2-Methyl­imidazolium tetra­kis­(2-thenoyltri­fluoroacetonato-κ2O,O′)neodymium(III)

Bravo-Arredondo, J.M.; Bernès, S.; Mejía, K.; Anzaldo, B.; Ramírez, E.; Moro, D.

doi:10.1107/S2414314625005693

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 6| June 2025| x250569

https://doi.org/10.1107/S2414314625005693

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2-Methylimidazolium tetrakis(2-thenoyltrifluoroacetonato-κ²O,O′)neodymium(III)

José Manuel Bravo-Arredondo,^a,^b Sylvain Bernès,^c ^* Karen Mejía,^d Bertin Anzaldo,^e Erick Ramírez ^f and David Moro ^e

^aPosgrado en Dispositivos Semiconductores, Benemérita Universidad Autónoma de Puebla, Prolongación 14 Sur, IC5, 72570 Puebla, Pue., Mexico, ^bFacultad de Ciencias Básicas, Ingeniería y Tecnología, Universidad Autónoma de Tlaxcala, De Apizaquito, 20 de Noviembre, 90401 Apizaco, Tlax., Mexico, ^cInstituto de Física Luis Rivera Terrazas, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico, ^dCentro de Química del Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, IC8, C.U., San Manuel, 72570 Puebla, Pue., Mexico, ^eFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico, and ^fInstituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: [email protected]

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 June 2025; accepted 23 June 2025; online 27 June 2025)

The title complex, (C₄H₇N₂)[Nd(C₈H₄F₃O₂S)₄], is a salt formed via the acid–base reaction between 2-thenoyltrifluoroacetone (HTTA) and 2-methylimidazole (MeIm) in presence of neodymium(III) trifluoromethanesulfonate. The resulting compound features [Nd(TTA)₄]⁻ anions with the central rare-earth metal cation placed on a twofold rotation axis, and [MeImH]⁺ cations, disordered over an inversion centre. Cations and anions are linked through N—H⋯O hydrogen bonds to form zigzag chains running along [001].

Keywords: crystal structure; neodymium; 2-thenoyltrifluoroacetone; disorder; hydrogen bonds.

CCDC reference: 2466617

Structure description

2-Thenoyltrifluoroacetone (HTTA) is a β-diketone ligand with chelating ability for rare-earth ions that can be used to produce highly luminescent complexes of Eu³⁺, Tb³⁺ and Sm³⁺, with high quantum yields and long luminescence lifetimes, because non-radiative decay pathways are minimized in the rigid coordination environment (Gujar et al., 2019 ). The ligand is also able to sensitize lanthanide-centred emission via an efficient antenna effect. Nd³⁺ has sharp and well-defined f–f transitions, which makes it ideal for near-infrared luminescence applications. By coordinating this metal with β-diketonates like TTA⁻, one can expect the development of more efficient luminescent materials, with practical applications in optoelectronics, catalysts and biomedicine (Ahmed et al., 2020 ).

In this context, we synthesized the title compound, [MeImH][Nd(TTA)₄] using MeIm (2-methylimidazole), HTTA, and neodymium(III) trifluoromethanesulfonate as starting materials. During the sonochemical reaction, an acid–base reaction occurs between MeIm (pK_b = 6.1) and HTTA (pK_a = 7.4) to form the title salt. The anion is placed on the twofold rotation axis in space group C2/c, while the cation is disordered over an inversion centre, with occupancy fixed to 1/2 in the asymmetric unit. The central ion Nd³⁺ forms a slightly distorted square-antiprismatic polyhedron with eight O atoms of the TTA⁻ ligands (Fig. 1). The distortion is reflected in Nd—O bond lengths in the range 2.396 (2) to 2.4758 (18) Å, which are comparable to bond lengths observed in other salts of the [Nd(TTA)₄]⁻ anion crystallized with pyridinium (Leipoldt et al., 1977 ), ammonium (Cary et al., 2018 ) or a derivative of diphenyliodonium (Chen et al., 1997 ). The anion [Ln(TTA)₄]⁻ has also been characterized with all other lanthanides, except with Ln = Ho and Ln = Lu. The coordination geometry is systematically close to square-antiprismatic, with idealized point group D_4d (e.g. Assunção et al., 2025 ; Ln = Eu). Ligands TTA⁻ are nearly planar: the dihedral angle between the thiophene and β-diketonate moieties is 13.91 (16) or 5.30 (16)°. The angle formed between the planes of the six-membered chelate rings Nd1–O1–C1–C2–C3–O3 and Nd1–O11–C11–C12–C13–O13 in the asymmetric unit is 89.45 (7)°, indicating an almost orthogonal arrangement for the independent TTA⁻ ligands.

