(2,2'-Bipyridine-κN,N')chlorido(1,4,7-trithia-cyclo-nonane-κS,S',S'')ruthenium(II) nitrate monohydrate.

In the title compound, [RuCl(C(10)H(8)N(2))(C(6)H(12)S(3))]NO(3)·H(2)O or [RuCl(bpy)([9]aneS(3))]NO(3)·H(2)O, ([9]aneS(3) is 1,4,7-tri-thia-cyclo-nonane and bpy is 2,2'-bipyridine), the Ru(II) cation has a slightly distorted octa-hedral environment composed of three facially coordinated S atoms from ([9]aneS(3)), two N atoms from bpy and a chloride anion. The nitrate counter-ion and the water mol-ecule of crystallization are engaged in O-H⋯O hydrogen-bonding inter-actions, leading to a supra-molecular 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 = 553.07

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.078

S = 1.08

5360 reflections

259 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.74 e Å−3

Δρmin = −0.60 e Å−3

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810046556/bg2373sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046556/bg2373Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[RuCl(C10H8N2)(C6H12S3)]NO3·H2O	F(000) = 1120
Mr = 553.07	Dx = 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

Bruker X8 Kappa CCD APEXII diffractometer	5360 independent reflections
Radiation source: fine-focus sealed tube	4179 reflections with I > 2σ(I)
graphite	Rint = 0.048
ω and φ scans	θmax = 29.1°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −10→9
Tmin = 0.941, Tmax = 0.976	k = −34→29
21232 measured reflections	l = −15→15

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(Fo2) + (0.026P)2 + 1.766P] where P = (Fo2 + 2Fc2)/3
5360 reflections	(Δ/σ)max = 0.002
259 parameters	Δρmax = 0.74 e Å−3
3 restraints	Δρmin = −0.60 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) ; (ii) .