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The potentially cytostatic title compound, mer-[RuCl3(C3H3NS)3], is the first RuIII-thz (thz is 1,3-thia­zole) complex characterized via X-ray diffraction and consists of discrete complex mol­ecules with an octahedral coordination sphere in which the metal centre is linked to three chloride ions and to three thz ligands through the N atoms. The Ru-Cl and Ru-N bond distances average 2.3462 (6) and 2.0851 (19) Å, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012191/qa0327sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012191/qa0327Isup2.hkl
Contains datablock I

CCDC reference: 152655

Comment top

On continuing our research efforts to prepare and structurally characterize complexes of platinum group metals of potential cytostatic and antitumoral activity (Cini et al., 1998; Pifferi & Cini, 1998; Cavaglioni & Cini, 1997; Cini, 1996), we have carried out the synthesis and the X-ray structural characterization of the title compound, (I), from the reaction of K3RuCl6 with thz (thz is 1,3-thiazole) in methanol. It is interesting to note that the thz group is frequently encountered in several biomolecules and active drugs (Hansch et al., 1990), and that other workers found that thz–metal complexes posses cytostatic activity (Van Beusichem & Farrell, 1992). Furthermore, several RuII and RuIII complexes have shown cytostatic and antitumoral activity (Clarke & Stubbs, 1996). The crystals of the title compound contain octahedral molecules in which the metal atom is linked to three chloride anions (meridional positions) and to three thz molecules through their N atoms. The S atoms do not have any significant contact distance to the metal. The Ru—Cl bond distances have the same values within three times the estimated standard uncertainty and are in the range 2.3446 (6)—2.3491 (6) Å, in agreement with previously published RuIII—Cl bond lengths (Ziegler et al., 1999). The Ru—N bond distances also are equal within three times the e.s.d. and are in the range 2.0826 (19)–2.0889 (18) Å; they are very close to the RuII–N(thz trans to thz) bond distances [average 2.094 (5) Å] previously found for trans-[RuCl2(PPh3)(thz)3] (Pifferi & Cini, 1998). The bond angles at the metal centre have almost idealized values; the largest deviations from 90 and 180° were found for Cl1—Ru—Cl2 [92.93 (3)°] and Cl1—Ru—Cl3 [175.47 (2)°]. All the three thz ligands are affected by a statistical disorder (see Experimental) and have a planar arrangement of the atoms. The type of disorder found in the present work has been reported previously for several metal–N(thz) complexes (Pifferi & Cini, 1998; Cavaglioni & Cini, 1997; Cornia et al., 1997; James et al., 1997); by contrast, a similar disorder for N1-coordinated imidazole (imz, a frequently encountered and biologically significant ligand) is rarely reported in the literature (see, for instance, Hu et al., 1997).

The molecule of the title compound is stabilized by eight intramolecular C—H···Cl interactions. Two C—H groups from trans thz(1) and thz(3) ligands interact with two Cl atoms each and have the shortest C···Cl distances (range 3.217–3.296 Å). The smallest C—N—Ru—Cl torsion angles for thz(1) and thz(3) are 27.6 (2) and 38.2 (2)° (absolute values), respectively, in agreement with the strongest interactions. The smallest C—N—Ru—Cl torsion angle for thz(2) is 51.3 (2)°. This means that the thz(2) system, which is closer to the Ru—N1/N3 vectors than to the Ru—Cl1/Cl3 ones, must experience a repulsive net effect from thz(1) and thz(3). The orientation of thz(2) can have a rationale through the intermolecular interactions to Cl2(-x + 0.5, y + 0.5, −z + 0.5) and Cl2(x + 0.5, −y + 0.5, z + 0.5), as well as through the stacking interactions to thz(3)(-x + 0.5, y + 0.5, −z + 0.5). It has to be noted that the unconventional M—Cl···H—C bonding mode may play a structural role for M—C bond-formation reactions (Huang et al., 1998; Cavaglioni & Cini, 1997), and for stabilizing electronically and coordinatively unsaturated organometallic and coordination compounds (Cini & Cavaglioni, 1999).

In conclusion, we have prepared and structurally characterized a new RuII complex that can exert some cytostatic activity via metal–nucleic acid interactions once the labile chloride ligands have been removed inside the cell. Furthermore, the analysis confirms that M—Cl···H—C-type interactions have a significant structural role in coordination compounds. Finally, the work says that twofold type disorders around the M–N(thz) vectors [and possibly around the M—N(imz) vectors] are highly probable. This indicates that very accurate structural determinations have to be performed in order to treat such a type of disorder for M–imz complexes, because the small geometrical and electronic differences between the CH and NH functions, when compared to those between the CH and S ones.

Experimental top

A suspension of K3RuCl6 (150 mg, 0.35 mmol) in MeOH (10 ml) was added to excess thiazole (350 mg, 4.1 mmol) and refluxed for 2 h. The mixture was cooled to 298 K and filtered. The filtrate (green) was concentrated by evaporating the solvent (298 K) and then stored at 278 K. Red crystals formed within 3–5 weeks. They were filtered off and stored in the air.

Refinement top

The three thz ligands are affected by statistical disorder around the Ru—N vectors with two distinct orientations each (pseudo-twofold type). The occupancies of the sets of atoms for the two orientations were refined to 0.609 (4)/0.391 (4), 0.581 (4)/0.419 (4) and 0.522 (4)/0.478 (4) for thz(1), thz(2), and thz(3), respectively. The C—S and C—C bond distances were restrained to be 1.70±0.02 and 1.36±0.01 Å, respectively. All the H atoms were set in calculated positions and allowed to ride on the respective C atoms during refinement. They were considered isotropic and their displacement parameters were restrained to 1.2Ueq of the atoms to which they are bound.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Johnson & Burnett, 1998); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).

mer-trichlorotris(thiazole)ruthenium(III) top
Crystal data top
C9H9Cl3N3RuS3F(000) = 908
Mr = 462.79Dx = 1.978 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.446 (1) ÅCell parameters from 33 reflections
b = 11.486 (1) Åθ = 7.5–20.0°
c = 14.342 (1) ŵ = 1.92 mm1
β = 93.14 (1)°T = 293 K
V = 1553.7 (2) Å3Prism, dark red
Z = 40.3 × 0.2 × 0.2 mm
Data collection top
Siemens P4
diffractometer
3111 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.013
Graphite monochromatorθmax = 27.5°, θmin = 2.3°
ω scansh = 112
Absorption correction: ψ scan (north, Phillips & Mathews, 1968)
?
k = 114
Tmin = 0.647, Tmax = 0.682l = 1818
4609 measured reflections3 standard reflections every 97 reflections
3564 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055H-atom parameters constrained
S = 1.01Calculated w = 1/[σ2(Fo2) + (0.0274P)2 + 0.8664P]
where P = (Fo2 + 2Fc2)/3
3564 reflections(Δ/σ)max = 0.001
235 parametersΔρmax = 0.34 e Å3
18 restraintsΔρmin = 0.46 e Å3
Crystal data top
C9H9Cl3N3RuS3V = 1553.7 (2) Å3
Mr = 462.79Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.446 (1) ŵ = 1.92 mm1
b = 11.486 (1) ÅT = 293 K
c = 14.342 (1) Å0.3 × 0.2 × 0.2 mm
β = 93.14 (1)°
Data collection top
Siemens P4
diffractometer
3111 reflections with I > 2σ(I)
Absorption correction: ψ scan (north, Phillips & Mathews, 1968)
?
Rint = 0.013
Tmin = 0.647, Tmax = 0.6823 standard reflections every 97 reflections
4609 measured reflections intensity decay: none
3564 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02318 restraints
wR(F2) = 0.055H-atom parameters constrained
S = 1.01Δρmax = 0.34 e Å3
3564 reflectionsΔρmin = 0.46 e Å3
235 parameters
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. 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*/UeqOcc. (<1)
Ru0.021766 (19)0.093457 (15)0.253768 (11)0.03161 (6)
Cl10.07192 (7)0.08113 (5)0.33377 (4)0.04742 (15)
Cl20.10548 (7)0.00144 (6)0.13108 (4)0.05125 (16)
Cl30.01480 (7)0.27537 (5)0.18156 (5)0.04971 (15)
N10.1666 (2)0.11056 (18)0.32163 (14)0.0398 (4)
N20.13125 (19)0.18154 (17)0.36286 (12)0.0349 (4)
N30.2096 (2)0.07691 (17)0.18534 (13)0.0386 (4)
S10.3869 (4)0.0549 (3)0.4065 (3)0.0711 (11)0.607 (4)
S1B0.3779 (6)0.1998 (4)0.3946 (4)0.0648 (10)0.393 (4)
C410.3417 (12)0.1958 (9)0.3966 (11)0.101 (6)0.607 (4)
H410.39020.25640.42360.122*0.607 (4)
C41B0.3689 (15)0.0515 (9)0.3854 (15)0.047 (3)0.393 (4)
H41B0.43810.00010.40370.057*0.393 (4)
C520.2371 (3)0.2582 (2)0.35269 (16)0.0406 (5)
H520.27230.27770.29540.049*
C530.3326 (3)0.0373 (3)0.22302 (18)0.0492 (6)
H530.34550.00660.28290.059*
C210.2439 (3)0.0200 (2)0.34699 (19)0.0497 (6)
H210.22070.05650.33290.060*
C510.2263 (3)0.2117 (3)0.3449 (2)0.0575 (7)
H510.19280.28430.32770.069*
C230.2225 (3)0.1104 (3)0.09660 (19)0.0551 (7)
H230.14570.13990.06070.066*
C220.1016 (3)0.1717 (2)0.45278 (16)0.0432 (5)
H220.03120.12210.47230.052*
S20.1984 (2)0.2533 (3)0.5269 (2)0.0477 (5)0.581 (4)
S2B0.3066 (6)0.3187 (6)0.4484 (3)0.0461 (7)0.419 (4)
S30.3781 (3)0.0973 (5)0.0546 (3)0.0606 (7)0.522 (4)
S3B0.4694 (5)0.0345 (7)0.1556 (3)0.0643 (9)0.478 (4)
C430.4374 (12)0.0482 (19)0.1609 (8)0.064 (4)0.522 (4)
H430.53200.03030.17590.077*0.522 (4)
C43B0.3614 (11)0.099 (2)0.0742 (9)0.075 (6)0.478 (4)
H43B0.39360.12600.01780.090*0.478 (4)
C420.2867 (17)0.3038 (15)0.4355 (6)0.056 (4)0.581 (4)
H420.36100.35690.44140.067*0.581 (4)
C42B0.1961 (16)0.2340 (15)0.5086 (8)0.066 (6)0.419 (4)
H42B0.19940.23040.57340.079*0.419 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru0.03553 (10)0.02971 (9)0.02953 (9)0.00194 (7)0.00138 (6)0.00023 (7)
Cl10.0554 (4)0.0383 (3)0.0497 (3)0.0097 (3)0.0134 (3)0.0120 (3)
Cl20.0613 (4)0.0498 (4)0.0416 (3)0.0069 (3)0.0058 (3)0.0091 (3)
Cl30.0596 (4)0.0365 (3)0.0516 (3)0.0034 (3)0.0099 (3)0.0086 (3)
N10.0334 (10)0.0403 (11)0.0456 (11)0.0009 (8)0.0016 (8)0.0072 (9)
N20.0353 (9)0.0366 (10)0.0330 (9)0.0016 (8)0.0019 (7)0.0008 (8)
N30.0441 (11)0.0388 (11)0.0334 (9)0.0000 (8)0.0063 (8)0.0007 (8)
S10.0464 (9)0.0913 (16)0.078 (2)0.0080 (9)0.0227 (10)0.0145 (11)
S1B0.045 (2)0.0641 (18)0.087 (2)0.0011 (12)0.0195 (13)0.0262 (14)
C410.053 (8)0.088 (7)0.164 (11)0.014 (5)0.014 (6)0.073 (7)
C41B0.055 (8)0.035 (4)0.054 (8)0.020 (4)0.016 (5)0.017 (4)
C520.0414 (12)0.0394 (13)0.0414 (13)0.0014 (10)0.0062 (10)0.0002 (10)
C530.0447 (14)0.0594 (17)0.0441 (13)0.0056 (12)0.0061 (11)0.0029 (12)
C210.0474 (14)0.0437 (14)0.0588 (16)0.0007 (12)0.0108 (12)0.0029 (12)
C510.0464 (15)0.0433 (15)0.083 (2)0.0019 (12)0.0095 (14)0.0173 (14)
C230.0652 (18)0.0608 (18)0.0399 (13)0.0017 (14)0.0097 (12)0.0081 (12)
C220.0432 (13)0.0512 (15)0.0354 (12)0.0014 (11)0.0043 (10)0.0014 (11)
S20.0462 (9)0.0616 (12)0.0345 (9)0.0012 (7)0.0046 (6)0.0089 (10)
S2B0.0423 (15)0.0509 (18)0.0448 (11)0.0064 (11)0.0012 (10)0.0083 (11)
S30.0565 (10)0.0812 (15)0.0464 (14)0.0062 (10)0.0241 (10)0.0020 (12)
S3B0.0456 (17)0.086 (2)0.0633 (14)0.0046 (13)0.0209 (10)0.0037 (13)
C430.040 (6)0.080 (7)0.073 (7)0.003 (6)0.006 (4)0.016 (5)
C43B0.096 (10)0.090 (8)0.044 (7)0.014 (6)0.047 (5)0.001 (5)
C420.041 (5)0.045 (5)0.081 (8)0.007 (3)0.005 (4)0.015 (4)
C42B0.098 (11)0.067 (9)0.031 (6)0.007 (6)0.004 (5)0.016 (5)
Geometric parameters (Å, º) top
Ru—N32.0826 (19)C52—S2B1.644 (5)
Ru—N12.0837 (19)C52—H520.9300
Ru—N22.0890 (18)C53—C431.374 (9)
Ru—Cl22.3446 (6)C53—S3B1.656 (5)
Ru—Cl12.3458 (6)C53—H530.9300
Ru—Cl32.3491 (6)C21—H210.9300
N1—C211.333 (3)C51—H510.9300
N1—C511.341 (3)C23—C43B1.375 (9)
N2—C221.339 (3)C23—S31.626 (4)
N2—C521.346 (3)C23—H230.9300
N3—C531.334 (3)C22—C42B1.368 (9)
N3—C231.341 (3)C22—S21.655 (4)
S1—C411.681 (9)C22—H220.9300
S1—C211.686 (4)S2—C421.694 (9)
S1B—C511.640 (5)S2B—C42B1.697 (9)
S1B—C41B1.711 (9)S3—C431.692 (9)
C41—C511.364 (8)S3B—C43B1.681 (9)
C41—H410.9300C43—H430.9300
C41B—C211.379 (9)C43B—H43B0.9300
C41B—H41B0.9300C42—H420.9300
C52—C421.358 (8)C42B—H42B0.9300
N3—Ru—N1179.69 (8)N3—C53—H53124.8
N3—Ru—N289.86 (7)C43—C53—H53124.8
N1—Ru—N290.28 (7)S3B—C53—H53117.7
N3—Ru—Cl291.08 (6)N1—C21—C41B113.5 (5)
N1—Ru—Cl288.77 (6)N1—C21—S1114.7 (2)
N2—Ru—Cl2178.50 (5)C41B—C21—S16.9 (12)
N3—Ru—Cl189.89 (6)N1—C21—H21122.6
N1—Ru—Cl190.40 (6)C41B—C21—H21123.5
N2—Ru—Cl188.24 (5)S1—C21—H21122.6
Cl2—Ru—Cl192.93 (3)N1—C51—C41112.2 (5)
N3—Ru—Cl388.96 (6)N1—C51—S1B115.1 (3)
N1—Ru—Cl390.77 (6)C41—C51—S1B7.9 (9)
N2—Ru—Cl387.37 (5)N1—C51—H51123.9
Cl2—Ru—Cl391.47 (2)C41—C51—H51123.9
Cl1—Ru—Cl3175.47 (2)S1B—C51—H51120.5
C21—N1—C51111.4 (2)N3—C23—C43B109.5 (5)
C21—N1—Ru123.25 (17)N3—C23—S3117.1 (3)
C51—N1—Ru125.38 (18)C43B—C23—S38.2 (6)
C22—N2—C52110.8 (2)N3—C23—H23121.4
C22—N2—Ru124.00 (16)C43B—C23—H23129.0
C52—N2—Ru125.16 (15)S3—C23—H23121.4
C53—N3—C23111.1 (2)N2—C22—C42B110.8 (5)
C53—N3—Ru125.84 (16)N2—C22—S2115.7 (2)
C23—N3—Ru123.01 (18)C42B—C22—S27.2 (8)
C41—S1—C2188.4 (4)N2—C22—H22122.2
C51—S1B—C41B90.1 (4)C42B—C22—H22126.8
C51—C41—S1112.9 (7)S2—C22—H22122.2
C51—C41—H41123.5C22—S2—C4288.6 (4)
C21—C41B—S1B109.8 (7)C52—S2B—C42B87.3 (4)
C21—C41B—H41B125.1C23—S3—C4387.6 (4)
S1B—C41B—H41B125.1C53—S3B—C43B86.2 (4)
N2—C52—C42112.3 (5)C53—C43—S3113.6 (7)
N2—C52—S2B116.8 (2)C53—C43—H43123.2
C42—C52—S2B4.5 (5)C23—C43B—S3B115.4 (7)
N2—C52—H52123.8C23—C43B—H43B122.3
C42—C52—H52123.8C52—C42—S2112.6 (7)
S2B—C52—H52119.4C52—C42—H42123.7
N3—C53—C43110.4 (5)C22—C42B—S2B113.7 (8)
N3—C53—S3B117.4 (2)C22—C42B—H42B123.1
C43—C53—S3B8.0 (8)

Experimental details

Crystal data
Chemical formulaC9H9Cl3N3RuS3
Mr462.79
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)9.446 (1), 11.486 (1), 14.342 (1)
β (°) 93.14 (1)
V3)1553.7 (2)
Z4
Radiation typeMo Kα
µ (mm1)1.92
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionψ scan (North, Phillips & Mathews, 1968)
Tmin, Tmax0.647, 0.682
No. of measured, independent and
observed [I > 2σ(I)] reflections
4609, 3564, 3111
Rint0.013
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.055, 1.01
No. of reflections3564
No. of parameters235
No. of restraints18
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.46

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Johnson & Burnett, 1998), CIFTAB (Sheldrick, 1997).

Selected geometric parameters (Å, º) top
Ru—N32.0826 (19)N1—C211.333 (3)
Ru—N12.0837 (19)N1—C511.341 (3)
Ru—N22.0890 (18)N2—C221.339 (3)
Ru—Cl22.3446 (6)N2—C521.346 (3)
Ru—Cl12.3458 (6)N3—C531.334 (3)
Ru—Cl32.3491 (6)N3—C231.341 (3)
N3—Ru—N1179.69 (8)N2—Ru—Cl387.37 (5)
N3—Ru—N289.86 (7)Cl2—Ru—Cl391.47 (2)
N1—Ru—N290.28 (7)Cl1—Ru—Cl3175.47 (2)
N3—Ru—Cl291.08 (6)C21—N1—C51111.4 (2)
N1—Ru—Cl288.77 (6)C21—N1—Ru123.25 (17)
N2—Ru—Cl2178.50 (5)C51—N1—Ru125.38 (18)
N3—Ru—Cl189.89 (6)C22—N2—C52110.8 (2)
N1—Ru—Cl190.40 (6)C22—N2—Ru124.00 (16)
N2—Ru—Cl188.24 (5)C52—N2—Ru125.16 (15)
Cl2—Ru—Cl192.93 (3)C53—N3—C23111.1 (2)
N3—Ru—Cl388.96 (6)C53—N3—Ru125.84 (16)
N1—Ru—Cl390.77 (6)C23—N3—Ru123.01 (18)
 

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