New Magnetic Nickel(II)-Thiolate Cluster-Based Coordination Polymer

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A new magnetic nickel(II)-thiolate cluster-based coordination polymer constructed from 2-mercaptonicotinic acid Ning Yuan, Chongbin Tian, Tianlu Sheng, Shengmin Hu, and Xintao Wu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01709 • Publication Date (Web): 10 Apr 2018 Downloaded from http://pubs.acs.org on April 10, 2018

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Crystal Growth & Design

A New Magnetic Nickel(II)-Thiolate Cluster-Based Coordination Polymer Constructed from 2Mercaptonicotinic Acid Ning Yuan,a* Chongbin Tian,b Tianlu Sheng,b Shengmin Hu,b Xintao Wub* a

School of Chemical & Environmental Engineering, China University of Mining & Technology,

Beijing 100083, China b

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou 350002, China Keywords Nickel-thiolate, cluster, coordination polymer, magnetism, 2-mercaptonicotinic acid

Abstract

A

new

nickel(II)-thiolate

cluster-based

coordination

polymer

[Ni9(mna)10(H2O)10]·(H2O)13 (1) has been constructed by the employment of nickel acetate tetrahydrate and 2-mercaptonicotinic acid (mna) as starting reactants under hydrothermal condition and further characterized by single-crystal X-ray diffraction, infrared spectroscopy, CHN elemental analysis, thermogravimetric analysis, powder X-ray diffraction and magnetic analysis. Single-crystal X-ray diffraction discloses that compound 1 consists of heptanuclear nickel-sulfur [Ni7S10] cluster and binuclear nickel-oxygen [Ni2O2] node, which results in the formation of covalent two-dimensional (4,4)-topological network. Intriguingly, nickel(II)-

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thiolate cluster [Ni7S10] plays the role of secondary building unit (SBU) in this infinite coordination polymer 1 instead of discrete and tiara-like cluster structure as previously reported literature. Furthermore, compound 1 displays a tightly packed three-dimensional construction through π···π stacking interactions. In addition, magnetic susceptibility measurements reveal that 1 displays overall anti-ferromagnetism interactions.

The past decades have witnessed a rapid development of the design and synthesis of coordination cluster-based compounds, owing to their intriguing structural features1–4 and their promising applications in varieties of fields, such as heterogeneous catalysis, gas molecules capture, magnetism and luminescence sensing.5–12 A considerable number of coordination clusters have been synthesized with the employment of bridging ligands including oxygen and/or nitrogen donors. For example, different types of multicarboxylate ligands have been adopted for the construction of this class of compounds.13 Meanwhile, coordination clusters on the basis of sulfur-containing ligands have also been investigated, and plenty of structures have been synthesized typically by the assembly of thiolates and d-block metal ions. As to nickel(II)-sulfur cluster-based compounds, most of the known structures display tiara-like [Ni(µ-SR)]n cluster configurations, and more than forty examples of such structures have been documented up to data.14–17 Zhang and co-workers reported tiara-like nickel(II)-thiolate clusters by employing two different thiolate bridging ligands and explored their nonlinear optical properties.14 Very recently, a novel hexagonal octanuclear nickel cluster with bipyramidal configuration has also been reported by Hamaguchi et al.18 Our research group has focused on the chemistry of cluster-based compounds for some time19 and developed a series of new tiara-like nickel(II)-thiolate clusters by in situ cleavage of disulfide bond recently.20–22 However, the previously reported structures usually exhibit discrete

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structures rather than act as SBUs in an infinite coordination polymer. To the best of our knowledge, only very limited examples with nickel(II)-sulfur coordination cluster-based coordination polymers have been exploited, and it is highly desirable to obtain this class of compounds and investigate their related properties.23 For the preparation of such infinite nickel(II)-sulfur cluster-based structures, a heterocyclic ligand 2-mercaptonicotinic acid (mna) has attracted our attention. This unique ligand contains potential oxygen, nitrogen and sulfur donors, and has been employed to synthesize coordination polymers by reaction with either d-block metal or lanthanide(III) ions.24–29 Most of the reported structures exhibit simple coordination polymer or isolated Ag(I) cluster configurations, and it is quite difficult to obtain compounds containing coordination clusters with high nuclearity. However, it is still a promising candidate for the construction of nickel(II)-sulfur cluster by consideration of its crowding coordination surroundings and the affiliation of nickel(II) with sulfur donor in this ligand. Herein, we present a new magnetic coordination cluster-based coordination

polymer

with

two-dimensional

framework

formulated

as

[Ni9(mna)10(H2O)10]·(H2O)13 (1; mna = 2-mercaptonicotinic acid) employing this mna ligand under hydrothermal condition. This compound comprises an unprecedented hepta-nuclear shieldlike nickel(II)-sulfur cluster acting as SBUs. Furthermore, the magnetic properties of this compound have also been investigated in detail in this article. Compound 1 was hydrothermally synthesized by 2-mercaptonicotinic acid (mna) and Ni(OAc)2·4H2O in an equivalent molar ratio at 180 °C. When the nickel(II) salt was replaced with NiX 2 (X = Cl − ,

