Crystal structure of a three-dimensional neodymium(III) coordination polymer, [Nd2(H2O)6(glutarato)(SO4)2]n

Yimklan, S.; Chimupala, Y.; Wongngam, S.; Kaeosamut, N.

doi:10.1107/S2056989022000159

research communications

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ISSN: 2056-9890

Volume 78| Part 2| February 2022| Pages 159-163

https://doi.org/10.1107/S2056989022000159

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Crystal structure of a three-dimensional neodymium(III) coordination polymer, [Nd₂(H₂O)₆(glutarato)(SO₄)₂]_n

Saranphong Yimklan,^a ^* Yothin Chimupala,^b Sutsiri Wongngam ^a and Nippich Kaeosamut ^a

^aDepartment of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand, and ^bDepartment of Industrial Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand
^*Correspondence e-mail: Saranphong.Yimklan@cmu.ac.th

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 14 September 2021; accepted 5 January 2022; online 11 January 2022)

A three-dimensional coordination polymer, poly[hexaaqua(μ₄-glutarato)bis(μ₃-sulfato)dineodymium(III)], [Nd₂(glutarato)(SO₄)₂(H₂O)₆]_n (glutarato^2– = C₅H₆O₄^2–), 1, consisting of cationic {Nd₂(H₂O)₆(SO₄)₂}_n²ⁿ⁺ layers linked by bridging glutarate ligands, was synthesized by the microwave-heating technique within few minutes. The crystal structure of 1 consists of two crystallographically independent TPRS-{Nd^IIIO₉} (TPRS is tricapped trigonal–prismatic geometry) units that form an edge-sharing dinuclear cluster interconnected to neighbouring dimers by the μ₃-SO₄^2– anions, yielding a cationic two-dimensional {Nd₂(H₂O)₆(SO₄)₂}_n²ⁿ⁺ sheet. Adjacent cationic layers are then linked via the μ₄-glutarato^2– ligands into a three-dimensional coordination network. Strong O—H⋯O hydrogen bonds are the predominant interaction in the crystal structure.

Keywords: crystal structure; coordination polymer; lanthanide; glutarate.

CCDC reference: 2107848

1. Chemical context

Coordination polymers (CPs) and metal–organic frameworks (MOFs) have attracted much attention because of the fascinating tuneability of their molecular architectures and functionalities that helps to adjust their properties for applications in different areas such as in sensing and magnetism, as well as catalysis. These properties are cooperatively provided by both the inorganic building units and the organic counterparts (Furukawa et al., 2013 ). Across the periodic table, the not-so-rare earth lanthanides (Ln) have become one of the promising choices for such materials because of their robust Ln—O bonds, versatile coordination geometries and high thermal stability with exotic properties, including photoluminescence and adaptive active sites for catalysis (Pagis et al., 2016 ). On the other hand, the flexibility of the organic linkers, such as aliphatic polycarboxylates, can also diversify the structural architecture that sometimes defines the macroscopic properties of the materials (Kim et al., 2017 ).

Herein, we report a microwave synthesis of a new three-dimensional coordination polymer, [Nd₂(H₂O)₆(glutarato)(SO₄)₂]_n (1). The crystal structure reveals that the glutarates act as bridging ligands binding the cationic {Nd₂(H₂O)₆(SO₄)₂}_n²ⁿ⁺ sheets into a three-dimensional network.

2. Structural commentary

The coordination network 1, [Nd₂(H₂O)₆(glutarato)(SO₄)₂]_n crystallizes in the monoclinic P2₁/c space group. There are two crystallographically independent Nd^III cations (Nd1 and Nd2), two sulfate anions, and six coordinated water molecules in the asymmetric unit, as illustrated in Fig. 1.

Figure 1
Graphical representations of (a) an extended asymmetric unit of 1 drawn with 50% probability ellipsoids, (b) coordination geometries of Nd1 (top) and Nd2 (bottom) and (c) coordination environment of Nd1 (left) and Nd2 (right). [Symmetry codes: (i) −x + 2, −y, −z; (ii) −x + 2, y - 1/2, −z − $[{1\over 2}]$ ; (iii) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iv) −x + 1, −y + 1, −z; (v) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vi) −x + 2, y + $[{1\over 2}]$ , −z − $[{1\over 2}]$ .]

Both Nd^III cations are nine-coordinated to O atoms from one bridging glutarate²⁻, two chelating glutarate²⁻, two chelating sulfate anions and three coordinated H₂O, adopting a distorted tricapped trigonal–prismatic geometry, TPRS-{Nd^IIIO₉} (see Fig. 1b), forming an edge-sharing dinuclear unit with its symmetry-related Nd^IIIO₉ polyhedron. The Nd^III—O bond distances are in the range of 2.383 (2)–2.785 (2) Å, which are reasonable and comparable to those reported for other Nd^III coordination polymers such as [Nd(H₂O)₄(glutarato)]Cl (Hussain et al., 2015 ), [Nd(H₂O)₄(glutarato)]Cl·2H₂O (Legendziewicz et al., 1999 ) and [Nd₂(H₂O)₂(glutarato)]·2H₂O (Głowiak et al., 1986 ). In contrast to the above-mentioned coordination polymers, [Nd(glutarato)(H₂O)₄]Cl (Hussain et al., 2015) and [Nd(glutarato)(H₂O)₄]Cl·2H₂O (Legendziewicz et al., 1999) consisting of cationic {Nd(H₂O)_x(glutarato)}_nⁿ⁺ (x = 2, 4) subunits compensated by uncoordinated chloride anions, each of the tetrahedral SO₄^2– ligands in 1 links three adjacent Nd^III atoms, forming a neutral two-dimensional network of [Nd₂(H₂O)₆(glutarato)(SO₄)₂]_n. The S—O bond distances are in the range 1.449 (3)–1.485 (2) Å, with O—S—O angles ranging from 107.78 (16) to 111.67 (15)°. The flexible glutarate linker exhibits a (μ₄-κ²O:κO′:κ²O′′:κO′′′ coordination mode with an anti–anti conformation as depicted in Fig. 2a. There are six crystallographically independent water molecules completing the coordination sites of the two Nd^III atoms (three H₂O molecules for each Nd^III atom, Fig. 2b).

Figure 2
Depictions of (a) the coordination modes of the glutarate and the sulfate ligands in 1 and (b) seven of the eleven crystallographically independent hydrogen bonds (dashed green lines) with bond distances. [Symmetry codes: (i) −x + 2, −y, −z; (ii) −x + 2, y − $[{1\over 2}]$ , −z − $[{1\over 2}]$ ; (iii) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iv) −x + 1, −y + 1, −z; (v) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vi) −x + 2, y + $[{1\over 2}]$ , −z − $[{1\over 2}]$ ; (vii) x + 1, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (viii) x − 1, y, z; (ix) −x + 1, y + $[{1\over 2}]$ , −z − $[{1\over 2}]$ ; (x) x, y, z − 1.]

3. Supramolecular features

The polymeric structure of 1 can be described as a three-dimensional non-porous framework, which is constructed from edge-sharing TPRS-{Nd^IIIO₉} polyhedra linked through sulfate anions, acting as tritopic inorganic linkers, into a cationic [Nd₂(H₂O)₆(SO₄)₂]_n²ⁿ⁺ sheets parallel to the (011) layers, as illustrated in Fig. 3a. It is noteworthy that these sheets also contain large inorganic [Nd(SO₄)]₄ rings further stabilized by O—H⋯O hydrogen bonds between the water molecules and sulfate anions (Table 1). Eventually, the final three-dimensional network is formed by connecting these adjacent cationic sheets by the glutarate ligands (Fig. 3b). This three-dimensional arrangement also features O—H⋯O hydrogen bonds between two water molecules or between a water molecule and oxygen atoms of the glutarate ligands (Fig. 2b). In total, all but one hydrogen atom from the six crystallographically independent water molecules are involved in hydrogen bonding (Table 1). Analysis of these hydrogen bonds revealed thirteen different first-order graph sets (Bernstein et al., 1995 ) consisting of five rings and eight different chains.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O16W—H16A⋯O3ⁱ	0.85	1.91	2.709 (4)	155
O16W—H16B⋯O6ⁱⁱ	0.85	1.94	2.774 (3)	165
O17W—H17A⋯O12Wⁱⁱⁱ	0.81 (2)	2.38 (4)	2.966 (4)	130 (4)
O17W—H17B⋯O3ⁱ	0.84 (2)	2.09 (2)	2.903 (4)	165 (4)
O12W—H12A⋯O6^iv	0.85	2.10	2.825 (4)	143
O12W—H12B⋯O17W^v	0.85	2.07	2.904 (4)	166
O13W—H13A⋯O12^vi	0.85	1.95	2.733 (3)	153
O13W—H13B⋯O3^vii	0.85	1.99	2.745 (4)	148
O14W—H14A⋯O13W^viii	0.85 (2)	2.13 (2)	2.966 (4)	165 (4)
O18—H18A⋯O6^ix	0.83 (2)	2.03 (2)	2.826 (3)	160 (3)
O18—H18B⋯O5ⁱⁱ	0.81 (2)	2.00 (2)	2.805 (3)	170 (4)
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) ; (v) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (vii) ; (viii) ; (ix) $[-x+2, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Figure 3
Views of (a) the [Nd₂(H₂O)₆(SO₄)₂]_n²ⁿ⁺ sheet and (b) the three-dimensional framework of 1.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) confirms that no Nd^III coordination polymer containing both glutarate^2– and SO₄^2– has been reported. However, several related polymeric structures, viz. catena-[(μ-pentanedioato)tetraaquaneodymium chloride] (NEMXIP; Hussain et al., 2015), catena-[(μ₄-glutarato)tetraaquadineodymium chloride dihydrate] (DIQZAE01; Marsh, 2005 ), catena-[bis(μ₄-pentane-1,5-dionato)(μ₂-pentane-1,5-dionato)diaquadineodymium(III) tetrahydrate] (FAQYUR; Legendziewicz et al., 1999) and catena-[tris(μ₃-glutarato-O,O,O′,O′′,O′′′)diaquadineodymium(III) dihydrate] (FAFGAU; Głowiak et al., 1986), have been reported.

5. Synthesis and crystallization

Complex 1 was synthesized by dissolving Nd₂(SO₄)₃·8H₂O (1 mmol, 0.721 g), glutaric acid (1 mmol, 0.132 g), and 4,4′-bipyridine (1 mmol, 0.156 g) in 40.0 mL of deionized water under ambient conditions. The solution was transferred into an open glass reactor and then irradiated by microwaves (800 W) for 10 minutes. The solution was let to cool to ambient temperature. Pale-purple block-shaped crystals crystallized from the solution within a few minutes. FT–IR (ATR Mode, cm⁻¹) of 1: ν_stretch(O—H) 3364, ν_stretch(C—H) 2990, ν_as(COO⁻) 1531, ν_s(COO⁻) 1430, δ(O—H) 1355, ν_s(S—O) 1101, ν_s(S—O) 1077, ν_s(SO₄^2–) 596.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Carbon-bound H atoms were positioned geometrically (C—H = 0.97 Å) and constrained using the riding-model approximation with U_iso(H) = 1.2U_eq(C). The H atoms from the water molecules were located in the residual electron-density map, and where necessary, refined with distance and angle restraints or riding on the parent oxygen atom.

Table 2
Experimental details

Crystal data
Chemical formula	[Nd₂(C₅H₆O₄)(SO₄)₂(H₂O)₆]
M_r	718.79
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.5461 (1), 12.6621 (1), 8.8883 (1)
β (°)	95.287 (1)
V (Å³)	1742.19 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	6.23
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	SuperNova, Single source at offset/far, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.448, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	38711, 3830, 3482
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.045, 1.08
No. of reflections	3830
No. of parameters	268
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)	0.62, −0.88
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2107848

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022000159/jq2009sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022000159/jq2009Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022000159/jq2009Isup3.mol

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: SHELXT2018/2 (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).

Poly[hexaaqua(µ₄-glutarato)bis(µ₃-sulfato)dineodymium(III)] top

Crystal data top

[Nd₂(C₅H₆O₄)(SO₄)₂(H₂O)₆]	F(000) = 1376
M_r = 718.79	D_x = 2.740 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.5461 (1) Å	Cell parameters from 25026 reflections
b = 12.6621 (1) Å	θ = 2.1–27.3°
c = 8.8883 (1) Å	µ = 6.23 mm⁻¹
β = 95.287 (1)°	T = 293 K
V = 1742.19 (3) Å³	Block, clear light violet
Z = 4	0.2 × 0.2 × 0.2 mm

Data collection top

SuperNova, Single source at offset/far, HyPix3000 diffractometer	3830 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	3482 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.067
ω scans	θ_max = 27.4°, θ_min = 2.1°
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2014)	h = −20→19
T_min = 0.448, T_max = 1.000	k = −16→16
38711 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.0106P)² + 1.2155P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.003
3830 reflections	Δρ_max = 0.62 e Å⁻³
268 parameters	Δρ_min = −0.88 e Å⁻³
9 restraints	Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00033 (5)

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. The structure of 1 was solved in the space group P21/c (No. 14) using direct methods in the SHELXT (Sheldrick, 2015a) structure-solution program and refined by full-matrix least-squares minimization on F2 using SHELXL 2018/3 (Sheldrick, 2015b).

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

	x	y	z	U_iso*/U_eq
Nd2	1.07588 (2)	0.09859 (2)	−0.12226 (2)	0.01075 (6)
Nd1	0.42661 (2)	0.43378 (2)	−0.18797 (2)	0.01254 (6)
S2	1.05205 (6)	0.38265 (6)	−0.21038 (9)	0.01194 (18)
S1	0.41004 (6)	0.35878 (6)	0.21539 (9)	0.01539 (19)
O11	0.93262 (15)	0.07269 (16)	−0.0510 (2)	0.0157 (5)
O6	1.11665 (15)	0.45391 (16)	−0.1313 (2)	0.0180 (5)
O5	1.04359 (16)	0.28751 (16)	−0.1153 (2)	0.0177 (5)
O8	0.96805 (15)	0.43635 (16)	−0.2326 (2)	0.0155 (5)
O16W	1.16897 (17)	0.0982 (2)	−0.3338 (3)	0.0265 (6)
H16A	1.222796	0.084873	−0.321649	0.040*
H16B	1.152057	0.070890	−0.418758	0.040*
O17W	1.21843 (18)	0.1988 (2)	−0.0366 (3)	0.0321 (7)
H17A	1.218 (3)	0.2626 (15)	−0.044 (5)	0.048*
H17B	1.259 (2)	0.177 (3)	−0.083 (4)	0.048*
O12	0.80870 (15)	0.03120 (18)	0.0300 (3)	0.0220 (6)
O12W	0.27085 (16)	0.37303 (19)	−0.2316 (3)	0.0258 (6)
H12A	0.237228	0.422979	−0.210018	0.039*
H12B	0.258297	0.362463	−0.325853	0.039*
O9	0.56170 (17)	0.41489 (18)	−0.0404 (3)	0.0236 (6)
O2	0.48805 (16)	0.42067 (18)	0.2617 (3)	0.0247 (6)
O13W	0.36280 (16)	0.5016 (2)	−0.4426 (3)	0.0283 (6)
H13A	0.309153	0.513771	−0.439262	0.042*
H13B	0.364813	0.453202	−0.508542	0.042*
O10	0.67742 (18)	0.4309 (2)	0.1157 (3)	0.0335 (7)
O14W	0.5138 (2)	0.3668 (2)	−0.4039 (3)	0.0425 (8)
H14A	0.545 (3)	0.400 (3)	−0.463 (4)	0.064*
H14B	0.498 (3)	0.313 (2)	−0.451 (5)	0.064*
O1	0.39367 (18)	0.3531 (2)	0.0516 (3)	0.0348 (7)
C4	0.8121 (2)	0.1900 (3)	−0.1158 (4)	0.0213 (8)
H4A	0.776496	0.167837	−0.205583	0.026*
H4B	0.856900	0.236004	−0.147741	0.026*
C1	0.6402 (2)	0.3905 (3)	−0.0018 (4)	0.0178 (8)
C5	0.8539 (2)	0.0942 (2)	−0.0408 (4)	0.0148 (8)
C2	0.6882 (3)	0.3205 (3)	−0.1001 (4)	0.0297 (10)
H2A	0.715651	0.364043	−0.171662	0.036*
H2B	0.647082	0.274906	−0.157345	0.036*
C3	0.7565 (2)	0.2524 (3)	−0.0148 (4)	0.0249 (9)
H3A	0.728270	0.203229	0.048365	0.030*
H3B	0.793796	0.297267	0.051188	0.030*
O18	0.97596 (18)	0.14621 (19)	−0.3490 (3)	0.0206 (6)
H18A	0.945 (2)	0.095 (2)	−0.376 (4)	0.031*
H18B	0.992 (2)	0.172 (3)	−0.425 (3)	0.031*
O7	1.08197 (15)	0.34921 (17)	−0.3553 (2)	0.0160 (5)
O4	0.4228 (2)	0.2533 (2)	0.2767 (3)	0.0447 (8)
O3	0.33686 (18)	0.4071 (2)	0.2790 (3)	0.0431 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Nd2	0.01192 (11)	0.01076 (10)	0.00957 (10)	0.00054 (7)	0.00104 (8)	0.00014 (7)
Nd1	0.01289 (12)	0.01314 (11)	0.01148 (10)	0.00009 (7)	0.00057 (8)	0.00022 (7)
S2	0.0158 (5)	0.0112 (4)	0.0089 (4)	0.0013 (3)	0.0013 (3)	0.0007 (3)
S1	0.0187 (5)	0.0147 (4)	0.0133 (4)	−0.0029 (4)	0.0047 (4)	0.0003 (3)
O11	0.0119 (13)	0.0187 (12)	0.0161 (13)	0.0037 (10)	0.0000 (11)	−0.0004 (10)
O6	0.0206 (14)	0.0169 (12)	0.0154 (12)	−0.0016 (11)	−0.0037 (11)	−0.0019 (10)
O5	0.0272 (15)	0.0134 (12)	0.0128 (12)	0.0019 (11)	0.0028 (11)	0.0042 (9)
O8	0.0177 (14)	0.0140 (12)	0.0152 (12)	0.0039 (10)	0.0036 (11)	0.0022 (9)
O16W	0.0175 (15)	0.0443 (17)	0.0177 (14)	−0.0005 (13)	0.0022 (12)	−0.0048 (12)
O17W	0.0298 (18)	0.0261 (15)	0.0389 (18)	−0.0074 (14)	−0.0057 (14)	0.0082 (14)
O12	0.0154 (14)	0.0191 (13)	0.0313 (14)	0.0002 (11)	0.0010 (12)	0.0079 (11)
O12W	0.0194 (15)	0.0312 (15)	0.0261 (14)	−0.0007 (12)	−0.0024 (12)	−0.0030 (12)
O9	0.0178 (15)	0.0285 (14)	0.0241 (14)	0.0071 (11)	0.0006 (12)	0.0010 (11)
O2	0.0240 (16)	0.0300 (14)	0.0193 (14)	−0.0128 (12)	−0.0021 (12)	0.0040 (11)
O13W	0.0205 (15)	0.0439 (17)	0.0201 (13)	0.0049 (13)	0.0003 (12)	−0.0037 (12)
O10	0.0281 (17)	0.0360 (16)	0.0342 (16)	0.0110 (13)	−0.0090 (14)	−0.0181 (13)
O14W	0.061 (2)	0.0426 (19)	0.0262 (17)	0.0041 (17)	0.0190 (16)	−0.0004 (14)
O1	0.0471 (19)	0.0486 (17)	0.0084 (12)	−0.0274 (15)	0.0015 (12)	−0.0004 (12)
C4	0.020 (2)	0.0195 (19)	0.024 (2)	0.0058 (16)	0.0006 (16)	0.0038 (15)
C1	0.015 (2)	0.0190 (18)	0.0188 (19)	0.0056 (15)	−0.0017 (16)	−0.0020 (15)
C5	0.015 (2)	0.0144 (17)	0.0149 (18)	0.0013 (15)	−0.0009 (15)	−0.0031 (14)
C2	0.029 (2)	0.038 (2)	0.022 (2)	0.0139 (19)	−0.0004 (18)	−0.0049 (17)
C3	0.030 (2)	0.023 (2)	0.0209 (19)	0.0139 (17)	0.0010 (17)	−0.0023 (16)
O18	0.0267 (16)	0.0193 (14)	0.0155 (13)	−0.0062 (11)	−0.0003 (12)	0.0043 (11)
O7	0.0188 (14)	0.0185 (12)	0.0111 (11)	0.0050 (10)	0.0030 (10)	−0.0002 (9)
O4	0.057 (2)	0.0187 (15)	0.0566 (19)	−0.0073 (14)	−0.0032 (17)	0.0138 (14)
O3	0.0171 (16)	0.069 (2)	0.0430 (18)	0.0099 (14)	0.0029 (14)	−0.0298 (15)

