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The title compound, [C5H14N2][UO2(H2O)(SO4)2], contains anionic [UO2(H2O)(SO4)2]2− chains with 1-methyl­piper­azinium cations balancing the charge. Each UVI atom is seven-coordinate in a pentagonal bipyramidal geometry, and each sulfate tetrahedron bridges two adjacent uranium centres. Neighbouring chains hydrogen bond to one another though the bound water mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011966/na6241sup1.cif
Contains datablocks USO-22, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011966/na6241Isup2.hkl
Contains datablock I

CCDC reference: 217368

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.021
  • wR factor = 0.054
  • Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The chemistry of open-framework metal phosphates is well known (Cheetham et al., 1999). Despite the depth of this investigation, little effort has been expended upon the analogous sulfate systems. Reports of organically templated metal sulfates have only appeared in the literature in the last two years. Compounds incorporating Sc (Bull et al., 2002), V (Paul, Choudhury, Nagarajan & Rao, 2003; Khan et al., 1999), Cd (Paul et al., 2002b; Choudhury et al., 2001), Fe (Paul et al., 2002a, 2002b, 2003; Paul, Choudhury, Sampathkumaran & Rao, 2003), Ce (Wang et al., 2002), La (Bataille & Louer, 2002; Xing et al., 2003) and U (Doran et al., 2002; Norquist et al., 2002, 2003; Thomas et al., 2003) are known. These compounds exhibit great structural diversity, with structures ranging from molecular anions to three-dimensional microporous materials. This report contains the synthesis and structure of an organically templated uranium(VI) sulfate. [C5H14N2][UO2(H2O)(SO4)2] is denoted USO-22 (uranium sulfate from Oxford).

One unique uranium centre is present in USO-22. U1 is seven coordinate, in a pentagonal bipyramidal geometry. Two short 'uranyl' bonds to axial oxides are observed. The U1 - O1 and U1 - O2 bond lengths are 1.780 (3) and 1.776 (3) Å respectively. This value is close to the average reported value of 1.758 (3) Å (Burns et al., 1997), and the O1 - U1 - O2 angle is close to 180 °, with a value of 178.31 (15) °. Four of the five equatorial coordination sites around U1 are occupied by oxide ligands that bridge between U1 and a sulfur centre, through distances ranging between 2.332 (3) and 2.405 (3) Å. The fifth equatorial coordination site is occupied by a bound water molecule through a longer U - O bond, the value of the U1 - O3 is 2.479 (4) Å. Two distinct sulfur site are observed in USO-22. Both S1 and S2 occupy the centre of [SO4] tetrahedra. Each sulfur centre is bound to two oxide ligands that bridge to adjacent uranium centres and two terminal oxides. The bonds to bridging oxides are longer than those to terminal oxides. The ranges of S - Obridging and S - Oterminal bond lengths are 1.483 (3) to 1.506 (3) Å and 1.453 (4) to 1.467 (3) Å respectively.

Chains are formed because each uranium centre is connect to two others through four bridging sulfate tetrahedra. This chain structure is known in uranium chemistry (Thomas et al., 2003; Norquist et al., 2002 & 2003; Tabachenko et al., 1984). Successive chains hydrogen-bond to one-another forming pseudo layers. See Figure 1. These 'layers' lie in the [0 1 1] plane, and stack in an aa sequence. See Figure 2. A thermal ellipsoid plot is shown in Figure 3.

Experimental top

0.3150 g (7.43 × 10−4 mol) of UO2(CH3CO2)2.2H2O, 0.4210 g (4.20 × 10−3 mol) of H2SO4, 0.0288 g (2.50 × 10−4 mol) of 1-amino-4-methylpiperzine and 0.9930 g (5.52 × 10−2 mol) of water were placed into a 23 ml teflon lined autoclave. The autoclave was heated to 453 K for 24 h, at which point the autoclave was slow cooled to 297 K over an additional 24 h. The autoclave was opened in air and the products recovered by filtration. Structural analysis was conducted at 150 K.

