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Acta Cryst. (2007). E63, m1985    [ doi:10.1107/S1600536807029534 ]

trans,cis-Dibromido[diethyl (ethane-1,2-diyldiimino)diacetate-[kappa]2N,N']dimethylplatinum(IV)

G. N. Kaluderovic, H. Schmidt, C. Wagner and D. Steinborn

Abstract top

The title complex, [PtBr2(CH3)2(C10H20N2O4)], has a slightly distorted octahedral coordination geometry as reflected in the bond lengths and angles around the PtIV atom. A crystallographic C2 rotation axis bisects the C-C bond of the central ethylene group and passes through the Pt atom.

Comment top

In this paper, we report the structure of trans,cis-dibromodimethyl(O,O'-diethyl-ethylenediamine- N,N'-diacetate)platinum(IV) (configuration index: OC-6–13) trans,cis-[PtBr2Me2(Et2edda)], prepared as part of our investigation on basic coordination modes and antitumoral activity of platinum(IV) complexes with esters of H2edda-type (ethylenediamine-N,N'-diacetatic acid) ligands (Kaluđerović, Đinović et al., 2005; Kaluđerović, Miljković et al., 2005; Kaluđerović, Schmidt, Schwieger et al., 2007).

The title compound crystallizes in the space group C2/c as isolated molecules and exhibits a crystallographically imposed C2 symmetry axis bisecting the C2—C2i bond and passing through the Pt atom. The Pt atom adopts a [Br2C2N2] distorted octahedral coordination; the Pt, C, N atoms lie in a plane with meaningless deviation from the mean plane: 0.004 (6) Å and 0.005 (9) Å for N and C1 atoms, respectively. Due to the C2 symmetry, the five-membered ring PtNC2C2iNi exibits an ideal half twisted conformation with a twist around the C2—C2i bond. Because of an inversion center within the unit cell the compound crystallized as a mixture of molecules with λ and δ oriented five-membered cycles in 1:1 ratio. Fig. 1 illustrates the λ oriented complex.

Almost all angles in the coordination polyhedron are very close to the ideal value of 90° (87.1 (5) − 91.0 (2)°), with the exception of angles N—Pt—Ni = 80.8 (3)° and C1—Pt—N = 96.0 (3)°, due to the constraints of the chelate binding Et2edda ligand. The angle N—Pt—Ni is smaller than in structures [PtCl4(R2edda)] (R = Me, 83.1 (6)°; Et, 84.0 (3)°, (I); Kaluđerović, Schmidt, Schwieger et al., 2007), [PtBr4(en)] (83.1 (9)°; Hindmarsh et al., 1997), [PdCl2(R4edta)] (R = Me, 85.9 (2)°; Et, 85.6 (3)°; Kaluđerović, Schmidt, Wagner et al., 2007) and in [PtMe2I2(tmeda)], (II), [PtMe2I(n-C3F7)(tmeda)], (III), and [PtMeI2(n-C3F7)(tmeda)], (IV), (tmeda = tetramethyl-N,N,N',N'-ethylenediamine; 82.3 (2) − 82.8 (5)°; Hughes et al., 2001).

The Pt—C1 bond length of 2.052 (8) Å is comparable to the Pt—C distances found in trans-[PtBr2Me2{o-Ph2P(S)C6H4SMe- κ2S,S}], 2.065 (6)/2.106 (5) Å (Contreras et al., 2001) and in [Pt(X)(OMe)(Me)2(tmeda)] structures (X = OH, OOH), 2.007 (8) − 2.07 (2) Å (Rostovtsev et al., 2002). The Pt—Br bond lengths (2.443 (1) Å) are similar to those found in (I) (2.447 (1)/2.460 (1) Å), [PtBr4(L)] (L = ethylenediamine, 2.461 (2)/2.448 (2) Å; 1,3-propylenediamine, 2.452 (4)/2.455 (4) Å; Hindmarsh et al., 1997). In accordance with the high trans influence of the Me ligand the Pt—N bond (2.234 (6) Å) is relatively long although comparable with structures (II), (III) and (IV) (2.226 (5) − 2.312 (7) Å; Hughes et al., 2001), in which the Me ligand is also trans to N atom. The Pt—N bonds with Cl ((I): 2.110 (6) Å) or Br ([PtBr4(L)]; L = ethylenediamine, 2.05 (2) Å; L = 1,3-propylenediamine, 2.04 (3) Å; Hindmarsh et al., 1997) trans to a N atom are shorter relative to corresponding bond length in the title compound. Weak intramolecular H-bond (C5—H···O1) may stabilize the structure (distance C5···O1 = 2.70 (1) Å).

