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Acta Cryst. (2013). E69, m218    [ doi:10.1107/S1600536813006545 ]

Chlorido[1,1'-(5-methyl-1,3-phenylene)bis(3,5-dimethyl-1H-imidazol-2-ylidene)]platinum(II)

K.-J. Peng, Z.-X. Wang and W. Wan

Abstract top

In the title compound, [Pt(C17H19N4)Cl], the PtII cation is C,C',C''-chelated by the 1,1'-(5-methyl-1,3-phenylene)bis(3,5-dimethyl-1H-imidazolylidene) anion and coordinated by a Cl- anion in a distorted square-planar coordination geometry. [pi]-[pi] stacking is observed between nearly parallel imidazole and benzene rings of adjacent molecules, the centroid-centroid distance being 3.802 (4) Å.

Comment top

Square planar Pt(II) complexes have attracted much attention due to their potential application in organic light-emitting diodes (Yang et al., 2008). Pt(N—C—N)X (where NCN,di(2-pyridinyl)benzene-based tridentate ligands, X=monoanionic ligands), are reported to have much higher quantum yield than Pt(C—N)(LX) (where CN,2-pyridylphenylbased bidentate ligands, LX, monoanionic ancillary ligands) with similar structures (Wang et al., 2010), so designing and studying tridentate Pt complexes for application in blue and white phosphorescent OLEDs is a worthwhile undertaking (Fleetham et al., 2012). Replacing pyridinyl group with methyl-imidazolyl group could potentially weaken the intermolecular interaction, resultingin a blue-shifted excimer emission (Bakken et al.,2012). Here we report a new Pt(C—C—C)X type of Pt complex using methyl-imidazolyl as ligands, structure shown in Figure 1.

In the title molecule the Pt(1)-C(1)-C(9) plane is almost coplanar with the benzene ring and with the plane of C(9)-N(1)-N(2) ring, the dihedral angles being 1.57° and 2.00°, respectively. The other Pt1 ring (Pt(1)-C(1)-C(10)) is, however, is slightly different, makes dihedral angles of 1.28° and 2.00° with the benzene ring and the plane of C(10)-N(3)-N(4), respectively. The Pt(II) centre forms a distorted square planar and makes an angle of 1.95° between the Pt(1)-C(1)-C(10) ring and Pt(1)-C(1)-C(9) ring; the bond lengths of Pt(1)—C(9) and Pt(1)—C(10) are almost the same, being 2.040 (4) and 2.045 (4), respectively. The angles of C(1)-Pt(1)-C(9) and C(1)-Pt(1)-C(10) being 79.38 (19)° and 79.62 (19)°, are also very near.

Related literature top

For the application of PtII complexes in organic light-emitting diodes, see: Yang et al. (2008); Bakken et al. (2012); Fleetham et al. (2012). For a related compound, see: Wang et al. (2010).

Experimental top

A mixture of 1,1'-[5-methyl-1,3-phenylene]bis[3,5-dimethyl-1H-imidazolium] diiodide (1 mmol) and 0.5 mmol silver oxide was stirred in a solution of 100 mL acetonitrile for 5 h at room temperature before 1equiv. Platinum chloride and 1eq. potassium carbonate were added. The reaction mixture was heated to reflux for an additional 24 h. Then the mixture was cooled to room temperature before 100 mL water was added. The resulting yellow precipitate was filtered off and washed with excessive methanol, water, and ether and dried under vacuum. The light yellowish product (in 20% yield) was obtained after thermal evaporation under high vacuum.1H NMR (500 MHz, δ in p.p.m., DMSO): 6.84 (s, 2H), 6.02 (s, 2H), 2.77 (s, 6H), 2.71(s, 6H), 2.35 (s, 3H).

