Crystal structure of poly[[di-μ3-acetato-tetra­aqua­bis­(μ2-cyclo­hexane-1,4-di­carboxyl­ato)dilanth­an­um(III)] dihydrate]

Drisya, R.; Mol, U.S.S.; Chandran, P.R.S.; Sithambaresan, M.; Sudarsankumar, M.R.

doi:10.1107/S2056989017016103

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Volume 73| Part 12| December 2017| Pages 1926-1930

https://doi.org/10.1107/S2056989017016103

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Crystal structure of poly[[di-μ₃-acetato-tetraaquabis(μ₂-cyclohexane-1,4-dicarboxylato)dilanthanum(III)] dihydrate]

R. Drisya,^a U. S. Soumya Mol,^a P. R. Satheesh Chandran,^a M. Sithambaresan ^b ^* and M. R. Sudarsankumar ^a

^aDepartment of Chemistry, Mahatma Gandhi College, Thiruvananthapuram 695 004, Kerala, India, and ^bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka
^*Correspondence e-mail: msithambaresan@gmail.com

Edited by A. Van der Lee, Université de Montpellier II, France (Received 2 September 2017; accepted 7 November 2017; online 21 November 2017)

The title compound, {[La₂(CH₃COO)₂(C₈H₁₀O₄)₂(H₂O)₄]·2H₂O}_n or [La₂(ac)₂(e,a-cis-1,4-chdc)₂(H₂O)₄]·2H₂O, where ac is acetate and 1,4-chdc is cyclohexane-1,4-dicarboxylate anion, is a binuclear lanthanum(III) complex. Each metal atom is decacoordinated by four O atoms from two distinct 1,4-chdc²⁻ ligands, four O atoms from three acetate groups and two O atoms from coordinated water molecules to form a distorted bicapped square-antiprismatic geometry. Two non-coordinated water molecules are also present in the formula unit. The most remarkable feature of this compound is that it possesses a only cis conformation for cyclohexane-1,4-dicarboxylic acid, although the raw material consists of a mixture of cis and trans isomers. The μ₃-η²:η² coordination mode of the bridging acetate group and the flexible dicarboxylate fragments of 1,4-chdc²⁻ results in the formation of infinite two-dimensional lanthanide–carboxylate layers within the crystal structure. The directionality of strong intermolecular O—H⋯O and weak C—H⋯O interactions provides robustness to the layers, which leads to the construction of a three-dimensional supramolecular network. The crystal studied was refined as a two-component twin.

Keywords: crystal structure; cyclohexane-1,4-dicarboxylic acid; lanthanum(III) complex.

CCDC reference: 1546730

1. Chemical context

1,4-Cyclohexanedicarboxyic acid (1,4-chdcH₂) is a flexible alicyclic, ditopic ligand having a chair-type backbone structure, which has been used for the construction of many coordination polymers (CPs) with remarkable architectures (Liu et al., 2010 ). It can exist in three different conformations – two trans isomers, (a,a) and (e,e), and one cis (e,a) form. From a thermodynamical point of view, the trans (e,e) form is the most stable of the three different conformations as a result of the equatorial–equatorial –COOH groups and the trans (a,a) isomer is the least stable because of 1,3-diaxial hindrance (Yu et al., 2007 ; Gong et al., 2005 ; Bi et al., 2003 ; Du et al., 2005 ; Chen et al., 2014 )·Theoretical calculations suggest that the isomers tend to cause conformational inversion within the ligand structure due to the flexibility of the C—C bond rotation and also because of the extremely low free energy change between them (Qiblawi et al., 2013 ; Lin & Tong, 2011 ; Liu et al., 2010). Furthermore, the isomeric separation of the organic ligand can be controlled by several factors such as the pH of the solution, the nature of the metal ion, the co-ligand, the reaction solvent and the temperature (Lin & Tong, 2011; Liu et al., 2010).

2. Structural commentary

The asymmetric unit of the title compound consists of one crystallographically unique La metal ion, a fully deprotonated 1,4-chdc²⁻ anion, an acetate moiety and three water molecules (two coordinated and one non-coordinated). From the molecular structure (Fig. 1), it is evident that each La^III atom has a distorted bicapped square-antiprismatic coordination sphere defined by four oxygen atoms from two distinct 1,4-chdc²⁻ ligands (O1, O2, O7, O8), four oxygen atoms from three acetate groups (O5, O6, O5′, O6′) and two oxygen atoms from coordinated water molecules (O3, O4) to form a [LaO₁₀] coordination polyhedron (Fig. 2). Of the three prevalent conformations of 1,4-chdcH₂, low temperature usually favours the cis (e,a) and high temperature favours the trans (e,e) conformational compounds (Lin & Tong, 2011; Lu et al., 2008 ; Bi et al., 2004 ). Here, the bent structure of the organic linker possesses an L-shaped cis (e,a) conformation within the crystal structure. The corresponding La—O bond lengths are in the range 2.506 (8)—2.792 (7) Å and the O—La—O bond angles vary from 46.51 (19) to 170.7 (2)°. The La—O bond distances are comparable with those in several reported structures in which 1,4-cyclohexanedicarboxylic acid exists in various coordination modes and conformations (Rao et al., 2007 ; Qi et al., 2008 ).

Figure 1
ORTEP view of the molecular structure of the title complex with the atom-numbering scheme and ellipsoids drawn at the 50% probability level..

Figure 2
Bicapped square-antiprismatic geometry of an [LaO₁₀] polyhedron. Displacement ellipsoids are drawn at the 80% probability level.

The bridging μ₃-η²:η² coordination mode (each oxygen atom connects two metal atoms) of the acetate group joins two [LaO₁₀] polyhedra by edge sharing to form a dimeric structure. The dimers are then interlinked by La—O—La bonding and as a consequence of this, infinite zigzag 1D [La₂O₂] chains are formed. Within these chains, La⋯La non-bonding distances are found to be 4.5835 (9) and 4.4125 (9) Å. Additionally, the bis-bidentate chelating μ₂-η¹:η¹:η¹:η¹ coordination mode of the dicarboxylate group of 1,4-chdc²⁻ connects two metal atoms and hence converts it into a 2D coordination polymeric structure parallel to the ab plane. A perspective view of the packing along the c axis in a wireframe model (Fig. 3) shows the formation of infinite 2D lanthanide–carboxylate layers. The [La₂O₂] chains are then further interconnected by a dicarboxylate anion from two 1,4-chdc²⁻ units to form a 24-membered macrocyclic ring as shown in Fig. 4. A series of organotin complexes of the cis and trans isomers of 1,4-chdcH₂ show similar 2D networks containing 26- and 36-membered tetratin macrocyclic rings (Ma et al., 2009 ).

Figure 3
Perspective view of the packing along the c axis.

Figure 4
The 24-membered macrocyclic ring formation by 1,4-chdc²⁻ between two [La₂O₂] chains.

3. Supramolecular features

From the polyhedral view along the a axis (Fig. 5), it is clear that the two lattice water molecules residing in the voids of the 1,4-chdc²⁻ units are responsible for the development of hydrophilic channels within the crystal structure. The hydrogen-bonding interactions (Table 1) shown in Fig. 6 play a vital role in increasing the stability and higher dimensionality of the crystal packing. Here, the oxygen atom O9 of the lattice water molecule acts as a donor for hydrogen bonds with oxygen atoms O1 and O2 of the carboxylate group of the 1,4-chdc²⁻ ligand [O9—H9A⋯O2 = 2.786 (12) Å and O9—H9B⋯O1ⁱⁱⁱ = 2.846 (11) Å]. It also acts as the hydrogen-bond acceptor for oxygen atoms O3 and O4 of the coordinated water molecules [O3—H3C⋯O9 = 2.858 (12) Å and O4—H4D⋯O9ⁱⁱ 2.812 (11) Å]. Similarly, oxygen atom O7 of the carboxylate group of 1,4-chdc acts as an acceptor to atoms O3 and O4 of the coordinated water molecules [O3—H3D⋯O7ⁱⁱ = 2.750 (11) Å and O4—H4C⋯O7ⁱ = 2.771 (10) Å]. Apart from this strong intermolecular hydrogen bonding, there are also weak C—H⋯O interactions between the carbon atom C10 of the coordinated acetate group and the O1 oxygen atom of a carboxylate group of the organic linker [C10—H10C⋯O1 = 3.295 (14) Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10C⋯O1	0.96	2.49	3.295 (14)	141
O4—H4C⋯O7ⁱ	0.90 (2)	1.92 (5)	2.771 (10)	158 (12)
O4—H4D⋯O9ⁱⁱ	0.89 (2)	1.96 (6)	2.812 (11)	158 (12)
O3—H3C⋯O9	0.90 (2)	1.97 (3)	2.858 (12)	172 (13)
O3—H3D⋯O7ⁱⁱ	0.90 (2)	1.86 (3)	2.750 (11)	170 (14)
O9—H9A⋯O2	0.90 (2)	2.20 (11)	2.786 (12)	122 (11)
O9—H9B⋯O1ⁱⁱⁱ	0.90 (2)	1.97 (5)	2.846 (11)	164 (13)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1; (iii) x-1, y, z.

Figure 5
Polyhedral view along the a axis showing the free water molecules.

Figure 6
Hydrogen-bonding interactions (dashed lines) in the structure of the title compound. For symmetry operations, see Table 1

4. Database survey

In the three-dimensional structures of [La₂(1,4-chdc)₃(H₂O)₄], [La₃(1,4-Hchdc)₂(1,4-chdc)₅(H₂O)₂]·H₂O and [La₂(1,4-chdc)₃(H₂O)]·2.5H₂O, the dicarboxylate anion exists in different conformations obtained under hydrothermal conditions (Rao et al., 2007). Similarly a two-dimensional lanthanum coordination polymer [La₂(1,10-phen)₂(1,4-chdc)₃]·2.5H₂O with π–π stacking was observed by the incorporation of 1,10-phenanthroline as a co-ligand along with 1,4-cyclohexanedicarboxylic acid (Qi et al., 2008). Additionally, dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) solvent-coordinated lanthanum complexes, one-dimensional [La(cis-chdc)(DMF)₂(NO₃)] and three-dimensional [La₂(trans-chdc)₃(DMSO)₄] have also been reported. The presence of solvent molecules can completely segregate the cis and trans conformations of 1,4-chdc (Tian et al., 2009 ).

5. Synthesis and crystallization

Single crystals of the title compound were prepared by the gel-diffusion technique at ambient temperature using sodium metasilicate nonahydrate (Na₂S₂O₃·9H₂O) as the gel medium. The optimum condition for crystal growth was obtained by dissolving 0.75 g of 1,4-H₂chdc in 25 ml of 1.04 g cm⁻³ dense gel medium. 5 ml of the above solution was poured into glass tubes and the pH of the solution was set to 7.0 by adding glacial acetic acid drop by drop. On completion of the gel-setting process, 3 ml of 0.5 M concentration of aqueous lanthanum nitrate solution was added as the upper reagent. The whole arrangement was kept undisturbed at room temperature and was covered to protect it from the foreign matter present in the atmosphere. Within seven days, transparent, colourless block-shaped crystals were observed at the gel interface. The diffusion of La³⁺ ions and 1,4-chdcH₂ through the fine pores of the gel media lead to the expected chemical reaction as shown below:

2La(NO₃)₃·6H₂O + 2C₈H₁₂O₄ + 2CH₃COOH → [La₂(CH₃COO)₂(C₈H₁₀O₄)₂(H₂O)₄]·2H₂O + 6HNO₃.

Elemental analysis calculated (%) for C₂₀H₃₈La₂O₁₈ (844.32): C, 28.42; H, 4.50. Found (%): C, 28.36; H, 4.33. IR (KBr, cm⁻¹): 3380, 2940, 1573, 1460, 743, 673, 597.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Carbon-bound hydrogen atoms were placed in calculated positions and included in the refinement in the riding-model approximation with C—H distances of 0.96–0.98 Å and with U_iso(H) = 1.2U_eq(C) for methyl hydrogen atoms and U_iso(H) = 1.2U_eq(C) for all others. Water hydrogen atoms were located from difference-Fourier maps and refined with an O—H distance restraint of 0.90 (2) Å and an H⋯H separation of 1.39 (2) Å. The isotropic displacement parameters of the hydrogen atoms attached to atoms O3, O4 and O9 were made equal by using an EDAP instruction. The crystal studied was refined as a two-component twin (BASF = 0.4203).

Table 2
Experimental details

Crystal data
Chemical formula	[La₂(C₂H₃O₂)₂(C₈H₁₀O₄)₂(H₂O)₄]·2H₂O
M_r	844.32
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	6.9341 (8), 8.9597 (13), 12.3030 (16)
α, β, γ (°)	110.217 (5), 91.060 (5), 93.280 (5)
V (Å³)	715.49 (16)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	3.02
Crystal size (mm)	0.20 × 0.15 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.60, 0.74
No. of measured, independent and observed [I > 2σ(I)] reflections	2818, 2815, 2447
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.146, 1.07
No. of reflections	2818
No. of parameters	204
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.17, −2.46
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SIR92 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2010 ), SHELXL2014 (Sheldrick, 2015) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1546730

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016103/vn2132sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016103/vn2132Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and publCIF (Westrip, 2010)'.

Poly[[di-µ₃-acetato-tetraaquabis(µ₂-cyclohexane-1,4-dicarboxylato)dilanthanum(III)] dihydrate] top

Crystal data top

[La₂(C₂H₃O₂)₂(C₈H₁₀O₄)₂(H₂O)₄]·2H₂O	Z = 1
M_r = 844.32	F(000) = 416
Triclinic, P1	D_x = 1.960 Mg m⁻³
a = 6.9341 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9597 (13) Å	Cell parameters from 7100 reflections
c = 12.3030 (16) Å	θ = 2.8–30.9°
α = 110.217 (5)°	µ = 3.02 mm⁻¹
β = 91.060 (5)°	T = 293 K
γ = 93.280 (5)°	Block, colourless
V = 715.49 (16) Å³	0.20 × 0.15 × 0.15 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2815 independent reflections
Radiation source: Sealed tube	2447 reflections with I > 2σ(I)
ω and φ scan	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
T_min = 0.60, T_max = 0.74	k = −11→10
2818 measured reflections	l = 0→15

Refinement top

Refinement on F²	9 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.0821P)² + 6.1459P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.005
2818 reflections	Δρ_max = 2.17 e Å⁻³
204 parameters	Δρ_min = −2.46 e Å⁻³

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.

Refinement. Refined as a two-component twin.

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

	x	y	z	U_iso*/U_eq
C1	0.2377 (17)	0.7936 (10)	0.7752 (7)	0.0203 (18)
C2	0.2486 (18)	0.7706 (11)	0.8920 (8)	0.030 (2)
H2	0.2447	0.8760	0.9522	0.036*
C3	0.0724 (17)	0.6681 (16)	0.9058 (11)	0.033 (3)
H3A	0.0698	0.6715	0.9855	0.040*
H3B	−0.0448	0.7116	0.8889	0.040*
C4	0.0778 (17)	0.4962 (14)	0.8253 (10)	0.030 (3)
H4A	0.0694	0.4919	0.7455	0.036*
H4B	−0.0331	0.4339	0.8379	0.036*
C5	0.2631 (16)	0.4239 (11)	0.8460 (7)	0.024 (2)
H5	0.2633	0.4196	0.9245	0.028*
C6	0.4375 (16)	0.5264 (15)	0.8372 (11)	0.030 (3)
H6A	0.4468	0.5213	0.7574	0.036*
H6B	0.5526	0.4836	0.8576	0.036*
C7	0.4325 (17)	0.6994 (14)	0.9147 (10)	0.028 (2)
H7A	0.5438	0.7602	0.9010	0.034*
H7B	0.4403	0.7067	0.9952	0.034*
C8	0.2736 (16)	0.2574 (10)	0.7614 (8)	0.0229 (19)
C9	0.7522 (14)	1.0347 (9)	0.6555 (7)	0.0141 (16)
C10	0.7542 (18)	1.0729 (13)	0.7831 (8)	0.030 (2)
H10A	0.7030	1.1749	0.8194	0.046*
H10B	0.8846	1.0758	0.8118	0.046*
H10C	0.6763	0.9926	0.8006	0.046*
O1	0.3916 (11)	0.7991 (10)	0.7225 (7)	0.0280 (18)
O2	0.0804 (11)	0.8116 (10)	0.7334 (7)	0.0272 (18)
O3	−0.0144 (11)	0.6946 (10)	0.4871 (7)	0.0310 (18)
O4	0.3865 (13)	0.6914 (10)	0.4470 (8)	0.039 (2)
O5	0.5999 (10)	0.9978 (10)	0.5957 (6)	0.0219 (16)
O6	0.9100 (10)	1.0455 (9)	0.6066 (6)	0.0220 (16)
O7	0.2827 (11)	0.2366 (7)	0.6530 (5)	0.0223 (14)
O8	0.2635 (12)	0.1397 (7)	0.7932 (5)	0.0283 (15)
O9	−0.2682 (13)	0.6345 (9)	0.6499 (7)	0.0384 (18)
La1	0.23952 (8)	0.92768 (5)	0.58722 (4)	0.01486 (18)
H4C	0.474 (15)	0.704 (14)	0.398 (8)	0.05 (3)*
H4D	0.326 (16)	0.597 (8)	0.406 (8)	0.05 (3)*
H3C	−0.088 (14)	0.668 (17)	0.538 (9)	0.06 (3)*
H3D	−0.105 (12)	0.705 (17)	0.437 (9)	0.06 (3)*
H9A	−0.207 (15)	0.687 (15)	0.719 (6)	0.06 (3)*
H9B	−0.388 (9)	0.669 (17)	0.663 (10)	0.06 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.026 (5)	0.012 (4)	0.025 (4)	−0.004 (4)	0.006 (5)	0.008 (3)
C2	0.047 (7)	0.023 (5)	0.019 (4)	0.003 (5)	−0.002 (5)	0.008 (4)
C3	0.029 (7)	0.041 (7)	0.034 (7)	0.011 (5)	0.007 (5)	0.017 (6)
C4	0.031 (7)	0.027 (6)	0.030 (6)	0.004 (5)	0.003 (4)	0.005 (5)
C5	0.030 (6)	0.026 (5)	0.016 (4)	−0.005 (4)	−0.002 (4)	0.011 (4)
C6	0.022 (6)	0.037 (7)	0.033 (6)	0.004 (5)	−0.005 (4)	0.014 (5)
C7	0.041 (8)	0.025 (6)	0.017 (5)	0.001 (5)	−0.004 (4)	0.007 (4)
C8	0.017 (5)	0.024 (5)	0.029 (5)	0.002 (4)	−0.001 (4)	0.012 (4)
C9	0.010 (4)	0.012 (3)	0.018 (4)	0.003 (4)	−0.002 (4)	0.001 (3)
C10	0.026 (6)	0.042 (6)	0.020 (4)	−0.006 (5)	0.003 (5)	0.007 (4)
O1	0.016 (4)	0.039 (5)	0.039 (5)	0.005 (3)	0.005 (3)	0.025 (4)
O2	0.026 (5)	0.031 (5)	0.028 (4)	0.004 (3)	−0.005 (3)	0.015 (4)
O3	0.026 (5)	0.035 (5)	0.034 (5)	−0.005 (3)	−0.002 (3)	0.017 (4)
O4	0.033 (5)	0.022 (4)	0.051 (5)	−0.009 (3)	0.023 (4)	−0.001 (4)
O5	0.012 (4)	0.037 (4)	0.020 (4)	−0.001 (3)	0.002 (3)	0.014 (3)
O6	0.011 (4)	0.032 (4)	0.025 (4)	−0.001 (3)	0.002 (3)	0.011 (3)
O7	0.025 (4)	0.024 (3)	0.018 (3)	0.001 (3)	0.006 (3)	0.007 (2)
O8	0.042 (4)	0.021 (3)	0.024 (3)	−0.001 (4)	−0.004 (3)	0.011 (3)
O9	0.023 (5)	0.033 (4)	0.057 (5)	0.004 (4)	0.004 (4)	0.013 (4)
La1	0.0121 (3)	0.0169 (3)	0.0169 (3)	0.0017 (2)	0.0015 (2)	0.00745 (18)

