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Acta Cryst. (2010). E66, m200    [ doi:10.1107/S1600536810002485 ]

Diacridinium tetrakis(thiocyanato-[kappa]S)platinate(II)

K. Ha

Abstract top

The asymmetric unit of the title compound, (C13H10N)2[Pt(NCS)4], contains a protonated acridine molecule and one half of a [Pt(NCS)4]2- anion. In the complex anion, the PtII ion is located on an inversion centre and is four-coordinated in a slightly distorted square-planar environment by four S atoms from four thiocyanate ligands. The compound displays numerous intermolecular [pi]-[pi] interactions between six-membered rings, with a shortest centroid-centroid distance of 3.682 (3) Å. The component ions interact by means of intermolecular N-H...N hydrogen bonds.

Comment top

The asymmetric unit of the title compound contains a protonated acridine cation and one half of a [Pt(NCS)4]2- anionic complex (Fig. 1). In the complex, the PtII ion is located on an inversion centre at the special position (1, 1/2, 1/2) and is four-coordinated in a slightly distorted square-planar environment by four S atoms from four NCS- ligands. The Pt—S bond lengths are nearly equivalent [2.3236 (17) and 2.3254 (17) Å] (Table 1). The cis S—Pt—S bond angles are 88.82 (6) and 91.18 (6)°. The thiocyanate anions are almost linear displaying S—C—N bond angles of 175.7 (6) and 176.9 (6)°. The S atoms coordinate to the Pt atom with nearly tetrahedral Pt—S—C bond angles of 105.9 (2) and 104.4 (2)°. The compound displays numerous intermolecular π–π interactions between six-membered rings, with a shortest centroid–centroid distance of 3.682 (3) Å. The component ions interact by means of intermolecular N—H···N hydrogen bonds (Fig. 2 and Table 2).

Related literature top

For related acridinium compounds, see: Hafiz (2006); Veldhuizen et al. (1997). For the crystal structures of [M(NCS)4]2- [M = Pt(II), Pd(II)] complexes, see: Aoki et al. (1999); Deplano et al. (2004); Rohde et al. (2000).

Experimental top

To a solution of K2PtCl6 (0.2002 g, 0.412 mmol) in H2O (20 ml) was added KNCS (0.3998 g, 4.114 mmol) and refluxed for 1 h. After cooling of the reaction mixture to room temperature, acridine (0.1479 g, 0.825 mmol) was added and refluxed for 3 h. The precipitate obtained was separated by filtration, washed with H2O and dried at 50 °C, to give an orange powder (0.1894 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a MeOH solution.

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C, N)].

