Dibromidodimethyl­dipyridine­platinum(IV)

Kelly, M.E.; Wagner, C.; Schmidt, H.

doi:10.1107/S160053680803208X

metal-organic compounds

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Volume 64| Part 11| November 2008| Page m1385

doi:10.1107/S160053680803208X

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Dibromidodimethyldipyridineplatinum(IV)

Mairéad E. Kelly,^a Christoph Wagner ^a and Harry Schmidt ^a ^*

^aInstitut für Chemie, Kurt-Mothes-Straße 2, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle, Germany
^*Correspondence e-mail: h.schmidt@chemie.uni-halle.de

(Received 19 September 2008; accepted 6 October 2008; online 11 October 2008)

In the title complex, [PtBr₂(CH₃)₂(C₅H₅N)₂], the Pt^IV metal centre lies on a twofold rotation axis and adopts a slightly distorted octahedral coordination geometry. The structure displays weak intramolecular C—H⋯Br hydrogen-bonding interactions.

Related literature

For the crystal structures of related compounds, see: Brammer et al. (2001 ); Burton et al. (1983 ); Canty et al. (1990 ); Clark et al. (1983 ); Contreras et al. (2001 ); Hall & Swile (1971 ); Hindmarch et al. (1997 ); Hughes et al. (2001 ); Kaluderović et al. (2007 ); Kelly, Gómez-Ruiz, Kluge et al. (2008 ); Kelly, Gómez-Ruiz, Schmidt et al. (2008 ); Kelly, Dietrich et al. (2008 ); Klingler et al. (1982 ). For bond-length data, see: Allen (2002 ).

Experimental

Crystal data

[PtBr₂(CH₃)₂(C₅H₅N)₂]
M_r = 543.18
Orthorhombic, P b c n
a = 13.297 (2) Å
b = 8.2906 (15) Å
c = 13.516 (3) Å
V = 1490.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 14.76 mm⁻¹
T = 220 (2) K
0.40 × 0.34 × 0.30 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: numerical (IPDS; Stoe & Cie, 1999 ) T_min = 0.024, T_max = 0.069
10568 measured reflections
1453 independent reflections
1166 reflections with I > 2σ(I)
R_int = 0.144

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.091
S = 1.01
1453 reflections
80 parameters
H-atom parameters constrained
Δρ_max = 1.71 e Å⁻³
Δρ_min = −1.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H8⋯Brⁱ	0.93	2.92	3.412 (6)	115
Symmetry code: (i) $[-x, y, -z+{\script{3\over 2}}]$ .

Data collection: IPDS Software (Stoe & Cie, 1999); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680803208X/rz2250sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803208X/rz2250Isup2.hkl

checkCIF report

Comment top

The structure of the title compound is one of a relatively small number of structures with the PtBr₂Me₂ moiety (Contreras et al., 2001; Kaluderović et al., 2007; Kelly, Gómez-Ruiz, Kluge et al., 2008; Kelly, Gómez-Ruiz, Schmidt et al., 2008; Kelly, Dietrich et al., 2008). The compound crystallizes in the orthorhombic space group Pbcn and half the molecule is generated by a twofold crystallographic axis bisecting the C—Pt—N axis as illustrated in Fig. 1. The ligating atoms have an approximate octahedral arrangement around the platinum atom. The Pt—N bond length (2.226 (5) Å) is slightly longer than expected for a platinum(IV)—N bond trans-configured to a ligating carbon atom (median: 2.156 Å; lower/upper quartile: 2.135/2.194 Å for 402 entries in the Cambridge Structural Database; CSD, Version 5.28, August 2007; Allen, 2002). The Pt—Br bond length (2.461 (1) Å) and the Pt—C bond length (2.053 (7) Å) are typical for bonds of these types (Clark et al., 1983; Klingler et al., 1982; Burton et al., 1983; Hughes et al., 2001; Canty et al., 1990; Hindmarch et al., 1997; Kelly, Gómez-Ruiz, Kluge et al., 2008; Kelly, Gómez-Ruiz, Schmidt et al., 2008; Kelly, Dietrich et al., 2008). A short intramolecular distance between the C6 carbon atom of the pyridine ligand and a bromo ligand of the same molecule is found, indicating the presence of weak C—H···Br interactions (Brammer et al., 2001).

Related literature top

For the crystal structures of related compounds, see: Brammer et al. (2001); Burton et al. (1983); Canty et al. (1990); Clark et al. (1983); Contreras et al. (2001); Hall & Swile (1971); Hindmarch et al. (1997); Hughes et al. (2001); Kaluderović et al. (2007); Kelly, Gómez-Ruiz, Kluge et al. (2008); Kelly, Gómez-Ruiz, Schmidt et al. (2008); Kelly, Dietrich et al. (2008); Klingler et al. (1982). For bond-length data, see: Allen (2002).

Experimental top

The title compound was prepared by dissolving [(PtBr₂Me₂)_n] in an excess of pyridine (Hall & Swile, 1971). Single crystals suitable for X-ray analysis were obtained by slow evaporation of a chloroform solution.

Computing details top

Data collection: IPDS (Stoe & Cie, 1999); cell refinement: IPDS (Stoe & Cie, 1999); data reduction: IPDS (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title complex with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x, y, -z + 3/2z].

Dibromidodimethyldipyridineplatinum(IV) top

Crystal data top

[PtBr₂(CH₃)₂(C₅H₅N)₂]	F(000) = 1000
M_r = 543.18	D_x = 2.421 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 8000 reflections
a = 13.297 (2) Å	θ = 2.2–25.9°
b = 8.2906 (15) Å	µ = 14.76 mm⁻¹
c = 13.516 (3) Å	T = 220 K
V = 1490.1 (5) Å³	Block, orange
Z = 4	0.40 × 0.34 × 0.30 mm

Data collection top

Stoe IPDS diffractometer	1453 independent reflections
Radiation source: fine-focus sealed tube	1166 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.144
area detector scans	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: numerical (IPDS; Stoe & Cie, 1999)	h = −16→16
T_min = 0.024, T_max = 0.069	k = −10→10
10568 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0472P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
1453 reflections	Δρ_max = 1.71 e Å⁻³
80 parameters	Δρ_min = −1.68 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0012 (2)

Crystal data top

[PtBr₂(CH₃)₂(C₅H₅N)₂]	V = 1490.1 (5) Å³
M_r = 543.18	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 13.297 (2) Å	µ = 14.76 mm⁻¹
b = 8.2906 (15) Å	T = 220 K
c = 13.516 (3) Å	0.40 × 0.34 × 0.30 mm

Data collection top

Stoe IPDS diffractometer	1453 independent reflections
Absorption correction: numerical (IPDS; Stoe & Cie, 1999)	1166 reflections with I > 2σ(I)
T_min = 0.024, T_max = 0.069	R_int = 0.144
10568 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.01	Δρ_max = 1.71 e Å⁻³
1453 reflections	Δρ_min = −1.68 e Å⁻³
80 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
C1	0.0667 (6)	−0.0872 (9)	0.6693 (6)	0.0487 (17)
H3	0.1207	−0.1336	0.7069	0.058*
H1	0.0928	−0.0434	0.6087	0.058*
H2	0.0179	−0.1690	0.6544	0.058*
C2	−0.1238 (5)	0.4045 (8)	0.7975 (5)	0.0412 (15)
H4	−0.1268	0.4089	0.7288	0.049*
C3	−0.1703 (5)	0.5237 (9)	0.8514 (6)	0.0479 (17)
H5	−0.2038	0.6070	0.8191	0.057*
C4	−0.1673 (5)	0.5196 (10)	0.9542 (6)	0.0526 (19)
H6	−0.1976	0.6001	0.9918	0.063*
C5	−0.1182 (5)	0.3930 (10)	0.9987 (6)	0.057 (2)
H7	−0.1161	0.3847	1.0673	0.068*
C6	−0.0716 (4)	0.2771 (9)	0.9396 (4)	0.0423 (15)
H8	−0.0373	0.1928	0.9699	0.051*
N	−0.0747 (3)	0.2833 (7)	0.8400 (3)	0.0355 (11)
Br	−0.14288 (5)	0.08616 (9)	0.63441 (5)	0.0465 (2)
Pt	0.0000	0.09312 (4)	0.7500	0.03167 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.055 (4)	0.047 (4)	0.044 (4)	−0.004 (3)	0.007 (3)	−0.012 (3)
C2	0.039 (3)	0.045 (4)	0.039 (4)	0.002 (3)	−0.001 (3)	0.003 (3)
C3	0.036 (3)	0.044 (4)	0.064 (5)	0.000 (3)	0.004 (3)	0.003 (4)
C4	0.035 (3)	0.062 (5)	0.061 (5)	−0.001 (3)	0.010 (3)	−0.023 (4)
C5	0.045 (4)	0.087 (7)	0.038 (4)	0.002 (3)	0.006 (3)	−0.010 (4)
C6	0.034 (3)	0.063 (4)	0.030 (3)	0.007 (3)	−0.002 (2)	−0.004 (3)
N	0.029 (2)	0.047 (3)	0.030 (3)	0.000 (2)	0.0029 (19)	0.003 (2)
Br	0.0385 (3)	0.0661 (5)	0.0347 (4)	−0.0103 (3)	−0.0087 (3)	0.0010 (3)
Pt	0.0312 (2)	0.0397 (2)	0.0242 (3)	0.000	−0.00189 (11)	0.000

