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metal-organic compounds
(2,2′-Bipyridine-κ2N,N′)chlorido[4′-(2,5-dimethoxyphenyl)-2,2′:6′,2′′-terpyridine-κ3N,N′,N′′]ruthenium(II) hexafluoridophosphate acetonitrile monosolvate
aDepartment of Industrial Systems Engineering, Cluster of Science and Technology, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan, and bDepartment of Science Education, Faculty of Education, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan
*Correspondence e-mail: daio@sss.fukushima-u.ac.jp
In the title compound, [RuCl(C10H8N2)(C23H19N3O2)]PF6·CH3CN, the ligand environment about the RuII atom is distorted octahedral, with the substituted terpyridyl ligand coordinated in a meridional fashion, the bipyridyl ligand coordinated in a cis fashion and the Cl atom trans to one of the bipyridyl N atoms. The Ru—N distances are in the range 2.036 (2)–2.084 (2) Å with the exception of the central Ru—N bond from the terpyridyl ligand, which is shorter [1.9503 (19) Å], as expected. The pendant dimethoxyphenyl substituent is not coplanar with the terpyridyl unit; the dihedral angle between the central pyridyl ring and the benzene ring is 46.72 (11)°. The anion is disordered equally over two positions around an F—P—F bond axis.
Related literature
For details of the synthesis, see: Takeuchi et al. (1984); Storrier et al. (1995
, 1998
). For related structures, see: Spek et al. (1994
); Fujihara et al. (2003
); Tseng et al. (2008
). For general background to catalytic water oxidation using mononuclear ruthenium complexes, see: Tseng et al. (2008
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: CrystalStructure (Rigaku Americas & Rigaku, 2007
); program(s) used to solve structure: SIR97 (Altomare et al., 1999
); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003
); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997
); software used to prepare material for publication: CrystalStructure.
Supporting information
10.1107/S1600536809032589/is2438sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809032589/is2438Isup2.hkl
The ligand 4'-(2,5-dimethoxyphenyl)-2,2':6',2''-terpyridine (tpyOMe) was prepared and purified as described by Storrier et al. (1995 and 1998). The title compound was prepared following a procedure similar to that for the synthesis of [RuCl(bpy)(tpy)]PF6 (bpy = 2,2'-bipyridine, tpy = 2,2':6',2''-terpyridine) (Takeuchi et al., 1984). X-ray quality crystals were grown by the diffusion of diethyl ether into an acetonitrile solution of the complex over a week.
Aromatic H atoms were fixed at C—H distances of 0.95 Å and refined as riding, with Uiso(H) = 1.2Ueq(C). Methyl H atoms were placed with idealized threefold symmetry and fixed C—H distances of 0.98 Å, and they were refined in a riding model with Uiso(H) = 1.5Ueq(C). Four F atoms in equatorial positions of the counter anion are disordered and were refined with the occupancy of all atoms fixed at 0.5.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku Americas & Rigaku, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku Americas & Rigaku, 2007).[RuCl(C10H8N2)(C23H19N3O2)]PF6·C2H3N | F(000) = 3424.00 |
Mr = 848.15 | Dx = 1.589 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 82995 reflections |
a = 13.8691 (3) Å | θ = 3.0–27.5° |
b = 16.1993 (3) Å | µ = 0.64 mm−1 |
c = 31.5514 (6) Å | T = 296 K |
V = 7088.7 (2) Å3 | Platelet, black |
Z = 8 | 0.60 × 0.40 × 0.08 mm |
Rigaku R-AXIS RAPID diffractometer | 5738 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.036 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −17→17 |
Tmin = 0.616, Tmax = 0.950 | k = −21→20 |
102710 measured reflections | l = −40→40 |
8092 independent reflections |
Refinement on F2 | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[0.0008Fo2 + σ(Fo2)]/(4Fo2) |
wR(F2) = 0.111 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.84 e Å−3 |
8092 reflections | Δρmin = −0.59 e Å−3 |
495 parameters |
[RuCl(C10H8N2)(C23H19N3O2)]PF6·C2H3N | V = 7088.7 (2) Å3 |
Mr = 848.15 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.8691 (3) Å | µ = 0.64 mm−1 |
b = 16.1993 (3) Å | T = 296 K |
c = 31.5514 (6) Å | 0.60 × 0.40 × 0.08 mm |
Rigaku R-AXIS RAPID diffractometer | 8092 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 5738 reflections with F2 > 2σ(F2) |
Tmin = 0.616, Tmax = 0.950 | Rint = 0.036 |
102710 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 495 parameters |
wR(F2) = 0.111 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.84 e Å−3 |
8092 reflections | Δρmin = −0.59 e Å−3 |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ru1 | 0.09533 (2) | 0.785150 (10) | 0.691700 (10) | 0.03190 (6) | |
Cl1 | −0.07112 (6) | 0.78760 (5) | 0.71355 (2) | 0.0516 (2) | |
P1 | 0.28023 (11) | 0.55855 (8) | 0.55490 (4) | 0.0907 (4) | |
F1 | 0.3430 (3) | 0.6325 (2) | 0.53818 (13) | 0.1835 (19) | |
F2 | 0.2173 (4) | 0.4867 (2) | 0.56854 (18) | 0.211 (2) | |
F3 | 0.1973 (5) | 0.6208 (4) | 0.5418 (2) | 0.135 (2)* | 0.50 |
F4 | 0.3566 (5) | 0.5038 (4) | 0.5779 (2) | 0.127 (2)* | 0.50 |
F5 | 0.2666 (6) | 0.6000 (4) | 0.6016 (2) | 0.132 (2)* | 0.50 |
F6 | 0.2894 (9) | 0.5187 (6) | 0.5111 (3) | 0.195 (3)* | 0.50 |
F7 | 0.2059 (6) | 0.6174 (5) | 0.5747 (3) | 0.163 (3)* | 0.50 |
F8 | 0.3705 (5) | 0.5057 (4) | 0.5349 (2) | 0.133 (2)* | 0.50 |
F9 | 0.3448 (7) | 0.5796 (5) | 0.5938 (2) | 0.160 (2)* | 0.50 |
F10 | 0.2239 (7) | 0.5570 (6) | 0.5108 (2) | 0.167 (3)* | 0.50 |
O1 | 0.12400 (18) | 0.83112 (16) | 0.90412 (7) | 0.0633 (7) | |
O2 | 0.41159 (19) | 0.59908 (16) | 0.92417 (8) | 0.0699 (8) | |
N1 | 0.11237 (17) | 0.90625 (13) | 0.71081 (7) | 0.0375 (6) | |
N2 | 0.13304 (17) | 0.76860 (12) | 0.75064 (6) | 0.0336 (5) | |
N3 | 0.09369 (16) | 0.65680 (14) | 0.69479 (6) | 0.0357 (5) | |
N4 | 0.23041 (16) | 0.78277 (12) | 0.66643 (7) | 0.0358 (5) | |
N5 | 0.06613 (18) | 0.80557 (13) | 0.62776 (7) | 0.0389 (6) | |
N6 | 0.1768 (3) | 0.4872 (2) | 0.86305 (15) | 0.1152 (17) | |
C1 | 0.1022 (2) | 0.97542 (19) | 0.68752 (10) | 0.0490 (8) | |
C2 | 0.1122 (2) | 1.0527 (2) | 0.70476 (12) | 0.0591 (10) | |
C3 | 0.1352 (2) | 1.06143 (18) | 0.74710 (11) | 0.0550 (9) | |
C4 | 0.1486 (2) | 0.99131 (17) | 0.77096 (10) | 0.0461 (8) | |
C5 | 0.1378 (2) | 0.91387 (16) | 0.75254 (8) | 0.0379 (7) | |
C6 | 0.15085 (19) | 0.83516 (15) | 0.77544 (8) | 0.0347 (6) | |
C7 | 0.1817 (2) | 0.82465 (17) | 0.81662 (8) | 0.0392 (7) | |
C8 | 0.1916 (2) | 0.74570 (17) | 0.83322 (8) | 0.0383 (7) | |
C9 | 0.1693 (2) | 0.67785 (17) | 0.80744 (8) | 0.0388 (7) | |
C10 | 0.1395 (2) | 0.69120 (15) | 0.76611 (8) | 0.0347 (6) | |
C11 | 0.1159 (2) | 0.62689 (16) | 0.73418 (8) | 0.0374 (7) | |
C12 | 0.1172 (2) | 0.54346 (17) | 0.74277 (9) | 0.0444 (8) | |
C13 | 0.0981 (2) | 0.48827 (19) | 0.71038 (11) | 0.0553 (9) | |
C14 | 0.0772 (2) | 0.5174 (2) | 0.67092 (11) | 0.0609 (10) | |
C15 | 0.0751 (2) | 0.60201 (18) | 0.66405 (9) | 0.0510 (9) | |
C16 | 0.2300 (2) | 0.73057 (17) | 0.87661 (8) | 0.0416 (7) | |
C17 | 0.1949 (2) | 0.77434 (19) | 0.91198 (9) | 0.0476 (8) | |
C18 | 0.2308 (2) | 0.7558 (2) | 0.95182 (10) | 0.0613 (10) | |
C19 | 0.3015 (2) | 0.6975 (2) | 0.95717 (10) | 0.0602 (10) | |
C20 | 0.3381 (2) | 0.6556 (2) | 0.92280 (10) | 0.0534 (9) | |
C21 | 0.3013 (2) | 0.67203 (18) | 0.88303 (9) | 0.0461 (8) | |
C22 | 0.0980 (4) | 0.8867 (3) | 0.93613 (16) | 0.125 (2) | |
C23 | 0.4600 (3) | 0.5899 (2) | 0.96367 (13) | 0.0905 (15) | |
C24 | 0.3119 (2) | 0.77412 (17) | 0.68875 (10) | 0.0448 (8) | |
C25 | 0.4017 (2) | 0.77157 (19) | 0.67025 (13) | 0.0561 (10) | |
C26 | 0.4093 (2) | 0.7782 (2) | 0.62678 (15) | 0.0699 (12) | |
C27 | 0.3254 (2) | 0.7889 (2) | 0.60369 (12) | 0.0678 (11) | |
C28 | 0.2365 (2) | 0.79113 (17) | 0.62360 (9) | 0.0436 (7) | |
C29 | 0.1442 (2) | 0.80328 (17) | 0.60169 (9) | 0.0427 (7) | |
C30 | 0.1343 (3) | 0.8150 (2) | 0.55851 (10) | 0.0622 (10) | |
C31 | 0.0462 (3) | 0.8315 (2) | 0.54151 (10) | 0.0658 (11) | |
C32 | −0.0323 (2) | 0.8366 (2) | 0.56786 (10) | 0.0592 (10) | |
C33 | −0.0201 (2) | 0.82218 (18) | 0.61080 (9) | 0.0475 (8) | |
C34 | 0.1426 (3) | 0.5146 (2) | 0.89184 (15) | 0.0766 (13) | |
C35 | 0.0968 (3) | 0.5501 (3) | 0.92876 (18) | 0.110 (2) | |
H1 | 0.0874 | 0.9705 | 0.6582 | 0.058* | |
H2 | 0.1031 | 1.1003 | 0.6876 | 0.071* | |
H3 | 0.1417 | 1.1145 | 0.7596 | 0.066* | |
H4 | 0.1654 | 0.9957 | 0.8001 | 0.055* | |
H5 | 0.1950 | 0.8714 | 0.8338 | 0.047* | |
H6 | 0.1746 | 0.6232 | 0.8182 | 0.046* | |
H7 | 0.1313 | 0.5241 | 0.7705 | 0.053* | |
H8 | 0.0983 | 0.4306 | 0.7157 | 0.066* | |
H9 | 0.0657 | 0.4804 | 0.6481 | 0.073* | |
H10 | 0.0596 | 0.6220 | 0.6366 | 0.061* | |
H11 | 0.2061 | 0.7844 | 0.9758 | 0.074* | |
H12 | 0.3250 | 0.6857 | 0.9848 | 0.072* | |
H13 | 0.3254 | 0.6426 | 0.8592 | 0.055* | |
H14 | 0.0702 | 0.9360 | 0.9229 | 0.150* | |
H15 | 0.0504 | 0.8615 | 0.9551 | 0.150* | |
H16 | 0.1554 | 0.9022 | 0.9524 | 0.150* | |
H17 | 0.4645 | 0.6440 | 0.9775 | 0.109* | |
H18 | 0.4241 | 0.5518 | 0.9819 | 0.109* | |
H19 | 0.5250 | 0.5682 | 0.9588 | 0.109* | |
H20 | 0.3077 | 0.7693 | 0.7187 | 0.054* | |
H21 | 0.4582 | 0.7652 | 0.6870 | 0.067* | |
H22 | 0.4702 | 0.7757 | 0.6130 | 0.083* | |
H23 | 0.3292 | 0.7949 | 0.5738 | 0.082* | |
H24 | 0.1893 | 0.8120 | 0.5407 | 0.075* | |
H25 | 0.0388 | 0.8399 | 0.5119 | 0.079* | |
H26 | −0.0943 | 0.8494 | 0.5568 | 0.071* | |
H27 | −0.0749 | 0.8244 | 0.6288 | 0.057* | |
H28 | 0.1419 | 0.5893 | 0.9417 | 0.132* | |
H29 | 0.0809 | 0.5067 | 0.9492 | 0.132* | |
H30 | 0.0378 | 0.5792 | 0.9205 | 0.132* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.03289 (13) | 0.03422 (12) | 0.02858 (12) | −0.00031 (9) | −0.00081 (8) | 0.00003 (8) |
Cl1 | 0.0380 (4) | 0.0673 (4) | 0.0496 (4) | 0.0000 (3) | 0.0067 (3) | 0.0027 (3) |
