6-(2-Chloro-benzyl-amino)purinium tetra-chlorido(dimethyl sulfoxide-κO)(nitrosyl-κN)ruthenate(III) monohydrate.

The asymmetric unit of the title complex salt, (C(12)H(11)ClN(5))[RuCl(4)(NO)(C(2)H(6)OS)]·H(2)O, contains a 6-(2-chloro-benzyl-amino)purinium cation, a tetra-chlorido(dimethyl sulfoxide)nitro-sylruthenate(III) anion and one solvent water mol-ecule. The Ru(III) atom is octa-hedrally coordinated by four Cl atoms in the equatorial plane, and by a dimethyl sulfoxide O atom and a nitrosyl N atom in axial positions. The cation is an N3-protonated N7 tautomer. Inter-molecular N-H⋯N hydrogen bonds connect two cations into centrosymmetric dimers, with an N⋯N distance of 2.821 (4) Å. The crystal structure also involves N-H⋯O, N-H⋯Cl and O-H⋯Cl hydrogen bonds.

Related literature

For related structures of 6-benzyl­amino­purine derivatives, see: Maloň et al. (2001 ▶, 2002 ▶); Trávníček et al. (2004 ▶, 2005 ▶, 2007 ▶); Trávníček & Matiková-Maľarová (2006 ▶). For the structure of a related Ru complex, see: Serli et al. (2002 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

(C12H11ClN5)[RuCl4(NO)(C2H6OS)]·H2O

M = 629.73

Orthorhombic,

a = 15.6229 (5) Å

b = 12.8014 (4) Å

c = 22.6866 (16) Å

V = 4537.2 (4) Å3

Z = 8

Mo Kα radiation

μ = 1.40 mm−1

T = 120 (2) K

0.40 × 0.30 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur2 diffractometer with CCD detector

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.604, T max = 0.721

36172 measured reflections

3984 independent reflections

3588 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 1.09

3984 reflections

279 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.25 e Å−3

Δρmin = −0.58 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006673/tk2253sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006673/tk2253Isup2.hkl

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

(C12H11ClN5)[RuCl4(NO)(C2H6OS)]·H2O	F000 = 2512
Mr = 629.73	Dx = 1.844 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 29289 reflections
a = 15.6229 (5) Å	θ = 2.6–31.9º
b = 12.8014 (4) Å	µ = 1.40 mm−1
c = 22.6866 (16) Å	T = 120 (2) K
V = 4537.2 (4) Å3	Prism, violet
Z = 8	0.40 × 0.30 × 0.25 mm

Oxford Diffraction Xcalibur2 diffractometer with CCD detector	3984 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3588 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.018
Detector resolution: 8.3611 pixels mm-1	θmax = 25.0º
T = 120(2) K	θmin = 2.6º
rotation method ω scans	h = −18→15
Absorption correction: multi-scan(CrysAlis RED; Oxford Diffraction, 2007)	k = −13→15
Tmin = 0.604, Tmax = 0.721	l = −26→26
36172 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079	w = 1/[σ2(Fo2) + (0.0366P)2 + 10.7079P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
3984 reflections	Δρmax = 1.25 e Å−3
279 parameters	Δρmin = −0.58 e Å−3
2 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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	0.616687 (16)	0.769508 (19)	0.208516 (10)	0.01845 (9)
S1	0.47079 (7)	0.93802 (7)	0.19053 (4)	0.0406 (3)
N1	0.57623 (16)	0.3182 (2)	0.47999 (11)	0.0210 (6)
O1	0.52917 (14)	0.85527 (17)	0.16242 (10)	0.0250 (5)
Cl2	0.67103 (5)	0.72294 (6)	0.11452 (3)	0.02083 (17)
C2	0.5321 (2)	0.2412 (2)	0.45576 (14)	0.0225 (7)
H2A	0.5052	0.2546	0.4190	0.027*
N2	0.68824 (19)	0.6944 (2)	0.24609 (12)	0.0285 (6)
O2	0.7319 (2)	0.6425 (2)	0.27444 (12)	0.0498 (8)
O3	0.87301 (19)	0.6670 (2)	0.18872 (13)	0.0445 (7)
Cl3	0.70383 (5)	0.92198 (7)	0.20765 (4)	0.0304 (2)
N3	0.52234 (16)	0.1460 (2)	0.47885 (11)	0.0199 (5)
H3A	0.4903	0.0986	0.4615	0.024*
Cl4	0.55053 (6)	0.81931 (7)	0.29846 (3)	0.0326 (2)
C4	0.56383 (19)	0.1251 (2)	0.53017 (13)	0.0183 (6)
Cl5	0.51797 (6)	0.63075 (7)	0.20103 (4)	0.0317 (2)
C5	0.61254 (19)	0.2011 (2)	0.55736 (14)	0.0198 (6)
Cl6	0.63017 (6)	0.69071 (6)	0.46836 (4)	0.0329 (2)
C6	0.61565 (18)	0.3025 (2)	0.53287 (14)	0.0189 (6)
N6	0.65345 (17)	0.3834 (2)	0.55878 (12)	0.0224 (6)
H6A	0.6813	0.3724	0.5919	0.027*
N7	0.64498 (18)	0.1527 (2)	0.60684 (12)	0.0237 (6)
H7A	0.6788	0.1809	0.6335	0.028*
C8	0.6151 (2)	0.0543 (3)	0.60655 (15)	0.0237 (7)
H8A	0.6287	0.0044	0.6361	0.028*
N9	0.56465 (17)	0.0337 (2)	0.56098 (12)	0.0219 (6)
C9	0.6513 (2)	0.4892 (2)	0.53527 (14)	0.0239 (7)
H9A	0.6635	0.5389	0.5676	0.029*
H9B	0.5928	0.5040	0.5207	0.029*
C10	0.7143 (2)	0.5083 (2)	0.48574 (14)	0.0210 (7)
C11	0.7108 (2)	0.6004 (2)	0.45299 (14)	0.0247 (7)
C12	0.7666 (2)	0.6214 (3)	0.40738 (15)	0.0306 (8)
H12A	0.7636	0.6859	0.3868	0.037*
C13	0.8268 (2)	0.5472 (3)	0.39215 (16)	0.0358 (9)
H13A	0.8648	0.5597	0.3602	0.043*
C14	0.8317 (2)	0.4551 (3)	0.42324 (17)	0.0357 (9)
H14A	0.8732	0.4041	0.4126	0.043*
C15	0.7766 (2)	0.4362 (3)	0.47003 (15)	0.0281 (7)
H15A	0.7815	0.3729	0.4916	0.034*
C16	0.3684 (3)	0.8778 (5)	0.1860 (3)	0.094 (2)
H16A	0.3664	0.8177	0.2128	0.142*
H16B	0.3583	0.8542	0.1455	0.142*
H16C	0.3242	0.9282	0.1973	0.142*
C17	0.4570 (3)	1.0279 (3)	0.13257 (18)	0.0391 (9)
H17A	0.5108	1.0654	0.1257	0.059*
H17B	0.4121	1.0780	0.1431	0.059*
H17C	0.4405	0.9905	0.0967	0.059*
H3W	0.860 (3)	0.606 (2)	0.2071 (18)	0.050*
H3V	0.9236 (18)	0.687 (3)	0.2050 (18)	0.050*

	U11	U22	U33	U12	U13	U23
Ru1	0.02301 (15)	0.01753 (15)	0.01482 (14)	−0.00037 (10)	−0.00315 (10)	−0.00055 (9)
S1	0.0678 (7)	0.0305 (5)	0.0233 (4)	0.0244 (5)	0.0070 (4)	−0.0014 (4)
N1	0.0198 (14)	0.0203 (14)	0.0229 (14)	−0.0022 (11)	−0.0009 (11)	0.0034 (11)
O1	0.0259 (12)	0.0285 (12)	0.0207 (11)	0.0062 (10)	−0.0028 (9)	−0.0053 (10)
Cl2	0.0188 (4)	0.0246 (4)	0.0191 (4)	0.0011 (3)	−0.0003 (3)	−0.0024 (3)
C2	0.0215 (16)	0.0227 (16)	0.0232 (17)	−0.0017 (13)	−0.0035 (13)	0.0038 (13)
N2	0.0396 (17)	0.0275 (15)	0.0183 (13)	0.0064 (14)	−0.0060 (13)	−0.0014 (12)
O2	0.062 (2)	0.0545 (18)	0.0328 (15)	0.0269 (16)	−0.0130 (14)	0.0043 (13)
O3	0.0407 (16)	0.0503 (18)	0.0424 (17)	−0.0016 (14)	−0.0104 (13)	0.0060 (14)
Cl3	0.0320 (5)	0.0241 (4)	0.0350 (5)	−0.0075 (3)	−0.0039 (4)	−0.0059 (3)
N3	0.0186 (13)	0.0181 (13)	0.0229 (14)	−0.0032 (11)	−0.0041 (11)	−0.0002 (11)
Cl4	0.0444 (5)	0.0349 (5)	0.0186 (4)	0.0014 (4)	0.0033 (4)	−0.0049 (3)
C4	0.0161 (15)	0.0169 (15)	0.0218 (16)	−0.0008 (12)	0.0021 (12)	−0.0004 (12)
Cl5	0.0378 (5)	0.0261 (4)	0.0312 (5)	−0.0117 (4)	0.0078 (4)	−0.0043 (3)
C5	0.0185 (15)	0.0197 (15)	0.0212 (15)	−0.0019 (13)	−0.0024 (12)	0.0025 (13)
Cl6	0.0488 (5)	0.0182 (4)	0.0316 (4)	0.0042 (4)	0.0020 (4)	−0.0021 (3)
C6	0.0148 (15)	0.0189 (15)	0.0231 (16)	−0.0004 (12)	0.0029 (12)	0.0012 (13)
N6	0.0259 (14)	0.0175 (13)	0.0238 (14)	−0.0049 (11)	−0.0042 (11)	0.0023 (11)
N7	0.0257 (14)	0.0228 (14)	0.0225 (14)	−0.0066 (12)	−0.0072 (11)	0.0039 (11)
C8	0.0257 (17)	0.0198 (16)	0.0257 (17)	−0.0049 (13)	−0.0057 (14)	0.0059 (13)
N9	0.0230 (14)	0.0187 (13)	0.0240 (14)	−0.0026 (11)	−0.0022 (11)	0.0041 (11)
C9	0.0279 (17)	0.0184 (16)	0.0255 (17)	−0.0014 (13)	0.0023 (14)	−0.0007 (13)
C10	0.0222 (16)	0.0188 (15)	0.0220 (16)	−0.0056 (13)	−0.0043 (13)	−0.0021 (13)
C11	0.0289 (18)	0.0214 (16)	0.0238 (17)	−0.0051 (14)	−0.0048 (14)	−0.0046 (13)
C12	0.037 (2)	0.0308 (19)	0.0239 (17)	−0.0133 (16)	−0.0009 (15)	0.0044 (14)
C13	0.0263 (19)	0.053 (2)	0.0280 (19)	−0.0101 (17)	0.0050 (15)	0.0023 (17)
C14	0.0235 (18)	0.045 (2)	0.038 (2)	0.0023 (16)	0.0033 (16)	−0.0018 (18)
C15	0.0237 (17)	0.0291 (18)	0.0317 (18)	−0.0014 (14)	−0.0010 (14)	0.0026 (15)
C16	0.050 (3)	0.075 (4)	0.158 (6)	0.028 (3)	0.062 (4)	0.052 (4)
C17	0.045 (2)	0.031 (2)	0.041 (2)	0.0084 (17)	0.0006 (18)	0.0047 (17)

Ru1—N2	1.703 (3)	N6—H6A	0.8800
Ru1—O1	2.042 (2)	N7—C8	1.344 (4)
Ru1—Cl5	2.3585 (9)	N7—H7A	0.8800
Ru1—Cl2	2.3713 (8)	C8—N9	1.326 (4)
Ru1—Cl4	2.3746 (8)	C8—H8A	0.9500
Ru1—Cl3	2.3798 (8)	C9—C10	1.514 (4)
S1—O1	1.536 (2)	C9—H9A	0.9900
S1—C17	1.761 (4)	C9—H9B	0.9900
S1—C16	1.778 (6)	C10—C15	1.388 (5)
N1—C2	1.323 (4)	C10—C11	1.394 (5)
N1—C6	1.363 (4)	C11—C12	1.379 (5)
C2—N3	1.335 (4)	C12—C13	1.382 (5)
C2—H2A	0.9500	C12—H12A	0.9500
N2—O2	1.149 (4)	C13—C14	1.376 (5)
O3—H3W	0.904 (19)	C13—H13A	0.9500
O3—H3V	0.909 (19)	C14—C15	1.388 (5)
N3—C4	1.359 (4)	C14—H14A	0.9500
N3—H3A	0.8800	C15—H15A	0.9500
C4—N9	1.363 (4)	C16—H16A	0.9800
C4—C5	1.380 (4)	C16—H16B	0.9800
C5—N7	1.379 (4)	C16—H16C	0.9800
C5—C6	1.412 (5)	C17—H17A	0.9800
Cl6—C11	1.745 (3)	C17—H17B	0.9800
C6—N6	1.329 (4)	C17—H17C	0.9800
N6—C9	1.457 (4)
N2—Ru1—O1	178.16 (12)	C5—N7—H7A	126.6
N2—Ru1—Cl5	92.30 (10)	N9—C8—N7	113.4 (3)
O1—Ru1—Cl5	86.00 (7)	N9—C8—H8A	123.3
N2—Ru1—Cl2	94.19 (10)	N7—C8—H8A	123.3
O1—Ru1—Cl2	85.09 (6)	C8—N9—C4	103.6 (3)
Cl5—Ru1—Cl2	88.86 (3)	N6—C9—C10	114.0 (3)
N2—Ru1—Cl4	90.41 (10)	N6—C9—H9A	108.7
O1—Ru1—Cl4	90.24 (7)	C10—C9—H9A	108.7
Cl5—Ru1—Cl4	88.82 (3)	N6—C9—H9B	108.7
Cl2—Ru1—Cl4	174.92 (3)	C10—C9—H9B	108.7
N2—Ru1—Cl3	95.26 (10)	H9A—C9—H9B	107.6
O1—Ru1—Cl3	86.44 (7)	C15—C10—C11	116.9 (3)
Cl5—Ru1—Cl3	172.39 (3)	C15—C10—C9	122.6 (3)
Cl2—Ru1—Cl3	89.65 (3)	C11—C10—C9	120.5 (3)
Cl4—Ru1—Cl3	92.06 (3)	C12—C11—C10	122.7 (3)
O1—S1—C17	102.31 (16)	C12—C11—Cl6	118.4 (3)
O1—S1—C16	102.2 (2)	C10—C11—Cl6	118.8 (3)
C17—S1—C16	97.5 (3)	C11—C12—C13	118.9 (3)
C2—N1—C6	119.4 (3)	C11—C12—H12A	120.5
S1—O1—Ru1	123.75 (13)	C13—C12—H12A	120.5
N1—C2—N3	125.2 (3)	C14—C13—C12	120.0 (3)
N1—C2—H2A	117.4	C14—C13—H13A	120.0
N3—C2—H2A	117.4	C12—C13—H13A	120.0
O2—N2—Ru1	175.0 (3)	C13—C14—C15	120.4 (4)
H3W—O3—H3V	104 (4)	C13—C14—H14A	119.8
C2—N3—C4	117.4 (3)	C15—C14—H14A	119.8
C2—N3—H3A	121.3	C14—C15—C10	121.1 (3)
C4—N3—H3A	121.3	C14—C15—H15A	119.5
N3—C4—N9	127.7 (3)	C10—C15—H15A	119.5
N3—C4—C5	120.5 (3)	S1—C16—H16A	109.5
N9—C4—C5	111.8 (3)	S1—C16—H16B	109.5
N7—C5—C4	104.5 (3)	H16A—C16—H16B	109.5
N7—C5—C6	136.1 (3)	S1—C16—H16C	109.5
C4—C5—C6	119.4 (3)	H16A—C16—H16C	109.5
N6—C6—N1	118.4 (3)	H16B—C16—H16C	109.5
N6—C6—C5	123.9 (3)	S1—C17—H17A	109.5
N1—C6—C5	117.8 (3)	S1—C17—H17B	109.5
C6—N6—C9	123.5 (3)	H17A—C17—H17B	109.5
C6—N6—H6A	118.2	S1—C17—H17C	109.5
C9—N6—H6A	118.2	H17A—C17—H17C	109.5
C8—N7—C5	106.8 (3)	H17B—C17—H17C	109.5
C8—N7—H7A	126.6

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N9i	0.88	1.97	2.821 (4)	164
N6—H6A···O3ii	0.88	2.41	3.046 (4)	130
N6—H6A···Cl2ii	0.88	2.66	3.312 (3)	132
N7—H7A···O3ii	0.88	2.45	2.976 (4)	119
N7—H7A···Cl2ii	0.88	2.68	3.290 (3)	127
N7—H7A···Cl3ii	0.88	2.82	3.424 (3)	128
O3—H3W···Cl3iii	0.904 (19)	2.56 (3)	3.386 (3)	152 (4)
O3—H3V···Cl4iv	0.909 (19)	2.61 (3)	3.402 (3)	146 (4)
O3—H3V···Cl5iv	0.909 (19)	2.69 (3)	3.406 (3)	136 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N9i	0.88	1.97	2.821 (4)	164
N6—H6A⋯O3ii	0.88	2.41	3.046 (4)	130
N6—H6A⋯Cl2ii	0.88	2.66	3.312 (3)	132
N7—H7A⋯O3ii	0.88	2.45	2.976 (4)	119
N7—H7A⋯Cl2ii	0.88	2.68	3.290 (3)	127
N7—H7A⋯Cl3ii	0.88	2.82	3.424 (3)	128
O3—H3W⋯Cl3iii	0.904 (19)	2.56 (3)	3.386 (3)	152 (4)
O3—H3V⋯Cl4iv	0.909 (19)	2.61 (3)	3.402 (3)	146 (4)
O3—H3V⋯Cl5iv	0.909 (19)	2.69 (3)	3.406 (3)	136 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .