Acta Cryst. (2007). E63, m1705-m1706 [ doi:10.1107/S1600536807024233 ]
The title compound, trans-[PtCl4(iso-NH2C3H7)2], was obtained by oxidation of trans-[PtCl2(iso-NH2C3H7)2] with chlorine gas. The crystal structure contains discrete centrosymmetric mononuclear complex molecules, with PtIV in a slightly distorted octahedral coordination environment. The slight distortion, as described by the angles at the PtIV atom, is due, in part, to intramolecular N-H
Cl hydrogen bonding [NCl = 2.897 (12) Å]. The Pt-N and Pt-Cl bond lengths are comparable to those in related structures. In the crystal structure, molecules are arranged in layers in the bc plane, with a shortest PtPt distance of 6.1105 (1) Å. The molecules are organized so that isopropylamine ligands project from the layers, forming organic interlayers.
Trans-Pt(iso-NH2C3H7)2Cl2 (2 g) was suspended in 40 ml of water and gaseous chorine was passed through the suspension for 2 h. The yellow substance obtained was filtered, washed with ethanol and dried in air at room temperature.
The structure determination was carried out by X-ray powder diffraction approach. The experimental data were collected using DRON-4 automatic diffractometer, equipped with a secondary flat graphite monochromator in conjunction with a scintillation detector. Cu Kα radiation was used (λ1=1.54056 Å, λ2=1.54439 Å). The sample was prepared by top-loading the standard quartz sample holder with cutting the excess of well grained substance. The diffraction pattern was scanned with the step of 0.02° 2θ and counting time of 5 sec./step in the most informative angular range from 8° to 90% 2θ at ambient temperature. Corundum was used as the external standard. The powder pattern of cis-(isopropylamine) aminne dichloro platimun(II) is presented in Fig.1. X-ray powder diffraction data were deposited in JCPDS-ICDD PDF2 database. Cell parameters were obtained from d-spaces by indexing and refining using programs described in (Visser, 1969, Kirik et al., 1979). The space group was determined from the analysis of systematic absences. The structural investigations were carried out using a full-profile structure analysis package based on a modified version of the Rietveld refinement program DBWS– 9006PC (Wiles & Young, 1981). The intensities of 50 reflections were estimated from the powder pattern by means of the full- profile fitting procedure (Le Bail et al., 1988) and used in the Patterson synthesis. Atoms of Pt and Cl were located directly from the Patterson map. Positions of light atoms N and C were defined from a difference Fourier synthesis. H-atoms were not located, but they were included in the refined structure models and rigidly connected to their C and N atoms. The final refinement was carried out by Rietveld method (Rietveld, 1969).
Data collection: DRON-4 (refernce?); cell refinement: POWDER (Kirik et al., 1979); program(s) used to solve structure: Modified DBWM (Wiles & Young, 1981); program(s) used to refine structure: Modified DBWM; molecular graphics: XP (Siemens, 1989) and PLATON (Spek, 2003).
![[Figure 1]](./lh2358fig1thm.gif)
| Fig. 1. Observed (dots), calculated (superimposed solid) and difference profiles after the Rietveld refinement. The reflection positions are marked by ticks. |
![[Figure 2]](./lh2358fig2thm.gif)
| Fig. 2. Molecular structure of the title compound showing 30% isotropic dispacement ellipsoids. |
![[Figure 3]](./lh2358fig3thm.gif)
| Fig. 3. Part of the crystal structure of trans-Pt(iso-NH2C3H7)2Cl4. |
| [PtCl4(C3H9N)2] | F(000) = 428.0 |
| Mr = 455.11 | Cell parameters are obtained from the Rietveld refinement |
| Monoclinic, P21/c | Dx = 2.288 Mg m−3 |
| Hall symbol: -P 2ybc | Cu Kα radiation, λ = 1.54056 Å |
| a = 8.8886 (1) Å | T = 293 K |
| b = 8.9464 (2) Å | Particle morphology: thin powder |
| c = 8.3255 (2) Å | yellow |
| β = 93.868 (1)° | circular flate plate, 20.0 × 20.0 mm |
| V = 660.54 (2) Å3 | Specimen preparation: Prepared at 293 K and 101 kPa, cooled at 0 K min−1 |
