# Syntheses and Crystal Structures of[Cu3{μ-(NSPh2)2N}2Cl2] and [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]Cl2

Authors: Takayoshi Fujii; Mihoko Kanno; Mitsuo Hirata
Journal: International Journal of Inorganic Chemistry
 (2010)

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## Abstract

We have prepared the trinuclear complexes[Cu3{μ-(NSPh2)2N}2Cl2] (3) and [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]Cl2 (4), from the reaction of CuCl2 with {N(Ph2SN)(Ph2SNH)} (1) and determined their structures by X-ray crystallographic analysis. In both complexes, two monoanions 1− chelate the Cu(II) center in square-planar geometry, whereas the terminal Cu(II) center is four-coordinate and a distorted tetrahedron.


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## Body

## 1. Introduction

The chemistry ofλ6-sulfanenitrile, bearing an SN triple bond, shows some interesting and fascinating features. Mews et al. prepared trifluoro-λ6-sulfanenitrile (F3S≡N) and its derivatives (F2RS≡N, e.g., R = Me2N–, F2(O=)S=N–), and investigated their metal coordination chemistry [1–3]. Recently, we prepared fluoro(diphenyl)-λ6-sulfanenitrile (Ph2FS≡N) and reported the formation of the various substituted λ6-sulfanenitriles [4–14].   Among them, new types of λ6-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{μ-(NSPh2)2N}2Cl2] (3) and [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]Cl2 (4).


## 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 Kα radiation (λ = 0.71075 Å). 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{μ-(NSPh2)2N}2Cl4] (3) and [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]Cl2 (4)

A solution of1 (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 100°C for 24 hours. Crystals suitable for X-ray analysis were obtained from metanol-ether (3) and dichloromethane-ether (4).Data for3
Green-yellow; Yield 93%, relative to1; mp. 221–223°C (decomp.); IR (KBr) 3055, 1475, 1445, 1146, 1078, 1065, 1024, 1009, 984 cm−1; UV-vis (MeOH, λmax, nm (ε, 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 for4
Green; Yield 97%, relative to1; mp. 151–152°C (decomp.); IR (KBr) 3383, 3055, 1473, 1444, 1227, 1159, 1067, 1007, 972 cm−1; UV-vis (MeOH, λmax, nm (ε, 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 Kα radiation (λ = 0.71075 Å).   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 2–4 were solved by the direct method using SHELXS-97 and were refined using SHELXL-97 [17]. Crystal data for [Cu3{μ-(NSPh2)2N}2Cl4] (3) and [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]Cl2 (4) are given in Table 1.Table 1
Crystallographic Data for Compounds3 and 4.
34·4H2OFormulaC96H80Cl8Cu6N12S8C96H88Cl2Cu3N12O4S8Fw2323.041991.87Cryst size (mm)0.23× 0.22 × 0.060.66× 0.29 × 0.28Temp (K)296(2)296(2)λ(Å)0.710750.71075Cryst systtriclinictriclinicSpace groupP-1P-1a (Å)9.294(4)13.527 (6)b(Å)14.015(5)15.760(6)c(Å)18.792(6)16.493(6)α (deg)93.941(12)60.552(14)β (deg)93.138(13)64.828(14)γ (deg)94.280(12)88.128(15)V (Å3)2430.7(14)2700.9(17)Z11ρc (Mg/m3)1.5871.220μ (mm-1)1.7340.839F(000)11781021Tmin/Tmax0.6912/0.90310.6073/0.7989θ range/deg3.00–27.483.01–27.48Reflns collcd2399526115Indp reflns1097312146Rint0.0960.04Data/restrains/params10973/0/58912146/0/565R1,wR20.0688, 0.10740.0683, 0.1961(I>2σ[I])R1,wR2 (all data)0.1542, 0.13370.1110, 0.2293GOF/F21.0241.018


## 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 Kα radiation (λ = 0.71075 Å). 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{μ-(NSPh2)2N}2Cl4] (3) and [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]Cl2 (4)

A solution of1 (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 100°C for 24 hours. Crystals suitable for X-ray analysis were obtained from metanol-ether (3) and dichloromethane-ether (4).Data for3
Green-yellow; Yield 93%, relative to1; mp. 221–223°C (decomp.); IR (KBr) 3055, 1475, 1445, 1146, 1078, 1065, 1024, 1009, 984 cm−1; UV-vis (MeOH, λmax, nm (ε, 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 for4
Green; Yield 97%, relative to1; mp. 151–152°C (decomp.); IR (KBr) 3383, 3055, 1473, 1444, 1227, 1159, 1067, 1007, 972 cm−1; UV-vis (MeOH, λmax, nm (ε, 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.


