In the title Schiff base binuclear lanthanum(III) complex, the two metal ions have the same environment and the LaIII ion is coordinated by three soft nitrogen atoms from the Schiff base ligand, four hard oxygen atoms from carboxylate co-ligands and two water oxygen atoms. Each LaIII ion is nine coordinate and its environment is best described as a tricapped trigonal–prismatic geometry.
Keywords: lanthanum; crystal structure; 2-hydrazinopyridine,hydrazone
Abstract
In the binuclear title complex, [La2(C2H3O2)4(C11H10N4)(H2O)4](NO3)2·0.5H2O, the two lanthanum ions are nine coordinate in a distorted trigonal–prismatic geometry. Each LaIII ion is bonded to three N atoms of the Schiff base, 1-(pyridin-2-yl)-2-(pyridin-2-ylmethylene)hydrazine and is coordinated by one acetate group, which acts in η2-bidentate mode and two acetate groups that act in μ2-mode between the two LaIII ions. Two η1-water molecules complete the coordination sphere. All bond lengths in the coordination environment of the LaIII ion are slightly larger than those observed in the isostructural NdIII and SmIII complexes. The LaIII⋯LaIII distance is 4.6696 (6) Å. In the crystal, extensive O—H⋯O hydrogen-bonding interactions involving the coordinated water molecules and the non-coordinating nitrate anions, as well as the oxygen atoms of the acetate groups, generate an overall three-dimensional supramolecular network.
1. Chemical context
Lanthanide–Schiff base complexes are widely used in applied and fundamental sciences. Chemists continue to pay much attention in the preparation of functional Schiff bases and their lanthanide complexes, which can be used in many fields such as catalysis (Bell et al., 2022 ▸), radiopharmaceuticals (Hu & Wilson, 2022 ▸), fluoroimmuno assay reagents (Wu et al., 2024 ▸; Dong et al., 2023 ▸), diagnostic tools in biology (Liu et al., 2020 ▸; Zapolotsky et al., 2022 ▸), and in laser development (Lapaev et al., 2019 ▸). The use of acyclic Schiff bases allows the introduction of two identical or different metal ions (Geng et al., 2022 ▸; Bryleva et al., 2023 ▸). The presence of multiple coordination sites and the versatile coordination modes provide several possible structures with lanthanide ions (Le Fur et al., 2018 ▸; Kariaka et al., 2019 ▸). Organic ligands that are used as precursors for the structural design of complexes can have hard and/or soft sites such as oxygen, nitrogen or sulfur atoms. Through proper design, the molecular structure of the ligand can be controlled to have suitable sites to coordinate metal ions to generate specific architectures. The introduction of co-ligands offers multiple possibilities to develop original structures. Carboxylate groups are versatile co-ligands, which can adopt various coordination modes, to generate different structures with the same ligand (Grebenyuk et al., 2021 ▸; Wang et al., 2012 ▸). However, lanthanides can have high and variable coordination numbers, depending on the synthesis conditions of the complexes. Indeed, the synthesis of these compounds is considerably influenced by the reaction procedures and conditions such as the nature of the solvent, pH, temperature and/or reaction time (Sinchow et al., 2019 ▸). This provides a versatility in coordination geometries that makes it difficult to predict the structures and properties of lanthanide compounds. In this context, for the synthesis of lanthanide(III) complexes, the Schiff base 1-(pyridin-2-ylmethylidene)-2-(pyridin-2-yl)hydrazine (HL), which provides three soft donor N atoms from two pyridine rings and an azomethine unit, was used in the presence of acetate anions as co-ligands, which provide hard donor O atoms. Several complexes from the ligand HL have been reported by our group (Gueye, Dieng et al., 2017 ▸; Ndiaye-Gueye, Dieng, Thiam, Sow et al., 2017 ▸; Sarr et al., 2018 ▸). In all of these complexes, the acetate group is either bidentate chelating η2-OOCH3, bridging μ2-OOCH3 or bidentate bridging η2:μ2-OOCH3. This report presents the synthesis, characterization, and X-ray structure of a lanthanum (III) complex derived from 1-(pyrydin-2yl)-2-(pyridine-2-ylmethylene)hydrazine (HL) and an acetate group as co-ligand.
2. Structural commentary
A mixture of the ligand HL [1-(pyridin-2-yl)-2-(pyridin-2-ylmethylene)hydrazine], lanthanum nitrate, and acetate salts in a 1:1:3 ratio yields the title compound, which crystallographic studies reveal to be a dicationic binuclear complex with a 1:1:2 stoichiometric ratio. The crystal structure exhibits disorder involving both the ligand and the nitrate group. The site occupancy factors (SOFs) for the two disordered parts of the ligand refine to 0.547 (9) and 0.453 (9). For the nitrate group, the SOFs refine to 0.826 (9) and 0.174 (9). The following analysis of the crystal structure focuses on the major disorder components. The structure of the lanthanum acetato-bridged complex is built from two identical entities {La(HL)(η2-OOCH3)(η1-HO2)2} bridged by two acetate anions acting in μ2-OOCH3 mode, yielding a binuclear dianionic complex containing two uncoordinated nitrate anions and a partial occupancy non-coordinating water molecule (Figs. 1 ▸ and 2 ▸). Each LaIII ion is coordinated by one HL ligand coordinated through two 2-pyridyl nitrogen atoms and one azomethine nitrogen atom. The coordination of the Schiff base forms two five-membered rings (LaNCNN) and (LaNCCN) with bite angles of 59.99 (9) and 59.43 (10)°, respectively, in the major disorder component. Additionally, each LaIII ion is coordinated by one chelating-bidentate acetate group acting in η2-OOCH3 mode and two chelating-monodentate water molecules acting in η1-HO2 mode. Thus, the LaIII ions are nine coordinate and their environments are best described as a strongly distorted tricapped trigonal–prismatic geometry. The atoms N4/N3/O5 and O2/O3/O4 define the slanted base faces of the trigonal–tricapped environment. These two planes are twisted and form a dihedral angle of 57.37 (2)°. The three caps are occupied by O1, N1 and N2 atoms. The lanthanum cation is situated 1.320 (4) Å out of the plane defined by the caps O1, N1 and N2 of the polyhedron. The La—N distances (Table 1 ▸) are slightly longer than those found for the analogous complex of the NdIII ion with the same ligand [2.675 (3), 2.637 (2) and 2.639 (2) Å] (Ndiaye-Gueye, Dieng, Thiam, Sow et al., 2017 ▸; Ndiaye-Gueye, Dieng, Thiam, Lo et al., 2017 ▸; Gueye, Dieng et al., 2017 ▸; Gueye, et al. 2021 ▸). The La—O distances s fall in the range reported for other carboxylate complexes (Gueye, Moussa et al., 2017 ▸; Bag et al., 2013 ▸; Chen et al., 2014 ▸). The distances for La—OH2 are comparable to the values in the complex [{Ln(HL(η2-OOCH3)2(η1-H2O)2}{μ2-OOCH3)2}{Ln(HL)(η2-OOCH3)2}(η1-H2O)2]·2NO3, (where Ln = Nd or Sm) (Ndiaye-Gueye, Dieng, Thiam, Lo, et al., 2017 ▸). The LaIII⋯LaIII distance is 4.6696 (6) Å and the value of the bridging angle O3— La1—O10 is 109.21 (5)°. The C6—N3 distance of 1.289 (7) Å is consistent with double-bond character. The bond lengths in the chain C—CH=N—NH—C bridging two pyridine rings are [1.443 (6) Å for PyC—C, 1.289 (7) Å for CH=N, 1.346 (6) Å for N—N and 1.377 (6) Å C—CPy] and are significantly different from the corresponding mean values for this ligand found in the CSD [1.450 (17), 1.283 (15), 1.349 (12) and 1.376 (16) Å, respectively].
Figure 1.
A view of the title compound, showing the atom-numbering scheme for the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
Figure 2.
The nature of disorder of the ligand and nitrate anion.
Table 1. Selected bond lengths (Å).
| La1—O1 | 2.5659 (14) | La1—O10 | 2.4814 (14) |
| La1—O2 | 2.5395 (15) | La1—N1 | 2.626 (8) |
| La1—O3 | 2.5184 (16) | La1—N3 | 2.683 (7) |
| La1—O4 | 2.5653 (15) | La1—N4 | 2.768 (6) |
| La1—O5 | 2.6073 (16) |
3. Supramolecular features
The title complex [{La(HL)(η2-OOCH3)(η1-H2O)2}{(μ2-OOCH3)2}{La(HL)(η2-OOCH3)(η1-H2O)2}]·2NO3·0.5(H2O) features both coordinated and solvent water molecules. The unbound solvent water is present at partial occupancy. An intramolecular hydrogen bond is formed between the OH group of a coordinated water molecule, acting as donor, and an oxygen atom (O7) of a free nitrate group, acting as acceptor (O1—H1B⋯O7). In addition, intermolecular hydrogen bonds involving the OH groups of coordinated water molecules are significant in the construction of the structure. These OH groups act as donors to the nitrate oxygen atoms of free nitrate groups (O1—H1A⋯O8i and O2—H2B⋯O7i; symmetry codes as in Table 1 ▸) and to oxygen atoms of bidentate chelating acetate groups (O2—H2A⋯O4ii). The NH group of the hydrazine moiety interacts with an oxygen atom of a bidentate chelating acetate group, further consolidating the structure through the hydrogen bond N2—H2⋯O5iii. Weak intermolecular C—H⋯O hydrogen bonds are also observed between CH groups and oxygen atoms of the bidentate chelating acetate groups, as summarized in Table 1 ▸. These hydrogen bonds collectively connect the molecules of the complex into a three-dimensional network (Table 2 ▸, Fig. 3 ▸).
Table 2. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H1A⋯O6 | 0.76 (1) | 2.27 (2) | 2.994 (3) | 158 (3) |
| O1—H1A⋯O7 | 0.76 (1) | 2.59 (2) | 3.273 (6) | 151 (2) |
| O1—H1A⋯O6′ | 0.76 (1) | 2.19 (2) | 2.901 (14) | 154 (2) |
| O1—H1B⋯O8i | 0.76 (1) | 2.03 (2) | 2.793 (4) | 176 (3) |
| O1—H1B⋯O8′i | 0.76 (1) | 1.97 (3) | 2.73 (2) | 171 (3) |
| O2—H2A⋯O4ii | 0.76 (1) | 1.95 (2) | 2.6971 (19) | 168 (3) |
| O2—H2B⋯O7i | 0.76 (1) | 2.03 (2) | 2.786 (4) | 171 (3) |
| O2—H2B⋯N5′i | 0.76 (1) | 2.68 (2) | 3.419 (16) | 164 (3) |
| O2—H2B⋯O7′i | 0.76 (1) | 1.79 (3) | 2.54 (2) | 167 (3) |
| C13—H13A⋯O7iii | 0.96 | 2.53 | 3.483 (5) | 170 |
| C13—H13A⋯O7′iii | 0.96 | 2.33 | 3.27 (3) | 167 |
| C13—H13C⋯O7iv | 0.96 | 2.65 | 3.544 (6) | 155 |
| C15—H15A⋯O9 | 0.96 | 2.62 | 3.350 (10) | 133 |
| C2—H2⋯O6v | 0.93 | 2.57 | 3.420 (6) | 153 |
| N2—H2C⋯O5iv | 0.86 | 2.13 | 2.898 (7) | 149 |
| C11—H11⋯O9 | 0.93 | 2.57 | 3.150 (10) | 121 |
| N2′—H2′A⋯O5iv | 0.86 | 2.30 | 3.028 (7) | 142 |
| C6′—H6′⋯O5iv | 0.93 | 2.32 | 3.067 (9) | 138 |
| C10′—H10′⋯O6′v | 0.93 | 2.34 | 3.260 (18) | 170 |
| O9—H9A⋯O6vi | 0.76 (2) | 2.66 (14) | 3.062 (9) | 115 (13) |
| O9—H9B⋯O8vi | 0.76 (2) | 2.57 (10) | 3.241 (11) | 147 (16) |
Symmetry codes: (i)
; (ii)
; (iii)
; (iv)
; (v)
; (vi)
.
Figure 3.
A partial packing plot showing diperiodic sheets that extend parallel to the bc plane.
4. Database survey
A search of the Cambridge Structural Database (CSD version 5.44, updates of September 2023; Groom et al., 2016 ▸) indicated 27 compounds incorporating the ligand 1-(pyridin-2-ylmethylidene)-2-(pyridin-2-yl)hydrazine, which has been widely used in coordination chemistry. Seven examples of complexes of the above ligand with f-block metal ions are known from the literature: BEHFUS and TESXOH (Gueye, Dieng et al., 2017 ▸), PCPHYB (Baraniak et al., 1976 ▸), TIKDAV and TIKCUO (Ndiaye-Gueye, Dieng, Thiam, Lo, et al., 2017 ▸), ZEFJOM (Gueye, Moussa et al., 2017 ▸), GIJYAD (Ndiaye-Gueye et al., 2022 ▸). Three structures are available for the Ca2+ metal ion: NIWLEM, NIWLIQ and NIWLOW (Vantomme, Hafezi et al., 2014 ▸). One Co2+ (PAPCOC10; Gerloch, 1966 ▸) and two Mn2+ [PEQMAC (Sarr et al., 2018 ▸), SIZPID01 (Diop et al., 2019 ▸)] structures are reported in the CSD. Nine entries for Cu2+ are found: DIMLEQ10 and DIMLIU01 (Rojo et al., 1988 ▸), JAWRII (Mesa et al., 1988 ▸), SAHDOU (Mesa et al., 1989 ▸), REJMEY and REJMIC (Ainscough et al., 1996 ▸), QUJTIZ (Chowdhury et al., 2009 ▸) TUSWEK (Mukherjee et al., 2010 ▸), FAFZOF (U-wang et al., 2020 ▸). Five Zn2+ structures: GECWAP and GECWIX (Vantomme, Jiang et al., 2014 ▸), SAVQAI and SAVQEM (Dumitru et al., 2005 ▸), SIZPOJ01 (Diop et al., 2019 ▸) are also reported in the CSD.
5. Synthesis and crystallization
A mixture of 2-hydrazinopyridine (1 mmol) and 2-pyridinecarbaldehyde (1 mmol) in ethanol (15 mL) was stirred under reflux for 30 min. A mixture of sodium acetate (3 mmol) and La(NO3)3·6H2O (1 mmol) in ethanol (10 mL) was added to the solution. The mixture was stirred for 30 min and the resulting yellow solution was filtered and the filtrate was kept at 298 K. A yellow powder appeared after one day and was collected by filtration. Recrystallization by slow evaporation of an ethanol solution gave X-ray quality crystals of the compound [C30H40LaN8O12]·2NO3·0.5H2O. Yield 65%. Analysis calculated C, 32.30; H, 3.70; N, 12.56. Found: C, 32.27; H, 3.73; N, 12.52. %.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. Hydrogen atoms were found in difference-Fourier maps, but subsequently included in the refinement using riding models, with constrained distances set to 0.93 Å (Csp2—H), 0.96 Å (RCH3) and 0.86 Å (Nsp2—H). Water hydrogen atoms were refined using 1,2 and 1,3 distance restraints. Uiso(H) parameters were set to values of either 1.2Ueq or 1.5Ueq (RCH3 and H2O only) of the attached atom. To ensure satisfactory refinement for disordered groups in the structure, a combination of constraints and restraints was employed. Constraints (SHELXL command EADP) were used to fix Uij of overlapping fragments. Restraints were used to ensure the integrity of ill-defined or disordered groups (SHELXL commands SAME, DFIX, CHIV, SIMU, and RIGU).
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | [La2(C2H3O2)4(C11H10N4)(H2O)4](NO3)2·0.5H2O |
| M r | 1115.55 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 11.1170 (11), 17.8366 (19), 11.8094 (12) |
| β (°) | 114.213 (3) |
| V (Å3) | 2135.7 (4) |
| Z | 2 |
| Radiation type | Mo Kα |
| μ (mm−1) | 2.06 |
| Crystal size (mm) | 0.2 × 0.2 × 0.1 |
| Data collection | |
| Diffractometer | Bruker X8 |
| Absorption correction | Numerical (SADABS; Krause et al., 2015 ▸) |
| Tmin, Tmax | 0.215, 0.424 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 72063, 10392, 7368 |
| R int | 0.084 |
| (sin θ/λ)max (Å−1) | 0.836 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.064, 1.04 |
| No. of reflections | 10392 |
| No. of parameters | 451 |
| No. of restraints | 781 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 1.26, −0.95 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989024012349/pk2715sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989024012349/pk2715Isup2.hkl
CCDC reference: 2412041
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
We thank the PMD2X X-ray diffraction facility of the CRM2 laboratory, Université de Lorraine, for the X-ray diffraction measurements, data processing and analysis, and providing of reports for publication: https://crm2.univ-lorraine.fr/plateformes/pmd2x.
supplementary crystallographic information
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Crystal data
| [La2(C2H3O2)4(C11H10N4)(H2O)4](NO3)2·0.5H2O | F(000) = 1106 |
| Mr = 1115.55 | Dx = 1.735 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 11.1170 (11) Å | Cell parameters from 21184 reflections |
| b = 17.8366 (19) Å | θ = 2.7–29.4° |
| c = 11.8094 (12) Å | µ = 2.06 mm−1 |
| β = 114.213 (3)° | T = 293 K |
| V = 2135.7 (4) Å3 | Block, metallic yellowish yellow |
| Z = 2 | 0.2 × 0.2 × 0.1 mm |
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Data collection
| Bruker X8 diffractometer | 7368 reflections with I > 2σ(I) |
| Detector resolution: 10 pixels mm-1 | Rint = 0.084 |
| Single crystals were positioned at 35, 40, 35, and 28 mm from the detector scans | θmax = 36.4°, θmin = 2.2° |
| Absorption correction: numerical (SADABS; Krause et al., 2015) | h = −16→18 |
| Tmin = 0.215, Tmax = 0.424 | k = −29→29 |
| 72063 measured reflections | l = −19→19 |
| 10392 independent reflections |
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Refinement
| Refinement on F2 | Hydrogen site location: mixed |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0112P)2 + 1.5461P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.064 | (Δ/σ)max = 0.003 |
| S = 1.04 | Δρmax = 1.26 e Å−3 |
| 10392 reflections | Δρmin = −0.94 e Å−3 |
| 451 parameters | Extinction correction: SHELXL (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 781 restraints | Extinction coefficient: 0.00071 (13) |
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| La1 | 0.56737 (2) | 0.95905 (2) | 0.20467 (2) | 0.01520 (3) | |
| O1 | 0.71353 (15) | 0.84746 (8) | 0.31638 (13) | 0.0207 (3) | |
| H1A | 0.737 (2) | 0.8335 (14) | 0.3831 (15) | 0.031* | |
| H1B | 0.753 (2) | 0.8249 (13) | 0.289 (2) | 0.031* | |
| O2 | 0.52181 (16) | 0.84992 (8) | 0.05463 (13) | 0.0247 (3) | |
| H2A | 0.490 (2) | 0.8580 (14) | −0.0147 (14) | 0.037* | |
| H2B | 0.574 (2) | 0.8205 (13) | 0.062 (2) | 0.037* | |
| O3 | 0.77181 (16) | 0.96048 (9) | 0.16251 (13) | 0.0295 (3) | |
| O4 | 0.57600 (14) | 1.10181 (8) | 0.18261 (12) | 0.0218 (3) | |
| O5 | 0.46089 (19) | 1.06485 (10) | 0.28544 (14) | 0.0360 (4) | |
| C12 | 0.5029 (2) | 1.11655 (12) | 0.23852 (17) | 0.0263 (5) | |
| C13 | 0.4664 (3) | 1.19661 (14) | 0.2475 (2) | 0.0449 (7) | |
| H13A | 0.431738 | 1.218889 | 0.166320 | 0.067* | |
| H13B | 0.543322 | 1.223772 | 0.300997 | 0.067* | |
| H13C | 0.400921 | 1.198418 | 0.280778 | 0.067* | |
| O10 | 0.37451 (14) | 0.99521 (9) | 0.01294 (13) | 0.0248 (3) | |
| C14 | 0.2633 (2) | 1.02384 (12) | −0.05024 (18) | 0.0207 (4) | |
| C15 | 0.1712 (3) | 1.04094 (18) | 0.0093 (2) | 0.0452 (7) | |
| H15A | 0.104232 | 1.002998 | −0.012831 | 0.068* | |
| H15B | 0.130825 | 1.088904 | −0.018859 | 0.068* | |
| H15C | 0.219407 | 1.041944 | 0.097847 | 0.068* | |
| N1 | 0.7389 (8) | 1.0127 (6) | 0.4165 (8) | 0.0154 (11) | 0.547 (8) |
| C1 | 0.8351 (10) | 1.0594 (7) | 0.4194 (8) | 0.0221 (14) | 0.547 (8) |
| H1 | 0.837759 | 1.072530 | 0.344276 | 0.026* | 0.547 (8) |
| C2 | 0.9305 (7) | 1.0891 (5) | 0.5271 (6) | 0.0234 (12) | 0.547 (8) |
| H2 | 0.993945 | 1.122342 | 0.524696 | 0.028* | 0.547 (8) |
| C3 | 0.9276 (6) | 1.0672 (4) | 0.6394 (5) | 0.0228 (10) | 0.547 (8) |
| H3 | 0.990764 | 1.085119 | 0.714130 | 0.027* | 0.547 (8) |
| C4 | 0.8317 (6) | 1.0194 (3) | 0.6390 (5) | 0.0207 (10) | 0.547 (8) |
| H4 | 0.828457 | 1.004507 | 0.713141 | 0.025* | 0.547 (8) |
| C5 | 0.7388 (6) | 0.9932 (4) | 0.5261 (5) | 0.0123 (9) | 0.547 (8) |
| N2 | 0.6401 (5) | 0.9460 (4) | 0.5246 (6) | 0.0156 (10) | 0.547 (8) |
| H2C | 0.637201 | 0.932701 | 0.593393 | 0.019* | 0.547 (8) |
| N3 | 0.5482 (6) | 0.9206 (4) | 0.4163 (6) | 0.0154 (10) | 0.547 (8) |
| C6 | 0.4571 (7) | 0.8775 (4) | 0.4207 (6) | 0.0175 (10) | 0.547 (8) |
| H6 | 0.455719 | 0.865341 | 0.496698 | 0.021* | 0.547 (8) |
| C7 | 0.3572 (5) | 0.8483 (3) | 0.3071 (5) | 0.0192 (9) | 0.547 (8) |
| C8 | 0.2639 (6) | 0.7974 (3) | 0.3128 (6) | 0.0279 (11) | 0.547 (8) |
| H8 | 0.266593 | 0.781473 | 0.388808 | 0.034* | 0.547 (8) |
| C9 | 0.1675 (5) | 0.7714 (3) | 0.2022 (7) | 0.0344 (13) | 0.547 (8) |
| H9 | 0.104301 | 0.737475 | 0.202871 | 0.041* | 0.547 (8) |
| C10 | 0.1663 (5) | 0.7966 (3) | 0.0905 (6) | 0.0344 (12) | 0.547 (8) |
| H10 | 0.101955 | 0.780214 | 0.015203 | 0.041* | 0.547 (8) |
| C11 | 0.2632 (6) | 0.8466 (4) | 0.0937 (6) | 0.0273 (12) | 0.547 (8) |
| H11 | 0.262204 | 0.863073 | 0.018597 | 0.033* | 0.547 (8) |
| N4 | 0.3581 (6) | 0.8727 (3) | 0.1988 (5) | 0.0187 (9) | 0.547 (8) |
| N1' | 0.3780 (8) | 0.8785 (5) | 0.2388 (6) | 0.0239 (13) | 0.453 (8) |
| C1' | 0.2781 (9) | 0.8502 (5) | 0.1387 (7) | 0.0324 (15) | 0.453 (8) |
| H1' | 0.271747 | 0.863508 | 0.060346 | 0.039* | 0.453 (8) |
| C2' | 0.1839 (8) | 0.8019 (5) | 0.1470 (8) | 0.0418 (16) | 0.453 (8) |
| H2' | 0.113781 | 0.784576 | 0.076477 | 0.050* | 0.453 (8) |
| C3' | 0.1993 (8) | 0.7806 (4) | 0.2654 (9) | 0.0414 (16) | 0.453 (8) |
| H3' | 0.140352 | 0.746774 | 0.274681 | 0.050* | 0.453 (8) |
| C4' | 0.2991 (7) | 0.8087 (4) | 0.3674 (8) | 0.0328 (14) | 0.453 (8) |
| H4' | 0.308199 | 0.795176 | 0.446545 | 0.039* | 0.453 (8) |
| C5' | 0.3880 (7) | 0.8582 (4) | 0.3514 (7) | 0.0202 (11) | 0.453 (8) |
| N2' | 0.4887 (7) | 0.8877 (4) | 0.4527 (6) | 0.0202 (12) | 0.453 (8) |
| H2'A | 0.493246 | 0.878841 | 0.525905 | 0.024* | 0.453 (8) |
| N3' | 0.5807 (7) | 0.9306 (5) | 0.4385 (7) | 0.0145 (12) | 0.453 (8) |
| C6' | 0.6765 (8) | 0.9552 (6) | 0.5382 (8) | 0.0174 (13) | 0.453 (8) |
| H6' | 0.680870 | 0.941845 | 0.615935 | 0.021* | 0.453 (8) |
| C7' | 0.7762 (7) | 1.0032 (5) | 0.5286 (7) | 0.0178 (13) | 0.453 (8) |
| C8' | 0.8745 (7) | 1.0334 (4) | 0.6364 (6) | 0.0236 (13) | 0.453 (8) |
| H8' | 0.879996 | 1.020580 | 0.714666 | 0.028* | 0.453 (8) |
| C9' | 0.9619 (8) | 1.0821 (4) | 0.6225 (7) | 0.0286 (14) | 0.453 (8) |
| H9' | 1.027339 | 1.103938 | 0.691992 | 0.034* | 0.453 (8) |
| C10' | 0.9537 (9) | 1.0992 (6) | 0.5056 (8) | 0.0290 (16) | 0.453 (8) |
| H10' | 1.013469 | 1.131946 | 0.495294 | 0.035* | 0.453 (8) |
| C11' | 0.8542 (12) | 1.0663 (8) | 0.4037 (10) | 0.0228 (17) | 0.453 (8) |
| H11' | 0.848158 | 1.078181 | 0.324895 | 0.027* | 0.453 (8) |
| N4' | 0.7676 (9) | 1.0191 (7) | 0.4134 (9) | 0.0162 (14) | 0.453 (8) |
| N5 | 0.8120 (3) | 0.7717 (2) | 0.6227 (3) | 0.0278 (7) | 0.826 (9) |
| O6 | 0.8757 (3) | 0.8140 (3) | 0.5847 (4) | 0.0629 (13) | 0.826 (9) |
| O7 | 0.6941 (4) | 0.7636 (2) | 0.5548 (5) | 0.0405 (8) | 0.826 (9) |
| O8 | 0.8623 (4) | 0.7415 (2) | 0.7271 (3) | 0.0445 (10) | 0.826 (9) |
| N5' | 0.8000 (16) | 0.7501 (9) | 0.5993 (15) | 0.0278 (7) | 0.174 (9) |
| O6' | 0.8688 (15) | 0.7717 (12) | 0.5480 (17) | 0.0629 (13) | 0.174 (9) |
| O7' | 0.6816 (18) | 0.7484 (13) | 0.543 (3) | 0.0405 (8) | 0.174 (9) |
| O8' | 0.854 (2) | 0.7191 (12) | 0.7010 (16) | 0.0445 (10) | 0.174 (9) |
| O9 | 0.0421 (9) | 0.8898 (6) | −0.1673 (8) | 0.062 (3) | 0.25 |
| H9A | 0.016 (14) | 0.907 (8) | −0.232 (6) | 0.093* | 0.25 |
| H9B | −0.010 (11) | 0.861 (7) | −0.170 (13) | 0.093* | 0.25 |
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| La1 | 0.01924 (6) | 0.01380 (5) | 0.01228 (5) | 0.00382 (5) | 0.00618 (4) | 0.00176 (4) |
| O1 | 0.0285 (8) | 0.0184 (7) | 0.0151 (6) | 0.0072 (6) | 0.0089 (6) | 0.0030 (5) |
| O2 | 0.0375 (9) | 0.0191 (7) | 0.0136 (6) | 0.0035 (6) | 0.0064 (6) | 0.0031 (5) |
| O3 | 0.0304 (8) | 0.0409 (9) | 0.0196 (7) | 0.0064 (7) | 0.0127 (6) | 0.0083 (7) |
| O4 | 0.0318 (8) | 0.0186 (7) | 0.0125 (6) | 0.0045 (6) | 0.0064 (6) | 0.0011 (5) |
| O5 | 0.0626 (12) | 0.0311 (9) | 0.0273 (8) | 0.0265 (8) | 0.0317 (8) | 0.0145 (7) |
| C12 | 0.0427 (13) | 0.0244 (11) | 0.0113 (8) | 0.0151 (10) | 0.0105 (8) | 0.0025 (7) |
| C13 | 0.083 (2) | 0.0246 (13) | 0.0345 (13) | 0.0207 (13) | 0.0311 (14) | 0.0021 (10) |
| O10 | 0.0201 (7) | 0.0258 (8) | 0.0238 (7) | 0.0059 (6) | 0.0043 (6) | 0.0010 (6) |
| C14 | 0.0190 (9) | 0.0258 (11) | 0.0193 (9) | 0.0010 (8) | 0.0098 (8) | 0.0030 (7) |
| C15 | 0.0315 (13) | 0.078 (2) | 0.0347 (13) | 0.0181 (14) | 0.0220 (11) | 0.0165 (14) |
| N1 | 0.015 (3) | 0.019 (2) | 0.0153 (16) | −0.002 (2) | 0.0085 (18) | −0.0007 (13) |
| C1 | 0.025 (3) | 0.027 (3) | 0.018 (2) | −0.004 (2) | 0.0123 (18) | 0.0013 (18) |
| C2 | 0.022 (3) | 0.023 (3) | 0.026 (2) | −0.0031 (18) | 0.0110 (18) | −0.0020 (18) |
| C3 | 0.018 (3) | 0.026 (3) | 0.0196 (19) | −0.0020 (19) | 0.0038 (17) | −0.0042 (18) |
| C4 | 0.019 (2) | 0.025 (2) | 0.0144 (16) | −0.0004 (18) | 0.0029 (17) | −0.0022 (15) |
| C5 | 0.011 (2) | 0.015 (2) | 0.0098 (14) | 0.0023 (17) | 0.0035 (17) | −0.0005 (13) |
| N2 | 0.017 (2) | 0.019 (2) | 0.012 (2) | −0.0026 (18) | 0.0074 (19) | 0.0022 (15) |
| N3 | 0.016 (3) | 0.014 (2) | 0.015 (2) | 0.0019 (17) | 0.0041 (18) | −0.0014 (15) |
| C6 | 0.020 (3) | 0.018 (2) | 0.017 (3) | −0.0020 (19) | 0.010 (2) | 0.0026 (19) |
| C7 | 0.017 (2) | 0.0185 (19) | 0.022 (2) | −0.0021 (15) | 0.0081 (18) | −0.0042 (17) |
| C8 | 0.027 (3) | 0.026 (2) | 0.033 (3) | −0.0114 (19) | 0.014 (2) | −0.003 (2) |
| C9 | 0.025 (2) | 0.035 (3) | 0.043 (3) | −0.0134 (19) | 0.013 (2) | −0.006 (2) |
| C10 | 0.025 (2) | 0.034 (2) | 0.039 (3) | −0.0091 (18) | 0.008 (2) | −0.006 (2) |
| C11 | 0.021 (2) | 0.030 (2) | 0.023 (2) | −0.0069 (17) | 0.001 (2) | −0.003 (2) |
| N4 | 0.019 (2) | 0.0191 (19) | 0.017 (2) | −0.0019 (15) | 0.0071 (19) | −0.0002 (19) |
| N1' | 0.027 (3) | 0.024 (2) | 0.019 (3) | 0.003 (2) | 0.008 (2) | −0.003 (2) |
| C1' | 0.031 (3) | 0.039 (3) | 0.025 (3) | −0.003 (2) | 0.009 (3) | −0.002 (3) |
| C2' | 0.035 (3) | 0.046 (4) | 0.038 (3) | −0.010 (3) | 0.009 (3) | −0.006 (3) |
| C3' | 0.035 (4) | 0.041 (4) | 0.046 (4) | −0.013 (3) | 0.015 (3) | −0.003 (3) |
| C4' | 0.030 (3) | 0.032 (3) | 0.038 (3) | −0.006 (2) | 0.015 (3) | −0.001 (3) |
| C5' | 0.021 (3) | 0.020 (2) | 0.022 (3) | 0.0015 (19) | 0.011 (2) | 0.000 (2) |
| N2' | 0.020 (3) | 0.025 (3) | 0.016 (3) | −0.002 (2) | 0.007 (2) | 0.000 (2) |
| N3' | 0.015 (3) | 0.016 (3) | 0.012 (3) | 0.001 (2) | 0.005 (2) | 0.0004 (19) |
| C6' | 0.018 (3) | 0.023 (3) | 0.0060 (19) | 0.002 (2) | −0.001 (2) | −0.0032 (19) |
| C7' | 0.013 (3) | 0.017 (3) | 0.020 (2) | 0.002 (2) | 0.004 (2) | −0.0022 (17) |
| C8' | 0.018 (3) | 0.030 (3) | 0.0148 (19) | −0.005 (2) | −0.002 (2) | −0.005 (2) |
| C9' | 0.022 (3) | 0.025 (3) | 0.030 (3) | −0.004 (2) | 0.002 (2) | −0.006 (2) |
| C10' | 0.026 (3) | 0.023 (3) | 0.033 (3) | −0.002 (2) | 0.007 (2) | −0.002 (2) |
| C11' | 0.021 (3) | 0.021 (3) | 0.026 (3) | −0.003 (2) | 0.010 (2) | −0.001 (2) |
| N4' | 0.014 (3) | 0.018 (3) | 0.015 (2) | 0.004 (2) | 0.005 (2) | −0.0002 (17) |
| N5 | 0.0304 (12) | 0.0219 (16) | 0.0343 (15) | 0.0066 (12) | 0.0165 (12) | 0.0098 (12) |
| O6 | 0.0440 (13) | 0.064 (3) | 0.090 (2) | 0.0082 (16) | 0.0369 (15) | 0.050 (2) |
| O7 | 0.0407 (14) | 0.025 (2) | 0.0347 (14) | −0.0131 (11) | −0.0054 (11) | 0.0036 (14) |
| O8 | 0.0282 (11) | 0.059 (3) | 0.0363 (16) | −0.0100 (16) | 0.0031 (13) | 0.0233 (15) |
| N5' | 0.0304 (12) | 0.0219 (16) | 0.0343 (15) | 0.0066 (12) | 0.0165 (12) | 0.0098 (12) |
| O6' | 0.0440 (13) | 0.064 (3) | 0.090 (2) | 0.0082 (16) | 0.0369 (15) | 0.050 (2) |
| O7' | 0.0407 (14) | 0.025 (2) | 0.0347 (14) | −0.0131 (11) | −0.0054 (11) | 0.0036 (14) |
| O8' | 0.0282 (11) | 0.059 (3) | 0.0363 (16) | −0.0100 (16) | 0.0031 (13) | 0.0233 (15) |
| O9 | 0.047 (5) | 0.069 (7) | 0.047 (5) | 0.007 (5) | −0.004 (4) | −0.017 (4) |
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Geometric parameters (Å, º)
| La1—O1 | 2.5659 (14) | C7—C8 | 1.400 (7) |
| La1—O2 | 2.5395 (15) | C7—N4 | 1.355 (6) |
| La1—O3 | 2.5184 (16) | C8—H8 | 0.9300 |
| La1—O4 | 2.5653 (15) | C8—C9 | 1.386 (6) |
| La1—O5 | 2.6073 (16) | C9—H9 | 0.9300 |
| La1—O10 | 2.4814 (14) | C9—C10 | 1.388 (7) |
| La1—N1 | 2.626 (8) | C10—H10 | 0.9300 |
| La1—N3 | 2.683 (7) | C10—C11 | 1.388 (7) |
| La1—N4 | 2.768 (6) | C11—H11 | 0.9300 |
| La1—N1' | 2.712 (8) | C11—N4 | 1.339 (6) |
| La1—N3' | 2.752 (8) | N1'—C1' | 1.345 (8) |
| La1—N4' | 2.771 (9) | N1'—C5' | 1.338 (7) |
| O1—H1A | 0.763 (14) | C1'—H1' | 0.9300 |
| O1—H1B | 0.760 (14) | C1'—C2' | 1.389 (10) |
| O2—H2A | 0.761 (14) | C2'—H2' | 0.9300 |
| O2—H2B | 0.761 (14) | C2'—C3' | 1.390 (9) |
| O3—C14i | 1.251 (2) | C3'—H3' | 0.9300 |
| O4—C12 | 1.267 (3) | C3'—C4' | 1.356 (8) |
| O5—C12 | 1.260 (3) | C4'—H4' | 0.9300 |
| C12—C13 | 1.500 (3) | C4'—C5' | 1.394 (8) |
| C13—H13A | 0.9600 | C5'—N2' | 1.365 (6) |
| C13—H13B | 0.9600 | N2'—H2'A | 0.8600 |
| C13—H13C | 0.9600 | N2'—N3' | 1.340 (8) |
| O10—C14 | 1.261 (2) | N3'—C6' | 1.298 (7) |
| C14—C15 | 1.491 (3) | C6'—H6' | 0.9300 |
| C15—H15A | 0.9600 | C6'—C7' | 1.441 (8) |
| C15—H15B | 0.9600 | C7'—C8' | 1.401 (8) |
| C15—H15C | 0.9600 | C7'—N4' | 1.355 (10) |
| N1—C1 | 1.345 (7) | C8'—H8' | 0.9300 |
| N1—C5 | 1.340 (8) | C8'—C9' | 1.363 (8) |
| C1—H1 | 0.9300 | C9'—H9' | 0.9300 |
| C1—C2 | 1.385 (9) | C9'—C10' | 1.379 (9) |
| C2—H2 | 0.9300 | C10'—H10' | 0.9300 |
| C2—C3 | 1.396 (7) | C10'—C11' | 1.386 (11) |
| C3—H3 | 0.9300 | C11'—H11' | 0.9300 |
| C3—C4 | 1.364 (6) | C11'—N4' | 1.319 (9) |
| C4—H4 | 0.9300 | N5—O6 | 1.238 (3) |
| C4—C5 | 1.390 (6) | N5—O7 | 1.233 (4) |
| C5—N2 | 1.377 (6) | N5—O8 | 1.248 (3) |
| N2—H2C | 0.8600 | N5'—O6' | 1.216 (14) |
| N2—N3 | 1.346 (6) | N5'—O7' | 1.208 (15) |
| N3—C6 | 1.289 (7) | N5'—O8' | 1.231 (15) |
| C6—H6 | 0.9300 | O9—H9A | 0.761 (16) |
| C6—C7 | 1.443 (6) | O9—H9B | 0.762 (16) |
| O1—La1—O5 | 131.31 (5) | N1—C1—C2 | 124.2 (6) |
| O1—La1—N1 | 74.6 (2) | C2—C1—H1 | 117.9 |
| O1—La1—N3 | 66.31 (17) | C1—C2—H2 | 121.4 |
| O1—La1—N4 | 85.96 (14) | C1—C2—C3 | 117.2 (5) |
| O1—La1—N1' | 83.07 (18) | C3—C2—H2 | 121.4 |
| O1—La1—N3' | 65.1 (2) | C2—C3—H3 | 120.2 |
| O1—La1—N4' | 74.6 (3) | C4—C3—C2 | 119.6 (5) |
| O2—La1—O1 | 70.56 (5) | C4—C3—H3 | 120.2 |
| O2—La1—O4 | 134.03 (4) | C3—C4—H4 | 120.5 |
| O2—La1—O5 | 145.03 (6) | C3—C4—C5 | 119.1 (5) |
| O2—La1—N1 | 143.4 (2) | C5—C4—H4 | 120.5 |
| O2—La1—N3 | 112.63 (15) | N1—C5—C4 | 123.0 (5) |
| O2—La1—N4 | 68.32 (13) | N1—C5—N2 | 117.5 (5) |
| O2—La1—N1' | 75.71 (16) | N2—C5—C4 | 119.5 (5) |
| O2—La1—N3' | 118.17 (18) | C5—N2—H2C | 119.7 |
| O2—La1—N4' | 140.7 (3) | N3—N2—C5 | 120.5 (5) |
| O3—La1—O1 | 71.15 (5) | N3—N2—H2C | 119.7 |
| O3—La1—O2 | 78.91 (6) | N2—N3—La1 | 118.6 (4) |
| O3—La1—O4 | 84.00 (5) | C6—N3—La1 | 123.6 (4) |
| O3—La1—O5 | 130.31 (6) | C6—N3—N2 | 117.8 (6) |
| O3—La1—N1 | 79.82 (16) | N3—C6—H6 | 120.1 |
| O3—La1—N3 | 127.56 (15) | N3—C6—C7 | 119.8 (5) |
| O3—La1—N4 | 144.90 (14) | C7—C6—H6 | 120.1 |
| O3—La1—N1' | 148.59 (18) | C8—C7—C6 | 119.5 (5) |
| O3—La1—N3' | 121.26 (17) | N4—C7—C6 | 117.4 (4) |
| O3—La1—N4' | 73.2 (2) | N4—C7—C8 | 123.1 (4) |
| O4—La1—O1 | 141.26 (5) | C7—C8—H8 | 120.9 |
| O4—La1—O5 | 50.23 (5) | C9—C8—C7 | 118.2 (5) |
| O4—La1—N1 | 72.1 (2) | C9—C8—H8 | 120.9 |
| O4—La1—N3 | 111.64 (16) | C8—C9—H9 | 120.3 |
| O4—La1—N4 | 128.03 (14) | C8—C9—C10 | 119.4 (5) |
| O4—La1—N1' | 127.18 (18) | C10—C9—H9 | 120.3 |
| O4—La1—N3' | 107.23 (19) | C9—C10—H10 | 120.8 |
| O4—La1—N4' | 69.9 (2) | C9—C10—C11 | 118.5 (5) |
| O5—La1—N1 | 69.4 (2) | C11—C10—H10 | 120.8 |
| O5—La1—N3 | 67.84 (17) | C10—C11—H11 | 118.1 |
| O5—La1—N4 | 84.78 (14) | N4—C11—C10 | 123.8 (5) |
| O5—La1—N1' | 80.33 (18) | N4—C11—H11 | 118.1 |
| O5—La1—N3' | 67.2 (2) | C7—N4—La1 | 119.1 (3) |
| O5—La1—N4' | 73.4 (2) | C11—N4—La1 | 123.4 (4) |
| O10—La1—O1 | 143.00 (5) | C11—N4—C7 | 117.1 (5) |
| O10—La1—O2 | 73.27 (5) | C1'—N1'—La1 | 118.7 (5) |
| O10—La1—O3 | 109.21 (5) | C5'—N1'—La1 | 122.6 (4) |
| O10—La1—O4 | 72.76 (5) | C5'—N1'—C1' | 118.2 (7) |
| O10—La1—O5 | 78.09 (5) | N1'—C1'—H1' | 118.5 |
| O10—La1—N1 | 142.4 (2) | N1'—C1'—C2' | 123.0 (7) |
| O10—La1—N3 | 123.20 (15) | C2'—C1'—H1' | 118.5 |
| O10—La1—N4 | 73.67 (12) | C1'—C2'—H2' | 121.5 |
| O10—La1—N1' | 80.82 (16) | C1'—C2'—C3' | 117.1 (6) |
| O10—La1—N3' | 129.37 (18) | C3'—C2'—H2' | 121.5 |
| O10—La1—N4' | 142.2 (3) | C2'—C3'—H3' | 119.6 |
| N1—La1—N3 | 60.63 (17) | C4'—C3'—C2' | 120.7 (6) |
| N1—La1—N4 | 120.08 (16) | C4'—C3'—H3' | 119.6 |
| N3—La1—N4 | 59.61 (13) | C3'—C4'—H4' | 120.6 |
| N1'—La1—N3' | 58.56 (16) | C3'—C4'—C5' | 118.8 (6) |
| N1'—La1—N4' | 117.50 (19) | C5'—C4'—H4' | 120.6 |
| N3'—La1—N4' | 59.0 (2) | N1'—C5'—C4' | 122.1 (6) |
| La1—O1—H1A | 131.3 (18) | N1'—C5'—N2' | 118.0 (6) |
| La1—O1—H1B | 123.4 (18) | N2'—C5'—C4' | 119.9 (6) |
| H1A—O1—H1B | 105 (2) | C5'—N2'—H2'A | 119.8 |
| La1—O2—H2A | 118.5 (19) | N3'—N2'—C5' | 120.3 (6) |
| La1—O2—H2B | 122 (2) | N3'—N2'—H2'A | 119.8 |
| H2A—O2—H2B | 105 (2) | N2'—N3'—La1 | 120.0 (4) |
| C14i—O3—La1 | 107.31 (13) | C6'—N3'—La1 | 122.3 (6) |
| C12—O4—La1 | 95.42 (13) | C6'—N3'—N2' | 117.6 (7) |
| C12—O5—La1 | 93.60 (13) | N3'—C6'—H6' | 120.0 |
| O4—C12—C13 | 118.9 (2) | N3'—C6'—C7' | 120.1 (7) |
| O5—C12—O4 | 120.66 (19) | C7'—C6'—H6' | 120.0 |
| O5—C12—C13 | 120.4 (2) | C8'—C7'—C6' | 119.7 (6) |
| C12—C13—H13A | 109.5 | N4'—C7'—C6' | 117.6 (6) |
| C12—C13—H13B | 109.5 | N4'—C7'—C8' | 122.6 (6) |
| C12—C13—H13C | 109.5 | C7'—C8'—H8' | 121.1 |
| H13A—C13—H13B | 109.5 | C9'—C8'—C7' | 117.7 (6) |
| H13A—C13—H13C | 109.5 | C9'—C8'—H8' | 121.1 |
| H13B—C13—H13C | 109.5 | C8'—C9'—H9' | 119.9 |
| La1—O10—La1i | 116.24 (6) | C8'—C9'—C10' | 120.2 (6) |
| C14—O10—La1i | 83.51 (11) | C10'—C9'—H9' | 119.9 |
| C14—O10—La1 | 156.33 (14) | C9'—C10'—H10' | 120.8 |
| O3i—C14—La1i | 50.25 (10) | C9'—C10'—C11' | 118.5 (7) |
| O3i—C14—O10 | 121.44 (19) | C11'—C10'—H10' | 120.8 |
| O3i—C14—C15 | 118.55 (19) | C10'—C11'—H11' | 118.5 |
| O10—C14—La1i | 72.88 (11) | N4'—C11'—C10' | 123.1 (8) |
| O10—C14—C15 | 120.00 (19) | N4'—C11'—H11' | 118.5 |
| C15—C14—La1i | 161.51 (17) | C7'—N4'—La1 | 120.9 (5) |
| C14—C15—H15A | 109.5 | C11'—N4'—La1 | 121.2 (6) |
| C14—C15—H15B | 109.5 | C11'—N4'—C7' | 117.9 (8) |
| C14—C15—H15C | 109.5 | O6—N5—O8 | 122.0 (3) |
| H15A—C15—H15B | 109.5 | O7—N5—O6 | 116.7 (3) |
| H15A—C15—H15C | 109.5 | O7—N5—O8 | 121.2 (4) |
| H15B—C15—H15C | 109.5 | O6'—N5'—O8' | 118.5 (17) |
| C1—N1—La1 | 120.6 (5) | O7'—N5'—O6' | 120.1 (19) |
| C5—N1—La1 | 122.5 (4) | O7'—N5'—O8' | 120.4 (19) |
| C5—N1—C1 | 116.8 (6) | H9A—O9—H9B | 104 (3) |
| N1—C1—H1 | 117.9 | ||
| La1—O4—C12—O5 | 3.1 (2) | C7—C8—C9—C10 | −0.2 (8) |
| La1—O4—C12—C13 | −176.59 (19) | C8—C7—N4—La1 | −172.4 (4) |
| La1—O5—C12—O4 | −3.0 (2) | C8—C7—N4—C11 | 0.8 (9) |
| La1—O5—C12—C13 | 176.64 (19) | C8—C9—C10—C11 | 0.6 (9) |
| La1—O10—C14—La1i | 148.0 (3) | C9—C10—C11—N4 | −0.4 (10) |
| La1i—O10—C14—O3i | 13.4 (2) | C10—C11—N4—La1 | 172.5 (5) |
| La1—O10—C14—O3i | 161.5 (2) | C10—C11—N4—C7 | −0.3 (10) |
| La1i—O10—C14—C15 | −165.5 (2) | N4—C7—C8—C9 | −0.6 (8) |
| La1—O10—C14—C15 | −17.4 (5) | N1'—C1'—C2'—C3' | −2.6 (13) |
| La1—N1—C1—C2 | −178.9 (9) | N1'—C5'—N2'—N3' | −5.7 (11) |
| La1—N1—C5—C4 | 177.9 (5) | C1'—N1'—C5'—C4' | 0.3 (11) |
| La1—N1—C5—N2 | −3.2 (10) | C1'—N1'—C5'—N2' | −179.3 (7) |
| La1—N3—C6—C7 | −1.0 (9) | C1'—C2'—C3'—C4' | 2.6 (12) |
| La1—N1'—C1'—C2' | 173.1 (7) | C2'—C3'—C4'—C5' | −1.3 (11) |
| La1—N1'—C5'—C4' | −171.4 (5) | C3'—C4'—C5'—N1' | −0.2 (11) |
| La1—N1'—C5'—N2' | 9.0 (9) | C3'—C4'—C5'—N2' | 179.4 (7) |
| La1—N3'—C6'—C7' | 4.1 (12) | C4'—C5'—N2'—N3' | 174.7 (8) |
| N1—C1—C2—C3 | 1.8 (15) | C5'—N1'—C1'—C2' | 1.2 (13) |
| N1—C5—N2—N3 | 0.3 (10) | C5'—N2'—N3'—La1 | −0.2 (10) |
| C1—N1—C5—C4 | 0.5 (12) | C5'—N2'—N3'—C6' | −177.8 (8) |
| C1—N1—C5—N2 | 179.4 (8) | N2'—N3'—C6'—C7' | −178.3 (8) |
| C1—C2—C3—C4 | −1.1 (11) | N3'—C6'—C7'—C8' | 175.9 (9) |
| C2—C3—C4—C5 | 0.3 (9) | N3'—C6'—C7'—N4' | −2.0 (13) |
| C3—C4—C5—N1 | 0.1 (10) | C6'—C7'—C8'—C9' | −176.0 (7) |
| C3—C4—C5—N2 | −178.8 (6) | C6'—C7'—N4'—La1 | −1.0 (12) |
| C4—C5—N2—N3 | 179.3 (6) | C6'—C7'—N4'—C11' | 176.2 (10) |
| C5—N1—C1—C2 | −1.5 (15) | C7'—C8'—C9'—C10' | −1.3 (11) |
| C5—N2—N3—La1 | 2.5 (8) | C8'—C7'—N4'—La1 | −178.9 (6) |
| C5—N2—N3—C6 | −179.0 (7) | C8'—C7'—N4'—C11' | −1.7 (15) |
| N2—N3—C6—C7 | −179.4 (6) | C8'—C9'—C10'—C11' | 0.7 (14) |
| N3—C6—C7—C8 | 175.6 (6) | C9'—C10'—C11'—N4' | −0.6 (18) |
| N3—C6—C7—N4 | −5.1 (9) | C10'—C11'—N4'—La1 | 178.2 (10) |
| C6—C7—C8—C9 | 178.7 (5) | C10'—C11'—N4'—C7' | 1.0 (18) |
| C6—C7—N4—La1 | 8.3 (7) | N4'—C7'—C8'—C9' | 1.8 (12) |
| C6—C7—N4—C11 | −178.5 (6) |
Symmetry code: (i) −x+1, −y+2, −z.
Di-µ-acetato-κ4O:O'-bis{(acetato-κ2O,O')tetraaqua[1-(pyridin-2-ylmethylidene-κN)-2-(pyridin-2-yl-κN)hydrazine-κN1]lanthanum(III)} dinitrate hemihydrate . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O6 | 0.76 (1) | 2.27 (2) | 2.994 (3) | 158 (3) |
| O1—H1A···O7 | 0.76 (1) | 2.59 (2) | 3.273 (6) | 151 (2) |
| O1—H1A···O6′ | 0.76 (1) | 2.19 (2) | 2.901 (14) | 154 (2) |
| O1—H1B···O8ii | 0.76 (1) | 2.03 (2) | 2.793 (4) | 176 (3) |
| O1—H1B···O8′ii | 0.76 (1) | 1.97 (3) | 2.73 (2) | 171 (3) |
| O2—H2A···O4i | 0.76 (1) | 1.95 (2) | 2.6971 (19) | 168 (3) |
| O2—H2B···O7ii | 0.76 (1) | 2.03 (2) | 2.786 (4) | 171 (3) |
| O2—H2B···N5′ii | 0.76 (1) | 2.68 (2) | 3.419 (16) | 164 (3) |
| O2—H2B···O7′ii | 0.76 (1) | 1.79 (3) | 2.54 (2) | 167 (3) |
| C13—H13A···O7iii | 0.96 | 2.53 | 3.483 (5) | 170 |
| C13—H13A···O7′iii | 0.96 | 2.33 | 3.27 (3) | 167 |
| C13—H13C···O7iv | 0.96 | 2.65 | 3.544 (6) | 155 |
| C15—H15A···O9 | 0.96 | 2.62 | 3.350 (10) | 133 |
| C2—H2···O6v | 0.93 | 2.57 | 3.420 (6) | 153 |
| N2—H2C···O5iv | 0.86 | 2.13 | 2.898 (7) | 149 |
| C11—H11···O9 | 0.93 | 2.57 | 3.150 (10) | 121 |
| N2′—H2′A···O5iv | 0.86 | 2.30 | 3.028 (7) | 142 |
| C6′—H6′···O5iv | 0.93 | 2.32 | 3.067 (9) | 138 |
| C10′—H10′···O6′v | 0.93 | 2.34 | 3.260 (18) | 170 |
| O9—H9A···O6vi | 0.76 (2) | 2.66 (14) | 3.062 (9) | 115 (13) |
| O9—H9B···O8vi | 0.76 (2) | 2.57 (10) | 3.241 (11) | 147 (16) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, −y+2, −z+1; (v) −x+2, −y+2, −z+1; (vi) x−1, y, z−1.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989024012349/pk2715sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989024012349/pk2715Isup2.hkl
CCDC reference: 2412041
Additional supporting information: crystallographic information; 3D view; checkCIF report



