Triaquatris(μ-oxydiacetato)dipraseodymium(III) pentahydrate and hexaaquatris(μ-oxydiacetato)dineodymium(III) oxydiacetic acid solvate dihydrate

Two new complexes of the Ln₂(oda)₃·nH₂O (oda =–O₂CCH₂OCH₂CO₂–) series are reported, i.e. {[Pr₂(C₄H₄O₅)₃(H₂O)₃]·5H₂O}_n and {[Nd₂(C₄H₄O₅)₃(H₂O)₆]·C₄H₆O₅·-2H₂O}_n. The former is isostructural with the reported La analogue, while the latter is a new structural variety within the series. Each compound exhibits two independent nine-coordinated Ln centres showing a variety of coordination geometries.

S1. Comment

The self-assembly of lanthanide(III) metal centres with oxydiacetate ligands (oda = –O₂CCH₂OCH₂CO₂–) leads to a series of crystalline coordination solids formulated as Ln₂(oda)₃.nH₂O with an interesting variety of crystal-packing motifs. This is in accordance with the experience that the crystal structures of the lanthanide compounds frequently change along the series as a result of the lanthanide contraction. The crystals formed by the larger lanthanum [La₂(C₄H₄O₅)₃(H₂O)₃. 5H₂O]n are hexagonal, P62c (Baggio et al., 1996), and present two nine coordinated La centres; those for the intermediate gadolinium and europium compounds are orthorhombic, Ama2 (Aramendia et al., 1999) and present a mixture of nine and eight coordinated Ln centres, as it is also the case for the smaller Er (Elding, 1977) and Y (Baggio et al., 1999) analogues, which crystallize in the orthorhombic space group C222 (1).

Focusing our attention primarily on the structural aspects of these extended polymeric 4f complexes we report herein the preparation and structural characterization of the analogous compounds comprising praseodymium and neodymium: [Pr₂(C₄H₄O₅)₃(H₂O)₃·5H₂O]_n, (I), and [Nd₂(C₄H₄O₅)₃(H₂O)₆·2H₂O·C₄H₆O₅]_n, (II). \sch

Compound (I) is isostructural to the lanthanum polymer (Baggio, 1996) and will not be described in too much detail here. Selected bond lengths and angles are listed in Table 1, and Figure 1 gives a sketch of its coordination scheme. The two metal centres are highly symmetric, with Pr2 occupying a site `a' of local symmetry 32, and coordinated to three tridentate oda units, while Pr1, which occupies a site `d' of symmetry \-6, receives six bonds from the outer carboxylate O atoms as well as those from three aqua molecules. Both coordination polyhedra have the shape of tricapped trigonal prisms, the one around Pr2 being regular and the one centred at Pr1 displaying a rotation of ca 13° between opposite triangular faces. The fact that all the carboxylate as well as the ether O atoms take part in the connectivity to the cations leads to a tightly woven three dimensional network, leaving only a few empty spaces, filled in turn by the (disordered) hydration water molecules, which attach to the main structure via hydrogen bonding (See Table 2 for short O···O contacts).

Compound (2) presents, instead, a novel disposition of the ligands, not found before in any member of the series. As already stated, two independent Nd centres are present: Nd1 is bonded to two tridentate oda groups (oda1 and oda2) and to two water molecules (O1W and O2W). The ninth bond (O41) is provided by a <010> translationally related oda1 ligand, to end up with a linear polymeric chain along the short unique b axis.

As it is often the case with lanthanide cations bound to three tridentate oda groups, or to two tridentate odas plus three extra monodentate units completing the ninefold environment (the present case), the Nd1 polyhedron displays a tricapped trigonal prismatic geometry. The three monodentate ligands (O1W, O2W and O41) adopt a planar configuration very much resembling that of the missing third oda unit. The resulting polyhedron is one with only slight modifications from the regular environment found in much more symmetric polyhedra [e.g. the one around Pr1 in (I)].

A completely different arrangement is found for Nd2, which is bonded to a single tridentate oxydiacetate group (oda3) and to six monodentate units, four of which are water molecules (O3W to O6W), and the remaining two, oxygen atoms from bridging carboxylates. One of these is O43 from a neigbouring (also a <010> translationally related) oxydiacetate unit, again to built up linear chains parallel to those already defined by the Nd1 polyhedra. The second, O42, is provided by these latter groups; the Nd—O42 bonds transversally link both types of linear arrays, acting as the rungs of a firmly connected ladder-like strip (Fig. 2).

The presence of a single tridentate, plus six monodentate ligands favours a less constrained environment around Nd2 in the form of a monocapped square antiprism in which O33 occupies the capping position; O13, O53, O4W and O5W the equatorial plane and the remaining two water molecules plus the two remaining bridging carboxylate O atoms (O42 and O43) the basal plane. The largest distortion in the polyhedron is observed at the rather long Nd2—O3W distance [2.674 (9) Å]. The structure is completed by two non-coordinated water molecules (O7 and a triply disordered O8W) and an H₂oda neutral molecule. All of them, as well as the six coordinated water molecules, play an active role as hydrogen donors in a dense hydrogen bonding network in which the oxygen atoms from the coordinated oda groups act mainly as acceptors. Although the H atoms bonded to O atoms could not be reliably located, the hydrogen bonding interaction scheme could be confidently guessed both from the shortest (< 3.0 Å) O···O contacts (shown in Table 4) as well as from some significant structural details (viz C14—O24 and C44—O44 are sensibly longer than C14—O14 and C44—O54, respectively, at the same time that O24···O22 and O44···O51 are rather short. Charge balance and IR data (see Experimental section) required the presence of two OH groups in oda4; the preceeding geometrical arguments, in turn, point almost unambigously to the protonated character of O24 and O44.

S2. Experimental

The reaction of Pr₂O₃ and Nd₂O₃ with excess oxydiacetic acid in water (1:7:100) and subsequent work-up afforded light-green crystals of (I) and light-blue crystals of (II) in good yields. The procedure has been described previously in detail (Baggio et al., 1996). The IR spectra of the two compounds show significant changes in the COOH range. In fact the IR spectrum of compound (II) shows the characteristic absorptions of the acyd carbonyl groups (1738–1683 cm^-1) in addition to the bands of the carboxylate anions (1597 and 1445 cm^-1) and water molecules (~1641 and ~3550–3400 cm^-1) also observed for compound (I). TGA measurements show that both compounds lose almost exactly eight water molecules per formula unit well below 450 K.

All chemicals were of reagent-grade purity and used as received. Water was purified by a Millipore milli-Q system. Elemental analyses (C,H) were performed on a Carlo Erba EA 1108 instrument. Infrared spectra were recorded as KBr discs with a Nicolet 510P FT—IR spectrophotometer. Thermogravimetric analyses were recorded on a Shimadzu DTG50 thermal analyzer under an atmosphere of air at a heating rate of 5 K min^-1.

S3. Refinement

In both structures some hydration water molecules appeared split in a number of sites of lower occupancy, turning thus difficult to assess their correct total number just from the X-ray data alone. They were accordingly refined with adjustable populations constrained to add up to the value given by the thermogravimetric analysis, and a unique, common isotropic displacement factor.

As the H atoms could not be found in the difference Fourier synthesis, only those attached to carbon were included in ideallized positions, and refined using a riding scheme, both in coordinates as in displacement factors.

Computing details

For both compounds, data collection: P3/P4-PC (Siemens, 1991); cell refinement: P3/P4-PC. Data reduction: XDISK in SHELXTL/PC (Sheldrick, 1991) for (I); XDISK in SHELXTL/PC (Sheldrick,1991) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b). Molecular graphics: XP in SHELXTL/PC for (I); XP in SHELXTL/PC (Sheldrick, 1991) for (II). For both compounds, software used to prepare material for publication: CIFTAB (Sheldrick, 1993), PARST (Nardelli, 1983) and CSD (Allen et al., 1983).

Figures

	Fig. 1. Molecular diagrams showing atom numbering and coordination schemes. In full line, independent atoms; in dotted lines, symmetry related ones. Thermal ellipsoids drawn at a 40% level. a) Compound (1); b) Compound (2).
	Fig. 2. Schematic diagram along a^*, showing a ladder-like strip in (2), built up along the uniq axis b.

(I) Praseodimium oxydiacetate

Crystal data

[Pr2(C4H4O5)3(H2O)3]·5H2O	Dx = 2.06 Mg m^−3
Mr = 822.16	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P62c	Cell parameters from 25 reflections
a = 9.4003 (12) Å	θ = 7.5–12.5°
c = 17.350 (4) Å	µ = 3.72 mm^−1
V = 1327.8 (4) Å^3	T = 293 K
Z = 2	Prisms, light green
F(000) = 804	0.35 × 0.15 × 0.14 mm

Data collection

Siemens R3m diffractometer	738 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 25.0°, θmin = 2.4°
ω/2θ scans	h = −11→0
Absorption correction: ψ-scan (XEMP in SHELXTL/PC; Sheldrick, 1991)	k = 0→11
Tmin = 0.35, Tmax = 0.60	l = 0→20
1693 measured reflections	2 standard reflections every 98 reflections
780 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: C-H:geom O-H:not found
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.059	Calculated w = 1/[σ^2(Fo^2) + (0.031P)^2 + 2.733P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.01
780 reflections	Δρmax = 0.94 e Å^−3
63 parameters	Δρmin = −0.87 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (4)

Special details

Refinement. The structure was solved by direct methods and refined on F², with anisotropic displacement factors for all non-H atoms with full occupancy.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pr1	0.6667	0.3333	0.2500	0.01639 (16)
Pr2	0.0000	0.0000	0.0000	0.01481 (16)
O1	0.2108 (5)	0.1722 (5)	0.0965 (2)	0.0321 (9)
O2	0.4473 (5)	0.2704 (5)	0.1572 (2)	0.0384 (10)
O3	0.2715 (6)	0.0000	0.0000	0.0299 (14)
C1	0.3484 (5)	0.1825 (14)	0.1061 (2)	0.0268 (11)
C2	0.4000 (8)	0.0929 (9)	0.0534 (4)	0.0442 (17)
H2A	0.4985	0.1703	0.0259	0.053*
H2B	0.4246	0.0201	0.0828	0.053*
O1W	0.5625 (9)	0.5502 (9)	0.2500	0.056 (2)
O2WA	0.158 (3)	0.285 (2)	0.2500	0.098 (4)*	0.692 (17)
O2WB	0.082 (6)	0.180 (4)	0.2500	0.098 (4)*	0.352 (17)
O2WC	0.226 (3)	−0.296 (3)	0.1299 (11)	0.098 (4)*	0.311 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pr1	0.02006 (19)	0.02006 (19)	0.0090 (2)	0.01003 (10)	0.000	0.000
Pr2	0.01558 (19)	0.01558 (19)	0.0133 (3)	0.00779 (9)	0.000	0.000
O1	0.026 (2)	0.041 (2)	0.032 (2)	0.0186 (18)	−0.0129 (18)	−0.0171 (18)
O2	0.037 (2)	0.042 (2)	0.036 (2)	0.0195 (19)	−0.019 (2)	−0.0143 (19)
O3	0.022 (2)	0.043 (4)	0.032 (3)	0.0216 (18)	−0.0098 (13)	−0.020 (3)
C1	0.024 (2)	0.034 (4)	0.021 (2)	0.014 (3)	−0.0084 (18)	−0.004 (4)
C2	0.030 (3)	0.060 (4)	0.052 (4)	0.029 (3)	−0.022 (3)	−0.033 (4)
O1W	0.066 (5)	0.037 (4)	0.064 (4)	0.025 (4)	0.000	0.000

Geometric parameters (Å, º)

Pr1—O2^i	2.444 (4)	Pr2—O1^viii	2.478 (4)
Pr1—O2^ii	2.444 (4)	Pr2—O1^ix	2.478 (4)
Pr1—O2^iii	2.444 (4)	Pr2—O1^x	2.478 (4)
Pr1—O2^iv	2.444 (4)	Pr2—O3^x	2.552 (5)
Pr1—O2	2.444 (4)	Pr2—O3	2.552 (5)
Pr1—O2^v	2.444 (4)	Pr2—O3^ix	2.552 (5)
Pr1—O1W^iv	2.666 (7)	O1—C1	1.259 (7)
Pr1—O1W^i	2.666 (7)	O2—C1	1.251 (7)
Pr1—O1W	2.666 (7)	O3—C2	1.423 (6)
Pr2—O1	2.478 (4)	O3—C2^vii	1.423 (6)
Pr2—O1^vi	2.478 (4)	C1—C2	1.480 (11)
Pr2—O1^vii	2.478 (4)
O1···O2WA	2.99 (1)	O1W···O2WA^xi	2.63 (2)
O1···O2WB	2.94 (2)	O1W···O2WB^xi	2.96 (3)
O2^i—Pr1—O2^ii	82.4 (2)	O1^vii—Pr2—O1^viii	79.36 (15)
O2^i—Pr1—O2^iii	135.79 (7)	O1—Pr2—O1^ix	79.36 (15)
O2^ii—Pr1—O2^iii	81.34 (15)	O1^vi—Pr2—O1^ix	86.9 (2)
O2^i—Pr1—O2^iv	81.34 (15)	O1^vii—Pr2—O1^ix	150.66 (18)
O2^ii—Pr1—O2^iv	135.79 (7)	O1^viii—Pr2—O1^ix	123.54 (17)
O2^iii—Pr1—O2^iv	82.4 (2)	O1—Pr2—O1^x	79.36 (15)
O2^i—Pr1—O2	81.34 (15)	O1^vi—Pr2—O1^x	123.54 (17)
O2^ii—Pr1—O2	135.79 (7)	O1^vii—Pr2—O1^x	86.9 (2)
O2^iii—Pr1—O2	135.79 (7)	O1^viii—Pr2—O1^x	150.66 (19)
O2^iv—Pr1—O2	81.34 (15)	O1^ix—Pr2—O1^x	79.36 (15)
O2^i—Pr1—O2^v	135.79 (7)	O1—Pr2—O3^x	136.57 (10)
O2^ii—Pr1—O2^v	81.34 (15)	O1^vi—Pr2—O3^x	61.77 (9)
O2^iii—Pr1—O2^v	81.34 (15)	O1^vii—Pr2—O3^x	75.33 (9)
O2^iv—Pr1—O2^v	135.79 (7)	O1^viii—Pr2—O3^x	136.57 (10)
O2—Pr1—O2^v	82.4 (2)	O1^ix—Pr2—O3^x	75.33 (9)
O2^i—Pr1—O1W^iv	69.57 (15)	O1^x—Pr2—O3^x	61.77 (9)
O2^ii—Pr1—O1W^iv	69.57 (15)	O1—Pr2—O3	61.77 (9)
O2^iii—Pr1—O1W^iv	66.24 (15)	O1^vi—Pr2—O3	136.57 (10)
O2^iv—Pr1—O1W^iv	66.24 (15)	O1^vii—Pr2—O3	61.77 (9)
O2—Pr1—O1W^iv	138.76 (10)	O1^viii—Pr2—O3	75.33 (9)
O2^v—Pr1—O1W^iv	138.76 (10)	O1^ix—Pr2—O3	136.57 (10)
O2^i—Pr1—O1W^i	66.24 (15)	O1^x—Pr2—O3	75.33 (9)
O2^ii—Pr1—O1W^i	66.24 (15)	O3^x—Pr2—O3	120.0
O2^iii—Pr1—O1W^i	138.76 (10)	O1—Pr2—O3^ix	75.33 (9)
O2^iv—Pr1—O1W^i	138.76 (10)	O1^vi—Pr2—O3^ix	75.33 (9)
O2—Pr1—O1W^i	69.57 (15)	O1^vii—Pr2—O3^ix	136.57 (10)
O2^v—Pr1—O1W^i	69.57 (15)	O1^viii—Pr2—O3^ix	61.77 (9)
O1W^iv—Pr1—O1W^i	120.0	O1^ix—Pr2—O3^ix	61.77 (9)
O2^i—Pr1—O1W	138.76 (10)	O1^x—Pr2—O3^ix	136.57 (10)
O2^ii—Pr1—O1W	138.76 (10)	O3^x—Pr2—O3^ix	120.0
O2^iii—Pr1—O1W	69.57 (15)	O3—Pr2—O3^ix	120.0
O2^iv—Pr1—O1W	69.57 (15)	C1—O1—Pr2	126.5 (5)
O2—Pr1—O1W	66.24 (15)	C1—O2—Pr1	152.3 (6)
O2^v—Pr1—O1W	66.24 (15)	C2—O3—C2^vii	114.4 (6)
O1W^iv—Pr1—O1W	120.000 (2)	C2—O3—Pr2	122.8 (3)
O1W^i—Pr1—O1W	120.000 (2)	C2^vii—O3—Pr2	122.8 (3)
O1—Pr2—O1^vi	150.66 (19)	O2—C1—O1	122.7 (9)
O1—Pr2—O1^vii	123.54 (17)	O2—C1—C2	117.8 (6)
O1^vi—Pr2—O1^vii	79.36 (15)	O1—C1—C2	119.4 (5)
O1—Pr2—O1^viii	86.9 (2)	O3—C2—C1	109.4 (4)
O1^vi—Pr2—O1^viii	79.36 (15)

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

(II) Neodimium oxydiacetate

Crystal data

[Nd2(C4H4O5)3(H2O)6]·2H2O·C4H6O5	F(000) = 1896
Mr = 962.91	Dx = 2.09 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.096 (2) Å	Cell parameters from 25 reflections
b = 6.844 (1) Å	θ = 7.5–15°
c = 32.223 (3) Å	µ = 3.46 mm^−1
β = 99.59 (1)°	T = 293 K
V = 3065.1 (6) Å^3	Plates, light blue
Z = 4	0.36 × 0.24 × 0.10 mm

Data collection

Siemens R3m diffractometer	3568 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
ω/2θ scans	h = 0→16
Absorption correction: ψ-scan (XEMP in SHELXTL/PC, Sheldrick, 1991)	k = 0→8
Tmin = 0.38, Tmax = 0.70	l = −38→37
5674 measured reflections	2 standard reflections every 98 reflections
5393 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: C-H:geom O-H:not found
wR(F^2) = 0.145	H-atom parameters constrained
S = 1.03	Calculated w = 1/[σ^2(Fo^2) + (0.065P)^2 + 37.22P] where P = (Fo^2 + 2Fc^2)/3
5393 reflections	(Δ/σ)max < 0.01
419 parameters	Δρmax = 0.77 e Å^−3
1 restraint	Δρmin = −0.89 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Nd1	0.01488 (4)	0.55193 (9)	0.138457 (16)	0.01857 (17)
Nd2	−0.02898 (4)	0.55690 (9)	0.328610 (16)	0.01806 (16)
O11	0.1722 (5)	0.4571 (12)	0.1783 (3)	0.0306 (18)
O21	0.3244 (6)	0.5260 (12)	0.2050 (3)	0.034 (2)
O31	0.1170 (5)	0.8153 (11)	0.1822 (3)	0.0298 (19)
O41	−0.0347 (5)	1.2212 (11)	0.1540 (3)	0.031 (2)
O51	−0.0383 (6)	0.9094 (11)	0.1321 (3)	0.032 (2)
C11	0.2384 (7)	0.5720 (17)	0.1940 (3)	0.024 (2)
C21	0.2138 (7)	0.7810 (16)	0.2005 (3)	0.023 (2)
H21A	0.2229	0.8099	0.2304	0.028*
H21B	0.2560	0.8655	0.1877	0.028*
C31	0.0847 (8)	1.0095 (15)	0.1872 (4)	0.029 (3)
H31A	0.1351	1.1011	0.1835	0.035*
H31B	0.0706	1.0260	0.2155	0.035*
C41	−0.0037 (8)	1.0514 (17)	0.1557 (4)	0.027 (2)
O12	−0.1031 (5)	0.5532 (14)	0.0750 (2)	0.0337 (19)
O22	−0.2494 (5)	0.5768 (15)	0.0373 (2)	0.040 (2)
O32	−0.1608 (5)	0.5670 (12)	0.1461 (2)	0.0233 (16)
O42	−0.1211 (5)	0.5717 (13)	0.2570 (2)	0.0313 (19)
O52	−0.0243 (5)	0.5780 (13)	0.2095 (2)	0.0296 (18)
C12	−0.1928 (7)	0.5627 (17)	0.0716 (3)	0.024 (2)
C22	−0.2364 (7)	0.5512 (19)	0.1107 (3)	0.026 (2)
H22A	−0.2823	0.6563	0.1111	0.031*
H22B	−0.2698	0.4278	0.1116	0.031*
C32	−0.1941 (7)	0.5595 (19)	0.1856 (3)	0.027 (2)
H32A	−0.2294	0.4393	0.1878	0.032*
H32B	−0.2367	0.6688	0.1881	0.032*
C42	−0.1074 (7)	0.5688 (18)	0.2202 (4)	0.029 (3)
O13	0.1307 (5)	0.4609 (11)	0.3665 (2)	0.0292 (18)
O23	0.2822 (5)	0.5262 (12)	0.3953 (3)	0.041 (2)
O33	0.0768 (5)	0.8191 (10)	0.3705 (2)	0.0241 (17)
O43	−0.0739 (5)	1.2220 (10)	0.3407 (2)	0.0249 (17)
O53	−0.0804 (6)	0.9045 (11)	0.3228 (2)	0.0303 (19)
C13	0.1969 (8)	0.5731 (17)	0.3838 (4)	0.026 (2)
C23	0.1721 (7)	0.7805 (16)	0.3927 (4)	0.026 (3)
H23A	0.1743	0.7990	0.4227	0.031*
H23B	0.2178	0.8691	0.3833	0.031*
C33	0.0466 (8)	1.0128 (16)	0.3758 (4)	0.027 (3)
H33A	0.0965	1.1040	0.3712	0.033*
H33B	0.0336	1.0313	0.4042	0.033*
C43	−0.0440 (8)	1.0480 (16)	0.3441 (3)	0.024 (2)
O14	0.0490 (6)	0.7483 (14)	0.4739 (3)	0.039 (2)
O24	0.0752 (6)	0.8449 (14)	0.5417 (2)	0.040 (2)
O34	−0.1322 (5)	0.6445 (13)	0.4795 (2)	0.034 (2)
O44	−0.3728 (6)	0.5164 (14)	0.4413 (3)	0.042 (2)
O54	−0.2438 (6)	0.5228 (16)	0.4115 (3)	0.047 (3)
C14	0.0228 (8)	0.7707 (17)	0.5075 (4)	0.029 (3)
C24	−0.0788 (8)	0.7265 (18)	0.5162 (3)	0.031 (3)
H24A	−0.0756	0.6356	0.5395	0.037*
H24B	−0.1093	0.8458	0.5236	0.037*
C34	−0.2268 (8)	0.592 (2)	0.4851 (4)	0.035 (3)
H34A	−0.2572	0.7001	0.4973	0.042*
H34B	−0.2250	0.4802	0.5036	0.042*
C44	−0.2815 (8)	0.5436 (17)	0.4419 (4)	0.028 (2)
O1W	0.1194 (8)	0.7023 (15)	0.0933 (3)	0.062 (3)
O2W	0.0736 (6)	0.3002 (12)	0.0895 (3)	0.035 (2)
O3W	0.0332 (6)	0.2991 (13)	0.2769 (3)	0.040 (2)
O4W	0.0845 (6)	0.6921 (13)	0.2847 (2)	0.034 (2)
O5W	−0.0583 (6)	0.5854 (14)	0.4016 (2)	0.040 (2)
O6W	−0.2106 (5)	0.5591 (13)	0.3277 (2)	0.0313 (18)
O7W	−0.3629 (7)	0.5492 (17)	0.2626 (3)	0.054 (3)
O8WA	0.1342 (16)	0.514 (3)	0.0209 (7)	0.062 (5)*	0.456 (10)
O8WB	0.003 (3)	0.832 (6)	0.0015 (12)	0.062 (5)*	0.303 (10)
O8WC	−0.029 (3)	0.741 (7)	−0.0015 (14)	0.062 (5)*	0.241 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nd1	0.0174 (3)	0.0188 (3)	0.0194 (3)	0.0005 (3)	0.0028 (2)	−0.0006 (3)
Nd2	0.0191 (3)	0.0172 (3)	0.0178 (3)	−0.0008 (3)	0.0030 (2)	−0.0004 (3)
O11	0.023 (4)	0.019 (4)	0.047 (5)	0.002 (4)	−0.002 (4)	−0.007 (4)
O21	0.029 (4)	0.023 (4)	0.047 (5)	0.002 (4)	−0.004 (4)	−0.006 (4)
O31	0.022 (4)	0.019 (4)	0.043 (5)	0.002 (3)	−0.008 (4)	−0.007 (4)
O41	0.028 (4)	0.014 (4)	0.053 (6)	0.003 (3)	0.010 (4)	0.001 (4)
O51	0.031 (4)	0.025 (5)	0.039 (5)	0.003 (4)	−0.002 (4)	0.001 (4)
C11	0.021 (5)	0.028 (6)	0.022 (5)	0.002 (5)	−0.001 (4)	0.005 (5)
C21	0.020 (5)	0.025 (6)	0.022 (6)	0.002 (5)	−0.001 (4)	−0.006 (5)
C31	0.034 (6)	0.015 (6)	0.035 (7)	0.011 (5)	−0.006 (5)	−0.013 (5)
C41	0.026 (6)	0.019 (6)	0.040 (7)	−0.006 (5)	0.017 (5)	0.007 (6)
O12	0.026 (4)	0.051 (5)	0.025 (4)	0.008 (4)	0.005 (3)	0.003 (4)
O22	0.025 (4)	0.068 (7)	0.024 (4)	0.004 (4)	0.000 (3)	−0.007 (5)
O32	0.020 (3)	0.037 (4)	0.012 (3)	0.005 (4)	0.000 (3)	−0.003 (4)
O42	0.025 (4)	0.051 (5)	0.017 (4)	−0.002 (4)	0.001 (3)	−0.006 (4)
O52	0.023 (4)	0.048 (5)	0.019 (4)	0.003 (4)	0.007 (3)	−0.003 (4)
C12	0.026 (6)	0.027 (6)	0.019 (5)	−0.003 (5)	−0.001 (4)	−0.004 (5)
C22	0.018 (5)	0.033 (6)	0.026 (6)	0.006 (5)	−0.002 (4)	0.000 (6)
C32	0.022 (5)	0.036 (6)	0.022 (6)	−0.004 (5)	0.006 (4)	−0.004 (6)
C42	0.021 (5)	0.031 (6)	0.033 (7)	0.001 (5)	0.000 (5)	−0.001 (6)
O13	0.031 (4)	0.017 (4)	0.037 (5)	0.004 (4)	−0.003 (3)	−0.003 (4)
O23	0.021 (4)	0.029 (5)	0.069 (7)	0.006 (4)	−0.005 (4)	−0.002 (5)
O33	0.023 (4)	0.015 (4)	0.032 (4)	0.005 (3)	−0.001 (3)	−0.005 (3)
O43	0.027 (4)	0.015 (4)	0.034 (5)	−0.008 (3)	0.010 (3)	0.000 (3)
O53	0.038 (4)	0.026 (5)	0.024 (4)	0.001 (4)	−0.002 (4)	−0.006 (4)
C13	0.024 (6)	0.027 (6)	0.029 (6)	0.002 (5)	0.006 (5)	0.006 (5)
C23	0.021 (5)	0.021 (6)	0.033 (6)	−0.005 (5)	−0.001 (5)	−0.001 (5)
C33	0.026 (6)	0.021 (6)	0.035 (7)	0.003 (5)	0.004 (5)	−0.002 (5)
C43	0.033 (6)	0.013 (5)	0.026 (6)	−0.003 (5)	0.008 (5)	0.010 (5)
O14	0.036 (5)	0.054 (6)	0.025 (5)	−0.001 (4)	0.002 (4)	−0.004 (4)
O24	0.037 (5)	0.057 (6)	0.023 (4)	−0.008 (4)	−0.002 (4)	−0.011 (4)
O34	0.027 (4)	0.052 (5)	0.022 (4)	−0.012 (4)	0.003 (3)	−0.016 (4)
O44	0.032 (5)	0.054 (6)	0.040 (5)	−0.003 (4)	0.005 (4)	−0.007 (4)
O54	0.037 (5)	0.081 (8)	0.021 (4)	−0.011 (5)	0.000 (4)	−0.010 (5)
C14	0.033 (6)	0.028 (6)	0.022 (7)	−0.003 (5)	−0.010 (5)	0.002 (5)
C24	0.038 (7)	0.036 (7)	0.018 (6)	−0.007 (6)	0.000 (5)	0.002 (5)
C34	0.036 (7)	0.045 (8)	0.025 (6)	−0.007 (6)	0.006 (5)	−0.005 (6)
C44	0.033 (6)	0.022 (6)	0.030 (6)	−0.004 (5)	0.003 (5)	0.004 (6)
O1W	0.078 (7)	0.052 (6)	0.068 (7)	−0.033 (6)	0.047 (6)	−0.021 (6)
O2W	0.041 (5)	0.032 (5)	0.034 (5)	0.015 (4)	0.012 (4)	−0.003 (4)
O3W	0.035 (5)	0.038 (5)	0.047 (5)	0.003 (4)	0.010 (4)	0.001 (4)
O4W	0.034 (4)	0.046 (5)	0.024 (4)	−0.012 (4)	0.011 (4)	−0.001 (4)
O5W	0.041 (5)	0.063 (6)	0.020 (4)	−0.015 (5)	0.015 (4)	−0.009 (4)
O6W	0.025 (4)	0.039 (5)	0.029 (4)	0.006 (4)	0.002 (3)	−0.008 (4)
O7W	0.053 (6)	0.069 (7)	0.035 (5)	0.012 (6)	−0.007 (4)	−0.008 (5)

Geometric parameters (Å, º)

Nd1—O12	2.412 (7)	C31—C41	1.499 (16)
Nd1—O41^i	2.445 (8)	O12—C12	1.253 (12)
Nd1—O52	2.448 (7)	O22—C12	1.256 (12)
Nd1—O11	2.457 (7)	O32—C32	1.430 (12)
Nd1—O1W	2.462 (9)	O32—C22	1.430 (12)
Nd1—O32	2.531 (7)	O42—C42	1.233 (13)
Nd1—O51	2.557 (8)	O52—C42	1.276 (13)
Nd1—O2W	2.566 (8)	C12—C22	1.491 (15)
Nd1—O31	2.575 (7)	C32—C42	1.512 (14)
Nd2—O43^i	2.426 (7)	O13—C13	1.264 (13)
Nd2—O42	2.455 (7)	O23—C13	1.240 (13)
Nd2—O13	2.463 (7)	O33—C33	1.412 (12)
Nd2—O5W	2.464 (7)	O33—C23	1.437 (12)
Nd2—O53	2.485 (8)	O43—C43	1.262 (13)
Nd2—O4W	2.485 (8)	O53—C43	1.257 (13)
Nd2—O6W	2.555 (7)	C13—C23	1.501 (15)
Nd2—O33	2.568 (7)	C33—C43	1.516 (15)
Nd2—O3W	2.674 (9)	O14—C14	1.208 (14)
O11—C11	1.260 (13)	O24—C14	1.322 (13)
O21—C11	1.246 (13)	O34—C24	1.409 (13)
O31—C21	1.415 (12)	O34—C34	1.421 (13)
O31—C31	1.423 (12)	O44—C44	1.298 (14)
O41—C41	1.239 (14)	O54—C44	1.200 (14)
O51—C41	1.280 (14)	C14—C24	1.536 (16)
C11—C21	1.494 (15)	C34—C44	1.511 (16)
O1W···O23^ii	2.61 (1)	O4W···O52	2.76 (1)
O1W···O8WA	2.70 (3)	O5W···O14	2.79 (1)
O2W···O41^i	2.83 (1)	O5W···O34	2.90 (1)
O2W···O23^iii	2.75 (1)	O5W···O54	2.72 (1)
O2W···O8WA	2.89 (3)	O6W···O43^i	2.99 (1)
O2W···O8WC^iv	2.81 (2)	O6W···O7W	2.74 (1)
O3W···O21^iii	2.73 (1)	O7W···O53^v	2.91 (1)
O3W···O43^i	2.79 (1)	O8WA···O22^iv	2.74 (2)
O3W···O52	2.90 (1)	O24···O22^vi	2.55 (1)
O4W···O21^ii	2.61 (1)	O44···O51^v	2.59 (1)
O12—Nd1—O41^i	89.8 (3)	O4W—Nd2—O33	70.5 (3)
O12—Nd1—O52	124.2 (2)	O6W—Nd2—O33	119.7 (2)
O41^i—Nd1—O52	76.1 (3)	O43^i—Nd2—O3W	66.3 (3)
O12—Nd1—O11	151.5 (3)	O42—Nd2—O3W	67.5 (3)
O41^i—Nd1—O11	85.0 (3)	O13—Nd2—O3W	76.4 (3)
O52—Nd1—O11	81.7 (3)	O5W—Nd2—O3W	140.6 (3)
O12—Nd1—O1W	83.8 (3)	O53—Nd2—O3W	135.0 (3)
O41^i—Nd1—O1W	136.7 (3)	O4W—Nd2—O3W	65.2 (3)
O52—Nd1—O1W	140.6 (3)	O6W—Nd2—O3W	115.4 (3)
O11—Nd1—O1W	81.0 (3)	O33—Nd2—O3W	124.5 (2)
O12—Nd1—O32	62.3 (2)	C11—O11—Nd1	126.0 (7)
O41^i—Nd1—O32	72.6 (3)	C21—O31—C31	114.3 (8)
O52—Nd1—O32	61.9 (2)	C21—O31—Nd1	121.7 (6)
O11—Nd1—O32	140.5 (3)	C31—O31—Nd1	123.8 (6)
O1W—Nd1—O32	137.1 (3)	C41—O41—Nd1^vii	140.0 (7)
O12—Nd1—O51	77.1 (3)	C41—O51—Nd1	127.0 (7)
O41^i—Nd1—O51	144.3 (3)	O21—C11—O11	125.2 (11)
O52—Nd1—O51	84.0 (3)	O21—C11—C21	116.0 (10)
O11—Nd1—O51	121.4 (3)	O11—C11—C21	118.7 (9)
O1W—Nd1—O51	75.5 (3)	O31—C21—C11	109.3 (8)
O32—Nd1—O51	72.0 (3)	O31—C31—C41	110.3 (9)
O12—Nd1—O2W	74.2 (3)	O41—C41—O51	126.1 (11)
O41^i—Nd1—O2W	68.7 (3)	O41—C41—C31	117.2 (10)
O52—Nd1—O2W	140.4 (3)	O51—C41—C31	116.7 (10)
O11—Nd1—O2W	77.8 (3)	C12—O12—Nd1	128.0 (7)
O1W—Nd1—O2W	68.3 (3)	C32—O32—C22	113.4 (8)
O32—Nd1—O2W	120.6 (3)	C32—O32—Nd1	123.9 (6)
O51—Nd1—O2W	135.5 (3)	C22—O32—Nd1	122.0 (6)
O12—Nd1—O31	134.8 (3)	C42—O42—Nd2	139.5 (7)
O41^i—Nd1—O31	133.5 (3)	C42—O52—Nd1	127.6 (7)
O52—Nd1—O31	68.3 (3)	O12—C12—O22	124.2 (10)
O11—Nd1—O31	61.7 (2)	O12—C12—C22	118.5 (9)
O1W—Nd1—O31	72.3 (3)	O22—C12—C22	117.3 (9)
O32—Nd1—O31	112.6 (2)	O32—C22—C12	108.2 (8)
O51—Nd1—O31	60.2 (2)	O32—C32—C42	108.0 (8)
O2W—Nd1—O31	126.8 (3)	O42—C42—O52	123.9 (10)
O43^i—Nd2—O42	94.5 (3)	O42—C42—C32	118.1 (9)
O43^i—Nd2—O13	84.8 (3)	O52—C42—C32	117.9 (10)
O42—Nd2—O13	140.6 (3)	C13—O13—Nd2	127.1 (7)
O43^i—Nd2—O5W	80.3 (3)	C33—O33—C23	112.8 (8)
O42—Nd2—O5W	138.4 (3)	C33—O33—Nd2	124.0 (6)
O13—Nd2—O5W	80.4 (3)	C23—O33—Nd2	123.1 (6)
O43^i—Nd2—O53	146.7 (3)	C43—O43—Nd2^vii	144.4 (7)
O42—Nd2—O53	77.8 (3)	C43—O53—Nd2	128.3 (7)
O13—Nd2—O53	121.6 (3)	O23—C13—O13	125.7 (11)
O5W—Nd2—O53	84.4 (3)	O23—C13—C23	115.6 (10)
O43^i—Nd2—O4W	130.7 (3)	O13—C13—C23	118.7 (9)
O42—Nd2—O4W	74.9 (3)	O33—C23—C13	107.9 (8)
O13—Nd2—O4W	76.1 (3)	O33—C33—C43	107.7 (9)
O5W—Nd2—O4W	137.8 (3)	O53—C43—O43	126.1 (10)
O53—Nd2—O4W	78.9 (3)	O53—C43—C33	117.7 (10)
O43^i—Nd2—O6W	73.7 (3)	O43—C43—C33	116.1 (10)
O42—Nd2—O6W	67.4 (2)	C24—O34—C34	112.0 (8)
O13—Nd2—O6W	146.9 (3)	O14—C14—O24	125.7 (11)
O5W—Nd2—O6W	71.6 (3)	O14—C14—C24	124.9 (10)
O53—Nd2—O6W	73.4 (3)	O24—C14—C24	109.3 (10)
O4W—Nd2—O6W	136.9 (3)	O34—C24—C14	107.9 (9)
O43^i—Nd2—O33	136.1 (3)	O34—C34—C44	106.5 (9)
O42—Nd2—O33	129.4 (3)	O54—C44—O44	122.9 (11)
O13—Nd2—O33	61.6 (2)	O54—C44—C34	123.5 (10)
O5W—Nd2—O33	67.5 (3)	O44—C44—C34	113.5 (10)
O53—Nd2—O33	60.5 (2)

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