Download citation
Download citation
link to html
The monoclinic (space group P21/c) title compound, [UO2(CH3O3S)2(H2O)]n, is a polymorphic modification of the known ortho­rhom­bic (space group Pbcn) variant of this stoichiometry [Wilson (1978). Acta Cryst. B34, 2302–2303]. The crystal structure consists of infinite [UO2(CH3SO3)2(H2O)] chains along the a axis. The coordination polyhedron of the U atom is a penta­gonal bipyramid, whose equatorial plane consists of the O atoms of four methane­sulfonate anions and one water mol­ecule. The axial positions are occupied by O atoms of a nearly linear and symmetrical uranyl group. The methane­sulfonate anions function as bidentate bridging ligands. The crystal structure involves intermolecular O—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807061016/is2245sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807061016/is2245Isup2.hkl
Contains datablock I

CCDC reference: 672756

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](S-C) = 0.003 Å
  • R factor = 0.022
  • wR factor = 0.054
  • Data-to-parameter ratio = 36.7

checkCIF/PLATON results

No syntax errors found



Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

In contrast to the title compound, the corresponding structure of the known orthorhombic polymorph contains infinite [(UO2)(CH3SO3)2(H2O)] layers (Wilson, 1978).

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms [symmetry codes: (i) -x + 2, -y, -z; (ii) -x + 1, -y, -z].
[Figure 2] Fig. 2. Polyhedral representation of the infinite chains parallel to [100] in the structure of (I). H atoms have been omitted.
[Figure 3] Fig. 3. The packing of infinite chain in the structure of (I), viewed down the a axis. H atoms have been omitted.
[Figure 4] Fig. 4. Polyhedral representation of the infinite sheets in the structure of (II). H atoms have been omitted.
catena-poly[[aquadioxidouranium(VI)]bis(µ-methanesulfonato-κ2O:O')] top
Crystal data top
[U(CH3O3S)2O2(H2O)]F(000) = 864
Mr = 478.23Dx = 3.310 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7994 reflections
a = 11.2613 (4) Åθ = 2.4–42.7°
b = 7.9178 (3) ŵ = 17.37 mm1
c = 10.9061 (4) ÅT = 100 K
β = 99.261 (1)°Prism, yellow
V = 959.76 (6) Å30.20 × 0.19 × 0.16 mm
Z = 4
Data collection top
Bruker Kappa APEXII area-detector
diffractometer
4958 independent reflections
Radiation source: fine-focus sealed tube4559 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ϕ and ω scansθmax = 37.5°, θmin = 3.2°
Absorption correction: numerical
(APEX2; Bruker, 2006)
h = 1915
Tmin = 0.039, Tmax = 0.062k = 813
10118 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H 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 parametersΔρmax = 3.27 e Å3
2 restraintsΔρmin = 3.39 e Å3
Crystal data top
[U(CH3O3S)2O2(H2O)]V = 959.76 (6) Å3
Mr = 478.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.2613 (4) ŵ = 17.37 mm1
b = 7.9178 (3) ÅT = 100 K
c = 10.9061 (4) Å0.20 × 0.19 × 0.16 mm
β = 99.261 (1)°
Data collection top
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 = 0.062Rint = 0.018
10118 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0222 restraints
wR(F2) = 0.054H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 3.27 e Å3
4958 reflectionsΔρmin = 3.39 e Å3
135 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
U10.752778 (6)0.121075 (10)0.011327 (7)0.00498 (3)
S20.94159 (4)0.25209 (7)0.04481 (5)0.00625 (8)
S10.43671 (4)0.23068 (7)0.10448 (5)0.00632 (8)
O50.54270 (14)0.1816 (2)0.01433 (17)0.0090 (3)
O60.90791 (14)0.0786 (2)0.07588 (19)0.0093 (3)
O40.33894 (16)0.1091 (3)0.1009 (2)0.0164 (4)
O70.86707 (16)0.3194 (3)0.06341 (19)0.0128 (3)
O20.77899 (15)0.2103 (2)0.16107 (19)0.0118 (3)
O30.39990 (17)0.4020 (2)0.0874 (2)0.0133 (3)
O10.72636 (16)0.0298 (2)0.13744 (18)0.0109 (3)
O81.07021 (15)0.2558 (2)0.0337 (2)0.0146 (4)
C10.4747 (2)0.2170 (3)0.2535 (2)0.0118 (4)
H20.54190.29340.25970.014*
H10.40520.24900.31510.014*
H30.49830.10080.26910.014*
C20.9270 (2)0.3769 (3)0.1739 (3)0.0116 (4)
H60.85980.33530.21230.014*
H41.00150.37120.23420.014*
H50.91170.49420.14740.014*
O90.70849 (15)0.4086 (2)0.0706 (2)0.0099 (3)
H80.666 (3)0.467 (5)0.036 (4)0.024 (11)*
H70.759 (4)0.465 (7)0.095 (6)0.029 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
U10.00484 (3)0.00440 (4)0.00563 (4)0.00024 (2)0.00061 (2)0.00022 (2)
S20.00544 (16)0.0047 (2)0.0088 (2)0.00047 (15)0.00190 (15)0.00041 (16)
S10.00586 (17)0.0063 (2)0.0068 (2)0.00020 (15)0.00102 (15)0.00188 (16)
O50.0060 (5)0.0124 (8)0.0081 (7)0.0013 (5)0.0001 (5)0.0020 (6)
O60.0087 (6)0.0060 (7)0.0127 (8)0.0014 (5)0.0006 (5)0.0001 (6)
O40.0082 (6)0.0165 (9)0.0232 (11)0.0041 (6)0.0015 (6)0.0119 (7)
O70.0174 (7)0.0103 (8)0.0100 (8)0.0035 (6)0.0001 (6)0.0004 (6)
O20.0123 (7)0.0127 (8)0.0096 (8)0.0020 (6)0.0005 (6)0.0022 (6)
O30.0174 (8)0.0102 (8)0.0125 (9)0.0057 (6)0.0034 (6)0.0011 (6)
O10.0149 (7)0.0083 (7)0.0089 (8)0.0010 (5)0.0000 (6)0.0010 (6)
O80.0072 (6)0.0082 (8)0.0301 (12)0.0019 (5)0.0083 (6)0.0045 (7)
C10.0153 (9)0.0131 (10)0.0072 (9)0.0020 (7)0.0024 (7)0.0001 (8)
C20.0142 (9)0.0096 (10)0.0110 (10)0.0004 (7)0.0023 (7)0.0030 (8)
O90.0099 (6)0.0059 (7)0.0144 (9)0.0000 (5)0.0036 (6)0.0006 (6)
Geometric parameters (Å, º) top
U1—O11.7570 (19)S1—O41.4677 (19)
U1—O21.760 (2)S1—O51.4712 (18)
U1—O62.3772 (17)S1—C11.749 (3)
U1—O8i2.3804 (17)C1—H20.9800
U1—O4ii2.3806 (19)C1—H10.9800
U1—O52.3857 (15)C1—H30.9800
U1—O92.4670 (19)C2—H60.9800
S2—O71.436 (2)C2—H40.9800
S2—O81.4733 (16)C2—H50.9800
S2—O61.4789 (19)O9—H80.80 (4)
S2—C21.749 (3)O9—H70.80 (5)
S1—O31.439 (2)
O1—U1—O2179.37 (9)O6—S2—C2106.25 (12)
O1—U1—O690.41 (8)O3—S1—O4112.44 (12)
O2—U1—O689.23 (8)O3—S1—O5112.45 (12)
O1—U1—O8i90.97 (8)O4—S1—O5109.90 (11)
O2—U1—O8i89.45 (8)O3—S1—C1107.32 (13)
O6—U1—O8i76.06 (6)O4—S1—C1106.30 (14)
O1—U1—O4ii92.52 (9)O5—S1—C1108.12 (11)
O2—U1—O4ii86.88 (9)S1—O5—U1144.49 (11)
O6—U1—O4ii73.50 (6)S2—O6—U1138.87 (11)
O8i—U1—O4ii149.38 (6)S1—O4—U1ii152.86 (13)
O1—U1—O587.53 (7)S2—O8—U1i151.07 (12)
O2—U1—O592.48 (7)S1—C1—H2109.5
O6—U1—O5146.71 (6)S1—C1—H1109.5
O8i—U1—O5137.16 (6)H2—C1—H1109.5
O4ii—U1—O573.41 (6)S1—C1—H3109.5
O1—U1—O992.91 (8)H2—C1—H3109.5
O2—U1—O987.67 (8)H1—C1—H3109.5
O6—U1—O9144.79 (6)S2—C2—H6109.5
O8i—U1—O968.85 (6)S2—C2—H4109.5
O4ii—U1—O9141.19 (6)H6—C2—H4109.5
O5—U1—O968.49 (6)S2—C2—H5109.5
O7—S2—O8112.15 (13)H6—C2—H5109.5
O7—S2—O6113.29 (11)H4—C2—H5109.5
O8—S2—O6109.22 (10)U1—O9—H8118 (3)
O7—S2—C2109.49 (12)U1—O9—H7121 (5)
O8—S2—C2106.03 (12)H8—O9—H7110 (6)
Symmetry codes: (i) x+2, y, z; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O9—H8···O3iii0.80 (4)1.94 (2)2.717 (3)164 (5)
O9—H7···O7iv0.80 (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)]
Mr478.23
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)11.2613 (4), 7.9178 (3), 10.9061 (4)
β (°) 99.261 (1)
V3)959.76 (6)
Z4
Radiation typeMo Kα
µ (mm1)17.37
Crystal size (mm)0.20 × 0.19 × 0.16
Data collection
DiffractometerBruker Kappa APEXII area-detector
diffractometer
Absorption correctionNumerical
(APEX2; Bruker, 2006)
Tmin, Tmax0.039, 0.062
No. of measured, independent and
observed [I > 2σ(I)] reflections
10118, 4958, 4559
Rint0.018
(sin θ/λ)max1)0.856
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.054, 1.04
No. of reflections4958
No. of parameters135
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)3.27, 3.39

Computer programs: APEX2 (Bruker, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top
U1—O11.7570 (19)U1—O4ii2.3806 (19)
U1—O21.760 (2)U1—O52.3857 (15)
U1—O62.3772 (17)U1—O92.4670 (19)
U1—O8i2.3804 (17)
O1—U1—O2179.37 (9)
Symmetry codes: (i) x+2, y, z; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O9—H8···O3iii0.80 (4)1.94 (2)2.717 (3)164 (5)
O9—H7···O7iv0.80 (5)2.09 (4)2.791 (3)145 (7)
Symmetry codes: (iii) x+1, y+1, z; (iv) x, y+1, z.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds