Bis(4′-chloro-2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)ruthenium(II) dichloride dihydrate

Wang, Y.; Jiao, R.; Qiu, X.-L.; Wang, J.; Huang, W.

doi:10.1107/S1600536812021459

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages m777-m778

doi:10.1107/S1600536812021459

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Bis(4′-chloro-2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)ruthenium(II) dichloride dihydrate

Ying Wang,^a Rui Jiao,^a Xiang-Lei Qiu,^a Jian Wang ^a and Wei Huang ^b ^*

^aDepartment of Chemistry and Chemical Engineering, Lianyungang Teacher's College, Lianyungang 222006, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn

(Received 21 April 2012; accepted 11 May 2012; online 16 May 2012)

In the cation of the title compound, [Ru(C₁₅H₁₀ClN₃)₂]Cl₂·2H₂O, the metal atom exhibits a distorted octahedral coordination geometry provided by the N atoms of two tridentate terpyridine ligands. The ligands are approximately planar [maximum deviation = 0.156 (5) Å] and form a dihedral angle of 87.0 (3)°. In the crystal, the cations, anions and water molecules are linked into a three-dimensional network by C—H⋯Cl, C—H⋯O and O—H⋯Cl hydrogen bonds.

Related literature

For the structures of the related hydrochloride tetrafluoridoborate and hydrochloride hexafluoridophosphorate derivatives, see: Huang & Qian (2007a ). For the structures of Ru^II, Cu^II, Zn^II, Ni^II, Fe^II, Cu^II and Cd^II complexes of 4′-chloro-2,2′:6′,2′′-terpyridine, see: Beves et al. (2008 ); Huang & Qian (2007b ); Huang et al. (2009 ); You et al. (2008 ); You et al. (2009 ).

Experimental

Crystal data

[Ru(C₁₅H₁₀ClN₃)₂]Cl₂·2H₂O
M_r = 743.42
Orthorhombic, P n a 2₁
a = 10.1367 (5) Å
b = 16.2964 (7) Å
c = 17.8995 (8) Å
V = 2956.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 291 K
0.18 × 0.16 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.850, T_max = 0.881
15880 measured reflections
5166 independent reflections
4736 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.084
S = 1.01
5166 reflections
389 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ), 2475 Friedel pairs
Flack parameter: 0.47 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cl4	0.93	2.68	3.590 (5)	169
C12—H12⋯O2ⁱ	0.93	2.57	3.391 (6)	148
C15—H15⋯O1ⁱⁱ	0.93	2.48	3.179 (7)	132
C16—H16⋯Cl4ⁱⁱⁱ	0.93	2.81	3.498 (5)	132
C27—H27⋯O1^iv	0.93	2.60	3.474 (7)	158
C28—H28⋯Cl4^iv	0.93	2.82	3.686 (4)	156
C30—H30⋯O2ⁱⁱ	0.93	2.54	3.203 (6)	128
O1—H1A⋯Cl4	0.85	2.76	3.231 (5)	116
O1—H1B⋯Cl4^v	0.85	2.68	3.176 (4)	118
O2—H2A⋯Cl3	0.85	2.51	3.156 (4)	133
O2—H2B⋯Cl3^vi	0.85	2.58	3.209 (4)	132
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021459/rz2748sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021459/rz2748Isup2.hkl

checkCIF report

Comment top

The crystal structures of the hydrochlorate tetrafluoroborate and hydrochlorate hexafluorophosphorate derivatives (Huang & Qian, 2007a) and of the Ru(II), Cu(II), Zn(II), Ni(II), Fe(II), Cu(II) and Cd(II) complexes (Huang & Qian, 2007b; Beves et al., 2008; You et al., 2008; You et al., 2009; Huang et al., 2009) of 4'-chloro-2,2':6',2''-terpyridine with metal/ligand ratios of 1:1 and 1:2 have been recently reported by our group. As a continuation of the research in this field, we report herein the crystal structure of a ruthenium(II) dichloride complex bearing the same 4'-chloro-2,2':6',2''-terpyridine ligand with a 1:2 metal/ligand ratio.

The asymmetric unit of the title compound consists of a dication of formula [Ru(C₁₅H₁₀N₃Cl)₂]²⁺, two chloride anions and two water molecules (Fig. 1). In the cation, the ruthenium(II) metal displays a distorted octahedral geometry where each 4'-chloro-2,2':6',2'-terpyridine molecule acts as a tridentate mer-arranged N-ligand. The six Ru—N bond lengths (1.977 (3)—2.079 (4) Å) fall in the normal ranges of values. The two 4'-chloro-2,2':6',2''-terpyridine ligands are approximately planar (maximum deviation 0.156 (5) Å for atom C13) and the dihedral angle between them is 87.0 (3)°. In the crystal structure, cations, anions and water molecules are linked into a three-dimensional network by C—H···Cl, C—H···O and O—H···Cl hydrogen bonds (Table 1).

Related literature top

For the structures of the related hydrochlorate tetrafluoridoborate and hydrochlorate hexafluoridophosphorate derivatives, see: Huang & Qian (2007a). For the structures of Ru^II, Cu^II, Zn^II, Ni^II, Fe^II, Cu^II and Cd^II complexes of 4'-chloro-2,2':6',2''-terpyridine, see: Beves et al. (2008); Huang & Qian (2007b); Huang et al. (2009); You et al. (2008); You et al. (2009).

Experimental top

The title compound was obtained by refluxing cis-[RuCl₂(DMSO)₄] (0.121 g, 0.25 mmol) and 4'-chloro-2,2':6',2''-terpyridine (0.134 g, 0.50 mmol) in ethanol for 4 h [0.146 g; yield 78.4% based on Ru(II)]. Single crystals suitable for X-ray diffraction measurement were obtained after 10 days by slow evaporation of an ethanol/water solution (3:1 v/v) at room temperature in air. Elemental analysis: calculated for C₂₄H₂₂RuN₆B₂F₈: C 43.08, H 3.31, N 12.56%; found: C 43.29, H 3.62, N 12.34%. Main FT–IR absorptions (KBr plates, cm^-1): 3423 (b, s), 1630 (s), 1591 (w), 1421 (m), 1385 (m), 1107 (m), 1026 (w) and 793 (m).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level.

Bis(4'-chloro-2,2':6',2''-terpyridine- κ³N,N',N'')ruthenium(II) dichloride dihydrate top

Crystal data top

[Ru(C₁₅H₁₀ClN₃)₂]Cl₂·2H₂O	F(000) = 1496
M_r = 743.42	D_x = 1.670 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 8095 reflections
a = 10.1367 (5) Å	θ = 2.3–27.6°
b = 16.2964 (7) Å	µ = 0.93 mm⁻¹
c = 17.8995 (8) Å	T = 291 K
V = 2956.8 (2) Å³	Block, red
Z = 4	0.18 × 0.16 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5166 independent reflections
Radiation source: fine-focus sealed tube	4736 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→12
T_min = 0.850, T_max = 0.881	k = −19→19
15880 measured reflections	l = −21→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0507P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
5166 reflections	Δρ_max = 0.78 e Å⁻³
389 parameters	Δρ_min = −0.42 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2475 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.47 (3)

Crystal data top

[Ru(C₁₅H₁₀ClN₃)₂]Cl₂·2H₂O	V = 2956.8 (2) Å³
M_r = 743.42	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 10.1367 (5) Å	µ = 0.93 mm⁻¹
b = 16.2964 (7) Å	T = 291 K
c = 17.8995 (8) Å	0.18 × 0.16 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5166 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4736 reflections with I > 2σ(I)
T_min = 0.850, T_max = 0.881	R_int = 0.069
15880 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.084	Δρ_max = 0.78 e Å⁻³
S = 1.01	Δρ_min = −0.42 e Å⁻³
5166 reflections	Absolute structure: Flack (1983), 2475 Friedel pairs
389 parameters	Absolute structure parameter: 0.47 (3)
1 restraint

Special details top

Experimental. The structure was solved by direct methods and successive difference Fourier syntheses.