Geometric parameters (Å, º) top

Nd2—O11	2.393 (2)	O11—C5	1.265 (4)
Nd2—O11ⁱ	2.670 (2)	O16W—H16A	0.8508
Nd2—O5	2.446 (2)	O16W—H16B	0.8501
Nd2—O8ⁱⁱ	2.487 (2)	O17W—H17A	0.811 (18)
Nd2—O16W	2.476 (3)	O17W—H17B	0.836 (18)
Nd2—O17W	2.606 (3)	O12—C5	1.268 (4)
Nd2—O12ⁱ	2.514 (2)	O12W—H12A	0.8534
Nd2—O18	2.502 (2)	O12W—H12B	0.8534
Nd2—O7ⁱⁱⁱ	2.456 (2)	O9—C1	1.275 (4)
Nd1—O12W	2.536 (2)	O13W—H13A	0.8513
Nd1—O9^iv	2.785 (2)	O13W—H13B	0.8508
Nd1—O9	2.383 (2)	O10—C1	1.255 (4)
Nd1—O2^iv	2.397 (2)	O14W—H14A	0.854 (19)
Nd1—O13W	2.536 (2)	O14W—H14B	0.831 (18)
Nd1—O10^iv	2.481 (3)	C4—H4A	0.9700
Nd1—O14W	2.592 (3)	C4—H4B	0.9700
Nd1—O1	2.457 (2)	C4—C5	1.502 (4)
Nd1—O4^v	2.390 (2)	C4—C3	1.523 (5)
S2—O6	1.479 (2)	C1—C2	1.491 (5)
S2—O5	1.485 (2)	C2—H2A	0.9700
S2—O8	1.470 (2)	C2—H2B	0.9700
S2—O7	1.472 (2)	C2—C3	1.516 (5)
S1—O2	1.471 (2)	C3—H3A	0.9700
S1—O1	1.457 (2)	C3—H3B	0.9700
S1—O4	1.449 (3)	O18—H18A	0.827 (18)
S1—O3	1.452 (3)	O18—H18B	0.814 (18)

