Powder and single-crystal X-ray diffraction study of the structure of [Y(H₂O)]₂(C₂O₄)(CO₃)₂

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.

Computing details

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.

(pow)

Crystal data

Y2(H2O)2(C2O4)(CO3)2	V = 1108.0 (1) Å^3
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

Siemens D500 diffractometer	k = ?→?
Germanium monochromator	l = ?→?
h = ?→?

Refinement

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

	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

(C)

Crystal data

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) Å^3	Prism, colourless
Z = 4	0.11 × 0.04 × 0.04 mm
F(000) = 808

Data collection

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

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(Fo^2) + (0.0077P)^2 + 7.7969P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/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)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Y1—OW1	2.347 (10)	Y2—O21	2.424 (7)
Y1—O21^i	2.377 (7)	Y2—O21^ii	2.424 (7)
Y1—O21^ii	2.377 (7)	Y2—C2	2.829 (10)
Y1—O11^iii	2.415 (7)	Y2—C2^ii	2.829 (10)
Y1—O11^iv	2.415 (7)	C1—O11	1.235 (9)
Y1—O23^v	2.433 (7)	C1—O12	1.261 (10)
Y1—O23^vi	2.433 (7)	C1—C1^ii	1.559 (8)
Y1—O22^vi	2.474 (7)	O11—Y1^viii	2.415 (7)
Y1—O22^v	2.474 (7)	C2—O21	1.270 (11)
Y1—C2^v	2.837 (9)	C2—O23	1.273 (12)
Y1—C2^vi	2.837 (9)	C2—O22	1.286 (5)
Y2—OW2	2.328 (11)	C2—Y1^ix	2.837 (9)
Y2—O12	2.352 (7)	O21—Y1^x	2.377 (7)
Y2—O12^ii	2.352 (7)	O22—Y1^ix	2.474 (7)
Y2—O23^vii	2.379 (7)	O23—Y2^xi	2.379 (7)
Y2—O23^vi	2.379 (7)	O23—Y1^ix	2.433 (7)
Y2—O22^ii	2.415 (7)	OW1—H1	0.969 (15)
Y2—O22	2.415 (7)	OW2—H2	0.976 (15)
OW1—Y1—O21^i	73.11 (15)	O23^vii—Y2—O22^ii	71.37 (18)
OW1—Y1—O21^ii	73.11 (15)	O23^vi—Y2—O22^ii	114.51 (19)
O21^i—Y1—O21^ii	146.2 (3)	OW2—Y2—O22	99.63 (9)
OW1—Y1—O11^iii	146.38 (18)	O12—Y2—O22	84.6 (2)
O21^i—Y1—O11^iii	135.3 (2)	O12^ii—Y2—O22	79.5 (2)
O21^ii—Y1—O11^iii	76.9 (2)	O23^vii—Y2—O22	114.51 (19)
OW1—Y1—O11^iv	146.38 (18)	O23^vi—Y2—O22	71.37 (19)
O21^i—Y1—O11^iv	76.9 (2)	O22^ii—Y2—O22	160.73 (18)
O21^ii—Y1—O11^iv	135.3 (2)	OW2—Y2—O21	75.94 (14)
O11^iii—Y1—O11^iv	67.2 (3)	O12—Y2—O21	129.4 (2)
OW1—Y1—O23^v	75.68 (15)	O12^ii—Y2—O21	76.5 (2)
O21^i—Y1—O23^v	62.24 (19)	O23^vii—Y2—O21	62.3 (2)
O21^ii—Y1—O23^v	108.8 (2)	O23^vi—Y2—O21	109.0 (3)
O11^iii—Y1—O23^v	129.3 (2)	O22^ii—Y2—O21	132.9 (2)
O11^iv—Y1—O23^v	77.2 (2)	O22—Y2—O21	53.18 (18)
OW1—Y1—O23^vi	75.68 (15)	OW2—Y2—O21^ii	75.94 (14)
O21^i—Y1—O23^vi	108.8 (2)	O12—Y2—O21^ii	76.5 (2)
O21^ii—Y1—O23^vi	62.24 (19)	O12^ii—Y2—O21^ii	129.4 (2)
O11^iii—Y1—O23^vi	77.2 (2)	O23^vii—Y2—O21^ii	109.0 (3)
O11^iv—Y1—O23^vi	129.3 (2)	O23^vi—Y2—O21^ii	62.3 (2)
O23^v—Y1—O23^vi	151.4 (3)	O22^ii—Y2—O21^ii	53.18 (18)
OW1—Y1—O22^vi	99.38 (8)	O22—Y2—O21^ii	132.9 (2)
O21^i—Y1—O22^vi	71.33 (19)	O21—Y2—O21^ii	151.9 (3)
O21^ii—Y1—O22^vi	114.51 (19)	OW2—Y2—C2	84.74 (8)
O11^iii—Y1—O22^vi	79.6 (2)	O12—Y2—C2	109.3 (2)
O11^iv—Y1—O22^vi	84.8 (2)	O12^ii—Y2—C2	79.7 (2)
O23^v—Y1—O22^vi	132.80 (17)	O23^vii—Y2—C2	88.8 (2)
O23^vi—Y1—O22^vi	53.21 (17)	O23^vi—Y2—C2	88.2 (2)
OW1—Y1—O22^v	99.38 (8)	O22^ii—Y2—C2	157.26 (14)
O21^i—Y1—O22^v	114.51 (19)	O22—Y2—C2	26.93 (13)
O21^ii—Y1—O22^v	71.33 (19)	O21—Y2—C2	26.6 (2)
O11^iii—Y1—O22^v	84.8 (2)	O21^ii—Y2—C2	148.18 (18)
O11^iv—Y1—O22^v	79.6 (2)	OW2—Y2—C2^ii	84.74 (8)
O23^v—Y1—O22^v	53.21 (17)	O12—Y2—C2^ii	79.7 (2)
O23^vi—Y1—O22^v	132.80 (17)	O12^ii—Y2—C2^ii	109.3 (2)
O22^vi—Y1—O22^v	161.24 (16)	O23^vii—Y2—C2^ii	88.2 (2)
OW1—Y1—C2^v	84.73 (9)	O23^vi—Y2—C2^ii	88.8 (2)
O21^i—Y1—C2^v	88.7 (2)	O22^ii—Y2—C2^ii	26.93 (13)
O21^ii—Y1—C2^v	88.2 (2)	O22—Y2—C2^ii	157.26 (14)
O11^iii—Y1—C2^v	109.3 (2)	O21—Y2—C2^ii	148.18 (18)
O11^iv—Y1—C2^v	79.8 (2)	O21^ii—Y2—C2^ii	26.6 (2)
O23^v—Y1—C2^v	26.6 (2)	C2—Y2—C2^ii	169.47 (17)
O23^vi—Y1—C2^v	148.10 (19)	O11—C1—O12	127.6 (4)
O22^vi—Y1—C2^v	157.16 (16)	O11—C1—C1^ii	116.8 (5)
O22^v—Y1—C2^v	26.92 (16)	O12—C1—C1^ii	115.6 (4)
OW1—Y1—C2^vi	84.73 (9)	C1—O11—Y1^viii	119.6 (6)
O21^i—Y1—C2^vi	88.2 (2)	C1—O12—Y2	120.2 (6)
O21^ii—Y1—C2^vi	88.7 (2)	O21—C2—O23	125.6 (4)
O11^iii—Y1—C2^vi	79.8 (2)	O21—C2—O22	115.9 (9)
O11^iv—Y1—C2^vi	109.3 (2)	O23—C2—O22	118.4 (8)
O23^v—Y1—C2^vi	148.10 (19)	O21—C2—Y2	58.7 (5)
O23^vi—Y1—C2^vi	26.6 (2)	O23—C2—Y2	165.8 (4)
O22^vi—Y1—C2^vi	26.92 (16)	O22—C2—Y2	58.3 (5)
O22^v—Y1—C2^vi	157.16 (16)	O21—C2—Y1^ix	166.2 (4)
C2^v—Y1—C2^vi	169.46 (18)	O23—C2—Y1^ix	58.7 (5)
OW2—Y2—O12	145.74 (19)	O22—C2—Y1^ix	60.6 (5)
OW2—Y2—O12^ii	145.74 (19)	Y2—C2—Y1^ix	113.77 (14)
O12—Y2—O12^ii	68.5 (4)	C2—O21—Y1^x	147.0 (6)
OW2—Y2—O23^vii	73.44 (15)	C2—O21—Y2	94.7 (5)
O12—Y2—O23^vii	135.6 (2)	Y1^x—O21—Y2	117.9 (3)
O12^ii—Y2—O23^vii	75.9 (2)	C2—O22—Y2	94.8 (6)
OW2—Y2—O23^vi	73.44 (14)	C2—O22—Y1^ix	92.5 (6)
O12—Y2—O23^vi	75.9 (2)	Y2—O22—Y1^ix	152.25 (15)
O12^ii—Y2—O23^vi	135.6 (2)	C2—O23—Y2^xi	147.3 (5)
O23^vii—Y2—O23^vi	146.9 (3)	C2—O23—Y1^ix	94.7 (5)
OW2—Y2—O22^ii	99.63 (9)	Y2^xi—O23—Y1^ix	117.5 (3)
O12—Y2—O22^ii	79.5 (2)	Y1—OW1—H1	123 (4)
O12^ii—Y2—O22^ii	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)

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···O11^xii	0.98 (2)	1.87 (4)	2.755 (9)	149 (6)

Symmetry code: (xii) x+1/2, y+1/2, z.