metal-organic compounds
Tris(1,10-phenanthroline-κ2N,N′)ruthenium(II) bis(perchlorate)
aInstitute of Chemistry, University of Bialystok, Hurtowa 1, 15-399 Bialystok, Poland
*Correspondence e-mail: k.brzezinski@uwb.edu.pl
The 12H8N2)3](ClO4)2, contains one octahedrally coordinated RuII cation of the ruthenium-phenanthroline complex and three differently occupied perchlorate anions: two, denoted A and B, are located on the twofold axis while another, denoted C, is positioned in the proximity of the twofold screw axis. Perchlorate anions B and C are severely disordered. The occupancies of the two major conformers of anion B refined to 0.302 (6) and 0.198 (6). Perchlorate ion C was modeled in two alternate conformations which refined to occupancies of 0.552 (10) and 0.448 (10).
of the title compound, [Ru(CRelated literature
For the preparation of phenanthroline complexes with transition metals, see: Burstall & Nyholm (1952). For the structures of salts of complexes of ruthenium with phenanthroline, see: Breu & Stoll (1996); Maloney & MacDonnell (1997); Otsuka et al. (2001); Wu et al. (2001); Ghazzali et al. (2008). For background to the properties and applications of phenanthroline complexes, see: Juris et al. (1988); D'Angelantonio et al. (1991); Balzani et al. (1996); Mills & Williams (1997); Yang et al. (1997); Miyasaka et al. (2001); Plonska et al. (2002); Winkler et al. (2006).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812048428/bx2430sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812048428/bx2430Isup2.hkl
The transition metal complex salt, [RuII(phen)3](ClO4)2 was prepared according to the procedure described by Burstall et al., 1952 and was recrystallized from methanol.
The solvent/anion region is highly disordered and the final difference minimum and maximum (-1.15 and 2.62 e Å-3) indicate an its imperfect modeling. The highest difference peak corresponds to solvent accessible void in the
The disordered perchlorate anion B and C are modeled in two alternative conformations with geometric restraints (DFIX and SADI instructions). Additionally, displacement parameter restraints (DELU and ISOR instructions) are applied for anion B. Due to a serious disorder of perchlorate anion C, its oxygen atoms are refined isotropically. All H atoms were located in electron density difference maps. C-bonded hydrogen atoms were constrained to idealized positions with C—H distances fixed at 0.95 Å and 1.2Ueq(C).Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[Ru(C12H8N2)3](ClO4)2 | F(000) = 3392 |
Mr = 840.57 | Dx = 1.662 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 28661 reflections |
a = 35.408 (7) Å | θ = 2.6–26.3° |
b = 16.106 (3) Å | µ = 0.69 mm−1 |
c = 12.056 (2) Å | T = 100 K |
β = 102.22 (3)° | Plate, red |
V = 6720 (2) Å3 | 0.22 × 0.19 × 0.10 mm |
Z = 8 |
Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer | 6867 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 5365 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.039 |
Detector resolution: 10.4052 pixels mm-1 | θmax = 26.4°, θmin = 2.8° |
ω scans | h = −44→44 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −20→20 |
Tmin = 0.859, Tmax = 1.000 | l = −14→15 |
28067 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1194P)2 + 53.7304P] where P = (Fo2 + 2Fc2)/3 |
6867 reflections | (Δ/σ)max = 0.001 |
545 parameters | Δρmax = 2.55 e Å−3 |
181 restraints | Δρmin = −1.22 e Å−3 |
[Ru(C12H8N2)3](ClO4)2 | V = 6720 (2) Å3 |
Mr = 840.57 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 35.408 (7) Å | µ = 0.69 mm−1 |
b = 16.106 (3) Å | T = 100 K |
c = 12.056 (2) Å | 0.22 × 0.19 × 0.10 mm |
β = 102.22 (3)° |
Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer | 6867 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 5365 reflections with I > 2σ(I) |
Tmin = 0.859, Tmax = 1.000 | Rint = 0.039 |
28067 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | 181 restraints |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1194P)2 + 53.7304P] where P = (Fo2 + 2Fc2)/3 |
6867 reflections | Δρmax = 2.55 e Å−3 |
545 parameters | Δρmin = −1.22 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
ClA | 0.5000 | 0.08518 (12) | 1.2500 | 0.0409 (4) | |
O1A | 0.4920 (2) | 0.0360 (6) | 1.1532 (7) | 0.137 (4) | |
O2A | 0.53245 (17) | 0.1346 (4) | 1.2483 (7) | 0.098 (2) | |
ClBA | 0.49125 (14) | 0.4508 (3) | 0.7332 (5) | 0.0377 (19) | 0.302 (6) |
O1BA | 0.45000 (16) | 0.4625 (5) | 0.7094 (9) | 0.048 (3) | 0.302 (6) |
O2BA | 0.5065 (3) | 0.4809 (5) | 0.6390 (9) | 0.062 (5) | 0.302 (6) |
O3BA | 0.5000 | 0.3639 (3) | 0.7500 | 0.060 (3) | 0.605 (13) |
O4BA | 0.5085 (3) | 0.4961 (5) | 0.8342 (8) | 0.064 (5) | 0.302 (6) |
ClBB | 0.5000 | 0.4583 (5) | 0.7500 | 0.032 (2) | 0.395 (13) |
O1BB | 0.5200 (4) | 0.5161 (10) | 0.8333 (10) | 0.046 (4) | 0.198 (6) |
O2BB | 0.4835 (3) | 0.3927 (7) | 0.8057 (11) | 0.035 (4) | 0.198 (6) |
O3BB | 0.5266 (3) | 0.4238 (8) | 0.6871 (10) | 0.044 (4) | 0.198 (6) |
O4BB | 0.4697 (3) | 0.5022 (12) | 0.6740 (12) | 0.047 (4) | 0.198 (6) |
ClCA | 0.26318 (8) | 0.5086 (2) | 0.4468 (2) | 0.0435 (11) | 0.552 (10) |
O1CA | 0.2538 (2) | 0.5648 (4) | 0.3520 (5) | 0.064 (3)* | 0.552 (10) |
O2CA | 0.23054 (19) | 0.5010 (6) | 0.4998 (7) | 0.277 (19)* | 0.552 (10) |
O3CA | 0.2726 (3) | 0.4284 (3) | 0.4073 (7) | 0.091 (4)* | 0.552 (10) |
O4CA | 0.29584 (19) | 0.5403 (5) | 0.5278 (6) | 0.092 (4)* | 0.552 (10) |
ClCB | 0.2615 (2) | 0.5258 (6) | 0.4462 (7) | 0.166 (5) | 0.448 (10) |
O1CB | 0.2576 (6) | 0.6144 (5) | 0.4546 (17) | 0.149 (9)* | 0.448 (10) |
O2CB | 0.2292 (2) | 0.4858 (6) | 0.4795 (8) | 0.049 (3)* | 0.448 (10) |
O3CB | 0.2619 (4) | 0.5039 (12) | 0.3306 (8) | 0.212 (14)* | 0.448 (10) |
O4CB | 0.2969 (2) | 0.4984 (13) | 0.5192 (13) | 0.117 (6)* | 0.448 (10) |