P1 | 0.1047 (10) | 0.0843 (8) | 0.0833 (7) | 0.0299 (7) | −0.0148 (7) | 0.0013 (6) |
F1 | 0.217 (4) | 0.135 (3) | 0.198 (4) | −0.048 (3) | 0.063 (3) | 0.027 (2) |
F2 | 0.232 (5) | 0.116 (2) | 0.286 (6) | −0.057 (3) | 0.019 (4) | 0.040 (3) |
O1 | 0.0577 (15) | 0.0826 (17) | 0.0495 (12) | 0.0089 (13) | 0.0019 (11) | −0.0175 (11) |
O2 | 0.0721 (18) | 0.0796 (17) | 0.0579 (14) | 0.0122 (13) | −0.0194 (12) | 0.0128 (12) |
N1 | 0.0372 (13) | 0.0350 (11) | 0.0403 (12) | 0.0010 (9) | −0.0004 (9) | 0.0022 (9) |
N2 | 0.0359 (12) | 0.0349 (10) | 0.0300 (10) | 0.0001 (9) | 0.0014 (9) | −0.0006 (8) |
N3 | 0.0386 (13) | 0.0371 (11) | 0.0316 (10) | −0.0018 (9) | −0.0006 (9) | −0.0034 (8) |
N4 | 0.0345 (12) | 0.0326 (10) | 0.0404 (11) | −0.0010 (9) | 0.0006 (9) | −0.0029 (9) |
N5 | 0.0438 (14) | 0.0383 (11) | 0.0346 (11) | −0.0040 (10) | −0.0026 (10) | 0.0008 (9) |
N6 | 0.164 (4) | 0.073 (2) | 0.109 (3) | −0.024 (2) | 0.049 (3) | −0.009 (2) |
C1 | 0.057 (2) | 0.0413 (15) | 0.0482 (16) | −0.0014 (14) | −0.0045 (14) | 0.0072 (12) |
C2 | 0.063 (2) | 0.0361 (15) | 0.078 (2) | 0.0009 (15) | −0.0082 (18) | 0.0108 (15) |
C3 | 0.052 (2) | 0.0349 (14) | 0.078 (2) | −0.0009 (14) | −0.0027 (18) | −0.0034 (14) |
C4 | 0.0459 (18) | 0.0400 (14) | 0.0526 (16) | −0.0036 (13) | −0.0030 (14) | −0.0071 (12) |
C5 | 0.0345 (15) | 0.0370 (13) | 0.0420 (14) | −0.0005 (11) | 0.0022 (12) | −0.0015 (11) |
C6 | 0.0311 (14) | 0.0362 (13) | 0.0368 (12) | −0.0002 (11) | 0.0030 (10) | −0.0050 (10) |
C7 | 0.0389 (16) | 0.0429 (14) | 0.0356 (13) | −0.0045 (12) | −0.0004 (11) | −0.0062 (11) |
C8 | 0.0342 (15) | 0.0467 (14) | 0.0341 (13) | −0.0025 (12) | 0.0007 (11) | −0.0013 (11) |
C9 | 0.0410 (16) | 0.0392 (14) | 0.0362 (13) | 0.0002 (12) | −0.0024 (11) | 0.0029 (11) |
C10 | 0.0337 (14) | 0.0344 (12) | 0.0361 (12) | 0.0005 (11) | −0.0004 (11) | −0.0029 (10) |
C11 | 0.0370 (16) | 0.0389 (14) | 0.0364 (13) | −0.0001 (11) | 0.0003 (11) | −0.0037 (11) |
C12 | 0.0468 (18) | 0.0384 (13) | 0.0480 (16) | 0.0015 (13) | −0.0011 (13) | −0.0006 (12) |
C13 | 0.064 (2) | 0.0365 (15) | 0.065 (2) | 0.0006 (14) | −0.0008 (17) | −0.0074 (14) |
C14 | 0.081 (2) | 0.0491 (18) | 0.0523 (18) | −0.0067 (17) | −0.0028 (18) | −0.0184 (15) |
C15 | 0.066 (2) | 0.0468 (16) | 0.0400 (15) | −0.0034 (15) | −0.0049 (14) | −0.0083 (12) |
C16 | 0.0433 (17) | 0.0496 (16) | 0.0318 (12) | −0.0108 (13) | −0.0016 (11) | 0.0009 (11) |
C17 | 0.0477 (18) | 0.0584 (18) | 0.0368 (14) | −0.0078 (15) | 0.0009 (12) | −0.0044 (12) |
C18 | 0.068 (2) | 0.083 (2) | 0.0324 (14) | −0.018 (2) | 0.0028 (15) | −0.0043 (15) |
C19 | 0.069 (2) | 0.077 (2) | 0.0344 (15) | −0.0134 (19) | −0.0092 (15) | 0.0111 (14) |
C20 | 0.059 (2) | 0.0560 (18) | 0.0455 (16) | −0.0121 (16) | −0.0117 (14) | 0.0101 (14) |
C21 | 0.0506 (19) | 0.0511 (16) | 0.0365 (14) | −0.0068 (14) | −0.0055 (12) | 0.0026 (12) |
C22 | 0.154 (5) | 0.132 (4) | 0.090 (3) | 0.062 (3) | −0.023 (3) | −0.053 (3) |
C23 | 0.104 (3) | 0.090 (2) | 0.077 (2) | 0.011 (2) | −0.047 (2) | 0.017 (2) |
C24 | 0.0373 (16) | 0.0424 (15) | 0.0546 (17) | 0.0003 (12) | −0.0027 (13) | −0.0055 (12) |
C25 | 0.0349 (17) | 0.0505 (18) | 0.083 (2) | −0.0001 (13) | −0.0053 (16) | −0.0052 (16) |
C26 | 0.041 (2) | 0.078 (2) | 0.091 (2) | −0.0019 (17) | 0.0197 (19) | −0.008 (2) |
C27 | 0.058 (2) | 0.091 (2) | 0.055 (2) | −0.006 (2) | 0.0189 (17) | −0.0058 (18) |
C28 | 0.0441 (17) | 0.0442 (15) | 0.0425 (14) | −0.0023 (13) | 0.0073 (12) | −0.0029 (12) |
C29 | 0.0496 (18) | 0.0418 (15) | 0.0369 (13) | −0.0055 (13) | 0.0016 (12) | −0.0018 (11) |
C30 | 0.073 (2) | 0.079 (2) | 0.0346 (15) | −0.010 (2) | 0.0076 (16) | −0.0001 (15) |
C31 | 0.087 (2) | 0.073 (2) | 0.0366 (15) | −0.011 (2) | −0.0155 (18) | 0.0067 (15) |
C32 | 0.071 (2) | 0.0543 (18) | 0.0524 (17) | −0.0112 (17) | −0.0247 (17) | 0.0096 (14) |
C33 | 0.0445 (18) | 0.0510 (16) | 0.0470 (15) | −0.0059 (14) | −0.0091 (13) | 0.0050 (13) |
C34 | 0.091 (3) | 0.058 (2) | 0.081 (2) | −0.014 (2) | 0.011 (2) | 0.003 (2) |
C35 | 0.112 (4) | 0.089 (3) | 0.128 (4) | −0.028 (2) | 0.042 (3) | −0.023 (3) |
Ru1—Cl1 | 2.4096 (8) | C16—C17 | 1.409 (3) |
Ru1—N1 | 2.066 (2) | C16—C21 | 1.385 (4) |
Ru1—N2 | 1.9503 (19) | C17—C18 | 1.385 (4) |
Ru1—N3 | 2.082 (2) | C18—C19 | 1.371 (5) |
Ru1—N4 | 2.036 (2) | C19—C20 | 1.376 (4) |
Ru1—N5 | 2.084 (2) | C20—C21 | 1.380 (4) |
P1—F1 | 1.573 (4) | C24—C25 | 1.376 (4) |
P1—F2 | 1.517 (4) | C25—C26 | 1.380 (6) |
P1—F3 | 1.585 (7) | C26—C27 | 1.383 (5) |
P1—F4 | 1.560 (7) | C27—C28 | 1.384 (5) |
P1—F5 | 1.631 (7) | C28—C29 | 1.468 (4) |
P1—F6 | 1.529 (10) | C29—C30 | 1.383 (4) |
P1—F7 | 1.537 (9) | C30—C31 | 1.360 (5) |
P1—F8 | 1.642 (7) | C31—C32 | 1.373 (5) |
P1—F9 | 1.557 (9) | C32—C33 | 1.385 (4) |
P1—F10 | 1.596 (9) | C34—C35 | 1.447 (7) |
O1—C17 | 1.369 (4) | C1—H1 | 0.950 |
O1—C22 | 1.400 (5) | C2—H2 | 0.950 |
O2—C20 | 1.371 (4) | C3—H3 | 0.950 |
O2—C23 | 1.423 (5) | C4—H4 | 0.950 |
N1—C1 | 1.347 (3) | C7—H5 | 0.950 |
N1—C5 | 1.369 (3) | C9—H6 | 0.950 |
N2—C6 | 1.355 (3) | C12—H7 | 0.950 |
N2—C10 | 1.348 (3) | C13—H8 | 0.950 |
N3—C11 | 1.369 (3) | C14—H9 | 0.950 |
N3—C15 | 1.340 (3) | C15—H10 | 0.950 |
N4—C24 | 1.339 (3) | C18—H11 | 0.950 |
N4—C28 | 1.361 (3) | C19—H12 | 0.950 |
N5—C29 | 1.361 (3) | C21—H13 | 0.950 |
N5—C33 | 1.337 (3) | C22—H14 | 0.980 |
N6—C34 | 1.116 (6) | C22—H15 | 0.980 |
C1—C2 | 1.372 (4) | C22—H16 | 0.980 |
C2—C3 | 1.381 (5) | C23—H17 | 0.980 |
C3—C4 | 1.375 (4) | C23—H18 | 0.980 |
C4—C5 | 1.391 (3) | C23—H19 | 0.980 |
C5—C6 | 1.477 (3) | C24—H20 | 0.950 |
C6—C7 | 1.378 (3) | C25—H21 | 0.950 |
C7—C8 | 1.389 (3) | C26—H22 | 0.950 |
C8—C9 | 1.402 (3) | C27—H23 | 0.950 |
C8—C16 | 1.489 (3) | C30—H24 | 0.950 |
C9—C10 | 1.385 (3) | C31—H25 | 0.950 |
C10—C11 | 1.486 (3) | C32—H26 | 0.950 |
C11—C12 | 1.379 (3) | C33—H27 | 0.950 |
C12—C13 | 1.384 (4) | C35—H28 | 0.980 |
C13—C14 | 1.363 (4) | C35—H29 | 0.980 |
C14—C15 | 1.387 (4) | C35—H30 | 0.980 |
Cl1—Ru1—N1 | 90.60 (6) | C8—C16—C21 | 120.1 (2) |
Cl1—Ru1—N2 | 89.22 (7) | C17—C16—C21 | 118.4 (2) |
Cl1—Ru1—N3 | 89.58 (6) | O1—C17—C16 | 116.3 (2) |
Cl1—Ru1—N4 | 173.57 (6) | O1—C17—C18 | 124.7 (2) |
Cl1—Ru1—N5 | 95.06 (7) | C16—C17—C18 | 119.0 (2) |
N1—Ru1—N2 | 79.72 (8) | C17—C18—C19 | 121.2 (3) |
N1—Ru1—N3 | 159.40 (8) | C18—C19—C20 | 120.4 (3) |
N1—Ru1—N4 | 91.55 (8) | O2—C20—C19 | 125.4 (3) |
N1—Ru1—N5 | 98.86 (8) | O2—C20—C21 | 115.6 (2) |
N2—Ru1—N3 | 79.69 (7) | C19—C20—C21 | 119.0 (3) |
N2—Ru1—N4 | 97.12 (9) | C16—C21—C20 | 121.9 (2) |
N2—Ru1—N5 | 175.52 (9) | N4—C24—C25 | 123.0 (3) |
N3—Ru1—N4 | 90.54 (8) | C24—C25—C26 | 119.2 (3) |
