metal-organic compounds
μ-Pyrazine-2,5-dicarboxylato-bis[chlorido(η6-p-cymene)ruthenium(II)] tert-butanol disolvate
aChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, England
*Correspondence e-mail: m.r.j.elsegood@lboro.ac.uk
A new tert-butanol solvate of [{(iPrC6H4Me)RuCl}2{μ-2,5-pyz(COO)2}] (pyz = pyrazine) has been crystallized and structurally characterized. The solvate, [Ru2(C10H14)2(C6H2N2O4)Cl2]·2C4H10O, contains one half-molecule of the ruthenium(II) complex and one molecule of tert-butanol in the The complex molecule lies on an inversion centre with the two chlorides trans. In contrast, the previously reported structure was solvent-free. Similar metric parameters are found between the butanol solvate and the solvent-free form and an intermolecular O—H⋯O hydrogen bond exists between μ-pyrazine-2,5-dicarboxylato-bis[chlorido(η6-p-cymene)ruthenium(II)] and the tert-butanol molecule.
Related literature
The structure of the solvent-free complex has been reported previously (Govindaswamy et al., 2007). One molecule adopts a trans configuration of the two chloro ligands while the second lies on a twofold axis giving the two chloro ligands a cis configuration. For other related literature, see: Cadierno et al. (2002); Carter et al. (1993); Dann et al. (2006); Dorcier et al. (2005); Drommi et al. (1995); Ganter (2003); Gemel et al. (2000); Grote et al. (2004); Ion et al. (2006); Konar et al. (2004); Lahuerta et al. (1988); Ma et al. (2004); Pinto et al. (2004).
Experimental
Crystal data
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Refinement
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Data collection: COLLECT (Hooft, 1998); cell DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Supporting information
10.1107/S1600536808000202/bv2088sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808000202/bv2088Isup2.hkl
Crystals of compound 1 were obtained unexpectedly from the experimental procedure outlined here. Boronic acid (0.004 g, 0.007 mmol) in warm tBuOH (10 ml) was added dropwise to a solution of [{(η6-p-iPrC6H4Me)RuCl}2{µ-2,5-pyz(COO)2}] (0.023 g, 0.0325 mmol) in CH2Cl2 (10 ml) affording an orange-red solution. The solution was stirred at room temperature for 3 h and the volume was concentrated to 2–3 ml. Suitable X-ray quality crystals of 1 were obtained by slow vapour diffusion of diethyl ether into the concentrated CH2Cl2/tBuOH solution.
H atoms were placed in geometric positions (C—H distance = 0.95 Å for aryl H; 0.98 Å for methine, 1.00 Å for methyl H; and 0.84 Å for O—H) using a riding model. Uiso values were set to 1.2Ueq (C) (1.5Ueq (C/O)for methyl H and OH atoms respectively).
Data collection: COLLECT (Hooft, 1998) or APEX2 (Bruker, 2000)?; cell
DENZO (Otwinowski & Minor, 1997) and COLLECT or APEX2 (Bruker, 2000)?; data reduction: DENZO and COLLECT or APEX2 (Bruker, 2000)?; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.[Ru2(C10H14)2(C6H2N2O4)Cl2]·2(C4H10O) | F(000) = 876 |
Mr = 855.80 | Dx = 1.550 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4336 reflections |
a = 9.8483 (2) Å | θ = 2.9–27.5° |
b = 11.3968 (3) Å | µ = 1.01 mm−1 |
c = 16.3448 (3) Å | T = 120 K |
β = 91.465 (2)° | Rod, brown |
V = 1833.93 (7) Å3 | 0.18 × 0.04 × 0.03 mm |
Z = 2 |
Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer | 4195 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 3594 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 4090x4096pixels/62x62mm pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | k = −14→14 |
Tmin = 0.839, Tmax = 0.970 | l = −20→21 |
18492 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0329P)2 + 10.5824P] where P = (Fo2 + 2Fc2)/3 |
4196 reflections | (Δ/σ)max = 0.034 |
215 parameters | Δρmax = 2.78 e Å−3 |
0 restraints | Δρmin = −1.04 e Å−3 |
[Ru2(C10H14)2(C6H2N2O4)Cl2]·2(C4H10O) | V = 1833.93 (7) Å3 |
Mr = 855.80 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.8483 (2) Å | µ = 1.01 mm−1 |
b = 11.3968 (3) Å | T = 120 K |
c = 16.3448 (3) Å | 0.18 × 0.04 × 0.03 mm |
β = 91.465 (2)° |
Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer | 4195 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 3594 reflections with I > 2σ(I) |
Tmin = 0.839, Tmax = 0.970 | Rint = 0.046 |
18492 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0329P)2 + 10.5824P] where P = (Fo2 + 2Fc2)/3 |
4196 reflections | Δρmax = 2.78 e Å−3 |
215 parameters | Δρmin = −1.04 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 | 0.09960 (3) | 0.28799 (3) | 0.037062 (19) | 0.01586 (11) | |
Cl1 | 0.13823 (11) | 0.29072 (9) | −0.10715 (6) | 0.0245 (2) | |
C1 | 0.0607 (4) | 0.3713 (4) | 0.1547 (2) | 0.0199 (8) | |
C2 | 0.1442 (4) | 0.2730 (4) | 0.1682 (2) | 0.0206 (8) | |
H2 | 0.1190 | 0.2153 | 0.2069 | 0.025* | |
C3 | 0.2668 (4) | 0.2590 (4) | 0.1243 (3) | 0.0231 (9) | |
H3A | 0.3213 | 0.1912 | 0.1335 | 0.028* | |
C4 | 0.3085 (4) | 0.3447 (4) | 0.0673 (3) | 0.0236 (9) | |
C5 | 0.2248 (4) | 0.4460 (4) | 0.0561 (3) | 0.0217 (8) | |
H5 | 0.2516 | 0.5056 | 0.0193 | 0.026* | |
C6 | 0.1045 (4) | 0.4591 (4) | 0.0982 (3) | 0.0216 (8) | |
H6 | 0.0506 | 0.5272 | 0.0893 | 0.026* | |
C7 | −0.0741 (5) | 0.3876 (4) | 0.1953 (3) | 0.0281 (10) | |
H7 | −0.1365 | 0.4297 | 0.1560 | 0.034* | |
C8 | −0.0512 (6) | 0.4661 (5) | 0.2700 (3) | 0.0360 (11) | |
H8A | 0.0074 | 0.4256 | 0.3103 | 0.054* | |
H8B | −0.1387 | 0.4839 | 0.2944 | 0.054* | |
H8C | −0.0076 | 0.5393 | 0.2533 | 0.054* | |
C9 | −0.1430 (5) | 0.2730 (5) | 0.2199 (3) | 0.0382 (12) | |
H9A | −0.1494 | 0.2205 | 0.1725 | 0.057* | |
H9B | −0.2344 | 0.2899 | 0.2392 | 0.057* | |
H9C | −0.0894 | 0.2352 | 0.2638 | 0.057* | |
C10 | 0.4356 (5) | 0.3291 (5) | 0.0202 (3) | 0.0363 (12) | |
H10A | 0.5109 | 0.3694 | 0.0487 | 0.054* | |
H10B | 0.4225 | 0.3623 | −0.0347 | 0.054* | |
H10C | 0.4565 | 0.2453 | 0.0159 | 0.054* | |
N1 | 0.0476 (3) | 0.1115 (3) | 0.01791 (19) | 0.0155 (6) | |
C11 | −0.0800 (4) | 0.0943 (3) | −0.0104 (2) | 0.0161 (7) | |
C12 | 0.1276 (4) | 0.0178 (3) | 0.0281 (2) | 0.0177 (8) | |
H12 | 0.2185 | 0.0280 | 0.0478 | 0.021* | |
C13 | −0.1656 (4) | 0.2038 (3) | −0.0213 (2) | 0.0171 (8) | |
O1 | −0.2818 (3) | 0.1959 (3) | −0.0502 (2) | 0.0293 (7) | |
O2 | −0.1073 (3) | 0.2977 (2) | 0.00366 (18) | 0.0205 (6) | |
C14 | −0.5253 (5) | 0.0313 (5) | −0.1783 (3) | 0.0391 (12) | |
C16 | −0.5410 (7) | 0.1587 (6) | −0.2005 (5) | 0.0596 (18) | |
H16A | −0.4918 | 0.1749 | −0.2506 | 0.089* | |
H16B | −0.5041 | 0.2073 | −0.1558 | 0.089* | |
H16C | −0.6375 | 0.1768 | −0.2095 | 0.089* | |
C17 | −0.6231 (8) | 0.0080 (8) | −0.1086 (5) | 0.081 (2) | |
H17A | −0.7153 | 0.0310 | −0.1260 | 0.122* | |
H17B | −0.5948 | 0.0538 | −0.0604 | 0.122* | |
H17C | −0.6218 | −0.0757 | −0.0949 | 0.122* | |
C15 | −0.5355 (14) | −0.0404 (12) | −0.2492 (7) | 0.176 (8) | |
H15A | −0.4682 | −0.0151 | −0.2887 | 0.264* | |
H15B | −0.6268 | −0.0333 | −0.2739 | 0.264* | |
H15C | −0.5184 | −0.1224 | −0.2340 | 0.264* | |
O3 | −0.3929 (4) | 0.0100 (3) | −0.1422 (3) | 0.0438 (10) | |
H3 | −0.3711 | 0.0663 | −0.1114 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01907 (17) | 0.01018 (16) | 0.01823 (17) | 0.00040 (12) | −0.00136 (11) | −0.00046 (12) |
Cl1 | 0.0329 (5) | 0.0211 (5) | 0.0194 (5) | 0.0014 (4) | 0.0014 (4) | −0.0001 (4) |
C1 | 0.0221 (19) | 0.0154 (19) | 0.022 (2) | −0.0005 (15) | −0.0016 (16) | −0.0046 (16) |
C2 | 0.028 (2) | 0.017 (2) | 0.0160 (19) | −0.0009 (16) | −0.0094 (16) | −0.0006 (15) |
C3 | 0.023 (2) | 0.019 (2) | 0.027 (2) | 0.0026 (16) | −0.0100 (17) | −0.0034 (17) |
C4 | 0.023 (2) | 0.023 (2) | 0.025 (2) | −0.0061 (17) | −0.0033 (16) | −0.0053 (17) |
C5 | 0.029 (2) | 0.0116 (18) | 0.025 (2) | −0.0073 (16) | −0.0016 (17) | −0.0005 (16) |
C6 | 0.031 (2) | 0.0112 (19) | 0.022 (2) | −0.0005 (16) | −0.0028 (17) | −0.0057 (16) |
C7 | 0.030 (2) | 0.028 (2) | 0.027 (2) | 0.0027 (19) | 0.0020 (18) | −0.0011 (19) |
C8 | 0.049 (3) | 0.031 (3) | 0.029 (2) | 0.003 (2) | 0.010 (2) | −0.006 (2) |
C9 | 0.032 (3) | 0.039 (3) | 0.044 (3) | −0.004 (2) | 0.012 (2) | −0.005 (2) |
C10 | 0.025 (2) | 0.040 (3) | 0.044 (3) | −0.005 (2) | 0.004 (2) | −0.012 (2) |
N1 | 0.0189 (15) | 0.0120 (15) | 0.0155 (15) | 0.0026 (12) | 0.0002 (12) | 0.0012 (12) |
C11 | 0.0156 (17) | 0.0163 (18) | 0.0163 (18) | 0.0013 (14) | −0.0009 (14) | 0.0015 (15) |
C12 | 0.0193 (18) | 0.0127 (18) | 0.021 (2) | 0.0029 (14) | −0.0025 (15) | 0.0024 (15) |
C13 | 0.0175 (18) | 0.0118 (18) | 0.022 (2) | 0.0012 (14) | −0.0015 (15) | 0.0016 (15) |
O1 | 0.0230 (15) | 0.0192 (16) | 0.045 (2) | 0.0034 (12) | −0.0097 (14) | −0.0013 (14) |
O2 | 0.0194 (14) | 0.0138 (14) | 0.0280 (16) | 0.0032 (11) | −0.0038 (11) | −0.0024 (12) |
C14 | 0.033 (3) | 0.045 (3) | 0.039 (3) | −0.004 (2) | −0.014 (2) | 0.010 (2) |
C16 | 0.048 (4) | 0.052 (4) | 0.077 (5) | 0.013 (3) | −0.018 (3) | 0.006 (3) |
C17 | 0.073 (5) | 0.079 (6) | 0.092 (6) | −0.014 (4) | 0.014 (5) | 0.027 (5) |
C15 | 0.225 (14) | 0.180 (13) | 0.117 (9) | 0.140 (12) | −0.123 (10) | −0.100 (9) |
O3 | 0.0337 (19) | 0.0284 (19) | 0.068 (3) | 0.0077 (15) | −0.0194 (18) | −0.0112 (18) |
Ru1—N1 | 2.097 (3) | C9—H9B | 0.9800 |
Ru1—O2 | 2.099 (3) | C9—H9C | 0.9800 |
Ru1—C3 | 2.176 (4) | C10—H10A | 0.9800 |
Ru1—C2 | 2.184 (4) | C10—H10B | 0.9800 |
Ru1—C1 | 2.187 (4) | C10—H10C | 0.9800 |
Ru1—C6 | 2.191 (4) | N1—C12 | 1.335 (5) |
Ru1—C5 | 2.200 (4) | N1—C11 | 1.343 (5) |
Ru1—C4 | 2.201 (4) | C11—C12i | 1.389 (5) |
Ru1—Cl1 | 2.3975 (11) | C11—C13 | 1.514 (5) |
C1—C2 | 1.404 (6) | C12—C11i | 1.389 (5) |
C1—C6 | 1.435 (6) | C12—H12 | 0.9500 |
C1—C7 | 1.511 (6) | C13—O1 | 1.231 (5) |
C2—C3 | 1.429 (6) | C13—O2 | 1.277 (5) |
C2—H2 | 0.9500 | C14—C15 | 1.419 (10) |
C3—C4 | 1.417 (6) | C14—O3 | 1.438 (6) |
C3—H3A | 0.9500 | C14—C16 | 1.503 (8) |
C4—C5 | 1.428 (6) | C14—C17 | 1.534 (9) |
C4—C10 | 1.496 (7) | C16—H16A | 0.9800 |
C5—C6 | 1.392 (6) | C16—H16B | 0.9800 |
C5—H5 | 0.9500 | C16—H16C | 0.9800 |
C6—H6 | 0.9500 | C17—H17A | 0.9800 |
C7—C8 | 1.525 (6) | C17—H17B | 0.9800 |
C7—C9 | 1.530 (7) | C17—H17C | 0.9800 |
C7—H7 | 1.0000 | C15—H15A | 0.9800 |
C8—H8A | 0.9800 | C15—H15B | 0.9800 |
C8—H8B | 0.9800 | C15—H15C | 0.9800 |
C8—H8C | 0.9800 | O3—H3 | 0.8400 |
C9—H9A | 0.9800 | ||
N1—Ru1—O2 | 77.29 (12) | C5—C6—Ru1 | 71.9 (2) |
N1—Ru1—C3 | 97.48 (14) | C1—C6—Ru1 | 70.7 (2) |
O2—Ru1—C3 | 153.12 (15) | C5—C6—H6 | 119.5 |
N1—Ru1—C2 | 96.53 (14) | C1—C6—H6 | 119.5 |
O2—Ru1—C2 | 115.40 (14) | Ru1—C6—H6 | 130.7 |
C3—Ru1—C2 | 38.27 (17) | C1—C7—C8 | 108.1 (4) |
N1—Ru1—C1 | 120.00 (14) | C1—C7—C9 | 114.3 (4) |
O2—Ru1—C1 | 90.86 (13) | C8—C7—C9 | 110.4 (4) |
C3—Ru1—C1 | 68.67 (16) | C1—C7—H7 | 108.0 |
C2—Ru1—C1 | 37.47 (15) | C8—C7—H7 | 108.0 |
N1—Ru1—C6 | 157.55 (15) | C9—C7—H7 | 108.0 |
O2—Ru1—C6 | 94.69 (14) | C7—C8—H8A | 109.5 |
C3—Ru1—C6 | 80.13 (16) | C7—C8—H8B | 109.5 |
C2—Ru1—C6 | 67.69 (15) | H8A—C8—H8B | 109.5 |
C1—Ru1—C6 | 38.28 (15) | C7—C8—H8C | 109.5 |
N1—Ru1—C5 | 160.06 (15) | H8A—C8—H8C | 109.5 |
O2—Ru1—C5 | 122.04 (14) | H8B—C8—H8C | 109.5 |
C3—Ru1—C5 | 67.62 (16) | C7—C9—H9A | 109.5 |
C2—Ru1—C5 | 80.04 (16) | C7—C9—H9B | 109.5 |
C1—Ru1—C5 | 68.30 (16) | H9A—C9—H9B | 109.5 |
C6—Ru1—C5 | 36.97 (16) | C7—C9—H9C | 109.5 |
N1—Ru1—C4 | 122.58 (15) | H9A—C9—H9C | 109.5 |
O2—Ru1—C4 | 159.86 (14) | H9B—C9—H9C | 109.5 |
C3—Ru1—C4 | 37.78 (17) | C4—C10—H10A | 109.5 |
C2—Ru1—C4 | 68.83 (16) | C4—C10—H10B | 109.5 |
C1—Ru1—C4 | 81.87 (16) | H10A—C10—H10B | 109.5 |
C6—Ru1—C4 | 68.07 (16) | C4—C10—H10C | 109.5 |
C5—Ru1—C4 | 37.87 (16) | H10A—C10—H10C | 109.5 |
N1—Ru1—Cl1 | 84.84 (9) | H10B—C10—H10C | 109.5 |
O2—Ru1—Cl1 | 85.47 (9) | C12—N1—C11 | 118.1 (3) |
C3—Ru1—Cl1 | 120.66 (13) | C12—N1—Ru1 | 127.4 (3) |
C2—Ru1—Cl1 | 158.93 (12) | C11—N1—Ru1 | 114.5 (3) |
C1—Ru1—Cl1 | 153.45 (11) | N1—C11—C12i | 121.0 (4) |
C6—Ru1—Cl1 | 115.75 (12) | N1—C11—C13 | 115.7 (3) |
C5—Ru1—Cl1 | 91.50 (12) | C12i—C11—C13 | 123.3 (3) |
C4—Ru1—Cl1 | 92.66 (12) | N1—C12—C11i | 121.0 (4) |
C2—C1—C6 | 118.2 (4) | N1—C12—H12 | 119.5 |
C2—C1—C7 | 123.1 (4) | C11i—C12—H12 | 119.5 |
C6—C1—C7 | 118.6 (4) | O1—C13—O2 | 126.2 (4) |
C2—C1—Ru1 | 71.2 (2) | O1—C13—C11 | 119.6 (3) |
C6—C1—Ru1 | 71.0 (2) | O2—C13—C11 | 114.2 (3) |
C7—C1—Ru1 | 128.0 (3) | C13—O2—Ru1 | 117.7 (2) |
C1—C2—C3 | 120.6 (4) | C15—C14—O3 | 106.4 (6) |
C1—C2—Ru1 | 71.4 (2) | C15—C14—C16 | 110.8 (7) |
C3—C2—Ru1 | 70.6 (2) | O3—C14—C16 | 110.4 (5) |
C1—C2—H2 | 119.7 | C15—C14—C17 | 118.3 (9) |
C3—C2—H2 | 119.7 | O3—C14—C17 | 104.3 (5) |
Ru1—C2—H2 | 131.2 | C16—C14—C17 | 106.4 (6) |
C4—C3—C2 | 121.1 (4) | C14—C16—H16A | 109.5 |
C4—C3—Ru1 | 72.1 (2) | C14—C16—H16B | 109.5 |
C2—C3—Ru1 | 71.2 (2) | H16A—C16—H16B | 109.5 |
C4—C3—H3A | 119.5 | C14—C16—H16C | 109.5 |
C2—C3—H3A | 119.5 | H16A—C16—H16C | 109.5 |
Ru1—C3—H3A | 129.9 | H16B—C16—H16C | 109.5 |
C3—C4—C5 | 117.7 (4) | C14—C17—H17A | 109.5 |
C3—C4—C10 | 121.1 (4) | C14—C17—H17B | 109.5 |
C5—C4—C10 | 121.2 (4) | H17A—C17—H17B | 109.5 |
C3—C4—Ru1 | 70.2 (2) | C14—C17—H17C | 109.5 |
C5—C4—Ru1 | 71.0 (2) | H17A—C17—H17C | 109.5 |
C10—C4—Ru1 | 129.7 (3) | H17B—C17—H17C | 109.5 |
C6—C5—C4 | 121.3 (4) | C14—C15—H15A | 109.5 |
C6—C5—Ru1 | 71.2 (2) | C14—C15—H15B | 109.5 |
C4—C5—Ru1 | 71.1 (2) | H15A—C15—H15B | 109.5 |
C6—C5—H5 | 119.4 | C14—C15—H15C | 109.5 |
C4—C5—H5 | 119.4 | H15A—C15—H15C | 109.5 |
Ru1—C5—H5 | 131.3 | H15B—C15—H15C | 109.5 |
C5—C6—C1 | 121.1 (4) | C14—O3—H3 | 109.5 |
N1—Ru1—C1—C2 | 57.5 (3) | Cl1—Ru1—C4—C10 | −26.2 (4) |
O2—Ru1—C1—C2 | 133.3 (2) | C3—C4—C5—C6 | −1.5 (6) |
C3—Ru1—C1—C2 | −28.8 (2) | C10—C4—C5—C6 | 178.2 (4) |
C6—Ru1—C1—C2 | −130.2 (4) | Ru1—C4—C5—C6 | 52.6 (4) |
C5—Ru1—C1—C2 | −102.3 (3) | C3—C4—C5—Ru1 | −54.1 (3) |
C4—Ru1—C1—C2 | −65.6 (3) | C10—C4—C5—Ru1 | 125.5 (4) |
Cl1—Ru1—C1—C2 | −145.2 (2) | N1—Ru1—C5—C6 | −147.6 (4) |
N1—Ru1—C1—C6 | −172.3 (2) | O2—Ru1—C5—C6 | 47.9 (3) |
O2—Ru1—C1—C6 | −96.5 (2) | C3—Ru1—C5—C6 | −103.8 (3) |
C3—Ru1—C1—C6 | 101.4 (3) | C2—Ru1—C5—C6 | −66.0 (3) |
C2—Ru1—C1—C6 | 130.2 (4) | C1—Ru1—C5—C6 | −28.8 (2) |
C5—Ru1—C1—C6 | 27.9 (2) | C4—Ru1—C5—C6 | −134.2 (4) |
C4—Ru1—C1—C6 | 64.7 (3) | Cl1—Ru1—C5—C6 | 133.5 (2) |
Cl1—Ru1—C1—C6 | −14.9 (4) | N1—Ru1—C5—C4 | −13.4 (6) |
N1—Ru1—C1—C7 | −60.3 (4) | O2—Ru1—C5—C4 | −178.0 (2) |
O2—Ru1—C1—C7 | 15.5 (4) | C3—Ru1—C5—C4 | 30.3 (3) |
C3—Ru1—C1—C7 | −146.6 (4) | C2—Ru1—C5—C4 | 68.2 (3) |
C2—Ru1—C1—C7 | −117.8 (5) | C1—Ru1—C5—C4 | 105.3 (3) |
C6—Ru1—C1—C7 | 112.0 (5) | C6—Ru1—C5—C4 | 134.2 (4) |
C5—Ru1—C1—C7 | 139.9 (4) | Cl1—Ru1—C5—C4 | −92.4 (2) |
C4—Ru1—C1—C7 | 176.6 (4) | C4—C5—C6—C1 | 0.3 (6) |
Cl1—Ru1—C1—C7 | 97.1 (4) | Ru1—C5—C6—C1 | 52.9 (3) |
C6—C1—C2—C3 | −2.4 (6) | C4—C5—C6—Ru1 | −52.6 (3) |
C7—C1—C2—C3 | 176.3 (4) | C2—C1—C6—C5 | 1.7 (6) |
Ru1—C1—C2—C3 | 52.6 (3) | C7—C1—C6—C5 | −177.0 (4) |
C6—C1—C2—Ru1 | −55.0 (3) | Ru1—C1—C6—C5 | −53.4 (3) |
C7—C1—C2—Ru1 | 123.6 (4) | C2—C1—C6—Ru1 | 55.1 (3) |
N1—Ru1—C2—C1 | −132.7 (2) | C7—C1—C6—Ru1 | −123.6 (4) |
O2—Ru1—C2—C1 | −53.7 (3) | N1—Ru1—C6—C5 | 151.4 (3) |
C3—Ru1—C2—C1 | 133.5 (4) | O2—Ru1—C6—C5 | −140.9 (2) |
C6—Ru1—C2—C1 | 30.7 (2) | C3—Ru1—C6—C5 | 65.7 (3) |
C5—Ru1—C2—C1 | 67.2 (3) | C2—Ru1—C6—C5 | 103.5 (3) |
C4—Ru1—C2—C1 | 104.8 (3) | C1—Ru1—C6—C5 | 133.7 (4) |
Cl1—Ru1—C2—C1 | 134.7 (3) | C4—Ru1—C6—C5 | 28.3 (2) |
N1—Ru1—C2—C3 | 93.8 (2) | Cl1—Ru1—C6—C5 | −53.7 (3) |
O2—Ru1—C2—C3 | 172.8 (2) | N1—Ru1—C6—C1 | 17.7 (5) |
C1—Ru1—C2—C3 | −133.5 (4) | O2—Ru1—C6—C1 | 85.4 (2) |
C6—Ru1—C2—C3 | −102.8 (3) | C3—Ru1—C6—C1 | −68.0 (2) |
C5—Ru1—C2—C3 | −66.3 (3) | C2—Ru1—C6—C1 | −30.1 (2) |
C4—Ru1—C2—C3 | −28.7 (2) | C5—Ru1—C6—C1 | −133.7 (4) |
Cl1—Ru1—C2—C3 | 1.2 (5) | C4—Ru1—C6—C1 | −105.3 (3) |
C1—C2—C3—C4 | 1.2 (6) | Cl1—Ru1—C6—C1 | 172.66 (19) |
Ru1—C2—C3—C4 | 54.2 (3) | C2—C1—C7—C8 | 97.1 (5) |
C1—C2—C3—Ru1 | −53.0 (3) | C6—C1—C7—C8 | −84.3 (5) |
N1—Ru1—C3—C4 | 135.8 (3) | Ru1—C1—C7—C8 | −171.7 (3) |
O2—Ru1—C3—C4 | −147.6 (3) | C2—C1—C7—C9 | −26.2 (6) |
C2—Ru1—C3—C4 | −133.1 (4) | C6—C1—C7—C9 | 152.5 (4) |
C1—Ru1—C3—C4 | −104.8 (3) | Ru1—C1—C7—C9 | 65.0 (5) |
C6—Ru1—C3—C4 | −66.8 (3) | O2—Ru1—N1—C12 | −177.7 (4) |
C5—Ru1—C3—C4 | −30.4 (3) | C3—Ru1—N1—C12 | −24.5 (4) |
Cl1—Ru1—C3—C4 | 47.4 (3) | C2—Ru1—N1—C12 | −63.0 (3) |
N1—Ru1—C3—C2 | −91.1 (2) | C1—Ru1—N1—C12 | −94.1 (4) |
O2—Ru1—C3—C2 | −14.5 (4) | C6—Ru1—N1—C12 | −106.7 (5) |
C1—Ru1—C3—C2 | 28.3 (2) | C5—Ru1—N1—C12 | 15.7 (6) |
C6—Ru1—C3—C2 | 66.3 (3) | C4—Ru1—N1—C12 | 6.0 (4) |
C5—Ru1—C3—C2 | 102.7 (3) | Cl1—Ru1—N1—C12 | 95.8 (3) |
C4—Ru1—C3—C2 | 133.1 (4) | O2—Ru1—N1—C11 | 4.7 (3) |
Cl1—Ru1—C3—C2 | −179.5 (2) | C3—Ru1—N1—C11 | 157.9 (3) |
C2—C3—C4—C5 | 0.8 (6) | C2—Ru1—N1—C11 | 119.3 (3) |
Ru1—C3—C4—C5 | 54.6 (3) | C1—Ru1—N1—C11 | 88.2 (3) |
C2—C3—C4—C10 | −178.9 (4) | C6—Ru1—N1—C11 | 75.6 (5) |
Ru1—C3—C4—C10 | −125.1 (4) | C5—Ru1—N1—C11 | −161.9 (4) |
C2—C3—C4—Ru1 | −53.8 (3) | C4—Ru1—N1—C11 | −171.7 (3) |
N1—Ru1—C4—C3 | −55.1 (3) | Cl1—Ru1—N1—C11 | −81.8 (3) |
O2—Ru1—C4—C3 | 135.3 (4) | C12—N1—C11—C12i | 0.3 (6) |
C2—Ru1—C4—C3 | 29.0 (3) | Ru1—N1—C11—C12i | 178.2 (3) |
C1—Ru1—C4—C3 | 65.4 (3) | C12—N1—C11—C13 | −179.6 (3) |
C6—Ru1—C4—C3 | 102.6 (3) | Ru1—N1—C11—C13 | −1.8 (4) |
C5—Ru1—C4—C3 | 130.3 (4) | C11—N1—C12—C11i | −0.3 (6) |
Cl1—Ru1—C4—C3 | −140.7 (2) | Ru1—N1—C12—C11i | −177.9 (3) |
N1—Ru1—C4—C5 | 174.6 (2) | N1—C11—C13—O1 | 176.9 (4) |
O2—Ru1—C4—C5 | 5.0 (6) | C12i—C11—C13—O1 | −3.0 (6) |
C3—Ru1—C4—C5 | −130.3 (4) | N1—C11—C13—O2 | −4.7 (5) |
C2—Ru1—C4—C5 | −101.3 (3) | C12i—C11—C13—O2 | 175.3 (4) |
C1—Ru1—C4—C5 | −64.9 (3) | O1—C13—O2—Ru1 | −172.8 (4) |
C6—Ru1—C4—C5 | −27.7 (2) | C11—C13—O2—Ru1 | 9.0 (4) |
Cl1—Ru1—C4—C5 | 89.0 (2) | N1—Ru1—O2—C13 | −7.8 (3) |
N1—Ru1—C4—C10 | 59.4 (5) | C3—Ru1—O2—C13 | −89.2 (4) |
O2—Ru1—C4—C10 | −110.3 (5) | C2—Ru1—O2—C13 | −99.1 (3) |
C3—Ru1—C4—C10 | 114.5 (5) | C1—Ru1—O2—C13 | −128.4 (3) |
C2—Ru1—C4—C10 | 143.5 (5) | C6—Ru1—O2—C13 | −166.6 (3) |
C1—Ru1—C4—C10 | 179.9 (5) | C5—Ru1—O2—C13 | 166.9 (3) |
C6—Ru1—C4—C10 | −143.0 (5) | C4—Ru1—O2—C13 | 163.3 (4) |
C5—Ru1—C4—C10 | −115.2 (5) | Cl1—Ru1—O2—C13 | 77.9 (3) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ru2(C10H14)2(C6H2N2O4)Cl2]·2(C4H10O) |
Mr | 855.80 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 9.8483 (2), 11.3968 (3), 16.3448 (3) |
β (°) | 91.465 (2) |
V (Å3) | 1833.93 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.01 |
Crystal size (mm) | 0.18 × 0.04 × 0.03 |
Data collection | |
Diffractometer | Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.839, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18492, 4195, 3594 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.115, 1.06 |
No. of reflections | 4196 |
No. of parameters | 215 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0329P)2 + 10.5824P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.78, −1.04 |
Computer programs: COLLECT (Hooft, 1998) or APEX2 (Bruker, 2000)?, DENZO (Otwinowski & Minor, 1997) and COLLECT or APEX2 (Bruker, 2000)?, DENZO and COLLECT or APEX2 (Bruker, 2000)?, SHELXTL (Sheldrick, 2001) and local programs.
Acknowledgements
The authors acknowledge the Loughborough University Development Fund for the provision of a studentship (to NMSB). The authors are also grateful to the EPSRC National Crystallography Service at the University of Southampton for the data collection.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
There has been considerable interest in the chemistry of areneruthenium(II) complexes for a variety of purposes. These range from their interesting and varied coordination chemistry (Cadierno et al., 2002; Drommi et al., 1995) including DNA binding studies (Dorcier et al., 2005) to applications in areas including supramolecular chemistry, as highly selective receptors and catalysis (Dann et al., 2006; Ganter, 2003; Grote et al., 2004; Ion et al., 2006). These organometallic ruthenium(II) fragments have also been used in the synthesis of chiral half-sandwich compounds (Ganter, 2003; Pinto et al., 2004). Pyrazine polycarboxylic acids are excellent ligands for metal coordination (Konar et al., 2004; Ma et al., 2004). Complexes of ruthenium(II) with pyrazine carboxylic acids are known and their redox behaviour has been studied by voltammetric methods (Govindaswamy et al., 2007). We report here the molecular structure of a new tert-butanol solvate of the ruthenium(II) complex [{(η6-p-iPrC6H4Me)RuCl}2{µ-2,5-pyz(COO)2}]\. tBuOH 1. The solvent free structure, 2, which contains one molecule with a trans configuration of the two chloro ligands and a second molecule with twofold symmetry that has two chloro ligands disposed in a cis configuration, has recently been reported (Govindaswamy et al., 2007).
The molecular structure of 1 is shown in Figure 1 and shows a typical piano-stool geometry at each ruthenium(II) centre with each metal bonded to an η6-p-iPrC6H4Me arene [Ru—Ccentroid 1.6689 (16) Å], a terminal chloride and a dianionic N,O-chelating pyrazine ligand. The Ru—Cl bond length in 1 [2.3975 (11) Å] is slightly shorter than that in the trans isomer [2.408 (5) Å] of 2 yet similar to the cis isomer [2.388 (3) Å, 2.399 (3) Å]. The Ru—O and Ru—N bond distances in 1 [2.099 (3) Å and 2.097 (3) Å respectively] are similar to those in the cis isomer of 2 [2.083 (10)/2.109 (9) Å and 2.102 (7)/2.074 (7) Å respectively] and with those of other related three-legged piano-stool ruthenium(II) complexes (Carter et al., 1993; Gemel et al., 2000; Lahuerta et al., 1988). The N(1)—Ru(1)—O(2) bite angle in 1 [77.29 (12)°] is broadly as expected for this type of five-membered chelating ligand. The η6-p-iPrC6H4Me arene ring is essentially planar with C—C bond lengths in the range 1.392 (6)–1.435 (6) Å. The Ru complex is hydrogen-bonded to a tBuOH molecule through a strong intermolecular O—H···O interaction.
In summary, we have reported the crystal structure of a new tert-butanol solvate form of [{(η6-p-iPrC6H4Me)RuCl}2{µ-2,5-pyz(COO)2}] 1 that displays very similar bond lengths and angles around the ruthenium(II) coordination sphere to complex 2 recently published (Govindaswamy et al., 2007).