Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012923/ci6234sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012923/ci6234Isup2.hkl |
CCDC reference: 217392
[UO2(DBM)2(Ph3PO)] was prepared by refuxing [UO2(DBM)2(H2O)2] (300 mg) with Ph3PO (112 mg) in chloroform for 15 min. The solution was filtered and layered with dodecane. The solution on slow evaporation yielded the title compound in 90% yield. Crystals suitable for the X-ray diffraction analyses were obtained from chloroform/toluene mixture.
All the H atoms were generated geometrically and were allowed to ride on their respective parent atoms with SHELXL97 (Sheldrick, 1997) defaults for bond lengths and isotropic displacement parameters.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
[UO2(C15H11O2)2(C18H15OP)] | F(000) = 1952 |
Mr = 994.78 | Dx = 1.604 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 18.345 (2) Å | θ = 10–15° |
b = 11.022 (4) Å | µ = 4.03 mm−1 |
c = 20.924 (4) Å | T = 293 K |
β = 103.170 (13)° | Rectangular block, orange |
V = 4119.5 (18) Å3 | 0.3 × 0.25 × 0.13 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | 5259 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω–2θ scans | h = 0→21 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→13 |
Tmin = 0.325, Tmax = 0.597 | l = −24→24 |
7464 measured reflections | 2 standard reflections every 60min min |
7221 independent reflections | intensity decay: <1% |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0316P)2 + 1.9225P] where P = (Fo2 + 2Fc2)/3 |
S = 1.29 | (Δ/σ)max < 0.001 |
7221 reflections | Δρmax = 0.96 e Å−3 |
515 parameters | Δρmin = −0.92 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: 0.00049 (6) |
[UO2(C15H11O2)2(C18H15OP)] | V = 4119.5 (18) Å3 |
Mr = 994.78 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 18.345 (2) Å | µ = 4.03 mm−1 |
b = 11.022 (4) Å | T = 293 K |
c = 20.924 (4) Å | 0.3 × 0.25 × 0.13 mm |
β = 103.170 (13)° |
Enraf-Nonius CAD-4 diffractometer | 5259 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.023 |
Tmin = 0.325, Tmax = 0.597 | 2 standard reflections every 60min min |
7464 measured reflections | intensity decay: <1% |
7221 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.29 | Δρmax = 0.96 e Å−3 |
7221 reflections | Δρmin = −0.92 e Å−3 |
515 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2374 (6) | 0.6889 (7) | 0.5628 (4) | 0.081 (3) | |
H1 | 0.2521 | 0.6696 | 0.5243 | 0.097* | |
C2 | 0.2526 (5) | 0.6062 (9) | 0.6142 (4) | 0.088 (3) | |
H2 | 0.2763 | 0.5330 | 0.6101 | 0.106* | |
C3 | 0.2317 (5) | 0.6352 (8) | 0.6704 (5) | 0.084 (3) | |
H3 | 0.2421 | 0.5817 | 0.7057 | 0.101* | |
C4 | 0.1960 (5) | 0.7407 (8) | 0.6759 (4) | 0.077 (3) | |
H4 | 0.1807 | 0.7580 | 0.7144 | 0.093* | |
C5 | 0.1819 (5) | 0.8239 (8) | 0.6242 (4) | 0.070 (2) | |
H5 | 0.1590 | 0.8974 | 0.6291 | 0.083* | |
C6 | 0.2016 (4) | 0.7983 (6) | 0.5657 (3) | 0.0516 (18) | |
C7 | 0.1875 (4) | 0.8807 (6) | 0.5087 (3) | 0.0441 (16) | |
C8 | 0.1378 (4) | 0.9775 (6) | 0.5034 (3) | 0.0564 (18) | |
H8 | 0.1150 | 0.9909 | 0.5381 | 0.068* | |
C9 | 0.1199 (4) | 1.0552 (5) | 0.4503 (3) | 0.0412 (15) | |
C10 | 0.0643 (4) | 1.1555 (6) | 0.4482 (3) | 0.0486 (17) | |
C11 | 0.0401 (4) | 1.1930 (7) | 0.5031 (4) | 0.065 (2) | |
H11 | 0.0548 | 1.1510 | 0.5424 | 0.078* | |
