trans-Bis(2,2′-bipyridine)dichlorido­ruthenium(II)

In the title compound, [RuCl₂(C₁₀H₈N₂)₂], the Ru atom is located on a crystallographic inversion center. The bipyridine (bpy) ligands are thus coordinated trans, leading to steric inter­actions between pairs of opposite ortho-H atoms. The result is a marked deviation from the expected planarity of some units; the two pyridine rings of an individual bpy ligand enclose a 23.8 (1)° angle. With the RuN₄ plane, the same pyridine rings enclose angles of 22.3 (1) and 21.0 (1)°. The octa­hedral environment of the Ru atom, however, is not markedly distorted, with the Ru—Cl axis enclosing a 87.32 (6)° angle with the RuN₄ plane. In the crystal structure, the most significant inter­molecular inter­action, besides the expected π stacking [3.424 (3) Å perpendicular distance of parallel-stacked rings, and 3.389 (3) Å closest ring–atom distance for an inclined contact], is a weak C—H...Cl hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.026
• wR factor = 0.058
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ru     -   Cl1     ..       9.63 su

Author Response: situation checked, assignment of scattering sites correct

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

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

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S1. Comment

The title compound, C₂₀H₁₆Cl₂N₄Ru, was obtained accidentally on the attempted preparation of [Ru(cis-CptdH_-2)(bipy)₂] (cis-CptdH_-2 = twofold deprotonated cis-1,2-cyclopentanediol, bipy = 2,2'-bipyridine).

The molecular structure is shown in Fig. 1. The five-membered chelate ring Ru—N1—C5—C6—N2 adopts an envelope conformation on Ru (Q₂ = 0.2785 (17) Å, ϕ₂ = 184.3 (5)°). Ring-puckering parameters (Cremer & Pople, 1975) were calculated with PLATON (Spek, 2003).

Bond lengths and angles are comparable to similar compounds (Weathers et al., 1997).

The molecular packing is shown in Fig. 2 which shows a layer of molecules of (I) in the bc plane. Hydrogen bonds of the C–H···Cl type connect these layers along [100]. [100]-stacking is supported by π stacking of aromatic rings that enclose a 23.8 (1)° angle, the closest ring···atom contact being 3.389 (3) Å.

π stacking is also observed for adjacent molecules along [001] between aromatic rings that are connected by an inversion center. The perpendicular ring distance is 3.424 (3) Å for this interaction.

Related literature

Sullivan et al. (1978) describe the respective cis-coordinated complex which was used as the starting material for the synthesis of the title compound. Weathers et al. (1997) describe a related complex cation with the chlorido ligands of the title compound substituted by aqua ligands. For ring puckering analysis, see: Cremer & Pople (1975).

S2. Experimental

The title compound was obtained accidentally on the attempted preparation of [Ru(cis-CptdH_-2)(bipy)₂] by refluxing 58 mg (0.12 mmol) cis-[RuCl₂(bipy)₂] (Sullivan et al., 1978), 27 mg (0.26 mmol) cis-1,2-cyclopentanediol and 15 mg (0.27 mmol) KOH for 4 h in a solution of 1.4 ml H₂O and 4 ml 2-propanol under an inert gas atmosphere (N₂). When the closed reaction flask was left standing at room temperature in bright daylight, violet-black crystals were obtained after several months.

S3. Refinement

All H atoms were included in calculated positions and refined as riding on their parent atoms with one common isotropic displacement parameter.

Computing details

Data collection: COLLECT (Hooft, 2004); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
	Fig. 2. A layer of molecules of (I) in the bc plane.

i>trans-Bis(2,2'-bipyridine)dichloridoruthenium(II)

Crystal data

[RuCl2(C10H8N2)2]	F(000) = 484
Mr = 484.34	Dx = 1.785 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6762 reflections
a = 7.0047 (3) Å	θ = 3.1–27.5°
b = 14.9489 (6) Å	µ = 1.18 mm^−1
c = 8.7301 (3) Å	T = 200 K
β = 99.692 (2)°	Platelet, black-violet
V = 901.10 (6) Å^3	0.15 × 0.10 × 0.06 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	2067 independent reflections
Radiation source: rotating anode	1719 reflections with I > 2σ(I)
MONTEL, graded multilayered X-ray optics monochromator	Rint = 0.041
ϕ and ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −9→8
Tmin = 0.763, Tmax = 0.932	k = −19→19
10312 measured reflections	l = −11→11

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.058	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.015P)^2 + 0.9494P] where P = (Fo^2 + 2Fc^2)/3
2067 reflections	(Δ/σ)max < 0.001
125 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Special details

Experimental. µ × r = 0.116, T_min/T_max = 0.899

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ru	0.0000	0.0000	0.0000	0.01748 (9)
Cl1	−0.18499 (9)	0.12549 (4)	−0.11057 (7)	0.02946 (15)
N1	−0.1977 (3)	−0.09044 (12)	−0.1129 (2)	0.0204 (4)
N2	0.1001 (3)	−0.02145 (12)	−0.2052 (2)	0.0206 (4)
C1	−0.3740 (3)	−0.11069 (15)	−0.0811 (3)	0.0243 (5)
H1	−0.4268	−0.0741	−0.0097	0.033 (3)*
C2	−0.4811 (3)	−0.18208 (16)	−0.1476 (3)	0.0290 (6)
H2	−0.6049	−0.1944	−0.1218	0.033 (3)*
C3	−0.4071 (4)	−0.23546 (17)	−0.2521 (3)	0.0339 (6)
H3	−0.4755	−0.2869	−0.2954	0.033 (3)*
C4	−0.2302 (4)	−0.21242 (16)	−0.2925 (3)	0.0319 (6)
H4	−0.1772	−0.2473	−0.3661	0.033 (3)*
C5	−0.1312 (3)	−0.13828 (15)	−0.2249 (3)	0.0223 (5)
C6	0.0355 (3)	−0.09807 (15)	−0.2809 (3)	0.0231 (5)
C7	0.1040 (4)	−0.12659 (18)	−0.4124 (3)	0.0307 (6)
H7	0.0631	−0.1823	−0.4589	0.033 (3)*
C8	0.2319 (4)	−0.07363 (19)	−0.4754 (3)	0.0344 (6)
H8	0.2803	−0.0920	−0.5658	0.033 (3)*
C9	0.2882 (4)	0.00714 (18)	−0.4039 (3)	0.0333 (6)
H9	0.3730	0.0460	−0.4465	0.033 (3)*
C10	0.2200 (4)	0.03048 (17)	−0.2706 (3)	0.0273 (5)
H10	0.2598	0.0860	−0.2226	0.033 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru	0.02017 (14)	0.01732 (13)	0.01542 (13)	0.00075 (10)	0.00439 (9)	−0.00161 (10)
Cl1	0.0339 (3)	0.0278 (3)	0.0268 (3)	0.0094 (3)	0.0055 (3)	0.0018 (3)
N1	0.0196 (10)	0.0255 (10)	0.0163 (9)	0.0011 (8)	0.0032 (8)	−0.0005 (8)
N2	0.0226 (10)	0.0228 (10)	0.0167 (9)	0.0017 (8)	0.0045 (8)	−0.0008 (7)
C1	0.0246 (12)	0.0245 (12)	0.0242 (13)	0.0042 (10)	0.0053 (10)	0.0006 (9)
C2	0.0206 (12)	0.0333 (13)	0.0328 (14)	−0.0006 (10)	0.0036 (11)	0.0009 (11)
C3	0.0306 (14)	0.0311 (13)	0.0395 (16)	−0.0061 (11)	0.0038 (12)	−0.0120 (12)
C4	0.0314 (14)	0.0300 (13)	0.0348 (15)	−0.0028 (11)	0.0074 (12)	−0.0133 (11)
C5	0.0233 (12)	0.0233 (11)	0.0203 (12)	0.0022 (9)	0.0036 (9)	−0.0036 (9)
C6	0.0244 (12)	0.0253 (12)	0.0191 (12)	0.0043 (9)	0.0022 (10)	−0.0030 (9)
C7	0.0288 (13)	0.0358 (14)	0.0275 (13)	0.0033 (11)	0.0048 (11)	−0.0110 (11)
C8	0.0322 (14)	0.0505 (16)	0.0224 (13)	0.0041 (13)	0.0097 (11)	−0.0054 (12)
C9	0.0319 (14)	0.0431 (15)	0.0279 (13)	0.0002 (12)	0.0136 (11)	0.0069 (12)
C10	0.0308 (13)	0.0275 (12)	0.0247 (13)	−0.0014 (10)	0.0084 (11)	0.0015 (10)

Geometric parameters (Å, º)

Ru—N2	2.0560 (19)	C3—C4	1.388 (4)
Ru—N2^i	2.0560 (19)	C3—H3	0.9500
Ru—N1	2.0632 (18)	C4—C5	1.385 (3)
Ru—N1^i	2.0632 (18)	C4—H4	0.9500
Ru—Cl1^i	2.3893 (6)	C5—C6	1.468 (3)
Ru—Cl1	2.3893 (6)	C6—C7	1.384 (3)
N1—C1	1.345 (3)	C7—C8	1.378 (4)
N1—C5	1.356 (3)	C7—H7	0.9500
N2—C10	1.340 (3)	C8—C9	1.386 (4)
N2—C6	1.361 (3)	C8—H8	0.9500
C1—C2	1.376 (3)	C9—C10	1.375 (4)
C1—H1	0.9500	C9—H9	0.9500
C2—C3	1.377 (4)	C10—H10	0.9500
C2—H2	0.9500
N2—Ru—N2^i	180.00 (9)	C3—C2—H2	120.3
N2—Ru—N1	77.38 (7)	C2—C3—C4	118.5 (2)
N2^i—Ru—N1	102.62 (7)	C2—C3—H3	120.8
N2—Ru—N1^i	102.62 (7)	C4—C3—H3	120.8
N2^i—Ru—N1^i	77.38 (7)	C5—C4—C3	119.6 (2)
N1—Ru—N1^i	180.00 (12)	C5—C4—H4	120.2
N2—Ru—Cl1^i	89.32 (5)	C3—C4—H4	120.2
N2^i—Ru—Cl1^i	90.68 (5)	N1—C5—C4	121.4 (2)
N1—Ru—Cl1^i	87.32 (5)	N1—C5—C6	114.42 (19)
N1^i—Ru—Cl1^i	92.68 (5)	C4—C5—C6	123.7 (2)
N2—Ru—Cl1	90.68 (5)	N2—C6—C7	121.9 (2)
N2^i—Ru—Cl1	89.32 (5)	N2—C6—C5	113.6 (2)
N1—Ru—Cl1	92.68 (5)	C7—C6—C5	123.8 (2)
N1^i—Ru—Cl1	87.31 (5)	C8—C7—C6	119.6 (2)
Cl1^i—Ru—Cl1	180.00 (3)	C8—C7—H7	120.2
C1—N1—C5	117.97 (19)	C6—C7—H7	120.2
C1—N1—Ru	127.93 (16)	C7—C8—C9	118.4 (2)
C5—N1—Ru	113.93 (15)	C7—C8—H8	120.8
C10—N2—C6	117.5 (2)	C9—C8—H8	120.8
C10—N2—Ru	127.67 (16)	C10—C9—C8	119.3 (2)
C6—N2—Ru	114.84 (16)	C10—C9—H9	120.4
N1—C1—C2	122.8 (2)	C8—C9—H9	120.4
N1—C1—H1	118.6	N2—C10—C9	123.0 (2)
C2—C1—H1	118.6	N2—C10—H10	118.5
C1—C2—C3	119.3 (2)	C9—C10—H10	118.5
C1—C2—H2	120.3
N2—Ru—N1—C1	−163.6 (2)	C1—N1—C5—C4	−7.4 (3)
N2^i—Ru—N1—C1	16.4 (2)	Ru—N1—C5—C4	168.23 (18)
Cl1^i—Ru—N1—C1	106.46 (19)	C1—N1—C5—C6	164.8 (2)
Cl1—Ru—N1—C1	−73.54 (19)	Ru—N1—C5—C6	−19.6 (2)
N2—Ru—N1—C5	21.26 (15)	C3—C4—C5—N1	3.9 (4)
N2^i—Ru—N1—C5	−158.74 (15)	C3—C4—C5—C6	−167.5 (2)
Cl1^i—Ru—N1—C5	−68.65 (15)	C10—N2—C6—C7	6.1 (3)
Cl1—Ru—N1—C5	111.35 (15)	Ru—N2—C6—C7	−173.60 (18)
N1—Ru—N2—C10	160.5 (2)	C10—N2—C6—C5	−164.9 (2)
N1^i—Ru—N2—C10	−19.5 (2)	Ru—N2—C6—C5	15.4 (2)
Cl1^i—Ru—N2—C10	−112.12 (19)	N1—C5—C6—N2	2.9 (3)
Cl1—Ru—N2—C10	67.88 (19)	C4—C5—C6—N2	174.9 (2)
N1—Ru—N2—C6	−19.82 (15)	N1—C5—C6—C7	−168.0 (2)
N1^i—Ru—N2—C6	160.18 (15)	C4—C5—C6—C7	4.0 (4)
Cl1^i—Ru—N2—C6	67.58 (15)	N2—C6—C7—C8	−4.3 (4)
Cl1—Ru—N2—C6	−112.42 (15)	C5—C6—C7—C8	165.8 (2)
C5—N1—C1—C2	5.6 (3)	C6—C7—C8—C9	0.1 (4)
Ru—N1—C1—C2	−169.29 (17)	C7—C8—C9—C10	2.0 (4)
N1—C1—C2—C3	−0.4 (4)	C6—N2—C10—C9	−4.0 (3)
C1—C2—C3—C4	−3.2 (4)	Ru—N2—C10—C9	175.73 (18)
C2—C3—C4—C5	1.5 (4)	C8—C9—C10—N2	0.0 (4)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1^ii	0.95	2.72	3.573 (3)	150

Symmetry code: (ii) −x−1, y−1/2, −z−1/2.