Refinement top

H atoms placed geometrically after each cycle

Computing details top

Data collection: COLLECT (Nonius BV, 1997); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1996); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al. 2001); molecular graphics: CAMERON (Watkin et al. 1996); software used to prepare material for publication: CRYSTALS (Watkin et al. 2001).

Figures top
[Figure 1] Fig. 1. Chains in USO-22. Green pentagonal bipyramids, and blue tetrahedra represent [UO7] and [SO4] respectively.
[Figure 2] Fig. 2. Three-dimensional packing of USO-22. Green pentagonal bipyramids, and blue tetrahedra represent [UO7] and [SO4] respectively.
[Figure 3] Fig. 3. Displacement ellipsoid plot of the title compound, with the atomic numbering scheme. Ellipsoids are drawn at the 50% probability level. Hydrogen atoms have been removed for clarity.
(I) top
Crystal data top
C5H16N2O11S2UZ = 2
Mr = 582.35F(000) = 523.717
Triclinic, P1Dx = 2.906 Mg m3
Hall symbol: -P 1Melting point: not measured K
a = 8.0031 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.1873 (2) ÅCell parameters from 2832 reflections
c = 10.8911 (3) Åθ = 5–27°
α = 72.704 (1)°µ = 12.57 mm1
β = 81.7766 (11)°T = 150 K
γ = 78.7917 (9)°Block, yellow
V = 665.60 (3) Å30.10 × 0.10 × 0.10 mm
Data collection top
Enraf Nonius Kappa CCD
diffractometer
2640 reflections with > 3.00σ(I)
Graphite monochromatorRint = 0.02
ω scansθmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan
(Otwinowsky & Minor, 1996)
h = 1010
Tmin = 0.28, Tmax = 0.28k = 1010
5594 measured reflectionsl = 1314
3026 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters not refined
R[F2 > 2σ(F2)] = 0.021 Chebychev polynomial with 5 parameters, Carruthers & Watkin , 1979, 8.86 4.95 9.20 0.122E-01 2.37
wR(F2) = 0.054(Δ/σ)max = 0.002
S = 1.01Δρmax = 0.99 e Å3
2640 reflectionsΔρmin = 0.92 e Å3
191 parametersExtinction correction: Larson 1970 Crystallographic Computing eq 22
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 16.5 (15)
Secondary atom site location: difference Fourier map
Crystal data top
C5H16N2O11S2Uγ = 78.7917 (9)°
Mr = 582.35V = 665.60 (3) Å3
Triclinic, P1Z = 2
a = 8.0031 (2) ÅMo Kα radiation
b = 8.1873 (2) ŵ = 12.57 mm1
c = 10.8911 (3) ÅT = 150 K
α = 72.704 (1)°0.10 × 0.10 × 0.10 mm
β = 81.7766 (11)°
Data collection top
Enraf Nonius Kappa CCD
diffractometer
3026 independent reflections
Absorption correction: multi-scan
(Otwinowsky & Minor, 1996)
2640 reflections with > 3.00σ(I)
Tmin = 0.28, Tmax = 0.28Rint = 0.02
5594 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.021191 parameters
wR(F2) = 0.054H-atom parameters not refined
S = 1.01Δρmax = 0.99 e Å3
2640 reflectionsΔρmin = 0.92 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
U10.61840 (2)0.25038 (2)1.251849 (15)0.0076
S10.70037 (14)0.10688 (15)1.51706 (11)0.0109
S20.26874 (14)0.36159 (14)1.00541 (11)0.0099
