Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008079/fl6028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008079/fl6028Isup2.hkl |
CCDC reference: 214584
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 (C═N), 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%.
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.
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.
Fig. 1. A perspective view of the title compound showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
[Ru(C5H10NS2)Cl(C10H14)] | Z = 2 |
Mr = 418.99 | F(000) = 428 |
Triclinic, P1 | Dx = 1.485 Mg m−3 |
a = 9.8886 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.0266 (5) Å | Cell parameters from 5443 reflections |
c = 10.9300 (5) Å | θ = 2.2–28.3° |
α = 100.548 (1)° | µ = 1.19 mm−1 |
β = 111.312 (1)° | T = 294 K |
γ = 103.620 (1)° | Block, red |
V = 937.01 (8) Å3 | 0.30 × 0.25 × 0.20 mm |
Bruker Apex CCD area-detector diffractometer | 4582 independent reflections |
Radiation source: fine-focus sealed tube | 4275 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.659, Tmax = 0.787 | k = −13→13 |
9910 measured reflections | l = −13→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-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 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Ru(C5H10NS2)Cl(C10H14)] | γ = 103.620 (1)° |
Mr = 418.99 | V = 937.01 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.8886 (5) Å | Mo Kα radiation |
b = 10.0266 (5) Å | µ = 1.19 mm−1 |
c = 10.9300 (5) Å | T = 294 K |
α = 100.548 (1)° | 0.30 × 0.25 × 0.20 mm |
β = 111.312 (1)° |
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 = 0.787 | Rint = 0.014 |
9910 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.41 e Å−3 |
4582 reflections | Δρmin = −0.41 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.752790 (14) | 0.172635 (14) | 0.478696 (13) | 0.03634 (5) | |
S1 | 0.81680 (5) | 0.21287 (5) | 0.29391 (5) | 0.04438 (11) | |
S2 | 0.52593 (5) | 0.17057 (6) | 0.29611 (5) | 0.04762 (11) | |
Cl1 | 0.68028 (6) | −0.08310 (5) | 0.37085 (5) | 0.05189 (12) | |
N1 | 0.5689 (2) | 0.18975 (17) | 0.06877 (16) | 0.0484 (4) | |
C1 | 0.8951 (2) | 0.1430 (2) | 0.67694 (19) | 0.0490 (4) | |
C2 | 0.9824 (2) | 0.2611 (2) | 0.65551 (19) | 0.0446 (4) | |
H2A | 1.0728 | 0.2555 | 0.6401 | 0.053* | |
