—U1—O5 | 94.1 (3) | C24—C23—C22 | 123.7 (8) |
O6—U1—O5 | 71.3 (2) | C24—C23—H23 | 118.1 |
O3—U1—O5 | 141.6 (2) | C22—C23—H23 | 118.1 |
O4—U1—O5 | 146.8 (2) | O4—C24—C23 | 123.9 (8) |
O1—U1—O7 | 86.8 (2) | O4—C24—C25 | 114.7 (7) |
O2—U1—O7 | 90.9 (2) | C23—C24—C25 | 121.2 (7) |
O6—U1—O7 | 145.0 (2) | C26—C25—C30 | 120.0 |
O3—U1—O7 | 142.7 (2) | C26—C25—C24 | 120.1 (5) |
O4—U1—O7 | 72.8 (2) | C30—C25—C24 | 119.9 (5) |
O5—U1—O7 | 74.0 (2) | C25—C26—C27 | 120.0 |
O7—S1—C37 | 104.7 (4) | C25—C26—H26 | 120.0 |
O7—S1—C38 | 104.7 (4) | C27—C26—H26 | 120.0 |
C37—S1—C38 | 97.3 (4) | C28—C27—C26 | 120.0 |
C22—O3—U1 | 140.5 (5) | C28—C27—H27 | 120.0 |
C24—O4—U1 | 135.0 (5) | C26—C27—H27 | 120.0 |
C7—O5—U1 | 137.5 (5) | C27—C28—C29 | 120.0 |
C9—O6—U1 | 139.2 (6) | C27—C28—H28 | 120.0 |
S1—O7—U1 | 121.1 (3) | C29—C28—H28 | 120.0 |
C2—C1—C6 | 120.0 | C28—C29—C30 | 120.0 |
C2—C1—H1 | 120.0 | C28—C29—H29 | 120.0 |
C6—C1—H1 | 120.0 | C30—C29—H29 | 120.0 |
C1—C2—C3 | 120.0 | C29—C30—C25 | 120.0 |
C1—C2—H2 | 120.0 | C29—C30—H30 | 120.0 |
C3—C2—H2 | 120.0 | C25—C30—H30 | 120.0 |
C4—C3—C2 | 120.0 | C32—C31—C36 | 120.0 |
C4—C3—H3 | 120.0 | C32—C31—H31 | 120.0 |
C2—C3—H3 | 120.0 | C36—C31—H31 | 120.0 |
C5—C4—C3 | 120.0 | C31—C32—C33 | 120.0 |
C5—C4—H4 | 120.0 | C31—C32—H32 | 120.0 |
C3—C4—H4 | 120.0 | C33—C32—H32 | 120.0 |
C4—C5—C6 | 120.0 | C34—C33—C32 | 120.0 |
C4—C5—H5 | 120.0 | C34—C33—H33 | 120.0 |
C6—C5—H5 | 120.0 | C32—C33—H33 | 120.0 |
C5—C6—C1 | 120.0 | C33—C34—C35 | 120.0 |
C5—C6—C7 | 122.1 (5) | C33—C34—H34 | 120.0 |
C1—C6—C7 | 117.5 (5) | C35—C34—H34 | 120.0 |
O5—C7—C8 | 123.2 (8) | C36—C35—C34 | 120.0 |
O5—C7—C6 | 118.2 (7) | C36—C35—H35 | 120.0 |
C8—C7—C6 | 118.5 (7) | C34—C35—H35 | 120.0 |
C7—C8—C9 | 125.4 (7) | C35—C36—C31 | 120.0 |
C7—C8—H8 | 117.3 | C35—C36—C37 | 119.1 (6) |
C9—C8—H8 | 117.3 | C31—C36—C37 | 120.9 (6) |
O6—C9—C8 | 121.2 (8) | C36—C37—S1 | 111.6 (6) |
O6—C9—C10 | 115.2 (7) | C36—C37—H37A | 109.3 |
C8—C9—C10 | 123.6 (7) | S1—C37—H37A | 109.3 |
C11—C10—C15 | 120.0 | C36—C37—H37B | 109.3 |
C11—C10—C9 | 121.0 (5) | S1—C37—H37B | 109.3 |
C15—C10—C9 | 119.0 (5) | H37A—C37—H37B | 108.0 |
C10—C11—C12 | 120.0 | C39—C38—S1 | 111.5 (6) |
C10—C11—H11 | 120.0 | C39—C38—H38A | 109.3 |
C12—C11—H11 | 120.0 | S1—C38—H38A | 109.3 |
C13—C12—C11 | 120.0 | C39—C38—H38B | 109.3 |
C13—C12—H12 | 120.0 | S1—C38—H38B | 109.3 |
C11—C12—H12 | 120.0 | H38A—C38—H38B | 108.0 |
C14—C13—C12 | 120.0 | C40—C39—C44 | 120.0 |
C14—C13—H13 | 120.0 | C40—C39—C38 | 121.1 (5) |
C12—C13—H13 | 120.0 | C44—C39—C38 | 118.8 (5) |
C13—C14—C15 | 120.0 | C41—C40—C39 | 120.0 |
C13—C14—H14 | 120.0 | C41—C40—H40 | 120.0 |
C15—C14—H14 | 120.0 | C39—C40—H40 | 120.0 |
C14—C15—C10 | 120.0 | C40—C41—C42 | 120.0 |
C14—C15—H15 | 120.0 | C40—C41—H41 | 120.0 |
C10—C15—H15 | 120.0 | C42—C41—H41 | 120.0 |
C17—C16—C21 | 120.0 | C41—C42—C43 | 120.0 |
C17—C16—H16 | 120.0 | C41—C42—H42 | 120.0 |
C21—C16—H16 | 120.0 | C43—C42—H42 | 120.0 |
C16—C17—C18 | 120.0 | C44—C43—C42 | 120.0 |
C16—C17—H17 | 120.0 | C44—C43—H43 | 120.0 |
C18—C17—H17 | 120.0 | C42—C43—H43 | 120.0 |
C19—C18—C17 | 120.0 | C43—C44—C39 | 120.0 |
C19—C18—H18 | 120.0 | C43—C44—H44 | 120.0 |
C17—C18—H18 | 120.0 | C39—C44—H44 | 120.0 |
C18—C19—C20 | 120.0 | ||
O1—U1—O3—C22 | 99.6 (9) | C12—C13—C14—C15 | 0.0 |
O2—U1—O3—C22 | −79.1 (9) | C13—C14—C15—C10 | 0.0 |
O6—U1—O3—C22 | −163.8 (9) | C11—C10—C15—C14 | 0.0 |
O4—U1—O3—C22 | 7.6 (8) | C9—C10—C15—C14 | 178.3 (6) |
O5—U1—O3—C22 | 177.1 (8) | C21—C16—C17—C18 | 0.0 |
O7—U1—O3—C22 | 19.8 (11) | C16—C17—C18—C19 | 0.0 |
O1—U1—O4—C24 | −106.9 (8) | C17—C18—C19—C20 | 0.0 |
O2—U1—O4—C24 | 75.4 (8) | C18—C19—C20—C21 | 0.0 |
O6—U1—O4—C24 | −7.6 (9) | C19—C20—C21—C16 | 0.0 |
O3—U1—O4—C24 | −21.0 (7) | C19—C20—C21—C22 | 177.4 (9) |
O5—U1—O4—C24 | 171.0 (6) | C17—C16—C21—C20 | 0.0 |
O7—U1—O4—C24 | 166.7 (8) | C17—C16—C21—C22 | −177.6 (9) |
O1—U1—O5—C7 | 80.7 (9) | U1—O3—C22—C23 | 2.4 (14) |
O2—U1—O5—C7 | −101.4 (9) | U1—O3—C22—C21 | 180.0 (6) |
O6—U1—O5—C7 | −16.4 (8) | C20—C21—C22—O3 | −172.0 (7) |
O3—U1—O5—C7 | 2.8 (11) | C16—C21—C22—O3 | 5.5 (11) |
O4—U1—O5—C7 | 164.6 (7) | C20—C21—C22—C23 | 5.6 (12) |
O7—U1—O5—C7 | 168.8 (9) | C16—C21—C22—C23 | −176.9 (7) |
O1—U1—O6—C9 | −79.0 (10) | O3—C22—C23—C24 | −7.2 (14) |
O2—U1—O6—C9 | 99.6 (10) | C21—C22—C23—C24 | 175.3 (9) |
O3—U1—O6—C9 | −163.6 (10) | U1—O4—C24—C23 | 24.9 (13) |
O4—U1—O6—C9 | −176.8 (8) | U1—O4—C24—C25 | −159.4 (5) |
O5—U1—O6—C9 | 4.0 (9) | C22—C23—C24—O4 | −5.8 (14) |
O7—U1—O6—C9 | 12.7 (12) | C22—C23—C24—C25 | 178.8 (8) |
C37—S1—O7—U1 | −177.3 (4) | O4—C24—C25—C26 | 154.5 (6) |
C38—S1—O7—U1 | 80.9 (4) | C23—C24—C25—C26 | −29.7 (10) |
O1—U1—O7—S1 | −16.1 (4) | O4—C24—C25—C30 | −24.9 (9) |
O2—U1—O7—S1 | 164.0 (4) | C23—C24—C25—C30 | 150.9 (7) |
O6—U1—O7—S1 | −110.4 (5) | C30—C25—C26—C27 | 0.0 |
O3—U1—O7—S1 | 63.7 (5) | C24—C25—C26—C27 | −179.4 (6) |
O4—U1—O7—S1 | 75.7 (4) | C25—C26—C27—C28 | 0.0 |
O5—U1—O7—S1 | −101.9 (4) | C26—C27—C28—C29 | 0.0 |
C6—C1—C2—C3 | 0.0 | C27—C28—C29—C30 | 0.0 |
C1—C2—C3—C4 | 0.0 | C28—C29—C30—C25 | 0.0 |
C2—C3—C4—C5 | 0.0 | C26—C25—C30—C29 | 0.0 |
C3—C4—C5—C6 | 0.0 | C24—C25—C30—C29 | 179.4 (6) |
C4—C5—C6—C1 | 0.0 | C36—C31—C32—C33 | 0.0 |
C4—C5—C6—C7 | −172.4 (6) | C31—C32—C33—C34 | 0.0 |
C2—C1—C6—C5 | 0.0 | C32—C33—C34—C35 | 0.0 |
C2—C1—C6—C7 | 172.8 (6) | C33—C34—C35—C36 | 0.0 |
U1—O5—C7—C8 | 20.8 (14) | C34—C35—C36—C31 | 0.0 |
U1—O5—C7—C6 | −159.6 (5) | C34—C35—C36—C37 | 177.7 (7) |
C5—C6—C7—O5 | 163.3 (6) | C32—C31—C36—C35 | 0.0 |
C1—C6—C7—O5 | −9.3 (9) | C32—C31—C36—C37 | −177.6 (7) |
C5—C6—C7—C8 | −17.1 (10) | C35—C36—C37—S1 | 96.2 (7) |
C1—C6—C7—C8 | 170.2 (7) | C31—C36—C37—S1 | −86.1 (7) |
O5—C7—C8—C9 | −6.9 (15) | O7—S1—C37—C36 | 74.1 (7) |
C6—C7—C8—C9 | 173.5 (8) | C38—S1—C37—C36 | −178.6 (7) |
U1—O6—C9—C8 | 2.7 (15) | O7—S1—C38—C39 | −165.7 (5) |
U1—O6—C9—C10 | −179.9 (6) | C37—S1—C38—C39 | 87.0 (6) |
C7—C8—C9—O6 | −3.9 (15) | S1—C38—C39—C40 | 68.7 (7) |
C7—C8—C9—C10 | 178.9 (8) | S1—C38—C39—C44 | −114.2 (5) |
O6—C9—C10—C11 | −166.9 (6) | C44—C39—C40—C41 | 0.0 |
C8—C9—C10—C11 | 10.5 (10) | C38—C39—C40—C41 | 177.1 (7) |
O6—C9—C10—C15 | 14.9 (10) | C39—C40—C41—C42 | 0.0 |
C8—C9—C10—C15 | −167.8 (7) | C40—C41—C42—C43 | 0.0 |
C15—C10—C11—C12 | 0.0 | C41—C42—C43—C44 | 0.0 |
C9—C10—C11—C12 | −178.2 (6) | C42—C43—C44—C39 | 0.0 |
C10—C11—C12—C13 | 0.0 | C40—C39—C44—C43 | 0.0 |
C11—C12—C13—C14 | 0.0 | C38—C39—C44—C43 | −177.2 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O1i | 0.93 | 2.48 | 3.15 (1) | 130 |
C28—H28···O1ii | 0.93 | 2.50 | 3.25 (1) | 138 |
C38—H38B···O2iii | 0.97 | 2.57 | 3.52 (1) | 166 |
C43—H43···O2iv | 0.93 | 2.57 | 3.44 (1) | 156 |
Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) −x+1/2, −y+1, z+1/2; (iii) x−1/2, −y+1/2, −z; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [U(C15H11O2)2(C14H14OS)O2] |
Mr | 946.82 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 183 |
a, b, c (Å) | 12.3178 (1), 15.5281 (1), 20.4617 (1) |
V (Å3) | 3913.75 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.25 |
Crystal size (mm) | 0.34 × 0.16 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.300, 0.507 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23363, 9217, 7611 |
Rint | 0.092 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.121, 0.98 |
No. of reflections | 9217 |
No. of parameters | 352 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.01, −3.10 |
Absolute structure | Flack (1983), 3842 Friedel reflections |
Absolute structure parameter | 0.023 (10) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O1i | 0.93 | 2.48 | 3.15 (1) | 130 |
C28—H28···O1ii | 0.93 | 2.50 | 3.25 (1) | 138 |
C38—H38B···O2iii | 0.97 | 2.57 | 3.52 (1) | 166 |
C43—H43···O2iv | 0.93 | 2.57 | 3.44 (1) | 156 |
Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) −x+1/2, −y+1, z+1/2; (iii) x−1/2, −y+1/2, −z; (iv) x−1, y, z. |
The chemistry of adducts of uranyl bis(β-diketonates) with neutral donor ligands is important for understanding the nature of the species extracted during the solvent-extraction separation of the uranyl ion using mixtures of β-diketones and neutral ligands (Ramakrishna & Patil, 1984).
We and several other research groups have isolated many of these compounds in the solid state, and these compounds have been characterized by spectroscopic and elemental analysis methods (Subramaniam & Viswanatha, 1969; Lu et al., 1977; Taylor & Waugh, 1977; Kramer et al., 1980; Nagar et al., 1989; Kannan & Venugopal, 1995; Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997, 2000, 2001a,b; Kannan & Ferguson, 1997; Kannan, 2000). We have also carried out extensive studies on the structures of these compounds using single-crystal X-ray diffraction methods and their relations with spectroscopic results Please clarify (Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997, 2000, 2001a,b; Kannan & Ferguson, 1997).
Recently, we have prepared adducts of uranyl bis(β-diketonates) with sulfoxide ligands, and found a stronger shielding effect due to the CH2 H atoms in diphenylmethylene sulfoxide compared with that in methyl-phenylmethylene sulfoxide. However, there are no structural studies to support this spectroscopic observation. As part of our systematic study, we have undertaken the X-ray structure determination of the title compound, (I), at 183 K, and the result is reported here. \sch
The bond lengths and angles in (I) (Fig. 1) are within the normal ranges (Allen et al., 1987). The structure of the molecule shows that the UVI ion is surrounded by seven O atoms in a pentagonal-bipyramidal geometry. Four O atoms (O3, O4, O5 and O6) of the diphenylpropane-1,3-dionato-O,O' (DBM) moieties, together with atom O7 of the sulfoxide, form a pentagon, while the two uranyl O atoms occupy the apices.
The pentagonal plane O3/O4/O5/O6/O7 is distorted from planarity towards a twisted conformation, with a local twofold axis passing through atom O7 and O3···O6. Atom U1 is displaced by 0.0574 (3) Å from the O3/O4/O5/O6/O7 mean plane. The O—U—O bond angles for the pentagon are in the range 70.5 (2)–74.0 (2)°, while the Opentagon—U—Oapex angle is 90.0 (3)°. The average U—Ouranyl distance is 1.792 Å, and the average U—Odiketonate distance is 2.344 Å. These values are acceptable, and agree with the values reported earlier (U—Ouranyl and U—Odiketonate in the ranges 1.727–1.788 Å and 2.308–2.417%A, respectively; Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997, 2000, 2001b; Kannan & Ferguson, 1997). The U—Osulfoxide bond distance [2.421 (6) Å] is also comparable with that reported earlier for uranyl bis(β-diketonate) sulfoxide complexes [2.375 Å (Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996) and 2.427 Å (Kannan et al., 2000)].
Both diphenylpropane-1,3-dionato-O,O' (DBM) systems in (I) are nearly planar, with their two phenyl rings having slightly different configurations, corresponding to dihedral angles of 13.3 (5) and 30.9 (4)° between them in the two DBM systems. The planarity of the DBM system is due to the C═O and C—C conjugation in the propane-1,3-dionato-O,O' moiety joining the two phenyl rings.
The propane-1,3-dionato-O,O' moieties, with the U, also form six-membered rings, O5/O6/C7/C8/C9/U1 and O3/O4/C22/C23/C24/U1, in which atom U1 is displaced by 0.2082 (3) and 0.3121 (3) Å from the O5/O6/C7/C8/C9 and O3/O4/C22/C23/C24 planes, respectively.
The configuration of the two phenylmethylene moieties is conditioned by the distorted tetrahedral geometry of the sulfoxide moiety. The angles subtended at atom S1 are 97.1 (4), 104.8 (4), and 104.9 (4)°, with S1—O7, S1—C37 and S1—C38 distances of 1.527 (6), 1.817 (9) and 1.831 (9) Å, respectively. The O7···C37, O7···C38 and C37···C38 distances are 2.66 (1), 2.67 (1) and 2.73 (1) Å, respectively. The aromatic rings of the two phenylmethylene moieties are nearly orthogonal, with a dihedral angle of 83.2 (4)°.
In the crystal structure of (I), there are hydrogen-bonding interactions involving the two uranyl O atoms, namely C19—H19A···O1, C28—H28A···O1, C38—H38B···O2 and C43—H43A···O2 (Table 2). These interactions link the molecules into a three-dimensional network (Fig. 2) and, along with dipole-dipole and van der Waals interactions, stabilize the noncentrosymmetric crystal packing.