Bis(2,2′:6′,2′′-terpyridine)­ruthenium(II) bis­(perchlorate) hemihydrate

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

doi:10.1107/S1600536812043917

Bis(2,2′:6′,2′′-terpyridine)ruthenium(II) bis(perchlorate) hemihydrate

M. Kozlowska, P. Rodziewicz, D. M. Brus, J. Breczko and K. Brzezinski

The asymmetric unit of the title compound, [Ru(C₁₅H₁₁N₃)₂](ClO₄)₂·0.5H₂O, contains one ruthenium–terpiridine complex cation, two perchlorate anions and one half-molecule of water. Face-to-face and face-to-edge π-stacking interactions between terpyridine units [centroid–centroid distances = 3.793 (2) and 3.801 (2) Å] stabilize the crystal lattice The partially occupied water molecule interacts with two perchlorate ions via O—H

O hydrogen bonds. In the crystal lattice, the complex cations, perchlorate ion-water pairs and the second perchlorate anions are arranged into columns along b direction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812043917/bt6849sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812043917/bt6849Isup2.hkl Contains datablock I

CCDC reference: 909756

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.005 Å
Disorder in solvent or counterion
R factor = 0.042
wR factor = 0.083
Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          2

Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of        Cl1A
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........    <I>CG</
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........    <I>CG</
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      4.455
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT975_ALERT_2_C Positive Residual Density at 1.03A from O4B    .       0.60 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 0.85A from O4B    .       0.51 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in CIF ...          ?
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       7.00
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................          5 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

A 2,2':6',2''-terpyridine (tpy) compound, as chelating N-donor, forms complexes with most of transition metals (Burstall et al., 1952). The polyimine complexes of divalent transition metal cations are well known due to their photophysical and electrochemical properties (Anders et al., 2004; Plonska et al., 2002; Winkler et al., 2003; Winkler et al., 2006). Ruthenium complexes with terpyridyl or bipyridyl ligands might catalyze photochemical water oxidation (Constable, 2007). The metal-to-ligand charge transfer processes in the visible region enable photo- and electroluminescence phenomena and make these applicable in a supramolecular chemistry (Constable, 2007).

The asymmetric unit contains one divalent cation of the ruthenium-terpiridine complex, two perchlorate anions and a water molecule with a half-occupancy (Fig. 1). The crystal lattice is stabilized by terpyridine moieties and respective face-to-face and face-to-edge π-stacking interactions. The partially occupied water molecule and one perchlorate anion are located in a proximity of the inversion center and a symmetry related water-anion pair is generated. Two hydrogen bonds O5—H5A···O1A and H5—H5B···O2A (equivalent anion -x + 2,-y + 1,-z) are formed between water molecule and oxygen atoms of perchlorate units. Geometrical parameters of hydrogen bond interactions are summarized in Table 1. In the crystal lattice each water molecule serves as a bridge between two symmetry dependent perchlorate units (Fig. 2). It is of note, that only one perchlorate unit and its symmetry-mates form hydrogen bonds with water molecules, whereas the second anion interacts with C-bonded hydrogen atoms (Fig 2).

Related literature top

For the preparation of terpyridine complexes with transition metals, see: Burstall et al. (1952). For the structures of salts of complexes of ruthenium with terpyridine, see: Craig et al. (1998); Lashgari et al. (1999); Pyo et al. (1999); Tovee et al. (2009); Walstrom et al. (2009). For background to the properties and applications of terpiridine complexes, see: Anders et al. (2004); Constable (2007); Plonska et al. (2002); Winkler et al. (2003, 2006).

Experimental top

The transition metal complex salt, [Ru^II(tpy)₂](ClO₄)₂ was prepared according to the procedure described by Burstall et al. (1952). Crystals suitable for X-ray diffraction study were obtained at room temperature by a slow evaporation of [Ru^II(tpy)₂](ClO₄)₂ solution in acetonitrile.

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, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing viewed along b direction. Dashed lines represent hydrogen bonds between half-molecule of water and perchlorate anions.