N3—Ru1—N5 | 101.64 (7) | C25—C26—C27 | 118.0 (3) |
N4—Ru1—N5 | 78.63 (9) | C26—C27—C28 | 120.9 (3) |
F1—P1—F2 | 176.8 (2) | N4—C28—C27 | 120.2 (2) |
F1—P1—F3 | 80.2 (3) | N4—C28—C29 | 115.3 (2) |
F1—P1—F4 | 102.3 (3) | C27—C28—C29 | 124.5 (2) |
F1—P1—F5 | 93.1 (3) | N5—C29—C28 | 114.4 (2) |
F1—P1—F6 | 88.5 (4) | N5—C29—C30 | 120.8 (3) |
F1—P1—F7 | 92.0 (3) | C28—C29—C30 | 124.8 (3) |
F1—P1—F8 | 81.1 (3) | C29—C30—C31 | 120.4 (3) |
F1—P1—F9 | 77.2 (3) | C30—C31—C32 | 119.0 (3) |
F1—P1—F10 | 89.5 (3) | C31—C32—C33 | 119.0 (3) |
F2—P1—F3 | 98.3 (3) | N5—C33—C32 | 122.4 (2) |
F2—P1—F4 | 79.8 (3) | N6—C34—C35 | 179.0 (5) |
F2—P1—F5 | 89.6 (3) | N1—C1—H1 | 118.9 |
F2—P1—F6 | 88.8 (4) | C2—C1—H1 | 119.0 |
F2—P1—F7 | 88.6 (3) | C1—C2—H2 | 120.2 |
F2—P1—F8 | 98.5 (3) | C3—C2—H2 | 119.8 |
F2—P1—F9 | 106.0 (4) | C2—C3—H3 | 121.1 |
F2—P1—F10 | 87.4 (4) | C4—C3—H3 | 120.5 |
F3—P1—F4 | 167.4 (4) | C3—C4—H4 | 120.1 |
F3—P1—F5 | 83.7 (4) | C5—C4—H4 | 119.8 |
F3—P1—F6 | 95.3 (5) | C6—C7—H5 | 120.0 |
F4—P1—F5 | 83.8 (3) | C8—C7—H5 | 120.0 |
F4—P1—F6 | 97.1 (5) | C8—C9—H6 | 120.4 |
F5—P1—F6 | 178.0 (5) | C10—C9—H6 | 120.3 |
F7—P1—F8 | 172.1 (4) | C11—C12—H7 | 120.5 |
F7—P1—F9 | 85.9 (5) | C13—C12—H7 | 120.5 |
F7—P1—F10 | 92.1 (5) | C12—C13—H8 | 120.3 |
F8—P1—F9 | 88.8 (4) | C14—C13—H8 | 120.3 |
F8—P1—F10 | 91.7 (4) | C13—C14—H9 | 120.6 |
F9—P1—F10 | 166.4 (4) | C15—C14—H9 | 120.0 |
C17—O1—C22 | 119.1 (3) | N3—C15—H10 | 118.6 |
C20—O2—C23 | 116.6 (2) | C14—C15—H10 | 119.0 |
Ru1—N1—C1 | 128.21 (19) | C17—C18—H11 | 119.1 |
Ru1—N1—C5 | 113.32 (16) | C19—C18—H11 | 119.7 |
C1—N1—C5 | 118.5 (2) | C18—C19—H12 | 119.8 |
Ru1—N2—C6 | 119.35 (16) | C20—C19—H12 | 119.8 |
Ru1—N2—C10 | 119.39 (16) | C16—C21—H13 | 118.7 |
C6—N2—C10 | 121.2 (2) | C20—C21—H13 | 119.4 |
Ru1—N3—C11 | 113.17 (16) | O1—C22—H14 | 108.6 |
Ru1—N3—C15 | 129.04 (17) | O1—C22—H15 | 110.4 |
C11—N3—C15 | 117.8 (2) | O1—C22—H16 | 109.5 |
Ru1—N4—C24 | 124.92 (19) | H14—C22—H15 | 109.5 |
Ru1—N4—C28 | 116.36 (18) | H14—C22—H16 | 109.5 |
C24—N4—C28 | 118.7 (2) | H15—C22—H16 | 109.5 |
Ru1—N5—C29 | 115.22 (19) | O2—C23—H17 | 109.0 |
Ru1—N5—C33 | 126.37 (19) | O2—C23—H18 | 110.0 |
C29—N5—C33 | 118.4 (2) | O2—C23—H19 | 109.5 |
N1—C1—C2 | 122.1 (2) | H17—C23—H18 | 109.5 |
C1—C2—C3 | 120.0 (3) | H17—C23—H19 | 109.5 |
C2—C3—C4 | 118.4 (2) | H18—C23—H19 | 109.5 |
C3—C4—C5 | 120.1 (2) | N4—C24—H20 | 118.7 |
N1—C5—C4 | 120.7 (2) | C25—C24—H20 | 118.4 |
N1—C5—C6 | 115.1 (2) | C24—C25—H21 | 120.9 |
C4—C5—C6 | 124.1 (2) | C26—C25—H21 | 119.9 |
N2—C6—C5 | 112.5 (2) | C25—C26—H22 | 121.2 |
N2—C6—C7 | 120.2 (2) | C27—C26—H22 | 120.8 |
C5—C6—C7 | 127.3 (2) | C26—C27—H23 | 119.3 |
C6—C7—C8 | 120.0 (2) | C28—C27—H23 | 119.8 |
C7—C8—C9 | 118.8 (2) | C29—C30—H24 | 119.8 |
C7—C8—C16 | 122.3 (2) | C31—C30—H24 | 119.9 |
C9—C8—C16 | 118.9 (2) | C30—C31—H25 | 120.9 |
C8—C9—C10 | 119.3 (2) | C32—C31—H25 | 120.1 |
N2—C10—C9 | 120.4 (2) | C31—C32—H26 | 120.5 |
N2—C10—C11 | 113.1 (2) | C33—C32—H26 | 120.5 |
C9—C10—C11 | 126.5 (2) | N5—C33—H27 | 118.9 |
N3—C11—C10 | 114.6 (2) | C32—C33—H27 | 118.7 |
N3—C11—C12 | 121.9 (2) | C34—C35—H28 | 108.3 |
C10—C11—C12 | 123.5 (2) | C34—C35—H29 | 110.0 |
C11—C12—C13 | 119.1 (2) | C34—C35—H30 | 110.1 |
C12—C13—C14 | 119.4 (2) | H28—C35—H29 | 109.5 |
C13—C14—C15 | 119.3 (3) | H28—C35—H30 | 109.5 |
N3—C15—C14 | 122.5 (2) | H29—C35—H30 | 109.5 |
C8—C16—C17 | 121.5 (2) | ||
Cl1—Ru1—N1—C1 | −92.6 (2) | Ru1—N4—C28—C27 | −179.0 (2) |
Cl1—Ru1—N1—C5 | 87.90 (18) | Ru1—N4—C28—C29 | 1.8 (2) |
Cl1—Ru1—N2—C6 | −90.20 (19) | C24—N4—C28—C27 | 1.3 (3) |
Cl1—Ru1—N2—C10 | 88.8 (2) | C24—N4—C28—C29 | −177.9 (2) |
Cl1—Ru1—N3—C11 | −87.82 (17) | C28—N4—C24—C25 | −1.4 (3) |
Cl1—Ru1—N3—C15 | 92.8 (2) | Ru1—N5—C29—C28 | −3.1 (2) |
Cl1—Ru1—N5—C29 | −175.68 (17) | Ru1—N5—C29—C30 | 179.3 (2) |
Cl1—Ru1—N5—C33 | 6.0 (2) | Ru1—N5—C33—C32 | 178.7 (2) |
N1—Ru1—N2—C6 | 0.6 (2) | C29—N5—C33—C32 | 0.4 (4) |
N1—Ru1—N2—C10 | 179.6 (2) | C33—N5—C29—C28 | 175.4 (2) |
N2—Ru1—N1—C1 | 178.3 (2) | C33—N5—C29—C30 | −2.2 (4) |
N2—Ru1—N1—C5 | −1.20 (18) | N1—C1—C2—C3 | 1.2 (5) |
N1—Ru1—N3—C11 | 2.8 (3) | C1—C2—C3—C4 | 0.8 (5) |
N1—Ru1—N3—C15 | −176.6 (2) | C2—C3—C4—C5 | −0.9 (4) |
N3—Ru1—N1—C1 | 177.0 (2) | C3—C4—C5—N1 | −1.0 (4) |
N3—Ru1—N1—C5 | −2.5 (3) | C3—C4—C5—C6 | 179.9 (2) |
N1—Ru1—N4—C24 | 78.3 (2) | N1—C5—C6—N2 | −1.2 (3) |
N1—Ru1—N4—C28 | −101.35 (18) | N1—C5—C6—C7 | 175.9 (2) |
N4—Ru1—N1—C1 | 81.4 (2) | C4—C5—C6—N2 | 177.9 (2) |
N4—Ru1—N1—C5 | −98.16 (19) | C4—C5—C6—C7 | −5.0 (4) |
N1—Ru1—N5—C29 | 92.92 (19) | N2—C6—C7—C8 | −2.0 (4) |
N1—Ru1—N5—C33 | −85.4 (2) | C5—C6—C7—C8 | −178.9 (2) |
N5—Ru1—N1—C1 | 2.6 (2) | C6—C7—C8—C9 | −0.4 (4) |
N5—Ru1—N1—C5 | −176.89 (19) | C6—C7—C8—C16 | 176.4 (2) |
N2—Ru1—N3—C11 | 1.47 (18) | C7—C8—C9—C10 | 1.0 (4) |
N2—Ru1—N3—C15 | −177.9 (2) | C7—C8—C16—C17 | 48.6 (4) |
N3—Ru1—N2—C6 | −179.91 (18) | C7—C8—C16—C21 | −131.9 (3) |
N3—Ru1—N2—C10 | −0.9 (2) | C9—C8—C16—C17 | −134.7 (3) |
N2—Ru1—N4—C24 | −1.5 (2) | C9—C8—C16—C21 | 44.8 (3) |
N2—Ru1—N4—C28 | 178.82 (18) | C16—C8—C9—C10 | −175.8 (2) |
N4—Ru1—N2—C6 | 90.8 (2) | C8—C9—C10—N2 | 0.7 (4) |
N4—Ru1—N2—C10 | −90.1 (2) | C8—C9—C10—C11 | 178.0 (2) |
N3—Ru1—N4—C24 | −81.2 (2) | N2—C10—C11—N3 | 1.1 (3) |
N3—Ru1—N4—C28 | 99.14 (18) | N2—C10—C11—C12 | −179.7 (2) |
N4—Ru1—N3—C11 | 98.61 (18) | C9—C10—C11—N3 | −176.4 (2) |
N4—Ru1—N3—C15 | −80.8 (2) | C9—C10—C11—C12 | 2.8 (4) |
N3—Ru1—N5—C29 | −85.07 (19) | N3—C11—C12—C13 | 1.8 (4) |
N3—Ru1—N5—C33 | 96.6 (2) | C10—C11—C12—C13 | −177.3 (2) |
N5—Ru1—N3—C11 | 177.11 (18) | C11—C12—C13—C14 | −0.8 (4) |
N5—Ru1—N3—C15 | −2.3 (2) | C12—C13—C14—C15 | −0.4 (5) |
N4—Ru1—N5—C29 | 3.12 (18) | C13—C14—C15—N3 | 0.6 (5) |
N4—Ru1—N5—C33 | −175.2 (2) | C8—C16—C17—O1 | −0.0 (3) |
N5—Ru1—N4—C24 | 177.0 (2) | C8—C16—C17—C18 | 177.8 (3) |
N5—Ru1—N4—C28 | −2.62 (17) | C8—C16—C21—C20 | −179.4 (2) |
C22—O1—C17—C16 | −168.8 (3) | C17—C16—C21—C20 | 0.2 (4) |
C22—O1—C17—C18 | 13.5 (5) | C21—C16—C17—O1 | −179.6 (2) |
C23—O2—C20—C19 | −7.0 (5) | C21—C16—C17—C18 | −1.7 (4) |
C23—O2—C20—C21 | 171.2 (3) | O1—C17—C18—C19 | 179.4 (3) |
Ru1—N1—C1—C2 | 177.5 (2) | C16—C17—C18—C19 | 1.8 (5) |
Ru1—N1—C5—C4 | −177.5 (2) | C17—C18—C19—C20 | −0.2 (5) |
Ru1—N1—C5—C6 | 1.6 (2) | C18—C19—C20—O2 | 176.8 (3) |
C1—N1—C5—C4 | 2.9 (4) | C18—C19—C20—C21 | −1.3 (5) |
C1—N1—C5—C6 | −178.0 (2) | O2—C20—C21—C16 | −177.0 (2) |
C5—N1—C1—C2 | −3.0 (4) | C19—C20—C21—C16 | 1.4 (4) |
Ru1—N2—C6—C5 | 0.2 (2) | N4—C24—C25—C26 | 0.0 (3) |
Ru1—N2—C6—C7 | −177.1 (2) | C24—C25—C26—C27 | 1.3 (5) |
