catena-Poly­[1-methyl­piperazinium [[aquadioxouranium(VI)]-di-μ-sulfato-κ⁴O:O′]]

The title compound, [C₅H₁₄N₂][UO₂(H₂O)(SO₄)₂], contains anionic [UO₂(H₂O)(SO₄)₂]²⁻ chains with 1-methyl­piper­azinium cations balancing the charge. Each U^VI 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.

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

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S1. Comment

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 - O_bridging and S - O_terminal 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.

S2. Experimental

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.

S3. Refinement

H atoms placed geometrically after each cycle

Computing details

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

	Fig. 1. Chains in USO-22. Green pentagonal bipyramids, and blue tetrahedra represent [UO7] and [SO4] respectively.
	Fig. 2. Three-dimensional packing of USO-22. Green pentagonal bipyramids, and blue tetrahedra represent [UO7] and [SO4] respectively.
	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)

Crystal data

C5H16N2O11S2U	Z = 2
Mr = 582.35	F(000) = 523.717
Triclinic, P1	Dx = 2.906 Mg m^−3
Hall symbol: -P 1	Melting point: not measured K
a = 8.0031 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1873 (2) Å	Cell parameters from 2832 reflections
c = 10.8911 (3) Å	θ = 5–27°
α = 72.704 (1)°	µ = 12.57 mm^−1
β = 81.7766 (11)°	T = 150 K
γ = 78.7917 (9)°	Block, yellow
V = 665.60 (3) Å^3	0.10 × 0.10 × 0.10 mm

Data collection

Enraf Nonius Kappa CCD diffractometer	2640 reflections with > 3.00σ(I)
Graphite monochromator	Rint = 0.02
ω scans	θmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan (Otwinowsky & Minor, 1996)	h = −10→10
Tmin = 0.28, Tmax = 0.28	k = −10→10
5594 measured reflections	l = −13→14
3026 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.021	Chebychev polynomial with 5 parameters, Carruthers & Watkin , 1979, 8.86 4.95 9.20 0.122E-01 2.37
wR(F^2) = 0.054	(Δ/σ)max = 0.002
S = 1.01	Δρmax = 0.99 e Å^−3
2640 reflections	Δρmin = −0.92 e Å^−3
191 parameters	Extinction correction: Larson 1970 Crystallographic Computing eq 22
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 16.5 (15)
Secondary atom site location: difference Fourier map

