Tris(1,10-phenanthroline-κ2N,N′)ruthenium(II) bis­(perchlorate)

Kozlowska, M.; Rodziewicz, P.; Brus, D.M.; Czyrko, J.; Brzezinski, K.

doi:10.1107/S1600536812048428

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1570-m1571

doi:10.1107/S1600536812048428

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Tris(1,10-phenanthroline-κ²N,N′)ruthenium(II) bis(perchlorate)

Mariana Kozlowska,^a Pawel Rodziewicz,^a Diana Malgorzata Brus,^a Justyna Czyrko ^a and Krzysztof Brzezinski ^a ^*

^aInstitute of Chemistry, University of Bialystok, Hurtowa 1, 15-399 Bialystok, Poland
^*Correspondence e-mail: k.brzezinski@uwb.edu.pl

(Received 14 November 2012; accepted 26 November 2012; online 30 November 2012)

The asymmetric unit of the title compound, [Ru(C₁₂H₈N₂)₃](ClO₄)₂, contains one octahedrally coordinated Ru^II 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).

Related 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

[Ru(C₁₂H₈N₂)₃](ClO₄)₂
M_r = 840.57
Monoclinic, C 2/c
a = 35.408 (7) Å
b = 16.106 (3) Å
c = 12.056 (2) Å
β = 102.22 (3)°
V = 6720 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 100 K
0.22 × 0.19 × 0.10 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.859, T_max = 1.000
28067 measured reflections
6867 independent reflections
5365 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.218
S = 1.04
6867 reflections
545 parameters
181 restraints
H-atom parameters constrained
Δρ_max = 2.55 e Å⁻³
Δρ_min = −1.22 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812048428/bx2430sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048428/bx2430Isup2.hkl

checkCIF report

Comment top

1,10-Phenanthroline (phen), forms complexes with most of transition metals. The polyimine complexes of divalent transition metal cations, such as [Ru^II(phen)₃](ClO₄)₂ or [Ru^II(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.

Related literature top

For the preparation of phenanthroline complexes with transition metals, see: Burstall et al. (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 et al. (1997); Yang et al. (1997); Miyasaka et al. (2001); Plonska et al. (2002); Winkler et al. (2006).

Experimental top

The transition metal complex salt, [Ru^II(phen)₃](ClO₄)₂ was prepared according to the procedure described by Burstall et al., 1952 and was recrystallized from methanol.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. For clarity, labels for atoms in the disordered perchlorate anions B and C are omitted.

Tris(1,10-phenanthroline-κ²N,N')ruthenium(II) bis(perchlorate) top

Crystal data top

[Ru(C₁₂H₈N₂)₃](ClO₄)₂	F(000) = 3392
M_r = 840.57	D_x = 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

Data collection top

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	R_int = 0.039
Detector resolution: 10.4052 pixels mm^-1	θ_max = 26.4°, θ_min = 2.8°
ω scans	h = −44→44
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −20→20
T_min = 0.859, T_max = 1.000	l = −14→15
28067 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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.218	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1194P)² + 53.7304P] where P = (F_o² + 2F_c²)/3
6867 reflections	(Δ/σ)_max = 0.001
545 parameters	Δρ_max = 2.55 e Å⁻³
181 restraints	Δρ_min = −1.22 e Å⁻³

Crystal data top

[Ru(C₁₂H₈N₂)₃](ClO₄)₂	V = 6720 (2) Å³
M_r = 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)°

Data collection top

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)
T_min = 0.859, T_max = 1.000	R_int = 0.039
28067 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	181 restraints
wR(F²) = 0.218	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1194P)² + 53.7304P] where P = (F_o² + 2F_c²)/3
6867 reflections	Δρ_max = 2.55 e Å⁻³
545 parameters	Δρ_min = −1.22 e Å⁻³

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	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.859, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	28067, 6867, 5365
R_int	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(F_o²) + (0.1194P)² + 53.7304P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (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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