C12 | −0.0065 (5) | 1.2947 (9) | 0.4989 (5) | 0.086 (3) | |
H12 | −0.0219 | 1.3203 | 0.5361 | 0.103* | |
C13 | −0.0294 (5) | 1.3560 (8) | 0.4427 (6) | 0.087 (3) | |
H13 | −0.0594 | 1.4245 | 0.4409 | 0.104* | |
C14 | −0.0076 (5) | 1.3153 (8) | 0.3875 (5) | 0.087 (3) | |
H14 | −0.0246 | 1.3548 | 0.3476 | 0.105* | |
C15 | 0.0385 (4) | 1.2179 (7) | 0.3910 (4) | 0.065 (2) | |
H15 | 0.0530 | 1.1929 | 0.3533 | 0.079* | |
C16 | 0.4287 (5) | 0.6525 (9) | 0.5145 (6) | 0.126 (5) | |
H16 | 0.3798 | 0.6353 | 0.4925 | 0.152* | |
C17 | 0.4636 (6) | 0.5802 (12) | 0.5657 (7) | 0.172 (7) | |
H17 | 0.4370 | 0.5167 | 0.5789 | 0.207* | |
C18 | 0.5372 (5) | 0.5990 (11) | 0.5982 (6) | 0.135 (5) | |
H18 | 0.5605 | 0.5482 | 0.6323 | 0.162* | |
C19 | 0.5741 (5) | 0.6932 (9) | 0.5791 (4) | 0.091 (3) | |
H19 | 0.6238 | 0.7078 | 0.6000 | 0.109* | |
C20 | 0.5387 (4) | 0.7679 (7) | 0.5287 (4) | 0.065 (2) | |
H20 | 0.5651 | 0.8325 | 0.5164 | 0.078* | |
C21 | 0.4650 (4) | 0.7497 (7) | 0.4956 (4) | 0.061 (2) | |
C22 | 0.4263 (4) | 0.8299 (6) | 0.4415 (3) | 0.0473 (16) | |
C23 | 0.4660 (4) | 0.9074 (7) | 0.4101 (4) | 0.0571 (18) | |
H23 | 0.5173 | 0.9137 | 0.4272 | 0.068* | |
C24 | 0.4351 (4) | 0.9769 (6) | 0.3548 (3) | 0.0491 (16) | |
C25 | 0.4847 (4) | 1.0425 (6) | 0.3192 (3) | 0.0520 (17) | |
C26 | 0.5529 (4) | 1.0865 (9) | 0.3508 (5) | 0.083 (3) | |
H26 | 0.5694 | 1.0751 | 0.3959 | 0.100* | |
C27 | 0.5981 (6) | 1.1482 (9) | 0.3164 (6) | 0.105 (4) | |
H27 | 0.6444 | 1.1779 | 0.3385 | 0.126* | |
C28 | 0.5747 (6) | 1.1651 (10) | 0.2508 (6) | 0.099 (3) | |
H28 | 0.6050 | 1.2067 | 0.2282 | 0.119* | |
C29 | 0.5077 (6) | 1.1221 (10) | 0.2182 (5) | 0.095 (3) | |
H29 | 0.4919 | 1.1344 | 0.1733 | 0.114* | |
C30 | 0.4618 (5) | 1.0584 (8) | 0.2524 (4) | 0.083 (3) | |
H30 | 0.4161 | 1.0271 | 0.2298 | 0.099* | |
C31 | 0.3202 (5) | 1.2707 (8) | 0.2035 (4) | 0.082 (3) | |
H31 | 0.3479 | 1.2780 | 0.2464 | 0.099* | |
C32 | 0.3545 (7) | 1.2872 (11) | 0.1518 (6) | 0.123 (4) | |
H32 | 0.4053 | 1.3050 | 0.1595 | 0.148* | |
C33 | 0.3128 (7) | 1.2768 (10) | 0.0898 (6) | 0.107 (4) | |
H33 | 0.3356 | 1.2903 | 0.0550 | 0.128* | |
C34 | 0.2402 (7) | 1.2480 (10) | 0.0766 (5) | 0.105 (4) | |
H34 | 0.2139 | 1.2385 | 0.0334 | 0.126* | |
C35 | 0.2036 (5) | 1.2319 (8) | 0.1280 (3) | 0.074 (2) | |
H35 | 0.1528 | 1.2140 | 0.1194 | 0.089* | |
C36 | 0.2448 (4) | 1.2434 (5) | 0.1914 (3) | 0.0450 (16) | |
C37 | 0.0639 (4) | 1.3319 (6) | 0.2074 (3) | 0.0542 (18) | |
H37 | 0.0897 | 1.4052 | 0.2109 | 0.065* | |
C38 | −0.0132 (5) | 1.3291 (7) | 0.1818 (4) | 0.070 (2) | |
H38 | −0.0388 | 1.4010 | 0.1689 | 0.084* | |
C39 | −0.0516 (4) | 1.2221 (8) | 0.1755 (4) | 0.071 (2) | |
H39 | −0.1028 | 1.2209 | 0.1576 | 0.085* | |
C40 | −0.0142 (4) | 1.1168 (9) | 0.1955 (4) | 0.079 (3) | |
H40 | −0.0405 | 1.0441 | 0.1919 | 0.095* | |
C41 | 0.0615 (4) | 1.1167 (7) | 0.2209 (4) | 0.0608 (19) | |
H41 | 0.0860 | 1.0439 | 0.2337 | 0.073* | |
C42 | 0.1022 (3) | 1.2244 (6) | 0.2276 (3) | 0.0436 (15) | |
C43 | 0.2099 (4) | 1.3547 (6) | 0.3730 (3) | 0.058 (2) | |
H43 | 0.1954 | 1.2825 | 0.3895 | 0.070* | |
C44 | 0.2208 (5) | 1.4595 (7) | 0.4106 (4) | 0.079 (3) | |
H44 | 0.2118 | 1.4576 | 0.4525 | 0.095* | |
C45 | 0.2441 (5) | 1.5650 (6) | 0.3881 (4) | 0.071 (2) | |
