Three isomorphous Ln complexes: {[Ln₂(bt)₆(bno)(H₂O)₄]·bno}_n (bt is but-2-enoate and bno is 4,4′-bipyridyl N,N′-dioxide), with Ln = Nd, Er and Y

The polymeric title compounds, namely catena-poly[[[di-μ-but-2-enoato-κ³O:O,O′;κ³O,O′:O′-bis­[diaqua­dibut-2-enoato-κO;κ²O,O′-neodymium(III)]]-μ-4,4′-bipyridyl N,N′-dioxide-κ²O:O′] 4,4′-bipyridyl N,N′-dioxide solvate] and the erbium(III) and yttrium(III) analogues, {[Ln₂(C₄H₅O₂)₆(C₁₀H₈N₂O₂)(H₂O)₄]·C₁₀H₈N₂O₂}_n (Ln = Nd, Er and Y), form from [Ln₂(bt)₆(H₂O)₄] dimers (bt is but-2-enoate) bridged by 4,4′-bipyridyl dioxide (bno) spacers into sets of parallel chains; these linear arrays are inter­connected by aqua-mediated hydrogen bonds into broad two-dimensional structures, which in turn inter­act with each other though the hydrogen-bonded bridged bno solvent units. Both independent bno units in the structures are bisected by symmetry centres.

S1. Comment

The construction of extended frameworks containing f elements bridged by carboxylate groups has attracted a great deal of interest because of the large variety of architectures that might result from the high and variable coordination numbers of the metal centers as well as the coordination versatility of the carboxylate ligands. In this respect, butenoic (crotonic) acid has proved to be highly efficient in coupling Ln^III ions (Rizzi et al., 2003; Baggio et al., 2005). In addition, we have observed that the incorporation of diimines during the synthetic procedure might favour crystallization, either through their inclusion as neutral ligands or counter-ions or even as external crystallization agents (Atria et al., 2006). In particular, 4,4'-bipyridine and its derivatives appear to be quite suitable – owing to their well known spacer properties – for generating grid or cluster structures, which are interesting not only from a structural point of view but also for their potential application in ion exchange, catalysis, molecular absorption, optical, electronic and magnetic areas.

In this context, we have recently reported (Muñoz et al., 2005) the synthesis and full characterization of an Ln* series formulated as {[Ln(bt)₃(H₂O)(bpy)_1/2]₂}_n [bt is butenoate (C₄H₅O₂), bpy is 4,4'-bipyridine (C₁₀H₈N₂), and Ln = Nd, Gd, Ho, Er and Y], structures which in what follows we shall refer to as (IV).

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

EDITOR: please inclue the following as a footnote:

(*): In this paper, we shall give the term `Ln' a broader sense than normal, so as to include the whole lanthanide family plus the `outlier' yttrium species.

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

Complementing the former, we report here the syntheses and crystal structures of a related, isomorphous series of general formula {[Ln(bt)₃(H₂O)₂(bno)_1/2]₂.(bno)}_n [bno is 4,4'-bipyridyldioxide (C₁₀H₈N₂O₂), and Ln = Nd, (I), Er, (II), and Y, (III)], which exhibit close similarities to as well as interesting differences from the above-mentioned series (IV).

The compounds crystallize in the triclinic space group P1, and their asymmetric unit is composed of a nine-coordinate Ln cation, three butenoate ligands, two aqua ligands and one independent half of a whole bno unit, bisected by a symmetry centre. In what follows, we shall describe compound (I), the Nd compound, as representative of the whole series, pointing out any significant difference with the rest when pertinent. Fig. 1 shows a molecular plot of (I), and Tables 1, 3 and 5, give selected bond distances for all three isostructural compounds.

The cation coordination sites are provided by five carboxylate O atoms from one monocoordinated and two chelating butenoate units, one of which also acts in a bridging mode linking to a neighbouring Ln cation and thus providing a sixth site. The independent bno O atom and two aqua ligands complete the ninefold coordination.

Coordination distances span the ranges 2.377 (3)–2.671 (3) Å in (I), 2.262 (4)–2.773 (4) Å in (II) and 2.277 (2)–2.761 (3) Å in (III), which can be considered normal for this kind of complex. The carboxylate groups bite in rather dissimilar ways. That at C21 does so in a rather symmetric way, with bond differences in the range of 1–3% (percentages refer to the lower value in the pair). That at C11, instead, presents a pronounced asymmetry due to the involvement of atom O12 in bridging; the resulting differences in the chelating distances are 5.7, 16.2 and 15.1% in (I)–(III), respectively. Still larger are the differences between chelating (long) versus bridging (short) distances for atom O12, which amount to 7.7, 18.3 and 17.5%, respectively.

The [Ln(bt)₃(H₂O)₂(bno)_1/2] group already described acts as the elemental motif of a linear array, through the combined effects of two independent symmetry centres in the structure. That at (1, 1, 1/2) generates dimeric units by joining neighbouring coordination polyhedra through an [Ln—O]₂ loop; these loops are characterized by Ln···Ln distances (Å)/O—Ln—O angles (°) of 4.373 (1)/63.9 (1), 4.369 (1)/63.0 (1) and 4.361 (1)/63.1 (1), respectively. The centre at (1/2, 1/2, 1/2), which duplicates the independent pyridyloxide group into a complete bno molecule, acts as the linkage between dimeric units, thus generating a linear chain that runs parallel to [110] and which is a distinctive feature in the structure (Fig. 2).

As expected from the existence of strong chelation restraints, the coordination polyhedron (Fig. 1) is rather difficult to describe within the limits of conventional geometries. However, it presents a good example of the applicability of the vector bond valence approach recently presented by Harvey et al. (2006). An extremely simplified idea of what is presented therein could be that if ligands are considered as `a whole' and their collective coordinative interaction represented by a unique coordination vector joining the ligands to the metal centre, in addition to some other surprising results, substantial simplifications in the geometry description can be achieved. A detailed application of the procedure is beyond the scope of this paper, but if in the case of the chelating carboxylates the direction of the `resultant interaction' is approximated by the Nd—C_carboxylate vector (a very reasonable guess), the geometry ends up being described by a quite regular pentagonal bipyramid with the base defined by atoms C21, O41, O1W, O2W and O12ⁱ [internal angle sequence: 71.0 (2), 72.2 (2), 67.3 (2), 72.7 (2), 77.0 (2) °; mean deviation from the least-squares plane: 0.087 (1) Å], with atoms C11 and O31 at the apices, deviating 5.3 (1) and 11.9 (1)°, respectively, from the plane normal.

Tables 2, 4 and 6 give information on the strong hydrogen bonds having the aqua H atoms as donors; those corresponding to entries 1 and 2 are intrachain and shown in Fig. 1. Interchain interactions (entries 3 and 4) can be envisaged as a two-step process leading first to the formation of two-dimensional structures parallel to (001), by way of of the hydrogen bond involving atom H1WA (third entry). These two-dimensional structures, in turn, are interconnected by the bno ligand, acting as a hydrogen-bonded bridge between planar arrays, into a final hydrogen-bonded three-dimensional structure.

A second type of nonbonding interaction providing packing stability is the C31—O32···Cgⁱⁱ contact [Cg is the centroid of the N51/C51–C55 ring; symmetry code: (ii) −x + 1, −y + 2, −z + 2; Fig. 3], weaker in structure (I), more important in the remaining two, whose parameters are summarized in Table 7.

The similarities with the series of structures (IV) reported by Muñoz et al. (2005) are many, and evident by inspection of both molecular diagrams; however, there are important differences as well, such as those derived from the presence of the solvent unit in (I), defining completely different packing patterns, or those resulting from the more open space left to coordination when the –ONC₅ group binds to the cation as in (I) instead of the –NC₅ group in (IV). In the latter case, the three carboxylate groups chelate the cation; in the former, instead, one of them `opens' by freeing O32, thus leaving room for the coordination of an extra aqua ligand, to which the same O32 atom makes a very strong intramolecular hydrogen bond, closing a wider Ln—O—H···O—C—O—Ln loop.

Related literature

For related literature, see: Baggio et al. (2005); Harvey et al. (2006); Muñoz, Atria, Baggio, Garland, Peña & Orrego (2005); Rizzi et al. (2003).

S2. Experimental

The three complexes were prepared using the same general method: a solution of 4,4'-dipyridyl N,N'-dioxide hydrate (1 mmol) in ethanol was added to an aqueous solution containing Ln₂O₃ (1 mmol) and crotonic acid (6 mmol). The resulting mixture was refluxed for 24 h, filtered while hot and then concentrated to 25 ml. The filtrate was left at room temperature. On standing, suitable crystals for single-crystal X-ray diffraction appeared and were used without further processing.