C3 | 0.92201 (19) | 0.37294 (19) | 0.62462 (18) | 0.0410 (4) | |
H3A | 0.9740 | 0.4431 | 0.5907 | 0.049* | |
C4 | 0.7764 (2) | 0.3711 (2) | 0.61931 (19) | 0.0423 (4) | |
C5 | 0.6906 (2) | 0.2514 (2) | 0.6438 (2) | 0.0476 (4) | |
H5A | 0.5820 | 0.2372 | 0.6220 | 0.057* | |
C6 | 0.7477 (2) | 0.1401 (2) | 0.6708 (2) | 0.0516 (5) | |
H6A | 0.6775 | 0.0503 | 0.6666 | 0.062* | |
C7 | 0.9535 (3) | 0.0201 (3) | 0.7021 (3) | 0.0694 (6) | |
H7A | 1.0119 | 0.0389 | 0.7990 | 0.104* | |
H7B | 1.0179 | 0.0101 | 0.6554 | 0.104* | |
H7C | 0.8680 | −0.0671 | 0.6678 | 0.104* | |
C8 | 0.7120 (2) | 0.4910 (2) | 0.5918 (2) | 0.0556 (5) | |
H8A | 0.5996 | 0.4500 | 0.5518 | 0.067* | |
C9 | 0.7534 (3) | 0.5619 (2) | 0.4941 (3) | 0.0618 (6) | |
H9A | 0.7202 | 0.4908 | 0.4080 | 0.093* | |
H9B | 0.8628 | 0.6074 | 0.5327 | 0.093* | |
H9C | 0.7037 | 0.6328 | 0.4793 | 0.093* | |
C10 | 0.7640 (5) | 0.6026 (3) | 0.7305 (3) | 0.0988 (11) | |
H10A | 0.7245 | 0.6798 | 0.7155 | 0.148* | |
H10B | 0.8743 | 0.6396 | 0.7753 | 0.148* | |
H10C | 0.7258 | 0.5581 | 0.7873 | 0.148* | |
C11 | 0.6282 (2) | 0.19248 (18) | 0.19932 (18) | 0.0414 (4) | |
C12 | 0.4043 (3) | 0.1692 (2) | −0.0054 (2) | 0.0581 (5) | |
H12A | 0.3495 | 0.1276 | 0.0437 | 0.070* | |
H12B | 0.3645 | 0.1013 | −0.0959 | 0.070* | |
C13 | 0.3724 (3) | 0.3051 (3) | −0.0214 (3) | 0.0776 (7) | |
H13A | 0.2637 | 0.2846 | −0.0703 | 0.116* | |
H13B | 0.4240 | 0.3458 | −0.0719 | 0.116* | |
H13D | 0.4091 | 0.3722 | 0.0678 | 0.116* | |
C14 | 0.6653 (3) | 0.2068 (2) | −0.0061 (2) | 0.0588 (5) | |
H14A | 0.6004 | 0.1635 | −0.1038 | 0.071* | |
H14C | 0.7373 | 0.1551 | 0.0210 | 0.071* | |
C15 | 0.7546 (3) | 0.3616 (3) | 0.0183 (3) | 0.0799 (8) | |
H15D | 0.8150 | 0.3648 | −0.0336 | 0.120* | |
H15A | 0.8213 | 0.4049 | 0.1144 | 0.120* | |
H15B | 0.6843 | 0.4133 | −0.0105 | 0.120* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.03198 (8) | 0.03748 (8) | 0.03834 (9) | 0.00802 (6) | 0.01401 (6) | 0.01495 (6) |
S1 | 0.0413 (2) | 0.0495 (3) | 0.0441 (2) | 0.01220 (19) | 0.01902 (19) | 0.0197 (2) |
S2 | 0.0357 (2) | 0.0540 (3) | 0.0482 (3) | 0.01190 (19) | 0.01271 (19) | 0.0184 (2) |
Cl1 | 0.0542 (3) | 0.0408 (2) | 0.0537 (3) | 0.00803 (19) | 0.0207 (2) | 0.0128 (2) |
N1 | 0.0588 (10) | 0.0395 (8) | 0.0387 (8) | 0.0149 (7) | 0.0123 (7) | 0.0129 (6) |
C1 | 0.0552 (11) | 0.0465 (10) | 0.0400 (9) | 0.0158 (9) | 0.0130 (8) | 0.0176 (8) |
C2 | 0.0368 (9) | 0.0489 (10) | 0.0425 (9) | 0.0132 (8) | 0.0113 (7) | 0.0141 (8) |
C3 | 0.0351 (8) | 0.0396 (9) | 0.0446 (9) | 0.0077 (7) | 0.0155 (7) | 0.0129 (7) |
C4 | 0.0402 (9) | 0.0439 (9) | 0.0439 (9) | 0.0129 (7) | 0.0195 (8) | 0.0129 (7) |
C5 | 0.0434 (9) | 0.0541 (11) | 0.0483 (10) | 0.0109 (8) | 0.0253 (8) | 0.0165 (8) |
C6 | 0.0594 (12) | 0.0480 (10) | 0.0454 (10) | 0.0066 (9) | 0.0242 (9) | 0.0200 (8) |
C7 | 0.0793 (16) | 0.0594 (13) | 0.0668 (14) | 0.0297 (12) | 0.0172 (12) | 0.0332 (11) |
C8 | 0.0490 (11) | 0.0563 (12) | 0.0737 (14) | 0.0268 (9) | 0.0301 (10) | 0.0261 (10) |
C9 | 0.0615 (13) | 0.0510 (12) | 0.0781 (15) | 0.0225 (10) | 0.0280 (12) | 0.0287 (11) |
C10 | 0.153 (3) | 0.089 (2) | 0.105 (2) | 0.081 (2) | 0.080 (2) | 0.0356 (18) |
C11 | 0.0461 (9) | 0.0313 (8) | 0.0421 (9) | 0.0111 (7) | 0.0136 (8) | 0.0129 (7) |
C12 | 0.0606 (13) | 0.0487 (11) | 0.0431 (10) | 0.0127 (9) | 0.0026 (9) | 0.0120 (8) |
C13 | 0.0777 (17) | 0.0605 (15) | 0.0838 (18) | 0.0330 (13) | 0.0180 (14) | 0.0178 (13) |
C14 | 0.0801 (15) | 0.0544 (12) | 0.0417 (10) | 0.0221 (11) | 0.0246 (10) | 0.0165 (9) |
C15 | 0.100 (2) | 0.0647 (15) | 0.0863 (19) | 0.0219 (14) | 0.0484 (17) | 0.0366 (14) |
Ru1—C3 | 2.1638 (17) | C6—H6A | 0.9800 |
Ru1—C5 | 2.1846 (18) | C7—H7A | 0.9600 |
Ru1—C4 | 2.1857 (18) | C7—H7B | 0.9600 |
Ru1—C6 | 2.1999 (19) | C7—H7C | 0.9600 |
Ru1—C2 | 2.2159 (18) | C8—C9 | 1.507 (3) |
Ru1—C1 | 2.2318 (18) | C8—C10 | 1.535 (4) |
Ru1—S2 | 2.3925 (5) | C8—H8A | 0.9800 |
Ru1—S1 | 2.3979 (5) | C9—H9A | 0.9600 |
Ru1—Cl1 | 2.4272 (5) | C9—H9B | 0.9600 |
S1—C11 | 1.7122 (19) | C9—H9C | 0.9600 |
S2—C11 | 1.717 (2) | C10—H10A | 0.9600 |
N1—C11 | 1.323 (2) | C10—H10B | 0.9600 |
N1—C14 | 1.467 (3) | C10—H10C | 0.9600 |
N1—C12 | 1.474 (3) | C12—C13 | 1.495 (3) |
C1—C2 | 1.403 (3) | C12—H12A | 0.9700 |
C1—C6 | 1.428 (3) | C12—H12B | 0.9700 |
C1—C7 | 1.507 (3) | C13—H13A | 0.9600 |
C2—C3 | 1.427 (2) | C13—H13B | 0.9600 |
C2—H2A | 0.9800 | C13—H13D | 0.9600 |
C3—C4 | 1.415 (2) | C14—C15 | 1.514 (3) |
C3—H3A | 0.9800 | C14—H14A | 0.9700 |
C4—C5 | 1.426 (3) | C14—H14C | 0.9700 |
C4—C8 | 1.515 (3) | C15—H15D | 0.9600 |
C5—C6 | 1.396 (3) | C15—H15A | 0.9600 |
C5—H5A | 0.9800 | C15—H15B | 0.9600 |
C3—Ru1—C5 | 67.87 (7) | C8—C4—Ru1 | 130.85 (14) |
C3—Ru1—C4 | 37.97 (6) | C6—C5—C4 | 121.22 (17) |
C5—Ru1—C4 | 38.10 (7) | C6—C5—Ru1 | 72.03 (11) |
C3—Ru1—C6 | 79.88 (7) | C4—C5—Ru1 | 70.99 (10) |
C5—Ru1—C6 | 37.14 (8) | C6—C5—H5A | 118.7 |
C4—Ru1—C6 | 68.22 (7) | C4—C5—H5A | 118.7 |
C3—Ru1—C2 | 38.00 (7) | Ru1—C5—H5A | 118.7 |
C5—Ru1—C2 | 79.66 (7) | C5—C6—C1 | 121.14 (18) |
C4—Ru1—C2 | 68.60 (7) | C5—C6—Ru1 | 70.84 (11) |
C6—Ru1—C2 | 66.86 (7) | C1—C6—Ru1 | 72.41 (11) |
C3—Ru1—C1 | 67.83 (7) | C5—C6—H6A | 118.8 |
C5—Ru1—C1 | 67.69 (8) | C1—C6—H6A | 118.8 |
C4—Ru1—C1 | 81.18 (7) | Ru1—C6—H6A | 118.8 |
C6—Ru1—C1 | 37.60 (8) | C1—C7—H7A | 109.5 |
C2—Ru1—C1 | 36.78 (7) | C1—C7—H7B | 109.5 |
C3—Ru1—S2 | 120.86 (5) | H7A—C7—H7B | 109.5 |
C5—Ru1—S2 | 95.52 (5) | C1—C7—H7C | 109.5 |
C4—Ru1—S2 | 94.66 (5) | H7A—C7—H7C | 109.5 |
C6—Ru1—S2 | 120.60 (6) | H7B—C7—H7C | 109.5 |
C2—Ru1—S2 | 158.55 (5) | C9—C8—C4 | 115.33 (17) |
C1—Ru1—S2 | 157.66 (6) | C9—C8—C10 | 110.5 (2) |
C3—Ru1—S1 | 93.58 (5) | C4—C8—C10 | 107.98 (19) |
C5—Ru1—S1 | 148.83 (5) | C9—C8—H8A | 107.6 |
C4—Ru1—S1 | 112.81 (5) | C4—C8—H8A | 107.6 |
C6—Ru1—S1 | 167.38 (6) | C10—C8—H8A | 107.6 |
C2—Ru1—S1 | 101.39 (5) | C8—C9—H9A | 109.5 |
C1—Ru1—S1 | 129.86 (6) | C8—C9—H9B | 109.5 |
S2—Ru1—S1 | 72.023 (17) | H9A—C9—H9B | 109.5 |
C3—Ru1—Cl1 | 150.38 (5) | C8—C9—H9C | 109.5 |
C5—Ru1—Cl1 | 120.94 (5) | H9A—C9—H9C | 109.5 |
C4—Ru1—Cl1 | 159.02 (5) | H9B—C9—H9C | 109.5 |
C6—Ru1—Cl1 | 92.64 (6) | C8—C10—H10A | 109.5 |
C2—Ru1—Cl1 | 112.81 (5) | C8—C10—H10B | 109.5 |
C1—Ru1—Cl1 | 88.74 (5) | H10A—C10—H10B | 109.5 |
S2—Ru1—Cl1 | 87.695 (18) | C8—C10—H10C | 109.5 |
S1—Ru1—Cl1 | 87.769 (18) | H10A—C10—H10C | 109.5 |
C11—S1—Ru1 | 88.63 (7) | H10B—C10—H10C | 109.5 |
C11—S2—Ru1 | 88.70 (6) | N1—C11—S1 | 124.63 (15) |
C11—N1—C14 | 120.86 (17) | N1—C11—S2 | 124.89 (15) |
C11—N1—C12 | 120.95 (18) | S1—C11—S2 | 110.45 (10) |
C14—N1—C12 | 118.19 (16) | N1—C12—C13 | 113.55 (19) |
C2—C1—C6 | 118.44 (17) | N1—C12—H12A | 108.9 |
C2—C1—C7 | 120.9 (2) | C13—C12—H12A | 108.9 |
C6—C1—C7 | 120.7 (2) | N1—C12—H12B | 108.9 |
C2—C1—Ru1 | 71.00 (10) | C13—C12—H12B | 108.9 |
C6—C1—Ru1 | 69.99 (11) | H12A—C12—H12B | 107.7 |
C7—C1—Ru1 | 129.32 (15) | C12—C13—H13A | 109.5 |
C1—C2—C3 | 120.21 (17) | C12—C13—H13B | 109.5 |
C1—C2—Ru1 | 72.23 (11) | H13A—C13—H13B | 109.5 |
C3—C2—Ru1 | 69.02 (10) | C12—C13—H13D | 109.5 |
C1—C2—H2A | 119.1 | H13A—C13—H13D | 109.5 |
C3—C2—H2A | 119.1 | H13B—C13—H13D | 109.5 |
Ru1—C2—H2A | 119.1 | N1—C14—C15 | 113.92 (19) |
C4—C3—C2 | 121.59 (17) | N1—C14—H14A | 108.8 |
C4—C3—Ru1 | 71.85 (10) | C15—C14—H14A | 108.8 |
C2—C3—Ru1 | 72.98 (10) | N1—C14—H14C | 108.8 |
C4—C3—H3A | 118.8 | C15—C14—H14C | 108.8 |
C2—C3—H3A | 118.8 | H14A—C14—H14C | 107.7 |
Ru1—C3—H3A | 118.8 | C14—C15—H15D | 109.5 |
C3—C4—C5 | 117.37 (17) | C14—C15—H15A | 109.5 |
C3—C4—C8 | 122.71 (17) | H15D—C15—H15A | 109.5 |
C5—C4—C8 | 119.91 (17) | C14—C15—H15B | 109.5 |
C3—C4—Ru1 | 70.18 (10) | H15D—C15—H15B | 109.5 |
C5—C4—Ru1 | 70.91 (11) | H15A—C15—H15B | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [Ru(C5H10NS2)Cl(C10H14)] |
Mr | 418.99 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 937.01 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker Apex CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.659, 0.787 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9910, 4582, 4275 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.061, 1.08 |
No. of reflections | 4582 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.41 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Ru1—C3 | 2.1638 (17) | Ru1—S1 | 2.3979 (5) |
Ru1—C5 | 2.1846 (18) | Ru1—Cl1 | 2.4272 (5) |
Ru1—C4 | 2.1857 (18) | S1—C11 | 1.7122 (19) |
Ru1—C6 | 2.1999 (19) | S2—C11 | 1.717 (2) |
Ru1—C2 | 2.2159 (18) | N1—C11 | 1.323 (2) |
Ru1—C1 | 2.2318 (18) | N1—C14 | 1.467 (3) |
Ru1—S2 | 2.3925 (5) | N1—C12 | 1.474 (3) |
C3—Ru1—S2 | 120.86 (5) | C3—Ru1—Cl1 | 150.38 (5) |
C5—Ru1—S2 | 95.52 (5) | C5—Ru1—Cl1 | 120.94 (5) |
C4—Ru1—S2 | 94.66 (5) | C4—Ru1—Cl1 | 159.02 (5) |
C6—Ru1—S2 | 120.60 (6) | C6—Ru1—Cl1 | 92.64 (6) |
C2—Ru1—S2 | 158.55 (5) | C2—Ru1—Cl1 | 112.81 (5) |
C1—Ru1—S2 | 157.66 (6) | C1—Ru1—Cl1 | 88.74 (5) |
C3—Ru1—S1 | 93.58 (5) | S2—Ru1—Cl1 | 87.695 (18) |
C5—Ru1—S1 | 148.83 (5) | S1—Ru1—Cl1 | 87.769 (18) |
C4—Ru1—S1 | 112.81 (5) | C11—S1—Ru1 | 88.63 (7) |
C6—Ru1—S1 | 167.38 (6) | C11—S2—Ru1 | 88.70 (6) |
C2—Ru1—S1 | 101.39 (5) | C11—N1—C14 | 120.86 (17) |
C1—Ru1—S1 | 129.86 (6) | C11—N1—C12 | 120.95 (18) |
S2—Ru1—S1 | 72.023 (17) |
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 C═N bond with a considerable double-bond character.