Tetra­bromido(di-2-pyridyl­amine-κ2N2,N2′)platinum(IV)

Ha, K.

doi:10.1107/S160053681203379X

metal-organic compounds

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Volume 68| Part 9| September 2012| Page m1141

doi:10.1107/S160053681203379X

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Tetrabromido(di-2-pyridylamine-κ²N²,N^2′)platinum(IV)

Kwang Ha ^a ^*

^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 23 July 2012; accepted 27 July 2012; online 1 August 2012)

The Pt^IV 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 Pt^IV 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 π–π interactions between the pyridine rings [centroid–centroid distance = 3.667 (4) Å] are also observed.

Related literature

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

Experimental

Crystal data

[PtBr₄(C₁₀H₉N₃)]
M_r = 685.93
Monoclinic, P 2₁ /m
a = 6.7876 (7) Å
b = 14.2860 (14) Å
c = 7.8893 (8) Å
β = 113.562 (2)°
V = 701.23 (12) Å³
Z = 2
Mo Kα radiation
μ = 21.39 mm⁻¹
T = 200 K
0.28 × 0.14 × 0.13 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.459, T_max = 1.000
4257 measured reflections
1400 independent reflections
1176 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.075
S = 1.04
1400 reflections
88 parameters
H-atom parameters constrained
Δρ_max = 1.89 e Å⁻³
Δρ_min = −1.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯Br2ⁱ	0.92	2.79	3.665 (8)	161
C3—H3⋯Br1ⁱⁱ	0.95	2.90	3.689 (7)	141
Symmetry codes: (i) x, y, z-1; (ii) $[-x, y-{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablock global. DOI: 10.1107/S160053681203379X/hy2577sup1.cif

checkCIF report

Comment top

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

The Pt^IV 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 Pt^II 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.

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. 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. 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,N^2')platinum(IV) top

Crystal data top

[PtBr₄(C₁₀H₉N₃)]	F(000) = 616
M_r = 685.93	D_x = 3.249 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2726 reflections
a = 6.7876 (7) Å	θ = 2.8–26.0°
b = 14.2860 (14) Å	µ = 21.39 mm⁻¹
c = 7.8893 (8) Å	T = 200 K
β = 113.562 (2)°	Block, red
V = 701.23 (12) Å³	0.28 × 0.14 × 0.13 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD diffractometer	1400 independent reflections
Radiation source: fine-focus sealed tube	1176 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
T_min = 0.459, T_max = 1.000	k = −17→15
4257 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0388P)² + 0.9524P] where P = (F_o² + 2F_c²)/3
1400 reflections	(Δ/σ)_max < 0.001
88 parameters	Δρ_max = 1.89 e Å⁻³
0 restraints	Δρ_min = −1.61 e Å⁻³

Crystal data top

[PtBr₄(C₁₀H₉N₃)]	V = 701.23 (12) Å³
M_r = 685.93	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 6.7876 (7) Å	µ = 21.39 mm⁻¹
b = 14.2860 (14) Å	T = 200 K
c = 7.8893 (8) Å	0.28 × 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)
T_min = 0.459, T_max = 1.000	R_int = 0.034
4257 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.04	Δρ_max = 1.89 e Å⁻³
1400 reflections	Δρ_min = −1.61 e Å⁻³
88 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

	x	y	z	U_iso*/U_eq
Pt1	0.02241 (6)	0.2500	0.81398 (5)	0.01565 (14)
Br1	−0.30563 (16)	0.2500	0.52614 (15)	0.0260 (3)
Br2	0.34926 (18)	0.2500	1.10292 (15)	0.0298 (3)
Br3	−0.14760 (13)	0.13183 (5)	0.93509 (11)	0.0306 (2)
N1	0.1651 (8)	0.1500 (3)	0.7074 (8)	0.0145 (11)
N2	0.1284 (13)	0.2500	0.4576 (11)	0.0193 (17)
H2N	0.1473	0.2500	0.3485	0.023*
C1	0.2280 (12)	0.0668 (5)	0.7949 (11)	0.0251 (16)
H1	0.2303	0.0591	0.9153	0.030*
C2	0.2881 (12)	−0.0059 (4)	0.7148 (11)	0.0250 (16)
H2	0.3358	−0.0632	0.7797	0.030*
C3	0.2786 (11)	0.0046 (5)	0.5396 (11)	0.0257 (17)
H3	0.3095	−0.0471	0.4784	0.031*
C4	0.2249 (11)	0.0890 (5)	0.4520 (10)	0.0224 (15)
H4	0.2227	0.0972	0.3318	0.027*
C5	0.1730 (11)	0.1634 (4)	0.5426 (10)	0.0193 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.0193 (2)	0.0115 (2)	0.0184 (2)	0.000	0.00991 (17)	0.000
Br1	0.0226 (6)	0.0189 (5)	0.0313 (6)	0.000	0.0053 (5)	0.000
Br2	0.0315 (6)	0.0315 (6)	0.0222 (6)	0.000	0.0063 (5)	0.000
Br3	0.0381 (5)	0.0239 (4)	0.0393 (5)	−0.0026 (3)	0.0254 (4)	0.0072 (3)
N1	0.014 (3)	0.012 (2)	0.017 (3)	−0.002 (2)	0.005 (2)	0.003 (2)
N2	0.023 (5)	0.017 (4)	0.019 (4)	0.000	0.010 (4)	0.000
C1	0.029 (4)	0.019 (3)	0.030 (4)	0.002 (3)	0.014 (3)	0.007 (3)
C2	0.023 (4)	0.012 (3)	0.042 (5)	0.001 (3)	0.015 (4)	0.006 (3)
C3	0.022 (4)	0.018 (4)	0.041 (5)	−0.002 (3)	0.017 (4)	−0.008 (3)
C4	0.023 (4)	0.019 (3)	0.028 (4)	0.001 (3)	0.014 (3)	−0.005 (3)
C5	0.018 (4)	0.011 (3)	0.031 (4)	0.000 (3)	0.012 (3)	0.001 (3)