H45 | 0.2507 | 1.6338 | 0.4145 | 0.086* | |
C46 | 0.2575 (5) | 1.5696 (7) | 0.3279 (4) | 0.070 (2) | |
H46 | 0.2751 | 1.6410 | 0.3131 | 0.084* | |
C47 | 0.2453 (5) | 1.4685 (6) | 0.2873 (4) | 0.065 (2) | |
H47 | 0.2533 | 1.4729 | 0.2450 | 0.077* | |
C48 | 0.2213 (3) | 1.3614 (5) | 0.3099 (3) | 0.0384 (14) | |
O1 | 0.2153 (2) | 0.8585 (4) | 0.32443 (18) | 0.0399 (10) | |
O2 | 0.3073 (2) | 1.0711 (4) | 0.44177 (19) | 0.0479 (11) | |
O3 | 0.2207 (3) | 0.8538 (4) | 0.4639 (2) | 0.0549 (12) | |
O4 | 0.1475 (2) | 1.0457 (4) | 0.3997 (2) | 0.0457 (10) | |
O5 | 0.3551 (2) | 0.8214 (4) | 0.4257 (2) | 0.0559 (12) | |
O6 | 0.3645 (2) | 0.9845 (4) | 0.3312 (2) | 0.0520 (12) | |
O7 | 0.2251 (2) | 1.1133 (4) | 0.29911 (18) | 0.0403 (10) | |
P1 | 0.20126 (9) | 1.22671 (14) | 0.25987 (7) | 0.0358 (4) | |
U1 | 0.262398 (12) | 0.965493 (19) | 0.382762 (10) | 0.03185 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.149 (9) | 0.056 (5) | 0.050 (5) | −0.003 (5) | 0.050 (5) | 0.013 (4) |
C2 | 0.132 (9) | 0.081 (6) | 0.058 (5) | 0.019 (6) | 0.034 (5) | 0.016 (5) |
C3 | 0.105 (7) | 0.070 (6) | 0.079 (6) | −0.003 (6) | 0.021 (5) | 0.031 (5) |
C4 | 0.106 (7) | 0.086 (6) | 0.044 (4) | −0.005 (6) | 0.027 (5) | 0.023 (4) |
C5 | 0.090 (6) | 0.071 (5) | 0.046 (4) | −0.005 (5) | 0.014 (4) | −0.002 (4) |
C6 | 0.069 (5) | 0.050 (4) | 0.036 (4) | −0.002 (4) | 0.012 (3) | −0.003 (3) |
C7 | 0.067 (4) | 0.044 (4) | 0.029 (3) | −0.016 (3) | 0.027 (3) | −0.004 (3) |
C8 | 0.076 (5) | 0.060 (4) | 0.041 (4) | −0.005 (4) | 0.032 (4) | −0.007 (4) |
C9 | 0.047 (4) | 0.042 (4) | 0.037 (3) | −0.006 (3) | 0.016 (3) | −0.001 (3) |
C10 | 0.040 (4) | 0.049 (4) | 0.060 (4) | −0.005 (3) | 0.017 (3) | −0.007 (3) |
C11 | 0.064 (5) | 0.072 (5) | 0.061 (5) | 0.006 (4) | 0.020 (4) | −0.010 (4) |
C12 | 0.074 (6) | 0.086 (7) | 0.095 (7) | 0.011 (5) | 0.015 (5) | −0.033 (5) |
C13 | 0.064 (6) | 0.065 (6) | 0.136 (9) | 0.020 (5) | 0.030 (6) | −0.011 (6) |
C14 | 0.070 (6) | 0.082 (6) | 0.122 (8) | 0.024 (5) | 0.047 (6) | 0.029 (6) |
C15 | 0.063 (5) | 0.073 (5) | 0.070 (5) | 0.017 (4) | 0.036 (4) | 0.021 (4) |
C16 | 0.068 (6) | 0.117 (9) | 0.169 (11) | −0.031 (6) | −0.025 (7) | 0.084 (8) |
C17 | 0.087 (8) | 0.170 (13) | 0.233 (15) | −0.029 (8) | −0.017 (9) | 0.146 (12) |
C18 | 0.053 (6) | 0.141 (10) | 0.184 (12) | 0.000 (6) | −0.029 (7) | 0.105 (10) |
C19 | 0.063 (6) | 0.108 (8) | 0.088 (7) | 0.006 (5) | −0.012 (5) | 0.034 (6) |
C20 | 0.048 (5) | 0.072 (5) | 0.070 (5) | −0.002 (4) | 0.002 (4) | 0.004 (4) |
C21 | 0.041 (4) | 0.051 (4) | 0.086 (6) | 0.007 (4) | 0.004 (4) | 0.015 (4) |
C22 | 0.037 (4) | 0.041 (4) | 0.060 (4) | 0.005 (3) | 0.002 (3) | 0.002 (3) |
C23 | 0.042 (4) | 0.054 (4) | 0.075 (5) | 0.004 (4) | 0.012 (4) | 0.008 (4) |
C24 | 0.048 (4) | 0.046 (4) | 0.055 (4) | 0.007 (4) | 0.016 (3) | −0.005 (3) |
C25 | 0.049 (4) | 0.056 (4) | 0.055 (4) | 0.008 (4) | 0.020 (3) | 0.011 (4) |
C26 | 0.055 (5) | 0.110 (7) | 0.089 (6) | −0.019 (5) | 0.024 (5) | 0.019 (6) |
C27 | 0.072 (7) | 0.107 (9) | 0.142 (10) | −0.019 (6) | 0.034 (7) | 0.011 (8) |
C28 | 0.086 (8) | 0.116 (9) | 0.112 (9) | 0.004 (7) | 0.059 (7) | 0.023 (7) |
C29 | 0.095 (8) | 0.127 (9) | 0.070 (6) | −0.003 (7) | 0.036 (6) | 0.014 (6) |
C30 | 0.074 (6) | 0.108 (8) | 0.070 (6) | −0.015 (5) | 0.027 (5) | −0.002 (5) |
