Tricaesium tris­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)lutetium(III) octa­hydrate

Legrand, V.; Aubert, F.; D'Aléo, A.; Rabiller, P.; Maury, O.

doi:10.1107/S1600536808029243

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1280-m1281

doi:10.1107/S1600536808029243

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Tricaesium tris(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)lutetium(III) octahydrate

Vincent Legrand,^a ^* Flavien Aubert,^b Anthony D'Aléo,^c Philippe Rabiller ^b and Olivier Maury ^c

^aInstitut Laue Langevin, 6 rue Jules Horowitz, B.P.156, 38042 Grenoble Cedex 9, France, ^bGroupe Matiere Condensee et Materiaux, UMR CNRS 6626, Universite de Rennes 1, Campus de Beaulieu, 35042 Rennes cedex, France, and ^cLaboratoire de Chimie, UMR CNRS 5182, ENS Lyon, 46 allee d'Italie, 69364 Lyon cedex 07, France
^*Correspondence e-mail: legrand@ill.fr

(Received 9 June 2008; accepted 11 September 2008; online 20 September 2008)

Colourless block crystals of the title compound, Cs₃[Lu(dipic)₃]·8H₂O [dipic is dipicolinate or pyridine-2,6-dicarboxylate, C₇H₃NO₄] were synthesized by slow evaporation of the solvent. The crystal structure of this Lu^III-complex, isostructural with the Dy^III and Eu^III complexes, was determined from a crystal twinned by inversion and consists of discrete [Lu(dipic)₃]³⁻ anions, Cs⁺ cations and water molecules involving hydrogen bonding. The Lu atom lies on a twofold rotation axis and is coordinated by six O atoms and three N atoms of three dipicolinate ligands. One Cs atom is also on a twofold axis. The unit cell can be regarded as successive layers along the crystallographic c-axis formed by [Lu(dipic)₃]³⁻ anionic planes and [Cs⁺, H₂O] cationic planes. In the crystal structure, although the H atoms attached to water molecules could not be located, short O—O contacts clearly indicate the occurrence of an intricate hydrogen-bonded network through contacts with other water molecules, Cs cations or with the O atoms of the dipicolinate ligands.

Related literature

For potential applications of lanthanide complexes as second-order non-linear optical materials, see: Tancrez et al. (2005 ); Sénéchal et al. (2004 ). For the isostructural Eu^III complex, see: Brayshaw et al. (1995 ). For other related complexes, see: Murray et al. (1990 ). For related literature, see: Flack & Bernardinelli (1999 , 2000 ).

Experimental

Crystal data

Cs₃[Lu(C₇H₃NO₄)₃]·8H₂O
M_r = 1213.14
Orthorhombic, C 222₁
a = 10.0406 (2) Å
b = 17.8109 (6) Å
c = 18.4221 (5) Å
V = 3294.46 (16) Å³
Z = 4
Mo Kα radiation
μ = 6.36 mm⁻¹
T = 100 (2) K
0.20 × 0.19 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur–Sapphire3 diffractometer
Absorption correction: Gaussian (ABSORB; DeTitta, 1985 ) T_min = 0.307, T_max = 0.425
51066 measured reflections
3520 independent reflections
3491 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.063
S = 1.46
3520 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 3.00 e Å⁻³
Δρ_min = −0.94 e Å⁻³
Absolute structure: Flack (1983 ), 1501 Friedel pairs
Flack parameter: 0.270 (12)

Data collection: CrysAlis CCD (Oxford Diffraction 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: SORTAV (Blessing, 1989 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808029243/dn2357sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029243/dn2357Isup2.hkl

checkCIF report

Comment top

Lanthanide complexes attract considerable interest due to their magnetic and luminescent properties, but also for their potentialities in the field of second-order nonlinear optics (Sénéchal et al., 2004; Tancrez et al., 2005). Lanthanides emission can be sensitized either by direct absorption in the forbidden f-f transitions or via energy transfer from an organic ligand acting as antenna. Pulsed excitations induce long luminescence decay of the lanthanides and this time-gated emission can be used in medicine as probes in biological system for diagnosis or therapeutic purposes. In this context, lanthanide tris-dipicolinate (= pyridine-2,6-dicarboxylate) have been extensively studied both in solution and in solid state. We report the synthesis and structural characterization by X-ray diffraction measurements of the following complex: Cs₃[Lu(dipic)₃].8H₂O, (I).

The compound (I) is isomorphous to the Eu^III complex (Brayshaw et al., 1995). The asymmetric unit contains one Lu^III atom located on a twofold rotation axis, one and a half dipicolinate carboxylate ligand, two Cs⁺ cations and water molecules (Fig. 1). The unit cell could be regarded as successive layers along the crystallographic c-axis formed by [Lu(dipic)₃]^3- anionic planes and [Cs⁺, H₂O] cationic planes (Fig. 2).

Two types of Cs⁺ cations, which are bridged by both carboxylate and water oxygen atoms, form a chain extending throughout the crystal (Fig. 2). The chain could be considered as a sequence of ten-coordinate caesium ions linked, through bridging coordination, to eight-coordinate caesium ions. All water molecules are involved in coordination either to Cs⁺, to other water molecules or to the oxygen atoms of the dipicolinate ligands.

The Lu^III atom, being nine-coordinated by six O and three N atoms of three dipicolinate ligands, is in the centre of a quite regular tricapped trigonal prismatic coordination sphere (Fig. 1). In those compounds, metal-to-metal distances play an important role concerning the electronic interactions affecting luminescence behaviour. For (I) the shortest Lu···Lu separation is 10.22 Å in contrast with the 4.50Å of the shortest Cs···Lu separation. These distances compare well with those observed in the Cs₃[Eu(dipic)₃].9H₂O (Brayshaw et al., 1995). Geometrical parameters of the dipicolinate ligand are found to be in agreement with those of other structures containing dipicolinate.

Although the H atoms attached to water molecules could not be located, short O—O contacts clearly indicate the occurrence of a complicated hydrogen-bonded network. The water molecules are positioned in a channel formed by the successive anionic and cationic layers. The water molecules in this channel appear to have considerable freedom of motion. The structural refinement of (I) reveals high values of the thermal motion parameters of the water oxygen atoms indicating that most of the water molecules are incorporated in the unit cell in disordered positions. This effect was also observed in the complexes Cs₃[Eu(dipic)₃].9H₂O, [Co(sar)][Lu(dipic)₃].13H₂O and Na₃[Eu(dipic)₃].nH₂O (Brayshaw et al., 1995; Murray et al., 1990) which have also been investigated by emission spectroscopy, showing that different arrangements of the water molecules induce different crystal field splittings, clearly pointed out in the emission spectra.

Related literature top

For potential applications of lanthanide complexes as second-order non-linear optical materials, see: Tancrez et al. (2005); Sénéchal et al. (2004). For the isomorphous Eu^III complex, see: Brayshaw et al. (1995). For other related complexes, see: Murray et al. (1990). For related literature, see: Flack & Bernardinelli (1999, 2000).

Experimental top

The caesium salt of the tris(dipicolinato)-Lu^III anion was prepared by reaction between dipicolinic acid (3Eq) and CsCO₃ acting as base and counter-anion in water. After stirring until everything dissolved, LuCl₃.6H₂O (1Eq) was added and the reaction was stirred at room temperature for two more hours. The water was evaporated and the white solid was dissolved in the minimum of boiling water. The complex was purified by three successive crystallizations at 4°C.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction 2006); cell refinement: CrysAlis RED (Oxford Diffraction 2006); data reduction: SORTAV (Blessing, 1989); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of [Lu(dipic)₃]^3- with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level and H atoms are omitted for clarity.
	Fig. 2. Crystal packing of Cs₃[Lu(dipic)₃].8H₂O with hydrogen bonds (in dotted line) and coordinate bonds to caesium. [Lu(dipic)₃]^3- anions and Cs⁺ cations are distributed in the cell as successive anionic/cationic layers along the crystallographic c-axis (Lu atoms are in green, Cs in yellow, O in red, C in grey and N in blue).

Tricaesium tris(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)lutetium(III) octahydrate top

Crystal data top

Cs₃[Lu(C₇H₃NO₄)₃]·8H₂O	F(000) = 2312
M_r = 1213.14	D_x = 2.446 Mg m⁻³
Orthorhombic, C222₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 17659 reflections
a = 10.0406 (2) Å	θ = 3.2–59.9°
b = 17.8109 (6) Å	µ = 6.36 mm⁻¹
c = 18.4221 (5) Å	T = 100 K
V = 3294.46 (16) Å³	Block, colourless
Z = 4	0.20 × 0.19 × 0.19 mm

Data collection top

Oxford Diffraction Xcalibur-Sapphire3 diffractometer	3520 independent reflections
Radiation source: fine-focus sealed tube	3491 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω scans	θ_max = 27.0°, θ_min = 3.2°
Absorption correction: gaussian (ABSORB; DeTitta, 1985)	h = −12→12
T_min = 0.308, T_max = 0.425	k = −22→22
51066 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.063	w = 1/[σ²(F_o²) + (0.0149P)² + 27.044P] where P = (F_o² + 2F_c²)/3
S = 1.46	(Δ/σ)_max < 0.001
3520 reflections	Δρ_max = 3.00 e Å⁻³
208 parameters	Δρ_min = −0.94 e Å⁻³
0 restraints	Absolute structure: Flack (1983),1501 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.270 (12)

