Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, {(C4H12N)[UO2(NO3)(SO4)]}n, contains one-dimensional anionic [UO2(NO3)(SO4)] chains, with the charge balanced by tetra­methyl­ammonium cations. Each U atom is seven-coordinate, in a pentagonal bipyramidal geometry. Each sulfate tetrahedron bridges three adjacent uranium centres and each nitrate anion shares an edge with a [UO7] polyhedron.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803010808/na6235sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803010808/na6235Isup2.hkl
Contains datablock I

CCDC reference: 214793

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](N-C) = 0.009 Å
  • R factor = 0.024
  • wR factor = 0.048
  • Data-to-parameter ratio = 13.1

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 analagous 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), Cd (Paul et al., 2002; Choudhury et al., 2001), Fe (Paul et al., 2002; Paul, Choudhury, 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 nitrate. (C4H12N)[UO2(NO3)(SO4)] is denoted USO-21 (uranium sulfate from Oxford). [The Paul et al. (2002) references need to be distinguished as 2002, 2002a or 2002b according to the reference list; also there are three Paul et al. (2002) references in the reference list and only two cited in the Comment]

One unique uranium centre is present in USO-21. 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 1.763 (6) and 1.763 (6) Å, respectively, close to the average reported value of 1.758 (4) Å (Burns et al., 1997) and the O1—U1—O2 angle is close to 180°, with a value of 178.1 (3)°. Three of the five equatorial coordination sites around U1 are occupied by oxide ligands that are bound to sulfur centres through bonds with distances ranging between 2.317 (4) and 2.320 (6) Å. The fourth and fifth equatorial coordination site is occupied by oxide ligands that are bound to a single nitrogen centre, with a U1—O3 distance of 2.498 (4) Å. One unique sulfur environment exists in USO-21. The sulfate tetrahedron, which contains S1, bridges between three adjacent uranium centres. The bonds between S1 and the bridging oxides, O4 and O5, are longer than the bond from S1 to the lone terminal oxide, O7, these lengths are 1.486 (4) × 2 and 1.493 (6) versus 1.433 (7) Å. The nitrate anion, containing N1, shares an edge with the [UO7] pentagonal bipyramid through bridging O3 ligands. These distances are longer than the bond from N1 to O6, the terminal oxide. The distances are 1.282 (5) Å × 2 versus 1.213 (9) 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; 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 nitrate anion. The tetramethylammonium cations, [C4H12N]+, reside between chains, balancing charge (Fig. 2). A displacement ellipsoid plot is shown in Fig. 3.

Experimental top

USO-21 was prepared by dissolving 0.2 g (8 × 10−5 mol) of (C4H12N)2[(UO2)6(H2O)2(SO4)7] (MUS-1; Doran et al., 2002) in 5 ml of a 2 M Mg(NO3)2.6H2O solution. The resulting solution was allowed to slowly evaporate. Yellow crystals were isolated after one month.

Refinement top

H atoms placed geometrically after each cycle.

Computing details top

Data collection: COLLECT (Nonius, 1997-2001); cell refinement: DENZO/SCALEPACK; 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.