C31 | 0.078 (6) | 0.113 (8) | 0.062 (5) | 0.002 (6) | 0.027 (5) | 0.016 (5) |
C32 | 0.109 (9) | 0.164 (12) | 0.116 (9) | 0.000 (8) | 0.067 (8) | 0.062 (9) |
C33 | 0.119 (9) | 0.121 (9) | 0.103 (9) | 0.033 (8) | 0.075 (8) | 0.055 (7) |
C34 | 0.127 (10) | 0.131 (10) | 0.058 (6) | 0.052 (9) | 0.025 (6) | 0.028 (6) |
C35 | 0.091 (6) | 0.099 (7) | 0.038 (4) | 0.026 (5) | 0.027 (4) | 0.020 (4) |
C36 | 0.049 (4) | 0.031 (3) | 0.057 (4) | −0.002 (3) | 0.017 (3) | 0.009 (3) |
C37 | 0.045 (4) | 0.050 (4) | 0.062 (5) | 0.014 (3) | 0.002 (3) | −0.001 (3) |
C38 | 0.068 (6) | 0.060 (5) | 0.077 (6) | 0.029 (4) | 0.008 (4) | −0.007 (4) |
C39 | 0.036 (4) | 0.100 (7) | 0.063 (5) | 0.011 (5) | −0.015 (4) | −0.018 (5) |
C40 | 0.043 (5) | 0.080 (6) | 0.112 (7) | −0.019 (4) | 0.014 (5) | −0.011 (5) |
C41 | 0.048 (4) | 0.047 (4) | 0.089 (6) | 0.001 (4) | 0.020 (4) | −0.002 (4) |
C42 | 0.043 (4) | 0.048 (4) | 0.042 (4) | 0.010 (3) | 0.014 (3) | −0.008 (3) |
C43 | 0.083 (6) | 0.046 (4) | 0.055 (4) | −0.015 (4) | 0.036 (4) | −0.005 (3) |
C44 | 0.119 (8) | 0.060 (5) | 0.059 (5) | −0.007 (5) | 0.024 (5) | 0.000 (4) |
C45 | 0.103 (7) | 0.039 (4) | 0.071 (6) | 0.003 (4) | 0.018 (5) | −0.013 (4) |
C46 | 0.089 (6) | 0.046 (5) | 0.073 (6) | −0.014 (4) | 0.018 (5) | 0.001 (4) |
C47 | 0.105 (6) | 0.041 (4) | 0.054 (4) | 0.006 (5) | 0.032 (4) | 0.002 (4) |
C48 | 0.035 (3) | 0.028 (3) | 0.047 (4) | −0.001 (3) | −0.002 (3) | 0.000 (3) |
O1 | 0.047 (2) | 0.038 (2) | 0.035 (2) | −0.0058 (19) | 0.0089 (19) | −0.0073 (18) |
O2 | 0.051 (3) | 0.051 (3) | 0.036 (2) | −0.011 (2) | 0.000 (2) | −0.0072 (19) |
O3 | 0.079 (3) | 0.044 (3) | 0.050 (3) | 0.001 (2) | 0.032 (3) | 0.011 (2) |
O4 | 0.045 (2) | 0.053 (3) | 0.042 (2) | 0.003 (2) | 0.018 (2) | 0.007 (2) |
O5 | 0.040 (3) | 0.048 (3) | 0.074 (3) | 0.000 (2) | 0.003 (2) | 0.012 (2) |
O6 | 0.042 (3) | 0.063 (3) | 0.050 (3) | 0.010 (2) | 0.010 (2) | 0.007 (2) |
O7 | 0.048 (3) | 0.035 (2) | 0.039 (2) | 0.008 (2) | 0.0134 (19) | 0.0169 (19) |
P1 | 0.0391 (9) | 0.0320 (8) | 0.0361 (8) | 0.0019 (7) | 0.0086 (7) | 0.0056 (7) |
U1 | 0.03523 (13) | 0.03071 (12) | 0.02900 (12) | −0.00034 (12) | 0.00623 (8) | 0.00140 (12) |
C1—C6 | 1.381 (10) | C27—C28 | 1.354 (13) |
C1—C2 | 1.389 (11) | C27—H27 | 0.93 |
C1—H1 | 0.93 | C28—C29 | 1.349 (13) |
C2—C3 | 1.356 (11) | C28—H28 | 0.93 |
C2—H2 | 0.93 | C29—C30 | 1.410 (11) |
C3—C4 | 1.353 (11) | C29—H29 | 0.93 |
C3—H3 | 0.93 | C30—H30 | 0.93 |
C4—C5 | 1.398 (10) | C31—C36 | 1.381 (10) |
C4—H4 | 0.93 | C31—C32 | 1.381 (11) |
C5—C6 | 1.381 (9) | C31—H31 | 0.93 |
C5—H5 | 0.93 | C32—C33 | 1.351 (15) |
C6—C7 | 1.473 (9) | C32—H32 | 0.93 |
C7—O3 | 1.265 (7) | C33—C34 | 1.336 (14) |
C7—C8 | 1.392 (9) | C33—H33 | 0.93 |
C8—C9 | 1.381 (9) | C34—C35 | 1.402 (12) |
C8—H8 | 0.93 | C34—H34 | 0.93 |
C9—O4 | 1.279 (7) | C35—C36 | 1.376 (10) |
C9—C10 | 1.497 (9) | C35—H35 | 0.93 |
C10—C15 | 1.368 (9) | C36—P1 | 1.801 (7) |
C10—C11 | 1.385 (9) | C37—C42 | 1.394 (8) |
C11—C12 | 1.401 (11) | C37—C38 | 1.394 (10) |
C11—H11 | 0.93 | C37—H37 | 0.93 |
C12—C13 | 1.338 (12) | C38—C39 | 1.364 (11) |
C12—H12 | 0.93 | C38—H38 | 0.93 |
C13—C14 | 1.380 (12) | C39—C40 | 1.364 (11) |
C13—H13 | 0.93 | C39—H39 | 0.93 |
C14—C15 | 1.358 (10) | C40—C41 | 1.369 (9) |
C14—H14 | 0.93 | C40—H40 | 0.93 |