O10.6476 (4)0.4238 (4)1.3239 (3)0.0144
O20.5951 (4)0.0800 (4)1.1778 (3)0.0131
O30.9302 (5)0.3046 (5)1.2312 (3)0.0202
O40.7485 (4)0.0775 (4)1.4377 (3)0.0130
O50.3965 (4)0.0968 (5)1.3785 (3)0.0141
O60.3500 (4)0.3244 (5)1.1399 (3)0.0144
O70.3142 (4)0.5528 (4)0.9467 (3)0.0140
O80.8554 (5)0.1780 (5)1.5744 (4)0.0208
O90.5933 (5)0.2107 (5)1.4386 (3)0.0174
O100.3315 (5)0.2662 (5)0.9326 (3)0.0172
O110.0823 (4)0.3178 (5)1.0078 (3)0.0161
N10.0591 (6)0.2568 (6)0.7538 (4)0.0183
N20.4122 (6)0.2749 (6)0.7823 (4)0.0183
C10.1699 (7)0.3628 (7)0.6450 (5)0.0225
C20.3045 (7)0.4266 (7)0.6957 (6)0.0235
C30.3022 (7)0.1738 (7)0.8877 (5)0.0187
C40.1731 (6)0.1093 (7)0.8331 (5)0.0167
C50.0697 (7)0.1945 (9)0.6991 (6)0.0273
H11.00880.28771.31230.0229*
H20.97540.33991.14460.0229*
H30.00540.32990.80950.0224*
H40.09530.46460.59260.0273*
H50.22890.28780.58820.0273*
H60.38030.48750.62110.0291*
H70.24770.50950.74590.0291*
H80.47570.19700.72980.0221*
H90.49550.31900.82000.0221*
H100.37560.07260.94330.0226*
H110.24020.24990.94290.0226*
H120.10180.03800.90580.0204*
H130.23460.03330.77780.0204*
H140.14290.12550.77020.0402*
H150.14520.29690.64610.0402*
H160.01020.12070.64220.0402*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
U10.0081 (1)0.0079 (1)0.0053 (1)0.00126 (6)0.00067 (6)0.00029 (6)
S10.0094 (5)0.0125 (5)0.0088 (5)0.0028 (4)0.0014 (4)0.0009 (4)
S20.0093 (5)0.0097 (5)0.0087 (5)0.0013 (4)0.0007 (4)0.0001 (4)
O10.0181 (17)0.0115 (16)0.0141 (16)0.0006 (13)0.0040 (13)0.0050 (13)
O20.0166 (16)0.0113 (16)0.0113 (16)0.0020 (13)0.0016 (13)0.0044 (13)
O30.0144 (17)0.029 (2)0.0125 (17)0.0077 (15)0.0025 (13)0.0013 (15)
O40.0122 (15)0.0154 (17)0.0070 (14)0.0020 (13)0.0009 (12)0.0036 (13)
O50.0124 (15)0.0192 (18)0.0089 (15)0.0006 (13)0.0033 (12)0.0012 (13)
O60.0145 (16)0.0201 (18)0.0051 (15)0.0040 (13)0.0018 (12)0.0030 (13)
O70.0167 (16)0.0085 (16)0.0137 (16)0.0021 (13)0.0001 (13)0.0010 (13)
O80.0147 (17)0.027 (2)0.0145 (17)0.0102 (15)0.0006 (14)0.0076 (15)
O90.0221 (18)0.0146 (17)0.0143 (17)0.0042 (14)0.0012 (14)0.0027 (14)
O100.0221 (18)0.0148 (17)0.0171 (18)0.0055 (14)0.0045 (14)0.0051 (14)
O110.0068 (15)0.0199 (18)0.0188 (17)0.0006 (13)0.0006 (13)0.0032 (15)
N10.014 (2)0.022 (2)0.020 (2)0.0028 (16)0.0048 (16)0.0098 (18)
N20.0136 (19)0.020 (2)0.022 (2)0.0024 (16)0.0042 (17)0.0051 (18)
C10.027 (3)0.020 (3)0.019 (3)0.002 (2)0.003 (2)0.004 (2)
C20.023 (3)0.020 (3)0.028 (3)0.002 (2)0.008 (2)0.005 (2)
C30.017 (2)0.023 (3)0.016 (2)0.0012 (19)0.0019 (19)0.006 (2)
C40.018 (2)0.016 (2)0.015 (2)0.0006 (19)0.0013 (18)0.0033 (19)
C50.013 (2)0.045 (4)0.036 (3)0.005 (2)0.005 (2)0.026 (3)
Geometric parameters (Å, º) top
U1—O11.780 (3)N2—C31.485 (7)
U1—O21.776 (3)C1—C21.516 (8)
U1—O32.479 (4)C3—C41.508 (7)
U1—O42.335 (3)N1—H31.000
U1—O52.332 (3)N2—H91.001
U1—O62.405 (3)N2—H81.000
U1—O7i2.342 (3)O3—H10.999
S1—O41.506 (3)O3—H20.999
S1—O5ii1.496 (3)C4—H121.009
