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Acta Cryst. (2012). E68, m1141    [ doi:10.1107/S160053681203379X ]

Tetrabromido(di-2-pyridylamine-[kappa]2N2,N2')platinum(IV)

K. Ha

Abstract top

The PtIV ion in the title complex, [PtBr4(C10H9N3)], is six-coordinated in a slightly distorted octahedral environment by two pyridine N atoms from a chelating di-2-pyridylamine (dpa) ligand and four Br- anions. The complex molecule has mirror symmetry, with the PtIV atom, two Br atoms and the central N atom of the dpa ligand lying on the mirror plane. The dpa ligand is not planar, showing a dihedral angle of 34.7 (2)° between the pyridine rings. The complex molecules are connected by intermolecular N-H...Br hydrogen bonds, forming chains along [001]. Intermolecular C-H...Br hydrogen bonds and [pi]-[pi] interactions between the pyridine rings [centroid-centroid distance = 3.667 (4) Å] are also observed.

Comment top

The title complex, [PtBr4(dpa)] (dpa = di-2-pyridylamine, C10H9N3), is a structural isomer of the previously reported chlorido PtIV complex [PtCl4(dpa)] (Ha, 2011).

The PtIV ion is six-coordinated in a slightly distorted octahedral environment defined by two pyridine N atoms from a chelating dpa ligand and four Br- anions (Fig. 1). The complex is disposed about a mirror plane, passing through the Pt1, Br1, Br2 and N2 atoms. The Pt—N and Pt—Br bond distances are comparable to those observed in the related PtII complex [PtBr2(dpa)] (Ha, 2012). In the crystal, the dpa ligand is not planar. The dihedral angle between the least-squares planes of the pyridine rings is 34.7 (2)°. The complex molecules are stacked in columns along the a axis and connected by intermolecular N—H···Br hydrogen bonds, forming chains along the c axis (Fig. 2, Table 1). Intermolecular π–π interactions between the pyridine rings are present, with a centroid–centroid distance of 3.667 (4) Å. Intermolecular C—H···Br hydrogen bonds are also observed (Table 1).

Related literature top

For the structures of the related complexes [PtCl4(dpa)] and [PtBr2(dpa)], see: Ha (2011, 2012).

Experimental top

To a solution of K2PtCl6 (0.240 g, 0.49 mmol) and KBr (0.745 g, 6.26 mmol) in H2O (50 ml) was added di-2-pyridylamine (0.086 g, 0.50 mmol), and the mixture was stirred for 24 h at room temperature. The formed precipitate was separated by filtration, washed with H2O and acetone, and recrystallized from a mixture of N,N-dimethylformamide and ether to give a red powder (0.144 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH3CN solution at room temperature.

Refinement top

C-bound H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.95 Å and with Uiso(H) = 1.2Ueq(C). N-bound H atom was located from a difference Fourier map and then allowed to ride on its parent atom in the final cycles of refinement, with N—H = 0.92 Å and Uiso(H) = 1.2Ueq(N). The highest peak (1.89 e Å-3) and the deepest hole (-1.62 e Å-3) in the difference Fourier map are located 0.85 Å and 0.67 Å from atoms Pt1 and Br1, respectively.

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 molecular structure of the title complex. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x, 1/2-y, z.]
[Figure 2] Fig. 2. A view of the crystal packing of the title complex. Intermolecular N—H···Br hydrogen bonds are shown as dashed lines.
Tetrabromido(di-2-pyridylamine-κ2N2,N2')platinum(IV) top
Crystal data top
[PtBr4(C10H9N3)]F(000) = 616
Mr = 685.93Dx = 3.249 Mg m−3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 2726 reflections
a = 6.7876 (7) Åθ = 2.8–26.0°
b = 14.2860 (14) ŵ = 21.39 mm−1
c = 7.8893 (8) ÅT = 200 K
β = 113.562 (2)°Block, red
V = 701.23 (12) Å30.28 × 0.14 × 0.13 mm
Z = 2
Data collection top
Bruker SMART 1000 CCD
diffractometer		1400 independent reflections
Radiation source: fine-focus sealed tube1176 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
φ and ω scansθmax = 26.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→8
Tmin = 0.459, Tmax = 1.000k = −17→15
4257 measured reflectionsl = −9→9
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0388P)2 + 0.9524P]
where P = (Fo2 + 2Fc2)/3
1400 reflections(Δ/σ)max < 0.001
88 parametersΔρmax = 1.89 e Å−3
0 restraintsΔρmin = −1.62 e Å−3
Crystal data top
[PtBr4(C10H9N3)]V = 701.23 (12) Å3
Mr = 685.93Z = 2
Monoclinic, P21/mMo Kα radiation
a = 6.7876 (7) ŵ = 21.39 mm−1
b = 14.2860 (14) ÅT = 200 K
c = 7.8893 (8) Å0.28 × 0.14 × 0.13 mm
β = 113.562 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		1400 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1176 reflections with I > 2σ(I)
Tmin = 0.459, Tmax = 1.000Rint = 0.034
4257 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.075Δρmax = 1.89 e Å−3
S = 1.04Δρmin = −1.62 e Å−3
1400 reflectionsAbsolute structure: ?
88 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
Pt10.02241 (6)0.25000.81398 (5)0.01565 (14)
Br1−0.30563 (16)0.25000.52614 (15)0.0260 (3)
Br20.34926 (18)0.25001.10292 (15)0.0298 (3)
Br3−0.14760 (13)0.13183 (5)0.93509 (11)0.0306 (2)
N10.1651 (8)0.1500 (3)0.7074 (8)0.0145 (11)
N20.1284 (13)0.25000.4576 (11)0.0193 (17)
H2N0.14730.25000.34850.023*
C10.2280 (12)0.0668 (5)0.7949 (11)0.0251 (16)
H10.23030.05910.91530.030*
C20.2881 (12)−0.0059 (4)0.7148 (11)0.0250 (16)
H20.3358−0.06320.77970.030*
C30.2786 (11)0.0046 (5)0.5396 (11)0.0257 (17)
H30.3095−0.04710.47840.031*
C40.2249 (11)0.0890 (5)0.4520 (10)0.0224 (15)
H40.22270.09720.33180.027*
C50.1730 (11)0.1634 (4)0.5426 (10)0.0193 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.0193 (2)0.0115 (2)0.0184 (2)0.0000.00991 (17)0.000
Br10.0226 (6)0.0189 (5)0.0313 (6)0.0000.0053 (5)0.000
Br20.0315 (6)0.0315 (6)0.0222 (6)0.0000.0063 (5)0.000
Br30.0381 (5)0.0239 (4)0.0393 (5)−0.0026 (3)0.0254 (4)0.0072 (3)
N10.014 (3)0.012 (2)0.017 (3)−0.002 (2)0.005 (2)0.003 (2)
N20.023 (5)0.017 (4)0.019 (4)0.0000.010 (4)0.000
C10.029 (4)0.019 (3)0.030 (4)0.002 (3)0.014 (3)0.007 (3)
C20.023 (4)0.012 (3)0.042 (5)0.001 (3)0.015 (4)0.006 (3)
C30.022 (4)0.018 (4)0.041 (5)−0.002 (3)0.017 (4)−0.008 (3)
C40.023 (4)0.019 (3)0.028 (4)0.001 (3)0.014 (3)−0.005 (3)
C50.018 (4)0.011 (3)0.031 (4)0.000 (3)0.012 (3)0.001 (3)
Geometric parameters (Å, º) top
Pt1—N12.082 (5)C1—C21.360 (10)
Pt1—Br32.4446 (7)C1—H10.9500
Pt1—Br12.4642 (12)C2—C31.366 (11)
Pt1—Br22.4647 (12)C2—H20.9500
N1—C51.337 (9)C3—C41.366 (10)
N1—C11.356 (8)C3—H30.9500
N2—C5i1.382 (7)C4—C51.401 (9)
N2—C51.382 (7)C4—H40.9500
N2—H2N0.9200
N1i—Pt1—N186.6 (3)C5i—N2—C5127.1 (8)
N1i—Pt1—Br3i93.02 (13)C5i—N2—H2N111.6
N1—Pt1—Br3i179.26 (15)C5—N2—H2N111.6
N1i—Pt1—Br3179.26 (15)N1—C1—C2121.7 (7)
N1—Pt1—Br393.02 (13)N1—C1—H1119.1
Br3i—Pt1—Br387.35 (4)C2—C1—H1119.1
N1i—Pt1—Br191.29 (16)C1—C2—C3118.9 (7)
N1—Pt1—Br191.29 (16)C1—C2—H2120.5
Br3i—Pt1—Br188.07 (3)C3—C2—H2120.5
Br3—Pt1—Br188.07 (3)C4—C3—C2120.3 (6)
N1i—Pt1—Br288.95 (15)C4—C3—H3119.9
N1—Pt1—Br288.95 (16)C2—C3—H3119.9
Br3i—Pt1—Br291.69 (3)C3—C4—C5118.8 (7)
Br3—Pt1—Br291.69 (3)C3—C4—H4120.6
Br1—Pt1—Br2179.67 (3)C5—C4—H4120.6
C5—N1—C1119.6 (6)N1—C5—N2120.9 (6)
C5—N1—Pt1120.1 (4)N1—C5—C4120.3 (6)
C1—N1—Pt1119.9 (4)N2—C5—C4118.9 (6)
N1i—Pt1—N1—C5−39.4 (6)C1—C2—C3—C44.8 (11)
Br3—Pt1—N1—C5139.9 (5)C2—C3—C4—C5−2.1 (10)
Br1—Pt1—N1—C551.8 (5)C1—N1—C5—N2−174.2 (7)
Br2—Pt1—N1—C5−128.4 (5)Pt1—N1—C5—N213.3 (9)
N1i—Pt1—N1—C1148.0 (4)C1—N1—C5—C46.5 (10)
Br3—Pt1—N1—C1−32.6 (5)Pt1—N1—C5—C4−166.1 (5)
Br1—Pt1—N1—C1−120.7 (5)C5i—N2—C5—N134.0 (13)
Br2—Pt1—N1—C159.0 (5)C5i—N2—C5—C4−146.7 (7)
C5—N1—C1—C2−3.8 (10)C3—C4—C5—N1−3.6 (10)
Pt1—N1—C1—C2168.8 (6)C3—C4—C5—N2177.0 (7)
N1—C1—C2—C3−1.9 (11)
Symmetry code: (i) x, −y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Br2ii0.922.793.665 (8)161
C3—H3···Br1iii0.952.903.689 (7)141
Symmetry codes: (ii) x, y, z−1; (iii) −x, y−1/2, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Br2i0.922.793.665 (8)161
C3—H3···Br1ii0.952.903.689 (7)141
Symmetry codes: (i) x, y, z−1; (ii) −x, y−1/2, −z+1.
Acknowledgements top

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
References top

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Ha, K. (2011). Z. Kristallogr. New Cryst. Struct. 226, 633–634.

Ha, K. (2012). Acta Cryst. E68, m453.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.