Crystal data top

Cs₃[Lu(C₇H₃NO₄)₃]·8H₂O	V = 3294.46 (16) Å³
M_r = 1213.14	Z = 4
Orthorhombic, C222₁	Mo Kα radiation
a = 10.0406 (2) Å	µ = 6.36 mm⁻¹
b = 17.8109 (6) Å	T = 100 K
c = 18.4221 (5) Å	0.20 × 0.19 × 0.19 mm

Data collection top

Oxford Diffraction Xcalibur-Sapphire3 diffractometer	3520 independent reflections
Absorption correction: gaussian (ABSORB; DeTitta, 1985)	3491 reflections with I > 2σ(I)
T_min = 0.308, T_max = 0.425	R_int = 0.045
51066 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.063	w = 1/[σ²(F_o²) + (0.0149P)² + 27.044P] where P = (F_o² + 2F_c²)/3
S = 1.46	Δρ_max = 3.00 e Å⁻³
3520 reflections	Δρ_min = −0.94 e Å⁻³
208 parameters	Absolute structure: Flack (1983),1501 Friedel pairs
0 restraints	Absolute structure parameter: 0.270 (12)

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	U_iso*/U_eq	Occ. (<1)
Lu1	0.75054 (5)	0.0000	0.0000	0.00950 (7)
Cs1	0.74407 (4)	0.021678 (17)	−0.24335 (2)	0.01702 (8)
Cs2	0.5000	−0.26389 (3)	−0.2500	0.01796 (11)
N11	0.8713 (4)	−0.1197 (2)	−0.0042 (3)	0.0107 (8)
O11	0.6846 (4)	−0.0835 (2)	−0.0950 (2)	0.0149 (8)
O12	0.7226 (5)	−0.1846 (3)	−0.1649 (2)	0.0228 (12)
O13	1.0389 (5)	−0.0907 (3)	0.1601 (2)	0.0174 (11)
O14	0.9174 (4)	−0.01382 (19)	0.0906 (2)	0.0124 (8)
C12	0.9612 (6)	−0.1355 (3)	0.0466 (3)	0.0131 (12)
C13	1.0349 (6)	−0.2016 (3)	0.0468 (3)	0.0187 (13)
H13	1.1001	−0.2089	0.0819	0.022*
C14	1.0140 (14)	−0.2518 (3)	−0.0006 (8)	0.040 (2)
H14	1.0567	−0.2980	0.0026	0.048*
C15	0.9185 (7)	−0.2357 (4)	−0.0624 (3)	0.0199 (13)
H15	0.9073	−0.2688	−0.1010	0.024*
C16	0.8496 (6)	−0.1693 (3)	−0.0580 (3)	0.0132 (11)
C17	0.7438 (8)	−0.1440 (3)	−0.1112 (3)	0.0146 (6)
C18	0.9756 (6)	−0.0754 (3)	0.1041 (4)	0.0146 (6)
N21	0.5071 (8)	0.0000	0.0000	0.0173 (12)
O21	0.4794 (7)	−0.1104 (3)	0.1573 (3)	0.0323 (15)
O22	0.6543 (5)	−0.0785 (2)	0.0880 (2)	0.0168 (9)
C22	0.4415 (7)	−0.0390 (4)	0.0490 (3)	0.0242 (9)
C23	0.3047 (7)	−0.0426 (4)	0.0509 (3)	0.0242 (9)
H23	0.2584	−0.0719	0.0843	0.029*
C24	0.2430 (13)	0.0000	0.0000	0.0242 (9)
H24	0.1503	0.0000	0.0000	0.029*
C25	0.5310 (6)	−0.0805 (4)	0.1040 (4)	0.0146 (6)
O1W	0.7467 (9)	−0.1739 (4)	−0.3818 (4)	0.0584 (17)
O2W	0.9514 (7)	−0.0907 (4)	−0.3228 (4)	0.0424 (18)
O3W	0.5456 (5)	−0.0888 (3)	−0.3207 (3)	0.0240 (12)
O4WA	0.6970 (8)	0.2031 (4)	−0.2207 (6)	0.032 (3)	0.69 (2)
O4WB	0.7228 (15)	0.1956 (8)	−0.1715 (11)	0.023 (6)	0.31 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Lu1	0.00740 (14)	0.01013 (12)	0.01097 (13)	0.000	0.000	−0.00081 (10)
Cs1	0.01540 (16)	0.02237 (15)	0.01327 (15)	−0.00244 (13)	0.00109 (19)	−0.00051 (11)
Cs2	0.0245 (3)	0.01430 (19)	0.0151 (2)	0.000	−0.0028 (2)	0.000
N11	0.008 (2)	0.0127 (18)	0.011 (2)	−0.0017 (15)	0.0012 (18)	0.0004 (17)
O11	0.013 (2)	0.013 (2)	0.018 (2)	−0.0015 (16)	−0.0019 (16)	−0.0004 (16)
O12	0.023 (4)	0.023 (2)	0.022 (2)	0.0013 (18)	−0.0084 (19)	−0.0097 (17)
O13	0.019 (3)	0.023 (3)	0.010 (2)	0.0014 (18)	−0.0035 (16)	0.0022 (17)
O14	0.010 (2)	0.008 (2)	0.018 (2)	0.0010 (14)	−0.0021 (15)	−0.0017 (14)
C12	0.015 (3)	0.011 (2)	0.014 (3)	−0.0009 (19)	0.001 (2)	0.002 (2)
C13	0.018 (4)	0.017 (3)	0.021 (3)	0.004 (2)	−0.004 (2)	0.001 (2)
C14	0.033 (6)	0.023 (3)	0.066 (5)	−0.003 (3)	−0.040 (5)	0.009 (3)
C15	0.026 (4)	0.018 (3)	0.016 (3)	0.007 (3)	−0.002 (2)	−0.005 (2)
C16	0.015 (3)	0.012 (3)	0.012 (3)	−0.002 (2)	0.003 (2)	0.001 (2)
C17	0.0135 (16)	0.0138 (13)	0.0166 (13)	−0.0096 (16)	0.0027 (15)	−0.0028 (10)
C18	0.0135 (16)	0.0138 (13)	0.0166 (13)	−0.0096 (16)	0.0027 (15)	−0.0028 (10)
N21	0.009 (3)	0.027 (3)	0.016 (3)	0.000	0.000	−0.010 (3)
O21	0.038 (4)	0.039 (3)	0.021 (2)	−0.021 (3)	0.014 (2)	−0.009 (2)
O22	0.020 (3)	0.013 (2)	0.0168 (19)	−0.0027 (17)	0.0040 (17)	−0.0020 (15)
C22	0.0106 (19)	0.048 (2)	0.0143 (17)	−0.007 (2)	0.0024 (15)	−0.0146 (17)
C23	0.0106 (19)	0.048 (2)	0.0143 (17)	−0.007 (2)	0.0024 (15)	−0.0146 (17)
C24	0.0106 (19)	0.048 (2)	0.0143 (17)	−0.007 (2)	0.0024 (15)	−0.0146 (17)
C25	0.0135 (16)	0.0138 (13)	0.0166 (13)	−0.0096 (16)	0.0027 (15)	−0.0028 (10)
O1W	0.046 (4)	0.079 (5)	0.051 (3)	0.016 (5)	−0.002 (4)	−0.012 (3)
O2W	0.047 (4)	0.021 (3)	0.059 (4)	0.003 (3)	0.028 (3)	0.001 (3)
O3W	0.018 (3)	0.032 (3)	0.022 (3)	−0.004 (2)	−0.005 (2)	0.004 (2)
O4WA	0.028 (4)	0.030 (4)	0.039 (6)	−0.002 (3)	−0.003 (3)	0.007 (3)
O4WB	0.012 (11)	0.018 (7)	0.038 (13)	0.005 (5)	0.011 (7)	0.015 (6)

