Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101018091/na1542sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101018091/na1542Isup2.hkl |
CCDC reference: 180146
[Ru(N,N-dps)2(N,S-dps)][PF6]2.H2O was prepared according to the method of Scopelliti et al. (2001). All other chemicals were reagent grade. An acetone-acetonitrile (1:1) solution (5 ml) of Ru(N,N-dps)2(N,S-dps)][PF6]2.H2O (48.68 mg, 0.05 mmol) was introduced into a test-tube and 0.1 ml of an aqueous solution of HBF4 (7.65M) added. Di-isopropyl ether (8 ml) was layered on top of the reaction mixture and the test tube was closed with parafilm. After 20 d colourless crystals were isolated and found to be suitable for X-ray structure investigation. The analysis of C24H24B2F8N6ORuS2 gave C 38.37 versus 38.40, H 3.22 versus 3.35, N 11.19 versus 11.10 and S 8.53 versus 8.50% for the calculated and found composition, respectively.
Reflection intensities were evaluated by profile fitting of a 96-steps peak scan among 2θ shells procedure (Diamond, 1969). H atoms were located in idealized positions and allowed to ride on their parent C atoms with isotropic displacement parameters related to the refined values of their corresponding parent atoms. In the last refinement cycles the water-H atoms were fixed in the idealized positions located by HYDROGEN (Nardelli, 1999). Both [BF4]- anions appear to be affected by the usual rotational disorder and one tetrahedral moiety was split in two orientations.
Data collection: XSCANS (Bruker,1999); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS90 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (SHELXTL; Siemens, 1996); software used to prepare material for publication: PARST97 (Nardelli, 1995) and SHELXL97.
[Ru(C2H3N)2(C10H8N2S)2].2(BF4).H2O | Z = 2 |
Mr = 751.30 | F(000) = 752 |
Triclinic, P1 | Dx = 1.627 Mg m−3 |
a = 10.0709 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.6595 (8) Å | Cell parameters from 37 reflections |
c = 13.547 (1) Å | θ = 8.2–16.0° |
α = 77.016 (7)° | µ = 0.73 mm−1 |
β = 75.004 (6)° | T = 298 K |
γ = 68.225 (6)° | Prysmatic, pale yellow |
V = 1533.3 (2) Å3 | 0.36 × 0.30 × 0.25 mm |
Siemens P4 diffractometer | 4761 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 26.0°, θmin = 1.6° |
2θ/ω scans | h = −11→1 |
Absorption correction: numerical by seven indexed faces (XPREPW in SHELXTL; Siemens, 1996) | k = −14→14 |
Tmin = 0.689, Tmax = 0.826 | l = −16→16 |
7496 measured reflections | 3 standard reflections every 197 reflections |
5922 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.9658P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.051 |
5922 reflections | Δρmax = 0.53 e Å−3 |
440 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0028 (5) |
[Ru(C2H3N)2(C10H8N2S)2].2(BF4).H2O | γ = 68.225 (6)° |
Mr = 751.30 | V = 1533.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.0709 (7) Å | Mo Kα radiation |
b = 12.6595 (8) Å | µ = 0.73 mm−1 |
c = 13.547 (1) Å | T = 298 K |
α = 77.016 (7)° | 0.36 × 0.30 × 0.25 mm |
β = 75.004 (6)° |
Siemens P4 diffractometer | 4761 reflections with I > 2σ(I) |
Absorption correction: numerical by seven indexed faces (XPREPW in SHELXTL; Siemens, 1996) | Rint = 0.030 |
Tmin = 0.689, Tmax = 0.826 | 3 standard reflections every 197 reflections |
7496 measured reflections | intensity decay: none |
5922 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.53 e Å−3 |
5922 reflections | Δρmin = −0.39 e Å−3 |
440 parameters |
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. One BF4- anion appeared to be affected by rotational disorder and it was splitted into two positions (0.53/0.47 occup.). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ru1 | 0.5000 | 0.5000 | 0.0000 | 0.03497 (10) | |
N1 | 0.5978 (3) | 0.3215 (2) | 0.02163 (17) | 0.0426 (5) | |
C1 | 0.5364 (4) | 0.2561 (3) | −0.0051 (2) | 0.0516 (7) | |
H1 | 0.4501 | 0.2926 | −0.0299 | 0.062* | |
C2 | 0.5949 (5) | 0.1389 (3) | 0.0026 (3) | 0.0697 (10) | |
H2 | 0.5488 | 0.0969 | −0.0158 | 0.084* | |
C3 | 0.7239 (6) | 0.0842 (3) | 0.0382 (3) | 0.0857 (13) | |
H3 | 0.7676 | 0.0049 | 0.0421 | 0.103* | |
C4 | 0.7862 (5) | 0.1480 (3) | 0.0676 (3) | 0.0745 (11) | |
H4 | 0.8726 | 0.1124 | 0.0923 | 0.089* | |
C5 | 0.7203 (3) | 0.2664 (3) | 0.0604 (2) | 0.0519 (7) | |
S1 | 0.80545 (9) | 0.34311 (8) | 0.10157 (7) | 0.0585 (2) | |
C6 | 0.6585 (3) | 0.4328 (3) | 0.1807 (2) | 0.0484 (7) | |
C7 | 0.6782 (4) | 0.4332 (3) | 0.2783 (3) | 0.0649 (9) | |
H7 | 0.7629 | 0.3841 | 0.3011 | 0.078* | |
C8 | 0.5719 (5) | 0.5065 (4) | 0.3405 (3) | 0.0741 (11) | |
H8 | 0.5844 | 0.5096 | 0.4054 | 0.089* | |
C9 | 0.4464 (4) | 0.5756 (3) | 0.3060 (2) | 0.0643 (9) | |
H9 | 0.3721 | 0.6254 | 0.3475 | 0.077* | |
C10 | 0.4319 (4) | 0.5702 (3) | 0.2092 (2) | 0.0504 (7) | |
H10 | 0.3456 | 0.6162 | 0.1872 | 0.060* | |
N2 | 0.5367 (3) | 0.5013 (2) | 0.14480 (17) | 0.0421 (5) | |
N3 | 0.6882 (3) | 0.5266 (2) | −0.07705 (17) | 0.0415 (5) | |
C11 | 0.7904 (3) | 0.5444 (3) | −0.1224 (2) | 0.0483 (7) | |
C12 | 0.9247 (4) | 0.5660 (4) | −0.1778 (3) | 0.0775 (11) | |
H12A | 1.0048 | 0.4950 | −0.1768 | 0.116* | |
H12B | 0.9415 | 0.6186 | −0.1452 | 0.116* | |
H12C | 0.9162 | 0.5987 | −0.2480 | 0.116* | |
Ru2 | 0.5000 | 0.0000 | 0.5000 | 0.03769 (10) | |
N4 | 0.3750 (2) | 0.17193 (19) | 0.51251 (19) | 0.0443 (5) | |
C13 | 0.3093 (3) | 0.2031 (3) | 0.6071 (3) | 0.0534 (7) | |
H13 | 0.3202 | 0.1464 | 0.6644 | 0.064* | |
C14 | 0.2278 (4) | 0.3138 (3) | 0.6228 (3) | 0.0679 (9) | |
H14 | 0.1876 | 0.3315 | 0.6895 | 0.081* | |
C15 | 0.2058 (4) | 0.3979 (3) | 0.5401 (4) | 0.0739 (11) | |
H15 | 0.1504 | 0.4735 | 0.5493 | 0.089* | |
C16 | 0.2673 (4) | 0.3687 (3) | 0.4426 (3) | 0.0638 (9) | |
H16 | 0.2525 | 0.4243 | 0.3849 | 0.077* | |
C17 | 0.3515 (3) | 0.2558 (3) | 0.4313 (2) | 0.0494 (7) | |
S2 | 0.43334 (10) | 0.22457 (7) | 0.30422 (6) | 0.0581 (2) | |
C18 | 0.3829 (3) | 0.1060 (3) | 0.3008 (2) | 0.0467 (7) | |
C19 | 0.3218 (3) | 0.1116 (3) | 0.2182 (2) | 0.0565 (8) | |
H19 | 0.3059 | 0.1769 | 0.1688 | 0.068* | |
C20 | 0.2852 (4) | 0.0209 (3) | 0.2099 (3) | 0.0624 (9) | |
H20 | 0.2468 | 0.0227 | 0.1538 | 0.075* | |
C21 | 0.3057 (3) | −0.0731 (3) | 0.2857 (3) | 0.0591 (8) | |
H21 | 0.2797 | −0.1353 | 0.2825 | 0.071* | |
C22 | 0.3655 (3) | −0.0734 (3) | 0.3665 (2) | 0.0496 (7) | |
H22 | 0.3774 | −0.1365 | 0.4182 | 0.060* | |
N5 | 0.4077 (2) | 0.0133 (2) | 0.37408 (17) | 0.0432 (5) | |
N6 | 0.6772 (3) | 0.0372 (2) | 0.41339 (18) | 0.0444 (5) | |
C23 | 0.7854 (3) | 0.0495 (3) | 0.3741 (2) | 0.0500 (7) | |
C24 | 0.9247 (4) | 0.0654 (4) | 0.3237 (3) | 0.0745 (11) | |
H24A | 0.9084 | 0.1344 | 0.2746 | 0.112* | |
H24B | 0.9858 | 0.0009 | 0.2887 | 0.112* | |
H24C | 0.9715 | 0.0715 | 0.3745 | 0.112* | |
B1 | 0.0766 (5) | 0.7393 (4) | 0.5048 (3) | 0.0661 (11) | |
F1 | −0.0135 (5) | 0.8416 (3) | 0.4887 (4) | 0.197 (2) | |
F2 | 0.0894 (4) | 0.6796 (3) | 0.4248 (2) | 0.1297 (11) | |
F3 | 0.2127 (3) | 0.7381 (3) | 0.5038 (2) | 0.1249 (11) | |
F4 | 0.0336 (3) | 0.6803 (3) | 0.5939 (2) | 0.1212 (10) | |
B2 | 0.1943 (6) | 0.2454 (4) | 0.9234 (4) | 0.0747 (12) | |
F5 | 0.3217 (14) | 0.1845 (13) | 0.8897 (15) | 0.202 (7) | 0.55 (2) |
F6 | 0.2077 (16) | 0.3463 (8) | 0.8939 (13) | 0.179 (6) | 0.55 (2) |
F7 | 0.1507 (17) | 0.2074 (14) | 1.0198 (9) | 0.205 (8) | 0.55 (2) |
F8 | 0.1033 (18) | 0.2267 (18) | 0.8888 (11) | 0.166 (5) | 0.55 (2) |
F5A | 0.3007 (18) | 0.1719 (10) | 0.8596 (9) | 0.120 (5) | 0.45 (2) |
F7A | 0.208 (3) | 0.1899 (12) | 1.0168 (12) | 0.165 (8) | 0.45 (2) |
F6A | 0.1953 (13) | 0.3471 (12) | 0.9400 (18) | 0.174 (8) | 0.45 (2) |
F8A | 0.0579 (13) | 0.2803 (10) | 0.8852 (8) | 0.088 (3) | 0.45 (2) |
O | 0.9078 (5) | 0.2009 (5) | 0.7862 (3) | 0.163 (2) | |
H0A | 0.9179 | 0.2317 | 0.7215 | 0.080* | |
H0B | 0.9564 | 0.2240 | 0.8135 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.03699 (17) | 0.04050 (18) | 0.03119 (16) | −0.01942 (13) | −0.00549 (12) | −0.00249 (12) |
N1 | 0.0471 (13) | 0.0449 (13) | 0.0358 (12) | −0.0205 (11) | −0.0031 (10) | −0.0028 (10) |
C1 | 0.0625 (19) | 0.0530 (18) | 0.0444 (16) | −0.0317 (15) | 0.0029 (14) | −0.0107 (13) |
C2 | 0.093 (3) | 0.056 (2) | 0.063 (2) | −0.038 (2) | 0.007 (2) | −0.0178 (17) |
C3 | 0.118 (4) | 0.046 (2) | 0.078 (3) | −0.012 (2) | −0.013 (3) | −0.0128 (19) |
C4 | 0.087 (3) | 0.054 (2) | 0.066 (2) | 0.0001 (19) | −0.022 (2) | −0.0096 (17) |
C5 | 0.0556 (18) | 0.0513 (17) | 0.0416 (16) | −0.0131 (14) | −0.0074 (13) | −0.0031 (13) |
S1 | 0.0474 (4) | 0.0689 (5) | 0.0579 (5) | −0.0153 (4) | −0.0194 (4) | −0.0030 (4) |
C6 | 0.0551 (18) | 0.0586 (18) | 0.0404 (15) | −0.0302 (15) | −0.0152 (13) | 0.0020 (13) |
C7 | 0.074 (2) | 0.086 (3) | 0.0491 (19) | −0.041 (2) | −0.0248 (17) | 0.0007 (18) |
C8 | 0.095 (3) | 0.109 (3) | 0.0407 (18) | −0.057 (3) | −0.0163 (19) | −0.0110 (19) |
C9 | 0.082 (2) | 0.082 (2) | 0.0418 (17) | −0.045 (2) | 0.0027 (17) | −0.0197 (16) |
C10 | 0.0575 (18) | 0.0567 (18) | 0.0418 (16) | −0.0283 (15) | −0.0029 (13) | −0.0081 (13) |
N2 | 0.0474 (13) | 0.0508 (13) | 0.0354 (12) | −0.0269 (11) | −0.0068 (10) | −0.0035 (10) |
N3 | 0.0429 (13) | 0.0481 (13) | 0.0373 (12) | −0.0215 (11) | −0.0076 (10) | −0.0028 (10) |
C11 | 0.0430 (16) | 0.0508 (17) | 0.0498 (17) | −0.0196 (14) | −0.0076 (14) | 0.0009 (13) |
C12 | 0.0457 (19) | 0.087 (3) | 0.089 (3) | −0.0318 (19) | 0.0035 (18) | 0.006 (2) |
Ru2 | 0.03723 (17) | 0.03944 (18) | 0.03546 (17) | −0.01596 (13) | −0.01024 (13) | 0.00574 (12) |
N4 | 0.0431 (13) | 0.0423 (13) | 0.0479 (14) | −0.0170 (10) | −0.0128 (11) | 0.0020 (10) |
C13 | 0.0521 (18) | 0.0529 (18) | 0.0535 (18) | −0.0164 (14) | −0.0110 (14) | −0.0056 (14) |
C14 | 0.066 (2) | 0.063 (2) | 0.076 (2) | −0.0145 (17) | −0.0143 (19) | −0.0222 (19) |
C15 | 0.075 (2) | 0.0477 (19) | 0.103 (3) | −0.0145 (17) | −0.028 (2) | −0.017 (2) |
C16 | 0.072 (2) | 0.0428 (17) | 0.084 (3) | −0.0246 (16) | −0.034 (2) | 0.0086 (17) |
C17 | 0.0482 (16) | 0.0452 (16) | 0.0589 (18) | −0.0223 (13) | −0.0204 (14) | 0.0079 (13) |
S2 | 0.0660 (5) | 0.0575 (5) | 0.0493 (4) | −0.0301 (4) | −0.0166 (4) | 0.0184 (4) |
C18 | 0.0401 (15) | 0.0548 (17) | 0.0377 (14) | −0.0133 (13) | −0.0072 (12) | 0.0035 (12) |
C19 | 0.0505 (18) | 0.070 (2) | 0.0380 (16) | −0.0109 (16) | −0.0113 (13) | −0.0001 (14) |
C20 | 0.0544 (19) | 0.083 (2) | 0.0460 (18) | −0.0114 (18) | −0.0148 (15) | −0.0162 (17) |
C21 | 0.0520 (18) | 0.070 (2) | 0.062 (2) | −0.0203 (16) | −0.0140 (16) | −0.0189 (17) |
C22 | 0.0474 (16) | 0.0520 (17) | 0.0515 (17) | −0.0197 (14) | −0.0126 (13) | −0.0026 (13) |
N5 | 0.0401 (12) | 0.0495 (13) | 0.0389 (12) | −0.0172 (10) | −0.0104 (10) | 0.0027 (10) |
N6 | 0.0411 (13) | 0.0467 (13) | 0.0430 (13) | −0.0170 (11) | −0.0085 (11) | 0.0032 (10) |
C23 | 0.0447 (17) | 0.0520 (17) | 0.0493 (17) | −0.0175 (14) | −0.0123 (14) | 0.0067 (13) |
C24 | 0.0491 (19) | 0.092 (3) | 0.075 (2) | −0.0329 (19) | −0.0046 (17) | 0.012 (2) |
B1 | 0.075 (3) | 0.065 (3) | 0.062 (3) | −0.030 (2) | −0.026 (2) | 0.012 (2) |
F1 | 0.228 (5) | 0.083 (2) | 0.251 (5) | 0.019 (2) | −0.137 (4) | 0.016 (3) |
F2 | 0.139 (3) | 0.183 (3) | 0.094 (2) | −0.073 (2) | −0.0276 (19) | −0.034 (2) |
F3 | 0.114 (2) | 0.187 (3) | 0.103 (2) | −0.093 (2) | −0.0193 (18) | −0.006 (2) |
F4 | 0.132 (2) | 0.152 (3) | 0.0819 (18) | −0.080 (2) | −0.0105 (17) | 0.0233 (18) |
B2 | 0.089 (3) | 0.075 (3) | 0.068 (3) | −0.026 (3) | −0.036 (3) | −0.004 (2) |
F5 | 0.097 (6) | 0.235 (12) | 0.312 (18) | −0.032 (6) | −0.003 (8) | −0.195 (13) |
F6 | 0.266 (13) | 0.079 (6) | 0.229 (12) | −0.088 (7) | −0.133 (9) | 0.062 (7) |
F7 | 0.196 (10) | 0.192 (11) | 0.074 (6) | 0.074 (8) | −0.008 (6) | 0.020 (5) |
F8 | 0.153 (10) | 0.199 (14) | 0.198 (9) | −0.073 (9) | −0.117 (8) | −0.005 (9) |
F5A | 0.164 (11) | 0.093 (6) | 0.084 (6) | −0.034 (5) | 0.002 (5) | −0.021 (5) |
F7A | 0.31 (2) | 0.106 (7) | 0.115 (10) | −0.059 (11) | −0.158 (13) | 0.033 (6) |
F6A | 0.104 (7) | 0.126 (9) | 0.35 (2) | −0.005 (6) | −0.104 (9) | −0.132 (13) |
F8A | 0.081 (5) | 0.115 (7) | 0.079 (5) | −0.027 (4) | −0.035 (4) | −0.020 (4) |
O | 0.172 (4) | 0.290 (6) | 0.095 (3) | −0.152 (4) | −0.033 (3) | −0.020 (3) |
Ru1—N3 | 2.022 (2) | C14—C15 | 1.363 (5) |
Ru1—N1 | 2.088 (2) | C14—H14 | 0.9300 |
Ru1—N2 | 2.092 (2) | C15—C16 | 1.374 (5) |
N1—C5 | 1.348 (4) | C15—H15 | 0.9300 |
N1—C1 | 1.353 (4) | C16—C17 | 1.385 (5) |
C1—C2 | 1.369 (5) | C16—H16 | 0.9300 |
C1—H1 | 0.9300 | C17—S2 | 1.768 (3) |
C2—C3 | 1.380 (6) | S2—C18 | 1.767 (3) |
C2—H2 | 0.9300 | C18—N5 | 1.346 (3) |
C3—C4 | 1.361 (6) | C18—C19 | 1.387 (4) |
C3—H3 | 0.9300 | C19—C20 | 1.364 (5) |
C4—C5 | 1.387 (5) | C19—H19 | 0.9300 |
C4—H4 | 0.9300 | C20—C21 | 1.376 (5) |
C5—S1 | 1.761 (3) | C20—H20 | 0.9300 |
S1—C6 | 1.763 (3) | C21—C22 | 1.378 (4) |
C6—N2 | 1.351 (4) | C21—H21 | 0.9300 |
C6—C7 | 1.389 (4) | C22—N5 | 1.347 (4) |
C7—C8 | 1.365 (5) | C22—H22 | 0.9300 |
C7—H7 | 0.9300 | N6—C23 | 1.133 (4) |
C8—C9 | 1.373 (5) | C23—C24 | 1.458 (4) |
C8—H8 | 0.9300 | C24—H24A | 0.9600 |
C9—C10 | 1.375 (4) | C24—H24B | 0.9600 |
C9—H9 | 0.9300 | C24—H24C | 0.9600 |
C10—N2 | 1.348 (4) | B1—F1 | 1.285 (5) |
C10—H10 | 0.9300 | B1—F4 | 1.329 (5) |
N3—C11 | 1.127 (4) | B1—F3 | 1.362 (5) |
C11—C12 | 1.457 (4) | B1—F2 | 1.410 (5) |
C12—H12A | 0.9600 | B2—F8 | 1.245 (13) |
C12—H12B | 0.9600 | B2—F5 | 1.253 (14) |
C12—H12C | 0.9600 | B2—F6 | 1.296 (10) |
Ru2—N6 | 2.018 (2) | B2—F7 | 1.307 (14) |
Ru2—N4 | 2.091 (2) | B2—F7A | 1.317 (13) |
Ru2—N5 | 2.093 (2) | B2—F6A | 1.360 (12) |
N4—C17 | 1.348 (4) | B2—F5A | 1.380 (14) |
N4—C13 | 1.353 (4) | B2—F8A | 1.472 (13) |
C13—C14 | 1.369 (4) | O—H0A | 0.872 |
C13—H13 | 0.9300 | O—H0B | 0.843 |
N3—Ru1—N3i | 180.000 (1) | C17—N4—C13 | 116.5 (3) |
N3—Ru1—N1i | 86.79 (9) | C17—N4—Ru2 | 124.2 (2) |
N3—Ru1—N1 | 93.21 (9) | C13—N4—Ru2 | 119.30 (19) |
N1i—Ru1—N1 | 180.00 (13) | N4—C13—C14 | 123.3 (3) |
N3—Ru1—N2i | 86.25 (9) | N4—C13—H13 | 118.3 |
N1—Ru1—N2i | 91.71 (9) | C14—C13—H13 | 118.3 |
N3—Ru1—N2 | 93.75 (9) | C15—C14—C13 | 119.6 (4) |
N1—Ru1—N2 | 88.29 (9) | C15—C14—H14 | 120.2 |
N2i—Ru1—N2 | 180.0 | C13—C14—H14 | 120.2 |
C5—N1—C1 | 117.2 (3) | C14—C15—C16 | 118.7 (3) |
C5—N1—Ru1 | 124.0 (2) | C14—C15—H15 | 120.7 |
C1—N1—Ru1 | 118.8 (2) | C16—C15—H15 | 120.7 |
N1—C1—C2 | 123.2 (3) | C15—C16—C17 | 119.4 (3) |
N1—C1—H1 | 118.4 | C15—C16—H16 | 120.3 |
C2—C1—H1 | 118.4 | C17—C16—H16 | 120.3 |
C1—C2—C3 | 118.7 (4) | N4—C17—C16 | 122.6 (3) |
C1—C2—H2 | 120.6 | N4—C17—S2 | 120.1 (2) |
C3—C2—H2 | 120.6 | C16—C17—S2 | 117.3 (3) |
C4—C3—C2 | 119.1 (4) | C18—S2—C17 | 102.4 (1) |
C4—C3—H3 | 120.5 | N5—C18—C19 | 122.2 (3) |
C2—C3—H3 | 120.5 | N5—C18—S2 | 120.7 (2) |
C3—C4—C5 | 119.7 (4) | C19—C18—S2 | 117.1 (2) |
C3—C4—H4 | 120.1 | C20—C19—C18 | 119.6 (3) |
C5—C4—H4 | 120.1 | C20—C19—H19 | 120.2 |
N1—C5—C4 | 121.9 (3) | C18—C19—H19 | 120.2 |
N1—C5—S1 | 120.8 (2) | C19—C20—C21 | 119.1 (3) |
C4—C5—S1 | 117.3 (3) | C19—C20—H20 | 120.5 |
C5—S1—C6 | 102.3 (1) | C21—C20—H20 | 120.5 |
N2—C6—C7 | 122.5 (3) | C20—C21—C22 | 118.7 (3) |
N2—C6—S1 | 120.7 (2) | C20—C21—H21 | 120.7 |
C7—C6—S1 | 116.6 (3) | C22—C21—H21 | 120.7 |
C8—C7—C6 | 119.2 (3) | N5—C22—C21 | 123.2 (3) |
C8—C7—H7 | 120.4 | N5—C22—H22 | 118.4 |
C6—C7—H7 | 120.4 | C21—C22—H22 | 118.4 |
C7—C8—C9 | 119.0 (3) | C18—N5—C22 | 117.2 (3) |
C7—C8—H8 | 120.5 | C18—N5—Ru2 | 123.7 (2) |
C9—C8—H8 | 120.5 | C22—N5—Ru2 | 119.00 (19) |
C8—C9—C10 | 119.1 (3) | C23—N6—Ru2 | 171.5 (2) |
C8—C9—H9 | 120.4 | N6—C23—C24 | 179.9 (4) |
C10—C9—H9 | 120.4 | C23—C24—H24A | 109.5 |
N2—C10—C9 | 123.2 (3) | C23—C24—H24B | 109.5 |
N2—C10—H10 | 118.4 | H24A—C24—H24B | 109.5 |
C9—C10—H10 | 118.4 | C23—C24—H24C | 109.5 |
C10—N2—C6 | 116.8 (2) | H24A—C24—H24C | 109.5 |
C10—N2—Ru1 | 119.4 (2) | H24B—C24—H24C | 109.5 |
C6—N2—Ru1 | 123.8 (2) | F1—B1—F4 | 112.9 (5) |
C11—N3—Ru1 | 177.5 (2) | F1—B1—F3 | 112.6 (4) |
N3—C11—C12 | 178.0 (3) | F4—B1—F3 | 107.7 (3) |
C11—C12—H12A | 109.5 | F1—B1—F2 | 108.5 (4) |
C11—C12—H12B | 109.5 | F4—B1—F2 | 107.9 (4) |
H12A—C12—H12B | 109.5 | F3—B1—F2 | 107.0 (4) |
C11—C12—H12C | 109.5 | F8—B2—F5 | 111.4 (9) |
H12A—C12—H12C | 109.5 | F8—B2—F6 | 116.5 (9) |
H12B—C12—H12C | 109.5 | F5—B2—F6 | 99.6 (11) |
N6ii—Ru2—N6 | 180.0 | F8—B2—F7 | 96.0 (12) |
N6ii—Ru2—N4 | 85.99 (9) | F5—B2—F7 | 110.9 (10) |
N6—Ru2—N4 | 94.01 (9) | F6—B2—F7 | 122.9 (12) |
N6—Ru2—N4ii | 85.99 (9) | F7A—B2—F6A | 96.8 (11) |
N4—Ru2—N4ii | 180.00 (14) | F7A—B2—F5A | 103.5 (10) |
N6—Ru2—N5ii | 85.12 (9) | F6A—B2—F5A | 126.3 (12) |
N6—Ru2—N5 | 94.88 (9) | F7A—B2—F8A | 122.5 (12) |
N4—Ru2—N5 | 88.61 (9) | F6A—B2—F8A | 102.3 (7) |
N4ii—Ru2—N5 | 91.39 (9) | F5A—B2—F8A | 107.2 (8) |
N5ii—Ru2—N5 | 180.000 (1) | H0A—O—H0B | 106.3 |
N3—Ru1—N1—C5 | 50.6 (2) | N6ii—Ru2—N4—C17 | −125.6 (2) |
N3i—Ru1—N1—C5 | −129.4 (2) | N6—Ru2—N4—C17 | 54.4 (2) |
N2i—Ru1—N1—C5 | 137.0 (2) | N5ii—Ru2—N4—C17 | 139.6 (2) |
N2—Ru1—N1—C5 | −43.0 (2) | N5—Ru2—N4—C17 | −40.4 (2) |
N3—Ru1—N1—C1 | −128.9 (2) | N6ii—Ru2—N4—C13 | 52.8 (2) |
N3i—Ru1—N1—C1 | 51.1 (2) | N6—Ru2—N4—C13 | −127.2 (2) |
N2i—Ru1—N1—C1 | −42.6 (2) | N5ii—Ru2—N4—C13 | −42.0 (2) |
N2—Ru1—N1—C1 | 137.4 (2) | N5—Ru2—N4—C13 | 138.0 (2) |
C5—N1—C1—C2 | −2.1 (4) | C17—N4—C13—C14 | −2.7 (5) |
Ru1—N1—C1—C2 | 177.6 (2) | Ru2—N4—C13—C14 | 178.8 (3) |
N1—C1—C2—C3 | −0.7 (5) | N4—C13—C14—C15 | 2.3 (5) |
C1—C2—C3—C4 | 2.0 (6) | C13—C14—C15—C16 | −0.3 (6) |
C2—C3—C4—C5 | −0.6 (6) | C14—C15—C16—C17 | −1.1 (5) |
C1—N1—C5—C4 | 3.6 (4) | C13—N4—C17—C16 | 1.2 (4) |
Ru1—N1—C5—C4 | −176.0 (3) | Ru2—N4—C17—C16 | 179.6 (2) |
C1—N1—C5—S1 | −177.9 (2) | C13—N4—C17—S2 | 179.5 (2) |
Ru1—N1—C5—S1 | 2.5 (3) | Ru2—N4—C17—S2 | −2.0 (3) |
C3—C4—C5—N1 | −2.3 (6) | C15—C16—C17—N4 | 0.7 (5) |
C3—C4—C5—S1 | 179.1 (3) | C15—C16—C17—S2 | −177.7 (3) |
N1—C5—S1—C6 | 49.1 (3) | N4—C17—S2—C18 | 51.9 (3) |
C4—C5—S1—C6 | −132.2 (3) | C16—C17—S2—C18 | −129.7 (3) |
C5—S1—C6—N2 | −53.4 (3) | C17—S2—C18—N5 | −52.0 (3) |
C5—S1—C6—C7 | 129.7 (3) | C17—S2—C18—C19 | 129.9 (2) |
N2—C6—C7—C8 | −1.0 (5) | N5—C18—C19—C20 | −0.1 (5) |
S1—C6—C7—C8 | 175.8 (3) | S2—C18—C19—C20 | 177.9 (2) |
C6—C7—C8—C9 | 1.9 (6) | C18—C19—C20—C21 | 2.0 (5) |
C7—C8—C9—C10 | −0.8 (5) | C19—C20—C21—C22 | −1.3 (5) |
C8—C9—C10—N2 | −1.2 (5) | C20—C21—C22—N5 | −1.3 (5) |
C9—C10—N2—C6 | 2.1 (4) | C19—C18—N5—C22 | −2.4 (4) |
C9—C10—N2—Ru1 | 179.4 (2) | S2—C18—N5—C22 | 179.7 (2) |
C7—C6—N2—C10 | −1.0 (4) | C19—C18—N5—Ru2 | 179.8 (2) |
S1—C6—N2—C10 | −177.7 (2) | S2—C18—N5—Ru2 | 1.9 (3) |
C7—C6—N2—Ru1 | −178.2 (2) | C21—C22—N5—C18 | 3.1 (4) |
S1—C6—N2—Ru1 | 5.2 (3) | C21—C22—N5—Ru2 | −179.0 (2) |
N3—Ru1—N2—C10 | 128.5 (2) | N6ii—Ru2—N5—C18 | 126.5 (2) |
N3i—Ru1—N2—C10 | −51.5 (2) | N6—Ru2—N5—C18 | −53.5 (2) |
N1i—Ru1—N2—C10 | 41.6 (2) | N4—Ru2—N5—C18 | 40.4 (2) |
N1—Ru1—N2—C10 | −138.4 (2) | N4ii—Ru2—N5—C18 | −139.6 (2) |
N3—Ru1—N2—C6 | −54.5 (2) | N6ii—Ru2—N5—C22 | −51.3 (2) |
N3i—Ru1—N2—C6 | 125.5 (2) | N6—Ru2—N5—C22 | 128.7 (2) |
N1i—Ru1—N2—C6 | −141.4 (2) | N4—Ru2—N5—C22 | −137.4 (2) |
N1—Ru1—N2—C6 | 38.6 (2) | N4ii—Ru2—N5—C22 | 42.6 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···F7Aiii | 0.93 | 2.45 | 3.05 (1) | 122 |
C20—H20···F7Aiii | 0.93 | 2.46 | 3.05 (1) | 121 |
C12—H12C···F4iv | 0.96 | 2.38 | 3.205 (5) | 144 |
C12—H12A···F6iv | 0.96 | 2.45 | 3.34 (1) | 154 |
O—H0A···F2v | 0.87 | 2.05 | 2.917 (5) | 171 |
O—H0B···F8vi | 0.84 | 2.02 | 2.83 (1) | 162 |
O—H0B···F8Avi | 0.84 | 1.96 | 2.81 (1) | 176 |
Symmetry codes: (iii) x, y, z−1; (iv) x+1, y, z−1; (v) −x+1, −y+1, −z+1; (vi) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Ru(C2H3N)2(C10H8N2S)2].2(BF4).H2O |
Mr | 751.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 10.0709 (7), 12.6595 (8), 13.547 (1) |
α, β, γ (°) | 77.016 (7), 75.004 (6), 68.225 (6) |
V (Å3) | 1533.3 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.73 |
Crystal size (mm) | 0.36 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Numerical by seven indexed faces (XPREPW in SHELXTL; Siemens, 1996) |
Tmin, Tmax | 0.689, 0.826 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7496, 5922, 4761 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.085, 1.06 |
No. of reflections | 5922 |
No. of parameters | 440 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.39 |
Computer programs: XSCANS (Bruker,1999), XSCANS, SHELXS90 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XPW (SHELXTL; Siemens, 1996), PARST97 (Nardelli, 1995) and SHELXL97.
Ru1—N3 | 2.022 (2) | Ru2—N6 | 2.018 (2) |
Ru1—N1 | 2.088 (2) | Ru2—N4 | 2.091 (2) |
Ru1—N2 | 2.092 (2) | Ru2—N5 | 2.093 (2) |
C5—S1 | 1.761 (3) | C17—S2 | 1.768 (3) |
S1—C6 | 1.763 (3) | S2—C18 | 1.767 (3) |
N3—C11 | 1.127 (4) | N6—C23 | 1.133 (4) |
C11—C12 | 1.457 (4) | C23—C24 | 1.458 (4) |
N3—Ru1—N1 | 93.21 (9) | N6—Ru2—N4 | 94.01 (9) |
N3—Ru1—N2 | 93.75 (9) | N6—Ru2—N5 | 94.88 (9) |
N1—Ru1—N2 | 88.29 (9) | N4—Ru2—N5 | 88.61 (9) |
N1—C5—S1 | 120.8 (2) | N4—C17—S2 | 120.1 (2) |
C5—S1—C6 | 102.3 (1) | C18—S2—C17 | 102.4 (1) |
N2—C6—S1 | 120.7 (2) | N5—C18—S2 | 120.7 (2) |
C11—N3—Ru1 | 177.5 (2) | C23—N6—Ru2 | 171.5 (2) |
N3—C11—C12 | 178.0 (3) | N6—C23—C24 | 179.9 (4) |
N1—C5—S1—C6 | 49.1 (3) | N4—C17—S2—C18 | 51.9 (3) |
C5—S1—C6—N2 | −53.4 (3) | C17—S2—C18—N5 | −52.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12C···F4i | 0.96 | 2.38 | 3.205 (5) | 144 |
O—H0A···F2ii | 0.87 | 2.05 | 2.917 (5) | 171 |
O—H0B···F8iii | 0.84 | 2.02 | 2.83 (1) | 162 |
O—H0B···F8Aiii | 0.84 | 1.96 | 2.81 (1) | 176 |
Symmetry codes: (i) x+1, y, z−1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z. |
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Following our interest in the chemistry of the flexible non-planar bipyridine-like ligands (Tresoldi et al., 1991, 1992) we were particularly interested to know how they would modify the chemical and physical properties of the ruthenium complexes (Bruno et al., 1995; Tresoldi et al., 1996). Recently taking advantage of the steric hindrance of the cis-Ru(N,N-dps)2-core and steric demanding nature of dps we were able to introduce into the above centre a N,S-coordinated dps ligand and provide the possibility for pairs of chemically distinct coordination modes being present in [Ru(N,N-dps)2(N,S-dps)][PF6]2 (Scopelliti et al., 2001). In this work the solvolysis of the last complex in the presence of an excess of HBF4 has led to the title complex (I).
It is the first example of a ruthenium complex in which two dps ligands adopt the trans arrangement.
The IR spectrum contains the characteristic bands of the dps ligands at 1589 (s), 1561 (ms), 783 (versus), 774 (versus), 752 (ms) and 723 (s). The 1H-NMR spectrum in CD3(CO)2 show a single ABMX system with signals at d 8.90, assigned to the proton H6 in ortho position with respect to the N atom, 7.82, assigned to the proton H5 in the meta position, 8.34, assigned to the proton H4 in the para position and 8.00, assigned to the proton H3 in the ortho position with respect to the S atom, while the 13C NMR show signals at d 146.87 (C6), 125.13 (C5), 143.18 (C4), 126.82 (C3) and 154.57 (C2). These data are in agreement with the presence of a trans isomer which has four equivalent pyridine rings. A cis isomer should have only two equivalent pyridyl rings.
Di-2-pyridyl sulfide and its derivatives are flexible ligands that can adopt several possible conformations and dynamic interconvertion depending on their chemical condition (protonated or unprotonated free molecule, chelating or bridging ligand) and on the physical state (Nicoló et al., 1996; and references therein).
The crystal packing of the title compound (I) shows two complex cations placed on two crystallographic independent inversion centres, in the 1:2 ratio with the tetrafluoroborate anions for charge balance. Then both molecules have the imposed Ci symmetry and appear equal within the experimental errors. The dps ligand adopts the twisted N,N inside `butterfly-like' arrangement and the resulting six-membered chelate rings show the usual boat conformation, as evidenced by the puckering analysis (Cremer & Pople, 1975) on Ru1,N1,C5,S1,C6,N2 [Ru2,N4,C17,S2,C18,N5] ring: θ=88.4 (2) [88.9 (2)]°, ϕ=2.4 (2) [-0.2 (2)]°, QT=0.897 (2) [0.898 (2)] Å and ΔS(Ru)=0.025 (1) [0.001 (1)], respectively. The C and N atoms lie on a plane from which the Ru and S atoms deviate 0.8148 (1) [0.8055 (1)] and 0.743 (1) [0.754 (1)]Å on the same side, respectively. The geometry of the trans-arrangement of the two chelating dps is very similar to that one found in the square-planar palladium cation [Pd(dps)2]2+ (Bruno et al., 1995) showing shorter metal-nitrogen bond lengths as expected by the different metal atom size. The geometry about the ruthenium(II) ion is distorted octahedral (Fig.1), with the coordination polyhedron defined by four N atoms of the two opposite chelating dps rings on the equatorial plane and the two acetonitrile N atoms along the axial direction. The Ru—Npy bonds are equivalent [av. 2.091 (3) Å] but significantly longer than the axial Ru—Nac due to the different electronic and steric properties of the two ligand types and the larger hindrance on the equatorial plane. In fact the dps chelating bite (average Npy—Ru—Npy and Npy···Npy are 88.5 (1)° and 2.918 (5) Å, respectively) is very similar in the cis-[Ru(dps)2Cl2] (Bruno et al., 1995) [88.5 (1)° and 2.893 (4) Å] and in one N,N-chelate ligand in [Ru(dps)3]2+ (Scopelliti et al., 2001) [89.5 (2)° and 2.918 (7) Å]. The main distortion from the regular coordination geometry is due to the hindering effect of the S atom on the axial acetonitrile ligand on the same side with respect to the equatorial plane, increasing the Npy—Ru—Nac up to the mean value of 93.5 (1) and 94.5 (1)° in the Ru1 and Ru2 cations, respectively.
In order to understand the structural modifications of the ligand induced by the dps coordination to the metal centre ab initio calculations [HF/6–31+G(d,p) method] were carried out on the free ligand by using GAUSSIAN98 (Frisch et al., 1998). The most important variations concern pyridyl-N atoms: the calculated N—C distances 1.318 and 1.321 Å in each ring are shorter than the experimental mean value 1.350 (5) Å while the N···N computed separation of 3.41 Å is significantly longer, mainly due to the N,N-coordination of dps. The calculated C—S bond lengths are slightly longer than the experimental mean value of 1.764 (4) Å], while the C—S—C computed bond angle of 101.5° is very close to the observed average 102.3 (2)°.