Crystal structure and Hirshfeld surface analysis of the anionic tetra­kis-complex of lanthanum(III) NMe4LaL4 with the CAPh-ligand dimeth­yl (2,2,2-tri­chloro­acet­yl)phospho­ramidate

Struhatska, M.B.; Kariaka, N.S.; Amirkhanov, V.M.; Dyakonenko, V.V.; Seredyuk, M.

doi:10.1107/S2056989021011750

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Volume 77| Part 12| December 2021| Pages 1307-1310

https://doi.org/10.1107/S2056989021011750

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Crystal structure and Hirshfeld surface analysis of the anionic tetrakis-complex of lanthanum(III) NMe₄LaL₄ with the CAPh-ligand dimethyl (2,2,2-trichloroacetyl)phosphoramidate

Mariia B. Struhatska,^a Nataliia S. Kariaka,^a Vladimir M. Amirkhanov,^a Viktoriya V. Dyakonenko ^b and Maksym Seredyuk ^a ^*

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine, and ^bSSI "Institute for Single Crystals" of National Academy of Sciences of Ukraine, Nauky ave. 60, 61001 Kharkiv, Ukraine
^*Correspondence e-mail: mlseredyuk@gmail.com

Edited by J. T. Mague, Tulane University, USA (Received 13 October 2021; accepted 5 November 2021; online 16 November 2021)

The anionic tetrakis-complex of lanthanum(III) NMe₄LaL₄ with the CAPh-ligand dimethyl (2,2,2-trichloroacetyl)phosphoramidate (HL), namely, tetramethylammonium tetrakis{2,2,2-trichloro-1-[(dimethoxyphosphoryl)imino]ethanolato}lanthanum(III), (C₄H₁₂N)[La(C₄H₆Cl₃NO₄P)₄], has been synthesized, crystallized and structurally characterized by X-ray diffraction. The lanthanide ion is surrounded by four anionic, bis-chelating CAPh ligands forming the complex anion with a coordination number of eight for La³⁺ and NMe₄⁺ as the counter-ion. The coordination polyhedron of the La³⁺ ion was interpreted as a triangular dodecahedron.

Keywords: crystal structure; lanthanum(III) complex; β-diketone derivatives; carbacylamidophopsphates; rare earth metals; coordination compound; Hirshfeld analysis.

CCDC reference: 2120335

1. Chemical context

Considerable interest in the luminescence properties of lanthanide coordination compounds results from their potential applications in modern technologies and medicine (Eliseeva et al., 2010 ; Kido et al., 2002 ; Tsukube et al., 2002 ). In particular, use of P,N-substituted analogues of β-diketone such as carbacylamidophopsphates (CAPh) (Amirkhanov et al., 2014 ) with the C(O)NHP(O) structural fragment as ligands is promising because of their powerful chelating properties (Skopenko et al., 2004 ; Amirkhanov et al., 2014) and ability to sensitize the luminescence of lanthanides (Kariaka et al., 2016 ; Pham et al., 2017 ; Kariaka et al., 2018 ). In this work, the synthesis and crystal structure of the anionic tetrakis-complex of lanthanum(III) containing the CAPh-ligand dimethyl (2,2,2-trichloroacetyl)phosphoramidate and a tetramethylammonium cation (formula NMe₄LaL₄) is reported.

