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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680301715X/ci6242sup1.cif
Contains datablocks global, USO-24

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680301715X/ci6242USO-24sup2.hkl
Contains datablock USO-24

CCDC reference: 222812

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](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

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., 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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot of the title compound, with the atomic numbering scheme. Ellipsoids are drawn at the 50% probability level. Atom O4# is at the symmetry position (x − 1/2, 1/2 − y, 1 − z) and O7# is at (1/2 + x, y, 1/2 − z).
[Figure 2] Fig. 2. Layers in USO-24. Green pentagonal bipyramids and blue tetrahedra represent [UO7] and [SO4], respectively.
[Figure 3] Fig. 3. The three-dimensional packing of USO-24. Green pentagonal bipyramids and blue tetrahedra represent [UO7] and [SO4], respectively.
(USO-24) top
Crystal data top
(C10H28N4)[(UO2)2(SO4)4]Dx = 2.766 Mg m3
Mr = 1128.66Melting point: not measured K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3482 reflections
a = 9.5831 (2) Åθ = 5–27°
b = 15.6060 (3) ŵ = 12.34 mm1
c = 18.1212 (3) ÅT = 150 K
V = 2710.10 (9) Å3Block, yellow
Z = 40.20 × 0.16 × 0.16 mm
F(000) = 2096.000
Data collection top
Enraf-Nonius KappaCCD
diffractometer
2219 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.02
ω scansθmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan
(Otwinowski & Minor, 1997)
h = 1212
Tmin = 0.11, Tmax = 0.14k = 2020
6194 measured reflectionsl = 2323
3091 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)] = 0.023 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 = 0.89Δρmax = 2.10 e Å3
2219 reflectionsΔρmin = 0.93 e Å3
182 parametersExtinction correction: Larson (1970), Crystallographic Computing eq 22
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 29.4 (27)
Crystal data top
(C10H28N4)[(UO2)2(SO4)4]V = 2710.10 (9) Å3
Mr = 1128.66Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 9.5831 (2) ŵ = 12.34 mm1
b = 15.6060 (3) ÅT = 150 K
c = 18.1212 (3) Å0.20 × 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 = 0.14Rint = 0.02
6194 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023182 parameters
wR(F2) = 0.053H-atom parameters not refined
S = 0.89Δρmax = 2.10 e Å3
2219 reflectionsΔρmin = 0.93 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
U10.424986 (19)0.299415 (12)0.367361 (11)0.0085
S10.72400 (14)0.29915 (9)0.48612 (7)0.0118
S20.19710 (14)0.35864 (9)0.25902 (8)0.0132
O10.3995 (4)0.1910 (3)0.3403 (2)0.0161
O20.4491 (4)0.4065 (3)0.3958 (2)0.0164
O70.1180 (4)0.2944 (3)0.2150 (2)0.0179
O50.1814 (4)0.3351 (3)0.3387 (2)0.0165
O60.3492 (4)0.3461 (3)0.2443 (2)0.0184
O40.7976 (4)0.2285 (3)0.5256 (2)0.0144
O80.6717 (5)0.3626 (3)0.5373 (3)0.0251
O30.6070 (4)0.2557 (3)0.4455 (2)0.0175
O100.1505 (5)0.4444 (3)0.2440 (3)0.0226
O90.8211 (5)0.3371 (3)0.4329 (2)0.0213
N10.1061 (5)0.0081 (3)0.0580 (3)0.0139
N20.4778 (6)0.1971 (4)0.1484 (3)0.0265
C10.0466 (6)0.0009 (4)0.0752 (3)0.0178
C40.3283 (7)0.0774 (5)0.1049 (4)0.0245
C30.1775 (7)0.0561 (4)0.1193 (4)0.0198
C20.1246 (7)0.0489 (4)0.0164 (4)0.0190
C50.3834 (11)0.1284 (7)0.1704 (5)0.0533
H20.05800.02900.12360.0215*
H30.08700.05990.07860.0215*
H90.38310.02330.09890.0291*
H80.33600.11260.05900.0291*
H70.17270.02040.16500.0239*
H60.12580.11100.12740.0239*
H40.22620.04990.02910.0242*
H50.08800.10890.01470.0242*
H110.43540.08840.20360.0652*
H100.30290.15390.19780.0652*
H140.51150.22810.19320.0322*
H130.55940.17250.12130.0322*
H120.42690.23790.11550.0322*
H10.15060.04970.05530.0166*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
U10.0068 (1)0.01131 (11)0.0075 (1)0.00065 (8)0.00020 (8)0.00045 (8)
S10.0108 (6)0.0126 (6)0.0121 (6)0.0001 (6)0.0031 (5)0.0009 (5)
S20.0094 (7)0.0165 (7)0.0137 (7)0.0015 (5)0.0017 (5)0.0025 (5)