Geometric parameters (Å, º) top

C1—O2	1.240 (13)	C9—La1ⁱⁱ	3.119 (8)
C1—O1	1.266 (13)	C10—H10A	0.9600
C1—C2	1.522 (12)	C10—H10B	0.9600
C1—La1	2.952 (8)	C10—H10C	0.9600
C2—C7	1.521 (17)	O1—La1	2.570 (7)
C2—C3	1.533 (17)	O2—La1	2.601 (8)
C2—H2	0.9800	O3—La1	2.588 (8)
C3—C4	1.519 (18)	O3—H3C	0.90 (2)
C3—H3A	0.9700	O3—H3D	0.90 (2)
C3—H3B	0.9700	O4—La1	2.506 (8)
C4—C5	1.527 (16)	O4—H4C	0.90 (2)
C4—H4A	0.9700	O4—H4D	0.89 (2)
C4—H4B	0.9700	O5—La1	2.533 (7)
C5—C8	1.502 (12)	O5—La1ⁱⁱ	2.792 (7)
C5—C6	1.505 (15)	O6—La1ⁱⁱⁱ	2.552 (7)
C5—H5	0.9800	O6—La1ⁱⁱ	2.674 (7)
C6—C7	1.516 (17)	O7—La1ⁱ	2.598 (6)
C6—H6A	0.9700	O8—La1ⁱ	2.585 (6)
C6—H6B	0.9700	O9—H9A	0.90 (2)
C7—H7A	0.9700	O9—H9B	0.90 (2)
C7—H7B	0.9700	La1—O6^iv	2.552 (7)
C8—O8	1.244 (11)	La1—O8^v	2.585 (6)
C8—O7	1.284 (11)	La1—O7^v	2.598 (6)
C8—La1ⁱ	2.983 (9)	La1—O6ⁱⁱ	2.674 (7)
C9—O5	1.237 (11)	La1—O5ⁱⁱ	2.792 (7)
C9—O6	1.273 (11)	La1—C8^v	2.983 (9)
C9—C10	1.487 (11)

O2—C1—O1	120.1 (8)	C9—O6—La1ⁱⁱ	98.1 (5)
O2—C1—C2	120.4 (9)	La1ⁱⁱⁱ—O6—La1ⁱⁱ	115.2 (3)
O1—C1—C2	119.5 (10)	C8—O7—La1ⁱ	94.3 (5)
O2—C1—La1	61.6 (5)	C8—O8—La1ⁱ	96.0 (5)
O1—C1—La1	60.2 (5)	H9A—O9—H9B	101 (3)
C2—C1—La1	164.8 (6)	O4—La1—O5	73.2 (3)
C1—C2—C7	114.2 (9)	O4—La1—O6^iv	135.8 (3)
C1—C2—C3	110.9 (9)	O5—La1—O6^iv	143.4 (2)
C7—C2—C3	109.4 (8)	O4—La1—O1	77.7 (3)
C1—C2—H2	107.4	O5—La1—O1	73.8 (2)
C7—C2—H2	107.4	O6^iv—La1—O1	126.4 (2)
C3—C2—H2	107.4	O4—La1—O8^v	146.0 (3)
C4—C3—C2	111.4 (9)	O5—La1—O8^v	82.5 (3)
C4—C3—H3A	109.4	O6^iv—La1—O8^v	76.9 (2)
C2—C3—H3A	109.4	O1—La1—O8^v	72.8 (2)
C4—C3—H3B	109.4	O4—La1—O3	67.5 (3)
C2—C3—H3B	109.4	O5—La1—O3	140.7 (3)
H3A—C3—H3B	108.0	O6^iv—La1—O3	73.0 (3)
C3—C4—C5	111.4 (10)	O1—La1—O3	96.1 (3)
C3—C4—H4A	109.4	O8^v—La1—O3	131.7 (3)
C5—C4—H4A	109.4	O4—La1—O7^v	138.0 (2)
C3—C4—H4B	109.4	O5—La1—O7^v	73.7 (2)
C5—C4—H4B	109.4	O6^iv—La1—O7^v	69.9 (2)
H4A—C4—H4B	108.0	O1—La1—O7^v	116.4 (2)
C8—C5—C6	110.0 (9)	O8^v—La1—O7^v	49.88 (18)
C8—C5—C4	111.2 (9)	O3—La1—O7^v	140.6 (2)
C6—C5—C4	110.4 (8)	O4—La1—O2	103.1 (3)
C8—C5—H5	108.4	O5—La1—O2	121.8 (2)
C6—C5—H5	108.4	O6^iv—La1—O2	78.8 (2)
C4—C5—H5	108.4	O1—La1—O2	49.7 (2)
C5—C6—C7	113.4 (9)	O8^v—La1—O2	69.9 (2)
C5—C6—H6A	108.9	O3—La1—O2	67.7 (3)
C7—C6—H6A	108.9	O7^v—La1—O2	116.2 (2)
C5—C6—H6B	108.9	O4—La1—O6ⁱⁱ	83.0 (3)
C7—C6—H6B	108.9	O5—La1—O6ⁱⁱ	107.7 (2)
H6A—C6—H6B	107.7	O6^iv—La1—O6ⁱⁱ	64.8 (3)
C6—C7—C2	111.4 (9)	O1—La1—O6ⁱⁱ	159.3 (3)
C6—C7—H7A	109.3	O8^v—La1—O6ⁱⁱ	127.8 (2)
C2—C7—H7A	109.3	O3—La1—O6ⁱⁱ	69.3 (2)
C6—C7—H7B	109.3	O7^v—La1—O6ⁱⁱ	83.2 (2)
C2—C7—H7B	109.3	O2—La1—O6ⁱⁱ	129.9 (2)
H7A—C7—H7B	108.0	O4—La1—O5ⁱⁱ	68.8 (3)
O8—C8—O7	119.6 (8)	O5—La1—O5ⁱⁱ	61.3 (3)
O8—C8—C5	121.6 (8)	O6^iv—La1—O5ⁱⁱ	103.7 (2)
O7—C8—C5	118.7 (7)	O1—La1—O5ⁱⁱ	129.6 (2)
O8—C8—La1ⁱ	59.5 (5)	O8^v—La1—O5ⁱⁱ	119.3 (2)
O7—C8—La1ⁱ	60.3 (4)	O3—La1—O5ⁱⁱ	104.2 (2)
C5—C8—La1ⁱ	172.5 (8)	O7^v—La1—O5ⁱⁱ	72.9 (2)
O5—C9—O6	118.9 (7)	O2—La1—O5ⁱⁱ	170.7 (2)
O5—C9—C10	121.7 (9)	O6ⁱⁱ—La1—O5ⁱⁱ	46.51 (19)
O6—C9—C10	119.4 (9)	O4—La1—C1	93.6 (3)
O5—C9—La1ⁱⁱ	63.3 (4)	O5—La1—C1	97.2 (3)
O6—C9—La1ⁱⁱ	58.1 (4)	O6^iv—La1—C1	101.4 (3)
C10—C9—La1ⁱⁱ	161.8 (6)	O1—La1—C1	25.3 (3)
C9—C10—H10A	109.5	O8^v—La1—C1	65.9 (2)
C9—C10—H10B	109.5	O3—La1—C1	84.1 (3)
H10A—C10—H10B	109.5	O7^v—La1—C1	115.7 (2)
C9—C10—H10C	109.5	O2—La1—C1	24.8 (3)
H10A—C10—H10C	109.5	O6ⁱⁱ—La1—C1	152.5 (3)
H10B—C10—H10C	109.5	O5ⁱⁱ—La1—C1	154.8 (3)
C1—O1—La1	94.4 (6)	O4—La1—C8^v	151.3 (3)
C1—O2—La1	93.6 (6)	O5—La1—C8^v	78.0 (3)
La1—O3—H3C	113 (9)	O6^iv—La1—C8^v	70.6 (3)
La1—O3—H3D	120 (9)	O1—La1—C8^v	94.8 (3)
H3C—O3—H3D	101 (3)	O8^v—La1—C8^v	24.5 (2)
La1—O4—H4C	121 (8)	O3—La1—C8^v	141.2 (3)
La1—O4—H4D	127 (8)	O7^v—La1—C8^v	25.4 (2)
H4C—O4—H4D	102 (3)	O2—La1—C8^v	92.3 (3)
C9—O5—La1	147.1 (6)	O6ⁱⁱ—La1—C8^v	105.7 (2)
C9—O5—La1ⁱⁱ	93.4 (5)	O5ⁱⁱ—La1—C8^v	97.0 (2)
La1—O5—La1ⁱⁱ	118.7 (3)	C1—La1—C8^v	90.4 (2)
C9—O6—La1ⁱⁱⁱ	138.0 (6)

O2—C1—C2—C7	161.8 (9)	C4—C5—C8—O7	63.7 (13)
O1—C1—C2—C7	−20.4 (13)	O2—C1—O1—La1	15.4 (9)
La1—C1—C2—C7	−105 (3)	C2—C1—O1—La1	−162.5 (7)
O2—C1—C2—C3	37.7 (12)	O1—C1—O2—La1	−15.2 (9)
O1—C1—C2—C3	−144.5 (9)	C2—C1—O2—La1	162.6 (7)
La1—C1—C2—C3	131 (3)	O6—C9—O5—La1	174.3 (8)
C1—C2—C3—C4	69.6 (12)	C10—C9—O5—La1	−8.2 (16)
C7—C2—C3—C4	−57.2 (11)	La1ⁱⁱ—C9—O5—La1	−168.1 (12)
C2—C3—C4—C5	57.2 (12)	O6—C9—O5—La1ⁱⁱ	−17.7 (8)
C3—C4—C5—C8	−176.5 (9)	C10—C9—O5—La1ⁱⁱ	159.9 (7)
C3—C4—C5—C6	−54.1 (12)	O5—C9—O6—La1ⁱⁱⁱ	−124.4 (8)
C8—C5—C6—C7	176.5 (9)	C10—C9—O6—La1ⁱⁱⁱ	58.0 (12)
C4—C5—C6—C7	53.4 (11)	La1ⁱⁱ—C9—O6—La1ⁱⁱⁱ	−143.1 (9)
C5—C6—C7—C2	−55.0 (12)	O5—C9—O6—La1ⁱⁱ	18.6 (9)
C1—C2—C7—C6	−69.6 (12)	C10—C9—O6—La1ⁱⁱ	−158.9 (7)
C3—C2—C7—C6	55.3 (11)	O8—C8—O7—La1ⁱ	4.7 (11)
C6—C5—C8—O8	124.8 (11)	C5—C8—O7—La1ⁱ	−171.5 (9)
C4—C5—C8—O8	−112.5 (12)	O7—C8—O8—La1ⁱ	−4.8 (11)
C6—C5—C8—O7	−59.0 (13)	C5—C8—O8—La1ⁱ	171.4 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···O1	0.96	2.49	3.295 (14)	141
O4—H4C···O7^vi	0.90 (2)	1.92 (5)	2.771 (10)	158 (12)
O4—H4D···O9^vii	0.89 (2)	1.96 (6)	2.812 (11)	158 (12)
O3—H3C···O9	0.90 (2)	1.97 (3)	2.858 (12)	172 (13)
O3—H3D···O7^vii	0.90 (2)	1.86 (3)	2.750 (11)	170 (14)
O9—H9A···O2	0.90 (2)	2.20 (11)	2.786 (12)	122 (11)
O9—H9B···O1^iv	0.90 (2)	1.97 (5)	2.846 (11)	164 (13)

Symmetry codes: (iv) x−1, y, z; (vi) −x+1, −y+1, −z+1; (vii) −x, −y+1, −z+1.

Acknowledgements

The authors are thankful to the authorities of SAIF, Kochi for instrumental facilities. We are indebted to Dr M. R. Prathachandra Kurup, Department of Applied Chemistry, Cochin University of Science and Technology, Kochi, for helping us to visualize the crystal structure using DIAMOND software. RD is thankful to the University of Kerala, Trivandrum, India, for the award of a University Research Fellowship.

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