From powder pattern indexing it has been demonstrated that [Y(H2O)]2(C2O4)(CO3)2, yttrium oxalate carbonate, crystallizes with orthorhombic symmetry, space group C2221, a = 7.8177 (7), b = 14.943 (1), c = 9.4845 (7) Å, V = 1108.0 (1) Å3, Z = 4. This unit cell displays a doubling of the c parameter, arising from weak diffraction lines observed in the powder diffraction pattern, with respect to results reported in the literature. The crystal structure has been solved ab initio using direct methods from powder data and has been confirmed by additional single-crystal data collected with a CCD area detector. The overall crystal structure is similar for both unit cells, except that an alternation of the carbonate groups in the direction parallel to the screw axis is displayed in the larger cell, while with the suggested half unit cell (space group C2mm) the carbonate groups would show only one orientation. The unit-cell determination strategy from single-crystal diffraction, collected with Nonius CAD-4 and Nonius Kappa CCD diffractometers, is discussed with respect to the results extracted from the powder diffraction pattern. The study demonstrates the power and usefulness of the full trace of a powder pattern for the detection of subtle structure details.
Supporting information
CCDC references: 156693; 156694
Data collection: KappaCCD for C. Cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997) for C. Data reduction: HKL DENZO and SCALEPACK(Otwinowski & Minor, 1997) for C. Program(s) used to solve structure: SIR97 (Cascarano, 1996) for C. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for C. Molecular graphics: DIAMOND 2.1c for C. Software used to prepare material for publication: SHELXL97 for C.
Crystal data top
Y2(H2O)2(C2O4)(CO3)2 | V = 1108.0 (1) Å3 |
Mr = 421.88 | Z = 4 |
Orthorhombic, C2221 | Dx = 2.526 Mg m−3 |
a = 7.8177 (7) Å | Cu Kα radiation, λ = 1.5406 Å |
b = 14.943 (1) Å | × × mm |
c = 9.4845 (7) Å | |
Data collection top
Siemens D500 diffractometer | k = ?→? |
Germanium monochromator | l = ?→? |
h = ?→? | |
Crystal data top
Y2(H2O)2(C2O4)(CO3)2 | c = 9.4845 (7) Å |
Mr = 421.88 | V = 1108.0 (1) Å3 |
Orthorhombic, C2221 | Z = 4 |
a = 7.8177 (7) Å | Cu Kα radiation |
b = 14.943 (1) Å | × × mm |
Data collection top
Siemens D500 diffractometer | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Biso*/Beq | |
Y1 | 0.0000 | 0.2932 (5) | 0.2500 | | |
Y2 | 0.5000 | 0.2074 (5) | 0.2500 | | |
C1 | 0.400 (1) | 0.007 (1) | 0.253 (5) | | |
O11 | 0.331 (2) | −0.0710 (9) | 0.246 (3) | | |
O12 | 0.334 (3) | 0.0815 (9) | 0.283 (2) | | |
C2 | 0.692 (1) | 0.225 (1) | 0.503 (2) | | |
O21 | 0.747 (2) | 0.263 (1) | 0.387 (1) | | |
O22 | 0.5498 (9) | 0.1851 (6) | 0.505 (2) | | |
O23 | 0.770 (2) | 0.237 (1) | 0.623 (1) | | |