Figures top
[Figure 1] Fig. 1. Chains in USO-21. Green pentagonal bipyramids, blue tetrahedra and red triangles represent [UO7], [SO4] and [NO3], respectively.
[Figure 2] Fig. 2. Three-dimensional packing of USO-21. Green pentagonal bipyramids, blue tetrahedra and red triangles represent [UO7], [SO4] and [NO3], 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. H atoms have been removed for clarity.
(I) top
Crystal data top
(C4H12N)[UO2(NO3)(SO4)]F(000) = 879.898
Mr = 502.24Dx = 2.728 Mg m3
Monoclinic, C2/mMelting point: not measured K
Hall symbol: -C 2yMo Kα radiation, λ = 0.71073 Å
a = 21.106 (1) ÅCell parameters from 1226 reflections
b = 6.9350 (3) Åθ = 5–27°
c = 8.4284 (5) ŵ = 13.48 mm1
β = 97.5468 (18)°T = 150 K
V = 1223.0 (1) Å3Block, yellow
Z = 40.02 × 0.02 × 0.02 mm
Data collection top
Enraf-Nonius KappaCCD
diffractometer
1240 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.03
ω scansθmax = 27.5°, θmin = 5.5°
Absorption correction: multi-scan
(Otwinowski & Minor, 1996)
h = 2727
Tmin = 0.76, Tmax = 0.76k = 78
2501 measured reflectionsl = 1010
1483 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)] = 0.025 Chebychev polynomial with 5 parameters (Carruthers & Watkin, 1979), 3.86 4.01 1.57 0.107 0.409
wR(F2) = 0.048(Δ/σ)max = 0.001
S = 0.86Δρmax = 0.93 e Å3
1240 reflectionsΔρmin = 0.89 e Å3
95 parametersExtinction correction: Larson 1970 Crystallographic Computing eq 22
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 6.3 (7)
Crystal data top
(C4H12N)[UO2(NO3)(SO4)]V = 1223.0 (1) Å3
Mr = 502.24Z = 4
Monoclinic, C2/mMo Kα radiation
a = 21.106 (1) ŵ = 13.48 mm1
b = 6.9350 (3) ÅT = 150 K
c = 8.4284 (5) Å0.02 × 0.02 × 0.02 mm
β = 97.5468 (18)°
Data collection top
Enraf-Nonius KappaCCD
diffractometer
1483 independent reflections
Absorption correction: multi-scan
(Otwinowski & Minor, 1996)
1240 reflections with I > 3σ(I)
Tmin = 0.76, Tmax = 0.76Rint = 0.03
2501 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02595 parameters
wR(F2) = 0.048H-atom parameters not refined
S = 0.86Δρmax = 0.93 e Å3
1240 reflectionsΔρmin = 0.89 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
U10.855337 (17)0.50000.64171 (4)0.0123
S10.79668 (9)0.00000.6245 (2)0.0155
O10.8845 (3)0.50000.4550 (7)0.0240
O20.8288 (3)0.50000.8315 (7)0.0226
O30.95723 (18)0.3443 (6)0.7616 (5)0.0247
O40.83883 (19)0.1705 (6)0.6171 (5)0.0258
O50.7494 (3)0.50000.5260 (7)0.0225
O61.0425 (3)0.50000.8688 (8)0.0305
O70.7647 (3)0.00000.7643 (8)0.0320
N10.9882 (3)0.50000.8006 (9)0.0196
N20.8761 (3)0.00000.1586 (9)0.0221
C10.9147 (5)0.00000.0227 (12)0.0344
C20.9221 (5)0.00000.3081 (11)0.0299
C30.8338 (3)0.1751 (9)0.1524 (8)0.0304
H10.88470.00000.08160.0461*
H20.94180.13220.02680.0461*
H30.95010.13220.31150.0368*
H40.89880.00000.40370.0368*
H50.80290.17270.05130.0374*
H60.86040.29430.15490.0374*
H70.80940.17430.24650.0374*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
U10.01471 (16)0.00708 (15)0.01436 (16)0.00000.0013 (1)0.0000
S10.0172 (9)0.0077 (8)0.0203 (9)0.00000.0024 (7)0.0000
O10.029 (3)0.020 (3)0.023 (3)0.00000.006 (3)0.0000
O20.024 (3)0.027 (3)0.016 (3)0.00000.000 (2)0.0000
O30.020 (2)0.014 (2)0.038 (2)0.0013 (17)0.0049 (17)0.0008 (19)
O40.028 (2)0.0075 (19)0.040 (3)0.0040 (16)0.0026 (19)0.0002 (18)
O50.018 (3)0.021 (3)0.027 (3)0.00000.004 (2)0.0000
O60.017 (3)0.036 (4)0.036 (4)0.00000.006 (3)0.0000
O70.031 (4)0.041 (4)0.025 (3)0.00000.008 (3)0.0000
N10.022 (4)0.014 (3)0.023 (4)0.00000.001 (3)0.0000
N20.027 (4)0.015 (3)0.025 (4)0.00000.006 (3)0.0000
C10.043 (6)0.031 (5)0.034 (5)0.00000.023 (4)0.0000
C20.033 (5)0.033 (5)0.024 (5)0.00000.001 (4)0.0000
C30.029 (3)0.017 (3)0.046 (4)0.004 (2)0.007 (3)0.006 (3)
Geometric parameters (Å, º) top
U1—O11.763 (6)N2—C11.491 (11)
U1—O21.763 (6)N2—C21.486 (11)
U1—O32.498 (4)N2—C31.504 (7)
U1—O42.317 (4)C1—H11.014
U1—O52.320 (6)C1—H21.079
N1—O31.282 (5)C2—H31.089
N1—O61.213 (9)C2—H40.997
S1—O41.486 (4)C3—H51.003
S1—O5i1.493 (6)C3—H60.998
S1—O71.433 (7)C3—H71.001
O1—U1—O2178.1 (3)O3—N1—O3ii114.7 (6)
O1—U1—O388.8 (2)O3—N1—O6122.6 (3)
O1—U1—O489.20 (12)C1—N2—C2106.8 (7)
O1—U1—O593.1 (3)C1—N2—C3110.8 (5)
O2—U1—O389.5 (2)C2—N2—C3110.4 (5)
O2—U1—O491.11 (12)C3—N2—C3iii107.7 (6)
O2—U1—O588.7 (2)N2—C1—H1108.901
O3—U1—O3ii51.23 (18)N2—C1—H2108.454
O3—U1—O473.81 (13)H1—C1—H2107.252
O3—U1—O4ii125.03 (13)H2—C1—H2iii116.338
O3—U1—O5154.33 (9)N2—C3—H5109.444
O4—U1—O4ii161.05 (19)N2—C3—H6109.789
O4—U1—O580.6 (1)H5—C3—H6109.435
O4—S1—O4iii105.4 (3)N2—C3—H7109.459
O4—S1—O5i106.9 (2)H5—C3—H7109.145
O4—S1—O7112.6 (2)H6—C3—H7109.553
O5i—S1—O7112.0 (4)N2—C2—H4110.344
U1—O3—N197.0 (3)N2—C2—H3108.319
U1—O4—S1149.9 (3)H4—C2—H3107.639
U1—O5—S1i147.3 (4)H3—C2—H3iii114.563
Symmetry codes: (i) x+3/2, y1/2, z+1; (ii) x, y1, z; (iii) x, y, z.

