trans-Bis(2,2′-bi­pyridine-4,4′-di­carb­oxy­lic acid-κ2N,N′)di­chlorido­ruthenium(III) perchlorate

Soares, L.G.L.; Padilha, D.S.; Amado, R.S.; Scarpellini, M.

doi:10.1107/S241431461801547X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 11| November 2018| x181547

https://doi.org/10.1107/S241431461801547X

Open

access

trans-Bis(2,2′-bipyridine-4,4′-dicarboxylic acid-κ²N,N′)dichloridoruthenium(III) perchlorate

Lívia Gonçalves Leida Soares,^a Diego Silva Padilha,^a Roberto Salgado Amado ^a and Marciela Scarpellini ^a ^*

^aInstituto de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, Bl. A, Lab. 628a. CEP 21941-909, Rio de Janeiro, Brazil
^*Correspondence e-mail: marciela@iq.ufrj.br

Edited by C. Massera, Università di Parma, Italy (Received 15 October 2018; accepted 1 November 2018; online 10 November 2018)

In the crystal structure of the ruthenium(III) complex, trans-[Ru^III(dcbpy)₂Cl₂]ClO₄ (dcbpy = 2,2′-bipyridine-4,4′-dicarboxylic acid, C₁₂H₈N₂O₄), the Ru^III atom lies on an inversion centre, showing a small distortion in its octahedral environment. The Ru—Cl bond lengths are shorter than those present in the analogous trans-ruthenium(II) compound containing the bipyridine ligand. The C—O distances in the two symmetry-independent carboxylic acid moieties of the ligand are similar in one group, but different in the other. This is probably due to the different intermolecular interactions they experience with neighbouring cationic complexes. The hydrogen-bonding interactions in which they are involved form a three-dimensional structure, similar to those found in coordination polymers.

Keywords: crystal structure; ruthenium; dcbpy ligand; trans configuration.

CCDC reference: 1865871

Structure description

Complexes of ruthenium(III) have been described in the literature for several purposes, such as: anticancer agents (Shoair et al., 2015 ; Zeng et al., 2017 ), water-oxidation catalysts (WOC) (Liu et al., 2018 ), precursors for new oxidants (Seok et al., 2012 ) and for their catalytic and biological activity (Thangadurai & Natarajan, 2001 ). Ruthenium complexes with polypyridine ligands in a trans configuration have been mostly designed for dye-sensitized solar cells (DSSC) applications (Barolo et al., 2013 ). In DSSC, ruthenium complexes are used as dyes, and are responsible for the electron injection into the conduction band of the semiconductor (usually TiO₂). Ligands in these complexes may have different functions, such as ancillary or anchoring. Anchoring ligands may present functional groups able to covalently bond to the semiconductor surface. The most often synthetically employed are phosphonic and carboxylic groups that guarantee the adsorption of the coordination compound on the desired surface (Pashaei et al., 2016 ). On the other hand, ancillary ligands are employed to finely modulate the redox potential of the central metal cation.

In this work, the molecular and crystal structures of the complex trans-Bis(2,2′-bipyridine-4,4′-dicarboxylic acid-κ²N,N′)dichloridoruthenium(III) perchlorate are described (Fig. 1). The ruthenium(III) ion, which lies on an inversion centre, is coordinated by two molecules of dcbpy and two chloride ions, showing a distorted N₄Cl₂ octahedral geometry. This mononuclear cationic complex was isolated with perchlorate as counter-ion.

Figure 1
The structures of the molecular entities in the title compound. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (i) $[{1\over 2}]$ − x, − $[{1\over 2}]$ − y, 1 − z; (ii) 1 − x, +y, $[{3\over 2}]$ − z].

The Ru1—Cl1 bond length (Table 1) is 2.2865 (13) Å, and is shorter than the value of 2.4123 (4) Å present in the cis-Ru^II analogue cis-[Ru^II(dcbpy)₂Cl₂] (Fujihara et al., 2004 ). This difference may be due to either the oxidation state of the central metal cation, as has been reported before (Seok et al., 2012), or to the configuration around the metal (cis or trans). The Ru1—Cl1 distance in the complex trans-[Ru^II(bpy)₂Cl₂] [2.3893 (6) Å, Klüfers & Zangl, 2007 ] shows a higher value than that of the title complex. This is observed because ruthenium(III) is a better Lewis acid than ruthenium(II), attracting the electrons and shortening the bond.

