(2,2′-Bipyridine-κ2N,N′)bromido(1,4,7-trithia­cyclo­nonane-κ3S,S′,S′′)ruthenium(II) hexa­fluoridophosphate

Fernandes, J.A.; Almeida Paz, F.A.; Ramos, A.I.; Santos, T.M.; Braga, S.S.

doi:10.1107/S1600536811002662

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page m263

doi:10.1107/S1600536811002662

Open

access

(2,2′-Bipyridine-κ²N,N′)bromido(1,4,7-trithiacyclononane-κ³S,S′,S′′)ruthenium(II) hexafluoridophosphate

José A. Fernandes,^a Filipe A. Almeida Paz,^a ^* Ana I. Ramos,^a Teresa M. Santos ^a and Susana S. Braga ^a

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 18 January 2011; accepted 19 January 2011; online 26 January 2011)

The title compound, [RuBr(C₁₀H₈N₂)(C₆H₁₂S₃)]PF₆ or [RuBr(bpy)([9]aneS₃)]PF₆ ([9]aneS₃ is 1,4,7-trithiacyclononane and bpy is 2,2′-bipyridine), exhibits a very similar octahedral coordination geometry for the Ru²⁺ atom to that of its [RuCl(bpy)([9]aneS₃)]⁺ analogue, with only the chloride ligand being substituted by a bromide ligand. The presence of a PF₆⁻ anion (alongside with the coordinated bromide ligand) promotes the existence of an extensive network of weak C—H⋯X (X = F, Br) interactions.

Related literature

For general background to the cytotoxic activity of compounds with the {Ru[9]aneS₃} moiety, see: Bratsos et al. (2008 ); Serli et al. (2005 ). For isotypic compounds based on the [RuCl(bpy)([9]aneS₃)]⁺ cation, see: Serli et al. (2005); Goodfellow et al. (1997 ); Fernandes et al. (2010 ). For previous work from our research group on the use of related compounds, see: Marques, Braga et al. (2009 ); Marques, Santos et al. (2009 ).

Experimental

Crystal data

[RuBr(C₁₀H₈N₂)(C₆H₁₂S₃)]PF₆
M_r = 662.47
Monoclinic, P 2₁ /c
a = 12.0660 (7) Å
b = 13.4377 (8) Å
c = 13.3359 (8) Å
β = 98.446 (3)°
V = 2138.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.03 mm⁻¹
T = 150 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker APEXII X8 KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.643, T_max = 0.752
38626 measured reflections
5736 independent reflections
4989 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.046
S = 1.06
5736 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Br1ⁱ	0.95	2.90	3.6274 (19)	135
C8—H8⋯F1ⁱⁱ	0.95	2.42	3.039 (2)	122
C11—H11A⋯F1ⁱⁱⁱ	0.99	2.41	3.292 (2)	149
C15—H15A⋯Br1^iv	0.99	2.84	3.7627 (18)	156
C16—H16A⋯F6^v	0.99	2.41	3.170 (2)	133
Symmetry codes: (i) -x+2, -y, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002662/cv5041sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002662/cv5041Isup2.hkl

checkCIF report

Comment top

The cytotoxic potential of ruthenium coordination complexes containing 1,4,7-trithiacyclononane ([9]aneS₃) is under study since 2005 (Bratsos et al., 2008; Serli et al., 2005). We have investigated the cytotoxicity of the [RuCl(glycinate)([9]aneS₃)] complex on human osteosarcoma and breast cancer cells (Marques, Santos et al., 2009), and the antimicrobial properties of the [RuCl(1,10-phenanthroline)([9]aneS₃)]Cl complex and its β- and permethylated β-cyclodextrin inclusion compounds (Marques, Braga et al., 2009). We are currently focused on complexes with ([9]aneS₃)Ru while bearing N,N-chelated 2,2'-bipyridine (bpy). Recently, we have successfully isolated the monohydrate form of the [RuCl(bpy)([9]aneS₃)]NO₃ compound (Fernandes et al., 2010). We wish to report here the structure of [RuBr(bpy)([9]aneS₃)]PF₆, isolated as a secondary product from a crystallization batch containing (among other entities) KBr.

