Poly[μ3-chlorido-μ2-chloridodichlorido(μ-dimethyl sulfoxide-κ2O:S)(dimethyl sulfoxide-κO)(μ-pyrimidine-κ2N:N′)­ruthenium(III)sodium]

Ferrara, S.; Kreider-Mueller, A.; Tanski, J.M.; Anderson, C.M.

doi:10.1107/S1600536811017211

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Pages m756-m757

doi:10.1107/S1600536811017211

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Poly[μ₃-chlorido-μ₂-chloridodichlorido(μ-dimethyl sulfoxide-κ²O:S)(dimethyl sulfoxide-κO)(μ-pyrimidine-κ²N:N′)ruthenium(III)sodium]

Skylar Ferrara,^a Ava Kreider-Mueller,^a Joseph M. Tanski ^b and Craig M. Anderson ^a ^*

^aDepartment of Chemistry, Bard College, Annandale-on-Hudson, NY 12504, USA, and ^bDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA
^*Correspondence e-mail: canderso@bard.edu

(Received 1 May 2011; accepted 6 May 2011; online 14 May 2011)

The title complex, [NaRuCl₄(C₄H₄N₂)(C₂H₆OS)₂]_n, is the sodium salt of monoanionic octahedral [Ru^IIICl₄(pyrimidine)(DMSO)]⁻ in which the sulfur-bound dimethyl sulfoxide (DMSO) and pyrimidine ligand are oriented trans to one another on the Ru^III atom. The average of the four Ru—Cl bond lengths is 2.355 (15) Å, and the Ru—S and Ru—N bond lengths are 2.2853 (3) and 2.1165 (11) Å, respectively. The complex forms a chain, with a six-coordinate sodium ion bridging the ruthenium(III) units. The sodium cation is coordinated by cis-chloride ligands on ruthenium [Na—Cl = 2.9576 (7) and 2.6988 (7) Å], chloride and DMSO ligands from the ruthenium complexes related by inversion [Na—Cl and Na—O = 2.8888 (7) and 2.2623 (12) Å, respectively], a nitrogen ligand from the pyrimidine of the tetrachloridoruthenium(III) complex related by the twofold rotation axis [Na—N = 2.5224 (14) Å] and an oxygen-bound DMSO [Na—O = 2.3165 (12) Å].

Related literature

For general background to ruthenium complexes as anti-cancer agents, see: Kostova (2006 ); Antonarakis & Emadi (2010 ); Silva (2010 ). For the synthesis of related complexes and precursors, see: Alessio et al. (1991 , 1993 ); Jaswal et al. (1990 ). For related structures with the tetrachloro ruthenium (III) motif and electron-withdrawing ligand, see: Alessio et al. (1995 ); Anderson & Beauchamp (1995 ). For related multi-nuclear species, see: Herman et al. (2008 ); Iengo et al. (1999 ). For a very closely related structure with pyrazine in place of pyrimidine, showing a very similar network bonding, see: Anderson et al. (2007 ).

Experimental

Crystal data

[NaRuCl₄(C₄H₄N₂)(C₂H₆OS)₂]
M_r = 502.21
Monoclinic, P 2/c
a = 12.5052 (6) Å
b = 10.9917 (5) Å
c = 13.1837 (6) Å
β = 91.680 (1)°
V = 1811.37 (15) Å³
Z = 4
Mo Kα radiation
μ = 1.71 mm⁻¹
T = 125 K
0.25 × 0.23 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.675, T_max = 0.848
25088 measured reflections
5227 independent reflections
4922 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.045
S = 1.07
5227 reflections
185 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.87 e Å⁻³

Data collection: APEX2 (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017211/om2427sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017211/om2427Isup2.hkl

checkCIF report

Comment top

Ruthenium complexes are thought to be good candidates for the next generation of metal-based anti-cancer agents following the very successful platinum complexes whose most famous example is cisplatin; platinum complexes struggle with general toxicity, drug resistance, and lack of water solubility (Kostova, 2006; Antonarakis & Emadi, 2010; Silva, 2010). For synthesis of ruthenium precursors see: Alessio et al. (1991) and Jaswal et al. (1990).

The title complex exhibits a nearly octahedral coordination geometry at ruthenium, and the dimethyl sulfoxide (DMSO) coordinated sodium cation is associated with the complex via cis-chloride ligands (Fig. 1). The sulfur-bound DMSO and pyrimidine ligands are trans, with Ru1—S1 and Ru1—N1 bond distances of 2.2853 (3)Å and 2.117 (1) Å, respectively, and an average Ru1—Cl distance of 2.35 (2) Å. The Ru1—Cl, Ru1—S1 and Ru1—N1 distances are very similar to those found in three related RuCl₄(DMSO)^-1 structures containing the aromatic nitrogen donor ligand pyrazine, [Na][RuCl₄(pyrazine)(DMSO)] (Anderson et al., 2007), Na₂[trans,cis,trans-Ru^IIICl₄(DMSO)(µ-pyrazine)]₂Pt^IICl₂, and (tetraphenylphospohium)₂[trans,trans,trans-Ru^IIICl₄(DMSO)(µ-pyrazine)]₂Pt^IICl₂ (Herman et al., 2008). The Ru—Cl bond distances are also similar to other Ru(III) tetrachloro complexes containing electron withdrawing ligands such as CO (Alessio et al., 1995) or nitroimidazole (Anderson & Beauchamp, 1995). The dimeric species Na₂[trans,trans-Ru^IIICl₄(DMSO)]₂(µ-pyrmidine)] (Iengo et al., 1999) and the monomeric species Na[trans-Ru^IIICl₄(DMSO)(imidazole)] (Alessio et al., 1993) show a similar coordination around the ruthenium centers.

The six-coordinate, distorted octahedral sodium cation acts to bridge the ruthenium complex into an infinite one-dimensional chain (Fig. 2). On each Ru center, cis-chloride ligands coordinate to sodium with Na1—Cl2 and Na1—Cl3 distances of 2.9576 (7)Å and 2.6988 (7) Å, respectively. A centrosymmetric dimer is formed by additional sodium coordination to Cl2ⁱ and the DMSO oxygen O1ⁱ of the neighboring ruthenium complex, with Na1—Cl2ⁱ distance of 2.8888 (7)Å and Na1—O1ⁱ distance of 2.262 (1) Å. The dimer is linked into an infinite one-dimensional chain by further coordination of the sodium ion to nitrogen N2ⁱⁱ of the pyrimidine lignd of the ruthenium complex related by the twofold rotation axis with a Na1—N2ⁱⁱ bond distance of 2.522 (1) Å. The final coordination site of the octahedral sodium ion is occupied by a molecule of DMSO, with Na1—O2 length 2.317 (1) Å. This infinite one-dimensional chain with the sodium cation acting as a bridge is similar to the related structure [Na][RuCl₄(pyrazine)(DMSO)] (Anderson et al., 2007), the difference being the slight twist observed in the pyrimidine complex due to the meta nitrogen donor atoms as opposed to a more linear case for the pyrazine complex with the para nitrogen donor atoms.

Related literature top

For general background to ruthenium complexes as anti-cancer agents, see: Kostova (2006); Antonarakis & Emadi (2010); Silva (2010). For the synthesis of related complexes and precursors, see: Alessio et al. (1991, 1993); Jaswal et al. (1990). For related structures with the tetrachloro ruthenium (III) motif and electron-withdrawing ligand, see: Alessio et al. (1995); Anderson & Beauchamp (1995). For related multi-nuclear species, see: Herman et al. (2008); Iengo et al. (1999). For a very closely related structure with pyrazine in place of pyrimidine, showing a very similar network bonding, see: Anderson et al. (2007).

Experimental top

The title complex was prepared by mixing a solution of [Na][RuCl₄(DMSO)₂] in acetone/DMSO (10:1) with an acetone solution of pyrimidine in fivefold excess. The resulting solution was mixed for several hours and then placed at 5 °C for several days. Large block-like crystals appeared; one was taken for X-ray diffraction studies. The others were used for spectroscopic characterization. For similar spectroscopic results see Anderson et al., (2007). Selected IR (cm^-1): 1596 (pyrimidine), 1085 s (DMSO-S), 431 m (Ru-S). Selected ¹H NMR: (D₂O/p.p.m.): -13.9 (br, DMSO-S), 5.15 (pyrimidine H); -0.85 (br, pyrimidine H).