Geometric parameters (Å, º) top

C1—Pt	2.053 (7)	C4—H6	0.9300
C1—H3	0.9600	C5—C6	1.394 (10)
C1—H1	0.9600	C5—H7	0.9300
C1—H2	0.9600	C6—N	1.347 (7)
C2—N	1.329 (8)	C6—H8	0.9300
C2—C3	1.375 (10)	N—Pt	2.226 (5)
C2—H4	0.9300	Br—Pt	2.4605 (7)
C3—C4	1.391 (10)	Pt—C1ⁱ	2.053 (7)
C3—H5	0.9300	Pt—Nⁱ	2.226 (5)
C4—C5	1.375 (11)	Pt—Brⁱ	2.4605 (7)

Pt—C1—H3	109.5	C5—C6—H8	118.9
Pt—C1—H1	109.5	C2—N—C6	118.4 (6)
H3—C1—H1	109.5	C2—N—Pt	121.2 (4)
Pt—C1—H2	109.5	C6—N—Pt	120.4 (5)
H3—C1—H2	109.5	C1—Pt—C1ⁱ	86.5 (4)
H1—C1—H2	109.5	C1—Pt—N	178.4 (2)
N—C2—C3	122.4 (7)	C1ⁱ—Pt—N	91.9 (3)
N—C2—H4	118.8	C1—Pt—Nⁱ	91.9 (3)
C3—C2—H4	118.8	C1ⁱ—Pt—Nⁱ	178.4 (2)
C2—C3—C4	119.9 (7)	N—Pt—Nⁱ	89.8 (3)
C2—C3—H5	120.0	C1—Pt—Brⁱ	89.2 (2)
C4—C3—H5	120.0	C1ⁱ—Pt—Brⁱ	88.8 (2)
C5—C4—C3	117.9 (7)	N—Pt—Brⁱ	90.80 (12)
C5—C4—H6	121.0	Nⁱ—Pt—Brⁱ	91.11 (12)
C3—C4—H6	121.0	C1—Pt—Br	88.8 (2)
C4—C5—C6	119.1 (7)	C1ⁱ—Pt—Br	89.2 (2)
C4—C5—H7	120.4	N—Pt—Br	91.11 (12)
C6—C5—H7	120.4	Nⁱ—Pt—Br	90.80 (12)
N—C6—C5	122.2 (7)	Brⁱ—Pt—Br	177.31 (4)
N—C6—H8	118.9

N—C2—C3—C4	−0.3 (10)	C5—C6—N—Pt	−179.4 (5)
C2—C3—C4—C5	−0.9 (11)	C2—N—Pt—Nⁱ	49.9 (4)
C3—C4—C5—C6	1.6 (11)	C6—N—Pt—Nⁱ	−130.6 (6)
C4—C5—C6—N	−1.3 (11)	C2—N—Pt—Brⁱ	141.0 (4)
C3—C2—N—C6	0.7 (9)	C6—N—Pt—Brⁱ	−39.5 (5)
C3—C2—N—Pt	−179.8 (5)	C2—N—Pt—Br	−40.9 (4)
C5—C6—N—C2	0.1 (10)	C6—N—Pt—Br	138.6 (5)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H8···Brⁱ	0.93	2.92	3.412 (6)	115

Symmetry code: (i) −x, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[PtBr₂(CH₃)₂(C₅H₅N)₂]
M_r	543.18
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	220
a, b, c (Å)	13.297 (2), 8.2906 (15), 13.516 (3)
V (Å³)	1490.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	14.76
Crystal size (mm)	0.40 × 0.34 × 0.30

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Numerical (IPDS; Stoe & Cie, 1999)
T_min, T_max	0.024, 0.069
No. of measured, independent and observed [I > 2σ(I)] reflections	10568, 1453, 1166
R_int	0.144
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.091, 1.01
No. of reflections	1453
No. of parameters	80
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.71, −1.68

Computer programs: IPDS (Stoe & Cie, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H8···Brⁱ	0.93	2.92	3.412 (6)	114.7

Symmetry code: (i) −x, y, −z+3/2.

Acknowledgements

The authors acknowledge the Deutsche Forschungsgemeinschaft for financial support and Merck for gifts of chemicals.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1385

doi:10.1107/S160053680803208X

Open

access