S3. Refinement

H atoms attached to carbon were placed at idealized positions (C—H = 0.96 Å for CH₃ and C—H = 0.93 Å for CH) and allowed to ride. Those corresponding to aqua ligands were found in difference maps and refined with restrained O—H distances [0.85 (2) Å]. All H atoms were assigned U_iso(H) parameters of xU_eq(host), with x = 1.2 except for methyl H atoms, for which x = 1.5.

Computing details

For all compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2001); data reduction: SAINT-NT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 2001); software used to prepare material for publication: SHELXTL-NT (Bruker, 2001) and PLATON (Spek, 2003).

Figures

	Fig. 1. : A molecular ellipsoid plot of (1). The independent part is shown in full 30% probability level displacement ellipsoids (and bonds); the symmetry related part is shown in open ellipsoids (and bonds). Note the way in which dimers and, in a second instance, chains are formed. Broken lines repreent intramolecular hydrogen bonds. Symmetry codes as in Table 1.
	Fig. 2. : A linear chain in (I), running along [110].
	Fig. 3. : The packing of (I), projected onto the (110) plane, showing the packing interactions. Note in projection the chains, binding each other into planes parallel to (001) by way of the interchain hydrogen bond involving O11^ii. Note also the bridging function of the bno solvent molecule, through the interplanar hydrogen bond involving atom O51^ii. Single fine broken lines represent intramolecular hydrogen bonds, heavy broken lines intermolecular hydrogen bonds, and double broken lines the C—O···π bonds. Symmetry codes as in Table 2.

(I) catena-poly[[[di-µ-but-2-enoato-κ³O:O,O';κ³O,O':O'-bis[diaquadibut-2-enoato-κO;κ²O,O'-neodymium(III)]]-µ-4,4'-bipyridyl dioxide-κ²O:O'] 4,4'-bipyridyl dioxide solvate]

Crystal data

[Nd2(C4H5O2)6(C10H8N2O2)(H2O)4]·C10H8N2O2	Z = 1
Mr = 1247.40	F(000) = 626
Triclinic, P1	Dx = 1.634 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3495 (10) Å	Cell parameters from 4712 reflections
b = 12.0160 (13) Å	θ = 3.6–24.7°
c = 12.8534 (14) Å	µ = 2.10 mm^−1
α = 84.498 (2)°	T = 298 K
β = 70.535 (2)°	Blocks, colourless
γ = 68.632 (2)°	0.21 × 0.18 × 0.13 mm
V = 1267.3 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	5490 independent reflections
Radiation source: fine-focus sealed tube	4882 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
phi and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −12→12
Tmin = 0.64, Tmax = 0.77	k = −15→15
10743 measured reflections	l = −16→16

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0427P)^2 + 2.6202P] where P = (Fo^2 + 2Fc^2)/3
5490 reflections	(Δ/σ)max = 0.006
331 parameters	Δρmax = 0.99 e Å^−3
6 restraints	Δρmin = −0.57 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Nd1	0.85200 (2)	0.889729 (17)	0.518790 (15)	0.02743 (7)
O11	0.7155 (3)	1.0614 (2)	0.4141 (2)	0.0391 (6)
O12	0.9047 (3)	1.0936 (2)	0.4560 (2)	0.0350 (6)
C11	0.8075 (4)	1.1193 (3)	0.4009 (3)	0.0323 (8)
C12	0.8088 (6)	1.2156 (4)	0.3221 (4)	0.0533 (12)
H12	0.8785	1.2561	0.3174	0.064*
C13	0.7196 (7)	1.2481 (5)	0.2589 (5)	0.0706 (16)
H13	0.6506	1.2068	0.2642	0.085*
C14	0.7168 (12)	1.3468 (8)	0.1773 (7)	0.132 (4)
H14A	0.7563	1.4018	0.1979	0.199*
H14B	0.6076	1.3881	0.1769	0.199*
H14C	0.7846	1.3133	0.1049	0.199*
O21	1.0502 (3)	0.8617 (2)	0.3243 (2)	0.0335 (6)
O22	1.0724 (3)	0.6987 (2)	0.4205 (2)	0.0413 (6)
C21	1.1162 (4)	0.7489 (3)	0.3319 (3)	0.0322 (8)
C22	1.2501 (5)	0.6785 (4)	0.2373 (4)	0.0446 (10)
H22	1.2808	0.5957	0.2392	0.054*
C23	1.3271 (6)	0.7232 (5)	0.1525 (4)	0.0563 (12)
H23	1.2878	0.8060	0.1486	0.068*
C24	1.4737 (7)	0.6570 (6)	0.0587 (5)	0.0788 (18)
H24A	1.5658	0.6735	0.0608	0.118*
H24B	1.4544	0.6825	−0.0101	0.118*
H24C	1.4948	0.5727	0.0653	0.118*
O31	0.8545 (4)	0.7376 (3)	0.6515 (2)	0.0458 (7)
O32	0.6197 (4)	0.7860 (4)	0.7873 (3)	0.0815 (13)
C31	0.7643 (6)	0.7204 (4)	0.7446 (4)	0.0505 (11)
C32	0.8347 (7)	0.6161 (5)	0.8070 (4)	0.0697 (16)
H32	0.7721	0.6104	0.8793	0.084*
C33	0.9721 (7)	0.5342 (5)	0.7709 (4)	0.0617 (13)
H33	1.0362	0.5423	0.6997	0.074*
C34	1.0426 (9)	0.4250 (6)	0.8310 (6)	0.092 (2)
H34A	0.9672	0.4263	0.9034	0.138*
H34B	1.1423	0.4246	0.8371	0.138*
H34C	1.0632	0.3545	0.7908	0.138*
O41	0.7395 (3)	0.8063 (2)	0.4107 (2)	0.0390 (6)
N41	0.6756 (4)	0.7218 (3)	0.4357 (3)	0.0306 (6)
C41	0.5452 (5)	0.7351 (4)	0.4073 (4)	0.0405 (9)
H41	0.5012	0.8031	0.3710	0.049*
C42	0.4758 (5)	0.6487 (4)	0.4316 (4)	0.0432 (10)
H42	0.3851	0.6594	0.4113	0.052*
C43	0.5377 (4)	0.5463 (3)	0.4855 (3)	0.0308 (8)
C44	0.6744 (5)	0.5350 (4)	0.5116 (4)	0.0404 (9)
H44	0.7218	0.4670	0.5466	0.048*
C45	0.7410 (5)	0.6231 (4)	0.4864 (4)	0.0414 (9)
H45	0.8327	0.6140	0.5049	0.050*
O51	0.5314 (4)	0.8810 (3)	0.1492 (3)	0.0619 (9)
N51	0.6597 (4)	0.9114 (3)	0.1090 (3)	0.0464 (9)
C51	0.7411 (5)	0.9207 (4)	0.1735 (3)	0.0459 (10)
H51	0.7063	0.9045	0.2481	0.055*
C52	0.8740 (5)	0.9534 (4)	0.1328 (3)	0.0463 (10)
H52	0.9287	0.9580	0.1800	0.056*
C53	0.9300 (5)	0.9802 (4)	0.0221 (3)	0.0409 (9)
C54	0.8465 (6)	0.9640 (5)	−0.0433 (4)	0.0574 (13)
H54	0.8814	0.9767	−0.1187	0.069*
C55	0.7153 (6)	0.9300 (5)	−0.0001 (4)	0.0591 (13)
H55	0.6628	0.9194	−0.0464	0.071*
O1W	0.5639 (3)	0.9276 (3)	0.6254 (3)	0.0505 (8)
H1WA	0.485 (4)	0.927 (4)	0.608 (3)	0.061*
H1WB	0.563 (5)	0.886 (4)	0.683 (3)	0.061*
O2W	0.7594 (4)	1.0102 (3)	0.6894 (2)	0.0492 (8)
H2WA	0.807 (4)	1.059 (3)	0.688 (4)	0.059*
H2WB	0.670 (3)	1.036 (4)	0.741 (3)	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nd1	0.02384 (11)	0.03345 (12)	0.03163 (11)	−0.01625 (8)	−0.01130 (8)	0.00408 (8)
O11	0.0320 (14)	0.0426 (15)	0.0558 (17)	−0.0217 (12)	−0.0233 (13)	0.0105 (13)
O12	0.0308 (13)	0.0423 (15)	0.0430 (15)	−0.0193 (12)	−0.0191 (12)	0.0029 (12)
C11	0.0269 (18)	0.0347 (19)	0.040 (2)	−0.0135 (15)	−0.0134 (15)	0.0012 (16)
C12	0.058 (3)	0.054 (3)	0.070 (3)	−0.035 (2)	−0.037 (3)	0.025 (2)
C13	0.080 (4)	0.074 (4)	0.089 (4)	−0.044 (3)	−0.058 (3)	0.042 (3)
C14	0.181 (9)	0.138 (7)	0.156 (8)	−0.104 (7)	−0.128 (7)	0.110 (7)
O21	0.0322 (13)	0.0355 (14)	0.0374 (14)	−0.0162 (11)	−0.0129 (11)	0.0036 (11)
O22	0.0398 (15)	0.0361 (15)	0.0428 (16)	−0.0098 (12)	−0.0125 (13)	0.0064 (12)
C21	0.0283 (18)	0.037 (2)	0.038 (2)	−0.0138 (16)	−0.0170 (16)	0.0002 (16)
C22	0.041 (2)	0.040 (2)	0.047 (3)	−0.0091 (19)	−0.0113 (19)	−0.0062 (19)
C23	0.059 (3)	0.059 (3)	0.047 (3)	−0.025 (2)	−0.006 (2)	−0.009 (2)
C24	0.073 (4)	0.092 (4)	0.054 (3)	−0.030 (3)	0.009 (3)	−0.024 (3)
O31	0.0463 (17)	0.0515 (17)	0.0409 (16)	−0.0251 (14)	−0.0102 (13)	0.0136 (13)
O32	0.048 (2)	0.112 (3)	0.061 (2)	−0.020 (2)	−0.0060 (18)	0.031 (2)
C31	0.051 (3)	0.059 (3)	0.045 (3)	−0.028 (2)	−0.015 (2)	0.015 (2)
C32	0.061 (3)	0.082 (4)	0.048 (3)	−0.023 (3)	−0.003 (2)	0.024 (3)
C33	0.069 (4)	0.057 (3)	0.056 (3)	−0.027 (3)	−0.013 (3)	0.009 (2)
C34	0.096 (5)	0.067 (4)	0.106 (5)	−0.020 (4)	−0.041 (4)	0.028 (4)
O41	0.0486 (16)	0.0434 (15)	0.0456 (16)	−0.0357 (13)	−0.0218 (13)	0.0106 (12)
N41	0.0324 (16)	0.0325 (16)	0.0356 (17)	−0.0196 (13)	−0.0135 (13)	0.0035 (13)
C41	0.040 (2)	0.040 (2)	0.052 (2)	−0.0209 (18)	−0.0251 (19)	0.0152 (19)
C42	0.041 (2)	0.043 (2)	0.066 (3)	−0.0262 (19)	−0.034 (2)	0.018 (2)
C43	0.0290 (18)	0.0319 (19)	0.039 (2)	−0.0167 (15)	−0.0144 (15)	0.0033 (16)
C44	0.041 (2)	0.035 (2)	0.058 (3)	−0.0201 (18)	−0.029 (2)	0.0140 (19)
C45	0.041 (2)	0.043 (2)	0.056 (3)	−0.0233 (19)	−0.028 (2)	0.0110 (19)
O51	0.0479 (19)	0.083 (2)	0.057 (2)	−0.0418 (18)	0.0039 (16)	−0.0114 (18)
N51	0.0379 (19)	0.055 (2)	0.043 (2)	−0.0213 (17)	−0.0038 (16)	−0.0009 (17)
C51	0.045 (2)	0.060 (3)	0.032 (2)	−0.025 (2)	−0.0057 (18)	0.0042 (19)
C52	0.046 (2)	0.067 (3)	0.031 (2)	−0.027 (2)	−0.0128 (18)	0.012 (2)
C53	0.035 (2)	0.054 (2)	0.033 (2)	−0.0154 (19)	−0.0113 (16)	0.0068 (18)
C54	0.051 (3)	0.098 (4)	0.033 (2)	−0.040 (3)	−0.016 (2)	0.016 (2)
C55	0.050 (3)	0.094 (4)	0.042 (3)	−0.037 (3)	−0.015 (2)	0.006 (3)
O1W	0.0278 (14)	0.084 (2)	0.0478 (18)	−0.0288 (15)	−0.0138 (13)	0.0046 (16)
O2W	0.0425 (17)	0.069 (2)	0.0434 (17)	−0.0376 (16)	0.0011 (13)	−0.0139 (15)

Geometric parameters (Å, º)

Nd1—O31	2.377 (3)	C33—C34	1.506 (8)
Nd1—O2W	2.466 (3)	C33—H33	0.9300
Nd1—O41	2.461 (2)	C34—H34A	0.9600
Nd1—O1W	2.471 (3)	C34—H34B	0.9600
Nd1—O12^i	2.480 (2)	C34—H34C	0.9600
Nd1—O11	2.528 (3)	O41—N41	1.320 (4)
Nd1—O21	2.533 (3)	N41—C41	1.337 (5)
Nd1—O22	2.546 (3)	N41—C45	1.339 (5)
Nd1—O12	2.671 (3)	C41—C42	1.374 (5)
O11—C11	1.252 (4)	C41—H41	0.9300
O12—C11	1.267 (4)	C42—C43	1.384 (5)
C11—C12	1.464 (6)	C42—H42	0.9300
C12—C13	1.289 (6)	C43—C44	1.383 (5)
C12—H12	0.9300	C43—C43^ii	1.481 (7)
C13—C14	1.504 (7)	C44—C45	1.377 (5)
C13—H13	0.9300	C44—H44	0.9300
C14—H14A	0.9600	C45—H45	0.9300
C14—H14B	0.9600	O51—N51	1.308 (4)
C14—H14C	0.9600	N51—C51	1.334 (6)
O21—C21	1.278 (4)	N51—C55	1.350 (6)
O22—C21	1.252 (5)	C51—C52	1.362 (6)
C21—C22	1.474 (5)	C51—H51	0.9300
C22—C23	1.281 (6)	C52—C53	1.393 (5)
C22—H22	0.9300	C52—H52	0.9300
C23—C24	1.501 (7)	C53—C54	1.391 (6)
C23—H23	0.9300	C53—C53^iii	1.473 (8)
C24—H24A	0.9600	C54—C55	1.359 (6)
C24—H24B	0.9600	C54—H54	0.9300
C24—H24C	0.9600	C55—H55	0.9300
O31—C31	1.262 (5)	O1W—H1WA	0.85 (4)
O32—C31	1.250 (6)	O1W—H1WB	0.85 (4)
C31—C32	1.485 (7)	O2W—H2WA	0.85 (4)
C32—C33	1.267 (7)	O2W—H2WB	0.85 (4)
C32—H32	0.9300
O31—Nd1—O2W	79.78 (11)	C23—C24—H24A	109.5
O31—Nd1—O41	93.90 (10)	C23—C24—H24B	109.5
O2W—Nd1—O41	139.26 (10)	H24A—C24—H24B	109.5
O31—Nd1—O1W	74.66 (11)	C23—C24—H24C	109.5
O2W—Nd1—O1W	67.29 (10)	H24A—C24—H24C	109.5
O41—Nd1—O1W	72.21 (10)	H24B—C24—H24C	109.5
O31—Nd1—O12^i	90.02 (9)	C31—O31—Nd1	138.5 (3)
O2W—Nd1—O12^i	72.66 (9)	O32—C31—O31	123.8 (4)
O41—Nd1—O12^i	148.01 (9)	O32—C31—C32	118.2 (4)
O1W—Nd1—O12^i	138.94 (10)	O31—C31—C32	117.9 (4)
O31—Nd1—O11	153.82 (10)	C33—C32—C31	126.0 (5)
O2W—Nd1—O11	94.42 (11)	C33—C32—H32	117.0
O41—Nd1—O11	73.80 (9)	C31—C32—H32	117.0
O1W—Nd1—O11	79.54 (10)	C32—C33—C34	126.8 (5)
O12^i—Nd1—O11	112.79 (8)	C32—C33—H33	116.6
O31—Nd1—O21	124.68 (9)	C34—C33—H33	116.6
O2W—Nd1—O21	140.67 (9)	C33—C34—H34A	109.5
O41—Nd1—O21	74.95 (9)	C33—C34—H34B	109.5
O1W—Nd1—O21	142.94 (9)	H34A—C34—H34B	109.5
O12^i—Nd1—O21	76.76 (8)	C33—C34—H34C	109.5
O11—Nd1—O21	75.20 (9)	H34A—C34—H34C	109.5
O31—Nd1—O22	73.64 (10)	H34B—C34—H34C	109.5
O2W—Nd1—O22	140.60 (11)	N41—O41—Nd1	129.7 (2)
O41—Nd1—O22	72.04 (10)	O41—N41—C41	118.7 (3)
O1W—Nd1—O22	129.63 (11)	O41—N41—C45	121.2 (3)
O12^i—Nd1—O22	78.72 (9)	C41—N41—C45	120.1 (3)
O11—Nd1—O22	121.77 (9)	N41—C41—C42	120.3 (4)
O21—Nd1—O22	51.20 (8)	N41—C41—H41	119.8
O31—Nd1—O12	147.20 (9)	C42—C41—H41	119.8
O2W—Nd1—O12	73.84 (9)	C41—C42—C43	121.6 (3)
O41—Nd1—O12	118.82 (8)	C41—C42—H42	119.2
O1W—Nd1—O12	111.37 (10)	C43—C42—H42	119.2
O12^i—Nd1—O12	63.87 (10)	C42—C43—C44	116.3 (3)
O11—Nd1—O12	49.44 (8)	C42—C43—C43^ii	122.2 (4)
O21—Nd1—O12	70.76 (8)	C44—C43—C43^ii	121.4 (4)
O22—Nd1—O12	116.57 (9)	C45—C44—C43	120.8 (4)
C11—O11—Nd1	98.2 (2)	C45—C44—H44	119.6
C11—O12—Nd1^i	148.7 (2)	C43—C44—H44	119.6
C11—O12—Nd1	91.0 (2)	N41—C45—C44	120.9 (3)
Nd1^i—O12—Nd1	116.13 (10)	N41—C45—H45	119.6
O11—C11—O12	119.6 (3)	C44—C45—H45	119.6
O11—C11—C12	122.2 (3)	O51—N51—C51	121.0 (4)
O12—C11—C12	118.2 (3)	O51—N51—C55	120.1 (4)
C13—C12—C11	124.3 (4)	C51—N51—C55	118.8 (4)
C13—C12—H12	117.8	N51—C51—C52	121.6 (4)
C11—C12—H12	117.8	N51—C51—H51	119.2
C12—C13—C14	126.0 (5)	C52—C51—H51	119.2
C12—C13—H13	117.0	C51—C52—C53	121.5 (4)
C14—C13—H13	117.0	C51—C52—H52	119.3
C13—C14—H14A	109.5	C53—C52—H52	119.3
C13—C14—H14B	109.5	C52—C53—C54	115.1 (4)
H14A—C14—H14B	109.5	C52—C53—C53^iii	122.1 (5)
C13—C14—H14C	109.5	C54—C53—C53^iii	122.9 (5)
H14A—C14—H14C	109.5	C55—C54—C53	121.7 (4)
H14B—C14—H14C	109.5	C55—C54—H54	119.1
C21—O21—Nd1	94.2 (2)	C53—C54—H54	119.1
C21—O22—Nd1	94.2 (2)	N51—C55—C54	121.1 (4)
O22—C21—O21	120.4 (3)	N51—C55—H55	119.4
O22—C21—C22	119.9 (3)	C54—C55—H55	119.4
O21—C21—C22	119.7 (3)	Nd1—O1W—H1WA	133 (3)
C23—C22—C21	124.7 (4)	Nd1—O1W—H1WB	107 (3)
C23—C22—H22	117.6	H1WA—O1W—H1WB	106 (4)
C21—C22—H22	117.6	Nd1—O2W—H2WA	116 (3)
C22—C23—C24	127.4 (5)	Nd1—O2W—H2WB	134 (3)
C22—C23—H23	116.3	H2WA—O2W—H2WB	106 (4)
C24—C23—H23	116.3

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WA···O21^i	0.85 (4)	1.87 (4)	2.703 (4)	168 (4)
O1W—H1WB···O32	0.85 (4)	1.80 (4)	2.625 (5)	164 (4)
O1W—H1WA···O11^iv	0.85 (4)	1.94 (4)	2.779 (4)	172 (5)
O2W—H2WB···O51^iv	0.85 (4)	1.91 (4)	2.753 (4)	171 (4)

Symmetry codes: (i) −x+2, −y+2, −z+1; (iv) −x+1, −y+2, −z+1.

(II) catena-poly[[[di-µ-but-2-enoato-κ³O:O,O';κ³O,O':O'-bis[diaquadibut-2-enoato-κO;κ²O,O'-erbium(III)]]-µ-4,4'-bipyridyl dioxide-κ²O:O'] 4,4'-bipyridyl dioxide solvate]

Crystal data

[Er2(C4H5O2)6(C10H8N2O2)(H2O)4]·C10H8N2O2	Z = 1
Mr = 1293.44	F(000) = 642
Triclinic, P1	Dx = 1.731 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1731 (9) Å	Cell parameters from 6237 reflections
b = 12.0358 (12) Å	θ = 4.1–25.1°
c = 12.7221 (13) Å	µ = 3.44 mm^−1
α = 85.728 (2)°	T = 298 K
β = 71.181 (1)°	Blocks, colourless
γ = 69.099 (1)°	0.18 × 0.14 × 0.12 mm
V = 1240.7 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	5394 independent reflections
Radiation source: fine-focus sealed tube	4772 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
phi and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −11→11
Tmin = 0.56, Tmax = 0.67	k = −15→15
9217 measured reflections	l = −15→16

