cis-Bis(2,2'-bipyrid­yl)dichloridoruthenium(II) dichloro­methane solvate

In the crystal structure of the title compound, [RuCl₂(C₁₀H₈N₂)₂]·CH₂Cl₂, the complex consists of two bidentate 2,2'-bipyridyl N-atom donors and two chloride ions coordinated to an Ru^II centre which lies on a crystallographic twofold rotation axis. Equivalent ligands are cis, each related by the twofold rotation. One dichloro­methane solvent mol­ecule per Ru complex is trapped in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.027
• wR factor = 0.064
• Data-to-parameter ratio = 19.4

checkCIF/PLATON results

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Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ru1    -   Cl1     ..       8.30 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ru1    -   N12     ..       5.05 su

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _reflns_number_total               2654
           Count of symmetry unique reflns         1394
           Completeness (_total/calc)            190.39%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1260
           Fraction of Friedel pairs measured     0.904
           Are heavy atom types Z>Si present        yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ru1         (3)       3.39
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

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

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S1. Comment

The structure of the title compound, (I), is shown in Fig. 1. A l l bond lengths and angles are normal. The complex has been reported earlier in lower symmetry space groups as the hydrate in C2/c (Eggleston et al., 1985), as an acetone solvate in P21/n (Lackner et al., 2004), and as an I₂ adduct in C2/c (Nag et al., 2006).

The structure of (I) displays distorted octahedral coordination to the metal cation, without any significant hydrogen bonding. The solvent molecule is free in the lattice and displays larger thermal displacements than seen in the Ru complex.

The 2,2'-bipyridyl ligand is planar. The five membered chelate ring is folded about the N1···N12 line with a dihedral angle between the plane of the ligand, and the N1/Ru1/N12 plane of 5.0 (2)°. The dihedral angle between the least square planes of the two fold rotation related 2,2'-bipyridyl ligands is 87.78°. The Cl1—Ru1—Cl1ⁱ [symmetry code: (i) -x, -y + 2, z] angle is 93.31 (5)°.

Related literature

For related literature, see: Eggleston et al. (1985); Lackner et al. (2004); Nag et al. (2006).

S2. Experimental

1.0 mmole ruthenium trichloride and 2.0 mmol 2,2'-dipyridyl were refluxed in absolute ethanol for 4 h followed with the addition of 11.8 mmol LiCl and further reflux for additional 1 h. The solvent was then removed by rotary evaporator and the crude product dissolved in dichloromethane, filtered and washed by water and reduced to 20 ml. Chromatography on alumina with 10:1 dichloromethane: methanol as eluent yielded 0.2 g of the neutral complex from the second dark-pink band. Suitable crystals of (I) were obtained upon recrystallization from dichloromethane and slow evapotation of solvent.

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H distances fixed at 0.93 Å (aromatic) and 0.97 Å (methylene) and with U_iso constrained to be 1.2U_eq of the carrier atom.

Computing details

Data collection: SMART (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus; program(s) used to solve structure: XS in SHELXTL (Bruker, 2003); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.

Figures

Fig. 1. The molecular structure of the title compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

cis-Bis(2,2'-bipyridyl)dichloridoruthenium(II) dichloromethane solvate

Crystal data

[RuCl2(C10H8N2)2]·CH2Cl2	F(000) = 1136
Mr = 569.26	Dx = 1.638 Mg m^−3
Orthorhombic, Aba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2ac	Cell parameters from 7381 reflections
a = 12.5658 (9) Å	θ = 2.6–29.6°
b = 15.4595 (11) Å	µ = 1.16 mm^−1
c = 11.8864 (9) Å	T = 298 K
V = 2309.1 (3) Å^3	Plate, red
Z = 4	0.25 × 0.22 × 0.03 mm

Data collection

Bruker/Siemens SMART APEX diffractometer	2654 independent reflections
Radiation source: normal-focus sealed tube, Bruker SMART APEX	2310 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 8.3 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −20→20
Tmin = 0.761, Tmax = 0.966	l = −15→15
16972 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0344P)^2 + 0.0898P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2654 reflections	Δρmax = 0.49 e Å^−3
137 parameters	Δρmin = −0.28 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1260 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (5)

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	Occ. (<1)
C2	0.2168 (3)	0.9265 (2)	0.3118 (3)	0.0486 (8)
H2	0.2240	0.9752	0.3572	0.058*
C3	0.2952 (3)	0.8648 (3)	0.3151 (4)	0.0588 (10)
H3	0.3537	0.8715	0.3622	0.071*
C4	0.2863 (2)	0.7930 (2)	0.2481 (4)	0.0594 (9)
H4	0.3387	0.7505	0.2485	0.071*
C5	0.1983 (3)	0.7851 (2)	0.1802 (3)	0.0507 (9)
H5	0.1906	0.7368	0.1343	0.061*
C6	0.1209 (2)	0.84917 (18)	0.1803 (3)	0.0361 (7)
C7	0.0243 (3)	0.84691 (19)	0.1115 (3)	0.0369 (7)
C8	0.0016 (3)	0.7830 (2)	0.0331 (3)	0.0488 (9)
H8	0.0487	0.7373	0.0225	0.059*
C9	−0.0896 (3)	0.7873 (2)	−0.0284 (3)	0.0569 (9)
H9	−0.1048	0.7451	−0.0818	0.068*
C10	−0.1594 (3)	0.8549 (2)	−0.0110 (3)	0.0505 (9)
H10	−0.2224	0.8587	−0.0519	0.061*
C11	−0.1340 (3)	0.9165 (2)	0.0681 (3)	0.0424 (7)
H11	−0.1810	0.9621	0.0798	0.051*
C13	0.5000	1.0000	0.1365 (7)	0.127 (5)
H13A	0.5485	1.0318	0.0883	0.152*	0.50
H13B	0.4515	0.9682	0.0883	0.152*	0.50
Cl1	0.07119 (7)	1.09792 (5)	0.38787 (7)	0.0464 (2)
Cl2	0.57183 (12)	0.92754 (9)	0.21546 (12)	0.1012 (5)
N1	0.13028 (16)	0.91993 (13)	0.2463 (3)	0.0345 (5)
N12	−0.0450 (2)	0.91362 (16)	0.1286 (2)	0.0334 (6)
Ru1	0.0000	1.0000	0.24825 (6)	0.02831 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0427 (18)	0.0461 (19)	0.057 (2)	0.0029 (15)	−0.0107 (17)	−0.0032 (16)
C3	0.0386 (18)	0.065 (2)	0.072 (3)	0.0103 (17)	−0.0118 (18)	0.010 (2)
C4	0.0447 (17)	0.0552 (19)	0.078 (2)	0.0240 (15)	0.004 (3)	0.008 (3)
C5	0.050 (2)	0.0377 (17)	0.064 (2)	0.0135 (15)	0.0081 (18)	−0.0020 (16)
C6	0.0382 (16)	0.0276 (14)	0.0424 (17)	0.0005 (12)	0.0058 (13)	0.0014 (13)
C7	0.0469 (18)	0.0267 (15)	0.0372 (16)	0.0018 (12)	0.0049 (13)	−0.0023 (13)
C8	0.061 (2)	0.0390 (19)	0.0468 (19)	0.0030 (16)	0.0043 (17)	−0.0140 (16)
C9	0.069 (2)	0.054 (2)	0.048 (2)	−0.0087 (18)	−0.0080 (19)	−0.0144 (17)
C10	0.052 (2)	0.056 (2)	0.0440 (19)	−0.0116 (17)	−0.0157 (17)	0.0007 (17)
C11	0.0425 (17)	0.0387 (17)	0.0460 (18)	0.0010 (14)	−0.0048 (14)	0.0035 (14)
C13	0.190 (11)	0.130 (8)	0.061 (5)	0.101 (7)	0.000	0.000
Cl1	0.0544 (5)	0.0369 (4)	0.0479 (4)	−0.0043 (4)	−0.0010 (4)	−0.0102 (4)
Cl2	0.1190 (12)	0.0895 (8)	0.0952 (11)	0.0280 (8)	−0.0265 (8)	0.0055 (8)
N1	0.0339 (11)	0.0295 (10)	0.0403 (12)	0.0028 (8)	−0.0011 (15)	0.0003 (14)
N12	0.0352 (13)	0.0269 (14)	0.0380 (14)	0.0006 (11)	0.0017 (12)	0.0019 (11)
Ru1	0.03049 (13)	0.02159 (12)	0.03284 (14)	0.00206 (12)	0.000	0.000

Geometric parameters (Å, º)

C2—N1	1.342 (4)	C9—H9	0.9300
C2—C3	1.372 (5)	C10—C11	1.376 (5)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.370 (6)	C11—N12	1.330 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.374 (5)	C13—Cl2^i	1.718 (5)
C4—H4	0.9300	C13—Cl2	1.718 (5)
C5—C6	1.388 (4)	C13—H13A	0.9700
C5—H5	0.9300	C13—H13B	0.9700
C6—N1	1.351 (4)	Cl1—Ru1	2.4179 (9)
C6—C7	1.464 (4)	N1—Ru1	2.052 (2)
C7—N12	1.365 (4)	N12—Ru1	2.031 (3)
C7—C8	1.388 (5)	Ru1—N12^ii	2.031 (3)
C8—C9	1.362 (5)	Ru1—N1^ii	2.052 (2)
C8—H8	0.9300	Ru1—Cl1^ii	2.4179 (9)
C9—C10	1.379 (5)
N1—C2—C3	123.0 (3)	C10—C11—H11	118.6
N1—C2—H2	118.5	Cl2^i—C13—Cl2	113.7 (5)
C3—C2—H2	118.5	Cl2^i—C13—H13A	108.8
C4—C3—C2	119.3 (3)	Cl2—C13—H13A	108.8
C4—C3—H3	120.4	Cl2^i—C13—H13B	108.8
C2—C3—H3	120.4	Cl2—C13—H13B	108.8
C3—C4—C5	118.6 (3)	H13A—C13—H13B	107.7
C3—C4—H4	120.7	C2—N1—C6	117.9 (3)
C5—C4—H4	120.7	C2—N1—Ru1	126.4 (2)
C4—C5—C6	120.0 (3)	C6—N1—Ru1	115.21 (19)
C4—C5—H5	120.0	C11—N12—C7	118.8 (3)
C6—C5—H5	120.0	C11—N12—Ru1	126.2 (2)
N1—C6—C5	121.2 (3)	C7—N12—Ru1	115.0 (2)
N1—C6—C7	114.5 (2)	N12—Ru1—N12^ii	91.08 (15)
C5—C6—C7	124.3 (3)	N12—Ru1—N1	79.47 (11)
N12—C7—C8	120.4 (3)	N12^ii—Ru1—N1	99.59 (11)
N12—C7—C6	115.3 (3)	N12—Ru1—N1^ii	99.59 (11)
C8—C7—C6	124.2 (3)	N12^ii—Ru1—N1^ii	79.47 (11)
C9—C8—C7	119.9 (3)	N1—Ru1—N1^ii	178.68 (19)
C9—C8—H8	120.0	N12—Ru1—Cl1	174.38 (8)
C7—C8—H8	120.0	N12^ii—Ru1—Cl1	88.07 (7)
C8—C9—C10	119.5 (3)	N1—Ru1—Cl1	95.19 (8)
C8—C9—H9	120.3	N1^ii—Ru1—Cl1	85.72 (8)
C10—C9—H9	120.3	N12—Ru1—Cl1^ii	88.07 (7)
C11—C10—C9	118.6 (3)	N12^ii—Ru1—Cl1^ii	174.38 (8)
C11—C10—H10	120.7	N1—Ru1—Cl1^ii	85.72 (8)
C9—C10—H10	120.7	N1^ii—Ru1—Cl1^ii	95.19 (8)
N12—C11—C10	122.8 (3)	Cl1—Ru1—Cl1^ii	93.31 (5)
N12—C11—H11	118.6

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