Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109054092/em3028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109054092/em3028Isup2.hkl |
CCDC reference: 774027
A hot aqueous solution of ferron (176 mg Riedel de-Hean) and UO2(NO3)2. 6H2O (125 mg, LOBA Chemie) were mixed in a 1:2 molar ratio and warmed in a water bath for 3 h, forming a red solution. After a few days of slow evaporation, red-coloured crystals of (I) were obtained. In the IR spectrum, a stretching band at 916 cm-1 (Malutan et al., 2008) characteristic of the UO22+ group is observed. Stretching bands at 1707.50, 1191.13 and 1045 cm-1 (Gonzalez-Baro et al., 2001) correspond to ν(CN), ν(CO) and ν(SO), respectively.
The H atoms of the aromatic groups were positioned geometrically. The water H atoms were located using difference Fourier synthesis and their positional parameters were initially refined with O—H distance restraints of 0.97 (2)Å and H···H restraints of 1.54 (2)Å. Subsequently, all H atoms were treated as riding atoms, with C—H and O—H distances of 0.93 and 0.88–0.95Å, respectively, and with isotropic displacement parameters of 1.2Ueq of the parent atom. H atoms could not be located reliably on O5W nor the second H atom on O4W and were not included in the model.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
[U(C9H4INO4S)O2(H2O)3]·2H2O | Z = 2 |
Mr = 707.20 | F(000) = 642 |
Triclinic, P1 | Dx = 2.671 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3742 (2) Å | Cell parameters from 6209 reflections |
b = 10.1785 (2) Å | θ = 1.8–33.5° |
c = 11.6146 (2) Å | µ = 11.17 mm−1 |
α = 74.958 (1)° | T = 293 K |
β = 84.717 (1)° | Prism, red |
γ = 66.701 (1)° | 0.15 × 0.13 × 0.12 mm |
V = 878.04 (3) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 6209 independent reflections |
Radiation source: fine-focus sealed tube | 5581 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 33.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −12→12 |
Tmin = 0.286, Tmax = 0.348 | k = −15→15 |
21488 measured reflections | l = −17→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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0276P)2 + 0.7169P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
6209 reflections | Δρmax = 1.70 e Å−3 |
218 parameters | Δρmin = −1.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2Θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00269 (19) |
[U(C9H4INO4S)O2(H2O)3]·2H2O | γ = 66.701 (1)° |
Mr = 707.20 | V = 878.04 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3742 (2) Å | Mo Kα radiation |
b = 10.1785 (2) Å | µ = 11.17 mm−1 |
c = 11.6146 (2) Å | T = 293 K |
α = 74.958 (1)° | 0.15 × 0.13 × 0.12 mm |