Experimental details

Crystal data
Chemical formula(C4H12N)[UO2(NO3)(SO4)]
Mr502.24
Crystal system, space groupMonoclinic, C2/m
Temperature (K)150
a, b, c (Å)21.106 (1), 6.9350 (3), 8.4284 (5)
β (°) 97.5468 (18)
V3)1223.0 (1)
Z4
Radiation typeMo Kα
µ (mm1)13.48
Crystal size (mm)0.02 × 0.02 × 0.02
Data collection
DiffractometerEnraf-Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(Otwinowski & Minor, 1996)
Tmin, Tmax0.76, 0.76
No. of measured, independent and
observed [I > 3σ(I)] reflections
2501, 1483, 1240
Rint0.03
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.048, 0.86
No. of reflections1240
No. of parameters95
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.93, 0.89

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

Selected geometric parameters (Å, º) top
U1—O11.763 (6)N1—O31.282 (5)
U1—O21.763 (6)N1—O61.213 (9)
U1—O32.498 (4)S1—O41.486 (4)
U1—O42.317 (4)S1—O5i1.493 (6)
U1—O52.320 (6)S1—O71.433 (7)
O1—U1—O2178.1 (3)O4—U1—O4ii161.05 (19)
O1—U1—O388.8 (2)O4—U1—O580.6 (1)
O1—U1—O489.20 (12)O4—S1—O4iii105.4 (3)
O1—U1—O593.1 (3)O4—S1—O5i106.9 (2)
O2—U1—O389.5 (2)O4—S1—O7112.6 (2)
O2—U1—O491.11 (12)O5i—S1—O7112.0 (4)
O2—U1—O588.7 (2)U1—O3—N197.0 (3)
O3—U1—O3ii51.23 (18)U1—O4—S1149.9 (3)
O3—U1—O473.81 (13)U1—O5—S1i147.3 (4)
O3—U1—O4ii125.03 (13)O3—N1—O3ii114.7 (6)
O3—U1—O5154.33 (9)O3—N1—O6122.6 (3)
Symmetry codes: (i) x+3/2, y1/2, z+1; (ii) x, y1, z; (iii) x, y, z.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds