Three lanthanide complexes derived from itaconic acid and 2,2'-bipyridine

The structures of three new polymeric lanthanide complexes, poly[[bis­(2,2'-bipyridine)-[mu]₄-itaconato-di-[mu]₃-itaconato-digadolinium(III)] tetra­hydrate], {[Gd₂(C₅H₄O₄)₃(C₁₀H₈N₂)₂]·4H₂O}_n, (I), poly[diaqua­(2,2'-bipyridine)di-[mu]₃-itaconato-[mu]₂-ita­conato-digadolinium(III)], [Gd₂(C₅H₄O₄)₃(C₁₀H₈N₂)(H₂O)₂]_n, (II), and poly­[[bis­(2,2'-bipyridine)-[mu]₄-itaconato-di-[mu]₃-itaconato-di­holmium(III)] dihydrate], {[Ho₂(C₅H₄O₄)₃(C₁₀H₈N₂)₂]·2H₂O}_n, (III), have been solved from twinned specimens. Compound (I) presents a two-dimensional polymeric structure parallel to (011) built up around two independent nine-coordinated Gd centres displaying similar GdO₇N₂ environments, with both N-donor atoms in each provided by a chelating 2,2'-bipyridine (bpy) unit. The coord­inating O atoms are from three different itaconate (ita) anions (itaconic acid is 2-methyl­idene­butane­dioic acid). Compound (II) also presents two independent Gd centres (one ten- and the other eight-coordinated), but the overall formula and individual coordinations are different from those of (I). The chemical unit is in this case completed by one bpy ligand, three ita anions (one of them displaying a new, hitherto unreported, [mu]₃-O,O':O',O'':O''' binding mode) and two aqua ligands. The whole structure is built up around a twofold rotation axis passing through both cations, as well as through the centre of the bpy ligand and one of the ita anions, thus making only half of the chemical unit independent. Finally, compound (III) presents a single independent Ho centre, a bpy unit and one and a half ita anions (one of them bisected by a twofold rotation axis) in the asymmetric unit, plus two (disordered) nonbonded solvent water mol­ecules. In compounds (II) and (III), those ita anions bisected by a symmetry element incompatible with the inter­nal symmetry of the ligand exhibit disorder in the C=CH₂ group.

S1. Comment

The generation of high-dimensional coordination polymers assembled from metal–organic compounds and characterized by open frameworks has been (and still is) an important branch of crystal engineering (see, for example, Eddaoudi et al., 2001), due to the expected potential properties of the eventual novel compounds, e.g. catalysis (Seo et al., 2000), ion-exchange (Yaghi et al., 1997), gas absorption (Yaghi et al., 2003), and so on. While carboxylic acids have been extensively exploited in order to provide promising functional frameworks, aliphatic acids in particular do not seem to have been adequately explored [although for a recent report on the subject, see Zhang et al. (2006)], in spite of their well known flexibility which would make them extremely suitable to achieve a variety of different architectures. One of these rather unexploited ligands is itaconic acid (hereinafter ita), the common name of methylene succinic acid (systematic name 2-methylidenebutanedioic acid), an extremely flexible ligand which, by way of its capability of binding through two carboxylic acid ends, can provide an extensive variety of coordination modes.

In spite of this potentiality there are only a limited number of reported complexes containing the coordinated ita anion. A survey of the Cambridge Structural Database (2008 version; Allen, 2002) showed that there are nine such complexes in total, three of them with the ligand bound to transition metals [Ni (Burrows, Harrington et al., 2004), Zn (Burrows, Donovan et al., 2004) and Cd (Contreras et al., 1997)], one to an alkaline earth [Ba (Briceño et al., 1999)] and five to lanthanides [La, Eu, Dy, Er and Yb (Liu et al., 2005)]. Surprisingly, in spite of this limited number of complexes, as many as ten different coordination modes could be distinguished for the ligand (coordination modes Nos. 1–10, shown in the second scheme).

The extended character of the molecule and its double-ended binding ability render it able to fulfil an efficient bridging role in (usually complex) three-dimensional structures in which voids and cavities can easily build up. Looking for new compounds of this kind, we have tried to synthesize via hydrothermal methods some lanthanide complexes bearing itaconate (ita) as the stabilizing anion and bipyridine (bpy) as an ancillary ligand. Unfortunately, and in spite of having attempted the synthesis with a diversity of lanthanide atoms, the process only afforded crystals for Ln = Gd [two different phases, compounds (I) and (II)] and Ho [compound (III)], and in all three cases the colourless thin rectangular plates obtained proved to be multiple or twinned to a greater or lesser degree. The results presented here are the outcome of a laborious and painstaking sample screening, which afforded the few crystals amenable to a full crystallographic study. However, the unaccountable effect of twinning showed up in the requirement for a large number of restraints in order to refine successfully the models obtained, as well as in the large residual electron density found in the final difference electron-density maps. In spite of these drawbacks, the structures obtained appear quite reasonable and they provide a rich survey of (at least qualitative) crystallographic results, in particular, a new, hitherto unreported, coordination mode for the ita anion (coordination mode No. 11 in the second scheme).

Tables 1, 2 and 3 present some relevant structural parameters for the three structures. Intermolecular interactions are surveyed in Tables 4 and 5.

Compound (I), [Gd₂(bpy)₂(ita)₃].4H₂O, is shown in Fig. 1. It presents a two-dimensional polymeric structure built up around two independent Gd atoms displaying similar GdO₇N₂ environments, with both N atoms provided by two chelating bpy units each. The coordinating O atoms are from the three different ita anions, which act in two well differentiated ways. (In what follows, trailing digits will indicate a definite group of atoms. Thus, ita3 indicates the anion composed of atoms C13–C53/O13–O43, etc.)

Ita3 and ita5 (Fig. 2a). present a µ₃-(O,O':O'',O''':O''') binding mode (coordination mode No. 4), bridging three symmetry-related Gd atoms of the same sort each, i.e. ita5 to atoms Gd1 and ita 3 to atoms Gd2. The bridging effect of these two anions is to generate columnar arrays of centrosymmetric dimers made up of either Gd1 or Gd2 coordination polyhedra, respectively, parallel to b (vertical arrays in Fig. 2a)

Ita4 (Fig. 2b) presents a µ₄-(O:O':O'':O''') coordination mode (No. 7) and joins neighbouring columns of different kinds through transverse bridging, i.e. Gd1 columns are joined to Gd2 columns (horizontal arrays in Fig. 2a), to generate the above-mentioned two-dimensional polymeric structure parallel to (011). The hydrophobic aromatic bpy groups stretch outwards, enlarging these sheets on both sides, and serve as interaction agents between neighbouring sheets through interdigitation (Fig. 2b), resulting in rather short interplanar π–π distances (Table 4).

Compound (II), [Gd₂(bpy)(ita)₃(H₂O)₂], is shown in Fig. 3. This second gadolinium phase also presents two independent Gd atoms, but the overall formula and individual coordination are different. The chemical unit is in this case constructed out of two Gd cations, one bpy ligand, three ita anions and two aqua ligands, to give the minimum formula shown above, but since the whole structure is built up around a twofold axis passing through both cations, as well as through the centre of the bpy ligand and one of the ita anions, only half of the chemical unit is independent (Z' = 0.5).

Contrasting with (I), the two coordination polyhedra of (II) are completely different from each other (Fig. 3). Gd1 is ten-coordinated by five chelating ligands, one bpy and four carboxylate groups from two pairs of symmetry-related ita2 and ita3 groups (coordination mode No. 4). Gd2, instead, receives four bonds from two very open –O—C₄—O– bites from ita2 and two extra bridging bonds from the vacant carboxylate atom O12, completing a new, hitherto unreported, µ₃-(O,O':O',O'':O''') binding mode for the ita2 anion (coordination mode No. 11). Two water molecules complete an eightfold coordination of the cation (Fig. 3).

The tight ita linkage drives the formation of very broad strips, the width of four coordination polyhedra, which run along [001] (Fig. 4a). In these arrays the hydrophobic bpy are located at the ribbon `edges', so that the structures link laterally (along [010]) in a rather feeble fashion through interdigitation of the distorted weakly interacting bpy groups (Fig. 4b and Table 4), to form a two-dimensional structure parallel to the (100) plane. The chains also interact at right angles to the latter contact, along [100], through a non-conventional C52—H52B···O42(3/2 - x, 1/2 - y, -z) bond [C—H = 0.93 Å, H···O = 2.380 (19) Å and C—H···O = 161°].

Compound (III), [Ho₂(bpy)₂(ita)₃].4H₂O, is shown in Fig. 5. The structure presents a single independent cation (Ho1), a bpy unit and one and a half ita anions in the coordination polyhedron, plus one non-bonded solvent water molecule (split over two disordered halves) stabilizing the structure. These entities are disposed around a centre of symmetry as dimeric units of general formula [Ho₂(bpy)₂(ita)₃].2H₂O, the cation being eight-coordinated by a chelating bpy and two chelating carboxylate groups from an ita2 unit and its [010] translational image (coordination mode No. 4), thus generating a chain structure along the b axis, similar to (I). The difference arises in the way in which the two bridging O atoms of the remaining ita3 unit interact. The result is an array of chains running along b, made up of dimers bridged by ita2, and these chains are in turn interconnected sideways by the centrosymmetric (and accordingly disordered at the C═CH₂ group) ita3. The two-dimensional structure parallel to (100) presents the bpy pointing outwards, so that interaction between sheets is provided, as in (I), by π–π contacts between interdigitated aromatic rings.