O10.017 (2)0.016 (2)0.0151 (19)0.0030 (17)0.0025 (16)0.0014 (17)
O20.016 (2)0.0152 (19)0.0178 (19)0.0031 (17)0.0013 (17)0.0005 (18)
O70.0108 (18)0.022 (2)0.021 (2)0.0008 (18)0.0041 (16)0.0052 (19)
O50.013 (2)0.025 (2)0.0108 (18)0.0025 (18)0.0013 (16)0.0038 (18)
O60.009 (2)0.032 (2)0.014 (2)0.0014 (19)0.0001 (17)0.003 (2)
O40.015 (2)0.016 (2)0.0123 (18)0.0014 (17)0.0038 (16)0.0015 (16)
O80.024 (3)0.024 (2)0.027 (3)0.009 (2)0.003 (2)0.007 (2)
O30.013 (2)0.021 (2)0.018 (2)0.0006 (18)0.0095 (16)0.0028 (18)
O100.021 (2)0.021 (2)0.025 (2)0.0002 (19)0.002 (2)0.005 (2)
O90.024 (2)0.020 (2)0.019 (2)0.006 (2)0.0018 (19)0.0055 (19)
N10.013 (3)0.010 (2)0.018 (2)0.0031 (19)0.0004 (19)0.0014 (19)
N20.028 (3)0.024 (3)0.027 (3)0.010 (3)0.002 (2)0.000 (3)
C10.014 (3)0.020 (3)0.019 (3)0.001 (2)0.007 (2)0.003 (2)
C40.023 (3)0.028 (4)0.023 (3)0.010 (3)0.006 (3)0.003 (3)
C30.017 (3)0.018 (3)0.024 (3)0.003 (2)0.006 (2)0.005 (3)
C20.016 (3)0.018 (3)0.023 (3)0.002 (2)0.000 (3)0.000 (3)
C50.066 (6)0.062 (6)0.032 (4)0.052 (5)0.007 (4)0.002 (4)
Geometric parameters (Å, º) top
U1—O11.778 (4)N1—H11.00
U1—O21.764 (4)N2—C51.458 (9)
U1—O32.348 (4)N2—H121.00
U1—O4i2.332 (4)N2—H131.00
U1—O52.455 (4)N2—H141.00
U1—O62.456 (4)C1—C2iii1.516 (9)
U1—O7ii2.378 (4)C1—H21.00
S1—O31.502 (4)C1—H31.00
S1—O41.492 (4)C2—H41.00
S1—O81.447 (5)C2—H51.00
S1—O91.465 (5)C3—H61.00
S2—O51.497 (4)C3—H71.00
S2—O61.494 (4)C4—C31.506 (9)
S2—O71.489 (4)C4—C51.52 (1)
S2—O101.437 (5)C4—H81.00
N1—C11.500 (7)C4—H91.00
N1—C21.503 (8)C5—H101.00
N1—C31.504 (8)C5—H111.00
O1—U1—O2178.93 (18)C1—N1—H1111.1
O1—U1—O389.54 (18)C2—N1—C3113.5 (5)
O1—U1—O4i88.82 (17)C2—N1—H1106.6
O1—U1—O591.55 (17)C3—N1—H1107.0
O1—U1—O689.51 (18)C5—N2—H12109.2
O1—U1—O7ii84.40 (17)C5—N2—H13109.7
O2—U1—O390.07 (18)C5—N2—H14109.5
O2—U1—O4i90.13 (17)H12—N2—H13109.476
O2—U1—O588.36 (17)H12—N2—H14109.476
O2—U1—O691.34 (18)H13—N2—H14109.476
O2—U1—O7ii96.49 (17)N1—C1—C2iii112.0 (5)
O3—U1—O4i80.39 (15)N1—C1—H2108.8
O3—U1—O5154.13 (15)N1—C1—H3108.8
O3—U1—O6148.60 (14)C2iii—C1—H2108.8
O3—U1—O7ii77.92 (15)C2iii—C1—H3108.9
O4i—U1—O573.79 (14)H2—C1—H3109.467
O4i—U1—O6130.96 (14)N1—C2—C1iii110.8 (5)
O4i—U1—O7ii157.30 (15)N1—C2—H4109.2
O5—U1—O657.26 (13)N1—C2—H5109.1
O5—U1—O7ii127.90 (14)C1iii—C2—H4109.1
O6—U1—O7ii70.76 (14)C1iii—C2—H5109.2
O3—S1—O4104.8 (3)H4—C2—H5109.467
O3—S1—O8111.4 (3)N1—C3—C4114.7 (5)
O3—S1—O9109.5 (3)N1—C3—H6108.1
O4—S1—O8111.2 (3)N1—C3—H7108.2
O4—S1—O9108.3 (3)C4—C3—H6108.2
O8—S1—O9111.4 (3)C4—C3—H7108.1
O5—S2—O6103.7 (2)H6—C3—H7109.467
O5—S2—O7107.5 (3)C3—C4—C5108.2 (6)
O5—S2—O10112.3 (3)C3—C4—H8109.7
O6—S2—O7108.2 (3)C3—C4—H9109.7
O6—S2—O10113.0 (3)C5—C4—H8109.6
O7—S2—O10111.6 (3)C5—C4—H9110.1
U1—O3—S1136.0 (3)H8—C4—H9109.467
U1iv—O4—S1141.7 (3)N2—C5—C4112.7 (7)
U1—O5—S299.5 (2)N2—C5—H10108.9
U1—O6—S299.5 (2)N2—C5—H11108.4
U1v—O7—S2135.2 (3)C4—C5—H10109.1
C1—N1—C2109.4 (5)C4—C5—H11108.3
C1—N1—C3109.2 (5)H10—C5—H11109.467
Symmetry codes: (i) x1/2, 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) x1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O9vi1.001.802.763 (7)161
N2—H12···O9v1.002.053.033 (7)168
N2—H13···O8vii1.001.942.894 (8)158
N2—H14···O7ii1.002.213.200 (7)171
Symmetry codes: (ii) x+1/2, y, z+1/2; (v) x1/2, y, z+1/2; (vi) x+1, y1/2, z+1/2; (vii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula(C10H28N4)[(UO2)2(SO4)4]
Mr1128.66
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)150
a, b, c (Å)9.5831 (2), 15.6060 (3), 18.1212 (3)
V3)2710.10 (9)
Z4
Radiation typeMo Kα
µ (mm1)12.34
Crystal size (mm)0.20 × 0.16 × 0.16
Data collection
DiffractometerEnraf-Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(Otwinowski & Minor, 1997)
Tmin, Tmax0.11, 0.14
No. of measured, independent and
observed [I > 3σ(I)] reflections
6194, 3091, 2219
Rint0.02
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.053, 0.89
No. of reflections2219
No. of parameters182
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)2.10, 0.93