Computing details top

Data collection: SMART (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: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (a) 2-x, 1-y, 1-z.]
[Figure 2] Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.
Diacridinium tetrakis(thiocyanato-κS)platinate(II) top
Crystal data top
(C13H10N)2[Pt(NCS)4]F(000) = 768
Mr = 787.85Dx = 1.804 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 720 reflections
a = 6.8358 (8) Åθ = 2.3–20.2°
b = 11.9833 (15) ŵ = 5.16 mm−1
c = 17.737 (2) ÅT = 293 K
β = 93.618 (2)°Block, orange
V = 1450.0 (3) Å30.11 × 0.10 × 0.10 mm
Z = 2
Data collection top
Bruker SMART 1000 CCD
diffractometer		2968 independent reflections
Radiation source: fine-focus sealed tube2003 reflections with I > 2σ(I)
graphiteRint = 0.039
φ and ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→8
Tmin = 0.463, Tmax = 1.000k = −14→14
8278 measured reflectionsl = −11→22
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0175P)2]
where P = (Fo2 + 2Fc2)/3
2968 reflections(Δ/σ)max < 0.001
187 parametersΔρmax = 0.89 e Å−3
0 restraintsΔρmin = −0.50 e Å−3
Crystal data top
(C13H10N)2[Pt(NCS)4]V = 1450.0 (3) Å3
Mr = 787.85Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.8358 (8) ŵ = 5.16 mm−1
b = 11.9833 (15) ÅT = 293 K
c = 17.737 (2) Å0.11 × 0.10 × 0.10 mm
β = 93.618 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		2968 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2003 reflections with I > 2σ(I)
Tmin = 0.463, Tmax = 1.000Rint = 0.039
8278 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.068Δρmax = 0.89 e Å−3
S = 1.02Δρmin = −0.50 e Å−3
2968 reflectionsAbsolute structure: ?
187 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt11.00000.50000.50000.05422 (12)
S10.8814 (3)0.44333 (14)0.38044 (9)0.0807 (5)
S21.2773 (2)0.56944 (17)0.44661 (10)0.0862 (6)
N10.6764 (7)0.2432 (4)0.3972 (3)0.0747 (16)
N21.1409 (9)0.6690 (5)0.3098 (3)0.095 (2)
C10.7597 (8)0.3255 (5)0.3932 (3)0.0609 (16)
C21.1910 (9)0.6278 (5)0.3653 (4)0.0686 (19)
N30.2844 (5)0.5161 (3)0.0610 (3)0.0497 (11)
H30.29170.58520.07400.060*
C30.2417 (6)0.4939 (5)−0.0132 (3)0.0454 (12)
C40.2091 (7)0.5803 (5)−0.0660 (4)0.0569 (15)
H40.21990.6546−0.05130.068*
C50.1610 (8)0.5522 (6)−0.1395 (4)0.0666 (18)
H50.13650.6083−0.17510.080*
C60.1481 (8)0.4401 (7)−0.1621 (4)0.0730 (18)
H60.11610.4233−0.21260.088*
C70.1808 (8)0.3563 (6)−0.1124 (4)0.0708 (19)
H70.17220.2826−0.12880.085*
C80.2283 (7)0.3802 (5)−0.0354 (3)0.0515 (14)
C90.2682 (7)0.2991 (5)0.0195 (4)0.0611 (17)
H90.26640.22450.00510.073*
C100.3109 (7)0.3256 (5)0.0957 (3)0.0521 (14)
C110.3508 (8)0.2451 (5)0.1531 (4)0.0675 (18)
H110.34960.16960.14110.081*
C120.3904 (9)0.2780 (6)0.2253 (4)0.077 (2)
H120.41960.22490.26260.092*
C130.3877 (8)0.3919 (6)0.2445 (4)0.0752 (19)
H130.41160.41260.29480.090*
C140.3509 (8)0.4722 (5)0.1915 (3)0.0614 (17)
H140.34880.54710.20520.074*
C150.3163 (7)0.4401 (5)0.1159 (3)0.0473 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.0612 (2)0.04675 (18)0.0540 (2)−0.00893 (17)−0.00227 (16)0.00275 (19)
S10.1100 (14)0.0712 (11)0.0591 (11)−0.0381 (11)−0.0097 (10)0.0064 (10)
S20.0712 (12)0.1146 (15)0.0721 (12)−0.0280 (11)−0.0007 (10)0.0130 (12)
N10.090 (4)0.052 (3)0.081 (4)−0.013 (3)−0.005 (3)0.006 (3)
N20.105 (5)0.113 (5)0.069 (4)−0.034 (4)0.008 (4)0.014 (4)
C10.071 (4)0.054 (4)0.056 (4)−0.001 (3)−0.011 (3)0.003 (3)
C20.072 (5)0.068 (5)0.067 (5)−0.029 (4)0.020 (4)−0.017 (4)