β = 84.717 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 6209 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 5581 reflections with I > 2σ(I) |
Tmin = 0.286, Tmax = 0.348 | Rint = 0.031 |
21488 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.70 e Å−3 |
6209 reflections | Δρmin = −1.16 e Å−3 |
218 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs 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 | 0.83651 (1) | 0.40488 (1) | 0.18502 (1) | 0.0211 (1) | |
I1 | 1.36043 (3) | −0.10809 (3) | 0.38234 (2) | 0.0337 (1) | |
S1 | 1.14938 (10) | 0.07535 (8) | 0.81480 (7) | 0.0218 (2) | |
O1 | 1.1654 (4) | 0.1983 (3) | 0.8492 (2) | 0.0324 (8) | |
O1W | 0.6314 (3) | 0.6480 (3) | 0.1954 (2) | 0.0289 (7) | |
O2 | 0.9900 (3) | 0.0575 (3) | 0.8612 (2) | 0.0295 (7) | |
O2W | 0.6822 (3) | 0.5032 (3) | −0.0048 (2) | 0.0327 (8) | |
O3 | 1.3010 (3) | −0.0600 (3) | 0.8463 (2) | 0.0327 (8) | |
O3W | 0.9851 (4) | 0.2297 (3) | 0.0650 (2) | 0.0319 (8) | |
O4 | 1.0557 (3) | 0.2085 (3) | 0.2951 (2) | 0.0319 (7) | |
O5 | 0.6803 (4) | 0.3274 (3) | 0.2348 (3) | 0.0371 (9) | |
O6 | 0.9827 (3) | 0.4927 (3) | 0.1361 (2) | 0.0300 (7) | |
N1 | 0.8534 (4) | 0.4080 (3) | 0.4071 (3) | 0.0282 (8) | |
C2 | 0.7515 (5) | 0.5084 (4) | 0.4624 (4) | 0.0388 (11) | |
C3 | 0.7617 (6) | 0.4958 (4) | 0.5842 (3) | 0.0387 (11) | |
C4 | 0.8843 (5) | 0.3723 (4) | 0.6522 (3) | 0.0302 (10) | |
C5 | 1.1270 (4) | 0.1244 (3) | 0.6586 (3) | 0.0206 (8) | |
C6 | 1.2272 (4) | 0.0215 (3) | 0.5972 (3) | 0.0220 (8) | |
C7 | 1.2059 (4) | 0.0481 (3) | 0.4738 (3) | 0.0227 (8) | |
C8 | 1.0817 (4) | 0.1770 (3) | 0.4108 (3) | 0.0234 (8) | |
C9 | 0.9969 (4) | 0.2594 (3) | 0.5987 (3) | 0.0215 (8) | |
C10 | 0.9757 (4) | 0.2832 (3) | 0.4747 (3) | 0.0215 (8) | |
O4W | 0.3336 (4) | 0.7506 (3) | 0.0782 (3) | 0.0398 (8) | |
O5W | 0.6486 (5) | 0.7462 (5) | −0.1660 (5) | 0.1049 (18) | |
H1A | 0.51490 | 0.69160 | 0.16630 | 0.0350* | |
H1B | 0.67660 | 0.72230 | 0.18440 | 0.0350* | |
H2 | 0.66760 | 0.59310 | 0.41730 | 0.0460* | |
H2A | 0.70340 | 0.56860 | −0.06770 | 0.0390* | |
H2B | 0.67230 | 0.43190 | −0.02960 | 0.0390* | |
H3 | 0.68660 | 0.57040 | 0.61860 | 0.0460* | |
H3A | 1.00770 | 0.12750 | 0.09120 | 0.0380* | |
H3B | 1.05210 | 0.24160 | −0.00450 | 0.0380* | |
H4 | 0.89370 | 0.36260 | 0.73340 | 0.0360* | |
H6 | 1.31020 | −0.06710 | 0.63820 | 0.0260* | |
H4B | 0.22820 | 0.81070 | 0.10610 | 0.0480* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.0228 (1) | 0.0173 (1) | 0.0203 (1) | −0.0047 (1) | −0.0020 (1) | −0.0035 (1) |
I1 | 0.0327 (1) | 0.0259 (1) | 0.0332 (1) | 0.0016 (1) | 0.0031 (1) | −0.0134 (1) |
S1 | 0.0269 (4) | 0.0187 (3) | 0.0173 (3) | −0.0064 (3) | −0.0008 (3) | −0.0040 (3) |
O1 | 0.0464 (16) | 0.0294 (12) | 0.0274 (13) | −0.0181 (12) | −0.0022 (11) | −0.0106 (10) |
O1W | 0.0260 (12) | 0.0202 (11) | 0.0341 (13) | −0.0026 (9) | −0.0061 (10) | −0.0041 (10) |
O2 | 0.0327 (13) | 0.0296 (12) | 0.0257 (12) | −0.0130 (11) | 0.0067 (10) | −0.0066 (10) |
O2W | 0.0350 (14) | 0.0337 (13) | 0.0253 (13) | −0.0110 (11) | −0.0064 (11) | −0.0019 (10) |
O3 | 0.0326 (14) | 0.0288 (13) | 0.0239 (12) | 0.0001 (10) | −0.0056 (10) | −0.0023 (10) |
O3W | 0.0447 (15) | 0.0230 (12) | 0.0242 (12) | −0.0091 (11) | 0.0053 (11) | −0.0077 (10) |
O4 | 0.0366 (14) | 0.0253 (12) | 0.0189 (11) | 0.0049 (10) | −0.0058 (10) | −0.0056 (9) |
O5 | 0.0407 (15) | 0.0336 (14) | 0.0419 (16) | −0.0211 (12) | 0.0065 (12) | −0.0085 (12) |
O6 | 0.0253 (12) | 0.0281 (12) | 0.0371 (14) | −0.0101 (10) | 0.0012 (10) | −0.0092 (11) |
N1 | 0.0313 (15) | 0.0198 (12) | 0.0233 (14) | 0.0010 (11) | −0.0020 (12) | −0.0052 (11) |
C2 | 0.039 (2) | 0.0266 (17) | 0.033 (2) | 0.0087 (15) | −0.0058 (16) | −0.0099 (15) |
C3 | 0.046 (2) | 0.0256 (17) | 0.0302 (19) | 0.0055 (15) | −0.0013 (17) | −0.0133 (15) |
C4 | 0.0352 (19) | 0.0276 (16) | 0.0235 (17) | −0.0054 (14) | 0.0017 (14) | −0.0103 (14) |
C5 | 0.0238 (15) | 0.0200 (13) | 0.0143 (13) | −0.0061 (11) | 0.0001 (11) | −0.0016 (11) |
C6 | 0.0223 (15) | 0.0168 (13) | 0.0208 (15) | −0.0025 (11) | −0.0001 (12) | −0.0025 (11) |
C7 | 0.0238 (15) | 0.0180 (13) | 0.0218 (15) | −0.0021 (11) | 0.0013 (12) | −0.0076 (11) |
C8 | 0.0236 (15) | 0.0199 (14) | 0.0205 (15) | −0.0027 (12) | 0.0002 (12) | −0.0038 (11) |
C9 | 0.0226 (15) | 0.0181 (13) | 0.0221 (15) | −0.0062 (11) | 0.0004 (12) | −0.0049 (11) |
C10 | 0.0198 (14) | 0.0175 (13) | 0.0210 (14) | −0.0023 (11) | 0.0002 (11) | −0.0025 (11) |
O4W | 0.0252 (13) | 0.0411 (15) | 0.0411 (16) | −0.0027 (11) | −0.0025 (12) | −0.0054 (12) |
O5W | 0.0347 (19) | 0.065 (3) | 0.145 (4) | 0.0000 (18) | 0.011 (2) | 0.056 (3) |
U1—O1W | 2.417 (3) | O3W—H3A | 0.9500 |
U1—O2W | 2.427 (2) | O4W—H4B | 0.9400 |
U1—O3W | 2.426 (3) | N1—C10 | 1.371 (5) |
U1—O4 | 2.281 (3) | N1—C2 | 1.317 (5) |
U1—O5 | 1.763 (3) | C2—C3 | 1.394 (6) |
U1—O6 | 1.759 (3) | C3—C4 | 1.368 (6) |
U1—N1 | 2.605 (3) | C4—C9 | 1.415 (5) |
I1—C7 | 2.080 (3) | C5—C6 | 1.376 (4) |
S1—O1 | 1.465 (3) | C5—C9 | 1.421 (4) |
S1—O2 | 1.454 (3) | C6—C7 | 1.402 (5) |
S1—O3 | 1.444 (3) | C7—C8 | 1.379 (4) |
S1—C5 | 1.759 (3) | C8—C10 | 1.429 (4) |
O4—C8 | 1.316 (4) | C9—C10 | 1.413 (5) |
O1W—H1A | 0.9500 | C2—H2 | 0.9300 |
O1W—H1B | 0.9500 | C3—H3 | 0.9300 |
O2W—H2B | 0.8800 | C4—H4 | 0.9300 |
O2W—H2A | 0.9100 | C6—H6 | 0.9300 |
O3W—H3B | 0.9500 | ||
