(2,2′-Bipyridine-4,4′-dicarb­oxy­lic acid-κ2N,N′)chlorido(2,2′:6′,2′′-terpyridyl-κ3N,N′,N′′)ruthenium(II) perchlorate ethanol monosolvate monohydrate

Nielsen, A.; McKenzie, C.J.; Bond, A.D.

doi:10.1107/S1600536811054195

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages m77-m78

doi:10.1107/S1600536811054195

Open

access

(2,2′-Bipyridine-4,4′-dicarboxylic acid-κ²N,N′)chlorido(2,2′:6′,2′′-terpyridyl-κ³N,N′,N′′)ruthenium(II) perchlorate ethanol monosolvate monohydrate

Anne Nielsen,^a Christine J. McKenzie ^a and Andrew D. Bond ^a ^*

^aUniversity of Southern Denmark, Department of Physics and Chemistry, Campusvej 55, 5230 Odense, Denmark
^*Correspondence e-mail: adb@chem.sdu.dk

(Received 12 December 2011; accepted 16 December 2011; online 23 December 2011)

In the title compound, [RuCl(C₁₅H₁₁N₃)(C₁₂H₈N₂O₄)]ClO₄·C₂H₅OH·H₂O, the geometry of the ClN₅ coordination set around the Ru^II atom is close to octahedral, but distorted on account of the limited bite angles of the polypyridyl ligands. The complexes are linked by O—H⋯O hydrogen bonds between the carboxyl groups and the crystal lattice water molecules into chains along [110]. Face-to-face stacking interactions are formed between terpyridine ligands, with interplanar separations of 3.66 (1) and 3.42 (1) Å, and between bipyridine-4,4′-dicarboxylic acid ligands, with interplanar separations of 3.65 (1) and 3.72 (1) Å. Three O atoms of the perchlorate ion are each disordered equally over two positions. The hydroxy group of the ethanol molecule is also disordered over two sites with refined occupancies of 0.794 (9) and 0.206 (9).

Related literature

For background literature concerning Ru^II complexes containing polypyridyl ligands, see: Kalyanasundaram (1982 ); Juris et al. (1988 ); Concepcion et al. (2008 ). For some other Ru^II complexes containing the 2,2′-bipyridine-4,4′-dicarboxylic acid-N,N′ ligand, see: Caspar et al. (2004 ); Eskelinen et al. (2000 ); Fujihara et al. (2004 ); Pearson et al. (2008 ); Philippopoulos et al. (2007 ). Synthesis details for the precursor RuCl₃(terpy) are given in Takeuchi et al. (1984 ).

Experimental

Crystal data

[RuCl(C₁₅H₁₁N₃)(C₁₂H₈N₂O₄)]ClO₄·C₂H₆O·H₂O
M_r = 777.53
Triclinic, $[P \overline 1]$
a = 8.7132 (5) Å
b = 11.9207 (7) Å
c = 15.9015 (8) Å
α = 90.913 (2)°
β = 104.110 (2)°
γ = 97.677 (2)°
V = 1585.44 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 180 K
0.20 × 0.12 × 0.10 mm

Data collection

Bruker–Nonius X8 APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.792, T_max = 0.931
22443 measured reflections
5961 independent reflections
4978 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.112
S = 1.08
5961 reflections
462 parameters
73 restraints
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1S	0.85	1.75	2.601 (5)	179
O2—H2⋯O1T	0.85	1.93	2.545 (18)	129
O4—H4⋯O1Wⁱ	0.85	1.72	2.569 (4)	179
O1W—H1W⋯O1ⁱⁱ	0.85	1.87	2.720 (4)	179
O1W—H2W⋯O2Cⁱⁱⁱ	0.85	1.95	2.795 (12)	178
O1S—H1S⋯O2A^iv	0.85	2.14	2.986 (8)	180
O1T—H1T⋯O2D^v	0.85	1.84	2.69 (3)	180
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+2, -z+1; (iii) x-1, y+1, z; (iv) -x+2, -y+1, -z+1; (v) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: SAINT (Bruker, 2003 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811054195/is5031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054195/is5031Isup2.hkl

checkCIF report

Comment top

Complexes of Ru^II with polypyridyl ligands are of interest on account of their photophysical and photochemical properties (Kalyanasundaram, 1982; Juris et al., 1988). Recent work in the area of the catalysis of water oxidation has indicated the utility of single-site Ru complexes (Concepcion et al., 2008). The next step towards realising artificial photosynthesis is to anchor these systems chemically to electrode materials. The title complex is intended to embody both required aspects: hydrolysis will result in replacement of the chloride ligand by hydroxide (the substrate of reaction), while the decorating carboxylate groups can be used as functionalities for linking the complex to surfaces.

Related literature top

For background literature concerning Ru^II complexes containing polypyridyl ligands, see: Kalyanasundaram (1982); Juris et al. (1988); Concepcion et al. (2008). For some other Ru^II complexes containing the 2,2'-bipyridine-4,4'-dicarboxylic acid-N,N' ligand, see: Caspar et al. (2004); Eskelinen et al. (2000); Fujihara et al. (2004); Pearson et al. (2008); Philippopoulos et al. (2007). Synthesis details for the precursor RuCl₃(terpy) are given in Takeuchi et al. (1984).