Ru1 | 0.379433 (12) | 0.21680 (3) | 0.62688 (4) | 0.03927 (19) | |
N8 | 0.42571 (13) | 0.2140 (3) | 0.7640 (4) | 0.0407 (11) | |
N36 | 0.33253 (14) | 0.2267 (3) | 0.4936 (5) | 0.0455 (12) | |
N29 | 0.40257 (13) | 0.2905 (3) | 0.5175 (4) | 0.0404 (11) | |
N22 | 0.35194 (13) | 0.1363 (4) | 0.7156 (4) | 0.0475 (12) | |
C26 | 0.33993 (17) | −0.0117 (5) | 0.7393 (6) | 0.0522 (16) | |
N1 | 0.36793 (14) | 0.3206 (4) | 0.7139 (5) | 0.0515 (13) | |
C31 | 0.44900 (18) | 0.3752 (4) | 0.4513 (6) | 0.0509 (15) | |
H31 | 0.4740 | 0.3998 | 0.4661 | 0.061* | |
C25 | 0.31696 (19) | 0.0092 (5) | 0.8174 (6) | 0.0602 (19) | |
H25 | 0.3044 | −0.0332 | 0.8510 | 0.072* | |
C17 | 0.42222 (17) | 0.0127 (4) | 0.4478 (5) | 0.0454 (13) | |
H17 | 0.4373 | 0.0055 | 0.3921 | 0.054* | |
C7 | 0.42374 (17) | 0.2736 (4) | 0.8443 (5) | 0.0468 (15) | |
C16 | 0.41419 (14) | 0.0922 (4) | 0.4812 (4) | 0.0360 (11) | |
H16 | 0.4239 | 0.1385 | 0.4470 | 0.043* | |
N15 | 0.39328 (12) | 0.1058 (3) | 0.5599 (4) | 0.0367 (10) | |
C35 | 0.33975 (18) | 0.2702 (4) | 0.4047 (6) | 0.0510 (16) | |
C30 | 0.43730 (16) | 0.3264 (3) | 0.5347 (5) | 0.0403 (12) | |
H30 | 0.4547 | 0.3187 | 0.6056 | 0.048* | |
C27 | 0.3471 (2) | −0.0933 (5) | 0.7063 (6) | 0.0586 (18) | |
H27 | 0.3358 | −0.1384 | 0.7386 | 0.070* | |
C11 | 0.4786 (2) | 0.2177 (4) | 0.9732 (5) | 0.0539 (17) | |
H11 | 0.4967 | 0.2179 | 1.0437 | 0.065* | |
C37 | 0.29761 (16) | 0.1926 (4) | 0.4833 (7) | 0.0560 (17) | |
H37 | 0.2924 | 0.1608 | 0.5448 | 0.067* | |
C39 | 0.2751 (2) | 0.2466 (6) | 0.2965 (8) | 0.077 (2) | |
H39 | 0.2554 | 0.2533 | 0.2301 | 0.093* | |
C12 | 0.4499 (2) | 0.2781 (4) | 0.9494 (6) | 0.0521 (17) | |
C40 | 0.3120 (2) | 0.2835 (5) | 0.3033 (7) | 0.066 (2) | |
C21 | 0.35678 (15) | 0.0539 (4) | 0.6894 (5) | 0.0441 (13) | |
C41 | 0.3230 (3) | 0.3303 (6) | 0.2160 (8) | 0.084 (3) | |
H41 | 0.3045 | 0.3397 | 0.1476 | 0.101* | |
C18 | 0.40855 (18) | −0.0547 (4) | 0.4948 (6) | 0.0501 (15) | |
H18 | 0.4141 | −0.1092 | 0.4724 | 0.060* | |
C14 | 0.4168 (2) | 0.4011 (5) | 0.9966 (7) | 0.067 (2) | |
H14 | 0.4150 | 0.4452 | 1.0476 | 0.080* | |
C2 | 0.33910 (19) | 0.3754 (5) | 0.6835 (8) | 0.063 (2) | |
H2 | 0.3223 | 0.3709 | 0.6111 | 0.076* | |
C4 | 0.3582 (2) | 0.4498 (5) | 0.8596 (8) | 0.071 (2) | |
H4 | 0.3542 | 0.4937 | 0.9083 | 0.086* | |
C9 | 0.45398 (16) | 0.1585 (4) | 0.7900 (5) | 0.0444 (13) | |
H9 | 0.4562 | 0.1173 | 0.7354 | 0.053* | |
C13 | 0.4454 (2) | 0.3449 (5) | 1.0251 (6) | 0.063 (2) | |
H13 | 0.4628 | 0.3493 | 1.0964 | 0.075* | |
C6 | 0.39295 (17) | 0.3319 (4) | 0.8162 (6) | 0.0493 (15) | |
C19 | 0.38602 (16) | −0.0429 (4) | 0.5768 (5) | 0.0451 (14) | |
C20 | 0.37928 (14) | 0.0384 (4) | 0.6065 (5) | 0.0380 (12) | |
C38 | 0.26831 (19) | 0.2015 (5) | 0.3861 (8) | 0.067 (2) | |
H38 | 0.2438 | 0.1764 | 0.3825 | 0.081* | |
C24 | 0.31276 (18) | 0.0892 (5) | 0.8445 (6) | 0.0612 (19) | |
H24 | 0.2978 | 0.1032 | 0.8985 | 0.073* | |