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0492P)^2] where P = (Fo^2 + 2Fc^2)/3
5394 reflections	(Δ/σ)max = 0.001
331 parameters	Δρmax = 1.09 e Å^−3
6 restraints	Δρmin = −1.61 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Er1	0.84952 (2)	0.889230 (18)	0.521512 (16)	0.03019 (9)
O11	0.7222 (4)	1.0533 (3)	0.4248 (3)	0.0418 (8)
O12	0.9138 (4)	1.0965 (4)	0.4560 (3)	0.0468 (9)
C11	0.8103 (5)	1.1167 (4)	0.4047 (4)	0.0331 (10)
C12	0.8064 (10)	1.2089 (6)	0.3260 (6)	0.0685 (19)
H12	0.8764	1.2505	0.3205	0.082*
C13	0.7188 (11)	1.2385 (8)	0.2646 (7)	0.088 (3)
H13	0.6493	1.1969	0.2682	0.106*
C14	0.7182 (15)	1.3397 (10)	0.1828 (10)	0.140 (5)
H14A	0.7706	1.3884	0.2010	0.210*
H14B	0.6067	1.3874	0.1883	0.210*
H14C	0.7768	1.3063	0.1084	0.210*
O21	1.0396 (4)	0.8627 (3)	0.3338 (3)	0.0312 (7)
O22	1.0650 (4)	0.7024 (3)	0.4287 (3)	0.0408 (8)
C21	1.1071 (6)	0.7511 (4)	0.3402 (4)	0.0329 (10)
C22	1.2422 (7)	0.6788 (5)	0.2444 (5)	0.0475 (13)
H22	1.2746	0.5964	0.2466	0.057*
C23	1.3179 (8)	0.7237 (6)	0.1576 (5)	0.0575 (16)
H23	1.2767	0.8060	0.1533	0.069*
C24	1.4652 (10)	0.6560 (8)	0.0638 (6)	0.088 (3)
H24A	1.5604	0.6692	0.0680	0.132*
H24B	1.4476	0.6827	−0.0056	0.132*
H24C	1.4821	0.5726	0.0687	0.132*
O31	0.8454 (4)	0.7488 (3)	0.6498 (3)	0.0443 (9)
O32	0.6091 (6)	0.8020 (5)	0.7890 (4)	0.0757 (14)
C31	0.7531 (7)	0.7342 (6)	0.7441 (5)	0.0523 (14)
C32	0.8237 (9)	0.6288 (7)	0.8056 (6)	0.0683 (19)
H32	0.7601	0.6238	0.8781	0.082*
C33	0.9626 (9)	0.5452 (6)	0.7685 (6)	0.0633 (18)
H33	1.0268	0.5525	0.6968	0.076*
C34	1.0345 (12)	0.4370 (8)	0.8262 (8)	0.094 (3)
H34A	0.9563	0.4354	0.8973	0.141*
H34B	1.1328	0.4389	0.8365	0.141*
H34C	1.0608	0.3670	0.7820	0.141*
O41	0.7417 (4)	0.8064 (3)	0.4151 (3)	0.0370 (8)
N41	0.6770 (5)	0.7221 (3)	0.4387 (3)	0.0304 (8)
C41	0.5455 (6)	0.7335 (4)	0.4091 (4)	0.0398 (12)
H41	0.5016	0.8000	0.3718	0.048*
C42	0.4749 (6)	0.6481 (5)	0.4332 (5)	0.0419 (12)
H42	0.3817	0.6587	0.4135	0.050*
C43	0.5390 (6)	0.5457 (4)	0.4864 (4)	0.0316 (10)
C44	0.6777 (6)	0.5365 (5)	0.5135 (5)	0.0415 (12)
H44	0.7261	0.4696	0.5487	0.050*
C45	0.7447 (6)	0.6241 (5)	0.4894 (5)	0.0405 (12)
H45	0.8378	0.6159	0.5083	0.049*
O51	0.5304 (5)	0.8752 (4)	0.1544 (3)	0.0597 (11)
N51	0.6594 (5)	0.9064 (4)	0.1121 (4)	0.0445 (11)
C51	0.7466 (7)	0.9165 (5)	0.1754 (4)	0.0468 (13)
H51	0.7155	0.8993	0.2501	0.056*
C52	0.8791 (6)	0.9513 (5)	0.1334 (4)	0.0421 (12)
H52	0.9371	0.9564	0.1797	0.051*
C53	0.9298 (6)	0.9791 (5)	0.0226 (4)	0.0379 (11)
C54	0.8420 (7)	0.9625 (6)	−0.0418 (4)	0.0516 (15)
H54	0.8747	0.9757	−0.1174	0.062*
C55	0.7081 (7)	0.9271 (6)	0.0024 (5)	0.0506 (14)
H55	0.6513	0.9175	−0.0429	0.061*
O1W	0.5649 (4)	0.9358 (4)	0.6189 (3)	0.0504 (10)
H1WA	0.481 (5)	0.939 (5)	0.602 (4)	0.060*
H1WB	0.564 (7)	0.894 (5)	0.676 (3)	0.060*
O2W	0.7644 (4)	1.0099 (4)	0.6826 (3)	0.0450 (9)
H2WA	0.808 (5)	1.061 (4)	0.684 (4)	0.054*
H2WB	0.672 (3)	1.034 (4)	0.733 (4)	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Er1	0.02365 (12)	0.03802 (14)	0.03297 (13)	−0.01541 (9)	−0.00872 (9)	−0.00060 (9)
O11	0.0291 (17)	0.0361 (18)	0.064 (2)	−0.0171 (15)	−0.0134 (17)	0.0003 (17)
O12	0.0280 (17)	0.071 (3)	0.047 (2)	−0.0212 (18)	−0.0107 (16)	−0.0144 (19)
C11	0.026 (2)	0.037 (3)	0.037 (2)	−0.013 (2)	−0.0079 (19)	−0.001 (2)
C12	0.082 (5)	0.059 (4)	0.074 (5)	−0.026 (4)	−0.039 (4)	0.016 (4)
C13	0.087 (6)	0.088 (6)	0.108 (7)	−0.043 (5)	−0.045 (5)	0.019 (5)
C14	0.190 (13)	0.127 (9)	0.158 (11)	−0.075 (9)	−0.124 (10)	0.094 (9)
O21	0.0278 (15)	0.0344 (17)	0.0353 (17)	−0.0151 (14)	−0.0100 (13)	−0.0003 (14)
O22	0.0382 (18)	0.0393 (19)	0.043 (2)	−0.0120 (16)	−0.0136 (16)	0.0110 (16)
C21	0.032 (2)	0.036 (3)	0.037 (3)	−0.017 (2)	−0.014 (2)	0.001 (2)
C22	0.044 (3)	0.043 (3)	0.049 (3)	−0.012 (3)	−0.009 (3)	−0.006 (3)
C23	0.061 (4)	0.059 (4)	0.048 (3)	−0.025 (3)	−0.004 (3)	−0.012 (3)
C24	0.083 (5)	0.107 (7)	0.054 (4)	−0.037 (5)	0.015 (4)	−0.032 (4)
O31	0.0415 (19)	0.054 (2)	0.0380 (19)	−0.0239 (18)	−0.0061 (16)	0.0041 (17)
O32	0.048 (3)	0.098 (4)	0.058 (3)	−0.017 (3)	0.002 (2)	0.015 (3)
C31	0.052 (3)	0.069 (4)	0.039 (3)	−0.029 (3)	−0.010 (3)	0.008 (3)
C32	0.066 (4)	0.080 (5)	0.048 (4)	−0.028 (4)	−0.005 (3)	0.022 (3)
C33	0.070 (5)	0.063 (4)	0.059 (4)	−0.034 (4)	−0.012 (3)	0.008 (3)
C34	0.103 (7)	0.078 (6)	0.099 (7)	−0.029 (5)	−0.036 (6)	0.025 (5)
O41	0.0411 (18)	0.0399 (19)	0.0444 (19)	−0.0296 (16)	−0.0168 (16)	0.0105 (15)
N41	0.0316 (19)	0.031 (2)	0.036 (2)	−0.0176 (17)	−0.0121 (17)	0.0009 (17)
C41	0.040 (3)	0.037 (3)	0.056 (3)	−0.020 (2)	−0.028 (2)	0.016 (2)
C42	0.037 (3)	0.045 (3)	0.062 (3)	−0.026 (2)	−0.029 (3)	0.017 (3)
C43	0.031 (2)	0.030 (2)	0.042 (3)	−0.0150 (19)	−0.017 (2)	0.002 (2)
C44	0.038 (3)	0.042 (3)	0.057 (3)	−0.022 (2)	−0.025 (2)	0.020 (3)
C45	0.040 (3)	0.044 (3)	0.055 (3)	−0.025 (2)	−0.029 (2)	0.014 (2)
O51	0.047 (2)	0.078 (3)	0.057 (3)	−0.042 (2)	0.0041 (19)	−0.009 (2)
N51	0.036 (2)	0.057 (3)	0.038 (2)	−0.023 (2)	−0.0002 (19)	−0.004 (2)
C51	0.046 (3)	0.059 (3)	0.034 (3)	−0.023 (3)	−0.007 (2)	0.006 (2)
C52	0.041 (3)	0.061 (3)	0.030 (2)	−0.023 (3)	−0.013 (2)	0.008 (2)
C53	0.034 (2)	0.047 (3)	0.029 (2)	−0.013 (2)	−0.006 (2)	0.005 (2)
C54	0.047 (3)	0.088 (4)	0.029 (3)	−0.035 (3)	−0.013 (2)	0.012 (3)
C55	0.043 (3)	0.072 (4)	0.039 (3)	−0.025 (3)	−0.011 (2)	0.003 (3)
O1W	0.0272 (18)	0.076 (3)	0.051 (2)	−0.0250 (19)	−0.0081 (17)	0.001 (2)
O2W	0.0389 (19)	0.059 (2)	0.042 (2)	−0.0330 (18)	0.0029 (16)	−0.0139 (17)

Geometric parameters (Å, º)

Er1—O31	2.262 (4)	C33—C34	1.492 (11)
Er1—O12^i	2.344 (3)	C33—H33	0.9300
Er1—O2W	2.350 (3)	C34—H34A	0.9600
Er1—O41	2.361 (3)	C34—H34B	0.9600
Er1—O1W	2.375 (3)	C34—H34C	0.9600
Er1—O11	2.387 (4)	O41—N41	1.320 (5)
Er1—O21	2.423 (3)	N41—C41	1.335 (6)
Er1—O22	2.465 (3)	N41—C45	1.348 (6)
Er1—O12	2.773 (4)	C41—C42	1.367 (7)
O11—C11	1.256 (5)	C41—H41	0.9300
O12—C11	1.265 (6)	C42—C43	1.392 (7)
C11—C12	1.437 (8)	C42—H42	0.9300
C12—C13	1.241 (9)	C43—C44	1.389 (7)
C12—H12	0.9300	C43—C43^ii	1.478 (9)
C13—C14	1.542 (12)	C44—C45	1.369 (7)
C13—H13	0.9300	C44—H44	0.9300
C14—H14A	0.9600	C45—H45	0.9300
C14—H14B	0.9600	O51—N51	1.307 (5)
C14—H14C	0.9600	N51—C51	1.343 (7)
O21—C21	1.271 (6)	N51—C55	1.354 (7)
O22—C21	1.242 (6)	C51—C52	1.359 (7)
C22—C23	1.295 (7)	C51—H51	0.9300
C22—H22	0.9300	C52—C53	1.390 (6)
C23—C24	1.494 (9)	C52—H52	0.9300
C23—H23	0.9300	C53—C54	1.388 (7)
C24—H24A	0.9600	C53—C53^iii	1.478 (10)
C24—H24B	0.9600	C54—C55	1.378 (8)
C24—H24C	0.9600	C54—H54	0.9300
O31—C31	1.268 (6)	C55—H55	0.9300
O32—C31	1.245 (7)	O1W—H1WA	0.85 (5)
C31—C32	1.494 (9)	O1W—H1WB	0.85 (5)
C32—C33	1.276 (8)	O2W—H2WA	0.85 (5)
C32—H32	0.9300	O2W—H2WB	0.85 (5)
O31—Er1—O12^i	90.99 (14)	C23—C24—H24B	109.5
O31—Er1—O2W	80.74 (14)	H24A—C24—H24B	109.5
O12^i—Er1—O2W	72.71 (12)	C23—C24—H24C	109.5
O31—Er1—O41	93.60 (12)	H24A—C24—H24C	109.5
O12^i—Er1—O41	146.49 (12)	H24B—C24—H24C	109.5
O2W—Er1—O41	140.78 (12)	C31—O31—Er1	139.1 (4)
O31—Er1—O1W	76.40 (14)	O32—C31—O31	124.5 (6)
O12^i—Er1—O1W	140.39 (13)	O32—C31—C32	118.2 (5)
O2W—Er1—O1W	68.29 (13)	O31—C31—C32	117.3 (5)
O41—Er1—O1W	72.64 (13)	C33—C32—C31	126.5 (6)
O31—Er1—O11	153.43 (13)	C33—C32—H32	116.8
O12^i—Er1—O11	111.30 (13)	C31—C32—H32	116.8
O2W—Er1—O11	91.96 (14)	C32—C33—C34	127.8 (7)
O41—Er1—O11	75.96 (12)	C32—C33—H33	116.1
O1W—Er1—O11	77.17 (13)	C34—C33—H33	116.1
O31—Er1—O21	126.51 (12)	C33—C34—H34A	109.5
O12^i—Er1—O21	76.16 (11)	C33—C34—H34B	109.5
O2W—Er1—O21	138.72 (11)	H34A—C34—H34B	109.5
O41—Er1—O21	74.49 (11)	C33—C34—H34C	109.5
O1W—Er1—O21	140.89 (12)	H34A—C34—H34C	109.5
O11—Er1—O21	74.80 (11)	H34B—C34—H34C	109.5
O31—Er1—O22	73.67 (12)	N41—O41—Er1	130.0 (3)
O12^i—Er1—O22	77.61 (12)	O41—N41—C41	119.1 (4)
O2W—Er1—O22	140.11 (13)	O41—N41—C45	120.7 (4)
O41—Er1—O22	71.96 (12)	C41—N41—C45	120.1 (4)
O1W—Er1—O22	131.34 (14)	N41—C41—C42	120.5 (4)
O11—Er1—O22	123.83 (12)	N41—C41—H41	119.7
O21—Er1—O22	52.93 (11)	C42—C41—H41	119.7
O31—Er1—O12	146.95 (12)	C41—C42—C43	121.7 (4)
O12^i—Er1—O12	62.99 (15)	C41—C42—H42	119.2
O2W—Er1—O12	72.53 (12)	C43—C42—H42	119.2
O41—Er1—O12	119.39 (11)	C44—C43—C42	115.8 (4)
O1W—Er1—O12	109.96 (13)	C44—C43—C43^ii	122.7 (5)
O11—Er1—O12	48.72 (10)	C42—C43—C43^ii	121.5 (5)
O21—Er1—O12	69.46 (10)	C45—C44—C43	121.3 (5)
O22—Er1—O12	116.13 (11)	C45—C44—H44	119.4
C11—O11—Er1	105.4 (3)	C43—C44—H44	119.4
C11—O12—Er1^i	152.3 (3)	N41—C45—C44	120.6 (4)
C11—O12—Er1	86.6 (3)	N41—C45—H45	119.7
Er1^i—O12—Er1	117.01 (15)	C44—C45—H45	119.7
O11—C11—O12	117.6 (5)	O51—N51—C51	121.0 (5)
O11—C11—C12	125.5 (5)	O51—N51—C55	119.8 (5)
O12—C11—C12	116.9 (5)	C51—N51—C55	119.2 (5)
C13—C12—C11	126.5 (8)	N51—C51—C52	121.9 (5)
C13—C12—H12	116.7	N51—C51—H51	119.1
C11—C12—H12	116.7	C52—C51—H51	119.1
C12—C13—C14	124.1 (9)	C51—C52—C53	121.4 (5)
C12—C13—H13	117.9	C51—C52—H52	119.3
C14—C13—H13	117.9	C53—C52—H52	119.3
C13—C14—H14A	109.5	C54—C53—C52	115.4 (5)
C13—C14—H14B	109.5	C54—C53—C53^iii	122.9 (5)
H14A—C14—H14B	109.5	C52—C53—C53^iii	121.6 (6)
C13—C14—H14C	109.5	C55—C54—C53	122.2 (5)
H14A—C14—H14C	109.5	C55—C54—H54	118.9
H14B—C14—H14C	109.5	C53—C54—H54	118.9
C21—O21—Er1	94.0 (3)	N51—C55—C54	119.9 (5)
C21—O22—Er1	92.8 (3)	N51—C55—H55	120.1
O22—C21—O21	120.2 (4)	C54—C55—H55	120.1
C23—C22—C21	123.8 (6)	Er1—O1W—H1WA	136 (4)
C23—C22—H22	118.1	Er1—O1W—H1WB	104 (4)
C21—C22—H22	118.1	H1WA—O1W—H1WB	105 (5)
C22—C23—C24	126.2 (7)	Er1—O2W—H2WA	120 (3)
C22—C23—H23	116.9	Er1—O2W—H2WB	130 (3)
C24—C23—H23	116.9	H2WA—O2W—H2WB	105 (5)
C23—C24—H24A	109.5

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WA···O21^i	0.85 (5)	1.88 (5)	2.703 (4)	164 (5)
O1W—H1WB···O32	0.85 (5)	1.81 (5)	2.650 (6)	167 (5)
O1W—H1WA···O11^iv	0.85 (5)	1.97 (5)	2.819 (5)	176 (5)
O2W—H2WB···O51^iv	0.85 (5)	1.94 (5)	2.769 (5)	166 (5)

Symmetry codes: (i) −x+2, −y+2, −z+1; (iv) −x+1, −y+2, −z+1.

(III) catena-poly[[[di-µ-but-2-enoato-κ³O:O,O';κ³O,O':O'-bis[diaquadibut-2-enoato-κO;κ²O,O'-yttrium(III)]]-µ-4,4'-bipyridyl dioxide-κ²O:O'] 4,4'-bipyridyl dioxide solvate]

Crystal data

[Y2(C4H5O2)6(C10H8N2O2)(H2O)4]·C10H8N2O2	Z = 1
Mr = 1136.74	F(000) = 584
Triclinic, P1	Dx = 1.519 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1865 (13) Å	Cell parameters from 7488 reflections
b = 12.0293 (17) Å	θ = 4.2–24.8°
c = 12.7275 (18) Å	µ = 2.40 mm^−1
α = 85.710 (2)°	T = 298 K
β = 71.079 (2)°	Blocks, colourless
γ = 69.175 (2)°	0.14 × 0.14 × 0.13 mm
V = 1242.3 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	5405 independent reflections
Radiation source: fine-focus sealed tube	4364 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
phi and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −11→12
Tmin = 0.71, Tmax = 0.74	k = −15→15
10592 measured reflections	l = −16→16

