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The title compound, (C6H16N2)[UO2(SO4)2]·2H2O, contains anionic [UO2(SO4)2]2− chains with cyclo­hexane-1,4-di­ammonium cations balancing the charge. Each UVI atom is seven-coordinate in a pentagonal bipyramidal geometry and the sulfate tetrahedra either bridge between two adjacent uranium centres or share an edge with a single [UO7] polyhedron.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803015836/cf6264sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803015836/cf6264Isup2.hkl
Contains datablock I

CCDC reference: 222813

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.020
  • wR factor = 0.047
  • Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.99
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 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 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

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, Chaudhury, 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, 2003; 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, [C6H16N2][UO2(SO4)2], (I), denoted USO-23 (uranium sulfate from Oxford).

One distinct uranium environment is observed in USO-23. U1 is seven-coordinate in a pentagonal bipyramidal geometry. It is bound to two oxide ligands through short `uranyl' bonds. The U1O1 and U1O2 distances are 1.761 (3) and 1.771 (3) Å, respectively; these distance are close to the average reported value of 1.758 (4) Å (Burns et al., 1997), and the O1—U1—O2 angle is close to linear, with a value of 178.73 (13)°. The five equatorial coordination sites are occupied by O atoms that belong to the sulfates·Atoms O3, O4 and O5 bridge to different sulfur centres, through U—O distances ranging between 2.354 (3) and 2.381 (3) Å. The remaining two O atoms are bound to a single sulfur centre. These U—O bonds are longer, with distances of 2.450 (3) and 2.451 (3) Å to O6 and O7, respectively. Two different sulfur environments are present in USO-23. Both S1 and S2 are bound to four O atoms in a tetrahedral fashion. However, the tetrahedron containing S1 bridges between three adjacent uranium centres, each through a single shared corner, while the S2 tetrahedra share an edge with a single uranium centre. The bridging O atoms exhibit longer S—O bonds, with lengths ranging between 1.480 (3) and 1.510 (3) Å, than the terminal O atoms. These S—Oterm bonds have lengths ranging between 1.445 (3) and 1.459 (3) Å.

The [UO7] and [SO4] polyhedra share three corners with one another, creating one-dimensional chains (Fig. 1). The formula of the chain backbone is [UO2(SO4)3/3]. This chain type is known in uranium chemistry (Norquist et al., 2003; Doran et al., 2003; Brandeburg & Loopstra, 1973; van der Putten & Loopstra, 1974; Zalkin et al., 1978; Serezhkin et al., 1981). The two non-backbone equatorial coordination sites on each [UO7] polyhedron are occupied by an edge-shared sulfate anion. The protonated 1,4-diaminocyclohexane cations, (C6H16N2)2+, reside between chains, balancing the charge (Fig. 2). A displacement ellipsoid plot is shown in Fig. 3.

Experimental top

0.4419 g (1.04 mmol) of UO2(CH3CO2)2·2H2O, 0.3001 g (3.06 mmol) of H2SO4, 0.024 g (0.211 mmol) of 1,4-diaminocyclohexane and 1.0002 g (55.5 mmol) of water were placed in a 23 ml teflon-lined autoclave. The autoclave was heated to 453 K for 24 h, at which point it was slowly 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 positioned geometrically, with bond lengths of 1.00 Å and Uiso set at 1.2Ueq of the carrier atom; the positions were recalculated after each refinement cycle.

Computing details top

Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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.