Figure 1
Structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Only one disordered cation is shown for clarity. Non-labelled S and O atoms are generated by symmetry operation 1 − x, y, $[{1\over 2}]$ − z. Only H atoms belonging to the NH groups in the cation are given. The antiprismatic coordination polyhedron around Nd1 is represented in the inset.

Supramolecular analysis of the title compound reveals intermolecular contacts between anions and cations, involving NH groups in the cation as donors and O3 as acceptor (Table 1 and Fig. 2). Zigzag chains alternating cations and anions are formed, running along [001]. These chains are stacked in the crystal with no significant contacts. Since cations are then sandwiched by two thiophene rings belonging to neighbouring anions along the chain, weak π–π interactions consolidate the crystal structure. In the asymmetric unit, the centroid-to-centroid separation between the thiophene ring S2 and the imidazole ring is 4.212 (6) Å, and corresponding mean planes form a dihedral angle of 23.4 (6)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.86	2.03	2.865 (6)	163
N2—H2A⋯O3	0.86	2.06	2.904 (6)	168
Symmetry code: (i) .

Figure 2
Part of the crystal structure, viewed nearly down [100]. One supramolecular chain is shown, with N—H⋯O hydrogen bonds represented as blue dashed bonds. All H atoms not involved in hydrogen-bonding have been omitted for clarity.

Synthesis and crystallization

Crystals of [MeImH][Nd(TTA)₄] were prepared via a sonochemical route using an Nd³⁺:HTTA = 1:2.5 stoichiometric ratio, starting from 1 mmol (0.591 g) of Nd(CF₃SO₃)₃ dissolved in 25 ml of methanol and mixed with 25 ml of the ligand solution [2.5 mmol (0.555 g) of HTTA and 2 mmol (0.164 g) of MeIm] in deionized water. All solutions were stirred, mixed, and sonicated at room temperature using an Ultrasonic Processor equipment UP400St, applying a frequency of 24 kHz and power of 400 W with 1 pulsation per second for 20 min, until precipitation occurred. After a few hours at room temperature, the precipitate was separated from the mother liquor by centrifugation and washed with deionized water to remove soluble byproducts and/or excess of precursor materials. The dried product was kept at 343 K overnight, affording single crystals suitable for X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The cation [MeImH]⁺ is placed close to an inversion centre, and is thus equally disordered over two positions by symmetry. The occupancy for the cation in the asymmetric unit was fixed to 1/2. All H atoms were placed in idealized positions (Sheldrick, 2015b ).

Table 2
Experimental details

Crystal data
Chemical formula	(C₄H₇N₂)[Nd(C₈H₄F₃O₂S)₄]
M_r	1112.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	17.3191 (4), 12.6547 (2), 20.5387 (4)
β (°)	103.772 (2)
V (Å³)	4372.01 (15)
Z	4
Radiation type	Ag Kα, λ = 0.56083 Å
μ (mm⁻¹)	0.78
Crystal size (mm)	0.31 × 0.26 × 0.24

Data collection
Diffractometer	Stoe Stadivari
Absorption correction	Multi-scan (X-AREA; Stoe & Cie, 2019 )
T_min, T_max	0.556, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	97427, 8697, 7163
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.782

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.113, 1.06
No. of reflections	8697
No. of parameters	313
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.90
Computer programs: X-AREA (Stoe & Cie, 2019), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2466617

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625005693/wm4231sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625005693/wm4231Isup2.hkl

checkCIF report

Computing details top

2-Methylimidazolium tetrakis(2-thenoyltrifluoroacetonato-κ²O,O')neodymium(III) top

Crystal data top

(C₄H₇N₂)[Nd(C₈H₄F₃O₂S)₄]	F(000) = 2196
M_r = 1112.04	D_x = 1.689 Mg m⁻³
Monoclinic, C2/c	Ag Kα radiation, λ = 0.56083 Å
a = 17.3191 (4) Å	Cell parameters from 122785 reflections
b = 12.6547 (2) Å	θ = 1.9–29.2°
c = 20.5387 (4) Å	µ = 0.78 mm⁻¹
β = 103.772 (2)°	T = 295 K
V = 4372.01 (15) Å³	Irregular, blue
Z = 4	0.31 × 0.26 × 0.24 mm

Data collection top

Stoe Stadivari diffractometer	8697 independent reflections
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source	7163 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	R_int = 0.043
Detector resolution: 5.81 pixels mm^-1	θ_max = 26.0°, θ_min = 1.9°
ω scans	h = −27→27
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2019)	k = −18→19
T_min = 0.556, T_max = 1.000	l = −32→32
97427 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0519P)² + 6.0925P] where P = (F_o² + 2F_c²)/3
8697 reflections	(Δ/σ)_max = 0.001
313 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.90 e Å⁻³
0 constraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Nd1	0.500000	0.38687 (2)	0.250000	0.03908 (6)
S1	0.36020 (8)	0.07268 (11)	0.11099 (5)	0.0853 (3)
O1	0.41250 (13)	0.23740 (15)	0.21178 (10)	0.0508 (4)
C1	0.39885 (15)	0.1532 (2)	0.23872 (13)	0.0435 (5)
F1	0.3888 (2)	0.2515 (3)	0.45231 (13)	0.1088 (10)
C2	0.41016 (19)	0.1387 (2)	0.30859 (14)	0.0508 (6)
H2	0.400999	0.072079	0.324391	0.061*
F2	0.51077 (18)	0.2131 (2)	0.46517 (11)	0.0966 (8)
S2	0.32140 (5)	0.68267 (7)	0.30984 (5)	0.0663 (2)
F3	0.4226 (3)	0.0935 (2)	0.43956 (12)	0.1309 (15)
O3	0.45289 (13)	0.31300 (15)	0.34528 (10)	0.0519 (4)
C3	0.43400 (18)	0.2183 (2)	0.35402 (13)	0.0499 (6)
C4	0.4388 (3)	0.1920 (3)	0.42796 (17)	0.0738 (11)
F4	0.71200 (14)	0.6641 (2)	0.43086 (17)	0.1057 (10)
C5	0.36846 (18)	0.0630 (2)	0.19456 (14)	0.0508 (6)
F5	0.73633 (12)	0.50159 (18)	0.43148 (12)	0.0720 (5)
F6	0.74347 (15)	0.5903 (4)	0.34738 (16)	0.1279 (14)
C6	0.3428 (3)	−0.0367 (3)	0.21092 (18)	0.0749 (11)
H6	0.342232	−0.058169	0.254091	0.090*
C7	0.3182 (4)	−0.0996 (3)	0.1533 (3)	0.1059 (19)
H7	0.298623	−0.167868	0.154069	0.127*
C8	0.3258 (3)	−0.0518 (4)	0.0976 (2)	0.0946 (15)
H8	0.313345	−0.083671	0.055615	0.114*
C11	0.47677 (16)	0.61847 (19)	0.33016 (14)	0.0446 (5)
O11	0.44749 (11)	0.53626 (15)	0.30053 (10)	0.0489 (4)
C12	0.56012 (17)	0.6335 (2)	0.35716 (17)	0.0511 (6)
H12	0.578136	0.699386	0.374301	0.061*
C13	0.61449 (15)	0.5539 (2)	0.35866 (14)	0.0455 (5)
O13	0.60391 (12)	0.46054 (15)	0.33646 (10)	0.0500 (4)
C14	0.70171 (17)	0.5786 (3)	0.39209 (18)	0.0564 (7)
C15	0.42182 (15)	0.7013 (2)	0.34063 (13)	0.0442 (5)
C16	0.43723 (18)	0.7944 (2)	0.37833 (15)	0.0521 (6)
H16	0.487658	0.819560	0.398658	0.063*
C17	0.3646 (2)	0.8451 (3)	0.38110 (18)	0.0625 (8)
H17	0.362778	0.907832	0.404259	0.075*
C18	0.2991 (2)	0.7944 (3)	0.3473 (2)	0.0672 (9)
H18	0.247536	0.817743	0.344799	0.081*
N1	0.5374 (5)	0.5365 (5)	0.5489 (3)	0.0672 (17)	0.5
H1A	0.529815	0.579440	0.579218	0.081*	0.5
N2	0.5165 (6)	0.4413 (6)	0.4631 (3)	0.0714 (19)	0.5
H2A	0.492977	0.410787	0.426307	0.086*	0.5