C42 | 0.3588 (3) | 0.3619 (6) | 0.2264 (8) | 0.079 (2) | |
H42 | 0.3651 | 0.3920 | 0.1649 | 0.095* | |
C33 | 0.3874 (2) | 0.3510 (4) | 0.3275 (6) | 0.0586 (17) | |
C23 | 0.33056 (17) | 0.1525 (5) | 0.7930 (6) | 0.0581 (18) | |
H23 | 0.3273 | 0.2085 | 0.8137 | 0.070* | |
C28 | 0.3692 (2) | −0.1095 (4) | 0.6305 (6) | 0.0595 (18) | |
H28 | 0.3738 | −0.1655 | 0.6123 | 0.071* | |
C5 | 0.3892 (2) | 0.3961 (5) | 0.8918 (6) | 0.0566 (17) | |
C10 | 0.48045 (17) | 0.1579 (4) | 0.8934 (5) | 0.0486 (15) | |
H10 | 0.4998 | 0.1161 | 0.9087 | 0.058* | |
C32 | 0.4242 (2) | 0.3874 (4) | 0.3480 (7) | 0.0584 (17) | |
H32 | 0.4319 | 0.4201 | 0.2911 | 0.070* | |
C34 | 0.37750 (17) | 0.3047 (4) | 0.4163 (6) | 0.0481 (14) | |
C3 | 0.3336 (2) | 0.4388 (5) | 0.7571 (8) | 0.074 (2) | |
H3 | 0.3122 | 0.4752 | 0.7354 | 0.088* |
U11 | U22 | U33 | U12 | U13 | U23 | |
ClA | 0.0410 (10) | 0.0385 (10) | 0.0390 (10) | 0.000 | −0.0006 (8) | 0.000 |
O1A | 0.106 (5) | 0.182 (9) | 0.104 (5) | 0.037 (6) | −0.021 (4) | −0.086 (6) |
O2A | 0.059 (3) | 0.079 (4) | 0.161 (7) | −0.008 (3) | 0.035 (4) | 0.029 (4) |
ClBA | 0.045 (3) | 0.035 (3) | 0.029 (3) | −0.007 (2) | −0.002 (3) | 0.001 (2) |
O1BA | 0.040 (5) | 0.052 (7) | 0.055 (7) | 0.002 (5) | 0.012 (5) | −0.014 (6) |
O2BA | 0.053 (7) | 0.079 (8) | 0.060 (7) | −0.014 (7) | 0.027 (6) | 0.010 (6) |
O3BA | 0.068 (6) | 0.043 (4) | 0.055 (6) | 0.000 | −0.017 (5) | 0.000 |
O4BA | 0.053 (8) | 0.074 (8) | 0.066 (7) | −0.010 (7) | 0.012 (6) | −0.033 (7) |
ClBB | 0.050 (4) | 0.026 (3) | 0.016 (3) | 0.000 | −0.004 (3) | 0.000 |
O1BB | 0.050 (6) | 0.043 (6) | 0.043 (5) | −0.009 (4) | 0.008 (4) | −0.007 (4) |
O2BB | 0.033 (6) | 0.035 (5) | 0.036 (6) | 0.002 (4) | 0.008 (4) | 0.002 (4) |
O3BB | 0.043 (6) | 0.046 (6) | 0.045 (6) | −0.007 (4) | 0.015 (4) | −0.007 (4) |
O4BB | 0.051 (6) | 0.045 (6) | 0.043 (5) | 0.007 (4) | 0.005 (4) | 0.006 (4) |
ClCA | 0.0446 (18) | 0.0573 (19) | 0.0324 (15) | −0.0289 (13) | 0.0166 (12) | −0.0096 (11) |
ClCB | 0.112 (7) | 0.231 (10) | 0.155 (8) | −0.029 (7) | 0.029 (6) | −0.011 (7) |
Ru1 | 0.0236 (3) | 0.0438 (3) | 0.0511 (3) | −0.00316 (17) | 0.00957 (19) | −0.0083 (2) |
N8 | 0.029 (2) | 0.052 (3) | 0.044 (3) | −0.011 (2) | 0.0141 (19) | −0.007 (2) |
N36 | 0.027 (2) | 0.046 (3) | 0.062 (3) | 0.0037 (19) | 0.006 (2) | −0.009 (2) |
N29 | 0.031 (2) | 0.036 (2) | 0.055 (3) | 0.0039 (18) | 0.011 (2) | −0.005 (2) |
N22 | 0.027 (2) | 0.062 (3) | 0.054 (3) | −0.011 (2) | 0.011 (2) | −0.008 (3) |
C26 | 0.033 (3) | 0.069 (4) | 0.052 (4) | −0.009 (3) | 0.005 (3) | 0.012 (3) |
N1 | 0.033 (2) | 0.054 (3) | 0.072 (4) | −0.006 (2) | 0.022 (2) | −0.015 (3) |
C31 | 0.044 (3) | 0.036 (3) | 0.076 (4) | 0.002 (2) | 0.020 (3) | −0.001 (3) |
C25 | 0.041 (3) | 0.083 (5) | 0.056 (4) | −0.019 (3) | 0.010 (3) | 0.008 (4) |
C17 | 0.039 (3) | 0.049 (3) | 0.047 (3) | 0.009 (3) | 0.008 (2) | 0.002 (3) |
C7 | 0.036 (3) | 0.057 (4) | 0.053 (3) | −0.020 (3) | 0.021 (3) | −0.013 (3) |
