supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2114    [ doi:10.1107/S1600536807033065 ]

Redetermination of cis-diacetonitrilebis(2,2'-bipyridine)ruthenium(II) hexafluorophosphate

F. Xu and W. Huang

Abstract top

The title compound, [Ru(C10H8N2)2(CH3CN)2](PF6)2, a six-coordinate ruthenium(II) complex, crystallizes in the monoclinic C2/c space group showing different symmetry from the previously reported P21/n. A crystallographic twofold rotation axis passes through the Ru atom. The two C atoms and H atoms of one acetonitrile ligand are disordered over two positions, with site occupancy factors of ca 0.55 and 0.45. Three F atoms are disordered over two positions, with similar site occupancy factors.

Comment top

The structures of cis-bis(acetonitrile)bis(2,2'-bipyridine) ruthenium(II) diperchlorate (Chattopadhyay et al., 2004), trans-bis(acetonitrile)bis(2,2'-bipyridine) ruthenium(II) diperchlorate (Cordes et al., 1992), and the title complex (Heeg et al., 1985) have been reported previously. We present herein the crystal structure of the title compound (I) again with the same unit cell as Heeg et al.'s within the experimental error, but it crystallizes in the monoclinic C2/c space group other than the earlier P21/n.

The atom-numbering scheme of compound (I) is shown in Fig.1, while selected bond distances and angles are given in Table 1. The Ru—N bond lengths and bond angles are comparable with those in literature. The presence of acetonitrile molecules in this Ru(II) complex can be verified by routine characterization. The main difference between our data and Heeg et al.'s is the assignment of the space group. Our results demonstrate the higher symmetry of molecule (C2/c instead of P21/n), and two carbon atoms of monodentate acetonitrile molecules are refined disorderly. We failed to solve this structure by assigning the reported P21/n space group.

Related literature top

For the earlier report of this crystal structure, see: Heeg et al. (1985). For analogous complexes, see: Chattopadhyay et al. (2004); Cordes et al. (1992).

Experimental top

The title complex (I) was obtained by refluxing equal molar ratio of Ru(bpy)2Cl2·H2O (0.02 g, 0.04 mmol) and a pre-synthesized schiff base, 4-[2-(pyridin-4-ylimino)-ethyl]-benzoic acid (0.01 g, 0.04 mmol) in 30 ml acetonitrile for 1 h. The mixture was cooled to room temperature and a 10 ml saturated NH4PF6 solution was added. Orange single-crystal of (I) suitable for the X-ray diffraction analysis was grown directly from the mother liquor as a by-product. Elemental analysis, calculated for RuC24H22N6P2F12: C, 36.70; H, 2.82; N, 10.70%; found: C, 36.55; H, 2.99; N, 10.48%. IR (KBr): 3123, 3094, 3003, 2938, 1606, 1468, 1449, 1314, 1276, 1243, 1164, 1040, 833, 762, and 557 cm−1. 1H NMR (d6-DMSO): δ (p.p.m.) 9.364 (2H), 8.778 (2H), 8.649 (2H), 8.353 (2H), 8.031 (2H), 7.931 (2H), 7.575 (2H), 7.373 (2H), 2.437 (6H).

Refinement top

The non-hydrogen atoms were refined anisotropically, whereas the H atoms were placed in geometrically idealized positions (C—H = 0.93–0.96 Å) and refined as riding atoms, with Uiso(H) = 1.5Ueq(for methyl C) or Uiso(H) = 1.2Ueq(C) for the other C atoms. F2, F3 and F6 atoms of hexafluorophosphate are refined over two sites with 0.557 (17):0.443 (17) site occupancy factors. Due to the disorder of acetonitrile molecules, the 'similar Uij' restraints (SIMU) were used to restrain the Uij components of neighboring atoms (N3—C11 and N3—C11', six for each). The effective standard deviations is set as 0.004 for N3—C11 and 0.003 for N3—C11', respectively.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A drawing of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and the H atoms are omitted for clarity.
cis-diacetonitrilebis(2,2'-bipyridine)ruthenium(II) hexafluorophosphate top
Crystal data top
[Ru(C10H8N2)2(C2H3N)2](F6P)2F(000) = 1560
Mr = 785.49Dx = 1.739 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1829 reflections
a = 17.2499 (18) Åθ = 2.3–19.1°
b = 10.5008 (11) ŵ = 0.73 mm−1
c = 16.6600 (17) ÅT = 291 K
β = 96.201 (2)°Block, orange
V = 3000.1 (5) Å30.16 × 0.12 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2641 independent reflections
Radiation source: fine-focus sealed tube1718 reflections with I > 2σ(I)
graphiteRint = 0.035
φ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −20→18
Tmin = 0.892, Tmax = 0.931k = −9→12
7231 measured reflectionsl = −19→15
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0345P)2 + 1.566P]
where P = (Fo2 + 2Fc2)/3
2641 reflections(Δ/σ)max < 0.001
251 parametersΔρmax = 0.54 e Å−3
12 restraintsΔρmin = −0.31 e Å−3
Crystal data top
[Ru(C10H8N2)2(C2H3N)2](F6P)2V = 3000.1 (5) Å3
Mr = 785.49Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.2499 (18) ŵ = 0.73 mm−1
b = 10.5008 (11) ÅT = 291 K
c = 16.6600 (17) Å0.16 × 0.12 × 0.10 mm
β = 96.201 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2641 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1718 reflections with I > 2σ(I)
Tmin = 0.892, Tmax = 0.931Rint = 0.035
7231 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.54 e Å−3
S = 0.99Δρmin = −0.31 e Å−3
2641 reflectionsAbsolute structure: ?
251 parametersFlack parameter: ?
12 restraintsRogers parameter: ?
Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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*/UeqOcc. (<1)
Ru10.00000.97826 (5)0.75000.0657 (2)
C10.0270 (3)1.1608 (4)0.8777 (3)0.0689 (12)
C20.0579 (4)1.2636 (5)0.9204 (3)0.1081 (19)
H20.03461.29430.96440.130*
C30.1238 (5)1.3207 (6)0.8976 (4)0.147 (3)
H30.14591.38980.92660.177*
C40.1562 (4)1.2770 (7)0.8338 (4)0.145 (3)
H40.20051.31530.81740.174*
C50.1225 (3)1.1744 (6)0.7932 (3)0.0982 (17)
H50.14561.14330.74920.118*
C6−0.0394 (3)1.0877 (4)0.8992 (3)0.0652 (12)
C7−0.0783 (3)1.1116 (5)0.9658 (3)0.0906 (15)
H7−0.06511.18180.99850.109*
C8−0.1358 (3)1.0317 (7)0.9831 (3)0.1064 (19)
H8−0.16191.04621.02820.128*
C9−0.1549 (3)0.9330 (7)0.9356 (3)0.120 (2)
H9−0.19440.87770.94700.144*
C10−0.1151 (3)0.9134 (6)0.8687 (3)0.1113 (19)
H10−0.12850.84350.83570.134*
C110.1279 (11)0.7826 (11)0.8336 (6)0.115 (3)0.546 (11)