Table 1
Selected bond lengths (Å)

Ru1—Cl1	2.2865 (13)	O1—C4	1.253 (6)
Ru1—N2	2.082 (3)	O3—C12	1.195 (7)
Ru1—N1	2.090 (3)	O2—C4	1.253 (6)
Cl2—O5	1.424 (7)	O4—C12	1.316 (6)
Cl2—O6	1.295 (6)

The Ru1—N1 and Ru1—N2 bond lengths are 2.090 (3) Å and 2.082 (3) Å, respectively, and are similar to the values reported for the analogous complex trans-[Ru^II(bpy)₂Cl₂] in which Ru1—N1 = 2.0632 (18) Å and Ru1—N2 = 2.0560 (19) Å (Klüfers & Zangl, 2007). In general, Ru—N values are comparable with the average bond lengths in similar complexes with a cis configuration: cis-[Ru^II(dcbpy)₂Cl₂] (Fujihara et al., 2004), cis-[Ru^III(bpy)₂Cl₂]Cl·2H₂O (Eggleston et al., 1985 ) and cis-[Ru^III(dmbpy)₂Cl₂](PF₆) (dmbpy: 2,2′-bipyridine-4,4′-dimethyl) (Seok et al., 2012). The N2—Ru—N1 angle is 76.47 (13)°, which is a smaller bite angle than the ideal 90°, as expected for bipyridines, because of the chelate constraints (Schwalbe et al., 2008 ). The average Cl—Ru—N angle is close to 90°, similar to what is reported for the complex trans-[Ru^II(bpy)₂Cl₂] (Klüfers & Zangl, 2007), showing a distortion in the octahedral coordination environment.

The angle between the mean planes of the two pyridine rings shows very different values depending on the configuration around the metal cation. In the title compound, this angle is 14.26 (16)°, which is higher than the average value of 9 (2)° in the cis complex, cis-[Ru^II(dcbpy)₂Cl₂] (Fujihara et al., 2004), but lower than the value of 23.8 (1)° in trans-[Ru^II(bpy)₂Cl₂] (Klüfers & Zangl, 2007).

The angle between the mean planes passing through Ru1—N1—N2—N1ⁱ—N2ⁱ [symmetry code: (i) $[{1\over 2}]$ − x, − $[{1\over 2}]$ − y, 1 − z) and N1—C6—C7—N2 (involved in the bite angle) is 18.9 (3)°, which is close to the value of 20.4997 (4)° reported for trans-[Ru^II(bpy)₂Cl₂] (Klüfers & Zangl, 2007).

The carboxylic group C4O1O2H2 shows very similar C—O bond lengths: C4—O2: 1.253 (6) Å and C4—O1: 1.253 (6) Å. This fact can be explained considering that it forms two hydrogen bonds (one as donor with O2—H2 and one as acceptor with O1) with the same group of a neighbouring complex. This is not observed for C12O3O4H4, in which only O4—H4 acts as hydrogen-bond donor towards the O5 atom of one perchlorate anion, while O3 is not involved in any interactions. This explains the lengthening of the C12—O4 bond [1.316 (6) Å], with respect to C12—O3, which shows a value of 1.195 (7) Å.

The hydrogen-bonding interactions between the carboxylic C4O1O2H2 of two neighbouring complexes (Table 2) form a linear ribbon aligned with the Ru1—N1 bond. On the other side, the carboxylic groups aligned with the Ru1—N2 bond (C12O3O4H4) and the perchlorate anions are also involved in hydrogen bonding; both the symmetry-related O5 atoms of the perchlorate anion interact with two cationic complexes in two different set of planes. These planes form an angle of 33.7 (3)° (Fig. 2; the angle has been calculated considering the mean planes passing through sets of O1—C4—O1 atoms) and comprise two sets of ribbons formed by the H-bonded C4O1O2H2 carboxylic groups (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.90	2.698 (5)	165.1
O4—H4⋯O5	0.82	1.93	2.752 (7)	175.5
(i) −x, 1 − y, 1 − z

Figure 2
View of the planes along which two sets of ribbons formed by the hydrogen-bonded carboxylic groups C4O1O2H2 propagate (hydrogen bonds are represented by blue dashed lines). Red dashed lines show the interactions between the perchlorate anion and the C12O3O4H4 carboxylate group.

