Bis(carbonyl-κC)(N,N-dimethyl­thio­carbamoyl-κ2 C,S)(pyridine-2-thiol­ato-κ2 N,S)(triphenyl­phosphine-κP)molybdenum(II)

Kuang-Hway Yih; Hsiao-Fen Wang; Gene-Hsiang Lee

doi:10.1107/S1600536810034562

. 2010 Sep 4;66(Pt 10):m1189–m1190. doi: 10.1107/S1600536810034562

Bis(carbonyl-κC)(N,N-dimethylthiocarbamoyl-κ² C,S)(pyridine-2-thiolato-κ² N,S)(triphenylphosphine-κP)molybdenum(II)

Kuang-Hway Yih ^a,^*, Hsiao-Fen Wang ^a, Gene-Hsiang Lee ^b,^*

PMCID: PMC2983129 PMID: 21587354

Abstract

There are two independent molecules with similar configurations in the title complex, [Mo(C₃H₆NS)(C₅H₄NS)(C₁₈H₁₅P)(CO)₂]. The geometry around the metal atom is that of a capped octahedron. The thiocabamoyl and pyridine-2-thiolate ligands coordinate to the molybdenum metal center through the C and S atoms, and N and S atoms, respectively. NMR, IR and MS analyses are in agreement with the structure of the title compound.

Related literature

Molybdenum complexes containing Mo—S and Mo—N bonds are of special interest because of their relevance to a variety of molybdenum-containing enzymes (Cramer et al., 1978 ▶) and hydrodesulfurization catalysts (Anzenhofer & de Boer, 1969 ▶). For complexes of group VI metals and the pyridine-2-thiolate ligand, see: Baker et al. (1995 ▶); Cotton & Ilsley (1981 ▶). For related structures of thiocabamoyl–molybdenum complexes, see: Anderson & Hill (1993 ▶); Foreman et al. (2003 ▶); Lim et al. (2005 ▶). For bond lengths in molybdenum–carbonyl complexes, see: Yih & Lee (2008 ▶) and references therein. For the SCNMe₂ ligand, see: Lin et al. (2004 ▶) and for typical bond lengths, see: Huheey (1983 ▶). For bond distances and angles in molybdenum–pyridine-2-thiolate complexes, see: Yih et al. (2003a ▶, 2003b ▶) and references therein.

Experimental

Crystal data

[Mo(C₃H₆NS)(C₅H₄NS)(C₁₈H₁₅P)(CO)₂]
M _r = 612.53
Monoclinic,
a = 20.0947 (8) Å
b = 15.8720 (6) Å
c = 17.8596 (7) Å
β = 107.563 (1)°
V = 5430.7 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 150 K
0.35 × 0.06 × 0.04 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.95, T _max = 0.97
41353 measured reflections
12460 independent reflections
8888 reflections with I > 2σ(I)
R _int = 0.089

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.123
S = 1.08
12460 reflections
653 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034562/bg2366sup1.cif

e-66-m1189-sup1.cif^{(32.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034562/bg2366Isup2.hkl

e-66-m1189-Isup2.hkl^{(609.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the National Science Council of the Republic of China for financial support (NSC98–2113-M-241–011-MY2).

supplementary crystallographic information

Comment

Molybdenum complexes containing Mo—S and Mo—N bonds are of special interest because of their relevance to a variety of molybdenum-containing enzymes (Cramer et al., 1978) and hydrodesulfurization catalysts (Anzenhofer & de Boer, 1969). For the group VI metals, several investigators have reported complexes relevant to pyridine-2-thiolate ligand (Cotton & Ilsley, 1981; Baker et al., 1995). Thiocarbamoyl Mo and W (VIB) complexes are known (Anderson & Hill, 1993). To our knowledge, no thiocarbamoyl complex of molybdenum (II) containing pyridine-2-thiolate has been described.

To synthesis of seven coordinated and NS-coordinated metal compound, complex [Mo(CO)₂(SCNMe₂)(PPh₃)₂Cl] was used to react with C₅H₄NSH in dichloromethane at room temperature. As a result, a chloride and triphenylphosphine displaced complex [Mo(CO)₂(SNC₅H₄)(SCNMe₂)(PPh₃)] was isolated with 82% yield. The X-ray crystal structure analysis has been carried out to provide structural parameters.

The molecular structure and the packing diagram of the title compound are shown in Fig. 1 and 2 respectively. X-ray analysis shows that the unit cell contains two independent molecules. There are small difference in bond distances (in the range of 0.002–0.025 Å) and bond angles (in the range of 0–3.32°) between the two independent molecules around the metal atoms. The geometry around the cations is midway a capped trigonal prism and a capped octahedron. The capped trigonal prism consists of a phosphorus atom, P1(P2), in the unique capping position [Mo—P(av) = 2.5651 (12)], carbonyl group, C1-O1(C29-O3) and sulfur atom of the thiocabamoyl group, S1(S3), and nitrogen and sulfur atoms of the pyridine-2-thiolate ligand, in the capped quadrilateral face [Mo—C1(C29)(av) = 1.946 (5); Mo—S1(S3)(av) = 2.5031 (12); Mo—N2(N4)(av) = 2.252 (4); Mo—S2(S4)(av) = 2.5393 (12)] and the other carbonyl group in the unique edge [Mo—C2(C30)(av) = 1.983 (5)]. In contrast the capped octahedron is made up of C3(C31) in the capping position, C3(C31), S1(S3), and C2(C30) in the capped face, and P1(P2), S2(S4), and N2(N4) in the uncapped face. The PPh₃ and carbonyl group is in trans position: P1—Mo—C(av) = 142.64 (14)°, while the pyridine-2-thiolate ligand and carbonyl and sulfur atom of the SCNMe₂ ligand are trans to each other: C1—Mo—N2(C29—Mo2—N4)(av) = 175.40 (16)° and S1—Mo—S2(S3—Mo2—S4) = 149.29 (4)°. The Mo—C—O angles of (I) are essentially linear in the region of 170.3 (4)–178.3 (4)° and similar to those found for other terminal carbonyls contained in Mo systems. The Mo—CO(av) (1.946 (5), 1.983 (5) Å) and C—O(av) distances (1.163 (5), 1.153 (5) Å) are both with the range of values reported for the other molybdenum carbonyl complexes (Yih & Lee, 2008 and references therein).

Within the SCNMe₂ ligand (Lin et al., 2004), the C—S(av) (1.694 (5) Å) and SC—N(av) (1.309 (5) Å) bond distances are typical for C—N and C—S bonds having partial double bond character and are certainly much shorter than the normal C—N (1.47 Å) and C—S (1.82 Å) single bonds (Huheey, 1983). The Me—N(av) bond distances (1.454 (6) and 1.470 (6) Å) are normal for a single bond. Within the SNC₅H₄ ligand, the S2—C6—N2(S4—C34—N4) bond distances and angles shows a geometrical environment characteristic of a sp² hybridization of the carbon atom. In addition, the S2—C6—N2(S4—C34—N4)(av) angle of 110.8 (3)° and the S2—Mo—N2(S4—Mo2—N4)(av) angle of 64.11 (10)° is similar to other molybdenum pyridine-2-thiolate complexes (Yih et al., 2003a, 2003b and references therein).

In the ¹H NMR spectrum of (I), three protons of the SNC₅H₄ ligand exhibits one doublet resonance at δ 6.21 and two triplet resonances at δ 6.46, 6.88 with ratio of 1:1:1. Two methyl resonances at δ 3.55 and δ 3.78 of the SCNMe² ligand are observed in the ¹H NMR spectra of complex (I), consistent with hindered rotation about the partially multiple C—N bond. In the ¹³C{¹H} NMR spectrum of (I), two singlet resonances appear at δ 45.2, δ 50.4 for the carbon atoms of N-methyl groups, respectively. Three singlet resonances appear at δ 176.8, 235.1 and 248.0 for the carbon atom of the NCS, CO and Me₂NCS groups, respectively. The ³¹P{¹H} NMR spectrum of (I) shows one resonance at δ 48.5.

It is also noted the IR spectrum of the title complex (I) shows five stretching bands at 1921 and 1824 cm^-1 for C=O, at 1563 cm^-1 for C=N, at 1481 and 1434 cm^-1 for C=S groups. In the FAB mass spectra, base peak with the typical Mo isotope distribution is in agreement with the [M⁺] molecular mass of (I).

Experimental

The synthesis of the title compound (I) was carried out as follows. CH₂Cl₂ (10 ml) was added to a flask (100 ml) containing C₅H₄NSH (0.111 g, 1.0 mmol) and [Mo(CO)₂(SCNMe₂)(PPh₃)₂Cl] (0.800 g, 1.0 mmol). The solution was stirred for 10 min at room temperature. The solution is concentrated under vacuum and MeOH (10 ml) was added to initiate precipitation. The orange solids were isolated by filtration (G4), washed with diethyl ether (2 x 10 ml) and subsequently drying under vacuum yielding [Mo(CO)₂(SNC₅H₄)(SCNMe₂)(PPh₃)] (0.501 g, 82%). Further purification was accomplished by recrystallization from 1/10 CH₂Cl₂/n-hexane. The orange crystals of (I) for X-ray structure analysis were obtained by slow diffusion of n-hexane into the CH₂Cl₂ solution of the title compound at room temperature for 3 days. Spectroscopic analysis: ¹H NMR (CDCl₃, 298 K, δ, p.p.m.): 3.55, 3.78 (s, 6H, NMe₂), 6.21 (d, 1H, NCH, ³J_H—H = 8.15 Hz), 6.46 (t, 1H, NCCH, ³J_H—H = 6.45 Hz), 6.88 (t, 1H, NCCCH, ³J_H—H = 7.25 Hz), 7.35–7.55 (m, 16H, Ph, HCCNS). ³¹P{¹H} NMR (CDCl₃, 298 K, δ, p.p.m.): δ 48.5. ¹³C{¹H} NMR (CDCl₃, 298 K, δ, p.p.m.): δ 45.2, 50.4 (s, NMe), 176.8 (s, NCS), 235.1 (s, CO), 248.0 (s, MeNCS). MS (m/z): 614 (M⁺). Anal. Calcd for C₂₈H₂₅N₂O₂PS₂Mo: C, 54.90; H, 4.11; N, 4.57. Found: C, 55.10; H, 4.25; N, 4.22.