Table of Contents
International Journal of Inorganic Chemistry
Volume 2010 (2010), Article ID 326568, 5 pages
http://dx.doi.org/10.1155/2010/326568
Research Article

Syntheses and Crystal Structures of and

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Izumi, Narashino, Chiba 275-8575, Japan

Received 31 August 2009; Accepted 10 November 2009

Academic Editor: J. D. Woollins

Copyright © 2010 Takayoshi Fujii et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

We have prepared the trinuclear complexes (3) and (4), from the reaction of with (1) and determined their structures by X-ray crystallographic analysis. In both complexes, two monoanions chelate the Cu(II) center in square-planar geometry, whereas the terminal Cu(II) center is four-coordinate and a distorted tetrahedron.

1. Introduction

The chemistry of 6-sulfanenitrile, bearing an SN triple bond, shows some interesting and fascinating features. Mews et al. prepared trifluoro- 6-sulfanenitrile (F3S N) and its derivatives (F2RS N, e.g., R = Me2N–, F2(O=)S=N–), and investigated their metal coordination chemistry [13]. Recently, we prepared fluoro(diphenyl)- 6-sulfanenitrile (Ph2FSN) and reported the formation of the various substituted 6-sulfanenitriles [414]. Among them, new types of 6-sulfanenitrile with nitrilo and imino groups (type A) or two nitrilo groups (ndsdsd, type B) at both ends have been shown to complexes as bidentate N,N’ ligands. For example, the reaction of ndsdsd with MCl2 (M = Co(II), Ni(II), and Cu(II)) gave the corresponding [MCl2(ndsdsd)] and [M(ndsdsd)2]Cl2, and their molecular structures were determined by X-ray crystallographic analysis [15]. The two terminal nitrogen atoms chelate to the metal center to form an eight-membered sulfur-nitrogen ring. We have also performed coordination studies of sulfanenitrile ligands of type A wherein the monoanions reacted with Ph2SnCl2 to give the corresponding tin-complexes [ClPh2Sn E(Ph2SN)2 ] (E = CH, N) in good yields [16]. The crystal structures of both compounds were determined by X-ray crystallographic analysis and showed to consist with a monomeric chelate structure that contains a distorted trigonal bipyramidal tin atom with a nitrogen and chlorine atom in the axial sites. In a further extension of these studies, we examined the reaction of 1 with CuCl2. Herein, we describe the preparation and crystal structure determination of [Cu3 -(NSPh2)2N 2Cl2] (3) and [Cu3 -(NSPh2)2N 2 (NSPh2)2N 2]Cl2 (4).

326568.sch.00

2. Experimental

2.1. Chemicals and General Methods

All reagents and solvents were obtained commercially and were further purified by general methods when necessary. The single crystal X-ray diffraction data were collected with a Rigaku RAXIS RAPID imaging plate using graphite monochromated Mo K radiation ( = 0.71075 ). IR spectra were recorded on a Shimadzu FTIR-8400S spectrometer. Melting points were measured on a Yanaco Mp-J3 melting point apparatus. Elemental analyses were carried out at the Chemical Analysis Center of the College of Science and Technology, Nihon University.

2.2. Syntheses

The free ligands N(Ph2SN)(Ph2SNH) (1) was synthesized as described previously [7].

2.2.1. Preparation of [Cu3 -(NSPh2)2N 2Cl4] (3) and [Cu3 -(NSPh2)2N 2 (NSPh2)2N 2]Cl2 (4)

A solution of 1 (166 mg, 0.4 mmol) and sodium methoxide (22 mg, 0.4 mmol) in methanol (1.0 mL) was slowly added to a solution of CuCl2 (81 mg, 0.6 mmol or 41 mg, 0.4 mmol) in the same solvent (1.0 mL) at ambient temperature, which started to precipitate a solid within 1 minute. The precipitate was then filtered, washed with methanol, and dried under vacuum at for 24 hours. Crystals suitable for X-ray analysis were obtained from metanol-ether (3) and dichloromethane-ether (4).

Data for 3
Green-yellow; Yield 93%, relative to 1; mp. 221– (decomp.); IR (KBr) 3055, 1475, 1445, 1146, 1078, 1065, 1024, 1009, 984 cm−1; UV-vis (MeOH, , nm ( , M−1cm−1)) 207 (9.3 104), 407 (sh, 3.5 103); Anal. Calcd for C48H40Cl4Cu3N6S4: C, 49.63; H, 3.47; N, 7.23; Found: C, 49.31; H, 3.38; N, 7.19.

Data for 4
Green; Yield 97%, relative to 1; mp. 151– (decomp.); IR (KBr) 3383, 3055, 1473, 1444, 1227, 1159, 1067, 1007, 972 cm−1; UV-vis (MeOH, , nm ( , M−1cm−1)) 208 (1.4 105), 392 (sh, 9.9 103); Anal. Calcd for C96H88Cl2Cu3N12O4S8: C, 57.89; H, 4.45; N, 8.44; Found: C, 57.82; H, 4.15; N, 8.42.

2.3. X-ray Crystallography

Diffraction data were collected with a Rigaku RAXIS RAPID imaging plate using graphite monochromated Mo K radiation ( = 0.71075  ). The data were corrected for Lorentz and polarization effects, and an empirical absorption correction was applied which resulted in transmission factors (see Table 1). The structures 24 were solved by the direct method using SHELXS-97 and were refined using SHELXL-97 [17]. Crystal data for [Cu3 -(NSPh2)2N 2Cl4] (3) and [Cu3 -(NSPh2)2N 2 (NSPh2)2N 2]Cl2 (4) are given in Table 1.

tab1
Table 1: Crystallographic Data for Compounds 3 and 4.

3. Results and Discussion

The addition of an equimolecular amount of 1 to CuCl2 in methanol at ambient temperature immediately gave a green-yellow solution and green precipitates. After filtering the precipitates and removing the solvent, the recrystallization of the residue from methanol-ether gave yellow crystals 2. On the other hand, the precipitates were recrystallized from methanol-ether to give green-yellow crystals 3. The compositions of 2 and 3 were identified by elemental analysis and IR spectroscopy, and their structures were determined by X-ray crystallographic analysis (Figure 1 and Supplementary Figure , in Supplementary Material available online at http://dx.doi.org/10.1155/2010/326568). Preliminary experiments indicated that 1 acts as the bridging ligands and base to form the trinuclear complex, [Cu3 -(NSPh2)2N 2Cl4] (3), and protonated compound, N(Ph2SNH)2 2CuCl4 (2), respectively, (Scheme 1). Therefore, complexe 3 was prepared effectively and almost quantitatively from the reaction of 1 and CuCl2 (1.5 equivalents) in the presence of sodium methoxide as the base in methanol at ambient temperature (Scheme 1). Furthermore, the reaction of 1 and CuCl2 in the ratio under the above conditions gave the corresponding compound [Cu3 -(NSPh2)2N 2 (NSPh2)2N 2]Cl2 (4) almost quantitatively (Scheme 1). Green crystals of 4 suitable for X-ray analysis were obtained by crystallization from dichloromethane-ether at ambient temperature.

326568.sch.001
Scheme 1: (i) CuCl2 (1.0 equiv.), MeOH, r.t.; (ii) CuCl2 (1.5 equiv.), MeONa, MeOH, r.t.; (iii) CuCl2 (0.75 equiv.), MeONa, MeOH, r.t..
326568.fig.001
Figure 1: ORTEP drawing of 3 (50% probability thermal ellipsoids; H and C atoms (apart from the C atoms of the phenyl rings) have been omitted for clarity).

