(2,2′-Bipyridine-κ2N,N′)chlorido(1,4,7-trithia­cyclo­nonane-κ3S,S′,S′′)ruthenium(II) nitrate monohydrate

Fernandes, J.A.; Almeida Paz, F.A.; Mota, M.J.P.; Braga, S.S.; Santos, T.M.

doi:10.1107/S1600536810046556

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1575

https://doi.org/10.1107/S1600536810046556

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(2,2′-Bipyridine-κ²N,N′)chlorido(1,4,7-trithiacyclononane-κ³S,S′,S′′)ruthenium(II) nitrate monohydrate

José A. Fernandes,^a Filipe A. Almeida Paz,^a ^* Maria João P. Mota,^a Susana S. Braga ^a and Teresa M. Santos ^a

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

(Received 14 October 2010; accepted 10 November 2010; online 13 November 2010)

In the title compound, [RuCl(C₁₀H₈N₂)(C₆H₁₂S₃)]NO₃·H₂O or [RuCl(bpy)([9]aneS₃)]NO₃·H₂O, ([9]aneS₃ is 1,4,7-trithiacyclononane and bpy is 2,2′-bipyridine), the Ru^II cation has a slightly distorted octahedral environment composed of three facially coordinated S atoms from ([9]aneS₃), two N atoms from bpy and a chloride anion. The nitrate counter-ion and the water molecule of crystallization are engaged in O—H⋯O hydrogen-bonding interactions, leading to a supramolecular chain running parallel to the c axis.

Related literature

For general background on the cytotoxic activity of compounds with the (Ru[9]aneS₃) unit, see: Bratsos et al. (2008 ); Serli et al. (2005 ). For related compounds, see: Sala et al. (2004 ); Marques, Braga et al. (2009 ); Marques, Santos et al. (2009 ); Marques et al. (2008 ). For compounds with the same cation as the title compound, see: Serli et al. (2005); Goodfellow et al. (1997 ). For graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999 )

Experimental

Crystal data

[RuCl(C₁₀H₈N₂)(C₆H₁₂S₃)]NO₃·H₂O
M_r = 553.07
Monoclinic, P 2₁ /c
a = 7.6523 (4) Å
b = 25.1887 (12) Å
c = 11.1099 (5) Å
β = 108.438 (2)°
V = 2031.52 (17) Å³
Z = 4
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 150 K
0.05 × 0.04 × 0.02 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.941, T_max = 0.976
21232 measured reflections
5360 independent reflections
4179 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.078
S = 1.08
5360 reflections
259 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1X⋯O3ⁱ	0.95 (3)	2.10 (3)	3.037 (4)	169 (4)
O1W—H1Y⋯O2ⁱⁱ	0.94 (3)	1.92 (2)	2.839 (4)	166 (4)
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x-1, y, z.

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: https://doi.org/10.1107/S1600536810046556/bg2373sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046556/bg2373Isup2.hkl

checkCIF report

Comment top

The ruthenium coordination complexes containing 1,4,7-trithiacyclonane ([9]aneS₃) have been studied for their activity as antitumoral agents (Bratsos et al., 2008; Serli et al., 2005). Some members of this family of compounds have been tested as cytotoxic (Marques, Santos et al., 2009) and antimicrobial (Marques, Braga et al., 2009) agents, or as catalysts (Sala et al., 2004). We have also studied the solid-state properties of the inclusion compounds of a number of these ruthenium compounds in cyclodextrins (Marques et al., 2008). While reacting the Ru^II precursor [Ru([9]aneS₃)(bpy)Cl]Cl with AgNO₃ we isolated the title compound as a secondary product.

The asymmetric unit of the title compound (see Scheme) comprises a whole [Ru([9]aneS₃)(bpy)Cl]⁺ cation, a charge-balancing nitrate anion and a water molecule of crystallization (Figure 1). A survey in the Cambridge Structural Database revealed that this Ru^II cation has already been described by other groups while co-crystallizing with different anions, namely chloride and trifluoromethanesulfonate (Serli et al., 2005; Goodfellow et al., 1997). This cation has an octahedral coordination environment for Ru^II with the tricoordinating [9]aneS₃ molecule occupying one of the faces of the polyhedron [Ru—S distances ranging from 2.2800 (9) to 2.4379 (8) Å]. The remaining three coordination sites are occupied by a chelating 2,2'-bipyridine (bpy) [Ru—N distances of 2.088 (3) and 2.093 (3) Å], and a chlorido anion [Ru—Cl distance of 2.4379 (8) Å]. The octahedral angles of the coordination polyhedron fall within a short range of the ideal values: while the cis angles range from 77.86 (10) to 98.04 (7)°, the trans angles are in the 174.02 (8)–177.46 (3)° range.

The water molecule of crystallization and the charge-balancing nitrate anion interact via strong hydrogen bonds (Table 1), leading to a polymeric H1Y—{O1W—H1X···O3—N3—O2···H1Y}_∞ chain running parallel to the c-axis (dashed pink lines in Figure 2), which can be described by a C²₂ graph set motif (Grell et al., 1999). Noteworthy, these hydrogen bonds are of strong nature [O···O distances of 3.037 (4) and 2.839 (4) Å] and highly directional [O—H···O angles of 169 (4) and 166 (4)°].

The title compound, based on the [Ru([9]aneS₃)(bpy)Cl]⁺ cation, is considerably different from the two previously related structures: while in our structure the charge-balancing nitrate co-crystallizes with one water molecule, the chloride and trifluoromethanesulfonate structures contain three and none of these entities, respectively (Goodfellow et al., 1997; Serli et al., 2005). Noteworthy, in the former structure (having three water molecules) the crystal packing exhibits a supramolecular two-dimensional network of hydrogen bonding interactions. In the title compound the presence of a single water molecule in the composition promotes the formation of only a one-dimensional supramolecular chain (see above). In summary, it is feasible to consider the title compound as an intermediary case between the two already known structures.

Related literature top

For general background to the cytotoxic activity of compounds with the (Ru[9]aneS₃) unit, see: Bratsos et al. (2008); Serli et al. (2005). For related compounds, see: Sala et al. (2004); Marques, Braga et al. (2009); Marques, Santos et al. (2009); Marques et al. (2008). For compounds with the same cation as the title compound, see: Serli et al. (2005); Goodfellow et al. (1997). For graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999)

Experimental top

The Ru^II precursor [Ru([9]aneS₃)(bpy)Cl]Cl was prepared according to reported methods (Goodfellow et al., 1997). Remaining chemicals were purchased from commercial sources and used as received without further purification. [Ru([9]aneS₃)(bpy)Cl]Cl (105.6 mg; 0.21 mmol) was treated with AgNO₃ (53.0 mg; 0.31 mmol) in order to produce an intermediate labile species by exchanging the coordinated Cl^- ligand by a solvent molecule (20 minutes stirring at room temperature in 50 ml of commercial grade ethanol). A white precipitate (AgCl) was filtered off through Celite, and the volume of the remaining red-orange solution was reduced to half by evaporation at 50 °C in a rotatory evaporator. After one month at -18 °C, the title compound was isolated as orange crystals.

Structure description top

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. Non-hydrogen atoms are represented as thermal ellipsoids drawn at the 50% probability level while hydrogen atoms are drawn 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 a axis. The C²₂ chain is highlighted in dashed pink lines. For geometrical details on the represented hydrogen bonding interactions see Table 1.

(2,2'-Bipyridine-κ²N,N')chlorido(1,4,7-trithiacyclononane- κ³S,S',S'')ruthenium(II) nitrate monohydrate top

Crystal data top

[RuCl(C₁₀H₈N₂)(C₆H₁₂S₃)]NO₃·H₂O	F(000) = 1120
M_r = 553.07	D_x = 1.808 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5581 reflections
a = 7.6523 (4) Å	θ = 2.5–30.4°
b = 25.1887 (12) Å	µ = 1.24 mm⁻¹
c = 11.1099 (5) Å	T = 150 K
β = 108.438 (2)°	Block, orange
V = 2031.52 (17) Å³	0.05 × 0.04 × 0.02 mm
Z = 4

