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The title compound, trans-[RuIICl2(N1-mepym)4] (mepym is 4-methylpyrimidine, C5H6N2), obtained from the reaction of trans,cis,cis-[RuIICl2(N1-mepym)2(SbPh3)2] (Ph is phenyl) with excess mepym in ethanol, has fourfold crystallographic symmetry and has the four pyrimidine bases coordinated through N1 and arranged in a propeller-like orientation. The Ru—N and Ru—Cl bond distances are 2.082 (2) and 2.400 (4) Å, respectively. The methyl group, and the N3 and Cl atoms are involved in intermolecular C—H...N and C—­H...Cl hydrogen-bond interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009647/na1526sup1.cif
Contains datablocks T69RABS4global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009647/na1526Isup2.hkl
Contains datablock I

CCDC reference: 173350

Comment top

The structural characterization of ruthenium complexes with pyrimidine and purine bases is an important preliminary step to understand the molecular mechanism for the cytostatic effects exerted by certain ruthenium compounds (Clarke et al., 1999, and references therein).

As part of a project from this laboratory devoted to the synthesis and the structural characterization of new ruthenium complexes which contain pyrimidine and purine bases (see for instance previously published papers by this group: Cini & Pifferi, 2000; Bellucci & Cini, 1999; Pifferi & Cini, 1998; Cini et al., 1993) we wish to report here on the X-ray diffraction analysis of the crystal and molecular structure of trans-[RuCl2(mepym)4], (I). \sch

The complex molecule contains the 4-methyl-1,3-pyrimidine ligand which can be considered a model of the nucleic acid pyrimidine bases. It has a pseudo-octahedral coordination sphere (see Fig. 1) in which the metal atom is linked to two Cl- anions (at apical positions) and to four N1 atoms from the mepym ligands. The Ru and Cl atoms are located on the fourfold crystallographic axis.

The Ru—Cl bond distances [average, 2.400 (4) Å] are in agreement with the corresponding values for other RuII-complexes (Bellucci & Cini, 1999; Pifferi & Cini, 1998). The Ru—N bond distances are 2.082 (2) Å, a value somewhat shorter than the Ru—N(mepym) lengths [2.131 (5) Å] found for trans,cis,cis-[RuCl2(mepym)2(SbPh3)2] (Cini et al., 2001). This fact is understandable on the basis of the larger trans influence exerted by triphenylstibine when compared to mepyn as well as on the high steric hindrance due to two cis SbPh3 ligands. Other Ru—N bond lengths for substituted pyrimidine agree well with the value found in this work and are 2.036 (3) Å (average) for cis,trans, cis-dichloro-bis(2-phenylazo)pyrimidine)ruthenium(II) (Santra et al., 1999) and 2.081 (2) Å (average) for trans,cis,cis,-dichloro-bis(2-phenylazo) pyrimidine)ruthenium(II) (Santra et al., 1999). The bond angles around the metal center have almost the idealized values of 90 and 180°.

The bond distances and angles within the mepym ligand have normal values when compared to other metal complexes, see for instance, trans-dichloro (phenyl)-bis(pyridine)(N1-4-methyl-1,3-pyrimidine)rhodium(III) (Cini et al., 1999) and catena[(µ2-N,S-thiocyanato)-(N-4-methylpyrimidine) copper(I)] (Teichert & Sheldrick, 1999). The orientation of the mepym planes with respect to the Ru—Cl vectors is almost exactly staggered, the C2—N1—Ru—Cl2 torsion angle being -39.3 (3)°. As a consequence, the arrangement of the four mepym ligands in the equatorial plane of the complex molecule can be described as propeller-like.

The existence of two C—H···Cl intramolecular hydrogen-bond type interactions per mepym ligand is not excluded on the basis of the contact distances and angles (see Table 2), even though an eclipsed conformation would bring to stronger C—H···Cl interactions.

The analysis of the crystal packing shows the existence of short intermolecular C—H···Cl and C—H···N contacts which involve the methyl group, and the chloride ligands and the N3 atoms. The selected contact distances and angles are quoted in Table 2. It has to be emphasized that interactions of the type C—H···X (X = O, N, halogen) attract increasing interest in the community of structural and bioinorganic chemists (see for instance: Taylor & Kennard, 1982; Sigel et al., 1998; Lippert et al., 2001; Huang et al., 1998; Cini & Cavaglioni, 1999).

Experimental top

The crystals of the title compound as red prisms were obtained on mixing a suspension of trans,cis,cis-[RuIICl2(N1-mepym)2(SbPh3)2] (Cini et al., 2001) in absolute ethanol with a hundred excess mepym and refluxing the mixture under an atmosphere of ultra-pure nitrogen for 30 min. The deaerated clear solution was then stored at 278 K; single crystals formed within 48 h.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEP-32/ORTEPIII (Farrugia, 1998); software used to prepare material for publication: CIFTAB (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. Molecular structure showing 30% probability displacement ellipsoids.
Trans-dichloro-tetrakis(N1-4-methyl-1,3-pyrimidine- ruthenium(II) top
Crystal data top
[RuCl2(C5H6N2)4]Dx = 1.552 Mg m3
Mr = 548.44Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4Cell parameters from 24 reflections
a = 11.295 (1) Åθ = 6–16°
c = 9.200 (1) ŵ = 0.92 mm1
V = 1173.7 (2) Å3T = 293 K
Z = 2Prism, red
F(000) = 5560.30 × 0.20 × 0.10 mm
Data collection top
Siemens P4
diffractometer
898 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 25.0°, θmin = 2.6°
ω scansh = 1012
Absorption correction: empirical (using intensity measurements) via ψ scan
(North et al., 1968)
k = 1311
Tmin = 0.872, Tmax = 0.912l = 910
2354 measured reflections3 standard reflections every 97 reflections
990 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.059Calculated w = 1/[σ2(Fo2) + (0.0304P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
990 reflectionsΔρmax = 0.29 e Å3
73 parametersΔρmin = 0.17 e Å3
1 restraintAbsolute structure: Flack, 1983
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.19 (5)
Crystal data top
[RuCl2(C5H6N2)4]Z = 2
Mr = 548.44Mo Kα radiation
Tetragonal, I4µ = 0.92 mm1
a = 11.295 (1) ÅT = 293 K
c = 9.200 (1) Å0.30 × 0.20 × 0.10 mm
V = 1173.7 (2) Å3
Data collection top
Siemens P4
diffractometer
898 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements) via ψ scan
(North et al., 1968)
Rint = 0.028
Tmin = 0.872, Tmax = 0.9123 standard reflections every 97 reflections
2354 measured reflections intensity decay: none
990 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.059Δρmax = 0.29 e Å3
S = 1.05Δρmin = 0.17 e Å3
990 reflectionsAbsolute structure: Flack, 1983
73 parametersAbsolute structure parameter: 0.19 (5)
1 restraint
Special details top

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. The assignment of the positions for the N3 and C5 atoms was based on the smallest values for the agreement factors and on the analysis of the intermolecular contacts. All the H atoms were set in calculated positions and allowed to ride on the respective C atoms during refinement. All the non-hydrogen atoms were treated anisotropically; whereas all the H atoms were considered isotropic and their displacement parameters were restrained to 1.2U(eq) of the atoms to which they are bound.

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 (Å2) top
xyzUiso*/Ueq
Ru0.00000.00000.04177 (17)0.04569 (19)
Cl10.00000.00000.3025 (3)0.0622 (14)
Cl20.00000.00000.2192 (3)0.0617 (14)
N10.1701 (2)0.0712 (2)0.0401 (8)0.0498 (6)
C20.2521 (4)0.0367 (4)0.0557 (5)0.0608 (12)
H20.23150.02280.12090.073*
N30.3626 (3)0.0815 (4)0.0651 (5)0.0738 (11)
C40.3924 (3)0.1682 (3)0.0325 (15)0.0569 (11)
C50.3127 (4)0.2042 (3)0.1335 (5)0.0549 (11)
H50.33290.26140.20180.066*
C60.2050 (4)0.1559 (4)0.1332 (5)0.0589 (11)
H60.15060.18260.20170.071*
C70.5139 (4)0.2197 (4)0.0248 (10)0.0805 (15)
H7A0.55690.18330.05340.121*
H7B0.55460.20550.11480.121*
H7C0.50850.30340.00800.121*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru0.0442 (2)0.0442 (2)0.0487 (3)0.0000.0000.000
Cl10.069 (2)0.069 (2)0.049 (3)0.0000.0000.000
Cl20.066 (2)0.066 (2)0.053 (3)0.0000.0000.000
N10.0470 (15)0.0466 (14)0.0557 (15)0.0008 (11)0.007 (5)0.000 (5)
C20.048 (2)0.063 (3)0.071 (3)0.0005 (19)0.001 (2)0.011 (2)
N30.056 (2)0.077 (3)0.088 (3)0.0004 (18)0.004 (2)0.005 (2)
C40.0551 (19)0.0463 (18)0.069 (3)0.0036 (14)0.004 (4)0.001 (5)
C50.055 (3)0.048 (2)0.062 (3)0.0088 (19)0.007 (2)0.0125 (19)
C60.061 (3)0.053 (3)0.062 (3)0.0004 (19)0.003 (2)0.006 (2)
C70.059 (2)0.083 (3)0.100 (5)0.0124 (19)0.001 (4)0.012 (4)
Geometric parameters (Å, º) top
Ru—N1i2.082 (2)N3—C41.371 (10)
Ru—N1ii2.082 (2)C4—C51.356 (11)
Ru—N12.082 (2)C4—C71.492 (5)
Ru—N1iii2.082 (2)C5—C61.333 (5)
Ru—Cl12.398 (4)C5—H50.9300
Ru—Cl22.400 (4)C6—H60.9300
N1—C21.337 (6)C7—H7A0.9600
N1—C61.343 (7)C7—H7B0.9600
C2—N31.349 (5)C7—H7C0.9600
C2—H20.9300
N1i—Ru—N1ii179.2 (4)N1—C2—H2117.5
N1i—Ru—N189.997 (3)N3—C2—H2117.5
N1ii—Ru—N189.997 (3)C2—N3—C4117.0 (4)
N1i—Ru—N1iii89.997 (3)C5—C4—N3120.0 (3)
N1ii—Ru—N1iii89.997 (3)C5—C4—C7121.8 (7)
N1—Ru—N1iii179.2 (4)N3—C4—C7118.3 (8)
N1i—Ru—Cl190.4 (2)C6—C5—C4118.8 (4)
N1ii—Ru—Cl190.4 (2)C6—C5—H5120.6
N1—Ru—Cl190.4 (2)C4—C5—H5120.6
N1iii—Ru—Cl190.4 (2)C5—C6—N1124.1 (4)
N1i—Ru—Cl289.6 (2)C5—C6—H6117.9
N1ii—Ru—Cl289.6 (2)N1—C6—H6117.9
N1—Ru—Cl289.6 (2)C4—C7—H7A109.5
N1iii—Ru—Cl289.6 (2)C4—C7—H7B109.5
Cl1—Ru—Cl2180.0H7A—C7—H7B109.5
C2—N1—C6115.1 (3)C4—C7—H7C109.5
C2—N1—Ru122.1 (4)H7A—C7—H7C109.5
C6—N1—Ru122.8 (4)H7B—C7—H7C109.5
N1—C2—N3125.0 (4)
Symmetry codes: (i) y, x, z; (ii) y, x, z; (iii) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl20.932.783.247 (5)112
C6—H6···Cl10.932.833.300 (5)113
C7—H7C···Cl1iv0.962.923.772 (6)149
Symmetry code: (iv) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[RuCl2(C5H6N2)4]
Mr548.44
Crystal system, space groupTetragonal, I4
Temperature (K)293
a, c (Å)11.295 (1), 9.200 (1)
V3)1173.7 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.92
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionEmpirical (using intensity measurements) via ψ scan
(North et al., 1968)
Tmin, Tmax0.872, 0.912
No. of measured, independent and
observed [I > 2σ(I)] reflections
2354, 990, 898
Rint0.028
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.059, 1.05
No. of reflections990
No. of parameters73
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.17
Absolute structureFlack, 1983
Absolute structure parameter0.19 (5)

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997a), ORTEP-32/ORTEPIII (Farrugia, 1998), CIFTAB (Sheldrick, 1997b).

Selected geometric parameters (Å, º) top
Ru—N12.082 (2)C2—N31.349 (5)
Ru—Cl12.398 (4)N3—C41.371 (10)
Ru—Cl22.400 (4)C4—C51.356 (11)
N1—C21.337 (6)C4—C71.492 (5)
N1—C61.343 (7)C5—C61.333 (5)
N1i—Ru—N189.997 (3)N1—C2—N3125.0 (4)
N1—Ru—N1ii179.2 (4)C2—N3—C4117.0 (4)
N1—Ru—Cl190.4 (2)C5—C4—N3120.0 (3)
N1—Ru—Cl289.6 (2)C5—C4—C7121.8 (7)
Cl1—Ru—Cl2180.0N3—C4—C7118.3 (8)
C2—N1—C6115.1 (3)C6—C5—C4118.8 (4)
C2—N1—Ru122.1 (4)C5—C6—N1124.1 (4)
C6—N1—Ru122.8 (4)
Symmetry codes: (i) y, x, z; (ii) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl20.932.783.247 (5)112
C6—H6···Cl10.932.833.300 (5)113
C7—H7C···Cl1iii0.962.923.772 (6)149
Symmetry code: (iii) x1/2, y+1/2, z+1/2.
 

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