U1···O1i | 3.948 (3) | O5W···O6ii | 3.064 (6) |
U1···O5Wii | 3.970 (5) | O5W···O2W | 2.616 (6) |
U1···O6ii | 3.935 (2) | O5W···U1ii | 3.970 (5) |
I1···O1Wiii | 3.669 (3) | O6···U1ii | 3.935 (2) |
I1···O4 | 3.194 (3) | O6···O2Wii | 3.078 (4) |
I1···C9iv | 3.837 (4) | O6···O2W | 3.079 (4) |
I1···H2iii | 3.0700 | O6···O4 | 2.862 (4) |
S1···H3Bv | 2.8900 | O6···O6ii | 3.118 (3) |
S1···H4 | 2.8300 | O6···N1 | 3.244 (4) |
S1···H1Bi | 2.9600 | O6···O3W | 2.992 (4) |
S1···H3Aiv | 2.8100 | O6···O1W | 2.853 (4) |
S1···H4Bvi | 3.0500 | O6···O1i | 2.935 (4) |
O1···O3Wv | 2.829 (4) | O6···O5Wii | 3.064 (6) |
O1···C4 | 3.083 (5) | O1···H3Bv | 1.9300 |
O1···O1Wi | 2.671 (4) | O1···H4 | 2.4800 |
O1···O6i | 2.935 (4) | O1···H1Bi | 1.7700 |
O1···U1i | 3.948 (3) | O1W···H2 | 2.5100 |
O1W···O2W | 2.977 (4) | O2···H3Aiv | 1.8100 |
O1W···O4W | 2.644 (4) | O2···H4 | 2.8900 |
O1W···C2 | 3.131 (5) | O2···H4Bvi | 1.8700 |
O1W···I1vii | 3.669 (3) | O2W···H2Bix | 2.7900 |
O1W···O1i | 2.671 (4) | O3···H3Aiv | 2.9100 |
O1W···N1 | 3.099 (4) | O3···H6 | 2.4300 |
O1W···O5 | 3.038 (4) | O3W···H2B | 2.7200 |
O1W···O6 | 2.853 (4) | O4···H3A | 2.8100 |
O2···C4 | 3.325 (4) | O4W···H1A | 1.7200 |
O2···O4Wvi | 2.798 (4) | O4W···H2Bix | 2.1000 |
O2···O2viii | 3.127 (3) | O5···H6iv | 2.6500 |
O2···O3Wiv | 2.752 (4) | O5W···H2A | 1.7800 |
O2W···O4Wix | 2.975 (4) | O6···H1B | 2.8300 |
O2W···O3W | 2.909 (4) | O6···H2Aii | 2.5500 |
O2W···O1W | 2.977 (4) | O6···H4i | 2.8600 |
O2W···O6ii | 3.078 (4) | O6···H3Bii | 2.6500 |
O2W···O6 | 3.079 (4) | N1···O1W | 3.099 (4) |
O2W···O2Wix | 3.069 (4) | N1···O4 | 2.632 (4) |
O2W···O5 | 2.894 (4) | N1···O5 | 3.018 (5) |
O2W···O5W | 2.616 (6) | N1···O6 | 3.244 (4) |
O3···O4Wx | 2.841 (4) | N1···C8 | 2.365 (4) |
O3···O5iv | 3.047 (4) | C4···O1 | 3.083 (5) |
O3···O5Wx | 2.813 (6) | C4···O2 | 3.325 (4) |
O3W···O2W | 2.909 (4) | C6···O5iv | 3.395 (4) |
O3W···O4Wix | 3.186 (5) | C9···I1iv | 3.837 (4) |
O3W···O2iv | 2.752 (4) | H1A···O4W | 1.7200 |
O3W···O1xi | 2.829 (4) | H1A···H4B | 2.3000 |
O3W···O6 | 2.992 (4) | H1B···S1i | 2.9600 |
O3W···O4 | 2.726 (3) | H1B···O1i | 1.7700 |
O3W···O5 | 3.078 (4) | H2···O1W | 2.5100 |
O4···O6 | 2.862 (4) | H2···I1vii | 3.0700 |
O4···O5Wii | 2.908 (6) | H2A···O6ii | 2.5500 |
O4···C10 | 2.354 (4) | H2A···O5W | 1.7800 |
O4···I1 | 3.194 (3) | H2B···O4Wix | 2.1000 |
O4···O3W | 2.726 (3) | H2B···O2Wix | 2.7900 |
O4···O5 | 2.965 (4) | H3A···S1iv | 2.8100 |
O4···N1 | 2.632 (4) | H3A···O3iv | 2.9100 |
O4W···O2Wix | 2.975 (4) | H3A···O2iv | 1.8100 |
O4W···O3xii | 2.841 (4) | H3B···O6ii | 2.6500 |
O4W···O1W | 2.644 (4) | H3B···O1xi | 1.9300 |
O4W···O3Wix | 3.186 (5) | H3B···S1xi | 2.8900 |
O4W···O2vi | 2.798 (4) | H4···O1 | 2.4800 |
O5···O1W | 3.038 (4) | H4···S1 | 2.8300 |
O5···O2W | 2.894 (4) | H4···O6i | 2.8600 |
O5···N1 | 3.018 (5) | H4···O2 | 2.8900 |
O5···O4 | 2.965 (4) | H4B···H1A | 2.3000 |
O5···O3iv | 3.047 (4) | H4B···O2vi | 1.8700 |
O5···C6iv | 3.395 (4) | H4B···S1vi | 3.0500 |
O5···O3W | 3.078 (4) | H6···O3 | 2.4300 |
O5W···O3xii | 2.813 (6) | H6···O5iv | 2.6500 |
O5W···O4ii | 2.908 (6) | ||
O1W—U1—O2W | 75.84 (9) | U1—O3W—H3A | 123.00 |
O1W—U1—O3W | 148.59 (8) | H3A—O3W—H3B | 107.00 |
O1W—U1—O4 | 139.84 (9) | U1—O3W—H3B | 129.00 |
O1W—U1—O5 | 91.87 (12) | C2—N1—C10 | 117.4 (3) |
O1W—U1—O6 | 84.63 (11) | U1—N1—C10 | 114.5 (2) |
O1W—U1—N1 | 76.08 (9) | U1—N1—C2 | 127.9 (3) |
O2W—U1—O3W | 73.66 (9) | N1—C2—C3 | 124.1 (4) |
O2W—U1—O4 | 144.25 (9) | C2—C3—C4 | 119.0 (4) |
O2W—U1—O5 | 85.84 (13) | C3—C4—C9 | 119.9 (3) |
O2W—U1—O6 | 93.32 (10) | S1—C5—C6 | 117.8 (2) |
O2W—U1—N1 | 150.13 (10) | C6—C5—C9 | 120.7 (3) |
O3W—U1—O4 | 70.69 (9) | S1—C5—C9 | 121.1 (2) |
O3W—U1—O5 | 93.23 (13) | C5—C6—C7 | 121.0 (3) |
O3W—U1—O6 | 89.79 (12) | I1—C7—C6 | 120.4 (2) |
O3W—U1—N1 | 135.24 (9) | C6—C7—C8 | 121.0 (3) |
O4—U1—O5 | 93.45 (13) | I1—C7—C8 | 118.6 (2) |
O4—U1—O6 | 89.22 (11) | O4—C8—C7 | 123.9 (3) |
O4—U1—N1 | 64.80 (9) | C7—C8—C10 | 118.1 (3) |
O5—U1—O6 | 176.50 (13) | O4—C8—C10 | 118.0 (3) |
O5—U1—N1 | 85.08 (13) | C4—C9—C10 | 116.6 (3) |
O6—U1—N1 | 94.03 (11) | C5—C9—C10 | 117.5 (3) |
O1—S1—O2 | 110.55 (18) | C4—C9—C5 | 125.9 (3) |
O1—S1—O3 | 112.96 (18) | C8—C10—C9 | 121.7 (3) |
O1—S1—C5 | 107.11 (14) | N1—C10—C8 | 115.2 (3) |
O2—S1—O3 | 112.50 (16) | N1—C10—C9 | 123.1 (3) |
O2—S1—C5 | 105.87 (16) | N1—C2—H2 | 118.00 |
O3—S1—C5 | 107.39 (14) | C3—C2—H2 | 118.00 |
U1—O4—C8 | 126.9 (2) | C2—C3—H3 | 121.00 |
U1—O1W—H1A | 125.00 | C4—C3—H3 | 121.00 |
U1—O1W—H1B | 117.00 | C3—C4—H4 | 120.00 |
H1A—O1W—H1B | 109.00 | C9—C4—H4 | 120.00 |
U1—O2W—H2A | 125.00 | C5—C6—H6 | 119.00 |
U1—O2W—H2B | 110.00 | C7—C6—H6 | 120.00 |
H2A—O2W—H2B | 110.00 | ||
O1W—U1—O4—C8 | 21.2 (4) | C10—N1—C2—C3 | 0.6 (6) |
O2W—U1—O4—C8 | −163.5 (2) | U1—N1—C10—C9 | −175.6 (3) |
O3W—U1—O4—C8 | −168.0 (3) | U1—N1—C10—C8 | 4.3 (4) |
O5—U1—O4—C8 | −75.8 (3) | C2—N1—C10—C8 | 179.4 (4) |
O6—U1—O4—C8 | 101.9 (3) | N1—C2—C3—C4 | 0.0 (7) |
N1—U1—O4—C8 | 7.1 (3) | C2—C3—C4—C9 | −0.6 (7) |
O1W—U1—N1—C2 | 9.3 (3) | C3—C4—C9—C10 | 0.7 (6) |
O1W—U1—N1—C10 | −176.2 (3) | C3—C4—C9—C5 | −178.5 (4) |
O2W—U1—N1—C2 | −11.1 (5) | C6—C5—C9—C4 | 178.9 (4) |
O2W—U1—N1—C10 | 163.4 (2) | S1—C5—C6—C7 | 174.6 (3) |
O3W—U1—N1—C2 | −173.5 (3) | C9—C5—C6—C7 | 1.2 (5) |
O3W—U1—N1—C10 | 1.0 (3) | S1—C5—C9—C4 | 5.7 (5) |
O4—U1—N1—C2 | 180.0 (4) | S1—C5—C9—C10 | −173.4 (3) |
O4—U1—N1—C10 | −5.5 (2) | C6—C5—C9—C10 | −0.2 (5) |
O5—U1—N1—C2 | −83.9 (4) | C5—C6—C7—I1 | 179.4 (3) |
O5—U1—N1—C10 | 90.6 (3) | C5—C6—C7—C8 | −1.2 (5) |
O6—U1—N1—C2 | 92.8 (4) | C6—C7—C8—C10 | 0.3 (5) |
O6—U1—N1—C10 | −92.8 (3) | I1—C7—C8—C10 | 179.7 (2) |
O1—S1—C5—C6 | 133.2 (3) | I1—C7—C8—O4 | −0.8 (5) |
O1—S1—C5—C9 | −53.5 (3) | C6—C7—C8—O4 | 179.8 (3) |
O2—S1—C5—C6 | −108.9 (3) | O4—C8—C10—N1 | 1.2 (5) |
O2—S1—C5—C9 | 64.5 (3) | O4—C8—C10—C9 | −178.9 (3) |
O3—S1—C5—C6 | 11.5 (3) | C7—C8—C10—N1 | −179.2 (3) |
O3—S1—C5—C9 | −175.1 (3) | C7—C8—C10—C9 | 0.7 (5) |
U1—O4—C8—C7 | 172.7 (3) | C4—C9—C10—C8 | −179.9 (3) |
U1—O4—C8—C10 | −7.7 (5) | C5—C9—C10—N1 | 179.2 (3) |
C2—N1—C10—C9 | −0.5 (6) | C5—C9—C10—C8 | −0.7 (5) |
U1—N1—C2—C3 | 174.9 (3) | C4—C9—C10—N1 | −0.1 (5) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) x+1, y−1, z; (iv) −x+2, −y, −z+1; (v) x, y, z+1; (vi) −x+1, −y+1, −z+1; (vii) x−1, y+1, z; (viii) −x+2, −y, −z+2; (ix) −x+1, −y+1, −z; (x) x+1, y−1, z+1; (xi) x, y, z−1; (xii) x−1, y+1, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O4W | 0.95 | 1.72 | 2.644 (4) | 163 |
O1W—H1B···O1i | 0.95 | 1.77 | 2.671 (4) | 157 |
O2W—H2A···O5W | 0.91 | 1.78 | 2.616 (6) | 153 |
O2W—H2A···O6ii | 0.91 | 2.55 | 3.078 (4) | 118 |
O2W—H2B···O4Wix | 0.88 | 2.10 | 2.975 (4) | 175 |
O3W—H3A···O2iv | 0.95 | 1.81 | 2.752 (4) | 170 |
O3W—H3B···O1xi | 0.95 | 1.93 | 2.829 (4) | 156 |
O4W—H4B···O2vi | 0.94 | 1.87 | 2.798 (4) | 172 |
C2—H2···O1W | 0.93 | 2.51 | 3.131 (5) | 124 |
C4—H4···O1 | 0.93 | 2.48 | 3.083 (5) | 122 |
C6—H6···O3 | 0.93 | 2.43 | 2.849 (4) | 107 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iv) −x+2, −y, −z+1; (vi) −x+1, −y+1, −z+1; (ix) −x+1, −y+1, −z; (xi) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [U(C9H4INO4S)O2(H2O)3]·2H2O |
Mr | 707.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.3742 (2), 10.1785 (2), 11.6146 (2) |
α, β, γ (°) | 74.958 (1), 84.717 (1), 66.701 (1) |
V (Å3) | 878.04 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 11.17 |
Crystal size (mm) | 0.15 × 0.13 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.286, 0.348 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21488, 6209, 5581 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.777 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.059, 1.04 |
No. of reflections | 6209 |
No. of parameters | 218 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.70, −1.16 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
U1—O1W | 2.417 (3) | U1—O5 | 1.763 (3) |
U1—O2W | 2.427 (2) | U1—O6 | 1.759 (3) |
U1—O3W | 2.426 (3) | U1—N1 | 2.605 (3) |
U1—O4 | 2.281 (3) | ||
O1W—U1—O2W | 75.84 (9) | O3W—U1—O5 | 93.23 (13) |
