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ISSN: 2056-9890

trans-Di­chloridobis(quinoline-κN)platinum(II)

aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 28 March 2012; accepted 29 March 2012; online 4 April 2012)

In the title complex, trans-[PtCl2(C9H7N)2], the PtII ion is four-coordinated in an essentially square-planar coordination environment defined by two N atoms from two quinoline (qu) ligands and two Cl anions. The Pt atom is located on an inversion centre and thus the asymmetric unit contains one half of the complex; the PtN2Cl2 unit is exactly planar. The dihedral angle between the PtN2Cl2 unit and the quinoline ligand is 85.1 (1)°. In the crystal, the complex mol­ecules are stacked into columns along the b axis. In the columns, several inter­molecular ππ inter­actions between the six-membered rings are present, the shortest ring centroid–centroid distance being 3.733 (5) Å between pyridine rings.

Related literature

For the crystal structure of (H-qu)2[PtCl6]·2H2O, see: Ha (2012a[Ha, K. (2012a). Z. Kristallogr. New Cryst. Struct. 227, 31-32.]). For the crystal structures of the related PtII complexes cis-[PtCl2(qu)2].0.25DMF (DMF = N,N-dimethyl­formamide) and cis-[PtCl2(qu)2].CH3NO2, see: Davies et al. (2001[Davies, M. S., Diakos, C. I., Messerle, B. A. & Hambley, T. W. (2001). Inorg. Chem. 40, 3048-3054.]); Ha (2012b[Ha, K. (2012b). Acta Cryst. E68, m491.]).

[Scheme 1]

Experimental

Crystal data
  • [PtCl2(C9H7N)2]

  • Mr = 524.30

  • Monoclinic, C 2/c

  • a = 16.3722 (18) Å

  • b = 6.9543 (7) Å

  • c = 16.0422 (17) Å

  • β = 118.684 (2)°

  • V = 1602.4 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 9.09 mm−1

  • T = 200 K

  • 0.21 × 0.08 × 0.07 mm

Data collection
  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.596, Tmax = 1.000

  • 4630 measured reflections

  • 1569 independent reflections

  • 1025 reflections with I > 2σ(I)

  • Rint = 0.053

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.080

  • S = 0.97

  • 1569 reflections

  • 106 parameters

  • H-atom parameters constrained

  • Δρmax = 1.74 e Å−3

  • Δρmin = −0.97 e Å−3

Table 1
Selected geometric parameters (Å, °)

Pt1—N1 2.036 (6)
Pt1—Cl1 2.297 (2)
N1—Pt1—Cl1 89.40 (18)

Data collection: SMART (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SADABS, SMART 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: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title complex, [PtCl2(qu)2] (qu = quinoline), was unexpected obtained as a byproduct from the reaction of K2PtCl6 with qu. The main product of the rection was found as the PtIV complex, (H-qu)2[PtCl6].2H2O, and its crystal structure has been previously reported (Ha, 2012a). It seems that the PtIV ion reduced partially to the PtII ion in the reaction.

In the complex, the PtII ion is four-coordinated in an essentially square-planar coordination environment defined by two N atoms from two qu ligands and two Cl- anions (Fig. 1 and Table 1). The Cl atoms are in trans conformation with respect to each other. By contrast, in the analogous PtII complexes [PtCl2(qu)2].0.25DMF (DMF = N,N-dimethylformamide) (Davies et al., 2001) and [PtCl2(qu)2].CH3NO2 (Ha, 2012b), the Cl atoms are in cis conformation. The cis-PtII complexes were synthesized from the reaction of K2PtCl4 with qu.

The Pt atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex; the PtN2Cl2 unit is exactly planar. The nearly planar qu ligands, with a maximum deviation of 0.012 (7) Å from the least-squares plane, are parallel. The dihedral angle between the PtN2Cl2 unit and qu ligand is 85.1 (1)°. The Cl atoms are almost perpendicular to the qu planes, with the bond angle of <N1—Pt1—Cl1 = 89.40 (18)°. In the crystal, the complex molecules are arranged in a V-shaped packing pattern and stacked into two distinct columns along the b axis (Fig. 2). In the columns, several intermolecular π-π interactions between the six-membered rings are present, the shortest ring centroid-centroid distance being 3.733 (5) Å between pyridine rings.

Related literature top

For the crystal structure of (H-qu)2[PtCl6].2H2O, see: Ha (2012a). For the crystal structures of the related PtII complexes cis-[PtCl2(qu)2].0.25DMF (DMF = N,N-dimethylformamide) and cis-[PtCl2(qu)2].CH3NO2, see: Davies et al. (2001); Ha (2012b).