O11—Nd2—O11ⁱ	68.86 (8)	O8—S2—O6	109.74 (13)
O11—Nd2—O5	85.94 (8)	O8—S2—O5	109.14 (14)
O11—Nd2—O8ⁱⁱ	78.84 (7)	O8—S2—O7	111.34 (13)
O11—Nd2—O16W	145.48 (8)	O7—S2—O6	109.63 (14)
O11—Nd2—O17W	140.93 (8)	O7—S2—O5	108.47 (13)
O11—Nd2—O12ⁱ	118.53 (7)	O1—S1—O2	111.67 (15)
O11—Nd2—O18	73.89 (8)	O4—S1—O2	107.78 (16)
O11—Nd2—O7ⁱⁱⁱ	74.65 (7)	O4—S1—O1	109.63 (16)
O5—Nd2—O11ⁱ	139.33 (7)	O4—S1—O3	109.07 (19)
O5—Nd2—O8ⁱⁱ	140.68 (7)	O3—S1—O2	108.79 (16)
O5—Nd2—O16W	99.03 (8)	O3—S1—O1	109.83 (17)
O5—Nd2—O17W	71.78 (8)	Nd2—O11—Nd2ⁱ	111.14 (8)
O5—Nd2—O12ⁱ	140.61 (7)	C5—O11—Nd2	156.8 (2)
O5—Nd2—O18	70.81 (7)	C5—O11—Nd2ⁱ	91.97 (19)
O5—Nd2—O7ⁱⁱⁱ	72.67 (7)	S2—O5—Nd2	138.58 (13)
O8ⁱⁱ—Nd2—O11ⁱ	66.58 (7)	S2—O8—Nd2^vi	130.54 (13)
O8ⁱⁱ—Nd2—O17W	137.65 (9)	Nd2—O16W—H16A	122.8
O8ⁱⁱ—Nd2—O12ⁱ	77.46 (7)	Nd2—O16W—H16B	121.4
O8ⁱⁱ—Nd2—O18	70.18 (7)	H16A—O16W—H16B	104.6
O16W—Nd2—O11ⁱ	119.98 (8)	Nd2—O17W—H17A	118 (3)
O16W—Nd2—O8ⁱⁱ	75.90 (8)	Nd2—O17W—H17B	111 (3)
O16W—Nd2—O17W	71.46 (9)	H17A—O17W—H17B	107 (3)
O16W—Nd2—O12ⁱ	78.27 (8)	C5—O12—Nd2ⁱ	99.3 (2)
O16W—Nd2—O18	75.62 (9)	Nd1—O12W—H12A	109.7
O17W—Nd2—O11ⁱ	108.23 (8)	Nd1—O12W—H12B	109.0
O12ⁱ—Nd2—O11ⁱ	49.67 (7)	H12A—O12W—H12B	104.3
O12ⁱ—Nd2—O17W	70.17 (8)	Nd1—O9—Nd1^iv	109.09 (9)
O18—Nd2—O11ⁱ	126.89 (7)	C1—O9—Nd1^iv	88.51 (19)
O18—Nd2—O17W	124.49 (8)	C1—O9—Nd1	161.0 (2)
O18—Nd2—O12ⁱ	142.32 (8)	S1—O2—Nd1^iv	142.78 (14)
O7ⁱⁱⁱ—Nd2—O11ⁱ	70.19 (7)	Nd1—O13W—H13A	109.5
O7ⁱⁱⁱ—Nd2—O8ⁱⁱ	135.02 (7)	Nd1—O13W—H13B	109.6
O7ⁱⁱⁱ—Nd2—O16W	139.53 (8)	H13A—O13W—H13B	104.6
O7ⁱⁱⁱ—Nd2—O17W	68.32 (8)	C1—O10—Nd1^iv	103.6 (2)
O7ⁱⁱⁱ—Nd2—O12ⁱ	84.15 (8)	Nd1—O14W—H14A	131 (3)
O7ⁱⁱⁱ—Nd2—O18	132.77 (8)	Nd1—O14W—H14B	120 (3)
O12W—Nd1—O9^iv	108.50 (8)	H14A—O14W—H14B	104 (3)
O12W—Nd1—O14W	110.17 (10)	S1—O1—Nd1	144.54 (15)
O9—Nd1—O12W	146.52 (8)	H4A—C4—H4B	107.7
O9—Nd1—O9^iv	70.91 (9)	C5—C4—H4A	108.8
O9—Nd1—O2^iv	75.27 (8)	C5—C4—H4B	108.8
O9—Nd1—O13W	141.04 (8)	C5—C4—C3	113.8 (3)
O9—Nd1—O10^iv	119.29 (8)	C3—C4—H4A	108.8
O9—Nd1—O14W	83.11 (10)	C3—C4—H4B	108.8
O9—Nd1—O1	74.03 (9)	O9—C1—Nd1^iv	66.63 (18)
O9—Nd1—O4^v	89.01 (9)	O9—C1—C2	120.3 (3)
O2^iv—Nd1—O12W	137.40 (8)	O10—C1—Nd1^iv	52.67 (17)
O2^iv—Nd1—O9^iv	70.71 (8)	O10—C1—O9	118.8 (3)
O2^iv—Nd1—O13W	71.12 (8)	O10—C1—C2	120.8 (3)
O2^iv—Nd1—O10^iv	85.99 (9)	C2—C1—Nd1^iv	167.7 (3)
O2^iv—Nd1—O14W	73.06 (9)	O11—C5—Nd2ⁱ	63.04 (17)
O2^iv—Nd1—O1	136.14 (8)	O11—C5—O12	118.9 (3)
O13W—Nd1—O12W	71.15 (8)	O11—C5—C4	121.6 (3)
O13W—Nd1—O9^iv	114.29 (7)	O12—C5—Nd2ⁱ	55.97 (16)
O13W—Nd1—O14W	68.79 (9)	O12—C5—C4	119.5 (3)
O10^iv—Nd1—O12W	67.24 (8)	C4—C5—Nd2ⁱ	175.3 (3)
O10^iv—Nd1—O9^iv	48.43 (8)	C1—C2—H2A	108.7
O10^iv—Nd1—O13W	77.67 (9)	C1—C2—H2B	108.7
O10^iv—Nd1—O14W	144.63 (9)	C1—C2—C3	114.2 (3)
O14W—Nd1—O9^iv	139.56 (9)	H2A—C2—H2B	107.6
O1—Nd1—O12W	74.58 (8)	C3—C2—H2A	108.7
O1—Nd1—O9^iv	70.08 (8)	C3—C2—H2B	108.7
O1—Nd1—O13W	144.93 (9)	C4—C3—H3A	108.7
O1—Nd1—O10^iv	82.52 (10)	C4—C3—H3B	108.7
O1—Nd1—O14W	132.11 (10)	C2—C3—C4	114.2 (3)
O4^v—Nd1—O12W	70.57 (9)	C2—C3—H3A	108.7
O4^v—Nd1—O9^iv	140.98 (9)	C2—C3—H3B	108.7
O4^v—Nd1—O2^iv	137.22 (10)	H3A—C3—H3B	107.6
O4^v—Nd1—O13W	102.45 (9)	Nd2—O18—H18A	110 (3)
O4^v—Nd1—O10^iv	135.22 (10)	Nd2—O18—H18B	123 (3)
O4^v—Nd1—O14W	65.60 (10)	H18A—O18—H18B	107 (3)
O4^v—Nd1—O1	72.38 (10)	S2—O7—Nd2^v	141.35 (13)
O6—S2—O5	108.45 (13)	S1—O4—Nd1ⁱⁱⁱ	164.56 (18)

Nd2—O11—C5—Nd2ⁱ	−174.9 (5)	O8—S2—O5—Nd2	128.04 (19)
Nd2—O11—C5—O12	−178.5 (3)	O8—S2—O7—Nd2^v	32.0 (3)
Nd2ⁱ—O11—C5—O12	−3.5 (3)	O9—C1—C2—C3	−148.9 (3)
Nd2—O11—C5—C4	4.0 (7)	O2—S1—O1—Nd1	−18.1 (4)
Nd2ⁱ—O11—C5—C4	179.0 (3)	O2—S1—O4—Nd1ⁱⁱⁱ	−137.7 (7)
Nd2ⁱ—O12—C5—O11	3.8 (3)	O10—C1—C2—C3	34.9 (5)
Nd2ⁱ—O12—C5—C4	−178.6 (2)	O1—S1—O2—Nd1^iv	31.5 (3)
Nd1—O9—C1—Nd1^iv	158.3 (7)	O1—S1—O4—Nd1ⁱⁱⁱ	−15.9 (8)
Nd1—O9—C1—O10	166.0 (5)	C1—C2—C3—C4	−173.6 (3)
Nd1^iv—O9—C1—O10	7.7 (3)	C5—C4—C3—C2	−157.3 (3)
Nd1^iv—O9—C1—C2	−168.6 (3)	C3—C4—C5—O11	−134.7 (3)
Nd1—O9—C1—C2	−10.3 (9)	C3—C4—C5—O12	47.8 (4)
Nd1^iv—O10—C1—O9	−8.9 (4)	O7—S2—O5—Nd2	6.6 (2)
Nd1^iv—O10—C1—C2	167.4 (3)	O7—S2—O8—Nd2^vi	−59.51 (19)
Nd1^iv—C1—C2—C3	89.6 (11)	O4—S1—O2—Nd1^iv	151.9 (3)
O6—S2—O5—Nd2	−112.4 (2)	O4—S1—O1—Nd1	−137.5 (3)
O6—S2—O8—Nd2^vi	62.05 (19)	O3—S1—O2—Nd1^iv	−89.9 (3)
O6—S2—O7—Nd2^v	−89.7 (2)	O3—S1—O1—Nd1	102.7 (3)
O5—S2—O8—Nd2^vi	−179.23 (14)	O3—S1—O4—Nd1ⁱⁱⁱ	104.4 (8)
O5—S2—O7—Nd2^v	152.09 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O16W—H16A···O3^vii	0.85	1.91	2.709 (4)	155
O16W—H16B···O6^v	0.85	1.94	2.774 (3)	165
O17W—H17A···O12W^viii	0.81 (2)	2.38 (4)	2.966 (4)	130 (4)
O17W—H17B···O3^vii	0.84 (2)	2.09 (2)	2.903 (4)	165 (4)
O12W—H12A···O6^ix	0.85	2.10	2.825 (4)	143
O12W—H12B···O17W^x	0.85	2.07	2.904 (4)	166
O13W—H13A···O12^xi	0.85	1.95	2.733 (3)	153
O13W—H13B···O3^xii	0.85	1.99	2.745 (4)	148
O14W—H14A···O13W^xiii	0.85 (2)	2.13 (2)	2.966 (4)	165 (4)
O18—H18A···O6ⁱⁱ	0.83 (2)	2.03 (2)	2.826 (3)	160 (3)
O18—H18B···O5^v	0.81 (2)	2.00 (2)	2.805 (3)	170 (4)

Symmetry codes: (ii) −x+2, y−1/2, −z−1/2; (v) x, −y+1/2, z−1/2; (vii) x+1, −y+1/2, z−1/2; (viii) x+1, y, z; (ix) x−1, y, z; (x) x−1, −y+1/2, z−1/2; (xi) −x+1, y+1/2, −z−1/2; (xii) x, y, z−1; (xiii) −x+1, −y+1, −z−1.

Acknowledgements

This research was partially supported by the CMU Junior Research Fellowship Program, Faculty of Science, Chiang Mai University, the Development and Promotion of Science and Technology Talent Project (DPST) through a research fund for graduates with first placement. The authors thank W. Booncharoen for chemical and physical analysis services during the COVID-19 pandemic. SY and YC acknowledge A. Rujiwatra for supervision in the DPST research fund. SW and NK also thank the DPST project for their research grants.

Funding information

Funding for this research was provided by: Faculty of Science, Chiang Mai University; Development and Promotion of Science and Technology Talent Project (DPST) through a research fund for graduates with first placement; CMU Junior Research Fellowship Program.

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