metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

trans-Di­bromido­tetra­kis­(pyridine-κN)ruthenium(II)

aDepartment of Applied Chemistry, School of Petrochemical Engineering, Changzhou University, Jiangsu 213164, People's Republic of China, and bInstitute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma'anshan, Anhui 243002, People's Republic of China
*Correspondence e-mail: zhangqf@ahut.edu.cn

(Received 25 December 2012; accepted 9 January 2013; online 16 January 2013)

The title complex, [RuBr2(C5H5N)4], contains two independent complex mol­ecules in each of which the RuII atom is located on a site of 222 symmetry and has a distorted octa­hedral coordination geometry with four pyridine N atoms and two Br atoms. The Br aroms are trans-disposed as a result of symmetry.

Related literature

For background to ruthenium complexes: see: Pagliaro et al. (2005[Pagliaro, M., Campestrini, S. & Ciriminna, R. (2005). Chem. Soc. Rev. 34, 837-845.]); van Rijt & Sadler (2009[Rijt, S. H. van & Sadler, P. J. (2009). Drug Discov. Today, 14, 1089-1097.]); Wu et al. (2009[Wu, F. H., Duan, T., Lu, L., Zhang, Q. F. & Leung, W. H. (2009). J. Organomet. Chem. 694, 3844-3851.]); Zhang et al. (2005[Zhang, Q. F., Cheung, K. M., Williams, I. D. & Leung, W. H. (2005). Eur. J. Inorg. Chem. pp. 4780-4787.]). For related structures, see: Mirza et al. (2003[Mirza, H. A., Farah, A. A., Stynes, D. V. & Lever, A. B. P. (2003). Acta Cryst. E59, m679-m680.]); Wong & Lau (1994[Wong, W.-T. & Lau, T.-C. (1994). Acta Cryst. C50, 1406-1407.]); Zhang et al. (2006[Zhang, L.-Y., Zhu, Y.-M., Shi, L.-X. & Chen, Z.-N. (2006). Chin. J. Inorg. Chem. 22, 1453-1466.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • [RuBr2(C5H5N)4]

  • Mr = 577.29

  • Orthorhombic, F d d d

  • a = 16.830 (4) Å

  • b = 22.032 (5) Å

  • c = 23.221 (5) Å

  • V = 8610 (3) Å3

  • Z = 16

  • Mo Kα radiation

  • μ = 4.45 mm−1

  • T = 296 K

  • 0.22 × 0.18 × 0.13 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.441, Tmax = 0.595

  • 13382 measured reflections

  • 2430 independent reflections

  • 1631 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.069

  • S = 1.04

  • 2430 reflections

  • 125 parameters

  • H-atom parameters constrained

  • Δρmax = 0.58 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Selected bond lengths (Å)

Ru1—N1 2.086 (2)
Ru1—Br1 2.5439 (7)
Ru2—N2 2.083 (2)
Ru2—Br2 2.5378 (7)

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Coordination chemistry of ruthenium complexes has been studied in last few decades because of their versatile and diverse applications in molecular catalysis (Pagliaro et al., 2005) and bioinorganic chemistry (van Rijt & Sadler, 2009). As part of our long-standing interest in the ruthenium complexes with σ-donor ligands such as thiolate, pyridine and phosphine (Zhang et al., 2005), we have investigated the reactivity of the starting ruthenium compounds such as RuCl2(PPh3)3, RuHCl(CO)(PPh3)3 and RuCl2(dmso)4 (dmso = dimethyl sulfoxide) with mono-, bi- and poly-dentate ligands (Wu et al., 2009). Here we report the crystal structure of the mononuclear ruthenium(II) complex.

In the title complex, there are two independent complex molecules with a perpendicular arrangement. Each RuII atom is located on a 222 symmetry. No significant differences in bonding parameters between these two molecules are found. One of the molecular structures is depicted in Fig. 1. The coordination geometry of the RuII atom is octahedral with four pyridine N atoms and two Br atoms. The Ru—N bond lengths (Table 1) are in the range of those found in related structures of ruthenium(II) complexes retrieved from the Cambridge Structural Database (Allen, 2002). The Ru—Br bond lengths are comparable to those reported in other ruthenium(II)-bromide complexes such as [Ru2Br2(pz)(py)8][PF6]2.2DMF (pz = pyrazine, py = pyridine) [av. 2.5524 (4) Å] (Mirza et al., 2003) and trans-[RuBr(py)4C(CN)3] [2.5453 (12) Å] (Zhang et al., 2006). Two Br atoms are trans disposed as indicated by the Br—Ru—Br bond angle of 180°, as a result of symmetry requirements. Similar case was found in analogous complex trans-[RuCl2(py)4] (Wong & Lau, 1994).

