metal-organic compounds
[2,6-Bis(5-chloropyrimidin-2-yl-κN)pyridine-κN](2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)ruthenium(II) bis(hexafluoridophosphate) acetonitrile disolvate
aDépartement de Chimie, Université de Montréal, CP 6128, Succ. Centre-ville, Montréal, Québec, Canada H3C 3J7
*Correspondence e-mail: garry.hanan@umontreal.ca
In the title compound, [Ru(C13H7Cl2N5)(C15H11N3)](PF6)2·2CH3CN, the RuII atom is coordinated in a distorted octahedral geometry by a tridentate 2,2′:6′,2′′-terpyridine ligand and a tridentate 2,6-bis(5-chloropyrimidin-2-yl)pyridine ligand. Least-squares mean-plane distortions of only 1.72 (2) and 2.91 (2)° of the pyrimidyl rings with respect to the central pyridine are observed for the bis(pyrimidyl)pyridine-based tridentate ligand, while the distal pyridyl rings of terpyridine twist by 13.43 (7) and 4.68 (9)° away from the central pyridine ring.
Related literature
For related literature, see: Fang et al. (2002); Groen et al. (1998); Medlycott & Hanan (2005); Polson et al. (2004); Pyo et al. (1999).
Experimental
Crystal data
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Data collection: SMART (Bruker, 1999); cell SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (local program) and Spek (2003).
Supporting information
10.1107/S1600536807068602/hy2110sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536807068602/hy2110Isup2.hkl
The title compound was synthesized following previously established procedures (Polson et al.,2004).
H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95Å and Uiso(H) = 1.2Ueq(C) for the ligands and with C—H = 0.98Å and Uiso(H) = 1.5Ueq(C) for the methyl group of acetonitrile. A final verification of possible voids was performed using the VOID routine of the PLATON program (Spek, 2003).
Data collection: SMART (Bruker, 1999); cell
SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (local program).[Ru(C13H7Cl2N5)(C15H11N3)](PF6)2·2C2H3N | F(000) = 8032 |
Mr = 1010.52 | Dx = 1.789 Mg m−3 |
Orthorhombic, Fdd2 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: F 2 -2d | Cell parameters from 7885 reflections |
a = 16.3846 (2) Å | θ = 2.8–72.9° |
b = 62.8985 (8) Å | µ = 6.44 mm−1 |
c = 14.5581 (2) Å | T = 100 K |
V = 15003.1 (3) Å3 | Block, red |
Z = 16 | 0.48 × 0.25 × 0.07 mm |
Bruker SMART 2K diffractometer | 7327 independent reflections |
Radiation source: X-ray Sealed Tube | 7121 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω scans | θmax = 73.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→18 |
Tmin = 0.190, Tmax = 0.640 | k = −77→77 |
45518 measured reflections | l = −17→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0495P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.002 |
7327 reflections | Δρmax = 0.71 e Å−3 |
534 parameters | Δρmin = −0.38 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 3439 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.052 (5) |
[Ru(C13H7Cl2N5)(C15H11N3)](PF6)2·2C2H3N | V = 15003.1 (3) Å3 |
Mr = 1010.52 | Z = 16 |
Orthorhombic, Fdd2 | Cu Kα radiation |
a = 16.3846 (2) Å | µ = 6.44 mm−1 |
b = 62.8985 (8) Å | T = 100 K |
c = 14.5581 (2) Å | 0.48 × 0.25 × 0.07 mm |
Bruker SMART 2K diffractometer | 7327 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 7121 reflections with I > 2σ(I) |
Tmin = 0.190, Tmax = 0.640 | Rint = 0.053 |
45518 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.072 | Δρmax = 0.71 e Å−3 |
S = 1.08 | Δρmin = −0.38 e Å−3 |
7327 reflections | Absolute structure: Flack (1983), 3439 Friedel pairs |
534 parameters | Absolute structure parameter: 0.052 (5) |
1 restraint |
Experimental. X-ray crystallographic data for the title compound were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis. |
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. |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.290100 (12) | 0.172144 (3) | 0.184589 (14) | 0.01338 (6) | |
N1 | 0.16426 (13) | 0.16743 (3) | 0.17514 (17) | 0.0127 (5) | |
N2 | 0.06878 (15) | 0.13822 (4) | 0.16488 (17) | 0.0192 (5) | |
N3 | 0.28547 (14) | 0.14071 (3) | 0.1797 (2) | 0.0158 (4) | |
N4 | 0.41289 (14) | 0.16477 (4) | 0.19327 (18) | 0.0162 (5) | |
N5 | 0.50172 (15) | 0.13428 (4) | 0.19511 (18) | 0.0185 (5) | |
N6 | 0.30146 (14) | 0.17985 (4) | 0.04606 (19) | 0.0161 (5) | |
N7 | 0.30453 (13) | 0.20369 (3) | 0.1912 (2) | 0.0171 (5) | |
N8 | 0.28073 (15) | 0.17725 (4) | 0.32451 (18) | 0.0164 (5) | |
Cl1 | −0.05599 (5) | 0.191627 (12) | 0.18178 (7) | 0.03047 (17) | |
Cl2 | 0.63956 (5) | 0.185785 (12) | 0.20297 (6) | 0.02663 (17) | |
C1 | 0.10321 (18) | 0.18085 (4) | 0.1752 (2) | 0.0187 (6) | |
H1 | 0.1139 | 0.1957 | 0.1764 | 0.022* | |
C2 | 0.02315 (19) | 0.17372 (5) | 0.1736 (2) | 0.0216 (6) | |
C3 | 0.00786 (18) | 0.15218 (5) | 0.1673 (2) | 0.0205 (6) | |
H3 | −0.0469 | 0.1473 | 0.1648 | 0.025* | |
C4 | 0.14379 (17) | 0.14580 (4) | 0.1707 (2) | 0.0161 (6) | |
C5 | 0.21284 (17) | 0.13084 (4) | 0.1747 (2) | 0.0166 (6) | |
C6 | 0.20777 (17) | 0.10876 (4) | 0.1748 (2) | 0.0179 (6) | |
H6 | 0.1563 | 0.1018 | 0.1723 | 0.021* | |
C7 | 0.27997 (18) | 0.09704 (4) | 0.1786 (2) | 0.0195 (6) | |
H7 | 0.2782 | 0.0819 | 0.1792 | 0.023* | |
C8 | 0.35412 (17) | 0.10751 (4) | 0.1814 (2) | 0.0184 (5) | |
H8 | 0.4036 | 0.0996 | 0.1816 | 0.022* | |
C9 | 0.35616 (16) | 0.12949 (4) | 0.1840 (2) | 0.0157 (5) | |
C10 | 0.42780 (17) | 0.14324 (4) | 0.1912 (2) | 0.0155 (5) | |
C11 | 0.56623 (19) | 0.14731 (5) | 0.1980 (2) | 0.0194 (6) | |
H11 | 0.6197 | 0.1415 | 0.1991 | 0.023* | |
C12 | 0.55631 (19) | 0.16922 (5) | 0.1993 (2) | 0.0195 (6) | |
C13 | 0.47850 (17) | 0.17753 (5) | 0.1987 (2) | 0.0175 (6) | |
H13 | 0.4711 | 0.1925 | 0.2022 | 0.021* | |
C21 | 0.30071 (18) | 0.16651 (5) | −0.0258 (2) | 0.0195 (6) | |
H21 | 0.2985 | 0.1516 | −0.0147 | 0.023* | |
C22 | 0.3031 (2) | 0.17365 (5) | −0.1157 (2) | 0.0246 (7) | |
H22 | 0.3032 | 0.1638 | −0.1651 | 0.029* | |
C23 | 0.3053 (2) | 0.19512 (6) | −0.1327 (2) | 0.0264 (7) | |
H23 | 0.3035 | 0.2003 | −0.1939 | 0.032* | |
C24 | 0.31023 (19) | 0.20912 (5) | −0.0588 (3) | 0.0236 (6) | |
H24 | 0.3144 | 0.2240 | −0.0690 | 0.028* | |
C25 | 0.30901 (18) | 0.20109 (5) | 0.0297 (2) | 0.0176 (6) | |
C26 | 0.31643 (18) | 0.21439 (5) | 0.1127 (2) | 0.0181 (6) | |
C27 | 0.3406 (2) | 0.23558 (5) | 0.1156 (2) | 0.0229 (7) | |
H27 | 0.3490 | 0.2434 | 0.0606 | 0.028* | |
C28 | 0.3523 (2) | 0.24505 (5) | 0.2008 (2) | 0.0283 (7) | |
H28 | 0.3690 | 0.2595 | 0.2040 | 0.034* | |
C29 | 0.3398 (2) | 0.23369 (5) | 0.2810 (2) | 0.0246 (7) | |
H29 | 0.3481 | 0.2402 | 0.3392 | 0.030* | |
C30 | 0.31470 (19) | 0.21252 (5) | 0.2749 (2) | 0.0193 (6) | |
C31 | 0.29853 (18) | 0.19766 (5) | 0.3507 (2) | 0.0191 (6) | |
C32 | 0.3001 (2) | 0.20342 (5) | 0.4418 (3) | 0.0257 (7) | |
H32 | 0.3149 | 0.2175 | 0.4591 | 0.031* | |
C33 | 0.2797 (2) | 0.18839 (6) | 0.5089 (2) | 0.0262 (7) | |
H33 | 0.2806 | 0.1922 | 0.5721 | 0.031* | |
C34 | 0.25841 (19) | 0.16815 (6) | 0.4826 (2) | 0.0241 (7) | |
H34 | 0.2430 | 0.1578 | 0.5270 | 0.029* | |
C35 | 0.25996 (19) | 0.16315 (5) | 0.3895 (2) | 0.0202 (6) | |
H35 | 0.2457 | 0.1491 | 0.3712 | 0.024* | |
P1 | 0.53369 (4) | 0.138455 (11) | −0.06986 (7) | 0.01995 (15) | |
F11 | 0.55805 (15) | 0.15979 (3) | −0.12300 (15) | 0.0394 (5) | |
F12 | 0.47251 (14) | 0.15156 (4) | −0.00468 (16) | 0.0489 (6) | |
F13 | 0.60507 (12) | 0.14221 (4) | 0.00174 (15) | 0.0395 (5) | |
F14 | 0.59497 (16) | 0.12565 (4) | −0.13491 (16) | 0.0478 (6) | |
F15 | 0.46190 (13) | 0.13468 (4) | −0.14174 (17) | 0.0456 (6) | |
F16 | 0.50911 (17) | 0.11725 (4) | −0.01669 (18) | 0.0514 (7) | |
P2 | 0.55212 (6) | 0.220273 (12) | 0.44248 (8) | 0.02989 (19) | |
F21 | 0.62202 (18) | 0.23668 (4) | 0.41314 (18) | 0.0620 (8) | |
F22 | 0.61423 (13) | 0.20103 (4) | 0.4277 (2) | 0.0494 (6) | |
F23 | 0.52253 (16) | 0.21836 (4) | 0.33806 (17) | 0.0481 (6) | |
F24 | 0.4896 (2) | 0.23943 (4) | 0.45789 (19) | 0.0691 (9) | |
F25 | 0.57961 (18) | 0.22231 (4) | 0.54775 (16) | 0.0499 (6) | |
F26 | 0.48287 (14) | 0.20363 (4) | 0.47239 (17) | 0.0412 (5) | |
C41 | 0.5921 (3) | 0.24842 (7) | 0.1749 (4) | 0.0671 (15) | |
H41A | 0.5672 | 0.2485 | 0.2362 | 0.101* | |
H41B | 0.6125 | 0.2341 | 0.1613 | 0.101* | |
H41C | 0.5511 | 0.2524 | 0.1291 | 0.101* | |
C42 | 0.6591 (3) | 0.26342 (6) | 0.1723 (3) | 0.0385 (9) | |
N43 | 0.7112 (2) | 0.27540 (5) | 0.1708 (3) | 0.0412 (9) | |
C51 | 0.5307 (3) | 0.20455 (7) | −0.0195 (3) | 0.0445 (10) | |
H51A | 0.5680 | 0.2005 | 0.0302 | 0.067* | |
H51B | 0.4951 | 0.1925 | −0.0341 | 0.067* | |
H51C | 0.4974 | 0.2167 | 0.0000 | 0.067* | |
C52 | 0.5776 (2) | 0.21037 (5) | −0.1004 (3) | 0.0301 (8) | |
N53 | 0.6152 (2) | 0.21498 (5) | −0.1637 (2) | 0.0403 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01374 (10) | 0.00810 (9) | 0.01831 (10) | 0.00004 (7) | 0.00117 (8) | 0.00034 (9) |
N1 | 0.0076 (10) | 0.0176 (11) | 0.0129 (12) | −0.0043 (8) | −0.0006 (9) | 0.0052 (10) |
N2 | 0.0179 (13) | 0.0198 (12) | 0.0198 (14) | −0.0043 (10) | −0.0001 (10) | 0.0000 (10) |
N3 | 0.0191 (11) | 0.0120 (10) | 0.0164 (11) | 0.0004 (8) | −0.0004 (10) | 0.0014 (12) |
N4 | 0.0171 (12) | 0.0150 (11) | 0.0167 (12) | −0.0012 (8) | 0.0020 (11) | −0.0005 (11) |
N5 | 0.0189 (12) | 0.0146 (11) | 0.0220 (13) | 0.0035 (8) | 0.0033 (11) | 0.0011 (10) |
N6 | 0.0139 (12) | 0.0110 (12) | 0.0233 (14) | −0.0003 (9) | 0.0007 (10) | 0.0012 (10) |
N7 | 0.0165 (12) | 0.0104 (10) | 0.0243 (13) | 0.0007 (8) | 0.0028 (12) | 0.0009 (11) |
N8 | 0.0151 (12) | 0.0151 (12) | 0.0191 (13) | −0.0002 (9) | −0.0001 (9) | −0.0003 (10) |
Cl1 | 0.0194 (3) | 0.0265 (4) | 0.0456 (5) | 0.0084 (3) | 0.0040 (4) | 0.0037 (4) |
Cl2 | 0.0186 (4) | 0.0253 (4) | 0.0360 (5) | −0.0046 (3) | 0.0018 (3) | −0.0041 (3) |
C1 | 0.0202 (14) | 0.0153 (12) | 0.0205 (15) | −0.0006 (10) | 0.0014 (13) | 0.0026 (11) |
C2 | 0.0188 (13) | 0.0230 (14) | 0.0230 (18) | 0.0043 (11) | 0.0024 (13) | 0.0019 (13) |
C3 | 0.0134 (14) | 0.0280 (15) | 0.0200 (16) | −0.0011 (11) | −0.0002 (11) | −0.0008 (12) |
C4 | 0.0182 (14) | 0.0148 (12) | 0.0153 (15) | −0.0016 (10) | 0.0032 (11) | −0.0023 (11) |
C5 | 0.0199 (13) | 0.0148 (12) | 0.0150 (15) | −0.0041 (10) | 0.0014 (11) | 0.0004 (12) |
C6 | 0.0207 (13) | 0.0128 (12) | 0.0202 (16) | −0.0050 (10) | 0.0020 (12) | −0.0008 (12) |
C7 | 0.0275 (15) | 0.0089 (11) | 0.0220 (15) | 0.0012 (10) | 0.0001 (13) | 0.0009 (13) |
C8 | 0.0240 (14) | 0.0129 (12) | 0.0183 (13) | 0.0039 (10) | 0.0012 (14) | 0.0025 (12) |
C9 | 0.0181 (13) | 0.0120 (12) | 0.0171 (13) | 0.0008 (9) | 0.0015 (13) | 0.0015 (12) |
C10 | 0.0179 (13) | 0.0139 (12) | 0.0146 (13) | 0.0043 (9) | 0.0001 (12) | 0.0011 (12) |
C11 | 0.0167 (14) | 0.0236 (14) | 0.0178 (15) | 0.0030 (11) | 0.0007 (12) | 0.0019 (12) |
C12 | 0.0185 (14) | 0.0202 (14) | 0.0197 (18) | −0.0038 (11) | 0.0021 (12) | −0.0029 (12) |
C13 | 0.0176 (14) | 0.0164 (13) | 0.0184 (15) | −0.0020 (10) | 0.0035 (12) | −0.0011 (11) |
C21 | 0.0166 (15) | 0.0147 (14) | 0.0272 (16) | −0.0008 (11) | −0.0005 (12) | −0.0031 (12) |
C22 | 0.0254 (17) | 0.0258 (17) | 0.0225 (17) | −0.0011 (13) | 0.0016 (13) | −0.0064 (13) |
C23 | 0.0259 (17) | 0.0316 (19) | 0.0218 (16) | −0.0009 (14) | 0.0022 (13) | 0.0042 (14) |
C24 | 0.0235 (15) | 0.0196 (14) | 0.0277 (17) | −0.0016 (11) | 0.0048 (15) | 0.0047 (14) |
C25 | 0.0160 (14) | 0.0130 (14) | 0.0237 (15) | −0.0031 (11) | 0.0010 (12) | 0.0025 (12) |
C26 | 0.0148 (14) | 0.0148 (14) | 0.0247 (16) | 0.0009 (11) | 0.0005 (12) | 0.0013 (12) |
C27 | 0.0269 (16) | 0.0126 (14) | 0.0293 (17) | −0.0019 (12) | 0.0033 (13) | 0.0021 (12) |
C28 | 0.0359 (19) | 0.0136 (14) | 0.035 (2) | −0.0055 (12) | 0.0036 (15) | −0.0036 (13) |
C29 | 0.0305 (17) | 0.0147 (14) | 0.0287 (17) | −0.0020 (12) | 0.0007 (14) | −0.0057 (12) |
C30 | 0.0168 (15) | 0.0174 (15) | 0.0237 (16) | 0.0009 (11) | 0.0008 (12) | −0.0040 (12) |
C31 | 0.0157 (15) | 0.0159 (15) | 0.0258 (17) | 0.0005 (11) | 0.0024 (12) | −0.0006 (12) |
C32 | 0.0273 (16) | 0.0277 (17) | 0.0222 (16) | −0.0046 (12) | −0.0017 (14) | −0.0065 (15) |
C33 | 0.0233 (17) | 0.034 (2) | 0.0213 (16) | −0.0021 (14) | 0.0001 (13) | −0.0002 (14) |
C34 | 0.0149 (16) | 0.0327 (18) | 0.0245 (16) | −0.0007 (13) | −0.0002 (13) | 0.0058 (14) |
C35 | 0.0159 (15) | 0.0171 (14) | 0.0277 (16) | −0.0009 (11) | 0.0008 (12) | 0.0045 (12) |
P1 | 0.0173 (3) | 0.0206 (3) | 0.0220 (4) | −0.0014 (3) | −0.0014 (3) | 0.0043 (4) |
F11 | 0.0604 (15) | 0.0288 (11) | 0.0290 (11) | −0.0096 (10) | −0.0010 (10) | 0.0081 (9) |
F12 | 0.0412 (13) | 0.0762 (18) | 0.0295 (12) | 0.0268 (12) | 0.0053 (10) | 0.0076 (12) |
F13 | 0.0272 (11) | 0.0636 (15) | 0.0277 (11) | −0.0158 (10) | −0.0083 (9) | 0.0098 (10) |
F14 | 0.0543 (15) | 0.0551 (15) | 0.0339 (12) | 0.0287 (12) | 0.0038 (11) | 0.0004 (11) |
F15 | 0.0329 (13) | 0.0671 (17) | 0.0369 (13) | −0.0200 (11) | −0.0104 (10) | 0.0106 (12) |
F16 | 0.0697 (17) | 0.0369 (13) | 0.0477 (15) | −0.0190 (12) | −0.0112 (13) | 0.0209 (11) |
P2 | 0.0418 (5) | 0.0167 (3) | 0.0312 (5) | −0.0054 (3) | 0.0004 (4) | −0.0044 (4) |
F21 | 0.093 (2) | 0.0467 (14) | 0.0464 (16) | −0.0465 (14) | −0.0020 (14) | 0.0039 (12) |
F22 | 0.0305 (11) | 0.0396 (12) | 0.0783 (18) | −0.0016 (9) | 0.0024 (13) | −0.0136 (14) |
F23 | 0.0615 (16) | 0.0487 (15) | 0.0342 (12) | −0.0094 (12) | −0.0039 (11) | −0.0094 (11) |
F24 | 0.116 (3) | 0.0338 (13) | 0.0576 (19) | 0.0370 (15) | 0.0013 (16) | −0.0069 (12) |
F25 | 0.0831 (19) | 0.0298 (12) | 0.0367 (13) | −0.0235 (12) | −0.0118 (12) | 0.0036 (10) |
F26 | 0.0352 (12) | 0.0343 (12) | 0.0541 (14) | −0.0045 (9) | 0.0122 (10) | −0.0061 (10) |
C41 | 0.074 (3) | 0.048 (3) | 0.080 (4) | −0.016 (2) | −0.032 (3) | 0.020 (3) |
C42 | 0.054 (2) | 0.0251 (17) | 0.036 (2) | 0.0097 (16) | −0.0056 (19) | 0.0037 (16) |
N43 | 0.050 (2) | 0.0265 (15) | 0.047 (2) | 0.0066 (14) | 0.0009 (16) | 0.0026 (15) |
C51 | 0.044 (2) | 0.044 (2) | 0.045 (2) | −0.0034 (18) | 0.0125 (19) | 0.0020 (19) |
C52 | 0.0322 (19) | 0.0219 (16) | 0.036 (2) | 0.0064 (13) | −0.0042 (15) | −0.0004 (14) |
N53 | 0.053 (2) | 0.0313 (17) | 0.0368 (18) | 0.0028 (14) | 0.0104 (16) | 0.0072 (14) |
Ru1—N1 | 2.088 (2) | C22—H22 | 0.95 |
Ru1—N3 | 1.980 (2) | C23—C24 | 1.393 (5) |
Ru1—N4 | 2.069 (2) | C23—H23 | 0.95 |
Ru1—N6 | 2.083 (3) | C24—C25 | 1.383 (5) |
Ru1—N7 | 2.000 (2) | C24—H24 | 0.95 |
Ru1—N8 | 2.068 (3) | C25—C26 | 1.475 (4) |
N1—C1 | 1.309 (4) | C26—C27 | 1.391 (4) |
N1—C4 | 1.403 (3) | C27—C28 | 1.389 (5) |
N2—C4 | 1.321 (4) | C27—H27 | 0.95 |
N2—C3 | 1.330 (4) | C28—C29 | 1.384 (5) |
N3—C5 | 1.344 (4) | C28—H28 | 0.95 |
N3—C9 | 1.358 (3) | C29—C30 | 1.396 (4) |
N4—C13 | 1.344 (4) | C29—H29 | 0.95 |
N4—C10 | 1.376 (3) | C30—C31 | 1.471 (4) |
N5—C10 | 1.337 (3) | C31—C32 | 1.375 (5) |
N5—C11 | 1.339 (4) | C32—C33 | 1.399 (5) |
N6—C21 | 1.342 (4) | C32—H32 | 0.95 |
N6—C25 | 1.363 (4) | C33—C34 | 1.375 (5) |
N7—C26 | 1.340 (4) | C33—H33 | 0.95 |
N7—C30 | 1.349 (4) | C34—C35 | 1.392 (4) |
N8—C35 | 1.341 (4) | C34—H34 | 0.95 |
N8—C31 | 1.370 (4) | C35—H35 | 0.95 |
Cl1—C2 | 1.722 (3) | P1—F13 | 1.584 (2) |
Cl2—C12 | 1.717 (3) | P1—F15 | 1.592 (2) |
C1—C2 | 1.386 (4) | P1—F16 | 1.594 (2) |
C1—H1 | 0.95 | P1—F14 | 1.598 (2) |
C2—C3 | 1.381 (4) | P1—F11 | 1.599 (2) |
C3—H3 | 0.95 | P1—F12 | 1.608 (2) |
C4—C5 | 1.473 (4) | P2—F22 | 1.596 (2) |
C5—C6 | 1.391 (4) | P2—F24 | 1.598 (3) |
C6—C7 | 1.395 (4) | P2—F21 | 1.600 (2) |
C6—H6 | 0.95 | P2—F23 | 1.600 (3) |
C7—C8 | 1.382 (4) | P2—F25 | 1.602 (2) |
C7—H7 | 0.95 | P2—F26 | 1.604 (2) |
C8—C9 | 1.383 (4) | C41—C42 | 1.448 (6) |
C8—H8 | 0.95 | C41—H41a | 0.98 |
C9—C10 | 1.462 (4) | C41—H41b | 0.98 |
C11—C12 | 1.387 (4) | C41—H41c | 0.98 |
C11—H11 | 0.95 | C42—N43 | 1.140 (5) |
C12—C13 | 1.378 (4) | C51—C52 | 1.453 (5) |
C13—H13 | 0.95 | C51—H51a | 0.98 |
C21—C22 | 1.383 (5) | C51—H51b | 0.98 |
C21—H21 | 0.95 | C51—H51c | 0.98 |
C22—C23 | 1.374 (5) | C52—N53 | 1.145 (5) |
N3—Ru1—N7 | 175.35 (9) | C24—C23—H23 | 120.5 |
N3—Ru1—N8 | 100.81 (12) | C25—C24—C23 | 119.2 (3) |
N7—Ru1—N8 | 78.90 (12) | C25—C24—H24 | 120.4 |
N3—Ru1—N4 | 79.37 (9) | C23—C24—H24 | 120.4 |
N7—Ru1—N4 | 96.00 (9) | N6—C25—C24 | 121.5 (3) |
N8—Ru1—N4 | 92.69 (10) | N6—C25—C26 | 114.8 (3) |
N3—Ru1—N6 | 101.62 (11) | C24—C25—C26 | 123.7 (3) |
N7—Ru1—N6 | 78.75 (11) | N7—C26—C27 | 119.8 (3) |
N8—Ru1—N6 | 157.58 (9) | N7—C26—C25 | 113.7 (3) |
N4—Ru1—N6 | 91.4 (1) | C27—C26—C25 | 126.3 (3) |
N3—Ru1—N1 | 79.51 (9) | C28—C27—C26 | 118.5 (3) |
N7—Ru1—N1 | 105.12 (9) | C28—C27—H27 | 120.7 |
N8—Ru1—N1 | 90.79 (10) | C26—C27—H27 | 120.7 |
N4—Ru1—N1 | 158.87 (9) | C29—C28—C27 | 120.7 (3) |
N6—Ru1—N1 | 93.3 (1) | C29—C28—H28 | 119.6 |
C1—N1—C4 | 116.3 (2) | C27—C28—H28 | 119.6 |
C1—N1—RU1 | 131.55 (19) | C28—C29—C30 | 118.8 (3) |
C4—N1—RU1 | 112.15 (18) | C28—C29—H29 | 120.6 |
C4—N2—C3 | 117.3 (3) | C30—C29—H29 | 120.6 |
C5—N3—C9 | 121.2 (2) | N7—C30—C29 | 119.1 (3) |
C5—N3—RU1 | 119.80 (18) | N7—C30—C31 | 113.2 (3) |
C9—N3—RU1 | 119.00 (18) | C29—C30—C31 | 127.7 (3) |
C13—N4—C10 | 116.5 (2) | N8—C31—C32 | 121.3 (3) |
C13—N4—RU1 | 130.4 (2) | N8—C31—C30 | 115.1 (3) |
C10—N4—RU1 | 113.08 (18) | C32—C31—C30 | 123.6 (3) |
C10—N5—C11 | 117.3 (2) | C31—C32—C33 | 119.4 (3) |
C21—N6—C25 | 118.5 (3) | C31—C32—H32 | 120.3 |
C21—N6—RU1 | 127.5 (2) | C33—C32—H32 | 120.3 |
C25—N6—RU1 | 113.9 (2) | C34—C33—C32 | 119.5 (3) |
C26—N7—C30 | 123.0 (2) | C34—C33—H33 | 120.3 |
C26—N7—RU1 | 118.3 (2) | C32—C33—H33 | 120.3 |
C30—N7—RU1 | 117.8 (2) | C33—C34—C35 | 118.4 (3) |
C35—N8—C31 | 118.5 (3) | C33—C34—H34 | 120.8 |
C35—N8—RU1 | 127.7 (2) | C35—C34—H34 | 120.8 |
C31—N8—RU1 | 113.8 (2) | N8—C35—C34 | 122.9 (3) |
N1—C1—C2 | 121.0 (3) | N8—C35—H35 | 118.6 |
N1—C1—H1 | 119.5 | C34—C35—H35 | 118.6 |
C2—C1—H1 | 119.5 | F13—P1—F15 | 179.9 (2) |
C3—C2—C1 | 119.3 (3) | F13—P1—F16 | 89.53 (13) |
C3—C2—CL1 | 120.6 (2) | F15—P1—F16 | 90.45 (13) |
C1—C2—CL1 | 120.0 (2) | F13—P1—F14 | 90.07 (13) |
N2—C3—C2 | 120.9 (3) | F15—P1—F14 | 89.98 (15) |
N2—C3—H3 | 119.6 | F16—P1—F14 | 91.42 (15) |
C2—C3—H3 | 119.6 | F13—P1—F11 | 90.51 (12) |
N2—C4—N1 | 125.1 (3) | F15—P1—F11 | 89.51 (13) |
N2—C4—C5 | 119.1 (3) | F16—P1—F11 | 179.77 (18) |
N1—C4—C5 | 115.7 (2) | F14—P1—F11 | 88.81 (14) |
N3—C5—C6 | 120.9 (3) | F13—P1—F12 | 89.74 (14) |
N3—C5—C4 | 112.8 (2) | F15—P1—F12 | 90.21 (13) |
C6—C5—C4 | 126.3 (3) | F16—P1—F12 | 89.14 (15) |
C5—C6—C7 | 118.5 (3) | F14—P1—F12 | 179.41 (16) |
C5—C6—H6 | 120.8 | F11—P1—F12 | 90.63 (14) |
C7—C6—H6 | 120.8 | F22—P2—F24 | 179.57 (19) |
C8—C7—C6 | 119.7 (2) | F22—P2—F21 | 89.79 (15) |
C8—C7—H7 | 120.2 | F24—P2—F21 | 90.59 (18) |
C6—C7—H7 | 120.2 | F22—P2—F23 | 90.44 (15) |
C7—C8—C9 | 119.9 (3) | F24—P2—F23 | 89.76 (15) |
C7—C8—H8 | 120.1 | F21—P2—F23 | 90.67 (14) |
C9—C8—H8 | 120.1 | F22—P2—F25 | 90.61 (16) |
N3—C9—C8 | 119.8 (2) | F24—P2—F25 | 89.19 (15) |
N3—C9—C10 | 112.4 (2) | F21—P2—F25 | 90.15 (13) |
C8—C9—C10 | 127.8 (2) | F23—P2—F25 | 178.67 (18) |
N5—C10—N4 | 125.1 (3) | F22—P2—F26 | 89.60 (12) |
N5—C10—C9 | 118.7 (2) | F24—P2—F26 | 90.02 (16) |
N4—C10—C9 | 116.2 (2) | F21—P2—F26 | 179.30 (17) |
N5—C11—C12 | 121.1 (3) | F23—P2—F26 | 89.68 (13) |
N5—C11—H11 | 119.5 | F25—P2—F26 | 89.51 (14) |
C12—C11—H11 | 119.5 | C42—C41—H41A | 109.5 |
C13—C12—C11 | 119.0 (3) | C42—C41—H41B | 109.5 |
C13—C12—CL2 | 120.3 (2) | H41A—C41—H41B | 109.5 |
C11—C12—CL2 | 120.7 (2) | C42—C41—H41C | 109.5 |
N4—C13—C12 | 120.9 (3) | H41A—C41—H41C | 109.5 |
N4—C13—H13 | 119.5 | H41B—C41—H41C | 109.5 |
C12—C13—H13 | 119.5 | N43—C42—C41 | 179.1 (5) |
N6—C21—C22 | 122.3 (3) | C52—C51—H51A | 109.5 |
N6—C21—H21 | 118.9 | C52—C51—H51B | 109.5 |
C22—C21—H21 | 118.9 | H51A—C51—H51B | 109.5 |
C23—C22—C21 | 119.4 (3) | C52—C51—H51C | 109.5 |
C23—C22—H22 | 120.3 | H51A—C51—H51C | 109.5 |
C21—C22—H22 | 120.3 | H51B—C51—H51C | 109.5 |
C22—C23—C24 | 118.9 (3) | N53—C52—C51 | 179.4 (5) |
C22—C23—H23 | 120.5 | ||
N3—RU1—N1—C1 | 178.0 (3) | N1—C4—C5—N3 | −1.7 (4) |
N7—RU1—N1—C1 | −1.6 (3) | N2—C4—C5—C6 | −1.3 (5) |
N8—RU1—N1—C1 | 77.1 (3) | N1—C4—C5—C6 | 177.6 (3) |
N4—RU1—N1—C1 | 176.7 (3) | N3—C5—C6—C7 | −1.1 (5) |
N6—RU1—N1—C1 | −80.8 (3) | C4—C5—C6—C7 | 179.7 (3) |
N3—RU1—N1—C4 | 0.1 (2) | C5—C6—C7—C8 | −0.5 (6) |
N7—RU1—N1—C4 | −179.5 (2) | C6—C7—C8—C9 | 2.5 (6) |
N8—RU1—N1—C4 | −100.8 (2) | C5—N3—C9—C8 | 1.3 (5) |
N4—RU1—N1—C4 | −1.3 (4) | RU1—N3—C9—C8 | 179.5 (3) |
N6—RU1—N1—C4 | 101.3 (2) | C5—N3—C9—C10 | −178.7 (3) |
N8—RU1—N3—C5 | 87.7 (3) | RU1—N3—C9—C10 | −0.5 (4) |
N4—RU1—N3—C5 | 178.4 (3) | C7—C8—C9—N3 | −2.9 (5) |
N6—RU1—N3—C5 | −92.3 (3) | C7—C8—C9—C10 | 177.1 (3) |
N1—RU1—N3—C5 | −1.1 (3) | C11—N5—C10—N4 | −2.5 (5) |
N8—RU1—N3—C9 | −90.5 (3) | C11—N5—C10—C9 | 177.4 (3) |
N4—RU1—N3—C9 | 0.2 (3) | C13—N4—C10—N5 | 0.7 (5) |
N6—RU1—N3—C9 | 89.5 (3) | RU1—N4—C10—N5 | 179.5 (3) |
N1—RU1—N3—C9 | −179.3 (3) | C13—N4—C10—C9 | −179.2 (3) |
N3—RU1—N4—C13 | 178.7 (3) | RU1—N4—C10—C9 | −0.4 (4) |
N7—RU1—N4—C13 | −1.7 (3) | N3—C9—C10—N5 | −179.4 (3) |
N8—RU1—N4—C13 | −80.8 (3) | C8—C9—C10—N5 | 0.6 (5) |
N6—RU1—N4—C13 | 77.2 (3) | N3—C9—C10—N4 | 0.6 (4) |
N1—RU1—N4—C13 | −179.9 (2) | C8—C9—C10—N4 | −179.4 (3) |
N3—RU1—N4—C10 | 0.1 (2) | C10—N5—C11—C12 | 1.7 (4) |
N7—RU1—N4—C10 | 179.7 (2) | N5—C11—C12—C13 | 0.7 (5) |
N8—RU1—N4—C10 | 100.6 (2) | N5—C11—C12—CL2 | −180.0 (2) |
N6—RU1—N4—C10 | −101.4 (2) | C10—N4—C13—C12 | 1.9 (4) |
N1—RU1—N4—C10 | 1.4 (4) | RU1—N4—C13—C12 | −176.7 (2) |
N3—RU1—N6—C21 | 3.4 (3) | C11—C12—C13—N4 | −2.6 (5) |
N7—RU1—N6—C21 | 178.7 (3) | CL2—C12—C13—N4 | 178.1 (2) |
N8—RU1—N6—C21 | −176.7 (2) | C25—N6—C21—C22 | −3.4 (5) |
N4—RU1—N6—C21 | 82.9 (3) | RU1—N6—C21—C22 | 175.4 (2) |
N1—RU1—N6—C21 | −76.5 (2) | N6—C21—C22—C23 | −0.8 (5) |
N3—RU1—N6—C25 | −177.8 (2) | C21—C22—C23—C24 | 3.9 (5) |
N7—RU1—N6—C25 | −2.5 (2) | C22—C23—C24—C25 | −2.9 (5) |
N8—RU1—N6—C25 | 2.2 (4) | C21—N6—C25—C24 | 4.5 (4) |
N4—RU1—N6—C25 | −98.3 (2) | RU1—N6—C25—C24 | −174.5 (2) |
N1—RU1—N6—C25 | 102.3 (2) | C21—N6—C25—C26 | −174.9 (3) |
N8—RU1—N7—C26 | 179.8 (2) | RU1—N6—C25—C26 | 6.1 (3) |
N4—RU1—N7—C26 | 88.3 (2) | C23—C24—C25—N6 | −1.3 (5) |
N6—RU1—N7—C26 | −2.0 (2) | C23—C24—C25—C26 | 178.0 (3) |
N1—RU1—N7—C26 | −92.4 (2) | C30—N7—C26—C27 | 0.2 (4) |
N8—RU1—N7—C30 | 10.2 (2) | RU1—N7—C26—C27 | −168.9 (2) |
N4—RU1—N7—C30 | −81.4 (2) | C30—N7—C26—C25 | 174.8 (3) |
N6—RU1—N7—C30 | −171.6 (2) | RU1—N7—C26—C25 | 5.7 (3) |
N1—RU1—N7—C30 | 98.0 (2) | N6—C25—C26—N7 | −7.7 (4) |
N3—RU1—N8—C35 | −12.3 (3) | C24—C25—C26—N7 | 172.9 (3) |
N7—RU1—N8—C35 | 172.5 (3) | N6—C25—C26—C27 | 166.5 (3) |
N4—RU1—N8—C35 | −91.9 (3) | C24—C25—C26—C27 | −12.9 (5) |
N6—RU1—N8—C35 | 167.8 (2) | N7—C26—C27—C28 | 0.4 (5) |
N1—RU1—N8—C35 | 67.2 (3) | C25—C26—C27—C28 | −173.5 (3) |
N3—RU1—N8—C31 | 167.6 (2) | C26—C27—C28—C29 | −0.2 (5) |
N7—RU1—N8—C31 | −7.6 (2) | C27—C28—C29—C30 | −0.4 (5) |
N4—RU1—N8—C31 | 87.9 (2) | C26—N7—C30—C29 | −0.9 (4) |
N6—RU1—N8—C31 | −12.3 (4) | RU1—N7—C30—C29 | 168.3 (2) |
N1—RU1—N8—C31 | −112.9 (2) | C26—N7—C30—C31 | −179.7 (3) |
C4—N1—C1—C2 | 1.8 (4) | RU1—N7—C30—C31 | −10.6 (3) |
RU1—N1—C1—C2 | −176.1 (2) | C28—C29—C30—N7 | 1.0 (5) |
N1—C1—C2—C3 | −3.1 (5) | C28—C29—C30—C31 | 179.6 (3) |
N1—C1—C2—CL1 | 175.5 (3) | C35—N8—C31—C32 | 3.9 (4) |
C4—N2—C3—C2 | 1.5 (4) | RU1—N8—C31—C32 | −176.0 (2) |
C1—C2—C3—N2 | 1.5 (5) | C35—N8—C31—C30 | −175.6 (3) |
CL1—C2—C3—N2 | −177.1 (2) | RU1—N8—C31—C30 | 4.5 (3) |
C3—N2—C4—N1 | −3.0 (4) | N7—C30—C31—N8 | 3.6 (4) |
C3—N2—C4—C5 | 175.8 (3) | C29—C30—C31—N8 | −175.1 (3) |
C1—N1—C4—N2 | 1.3 (4) | N7—C30—C31—C32 | −175.9 (3) |
RU1—N1—C4—N2 | 179.6 (2) | C29—C30—C31—C32 | 5.4 (5) |
C1—N1—C4—C5 | −177.4 (3) | N8—C31—C32—C33 | −2.8 (5) |
RU1—N1—C4—C5 | 0.8 (3) | C30—C31—C32—C33 | 176.7 (3) |
C9—N3—C5—C6 | 0.7 (6) | C31—C32—C33—C34 | 0.0 (5) |
RU1—N3—C5—C6 | −177.5 (3) | C32—C33—C34—C35 | 1.6 (5) |
C9—N3—C5—C4 | 180.0 (3) | C31—N8—C35—C34 | −2.3 (5) |
RU1—N3—C5—C4 | 1.8 (4) | RU1—N8—C35—C34 | 177.6 (2) |
N2—C4—C5—N3 | 179.5 (3) | C33—C34—C35—N8 | −0.5 (5) |
Experimental details
Crystal data | |
Chemical formula | [Ru(C13H7Cl2N5)(C15H11N3)](PF6)2·2C2H3N |
Mr | 1010.52 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 100 |
a, b, c (Å) | 16.3846 (2), 62.8985 (8), 14.5581 (2) |
V (Å3) | 15003.1 (3) |
Z | 16 |
Radiation type | Cu Kα |
µ (mm−1) | 6.44 |
Crystal size (mm) | 0.48 × 0.25 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART 2K diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.190, 0.640 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45518, 7327, 7121 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.620 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.072, 1.08 |
No. of reflections | 7327 |
No. of parameters | 534 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.71, −0.38 |
Absolute structure | Flack (1983), 3439 Friedel pairs |
Absolute structure parameter | 0.052 (5) |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1997), UdMX (local program).
Ru1—N1 | 2.088 (2) | Ru1—N6 | 2.083 (3) |
Ru1—N3 | 1.980 (2) | Ru1—N7 | 2.000 (2) |
Ru1—N4 | 2.069 (2) | Ru1—N8 | 2.068 (3) |
