key: cord-0691859-b88b9e4k
authors: Yimklan, Saranphong; Chimupala, Yothin; Wongngam, Sutsiri; Kaeosamut, Nippich
title: Crystal structure of a three-dimensional neodymium(III) coordination polymer, [Nd(2)(H(2)O)(6)(glutarato)(SO(4))(2)]( n )
date: 2022-01-11
journal: Acta Crystallogr E Crystallogr Commun
DOI: 10.1107/s2056989022000159
sha: c73b0376c2f9f23bbaeb233fba22793b559bc081
doc_id: 691859
cord_uid: b88b9e4k

A three-dimensional coordination polymer, poly[hexa­aqua­(μ(4)-glutarato)bis(μ(3)-sulfato)­dineodymium(III)], [Nd(2)(glutarato)(SO(4))(2)(H(2)O)(6)]( n ) (glutarato(2–) = C(5)H(6)O(4) (2–)), 1, consisting of cationic {Nd(2)(H(2)O)(6)(SO(4))(2)}( n ) (2n+) 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(III)O(9)} (TPRS is tricapped trigonal–prismatic geometry) units that form an edge-sharing dinuclear cluster inter­connected to neighbouring dimers by the μ(3)-SO(4) (2–) anions, yielding a cationic two-dimensional {Nd(2)(H(2)O)(6)(SO(4))(2)}( n ) (2n+) sheet. Adjacent cationic layers are then linked via the μ(4)-glutarato(2–) ligands into a three-dimensional coordination network. Strong O—H⋯O hydrogen bonds are the predominant inter­action in the crystal structure.

A three-dimensional coordination polymer, poly[hexaaqua( 4 -glutarato)bis-( 3 -sulfato)dineodymium(III)], [Nd 2 (glutarato)(SO 4 ) 2 (H 2 O) 6 ] n (glutarato 2-= C 5 H 6 O 4 2-), 1, consisting of cationic {Nd 2 (H 2 O) 6 (SO 4 ) 2 } n 2n+ 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 III O 9 } (TPRS is tricapped trigonal-prismatic geometry) units that form an edge-sharing dinuclear cluster interconnected to neighbouring dimers by the 3 -SO 4 2anions, yielding a cationic two-dimensional {Nd 2 (H 2 O) 6 (SO 4 ) 2 } n 2n+ sheet. Adjacent cationic layers are then linked via the 4glutarato 2ligands into a three-dimensional coordination network. Strong O-HÁ Á ÁO hydrogen bonds are the predominant interaction in the crystal structure.

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 threedimensional coordination polymer, [Nd 2 (H 2 O) 6 (glutarato)-(SO 4 ) 2 ] n (1). The crystal structure reveals that the glutarates act as bridging ligands binding the cationic {Nd 2 (H 2 O) 6 -(SO 4 ) 2 } n 2n+ sheets into a three-dimensional network.

The coordination network 1, [Nd 2 (H 2 O) 6 (glutarato)(SO 4 ) 2 ] n crystallizes in the monoclinic P2 1 /c space group. There are two crystallographically independent Nd III cations (Nd1 and Nd2), ISSN 2056-9890 two sulfate anions, and six coordinated water molecules in the asymmetric unit, as illustrated in Fig. 1 (Głowiak et al., 1986) . In contrast to the above-mentioned coordination polymers, [Nd(glutarato)(H 2 O) 4 ]Cl (Hussain et al., 2015) and [Nd(glutarato)(H 2 O) 4 ]ClÁ2H 2 O (Legendziewicz et al., 1999) 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) Àx + 2, Ày, Àz; (ii) Àx + 2, y -1/2, Àz À 1 2 ; (iii) x, Ày + 1 2 , z + 1 2 ; (iv) Àx + 1, Ày + 1, Àz; (v) x, Ày + 1 2 , z À 1 2 ; (vi) Àx + 2, y + 1 2 , Àz À 1 2 .] molecules completing the coordination sites of the two Nd III atoms (three H 2 O molecules for each Nd III atom, Fig. 2b ).

The polymeric structure of 1 can be described as a threedimensional non-porous framework, which is constructed from edge-sharing TPRS-{Nd III O 9 } polyhedra linked through sulfate anions, acting as tritopic inorganic linkers, into a cationic [Nd 2 (H 2 O) 6 (SO 4 ) 2 ] n 2n+ sheets parallel to the (011) layers, as illustrated in Fig. 3a . It is noteworthy that these sheets also contain large inorganic [Nd(SO 4 )] 4 rings further stabilized by O-HÁ Á ÁO 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-HÁ Á ÁO 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. 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) Àx + 2, Ày, Àz; (ii) Àx + 2, y À 1 2 , Àz À 1 2 ; (iii) x, Ày + 1 2 , z + 1 2 ; (iv) Àx + 1, Legendziewicz et al., 1999) and Głowiak et al., 1986) , have been reported. 

Ày + 1, Àz; (v) x, Ày + 1 2 , z À 1 2 ; (vi) Àx + 2, y + 1 2 , Àz À 1 2 ; (vii) x + 1, Ày + 1 2 , z À 1 2 ; (viii) x À 1, y, z; (ix) Àx + 1, y + 1 2 , Àz À 1 2 ; (x) x, y, z À 1.] related polymeric structures, viz. catena-[(-pentanedio- ato)tetraaquaneodymium chloride] (NEMXIP; Hussain et al., 2015), catena-[( 4 -glutarato)tetraaquadineodymium chloride dihydrate] (DIQZAE01; Marsh, 2005), catena-[bis( 4 -pen- tane-1,5-dionato)( 2 -pentane-1,5-dionato)diaquadineodym- ium(III) tetrahydrate] (FAQYUR;catena-[tris( 3 -glutarato-O,O,O 0 ,O 00 ,O 000 )diaquadineo- dymium(III) dihydrate] (FAFGAU;

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 (3) 170 (4) Symmetry codes: (i) x þ 1; Ày þ 1 2 ; z À 1 2 ; (ii) x; Ày þ 1 2 ; z À 1 2 ; (iii) x þ 1; y; z; (iv) x À 1; y; z; (v) x À 1; Ày þ 1 2 ; z À 1 2 ; (vi) Àx þ 1; y þ 1 2 ; Àz À 1 2 ; (vii) x; y; z À 1; (viii) Àx þ 1; Ày þ 1; Àz À 1; (ix) Àx þ 2; y À 1 2 ; Àz À 1 2 . 

Views of (a) the [Nd 2 (H 2 O) 6 (SO 4 ) 2 ] n 2n+ sheet and (b) the three-dimensional framework of 1.

necessary, refined with distance and angle restraints or riding on the parent oxygen atom.

Acta Cryst. 

Crystal data 

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) .

x y z U iso */U eq Nd2 1.07588 (2) 0.09859 (2) −0.12226 (2) 0.01075 (6) 

CrysAlis PRO. Agilent Technologies Ltd

Acta Cryst. B61, 359. Pagis

14 (14) O11-Nd2-O8 ii 78

) O3-S1-O2 108.79 (16) O5-Nd2-O16W 99.03 (8) O3-S1-O1 109

O4 v -Nd1-O2 iv

) 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

Nd2-O11-C5-Nd2 i −

) 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

51 (19) Nd1 iv -C1-C2-C3 89

O6-S2-O8-Nd2 vi 62.05 (19) O3-S1-O2-Nd1 iv −

O6-S2-O7-Nd2 v −89.7 (2) O3-S1-O1-Nd1

−z; (ii) −x+2, y−1/2, −z−1/2; (iii) x, −y+1/2, z+1/2; (iv) −x+1, −y+1

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 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.

Hydrogen-bond geometry (Å, º)