Figure 3
Crystal packing of [Ru^III(dcbpy)₂Cl₂]ClO₄ (top, middle), and perpendicular view of the layers in which the ribbons propagate (bottom).

The distance between the closest O2—C4—O1 centroids is 7.3833 (7) Å, while the distance between two adjacent ruthenium(III) atoms is 16.5316 (10) Å, and that of the closest ruthenium(III) atoms in the two different planes is of 13.0452 (10) Å.

Focusing on the dcbpy ligand, Fujihara et al. (2004) described the analogous cis compound, cis-[Ru^II(dcbpy)₂Cl₂]. Analyzing ruthenium(III) complexes, only two similar compounds have been found in the literature: cis-[Ru^III(bpy)₂Cl₂]Cl·2H₂O (bpy: 2,2′-bipyridine) (Eggleston et al., 1985) and cis-[Ru^III(dmbpy)₂Cl₂](PF₆) (Seok et al., 2012). In addition, Klüfers & Zangl (2007) presented a ruthenium(III) complex in a trans configuration with 2,2′-bipyridine, trans-[Ru^III(bpy)₂Cl₂]. To the best of our knowledge, these are the only few examples of crystal structures of trans-ruthenium(III) complexes comprising bipyridine and a monodentate halogenido group as ligands.

Synthesis and crystallization

While attempting to synthesize the complex cis-[Ru^II(dcbpy)₂(4m4but)] (4m4but = N-butyl-4′-methyl-[2,2′-bipyridine]-4-methanamine), a mixture of cis-[Ru^II(dcbpy)₂Cl₂] and 4m4but (1:1) in MeOH/NaOH solution was refluxed for 3 h, in the dark, under an argon atmosphere. After this time, the solvent was removed under reduced pressure, and a red solid was obtained. Orange single crystals of the title trans complex were serendipitously obtained by recrystallization of this solid from a HClO₄ solution (1.5 M) after several months.

IR (cm⁻¹, CsI): 3449 (m), 2928 (w), 2855 (w), 1725 (m), 1697 (sh), 1619 (w), 1556 (w), 1448 (sh), 1408 (w), 1370 (w), 1318 (w), 1266 (w), 1233, 1105 (s), 1084 (sh), 1023 (w), 901 (w), 818 (w), 769 (w), 630 (s). Diffuse reflectance (nm, BaSO₄): 248, 293, 467, 540 (sh), 679 (sh).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[RuCl₂(C₁₂H₈N₂O₄)₂]ClO₄
M_r	759.83
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	22.3394 (19), 8.1249 (7), 14.7667 (14)
β (°)	93.162 (4)
V (Å³)	2676.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.96
Crystal size (mm)	0.24 × 0.10 × 0.06

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.697, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	18342, 2741, 2135
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.112, 1.07
No. of reflections	2741
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.63
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT2018 (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1865871

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461801547X/xi4002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461801547X/xi4002Isup2.hkl

Letter to the referees. DOI: https://doi.org/10.1107/S241431461801547X/xi4002sup3.pdf

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009), Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

trans-Bis(2,2'-bipyridine-4,4'-dicarboxylic acid-κ²N,N')dichloridoruthenium(III) perchlorate top

Crystal data top

[RuCl₂(C₁₂H₈N₂O₄)₂]ClO₄	F(000) = 1516
M_r = 759.83	D_x = 1.886 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.3394 (19) Å	Cell parameters from 4234 reflections
b = 8.1249 (7) Å	θ = 2.7–26.0°
c = 14.7667 (14) Å	µ = 0.96 mm⁻¹
β = 93.162 (4)°	T = 273 K
V = 2676.2 (4) Å³	Irregular, orange
Z = 4	0.24 × 0.10 × 0.06 mm

Data collection top

Bruker D8 Venture diffractometer	2135 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.080
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θ_max = 26.4°, θ_min = 2.7°
T_min = 0.697, T_max = 0.745	h = −27→27
18342 measured reflections	k = −10→10
2741 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0449P)² + 15.531P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2741 reflections	Δρ_max = 0.92 e Å⁻³
202 parameters	Δρ_min = −0.63 e Å⁻³
0 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq
Ru1	0.250000	−0.250000	0.500000	0.02162 (16)
Cl1	0.29145 (6)	−0.09129 (15)	0.39197 (9)	0.0401 (3)
Cl2	0.500000	0.6986 (3)	0.750000	0.0497 (5)
N2	0.28196 (15)	−0.0850 (4)	0.5991 (2)	0.0246 (8)
N1	0.17958 (15)	−0.0825 (4)	0.5090 (2)	0.0233 (8)
O1	0.00398 (16)	0.2932 (5)	0.4656 (3)	0.0535 (11)
C7	0.25357 (18)	0.0625 (5)	0.5975 (3)	0.0216 (9)
C6	0.19433 (18)	0.0614 (5)	0.5491 (3)	0.0224 (9)
O3	0.3334 (2)	0.4578 (5)	0.7421 (3)	0.0662 (13)
O2	0.07193 (17)	0.4483 (5)	0.5417 (4)	0.0696 (15)
H2	0.047154	0.520833	0.530143	0.104*
C5	0.1549 (2)	0.1923 (5)	0.5500 (3)	0.0270 (10)
H5	0.166383	0.291296	0.577413	0.032*
C8	0.2776 (2)	0.1957 (5)	0.6436 (3)	0.0272 (10)
H8	0.257691	0.296196	0.641492	0.033*
C11	0.3307 (2)	−0.1043 (6)	0.6549 (3)	0.0338 (12)
H11	0.346985	−0.209010	0.662892	0.041*
C9	0.3318 (2)	0.1797 (6)	0.6932 (3)	0.0291 (10)
O4	0.41452 (19)	0.3021 (6)	0.7693 (4)	0.0716 (14)
H4	0.431618	0.390156	0.778970	0.107*
C3	0.0978 (2)	0.1736 (6)	0.5094 (3)	0.0290 (10)
C2	0.0818 (2)	0.0235 (6)	0.4735 (4)	0.0334 (11)
H2A	0.043392	0.006857	0.447597	0.040*
C1	0.1231 (2)	−0.1027 (6)	0.4759 (3)	0.0325 (11)
H1	0.111260	−0.205576	0.453870	0.039*
C10	0.3574 (2)	0.0258 (6)	0.7008 (3)	0.0373 (12)
H10	0.392536	0.010067	0.736548	0.045*
C12	0.3593 (2)	0.3296 (7)	0.7372 (4)	0.0418 (13)
C4	0.0543 (2)	0.3163 (6)	0.5054 (4)	0.0372 (12)
O5	0.4698 (3)	0.5970 (9)	0.8115 (5)	0.140 (3)
O6	0.5377 (4)	0.7789 (11)	0.8031 (6)	0.181 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.0194 (2)	0.0161 (2)	0.0290 (3)	0.0071 (2)	−0.00141 (18)	−0.0053 (2)
Cl1	0.0533 (8)	0.0254 (6)	0.0429 (7)	0.0029 (5)	0.0158 (6)	−0.0004 (5)
Cl2	0.0304 (9)	0.0567 (12)	0.0608 (13)	0.000	−0.0079 (9)	0.000
N2	0.0227 (19)	0.0222 (19)	0.028 (2)	0.0088 (15)	−0.0035 (16)	−0.0064 (15)
N1	0.0201 (18)	0.0184 (18)	0.031 (2)	0.0059 (14)	−0.0016 (15)	−0.0044 (15)
O1	0.0272 (19)	0.040 (2)	0.091 (3)	0.0158 (16)	−0.014 (2)	−0.008 (2)
C7	0.019 (2)	0.018 (2)	0.027 (2)	0.0042 (17)	0.0004 (18)	−0.0015 (17)
C6	0.020 (2)	0.020 (2)	0.027 (2)	0.0056 (17)	0.0014 (18)	−0.0033 (18)
O3	0.065 (3)	0.037 (2)	0.094 (3)	0.000 (2)	−0.021 (3)	−0.022 (2)
O2	0.036 (2)	0.028 (2)	0.143 (4)	0.0180 (17)	−0.018 (2)	−0.022 (2)
C5	0.027 (2)	0.017 (2)	0.038 (3)	0.0061 (18)	0.003 (2)	−0.0054 (18)
C8	0.030 (2)	0.020 (2)	0.032 (3)	0.0054 (18)	0.002 (2)	−0.0040 (18)
C11	0.034 (3)	0.030 (3)	0.036 (3)	0.017 (2)	−0.010 (2)	−0.009 (2)
C9	0.027 (2)	0.031 (2)	0.029 (2)	0.001 (2)	0.002 (2)	−0.007 (2)
O4	0.046 (3)	0.066 (3)	0.100 (4)	−0.009 (2)	−0.022 (3)	−0.024 (3)
C3	0.022 (2)	0.024 (2)	0.041 (3)	0.0083 (19)	0.004 (2)	0.000 (2)
C2	0.018 (2)	0.033 (3)	0.049 (3)	0.0047 (19)	−0.002 (2)	−0.008 (2)
C1	0.025 (2)	0.027 (3)	0.046 (3)	0.0035 (19)	0.000 (2)	−0.011 (2)
C10	0.028 (3)	0.047 (3)	0.035 (3)	0.012 (2)	−0.009 (2)	−0.014 (2)
C12	0.038 (3)	0.046 (3)	0.041 (3)	−0.005 (3)	−0.002 (2)	−0.013 (3)
C4	0.028 (3)	0.025 (2)	0.059 (3)	0.009 (2)	0.002 (2)	0.000 (2)
O5	0.163 (7)	0.147 (6)	0.115 (5)	−0.105 (5)	0.060 (5)	−0.055 (5)
O6	0.168 (7)	0.224 (9)	0.142 (7)	−0.132 (7)	−0.063 (6)	0.025 (6)

Geometric parameters (Å, º) top

Ru1—Cl1ⁱ	2.2865 (13)	O2—H2	0.8200
Ru1—Cl1	2.2865 (13)	O2—C4	1.253 (6)
Ru1—N2ⁱ	2.082 (3)	C5—H5	0.9300
Ru1—N2	2.082 (3)	C5—C3	1.388 (6)
Ru1—N1	2.090 (3)	C8—H8	0.9300
Ru1—N1ⁱ	2.090 (3)	C8—C9	1.385 (6)
Cl2—O5ⁱⁱ	1.424 (6)	C11—H11	0.9300
Cl2—O5	1.424 (7)	C11—C10	1.374 (7)
Cl2—O6	1.295 (6)	C9—C10	1.378 (7)
Cl2—O6ⁱⁱ	1.295 (6)	C9—C12	1.496 (7)
N2—C7	1.356 (5)	O4—H4	0.8200
N2—C11	1.338 (5)	O4—C12	1.316 (6)
N1—C6	1.344 (5)	C3—C2	1.369 (7)
N1—C1	1.338 (5)	C3—C4	1.511 (6)
O1—C4	1.253 (6)	C2—H2A	0.9300
C7—C6	1.469 (6)	C2—C1	1.378 (6)
C7—C8	1.372 (6)	C1—H1	0.9300
C6—C5	1.382 (6)	C10—H10	0.9300
O3—C12	1.195 (7)