| Z = 2 |
| DRON-4 powder diffractometer | Specimen mounting: packed powder pellet |
| Radiation source: conventional sealed tube | Data collection mode: reflection |
| graphite | 2θmin = 8.0°, 2θmax = 90.0°, 2θstep = 0.02° |
| Refinement on F2 | Excluded region(s): none |
| Least-squares matrix: full | Profile function: Pearson VII |
| Rp = 0.078 | 42 parameters |
| Rwp = 0.107 | 0 restraints |
| Rexp = 0.073 | 0 constraints |
| RBragg = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| R(F2) = 0.036 | Weighting scheme based on measured s.u.'s |
| χ2 = 2.132 | (Δ/σ)max = 0.1 |
| ? data points | Preferred orientation correction: March-Dollase correction |
| [PtCl4(C3H9N)2] | β = 93.868 (1)° |
| Mr = 455.11 | V = 660.54 (2) Å3 |
| Monoclinic, P21/c | Z = 2 |
| a = 8.8886 (1) Å | Cu Kα radiation, λ = 1.54056 Å |
| b = 8.9464 (2) Å | T = 293 K |
| c = 8.3255 (2) Å | circular flate plate, 20.0 × 20.0 mm |
| DRON-4 powder diffractometer | Scan method: ? |
| Specimen mounting: packed powder pellet | 2θmin = 8.0°, 2θmax = 90.0°, 2θstep = 0.02° |
| Data collection mode: reflection |
| Rp = 0.078 | χ2 = 2.132 |
| Rwp = 0.107 | ? data points |
| Rexp = 0.073 | 42 parameters |
| RBragg = 0.040 | 0 restraints |
| R(F) = ? | H atoms treated by a mixture of independent and constrained refinement |
| R(F2) = 0.036 | (Δ/σ)max = 0.1 |
| x | y | z | Uiso*/Ueq | ||
| Pt | 0.0000 | 0.0000 | 0.0000 | 0.0121* | |
| Cl1 | 0.2013 (5) | 0.0270 (12) | 0.1921 (6) | 0.0151* | |
| Cl2 | 0.0140 (12) | −0.2571 (6) | 0.0170 (12) | 0.0153* | |
| C1 | 0.2950 (10) | −0.0360 (10) | −0.1890 (10) | 0.0256* | |
| H1A | 0.3287 (10) | −0.1102 (10) | −0.1115 (10) | 0.1520* | |
| C2 | 0.3450 (10) | −0.0720 (10) | −0.3560 (10) | 0.0393* | |
| H2A | 0.3072 (10) | −0.1685 (10) | −0.3890 (10) | 0.1520* | |
| H2B | 0.3062 (10) | 0.0023 (10) | −0.4310 (10) | 0.1520* | |
| H2C | 0.4531 (10) | −0.0725 (10) | −0.3533 (10) | 0.1520* | |
| C3 | 0.3600 (9) | 0.1200 (9) | −0.1450 (9) | 0.0316* | |
| H3A | 0.4681 (9) | 0.1152 (9) | −0.1367 (9) | 0.152* | |
| H3B | 0.3274 (9) | 0.1904 (9) | −0.2271 (9) | 0.152* | |
| H3C | 0.3249 (9) | 0.1513 (9) | −0.0438 (9) | 0.152* | |
| N | 0.1240 (10) | −0.0200 (10) | −0.2000 (10) | 0.0251* | |
| H4A | 0.1007 (10) | 0.0660 (10) | −0.2660 (10) | 0.1520* | |
| H4B | 0.0845 (10) | −0.1050 (10) | −0.2591 (10) | 0.1520* |
| Pt—N | 2.066 (9) | N—H4B | 0.96 (1) |
| Pt—Cl1 | 2.331 (5) | C3—H3A | 0.96 (1) |
| Pt—Cl2 | 2.307 (5) | C3—H3B | 0.96 (1) |
| C1—C3 | 1.545 (12) | C3—H3C | 0.96 (1) |
| C1—C2 | 1.522 (12) | C2—H2A | 0.96 (1) |
| C1—N | 1.523 (13) | C2—H2B | 0.96 (1) |
| Pt—Pti | 6.1105 (1) | C2—H2C | 0.96 (1) |
| N—H4A | 0.96 (1) | C1—H1A | 0.96 (1) |
| Cl1—Pt—Cl2 | 91.5 (4) | Pt—N—H4B | 106.3 (6) |
| Cl1—Pt—N | 97.7 (3) | N—C1—H1A | 111.8 (8) |
| Cl2—Pt—N | 86.2 (3) | C1—C2—H2A | 109.5 (8) |
| C2—C1—C3 | 106.3 (6) | C1—C2—H2B | 109.5 (8) |
| Pt—N—C1 | 123.0 (6) | C1—C2—H2C | 109.5 (8) |
| N—C1—C2 | 108.5 (7) | C1—C3—H3A | 109.5 (7) |
| N—C1—C3 | 106.6 (7) | C1—C3—H3B | 109.5 (7) |
| Pt—N—H4A | 106.3 (6) | C1—C3—H3C | 109.5 (7) |
| Symmetry codes: (i) −x, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N—H4A···Cl2ii | 0.960 (12) | 2.761 (12) | 3.683 (12) | 161.3 (9) |
| N—H4B···Cl2iii | 0.959 (12) | 2.287 (12) | 3.190 (12) | 156.4 (9) |
| Symmetry codes: (ii) −x, y+1/2, −z−1/2; (iii) x, −y−1/2, z−1/2. |
| Pt—N | 2.066 (9) | Pt—Cl2 | 2.307 (5) |
| Pt—Cl1 | 2.331 (5) | Pt—Pti | 6.1105 (1) |
| Cl1—Pt—Cl2 | 91.5 (4) | Pt—N—C1 | 123.0 (6) |
| Cl1—Pt—N | 97.7 (3) | N—C1—C2 | 108.5 (7) |
| Cl2—Pt—N | 86.2 (3) | N—C1—C3 | 106.6 (7) |
| C2—C1—C3 | 106.3 (6) |
| Symmetry codes: (i) −x, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N—H4A···Cl2ii | 0.960 (12) | 2.761 (12) | 3.683 (12) | 161.3 (9) |
| N—H4B···Cl2iii | 0.959 (12) | 2.287 (12) | 3.190 (12) | 156.4 (9) |
| Symmetry codes: (ii) −x, y+1/2, −z−1/2; (iii) x, −y−1/2, z−1/2. |
X-ray powder diffraction data preparation was supported by the ICDD (Grand-in-Aid 9310) and grant RFBR-KSF 07–03–96805.
