Crystal structure of [3-amino-2-(phenyl­diazenyl)­pyridine]chlorido­(η6-p-cymene)­ruthenium(II) chloride

Hansongnern, K.; Sansook, S.; Romin, T.; Nimthong Roldan, A.; Pakawatchai, C.

doi:10.1107/S2056989015017466

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages m185-m186

doi:10.1107/S2056989015017466

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Crystal structure of [3-amino-2-(phenyldiazenyl)pyridine]chlorido(η⁶-p-cymene)ruthenium(II) chloride

Kanidtha Hansongnern,^a ^* Supojjanee Sansook,^a Thassani Romin,^a Arunpatcha Nimthong Roldan ^b and Chaveng Pakawatchai ^a

^aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand, and ^bDepartment of Chemistry, Youngstown State University, 1 University Plaza, 44555, Youngstown, OH, USA
^*Correspondence e-mail: kanidtha.h@gmail.com

Edited by O. Blacque, University of Zürich, Switzerland (Received 9 September 2015; accepted 18 September 2015; online 26 September 2015)

The title compound, [RuCl(C₁₀H₁₄)(C₁₁H₁₀N₄)]Cl is an Ru^II complex in which an η⁶-p-cymene ligand, two N atoms of 3-amino-2-(phenylazo)pyridine and one Cl ion form a piano-stool coordination environment around the metal ion. In the crystal structure, N—H⋯Cl hydrogen bonds play an important role in the formation of the supramolecular zigzag chain along the a-axis direction. Disorder is observed for the isopropyl group with site-occupancy factors refined to 0.78 (5) and 0.22 (5).

Keywords: crystal structure; 3-amino-2-(phenylazo)pyridine; ruthenium complex; N—H⋯Cl hydrogen bonds.

CCDC reference: 1425731

1. Related literature

For anticancer activity of organometallic ruthenium complexes, see: Almodares et al. (2014 ); Stepanenko et al. (2011 ). For the use of a similar azopyridine ligand to stabilize ruthenium complexes, see: Velders et al. (2000 ). For related η⁶-p-cymene ruthenium complexes, see: Singh et al. (2002 ), Kumar et al. (2008 ). For the crystal structure of an η⁶-p-cymene ruthenium complex with an azopyridine ligand, see: Dougan et al. (2006 ).

2. Experimental

2.1. Crystal data

[RuCl(C₁₀H₁₄)(C₁₁H₁₀N₄)]Cl
M_r = 504.41
Orthorhombic, P b c a
a = 8.9642 (8) Å
b = 17.6283 (16) Å
c = 26.976 (3) Å
V = 4262.8 (7) Å³
Z = 8
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 293 K
0.44 × 0.10 × 0.07 mm

2.2. Data collection

Bruker SMART APEX CCD Diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.693, T_max = 1.000
40186 measured reflections
5127 independent reflections
4242 reflections with I > 2σ(I)
R_int = 0.069

2.3. Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.136
S = 1.12
5127 reflections
265 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −1.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯Cl2	0.86	2.34	3.200 (5)	176
N4—H4B⋯Cl2ⁱ	0.86	2.37	3.152 (5)	151
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2015 ) and SHELXLE (Hübschle et al., 2011 ); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1425731

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015017466/zq2235sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017466/zq2235Isup2.hkl

checkCIF report

Synthesis and crystallization top

3-amino-2-(phenylazo)pyridine (3aazpy) was prepared by condensation of 2,3-diamino-pyridine (14 mg, 2 mmol) with nitrosobenzene (217 mg, 2.1 mmol) in a mixture of 30 M NaOH (3 mL) and 35 mL of benzene solution. The reaction mixture was stirred and heated under reflux for 14 h. The product was extracted many times with benzene to obtain the brown solution. Then the volume was reduced to 3 mL. The residue was purified by column chromatography. The red-orange band was collected and evaporated to dryness (yield : 37%).

The title compound was obtained by the following procedure: [(η⁶-p-cym)RuCl₂]₂ (0.05 mmol) was added to a THF solution of 3aazpy (0.1 mmol); the solution color change from red to purple. The solution was stirred at ambient temperature for 2 h. The precipitate was collected by filtration, washed with a small amount of THF. Monocrystals were obtained by diffusion of ether into a dichloromethane solution of the complex (yield: 82%).

Refinement top

H atoms bonded to C and N atoms were included in calculated positions and were refined with a riding model using distances of 0.93 Å (aryl H), and U_iso(H) = 1.2U_eq(C); 0.98 Å (CH) and U_iso(H) = 1.5U_eq(C); 0.96 Å (CH₃) and U_iso(H) = 1.5U_eq(C); 0.86 Å (NH₂), and U_iso(H) = 1.2U_eq(N). A disorder is observed for the isopropyl group with site-occupancy factors refined to 0.78 (5) and 0.22 (5).

Results and discussion top

Organometallic ruthenium complexes have gained much interest due to promising anticancer activity (Almodares et al., 2014; Stepanenko et al., 2011). These arene complexes consist of a chelating ligand and one chloride ion. In this work, a new ruthenium(II) complex of this type is reported.

The title complex exists as a half sandwich complex with the neutral arene ring bonded to the ruthenium center along with two N atoms from 3-amino-2-(phenylazo)pyridine (3aazpy) and one chloride ion (Fig. 1). The 3aazpy ligand contains the –N=N—C=N linkage which is similar to 2-(phenylazo)pyridine (azpy). Azo ligands of this type can stabilize metals in their lower oxidation states (Velders et al., 2000). The ruthenium atom is π-bonded to the p-cymene ligand with an average Ru—C bond length of 2.215 (6) Å (range 2.185 (6) - 2.243 (5) Å) similar to those observed in related η⁶-p-cymene ruthenium complexes (Singh et al., 2002, Kumar et al., 2008). The p-cymene ring is almost planar and the C—C bond lengths within the ring are in the range 1.376 – 1.435 Å. The ruthenium center is also coordinated to N1 (azo moiety, 2.078 (4) Å) and to N3 (pyridine, 2.077 (4) Å) of 3aazpy. These Ru—N bond lengths are longer than those in [(η⁶-p-cymene)Ru(azpy)Cl](PF₆) (Dougan et al., 2006). It indicates that azpy is a better ligand to stabilize the ruthenium(II) center than 3aazpy. Meanwhile, the bite angle of 75.6 (2)° of the chelate ligand and the Ru—Cl bond distance of 2.3938 (15) Å are comparable to those in [(η⁶-p-cym)Ru(azpy)Cl](PF₆). In the crystal structure, chloride ions are linked with the complex molecule through N4—H4A···Cl2ⁱ and N4—H4B···Cl2 hydrogen bonds leading to the formation of a 1-D zigzag chain along the a-axis (see Table 1 and Fig. 2). A disorder is observed for the isopropyl group with site-occupancy factors refined to 0.78 (5) and 0.22 (5).

Related literature top

For anticancer activity of organometallic ruthenium complexes, see: Almodares et al. (2014); Stepanenko et al. (2011). For the use of a similar azopyridine ligand to stabilize ruthenium complexes, see: Velders et al. (2000). For related η⁶-p-cymene ruthenium complexes, see: Singh et al. (2002), Kumar et al. (2008). For the crystal structure of an η⁶-p-cymene ruthenium complex with an azopyridine ligand, see: Dougan et al. (2006).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2015) and SHELXLE (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Crystal packing of the title compound showing the N—H···Cl hydrogen bonds along the a axis.