Geometric parameters (Å, º) top

Lu1—O22ⁱ	2.348 (4)	O11—C17	1.267 (8)
Lu1—O22	2.348 (4)	O12—C17	1.244 (7)
Lu1—O14	2.377 (4)	O13—C18	1.242 (9)
Lu1—O14ⁱ	2.377 (4)	O13—Cs1^ix	3.070 (5)
Lu1—O11	2.390 (4)	O13—Cs2^x	3.100 (5)
Lu1—O11ⁱ	2.390 (4)	O13—Cs1ⁱ	3.553 (5)
Lu1—N21	2.445 (8)	O14—C18	1.267 (8)
Lu1—N11ⁱ	2.454 (4)	O14—Cs1ⁱ	3.312 (4)
Lu1—N11	2.454 (4)	C12—C13	1.390 (8)
Lu1—Cs1	4.5002 (4)	C12—C18	1.513 (8)
Lu1—Cs1ⁱ	4.5002 (4)	C13—C14	1.267 (13)
Cs1—O13ⁱⁱ	3.070 (5)	C13—Cs2^x	3.810 (6)
Cs1—O3W	3.142 (5)	C13—H13	0.9300
Cs1—O22ⁱ	3.167 (4)	C14—C15	1.517 (12)
Cs1—O2W	3.237 (6)	C14—H14	0.9300
Cs1—O4WA	3.293 (8)	C15—C16	1.373 (9)
Cs1—O21ⁱⁱⁱ	3.299 (6)	C15—H15	0.9300
Cs1—O14ⁱ	3.312 (4)	C16—C17	1.514 (9)
Cs1—O11	3.367 (4)	C18—Cs1ⁱ	3.592 (6)
Cs1—O4WB	3.375 (16)	N21—C22ⁱ	1.315 (8)
Cs1—O21ⁱ	3.474 (6)	N21—C22	1.315 (8)
Cs1—C25ⁱ	3.502 (6)	O21—C25	1.230 (9)
Cs1—O13ⁱ	3.553 (5)	O21—Cs1^xi	3.299 (6)
Cs2—O12	3.073 (5)	O21—Cs1ⁱ	3.474 (6)
Cs2—O12^iv	3.073 (5)	O22—C25	1.273 (8)
Cs2—O13^v	3.100 (5)	O22—Cs1ⁱ	3.167 (4)
Cs2—O13^vi	3.100 (5)	C22—C23	1.376 (10)
Cs2—O4WA^vii	3.145 (8)	C22—C25	1.544 (10)
Cs2—O4WA^viii	3.145 (8)	C23—C24	1.356 (9)
Cs2—O4WB^vii	3.219 (14)	C23—Cs1^xi	3.840 (6)
Cs2—O4WB^viii	3.219 (14)	C23—H23	0.9300
Cs2—O3W	3.410 (6)	C24—C23ⁱ	1.356 (9)
Cs2—O3W^iv	3.410 (6)	C24—H24	0.9300
Cs2—C13^v	3.810 (6)	C25—Cs1ⁱ	3.502 (6)
Cs2—C13^vi	3.810 (6)	O3W—Cs1^iv	3.705 (6)
N11—C12	1.330 (7)	O4WA—Cs2^xii	3.145 (8)
N11—C16	1.345 (7)	O4WB—Cs2^xii	3.219 (14)

O22ⁱ—Lu1—O22	131.4 (2)	O13^v—Cs2—O4WA^viii	82.77 (19)
O22ⁱ—Lu1—O14	146.72 (14)	O13^vi—Cs2—O4WA^viii	79.26 (18)
O22—Lu1—O14	75.16 (15)	O4WA^vii—Cs2—O4WA^viii	158.5 (3)
O22ⁱ—Lu1—O14ⁱ	75.16 (15)	O12—Cs2—O4WB^vii	120.2 (4)
O22—Lu1—O14ⁱ	146.72 (14)	O12^iv—Cs2—O4WB^vii	72.8 (3)
O14—Lu1—O14ⁱ	90.4 (2)	O13^v—Cs2—O4WB^vii	86.8 (3)
O22ⁱ—Lu1—O11	75.58 (13)	O13^vi—Cs2—O4WB^vii	71.4 (3)
O22—Lu1—O11	91.20 (14)	O4WA^vii—Cs2—O4WB^vii	17.2 (3)
O14—Lu1—O11	130.16 (14)	O4WA^viii—Cs2—O4WB^vii	150.6 (3)
O14ⁱ—Lu1—O11	75.28 (14)	O12—Cs2—O4WB^viii	72.8 (3)
O22ⁱ—Lu1—O11ⁱ	91.20 (14)	O12^iv—Cs2—O4WB^viii	120.2 (4)
O22—Lu1—O11ⁱ	75.58 (13)	O13^v—Cs2—O4WB^viii	71.4 (3)
O14—Lu1—O11ⁱ	75.28 (14)	O13^vi—Cs2—O4WB^viii	86.8 (3)
O14ⁱ—Lu1—O11ⁱ	130.16 (14)	O4WA^vii—Cs2—O4WB^viii	150.6 (3)
O11—Lu1—O11ⁱ	147.8 (2)	O4WA^viii—Cs2—O4WB^viii	17.2 (3)
O22ⁱ—Lu1—N21	65.71 (12)	O4WB^vii—Cs2—O4WB^viii	154.1 (5)
O22—Lu1—N21	65.71 (12)	O12—Cs2—O3W	71.14 (12)
O14—Lu1—N21	134.81 (10)	O12^iv—Cs2—O3W	58.84 (12)
O14ⁱ—Lu1—N21	134.81 (10)	O13^v—Cs2—O3W	125.24 (14)
O11—Lu1—N21	73.90 (11)	O13^vi—Cs2—O3W	162.07 (13)
O11ⁱ—Lu1—N21	73.90 (11)	O4WA^vii—Cs2—O3W	111.48 (18)
O22ⁱ—Lu1—N11ⁱ	73.00 (16)	O4WA^viii—Cs2—O3W	88.59 (17)
O22—Lu1—N11ⁱ	134.33 (16)	O4WB^vii—Cs2—O3W	119.5 (3)
O14—Lu1—N11ⁱ	73.72 (14)	O4WB^viii—Cs2—O3W	85.3 (3)
O14ⁱ—Lu1—N11ⁱ	65.42 (14)	O12—Cs2—O3W^iv	58.84 (12)
O11—Lu1—N11ⁱ	134.47 (16)	O12^iv—Cs2—O3W^iv	71.14 (12)
O11ⁱ—Lu1—N11ⁱ	64.75 (15)	O13^v—Cs2—O3W^iv	162.07 (13)
N21—Lu1—N11ⁱ	119.60 (10)	O13^vi—Cs2—O3W^iv	125.24 (14)
O22ⁱ—Lu1—N11	134.33 (16)	O4WA^vii—Cs2—O3W^iv	88.59 (17)
O22—Lu1—N11	73.00 (16)	O4WA^viii—Cs2—O3W^iv	111.48 (19)
O14—Lu1—N11	65.42 (14)	O4WB^vii—Cs2—O3W^iv	85.3 (3)
O14ⁱ—Lu1—N11	73.72 (14)	O4WB^viii—Cs2—O3W^iv	119.5 (3)
O11—Lu1—N11	64.75 (15)	O3W—Cs2—O3W^iv	47.76 (19)
O11ⁱ—Lu1—N11	134.47 (16)	O12—Cs2—C13^v	129.96 (13)
N21—Lu1—N11	119.60 (10)	O12^iv—Cs2—C13^v	60.42 (13)
N11ⁱ—Lu1—N11	120.8 (2)	O13^v—Cs2—C13^v	47.80 (13)
O22ⁱ—Lu1—Cs1	41.88 (11)	O13^vi—Cs2—C13^v	113.68 (13)
O22—Lu1—Cs1	137.11 (11)	O4WA^vii—Cs2—C13^v	92.8 (2)
O14—Lu1—Cs1	135.91 (10)	O4WA^viii—Cs2—C13^v	83.7 (2)
O14ⁱ—Lu1—Cs1	45.74 (10)	O4WB^vii—Cs2—C13^v	109.0 (4)
O11—Lu1—Cs1	47.15 (10)	O4WB^viii—Cs2—C13^v	66.5 (4)
O11ⁱ—Lu1—Cs1	132.23 (10)	O3W—Cs2—C13^v	77.57 (13)
N21—Lu1—Cs1	89.173 (8)	O3W^iv—Cs2—C13^v	120.70 (13)
N11ⁱ—Lu1—Cs1	87.94 (12)	O12—Cs2—C13^vi	60.42 (13)
N11—Lu1—Cs1	92.88 (12)	O12^iv—Cs2—C13^vi	129.96 (13)
O22ⁱ—Lu1—Cs1ⁱ	137.11 (11)	O13^v—Cs2—C13^vi	113.68 (13)
O22—Lu1—Cs1ⁱ	41.88 (11)	O13^vi—Cs2—C13^vi	47.80 (13)
O14—Lu1—Cs1ⁱ	45.74 (10)	O4WA^vii—Cs2—C13^vi	83.7 (2)
O14ⁱ—Lu1—Cs1ⁱ	135.91 (10)	O4WA^viii—Cs2—C13^vi	92.8 (2)
O11—Lu1—Cs1ⁱ	132.23 (10)	O4WB^vii—Cs2—C13^vi	66.5 (4)
O11ⁱ—Lu1—Cs1ⁱ	47.15 (10)	O4WB^viii—Cs2—C13^vi	109.0 (4)
N21—Lu1—Cs1ⁱ	89.173 (8)	O3W—Cs2—C13^vi	120.70 (13)
N11ⁱ—Lu1—Cs1ⁱ	92.88 (12)	O3W^iv—Cs2—C13^vi	77.57 (13)
N11—Lu1—Cs1ⁱ	87.94 (12)	C13^v—Cs2—C13^vi	161.41 (18)
Cs1—Lu1—Cs1ⁱ	178.347 (17)	C12—N11—C16	119.3 (5)
O13ⁱⁱ—Cs1—O3W	115.98 (14)	C12—N11—Lu1	119.8 (4)
O13ⁱⁱ—Cs1—O22ⁱ	126.72 (12)	C16—N11—Lu1	120.9 (4)
O3W—Cs1—O22ⁱ	115.44 (13)	C17—O11—Lu1	124.9 (4)
O13ⁱⁱ—Cs1—O2W	61.89 (12)	C17—O11—Cs1	101.4 (3)
O3W—Cs1—O2W	79.37 (13)	Lu1—O11—Cs1	101.50 (14)
O22ⁱ—Cs1—O2W	142.10 (16)	C17—O12—Cs2	142.9 (5)
O13ⁱⁱ—Cs1—O4WA	77.43 (18)	C18—O13—Cs1^ix	139.2 (4)
O3W—Cs1—O4WA	125.53 (19)	C18—O13—Cs2^x	124.2 (4)
O22ⁱ—Cs1—O4WA	62.0 (2)	Cs1^ix—O13—Cs2^x	96.56 (13)
O2W—Cs1—O4WA	139.14 (19)	C18—O13—Cs1ⁱ	81.8 (4)
O13ⁱⁱ—Cs1—O21ⁱⁱⁱ	88.27 (12)	Cs1^ix—O13—Cs1ⁱ	101.70 (14)
O3W—Cs1—O21ⁱⁱⁱ	67.47 (13)	Cs2^x—O13—Cs1ⁱ	87.33 (12)
O22ⁱ—Cs1—O21ⁱⁱⁱ	98.92 (14)	C18—O14—Lu1	123.5 (4)
O2W—Cs1—O21ⁱⁱⁱ	118.85 (19)	C18—O14—Cs1ⁱ	92.2 (4)
O4WA—Cs1—O21ⁱⁱⁱ	60.2 (2)	Lu1—O14—Cs1ⁱ	103.33 (13)
O13ⁱⁱ—Cs1—O14ⁱ	97.84 (11)	N11—C12—C13	122.8 (5)
O3W—Cs1—O14ⁱ	133.79 (12)	N11—C12—C18	114.0 (5)
O22ⁱ—Cs1—O14ⁱ	52.77 (10)	C13—C12—C18	123.1 (5)
O2W—Cs1—O14ⁱ	91.16 (16)	C14—C13—C12	120.5 (7)
O4WA—Cs1—O14ⁱ	90.54 (19)	C14—C13—Cs2^x	123.1 (7)
O21ⁱⁱⁱ—Cs1—O14ⁱ	148.13 (12)	C12—C13—Cs2^x	95.2 (4)
O13ⁱⁱ—Cs1—O11	144.99 (12)	C14—C13—H13	119.7
O3W—Cs1—O11	84.68 (12)	C12—C13—H13	119.7
O22ⁱ—Cs1—O11	52.66 (10)	Cs2^x—C13—H13	50.1
O2W—Cs1—O11	97.89 (14)	C13—C14—C15	119.3 (7)
O4WA—Cs1—O11	114.7 (2)	C13—C14—H14	120.4
O21ⁱⁱⁱ—Cs1—O11	126.59 (13)	C15—C14—H14	120.4
O14ⁱ—Cs1—O11	51.67 (10)	C16—C15—C14	115.9 (6)
O13ⁱⁱ—Cs1—O4WB	84.6 (3)	C16—C15—H15	122.1
O3W—Cs1—O4WB	135.4 (3)	C14—C15—H15	122.1
O22ⁱ—Cs1—O4WB	48.2 (3)	N11—C16—C15	121.9 (5)
O2W—Cs1—O4WB	141.8 (3)	N11—C16—C17	113.3 (5)
O4WA—Cs1—O4WB	16.4 (3)	C15—C16—C17	124.8 (5)
O21ⁱⁱⁱ—Cs1—O4WB	74.7 (4)	O12—C17—O11	127.0 (7)
O14ⁱ—Cs1—O4WB	74.8 (4)	O12—C17—C16	117.5 (6)
O11—Cs1—O4WB	100.4 (3)	O11—C17—C16	115.5 (5)
O13ⁱⁱ—Cs1—O21ⁱ	128.72 (14)	O12—C17—Cs1	86.7 (3)
O3W—Cs1—O21ⁱ	90.39 (15)	O11—C17—Cs1	59.6 (3)
O22ⁱ—Cs1—O21ⁱ	39.15 (12)	C16—C17—Cs1	129.9 (4)
O2W—Cs1—O21ⁱ	168.30 (16)	O13—C18—O14	126.1 (6)
O4WA—Cs1—O21ⁱ	52.14 (18)	O13—C18—C12	118.4 (6)
O21ⁱⁱⁱ—Cs1—O21ⁱ	61.01 (17)	O14—C18—C12	115.5 (5)
O14ⁱ—Cs1—O21ⁱ	91.90 (11)	O13—C18—Cs1ⁱ	78.2 (4)
O11—Cs1—O21ⁱ	75.32 (12)	O14—C18—Cs1ⁱ	67.2 (3)
O4WB—Cs1—O21ⁱ	49.9 (3)	C12—C18—Cs1ⁱ	128.8 (4)
O13ⁱⁱ—Cs1—C25ⁱ	137.62 (15)	C22ⁱ—N21—C22	119.9 (9)
O3W—Cs1—C25ⁱ	97.62 (14)	C22ⁱ—N21—Lu1	120.0 (4)
O22ⁱ—Cs1—C25ⁱ	21.25 (13)	C22—N21—Lu1	120.0 (4)
O2W—Cs1—C25ⁱ	155.39 (16)	C25—O21—Cs1^xi	121.5 (5)
O4WA—Cs1—C25ⁱ	61.7 (2)	C25—O21—Cs1ⁱ	81.1 (4)
O21ⁱⁱⁱ—Cs1—C25ⁱ	81.26 (15)	Cs1^xi—O21—Cs1ⁱ	92.82 (13)
O14ⁱ—Cs1—C25ⁱ	73.18 (12)	C25—O22—Lu1	125.2 (4)
O11—Cs1—C25ⁱ	57.51 (13)	C25—O22—Cs1ⁱ	94.4 (4)
O4WB—Cs1—C25ⁱ	53.1 (3)	Lu1—O22—Cs1ⁱ	108.45 (15)
O21ⁱ—Cs1—C25ⁱ	20.31 (14)	N21—C22—C23	122.8 (7)
O13ⁱⁱ—Cs1—O13ⁱ	61.34 (14)	N21—C22—C25	114.3 (6)
O3W—Cs1—O13ⁱ	160.15 (13)	C23—C22—C25	122.8 (6)
O22ⁱ—Cs1—O13ⁱ	74.71 (11)	C24—C23—C22	114.3 (8)
O2W—Cs1—O13ⁱ	82.72 (16)	C24—C23—Cs1^xi	124.7 (4)
O4WA—Cs1—O13ⁱ	74.07 (18)	C22—C23—Cs1^xi	98.5 (4)
O21ⁱⁱⁱ—Cs1—O13ⁱ	129.85 (12)	C24—C23—H23	122.8
O14ⁱ—Cs1—O13ⁱ	37.82 (10)	C22—C23—H23	122.8
O11—Cs1—O13ⁱ	89.41 (11)	Cs1^xi—C23—H23	48.6
O4WB—Cs1—O13ⁱ	64.3 (3)	C23ⁱ—C24—C23	125.6 (11)
O21ⁱ—Cs1—O13ⁱ	106.43 (12)	C23ⁱ—C24—H24	117.2
C25ⁱ—Cs1—O13ⁱ	95.10 (14)	C23—C24—H24	117.2
O12—Cs2—O12^iv	125.26 (18)	O21—C25—O22	127.3 (7)
O12—Cs2—O13^v	138.44 (13)	O21—C25—C22	119.0 (6)
O12^iv—Cs2—O13^v	91.16 (13)	O22—C25—C22	113.6 (5)
O12—Cs2—O13^vi	91.16 (13)	O21—C25—Cs1ⁱ	78.6 (4)
O12^iv—Cs2—O13^vi	138.44 (13)	O22—C25—Cs1ⁱ	64.4 (3)
O13^v—Cs2—O13^vi	66.60 (18)	C22—C25—Cs1ⁱ	133.9 (4)
O12—Cs2—O4WA^vii	134.6 (2)	Cs1—O3W—Cs2	119.00 (16)
O12^iv—Cs2—O4WA^vii	58.0 (2)	Cs1—O3W—Cs1^iv	91.19 (14)
O13^v—Cs2—O4WA^vii	79.26 (18)	Cs2—O3W—Cs1^iv	104.99 (14)
O13^vi—Cs2—O4WA^vii	82.77 (19)	Cs2^xii—O4WA—Cs1	91.3 (2)
O12—Cs2—O4WA^viii	58.0 (2)	Cs2^xii—O4WB—Cs1	88.6 (4)
O12^iv—Cs2—O4WA^viii	134.6 (2)

Symmetry codes: (i) x, −y, −z; (ii) −x+2, −y, z−1/2; (iii) −x+1, −y, z−1/2; (iv) −x+1, y, −z−1/2; (v) −x+3/2, −y−1/2, z−1/2; (vi) x−1/2, −y−1/2, −z; (vii) x−1/2, y−1/2, z; (viii) −x+3/2, y−1/2, −z−1/2; (ix) −x+2, −y, z+1/2; (x) −x+3/2, −y−1/2, z+1/2; (xi) −x+1, −y, z+1/2; (xii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	Cs₃[Lu(C₇H₃NO₄)₃]·8H₂O
M_r	1213.14
Crystal system, space group	Orthorhombic, C222₁
Temperature (K)	100
a, b, c (Å)	10.0406 (2), 17.8109 (6), 18.4221 (5)
V (Å³)	3294.46 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.36
Crystal size (mm)	0.20 × 0.19 × 0.19

Data collection
Diffractometer	Oxford Diffraction Xcalibur-Sapphire3 diffractometer
Absorption correction	Gaussian (ABSORB; DeTitta, 1985)
T_min, T_max	0.308, 0.425
No. of measured, independent and observed [I > 2σ(I)] reflections	51066, 3520, 3491
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.063, 1.46
No. of reflections	3520
No. of parameters	208
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0149P)² + 27.044P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	3.00, −0.94
Absolute structure	Flack (1983),1501 Friedel pairs
Absolute structure parameter	0.270 (12)

Computer programs: CrysAlis CCD (Oxford Diffraction 2006), CrysAlis RED (Oxford Diffraction 2006), SORTAV (Blessing, 1989), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

References

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