Experimental top

The precursor RuCl₃(terpy) was synthesized according to Takeuchi et al. (1984). RuCl₃(terpy) (345 mg, 0.08 mmol), H₂(bipy-dca)H (bipy-dca = 2,2'-bipyridine-4,4'-dicarboxylic acid, 191 mg, 0.8 mmol) and triethylamine (380 ml, 2.7 mmol) were mixed in ethanol (30 ml) and water (10 ml) and heated under reflux overnight. The reaction mixture was cooled to room temperature and a small amount of black precipitate was removed by filtration. The filtrate was adjusted to pH 2 with perchloric acid (70% aqueous solution) and orange crystals were deposited over 24 h.

Computing details top

Data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure with displacement ellipsoids shown at 50% probability for non-H atoms.
	Fig. 2. Hydrogen-bonded chains running along [110]. Only one orientaton is shown for the disordered ethanol molecule and perchlorate anion.

(2,2'-Bipyridine-4,4'-dicarboxylic acid-κ²N,N')chlorido(2,2':6',2''-terpyridyl- κ³N,N',N'')ruthenium(II) perchlorate ethanol monosolvate monohydrate top

Crystal data top

[RuCl(C₁₅H₁₁N₃)(C₁₂H₈N₂O₄)]ClO₄·C₂H₆O·H₂O	Z = 2
M_r = 777.53	F(000) = 788
Triclinic, P1	D_x = 1.629 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7132 (5) Å	Cell parameters from 8777 reflections
b = 11.9207 (7) Å	θ = 2.5–25.5°
c = 15.9015 (8) Å	µ = 0.73 mm⁻¹
α = 90.913 (2)°	T = 180 K
β = 104.110 (2)°	Block, brown
γ = 97.677 (2)°	0.20 × 0.12 × 0.10 mm
V = 1585.44 (15) Å³

Data collection top

Bruker–Nonius X8 APEXII CCD diffractometer	5961 independent reflections
Radiation source: fine-focus sealed tube	4978 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
thin–slice ω and ϕ scans	θ_max = 25.7°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
T_min = 0.792, T_max = 0.931	k = −14→14
22443 measured reflections	l = −19→17

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0608P)² + 1.3719P] where P = (F_o² + 2F_c²)/3
5961 reflections	(Δ/σ)_max = 0.001
462 parameters	Δρ_max = 0.91 e Å⁻³
73 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[RuCl(C₁₅H₁₁N₃)(C₁₂H₈N₂O₄)]ClO₄·C₂H₆O·H₂O	γ = 97.677 (2)°
M_r = 777.53	V = 1585.44 (15) Å³
Triclinic, P1	Z = 2
a = 8.7132 (5) Å	Mo Kα radiation
b = 11.9207 (7) Å	µ = 0.73 mm⁻¹
c = 15.9015 (8) Å	T = 180 K
α = 90.913 (2)°	0.20 × 0.12 × 0.10 mm
β = 104.110 (2)°

