Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104010339/tr1090sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104010339/tr1090Isup2.hkl |
CCDC reference: 245870
Compound (I) was obtained during investigation of the Ba(NCS)2—UO2(C2O4)-H2O system. Solid UO2(C2O4) was added to a hot aqueous solution of barium isothiocyanate with the molar ratio 1.5:1, giving a clear orange solution. After slow evaporation at room temperature, orange lath-shaped crystals precipitated which were identified as Ba3UO2(C2O4)2(NCS)2·8H2O (Markov & Sergeeva, 1961). These were filtered off and the solution was left for some time, resulting in a light-yellow crystalline precipitate, which appeared as a mixture of a fine yellow crystalline powder and colourless opaque plate-shaped crystals of (I).
After being located from a difference electron-density map, the positions of the water H atoms were refined with the O—H and H···H distances restrained to 0.82(s.u.?) and 1.36(s.u.?)Å, respectively, to give reasonable H—O—H angles, and with a Uiso value of 0.05 Å2.
Data collection: CAD-4 Software (Enraf-Nonius, 1988); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TOPOS4.0 (Blatov et al., 2000); software used to prepare material for publication: local programs.
[Ba2(C2O4)(H2O)6](NCS)2 | Z = 1 |
Mr = 586.96 | F(000) = 274 |
Triclinic, P1 | Dx = 2.421 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8990 (9) Å | Cell parameters from 24 reflections |
b = 6.9441 (6) Å | θ = 9–15° |
c = 9.6383 (10) Å | µ = 5.16 mm−1 |
α = 85.517 (8)° | T = 293 K |
β = 71.498 (9)° | Plate, colourless |
γ = 67.037 (8)° | 0.11 × 0.11 × 0.06 mm |
V = 402.63 (8) Å3 |
Enraf-Nonius CAD-4 diffractometer | 1291 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω/2θ scans | h = −7→8 |
Absorption correction: integration (SHELX76; Sheldrick, 1986) | k = −8→8 |
Tmin = 0.428, Tmax = 0.819 | l = 0→11 |
1539 measured reflections | 3 standard reflections every 60 min |
1411 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | Only H-atom coordinates refined |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0979P)2 + 5.3664P] where P = (Fo2 + 2Fc2)/3 |
1411 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 1.70 e Å−3 |
9 restraints | Δρmin = −1.81 e Å−3 |
[Ba2(C2O4)(H2O)6](NCS)2 | γ = 67.037 (8)° |
Mr = 586.96 | V = 402.63 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.8990 (9) Å | Mo Kα radiation |
b = 6.9441 (6) Å | µ = 5.16 mm−1 |
c = 9.6383 (10) Å | T = 293 K |
α = 85.517 (8)° | 0.11 × 0.11 × 0.06 mm |
β = 71.498 (9)° |
Enraf-Nonius CAD-4 diffractometer | 1291 reflections with I > 2σ(I) |
Absorption correction: integration (SHELX76; Sheldrick, 1986) | Rint = 0.025 |
Tmin = 0.428, Tmax = 0.819 | 3 standard reflections every 60 min |
1539 measured reflections | intensity decay: none |
1411 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 9 restraints |
wR(F2) = 0.157 | Only H-atom coordinates refined |
S = 1.19 | Δρmax = 1.70 e Å−3 |
1411 reflections | Δρmin = −1.81 e Å−3 |
109 parameters |
Experimental. none |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ba1 | 0.19564 (9) | 0.69341 (8) | 0.49723 (7) | 0.0203 (3) | |
C1 | 0.3930 (18) | 0.1007 (19) | 0.5118 (12) | 0.025 (2) | |
O1 | 0.4107 (13) | 0.2747 (12) | 0.5167 (9) | 0.0264 (17) | |
O2 | 0.2211 (12) | 0.0772 (12) | 0.5164 (9) | 0.0271 (17) | |
O3 | 0.3841 (16) | 0.5406 (16) | 0.7351 (10) | 0.037 (2) | |
H31 | 0.38 (3) | 0.640 (15) | 0.776 (14) | 0.050* | |
H32 | 0.38 (3) | 0.445 (16) | 0.789 (12) | 0.050* | |
O4 | 0.1388 (18) | 0.9715 (17) | 0.2599 (10) | 0.044 (2) | |
H41 | 0.06 (2) | 0.97 (3) | 0.213 (13) | 0.050* | |
H42 | 0.23 (2) | 1.02 (3) | 0.211 (13) | 0.050* | |
O5 | 0.1047 (14) | 0.4702 (13) | 0.3054 (10) | 0.0303 (18) | |
H51 | 0.218 (16) | 0.364 (15) | 0.282 (13) | 0.050* | |
H52 | 0.07 (2) | 0.52 (2) | 0.232 (9) | 0.050* | |
N1 | 0.478 (2) | −0.1252 (18) | 0.8393 (14) | 0.043 (3) | |
C2 | 0.327 (2) | 0.0227 (18) | 0.8799 (14) | 0.029 (3) | |
S1 | 0.1100 (6) | 0.2401 (6) | 0.9390 (4) | 0.0444 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ba1 | 0.0137 (4) | 0.0126 (4) | 0.0361 (5) | −0.0059 (3) | −0.0086 (3) | 0.0003 (3) |
C1 | 0.018 (5) | 0.032 (6) | 0.028 (6) | −0.019 (5) | 0.003 (4) | −0.009 (5) |
O1 | 0.028 (4) | 0.025 (4) | 0.036 (4) | −0.017 (3) | −0.014 (4) | 0.005 (3) |
O2 | 0.014 (4) | 0.023 (4) | 0.049 (5) | −0.011 (3) | −0.011 (3) | −0.002 (4) |
O3 | 0.042 (5) | 0.037 (5) | 0.037 (5) | −0.022 (4) | −0.007 (4) | −0.002 (4) |
O4 | 0.048 (6) | 0.055 (6) | 0.037 (5) | −0.035 (5) | −0.009 (4) | 0.011 (5) |
O5 | 0.024 (4) | 0.022 (4) | 0.041 (5) | −0.003 (3) | −0.009 (4) | −0.007 (4) |
N1 | 0.034 (6) | 0.027 (6) | 0.062 (8) | −0.001 (5) | −0.016 (6) | −0.010 (5) |
C2 | 0.026 (6) | 0.019 (6) | 0.039 (6) | −0.005 (5) | −0.008 (5) | −0.004 (5) |
S1 | 0.0407 (19) | 0.0367 (19) | 0.0363 (18) | 0.0005 (15) | −0.0062 (15) | 0.0012 (14) |
Ba1—O1 | 2.723 (8) | C1—O2 | 1.246 (13) |
Ba1—O1i | 2.771 (8) | N1—C2 | 1.122 (17) |
Ba1—O2ii | 2.730 (8) | C2—S1 | 1.637 (12) |
Ba1—O2iii | 2.762 (8) | O1—Ba1i | 2.771 (8) |
Ba1—O3 | 2.916 (10) | O2—Ba1ii | 2.730 (8) |
Ba1—O3i | 2.972 (10) | O2—Ba1vi | 2.762 (8) |
Ba1—O4 | 2.899 (10) | O3—Ba1i | 2.972 (10) |
Ba1—O4iv | 3.074 (11) | O3—H31 | 0.81 (16) |
Ba1—O5 | 2.856 (8) | O3—H32 | 0.81 (11) |
Ba1—O5ii | 2.864 (9) | O4—Ba1iv | 3.074 (11) |
Ba1—Ba1i | 4.0215 (12) | O4—H41 | 0.81 (15) |
Ba1—Ba1iv | 4.0491 (12) | O4—H42 | 0.83 (17) |
Ba1—Ba1ii | 4.4777 (11) | O5—Ba1ii | 2.864 (9) |
C1—C1v | 1.55 (2) | O5—H51 | 0.82 (11) |
C1—O1 | 1.266 (14) | O5—H52 | 0.83 (10) |
O1—Ba1—O2ii | 131.4 (2) | O3i—Ba1—Ba1i | 46.35 (19) |
O1—Ba1—O2iii | 143.1 (2) | O4iv—Ba1—Ba1i | 124.4 (2) |
O2ii—Ba1—O2iii | 85.0 (2) | O1—Ba1—Ba1iv | 172.56 (17) |
O1—Ba1—O1i | 85.9 (2) | O2ii—Ba1—Ba1iv | 42.82 (16) |
O2ii—Ba1—O1i | 142.6 (2) | O2iii—Ba1—Ba1iv | 42.20 (16) |
O2iii—Ba1—O1i | 58.4 (2) | O1i—Ba1—Ba1iv | 100.27 (17) |
O1—Ba1—O5 | 71.0 (2) | O5—Ba1—Ba1iv | 107.42 (17) |
O2ii—Ba1—O5 | 71.9 (2) | O5ii—Ba1—Ba1iv | 102.07 (16) |
O2iii—Ba1—O5 | 138.3 (3) | O4—Ba1—Ba1iv | 49.2 (2) |
O1i—Ba1—O5 | 129.9 (2) | O3—Ba1—Ba1iv | 119.48 (19) |
O1—Ba1—O5ii | 70.5 (2) | O3i—Ba1—Ba1iv | 126.29 (19) |
O2ii—Ba1—O5ii | 71.5 (2) | O4iv—Ba1—Ba1iv | 45.52 (18) |
O2iii—Ba1—O5ii | 128.4 (2) | Ba1i—Ba1—Ba1iv | 142.59 (3) |
O1i—Ba1—O5ii | 136.4 (2) | O1—Ba1—Ba1ii | 65.08 (16) |
O5—Ba1—O5ii | 77.0 (3) | O2ii—Ba1—Ba1ii | 66.32 (16) |
O1—Ba1—O4 | 135.3 (3) | O2iii—Ba1—Ba1ii | 150.80 (16) |
O2ii—Ba1—O4 | 60.5 (3) | O1i—Ba1—Ba1ii | 150.74 (17) |
O2iii—Ba1—O4 | 61.8 (3) | O5—Ba1—Ba1ii | 38.54 (18) |
O1i—Ba1—O4 | 92.4 (3) | O5ii—Ba1—Ba1ii | 38.42 (17) |
O5—Ba1—O4 | 76.5 (3) | O4—Ba1—Ba1ii | 105.3 (2) |
O5ii—Ba1—O4 | 130.2 (3) | O3—Ba1—Ba1ii | 104.22 (18) |
O1—Ba1—O3 | 60.0 (3) | O3i—Ba1—Ba1ii | 100.74 (18) |
O2ii—Ba1—O3 | 134.5 (3) | O4iv—Ba1—Ba1ii | 100.27 (18) |
O2iii—Ba1—O3 | 91.6 (3) | Ba1i—Ba1—Ba1ii | 108.41 (2) |
O1i—Ba1—O3 | 60.8 (2) | Ba1iv—Ba1—Ba1ii | 108.95 (2) |
O5—Ba1—O3 | 129.3 (3) | O2—C1—O1 | 125.6 (11) |
O5ii—Ba1—O3 | 75.6 (3) | O2—C1—C1v | 116.9 (12) |
O4—Ba1—O3 | 150.4 (3) | O1—C1—C1v | 117.4 (11) |
O1—Ba1—O3i | 60.5 (3) | C1—O1—Ba1 | 142.2 (7) |
O2ii—Ba1—O3i | 131.2 (3) | C1—O1—Ba1i | 122.9 (7) |
O2iii—Ba1—O3i | 102.5 (2) | Ba1—O1—Ba1i | 94.1 (2) |
O1i—Ba1—O3i | 58.8 (2) | C1—O2—Ba1ii | 140.0 (8) |
O5—Ba1—O3i | 71.2 (2) | C1—O2—Ba1vi | 124.3 (7) |
O5ii—Ba1—O3i | 127.8 (2) | Ba1ii—O2—Ba1vi | 95.0 (2) |
O4—Ba1—O3i | 80.6 (3) | Ba1—O3—Ba1i | 86.1 (2) |
O3—Ba1—O3i | 93.9 (2) | Ba1—O3—H31 | 109 (10) |
O1—Ba1—O4iv | 129.4 (3) | Ba1i—O3—H31 | 116 (10) |
O2ii—Ba1—O4iv | 59.8 (3) | Ba1—O3—H32 | 131 (10) |
O2iii—Ba1—O4iv | 58.0 (2) | Ba1i—O3—H32 | 99 (10) |
O1i—Ba1—O4iv | 101.3 (3) | H31—O3—H32 | 113 (13) |
O5—Ba1—O4iv | 127.9 (3) | Ba1—O4—Ba1iv | 85.3 (3) |
O5ii—Ba1—O4iv | 70.5 (2) | Ba1—O4—H41 | 120 (10) |
O4—Ba1—O4iv | 94.7 (3) | Ba1iv—O4—H41 | 101 (10) |
O3—Ba1—O4iv | 80.1 (3) | Ba1—O4—H42 | 123 (10) |
O3i—Ba1—O4iv | 159.0 (3) | Ba1iv—O4—H42 | 108 (10) |
O1—Ba1—Ba1i | 43.42 (16) | H41—O4—H42 | 110 (15) |
O2ii—Ba1—Ba1i | 174.36 (16) | Ba1—O5—Ba1ii | 103.0 (3) |
O2iii—Ba1—Ba1i | 100.41 (16) | Ba1—O5—H51 | 102 (10) |
O1i—Ba1—Ba1i | 42.49 (16) | Ba1ii—O5—H51 | 100 (10) |
O5—Ba1—Ba1i | 102.81 (17) | Ba1—O5—H52 | 122 (10) |
O5ii—Ba1—Ba1i | 105.83 (17) | Ba1ii—O5—H52 | 116 (10) |
O4—Ba1—Ba1i | 120.7 (2) | H51—O5—H52 | 110 (12) |
O3—Ba1—Ba1i | 47.51 (19) | N1—C2—S1 | 179.2 (13) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x, y+1, z; (iv) −x, −y+2, −z+1; (v) −x+1, −y, −z+1; (vi) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Ba2(C2O4)(H2O)6](NCS)2 |
Mr | 586.96 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.8990 (9), 6.9441 (6), 9.6383 (10) |
α, β, γ (°) | 85.517 (8), 71.498 (9), 67.037 (8) |
V (Å3) | 402.63 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 5.16 |
Crystal size (mm) | 0.11 × 0.11 × 0.06 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Integration (SHELX76; Sheldrick, 1986) |
Tmin, Tmax | 0.428, 0.819 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1539, 1411, 1291 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.157, 1.19 |
No. of reflections | 1411 |
No. of parameters | 109 |
No. of restraints | 9 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 1.70, −1.81 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1988), CAD-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TOPOS4.0 (Blatov et al., 2000), local programs.
