trans-Bis(3-hy­droxy­pyridine-κN)diiodidoplatinum(II) dimethyl sulfoxide disolvate

Huq, F.; Danish, M.; Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536811015893

metal-organic compounds

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Volume 67| Part 6| June 2011| Page m721

doi:10.1107/S1600536811015893

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trans-Bis(3-hydroxypyridine-κN)diiodidoplatinum(II) dimethyl sulfoxide disolvate

Fazlul Huq,^a ^* Muhammed Danish,^b Wojciech Starosta ^c and Janusz Leciejewicz ^c

^aSydney Medical School, The University of Sydney, Cumberland Campus, 75 East Street, Lidcombe, NSW 1825, Australia, ^bDepartment of Chemistry, University of Gujrat, Hafiz Hayat Campus, Gujrat 50700, Pakistan, and ^cInstitute of Nuclear Chemistry and Technology, ul.Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: fazlul.huq@sydney.edu.au

(Received 6 April 2011; accepted 26 April 2011; online 7 May 2011)

In the title compound, [PtI₂(C₅H₅NO)₂]·2(CH₃)₂SO, the Pt^II ion lies on an inversion center and is coordinated in a slightly distorted square-planar environment by two trans iodide ligands and two pyridine N atoms. In the crystal, complex molecules and solvent dimethyl sulfoxide molecules are linked by intermolecular O—H⋯O hydrogen bonds.

Related literature

For the results of activity, cell uptake and DNA binding studies of some trans-planar platinum complexes, see: Farrell et al. (1992 ); Bierbach et al. (1999 ); Huq et al. (2004 ); Daghriri et al. (2004 ); Chowdhury et al. (2005 ). For the structure of trans-dichloridoplatinum(II), see: Beusichem & Farrell (1992 ).

Experimental

Crystal data

[PtI₂(C₅H₅NO)₂]·2C₂H₆OS
M_r = 795.35
Triclinic, $[P \overline 1]$
a = 6.0870 (12) Å
b = 7.8070 (16) Å
c = 12.305 (3) Å
α = 76.52 (3)°
β = 82.95 (3)°
γ = 81.87 (3)°
V = 560.5 (2) Å³
Z = 1
Mo Kα radiation
μ = 9.22 mm⁻¹
T = 293 K
0.19 × 0.15 × 0.05 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008) $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ T_min = 0.091, T_max = 0.467
3570 measured reflections
3281 independent reflections
2568 reflections with I > 2σ(I)
R_int = 0.027
3 standard reflections every 200 reflections intensity decay: 25.2%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.114
S = 1.07
3281 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 1.59 e Å⁻³
Δρ_min = −2.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.77	2.583 (7)	173
Symmetry code: (i) -x+2, -y, -z+2.

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); 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/S1600536811015893/lh5232sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015893/lh5232Isup2.hkl

checkCIF report

Comment top

Currently, attention is focused on platinum compounds that can bind to DNA differently than cisplatin with the idea that the different nature of binding with DNA may result into an altered spectrum of activity (Daghriri et al., 2004). One such class of compounds are trans- planaramineplatinum complexes that bind with DNA to form mainly interstrand bifunctional 1,2-Pt(GG) adduct whereas cisplatin and its analogues form mainly intrastrand 1,2-Pt(GG) and 1,2-Pt(AG) adducts (Huq et al., 2004). A number of trans-planaramineplatinum complexes have been prepared (Huq et al., 2004; Chowdhury et al., 2005; Beusichem & Farrell, 1992; Bierbach et al., 1999; Farrell et al., 1992). They have shown in vitro activity similar to cisplatin against various cancer cell lines. One of these compounds is trans-dichloro-bis(3-hydroxypyridine) platinum(II) (Huq et al., 2004). In the title compound the chloride ligands have been replaced by iodide ligands. The crystal structure contains discrete molecules in which Pt^II ions lie on inversion centers (Fig. 1). Pt^II ions are coordinated to two symmetry related 3-hydroxypyridine ligand molecules via the pyridine N atoms and by two iodide ligands in a trans mode. The 3-hydroxypyridine ligand is planar with an r.m.s. of 0.0060 (2) Å. The coordination plane Pt/N1/I1/N1ⁱ/I1ⁱ (Symmetry code: (i) -x+1, -y+1, -z+1) forms an angle of 72.8 (2)° with the ligand plane (N1/C2-C6/O1). In the crystal, complex molecules and solvent dimethyl sulfoxide molecules are linked by intermolecular O—H···O hydrogen bonds (Fig. 2).

