cis-Diammine(glycolato-κ2O1,O2)platinum(II)

Wang, Q.-K.; Pu, S.-P.; Cong, Y.-W.; Li, Y.-N.; Luan, C.-F.

doi:10.1107/S1600536809049757

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1687

doi:10.1107/S1600536809049757

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cis-Diammine(glycolato-κ²O¹,O²)platinum(II)

Qing-Kun Wang,^a Shao-Ping Pu,^b,^c ^* Yan-Wei Cong,^b Yong-Nian Li ^b and Chun-Fang Luan ^b

^aKunming Institute of Precious Metals, Kunming 650106, People's Republic of China, ^bKunming IPM Pharmaceutical Co Ltd, Department of Materials, Kunming University of Science and Technology, Kunming 650106, People's Republic of China, and ^cEngineering School of Materials and Metallurgy, Kunming University of Science and Technology, Kunming 650093, People's Republic of China
^*Correspondence e-mail: JRSS1979@163.COM

(Received 3 March 2009; accepted 20 November 2009; online 28 November 2009)

The reaction of cis-[Pt(NO₃)₂(NH₃)₂] and sodium glycolate yielded the title compound, [Pt(C₂H₂O₃)(NH₃)₂]. The Pt^II 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.

Related literature

The title compound is a second-generation platinum derivative that has an antitumour activity comparable to that of cisplatin, one of the most effective anti-cancer drugs for testicular, lung, bladder and other carcinomas, but which is less toxic to the kidney, see: Inuyama et al. (1992 ); Kameyama et al. (1990 ); Noda et al. (1992 ); Taguchi et al. (1992 ); Yamamoto et al. (2000 ). For related structures, see: Yuge & Miyamoto (1998 ); Griffith et al. (2007 ).

Experimental

Crystal data

[Pt(C₂H₂O₃)(NH₃)₂]
M_r = 303.19
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.6293 (6) Å
b = 7.2853 (8) Å
c = 14.1107 (16) Å
V = 578.70 (11) Å³
Z = 4
Mo Kα radiation
μ = 24.17 mm⁻¹
T = 298 K
0.24 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.068, T_max = 0.196
3739 measured reflections
1354 independent reflections
1307 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.042
S = 0.99
1354 reflections
76 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −1.10 e Å⁻³
Absolute structure: Flack (1983 ), 489 Friedel pairs
Flack parameter: 0.013 (17)

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O3^iv	0.89	2.00	2.888 (7)	173
N2—H2C⋯O3^v	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) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (v) $[-x-{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049757/rn2056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049757/rn2056Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

the title compound is a second-generation platinum derivative that has an antitumour activity comparable to that of cisplatin, one of the most effective anti-cancer drugs for testicular, lung, bladder and other carcinomas, but which is less toxic to the kidney, see: IInuyama et al. (1992); Kameyama et al. (1990); Noda et al. (1992); Taguchi et al. (1992); Yamamoto et al. (2000).For related structures, see: Yuge & Miyamoto (1998); Griffith et al. (2007).

Experimental top

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.

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of title complex with the atomic labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	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.

cis-Diammine(glycolato-κ²O¹,O²)platinum(II) top

Crystal data top

[Pt(C₂H₂O₃)(NH₃)₂]	D_x = 3.480 Mg m⁻³
M_r = 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

Data collection top

Bruker APEXII CCD area-detector diffractometer	1354 independent reflections
Radiation source: fine-focus sealed tube	1307 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
phi and ω scans	θ_max = 28.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −6→7
T_min = 0.068, T_max = 0.196	k = −9→9
3739 measured reflections	l = −17→18

Refinement top

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(F_o²) + (0.0103P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.042	(Δ/σ)_max = 0.001
S = 0.99	Δρ_max = 1.24 e Å⁻³
1354 reflections	Δρ_min = −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	Absolute structure parameter: 0.013 (17)

Crystal data top

[Pt(C₂H₂O₃)(NH₃)₂]	V = 578.70 (11) Å³
M_r = 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

Data collection top

Bruker APEXII CCD area-detector diffractometer	1354 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	1307 reflections with I > 2σ(I)
T_min = 0.068, T_max = 0.196	R_int = 0.034
3739 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	H-atom parameters constrained
wR(F²) = 0.042	Δρ_max = 1.24 e Å⁻³
S = 0.99	Δρ_min = −1.10 e Å⁻³
1354 reflections	Absolute structure: Flack (1983), 489 Friedel pairs
76 parameters	Absolute structure parameter: 0.013 (17)
0 restraints

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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.89	2.00	2.888 (7)	173
N2—H2C···O3^v	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.

Experimental details

Crystal data
Chemical formula	[Pt(C₂H₂O₃)(NH₃)₂]
M_r	303.19
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	5.6293 (6), 7.2853 (8), 14.1107 (16)
V (Å³)	578.70 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	24.17
Crystal size (mm)	0.24 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.068, 0.196
No. of measured, independent and observed [I > 2σ(I)] reflections	3739, 1354, 1307
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.042, 0.99
No. of reflections	1354
No. of parameters	76
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −1.10
Absolute structure	Flack (1983), 489 Friedel pairs
Absolute structure parameter	0.013 (17)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2ⁱ	0.89	2.01	2.883 (8)	166.5
N1—H1B···O2ⁱⁱ	0.89	2.44	3.107 (7)	132.4
N1—H1B···O3ⁱⁱⁱ	0.89	2.45	3.049 (7)	124.6
N1—H1A···O3^iv	0.89	2.00	2.888 (7)	173.1
N2—H2C···O3^v	0.89	2.32	3.108 (7)	147.2
N2—H2B···O2ⁱⁱ	0.89	2.21	3.014 (8)	150.3
N2—H2A···O3ⁱⁱⁱ	0.89	2.26	3.010 (7)	142.3

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.

Acknowledgements

This work was supported by the Kunming Innovation Fund for Technology, Kunming IPM Pharmaceutical Co Ltd (08 G100110).

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