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Bradner, W. T., Rose, W. C. & Hyftalen, J. B. (1980). Cisplatin. Current Status and New developments, p. 171. New York: Academic Press.
Hydes, P. C. (1981). GB Patent No. 2060615 cl. C 01.G 55/00.
Kirik, S. D., Borisov, S. V. & Fedorov, V. E. (1979). Zh. Strukt. Khim. 20, 359–364. (In Russian.)
Le Bail, A., Duroy, H. & Fourquet, J. L. (1988). Mater. Res. Bull. 23, 447–452.
Milburn, G. H. W. & Truter, M. R. (1966). J. Chem. Soc. A: Inorg. Phys. Theor. pp. 1609–1616.
Rietveld, H. M. (1969). J. Appl. Cryst. 2, 65–71.
Siemens (1989). XP. Version 4.0. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Visser, J. W. (1969). J. Appl. Cryst. 2, 89–95.
Wells, A. F. (1984). Structural Inorganic Chemistry, 5th ed., pp. 236–242. Oxford: Clarendon. (Russian translation.).
Wiles, D. B. & Young, R. A. (1981). J. Appl. Cryst. 14, 149–151.
Zhelegovskay, H. H., Dyakova, G. B., Fat'kin, L. Yu. & Bokareva, C. C. (1991). Koord. Khim. 17, 1412–1415. (In Russian.)
Zhelegovskay, H. H. & Fat'kin, L. Yu. (1986). Koord. Khim. 12, 1127–1131. (In Russian.)
Asymmetric diamine dichloro platimun(II) complexes, e.g. cis-bis(isopropylamine) dichloro platimun(II) and related compounds (Bradner et al., 1980; Hydes, 1981) can exhibit high anticancer activity. The synthesis of cis-(isopropylamine)amine dichloro platinum(II) has been described by Hydes (1981), Zhelegovskay & Fat'kin (1986) and Zhelegovskay et al. (1991). This is based on the reaction of tetrachloroplatinate(II) potassium with isopropylamine followed by refinement of the target product. The main synthetic difficulties stem from the requirements of low level of impurities because of the medical application. It justifies the interest in possible subsidiary reactions and by-products at the synthesis stage of target compounds. In the present paper, results of a synthesis and a crystal structure determination of trans-bis(isopropylamine) tetrachloro platimun(IV), performed using X-ray powder diffraction technique, are presented.
The crystal structure of trans-bis(isopropylamine) tetrachloro platimun(IV) is of the molecular type with two symmetrically equivalent molecules in unit cell. The molecular structure of the title compound presented in Fig. 2. The Pt atom lies on a center of inversion in a slightly distorted octahedral coordination environment consisting of two N and four Cl atoms. The Pt—N and Pt—Cl distances compare well to literature values (Wells, 1984, Allen, 2002). Isopropylamine as ligand induces more distortion at atom Pt in comparison to an amine as a ligand (Milburn & Truter, 1966). The N—Pt—Cl1 and N—Pt—Cl2 angles are 97.7 (3) and 86.2 (3)° respectively. The N—Cl1 distance of ca 2.89Å allows us to suppose that the distortion in the molecule is induced, in part, by intramolecular hydrogen bonds of the N—H···Cl1 type. In addition, isopropylamine ligands are connected to other molecules by intermolecular hydrogen bonds (see Table 2) and Van der Waals forces also contribute to the crystal packing. The molecules arrange in layers stretched along (bc)-plane with the shortest distances Pd···Pd within a layer about 6.1105 (2)° A. The Pt···Pt distance between layers is substantially longer ca 8.88° A. The molecules orientate in the layers, so that the bulky isopropylamine ligands project above and below each layer comprising organic interlayers (Fig. 3).