Bis(2,2':6',2''-terpyridine)ruthenium(II) bis(perchlorate) hemihydrate top

Crystal data top

[Ru(C₁₅H₁₁N₃)₂](ClO₄)₂·0.5H₂O	F(000) = 1564
M_r = 775.51	D_x = 1.706 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7538 reflections
a = 8.7676 (2) Å	θ = 2.5–26.3°
b = 8.8221 (9) Å	µ = 0.76 mm⁻¹
c = 39.118 (4) Å	T = 100 K
β = 93.582 (5)°	Plate, red
V = 3019.8 (4) Å³	0.15 × 0.12 × 0.03 mm
Z = 4

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	6158 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	5858 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.4052 pixels mm^-1	θ_max = 26.4°, θ_min = 2.5°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = 0→11
T_min = 0.801, T_max = 1.000	l = 0→48
16537 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	w = 1/[σ²(F_o²) + (0.0111P)² + 7.0042P] where P = (F_o² + 2F_c²)/3
6158 reflections	(Δ/σ)_max = 0.001
439 parameters	Δρ_max = 0.65 e Å⁻³
3 restraints	Δρ_min = −1.17 e Å⁻³

Crystal data top

[Ru(C₁₅H₁₁N₃)₂](ClO₄)₂·0.5H₂O	V = 3019.8 (4) Å³
M_r = 775.51	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.7676 (2) Å	µ = 0.76 mm⁻¹
b = 8.8221 (9) Å	T = 100 K
c = 39.118 (4) Å	0.15 × 0.12 × 0.03 mm
β = 93.582 (5)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	6158 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	5858 reflections with I > 2σ(I)
T_min = 0.801, T_max = 1.000	R_int = 0.027
16537 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	3 restraints
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	Δρ_max = 0.65 e Å⁻³
6158 reflections	Δρ_min = −1.17 e Å⁻³
439 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ru1	0.35193 (3)	0.33315 (3)	0.127794 (6)	0.01027 (7)
N1A	0.2631 (3)	0.1164 (3)	0.12359 (7)	0.0121 (5)
N3A	0.4324 (3)	0.5408 (3)	0.11162 (7)	0.0122 (5)
C15A	0.4968 (3)	0.6520 (4)	0.13099 (8)	0.0142 (6)
H15A	0.5039	0.6399	0.1552	0.017*
C1A	0.2479 (3)	0.0135 (4)	0.14867 (8)	0.0155 (7)
H1A	0.2837	0.0386	0.1714	0.019*
C10A	0.3495 (3)	0.4333 (4)	0.05723 (8)	0.0139 (6)
C10B	0.5227 (3)	0.3134 (4)	0.19339 (8)	0.0145 (6)
C11A	0.4207 (3)	0.5607 (4)	0.07649 (8)	0.0145 (6)
C5A	0.2170 (3)	0.0758 (4)	0.09058 (8)	0.0142 (6)
C12A	0.4743 (4)	0.6915 (4)	0.06155 (9)	0.0179 (7)
H12A	0.4635	0.7042	0.0374	0.022*
C2A	0.1819 (4)	−0.1275 (4)	0.14247 (9)	0.0181 (7)
H2A	0.1724	−0.1975	0.1607	0.022*
C15B	0.6578 (3)	0.1840 (4)	0.11219 (8)	0.0156 (7)
H15B	0.6228	0.1879	0.0887	0.019*
C4A	0.1491 (4)	−0.0635 (4)	0.08320 (9)	0.0174 (7)
H4A	0.1162	−0.0888	0.0603	0.021*
C12B	0.7609 (4)	0.1731 (4)	0.17951 (9)	0.0199 (7)
H12B	0.7949	0.1700	0.2030	0.024*
C8A	0.2508 (4)	0.2943 (4)	0.00816 (8)	0.0213 (7)
H8A	0.2296	0.2866	−0.0159	0.026*
C9A	0.3187 (4)	0.4247 (4)	0.02177 (8)	0.0184 (7)
H9A	0.3437	0.5064	0.0073	0.022*
C14A	0.5534 (4)	0.7834 (4)	0.11718 (9)	0.0189 (7)
H14A	0.5985	0.8594	0.1317	0.023*
C3A	0.1300 (4)	−0.1650 (4)	0.10941 (9)	0.0211 (7)