C16 | 0.029 (2) | 0.039 (3) | 0.038 (3) | 0.001 (2) | 0.003 (2) | −0.001 (2) |
N15 | 0.026 (2) | 0.041 (2) | 0.042 (2) | 0.0037 (18) | 0.0020 (18) | 0.001 (2) |
C35 | 0.033 (3) | 0.045 (3) | 0.070 (4) | 0.010 (2) | 0.001 (3) | −0.008 (3) |
C30 | 0.035 (3) | 0.033 (3) | 0.054 (3) | 0.001 (2) | 0.011 (2) | −0.006 (2) |
C27 | 0.048 (4) | 0.059 (4) | 0.067 (4) | −0.008 (3) | 0.008 (3) | 0.021 (3) |
C11 | 0.053 (4) | 0.074 (5) | 0.037 (3) | −0.026 (3) | 0.014 (3) | 0.002 (3) |
C37 | 0.025 (3) | 0.053 (4) | 0.085 (5) | 0.003 (3) | 0.002 (3) | −0.018 (3) |
C39 | 0.041 (4) | 0.076 (5) | 0.098 (6) | 0.019 (4) | −0.021 (4) | −0.015 (4) |
C12 | 0.053 (4) | 0.063 (4) | 0.045 (3) | −0.030 (3) | 0.023 (3) | −0.009 (3) |
C40 | 0.044 (4) | 0.062 (5) | 0.080 (5) | 0.011 (3) | −0.010 (4) | 0.012 (4) |
C21 | 0.028 (3) | 0.054 (4) | 0.049 (3) | −0.006 (2) | 0.004 (2) | 0.001 (3) |
C41 | 0.071 (5) | 0.087 (6) | 0.079 (6) | 0.010 (5) | −0.022 (4) | 0.013 (5) |
C18 | 0.043 (3) | 0.043 (3) | 0.063 (4) | 0.011 (3) | 0.006 (3) | 0.005 (3) |
C14 | 0.080 (5) | 0.068 (5) | 0.065 (5) | −0.034 (4) | 0.044 (4) | −0.024 (4) |
C2 | 0.039 (3) | 0.058 (4) | 0.098 (6) | −0.005 (3) | 0.026 (3) | −0.023 (4) |
C4 | 0.063 (5) | 0.065 (5) | 0.097 (6) | −0.023 (4) | 0.043 (4) | −0.035 (4) |
C9 | 0.034 (3) | 0.055 (4) | 0.046 (3) | −0.008 (3) | 0.012 (2) | 0.003 (3) |
C13 | 0.067 (4) | 0.076 (5) | 0.052 (4) | −0.028 (4) | 0.025 (3) | −0.021 (4) |
C6 | 0.041 (3) | 0.056 (4) | 0.059 (4) | −0.016 (3) | 0.027 (3) | −0.016 (3) |
C19 | 0.036 (3) | 0.042 (3) | 0.053 (3) | 0.006 (2) | 0.001 (2) | 0.010 (3) |
C20 | 0.026 (2) | 0.043 (3) | 0.042 (3) | −0.004 (2) | 0.000 (2) | 0.000 (2) |
C38 | 0.031 (3) | 0.062 (4) | 0.101 (6) | 0.011 (3) | −0.005 (3) | −0.018 (4) |
C24 | 0.035 (3) | 0.094 (6) | 0.058 (4) | −0.019 (3) | 0.019 (3) | −0.007 (4) |
C42 | 0.081 (6) | 0.078 (6) | 0.071 (5) | 0.015 (5) | 0.002 (4) | 0.022 (4) |
C33 | 0.057 (4) | 0.052 (4) | 0.065 (4) | 0.012 (3) | 0.007 (3) | 0.006 (3) |
C23 | 0.032 (3) | 0.079 (5) | 0.066 (4) | −0.014 (3) | 0.018 (3) | −0.020 (4) |
C28 | 0.053 (4) | 0.046 (4) | 0.074 (5) | 0.004 (3) | 0.000 (3) | 0.014 (3) |
C5 | 0.051 (4) | 0.060 (4) | 0.069 (4) | −0.017 (3) | 0.038 (3) | −0.018 (3) |
C10 | 0.041 (3) | 0.065 (4) | 0.040 (3) | −0.016 (3) | 0.007 (2) | 0.008 (3) |
C32 | 0.060 (4) | 0.047 (4) | 0.072 (5) | 0.002 (3) | 0.022 (4) | 0.008 (3) |
C34 | 0.037 (3) | 0.041 (3) | 0.062 (4) | 0.007 (2) | 0.004 (3) | 0.001 (3) |
C3 | 0.049 (4) | 0.059 (4) | 0.123 (7) | 0.001 (3) | 0.040 (4) | −0.027 (5) |
ClA—O1A | 1.389 (6) | C16—N15 | 1.339 (7) |
ClA—O1Ai | 1.389 (6) | C16—H16 | 0.9500 |
ClA—O2A | 1.402 (6) | N15—C20 | 1.363 (7) |
ClA—O2Ai | 1.402 (6) | C35—C40 | 1.413 (10) |
ClBA—O4BA | 1.4398 (8) | C35—C34 | 1.427 (9) |
ClBA—O1BA | 1.4399 (8) | C30—H30 | 0.9500 |
ClBA—O3BA | 1.4400 (8) | C27—C28 | 1.350 (11) |
ClBA—O2BA | 1.4401 (8) | C27—H27 | 0.9500 |
ClBB—O1BB | 1.4399 (8) | C11—C10 | 1.373 (10) |
ClBB—O3BB | 1.4399 (8) | C11—C12 | 1.393 (11) |
ClBB—O2BB | 1.4401 (8) | C11—H11 | 0.9500 |
ClBB—O4BB | 1.4402 (11) | C37—C38 | 1.399 (10) |
ClCA—O2CA | 1.4399 (8) | C37—H37 | 0.9500 |
ClCA—O4CA | 1.4402 (9) | C39—C38 | 1.366 (13) |
ClCA—O3CA | 1.4405 (8) | C39—C40 | 1.421 (12) |
ClCA—O1CA | 1.4407 (8) | C39—H39 | 0.9500 |
ClCB—O4CB | 1.4400 (11) | C12—C13 | 1.440 (10) |
ClCB—O1CB | 1.4400 (8) | C40—C41 | 1.415 (13) |
ClCB—O2CB | 1.4400 (8) | C21—C20 | 1.426 (8) |
ClCB—O3CB | 1.4403 (8) | C41—C42 | 1.347 (13) |
Ru1—N22 | 2.053 (5) | C41—H41 | 0.9500 |
Ru1—N36 | 2.058 (5) | C18—C19 | 1.409 (9) |
Ru1—N1 | 2.059 (5) | C18—H18 | 0.9500 |
Ru1—N15 | 2.063 (5) | C14—C13 | 1.347 (12) |
Ru1—N8 | 2.067 (5) | C14—C5 | 1.426 (11) |
Ru1—N29 | 2.068 (5) | C14—H14 | 0.9500 |
N8—C9 | 1.329 (8) | C2—C3 | 1.393 (10) |
N8—C7 | 1.376 (8) | C2—H2 | 0.9500 |
N36—C37 | 1.334 (8) | C4—C3 | 1.365 (12) |
N36—C35 | 1.349 (9) | C4—C5 | 1.387 (11) |
N29—C30 | 1.335 (7) | C4—H4 | 0.9500 |
N29—C34 | 1.368 (8) | C9—C10 | 1.392 (8) |
N22—C23 | 1.346 (8) | C9—H9 | 0.9500 |
N22—C21 | 1.383 (8) | C13—H13 | 0.9500 |
C26—C25 | 1.410 (10) | C6—C5 | 1.403 (9) |
C26—C21 | 1.410 (9) | C19—C20 | 1.392 (8) |
C26—C27 | 1.410 (11) | C19—C28 | 1.444 (9) |
N1—C2 | 1.340 (9) | C38—H38 | 0.9500 |
N1—C6 | 1.370 (8) | C24—C23 | 1.409 (10) |
C31—C32 | 1.378 (10) | C24—H24 | 0.9500 |
C31—C30 | 1.406 (9) | C42—C33 | 1.421 (11) |
C31—H31 | 0.9500 | C42—H42 | 0.9500 |
C25—C24 | 1.346 (11) | C33—C32 | 1.401 (10) |
C25—H25 | 0.9500 | C33—C34 | 1.409 (10) |
C17—C18 | 1.361 (9) | C23—H23 | 0.9500 |
C17—C16 | 1.388 (8) | C28—H28 | 0.9500 |
C17—H17 | 0.9500 | C10—H10 | 0.9500 |
C7—C12 | 1.405 (9) | C32—H32 | 0.9500 |
C7—C6 | 1.424 (10) | C3—H3 | 0.9500 |
O1A—ClA—O1Ai | 110.5 (9) | C31—C30—H30 | 118.9 |
O1A—ClA—O2A | 109.5 (6) | C28—C27—C26 | 122.4 (6) |
O1Ai—ClA—O2A | 108.3 (4) | C28—C27—H27 | 118.8 |
O1A—ClA—O2Ai | 108.3 (4) | C26—C27—H27 | 118.8 |
O1Ai—ClA—O2Ai | 109.5 (6) | C10—C11—C12 | 119.2 (6) |
O2A—ClA—O2Ai | 110.8 (6) | C10—C11—H11 | 120.4 |
O4BA—ClBA—O1BA | 109.48 (6) | C12—C11—H11 | 120.4 |
O4BA—ClBA—O3BA | 109.49 (6) | N36—C37—C38 | 122.9 (8) |
O1BA—ClBA—O3BA | 109.48 (6) | N36—C37—H37 | 118.5 |
O4BA—ClBA—O2BA | 109.48 (6) | C38—C37—H37 | 118.5 |
O1BA—ClBA—O2BA | 109.47 (6) | C38—C39—C40 | 119.4 (7) |
O3BA—ClBA—O2BA | 109.44 (6) | C38—C39—H39 | 120.3 |
O1BB—ClBB—O3BB | 109.7 (2) | C40—C39—H39 | 120.3 |
O1BB—ClBB—O2BB | 109.7 (2) | C11—C12—C7 | 117.5 (6) |
O3BB—ClBB—O2BB | 109.7 (2) | C11—C12—C13 | 124.4 (7) |
O1BB—ClBB—O4BB | 108.4 (12) | C7—C12—C13 | 118.0 (7) |
O3BB—ClBB—O4BB | 109.7 (2) | C35—C40—C41 | 118.4 (7) |
O2BB—ClBB—O4BB | 109.7 (3) | C35—C40—C39 | 116.7 (8) |
O2CA—ClCA—O4CA | 109.52 (6) | C41—C40—C39 | 125.0 (8) |
O2CA—ClCA—O3CA | 109.50 (6) | N22—C21—C26 | 122.5 (6) |
O4CA—ClCA—O3CA | 109.46 (6) | N22—C21—C20 | 116.3 (5) |
O2CA—ClCA—O1CA | 109.49 (6) | C26—C21—C20 | 121.1 (6) |
O4CA—ClCA—O1CA | 109.44 (6) | C42—C41—C40 | 122.2 (7) |
O3CA—ClCA—O1CA | 109.43 (6) | C42—C41—H41 | 118.9 |
O4CB—ClCB—O1CB | 110.1 (15) | C40—C41—H41 | 118.9 |
O4CB—ClCB—O2CB | 109.4 (3) | C17—C18—C19 | 119.2 (6) |
O1CB—ClCB—O2CB | 109.4 (3) | C17—C18—H18 | 120.4 |
O4CB—ClCB—O3CB | 109.3 (3) | C19—C18—H18 | 120.4 |
O1CB—ClCB—O3CB | 109.3 (3) | C13—C14—C5 | 121.6 (7) |
O2CB—ClCB—O3CB | 109.3 (3) | C13—C14—H14 | 119.2 |
N22—Ru1—N36 | 93.6 (2) | C5—C14—H14 | 119.2 |
N22—Ru1—N1 | 94.6 (2) | N1—C2—C3 | 120.6 (8) |
N36—Ru1—N1 | 96.9 (2) | N1—C2—H2 | 119.7 |
N22—Ru1—N15 | 80.5 (2) | C3—C2—H2 | 119.7 |
N36—Ru1—N15 | 88.90 (18) | C3—C4—C5 | 119.2 (7) |
N1—Ru1—N15 | 172.6 (2) | C3—C4—H4 | 120.4 |
N22—Ru1—N8 | 87.27 (19) | C5—C4—H4 | 120.4 |
N36—Ru1—N8 | 176.5 (2) | N8—C9—C10 | 123.2 (6) |
N1—Ru1—N8 | 79.6 (2) | N8—C9—H9 | 118.4 |
N15—Ru1—N8 | 94.60 (18) | C10—C9—H9 | 118.4 |
N22—Ru1—N29 | 172.08 (19) | C14—C13—C12 | 121.3 (7) |
N36—Ru1—N29 | 79.7 (2) | C14—C13—H13 | 119.4 |
N1—Ru1—N29 | 90.4 (2) | C12—C13—H13 | 119.4 |
N15—Ru1—N29 | 95.09 (18) | N1—C6—C5 | 123.4 (6) |
N8—Ru1—N29 | 99.70 (19) | N1—C6—C7 | 116.3 (5) |
C9—N8—C7 | 116.8 (5) | C5—C6—C7 | 120.3 (6) |
C9—N8—Ru1 | 129.3 (4) | C20—C19—C18 | 117.4 (6) |
C7—N8—Ru1 | 113.4 (4) | C20—C19—C28 | 118.3 (6) |
C37—N36—C35 | 117.9 (6) | C18—C19—C28 | 124.3 (6) |
C37—N36—Ru1 | 128.2 (5) | N15—C20—C19 | 123.1 (5) |
C35—N36—Ru1 | 113.8 (4) | N15—C20—C21 | 117.1 (5) |
C30—N29—C34 | 117.9 (5) | C19—C20—C21 | 119.8 (5) |
C30—N29—Ru1 | 128.8 (4) | C39—C38—C37 | 119.6 (7) |
C34—N29—Ru1 | 113.3 (4) | C39—C38—H38 | 120.2 |
C23—N22—C21 | 117.3 (6) | C37—C38—H38 | 120.2 |
C23—N22—Ru1 | 129.6 (5) | C25—C24—C23 | 120.2 (7) |
C21—N22—Ru1 | 113.0 (4) | C25—C24—H24 | 119.9 |
C25—C26—C21 | 117.5 (7) | C23—C24—H24 | 119.9 |
C25—C26—C27 | 125.0 (7) | C41—C42—C33 | 121.3 (8) |
C21—C26—C27 | 117.5 (6) | C41—C42—H42 | 119.4 |
C2—N1—C6 | 117.9 (6) | C33—C42—H42 | 119.4 |
C2—N1—Ru1 | 128.1 (5) | C32—C33—C34 | 117.3 (6) |
C6—N1—Ru1 | 114.0 (4) | C32—C33—C42 | 124.5 (8) |
C32—C31—C30 | 119.8 (6) | C34—C33—C42 | 118.1 (7) |
C32—C31—H31 | 120.1 | N22—C23—C24 | 122.4 (7) |
C30—C31—H31 | 120.1 | N22—C23—H23 | 118.8 |
C24—C25—C26 | 120.0 (7) | C24—C23—H23 | 118.8 |
C24—C25—H25 | 120.0 | C27—C28—C19 | 120.9 (7) |
C26—C25—H25 | 120.0 | C27—C28—H28 | 119.6 |
C18—C17—C16 | 120.2 (6) | C19—C28—H28 | 119.6 |
C18—C17—H17 | 119.9 | C4—C5—C6 | 117.1 (7) |
C16—C17—H17 | 119.9 | C4—C5—C14 | 124.4 (7) |
N8—C7—C12 | 123.3 (6) | C6—C5—C14 | 118.5 (7) |
N8—C7—C6 | 116.3 (6) | C11—C10—C9 | 119.9 (7) |
C12—C7—C6 | 120.4 (6) | C11—C10—H10 | 120.0 |
N15—C16—C17 | 122.3 (5) | C9—C10—H10 | 120.0 |
N15—C16—H16 | 118.9 | C31—C32—C33 | 119.4 (7) |
C17—C16—H16 | 118.9 | C31—C32—H32 | 120.3 |
C16—N15—C20 | 117.7 (5) | C33—C32—H32 | 120.3 |
C16—N15—Ru1 | 129.2 (4) | N29—C34—C33 | 123.2 (6) |