2. Structural commentary

The title compound (C₄H₁₂N)[La(C₄H₆Cl₃NO₄P)₄] crystallizes in the monoclinic crystal system with two molecules in the unit cell. Both the cation and the anion have crystallographically-imposed C₂ symmetry with atoms La1 and N3 located on the twofold axis. The molecular structure of the complex is shown in Fig. 1. In the complex, the La³⁺ ion has a triangular dodecahedral coordination environment formed by the eight O atoms of the bidentate CAPh ligands and the N(CH₃)₄⁺ unit acts as the counter-ion (Fig. 1). The average La—O bond length is 2.494 Å while the La—O(C) bond lengths [2.534 (3)–2.566 (3) Å] are all longer than the La—O(P) bonds [2.432 (3)–2.445 (3) Å]. Deprotonation of the ligands leads to increasing π-conjugation in the chelating fragment and results in the bond-length changes. The C—O and P—O bond lengths are in the ranges 1.225 (5)–1.240 (6) Å and 1.475 (3)–1.476 (4) Å, respectively, with corresponding average values of 1.233 and 1.476 Å. The corresponding bond lengths in the neutral ligand HL are 1.202 (2) and 1.459 (2) Å (Amirkhanov et al., 2014). The C—O and P—O bonds of the ligand in the complex are longer than those in the neutral ligand (HL), indicating greater C=O and P=O double-bond character in HL than in NMe₄LaL₄. The C—N and P—N bonds, with lengths in the ranges 1.291 (6)–1.292 (6) and 1.598 (4)–1.602 (5) Å, respectively, in NMe₄LaL₄ are shorter compared to those in the free ligand, in which the reported C—N bond length is 1.347 (2) Å and P—N is 1.676 (1) Å (Amirkhanov et al., 1995 ).

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 25% probability level. Hydrogen atoms are omitted for clarity [Symmetry code: (i) −x + $[{1\over 2}]$ , y, −z + $[{1\over 2}]$ ).

3. Supramolecular features

There are no classical hydrogen bonds in the crystal structure of the title compound, although the complexes are linked via numerous weak C—H⋯O and Cl⋯Cl intermolecular interactions (Table 1). In particular, the PO and OCH₃ groups of the ligands are involved in the formation of interactions with the hydrogen atoms of the tetramethylammonium cation, linking the complex anion and the counter-ion in a chain along the b-axis direction. The Cl12A⋯Cl12Aⁱⁱ [symmetry code (ii): −x, −y + 1, −z + 1] interactions, at 3.475 (12) Å, are only 0.03 Å less than the sum of the van der Waals radii but definitely below the maximum separation (4.0 Å) considered to represent at least weak, attractive Cl⋯Cl interactions (Capdevila-Cortada et al., 2016 ). These serve to connect neighbouring chains. The crystal packing of the title compound is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O6	0.96	2.35	3.184 (7)	145
C10—H10C⋯O2ⁱ	0.96	2.33	3.218 (8)	154
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+1, -z+{\script{3\over 2}}]$ .

Figure 2
The crystal packing of the title compound viewed along the b-axis direction.

4. Hirshfeld surface analysis and fingerprint plots

To visualize the intermolecular interactions in the title compound, the Hirshfeld surface and its corresponding two-dimensional fingerprint plots (Spackman et al., 2009 ) were calculated using CrystalExplorer17 (Turner et al., 2017 ). There are several light-red spots on the d_norm surface (Fig. 3), which correspond to O⋯H/H⋯O contacts. They are located near the oxygen atoms of the ligand PO groups and the hydrogen atoms of the tetramethylammonium cation. Thus, the strongest contacts in the crystal of the title compound exist between the NMe₄⁺ cation and the complex anion.

Figure 3
The Hirshfeld surface mapped over d_norm and two-dimensional fingerprint plots for the Cl⋯H/H⋯Cl (50.7%), H⋯H (20.8%), O⋯H/H⋯O (13.6%), Cl⋯Cl (11.6%) and N⋯H/H⋯N (3.1%) interactions in NMe₄[LaL₄].

The two-dimensional fingerprint plots show distances from the Hirshfeld surface to the nearest exterior atom (d_e plots) and from an interior atom to the surface (d_i plots), specify atom⋯atom contacts in a crystal and provide a quantitative idea of the types of intermolecular contacts experienced by molecules. An analysis of the fingerprint plots (Fig. 3) shows that the Cl⋯H/H⋯Cl contacts make the major contribution to the Hirshfeld surface at 50.7%. The closest Cl⋯H/H⋯Cl contact occurs at d_i = d_e = 2.9 Å. The next largest contributions come from H⋯H contacts (20.8%), O⋯H/H⋯O contacts (13.6%) and Cl⋯Cl contacts (11.6%). The closest O⋯H/H⋯O contact occurs at d_i = d_e= 1.35 Å. The smallest percentage contributions to the Hirshfeld surface come from the N⋯H/H⋯N (3,1%), Cl⋯O/O⋯Cl (0.1%) and O⋯O (0.1%) interatomic contacts.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.41, update of March 2020; Groom et al., 2016 ) for lanthanide complexes containing bidentate-coordinated CAPh ligands yielded 48 hits. Eight of them are tetrakis complexes Cat[Ln(CAPh)₄] of which five crystallize with two tetrakis complexes in the asymmetric unit. Using SHAPE analysis (SHAPE2.1; Llunell et al., 2013 ), the nine coordination polyhedra have been interpreted as square antiprismatic (D4d) and, for the other polyhedra, as triangular dodecahedral (D2d).

No CAPh-based lanthanum tetrakis complexes have been reported to date. However, seven lanthanum complexes containing CAPhs coordinated in a bidentate manner are known. The average La—O(C) bond length is 2.411 Å while the average La—O(P) bond length is 2.351 Å. Only one tetrakis complex based on dimethyl (2,2,2-trichloroacetyl)phosphoramidate (NaErL₄) has been reported to date. The lengths of the CO, PO, PN and CN bonds in this complex are in the ranges 1.206–1.335, 1.422–1.489, 1.565–1.608 and 1.250–1.334 Å, respectively.

6. Synthesis and crystallization

The ¹H NMR spectrum of a solution of the title compound in DMSO-d₆ was recorded on a Varian 400 NMR spectrometer at room temperature. The infrared (IR) spectrum was recorded on a Perkin–Elmer BX-II Bruker spectrometer using a KBr pellet.

Preparation of NMe₄LaL_4. LaCl₃·7H₂O (0.0371 g, 0.1 mmol) in the presence of HC(OC₂H₅)₃ (0.14 ml, 0.7 mmol) as dehydrating agent was dissolved in 2-propanol under heating. In a separate flask, NaL (0.1122 g, 0.4 mmol) was dissolved in acetone and NMe₄Cl (0.0121 g, 0.11 mmol) was added under stirring and heating. The two mixtures were combined and boiled for a minute, then cooled to room temperature. A white precipitate of NaCl was formed and was filtered off and the filtrate left in a flask in a desiccator over CaCl₂. After two days, colourless crystals suitable for X-ray diffraction studies were obtained. The crystals were filtered off, washed with 2-propanol and dried in air.

IR (KBr pellet, cm⁻¹): 2954 [w, ν(C—H_aliph)], 1614 [s, ν(C=O)],1487 (w), 1367 [s, ν(C—N)], 1187 [m, ρ(CH₃)], 1158 [s, ν(P=O)], 1042 [s, δ(POC)], 1011 (m), 880 (s), 846 (m), 822 (m), 781 (w), 722 (m), 677 [m, ν(CCl)], 548 [m, δ(PNC)], 502 (m).

¹H NMR (400 MHz, DMSO-d₆, 293 K): 3.61, 3.59 (d, 24H, CH₃ [L]⁻), 3.18 (s, 12H, CH₃ [NMe₄]⁺).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were placed in calculated positions and refined with a riding model: C—H = 0.96 Å with U_iso(H) = 1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	(C₄H₁₂N)[La(C₄H₆Cl₃NO₄P)₄]
M_r	1290.73
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	294
a, b, c (Å)	12.1452 (4), 10.2003 (4), 21.2846 (7)
β (°)	94.521 (3)
V (Å³)	2628.64 (15)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.60
Crystal size (mm)	0.6 × 0.4 × 0.2

Data collection
Diffractometer	Agilent Technologies Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.694, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22447, 6050, 4597
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.134, 1.01
No. of reflections	6050
No. of parameters	296
No. of restraints	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.91
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

The structure exhibits disorder of the Cl atoms of one CCl₃ substituent. All Cl—C bond distances were restrained to be similar to each other (within a standard deviation of 0.005 Å) with a target value of 1.745 Å. U^ij values of the disordered chlorine atoms were restrained to be similar to each other (within a standard deviation of 0.02 Å²). The disorder ratio is 50 to 50.

Supporting information

CCDC reference: 2120335

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011750/mw2180sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011750/mw2180Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021011750/mw2180Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989021011750/mw2180Isup4.cdx

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Tetramethylammonium tetrakis{2,2,2-trichloro-1-[(dimethoxyphosphoryl)imino]ethanolato}lanthanum(III) top

Crystal data top

(C₄H₁₂N)[La(C₄H₆Cl₃NO₄P)₄]	F(000) = 1280
M_r = 1290.73	D_x = 1.631 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.1452 (4) Å	Cell parameters from 3067 reflections
b = 10.2003 (4) Å	θ = 3.2–23.6°
c = 21.2846 (7) Å	µ = 1.60 mm⁻¹
β = 94.521 (3)°	T = 294 K
V = 2628.64 (15) Å³	Block, colourless
Z = 2	0.6 × 0.4 × 0.2 mm

Data collection top

Agilent Technologies Xcalibur, Sapphire3 diffractometer	6050 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4597 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 16.1827 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2014)	k = −13→12
T_min = 0.694, T_max = 1.000	l = −25→27
22447 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.057P)² + 0.0726P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
6050 reflections	Δρ_max = 0.92 e Å⁻³
296 parameters	Δρ_min = −0.91 e Å⁻³
73 restraints

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	Occ. (<1)
La1	0.250000	0.21428 (4)	0.750000	0.03981 (13)
Cl1A	0.3621 (6)	0.4311 (8)	0.5516 (5)	0.161 (4)	0.5
Cl1B	0.3145 (7)	0.4844 (6)	0.5495 (4)	0.144 (3)	0.5
Cl2A	0.1378 (7)	0.4598 (8)	0.5184 (4)	0.192 (4)	0.5
Cl2B	0.1311 (6)	0.3878 (10)	0.4787 (4)	0.198 (4)	0.5
Cl3A	0.2545 (8)	0.2694 (7)	0.4592 (2)	0.173 (4)	0.5
Cl3B	0.3288 (8)	0.2511 (8)	0.4835 (4)	0.189 (4)	0.5
Cl4	0.45286 (16)	−0.0370 (2)	0.58761 (10)	0.1269 (9)
Cl5	0.63096 (17)	−0.0478 (2)	0.68243 (11)	0.1275 (8)
Cl6	0.63761 (15)	0.1310 (2)	0.57995 (9)	0.1166 (7)
P1	0.12224 (10)	0.04178 (13)	0.61305 (6)	0.0523 (3)
P2	0.51080 (11)	0.38211 (15)	0.72817 (7)	0.0647 (4)
O1	0.2329 (3)	0.3040 (3)	0.63703 (15)	0.0652 (10)
O2	0.1564 (3)	0.0524 (3)	0.68093 (14)	0.0552 (8)
O3	−0.0061 (3)	0.0420 (4)	0.60037 (19)	0.0790 (11)
O4	0.1617 (3)	−0.0966 (3)	0.59196 (15)	0.0657 (9)
O5	0.4069 (3)	0.1198 (3)	0.69257 (18)	0.0656 (10)
O6	0.4008 (3)	0.3734 (3)	0.75292 (16)	0.0596 (9)
O7	0.5136 (4)	0.5137 (4)	0.6907 (2)	0.0980 (14)
O8	0.6052 (4)	0.4070 (6)	0.7800 (2)	0.1051 (15)
N1	0.1613 (4)	0.1495 (4)	0.56501 (18)	0.0629 (11)
N2	0.5497 (3)	0.2658 (5)	0.6845 (2)	0.0689 (13)
C1	0.2094 (4)	0.2568 (5)	0.5840 (2)	0.0564 (13)
C2	0.2429 (3)	0.3432 (4)	0.52989 (18)	0.0770 (17)
C3	−0.0712 (5)	−0.0440 (9)	0.6346 (4)	0.134 (3)
H3A	−0.056390	−0.133010	0.623339	0.201*
H3B	−0.148061	−0.025051	0.624583	0.201*
H3C	−0.053309	−0.031932	0.678933	0.201*
C4	0.1430 (7)	−0.1401 (7)	0.5277 (3)	0.106 (2)
H4A	0.176063	−0.079196	0.500412	0.159*
H4B	0.064984	−0.144940	0.516385	0.159*
H4C	0.175366	−0.225158	0.523438	0.159*
C5	0.4942 (4)	0.1588 (5)	0.6742 (2)	0.0566 (12)
C6	0.5510 (4)	0.0575 (6)	0.6321 (3)	0.0686 (15)
C7	0.6023 (7)	0.5480 (8)	0.6526 (5)	0.153 (4)
H7A	0.611203	0.480202	0.622176	0.230*
H7B	0.669571	0.557443	0.679135	0.230*
H7C	0.585323	0.629264	0.631261	0.230*
C8	0.6282 (9)	0.3183 (11)	0.8254 (6)	0.193 (5)
H8A	0.607447	0.232728	0.809925	0.289*
H8B	0.587835	0.338915	0.861107	0.289*
H8C	0.705986	0.319673	0.837739	0.289*
N3	0.250000	0.7094 (6)	0.750000	0.0726 (18)
C9	0.2854 (6)	0.6266 (6)	0.8055 (3)	0.103 (2)
H9A	0.346838	0.573073	0.795873	0.154*
H9B	0.225194	0.571408	0.815623	0.154*
H9C	0.306877	0.681805	0.840903	0.154*
C10	0.3433 (5)	0.7929 (6)	0.7331 (4)	0.098 (2)
H10A	0.322433	0.839259	0.694795	0.148*
H10B	0.406334	0.738757	0.727330	0.148*
H10C	0.361400	0.854619	0.766399	0.148*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0393 (2)	0.0445 (2)	0.0364 (2)	0.000	0.00772 (15)	0.000
Cl1A	0.155 (5)	0.215 (8)	0.110 (4)	−0.118 (6)	−0.006 (4)	0.053 (6)
Cl1B	0.275 (9)	0.089 (3)	0.070 (3)	−0.080 (5)	0.027 (5)	0.002 (3)
Cl2A	0.251 (8)	0.159 (6)	0.163 (6)	0.071 (6)	0.005 (5)	0.103 (5)
Cl2B	0.185 (6)	0.237 (9)	0.158 (6)	−0.055 (6)	−0.075 (5)	0.138 (6)
Cl3A	0.343 (11)	0.137 (5)	0.049 (2)	−0.122 (6)	0.069 (4)	−0.026 (3)
Cl3B	0.271 (9)	0.138 (5)	0.183 (7)	0.040 (6)	0.173 (7)	0.041 (5)
Cl4	0.0931 (12)	0.178 (2)	0.1139 (15)	−0.0351 (13)	0.0339 (12)	−0.0808 (15)
Cl5	0.1168 (15)	0.1399 (18)	0.1283 (17)	0.0669 (14)	0.0249 (13)	0.0000 (14)
Cl6	0.1028 (13)	0.1584 (19)	0.0973 (13)	−0.0220 (12)	0.0623 (11)	−0.0242 (13)
P1	0.0515 (7)	0.0621 (8)	0.0423 (7)	−0.0098 (6)	−0.0031 (6)	0.0026 (6)
P2	0.0508 (7)	0.0657 (9)	0.0790 (10)	−0.0134 (6)	0.0141 (7)	−0.0072 (8)
O1	0.099 (3)	0.061 (2)	0.0360 (18)	−0.0053 (19)	0.0088 (19)	−0.0010 (16)
O2	0.067 (2)	0.058 (2)	0.0399 (17)	−0.0198 (16)	−0.0003 (16)	0.0034 (15)
O3	0.052 (2)	0.099 (3)	0.084 (3)	−0.005 (2)	−0.007 (2)	0.010 (2)
O4	0.081 (2)	0.067 (2)	0.0484 (19)	0.0014 (19)	0.0001 (18)	−0.0004 (17)
O5	0.059 (2)	0.062 (2)	0.082 (3)	−0.0047 (17)	0.0393 (19)	−0.0126 (19)
O6	0.0552 (19)	0.056 (2)	0.069 (2)	−0.0110 (16)	0.0149 (17)	−0.0134 (17)
O7	0.105 (3)	0.070 (3)	0.126 (4)	−0.009 (2)	0.050 (3)	0.010 (3)
O8	0.072 (3)	0.131 (4)	0.111 (4)	−0.033 (3)	−0.003 (3)	−0.023 (3)
N1	0.077 (3)	0.069 (3)	0.042 (2)	−0.019 (2)	−0.005 (2)	0.007 (2)
N2	0.049 (2)	0.078 (3)	0.082 (3)	−0.010 (2)	0.022 (2)	−0.014 (3)
C1	0.064 (3)	0.062 (3)	0.043 (3)	0.007 (3)	0.010 (2)	0.013 (2)
C2	0.109 (5)	0.073 (4)	0.048 (3)	−0.009 (4)	0.004 (3)	0.012 (3)
C3	0.063 (4)	0.194 (9)	0.143 (7)	−0.033 (5)	0.006 (5)	0.043 (7)
C4	0.154 (7)	0.105 (6)	0.057 (4)	0.012 (5)	0.005 (4)	−0.018 (4)
C5	0.049 (3)	0.076 (4)	0.047 (3)	0.003 (3)	0.016 (2)	−0.004 (3)
C6	0.053 (3)	0.094 (4)	0.062 (3)	0.000 (3)	0.019 (3)	−0.012 (3)
C7	0.148 (8)	0.114 (7)	0.212 (11)	−0.012 (6)	0.101 (8)	0.048 (7)
C8	0.168 (9)	0.215 (11)	0.183 (10)	−0.071 (8)	−0.057 (8)	0.081 (9)
N3	0.095 (5)	0.044 (3)	0.078 (4)	0.000	0.004 (4)	0.000
C9	0.162 (7)	0.071 (4)	0.071 (4)	0.034 (5)	−0.016 (4)	−0.008 (3)
C10	0.100 (5)	0.073 (4)	0.127 (6)	−0.009 (4)	0.035 (5)	−0.027 (4)

Geometric parameters (Å, º) top

La1—O1	2.566 (3)	O7—C7	1.442 (7)
La1—O1ⁱ	2.566 (3)	O8—C8	1.337 (9)
La1—O2	2.432 (3)	N1—C1	1.291 (6)
La1—O2ⁱ	2.432 (3)	N2—C5	1.292 (6)
La1—O5ⁱ	2.534 (3)	C1—C2	1.531 (6)
La1—O5	2.534 (3)	C3—H3A	0.9600
La1—O6	2.445 (3)	C3—H3B	0.9600
La1—O6ⁱ	2.445 (3)	C3—H3C	0.9600
Cl1A—C2	1.735 (5)	C4—H4A	0.9600
Cl1B—C2	1.716 (5)	C4—H4B	0.9600
Cl2A—C2	1.747 (4)	C4—H4C	0.9600
Cl2B—C2	1.733 (4)	C5—C6	1.564 (7)
Cl3A—C2	1.698 (4)	C7—H7A	0.9600
Cl3B—C2	1.764 (4)	C7—H7B	0.9600
Cl4—C6	1.751 (6)	C7—H7C	0.9600
Cl5—C6	1.756 (6)	C8—H8A	0.9600
Cl6—C6	1.756 (5)	C8—H8B	0.9600
P1—O2	1.475 (3)	C8—H8C	0.9600
P1—O3	1.561 (4)	N3—C9	1.488 (6)
P1—O4	1.568 (4)	N3—C9ⁱ	1.488 (6)
P1—N1	1.598 (4)	N3—C10ⁱ	1.484 (6)
P2—O6	1.476 (3)	N3—C10	1.484 (7)
P2—O7	1.563 (4)	C9—H9A	0.9600
P2—O8	1.548 (5)	C9—H9B	0.9600
P2—N2	1.602 (5)	C9—H9C	0.9600
O1—C1	1.240 (6)	C10—H10A	0.9600
O3—C3	1.419 (7)	C10—H10B	0.9600
O4—C4	1.439 (6)	C10—H10C	0.9600
O5—C5	1.225 (5)

O1ⁱ—La1—O1	138.20 (15)	Cl3A—C2—Cl2A	106.8 (5)
O2ⁱ—La1—O1ⁱ	71.11 (10)	C1—C2—Cl1A	111.3 (4)
O2ⁱ—La1—O1	143.90 (11)	C1—C2—Cl1B	117.3 (4)
O2—La1—O1ⁱ	143.90 (11)	C1—C2—Cl2A	105.2 (4)
O2—La1—O1	71.11 (10)	C1—C2—Cl2B	112.5 (4)
O2ⁱ—La1—O2	94.48 (15)	C1—C2—Cl3A	117.2 (4)
O2ⁱ—La1—O5	72.55 (11)	C1—C2—Cl3B	108.6 (4)
O2ⁱ—La1—O5ⁱ	77.50 (11)	O3—C3—H3A	109.5
O2—La1—O5ⁱ	72.55 (11)	O3—C3—H3B	109.5
O2—La1—O5	77.50 (11)	O3—C3—H3C	109.5
O2—La1—O6	141.22 (11)	H3A—C3—H3B	109.5
O2—La1—O6ⁱ	97.00 (12)	H3A—C3—H3C	109.5
O2ⁱ—La1—O6	97.00 (12)	H3B—C3—H3C	109.5
O2ⁱ—La1—O6ⁱ	141.22 (11)	O4—C4—H4A	109.5
O5—La1—O1ⁱ	125.40 (12)	O4—C4—H4B	109.5
O5—La1—O1	72.06 (12)	O4—C4—H4C	109.5
O5ⁱ—La1—O1ⁱ	72.06 (12)	H4A—C4—H4B	109.5
O5ⁱ—La1—O1	125.40 (12)	H4A—C4—H4C	109.5
O5ⁱ—La1—O5	135.31 (15)	H4B—C4—H4C	109.5
O6ⁱ—La1—O1ⁱ	78.01 (12)	O5—C5—N2	132.3 (5)
O6—La1—O1ⁱ	74.58 (12)	O5—C5—C6	113.6 (5)
O6ⁱ—La1—O1	74.58 (12)	N2—C5—C6	114.0 (4)
O6—La1—O1	78.01 (12)	Cl4—C6—Cl5	108.3 (3)
O6—La1—O5ⁱ	146.17 (12)	Cl4—C6—Cl6	108.0 (3)
O6ⁱ—La1—O5	146.17 (12)	Cl5—C6—Cl6	108.5 (3)
O6—La1—O5	70.98 (11)	C5—C6—Cl4	111.2 (3)
O6ⁱ—La1—O5ⁱ	70.98 (11)	C5—C6—Cl5	107.6 (4)
O6—La1—O6ⁱ	96.81 (16)	C5—C6—Cl6	113.2 (4)
O2—P1—O3	111.7 (2)	O7—C7—H7A	109.5
O2—P1—O4	106.12 (19)	O7—C7—H7B	109.5
O2—P1—N1	120.1 (2)	O7—C7—H7C	109.5
O3—P1—O4	106.0 (2)	H7A—C7—H7B	109.5
O3—P1—N1	103.4 (2)	H7A—C7—H7C	109.5
O4—P1—N1	108.8 (2)	H7B—C7—H7C	109.5
O6—P2—O7	106.9 (2)	O8—C8—H8A	109.5
O6—P2—O8	113.3 (2)	O8—C8—H8B	109.5
O6—P2—N2	118.6 (2)	O8—C8—H8C	109.5
O7—P2—N2	108.7 (3)	H8A—C8—H8B	109.5
O8—P2—O7	100.2 (3)	H8A—C8—H8C	109.5
O8—P2—N2	107.4 (3)	H8B—C8—H8C	109.5
C1—O1—La1	135.3 (3)	C9ⁱ—N3—C9	110.8 (6)
P1—O2—La1	136.36 (18)	C10—N3—C9ⁱ	108.2 (4)
C3—O3—P1	120.0 (4)	C10—N3—C9	109.9 (4)
C4—O4—P1	121.4 (4)	C10ⁱ—N3—C9ⁱ	109.9 (4)
C5—O5—La1	137.2 (3)	C10ⁱ—N3—C9	108.2 (4)
P2—O6—La1	136.72 (19)	C10ⁱ—N3—C10	110.0 (6)
C7—O7—P2	122.8 (4)	N3—C9—H9A	109.5
C8—O8—P2	120.3 (6)	N3—C9—H9B	109.5
C1—N1—P1	122.2 (3)	N3—C9—H9C	109.5
C5—N2—P2	123.4 (4)	H9A—C9—H9B	109.5
O1—C1—N1	132.9 (5)	H9A—C9—H9C	109.5
O1—C1—C2	113.9 (4)	H9B—C9—H9C	109.5
N1—C1—C2	113.2 (4)	N3—C10—H10A	109.5
Cl1A—C2—Cl2A	105.7 (5)	N3—C10—H10B	109.5
Cl1B—C2—Cl2B	106.9 (5)	N3—C10—H10C	109.5
Cl1B—C2—Cl3B	105.8 (5)	H10A—C10—H10B	109.5
Cl2B—C2—Cl3B	104.9 (5)	H10A—C10—H10C	109.5
Cl3A—C2—Cl1A	109.8 (5)	H10B—C10—H10C	109.5