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

A solution of1 (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 100°C for 24 hours. Crystals suitable for X-ray analysis were obtained from metanol-ether (3) and dichloromethane-ether (4).Data for3
Green-yellow; Yield 93%, relative to1; mp. 221–223°C (decomp.); IR (KBr) 3055, 1475, 1445, 1146, 1078, 1065, 1024, 1009, 984 cm−1; UV-vis (MeOH, λmax, nm (ε, 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 for4
Green; Yield 97%, relative to1; mp. 151–152°C (decomp.); IR (KBr) 3383, 3055, 1473, 1444, 1227, 1159, 1067, 1007, 972 cm−1; UV-vis (MeOH, λmax, nm (ε, 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 Kα radiation (λ = 0.71075 Å).   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 2–4 were solved by the direct method using SHELXS-97 and were refined using SHELXL-97 [17]. Crystal data for [Cu3{μ-(NSPh2)2N}2Cl4] (3) and [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]Cl2 (4) are given in Table 1.Table 1
Crystallographic Data for Compounds3 and 4.
34·4H2OFormulaC96H80Cl8Cu6N12S8C96H88Cl2Cu3N12O4S8Fw2323.041991.87Cryst size (mm)0.23× 0.22 × 0.060.66× 0.29 × 0.28Temp (K)296(2)296(2)λ(Å)0.710750.71075Cryst systtriclinictriclinicSpace groupP-1P-1a (Å)9.294(4)13.527 (6)b(Å)14.015(5)15.760(6)c(Å)18.792(6)16.493(6)α (deg)93.941(12)60.552(14)β (deg)93.138(13)64.828(14)γ (deg)94.280(12)88.128(15)V (Å3)2430.7(14)2700.9(17)Z11ρc (Mg/m3)1.5871.220μ (mm-1)1.7340.839F(000)11781021Tmin/Tmax0.6912/0.90310.6073/0.7989θ range/deg3.00–27.483.01–27.48Reflns collcd2399526115Indp reflns1097312146Rint0.0960.04Data/restrains/params10973/0/58912146/0/565R1,wR20.0688, 0.10740.0683, 0.1961(I>2σ[I])R1,wR2 (all data)0.1542, 0.13370.1110, 0.2293GOF/F21.0241.018


## 3. Results and Discussion

The addition of an equimolecular amount of1 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 S1, in Supplementary Material available online at doi:10.1155/2010/326568). Preliminary experiments indicated that 1 acts as the bridging ligands and base to form the trinuclear complex, [Cu3{μ-(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 4:3 under the above conditions gave the corresponding compound [Cu3{μ-(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.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..Figure 1
ORTEP drawing of3 (50% probability thermal ellipsoids; H and C atoms (apart from the Cα atoms of the phenyl rings) have been omitted for clarity).In order to confirm the identity of [Cu3{μ-(NSPh2)2N}2Cl4] (3) and [Cu3{μ-(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.Table 2
Selected Bond Lenghts (Å) and angles (deg) Compounds 3 and 4.
3Cu(1)–N(1)1.962(4)Cu(2)–N(3)*2.079(5)Cu(1)–N(3)1.990(4)S(1)–N(1)1.508(4)Cu(2)–Cl(1)2.227(2)S(1)–N(2)1.601(5)Cu(2)–Cl(2)2.196(2)S(2)–N(2)1.597(5)Cu(2)–N(1)1.975(4)S(2)–N(3)1.503(4)N(1)–Cu(1)–N(3)97.50(18)N(2)–S(2)–N(3)119.0(2)N(1)–Cu(1)–N(3)*82.50(18)Cu(1)–N(1)–Cu(2)100.99(19)Cl(1)–Cu(2)–Cl(2)101.58(8)Cu(1)–N(1)–S(1)124.8(3)Cl(1)–Cu(2)–N(1)104.63(15)Cu(2)–N(1)–S(1)132.8(3)Cl(1)–Cu(2)–N(3)*132.08(15)S(1)–N(2)–S(2)118.1(3)Cl(2)–Cu(2)–N(1)138.61(17)Cu(1)–N(3)–Cu(2)*96.55(18)Cl(2)–Cu(2)–N(3)*105.00(15)Cu(1)–N(3)–S(2)123.8(3)N(1)–Cu(2)–N(3)*79.95(18)Cu(2)*–N(3)–S(2)131.9(3)N(1)–S(1)–N(2)116.5(3)4Cu(1)–N(1)1.966(4)S(1)–N(2)1.590(3)Cu(1)–N(3)1.976(3)S(2)–N(2)1.597(3)Cu(2)–N(1)*2.014(3)S(2)–N(3)1.480(4)Cu(2)–N(3)2.012(3)S(3)–N(4)1.472(4)Cu(2)–N(4)1.915(4)S(3)–N(5)1.590(4)Cu(2)–N(6)1.913(4)S(4)–N(5)1.586(4)S(1)–N(1)1.489(3)S(4)–N(6)1.478(4)N(1)–Cu(1)–N(3)97.50(14)N(5)–S(4)–N(6)123.5(2)N(1)–Cu(1)–N(3)*82.50(14)Cu(1)–N(1)–Cu(2)*98.69(15)N(1)*–Cu(2)–N(3)80.42(14)Cu(1)–N(1)–S(1)126.42(19)N(1)*–Cu(2)–N(4)143.23(19)Cu(2)*–N(1)–S(1)133.5(2)N(1)*–Cu(2)–N(6)100.69(15)S(1)–N(2)–S(2)119.0(2)N(3)–Cu(2)–N(4)100.60(16)Cu(1)–N(3)–Cu(2)98.39(15)N(3)–Cu(2)–N(6)143.14(19)Cu(1)–N(3)–S(2)126.4(2)N(4)–Cu(2)–N(6)99.65(16)Cu(2)–N(3)–S(2)133.9(2)N(1)–S(1)–N(2)118.63(18)Cu(2)–N(4)–S(3)125.5(2)N(2)–S(2)–N(3)118.64(18)S(3)–N(5)–S(4)118.6(2)N(4)–S(3)–N(5)123.3(2)Cu(2)–N(6)–S(4)125.2(2)The atom labeling scheme is shown in Figure1 and 2.Figure 2
ORTEP drawing of4 (50% probability thermal ellipsoids; H, C atoms (apart from the Cα atoms of the phenyl rings), two chloride anions, and uncoordinated water molecules have been omitted for clarity).The X-ray structure of3 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 1- act as a bridging ligand to form the three linearly arranged copper(II) ions with a Cu⋯Cu separation of 3.0377(11) Å.  The ligand adopts a boat form conformation wherein the Cu(1) and the central nitrogen (N(2)) atoms lie 0.365 and 0.489 Å, 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 Å) is considerably larger than that of the free ligand 1 (mean 1.486 Å) [8] and is close to that of [CuCl2(μ-NSPh3)]2 (1.505(4) Å) [18]. The internal S–N bond lengths (mean 1.599 Å) and S(1)–N(2)–S(2) angle (118.1(3)°) are close to those of the free ligand 1 (S–N; mean 1.615 Å, S–N–S; 117.5(1)°) [8].  The central Cu(II) atom adopts a square-planar geometry, being linked to four nitrogen atoms (N(1), N(3), N(1)*, and N(3)*) of ligand 1-.   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) Å; mean 2.002 Å) and Cu(2)–Cl (2.196(2)–2.227(2) Å; mean 2.212 Å) in 3 are similar to those of [CuCl2(μ-NSPh3)]2 (Cu–N; mean 2.016 Å, Cu–Cl; mean 2.217 Å) [18].The structure of4 consists of a separated [Cu3{μ-(NSPh2)2N}2{(NSPh2)2N}2]2+ cation,  two Cl- 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 Cu(1)⋯Cu(2) distance is 3.0194(13) Å.   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) Å; mean 1.992 Å) 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) Å, 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 ofλ6-sulfanenitrile-copper(II) complexes, [Cu3{μ-(NSPh2)2N}2Cl2] (3) and [Cu3{μ-(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.



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