[3-Amino-2-(phenyldiazenyl)pyridine]chlorido(η⁶-p-cymene)ruthenium(II) chloride top

Crystal data top

[RuCl(C₁₀H₁₄)(C₁₁H₁₀N₄)]Cl	D_x = 1.572 Mg m⁻³
M_r = 504.41	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 7302 reflections
a = 8.9642 (8) Å	θ = 2.3–27.9°
b = 17.6283 (16) Å	µ = 1.00 mm⁻¹
c = 26.976 (3) Å	T = 293 K
V = 4262.8 (7) Å³	Block, colorless
Z = 8	0.44 × 0.10 × 0.07 mm
F(000) = 2048

Data collection top

Bruker SMART APEX CCD Diffractometer	4242 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.069
φ and ω scans	θ_max = 28.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→11
T_min = 0.693, T_max = 1.000	k = −23→23
40186 measured reflections	l = −35→35
5127 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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0276P)² + 25.095P] where P = (F_o² + 2F_c²)/3
5127 reflections	(Δ/σ)_max = 0.002
265 parameters	Δρ_max = 0.71 e Å⁻³
15 restraints	Δρ_min = −1.61 e Å⁻³

Crystal data top

[RuCl(C₁₀H₁₄)(C₁₁H₁₀N₄)]Cl	V = 4262.8 (7) Å³
M_r = 504.41	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.9642 (8) Å	µ = 1.00 mm⁻¹
b = 17.6283 (16) Å	T = 293 K
c = 26.976 (3) Å	0.44 × 0.10 × 0.07 mm

Data collection top

Bruker SMART APEX CCD Diffractometer	5127 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	4242 reflections with I > 2σ(I)
T_min = 0.693, T_max = 1.000	R_int = 0.069
40186 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	15 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0276P)² + 25.095P] where P = (F_o² + 2F_c²)/3
5127 reflections	Δρ_max = 0.71 e Å⁻³
265 parameters	Δρ_min = −1.61 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ru1	0.62601 (5)	0.03668 (2)	0.38760 (2)	0.03006 (13)
Cl1	0.73313 (19)	−0.03312 (8)	0.45488 (5)	0.0473 (4)
Cl2	0.98928 (17)	−0.30554 (8)	0.21404 (6)	0.0434 (4)
N1	0.5259 (5)	−0.0663 (2)	0.37034 (16)	0.0298 (9)
N2	0.5993 (5)	−0.1133 (2)	0.34347 (16)	0.0310 (10)
N3	0.7791 (5)	−0.0169 (2)	0.34159 (16)	0.0283 (9)
N4	0.7774 (5)	−0.2032 (3)	0.28221 (19)	0.0450 (13)
H4A	0.8322	−0.2296	0.2625	0.054*
H4B	0.6955	−0.2218	0.2935	0.054*
C1	0.3803 (6)	−0.0944 (3)	0.3838 (2)	0.0352 (12)
C2	0.3052 (7)	−0.0609 (3)	0.4228 (2)	0.0410 (14)
H2	0.3527	−0.0249	0.4423	0.049*
C3	0.1594 (7)	−0.0812 (4)	0.4325 (3)	0.0511 (17)
H3	0.1065	−0.0564	0.4574	0.061*
C4	0.0923 (8)	−0.1376 (4)	0.4057 (3)	0.0571 (19)
H4	−0.0057	−0.1514	0.4125	0.069*
C5	0.1712 (8)	−0.1743 (4)	0.3684 (3)	0.0542 (18)
H5	0.1273	−0.2140	0.3510	0.065*
C6	0.3139 (7)	−0.1520 (3)	0.3573 (2)	0.0413 (14)
H6	0.3658	−0.1757	0.3318	0.050*
C7	0.7341 (6)	−0.0871 (3)	0.32750 (18)	0.0270 (10)
C8	0.8194 (6)	−0.1338 (3)	0.2952 (2)	0.0311 (11)
C9	0.9527 (6)	−0.1018 (3)	0.2774 (2)	0.0389 (13)
H9	1.0131	−0.1291	0.2558	0.047*
C10	0.9932 (7)	−0.0306 (3)	0.2921 (2)	0.0477 (15)
H10	1.0801	−0.0090	0.2796	0.057*
C11	0.9061 (6)	0.0096 (3)	0.3252 (2)	0.0396 (14)
H11	0.9388	0.0568	0.3361	0.048*
C12	0.6938 (7)	0.1496 (3)	0.4186 (2)	0.0374 (13)
C13	0.5524 (8)	0.1272 (3)	0.4388 (3)	0.0495 (17)
H13	0.5459	0.1158	0.4743	0.059*
C14	0.4329 (8)	0.1095 (3)	0.4089 (3)	0.0565 (19)
H14	0.3456	0.0853	0.4240	0.068*
C15	0.4465 (8)	0.1082 (3)	0.3565 (3)	0.0549 (18)
C16	0.5835 (7)	0.1301 (3)	0.3363 (2)	0.0447 (15)
H16	0.6012	0.1223	0.3008	0.054*
C17	0.7038 (7)	0.1516 (3)	0.3669 (2)	0.0382 (13)
H17	0.8028	0.1568	0.3518	0.046*
C18	0.3198 (8)	0.0843 (5)	0.3244 (3)	0.081 (3)
H18A	0.3575	0.0676	0.2929	0.121*
H18B	0.2536	0.1264	0.3195	0.121*
H18C	0.2667	0.0436	0.3401	0.121*
C19	0.8212 (9)	0.1721 (4)	0.4513 (3)	0.0580 (19)	0.78 (5)
H19	0.7999	0.1522	0.4845	0.070*	0.78 (5)
C20	0.9735 (12)	0.1408 (13)	0.4358 (7)	0.066 (4)	0.78 (5)
H20A	0.9682	0.0865	0.4335	0.099*	0.78 (5)
H20B	1.0471	0.1547	0.4600	0.099*	0.78 (5)
H20C	1.0006	0.1614	0.4041	0.099*	0.78 (5)
C21	0.824 (3)	0.2586 (7)	0.4555 (12)	0.111 (8)	0.78 (5)
H21A	0.9016	0.2735	0.4781	0.167*	0.78 (5)
H21B	0.7298	0.2763	0.4675	0.167*	0.78 (5)
H21C	0.8437	0.2802	0.4234	0.167*	0.78 (5)
C19B	0.8212 (9)	0.1721 (4)	0.4513 (3)	0.0580 (19)	0.22 (5)
H19B	0.8245	0.1339	0.4777	0.070*	0.22 (5)
C20B	0.974 (4)	0.169 (4)	0.426 (2)	0.066 (4)	0.22 (5)
H20D	0.9845	0.1215	0.4094	0.099*	0.22 (5)
H20E	1.0504	0.1738	0.4510	0.099*	0.22 (5)
H20F	0.9819	0.2098	0.4030	0.099*	0.22 (5)
C21B	0.791 (9)	0.247 (3)	0.477 (3)	0.111 (8)	0.22 (5)
H21D	0.8799	0.2637	0.4939	0.167*	0.22 (5)
H21E	0.7125	0.2405	0.5011	0.167*	0.22 (5)
H21F	0.7618	0.2844	0.4533	0.167*	0.22 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.0334 (2)	0.02129 (19)	0.0355 (2)	0.00223 (18)	0.00250 (19)	−0.00160 (17)
Cl1	0.0641 (10)	0.0363 (7)	0.0414 (8)	0.0089 (7)	−0.0093 (7)	0.0017 (6)
Cl2	0.0424 (8)	0.0322 (7)	0.0558 (9)	−0.0014 (6)	0.0150 (7)	−0.0051 (6)
N1	0.033 (2)	0.024 (2)	0.032 (2)	−0.0030 (19)	0.0057 (19)	−0.0007 (17)
N2	0.030 (2)	0.023 (2)	0.040 (2)	0.0006 (18)	0.0072 (19)	−0.0019 (18)
N3	0.028 (2)	0.021 (2)	0.036 (2)	−0.0013 (17)	−0.0003 (19)	−0.0040 (17)
N4	0.039 (3)	0.031 (3)	0.065 (3)	−0.004 (2)	0.019 (3)	−0.011 (2)
C1	0.032 (3)	0.032 (3)	0.041 (3)	−0.002 (2)	0.009 (3)	0.006 (2)
C2	0.043 (3)	0.036 (3)	0.044 (3)	0.002 (3)	0.011 (3)	0.001 (3)
C3	0.049 (4)	0.050 (4)	0.054 (4)	0.006 (3)	0.023 (3)	0.009 (3)
C4	0.036 (4)	0.069 (5)	0.066 (5)	−0.005 (3)	0.006 (3)	0.020 (4)
C5	0.047 (4)	0.047 (4)	0.069 (5)	−0.016 (3)	0.002 (3)	0.001 (3)
C6	0.038 (3)	0.037 (3)	0.049 (4)	−0.008 (3)	0.009 (3)	−0.004 (3)
C7	0.025 (2)	0.024 (2)	0.032 (3)	−0.001 (2)	0.000 (2)	0.000 (2)
C8	0.034 (3)	0.025 (3)	0.035 (3)	0.004 (2)	0.004 (2)	0.002 (2)
C9	0.031 (3)	0.040 (3)	0.046 (3)	0.008 (2)	0.010 (3)	−0.004 (3)
C10	0.036 (3)	0.045 (3)	0.062 (4)	−0.011 (3)	0.014 (3)	−0.006 (3)
C11	0.032 (3)	0.034 (3)	0.053 (4)	−0.004 (2)	0.010 (3)	−0.011 (3)
C12	0.060 (4)	0.015 (2)	0.037 (3)	0.001 (2)	0.004 (3)	0.002 (2)
C13	0.076 (5)	0.021 (3)	0.052 (4)	0.006 (3)	0.020 (4)	−0.004 (3)
C14	0.050 (4)	0.026 (3)	0.093 (6)	0.011 (3)	0.019 (4)	−0.005 (3)
C15	0.048 (4)	0.030 (3)	0.087 (5)	0.011 (3)	−0.014 (4)	0.002 (3)
C16	0.055 (4)	0.031 (3)	0.049 (4)	0.010 (3)	−0.007 (3)	0.008 (3)
C17	0.045 (3)	0.024 (3)	0.045 (3)	0.003 (3)	0.002 (3)	0.006 (2)
C18	0.053 (5)	0.064 (5)	0.126 (8)	0.007 (4)	−0.038 (5)	0.020 (5)
C19	0.089 (6)	0.036 (3)	0.049 (4)	−0.013 (4)	−0.013 (4)	−0.012 (3)
C20	0.066 (6)	0.064 (10)	0.068 (8)	−0.018 (6)	−0.016 (5)	−0.002 (7)
C21	0.147 (15)	0.048 (6)	0.14 (2)	−0.010 (8)	−0.054 (14)	−0.032 (9)
C19B	0.089 (6)	0.036 (3)	0.049 (4)	−0.013 (4)	−0.013 (4)	−0.012 (3)
C20B	0.066 (6)	0.064 (10)	0.068 (8)	−0.018 (6)	−0.016 (5)	−0.002 (7)
C21B	0.147 (15)	0.048 (6)	0.14 (2)	−0.010 (8)	−0.054 (14)	−0.032 (9)

Geometric parameters (Å, º) top

Ru1—N3	2.077 (4)	C10—H10	0.9300
Ru1—N1	2.078 (4)	C11—H11	0.9300
Ru1—C16	2.185 (6)	C12—C17	1.398 (8)
Ru1—C15	2.210 (6)	C12—C13	1.435 (9)
Ru1—C13	2.211 (6)	C12—C19	1.498 (9)
Ru1—C17	2.215 (5)	C13—C14	1.376 (10)
Ru1—C14	2.231 (6)	C13—H13	0.9800
Ru1—C12	2.243 (5)	C14—C15	1.419 (10)
Ru1—Cl1	2.3938 (15)	C14—H14	0.9800
N1—N2	1.283 (6)	C15—C16	1.398 (9)
N1—C1	1.442 (7)	C15—C18	1.489 (10)
N2—C7	1.363 (6)	C16—C17	1.411 (8)
N3—C11	1.307 (7)	C16—H16	0.9800
N3—C7	1.356 (6)	C17—H17	0.9800
N4—C8	1.327 (7)	C18—H18A	0.9600
N4—H4A	0.8600	C18—H18B	0.9600
N4—H4B	0.8600	C18—H18C	0.9600
C1—C6	1.376 (8)	C19—C21	1.529 (12)
C1—C2	1.381 (8)	C19—C20	1.531 (12)
C2—C3	1.381 (8)	C19—H19	0.9800
C2—H2	0.9300	C20—H20A	0.9600
C3—C4	1.368 (10)	C20—H20B	0.9600
C3—H3	0.9300	C20—H20C	0.9600
C4—C5	1.389 (10)	C21—H21A	0.9600
C4—H4	0.9300	C21—H21B	0.9600
C5—C6	1.371 (8)	C21—H21C	0.9600
C5—H5	0.9300	C20B—H20D	0.9600
C6—H6	0.9300	C20B—H20E	0.9600
C7—C8	1.422 (7)	C20B—H20F	0.9600
C8—C9	1.406 (8)	C21B—H21D	0.9600
C9—C10	1.365 (8)	C21B—H21E	0.9600
C9—H9	0.9300	C21B—H21F	0.9600
C10—C11	1.382 (8)