Data collection top

Bruker–Nonius X8 APEXII CCD diffractometer	5961 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	4978 reflections with I > 2σ(I)
T_min = 0.792, T_max = 0.931	R_int = 0.031
22443 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	73 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.08	Δρ_max = 0.91 e Å⁻³
5961 reflections	Δρ_min = −0.74 e Å⁻³
462 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	0.30449 (3)	0.52232 (3)	0.229857 (17)	0.03172 (12)
Cl1	0.38277 (11)	0.64610 (8)	0.12517 (6)	0.0394 (2)
O1	0.6470 (4)	0.9485 (3)	0.5612 (2)	0.0648 (9)
O2	0.5089 (4)	0.8261 (3)	0.6277 (2)	0.0655 (9)
H2	0.5578	0.8627	0.6751	0.098*
O3	0.0613 (4)	0.3562 (3)	0.59862 (19)	0.0588 (9)
O4	−0.0105 (4)	0.1927 (3)	0.5215 (2)	0.0648 (9)
H4	−0.0493	0.1692	0.5632	0.097*
N1	0.3926 (3)	0.6406 (3)	0.33304 (19)	0.0334 (7)
N2	0.2417 (3)	0.4362 (3)	0.32745 (19)	0.0329 (7)
N3	0.5009 (4)	0.4411 (3)	0.23588 (19)	0.0348 (7)
N4	0.2151 (4)	0.4007 (3)	0.14012 (18)	0.0345 (7)
N5	0.0728 (4)	0.5593 (3)	0.18561 (19)	0.0361 (7)
C1	0.4864 (5)	0.7410 (3)	0.3332 (2)	0.0404 (9)
H1A	0.5156	0.7623	0.2813	0.048*
C2	0.5406 (5)	0.8132 (3)	0.4058 (3)	0.0409 (9)
H2A	0.6078	0.8823	0.4040	0.049*
C3	0.4968 (5)	0.7846 (3)	0.4814 (2)	0.0374 (9)
C4	0.4015 (4)	0.6820 (3)	0.4819 (2)	0.0365 (8)
H4A	0.3699	0.6603	0.5331	0.044*
C5	0.3525 (4)	0.6115 (3)	0.4079 (2)	0.0316 (8)
C6	0.5576 (5)	0.8626 (4)	0.5610 (3)	0.0463 (10)
C7	0.2617 (4)	0.4974 (3)	0.4037 (2)	0.0317 (8)
C8	0.2015 (4)	0.4523 (3)	0.4706 (2)	0.0329 (8)
H8A	0.2124	0.4975	0.5220	0.039*
C9	0.1257 (4)	0.3418 (3)	0.4633 (2)	0.0347 (8)
C10	0.1133 (4)	0.2776 (3)	0.3876 (2)	0.0370 (8)
H10A	0.0654	0.2006	0.3814	0.044*
C11	0.1712 (4)	0.3272 (3)	0.3219 (2)	0.0376 (9)
H11A	0.1613	0.2827	0.2702	0.045*
C12	0.0563 (5)	0.2980 (3)	0.5357 (2)	0.0395 (9)
C13	0.6499 (4)	0.4691 (3)	0.2879 (2)	0.0384 (9)
H13A	0.6713	0.5352	0.3254	0.046*
C14	0.7705 (5)	0.4068 (4)	0.2889 (3)	0.0450 (10)
H14A	0.8734	0.4290	0.3265	0.054*
C15	0.7406 (5)	0.3105 (4)	0.2340 (3)	0.0480 (10)
H15A	0.8219	0.2646	0.2345	0.058*
C16	0.5917 (5)	0.2826 (4)	0.1791 (3)	0.0448 (10)
H16A	0.5704	0.2184	0.1397	0.054*
C17	0.4732 (5)	0.3474 (3)	0.1807 (2)	0.0374 (8)
C18	0.3086 (5)	0.3238 (3)	0.1254 (2)	0.0388 (9)
C19	0.2449 (5)	0.2350 (4)	0.0640 (3)	0.0482 (10)
H19A	0.3095	0.1813	0.0526	0.058*
C20	0.0859 (5)	0.2262 (4)	0.0198 (3)	0.0540 (11)
H20A	0.0405	0.1650	−0.0216	0.065*
C21	−0.0074 (5)	0.3047 (4)	0.0351 (3)	0.0467 (10)
H21A	−0.1166	0.2982	0.0044	0.056*
C22	0.0595 (4)	0.3930 (3)	0.0957 (2)	0.0380 (9)
C23	−0.0195 (4)	0.4848 (3)	0.1210 (2)	0.0370 (9)
C24	−0.1768 (5)	0.4973 (4)	0.0825 (3)	0.0464 (10)
H24A	−0.2396	0.4451	0.0375	0.056*
C25	−0.2408 (5)	0.5863 (4)	0.1104 (3)	0.0516 (11)
H25A	−0.3483	0.5962	0.0846	0.062*
C26	−0.1489 (5)	0.6602 (4)	0.1753 (3)	0.0495 (11)
H26A	−0.1924	0.7214	0.1953	0.059*
C27	0.0078 (5)	0.6455 (3)	0.2118 (2)	0.0402 (9)
H27A	0.0713	0.6976	0.2567	0.048*
Cl2	0.8935 (2)	0.01878 (13)	0.17808 (11)	0.0846 (4)
O2A	1.0065 (6)	0.1063 (4)	0.2176 (3)	0.1302 (19)
O2B	0.8067 (15)	0.0204 (11)	0.0971 (6)	0.166 (5)	0.50
O2C	0.9907 (13)	−0.0746 (7)	0.1832 (8)	0.135 (4)	0.50
O2D	0.8001 (17)	−0.0137 (14)	0.2390 (9)	0.233 (12)	0.50
O2E	0.8421 (13)	−0.0554 (9)	0.2330 (7)	0.116 (4)	0.50
O2F	0.9463 (14)	−0.0316 (9)	0.1130 (7)	0.143 (4)	0.50
O2G	0.7602 (10)	0.0775 (8)	0.1339 (7)	0.120 (4)	0.50
O1W	0.1323 (4)	0.8776 (3)	0.3538 (2)	0.0649 (9)
H1W	0.2019	0.9317	0.3804	0.097*
H2W	0.0882	0.8906	0.3017	0.097*
O1S	0.6600 (6)	0.9364 (4)	0.7731 (3)	0.0729 (18)	0.794 (9)
H1S	0.7550	0.9243	0.7757	0.109*	0.794 (9)
C1S	0.6167 (16)	1.0330 (11)	0.8050 (8)	0.181 (5)	0.794 (9)
H2S	0.5003	1.0299	0.7802	0.217*	0.794 (9)
H3S	0.6694	1.0981	0.7796	0.217*	0.794 (9)
O1T	0.485 (3)	0.9761 (15)	0.7379 (11)	0.087 (9)	0.206 (9)
H1T	0.3954	0.9877	0.7453	0.131*	0.206 (9)
C1T	0.6167 (16)	1.0330 (11)	0.8050 (8)	0.181 (5)	0.206 (9)
H2T	0.6421	1.1071	0.7805	0.217*	0.206 (9)
