Poly[μ(3)-chlorido-μ(2)-chloridodichlorido(μ-dimethyl sulfoxide-κO:S)(dimethyl sulfoxide-κO)(μ-pyrimidine-κN:N')-ruthenium(III)sodium].

The title complex, [NaRuCl(4)(C(4)H(4)N(2))(C(2)H(6)OS)(2)](n), is the sodium salt of monoanionic octa-hedral [Ru(III)Cl(4)(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 nitro-gen ligand from the pyrimidine of the tetrachlorido-ruthenium(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 = 502.21

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.045

S = 1.07

5227 reflections

185 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[NaRuCl4(C4H4N2)(C2H6OS)2]	F(000) = 996
Mr = 502.21	Dx = 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

Bruker APEXII CCD diffractometer	5227 independent reflections
Radiation source: fine-focus sealed tube	4922 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scans	θmax = 30.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −17→17
Tmin = 0.675, Tmax = 0.848	k = −15→15
25088 measured reflections	l = −17→17

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(Fo2) + (0.0191P)2 + 1.3448P] where P = (Fo2 + 2Fc2)/3
5227 reflections	(Δ/σ)max = 0.003
185 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.87 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)