N30.043 (2)0.048 (3)0.058 (3)0.004 (2)0.007 (2)−0.004 (3)
C30.032 (3)0.053 (3)0.053 (3)0.000 (3)0.011 (2)−0.006 (3)
C40.042 (3)0.060 (4)0.069 (4)0.001 (3)0.005 (3)0.003 (4)
C50.043 (3)0.092 (5)0.066 (5)0.006 (3)0.010 (3)0.011 (4)
C60.062 (4)0.097 (5)0.060 (4)0.006 (4)0.009 (4)−0.015 (5)
C70.054 (4)0.073 (5)0.086 (5)−0.005 (3)0.015 (4)−0.027 (4)
C80.039 (3)0.058 (4)0.060 (4)−0.005 (3)0.015 (3)−0.013 (3)
C90.044 (3)0.048 (4)0.093 (5)−0.003 (3)0.021 (4)−0.011 (4)
C100.042 (3)0.056 (4)0.060 (4)0.006 (3)0.009 (3)−0.001 (3)
C110.053 (4)0.051 (4)0.099 (6)0.010 (3)0.012 (4)0.011 (4)
C120.073 (5)0.081 (5)0.078 (5)0.010 (4)0.014 (4)0.027 (5)
C130.062 (4)0.102 (6)0.062 (4)0.009 (4)0.006 (4)0.008 (5)
C140.060 (4)0.063 (4)0.061 (4)0.005 (3)0.003 (3)−0.003 (3)
C150.038 (3)0.048 (3)0.057 (4)0.003 (3)0.009 (3)0.001 (3)
Geometric parameters (Å, °) top
Pt1—S12.3236 (17)C6—H60.9300
Pt1—S22.3254 (17)C7—C81.414 (7)
S1—C11.661 (6)C7—H70.9300
S2—C21.676 (7)C8—C91.390 (7)
N1—C11.143 (6)C9—C101.400 (7)
N2—C21.135 (7)C9—H90.9300
N3—C151.341 (6)C10—C111.417 (7)
N3—C31.357 (6)C10—C151.417 (7)
N3—H30.8600C11—C121.350 (8)
C3—C41.403 (7)C11—H110.9300
C3—C81.419 (7)C12—C131.408 (8)
C4—C51.367 (7)C12—H120.9300
C4—H40.9300C13—C141.358 (7)
C5—C61.403 (9)C13—H130.9300
C5—H50.9300C14—C151.402 (7)
C6—C71.345 (8)C14—H140.9300
S1i—Pt1—S1180.0C6—C7—H7120.0
S1i—Pt1—S291.18 (6)C8—C7—H7120.0
S1—Pt1—S288.82 (6)C9—C8—C7123.9 (6)
S1i—Pt1—S2i88.82 (6)C9—C8—C3118.1 (5)
S1—Pt1—S2i91.18 (6)C7—C8—C3118.0 (6)
S2—Pt1—S2i180.0C8—C9—C10122.5 (5)
C1—S1—Pt1105.9 (2)C8—C9—H9118.8
C2—S2—Pt1104.4 (2)C10—C9—H9118.8
N1—C1—S1175.7 (6)C9—C10—C11123.9 (6)
N2—C2—S2176.9 (7)C9—C10—C15117.6 (6)
C15—N3—C3125.9 (5)C11—C10—C15118.4 (6)
C15—N3—H3117.1C12—C11—C10120.1 (6)
C3—N3—H3117.1C12—C11—H11120.0
N3—C3—C4121.2 (5)C10—C11—H11120.0
N3—C3—C8117.6 (5)C11—C12—C13120.5 (6)
C4—C3—C8121.2 (5)C11—C12—H12119.8
C5—C4—C3118.3 (6)C13—C12—H12119.8
C5—C4—H4120.9C14—C13—C12121.7 (6)
C3—C4—H4120.9C14—C13—H13119.2
C4—C5—C6121.0 (6)C12—C13—H13119.2
C4—C5—H5119.5C13—C14—C15118.7 (6)
C6—C5—H5119.5C13—C14—H14120.6
C7—C6—C5121.5 (6)C15—C14—H14120.6
C7—C6—H6119.2N3—C15—C14121.2 (5)
C5—C6—H6119.2N3—C15—C10118.3 (5)
C6—C7—C8120.0 (6)C14—C15—C10120.6 (6)
S2—Pt1—S1—C1145.5 (2)C7—C8—C9—C10−178.7 (5)
S2i—Pt1—S1—C1−34.5 (2)C3—C8—C9—C103.3 (8)
S1i—Pt1—S2—C2−140.0 (2)C8—C9—C10—C11179.5 (5)
S1—Pt1—S2—C240.0 (2)C8—C9—C10—C15−1.2 (8)
C15—N3—C3—C4179.4 (4)C9—C10—C11—C12−179.9 (5)
C15—N3—C3—C80.3 (7)C15—C10—C11—C120.8 (8)
N3—C3—C4—C5−178.1 (5)C10—C11—C12—C131.6 (9)
C8—C3—C4—C50.9 (7)C11—C12—C13—C14−1.8 (10)
C3—C4—C5—C6−1.2 (8)C12—C13—C14—C15−0.4 (9)
C4—C5—C6—C70.5 (9)C3—N3—C15—C14−177.1 (5)
C5—C6—C7—C80.4 (9)C3—N3—C15—C101.8 (7)
C6—C7—C8—C9−178.7 (5)C13—C14—C15—N3−178.2 (5)
C6—C7—C8—C3−0.7 (8)C13—C14—C15—C102.9 (8)
N3—C3—C8—C9−2.8 (7)C9—C10—C15—N3−1.3 (7)
C4—C3—C8—C9178.1 (5)C11—C10—C15—N3178.0 (5)
N3—C3—C8—C7179.0 (4)C9—C10—C15—C14177.6 (5)
C4—C3—C8—C70.0 (7)C11—C10—C15—C14−3.1 (7)
Symmetry codes: (i) −x+2, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···N1ii0.861.972.829 (6)177
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Pt1—S12.3236 (17)Pt1—S22.3254 (17)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···N1i0.861.972.829 (6)177
Symmetry codes: (i) −x+1, y+1/2, −z+1/2.
Acknowledgements top

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2009–0074570).

references
References top

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