C15—H15 | 0.93 | C41—C42 | 1.392 (9) |
C16—C21 | 1.367 (11) | C41—H41 | 0.93 |
C16—C17 | 1.371 (12) | C42—P1 | 1.789 (6) |
C16—H16 | 0.93 | C43—C48 | 1.383 (9) |
C17—C18 | 1.382 (13) | C43—C44 | 1.387 (10) |
C17—H17 | 0.93 | C43—H43 | 0.93 |
C18—C19 | 1.350 (13) | C44—C45 | 1.359 (10) |
C18—H18 | 0.93 | C44—H44 | 0.93 |
C19—C20 | 1.379 (10) | C45—C46 | 1.339 (11) |
C19—H19 | 0.93 | C45—H45 | 0.93 |
C20—C21 | 1.385 (9) | C46—C47 | 1.388 (10) |
C20—H20 | 0.93 | C46—H46 | 0.93 |
C21—C22 | 1.484 (9) | C47—C48 | 1.382 (9) |
C22—O5 | 1.276 (7) | C47—H47 | 0.93 |
C22—C23 | 1.382 (9) | C48—P1 | 1.806 (6) |
C23—C24 | 1.397 (9) | O1—U1 | 1.774 (4) |
C23—H23 | 0.93 | O2—U1 | 1.759 (4) |
C24—O6 | 1.278 (8) | O3—U1 | 2.361 (4) |
C24—C25 | 1.488 (9) | O4—U1 | 2.385 (4) |
C25—C26 | 1.364 (10) | O5—U1 | 2.350 (4) |
C25—C30 | 1.377 (10) | O6—U1 | 2.375 (4) |
C26—C27 | 1.394 (12) | O7—P1 | 1.505 (4) |
C26—H26 | 0.93 | O7—U1 | 2.375 (4) |
C6—C1—C2 | 123.5 (8) | C25—C30—H30 | 120.1 |
C6—C1—H1 | 118.3 | C29—C30—H30 | 120.1 |
C2—C1—H1 | 118.3 | C36—C31—C32 | 120.1 (9) |
C3—C2—C1 | 118.1 (9) | C36—C31—H31 | 120.0 |
C3—C2—H2 | 120.9 | C32—C31—H31 | 120.0 |
C1—C2—H2 | 120.9 | C33—C32—C31 | 118.8 (11) |
C4—C3—C2 | 121.0 (8) | C33—C32—H32 | 120.6 |
C4—C3—H3 | 119.5 | C31—C32—H32 | 120.6 |
C2—C3—H3 | 119.5 | C34—C33—C32 | 122.5 (10) |
C3—C4—C5 | 120.4 (8) | C34—C33—H33 | 118.7 |
C3—C4—H4 | 119.8 | C32—C33—H33 | 118.7 |
C5—C4—H4 | 119.8 | C33—C34—C35 | 120.1 (10) |
C6—C5—C4 | 120.9 (8) | C33—C34—H34 | 120.0 |
C6—C5—H5 | 119.6 | C35—C34—H34 | 120.0 |
C4—C5—H5 | 119.6 | C36—C35—C34 | 118.3 (9) |
C5—C6—C1 | 116.2 (7) | C36—C35—H35 | 120.9 |
C5—C6—C7 | 123.9 (7) | C34—C35—H35 | 120.9 |
C1—C6—C7 | 119.9 (6) | C35—C36—C31 | 120.2 (7) |
O3—C7—C8 | 122.5 (6) | C35—C36—P1 | 120.8 (6) |
O3—C7—C6 | 115.5 (6) | C31—C36—P1 | 119.0 (6) |
C8—C7—C6 | 121.9 (6) | C42—C37—C38 | 119.6 (7) |
C9—C8—C7 | 124.9 (6) | C42—C37—H37 | 120.2 |
C9—C8—H8 | 117.5 | C38—C37—H37 | 120.2 |
C7—C8—H8 | 117.5 | C39—C38—C37 | 120.8 (7) |
O4—C9—C8 | 123.3 (6) | C39—C38—H38 | 119.6 |
O4—C9—C10 | 115.6 (5) | C37—C38—H38 | 119.6 |
C8—C9—C10 | 121.2 (6) | C38—C39—C40 | 119.6 (7) |
C15—C10—C11 | 117.5 (7) | C38—C39—H39 | 120.2 |
C15—C10—C9 | 119.7 (6) | C40—C39—H39 | 120.2 |
C11—C10—C9 | 122.7 (7) | C39—C40—C41 | 120.9 (8) |
C10—C11—C12 | 119.6 (8) | C39—C40—H40 | 119.5 |
C10—C11—H11 | 120.2 | C41—C40—H40 | 119.5 |
C12—C11—H11 | 120.2 | C40—C41—C42 | 120.8 (7) |
C13—C12—C11 | 121.6 (9) | C40—C41—H41 | 119.6 |
C13—C12—H12 | 119.2 | C42—C41—H41 | 119.6 |
C11—C12—H12 | 119.2 | C41—C42—C37 | 118.2 (6) |
C12—C13—C14 | 118.6 (8) | C41—C42—P1 | 121.7 (5) |
C12—C13—H13 | 120.7 | C37—C42—P1 | 120.0 (5) |
C14—C13—H13 | 120.7 | C48—C43—C44 | 117.6 (7) |
C15—C14—C13 | 120.5 (9) | C48—C43—H43 | 121.2 |
C15—C14—H14 | 119.8 | C44—C43—H43 | 121.2 |
C13—C14—H14 | 119.8 | C45—C44—C43 | 122.2 (8) |
C14—C15—C10 | 122.2 (8) | C45—C44—H44 | 118.9 |
C14—C15—H15 | 118.9 | C43—C44—H44 | 118.9 |
C10—C15—H15 | 118.9 | C46—C45—C44 | 119.9 (7) |
C21—C16—C17 | 120.6 (9) | C46—C45—H45 | 120.1 |
C21—C16—H16 | 119.7 | C44—C45—H45 | 120.1 |
C17—C16—H16 | 119.7 | C45—C46—C47 | 120.5 (7) |
C16—C17—C18 | 121.9 (10) | C45—C46—H46 | 119.8 |
C16—C17—H17 | 119.1 | C47—C46—H46 | 119.8 |
C18—C17—H17 | 119.1 | C48—C47—C46 | 119.7 (7) |
