A new monoclinic polymorph of dichlorido-tetra-kis(dimethyl sulfoxide)-ruthenium(II).

The title compound, cis,fac-dichloridotetra-kis(dimethyl sulfoxide)-κ(3)S,κO-ruthenium(II), [RuCl(2)(C(2)H(6)OS)(4)], was obtained from newly synthesized ruthenium complexes of 3-amino-2-chloro-pyridine. The Ru atom has a distorted octa-hedral coordination with two cis-oriented chloride ligands and four dimethyl sulfoxide ligands. Three of the sulfoxide ligands are S-bonded in a fac configuration, while the fourth is O-bonded. The title compound represents a new, and fourth, polymorph of the complex. Two other monoclinic forms and an ortho-rhom-bic modification have been reported previously.

Related literature

For the geometric parameters and crystal structures of related polymorphs, see: Alessio et al. (1988 ▶); Attia & Calligaris (1987 ▶); Galanski et al. (2003 ▶); Mercer & Trotter (1975 ▶); Pigge et al. (2005 ▶); Srivastava & Fronczek (2003 ▶).

Experimental

Crystal data

[RuCl2(C2H6OS)4]

M = 484.48

Monoclinic,

a = 10.1479 (3) Å

b = 10.4626 (3) Å

c = 18.4280 (4) Å

β = 99.795 (14)°

V = 1928.04 (12) Å3

Z = 4

Mo Kα radiation

μ = 1.53 mm−1

T = 290 (2) K

0.29 × 0.26 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

7705 measured reflections

3777 independent reflections

2953 reflections with I > 2σ(I)

R int = 0.045

3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.077

S = 1.03

3777 reflections

172 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.64 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801996X/fj2125sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801996X/fj2125Isup2.hkl

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

[RuCl2(C2H6OS)4]	F(000) = 984
Mr = 484.48	Dx = 1.669 Mg m−3
Monoclinic, P21/c	Melting point: not measured K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.1479 (3) Å	Cell parameters from 22 reflections
b = 10.4626 (3) Å	θ = 18.2–19.2°
c = 18.4280 (4) Å	µ = 1.53 mm−1
β = 99.795 (14)°	T = 290 K
V = 1928.04 (12) Å3	Prism, orange
Z = 4	0.29 × 0.26 × 0.25 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.045
Radiation source: Enraf Nonius FR590	θmax = 26.0°, θmin = 2.0°
graphite	h = 0→12
non–profiled ω/2θ scans	k = −12→12
7705 measured reflections	l = −22→22
3777 independent reflections	3 standard reflections every 120 min
2953 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0294P)2] where P = (Fo2 + 2Fc2)/3
3777 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.64 e Å−3

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
O11	0.2531 (3)	−0.0625 (3)	0.32395 (16)	0.0530 (8)
O21	0.0063 (3)	0.0806 (3)	0.41116 (15)	0.0465 (7)
O31	0.0400 (3)	0.1627 (3)	0.23279 (15)	0.0543 (8)
O41	0.2122 (3)	0.4088 (2)	0.42297 (14)	0.0400 (6)
C12	0.5002 (4)	0.0204 (5)	0.3510 (2)	0.0603 (13)
H12A	0.5531	0.0958	0.3487	0.09*
H12B	0.5283	−0.0448	0.3203	0.09*
H12C	0.5116	−0.0095	0.4009	0.09*
C13	0.3327 (5)	0.0822 (4)	0.2244 (2)	0.0566 (13)
H13A	0.2448	0.1037	0.1992	0.085*
H13B	0.3627	0.0057	0.2036	0.085*
H13C	0.3931	0.1509	0.2192	0.085*
C22	0.1268 (5)	0.2105 (4)	0.5245 (2)	0.0557 (12)
H22A	0.0838	0.2906	0.5104	0.084*
H22B	0.214	0.226	0.5527	0.084*
H22C	0.0742	0.163	0.5538	0.084*
C23	0.2246 (4)	−0.0186 (4)	0.4854 (2)	0.0539 (12)
H23A	0.3144	0.0027	0.5077	0.081*
H23B	0.2265	−0.0832	0.4486	0.081*
H23C	0.1769	−0.0502	0.5224	0.081*
C32	−0.0494 (4)	0.3293 (5)	0.3199 (2)	0.0556 (12)
H32A	−0.0207	0.3982	0.3532	0.083*
H32B	−0.087	0.2625	0.3457	0.083*
H32C	−0.1158	0.3599	0.2803	0.083*
C33	0.1154 (5)	0.4007 (4)	0.2276 (2)	0.0583 (13)
H33A	0.191	0.3842	0.2039	0.087*
H33B	0.132	0.4759	0.2576	0.087*
H33C	0.0372	0.4134	0.1909	0.087*
C42	0.2707 (6)	0.6430 (4)	0.3906 (3)	0.0814 (19)
H42A	0.2891	0.6265	0.3421	0.122*
H42B	0.3193	0.7174	0.4105	0.122*
H42C	0.1766	0.6575	0.3881	0.122*
C43	0.2747 (6)	0.5653 (6)	0.5310 (3)	0.094 (2)
H43A	0.2969	0.5016	0.5686	0.141*
H43B	0.1803	0.5815	0.5234	0.141*
H43C	0.3223	0.6428	0.546	0.141*
Ru1	0.26756 (3)	0.23282 (3)	0.374946 (14)	0.02744 (9)
Cl1	0.44805 (10)	0.21704 (9)	0.48035 (5)	0.0419 (2)
Cl2	0.41776 (11)	0.35631 (11)	0.31431 (6)	0.0504 (3)
S11	0.32820 (10)	0.05696 (9)	0.31955 (5)	0.0368 (2)
S21	0.14273 (9)	0.12074 (9)	0.44360 (5)	0.0336 (2)
S31	0.08979 (10)	0.26855 (9)	0.28370 (5)	0.0367 (2)
S41	0.32033 (11)	0.50995 (9)	0.44793 (6)	0.0416 (3)

	U11	U22	U33	U12	U13	U23
O11	0.069 (2)	0.0322 (15)	0.0534 (18)	−0.0047 (15)	−0.0011 (16)	−0.0051 (13)
O21	0.0335 (15)	0.0581 (18)	0.0453 (16)	−0.0134 (13)	−0.0011 (13)	0.0070 (14)
O31	0.0523 (18)	0.0505 (18)	0.0508 (18)	0.0058 (15)	−0.0175 (15)	−0.0114 (14)
O41	0.0403 (15)	0.0342 (14)	0.0439 (16)	−0.0031 (12)	0.0024 (13)	−0.0058 (12)
C12	0.046 (3)	0.073 (3)	0.056 (3)	0.024 (2)	−0.007 (2)	−0.014 (2)
C13	0.072 (3)	0.071 (3)	0.027 (2)	0.020 (3)	0.009 (2)	−0.005 (2)
C22	0.063 (3)	0.070 (3)	0.037 (2)	−0.018 (2)	0.019 (2)	−0.010 (2)
C23	0.053 (3)	0.051 (3)	0.056 (3)	−0.001 (2)	0.005 (2)	0.023 (2)
C32	0.041 (2)	0.071 (3)	0.052 (3)	0.021 (2)	−0.002 (2)	0.001 (2)
C33	0.073 (3)	0.058 (3)	0.041 (2)	0.009 (3)	0.001 (2)	0.020 (2)
C42	0.101 (4)	0.033 (2)	0.096 (4)	−0.009 (3)	−0.023 (4)	0.012 (3)
C43	0.129 (6)	0.099 (5)	0.059 (3)	−0.055 (4)	0.029 (4)	−0.043 (3)
Ru1	0.02955 (16)	0.02723 (15)	0.02414 (15)	−0.00181 (12)	0.00061 (11)	0.00173 (12)
Cl1	0.0378 (5)	0.0465 (6)	0.0364 (5)	−0.0057 (4)	−0.0081 (4)	0.0024 (4)
Cl2	0.0538 (7)	0.0539 (6)	0.0456 (6)	−0.0136 (5)	0.0145 (5)	0.0090 (5)
S11	0.0389 (5)	0.0376 (5)	0.0310 (5)	0.0053 (4)	−0.0018 (4)	−0.0038 (4)
S21	0.0341 (5)	0.0369 (5)	0.0285 (5)	−0.0058 (4)	0.0010 (4)	0.0031 (4)
S31	0.0396 (5)	0.0357 (5)	0.0311 (5)	0.0054 (4)	−0.0045 (4)	0.0015 (4)
S41	0.0448 (6)	0.0339 (5)	0.0433 (6)	−0.0039 (4)	−0.0007 (5)	−0.0037 (4)

O11—S11	1.473 (3)	C32—S31	1.779 (4)
O21—S21	1.473 (3)	C32—H32A	0.96
O31—S31	1.484 (3)	C32—H32B	0.96
O41—S41	1.538 (3)	C32—H32C	0.96
O41—Ru1	2.158 (3)	C33—S31	1.772 (4)
C12—S11	1.784 (4)	C33—H33A	0.96
C12—H12A	0.96	C33—H33B	0.96
C12—H12B	0.96	C33—H33C	0.96
C12—H12C	0.96	C42—S41	1.769 (4)
C13—S11	1.781 (4)	C42—H42A	0.96
C13—H13A	0.96	C42—H42B	0.96
C13—H13B	0.96	C42—H42C	0.96
C13—H13C	0.96	C43—S41	1.770 (5)
C22—S21	1.792 (4)	C43—H43A	0.96
C22—H22A	0.96	C43—H43B	0.96
C22—H22B	0.96	C43—H43C	0.96
C22—H22C	0.96	Ru1—S11	2.2404 (10)
C23—S21	1.786 (4)	Ru1—S21	2.2640 (10)
C23—H23A	0.96	Ru1—S31	2.2780 (10)
C23—H23B	0.96	Ru1—Cl2	2.4126 (11)
C23—H23C	0.96	Ru1—Cl1	2.4380 (10)
S41—O41—Ru1	119.18 (15)	S41—C43—H43A	109.5
S11—C12—H12A	109.5	S41—C43—H43B	109.5
S11—C12—H12B	109.5	H43A—C43—H43B	109.5
H12A—C12—H12B	109.5	S41—C43—H43C	109.5
S11—C12—H12C	109.5	H43A—C43—H43C	109.5
H12A—C12—H12C	109.5	H43B—C43—H43C	109.5
H12B—C12—H12C	109.5	O41—Ru1—S11	176.60 (8)
S11—C13—H13A	109.5	O41—Ru1—S21	90.19 (8)
S11—C13—H13B	109.5	S11—Ru1—S21	93.00 (4)
H13A—C13—H13B	109.5	O41—Ru1—S31	86.21 (7)
S11—C13—H13C	109.5	S11—Ru1—S31	92.46 (3)
H13A—C13—H13C	109.5	S21—Ru1—S31	92.82 (4)
H13B—C13—H13C	109.5	O41—Ru1—Cl2	87.83 (8)
S21—C22—H22A	109.5	S11—Ru1—Cl2	89.12 (4)
S21—C22—H22B	109.5	S21—Ru1—Cl2	173.64 (4)
H22A—C22—H22B	109.5	S31—Ru1—Cl2	93.07 (4)
S21—C22—H22C	109.5	O41—Ru1—Cl1	86.78 (7)
H22A—C22—H22C	109.5	S11—Ru1—Cl1	94.59 (4)
H22B—C22—H22C	109.5	S21—Ru1—Cl1	86.31 (3)
S21—C23—H23A	109.5	S31—Ru1—Cl1	172.93 (4)
S21—C23—H23B	109.5	Cl2—Ru1—Cl1	87.54 (4)
H23A—C23—H23B	109.5	O11—S11—C13	106.3 (2)
S21—C23—H23C	109.5	O11—S11—C12	106.7 (2)
H23A—C23—H23C	109.5	C13—S11—C12	99.4 (2)
H23B—C23—H23C	109.5	O11—S11—Ru1	119.14 (14)
S31—C32—H32A	109.5	C13—S11—Ru1	112.43 (15)
S31—C32—H32B	109.5	C12—S11—Ru1	110.94 (15)
H32A—C32—H32B	109.5	O21—S21—C23	106.15 (19)
S31—C32—H32C	109.5	O21—S21—C22	106.02 (19)
H32A—C32—H32C	109.5	C23—S21—C22	99.8 (2)
H32B—C32—H32C	109.5	O21—S21—Ru1	119.85 (12)
S31—C33—H33A	109.5	C23—S21—Ru1	113.59 (15)
S31—C33—H33B	109.5	C22—S21—Ru1	109.35 (15)
H33A—C33—H33B	109.5	O31—S31—C33	106.36 (19)
S31—C33—H33C	109.5	O31—S31—C32	107.3 (2)
H33A—C33—H33C	109.5	C33—S31—C32	98.3 (2)
H33B—C33—H33C	109.5	O31—S31—Ru1	119.07 (12)
S41—C42—H42A	109.5	C33—S31—Ru1	112.47 (16)
S41—C42—H42B	109.5	C32—S31—Ru1	111.21 (14)
H42A—C42—H42B	109.5	O41—S41—C42	104.3 (2)
S41—C42—H42C	109.5	O41—S41—C43	101.9 (2)
H42A—C42—H42C	109.5	C42—S41—C43	99.7 (3)
H42B—C42—H42C	109.5
S41—O41—Ru1—S21	135.85 (16)	S11—Ru1—S21—C23	45.78 (17)
S41—O41—Ru1—S31	−131.33 (16)	S31—Ru1—S21—C23	138.39 (17)
S41—O41—Ru1—Cl2	−38.11 (16)	Cl1—Ru1—S21—C23	−48.64 (17)
S41—O41—Ru1—Cl1	49.55 (16)	O41—Ru1—S21—C22	−24.90 (19)
S21—Ru1—S11—O11	15.75 (14)	S11—Ru1—S21—C22	156.27 (17)
S31—Ru1—S11—O11	−77.21 (14)	S31—Ru1—S21—C22	−111.12 (17)
Cl2—Ru1—S11—O11	−170.25 (14)	Cl1—Ru1—S21—C22	61.86 (17)
Cl1—Ru1—S11—O11	102.29 (14)	O41—Ru1—S31—O31	−165.41 (17)
S21—Ru1—S11—C13	141.01 (18)	S11—Ru1—S31—O31	17.72 (16)
S31—Ru1—S11—C13	48.05 (18)	S21—Ru1—S31—O31	−75.41 (16)
Cl2—Ru1—S11—C13	−44.99 (18)	Cl2—Ru1—S31—O31	106.97 (16)
Cl1—Ru1—S11—C13	−132.46 (18)	O41—Ru1—S31—C33	69.24 (19)
S21—Ru1—S11—C12	−108.64 (18)	S11—Ru1—S31—C33	−107.63 (18)
S31—Ru1—S11—C12	158.40 (18)	S21—Ru1—S31—C33	159.24 (17)
Cl2—Ru1—S11—C12	65.36 (18)	Cl2—Ru1—S31—C33	−18.38 (18)
Cl1—Ru1—S11—C12	−22.10 (18)	O41—Ru1—S31—C32	−39.94 (19)
O41—Ru1—S21—O21	97.69 (16)	S11—Ru1—S31—C32	143.19 (18)
S11—Ru1—S21—O21	−81.13 (15)	S21—Ru1—S31—C32	50.06 (18)
S31—Ru1—S21—O21	11.48 (15)	Cl2—Ru1—S31—C32	−127.56 (18)
Cl1—Ru1—S21—O21	−175.54 (15)	Ru1—O41—S41—C42	116.2 (2)
O41—Ru1—S21—C23	−135.40 (18)	Ru1—O41—S41—C43	−140.4 (3)