Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111004227/sq3279sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111004227/sq3279Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111004227/sq3279IIsup3.hkl |
CCDC references: 791807; 791808
For related literature, see: Borkowski & Cahill (2006); Frisch & Cahill (2005); Masci & Thuéry (2008); Sasikumar & Muthiah (2010); Spek (2009); Szigethy & Raymond (2009); Thuéry (2008); Thuery & Masci (2008).
With uranium being a radioactive and chemically toxic element, uranium-containing samples must be handled with suitable care and protection. All starting materials used in these synthetic reactions are available commercially and were used as obtained from the supplier.
For the preparation of (I), dioxouranium (VI) nitrate hexahydrate {[UO2(NO3)2].6H2O; 0.1505 g, Loba Chemie) was dissolved in a methanol–water solution (1:1v/v, 20 ml) and 5-chlorothiophene-2-carboxylic acid (0.0850 g, Hoechst Aktiengesellschaft) was dissolved in acetonitrile (20 ml). Both solutions were stirred separately for 30 min at 313 K. On mixing the two solutions, a pale-yellow solution was obtained. Then 4,4'-bipyridine (0.0442 g, Aldrich) was added directly to the warm solution with stirring and heating was continued for 30 min. The resulting clear, pale-yellow solution was kept undisturbed at room temperature for crystallization. After 30 d, clear, yellow, plate-shaped crystals formed on the surface of the mother liquor. The crystals were isolated, washed with small portions of methanol and dried in air.
For the preparation of (II), the same procedure was used with 1,2-bis(4-pyridyl)ethane in place of 4,4'-bipyridine. Yellow, plate-shaped crystals were obtained. The approximate yield of the crystals for both (I) and (II) is about 52%.
All C- and N-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and N—H = 0.86 Å and with Uiso(H) = 1.2Ueq(C or N). The water H atoms of (I) and (II) were located in difference Fourier maps and refined using O—H distance restraints of 0.82 Å and H···H restraints of 1.40 [for (I)] and 1.38 Å [for (II)] via DFIX commands with fixed Uiso(H) = 1.2Ueq(O).
For both compounds, 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).
(C10H10N2)0.5[U(C5H2ClO2S)3O2]·H2O | F(000) = 1612.0 |
Mr = 851.90 | Dx = 2.080 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.1630 (5) Å | Cell parameters from 9658 reflections |
b = 17.5777 (6) Å | θ = 2.2–27.1° |
c = 11.2915 (4) Å | µ = 6.54 mm−1 |
β = 104.595 (2)° | T = 296 K |
V = 2720.34 (16) Å3 | Plate, yellow |
Z = 4 | 0.08 × 0.06 × 0.05 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 8824 independent reflections |
Radiation source: fine-focus sealed tube | 5253 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ϕ and ω scans | θmax = 31.2°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −20→20 |
Tmin = 0.577, Tmax = 0.698 | k = −20→25 |
33776 measured reflections | l = −16→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0377P)2 + 0.918P] where P = (Fo2 + 2Fc2)/3 |
8747 reflections | (Δ/σ)max = 0.001 |
313 parameters | Δρmax = 1.16 e Å−3 |
3 restraints | Δρmin = −1.03 e Å−3 |
(C10H10N2)0.5[U(C5H2ClO2S)3O2]·H2O | V = 2720.34 (16) Å3 |
Mr = 851.90 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.1630 (5) Å | µ = 6.54 mm−1 |
b = 17.5777 (6) Å | T = 296 K |
c = 11.2915 (4) Å | 0.08 × 0.06 × 0.05 mm |
β = 104.595 (2)° |
Bruker SMART APEXII CCD area-detector diffractometer | 8824 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 5253 reflections with I > 2σ(I) |
Tmin = 0.577, Tmax = 0.698 | Rint = 0.042 |
33776 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 3 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 1.16 e Å−3 |
8747 reflections | Δρmin = −1.03 e Å−3 |
313 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 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 | 0.22068 (1) | 0.42260 (1) | 0.67302 (1) | 0.0406 (1) | |
Cl1 | 0.29668 (19) | 0.58763 (11) | 0.02601 (17) | 0.1245 (9) | |
Cl2 | 0.45307 (19) | 0.30120 (14) | 1.39093 (15) | 0.1466 (10) | |
Cl3 | −0.31280 (12) | 0.23218 (9) | 0.67844 (13) | 0.0788 (6) | |
S1 | 0.24253 (11) | 0.52405 (8) | 0.24043 (11) | 0.0664 (5) | |
S2 | 0.34734 (13) | 0.33002 (10) | 1.13378 (13) | 0.0866 (6) | |
S3 | −0.11079 (10) | 0.29068 (7) | 0.71611 (10) | 0.0550 (4) | |
O1 | 0.2572 (3) | 0.33319 (18) | 0.6313 (3) | 0.0671 (14) | |
O2 | 0.1817 (2) | 0.51121 (16) | 0.7141 (3) | 0.0531 (11) | |
O3 | 0.2041 (2) | 0.4629 (2) | 0.4623 (3) | 0.0599 (13) | |
O4 | 0.3455 (2) | 0.4863 (2) | 0.5907 (3) | 0.0599 (11) | |
O5 | 0.3724 (2) | 0.43507 (18) | 0.8391 (3) | 0.0550 (11) | |
O6 | 0.2509 (2) | 0.37585 (19) | 0.8838 (3) | 0.0616 (11) | |
O7 | 0.0808 (2) | 0.36017 (18) | 0.7270 (3) | 0.0571 (11) | |
O8 | 0.0532 (2) | 0.39807 (19) | 0.5374 (3) | 0.0534 (11) | |
C1 | 0.2894 (4) | 0.4889 (3) | 0.4836 (4) | 0.0507 (16) | |
C2 | 0.3229 (4) | 0.5220 (3) | 0.3818 (4) | 0.0498 (17) | |
C3 | 0.4093 (4) | 0.5529 (3) | 0.3782 (6) | 0.072 (2) | |
C4 | 0.4115 (5) | 0.5780 (3) | 0.2594 (7) | 0.083 (3) | |
C5 | 0.3262 (5) | 0.5657 (3) | 0.1791 (5) | 0.071 (2) | |
C6 | 0.3387 (4) | 0.4001 (3) | 0.9163 (4) | 0.0466 (16) | |
C7 | 0.3957 (3) | 0.3866 (3) | 1.0414 (4) | 0.0460 (16) | |
C8 | 0.4827 (4) | 0.4136 (3) | 1.1024 (5) | 0.0609 (19) | |
C9 | 0.5121 (4) | 0.3899 (3) | 1.2253 (4) | 0.0637 (17) | |
C10 | 0.4478 (5) | 0.3441 (3) | 1.2529 (4) | 0.071 (2) | |
C11 | 0.0233 (3) | 0.3655 (2) | 0.6210 (4) | 0.0430 (16) | |
C12 | −0.0761 (3) | 0.3363 (2) | 0.5984 (4) | 0.0433 (16) | |
C13 | −0.1504 (4) | 0.3407 (3) | 0.4966 (4) | 0.0547 (16) | |
C14 | −0.2368 (4) | 0.3065 (3) | 0.5106 (5) | 0.0655 (19) | |
C15 | −0.2253 (4) | 0.2779 (3) | 0.6248 (4) | 0.0554 (17) | |
N1 | 0.0689 (3) | 0.3634 (3) | 0.2272 (4) | 0.0685 (17) | |