1

2

SO 24− , NO3− , etc) , no crystalline products can be obtained. This may

probably be interpreted by the buffering effect of acetic anion that benefits the assembly of nickel(II) ion and ligand for the formation of 1. Single-crystal X-ray crystallography reveals that

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complex

1

crystallizes

in

monoclinic

space

group

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P21/c

with

general

formula

[Ni9(mna)10(H2O)10]·(H2O)13, whose structure can be described as a two-dimensional wave-like (4,4)-topological network constructed with binuclear nickel nodes and octanuclear nickel clusters acting as spacers (Figures 1 and 2). The crystallographic data and other pertinent information are summarized in Table 1.

Table 1. Crystallographic Data and Refinement Details for 1.a Compound 1 Formula Ni9C60H78N10S10O43 Mr 2476.31 Cryst syst monoclinic Space group P2(1)/c a/Å 19.373(4) b/Å 22.210(5) c/Å 20.488(5) β/deg 94.885(4) 3 Vol/Å 8784(3) Z 4 dcalcd, g/cm3 1.873 µ(mm-1) 2.222 temp, K 293(2) F(000) 5056 R(int) 0.0550 GOF on F2 0.991 R 0.0595 Rw 0.1827 a R = Σ(||Fo|-|Fc||)/Σ|Fo|. Rw = {Σw[(Fo2-Fc2 )2]/Σw[(Fo2)2]}1/2, w = 1/[σ2(Fo2)+(aP)2+bP], P = 2 (Fo +2Fc2)/3. a = 0.1518, b = 10.9820.

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Figure 1. (a) View of the asymmetric unit of 1; (b) and the skeleton of the shield-shaped heptanuclear nickel-sulfur cluster [Ni7S10].

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Figure 2. The schematic representation of 3D supermolecular structure of 1 assembled by π···π stacking interaction. The asymmetric unit of complex 1 consists of an octanuclear nickel cluster and another nickel ion acting as node in the two-dimensional network (half of the binuclear nickel-oxygen node discussed below) as well as thirteen free water molecules. There are five types of coordination modes for nine crystallographically independent Ni(II) ions, whose coordination number are all six and coordinated surroundings are generally viewed as distorted octahedral geometries (Figure 1). (a) Ni1 and Ni2 are bound to four different ligands with six sulfur atoms and two oxygen atoms. (b) Ni4 and Ni6 are coordinated to three ligands via three sulfur atoms, two oxygen atoms and one nitrogen atom. (c) Both Ni3 and Ni8 are attached to three mna ligands with a bichelation mode each. (d) Ni7 is connected by two sulfur atoms and two oxygen atoms of carboxylate groups from two different mna ligands as well as two water molecules. (e) Six

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oxygen atoms coordinate to Ni5 and Ni9, among which Ni5 is coordinated to three atoms of carboxylate groups and another three ones of water molecules, whereas Ni9 to one atom of carboxylate groups and five ones of water molecules. Among such, it should be noted that type b is rarely documented for nickel element in previous publications and only one example has been reported in literature.30 The Ni─S bond length in complex 1 is in the range of 2.332─2.458 Å, while Ni─N in 2.032─2.101 Å and Ni─O in 2.003─2.180 Å. O

O

O

O N H

S

Ni

N

Ni

Ni

S Ni

mna-1

mna-2 Ni

O

O O

N

S

O Ni

N

Ni

S

Ni

Ni

mna-3

mna-4

Ni

Scheme 1. Different types of coordination modes of the mna ligand. These ten mna ligand in complex 1 can be categorized into four different types (mna-1, mna2, mna-3 and mna-4) in terms of coordination modes (as shown in Scheme 1). (1) The mna-1 (µ3-η1:2-coordination mode) is partially deprotonated with a sum charge of −1 compared to the other three totally deprotonated case with a sum charge of −2, thereby meeting the charge balance. (2) The mna-2 (µ4-η1:2:1-coordination mode) is bound to two Ni(II) ions via nitrogen, oxygen and sulfur atoms. (3) The mna-3 (µ5-η1:1:2:1-coordination mode) is coordinated to an additional Ni(II) ion via an oxygen atom of carboxylate group compared to mna-2, and thus shows η5-coordination mode. (4) To our best knowledge, the µ5-η1:3:1-coordination mode

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involved in mna-4 is not reported yet for mna ligand so far, in contrast to the documented structures in the past decade. In addition, all these four types of ligands show a rarely seen sixmembered chelate ring (S─C─C─C─O─Ni). The octanuclear nickel (the partially labeled structure is shown in Figure 1a) spacer is comprised of a shield-shaped heptanuclear nickel-sulfur cluster [Ni7S10] and one relatively isolated nickel ion bridging to such nickel-sulfur cluster via carboxylic group of mna ligand. The metal-sulfur skeleton of this heptanuclear cluster is illustrated in Figure 1b, from which it can be seen that this shield-like heptanuclear nickel-sulfur cluster is generally disposed in a particular arrangement with C2 symmetry. Four nickel atoms connected with for sulfur atoms from the mna ligand, approximately in a coplanar distribution, are located at the top section of the shield, whilst a nickel atom along the two-fold axis is located at the bottom and another two nickel atoms lying on the midst link to the top and bottom parts of the shield via four and two edgesharing µ2-sulfur atoms, respectively. In addition, there exists a nickel atom linked to the heptanuclear nickel-sulfur cluster by carboxylic group of mna ligand. It is worth noting that the sulfur atom of mercapto group from mna adopts two types of coordination configuration, namely, µ2- and µ3-coordination modes, and to the best of our knowledge, the latter is the first time reported for mercaptoaromatic groups (based on Cambridge Structural Database), and it is believed to play a crucial role in the stabilization of the cluster. The rhombus binuclear nickel-oxygen nodes [Ni2O2] with dimensions of 2.100 Å×2.111 Å connect the octanuclear nickel spacer via each apex of the rhombus. The distance of the two nickel atoms is 3.18 Å. Therefore, from the top of view, the shield-shaped octanuclear nickel spacers are constructed to two-dimensional wave-like (4, 4)-topological network with the help of four-connection nickel-oxygen nodes [Ni2O2].

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The striking feature of complex 1 is its heptanuclear nickel-sulfur cluster [Ni7S10], which represents one of the largest nickel-sulfur clusters in an infinite two-dimensional coordination network. As is known, most of the previous reported nickel-sulfur clusters display discrete tiaralike structures rather than act as SBUs in an infinite coordination polymer.14–17 In addition, the separation of the pyridine rings of mna ligands in neighboring layers is in 3.8737 Å with a shift value 3.3568 Å, indicating a week π···π stacking interaction between them, which gives rise to a tightly packed three-dimensional network (Figure 2).

Figure 3. Thermogravimetric analysis (TGA) curve of 1. The thermal stability of compound 1 was studied by thermogravimetric analysis (TGA). As displayed in Figure 3, the first major weight loss of ca. 15.3% corresponds to the release of water molecules in the structure. Compound 1 remains the stabilization and no significant weight loss occurs until about 300 °C, indicative of its relatively high thermal stability. And then a remarkable weight loss between 300–430 °C was observed, which can be attributed to the structure collapse. In addition, infrared spectrum (Figure S1) and X-ray powder diffraction (Figure S2) measurements were also performed to check its chemical structure and purity, respectively.

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Figure 4. Plots of the temperature dependence of χMT and χM for compound 1. The magnetic susceptibility measurement for 1 was performed with polycrystalline samples in the temperature range of 2–300 K under an applied field of 1 kOe. As depicted in Figure 4, the experimental χMT value per [Ni9] unit for compound 1 at room temperature is calculated 6.38 cm3 K mol−1, considerably lower than the expected theoretical value 9 cm3 K mol−1 for nine noninteracting spin-only Ni(II) ions in octahedral environment assuming g = 2, a reasonable value for polynuclear Ni(II) species.31 This case has been documented by previous works32,33 and indicates strong anti-ferromagnetic exchange coupling among the Ni9 cluster.34 Upon decreasing the temperature, the χMT value declines almost linearly to 3.63 cm3 K mol−1 at 55 K, also indicative of the existence of a dominant anti-ferromagnetic exchange coupling.35,36 The further decrease in temperature witnesses a slight increase of χMT value to 3.74 cm3 K mol−1 at 16 K, which may be contributed to the presence of weak intramolecular ferromagnetic interaction37,38 and spin frustration39. Below 16 K, the χMT value declines rapidly to 2.75 cm3 K mol−1 at 2 K, suggesting the presence of intermolecular anti-ferromagnetic interactions. Unfortunately, because of the complexity in molecular structure, it is unrealistic to fit the experimental magnetic data of this two-dimensional heteropolymetallic spin system using a suitable theoretical model.

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To conclude, a new magnetic cluster-based coordination polymer featuring high-nuclear nickel(II)-thiolate SBUs has been successfully prepared and structurally characterized by singlecrystal X-ray diffraction along with infrared spectroscopy (IR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and elemental analyses. Single-crystal X-ray crystallography reveals that compound 1 contains [Ni7S10] cluster, and further form threedimensional molecular structures through covalently linked nickel-oxygen bridging nodes and π···π stacking interaction. Magnetic properties were further investigated, indicative of the presence of overall intermolecular anti-ferromagnetic interactions between nickel(II) ions and

mna ligand. Acknowledgements We thank the Fundamental Research Funds for the Central Universities (2017QH01), the National Science Foundation of China (21233009), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20010200) and the 973 Program (2014CB845603) for financial support.

Corresponding Author *To whom correspondence should be addressed. E-mail: [email protected] (Ning Yuan); [email protected] (Xintao Wu).

Notes CCDC reference number 1526814.

Supporting Information Available: X-ray crystallographic data in CIF format and additional figures. This material is available free of charge via the Internet at http://pubs.acs.org.

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Dalt. Trans. 2007, 1661–1664. (29) Humphrey, S. M.; Alberola, A.; García, C. J. G.; Wood, P. T. A New Co(II) Coordination Solid with Mixed Oxygen, Carboxylate, Pyridine and Thiolate Donors Exhibiting Canted Antiferromagnetism with TC≈68 K. Chem. Commun. 2006, 1607–1609. (30) Cristurean, A.; Irisli, S.; Marginean, D.; Rat, C.; Silvestru, A. Dimeric versus monomeric nickel(II)

complexes

structures

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tetraorganodichalcogenoimidodiphosphinato

Ni2[(OPPh2)2N]4·CH2Cl2,

ligands:

Crystal

Ni[(OPPh2)2N]2(DMF)2·2H2O

and

[KNi[(SPPh2){OP(OEt)2}N]3]2. Polyhedron 2008, 27, 2143–2150. (31) Diamantopoulou, E.; Raptopoulou, C. P.; Terzis, A.; Tangoulis, V.; Perlepes, S. P. Heptanuclearity in nickel(II) chemistry: preparation, characterization, crystal structure and

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magnetic properties of [Ni7(OH)2(acac)8(btaO)4(H2O)2] (btaO = the 1-hydroxybenzotriazolate ion). Polyhedron 2002, 21, 2117–2126. (32) Jiang, Y.; Kou, H.; Wang, R.; Cui, A.; Ribas, J. Synthesis, Crystal Structure, and Magnetic Properties of Oxime-Bridged Polynuclear Ni(II) and Cu(II) Complexes. Inorg. Chem.

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J.-P.; Perlepes, S. P. A General Synthetic Route for the Preparation of High-Spin Molecules: Replacement of Bridging Hydroxo Ligands in Molecular Clusters by End-on Azido Ligands.

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S.

P.

The

first

tridecanuclear

nickel(II)

cluster:

[Ni13(OH)6(O2CMe)8(btaO)12(H2O)6(nPrOH)4] (btaOH = 1-hydroxybenzotriazole). Inorg. Chem.

Commun. 2008, 11, 454–460.

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For Table of Contents Use Only

A New Magnetic Nickel(II)-Thiolate Cluster-Based Coordination Polymer Constructed from 2-Mercaptonicotinic Acid Ning Yuan,a* Chongbin Tian,b Tianlu Sheng,b Shengmin Hu,b Xintao Wub* a

School of Chemical & Environmental Engineering, China University of Mining & Technology,

Beijing 100083, China b

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou 350002, China *To whom correspondence should be addressed. E-mail: [email protected] (Ning Yuan); [email protected] (Xintao Wu).

A new magnetic coordination polymer containing nickel(II)-thiolate cluster [Ni7S10] as secondary building unit has been successfully synthesized and fully characterized.

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