The asymmetric unit of the title compound is composed of a whole [RuBr(bpy)([9]aneS₃)]⁺ cation and a charge-balancing PF₆^- anion. The cation of the title compound shares striking similarities with its [RuCl(bpy)([9]aneS₃)]⁺ analogue (Serli et al., 2005; Goodfellow et al., 1997; Fernandes et al., 2010), with comparable bond lengths and angles of the coordination environments of Ru²⁺. The difference resides in the substitution of the chlorido ligand by a bromido one, with the Ru1—Br1 distance being enlongated to 2.5720 (2) Å.

The crystal packing is governed by the need to fill the available space and an overall minimization of the interionic distances (Figure 2). Nevertheless, a handful of weak hydrogen bonding interactions is present, namely C—H groups (both aromatic and methylene) interacting with Br and F of neighbouring ions (not shown; see Table 1 for details). Indeed, the existence of several C—H···F interactions seems to be the structural reason for the absence of the disorder typically associated with the PF₆^- anion.

Related literature top

For general background to the cytotoxic activity of compounds with the {Ru[9]aneS₃} moiety, see: Bratsos et al. (2008); Serli et al. (2005). For isotypic compounds based on the [Cl(bpy)([9]aneS₃)Ru]⁺ cation, see: Serli et al. (2005); Goodfellow et al. (1997); Fernandes et al. (2010). For previous work from our research group on the use of related compounds, see: Marques, Braga et al. (2009); Marques, Santos et al. (2009).

Experimental top

Chemicals were purchased from commercial sources and were used as received without purification.

Solid KBr (0.0945 g, 79.4 µmol, Sigma-Aldrich) was added to an aqueous solution (2 ml) of γ-cyclodextrin (0.130 g, 101 µmol, Wacker). The resulting solution was poured into a sample holder containing [RuCl([9]aneS₃)bpy]PF₆ (0.0248 g, 40.1 µmol). The mixture was magnetically stirred for 1 h at 60 °C. The total volume was then increased by adding 2 ml of distilled water and the temperature was also raised to 70 °C. The mixture was allowed to stir for another hour, after which it was syringe-filtered (nylon, 0.2 µm). The clear solution was allowed to crystallize by slow cooling to ambient temperature inside a sealed container. Orange crystals of the title compound were formed and isolated after two days.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title compound, with non-hydrogen atoms represented as displacement ellipsoids drawn at the 70% probability level and hydrogen atoms as small spheres with arbitrary radii. The labelling scheme is provided for all non-hydrogen atoms.
	Fig. 2. Crystal packing of the title compound viewed in perspective along the b axis.

(2,2'-Bipyridine-κ²N,N')bromido(1,4,7-trithiacyclononane- κ³S,S',S'')ruthenium(II) hexafluoridophosphate top

Crystal data top

[RuBr(C₁₀H₈N₂)(C₆H₁₂S₃)]PF₆	F(000) = 1304
M_r = 662.47	D_x = 2.057 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9897 reflections
a = 12.0660 (7) Å	θ = 2.6–30.4°
b = 13.4377 (8) Å	µ = 3.03 mm⁻¹
c = 13.3359 (8) Å	T = 150 K
β = 98.446 (3)°	Block, orange
V = 2138.8 (2) Å³	0.16 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII X8 KappaCCD diffractometer	5736 independent reflections
Radiation source: fine-focus sealed tube	4989 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and ϕ scans	θ_max = 29.1°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −16→13
T_min = 0.643, T_max = 0.752	k = −14→18
38626 measured reflections	l = −18→15

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: inferred from neighbouring sites
wR(F²) = 0.046	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0166P)² + 1.1306P] where P = (F_o² + 2F_c²)/3
5736 reflections	(Δ/σ)_max = 0.002
271 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[RuBr(C₁₀H₈N₂)(C₆H₁₂S₃)]PF₆	V = 2138.8 (2) Å³
M_r = 662.47	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0660 (7) Å	µ = 3.03 mm⁻¹
b = 13.4377 (8) Å	T = 150 K
c = 13.3359 (8) Å	0.16 × 0.12 × 0.10 mm
β = 98.446 (3)°

Data collection top

Bruker APEXII X8 KappaCCD diffractometer	5736 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	4989 reflections with I > 2σ(I)
T_min = 0.643, T_max = 0.752	R_int = 0.035
38626 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.046	H-atom parameters constrained
S = 1.06	Δρ_max = 0.52 e Å⁻³
5736 reflections	Δρ_min = −0.63 e Å⁻³
271 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.

