Dicarbonyl­chlorido(phen­oxy­thio­carbonyl-κ2 C,S)bis­(triphenyl­phosphane-κP)molybdenum(II)

Gene-Hsiang Lee; Hsiao-Fen Wang; Kuang-Hway Yih; Shou-Ling Huang

doi:10.1107/S1600536810052530

. 2010 Dec 24;67(Pt 1):m117–m118. doi: 10.1107/S1600536810052530

Dicarbonylchlorido(phenoxythiocarbonyl-κ² C,S)bis(triphenylphosphane-κP)molybdenum(II)

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

PMCID: PMC3050204 PMID: 21522529

Abstract

In the title complex, [Mo(C₇H₅OS)Cl(C₁₈H₁₅P)₂(CO)₂], the geometry around the metal atom is a capped octahedron. The phenoxythiocarbonyl ligand coordinates the Mo^II atom through the C and S atoms. A one-dimensional structure is formed by π–π intermolecular interactions and a supramolecular aggregation is determined by intermolecular C—H⋯O, C—H⋯Cl, C—H⋯π(arene) hydrogen bonds and CO⋯π(arene) interactions [O⋯centroid distances = 3.485 (4) and 3.722 (3) Å].

Related literature

For the use of metallocarboxylic acids as intermediates in the homogeneous catalysis of the water gas shift reaction, see: Yoshida et al. (1978 ▶). For O-Aryl thiocarbonate, benzoxazoline-2-thione, chromene-2-thione and N,N-dimethylthiocarbamate metal complexes, see: Chen et al. (1978 ▶); McFarlane et al. (1998 ▶); Zheng et al. (2006 ▶) and Zhang & Shi (2004 ▶), respectively. For phenoxylcarbonyl metal complexes, see: Anderson et al. (2001 ▶). We are interested in the synthesis of dithiocarbamate, pyridine-2-thionate (Yih et al., 2010 ▶) and N,N-dimethyldithiocarbarmoyl (Yih & Lee, 2010 ▶) metal complexes. For a phenoxythiocarbonyl–palladium complex, see: Yih & Lee (2004 ▶). For C—H⋯O interactions, see: Strasser et al. (2009 ▶); Arumugam et al. (2010 ▶). For C—H⋯π interactions, see: Suresh et al. (2007 ▶). For π–π interactions, see: Bartholomä et al. (2009) ▶; Hu et al. (2009 ▶). For the C—H⋯Cl interactions, see: Shawkataly et al. (2010 ▶); Qi et al. (2009 ▶). For C—H⋯S interactions, see: Asad et al. (2010 ▶); Goh et al. (2010 ▶). For C–H⋯acceptor interactions, see: Steiner (1996 ▶). For typical C—O and C—S bond lengths, see: Huheey (1983 ▶). For Mo—CO and C—O bond lengths in other molybdenum–carbonyl complexes, see: Yih & Lee (2008 ▶) and references therein.

Experimental

Crystal data

[Mo(C₇H₅OS)Cl(C₁₈H₁₅P)₂(CO)₂]
M _r = 849.12
Triclinic,
a = 10.5685 (10) Å
b = 12.5224 (11) Å
c = 16.3983 (14) Å
α = 82.088 (2)°
β = 77.476 (2)°
γ = 67.212 (2)°
V = 1949.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 150 K
0.16 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.913, T _max = 0.944
25423 measured reflections
8942 independent reflections
6714 reflections with I > 2σ(I)
R _int = 0.075

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.128
S = 1.00
8942 reflections
478 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.81 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/S1600536810052530/bg2377sup1.cif

e-67-0m117-sup1.cif^{(26.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052530/bg2377Isup2.hkl

e-67-0m117-Isup2.hkl^{(437.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg2, Cg3 and Cg7 are the centroids of the C4–C9, C10–C15, C16–C21 and C40–C45 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23⋯O3	0.95	2.31	3.208 (5)	157
C24—H24⋯O1ⁱ	0.95	2.58	3.199 (5)	123
C39—H39⋯Cl1	0.95	2.80	3.573 (4)	139
C9—H9⋯Cg3	0.95	2.97	3.896 (5)	165
C14—H14⋯Cg7ⁱⁱ	0.95	2.83	3.663 (5)	147
C20—H20⋯Cg1ⁱⁱⁱ	0.95	2.97	3.802 (4)	147
C27—H27⋯Cg2	0.95	2.84	3.636 (5)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

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

The interest in the M—C(S)OPh moiety is due to its analogy with metallocarboxylic acid esters (M—C(O)OR) and metallocarboxylic acids themselves. Metallocarboxylic acids have been proposed to be the key intermediates in the homogeneous catalysis of the water gas shift reaction (Yoshida et al., 1978). O-Aryl thiocarbonate (Chen et al., 1978), benzoxazoline-2-thione (McFarlane et al., 1998), chromene-2-thione (Zheng et al., 2006), and N,N-dimethylthiocarbamate (Zhang et al., 2004) metal complexes have been reported but few phenoxylcarbonyl metal complexes have been studied (Anderson et al., 2001). We are interested in the synthesis of dithiocarbamate, pyridine-2-thionate (Yih et al., 2010) and N,N-dimethyldithiocarbarmoyl (Yih & Lee, 2010) metal complexes. To our knowledge, no chelating phenoxythiocarbonyl crystal structure has been described so far.

The molecular structure of the title compound [Mo(CO)₂(SCOPh)(PPh₃)₂Cl], (I),is shown in Fig. 1. The geometry around the metal atom is midway a capped trigonal prism and a capped octahedron. The capped trigonal prism consist of a phosphorus atom, P2, in the unique capping position [Mo1—P2 = 2.5509 (10) Å]. Two carbonyl groups, C1-O1 and C2-O2, Cl1, and the sulfur atom S1 of the phenoxythiocarbonyl ligand are present in the capped quadrilateral face [Mo—C1 = 1.938 (4) Å; Mo—C2 = 1.998 (4) Å; Mo—Cl1 = 2.5160 (9) Å; Mo—S1 = 2.6553 (10) Å] and the phenoxythiocarbonyl ligand is at the unique edge [Mo—S1 = 2.6553 (10) Å; Mo—C3 = 2.025 (4) Å]. In contrast the capped octahedron is made up of C3 in the capping position, C1, S1, and P2 in the capped face, and P1, C2, and Cl1 in the uncapped face. Two PPh₃ ligands are in trans position: P1—Mo—P2, 173.19 (3)°, while the sulfur atom of the phenoxythiocarbonyl ligand, chloride and two carbonyl groups are trans to each other: C2—Mo—S1, 170.67 (11)°, C1—Mo—Cl1, 154.93 (12)°. The mean Mo—C—O angle of (I) ( 176.4 (3)° ) shows the group to be essentially linear, similarly to other terminal carbonyls of Mo. The Mo—CO (1.938 (4), 1.998 (4) Å) and C—O (1.163 (4), 1.146 (4) Å) distances are both consistent with the range of values reported for the other molybdenum carbonyl complexes (Yih & Lee, 2008 and references therein). The Mo—C1 bond distance is clearly shorter than that of Mo—C2 due to the larger trans influence of the sulfur atom of phenoxythiocarbonyl ligand than that of the chlorine ligand.

Within the SCOPh ligand, the C—S (1.650 (4) Å) and SC—O (1.319 (4) Å) bond distances are typical for C—O and C—S bonds having partial double bond character and are certainly much shorter than typical C—O (1.43 Å) and C—S (1.82 Å) single bonds (Huheey, 1983). The S1—C3—O3 group shows a geometrical environment characteristic of sp² hybridization of the carbon atom. In addition, the S1—C3—O3 angle of 129.0 (3)° is larger than that found in the palladium phenoxythiocarbonyl complex (125.2 (6)°) (Yih et al., 2004). To our knowledge, the title complex is the first chelating phenoxythiocarbonyl-metal complex in the literature.

Three weak intramolecular hydrogen bonds and one intermolecular hydrogen bond are present in the structure (Table 1, entries 1-4). In addition, the phenyl ring (C4—C9) of the phenoxythiocarbonyl ligand and a phenyl ring (C10—C15) from the triphenylphosphane are nearly parallel, with an intercentroid distance of 3.938 (3)Å and a shortest inter-ring distance of 3.160 (2) Å. The resulting π-π interaction links molecules into a 1-D chain structure (Fig. 2).Finally, a supramolecular aggregation is determined by four C—H···π(arene) hydrogen bonds (Fig. 3 and Table 1, entries 5-8). The structure also presents some short CO···π(arene) contacts, O1···Cg5: 3.485 (4) and O2···Cg2^iv:3.722 (3)Å, ( iv = -x + 2,-y_2,-z + 1)

In the ¹H NMR spectrum of (I), 35 protons of the seven phenyl exhibit multiple resonances in the region of δ 7.12–7.73. In the ¹³C{¹H} NMR spectrum of (I), two triplet resonances appear at δ 229.3 and δ 238.6 with ²J_P—C = 12.95, 11.95 Hz couplings for the two inequivalent carbonyl groups, respectively. The ³¹P{¹H} NMR spectrum of (I) shows one resonance at δ 34.2.

It is also noted that the IR spectrum of the title complex (I) shows four stretching bands, two at 1965, 1891 cm^-1 for C=O and two at 1483, 1434 cm^-1 for C-OPh groups. In the FAB mass spectra, the 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. PhOCSCl (0.135 g, 1.1 mmol) was added to a flask (100 ml) containing CH₂Cl₂ (10 ml) and [Mo(CH₃CN)₂(CO)₂(PPh₃)₂] (0.758 g, 1.0 mmol) at room temperature. The color of the solution was changed from yellow to red immediately. The solution was concentrated under vacuum and n-hexane (10 ml) was added to initiate a yellow-brown precipitation. The resulting bright-yellow solid was isolated by filtration (G4), washed with diethyl ether (2 x 10 ml) and subsequently dried under vacuum, yielding [Mo(CO)₂(SCOPh)(PPh₃)₂Cl] (0.764 g, 90%). 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.): δ 7.12–7.73 (m, 35H, Ph). ³¹P{¹H} NMR (CDCl₃, 298 K, δ, p.p.m.): δ 34.3. ¹³C{¹H} NMR (CDCl₃, 298 K, δ, p.p.m.): δ 127.9- 134.2 (m, C of Ph), 159.7 (s, O—Ph), 229.3, 238.6 (t, CO, ²J_P—C = 12.95, 11.95 Hz). MS (m/z): 850 (M⁺). Anal. Calcd for C₄₅H₃₅ClO₃P₂SMo: C, 63.65; H, 4.16. Found: C, 63.50; H, 4.05.