H3T	0.7059	0.9909	0.8019	0.217*	0.206 (9)
C2S	0.6458 (13)	1.0616 (8)	0.8968 (6)	0.156 (4)
H4S	0.6063	1.1332	0.9049	0.233*
H5S	0.7609	1.0696	0.9236	0.233*
H6S	0.5900	1.0013	0.9241	0.233*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.02898 (18)	0.0418 (2)	0.02243 (17)	−0.00185 (12)	0.00673 (11)	−0.00504 (12)
Cl1	0.0347 (5)	0.0531 (6)	0.0295 (5)	−0.0012 (4)	0.0101 (4)	0.0001 (4)
O1	0.091 (3)	0.0474 (18)	0.0447 (18)	−0.0189 (18)	0.0104 (17)	−0.0117 (14)
O2	0.097 (3)	0.0547 (19)	0.0401 (18)	−0.0176 (18)	0.0235 (17)	−0.0175 (14)
O3	0.078 (2)	0.0578 (19)	0.0398 (17)	−0.0216 (16)	0.0298 (16)	−0.0117 (14)
O4	0.093 (3)	0.0508 (19)	0.0516 (19)	−0.0214 (17)	0.0374 (18)	−0.0060 (14)
N1	0.0284 (15)	0.0400 (17)	0.0299 (16)	0.0002 (13)	0.0063 (12)	−0.0012 (13)
N2	0.0285 (16)	0.0404 (17)	0.0283 (15)	0.0014 (13)	0.0067 (12)	−0.0052 (13)
N3	0.0321 (16)	0.0452 (18)	0.0262 (15)	0.0002 (14)	0.0086 (13)	−0.0022 (13)
N4	0.0328 (16)	0.0453 (18)	0.0241 (15)	−0.0017 (14)	0.0089 (12)	−0.0052 (13)
N5	0.0349 (17)	0.0479 (19)	0.0252 (15)	−0.0008 (14)	0.0106 (13)	0.0001 (13)
C1	0.041 (2)	0.044 (2)	0.033 (2)	−0.0052 (18)	0.0091 (17)	−0.0013 (17)
C2	0.039 (2)	0.038 (2)	0.040 (2)	−0.0062 (17)	0.0068 (17)	−0.0034 (17)
C3	0.040 (2)	0.037 (2)	0.033 (2)	0.0024 (17)	0.0058 (16)	−0.0048 (16)
C4	0.041 (2)	0.039 (2)	0.0299 (19)	0.0023 (17)	0.0100 (16)	−0.0026 (15)
C5	0.0281 (18)	0.0376 (19)	0.0283 (18)	0.0016 (15)	0.0073 (14)	−0.0015 (15)
C6	0.058 (3)	0.041 (2)	0.036 (2)	0.002 (2)	0.0069 (19)	−0.0059 (17)
C7	0.0280 (18)	0.040 (2)	0.0242 (17)	0.0028 (15)	0.0021 (14)	−0.0053 (15)
C8	0.0331 (19)	0.039 (2)	0.0242 (17)	0.0001 (16)	0.0053 (14)	−0.0048 (14)
C9	0.0340 (19)	0.043 (2)	0.0250 (18)	0.0026 (16)	0.0052 (15)	0.0005 (15)
C10	0.039 (2)	0.034 (2)	0.036 (2)	−0.0003 (16)	0.0081 (16)	−0.0031 (16)
C11	0.039 (2)	0.041 (2)	0.033 (2)	0.0010 (17)	0.0109 (16)	−0.0075 (16)
C12	0.039 (2)	0.045 (2)	0.032 (2)	−0.0023 (17)	0.0079 (16)	0.0006 (17)
C13	0.037 (2)	0.047 (2)	0.0283 (19)	0.0020 (17)	0.0062 (16)	−0.0014 (16)
C14	0.034 (2)	0.058 (3)	0.040 (2)	0.0058 (19)	0.0040 (17)	0.0020 (19)
C15	0.042 (2)	0.055 (3)	0.049 (2)	0.010 (2)	0.0122 (19)	0.000 (2)
C16	0.045 (2)	0.049 (2)	0.040 (2)	0.0041 (19)	0.0134 (18)	−0.0054 (18)
C17	0.040 (2)	0.042 (2)	0.0299 (19)	0.0008 (17)	0.0109 (16)	−0.0029 (16)
C18	0.039 (2)	0.047 (2)	0.0296 (19)	0.0006 (17)	0.0102 (16)	−0.0048 (16)
C19	0.053 (3)	0.050 (2)	0.040 (2)	0.002 (2)	0.012 (2)	−0.0126 (19)
C20	0.054 (3)	0.058 (3)	0.041 (2)	−0.005 (2)	0.002 (2)	−0.016 (2)
C21	0.042 (2)	0.057 (3)	0.033 (2)	−0.007 (2)	0.0036 (17)	−0.0053 (18)
C22	0.033 (2)	0.052 (2)	0.0259 (19)	−0.0044 (17)	0.0073 (15)	0.0001 (16)
C23	0.033 (2)	0.052 (2)	0.0246 (18)	−0.0035 (17)	0.0100 (15)	−0.0006 (16)
C24	0.034 (2)	0.072 (3)	0.032 (2)	−0.002 (2)	0.0100 (17)	0.0024 (19)
C25	0.034 (2)	0.084 (3)	0.041 (2)	0.013 (2)	0.0152 (19)	0.009 (2)
C26	0.044 (2)	0.067 (3)	0.042 (2)	0.014 (2)	0.018 (2)	0.002 (2)
C27	0.040 (2)	0.052 (2)	0.032 (2)	0.0059 (18)	0.0151 (17)	−0.0007 (17)
Cl2	0.1002 (12)	0.0709 (9)	0.0767 (10)	0.0131 (8)	0.0115 (9)	−0.0187 (8)
O2A	0.132 (4)	0.099 (3)	0.133 (4)	−0.013 (3)	0.002 (3)	−0.039 (3)
O2B	0.162 (9)	0.191 (10)	0.115 (8)	0.046 (8)	−0.030 (7)	−0.002 (7)
O2C	0.172 (8)	0.108 (6)	0.114 (7)	0.063 (6)	−0.008 (6)	−0.021 (6)
O2D	0.238 (15)	0.264 (15)	0.222 (14)	0.041 (10)	0.102 (10)	0.045 (10)
O2E	0.107 (7)	0.117 (7)	0.123 (7)	0.006 (6)	0.031 (6)	0.044 (6)
O2F	0.192 (9)	0.122 (7)	0.130 (8)	0.062 (7)	0.049 (7)	−0.053 (6)
O2G	0.112 (7)	0.122 (7)	0.129 (7)	0.068 (6)	0.012 (6)	0.000 (6)
O1W	0.084 (2)	0.060 (2)	0.0427 (17)	−0.0258 (17)	0.0212 (16)	−0.0058 (15)
O1S	0.090 (4)	0.064 (3)	0.055 (3)	0.007 (2)	0.002 (2)	−0.023 (2)
C1S	0.207 (9)	0.176 (8)	0.162 (8)	0.027 (7)	0.049 (7)	0.059 (7)
O1T	0.13 (2)	0.062 (12)	0.055 (11)	−0.032 (11)	0.017 (11)	−0.030 (9)
C1T	0.207 (9)	0.176 (8)	0.162 (8)	0.027 (7)	0.049 (7)	0.059 (7)
C2S	0.207 (8)	0.136 (6)	0.107 (6)	0.059 (6)	−0.008 (5)	−0.060 (5)

Geometric parameters (Å, º) top

Ru1—N1	2.072 (3)	C14—C15	1.387 (6)
Ru1—N2	2.019 (3)	C14—H14A	0.950
Ru1—N3	2.060 (3)	C15—C16	1.371 (6)
Ru1—N4	1.959 (3)	C15—H15A	0.950
Ru1—N5	2.079 (3)	C16—C17	1.374 (6)
Ru1—Cl1	2.4035 (9)	C16—H16A	0.950
O1—C6	1.201 (5)	C17—C18	1.476 (5)
O2—C6	1.297 (5)	C18—C19	1.388 (5)
O2—H2	0.850	C19—C20	1.381 (6)
O3—C12	1.197 (5)	C19—H19A	0.950
O4—C12	1.303 (5)	C20—C21	1.374 (6)
O4—H4	0.850	C20—H20A	0.950
N1—C1	1.356 (5)	C21—C22	1.382 (6)
N1—C5	1.357 (4)	C21—H21A	0.950
N2—C11	1.353 (5)	C22—C23	1.467 (6)
N2—C7	1.367 (4)	C23—C24	1.386 (5)
N3—C13	1.354 (5)	C24—C25	1.378 (6)
N3—C17	1.367 (5)	C24—H24A	0.950
N4—C22	1.357 (5)	C25—C26	1.364 (6)
N4—C18	1.358 (5)	C25—H25A	0.950
N5—C27	1.343 (5)	C26—C27	1.384 (6)
N5—C23	1.368 (5)	C26—H26A	0.950
C1—C2	1.374 (5)	C27—H27A	0.950
C1—H1A	0.950	Cl2—O2A	1.362 (4)
C2—C3	1.382 (5)	Cl2—O2B	1.327 (7)
C2—H2A	0.950	Cl2—O2C	1.478 (7)
C3—C4	1.384 (5)	Cl2—O2D	1.436 (8)
C3—C6	1.501 (5)	Cl2—O2E	1.362 (7)
C4—C5	1.379 (5)	Cl2—O2F	1.389 (7)
C4—H4A	0.950	Cl2—O2G	1.472 (6)
C5—C7	1.471 (5)	O1W—H1W	0.850
C7—C8	1.383 (5)	O1W—H2W	0.850
C8—C9	1.381 (5)	O1S—C1S	1.384 (14)
C8—H8A	0.950	O1S—H1S	0.850
C9—C10	1.389 (5)	C1S—C2S	1.447 (13)
C9—C12	1.497 (5)	C1S—H2S	0.990
C10—C11	1.376 (5)	C1S—H3S	0.990
C10—H10A	0.950	O1T—H1T	0.850
C11—H11A	0.950	C2S—H4S	0.980
C13—C14	1.363 (5)	C2S—H5S	0.980
C13—H13A	0.950	C2S—H6S	0.980