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	0.833904 (11)	0.100271 (10)	0.308671 (10)	0.01013 (4)
Br1	0.971376 (14)	0.213830 (13)	0.421622 (13)	0.01640 (5)
S1	0.71000 (3)	0.00388 (3)	0.20501 (3)	0.01421 (9)
S2	0.88870 (4)	0.17069 (3)	0.16651 (3)	0.01378 (9)
S3	0.96835 (3)	−0.02031 (3)	0.29973 (3)	0.01433 (9)
N1	0.77196 (11)	0.04462 (11)	0.43571 (10)	0.0125 (3)
N2	0.71002 (12)	0.20371 (11)	0.32732 (10)	0.0126 (3)
C1	0.81031 (15)	−0.03531 (14)	0.49059 (13)	0.0173 (4)
H1	0.8766	−0.0668	0.4760	0.021*
C2	0.75773 (16)	−0.07386 (15)	0.56726 (14)	0.0197 (4)
H2	0.7866	−0.1313	0.6035	0.024*
C3	0.66248 (16)	−0.02759 (14)	0.59036 (14)	0.0195 (4)
H3	0.6240	−0.0534	0.6419	0.023*
C4	0.62398 (15)	0.05704 (14)	0.53721 (13)	0.0182 (4)
H4	0.5599	0.0911	0.5534	0.022*
C5	0.67964 (14)	0.09190 (13)	0.46003 (13)	0.0135 (3)
C6	0.64656 (14)	0.18211 (13)	0.40071 (13)	0.0128 (3)
C7	0.55971 (14)	0.24479 (14)	0.41964 (13)	0.0165 (4)
H7	0.5145	0.2275	0.4696	0.020*
C8	0.53990 (15)	0.33168 (14)	0.36549 (14)	0.0191 (4)
H8	0.4811	0.3750	0.3777	0.023*
C9	0.60684 (15)	0.35527 (14)	0.29292 (14)	0.0186 (4)
H9	0.5958	0.4156	0.2556	0.022*
C10	0.68995 (15)	0.28951 (14)	0.27577 (13)	0.0169 (4)
H10	0.7350	0.3055	0.2253	0.020*
C11	0.69306 (15)	0.07354 (14)	0.08615 (13)	0.0177 (4)
H11A	0.6553	0.0307	0.0311	0.021*
H11B	0.6441	0.1317	0.0922	0.021*
C12	0.80353 (15)	0.10941 (14)	0.05783 (13)	0.0176 (4)
H12A	0.7890	0.1569	0.0006	0.021*
H12B	0.8454	0.0521	0.0355	0.021*
C13	1.02665 (15)	0.11727 (14)	0.16039 (15)	0.0185 (4)
H13A	1.0454	0.1271	0.0913	0.022*
H13B	1.0831	0.1534	0.2083	0.022*
C14	1.03368 (15)	0.00714 (14)	0.18570 (14)	0.0188 (4)
H14A	1.1132	−0.0137	0.1976	0.023*
H14B	0.9952	−0.0315	0.1275	0.023*
C15	0.88524 (15)	−0.12899 (13)	0.25441 (14)	0.0168 (4)
H15A	0.9348	−0.1787	0.2289	0.020*
H15B	0.8544	−0.1593	0.3120	0.020*
C16	0.78971 (15)	−0.10518 (13)	0.17114 (14)	0.0180 (4)
H16A	0.7391	−0.1633	0.1596	0.022*
H16B	0.8199	−0.0915	0.1074	0.022*
P1	0.34992 (4)	0.16856 (4)	0.13197 (4)	0.01782 (10)
F1	0.39585 (10)	0.13350 (10)	0.03098 (9)	0.0359 (3)
F2	0.41610 (11)	0.27096 (10)	0.12942 (10)	0.0384 (3)
F3	0.45640 (10)	0.11898 (10)	0.19885 (10)	0.0372 (3)
F4	0.28321 (10)	0.06540 (9)	0.13318 (10)	0.0327 (3)
F5	0.24266 (10)	0.21698 (10)	0.06555 (10)	0.0367 (3)
F6	0.30399 (11)	0.20190 (9)	0.23321 (9)	0.0343 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01007 (7)	0.00943 (7)	0.01135 (7)	0.00047 (5)	0.00314 (5)	−0.00005 (5)
Br1	0.01564 (9)	0.01541 (10)	0.01780 (9)	−0.00099 (7)	0.00133 (7)	−0.00329 (7)
S1	0.0131 (2)	0.0135 (2)	0.0161 (2)	−0.00181 (17)	0.00253 (16)	0.00033 (17)
S2	0.0153 (2)	0.0123 (2)	0.0147 (2)	−0.00110 (17)	0.00545 (16)	0.00033 (17)
S3	0.0128 (2)	0.0124 (2)	0.0185 (2)	0.00123 (17)	0.00418 (16)	0.00010 (18)
N1	0.0130 (7)	0.0127 (8)	0.0120 (7)	0.0009 (6)	0.0023 (5)	−0.0006 (6)
N2	0.0132 (7)	0.0121 (8)	0.0123 (7)	0.0007 (6)	0.0017 (5)	−0.0012 (6)
C1	0.0190 (9)	0.0166 (10)	0.0163 (9)	0.0032 (8)	0.0022 (7)	0.0006 (7)
C2	0.0264 (10)	0.0165 (10)	0.0160 (9)	0.0005 (8)	0.0027 (7)	0.0036 (8)
C3	0.0252 (10)	0.0192 (10)	0.0155 (9)	−0.0027 (8)	0.0073 (7)	0.0021 (8)
C4	0.0184 (9)	0.0188 (10)	0.0183 (9)	0.0003 (8)	0.0061 (7)	−0.0009 (8)
C5	0.0141 (8)	0.0131 (9)	0.0130 (8)	−0.0011 (7)	0.0013 (6)	−0.0028 (7)
C6	0.0118 (8)	0.0142 (9)	0.0122 (8)	−0.0008 (7)	0.0008 (6)	−0.0019 (7)
C7	0.0138 (8)	0.0198 (10)	0.0167 (9)	0.0007 (7)	0.0047 (7)	−0.0016 (8)
C8	0.0175 (9)	0.0193 (10)	0.0202 (9)	0.0074 (8)	0.0021 (7)	−0.0022 (8)
C9	0.0234 (9)	0.0144 (9)	0.0174 (9)	0.0047 (8)	0.0013 (7)	0.0020 (7)
C10	0.0186 (9)	0.0169 (10)	0.0160 (9)	0.0014 (7)	0.0051 (7)	0.0012 (7)
C11	0.0187 (9)	0.0181 (10)	0.0154 (9)	−0.0013 (8)	−0.0011 (7)	0.0017 (8)
C12	0.0206 (9)	0.0185 (10)	0.0137 (9)	−0.0014 (8)	0.0026 (7)	−0.0004 (7)
C13	0.0152 (8)	0.0183 (10)	0.0239 (10)	−0.0026 (8)	0.0093 (7)	−0.0004 (8)
C14	0.0174 (9)	0.0177 (10)	0.0237 (10)	0.0007 (8)	0.0108 (7)	−0.0011 (8)
C15	0.0207 (9)	0.0094 (9)	0.0214 (9)	0.0014 (7)	0.0067 (7)	0.0001 (7)
C16	0.0217 (9)	0.0110 (9)	0.0215 (10)	−0.0013 (7)	0.0036 (7)	−0.0031 (7)
P1	0.0179 (2)	0.0200 (3)	0.0164 (2)	−0.0014 (2)	0.00541 (18)	0.0004 (2)
F1	0.0393 (7)	0.0464 (8)	0.0265 (7)	−0.0168 (6)	0.0197 (5)	−0.0138 (6)
F2	0.0476 (8)	0.0305 (7)	0.0366 (7)	−0.0212 (6)	0.0052 (6)	−0.0047 (6)
F3	0.0240 (6)	0.0488 (8)	0.0377 (7)	0.0119 (6)	0.0007 (5)	0.0029 (6)
F4	0.0318 (7)	0.0226 (6)	0.0474 (8)	−0.0071 (5)	0.0185 (6)	0.0020 (6)
F5	0.0310 (7)	0.0393 (8)	0.0368 (7)	0.0034 (6)	−0.0051 (6)	0.0124 (6)
F6	0.0441 (7)	0.0375 (8)	0.0246 (6)	0.0123 (6)	0.0157 (6)	−0.0023 (6)

Geometric parameters (Å, º) top

Ru1—N1	2.0881 (14)	C7—H7	0.9500
Ru1—N2	2.0826 (14)	C8—C9	1.385 (3)
Ru1—S1	2.2840 (5)	C8—H8	0.9500
Ru1—S2	2.3011 (4)	C9—C10	1.381 (3)
Ru1—S3	2.3083 (5)	C9—H9	0.9500
Ru1—Br1	2.5720 (2)	C10—H10	0.9500
S1—C11	1.8264 (18)	C11—C12	1.516 (2)
S1—C16	1.8451 (18)	C11—H11A	0.9900
S2—C13	1.8255 (18)	C11—H11B	0.9900
S2—C12	1.8432 (18)	C12—H12A	0.9900
S3—C15	1.8236 (19)	C12—H12B	0.9900
S3—C14	1.8499 (17)	C13—C14	1.517 (3)
N1—C1	1.343 (2)	C13—H13A	0.9900
N1—C5	1.362 (2)	C13—H13B	0.9900
N2—C10	1.346 (2)	C14—H14A	0.9900
N2—C6	1.360 (2)	C14—H14B	0.9900
C1—C2	1.381 (2)	C15—C16	1.513 (3)
C1—H1	0.9500	C15—H15A	0.9900
C2—C3	1.381 (3)	C15—H15B	0.9900
C2—H2	0.9500	C16—H16A	0.9900
C3—C4	1.384 (3)	C16—H16B	0.9900
C3—H3	0.9500	P1—F2	1.5938 (13)
C4—C5	1.390 (2)	P1—F5	1.5956 (13)
C4—H4	0.9500	P1—F6	1.5970 (12)
C5—C6	1.470 (2)	P1—F3	1.5980 (13)
C6—C7	1.396 (2)	P1—F1	1.6007 (12)
C7—C8	1.375 (3)	P1—F4	1.6043 (12)

N2—Ru1—N1	78.08 (5)	C8—C9—H9	120.6
N2—Ru1—S1	91.91 (4)	N2—C10—C9	122.97 (16)
N1—Ru1—S1	90.43 (4)	N2—C10—H10	118.5
N2—Ru1—S2	97.01 (4)	C9—C10—H10	118.5
S1—Ru1—S2	88.644 (16)	C12—C11—S1	112.87 (13)
N1—Ru1—S3	97.38 (4)	C12—C11—H11A	109.0
S1—Ru1—S3	88.460 (17)	S1—C11—H11A	109.0
S2—Ru1—S3	87.533 (16)	C12—C11—H11B	109.0
N2—Ru1—Br1	86.93 (4)	S1—C11—H11B	109.0
N1—Ru1—Br1	90.81 (4)	H11A—C11—H11B	107.8
S2—Ru1—Br1	89.993 (13)	C11—C12—S2	110.80 (12)
S3—Ru1—Br1	92.811 (13)	C11—C12—H12A	109.5
N1—Ru1—S2	174.97 (4)	S2—C12—H12A	109.5
N2—Ru1—S3	175.45 (4)	C11—C12—H12B	109.5
S1—Ru1—Br1	178.095 (13)	S2—C12—H12B	109.5
C11—S1—C16	100.98 (9)	H12A—C12—H12B	108.1
C11—S1—Ru1	102.38 (6)	C14—C13—S2	113.27 (12)
C16—S1—Ru1	106.28 (6)	C14—C13—H13A	108.9
C13—S2—C12	101.30 (9)	S2—C13—H13A	108.9
C13—S2—Ru1	104.44 (6)	C14—C13—H13B	108.9
C12—S2—Ru1	105.64 (6)	S2—C13—H13B	108.9
C15—S3—C14	99.63 (8)	H13A—C13—H13B	107.7
C15—S3—Ru1	102.88 (6)	C13—C14—S3	111.14 (12)
C14—S3—Ru1	106.86 (6)	C13—C14—H14A	109.4
C1—N1—C5	118.13 (14)	S3—C14—H14A	109.4
C1—N1—Ru1	126.36 (11)	C13—C14—H14B	109.4
C5—N1—Ru1	115.39 (11)	S3—C14—H14B	109.4
C10—N2—C6	118.19 (15)	H14A—C14—H14B	108.0
C10—N2—Ru1	126.09 (11)	C16—C15—S3	113.37 (13)
C6—N2—Ru1	115.69 (11)	C16—C15—H15A	108.9
N1—C1—C2	122.99 (17)	S3—C15—H15A	108.9
N1—C1—H1	118.5	C16—C15—H15B	108.9
C2—C1—H1	118.5	S3—C15—H15B	108.9
C3—C2—C1	118.96 (18)	H15A—C15—H15B	107.7
C3—C2—H2	120.5	C15—C16—S1	110.89 (12)
C1—C2—H2	120.5	C15—C16—H16A	109.5
C2—C3—C4	118.92 (16)	S1—C16—H16A	109.5
C2—C3—H3	120.5	C15—C16—H16B	109.5
C4—C3—H3	120.5	S1—C16—H16B	109.5
C3—C4—C5	119.58 (17)	H16A—C16—H16B	108.0
C3—C4—H4	120.2	F2—P1—F5	90.24 (7)
C5—C4—H4	120.2	F2—P1—F6	90.75 (7)
N1—C5—C4	121.33 (16)	F5—P1—F6	90.06 (7)
N1—C5—C6	115.04 (14)	F2—P1—F3	90.43 (8)
C4—C5—C6	123.61 (16)	F5—P1—F3	179.30 (8)
N2—C6—C7	121.23 (16)	F6—P1—F3	89.74 (7)
N2—C6—C5	115.22 (14)	F2—P1—F1	89.98 (7)
C7—C6—C5	123.49 (15)	F5—P1—F1	90.33 (7)
C8—C7—C6	119.64 (16)	F6—P1—F1	179.17 (8)
C8—C7—H7	120.2	F3—P1—F1	89.86 (7)
C6—C7—H7	120.2	F2—P1—F4	179.36 (7)
C7—C8—C9	119.13 (17)	F5—P1—F4	89.46 (7)
C7—C8—H8	120.4	F6—P1—F4	89.83 (7)
C9—C8—H8	120.4	F3—P1—F4	89.86 (7)
C10—C9—C8	118.78 (17)	F1—P1—F4	89.45 (7)
C10—C9—H9	120.6

N2—Ru1—S1—C11	75.99 (7)	Ru1—N1—C1—C2	−173.00 (14)
N1—Ru1—S1—C11	154.07 (7)	N1—C1—C2—C3	−1.2 (3)
S2—Ru1—S1—C11	−20.99 (6)	C1—C2—C3—C4	−1.2 (3)
S3—Ru1—S1—C11	−108.55 (6)	C2—C3—C4—C5	1.9 (3)
N2—Ru1—S1—C16	−178.51 (7)	C1—N1—C5—C4	−2.1 (2)
N1—Ru1—S1—C16	−100.42 (7)	Ru1—N1—C5—C4	174.23 (13)
S2—Ru1—S1—C16	84.52 (6)	C1—N1—C5—C6	176.53 (15)
S3—Ru1—S1—C16	−3.05 (6)	Ru1—N1—C5—C6	−7.18 (19)
N2—Ru1—S2—C13	161.69 (8)	C3—C4—C5—N1	−0.3 (3)
S1—Ru1—S2—C13	−106.56 (7)	C3—C4—C5—C6	−178.74 (17)
S3—Ru1—S2—C13	−18.04 (7)	C10—N2—C6—C7	2.6 (2)
Br1—Ru1—S2—C13	74.78 (6)	Ru1—N2—C6—C7	−179.04 (13)
N2—Ru1—S2—C12	−91.93 (7)	C10—N2—C6—C5	−174.73 (15)
S1—Ru1—S2—C12	−0.17 (6)	Ru1—N2—C6—C5	3.59 (19)
S3—Ru1—S2—C12	88.35 (6)	N1—C5—C6—N2	2.4 (2)
Br1—Ru1—S2—C12	−178.84 (6)	C4—C5—C6—N2	−179.06 (16)
N1—Ru1—S3—C15	72.45 (7)	N1—C5—C6—C7	−174.92 (16)
S1—Ru1—S3—C15	−17.78 (6)	C4—C5—C6—C7	3.6 (3)
S2—Ru1—S3—C15	−106.49 (6)	N2—C6—C7—C8	−2.1 (3)
Br1—Ru1—S3—C15	163.64 (6)	C5—C6—C7—C8	175.04 (17)
N1—Ru1—S3—C14	176.84 (8)	C6—C7—C8—C9	0.0 (3)
S1—Ru1—S3—C14	86.61 (7)	C7—C8—C9—C10	1.4 (3)
S2—Ru1—S3—C14	−2.10 (7)	C6—N2—C10—C9	−1.2 (3)
Br1—Ru1—S3—C14	−91.97 (7)	Ru1—N2—C10—C9	−179.30 (14)
N2—Ru1—N1—C1	−177.12 (15)	C8—C9—C10—N2	−0.8 (3)
S1—Ru1—N1—C1	91.02 (14)	C16—S1—C11—C12	−64.36 (15)
S3—Ru1—N1—C1	2.51 (15)	Ru1—S1—C11—C12	45.21 (14)
Br1—Ru1—N1—C1	−90.43 (14)	S1—C11—C12—S2	−48.58 (17)
N2—Ru1—N1—C5	6.94 (12)	C13—S2—C12—C11	135.80 (13)
S1—Ru1—N1—C5	−84.92 (12)	Ru1—S2—C12—C11	27.14 (14)
S3—Ru1—N1—C5	−173.42 (11)	C12—S2—C13—C14	−68.39 (15)
Br1—Ru1—N1—C5	93.64 (12)	Ru1—S2—C13—C14	41.20 (15)
N1—Ru1—N2—C10	172.54 (15)	S2—C13—C14—S3	−45.34 (17)
S1—Ru1—N2—C10	−97.42 (14)	C15—S3—C14—C13	133.84 (14)
S2—Ru1—N2—C10	−8.56 (15)	Ru1—S3—C14—C13	27.13 (15)
Br1—Ru1—N2—C10	81.06 (14)	C14—S3—C15—C16	−67.85 (14)
N1—Ru1—N2—C6	−5.62 (12)	Ru1—S3—C15—C16	42.06 (13)
S1—Ru1—N2—C6	84.42 (12)	S3—C15—C16—S1	−47.66 (15)
S2—Ru1—N2—C6	173.28 (11)	C11—S1—C16—C15	135.46 (13)
Br1—Ru1—N2—C6	−97.10 (12)	Ru1—S1—C16—C15	28.95 (13)
C5—N1—C1—C2	2.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1ⁱ	0.95	2.90	3.6274 (19)	135
C8—H8···F1ⁱⁱ	0.95	2.42	3.039 (2)	122
C11—H11A···F1ⁱⁱⁱ	0.99	2.41	3.292 (2)	149
C15—H15A···Br1^iv	0.99	2.84	3.7627 (18)	156
C16—H16A···F6^v	0.99	2.41	3.170 (2)	133

