Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803010808/na6235sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803010808/na6235Isup2.hkl |
CCDC reference: 214793
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.
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.
(C4H12N)[UO2(NO3)(SO4)] | F(000) = 879.898 |
Mr = 502.24 | Dx = 2.728 Mg m−3 |
Monoclinic, C2/m | Melting point: not measured K |
Hall symbol: -C 2y | Mo Kα radiation, λ = 0.71073 Å |
a = 21.106 (1) Å | Cell parameters from 1226 reflections |
b = 6.9350 (3) Å | θ = 5–27° |
c = 8.4284 (5) Å | µ = 13.48 mm−1 |
β = 97.5468 (18)° | T = 150 K |
V = 1223.0 (1) Å3 | Block, yellow |
Z = 4 | 0.02 × 0.02 × 0.02 mm |
Enraf-Nonius KappaCCD diffractometer | 1240 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.03 |
ω scans | θmax = 27.5°, θmin = 5.5° |
Absorption correction: multi-scan (Otwinowski & Minor, 1996) | h = −27→27 |
Tmin = 0.76, Tmax = 0.76 | k = −7→8 |
2501 measured reflections | l = −10→10 |
1483 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-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 = 0.86 | Δρmax = 0.93 e Å−3 |
1240 reflections | Δρmin = −0.89 e Å−3 |
95 parameters | Extinction correction: Larson 1970 Crystallographic Computing eq 22 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 6.3 (7) |
(C4H12N)[UO2(NO3)(SO4)] | V = 1223.0 (1) Å3 |
Mr = 502.24 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 21.106 (1) Å | µ = 13.48 mm−1 |
b = 6.9350 (3) Å | T = 150 K |
c = 8.4284 (5) Å | 0.02 × 0.02 × 0.02 mm |
β = 97.5468 (18)° |
Enraf-Nonius KappaCCD diffractometer | 1483 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1996) | 1240 reflections with I > 3σ(I) |
Tmin = 0.76, Tmax = 0.76 | Rint = 0.03 |
2501 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 95 parameters |
wR(F2) = 0.048 | H-atom parameters not refined |
S = 0.86 | Δρmax = 0.93 e Å−3 |
1240 reflections | Δρmin = −0.89 e Å−3 |
x | y | z | Uiso*/Ueq | ||
U1 | 0.855337 (17) | −0.5000 | 0.64171 (4) | 0.0123 | |
S1 | 0.79668 (9) | 0.0000 | 0.6245 (2) | 0.0155 | |
O1 | 0.8845 (3) | −0.5000 | 0.4550 (7) | 0.0240 | |
O2 | 0.8288 (3) | −0.5000 | 0.8315 (7) | 0.0226 | |
O3 | 0.95723 (18) | −0.3443 (6) | 0.7616 (5) | 0.0247 | |
O4 | 0.83883 (19) | −0.1705 (6) | 0.6171 (5) | 0.0258 | |
O5 | 0.7494 (3) | −0.5000 | 0.5260 (7) | 0.0225 | |
O6 | 1.0425 (3) | −0.5000 | 0.8688 (8) | 0.0305 | |
O7 | 0.7647 (3) | 0.0000 | 0.7643 (8) | 0.0320 | |
N1 | 0.9882 (3) | −0.5000 | 0.8006 (9) | 0.0196 | |
N2 | 0.8761 (3) | 0.0000 | 0.1586 (9) | 0.0221 | |
C1 | 0.9147 (5) | 0.0000 | 0.0227 (12) | 0.0344 | |
C2 | 0.9221 (5) | 0.0000 | 0.3081 (11) | 0.0299 | |
C3 | 0.8338 (3) | −0.1751 (9) | 0.1524 (8) | 0.0304 | |
H1 | 0.8847 | 0.0000 | −0.0816 | 0.0461* | |
H2 | 0.9418 | 0.1322 | 0.0268 | 0.0461* | |
H3 | 0.9501 | 0.1322 | 0.3115 | 0.0368* | |
H4 | 0.8988 | 0.0000 | 0.4037 | 0.0368* | |
H5 | 0.8029 | −0.1727 | 0.0513 | 0.0374* | |
H6 | 0.8604 | −0.2943 | 0.1549 | 0.0374* | |
H7 | 0.8094 | −0.1743 | 0.2465 | 0.0374* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.01471 (16) | 0.00708 (15) | 0.01436 (16) | 0.0000 | −0.0013 (1) | 0.0000 |
S1 | 0.0172 (9) | 0.0077 (8) | 0.0203 (9) | 0.0000 | −0.0024 (7) | 0.0000 |
O1 | 0.029 (3) | 0.020 (3) | 0.023 (3) | 0.0000 | 0.006 (3) | 0.0000 |
O2 | 0.024 (3) | 0.027 (3) | 0.016 (3) | 0.0000 | 0.000 (2) | 0.0000 |
O3 | 0.020 (2) | 0.014 (2) | 0.038 (2) | −0.0013 (17) | −0.0049 (17) | 0.0008 (19) |
O4 | 0.028 (2) | 0.0075 (19) | 0.040 (3) | 0.0040 (16) | −0.0026 (19) | −0.0002 (18) |
O5 | 0.018 (3) | 0.021 (3) | 0.027 (3) | 0.0000 | −0.004 (2) | 0.0000 |