Related literature top

For the results of activity, cell uptake and DNA binding studies of some trans-planar platinum complexes, see: Farrell et al. (1992); Bierbach et al. (1999); Huq et al. (2004); Daghriri et al. (2004); Chowdhury et al. (2005). For the structure of trans-dichlorobis(thiazole)platinum (II), see: Beusichem & Farrell (1992).

Experimental top

1.0 mmol (415 mg) of K₂PtCl₄ was dissolved in 10 ml of ml water and 12 mmol (2.0 g) of KI was added and stirred for 30 min. 2.0 mmol (192 mg) of 3-hydroxypyridine, dissolved in 5 ml of ml water by sonification, was added with stirring to the mixture that was kept in ice. The mixture was stirred at room temperature for about 24 h. The yellow precipitate of Pt(3-hydroxypyridine)₂I₂ was collected by filtration, washed with ice cold water and ethanol, then air-dried. The precipitate was dissolved in a 1:1 DMSO:water mixture on heating and left standing. Crystals were obtained after 15 days.

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); data reduction: DATAPROC (Kuma, 2001); 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 labeled asymmetric unit and symmetry generated (-x+1, -y+1, -z+1) atoms of the complex molecule of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

(I) top

Crystal data top

[PtI₂(C₅H₅NO)₂]·2C₂H₆OS	Z = 1
M_r = 795.35	F(000) = 368
Triclinic, P1	D_x = 2.356 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0870 (12) Å	Cell parameters from 25 reflections
b = 7.8070 (16) Å	θ = 6–15°
c = 12.305 (3) Å	µ = 9.22 mm⁻¹
α = 76.52 (3)°	T = 293 K
β = 82.95 (3)°	Plate, pale yellow
γ = 81.87 (3)°	0.19 × 0.15 × 0.05 mm
V = 560.5 (2) Å³

Data collection top

Kuma KM-4 four-circle diffractometer	2568 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 30.1°, θ_min = 1.7°
profile data from ω/2θ scans	h = 0→8
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −10→10
T_min = 0.091, T_max = 0.467	l = −17→17
3570 measured reflections	3 standard reflections every 200 reflections
3281 independent reflections	intensity decay: 25.2%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0739P)² + 0.7284P] where P = (F_o² + 2F_c²)/3
3281 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 1.59 e Å⁻³
0 restraints	Δρ_min = −2.75 e Å⁻³

Crystal data top

[PtI₂(C₅H₅NO)₂]·2C₂H₆OS	γ = 81.87 (3)°
M_r = 795.35	V = 560.5 (2) Å³
Triclinic, P1	Z = 1
a = 6.0870 (12) Å	Mo Kα radiation
b = 7.8070 (16) Å	µ = 9.22 mm⁻¹
c = 12.305 (3) Å	T = 293 K
α = 76.52 (3)°	0.19 × 0.15 × 0.05 mm
β = 82.95 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	2568 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.027
T_min = 0.091, T_max = 0.467	3 standard reflections every 200 reflections
3570 measured reflections	intensity decay: 25.2%
3281 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.07	Δρ_max = 1.59 e Å⁻³
3281 reflections	Δρ_min = −2.75 e Å⁻³
118 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