C16 | 0.0134 (3) | 0.4691 (3) | 0.0473 (4) | 0.0500 (18) | |
C17 | −0.0058 (4) | 0.4788 (3) | 0.1609 (4) | 0.0653 (19) | |
C18 | 0.0238 (4) | 0.4250 (4) | 0.2494 (5) | 0.070 (2) | |
C19 | 0.0868 (5) | 0.3503 (3) | 0.1184 (5) | 0.075 (2) | |
C20 | 0.0589 (5) | 0.4032 (3) | 0.0271 (5) | 0.070 (2) | |
O1W | 0.1513 (3) | 0.2639 (2) | 0.4031 (3) | 0.0852 (16) | |
H3 | 0.46200 | 0.55740 | 0.44640 | 0.0860* | |
H4 | 0.46540 | 0.60010 | 0.24010 | 0.0990* | |
H8 | 0.52040 | 0.44530 | 1.06670 | 0.0730* | |
H9 | 0.56980 | 0.40490 | 1.28000 | 0.0760* | |
H13 | −0.14500 | 0.36390 | 0.42460 | 0.0660* | |
H14 | −0.29450 | 0.30390 | 0.44920 | 0.0790* | |
H1 | 0.08760 | 0.33050 | 0.28470 | 0.0820* | |
H17 | −0.03890 | 0.52180 | 0.17670 | 0.0780* | |
H18 | 0.01210 | 0.43200 | 0.32610 | 0.0840* | |
H19 | 0.11780 | 0.30570 | 0.10470 | 0.0900* | |
H20 | 0.07080 | 0.39430 | −0.04900 | 0.0840* | |
H1W | 0.164 (4) | 0.2230 (19) | 0.378 (5) | 0.1020* | |
H2W | 0.190 (4) | 0.280 (3) | 0.465 (4) | 0.1020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.0460 (1) | 0.0456 (1) | 0.0301 (1) | −0.0037 (1) | 0.0092 (1) | 0.0001 (1) |
Cl1 | 0.174 (2) | 0.1443 (17) | 0.0763 (11) | 0.0503 (14) | 0.0708 (13) | 0.0543 (11) |
Cl2 | 0.179 (2) | 0.176 (2) | 0.0559 (10) | −0.0633 (18) | −0.0242 (12) | 0.0504 (12) |
Cl3 | 0.0739 (9) | 0.0956 (11) | 0.0757 (9) | −0.0308 (9) | 0.0353 (8) | −0.0111 (8) |
S1 | 0.0740 (10) | 0.0858 (10) | 0.0410 (7) | −0.0052 (8) | 0.0176 (6) | 0.0066 (6) |
S2 | 0.0869 (11) | 0.1075 (12) | 0.0505 (8) | −0.0490 (10) | −0.0101 (7) | 0.0249 (8) |
S3 | 0.0580 (8) | 0.0654 (8) | 0.0402 (6) | −0.0106 (6) | 0.0096 (5) | 0.0082 (5) |
O1 | 0.075 (3) | 0.057 (2) | 0.062 (2) | 0.0116 (18) | 0.0037 (19) | −0.0114 (17) |
O2 | 0.068 (2) | 0.0491 (18) | 0.0473 (17) | −0.0002 (16) | 0.0241 (16) | −0.0012 (14) |
O3 | 0.049 (2) | 0.098 (3) | 0.0333 (16) | −0.0195 (19) | 0.0116 (14) | 0.0051 (17) |
O4 | 0.052 (2) | 0.091 (2) | 0.0363 (16) | −0.0151 (18) | 0.0102 (15) | 0.0018 (17) |
O5 | 0.052 (2) | 0.071 (2) | 0.0406 (17) | −0.0158 (16) | 0.0091 (15) | 0.0047 (15) |
O6 | 0.058 (2) | 0.077 (2) | 0.0393 (17) | −0.0271 (19) | −0.0073 (15) | 0.0162 (16) |
O7 | 0.053 (2) | 0.077 (2) | 0.0357 (16) | −0.0204 (17) | 0.0006 (14) | 0.0149 (15) |
O8 | 0.050 (2) | 0.072 (2) | 0.0363 (16) | −0.0086 (17) | 0.0071 (14) | 0.0082 (15) |
C1 | 0.054 (3) | 0.064 (3) | 0.039 (2) | −0.006 (3) | 0.021 (2) | 0.000 (2) |
C2 | 0.049 (3) | 0.057 (3) | 0.048 (3) | −0.001 (2) | 0.021 (2) | 0.003 (2) |
C3 | 0.054 (3) | 0.087 (4) | 0.079 (4) | 0.002 (3) | 0.027 (3) | 0.013 (3) |
C4 | 0.079 (5) | 0.087 (4) | 0.103 (5) | 0.006 (4) | 0.063 (4) | 0.032 (4) |
C5 | 0.088 (5) | 0.077 (4) | 0.060 (3) | 0.020 (3) | 0.042 (3) | 0.018 (3) |
C6 | 0.050 (3) | 0.048 (3) | 0.039 (2) | −0.007 (2) | 0.006 (2) | 0.003 (2) |
C7 | 0.049 (3) | 0.050 (3) | 0.034 (2) | −0.010 (2) | 0.0013 (19) | 0.0006 (19) |
C8 | 0.052 (3) | 0.070 (4) | 0.054 (3) | −0.009 (3) | 0.001 (2) | 0.007 (2) |
C9 | 0.062 (3) | 0.065 (3) | 0.050 (3) | −0.007 (3) | −0.012 (2) | 0.003 (3) |
C10 | 0.089 (4) | 0.072 (4) | 0.040 (3) | −0.015 (3) | −0.007 (3) | 0.008 (2) |
C11 | 0.046 (3) | 0.049 (3) | 0.032 (2) | −0.004 (2) | 0.0063 (19) | 0.0057 (19) |
C12 | 0.047 (3) | 0.050 (3) | 0.032 (2) | −0.003 (2) | 0.0082 (19) | 0.0039 (18) |
C13 | 0.055 (3) | 0.069 (3) | 0.037 (2) | −0.009 (3) | 0.006 (2) | 0.009 (2) |
C14 | 0.056 (3) | 0.084 (4) | 0.053 (3) | −0.011 (3) | 0.007 (3) | 0.000 (3) |
C15 | 0.055 (3) | 0.059 (3) | 0.053 (3) | −0.013 (2) | 0.015 (2) | −0.006 (2) |
N1 | 0.062 (3) | 0.087 (3) | 0.052 (3) | −0.006 (3) | 0.006 (2) | 0.022 (2) |
C16 | 0.041 (3) | 0.080 (4) | 0.028 (2) | −0.010 (2) | 0.0068 (18) | 0.004 (2) |
C17 | 0.058 (3) | 0.102 (4) | 0.043 (3) | 0.016 (3) | 0.026 (2) | 0.015 (3) |
C18 | 0.059 (3) | 0.120 (5) | 0.033 (2) | 0.002 (3) | 0.014 (2) | 0.016 (3) |
C19 | 0.094 (5) | 0.077 (4) | 0.057 (3) | −0.002 (3) | 0.024 (3) | 0.003 (3) |
C20 | 0.096 (5) | 0.076 (4) | 0.041 (3) | −0.005 (3) | 0.021 (3) | −0.003 (3) |
O1W | 0.125 (4) | 0.057 (2) | 0.057 (2) | 0.023 (2) | −0.008 (2) | −0.0178 (18) |
U1—O1 | 1.756 (3) | C1—C2 | 1.470 (7) |
U1—O2 | 1.754 (3) | C2—C3 | 1.349 (8) |
U1—O3 | 2.437 (3) | C3—C4 | 1.420 (10) |
U1—O4 | 2.464 (3) | C4—C5 | 1.333 (10) |
U1—O5 | 2.480 (3) | C6—C7 | 1.459 (6) |
U1—O6 | 2.451 (3) | C7—C8 | 1.338 (7) |
U1—O7 | 2.472 (3) | C8—C9 | 1.408 (7) |
U1—O8 | 2.515 (3) | C9—C10 | 1.311 (8) |
Cl1—C5 | 1.717 (6) | C11—C12 | 1.459 (6) |
Cl2—C10 | 1.716 (5) | C12—C13 | 1.351 (7) |
Cl3—C15 | 1.711 (6) | C13—C14 | 1.408 (8) |
S1—C2 | 1.712 (5) | C14—C15 | 1.355 (7) |
S1—C5 | 1.683 (7) | C3—H3 | 0.9300 |
S2—C7 | 1.705 (5) | C4—H4 | 0.9300 |
S2—C10 | 1.712 (6) | C8—H8 | 0.9300 |
S3—C12 | 1.726 (4) | C9—H9 | 0.9300 |
S3—C15 | 1.703 (5) | C13—H13 | 0.9300 |
O3—C1 | 1.257 (6) | C14—H14 | 0.9300 |
O4—C1 | 1.270 (6) | C16—C17 | 1.387 (6) |
O5—C6 | 1.255 (6) | C16—C20 | 1.372 (8) |
O6—C6 | 1.278 (6) | C16—C16i | 1.504 (7) |
O7—C11 | 1.270 (5) | C17—C18 | 1.363 (8) |
O8—C11 | 1.265 (5) | C19—C20 | 1.371 (8) |
O1W—H2W | 0.82 (5) | C17—H17 | 0.9300 |
O1W—H1W | 0.81 (4) | C18—H18 | 0.9300 |
N1—C18 | 1.313 (8) | C19—H19 | 0.9300 |
N1—C19 | 1.336 (7) | C20—H20 | 0.9300 |
N1—H1 | 0.8600 | ||
Cl1···C6ii | 3.623 (6) | O1···H2W | 2.10 (5) |
Cl1···Cl3iii | 3.479 (2) | O1W···H1 | 1.8300 |
Cl3···C9iv | 3.420 (6) | O1W···H19viii | 2.7300 |
Cl3···Cl1v | 3.479 (2) | O2···H17xi | 2.6800 |
Cl1···H8vi | 3.0800 | O2···H18xi | 2.8500 |
Cl2···H3vii | 3.1400 | O2···H13xi | 2.6700 |
Cl3···H14viii | 3.0700 | O3···H18 | 2.8200 |
S1···O3 | 2.901 (4) | O4···H3 | 2.8800 |
S1···C16 | 3.557 (5) | O4···H9vii | 2.5200 |
S1···C17 | 3.495 (6) | O5···H4vi | 2.7400 |
S1···C18 | 3.577 (6) | O5···H8vii | 2.6500 |
S2···O6 | 2.922 (4) | O5···H8 | 2.8800 |
S2···C19ix | 3.668 (7) | O6···H20ix | 2.8600 |
S2···O1viii | 3.137 (4) | O6···H1Wviii | 2.12 (4) |
S3···O7 | 2.950 (3) | O7···H17xi | 2.4800 |
S2···H2Wviii | 3.19 (5) | O7···H1Wviii | 2.33 (5) |
O1···O1W | 2.903 (5) | O7···H20ix | 2.6400 |
O1···O3 | 2.947 (5) | O8···H18 | 2.3800 |
O1···O4 | 3.051 (5) | O8···H13 | 2.8400 |
O1···O5 | 3.073 (5) | N1···O1W | 2.683 (6) |
O1···O6 | 2.971 (5) | C2···C14xi | 3.577 (8) |
O1···O7 | 2.999 (5) | C6···Cl1ix | 3.623 (6) |
O1···O8 | 3.038 (5) | C8···O5vii | 3.323 (6) |
O1···C1 | 3.296 (6) | C9···Cl3xii | 3.420 (6) |
O1···C6 | 3.347 (6) | C9···O4vii | 3.318 (6) |
O1···C11 | 3.334 (6) | C14···C2xi | 3.577 (8) |
O1···S2x | 3.137 (4) | C16···S1 | 3.557 (5) |
O1W···O6x | 2.868 (5) | C17···O2xi | 3.163 (6) |
O1W···N1 | 2.683 (6) | C17···O7xi | 3.379 (6) |
O1W···O1 | 2.903 (5) | C17···S1 | 3.495 (6) |
O1W···O7x | 2.951 (5) | C18···O2xi | 3.241 (7) |
O2···O4 | 3.024 (4) | C18···S1 | 3.577 (6) |
O2···O7 | 3.036 (4) | C18···O8 | 3.208 (6) |
O2···C11 | 3.393 (5) | C18···O3 | 3.106 (7) |
O2···O3 | 3.059 (5) | C19···S2ii | 3.668 (7) |
O2···C6 | 3.378 (6) | C3···H3vi | 3.0300 |
O2···O6 | 3.057 (4) | C11···H17xi | 2.9900 |
O2···C17xi | 3.163 (6) | C17···H20i | 2.6100 |
O2···C18xi | 3.241 (7) | C20···H17i | 2.6000 |
O2···C1 | 3.355 (6) | H1···O1W | 1.8300 |
O2···O8 | 3.069 (4) | H1···H2W | 2.3600 |
O2···O5 | 3.026 (4) | H1···H1W | 2.3000 |
O3···O4 | 2.195 (4) | H1W···H1 | 2.3000 |
O3···O1 | 2.947 (5) | H1W···O7x | 2.33 (5) |
O3···O2 | 3.059 (5) | H1W···O6x | 2.12 (4) |
O3···C18 | 3.106 (7) | H2W···O1 | 2.10 (5) |
O3···S1 | 2.901 (4) | H2W···S2x | 3.19 (5) |
O3···O8 | 2.738 (4) | H2W···H19viii | 2.5700 |
O4···O2 | 3.024 (4) | H2W···H1 | 2.3600 |
O4···C9vii | 3.318 (6) | H3···C3vi | 3.0300 |
O4···O3 | 2.195 (4) | H3···Cl2vii | 3.1400 |
O4···O5 | 2.878 (5) | H3···O4 | 2.8800 |
O4···O1 | 3.051 (5) | H3···H3vi | 2.4600 |
O5···O2 | 3.026 (4) | H4···O5vi | 2.7400 |
O5···O6 | 2.177 (4) | H8···H8vii | 2.4200 |
O5···C8vii | 3.323 (6) | H8···O5 | 2.8800 |
O5···O1 | 3.073 (5) | H8···Cl1vi | 3.0800 |
O5···O4 | 2.878 (5) | H8···O5vii | 2.6500 |
O6···O1Wviii | 2.868 (5) | H9···O4vii | 2.5200 |
O6···S2 | 2.922 (4) | H13···O2xi | 2.6700 |
O6···O5 | 2.177 (4) | H13···O8 | 2.8400 |
O6···O1 | 2.971 (5) | H14···Cl3x | 3.0700 |
O6···O7 | 2.620 (4) | H17···H20i | 2.0300 |
O6···O2 | 3.057 (4) | H17···O7xi | 2.4800 |
O7···O8 | 2.181 (5) | H17···O2xi | 2.6800 |
O7···S3 | 2.950 (3) | H17···C11xi | 2.9900 |
O7···C17xi | 3.379 (6) | H17···C20i | 2.6000 |
O7···O6 | 2.620 (4) | H18···O3 | 2.8200 |
O7···O2 | 3.036 (4) | H18···O2xi | 2.8500 |
O7···O1Wviii | 2.951 (5) | H18···O8 | 2.3800 |
O7···O1 | 2.999 (5) | H19···O1Wx | 2.7300 |
O8···C18 | 3.208 (6) | H19···H2Wx | 2.5700 |
O8···O7 | 2.181 (5) | H20···C17i | 2.6100 |
O8···O2 | 3.069 (4) | H20···H17i | 2.0300 |
O8···O3 | 2.738 (4) | H20···O6ii | 2.8600 |
O8···O1 | 3.038 (5) | H20···O7ii | 2.6400 |
O1—U1—O2 | 178.81 (17) | S1—C5—C4 | 113.7 (5) |
O1—U1—O3 | 87.75 (13) | O5—C6—C7 | 122.5 (5) |
O1—U1—O4 | 91.01 (15) | O6—C6—C7 | 119.0 (4) |
O1—U1—O5 | 91.39 (14) | O5—C6—O6 | 118.5 (4) |
O1—U1—O6 | 88.24 (13) | S2—C7—C6 | 118.5 (4) |
O1—U1—O7 | 88.71 (15) | S2—C7—C8 | 110.6 (4) |
O1—U1—O8 | 88.83 (15) | C6—C7—C8 | 130.8 (5) |
O2—U1—O3 | 92.34 (13) | C7—C8—C9 | 114.1 (5) |
O2—U1—O4 | 89.99 (13) | C8—C9—C10 | 111.4 (5) |
O2—U1—O5 | 89.54 (13) | Cl2—C10—C9 | 127.7 (4) |
O2—U1—O6 | 91.75 (13) | S2—C10—C9 | 113.1 (4) |
O2—U1—O7 | 90.22 (12) | Cl2—C10—S2 | 119.2 (4) |
O2—U1—O8 | 90.11 (13) | O7—C11—C12 | 120.0 (4) |
O3—U1—O4 | 53.22 (10) | O8—C11—C12 | 121.2 (4) |
O3—U1—O5 | 124.37 (10) | O7—C11—O8 | 118.8 (4) |
O3—U1—O6 | 174.76 (10) | S3—C12—C13 | 111.7 (4) |
O3—U1—O7 | 118.94 (10) | C11—C12—C13 | 129.7 (4) |
O3—U1—O8 | 67.13 (10) | S3—C12—C11 | 118.6 (3) |
O4—U1—O5 | 71.20 (10) | C12—C13—C14 | 113.1 (4) |
O4—U1—O6 | 123.52 (10) | C13—C14—C15 | 111.5 (5) |
O4—U1—O7 | 172.16 (11) | Cl3—C15—C14 | 126.0 (4) |
O4—U1—O8 | 120.29 (11) | S3—C15—C14 | 113.3 (4) |
O5—U1—O6 | 52.37 (10) | Cl3—C15—S3 | 120.8 (3) |
O5—U1—O7 | 116.64 (10) | C4—C3—H3 | 123.00 |
O5—U1—O8 | 168.50 (10) | C2—C3—H3 | 124.00 |
O6—U1—O7 | 64.31 (10) | C3—C4—H4 | 124.00 |
O6—U1—O8 | 116.16 (10) | C5—C4—H4 | 124.00 |
O7—U1—O8 | 51.87 (11) | C7—C8—H8 | 123.00 |
C2—S1—C5 | 91.2 (3) | C9—C8—H8 | 123.00 |
C7—S2—C10 | 90.8 (3) | C10—C9—H9 | 124.00 |
C12—S3—C15 | 90.4 (2) | C8—C9—H9 | 124.00 |
U1—O3—C1 | 93.9 (3) | C14—C13—H13 | 123.00 |
U1—O4—C1 | 92.3 (3) | C12—C13—H13 | 123.00 |
U1—O5—C6 | 94.2 (3) | C13—C14—H14 | 124.00 |
U1—O6—C6 | 95.0 (3) | C15—C14—H14 | 124.00 |
U1—O7—C11 | 95.6 (3) | C16i—C16—C20 | 122.5 (4) |
U1—O8—C11 | 93.7 (3) | C17—C16—C20 | 117.9 (5) |
H1W—O1W—H2W | 116 (5) | C16i—C16—C17 | 119.7 (4) |
C18—N1—C19 | 122.2 (5) | C16—C17—C18 | 119.8 (5) |
C18—N1—H1 | 119.00 | N1—C18—C17 | 120.5 (5) |
C19—N1—H1 | 119.00 | N1—C19—C20 | 119.3 (5) |
O3—C1—O4 | 120.7 (4) | C16—C20—C19 | 120.4 (5) |
O4—C1—C2 | 120.8 (5) | C16—C17—H17 | 120.00 |
O3—C1—C2 | 118.6 (4) | C18—C17—H17 | 120.00 |
S1—C2—C3 | 111.0 (4) | C17—C18—H18 | 120.00 |
S1—C2—C1 | 117.9 (4) | N1—C18—H18 | 120.00 |
C1—C2—C3 | 131.1 (5) | N1—C19—H19 | 120.00 |
C2—C3—C4 | 112.9 (6) | C20—C19—H19 | 120.00 |
C3—C4—C5 | 111.1 (6) | C16—C20—H20 | 120.00 |
Cl1—C5—C4 | 126.7 (6) | C19—C20—H20 | 120.00 |
Cl1—C5—S1 | 119.6 (4) | ||
O1—U1—O3—C1 | −92.6 (3) | U1—O4—C1—O3 | 0.6 (5) |
O2—U1—O3—C1 | 88.6 (3) | U1—O4—C1—C2 | −179.1 (4) |
O4—U1—O3—C1 | 0.3 (3) | U1—O5—C6—O6 | −0.7 (5) |
O5—U1—O3—C1 | −2.5 (3) | U1—O5—C6—C7 | 179.7 (5) |
O7—U1—O3—C1 | −179.9 (3) | U1—O6—C6—O5 | 0.7 (5) |
O8—U1—O3—C1 | 177.7 (3) | U1—O6—C6—C7 | −179.6 (4) |
O1—U1—O4—C1 | 86.1 (3) | U1—O7—C11—O8 | −1.5 (4) |
O2—U1—O4—C1 | −93.3 (3) | U1—O7—C11—C12 | −179.7 (3) |
O3—U1—O4—C1 | −0.3 (3) | U1—O8—C11—O7 | 1.4 (4) |
O5—U1—O4—C1 | 177.2 (3) | U1—O8—C11—C12 | 179.7 (3) |
O6—U1—O4—C1 | 174.7 (3) | C18—N1—C19—C20 | 1.1 (9) |