Experimental top

The single crystals of the title complex were obtained as a byproduct from the reaction of K2PtCl6 (0.2432 g, 0.500 mmol) with quinoline (0.1569 g, 1.215 mmol) in H2O (30 ml). After refluxing of the reaction mixture for 3 h, the formed brown precipitate was removed by filtration, and the solvent of the filtrate was evaporated. The residue was washed with H2O/acetone (1:5) and dried at 50 °C, to give a yellow powder (0.2072 g) (Ha, 2012a). Crystals suitable for X-ray analysis were obtained by slow evaporation at 60 °C from an N,N-dimethylformamide (DMF) solution, which was obtained after filtration of the product over the solid-phase extraction column (4 ml) with silica (200 mg).

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective parent atoms: C—H = 0.95 Å with Uiso(H) = 1.2Ueq(C). The highest peak (1.74 e Å-3) and the deepest hole (-0.97 e Å-3) in the difference Fourier map are located 1.10 Å and 1.51 Å, respectively, from the atoms Pt1 and N1.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title complex, with displacement ellipsoids drawn at the 50% probability level and the atom numbering. Unlabelled atoms are related to the reference atoms by the (-x, 1 - y, -z) symmetry transformation.
[Figure 2] Fig. 2. A view of the unit-cell contents of the title complex.
trans-Dichloridobis(quinoline-κN)platinum(II) top
Crystal data top
[PtCl2(C9H7N)2]F(000) = 992
Mr = 524.30Dx = 2.173 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2043 reflections
a = 16.3722 (18) Åθ = 2.8–25.9°
b = 6.9543 (7) ŵ = 9.09 mm1
c = 16.0422 (17) ÅT = 200 K
β = 118.684 (2)°Block, yellow
V = 1602.4 (3) Å30.21 × 0.08 × 0.07 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer
1569 independent reflections
Radiation source: fine-focus sealed tube1025 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ϕ and ω scansθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 2017
Tmin = 0.596, Tmax = 1.000k = 88
4630 measured reflectionsl = 1919
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0357P)2]
where P = (Fo2 + 2Fc2)/3
1569 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 1.74 e Å3
0 restraintsΔρmin = 0.97 e Å3
Crystal data top
[PtCl2(C9H7N)2]V = 1602.4 (3) Å3
Mr = 524.30Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.3722 (18) ŵ = 9.09 mm1
b = 6.9543 (7) ÅT = 200 K
c = 16.0422 (17) Å0.21 × 0.08 × 0.07 mm
β = 118.684 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
1569 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1025 reflections with I > 2σ(I)
Tmin = 0.596, Tmax = 1.000Rint = 0.053
4630 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.080H-atom parameters constrained
S = 0.97Δρmax = 1.74 e Å3
1569 reflectionsΔρmin = 0.97 e Å3
106 parameters
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
Pt10.00000.50000.00000.02655 (16)
Cl10.01185 (14)0.3931 (3)0.12923 (14)0.0373 (5)
N10.1091 (4)0.3178 (9)0.0354 (4)0.0270 (15)
C10.0927 (5)0.1473 (11)0.0038 (5)0.0297 (19)
H10.03040.11670.04920.036*
C20.1608 (6)0.0079 (12)0.0170 (6)0.0353 (18)
H20.14550.11330.01410.042*
C30.2506 (6)0.0500 (11)0.0836 (6)0.036 (2)
H30.29860.04260.09980.043*
C40.2710 (5)0.2304 (11)0.1273 (5)0.0247 (17)
C50.3626 (5)0.2867 (13)0.1961 (5)0.036 (2)
H50.41250.19820.21420.043*
C60.3801 (6)0.4626 (12)0.2362 (6)0.036 (2)
H60.44160.49700.28210.043*
C70.3073 (6)0.5943 (14)0.2100 (6)0.037 (2)
H70.32010.71840.23820.044*
C80.2177 (6)0.5482 (11)0.1443 (6)0.031 (2)
H80.16910.63930.12750.037*
C90.1986 (5)0.3668 (11)0.1025 (5)0.0257 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.0162 (2)0.0315 (2)0.0279 (2)0.0031 (3)0.00741 (16)0.0021 (3)
Cl10.0322 (11)0.0474 (13)0.0335 (10)0.0094 (11)0.0169 (9)0.0103 (11)
N10.016 (3)0.031 (4)0.033 (3)0.000 (3)0.011 (3)0.003 (3)
C10.023 (4)0.027 (5)0.033 (4)0.003 (4)0.009 (4)0.005 (4)
C20.041 (5)0.025 (4)0.045 (4)0.001 (5)0.025 (4)0.001 (5)
C30.034 (5)0.037 (6)0.045 (5)0.011 (4)0.025 (4)0.011 (4)
C40.025 (4)0.023 (4)0.033 (4)0.002 (3)0.018 (4)0.007 (4)
C50.019 (4)0.050 (6)0.036 (5)0.008 (4)0.011 (4)0.009 (4)
C60.025 (4)0.054 (7)0.029 (4)0.000 (4)0.013 (4)0.000 (4)
C70.030 (5)0.042 (5)0.033 (4)0.005 (4)0.011 (4)0.008 (4)
C80.023 (4)0.036 (6)0.034 (4)0.001 (3)0.014 (4)0.005 (4)
C90.022 (4)0.030 (5)0.026 (4)0.002 (4)0.013 (4)0.004 (4)
Geometric parameters (Å, º) top
Pt1—N1i2.036 (6)C3—H30.9500
Pt1—N12.036 (6)C4—C91.418 (10)
Pt1—Cl1i2.297 (2)C4—C51.425 (10)
Pt1—Cl12.297 (2)C5—C61.347 (10)
N1—C11.308 (9)C5—H50.9500
N1—C91.382 (9)C6—C71.398 (12)
C1—C21.392 (10)C6—H60.9500
C1—H10.9500C7—C81.371 (11)
C2—C31.371 (12)C7—H70.9500
C2—H20.9500C8—C91.392 (11)
C3—C41.398 (10)C8—H80.9500
N1i—Pt1—N1180.0C3—C4—C9119.6 (7)
N1i—Pt1—Cl1i89.40 (18)C3—C4—C5123.0 (8)
N1—Pt1—Cl1i90.60 (18)C9—C4—C5117.4 (7)
N1i—Pt1—Cl190.60 (18)C6—C5—C4121.5 (8)
N1—Pt1—Cl189.40 (18)C6—C5—H5119.2
Cl1i—Pt1—Cl1180.00 (10)C4—C5—H5119.2
C1—N1—C9119.7 (7)C5—C6—C7119.7 (8)
C1—N1—Pt1118.7 (5)C5—C6—H6120.1
C9—N1—Pt1121.6 (5)C7—C6—H6120.1
N1—C1—C2124.0 (7)C8—C7—C6121.4 (8)
N1—C1—H1118.0C8—C7—H7119.3
C2—C1—H1118.0C6—C7—H7119.3
C3—C2—C1118.3 (8)C7—C8—C9119.5 (7)
C3—C2—H2120.8C7—C8—H8120.2
C1—C2—H2120.8C9—C8—H8120.2
C2—C3—C4119.4 (8)N1—C9—C8120.6 (7)
C2—C3—H3120.3N1—C9—C4119.0 (7)
C4—C3—H3120.3C8—C9—C4120.5 (7)
Cl1i—Pt1—N1—C186.2 (6)C5—C6—C7—C80.3 (13)
Cl1—Pt1—N1—C193.8 (6)C6—C7—C8—C90.2 (12)
Cl1i—Pt1—N1—C996.8 (5)C1—N1—C9—C8179.3 (7)
Cl1—Pt1—N1—C983.2 (5)Pt1—N1—C9—C83.7 (9)
C9—N1—C1—C20.6 (12)C1—N1—C9—C40.1 (10)
Pt1—N1—C1—C2177.7 (6)Pt1—N1—C9—C4177.1 (5)
N1—C1—C2—C30.9 (13)C7—C8—C9—N1179.3 (7)
C1—C2—C3—C40.6 (12)C7—C8—C9—C40.1 (12)
C2—C3—C4—C90.2 (12)C3—C4—C9—N10.1 (11)
C2—C3—C4—C5179.1 (7)C5—C4—C9—N1179.4 (7)
C3—C4—C5—C6179.2 (8)C3—C4—C9—C8179.1 (7)
C9—C4—C5—C60.1 (11)C5—C4—C9—C80.2 (11)
C4—C5—C6—C70.2 (12)
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula[PtCl2(C9H7N)2]
Mr524.30
Crystal system, space groupMonoclinic, C2/c
Temperature (K)200
a, b, c (Å)16.3722 (18), 6.9543 (7), 16.0422 (17)
β (°) 118.684 (2)
V3)1602.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)9.09
Crystal size (mm)0.21 × 0.08 × 0.07
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.596, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
4630, 1569, 1025
Rint0.053
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.080, 0.97
No. of reflections1569
No. of parameters106
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.74, 0.97

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
Pt1—N12.036 (6)Pt1—Cl12.297 (2)
N1—Pt1—Cl189.40 (18)
 

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011–0030747).

References

First citationBruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDavies, M. S., Diakos, C. I., Messerle, B. A. & Hambley, T. W. (2001). Inorg. Chem. 40, 3048–3054.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationHa, K. (2012a). Z. Kristallogr. New Cryst. Struct. 227, 31–32.  CAS Google Scholar
First citationHa, K. (2012b). Acta Cryst. E68, m491.  CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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