	x	y	z	U_iso*/U_eq
Pt1	0.5000	0.5000	0.5000	0.03310 (11)
I1	0.52440 (7)	0.68468 (5)	0.64805 (4)	0.04702 (13)
S1	0.9980 (3)	0.2348 (2)	0.93997 (17)	0.0497 (4)
N1	0.6905 (8)	0.2937 (6)	0.5856 (4)	0.0358 (9)
O1	0.6176 (9)	−0.0245 (7)	0.8443 (5)	0.0581 (14)
H1	0.7052	−0.0992	0.8805	0.087*
O2	1.1336 (10)	0.2639 (7)	1.0279 (5)	0.0606 (14)
C2	0.6050 (10)	0.1983 (8)	0.6833 (5)	0.0407 (12)
H2	0.4573	0.2293	0.7080	0.049*
C3	0.7252 (10)	0.0565 (7)	0.7490 (5)	0.0385 (11)
C6	0.9025 (10)	0.2500 (8)	0.5501 (6)	0.0425 (13)
H6	0.9629	0.3151	0.4826	0.051*
C4	0.9432 (11)	0.0105 (8)	0.7117 (6)	0.0449 (13)
H4	1.0283	−0.0857	0.7528	0.054*
C5	1.0354 (11)	0.1105 (9)	0.6109 (6)	0.0470 (14)
H5	1.1835	0.0837	0.5852	0.056*
C11	1.0277 (16)	0.4169 (11)	0.8257 (7)	0.063 (2)
H11A	0.9749	0.5250	0.8500	0.095*
H11B	0.9423	0.4073	0.7673	0.095*
H11C	1.1819	0.4176	0.7978	0.095*
C12	0.7179 (15)	0.2967 (17)	0.9862 (10)	0.087 (3)
H12A	0.6764	0.2172	1.0555	0.130*
H12B	0.6230	0.2911	0.9306	0.130*
H12C	0.7020	0.4156	0.9976	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.02968 (15)	0.02872 (14)	0.03610 (16)	0.00271 (9)	−0.00194 (10)	−0.00172 (10)
I1	0.0506 (2)	0.0420 (2)	0.0489 (3)	0.00216 (18)	−0.00824 (19)	−0.01362 (18)
S1	0.0558 (9)	0.0362 (7)	0.0553 (10)	−0.0041 (6)	−0.0098 (8)	−0.0051 (7)
N1	0.039 (2)	0.0284 (19)	0.036 (2)	0.0004 (17)	−0.0004 (18)	−0.0029 (17)
O1	0.048 (3)	0.055 (3)	0.057 (3)	−0.006 (2)	−0.005 (2)	0.017 (2)
O2	0.070 (3)	0.047 (3)	0.063 (3)	−0.002 (2)	−0.027 (3)	0.000 (2)
C2	0.035 (3)	0.037 (3)	0.045 (3)	0.006 (2)	−0.006 (2)	−0.003 (2)
C3	0.040 (3)	0.030 (2)	0.042 (3)	−0.003 (2)	−0.003 (2)	−0.002 (2)
C6	0.037 (3)	0.040 (3)	0.046 (3)	0.004 (2)	−0.001 (2)	−0.006 (2)
C4	0.044 (3)	0.040 (3)	0.048 (3)	0.004 (2)	−0.012 (3)	−0.007 (3)
C5	0.036 (3)	0.050 (3)	0.051 (4)	0.008 (2)	−0.004 (2)	−0.011 (3)
C11	0.082 (6)	0.053 (4)	0.045 (4)	0.006 (4)	−0.003 (4)	0.000 (3)
C12	0.052 (5)	0.111 (8)	0.099 (8)	−0.030 (5)	0.011 (5)	−0.024 (7)

Geometric parameters (Å, º) top

Pt1—N1ⁱ	2.007 (5)	C3—C4	1.376 (9)
Pt1—N1	2.007 (5)	C6—C5	1.385 (8)
Pt1—I1	2.6021 (8)	C6—H6	0.9300
Pt1—I1ⁱ	2.6021 (8)	C4—C5	1.402 (10)
S1—O2	1.514 (6)	C4—H4	0.9300
S1—C11	1.763 (8)	C5—H5	0.9300
S1—C12	1.767 (10)	C11—H11A	0.9600
N1—C6	1.334 (7)	C11—H11B	0.9600
N1—C2	1.345 (8)	C11—H11C	0.9600
O1—C3	1.336 (8)	C12—H12A	0.9600
O1—H1	0.8200	C12—H12B	0.9600
C2—C3	1.383 (8)	C12—H12C	0.9600
C2—H2	0.9300

N1ⁱ—Pt1—N1	179.999 (1)	N1—C6—H6	119.0
N1ⁱ—Pt1—I1	89.13 (15)	C5—C6—H6	119.0
N1—Pt1—I1	90.87 (15)	C3—C4—C5	119.1 (6)
N1ⁱ—Pt1—I1ⁱ	90.87 (15)	C3—C4—H4	120.5
N1—Pt1—I1ⁱ	89.13 (15)	C5—C4—H4	120.5
I1—Pt1—I1ⁱ	180.0	C6—C5—C4	119.0 (6)
O2—S1—C11	105.5 (4)	C6—C5—H5	120.5
O2—S1—C12	105.1 (5)	C4—C5—H5	120.5
C11—S1—C12	97.6 (5)	S1—C11—H11A	109.5
C6—N1—C2	118.5 (5)	S1—C11—H11B	109.5
C6—N1—Pt1	122.1 (4)	H11A—C11—H11B	109.5
C2—N1—Pt1	119.5 (4)	S1—C11—H11C	109.5
C3—O1—H1	109.5	H11A—C11—H11C	109.5
N1—C2—C3	123.5 (5)	H11B—C11—H11C	109.5
N1—C2—H2	118.3	S1—C12—H12A	109.5
C3—C2—H2	118.3	S1—C12—H12B	109.5
O1—C3—C4	125.5 (5)	H12A—C12—H12B	109.5
O1—C3—C2	116.5 (6)	S1—C12—H12C	109.5
C4—C3—C2	118.0 (6)	H12A—C12—H12C	109.5
N1—C6—C5	121.9 (6)	H12B—C12—H12C	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱⁱ	0.82	1.77	2.583 (7)	173

Symmetry code: (ii) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[PtI₂(C₅H₅NO)₂]·2C₂H₆OS
M_r	795.35
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.0870 (12), 7.8070 (16), 12.305 (3)
α, β, γ (°)	76.52 (3), 82.95 (3), 81.87 (3)
V (Å³)	560.5 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	9.22
Crystal size (mm)	0.19 × 0.15 × 0.05

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.091, 0.467
No. of measured, independent and observed [I > 2σ(I)] reflections	3570, 3281, 2568
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.114, 1.07
No. of reflections	3281
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.59, −2.75

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), 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
O1—H1···O2ⁱ	0.82	1.77	2.583 (7)	173

Symmetry code: (i) −x+2, −y, −z+2.

References

Beusichem, N. V. & Farrell, N. (1992). Inorg. Chem. 31, 634–639. Google Scholar
Bierbach, U., Qu, Y., Hambley, T.W., Peroutka, J., Nguyen, H.L., Doedee, M. & Farrell, N. (1999). Inorg. Chem. 38, 3535–3542. CrossRef PubMed CAS Google Scholar
Chowdhury, A., Huq, F., Abdullah, A., Beale, P. & Fisher, K. (2005). Inorg. Biochem. 99, 1098–1112. CrossRef CAS Google Scholar
Daghriri, H., Huq, F. & Beale, P. (2004). Inorg. Biochem. 98, 1722–1733. CrossRef CAS Google Scholar
Farrell, N., Kelland, L. R., Roberts, J. D. & Beusichem, M. V. (1992). Cancer Res. 52, 5065–5072. PubMed CAS Web of Science Google Scholar
Huq, F., Yu, J. Q., Daghriri, H. & Beale, P. (2004). Inorg. Biochem. 98, 1261–1270. CrossRef CAS Google Scholar
Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m721

doi:10.1107/S1600536811015893

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		EndNote
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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

trans-Bis(3-hy­dr­oxy­pyridine-κN)di­iodidoplatinum(II) di­methyl sulfoxide disolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

trans-Bis(3-hydroxypyridine-κN)diiodidoplatinum(II) dimethyl sulfoxide disolvate