Figures top
[Figure 1] Fig. 1. Chains in USO-23. Green pentagonal bipyramids and blue tetrahedra represent [UO7] and [SO4], respectively.
[Figure 2] Fig. 2. Three-dimensional packing of USO-23. Green pentagonal bipyramids and blue tetrahedra represent [UO7] and [SO4], respectively. H atoms have been omitted for clarity.
[Figure 3] Fig. 3. Displacement ellipsoid plot of the title compound, with the atomic numbering scheme. Ellipsoids are drawn at the 50% probability level.
(I) top
Crystal data top
(C6H16N2)[UO2(SO4)2]·2H2OZ = 2
Mr = 614.39F(000) = 559.718
Triclinic, P1Dx = 2.508 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7813 (1) ÅCell parameters from 3432 reflections
b = 10.0636 (2) Åθ = 5–27°
c = 12.9753 (3) ŵ = 10.30 mm1
α = 76.7537 (7)°T = 150 K
β = 75.6074 (7)°Rod, yellow
γ = 74.3971 (13)°0.50 × 0.06 × 0.04 mm
V = 813.50 (4) Å3
Data collection top
Enraf Nonius Kappa CCD
diffractometer
3353 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.020
ω scansθmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan
(Otwinowski & Minor, 1997)
h = 88
Tmin = 0.51, Tmax = 0.66k = 1313
6840 measured reflectionsl = 1616
3700 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)] = 0.020 Chebychev polynomial with 5 parameters (Carruthers & Watkin, 1979), 13.4, 18.9, 11.8, 4.59, 1.99
wR(F2) = 0.047(Δ/σ)max = 0.001
S = 0.87Δρmax = 1.31 e Å3
3353 reflectionsΔρmin = 1.11 e Å3
209 parametersExtinction correction: Larson (1970), equation 22
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 15.9 (15)
Crystal data top
(C6H16N2)[UO2(SO4)2]·2H2Oγ = 74.3971 (13)°
Mr = 614.39V = 813.50 (4) Å3
Triclinic, P1Z = 2
a = 6.7813 (1) ÅMo Kα radiation
b = 10.0636 (2) ŵ = 10.30 mm1
c = 12.9753 (3) ÅT = 150 K
α = 76.7537 (7)°0.50 × 0.06 × 0.04 mm
β = 75.6074 (7)°
Data collection top
Enraf Nonius Kappa CCD
diffractometer
3700 independent reflections
Absorption correction: multi-scan
(Otwinowski & Minor, 1997)
3353 reflections with I > 3σ(I)
Tmin = 0.51, Tmax = 0.66Rint = 0.020
6840 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.020209 parameters
wR(F2) = 0.047H-atom parameters not refined
S = 0.87Δρmax = 1.31 e Å3
3353 reflectionsΔρmin = 1.11 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
U10.23167 (2)0.667358 (14)0.165208 (11)0.0078
S10.25911 (13)0.54458 (9)0.09811 (7)0.0111
S20.25331 (14)0.90528 (9)0.36488 (7)0.0135
O90.3559 (5)0.8790 (4)0.4724 (2)0.0247
O10.0897 (4)0.7874 (3)0.0788 (2)0.0165
O20.3693 (4)0.5469 (3)0.2532 (2)0.0148
O50.0747 (4)0.5985 (3)0.1635 (2)0.0162
O100.1602 (5)1.0536 (3)0.3631 (3)0.0217
O70.4009 (4)0.8468 (3)0.2883 (2)0.0169
O60.0863 (4)0.8228 (3)0.3166 (2)0.0181
N10.1853 (5)0.2402 (4)0.4222 (3)0.0180
O80.2639 (4)0.4160 (3)0.1297 (2)0.0174
O40.2467 (4)0.4785 (3)0.0179 (2)0.0148
O30.5512 (4)0.6548 (3)0.1145 (2)0.0159
N20.4591 (6)0.2429 (4)0.1654 (3)0.0202
C50.3385 (6)0.0279 (4)0.0659 (3)0.0173
C10.0918 (6)0.3915 (4)0.4335 (3)0.0158
C60.6671 (6)0.0754 (4)0.0409 (3)0.0189
C40.4472 (6)0.1393 (4)0.0611 (3)0.0153
C30.2290 (6)0.4443 (4)0.4847 (3)0.0179
C20.1289 (6)0.4034 (4)0.5006 (3)0.0192
O110.1043 (5)0.2817 (3)0.2505 (3)0.0245
O120.2903 (5)0.9040 (4)0.6784 (3)0.0333
H170.41880.02340.12700.0217*
H180.19350.07190.07810.0217*
H80.08290.45230.36090.0182*
H200.73560.15120.03880.0227*
H190.75150.02410.10140.0227*
H160.36290.18780.00080.0170*
H110.24450.38440.55680.0220*
H120.37170.43910.43680.0220*
H100.12320.34290.57350.0232*
H90.21540.37020.46370.0232*
H60.33080.23090.37800.0218*
H50.19040.18130.49560.0218*
H70.09850.20670.38590.0218*
H140.31510.28650.17990.0237*
H150.52590.31820.16060.0237*
H130.54440.19370.22640.0237*
H20.13360.19400.28080.0292*
H10.04230.29990.20810.0292*
H30.13790.93180.67940.0389*
H40.31100.86850.60250.0389*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
U10.00624 (8)0.00908 (8)0.00811 (8)0.00227 (4)0.00245 (4)0.00009 (4)
S10.0087 (4)0.0130 (4)0.0119 (4)0.0040 (3)0.0033 (3)0.0003 (3)
S20.0152 (4)0.0124 (4)0.0128 (4)0.0040 (3)0.0048 (3)0.0014 (3)
O90.0295 (16)0.0301 (17)0.0153 (14)0.0085 (13)0.0032 (12)0.0044 (12)
O10.0179 (13)0.0161 (13)0.0164 (13)0.002 (1)0.0052 (11)0.0045 (11)
O20.0159 (13)0.0140 (13)0.0138 (12)0.004 (1)0.002 (1)0.002 (1)
O50.0141 (13)0.0232 (14)0.0134 (12)0.0101 (11)0.004 (1)0.0011 (11)
O100.0246 (15)0.0151 (14)0.0246 (15)0.0033 (11)0.0090 (12)0.0011 (11)
O70.0165 (13)0.0182 (14)0.0175 (13)0.0068 (11)0.0070 (11)0.0016 (11)
O60.0178 (13)0.0162 (13)0.0215 (14)0.0075 (11)0.0084 (11)0.0038 (11)
N10.0192 (16)0.0160 (16)0.0192 (16)0.0035 (13)0.0048 (13)0.0035 (13)
O80.0155 (13)0.0155 (13)0.0229 (14)0.005 (1)0.0046 (11)0.0044 (11)
O40.0154 (13)0.0172 (13)0.0111 (12)0.004 (1)0.005 (1)0.002 (1)
O30.0142 (13)0.0134 (13)0.0189 (13)0.000 (1)0.006 (1)0.001 (1)
N20.0222 (17)0.0143 (16)0.0231 (18)0.0044 (13)0.0063 (14)0.0006 (13)
C50.0175 (18)0.0159 (18)0.0227 (19)0.0059 (14)0.0085 (15)0.0040 (15)
C10.0144 (17)0.0150 (17)0.0180 (18)0.0025 (14)0.0045 (14)0.0027 (14)
C60.0198 (19)0.0163 (18)0.0222 (19)0.0068 (15)0.0069 (15)0.0001 (15)
C40.0178 (18)0.0093 (16)0.0169 (18)0.0011 (13)0.0024 (14)0.0021 (13)
C30.0126 (17)0.0194 (19)0.0227 (19)0.0025 (14)0.0042 (14)0.0062 (15)
C20.0182 (19)0.0200 (19)0.0212 (19)0.0080 (15)0.0020 (15)0.0049 (15)
O110.0214 (15)0.0252 (16)0.0263 (16)0.0022 (12)0.0044 (12)0.0073 (13)
O120.0248 (17)0.051 (2)0.0213 (16)0.0002 (15)0.0058 (13)0.0087 (15)
Geometric parameters (Å, º) top
U1—O11.761 (3)C5—C6iv1.529 (6)
U1—O21.771 (3)O11—H11.000
U1—O32.381 (3)O11—H21.000
U1—O42.367 (3)O12—H30.998
U1—O52.354 (3)O12—H40.999
U1—O62.450 (3)N1—H51.003
U1—O72.451 (3)N1—H61.002
S1—O3i1.480 (3)N1—H71.000
S1—O4ii1.489 (3)N2—H131.002
S1—O51.485 (3)N2—H141.002
S1—O81.454 (3)N2—H151.002
S2—O61.510 (3)C1—H81.004
S2—O71.498 (3)C2—H91.001
S2—O91.445 (3)C2—H101.004
S2—O101.459 (3)C3—H111.003
N1—C11.510 (5)C3—H121.007
N2—C41.506 (5)C4—H161.005
C1—C21.522 (5)C5—H171.007
C1—C31.524 (5)C5—H181.000
C2iii—C31.536 (6)C6—H191.007
C4—C51.517 (5)C6—H201.002
C4—C61.519 (5)
O1—U1—O2178.73 (13)N2—C4—C6108.7 (3)
O1—U1—O392.29 (11)C5—C4—C6111.6 (3)
O1—U1—O491.55 (11)C4—C5—C6iv108.4 (3)
O1—U1—O590.89 (12)C4—C6—C5iv110.4 (3)
O1—U1—O690.48 (12)C1—N1—H5109.552
O1—U1—O791.12 (12)C1—N1—H6109.678
O2—U1—O388.97 (11)C1—N1—H7109.968
O2—U1—O488.81 (11)H5—N1—H6109.057
O2—U1—O587.97 (11)H5—N1—H7109.274
O2—U1—O688.67 (11)H6—N1—H7109.293
O2—U1—O789.22 (11)C4—N2—H13109.612
O3—U1—O476.52 (9)C4—N2—H14109.854
O3—U1—O5157.2 (1)C4—N2—H15109.942
O3—U1—O6128.23 (9)H13—N2—H14109.146
O3—U1—O771.36 (9)H13—N2—H15109.134
O4—U1—O580.81 (9)H14—N2—H15109.132
O4—U1—O6155.06 (9)N1—C1—H8110.892
O4—U1—O7147.84 (9)C2—C1—H8107.993
O5—U1—O674.31 (9)C3—C1—H8107.522
O5—U1—O7131.18 (9)C1—C2—H9109.473
O6—U1—O756.91 (9)C1—C2—H10109.107
O3i—S1—O4ii107.76 (16)C3iii—C2—H9109.583
O3i—S1—O5107.99 (17)C3iii—C2—H10109.069
O3i—S1—O8111.13 (16)H9—C2—H10109.067
O4ii—S1—O5107.95 (15)C1—C3—H11109.818
O4ii—S1—O8111.40 (17)C1—C3—H12109.724
O5—S1—O8110.47 (17)C2iii—C3—H11109.486
O6—S2—O7101.85 (16)C2iii—C3—H12109.541
O6—S2—O9111.16 (18)H11—C3—H12108.679
O6—S2—O10109.02 (17)N2—C4—H16110.272
O7—S2—O9110.66 (18)C5—C4—H16107.208
O7—S2—O10111.43 (17)C6—C4—H16108.670
O9—S2—O10112.26 (19)C4—C5—H17109.614
U1—O3—S1v135.88 (17)C4—C5—H18110.294
U1—O4—S1ii137.50 (17)C6iv—C5—H17109.325
U1—O5—S1147.46 (17)C6iv—C5—H18110.295
U1—O6—S2100.44 (14)H17—C5—H18108.902
U1—O7—S2100.74 (14)C4—C6—H19109.221
N1—C1—C2108.8 (3)C4—C6—H20109.862
N1—C1—C3109.9 (3)C5iv—C6—H19108.934
C2—C1—C3111.7 (3)C5iv—C6—H20109.716
C1—C2—C3iii110.5 (3)H19—C6—H20108.702
C1—C3—C2iii109.6 (3)H2—O11—H1109.438
N2—C4—C5110.4 (3)H3—O12—H4109.765
Symmetry codes: (i) x1, y, z; (ii) x, y+1, z; (iii) x, y+1, z+1; (iv) x+1, y, z; (v) x+1, y, z.

