Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024233/lh2358sup1.cif | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600536807024233/lh2358Isup2.rtv |
CCDC reference: 650699
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).
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).
For related literature, see: Bradner et al. (1980); Hydes (1981); Milburn & Truter (1966); Wells (1984); Zhelegovskay & Fat'kin (1986); Zhelegovskay et al. (1991). One of the figures is missing from the supplementary materials; the figure that we have labelled as figure 1 is actually figure 2 according to the CIF (the ellipsoid plot). The real figure 1 (Rietveld refinement profiles) is missing.
For related literature, see: Allen (2002); Le Bail et al. (1988); Rietveld (1969); Visser (1969).
For related literature, see: Le Bail, Duroy & Fourquet (1988).
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).
[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 |
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 monochromator | 2θmin = 8.0°, 2θmax = 90.0°, 2θstep = 0.02° |
Refinement on F2 | Profile function: Pearson VII |
Least-squares matrix: full | 42 parameters |
Rp = 0.078 | 0 restraints |
Rwp = 0.107 | 0 constraints |
Rexp = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
RBragg = 0.040 | Weighting scheme based on measured s.u.'s |
R(F2) = 0.036 | (Δ/σ)max = 0.1 |
Excluded region(s): none | 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 |
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 | Data collection mode: reflection |
Specimen mounting: packed powder pellet | 2θmin = 8.0°, 2θmax = 90.0°, 2θstep = 0.02° |
Rp = 0.078 | 42 parameters |
Rwp = 0.107 | 0 restraints |
Rexp = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
RBragg = 0.040 | (Δ/σ)max = 0.1 |
R(F2) = 0.036 |
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 code: (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. |
Experimental details
Crystal data | |
Chemical formula | [PtCl4(C3H9N)2] |
Mr | 455.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.8886 (1), 8.9464 (2), 8.3255 (2) |
β (°) | 93.868 (1) |
V (Å3) | 660.54 (2) |
Z | 2 |
Radiation type | Cu Kα |
Specimen shape, size (mm) | Circular flate plate, 20.0 × 20.0 |
Data collection | |
Diffractometer | DRON-4 powder diffractometer |
Specimen mounting | Packed powder pellet |
Data collection mode | Reflection |
Scan method | ? |
2θ values (°) | 2θmin = 8.0 2θmax = 90.0 2θstep = 0.02 |
Refinement | |
R factors and goodness of fit | Rp = 0.078, Rwp = 0.107, Rexp = 0.073, RBragg = 0.040, R(F2) = 0.036, χ2 = 2.132 |
No. of parameters | 42 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
(Δ/σ)max | 0.1 |
Computer programs: DRON-4 (refernce?), POWDER (Kirik et al., 1979), Modified DBWM (Wiles & Young, 1981), Modified DBWM, XP (Siemens, 1989) and PLATON (Spek, 2003).
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 code: (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. |
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).