Besides trans-[PtBr2Me2{o-Ph2P(S)C6H4SMe- κ2S,S}] (Contreras et al., 2001), the title complex is the only other mononuclear dibromodimethylplatinum(IV) complex that has been structurally characterized to date.

Related literature top

For background information, see: Kaluđerović, Đinović et al. (2005); Kaluđerović, Miljković et al. (2005); Kaluđerović, Schmidt, Schwieger et al. (2007); Kaluđerović, Schmidt, Wagner et al. (2007). For related literature, see: Contreras et al. (2001); Hindmarsh et al. (1997); Hughes et al. (2001); Rostovtsev et al. (2002).

Experimental top

[{PtBr2Me2}n] (0.3 mmol) and Et2edda.2HCl (0.3 mmol) were suspended in methanol-chloroform solution (10 ml, 1:1 v/v). The mixture was stirred under reflux for 2 h. From the resulting yellow solution the title complex crystallized as well shaped crystals within one week at room temperature.

Refinement top

H atoms were included in calculated positions [C—H = 0.97–0.98 Å; N—H = 0.92 Å] and included in the refinement in a riding-model approximation with Uiso(H) = 1.2Ueq(C) and Uiso(H6) = 0.023 Å3.

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular structure of the λ oriented complex. Displacement ellipsoids are plotted at the 30% probability level and H atoms are shown as small spheres of arbitrary radii [Symmetry code: (i) −x − 1, y, −z + 5/2].
trans,cis-Dibromido[diethyl (ethane-1,2-diyldiimino)diacetate- κ2N,N']dimethylplatinum(IV) top
Crystal data top
[PtBr2(C1H3)2(C10H20N2O4)]F000 = 1168
Mr = 617.26Dx = 2.207 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8000 reflections
a = 21.419 (4) Åθ = 4.2–51.7º
b = 8.1405 (12) ŵ = 11.87 mm−1
c = 12.153 (2) ÅT = 220 (2) K
β = 118.75 (3)ºBlock, yellow
V = 1857.9 (6) Å30.25 × 0.22 × 0.18 mm
Z = 4
Data collection top
Stoe IPDS
diffractometer		1754 independent reflections
Radiation source: fine-focus sealed tube1644 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.088
T = 220(2) Kθmax = 25.9º
area detector scansθmin = 3.6º
Absorption correction: numerical
(IPDS Software; Stoe & Cie, 1999)		h = −26→26
Tmin = 0.086, Tmax = 0.186k = −9→9
5983 measured reflectionsl = −14→14
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044  w = 1/[σ2(Fo2) + (0.0673P)2 + 23.535P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.116(Δ/σ)max < 0.001
S = 1.05Δρmax = 3.61 e Å−3
1754 reflectionsΔρmin = −3.25 e Å−3
98 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0019 (4)
Secondary atom site location: difference Fourier map
Crystal data top
[PtBr2(C1H3)2(C10H20N2O4)]V = 1857.9 (6) Å3
Mr = 617.26Z = 4
Monoclinic, C2/cMo Kα
a = 21.419 (4) ŵ = 11.87 mm−1
b = 8.1405 (12) ÅT = 220 (2) K
c = 12.153 (2) Å0.25 × 0.22 × 0.18 mm
β = 118.75 (3)º
Data collection top
Stoe IPDS
diffractometer		1754 independent reflections
Absorption correction: numerical
(IPDS Software; Stoe & Cie, 1999)		1644 reflections with I > 2σ(I)
Tmin = 0.086, Tmax = 0.186Rint = 0.088
5983 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.116  w = 1/[σ2(Fo2) + (0.0673P)2 + 23.535P]
where P = (Fo2 + 2Fc2)/3
S = 1.05Δρmax = 3.61 e Å−3
1754 reflectionsΔρmin = −3.25 e Å−3
98 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
xyzUiso*/Ueq
C1−0.5342 (5)−0.3798 (9)−0.8827 (8)0.0342 (17)
H2−0.4982−0.2945−0.85640.041*
H1−0.5782−0.3334−0.89210.041*
H3−0.5423−0.4251−0.96230.041*
C2−0.5342 (4)−0.9177 (9)−0.8120 (7)0.0253 (15)
H4−0.5372−1.0180−0.85890.030*
H5−0.5753−0.9149−0.79700.030*
C3−0.6049 (4)−0.7510 (9)−0.9974 (7)0.0277 (15)
H7−0.6055−0.6461−1.03760.033*
H8−0.6416−0.7462−0.97150.033*
C4−0.6227 (4)−0.8873 (10)−1.0917 (7)0.0281 (15)
C5−0.7193 (5)−1.0109 (14)−1.2714 (10)0.051 (3)
H10−0.7643−1.0599−1.28530.061*
H9−0.6848−1.0997−1.25290.061*
C6−0.7306 (8)−0.9233 (19)−1.3865 (12)0.079 (4)
H11−0.7488−0.9995−1.45650.095*
H12−0.6857−0.8779−1.37380.095*
H13−0.7646−0.8351−1.40460.095*
N−0.5353 (3)−0.7714 (7)−0.8859 (5)0.0218 (12)
H6−0.5018−0.7864−0.91180.023*
O1−0.5801 (3)−0.9721 (9)−1.1044 (6)0.0436 (16)
O2−0.6931 (3)−0.8978 (8)−1.1645 (6)0.0406 (15)
Br−0.61452 (5)−0.56041 (10)−0.75172 (9)0.0390 (3)
Pt−0.5000−0.56242 (4)−0.75000.02106 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.055 (5)0.018 (4)0.027 (4)−0.003 (3)0.018 (4)0.003 (3)
C20.037 (4)0.022 (3)0.012 (3)−0.005 (3)0.008 (3)−0.001 (3)
C30.033 (3)0.024 (3)0.020 (4)0.003 (3)0.008 (3)−0.001 (3)
C40.031 (3)0.027 (4)0.023 (4)−0.002 (3)0.010 (3)−0.001 (3)
C50.034 (4)0.057 (6)0.052 (6)−0.010 (4)0.012 (4)−0.030 (5)
C60.082 (8)0.102 (11)0.035 (7)−0.002 (7)0.014 (6)−0.019 (7)
N0.033 (3)0.017 (3)0.015 (3)0.001 (2)0.012 (2)0.001 (2)
O10.031 (3)0.060 (4)0.035 (4)0.005 (3)0.012 (3)−0.020 (3)
O20.029 (3)0.043 (3)0.039 (4)−0.001 (2)0.008 (3)−0.018 (3)
Br0.0423 (5)0.0406 (5)0.0378 (5)0.0055 (3)0.0222 (4)−0.0027 (3)
Pt0.0311 (3)0.0134 (2)0.0187 (3)0.0000.01205 (19)0.000
Geometric parameters (Å, °) top
C1—Pt2.052 (8)C5—O21.466 (11)
C1—H20.9700C5—C61.483 (19)
C1—H10.9700C5—H100.9800
C1—H30.9700C5—H90.9800
C2—N1.485 (9)C6—H110.9700
C2—C2i1.515 (14)C6—H120.9700
C2—H40.9800C6—H130.9700
C2—H50.9800N—Pt2.234 (6)
C3—N1.464 (9)N—H60.9200
C3—C41.506 (11)Br—Pt2.4431 (10)
C3—H70.9800Pt—C1i2.052 (8)
C3—H80.9800Pt—Ni2.234 (6)
C4—O11.213 (10)Pt—Bri2.4431 (10)
C4—O21.334 (9)
Pt—C1—H2109.5C5—C6—H12109.5
Pt—C1—H1109.5H11—C6—H12109.5
H2—C1—H1109.5C5—C6—H13109.5
Pt—C1—H3109.5H11—C6—H13109.5
H2—C1—H3109.5H12—C6—H13109.5
H1—C1—H3109.5C3—N—C2111.3 (5)
N—C2—C2i109.1 (5)C3—N—Pt115.5 (4)
N—C2—H4109.9C2—N—Pt105.2 (4)
C2i—C2—H4109.9C3—N—H6108.2
N—C2—H5109.9C2—N—H6108.2
C2i—C2—H5109.9Pt—N—H6108.2
H4—C2—H5108.3C4—O2—C5117.2 (6)
N—C3—C4113.2 (6)C1i—Pt—C187.1 (5)
N—C3—H7108.9C1i—Pt—N176.8 (3)
C4—C3—H7108.9C1—Pt—N96.0 (3)
N—C3—H8108.9C1i—Pt—Ni96.0 (3)
C4—C3—H8108.9C1—Pt—Ni176.8 (3)
H7—C3—H8107.8N—Pt—Ni80.8 (3)
O1—C4—O2124.0 (7)C1i—Pt—Br88.8 (2)
O1—C4—C3125.8 (7)C1—Pt—Br90.7 (2)
O2—C4—C3110.2 (6)N—Pt—Br91.01 (15)
O2—C5—C6110.7 (10)Ni—Pt—Br89.58 (15)
O2—C5—H10109.5C1i—Pt—Bri90.7 (2)
C6—C5—H10109.5C1—Pt—Bri88.8 (2)
O2—C5—H9109.5N—Pt—Bri89.58 (15)
C6—C5—H9109.5Ni—Pt—Bri91.01 (15)
H10—C5—H9108.1Br—Pt—Bri179.23 (4)
C5—C6—H11109.5
N—C3—C4—O1−25.8 (12)C3—N—Pt—C1−41.3 (5)
N—C3—C4—O2156.9 (7)C2—N—Pt—C1−164.5 (5)
C4—C3—N—C2−65.9 (8)C3—N—Pt—Ni138.8 (6)
C4—C3—N—Pt174.2 (5)C2—N—Pt—Ni15.7 (3)
C2i—C2—N—C3−170.9 (7)C3—N—Pt—Br49.4 (5)
C2i—C2—N—Pt−45.2 (7)C2—N—Pt—Br−73.7 (4)
O1—C4—O2—C5−4.6 (13)C3—N—Pt—Bri−130.1 (5)
C3—C4—O2—C5172.7 (8)C2—N—Pt—Bri106.8 (4)
C6—C5—O2—C4−93.6 (11)
Symmetry codes: (i) −x−1, y, −z−3/2.
Table 1
Selected geometric parameters (Å, °) top
C1—Pt2.052 (8)Br—Pt2.4431 (10)
N—Pt2.234 (6)
C1i—Pt—C187.1 (5)N—Pt—Br91.01 (15)
C1—Pt—N96.0 (3)C1—Pt—Bri88.8 (2)
C1—Pt—Ni176.8 (3)N—Pt—Bri89.58 (15)
N—Pt—Ni80.8 (3)Br—Pt—Bri179.23 (4)
C1—Pt—Br90.7 (2)
Symmetry codes: (i) −x−1, y, −z−3/2.
Acknowledgements top