O6 | 0.017 (3) | 0.036 (4) | 0.036 (4) | 0.0000 | −0.006 (3) | 0.0000 |
O7 | 0.031 (4) | 0.041 (4) | 0.025 (3) | 0.0000 | 0.008 (3) | 0.0000 |
N1 | 0.022 (4) | 0.014 (3) | 0.023 (4) | 0.0000 | 0.001 (3) | 0.0000 |
N2 | 0.027 (4) | 0.015 (3) | 0.025 (4) | 0.0000 | 0.006 (3) | 0.0000 |
C1 | 0.043 (6) | 0.031 (5) | 0.034 (5) | 0.0000 | 0.023 (4) | 0.0000 |
C2 | 0.033 (5) | 0.033 (5) | 0.024 (5) | 0.0000 | 0.001 (4) | 0.0000 |
C3 | 0.029 (3) | 0.017 (3) | 0.046 (4) | −0.004 (2) | 0.007 (3) | −0.006 (3) |
U1—O1 | 1.763 (6) | N2—C1 | 1.491 (11) |
U1—O2 | 1.763 (6) | N2—C2 | 1.486 (11) |
U1—O3 | 2.498 (4) | N2—C3 | 1.504 (7) |
U1—O4 | 2.317 (4) | C1—H1 | 1.014 |
U1—O5 | 2.320 (6) | C1—H2 | 1.079 |
N1—O3 | 1.282 (5) | C2—H3 | 1.089 |
N1—O6 | 1.213 (9) | C2—H4 | 0.997 |
S1—O4 | 1.486 (4) | C3—H5 | 1.003 |
S1—O5i | 1.493 (6) | C3—H6 | 0.998 |
S1—O7 | 1.433 (7) | C3—H7 | 1.001 |
O1—U1—O2 | 178.1 (3) | O3—N1—O3ii | 114.7 (6) |
O1—U1—O3 | 88.8 (2) | O3—N1—O6 | 122.6 (3) |
O1—U1—O4 | 89.20 (12) | C1—N2—C2 | 106.8 (7) |
O1—U1—O5 | 93.1 (3) | C1—N2—C3 | 110.8 (5) |
O2—U1—O3 | 89.5 (2) | C2—N2—C3 | 110.4 (5) |
O2—U1—O4 | 91.11 (12) | C3—N2—C3iii | 107.7 (6) |
O2—U1—O5 | 88.7 (2) | N2—C1—H1 | 108.901 |
O3—U1—O3ii | 51.23 (18) | N2—C1—H2 | 108.454 |
O3—U1—O4 | 73.81 (13) | H1—C1—H2 | 107.252 |
O3—U1—O4ii | 125.03 (13) | H2—C1—H2iii | 116.338 |
O3—U1—O5 | 154.33 (9) | N2—C3—H5 | 109.444 |
O4—U1—O4ii | 161.05 (19) | N2—C3—H6 | 109.789 |
O4—U1—O5 | 80.6 (1) | H5—C3—H6 | 109.435 |
O4—S1—O4iii | 105.4 (3) | N2—C3—H7 | 109.459 |
O4—S1—O5i | 106.9 (2) | H5—C3—H7 | 109.145 |
O4—S1—O7 | 112.6 (2) | H6—C3—H7 | 109.553 |
O5i—S1—O7 | 112.0 (4) | N2—C2—H4 | 110.344 |
U1—O3—N1 | 97.0 (3) | N2—C2—H3 | 108.319 |
U1—O4—S1 | 149.9 (3) | H4—C2—H3 | 107.639 |
U1—O5—S1i | 147.3 (4) | H3—C2—H3iii | 114.563 |
Symmetry codes: (i) −x+3/2, −y−1/2, −z+1; (ii) x, −y−1, z; (iii) x, −y, z. |
Experimental details
Crystal data | |
Chemical formula | (C4H12N)[UO2(NO3)(SO4)] |
Mr | 502.24 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 150 |
a, b, c (Å) | 21.106 (1), 6.9350 (3), 8.4284 (5) |
β (°) | 97.5468 (18) |
V (Å3) | 1223.0 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 13.48 |
Crystal size (mm) | 0.02 × 0.02 × 0.02 |
Data collection | |
Diffractometer | Enraf-Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Otwinowski & Minor, 1996) |
Tmin, Tmax | 0.76, 0.76 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 2501, 1483, 1240 |
Rint | 0.03 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.048, 0.86 |
No. of reflections | 1240 |
No. of parameters | 95 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 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.
U1—O1 | 1.763 (6) | N1—O3 | 1.282 (5) |
U1—O2 | 1.763 (6) | N1—O6 | 1.213 (9) |
U1—O3 | 2.498 (4) | S1—O4 | 1.486 (4) |
U1—O4 | 2.317 (4) | S1—O5i | 1.493 (6) |
U1—O5 | 2.320 (6) | S1—O7 | 1.433 (7) |
O1—U1—O2 | 178.1 (3) | O4—U1—O4ii | 161.05 (19) |
O1—U1—O3 | 88.8 (2) | O4—U1—O5 | 80.6 (1) |
O1—U1—O4 | 89.20 (12) | O4—S1—O4iii | 105.4 (3) |
O1—U1—O5 | 93.1 (3) | O4—S1—O5i | 106.9 (2) |
O2—U1—O3 | 89.5 (2) | O4—S1—O7 | 112.6 (2) |
O2—U1—O4 | 91.11 (12) | O5i—S1—O7 | 112.0 (4) |
O2—U1—O5 | 88.7 (2) | U1—O3—N1 | 97.0 (3) |
O3—U1—O3ii | 51.23 (18) | U1—O4—S1 | 149.9 (3) |
O3—U1—O4 | 73.81 (13) | U1—O5—S1i | 147.3 (4) |
O3—U1—O4ii | 125.03 (13) | O3—N1—O3ii | 114.7 (6) |
O3—U1—O5 | 154.33 (9) | O3—N1—O6 | 122.6 (3) |
Symmetry codes: (i) −x+3/2, −y−1/2, −z+1; (ii) x, −y−1, z; (iii) x, −y, z. |
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.