Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807061016/is2245sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807061016/is2245Isup2.hkl |
CCDC reference: 672756
The title compound (I) was obtained unintentionally as the product of an attempted synthesis of uranyl methanesulfonate with guanidinium cation in the outer sphere. 50 mg (0.175 mmol) of uranium oxide UO3 was dissolved in 0.7 ml of 0.5 M methanesulfonic acid. Then 0.175 ml of 0.5 M solution of diguanidinium carbonte neutralized by 0.35 ml of 0.5 M methanesulfonic acid was added. The guanidinium:U molar ratio in the resulting mixture is 1:1. The single crystals were obtained after 2 days of isothermal (at ~22 °C) evaporation of the solution.
NIR/Vis and IR spectra were measured using Shimadzu UV3100 and Specord M80 spectrometers, respectively. The vibration frequencies of functional groups SO3 and CS are slightly shifted to higher energies as compared to the free methanesulfonic acid. The stretching vibrations of UO22+ group are observed in typical for uranyl compounds region. The vibration frequencies (cm-1) and their assignments: 3340, 3236m - ν(HOH); 1236 s, 1138 s - νas(SO3); 3028w - νas(CH3); 1098 s, 1052 s - νs(SO3); 2944w - νs(CH3), 980vw - ρ(CH3); 1644m- d(H2O); 942m, 915s h - ν (UO22+); 1422m- d(CH3); 790m - ν(CS); 1332w- ds(CH3); 560m, 528w- d(SO3).
H atoms of water molecule were located in a difference map and refined isotropically, with distance restraints of O–H = 0.82 (2) Å. Other H atoms were treated as riding atoms, with distances C–H = 0.98 (CH3), and with Uiso(H) = 1.2Ueq(C). The highest residual electron density peak and the deepest hole are located 0.67 and 0.45 Å, respectively, from atom U1.
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: APEX2 (Bruker, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[U(CH3O3S)2O2(H2O)] | F(000) = 864 |
Mr = 478.23 | Dx = 3.310 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7994 reflections |
a = 11.2613 (4) Å | θ = 2.4–42.7° |
b = 7.9178 (3) Å | µ = 17.37 mm−1 |
c = 10.9061 (4) Å | T = 100 K |
β = 99.261 (1)° | Prism, yellow |
V = 959.76 (6) Å3 | 0.20 × 0.19 × 0.16 mm |
Z = 4 |
Bruker Kappa APEXII area-detector diffractometer | 4958 independent reflections |
Radiation source: fine-focus sealed tube | 4559 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 37.5°, θmin = 3.2° |
Absorption correction: numerical (APEX2; Bruker, 2006) | h = −19→15 |
Tmin = 0.039, Tmax = 0.062 | k = −8→13 |
10118 measured reflections | l = −18→18 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.029P)2 + 1.1P] where P = (Fo2 + 2Fc2)/3 |
4958 reflections | (Δ/σ)max = 0.001 |
135 parameters | Δρmax = 3.27 e Å−3 |
2 restraints | Δρmin = −3.39 e Å−3 |
[U(CH3O3S)2O2(H2O)] | V = 959.76 (6) Å3 |
Mr = 478.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.2613 (4) Å | µ = 17.37 mm−1 |
b = 7.9178 (3) Å | T = 100 K |
c = 10.9061 (4) Å | 0.20 × 0.19 × 0.16 mm |
β = 99.261 (1)° |
Bruker Kappa APEXII area-detector diffractometer | 4958 independent reflections |
Absorption correction: numerical (APEX2; Bruker, 2006) | 4559 reflections with I > 2σ(I) |
Tmin = 0.039, Tmax = 0.062 | Rint = 0.018 |
10118 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 2 restraints |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 3.27 e Å−3 |
4958 reflections | Δρmin = −3.39 e Å−3 |
135 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 | ||
U1 | 0.752778 (6) | 0.121075 (10) | 0.011327 (7) | 0.00498 (3) | |
S2 | 0.94159 (4) | −0.25209 (7) | 0.04481 (5) | 0.00625 (8) | |
S1 | 0.43671 (4) | 0.23068 (7) | −0.10448 (5) | 0.00632 (8) | |
O5 | 0.54270 (14) | 0.1816 (2) | −0.01433 (17) | 0.0090 (3) | |
O6 | 0.90791 (14) | −0.0786 (2) | 0.07588 (19) | 0.0093 (3) | |
O4 | 0.33894 (16) | 0.1091 (3) | −0.1009 (2) | 0.0164 (4) | |
O7 | 0.86707 (16) | −0.3194 (3) | −0.06341 (19) | 0.0128 (3) | |
O2 | 0.77899 (15) | 0.2103 (2) | 0.16107 (19) | 0.0118 (3) | |
O3 | 0.39990 (17) | 0.4020 (2) | −0.0874 (2) | 0.0133 (3) | |
O1 | 0.72636 (16) | 0.0298 (2) | −0.13744 (18) | 0.0109 (3) | |
O8 | 1.07021 (15) | −0.2558 (2) | 0.0337 (2) | 0.0146 (4) | |
C1 | 0.4747 (2) | 0.2170 (3) | −0.2535 (2) | 0.0118 (4) | |
H2 | 0.5419 | 0.2934 | −0.2597 | 0.014* | |
H1 | 0.4052 | 0.2490 | −0.3151 | 0.014* | |
H3 | 0.4983 | 0.1008 | −0.2691 | 0.014* | |
C2 | 0.9270 (2) | −0.3769 (3) | 0.1739 (3) | 0.0116 (4) | |
H6 | 0.8598 | −0.3353 | 0.2123 | 0.014* | |
H4 | 1.0015 | −0.3712 | 0.2342 | 0.014* | |
H5 | 0.9117 | −0.4942 | 0.1474 | 0.014* | |
O9 | 0.70849 (15) | 0.4086 (2) | −0.0706 (2) | 0.0099 (3) | |
H8 | 0.666 (3) | 0.467 (5) | −0.036 (4) | 0.024 (11)* | |
H7 | 0.759 (4) | 0.465 (7) | −0.095 (6) | 0.029 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.00484 (3) | 0.00440 (4) | 0.00563 (4) | −0.00024 (2) | 0.00061 (2) | −0.00022 (2) |
S2 | 0.00544 (16) | 0.0047 (2) | 0.0088 (2) | −0.00047 (15) | 0.00190 (15) | 0.00041 (16) |
S1 | 0.00586 (17) | 0.0063 (2) | 0.0068 (2) | 0.00020 (15) | 0.00102 (15) | 0.00188 (16) |
O5 | 0.0060 (5) | 0.0124 (8) | 0.0081 (7) | 0.0013 (5) | 0.0001 (5) | 0.0020 (6) |
O6 | 0.0087 (6) | 0.0060 (7) | 0.0127 (8) | 0.0014 (5) | 0.0006 (5) | −0.0001 (6) |
O4 | 0.0082 (6) | 0.0165 (9) | 0.0232 (11) | −0.0041 (6) | −0.0015 (6) | 0.0119 (7) |
O7 | 0.0174 (7) | 0.0103 (8) | 0.0100 (8) | −0.0035 (6) | 0.0001 (6) | −0.0004 (6) |
O2 | 0.0123 (7) | 0.0127 (8) | 0.0096 (8) | 0.0020 (6) | −0.0005 (6) | −0.0022 (6) |
O3 | 0.0174 (8) | 0.0102 (8) | 0.0125 (9) | 0.0057 (6) | 0.0034 (6) | −0.0011 (6) |
O1 | 0.0149 (7) | 0.0083 (7) | 0.0089 (8) | 0.0010 (5) | 0.0000 (6) | −0.0010 (6) |
O8 | 0.0072 (6) | 0.0082 (8) | 0.0301 (12) | 0.0019 (5) | 0.0083 (6) | 0.0045 (7) |
C1 | 0.0153 (9) | 0.0131 (10) | 0.0072 (9) | 0.0020 (7) | 0.0024 (7) | 0.0001 (8) |
C2 | 0.0142 (9) | 0.0096 (10) | 0.0110 (10) | 0.0004 (7) | 0.0023 (7) | 0.0030 (8) |
O9 | 0.0099 (6) | 0.0059 (7) | 0.0144 (9) | 0.0000 (5) | 0.0036 (6) | 0.0006 (6) |
U1—O1 | 1.7570 (19) | S1—O4 | 1.4677 (19) |
U1—O2 | 1.760 (2) | S1—O5 | 1.4712 (18) |
U1—O6 | 2.3772 (17) | S1—C1 | 1.749 (3) |
U1—O8i | 2.3804 (17) | C1—H2 | 0.9800 |
U1—O4ii | 2.3806 (19) | C1—H1 | 0.9800 |
U1—O5 | 2.3857 (15) | C1—H3 | 0.9800 |
U1—O9 | 2.4670 (19) | C2—H6 | 0.9800 |
S2—O7 | 1.436 (2) | C2—H4 | 0.9800 |
S2—O8 | 1.4733 (16) | C2—H5 | 0.9800 |
S2—O6 | 1.4789 (19) | O9—H8 | 0.80 (4) |
S2—C2 | 1.749 (3) | O9—H7 | 0.80 (5) |
S1—O3 | 1.439 (2) | ||
O1—U1—O2 | 179.37 (9) | O6—S2—C2 | 106.25 (12) |
O1—U1—O6 | 90.41 (8) | O3—S1—O4 | 112.44 (12) |
O2—U1—O6 | 89.23 (8) | O3—S1—O5 | 112.45 (12) |
O1—U1—O8i | 90.97 (8) | O4—S1—O5 | 109.90 (11) |
O2—U1—O8i | 89.45 (8) | O3—S1—C1 | 107.32 (13) |
O6—U1—O8i | 76.06 (6) | O4—S1—C1 | 106.30 (14) |
O1—U1—O4ii | 92.52 (9) | O5—S1—C1 | 108.12 (11) |
O2—U1—O4ii | 86.88 (9) | S1—O5—U1 | 144.49 (11) |
O6—U1—O4ii | 73.50 (6) | S2—O6—U1 | 138.87 (11) |
O8i—U1—O4ii | 149.38 (6) | S1—O4—U1ii | 152.86 (13) |
O1—U1—O5 | 87.53 (7) | S2—O8—U1i | 151.07 (12) |
O2—U1—O5 | 92.48 (7) | S1—C1—H2 | 109.5 |
O6—U1—O5 | 146.71 (6) | S1—C1—H1 | 109.5 |
O8i—U1—O5 | 137.16 (6) | H2—C1—H1 | 109.5 |
O4ii—U1—O5 | 73.41 (6) | S1—C1—H3 | 109.5 |
O1—U1—O9 | 92.91 (8) | H2—C1—H3 | 109.5 |
O2—U1—O9 | 87.67 (8) | H1—C1—H3 | 109.5 |
O6—U1—O9 | 144.79 (6) | S2—C2—H6 | 109.5 |
O8i—U1—O9 | 68.85 (6) | S2—C2—H4 | 109.5 |
O4ii—U1—O9 | 141.19 (6) | H6—C2—H4 | 109.5 |
O5—U1—O9 | 68.49 (6) | S2—C2—H5 | 109.5 |
O7—S2—O8 | 112.15 (13) | H6—C2—H5 | 109.5 |
O7—S2—O6 | 113.29 (11) | H4—C2—H5 | 109.5 |
O8—S2—O6 | 109.22 (10) | U1—O9—H8 | 118 (3) |
O7—S2—C2 | 109.49 (12) | U1—O9—H7 | 121 (5) |
O8—S2—C2 | 106.03 (12) | H8—O9—H7 | 110 (6) |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H8···O3iii | 0.80 (4) | 1.94 (2) | 2.717 (3) | 164 (5) |
O9—H7···O7iv | 0.80 (5) | 2.09 (4) | 2.791 (3) | 145 (7) |
Symmetry codes: (iii) −x+1, −y+1, −z; (iv) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [U(CH3O3S)2O2(H2O)] |
Mr | 478.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 11.2613 (4), 7.9178 (3), 10.9061 (4) |
β (°) | 99.261 (1) |
V (Å3) | 959.76 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 17.37 |
Crystal size (mm) | 0.20 × 0.19 × 0.16 |
Data collection | |
Diffractometer | Bruker Kappa APEXII area-detector diffractometer |
Absorption correction | Numerical (APEX2; Bruker, 2006) |
Tmin, Tmax | 0.039, 0.062 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10118, 4958, 4559 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.856 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.054, 1.04 |
No. of reflections | 4958 |
No. of parameters | 135 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 3.27, −3.39 |
Computer programs: APEX2 (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).
U1—O1 | 1.7570 (19) | U1—O4ii | 2.3806 (19) |
U1—O2 | 1.760 (2) | U1—O5 | 2.3857 (15) |
U1—O6 | 2.3772 (17) | U1—O9 | 2.4670 (19) |
U1—O8i | 2.3804 (17) | ||
O1—U1—O2 | 179.37 (9) |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H8···O3iii | 0.80 (4) | 1.94 (2) | 2.717 (3) | 164 (5) |
O9—H7···O7iv | 0.80 (5) | 2.09 (4) | 2.791 (3) | 145 (7) |
Symmetry codes: (iii) −x+1, −y+1, −z; (iv) x, y+1, z. |
The structure of the title compound, (I), is shown in Fig. 1. The uranyl group is near linear and symmetrical. Coordination polyhedron of uranium atom is pentagonal bipyramide. Its equatorial plane is formed by oxygen atoms of one water molecule and four different methanesulfonate anions. The equatorial U—O distances are equal to 2.3772 (17)–2.3857 (15) and 2.4671 (18) Å for oxygen atoms of CH3SO3 anions and water molecule, respectively. Methanesulfonate anions function as bidentate bridging ligands linking adjacent uranium coordination polyhedra into infinite chains parallel to [100] (Figs. 2 and 3). In contrast to the compound (I), the corresponding structure of the known orthorhombic polymorph (II) contains infinite [(UO2)(CH3SO3)2(H2O)] layers (Fig. 4; Wilson, 1978).