S1—O81.453 (4)C4—H131.005
S1—O91.458 (4)C3—H111.006
S2—O61.483 (3)C3—H101.006
S2—O71.497 (3)C1—H40.999
S2—O101.458 (4)C1—H51.006
S2—O111.467 (3)C2—H70.999
N1—C11.527 (7)C2—H61.006
N1—C41.488 (6)C5—H151.008
N1—C51.496 (7)C5—H141.001
N2—C21.515 (7)C5—H161.002
O1—U1—O2178.31 (15)N1—C1—C2112.1 (5)
O1—U1—O389.18 (15)N2—C2—C1110.0 (4)
O1—U1—O490.83 (14)N2—C3—C4110.7 (4)
O1—U1—O591.77 (14)N1—C4—C3110.8 (4)
O1—U1—O691.66 (14)C4—N1—H3109.278
O1—U1—O7i90.42 (14)C1—N1—H3110.404
O2—U1—O389.25 (14)C5—N1—H3107.340
O2—U1—O489.29 (14)C3—N2—H9109.830
O2—U1—O589.88 (14)C2—N2—H9109.360
O2—U1—O689.21 (14)C3—N2—H8108.413
O2—U1—O7i88.42 (14)C2—N2—H8108.909
O3—U1—O472.07 (12)H9—N2—H8109.698
O3—U1—O5146.50 (12)U1—O3—H1117.766
O3—U1—O6142.97 (11)U1—O3—H2121.016
O3—U1—O7i68.63 (12)H1—O3—H2121.207
O4—U1—O574.44 (11)N1—C4—H12109.346
O4—U1—O6144.89 (11)C3—C4—H12109.694
O4—U1—O7i140.65 (12)N1—C4—H13109.257
O5—U1—O670.48 (11)C3—C4—H13109.424
O5—U1—O7i144.81 (12)H12—C4—H13108.298
O6—U1—O7i74.35 (11)N2—C3—H11109.225
O4—S1—O5ii105.6 (2)C4—C3—H11109.210
O4—S1—O8109.0 (2)N2—C3—H10109.499
O4—S1—O9110.9 (2)C4—C3—H10109.668
O5ii—S1—O8109.4 (2)H11—C3—H10108.459
O5ii—S1—O9110.3 (2)N1—C1—H4109.161
O8—S1—O9111.4 (2)C2—C1—H4109.077
O6—S2—O7106.5 (2)N1—C1—H5108.642
O6—S2—O10110.8 (2)C2—C1—H5108.717
O6—S2—O11109.2 (2)H4—C1—H5109.053
O7—S2—O10110.5 (2)N2—C2—H7109.322
O7—S2—O11108.6 (2)C1—C2—H7109.580
O10—S2—O11111.2 (2)N2—C2—H6109.313
U1—O4—S1132.9 (2)C1—C2—H6109.536
U1—O5—S1ii141.6 (2)H7—C2—H6109.108
U1—O6—S2137.6 (2)N1—C5—H15109.680
U1i—O7—S2139.7 (2)N1—C5—H14110.367
C1—N1—C4108.3 (4)H15—C5—H14108.794
C1—N1—C5110.2 (4)N1—C5—H16109.963
C2—N2—C3110.6 (4)H15—C5—H16108.718
C4—N1—C5111.3 (4)H14—C5—H16109.285
Symmetry codes: (i) x1, y+1, z+2; (ii) x1, y, z+3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H3···S21.002.813.687 (5)147
N1—H3···O111.002.142.982 (6)141
O3—H2···S2iii1.002.923.786 (4)145
O3—H2···O111.001.892.838 (5)157
N2—H8···O2iv1.002.272.924 (5)122
C4—H13···O5iv1.002.373.364 (7)169
N2—H8···O9iv1.001.922.761 (6)140
C2—H7···O6v1.002.413.184 (8)134
N2—H9···O10vi1.001.882.780 (7)147
Symmetry codes: (iii) x1, y, z; (iv) x, y, z+2; (v) x, y+1, z+2; (vi) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC5H16N2O11S2U
Mr582.35
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)8.0031 (2), 8.1873 (2), 10.8911 (3)
α, β, γ (°)72.704 (1), 81.7766 (11), 78.7917 (9)
V3)665.60 (3)
Z2
Radiation typeMo Kα
µ (mm1)12.57
Crystal size (mm)0.10 × 0.10 × 0.10
Data collection
DiffractometerEnraf Nonius Kappa CCD
diffractometer
Absorption correctionMulti-scan
(Otwinowsky & Minor, 1996)
Tmin, Tmax0.28, 0.28
No. of measured, independent and
observed [ > 3.00σ(I)] reflections
5594, 3026, 2640
Rint0.02
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.054, 1.01
No. of reflections2640
No. of parameters191
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.99, 0.92

