Crystal structure of cis,fac-{N,N-bis­[(pyridin-2-yl)meth­yl]methyl­amine-κ3N,N′,N′′}di­chlorido­(dimethyl sulfoxide-κS)ruthenium(II)

Trotter, K.; Arulsamy, N.; Hulley, E.

doi:10.1107/S2056989015014875

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 9| September 2015| Pages m169-m170

https://doi.org/10.1107/S2056989015014875

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Crystal structure of cis,fac-{N,N-bis[(pyridin-2-yl)methyl]methylamine-κ³N,N′,N′′}dichlorido(dimethyl sulfoxide-κS)ruthenium(II)

Kasey Trotter,^a Navamoney Arulsamy ^a and Elliott Hulley ^a ^*

^aUniversity of Wyoming, 1000 E University Ave, Dept. 3838, Laramie, WY 82071, USA
^*Correspondence e-mail: ehulley@uwyo.edu

Edited by O. Blacque, University of Zürich, Switzerland (Received 28 July 2015; accepted 8 August 2015; online 22 August 2015)

The reaction of dichloridotetrakis(dimethyl sulfoxide)ruthenium(II) with N,N-bis[(pyridin-2-yl)methyl]methylamine affords the title complex, [RuCl₂(C₁₃H₁₅N₃)(C₂H₆OS)]. The asymmetric unit contains a well-ordered complex molecule. The N,N-bis[(pyridin-2-yl)methyl]methylamine (bpma) ligand binds the cation through its two pyridyl N atoms and one aliphatic N atom in a facial manner. The coordination sphere of the low-spin d⁶ Ru^II is distorted octahedral. The dimethyl sulfoxide (dmso) ligand coordinates to the cation through its S atom and is cis to the aliphatic N atom. The two chloride ligands occupy the remaining sites. The bpma ligand is folded with the dihedral angle between the mean planes passing through its two pyridine rings being 64.55 (8)°. The two N—Ru—N bite angles of the ligand at 81.70 (7) and 82.34 (8)° illustrate the distorted octahedral coordination geometry of the Ru^II cation. Two neighboring molecules are weakly associated through mutual intermolecular hydrogen bonding involving the O atom and one of the methyl groups of the dmso ligand. One of the chloride ligands is also weakly hydrogen bonded to a pyridyl H atom of another molecule.

Keywords: crystal structure; ruthenium(II) complex; S-bound dimethyl sulfoxide; distorted octahedral coordination geometry.

CCDC reference: 1417672

1. Related literature

For the synthesis of bpma, see: Astner et al. (2008 ). For the synthesis of RuCl₂(dmso)₄ (dmso is dimethyl sulfoxide), see: Evans et al. (1973 ). Ruthenium(II) complexes of pyridine-based ligands which also contain a dmso ligand act as catalytic initiators (Bressan & Morvillo, 1992 ; Carvalho et al., 2014 ; Ferrer et al., 2013 ). The ambidentate dmso ligand exhibits preferential binding through its S atom with low-spin d⁶ Ru^II cations and through its O atom with Ru^III cations (Roeser et al., 2013 ; Smith et al., 2000 ). Ruthenium(II) complexes containing the labile dmso and chloride ligands are particularly attractive precursors for the synthesis of specifically designed catalysts. For the synthesis and structures of such complexes, see: Fischer et al. (2009 ); Mola et al. (2007 ). For complexes containing facially coordinated tridentate ligands, see: Dakkach et al. (2013 ); Fischer et al. (2009); Mishra et al. (2009 ); Matsuya et al. (2009 ); Mola et al. (2006 , 2007, 2009 ); Rodriguez et al. (2001 ); Sala et al. (2008 ); Serrano et al. (2006 ); Shimizu et al. (2008 ); Suzuki et al. (2014 )

2. Experimental

2.1. Crystal data

[RuCl₂(C₁₃H₁₅N₃)(C₂H₆OS)]
M_r = 463.38
Monoclinic, C 2/c
a = 14.6117 (3) Å
b = 9.3345 (2) Å
c = 27.3451 (7) Å
β = 102.734 (1)°
V = 3637.94 (14) Å³
Z = 8
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 150 K
0.21 × 0.17 × 0.11 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SAINT; Bruker, 2009 ) T_min = 0.647, T_max = 0.747
33234 measured reflections
7273 independent reflections
5265 reflections with I > 2σ(I)
R_int = 0.068

2.3. Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.085
S = 1.01
7273 reflections
292 parameters
All H-atom parameters refined
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14A⋯O1ⁱ	0.91 (4)	2.54 (4)	3.431 (3)	169 (3)
C4—H4⋯Cl1ⁱⁱ	0.93 (3)	2.58 (3)	3.487 (2)	165 (2)
C1—H1C⋯O1	0.99 (3)	2.32 (3)	3.182 (4)	145 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1417672

Crystal structure: contains datablocks New_Global_Publ_Block, I. DOI: https://doi.org/10.1107/S2056989015014875/zq2232sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015014875/zq2232Isup2.hkl

Structural commentary. DOI: https://doi.org/10.1107/S2056989015014875/zq2232sup3.docx

Supporting information file. DOI: https://doi.org/10.1107/S2056989015014875/zq2232sup3.pdf

checkCIF report

Comment top

Ruthenium(II) complexes of pyridine-based ligands which also contain a dimethylsulfoxide (dmso) ligand act as catalytic initiators (Bressan & Morvillo, 1992; Carvalho et al., 2014; Ferrer et al., 2013). The ambidentate dmso appears to show preferential binding through its S atom with Ru^II centers, and its O atom with Ru^III centers (Roeser et al., 2013; Smith et al., 2000). Ruthenium(II) complexes containing the labile dmso and chloride ligands are particularly attractive precursors for the synthesis of specifically-designed catalysts. Our research project is aimed at the catalytic reduction of stable anions such as perchlorates using Ru^II precatalysts. Multidentate ligands are expected to stabilize ruthenium(IV)–oxido intermediates suggested as intermediates in the catalytic oxidation of a variety of organic substrates in the presence of hypochlorite, perchlorate and other oxidizers (Bressan & Morvillo 1992). Here we report the X-ray crystal structural determination of a potential precursor ruthenium complex. The title compound, RuCl₂(bpma)(dmso), is synthesized from the reaction of RuCl₂(dmso)₄ (Evans et al., 1973 ) with N,N-bis(pyridin-2-ylmethyl)methylamine (bpma) (Astner et al., 2008).

Structural commentary top

The asymmetric unit contains a well-ordered RuCl₂(bpma)(dmso) molecule. The metal center is in a distorted octahedral geometry with the tridentate bpma ligand binding through its two pyridyl N atoms and aliphatic N atom in a facial mode, as shown in Fig. 1. The two chloride ligands occupy two adjacent sites, and the dmso ligand is present trans to one of the pyridyl N atoms. The tridentate ligand is folded to achieve facial coordination, and the extent of folding is reflected in the small dihedral angle of 64.55 (8)° between the mean planes passing through the two pyridine rings. The two N—Ru—N bite angles of the ligand at 81.70 (7) and 82.34 (8)° are illustrative of the distorted octahedral geometry of the metal center. The complex can be represented as the cis,fac-isomer to indicate the cis-geometry of the dmso ligand to the aliphatic N atom and the facial coordination mode of bpma. A literature survey of Ru^II complexes of bpma and those of closely related bis(pyridin-2-ylmethyl)alkylamine ligands reveals that an overwhelming majority of the complexes contain facially coordinated tridentate ligands (Dakkach et al., 2013; Fischer et al., 2009; Mishra et al., 2009; Matsuya et al., 2009; Mola et al., 2006, 2007, 2009; Rodriguez et al., 2001; Sala et al., 2008; Serrano et al., 2006; Shimizu et al., 2008; Suzuki et al., 2014). cis,fac-isomer is the thermodynamically favored (Mola et al., 2007), and therefore the more frequent occurrence of this isomer is unsurprising. However, Shimuzu et al. suggest that the binding mode of the tridentate ligand depends on the nature of the other ligands with the hydroxo and methoxo ligands favoring meridional coordination mode for the tridentate ligands (Shimizu et al., 2008). The Ru—N_py distances in the present complex are unequal as they have either a chloride or dmso ligands in their respective trans positions. The Ru—dmso bond is unexceptional at 2.2207 (6) Å, and comparable to those found in cis,fac-RuCl₂(bpma)(dmso) and trans,mer-RuCl₂(bpea)(dmso) (Mola et al., 2007).

Related literature top

For the synthesis of bpma, see: Astner et al. (2008). For the synthesis of RuCl₂(dmso)₄ (dmso is dimethyl sulfoxide), see: Evans et al. (1973). Ruthenium(II) complexes of pyridine-based ligands which also contain a dmso ligand act as catalytic initiators (Bressan & Morvillo, 1992; Carvalho et al., 2014; Ferrer et al., 2013). The ambidentate dmso ligand exhibits preferential binding through its S atom with low-spin d⁶ Ru^II centers, and through its O atom with Ru^III centers (Roeser et al., 2013; Smith et al., 2000). Ruthenium(II) complexes containing the labile dmso and chloride ligands are particularly attractive precursors for the synthesis of specifically designed catalysts. For the synthesis and structures of such complexes, see: Fischer et al. (2009); Mola et al. (2007). For complexes containing facially coordinated tridentate ligands, see: Dakkach et al. (2013); Fischer et al. (2009); Mishra et al. (2009); Matsuya et al. (2009); Mola et al. (2006, 2007, 2009); Rodriguez et al. (2001); Sala et al. (2008); Serrano et al. (2006); Shimizu et al. (2008); Suzuki et al. (2014)

Structure description top

For the synthesis of bpma, see: Astner et al. (2008). For the synthesis of RuCl₂(dmso)₄ (dmso is dimethyl sulfoxide), see: Evans et al. (1973). Ruthenium(II) complexes of pyridine-based ligands which also contain a dmso ligand act as catalytic initiators (Bressan & Morvillo, 1992; Carvalho et al., 2014; Ferrer et al., 2013). The ambidentate dmso ligand exhibits preferential binding through its S atom with low-spin d⁶ Ru^II centers, and through its O atom with Ru^III centers (Roeser et al., 2013; Smith et al., 2000). Ruthenium(II) complexes containing the labile dmso and chloride ligands are particularly attractive precursors for the synthesis of specifically designed catalysts. For the synthesis and structures of such complexes, see: Fischer et al. (2009); Mola et al. (2007). For complexes containing facially coordinated tridentate ligands, see: Dakkach et al. (2013); Fischer et al. (2009); Mishra et al. (2009); Matsuya et al. (2009); Mola et al. (2006, 2007, 2009); Rodriguez et al. (2001); Sala et al. (2008); Serrano et al. (2006); Shimizu et al. (2008); Suzuki et al. (2014)

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of RuCl₂(dpma)(dmso). H atoms have been omitted and displacement parameters are drawn at the 50% probability level.

(I) top

Crystal data top

[RuCl₂(C₁₃H₁₅N₃)(C₂H₆OS)]	F(000) = 1872
M_r = 463.38	D_x = 1.692 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.6117 (3) Å	Cell parameters from 4846 reflections
b = 9.3345 (2) Å	θ = 2.6–29.0°
c = 27.3451 (7) Å	µ = 1.28 mm⁻¹
β = 102.734 (1)°	T = 150 K
V = 3637.94 (14) Å³	Rectangular, yellow
Z = 8	0.21 × 0.17 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	5265 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.068
Absorption correction: multi-scan (SAINT; Bruker, 2009)	θ_max = 33.7°, θ_min = 2.6°
T_min = 0.647, T_max = 0.747	h = −19→22
33234 measured reflections	k = −14→14
7273 independent reflections	l = −42→42

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	All H-atom parameters refined
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0338P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
7273 reflections	Δρ_max = 1.13 e Å⁻³
292 parameters	Δρ_min = −0.92 e Å⁻³

Crystal data top

[RuCl₂(C₁₃H₁₅N₃)(C₂H₆OS)]	V = 3637.94 (14) Å³
M_r = 463.38	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.6117 (3) Å	µ = 1.28 mm⁻¹
b = 9.3345 (2) Å	T = 150 K
c = 27.3451 (7) Å	0.21 × 0.17 × 0.11 mm
β = 102.734 (1)°

Data collection top

Bruker APEXII CCD diffractometer	7273 independent reflections
Absorption correction: multi-scan (SAINT; Bruker, 2009)	5265 reflections with I > 2σ(I)
T_min = 0.647, T_max = 0.747	R_int = 0.068
33234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.085	All H-atom parameters refined
S = 1.01	Δρ_max = 1.13 e Å⁻³
7273 reflections	Δρ_min = −0.92 e Å⁻³
292 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
Ru1	0.67345 (2)	0.51144 (2)	0.37644 (2)	0.01639 (5)
Cl1	0.54447 (4)	0.65278 (5)	0.33000 (2)	0.02026 (11)
Cl2	0.77049 (4)	0.72523 (6)	0.39465 (2)	0.02641 (13)
N1	0.78992 (14)	0.3807 (2)	0.40882 (7)	0.0224 (4)
N2	0.72321 (14)	0.47141 (18)	0.31136 (7)	0.0169 (3)
N3	0.61032 (14)	0.31637 (19)	0.35845 (7)	0.0195 (4)
S1	0.61157 (5)	0.53018 (6)	0.44340 (2)	0.02421 (13)
O1	0.64939 (15)	0.4440 (2)	0.48897 (7)	0.0394 (5)
C14	0.4890 (2)	0.4893 (3)	0.42722 (10)	0.0321 (6)
H14A	0.459 (3)	0.515 (3)	0.4517 (13)	0.045 (10)*
H14B	0.461 (2)	0.541 (3)	0.3971 (12)	0.038 (8)*
H14C	0.485 (2)	0.388 (4)	0.4213 (11)	0.042 (9)*
C15	0.6052 (2)	0.7116 (3)	0.46376 (11)	0.0346 (6)
H15A	0.571 (2)	0.713 (3)	0.4902 (11)	0.037 (8)*
H15B	0.673 (3)	0.748 (4)	0.4742 (12)	0.063 (11)*
H15C	0.576 (2)	0.775 (3)	0.4363 (10)	0.033 (8)*
C1	0.8474 (2)	0.4251 (3)	0.45892 (9)	0.0308 (6)
H1A	0.8987 (18)	0.356 (3)	0.4712 (9)	0.018 (6)*
H1B	0.873 (2)	0.523 (3)	0.4570 (11)	0.033 (8)*
H1C	0.805 (2)	0.427 (3)	0.4826 (10)	0.028 (7)*
C2	0.85411 (17)	0.3835 (3)	0.37313 (8)	0.0235 (5)
H2A	0.8994 (19)	0.303 (3)	0.3795 (9)	0.027 (7)*
H2B	0.891 (2)	0.477 (3)	0.3815 (11)	0.030 (8)*
C3	0.80268 (16)	0.3934 (2)	0.31945 (8)	0.0181 (4)
C4	0.83608 (18)	0.3340 (2)	0.28026 (9)	0.0221 (5)
H4	0.892 (2)	0.283 (3)	0.2870 (9)	0.025 (7)*
C5	0.78772 (18)	0.3565 (2)	0.23159 (9)	0.0230 (5)
H5	0.8051 (18)	0.312 (3)	0.2059 (9)	0.022 (7)*
C6	0.70671 (17)	0.4370 (3)	0.22333 (8)	0.0220 (5)
H6	0.6718 (19)	0.455 (3)	0.1914 (10)	0.024 (7)*
C7	0.67585 (17)	0.4919 (2)	0.26393 (8)	0.0189 (4)
H7	0.617 (2)	0.545 (3)	0.2603 (10)	0.027 (7)*
C8	0.7522 (2)	0.2349 (3)	0.41426 (10)	0.0293 (6)
H8A	0.736 (2)	0.230 (3)	0.4470 (11)	0.041 (9)*
H8B	0.795 (2)	0.167 (3)	0.4131 (10)	0.027 (7)*
C9	0.66441 (17)	0.2018 (2)	0.37632 (8)	0.0231 (5)
C10	0.6356 (2)	0.0633 (3)	0.36206 (11)	0.0315 (6)
H10	0.674 (2)	−0.012 (3)	0.3745 (10)	0.028 (8)*
C11	0.5508 (2)	0.0411 (3)	0.33028 (12)	0.0355 (7)
H11	0.532 (2)	−0.043 (4)	0.3154 (12)	0.046 (9)*
C12	0.4947 (2)	0.1582 (3)	0.31229 (11)	0.0318 (6)
H12	0.4356 (19)	0.140 (3)	0.2891 (10)	0.024 (7)*
C13	0.52796 (18)	0.2934 (3)	0.32657 (9)	0.0240 (5)
H13	0.499 (2)	0.370 (3)	0.3156 (10)	0.029 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01879 (10)	0.01715 (8)	0.01358 (7)	0.00499 (7)	0.00432 (6)	0.00194 (6)
Cl1	0.0204 (3)	0.0194 (2)	0.0211 (2)	0.0071 (2)	0.0046 (2)	0.00371 (18)
Cl2	0.0289 (3)	0.0227 (3)	0.0249 (3)	−0.0001 (2)	0.0002 (2)	−0.0007 (2)
N1	0.0228 (11)	0.0253 (9)	0.0193 (8)	0.0090 (8)	0.0051 (7)	0.0030 (7)
N2	0.0187 (9)	0.0165 (8)	0.0160 (8)	0.0026 (7)	0.0049 (7)	0.0007 (6)
N3	0.0237 (10)	0.0179 (8)	0.0193 (8)	0.0050 (7)	0.0099 (7)	0.0034 (7)
S1	0.0300 (3)	0.0280 (3)	0.0163 (2)	0.0123 (2)	0.0088 (2)	0.0041 (2)
O1	0.0504 (13)	0.0511 (12)	0.0208 (8)	0.0271 (10)	0.0167 (8)	0.0156 (8)
C14	0.0352 (16)	0.0393 (15)	0.0273 (12)	0.0084 (12)	0.0185 (11)	0.0049 (11)
C15	0.0433 (18)	0.0339 (14)	0.0287 (13)	0.0102 (13)	0.0123 (13)	−0.0069 (11)
C1	0.0302 (15)	0.0411 (15)	0.0178 (11)	0.0101 (12)	−0.0017 (10)	0.0010 (10)
C2	0.0172 (12)	0.0316 (12)	0.0218 (10)	0.0084 (10)	0.0044 (9)	0.0020 (9)
C3	0.0181 (11)	0.0184 (9)	0.0179 (9)	0.0012 (8)	0.0038 (8)	0.0018 (7)
C4	0.0199 (12)	0.0243 (11)	0.0231 (10)	0.0044 (9)	0.0070 (9)	−0.0015 (8)
C5	0.0240 (13)	0.0254 (11)	0.0217 (10)	0.0001 (9)	0.0093 (9)	−0.0050 (9)
C6	0.0228 (12)	0.0259 (11)	0.0174 (10)	0.0012 (9)	0.0047 (9)	0.0010 (8)
C7	0.0193 (11)	0.0217 (10)	0.0156 (9)	0.0013 (9)	0.0038 (8)	0.0004 (8)
C8	0.0311 (15)	0.0254 (11)	0.0316 (13)	0.0110 (11)	0.0073 (11)	0.0113 (10)
C9	0.0269 (13)	0.0197 (10)	0.0251 (11)	0.0058 (9)	0.0113 (9)	0.0058 (8)
C10	0.0382 (16)	0.0195 (11)	0.0423 (15)	0.0079 (11)	0.0211 (13)	0.0063 (10)
C11	0.0410 (17)	0.0200 (11)	0.0512 (17)	−0.0061 (11)	0.0224 (14)	−0.0047 (11)
C12	0.0298 (15)	0.0251 (12)	0.0414 (15)	−0.0065 (11)	0.0101 (12)	−0.0044 (10)
C13	0.0236 (13)	0.0223 (11)	0.0276 (11)	0.0025 (9)	0.0087 (10)	0.0021 (9)

Geometric parameters (Å, º) top

Ru1—N3	2.0515 (19)	C1—H1C	0.99 (3)
Ru1—N2	2.0989 (18)	C2—C3	1.497 (3)
Ru1—N1	2.1224 (19)	C2—H2A	0.99 (3)
Ru1—S1	2.2207 (6)	C2—H2B	1.02 (3)
Ru1—Cl1	2.4187 (5)	C3—C4	1.387 (3)
Ru1—Cl2	2.4352 (6)	C4—C5	1.378 (3)
N1—C8	1.489 (3)	C4—H4	0.93 (3)
N1—C2	1.495 (3)	C5—C6	1.378 (3)
N1—C1	1.499 (3)	C5—H5	0.90 (2)
N2—C7	1.342 (3)	C6—C7	1.385 (3)
N2—C3	1.347 (3)	C6—H6	0.92 (3)
N3—C13	1.339 (3)	C7—H7	0.97 (3)
N3—C9	1.355 (3)	C8—C9	1.493 (4)
S1—O1	1.4838 (18)	C8—H8A	0.98 (3)
S1—C14	1.788 (3)	C8—H8B	0.89 (3)
S1—C15	1.791 (3)	C9—C10	1.389 (3)
C14—H14A	0.91 (4)	C10—C11	1.364 (4)
C14—H14B	0.96 (3)	C10—H10	0.92 (3)
C14—H14C	0.96 (3)	C11—C12	1.390 (4)
C15—H15A	0.97 (3)	C11—H11	0.90 (3)
C15—H15B	1.03 (4)	C12—C13	1.378 (3)
C15—H15C	0.97 (3)	C12—H12	0.97 (3)
C1—H1A	0.99 (3)	C13—H13	0.85 (3)
C1—H1B	0.99 (3)

N3—Ru1—N2	81.96 (7)	H1A—C1—H1B	110 (2)
N3—Ru1—N1	82.34 (8)	N1—C1—H1C	107.1 (17)
N2—Ru1—N1	81.70 (7)	H1A—C1—H1C	109 (2)
N3—Ru1—S1	91.40 (5)	H1B—C1—H1C	109 (2)
N2—Ru1—S1	173.35 (5)	N1—C2—C3	112.92 (19)
N1—Ru1—S1	97.82 (5)	N1—C2—H2A	111.3 (15)
N3—Ru1—Cl1	95.80 (5)	C3—C2—H2A	113.0 (15)
N2—Ru1—Cl1	91.57 (5)	N1—C2—H2B	104.0 (17)
N1—Ru1—Cl1	173.20 (5)	C3—C2—H2B	107.0 (17)
S1—Ru1—Cl1	88.75 (2)	H2A—C2—H2B	108 (2)
N3—Ru1—Cl2	170.84 (6)	N2—C3—C4	121.8 (2)
N2—Ru1—Cl2	91.40 (5)	N2—C3—C2	114.98 (19)
N1—Ru1—Cl2	90.49 (6)	C4—C3—C2	123.2 (2)
S1—Ru1—Cl2	95.24 (2)	C5—C4—C3	119.5 (2)
Cl1—Ru1—Cl2	90.66 (2)	C5—C4—H4	120.7 (16)
C8—N1—C2	112.4 (2)	C3—C4—H4	119.8 (16)
C8—N1—C1	107.8 (2)	C6—C5—C4	118.7 (2)
C2—N1—C1	106.6 (2)	C6—C5—H5	120.2 (17)
C8—N1—Ru1	106.67 (15)	C4—C5—H5	120.8 (16)
C2—N1—Ru1	106.15 (13)	C5—C6—C7	119.3 (2)
C1—N1—Ru1	117.32 (15)	C5—C6—H6	122.0 (17)
C7—N2—C3	118.54 (19)	C7—C6—H6	118.6 (17)
C7—N2—Ru1	126.34 (16)	N2—C7—C6	122.2 (2)
C3—N2—Ru1	113.84 (14)	N2—C7—H7	115.1 (16)
C13—N3—C9	118.5 (2)	C6—C7—H7	122.7 (16)
C13—N3—Ru1	126.20 (16)	N1—C8—C9	113.56 (19)
C9—N3—Ru1	114.71 (16)	N1—C8—H8A	108.0 (18)
O1—S1—C14	105.03 (13)	C9—C8—H8A	106.0 (18)
O1—S1—C15	106.66 (13)	N1—C8—H8B	111.6 (18)
C14—S1—C15	99.25 (15)	C9—C8—H8B	109.2 (18)
O1—S1—Ru1	120.38 (8)	H8A—C8—H8B	108 (2)
C14—S1—Ru1	110.28 (9)	N3—C9—C10	121.1 (2)
C15—S1—Ru1	112.91 (11)	N3—C9—C8	115.5 (2)
S1—C14—H14A	112 (2)	C10—C9—C8	123.2 (2)
S1—C14—H14B	108.9 (19)	C11—C10—C9	119.8 (2)
H14A—C14—H14B	108 (3)	C11—C10—H10	121.3 (18)
S1—C14—H14C	105.6 (19)	C9—C10—H10	118.9 (18)
H14A—C14—H14C	112 (3)	C10—C11—C12	119.3 (2)
H14B—C14—H14C	111 (3)	C10—C11—H11	124 (2)
S1—C15—H15A	108.2 (18)	C12—C11—H11	115 (2)
S1—C15—H15B	107 (2)	C13—C12—C11	118.4 (3)
H15A—C15—H15B	115 (3)	C13—C12—H12	123.9 (16)
S1—C15—H15C	112.1 (17)	C11—C12—H12	117.6 (16)
H15A—C15—H15C	111 (2)	N3—C13—C12	122.8 (2)
H15B—C15—H15C	104 (3)	N3—C13—H13	113 (2)
N1—C1—H1A	111.2 (14)	C12—C13—H13	124 (2)
N1—C1—H1B	110.4 (18)

N1—C8—C9—N3	−28.0 (3)	N1—C2—C3—N2	34.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O1ⁱ	0.91 (4)	2.54 (4)	3.431 (3)	169 (3)
C4—H4···Cl1ⁱⁱ	0.93 (3)	2.58 (3)	3.487 (2)	165 (2)
C1—H1C···O1	0.99 (3)	2.32 (3)	3.182 (4)	145 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O1ⁱ	0.91 (4)	2.54 (4)	3.431 (3)	169 (3)
C4—H4···Cl1ⁱⁱ	0.93 (3)	2.58 (3)	3.487 (2)	165 (2)
C1—H1C···O1	0.99 (3)	2.32 (3)	3.182 (4)	145 (2)

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

Acknowledgements

We gratefully acknowledge the University of Wyoming (AN and EBH), the Wyoming NASA Space Grant Consortium (NASA grant No. NNX10AO95H) and the National Science Foundation REU Program (KT, CHE-1358498) for financial support.

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