C20—N15—Ru1 | 113.1 (4) | N29—C34—C35 | 116.1 (6) |
N36—C35—C40 | 123.5 (6) | C33—C34—C35 | 120.7 (6) |
N36—C35—C34 | 117.1 (6) | C4—C3—C2 | 121.5 (8) |
C40—C35—C34 | 119.4 (7) | C4—C3—H3 | 119.2 |
N29—C30—C31 | 122.2 (6) | C2—C3—H3 | 119.2 |
N29—C30—H30 | 118.9 |
Symmetry code: (i) −x+1, y, −z+5/2. |
Experimental details
Crystal data | |
Chemical formula | [Ru(C12H8N2)3](ClO4)2 |
Mr | 840.57 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 35.408 (7), 16.106 (3), 12.056 (2) |
β (°) | 102.22 (3) |
V (Å3) | 6720 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.22 × 0.19 × 0.10 |
Data collection | |
Diffractometer | Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.859, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28067, 6867, 5365 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.218, 1.04 |
No. of reflections | 6867 |
No. of parameters | 545 |
No. of restraints | 181 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.1194P)2 + 53.7304P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.55, −1.22 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXD (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).
Acknowledgements
This work was supported by the HOMING PLUS project of the Foundation for Polish Science (MK and PR). The X-ray diffractometer was funded by the EFRD as part of the Operational Programme Development of Eastern Poland 2007–2013, project: POPW.01.03.00–20–034/09–00.
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1,10-Phenanthroline (phen), forms complexes with most of transition metals. The polyimine complexes of divalent transition metal cations, such as [RuII(phen)3](ClO4)2 or [RuII(bpy)3](ClO4)2 (bpy-2,2'-bipyridine), are well known potent photosensitizers (Juris et al., 1988). These compounds reveal also other interesting properties due to their redox (Plonska et al., 2002; Winkler et al., 2006) and magnetic properties (Miyasaka et al., 2001), excited-state reactivity (D'Angelantonio et al., 1991), and emission and lifetime characteristics (Juris et al., 1988; Balzani et al., 1996). A high photostability, long excited-state lifetimes and high quantum yields of luminescence, enabled to use them as oxygen optical sensors (Mills et al., 1997). A binding of these complexes to calf thymus DNA has been also investigated (Yang et al., 1997).
The asymmetric unit contains one divalent cation of the ruthenium-phenanthroline complex and three differently occupied perchlorate anions (Fig. 1). The half-ion of perchlorate A is located on the twofold axis and the complete anion is generated by the symmetry operation. Perchlorate anions, B and C are disordered and each one of them is modeled in two alternative conformations. The occupancy of two major conformers is refined to 0.302 (6) and 0.198 (6) or 0.552 (10) and 0.448 (10) for anion B or C, respectively. Conformers of perchlorate ion B are located on the twofold axis.