Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014878/na6084sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014878/na6084IIsup2.hkl |
CCDC reference: 118726
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.005 Å
- R factor = 0.052
- wR factor = 0.117
- Data-to-parameter ratio = 23.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 38.62 From the CIF: _reflns_number_total 9359 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 13764 Completeness (_total/calc) 68.00% Alert A: < 85% complete (theta max?) PLAT_706 Alert A H...A Calc 3.07(5), Rep 2.68(4), Dev. 7.80 Sigma H10C -CL1 1.555 1.555 PLAT_706 Alert A H...A Calc 27.65(4), Rep 2.73(5), Dev. 623.00 Sigma H4 -CL1 1.555 6.555 PLAT_706 Alert A H...A Calc 19.95(4), Rep 2.65(4), Dev. 432.50 Sigma H14 -CL2 1.555 3.455 PLAT_707 Alert A D...A Calc 27.139(3), Rep 3.522(3), Dev. 7872.33 Sigma C4 -CL1 1.555 6.555 PLAT_707 Alert A D...A Calc 19.619(4), Rep 3.606(4), Dev. 4003.25 Sigma C14 -CL2 1.555 3.455 PLAT_708 Alert A D-H..A Calc 81(3), Rep 104(3), Dev. 7.67 Sigma C10 -H10C -CL1 1.555 1.555 1.555 PLAT_708 Alert A D-H..A Calc 52(3), Rep 158(4), Dev. 35.33 Sigma C4 -H4 -CL1 1.555 1.555 6.555 PLAT_708 Alert A D-H..A Calc 69(2), Rep 170(3), Dev. 50.50 Sigma C14 -H14 -CL2 1.555 1.555 3.455
Alert Level B:
CRYSS_02 Alert B The value of _exptl_crystal_size_min is > 0.6 Minimum crystal size given = 0.900 CRYSS_02 Alert B The value of _exptl_crystal_size_mid is > 0.8 Mid crystal size given = 1.200 CRYSS_02 Alert B The value of _exptl_crystal_size_max is > 1.0 Maximum crystal size given = 1.200
Alert Level C:
PLAT_362 Alert C Short C(sp3)-C(sp2) Bond C(1) - C(6) = 1.39 Ang. PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 1 N4 -RU1 -N1 -C5 97.00 4.00 1.555 1.555 1.555 1.555 PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 6 N4 -RU1 -N1 -C1 -79.00 4.00 1.555 1.555 1.555 1.555 PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 41 N1 -RU1 -N4 -C12 135.00 3.00 1.555 1.555 1.555 1.555 PLAT_710 Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 46 N1 -RU1 -N4 -C16 -42.00 4.00 1.555 1.555 1.555 1.555 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 38.62 From the CIF: _reflns_number_total 9359 From the CIF: _diffrn_reflns_limit_ max hkl 20. 20. 43. From the CIF: _diffrn_reflns_limit_ min hkl -10. -13. -10. TEST1: Expected hkl limits for theta max Calculated maximum hkl 22. 24. 47. Calculated minimum hkl -22. -24. -47. ALERT: Expected hkl max differ from CIF values
9 Alert Level A = Potentially serious problem
3 Alert Level B = Potential problem
5 Alert Level C = Please check
A solution of {Ru}N≡N{Ru}, (I) (128 mg, 0.2 mmol), and py (32 mg, 0.4 mmol) in THF (30 ml) was stirred for 1 h at 298 K. During the course of the reaction, the colour of the solution turned from brown to red and the turbidity disappeared. The reaction mixture was then concentrated to 5 ml and n-pentane (50 ml) was added. The supernatant liquid was carefully decanted and the residue was dried in vacuo to yield (II) [150 mg, 95% yield based on (I)] as a red–brown solid. By diffusion of n-pentane into a dichlormethane/n-pentane solution of (II), which has been endowed with toluene, at 298 K, single crystals of (II) could be obtained. M.p.: [K] 302 (decomposition). 1H NMR (CDCl3, p.p.m.): [δ] 2.38 (s, 12 H, NMe2), 4.03 (s, 4H, CH2), 7.1–7.2 (m, 2H, C6H3), 7.3–7.4 (m, 3 H, C5H5N), 7.7–7.8 (m, 1H, C5H3N), 9.6–9.7 (m, 2H, C5H5N). 13C{1H} NMR (CDCl3, p.p.m.): [δ] 53.6 (NMe2), 72.1 (CH2), 118.6 (CH/C5H3N), 123.5 (CH/C5H5N), 130.4 (i-C/C5H3N), 133.6 (CH/C5H5N), 156.4 (CH/C5H5N), 163.2 (CH/C5H3N). Analysis calculated for C16H24Cl2N4Ru (440.40): C 43.24, H 5.44, N 12.61%; found: C 43.79, H 5.78, N 12.23%.