N4—Ru1—N2	95.74 (12)	C14—C13—H13A	118.5
N4—Ru1—N3	79.16 (12)	C13—C14—C15	119.0 (4)
N2—Ru1—N3	93.30 (12)	C13—C14—H14A	120.5
N4—Ru1—N1	174.59 (12)	C15—C14—H14A	120.5
N2—Ru1—N1	78.86 (12)	C16—C15—C14	118.9 (4)
N3—Ru1—N1	100.75 (11)	C16—C15—H15A	120.6
N4—Ru1—N5	79.40 (12)	C14—C15—H15A	120.6
N2—Ru1—N5	90.51 (11)	C15—C16—C17	120.2 (4)
N3—Ru1—N5	158.49 (12)	C15—C16—H16A	119.9
N1—Ru1—N5	100.76 (12)	C17—C16—H16A	119.9
N4—Ru1—Cl1	91.15 (9)	N3—C17—C16	121.2 (4)
N2—Ru1—Cl1	172.75 (9)	N3—C17—C18	114.3 (3)
N3—Ru1—Cl1	90.22 (9)	C16—C17—C18	124.5 (4)
N1—Ru1—Cl1	94.26 (9)	N4—C18—C19	119.8 (4)
N5—Ru1—Cl1	88.52 (8)	N4—C18—C17	112.6 (3)
C6—O2—H2	113.7	C19—C18—C17	127.6 (4)
C12—O4—H4	111.5	C20—C19—C18	118.8 (4)
C1—N1—C5	117.9 (3)	C20—C19—H19A	120.6
C1—N1—Ru1	126.9 (2)	C18—C19—H19A	120.6
C5—N1—Ru1	115.2 (2)	C21—C20—C19	120.8 (4)
C11—N2—C7	117.8 (3)	C21—C20—H20A	119.6
C11—N2—Ru1	126.0 (2)	C19—C20—H20A	119.6
C7—N2—Ru1	116.1 (2)	C20—C21—C22	119.2 (4)
C13—N3—C17	117.8 (3)	C20—C21—H21A	120.4
C13—N3—Ru1	127.7 (3)	C22—C21—H21A	120.4
C17—N3—Ru1	114.5 (2)	N4—C22—C21	120.0 (4)
C22—N4—C18	121.4 (3)	N4—C22—C23	112.7 (3)
C22—N4—Ru1	119.3 (3)	C21—C22—C23	127.4 (4)
C18—N4—Ru1	119.3 (2)	N5—C23—C24	121.2 (4)
C27—N5—C23	118.6 (3)	N5—C23—C22	115.5 (3)
C27—N5—Ru1	128.3 (3)	C24—C23—C22	123.3 (4)
C23—N5—Ru1	113.1 (2)	C25—C24—C23	119.2 (4)
N1—C1—C2	122.4 (4)	C25—C24—H24A	120.4
N1—C1—H1A	118.8	C23—C24—H24A	120.4
C2—C1—H1A	118.8	C26—C25—C24	119.6 (4)
C1—C2—C3	119.6 (4)	C26—C25—H25A	120.2
C1—C2—H2A	120.2	C24—C25—H25A	120.2
C3—C2—H2A	120.2	C25—C26—C27	119.7 (4)
C2—C3—C4	118.4 (3)	C25—C26—H26A	120.2
C2—C3—C6	119.6 (4)	C27—C26—H26A	120.2
C4—C3—C6	121.9 (3)	N5—C27—C26	121.8 (4)
C5—C4—C3	119.8 (3)	N5—C27—H27A	119.1
C5—C4—H4A	120.1	C26—C27—H27A	119.1
C3—C4—H4A	120.1	O2B—Cl2—O2E	119.5 (8)
N1—C5—C4	121.8 (3)	O2B—Cl2—O2A	123.0 (6)
N1—C5—C7	114.2 (3)	O2E—Cl2—O2A	114.9 (5)
C4—C5—C7	123.9 (3)	O2E—Cl2—O2F	114.3 (6)
O1—C6—O2	124.8 (4)	O2A—Cl2—O2F	108.7 (5)
O1—C6—C3	121.4 (4)	O2B—Cl2—O2D	113.6 (7)
O2—C6—C3	113.8 (4)	O2A—Cl2—O2D	106.4 (6)
N2—C7—C8	121.2 (3)	O2E—Cl2—O2G	109.1 (6)
N2—C7—C5	114.6 (3)	O2A—Cl2—O2G	102.5 (4)
C8—C7—C5	124.2 (3)	O2F—Cl2—O2G	106.3 (6)
C9—C8—C7	120.5 (3)	O2B—Cl2—O2C	108.5 (6)
C9—C8—H8A	119.8	O2A—Cl2—O2C	101.1 (5)
C7—C8—H8A	119.8	O2D—Cl2—O2C	101.5 (6)
C8—C9—C10	118.3 (3)	H1W—O1W—H2W	113.9
C8—C9—C12	118.7 (3)	C1S—O1S—H1S	125.9
C10—C9—C12	123.0 (3)	O1S—C1S—C2S	122.9 (9)
C11—C10—C9	119.1 (3)	O1S—C1S—H2S	106.6
C11—C10—H10A	120.4	C2S—C1S—H2S	106.6
C9—C10—H10A	120.4	O1S—C1S—H3S	106.6
N2—C11—C10	123.0 (3)	C2S—C1S—H3S	106.6
N2—C11—H11A	118.5	H2S—C1S—H3S	106.6
C10—C11—H11A	118.5	C1S—C2S—H4S	109.5
O3—C12—O4	125.1 (4)	C1S—C2S—H5S	109.5
O3—C12—C9	122.1 (4)	H4S—C2S—H5S	109.5
O4—C12—C9	112.8 (3)	C1S—C2S—H6S	109.5
N3—C13—C14	122.9 (4)	H4S—C2S—H6S	109.5
N3—C13—H13A	118.5	H5S—C2S—H6S	109.5

N4—Ru1—N1—C1	169.1 (11)	C4—C3—C6—O2	−1.8 (6)
N2—Ru1—N1—C1	171.8 (3)	C11—N2—C7—C8	−4.7 (5)
N3—Ru1—N1—C1	80.5 (3)	Ru1—N2—C7—C8	170.4 (3)
N5—Ru1—N1—C1	−99.8 (3)	C11—N2—C7—C5	174.5 (3)
Cl1—Ru1—N1—C1	−10.5 (3)	Ru1—N2—C7—C5	−10.4 (4)
N4—Ru1—N1—C5	−9.8 (14)	N1—C5—C7—N2	4.2 (4)
N2—Ru1—N1—C5	−7.1 (2)	C4—C5—C7—N2	−172.5 (3)
N3—Ru1—N1—C5	−98.4 (3)	N1—C5—C7—C8	−176.6 (3)
N5—Ru1—N1—C5	81.3 (3)	C4—C5—C7—C8	6.7 (6)
Cl1—Ru1—N1—C5	170.6 (2)	N2—C7—C8—C9	3.0 (5)
N4—Ru1—N2—C11	3.9 (3)	C5—C7—C8—C9	−176.2 (3)
N3—Ru1—N2—C11	−75.5 (3)	C7—C8—C9—C10	0.7 (5)
N1—Ru1—N2—C11	−175.8 (3)	C7—C8—C9—C12	−177.5 (3)
N5—Ru1—N2—C11	83.3 (3)	C8—C9—C10—C11	−2.4 (5)
Cl1—Ru1—N2—C11	165.6 (5)	C12—C9—C10—C11	175.7 (3)
N4—Ru1—N2—C7	−170.7 (3)	C7—N2—C11—C10	3.0 (5)
N3—Ru1—N2—C7	109.8 (3)	Ru1—N2—C11—C10	−171.6 (3)
N1—Ru1—N2—C7	9.5 (2)	C9—C10—C11—N2	0.6 (6)
N5—Ru1—N2—C7	−91.3 (3)	C8—C9—C12—O3	1.8 (6)
Cl1—Ru1—N2—C7	−9.1 (8)	C10—C9—C12—O3	−176.3 (4)
N4—Ru1—N3—C13	178.9 (3)	C8—C9—C12—O4	−179.4 (4)
N2—Ru1—N3—C13	−85.9 (3)	C10—C9—C12—O4	2.6 (5)
N1—Ru1—N3—C13	−6.6 (3)	C17—N3—C13—C14	−1.7 (6)
N5—Ru1—N3—C13	174.3 (3)	Ru1—N3—C13—C14	177.5 (3)
Cl1—Ru1—N3—C13	87.7 (3)	N3—C13—C14—C15	0.3 (6)
N4—Ru1—N3—C17	−1.9 (2)	C13—C14—C15—C16	1.6 (6)
N2—Ru1—N3—C17	93.3 (3)	C14—C15—C16—C17	−2.1 (6)
N1—Ru1—N3—C17	172.6 (2)	C13—N3—C17—C16	1.1 (5)
N5—Ru1—N3—C17	−6.5 (5)	Ru1—N3—C17—C16	−178.2 (3)
Cl1—Ru1—N3—C17	−93.0 (2)	C13—N3—C17—C18	−179.1 (3)
N2—Ru1—N4—C22	87.8 (3)	Ru1—N3—C17—C18	1.6 (4)
N3—Ru1—N4—C22	−179.9 (3)	C15—C16—C17—N3	0.7 (6)
N1—Ru1—N4—C22	90.5 (13)	C15—C16—C17—C18	−179.0 (4)
N5—Ru1—N4—C22	−1.6 (3)	C22—N4—C18—C19	−0.3 (6)
Cl1—Ru1—N4—C22	−89.9 (3)	Ru1—N4—C18—C19	177.8 (3)
N2—Ru1—N4—C18	−90.3 (3)	C22—N4—C18—C17	−179.8 (3)
N3—Ru1—N4—C18	2.0 (3)	Ru1—N4—C18—C17	−1.7 (4)
N1—Ru1—N4—C18	−87.6 (13)	N3—C17—C18—N4	0.0 (5)
N5—Ru1—N4—C18	−179.7 (3)	C16—C17—C18—N4	179.7 (4)
Cl1—Ru1—N4—C18	92.0 (3)	N3—C17—C18—C19	−179.5 (4)
N4—Ru1—N5—C27	−178.7 (3)	C16—C17—C18—C19	0.3 (7)
N2—Ru1—N5—C27	85.5 (3)	N4—C18—C19—C20	−0.8 (6)
N3—Ru1—N5—C27	−174.1 (3)	C17—C18—C19—C20	178.6 (4)
N1—Ru1—N5—C27	6.8 (3)	C18—C19—C20—C21	1.1 (7)
Cl1—Ru1—N5—C27	−87.3 (3)	C19—C20—C21—C22	−0.2 (7)
N4—Ru1—N5—C23	0.4 (2)	C18—N4—C22—C21	1.1 (5)
N2—Ru1—N5—C23	−95.3 (2)	Ru1—N4—C22—C21	−177.0 (3)
N3—Ru1—N5—C23	5.0 (5)	C18—N4—C22—C23	−179.5 (3)
N1—Ru1—N5—C23	−174.1 (2)	Ru1—N4—C22—C23	2.4 (4)
Cl1—Ru1—N5—C23	91.8 (2)	C20—C21—C22—N4	−0.8 (6)
C5—N1—C1—C2	−0.2 (6)	C20—C21—C22—C23	179.9 (4)
Ru1—N1—C1—C2	−179.1 (3)	C27—N5—C23—C24	0.3 (5)
N1—C1—C2—C3	−1.2 (6)	Ru1—N5—C23—C24	−178.9 (3)
C1—C2—C3—C4	1.3 (6)	C27—N5—C23—C22	179.9 (3)
C1—C2—C3—C6	179.2 (4)	Ru1—N5—C23—C22	0.7 (4)
C2—C3—C4—C5	−0.1 (6)	N4—C22—C23—N5	−2.0 (5)
C6—C3—C4—C5	−178.0 (4)	C21—C22—C23—N5	177.4 (4)
C1—N1—C5—C4	1.5 (5)	N4—C22—C23—C24	177.7 (3)
Ru1—N1—C5—C4	−179.5 (3)	C21—C22—C23—C24	−3.0 (6)
C1—N1—C5—C7	−175.3 (3)	N5—C23—C24—C25	−0.3 (6)
Ru1—N1—C5—C7	3.7 (4)	C22—C23—C24—C25	−179.9 (4)
C3—C4—C5—N1	−1.3 (6)	C23—C24—C25—C26	−0.2 (6)
C3—C4—C5—C7	175.1 (3)	C24—C25—C26—C27	0.6 (6)
C2—C3—C6—O1	−1.8 (6)	C23—N5—C27—C26	0.1 (5)
C4—C3—C6—O1	176.0 (4)	Ru1—N5—C27—C26	179.2 (3)
C2—C3—C6—O2	−179.6 (4)	C25—C26—C27—N5	−0.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1S	0.85	1.75	2.601 (5)	179
O2—H2···O1T	0.85	1.93	2.545 (18)	129
O4—H4···O1Wⁱ	0.85	1.72	2.569 (4)	179
O1W—H1W···O1ⁱⁱ	0.85	1.87	2.720 (4)	179
O1W—H2W···O2Cⁱⁱⁱ	0.85	1.95	2.795 (12)	178
O1S—H1S···O2A^iv	0.85	2.14	2.986 (8)	180
O1T—H1T···O2D^v	0.85	1.84	2.69 (3)	180