N3—Ru1—N1	75.80 (16)	C9—C10—C11	120.6 (5)
N3—Ru1—C16	94.5 (2)	C9—C10—H10	119.7
N1—Ru1—C16	116.2 (2)	C11—C10—H10	119.7
N3—Ru1—C15	120.9 (2)	N3—C11—C10	121.8 (5)
N1—Ru1—C15	95.7 (2)	N3—C11—H11	119.1
C16—Ru1—C15	37.1 (2)	C10—C11—H11	119.1
N3—Ru1—C13	153.9 (2)	C17—C12—C13	116.3 (6)
N1—Ru1—C13	129.9 (2)	C17—C12—C19	122.2 (6)
C16—Ru1—C13	78.4 (2)	C13—C12—C19	121.5 (6)
C15—Ru1—C13	66.9 (3)	C17—C12—Ru1	70.6 (3)
N3—Ru1—C17	93.25 (19)	C13—C12—Ru1	70.0 (3)
N1—Ru1—C17	151.50 (19)	C19—C12—Ru1	131.4 (4)
C16—Ru1—C17	37.4 (2)	C14—C13—C12	121.9 (6)
C15—Ru1—C17	67.1 (2)	C14—C13—Ru1	72.7 (4)
C13—Ru1—C17	65.9 (2)	C12—C13—Ru1	72.4 (3)
N3—Ru1—C14	158.2 (2)	C14—C13—H13	118.6
N1—Ru1—C14	103.0 (2)	C12—C13—H13	118.6
C16—Ru1—C14	66.1 (3)	Ru1—C13—H13	118.6
C15—Ru1—C14	37.3 (3)	C13—C14—C15	121.3 (7)
C13—Ru1—C14	36.1 (3)	C13—C14—Ru1	71.2 (4)
C17—Ru1—C14	77.5 (2)	C15—C14—Ru1	70.6 (4)
N3—Ru1—C12	116.54 (19)	C13—C14—H14	118.5
N1—Ru1—C12	167.39 (19)	C15—C14—H14	118.5
C16—Ru1—C12	67.3 (2)	Ru1—C14—H14	118.5
C15—Ru1—C12	80.3 (2)	C16—C15—C14	117.4 (7)
C13—Ru1—C12	37.6 (2)	C16—C15—C18	121.3 (7)
C17—Ru1—C12	36.5 (2)	C14—C15—C18	121.2 (7)
C14—Ru1—C12	66.6 (2)	C16—C15—Ru1	70.5 (3)
N3—Ru1—Cl1	87.39 (12)	C14—C15—Ru1	72.2 (4)
N1—Ru1—Cl1	83.92 (13)	C18—C15—Ru1	127.9 (5)
C16—Ru1—Cl1	159.70 (18)	C15—C16—C17	121.1 (6)
C15—Ru1—Cl1	150.8 (2)	C15—C16—Ru1	72.4 (4)
C13—Ru1—Cl1	91.00 (19)	C17—C16—Ru1	72.5 (3)
C17—Ru1—Cl1	122.36 (16)	C15—C16—H16	119.1
C14—Ru1—Cl1	114.3 (2)	C17—C16—H16	119.1
C12—Ru1—Cl1	93.73 (15)	Ru1—C16—H16	119.1
N2—N1—C1	112.6 (4)	C12—C17—C16	121.9 (6)
N2—N1—Ru1	118.0 (3)	C12—C17—Ru1	72.8 (3)
C1—N1—Ru1	129.4 (3)	C16—C17—Ru1	70.1 (3)
N1—N2—C7	114.5 (4)	C12—C17—H17	118.3
C11—N3—C7	119.4 (4)	C16—C17—H17	118.3
C11—N3—Ru1	128.0 (4)	Ru1—C17—H17	118.3
C7—N3—Ru1	112.7 (3)	C15—C18—H18A	109.5
C8—N4—H4A	120.0	C15—C18—H18B	109.5
C8—N4—H4B	120.0	H18A—C18—H18B	109.5
H4A—N4—H4B	120.0	C15—C18—H18C	109.5
C6—C1—C2	120.0 (5)	H18A—C18—H18C	109.5
C6—C1—N1	120.9 (5)	H18B—C18—H18C	109.5
C2—C1—N1	119.0 (5)	C12—C19—C21	108.7 (9)
C3—C2—C1	119.8 (6)	C12—C19—C20	115.0 (7)
C3—C2—H2	120.1	C21—C19—C20	111.3 (10)
C1—C2—H2	120.1	C12—C19—H19	107.2
C4—C3—C2	120.2 (6)	C21—C19—H19	107.2
C4—C3—H3	119.9	C20—C19—H19	107.2
C2—C3—H3	119.9	C19—C20—H20A	109.5
C3—C4—C5	119.8 (6)	C19—C20—H20B	109.5
C3—C4—H4	120.1	H20A—C20—H20B	109.5
C5—C4—H4	120.1	C19—C20—H20C	109.5
C6—C5—C4	120.0 (7)	H20A—C20—H20C	109.5
C6—C5—H5	120.0	H20B—C20—H20C	109.5
C4—C5—H5	120.0	C19—C21—H21A	109.5
C5—C6—C1	120.0 (6)	C19—C21—H21B	109.5
C5—C6—H6	120.0	H21A—C21—H21B	109.5
C1—C6—H6	120.0	C19—C21—H21C	109.5
N3—C7—N2	119.0 (4)	H21A—C21—H21C	109.5
N3—C7—C8	122.7 (5)	H21B—C21—H21C	109.5
N2—C7—C8	118.2 (4)	H20D—C20B—H20E	109.5
N4—C8—C9	121.4 (5)	H20D—C20B—H20F	109.5
N4—C8—C7	123.0 (5)	H20E—C20B—H20F	109.5
C9—C8—C7	115.7 (5)	H21D—C21B—H21E	109.5
C10—C9—C8	119.8 (5)	H21D—C21B—H21F	109.5
C10—C9—H9	120.1	H21E—C21B—H21F	109.5
C8—C9—H9	120.1

C1—N1—N2—C7	176.3 (4)	C19—C12—C13—C14	177.3 (6)
Ru1—N1—N2—C7	−3.0 (6)	Ru1—C12—C13—C14	−55.7 (5)
N2—N1—C1—C6	−19.8 (7)	C17—C12—C13—Ru1	55.0 (4)
Ru1—N1—C1—C6	159.5 (4)	C19—C12—C13—Ru1	−127.0 (5)
N2—N1—C1—C2	162.6 (5)	C12—C13—C14—C15	3.7 (9)
Ru1—N1—C1—C2	−18.2 (7)	Ru1—C13—C14—C15	−51.8 (5)
C6—C1—C2—C3	−5.1 (9)	C12—C13—C14—Ru1	55.5 (5)
N1—C1—C2—C3	172.7 (5)	C13—C14—C15—C16	−3.7 (9)
C1—C2—C3—C4	4.1 (10)	Ru1—C14—C15—C16	−55.8 (5)
C2—C3—C4—C5	−0.3 (10)	C13—C14—C15—C18	176.1 (6)
C3—C4—C5—C6	−2.5 (11)	Ru1—C14—C15—C18	124.0 (6)
C4—C5—C6—C1	1.5 (10)	C13—C14—C15—Ru1	52.1 (5)
C2—C1—C6—C5	2.3 (9)	C14—C15—C16—C17	0.7 (9)
N1—C1—C6—C5	−175.4 (6)	C18—C15—C16—C17	−179.1 (6)
C11—N3—C7—N2	−177.9 (5)	Ru1—C15—C16—C17	−55.9 (5)
Ru1—N3—C7—N2	1.0 (6)	C14—C15—C16—Ru1	56.6 (5)
C11—N3—C7—C8	−0.1 (8)	C18—C15—C16—Ru1	−123.2 (6)
Ru1—N3—C7—C8	178.8 (4)	C13—C12—C17—C16	−2.3 (8)
N1—N2—C7—N3	1.3 (7)	C19—C12—C17—C16	179.7 (5)
N1—N2—C7—C8	−176.6 (4)	Ru1—C12—C17—C16	52.4 (5)
N3—C7—C8—N4	178.4 (5)	C13—C12—C17—Ru1	−54.7 (4)
N2—C7—C8—N4	−3.8 (8)	C19—C12—C17—Ru1	127.4 (5)
N3—C7—C8—C9	−1.8 (7)	C15—C16—C17—C12	2.3 (9)
N2—C7—C8—C9	176.0 (5)	Ru1—C16—C17—C12	−53.6 (5)
N4—C8—C9—C10	−179.2 (6)	C15—C16—C17—Ru1	55.9 (5)
C7—C8—C9—C10	0.9 (8)	C17—C12—C19—C21	81.0 (17)
C8—C9—C10—C11	1.6 (10)	C13—C12—C19—C21	−96.8 (16)
C7—N3—C11—C10	2.9 (9)	Ru1—C12—C19—C21	172.9 (15)
Ru1—N3—C11—C10	−175.8 (5)	C17—C12—C19—C20	−44.5 (14)
C9—C10—C11—N3	−3.7 (10)	C13—C12—C19—C20	137.7 (12)
C17—C12—C13—C14	−0.7 (8)	Ru1—C12—C19—C20	47.4 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···Cl2	0.86	2.34	3.200 (5)	176
N4—H4B···Cl2ⁱ	0.86	2.37	3.152 (5)	151

Symmetry code: (i) x−1/2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···Cl2	0.86	2.34	3.200 (5)	175.8
N4—H4B···Cl2ⁱ	0.86	2.37	3.152 (5)	150.7

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

Financial support from the Center of Excellence for Innovation of Chemistry (PERCH–CIC), Office of the Higher Education Commission, Ministry of Education, Department of Chemistry, and Graduate School, Prince of Songkla University are gratefully acknowledged.

References

Almodares, Z., Lucas, S. J., Crossley, B. D., Basri, A. M., Pask, C. M., Hebden, A. J., Phillips, R. M. & McGowan, P. C. (2014). Inorg. Chem. 53, 727–736. CSD CrossRef CAS PubMed Google Scholar
Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dougan, S. J., Melchart, M., Habtemariam, A., Parsons, S. & Sadler, P. J. (2006). Inorg. Chem. 45, 10882–10894. CSD CrossRef PubMed CAS Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Kumar, K. N., Venkatachalam, G., Ramesh, R. & Liu, Y. (2008). Polyhedron, 27, 157–166. CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Singh, A., Singh, N. & Pandey, D. S. (2002). J. Organomet. Chem. 642, 48–57. Web of Science CSD CrossRef CAS Google Scholar
Stepanenko, I. N., Novak, M. S., Mühlgassner, M., Roller, A., Hejl, M., Arion, V. B., Jakupec, M. A. & Keppler, B. K. (2011). Inorg. Chem. 50, 11715–11728. CSD CrossRef CAS PubMed Google Scholar
Velders, A. H., Kooijman, H., Spek, A. L., Haasnoot, J. G., de Vos, D. & Reedijk, J. (2000). Inorg. Chem. 39, 2966–2967. Web of Science CSD CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 10| October 2015| Pages m185-m186

doi:10.1107/S2056989015017466

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