Ba1—O1 | 2.723 (8) | Ba1—O5 | 2.856 (8) |
Ba1—O1i | 2.771 (8) | Ba1—O5ii | 2.864 (9) |
Ba1—O2ii | 2.730 (8) | C1—C1v | 1.55 (2) |
Ba1—O2iii | 2.762 (8) | C1—O1 | 1.266 (14) |
Ba1—O3 | 2.916 (10) | C1—O2 | 1.246 (13) |
Ba1—O3i | 2.972 (10) | N1—C2 | 1.122 (17) |
Ba1—O4 | 2.899 (10) | C2—S1 | 1.637 (12) |
Ba1—O4iv | 3.074 (11) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x, y+1, z; (iv) −x, −y+2, −z+1; (v) −x+1, −y, −z+1. |
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By varying the experimental conditions, different barium oxalate salts can be obtained. The structures of [Ba(C2O4)(H2C2O4)(H2O)2] (Chaix-Pluchery et al., 1989), [Ba(C2O4)(H2C2O4)] (Mutin et al., 1979), [Ba2(C2O4)2(H2O)] (Mutin et al., 1981), [Ba(C2O4)(H2O)2] (Christensen et al., 1995), [Ba(C2O4)(H2O)] (Mutin et al., 1974; Huang & Mak, 1990), [Ba2(C2O4)2(H2O)7] (Neder et al., 1997) and [Ba2(C2O4)2(H2C2O4)(H2O)2] (Mutin & Dusausoy, 1981) have been determined by single-crystal and powder diffraction. In addition, various complexes containing transition metal cations, Ba2+ and oxalate are known. However, there are no structurally characterized compounds containing Ba2+, C2O42−, water and anions such as halide, pseudo-halide, chalcogenide, etc. In this article, we present the first example of such a compound, [Ba2(C2O4)(H2O)6](NCS)2, (I) (Fig. 1). \sch
The connectivity and dimensionality of barium oxalate structures have been analysed with the program package TOPOS using algorithms based on Voronoi-Dirichlet partition (Blatov et al., 2000), without assumption of any atomic radii. We have found that the structure of (I) is layered, in contrast with all previously known barium oxalates which have a three-dimensional polymeric structure, with the sole exception of [Ba2(C2O4)2(H2O)7] (Neder et al., 1997), which is also layered.
In the structure of (I), positively charged planar covalent layers of Ba2+ cations, oxalate anions and water molecules are interspersed with NCS− anions (Fig. 2). Ten O atoms are coordinated to a Ba2+ cation, four of them belonging to oxalates and six to water molecules. The oxalate anion sits on a centre of inversion and is planar, with each O atom being bonded to two Ba2+ cations. Each water molecule is coordinated to two Ba2+ cations. Therefore, the structure of the layer can be described as [Ba(C2O4)3/6(H2O)6/2]∞∞n+ or [Ba2(µ6,η4-C2O4)(µ2-H2O)6]2+, or A2K42M62 (Porai-Koshits & Serezhkin, 1994).
Both the oxalate anion and Ba2+ cation centres form their own distorted triangular nets. Such motifs are typical for oxalates, according to Naumov et al. (1996). The topology of the layer is different from that found in [Ba2(C2O4)2(H2O)7], where Ba2+ forms regular hexagonal nets and the oxalate anion centres form distorted rectangular nets.
Weak hydrogen bonds between water molecules and the N atoms of the isothiocyanate anions join the layers together in (I). The O(water)···N distances are in the range 2.927 (12)–3.08 (2) Å. There is also a weak O(water)···S(CN) interaction, with an S···H distance of 2.51 (11) Å, between the isothiocyanate anion and one of the µ2-H2O molecules.