Poly[di-μ₂-chlorido-dichlorido(μ₃-di­methyl sulfoxide-κ³O:O:S)(μ₂-di­methyl sulfoxide-κ²O:S)ruthenium(III)sodium]

The structure of the title compound, [NaRuCl₄(C₂H₆OS)₂]_n, comprises centrosymmetric [RuCl₂(DMSO)Na(DMSO)Cl₂Ru] units (DMSO is dimethyl sulfoxide, C₂H₆OS), with two Ru atoms, each lying on a crystallographic centre of inversion, connected via Na atoms, DMSO and chloride ligands into a two-dimensional (110) array. Both Ru^III atoms are octa­hedrally coordinated by four chloride ligands in the equatorial plane and by two DMSO mol­ecules in apical positions within a RuCl₄S₂ donor set. The Na atom is surrounded by three chloride anions and three O atoms derived from three DMSO mol­ecules, with the resulting Cl₃O₃ donor set defining an octa­hedron. The crystal structure is further stabilized by inter­atomic inter­actions of the types C...Cl [C—Cl = 3.284 (2) Å], C—H...Cl [C...Cl = 3.903 (3) Å] and C—H...O [C...O = 3.376 (3) Å].

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](S-C) = 0.002 Å
• R factor = 0.018
• wR factor = 0.050
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1

Alert level G
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.21 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

The title complex, (I), was prepared as a part of our study of simple ruthenium(III) complexes of the composition M[RuCl₄(DMSO)₂] with the different types of inorganic and organic cations [M]. In the crystal structure of (I), the centrosymmetric [RuCl₂(DMSO)Na(DMSO)Cl₂Ru] units are present; each ruthenium atom lies on a crystallographic centre of inversion whereas all other atoms lie in general positions. Each of the Ru^III atoms is hexacoordinated by two sulphur atoms from two DMSO molecules in apical positions and four chlorido ligands in an equatorial plane (Fig. 1). Each ruthenium atom exists within an octahedral trans-RuCl₄S₂ donor set.

Both octahedra exhibit similar Ru—S bond lengths [Ru1—S1 = 2.3350 (5) and Ru2—S2= 2.3373 (6) Å] in contrast to the Ru—Cl bond lengths, which exhibit similar values in the Ru1 octahedron [2.3551 (5) and 2.3509 (5) Å] but differ significantly in the Ru2 octahedron [2.3353 (6) and 2.3663 (6) Å]. The Ru—Cl bond lengths within the [RuCl₂(DMSO)Na(DMSO)Cl₂Ru] unit do not differ markedly from those observed in Na[trans-RuCl₄(DMSO)(pyr)].DMSO, where pyr = 1,4-pyrazine, [Ru—Cl = (2.3395 (8) - 2.3754 (7) Å] (Anderson et al., 2007) and in Na₂[{trans-RuCl₄(DMSO)}₂(µ-pyrimidine)], where the Ru—Cl bond lengths are in the range of 2.338 (2) - 2.361 (2) Å (Iengo et al., 1999), while the Ru—S distances in (I) are slightly longer than those observed in the above-mentioned complexes (Ru—S are in the range of 2.281 (2) - 2.3027 (7) Å).

The Na cation has six atoms in its closest octahedrally coordinated environment with the resulting Cl₃O₃ donor set and it is surrounded by six donor interactions, represented by dashed lines (Figs. 1 and 2). The distance between the two nearest Na atoms equals 3.4968 (19) Å. The distances of the Na—O and Na—Cl donor interactions vary from 2.2974 (18) to 2.4155 (18) Å, and from 2.7773 (11) to 2.9374 (10) Å, respectively. Similar values of the Na—O distances [2.272 (4) - 2.418 (4) Å] were found in Na[trans-RuCl₄(DMSO)(NH₃)].DMSO (Alessio et al., 1993) and similar Na—Cl distances [2.776 (2) - 2.922 (2) Å] were observed in Na[trans-RuCl₄(DMSO)(pyr)].DMSO (Anderson et al., 2007).

The trans-[Ru(DMSO)₂Cl₄] complex anion is connected to four sodium cations, two DMSO molecules and four chlorido ligands into infinite two dimensional array in the ab plane (Fig. 2). The crystal strucure of (I) is furter stabilized by non-bonding interactions of the C···Cl type [C4···Cl3ⁱⁱ is 3.284 (2) Å (ii = x, y+1, z)], which connect two Ru2 anions in the b direction (Fig. 2). The planes are cross connected, in the c direction, by the weak C···Cl [C3—Cl4^vii is 3.903 (3) Å] and C—H···O [C1···O2^vii is 3.376 (3) Å (vii = x, 1/2-y, -1/2+z)] type interactions (Fig. 3).

Related literature

For structures of similar ruthenium complexes, see: Alessio et al. (1993); Piggot et al. (2004); Anderson et al. (2007). For Na—O and Na—Cl distances in related structures, see: Alessio et al. (1991); Iengo et al. (1999).

S2. Experimental

The title complex was prepared by a slightly modified literature procedure (Alessio et al., 1991). The salt [H⁺(DMSO)₂][trans-Ru(DMSO)₂Cl₄] (1 mmol) was dissolved in a mixture of ethanol (20 ml) and distilled water (0.3 ml). The orange solution was filtered, and then, an aqueous solution (0.3 ml) of NaCl (0.07 g, 2.8 mmol) was added during stirring. The yellow precipitate which formed after several minutes was filtered off, washed with cold acetone, and dried in air (yield 50%). Single crystals were obtained from the filtrate by slow evaporation after several days.

S3. Refinement

All H-atoms were located in difference maps and refined using a riding model, with C–H distances of 0.98 Å, and with U_iso(H) = 1.5U_eq(C).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Part of the crystal structure of the title compound (I). The non-H atoms are drawn as 70% probability displacement ellipsoids. Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y+1, z; (iii) -x+1, -y, -z+1; (iv) -x, -y, 1-z; (v) x, y-1, z; (vi) -1+x, -1+y, z.
	Fig. 2. Part of the crystal structure of (I), showing the formation of the two dimensional array (a view along the c axis). Dashed lines represent non-covalent interactions of the C···Cl, Na···O and Na···Cl types. The H-atoms have been omitted for clarity. Symmetry code: (ii) x, 1+y, z.
	Fig. 3. Part of the crystal structure of (I), showing the formation of the two dimensional array (a view along the b axis). The H-atoms have been omitted for clarity. Dashed lines represent interactions of the C···Cl and C—H···O types. Symmetry code: (vii) x, 1/2-y, -1/2+z.

Poly[di-µ₂-chlorido-dichlorido(µ₃-dimethyl sulfoxide-κ³O:O:S)(µ₂-dimethyl sulfoxide-κ²O:S)ruthenium(III)sodium]

Crystal data

[NaRuCl4(C2H6OS)2]	F(000) = 828
Mr = 422.12	Dx = 2.140 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10079 reflections
a = 11.9042 (3) Å	θ = 2.9–32.0°
b = 8.0692 (2) Å	µ = 2.34 mm^−1
c = 13.7873 (3) Å	T = 120 K
β = 98.470 (2)°	Prism, orange
V = 1309.93 (5) Å^3	0.20 × 0.20 × 0.15 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur2 CCD diffractometer	2300 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
Enhance (Mo) X-ray Source monochromator	Rint = 0.021
Detector resolution: 8.3611 pixels mm^-1	θmax = 25.0°, θmin = 2.9°
rotation method, ω–scan	h = −14→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −9→9
Tmin = 0.652, Tmax = 0.721	l = −14→16
10197 measured reflections

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)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.050	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0269P)^2 + 0.8654P] where P = (Fo^2 + 2Fc^2)/3
2300 reflections	(Δ/σ)max = 0.001
134 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.5000	0.5000	0.5000	0.00777 (8)
S1	0.45936 (5)	0.30580 (7)	0.37416 (4)	0.00948 (13)
Cl1	0.35603 (5)	0.67940 (7)	0.42755 (4)	0.01284 (13)
Na1	0.35677 (8)	0.00303 (10)	0.51520 (7)	0.0144 (2)
O1	0.47177 (13)	0.12823 (19)	0.40510 (11)	0.0125 (3)
C1	0.31978 (19)	0.3274 (3)	0.30958 (17)	0.0148 (5)
H1A	0.3050	0.2387	0.2608	0.022*
H1B	0.3125	0.4351	0.2765	0.022*
H1C	0.2648	0.3202	0.3558	0.022*
Ru2	0.0000	0.0000	0.5000	0.00862 (9)
S2	0.12479 (5)	−0.14419 (7)	0.61717 (4)	0.01206 (13)
Cl2	0.63676 (5)	0.64639 (7)	0.42686 (4)	0.01285 (13)
O2	0.24699 (13)	−0.0998 (2)	0.62514 (11)	0.0147 (4)
C2	0.5426 (2)	0.3346 (3)	0.27921 (16)	0.0145 (5)
H2A	0.5163	0.2593	0.2249	0.022*
H2B	0.6224	0.3112	0.3042	0.022*
H2C	0.5352	0.4494	0.2559	0.022*
Cl3	0.07120 (5)	0.23663 (7)	0.58529 (4)	0.01694 (14)
C3	0.0887 (2)	−0.1226 (4)	0.73698 (18)	0.0224 (6)
H3A	0.1455	−0.1794	0.7841	0.034*
H3B	0.0138	−0.1718	0.7390	0.034*
H3C	0.0868	−0.0048	0.7539	0.034*
Cl4	−0.14497 (5)	−0.01787 (7)	0.59997 (4)	0.01570 (14)
C4	0.1151 (2)	−0.3619 (3)	0.6015 (2)	0.0262 (6)
H4A	0.1588	−0.4168	0.6583	0.039*
H4B	0.1458	−0.3934	0.5420	0.039*
H4C	0.0354	−0.3960	0.5956	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.00907 (15)	0.00689 (15)	0.00724 (14)	0.00048 (9)	0.00081 (11)	0.00072 (9)
S1	0.0118 (3)	0.0075 (3)	0.0088 (3)	0.0004 (2)	0.0006 (2)	0.0000 (2)
Cl1	0.0137 (3)	0.0105 (3)	0.0133 (3)	0.0032 (2)	−0.0017 (2)	0.0002 (2)
Na1	0.0131 (5)	0.0128 (5)	0.0173 (5)	−0.0001 (3)	0.0023 (4)	0.0027 (4)
O1	0.0165 (9)	0.0073 (8)	0.0136 (8)	0.0005 (6)	0.0015 (7)	0.0005 (6)
C1	0.0134 (12)	0.0148 (12)	0.0148 (12)	0.0005 (10)	−0.0027 (10)	−0.0016 (10)
Ru2	0.00868 (15)	0.00670 (15)	0.01060 (15)	−0.00093 (9)	0.00177 (11)	−0.00048 (9)
S2	0.0113 (3)	0.0106 (3)	0.0142 (3)	−0.0004 (2)	0.0014 (2)	0.0025 (2)
Cl2	0.0140 (3)	0.0126 (3)	0.0126 (3)	−0.0021 (2)	0.0042 (2)	0.0007 (2)
O2	0.0108 (8)	0.0183 (9)	0.0148 (8)	0.0001 (7)	0.0013 (7)	0.0030 (7)
C2	0.0195 (13)	0.0135 (12)	0.0110 (11)	−0.0006 (10)	0.0042 (10)	−0.0009 (9)
Cl3	0.0202 (3)	0.0107 (3)	0.0194 (3)	−0.0040 (2)	0.0013 (3)	−0.0048 (2)
C3	0.0176 (13)	0.0349 (16)	0.0147 (12)	0.0010 (11)	0.0022 (11)	0.0066 (11)
Cl4	0.0116 (3)	0.0220 (3)	0.0142 (3)	−0.0003 (2)	0.0040 (2)	0.0019 (2)
C4	0.0267 (15)	0.0113 (13)	0.0383 (16)	0.0002 (11)	−0.0032 (13)	0.0039 (11)

Geometric parameters (Å, º)

Ru1—S1	2.3350 (5)	Ru2—Cl3^iv	2.3353 (6)
Ru1—S1^i	2.3351 (5)	Ru2—Cl3	2.3353 (6)
Ru1—Cl1	2.3509 (5)	Ru2—S2^iv	2.3373 (6)
Ru1—Cl1^i	2.3509 (5)	Ru2—S2	2.3373 (6)
Ru1—Cl2^i	2.3551 (5)	Ru2—Cl4^iv	2.3663 (6)
Ru1—Cl2	2.3551 (5)	Ru2—Cl4	2.3663 (6)
S1—O1	1.4962 (16)	S2—O2	1.4863 (16)
S1—C2	1.770 (2)	S2—C4	1.772 (3)
S1—C1	1.774 (2)	S2—C3	1.776 (2)
Cl1—Na1^ii	2.8769 (10)	Cl2—Na1^i	2.9374 (10)
Na1—O2	2.2974 (18)	C2—H2A	0.9800
Na1—O1	2.4105 (17)	C2—H2B	0.9800
Na1—O1^iii	2.4155 (18)	C2—H2C	0.9800
Na1—Cl4^iv	2.7773 (11)	C3—H3A	0.9800
Na1—Cl1^v	2.8769 (10)	C3—H3B	0.9800
Na1—Cl2^i	2.9374 (10)	C3—H3C	0.9800
Na1—Na1^iii	3.4968 (19)	Cl4—Na1^iv	2.7772 (11)
O1—Na1^iii	2.4156 (18)	C4—H4A	0.9800
C1—H1A	0.9800	C4—H4B	0.9800
C1—H1B	0.9800	C4—H4C	0.9800
C1—H1C	0.9800
S1—Ru1—S1^i	179.999 (1)	S1—C1—H1B	109.5
S1—Ru1—Cl1	92.250 (19)	H1A—C1—H1B	109.5
S1^i—Ru1—Cl1	87.751 (19)	S1—C1—H1C	109.5
S1—Ru1—Cl1^i	87.751 (19)	H1A—C1—H1C	109.5
S1^i—Ru1—Cl1^i	92.248 (19)	H1B—C1—H1C	109.5
Cl1—Ru1—Cl1^i	180.0	Cl3^iv—Ru2—Cl3	179.999 (1)
S1—Ru1—Cl2^i	84.313 (19)	Cl3^iv—Ru2—S2^iv	84.97 (2)
S1^i—Ru1—Cl2^i	95.687 (19)	Cl3—Ru2—S2^iv	95.03 (2)
Cl1—Ru1—Cl2^i	89.091 (19)	Cl3^iv—Ru2—S2	95.03 (2)
Cl1^i—Ru1—Cl2^i	90.909 (19)	Cl3—Ru2—S2	84.97 (2)
S1—Ru1—Cl2	95.686 (19)	S2^iv—Ru2—S2	179.999 (1)
S1^i—Ru1—Cl2	84.314 (19)	Cl3^iv—Ru2—Cl4^iv	89.90 (2)
Cl1—Ru1—Cl2	90.909 (19)	Cl3—Ru2—Cl4^iv	90.10 (2)
Cl1^i—Ru1—Cl2	89.091 (19)	S2^iv—Ru2—Cl4^iv	90.63 (2)
Cl2^i—Ru1—Cl2	180.0	S2—Ru2—Cl4^iv	89.37 (2)
O1—S1—C2	107.12 (10)	Cl3^iv—Ru2—Cl4	90.10 (2)
O1—S1—C1	106.43 (10)	Cl3—Ru2—Cl4	89.90 (2)
C2—S1—C1	101.59 (11)	S2^iv—Ru2—Cl4	89.37 (2)
O1—S1—Ru1	115.46 (7)	S2—Ru2—Cl4	90.63 (2)
C2—S1—Ru1	112.59 (8)	Cl4^iv—Ru2—Cl4	180.0
C1—S1—Ru1	112.54 (8)	O2—S2—C4	107.04 (12)
Ru1—Cl1—Na1^ii	115.06 (3)	O2—S2—C3	106.03 (11)
O2—Na1—O1	176.27 (7)	C4—S2—C3	100.97 (14)
O2—Na1—O1^iii	93.79 (6)	O2—S2—Ru2	116.54 (7)
O1—Na1—O1^iii	87.14 (6)	C4—S2—Ru2	112.72 (10)
O2—Na1—Cl4^iv	80.56 (5)	C3—S2—Ru2	112.19 (9)
O1—Na1—Cl4^iv	100.01 (5)	Ru1—Cl2—Na1^i	111.02 (3)
O1^iii—Na1—Cl4^iv	156.08 (5)	S2—O2—Na1	133.14 (10)
O2—Na1—Cl1^v	88.98 (5)	S1—C2—H2A	109.5
O1—Na1—Cl1^v	94.75 (5)	S1—C2—H2B	109.5
O1^iii—Na1—Cl1^v	75.12 (4)	H2A—C2—H2B	109.5
Cl4^iv—Na1—Cl1^v	81.52 (3)	S1—C2—H2C	109.5
O2—Na1—Cl2^i	99.39 (5)	H2A—C2—H2C	109.5
O1—Na1—Cl2^i	76.89 (4)	H2B—C2—H2C	109.5
O1^iii—Na1—Cl2^i	108.18 (5)	S2—C3—H3A	109.5
Cl4^iv—Na1—Cl2^i	95.69 (3)	S2—C3—H3B	109.5
Cl1^v—Na1—Cl2^i	170.66 (4)	H3A—C3—H3B	109.5
O2—Na1—Na1^iii	137.18 (6)	S2—C3—H3C	109.5
O1—Na1—Na1^iii	43.63 (4)	H3A—C3—H3C	109.5
O1^iii—Na1—Na1^iii	43.51 (4)	H3B—C3—H3C	109.5
Cl4^iv—Na1—Na1^iii	138.71 (5)	Ru2—Cl4—Na1^iv	110.05 (3)
Cl1^v—Na1—Na1^iii	83.09 (3)	S2—C4—H4A	109.5
Cl2^i—Na1—Na1^iii	93.39 (4)	S2—C4—H4B	109.5
S1—O1—Na1	122.65 (9)	H4A—C4—H4B	109.5
S1—O1—Na1^iii	126.22 (9)	S2—C4—H4C	109.5
Na1—O1—Na1^iii	92.86 (6)	H4A—C4—H4C	109.5
S1—C1—H1A	109.5	H4B—C4—H4C	109.5

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) −x+1, −y, −z+1; (iv) −x, −y, −z+1; (v) x, y−1, z.