Computer programs: COLLECT (Nonius BV, 1997), DENZO/SCALEPACK (Otwinowski & Minor, 1996), SIR92 (Altomare et al., 1994), CRYSTALS (Watkin et al. 2001), CAMERON (Watkin et al. 1996).

Selected geometric parameters (Å, º) top
U1—O11.780 (3)S2—O61.483 (3)
U1—O21.776 (3)S2—O71.497 (3)
U1—O32.479 (4)S2—O101.458 (4)
U1—O42.335 (3)S2—O111.467 (3)
U1—O52.332 (3)N1—C11.527 (7)
U1—O62.405 (3)N1—C41.488 (6)
U1—O7i2.342 (3)N1—C51.496 (7)
S1—O41.506 (3)N2—C21.515 (7)
S1—O5ii1.496 (3)N2—C31.485 (7)
S1—O81.453 (4)C1—C21.516 (8)
S1—O91.458 (4)C3—C41.508 (7)
O1—U1—O2178.31 (15)O5—U1—O7i144.81 (12)
O1—U1—O389.18 (15)O6—U1—O7i74.35 (11)
O1—U1—O490.83 (14)O4—S1—O5ii105.6 (2)
O1—U1—O591.77 (14)O4—S1—O8109.0 (2)
O1—U1—O691.66 (14)O4—S1—O9110.9 (2)
O1—U1—O7i90.42 (14)O5ii—S1—O8109.4 (2)
O2—U1—O389.25 (14)O5ii—S1—O9110.3 (2)
O2—U1—O489.29 (14)O8—S1—O9111.4 (2)
O2—U1—O589.88 (14)O6—S2—O7106.5 (2)
O2—U1—O689.21 (14)O6—S2—O10110.8 (2)
O2—U1—O7i88.42 (14)O6—S2—O11109.2 (2)
O3—U1—O472.07 (12)O7—S2—O10110.5 (2)
O3—U1—O5146.50 (12)O7—S2—O11108.6 (2)
O3—U1—O6142.97 (11)O10—S2—O11111.2 (2)
O3—U1—O7i68.63 (12)U1—O4—S1132.9 (2)
O4—U1—O574.44 (11)U1—O5—S1ii141.6 (2)
O4—U1—O6144.89 (11)U1—O6—S2137.6 (2)
O4—U1—O7i140.65 (12)U1i—O7—S2139.7 (2)
O5—U1—O670.48 (11)
Symmetry codes: (i) x1, y+1, z+2; (ii) x1, y, z+3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H3···S21.002.813.687 (5)147
N1—H3···O111.002.142.982 (6)141
O3—H2···S2iii1.002.923.786 (4)145
O3—H2···O111.001.892.838 (5)157
N2—H8···O2iv1.002.272.924 (5)122
C4—H13···O5iv1.002.373.364 (7)169
N2—H8···O9iv1.001.922.761 (6)140
C2—H7···O6v1.002.413.184 (8)134
N2—H9···O10vi1.001.882.780 (7)147
Symmetry codes: (iii) x1, y, z; (iv) x, y, z+2; (v) x, y+1, z+2; (vi) x+1, y, z.
 

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