C21	0.4825 (6)	0.5068 (19)	0.4964 (11)	0.070 (4)	0.5
C22	0.5920 (11)	0.4282 (12)	0.4934 (7)	0.079 (4)	0.5
H22	0.627250	0.383783	0.478873	0.094*	0.5
C23	0.6100 (10)	0.4887 (11)	0.5485 (6)	0.073 (3)	0.5
H23	0.658822	0.496792	0.578961	0.087*	0.5
C24	0.3995 (9)	0.5422 (14)	0.4791 (8)	0.097 (5)	0.5
H24A	0.365313	0.483663	0.482293	0.146*	0.5
H24B	0.386518	0.569207	0.434144	0.146*	0.5
H24C	0.392314	0.596802	0.509566	0.146*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd1	0.04478 (10)	0.03509 (8)	0.03947 (9)	0.000	0.01416 (7)	0.000
S1	0.1074 (8)	0.0947 (7)	0.0497 (4)	−0.0175 (6)	0.0106 (5)	−0.0124 (4)
O1	0.0579 (11)	0.0472 (9)	0.0457 (9)	−0.0091 (8)	0.0094 (8)	−0.0007 (7)
C1	0.0419 (11)	0.0438 (11)	0.0446 (12)	−0.0046 (9)	0.0095 (9)	−0.0045 (9)
F1	0.141 (3)	0.132 (2)	0.0769 (16)	−0.033 (2)	0.0713 (18)	−0.0225 (15)
C2	0.0627 (16)	0.0455 (12)	0.0450 (13)	−0.0166 (11)	0.0146 (12)	−0.0038 (9)
F2	0.117 (2)	0.116 (2)	0.0475 (11)	−0.0292 (17)	0.0014 (12)	0.0016 (12)
S2	0.0474 (4)	0.0646 (5)	0.0862 (6)	0.0010 (3)	0.0143 (4)	−0.0178 (4)
F3	0.254 (4)	0.0848 (16)	0.0529 (13)	−0.078 (2)	0.0341 (19)	0.0033 (11)
O3	0.0697 (12)	0.0464 (9)	0.0460 (9)	−0.0154 (8)	0.0265 (9)	−0.0084 (7)
C3	0.0585 (15)	0.0526 (13)	0.0419 (12)	−0.0170 (12)	0.0185 (11)	−0.0056 (10)
C4	0.108 (3)	0.070 (2)	0.0467 (15)	−0.036 (2)	0.0250 (18)	−0.0092 (14)
F4	0.0641 (13)	0.0690 (14)	0.160 (3)	0.0003 (11)	−0.0209 (15)	−0.0394 (16)
C5	0.0529 (14)	0.0501 (13)	0.0461 (13)	−0.0021 (11)	0.0051 (11)	−0.0091 (10)
F5	0.0547 (10)	0.0712 (12)	0.0823 (14)	0.0083 (9)	0.0007 (10)	0.0047 (10)
F6	0.0552 (13)	0.243 (4)	0.0871 (19)	−0.0286 (18)	0.0194 (13)	0.047 (2)
C6	0.113 (3)	0.0473 (15)	0.0555 (17)	−0.0206 (17)	0.0030 (19)	−0.0096 (13)
C7	0.153 (5)	0.060 (2)	0.089 (3)	−0.025 (3)	−0.002 (3)	−0.023 (2)
C8	0.104 (3)	0.093 (3)	0.072 (3)	−0.003 (3)	−0.007 (2)	−0.040 (2)
C11	0.0472 (12)	0.0408 (11)	0.0480 (12)	−0.0004 (9)	0.0154 (10)	−0.0020 (9)
O11	0.0450 (9)	0.0439 (9)	0.0598 (11)	−0.0013 (7)	0.0163 (8)	−0.0127 (8)
C12	0.0442 (12)	0.0396 (11)	0.0690 (17)	−0.0025 (9)	0.0123 (12)	−0.0091 (11)
C13	0.0429 (12)	0.0436 (11)	0.0504 (13)	−0.0022 (9)	0.0117 (10)	0.0001 (9)
O13	0.0503 (10)	0.0433 (9)	0.0548 (11)	0.0033 (7)	0.0089 (8)	−0.0053 (7)
C14	0.0434 (13)	0.0528 (14)	0.0712 (19)	−0.0011 (11)	0.0100 (13)	0.0008 (13)
C15	0.0433 (12)	0.0419 (11)	0.0485 (12)	0.0015 (9)	0.0133 (10)	−0.0030 (9)
C16	0.0554 (15)	0.0487 (13)	0.0519 (14)	0.0109 (11)	0.0123 (12)	−0.0075 (11)
C17	0.0682 (19)	0.0487 (14)	0.074 (2)	0.0105 (14)	0.0232 (16)	−0.0099 (14)
C18	0.0555 (17)	0.0618 (18)	0.088 (2)	0.0146 (14)	0.0246 (17)	−0.0015 (16)
N1	0.099 (5)	0.060 (3)	0.048 (3)	−0.021 (4)	0.029 (4)	−0.013 (2)
N2	0.108 (6)	0.066 (4)	0.048 (3)	−0.035 (4)	0.033 (4)	−0.017 (3)
C21	0.095 (11)	0.070 (6)	0.048 (5)	−0.032 (10)	0.026 (9)	−0.004 (4)
C22	0.104 (10)	0.066 (5)	0.077 (8)	−0.023 (5)	0.043 (8)	−0.013 (5)
C23	0.086 (7)	0.074 (6)	0.057 (5)	−0.027 (5)	0.017 (5)	−0.004 (4)
C24	0.084 (8)	0.113 (19)	0.091 (15)	−0.030 (11)	0.016 (12)	0.023 (9)

Geometric parameters (Å, º) top

Nd1—O13ⁱ	2.396 (2)	C7—H7	0.9300
Nd1—O13	2.396 (2)	C8—H8	0.9300
Nd1—O1ⁱ	2.4340 (19)	C11—O11	1.250 (3)
Nd1—O1	2.4340 (19)	C11—C12	1.430 (4)
Nd1—O11ⁱ	2.4346 (18)	C11—C15	1.466 (3)
Nd1—O11	2.4346 (17)	C12—C13	1.374 (4)
Nd1—O3	2.4758 (18)	C12—H12	0.9300
Nd1—O3ⁱ	2.4758 (18)	C13—O13	1.263 (3)
S1—C8	1.683 (5)	C13—C14	1.535 (4)
S1—C5	1.693 (3)	C15—C16	1.400 (4)
O1—C1	1.249 (3)	C16—C17	1.424 (4)
C1—C2	1.413 (4)	C16—H16	0.9300
C1—C5	1.475 (4)	C17—C18	1.345 (5)
F1—C4	1.330 (5)	C17—H17	0.9300
C2—C3	1.369 (4)	C18—H18	0.9300
C2—H2	0.9300	N1—C21	1.31 (2)
F2—C4	1.325 (5)	N1—C23	1.398 (19)
S2—C18	1.698 (4)	N1—H1A	0.8600
S2—C15	1.720 (3)	N2—C21	1.30 (2)
F3—C4	1.312 (4)	N2—C22	1.32 (2)
O3—C3	1.266 (3)	N2—H2A	0.8600
C3—C4	1.538 (4)	C21—C24	1.47 (2)
F4—C14	1.330 (4)	C22—C23	1.340 (13)
C5—C6	1.404 (4)	C22—H22	0.9300
F5—C14	1.316 (4)	C23—H23	0.9300
F6—C14	1.306 (4)	C24—H24A	0.9600
C6—C7	1.406 (5)	C24—H24B	0.9600
C6—H6	0.9300	C24—H24C	0.9600
C7—C8	1.327 (8)

O13ⁱ—Nd1—O13	134.20 (9)	C6—C7—H7	123.4
O13ⁱ—Nd1—O1ⁱ	147.31 (7)	C7—C8—S1	112.9 (3)
O13—Nd1—O1ⁱ	76.30 (7)	C7—C8—H8	123.5
O13ⁱ—Nd1—O1	76.30 (7)	S1—C8—H8	123.5
O13—Nd1—O1	147.31 (7)	O11—C11—C12	123.6 (2)
O1ⁱ—Nd1—O1	78.00 (10)	O11—C11—C15	117.7 (2)
O13ⁱ—Nd1—O11ⁱ	70.90 (6)	C12—C11—C15	118.6 (2)
O13—Nd1—O11ⁱ	73.91 (7)	C11—O11—Nd1	134.77 (17)
O1ⁱ—Nd1—O11ⁱ	118.29 (7)	C13—C12—C11	122.3 (2)
O1—Nd1—O11ⁱ	137.14 (7)	C13—C12—H12	118.9
O13ⁱ—Nd1—O11	73.91 (7)	C11—C12—H12	118.9
O13—Nd1—O11	70.90 (6)	O13—C13—C12	129.6 (3)
O1ⁱ—Nd1—O11	137.15 (7)	O13—C13—C14	113.2 (2)
O1—Nd1—O11	118.28 (7)	C12—C13—C14	117.2 (2)
O11ⁱ—Nd1—O11	78.11 (9)	C13—O13—Nd1	130.54 (18)
O13ⁱ—Nd1—O3	113.71 (7)	F6—C14—F5	105.6 (3)
O13—Nd1—O3	83.79 (7)	F6—C14—F4	108.1 (3)
O1ⁱ—Nd1—O3	75.45 (7)	F5—C14—F4	105.0 (3)
O1—Nd1—O3	70.39 (6)	F6—C14—C13	111.0 (3)
O11ⁱ—Nd1—O3	148.98 (7)	F5—C14—C13	112.3 (3)
O11—Nd1—O3	74.30 (7)	F4—C14—C13	114.3 (3)
O13ⁱ—Nd1—O3ⁱ	83.79 (7)	C16—C15—C11	129.7 (3)
O13—Nd1—O3ⁱ	113.71 (7)	C16—C15—S2	111.2 (2)
O1ⁱ—Nd1—O3ⁱ	70.39 (6)	C11—C15—S2	118.89 (19)
O1—Nd1—O3ⁱ	75.45 (7)	C15—C16—C17	110.3 (3)
O11ⁱ—Nd1—O3ⁱ	74.30 (7)	C15—C16—H16	124.8
O11—Nd1—O3ⁱ	148.98 (7)	C17—C16—H16	124.8
O3—Nd1—O3ⁱ	135.63 (9)	C18—C17—C16	114.2 (3)
C8—S1—C5	92.2 (2)	C18—C17—H17	122.9
C1—O1—Nd1	133.56 (17)	C16—C17—H17	122.9
O1—C1—C2	124.5 (2)	C17—C18—S2	112.1 (2)
O1—C1—C5	117.7 (2)	C17—C18—H18	124.0
C2—C1—C5	117.8 (2)	S2—C18—H18	124.0
C3—C2—C1	122.9 (2)	C21—N1—C23	110.4 (10)
C3—C2—H2	118.6	C21—N1—H1A	124.8
C1—C2—H2	118.6	C23—N1—H1A	124.8
C18—S2—C15	92.21 (16)	C21—N2—C22	110.7 (9)
C3—O3—Nd1	127.90 (16)	C21—N2—H2A	124.6
O3—C3—C2	130.3 (3)	C22—N2—H2A	124.6
O3—C3—C4	112.9 (2)	N2—C21—N1	106.5 (10)
C2—C3—C4	116.8 (3)	N2—C21—C24	127.4 (17)
F3—C4—F2	107.4 (4)	N1—C21—C24	126.1 (18)
F3—C4—F1	106.5 (4)	N2—C22—C23	109.4 (17)
F2—C4—F1	106.0 (3)	N2—C22—H22	125.3
F3—C4—C3	114.9 (3)	C23—C22—H22	125.3
F2—C4—C3	110.4 (3)	C22—C23—N1	102.9 (15)
F1—C4—C3	111.2 (4)	C22—C23—H23	128.6
C6—C5—C1	129.4 (3)	N1—C23—H23	128.6
C6—C5—S1	110.7 (2)	C21—C24—H24A	109.5
C1—C5—S1	119.9 (2)	C21—C24—H24B	109.5
C5—C6—C7	110.9 (4)	H24A—C24—H24B	109.5
C5—C6—H6	124.5	C21—C24—H24C	109.5
C7—C6—H6	124.5	H24A—C24—H24C	109.5
C8—C7—C6	113.3 (4)	H24B—C24—H24C	109.5
C8—C7—H7	123.4