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	5360 independent reflections
Radiation source: fine-focus sealed tube	4179 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω and φ scans	θ_max = 29.1°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −10→9
T_min = 0.941, T_max = 0.976	k = −34→29
21232 measured reflections	l = −15→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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.026P)² + 1.766P] where P = (F_o² + 2F_c²)/3
5360 reflections	(Δ/σ)_max = 0.002
259 parameters	Δρ_max = 0.74 e Å⁻³
3 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[RuCl(C₁₀H₈N₂)(C₆H₁₂S₃)]NO₃·H₂O	V = 2031.52 (17) Å³
M_r = 553.07	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6523 (4) Å	µ = 1.24 mm⁻¹
b = 25.1887 (12) Å	T = 150 K
c = 11.1099 (5) Å	0.05 × 0.04 × 0.02 mm
β = 108.438 (2)°

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	5360 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	4179 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.976	R_int = 0.048
21232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	3 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.74 e Å⁻³
5360 reflections	Δρ_min = −0.60 e Å⁻³
259 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	0.57746 (4)	0.910714 (10)	0.22233 (2)	0.01142 (7)
S1	0.38460 (11)	0.90192 (3)	0.01591 (7)	0.01507 (17)
S2	0.68086 (11)	0.82613 (3)	0.20539 (7)	0.01433 (17)
S3	0.35078 (11)	0.87415 (3)	0.28829 (7)	0.01582 (17)
Cl1	0.81988 (11)	0.94626 (3)	0.14642 (7)	0.01768 (17)
N1	0.5087 (4)	0.98857 (10)	0.2537 (2)	0.0143 (6)
N2	0.7509 (4)	0.92503 (10)	0.4070 (2)	0.0147 (6)
N3	0.9073 (4)	0.70605 (11)	0.2395 (3)	0.0225 (7)
O1	0.7828 (3)	0.70188 (10)	0.1357 (2)	0.0280 (6)
O2	1.0661 (4)	0.71932 (12)	0.2423 (2)	0.0385 (7)
O3	0.8748 (4)	0.69717 (11)	0.3408 (2)	0.0355 (7)
C1	0.3886 (5)	1.02027 (13)	0.1688 (3)	0.0189 (7)
H1	0.3243	1.0063	0.0874	0.023*
C2	0.3555 (5)	1.07204 (13)	0.1954 (3)	0.0206 (7)
H2	0.2682	1.0928	0.1335	0.025*
C3	0.4493 (5)	1.09354 (14)	0.3120 (3)	0.0233 (8)
H3	0.4284	1.1292	0.3317	0.028*
C4	0.5749 (5)	1.06186 (14)	0.3996 (3)	0.0199 (7)
H4	0.6424	1.0758	0.4804	0.024*
C5	0.6021 (4)	1.00952 (13)	0.3691 (3)	0.0143 (7)
C6	0.7357 (4)	0.97384 (13)	0.4554 (3)	0.0153 (7)
C7	0.8451 (5)	0.98784 (14)	0.5772 (3)	0.0187 (7)
H7	0.8325	1.0219	0.6104	0.022*
C8	0.9720 (5)	0.95207 (15)	0.6495 (3)	0.0224 (8)
H8	1.0458	0.9610	0.7332	0.027*
C9	0.9903 (5)	0.90346 (14)	0.5989 (3)	0.0214 (8)
H9	1.0786	0.8786	0.6464	0.026*
C10	0.8781 (5)	0.89129 (14)	0.4777 (3)	0.0185 (7)
H10	0.8917	0.8577	0.4430	0.022*
C11	0.4255 (5)	0.83499 (13)	−0.0368 (3)	0.0179 (7)
H11A	0.3333	0.8101	−0.0234	0.021*
H11B	0.4098	0.8358	−0.1287	0.021*
C12	0.6176 (5)	0.81530 (13)	0.0351 (3)	0.0172 (7)
H12A	0.7076	0.8337	0.0024	0.021*
H12B	0.6248	0.7769	0.0189	0.021*
C13	0.5226 (5)	0.78117 (13)	0.2499 (3)	0.0169 (7)
H13A	0.4228	0.7702	0.1727	0.020*
H13B	0.5901	0.7489	0.2900	0.020*
C14	0.4398 (5)	0.80803 (13)	0.3412 (3)	0.0179 (7)
H14A	0.5350	0.8109	0.4255	0.022*
H14B	0.3385	0.7857	0.3508	0.022*
C15	0.1622 (4)	0.85625 (14)	0.1442 (3)	0.0191 (7)
H15A	0.1780	0.8190	0.1211	0.023*
H15B	0.0433	0.8589	0.1614	0.023*
C16	0.1581 (4)	0.89212 (14)	0.0344 (3)	0.0189 (7)
H16A	0.1075	0.9271	0.0472	0.023*
H16B	0.0743	0.8767	−0.0448	0.023*
O1W	0.1468 (4)	0.72516 (12)	0.0102 (3)	0.0371 (7)
H1X	0.058 (4)	0.7458 (15)	−0.051 (3)	0.056*
H1Y	0.106 (5)	0.7187 (17)	0.080 (2)	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01225 (13)	0.01040 (12)	0.01162 (11)	−0.00014 (11)	0.00379 (9)	−0.00145 (10)
S1	0.0154 (4)	0.0154 (4)	0.0138 (3)	0.0000 (3)	0.0038 (3)	−0.0017 (3)
S2	0.0147 (4)	0.0127 (4)	0.0161 (4)	−0.0002 (3)	0.0057 (3)	−0.0014 (3)
S3	0.0167 (4)	0.0155 (4)	0.0169 (4)	−0.0006 (4)	0.0077 (3)	−0.0015 (3)
Cl1	0.0169 (4)	0.0177 (4)	0.0201 (4)	−0.0022 (3)	0.0082 (3)	−0.0017 (3)
N1	0.0150 (14)	0.0133 (14)	0.0166 (12)	0.0005 (12)	0.0078 (11)	−0.0011 (10)
N2	0.0174 (15)	0.0122 (14)	0.0152 (12)	−0.0022 (12)	0.0062 (11)	0.0004 (10)
N3	0.0270 (18)	0.0167 (15)	0.0242 (15)	0.0051 (14)	0.0085 (13)	0.0028 (12)
O1	0.0273 (15)	0.0213 (14)	0.0292 (14)	0.0035 (12)	0.0002 (11)	−0.0024 (11)
O2	0.0268 (16)	0.0520 (19)	0.0373 (16)	−0.0106 (15)	0.0109 (12)	−0.0049 (14)
O3	0.0439 (18)	0.0402 (17)	0.0278 (14)	0.0133 (15)	0.0187 (13)	0.0132 (12)
C1	0.0197 (18)	0.0180 (18)	0.0209 (16)	0.0022 (15)	0.0094 (14)	0.0007 (13)
C2	0.0216 (19)	0.0142 (17)	0.0294 (18)	0.0067 (15)	0.0126 (15)	0.0052 (14)
C3	0.029 (2)	0.0152 (17)	0.0317 (18)	−0.0002 (17)	0.0179 (16)	−0.0038 (14)
C4	0.0220 (19)	0.0204 (18)	0.0211 (16)	−0.0023 (16)	0.0124 (14)	−0.0053 (14)
C5	0.0139 (16)	0.0161 (17)	0.0173 (15)	−0.0035 (14)	0.0114 (13)	−0.0020 (12)
C6	0.0155 (17)	0.0163 (17)	0.0163 (15)	−0.0073 (14)	0.0080 (13)	−0.0025 (12)
C7	0.0206 (18)	0.0195 (18)	0.0167 (15)	−0.0086 (15)	0.0078 (13)	−0.0065 (13)
C8	0.0209 (19)	0.031 (2)	0.0132 (15)	−0.0135 (17)	0.0025 (13)	−0.0018 (14)
C9	0.0181 (18)	0.0226 (19)	0.0202 (16)	−0.0038 (16)	0.0019 (13)	0.0050 (14)
C10	0.0184 (18)	0.0172 (17)	0.0181 (15)	−0.0027 (15)	0.0028 (13)	0.0002 (13)
C11	0.0224 (18)	0.0160 (17)	0.0147 (15)	−0.0014 (15)	0.0053 (13)	−0.0066 (12)
C12	0.0242 (19)	0.0137 (16)	0.0162 (15)	0.0012 (15)	0.0096 (13)	−0.0034 (12)
C13	0.0205 (18)	0.0113 (15)	0.0204 (16)	0.0001 (14)	0.0085 (13)	0.0027 (13)
C14	0.0217 (18)	0.0162 (17)	0.0180 (16)	−0.0017 (15)	0.0095 (14)	0.0031 (13)
C15	0.0111 (17)	0.0217 (18)	0.0237 (17)	−0.0013 (15)	0.0046 (13)	−0.0044 (14)
C16	0.0123 (17)	0.0213 (18)	0.0215 (16)	−0.0006 (15)	0.0031 (13)	−0.0016 (13)
O1W	0.0376 (17)	0.0435 (18)	0.0324 (15)	−0.0048 (15)	0.0139 (13)	0.0038 (13)

Geometric parameters (Å, º) top

Ru1—N1	2.088 (3)	C5—C6	1.467 (5)
Ru1—N2	2.093 (3)	C6—C7	1.392 (4)
Ru1—S3	2.2800 (9)	C7—C8	1.381 (5)
Ru1—S2	2.3012 (8)	C7—H7	0.9500
Ru1—S1	2.3120 (8)	C8—C9	1.372 (5)
Ru1—Cl1	2.4379 (8)	C8—H8	0.9500
S1—C16	1.825 (3)	C9—C10	1.382 (4)
S1—C11	1.843 (3)	C9—H9	0.9500
S2—C12	1.819 (3)	C10—H10	0.9500
S2—C13	1.836 (3)	C11—C12	1.517 (5)
S3—C14	1.825 (3)	C11—H11A	0.9900
S3—C15	1.841 (3)	C11—H11B	0.9900
N1—C1	1.350 (4)	C12—H12A	0.9900
N1—C5	1.361 (4)	C12—H12B	0.9900
N2—C10	1.343 (4)	C13—C14	1.515 (4)
N2—C6	1.361 (4)	C13—H13A	0.9900
N3—O1	1.247 (4)	C13—H13B	0.9900
N3—O3	1.247 (4)	C14—H14A	0.9900
N3—O2	1.251 (4)	C14—H14B	0.9900
C1—C2	1.378 (5)	C15—C16	1.510 (5)
C1—H1	0.9500	C15—H15A	0.9900
C2—C3	1.378 (5)	C15—H15B	0.9900
C2—H2	0.9500	C16—H16A	0.9900
C3—C4	1.385 (5)	C16—H16B	0.9900
C3—H3	0.9500	O1W—H1X	0.95 (3)
C4—C5	1.393 (4)	O1W—H1Y	0.94 (3)
C4—H4	0.9500

N1—Ru1—N2	77.86 (10)	C7—C6—C5	124.1 (3)
N1—Ru1—S3	93.92 (8)	C8—C7—C6	119.8 (3)
N2—Ru1—S3	93.76 (8)	C8—C7—H7	120.1
N1—Ru1—S2	174.02 (8)	C6—C7—H7	120.1
N2—Ru1—S2	96.43 (8)	C9—C8—C7	119.2 (3)
S3—Ru1—S2	88.19 (3)	C9—C8—H8	120.4
N1—Ru1—S1	98.04 (7)	C7—C8—H8	120.4
N2—Ru1—S1	175.57 (8)	C8—C9—C10	119.0 (3)
S3—Ru1—S1	88.18 (3)	C8—C9—H9	120.5
S2—Ru1—S1	87.61 (3)	C10—C9—H9	120.5
N1—Ru1—Cl1	88.41 (8)	N2—C10—C9	122.7 (3)
N2—Ru1—Cl1	87.70 (8)	N2—C10—H10	118.6
S3—Ru1—Cl1	177.46 (3)	C9—C10—H10	118.6
S2—Ru1—Cl1	89.59 (3)	C12—C11—S1	111.4 (2)
S1—Ru1—Cl1	90.51 (3)	C12—C11—H11A	109.3
C16—S1—C11	100.05 (16)	S1—C11—H11A	109.3
C16—S1—Ru1	103.44 (11)	C12—C11—H11B	109.3
C11—S1—Ru1	106.47 (10)	S1—C11—H11B	109.3
C12—S2—C13	101.89 (15)	H11A—C11—H11B	108.0
C12—S2—Ru1	103.80 (11)	C11—C12—S2	113.2 (2)
C13—S2—Ru1	106.02 (11)	C11—C12—H12A	108.9
C14—S3—C15	99.61 (16)	S2—C12—H12A	108.9
C14—S3—Ru1	103.17 (11)	C11—C12—H12B	108.9
C15—S3—Ru1	106.61 (11)	S2—C12—H12B	108.9
C1—N1—C5	117.8 (3)	H12A—C12—H12B	107.8
C1—N1—Ru1	126.2 (2)	C14—C13—S2	110.8 (2)
C5—N1—Ru1	115.9 (2)	C14—C13—H13A	109.5
C10—N2—C6	118.5 (3)	S2—C13—H13A	109.5
C10—N2—Ru1	125.6 (2)	C14—C13—H13B	109.5
C6—N2—Ru1	115.8 (2)	S2—C13—H13B	109.5
O1—N3—O3	120.4 (3)	H13A—C13—H13B	108.1
O1—N3—O2	119.8 (3)	C13—C14—S3	112.6 (2)
O3—N3—O2	119.7 (3)	C13—C14—H14A	109.1
N1—C1—C2	122.8 (3)	S3—C14—H14A	109.1
N1—C1—H1	118.6	C13—C14—H14B	109.1
C2—C1—H1	118.6	S3—C14—H14B	109.1
C3—C2—C1	119.7 (3)	H14A—C14—H14B	107.8
C3—C2—H2	120.1	C16—C15—S3	111.5 (2)
C1—C2—H2	120.1	C16—C15—H15A	109.3
C2—C3—C4	118.3 (3)	S3—C15—H15A	109.3
C2—C3—H3	120.8	C16—C15—H15B	109.3
C4—C3—H3	120.8	S3—C15—H15B	109.3
C3—C4—C5	119.9 (3)	H15A—C15—H15B	108.0
C3—C4—H4	120.1	C15—C16—S1	113.2 (2)
C5—C4—H4	120.1	C15—C16—H16A	108.9
N1—C5—C4	121.5 (3)	S1—C16—H16A	108.9
N1—C5—C6	115.3 (3)	C15—C16—H16B	108.9
C4—C5—C6	123.2 (3)	S1—C16—H16B	108.9
N2—C6—C7	120.8 (3)	H16A—C16—H16B	107.8
N2—C6—C5	115.1 (3)	H1X—O1W—H1Y	109.6 (15)

N1—Ru1—S1—C16	−76.63 (14)	Ru1—N1—C1—C2	−177.6 (2)
S3—Ru1—S1—C16	17.07 (12)	N1—C1—C2—C3	1.1 (5)
S2—Ru1—S1—C16	105.33 (12)	C1—C2—C3—C4	−0.2 (5)
Cl1—Ru1—S1—C16	−165.10 (12)	C2—C3—C4—C5	−0.6 (5)
N1—Ru1—S1—C11	178.43 (14)	C1—N1—C5—C4	0.3 (4)
S3—Ru1—S1—C11	−87.87 (12)	Ru1—N1—C5—C4	177.1 (2)
S2—Ru1—S1—C11	0.39 (12)	C1—N1—C5—C6	−177.7 (3)
Cl1—Ru1—S1—C11	89.96 (12)	Ru1—N1—C5—C6	−1.0 (3)
N2—Ru1—S2—C12	−158.31 (14)	C3—C4—C5—N1	0.6 (5)
S3—Ru1—S2—C12	108.11 (12)	C3—C4—C5—C6	178.5 (3)
S1—Ru1—S2—C12	19.86 (12)	C10—N2—C6—C7	−2.2 (4)
Cl1—Ru1—S2—C12	−70.67 (12)	Ru1—N2—C6—C7	−179.6 (2)
N2—Ru1—S2—C13	94.76 (13)	C10—N2—C6—C5	176.1 (3)
S3—Ru1—S2—C13	1.18 (11)	Ru1—N2—C6—C5	−1.3 (3)
S1—Ru1—S2—C13	−87.07 (11)	N1—C5—C6—N2	1.5 (4)
Cl1—Ru1—S2—C13	−177.60 (11)	C4—C5—C6—N2	−176.5 (3)
N1—Ru1—S3—C14	−154.39 (13)	N1—C5—C6—C7	179.7 (3)
N2—Ru1—S3—C14	−76.32 (13)	C4—C5—C6—C7	1.7 (5)
S2—Ru1—S3—C14	20.01 (11)	N2—C6—C7—C8	0.6 (5)
S1—Ru1—S3—C14	107.67 (11)	C5—C6—C7—C8	−177.5 (3)
N1—Ru1—S3—C15	101.21 (14)	C6—C7—C8—C9	1.2 (5)
N2—Ru1—S3—C15	179.28 (14)	C7—C8—C9—C10	−1.3 (5)
S2—Ru1—S3—C15	−84.39 (12)	C6—N2—C10—C9	2.1 (5)
S1—Ru1—S3—C15	3.27 (12)	Ru1—N2—C10—C9	179.2 (2)
N2—Ru1—N1—C1	176.7 (3)	C8—C9—C10—N2	−0.3 (5)
S3—Ru1—N1—C1	−90.3 (3)	C16—S1—C11—C12	−133.3 (2)
S1—Ru1—N1—C1	−1.6 (3)	Ru1—S1—C11—C12	−26.0 (2)
Cl1—Ru1—N1—C1	88.7 (3)	S1—C11—C12—S2	45.9 (3)
N2—Ru1—N1—C5	0.2 (2)	C13—S2—C12—C11	67.2 (3)
S3—Ru1—N1—C5	93.2 (2)	Ru1—S2—C12—C11	−42.9 (2)
S1—Ru1—N1—C5	−178.1 (2)	C12—S2—C13—C14	−136.2 (2)
Cl1—Ru1—N1—C5	−87.8 (2)	Ru1—S2—C13—C14	−27.9 (2)
N1—Ru1—N2—C10	−176.6 (3)	S2—C13—C14—S3	48.1 (3)
S3—Ru1—N2—C10	90.2 (3)	C15—S3—C14—C13	65.5 (3)
S2—Ru1—N2—C10	1.6 (3)	Ru1—S3—C14—C13	−44.2 (3)
Cl1—Ru1—N2—C10	−87.7 (3)	C14—S3—C15—C16	−135.6 (2)
N1—Ru1—N2—C6	0.6 (2)	Ru1—S3—C15—C16	−28.6 (3)
S3—Ru1—N2—C6	−92.6 (2)	S3—C15—C16—S1	46.3 (3)
S2—Ru1—N2—C6	178.8 (2)	C11—S1—C16—C15	69.2 (3)
Cl1—Ru1—N2—C6	89.5 (2)	Ru1—S1—C16—C15	−40.6 (3)
C5—N1—C1—C2	−1.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1X···O3ⁱ	0.95 (3)	2.10 (3)	3.037 (4)	169 (4)
O1W—H1Y···O2ⁱⁱ	0.94 (3)	1.92 (2)	2.839 (4)	166 (4)

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

Experimental details

Crystal data
Chemical formula	[RuCl(C₁₀H₈N₂)(C₆H₁₂S₃)]NO₃·H₂O
M_r	553.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.6523 (4), 25.1887 (12), 11.1099 (5)
β (°)	108.438 (2)
V (Å³)	2031.52 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.24
Crystal size (mm)	0.05 × 0.04 × 0.02

Data collection
Diffractometer	Bruker X8 Kappa CCD APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.941, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	21232, 5360, 4179
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.078, 1.08
No. of reflections	5360
No. of parameters	259
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.60

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
O1W—H1X···O3ⁱ	0.95 (3)	2.10 (3)	3.037 (4)	169 (4)
O1W—H1Y···O2ⁱⁱ	0.94 (3)	1.916 (15)	2.839 (4)	166 (4)

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

Acknowledgements

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

References

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