trans-Bis(iso­thio­cyanato)­tetra­pyridine­ruthenium(II) di­chloro­methane disolvate

The title compound, trans-[Ru(NCS)₂(C₅H₅N)₄]·2CH₂Cl₂, was prepared by the reaction between trans-di­chloro­tetra­pyridine­ruthenium(II) and excess KSCN in refluxing aqueous pyri­dine. The Ru atom is in a pseudo-octahedral environment, with two N-donors from two monodentate NCS groups and four N-donors from the pyridine ligands. The complex molecule lies on a crystallographic twofold rotation axis, passing through Ru and the two pyridine ligands

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.047
• wR factor = 0.117
• Data-to-parameter ratio = 16.3

checkCIF results

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S1. Comment

The crystal structure of the title compound, (I), consists of discrete trans-[Ru(NCS)₂(C₅H₅N)₄] molecules and dichloromethane solvate molecules. The Ru atom is coordinated octahedrally by four N atoms from the pyridine ligands and by two N atoms from the monodentate NCS groups in an octahedral arrangement. The Ru—N(C₅H₅N) lengths are in the range 2.072 (5)–2.096 (5) Å, close to those in the reported compounds trans-Ru(CN)₂(C₅H₅N)₄·2MeCN (Coe et al., 1995a) and trans-[RuCl(C₅H₅N)₄(PhCN)]PF₆ (Coe et al., 1995b). The NCS groups are essentially linear. The N4—C1 [1.159 (5) Å] and C1—S1 [1.632 (4) Å] lengths indicate triple- and single-bond character, respectively, and are similar to those in the reported complexes Ni(NCS)₂(C₅H₅N)₄ (Valach et al., 1984) and Ni(en)₂(NCS)₂·C₆H₆ (Squattrito et al., 1996). The C—C [1.339 (9)–1.389 (7) Å] and C—N [1.323 (6)–1.346 (5) Å] lengths are in the normal ranges for pyridine ligands (Evans et al., 1973; Coe et al., 1995). The mean bond angles in the pyridine [C—N—C = 116.2 (7)°, N—C—C = 123.4 (8)°, and C—C—C = 118.4 (4) and 119.6 (4)°] are similar to those observed in Ni(NCS)₂(py)₄ [C—N—C = 116.8 (5)°, N—C—C = 122.8 (5)°, and C—C—C = 117.1 (6) and 120.2 (6)°; Valach et al., 1984].

S2. Experimental

The title compound was synthesized by the reaction of a pyridine solution of trans-RuCl₂(C₅H₅N)₄ (Evans et al., 1973) with an excess aqueous solution of KSCN. After refluxing for 1 h, the solution was put aside at room temperature to give a yellow precipitate. The solid was then filtered off, washed with methanol and ether, and dried in air. Well shaped crystals were grown by slow diffusion of hexane into the dichloromethane solution at room temperature.

S3. Refinement

The positions of the H atoms were genetared geometrically (C—H bond fixed at 0.96 Å), assigned isotropic displacement parameters and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS96 (Sheldrick, 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the title complex with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Trans-bis(isothiocyanato)tetrakis(pyridine)ruthenium(II)

Crystal data

[Ru(NCS)2(C5H5N)4]·2CH2Cl2	F(000) = 1416
Mr = 703.48	Dx = 1.474 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.9410 (8) Å	Cell parameters from 3186 reflections
b = 16.1308 (11) Å	θ = 2.0–25.0°
c = 15.4715 (11) Å	µ = 0.99 mm^−1
β = 100.988 (2)°	T = 293 K
V = 3170.4 (4) Å^3	Prism, yellow
Z = 4	0.40 × 0.35 × 0.28 mm

Data collection

Siemens SMART CCD diffractometer	2765 independent reflections
Radiation source: fine-focus sealed tube	2352 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −14→15
Tmin = 0.681, Tmax = 0.759	k = −19→10
4923 measured reflections	l = −13→18

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 11.5869P] where P = (Fo^2 + 2Fc^2)/3
2765 reflections	(Δ/σ)max < 0.001
170 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.86 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	0.5000	0.27597 (3)	0.7500	0.04076 (17)
Cl1	0.1692 (3)	0.4684 (2)	1.0558 (3)	0.2039 (16)
Cl2	0.3637 (2)	0.43891 (18)	1.0005 (2)	0.1525 (10)
S1	0.15016 (10)	0.27837 (10)	0.81361 (11)	0.0709 (4)
N1	0.5000	0.4059 (3)	0.7500	0.0498 (13)
N2	0.5533 (3)	0.2763 (2)	0.8858 (2)	0.0464 (8)
N3	0.5000	0.1475 (3)	0.7500	0.0465 (12)
N4	0.3503 (3)	0.2757 (2)	0.7712 (2)	0.0448 (8)
C1	0.2672 (3)	0.2768 (3)	0.7889 (3)	0.0427 (9)
C2	0.2545 (8)	0.3953 (6)	1.0315 (6)	0.137 (3)
H2A	0.2183	0.3605	0.9842	0.165*
H2B	0.2770	0.3604	1.0827	0.165*
C12	0.4372 (5)	0.4496 (4)	0.7907 (5)	0.092 (2)
H12A	0.3920	0.4213	0.8206	0.110*
C13	0.4355 (6)	0.5348 (4)	0.7911 (6)	0.113 (3)
H13A	0.3891	0.5626	0.8201	0.136*
C14	0.5000	0.5782 (6)	0.7500	0.093 (3)
H14A	0.5000	0.6359	0.7500	0.112*
C22	0.6299 (4)	0.3278 (3)	0.9244 (3)	0.0573 (12)
H22A	0.6604	0.3630	0.8887	0.069*
C23	0.6658 (5)	0.3311 (4)	1.0139 (4)	0.0746 (16)
H23A	0.7192	0.3676	1.0379	0.090*
C24	0.6217 (6)	0.2797 (4)	1.0673 (3)	0.0820 (19)
H24A	0.6444	0.2811	1.1280	0.098*
C25	0.5438 (5)	0.2265 (4)	1.0300 (3)	0.0779 (17)
H25A	0.5131	0.1908	1.0651	0.093*
C26	0.5109 (4)	0.2262 (3)	0.9392 (3)	0.0615 (13)
H26A	0.4575	0.1899	0.9143	0.074*
C32	0.5857 (4)	0.1030 (3)	0.7852 (3)	0.0600 (13)
H32A	0.6466	0.1315	0.8101	0.072*
C33	0.5880 (5)	0.0176 (4)	0.7865 (4)	0.0815 (18)
H33A	0.6492	−0.0102	0.8120	0.098*
C34	0.5000	−0.0257 (5)	0.7500	0.089 (3)
H34A	0.5000	−0.0834	0.7500	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0378 (3)	0.0470 (3)	0.0384 (3)	0.000	0.00963 (19)	0.000
Cl1	0.219 (4)	0.166 (3)	0.264 (4)	−0.026 (3)	0.141 (3)	−0.022 (3)
Cl2	0.157 (2)	0.149 (2)	0.158 (2)	−0.0054 (18)	0.0447 (19)	−0.0049 (18)
S1	0.0489 (7)	0.0770 (9)	0.0947 (10)	−0.0012 (7)	0.0334 (7)	−0.0080 (8)
N1	0.048 (3)	0.052 (3)	0.048 (3)	0.000	0.005 (2)	0.000
N2	0.0443 (19)	0.053 (2)	0.0428 (19)	0.0067 (17)	0.0102 (16)	−0.0030 (17)
N3	0.044 (3)	0.060 (3)	0.036 (3)	0.000	0.007 (2)	0.000
N4	0.043 (2)	0.051 (2)	0.0411 (19)	0.0003 (17)	0.0097 (15)	−0.0002 (17)
C1	0.046 (2)	0.039 (2)	0.043 (2)	0.001 (2)	0.0102 (18)	0.0039 (19)
C2	0.175 (9)	0.102 (6)	0.133 (7)	−0.028 (6)	0.024 (7)	0.023 (6)
C12	0.099 (5)	0.062 (4)	0.130 (6)	−0.011 (3)	0.059 (4)	−0.029 (4)
C13	0.120 (6)	0.060 (4)	0.173 (8)	−0.002 (4)	0.061 (6)	−0.039 (5)
C14	0.104 (8)	0.060 (6)	0.108 (8)	0.000	0.002 (6)	0.000
C22	0.060 (3)	0.062 (3)	0.047 (3)	0.005 (2)	0.001 (2)	−0.006 (2)
C23	0.082 (4)	0.077 (4)	0.055 (3)	0.010 (3)	−0.010 (3)	−0.016 (3)
C24	0.103 (5)	0.101 (5)	0.037 (3)	0.033 (4)	0.002 (3)	−0.006 (3)
C25	0.088 (4)	0.102 (5)	0.049 (3)	0.025 (4)	0.027 (3)	0.014 (3)
C26	0.063 (3)	0.073 (3)	0.051 (3)	0.000 (3)	0.016 (2)	0.010 (3)
C32	0.059 (3)	0.054 (3)	0.062 (3)	0.004 (2)	−0.002 (2)	0.003 (2)
C33	0.083 (4)	0.060 (4)	0.096 (5)	0.013 (3)	0.004 (3)	0.012 (3)
C34	0.110 (8)	0.045 (5)	0.111 (7)	0.000	0.018 (6)	0.000

Geometric parameters (Å, º)

Ru1—N4^i	2.025 (3)	C13—C14	1.339 (9)
Ru1—N4	2.025 (3)	C13—H13A	0.9300
Ru1—N3	2.072 (5)	C14—C13^i	1.339 (9)
Ru1—N2^i	2.082 (3)	C14—H14A	0.9300
Ru1—N2	2.082 (3)	C22—C23	1.376 (7)
Ru1—N1	2.096 (5)	C22—H22A	0.9300
Cl1—C2	1.705 (10)	C23—C24	1.368 (9)
Cl2—C2	1.727 (9)	C23—H23A	0.9300
S1—C1	1.632 (4)	C24—C25	1.366 (9)
N1—C12^i	1.323 (6)	C24—H24A	0.9300
N1—C12	1.323 (6)	C25—C26	1.389 (7)
N2—C22	1.343 (6)	C25—H25A	0.9300
N2—C26	1.346 (6)	C26—H26A	0.9300
N3—C32^i	1.346 (5)	C32—C33	1.378 (7)
N3—C32	1.346 (5)	C32—H32A	0.9300
N4—C1	1.159 (5)	C33—C34	1.364 (7)
C2—H2A	0.9700	C33—H33A	0.9300
C2—H2B	0.9700	C34—C33^i	1.364 (7)
C12—C13	1.375 (9)	C34—H34A	0.9300
C12—H12A	0.9300
N4^i—Ru1—N4	179.8 (2)	N1—C12—H12A	118.4
N4^i—Ru1—N3	89.88 (11)	C13—C12—H12A	118.4
N4—Ru1—N3	89.88 (11)	C14—C13—C12	120.6 (7)
N4^i—Ru1—N2^i	88.84 (13)	C14—C13—H13A	119.7
N4—Ru1—N2^i	91.16 (13)	C12—C13—H13A	119.7
N3—Ru1—N2^i	90.16 (11)	C13—C14—C13^i	117.0 (9)
N4^i—Ru1—N2	91.16 (13)	C13—C14—H14A	121.5
N4—Ru1—N2	88.84 (13)	C13^i—C14—H14A	121.5
N3—Ru1—N2	90.16 (11)	N2—C22—C23	123.4 (5)
N2^i—Ru1—N2	179.7 (2)	N2—C22—H22A	118.3
N4^i—Ru1—N1	90.12 (11)	C23—C22—H22A	118.3
N4—Ru1—N1	90.12 (11)	C24—C23—C22	119.0 (6)
N3—Ru1—N1	180.000 (1)	C24—C23—H23A	120.5
N2^i—Ru1—N1	89.84 (11)	C22—C23—H23A	120.5
N2—Ru1—N1	89.84 (11)	C25—C24—C23	119.1 (5)
C12^i—N1—C12	115.6 (7)	C25—C24—H24A	120.5
C12^i—N1—Ru1	122.2 (4)	C23—C24—H24A	120.5
C12—N1—Ru1	122.2 (4)	C24—C25—C26	119.2 (6)
C22—N2—C26	116.9 (4)	C24—C25—H25A	120.4
C22—N2—Ru1	121.6 (3)	C26—C25—H25A	120.4
C26—N2—Ru1	121.5 (3)	N2—C26—C25	122.5 (5)
C32^i—N3—C32	115.5 (6)	N2—C26—H26A	118.8
C32^i—N3—Ru1	122.2 (3)	C25—C26—H26A	118.8
C32—N3—Ru1	122.2 (3)	N3—C32—C33	123.6 (5)
C1—N4—Ru1	175.6 (3)	N3—C32—H32A	118.2
N4—C1—S1	179.9 (5)	C33—C32—H32A	118.2
Cl1—C2—Cl2	112.2 (5)	C34—C33—C32	119.5 (6)
Cl1—C2—H2A	109.2	C34—C33—H33A	120.2
Cl2—C2—H2A	109.2	C32—C33—H33A	120.2
Cl1—C2—H2B	109.2	C33—C34—C33^i	118.3 (8)
Cl2—C2—H2B	109.2	C33—C34—H34A	120.9
H2A—C2—H2B	107.9	C33^i—C34—H34A	120.9
N1—C12—C13	123.1 (6)

Symmetry code: (i) −x+1, y, −z+3/2.