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
U1	−0.61840 (2)	0.25038 (2)	1.251849 (15)	0.0076
S1	−0.70037 (14)	−0.10688 (15)	1.51706 (11)	0.0109
S2	−0.26874 (14)	0.36159 (14)	1.00541 (11)	0.0099
O1	−0.6476 (4)	0.4238 (4)	1.3239 (3)	0.0144
O2	−0.5951 (4)	0.0800 (4)	1.1778 (3)	0.0131
O3	−0.9302 (5)	0.3046 (5)	1.2312 (3)	0.0202
O4	−0.7485 (4)	0.0775 (4)	1.4377 (3)	0.0130
O5	−0.3965 (4)	0.0968 (5)	1.3785 (3)	0.0141
O6	−0.3500 (4)	0.3244 (5)	1.1399 (3)	0.0144
O7	−0.3142 (4)	0.5528 (4)	0.9467 (3)	0.0140
O8	−0.8554 (5)	−0.1780 (5)	1.5744 (4)	0.0208
O9	−0.5933 (5)	−0.2107 (5)	1.4386 (3)	0.0174
O10	−0.3315 (5)	0.2662 (5)	0.9326 (3)	0.0172
O11	−0.0823 (4)	0.3178 (5)	1.0078 (3)	0.0161
N1	0.0591 (6)	0.2568 (6)	0.7538 (4)	0.0183
N2	0.4122 (6)	0.2749 (6)	0.7823 (4)	0.0183
C1	0.1699 (7)	0.3628 (7)	0.6450 (5)	0.0225
C2	0.3045 (7)	0.4266 (7)	0.6957 (6)	0.0235
C3	0.3022 (7)	0.1738 (7)	0.8877 (5)	0.0187
C4	0.1731 (6)	0.1093 (7)	0.8331 (5)	0.0167
C5	−0.0697 (7)	0.1945 (9)	0.6991 (6)	0.0273
H1	−1.0088	0.2877	1.3123	0.0229*
H2	−0.9754	0.3399	1.1446	0.0229*
H3	−0.0054	0.3299	0.8095	0.0224*
H4	0.0953	0.4646	0.5926	0.0273*
H5	0.2289	0.2878	0.5882	0.0273*
H6	0.3803	0.4875	0.6211	0.0291*
H7	0.2477	0.5095	0.7459	0.0291*
H8	0.4757	0.1970	0.7298	0.0221*
H9	0.4955	0.3190	0.8200	0.0221*
H10	0.3756	0.0726	0.9433	0.0226*
H11	0.2402	0.2499	0.9429	0.0226*
H12	0.1018	0.0380	0.9058	0.0204*
H13	0.2346	0.0333	0.7778	0.0204*
H14	−0.1429	0.1255	0.7702	0.0402*
H15	−0.1452	0.2969	0.6461	0.0402*
H16	−0.0102	0.1207	0.6422	0.0402*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.0081 (1)	0.0079 (1)	0.0053 (1)	−0.00126 (6)	−0.00067 (6)	0.00029 (6)
S1	0.0094 (5)	0.0125 (5)	0.0088 (5)	−0.0028 (4)	−0.0014 (4)	0.0009 (4)
S2	0.0093 (5)	0.0097 (5)	0.0087 (5)	−0.0013 (4)	−0.0007 (4)	0.0001 (4)
O1	0.0181 (17)	0.0115 (16)	0.0141 (16)	0.0006 (13)	−0.0040 (13)	−0.0050 (13)
O2	0.0166 (16)	0.0113 (16)	0.0113 (16)	−0.0020 (13)	0.0016 (13)	−0.0044 (13)
O3	0.0144 (17)	0.029 (2)	0.0125 (17)	−0.0077 (15)	0.0025 (13)	0.0013 (15)
O4	0.0122 (15)	0.0154 (17)	0.0070 (14)	−0.0020 (13)	−0.0009 (12)	0.0036 (13)
O5	0.0124 (15)	0.0192 (18)	0.0089 (15)	−0.0006 (13)	−0.0033 (12)	−0.0012 (13)
O6	0.0145 (16)	0.0201 (18)	0.0051 (15)	−0.0040 (13)	−0.0018 (12)	0.0030 (13)
O7	0.0167 (16)	0.0085 (16)	0.0137 (16)	−0.0021 (13)	−0.0001 (13)	0.0010 (13)
O8	0.0147 (17)	0.027 (2)	0.0145 (17)	−0.0102 (15)	−0.0006 (14)	0.0076 (15)
O9	0.0221 (18)	0.0146 (17)	0.0143 (17)	−0.0042 (14)	0.0012 (14)	−0.0027 (14)
O10	0.0221 (18)	0.0148 (17)	0.0171 (18)	−0.0055 (14)	−0.0045 (14)	−0.0051 (14)
O11	0.0068 (15)	0.0199 (18)	0.0188 (17)	0.0006 (13)	−0.0006 (13)	−0.0032 (15)
N1	0.014 (2)	0.022 (2)	0.020 (2)	0.0028 (16)	−0.0048 (16)	−0.0098 (18)
N2	0.0136 (19)	0.020 (2)	0.022 (2)	−0.0024 (16)	−0.0042 (17)	−0.0051 (18)
C1	0.027 (3)	0.020 (3)	0.019 (3)	−0.002 (2)	−0.003 (2)	−0.004 (2)
C2	0.023 (3)	0.020 (3)	0.028 (3)	−0.002 (2)	−0.008 (2)	−0.005 (2)
C3	0.017 (2)	0.023 (3)	0.016 (2)	−0.0012 (19)	−0.0019 (19)	−0.006 (2)
C4	0.018 (2)	0.016 (2)	0.015 (2)	−0.0006 (19)	−0.0013 (18)	−0.0033 (19)
C5	0.013 (2)	0.045 (4)	0.036 (3)	−0.005 (2)	−0.005 (2)	−0.026 (3)

Geometric parameters (Å, º)

