Crystal structure of cis,fac-{N,N-bis-[(pyridin-2-yl)meth-yl]methyl-amine-κ(3) N,N',N''}di-chlorido-(dimethyl sulfoxide-κS)ruthenium(II).

The reaction of di-chlorido-tetra-kis-(dimethyl sulfoxide)-ruthen-ium(II) with N,N-bis[(pyridin-2-yl)meth-yl]methyl-amine aff-ords the title complex, [RuCl2(C13H15N3)(C2H6OS)]. The asymmetric unit contains a well-ordered complex mol-ecule. The N,N-bis-[(pyridin-2-yl)meth-yl]methyl-amine (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 d (6) 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 octa-hedral 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.

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 d 6 RuII cations and through its O atom with RuIII 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 ▸)

Experimental

Crystal data

[RuCl2(C13H15N3)(C2H6OS)]

M = 463.38

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.085

S = 1.01

7273 reflections

292 parameters

All H-atom parameters refined

Δρmax = 1.13 e Å−3

Δρmin = −0.92 e Å−3

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.

Crystal structure: contains datablock(s) New_Global_Publ_Block, I. DOI: 10.1107/S2056989015014875/zq2232sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014875/zq2232Isup2.hkl

Click here for additional data file.

Structural commentary. DOI: 10.1107/S2056989015014875/zq2232sup3.docx

Supporting information file. DOI: 10.1107/S2056989015014875/zq2232sup3.pdf

Click here for additional data file.

2 . DOI: 10.1107/S2056989015014875/zq2232fig1.tif

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

CCDC reference: 1417672

Additional supporting information: crystallographic information; 3D view; checkCIF report

[RuCl2(C13H15N3)(C2H6OS)]	F(000) = 1872
Mr = 463.38	Dx = 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

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

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(Fo2) + (0.0338P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.002
7273 reflections	Δρmax = 1.13 e Å−3
292 parameters	Δρmin = −0.92 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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C14H14AO1i	0.91(4)	2.54(4)	3.431(3)	169(3)
C4H4Cl1ii	0.93(3)	2.58(3)	3.487(2)	165(2)
C1H1CO1	0.99(3)	2.32(3)	3.182(4)	145(2)

Symmetry codes: (i) ; (ii) .