O1W—U1—O3W | 148.59 (8) | O3W—U1—O6 | 89.79 (12) |
O1W—U1—O4 | 139.84 (9) | O3W—U1—N1 | 135.24 (9) |
O1W—U1—O5 | 91.87 (12) | O4—U1—O5 | 93.45 (13) |
O1W—U1—O6 | 84.63 (11) | O4—U1—O6 | 89.22 (11) |
O1W—U1—N1 | 76.08 (9) | O4—U1—N1 | 64.80 (9) |
O2W—U1—O3W | 73.66 (9) | O5—U1—O6 | 176.50 (13) |
O2W—U1—O4 | 144.25 (9) | O5—U1—N1 | 85.08 (13) |
O2W—U1—O5 | 85.84 (13) | O6—U1—N1 | 94.03 (11) |
O2W—U1—O6 | 93.32 (10) | O1—S1—O2 | 110.55 (18) |
O2W—U1—N1 | 150.13 (10) | O1—S1—O3 | 112.96 (18) |
O3W—U1—O4 | 70.69 (9) | O2—S1—O3 | 112.50 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O4W | 0.95 | 1.72 | 2.644 (4) | 163 |
O1W—H1B···O1i | 0.95 | 1.77 | 2.671 (4) | 157 |
O2W—H2A···O5W | 0.91 | 1.78 | 2.616 (6) | 153 |
O2W—H2B···O4Wii | 0.88 | 2.10 | 2.975 (4) | 175 |
O3W—H3A···O2iii | 0.95 | 1.81 | 2.752 (4) | 170 |
O3W—H3B···O1iv | 0.95 | 1.93 | 2.829 (4) | 156 |
O4W—H4B···O2v | 0.94 | 1.87 | 2.798 (4) | 172 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) −x+2, −y, −z+1; (iv) x, y, z−1; (v) −x+1, −y+1, −z+1. |
The most common uranium compounds are those containing the linear, symmetrical UO22+ ion (uranyl ion). The number of known complexes of UO22+ is enormous and virtually every kind of oxygen donor ligand, as well as many nitrogen donors, and even sulfur donors, have been found in such complexes (Cotton et al., 1999). Derivatives of 8-hydroxyquinoline (oxine) are known for their anti-amoebic, antibacterial and antifungal activities, which are correlated with their metal-chelating ability (Banerjee & Saha, 1986). The biological activities of oxine derivatives have been correlated with their capacity for metal chelation. Oxine and its derivatives have long been extensively used in analytical chemistry (Hollingshead, 1954–1956), and oxine derivatives are fluorogenic ligands for many metal ions (Launay et al., 2001). Various coordination modes of 8-hydroxyquinoline-5-sulfonic acid (HQS) and 7-iodo-8-hydroxyquinoline-5-sulfonic acid (ferron) have been reported. The crystal structures of copper complexes of HQS (Petit, Coquerel & Perez, 1993; Petit, Ammor et al., 1993) have also been investigated. We have reported the crystal structures of: 7-iodo-8-hydroxyquinoline-5-sulfonic acid (Balasubramanian & Muthiah, 1996); sodium, copper, strontium, zinc and nickel complexes of ferron (Raj et al., 2003; Francis et al., 2003a; Balasubramani et al., 2004; Francis et al., 2003c; Raj et al., 2001, respectively); and potassium complexes of HQS (Francis et al., 2003b). The crystal structures of uranyl complexes of 4,4'-bipyridine (Thuéry, 2007), uranyl-n-pentane-1,5-dicarboxylate (Borkowski et al., 2005) and uranyl pyridazine-3-carboxylate dihydrate (Leciejewicz et al., 2009) have also been reported. The crystal structure of the title complex, [U(C9H4INO4S)O2(H2O)3].2H20, (I), is presented here.
In the crystal structure of (I), the asymmetric unit contains a UO22+ ion, a 7-iodo-8-quinolinolato-5-sulfonate (ferron) anion, three coordinated water molecules and two uncoordinated water molecules, as shown in Fig. 1. The uranium ion adopts seven-coordinate pentagonal bipyrimidal geometry. Two short uranyl oxygen bonds are observed in axial positions, with U—O distances (Table 1) close to the average reported value of 1.758 (3) Å (Burns et al., 1997). The O5—U1—O6 angle is close to 180°. The N and O atoms of the oxine ring (bidentate chelation) moiety and the three water molecules (O1W, O2W and O3W) are coordinated to the metal in the equatorial positions (Table 1). In the chelate, the U1—O4 bond distance is significantly shorter than the U1—N1 bond distance. This trend has also been observed in various metal complexes of ferron and related ligands (Francis et al., 2003a,b, 2004; Raj et al., 2001; Thuéry, 2007; Leciejewicz et al., 2009). Hydrogen-bonding patterns involving the sulfonate oxygen in biological systems and metal complexes are of current interest (Onoda et al., 2001). The sulfonate O atoms are not involved in the coordination but make an extensive network of O—H···O hydrogen bonds with all of the coordinated and uncoordinated water molecules (Table 2). The sulfonate O atoms (O1 and O2) interact with the coordinated and uncoordinated water molecules to form a chain of R33(10) rings (Etter, 1990; Bernstein et al., 1995) running parallel to [001]. These chains are interlinked by the coordinated water molecule of (O1W) acting as a donor, one uncoordinated water molecule (O4W) acting as both donor and acceptor and the sulfonate oxygen (O2) as an acceptor, via further O—H···O hydrogen bonds (Table 2), to form a supramolecular sheet which lies parallel to (110) (Fig. 2). The organic ligands are stacked over one another. Each pair of the adjacent ligands stack, in an inversion-related manner, and are linked to one another via O—H···O hydrogen bonds involving one of the coordinated water molecules (O1W and O3W) and sulfonate O atoms to form a ladder. These supramolecular ladder are crosslinked via O—H···O hydrogen bonds to form the three-dimensional network (Fig. 3). π–π stacking interactions between oxine rings, with a perpendicular separatiion of 3.5989 (16)Å, a centroid–centriod distance of 3.632 (2)Å and a slip angle (the angle between the centroid vector and the normal to the plane) of 7.76°, further stabilize the crystal structure.