La1—O1—C1—N1	17.5 (10)	O5—C5—C6—Cl6	154.3 (4)
La1—O1—C1—C2	−163.2 (3)	O6—P2—O7—C7	−171.5 (6)
La1—O5—C5—N2	10.5 (10)	O6—P2—O8—C8	63.4 (8)
La1—O5—C5—C6	−171.8 (3)	O6—P2—N2—C5	−6.4 (6)
P1—N1—C1—O1	−2.6 (9)	O7—P2—O6—La1	126.7 (3)
P1—N1—C1—C2	178.1 (3)	O7—P2—O8—C8	176.9 (8)
P2—N2—C5—O5	−0.1 (9)	O7—P2—N2—C5	−128.7 (5)
P2—N2—C5—C6	−177.8 (4)	O8—P2—O6—La1	−123.8 (3)
O1—C1—C2—Cl1A	32.5 (6)	O8—P2—O7—C7	70.2 (7)
O1—C1—C2—Cl1B	4.1 (7)	O8—P2—N2—C5	123.6 (5)
O1—C1—C2—Cl2A	−81.5 (6)	N1—P1—O2—La1	8.3 (4)
O1—C1—C2—Cl2B	−120.5 (6)	N1—P1—O3—C3	179.4 (5)
O1—C1—C2—Cl3A	160.0 (5)	N1—P1—O4—C4	−48.8 (5)
O1—C1—C2—Cl3B	123.9 (6)	N1—C1—C2—Cl1A	−148.0 (5)
O2—P1—O3—C3	−50.1 (6)	N1—C1—C2—Cl1B	−176.4 (5)
O2—P1—O4—C4	−179.4 (5)	N1—C1—C2—Cl2A	98.0 (6)
O2—P1—N1—C1	−10.0 (6)	N1—C1—C2—Cl2B	59.0 (7)
O3—P1—O2—La1	−112.9 (3)	N1—C1—C2—Cl3A	−20.5 (7)
O3—P1—O4—C4	61.8 (5)	N1—C1—C2—Cl3B	−56.6 (6)
O3—P1—N1—C1	115.2 (5)	N2—P2—O6—La1	3.5 (4)
O4—P1—O2—La1	132.1 (3)	N2—P2—O7—C7	−42.3 (7)
O4—P1—O3—C3	65.0 (6)	N2—P2—O8—C8	−69.6 (8)
O4—P1—N1—C1	−132.4 (4)	N2—C5—C6—Cl4	−149.4 (4)
O5—C5—C6—Cl4	32.5 (6)	N2—C5—C6—Cl5	92.3 (5)
O5—C5—C6—Cl5	−85.9 (5)	N2—C5—C6—Cl6	−27.5 (6)

Symmetry code: (i) −x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O6	0.96	2.35	3.184 (7)	145
C10—H10C···O2ⁱⁱ	0.96	2.33	3.218 (8)	154

Symmetry code: (ii) −x+1/2, y+1, −z+3/2.

Acknowledgements

The authors acknowledge Svitlana V. Shishkina, Head of the Department of X-ray Diffraction Study and Quantum Chemistry, SSI "Institute for Single Crystals" of the National Academy of Sciences of Ukraine for the data collection.

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