C19—C18—C17 | 118.0 (9) | C48—C47—H47 | 120.1 |
C19—C18—H18 | 121.0 | C46—C47—H47 | 120.1 |
C17—C18—H18 | 121.0 | C47—C48—C43 | 120.1 (6) |
C18—C19—C20 | 120.3 (9) | C47—C48—P1 | 122.8 (5) |
C18—C19—H19 | 119.8 | C43—C48—P1 | 117.0 (5) |
C20—C19—H19 | 119.8 | C7—O3—U1 | 134.5 (4) |
C19—C20—C21 | 122.1 (8) | C9—O4—U1 | 133.1 (4) |
C19—C20—H20 | 118.9 | C22—O5—U1 | 131.1 (4) |
C21—C20—H20 | 118.9 | C24—O6—U1 | 130.8 (4) |
C16—C21—C20 | 117.0 (7) | P1—O7—U1 | 166.2 (3) |
C16—C21—C22 | 120.5 (7) | O7—P1—C42 | 109.8 (3) |
C20—C21—C22 | 122.5 (7) | O7—P1—C36 | 113.0 (3) |
O5—C22—C23 | 122.8 (6) | C42—P1—C36 | 107.3 (3) |
O5—C22—C21 | 116.0 (6) | O7—P1—C48 | 111.8 (3) |
C23—C22—C21 | 121.2 (6) | C42—P1—C48 | 106.6 (3) |
C22—C23—C24 | 125.0 (7) | C36—P1—C48 | 108.0 (3) |
C22—C23—H23 | 117.5 | O2—U1—O1 | 178.51 (19) |
C24—C23—H23 | 117.5 | O2—U1—O5 | 89.82 (18) |
O6—C24—C23 | 122.7 (6) | O1—U1—O5 | 90.56 (18) |
O6—C24—C25 | 117.2 (6) | O2—U1—O3 | 90.97 (18) |
C23—C24—C25 | 120.1 (6) | O1—U1—O3 | 87.77 (17) |
C26—C25—C30 | 118.8 (7) | O5—U1—O3 | 72.39 (16) |
C26—C25—C24 | 121.9 (7) | O2—U1—O7 | 94.22 (17) |
C30—C25—C24 | 119.3 (7) | O1—U1—O7 | 86.32 (16) |
C25—C26—C27 | 120.7 (9) | O5—U1—O7 | 143.79 (15) |
C25—C26—H26 | 119.6 | O3—U1—O7 | 143.29 (15) |
C27—C26—H26 | 119.6 | O2—U1—O6 | 88.20 (18) |
C28—C27—C26 | 120.2 (10) | O1—U1—O6 | 93.28 (17) |
C28—C27—H27 | 119.9 | O5—U1—O6 | 69.91 (15) |
C26—C27—H27 | 119.9 | O3—U1—O6 | 142.29 (16) |
C29—C28—C27 | 120.4 (10) | O7—U1—O6 | 74.26 (14) |
C29—C28—H28 | 119.8 | O2—U1—O4 | 86.51 (18) |
C27—C28—H28 | 119.8 | O1—U1—O4 | 92.30 (17) |
C28—C29—C30 | 120.0 (9) | O5—U1—O4 | 141.31 (15) |
C28—C29—H29 | 120.0 | O3—U1—O4 | 69.19 (15) |
C30—C29—H29 | 120.0 | O7—U1—O4 | 74.90 (13) |
C25—C30—C29 | 119.9 (9) | O6—U1—O4 | 148.20 (14) |
C6—C1—C2—C3 | −0.7 (15) | C38—C37—C42—C41 | 0.5 (10) |
C1—C2—C3—C4 | 1.1 (15) | C38—C37—C42—P1 | 179.5 (6) |
C2—C3—C4—C5 | −2.0 (15) | C48—C43—C44—C45 | −2.0 (14) |
C3—C4—C5—C6 | 2.4 (14) | C43—C44—C45—C46 | −0.2 (15) |
C4—C5—C6—C1 | −1.9 (12) | C44—C45—C46—C47 | 2.2 (14) |
C4—C5—C6—C7 | 179.1 (7) | C45—C46—C47—C48 | −1.9 (13) |
C2—C1—C6—C5 | 1.1 (13) | C46—C47—C48—C43 | −0.4 (11) |
C2—C1—C6—C7 | −179.8 (8) | C46—C47—C48—P1 | 178.0 (6) |
C5—C6—C7—O3 | 167.7 (7) | C44—C43—C48—C47 | 2.3 (11) |
C1—C6—C7—O3 | −11.3 (10) | C44—C43—C48—P1 | −176.2 (6) |
C5—C6—C7—C8 | −15.6 (11) | C8—C7—O3—U1 | 30.0 (10) |
C1—C6—C7—C8 | 165.4 (8) | C6—C7—O3—U1 | −153.3 (5) |
O3—C7—C8—C9 | −1.0 (11) | C8—C9—O4—U1 | −27.4 (9) |
C6—C7—C8—C9 | −177.4 (6) | C10—C9—O4—U1 | 154.2 (4) |
C7—C8—C9—O4 | 0.2 (11) | C23—C22—O5—U1 | −31.2 (10) |
C7—C8—C9—C10 | 178.6 (6) | C21—C22—O5—U1 | 149.8 (5) |
O4—C9—C10—C15 | 9.3 (9) | C23—C24—O6—U1 | 27.7 (10) |
C8—C9—C10—C15 | −169.2 (7) | C25—C24—O6—U1 | −154.5 (4) |
O4—C9—C10—C11 | −167.3 (6) | U1—O7—P1—C42 | −99.4 (10) |
C8—C9—C10—C11 | 14.2 (10) | U1—O7—P1—C36 | 140.8 (10) |
C15—C10—C11—C12 | −2.6 (11) | U1—O7—P1—C48 | 18.7 (11) |
C9—C10—C11—C12 | 174.0 (7) | C41—C42—P1—O7 | −20.8 (6) |
C10—C11—C12—C13 | 1.0 (14) | C37—C42—P1—O7 | 160.3 (5) |
C11—C12—C13—C14 | 1.6 (15) | C41—C42—P1—C36 | 102.4 (6) |
C12—C13—C14—C15 | −2.6 (14) | C37—C42—P1—C36 | −76.5 (6) |
C13—C14—C15—C10 | 0.9 (14) | C41—C42—P1—C48 | −142.1 (6) |
