Acta Cryst. (2009). E65, m1687 [ doi:10.1107/S1600536809049757 ]
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2O1,O2)platinum(II)The reaction of cis-[Pt(NO3)2(NH3)2] and sodium glycolate yielded the title compound, [Pt(C2H2O3)(NH3)2]. The PtII atom, coordinated by two N atoms of ammine and two O atoms of the carboxylate and oxido groups of the glycolate ligand, is in a square-planar environment. In the crystal structure, molecules are connected by intermolecular N-H
O hydrogen bonds, forming a three-dimensional network.
Cis-[Pt(NO3)2(NH3)2] (2.0 nmol) was dissolved in 50 ml water and sodium glycolate (2.0 mmol in 50 ml water) was added thereto. The mixture was adjusted to pH=7 with NaOH solution and stirred at 323k for 3 h. The solution was condensed at 313k under reduced pressure to 5 ml, then a yellow crystalline product was precipitated. The compound was crystallized from water to obtain crystals suitable for X-ray structure analysis.
All H atoms were initially located in a difference Fourier map. The H atoms bonded to carbon and nitrogen were placed at calculated positions (C—H = 0.97Å and N—H = 0.89 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2Ueq(C), Uiso(H) = 1.5Ueq(N).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./rn2056fig1thm.gif)
| Fig. 1. The molecular structure of title complex with the atomic labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./rn2056fig2thm.gif)
| Fig. 2. The crystal packing, showing the N—H···O hydrogen-bond network. Only the H atoms involved in hydrogen bonding are shown. Hydrogen bonds are shown as dashed lines. |
| [Pt(C2H2O3)(NH3)2] | Dx = 3.480 Mg m−3 |
| Mr = 303.19 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, P212121 | Cell parameters from 1354 reflections |
| a = 5.6293 (6) Å | θ = 2.9–28.3° |
| b = 7.2853 (8) Å | µ = 24.17 mm−1 |
| c = 14.1107 (16) Å | T = 298 K |
| V = 578.70 (11) Å3 | Block, colourless |
| Z = 4 | 0.24 × 0.12 × 0.10 mm |
| F(000) = 544 |
| Bruker APEXII CCD area-detector diffractometer | 1354 independent reflections |
| Radiation source: fine-focus sealed tube | 1307 reflections with I > 2σ(I) |
| graphite | Rint = 0.034 |
| phi and ω scans | θmax = 28.3°, θmin = 2.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −6→7 |
| Tmin = 0.068, Tmax = 0.196 | k = −9→9 |
| 3739 measured reflections | l = −17→18 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.020 | w = 1/[σ2(Fo2) + (0.0103P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.042 | (Δ/σ)max = 0.001 |
| S = 0.99 | Δρmax = 1.24 e Å−3 |
| 1354 reflections | Δρmin = −1.10 e Å−3 |
| 76 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0087 (3) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 489 Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: 0.013 (17) |
| [Pt(C2H2O3)(NH3)2] | V = 578.70 (11) Å3 |
| Mr = 303.19 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 5.6293 (6) Å | µ = 24.17 mm−1 |
| b = 7.2853 (8) Å | T = 298 K |
| c = 14.1107 (16) Å | 0.24 × 0.12 × 0.10 mm |
| Bruker APEXII CCD area-detector diffractometer | 1354 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1307 reflections with I > 2σ(I) |
| Tmin = 0.068, Tmax = 0.196 | Rint = 0.034 |
| 3739 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
| wR(F2) = 0.042 | Δρmax = 1.24 e Å−3 |
| S = 0.99 | Δρmin = −1.10 e Å−3 |