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

Experimental details

Crystal data
Chemical formula	[RuBr(C₁₀H₈N₂)(C₆H₁₂S₃)]PF₆
M_r	662.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	12.0660 (7), 13.4377 (8), 13.3359 (8)
β (°)	98.446 (3)
V (Å³)	2138.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.03
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII X8 KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.643, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections	38626, 5736, 4989
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.046, 1.06
No. of reflections	5736
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.63

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1ⁱ	0.95	2.90	3.6274 (19)	135
C8—H8···F1ⁱⁱ	0.95	2.42	3.039 (2)	122
C11—H11A···F1ⁱⁱⁱ	0.99	2.41	3.292 (2)	149
C15—H15A···Br1^iv	0.99	2.84	3.7627 (18)	156
C16—H16A···F6^v	0.99	2.41	3.170 (2)	133

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

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support (R&D project PTDC/QUI/69302/2006), for the post-doctoral research grant No. SFRH/BPD/63736/2009 (to JAF) and for specific funding toward the purchase of the single-crystal diffractometer.

References

Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bratsos, I., Jedner, S., Bergamo, A., Sava, G., Gianferrara, T., Zangrando, E. & Alessio, E. (2008). J. Inorg. Biochem. 102, 1120–1133. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2005). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fernandes, J. A., Almeida Paz, F. A., Mota, M. J., Braga, S. S. & Santos, T. M. (2010). Acta Cryst. E66, m1575. Web of Science CSD CrossRef IUCr Journals Google Scholar
Goodfellow, B. J., Félix, V., Pacheco, S. M. D., Jesus, J. P. & Drew, M. G. B. (1997). Polyhedron, 16, 393–401. CSD CrossRef CAS Web of Science Google Scholar
Marques, J., Braga, T. M., Paz, F. A. A., Santos, T. M., Lopes, M. D. S. & Braga, S. S. (2009). Biometals, 22, 541–556. Web of Science CrossRef PubMed CAS Google Scholar
Marques, J., Santos, T. M., Marques, M. P. & Braga, S. S. (2009). Dalton Trans. pp. 9812–9819. Web of Science CrossRef Google Scholar
Serli, B., Zangrando, E., Gianferrara, T., Scolaro, C., Dyson, P. J., Bergamo, A. & Alessio, E. (2005). Eur. J. Inorg. Chem. pp. 3423–3434. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (1998). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.