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trans-Di­chlorido­tetra­pyrazine­ruthenium(II) di­chloro­methane disolvate

aDepartment of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX 76203-5070, USA, and bDepartment of Chemistry, Austin College, 900 North Grand, Sherman, TX 75090-4400, USA
*Correspondence e-mail: bsmucker@austincollege.edu

(Received 2 August 2012; accepted 14 August 2012; online 23 August 2012)

In the title compound, [RuCl2(C4H4N2)4]·2CH2Cl2, the RuII atom occupies a position of 222 symmetry and the C atom of the solvent mol­ecule occupies a site with twofold symmetry. The RuII atom has a slightly distorted octa­hedral geometry. The pyrazine rings are propeller-like and rotated 45.1 (1)° from the RuN4 plane. In the crystal, the complex and solvent mol­ecules are bridged by weak C—H⋯N hydrogen bonds along the c axis. Weak inter­molecular C—H⋯Cl contacts link the complexes in the ab plane, forming a network.

Related literature

The synthesis of the title complex and its use as a building block in coordination networks are described by Carlucci et al. (2002[Carlucci, L., Ciani, G., Porta, F., Proserpio, D. M. & Santagostini, L. (2002). Angew. Chem. Int. Ed. 41, 1907-1911.]) and Coe (2004[Coe, B. J. (2004). J. Chem. Ed. 81, 718-721.]). For related structures using pyridine and varying trans ligands, see: Coe et al. (1995[Coe, B. J., Meyer, T. J. & White, P. S. (1995). Inorg. Chem. 34, 593-602.]); Desjardins et al. (1999[Desjardins, P., Yap, G. P. A. & Crutchley, R. J. (1999). Inorg. Chem. 38, 5901-5905.]).

[Scheme 1]

Experimental

Crystal data
  • [RuCl2(C4H4N2)4]·2CH2Cl2

  • Mr = 662.19

  • Tetragonal, I 41 22

  • a = 7.3059 (2) Å

  • c = 47.3659 (16) Å

  • V = 2528.21 (14) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.28 mm−1

  • T = 100 K

  • 0.10 × 0.10 × 0.08 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1996[Bruker (1996). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.882, Tmax = 0.908

  • 15409 measured reflections

  • 1399 independent reflections

  • 1363 reflections with I > 2σ(I)

  • Rint = 0.030

Refinement
  • R[F2 > 2σ(F2)] = 0.016

  • wR(F2) = 0.040

  • S = 1.03

  • 1399 reflections

  • 81 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 1.01 e Å−3

  • Δρmin = −0.38 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 508 Friedel pairs

  • Flack parameter: 0.26 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3A⋯Cl1i 0.95 2.88 3.555 (2) 129
C5—H5A⋯N2ii 0.92 (2) 2.46 (2) 3.338 (2) 158 (2)
Symmetry codes: (i) -x+1, -y+1, z; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 4}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2. 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

The pyrazine ligands are rotated 45.1 (1)° from the N—Ru—N plane (Fig. 1) consistent with other propeller-like structures (Coe et al., 1995 and references therein). The terminal chloride atoms on the Ru(pz)4Cl2 complexes are 2.86 - 2.94 Å from the four hydrogen atoms belonging to neighboring pyrazine groups (Fig. 2). This additional interaction enhances the stability of the propeller-like structure.

The Ru—Cl bond length is 2.3920 (5) Å and the Ru—N bond length is 2.0620 (14) Å. These distances are on the low side of the narrow range of bond lengths when this complex is used in supramolecular assemblies (Carlucci et al., 2002), indicating very little influence on bond distance upon further coordination of this metal-based building block. Ru—N distances in tetrakis(pyridine)RuL2, are 2.09 Å (L = 2-chlorophenylcyanamide) (Desjardins, et al., 1999), or 2.08 Å (L = one chloride and one benzonitrile) (Coe et al., 1995).

H-bonds and intermolecular contacts form a network in the crystal. Atom Cl1 has an intermolecular contact with a hydrogen atom on two pyrazine ligands on a neighboring complex (Fig. 3 and Table 1). At the same time, the hydrogen atoms of the dichloromethane solvate have weak hydrogen bonds between two terminal N-atoms on the pyrazine ligands of two separate Ru(pz)4Cl2 complexes (Fig. 4 and Table 1). Additionally, the solvent chloride atom is 3.383 (3) Å from the C2 atom near the uncoordinated nitrogen on the pyrazine ligand.

Related literature top

The synthesis of the title complex and its use as a building block in coordination networks are described by Carlucci et al. (2002) and Coe (2004). For related structures using pyridine and varying trans ligands, see: Coe et al. (1995); Desjardins et al. (1999).

Experimental top

The ruthenium complex was synthesized by the student co-authors in the laboratory component of Austin College's advanced inorganic course according to procedures by Carlucci et al. (2002) and Coe (2004). Crystals of the title compound were grown from a slow diffusion of hexanes into a solution of the ruthenium complex dissolved in dichloromethane.

Refinement top

The H atoms attached to C atoms of the pyrazine molecules were placed in idealized positions (C—H = 0.95 Å) and allowed to ride on their parent atoms. Their positions were constrained so that the Uiso(H) was equal to 1.2Ueq of their respective parent atoms. The solvent molecule, CH2Cl2, occupies a special position in the unit cell so the H atom was located using a difference map and was refined with a constrained Uiso(H) equal to 1.2Ueq of its parent atom.

The maximum and minimum residual electron density peaks of 1.01 and 0.37 eÅ-3, respectively, were located 1.44 Å and 0.76 Å from the H4A and Ru1 atoms, respectively, with the large residue most likely due to imperfect absorption corrections frequently encountered in heavy-metal atom structures.

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. View of the title compound with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. View of the title compound showing intramolecular Cl···H contacts.
[Figure 3] Fig. 3. Fragment of the crystal packing of the compound along a c axis (dashed lines are Cl···H contacts).
[Figure 4] Fig. 4. Fragment of the crystal packing of the compound along an a axis (dashed lines are C—H···N H-bonds).
trans-Dichloridotetrapyrazineruthenium(II) dichloromethane disolvate top
Crystal data top
[RuCl2(C4H4N2)4]·2CH2Cl2Dx = 1.740 Mg m3
Mr = 662.19Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4122Cell parameters from 8671 reflections
Hall symbol: I 4bw 2bwθ = 2.8–27.0°
a = 7.3059 (2) ŵ = 1.28 mm1
c = 47.3659 (16) ÅT = 100 K
V = 2528.21 (14) Å3Plate, black
Z = 40.10 × 0.10 × 0.08 mm
F(000) = 1320
Data collection top
Bruker APEXII CCD
diffractometer
1399 independent reflections
Radiation source: fine-focus sealed tube1363 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω scansθmax = 27.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 1996)
h = 99
Tmin = 0.882, Tmax = 0.908k = 99
15409 measured reflectionsl = 6060
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.016H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.040 w = 1/[σ2(Fo2) + (0.022P)2 + 2.540P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
1399 reflectionsΔρmax = 1.01 e Å3
81 parametersΔρmin = 0.38 e Å3
0 restraintsAbsolute structure: Flack (1983), 508 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.26 (4)
Crystal data top
[RuCl2(C4H4N2)4]·2CH2Cl2Z = 4
Mr = 662.19Mo Kα radiation
Tetragonal, I4122µ = 1.28 mm1
a = 7.3059 (2) ÅT = 100 K
c = 47.3659 (16) Å0.10 × 0.10 × 0.08 mm
V = 2528.21 (14) Å3
Data collection top
Bruker APEXII CCD
diffractometer
1399 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1996)
1363 reflections with I > 2σ(I)
Tmin = 0.882, Tmax = 0.908Rint = 0.030
15409 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.016H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.040Δρmax = 1.01 e Å3
S = 1.03Δρmin = 0.38 e Å3
1399 reflectionsAbsolute structure: Flack (1983), 508 Friedel pairs
81 parametersAbsolute structure parameter: 0.26 (4)
0 restraints
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
xyzUiso*/Ueq
Ru11.00000.50000.25000.01016 (7)
Cl10.76849 (5)0.26849 (5)0.25000.01419 (11)
N10.8611 (2)0.6437 (2)0.21927 (3)0.0125 (3)
C10.9492 (2)0.7136 (2)0.19664 (3)0.0140 (3)
H1A1.07750.69610.19490.017*
Cl20.74959 (8)0.41921 (8)0.141441 (10)0.02798 (12)
N20.6770 (2)0.8453 (2)0.17735 (3)0.0194 (3)
C20.8562 (2)0.8101 (2)0.17601 (4)0.0163 (4)
H2A0.92300.85340.16010.020*
C30.5910 (3)0.7769 (3)0.19991 (4)0.0178 (4)
H3A0.46340.79870.20190.021*
C40.6795 (3)0.6757 (2)0.22056 (3)0.0146 (3)
H4A0.61080.62790.23590.018*
C50.6136 (4)0.25000.12500.0271 (6)
H5A0.546 (3)0.309 (3)0.1112 (4)0.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.00969 (8)0.00969 (8)0.01110 (12)0.00041 (10)0.0000.000
Cl10.01315 (16)0.01315 (16)0.0163 (2)0.0024 (2)0.00218 (17)0.00218 (17)
N10.0128 (8)0.0111 (7)0.0134 (6)0.0000 (5)0.0006 (6)0.0012 (6)
C10.0121 (8)0.0141 (8)0.0159 (8)0.0009 (6)0.0015 (6)0.0008 (7)
Cl20.0296 (3)0.0277 (3)0.0266 (3)0.0024 (2)0.0107 (2)0.0016 (2)
N20.0207 (8)0.0184 (8)0.0191 (7)0.0031 (6)0.0011 (7)0.0044 (6)
C20.0187 (9)0.0150 (9)0.0153 (8)0.0017 (7)0.0023 (7)0.0015 (7)
C30.0133 (9)0.0194 (9)0.0207 (9)0.0024 (7)0.0013 (7)0.0011 (7)
C40.0135 (9)0.0147 (9)0.0157 (7)0.0000 (6)0.0011 (7)0.0005 (7)
C50.0182 (14)0.0382 (19)0.0249 (14)0.0000.0000.0117 (14)
Geometric parameters (Å, º) top
Ru1—N12.0620 (14)Cl2—C51.7668 (17)
Ru1—N1i2.0620 (14)N2—C21.336 (2)
Ru1—N1ii2.0620 (14)N2—C31.337 (2)
Ru1—N1iii2.0620 (14)C2—H2A0.9500
Ru1—Cl1iii2.3920 (5)C3—C41.386 (3)
Ru1—Cl12.3920 (5)C3—H3A0.9500
N1—C41.349 (2)C4—H4A0.9500
N1—C11.351 (2)C5—Cl2iv1.7668 (17)
C1—C21.383 (2)C5—H5A0.92 (2)
C1—H1A0.9500
N1—Ru1—N1i89.82 (8)C1—N1—Ru1121.20 (12)
N1—Ru1—N1ii178.62 (9)N1—C1—C2121.29 (16)
N1i—Ru1—N1ii90.20 (7)N1—C1—H1A119.4
N1—Ru1—N1iii90.20 (7)C2—C1—H1A119.4
N1i—Ru1—N1iii178.62 (9)C2—N2—C3115.27 (16)
N1ii—Ru1—N1iii89.82 (7)N2—C2—C1123.07 (17)
N1—Ru1—Cl1iii89.31 (5)N2—C2—H2A118.5
N1i—Ru1—Cl1iii90.69 (5)C1—C2—H2A118.5
N1ii—Ru1—Cl1iii89.31 (5)N2—C3—C4122.98 (17)
N1iii—Ru1—Cl1iii90.69 (5)N2—C3—H3A118.5
N1—Ru1—Cl190.69 (5)C4—C3—H3A118.5
N1i—Ru1—Cl189.31 (5)N1—C4—C3121.27 (16)
N1ii—Ru1—Cl190.69 (5)N1—C4—H4A119.4
N1iii—Ru1—Cl189.31 (5)C3—C4—H4A119.4
Cl1iii—Ru1—Cl1180.0Cl2—C5—Cl2iv111.58 (16)
C4—N1—C1116.08 (15)Cl2—C5—H5A106.7 (15)
C4—N1—Ru1122.71 (12)Cl2iv—C5—H5A108.1 (15)
Symmetry codes: (i) y+3/2, x+3/2, z+1/2; (ii) y+1/2, x1/2, z+1/2; (iii) x+2, y+1, z; (iv) x, y+1/2, z+1/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···Cl1v0.952.883.555 (2)129
C5—H5A···N2vi0.92 (2)2.46 (2)3.338 (2)158 (2)
Symmetry codes: (v) x+1, y+1, z; (vi) x+1, y1/2, z+1/4.

Experimental details

Crystal data
Chemical formula[RuCl2(C4H4N2)4]·2CH2Cl2
Mr662.19
Crystal system, space groupTetragonal, I4122
Temperature (K)100
a, c (Å)7.3059 (2), 47.3659 (16)
V3)2528.21 (14)
Z4
Radiation typeMo Kα
µ (mm1)1.28
Crystal size (mm)0.10 × 0.10 × 0.08
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1996)
Tmin, Tmax0.882, 0.908
No. of measured, independent and
observed [I > 2σ(I)] reflections
15409, 1399, 1363
Rint0.030
(sin θ/λ)max1)0.640
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.016, 0.040, 1.03
No. of reflections1399
No. of parameters81
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.01, 0.38
Absolute structureFlack (1983), 508 Friedel pairs
Absolute structure parameter0.26 (4)

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···Cl1i0.952.883.555 (2)129
C5—H5A···N2ii0.92 (2)2.46 (2)3.338 (2)158 (2)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y1/2, z+1/4.
 

Acknowledgements

We thank Austin College (Cullen Funds) for supporting innovative undergraduate education and the Welch Foundation (AD-0007) for a chemistry department grant furthering undergraduate research. We also recognize the work of Jessie H. Berger, Tehreem Bilal, Michela L. Brumfield, Raven M. Clark, Edward J. Selvik, Jacob B. Smith, and Hans H. Yoon, who, as fellow students with WK and AER in an advanced inorganic lab, synthesized and attempted to grow crystals of the title compound.

References

First citationBruker (1996). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationBruker (2007). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationCarlucci, L., Ciani, G., Porta, F., Proserpio, D. M. & Santagostini, L. (2002). Angew. Chem. Int. Ed. 41, 1907–1911.  CrossRef CAS
First citationCoe, B. J. (2004). J. Chem. Ed. 81, 718–721.  CrossRef CAS
First citationCoe, B. J., Meyer, T. J. & White, P. S. (1995). Inorg. Chem. 34, 593–602.  CSD CrossRef CAS Web of Science
First citationDesjardins, P., Yap, G. P. A. & Crutchley, R. J. (1999). Inorg. Chem. 38, 5901–5905.  Web of Science CSD CrossRef CAS
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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