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
Ru1	0.29385 (2)	0.487615 (16)	0.79324 (2)	0.03652 (10)
Cl1	0.31009 (13)	0.88127 (6)	0.76928 (7)	0.0702 (4)
Cl2	0.29576 (11)	0.09346 (6)	0.80920 (7)	0.0620 (4)
N1	0.4328 (4)	0.5037 (2)	0.7093 (2)	0.0403 (8)
N2	0.2981 (3)	0.60884 (17)	0.7856 (3)	0.0387 (8)
N3	0.1519 (3)	0.52045 (18)	0.87155 (19)	0.0405 (7)
N4	0.1469 (3)	0.4589 (2)	0.71801 (18)	0.0383 (7)
N5	0.2922 (3)	0.36654 (16)	0.8003 (3)	0.0366 (7)
N6	0.4377 (4)	0.46780 (19)	0.8739 (2)	0.0402 (8)
C1	0.4956 (4)	0.4461 (3)	0.6702 (2)	0.0495 (10)
H1	0.4762	0.3914	0.6798	0.059*
C2	0.5882 (5)	0.4642 (3)	0.6161 (3)	0.0555 (12)
H2	0.6295	0.4222	0.5898	0.067*
C3	0.6187 (4)	0.5436 (3)	0.6016 (3)	0.0590 (12)
H3	0.6823	0.5565	0.5660	0.071*
C4	0.5543 (4)	0.6052 (3)	0.6402 (2)	0.0497 (10)
H4	0.5731	0.6599	0.6303	0.060*
C5	0.4605 (4)	0.5844 (2)	0.6942 (2)	0.0419 (9)
C6	0.3842 (4)	0.6443 (2)	0.7371 (2)	0.0415 (9)
C7	0.3893 (4)	0.7289 (2)	0.7306 (2)	0.0490 (10)
H7	0.4468	0.7541	0.6972	0.059*
C8	0.3062 (4)	0.7747 (2)	0.7753 (2)	0.0487 (13)
C9	0.2190 (4)	0.7392 (3)	0.8253 (3)	0.0488 (10)
H9	0.1661	0.7703	0.8570	0.059*
C10	0.2161 (4)	0.6537 (2)	0.8288 (2)	0.0389 (9)
C11	0.1303 (4)	0.6035 (2)	0.8758 (2)	0.0415 (9)
C12	0.0307 (4)	0.6351 (3)	0.9204 (2)	0.0513 (10)
H12	0.0168	0.6914	0.9229	0.062*
C13	−0.0476 (4)	0.5823 (3)	0.9609 (3)	0.0584 (12)
H13	−0.1157	0.6027	0.9904	0.070*
C14	−0.0248 (6)	0.5004 (4)	0.9576 (4)	0.0618 (15)
H14	−0.0772	0.4641	0.9846	0.074*
C15	0.0791 (5)	0.4711 (3)	0.9129 (3)	0.0494 (11)
H15	0.0971	0.4151	0.9125	0.059*
C16	0.0690 (5)	0.5099 (3)	0.6799 (3)	0.0460 (11)
H16	0.0848	0.5660	0.6838	0.055*
C17	−0.0323 (6)	0.4844 (3)	0.6356 (3)	0.0523 (13)
H17	−0.0843	0.5226	0.6107	0.063*
C18	−0.0577 (4)	0.4009 (3)	0.6278 (2)	0.0534 (11)
H18	−0.1270	0.3822	0.5984	0.064*
C19	0.0235 (4)	0.3467 (3)	0.6653 (2)	0.0468 (10)
H19	0.0115	0.2904	0.6599	0.056*
C20	0.1226 (4)	0.3762 (2)	0.7108 (2)	0.0400 (9)
C21	0.2080 (4)	0.3234 (2)	0.7571 (2)	0.0381 (8)
C22	0.2096 (4)	0.2384 (2)	0.7582 (2)	0.0451 (10)
H22	0.1552	0.2083	0.7266	0.054*
C23	0.2942 (4)	0.1997 (2)	0.8073 (3)	0.0443 (11)
C24	0.3774 (4)	0.2437 (2)	0.8535 (2)	0.0467 (10)
H24	0.4327	0.2170	0.8870	0.056*
C25	0.3762 (4)	0.3286 (2)	0.8485 (2)	0.0384 (9)
C26	0.4577 (4)	0.3863 (2)	0.8907 (2)	0.0410 (9)
C27	0.5518 (4)	0.3629 (3)	0.9433 (3)	0.0501 (10)
H27	0.5654	0.3077	0.9541	0.060*
C28	0.6242 (4)	0.4223 (3)	0.9789 (2)	0.0559 (12)
H28	0.6876	0.4072	1.0139	0.067*
C29	0.6039 (5)	0.5037 (3)	0.9635 (3)	0.0548 (13)
H29	0.6520	0.5441	0.9880	0.066*
C30	0.5092 (4)	0.5244 (3)	0.9101 (2)	0.0472 (10)
H30	0.4953	0.5795	0.8992	0.057*
O1	0.8180 (4)	0.6796 (3)	0.5095 (3)	0.0911 (12)
H1A	0.7593	0.7075	0.4870	0.137*
H1B	0.8513	0.7082	0.5445	0.137*
O2	0.6110 (4)	0.3114 (2)	0.4811 (2)	0.0952 (14)
H2A	0.6240	0.2689	0.5077	0.143*
H2B	0.5485	0.3394	0.4998	0.143*
Cl3	0.82738 (13)	0.20222 (8)	0.55975 (9)	0.0755 (4)
Cl4	0.60880 (13)	0.81073 (7)	0.57497 (8)	0.0725 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.04084 (15)	0.02974 (15)	0.03897 (15)	0.00017 (10)	−0.00122 (19)	0.00334 (18)
Cl1	0.0967 (8)	0.0306 (5)	0.0833 (11)	−0.0047 (5)	−0.0244 (7)	0.0081 (5)
Cl2	0.0896 (8)	0.0288 (4)	0.0676 (10)	0.0044 (5)	0.0194 (6)	0.0067 (5)
N1	0.040 (2)	0.0425 (19)	0.039 (2)	−0.0004 (15)	−0.0031 (16)	0.0033 (15)
N2	0.0425 (15)	0.0282 (14)	0.045 (2)	−0.0023 (11)	−0.0037 (16)	0.0026 (18)
N3	0.0423 (18)	0.0379 (19)	0.0412 (19)	−0.0049 (14)	−0.0018 (15)	0.0015 (14)
N4	0.0407 (17)	0.0389 (17)	0.0354 (18)	−0.0009 (14)	0.0011 (14)	0.0015 (14)
N5	0.0437 (15)	0.0285 (13)	0.0377 (19)	0.0032 (11)	0.0077 (16)	0.0027 (18)
N6	0.044 (2)	0.0368 (16)	0.040 (2)	0.0002 (16)	0.0019 (15)	0.0035 (16)
C1	0.049 (2)	0.051 (3)	0.049 (3)	0.0090 (19)	−0.004 (2)	0.003 (2)
C2	0.045 (3)	0.074 (3)	0.047 (3)	0.009 (3)	0.001 (2)	0.000 (3)
C3	0.044 (3)	0.082 (4)	0.050 (3)	−0.003 (2)	−0.004 (2)	0.008 (3)
C4	0.047 (2)	0.058 (3)	0.043 (2)	−0.0064 (19)	−0.0035 (19)	0.0075 (19)
C5	0.040 (2)	0.041 (2)	0.045 (2)	−0.0038 (16)	−0.0098 (18)	0.0067 (17)
C6	0.043 (2)	0.039 (2)	0.043 (2)	−0.0068 (17)	−0.0092 (18)	0.0042 (16)
C7	0.058 (3)	0.039 (2)	0.049 (3)	−0.0110 (19)	−0.013 (2)	0.0118 (18)
C8	0.064 (3)	0.0271 (18)	0.055 (4)	−0.0050 (16)	−0.020 (2)	0.0069 (17)
C9	0.057 (3)	0.037 (2)	0.052 (2)	0.0085 (18)	−0.015 (2)	−0.0036 (18)
C10	0.041 (2)	0.034 (2)	0.042 (2)	0.0035 (15)	−0.0067 (17)	−0.0009 (16)
C11	0.039 (2)	0.047 (2)	0.039 (2)	0.0063 (16)	−0.0065 (17)	−0.0016 (17)
C12	0.054 (3)	0.054 (3)	0.045 (3)	0.005 (2)	−0.004 (2)	−0.0063 (19)
C13	0.052 (3)	0.073 (3)	0.050 (3)	0.008 (2)	0.004 (2)	−0.017 (2)
C14	0.053 (4)	0.082 (4)	0.050 (3)	−0.013 (3)	0.009 (3)	−0.002 (2)
C15	0.057 (3)	0.047 (2)	0.044 (3)	−0.007 (2)	0.000 (2)	−0.002 (2)
C16	0.049 (3)	0.043 (2)	0.046 (3)	0.0086 (19)	0.002 (2)	0.0062 (19)
C17	0.057 (3)	0.060 (3)	0.041 (3)	0.013 (2)	−0.007 (2)	0.002 (2)
C18	0.047 (3)	0.069 (3)	0.044 (3)	−0.004 (2)	−0.004 (2)	−0.006 (2)
C19	0.046 (2)	0.049 (2)	0.046 (2)	−0.0081 (18)	0.0012 (19)	−0.0030 (18)
C20	0.043 (2)	0.039 (2)	0.039 (2)	0.0009 (16)	0.0083 (17)	−0.0016 (16)
C21	0.042 (2)	0.032 (2)	0.041 (2)	0.0008 (15)	0.0046 (16)	0.0014 (16)
C22	0.049 (2)	0.035 (2)	0.051 (2)	−0.0050 (16)	0.0085 (18)	−0.0046 (18)
C23	0.059 (2)	0.0281 (17)	0.046 (3)	0.0025 (16)	0.0182 (19)	0.0032 (17)
C24	0.056 (2)	0.041 (2)	0.043 (2)	0.0148 (18)	0.0087 (19)	0.0076 (17)
C25	0.045 (2)	0.0344 (19)	0.035 (2)	0.0035 (16)	0.0074 (17)	0.0060 (15)
C26	0.042 (2)	0.044 (2)	0.037 (2)	0.0072 (17)	0.0027 (17)	0.0048 (16)
C27	0.054 (3)	0.051 (3)	0.045 (2)	0.010 (2)	0.0010 (19)	0.0077 (19)
C28	0.044 (3)	0.081 (3)	0.043 (3)	0.011 (2)	−0.0042 (19)	0.002 (2)
C29	0.049 (3)	0.068 (3)	0.047 (3)	−0.004 (2)	−0.002 (2)	−0.008 (2)
C30	0.045 (2)	0.046 (3)	0.051 (3)	−0.0013 (19)	0.001 (2)	−0.003 (2)
O1	0.094 (3)	0.079 (3)	0.100 (3)	0.001 (2)	0.011 (2)	−0.014 (2)
O2	0.109 (3)	0.067 (2)	0.109 (3)	0.024 (2)	0.035 (3)	0.012 (2)
Cl3	0.0685 (7)	0.0689 (8)	0.0892 (10)	−0.0103 (6)	−0.0019 (7)	−0.0065 (7)
Cl4	0.0767 (8)	0.0468 (6)	0.0941 (10)	−0.0041 (5)	0.0233 (7)	0.0034 (6)

Geometric parameters (Å, º) top

Ru1—N1	2.075 (4)	C11—C12	1.387 (6)
Ru1—N2	1.981 (3)	C12—C13	1.377 (7)
Ru1—N3	2.079 (4)	C12—H12	0.9300
Ru1—N4	2.062 (3)	C13—C14	1.355 (7)
Ru1—N5	1.977 (3)	C13—H13	0.9300
Ru1—N6	2.077 (4)	C14—C15	1.407 (8)
Cl1—C8	1.740 (4)	C14—H14	0.9300
Cl2—C23	1.732 (4)	C15—H15	0.9300
N1—C1	1.333 (6)	C16—C17	1.362 (7)
N1—C5	1.371 (5)	C16—H16	0.9300
N2—C10	1.350 (5)	C17—C18	1.392 (6)
N2—C6	1.360 (5)	C17—H17	0.9300
N3—C15	1.318 (6)	C18—C19	1.381 (6)
N3—C11	1.373 (5)	C18—H18	0.9300
N4—C16	1.334 (5)	C19—C20	1.379 (5)
N4—C20	1.376 (5)	C19—H19	0.9300
N5—C21	1.348 (5)	C20—C21	1.475 (5)
N5—C25	1.361 (5)	C21—C22	1.385 (6)
N6—C30	1.340 (5)	C22—C23	1.380 (6)
N6—C26	1.377 (5)	C22—H22	0.9300
C1—C2	1.380 (7)	C23—C24	1.382 (6)
C1—H1	0.9300	C24—C25	1.387 (5)
C2—C3	1.355 (7)	C24—H24	0.9300
C2—H2	0.9300	C25—C26	1.462 (6)
C3—C4	1.383 (7)	C26—C27	1.393 (6)
C3—H3	0.9300	C27—C28	1.373 (7)
C4—C5	1.398 (6)	C27—H27	0.9300
C4—H4	0.9300	C28—C29	1.370 (7)
C5—C6	1.463 (5)	C28—H28	0.9300
C6—C7	1.385 (6)	C29—C30	1.396 (7)
C7—C8	1.380 (6)	C29—H29	0.9300
C7—H7	0.9300	C30—H30	0.9300
C8—C9	1.386 (6)	O1—H1A	0.8501
C9—C10	1.394 (6)	O1—H1B	0.8500
C9—H9	0.9299	O2—H2A	0.8500
C10—C11	1.462 (6)	O2—H2B	0.8500

N5—Ru1—N2	179.19 (14)	N3—C11—C12	120.9 (4)
N5—Ru1—N4	78.99 (14)	N3—C11—C10	115.2 (3)
N2—Ru1—N4	101.35 (14)	C12—C11—C10	123.8 (4)
N5—Ru1—N1	100.25 (14)	C13—C12—C11	119.4 (4)
N2—Ru1—N1	79.01 (15)	C13—C12—H12	120.3
N4—Ru1—N1	92.66 (14)	C11—C12—H12	120.3
N5—Ru1—N6	78.84 (14)	C14—C13—C12	119.6 (5)
N2—Ru1—N6	100.83 (14)	C14—C13—H13	120.2
N4—Ru1—N6	157.79 (12)	C12—C13—H13	120.2
N1—Ru1—N6	92.64 (11)	C13—C14—C15	119.2 (5)
N5—Ru1—N3	102.01 (14)	C13—C14—H14	120.4
N2—Ru1—N3	78.74 (14)	C15—C14—H14	120.4
N4—Ru1—N3	89.93 (12)	N3—C15—C14	122.1 (5)
N1—Ru1—N3	157.68 (12)	N3—C15—H15	119.0
N6—Ru1—N3	93.28 (14)	C14—C15—H15	119.0
C1—N1—C5	118.3 (4)	N4—C16—C17	123.6 (4)
C1—N1—Ru1	128.0 (3)	N4—C16—H16	118.2
C5—N1—Ru1	113.8 (3)	C17—C16—H16	118.2
C10—N2—C6	122.0 (3)	C16—C17—C18	119.7 (4)
C10—N2—Ru1	119.2 (3)	C16—C17—H17	120.1
C6—N2—Ru1	118.8 (3)	C18—C17—H17	120.1
C15—N3—C11	118.7 (4)	C19—C18—C17	117.8 (4)
C15—N3—Ru1	127.5 (3)	C19—C18—H18	121.1
C11—N3—Ru1	113.7 (3)	C17—C18—H18	121.1
C16—N4—C20	117.2 (4)	C20—C19—C18	119.8 (4)
C16—N4—Ru1	128.3 (3)	C20—C19—H19	120.1
C20—N4—Ru1	114.4 (3)	C18—C19—H19	120.1
C21—N5—C25	121.5 (3)	N4—C20—C19	121.8 (4)
C21—N5—Ru1	119.3 (3)	N4—C20—C21	114.4 (3)
C25—N5—Ru1	119.2 (3)	C19—C20—C21	123.8 (3)
C30—N6—C26	118.5 (4)	N5—C21—C22	120.4 (4)
C30—N6—Ru1	127.5 (3)	N5—C21—C20	112.9 (3)
C26—N6—Ru1	113.9 (3)	C22—C21—C20	126.7 (4)
N1—C1—C2	122.9 (4)	C23—C22—C21	118.2 (4)
N1—C1—H1	118.5	C23—C22—H22	120.9
C2—C1—H1	118.5	C21—C22—H22	120.9
C3—C2—C1	119.6 (5)	C22—C23—C24	121.6 (4)
C3—C2—H2	120.2	C22—C23—Cl2	118.4 (3)
C1—C2—H2	120.2	C24—C23—Cl2	120.0 (3)
C2—C3—C4	119.3 (4)	C23—C24—C25	118.3 (4)
C2—C3—H3	120.4	C23—C24—H24	120.9
C4—C3—H3	120.4	C25—C24—H24	120.9
C3—C4—C5	119.4 (4)	N5—C25—C24	119.9 (4)
C3—C4—H4	120.3	N5—C25—C26	112.9 (3)
C5—C4—H4	120.3	C24—C25—C26	127.1 (3)
N1—C5—C4	120.5 (4)	N6—C26—C27	120.9 (4)
N1—C5—C6	115.4 (4)	N6—C26—C25	115.1 (3)
C4—C5—C6	124.1 (4)	C27—C26—C25	124.0 (4)
N2—C6—C7	120.0 (4)	C28—C27—C26	119.1 (4)
N2—C6—C5	113.0 (3)	C28—C27—H27	120.5
C7—C6—C5	127.0 (4)	C26—C27—H27	120.5
C8—C7—C6	117.9 (4)	C29—C28—C27	120.6 (4)
C8—C7—H7	121.1	C29—C28—H28	119.7
C6—C7—H7	121.1	C27—C28—H28	119.7
C7—C8—C9	122.5 (4)	C28—C29—C30	118.4 (5)
C7—C8—Cl1	119.4 (3)	C28—C29—H29	120.8
C9—C8—Cl1	118.1 (3)	C30—C29—H29	120.8
C8—C9—C10	117.3 (4)	N6—C30—C29	122.5 (4)
C8—C9—H9	122.3	N6—C30—H30	118.8
C10—C9—H9	120.4	C29—C30—H30	118.8
N2—C10—C9	120.2 (4)	H1A—O1—H1B	109.5
N2—C10—C11	113.1 (3)	H2A—O2—H2B	109.5
C9—C10—C11	126.7 (4)

N5—Ru1—N1—C1	3.0 (4)	C4—C5—C6—C7	1.6 (6)
N2—Ru1—N1—C1	−177.4 (4)	N2—C6—C7—C8	0.9 (5)
N4—Ru1—N1—C1	−76.3 (4)	C5—C6—C7—C8	178.4 (4)
N6—Ru1—N1—C1	82.1 (4)	C6—C7—C8—C9	−0.3 (6)
N3—Ru1—N1—C1	−172.6 (3)	C6—C7—C8—Cl1	179.6 (3)
N5—Ru1—N1—C5	−176.9 (3)	C7—C8—C9—C10	−0.8 (6)
N2—Ru1—N1—C5	2.7 (3)	Cl1—C8—C9—C10	179.3 (3)
N4—Ru1—N1—C5	103.8 (3)	C6—N2—C10—C9	−0.8 (6)
N6—Ru1—N1—C5	−97.8 (3)	Ru1—N2—C10—C9	178.8 (3)
N3—Ru1—N1—C5	7.5 (6)	C6—N2—C10—C11	179.0 (3)
N4—Ru1—N2—C10	87.1 (3)	Ru1—N2—C10—C11	−1.3 (5)
N1—Ru1—N2—C10	177.6 (3)	C8—C9—C10—N2	1.4 (5)
N6—Ru1—N2—C10	−91.8 (3)	C8—C9—C10—C11	−178.4 (4)
N3—Ru1—N2—C10	−0.6 (3)	C15—N3—C11—C12	−2.5 (6)
N4—Ru1—N2—C6	−93.2 (3)	Ru1—N3—C11—C12	174.2 (3)
N1—Ru1—N2—C6	−2.7 (3)	C15—N3—C11—C10	179.4 (4)
N6—Ru1—N2—C6	87.9 (3)	Ru1—N3—C11—C10	−3.9 (4)
N3—Ru1—N2—C6	179.1 (3)	N2—C10—C11—N3	3.5 (5)
N5—Ru1—N3—C15	−1.5 (4)	C9—C10—C11—N3	−176.7 (4)
N2—Ru1—N3—C15	178.8 (4)	N2—C10—C11—C12	−174.6 (4)
N4—Ru1—N3—C15	77.2 (4)	C9—C10—C11—C12	5.2 (6)
N1—Ru1—N3—C15	174.1 (4)	N3—C11—C12—C13	0.0 (6)
N6—Ru1—N3—C15	−80.8 (4)	C10—C11—C12—C13	178.0 (4)
N5—Ru1—N3—C11	−177.8 (3)	C11—C12—C13—C14	1.1 (7)
N2—Ru1—N3—C11	2.5 (3)	C12—C13—C14—C15	0.2 (8)
N4—Ru1—N3—C11	−99.1 (3)	C11—N3—C15—C14	3.9 (7)
N1—Ru1—N3—C11	−2.3 (5)	Ru1—N3—C15—C14	−172.3 (4)
N6—Ru1—N3—C11	102.9 (3)	C13—C14—C15—N3	−2.8 (8)
N5—Ru1—N4—C16	175.6 (4)	C20—N4—C16—C17	0.6 (6)
N2—Ru1—N4—C16	−5.1 (4)	Ru1—N4—C16—C17	−174.8 (4)
N1—Ru1—N4—C16	−84.4 (4)	N4—C16—C17—C18	−0.8 (8)
N6—Ru1—N4—C16	171.9 (4)	C16—C17—C18—C19	−0.8 (7)
N3—Ru1—N4—C16	73.4 (4)	C17—C18—C19—C20	2.4 (6)
N5—Ru1—N4—C20	0.1 (3)	C16—N4—C20—C19	1.1 (5)
N2—Ru1—N4—C20	179.4 (3)	Ru1—N4—C20—C19	177.1 (3)
N1—Ru1—N4—C20	100.0 (3)	C16—N4—C20—C21	−177.3 (3)
N6—Ru1—N4—C20	−3.6 (5)	Ru1—N4—C20—C21	−1.2 (4)
N3—Ru1—N4—C20	−102.1 (3)	C18—C19—C20—N4	−2.6 (6)
N4—Ru1—N5—C21	1.1 (3)	C18—C19—C20—C21	175.5 (4)
N1—Ru1—N5—C21	−89.6 (3)	C25—N5—C21—C22	−3.3 (6)
N6—Ru1—N5—C21	179.7 (3)	Ru1—N5—C21—C22	176.7 (3)
N3—Ru1—N5—C21	88.7 (3)	C25—N5—C21—C20	178.0 (3)
N4—Ru1—N5—C25	−178.9 (3)	Ru1—N5—C21—C20	−2.1 (5)
N1—Ru1—N5—C25	90.3 (3)	N4—C20—C21—N5	2.1 (5)
N6—Ru1—N5—C25	−0.3 (3)	C19—C20—C21—N5	−176.2 (4)
N3—Ru1—N5—C25	−91.4 (3)	N4—C20—C21—C22	−176.6 (4)
N5—Ru1—N6—C30	−179.7 (4)	C19—C20—C21—C22	5.1 (6)
N2—Ru1—N6—C30	1.1 (4)	N5—C21—C22—C23	3.5 (6)
N4—Ru1—N6—C30	−176.0 (3)	C20—C21—C22—C23	−178.0 (4)
N1—Ru1—N6—C30	80.4 (4)	C21—C22—C23—C24	−1.2 (6)
N3—Ru1—N6—C30	−78.1 (3)	C21—C22—C23—Cl2	179.6 (3)
N5—Ru1—N6—C26	−0.3 (3)	C22—C23—C24—C25	−1.3 (6)
N2—Ru1—N6—C26	−179.5 (3)	Cl2—C23—C24—C25	177.9 (3)
N4—Ru1—N6—C26	3.4 (6)	C21—N5—C25—C24	0.7 (6)
N1—Ru1—N6—C26	−100.2 (3)	Ru1—N5—C25—C24	−179.2 (3)
N3—Ru1—N6—C26	101.3 (3)	C21—N5—C25—C26	−179.2 (3)
C5—N1—C1—C2	0.9 (6)	Ru1—N5—C25—C26	0.8 (4)
Ru1—N1—C1—C2	−179.0 (3)	C23—C24—C25—N5	1.5 (5)
N1—C1—C2—C3	0.4 (7)	C23—C24—C25—C26	−178.6 (4)
C1—C2—C3—C4	−1.3 (6)	C30—N6—C26—C27	−1.1 (6)
C2—C3—C4—C5	0.9 (6)	Ru1—N6—C26—C27	179.4 (3)
C1—N1—C5—C4	−1.3 (6)	C30—N6—C26—C25	−179.7 (3)
Ru1—N1—C5—C4	178.6 (3)	Ru1—N6—C26—C25	0.8 (4)
C1—N1—C5—C6	177.6 (3)	N5—C25—C26—N6	−1.1 (5)
Ru1—N1—C5—C6	−2.4 (4)	C24—C25—C26—N6	179.0 (4)
C3—C4—C5—N1	0.4 (6)	N5—C25—C26—C27	−179.6 (4)
C3—C4—C5—C6	−178.5 (4)	C24—C25—C26—C27	0.5 (6)
C10—N2—C6—C7	−0.3 (6)	N6—C26—C27—C28	0.6 (6)
Ru1—N2—C6—C7	180.0 (3)	C25—C26—C27—C28	179.1 (4)
C10—N2—C6—C5	−178.2 (4)	C26—C27—C28—C29	0.4 (7)
Ru1—N2—C6—C5	2.2 (4)	C27—C28—C29—C30	−0.8 (7)
N1—C5—C6—N2	0.3 (5)	C26—N6—C30—C29	0.7 (6)
C4—C5—C6—N2	179.2 (4)	Ru1—N6—C30—C29	−179.9 (3)
N1—C5—C6—C7	−177.3 (4)	C28—C29—C30—N6	0.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl4	0.93	2.68	3.590 (5)	169
C12—H12···O2ⁱ	0.93	2.57	3.391 (6)	148
C15—H15···O1ⁱⁱ	0.93	2.48	3.179 (7)	132
C16—H16···Cl4ⁱⁱⁱ	0.93	2.81	3.498 (5)	132
C27—H27···O1^iv	0.93	2.60	3.474 (7)	158
C28—H28···Cl4^iv	0.93	2.82	3.686 (4)	156
C30—H30···O2ⁱⁱ	0.93	2.54	3.203 (6)	128
O1—H1A···Cl4	0.85	2.76	3.231 (5)	116
O1—H1B···Cl4^v	0.85	2.68	3.176 (4)	118
O2—H2A···Cl3	0.85	2.51	3.156 (4)	133
O2—H2B···Cl3^vi	0.85	2.58	3.209 (4)	132

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

Experimental details

Crystal data
Chemical formula	[Ru(C₁₅H₁₀ClN₃)₂]Cl₂·2H₂O
M_r	743.42
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	291
a, b, c (Å)	10.1367 (5), 16.2964 (7), 17.8995 (8)
V (Å³)	2956.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.18 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.850, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	15880, 5166, 4736
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.084, 1.01
No. of reflections	5166
No. of parameters	389
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.42
Absolute structure	Flack (1983), 2475 Friedel pairs
Absolute structure parameter	0.47 (3)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl4	0.93	2.68	3.590 (5)	169
C12—H12···O2ⁱ	0.93	2.57	3.391 (6)	148
C15—H15···O1ⁱⁱ	0.93	2.48	3.179 (7)	132.3
C16—H16···Cl4ⁱⁱⁱ	0.93	2.81	3.498 (5)	132
C27—H27···O1^iv	0.93	2.60	3.474 (7)	158
C28—H28···Cl4^iv	0.93	2.82	3.686 (4)	156
C30—H30···O2ⁱⁱ	0.93	2.54	3.203 (6)	128
O1—H1A···Cl4	0.85	2.76	3.231 (5)	116
O1—H1B···Cl4^v	0.85	2.68	3.176 (4)	118
O2—H2A···Cl3	0.85	2.51	3.156 (4)	133
O2—H2B···Cl3^vi	0.85	2.58	3.209 (4)	132

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

Acknowledgements

WH would like to acknowledge the National Natural Science Foundation of China (No. 21171088) for financial aid.

References

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