Related literature top

For background to ruthenium complexes: see: Pagliaro et al. (2005); van Rijt & Sadler (2009); Wu et al. (2009); Zhang et al. (2005). For related structures, see: Mirza et al. (2003); Wong & Lau (1994); Zhang et al. (2006). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a THF solution (10 ml) of RuCl2(DMSO)4 (97 mg, 0.2 mmol) was added pyridine (63 mg, 0.8 mmol) and Br2 (32 mg, 0.2 mmol) under a nitrogen atmosphere. The reaction mixture was refluxed for 2 h, developing red. The solvent was evaporated in vacuo and the residue was washed with hexane. Recrystallization from CH2Cl2/hexane afforded red crystals of the title complex within two days (yield: 75 mg, 65 % based on Ru). Analysis, calculated for C20H20Br2N4Ru: C 41.61, H 3.49, N 9.70%; found: C 41.53, H 3.44, N 9.63%.

Refinement top

H atoms were placed in geometrically idealized positions and refined as riding atoms, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing one of the two independent molecules. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (A) x, 1/4-y, 1/4-z; (B) 1/4-x, y, 1/4-z; (C) 1/4-x, 1/4-y, z.]
[Figure 2] Fig. 2. Packing diagram of the title compound in a unit cell, viewed along the c axis.
trans-Dibromidotetrakis(pyridine-κN)ruthenium(II) top
Crystal data top
[RuBr2(C5H5N)4]F(000) = 4512
Mr = 577.29Dx = 1.781 Mg m3
Orthorhombic, FdddMo Kα radiation, λ = 0.71073 Å
Hall symbol: -F 2uv 2vwCell parameters from 2149 reflections
a = 16.830 (4) Åθ = 2.2–26.4°
b = 22.032 (5) ŵ = 4.45 mm1
c = 23.221 (5) ÅT = 296 K
V = 8610 (3) Å3Block, red
Z = 160.22 × 0.18 × 0.13 mm
Data collection top
Bruker APEXII CCD
diffractometer
2430 independent reflections
Radiation source: fine-focus sealed tube1631 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2121
Tmin = 0.441, Tmax = 0.595k = 2828
13382 measured reflectionsl = 2926
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0292P)2 + 11.6805P]
where P = (Fo2 + 2Fc2)/3
2430 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
[RuBr2(C5H5N)4]V = 8610 (3) Å3
Mr = 577.29Z = 16
Orthorhombic, FdddMo Kα radiation
a = 16.830 (4) ŵ = 4.45 mm1
b = 22.032 (5) ÅT = 296 K
c = 23.221 (5) Å0.22 × 0.18 × 0.13 mm
Data collection top
Bruker APEXII CCD
diffractometer
2430 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1631 reflections with I > 2σ(I)
Tmin = 0.441, Tmax = 0.595Rint = 0.034
13382 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.069H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0292P)2 + 11.6805P]
where P = (Fo2 + 2Fc2)/3
2430 reflectionsΔρmax = 0.58 e Å3
125 parametersΔρmin = 0.34 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
Ru10.12500.12500.12500.03562 (11)
Ru20.62500.12500.12500.03634 (11)
Br10.12500.009537 (19)0.12500.05758 (14)
Br20.62500.12500.015713 (18)0.06143 (15)
N10.03782 (12)0.12460 (9)0.18885 (9)0.0409 (5)
N20.71241 (13)0.19195 (10)0.12552 (9)0.0428 (5)
C10.02375 (16)0.08600 (14)0.18763 (12)0.0513 (7)
H10.02800.05940.15670.062*
C20.08052 (18)0.08388 (16)0.22953 (14)0.0643 (9)
H20.12230.05640.22680.077*
C30.0757 (2)0.12230 (16)0.27562 (15)0.0664 (9)
H30.11370.12160.30470.080*
C40.01284 (18)0.16198 (15)0.27768 (13)0.0565 (8)
H40.00770.18870.30840.068*
C50.04201 (16)0.16198 (13)0.23442 (11)0.0463 (6)
H50.08420.18910.23660.056*
C60.77437 (16)0.19016 (13)0.16161 (13)0.0513 (7)
H60.77830.15770.18700.062*
C70.83202 (18)0.23371 (16)0.16297 (15)0.0655 (9)
H70.87400.23040.18880.079*
C80.8280 (2)0.28178 (15)0.12661 (16)0.0721 (10)
H80.86700.31170.12690.086*
C90.76494 (19)0.28493 (15)0.08948 (16)0.0656 (9)
H90.76010.31750.06420.079*
C100.70898 (16)0.23981 (13)0.08982 (13)0.0509 (7)
H100.66670.24240.06420.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.0287 (2)0.0399 (2)0.0383 (2)0.0000.0000.000
Ru20.0285 (2)0.0431 (2)0.0374 (2)0.0000.0000.000
Br10.0600 (3)0.0459 (2)0.0668 (3)0.0000.0158 (2)0.000
Br20.0616 (3)0.0806 (3)0.0421 (2)0.0070 (2)0.0000.000
N10.0331 (11)0.0465 (12)0.0430 (12)0.0042 (10)0.0006 (9)0.0007 (10)
N20.0326 (11)0.0461 (12)0.0497 (13)0.0005 (9)0.0006 (10)0.0022 (11)
C10.0398 (15)0.0614 (18)0.0526 (17)0.0119 (14)0.0014 (13)0.0002 (14)
C20.0449 (18)0.081 (2)0.067 (2)0.0174 (16)0.0047 (15)0.0060 (18)
C30.0495 (18)0.091 (2)0.0590 (19)0.0018 (18)0.0172 (15)0.0106 (18)
C40.0482 (17)0.072 (2)0.0490 (17)0.0020 (15)0.0079 (13)0.0041 (15)
C50.0392 (15)0.0486 (16)0.0512 (17)0.0019 (12)0.0030 (12)0.0028 (13)
C60.0382 (15)0.0530 (17)0.0627 (19)0.0023 (13)0.0086 (14)0.0006 (14)
C70.0407 (17)0.068 (2)0.088 (2)0.0039 (15)0.0146 (17)0.0092 (18)
C80.0504 (19)0.053 (2)0.112 (3)0.0150 (15)0.001 (2)0.004 (2)
C90.0528 (19)0.056 (2)0.088 (2)0.0023 (15)0.0069 (18)0.0133 (18)
C100.0380 (15)0.0549 (18)0.0597 (18)0.0009 (13)0.0018 (13)0.0077 (14)
Geometric parameters (Å, º) top
Ru1—N1i2.086 (2)C1—H10.9300
Ru1—N1ii2.086 (2)C2—C31.367 (5)
Ru1—N12.086 (2)C2—H20.9300
Ru1—N1iii2.086 (2)C3—C41.373 (4)
Ru1—Br12.5439 (7)C3—H30.9300
Ru1—Br1ii2.5439 (7)C4—C51.364 (4)
Ru2—N2iv2.083 (2)C4—H40.9300
Ru2—N22.083 (2)C5—H50.9300
Ru2—N2i2.083 (2)C6—C71.365 (4)
Ru2—N2v2.083 (2)C6—H60.9300
Ru2—Br22.5378 (7)C7—C81.356 (5)
Ru2—Br2v2.5378 (7)C7—H70.9300
N1—C11.341 (3)C8—C91.370 (5)
N1—C51.343 (3)C8—H80.9300
N2—C61.339 (3)C9—C101.369 (4)
N2—C101.342 (3)C9—H90.9300
C1—C21.365 (4)C10—H100.9300
N1i—Ru1—N1ii179.52 (12)C6—N2—C10116.3 (2)
N1i—Ru1—N190.60 (12)C6—N2—Ru2122.20 (18)
N1ii—Ru1—N189.40 (12)C10—N2—Ru2121.48 (18)
N1i—Ru1—N1iii89.40 (12)N1—C1—C2123.2 (3)
N1ii—Ru1—N1iii90.60 (12)N1—C1—H1118.4
N1—Ru1—N1iii179.52 (12)C2—C1—H1118.4
N1i—Ru1—Br190.24 (6)C1—C2—C3119.7 (3)
N1ii—Ru1—Br190.24 (6)C1—C2—H2120.2
N1—Ru1—Br189.76 (6)C3—C2—H2120.2
N1iii—Ru1—Br189.76 (6)C2—C3—C4117.9 (3)
N1i—Ru1—Br1ii89.76 (6)C2—C3—H3121.1
N1ii—Ru1—Br1ii89.76 (6)C4—C3—H3121.1
N1—Ru1—Br1ii90.24 (6)C5—C4—C3119.7 (3)
N1iii—Ru1—Br1ii90.24 (6)C5—C4—H4120.2
Br1—Ru1—Br1ii180.0C3—C4—H4120.2
N2iv—Ru2—N2179.34 (11)N1—C5—C4123.0 (3)
N2iv—Ru2—N2i89.84 (12)N1—C5—H5118.5
N2—Ru2—N2i90.16 (12)C4—C5—H5118.5
N2iv—Ru2—N2v90.16 (12)N2—C6—C7123.2 (3)
N2—Ru2—N2v89.84 (12)N2—C6—H6118.4
N2i—Ru2—N2v179.34 (11)C7—C6—H6118.4
N2iv—Ru2—Br290.33 (6)C8—C7—C6120.0 (3)
N2—Ru2—Br290.33 (6)C8—C7—H7120.0
N2i—Ru2—Br289.67 (6)C6—C7—H7120.0
N2v—Ru2—Br289.67 (6)C7—C8—C9118.0 (3)
N2iv—Ru2—Br2v89.67 (6)C7—C8—H8121.0
N2—Ru2—Br2v89.67 (6)C9—C8—H8121.0
N2i—Ru2—Br2v90.33 (6)C10—C9—C8119.5 (3)
N2v—Ru2—Br2v90.33 (6)C10—C9—H9120.2
Br2—Ru2—Br2v180.0C8—C9—H9120.2
C1—N1—C5116.5 (2)N2—C10—C9123.0 (3)
C1—N1—Ru1122.09 (18)N2—C10—H10118.5
C5—N1—Ru1121.38 (17)C9—C10—H10118.5
Symmetry codes: (i) x, y+1/4, z+1/4; (ii) x+1/4, y+1/4, z; (iii) x+1/4, y, z+1/4; (iv) x+5/4, y+1/4, z; (v) x+5/4, y, z+1/4.

