The title complexes, [RuCl(C
9H
21N
3)(C
12H
12N
2O
2)]ClO
4·2C
2H
3N, (I), and [Ru(C
9H
21N
3)(C
12H
12N
2O
2)(H
2O)](ClO
4)
2·2H
2O, (II), display similar structures with the Ru atom in a distorted octahedral environment. In the crystal packing of the chloride complex, (I), the Ru complex molecules are held together in pairs through C—H
Cl interactions of the 4,4′-dimethoxy-2,2′-bipyridine and chloride ligands. In the case of the aqua complex, (II), hydrogen bonding affords a tetrameric hydrogen-bonded network. These two structures are the first examples of complexes with the {Ru(1,4,7-trimethyl-1,4,7-triazacyclononane)} motif and an electron-rich substituted 2,2′-bipyridine ligand.
Supporting information
CCDC references: 879452; 879453
For the preparation of (I), [Ru(tmtacn)]Cl3.H2O (100.5 mg, 0.25 mmol;
Neubold et al., 1989), 4,4'-dimethoxy-2,2'-bipyridine (81.3 mg, 0.38 mmol) and Zn/Hg (150 mg) were suspended in H2O (20 ml) and refluxed for 1 h
under an Ar atmosphere. The reactants dissolved slowly to yield a pale-green
solution which along the reaction time became deeply burgundy. At this point
the insolubles were removed from the reaction mixture by filtration and the
solution was concentrated on a rotary evaporator to less than 5 ml. Addition
of NaClO4 (600 mg, 4.90 mmol) induced the precipitation of the product as a
fine powder, which upon standing overnight in the refrigerator was collected
by filtration, washed with chilled water and dried over silica gel. A small
amount of a white material (most probably an excess of the ligand) was removed
with diethyl ether. The deeply colored material was finally dissolved in water
and allowed to evaporate slowly at room temperature to yield 153 mg (80%) of
the product. The material obtained in this way was suitable for X-ray
analysis.
For the preparation of (II), a solution of
[Ru(tmtacn){4,4'-(MeO)2bpy}(H2O)](ClO4)2.2H2O in water originally
intended to be used to grow large single crystals was accidentally
contaminated with NaCl. Full evaporation of the solvent yielded a red
material, which was suspended in acetonitrile and filtered to remove insoluble
inorganic salts. Slow diffusion of diethyl ether yielded red single crystals
that turned out to be compound (II).
In both structures, all the C-bound H atoms were clearly seen in a difference
Fourier map but were repositioned at their expected locations and allowed to
ride, with C—H = 0.93 (aromatic) and 0.97 Å (methylene and methyl). For
the O—H and methyl H atoms, Uiso(H) = 1.5Ueq(parent atom), while
Uiso(H) = 1.2Ueq(parent atom) for all other H atoms.
In (I), in order to make the acetonitrile solvent molecules refinement fully
anisotropic, all their C and N atoms were subjected to a 'rigid bond'
restraint (DELU instruction in SHELXTL; Sheldrick, 2008)), i.e. the
components of the (anisotropic) displacement parameters in the direction of
the corresponding bonds were restrained to be equal within an effective
standard uncertainty of 0.02 Å. In addition, within this same set of atoms,
those closer than 1.7 Å were restrained with an effective standard
uncertainty of 0.04 Å to have the same Uij components (SIMU
instruction).
In (II), coordinated water O atom H atoms were located in a difference Fourier
map and accordingly positionated; while the H atoms of the water solvent
molecules were not located in the difference map but were geometrically
positionated using the CALC-OH algorithm (Nardelli, 1999) for further
refinement. H atoms attached to O atoms were refined with restrained O—H
distances of 0.84 (2) Å and the water H···H distances were restrained to
1.30 (4) Å.
The refinement of the H atoms of the water solvent molecules in (II) required
the inclusion of some constraints to avoid convergence to a nonreasonable
water molecules H···H intermolecular distances. The H···O intermolecular
shortest contact distances were constrained to 2.30 (2) Å. In this way,
refinement converged to a reasonable hydrogen-bonded network structure
although no significant improvement in the overall statistics was achieved.
For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: DIAMOND (Crystal Impact, 1999).
(I) Chlorido(4,4'-dimethoxy-2,2'-bipyridine)(1,4,7-trimethyl-1,4,7-
triazacyclononane)ruthenium(II) perchlorate acetonitrile disolvate
top
Crystal data top
[RuCl(C9H21N3)(C12H12N2O2)]ClO4·2C2H3N | F(000) = 2912 |
Mr = 705.60 | Dx = 1.510 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4271 reflections |
a = 17.8073 (9) Å | θ = 3.6–28.9° |
b = 12.3587 (7) Å | µ = 0.73 mm−1 |
c = 28.5276 (18) Å | T = 298 K |
β = 98.603 (6)° | Block, red |
V = 6207.6 (6) Å3 | 0.38 × 0.28 × 0.12 mm |
Z = 8 | |
Data collection top
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 6674 independent reflections |
Radiation source: fine-focus sealed tube | 3528 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 16.1158 pixels mm-1 | θmax = 27.0°, θmin = 3.6° |
ω scans | h = −22→19 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −15→14 |
Tmin = 0.816, Tmax = 1.000 | l = −36→36 |
13768 measured reflections | |
Refinement top
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 0.87 | w = 1/[σ2(Fo2) + (0.0612P)2] where P = (Fo2 + 2Fc2)/3 |
6674 reflections | (Δ/σ)max = 0.001 |
372 parameters | Δρmax = 0.59 e Å−3 |
30 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
[RuCl(C9H21N3)(C12H12N2O2)]ClO4·2C2H3N | V = 6207.6 (6) Å3 |
Mr = 705.60 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.8073 (9) Å | µ = 0.73 mm−1 |
b = 12.3587 (7) Å | T = 298 K |
c = 28.5276 (18) Å | 0.38 × 0.28 × 0.12 mm |
β = 98.603 (6)° | |
Data collection top
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 6674 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 3528 reflections with I > 2σ(I) |
Tmin = 0.816, Tmax = 1.000 | Rint = 0.051 |
13768 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 30 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.59 e Å−3 |
6674 reflections | Δρmin = −0.42 e Å−3 |
372 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 | x | y | z | Uiso*/Ueq | |
C1 | 0.0616 (2) | 0.2894 (3) | 0.34915 (16) | 0.0531 (12) | |
H1 | 0.0999 | 0.2523 | 0.3684 | 0.064* | |
C2 | 0.0029 (3) | 0.2296 (3) | 0.32605 (16) | 0.0560 (12) | |
H2 | 0.0016 | 0.1550 | 0.3300 | 0.067* | |
C3 | −0.0539 (3) | 0.2815 (3) | 0.29696 (15) | 0.0515 (11) | |
C4 | −0.0511 (2) | 0.3937 (3) | 0.29453 (13) | 0.0455 (10) | |
H4 | −0.0899 | 0.4315 | 0.2760 | 0.055* | |
C5 | 0.0099 (2) | 0.4497 (3) | 0.31985 (13) | 0.0369 (9) | |
C6 | 0.0120 (2) | 0.5683 (3) | 0.32329 (13) | 0.0393 (10) | |
C7 | −0.0443 (2) | 0.6340 (3) | 0.29916 (13) | 0.0433 (10) | |
H7 | −0.0824 | 0.6045 | 0.2770 | 0.052* | |
C8 | −0.0431 (3) | 0.7438 (3) | 0.30847 (15) | 0.0507 (11) | |
C9 | 0.0132 (3) | 0.7828 (3) | 0.34251 (15) | 0.0555 (12) | |
H9 | 0.0139 | 0.8555 | 0.3510 | 0.067* | |
C10 | 0.0683 (2) | 0.7141 (3) | 0.36382 (15) | 0.0539 (12) | |
H10 | 0.1066 | 0.7430 | 0.3860 | 0.065* | |
C11 | −0.1165 (3) | 0.1208 (4) | 0.2679 (2) | 0.0952 (19) | |
H11A | −0.1628 | 0.0981 | 0.2488 | 0.143* | |
H11B | −0.1137 | 0.0903 | 0.2991 | 0.143* | |
H11C | −0.0739 | 0.0965 | 0.2537 | 0.143* | |
C12 | −0.1512 (3) | 0.7835 (4) | 0.25109 (18) | 0.0826 (17) | |
H12A | −0.1819 | 0.8444 | 0.2396 | 0.124* | |
H12B | −0.1822 | 0.7300 | 0.2633 | 0.124* | |
H12C | −0.1286 | 0.7529 | 0.2256 | 0.124* | |
C13 | 0.3192 (2) | 0.4378 (3) | 0.38647 (16) | 0.0539 (11) | |
H13A | 0.3217 | 0.4548 | 0.3536 | 0.065* | |
H13B | 0.3625 | 0.3927 | 0.3982 | 0.065* | |
C14 | 0.3227 (3) | 0.5407 (4) | 0.41482 (17) | 0.0630 (13) | |
H14A | 0.3317 | 0.5235 | 0.4484 | 0.076* | |
H14B | 0.3647 | 0.5846 | 0.4077 | 0.076* | |
C15 | 0.2267 (3) | 0.6424 (3) | 0.44868 (15) | 0.0586 (13) | |
H15A | 0.1861 | 0.6948 | 0.4415 | 0.070* | |
H15B | 0.2693 | 0.6783 | 0.4677 | 0.070* | |
C16 | 0.2001 (3) | 0.5504 (4) | 0.47651 (15) | 0.0613 (12) | |
H16A | 0.1742 | 0.5795 | 0.5014 | 0.074* | |
H16B | 0.2438 | 0.5098 | 0.4915 | 0.074* | |
C17 | 0.1716 (3) | 0.3608 (3) | 0.45568 (16) | 0.0602 (13) | |
H17A | 0.1323 | 0.3126 | 0.4404 | 0.072* | |
H17B | 0.1772 | 0.3477 | 0.4896 | 0.072* | |
C18 | 0.2452 (3) | 0.3352 (3) | 0.43826 (15) | 0.0550 (12) | |
H18A | 0.2868 | 0.3659 | 0.4601 | 0.066* | |
H18B | 0.2521 | 0.2574 | 0.4381 | 0.066* | |
C19 | 0.0691 (3) | 0.4899 (3) | 0.45520 (16) | 0.0593 (11) | |
H19A | 0.0359 | 0.4429 | 0.4349 | 0.089* | |
H19B | 0.0539 | 0.5637 | 0.4491 | 0.089* | |
H19C | 0.0664 | 0.4726 | 0.4877 | 0.089* | |
C20 | 0.2469 (3) | 0.2871 (3) | 0.35512 (16) | 0.0631 (13) | |
H20A | 0.2019 | 0.2446 | 0.3557 | 0.095* | |
H20B | 0.2909 | 0.2424 | 0.3636 | 0.095* | |
H20C | 0.2469 | 0.3157 | 0.3238 | 0.095* | |
C21 | 0.2634 (3) | 0.6967 (3) | 0.37392 (17) | 0.0642 (14) | |
H21A | 0.2782 | 0.6716 | 0.3448 | 0.096* | |
H21B | 0.3029 | 0.7412 | 0.3905 | 0.096* | |
H21C | 0.2175 | 0.7382 | 0.3671 | 0.096* | |
Cl1 | 0.18827 (6) | 0.51560 (8) | 0.29331 (4) | 0.0539 (3) | |
N1 | 0.06854 (19) | 0.3979 (2) | 0.34630 (11) | 0.0425 (8) | |
N2 | 0.07061 (18) | 0.6068 (2) | 0.35457 (11) | 0.0395 (8) | |
N3 | 0.25028 (19) | 0.6032 (3) | 0.40371 (12) | 0.0472 (9) | |
N4 | 0.24841 (19) | 0.3781 (2) | 0.38968 (12) | 0.0444 (8) | |
N5 | 0.14719 (19) | 0.4754 (2) | 0.44591 (11) | 0.0468 (8) | |
O1 | −0.11519 (19) | 0.2343 (2) | 0.27114 (12) | 0.0749 (10) | |
O2 | −0.09296 (18) | 0.8177 (2) | 0.28774 (11) | 0.0666 (9) | |
Ru1 | 0.159148 (17) | 0.49683 (2) | 0.373612 (10) | 0.03929 (12) | |
Cl2 | 0.38146 (8) | 0.51358 (9) | 0.08124 (5) | 0.0689 (4) | |
O3 | 0.4606 (3) | 0.5200 (3) | 0.08513 (19) | 0.1126 (15) | |
O4 | 0.3527 (3) | 0.4139 (3) | 0.06576 (16) | 0.1195 (17) | |
O5 | 0.3674 (4) | 0.5277 (4) | 0.1293 (2) | 0.153 (2) | |
O6 | 0.3457 (3) | 0.5964 (3) | 0.05493 (18) | 0.135 (2) | |
C22 | 0.3146 (6) | −0.0184 (5) | 0.3627 (4) | 0.176 (5) | |
H22A | 0.3033 | 0.0192 | 0.3331 | 0.264* | |
H22B | 0.2681 | −0.0395 | 0.3734 | 0.264* | |
H22C | 0.3442 | −0.0817 | 0.3586 | 0.264* | |
C23 | 0.3561 (6) | 0.0504 (7) | 0.3967 (4) | 0.112 (3) | |
N7 | 0.3883 (5) | 0.1126 (7) | 0.4209 (3) | 0.148 (3) | |
C24 | 0.4845 (4) | 0.6830 (6) | −0.0138 (2) | 0.122 (2) | |
H24A | 0.4600 | 0.7326 | −0.0371 | 0.183* | |
H24B | 0.4471 | 0.6498 | 0.0025 | 0.183* | |
H24C | 0.5103 | 0.6283 | −0.0292 | 0.183* | |
C25 | 0.5374 (4) | 0.7394 (5) | 0.0189 (3) | 0.094 (2) | |
N8 | 0.5795 (4) | 0.7861 (5) | 0.0441 (3) | 0.143 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.051 (3) | 0.037 (2) | 0.068 (3) | 0.001 (2) | −0.002 (2) | 0.004 (2) |
C2 | 0.065 (3) | 0.034 (2) | 0.069 (3) | −0.013 (2) | 0.007 (3) | −0.002 (2) |
C3 | 0.049 (3) | 0.052 (3) | 0.053 (3) | −0.012 (2) | 0.006 (2) | −0.008 (2) |
C4 | 0.043 (3) | 0.053 (2) | 0.039 (2) | −0.003 (2) | 0.0003 (19) | −0.0036 (19) |
C5 | 0.036 (2) | 0.041 (2) | 0.035 (2) | −0.0046 (19) | 0.0082 (18) | 0.0011 (17) |
C6 | 0.046 (3) | 0.037 (2) | 0.033 (2) | −0.0012 (19) | −0.0015 (18) | 0.0023 (16) |
C7 | 0.041 (3) | 0.046 (2) | 0.041 (2) | 0.003 (2) | 0.0015 (19) | −0.0035 (18) |
C8 | 0.059 (3) | 0.044 (2) | 0.047 (3) | 0.006 (2) | −0.001 (2) | 0.0027 (19) |
C9 | 0.062 (3) | 0.036 (2) | 0.063 (3) | 0.003 (2) | −0.007 (2) | −0.006 (2) |
C10 | 0.052 (3) | 0.047 (2) | 0.056 (3) | 0.001 (2) | −0.012 (2) | −0.013 (2) |
C11 | 0.098 (5) | 0.073 (3) | 0.111 (5) | −0.040 (3) | 0.004 (4) | −0.016 (3) |
C12 | 0.092 (4) | 0.079 (3) | 0.068 (3) | 0.026 (3) | −0.018 (3) | −0.004 (3) |
C13 | 0.044 (3) | 0.056 (3) | 0.061 (3) | 0.002 (2) | 0.002 (2) | 0.002 (2) |
C14 | 0.046 (3) | 0.064 (3) | 0.072 (3) | −0.003 (2) | −0.011 (2) | −0.006 (2) |
C15 | 0.068 (3) | 0.049 (2) | 0.051 (3) | 0.002 (2) | −0.016 (2) | −0.013 (2) |
C16 | 0.060 (3) | 0.073 (3) | 0.048 (3) | 0.000 (3) | −0.001 (2) | −0.006 (2) |
C17 | 0.064 (3) | 0.056 (3) | 0.058 (3) | 0.003 (2) | 0.003 (2) | 0.017 (2) |
C18 | 0.061 (3) | 0.050 (2) | 0.050 (3) | 0.007 (2) | −0.006 (2) | 0.011 (2) |
C19 | 0.048 (3) | 0.075 (3) | 0.057 (3) | 0.008 (3) | 0.016 (2) | 0.005 (2) |
C20 | 0.065 (3) | 0.057 (3) | 0.065 (3) | 0.017 (2) | 0.005 (2) | −0.006 (2) |
C21 | 0.065 (3) | 0.052 (2) | 0.071 (3) | −0.017 (2) | −0.004 (3) | 0.004 (2) |
Cl1 | 0.0534 (6) | 0.0642 (7) | 0.0413 (5) | −0.0034 (5) | −0.0026 (4) | 0.0033 (5) |
N1 | 0.044 (2) | 0.0386 (17) | 0.044 (2) | −0.0008 (16) | 0.0026 (16) | −0.0052 (15) |
N2 | 0.040 (2) | 0.0362 (17) | 0.0403 (19) | −0.0010 (15) | −0.0014 (15) | 0.0001 (14) |
N3 | 0.044 (2) | 0.0472 (19) | 0.048 (2) | −0.0034 (16) | −0.0017 (17) | −0.0044 (16) |
N4 | 0.042 (2) | 0.0391 (17) | 0.049 (2) | 0.0006 (16) | −0.0014 (16) | 0.0027 (15) |
N5 | 0.044 (2) | 0.054 (2) | 0.0394 (18) | −0.0021 (16) | −0.0038 (15) | 0.0037 (15) |
O1 | 0.071 (2) | 0.062 (2) | 0.086 (2) | −0.0270 (18) | −0.0068 (19) | −0.0165 (17) |
O2 | 0.067 (2) | 0.0535 (18) | 0.071 (2) | 0.0199 (16) | −0.0182 (17) | −0.0049 (15) |
Ru1 | 0.03942 (18) | 0.03668 (18) | 0.03895 (17) | −0.00016 (16) | −0.00329 (12) | −0.00029 (15) |
Cl2 | 0.0714 (9) | 0.0486 (7) | 0.0814 (9) | 0.0038 (6) | −0.0056 (7) | 0.0024 (6) |
O3 | 0.073 (3) | 0.098 (3) | 0.162 (5) | 0.001 (2) | 0.002 (3) | 0.003 (3) |
O4 | 0.128 (4) | 0.0465 (19) | 0.165 (4) | −0.002 (2) | −0.041 (3) | −0.009 (2) |
O5 | 0.153 (5) | 0.179 (5) | 0.130 (5) | −0.009 (4) | 0.031 (4) | −0.021 (4) |
O6 | 0.138 (4) | 0.060 (2) | 0.184 (5) | 0.016 (2) | −0.052 (3) | 0.033 (3) |
C22 | 0.186 (10) | 0.087 (5) | 0.292 (13) | −0.020 (5) | 0.157 (9) | −0.037 (6) |
C23 | 0.129 (9) | 0.091 (6) | 0.131 (8) | 0.050 (5) | 0.064 (6) | 0.051 (5) |
N7 | 0.138 (7) | 0.194 (8) | 0.112 (6) | 0.067 (6) | 0.017 (5) | 0.039 (5) |
C24 | 0.133 (7) | 0.127 (6) | 0.111 (6) | −0.024 (5) | 0.033 (4) | −0.012 (4) |
C25 | 0.081 (5) | 0.077 (4) | 0.121 (6) | 0.024 (4) | 0.010 (4) | 0.028 (4) |
N8 | 0.105 (5) | 0.107 (5) | 0.199 (8) | 0.006 (4) | −0.033 (5) | 0.027 (4) |
Geometric parameters (Å, º) top
C1—N1 | 1.350 (5) | C16—H16A | 0.9700 |
C1—C2 | 1.366 (5) | C16—H16B | 0.9700 |
C1—H1 | 0.9300 | C17—N5 | 1.496 (5) |
C2—C3 | 1.367 (6) | C17—C18 | 1.504 (6) |
C2—H2 | 0.9300 | C17—H17A | 0.9700 |
C3—O1 | 1.355 (5) | C17—H17B | 0.9700 |
C3—C4 | 1.390 (5) | C18—N4 | 1.493 (5) |
C4—C5 | 1.395 (5) | C18—H18A | 0.9700 |
C4—H4 | 0.9300 | C18—H18B | 0.9700 |
C5—N1 | 1.354 (5) | C19—N5 | 1.465 (5) |
C5—C6 | 1.469 (5) | C19—H19A | 0.9600 |
C6—N2 | 1.355 (4) | C19—H19B | 0.9600 |
C6—C7 | 1.390 (5) | C19—H19C | 0.9600 |
C7—C8 | 1.381 (5) | C20—N4 | 1.493 (5) |
C7—H7 | 0.9300 | C20—H20A | 0.9600 |
C8—O2 | 1.347 (4) | C20—H20B | 0.9600 |
C8—C9 | 1.376 (5) | C20—H20C | 0.9600 |
C9—C10 | 1.369 (5) | C21—N3 | 1.473 (5) |
C9—H9 | 0.9300 | C21—H21A | 0.9600 |
C10—N2 | 1.354 (4) | C21—H21B | 0.9600 |
C10—H10 | 0.9300 | C21—H21C | 0.9600 |
C11—O1 | 1.405 (5) | Cl1—Ru1 | 2.4343 (11) |
C11—H11A | 0.9600 | N1—Ru1 | 2.081 (3) |
C11—H11B | 0.9600 | N2—Ru1 | 2.091 (3) |
C11—H11C | 0.9600 | N3—Ru1 | 2.164 (3) |
C12—O2 | 1.422 (5) | N4—Ru1 | 2.161 (3) |
C12—H12A | 0.9600 | N5—Ru1 | 2.121 (3) |
C12—H12B | 0.9600 | Cl2—O6 | 1.369 (3) |
C12—H12C | 0.9600 | Cl2—O4 | 1.381 (3) |
C13—N4 | 1.474 (5) | Cl2—O3 | 1.399 (4) |
C13—C14 | 1.503 (6) | Cl2—O5 | 1.440 (6) |
C13—H13A | 0.9700 | C22—C23 | 1.413 (12) |
C13—H13B | 0.9700 | C22—H22A | 0.9600 |
C14—N3 | 1.496 (5) | C22—H22B | 0.9600 |
C14—H14A | 0.9700 | C22—H22C | 0.9600 |
C14—H14B | 0.9700 | C23—N7 | 1.129 (10) |
C15—N3 | 1.489 (5) | C24—C25 | 1.407 (9) |
C15—C16 | 1.504 (6) | C24—H24A | 0.9600 |
C15—H15A | 0.9700 | C24—H24B | 0.9600 |
C15—H15B | 0.9700 | C24—H24C | 0.9600 |
C16—N5 | 1.504 (5) | C25—N8 | 1.120 (8) |
| | | |
C4···C4i | 3.339 (5) | | |
| | | |
N1—C1—C2 | 125.3 (4) | N5—C19—H19B | 109.5 |
N1—C1—H1 | 117.3 | H19A—C19—H19B | 109.5 |
C2—C1—H1 | 117.3 | N5—C19—H19C | 109.5 |
C1—C2—C3 | 118.8 (4) | H19A—C19—H19C | 109.5 |
C1—C2—H2 | 120.6 | H19B—C19—H19C | 109.5 |
C3—C2—H2 | 120.6 | N4—C20—H20A | 109.5 |
O1—C3—C2 | 126.2 (4) | N4—C20—H20B | 109.5 |
O1—C3—C4 | 115.8 (4) | H20A—C20—H20B | 109.5 |
C2—C3—C4 | 118.0 (4) | N4—C20—H20C | 109.5 |
C3—C4—C5 | 120.0 (4) | H20A—C20—H20C | 109.5 |
C3—C4—H4 | 120.0 | H20B—C20—H20C | 109.5 |
C5—C4—H4 | 120.0 | N3—C21—H21A | 109.5 |
