112
J. Schroer et al. / Polyhedron 34 (2012) 108–113
Table 4
X-ray structure data collection and refinement parameters.
[RuCl2(PPh3)(H2L1)(CH3CN)]ꢁCHCl3
[(H2L1)(PPh3)Ru(
l
-Cl)2Ru(PPh3)(H2L1)]ꢁ0.5CH2Cl2
[RuCl2(H2L1)2]
[RuCl2(dmso)2(H2L1)]ꢁCH2Cl2
Formula
Mw
Crystal system
a (Å)
b (Å)
c (Å)
C40H37Cl5N2P2Ru
885.98
monoclinic
10.393(1)
22.807(2)
17.106(1)
90
93.72(1)
90
4046.1(6)
P21/n
C74.5H67Cl5N2P4Ru2
1493.57
triclinic
13.285(2)
14.175(2)
C38H36Cl2N2P2Ru
754.60
monoclinic
20.698(2)
16.289(1)
10.213(1)
90
103.57(1)
90
3347.2(5)
P21/c
C24H32Cl4NO2PRuS2
704.51
triclinic
9.205(2)
13.615(3)
14.031(3)
61.31(2)
84.53(2)
87.41(2)
18.120(2)
a
(°)
103.830(10)
91.230(10
95.860(10)
3292.3(8)
b (°)
c
(°)
V (Å3)
1535.5(6)
ꢀ
ꢀ
Space group
P1
P1
Z
4
2
4
2
Dcalc (g cmꢀ3
)
1.454
0.828
19078
7017
453
0.0683, 0.1116
0.893
1.507
0.805
1.497
0.755
18439
7221
407
0.0536, 0.1416
0.892
1.524
1.069
16451
8080
339
0.0591, 0.1530
0.833
l
(mmꢀ1
)
Number of reflections
Number of independent
Number of parameters
R1, wR2
25383
12767
802
0.0790, 0.1254
0.860
GOF
The color of the solution turned to orange-brown and a pink solid
precipitated. The complex was filtered off and washed with diethyl
ether. The product is almost insoluble in all common solvents.
Thus, red single crystals for X-ray diffraction were produced by
slow diffusion of a solution of H2L1 in diethyl ether into a saturated
CHCl3 solution of [RuCl2(PPh3)3]. Yield: 43 mg (59%). Anal.Calc. for
Anal. Calc. for C23H30Cl2NP2S2Ru: C, 44.59; H, 4.88; N, 2.26; S,
10.35. Found: C, 44.21; H, 3.51; N, 2.20; S, 10.75%. IR(
max, cmꢀ1):
3240 (m), 3190 (m), 3109 (st), 3058 (m), 3004 (m), 2916 (w), 1608
(m), 1581 (m), 1496 (m), 1458 (m), 1434 (st), 1404 (m), 1307 (w),
1137 (m), 1114 (st), 1087 (st), 1022 (m), 968 (m), 910 (m), 871
(m), 837 (m), 767 (st), 744 (m), 698 (st), 516 (st), 428 (m).
m
C
74H66Cl4N2P4Ru2: C, 60.25; H, 4.58; N, 1.93. Found: C, 59.87; H,
2.92; N, 1.77%. IR(
m
max, cmꢀ1): 3317 (w), 3224 (w), 3051 (st),
3.5. X-ray structure determinations
2958 (w), 2916 (w), 1562 (m), 1481 (m), 1434 (st), 1188 (w),
1157 (w), 1087 (m), 1034 (m), 871 (m), 841 (m), 744 (st), 694
The intensities for the X-ray determinations were collected on a
STOE IPDS automated single crystal diffractometer with Mo Ka radi-
(st), 524 (st), 501 (m) cmꢀ1
.
ation at 200(2) K. The structures were solved by direct
([RuCl2(PPh3)(H2L1)(CH3CN)],[RuCl2(H2L1)2], [RuCl2(dmso)2(H2L1)])
3.3. [RuCl2(H2L1)2]
and Patterson methods ([(H2L1)(PPh3)Ru( -Cl)2Ru(PPh3)(H2L1)])
l
H2L1 (60 mg, 0.2 mmol) was dissolved in 10 mL of degassed
CH2Cl2 under an atmosphere of dry argon. [RuCl2(PPh3)3] (100 mg,
0.1 mmol) was added to the colorless solution. The color changed
within a few minutes to red. The reaction was heated under reflux
for 4 h, which resulted in another color change and a sparingly sol-
uble, yellow solid precipitated from the resulting yellow solution,
which was filtered off and washed with diethyl ether. Single crystals
for X-ray diffraction were obtained by a slow diffusion of H2L1
(60 mg, 0.2 mmol) into a saturated CHCl3 solution of [RuCl2(PPh3)3].
The initially formed red crystals redissolve within a few weeks and
finally only clear yellow single-crystals of [RuCl2(H2L1)2] were ob-
tained. Yield: 35 mg (46 mg). Anal. Calc. for C38H36Cl2N2P2Ru: C,
using SHELXS-97 [21]. Subsequent Fourier difference map analyses
yielded the position of the non-hydrogen atoms. Refinement was
performed using SHELXL-97 [21]. Hydrogen atom positions were
calculated for idealized positions and treated with the ‘riding model’
option of SHELXL. Crystal data and more details of the data collections
and refinements are contained in Table 4.
Acknowledgement
We gratefully acknowledge support fron DAAD (Germany) and
CAPES (Brazil).
60.48; H, 4.81; N, 3.71. Found: C, 59.97; H, 3.76; N, 3.34%. IR(mmax
,
Appendix A. Supplementary data
cmꢀ1): 3283 (m), 3232 (w), 3133 (w), 3056 (w), 2946 (w), 2905
(w), 1613 (w), 1574 (m), 1496 (m), 1456 (m), 1433 m), 1309 (w),
1262 (w), 1243 (m), 1220 (w), 1187 (w), 1091 (st), 1073 (m), 1048
(m), 1027 (st), 921 (w), 865 (m), 830 (st), 756 (st), 745 (m), 736
(st), 691 (st), 616 (m), 595 (st), 562 (m). 1H NMR (dmso-d6, d,
ppm): 3.78 (m, 4H, PCH2), 6.68 (m, 2H, CHarom), 6.85 (m, 10H, CHar-
om), 6.90–7.12 ppm (m, 16H, CHarom). 31P NMR (dmso, d): 64.17 ppm.
+ESI-MS: 720 [MꢀCl]+, 797 [MꢀCl+dmso]+. High resolution MS of
the ion [MꢀCl]+ calcd: 719.1086, found: 719.1069.
CCDC 842635, 842636, 842637 and 842636 contain the supple-
mentary crystallographic data for [RuCl2(PPh3)(H2L1)(CH3CN)],
[(H2L1)(PPh3)Ru( -Cl)2Ru(PPh3)(H2L1)], [RuCl2(H2L1)2] and [RuCl2
l
(dmso)2(H2L1)], respectively. These data can be obtained free of
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
3.4. [RuCl2(dmso)2(H2L1)]
References
[1] (a) D.B. Watson (Ed.), Ruthenium, Properties, Production and Applications,
Nova Science Publishers Inc., Hauppauge, NY, 2011;
[RuCl2(dmso)4] (50 mg, 0.1 mmol) was dissolved in 10 mL of
degassed CH2Cl2 and H2L1 (30 mg, 0.11 mmol) was added. The
solution was stirred for 4 h at room temperature. During this time,
a pale yellow solid precipitated. Yield: 34 mg (48%). Single crystals
of the almost insoluble compound for X-ray diffraction were ob-
tained by the method described for [RuCl2(PPh3)(H2L1)(CH3CN)].
(b) T. Kondo, Bull. Chem. Soc. Jpn. 84 (2011) 441;
(c) P.H. Dixneuf, Nat. Chem. 3 (2011) 578.
[2] I. Bratsos, T. Gianferrara, E. Alessio, C.G. Hartinger, M.A. Jakupec, B.K. Keppler,
Ruthenium and other non-platinum anticancer compounds, in: E. Alessio (Ed.),
Bioinorganic Medicinal Chemistry, Wiley VCH, Weinheim, 2011.
[3] P.J. Dyson, Chimia 61 (2007) 698.