In order to confirm the identity of [Cu3 -(NSPh2)2N 2Cl4] (3) and [Cu3 -(NSPh2)2N 2 (NSPh2)2N 2]Cl2 (4), single crystal X-ray structure determinations were carried out. ORTEP drawings of 3 and 4 are depicted in Figures 1 and 2. Selected bond lengths and angles for complexes 3 and 4 are collected in Table 2.

tab2
Table 2: Selected Bond Lenghts ( ) and angles (deg) Compounds 3 and 4.
326568.fig.002
Figure 2: ORTEP drawing of 4 (50% probability thermal ellipsoids; H, C atoms (apart from the C atoms of the phenyl rings), two chloride anions, and uncoordinated water molecules have been omitted for clarity).

The X-ray structure of 3 shows two independent molecules with nearly identical bond lengths and angles (an ORTEP drawing of one of two independent molecules). The X-ray analysis clearly reveals that it is centrosymmetric trinuclear complex containing two six-membered CuN3S2 and two four-membered Cu2N2 rings (Figure 1). The two monoanions act as a bridging ligand to form the three linearly arranged copper(II) ions with a separation of 3.0377(11)  . The ligand adopts a boat form conformation wherein the Cu(1) and the central nitrogen (N(2)) atoms lie 0.365 and 0.489  , respectively, outside the quasi-plane formed by the S2N2 of the ring. The terminal nitrogen atoms of the ligand are fixed in a bridging position and the mean value of the terminal S–N bond lengths (1.506  ) is considerably larger than that of the free ligand (mean 1.486  ) [8] and is close to that of [CuCl2( -NSPh3)]2 (1.505(4)  ) [18]. The internal S–N bond lengths (mean 1.599  ) and S(1)–N(2)–S(2) angle (118.1 ) are close to those of the free ligand 1 (S–N; mean 1.615  , S–N–S; 117.5 ) [8]. The central Cu(II) atom adopts a square-planar geometry, being linked to four nitrogen atoms (N(1), N(3), N , and N ) of ligand . The bond angles around the terminal Cu(II) atom with two nitrogen and two chlorine atoms span the range of 79.95(18)–138.61(17)°, substantially deviating from the ideal tetrahedral angle. The dihedral angle of 63.06° between the N(1)–Cu(2)–N(3) and Cl(1)–Cu(2)–Cl(2) planes shows significant deviation from the ideal 90° for a tetrahedral arrangement. The bond lengths of Cu–N (1.962(5)–2.079(5)  ; mean 2.002  ) and Cu(2)–Cl (2.196(2)–2.227(2)  ; mean 2.212  ) in 3 are similar to those of [CuCl2( -NSPh3)]2 (Cu–N; mean 2.016  , Cu–Cl; mean 2.217  ) [18].

The structure of 4 consists of a separated [Cu3 -(NSPh2)2N 2 (NSPh2)2N 2]2+ cation, two anions, and four water molecules. The cation moiety contains a square-plannar central Cu(II) and two distorted tetrahedral Cu(II) atoms (Figure 2). The distance is 3.0194(13)  . Although the conformation of the bridging ligand (the Cu–N bond lengths in the four-membered Cu2N2 ring are 1.966(4)–2.014(3)  ; mean 1.992  ) is similar to that of 3, the bidentate ligand adopts a twist boat conformation (the Cu(2)–N bond lengths in the six-membered Cu(2)N3S2 ring are 1.913(3) and 1.915(3)  , respectively). The terminal and internal S–N bond lengths of the bidentate ligand are slightly shorter than those of the corresponding bridging ligand.

4. Conclusions

In summary, we have demonstrated the formation of new types of 6-sulfanenitrile-copper(II) complexes, [Cu3 -(NSPh2)2N 2Cl2] (3) and [Cu3 -(NSPh2)2N 2 (NSPh2)2N 2]Cl2 (4), and determined their molecular structures. As magnetic orbital interactions between the copper ions in many multinuclear systems result in ferromagnetic coupling, further investigation of the chemistry of our trinuclear system including the magnetic properties is now in progress.

Acknowledgments

This work was partially supported by a Grants-in-Aid for Scientific Research (no. 16750030 and 19550051) from the Ministry of Education, Culture, Sports, Science and Technology of Japan and supported by a grant from High Technology Research Center, College of Industrial Technology, Nihon University.

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