GNK gratefully acknowledges financial support from the Alexander von Humboldt Foundation.

references
References top

Contreras, R., Valderrama, M., Beroggi, C. & Boys, D. (2001). Polyhedron, 20, 3127–3132.

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

Hindmarsh, K., House, D. A. & Turnbull, M. M. (1997). Inorg. Chim. Acta, 257, 11–18.

Hughes, R. P., Sweetser, J. T., Tawa, M. D., Williamson, A., Incarvito, C. D., Rhatigan, B., Rheingold, A. L. & Rossi, G. (2001). Organometallics, 20, 3800–3810.

Kaluđerović, G. N., Đinović, V. M., Juranić, Z. D., Stanojković, T. P. & Sabo, T. J. (2005). J. Inorg. Biochem. 99, 488–498.

Kaluđerović, G. N., Miljković, Dj., Momčilović, M., Đinović, V. M., Mostarica Stojković, M., Sabo, T. J. & Trajković, V. (2005). Int. J. Cancer, 116, 479–486.

Kaluđerović, G. N., Schmidt, H., Schwieger, S., Wagner, Ch., Paschke, R., Dietrich, A., Mueller, T. & Steinborn, D. (2007). Inorg. Chim. Acta Submitted.. Update?

Kaluđerović, G. N., Schmidt, H., Wagner, Ch., Merzweiler, K. & Steinborn, D. (2007). Collect. Czech. Chem. Commun. 72, 560–568.

Rostovtsev, V. V., Henling, L. M., Labinger, J. A. & Bercaw, J. E. (2002). Inorg. Chem. 41, 3608–3619.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Stoe & Cie (1999). IPDS Software (Version 2.90). Stoe & Cie, Darmstadt, Germany.