Refinement top

Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion refined to fit the electron density with Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions with C—H = 0.93 Å and refined in riding mode, 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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 50% probability displacement ellipsoids (arbitrary spheres for H atoms)
Chlorido[1,1'-(5-methyl-1,3-phenylene)bis(3,5-dimethyl-1H-imidazol-2-ylidene)]platinum(II) top
Crystal data top
[Pt(C17H19N4)Cl]F(000) = 976
Mr = 509.90Dx = 2.036 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4377 reflections
a = 11.042 (5) Åθ = 2.4–27.5°
b = 14.552 (6) ŵ = 8.60 mm1
c = 11.524 (5) ÅT = 296 K
β = 116.049 (4)°Block, colorless
V = 1663.6 (12) Å30.16 × 0.13 × 0.07 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
2958 independent reflections
Radiation source: fine-focus sealed tube2579 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 10 pixels mm-1θmax = 25.0°, θmin = 2.1°
φ and ω scansh = 1213
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
k = 1617
Tmin = 0.340, Tmax = 0.584l = 1213
8411 measured reflections
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0412P)2 + 5.3708P]
where P = (Fo2 + 2Fc2)/3
2958 reflections(Δ/σ)max = 0.001
189 parametersΔρmax = 1.78 e Å3
0 restraintsΔρmin = 2.04 e Å3
Crystal data top
[Pt(C17H19N4)Cl]V = 1663.6 (12) Å3
Mr = 509.90Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.042 (5) ŵ = 8.60 mm1
b = 14.552 (6) ÅT = 296 K
c = 11.524 (5) Å0.16 × 0.13 × 0.07 mm
β = 116.049 (4)°
Data collection top
Bruker APEXII CCD
diffractometer
2958 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
2579 reflections with I > 2σ(I)
Tmin = 0.340, Tmax = 0.584Rint = 0.026
8411 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.080Δρmax = 1.78 e Å3
S = 1.07Δρmin = 2.04 e Å3
2958 reflectionsAbsolute structure: ?
189 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Pt10.48107 (2)0.137708 (16)0.63220 (2)0.02999 (11)
C10.6140 (6)0.1354 (4)0.5684 (6)0.0310 (14)
C20.6974 (6)0.0590 (4)0.5917 (6)0.0296 (13)
C30.7964 (6)0.0559 (4)0.5471 (6)0.0345 (14)
H30.85220.00490.56310.041*
C40.8098 (7)0.1319 (4)0.4772 (7)0.0390 (16)
C50.7255 (6)0.2074 (4)0.4513 (6)0.0335 (14)
H50.73400.25660.40390.040*
C60.6260 (6)0.2085 (4)0.4978 (6)0.0287 (13)
C70.5042 (7)0.3599 (4)0.4217 (7)0.0387 (16)
C80.3955 (7)0.3958 (5)0.4341 (7)0.0450 (17)
H80.35400.45190.40230.054*
C90.4420 (6)0.2595 (4)0.5339 (6)0.0340 (7)
C100.5694 (6)0.0138 (4)0.7018 (6)0.0362 (7)
C110.6528 (8)0.1257 (5)0.7757 (7)0.0462 (18)
H110.66550.18250.81640.055*
C120.7198 (7)0.0930 (4)0.7090 (6)0.0362 (14)
C130.9173 (9)0.1298 (6)0.4307 (10)0.060 (2)
H13A0.90790.18250.37730.091*
H13B0.90820.07490.38150.091*
H13C1.00450.13080.50350.091*
C140.2445 (8)0.3377 (6)0.5408 (9)0.056 (2)
H14A0.17130.29980.48380.084*
H14B0.21460.40030.53410.084*
H14C0.27440.31670.62810.084*
C150.5829 (8)0.4025 (5)0.3576 (8)0.053 (2)
H15A0.67670.40440.41750.080*
H15B0.55100.46390.33080.080*
H15C0.57140.36670.28360.080*
C160.4651 (9)0.0611 (6)0.8318 (8)0.057 (2)
H16A0.46070.00180.86610.085*
H16B0.49620.10560.90030.085*
H16C0.37710.07830.76770.085*
C170.8297 (8)0.1388 (4)0.6863 (8)0.0439 (17)
H17A0.80810.13590.59610.066*
H17B0.83750.20190.71300.066*
H17C0.91360.10780.73530.066*
Cl10.3130 (2)0.14031 (13)0.7148 (2)0.0560 (5)
N10.5316 (5)0.2784 (4)0.4818 (5)0.0340 (7)
N20.3591 (5)0.3319 (4)0.5039 (5)0.0340 (7)
N30.6696 (5)0.0091 (4)0.6648 (5)0.0362 (7)
N40.5613 (5)0.0576 (4)0.7712 (5)0.0362 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.02833 (16)0.03514 (16)0.03016 (16)0.00059 (10)0.01622 (11)0.00590 (10)
C10.025 (3)0.035 (3)0.033 (3)0.000 (3)0.013 (3)0.007 (3)
C20.032 (3)0.027 (3)0.029 (3)0.003 (3)0.013 (3)0.000 (2)
C30.032 (3)0.036 (3)0.037 (4)0.008 (3)0.017 (3)0.003 (3)
C40.034 (4)0.048 (4)0.041 (4)0.007 (3)0.021 (3)0.002 (3)
C50.035 (3)0.033 (3)0.035 (3)0.002 (3)0.018 (3)0.004 (3)
C60.031 (3)0.026 (3)0.027 (3)0.005 (2)0.012 (3)0.001 (2)
C70.041 (4)0.039 (4)0.035 (4)0.004 (3)0.016 (3)0.002 (3)
C80.048 (4)0.038 (4)0.049 (4)0.014 (3)0.022 (4)0.004 (3)
C90.0303 (17)0.0384 (17)0.0344 (18)0.0063 (14)0.0151 (14)0.0035 (14)
C100.0376 (18)0.0386 (18)0.0329 (18)0.0016 (15)0.0159 (15)0.0006 (14)
C110.051 (4)0.041 (4)0.039 (4)0.000 (3)0.012 (4)0.008 (3)
C120.040 (4)0.032 (3)0.030 (3)0.002 (3)0.009 (3)0.001 (3)
C130.053 (5)0.069 (6)0.081 (6)0.021 (4)0.050 (5)0.019 (4)
C140.052 (5)0.061 (5)0.064 (5)0.024 (4)0.033 (4)0.002 (4)
C150.067 (5)0.046 (4)0.062 (5)0.017 (4)0.042 (4)0.024 (4)
C160.071 (5)0.067 (5)0.044 (4)0.012 (4)0.036 (4)0.001 (4)
C170.045 (4)0.038 (4)0.048 (4)0.003 (3)0.019 (4)0.003 (3)
Cl10.0584 (12)0.0608 (12)0.0749 (14)0.0069 (9)0.0531 (12)0.0027 (9)
N10.0303 (17)0.0384 (17)0.0344 (18)0.0063 (14)0.0151 (14)0.0035 (14)
N20.0303 (17)0.0384 (17)0.0344 (18)0.0063 (14)0.0151 (14)0.0035 (14)
N30.0376 (18)0.0386 (18)0.0329 (18)0.0016 (15)0.0159 (15)0.0006 (14)
N40.0376 (18)0.0386 (18)0.0329 (18)0.0016 (15)0.0159 (15)0.0006 (14)
Geometric parameters (Å, º) top
Pt1—C11.909 (6)C10—N31.389 (8)
Pt1—C92.045 (6)C11—C121.366 (10)
Pt1—C102.040 (6)C11—N41.400 (9)
Pt1—Cl12.4295 (19)C11—H110.9300
C1—C61.380 (8)C12—N31.345 (8)
C1—C21.392 (8)C12—C171.504 (10)
C2—C31.398 (8)C13—H13A0.9600
C2—N31.419 (8)C13—H13B0.9600
C3—C41.414 (9)C13—H13C0.9600
C3—H30.9300C14—N21.504 (9)
C4—C51.385 (9)C14—H14A0.9600
C4—C131.502 (10)C14—H14B0.9600
C5—C61.419 (8)C14—H14C0.9600
C5—H50.9300C15—H15A0.9600
C6—N11.409 (7)C15—H15B0.9600
C7—N11.339 (8)C15—H15C0.9600
C7—C81.372 (10)C16—N41.507 (9)
C7—C151.499 (10)C16—H16A0.9600
C8—N21.399 (9)C16—H16B0.9600
C8—H80.9300C16—H16C0.9600
C9—N21.337 (8)C17—H17A0.9600
C9—N11.393 (8)C17—H17B0.9600
C10—N41.338 (8)C17—H17C0.9600
C1—Pt1—C1079.6 (3)C4—C13—H13A109.5
C1—Pt1—C979.2 (2)C4—C13—H13B109.5
C10—Pt1—C9158.8 (2)H13A—C13—H13B109.5
C1—Pt1—Cl1179.6 (2)C4—C13—H13C109.5
C10—Pt1—Cl1100.12 (18)H13A—C13—H13C109.5
C9—Pt1—Cl1101.06 (17)H13B—C13—H13C109.5
C6—C1—C2120.2 (6)N2—C14—H14A109.5
C6—C1—Pt1120.1 (4)N2—C14—H14B109.5
C2—C1—Pt1119.6 (5)H14A—C14—H14B109.5
C1—C2—C3120.9 (6)N2—C14—H14C109.5
C1—C2—N3112.1 (5)H14A—C14—H14C109.5
C3—C2—N3127.1 (5)H14B—C14—H14C109.5
C2—C3—C4118.5 (6)C7—C15—H15A109.5
C2—C3—H3120.7C7—C15—H15B109.5
C4—C3—H3120.7H15A—C15—H15B109.5
C5—C4—C3121.0 (6)C7—C15—H15C109.5
C5—C4—C13120.0 (6)H15A—C15—H15C109.5
C3—C4—C13119.0 (6)H15B—C15—H15C109.5
C4—C5—C6119.1 (6)N4—C16—H16A109.5
C4—C5—H5120.4N4—C16—H16B109.5
C6—C5—H5120.4H16A—C16—H16B109.5
C1—C6—N1112.2 (5)N4—C16—H16C109.5
C1—C6—C5120.2 (5)H16A—C16—H16C109.5
N1—C6—C5127.6 (5)H16B—C16—H16C109.5
N1—C7—C8107.0 (6)C12—C17—H17A109.5
N1—C7—C15124.9 (6)C12—C17—H17B109.5
C8—C7—C15128.1 (6)H17A—C17—H17B109.5
C7—C8—N2107.0 (6)C12—C17—H17C109.5
C7—C8—H8126.5H17A—C17—H17C109.5
N2—C8—H8126.5H17B—C17—H17C109.5
N2—C9—N1105.5 (5)C7—N1—C9110.9 (5)
N2—C9—Pt1141.3 (5)C7—N1—C6133.9 (6)
N1—C9—Pt1113.2 (4)C9—N1—C6115.1 (5)
N4—C10—N3105.6 (5)C9—N2—C8109.6 (5)
N4—C10—Pt1140.8 (5)C9—N2—C14122.4 (6)
N3—C10—Pt1113.5 (4)C8—N2—C14128.0 (6)
C12—C11—N4107.0 (6)C12—N3—C10110.7 (5)
C12—C11—H11126.5C12—N3—C2134.3 (5)
N4—C11—H11126.5C10—N3—C2115.1 (5)
N3—C12—C11107.1 (6)C10—N4—C11109.6 (6)
N3—C12—C17124.5 (6)C10—N4—C16123.4 (6)
C11—C12—C17128.4 (6)C11—N4—C16127.0 (6)
Selected bond lengths (Å) top
Pt1—C11.909 (6)Pt1—C102.040 (6)
Pt1—C92.045 (6)Pt1—Cl12.4295 (19)
Acknowledgements top

Z-XW thanks the Foundation for SRF for ROCS, SEM, Innovative Foundation of Shanghai University, and Shanghai Municipal Education Commission Special Research Fund for Excellent Young College and University Teachers.

references
References top

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