N3—Ru1—N7 | 175.35 (9) | N8—Ru1—N6 | 157.58 (9) |
N3—Ru1—N8 | 100.81 (12) | N4—Ru1—N6 | 91.4 (1) |
N7—Ru1—N8 | 78.90 (12) | N3—Ru1—N1 | 79.51 (9) |
N3—Ru1—N4 | 79.37 (9) | N7—Ru1—N1 | 105.12 (9) |
N7—Ru1—N4 | 96.00 (9) | N8—Ru1—N1 | 90.79 (10) |
N8—Ru1—N4 | 92.69 (10) | N4—Ru1—N1 | 158.87 (9) |
N3—Ru1—N6 | 101.62 (11) | N6—Ru1—N1 | 93.3 (1) |
N7—Ru1—N6 | 78.75 (11) |
Acknowledgements
We are grateful to the Natural Sciences and Engineering Research Council of Canada and the Ministère de l'Education du Québec for financial support.
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Ruthenium(II) complexes of tridentate polypyridine ligands have gained much attention in the last few decades due to their interesting photophysical properties. There have been many attempts to try and improve the photophysical properties of these complexes both in the ground state and excited states (Medlycott & Hanan, 2005). Manipulation of the electronic properties of the coordinated ligands can result in an improvement of the photophysical properties of the complex. We have previously employed this strategy by using electron-deficient trazine-based tridenate ligands (Polson et al., 2004) to lower the energy of the 3MLCT emitting state. Herein, we employ a functionalized bis(pyrimidin-2-yl)pyridine tridentate ligand for the synthesis of a ruthenium(II) complex in order to manipulate the energy of the 3MLCT emitting state. A structurally similar ligand, namely bis(pyrimidin-2-yl)pyridine, has previously been employed for the synthesis of palladium(II) complexes in order to study the dynamic behviour of such complexes in solution (Groen et al., 1998). However, the electronic behaviour and solid state structures of these systems were not reported.
The title compound crystalizes in the orthorhombic space group Fdd2 with one complex cation, two PF6- anions and two acetonitrile molecules in the asymmetric unit. The complex possesses octahedral geometry with significant distortions due to the tridentate nature of the coordinating ligands as previously observed in the parent complex [Ru(tpy)2]2+ (tpy = 2,2':6',2"-terpyridine) (Pyo et al., 1999). Small variations in the Ru—N bond distances are observed between the two coordinated ligands indicating minimal changes in the electronic (solid state) ground-state properties of the complex compared to [Ru(tpy)2]2+ (Pyo et al., 1999). Similarly, small changes are observed in the N,N,N-tridentate bite angles on the pyrimidyl-substituted ligand 158.87 (9)° compared to the coordinated tpy, 157.58 (9)°, indicating that introducing a pyrimidyl ring has minimal steric effects on the ligand field of the complex.
Comparison of the planarity of the two coordinated ligands in the title compound shows us that the bis(pyrimidin-2-yl)pyridine-based ligand lies planar. Least-square mean plane distortions of only 1.72 (2)° and 2.91 (2)° of the pyrimidyl rings with respect to the central pyridine are observed. However, the distal pyridyl-rings of terpyridine twist by 13.43 (7)° and 4.68 (9)° away from the central pyridine ring. This difference may be explained on considering the uncoordinated pyrimidyl-N atoms forming favourable intramolecular C–H···N interactions with the central pyridine ring. This coplanar effect has previously been shown to dramatically enhance the photophysical properties of such complexes (Fang et al., 2002).
We are currently investigating the consequences of pyrimidyl substitution of tridentate-tpy based ligands on the photophysical properties of their ruthenium(II) complexes.