Summarizing, in the structures reported here the itaconate ligand has again shown a great coordination capability giving rise to tightly interconnected structures, all of them polymeric. Compounds (I) and (III) present two-dimensional arrays further connected by weaker π–π contacts, while compound (II) shows instead a broad strip-like formation packed via an assembly of diverse interactions. In compounds (II) and (III), some of the itaconate units present a disordered structure (in the C═CH₂ group) due to the ligand being bisected by a symmetry element incompatible with its internal symmetry. This is not an unusual feature in the anion, and it has already been found in many of the previously reported itaconate structures, viz. nickel itaconate (Burrows, Harrington et al., 2004), and many of the lanthanide itaconate complexes, viz. Ln = Eu, Dy, Er and Yb (Liu et al., 2005).

S2. Experimental

The reactants for the syntheses were the corresponding lanthanide oxides (Gd₂O₃ or Ho₂O₃, 5.0 × 10^-4 M), itaconic acid (1.5 × 10^-3 M) and 2,2'-bipyridine (5.0 or 10.0 × 10^-4 M), corresponding to molar ratios 1:3:2 for (I), 1:3:1 for (II) and 1:3:1 for (III). Starting materials were used as purchased, without further purification. The mixture of the corresponding oxide in H₂O (50 ml) was heated under reflux for about 30 min, after which the itaconic acid was added and then the base, in that specific order. This was relevant, since on inversion of the sequence the reaction would not take place. On standing, colourless crystals for the gadolinium complexes, and pink for the holmium one, appeared. In all three cases the crystals obtained were multiple to a larger or smaller degree, necessitating a lengthy screening process to find the most suitable (though far from perfect) crystals for X-ray diffraction analysis. The first two compounds came out formulated as planned in the synthesis, i.e. in 1:3:2 and 1:3:1 ratios, respectively. Compound (III) instead appeared in a 1:3:2 ratio, with a doubling of the (expected) bpy content. Hydrothermal methods were also tried in the (unsuccessful) search for better specimens.

S3. Refinement

As already stated, the specimens were multiply twinned in a way that made it impossible to find an adequate twin law to separate them. However, in the three crystals finally chosen for data collection it was possible to integrate the main contribution as an independent set by appropriately setting the orientation matrix, which thus acted as a filter. This worked fine with structures (II) and (III), but not so well for structure (I), where severe overlap forced the rejection of a fraction of the data set (ca 13%). In the remaining two structures, the final integrated fraction at a level of 2θ = 50° was almost unity.

Structure resolution was in all cases straightforward by standard direct methods, but refinement was only possible by applying similarity restraints to (expected) similar bonds and angles in different ligands. This was directly linked to the degree of difficulty found in the integration of each structure. Thus, (I) required the full power of the SHELXL97 package (Sheldrick, 2008) (instructions SADI, DELU, SIMU and, in a few pathological cases, ISOR, DFIX and DANG). Structures (II) and (III) required milder restrictions.

The unavoidable problems resulting from poor data quality were evident in the high R values obtained, the unusual SHELXL97 weighting schemes and the large unaccounted-for electron-density peaks and holes, which were, for (I): 7.17 e A^-3 (0.36 Å from C45) and -3.02 e A^-3 (1.16 Å from C43); for (II): 1.83 e A^-3 (0.74 Å from C23) and -4.17 e A^-3 (1.29 Å from H41); for (III): 10.21 e A^-3 (1.02 Å from HO1) and -3.30 e A^-3 (1.02 Å from H81)

C-bound H atoms were placed in their expected positions and allowed to ride in both coordinates (C—H = 0.93–0.97 Å) and isotropic displacement parameters [U_iso(H) = 1.2 or 1.5U_eq(C)]. O-bound H atoms could not be found and were not included in the model.

Computing details

For all compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2002); data reduction: SAINT-NT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. The two Gd coordination polyhedra in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1, -y, -z; (ii) x + 1, y, z; (iii) -x + 1, -y + 1, -z - 1; (iv) -x, -y + 1, -z - 1.]
	Fig. 2. Packing views of (I). (a) Showing the binding modes displayed by ita3 and ita5. (b) Showing the binding mode displayed by ita4 and the interdigitation of the bpy groups. Gd1-only columns are along the A–A lines and Gd2-only columns along the B–B lines.
	Fig. 3. The elemental dimeric unit in (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1, y, -z + 1/2; (ii) -x + 1, -y + 1, -z; (iii) x, -y + 1, z + 1/2.]
	Fig. 4. Packing views of (II). (a) Showing the formation of the broad strips running along c. (b) Viewed down the strip direction, showing their mutual interactions. [Symmetry code: (i) 1/2 - x, 1/2 - y, 1 - z.]
	Fig. 5. The centrosymmetric dimeric unit in (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 2, -y + 1, -z + 1; (ii) -x + 2, -y, -z + 1; (iii) x, y + 1, z.]
	Fig. 6. Packing views of (III). (a) Showing the formation of chains running along c. (b) Viewed down the chain direction, showing their mutual interactions. [Symmetry code: (i) -x + 2, -y + 1, -z + 1.]

(I) Poly[[bis(2,2'-bipyridine)-µ₄-itaconato-di-µ₃-itaconato-digadolinium(III)] tetrahydrate]

Crystal data

[Gd2(C5H4O4)3(C10H8N2)2]·4H2O	Z = 2
Mr = 1083.18	F(000) = 1060
Triclinic, P1	Dx = 1.928 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5507 (19) Å	Cell parameters from 8754 reflections
b = 12.598 (3) Å	θ = 2.0–26.3°
c = 17.582 (4) Å	µ = 3.60 mm^−1
α = 71.60 (3)°	T = 293 K
β = 82.32 (3)°	Plate, colourless
γ = 68.39 (3)°	0.20 × 0.15 × 0.08 mm
V = 1865.9 (9) Å^3

Data collection

Bruker SMART? CCD area-detector diffractometer	6922 independent reflections
Radiation source: fine-focus sealed tube	5639 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ϕ and ω scans	θmax = 27.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −11→12
Tmin = 0.50, Tmax = 0.75	k = −15→16
9794 measured reflections	l = −21→22

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.204	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.1319P)^2 + 23.4752P] where P = (Fo^2 + 2Fc^2)/3
6922 reflections	(Δ/σ)max = 0.001
512 parameters	Δρmax = 7.16 e Å^−3
541 restraints	Δρmin = −3.02 e Å^−3

Special details

Experimental. Data collected from twinned crystals

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
Gd1	0.54142 (6)	0.08123 (5)	0.07013 (3)	0.02018 (18)
Gd2	0.33097 (6)	0.64895 (4)	−0.49861 (3)	0.01835 (18)
N11	0.5043 (12)	0.1010 (10)	0.2137 (7)	0.039 (2)
N21	0.4343 (13)	0.2964 (11)	0.0841 (6)	0.040 (2)
C11	0.5467 (16)	−0.0002 (14)	0.2747 (7)	0.045 (3)
H11	0.5899	−0.0731	0.2635	0.054*
C21	0.5271 (18)	0.0021 (15)	0.3536 (8)	0.054 (3)
H21	0.5518	−0.0683	0.3954	0.065*
C31	0.4702 (19)	0.1114 (13)	0.3687 (10)	0.059 (4)
H31	0.4511	0.1160	0.4211	0.070*
C41	0.4420 (19)	0.2142 (16)	0.3049 (8)	0.057 (4)
H41	0.4193	0.2876	0.3140	0.068*
C51	0.4477 (17)	0.2077 (12)	0.2275 (8)	0.047 (3)
C61	0.4101 (17)	0.3160 (12)	0.1558 (8)	0.045 (3)
C71	0.341 (2)	0.4301 (12)	0.1616 (11)	0.060 (4)
H71	0.3272	0.4423	0.2120	0.073*
C81	0.292 (2)	0.5270 (17)	0.0952 (9)	0.072 (4)
H81	0.2412	0.6032	0.1004	0.087*
C91	0.322 (2)	0.5074 (14)	0.0205 (12)	0.069 (4)
H91	0.2907	0.5693	−0.0263	0.083*
C101	0.4005 (19)	0.3915 (11)	0.0189 (10)	0.054 (3)
H101	0.4321	0.3786	−0.0308	0.065*
N12	0.2390 (14)	0.7852 (9)	−0.4029 (6)	0.039 (2)
N22	0.2316 (12)	0.8729 (9)	−0.5647 (6)	0.035 (2)
C12	0.2394 (18)	0.7356 (13)	−0.3233 (8)	0.049 (3)
H12	0.2661	0.6533	−0.3022	0.058*
C22	0.200 (2)	0.8069 (12)	−0.2728 (10)	0.053 (3)
H22	0.1973	0.7743	−0.2175	0.064*
C32	0.165 (2)	0.9282 (12)	−0.3072 (9)	0.054 (3)
H32	0.1437	0.9766	−0.2736	0.064*
C42	0.1588 (18)	0.9812 (13)	−0.3890 (8)	0.049 (3)
H42	0.1334	1.0631	−0.4115	0.058*
C52	0.1932 (16)	0.9038 (10)	−0.4355 (8)	0.039 (3)
C62	0.1917 (16)	0.9551 (9)	−0.5252 (8)	0.038 (3)
C72	0.1478 (19)	1.0763 (11)	−0.5631 (9)	0.051 (3)
H72	0.1209	1.1307	−0.5336	0.061*
C82	0.1448 (19)	1.1143 (12)	−0.6455 (8)	0.052 (3)
H82	0.1168	1.1953	−0.6725	0.062*
C92	0.1834 (18)	1.0320 (10)	−0.6881 (9)	0.049 (3)
H92	0.1818	1.0560	−0.7439	0.058*
C102	0.2246 (16)	0.9128 (10)	−0.6451 (7)	0.037 (3)
H102	0.2489	0.8570	−0.6734	0.045*
O13	0.1201 (9)	0.6941 (8)	−0.5862 (5)	0.034 (2)
O23	0.0762 (9)	0.6483 (8)	−0.4540 (4)	0.0285 (18)
O33	−0.3706 (9)	0.5375 (6)	−0.4844 (5)	0.0260 (17)
O43	−0.4711 (8)	0.7276 (6)	−0.4863 (6)	0.0272 (18)
C13	0.0305 (9)	0.6616 (11)	−0.5252 (5)	0.034 (2)
C23	−0.1234 (8)	0.6718 (6)	−0.5386 (5)	0.024 (2)
C33	−0.1988 (8)	0.6296 (9)	−0.4617 (5)	0.026 (2)
H33A	−0.2071	0.6806	−0.4287	0.031*
H33B	−0.1346	0.5498	−0.4340	0.031*
C43	−0.3522 (9)	0.6268 (7)	−0.4678 (7)	0.0217 (19)
C53	−0.1760 (14)	0.7136 (12)	−0.6109 (6)	0.041 (3)
H53A	−0.1162	0.7373	−0.6544	0.049*
H53B	−0.2733	0.7198	−0.6189	0.049*
O14	0.4750 (12)	0.1058 (8)	−0.1445 (5)	0.034 (2)
O24	0.4983 (12)	0.2025 (8)	−0.0628 (4)	0.037 (2)
O34	0.3925 (9)	0.5320 (6)	−0.3922 (4)	0.0205 (15)
O44	0.5557 (10)	0.3423 (7)	−0.3765 (5)	0.037 (2)
C14	0.4915 (19)	0.2033 (10)	−0.1380 (5)	0.047 (3)
C24	0.5472 (16)	0.2844 (12)	−0.2068 (6)	0.074 (4)
H24A	0.6146	0.2388	−0.2407	0.089*
H24B	0.6031	0.3202	−0.1868	0.089*
C34	0.4163 (19)	0.3810 (14)	−0.2552 (6)	0.087 (5)
C44	0.4433 (15)	0.4161 (9)	−0.3437 (5)	0.045 (3)
C54	0.288 (2)	0.428 (2)	−0.2179 (12)	0.116 (8)
H54A	0.2066	0.4868	−0.2475	0.140*
H54B	0.2795	0.4011	−0.1624	0.140*
O15	−0.2119 (9)	−0.0298 (8)	0.1379 (5)	0.034 (2)
O25	−0.2449 (8)	0.1484 (7)	0.0479 (5)	0.0283 (18)
O35	0.3230 (8)	0.0445 (7)	0.0087 (5)	0.0280 (17)
O45	0.2615 (9)	0.1472 (8)	0.0960 (5)	0.0299 (18)
C15	−0.1499 (8)	0.0477 (7)	0.0917 (5)	0.0174 (13)
C25	0.0092 (8)	0.0311 (7)	0.0992 (5)	0.026 (2)
C35	0.0502 (8)	0.1281 (8)	0.0410 (6)	0.027 (2)
H35A	0.0250	0.1323	−0.0118	0.033*
H35B	−0.0138	0.2021	0.0518	0.033*
C45	0.2035 (9)	0.1239 (8)	0.0370 (6)	0.0174 (13)
C55	0.0973 (14)	−0.0594 (11)	0.1516 (8)	0.042 (3)
H55A	0.1972	−0.0669	0.1545	0.051*
H55B	0.0603	−0.1165	0.1861	0.051*
O1W	0.066 (2)	0.2802 (13)	−0.1664 (11)	0.090 (5)
O2W	−0.034 (2)	0.5836 (17)	−0.2922 (11)	0.101 (6)
O3W	−0.157 (2)	0.3996 (15)	−0.2784 (10)	0.087 (5)
O4W	−0.024 (2)	0.648 (2)	−0.1446 (18)	0.148 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Gd1	0.0152 (3)	0.0299 (3)	0.0176 (3)	−0.0106 (2)	0.0006 (2)	−0.0068 (2)
Gd2	0.0127 (3)	0.0149 (3)	0.0258 (3)	−0.0051 (2)	−0.0027 (2)	−0.0023 (2)
N11	0.020 (5)	0.065 (6)	0.051 (6)	−0.025 (4)	0.001 (4)	−0.030 (5)
N21	0.031 (5)	0.046 (5)	0.058 (6)	−0.021 (4)	0.006 (5)	−0.029 (5)
C11	0.029 (6)	0.078 (7)	0.046 (6)	−0.024 (5)	−0.003 (5)	−0.032 (6)
C21	0.041 (6)	0.085 (8)	0.042 (6)	−0.015 (6)	−0.003 (5)	−0.034 (6)
C31	0.042 (7)	0.085 (8)	0.048 (7)	−0.013 (6)	0.003 (6)	−0.032 (6)
C41	0.043 (6)	0.078 (8)	0.054 (7)	−0.015 (6)	0.007 (6)	−0.033 (6)
C51	0.029 (5)	0.064 (6)	0.055 (6)	−0.018 (5)	0.008 (5)	−0.031 (5)
C61	0.034 (5)	0.055 (6)	0.059 (6)	−0.016 (5)	0.012 (5)	−0.037 (5)
C71	0.056 (7)	0.054 (7)	0.072 (8)	−0.014 (6)	0.012 (6)	−0.031 (6)
C81	0.064 (8)	0.060 (7)	0.082 (8)	−0.012 (7)	0.015 (7)	−0.024 (7)
C91	0.061 (8)	0.057 (7)	0.080 (8)	−0.014 (7)	0.015 (7)	−0.022 (7)
C101	0.050 (7)	0.047 (6)	0.069 (7)	−0.017 (6)	0.010 (6)	−0.026 (6)
N12	0.037 (5)	0.039 (5)	0.049 (5)	−0.011 (4)	0.008 (5)	−0.030 (5)
N22	0.027 (5)	0.026 (4)	0.051 (6)	−0.010 (4)	−0.007 (4)	−0.006 (4)
C12	0.042 (6)	0.051 (6)	0.052 (6)	−0.010 (5)	0.011 (5)	−0.026 (6)
C22	0.049 (7)	0.058 (7)	0.052 (7)	−0.016 (6)	0.013 (6)	−0.024 (6)
C32	0.051 (7)	0.053 (7)	0.061 (7)	−0.016 (6)	0.005 (6)	−0.025 (6)
C42	0.045 (6)	0.042 (6)	0.064 (7)	−0.013 (5)	0.003 (6)	−0.026 (6)
C52	0.035 (5)	0.033 (5)	0.057 (6)	−0.017 (4)	0.000 (5)	−0.021 (5)
C62	0.030 (5)	0.028 (5)	0.057 (6)	−0.012 (4)	0.001 (5)	−0.013 (5)
C72	0.045 (6)	0.029 (6)	0.069 (7)	−0.013 (5)	0.000 (6)	−0.001 (6)
C82	0.046 (7)	0.027 (5)	0.066 (7)	−0.012 (5)	−0.005 (6)	0.008 (6)
C92	0.042 (6)	0.031 (6)	0.057 (7)	−0.009 (5)	−0.011 (6)	0.008 (5)
C102	0.033 (6)	0.026 (5)	0.048 (6)	−0.009 (4)	−0.011 (5)	−0.001 (5)
O13	0.019 (4)	0.039 (5)	0.040 (5)	−0.014 (4)	0.010 (4)	−0.004 (4)
O23	0.027 (3)	0.030 (3)	0.032 (3)	−0.016 (2)	0.000 (2)	−0.006 (2)
O33	0.023 (4)	0.020 (4)	0.029 (4)	−0.002 (3)	−0.005 (3)	−0.005 (3)
O43	0.019 (4)	0.020 (4)	0.046 (5)	−0.010 (3)	−0.003 (3)	−0.010 (4)
C13	0.021 (5)	0.030 (5)	0.038 (5)	0.001 (4)	−0.001 (4)	−0.006 (4)
C23	0.016 (4)	0.028 (4)	0.030 (5)	−0.010 (4)	0.003 (4)	−0.010 (4)
C33	0.017 (5)	0.028 (5)	0.029 (5)	−0.005 (4)	−0.004 (4)	−0.006 (4)
C43	0.020 (3)	0.019 (3)	0.028 (3)	−0.010 (2)	0.005 (2)	−0.009 (2)
C53	0.024 (6)	0.050 (7)	0.045 (7)	−0.014 (5)	−0.002 (5)	−0.004 (6)
O14	0.053 (5)	0.040 (5)	0.014 (4)	−0.026 (4)	−0.001 (4)	−0.002 (4)
O24	0.050 (5)	0.040 (5)	0.016 (4)	−0.013 (4)	−0.006 (4)	−0.004 (4)
O34	0.0202 (18)	0.0219 (17)	0.0222 (17)	−0.0059 (10)	−0.0031 (10)	−0.0109 (11)
O44	0.039 (5)	0.033 (5)	0.029 (4)	−0.004 (4)	0.003 (4)	−0.006 (4)
C14	0.063 (6)	0.052 (6)	0.025 (5)	−0.020 (5)	−0.002 (5)	−0.007 (5)
C24	0.085 (8)	0.069 (7)	0.044 (7)	−0.013 (7)	−0.002 (7)	0.001 (6)
C34	0.079 (8)	0.075 (7)	0.054 (7)	0.001 (7)	0.014 (6)	0.012 (6)
C44	0.042 (5)	0.046 (5)	0.031 (5)	−0.005 (5)	0.002 (5)	−0.002 (5)
C54	0.100 (11)	0.095 (11)	0.081 (10)	0.006 (10)	0.017 (10)	0.019 (10)
O15	0.020 (4)	0.044 (5)	0.037 (5)	−0.012 (4)	−0.001 (4)	−0.012 (4)
O25	0.023 (3)	0.030 (3)	0.030 (3)	−0.009 (2)	0.005 (2)	−0.007 (2)
O35	0.025 (4)	0.034 (4)	0.025 (4)	−0.009 (3)	0.002 (3)	−0.010 (3)
O45	0.021 (4)	0.041 (4)	0.031 (4)	−0.007 (3)	0.002 (3)	−0.021 (3)
C15	0.019 (2)	0.017 (2)	0.021 (2)	−0.0111 (18)	0.0110 (19)	−0.0113 (19)
C25	0.025 (5)	0.027 (4)	0.029 (5)	−0.008 (4)	0.004 (4)	−0.013 (4)
C35	0.027 (5)	0.023 (5)	0.028 (5)	−0.006 (4)	0.006 (4)	−0.008 (4)
C45	0.019 (2)	0.017 (2)	0.021 (2)	−0.0111 (18)	0.0110 (19)	−0.0113 (19)
C55	0.025 (6)	0.045 (7)	0.049 (7)	−0.010 (5)	−0.006 (5)	−0.004 (6)
O1W	0.100 (13)	0.053 (8)	0.092 (12)	−0.020 (8)	−0.024 (10)	0.015 (8)
O2W	0.116 (15)	0.096 (13)	0.089 (13)	−0.032 (12)	0.003 (11)	−0.034 (11)
O3W	0.106 (13)	0.077 (10)	0.089 (12)	−0.033 (9)	−0.022 (10)	−0.030 (9)
O4W	0.084 (14)	0.134 (19)	0.23 (3)	0.017 (13)	−0.046 (16)	−0.10 (2)

Geometric parameters (Å, º)

Gd1—O35^i	2.346 (7)	C32—H32	0.9300
Gd1—O24	2.346 (8)	C42—C52	1.385 (10)
Gd1—O14^i	2.358 (8)	C42—H42	0.9300
Gd1—O25^ii	2.426 (8)	C52—C62	1.503 (16)
Gd1—O15^ii	2.489 (9)	C62—C72	1.383 (10)
Gd1—O45	2.514 (8)	C72—C82	1.376 (11)
Gd1—N11	2.580 (11)	C72—H72	0.9300
Gd1—N21	2.600 (11)	C82—C92	1.380 (11)
Gd1—O35	2.713 (8)	C82—H82	0.9300
Gd1—Gd1^i	3.9748 (13)	C92—C102	1.382 (10)
Gd2—O34	1.983 (7)	C92—H92	0.9300
Gd2—O44^iii	2.304 (8)	C102—H102	0.9300
Gd2—O33^iv	2.347 (7)	O13—C13	1.336 (9)
Gd2—O23	2.456 (8)	O23—C13	1.321 (9)
Gd2—O13	2.487 (9)	O33—C43	1.322 (8)
Gd2—O43^ii	2.496 (7)	O43—C43	1.336 (9)
Gd2—N22	2.542 (11)	C13—C23	1.472 (8)
Gd2—N12	2.621 (10)	C23—C53	1.303 (9)
Gd2—O33^ii	2.679 (8)	C23—C33	1.482 (8)
Gd2—Gd2^iii	3.9573 (19)	C33—C43	1.498 (8)
N11—C51	1.340 (11)	C33—H33A	0.9700
N11—C11	1.346 (11)	C33—H33B	0.9700
N21—C61	1.334 (11)	C53—H53A	0.9300
N21—C101	1.342 (11)	C53—H53B	0.9300
C11—C21	1.383 (10)	O14—C14	1.335 (9)
C11—H11	0.9300	O24—C14	1.329 (9)
C21—C31	1.380 (11)	O34—C44	1.378 (9)
C21—H21	0.9300	O44—C44	1.336 (9)
C31—C41	1.384 (11)	C14—C24	1.496 (9)
C31—H31	0.9300	C24—C34	1.510 (12)
C41—C51	1.381 (11)	C24—H24A	0.9700
C41—H41	0.9300	C24—H24B	0.9700
C51—C61	1.501 (17)	C34—C54	1.33 (2)
C61—C71	1.375 (11)	C34—C44	1.492 (8)
C71—C81	1.378 (11)	C54—H54A	0.9300
C71—H71	0.9300	C54—H54B	0.9300
C81—C91	1.39 (2)	O15—C15	1.327 (8)
C81—H81	0.9300	O25—C15	1.322 (8)
C91—C101	1.381 (11)	O35—C45	1.368 (8)
C91—H91	0.9300	O45—C45	1.390 (9)
C101—H101	0.9300	C15—C25	1.473 (8)
N12—C12	1.340 (11)	C15—Gd1^v	2.880 (8)
N12—C52	1.341 (11)	C25—C55	1.301 (9)
N22—C62	1.339 (10)	C25—C35	1.466 (8)
N22—C102	1.345 (11)	C35—C45	1.439 (8)
C12—C22	1.380 (11)	C35—H35A	0.9700
C12—H12	0.9300	C35—H35B	0.9700
C22—C32	1.381 (11)	C55—H55A	0.9300
C22—H22	0.9300	C55—H55B	0.9300
C32—C42	1.382 (11)
O35^i—Gd1—O24	75.0 (3)	C51—C41—C31	120.0 (16)
O35^i—Gd1—O14^i	76.2 (3)	C51—C41—H41	120.0
O24—Gd1—O14^i	135.9 (3)	C31—C41—H41	120.0
O35^i—Gd1—O25^ii	85.6 (3)	N11—C51—C41	119.4 (14)
O24—Gd1—O25^ii	80.3 (3)	N11—C51—C61	117.3 (11)
O14^i—Gd1—O25^ii	129.5 (3)	C41—C51—C61	122.9 (12)
O35^i—Gd1—O15^ii	76.5 (3)	N21—C61—C71	120.2 (14)
O24—Gd1—O15^ii	127.4 (3)	N21—C61—C51	116.6 (11)
O14^i—Gd1—O15^ii	75.8 (3)	C71—C61—C51	123.0 (12)
O25^ii—Gd1—O15^ii	54.2 (2)	C61—C71—C81	122.0 (17)
O35^i—Gd1—O45	126.0 (2)	C61—C71—H71	119.0
O24—Gd1—O45	89.1 (3)	C81—C71—H71	119.0
O14^i—Gd1—O45	81.7 (3)	C71—C81—C91	117.9 (17)
O25^ii—Gd1—O45	142.8 (3)	C71—C81—H81	121.1
O15^ii—Gd1—O45	142.9 (3)	C91—C81—H81	121.1
O35^i—Gd1—N11	144.0 (3)	C101—C91—C81	116.9 (17)
O24—Gd1—N11	139.6 (3)	C101—C91—H91	121.6
O14^i—Gd1—N11	78.9 (3)	C81—C91—H91	121.6
O25^ii—Gd1—N11	90.7 (3)	N21—C101—C91	124.6 (16)
O15^ii—Gd1—N11	72.4 (3)	N21—C101—H101	117.7
O45—Gd1—N11	74.6 (3)	C91—C101—H101	117.7
O35^i—Gd1—N21	147.5 (3)	C12—N12—C52	121.7 (11)
O24—Gd1—N21	76.5 (3)	C12—N12—Gd2	119.8 (8)
O14^i—Gd1—N21	136.2 (3)	C52—N12—Gd2	118.5 (8)
O25^ii—Gd1—N21	74.6 (3)	C62—N22—C102	117.0 (11)
O15^ii—Gd1—N21	109.9 (3)	C62—N22—Gd2	124.5 (8)
O45—Gd1—N21	68.3 (3)	C102—N22—Gd2	118.4 (7)
N11—Gd1—N21	63.2 (3)	N12—C12—C22	119.8 (14)
O35^i—Gd1—O35	76.7 (3)	N12—C12—H12	120.1
O24—Gd1—O35	70.7 (3)	C22—C12—H12	120.1
O14^i—Gd1—O35	70.7 (3)	C12—C22—C32	117.8 (15)
O25^ii—Gd1—O35	149.0 (3)	C12—C22—H22	121.1
O15^ii—Gd1—O35	141.0 (3)	C32—C22—H22	121.1
O45—Gd1—O35	49.52 (19)	C22—C32—C42	123.0 (15)
N11—Gd1—O35	118.5 (3)	C22—C32—H32	118.5
N21—Gd1—O35	107.9 (3)	C42—C32—H32	118.5
O35^i—Gd1—C15^ii	76.7 (3)	C32—C42—C52	115.5 (14)
O24—Gd1—C15^ii	102.6 (3)	C32—C42—H42	122.3
O14^i—Gd1—C15^ii	102.4 (3)	C52—C42—H42	122.3
O25^ii—Gd1—C15^ii	27.15 (18)	N12—C52—C42	121.8 (12)
O15^ii—Gd1—C15^ii	27.40 (19)	N12—C52—C62	119.6 (10)
O45—Gd1—C15^ii	156.9 (2)	C42—C52—C62	118.3 (10)
N11—Gd1—C15^ii	83.8 (3)	N22—C62—C72	123.2 (13)
N21—Gd1—C15^ii	94.8 (3)	N22—C62—C52	113.8 (10)
O35—Gd1—C15^ii	153.4 (2)	C72—C62—C52	122.9 (11)
O35^i—Gd1—Gd1^i	41.6 (2)	C82—C72—C62	118.4 (14)
O24—Gd1—Gd1^i	67.7 (2)	C82—C72—H72	120.8
O14^i—Gd1—Gd1^i	68.52 (18)	C62—C72—H72	120.8
O25^ii—Gd1—Gd1^i	122.7 (2)	C72—C82—C92	119.9 (14)
O15^ii—Gd1—Gd1^i	113.2 (2)	C72—C82—H82	120.0
O45—Gd1—Gd1^i	84.49 (15)	C92—C82—H82	120.0
N11—Gd1—Gd1^i	143.4 (2)	C82—C92—C102	117.7 (14)
N21—Gd1—Gd1^i	135.1 (3)	C82—C92—H92	121.2
O35—Gd1—Gd1^i	35.05 (14)	C102—C92—H92	121.2
C15^ii—Gd1—Gd1^i	118.32 (19)	N22—C102—C92	123.8 (13)
O34—Gd2—O44^iii	131.3 (3)	N22—C102—H102	118.1
O34—Gd2—O33^iv	74.6 (3)	C92—C102—H102	118.1
O44^iii—Gd2—O33^iv	75.5 (3)	C13—O13—Gd2	94.2 (5)
O34—Gd2—O23	84.7 (3)	C13—O23—Gd2	96.0 (5)
O44^iii—Gd2—O23	129.5 (3)	C43—O33—Gd2^iv	163.3 (6)
O33^iv—Gd2—O23	84.8 (3)	C43—O33—Gd2^v	92.6 (5)
O34—Gd2—O13	131.4 (3)	Gd2^iv—O33—Gd2^v	103.7 (3)
O44^iii—Gd2—O13	76.6 (3)	C43—O43—Gd2^v	100.7 (5)
O33^iv—Gd2—O13	77.4 (3)	O23—C13—O13	114.3 (7)
O23—Gd2—O13	53.7 (2)	O23—C13—C23	122.4 (7)
O34—Gd2—O43^ii	87.5 (3)	O13—C13—C23	121.4 (7)
O44^iii—Gd2—O43^ii	80.5 (3)	O23—C13—Gd2	57.2 (4)
O33^iv—Gd2—O43^ii	126.6 (2)	O13—C13—Gd2	58.6 (5)
O23—Gd2—O43^ii	144.0 (3)	C23—C13—Gd2	178.3 (7)
O13—Gd2—O43^ii	140.8 (3)	C53—C23—C13	120.4 (8)
O34—Gd2—N22	140.4 (3)	C53—C23—C33	128.7 (8)
O44^iii—Gd2—N22	79.8 (3)	C13—C23—C33	110.9 (6)
O33^iv—Gd2—N22	144.4 (3)	C23—C33—C43	116.0 (7)
O23—Gd2—N22	91.6 (3)	C23—C33—H33A	108.3
O13—Gd2—N22	72.1 (3)	C43—C33—H33A	108.3
O43^ii—Gd2—N22	72.8 (3)	C23—C33—H33B	108.3
O34—Gd2—N12	77.8 (3)	C43—C33—H33B	108.3
O44^iii—Gd2—N12	137.3 (3)	H33A—C33—H33B	107.4
O33^iv—Gd2—N12	147.0 (3)	O33—C43—O43	113.2 (7)
O23—Gd2—N12	74.8 (3)	O33—C43—C33	121.7 (7)
O13—Gd2—N12	108.9 (3)	O43—C43—C33	120.8 (7)
O43^ii—Gd2—N12	69.2 (3)	O33—C43—Gd2^v	61.6 (4)
N22—Gd2—N12	63.2 (3)	O43—C43—Gd2^v	53.8 (4)
O34—Gd2—O33^ii	66.2 (3)	C33—C43—Gd2^v	172.7 (7)
O44^iii—Gd2—O33^ii	69.9 (3)	C23—C53—H53A	120.0
O33^iv—Gd2—O33^ii	76.3 (3)	C23—C53—H53B	120.0
O23—Gd2—O33^ii	148.5 (3)	H53A—C53—H53B	120.0
O13—Gd2—O33^ii	141.5 (3)	C14—O14—Gd1^i	143.5 (6)
O43^ii—Gd2—O33^ii	50.62 (19)	C14—O24—Gd1	144.6 (7)
N22—Gd2—O33^ii	118.4 (3)	C44—O34—Gd2	150.7 (7)
N12—Gd2—O33^ii	108.6 (3)	C44—O44—Gd2^iii	136.2 (6)
O34—Gd2—C13	106.6 (3)	O24—C14—O14	113.9 (8)
O44^iii—Gd2—C13	102.6 (3)	O24—C14—C24	121.5 (9)
O33^iv—Gd2—C13	76.4 (3)	O14—C14—C24	121.7 (9)
O23—Gd2—C13	26.87 (19)	C14—C24—C34	110.1 (10)
O13—Gd2—C13	27.27 (19)	C14—C24—H24A	109.6
O43^ii—Gd2—C13	156.2 (3)	C34—C24—H24A	109.6
N22—Gd2—C13	84.5 (3)	C14—C24—H24B	109.6
N12—Gd2—C13	94.7 (4)	C34—C24—H24B	109.6
O33^ii—Gd2—C13	152.7 (3)	H24A—C24—H24B	108.1
O34—Gd2—C43^ii	71.8 (3)	C54—C34—C44	125.0 (12)
O44^iii—Gd2—C43^ii	77.9 (3)	C54—C34—C24	119.7 (11)
O33^iv—Gd2—C43^ii	102.0 (2)	C44—C34—C24	115.4 (8)
O23—Gd2—C43^ii	152.5 (3)	O44—C44—O34	113.8 (8)
O13—Gd2—C43^ii	153.7 (3)	O44—C44—C34	119.5 (7)
O43^ii—Gd2—C43^ii	25.57 (18)	O34—C44—C34	123.8 (8)
N22—Gd2—C43^ii	97.4 (3)	C34—C54—H54A	120.0
N12—Gd2—C43^ii	86.1 (3)	C34—C54—H54B	120.0
O33^ii—Gd2—C43^ii	25.73 (17)	H54A—C54—H54B	120.0
C13—Gd2—C43^ii	178.1 (3)	C15—O15—Gd1^v	92.9 (5)
O34—Gd2—Gd2^iii	64.5 (2)	C15—O25—Gd1^v	96.0 (5)
O44^iii—Gd2—Gd2^iii	67.6 (2)	C45—O35—Gd1^i	159.1 (6)
O33^iv—Gd2—Gd2^iii	41.13 (19)	C45—O35—Gd1	96.5 (5)
O23—Gd2—Gd2^iii	121.5 (2)	Gd1^i—O35—Gd1	103.3 (3)
O13—Gd2—Gd2^iii	113.6 (2)	C45—O45—Gd1	105.0 (5)
O43^ii—Gd2—Gd2^iii	85.65 (15)	O25—C15—O15	115.4 (7)
N22—Gd2—Gd2^iii	143.5 (2)	O25—C15—C25	122.1 (6)
N12—Gd2—Gd2^iii	135.5 (3)	O15—C15—C25	121.7 (7)
O33^ii—Gd2—Gd2^iii	35.19 (14)	O25—C15—Gd1^v	56.9 (4)
C13—Gd2—Gd2^iii	117.5 (2)	O15—C15—Gd1^v	59.7 (4)
C43^ii—Gd2—Gd2^iii	60.89 (15)	C25—C15—Gd1^v	177.7 (6)
C51—N11—C11	120.9 (12)	C55—C25—C35	126.5 (9)
C51—N11—Gd1	121.6 (9)	C55—C25—C15	122.5 (8)
C11—N11—Gd1	117.5 (8)	C35—C25—C15	111.0 (6)
C61—N21—C101	117.8 (13)	C45—C35—C25	118.8 (8)
C61—N21—Gd1	121.4 (9)	C45—C35—H35A	107.6
C101—N21—Gd1	120.8 (9)	C25—C35—H35A	107.6
N11—C11—C21	121.2 (14)	C45—C35—H35B	107.6
N11—C11—H11	119.4	C25—C35—H35B	107.6
C21—C11—H11	119.4	H35A—C35—H35B	107.0
C31—C21—C11	118.4 (16)	O35—C45—O45	105.5 (7)
C31—C21—H21	120.8	O35—C45—C35	124.6 (7)
C11—C21—H21	120.8	O45—C45—C35	121.5 (7)
C21—C31—C41	119.1 (15)	C25—C55—H55A	120.0
C21—C31—H31	120.5	C25—C55—H55B	120.0
C41—C31—H31	120.5	H55A—C55—H55B	120.0

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

(II) Poly[diaqua(2,2'-bipyridine)di-µ₃-itaconato-µ₂-itaconato- digadolinium(III)]

Crystal data

[Gd2(C5H4O4)3(C10H8N2)(H2O)2]	F(000) = 1712
Mr = 890.96	Dx = 2.085 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8794 reflections
a = 16.427 (5) Å	θ = 1.9–26.9°
b = 18.645 (5) Å	µ = 4.71 mm^−1
c = 9.300 (3) Å	T = 293 K
β = 94.949 (6)°	Plate, colourless
V = 2837.7 (14) Å^3	0.30 × 0.25 × 0.10 mm
Z = 4

Data collection

Bruker SMART? CCD area-detector diffractometer	3098 independent reflections
Radiation source: fine-focus sealed tube	2689 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.105
ϕ and ω scans	θmax = 27.8°, θmin = 1.7°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −21→21
Tmin = 0.25, Tmax = 0.62	k = −23→23
9298 measured reflections	l = −12→12

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0517P)^2 + 103.4472P] where P = (Fo^2 + 2Fc^2)/3
3098 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 1.83 e Å^−3
150 restraints	Δρmin = −4.17 e Å^−3

Special details

Experimental. Data collected from twinned crystals

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	Occ. (<1)
Gd1	0.5000	0.21882 (4)	0.2500	0.0331 (2)
Gd2	0.5000	0.43946 (3)	0.2500	0.01846 (19)
N11	0.5779 (8)	0.1029 (6)	0.3113 (13)	0.050 (3)
C11	0.6484 (11)	0.1063 (8)	0.3928 (17)	0.060 (4)
H11	0.6760	0.1498	0.4030	0.073*
C21	0.6816 (13)	0.0458 (11)	0.463 (2)	0.080 (5)
H21	0.7330	0.0470	0.5135	0.097*
C31	0.6368 (13)	−0.0141 (11)	0.455 (2)	0.085 (6)
H31	0.6532	−0.0528	0.5140	0.102*
C41	0.5691 (13)	−0.0201 (10)	0.366 (2)	0.078 (5)
H41	0.5432	−0.0642	0.3529	0.093*
C51	0.5372 (8)	0.0409 (7)	0.2915 (15)	0.045 (3)
O12	0.5749 (5)	0.4617 (4)	−0.1544 (8)	0.0327 (17)
O22	0.5910 (5)	0.4710 (4)	0.0827 (7)	0.0267 (15)
O32	0.5644 (5)	0.3314 (4)	0.1796 (9)	0.0360 (18)
O42	0.6508 (6)	0.2446 (5)	0.2084 (11)	0.054 (3)
C12	0.6088 (6)	0.4432 (5)	−0.0358 (11)	0.024 (2)
C22	0.6712 (7)	0.3861 (6)	−0.0265 (13)	0.032 (2)
C32	0.6989 (8)	0.3539 (7)	0.1154 (14)	0.041 (3)
H32A	0.7127	0.3921	0.1842	0.050*
H32B	0.7480	0.3261	0.1056	0.050*
C42	0.6355 (7)	0.3063 (6)	0.1735 (12)	0.033 (2)
C52	0.7024 (10)	0.3670 (8)	−0.1438 (17)	0.059 (4)
H52A	0.6854	0.3892	−0.2308	0.071*
H52B	0.7419	0.3312	−0.1410	0.071*
O13	0.5309 (7)	0.1816 (5)	0.0072 (10)	0.060 (3)
O23	0.4288 (6)	0.2548 (4)	0.0199 (9)	0.041 (2)
C13	0.4747 (8)	0.2186 (6)	−0.0533 (12)	0.038 (3)
C23	0.4674 (8)	0.2241 (6)	−0.2172 (14)	0.044 (3)
C53	0.4022 (18)	0.2275 (15)	−0.269 (3)	0.053 (7)	0.50
H53A	0.3925	0.2307	−0.3688	0.064*	0.50
H53B	0.3586	0.2271	−0.2115	0.064*	0.50
O1W	0.5856 (5)	0.3969 (4)	0.4555 (8)	0.0347 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Gd1	0.0624 (6)	0.0188 (4)	0.0203 (4)	0.000	0.0161 (3)	0.000
Gd2	0.0240 (4)	0.0180 (3)	0.0136 (3)	0.000	0.0024 (2)	0.000
N11	0.071 (7)	0.035 (5)	0.047 (6)	0.006 (5)	0.026 (5)	0.005 (4)
C11	0.078 (8)	0.050 (7)	0.055 (7)	0.006 (6)	0.016 (6)	0.007 (6)
C21	0.084 (9)	0.086 (9)	0.073 (9)	0.018 (7)	0.014 (7)	0.017 (7)
C31	0.095 (9)	0.079 (9)	0.084 (9)	0.000 (8)	0.019 (8)	0.025 (7)
C41	0.089 (9)	0.064 (8)	0.084 (9)	0.001 (7)	0.029 (7)	−0.001 (7)
C51	0.052 (5)	0.038 (4)	0.046 (5)	0.010 (4)	0.014 (4)	0.002 (4)
O12	0.047 (4)	0.035 (4)	0.018 (3)	0.012 (3)	0.013 (3)	0.000 (3)
O22	0.040 (4)	0.025 (3)	0.017 (3)	0.002 (3)	0.011 (3)	−0.004 (3)
O32	0.045 (4)	0.027 (3)	0.038 (4)	0.005 (3)	0.013 (3)	0.011 (3)
O42	0.065 (6)	0.037 (4)	0.065 (6)	0.021 (4)	0.024 (5)	0.019 (4)
C12	0.031 (5)	0.021 (4)	0.022 (4)	0.000 (4)	0.006 (4)	0.007 (4)
C22	0.032 (5)	0.033 (5)	0.035 (5)	0.005 (4)	0.017 (4)	0.010 (4)
C32	0.042 (6)	0.039 (5)	0.043 (6)	0.001 (5)	0.004 (5)	0.014 (5)
C42	0.044 (6)	0.027 (5)	0.029 (5)	0.009 (4)	0.013 (4)	0.002 (4)
C52	0.069 (7)	0.054 (7)	0.055 (7)	0.022 (6)	0.013 (6)	0.006 (6)
O13	0.089 (6)	0.055 (5)	0.037 (5)	0.032 (5)	0.018 (4)	0.006 (4)
O23	0.061 (5)	0.032 (4)	0.030 (4)	0.010 (4)	0.012 (4)	−0.011 (3)
C13	0.062 (7)	0.032 (5)	0.024 (5)	−0.001 (5)	0.016 (5)	−0.001 (4)
C23	0.053 (5)	0.037 (4)	0.039 (4)	0.021 (4)	−0.010 (4)	−0.005 (3)
C53	0.050 (10)	0.064 (11)	0.050 (10)	−0.013 (8)	0.025 (8)	−0.003 (8)
O1W	0.054 (5)	0.030 (4)	0.019 (3)	0.000 (3)	−0.003 (3)	−0.001 (3)

Geometric parameters (Å, º)

Gd1—O23^i	2.443 (9)	C31—C41	1.33 (3)
Gd1—O23	2.443 (9)	C31—H31	0.9300
Gd1—O13	2.456 (9)	C41—C51	1.41 (2)
Gd1—O13^i	2.456 (9)	C41—H41	0.9300
Gd1—O32^i	2.464 (7)	C51—C51^i	1.39 (3)
Gd1—O32	2.464 (7)	O12—C12	1.241 (13)
Gd1—N11^i	2.551 (11)	O12—Gd2^ii	2.348 (8)
Gd1—N11	2.551 (11)	O22—C12	1.275 (12)
Gd1—O42^i	2.585 (10)	O32—C42	1.264 (13)
Gd1—O42	2.585 (10)	O42—C42	1.216 (13)
Gd1—Gd2	4.1139 (15)	C12—C22	1.476 (14)
Gd2—O22^i	2.324 (7)	C22—C52	1.294 (18)
Gd2—O22	2.324 (7)	C22—C32	1.485 (16)
Gd2—O12^ii	2.348 (8)	C32—C42	1.504 (16)
Gd2—O12^iii	2.348 (8)	C32—H32A	0.9700
Gd2—O32^i	2.394 (8)	C32—H32B	0.9700
Gd2—O32	2.394 (8)	C52—H52A	0.9300
Gd2—O1W^i	2.407 (8)	C52—H52B	0.9300
Gd2—O1W	2.407 (8)	O13—C13	1.248 (16)
N11—C51	1.339 (17)	O23—C13	1.254 (14)
N11—C11	1.33 (2)	C13—C23	1.522 (17)
C11—C21	1.39 (2)	C23—C53	1.14 (3)
C11—H11	0.9300	C23—C23^iv	1.28 (3)
C21—C31	1.34 (3)	C53—H53A	0.9300
C21—H21	0.9300	C53—H53B	0.9300
O23^i—Gd1—O23	148.2 (4)	O22—Gd2—O32	72.9 (2)
O23^i—Gd1—O13	139.6 (3)	O12^ii—Gd2—O32	141.9 (3)
O23—Gd1—O13	52.7 (3)	O12^iii—Gd2—O32	122.3 (3)
O23^i—Gd1—O13^i	52.7 (3)	O32^i—Gd2—O32	65.3 (4)
O23—Gd1—O13^i	139.6 (3)	O22^i—Gd2—O1W^i	104.4 (3)
O13—Gd1—O13^i	147.2 (5)	O22—Gd2—O1W^i	85.3 (3)
O23^i—Gd1—O32^i	73.6 (3)	O12^ii—Gd2—O1W^i	73.0 (3)
O23—Gd1—O32^i	79.3 (3)	O12^iii—Gd2—O1W^i	144.1 (3)
O13—Gd1—O32^i	127.8 (3)	O32^i—Gd2—O1W^i	72.4 (3)
O13^i—Gd1—O32^i	82.5 (3)	O32—Gd2—O1W^i	75.4 (3)
O23^i—Gd1—O32	79.3 (3)	O22^i—Gd2—O1W	85.3 (3)
O23—Gd1—O32	73.6 (3)	O22—Gd2—O1W	104.4 (3)
O13—Gd1—O32	82.5 (3)	O12^ii—Gd2—O1W	144.1 (3)
O13^i—Gd1—O32	127.8 (3)	O12^iii—Gd2—O1W	73.0 (3)
O32^i—Gd1—O32	63.2 (4)	O32^i—Gd2—O1W	75.4 (3)
O23^i—Gd1—N11^i	128.4 (3)	O32—Gd2—O1W	72.4 (3)
O23—Gd1—N11^i	81.0 (4)	O1W^i—Gd2—O1W	141.5 (4)
O13—Gd1—N11^i	72.2 (4)	C51—N11—C11	121.3 (13)
O13^i—Gd1—N11^i	80.0 (3)	C51—N11—Gd1	117.7 (9)
O32^i—Gd1—N11^i	124.2 (3)	C11—N11—Gd1	118.8 (10)
O32—Gd1—N11^i	151.7 (3)	N11—C11—C21	121.0 (17)
O23^i—Gd1—N11	81.0 (4)	N11—C11—H11	119.5
O23—Gd1—N11	128.4 (3)	C21—C11—H11	119.5
O13—Gd1—N11	80.0 (3)	C31—C21—C11	117 (2)
O13^i—Gd1—N11	72.2 (4)	C31—C21—H21	121.3
O32^i—Gd1—N11	151.7 (3)	C11—C21—H21	121.3
O32—Gd1—N11	124.2 (3)	C21—C31—C41	122 (2)
N11^i—Gd1—N11	64.1 (6)	C21—C31—H31	119.0
O23^i—Gd1—O42^i	102.2 (3)	C41—C31—H31	119.0
O23—Gd1—O42^i	71.8 (3)	C31—C41—C51	119.6 (18)
O13—Gd1—O42^i	117.8 (4)	C31—C41—H41	120.2
O13^i—Gd1—O42^i	68.8 (4)	C51—C41—H41	120.2
O32^i—Gd1—O42^i	50.4 (3)	N11—C51—C51^i	118.8 (8)
O32—Gd1—O42^i	108.7 (3)	N11—C51—C41	117.9 (14)
N11^i—Gd1—O42^i	73.9 (3)	C51^i—C51—C41	123.1 (11)
N11—Gd1—O42^i	126.3 (3)	C12—O12—Gd2^ii	137.3 (7)
O23^i—Gd1—O42	71.8 (3)	C12—O22—Gd2	133.2 (6)
O23—Gd1—O42	102.2 (3)	C42—O32—Gd2	139.1 (8)
O13—Gd1—O42	68.8 (4)	C42—O32—Gd1	96.7 (6)
O13^i—Gd1—O42	117.8 (4)	Gd2—O32—Gd1	115.7 (3)
O32^i—Gd1—O42	108.7 (3)	C42—O42—Gd1	92.1 (7)
O32—Gd1—O42	50.4 (3)	O12—C12—O22	122.5 (9)
N11^i—Gd1—O42	126.3 (3)	O12—C12—C22	120.6 (10)
N11—Gd1—O42	73.9 (3)	O22—C12—C22	117.0 (9)
O42^i—Gd1—O42	158.6 (4)	C52—C22—C12	118.2 (12)
O23^i—Gd1—C13	153.7 (3)	C52—C22—C32	121.7 (12)
O23—Gd1—C13	26.4 (3)	C12—C22—C32	120.1 (10)
O13—Gd1—C13	26.3 (3)	C22—C32—C42	112.9 (11)
O13^i—Gd1—C13	153.6 (3)	C22—C32—H32A	109.0
O32^i—Gd1—C13	103.7 (3)	C42—C32—H32A	109.0
O32—Gd1—C13	76.4 (3)	C22—C32—H32B	109.0
N11^i—Gd1—C13	75.3 (4)	C42—C32—H32B	109.0
N11—Gd1—C13	104.5 (4)	H32A—C32—H32B	107.8
O42^i—Gd1—C13	95.1 (4)	O42—C42—O32	120.5 (11)
O42—Gd1—C13	84.9 (4)	O42—C42—C32	121.4 (11)
O23^i—Gd1—C13^i	26.4 (3)	O32—C42—C32	118.0 (10)
O23—Gd1—C13^i	153.7 (3)	O42—C42—Gd1	63.1 (7)
O13—Gd1—C13^i	153.6 (3)	O32—C42—Gd1	57.6 (6)
O13^i—Gd1—C13^i	26.3 (3)	C32—C42—Gd1	172.3 (9)
O32^i—Gd1—C13^i	76.4 (3)	C22—C52—H52A	120.0
O32—Gd1—C13^i	103.7 (3)	C22—C52—H52B	120.0
N11^i—Gd1—C13^i	104.5 (4)	H52A—C52—H52B	120.0
N11—Gd1—C13^i	75.3 (4)	C13—O13—Gd1	93.1 (7)
O42^i—Gd1—C13^i	84.9 (4)	C13—O23—Gd1	93.6 (8)
O42—Gd1—C13^i	95.1 (4)	O13—C13—O23	120.6 (11)
C13—Gd1—C13^i	179.8 (5)	O13—C13—C23	118.7 (10)
O22^i—Gd2—O22	150.7 (3)	O23—C13—C23	120.5 (11)
O22^i—Gd2—O12^ii	73.0 (2)	O13—C13—Gd1	60.6 (6)
O22—Gd2—O12^ii	83.9 (3)	O23—C13—Gd1	60.0 (6)
O22^i—Gd2—O12^iii	83.9 (3)	C23—C13—Gd1	174.4 (9)
O22—Gd2—O12^iii	73.0 (2)	C53—C23—C23^iv	127 (2)
O12^ii—Gd2—O12^iii	76.6 (4)	C53—C23—C13	114.6 (19)
O22^i—Gd2—O32^i	72.9 (2)	C23^iv—C23—C13	118.8 (15)
O22—Gd2—O32^i	136.2 (2)	C23—C53—H53A	120.0
O12^ii—Gd2—O32^i	122.3 (3)	C23—C53—H53B	120.0
O12^iii—Gd2—O32^i	141.9 (3)	H53A—C53—H53B	120.0
O22^i—Gd2—O32	136.2 (2)

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

(III) poly[[bis(2,2'-bipyridine)-µ₄-itaconato-di-µ₃-itaconato-diholmium(III)] dihydrate]

Crystal data

[Ho2(C5H4O4)3(C10H8N2)2]·2H2O	F(000) = 2064
Mr = 1062.51	Dx = 1.804 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8672 reflections
a = 25.023 (5) Å	θ = 2.0–25.0°
b = 9.3994 (19) Å	µ = 4.09 mm^−1
c = 18.229 (4) Å	T = 293 K
β = 114.13 (3)°	Plate, colourless
V = 3912.8 (17) Å^3	0.30 × 0.25 × 0.15 mm
Z = 4

Data collection

Bruker SMART? CCD area-detector diffractometer	4299 independent reflections
Radiation source: fine-focus sealed tube	3770 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ϕ and ω scans	θmax = 27.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −31→29
Tmin = 0.28, Tmax = 0.54	k = −12→12
15034 measured reflections	l = −22→23

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.223	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.159P)^2 + 95.0201P] where P = (Fo^2 + 2Fc^2)/3
4299 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 10.21 e Å^−3
34 restraints	Δρmin = −3.30 e Å^−3

Special details

Experimental. Data collected from twinned crystals

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	Occ. (<1)
Ho1	0.923904 (18)	0.39931 (4)	0.44997 (3)	0.0243 (2)
N11	0.8197 (5)	0.4134 (11)	0.4471 (8)	0.046 (3)
N21	0.8370 (4)	0.3439 (11)	0.3155 (6)	0.042 (2)
C11	0.8112 (7)	0.450 (2)	0.5125 (11)	0.065 (4)
H11	0.8439	0.4766	0.5579	0.078*
C21	0.7579 (8)	0.451 (2)	0.5179 (14)	0.080 (5)
H21	0.7550	0.4755	0.5655	0.096*
C31	0.7078 (9)	0.4135 (18)	0.4483 (15)	0.074 (6)
H31	0.6704	0.4151	0.4474	0.089*
C41	0.7170 (7)	0.3764 (19)	0.3853 (17)	0.083 (7)
H41	0.6849	0.3504	0.3390	0.100*
C51	0.7726 (6)	0.3735 (14)	0.3832 (12)	0.059 (4)
C61	0.7827 (5)	0.3348 (13)	0.3107 (8)	0.046 (3)
C71	0.7382 (6)	0.278 (2)	0.2383 (12)	0.074 (5)
H71	0.7002	0.2665	0.2347	0.089*
C81	0.7503 (8)	0.241 (2)	0.1768 (11)	0.078 (5)
H81	0.7212	0.2046	0.1303	0.093*
C91	0.8068 (8)	0.258 (2)	0.1818 (10)	0.072 (5)
H91	0.8166	0.2346	0.1394	0.087*
C101	0.8480 (6)	0.3128 (18)	0.2537 (9)	0.060 (4)
H101	0.8858	0.3279	0.2577	0.072*
O1W	0.9281 (14)	0.187 (5)	0.6855 (17)	0.116 (12)	0.50
O2W	0.9471 (15)	0.061 (3)	0.2613 (15)	0.091 (10)	0.50
O12	0.9308 (4)	0.1558 (9)	0.4104 (5)	0.0410 (19)
O22	0.9112 (4)	0.1850 (9)	0.5152 (6)	0.051 (2)
C12	0.9207 (5)	0.1060 (9)	0.4671 (7)	0.036 (3)
C22	0.9219 (5)	−0.0519 (10)	0.4768 (6)	0.036 (2)
C32	0.9283 (5)	−0.1368 (11)	0.4133 (6)	0.035 (2)
H32A	0.9642	−0.1091	0.4089	0.042*
H32B	0.8960	−0.1152	0.3625	0.042*
C42	0.9296 (4)	−0.2944 (12)	0.4274 (6)	0.031 (2)
C52	0.9191 (8)	−0.1104 (13)	0.5413 (9)	0.063 (4)
H52A	0.9213	−0.2087	0.5476	0.075*
H52B	0.9151	−0.0531	0.5804	0.075*
O32	0.9784 (3)	−0.3555 (8)	0.4715 (4)	0.0313 (15)
O42	0.8837 (4)	−0.3705 (8)	0.3958 (6)	0.0416 (19)
O13	0.9683 (3)	0.4257 (8)	0.3623 (5)	0.0361 (17)
O23	1.0590 (3)	0.5139 (9)	0.4245 (4)	0.0381 (17)
C13	1.0154 (4)	0.4730 (12)	0.3633 (6)	0.038 (2)
C23	1.0256 (4)	0.476 (2)	0.2882 (5)	0.088 (6)
C53	1.0794 (5)	0.478 (3)	0.2917 (13)	0.18 (2)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ho1	0.0277 (3)	0.0171 (3)	0.0260 (3)	−0.00029 (14)	0.0088 (2)	−0.00045 (14)
N11	0.034 (5)	0.039 (6)	0.069 (8)	0.008 (4)	0.025 (5)	0.011 (5)
N21	0.034 (5)	0.039 (6)	0.042 (5)	−0.013 (4)	0.005 (4)	−0.018 (4)
C11	0.047 (8)	0.081 (11)	0.081 (11)	−0.002 (8)	0.040 (8)	−0.010 (9)
C21	0.074 (11)	0.081 (12)	0.102 (15)	0.009 (10)	0.054 (12)	0.005 (12)
C31	0.065 (11)	0.061 (10)	0.114 (17)	0.026 (8)	0.055 (12)	0.031 (10)
C41	0.038 (8)	0.061 (10)	0.14 (2)	−0.005 (7)	0.023 (10)	0.024 (12)
C51	0.042 (7)	0.027 (6)	0.108 (13)	0.008 (5)	0.032 (8)	0.019 (7)
C61	0.039 (6)	0.028 (6)	0.052 (7)	−0.004 (5)	0.000 (5)	−0.001 (5)
C71	0.039 (7)	0.072 (12)	0.083 (12)	−0.014 (7)	−0.004 (8)	0.000 (9)
C81	0.063 (10)	0.089 (13)	0.061 (10)	−0.004 (9)	0.004 (8)	−0.008 (9)
C91	0.075 (10)	0.081 (12)	0.046 (8)	−0.026 (9)	0.010 (8)	−0.024 (8)
C101	0.044 (7)	0.072 (10)	0.053 (8)	−0.016 (7)	0.008 (6)	−0.013 (7)
O1W	0.11 (2)	0.17 (4)	0.062 (16)	−0.06 (2)	0.030 (16)	−0.01 (2)
O2W	0.17 (3)	0.069 (14)	0.067 (15)	0.063 (18)	0.085 (19)	0.031 (13)
O12	0.054 (5)	0.024 (4)	0.042 (5)	0.004 (4)	0.018 (4)	−0.002 (3)
O22	0.063 (5)	0.023 (4)	0.085 (7)	0.007 (4)	0.048 (5)	0.004 (4)
C12	0.033 (6)	0.022 (6)	0.051 (7)	0.001 (4)	0.015 (5)	−0.005 (4)
C22	0.032 (5)	0.020 (5)	0.049 (6)	−0.004 (4)	0.010 (5)	−0.010 (5)
C32	0.046 (6)	0.011 (4)	0.039 (6)	0.009 (4)	0.009 (5)	0.006 (4)
C42	0.030 (5)	0.029 (5)	0.029 (5)	−0.002 (4)	0.006 (4)	0.004 (4)
C52	0.093 (12)	0.038 (8)	0.073 (11)	0.007 (7)	0.050 (10)	0.006 (6)
O32	0.032 (4)	0.028 (4)	0.028 (3)	0.009 (3)	0.005 (3)	0.010 (3)
O42	0.039 (4)	0.020 (4)	0.052 (5)	−0.003 (3)	0.005 (4)	0.000 (3)
O13	0.037 (4)	0.036 (4)	0.032 (4)	−0.004 (3)	0.011 (3)	−0.008 (3)
O23	0.036 (4)	0.049 (5)	0.030 (4)	−0.007 (4)	0.015 (3)	−0.009 (3)
C13	0.042 (6)	0.044 (7)	0.029 (5)	0.002 (5)	0.014 (5)	0.001 (5)
C23	0.052 (8)	0.18 (2)	0.028 (6)	−0.014 (11)	0.015 (6)	0.000 (10)
C53	0.071 (17)	0.42 (7)	0.06 (2)	−0.05 (4)	0.034 (18)	0.01 (4)

Geometric parameters (Å, º)

Ho1—O23^i	2.298 (7)	C71—C81	1.32 (3)
Ho1—O13	2.303 (8)	C71—H71	0.9300
Ho1—O32^ii	2.310 (7)	C81—C91	1.39 (3)
Ho1—O42^iii	2.421 (8)	C81—H81	0.9300
Ho1—O22	2.425 (9)	C91—C101	1.392 (19)
Ho1—O12	2.427 (8)	C91—H91	0.9300
Ho1—N21	2.579 (9)	C101—H101	0.9300
Ho1—N11	2.590 (10)	O12—C12	1.251 (11)
Ho1—O32^iii	2.624 (8)	O22—C12	1.244 (11)
Ho1—Ho1^i	3.967 (2)	C12—C22	1.494 (12)
N11—C11	1.34 (2)	C22—C52	1.325 (15)
N11—C51	1.33 (2)	C22—C32	1.468 (14)
N21—C101	1.298 (19)	C32—C42	1.501 (15)
N21—C61	1.327 (16)	C32—H32A	0.9700
C11—C21	1.38 (2)	C32—H32B	0.9700
C11—H11	0.9300	C42—O42	1.274 (13)
C21—C31	1.42 (3)	C42—O32	1.289 (12)
C21—H21	0.9300	C52—H52A	0.9300
C31—C41	1.31 (3)	C52—H52B	0.9300
C31—H31	0.9300	O13—C13	1.253 (10)
C41—C51	1.41 (2)	O23—C13	1.261 (10)
C41—H41	0.9300	C13—C23	1.491 (12)
C51—C61	1.49 (2)	C23—C53	1.320 (9)
C61—C71	1.44 (2)	C23—C23^iv	1.458 (15)
O23^i—Ho1—O13	134.9 (3)	C51—C41—H41	118.0
O23^i—Ho1—O32^ii	74.2 (3)	N11—C51—C41	120.3 (19)
O13—Ho1—O32^ii	76.2 (3)	N11—C51—C61	115.8 (12)
O23^i—Ho1—O42^iii	88.0 (3)	C41—C51—C61	123.8 (18)
O13—Ho1—O42^iii	81.9 (3)	N21—C61—C71	118.2 (14)
O32^ii—Ho1—O42^iii	124.8 (3)	N21—C61—C51	117.8 (11)
O23^i—Ho1—O12	128.6 (3)	C71—C61—C51	123.8 (14)
O13—Ho1—O12	77.4 (3)	C81—C71—C61	121.0 (16)
O32^ii—Ho1—O12	80.2 (3)	C81—C71—H71	119.5
O42^iii—Ho1—O12	142.2 (3)	C61—C71—H71	119.5
O23^i—Ho1—O22	79.3 (3)	C71—C81—C91	119.7 (17)
O13—Ho1—O22	128.8 (3)	C71—C81—H81	120.1
O32^ii—Ho1—O22	82.3 (3)	C91—C81—H81	120.1
O42^iii—Ho1—O22	145.8 (3)	C81—C91—C101	116.5 (16)
O12—Ho1—O22	53.3 (3)	C81—C91—H91	121.7
O23^i—Ho1—N21	139.4 (3)	C101—C91—H91	121.7
O13—Ho1—N21	79.7 (3)	N21—C101—C91	124.2 (14)
O32^ii—Ho1—N21	145.2 (3)	N21—C101—H101	117.9
O42^iii—Ho1—N21	75.2 (3)	C91—C101—H101	117.9
O12—Ho1—N21	70.2 (3)	C12—O12—Ho1	92.5 (6)
O22—Ho1—N21	94.0 (4)	C12—O22—Ho1	92.8 (6)
O23^i—Ho1—N11	77.2 (4)	O22—C12—O12	121.4 (9)
O13—Ho1—N11	138.4 (4)	O22—C12—C22	120.6 (9)
O32^ii—Ho1—N11	145.4 (3)	O12—C12—C22	118.0 (9)
O42^iii—Ho1—N11	72.5 (3)	O22—C12—Ho1	60.7 (5)
O12—Ho1—N11	103.6 (3)	C52—C22—C32	122.4 (10)
O22—Ho1—N11	73.7 (3)	C52—C22—C12	120.8 (10)
N21—Ho1—N11	62.6 (4)	C32—C22—C12	116.7 (9)
O23^i—Ho1—O32^iii	70.5 (3)	C22—C32—C42	113.8 (9)
O13—Ho1—O32^iii	68.9 (3)	C22—C32—H32A	108.8
O32^ii—Ho1—O32^iii	73.2 (3)	C42—C32—H32A	108.8
O42^iii—Ho1—O32^iii	51.7 (3)	C22—C32—H32B	108.8
O12—Ho1—O32^iii	141.0 (3)	C42—C32—H32B	108.8
O22—Ho1—O32^iii	145.1 (3)	H32A—C32—H32B	107.7
N21—Ho1—O32^iii	120.3 (3)	O42—C42—O32	118.7 (10)
N11—Ho1—O32^iii	114.5 (3)	O42—C42—C32	121.5 (9)
C11—N11—C51	116.4 (13)	O32—C42—C32	119.7 (9)
C11—N11—Ho1	121.4 (10)	C22—C52—H52A	120.0
C51—N11—Ho1	121.9 (10)	C22—C52—H52B	120.0
C101—N21—C61	120.2 (11)	H52A—C52—H52B	120.0
C101—N21—Ho1	118.3 (8)	C42—O32—Ho1^ii	163.3 (7)
C61—N21—Ho1	121.2 (9)	C42—O32—Ho1^v	89.8 (6)
N11—C11—C21	125.3 (17)	Ho1^ii—O32—Ho1^v	106.8 (3)
N11—C11—H11	117.4	C42—O42—Ho1^v	99.7 (7)
C21—C11—H11	117.4	C13—O13—Ho1	138.3 (7)
C11—C21—C31	117.6 (18)	C13—O23—Ho1^i	137.0 (6)
C11—C21—H21	121.2	O13—C13—O23	126.1 (9)
C31—C21—H21	121.2	O13—C13—C23	120.4 (9)
C41—C31—C21	116.3 (17)	O23—C13—C23	113.4 (8)
C41—C31—H31	121.9	C53—C23—C23^iv	121.8 (13)
C21—C31—H31	121.9	C53—C23—C13	120.6 (12)
C31—C41—C51	124 (2)	C23^iv—C23—C13	117.6 (12)
C31—C41—H41	118.0

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