Cl1—Ru1—Cl1ⁱ	180.00 (6)	C4—O2—H2	109.5
N2—Ru1—Cl1	89.48 (11)	C6—C5—H5	120.5
N2—Ru1—Cl1ⁱ	90.51 (11)	C6—C5—C3	118.9 (4)
N2ⁱ—Ru1—Cl1ⁱ	89.49 (11)	C3—C5—H5	120.5
N2ⁱ—Ru1—Cl1	90.51 (11)	C7—C8—H8	120.2
N2—Ru1—N2ⁱ	180.0	C7—C8—C9	119.7 (4)
N2—Ru1—N1ⁱ	103.53 (13)	C9—C8—H8	120.2
N2ⁱ—Ru1—N1ⁱ	76.47 (13)	N2—C11—H11	119.0
N2ⁱ—Ru1—N1	103.53 (13)	N2—C11—C10	122.0 (4)
N2—Ru1—N1	76.47 (13)	C10—C11—H11	119.0
N1ⁱ—Ru1—Cl1ⁱ	90.70 (11)	C8—C9—C12	118.6 (4)
N1—Ru1—Cl1	90.70 (11)	C10—C9—C8	118.4 (4)
N1ⁱ—Ru1—Cl1	89.30 (11)	C10—C9—C12	123.0 (4)
N1—Ru1—Cl1ⁱ	89.30 (11)	C12—O4—H4	109.5
N1ⁱ—Ru1—N1	180.00 (12)	C5—C3—C4	120.4 (4)
O5—Cl2—O5ⁱⁱ	109.1 (6)	C2—C3—C5	118.6 (4)
O6ⁱⁱ—Cl2—O5ⁱⁱ	102.8 (4)	C2—C3—C4	121.0 (4)
O6ⁱⁱ—Cl2—O5	111.3 (6)	C3—C2—H2A	120.2
O6—Cl2—O5ⁱⁱ	111.3 (6)	C3—C2—C1	119.5 (4)
O6—Cl2—O5	102.8 (4)	C1—C2—H2A	120.2
O6ⁱⁱ—Cl2—O6	119.5 (9)	N1—C1—C2	122.3 (4)
C7—N2—Ru1	114.5 (3)	N1—C1—H1	118.9
C11—N2—Ru1	126.4 (3)	C2—C1—H1	118.9
C11—N2—C7	118.6 (4)	C11—C10—C9	119.4 (4)
C6—N1—Ru1	115.3 (3)	C11—C10—H10	120.3
C1—N1—Ru1	126.5 (3)	C9—C10—H10	120.3
C1—N1—C6	118.1 (4)	O3—C12—C9	123.2 (5)
N2—C7—C6	114.3 (4)	O3—C12—O4	124.9 (5)
N2—C7—C8	121.2 (4)	O4—C12—C9	111.9 (5)
C8—C7—C6	124.3 (4)	O1—C4—O2	125.6 (4)
N1—C6—C7	114.4 (4)	O1—C4—C3	117.5 (5)
N1—C6—C5	122.2 (4)	O2—C4—C3	116.9 (4)
C5—C6—C7	123.3 (4)

Ru1—N2—C7—C6	19.6 (5)	C5—C3—C2—C1	−2.0 (8)
Ru1—N2—C7—C8	−164.9 (3)	C5—C3—C4—O1	178.1 (5)
Ru1—N2—C11—C10	162.3 (4)	C5—C3—C4—O2	−1.4 (8)
Ru1—N1—C6—C7	−13.0 (5)	C8—C7—C6—N1	−179.7 (4)
Ru1—N1—C6—C5	171.6 (4)	C8—C7—C6—C5	−4.4 (7)
Ru1—N1—C1—C2	−170.4 (4)	C8—C9—C10—C11	3.8 (8)
N2—C7—C6—N1	−4.3 (6)	C8—C9—C12—O3	10.4 (8)
N2—C7—C6—C5	171.0 (4)	C8—C9—C12—O4	−169.8 (5)
N2—C7—C8—C9	−0.4 (7)	C11—N2—C7—C6	−168.0 (4)
N2—C11—C10—C9	3.5 (8)	C11—N2—C7—C8	7.6 (7)
N1—C6—C5—C3	1.1 (7)	C3—C2—C1—N1	−2.9 (8)
C7—N2—C11—C10	−9.2 (7)	C2—C3—C4—O1	−2.1 (8)
C7—C6—C5—C3	−173.9 (4)	C2—C3—C4—O2	178.4 (6)
C7—C8—C9—C10	−5.3 (7)	C1—N1—C6—C7	169.6 (4)
C7—C8—C9—C12	175.5 (4)	C1—N1—C6—C5	−5.9 (7)
C6—N1—C1—C2	6.8 (7)	C10—C9—C12—O3	−168.8 (6)
C6—C7—C8—C9	174.7 (4)	C10—C9—C12—O4	11.1 (8)
C6—C5—C3—C2	2.9 (7)	C12—C9—C10—C11	−177.1 (5)
C6—C5—C3—C4	−177.3 (4)	C4—C3—C2—C1	178.2 (5)

