2-[Tris(pyridin-2-yl)meth­yl]pyridinium trans-bis­(aceto­nitrile)­tetra­chlorido­ruthenate(III) aceto­nitrile monosolvate

Matsumoto, K.; Kannami, M.; Oda, M.

doi:10.1107/S2414314617013712

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 9| September 2017| x171371

https://doi.org/10.1107/S2414314617013712

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2-[Tris(pyridin-2-yl)methyl]pyridinium trans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate

Kouzou Matsumoto,^a ^* Masaki Kannami ^b and Masaji Oda ^b

^aInstitute of Natural Sciences, Senshu University, Higashimita 2-1-1, Kawasaki, Kanagawa 214-8580, Japan, and ^bDepartment of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
^*Correspondence e-mail: matsumoto@isc.senshu-u.ac.jp

Edited by H. Ishida, Okayama University, Japan (Received 13 September 2017; accepted 25 September 2017; online 29 September 2017)

The asymmetric unit of the title compound, [(C₅H₄N)₃C(C₅H₅N)][RuCl₄(CH₃CN)₂]·CH₃CN, contains one 2-[tris(pyridin-2-yl)methyl]pyridinium cation, one trans-bis(acetonitrile)tetrachloridoruthenate(III) anion and one acetonitrile solvent molecule. The Ru^III ion is coordinated by four Cl⁻ anions in the equatorial plane and by two acetonitrile ligands in the axial positions, forming a distorted octahedral geometry. The cation, the monoprotonated species of tetrakis(pyridin-2-yl)methane, forms an intramolecular N—H⋯N hydrogen bond between the pyridinium ring and one of the pyridine rings. The complex anions are linked to each other via C—H⋯Cl hydrogen bonds, forming an undulating sheet parallel to the ac plane. A C—H⋯N hydrogen bond between the cation and the anion is also observed. The solvate acetonitrile molecule forms C—H⋯N and C—H⋯Cl hydrogen bonds, respectively, with the cation and the anion.

Keywords: crystal structure; pyridine; pyridinium ion; ruthenium(III) complex; hydrogen bonding.

CCDC reference: 1576273

Structure description

We have investigated the synthesis and properties of tetrakis(pyridin-2-yl)methane (py₄C) over the last decade (Matsumoto et al., 2003 , 2004 ). In the course of our studies on py₄C, we are interested in the ruthenium complex with py₄C because of the fascinating properties of ruthenium polypyridine complexes (Juris et al., 1988 ; Balzani et al., 1996 ). Although we did not obtain the desired ruthenium complex, we obtained single crystals of the title compound instead. This is the first report of the crystal structure including the monoprotonated py₄C cation, [(py₄C)·H]⁺.

The asymmetric unit consists of one molecule of [(py₄C)·H]⁺, one molecule of trans-bis(acetonitrile)tetrachloridoruthenate(III), [RuCl₄(CH₃CN)₂]⁻, and one acetonitrile molecule (Fig. 1). It should be noted that an intramolecular N—H⋯N hydrogen bond is formed in the cation (Fig. 1 and Table 1). Although py₄C often takes a highly symmetric part in the crystal structure, the cation shows an unsymmetrical structure, where atom C1 occupies a general position. On the other hand, the structure of [RuCl₄(CH₃CN)₂]⁻ resembles those in previous reports (Gheller et al., 1995 ; Appelbaum et al., 1999 ; Jabłońska-Wawrzycka et al., 2013 ). The Ru^III ion adopts an octahedral coordination geometry, with four Cl atoms occupying equatorial positions and two acetonitrile molecules in the axial positions. The Ru^III and four Cl atoms essentially lie in a plane and two acetonitrile molecules are approximately perpendicular to the RuCl₄ plane. The average Ru—Cl and Ru—N bond lengths are 2.36 and 2.02 Å, respectively.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2	0.87 (2)	1.87 (2)	2.615 (2)	143.3 (19)
C22—H18⋯Cl1ⁱ	0.98	2.69	3.5521 (19)	146
C22—H19⋯Cl4ⁱ	0.98	2.78	3.5972 (19)	142
C24—H21⋯Cl1ⁱⁱ	0.98	2.77	3.7393 (18)	172
C24—H22⋯Cl2ⁱⁱⁱ	0.98	2.77	3.6346 (18)	147
C24—H23⋯N4ⁱⁱ	0.98	2.65	3.606 (2)	165
C6—H5⋯N7	0.95	2.45	3.248 (3)	142
C26—H26⋯Cl4^iv	0.98	2.84	3.749 (3)	154
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
A view of the molecular components of the title compound, showing the atom-labelling and displacement ellipsoids drawn at the 50% probability level for non-H atoms. The intramolecular N—H⋯N hydrogen bond and the C—H⋯N hydrogen bond are shown as dashed lines.

In the crystal, the anions form an undulating sheet parallel to the ac plane via C—H⋯Cl hydrogen bonds (C22—H18⋯Cl1ⁱ, C22—H19⋯Cl4ⁱ, C24—H21⋯Cl1ⁱⁱ and C24—H22⋯Cl2ⁱⁱⁱ; symmetry codes as in Table 1). A C—H⋯N hydrogen bond between [(py₄C)·H]⁺ and [RuCl₄(CH₃CN)₂]⁻ is also formed (C24—H23⋯N4ⁱⁱ; Table 1). The acetonitrile solvent molecule forms C—H⋯N and C—H⋯Cl hydrogen bonds (C6—H5⋯N7 and C26—H26⋯Cl4^iv; Table 1), respectively, with [(py₄C)·H]⁺ and [RuCl₄(CH₃CN)₂]⁻.

Synthesis and crystallization

A solution of ruthenium(III) chloride n-hydrate (100 mg) in ethanol (6 ml) and water (4 ml) was refluxed for 4 h. Tetrakis(pyridin-2-yl)methane (324 mg) in ethanol (120 ml) was added to the refluxing solution and the reflux was continued for additional 4 h. After cooling to room temperature, the solvents were evaporated and dried under vacuum. Acetonitrile (50 ml) was added to the residue and the insoluble substances were removed by filtration. Brown prisms (70 mg, 21%) appeared from the filtrate by slow evaporation at room temperature. Although the residue obtained from the reaction mixture might have included the desired ruthenium complex, acetonitrile molecules coordinating the ruthenium ion resulted in formation of the title compound. Analysis calculated for C₂₇H₂₆Cl₄N₇Ru: C 46.90, H 3.79, N 14.18%; found: C 46.86, H 3.78, N 14.24%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N—H atom H1 was located in a difference Fourier map and refined freely. The CH hydrogen atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	(C₂₁H₁₇N₄)[RuCl₄(C₂H₃N)₂]·C₂H₃N
M_r	691.42
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	7.6796 (3), 30.3330 (14), 13.1153 (6)
β (°)	100.194 (2)
V (Å³)	3006.9 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.91
Crystal size (mm)	0.2 × 0.2 × 0.1

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.739, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	28746, 6815, 6043
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.059, 1.06
No. of reflections	6815
No. of parameters	359
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.25
Computer programs: PROCESS-AUTO (Rigaku, 1998 ), SIR92 (Altomare et al., 1994 ), SHELXL2017 (Sheldrick, 2015 ), Yadokari-XG 2009 (Wakita, 2001 ) and ORTEP-3 for Windows (Farrugia, 2012 ), CrystalStructure (Rigaku, 2011 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1576273

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617013712/is4018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617013712/is4018Isup2.hkl

checkCIF report

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: Yadokari-XG 2009 (Wakita, 2001) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2011), Yadokari-XG 2009 (Wakita, 2001) and publCIF (Westrip, 2010).

2-[Tris(pyridin-2-yl)methyl]pyridinium trans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate top

Crystal data top

(C₂₁H₁₇N₄)[RuCl₄(C₂H₃N)₂]·C₂H₃N	F(000) = 1396
M_r = 691.42	D_x = 1.527 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
a = 7.6796 (3) Å	Cell parameters from 21524 reflections
b = 30.3330 (14) Å	θ = 3.0–27.4°
c = 13.1153 (6) Å	µ = 0.91 mm⁻¹
β = 100.194 (2)°	T = 200 K
V = 3006.9 (2) Å³	Prism, brown
Z = 4	0.2 × 0.2 × 0.1 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	6043 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 27.4°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.739, T_max = 0.913	k = −39→38
28746 measured reflections	l = −16→16
6815 independent 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)] = 0.022	Hydrogen site location: mixed
wR(F²) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.027P)² + 1.1697P] where P = (F_o² + 2F_c²)/3
6815 reflections	(Δ/σ)_max = 0.001
359 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

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.