C120.1854 (8)0.6918 (10)0.8694 (6)0.109 (5)0.546 (11)
H12A0.23630.72930.87120.163*0.546 (11)
H12B0.17440.67170.92320.163*0.546 (11)
H12C0.18370.61540.83760.163*0.546 (11)
C11'0.0731 (12)0.7344 (15)0.8298 (8)0.120 (2)0.454 (11)
C12'0.1042 (13)0.6169 (14)0.8608 (8)0.141 (9)0.454 (11)
H12D0.06520.55390.86760.212*0.454 (11)
H12E0.13920.58540.82440.212*0.454 (11)
H12F0.13300.63510.91220.212*0.454 (11)
F10.6154 (3)0.8889 (5)0.6588 (3)0.220 (3)
F20.7125 (6)1.035 (2)0.5688 (7)0.183 (7)0.559 (18)
F30.7302 (9)0.9507 (18)0.6692 (13)0.203 (8)0.559 (18)
F40.6351 (8)1.0821 (9)0.6847 (6)0.384 (7)
F50.5853 (3)1.0436 (9)0.5748 (5)0.288 (4)
F60.7016 (15)0.887 (2)0.587 (2)0.326 (13)0.559 (18)
F2'0.6890 (14)1.1222 (15)0.5882 (13)0.180 (9)0.441 (18)
F3'0.7146 (12)1.006 (3)0.7012 (8)0.187 (11)0.441 (18)
F6'0.6389 (14)0.9189 (12)0.5469 (6)0.168 (8)0.441 (18)
N10.0599 (2)1.1177 (3)0.8125 (2)0.0642 (9)
N2−0.0591 (2)0.9896 (3)0.8497 (2)0.0687 (10)
N30.0682 (3)0.8417 (4)0.8050 (2)0.1189 (17)
P10.65715 (12)0.9967 (2)0.62417 (10)0.1139 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.0907 (4)0.0551 (3)0.0515 (3)0.0000.0074 (3)0.000
C10.085 (4)0.057 (3)0.061 (3)0.000 (3)−0.008 (3)0.000 (2)
C20.166 (6)0.082 (4)0.074 (4)−0.031 (4)0.005 (4)−0.012 (3)
C30.218 (8)0.130 (6)0.089 (5)−0.103 (6)−0.004 (5)−0.003 (4)
C40.155 (6)0.197 (8)0.078 (5)−0.096 (6)−0.013 (5)0.013 (5)
C50.084 (4)0.144 (5)0.064 (3)−0.033 (4)−0.006 (3)0.009 (3)
C60.075 (3)0.064 (3)0.056 (3)0.011 (3)0.003 (2)0.005 (2)
C70.107 (4)0.096 (4)0.071 (4)0.021 (4)0.015 (3)−0.005 (3)
C80.088 (4)0.159 (6)0.075 (4)0.011 (4)0.021 (3)0.016 (4)
C90.094 (4)0.193 (7)0.074 (4)−0.050 (5)0.012 (4)0.019 (4)
C100.135 (5)0.132 (5)0.069 (4)−0.059 (4)0.016 (4)−0.002 (3)
C110.205 (7)0.081 (5)0.061 (4)0.052 (4)0.028 (5)0.010 (4)
C120.146 (12)0.082 (8)0.099 (8)0.034 (8)0.013 (7)0.020 (6)
C11'0.213 (6)0.087 (4)0.063 (4)0.059 (4)0.028 (4)0.012 (3)
C12'0.22 (2)0.096 (11)0.115 (11)0.073 (13)0.047 (12)0.043 (9)
F10.222 (5)0.218 (5)0.208 (5)−0.120 (4)−0.027 (4)0.087 (4)
F20.142 (7)0.30 (2)0.126 (7)0.003 (13)0.080 (6)0.050 (12)
F30.191 (11)0.197 (13)0.198 (16)0.025 (9)−0.082 (11)0.049 (11)
F40.569 (16)0.342 (11)0.225 (8)0.239 (12)−0.031 (10)−0.106 (8)
F50.146 (4)0.454 (12)0.262 (7)0.016 (6)0.007 (5)0.195 (8)
F60.228 (19)0.34 (2)0.42 (3)0.023 (18)0.09 (2)−0.14 (2)
F2'0.217 (19)0.117 (10)0.193 (15)−0.078 (10)−0.044 (12)0.073 (9)
F3'0.181 (15)0.29 (2)0.084 (7)−0.153 (17)0.000 (8)−0.019 (9)
F6'0.26 (2)0.150 (9)0.084 (7)0.009 (11)−0.018 (8)−0.029 (6)
N10.068 (3)0.069 (2)0.054 (2)−0.006 (2)−0.0019 (19)0.0053 (18)
N20.081 (3)0.072 (3)0.053 (2)−0.017 (2)0.0063 (19)0.0030 (19)
N30.213 (5)0.085 (3)0.061 (2)0.061 (3)0.027 (3)0.012 (2)
P10.1182 (15)0.1435 (18)0.0797 (11)−0.0289 (14)0.0096 (12)0.0056 (12)
Geometric parameters (Å, °) top
Ru1—N3i2.012 (4)C9—C101.387 (7)
Ru1—N32.012 (4)C9—H90.9300
Ru1—N12.016 (3)C10—N21.319 (6)
Ru1—N1i2.016 (3)C10—H100.9300
Ru1—N22.045 (3)C11—N31.251 (14)
Ru1—N2i2.045 (3)C11—C121.456 (13)
C1—N11.358 (5)C12—H12A0.9599
C1—C21.369 (6)C12—H12B0.9601
C1—C61.455 (6)C12—H12C0.9600
C2—C31.375 (8)C11'—N31.200 (15)
C2—H20.9300C11'—C12'1.421 (15)
C3—C41.335 (9)C12'—H12D0.9600
C3—H30.9300C12'—H12E0.9600
C4—C51.368 (7)C12'—H12F0.9601
C4—H40.9300F1—P11.490 (4)