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0633P)^2] where P = (Fo^2 + 2Fc^2)/3
5405 reflections	(Δ/σ)max = 0.001
331 parameters	Δρmax = 0.89 e Å^−3
6 restraints	Δρmin = −0.48 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
Y1	0.84968 (3)	0.88953 (3)	0.52118 (3)	0.03172 (12)
O11	0.7217 (3)	1.0538 (2)	0.4236 (2)	0.0440 (6)
O12	0.9144 (3)	1.0957 (2)	0.4552 (2)	0.0478 (6)
C11	0.8109 (4)	1.1162 (3)	0.4046 (3)	0.0347 (7)
C12	0.8066 (6)	1.2106 (4)	0.3258 (4)	0.0738 (13)
H12	0.8759	1.2528	0.3204	0.089*
C13	0.7175 (7)	1.2397 (5)	0.2646 (5)	0.0929 (17)
H13	0.6465	1.1990	0.2697	0.112*
C14	0.7193 (10)	1.3394 (6)	0.1813 (7)	0.146 (3)
H14A	0.8010	1.3713	0.1824	0.219*
H14B	0.6133	1.4015	0.2017	0.219*
H14C	0.7448	1.3075	0.1079	0.219*
O21	1.0404 (3)	0.86271 (19)	0.33308 (18)	0.0342 (5)
O22	1.0667 (3)	0.7018 (2)	0.4284 (2)	0.0420 (6)
C21	1.1092 (4)	0.7511 (3)	0.3392 (3)	0.0345 (7)
C22	1.2435 (5)	0.6795 (3)	0.2436 (3)	0.0490 (9)
H22	1.2758	0.5971	0.2463	0.059*
C23	1.3186 (5)	0.7226 (4)	0.1577 (3)	0.0605 (11)
H23	1.2773	0.8049	0.1535	0.073*
C24	1.4656 (7)	0.6564 (5)	0.0625 (4)	0.0953 (18)
H24A	1.5618	0.6656	0.0692	0.143*
H24B	1.4499	0.6877	−0.0063	0.143*
H24C	1.4791	0.5734	0.0634	0.143*
O31	0.8452 (3)	0.7479 (2)	0.6500 (2)	0.0464 (6)
O32	0.6093 (4)	0.8018 (3)	0.7882 (3)	0.0790 (10)
C31	0.7531 (5)	0.7348 (4)	0.7446 (3)	0.0534 (10)
C32	0.8244 (6)	0.6293 (4)	0.8060 (4)	0.0705 (13)
H32	0.7615	0.6243	0.8787	0.085*
C33	0.9620 (6)	0.5461 (4)	0.7687 (4)	0.0683 (12)
H33	1.0262	0.5534	0.6970	0.082*
C34	1.0330 (7)	0.4375 (5)	0.8265 (5)	0.0955 (18)
H34A	0.9559	0.4374	0.8985	0.143*
H34B	1.1331	0.4378	0.8348	0.143*
H34C	1.0556	0.3677	0.7834	0.143*
O41	0.7425 (3)	0.8054 (2)	0.41473 (19)	0.0389 (5)
N41	0.6777 (3)	0.7215 (2)	0.4384 (2)	0.0331 (6)
C41	0.5457 (4)	0.7333 (3)	0.4093 (3)	0.0421 (8)
H41	0.5015	0.8001	0.3726	0.050*
C42	0.4751 (4)	0.6476 (3)	0.4333 (3)	0.0444 (9)
H42	0.3824	0.6580	0.4134	0.053*
C43	0.5383 (4)	0.5463 (3)	0.4863 (3)	0.0331 (7)
C44	0.6777 (4)	0.5363 (3)	0.5128 (3)	0.0414 (8)
H44	0.7261	0.4690	0.5475	0.050*
C45	0.7445 (4)	0.6236 (3)	0.4888 (3)	0.0424 (8)
H45	0.8375	0.6153	0.5076	0.051*
O51	0.5306 (3)	0.8759 (3)	0.1537 (2)	0.0629 (8)
N51	0.6593 (4)	0.9071 (3)	0.1116 (3)	0.0474 (8)
C51	0.7472 (5)	0.9154 (3)	0.1744 (3)	0.0484 (9)
H51	0.7174	0.8961	0.2486	0.058*
C52	0.8788 (4)	0.9511 (3)	0.1331 (3)	0.0455 (9)
H52	0.9358	0.9568	0.1797	0.055*
C53	0.9297 (4)	0.9793 (3)	0.0231 (3)	0.0408 (8)
C54	0.8408 (5)	0.9631 (4)	−0.0415 (3)	0.0557 (10)
H54	0.8723	0.9770	−0.1170	0.067*
C55	0.7089 (5)	0.9274 (4)	0.0036 (3)	0.0562 (10)
H55	0.6526	0.9172	−0.0418	0.067*
O1W	0.5639 (3)	0.9353 (3)	0.6192 (2)	0.0523 (7)
H1WA	0.483 (3)	0.936 (3)	0.601 (3)	0.063*
H1WB	0.568 (5)	0.888 (3)	0.671 (3)	0.063*
O2W	0.7631 (3)	1.0110 (2)	0.6830 (2)	0.0483 (6)
H2WA	0.811 (3)	1.057 (3)	0.687 (3)	0.058*
H2WB	0.670 (2)	1.034 (3)	0.733 (2)	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Y1	0.02625 (17)	0.0395 (2)	0.03501 (19)	−0.01714 (13)	−0.01064 (13)	0.00106 (13)
O11	0.0351 (12)	0.0399 (13)	0.0660 (17)	−0.0222 (11)	−0.0181 (12)	0.0036 (12)
O12	0.0316 (12)	0.0643 (17)	0.0534 (16)	−0.0194 (12)	−0.0158 (11)	−0.0097 (13)
C11	0.0319 (16)	0.0356 (18)	0.0402 (19)	−0.0147 (14)	−0.0123 (15)	−0.0007 (14)
C12	0.082 (3)	0.068 (3)	0.080 (3)	−0.029 (3)	−0.037 (3)	0.016 (3)
C13	0.092 (4)	0.096 (4)	0.113 (5)	−0.047 (3)	−0.051 (4)	0.025 (4)
C14	0.197 (8)	0.132 (6)	0.169 (7)	−0.084 (6)	−0.129 (7)	0.108 (6)
O21	0.0323 (11)	0.0348 (13)	0.0389 (13)	−0.0151 (10)	−0.0124 (10)	0.0025 (10)
O22	0.0406 (13)	0.0397 (13)	0.0455 (15)	−0.0124 (11)	−0.0173 (11)	0.0105 (11)
C21	0.0296 (16)	0.0400 (19)	0.0400 (19)	−0.0148 (15)	−0.0154 (15)	−0.0007 (15)
C22	0.050 (2)	0.044 (2)	0.051 (2)	−0.0146 (18)	−0.0134 (19)	−0.0041 (18)
C23	0.062 (3)	0.064 (3)	0.050 (3)	−0.024 (2)	−0.005 (2)	−0.010 (2)
C24	0.086 (4)	0.109 (4)	0.067 (3)	−0.035 (3)	0.014 (3)	−0.030 (3)
O31	0.0456 (14)	0.0540 (16)	0.0419 (15)	−0.0264 (12)	−0.0083 (12)	0.0086 (12)
O32	0.0479 (17)	0.107 (3)	0.064 (2)	−0.0214 (18)	−0.0033 (15)	0.0200 (19)
C31	0.051 (2)	0.070 (3)	0.044 (2)	−0.032 (2)	−0.010 (2)	0.007 (2)
C32	0.069 (3)	0.083 (3)	0.049 (3)	−0.030 (3)	−0.004 (2)	0.018 (2)
C33	0.078 (3)	0.072 (3)	0.060 (3)	−0.037 (3)	−0.019 (3)	0.011 (2)
C34	0.099 (4)	0.082 (4)	0.105 (5)	−0.028 (3)	−0.041 (4)	0.021 (3)
O41	0.0465 (13)	0.0405 (13)	0.0474 (14)	−0.0315 (11)	−0.0223 (11)	0.0131 (11)
N41	0.0343 (14)	0.0353 (15)	0.0366 (15)	−0.0197 (12)	−0.0126 (12)	0.0044 (12)
C41	0.0413 (19)	0.042 (2)	0.057 (2)	−0.0220 (16)	−0.0279 (18)	0.0142 (17)
C42	0.0390 (19)	0.047 (2)	0.065 (2)	−0.0241 (17)	−0.0327 (18)	0.0168 (18)
C43	0.0323 (16)	0.0327 (17)	0.0394 (19)	−0.0168 (14)	−0.0123 (15)	0.0025 (14)
C44	0.0426 (19)	0.0382 (19)	0.058 (2)	−0.0222 (16)	−0.0286 (18)	0.0163 (17)
C45	0.0426 (19)	0.041 (2)	0.060 (2)	−0.0226 (16)	−0.0296 (18)	0.0131 (17)
O51	0.0505 (16)	0.081 (2)	0.0583 (18)	−0.0412 (15)	0.0038 (13)	−0.0083 (15)
N51	0.0396 (16)	0.058 (2)	0.0424 (18)	−0.0237 (15)	−0.0018 (14)	−0.0025 (15)
C51	0.053 (2)	0.059 (2)	0.034 (2)	−0.0267 (19)	−0.0077 (17)	0.0106 (18)
C52	0.0421 (19)	0.064 (2)	0.0311 (19)	−0.0220 (18)	−0.0105 (16)	0.0087 (17)
C53	0.0355 (18)	0.053 (2)	0.0328 (18)	−0.0169 (16)	−0.0099 (15)	0.0092 (16)
C54	0.051 (2)	0.089 (3)	0.034 (2)	−0.035 (2)	−0.0117 (18)	0.012 (2)
C55	0.047 (2)	0.081 (3)	0.048 (2)	−0.030 (2)	−0.0153 (19)	0.002 (2)
O1W	0.0324 (13)	0.078 (2)	0.0532 (17)	−0.0274 (14)	−0.0144 (12)	0.0043 (14)
O2W	0.0399 (14)	0.0654 (18)	0.0458 (15)	−0.0357 (13)	0.0008 (11)	−0.0131 (13)

Geometric parameters (Å, º)

Y1—O31	2.277 (2)	C33—C34	1.494 (7)
Y1—O12^i	2.350 (2)	C33—H33	0.9300
Y1—O2W	2.360 (2)	C34—H34A	0.9600
Y1—O41	2.368 (2)	C34—H34B	0.9600
Y1—O1W	2.388 (2)	C34—H34C	0.9600
Y1—O11	2.399 (2)	O41—N41	1.316 (3)
Y1—O21	2.429 (2)	N41—C41	1.337 (4)
Y1—O22	2.478 (2)	N41—C45	1.343 (4)
Y1—O12	2.761 (3)	C41—C42	1.369 (4)
O11—C11	1.255 (4)	C41—H41	0.9300
O12—C11	1.259 (4)	C42—C43	1.380 (5)
C11—C12	1.457 (5)	C42—H42	0.9300
C12—C13	1.252 (7)	C43—C44	1.390 (4)
C12—H12	0.9300	C43—C43^ii	1.483 (6)
C13—C14	1.541 (7)	C44—C45	1.365 (4)
C13—H13	0.9300	C44—H44	0.9300
C14—H14A	0.9600	C45—H45	0.9300
C14—H14B	0.9600	O51—N51	1.303 (4)
C14—H14C	0.9600	N51—C55	1.334 (5)
O21—C21	1.273 (4)	N51—C51	1.339 (5)
O22—C21	1.252 (4)	C51—C52	1.359 (5)
C22—C23	1.273 (4)	C51—H51	0.9300
C22—H22	0.9300	C52—C53	1.382 (5)
C23—C24	1.499 (6)	C52—H52	0.9300
C23—H23	0.9300	C53—C54	1.397 (5)
C24—H24A	0.9600	C53—C53^iii	1.477 (6)
C24—H24B	0.9600	C54—C55	1.366 (5)
C24—H24C	0.9600	C54—H54	0.9300
O31—C31	1.263 (4)	C55—H55	0.9300
O32—C31	1.240 (5)	O1W—H1WA	0.85 (3)
C31—C32	1.498 (6)	O1W—H1WB	0.85 (3)
C32—C33	1.268 (4)	O2W—H2WA	0.85 (3)
C32—H32	0.9300	O2W—H2WB	0.85 (3)
O31—Y1—O12^i	90.89 (9)	C23—C24—H24B	109.5
O31—Y1—O2W	80.95 (9)	H24A—C24—H24B	109.5
O12^i—Y1—O2W	72.59 (8)	C23—C24—H24C	109.5
O31—Y1—O41	93.21 (8)	H24A—C24—H24C	109.5
O12^i—Y1—O41	146.69 (9)	H24B—C24—H24C	109.5
O2W—Y1—O41	140.68 (8)	C31—O31—Y1	138.5 (3)
O31—Y1—O1W	76.24 (9)	O32—C31—O31	124.6 (4)
O12^i—Y1—O1W	140.14 (9)	O32—C31—C32	118.8 (4)
O2W—Y1—O1W	68.24 (9)	O31—C31—C32	116.6 (4)
O41—Y1—O1W	72.59 (9)	C33—C32—C31	126.5 (4)
O31—Y1—O11	153.31 (9)	C33—C32—H32	116.7
O12^i—Y1—O11	111.66 (8)	C31—C32—H32	116.7
O2W—Y1—O11	92.04 (9)	C32—C33—C34	127.6 (5)
O41—Y1—O11	75.95 (8)	C32—C33—H33	116.2
O1W—Y1—O11	77.24 (9)	C34—C33—H33	116.2
O31—Y1—O21	126.33 (8)	C33—C34—H34A	109.5
O12^i—Y1—O21	76.51 (8)	C33—C34—H34B	109.5
O2W—Y1—O21	138.88 (8)	H34A—C34—H34B	109.5
O41—Y1—O21	74.50 (7)	C33—C34—H34C	109.5
O1W—Y1—O21	140.92 (8)	H34A—C34—H34C	109.5
O11—Y1—O21	74.82 (8)	H34B—C34—H34C	109.5
O31—Y1—O22	73.48 (8)	N41—O41—Y1	130.26 (18)
O12^i—Y1—O22	77.61 (8)	O41—N41—C41	119.2 (3)
O2W—Y1—O22	140.07 (9)	O41—N41—C45	120.8 (3)
O41—Y1—O22	71.98 (8)	C41—N41—C45	120.0 (3)
O1W—Y1—O22	131.26 (9)	N41—C41—C42	120.5 (3)
O11—Y1—O22	123.84 (8)	N41—C41—H41	119.8
O21—Y1—O22	52.92 (7)	C42—C41—H41	119.8
O31—Y1—O12	147.25 (8)	C41—C42—C43	121.6 (3)
O12^i—Y1—O12	63.09 (10)	C41—C42—H42	119.2
O2W—Y1—O12	72.73 (8)	C43—C42—H42	119.2
O41—Y1—O12	119.51 (7)	C42—C43—C44	116.1 (3)
O1W—Y1—O12	110.30 (9)	C42—C43—C43^ii	122.0 (3)
O11—Y1—O12	48.93 (7)	C44—C43—C43^ii	121.9 (4)
O21—Y1—O12	69.35 (7)	C45—C44—C43	121.0 (3)
O22—Y1—O12	115.92 (8)	C45—C44—H44	119.5
C11—O11—Y1	104.2 (2)	C43—C44—H44	119.5
C11—O12—Y1^i	152.6 (2)	N41—C45—C44	120.8 (3)
C11—O12—Y1	86.69 (19)	N41—C45—H45	119.6
Y1^i—O12—Y1	116.91 (10)	C44—C45—H45	119.6
O11—C11—O12	118.7 (3)	O51—N51—C55	120.3 (3)
O11—C11—C12	124.8 (3)	O51—N51—C51	121.0 (3)
O12—C11—C12	116.6 (3)	C55—N51—C51	118.7 (3)
C13—C12—C11	125.5 (5)	N51—C51—C52	121.9 (3)
C13—C12—H12	117.2	N51—C51—H51	119.0
C11—C12—H12	117.2	C52—C51—H51	119.0
C12—C13—C14	123.5 (5)	C51—C52—C53	121.4 (3)
C12—C13—H13	118.3	C51—C52—H52	119.3
C14—C13—H13	118.3	C53—C52—H52	119.3
C13—C14—H14A	109.5	C52—C53—C54	115.0 (3)
C13—C14—H14B	109.5	C52—C53—C53^iii	122.3 (4)
H14A—C14—H14B	109.5	C54—C53—C53^iii	122.6 (4)
C13—C14—H14C	109.5	C55—C54—C53	121.6 (4)
H14A—C14—H14C	109.5	C55—C54—H54	119.2
H14B—C14—H14C	109.5	C53—C54—H54	119.2
C21—O21—Y1	94.41 (19)	N51—C55—C54	121.1 (4)
C21—O22—Y1	92.66 (19)	N51—C55—H55	119.4
O22—C21—O21	119.9 (3)	C54—C55—H55	119.4
C23—C22—C21	124.6 (4)	Y1—O1W—H1WA	134 (3)
C23—C22—H22	117.7	Y1—O1W—H1WB	101 (3)
C21—C22—H22	117.7	H1WA—O1W—H1WB	106 (3)
C22—C23—C24	127.7 (5)	Y1—O2W—H2WA	121 (2)
C22—C23—H23	116.2	Y1—O2W—H2WB	129 (2)
C24—C23—H23	116.2	H2WA—O2W—H2WB	107 (3)
C23—C24—H24A	109.5

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WA···O21^i	0.84 (3)	1.88 (3)	2.697 (3)	166 (3)
O1W—H1WB···O32	0.85 (3)	1.81 (3)	2.639 (4)	167 (3)
O1W—H1WA···O11^iv	0.85 (3)	1.96 (3)	2.806 (3)	173 (4)
O2W—H2WB···O51^iv	0.84 (3)	1.94 (3)	2.762 (4)	166 (3)

Symmetry codes: (i) −x+2, −y+2, −z+1; (iv) −x+1, −y+2, −z+1.