Ru1—N2—C10—C9 | 177.8 (2) | C25—C26—C27—C28 | −1.3 (5) |
Ru1—N2—C10—C11 | 0.2 (2) | C26—C27—C28—N4 | −0.0 (4) |
C6—N2—C10—C9 | −3.1 (4) | C26—C27—C28—C29 | 179.2 (3) |
C6—N2—C10—C11 | 179.2 (2) | N4—C28—C29—N5 | 0.9 (3) |
C10—N2—C6—C5 | −178.9 (2) | N4—C28—C29—C30 | 178.4 (2) |
C10—N2—C6—C7 | 3.8 (3) | C27—C28—C29—N5 | −178.3 (2) |
Ru1—N3—C11—C10 | −1.8 (2) | C27—C28—C29—C30 | −0.8 (4) |
Ru1—N3—C11—C12 | 179.0 (2) | N5—C29—C30—C31 | 2.0 (4) |
Ru1—N3—C15—C14 | 179.7 (2) | C28—C29—C30—C31 | −175.4 (3) |
C11—N3—C15—C14 | 0.3 (4) | C29—C30—C31—C32 | 0.2 (4) |
C15—N3—C11—C10 | 177.7 (2) | C30—C31—C32—C33 | −1.9 (5) |
C15—N3—C11—C12 | −1.5 (4) | C31—C32—C33—N5 | 1.7 (4) |
Ru1—N4—C24—C25 | 179.0 (2) |
Experimental details
Crystal data | |
Chemical formula | [RuCl(C10H8N2)(C23H19N3O2)]PF6·C2H3N |
Mr | 848.15 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 13.8691 (3), 16.1993 (3), 31.5514 (6) |
V (Å3) | 7088.7 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.60 × 0.40 × 0.08 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.616, 0.950 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 102710, 8092, 5738 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.111, 1.01 |
No. of reflections | 8092 |
No. of parameters | 495 |
No. of restraints | ? |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.84, −0.59 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku Americas & Rigaku, 2007), SIR97 (Altomare et al., 1999), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997).
Ru1—Cl1 | 2.4096 (8) | Ru1—N3 | 2.082 (2) |
Ru1—N1 | 2.066 (2) | Ru1—N4 | 2.036 (2) |
Ru1—N2 | 1.9503 (19) | Ru1—N5 | 2.084 (2) |
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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 have been numerous reports of ruthenium(II) polypyridyl complexes. In particular, a series of mononuclear ruthenium(II) complexes with both 2,2':6',2''-terpyridine (tpy) and bidentate pyridyl ligands (NN) has exhibited the catalytic activity toward water oxidation (Tseng et al., 2008). We newly investigated the synthesis of ruthenium complexes bearing the substituted terpyridyl ligand because the absorption energies of the MLCT bands and the redox potentials of the complexes described above were consistent with their structures.
The ligand environment about the Ru atom is distorted octahedral, with the substituted terpyridyl ligand coordinated in a meridional fashion, the bipyridyl ligand coordinated in a cis fashion and the Cl atom trans to one of the bipyridyl N atoms (Fig. 1). The Ru—N distances are in the range of 2.036 (2)–2.084 (2) Å with the exception of the central Ru—N bond of the terpyridyl ligand, which is shorter [1.9503 (19) Å] as expected (Table 1). The Ru—Cl distance of 2.4096 (8) Å observed in this structure is similar to those found in other ruthenium(II)-terpyridine- chlorido complexes (Spek et al., 1994; Fujihara et al., 2003; Tseng et al., 2008). The pendant dimethoxyphenyl substituent is not coplanar with the terpyridyl moiety; the dihedral angle between the central pyridyl and the dimethoxyphenyl ring is 46.72 (11)°. This result is essentially comparable to that found for the free ligand (50.2°) (Storrier et al., 1998).