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The structure of the title compound, [Ru(C5H10NS2)Cl(η6-C10H14)], consists of a ruthenium center bonded to an η6-p-cymene, a chelating diethyl­di­thio­carbamate and a terminal chloride. The Ru atom adopts an octahedral configuration. The metal–ligand distances are Ru—Cl = 2.4276 (5) Å, Ru—S = 2.3978 (5) Å and Ru—S = 2.3925 (5) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008079/fl6028sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008079/fl6028Isup2.hkl
Contains datablock I

CCDC reference: 214584

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.024
  • wR factor = 0.061
  • Data-to-parameter ratio = 25.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_601 Alert C Structure Contains Solvent Accessible VOIDS of 56.00 A   3
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The chemistry of transition metal–sulfur compounds has attracted much interest for their importance in the field of metalloenzymes, materials precursors, and catalysts (Hidai et al., 2000). In recent years there has been an increased interest in ruthenium complexes with sulfur-donor ligands, in part because of the high catalytic activity of RuS2 in various hydrotreating processes (Vit & Zdrazil, 1989). As part of this development, many examples of ruthenium–thiolate complexes have been reported, however, ruthenium complexes with dithio ligands are rare (Sellmann et al., 1999). Because the arene–ruthenium complexes, such as [RuCl2(arene)]2 and [RuCl2(PR3)(arene)], have been used as homogenous catalysts (Lavastre & Dixneuf, 1995), the [(arene)Ru] species may act as an effective mode to be used to expand its reactivity and catalytic property (Pearson et al., 1996). In our research to prepare the ruthenium complexes with sulfur- and selenium-donor ligands (Zhang et al., 2001), we have synthesized the arene–ruthenium complexes with bidentate dithiocarbamate ligands, and have attempted to establish the structural characterization of this typical complex. In this paper, the results of this work are initially reported.

The molecular structure of the title complex, (I), consists of discrete monomeric molecules with distorted octchedral configuration around the Ru atom having a p-cymene ring at one face. The (η6-p-cymene)Ru fragment is coordinated with S atoms of a symmetrically chelated diethyldithiocarbamate group and a terminal chloride ligand. The ruthenium atom is situated 1.749 (2) Å from the center of the planar phenyl in the p-cymene moiety. All Ru—C bond distances in (I) are in the range of 2.1604 (17)—2.2319 (17) Å, in good agreement with the values in other related complexes, such as [(η6-p-cymene)RuCl2(PH2Cy)] (Van der Maelen Uría et al., 1994) and [(η6-p-cymene)RuCl(µ-N3)] (Bates et al., 1990). The two Ru—S bond distances are essentially the same [2.3925 (5) and 2.3978 (5) Å], slightly shorter than those in [(η6-p-cymene)Ru{S2P(OMe)2}(PPh3)][BPh4] [2.431 (2) and 2.4312 (14) Å] with a chelated dithiophosphate ligand (Jain & Jakkal, 1996). The Ru—Cl bond length of 2.4276 (5) Å in (I) is slightly longer that those reported in the other complexes, such as in [(p-cymene)RuCl(Me2PCH2CH2SMe)][BPh4] [2.389 (2) Å] (Suzuki et al., 1996) and [(η6-p-cymene)RuCl2(PH2Cy)] [2.408 (1) and 2.411 (1) Å; Van der Maelen Uría et al., 1994]. One of the angles around the ruthenium, S1—Ru1—S2, is considerably reduced [72.019 (17)°] due to the small bite of the dithio ligand. The four-membered chelete ring RuS2C is approximately planar, with deviations of 0.0262 Å from the least-squares plane. The short C11—N1 bond length of 1.325 (2) Å in (I) indicates considerable partial double-bond character as is typical for the chelating 1,1-dithiolate ligands (Eisenberg, 1970). In the The FT–IR spectrum of (I) also shows that the strong absorption at 1482 cm−1 is due to the stretching vibration of the CN bond with a considerable double-bond character.

Experimental top

To a THF solution (25 ml) of [(η6-p-cymene)RuCl2]2 (225 mg, 0.45 mmol) was added one equivalent of diethyldithiocarbamate sodium Et2NCS2Na·3H2O (101 mg, 0.45 mmol). The mixture was stirred at room temperature for 6 h during which time a brown solution was obtained. The solvent was pumped off and the residue was washed with diethyl ether and hexane. The dark-orange solid was recrystallized from CH2Cl2/hexane to give orange block crystals. 1H NMR (CDCl3, p.p.m.): δ 1.20 (m, CH2CH3), 1.30 [d, 7.2 Hz, CH(CH3)2], 2.98 [septet, 7.8 Hz, CH(CH3)2], 3.48 (m, CH2CH3), 5.47 and 5.78 (dd, each 6.2 Hz, C6H4). MS (FAB): m/z 420 (M+ + 1). IR (KBr pellets, cm−1): ν (CN), 1482 (s); (C—S), 992 (s), 926 (m). Analysis calculated for C15H24ClNRuS2: C 42.96, H 5.73, N 3.34%; found: C 42.58, H 5.71, N 3.33%.

Refinement top

The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; using two different ϕ angles (0,88 and 180°) for the crystal and each exposure of 20 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible. There is avoid of 56 Å3 in the cell but while the final difference map showed some fairly large ripples around the Ru atoms there was nothing of any significance in the void.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A perspective view of the title compound showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
(I) top
Crystal data top
[Ru(C5H10NS2)Cl(C10H14)]Z = 2
Mr = 418.99F(000) = 428
Triclinic, P1Dx = 1.485 Mg m3
a = 9.8886 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.0266 (5) ÅCell parameters from 5443 reflections
c = 10.9300 (5) Åθ = 2.2–28.3°
α = 100.548 (1)°µ = 1.19 mm1
β = 111.312 (1)°T = 294 K
γ = 103.620 (1)°Block, red
V = 937.01 (8) Å30.30 × 0.25 × 0.20 mm
Data collection top
Bruker Apex CCD area-detector
diffractometer
4582 independent reflections
Radiation source: fine-focus sealed tube4275 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
ϕ and ω scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1313
Tmin = 0.659, Tmax = 0.787k = 1313
9910 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0296P)2 + 0.1488P]
where P = (Fo2 + 2Fc2)/3
4582 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
[Ru(C5H10NS2)Cl(C10H14)]γ = 103.620 (1)°
Mr = 418.99V = 937.01 (8) Å3
Triclinic, P1Z = 2
a = 9.8886 (5) ÅMo Kα radiation
b = 10.0266 (5) ŵ = 1.19 mm1
c = 10.9300 (5) ÅT = 294 K
α = 100.548 (1)°0.30 × 0.25 × 0.20 mm
β = 111.312 (1)°
Data collection top
Bruker Apex CCD area-detector
diffractometer
4582 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4275 reflections with I > 2σ(I)
Tmin = 0.659, Tmax = 0.787Rint = 0.014
9910 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.08Δρmax = 0.41 e Å3
4582 reflectionsΔρmin = 0.41 e Å3
181 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ru10.752790 (14)0.172635 (14)0.478696 (13)0.03634 (5)
S10.81680 (5)0.21287 (5)0.29391 (5)0.04438 (11)
S20.52593 (5)0.17057 (6)0.29611 (5)0.04762 (11)
Cl10.68028 (6)0.08310 (5)0.37085 (5)0.05189 (12)
N10.5689 (2)0.18975 (17)0.06877 (16)0.0484 (4)
C10.8951 (2)0.1430 (2)0.67694 (19)0.0490 (4)
C20.9824 (2)0.2611 (2)0.65551 (19)0.0446 (4)
H2A1.07280.25550.64010.053*
C30.92201 (19)0.37294 (19)0.62462 (18)0.0410 (4)
H3A0.97400.44310.59070.049*
C40.7764 (2)0.3711 (2)0.61931 (19)0.0423 (4)
C50.6906 (2)0.2514 (2)0.6438 (2)0.0476 (4)
H5A0.58200.23720.62200.057*
C60.7477 (2)0.1401 (2)0.6708 (2)0.0516 (5)
H6A0.67750.05030.66660.062*
C70.9535 (3)0.0201 (3)0.7021 (3)0.0694 (6)
H7A1.01190.03890.79900.104*
H7B1.01790.01010.65540.104*
H7C0.86800.06710.66780.104*
C80.7120 (2)0.4910 (2)0.5918 (2)0.0556 (5)
H8A0.59960.45000.55180.067*
C90.7534 (3)0.5619 (2)0.4941 (3)0.0618 (6)
H9A0.72020.49080.40800.093*
H9B0.86280.60740.53270.093*
H9C0.70370.63280.47930.093*
C100.7640 (5)0.6026 (3)0.7305 (3)0.0988 (11)
H10A0.72450.67980.71550.148*
H10B0.87430.63960.77530.148*
H10C0.72580.55810.78730.148*
C110.6282 (2)0.19248 (18)0.19932 (18)0.0414 (4)
C120.4043 (3)0.1692 (2)0.0054 (2)0.0581 (5)
H12A0.34950.12760.04370.070*
H12B0.36450.10130.09590.070*
C130.3724 (3)0.3051 (3)0.0214 (3)0.0776 (7)
H13A0.26370.28460.07030.116*
H13B0.42400.34580.07190.116*
H13D0.40910.37220.06780.116*
C140.6653 (3)0.2068 (2)0.0061 (2)0.0588 (5)
H14A0.60040.16350.10380.071*
H14C0.73730.15510.02100.071*
C150.7546 (3)0.3616 (3)0.0183 (3)0.0799 (8)
H15D0.81500.36480.03360.120*
H15A0.82130.40490.11440.120*
H15B0.68430.41330.01050.120*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.03198 (8)0.03748 (8)0.03834 (9)0.00802 (6)0.01401 (6)0.01495 (6)
S10.0413 (2)0.0495 (3)0.0441 (2)0.01220 (19)0.01902 (19)0.0197 (2)
S20.0357 (2)0.0540 (3)0.0482 (3)0.01190 (19)0.01271 (19)0.0184 (2)
Cl10.0542 (3)0.0408 (2)0.0537 (3)0.00803 (19)0.0207 (2)0.0128 (2)
N10.0588 (10)0.0395 (8)0.0387 (8)0.0149 (7)0.0123 (7)0.0129 (6)
C10.0552 (11)0.0465 (10)0.0400 (9)0.0158 (9)0.0130 (8)0.0176 (8)
C20.0368 (9)0.0489 (10)0.0425 (9)0.0132 (8)0.0113 (7)0.0141 (8)
C30.0351 (8)0.0396 (9)0.0446 (9)0.0077 (7)0.0155 (7)0.0129 (7)
C40.0402 (9)0.0439 (9)0.0439 (9)0.0129 (7)0.0195 (8)0.0129 (7)
C50.0434 (9)0.0541 (11)0.0483 (10)0.0109 (8)0.0253 (8)0.0165 (8)
C60.0594 (12)0.0480 (10)0.0454 (10)0.0066 (9)0.0242 (9)0.0200 (8)
C70.0793 (16)0.0594 (13)0.0668 (14)0.0297 (12)0.0172 (12)0.0332 (11)
C80.0490 (11)0.0563 (12)0.0737 (14)0.0268 (9)0.0301 (10)0.0261 (10)
C90.0615 (13)0.0510 (12)0.0781 (15)0.0225 (10)0.0280 (12)0.0287 (11)
C100.153 (3)0.089 (2)0.105 (2)0.081 (2)0.080 (2)0.0356 (18)
C110.0461 (9)0.0313 (8)0.0421 (9)0.0111 (7)0.0136 (8)0.0129 (7)
C120.0606 (13)0.0487 (11)0.0431 (10)0.0127 (9)0.0026 (9)0.0120 (8)
C130.0777 (17)0.0605 (15)0.0838 (18)0.0330 (13)0.0180 (14)0.0178 (13)
C140.0801 (15)0.0544 (12)0.0417 (10)0.0221 (11)0.0246 (10)0.0165 (9)
C150.100 (2)0.0647 (15)0.0863 (19)0.0219 (14)0.0484 (17)0.0366 (14)
Geometric parameters (Å, º) top
Ru1—C32.1638 (17)C6—H6A0.9800
Ru1—C52.1846 (18)C7—H7A0.9600
Ru1—C42.1857 (18)C7—H7B0.9600
Ru1—C62.1999 (19)C7—H7C0.9600
Ru1—C22.2159 (18)C8—C91.507 (3)
Ru1—C12.2318 (18)C8—C101.535 (4)
Ru1—S22.3925 (5)C8—H8A0.9800
Ru1—S12.3979 (5)C9—H9A0.9600
Ru1—Cl12.4272 (5)C9—H9B0.9600
S1—C111.7122 (19)C9—H9C0.9600
S2—C111.717 (2)C10—H10A0.9600
N1—C111.323 (2)C10—H10B0.9600
N1—C141.467 (3)C10—H10C0.9600
N1—C121.474 (3)C12—C131.495 (3)
C1—C21.403 (3)C12—H12A0.9700
C1—C61.428 (3)C12—H12B0.9700
C1—C71.507 (3)C13—H13A0.9600
C2—C31.427 (2)C13—H13B0.9600
C2—H2A0.9800C13—H13D0.9600
C3—C41.415 (2)C14—C151.514 (3)
C3—H3A0.9800C14—H14A0.9700
C4—C51.426 (3)C14—H14C0.9700
C4—C81.515 (3)C15—H15D0.9600
C5—C61.396 (3)C15—H15A0.9600
C5—H5A0.9800C15—H15B0.9600
C3—Ru1—C567.87 (7)C8—C4—Ru1130.85 (14)
C3—Ru1—C437.97 (6)C6—C5—C4121.22 (17)
C5—Ru1—C438.10 (7)C6—C5—Ru172.03 (11)
C3—Ru1—C679.88 (7)C4—C5—Ru170.99 (10)
C5—Ru1—C637.14 (8)C6—C5—H5A118.7
C4—Ru1—C668.22 (7)C4—C5—H5A118.7
C3—Ru1—C238.00 (7)Ru1—C5—H5A118.7
C5—Ru1—C279.66 (7)C5—C6—C1121.14 (18)
C4—Ru1—C268.60 (7)C5—C6—Ru170.84 (11)
C6—Ru1—C266.86 (7)C1—C6—Ru172.41 (11)
C3—Ru1—C167.83 (7)C5—C6—H6A118.8
C5—Ru1—C167.69 (8)C1—C6—H6A118.8
C4—Ru1—C181.18 (7)Ru1—C6—H6A118.8
C6—Ru1—C137.60 (8)C1—C7—H7A109.5
C2—Ru1—C136.78 (7)C1—C7—H7B109.5
C3—Ru1—S2120.86 (5)H7A—C7—H7B109.5
C5—Ru1—S295.52 (5)C1—C7—H7C109.5
C4—Ru1—S294.66 (5)H7A—C7—H7C109.5
C6—Ru1—S2120.60 (6)H7B—C7—H7C109.5
C2—Ru1—S2158.55 (5)C9—C8—C4115.33 (17)
C1—Ru1—S2157.66 (6)C9—C8—C10110.5 (2)
C3—Ru1—S193.58 (5)C4—C8—C10107.98 (19)
C5—Ru1—S1148.83 (5)C9—C8—H8A107.6
C4—Ru1—S1112.81 (5)C4—C8—H8A107.6
C6—Ru1—S1167.38 (6)C10—C8—H8A107.6
C2—Ru1—S1101.39 (5)C8—C9—H9A109.5
C1—Ru1—S1129.86 (6)C8—C9—H9B109.5
S2—Ru1—S172.023 (17)H9A—C9—H9B109.5
C3—Ru1—Cl1150.38 (5)C8—C9—H9C109.5
C5—Ru1—Cl1120.94 (5)H9A—C9—H9C109.5
C4—Ru1—Cl1159.02 (5)H9B—C9—H9C109.5
C6—Ru1—Cl192.64 (6)C8—C10—H10A109.5
C2—Ru1—Cl1112.81 (5)C8—C10—H10B109.5
C1—Ru1—Cl188.74 (5)H10A—C10—H10B109.5
S2—Ru1—Cl187.695 (18)C8—C10—H10C109.5
S1—Ru1—Cl187.769 (18)H10A—C10—H10C109.5
C11—S1—Ru188.63 (7)H10B—C10—H10C109.5
C11—S2—Ru188.70 (6)N1—C11—S1124.63 (15)
C11—N1—C14120.86 (17)N1—C11—S2124.89 (15)
C11—N1—C12120.95 (18)S1—C11—S2110.45 (10)
C14—N1—C12118.19 (16)N1—C12—C13113.55 (19)
C2—C1—C6118.44 (17)N1—C12—H12A108.9
C2—C1—C7120.9 (2)C13—C12—H12A108.9
C6—C1—C7120.7 (2)N1—C12—H12B108.9
C2—C1—Ru171.00 (10)C13—C12—H12B108.9
C6—C1—Ru169.99 (11)H12A—C12—H12B107.7
C7—C1—Ru1129.32 (15)C12—C13—H13A109.5
C1—C2—C3120.21 (17)C12—C13—H13B109.5
C1—C2—Ru172.23 (11)H13A—C13—H13B109.5
C3—C2—Ru169.02 (10)C12—C13—H13D109.5
C1—C2—H2A119.1H13A—C13—H13D109.5
C3—C2—H2A119.1H13B—C13—H13D109.5
Ru1—C2—H2A119.1N1—C14—C15113.92 (19)
C4—C3—C2121.59 (17)N1—C14—H14A108.8
C4—C3—Ru171.85 (10)C15—C14—H14A108.8
C2—C3—Ru172.98 (10)N1—C14—H14C108.8
C4—C3—H3A118.8C15—C14—H14C108.8
C2—C3—H3A118.8H14A—C14—H14C107.7
Ru1—C3—H3A118.8C14—C15—H15D109.5
C3—C4—C5117.37 (17)C14—C15—H15A109.5
C3—C4—C8122.71 (17)H15D—C15—H15A109.5
C5—C4—C8119.91 (17)C14—C15—H15B109.5
C3—C4—Ru170.18 (10)H15D—C15—H15B109.5
C5—C4—Ru170.91 (11)H15A—C15—H15B109.5

Experimental details

Crystal data
Chemical formula[Ru(C5H10NS2)Cl(C10H14)]
Mr418.99
Crystal system, space groupTriclinic, P1
Temperature (K)294
a, b, c (Å)9.8886 (5), 10.0266 (5), 10.9300 (5)
α, β, γ (°)100.548 (1), 111.312 (1), 103.620 (1)
V3)937.01 (8)
Z2
Radiation typeMo Kα
µ (mm1)1.19
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker Apex CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.659, 0.787
No. of measured, independent and
observed [I > 2σ(I)] reflections
9910, 4582, 4275
Rint0.014
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.061, 1.08
No. of reflections4582
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.41, 0.41

Computer programs: SMART (Bruker, 1998), SMART, SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) top
Ru1—C32.1638 (17)Ru1—S12.3979 (5)
Ru1—C52.1846 (18)Ru1—Cl12.4272 (5)
Ru1—C42.1857 (18)S1—C111.7122 (19)
Ru1—C62.1999 (19)S2—C111.717 (2)
Ru1—C22.2159 (18)N1—C111.323 (2)
Ru1—C12.2318 (18)N1—C141.467 (3)
Ru1—S22.3925 (5)N1—C121.474 (3)
C3—Ru1—S2120.86 (5)C3—Ru1—Cl1150.38 (5)
C5—Ru1—S295.52 (5)C5—Ru1—Cl1120.94 (5)
C4—Ru1—S294.66 (5)C4—Ru1—Cl1159.02 (5)
C6—Ru1—S2120.60 (6)C6—Ru1—Cl192.64 (6)
C2—Ru1—S2158.55 (5)C2—Ru1—Cl1112.81 (5)
C1—Ru1—S2157.66 (6)C1—Ru1—Cl188.74 (5)
C3—Ru1—S193.58 (5)S2—Ru1—Cl187.695 (18)
C5—Ru1—S1148.83 (5)S1—Ru1—Cl187.769 (18)
C4—Ru1—S1112.81 (5)C11—S1—Ru188.63 (7)
C6—Ru1—S1167.38 (6)C11—S2—Ru188.70 (6)
C2—Ru1—S1101.39 (5)C11—N1—C14120.86 (17)
C1—Ru1—S1129.86 (6)C11—N1—C12120.95 (18)
S2—Ru1—S172.023 (17)
 

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