C5—N11.303 (5)F2—P11.455 (10)
C5—H50.9300F3—P11.477 (12)
C6—N21.340 (5)F4—P11.432 (7)
C6—C71.381 (6)F5—P11.495 (5)
C7—C81.354 (7)F6—P11.549 (17)
C7—H70.9300F2'—P11.571 (11)
C8—C91.323 (8)F3'—P11.538 (15)
C8—H80.9300F6'—P11.529 (10)
N3i—Ru1—N389.1 (3)H12A—C12—H12F145.9
N3i—Ru1—N1174.27 (17)H12C—C12—H12F86.5
N3—Ru1—N192.31 (17)H12E—C12—H12F65.8
N3i—Ru1—N1i92.31 (17)N3—C11'—C12'161.9 (19)
N3—Ru1—N1i174.27 (17)C11'—C12'—H12C104.0
N1—Ru1—N1i86.83 (19)C11'—C12'—H12D113.5
N3i—Ru1—N295.34 (16)H12C—C12'—H12D135.4
N3—Ru1—N289.42 (15)C11'—C12'—H12E108.0
N1—Ru1—N279.13 (15)H12D—C12'—H12E109.5
N1i—Ru1—N295.98 (15)C11'—C12'—H12F106.9
N3i—Ru1—N2i89.42 (15)H12C—C12'—H12F80.2
N3—Ru1—N2i95.34 (16)H12D—C12'—H12F109.5
N1—Ru1—N2i95.98 (15)H12E—C12'—H12F109.5
N1i—Ru1—N2i79.13 (15)C5—N1—C1118.4 (4)
N2—Ru1—N2i173.3 (2)C5—N1—Ru1126.7 (4)
N1—C1—C2120.4 (5)C1—N1—Ru1114.8 (3)
N1—C1—C6115.5 (4)C10—N2—C6117.6 (4)
C2—C1—C6124.1 (5)C10—N2—Ru1127.0 (3)
C1—C2—C3119.2 (6)C6—N2—Ru1115.4 (3)
C1—C2—H2120.4C11'—N3—C1151.6 (9)
C3—C2—H2120.4C11'—N3—Ru1147.3 (12)
C4—C3—C2120.0 (6)C11—N3—Ru1160.7 (9)
C4—C3—H3120.0F4—P1—F2121.0 (11)
C2—C3—H3120.0F4—P1—F397.1 (10)
C3—C4—C5118.2 (6)F2—P1—F380.2 (10)
C3—C4—H4120.9F4—P1—F191.5 (6)
C5—C4—H4120.9F2—P1—F1146.6 (10)
N1—C5—C4123.8 (6)F3—P1—F188.7 (6)
N1—C5—H5118.1F4—P1—F585.0 (6)
C4—C5—H5118.1F2—P1—F597.0 (6)
N2—C6—C7121.4 (5)F3—P1—F5177.1 (9)
N2—C6—C1114.1 (4)F1—P1—F593.2 (3)
C7—C6—C1124.4 (5)F4—P1—F6'151.9 (10)
C8—C7—C6119.3 (5)F2—P1—F6'72.8 (13)
C8—C7—H7120.4F3—P1—F6'109.9 (15)
C6—C7—H7120.4F1—P1—F6'81.8 (6)
C9—C8—C7120.0 (6)F5—P1—F6'68.3 (8)
C9—C8—H8120.0F4—P1—F3'64.3 (9)
C7—C8—H8120.0F2—P1—F3'95.9 (8)
C8—C9—C10118.9 (6)F1—P1—F3'91.2 (7)
C8—C9—H9120.5F5—P1—F3'149.1 (12)
C10—C9—H9120.5F6'—P1—F3'142.6 (15)
N2—C10—C9122.8 (5)F4—P1—F6158.4 (15)
N2—C10—H10118.6F2—P1—F664.1 (9)
C9—C10—H10118.6F3—P1—F662.0 (18)
N3—C11—C12167.6 (14)F1—P1—F682.8 (9)
C11—C12—H12A109.0F5—P1—F6116.1 (15)
C11—C12—H12B109.4F6'—P1—F647.9 (10)
H12A—C12—H12B109.5F3'—P1—F694.8 (19)
C11—C12—H12C110.0F4—P1—F2'82.7 (11)
H12A—C12—H12C109.5F3—P1—F2'98.8 (9)
H12B—C12—H12C109.5F1—P1—F2'171.1 (11)
C11—C12—H12E89.0F5—P1—F2'79.5 (7)
H12A—C12—H12E138.1F6'—P1—F2'100.1 (11)
H12B—C12—H12E98.8F3'—P1—F2'92.4 (9)
C11—C12—H12F92.2F6—P1—F2'105.0 (12)
Symmetry codes: (i) −x, y, −z+3/2.
Table 1
Selected geometric parameters (Å, °) top
Ru1—N32.012 (4)C6—N21.340 (5)
Ru1—N12.016 (3)C10—N21.319 (6)
Ru1—N22.045 (3)C11—N31.251 (14)
C1—N11.358 (5)C11'—N31.200 (15)
C5—N11.303 (5)
N3—Ru1—N192.31 (17)N1—Ru1—N279.13 (15)
N3—Ru1—N289.42 (15)
Acknowledgements top

We are indebted to the Major State Basic Research Development Program (No. 2006CB806104) and the National Natural Science Foundation of China (project No. 20301009) for financial support.

references
References top

Bruker (2000). SMART (Version 5.622), SAINT (Version 6.02a), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Chattopadhyay, S. K., Mitra, K., Biswas, S., Naskar, S., Mishra, D., Adhikary, B., Harrison, R. G. & Cannon, J. F. (2004). Transition Met. Chem. 29, 1–6.

Cordes, A. W., Durham, B., Pennington, W. T., Kuntz, B. & Allen, L. (1992). J. Crystallogr. Spectrosc. Res. 22, 699–704.

Heeg, M. J., Kroener, R. & Deutsch, E. (1985). Acta Cryst. C41, 684–686.