C11—C10—C15—C14 | 1.7 (12) | C37—C42—P1—C48 | 39.0 (6) |
C9—C10—C15—C14 | −175.1 (7) | C35—C36—P1—O7 | 110.6 (6) |
C21—C16—C17—C18 | −3 (2) | C31—C36—P1—O7 | −70.9 (7) |
C16—C17—C18—C19 | 1 (3) | C35—C36—P1—C42 | −10.6 (7) |
C17—C18—C19—C20 | 0 (2) | C31—C36—P1—C42 | 167.9 (6) |
C18—C19—C20—C21 | −0.4 (16) | C35—C36—P1—C48 | −125.3 (6) |
C17—C16—C21—C20 | 2.4 (18) | C31—C36—P1—C48 | 53.3 (7) |
C17—C16—C21—C22 | −178.1 (12) | C47—C48—P1—O7 | 142.6 (6) |
C19—C20—C21—C16 | −0.9 (14) | C43—C48—P1—O7 | −38.9 (6) |
C19—C20—C21—C22 | 179.6 (8) | C47—C48—P1—C42 | −97.4 (6) |
C16—C21—C22—O5 | 16.3 (12) | C43—C48—P1—C42 | 81.1 (6) |
C20—C21—C22—O5 | −164.3 (7) | C47—C48—P1—C36 | 17.7 (7) |
C16—C21—C22—C23 | −162.7 (9) | C43—C48—P1—C36 | −163.8 (5) |
C20—C21—C22—C23 | 16.7 (12) | C22—O5—U1—O2 | −46.6 (6) |
O5—C22—C23—C24 | −5.7 (12) | C22—O5—U1—O1 | 134.9 (6) |
C21—C22—C23—C24 | 173.3 (7) | C22—O5—U1—O3 | −137.7 (6) |
C22—C23—C24—O6 | 7.1 (12) | C22—O5—U1—O7 | 50.3 (7) |
C22—C23—C24—C25 | −170.7 (7) | C22—O5—U1—O6 | 41.6 (6) |
O6—C24—C25—C26 | 150.7 (7) | C22—O5—U1—O4 | −130.8 (6) |
C23—C24—C25—C26 | −31.4 (11) | C7—O3—U1—O2 | 49.8 (6) |
O6—C24—C25—C30 | −30.0 (10) | C7—O3—U1—O1 | −129.4 (6) |
C23—C24—C25—C30 | 147.9 (8) | C7—O3—U1—O5 | 139.3 (6) |
C30—C25—C26—C27 | 1.1 (13) | C7—O3—U1—O7 | −48.6 (7) |
C24—C25—C26—C27 | −179.6 (8) | C7—O3—U1—O6 | 138.2 (6) |
C25—C26—C27—C28 | −0.1 (16) | C7—O3—U1—O4 | −36.1 (6) |
C26—C27—C28—C29 | −0.3 (18) | P1—O7—U1—O2 | −29.9 (11) |
C27—C28—C29—C30 | −0.4 (17) | P1—O7—U1—O1 | 148.7 (11) |
C26—C25—C30—C29 | −1.7 (13) | P1—O7—U1—O5 | −125.4 (10) |
C24—C25—C30—C29 | 179.0 (8) | P1—O7—U1—O3 | 67.4 (11) |
C28—C29—C30—C25 | 1.4 (15) | P1—O7—U1—O6 | −116.8 (11) |
C36—C31—C32—C33 | 0.4 (17) | P1—O7—U1—O4 | 55.3 (10) |
C31—C32—C33—C34 | −2 (2) | C24—O6—U1—O2 | 50.8 (6) |
C32—C33—C34—C35 | 2.6 (19) | C24—O6—U1—O1 | −129.0 (6) |
C33—C34—C35—C36 | −1.8 (15) | C24—O6—U1—O5 | −39.6 (6) |
C34—C35—C36—C31 | 0.4 (12) | C24—O6—U1—O3 | −38.4 (7) |
C34—C35—C36—P1 | 178.9 (6) | C24—O6—U1—O7 | 145.7 (6) |
C32—C31—C36—C35 | 0.3 (13) | C24—O6—U1—O4 | 131.3 (5) |
C32—C31—C36—P1 | −178.2 (8) | C9—O4—U1—O2 | −58.2 (5) |
C42—C37—C38—C39 | −0.9 (12) | C9—O4—U1—O1 | 120.9 (5) |
C37—C38—C39—C40 | 1.1 (13) | C9—O4—U1—O5 | 27.1 (6) |
C38—C39—C40—C41 | −1.1 (13) | C9—O4—U1—O3 | 34.2 (5) |
C39—C40—C41—C42 | 0.8 (13) | C9—O4—U1—O7 | −153.5 (5) |
C40—C41—C42—C37 | −0.5 (11) | C9—O4—U1—O6 | −139.1 (5) |
C40—C41—C42—P1 | −179.4 (6) |
Experimental details
Crystal data | |
Chemical formula | [UO2(C15H11O2)2(C18H15OP)] |
Mr | 994.78 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 18.345 (2), 11.022 (4), 20.924 (4) |
β (°) | 103.170 (13) |
V (Å3) | 4119.5 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.03 |
Crystal size (mm) | 0.3 × 0.25 × 0.13 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.325, 0.597 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7464, 7221, 5259 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.084, 1.29 |
No. of reflections | 7221 |
No. of parameters | 515 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.96, −0.92 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
C7—O3 | 1.265 (7) | O2—U1 | 1.759 (4) |
C9—O4 | 1.279 (7) | O3—U1 | 2.361 (4) |
C22—O5 | 1.276 (7) | O4—U1 | 2.385 (4) |
C24—O6 | 1.278 (8) | O5—U1 | 2.350 (4) |
C36—P1 | 1.801 (7) | O6—U1 | 2.375 (4) |
C42—P1 | 1.789 (6) | O7—P1 | 1.505 (4) |
C48—P1 | 1.806 (6) | O7—U1 | 2.375 (4) |
O1—U1 | 1.774 (4) | ||
C9—C8—C7 | 124.9 (6) | O2—U1—O6 | 88.20 (18) |
C22—C23—C24 | 125.0 (7) | O1—U1—O6 | 93.28 (17) |
O2—U1—O1 | 178.51 (19) | O5—U1—O6 | 69.91 (15) |
O2—U1—O5 | 89.82 (18) | O3—U1—O6 | 142.29 (16) |
O1—U1—O5 | 90.56 (18) | O7—U1—O6 | 74.26 (14) |
O2—U1—O3 | 90.97 (18) | O2—U1—O4 | 86.51 (18) |
O1—U1—O3 | 87.77 (17) | O1—U1—O4 | 92.30 (17) |
O5—U1—O3 | 72.39 (16) | O5—U1—O4 | 141.31 (15) |
O2—U1—O7 | 94.22 (17) | O3—U1—O4 | 69.19 (15) |
O1—U1—O7 | 86.32 (16) | O7—U1—O4 | 74.90 (13) |
O5—U1—O7 | 143.79 (15) | O6—U1—O4 | 148.20 (14) |
O3—U1—O7 | 143.29 (15) |
The compounds of uranyl bis(β-diketonates) with neutral donor ligands are of importance to understand 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). An increase (or synergism) in solvent extraction separation of uranyl ion from nitric acid medium by using mixtures of β-diketones and phosphine oxides or phosphate have been reported (Irving & Edgington, 1960; Healy, 1961; Akiba, 1977). The species responsible for the extraction have been isolated in solid state for some of the systems and characterized by IR (Ferraro & Healy, 1962), 1H, 19F NMR (Subramanian & Viswanatha, 1969) spectroscopic and elemental analyses methods. In few of the cases it has been characterized using single-crystal X-ray diffraction methods (Taylor & McLaren, 1979; Lu et al., 1977; Taylor & Waugh, 1977a,b; Kannan et al., 2001a). In continuation of our work on uranyl bis(/b-diketones) with neutral donor ligands (Kannan & Venugopal, 1995; Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlmber, 1996; Kannan et al., 1997, 2001a,b; Kannan & Ferguson, 1997; Kannan, 2000; Fun et al., 2002; Rajagopal et al., 2002), we report here the structure of [UO2(DBM)2(Ph3PO)], (I), where DBM is dibenzoyl methanate.
The structure of (I) is shown in Fig. 1. Selected bond distances and angles are listed in Table 1. The structure of the molecule shows that the U atom is surrounded by seven O atoms in a pentagonal–bipyramidal geometry. Four O atoms of the DBM and one O atom of phosphine oxide form a planar pentagon and two uranyl O atoms occupy the apices. The average of U—Ouranyl [1.767 (4) Å], U—ODBM [2.365 (4) Å] distances are within the accepted ranges (Taylor & McLaren, 1979; Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlmber, 1996; Kannan et al., 1997, 2000, 2001b). The U—O(P) phosphine oxide distance [2.375 (4) Å] is comparable with those reported earlier for uranyl bis(β-diketone)–phosphine adducts (Taylor & McLaren, 1979; Lu et al., 1977; Kannan et al. 2001a). The overall bond lengths and angles show that the U atom has a distorted pentogonal bi-pyramidal geometry. In both the DBM ligands, the benzene rings are not coplanar and they form dihedral angles of 11.9 (4) and 32.9 (5)°, respectively. Fig. 2 shows the crystal packing of the title compound viewed down the b axis. The structure is stabilized by van der Waals interactions. It is noteworthy that the O atoms belonging to the DBM and phosphine oxide moieties participating in the uranium(VI) coordination, are not at all involved in any hydrogen bonding.