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Ru1	0.13693 (2)	0.17595 (2)	0.31885 (2)	0.02132 (4)
Cl1	0.23972 (6)	0.23538 (2)	0.22993 (3)	0.03010 (9)
Cl2	0.04670 (5)	0.22761 (2)	0.43493 (3)	0.02920 (9)
Cl3	0.02924 (6)	0.11680 (2)	0.40743 (3)	0.03249 (9)
Cl4	0.22432 (6)	0.12549 (2)	0.20175 (3)	0.02980 (9)
N1	0.03878 (19)	0.32851 (4)	0.29181 (11)	0.0257 (3)
H1	0.119 (3)	0.3148 (7)	0.3352 (16)	0.037 (6)*
N2	0.33833 (18)	0.32182 (4)	0.42140 (11)	0.0282 (3)
N3	0.00392 (19)	0.42519 (5)	0.44106 (11)	0.0325 (3)
N4	0.3292 (2)	0.41845 (5)	0.19756 (11)	0.0308 (3)
N5	−0.10403 (19)	0.18046 (4)	0.22930 (11)	0.0271 (3)
N6	0.37875 (19)	0.17269 (4)	0.41090 (11)	0.0257 (3)
N7	−0.1595 (3)	0.49066 (7)	0.10578 (18)	0.0695 (6)
C1	0.2296 (2)	0.39335 (5)	0.35306 (12)	0.0229 (3)
C2	0.0678 (2)	0.37197 (5)	0.28477 (12)	0.0235 (3)
C3	−0.1004 (2)	0.30712 (6)	0.23517 (14)	0.0330 (4)
H2	−0.113620	0.276230	0.242896	0.040*
C4	−0.2220 (2)	0.33032 (6)	0.16662 (14)	0.0367 (4)
H3	−0.319864	0.315804	0.125818	0.044*
C5	−0.1990 (2)	0.37557 (7)	0.15810 (13)	0.0363 (4)
H4	−0.282418	0.392278	0.111461	0.044*
C6	−0.0557 (2)	0.39630 (6)	0.21712 (13)	0.0315 (4)
H5	−0.041347	0.427264	0.211507	0.038*
C7	0.3840 (2)	0.36092 (5)	0.38549 (11)	0.0228 (3)
C8	0.4657 (2)	0.29287 (6)	0.45778 (14)	0.0330 (4)
H6	0.432529	0.265062	0.481619	0.040*
C9	0.6437 (2)	0.30171 (6)	0.46217 (14)	0.0330 (4)
H7	0.731354	0.280592	0.488755	0.040*
C10	0.6897 (2)	0.34202 (6)	0.42687 (14)	0.0331 (4)
H8	0.810860	0.349216	0.429875	0.040*
C11	0.5595 (2)	0.37222 (6)	0.38685 (13)	0.0289 (3)
H9	0.589818	0.399919	0.361057	0.035*
C12	0.1711 (2)	0.41119 (5)	0.45254 (12)	0.0246 (3)
C13	−0.0499 (3)	0.44280 (7)	0.52414 (15)	0.0412 (4)
H10	−0.168848	0.452695	0.516620	0.049*
C14	0.0566 (3)	0.44738 (7)	0.61927 (15)	0.0414 (4)
H11	0.013023	0.460603	0.675424	0.050*
C15	0.2287 (3)	0.43228 (7)	0.63130 (14)	0.0420 (4)
H12	0.305565	0.434512	0.696352	0.050*
C16	0.2875 (2)	0.41376 (6)	0.54648 (13)	0.0349 (4)
H13	0.405156	0.403048	0.552629	0.042*
C17	0.2905 (2)	0.43121 (5)	0.28908 (12)	0.0253 (3)
C18	0.3850 (3)	0.44934 (6)	0.13796 (15)	0.0375 (4)
H14	0.414699	0.440486	0.073710	0.045*
C19	0.4017 (3)	0.49347 (6)	0.16468 (17)	0.0431 (5)
H15	0.440902	0.514366	0.119743	0.052*
C20	0.3602 (3)	0.50621 (6)	0.25791 (17)	0.0420 (5)
H16	0.369078	0.536291	0.278364	0.050*
C21	0.3050 (2)	0.47458 (5)	0.32215 (15)	0.0337 (4)
H17	0.277691	0.482619	0.387538	0.040*
C22	−0.4196 (2)	0.18499 (7)	0.11958 (15)	0.0366 (4)
H18	−0.483352	0.209827	0.143506	0.055*
H19	−0.483417	0.157542	0.127168	0.055*
H20	−0.411174	0.189300	0.046559	0.055*
C23	−0.2424 (2)	0.18244 (5)	0.18128 (13)	0.0276 (3)
C24	0.6850 (2)	0.17443 (6)	0.53247 (14)	0.0324 (4)
H21	0.690383	0.199937	0.578794	0.049*
H22	0.779032	0.176740	0.491025	0.049*
H23	0.700991	0.147313	0.573680	0.049*
C25	0.5133 (2)	0.17341 (5)	0.46386 (13)	0.0256 (3)
C26	−0.0305 (4)	0.56800 (8)	0.0851 (2)	0.0668 (7)
H24	−0.122484	0.590094	0.088294	0.100*
H25	0.008716	0.570030	0.018113	0.100*
H26	0.070138	0.573380	0.140994	0.100*
C27	−0.1013 (3)	0.52436 (7)	0.09689 (17)	0.0506 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.02089 (7)	0.02070 (7)	0.02179 (7)	0.00083 (5)	0.00222 (5)	0.00059 (4)
Cl1	0.0362 (2)	0.02404 (18)	0.0321 (2)	0.00159 (16)	0.01156 (16)	0.00320 (15)
Cl2	0.0315 (2)	0.02802 (19)	0.02932 (19)	0.00249 (16)	0.00885 (16)	−0.00262 (15)
Cl3	0.0360 (2)	0.0302 (2)	0.0315 (2)	−0.00501 (17)	0.00631 (17)	0.00562 (16)
Cl4	0.0355 (2)	0.02499 (18)	0.02973 (19)	0.00138 (16)	0.00792 (16)	−0.00290 (15)
N1	0.0234 (7)	0.0236 (6)	0.0290 (7)	0.0004 (5)	0.0014 (6)	−0.0024 (5)
N2	0.0242 (7)	0.0238 (6)	0.0351 (8)	0.0011 (5)	0.0008 (6)	0.0022 (5)
N3	0.0287 (7)	0.0374 (8)	0.0320 (7)	0.0041 (6)	0.0072 (6)	−0.0055 (6)
N4	0.0360 (8)	0.0285 (7)	0.0290 (7)	0.0016 (6)	0.0085 (6)	0.0018 (6)
N5	0.0268 (7)	0.0268 (7)	0.0269 (7)	0.0004 (6)	0.0027 (6)	−0.0002 (5)
N6	0.0265 (7)	0.0235 (6)	0.0271 (7)	0.0007 (5)	0.0046 (6)	0.0002 (5)
N7	0.0874 (17)	0.0433 (11)	0.0750 (15)	−0.0007 (11)	0.0065 (13)	0.0190 (10)
C1	0.0233 (7)	0.0206 (7)	0.0247 (7)	0.0006 (6)	0.0037 (6)	−0.0004 (6)
C2	0.0244 (7)	0.0250 (7)	0.0214 (7)	0.0010 (6)	0.0050 (6)	−0.0024 (6)
C3	0.0272 (8)	0.0306 (8)	0.0398 (10)	−0.0034 (7)	0.0020 (7)	−0.0085 (7)
C4	0.0275 (9)	0.0465 (10)	0.0336 (9)	−0.0012 (8)	−0.0014 (7)	−0.0113 (8)
C5	0.0312 (9)	0.0483 (11)	0.0266 (8)	0.0094 (8)	−0.0023 (7)	0.0012 (7)
C6	0.0326 (9)	0.0317 (8)	0.0293 (8)	0.0037 (7)	0.0028 (7)	0.0025 (7)
C7	0.0236 (7)	0.0228 (7)	0.0218 (7)	0.0014 (6)	0.0032 (6)	−0.0022 (6)
C8	0.0319 (9)	0.0245 (8)	0.0399 (10)	0.0014 (7)	−0.0014 (7)	0.0045 (7)
C9	0.0274 (8)	0.0340 (9)	0.0353 (9)	0.0089 (7)	−0.0006 (7)	−0.0005 (7)
C10	0.0215 (8)	0.0448 (10)	0.0329 (9)	0.0012 (7)	0.0048 (7)	−0.0018 (8)
C11	0.0267 (8)	0.0315 (8)	0.0292 (8)	−0.0025 (7)	0.0065 (7)	0.0017 (7)
C12	0.0278 (8)	0.0204 (7)	0.0266 (8)	−0.0025 (6)	0.0077 (6)	−0.0015 (6)
C13	0.0364 (10)	0.0474 (11)	0.0422 (10)	0.0079 (9)	0.0135 (8)	−0.0104 (9)
C14	0.0490 (12)	0.0438 (10)	0.0354 (10)	−0.0013 (9)	0.0182 (9)	−0.0105 (8)
C15	0.0464 (11)	0.0515 (11)	0.0274 (9)	−0.0033 (9)	0.0049 (8)	−0.0094 (8)
C16	0.0316 (9)	0.0429 (10)	0.0297 (9)	0.0018 (8)	0.0041 (7)	−0.0059 (7)
C17	0.0246 (8)	0.0223 (7)	0.0290 (8)	0.0014 (6)	0.0045 (6)	0.0019 (6)
C18	0.0394 (10)	0.0412 (10)	0.0338 (9)	0.0013 (8)	0.0113 (8)	0.0097 (8)
C19	0.0416 (11)	0.0348 (10)	0.0548 (12)	−0.0031 (8)	0.0137 (9)	0.0166 (9)
C20	0.0412 (11)	0.0226 (8)	0.0639 (13)	−0.0023 (8)	0.0136 (10)	0.0022 (8)
C21	0.0357 (9)	0.0247 (8)	0.0421 (10)	−0.0010 (7)	0.0110 (8)	−0.0040 (7)
C22	0.0221 (8)	0.0481 (10)	0.0382 (10)	0.0020 (8)	0.0009 (7)	0.0043 (8)
C23	0.0276 (8)	0.0288 (8)	0.0270 (8)	0.0003 (7)	0.0063 (7)	0.0016 (6)
C24	0.0250 (8)	0.0352 (9)	0.0349 (9)	−0.0015 (7)	0.0001 (7)	0.0003 (7)
C25	0.0267 (8)	0.0223 (7)	0.0282 (8)	0.0007 (6)	0.0063 (7)	−0.0004 (6)
C26	0.091 (2)	0.0409 (12)	0.0603 (15)	−0.0159 (13)	−0.0104 (14)	0.0066 (11)
C27	0.0656 (14)	0.0373 (11)	0.0438 (11)	0.0032 (10)	−0.0040 (10)	0.0086 (9)

Geometric parameters (Å, º) top

Ru1—N5	2.0132 (14)	C9—C10	1.375 (3)
Ru1—N6	2.0304 (14)	C9—H7	0.9500
Ru1—Cl1	2.3576 (4)	C10—C11	1.389 (2)
Ru1—Cl2	2.3720 (4)	C10—H8	0.9500
Ru1—Cl3	2.3649 (4)	C11—H9	0.9500
Ru1—Cl4	2.3488 (4)	C12—C16	1.390 (2)
N1—C2	1.343 (2)	C13—C14	1.372 (3)
N1—C3	1.354 (2)	C13—H10	0.9500
N1—H1	0.87 (2)	C14—C15	1.381 (3)
N2—C8	1.338 (2)	C14—H11	0.9500
N2—C7	1.345 (2)	C15—C16	1.391 (2)
N3—C12	1.335 (2)	C15—H12	0.9500
N3—C13	1.343 (2)	C16—H13	0.9500
N4—C17	1.344 (2)	C17—C21	1.383 (2)
N4—C18	1.338 (2)	C18—C19	1.384 (3)
N5—C23	1.137 (2)	C18—H14	0.9500
N6—C25	1.139 (2)	C19—C20	1.373 (3)
N7—C27	1.130 (3)	C19—H15	0.9500
C1—C2	1.540 (2)	C20—C21	1.392 (3)
C1—C7	1.541 (2)	C20—H16	0.9500
C1—C12	1.551 (2)	C21—H17	0.9500
C1—C17	1.543 (2)	C22—C23	1.457 (2)
C2—C6	1.391 (2)	C22—H18	0.9800
C3—C4	1.371 (3)	C22—H19	0.9800
C3—H2	0.9500	C22—H20	0.9800
C4—C5	1.391 (3)	C24—C25	1.459 (2)
C4—H3	0.9500	C24—H21	0.9800
C5—C6	1.380 (3)	C24—H22	0.9800
C5—H4	0.9500	C24—H23	0.9800
C6—H5	0.9500	C26—C27	1.450 (3)
C7—C11	1.388 (2)	C26—H24	0.9800
C8—C9	1.384 (2)	C26—H25	0.9800
C8—H6	0.9500	C26—H26	0.9800

Cl1—Ru1—Cl2	88.500 (15)	C11—C10—H8	119.9
Cl1—Ru1—Cl3	179.093 (16)	C7—C11—C10	118.32 (15)
Cl1—Ru1—Cl4	90.883 (15)	C7—C11—H9	120.8
Cl2—Ru1—Cl3	91.067 (15)	C10—C11—H9	120.8
Cl2—Ru1—Cl4	179.116 (15)	N3—C12—C16	122.46 (15)
Cl3—Ru1—Cl4	89.542 (15)	N3—C12—C1	115.59 (14)
N5—Ru1—Cl1	90.76 (4)	C1—C12—C16	121.91 (14)
N5—Ru1—Cl2	89.25 (4)	N3—C13—C14	123.96 (18)
N5—Ru1—Cl3	88.44 (4)	N3—C13—H10	118.0
N5—Ru1—Cl4	90.13 (4)	C14—C13—H10	118.0
N6—Ru1—Cl1	88.87 (4)	C13—C14—C15	118.33 (17)
N6—Ru1—Cl2	89.48 (4)	C13—C14—H11	120.8
N6—Ru1—Cl3	91.92 (4)	C15—C14—H11	120.8
N6—Ru1—Cl4	91.14 (4)	C14—C15—C16	118.82 (18)
N5—Ru1—N6	178.68 (5)	C14—C15—H12	120.6
C2—N1—C3	123.85 (15)	C16—C15—H12	120.6
C2—N1—H1	114.1 (14)	C12—C16—C15	118.85 (17)
C3—N1—H1	122.0 (14)	C12—C16—H13	120.6
C7—N2—C8	118.95 (14)	C15—C16—H13	120.6
C12—N3—C13	117.57 (16)	N4—C17—C1	114.06 (13)
C17—N4—C18	117.67 (15)	N4—C17—C21	122.40 (15)
C23—N5—Ru1	177.78 (14)	C1—C17—C21	123.55 (15)
C25—N6—Ru1	175.99 (13)	N4—C18—C19	123.67 (18)
C2—C1—C7	113.18 (12)	N4—C18—H14	118.2
C2—C1—C12	108.21 (12)	C19—C18—H14	118.2
C2—C1—C17	106.74 (12)	C18—C19—C20	118.17 (17)
C7—C1—C12	108.28 (12)	C18—C19—H15	120.9
C7—C1—C17	109.44 (12)	C20—C19—H15	120.9
C12—C1—C17	111.01 (12)	C19—C20—C21	119.26 (17)
N1—C2—C1	120.01 (14)	C19—C20—H16	120.4
N1—C2—C6	117.51 (15)	C21—C20—H16	120.4
C1—C2—C6	122.45 (14)	C17—C21—C20	118.82 (17)
N1—C3—C4	119.61 (17)	C17—C21—H17	120.6
N1—C3—H2	120.2	C20—C21—H17	120.6
C4—C3—H2	120.2	C23—C22—H18	109.5
C3—C4—C5	118.54 (17)	C23—C22—H19	109.5
C3—C4—H3	120.7	C23—C22—H20	109.5
C5—C4—H3	120.7	H18—C22—H19	109.5
C4—C5—C6	120.30 (17)	H18—C22—H20	109.5
C4—C5—H4	119.8	H19—C22—H20	109.5
C6—C5—H4	119.8	N5—C23—C22	179.9 (2)
C2—C6—C5	120.15 (16)	C25—C24—H21	109.5
C2—C6—H5	119.9	C25—C24—H22	109.5
C5—C6—H5	119.9	C25—C24—H23	109.5
N2—C7—C1	115.07 (13)	H21—C24—H22	109.5
N2—C7—C11	121.74 (14)	H21—C24—H23	109.5
C1—C7—C11	122.94 (14)	H22—C24—H23	109.5
N2—C8—C9	122.81 (16)	N6—C25—C24	179.5 (2)
N2—C8—H6	118.6	C27—C26—H24	109.5
C9—C8—H6	118.6	C27—C26—H25	109.5
C8—C9—C10	117.96 (16)	C27—C26—H26	109.5
C8—C9—H7	121.0	H24—C26—H25	109.5
C10—C9—H7	121.0	H24—C26—H26	109.5
C9—C10—C11	120.20 (16)	H25—C26—H26	109.5
C9—C10—H8	119.9	N7—C27—C26	178.7 (3)

C3—N1—C2—C6	1.8 (2)	N3—C12—C1—C7	−154.96 (14)
C3—N1—C2—C1	179.64 (15)	C16—C12—C1—C7	27.2 (2)
C13—N3—C12—C16	0.9 (3)	N3—C12—C1—C17	84.89 (17)
C13—N3—C12—C1	−176.98 (15)	C16—C12—C1—C17	−93.00 (18)
C18—N4—C17—C21	0.6 (2)	C2—N1—C3—C4	−0.6 (3)
C18—N4—C17—C1	−179.28 (15)	N1—C3—C4—C5	−0.6 (3)
C8—N2—C7—C11	−1.1 (2)	N3—C12—C16—C15	−1.1 (3)
C8—N2—C7—C1	−175.54 (15)	C1—C12—C16—C15	176.61 (16)
N1—C2—C1—C7	26.4 (2)	N2—C7—C11—C10	−0.2 (2)
C6—C2—C1—C7	−155.90 (14)	C1—C7—C11—C10	173.82 (14)
N1—C2—C1—C17	146.83 (14)	C7—N2—C8—C9	1.4 (3)
C6—C2—C1—C17	−35.45 (19)	C10—C9—C8—N2	−0.3 (3)
N1—C2—C1—C12	−93.63 (16)	N1—C2—C6—C5	−1.8 (2)
C6—C2—C1—C12	84.10 (18)	C1—C2—C6—C5	−179.56 (15)
N2—C7—C1—C2	−47.00 (18)	C8—C9—C10—C11	−1.0 (3)
C11—C7—C1—C2	138.63 (15)	C7—C11—C10—C9	1.2 (3)
N2—C7—C1—C17	−165.91 (13)	N4—C17—C21—C20	0.6 (3)
C11—C7—C1—C17	19.7 (2)	C1—C17—C21—C20	−179.60 (16)
N2—C7—C1—C12	72.96 (16)	C17—N4—C18—C19	−1.1 (3)
C11—C7—C1—C12	−101.41 (17)	C12—N3—C13—C14	0.3 (3)
N4—C17—C1—C2	−57.10 (17)	C15—C14—C13—N3	−1.2 (3)
C21—C17—C1—C2	123.06 (17)	C2—C6—C5—C4	0.7 (3)
N4—C17—C1—C7	65.73 (17)	C3—C4—C5—C6	0.5 (3)
C21—C17—C1—C7	−114.12 (17)	C17—C21—C20—C19	−1.2 (3)
N4—C17—C1—C12	−174.81 (14)	C13—C14—C15—C16	1.0 (3)
C21—C17—C1—C12	5.3 (2)	C12—C16—C15—C14	0.2 (3)
N3—C12—C1—C2	−31.93 (18)	C21—C20—C19—C18	0.6 (3)
C16—C12—C1—C2	150.18 (15)	N4—C18—C19—C20	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.87 (2)	1.87 (2)	2.615 (2)	143.3 (19)
C22—H18···Cl1ⁱ	0.98	2.69	3.5521 (19)	146
C22—H19···Cl4ⁱ	0.98	2.78	3.5972 (19)	142
C24—H21···Cl1ⁱⁱ	0.98	2.77	3.7393 (18)	172
C24—H22···Cl2ⁱⁱⁱ	0.98	2.77	3.6346 (18)	147
C24—H23···N4ⁱⁱ	0.98	2.65	3.606 (2)	165
C6—H5···N7	0.95	2.45	3.248 (3)	142
C26—H26···Cl4^iv	0.98	2.84	3.749 (3)	154

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

Funding information

Funding for this research was provided by: Japan Society for the Promotion of Science (Grant-in-Aid for Scientific Research No. 24550049).

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