H3A	0.0816	−0.2599	0.1048	0.025*
C13A	0.5437 (4)	0.8035 (4)	0.08197 (9)	0.0205 (7)
H13A	0.5838	0.8921	0.0720	0.025*
C4B	0.0091 (4)	0.5255 (4)	0.18713 (9)	0.0193 (7)
H4B	0.0076	0.5521	0.2106	0.023*
C7B	0.3040 (4)	0.4475 (4)	0.23114 (8)	0.0196 (7)
H7B	0.2281	0.4937	0.2440	0.024*
N2B	0.3874 (3)	0.3573 (3)	0.17813 (6)	0.0124 (5)
C6B	0.2779 (3)	0.4223 (4)	0.19610 (8)	0.0143 (6)
C14B	0.7970 (4)	0.1152 (4)	0.12103 (9)	0.0184 (7)
H14B	0.8565	0.0731	0.1039	0.022*
C1B	0.0186 (4)	0.4455 (4)	0.11975 (9)	0.0163 (7)
H1B	0.0203	0.4168	0.0964	0.020*
C13B	0.8476 (4)	0.1089 (4)	0.15514 (9)	0.0216 (7)
H13B	0.9417	0.0606	0.1618	0.026*
C5B	0.1388 (4)	0.4593 (4)	0.17462 (8)	0.0149 (7)
C2B	−0.1131 (4)	0.5101 (4)	0.13105 (9)	0.0208 (7)
H2B	−0.1997	0.5253	0.1156	0.025*
C3B	−0.1173 (4)	0.5522 (4)	0.16509 (9)	0.0223 (8)
H3B	−0.2059	0.5988	0.1732	0.027*
C8B	0.4433 (4)	0.4036 (4)	0.24683 (9)	0.0215 (7)
H8B	0.4625	0.4199	0.2707	0.026*
C9B	0.5547 (4)	0.3367 (4)	0.22841 (8)	0.0192 (7)
H9B	0.6501	0.3074	0.2393	0.023*
N1B	0.1441 (3)	0.4219 (3)	0.14059 (7)	0.0127 (5)
N2A	0.3132 (3)	0.3157 (3)	0.07744 (6)	0.0126 (5)
C6A	0.2464 (3)	0.1891 (4)	0.06429 (8)	0.0142 (6)
N3B	0.5705 (3)	0.2454 (3)	0.13564 (6)	0.0123 (5)
C7A	0.2136 (4)	0.1753 (4)	0.02910 (8)	0.0198 (7)
H7A	0.1668	0.0862	0.0197	0.024*
C11B	0.6234 (3)	0.2424 (4)	0.16936 (8)	0.0146 (7)
Cl1A	0.78661 (9)	0.20109 (9)	0.02625 (2)	0.01935 (18)
O2A	0.8387 (3)	0.2126 (3)	−0.00779 (6)	0.0306 (6)
O4A	0.6256 (3)	0.2268 (4)	0.02484 (7)	0.0426 (8)
O3A	0.8209 (4)	0.0534 (3)	0.03981 (7)	0.0383 (7)
O1A	0.8611 (4)	0.3124 (3)	0.04797 (7)	0.0407 (7)
Cl1B	0.52415 (9)	0.83287 (10)	0.22156 (2)	0.02087 (18)
O2B	0.5394 (3)	0.7741 (3)	0.25576 (7)	0.0369 (7)
O1B	0.3911 (3)	0.7690 (3)	0.20366 (6)	0.0279 (6)
O3B	0.5070 (3)	0.9946 (3)	0.22300 (7)	0.0297 (6)
O4B	0.6574 (3)	0.7965 (4)	0.20354 (7)	0.0433 (8)
O5	0.9985 (6)	0.6020 (6)	0.05038 (12)	0.0266 (11)	0.50
H5A	1.044 (8)	0.639 (8)	0.0339 (13)	0.040*	0.50
H5B	0.950 (8)	0.523 (6)	0.0438 (18)	0.040*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.00989 (12)	0.00929 (12)	0.01172 (13)	−0.00013 (10)	0.00132 (9)	−0.00072 (10)
N1A	0.0079 (12)	0.0103 (13)	0.0179 (13)	0.0022 (10)	0.0002 (10)	−0.0004 (11)
N3A	0.0100 (12)	0.0096 (13)	0.0173 (13)	0.0017 (10)	0.0025 (10)	−0.0008 (11)
C15A	0.0119 (14)	0.0129 (16)	0.0179 (16)	0.0005 (12)	0.0008 (12)	−0.0028 (13)
C1A	0.0130 (15)	0.0161 (17)	0.0171 (16)	0.0008 (13)	0.0000 (12)	0.0015 (13)
C10A	0.0114 (15)	0.0123 (16)	0.0181 (16)	0.0039 (12)	0.0010 (12)	0.0001 (13)
C10B	0.0158 (15)	0.0109 (16)	0.0168 (16)	−0.0039 (12)	0.0002 (12)	0.0007 (13)
C11A	0.0123 (15)	0.0145 (16)	0.0171 (16)	0.0030 (13)	0.0031 (12)	−0.0005 (13)
C5A	0.0101 (15)	0.0129 (16)	0.0194 (16)	0.0024 (12)	0.0003 (12)	−0.0015 (13)
C12A	0.0190 (16)	0.0153 (17)	0.0198 (17)	−0.0005 (13)	0.0031 (13)	0.0031 (14)
C2A	0.0150 (16)	0.0119 (16)	0.0273 (18)	0.0037 (13)	0.0013 (13)	0.0053 (14)
C15B	0.0171 (16)	0.0126 (16)	0.0175 (16)	−0.0028 (13)	0.0047 (12)	−0.0005 (13)
C4A	0.0153 (16)	0.0145 (17)	0.0221 (17)	0.0000 (13)	−0.0012 (13)	−0.0031 (14)
C12B	0.0168 (16)	0.0195 (17)	0.0228 (17)	−0.0005 (14)	−0.0030 (13)	0.0026 (15)
C8A	0.0236 (18)	0.028 (2)	0.0122 (16)	−0.0017 (15)	0.0000 (13)	−0.0018 (14)
C9A	0.0204 (17)	0.0187 (18)	0.0162 (16)	0.0000 (14)	0.0026 (13)	0.0009 (14)
C14A	0.0165 (16)	0.0143 (16)	0.0260 (18)	−0.0020 (13)	0.0018 (13)	−0.0038 (14)
C3A	0.0157 (16)	0.0118 (16)	0.036 (2)	−0.0042 (14)	0.0000 (14)	−0.0010 (15)
C13A	0.0193 (17)	0.0129 (17)	0.0297 (19)	−0.0023 (13)	0.0047 (14)	0.0044 (14)
C4B	0.0207 (17)	0.0141 (17)	0.0240 (18)	0.0010 (14)	0.0093 (14)	0.0003 (14)
C7B	0.0258 (18)	0.0160 (17)	0.0178 (17)	−0.0032 (14)	0.0088 (13)	−0.0030 (14)
N2B	0.0133 (13)	0.0081 (13)	0.0161 (13)	−0.0015 (10)	0.0028 (10)	−0.0007 (10)
C6B	0.0149 (15)	0.0089 (15)	0.0195 (16)	−0.0024 (12)	0.0044 (12)	−0.0017 (13)
C14B	0.0152 (16)	0.0146 (16)	0.0262 (18)	0.0000 (13)	0.0073 (13)	−0.0003 (14)
C1B	0.0159 (16)	0.0100 (16)	0.0228 (17)	−0.0028 (13)	0.0005 (13)	0.0017 (13)
C13B	0.0147 (16)	0.0184 (18)	0.032 (2)	0.0010 (14)	0.0013 (14)	0.0041 (15)
C5B	0.0184 (16)	0.0076 (15)	0.0194 (16)	−0.0023 (12)	0.0065 (13)	0.0006 (13)
C2B	0.0134 (16)	0.0159 (17)	0.033 (2)	0.0005 (13)	0.0019 (14)	0.0046 (15)
C3B	0.0167 (17)	0.0157 (17)	0.036 (2)	0.0030 (14)	0.0111 (14)	0.0021 (15)
C8B	0.0292 (19)	0.0219 (19)	0.0134 (16)	−0.0064 (15)	0.0008 (13)	−0.0018 (14)
C9B	0.0212 (17)	0.0187 (17)	0.0171 (16)	−0.0012 (14)	−0.0049 (13)	0.0000 (14)
N1B	0.0122 (13)	0.0083 (13)	0.0179 (14)	−0.0028 (10)	0.0030 (10)	−0.0004 (11)
N2A	0.0111 (12)	0.0111 (13)	0.0155 (13)	0.0013 (10)	0.0012 (10)	0.0000 (11)
C6A	0.0116 (14)	0.0127 (16)	0.0185 (16)	0.0030 (12)	0.0017 (12)	−0.0027 (13)
N3B	0.0111 (12)	0.0101 (13)	0.0155 (13)	−0.0026 (10)	0.0000 (10)	0.0010 (11)
C7A	0.0198 (16)	0.0204 (18)	0.0190 (17)	−0.0021 (15)	−0.0010 (13)	−0.0044 (14)
C11B	0.0144 (15)	0.0120 (16)	0.0175 (16)	−0.0049 (13)	0.0008 (12)	0.0004 (13)
Cl1A	0.0207 (4)	0.0201 (4)	0.0172 (4)	0.0005 (3)	0.0013 (3)	−0.0022 (3)
O2A	0.0369 (15)	0.0372 (16)	0.0184 (13)	0.0012 (13)	0.0073 (11)	−0.0027 (12)
O4A	0.0226 (14)	0.072 (2)	0.0337 (16)	0.0097 (15)	0.0027 (12)	0.0139 (16)
O3A	0.062 (2)	0.0264 (15)	0.0263 (15)	0.0128 (14)	−0.0007 (13)	0.0011 (12)
O1A	0.0560 (19)	0.0395 (18)	0.0263 (15)	−0.0183 (15)	0.0012 (13)	−0.0127 (13)
Cl1B	0.0236 (4)	0.0194 (4)	0.0191 (4)	0.0054 (3)	−0.0023 (3)	−0.0056 (3)
O2B	0.0604 (19)	0.0273 (15)	0.0211 (14)	0.0101 (14)	−0.0127 (13)	0.0005 (12)
O1B	0.0301 (14)	0.0306 (15)	0.0218 (13)	−0.0036 (12)	−0.0073 (11)	−0.0022 (11)
O3B	0.0389 (16)	0.0187 (13)	0.0330 (15)	−0.0019 (12)	0.0143 (12)	−0.0010 (12)
O4B	0.0276 (15)	0.059 (2)	0.0432 (17)	0.0136 (14)	0.0025 (13)	−0.0240 (16)
O5	0.034 (3)	0.025 (3)	0.021 (3)	−0.010 (2)	−0.002 (2)	0.005 (2)

Geometric parameters (Å, º) top

Ru1—N2A	1.984 (3)	C14A—C13A	1.386 (5)
Ru1—N2B	1.986 (3)	C14A—H14A	0.9500
Ru1—N1A	2.067 (3)	C3A—H3A	0.9500
Ru1—N3B	2.072 (3)	C13A—H13A	0.9500
Ru1—N1B	2.073 (3)	C4B—C3B	1.381 (5)
Ru1—N3A	2.076 (3)	C4B—C5B	1.394 (4)
N1A—C1A	1.350 (4)	C4B—H4B	0.9500
N1A—C5A	1.376 (4)	C7B—C8B	1.388 (5)
N3A—C15A	1.342 (4)	C7B—C6B	1.393 (4)
N3A—C11A	1.383 (4)	C7B—H7B	0.9500
C15A—C14A	1.384 (5)	N2B—C6B	1.352 (4)
C15A—H15A	0.9500	C6B—C5B	1.474 (4)
C1A—C2A	1.387 (5)	C14B—C13B	1.381 (5)
C1A—H1A	0.9500	C14B—H14B	0.9500
C10A—N2A	1.354 (4)	C1B—N1B	1.345 (4)
C10A—C9A	1.399 (4)	C1B—C2B	1.384 (5)
C10A—C11A	1.470 (4)	C1B—H1B	0.9500
C10B—N2B	1.351 (4)	C13B—H13B	0.9500
C10B—C9B	1.396 (4)	C5B—N1B	1.375 (4)
C10B—C11B	1.469 (4)	C2B—C3B	1.385 (5)
C11A—C12A	1.389 (4)	C2B—H2B	0.9500
C5A—C4A	1.388 (4)	C3B—H3B	0.9500
C5A—C6A	1.468 (4)	C8B—C9B	1.382 (5)
C12A—C13A	1.387 (5)	C8B—H8B	0.9500
C12A—H12A	0.9500	C9B—H9B	0.9500
C2A—C3A	1.384 (5)	N2A—C6A	1.349 (4)
C2A—H2A	0.9500	C6A—C7A	1.394 (4)
C15B—N3B	1.344 (4)	N3B—C11B	1.371 (4)
C15B—C14B	1.388 (4)	C7A—H7A	0.9500
C15B—H15B	0.9500	Cl1A—O4A	1.427 (3)
C4A—C3A	1.380 (5)	Cl1A—O1A	1.430 (3)
C4A—H4A	0.9500	Cl1A—O3A	1.432 (3)
C12B—C13B	1.378 (5)	Cl1A—O2A	1.438 (3)
C12B—C11B	1.387 (4)	Cl1B—O2B	1.433 (3)
C12B—H12B	0.9500	Cl1B—O3B	1.437 (3)
C8A—C7A	1.384 (5)	Cl1B—O1B	1.437 (3)
C8A—C9A	1.386 (5)	Cl1B—O4B	1.438 (3)
C8A—H8A	0.9500	O5—H5A	0.85 (2)
C9A—H9A	0.9500	O5—H5B	0.85 (2)

N2A—Ru1—N2B	178.09 (11)	C12A—C13A—H13A	120.7
N2A—Ru1—N1A	78.99 (10)	C3B—C4B—C5B	119.5 (3)
N2B—Ru1—N1A	102.30 (10)	C3B—C4B—H4B	120.2
N2A—Ru1—N3B	102.56 (10)	C5B—C4B—H4B	120.2
N2B—Ru1—N3B	78.88 (10)	C8B—C7B—C6B	118.4 (3)
N1A—Ru1—N3B	90.37 (10)	C8B—C7B—H7B	120.8
N2A—Ru1—N1B	99.82 (10)	C6B—C7B—H7B	120.8
N2B—Ru1—N1B	78.78 (10)	C6B—N2B—C10B	121.6 (3)
N1A—Ru1—N1B	92.06 (10)	C6B—N2B—Ru1	119.3 (2)
N3B—Ru1—N1B	157.54 (10)	C10B—N2B—Ru1	119.1 (2)
N2A—Ru1—N3A	78.81 (10)	N2B—C6B—C7B	120.1 (3)
N2B—Ru1—N3A	99.93 (10)	N2B—C6B—C5B	112.7 (3)
N1A—Ru1—N3A	157.73 (10)	C7B—C6B—C5B	127.2 (3)
N3B—Ru1—N3A	92.65 (10)	C13B—C14B—C15B	118.9 (3)
N1B—Ru1—N3A	93.49 (10)	C13B—C14B—H14B	120.5
C1A—N1A—C5A	118.1 (3)	C15B—C14B—H14B	120.5
C1A—N1A—Ru1	128.2 (2)	N1B—C1B—C2B	122.5 (3)
C5A—N1A—Ru1	113.7 (2)	N1B—C1B—H1B	118.7
C15A—N3A—C11A	118.1 (3)	C2B—C1B—H1B	118.7
C15A—N3A—Ru1	127.7 (2)	C12B—C13B—C14B	119.6 (3)
C11A—N3A—Ru1	114.1 (2)	C12B—C13B—H13B	120.2
N3A—C15A—C14A	122.7 (3)	C14B—C13B—H13B	120.2
N3A—C15A—H15A	118.7	N1B—C5B—C4B	121.2 (3)
C14A—C15A—H15A	118.7	N1B—C5B—C6B	114.9 (3)
N1A—C1A—C2A	122.4 (3)	C4B—C5B—C6B	123.8 (3)
N1A—C1A—H1A	118.8	C1B—C2B—C3B	119.4 (3)
C2A—C1A—H1A	118.8	C1B—C2B—H2B	120.3
N2A—C10A—C9A	120.0 (3)	C3B—C2B—H2B	120.3
N2A—C10A—C11A	113.2 (3)	C4B—C3B—C2B	119.1 (3)
C9A—C10A—C11A	126.8 (3)	C4B—C3B—H3B	120.5
N2B—C10B—C9B	120.5 (3)	C2B—C3B—H3B	120.5
N2B—C10B—C11B	112.7 (3)	C9B—C8B—C7B	121.3 (3)
C9B—C10B—C11B	126.8 (3)	C9B—C8B—H8B	119.3
N3A—C11A—C12A	121.1 (3)	C7B—C8B—H8B	119.3
N3A—C11A—C10A	114.5 (3)	C8B—C9B—C10B	118.0 (3)
C12A—C11A—C10A	124.3 (3)	C8B—C9B—H9B	121.0
N1A—C5A—C4A	121.5 (3)	C10B—C9B—H9B	121.0
N1A—C5A—C6A	115.2 (3)	C1B—N1B—C5B	118.3 (3)
C4A—C5A—C6A	123.3 (3)	C1B—N1B—Ru1	127.6 (2)
C13A—C12A—C11A	119.8 (3)	C5B—N1B—Ru1	114.1 (2)
C13A—C12A—H12A	120.1	C6A—N2A—C10A	121.6 (3)
C11A—C12A—H12A	120.1	C6A—N2A—Ru1	119.1 (2)
C3A—C2A—C1A	119.2 (3)	C10A—N2A—Ru1	119.2 (2)
C3A—C2A—H2A	120.4	N2A—C6A—C7A	120.5 (3)
C1A—C2A—H2A	120.4	N2A—C6A—C5A	112.8 (3)
N3B—C15B—C14B	122.4 (3)	C7A—C6A—C5A	126.7 (3)
N3B—C15B—H15B	118.8	C15B—N3B—C11B	118.5 (3)
C14B—C15B—H15B	118.8	C15B—N3B—Ru1	127.6 (2)
C3A—C4A—C5A	119.4 (3)	C11B—N3B—Ru1	113.8 (2)
C3A—C4A—H4A	120.3	C8A—C7A—C6A	118.5 (3)
C5A—C4A—H4A	120.3	C8A—C7A—H7A	120.8
C13B—C12B—C11B	119.4 (3)	C6A—C7A—H7A	120.8
C13B—C12B—H12B	120.3	N3B—C11B—C12B	121.3 (3)
C11B—C12B—H12B	120.3	N3B—C11B—C10B	115.3 (3)
C7A—C8A—C9A	120.9 (3)	C12B—C11B—C10B	123.4 (3)
C7A—C8A—H8A	119.5	O4A—Cl1A—O1A	109.1 (2)
C9A—C8A—H8A	119.5	O4A—Cl1A—O3A	110.07 (19)
C8A—C9A—C10A	118.5 (3)	O1A—Cl1A—O3A	109.10 (18)
C8A—C9A—H9A	120.7	O4A—Cl1A—O2A	108.88 (16)
C10A—C9A—H9A	120.7	O1A—Cl1A—O2A	109.99 (17)
C15A—C14A—C13A	119.6 (3)	O3A—Cl1A—O2A	109.65 (17)
C15A—C14A—H14A	120.2	O2B—Cl1B—O3B	109.08 (16)
C13A—C14A—H14A	120.2	O2B—Cl1B—O1B	109.78 (17)
C4A—C3A—C2A	119.4 (3)	O3B—Cl1B—O1B	108.93 (16)
C4A—C3A—H3A	120.3	O2B—Cl1B—O4B	110.22 (18)
C2A—C3A—H3A	120.3	O3B—Cl1B—O4B	109.33 (18)
C14A—C13A—C12A	118.6 (3)	O1B—Cl1B—O4B	109.47 (16)
C14A—C13A—H13A	120.7	H5A—O5—H5B	110 (5)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centoids of the N3A–C15A and N3B–C15B rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2Aⁱ	0.85 (2)	1.98 (3)	2.790 (6)	159 (7)
O5—H5B···O1A	0.85 (2)	2.03 (3)	2.824 (6)	157 (7)
C2B—H2B···Cg1ⁱⁱ	0.95	3.09 (1)	3.945 (4)	45 (1)
C14A—H14A···Cg2ⁱⁱⁱ	0.95	3.01 (1)	3.878 (4)	43 (1)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x−1, y, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Ru(C₁₅H₁₁N₃)₂](ClO₄)₂·0.5H₂O
M_r	775.51
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.7676 (2), 8.8221 (9), 39.118 (4)
β (°)	93.582 (5)
V (Å³)	3019.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.15 × 0.12 × 0.03

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.801, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16537, 6158, 5858
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.083, 1.27
No. of reflections	6158
No. of parameters	439
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −1.17

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXD (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).