Nd1—O1—C1—C2	25.1 (4)	C11—C12—C13—O13	2.6 (5)
Nd1—O1—C1—C5	−155.3 (2)	C11—C12—C13—C14	−177.1 (3)
O1—C1—C2—C3	3.2 (5)	C12—C13—O13—Nd1	23.9 (5)
C5—C1—C2—C3	−176.4 (3)	C14—C13—O13—Nd1	−156.4 (2)
Nd1—O3—C3—C2	−22.7 (5)	O13—C13—C14—F6	74.2 (4)
Nd1—O3—C3—C4	157.8 (2)	C12—C13—C14—F6	−106.0 (4)
C1—C2—C3—O3	−3.1 (6)	O13—C13—C14—F5	−43.7 (4)
C1—C2—C3—C4	176.4 (3)	C12—C13—C14—F5	136.0 (3)
O3—C3—C4—F3	−177.5 (4)	O13—C13—C14—F4	−163.1 (3)
C2—C3—C4—F3	2.9 (6)	C12—C13—C14—F4	16.6 (4)
O3—C3—C4—F2	−55.9 (4)	O11—C11—C15—C16	171.8 (3)
C2—C3—C4—F2	124.5 (3)	C12—C11—C15—C16	−5.0 (4)
O3—C3—C4—F1	61.5 (4)	O11—C11—C15—S2	−1.8 (3)
C2—C3—C4—F1	−118.1 (3)	C12—C11—C15—S2	−178.7 (2)
O1—C1—C5—C6	−174.7 (3)	C18—S2—C15—C16	−1.2 (2)
C2—C1—C5—C6	5.0 (5)	C18—S2—C15—C11	173.5 (2)
O1—C1—C5—S1	4.9 (4)	C11—C15—C16—C17	−172.8 (3)
C2—C1—C5—S1	−175.5 (2)	S2—C15—C16—C17	1.2 (3)
C8—S1—C5—C6	−1.1 (3)	C15—C16—C17—C18	−0.6 (4)
C8—S1—C5—C1	179.3 (3)	C16—C17—C18—S2	−0.3 (4)
C1—C5—C6—C7	179.9 (4)	C15—S2—C18—C17	0.9 (3)
S1—C5—C6—C7	0.3 (5)	C22—N2—C21—N1	0.3 (19)
C5—C6—C7—C8	0.9 (8)	C22—N2—C21—C24	179.8 (18)
C6—C7—C8—S1	−1.8 (8)	C23—N1—C21—N2	0.7 (18)
C5—S1—C8—C7	1.7 (5)	C23—N1—C21—C24	−178.7 (17)
C12—C11—O11—Nd1	−16.4 (4)	C21—N2—C22—C23	−1 (2)
C15—C11—O11—Nd1	166.90 (18)	N2—C22—C23—N1	1.6 (19)
O11—C11—C12—C13	−6.8 (5)	C21—N1—C23—C22	−1.5 (18)
C15—C11—C12—C13	169.9 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···F3ⁱⁱ	0.93	2.60	3.429 (4)	149
N1—H1A···O3ⁱⁱⁱ	0.86	2.03	2.865 (6)	163
N2—H2A···O3	0.86	2.06	2.904 (6)	168
C24—H24B···S2	0.96	2.91	3.852 (15)	167

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

Funding information

Funding for this research was provided by: CONAHCyT (grant No. 268178; scholarship No. 175419 to J. M. Bravo-Arredondo; scholarship No. 546339 to E. Ramírez).

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