OW1 | 0.0000 | 0.143 (3) | 0.2500 | | |
OW2 | 0.5000 | 0.371 (3) | 0.2500 | | |
Crystal data top
Y2(H2O)2(C2O4)(CO3)2 | Dx = 2.526 Mg m−3 |
Mr = 421.88 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, C2221 | Cell parameters from 2298 reflections |
a = 7.8198 (5) Å | θ = 1.0–35.0° |
b = 14.949 (1) Å | µ = 10.47 mm−1 |
c = 9.4908 (5) Å | T = 293 K |
V = 1109.4 (1) Å3 | Prism, colourless |
Z = 4 | 0.11 × 0.04 × 0.04 mm |
F(000) = 808 | |
Data collection top
KappaCCD diffractometer | 2431 independent reflections |
Radiation source: fine-focus sealed tube | 1517 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
CCD scans | θmax = 35.0°, θmin = 2.9° |
Absorption correction: integration Gaussian integration (Coppens, 1970) | h = 0→12 |
Tmin = 0.409, Tmax = 0.634 | k = 0→24 |
2431 measured reflections | l = −15→15 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0077P)2 + 7.7969P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.104 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 1.02 e Å−3 |
2431 reflections | Δρmin = −0.80 e Å−3 |
91 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.00086 (19) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.12 (10) |
Crystal data top
Y2(H2O)2(C2O4)(CO3)2 | V = 1109.4 (1) Å3 |
Mr = 421.88 | Z = 4 |
Orthorhombic, C2221 | Mo Kα radiation |
a = 7.8198 (5) Å | µ = 10.47 mm−1 |
b = 14.949 (1) Å | T = 293 K |
c = 9.4908 (5) Å | 0.11 × 0.04 × 0.04 mm |
Data collection top
KappaCCD diffractometer | 2431 independent reflections |
Absorption correction: integration Gaussian integration (Coppens, 1970) | 1517 reflections with I > 2σ(I) |
Tmin = 0.409, Tmax = 0.634 | Rint = 0.000 |
2431 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.104 | Δρmax = 1.02 e Å−3 |
S = 1.09 | Δρmin = −0.80 e Å−3 |
2431 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
91 parameters | Absolute structure parameter: 0.12 (10) |
2 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Y1 | 0.0000 | 0.29284 (7) | 0.2500 | 0.0095 (2) | |
Y2 | 0.5000 | 0.20723 (7) | 0.2500 | 0.0095 (2) | |
C1 | 0.4007 (5) | 0.0011 (6) | 0.2573 (5) | 0.0155 (8) | |
O11 | 0.3297 (11) | −0.0726 (3) | 0.2630 (9) | 0.0180 (14) | |
O12 | 0.3315 (11) | 0.0772 (3) | 0.2639 (8) | 0.0194 (15) | |
C2 | 0.6951 (5) | 0.2246 (3) | 0.4995 (11) | 0.0130 (8) | |
O21 | 0.7559 (10) | 0.2466 (4) | 0.3803 (7) | 0.0214 (15) | |
O22 | 0.5543 (4) | 0.1802 (2) | 0.4968 (8) | 0.0155 (6) | |
O23 | 0.7559 (10) | 0.2474 (4) | 0.6186 (7) | 0.0214 (15) | |
OW1 | 0.0000 | 0.1358 (7) | 0.2500 | 0.061 (5) | |
OW2 | 0.5000 | 0.3630 (7) | 0.2500 | 0.082 (7) | |
H2 | 0.601 (6) | 0.398 (4) | 0.226 (7) | 0.025* | |
H1 | 0.065 (8) | 0.101 (4) | 0.317 (6) | 0.025* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Y1 | 0.0072 (5) | 0.0117 (5) | 0.0098 (5) | 0.000 | −0.0013 (6) | 0.000 |
Y2 | 0.0086 (5) | 0.0097 (5) | 0.0101 (5) | 0.000 | 0.0000 (6) | 0.000 |
C1 | 0.0119 (15) | 0.0153 (17) | 0.0195 (17) | −0.013 (4) | −0.0017 (17) | −0.002 (4) |
O11 | 0.009 (3) | 0.007 (2) | 0.038 (4) | −0.001 (2) | −0.001 (3) | −0.001 (3) |
O12 | 0.014 (4) | 0.015 (3) | 0.029 (4) | 0.002 (3) | 0.003 (3) | 0.000 (3) |
C2 | 0.0126 (17) | 0.0163 (18) | 0.0101 (16) | 0.0005 (15) | 0.008 (4) | 0.008 (4) |
O21 | 0.019 (4) | 0.033 (4) | 0.012 (3) | −0.012 (3) | −0.002 (3) | 0.012 (2) |
O22 | 0.0096 (11) | 0.0252 (16) | 0.0116 (13) | −0.0065 (11) | −0.003 (3) | 0.007 (3) |
O23 | 0.019 (4) | 0.039 (4) | 0.006 (2) | −0.015 (3) | −0.005 (3) | 0.010 (2) |
OW1 | 0.009 (6) | 0.011 (5) | 0.161 (16) | 0.000 | 0.006 (9) | 0.000 |
OW2 | 0.016 (8) | 0.015 (6) | 0.21 (2) | 0.000 | −0.001 (11) | 0.000 |
Geometric parameters (Å, º) top
Y1—OW1 | 2.347 (10) | Y2—O21 | 2.424 (7) |
Y1—O21i | 2.377 (7) | Y2—O21ii | 2.424 (7) |
Y1—O21ii | 2.377 (7) | Y2—C2 | 2.829 (10) |
Y1—O11iii | 2.415 (7) | Y2—C2ii | 2.829 (10) |
Y1—O11iv | 2.415 (7) | C1—O11 | 1.235 (9) |
Y1—O23v | 2.433 (7) | C1—O12 | 1.261 (10) |
Y1—O23vi | 2.433 (7) | C1—C1ii | 1.559 (8) |
Y1—O22vi | 2.474 (7) | O11—Y1viii | 2.415 (7) |
Y1—O22v | 2.474 (7) | C2—O21 | 1.270 (11) |
Y1—C2v | 2.837 (9) | C2—O23 | 1.273 (12) |
Y1—C2vi | 2.837 (9) | C2—O22 | 1.286 (5) |
Y2—OW2 | 2.328 (11) | C2—Y1ix | 2.837 (9) |
Y2—O12 | 2.352 (7) | O21—Y1x | 2.377 (7) |
Y2—O12ii | 2.352 (7) | O22—Y1ix | 2.474 (7) |
Y2—O23vii | 2.379 (7) | O23—Y2xi | 2.379 (7) |
Y2—O23vi | 2.379 (7) | O23—Y1ix | 2.433 (7) |
Y2—O22ii | 2.415 (7) | OW1—H1 | 0.969 (15) |
Y2—O22 | 2.415 (7) | OW2—H2 | 0.976 (15) |
| | | |
OW1—Y1—O21i | 73.11 (15) | O23vii—Y2—O22ii | 71.37 (18) |
OW1—Y1—O21ii | 73.11 (15) | O23vi—Y2—O22ii | 114.51 (19) |
O21i—Y1—O21ii | 146.2 (3) | OW2—Y2—O22 | 99.63 (9) |
OW1—Y1—O11iii | 146.38 (18) | O12—Y2—O22 | 84.6 (2) |
O21i—Y1—O11iii | 135.3 (2) | O12ii—Y2—O22 | 79.5 (2) |
O21ii—Y1—O11iii | 76.9 (2) | O23vii—Y2—O22 | 114.51 (19) |
OW1—Y1—O11iv | 146.38 (18) | O23vi—Y2—O22 | 71.37 (19) |
O21i—Y1—O11iv | 76.9 (2) | O22ii—Y2—O22 | 160.73 (18) |
O21ii—Y1—O11iv | 135.3 (2) | OW2—Y2—O21 | 75.94 (14) |
O11iii—Y1—O11iv | 67.2 (3) | O12—Y2—O21 | 129.4 (2) |
OW1—Y1—O23v | 75.68 (15) | O12ii—Y2—O21 | 76.5 (2) |
O21i—Y1—O23v | 62.24 (19) | O23vii—Y2—O21 | 62.3 (2) |
O21ii—Y1—O23v | 108.8 (2) | O23vi—Y2—O21 | 109.0 (3) |
O11iii—Y1—O23v | 129.3 (2) | O22ii—Y2—O21 | 132.9 (2) |
O11iv—Y1—O23v | 77.2 (2) | O22—Y2—O21 | 53.18 (18) |
OW1—Y1—O23vi | 75.68 (15) | OW2—Y2—O21ii | 75.94 (14) |
O21i—Y1—O23vi | 108.8 (2) | O12—Y2—O21ii | 76.5 (2) |
O21ii—Y1—O23vi | 62.24 (19) | O12ii—Y2—O21ii | 129.4 (2) |
O11iii—Y1—O23vi | 77.2 (2) | O23vii—Y2—O21ii | 109.0 (3) |
O11iv—Y1—O23vi | 129.3 (2) | O23vi—Y2—O21ii | 62.3 (2) |
O23v—Y1—O23vi | 151.4 (3) | O22ii—Y2—O21ii | 53.18 (18) |
OW1—Y1—O22vi | 99.38 (8) | O22—Y2—O21ii | 132.9 (2) |
O21i—Y1—O22vi | 71.33 (19) | O21—Y2—O21ii | 151.9 (3) |
O21ii—Y1—O22vi | 114.51 (19) | OW2—Y2—C2 | 84.74 (8) |
O11iii—Y1—O22vi | 79.6 (2) | O12—Y2—C2 | 109.3 (2) |
O11iv—Y1—O22vi | 84.8 (2) | O12ii—Y2—C2 | 79.7 (2) |
O23v—Y1—O22vi | 132.80 (17) | O23vii—Y2—C2 | 88.8 (2) |
O23vi—Y1—O22vi | 53.21 (17) | O23vi—Y2—C2 | 88.2 (2) |
OW1—Y1—O22v | 99.38 (8) | O22ii—Y2—C2 | 157.26 (14) |
O21i—Y1—O22v | 114.51 (19) | O22—Y2—C2 | 26.93 (13) |
O21ii—Y1—O22v | 71.33 (19) | O21—Y2—C2 | 26.6 (2) |
O11iii—Y1—O22v | 84.8 (2) | O21ii—Y2—C2 | 148.18 (18) |
O11iv—Y1—O22v | 79.6 (2) | OW2—Y2—C2ii | 84.74 (8) |
O23v—Y1—O22v | 53.21 (17) | O12—Y2—C2ii | 79.7 (2) |
O23vi—Y1—O22v | 132.80 (17) | O12ii—Y2—C2ii | 109.3 (2) |
O22vi—Y1—O22v | 161.24 (16) | O23vii—Y2—C2ii | 88.2 (2) |
OW1—Y1—C2v | 84.73 (9) | O23vi—Y2—C2ii | 88.8 (2) |
O21i—Y1—C2v | 88.7 (2) | O22ii—Y2—C2ii | 26.93 (13) |
O21ii—Y1—C2v | 88.2 (2) | O22—Y2—C2ii | 157.26 (14) |
O11iii—Y1—C2v | 109.3 (2) | O21—Y2—C2ii | 148.18 (18) |
O11iv—Y1—C2v | 79.8 (2) | O21ii—Y2—C2ii | 26.6 (2) |
O23v—Y1—C2v | 26.6 (2) | C2—Y2—C2ii | 169.47 (17) |
O23vi—Y1—C2v | 148.10 (19) | O11—C1—O12 | 127.6 (4) |
O22vi—Y1—C2v | 157.16 (16) | O11—C1—C1ii | 116.8 (5) |
O22v—Y1—C2v | 26.92 (16) | O12—C1—C1ii | 115.6 (4) |
OW1—Y1—C2vi | 84.73 (9) | C1—O11—Y1viii | 119.6 (6) |
O21i—Y1—C2vi | 88.2 (2) | C1—O12—Y2 | 120.2 (6) |
O21ii—Y1—C2vi | 88.7 (2) | O21—C2—O23 | 125.6 (4) |
O11iii—Y1—C2vi | 79.8 (2) | O21—C2—O22 | 115.9 (9) |
O11iv—Y1—C2vi | 109.3 (2) | O23—C2—O22 | 118.4 (8) |
O23v—Y1—C2vi | 148.10 (19) | O21—C2—Y2 | 58.7 (5) |
O23vi—Y1—C2vi | 26.6 (2) | O23—C2—Y2 | 165.8 (4) |
O22vi—Y1—C2vi | 26.92 (16) | O22—C2—Y2 | 58.3 (5) |
O22v—Y1—C2vi | 157.16 (16) | O21—C2—Y1ix | 166.2 (4) |
C2v—Y1—C2vi | 169.46 (18) | O23—C2—Y1ix | 58.7 (5) |
OW2—Y2—O12 | 145.74 (19) | O22—C2—Y1ix | 60.6 (5) |
OW2—Y2—O12ii | 145.74 (19) | Y2—C2—Y1ix | 113.77 (14) |
O12—Y2—O12ii | 68.5 (4) | C2—O21—Y1x | 147.0 (6) |
OW2—Y2—O23vii | 73.44 (15) | C2—O21—Y2 | 94.7 (5) |
O12—Y2—O23vii | 135.6 (2) | Y1x—O21—Y2 | 117.9 (3) |
O12ii—Y2—O23vii | 75.9 (2) | C2—O22—Y2 | 94.8 (6) |
OW2—Y2—O23vi | 73.44 (14) | C2—O22—Y1ix | 92.5 (6) |
O12—Y2—O23vi | 75.9 (2) | Y2—O22—Y1ix | 152.25 (15) |
O12ii—Y2—O23vi | 135.6 (2) | C2—O23—Y2xi | 147.3 (5) |
O23vii—Y2—O23vi | 146.9 (3) | C2—O23—Y1ix | 94.7 (5) |
OW2—Y2—O22ii | 99.63 (9) | Y2xi—O23—Y1ix | 117.5 (3) |
O12—Y2—O22ii | 79.5 (2) | Y1—OW1—H1 | 123 (4) |
O12ii—Y2—O22ii | 84.6 (2) | Y2—OW2—H2 | 122 (4) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x−1/2, y+1/2, z; (v) −x+1/2, −y+1/2, z−1/2; (vi) x−1/2, −y+1/2, −z+1; (vii) −x+3/2, −y+1/2, z−1/2; (viii) x+1/2, y−1/2, z; (ix) −x+1/2, −y+1/2, z+1/2; (x) x+1, y, z; (xi) −x+3/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1···O12 | 0.97 (2) | 2.17 (7) | 2.739 (10) | 116 (5) |
OW2—H2···O11xii | 0.98 (2) | 1.87 (4) | 2.755 (9) | 149 (6) |
Symmetry code: (xii) x+1/2, y+1/2, z. |
Experimental details
| (pow) | (C) |
Crystal data |
Chemical formula | Y2(H2O)2(C2O4)(CO3)2 | Y2(H2O)2(C2O4)(CO3)2 |
Mr | 421.88 | 421.88 |
Crystal system, space group | Orthorhombic, C2221 | Orthorhombic, C2221 |
Temperature (K) | ? | 293 |
a, b, c (Å) | 7.8177 (7), 14.943 (1), 9.4845 (7) | 7.8198 (5), 14.949 (1), 9.4908 (5) |
V (Å3) | 1108.0 (1) | 1109.4 (1) |
Z | 4 | 4 |
Radiation type | Cu Kα | Mo Kα |
µ (mm−1) | ? | 10.47 |
Crystal size (mm) | × × | 0.11 × 0.04 × 0.04 |
|
Data collection |
Diffractometer | Siemens D500 diffractometer | KappaCCD diffractometer |
Absorption correction | ? | Integration Gaussian integration (Coppens, 1970) |
Tmin, Tmax | ?, ? | 0.409, 0.634 |
No. of measured, independent and observed reflections | ?, ?, ? (?) | 2431, 2431, 1517 [I > 2σ(I)] |
Rint | ? | 0.000 |
Distance from source to specimen (mm) | – | 0.808 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | ?, ?, ? | 0.046, 0.104, 1.09 |
No. of reflections | ? | 2431 |
No. of parameters | ? | 91 |
No. of restraints | ? | 2 |
H-atom treatment | ? | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | ?, ? | 1.02, −0.80 |
Absolute structure | ? | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | ? | 0.12 (10) |
Selected geometric parameters (Å, º) for (C) topY1—OW1 | 2.347 (10) | Y2—O23vi | 2.379 (7) |
Y1—O21i | 2.377 (7) | Y2—O22ii | 2.415 (7) |
Y1—O21ii | 2.377 (7) | Y2—O22 | 2.415 (7) |
Y1—O11iii | 2.415 (7) | Y2—O21 | 2.424 (7) |
Y1—O11iv | 2.415 (7) | Y2—O21ii | 2.424 (7) |
Y1—O23v | 2.433 (7) | C1—O11 | 1.235 (9) |
Y1—O23vi | 2.433 (7) | C1—O12 | 1.261 (10) |
Y1—O22vi | 2.474 (7) | C1—C1ii | 1.559 (8) |
Y1—O22v | 2.474 (7) | C2—O21 | 1.270 (11) |
Y2—OW2 | 2.328 (11) | C2—O23 | 1.273 (12) |
Y2—O12 | 2.352 (7) | C2—O22 | 1.286 (5) |
Y2—O12ii | 2.352 (7) | OW1—H1 | 0.969 (15) |
Y2—O23vii | 2.379 (7) | OW2—H2 | 0.976 (15) |
| | | |
O11—C1—O12 | 127.6 (4) | O21—C2—O23 | 125.6 (4) |
O11—C1—C1ii | 116.8 (5) | O21—C2—O22 | 115.9 (9) |
O12—C1—C1ii | 115.6 (4) | O23—C2—O22 | 118.4 (8) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x−1/2, y+1/2, z; (v) −x+1/2, −y+1/2, z−1/2; (vi) x−1/2, −y+1/2, −z+1; (vii) −x+3/2, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) for (C) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1···O12 | 0.969 (15) | 2.17 (7) | 2.739 (10) | 116 (5) |
OW2—H2···O11viii | 0.976 (15) | 1.87 (4) | 2.755 (9) | 149 (6) |
Symmetry code: (viii) x+1/2, y+1/2, z. |