Experimental details

Crystal data
Chemical formula(C6H16N2)[UO2(SO4)2]·2H2O
Mr614.39
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)6.7813 (1), 10.0636 (2), 12.9753 (3)
α, β, γ (°)76.7537 (7), 75.6074 (7), 74.3971 (13)
V3)813.50 (4)
Z2
Radiation typeMo Kα
µ (mm1)10.30
Crystal size (mm)0.50 × 0.06 × 0.04
Data collection
DiffractometerEnraf Nonius Kappa CCD
diffractometer
Absorption correctionMulti-scan
(Otwinowski & Minor, 1997)
Tmin, Tmax0.51, 0.66
No. of measured, independent and
observed [I > 3σ(I)] reflections
6840, 3700, 3353
Rint0.020
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.047, 0.87
No. of reflections3353
No. of parameters209
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)1.31, 1.11

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

Selected geometric parameters (Å, º) top
U1—O11.761 (3)S1—O4ii1.489 (3)
U1—O21.771 (3)S1—O51.485 (3)
U1—O32.381 (3)S1—O81.454 (3)
U1—O42.367 (3)S2—O61.510 (3)
U1—O52.354 (3)S2—O71.498 (3)
U1—O62.450 (3)S2—O91.445 (3)
U1—O72.451 (3)S2—O101.459 (3)
S1—O3i1.480 (3)
O1—U1—O2178.73 (13)O4ii—S1—O5107.95 (15)
O1—U1—O392.29 (11)O4ii—S1—O8111.40 (17)
O1—U1—O491.55 (11)O5—S1—O8110.47 (17)
O1—U1—O590.89 (12)O6—S2—O7101.85 (16)
O1—U1—O690.48 (12)O6—S2—O9111.16 (18)
O1—U1—O791.12 (12)O6—S2—O10109.02 (17)
O2—U1—O388.97 (11)O7—S2—O9110.66 (18)
O2—U1—O488.81 (11)O7—S2—O10111.43 (17)
O2—U1—O587.97 (11)O9—S2—O10112.26 (19)
O2—U1—O688.67 (11)U1—O3—S1iii135.88 (17)
O2—U1—O789.22 (11)U1—O4—S1ii137.50 (17)
O3—U1—O476.52 (9)U1—O5—S1147.46 (17)
O3—U1—O5157.2 (1)U1—O6—S2100.44 (14)
O3—U1—O6128.23 (9)U1—O7—S2100.74 (14)
O3—U1—O771.36 (9)N1—C1—C2108.8 (3)
O4—U1—O580.81 (9)N1—C1—C3109.9 (3)
O4—U1—O6155.06 (9)C2—C1—C3111.7 (3)
O4—U1—O7147.84 (9)C1—C2—C3iv110.5 (3)
O5—U1—O674.31 (9)C1—C3—C2iv109.6 (3)
O5—U1—O7131.18 (9)N2—C4—C5110.4 (3)
O6—U1—O756.91 (9)N2—C4—C6108.7 (3)
O3i—S1—O4ii107.76 (16)C5—C4—C6111.6 (3)
O3i—S1—O5107.99 (17)C4—C5—C6v108.4 (3)
O3i—S1—O8111.13 (16)C4—C6—C5v110.4 (3)
Symmetry codes: (i) x1, y, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y+1, z+1; (v) x+1, y, z.
 

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