Orthorhombic cis-di­chloro­tetrakis­(di­methyl sulfoxide)­ruthenium(II) at 120 K

Refinement of the structure of the Pccn polymorph of the title compound, [RuCl₂(C₂H₆OS)₄], using low-temperature data, has led to an increase in precision by a factor of 2-3 over the previous room-temperature results [Attia & Calligaris (1987). Acta Cryst. C43, 1426-1427] and those for the P2₁/n polymorph [Mercer & Trotter (1975). J. Chem. Soc. Dalton Trans. pp. 2480-2483; Alessio et al. (1988) Inorg. Chem. 27, 4099-4106]. The chloro ligands are cis, with Ru-Cl distances of 2.4165 (8) and 2.4352 (8) Å, and the di­methyl sulfoxide (DMSO) ligands trans to them are S-bonded, with Ru-S distances of 2.2717 (8) and 2.2734 (9) Å. One of the two mutually trans DMSO ligands is O-bonded, and the Ru-S distance trans to it is shortened, at 2.2480 (9) Å.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](S-C) = 0.004 Å
• R factor = 0.046
• wR factor = 0.088
• Data-to-parameter ratio = 37.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

During the course of our studies of ruthenium complexes containing coordinated dimethyl sulfoxide and tetramethylene sulfoxide, mer-RuCl₃(DMSO)₃ was treated with 1,2-bis(diphenylphosphino)ethane (dppe) in the presence of excess DMSO in an attempt to introduce the dppe ligand onto the metal center. The resulting orange crystals were determined by crystal structure determination to be cis-RuCl₂(DMSO)₄, (I), for which both monoclinic (Mercer & Trotter, 1975; Alessio et al., 1988) and orthorhombic (Attia & Calligaris, 1987) polymorphs have been previously reported at room temperature. The sample reported here is identical to the orthorhombic polymorph, and refinement versus 120 K data has led to an increase in precision by a factor of 2.5–3.0, with excellent agreement. These results are also approximately twice as precise as the room-temperature results for the monoclinic (P2₁/n) polymorph. Of the four DMSO ligands, three are S-coordinated, including both trans to Cl. As reported by Mercer & Trotter (1975), the Ru—S distance trans to the O-bonded DMSO is significantly shortened, being more than 0.02 Å shorter than the other two. The S—O distance in the O-bonded DMSO ligand is indicative of less double bond character than the other three, being about 0.05 Å longer.

Alessio et al. (1991) have reported the structures of trans-RuCl₄(DMSO)₂, which has S-bonded DMSO ligands, and also mer-RuCl₃(DMSO)₃, which has one O-bonded DMSO. However, in that case, the O-bonded DMSO is trans to Cl rather than to S-bonded DMSO. That paper also reports a scheme for the reduction of mer-RuCl₃(DMSO)₃ to the title compound.

S2. Experimental

To 0.264 g, 0.597 mmol of mer-RuCl₃(DMSO)₃ dissolved in chloroform (10 ml) and 2 ml of DMSO were added 0.10 g, 0.25 mmol of solid dppe. The mixture was stirred for 24 h, yielding a brown solution. The solution was concentrated to one third of its volume on a rotary evaporator and was slowly evaporated at room temperature to yield orange crystals. The product was filtered, washed with diethyl ether and then vacuum dried (70% yield).

S3. Refinement

H atoms were placed in idealized positions, with C—H bond distances of 0.98 Å, utilizing difference maps in the expected toruses, and thereafter treated as riding, with a torsional parameter refined for each methyl group. Displacement parameters for H were assigned as U_iso = 1.5U_eq of the attached atom.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: Coordinates of Attia & Calligaris (1987); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The numbering scheme and ellipsoids at the 50% probability level.

cis-dichlorotetrakis(dimethyl sulfoxide)ruthenium(II)

Crystal data

[RuCl2(C2H6OS)4]	F(000) = 1968
Mr = 484.48	Dx = 1.813 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 6991 reflections
a = 28.167 (7) Å	θ = 2.5–33.1°
b = 10.817 (2) Å	µ = 1.66 mm^−1
c = 11.648 (2) Å	T = 120 K
V = 3548.9 (13) Å^3	Fragment, orange
Z = 8	0.20 × 0.17 × 0.12 mm

Data collection

KappaCCD (with Oxford Cryostream cooler) diffractometer	6724 independent reflections
Radiation source: fine-focus sealed tube	3830 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ω scans with κ offsets	θmax = 33.2°, θmin = 2.8°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	h = −43→43
Tmin = 0.748, Tmax = 0.819	k = −16→16
25051 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0256P)^2] where P = (Fo^2 + 2Fc^2)/3
6724 reflections	(Δ/σ)max = 0.001
180 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.95 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ru1	0.125124 (9)	0.45806 (2)	0.326081 (19)	0.01115 (6)
Cl1	0.08894 (3)	0.40538 (8)	0.50771 (6)	0.02033 (19)
Cl2	0.20040 (3)	0.40373 (8)	0.41566 (6)	0.01772 (18)
S1	0.12775 (3)	0.65750 (8)	0.37996 (6)	0.01643 (17)
S2	0.05319 (3)	0.47937 (8)	0.23980 (6)	0.01500 (18)
S3	0.16648 (3)	0.49058 (8)	0.16140 (6)	0.01322 (17)
S4	0.12993 (3)	0.16095 (8)	0.35765 (6)	0.01347 (17)
O1	0.14006 (8)	0.7534 (2)	0.29499 (18)	0.0239 (6)
O2	0.03469 (9)	0.6034 (2)	0.2101 (2)	0.0260 (6)
O3	0.14209 (8)	0.5386 (2)	0.05727 (16)	0.0160 (5)
O4	0.11993 (7)	0.2685 (2)	0.27505 (17)	0.0135 (5)
C11	0.07502 (13)	0.7077 (3)	0.4487 (3)	0.0285 (9)
H11A	0.0810	0.7864	0.4878	0.043*
H11B	0.0650	0.6456	0.5049	0.043*
H11C	0.0500	0.7189	0.3913	0.043*
C12	0.16782 (15)	0.6762 (4)	0.4977 (3)	0.0378 (11)
H12A	0.2002	0.6577	0.4723	0.057*
H12B	0.1589	0.6196	0.5597	0.057*
H12C	0.1663	0.7616	0.5256	0.057*
C21	0.00767 (12)	0.4021 (4)	0.3199 (3)	0.0238 (8)
H21A	−0.0002	0.4508	0.3883	0.036*
H21B	0.0190	0.3202	0.3433	0.036*
H21C	−0.0207	0.3930	0.2720	0.036*
C22	0.04970 (13)	0.3886 (4)	0.1133 (3)	0.0236 (8)
H22A	0.0175	0.3934	0.0818	0.035*
H22B	0.0573	0.3025	0.1316	0.035*
H22C	0.0724	0.4200	0.0565	0.035*
C31	0.19562 (13)	0.3514 (3)	0.1196 (3)	0.0192 (8)
H31A	0.1720	0.2915	0.0926	0.029*
H31B	0.2127	0.3169	0.1856	0.029*
H31C	0.2182	0.3692	0.0577	0.029*
C32	0.21743 (12)	0.5869 (3)	0.1818 (3)	0.0214 (8)
H32A	0.2369	0.5861	0.1120	0.032*
H32B	0.2362	0.5557	0.2465	0.032*
H32C	0.2071	0.6717	0.1980	0.032*
C41	0.17782 (12)	0.0797 (3)	0.2938 (3)	0.0235 (8)
H41A	0.1737	0.0782	0.2103	0.035*
H41B	0.1785	−0.0052	0.3232	0.035*
H41C	0.2078	0.1211	0.3128	0.035*
C42	0.08438 (12)	0.0547 (3)	0.3193 (3)	0.0177 (7)
H42A	0.0536	0.0867	0.3449	0.027*
H42B	0.0905	−0.0252	0.3560	0.027*
H42C	0.0840	0.0441	0.2357	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.01338 (13)	0.01069 (12)	0.00938 (11)	0.00118 (11)	−0.00019 (10)	0.00063 (10)
Cl1	0.0294 (5)	0.0186 (4)	0.0130 (4)	0.0019 (4)	0.0052 (3)	0.0019 (3)
Cl2	0.0177 (4)	0.0185 (4)	0.0169 (4)	0.0008 (4)	−0.0052 (3)	0.0027 (3)
S1	0.0220 (5)	0.0114 (4)	0.0158 (4)	0.0018 (4)	−0.0022 (4)	−0.0005 (3)
S2	0.0134 (4)	0.0152 (4)	0.0164 (4)	0.0017 (3)	−0.0001 (3)	0.0030 (3)
S3	0.0137 (4)	0.0138 (4)	0.0122 (4)	0.0010 (3)	0.0001 (3)	0.0019 (3)
S4	0.0157 (4)	0.0117 (4)	0.0130 (3)	0.0006 (3)	−0.0014 (3)	0.0013 (3)
O1	0.0312 (16)	0.0134 (13)	0.0272 (13)	−0.0011 (11)	0.0036 (11)	0.0036 (11)
O2	0.0238 (15)	0.0149 (14)	0.0393 (14)	0.0036 (11)	−0.0079 (12)	0.0046 (12)
O3	0.0190 (12)	0.0190 (13)	0.0102 (10)	0.0003 (11)	−0.0005 (9)	0.0045 (10)
O4	0.0165 (13)	0.0108 (12)	0.0131 (10)	0.0004 (10)	−0.0035 (9)	0.0004 (9)
C11	0.034 (2)	0.015 (2)	0.036 (2)	0.0060 (17)	0.0154 (18)	−0.0020 (17)
C12	0.052 (3)	0.027 (2)	0.034 (2)	0.006 (2)	−0.024 (2)	−0.0146 (19)
C21	0.0134 (18)	0.033 (2)	0.0245 (17)	−0.0018 (16)	0.0049 (15)	0.0032 (17)
C22	0.019 (2)	0.034 (2)	0.0180 (17)	−0.0021 (17)	−0.0060 (14)	−0.0041 (17)
C31	0.023 (2)	0.0175 (19)	0.0171 (16)	0.0074 (15)	0.0052 (14)	0.0025 (15)
C32	0.0159 (18)	0.0226 (19)	0.0256 (18)	−0.0075 (15)	0.0001 (15)	0.0056 (17)
C41	0.019 (2)	0.021 (2)	0.0310 (19)	0.0048 (16)	0.0025 (15)	0.0044 (16)
C42	0.0187 (18)	0.0153 (18)	0.0191 (15)	−0.0032 (14)	−0.0011 (14)	0.0037 (15)

Geometric parameters (Å, º)

Ru1—O4	2.140 (2)	C12—H12A	0.98
Ru1—S1	2.2480 (9)	C12—H12B	0.98
Ru1—S2	2.2734 (9)	C12—H12C	0.98
Ru1—S3	2.2717 (8)	C21—H21A	0.98
Ru1—Cl1	2.4165 (8)	C21—H21B	0.98
Ru1—Cl2	2.4352 (8)	C21—H21C	0.98
S1—O1	1.475 (2)	C22—H22A	0.98
S1—C11	1.773 (3)	C22—H22B	0.98
S1—C12	1.787 (3)	C22—H22C	0.98
S2—O2	1.480 (3)	C31—H31A	0.98
S2—C22	1.774 (3)	C31—H31B	0.98
S2—C21	1.793 (3)	C31—H31C	0.98
S3—O3	1.488 (2)	C32—H32A	0.98
S3—C31	1.782 (3)	C32—H32B	0.98
S3—C32	1.789 (3)	C32—H32C	0.98
S4—O4	1.536 (2)	C41—H41A	0.98
S4—C41	1.773 (3)	C41—H41B	0.98
S4—C42	1.780 (3)	C41—H41C	0.98
C11—H11A	0.98	C42—H42A	0.98
C11—H11B	0.98	C42—H42B	0.98
C11—H11C	0.98	C42—H42C	0.98
O4—Ru1—S1	177.96 (6)	S1—C12—H12A	109.5
O4—Ru1—S3	87.07 (6)	S1—C12—H12B	109.5
S1—Ru1—S3	94.03 (3)	H12A—C12—H12B	109.5
O4—Ru1—S2	85.03 (6)	S1—C12—H12C	109.5
S1—Ru1—S2	93.18 (3)	H12A—C12—H12C	109.5
S3—Ru1—S2	93.90 (3)	H12B—C12—H12C	109.5
O4—Ru1—Cl1	89.34 (6)	S2—C21—H21A	109.5
S1—Ru1—Cl1	89.76 (3)	S2—C21—H21B	109.5
S3—Ru1—Cl1	172.79 (3)	H21A—C21—H21B	109.5
S2—Ru1—Cl1	92.01 (3)	S2—C21—H21C	109.5
O4—Ru1—Cl2	86.98 (6)	H21A—C21—H21C	109.5
S1—Ru1—Cl2	94.78 (3)	H21B—C21—H21C	109.5
S3—Ru1—Cl2	87.29 (3)	S2—C22—H22A	109.5
S2—Ru1—Cl2	171.85 (3)	S2—C22—H22B	109.5
Cl1—Ru1—Cl2	86.28 (3)	H22A—C22—H22B	109.5
O1—S1—C11	106.51 (16)	S2—C22—H22C	109.5
O1—S1—C12	106.67 (18)	H22A—C22—H22C	109.5
C11—S1—C12	98.51 (19)	H22B—C22—H22C	109.5
O1—S1—Ru1	119.70 (10)	S3—C31—H31A	109.5
C11—S1—Ru1	113.11 (13)	S3—C31—H31B	109.5
C12—S1—Ru1	110.10 (14)	H31A—C31—H31B	109.5
O2—S2—C22	106.73 (16)	S3—C31—H31C	109.5
O2—S2—C21	107.01 (16)	H31A—C31—H31C	109.5
C22—S2—C21	97.75 (17)	H31B—C31—H31C	109.5
O2—S2—Ru1	120.59 (11)	S3—C32—H32A	109.5
C22—S2—Ru1	111.15 (12)	S3—C32—H32B	109.5
C21—S2—Ru1	111.11 (12)	H32A—C32—H32B	109.5
O3—S3—C31	106.55 (14)	S3—C32—H32C	109.5
O3—S3—C32	105.99 (15)	H32A—C32—H32C	109.5
C31—S3—C32	99.15 (18)	H32B—C32—H32C	109.5
O3—S3—Ru1	120.37 (9)	S4—C41—H41A	109.5
C31—S3—Ru1	109.62 (11)	S4—C41—H41B	109.5
C32—S3—Ru1	112.92 (11)	H41A—C41—H41B	109.5
O4—S4—C41	104.63 (14)	S4—C41—H41C	109.5
O4—S4—C42	101.51 (14)	H41A—C41—H41C	109.5
C41—S4—C42	97.06 (17)	H41B—C41—H41C	109.5
S4—O4—Ru1	122.64 (12)	S4—C42—H42A	109.5
S1—C11—H11A	109.5	S4—C42—H42B	109.5
S1—C11—H11B	109.5	H42A—C42—H42B	109.5
H11A—C11—H11B	109.5	S4—C42—H42C	109.5
S1—C11—H11C	109.5	H42A—C42—H42C	109.5
H11A—C11—H11C	109.5	H42B—C42—H42C	109.5
H11B—C11—H11C	109.5
S3—Ru1—S1—O1	16.53 (12)	S1—Ru1—S2—C21	−109.17 (14)
S2—Ru1—S1—O1	−77.61 (12)	S3—Ru1—S2—C21	156.57 (14)
Cl1—Ru1—S1—O1	−169.61 (12)	Cl1—Ru1—S2—C21	−19.30 (14)
Cl2—Ru1—S1—O1	104.14 (12)	O4—Ru1—S3—O3	96.81 (13)
S3—Ru1—S1—C11	143.34 (14)	S1—Ru1—S3—O3	−81.48 (12)
S2—Ru1—S1—C11	49.20 (14)	S2—Ru1—S3—O3	11.99 (12)
Cl1—Ru1—S1—C11	−42.80 (14)	Cl2—Ru1—S3—O3	−176.08 (12)
Cl2—Ru1—S1—C11	−129.05 (14)	O4—Ru1—S3—C31	−27.21 (14)
S3—Ru1—S1—C12	−107.54 (16)	S1—Ru1—S3—C31	154.51 (13)
S2—Ru1—S1—C12	158.31 (16)	S2—Ru1—S3—C31	−112.03 (13)
Cl1—Ru1—S1—C12	66.31 (16)	Cl2—Ru1—S3—C31	59.90 (13)
Cl2—Ru1—S1—C12	−19.94 (16)	O4—Ru1—S3—C32	−136.72 (15)
O4—Ru1—S2—O2	−163.81 (13)	S1—Ru1—S3—C32	44.99 (14)
S1—Ru1—S2—O2	17.16 (12)	S2—Ru1—S3—C32	138.46 (14)
S3—Ru1—S2—O2	−77.10 (12)	Cl2—Ru1—S3—C32	−49.61 (14)
Cl1—Ru1—S2—O2	107.03 (12)	C41—S4—O4—Ru1	−119.66 (17)
O4—Ru1—S2—C22	−37.85 (15)	C42—S4—O4—Ru1	139.80 (15)
S1—Ru1—S2—C22	143.12 (14)	S3—Ru1—O4—S4	133.58 (14)
S3—Ru1—S2—C22	48.86 (14)	S2—Ru1—O4—S4	−132.25 (14)
Cl1—Ru1—S2—C22	−127.01 (14)	Cl1—Ru1—O4—S4	−40.17 (14)
O4—Ru1—S2—C21	69.86 (15)	Cl2—Ru1—O4—S4	46.14 (13)