Recently, interest has been focused on the chemistry of bis-orthochelating aromatic ligands (Rietveld et al., 1997). This was due to their applicability to catalytic processes (Abbenhuis, del Río et al., 1998) or materials science (Steenwinkel et al., 1998). In this context, the dinitrogen-bridged bis-ruthenium complex {Ru}N≡N{Ru}, (I) [{Ru} = mer,trans-(C5H3N(CH2NMe2)2-2,6)-RuCl2] (Abbenhuis, Boersma & van Koten, 1998), has been studied in the synthesis of bioactive arylpiperazines. In order to gain a deeper insight into the catalytic behaviour of (I), this homodinuclear complex was reacted with various N-donor molecules (del R\'io et al., 2000). Treatment of (I) with two equivalents of py (py = pyridine, C5H5N) leads to the formation of the title compound {Ru}py·C7H8, (II), in high yield by loss of N2. We report here on the structure of the (II), which incorporates two structural type pyridine ligands, i.e. C5H5N and C5H3N(CH2NMe2)2-2,6.
The X-ray diffraction study confirms the general structure of (II) in solution, suggested on the basis of the NMR (1H, 13C{1H}) and IR data of (II) (Fig. 1).
In (II), the RuII centre occupies a distorted octahedral environment, with the three N-donor atoms of the NN'N-ligand in a meridional position. The Cl atoms are forced in the apical positions and are trans-orientated to each other. In general, the Ru—Npy, Ru—NNMe and Ru—Cl distances Ru1—Cl1 [2.3502 (7) Å], Ru1—Cl2 [2.3581 (7) Å], Ru1—N1 [1.962 (2) Å], Ru1—N2 [2.348 (3) Å] and Ru1—N3 [2.251 (3) Å], as well as the angles around the RuII centre Cl1—Ru1—Cl2 [177.19 (3)] and N2—Ru1—N3 [160.57 (9)°] of the {Ru} building block are consistent with those values reported for this type of complex fragment (del Rio et al., 2000). The length of the Ru1—N4 bond of 2.096 (2) Å is elongated when compared to the Ru1—N1 bond, but lies in the range of distances reported for other RuII–pyridine complexes, e.g. [Ru(py)6]2+ with 2.10–2.14 Å (Templeton, 1979). Similar Ru—Npy distances are, e.g., found in [RuCl(py)4(pz)]+ with 2.105 (4) Å (Coe et al., 1995). This relatively short Ru1—N1 distance can best be explained by the imbedding of the RuII centre into the framework of the bis-orthochelating NN'N ligand. The angle N1—Ru1—N4 [178.37 (9)°] resembles the linearity of this array. The planes of the two pyridine ligands are tilted by 54.33 (10)°.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai & Huttner, 1994); software used to prepare material for publication: SHELX97.
Fig. 1. ZORTEP plot (50% probability) of complex (II) with molecular geometry and atom-numbering scheme (the toluene solvate molecule is not shown for clarity). |
[RuCl2(C11H19N3)(C5H5N)]·C7H8 | Dx = 1.470 Mg m−3 |
Mr = 536.50 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 31497 reflections |
a = 12.7109 (1) Å | θ = 1.5–38.6° |
b = 14.1115 (2) Å | µ = 0.88 mm−1 |
c = 27.0317 (3) Å | T = 173 K |
V = 4848.67 (10) Å3 | Block, dark red |
Z = 8 | 1.20 × 1.20 × 0.90 mm |
F(000) = 2208 |
Bruker SMART CCD diffractometer | 9359 independent reflections |
Radiation source: fine-focus sealed tube | 7687 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 38.6°, θmin = 1.5° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2000) | h = −10→20 |
Tmin = 0.374, Tmax = 0.451 | k = −13→20 |
43809 measured reflections | l = −10→43 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0208P)2 + 13.1818P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.015 |
9359 reflections | Δρmax = 2.07 e Å−3 |
400 parameters | Δρmin = −1.86 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00058 (9) |
[RuCl2(C11H19N3)(C5H5N)]·C7H8 | V = 4848.67 (10) Å3 |
Mr = 536.50 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 12.7109 (1) Å | µ = 0.88 mm−1 |
b = 14.1115 (2) Å | T = 173 K |
c = 27.0317 (3) Å | 1.20 × 1.20 × 0.90 mm |
Bruker SMART CCD diffractometer | 9359 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2000) | 7687 reflections with I > 2σ(I) |
Tmin = 0.374, Tmax = 0.451 | Rint = 0.041 |
43809 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0208P)2 + 13.1818P] where P = (Fo2 + 2Fc2)/3 |
9359 reflections | Δρmax = 2.07 e Å−3 |
400 parameters | Δρmin = −1.86 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.025486 (15) | 0.384516 (16) | 0.129116 (7) | 0.01901 (6) | |
Cl1 | −0.08681 (5) | 0.33484 (6) | 0.19313 (2) | 0.02838 (14) | |
Cl2 | 0.13228 (6) | 0.43118 (6) | 0.06208 (3) | 0.03079 (15) | |
N1 | 0.10360 (17) | 0.45844 (18) | 0.17839 (8) | 0.0222 (4) | |
N2 | −0.04352 (18) | 0.53882 (19) | 0.12952 (9) | 0.0248 (4) | |
N3 | 0.12600 (19) | 0.2586 (2) | 0.14864 (9) | 0.0267 (5) | |
N4 | −0.06081 (18) | 0.30413 (19) | 0.07806 (8) | 0.0238 (4) | |
C1 | 0.0713 (2) | 0.5483 (2) | 0.19879 (10) | 0.0263 (5) | |
C2 | 0.1231 (3) | 0.6000 (3) | 0.23496 (11) | 0.0341 (7) | |
H2 | 0.102 (3) | 0.660 (3) | 0.2475 (14) | 0.028 (9)* | |
C3 | 0.2067 (3) | 0.5551 (3) | 0.25109 (12) | 0.0402 (8) | |
H3 | 0.240 (3) | 0.586 (3) | 0.2770 (14) | 0.041 (11)* | |
C4 | 0.2387 (2) | 0.4618 (3) | 0.23040 (11) | 0.0356 (7) | |
H4 | 0.292 (4) | 0.433 (3) | 0.2413 (16) | 0.044 (12)* | |
C5 | 0.1861 (2) | 0.4154 (2) | 0.19298 (10) | 0.0280 (6) | |
C6 | −0.0259 (2) | 0.5780 (2) | 0.18130 (11) | 0.0284 (5) | |
H6A | −0.034 (3) | 0.654 (3) | 0.1820 (13) | 0.030 (10)* | |
H6B | −0.073 (4) | 0.542 (3) | 0.2048 (16) | 0.046 (12)* | |
C7 | 0.0005 (3) | 0.6164 (3) | 0.09532 (14) | 0.0353 (7) | |
H7A | −0.010 (3) | 0.593 (3) | 0.0604 (17) | 0.045 (12)* | |
H7B | 0.069 (4) | 0.618 (3) | 0.1014 (16) | 0.044 (12)* | |
H7C | −0.030 (3) | 0.683 (3) | 0.0998 (15) | 0.042 (12)* | |
C8 | −0.1476 (3) | 0.5401 (3) | 0.12053 (14) | 0.0361 (7) | |
H8A | −0.153 (3) | 0.524 (3) | 0.0851 (15) | 0.038 (11)* | |
H8B | −0.178 (4) | 0.493 (4) | 0.1420 (16) | 0.046 (12)* | |
H8C | −0.173 (3) | 0.613 (3) | 0.1274 (14) | 0.038 (11)* | |
C9 | 0.2127 (2) | 0.3193 (3) | 0.16368 (12) | 0.0315 (6) | |
H9A | 0.242 (3) | 0.344 (3) | 0.1336 (13) | 0.034 (10)* | |
H9B | 0.253 (3) | 0.273 (3) | 0.1820 (13) | 0.029 (9)* | |
C10 | 0.0960 (3) | 0.1941 (3) | 0.19153 (12) | 0.0326 (6) | |
H10A | 0.085 (3) | 0.237 (3) | 0.2192 (13) | 0.028 (9)* | |
H10B | 0.145 (3) | 0.137 (3) | 0.2005 (14) | 0.035 (10)* | |
H10C | 0.042 (4) | 0.152 (3) | 0.1840 (15) | 0.043 (12)* | |
C11 | 0.1532 (3) | 0.1858 (3) | 0.10808 (13) | 0.0346 (7) | |
H11A | 0.202 (4) | 0.141 (4) | 0.1183 (17) | 0.059 (15)* | |
H11B | 0.104 (3) | 0.141 (3) | 0.1001 (15) | 0.038 (11)* | |
H11C | 0.172 (3) | 0.229 (3) | 0.0792 (13) | 0.025 (9)* | |
C12 | −0.0862 (2) | 0.3479 (3) | 0.03433 (10) | 0.0294 (6) | |
H12 | −0.063 (3) | 0.419 (3) | 0.0269 (13) | 0.026 (9)* | |
C13 | −0.1474 (3) | 0.2998 (3) | 0.00140 (11) | 0.0380 (8) | |
H13 | −0.165 (3) | 0.332 (3) | −0.0289 (15) | 0.042 (12)* | |
C14 | −0.1821 (3) | 0.2006 (3) | 0.01172 (12) | 0.0388 (8) | |
H14 | −0.224 (3) | 0.163 (3) | −0.0108 (15) | 0.041 (11)* | |
C15 | −0.1552 (2) | 0.1540 (3) | 0.05585 (12) | 0.0327 (6) | |
H15 | −0.172 (3) | 0.087 (3) | 0.0663 (13) | 0.029 (9)* | |
C16 | −0.0964 (2) | 0.2084 (2) | 0.08794 (11) | 0.0279 (6) | |
H16 | −0.082 (3) | 0.178 (3) | 0.1168 (13) | 0.026 (9)* | |
C17 | −0.0734 (3) | 0.8834 (3) | 0.07210 (11) | 0.0322 (6) | |
C18 | 0.0140 (3) | 0.9106 (3) | 0.09256 (14) | 0.0392 (7) | |
H18 | 0.065 (4) | 0.928 (4) | 0.0704 (16) | 0.050 (13)* | |
C19 | 0.0257 (3) | 0.9142 (3) | 0.14351 (17) | 0.0482 (10) | |
H19 | 0.081 (4) | 0.933 (4) | 0.1562 (16) | 0.047 (13)* | |
C20 | −0.0489 (3) | 0.8921 (3) | 0.17501 (14) | 0.0431 (8) | |
H20 | −0.039 (4) | 0.893 (4) | 0.208 (2) | 0.067 (16)* | |
C21 | −0.1364 (3) | 0.8664 (3) | 0.15506 (14) | 0.0425 (8) | |
H21 | −0.188 (4) | 0.852 (3) | 0.1765 (15) | 0.043 (12)* | |
C22 | −0.1482 (3) | 0.8620 (3) | 0.10411 (13) | 0.0357 (7) | |
H22 | −0.205 (4) | 0.838 (4) | 0.0889 (16) | 0.050 (13)* | |
C23 | −0.0860 (4) | 0.8734 (4) | 0.01697 (14) | 0.0479 (10) | |
H23A | −0.034 (5) | 0.907 (4) | −0.002 (2) | 0.071 (17)* | |
H23B | −0.089 (4) | 0.801 (4) | 0.0086 (18) | 0.062 (15)* | |
H23C | −0.130 (5) | 0.914 (5) | 0.007 (2) | 0.08 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01597 (9) | 0.02393 (10) | 0.01713 (8) | 0.00102 (7) | 0.00060 (6) | 0.00107 (7) |
Cl1 | 0.0239 (3) | 0.0370 (4) | 0.0242 (3) | 0.0019 (3) | 0.0070 (2) | 0.0049 (2) |
Cl2 | 0.0253 (3) | 0.0383 (4) | 0.0287 (3) | 0.0013 (3) | 0.0101 (2) | 0.0042 (3) |
N1 | 0.0162 (9) | 0.0314 (12) | 0.0188 (8) | 0.0006 (8) | −0.0014 (7) | 0.0005 (8) |
N2 | 0.0179 (10) | 0.0305 (12) | 0.0260 (10) | 0.0042 (8) | 0.0014 (8) | 0.0035 (9) |
N3 | 0.0178 (10) | 0.0336 (13) | 0.0289 (11) | 0.0046 (9) | 0.0007 (8) | 0.0014 (9) |
N4 | 0.0189 (10) | 0.0337 (13) | 0.0189 (9) | 0.0002 (9) | −0.0021 (7) | 0.0015 (8) |
C1 | 0.0214 (12) | 0.0330 (15) | 0.0246 (11) | −0.0020 (10) | 0.0048 (9) | −0.0037 (10) |
C2 | 0.0315 (15) | 0.0439 (19) | 0.0270 (12) | −0.0107 (13) | 0.0062 (11) | −0.0103 (12) |
C3 | 0.0285 (15) | 0.068 (3) | 0.0246 (12) | −0.0177 (15) | −0.0006 (11) | −0.0020 (15) |
C4 | 0.0202 (13) | 0.059 (2) | 0.0281 (13) | −0.0074 (13) | −0.0063 (10) | 0.0092 (13) |
C5 | 0.0172 (12) | 0.0424 (17) | 0.0244 (11) | −0.0029 (10) | −0.0015 (9) | 0.0062 (11) |
C6 | 0.0236 (13) | 0.0311 (15) | 0.0307 (13) | 0.0044 (11) | 0.0041 (10) | −0.0044 (11) |
C7 | 0.0330 (16) | 0.0325 (17) | 0.0403 (16) | 0.0057 (13) | 0.0073 (12) | 0.0131 (14) |
C8 | 0.0223 (14) | 0.046 (2) | 0.0403 (17) | 0.0089 (13) | −0.0020 (11) | 0.0017 (14) |
C9 | 0.0178 (12) | 0.0397 (18) | 0.0370 (15) | 0.0060 (11) | −0.0012 (10) | 0.0042 (13) |
C10 | 0.0274 (15) | 0.0357 (17) | 0.0346 (14) | 0.0042 (12) | −0.0006 (11) | 0.0111 (13) |
C11 | 0.0312 (16) | 0.0331 (17) | 0.0394 (16) | 0.0072 (13) | 0.0054 (12) | −0.0056 (13) |
C12 | 0.0216 (12) | 0.0440 (18) | 0.0227 (11) | −0.0036 (12) | −0.0010 (9) | 0.0031 (11) |
C13 | 0.0250 (14) | 0.067 (3) | 0.0219 (12) | −0.0036 (14) | −0.0037 (10) | −0.0009 (14) |
C14 | 0.0205 (14) | 0.062 (2) | 0.0341 (15) | −0.0043 (14) | −0.0022 (11) | −0.0149 (15) |
C15 | 0.0227 (13) | 0.0381 (18) | 0.0374 (15) | −0.0062 (12) | 0.0031 (11) | −0.0075 (13) |
C16 | 0.0202 (12) | 0.0369 (16) | 0.0267 (12) | −0.0009 (11) | 0.0011 (9) | 0.0004 (11) |
C17 | 0.0316 (15) | 0.0330 (16) | 0.0320 (13) | 0.0038 (12) | 0.0006 (11) | 0.0013 (12) |
C18 | 0.0361 (18) | 0.0371 (18) | 0.0443 (18) | −0.0020 (14) | 0.0015 (14) | −0.0028 (14) |
C19 | 0.035 (2) | 0.053 (2) | 0.057 (2) | 0.0045 (17) | −0.0133 (17) | −0.0125 (19) |
C20 | 0.050 (2) | 0.044 (2) | 0.0354 (16) | 0.0105 (17) | −0.0055 (15) | −0.0091 (15) |
C21 | 0.0395 (19) | 0.051 (2) | 0.0373 (16) | 0.0071 (16) | 0.0087 (14) | −0.0044 (15) |
C22 | 0.0299 (16) | 0.0398 (19) | 0.0373 (15) | 0.0056 (13) | 0.0019 (12) | −0.0034 (13) |
C23 | 0.048 (2) | 0.062 (3) | 0.0334 (16) | 0.004 (2) | 0.0003 (15) | 0.0008 (17) |
Ru1—Cl1 | 2.3501 (7) | C9—H9A | 0.96 (4) |
Ru1—Cl2 | 2.3580 (7) | C9—H9B | 0.97 (4) |
Ru1—N1 | 1.962 (2) | C10—H10A | 0.98 (4) |
Ru1—N2 | 2.348 (3) | C10—H10B | 1.04 (4) |
Ru1—N3 | 2.251 (3) | C10—H10C | 0.93 (5) |
Ru1—N4 | 2.096 (2) | C11—H11A | 0.93 (6) |
N1—C5 | 1.274 (4) | C11—H11B | 0.91 (5) |
N1—C1 | 1.442 (4) | C11—H11C | 1.02 (4) |
N2—C8 | 1.345 (4) | C12—C13 | 1.363 (4) |
N2—C6 | 1.521 (4) | C12—H12 | 1.06 (4) |
N2—C7 | 1.538 (4) | C13—C14 | 1.495 (6) |
N3—C9 | 1.453 (4) | C13—H13 | 0.96 (4) |
N3—C10 | 1.522 (4) | C14—C15 | 1.404 (5) |
N3—C11 | 1.542 (4) | C14—H14 | 0.97 (4) |
N4—C12 | 1.373 (4) | C15—C16 | 1.379 (4) |
N4—C16 | 1.449 (4) | C15—H15 | 1.01 (4) |
C1—C2 | 1.386 (4) | C16—H16 | 0.91 (4) |
C1—C6 | 1.388 (4) | C17—C18 | 1.298 (5) |
C2—C3 | 1.312 (5) | C17—C22 | 1.321 (5) |
C2—H2 | 0.95 (4) | C17—C23 | 1.505 (5) |
C3—C4 | 1.487 (6) | C18—C19 | 1.386 (6) |
C3—H3 | 0.93 (4) | C18—H18 | 0.91 (5) |
C4—C5 | 1.378 (4) | C19—C20 | 1.312 (6) |
C4—H4 | 0.85 (5) | C19—H19 | 0.82 (5) |
C5—C9 | 1.607 (5) | C20—C21 | 1.287 (6) |
C6—H6A | 1.08 (4) | C20—H20 | 0.90 (5) |
C6—H6B | 1.01 (5) | C21—C22 | 1.387 (5) |
C7—H7A | 1.01 (5) | C21—H21 | 0.90 (4) |
C7—H7B | 0.89 (5) | C22—H22 | 0.90 (5) |
C7—H7C | 1.02 (5) | C23—H23A | 0.96 (6) |
C8—H8A | 0.99 (4) | C23—H23B | 1.05 (6) |
C8—H8B | 0.96 (5) | C23—H23C | 0.85 (7) |
C8—H8C | 1.10 (5) | ||
Cl1—Ru1—Cl2 | 177.19 (3) | H8A—C8—H8B | 114 (4) |
Cl1—Ru1—N4 | 90.31 (7) | N2—C8—H8C | 106 (2) |
Cl2—Ru1—N4 | 86.93 (7) | H8A—C8—H8C | 111 (3) |
N1—Ru1—N2 | 72.10 (9) | H8B—C8—H8C | 115 (3) |
N1—Ru1—N3 | 88.47 (10) | N3—C9—C5 | 118.4 (2) |
N2—Ru1—N3 | 160.57 (9) | N3—C9—H9A | 106 (2) |
N1—Ru1—N4 | 178.38 (9) | C5—C9—H9A | 101 (3) |
N4—Ru1—N3 | 91.39 (10) | N3—C9—H9B | 99 (2) |
N4—Ru1—N2 | 108.03 (9) | C5—C9—H9B | 115 (2) |
N1—Ru1—Cl1 | 88.06 (7) | H9A—C9—H9B | 118 (3) |
N3—Ru1—Cl1 | 86.37 (7) | N3—C10—H10A | 104 (2) |
N2—Ru1—Cl1 | 92.65 (6) | N3—C10—H10B | 119 (2) |
N1—Ru1—Cl2 | 94.70 (7) | H10A—C10—H10B | 113 (3) |
N3—Ru1—Cl2 | 94.24 (7) | N3—C10—H10C | 113 (3) |
N2—Ru1—Cl2 | 87.69 (6) | H10A—C10—H10C | 117 (3) |
C5—N1—C1 | 122.3 (3) | H10B—C10—H10C | 90 (4) |
C5—N1—Ru1 | 111.9 (2) | N3—C11—H11A | 113 (3) |
C1—N1—Ru1 | 125.66 (18) | N3—C11—H11B | 118 (3) |
C8—N2—C6 | 107.8 (2) | H11A—C11—H11B | 93 (4) |
C8—N2—C7 | 103.9 (3) | N3—C11—H11C | 101 (2) |
C6—N2—C7 | 103.9 (3) | H11A—C11—H11C | 119 (4) |
C8—N2—Ru1 | 112.3 (2) | H11B—C11—H11C | 113 (3) |
C6—N2—Ru1 | 106.65 (17) | C13—C12—N4 | 118.2 (3) |
C7—N2—Ru1 | 121.41 (19) | C13—C12—H12 | 120.4 (19) |
C9—N3—C10 | 109.2 (2) | N4—C12—H12 | 121.4 (19) |
C9—N3—C11 | 114.9 (2) | C12—C13—C14 | 120.9 (3) |
C10—N3—C11 | 101.5 (3) | C12—C13—H13 | 117 (3) |
C9—N3—Ru1 | 91.76 (19) | C14—C13—H13 | 122 (3) |
C10—N3—Ru1 | 120.52 (18) | C15—C14—C13 | 121.7 (3) |
C11—N3—Ru1 | 119.13 (19) | C15—C14—H14 | 114 (3) |
C12—N4—C16 | 120.3 (2) | C13—C14—H14 | 124 (3) |
C12—N4—Ru1 | 116.5 (2) | C16—C15—C14 | 113.9 (3) |
C16—N4—Ru1 | 123.11 (17) | C16—C15—H15 | 117 (2) |
C2—C1—C6 | 120.3 (3) | C14—C15—H15 | 129 (2) |
C2—C1—N1 | 126.7 (3) | C15—C16—N4 | 124.9 (3) |
C6—C1—N1 | 112.9 (3) | C15—C16—H16 | 112 (2) |
C3—C2—C1 | 111.4 (3) | N4—C16—H16 | 123 (2) |
C3—C2—H2 | 123 (2) | C18—C17—C22 | 113.8 (3) |
C1—C2—H2 | 126 (2) | C18—C17—C23 | 122.7 (4) |
C2—C3—C4 | 121.6 (3) | C22—C17—C23 | 123.4 (4) |
C2—C3—H3 | 113 (3) | C17—C18—C19 | 121.7 (4) |
C4—C3—H3 | 125 (3) | C17—C18—H18 | 114 (3) |
C5—C4—C3 | 124.4 (3) | C19—C18—H18 | 124 (3) |
C5—C4—H4 | 114 (3) | C20—C19—C18 | 124.0 (4) |
C3—C4—H4 | 121 (3) | C20—C19—H19 | 115 (3) |
N1—C5—C4 | 113.6 (3) | C18—C19—H19 | 121 (3) |
N1—C5—C9 | 115.0 (3) | C21—C20—C19 | 114.8 (4) |
C4—C5—C9 | 131.4 (3) | C21—C20—H20 | 123 (3) |
C1—C6—N2 | 109.5 (2) | C19—C20—H20 | 122 (3) |
C1—C6—H6A | 112 (2) | C20—C21—C22 | 121.5 (4) |
N2—C6—H6A | 111 (2) | C20—C21—H21 | 115 (3) |
C1—C6—H6B | 99 (3) | C22—C21—H21 | 123 (3) |
N2—C6—H6B | 108 (3) | C17—C22—C21 | 124.2 (4) |
H6A—C6—H6B | 115 (3) | C17—C22—H22 | 112 (3) |
N2—C7—H7A | 106 (3) | C21—C22—H22 | 124 (3) |
N2—C7—H7B | 105 (3) | C17—C23—H23A | 114 (3) |
H7A—C7—H7B | 108 (4) | C17—C23—H23B | 108 (3) |
N2—C7—H7C | 116 (2) | H23A—C23—H23B | 113 (4) |
H7A—C7—H7C | 111 (3) | C17—C23—H23C | 110 (4) |
H7B—C7—H7C | 109 (4) | H23A—C23—H23C | 87 (5) |
N2—C8—H8A | 104 (2) | H23B—C23—H23C | 124 (5) |
N2—C8—H8B | 106 (3) | ||
N4—Ru1—N1—C5 | 97 (4) | N1—Ru1—N4—C16 | −42 (4) |
N3—Ru1—N1—C5 | 12.4 (2) | N3—Ru1—N4—C16 | 42.7 (2) |
N2—Ru1—N1—C5 | −167.8 (2) | N2—Ru1—N4—C16 | −136.5 (2) |
Cl1—Ru1—N1—C5 | 98.82 (19) | Cl1—Ru1—N4—C16 | −43.6 (2) |
Cl2—Ru1—N1—C5 | −81.73 (19) | Cl2—Ru1—N4—C16 | 136.9 (2) |
N4—Ru1—N1—C1 | −79 (4) | C5—N1—C1—C2 | 1.1 (4) |
N3—Ru1—N1—C1 | −164.1 (2) | Ru1—N1—C1—C2 | 177.3 (2) |
N2—Ru1—N1—C1 | 15.7 (2) | C5—N1—C1—C6 | −173.9 (3) |
Cl1—Ru1—N1—C1 | −77.7 (2) | Ru1—N1—C1—C6 | 2.3 (3) |
Cl2—Ru1—N1—C1 | 101.7 (2) | C6—C1—C2—C3 | 172.1 (3) |
N1—Ru1—N2—C8 | −146.0 (2) | N1—C1—C2—C3 | −2.6 (4) |
N4—Ru1—N2—C8 | 32.3 (2) | C1—C2—C3—C4 | 1.5 (5) |
N3—Ru1—N2—C8 | −145.5 (3) | C2—C3—C4—C5 | 0.9 (5) |
Cl1—Ru1—N2—C8 | −58.9 (2) | C1—N1—C5—C4 | 1.4 (4) |
Cl2—Ru1—N2—C8 | 118.3 (2) | Ru1—N1—C5—C4 | −175.2 (2) |
N1—Ru1—N2—C6 | −28.10 (17) | C1—N1—C5—C9 | −176.6 (2) |
N4—Ru1—N2—C6 | 150.20 (17) | Ru1—N1—C5—C9 | 6.7 (3) |
N3—Ru1—N2—C6 | −27.6 (3) | C3—C4—C5—N1 | −2.4 (4) |
Cl1—Ru1—N2—C6 | 59.00 (17) | C3—C4—C5—C9 | 175.2 (3) |
Cl2—Ru1—N2—C6 | −123.79 (17) | C2—C1—C6—N2 | 155.6 (3) |
N1—Ru1—N2—C7 | 90.4 (2) | N1—C1—C6—N2 | −29.0 (4) |
N4—Ru1—N2—C7 | −91.3 (2) | C8—N2—C6—C1 | 159.2 (3) |
N3—Ru1—N2—C7 | 90.9 (3) | C7—N2—C6—C1 | −90.9 (3) |
Cl1—Ru1—N2—C7 | 177.5 (2) | Ru1—N2—C6—C1 | 38.4 (3) |
Cl2—Ru1—N2—C7 | −5.3 (2) | C10—N3—C9—C5 | −84.5 (3) |
N1—Ru1—N3—C9 | −27.51 (17) | C11—N3—C9—C5 | 162.3 (3) |
N4—Ru1—N3—C9 | 154.10 (17) | Ru1—N3—C9—C5 | 38.8 (3) |
N2—Ru1—N3—C9 | −28.0 (3) | N1—C5—C9—N3 | −37.7 (4) |
Cl1—Ru1—N3—C9 | −115.67 (17) | C4—C5—C9—N3 | 144.7 (3) |
Cl2—Ru1—N3—C9 | 67.08 (17) | C16—N4—C12—C13 | 1.5 (4) |
N1—Ru1—N3—C10 | 86.1 (2) | Ru1—N4—C12—C13 | −176.3 (2) |
N4—Ru1—N3—C10 | −92.3 (2) | N4—C12—C13—C14 | −2.4 (5) |
N2—Ru1—N3—C10 | 85.6 (4) | C12—C13—C14—C15 | 1.3 (5) |
Cl1—Ru1—N3—C10 | −2.1 (2) | C13—C14—C15—C16 | 0.9 (5) |
Cl2—Ru1—N3—C10 | −179.3 (2) | C14—C15—C16—N4 | −1.9 (5) |
N1—Ru1—N3—C11 | −147.5 (2) | C12—N4—C16—C15 | 0.8 (4) |
N4—Ru1—N3—C11 | 34.1 (2) | Ru1—N4—C16—C15 | 178.5 (2) |
N2—Ru1—N3—C11 | −148.0 (3) | C22—C17—C18—C19 | 1.2 (6) |
Cl1—Ru1—N3—C11 | 124.3 (2) | C23—C17—C18—C19 | −176.4 (4) |
Cl2—Ru1—N3—C11 | −52.9 (2) | C17—C18—C19—C20 | −0.8 (7) |
N1—Ru1—N4—C12 | 135 (3) | C18—C19—C20—C21 | −0.3 (7) |
N3—Ru1—N4—C12 | −139.5 (2) | C19—C20—C21—C22 | 0.8 (6) |
N2—Ru1—N4—C12 | 41.2 (2) | C18—C17—C22—C21 | −0.7 (6) |
Cl1—Ru1—N4—C12 | 134.1 (2) | C23—C17—C22—C21 | 176.8 (4) |
Cl2—Ru1—N4—C12 | −45.3 (2) | C20—C21—C22—C17 | −0.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···Cl1 | 0.96 (5) | 2.87 (5) | 3.583 (4) | 132 (4) |
C9—H9A···Cl2 | 0.96 (4) | 2.68 (4) | 3.329 (4) | 125 (3) |
C10—H10C···Cl1 | 0.97 (4) | 2.68 (4) | 3.057 (4) | 104 (3) |
C12—H12···Cl2 | 1.06 (4) | 2.66 (4) | 3.107 (3) | 105 (2) |
C4—H4···Cl1i | 0.84 (5) | 2.73 (5) | 3.522 (3) | 158 (4) |
C14—H14···Cl2ii | 0.97 (4) | 2.65 (4) | 3.606 (4) | 170 (3) |
Symmetry codes: (i) x−1/2, y, −z−1/2; (ii) −x−1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [RuCl2(C11H19N3)(C5H5N)]·C7H8 |
Mr | 536.50 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 12.7109 (1), 14.1115 (2), 27.0317 (3) |
V (Å3) | 4848.67 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 1.20 × 1.20 × 0.90 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.374, 0.451 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43809, 9359, 7687 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.878 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.117, 1.19 |
No. of reflections | 9359 |
No. of parameters | 400 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0208P)2 + 13.1818P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.07, −1.86 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai & Huttner, 1994), SHELX97.
Ru1—Cl1 | 2.3501 (7) | Ru1—N2 | 2.348 (3) |
Ru1—Cl2 | 2.3580 (7) | Ru1—N3 | 2.251 (3) |
Ru1—N1 | 1.962 (2) | Ru1—N4 | 2.096 (2) |
Cl1—Ru1—Cl2 | 177.19 (3) | N1—Ru1—N3 | 88.47 (10) |
Cl1—Ru1—N4 | 90.31 (7) | N2—Ru1—N3 | 160.57 (9) |
Cl2—Ru1—N4 | 86.93 (7) | N1—Ru1—N4 | 178.38 (9) |
N1—Ru1—N2 | 72.10 (9) |
Recently, interest has been focused on the chemistry of bis-orthochelating aromatic ligands (Rietveld et al., 1997). This was due to their applicability to catalytic processes (Abbenhuis, del Río et al., 1998) or materials science (Steenwinkel et al., 1998). In this context, the dinitrogen-bridged bis-ruthenium complex {Ru}N≡N{Ru}, (I) [{Ru} = mer,trans-(C5H3N(CH2NMe2)2-2,6)-RuCl2] (Abbenhuis, Boersma & van Koten, 1998), has been studied in the synthesis of bioactive arylpiperazines. In order to gain a deeper insight into the catalytic behaviour of (I), this homodinuclear complex was reacted with various N-donor molecules (del R\'io et al., 2000). Treatment of (I) with two equivalents of py (py = pyridine, C5H5N) leads to the formation of the title compound {Ru}py·C7H8, (II), in high yield by loss of N2. We report here on the structure of the (II), which incorporates two structural type pyridine ligands, i.e. C5H5N and C5H3N(CH2NMe2)2-2,6.
The X-ray diffraction study confirms the general structure of (II) in solution, suggested on the basis of the NMR (1H, 13C{1H}) and IR data of (II) (Fig. 1).
In (II), the RuII centre occupies a distorted octahedral environment, with the three N-donor atoms of the NN'N-ligand in a meridional position. The Cl atoms are forced in the apical positions and are trans-orientated to each other. In general, the Ru—Npy, Ru—NNMe and Ru—Cl distances Ru1—Cl1 [2.3502 (7) Å], Ru1—Cl2 [2.3581 (7) Å], Ru1—N1 [1.962 (2) Å], Ru1—N2 [2.348 (3) Å] and Ru1—N3 [2.251 (3) Å], as well as the angles around the RuII centre Cl1—Ru1—Cl2 [177.19 (3)] and N2—Ru1—N3 [160.57 (9)°] of the {Ru} building block are consistent with those values reported for this type of complex fragment (del Rio et al., 2000). The length of the Ru1—N4 bond of 2.096 (2) Å is elongated when compared to the Ru1—N1 bond, but lies in the range of distances reported for other RuII–pyridine complexes, e.g. [Ru(py)6]2+ with 2.10–2.14 Å (Templeton, 1979). Similar Ru—Npy distances are, e.g., found in [RuCl(py)4(pz)]+ with 2.105 (4) Å (Coe et al., 1995). This relatively short Ru1—N1 distance can best be explained by the imbedding of the RuII centre into the framework of the bis-orthochelating NN'N ligand. The angle N1—Ru1—N4 [178.37 (9)°] resembles the linearity of this array. The planes of the two pyridine ligands are tilted by 54.33 (10)°.