Computing details top

Data collection: APEX2 (Bruker 2007); cell refinement: SAINT (Bruker 2007); data reduction: SAINT (Bruker 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, with displacement ellipsoids shown at the 50% probability level.
	Fig. 2. A view of the one-dimensional chain with displacement ellipsoids shown at the 50% probability level. Hydrogen atoms have been removed for clarity. [Symmetry codes: (i) -x + 1, -y, -z + 1; (ii) -x + 1, y, -z + 1/2; (iii) x, -y, z + 1/2].

Poly[µ₃-chlorido-µ₂-chloridodichlorido(µ-dimethyl sulfoxide-κ²O:S)(dimethyl sulfoxide-κO)(µ-pyrimidine- κ²N:N')ruthenium(III)sodium] top

Crystal data top

[NaRuCl₄(C₄H₄N₂)(C₂H₆OS)₂]	F(000) = 996
M_r = 502.21	D_x = 1.842 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 9970 reflections
a = 12.5052 (6) Å	θ = 2.5–30.4°
b = 10.9917 (5) Å	µ = 1.71 mm⁻¹
c = 13.1837 (6) Å	T = 125 K
β = 91.680 (1)°	Block, orange
V = 1811.37 (15) Å³	0.25 × 0.23 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5227 independent reflections
Radiation source: fine-focus sealed tube	4922 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 30.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −17→17
T_min = 0.675, T_max = 0.848	k = −15→15
25088 measured reflections	l = −17→17

Refinement top

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)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.045	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0191P)² + 1.3448P] where P = (F_o² + 2F_c²)/3
5227 reflections	(Δ/σ)_max = 0.003
185 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

[NaRuCl₄(C₄H₄N₂)(C₂H₆OS)₂]	V = 1811.37 (15) Å³
M_r = 502.21	Z = 4
Monoclinic, P2/c	Mo Kα radiation
a = 12.5052 (6) Å	µ = 1.71 mm⁻¹
b = 10.9917 (5) Å	T = 125 K
c = 13.1837 (6) Å	0.25 × 0.23 × 0.10 mm
β = 91.680 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5227 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	4922 reflections with I > 2σ(I)
T_min = 0.675, T_max = 0.848	R_int = 0.018
25088 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.045	H-atom parameters constrained
S = 1.07	Δρ_max = 0.61 e Å⁻³
5227 reflections	Δρ_min = −0.87 e Å⁻³
185 parameters

Special details top

Experimental. A suitable crystal was mounted in a nylon loop with Paratone-N cryoprotectant oil and data was collected on a Bruker APEX II CCD platform diffractometer. The structure was solved using direct methods and standard difference map techniques, and was refined by full-matrix least-squares procedures on F² with SHELXTL Version 6.14 (Sheldrick, 2008).

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

	x	y	z	U_iso*/U_eq
Ru1	0.710023 (8)	0.198037 (9)	0.478554 (8)	0.01123 (3)
Cl1	0.85124 (3)	0.11358 (3)	0.38991 (3)	0.01888 (7)
Cl2	0.58872 (3)	0.05284 (3)	0.41162 (2)	0.01429 (6)
Cl3	0.56492 (3)	0.28961 (3)	0.56229 (3)	0.01702 (7)
Cl4	0.81971 (3)	0.35246 (3)	0.54845 (3)	0.01820 (7)
S1	0.75569 (3)	0.07509 (3)	0.61274 (2)	0.01419 (6)
S2	0.15245 (3)	0.26924 (4)	0.56476 (3)	0.02733 (9)
Na1	0.39260 (5)	0.17477 (5)	0.47975 (4)	0.01674 (11)
O1	0.72781 (9)	−0.05555 (9)	0.60442 (8)	0.0226 (2)
O2	0.27052 (9)	0.29182 (10)	0.56554 (9)	0.0234 (2)
N1	0.67216 (9)	0.30751 (10)	0.35040 (9)	0.0143 (2)
N2	0.63506 (11)	0.31171 (11)	0.17229 (9)	0.0190 (2)
C1	0.65932 (11)	0.42887 (13)	0.35492 (11)	0.0172 (3)
H1B	0.6663	0.4691	0.4185	0.021*
C2	0.63608 (12)	0.49591 (13)	0.26817 (12)	0.0209 (3)
H2B	0.6289	0.5819	0.2706	0.025*
C3	0.62363 (12)	0.43273 (13)	0.17765 (11)	0.0207 (3)
H3A	0.6064	0.4767	0.1173	0.025*
C4	0.66019 (11)	0.25468 (13)	0.25867 (10)	0.0167 (3)
H4A	0.6706	0.1692	0.2554	0.020*
C5	0.70393 (15)	0.12935 (16)	0.72786 (12)	0.0282 (3)
H5A	0.7338	0.0815	0.7846	0.042*
H5B	0.6258	0.1216	0.7256	0.042*
H5C	0.7235	0.2150	0.7371	0.042*
C6	0.89514 (13)	0.07824 (16)	0.64379 (13)	0.0270 (3)
H6A	0.9099	0.0267	0.7032	0.041*
H6B	0.9172	0.1620	0.6591	0.041*
H6C	0.9351	0.0478	0.5862	0.041*
C7	0.10238 (14)	0.30545 (16)	0.44103 (14)	0.0286 (3)
H7A	0.1303	0.2470	0.3923	0.043*
H7B	0.1252	0.3877	0.4229	0.043*
H7C	0.0241	0.3016	0.4396	0.043*
C8	0.09779 (13)	0.39468 (17)	0.63121 (13)	0.0280 (3)
H8A	0.1257	0.3946	0.7015	0.042*
H8B	0.0196	0.3877	0.6307	0.042*
H8C	0.1179	0.4707	0.5980	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01237 (5)	0.01042 (5)	0.01084 (5)	−0.00154 (3)	−0.00045 (3)	−0.00023 (3)
Cl1	0.01630 (15)	0.02092 (16)	0.01953 (15)	0.00148 (12)	0.00268 (11)	−0.00202 (12)
Cl2	0.01616 (14)	0.01303 (13)	0.01361 (13)	−0.00274 (11)	−0.00093 (10)	−0.00138 (11)
Cl3	0.01559 (14)	0.01744 (15)	0.01805 (15)	−0.00118 (11)	0.00076 (11)	−0.00633 (11)
Cl4	0.01779 (15)	0.01504 (14)	0.02153 (16)	−0.00515 (11)	−0.00358 (12)	−0.00077 (12)
S1	0.01623 (15)	0.01305 (14)	0.01310 (14)	−0.00307 (11)	−0.00283 (11)	0.00139 (11)
S2	0.02289 (19)	0.02494 (19)	0.0341 (2)	−0.00204 (15)	−0.00019 (15)	0.00201 (16)
Na1	0.0173 (3)	0.0158 (3)	0.0170 (3)	−0.0015 (2)	−0.0024 (2)	−0.0016 (2)
O1	0.0303 (6)	0.0128 (5)	0.0239 (5)	−0.0053 (4)	−0.0103 (4)	0.0034 (4)
O2	0.0188 (5)	0.0248 (6)	0.0265 (6)	0.0019 (4)	−0.0004 (4)	−0.0036 (4)
N1	0.0159 (5)	0.0127 (5)	0.0141 (5)	−0.0003 (4)	−0.0005 (4)	0.0009 (4)
N2	0.0240 (6)	0.0179 (6)	0.0152 (6)	0.0009 (5)	−0.0002 (5)	0.0027 (4)
C1	0.0183 (6)	0.0142 (6)	0.0188 (6)	−0.0015 (5)	−0.0015 (5)	−0.0007 (5)
C2	0.0245 (7)	0.0137 (6)	0.0242 (7)	−0.0001 (5)	−0.0026 (6)	0.0036 (5)
C3	0.0246 (7)	0.0178 (7)	0.0195 (7)	0.0012 (5)	−0.0019 (5)	0.0062 (5)
C4	0.0217 (7)	0.0139 (6)	0.0144 (6)	0.0000 (5)	0.0007 (5)	0.0007 (5)
C5	0.0424 (10)	0.0282 (8)	0.0140 (7)	0.0057 (7)	0.0034 (6)	0.0030 (6)
C6	0.0187 (7)	0.0309 (8)	0.0309 (8)	−0.0042 (6)	−0.0096 (6)	0.0104 (7)
C7	0.0231 (8)	0.0313 (9)	0.0312 (9)	−0.0011 (6)	−0.0048 (6)	−0.0054 (7)
C8	0.0190 (7)	0.0344 (9)	0.0308 (8)	−0.0002 (6)	0.0039 (6)	−0.0024 (7)

Geometric parameters (Å, º) top

Ru1—N1	2.1165 (11)	N2—C4	1.3294 (18)
Ru1—S1	2.2853 (3)	N2—C3	1.3400 (19)
Ru1—Cl1	2.3381 (4)	N2—Na1ⁱⁱ	2.5224 (14)
Ru1—Cl4	2.3532 (3)	C1—C2	1.384 (2)
Ru1—Cl2	2.3555 (3)	C1—H1B	0.9500
Ru1—Cl3	2.3753 (3)	C2—C3	1.386 (2)
Cl2—Na1ⁱ	2.8888 (7)	C2—H2B	0.9500
Cl2—Na1	2.9576 (7)	C3—H3A	0.9500
Cl3—Na1	2.6988 (7)	C4—H4A	0.9500
S1—O1	1.4811 (11)	C5—H5A	0.9800
S1—C5	1.7708 (16)	C5—H5B	0.9800
S1—C6	1.7798 (16)	C5—H5C	0.9800
S2—O2	1.4969 (12)	C6—H6A	0.9800
S2—C7	1.7753 (18)	C6—H6B	0.9800
S2—C8	1.7806 (18)	C6—H6C	0.9800
Na1—O1ⁱ	2.2623 (12)	C7—H7A	0.9800
Na1—O2	2.3165 (12)	C7—H7B	0.9800
Na1—N2ⁱⁱ	2.5224 (14)	C7—H7C	0.9800
Na1—Cl2ⁱ	2.8888 (7)	C8—H8A	0.9800
O1—Na1ⁱ	2.2623 (12)	C8—H8B	0.9800
N1—C1	1.3451 (17)	C8—H8C	0.9800
N1—C4	1.3459 (18)

N1—Ru1—S1	177.55 (3)	S2—O2—Na1	124.66 (7)
N1—Ru1—Cl1	88.93 (3)	C1—N1—C4	117.21 (12)
S1—Ru1—Cl1	88.676 (13)	C1—N1—Ru1	123.55 (10)
N1—Ru1—Cl4	90.96 (3)	C4—N1—Ru1	119.24 (9)
S1—Ru1—Cl4	89.645 (12)	C4—N2—C3	116.47 (13)
Cl1—Ru1—Cl4	92.407 (13)	C4—N2—Na1ⁱⁱ	115.02 (9)
N1—Ru1—Cl2	87.68 (3)	C3—N2—Na1ⁱⁱ	128.45 (10)
S1—Ru1—Cl2	91.887 (12)	N1—C1—C2	120.92 (13)
Cl1—Ru1—Cl2	91.791 (13)	N1—C1—H1B	119.5
Cl4—Ru1—Cl2	175.564 (12)	C2—C1—H1B	119.5
N1—Ru1—Cl3	88.51 (3)	C1—C2—C3	117.41 (13)
S1—Ru1—Cl3	93.885 (13)	C1—C2—H2B	121.3
Cl1—Ru1—Cl3	177.438 (13)	C3—C2—H2B	121.3
Cl4—Ru1—Cl3	87.525 (12)	N2—C3—C2	122.24 (13)
Cl2—Ru1—Cl3	88.217 (12)	N2—C3—H3A	118.9
Ru1—Cl2—Na1ⁱ	111.055 (16)	C2—C3—H3A	118.9
Ru1—Cl2—Na1	96.306 (15)	N2—C4—N1	125.70 (13)
Na1ⁱ—Cl2—Na1	107.313 (17)	N2—C4—H4A	117.1
Ru1—Cl3—Na1	103.076 (17)	N1—C4—H4A	117.1
O1—S1—C5	107.39 (8)	S1—C5—H5A	109.5
O1—S1—C6	105.24 (7)	S1—C5—H5B	109.5
C5—S1—C6	100.18 (9)	H5A—C5—H5B	109.5
O1—S1—Ru1	117.58 (4)	S1—C5—H5C	109.5
C5—S1—Ru1	112.02 (6)	H5A—C5—H5C	109.5
C6—S1—Ru1	112.80 (6)	H5B—C5—H5C	109.5
O2—S2—C7	106.88 (8)	S1—C6—H6A	109.5
O2—S2—C8	105.14 (7)	S1—C6—H6B	109.5
C7—S2—C8	98.53 (8)	H6A—C6—H6B	109.5
O1ⁱ—Na1—O2	97.03 (5)	S1—C6—H6C	109.5
O1ⁱ—Na1—N2ⁱⁱ	83.22 (4)	H6A—C6—H6C	109.5
O2—Na1—N2ⁱⁱ	88.83 (5)	H6B—C6—H6C	109.5
O1ⁱ—Na1—Cl3	168.75 (4)	S2—C7—H7A	109.5
O2—Na1—Cl3	94.20 (3)	S2—C7—H7B	109.5
N2ⁱⁱ—Na1—Cl3	97.50 (4)	H7A—C7—H7B	109.5
O1ⁱ—Na1—Cl2ⁱ	77.56 (3)	S2—C7—H7C	109.5
O2—Na1—Cl2ⁱ	106.49 (4)	H7A—C7—H7C	109.5
N2ⁱⁱ—Na1—Cl2ⁱ	156.63 (4)	H7B—C7—H7C	109.5
Cl3—Na1—Cl2ⁱ	98.81 (2)	S2—C8—H8A	109.5
O1ⁱ—Na1—Cl2	97.73 (4)	S2—C8—H8B	109.5
O2—Na1—Cl2	164.62 (4)	H8A—C8—H8B	109.5
N2ⁱⁱ—Na1—Cl2	97.16 (4)	S2—C8—H8C	109.5
Cl3—Na1—Cl2	71.032 (17)	H8A—C8—H8C	109.5
Cl2ⁱ—Na1—Cl2	72.685 (17)	H8B—C8—H8C	109.5
S1—O1—Na1ⁱ	138.58 (7)

N1—Ru1—Cl2—Na1ⁱ	169.07 (4)	Na1ⁱ—Cl2—Na1—O2	89.29 (15)
S1—Ru1—Cl2—Na1ⁱ	−8.520 (18)	Ru1—Cl2—Na1—N2ⁱⁱ	87.18 (3)
Cl1—Ru1—Cl2—Na1ⁱ	80.213 (18)	Na1ⁱ—Cl2—Na1—N2ⁱⁱ	−158.42 (4)
Cl4—Ru1—Cl2—Na1ⁱ	−118.67 (16)	Ru1—Cl2—Na1—Cl3	−8.327 (15)
Cl3—Ru1—Cl2—Na1ⁱ	−102.351 (18)	Na1ⁱ—Cl2—Na1—Cl3	106.070 (19)
N1—Ru1—Cl2—Na1	−79.63 (3)	Ru1—Cl2—Na1—Cl2ⁱ	−114.397 (16)
S1—Ru1—Cl2—Na1	102.787 (16)	Na1ⁱ—Cl2—Na1—Cl2ⁱ	0.0
Cl1—Ru1—Cl2—Na1	−168.480 (16)	C5—S1—O1—Na1ⁱ	102.49 (12)
Cl4—Ru1—Cl2—Na1	−7.36 (16)	C6—S1—O1—Na1ⁱ	−151.41 (11)
Cl3—Ru1—Cl2—Na1	8.957 (16)	Ru1—S1—O1—Na1ⁱ	−24.88 (13)
N1—Ru1—Cl3—Na1	77.70 (4)	C7—S2—O2—Na1	−69.98 (10)
S1—Ru1—Cl3—Na1	−101.797 (18)	C8—S2—O2—Na1	−174.02 (8)
Cl1—Ru1—Cl3—Na1	80.2 (3)	O1ⁱ—Na1—O2—S2	6.47 (9)
Cl4—Ru1—Cl3—Na1	168.727 (18)	N2ⁱⁱ—Na1—O2—S2	89.50 (8)
Cl2—Ru1—Cl3—Na1	−10.026 (18)	Cl3—Na1—O2—S2	−173.06 (8)
N1—Ru1—S1—O1	−63.0 (8)	Cl2ⁱ—Na1—O2—S2	−72.58 (8)
Cl1—Ru1—S1—O1	−74.84 (6)	Cl2—Na1—O2—S2	−157.17 (10)
Cl4—Ru1—S1—O1	−167.26 (6)	S1—Ru1—N1—C1	−140.4 (7)
Cl2—Ru1—S1—O1	16.91 (6)	Cl1—Ru1—N1—C1	−128.53 (11)
Cl3—Ru1—S1—O1	105.25 (6)	Cl4—Ru1—N1—C1	−36.14 (11)
N1—Ru1—S1—C5	171.9 (8)	Cl2—Ru1—N1—C1	139.63 (11)
Cl1—Ru1—S1—C5	160.06 (7)	Cl3—Ru1—N1—C1	51.36 (11)
Cl4—Ru1—S1—C5	67.64 (7)	S1—Ru1—N1—C4	39.4 (8)
Cl2—Ru1—S1—C5	−108.20 (7)	Cl1—Ru1—N1—C4	51.30 (10)
Cl3—Ru1—S1—C5	−19.86 (7)	Cl4—Ru1—N1—C4	143.68 (10)
N1—Ru1—S1—C6	59.8 (8)	Cl2—Ru1—N1—C4	−40.54 (10)
Cl1—Ru1—S1—C6	47.92 (7)	Cl3—Ru1—N1—C4	−128.82 (10)
Cl4—Ru1—S1—C6	−44.49 (7)	C4—N1—C1—C2	−0.8 (2)
Cl2—Ru1—S1—C6	139.67 (7)	Ru1—N1—C1—C2	179.06 (11)
Cl3—Ru1—S1—C6	−131.99 (7)	N1—C1—C2—C3	1.8 (2)
Ru1—Cl3—Na1—O1ⁱ	6.4 (2)	C4—N2—C3—C2	−0.6 (2)
Ru1—Cl3—Na1—O2	−175.98 (3)	Na1ⁱⁱ—N2—C3—C2	176.46 (11)
Ru1—Cl3—Na1—N2ⁱⁱ	−86.60 (3)	C1—C2—C3—N2	−1.1 (2)
Ru1—Cl3—Na1—Cl2ⁱ	76.60 (2)	C3—N2—C4—N1	1.9 (2)
Ru1—Cl3—Na1—Cl2	8.427 (15)	Na1ⁱⁱ—N2—C4—N1	−175.64 (11)
Ru1—Cl2—Na1—O1ⁱ	171.27 (3)	C1—N1—C4—N2	−1.2 (2)
Na1ⁱ—Cl2—Na1—O1ⁱ	−74.33 (3)	Ru1—N1—C4—N2	178.99 (12)
Ru1—Cl2—Na1—O2	−25.10 (15)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[NaRuCl₄(C₄H₄N₂)(C₂H₆OS)₂]
M_r	502.21
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	125
a, b, c (Å)	12.5052 (6), 10.9917 (5), 13.1837 (6)
β (°)	91.680 (1)
V (Å³)	1811.37 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.71
Crystal size (mm)	0.25 × 0.23 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.675, 0.848
No. of measured, independent and observed [I > 2σ(I)] reflections	25088, 5227, 4922
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.045, 1.07
No. of reflections	5227
No. of parameters	185
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.87

Computer programs: APEX2 (Bruker 2007), SAINT (Bruker 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by Bard College. X-ray facilities were provided by the US National Science Foundation (grant No. 0521237 to JMT).

References

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