Geometric parameters (Å, º) top

Pt1—N1	2.082 (5)	C1—C2	1.360 (10)
Pt1—Br3	2.4446 (7)	C1—H1	0.9500
Pt1—Br1	2.4642 (12)	C2—C3	1.366 (11)
Pt1—Br2	2.4647 (12)	C2—H2	0.9500
N1—C5	1.337 (9)	C3—C4	1.366 (10)
N1—C1	1.356 (8)	C3—H3	0.9500
N2—C5ⁱ	1.382 (7)	C4—C5	1.401 (9)
N2—C5	1.382 (7)	C4—H4	0.9500
N2—H2N	0.9200

N1ⁱ—Pt1—N1	86.6 (3)	C5ⁱ—N2—C5	127.1 (8)
N1ⁱ—Pt1—Br3ⁱ	93.02 (13)	C5ⁱ—N2—H2N	111.6
N1—Pt1—Br3ⁱ	179.26 (15)	C5—N2—H2N	111.6
N1ⁱ—Pt1—Br3	179.26 (15)	N1—C1—C2	121.7 (7)
N1—Pt1—Br3	93.02 (13)	N1—C1—H1	119.1
Br3ⁱ—Pt1—Br3	87.35 (4)	C2—C1—H1	119.1
N1ⁱ—Pt1—Br1	91.29 (16)	C1—C2—C3	118.9 (7)
N1—Pt1—Br1	91.29 (16)	C1—C2—H2	120.5
Br3ⁱ—Pt1—Br1	88.07 (3)	C3—C2—H2	120.5
Br3—Pt1—Br1	88.07 (3)	C4—C3—C2	120.3 (6)
N1ⁱ—Pt1—Br2	88.95 (15)	C4—C3—H3	119.9
N1—Pt1—Br2	88.95 (16)	C2—C3—H3	119.9
Br3ⁱ—Pt1—Br2	91.69 (3)	C3—C4—C5	118.8 (7)
Br3—Pt1—Br2	91.69 (3)	C3—C4—H4	120.6
Br1—Pt1—Br2	179.67 (3)	C5—C4—H4	120.6
C5—N1—C1	119.6 (6)	N1—C5—N2	120.9 (6)
C5—N1—Pt1	120.1 (4)	N1—C5—C4	120.3 (6)
C1—N1—Pt1	119.9 (4)	N2—C5—C4	118.9 (6)

N1ⁱ—Pt1—N1—C5	−39.4 (6)	C1—C2—C3—C4	4.8 (11)
Br3—Pt1—N1—C5	139.9 (5)	C2—C3—C4—C5	−2.1 (10)
Br1—Pt1—N1—C5	51.8 (5)	C1—N1—C5—N2	−174.2 (7)
Br2—Pt1—N1—C5	−128.4 (5)	Pt1—N1—C5—N2	13.3 (9)
N1ⁱ—Pt1—N1—C1	148.0 (4)	C1—N1—C5—C4	6.5 (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—N1	34.0 (13)
Br2—Pt1—N1—C1	59.0 (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—C2	168.8 (6)	C3—C4—C5—N2	177.0 (7)
N1—C1—C2—C3	−1.9 (11)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Br2ⁱⁱ	0.92	2.79	3.665 (8)	161
C3—H3···Br1ⁱⁱⁱ	0.95	2.90	3.689 (7)	141

Symmetry codes: (ii) x, y, z−1; (iii) −x, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[PtBr₄(C₁₀H₉N₃)]
M_r	685.93
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	200
a, b, c (Å)	6.7876 (7), 14.2860 (14), 7.8893 (8)
β (°)	113.562 (2)
V (Å³)	701.23 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	21.39
Crystal size (mm)	0.28 × 0.14 × 0.13

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.459, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4257, 1400, 1176
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.075, 1.04
No. of reflections	1400
No. of parameters	88
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.89, −1.61

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Br2ⁱ	0.92	2.79	3.665 (8)	161
C3—H3···Br1ⁱⁱ	0.95	2.90	3.689 (7)	141

Symmetry codes: (i) x, y, z−1; (ii) −x, y−1/2, −z+1.

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

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