Experimental details

Crystal data
Chemical formula[RuBr2(C5H5N)4]
Mr577.29
Crystal system, space groupOrthorhombic, Fddd
Temperature (K)296
a, b, c (Å)16.830 (4), 22.032 (5), 23.221 (5)
V3)8610 (3)
Z16
Radiation typeMo Kα
µ (mm1)4.45
Crystal size (mm)0.22 × 0.18 × 0.13
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.441, 0.595
No. of measured, independent and
observed [I > 2σ(I)] reflections
13382, 2430, 1631
Rint0.034
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.069, 1.04
No. of reflections2430
No. of parameters125
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0292P)2 + 11.6805P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.58, 0.34

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Ru1—N12.086 (2)Ru2—N22.083 (2)
Ru1—Br12.5439 (7)Ru2—Br22.5378 (7)
 

Acknowledgements

This project was supported by the Natural Science Foundation of China (grant Nos. 20771003 and 21201003).

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationMirza, H. A., Farah, A. A., Stynes, D. V. & Lever, A. B. P. (2003). Acta Cryst. E59, m679–m680.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationPagliaro, M., Campestrini, S. & Ciriminna, R. (2005). Chem. Soc. Rev. 34, 837–845.  Web of Science CrossRef PubMed CAS Google Scholar
First citationRijt, S. H. van & Sadler, P. J. (2009). Drug Discov. Today, 14, 1089–1097.  Web of Science PubMed Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWong, W.-T. & Lau, T.-C. (1994). Acta Cryst. C50, 1406–1407.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationWu, F. H., Duan, T., Lu, L., Zhang, Q. F. & Leung, W. H. (2009). J. Organomet. Chem. 694, 3844–3851.  Web of Science CSD CrossRef CAS Google Scholar
First citationZhang, Q. F., Cheung, K. M., Williams, I. D. & Leung, W. H. (2005). Eur. J. Inorg. Chem. pp. 4780–4787.  Web of Science CSD CrossRef Google Scholar
First citationZhang, L.-Y., Zhu, Y.-M., Shi, L.-X. & Chen, Z.-N. (2006). Chin. J. Inorg. Chem. 22, 1453–1466.  CAS Google Scholar

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