Synthesis and crystal structure of a new coordination polymer based on lanthanum and 1,4-phenyl­enedi­acetate ligands

Camara, M.; Badiane, I.; Diallo, M.; Daiguebonne, C.; Guillou, O.

doi:10.1107/S2056989019002378

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ISSN: 2056-9890

Volume 75| Part 3| March 2019| Pages 378-382

https://doi.org/10.1107/S2056989019002378

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Synthesis and crystal structure of a new coordination polymer based on lanthanum and 1,4-phenylenediacetate ligands

Magatte Camara,^a ^* Insa Badiane,^a Mamoudou Diallo,^a Carole Daiguebonne ^b and Olivier Guillou ^b

^aUniversité Assane Seck de Ziguinchor, LCPM-Groupe Matériaux Inorganiques Chimie Douce et Cristallographie, BP 523 Ziguinchor, Senegal, and ^bUniversité de Rennes, INSA Rennes, CNRS UMR 6226, Institut des Sciences Chimiques de Rennes, F-35708 Rennes, France
^*Correspondence e-mail: magatte.camara@univ-zig.sn

Edited by A. Van der Lee, Université de Montpellier II, France (Received 6 February 2019; accepted 15 February 2019; online 22 February 2019)

Reaction in gel between the sodium salt of 1,4-phenylenediacetic acid (Na₂C₁₀O₄H₈–Na₂p-pda) and lanthanum chloride yields single crystals of the three-dimensional coordination polymer poly[[tetraaquatris(μ-1,4-phenylenediacetato)dilanthanum(III)] octahydrate], {[La₂(C₁₀H₈O₄)₃(H₂O)₄]·8H₂O}_∞. The La^III coordination polyhedron can be described as a slightly distorted monocapped square antiprism. One of the two p-pda²⁻ ligands is bound to four La^III ions and the other to two La^III ions. Each La^III atom is coordinated by five ligands, thereby generating a metal–organic framework with potential porosity properties.

Keywords: lanthanum ion; coordination polymer; crystal structure.

CCDC reference: 1875083

1. Chemical context

In recent years, one of the most important fields of research in coordination chemistry and crystal engineering has been the design of metal–organic frameworks (MOFs), because of their intriguing network topologies and possible applications in gas storage (Eddaoudi et al., 2002 ; Reneike et al., 1999 ; Luo et al., 2011a ,b ; Kustaryono et al., 2010 ), catalysis (Lee et al., 2009 ), separation (Hamon et al., 2009 ), luminescence (Cui et al., 2012 ; Daiguebonne et al., 2008 ; Binnemans, 2009 ;) and molecular magnetism (Calvez et al., 2008 ; Sessoli et al., 2009 ). Our group has been involved in this field for more than a decade (Freslon et al., 2014 ; Fan et al., 2014 ; Luo et al., 2011a,b; Badiane et al., 2017a ,b ). The search for new ligands that can lead to new structural networks and/or new physical properties is a continuous concern (Qiu et al., 2007 ; Fan et al., 2015 ).

For the synthesis of MOFs, usually two complementary molecular precursors, a cation with vacant coordination sites and a bridging anion, are used to form the coordination polymer. This procedure offers the prospect of rationally designing extended solids with interesting properties. Most of the organic ligands used in MOF chemistry are rigid aromatic carboxylates (Luo et al., 2007 ; Huang et al., 2009 ). Compared to the rigid ligands, using flexible ligands such as 1,2- (Xin et al., 2011 ), 1,3- (Wang et al., 2012 ) or 1,4-phenylenediacetate (Fabelo et al., 2009a ,b ) to construct coordination polymers seems to be more difficult, and developing synthetic methodologies is still a challenge. However, flexibility of the ligand can promote structural and functional diversity.

Numerous coordination polymers have been reported so far that involve d-block metal ions such as Cu^II (Singh & Barua, 2009 ; Fabelo et al., 2009a,b; Chen et al., 2010a ,b ,c ), Zn^II (Singh & Barua, 2009), Cd^II (Chen et al., 2010a,b,c; Singh & Barua, 2009; Li et al., 2009 ), Mn^II (Singh & Barua, 2009; Chen et al., 2010a,b,c, Co^II (Fabelo et al., 2009a,b; Chen et al., 2010a,b,c; Uebler & LaDuca, 2012 ; Li et al., 2009) and Ni^II (Chen et al., 2010a,b,c; Uebler & LaDuca, 2012; Li et al., 2009). Lanthanide(III) ions have higher and variable coordination numbers (generally between 7 and 12) and incorporate in addition, apart from the main ligands, ancillary ligands such as water molecules into the lanthanide coordination sphere. A large number of studies have been reported on lanthanide coordination polymers based on 1,4-phenylenediacetic acid (Singh & Barua, 2009; Fabelo et al., 2009a,b; Chen et al., 2010a,b,c; Uebler & LaDuca, 2012; Li et al., 2009; Rusinek et al., 2013 ) as well as on other isomers of this acid such as 1,2- (Badiane et al., 2017a,b; Xin et al., 2011) and 1,3-phenylenediacetic acid (Wang et al., 2012), and most of them tend to make porous materials through solvothermal synthesis.

Isomers of phenylenediacetic acid are flexible ligands and can therefore adopt different conformations in the crystal structure. 1,4-Phenylendiacetic acid is used as a readily available ligand that can coordinate two or more metal ions in bridging-mode, forming extended molecular networks (Pan et al., 2003 ; Chen et al., 2010a,b,c). The different coordination modes (Chen et al., 2010a,b,c; Rusinek et al., 2013; Ren et al., 2011 ; Pan et al., 2003; Singha et al., 2014 ; Singha et al., 2015 ) of the ligand with lanthanide ions that have been reported to date are shown in Fig. 1.

Figure 1
Bonding modes in lanthanide-containing coordination polymers with 1,4-phenylenediacetate ligands (p-pda²⁻) reported in the literature to date.

In this paper we report the synthesis and the crystal structure of a new coordination polymer with chemical formula [La₂(p-pda)₃(H₂O)₄·8H₂O]_∞.

2. Structural commentary

The crystallographically independent La³⁺ ion is nona-coordinated by seven oxygen atoms (O1, O2, O3, O4, O5, O6, O3^') from five p-pda²⁻ ligands and two oxygen atoms (O8 and O7) from the coordinating water molecules (Fig. 2). The coordination polyhedron can be described as a monocapped distorted square antiprism with atom O3′ capping the polyhedron [symmetry code: (′) 2 − x, 1 − y, 1 − z]. The two square sides of the antiprism are formed by atoms O7, O6, O2, O5 and O8, O3, O1, O4, respectively. The dihedral angle between the two faces is 5.21 (9)°. There are three independent ligands: L1, L2 and L3 (Fig. 3). The twisted ligand L3 exhibits a coordination mode that has never previously been observed in lanthanide-based coordination polymers involving the p-pda²⁻ ligand.

Figure 2
Coordination environment of La³⁺ in [La₂(p-pda)₃(H₂O)₄·8H₂O]_∞. Symmetry code: (′) 2 − x, 1 − y, 1 − z. Hydrogen atoms of the water molecules have been omitted for clarity.

Figure 3
Coordination modes of ligand L1 (μ-4 bis-bidentate mode: (η¹-η¹-μ₂)-(η¹-η¹-μ₂)-μ₄), L2 (μ-4 bis-tridentate bridging and chelating mode: (η²-η¹-μ₂)-(η²-η¹-μ₂)-μ₄) and L3 (μ-2 bis-bidentate-chelating mode: (η¹-η¹-μ₁)-(η¹-η¹-μ₁)-μ₂)).

The monocapped square antiprisms are connected to each other by alternating L1 bridging carboxylate oxygen atoms (O5 and O6) and edge-sharing polyhedra through L2 oxygen atoms (O3), forming molecular chains along the a-axis direction (Fig. 4). These chains are connected to each other through ligands L1 and L2, which play the role of spacers, forming molecular layers that extend parallel to the ab plane (Fig. 4). These layers are further connected through the twisted ligand L3, leading to a three-dimensional molecular framework (Fig. 5). Ligand L3 acts as a spacer between the different polymeric layers because of its anti–anti conformation.

Figure 4
(Top) Projection view of a molecular chain extending parallel to the a axis. (Bottom) Projection view along the c axis of the of the two-dimensional molecular network of [La₂(p-pda)₃(H₂O)₄·8H₂O]_∞. Hydrogen atoms have been omitted for clarity.

Figure 5
Perspective view along the a axis of [La₂(p-pda)₃(H₂O)₄·8H₂O]_∞. Hydrogen atoms have been omitted for clarity.

The framework has channels along the a-axis direction in which the water molecules of crystallization are located. They are bound to the molecular skeleton via a hydrogen-bonded network (Table 1). As can be seen from Fig. 6, the three-dimensional crystal structure could potentially present some porosity properties. Indeed, removal of the water molecules of crystallization could create empty channels, as has been reported previously (Kustaryono et al., 2010; Kerbellec et al., 2008 ). For the coordination polymer in this study, the potential porosity is calculated to be 750 (20) m² g⁻¹ for N₂ with a kinetic radius of 1.83 Å. The calculation was performed using a method described elsewhere (Kustaryono et al., 2010; Kerbellec et al., 2008).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—HW1A⋯OW1ⁱⁱⁱ	0.87 (9)	2.40 (11)	3.067 (13)	133 (9)
OW1—HW1B⋯OW4^iv	0.89 (9)	2.54 (10)	3.298 (11)	145 (7)
OW2—HW2A⋯O4ⁱ	0.82 (6)	2.10 (6)	2.895 (5)	164 (6)
OW2—HW2B⋯OW4^v	0.82 (6)	2.20 (5)	2.855 (8)	137 (5)
OW3—HW3A⋯O6ⁱ	0.82 (8)	2.02 (8)	2.780 (8)	154 (7)
OW3—HW3B⋯OW1ⁱⁱⁱ	0.81 (7)	2.40 (8)	3.162 (11)	156 (8)
OW4—HW4A⋯OW2^vi	0.81 (10)	2.49 (9)	2.855 (8)	109 (9)
O7—H7A⋯O2ⁱ	0.82 (4)	1.95 (4)	2.741 (5)	161 (5)
O7—H7B⋯OW4	0.81 (5)	2.03 (5)	2.800 (9)	160 (5)
OW4—HW4B⋯OW3^vii	0.84 (9)	2.11 (10)	2.824 (11)	143 (8)
O8—H8A⋯OW3ⁱ	0.82 (4)	2.38 (4)	3.175 (8)	165 (4)
O8—H8B⋯O1ⁱⁱ	0.83 (4)	1.92 (4)	2.725 (5)	163 (5)
C7—H7D⋯O4ⁱ	0.97	2.54	3.442 (6)	154
C12—H12B⋯O6ⁱⁱ	0.97	2.51	3.406 (6)	154
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y, -z+1; (iv) x, y-1, z; (v) x, y, z+1; (vi) x, y, z-1; (vii) x+1, y+1, z.

Figure 6
Projection view along the a axis of the molecular skeleton of [La₂(p-pda)₃(H₂O)₄·8H₂O]_∞ in space-filling mode. Hydrogen atoms and crystallization water molecules have been omitted.

Other crystal structures of lanthanide coordination polymers with the p-pda²⁻ ligand have been reported previously. This series of compounds, first described by Pan et al. (2003) has been widely studied because of potential applications in various fields such as explosives detection (Singha et al., 2014, 2015), gas sorption (Pan et al., 2003) or catalysis (Ren et al., 2011). These compounds, with general chemical formula [Ln₂(p-pda)₃(H₂O)·2H₂O]_∞ with Ln = La–Ho have been obtained by hydrothermal synthesis and therefore present a lower hydration rate and a higher density than [La₂(p-pda)₃(H₂O)₄·8H₂O]_∞ {D_calc = 1871 g cm⁻³ for [Ln₂(p-pda)₃(H₂O)·2H₂O]_∞}. Their three-dimensional crystal structures can be described on the basis of helicoidal molecular chains linked by p-pda²⁻ ligands.

The luminescent and porosity properties of these compounds are interesting, which suggests that the physical properties of compounds isostructural to [La₂(p-pda)₃(H₂O)₄·8H₂O]_∞ and involving other lanthanide ions (lanthanum is a diamagnetic non-luminescent ion) would be worth studying. Unfortunately, despite great synthetic efforts, no such compound has been obtained to date.

The compound reported here was obtained by crystallization in a gel (see next section; Luo et al., 2013 ), and as such is the first result from our group related to lanthanide-based coordination polymers with 1,4-phenylenediacetate ligands.

3. Synthesis and crystallization

Lanthanum oxide (La₂O₃) was suspended in a small quantity of water. The suspension was then brought to about 323 K and concentrated hydrochloric acid was added dropwise under magnetic stirring, until a clear solution was obtained. The solution was then evaporated to dryness and the resulting solid was dissolved in absolute ethanol for removal of the residual hydrochloric acid. Crystallization of the salt was then obtained by adding diethyl ether (Et₂O). The obtained microcrystalline solid was filtered and dried in the open air. The product LaCl₃·7H₂O was obtained in close to 100% yield.

1,4-Phenylenediacetic acid, H₂(p-pda), was purchased from Sigma–Aldrich and used without further purification. Its disodium salt was prepared by addition of two equivalents of sodium hydroxide to a suspension of the acid in de-ionized water. The obtained clear solution was evaporated to dryness and then refluxed in ethanol for one h. Addition of diethyl ether provoked precipitation of Na₂(p-pda) in 90% yield. UV–vis absorption spectrum of a 4.3 × 10 ⁻⁴ mol L⁻¹ aqueous solution of the disodium salt of H₂(p-pda) was measured with a Perkin–Elmer Lambda 650 spectrometer equipped with a 60 mm integrating sphere. It showed a maximum absorption at 225 nm. This short absorption wavelength, compared to other ligands in the literature (Badiane et al., 2017a,b; Freslon et al., 2016 ; Fan et al., 2015; Badiane et al., 2018 ), can be related to the –CH₂– groups that cut conjugation.

Single crystals of the coordination polymer were obtained by slow diffusion of dilute aqueous solutions of lanthanum chloride (0.25 mmol in 10 mL) and of the sodium salt of para-phenylenediacetate (0.25 mmol in 10 mL) through an agar-agar gel in a U-shaped tube. The gel was purchased from Acros Organics and jellified according to established procedures (Henisch, 1988 ; Daiguebonne et al., 2003 ). After several weeks, prismatic single crystals were obtained.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms bound to the organic ligands were placed at idealized positions (C—H = 0.93–0.97 Å) and refined as riding with U_iso(H) = 1.2U_eq(C). The water hydrogen atoms were localized and constrained. The thermal agitation of the two water molecules of crystallization was constrained. In order to stabilize the refinement several restraints (DANG, DFIX) were used for the hydrogen atoms bound to water oxygens.

Table 2
Experimental details

Crystal data
Chemical formula	[La₂(C₁₀H₈O₄)₃(H₂O)₄]·8H₂O
M_r	1070.05
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	9.1197 (2), 11.1231 (2), 11.9434 (2)
α, β, γ (°)	107.049 (1), 107.729 (1), 106.622 (1)
V (Å³)	1005.21 (3)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	2.18
Crystal size (mm)	0.08 × 0.06 × 0.05

Data collection
Diffractometer	Nonius KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections	4588, 4588, 3751
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.068, 1.03
No. of reflections	4588
No. of parameters	283
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.76, −0.65
Computer programs: COLLECT (Bruker, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2001 ), WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1875083

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989019002378/vn2143sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019002378/vn2143Isup2.hkl

Table 2. Valence angles and torsion angles around the ligands. DOI: https://doi.org/10.1107/S2056989019002378/vn2143sup3.pdf

checkCIF report

Computing details top

Data collection: COLLECT (Bruker, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Poly[[tetraaquatris(µ-1,4-phenylenediacetato)dilanthanum(III)] octahydrate] top

Crystal data top

[La₂(C₁₀H₈O₄)₃(H₂O)₄]·8H₂O	Z = 1
M_r = 1070.05	F(000) = 534
Triclinic, P1	D_x = 1.768 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1197 (2) Å	Cell parameters from 15558 reflections
b = 11.1231 (2) Å	θ = 2.9–27.5°
c = 11.9434 (2) Å	µ = 2.18 mm⁻¹
α = 107.049 (1)°	T = 293 K
β = 107.729 (1)°	Prism, colorless
γ = 106.622 (1)°	0.08 × 0.06 × 0.05 mm
V = 1005.21 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	3751 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	R_int = 0.045
Horizonally mounted graphite crystal monochromator	θ_max = 27.5°, θ_min = 3.6°
Detector resolution: 9 pixels mm^-1	h = −10→11
CCD rotation images, thick slices scans	k = −14→14
4588 measured reflections	l = −15→15
4588 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: dual
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: mixed
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0308P)²] where P = (F_o² + 2F_c²)/3
4588 reflections	(Δ/σ)_max = 0.001
283 parameters	Δρ_max = 1.76 e Å⁻³
18 restraints	Δρ_min = −0.65 e Å⁻³
0 constraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
La1	0.75090 (2)	0.52031 (2)	0.47969 (2)	0.02048 (7)
O5	0.4472 (3)	0.3677 (2)	0.4069 (2)	0.0332 (6)
O3	1.0575 (3)	0.5881 (3)	0.6253 (2)	0.0323 (6)
O1	0.7627 (3)	0.3041 (3)	0.5311 (2)	0.0336 (6)
O6	0.8146 (3)	0.7579 (3)	0.6435 (3)	0.0362 (6)
O2	0.7422 (3)	0.4674 (3)	0.6736 (2)	0.0351 (6)
O4	0.6840 (3)	0.3616 (3)	0.2490 (2)	0.0415 (7)
O7	0.5690 (4)	0.5882 (4)	0.3233 (3)	0.0486 (8)
H7A	0.468 (3)	0.558 (4)	0.307 (5)	0.058*
H7B	0.591 (5)	0.651 (4)	0.302 (5)	0.058*
O8	0.9316 (4)	0.7051 (3)	0.4326 (4)	0.0503 (8)
H8A	0.947 (6)	0.785 (3)	0.470 (4)	0.060*
H8B	1.026 (4)	0.712 (4)	0.435 (5)	0.060*
C6	0.6834 (4)	0.7426 (3)	0.6621 (3)	0.0260 (7)
C11	0.8165 (4)	0.3436 (3)	0.2659 (3)	0.0261 (7)
C1	0.7640 (4)	0.3589 (4)	0.6405 (4)	0.0315 (8)
C13	0.6579 (5)	0.1147 (4)	0.0739 (4)	0.0340 (9)
C12	0.8247 (5)	0.2382 (4)	0.1565 (4)	0.0390 (9)
H12A	0.857342	0.281262	0.102898	0.058*
H12B	0.910563	0.207990	0.192279	0.058*
C14	0.6017 (5)	0.0190 (4)	0.1196 (4)	0.0427 (10)
H14	0.669560	0.030195	0.201149	0.051*
C8	0.8472 (5)	0.9325 (4)	0.8881 (4)	0.0340 (9)
C10	0.9564 (5)	1.0646 (4)	0.9217 (4)	0.0433 (10)
H10	0.928413	1.109955	0.869797	0.052*
C15	0.5547 (5)	0.0946 (4)	−0.0469 (4)	0.0412 (10)
H15	0.589046	0.157191	−0.080797	0.049*
C7	0.6832 (5)	0.8578 (4)	0.7675 (4)	0.0445 (11)
H7C	0.660724	0.923722	0.734480	0.067*
H7D	0.592152	0.819798	0.789973	0.067*
C9	0.8927 (6)	0.8687 (4)	0.9685 (4)	0.0461 (11)
H9	0.820475	0.779508	0.948162	0.055*
C3	0.8997 (5)	0.3972 (4)	0.8732 (4)	0.0392 (9)
C4	1.0738 (6)	0.4427 (5)	0.9267 (4)	0.0514 (11)
H4	1.125405	0.405378	0.878263	0.062*
C5	0.8281 (6)	0.4561 (5)	0.9477 (4)	0.0501 (11)
H5	0.711419	0.427472	0.913133	0.060*
C2	0.7931 (6)	0.2928 (4)	0.7347 (4)	0.0460 (10)
H2A	0.684726	0.235879	0.727251	0.069*
H2B	0.848359	0.233001	0.711571	0.069*
OW1	0.6313 (10)	0.0072 (5)	0.4440 (6)	0.1327 (17)
HW1A	0.589 (11)	−0.025 (9)	0.491 (8)	0.159*
HW1B	0.639 (13)	−0.072 (6)	0.411 (8)	0.159*
OW2	0.5351 (5)	0.6185 (4)	0.9718 (4)	0.0741 (11)
HW2A	0.476 (7)	0.639 (6)	0.920 (5)	0.111*
HW2B	0.622 (6)	0.678 (5)	1.033 (5)	0.111*
OW3	0.0357 (9)	0.0056 (6)	0.3870 (6)	0.1327 (17)
HW3A	0.059 (10)	0.059 (7)	0.354 (7)	0.159*
HW3B	0.122 (7)	0.023 (10)	0.447 (6)	0.159*
OW4	0.7105 (10)	0.7873 (7)	0.2433 (6)	0.154 (3)
HW4A	0.649 (10)	0.805 (11)	0.192 (8)	0.185*
HW4B	0.810 (5)	0.831 (11)	0.255 (10)	0.185*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.01729 (10)	0.02001 (10)	0.01850 (10)	0.00633 (7)	0.00482 (7)	0.00498 (7)
O5	0.0242 (13)	0.0258 (13)	0.0312 (13)	0.0032 (10)	0.0034 (11)	0.0040 (11)
O3	0.0227 (13)	0.0340 (14)	0.0229 (12)	0.0074 (11)	0.0027 (10)	0.0011 (11)
O1	0.0352 (14)	0.0353 (14)	0.0339 (14)	0.0161 (12)	0.0168 (12)	0.0155 (12)
O6	0.0247 (13)	0.0283 (13)	0.0415 (15)	0.0089 (10)	0.0129 (12)	−0.0005 (11)
O2	0.0403 (15)	0.0427 (15)	0.0332 (14)	0.0254 (13)	0.0173 (12)	0.0200 (12)
O4	0.0267 (14)	0.0515 (17)	0.0253 (13)	0.0175 (12)	0.0040 (11)	−0.0052 (12)
O7	0.0425 (17)	0.075 (2)	0.067 (2)	0.0390 (17)	0.0345 (17)	0.0532 (18)
O8	0.0456 (18)	0.0523 (18)	0.088 (2)	0.0315 (16)	0.0434 (18)	0.0469 (19)
C6	0.0228 (17)	0.0219 (17)	0.0260 (17)	0.0100 (14)	0.0051 (14)	0.0052 (14)
C11	0.0187 (16)	0.0250 (17)	0.0236 (16)	0.0060 (13)	0.0062 (14)	0.0018 (14)
C1	0.0184 (17)	0.041 (2)	0.0332 (19)	0.0099 (15)	0.0083 (15)	0.0177 (17)
C13	0.0261 (19)	0.030 (2)	0.0297 (19)	0.0117 (16)	0.0070 (16)	−0.0041 (16)
C12	0.0233 (18)	0.040 (2)	0.0318 (19)	0.0098 (16)	0.0074 (16)	−0.0057 (17)
C14	0.039 (2)	0.044 (2)	0.028 (2)	0.0198 (19)	0.0002 (18)	0.0047 (18)
C8	0.031 (2)	0.0293 (19)	0.0290 (19)	0.0102 (16)	0.0138 (16)	−0.0032 (16)
C10	0.042 (2)	0.033 (2)	0.037 (2)	0.0058 (18)	0.0114 (19)	0.0059 (18)
C15	0.043 (2)	0.037 (2)	0.031 (2)	0.0133 (19)	0.0076 (18)	0.0078 (17)
C7	0.026 (2)	0.040 (2)	0.043 (2)	0.0127 (17)	0.0102 (18)	−0.0078 (19)
C9	0.042 (2)	0.0225 (19)	0.048 (2)	−0.0033 (17)	0.016 (2)	0.0006 (18)
C3	0.043 (2)	0.044 (2)	0.035 (2)	0.0206 (19)	0.0123 (18)	0.0260 (18)
C4	0.051 (3)	0.073 (3)	0.041 (2)	0.037 (2)	0.022 (2)	0.023 (2)
C5	0.032 (2)	0.077 (3)	0.042 (2)	0.024 (2)	0.0112 (19)	0.027 (2)
C2	0.055 (3)	0.040 (2)	0.039 (2)	0.017 (2)	0.012 (2)	0.0233 (19)
OW1	0.192 (4)	0.069 (2)	0.109 (3)	0.009 (3)	0.079 (3)	0.028 (2)
OW2	0.063 (3)	0.086 (3)	0.074 (3)	0.032 (2)	0.020 (2)	0.043 (2)
OW3	0.192 (4)	0.069 (2)	0.109 (3)	0.009 (3)	0.079 (3)	0.028 (2)
OW4	0.158 (6)	0.115 (4)	0.103 (4)	−0.017 (4)	−0.019 (4)	0.084 (4)

Geometric parameters (Å, º) top

La1—O5	2.507 (2)	C12—H12B	0.9700
La1—O5ⁱ	2.905 (3)	C14—H14	0.9300
La1—O3ⁱⁱ	2.781 (2)	C14—C15ⁱⁱⁱ	1.399 (6)
La1—O3	2.545 (2)	C8—C10	1.373 (6)
La1—O1	2.673 (2)	C8—C7	1.509 (5)
La1—O6	2.559 (2)	C8—C9	1.388 (6)
La1—O2	2.569 (2)	C10—H10	0.9300
La1—O4	2.566 (2)	C10—C9^iv	1.382 (6)
La1—O7	2.543 (3)	C15—H15	0.9300
La1—O8	2.562 (3)	C7—H7C	0.9700
La1—C11	3.066 (3)	C7—H7D	0.9700
La1—C1	2.988 (4)	C9—H9	0.9300
O5—C6ⁱ	1.255 (4)	C3—C4	1.385 (6)
O3—C11ⁱⁱ	1.264 (4)	C3—C5	1.381 (6)
O1—C1	1.264 (4)	C3—C2	1.509 (6)
O6—C6	1.256 (4)	C4—H4	0.9300
O2—C1	1.248 (4)	C4—C5^v	1.391 (6)
O4—C11	1.246 (4)	C5—H5	0.9300
O7—H7A	0.824 (19)	C2—H2A	0.9700
O7—H7B	0.806 (18)	C2—H2B	0.9700
O8—H8A	0.815 (19)	OW1—HW1A	0.87 (2)
O8—H8B	0.833 (19)	OW1—HW1B	0.88 (2)
C6—C7	1.512 (5)	OW2—HW2A	0.821 (19)
C11—C12	1.516 (5)	OW2—HW2B	0.81 (2)
C1—C2	1.514 (5)	OW3—HW3A	0.82 (2)
C13—C12	1.507 (5)	OW3—HW3B	0.81 (2)
C13—C14	1.376 (6)	OW4—HW4A	0.81 (2)
C13—C15	1.371 (5)	OW4—HW4B	0.84 (2)
C12—H12A	0.9700

O5—La1—O5ⁱ	61.48 (9)	C11—O4—La1	101.3 (2)
O5—La1—O3	146.45 (9)	La1—O7—H7A	116 (3)
O5—La1—O3ⁱⁱ	118.58 (7)	La1—O7—H7B	133 (3)
O5—La1—O1	75.87 (8)	H7A—O7—H7B	109 (3)
O5—La1—O6	107.86 (8)	La1—O8—H8A	118 (3)
O5—La1—O2	75.29 (8)	La1—O8—H8B	122 (3)
O5—La1—O4	80.33 (8)	H8A—O8—H8B	104 (3)
O5—La1—O7	71.93 (9)	O5ⁱ—C6—La1	68.28 (18)
O5—La1—O8	140.13 (9)	O5ⁱ—C6—O6	120.2 (3)
O5ⁱ—La1—C11	156.28 (8)	O5ⁱ—C6—C7	120.1 (3)
O5—La1—C11	98.48 (8)	O6—C6—La1	52.33 (16)
O5—La1—C1	75.84 (9)	O6—C6—C7	119.7 (3)
O5ⁱ—La1—C1	88.69 (9)	C7—C6—La1	169.6 (2)
O3—La1—O5ⁱ	118.22 (7)	O3ⁱⁱ—C11—La1	65.08 (17)
O3ⁱⁱ—La1—O5ⁱ	179.00 (7)	O3ⁱⁱ—C11—C12	120.3 (3)
O3—La1—O3ⁱⁱ	61.11 (8)	O4—C11—La1	55.16 (17)
O3—La1—O1	73.20 (8)	O4—C11—O3ⁱⁱ	119.9 (3)
O3—La1—O6	80.93 (8)	O4—C11—C12	119.8 (3)
O3—La1—O2	74.87 (8)	C12—C11—La1	171.2 (2)
O3—La1—O4	108.82 (8)	O1—C1—La1	63.39 (19)
O3—La1—O8	73.39 (9)	O1—C1—C2	119.8 (3)
O3ⁱⁱ—La1—C11	24.36 (8)	O2—C1—La1	58.58 (18)
O3—La1—C11	85.47 (8)	O2—C1—O1	121.5 (3)
O3—La1—C1	70.64 (9)	O2—C1—C2	118.7 (3)
O3ⁱⁱ—La1—C1	90.37 (9)	C2—C1—La1	172.4 (3)
O1—La1—O5ⁱ	109.68 (7)	C14—C13—C12	120.5 (4)
O1—La1—O3ⁱⁱ	69.49 (8)	C15—C13—C12	122.1 (4)
O1—La1—C11	74.29 (9)	C15—C13—C14	117.4 (4)
O1—La1—C1	25.01 (9)	C11—C12—H12A	109.2
O6—La1—O5ⁱ	46.41 (7)	C11—C12—H12B	109.2
O6—La1—O3ⁱⁱ	133.56 (8)	C13—C12—C11	112.0 (3)
O6—La1—O1	126.21 (9)	C13—C12—H12A	109.2
O6—La1—O2	78.86 (9)	C13—C12—H12B	109.2
O6—La1—O4	149.49 (10)	H12A—C12—H12B	107.9
O6—La1—O8	71.55 (10)	C13—C14—H14	119.1
O6—La1—C11	149.62 (9)	C13—C14—C15ⁱⁱⁱ	121.8 (4)
O6—La1—C1	101.90 (10)	C15ⁱⁱⁱ—C14—H14	119.1
O2—La1—O5ⁱ	66.57 (8)	C10—C8—C7	121.6 (4)
O2—La1—O3ⁱⁱ	112.44 (8)	C10—C8—C9	117.8 (4)
O2—La1—O1	49.39 (8)	C9—C8—C7	120.6 (4)
O2—La1—C11	123.42 (9)	C8—C10—H10	119.5
O2—La1—C1	24.50 (9)	C8—C10—C9^iv	121.1 (4)
O4—La1—O5ⁱ	132.95 (7)	C9^iv—C10—H10	119.5
O4—La1—O3ⁱⁱ	47.75 (7)	C13—C15—C14ⁱⁱⁱ	120.7 (4)
O4—La1—O1	84.13 (9)	C13—C15—H15	119.6
O4—La1—O2	131.27 (9)	C14ⁱⁱⁱ—C15—H15	119.6
O4—La1—C11	23.49 (8)	C6—C7—H7C	108.9
O4—La1—C1	108.61 (10)	C6—C7—H7D	108.9
O7—La1—O5ⁱ	70.81 (9)	C8—C7—C6	113.4 (3)
O7—La1—O3	141.53 (10)	C8—C7—H7C	108.9
O7—La1—O3ⁱⁱ	110.19 (9)	C8—C7—H7D	108.9
O7—La1—O1	142.43 (10)	H7C—C7—H7D	107.7
O7—La1—O6	82.59 (10)	C8—C9—H9	119.4
O7—La1—O2	134.87 (9)	C10^iv—C9—C8	121.1 (4)
O7—La1—O4	71.95 (10)	C10^iv—C9—H9	119.4
O7—La1—O8	68.46 (10)	C4—C3—C2	120.7 (4)
O7—La1—C11	91.69 (10)	C5—C3—C4	118.0 (4)
O7—La1—C1	147.21 (10)	C5—C3—C2	121.2 (4)
O8—La1—O5ⁱ	108.04 (8)	C3—C4—H4	119.8
O8—La1—O3ⁱⁱ	72.59 (9)	C3—C4—C5^v	120.4 (4)
O8—La1—O1	138.11 (8)	C5^v—C4—H4	119.8
O8—La1—O2	139.28 (10)	C3—C5—C4^v	121.6 (4)
O8—La1—O4	83.41 (11)	C3—C5—H5	119.2
O8—La1—C11	78.57 (10)	C4^v—C5—H5	119.2
O8—La1—C1	144.03 (10)	C1—C2—H2A	109.0
C1—La1—C11	98.95 (10)	C1—C2—H2B	109.0
La1—O5—La1ⁱ	118.52 (9)	C3—C2—C1	112.8 (3)
C6ⁱ—O5—La1ⁱ	88.1 (2)	C3—C2—H2A	109.0
C6ⁱ—O5—La1	153.4 (2)	C3—C2—H2B	109.0
La1—O3—La1ⁱⁱ	118.89 (8)	H2A—C2—H2B	107.8
C11ⁱⁱ—O3—La1	150.5 (2)	HW1A—OW1—HW1B	88 (7)
C11ⁱⁱ—O3—La1ⁱⁱ	90.56 (19)	HW2A—OW2—HW2B	121 (5)
C1—O1—La1	91.6 (2)	HW3A—OW3—HW3B	108 (4)
C6—O6—La1	104.8 (2)	HW4A—OW4—HW4B	107 (4)
C1—O2—La1	96.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1A···OW1^vi	0.87 (9)	2.40 (11)	3.067 (13)	133 (9)
OW1—HW1B···OW4^vii	0.89 (9)	2.54 (10)	3.298 (11)	145 (7)
OW2—HW2A···O4ⁱ	0.82 (6)	2.10 (6)	2.895 (5)	164 (6)
OW2—HW2B···OW4^viii	0.82 (6)	2.20 (5)	2.855 (8)	137 (5)
OW3—HW3A···O6ⁱ	0.82 (8)	2.02 (8)	2.780 (8)	154 (7)
OW3—HW3B···OW1^vi	0.81 (7)	2.40 (8)	3.162 (11)	156 (8)
OW4—HW4A···OW2^ix	0.81 (10)	2.49 (9)	2.855 (8)	109 (9)
O7—H7A···O2ⁱ	0.82 (4)	1.95 (4)	2.741 (5)	161 (5)
O7—H7B···OW4	0.81 (5)	2.03 (5)	2.800 (9)	160 (5)
OW4—HW4B···OW3^x	0.84 (9)	2.11 (10)	2.824 (11)	143 (8)
O8—H8A···OW3ⁱ	0.82 (4)	2.38 (4)	3.175 (8)	165 (4)
O8—H8B···O1ⁱⁱ	0.83 (4)	1.92 (4)	2.725 (5)	163 (5)
C7—H7D···O4ⁱ	0.97	2.54	3.442 (6)	154
C12—H12B···O6ⁱⁱ	0.97	2.51	3.406 (6)	154

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

Acknowledgements

The French Cooperation Agency in Senegal is acknowledged for financial support.

References

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