N1—C5—C4 | 122.0 (3) | N3—C21—H21B | 109.5 |
N1—C5—C6 | 115.2 (3) | H21A—C21—H21B | 109.5 |
C4—C5—C6 | 122.6 (4) | N3—C21—H21C | 109.5 |
N2—C6—C7 | 123.3 (3) | H21A—C21—H21C | 109.5 |
N2—C6—C5 | 113.8 (3) | H21B—C21—H21C | 109.5 |
C7—C6—C5 | 122.8 (3) | C1—N1—C5 | 115.7 (3) |
C8—C7—C6 | 119.3 (4) | C1—N1—Ru1 | 129.4 (3) |
C8—C7—H7 | 120.4 | C5—N1—Ru1 | 114.9 (2) |
C6—C7—H7 | 120.4 | C10—N2—C6 | 115.5 (3) |
O2—C8—C9 | 115.8 (3) | C10—N2—Ru1 | 129.0 (3) |
O2—C8—C7 | 126.2 (4) | C6—N2—Ru1 | 114.8 (2) |
C9—C8—C7 | 118.0 (4) | C21—N3—C15 | 109.4 (3) |
C10—C9—C8 | 119.6 (4) | C21—N3—C14 | 108.8 (4) |
C10—C9—H9 | 120.2 | C15—N3—C14 | 109.3 (3) |
C8—C9—H9 | 120.2 | C21—N3—Ru1 | 114.9 (2) |
N2—C10—C9 | 124.1 (4) | C15—N3—Ru1 | 104.4 (3) |
N2—C10—H10 | 117.9 | C14—N3—Ru1 | 110.0 (2) |
C9—C10—H10 | 117.9 | C13—N4—C18 | 112.8 (3) |
O1—C11—H11A | 109.5 | C13—N4—C20 | 105.5 (3) |
O1—C11—H11B | 109.5 | C18—N4—C20 | 110.3 (3) |
H11A—C11—H11B | 109.5 | C13—N4—Ru1 | 104.8 (2) |
O1—C11—H11C | 109.5 | C18—N4—Ru1 | 108.0 (3) |
H11A—C11—H11C | 109.5 | C20—N4—Ru1 | 115.5 (2) |
H11B—C11—H11C | 109.5 | C19—N5—C17 | 109.8 (3) |
O2—C12—H12A | 109.5 | C19—N5—C16 | 110.4 (3) |
O2—C12—H12B | 109.5 | C17—N5—C16 | 109.7 (3) |
H12A—C12—H12B | 109.5 | C19—N5—Ru1 | 113.4 (2) |
O2—C12—H12C | 109.5 | C17—N5—Ru1 | 103.3 (2) |
H12A—C12—H12C | 109.5 | C16—N5—Ru1 | 110.0 (3) |
H12B—C12—H12C | 109.5 | C3—O1—C11 | 118.0 (4) |
N4—C13—C14 | 110.9 (4) | C8—O2—C12 | 118.7 (3) |
N4—C13—H13A | 109.5 | N1—Ru1—N2 | 76.86 (12) |
C14—C13—H13A | 109.5 | N1—Ru1—N5 | 96.07 (12) |
N4—C13—H13B | 109.5 | N2—Ru1—N5 | 98.76 (13) |
C14—C13—H13B | 109.5 | N1—Ru1—N4 | 100.65 (12) |
H13A—C13—H13B | 108.0 | N2—Ru1—N4 | 176.76 (11) |
N3—C14—C13 | 111.0 (3) | N5—Ru1—N4 | 83.50 (13) |
N3—C14—H14A | 109.4 | N1—Ru1—N3 | 177.62 (13) |
C13—C14—H14A | 109.4 | N2—Ru1—N3 | 101.51 (12) |
N3—C14—H14B | 109.4 | N5—Ru1—N3 | 82.44 (13) |
C13—C14—H14B | 109.4 | N4—Ru1—N3 | 81.05 (12) |
H14A—C14—H14B | 108.0 | N1—Ru1—Cl1 | 88.06 (9) |
N3—C15—C16 | 111.2 (3) | N2—Ru1—Cl1 | 87.25 (9) |
N3—C15—H15A | 109.4 | N5—Ru1—Cl1 | 173.35 (9) |
C16—C15—H15A | 109.4 | N4—Ru1—Cl1 | 90.62 (10) |
N3—C15—H15B | 109.4 | N3—Ru1—Cl1 | 93.60 (10) |
C16—C15—H15B | 109.4 | O6—Cl2—O4 | 111.8 (3) |
H15A—C15—H15B | 108.0 | O6—Cl2—O3 | 112.4 (3) |
C15—C16—N5 | 112.3 (3) | O4—Cl2—O3 | 113.4 (3) |
C15—C16—H16A | 109.1 | O6—Cl2—O5 | 107.4 (3) |
N5—C16—H16A | 109.1 | O4—Cl2—O5 | 107.7 (3) |
C15—C16—H16B | 109.1 | O3—Cl2—O5 | 103.5 (3) |
N5—C16—H16B | 109.1 | C23—C22—H22A | 109.5 |
H16A—C16—H16B | 107.9 | C23—C22—H22B | 109.5 |
N5—C17—C18 | 112.3 (4) | H22A—C22—H22B | 109.5 |
N5—C17—H17A | 109.1 | C23—C22—H22C | 109.5 |
C18—C17—H17A | 109.1 | H22A—C22—H22C | 109.5 |
N5—C17—H17B | 109.1 | H22B—C22—H22C | 109.5 |
C18—C17—H17B | 109.1 | N7—C23—C22 | 173.7 (10) |
H17A—C17—H17B | 107.9 | C25—C24—H24A | 109.5 |
N4—C18—C17 | 112.9 (3) | C25—C24—H24B | 109.5 |
N4—C18—H18A | 109.0 | H24A—C24—H24B | 109.5 |
C17—C18—H18A | 109.0 | C25—C24—H24C | 109.5 |
N4—C18—H18B | 109.0 | H24A—C24—H24C | 109.5 |
C17—C18—H18B | 109.0 | H24B—C24—H24C | 109.5 |
H18A—C18—H18B | 107.8 | N8—C25—C24 | 178.3 (9) |
N5—C19—H19A | 109.5 | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4i—H4i···Cl1 | 0.93 | 2.65 | 3.562 (4) | 167 |
C7i—H7i···Cl1 | 0.93 | 2.77 | 3.695 (4) | 176 |
Symmetry code: (i) −x, y, −z+1/2. |
(II) aqua(4,4'-dimethoxy-2,2'-bipyridine)(1,4,7-trimethyl-1,4,7-
triazacyclononane)ruthenium(II) bis(perchlorate) dihydrate
top
Crystal data top
[Ru(C9H21N3)(C12H12N2O2)(H2O)](ClO4)2·2H2O | Z = 2 |
Mr = 741.54 | F(000) = 764 |
Triclinic, P1 | Dx = 1.656 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.1705 (6) Å | Cell parameters from 4349 reflections |
b = 10.3825 (11) Å | θ = 3.5–29.0° |
c = 18.1967 (15) Å | µ = 0.78 mm−1 |
α = 92.464 (7)° | T = 298 K |
β = 96.740 (7)° | Plate, red |
γ = 103.386 (8)° | 0.30 × 0.12 × 0.05 mm |
V = 1487.4 (2) Å3 | |
Data collection top
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 6429 independent reflections |
Radiation source: fine-focus sealed tube | 4889 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 16.1 pixels mm-1 | θmax = 27.0°, θmin = 3.5° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −13→13 |
Tmin = 0.946, Tmax = 1.000 | l = −23→23 |
18945 measured reflections | |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0702P)2] where P = (Fo2 + 2Fc2)/3 |
6429 reflections | (Δ/σ)max = 0.001 |
397 parameters | Δρmax = 1.17 e Å−3 |
11 restraints | Δρmin = −1.00 e Å−3 |
Crystal data top
[Ru(C9H21N3)(C12H12N2O2)(H2O)](ClO4)2·2H2O | γ = 103.386 (8)° |
Mr = 741.54 | V = 1487.4 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1705 (6) Å | Mo Kα radiation |
b = 10.3825 (11) Å | µ = 0.78 mm−1 |
c = 18.1967 (15) Å | T = 298 K |
α = 92.464 (7)° | 0.30 × 0.12 × 0.05 mm |
β = 96.740 (7)° | |
Data collection top
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 6429 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 4889 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 1.000 | Rint = 0.078 |
18945 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 11 restraints |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.17 e Å−3 |
6429 reflections | Δρmin = −1.00 e Å−3 |
397 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | x | y | z | Uiso*/Ueq | |
C1 | 0.4941 (6) | 0.0962 (5) | 0.3600 (2) | 0.0460 (11) | |
H1 | 0.4488 | 0.1349 | 0.3973 | 0.055* | |
C2 | 0.5790 (6) | 0.0016 (5) | 0.3792 (2) | 0.0478 (11) | |
H2 | 0.5880 | −0.0243 | 0.4275 | 0.057* | |
C3 | 0.6512 (5) | −0.0547 (4) | 0.3254 (2) | 0.0407 (10) | |
C4 | 0.6318 (5) | −0.0123 (4) | 0.2541 (2) | 0.0398 (10) | |
H4 | 0.6765 | −0.0501 | 0.2162 | 0.048* | |
C5 | 0.5477 (5) | 0.0841 (4) | 0.2396 (2) | 0.0335 (9) | |
C6 | 0.5457 (5) | 0.1498 (4) | 0.1693 (2) | 0.0360 (9) | |
C7 | 0.6255 (6) | 0.1133 (5) | 0.1121 (2) | 0.0428 (10) | |
H7 | 0.6698 | 0.0385 | 0.1143 | 0.051* | |
C8 | 0.6394 (6) | 0.1890 (5) | 0.0509 (2) | 0.0472 (12) | |
C9 | 0.5732 (6) | 0.2980 (5) | 0.0500 (2) | 0.0506 (12) | |
H9 | 0.5838 | 0.3526 | 0.0108 | 0.061* | |
C10 | 0.4904 (6) | 0.3260 (5) | 0.1081 (2) | 0.0507 (12) | |
H10 | 0.4438 | 0.3997 | 0.1062 | 0.061* | |
C11 | 0.7396 (9) | 0.2241 (7) | −0.0666 (3) | 0.088 (2) | |
H11A | 0.7970 | 0.1833 | −0.1008 | 0.133* | |
H11B | 0.8050 | 0.3123 | −0.0510 | 0.133* | |
H11C | 0.6299 | 0.2279 | −0.0906 | 0.133* | |
C12 | 0.7763 (7) | −0.1812 (5) | 0.4119 (3) | 0.0584 (14) | |
H12A | 0.8412 | −0.2475 | 0.4130 | 0.088* | |
H12B | 0.6714 | −0.2151 | 0.4312 | 0.088* | |
H12C | 0.8398 | −0.1032 | 0.4418 | 0.088* | |
C13 | 0.0079 (6) | 0.2969 (6) | 0.3046 (3) | 0.0696 (18) | |
H13A | −0.0640 | 0.2177 | 0.2773 | 0.084* | |
H13B | −0.0528 | 0.3221 | 0.3435 | 0.084* | |
C14 | 0.0349 (6) | 0.4015 (6) | 0.2552 (3) | 0.0670 (17) | |
H14A | 0.0625 | 0.4861 | 0.2841 | 0.080* | |
H14B | −0.0699 | 0.3960 | 0.2228 | 0.080* | |
C15 | 0.2914 (6) | 0.5298 (5) | 0.2137 (3) | 0.0540 (12) | |
H15A | 0.3565 | 0.5344 | 0.1722 | 0.065* | |
H15B | 0.2270 | 0.5973 | 0.2095 | 0.065* | |
C16 | 0.4090 (7) | 0.5586 (5) | 0.2832 (3) | 0.0600 (14) | |
H16A | 0.3539 | 0.5945 | 0.3209 | 0.072* | |
H16B | 0.5078 | 0.6265 | 0.2754 | 0.072* | |
C17 | 0.4356 (6) | 0.4262 (6) | 0.3899 (2) | 0.0562 (13) | |
H17A | 0.5042 | 0.3701 | 0.4124 | 0.067* | |
H17B | 0.4716 | 0.5129 | 0.4167 | 0.067* | |
C18 | 0.2560 (7) | 0.3690 (6) | 0.3979 (3) | 0.0591 (14) | |
H18A | 0.1970 | 0.4401 | 0.3977 | 0.071* | |
H18B | 0.2510 | 0.3318 | 0.4458 | 0.071* | |
C19 | 0.1040 (7) | 0.1352 (5) | 0.3716 (3) | 0.0578 (14) | |
H19A | 0.1995 | 0.1072 | 0.3958 | 0.087* | |
H19B | 0.0448 | 0.0698 | 0.3328 | 0.087* | |
H19C | 0.0288 | 0.1453 | 0.4071 | 0.087* | |
C20 | 0.0906 (7) | 0.3641 (6) | 0.1306 (3) | 0.0571 (14) | |
H20A | 0.1758 | 0.3587 | 0.0993 | 0.086* | |
H20B | 0.0342 | 0.4317 | 0.1150 | 0.086* | |
H20C | 0.0093 | 0.2802 | 0.1272 | 0.086* | |
C21 | 0.6517 (6) | 0.4625 (6) | 0.3095 (3) | 0.0664 (15) | |
H21A | 0.6743 | 0.4707 | 0.2591 | 0.100* | |
H21B | 0.6906 | 0.3887 | 0.3288 | 0.100* | |
H21C | 0.7099 | 0.5424 | 0.3389 | 0.100* | |
N1 | 0.4703 (4) | 0.1382 (4) | 0.29174 (17) | 0.0352 (8) | |
N2 | 0.4723 (4) | 0.2537 (3) | 0.16755 (17) | 0.0355 (8) | |
N3 | 0.4675 (4) | 0.4404 (4) | 0.31197 (18) | 0.0381 (8) | |
N4 | 0.1720 (4) | 0.3977 (4) | 0.20902 (18) | 0.0371 (8) | |
N5 | 0.1644 (4) | 0.2643 (4) | 0.33949 (18) | 0.0366 (8) | |
O1 | 0.1448 (4) | 0.0930 (3) | 0.19619 (17) | 0.0459 (7) | |
H1W | 0.133 (7) | 0.015 (2) | 0.206 (3) | 0.069* | |
H2W | 0.122 (7) | 0.084 (5) | 0.1511 (11) | 0.069* | |
O2 | 0.7198 (5) | 0.1467 (4) | −0.00285 (19) | 0.0712 (12) | |
O3 | 0.7410 (4) | −0.1479 (3) | 0.33649 (17) | 0.0516 (8) | |
Ru1 | 0.32092 (4) | 0.26530 (3) | 0.252483 (16) | 0.03299 (13) | |
Cl1 | 0.79058 (16) | 0.25418 (13) | 0.54157 (6) | 0.0509 (3) | |
O4 | 0.6236 (5) | 0.2729 (5) | 0.5282 (2) | 0.0890 (14) | |
O5 | 0.7854 (7) | 0.1170 (4) | 0.5450 (3) | 0.1066 (17) | |
O6 | 0.8800 (7) | 0.2996 (6) | 0.4840 (3) | 0.124 (2) | |
O7 | 0.8740 (7) | 0.3223 (6) | 0.6096 (2) | 0.1074 (18) | |
Cl2 | 0.78373 (16) | 0.69460 (13) | 0.11282 (7) | 0.0547 (3) | |
O8 | 0.7950 (7) | 0.6418 (6) | 0.0416 (2) | 0.1103 (18) | |
O9 | 0.8883 (6) | 0.6447 (4) | 0.1663 (2) | 0.0874 (13) | |
O10 | 0.8399 (7) | 0.8359 (4) | 0.1158 (3) | 0.1008 (15) | |
O11 | 0.6148 (6) | 0.6606 (6) | 0.1269 (3) | 0.1103 (18) | |
O12 | 0.1500 (6) | 0.8542 (5) | 0.2555 (2) | 0.0820 (12) | |
H5W | 0.066 (7) | 0.793 (6) | 0.238 (4) | 0.123* | |
H6W | 0.152 (9) | 0.850 (7) | 0.3009 (12) | 0.123* | |
O13 | 0.1485 (7) | 0.0813 (4) | 0.0462 (2) | 0.0847 (13) | |
H3W | 0.163 (8) | 0.156 (4) | 0.020 (4) | 0.127* | |
H4W | 0.228 (5) | 0.054 (3) | 0.034 (4) | 0.127* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.059 (3) | 0.056 (3) | 0.033 (2) | 0.030 (2) | 0.013 (2) | 0.009 (2) |
C2 | 0.056 (3) | 0.057 (3) | 0.038 (2) | 0.026 (2) | 0.010 (2) | 0.019 (2) |
C3 | 0.040 (2) | 0.041 (2) | 0.045 (2) | 0.015 (2) | 0.0039 (19) | 0.012 (2) |
C4 | 0.040 (2) | 0.045 (3) | 0.038 (2) | 0.018 (2) | 0.0078 (18) | 0.003 (2) |
C5 | 0.033 (2) | 0.039 (2) | 0.031 (2) | 0.0113 (18) | 0.0081 (16) | 0.0081 (18) |
C6 | 0.036 (2) | 0.041 (2) | 0.033 (2) | 0.0114 (19) | 0.0089 (17) | 0.0040 (19) |
C7 | 0.052 (3) | 0.048 (3) | 0.037 (2) | 0.026 (2) | 0.0152 (19) | 0.011 (2) |
C8 | 0.054 (3) | 0.067 (3) | 0.029 (2) | 0.025 (3) | 0.0184 (19) | 0.008 (2) |
C9 | 0.062 (3) | 0.062 (3) | 0.039 (2) | 0.026 (3) | 0.021 (2) | 0.019 (2) |
C10 | 0.066 (3) | 0.052 (3) | 0.045 (3) | 0.024 (3) | 0.025 (2) | 0.019 (2) |
C11 | 0.117 (6) | 0.125 (6) | 0.056 (3) | 0.066 (5) | 0.058 (4) | 0.038 (4) |
C12 | 0.060 (3) | 0.063 (3) | 0.056 (3) | 0.026 (3) | −0.005 (2) | 0.021 (3) |
C13 | 0.048 (3) | 0.097 (5) | 0.088 (4) | 0.041 (3) | 0.042 (3) | 0.050 (4) |
C14 | 0.053 (3) | 0.115 (5) | 0.056 (3) | 0.050 (3) | 0.028 (2) | 0.041 (3) |
C15 | 0.060 (3) | 0.039 (3) | 0.070 (3) | 0.022 (2) | 0.013 (3) | 0.016 (2) |
C16 | 0.066 (3) | 0.044 (3) | 0.067 (3) | 0.007 (3) | 0.002 (3) | 0.016 (3) |
C17 | 0.064 (3) | 0.065 (3) | 0.036 (2) | 0.009 (3) | 0.005 (2) | 0.001 (2) |
C18 | 0.074 (4) | 0.066 (4) | 0.042 (3) | 0.017 (3) | 0.025 (2) | 0.005 (3) |
C19 | 0.073 (3) | 0.056 (3) | 0.061 (3) | 0.029 (3) | 0.038 (3) | 0.028 (3) |
C20 | 0.065 (3) | 0.071 (4) | 0.044 (3) | 0.035 (3) | 0.000 (2) | 0.014 (3) |
C21 | 0.041 (3) | 0.070 (4) | 0.087 (4) | 0.010 (3) | 0.012 (3) | −0.005 (3) |
N1 | 0.0392 (19) | 0.042 (2) | 0.0302 (16) | 0.0185 (16) | 0.0090 (14) | 0.0092 (15) |
N2 | 0.0425 (19) | 0.0386 (19) | 0.0308 (17) | 0.0158 (16) | 0.0120 (14) | 0.0093 (15) |
N3 | 0.0365 (19) | 0.044 (2) | 0.0373 (18) | 0.0145 (17) | 0.0068 (14) | 0.0046 (16) |
N4 | 0.0377 (19) | 0.048 (2) | 0.0332 (17) | 0.0189 (17) | 0.0121 (14) | 0.0136 (16) |
N5 | 0.0395 (19) | 0.044 (2) | 0.0330 (17) | 0.0164 (17) | 0.0138 (15) | 0.0129 (16) |
O1 | 0.057 (2) | 0.0408 (18) | 0.0399 (16) | 0.0102 (16) | 0.0068 (15) | 0.0079 (15) |
O2 | 0.097 (3) | 0.094 (3) | 0.0526 (19) | 0.062 (3) | 0.045 (2) | 0.027 (2) |
O3 | 0.058 (2) | 0.055 (2) | 0.0511 (18) | 0.0284 (17) | 0.0072 (15) | 0.0166 (17) |
Ru1 | 0.0370 (2) | 0.0383 (2) | 0.02922 (19) | 0.01549 (16) | 0.01107 (14) | 0.00989 (14) |
Cl1 | 0.0566 (7) | 0.0599 (8) | 0.0433 (6) | 0.0248 (6) | 0.0128 (5) | 0.0067 (6) |
O4 | 0.070 (3) | 0.128 (4) | 0.084 (3) | 0.052 (3) | 0.008 (2) | 0.021 (3) |
O5 | 0.104 (4) | 0.062 (3) | 0.154 (5) | 0.030 (3) | −0.005 (3) | 0.019 (3) |
O6 | 0.132 (4) | 0.161 (5) | 0.094 (3) | 0.032 (4) | 0.069 (3) | 0.044 (4) |
O7 | 0.128 (4) | 0.133 (4) | 0.070 (3) | 0.080 (4) | −0.029 (3) | −0.045 (3) |
Cl2 | 0.0572 (7) | 0.0613 (8) | 0.0483 (6) | 0.0142 (6) | 0.0129 (5) | 0.0186 (6) |
O8 | 0.130 (4) | 0.148 (5) | 0.058 (3) | 0.046 (4) | 0.014 (3) | −0.013 (3) |
O9 | 0.106 (3) | 0.083 (3) | 0.078 (3) | 0.040 (3) | −0.010 (2) | 0.025 (2) |
O10 | 0.121 (4) | 0.060 (3) | 0.125 (4) | 0.018 (3) | 0.027 (3) | 0.036 (3) |
O11 | 0.063 (3) | 0.147 (5) | 0.130 (4) | 0.020 (3) | 0.040 (3) | 0.061 (4) |
O12 | 0.102 (4) | 0.067 (3) | 0.071 (3) | 0.011 (2) | 0.001 (2) | 0.019 (2) |
O13 | 0.129 (4) | 0.076 (3) | 0.050 (2) | 0.023 (3) | 0.015 (2) | 0.013 (2) |
Geometric parameters (Å, º) top
C1—N1 | 1.341 (5) | C16—H16A | 0.9700 |
C1—C2 | 1.363 (6) | C16—H16B | 0.9700 |
C1—H1 | 0.9300 | C17—C18 | 1.477 (7) |
C2—C3 | 1.376 (6) | C17—N3 | 1.478 (5) |
C2—H2 | 0.9300 | C17—H17A | 0.9700 |
C3—O3 | 1.351 (5) | C17—H17B | 0.9700 |
C3—C4 | 1.392 (6) | C18—N5 | 1.486 (6) |
C4—C5 | 1.357 (6) | C18—H18A | 0.9700 |
C4—H4 | 0.9300 | C18—H18B | 0.9700 |
C5—N1 | 1.369 (5) | C19—N5 | 1.487 (5) |
C5—C6 | 1.475 (5) | C19—H19A | 0.9600 |
C6—N2 | 1.350 (5) | C19—H19B | 0.9600 |
C6—C7 | 1.376 (5) | C19—H19C | 0.9600 |
C7—C8 | 1.392 (6) | C20—N4 | 1.492 (6) |
C7—H7 | 0.9300 | C20—H20A | 0.9600 |
C8—O2 | 1.352 (5) | C20—H20B | 0.9600 |
C8—C9 | 1.363 (6) | C20—H20C | 0.9600 |
C9—C10 | 1.375 (6) | C21—N3 | 1.475 (6) |
C9—H9 | 0.9300 | C21—H21A | 0.9600 |
C10—N2 | 1.345 (5) | C21—H21B | 0.9600 |
C10—H10 | 0.9300 | C21—H21C | 0.9600 |
C11—O2 | 1.443 (6) | N1—Ru1 | 2.089 (3) |
C11—H11A | 0.9600 | N2—Ru1 | 2.106 (3) |
C11—H11B | 0.9600 | N3—Ru1 | 2.104 (4) |
C11—H11C | 0.9600 | N4—Ru1 | 2.154 (3) |
C12—O3 | 1.443 (5) | N5—Ru1 | 2.148 (3) |
C12—H12A | 0.9600 | O1—Ru1 | 2.151 (3) |
C12—H12B | 0.9600 | O1—H1W | 0.822 (19) |
C12—H12C | 0.9600 | O1—H2W | 0.817 (19) |
C13—C14 | 1.434 (7) | Cl1—O6 | 1.385 (4) |
C13—N5 | 1.477 (6) | Cl1—O7 | 1.414 (4) |
C13—H13A | 0.9700 | Cl1—O4 | 1.417 (4) |
C13—H13B | 0.9700 | Cl1—O5 | 1.420 (4) |
C14—N4 | 1.484 (5) | Cl2—O11 | 1.400 (4) |
C14—H14A | 0.9700 | Cl2—O8 | 1.407 (4) |
C14—H14B | 0.9700 | Cl2—O9 | 1.414 (4) |
C15—C16 | 1.470 (7) | Cl2—O10 | 1.429 (4) |
C15—N4 | 1.479 (6) | O12—H5W | 0.84 (2) |
C15—H15A | 0.9700 | O12—H6W | 0.83 (2) |
C15—H15B | 0.9700 | O13—H3W | 0.926 (15) |
C16—N3 | 1.509 (6) | O13—H4W | 0.82 (2) |
| | | |
N1—C1—C2 | 125.5 (4) | H18A—C18—H18B | 107.5 |
N1—C1—H1 | 117.2 | N5—C19—H19A | 109.5 |
C2—C1—H1 | 117.2 | N5—C19—H19B | 109.5 |
C1—C2—C3 | 118.4 (4) | H19A—C19—H19B | 109.5 |
C1—C2—H2 | 120.8 | N5—C19—H19C | 109.5 |
C3—C2—H2 | 120.8 | H19A—C19—H19C | 109.5 |
O3—C3—C2 | 125.0 (4) | H19B—C19—H19C | 109.5 |
O3—C3—C4 | 117.1 (4) | N4—C20—H20A | 109.5 |
C2—C3—C4 | 117.9 (4) | N4—C20—H20B | 109.5 |
C5—C4—C3 | 120.2 (4) | H20A—C20—H20B | 109.5 |
C5—C4—H4 | 119.9 | N4—C20—H20C | 109.5 |
C3—C4—H4 | 119.9 | H20A—C20—H20C | 109.5 |
C4—C5—N1 | 122.7 (4) | H20B—C20—H20C | 109.5 |
C4—C5—C6 | 123.4 (4) | N3—C21—H21A | 109.5 |
N1—C5—C6 | 113.6 (3) | N3—C21—H21B | 109.5 |
N2—C6—C7 | 122.8 (4) | H21A—C21—H21B | 109.5 |
N2—C6—C5 | 115.5 (3) | N3—C21—H21C | 109.5 |
C7—C6—C5 | 121.6 (4) | H21A—C21—H21C | 109.5 |
C6—C7—C8 | 119.5 (4) | H21B—C21—H21C | 109.5 |
C6—C7—H7 | 120.2 | C1—N1—C5 | 115.1 (3) |
C8—C7—H7 | 120.2 | C1—N1—Ru1 | 129.2 (3) |
O2—C8—C9 | 125.8 (4) | C5—N1—Ru1 | 115.5 (2) |
O2—C8—C7 | 115.9 (4) | C10—N2—C6 | 116.1 (3) |
C9—C8—C7 | 118.3 (4) | C10—N2—Ru1 | 128.9 (3) |
C8—C9—C10 | 119.0 (4) | C6—N2—Ru1 | 114.5 (2) |
C8—C9—H9 | 120.5 | C21—N3—C17 | 108.5 (4) |
C10—C9—H9 | 120.5 | C21—N3—C16 | 108.8 (4) |
N2—C10—C9 | 124.2 (4) | C17—N3—C16 | 109.8 (4) |
N2—C10—H10 | 117.9 | C21—N3—Ru1 | 114.4 (3) |
C9—C10—H10 | 117.9 | C17—N3—Ru1 | 105.6 (3) |
O2—C11—H11A | 109.5 | C16—N3—Ru1 | 109.7 (3) |
O2—C11—H11B | 109.5 | C15—N4—C14 | 110.1 (4) |
H11A—C11—H11B | 109.5 | C15—N4—C20 | 108.6 (4) |
O2—C11—H11C | 109.5 | C14—N4—C20 | 107.3 (4) |
H11A—C11—H11C | 109.5 | C15—N4—Ru1 | 105.5 (3) |
H11B—C11—H11C | 109.5 | C14—N4—Ru1 | 109.9 (3) |
O3—C12—H12A | 109.5 | C20—N4—Ru1 | 115.4 (3) |
O3—C12—H12B | 109.5 | C13—N5—C18 | 110.5 (4) |
H12A—C12—H12B | 109.5 | C13—N5—C19 | 104.4 (4) |
O3—C12—H12C | 109.5 | C18—N5—C19 | 111.3 (3) |
H12A—C12—H12C | 109.5 | C13—N5—Ru1 | 105.4 (2) |
H12B—C12—H12C | 109.5 | C18—N5—Ru1 | 108.0 (3) |
C14—C13—N5 | 114.7 (4) | C19—N5—Ru1 | 116.9 (3) |
C14—C13—H13A | 108.6 | Ru1—O1—H1W | 128 (4) |
N5—C13—H13A | 108.6 | Ru1—O1—H2W | 122 (4) |
C14—C13—H13B | 108.6 | H1W—O1—H2W | 101 (4) |
N5—C13—H13B | 108.6 | C8—O2—C11 | 117.6 (4) |
H13A—C13—H13B | 107.6 | C3—O3—C12 | 116.9 (4) |
C13—C14—N4 | 113.8 (4) | N1—Ru1—N3 | 97.34 (13) |
C13—C14—H14A | 108.8 | N1—Ru1—N2 | 76.74 (12) |
N4—C14—H14A | 108.8 | N3—Ru1—N2 | 99.22 (13) |
C13—C14—H14B | 108.8 | N1—Ru1—N5 | 100.69 (12) |
N4—C14—H14B | 108.8 | N3—Ru1—N5 | 83.39 (13) |
H14A—C14—H14B | 107.7 | N2—Ru1—N5 | 176.51 (13) |
C16—C15—N4 | 113.1 (4) | N1—Ru1—O1 | 87.40 (13) |
C16—C15—H15A | 109.0 | N3—Ru1—O1 | 173.05 (12) |
N4—C15—H15A | 109.0 | N2—Ru1—O1 | 86.79 (13) |
C16—C15—H15B | 109.0 | N5—Ru1—O1 | 90.75 (13) |
N4—C15—H15B | 109.0 | N1—Ru1—N4 | 178.07 (11) |
H15A—C15—H15B | 107.8 | N3—Ru1—N4 | 82.64 (13) |
C15—C16—N3 | 114.6 (4) | N2—Ru1—N4 | 101.36 (12) |
C15—C16—H16A | 108.6 | N5—Ru1—N4 | 81.22 (12) |
N3—C16—H16A | 108.6 | O1—Ru1—N4 | 92.79 (13) |
C15—C16—H16B | 108.6 | O6—Cl1—O7 | 110.2 (4) |
N3—C16—H16B | 108.6 | O6—Cl1—O4 | 109.9 (3) |
H16A—C16—H16B | 107.6 | O7—Cl1—O4 | 110.1 (3) |
C18—C17—N3 | 113.7 (4) | O6—Cl1—O5 | 107.7 (4) |
C18—C17—H17A | 108.8 | O7—Cl1—O5 | 108.9 (3) |
N3—C17—H17A | 108.8 | O4—Cl1—O5 | 110.0 (3) |
C18—C17—H17B | 108.8 | O11—Cl2—O8 | 109.6 (4) |
N3—C17—H17B | 108.8 | O11—Cl2—O9 | 110.4 (3) |
H17A—C17—H17B | 107.7 | O8—Cl2—O9 | 109.6 (3) |
C17—C18—N5 | 114.9 (4) | O11—Cl2—O10 | 109.0 (3) |
C17—C18—H18A | 108.5 | O8—Cl2—O10 | 109.0 (3) |
N5—C18—H18A | 108.5 | O9—Cl2—O10 | 109.3 (3) |
C17—C18—H18B | 108.5 | H5W—O12—H6W | 103 (4) |
N5—C18—H18B | 108.5 | H3W—O13—H4W | 98 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1W···O12i | 0.82 (3) | 1.96 (4) | 2.751 (6) | 161 (5) |
O1—H2W···O13 | 0.82 (2) | 1.94 (2) | 2.729 (5) | 162 (6) |
O13—H3W···O8ii | 0.93 (4) | 2.39 (4) | 3.314 (7) | 175 (5) |
O13—H3W···O10ii | 0.93 (4) | 2.46 (5) | 3.112 (7) | 128 (4) |
O13—H4W···O2iii | 0.81 (4) | 2.28 (4) | 2.936 (6) | 138 (3) |
O12—H5W···O9iv | 0.84 (5) | 2.13 (5) | 2.945 (7) | 164 (5) |
O12—H6W···O7v | 0.83 (2) | 2.46 (5) | 3.126 (7) | 138 (5) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y, −z; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [RuCl(C9H21N3)(C12H12N2O2)]ClO4·2C2H3N | [Ru(C9H21N3)(C12H12N2O2)(H2O)](ClO4)2·2H2O |
Mr | 705.60 | 741.54 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 17.8073 (9), 12.3587 (7), 28.5276 (18) | 8.1705 (6), 10.3825 (11), 18.1967 (15) |
α, β, γ (°) | 90, 98.603 (6), 90 | 92.464 (7), 96.740 (7), 103.386 (8) |
V (Å3) | 6207.6 (6) | 1487.4 (2) |
Z | 8 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.73 | 0.78 |
Crystal size (mm) | 0.38 × 0.28 × 0.12 | 0.30 × 0.12 × 0.05 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur Eos Gemini diffractometer | Oxford Diffraction Xcalibur Eos Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.816, 1.000 | 0.946, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13768, 6674, 3528 | 18945, 6429, 4889 |
Rint | 0.051 | 0.078 |
(sin θ/λ)max (Å−1) | 0.639 | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.122, 0.87 | 0.053, 0.144, 1.03 |
No. of reflections | 6674 | 6429 |
No. of parameters | 372 | 397 |
No. of restraints | 30 | 11 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.59, −0.42 | 1.17, −1.00 |
Selected interatomic distances (Å) for (I) topCl1—Ru1 | 2.4343 (11) | N3—Ru1 | 2.164 (3) |
N1—Ru1 | 2.081 (3) | N4—Ru1 | 2.161 (3) |
N2—Ru1 | 2.091 (3) | N5—Ru1 | 2.121 (3) |
| | | |
C4···C4i | 3.339 (5) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4i—H4i···Cl1 | 0.93 | 2.65 | 3.562 (4) | 167 |
C7i—H7i···Cl1 | 0.93 | 2.77 | 3.695 (4) | 176 |
Symmetry code: (i) −x, y, −z+1/2. |
Selected bond lengths (Å) for (II) topN1—Ru1 | 2.089 (3) | N4—Ru1 | 2.154 (3) |
N2—Ru1 | 2.106 (3) | N5—Ru1 | 2.148 (3) |
N3—Ru1 | 2.104 (4) | O1—Ru1 | 2.151 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1W···O12i | 0.82 (3) | 1.96 (4) | 2.751 (6) | 161 (5) |
O1—H2W···O13 | 0.82 (2) | 1.94 (2) | 2.729 (5) | 162 (6) |
O13—H3W···O8ii | 0.93 (4) | 2.39 (4) | 3.314 (7) | 175 (5) |
O13—H3W···O10ii | 0.93 (4) | 2.46 (5) | 3.112 (7) | 128 (4) |
O13—H4W···O2iii | 0.81 (4) | 2.28 (4) | 2.936 (6) | 138 (3) |
O12—H5W···O9iv | 0.84 (5) | 2.13 (5) | 2.945 (7) | 164 (5) |
O12—H6W···O7v | 0.83 (2) | 2.46 (5) | 3.126 (7) | 138 (5) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y, −z; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
Ruthenium(II)–tmtacn (tmtacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) complexes containing aromatic diimine ligands such as 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) are of considerable interest in catalysis, including a huge amount of reactions as epoxidation of alkenes, oxidation of alkanes, alcohols, aldehydes, and arenes, oxidative cleavage of C═C and C—C bonds, cis-dihydroxylation of alkene, and amination of saturated C—H bonds (Chan et al., 2011). Tuning of the redox potential of the metal-centered processes is a key issue in the design of these catalysis reagents to facilitate access to high Ru oxidation states. In this sense, modification of the electronic properties of the co-ligands has become the preferable approach to work on this problematic.
The synthesis of [Ru(bpy)(tmtacn)(H2O)](ClO4)2 was reported several years ago Cheng et al. (1994). The preparation involves the reaction under reflux between stoichiometric amounts of Ru(tmtacn)Cl3 and bpy in water in the presence of Zn0. We followed this strategy to prepare and crystallize the analogue [Ru(tmtacn){4,4'-(MeO)2bpy}(H2O)](ClO4)2.2H2O, (II), bearing the electron-rich bpy derivative 4,4'-dimethoxy-2,2'-bipyridine [4,4'-(MeO)2bpy]. A serendipitous event, the accidental contamination of a crystallization flask with NaCl, allowed us to obtain and crystallize the chloro derivative [RuCl(tmtacn){4,4'-(MeO)2bpy}]ClO4.2CH3CN, (I).
Complex (I) crystallizes in the monoclinic C2/c space group, with one perchlorate anion as counter-ion and two acetonitrile solvent molecules, whereas complex (II) crystallizes in the triclinic P1 space group with two perchlorate anions as counter-ions and two water solvent molecules. With respect to the metal center coordination sphere, complexes (I) and (II) display similar structures (Figs. 1 and 2, respectively). The coordination geometry around the Ru atom in each case is distorted octahedral. As expected, the tmtacn ligand facially coordinates to the Ru atom with N5 trans to the chloride ligand in (I) and N3 trans to the O atom of the coordinated water ligand in (II). The bidentate 4,4'-(MeO)2bpy ligand completes the octahedral environment. In (I), the Ru—Cl distance of 2.4343 (11) Å is slightly longer than that observed in the only other chloro-containing RuII complex with an {Ru(tmtacn)} moiety reported in the literature, namely [RuCl(tmtacn)(CO)2]PF6 (Yang et al., 1995), which features an Ru—Cl distance of 2.410 (2) Å. In (II), the Ru—O distance of 2.149 (4) Å is shorter than that observed in the bipyridine parent compound [Ru(tmtacn)(bpy)(H2O)](ClO4)2 (Cheng et al., 1994), with an Ru—O distance of 2.168 (3) Å. As a consequence, the trans N atom of the tmtacn ligand exhibits a larger Ru—N distance than that observed in the previously published analogue [2.103 (4) Å versus. 2.087 (4) Å]. With respect to this tmtacn trans N atom in complex (I), the presence of the donor chloride ligand affords an even longer Ru—N bond length of 2.121 (3) Å. The remaining donor N atoms of the tmtacn ligand in both complexes exhibit similar Ru—N bond lengths that also agree with those observed in [Ru(tmtacn)(bpy)(H2O)]2+. A similar situation is observed for the Ru—N bond lengths of the coordinated 4,4'-(MeO)2bpy ligand. In the aqua complexes (II) and [Ru(tmtacn)(bpy)(H2O)]2+, the Ru—N bond lengths are statistically equivalent.
In both complexes, the planar 4,4'-(MeO)2bpy ligand appears tilted with respect to the plane containing this ligand N atoms and the Ru center, with dihedral angles of 16.85 (12) and 16.17 (18)° in (I) and (II), respectively. For the calculation of these angles, the plane containing the 12-membered ring (ten C and two N) of the 4,4'-(MeO)2bpy and the plane containing the Ru atom together with the 4,4'-(MeO)2bpy N atoms and the equatorial tmtacn ligand N atoms were considered. The tilting direction is toward the L ligand (aqua and chloride in this case) and it is most probably due to the steric hindrance caused by the methyl group from the tmtacn ligand. The same behavior is observed in related complexes (Cheng et al., 1994, 1996; Wong et al., 2009).
In the crystal packing of (I), the Ru complex cations are held together in pairs through Cl···H—C interactions involving the coordinated chloride ligand and the 4,4'-(MeO)2bpy ligand, with Cl···H—C contact distances of Cl1···H4(-x, y, -z+1/2) = 2.65 Å and Cl1···H7(-x, y, -z+1/2) = 2.77 Å. This affords an apparent stacking of the 4,4'-dimethoxy-2,2'-bipyridine ligands, with the shortest C···C contact being C4···C4(-x, y, -z+1/2) of 3.339 (5) Å (Fig. 3, and Tables 1 and 2). The perchlorate counter-ion and the acetonitrile solvent molecules are also involved in short-contact interactions.
Regarding the crystal packing of (II), no 4,4'-(MeO)2bpy stacking is observed. Instead, hydrogen-bonding interactions involving the O atoms of the coordinated water molecule, the O atoms of the 4,4'-(MeO)2bpy and the O atoms of the solvent water molecules afford a tetrameric hydrogen-bonded network scheme (Fig. 4). The hydrogen-bond interactions and distances are listed in Table 4.
Complexes (I) and (II) are the first examples of structurally characterized ruthenium fragments bearing the {Ru(tmtacn)(bpy)}2+ motif with an electron rich bpy-type ligand. Moreover, the chloro derivative is only the second reported structure of an RuII complex with the general motif {Ru(tmtacn)} and containing any Ru—Cl bond. Both appear to be promising ruthenium complexes to explore their high-oxidation-state derivatives and their potential catalysis capability.