The title compound, {(C10H28N4)[(UO2)2(SO4)4]}n, contains two-dimensional [(UO2)2(SO4)4]4− layers with 1,4-bis-(3-aminopropyl)piperazinium cations balancing the charge. Each UVI cation is seven-coordinate in a pentagonal bipyramidal geometry, and each sulfate tetrahedron bridges beween two adjacent uranium centres to form layers.
Supporting information
CCDC reference: 222812
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.010 Å
- R factor = 0.023
- wR factor = 0.053
- Data-to-parameter ratio = 12.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.99
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.26
PLAT213_ALERT_2_C Atom C5 has ADP max/min Ratio ............. 3.20 prolat
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.99 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.93 Ratio
PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors .... C5
PLAT250_ALERT_2_C Large U3/U1 ratio for average U(i,j) tensor .... 2.53
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 10
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
11 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
5 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0.2585 g (6.10 × 10−4 mol) of UO2(CH3CO2)2·2H2O, 0.4048 g (4.13 × 10−3 mol) of H2SO4, 0.1234 g (6.17 × 10−4 mol) of 1,4-bis(3-aminopropyl)piperazine and 1.0168 g (5.65 × 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.
H atoms were placed geometrically, with C—H and N—H distances fixed at 1.00 Å, and were unrefined. The highest peak in the difference map was located 1.89 Å from H11. Refinement treating this as a solvent water O atom resulted in a partial occupancy of 0.28 (1). Although the inclusion of this atom improves the various agreement analyses, it was not included in the final refinement as it is not chemically significant.
Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); 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.
Crystal data top
(C10H28N4)[(UO2)2(SO4)4] | Dx = 2.766 Mg m−3 |
Mr = 1128.66 | Melting point: not measured K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3482 reflections |
a = 9.5831 (2) Å | θ = 5–27° |
b = 15.6060 (3) Å | µ = 12.34 mm−1 |
c = 18.1212 (3) Å | T = 150 K |
V = 2710.10 (9) Å3 | Block, yellow |
Z = 4 | 0.20 × 0.16 × 0.16 mm |
F(000) = 2096.000 | |
Data collection top
Enraf-Nonius KappaCCD diffractometer | 2219 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.02 |
ω scans | θmax = 27.5°, θmin = 5.1° |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | h = −12→12 |
Tmin = 0.11, Tmax = 0.14 | k = −20→20 |
6194 measured reflections | l = −23→23 |
3091 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.023 | Chebychev polynomial with 5 parameters (Carruthers & Watkin, 1979):
7.01, 10.1, 6.10, 2.43 and 1.09 |
wR(F2) = 0.053 | (Δ/σ)max = 0.001 |
S = 0.89 | Δρmax = 2.10 e Å−3 |
2219 reflections | Δρmin = −0.93 e Å−3 |
182 parameters | Extinction correction: Larson (1970), Crystallographic Computing eq 22 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 29.4 (27) |
Crystal data top
(C10H28N4)[(UO2)2(SO4)4] | V = 2710.10 (9) Å3 |
Mr = 1128.66 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.5831 (2) Å | µ = 12.34 mm−1 |
b = 15.6060 (3) Å | T = 150 K |
c = 18.1212 (3) Å | 0.20 × 0.16 × 0.16 mm |
Data collection top
Enraf-Nonius KappaCCD diffractometer | 3091 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 2219 reflections with I > 3σ(I) |
Tmin = 0.11, Tmax = 0.14 | Rint = 0.02 |
6194 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.023 | 182 parameters |
wR(F2) = 0.053 | H-atom parameters not refined |
S = 0.89 | Δρmax = 2.10 e Å−3 |
2219 reflections | Δρmin = −0.93 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
U1 | 0.424986 (19) | 0.299415 (12) | 0.367361 (11) | 0.0085 | |
S1 | 0.72400 (14) | 0.29915 (9) | 0.48612 (7) | 0.0118 | |
S2 | 0.19710 (14) | 0.35864 (9) | 0.25902 (8) | 0.0132 | |
O1 | 0.3995 (4) | 0.1910 (3) | 0.3403 (2) | 0.0161 | |
O2 | 0.4491 (4) | 0.4065 (3) | 0.3958 (2) | 0.0164 | |
O7 | 0.1180 (4) | 0.2944 (3) | 0.2150 (2) | 0.0179 | |
O5 | 0.1814 (4) | 0.3351 (3) | 0.3387 (2) | 0.0165 | |
O6 | 0.3492 (4) | 0.3461 (3) | 0.2443 (2) | 0.0184 | |
O4 | 0.7976 (4) | 0.2285 (3) | 0.5256 (2) | 0.0144 | |
O8 | 0.6717 (5) | 0.3626 (3) | 0.5373 (3) | 0.0251 | |
O3 | 0.6070 (4) | 0.2557 (3) | 0.4455 (2) | 0.0175 | |
O10 | 0.1505 (5) | 0.4444 (3) | 0.2440 (3) | 0.0226 | |
O9 | 0.8211 (5) | 0.3371 (3) | 0.4329 (2) | 0.0213 | |
N1 | 0.1061 (5) | 0.0081 (3) | 0.0580 (3) | 0.0139 | |
N2 | 0.4778 (6) | 0.1971 (4) | 0.1484 (3) | 0.0265 | |
C1 | −0.0466 (6) | 0.0009 (4) | 0.0752 (3) | 0.0178 | |
C4 | 0.3283 (7) | 0.0774 (5) | 0.1049 (4) | 0.0245 | |
C3 | 0.1775 (7) | 0.0561 (4) | 0.1193 (4) | 0.0198 | |
C2 | 0.1246 (7) | 0.0489 (4) | −0.0164 (4) | 0.0190 | |
C5 | 0.3834 (11) | 0.1284 (7) | 0.1704 (5) | 0.0533 | |
H2 | −0.0580 | −0.0290 | 0.1236 | 0.0215* | |
H3 | −0.0870 | 0.0599 | 0.0786 | 0.0215* | |
H9 | 0.3831 | 0.0233 | 0.0989 | 0.0291* | |
H8 | 0.3360 | 0.1126 | 0.0590 | 0.0291* | |
H7 | 0.1727 | 0.0204 | 0.1650 | 0.0239* | |
H6 | 0.1258 | 0.1110 | 0.1274 | 0.0239* | |
H4 | 0.2262 | 0.0499 | −0.0291 | 0.0242* | |
H5 | 0.0880 | 0.1089 | −0.0147 | 0.0242* | |
H11 | 0.4354 | 0.0884 | 0.2036 | 0.0652* | |
H10 | 0.3029 | 0.1539 | 0.1978 | 0.0652* | |
H14 | 0.5115 | 0.2281 | 0.1932 | 0.0322* | |
H13 | 0.5594 | 0.1725 | 0.1213 | 0.0322* | |
H12 | 0.4269 | 0.2379 | 0.1155 | 0.0322* | |
H1 | 0.1506 | −0.0497 | 0.0553 | 0.0166* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
U1 | 0.0068 (1) | 0.01131 (11) | 0.0075 (1) | −0.00065 (8) | 0.00020 (8) | 0.00045 (8) |
S1 | 0.0108 (6) | 0.0126 (6) | 0.0121 (6) | −0.0001 (6) | −0.0031 (5) | 0.0009 (5) |
S2 | 0.0094 (7) | 0.0165 (7) | 0.0137 (7) | −0.0015 (5) | −0.0017 (5) | 0.0025 (5) |
O1 | 0.017 (2) | 0.016 (2) | 0.0151 (19) | −0.0030 (17) | 0.0025 (16) | −0.0014 (17) |
O2 | 0.016 (2) | 0.0152 (19) | 0.0178 (19) | −0.0031 (17) | 0.0013 (17) | 0.0005 (18) |
O7 | 0.0108 (18) | 0.022 (2) | 0.021 (2) | −0.0008 (18) | −0.0041 (16) | −0.0052 (19) |
O5 | 0.013 (2) | 0.025 (2) | 0.0108 (18) | −0.0025 (18) | 0.0013 (16) | 0.0038 (18) |
O6 | 0.009 (2) | 0.032 (2) | 0.014 (2) | −0.0014 (19) | 0.0001 (17) | 0.003 (2) |
O4 | 0.015 (2) | 0.016 (2) | 0.0123 (18) | 0.0014 (17) | −0.0038 (16) | 0.0015 (16) |
O8 | 0.024 (3) | 0.024 (2) | 0.027 (3) | 0.009 (2) | −0.003 (2) | −0.007 (2) |
O3 | 0.013 (2) | 0.021 (2) | 0.018 (2) | 0.0006 (18) | −0.0095 (16) | 0.0028 (18) |
O10 | 0.021 (2) | 0.021 (2) | 0.025 (2) | −0.0002 (19) | −0.002 (2) | 0.005 (2) |
O9 | 0.024 (2) | 0.020 (2) | 0.019 (2) | −0.006 (2) | 0.0018 (19) | 0.0055 (19) |
N1 | 0.013 (3) | 0.010 (2) | 0.018 (2) | −0.0031 (19) | −0.0004 (19) | −0.0014 (19) |
N2 | 0.028 (3) | 0.024 (3) | 0.027 (3) | −0.010 (3) | −0.002 (2) | 0.000 (3) |
C1 | 0.014 (3) | 0.020 (3) | 0.019 (3) | −0.001 (2) | 0.007 (2) | −0.003 (2) |
C4 | 0.023 (3) | 0.028 (4) | 0.023 (3) | −0.010 (3) | −0.006 (3) | 0.003 (3) |
C3 | 0.017 (3) | 0.018 (3) | 0.024 (3) | 0.003 (2) | −0.006 (2) | −0.005 (3) |
C2 | 0.016 (3) | 0.018 (3) | 0.023 (3) | −0.002 (2) | 0.000 (3) | −0.000 (3) |
C5 | 0.066 (6) | 0.062 (6) | 0.032 (4) | −0.052 (5) | −0.007 (4) | 0.002 (4) |
Geometric parameters (Å, º) top
U1—O1 | 1.778 (4) | N1—H1 | 1.00 |
U1—O2 | 1.764 (4) | N2—C5 | 1.458 (9) |
U1—O3 | 2.348 (4) | N2—H12 | 1.00 |
U1—O4i | 2.332 (4) | N2—H13 | 1.00 |
U1—O5 | 2.455 (4) | N2—H14 | 1.00 |
U1—O6 | 2.456 (4) | C1—C2iii | 1.516 (9) |
U1—O7ii | 2.378 (4) | C1—H2 | 1.00 |
S1—O3 | 1.502 (4) | C1—H3 | 1.00 |
S1—O4 | 1.492 (4) | C2—H4 | 1.00 |
S1—O8 | 1.447 (5) | C2—H5 | 1.00 |
S1—O9 | 1.465 (5) | C3—H6 | 1.00 |
S2—O5 | 1.497 (4) | C3—H7 | 1.00 |
S2—O6 | 1.494 (4) | C4—C3 | 1.506 (9) |
S2—O7 | 1.489 (4) | C4—C5 | 1.52 (1) |
S2—O10 | 1.437 (5) | C4—H8 | 1.00 |
N1—C1 | 1.500 (7) | C4—H9 | 1.00 |
N1—C2 | 1.503 (8) | C5—H10 | 1.00 |
N1—C3 | 1.504 (8) | C5—H11 | 1.00 |
| | | |
O1—U1—O2 | 178.93 (18) | C1—N1—H1 | 111.1 |
O1—U1—O3 | 89.54 (18) | C2—N1—C3 | 113.5 (5) |
O1—U1—O4i | 88.82 (17) | C2—N1—H1 | 106.6 |
O1—U1—O5 | 91.55 (17) | C3—N1—H1 | 107.0 |
O1—U1—O6 | 89.51 (18) | C5—N2—H12 | 109.2 |
O1—U1—O7ii | 84.40 (17) | C5—N2—H13 | 109.7 |
O2—U1—O3 | 90.07 (18) | C5—N2—H14 | 109.5 |
O2—U1—O4i | 90.13 (17) | H12—N2—H13 | 109.476 |
O2—U1—O5 | 88.36 (17) | H12—N2—H14 | 109.476 |
O2—U1—O6 | 91.34 (18) | H13—N2—H14 | 109.476 |
O2—U1—O7ii | 96.49 (17) | N1—C1—C2iii | 112.0 (5) |
O3—U1—O4i | 80.39 (15) | N1—C1—H2 | 108.8 |
O3—U1—O5 | 154.13 (15) | N1—C1—H3 | 108.8 |
O3—U1—O6 | 148.60 (14) | C2iii—C1—H2 | 108.8 |
O3—U1—O7ii | 77.92 (15) | C2iii—C1—H3 | 108.9 |
O4i—U1—O5 | 73.79 (14) | H2—C1—H3 | 109.467 |
O4i—U1—O6 | 130.96 (14) | N1—C2—C1iii | 110.8 (5) |
O4i—U1—O7ii | 157.30 (15) | N1—C2—H4 | 109.2 |
O5—U1—O6 | 57.26 (13) | N1—C2—H5 | 109.1 |
O5—U1—O7ii | 127.90 (14) | C1iii—C2—H4 | 109.1 |
O6—U1—O7ii | 70.76 (14) | C1iii—C2—H5 | 109.2 |
O3—S1—O4 | 104.8 (3) | H4—C2—H5 | 109.467 |
O3—S1—O8 | 111.4 (3) | N1—C3—C4 | 114.7 (5) |
O3—S1—O9 | 109.5 (3) | N1—C3—H6 | 108.1 |
O4—S1—O8 | 111.2 (3) | N1—C3—H7 | 108.2 |
O4—S1—O9 | 108.3 (3) | C4—C3—H6 | 108.2 |
O8—S1—O9 | 111.4 (3) | C4—C3—H7 | 108.1 |
O5—S2—O6 | 103.7 (2) | H6—C3—H7 | 109.467 |
O5—S2—O7 | 107.5 (3) | C3—C4—C5 | 108.2 (6) |
O5—S2—O10 | 112.3 (3) | C3—C4—H8 | 109.7 |
O6—S2—O7 | 108.2 (3) | C3—C4—H9 | 109.7 |
O6—S2—O10 | 113.0 (3) | C5—C4—H8 | 109.6 |
O7—S2—O10 | 111.6 (3) | C5—C4—H9 | 110.1 |
U1—O3—S1 | 136.0 (3) | H8—C4—H9 | 109.467 |
U1iv—O4—S1 | 141.7 (3) | N2—C5—C4 | 112.7 (7) |
U1—O5—S2 | 99.5 (2) | N2—C5—H10 | 108.9 |
U1—O6—S2 | 99.5 (2) | N2—C5—H11 | 108.4 |
U1v—O7—S2 | 135.2 (3) | C4—C5—H10 | 109.1 |
C1—N1—C2 | 109.4 (5) | C4—C5—H11 | 108.3 |
C1—N1—C3 | 109.2 (5) | H10—C5—H11 | 109.467 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, y, −z+1/2; (iii) −x, −y, −z; (iv) x+1/2, −y+1/2, −z+1; (v) x−1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O9vi | 1.00 | 1.80 | 2.763 (7) | 161 |
N2—H12···O9v | 1.00 | 2.05 | 3.033 (7) | 168 |
N2—H13···O8vii | 1.00 | 1.94 | 2.894 (8) | 158 |
N2—H14···O7ii | 1.00 | 2.21 | 3.200 (7) | 171 |
Symmetry codes: (ii) x+1/2, y, −z+1/2; (v) x−1/2, y, −z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | (C10H28N4)[(UO2)2(SO4)4] |
Mr | 1128.66 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 150 |
a, b, c (Å) | 9.5831 (2), 15.6060 (3), 18.1212 (3) |
V (Å3) | 2710.10 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 12.34 |
Crystal size (mm) | 0.20 × 0.16 × 0.16 |
|
Data collection |
Diffractometer | Enraf-Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.11, 0.14 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 6194, 3091, 2219 |
Rint | 0.02 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.053, 0.89 |
No. of reflections | 2219 |
No. of parameters | 182 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 2.10, −0.93 |
Selected geometric parameters (Å, º) topU1—O1 | 1.778 (4) | S2—O5 | 1.497 (4) |
U1—O2 | 1.764 (4) | S2—O6 | 1.494 (4) |
U1—O3 | 2.348 (4) | S2—O7 | 1.489 (4) |
U1—O4i | 2.332 (4) | S2—O10 | 1.437 (5) |
U1—O5 | 2.455 (4) | N1—C1 | 1.500 (7) |
U1—O6 | 2.456 (4) | N1—C2 | 1.503 (8) |
U1—O7ii | 2.378 (4) | N1—C3 | 1.504 (8) |
S1—O3 | 1.502 (4) | N2—C5 | 1.458 (9) |
S1—O4 | 1.492 (4) | C1—C2iii | 1.516 (9) |
S1—O8 | 1.447 (5) | C4—C3 | 1.506 (9) |
S1—O9 | 1.465 (5) | C4—C5 | 1.52 (1) |
| | | |
O1—U1—O2 | 178.93 (18) | O3—S1—O9 | 109.5 (3) |
O1—U1—O3 | 89.54 (18) | O4—S1—O8 | 111.2 (3) |
O1—U1—O4i | 88.82 (17) | O4—S1—O9 | 108.3 (3) |
O1—U1—O5 | 91.55 (17) | O8—S1—O9 | 111.4 (3) |
O1—U1—O6 | 89.51 (18) | O5—S2—O6 | 103.7 (2) |
O1—U1—O7ii | 84.40 (17) | O5—S2—O7 | 107.5 (3) |
O2—U1—O3 | 90.07 (18) | O5—S2—O10 | 112.3 (3) |
O2—U1—O4i | 90.13 (17) | O6—S2—O7 | 108.2 (3) |
O2—U1—O5 | 88.36 (17) | O6—S2—O10 | 113.0 (3) |
O2—U1—O6 | 91.34 (18) | O7—S2—O10 | 111.6 (3) |
O2—U1—O7ii | 96.49 (17) | U1—O3—S1 | 136.0 (3) |
O3—U1—O4i | 80.39 (15) | U1iv—O4—S1 | 141.7 (3) |
O3—U1—O5 | 154.13 (15) | U1—O5—S2 | 99.5 (2) |
O3—U1—O6 | 148.60 (14) | U1—O6—S2 | 99.5 (2) |
O3—U1—O7ii | 77.92 (15) | U1v—O7—S2 | 135.2 (3) |
O4i—U1—O5 | 73.79 (14) | C1—N1—C2 | 109.4 (5) |
O4i—U1—O6 | 130.96 (14) | C1—N1—C3 | 109.2 (5) |
O4i—U1—O7ii | 157.30 (15) | C2—N1—C3 | 113.5 (5) |
O5—U1—O6 | 57.26 (13) | N1—C1—C2iii | 112.0 (5) |
O5—U1—O7ii | 127.90 (14) | N1—C2—C1iii | 110.8 (5) |
O6—U1—O7ii | 70.76 (14) | N1—C3—C4 | 114.7 (5) |
O3—S1—O4 | 104.8 (3) | C3—C4—C5 | 108.2 (6) |
O3—S1—O8 | 111.4 (3) | N2—C5—C4 | 112.7 (7) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, y, −z+1/2; (iii) −x, −y, −z; (iv) x+1/2, −y+1/2, −z+1; (v) x−1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O9vi | 1.00 | 1.80 | 2.763 (7) | 161 |
N2—H12···O9v | 1.00 | 2.05 | 3.033 (7) | 168 |
N2—H13···O8vii | 1.00 | 1.94 | 2.894 (8) | 158 |
N2—H14···O7ii | 1.00 | 2.21 | 3.200 (7) | 171 |
Symmetry codes: (ii) x+1/2, y, −z+1/2; (v) x−1/2, y, −z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x, −y+1/2, z−1/2. |
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., 2002, 2002a; Paul, Choudhury & Rao, 2003), Ce (Wang et al., 2002), La (Bataille & Louer, 2002; Xing et al., 2003) and U (Doran et al., 2002, 2003a; Norquist et al., 2002, 2003; Stuart et al., 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. [C10H28N4][(UO2)2(SO4)4] is denoted USO-24 (uranium sulfate from Oxford). A displacement ellipsoid plot of USO-24 is shown in Fig. 1.
One unique uranium centre is present in USO-24. Atom U1 is seven-coordinate in a pentagonal bipyramidal geometry. Two short `uranyl' bonds to axial oxides are observed. The U1—O1 and U1—O2 bonds have lengths of 1.778 (4) and 1.764 (4) Å, respectively. These values are 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 178.93 (18)°. All five equatorial coordination sites around U1 are occupied by oxide ligands that bridge to adjacent sulfur centres, through distances ranging between 2.332 (4) and 2.456 (4) Å. Two distinct sulfur sites are observed in USO-24. Both S1 and S2 are at the centre of [SO4] tetrahedra. Atom S1 is bound to two oxide ligands that bridge to adjacent uranium centres and two terminal oxides. S1—Obridging distances are 1.492 (4) and 1.502 (4) Å, and S1—Oterminal distances are 1.447 (5) and 1.465 (5) Å. Atom S2 is bound to three oxide ligands that bridge to uranium centres and one terminal oxide. Atoms O5 and O6 bridge the same [UO2]2+ cation, resulting in a shared edge between the U1 and S1 polyhedra. These S—O bridging distances are 1.494 (4) and 1.497 (4) Å. The S2—Oterminal distance is 1.437 (5) Å.
Layers are formed because each uranium centre is connected to four others through four bridging sulfate tetrahedra (see Fig. 2). This layer structure is known in uranium chemistry (Doran et al., 2003b). These layers lie in the (101) plane and are separated by the template cations (See Fig. 3). The template cation is involved in hydrogen bonding with the layer (Table 2).