Symmetry codes: (i) −x+1/2, −y−1/2, −z+1; (ii) −x+1, y, −z+3/2.

Hydrogen-bond geometry () top

D—H···A

O1—H2···O2ⁱⁱⁱ

O4—H4···O5

Symmetry code: (iii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °) top

D-H···A	D-H	H···A	D···A	D-H···A
O2-H2···O1ⁱ	0.82	1.90	2.698 (5)	165.1
O4-H4···O5	0.82	1.93	2.752 (7)	175.5

(i) -x, 1-y, 1-z

Acknowledgements

The authors thank Laboratório Multiusuário de Difração de Raios X da Universidade Federal Fluminense (LDRX/UFF) for the use of the laboratory facilities.

Funding information

Funding for this research was provided by: Conselho Nacional de Desenvolvimento Científico e Tecnológico (studentship No. 155671/2014-6 to L. Gonçalves Leida Soares; studentship No. 141606/2014-2 to D. Silva Padilha); Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (grant No. 3100.101.7006 P6); Fundação Carlos Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro (grant No. E-26/010.001499/2014).

References

Barolo, C., Yum, J.-H., Artuso, E., Barbero, N., Di Censo, D., Lobello, M. G., Fantacci, S., De Angelis, F., Grätzel, M., Nazeeruddin, M. K. & Viscardi, G. (2013). ChemSusChem, 6, 2170–2180. CrossRef PubMed Google Scholar
Bruker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Eggleston, D. S., Goldsby, K. A., Hodgson, D. J. & Meyer, T. J. (1985). Inorg. Chem. 24, 4573–4580. CrossRef CAS Web of Science Google Scholar
Fujihara, T., Kobayashi, A., Iwai, M. & Nagasawa, A. (2004). Acta Cryst. E60, m1172–m1174. Web of Science CrossRef IUCr Journals Google Scholar
Klüfers, P. & Zangl, A. (2007). Acta Cryst. E63, m3088. Web of Science CrossRef IUCr Journals Google Scholar
Liu, Y., Chen, G., Yiu, S.-M., Wong, C.-Y. & Lau, T.-C. (2018). ChemCatChem, 10, 501–504. CrossRef Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Pashaei, B., Shahroosvand, H., Grätzel, M. & Nazeeruddin, M. K. (2016). Chem. Rev. 116, 9485–9564. CrossRef PubMed Google Scholar
Schwalbe, M., Schäfer, B., Görls, H., Rau, S., Tschierlei, S., Schmitt, M., Popp, J., Vaughan, G., Henry, W. & Vos, J. G. (2008). Eur. J. Inorg. Chem. pp. 3310–3319. Web of Science CrossRef Google Scholar
Seok, W. K., Ran Jo, M., Kim, N. & Yun, H. (2012). Z. Anorg. Allg. Chem. 638, 754–757. CrossRef Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shoair, A. G. F., Toson, E. A. & El-mezayen, H. A. (2015). Appl. Organomet. Chem. 29, 412–418. CrossRef Google Scholar
Thangadurai, T. D. & Natarajan, K. (2001). Synth. React. Inorg. Met.-Org. Chem. 31, 549–567. CrossRef Google Scholar
Zeng, L., Gupta, P., Chen, Y., Wang, E., Ji, L., Chao, H. & Chen, Z.-S. (2017). Chem. Soc. Rev. 46, 5771–5804. CrossRef PubMed 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.