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

Experimental details

Crystal data
Chemical formula	[RuCl(C₁₅H₁₁N₃)(C₁₂H₈N₂O₄)]ClO₄·C₂H₆O·H₂O
M_r	777.53
Crystal system, space group	Triclinic, P1
Temperature (K)	180
a, b, c (Å)	8.7132 (5), 11.9207 (7), 15.9015 (8)
α, β, γ (°)	90.913 (2), 104.110 (2), 97.677 (2)
V (Å³)	1585.44 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.20 × 0.12 × 0.10

Data collection
Diffractometer	Bruker–Nonius X8 APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.792, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	22443, 5961, 4978
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.112, 1.08
No. of reflections	5961
No. of parameters	462
No. of restraints	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.74

Computer programs: APEX2 (Bruker–Nonius, 2004), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1S	0.85	1.75	2.601 (5)	179.2
O2—H2···O1T	0.85	1.93	2.545 (18)	128.6
O4—H4···O1Wⁱ	0.85	1.72	2.569 (4)	178.6
O1W—H1W···O1ⁱⁱ	0.85	1.87	2.720 (4)	179.3
O1W—H2W···O2Cⁱⁱⁱ	0.85	1.95	2.795 (12)	178.2
O1S—H1S···O2A^iv	0.85	2.14	2.986 (8)	180.0
O1T—H1T···O2D^v	0.85	1.84	2.69 (3)	179.7

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

Acknowledgements

We are grateful to the Danish Natural Sciences Research Council and the Carlsberg Foundation for provision of the X-ray equipment.

References

Bruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker–Nonius (2004). APEX2. Bruker–Nonius BV, Delft, The Netherlands. Google Scholar
Caspar, R., Musatkina, L., Tatosyan, A., Amouri, H., Gruselle, M., Guyard-Duhayon, C., Duval, R. & Cordier, C. (2004). Inorg. Chem. 43, 7986–7993. Web of Science CSD CrossRef PubMed CAS Google Scholar
Concepcion, J. J., Jurss, J. W., Templeton, J. L. & Meyer, T. J. (2008). J. Am. Chem. Soc. 130, 16462–16463. Web of Science CrossRef PubMed CAS Google Scholar
Eskelinen, E., Luukkanen, S., Haukka, M., Ahlgren, M. & Pakkanen, T. A. (2000). J. Chem. Soc. Dalton Trans. pp. 2745–2752. Web of Science CSD CrossRef Google Scholar
Fujihara, T., Kobayashi, A., Iwai, M. & Nagasawa, A. (2004). Acta Cryst. E60, m1172–m1174. Web of Science CSD CrossRef IUCr Journals Google Scholar
Juris, A., Balzani, V., Barigelletti, F., Campagna, S., Belser, P. & von Zelewsky, A. (1988). Coord. Chem. Rev. 84, 85–277. CrossRef CAS Web of Science Google Scholar
Kalyanasundaram, K. (1982). Coord. Chem. Rev. 46, 159–244. CrossRef CAS Web of Science Google Scholar
Pearson, P., Bond, A. M., Deacon, G. B., Forsyth, C. & Spiccia, L. (2008). Inorg. Chim. Acta, 361, 601–612. Web of Science CSD CrossRef CAS Google Scholar
Philippopoulos, A. I., Terzis, A., Raptopoulou, C. P., Catalano, V. J. & Falaras, P. (2007). Eur. J. Inorg. Chem. pp. 5633–5644. CrossRef Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takeuchi, K. J., Thompson, M. S., Pipes, D. W. & Meyer, T. J. (1984). Inorg. Chem. 19, 1404–1407. Google Scholar

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.