Computer programs: COLLECT (Nonius, 1997), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 1985), CRYSTALS (Watkin et al., 2001), CAMERON (Watkin et al., 1996), CRYSTALS.

Selected geometric parameters (Å, º) top
U1—O11.778 (4)S2—O51.497 (4)
U1—O21.764 (4)S2—O61.494 (4)
U1—O32.348 (4)S2—O71.489 (4)
U1—O4i2.332 (4)S2—O101.437 (5)
U1—O52.455 (4)N1—C11.500 (7)
U1—O62.456 (4)N1—C21.503 (8)
U1—O7ii2.378 (4)N1—C31.504 (8)
S1—O31.502 (4)N2—C51.458 (9)
S1—O41.492 (4)C1—C2iii1.516 (9)
S1—O81.447 (5)C4—C31.506 (9)
S1—O91.465 (5)C4—C51.52 (1)
O1—U1—O2178.93 (18)O3—S1—O9109.5 (3)
O1—U1—O389.54 (18)O4—S1—O8111.2 (3)
O1—U1—O4i88.82 (17)O4—S1—O9108.3 (3)
O1—U1—O591.55 (17)O8—S1—O9111.4 (3)
O1—U1—O689.51 (18)O5—S2—O6103.7 (2)
O1—U1—O7ii84.40 (17)O5—S2—O7107.5 (3)
O2—U1—O390.07 (18)O5—S2—O10112.3 (3)
O2—U1—O4i90.13 (17)O6—S2—O7108.2 (3)
O2—U1—O588.36 (17)O6—S2—O10113.0 (3)
O2—U1—O691.34 (18)O7—S2—O10111.6 (3)
O2—U1—O7ii96.49 (17)U1—O3—S1136.0 (3)
O3—U1—O4i80.39 (15)U1iv—O4—S1141.7 (3)
O3—U1—O5154.13 (15)U1—O5—S299.5 (2)
O3—U1—O6148.60 (14)U1—O6—S299.5 (2)
O3—U1—O7ii77.92 (15)U1v—O7—S2135.2 (3)
O4i—U1—O573.79 (14)C1—N1—C2109.4 (5)
O4i—U1—O6130.96 (14)C1—N1—C3109.2 (5)
O4i—U1—O7ii157.30 (15)C2—N1—C3113.5 (5)
O5—U1—O657.26 (13)N1—C1—C2iii112.0 (5)
O5—U1—O7ii127.90 (14)N1—C2—C1iii110.8 (5)
O6—U1—O7ii70.76 (14)N1—C3—C4114.7 (5)
O3—S1—O4104.8 (3)C3—C4—C5108.2 (6)
O3—S1—O8111.4 (3)N2—C5—C4112.7 (7)
Symmetry codes: (i) x1/2, 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) x1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O9vi1.001.802.763 (7)161
N2—H12···O9v1.002.053.033 (7)168
N2—H13···O8vii1.001.942.894 (8)158
N2—H14···O7ii1.002.213.200 (7)171
Symmetry codes: (ii) x+1/2, y, z+1/2; (v) x1/2, y, z+1/2; (vi) x+1, y1/2, z+1/2; (vii) x, y+1/2, z1/2.
 

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