O8—U1—O4—C1 | −3.2 (3) | C19—N1—C18—C17 | −0.7 (9) |
O1—U1—O5—C6 | −86.3 (3) | O3—C1—C2—C3 | −179.4 (6) |
O2—U1—O5—C6 | 93.0 (3) | O3—C1—C2—S1 | 0.8 (7) |
O3—U1—O5—C6 | −174.5 (3) | O4—C1—C2—S1 | −179.5 (4) |
O4—U1—O5—C6 | −176.9 (3) | O4—C1—C2—C3 | 0.3 (9) |
O6—U1—O5—C6 | 0.4 (3) | S1—C2—C3—C4 | −0.7 (6) |
O7—U1—O5—C6 | 3.0 (3) | C1—C2—C3—C4 | 179.6 (5) |
O1—U1—O6—C6 | 92.7 (3) | C2—C3—C4—C5 | 0.8 (7) |
O2—U1—O6—C6 | −88.5 (3) | C3—C4—C5—S1 | −0.5 (7) |
O4—U1—O6—C6 | 2.7 (3) | C3—C4—C5—Cl1 | 179.7 (4) |
O5—U1—O6—C6 | −0.4 (3) | O6—C6—C7—S2 | 7.1 (7) |
O7—U1—O6—C6 | −177.9 (3) | O5—C6—C7—S2 | −173.2 (4) |
O8—U1—O6—C6 | −179.5 (3) | O5—C6—C7—C8 | 9.2 (9) |
O1—U1—O7—C11 | −88.7 (3) | O6—C6—C7—C8 | −170.4 (5) |
O2—U1—O7—C11 | 90.8 (2) | S2—C7—C8—C9 | −0.5 (6) |
O3—U1—O7—C11 | −2.0 (3) | C6—C7—C8—C9 | 177.2 (5) |
O5—U1—O7—C11 | −179.6 (2) | C7—C8—C9—C10 | 1.7 (7) |
O6—U1—O7—C11 | −177.4 (3) | C8—C9—C10—Cl2 | 179.7 (5) |
O8—U1—O7—C11 | 0.8 (2) | C8—C9—C10—S2 | −2.0 (6) |
O1—U1—O8—C11 | 88.5 (3) | O7—C11—C12—C13 | 174.9 (4) |
O2—U1—O8—C11 | −91.0 (3) | O7—C11—C12—S3 | −3.2 (5) |
O3—U1—O8—C11 | 176.5 (3) | O8—C11—C12—C13 | −3.3 (7) |
O4—U1—O8—C11 | 178.9 (2) | O8—C11—C12—S3 | 178.6 (3) |
O6—U1—O8—C11 | 1.0 (3) | C11—C12—C13—C14 | −179.0 (4) |
O7—U1—O8—C11 | −0.8 (2) | S3—C12—C13—C14 | −0.8 (5) |
C5—S1—C2—C1 | −179.9 (4) | C12—C13—C14—C15 | 0.9 (7) |
C5—S1—C2—C3 | 0.3 (5) | C13—C14—C15—S3 | −0.7 (6) |
C2—S1—C5—Cl1 | 180.0 (4) | C13—C14—C15—Cl3 | 179.9 (4) |
C2—S1—C5—C4 | 0.1 (5) | C20—C16—C17—C18 | 2.5 (8) |
C10—S2—C7—C6 | −178.5 (4) | C16i—C16—C17—C18 | −176.0 (5) |
C10—S2—C7—C8 | −0.5 (4) | C17—C16—C20—C19 | −2.0 (9) |
C7—S2—C10—Cl2 | 179.9 (4) | C16i—C16—C20—C19 | 176.4 (5) |
C7—S2—C10—C9 | 1.5 (5) | C17—C16—C16i—C17i | 180.0 (5) |
C15—S3—C12—C11 | 178.7 (3) | C17—C16—C16i—C20i | −1.6 (7) |
C15—S3—C12—C13 | 0.3 (4) | C20—C16—C16i—C17i | 1.6 (7) |
C12—S3—C15—Cl3 | 179.7 (3) | C20—C16—C16i—C20i | −180.0 (6) |
C12—S3—C15—C14 | 0.2 (4) | C16—C17—C18—N1 | −1.2 (9) |
U1—O3—C1—O4 | −0.6 (5) | N1—C19—C20—C16 | 0.3 (10) |
U1—O3—C1—C2 | 179.1 (4) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z−1; (iii) −x, y+1/2, −z+1/2; (iv) x−1, −y+1/2, z−1/2; (v) −x, y−1/2, −z+1/2; (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y+1, −z+2; (viii) x, −y+1/2, z+1/2; (ix) x, y, z+1; (x) x, −y+1/2, z−1/2; (xi) −x, −y+1, −z+1; (xii) x+1, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.86 | 1.83 | 2.683 (6) | 169 |
O1W—H1W···O6x | 0.81 (4) | 2.12 (4) | 2.868 (5) | 154 (5) |
O1W—H1W···O7x | 0.81 (4) | 2.33 (5) | 2.951 (5) | 134 (5) |
O1W—H2W···O1 | 0.82 (5) | 2.10 (5) | 2.903 (5) | 166 (5) |
C9—H9···O4vii | 0.93 | 2.52 | 3.318 (6) | 144 |
C17—H17···O7xi | 0.93 | 2.48 | 3.379 (6) | 162 |
C18—H18···O8 | 0.93 | 2.38 | 3.208 (6) | 147 |
Symmetry codes: (vii) −x+1, −y+1, −z+2; (x) x, −y+1/2, z−1/2; (xi) −x, −y+1, −z+1. |
(C12H14N2)0.5[U(C5H2ClO2S)3O2]·H2O | F(000) = 1644.0 |
Mr = 865.92 | Dx = 1.978 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.5189 (2) Å | Cell parameters from 9391 reflections |
b = 18.1169 (3) Å | θ = 2.5–23.6° |
c = 11.1399 (2) Å | µ = 6.12 mm−1 |
β = 97.123 (1)° | T = 296 K |
V = 2907.60 (8) Å3 | Plate, yellow |
Z = 4 | 0.10 × 0.08 × 0.05 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 7244 independent reflections |
Radiation source: fine-focus sealed tube | 4711 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ϕ and ω scans | θmax = 28.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −16→19 |
Tmin = 0.531, Tmax = 0.713 | k = −24→20 |
32147 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3 |
7244 reflections | (Δ/σ)max = 0.020 |
328 parameters | Δρmax = 1.32 e Å−3 |
3 restraints | Δρmin = −0.68 e Å−3 |
(C12H14N2)0.5[U(C5H2ClO2S)3O2]·H2O | V = 2907.60 (8) Å3 |
Mr = 865.92 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.5189 (2) Å | µ = 6.12 mm−1 |
b = 18.1169 (3) Å | T = 296 K |
c = 11.1399 (2) Å | 0.10 × 0.08 × 0.05 mm |
β = 97.123 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 7244 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 4711 reflections with I > 2σ(I) |
Tmin = 0.531, Tmax = 0.713 | Rint = 0.049 |
32147 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 3 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 1.32 e Å−3 |
7244 reflections | Δρmin = −0.68 e Å−3 |
328 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 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 | 0.23722 (1) | 0.42379 (1) | 0.71943 (2) | 0.0490 (1) | |
Cl1 | 0.4756 (2) | 0.30454 (18) | 1.4024 (2) | 0.1888 (15) | |
Cl2 | 0.29337 (16) | 0.59360 (13) | 0.04965 (18) | 0.1169 (9) | |
Cl3 | −0.27346 (18) | 0.21642 (17) | 0.7309 (3) | 0.1577 (14) | |
S1 | 0.36345 (14) | 0.33663 (12) | 1.16820 (15) | 0.1050 (8) | |
S2 | 0.24680 (11) | 0.52615 (11) | 0.27535 (13) | 0.0769 (7) | |
S3 | −0.08681 (13) | 0.28445 (10) | 0.77881 (16) | 0.0862 (7) | |
O1 | 0.2003 (3) | 0.5097 (2) | 0.7668 (3) | 0.0708 (14) | |
O2 | 0.2739 (3) | 0.3369 (2) | 0.6748 (3) | 0.0709 (14) | |
O3 | 0.2655 (3) | 0.3802 (2) | 0.9290 (3) | 0.0668 (14) | |
O4 | 0.3816 (3) | 0.43778 (19) | 0.8615 (4) | 0.0616 (12) | |
O5 | 0.3541 (3) | 0.4841 (2) | 0.6096 (3) | 0.0685 (14) | |
O6 | 0.2185 (3) | 0.4620 (3) | 0.5089 (3) | 0.0781 (14) | |
O7 | 0.0805 (3) | 0.4027 (2) | 0.6093 (3) | 0.0697 (14) | |
O8 | 0.0988 (2) | 0.3598 (2) | 0.7927 (3) | 0.0686 (14) | |
C1 | 0.3505 (4) | 0.4032 (3) | 0.9452 (5) | 0.0562 (19) | |
C2 | 0.4063 (4) | 0.3890 (3) | 1.0611 (5) | 0.0594 (19) | |
C3 | 0.4929 (4) | 0.4139 (3) | 1.1028 (7) | 0.074 (3) | |
C4 | 0.5258 (5) | 0.3886 (4) | 1.2208 (7) | 0.091 (3) | |
C5 | 0.4645 (6) | 0.3465 (4) | 1.2642 (6) | 0.098 (3) | |
C6 | 0.2995 (4) | 0.4879 (3) | 0.5122 (5) | 0.066 (2) | |
C7 | 0.3272 (4) | 0.5210 (3) | 0.4029 (5) | 0.063 (2) | |
C8 | 0.4082 (5) | 0.5507 (4) | 0.3817 (6) | 0.085 (3) | |
C9 | 0.4079 (5) | 0.5776 (4) | 0.2641 (7) | 0.089 (3) | |
C10 | 0.3263 (5) | 0.5682 (3) | 0.1976 (6) | 0.077 (3) | |
C11 | 0.0509 (4) | 0.3676 (3) | 0.6931 (5) | 0.0568 (19) | |
C12 | −0.0435 (4) | 0.3358 (3) | 0.6716 (5) | 0.0613 (17) | |
C13 | −0.1068 (3) | 0.3399 (3) | 0.5665 (4) | 0.0540 (19) | |
C14 | −0.1895 (5) | 0.3012 (5) | 0.5789 (7) | 0.106 (3) | |
C15 | −0.1871 (4) | 0.2695 (4) | 0.6864 (7) | 0.089 (3) | |
N1 | 0.8874 (3) | 0.6585 (3) | 0.7066 (4) | 0.0686 (17) | |
C16 | 0.9848 (4) | 0.5792 (3) | 0.8867 (5) | 0.0542 (17) | |
C17 | 0.9871 (4) | 0.5622 (3) | 0.7662 (5) | 0.062 (2) | |
C18 | 0.9384 (4) | 0.6030 (4) | 0.6774 (5) | 0.064 (2) | |
C19 | 0.8825 (5) | 0.6779 (3) | 0.8215 (6) | 0.074 (3) | |
C20 | 0.9301 (4) | 0.6385 (3) | 0.9125 (5) | 0.064 (2) | |
C21 | 1.0326 (4) | 0.5316 (3) | 0.9854 (5) | 0.065 (2) | |
O1W | 0.7857 (4) | 0.7369 (2) | 0.5419 (4) | 0.105 (2) | |
H3 | 0.52720 | 0.44460 | 1.05810 | 0.0900* | |
H4 | 0.58350 | 0.40040 | 1.26210 | 0.1100* | |
H8 | 0.45990 | 0.55330 | 0.44000 | 0.1010* | |
H9 | 0.45890 | 0.59940 | 0.23570 | 0.1070* | |
H13 | −0.09580 | 0.36510 | 0.49690 | 0.0650* | |
H14 | −0.23970 | 0.29840 | 0.51870 | 0.1270* | |
H1 | 0.85610 | 0.68340 | 0.64970 | 0.0820* | |
H17 | 1.02240 | 0.52240 | 0.74550 | 0.0740* | |
H18 | 0.94110 | 0.59160 | 0.59650 | 0.0760* | |
H19 | 0.84670 | 0.71810 | 0.83880 | 0.0890* | |
H20 | 0.92600 | 0.65130 | 0.99250 | 0.0770* | |
H21A | 1.04990 | 0.56110 | 1.05740 | 0.0780* | |
H21B | 1.08880 | 0.51110 | 0.96010 | 0.0780* | |
H1W | 0.740 (4) | 0.711 (3) | 0.558 (8) | 0.1260* | |
H2W | 0.776 (5) | 0.7808 (12) | 0.554 (7) | 0.1260* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.0500 (1) | 0.0602 (2) | 0.0365 (1) | −0.0088 (1) | 0.0047 (1) | −0.0030 (1) |
Cl1 | 0.229 (3) | 0.234 (3) | 0.0820 (15) | −0.063 (3) | −0.0654 (18) | 0.0601 (18) |
Cl2 | 0.1184 (17) | 0.1739 (19) | 0.0618 (11) | 0.0094 (14) | 0.0252 (11) | 0.0400 (12) |
Cl3 | 0.126 (2) | 0.192 (3) | 0.162 (2) | −0.0884 (19) | 0.0451 (19) | −0.0196 (19) |
S1 | 0.1045 (15) | 0.1461 (17) | 0.0568 (10) | −0.0560 (13) | −0.0201 (9) | 0.0278 (11) |
S2 | 0.0703 (11) | 0.1122 (14) | 0.0484 (8) | −0.0140 (9) | 0.0082 (7) | 0.0096 (9) |
S3 | 0.0799 (12) | 0.1057 (13) | 0.0733 (11) | −0.0277 (10) | 0.0111 (9) | 0.0029 (10) |
O1 | 0.075 (3) | 0.071 (2) | 0.066 (2) | −0.001 (2) | 0.007 (2) | −0.010 (2) |
O2 | 0.084 (3) | 0.071 (2) | 0.057 (2) | −0.004 (2) | 0.006 (2) | −0.016 (2) |
O3 | 0.061 (2) | 0.088 (3) | 0.048 (2) | −0.027 (2) | −0.0061 (18) | 0.009 (2) |
O4 | 0.055 (2) | 0.077 (2) | 0.052 (2) | −0.0167 (18) | 0.0035 (19) | 0.0091 (19) |
O5 | 0.052 (2) | 0.103 (3) | 0.050 (2) | −0.018 (2) | 0.0040 (19) | 0.011 (2) |
O6 | 0.052 (2) | 0.132 (3) | 0.049 (2) | −0.030 (2) | 0.0007 (18) | 0.022 (2) |
O7 | 0.054 (2) | 0.111 (3) | 0.043 (2) | −0.020 (2) | 0.0016 (18) | 0.007 (2) |
O8 | 0.061 (2) | 0.105 (3) | 0.038 (2) | −0.024 (2) | −0.0007 (18) | 0.003 (2) |
C1 | 0.055 (4) | 0.059 (3) | 0.054 (3) | −0.012 (3) | 0.005 (3) | −0.005 (3) |
C2 | 0.070 (4) | 0.056 (3) | 0.049 (3) | −0.007 (3) | −0.005 (3) | −0.005 (3) |
C3 | 0.058 (4) | 0.073 (4) | 0.085 (5) | −0.010 (3) | −0.019 (3) | 0.004 (3) |
C4 | 0.076 (5) | 0.091 (5) | 0.095 (6) | −0.002 (4) | −0.036 (4) | 0.004 (4) |
C5 | 0.122 (6) | 0.105 (5) | 0.057 (4) | −0.019 (5) | −0.029 (4) | 0.008 (4) |
C6 | 0.056 (4) | 0.089 (4) | 0.051 (3) | −0.003 (3) | 0.005 (3) | 0.004 (3) |
C7 | 0.055 (4) | 0.076 (4) | 0.058 (3) | −0.001 (3) | 0.012 (3) | 0.007 (3) |
C8 | 0.063 (4) | 0.117 (5) | 0.073 (4) | −0.001 (4) | 0.006 (3) | 0.033 (4) |
C9 | 0.062 (4) | 0.123 (6) | 0.085 (5) | −0.008 (4) | 0.023 (4) | 0.034 (4) |
C10 | 0.078 (5) | 0.099 (5) | 0.058 (4) | 0.009 (4) | 0.027 (4) | 0.014 (3) |
C11 | 0.059 (3) | 0.075 (4) | 0.038 (3) | −0.019 (3) | 0.012 (3) | −0.013 (3) |
C12 | 0.056 (3) | 0.074 (3) | 0.056 (3) | −0.017 (3) | 0.015 (3) | −0.011 (3) |
C13 | 0.033 (3) | 0.091 (4) | 0.036 (3) | −0.019 (3) | −0.004 (2) | 0.000 (3) |
C14 | 0.083 (6) | 0.153 (7) | 0.078 (5) | −0.007 (5) | −0.005 (4) | −0.012 (5) |
C15 | 0.061 (4) | 0.104 (5) | 0.105 (6) | −0.036 (4) | 0.018 (4) | −0.030 (5) |
N1 | 0.070 (3) | 0.075 (3) | 0.057 (3) | −0.001 (3) | −0.007 (2) | 0.028 (3) |
C16 | 0.054 (3) | 0.067 (3) | 0.040 (3) | −0.003 (3) | −0.001 (2) | 0.012 (3) |
C17 | 0.060 (4) | 0.078 (4) | 0.047 (3) | 0.008 (3) | 0.003 (3) | −0.001 (3) |
C18 | 0.062 (4) | 0.091 (4) | 0.037 (3) | −0.007 (3) | 0.004 (3) | 0.003 (3) |
C19 | 0.090 (5) | 0.066 (4) | 0.068 (4) | 0.011 (3) | 0.013 (4) | 0.011 (3) |
C20 | 0.082 (4) | 0.071 (4) | 0.036 (3) | 0.005 (3) | 0.001 (3) | 0.007 (3) |
C21 | 0.068 (4) | 0.075 (4) | 0.047 (3) | 0.009 (3) | −0.011 (3) | 0.012 (3) |
O1W | 0.160 (5) | 0.072 (3) | 0.069 (3) | 0.037 (3) | −0.040 (3) | −0.011 (3) |
U1—O1 | 1.749 (4) | C2—C3 | 1.362 (8) |
U1—O2 | 1.753 (4) | C3—C4 | 1.418 (11) |
U1—O3 | 2.451 (3) | C4—C5 | 1.309 (11) |
U1—O4 | 2.478 (4) | C6—C7 | 1.458 (8) |
U1—O5 | 2.467 (4) | C7—C8 | 1.341 (9) |
U1—O6 | 2.428 (4) | C8—C9 | 1.397 (10) |
U1—O7 | 2.477 (4) | C9—C10 | 1.328 (10) |
U1—O8 | 2.541 (3) | C11—C12 | 1.479 (8) |
Cl1—C5 | 1.707 (7) | C12—C13 | 1.398 (7) |
Cl2—C10 | 1.721 (7) | C13—C14 | 1.412 (9) |
Cl3—C15 | 1.702 (7) | C14—C15 | 1.325 (11) |
S1—C2 | 1.701 (6) | C3—H3 | 0.9300 |
S1—C5 | 1.714 (8) | C4—H4 | 0.9300 |
S2—C7 | 1.726 (6) | C8—H8 | 0.9300 |
S2—C10 | 1.706 (7) | C9—H9 | 0.9300 |
S3—C12 | 1.695 (6) | C13—H13 | 0.9300 |
S3—C15 | 1.698 (7) | C14—H14 | 0.9300 |
O3—C1 | 1.294 (7) | C16—C21 | 1.498 (8) |
O4—C1 | 1.253 (7) | C16—C20 | 1.387 (8) |
O5—C6 | 1.264 (7) | C16—C17 | 1.382 (8) |
O6—C6 | 1.263 (7) | C17—C18 | 1.361 (8) |
O7—C11 | 1.249 (7) | C19—C20 | 1.357 (9) |
O8—C11 | 1.242 (6) | C21—C21i | 1.546 (8) |
O1W—H2W | 0.82 (3) | C17—H17 | 0.9300 |
O1W—H1W | 0.85 (6) | C18—H18 | 0.9300 |
N1—C19 | 1.338 (8) | C19—H19 | 0.9300 |
N1—C18 | 1.313 (8) | C20—H20 | 0.9300 |
N1—H1 | 0.8600 | C21—H21B | 0.9700 |
C1—C2 | 1.460 (8) | C21—H21A | 0.9700 |
Cl3···C4ii | 3.471 (8) | O1···H21Bviii | 2.8500 |
Cl2···H3iii | 3.0800 | O1W···H1 | 1.7700 |
Cl3···H4ii | 3.0200 | O1W···H19ix | 2.6600 |
S1···O3 | 2.968 (4) | O2···H1Wiii | 2.72 (9) |
S1···O1Wiv | 3.489 (5) | O2···H19iv | 2.7700 |
S1···O2v | 3.406 (4) | O3···H2Wiv | 1.92 (3) |
S1···C19vi | 3.597 (8) | O4···H3vi | 2.6100 |
S2···C14vii | 3.667 (9) | O4···H9iii | 2.7600 |
S2···C18iii | 3.651 (7) | O4···H3 | 2.8500 |
S2···O6 | 2.925 (4) | O5···H4vi | 2.6300 |
S3···O8 | 3.008 (4) | O5···H8 | 2.8700 |
S1···H19vi | 3.2000 | O5···H8iii | 2.9000 |
S1···H2Wiv | 3.16 (7) | O6···H18iii | 2.6500 |
O1···O3 | 3.040 (5) | O7···H13 | 2.7900 |
O1···O4 | 3.009 (6) | O7···H18iii | 2.2800 |
O1···O5 | 3.039 (6) | O7···H17viii | 2.8300 |
O1···O6 | 3.043 (5) | O8···H20vi | 2.4700 |
O1···O7 | 3.017 (5) | O8···H2Wiv | 2.74 (7) |
O1···O8 | 3.120 (5) | N1···O1W | 2.625 (7) |
O1···C1 | 3.369 (7) | N1···H1W | 2.71 (7) |
O1···C6 | 3.360 (7) | C3···O4vi | 3.243 (7) |
O1···C11 | 3.401 (7) | C4···Cl3xii | 3.471 (8) |
O1···C17viii | 3.238 (7) | C4···O5vi | 3.334 (8) |
O1W···O2iii | 2.801 (6) | C11···C19iv | 3.579 (8) |
O1W···C19ix | 3.353 (8) | C14···S2vii | 3.667 (9) |
O1W···N1 | 2.625 (7) | C17···O1xiii | 3.238 (7) |
O1W···O8x | 3.225 (6) | C18···S2iii | 3.651 (7) |
O1W···S1x | 3.489 (5) | C18···O6iii | 3.116 (7) |
O1W···O3x | 2.731 (5) | C18···O7iii | 3.173 (6) |
O2···O4 | 3.050 (5) | C19···O1Wxiv | 3.353 (8) |
O2···S1xi | 3.406 (4) | C19···C11x | 3.579 (8) |
O2···O8 | 3.031 (5) | C19···S1vi | 3.597 (8) |
O2···C6 | 3.327 (7) | C20···O8vi | 3.362 (6) |
O2···C11 | 3.316 (7) | C1···H2Wiv | 2.88 (5) |
O2···O7 | 3.055 (6) | C11···H17viii | 2.9000 |
O2···O1Wiii | 2.801 (6) | C17···H21Ai | 3.0700 |
O2···O6 | 2.972 (6) | C20···H21Bi | 3.0900 |
O2···O3 | 2.956 (5) | H1···H1W | 1.9300 |
O2···C1 | 3.305 (7) | H1···H2W | 2.3000 |
O2···O5 | 3.034 (5) | H1···O1W | 1.7700 |
O3···O1 | 3.040 (5) | H1W···O2iii | 2.72 (9) |
O3···O4 | 2.193 (6) | H1W···N1 | 2.71 (7) |
O3···S1 | 2.968 (4) | H1W···H1 | 1.9300 |
O3···O2 | 2.956 (5) | H2W···H1 | 2.3000 |
O3···O1Wiv | 2.731 (5) | H2W···S1x | 3.16 (7) |
O3···O8 | 2.718 (5) | H2W···O3x | 1.92 (3) |
O4···O5 | 2.909 (5) | H2W···C1x | 2.88 (5) |
O4···C3vi | 3.243 (7) | H2W···O8x | 2.74 (6) |
O4···O3 | 2.193 (6) | H3···O4 | 2.8500 |
O4···O2 | 3.050 (5) | H3···O4vi | 2.6100 |
O4···O1 | 3.009 (6) | H3···H3vi | 2.4600 |
O5···O4 | 2.909 (5) | H3···Cl2iii | 3.0800 |
O5···O6 | 2.179 (6) | H4···Cl3xii | 3.0200 |
O5···O2 | 3.034 (5) | H4···O5vi | 2.6300 |
O5···O1 | 3.039 (6) | H8···O5 | 2.8700 |
O5···C4vi | 3.334 (8) | H8···O5iii | 2.9000 |
O6···O7 | 2.641 (6) | H8···H8iii | 2.5500 |
O6···C18iii | 3.116 (7) | H9···O4iii | 2.7600 |
O6···O1 | 3.043 (5) | H13···O7 | 2.7900 |
O6···O5 | 2.179 (6) | H17···O7xiii | 2.8300 |
O6···O2 | 2.972 (6) | H17···C11xiii | 2.9000 |
O6···S2 | 2.925 (4) | H17···H21B | 2.4700 |
O7···O2 | 3.055 (6) | H17···O1xiii | 2.5700 |
O7···C18iii | 3.173 (6) | H18···O6iii | 2.6500 |
O7···O8 | 2.171 (5) | H18···O7iii | 2.2800 |
O7···O1 | 3.017 (5) | H19···S1vi | 3.2000 |
O7···O6 | 2.641 (6) | H19···O1Wxiv | 2.6600 |
O8···O1Wiv | 3.225 (6) | H19···O2x | 2.7700 |
O8···O3 | 2.718 (5) | H20···O8vi | 2.4700 |
O8···C20vi | 3.362 (6) | H20···H21A | 2.4700 |
O8···O1 | 3.120 (5) | H21A···H20 | 2.4700 |
O8···O7 | 2.171 (5) | H21A···C17i | 3.0700 |
O8···S3 | 3.008 (4) | H21B···H17 | 2.4700 |
O8···O2 | 3.031 (5) | H21B···C20i | 3.0900 |
O1···H17viii | 2.5700 | H21B···O1xiii | 2.8500 |
O1—U1—O2 | 178.84 (16) | O5—C6—O6 | 119.2 (5) |
O1—U1—O3 | 91.19 (14) | S2—C7—C8 | 110.6 (5) |
O1—U1—O4 | 89.02 (16) | C6—C7—C8 | 130.6 (6) |
O1—U1—O5 | 90.62 (16) | S2—C7—C6 | 118.8 (4) |
O1—U1—O6 | 92.06 (16) | C7—C8—C9 | 113.9 (6) |
O1—U1—O7 | 89.40 (16) | C8—C9—C10 | 112.2 (7) |
O1—U1—O8 | 91.42 (16) | Cl2—C10—S2 | 118.7 (4) |
O2—U1—O3 | 87.70 (14) | Cl2—C10—C9 | 128.5 (6) |
O2—U1—O4 | 90.59 (16) | S2—C10—C9 | 112.8 (5) |
O2—U1—O5 | 90.30 (16) | O7—C11—O8 | 121.3 (5) |
O2—U1—O6 | 89.07 (16) | O7—C11—C12 | 118.4 (5) |
O2—U1—O7 | 90.79 (16) | O8—C11—C12 | 120.4 (5) |
O2—U1—O8 | 87.80 (16) | S3—C12—C13 | 110.9 (4) |
O3—U1—O4 | 52.84 (14) | C11—C12—C13 | 127.9 (5) |
O3—U1—O5 | 124.82 (13) | S3—C12—C11 | 121.1 (4) |
O3—U1—O6 | 176.02 (15) | C12—C13—C14 | 111.7 (5) |
O3—U1—O7 | 117.21 (13) | C13—C14—C15 | 112.1 (6) |
O3—U1—O8 | 65.96 (12) | Cl3—C15—C14 | 124.8 (6) |
O4—U1—O5 | 72.06 (13) | S3—C15—C14 | 113.8 (5) |
O4—U1—O6 | 124.91 (14) | Cl3—C15—S3 | 121.4 (5) |
O4—U1—O7 | 169.88 (13) | C4—C3—H3 | 123.00 |
O4—U1—O8 | 118.79 (12) | C2—C3—H3 | 123.00 |
O5—U1—O6 | 52.85 (14) | C3—C4—H4 | 124.00 |
O5—U1—O7 | 117.96 (12) | C5—C4—H4 | 124.00 |
O5—U1—O8 | 168.98 (11) | C7—C8—H8 | 123.00 |
O6—U1—O7 | 65.14 (13) | C9—C8—H8 | 123.00 |
O6—U1—O8 | 116.24 (13) | C10—C9—H9 | 124.00 |
O7—U1—O8 | 51.26 (11) | C8—C9—H9 | 124.00 |
C2—S1—C5 | 91.2 (3) | C12—C13—H13 | 124.00 |
C7—S2—C10 | 90.6 (3) | C14—C13—H13 | 124.00 |
C12—S3—C15 | 91.5 (3) | C13—C14—H14 | 124.00 |
U1—O3—C1 | 94.2 (3) | C15—C14—H14 | 124.00 |
U1—O4—C1 | 94.0 (3) | C17—C16—C20 | 117.2 (5) |
U1—O5—C6 | 93.0 (3) | C20—C16—C21 | 121.3 (5) |
U1—O6—C6 | 94.9 (3) | C17—C16—C21 | 121.3 (5) |
U1—O7—C11 | 95.1 (3) | C16—C17—C18 | 120.8 (5) |
U1—O8—C11 | 92.2 (3) | N1—C18—C17 | 119.6 (5) |
H1W—O1W—H2W | 110 (7) | N1—C19—C20 | 119.6 (6) |
C18—N1—C19 | 122.5 (5) | C16—C20—C19 | 120.3 (5) |
C18—N1—H1 | 119.00 | C16—C21—C21i | 109.9 (5) |
C19—N1—H1 | 119.00 | C18—C17—H17 | 120.00 |
O3—C1—O4 | 118.9 (5) | C16—C17—H17 | 120.00 |
O3—C1—C2 | 118.8 (5) | N1—C18—H18 | 120.00 |
O4—C1—C2 | 122.3 (5) | C17—C18—H18 | 120.00 |
S1—C2—C3 | 110.4 (5) | N1—C19—H19 | 120.00 |
C1—C2—C3 | 129.1 (6) | C20—C19—H19 | 120.00 |
S1—C2—C1 | 120.5 (4) | C19—C20—H20 | 120.00 |
C2—C3—C4 | 113.6 (6) | C16—C20—H20 | 120.00 |
C3—C4—C5 | 111.4 (7) | C16—C21—H21A | 110.00 |
Cl1—C5—S1 | 119.6 (5) | C16—C21—H21B | 110.00 |
S1—C5—C4 | 113.5 (6) | C21i—C21—H21A | 110.00 |
Cl1—C5—C4 | 126.9 (7) | C21i—C21—H21B | 110.00 |
O5—C6—C7 | 122.1 (5) | H21A—C21—H21B | 108.00 |
O6—C6—C7 | 118.8 (5) | ||
O1—U1—O3—C1 | −89.6 (3) | U1—O3—C1—C2 | −177.9 (4) |
O2—U1—O3—C1 | 90.8 (3) | U1—O4—C1—O3 | −3.0 (5) |
O4—U1—O3—C1 | −1.7 (3) | U1—O4—C1—C2 | 178.0 (5) |
O5—U1—O3—C1 | 2.0 (4) | U1—O5—C6—O6 | −1.0 (5) |
O7—U1—O3—C1 | −179.5 (3) | U1—O5—C6—C7 | 179.3 (5) |
O8—U1—O3—C1 | 179.4 (3) | U1—O6—C6—O5 | 1.0 (6) |
O1—U1—O4—C1 | 94.0 (3) | U1—O6—C6—C7 | −179.3 (4) |
O2—U1—O4—C1 | −84.9 (3) | U1—O7—C11—O8 | 4.5 (6) |
O3—U1—O4—C1 | 1.8 (3) | U1—O7—C11—C12 | −176.1 (4) |
O5—U1—O4—C1 | −175.0 (3) | U1—O8—C11—O7 | −4.4 (5) |
O6—U1—O4—C1 | −174.2 (3) | U1—O8—C11—C12 | 176.2 (5) |
O8—U1—O4—C1 | 2.9 (3) | C18—N1—C19—C20 | −1.3 (9) |
O1—U1—O5—C6 | −91.5 (3) | C19—N1—C18—C17 | 1.3 (9) |
O2—U1—O5—C6 | 89.2 (3) | O3—C1—C2—C3 | −172.8 (6) |
O3—U1—O5—C6 | 176.6 (3) | O3—C1—C2—S1 | 5.4 (7) |
O4—U1—O5—C6 | 179.7 (3) | O4—C1—C2—S1 | −175.7 (4) |
O6—U1—O5—C6 | 0.6 (3) | O4—C1—C2—C3 | 6.2 (9) |
O7—U1—O5—C6 | −1.9 (3) | S1—C2—C3—C4 | 1.8 (7) |
O1—U1—O6—C6 | 88.7 (4) | C1—C2—C3—C4 | −180.0 (6) |
O2—U1—O6—C6 | −91.7 (4) | C2—C3—C4—C5 | −0.2 (9) |
O4—U1—O6—C6 | −1.6 (4) | C3—C4—C5—S1 | −1.5 (8) |
O5—U1—O6—C6 | −0.6 (3) | C3—C4—C5—Cl1 | 180.0 (6) |
O7—U1—O6—C6 | 177.0 (4) | O6—C6—C7—S2 | 2.2 (7) |
O8—U1—O6—C6 | −178.7 (3) | O5—C6—C7—S2 | −178.1 (4) |
O1—U1—O7—C11 | −94.7 (3) | O5—C6—C7—C8 | 1.1 (10) |
O2—U1—O7—C11 | 84.1 (3) | O6—C6—C7—C8 | −178.6 (7) |
O3—U1—O7—C11 | −3.7 (4) | S2—C7—C8—C9 | −0.3 (8) |
O5—U1—O7—C11 | 174.9 (3) | C6—C7—C8—C9 | −179.6 (6) |
O6—U1—O7—C11 | 172.8 (4) | C7—C8—C9—C10 | 0.3 (9) |
O8—U1—O7—C11 | −2.4 (3) | C8—C9—C10—Cl2 | 179.0 (5) |
O1—U1—O8—C11 | 90.5 (3) | C8—C9—C10—S2 | −0.1 (8) |
O2—U1—O8—C11 | −90.4 (3) | O7—C11—C12—C13 | −0.2 (9) |
O3—U1—O8—C11 | −178.8 (3) | O7—C11—C12—S3 | 177.4 (4) |
O4—U1—O8—C11 | −179.8 (3) | O8—C11—C12—C13 | 179.2 (5) |
O6—U1—O8—C11 | −2.5 (4) | O8—C11—C12—S3 | −3.1 (8) |
O7—U1—O8—C11 | 2.4 (3) | C11—C12—C13—C14 | 178.6 (6) |
C5—S1—C2—C1 | 179.4 (5) | S3—C12—C13—C14 | 0.8 (7) |
C5—S1—C2—C3 | −2.2 (5) | C12—C13—C14—C15 | −0.8 (9) |
C2—S1—C5—Cl1 | −179.2 (5) | C13—C14—C15—S3 | 0.4 (9) |
C2—S1—C5—C4 | 2.1 (6) | C13—C14—C15—Cl3 | −178.1 (5) |
C10—S2—C7—C6 | 179.6 (5) | C20—C16—C17—C18 | 0.9 (9) |
C10—S2—C7—C8 | 0.2 (5) | C21—C16—C17—C18 | 175.6 (6) |
C7—S2—C10—Cl2 | −179.3 (4) | C17—C16—C20—C19 | −0.9 (9) |
C7—S2—C10—C9 | −0.1 (5) | C21—C16—C20—C19 | −175.6 (6) |
C15—S3—C12—C11 | −178.5 (5) | C17—C16—C21—C21i | −86.5 (6) |
C15—S3—C12—C13 | −0.5 (5) | C20—C16—C21—C21i | 88.0 (6) |
C12—S3—C15—Cl3 | 178.6 (5) | C16—C17—C18—N1 | −1.1 (9) |
C12—S3—C15—C14 | 0.1 (6) | N1—C19—C20—C16 | 1.1 (9) |
U1—O3—C1—O4 | 3.1 (5) | C16—C21—C21i—C16i | −180.0 (5) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x−1, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y−1/2, −z+3/2; (v) x, −y+1/2, z+1/2; (vi) −x+1, −y+1, −z+2; (vii) −x, −y+1, −z+1; (viii) x−1, y, z; (ix) x, −y+3/2, z−1/2; (x) −x+1, y+1/2, −z+3/2; (xi) x, −y+1/2, z−1/2; (xii) x+1, −y+1/2, z+1/2; (xiii) x+1, y, z; (xiv) x, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.86 | 1.77 | 2.625 (7) | 175 |
O1W—H2W···O3x | 0.82 (3) | 1.92 (3) | 2.731 (5) | 171 (8) |
C17—H17···O1xiii | 0.93 | 2.57 | 3.238 (7) | 129 |
C18—H18···O7iii | 0.93 | 2.28 | 3.173 (6) | 161 |
C20—H20···O8vi | 0.93 | 2.47 | 3.362 (6) | 160 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (vi) −x+1, −y+1, −z+2; (x) −x+1, y+1/2, −z+3/2; (xiii) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C10H10N2)0.5[U(C5H2ClO2S)3O2]·H2O | (C12H14N2)0.5[U(C5H2ClO2S)3O2]·H2O |
Mr | 851.90 | 865.92 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 14.1630 (5), 17.5777 (6), 11.2915 (4) | 14.5189 (2), 18.1169 (3), 11.1399 (2) |
β (°) | 104.595 (2) | 97.123 (1) |
V (Å3) | 2720.34 (16) | 2907.60 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 6.54 | 6.12 |
Crystal size (mm) | 0.08 × 0.06 × 0.05 | 0.10 × 0.08 × 0.05 |
Data collection | ||
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.577, 0.698 | 0.531, 0.713 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33776, 8824, 5253 | 32147, 7244, 4711 |
Rint | 0.042 | 0.049 |
(sin θ/λ)max (Å−1) | 0.729 | 0.668 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.087, 0.99 | 0.040, 0.098, 1.01 |
No. of reflections | 8747 | 7244 |
No. of parameters | 313 | 328 |
No. of restraints | 3 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.16, −1.03 | 1.32, −0.68 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.86 | 1.83 | 2.683 (6) | 169 |
O1W—H1W···O6i | 0.81 (4) | 2.12 (4) | 2.868 (5) | 154 (5) |
O1W—H1W···O7i | 0.81 (4) | 2.33 (5) | 2.951 (5) | 134 (5) |
O1W—H2W···O1 | 0.82 (5) | 2.10 (5) | 2.903 (5) | 166 (5) |
C9—H9···O4ii | 0.93 | 2.52 | 3.318 (6) | 144 |
C17—H17···O7iii | 0.93 | 2.48 | 3.379 (6) | 162 |
C18—H18···O8 | 0.93 | 2.38 | 3.208 (6) | 147 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+2; (iii) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.86 | 1.77 | 2.625 (7) | 175 |
O1W—H2W···O3i | 0.82 (3) | 1.92 (3) | 2.731 (5) | 171 (8) |
C17—H17···O1ii | 0.93 | 2.57 | 3.238 (7) | 129 |
C18—H18···O7iii | 0.93 | 2.28 | 3.173 (6) | 161 |
C20—H20···O8iv | 0.93 | 2.47 | 3.362 (6) | 160 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z+2. |
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Uranium chelation has been an ongoing area of study (Szigethy & Raymond, 2009) in large part due to the metal's role as the feedstock material for most nuclear power sources. Simple ligands that can effectively chelate and remove actinides from the environment or in vivo are of interest in this context. Systematic pairing of aromatic pyridyl-functionalized linkers with carboxylic and polycarboxylic acids of varying lengths and their influence on the three-dimensional architecture of uranyl-containing polymers have been extensively studied (Borkowski & Cahill, 2006). The uranyl ion (UO22+), a particularly stable form of oxidized uranium that is involved in nuclear fuel processing, has a high affinity for oxygen donors and a wide variety of resulting architectures are obtained in so-called uranyl–organic frameworks (UOFs) (Thuery & Masci, 2008). The UO22+ cation maintains its linearity to within a couple of degrees in all of its coordination complexes, relegating coordinative variation to a square, pentagonal or hexagonal equatorial plane of coordinated carboxylate groups perpendicular to the O═U═O unit (Frisch & Cahill, 2005; Szigethy & Raymond, 2009). The combination of 5-chlorothiophene-2-carboxylic acid, a bipyridyl species and UO22+ has resulted in the synthesis of two new compounds containing the same uranyl complex with different organic linker cations, hemi(4,4'-bipyridinium) tris(5-chlorothiophene-2-carboxylato)dioxidouranate(VI) monohydrate, (C10H10N2)0.5[U(C5H2ClOO2S)3O2].H2O, (I), and hemi[4,4'-(ethane-1,2-diyl)dipyridinium] tris(5-chlorothiophene-2-carboxylato)dioxidouranate(VI)monohydrate, (C12H14N2)0.5[U(C5H2ClO2S)3O2].H2O, (II).
Both (I) and (II) contain the same anionic coordination complex. The coordination of the single crystallographically unique U site consists of a central near-linear UO22+ cation [O═U═O angle 178.81 (17)°] with six oxygen atoms from three bidentate 5-chlorothiophene-2-carboxylate ions in the equatorial plane, leading to an overall hexagonal bipyramidal coordination (Fig. 1). The short U—O axial bond lengths [1.756 (3) and 1.754 (3) Å] in (I) are in good agreement with the reported average uranyl bond length of 1.759 (4) Å (Thuery & Masci, 2008; Sasikumar & Muthiah, 2010; Thuéry, 2008; Masci & Thuéry, 2008). The U—O equatorial bond distances [2.437 (3)–2.515 (3) Å] are longer than the axial distances and the O—U—O bite angles of the bidentate carboxylate groups in the equatorial plane range from 51.87 (11) to 53.22 (10)°, as compared to the ideal 60° for a regular hexagonal arrangement. The bipyridinium cation is relatively flat with a C20—C16—C16a—C17a torsion angle of 1.6 (7)° [symmetry code: (a) -x, 1 - y, -z ].
In (I) two anionic [UO2X3]- units are linked by a protonated 4,4'-bipyridinium cation (located on a centre of inversion) as well as water molecules via N—H···O and O—H···O hydrogen bonds (Fig. 2). The water molecule acts as a hydrogen-bond acceptor from the protonated N atom of 4,4'-bipyridinium (O1W···H1—N1) while one H atom is involved in a bifurcated hydrogen bond with O atoms from two different coordinated carboxylates (O1W—H1W···O6i and O1W—H1W···O7i) [symmetry code: (i) x, -y + 1/2, z - 1/2] and the other is hydrogen bonded to a uranyl oxygen (O1W—H2W···O1) (Fig. 2). The π–π stacking is observed between nearly parallel coordinated 5-chlorothiophene rings of adjacent complexes (S1, C2, C3, C4, C5) and (S2, C7, C8, C9, C10)b [symmetry code: (b) x, y, -1 + z] with a centroid–centroid distance of 3.841 (3) Å. Intermolecular hydrogen bonds are found in between C9—H9 of an anionic unit and O4ii [symmetry code: (ii) -x + 1, -y + 1, -z + 2] of the next anionic unit which leads to the formation of a ring. The ring is formed by 16 atoms made up of U1, O5, C6, C7, C8, C9, H9, O4ii, U1ii, O5ii, C6ii, C7ii, C8ii, C9ii, H9ii and O4.
In (II), the same anionic uranyl complexes are paired with protonated 1,2-bis(4-pyridinium)ethane cations that are also situated on inversion centres with a non-coordinated water molecule present as well (Fig. 3). The geometric parameters in the complex are essentially the same as those in (I). As in (I), the metal complexes are linked by N1—H1···O1W and O1W—H2W···O3i hydrogen bonds [symmetry code: (i) -x + 1, y + 1/2, -z + 3/2] involving the protonated 1,2-bis(4-pyridinium)ethane cation, water molecules and carboxylate O atoms (Fig. 4). Unlike the case in (I), only one of the water H atoms is involved in a hydrogen bond in (II). C—H···O interactions [C18—H18···O7iii and C20—H20···O8iv; symmetry codes: (iii) -x + 1, -y + 1, -z + 1 and (iv) -x + 1, -y + 1, -z + 2] connect the bipyridinium cations and the anionic centres. The oxo ion O1ii [symmetry code: (ii) x + 1, y, z] is hydrogen bonded to the bipyridine moiety via C17 and H17. As in (I), π–π stacking interactions occur between nearly parallel 5-chlorothiophene rings (S1, C2, C3, C4, C5) and (S2, C7, C8, C9, C10)c [symmetry code: (c) x, y, 1 + z] with a centroid–centroid distance of 3.928 (4) Å.
We have crystallized the tris(5-chlorothiophene-2-carboxylato)uranyl(VI) complex using two different bipyridinium cations. Although there are reports of several similar [(UO22+)(RCOO-)3] complexes showing the puckered hexagonal bipyramidal geometry (Borkowski & Cahill, 2006), this is the first pair of uranium complexes with the 5-chlorothiophene-2-carboxylate ligand. The similarity of the organic cations results in quite similar crystal packing and intermolecular interactions. In both salts, there are alternating layers of anionic complexes and cations that are parallel to the a–c plane and stack along the b axis. The bipyridinium cation of (I) contains two pyridine rings connected directly by a C—C bond, while in the 1,2-bis(4-pyridinium)ethane cation in (II) the pyridine rings are connected by a small alkyl chain which extends the distance between the rings. This leads to small elongations in the a and b unit-cell axes, which is important from a crystal engineering point of view.