U1—O1	1.780 (3)	N2—C3	1.485 (7)
U1—O2	1.776 (3)	C1—C2	1.516 (8)
U1—O3	2.479 (4)	C3—C4	1.508 (7)
U1—O4	2.335 (3)	N1—H3	1.000
U1—O5	2.332 (3)	N2—H9	1.001
U1—O6	2.405 (3)	N2—H8	1.000
U1—O7^i	2.342 (3)	O3—H1	0.999
S1—O4	1.506 (3)	O3—H2	0.999
S1—O5^ii	1.496 (3)	C4—H12	1.009
S1—O8	1.453 (4)	C4—H13	1.005
S1—O9	1.458 (4)	C3—H11	1.006
S2—O6	1.483 (3)	C3—H10	1.006
S2—O7	1.497 (3)	C1—H4	0.999
S2—O10	1.458 (4)	C1—H5	1.006
S2—O11	1.467 (3)	C2—H7	0.999
N1—C1	1.527 (7)	C2—H6	1.006
N1—C4	1.488 (6)	C5—H15	1.008
N1—C5	1.496 (7)	C5—H14	1.001
N2—C2	1.515 (7)	C5—H16	1.002
O1—U1—O2	178.31 (15)	N1—C1—C2	112.1 (5)
O1—U1—O3	89.18 (15)	N2—C2—C1	110.0 (4)
O1—U1—O4	90.83 (14)	N2—C3—C4	110.7 (4)
O1—U1—O5	91.77 (14)	N1—C4—C3	110.8 (4)
O1—U1—O6	91.66 (14)	C4—N1—H3	109.278
O1—U1—O7^i	90.42 (14)	C1—N1—H3	110.404
O2—U1—O3	89.25 (14)	C5—N1—H3	107.340
O2—U1—O4	89.29 (14)	C3—N2—H9	109.830
O2—U1—O5	89.88 (14)	C2—N2—H9	109.360
O2—U1—O6	89.21 (14)	C3—N2—H8	108.413
O2—U1—O7^i	88.42 (14)	C2—N2—H8	108.909
O3—U1—O4	72.07 (12)	H9—N2—H8	109.698
O3—U1—O5	146.50 (12)	U1—O3—H1	117.766
O3—U1—O6	142.97 (11)	U1—O3—H2	121.016
O3—U1—O7^i	68.63 (12)	H1—O3—H2	121.207
O4—U1—O5	74.44 (11)	N1—C4—H12	109.346
O4—U1—O6	144.89 (11)	C3—C4—H12	109.694
O4—U1—O7^i	140.65 (12)	N1—C4—H13	109.257
O5—U1—O6	70.48 (11)	C3—C4—H13	109.424
O5—U1—O7^i	144.81 (12)	H12—C4—H13	108.298
O6—U1—O7^i	74.35 (11)	N2—C3—H11	109.225
O4—S1—O5^ii	105.6 (2)	C4—C3—H11	109.210
O4—S1—O8	109.0 (2)	N2—C3—H10	109.499
O4—S1—O9	110.9 (2)	C4—C3—H10	109.668
O5^ii—S1—O8	109.4 (2)	H11—C3—H10	108.459
O5^ii—S1—O9	110.3 (2)	N1—C1—H4	109.161
O8—S1—O9	111.4 (2)	C2—C1—H4	109.077
O6—S2—O7	106.5 (2)	N1—C1—H5	108.642
O6—S2—O10	110.8 (2)	C2—C1—H5	108.717
O6—S2—O11	109.2 (2)	H4—C1—H5	109.053
O7—S2—O10	110.5 (2)	N2—C2—H7	109.322
O7—S2—O11	108.6 (2)	C1—C2—H7	109.580
O10—S2—O11	111.2 (2)	N2—C2—H6	109.313
U1—O4—S1	132.9 (2)	C1—C2—H6	109.536
U1—O5—S1^ii	141.6 (2)	H7—C2—H6	109.108
U1—O6—S2	137.6 (2)	N1—C5—H15	109.680
U1^i—O7—S2	139.7 (2)	N1—C5—H14	110.367
C1—N1—C4	108.3 (4)	H15—C5—H14	108.794
C1—N1—C5	110.2 (4)	N1—C5—H16	109.963
C2—N2—C3	110.6 (4)	H15—C5—H16	108.718
C4—N1—C5	111.3 (4)	H14—C5—H16	109.285

Symmetry codes: (i) −x−1, −y+1, −z+2; (ii) −x−1, −y, −z+3.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3···S2	1.00	2.81	3.687 (5)	147
N1—H3···O11	1.00	2.14	2.982 (6)	141
O3—H2···S2^iii	1.00	2.92	3.786 (4)	145
O3—H2···O11	1.00	1.89	2.838 (5)	157
N2—H8···O2^iv	1.00	2.27	2.924 (5)	122
C4—H13···O5^iv	1.00	2.37	3.364 (7)	169
N2—H8···O9^iv	1.00	1.92	2.761 (6)	140
C2—H7···O6^v	1.00	2.41	3.184 (8)	134
N2—H9···O10^vi	1.00	1.88	2.780 (7)	147

Symmetry codes: (iii) x−1, y, z; (iv) −x, −y, −z+2; (v) −x, −y+1, −z+2; (vi) x+1, y, z.