| 1354 reflections | Absolute structure: Flack (1983), 489 Friedel pairs |
| 76 parameters | Flack parameter: 0.013 (17) |
| 0 restraints |
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. |
| x | y | z | Uiso*/Ueq | ||
| Pt1 | 0.10734 (4) | 0.96205 (3) | 0.178777 (16) | 0.01860 (9) | |
| N2 | 0.0429 (10) | 0.9713 (9) | 0.3193 (4) | 0.0310 (12) | |
| H2A | 0.1574 | 1.0347 | 0.3479 | 0.047* | |
| H2B | 0.0392 | 0.8577 | 0.3424 | 0.047* | |
| H2C | −0.0964 | 1.0256 | 0.3296 | 0.047* | |
| N1 | 0.4267 (10) | 0.8432 (8) | 0.2082 (3) | 0.0272 (13) | |
| H1A | 0.4471 | 0.7457 | 0.1711 | 0.041* | |
| H1B | 0.4298 | 0.8085 | 0.2686 | 0.041* | |
| H1C | 0.5427 | 0.9237 | 0.1976 | 0.041* | |
| O1 | 0.1557 (8) | 0.9447 (7) | 0.0377 (3) | 0.0308 (11) | |
| O2 | −0.2005 (8) | 1.0830 (7) | 0.1425 (3) | 0.0263 (11) | |
| C1 | −0.0264 (12) | 0.9948 (9) | −0.0099 (4) | 0.0230 (15) | |
| C2 | −0.2372 (12) | 1.0639 (11) | 0.0439 (5) | 0.0332 (17) | |
| H2E | −0.2827 | 1.1823 | 0.0182 | 0.040* | |
| H2D | −0.3688 | 0.9803 | 0.0337 | 0.040* | |
| O3 | −0.0334 (8) | 0.9898 (7) | −0.0983 (3) | 0.0288 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pt1 | 0.02166 (13) | 0.02149 (13) | 0.01266 (12) | −0.00028 (10) | −0.00029 (9) | 0.00010 (9) |
| N2 | 0.030 (3) | 0.043 (3) | 0.020 (3) | 0.003 (2) | 0.001 (2) | −0.003 (3) |
| N1 | 0.033 (3) | 0.036 (3) | 0.012 (2) | 0.010 (3) | 0.005 (2) | 0.003 (2) |
| O1 | 0.028 (3) | 0.046 (3) | 0.018 (2) | 0.004 (2) | 0.0023 (19) | −0.006 (2) |
| O2 | 0.027 (2) | 0.038 (3) | 0.014 (2) | 0.008 (2) | −0.0030 (18) | −0.0067 (19) |
| C1 | 0.027 (3) | 0.024 (4) | 0.018 (3) | −0.003 (2) | 0.003 (2) | 0.003 (2) |
| C2 | 0.032 (4) | 0.052 (5) | 0.016 (3) | 0.011 (3) | −0.002 (3) | −0.004 (3) |
| O3 | 0.036 (3) | 0.038 (3) | 0.012 (2) | −0.002 (2) | −0.0002 (18) | −0.0005 (19) |
| Pt1—O2 | 2.010 (5) | N1—H1B | 0.8900 |
| Pt1—O1 | 2.013 (4) | N1—H1C | 0.8900 |
| Pt1—N2 | 2.017 (5) | O1—C1 | 1.279 (8) |
| Pt1—N1 | 2.038 (5) | O2—C2 | 1.413 (7) |
| N2—H2A | 0.8900 | C1—O3 | 1.248 (8) |
| N2—H2B | 0.8900 | C1—C2 | 1.496 (9) |
| N2—H2C | 0.8900 | C2—H2E | 0.9700 |
| N1—H1A | 0.8900 | C2—H2D | 0.9700 |
| O2—Pt1—O1 | 83.82 (18) | Pt1—N1—H1C | 109.5 |
| O2—Pt1—N2 | 94.6 (2) | H1A—N1—H1C | 109.5 |
| O1—Pt1—N2 | 176.9 (2) | H1B—N1—H1C | 109.5 |
| O2—Pt1—N1 | 176.77 (19) | C1—O1—Pt1 | 113.2 (4) |
| O1—Pt1—N1 | 93.18 (18) | C2—O2—Pt1 | 109.5 (4) |
| N2—Pt1—N1 | 88.4 (2) | O3—C1—O1 | 122.8 (6) |
| Pt1—N2—H2A | 109.5 | O3—C1—C2 | 119.5 (6) |
| Pt1—N2—H2B | 109.5 | O1—C1—C2 | 117.7 (5) |
| H2A—N2—H2B | 109.5 | O2—C2—C1 | 114.7 (6) |
| Pt1—N2—H2C | 109.5 | O2—C2—H2E | 108.6 |
| H2A—N2—H2C | 109.5 | C1—C2—H2E | 108.6 |
| H2B—N2—H2C | 109.5 | O2—C2—H2D | 108.6 |
| Pt1—N1—H1A | 109.5 | C1—C2—H2D | 108.6 |
| Pt1—N1—H1B | 109.5 | H2E—C2—H2D | 107.6 |
| H1A—N1—H1B | 109.5 | ||
| O2—Pt1—O1—C1 | −6.9 (4) | Pt1—O1—C1—O3 | −178.2 (5) |
| N2—Pt1—O1—C1 | 53 (5) | Pt1—O1—C1—C2 | 2.4 (8) |
| N1—Pt1—O1—C1 | 174.3 (5) | Pt1—O2—C2—C1 | −11.1 (7) |
| O1—Pt1—O2—C2 | 9.7 (4) | O3—C1—C2—O2 | −173.3 (6) |
| N2—Pt1—O2—C2 | −167.7 (5) | O1—C1—C2—O2 | 6.1 (10) |
| N1—Pt1—O2—C2 | 31 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1C···O2i | 0.89 | 2.01 | 2.883 (8) | 167 |
| N1—H1B···O2ii | 0.89 | 2.44 | 3.107 (7) | 132 |
| N1—H1B···O3iii | 0.89 | 2.45 | 3.049 (7) | 125 |
| N1—H1A···O3iv | 0.89 | 2.00 | 2.888 (7) | 173 |
| N2—H2C···O3v | 0.89 | 2.32 | 3.108 (7) | 147 |
| N2—H2B···O2ii | 0.89 | 2.21 | 3.014 (8) | 150 |
| N2—H2A···O3iii | 0.89 | 2.26 | 3.010 (7) | 142 |
| Symmetry codes: (i) x+1, y, z; (ii) −x, y−1/2, −z+1/2; (iii) −x+1/2, −y+2, z+1/2; (iv) x+1/2, −y+3/2, −z; (v) −x−1/2, −y+2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1C···O2i | 0.89 | 2.01 | 2.883 (8) | 167 |
| N1—H1B···O2ii | 0.89 | 2.44 | 3.107 (7) | 132 |
| N1—H1B···O3iii | 0.89 | 2.45 | 3.049 (7) | 125 |
| N1—H1A···O3iv | 0.89 | 2.00 | 2.888 (7) | 173 |
| N2—H2C···O3v | 0.89 | 2.32 | 3.108 (7) | 147 |
| N2—H2B···O2ii | 0.89 | 2.21 | 3.014 (8) | 150 |
| N2—H2A···O3iii | 0.89 | 2.26 | 3.010 (7) | 142 |
| Symmetry codes: (i) x+1, y, z; (ii) −x, y−1/2, −z+1/2; (iii) −x+1/2, −y+2, z+1/2; (iv) x+1/2, −y+3/2, −z; (v) −x−1/2, −y+2, z+1/2. |
This work was supported by the Kunming Innovation Fund for Technology, Kunming IPM Pharmaceutical Co Ltd (08 G100110).
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Griffith, D., Bergamo, A., Pin, S., Vadori, M., Helge, M. B., Sava, G. & Marmion, C. (2007). Polyhedron, 26, 4697–4706.
Inuyama, Y., Miyake, H., Horiuchi, M., Hayasaki, K., Komiyama, S. & Ota, K. (1992). Gan To Kagaku Ryoho, 19, 871–877.
Kameyama, Y., Okazaki, N., Nakagawa, M., Koshida, H., Nakamura, M. & Gemba, M. (1990). Toxicol. Lett. 52,15–24.
Noda, K., Ikeda, M., Yakushiji, M., Nishimura, H., Terashima, Y., Sasaki, H., Hata, T., Kuramoto, H., Tanaka, K., Takahashi, T., Hirabayashi, K., Yamabe, T. & Hatae, M. (1992). Gan To Kagaku Ryoho, 19, 885–892.
Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Taguchi, T., Wakui, A., Nabeya, K., Kurihara, M., Isono, K., Kakegawa, T. & Oka, K. (1992). Gan To Kagaku Ryoho, 19, 483–488.
Yamamoto, N., Tamura, T., Kurata, T., Yamamoto, N., Sekine, I., Kunitoh, H., Kodama, T. & Saijo, N. (2000). Proc. Am. Soc. Clin. Oncol. 19, 203a (abstr 792).
Yuge, H. & Miyamoto, T. K. (1998). Inorg. Chim. Acta, 297, 105–110.
Cis-diamminedichloro-platinum(II) (cisplatin) is one of the most effective anti-cancer drugs for testicular, lung, bladder and other carcinomas. However, the clinical usefulness of this drug has frequently been limited by serious nephrotoxicity and gastrointestinal toxicity and the development of acquired resistance. In an attempt to overcome these drawbacks of cisplatin, numerous analogues have been prepared and evaluated in a search for alternative active agents. Among these compounds, the title compound, cis-diammine(glycolato-o,o')platinum(II), is a second-generation platinum derivative that has an antitumour activity comparable to cisplatin but is less toxic to the kidney (Kameyama et al.,1990), as seen in preclinical experiments. It produced promising response rates in phase II trials for treatment of squamous cell carcinoma arising from the head and neck (Inuyama et al.,1992), lung (Yamamoto et al.,2000), oesophagus (Taguchi et al.,1992), and uterine cervix (Noda et al., 1992). For related structures see: (Yuge & Miyamoto, 1998; Griffith et al., 2007) The compound forms a hydrogen-bonded structure (Fig. 2), in which one of the H atoms of ammonia serves as a donor to the O atom of the glycollate of an adjacent molecule and these hydrogen-bond interactions give rise to a three-dimensional network.