trans-Chlorido(dimethyl sulfoxide-κS)(pyridine-2-carboxyl­ato-κ2N,O)platinum(II)

Ha, K.

doi:10.1107/S1600536810005520

metal-organic compounds

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Volume 66| Part 3| March 2010| Page m295

doi:10.1107/S1600536810005520

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trans-Chlorido(dimethyl sulfoxide-κS)(pyridine-2-carboxylato-κ²N,O)platinum(II)

Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 5 February 2010; accepted 10 February 2010; online 13 February 2010)

In the title complex, [Pt(C₆H₄NO₂)Cl(C₂H₆OS)], the Pt^II ion is in a distorted square-planar environment defined by the N and O atoms from the chelating pyridine-2-carboxylate (pic) anionic ligand, one S atom of the dimethyl sulfoxide molecule and one Cl ion. The complex is disposed about a crystallographic mirror plane parallel to the ac plane passing through all the atoms of the complex except the methyl atoms of the dimethyl sulfoxide. The molecules are stacked in columns along the b axis with a Pt⋯Pt distance of 4.9508 (5) Å. Within the column, intermolecular C—H⋯O hydrogen bonds and weak π–π interactions between adjacent pyridine rings are present, the shortest centroid–centroid distance being 5.153 (4) Å.

Related literature

For the crystal structure of the title complex with the monoclinic space group P2₁/n, see: Annibale et al. (1986 ). For details of Pt(IV)–pic complexes, see: Griffith et al. (2005 ); Kim et al. (2009 ).

Experimental

Crystal data

[Pt(C₆H₄NO₂)Cl(C₂H₆OS)]
M_r = 430.77
Orthorhombic, P n m a
a = 19.5900 (15) Å
b = 6.9450 (6) Å
c = 8.1266 (6) Å
V = 1105.64 (15) Å³
Z = 4
Mo Kα radiation
μ = 13.11 mm⁻¹
T = 200 K
0.21 × 0.17 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.631, T_max = 1.000
6423 measured reflections
1169 independent reflections
1085 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.065
S = 1.10
1169 reflections
89 parameters
H-atom parameters constrained
Δρ_max = 2.60 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pt1—O1	2.020 (5)
Pt1—N1	2.031 (7)
Pt1—S1	2.202 (2)
Pt1—Cl1	2.2945 (19)

O1—Pt1—N1	81.0 (2)
O1—Pt1—S1	177.70 (16)
N1—Pt1—S1	101.31 (19)
O1—Pt1—Cl1	88.98 (16)
N1—Pt1—Cl1	169.97 (19)
S1—Pt1—Cl1	88.72 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O3	0.95	2.16	2.995 (11)	145
C2—H2⋯O1ⁱ	0.95	2.35	3.255 (11)	158
C7—H7A⋯O2ⁱⁱ	0.98	2.42	3.323 (8)	152
C7—H7B⋯Cl1	0.98	2.77	3.355 (7)	119
Symmetry codes: (i) x, y, z-1; (ii) $[-x, y-{\script{1\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536810005520/si2243sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005520/si2243Isup2.hkl

checkCIF report

Comment top

The title complex, [Pt(C₆H₄NO₂)Cl(C₂H₆OS)], crystallized in the orthorhombic space group Pnma, whereas, in the previously reported X-ray structure analysis, the complex crystallized in the monoclinic space group P2₁/n (Annibale et al., 1986). The Pt^II ion lies in a distorted square-planar environment defined by the N and O atoms from the chelating pyridine-2-carboxylate (pic) anionic ligand, one S atom of the dimethyl sulfoxide molecule and one Cl ion (Fig. 1). The tight O1—Pt1—N1 chelate angle [81.0 (2)°] results in non-linear trans axes [<O1—Pt1—S1 = 177.70 (16)° and <N1—Pt1—Cl1 = 169.97 (19)°] (Table 1). The complex is disposed about a crystallographic mirror plane parallel to the ac plane passing through all the atoms of the complex at the special positions (x,1/4,z), except the methyl atoms of the dimethyl sulfoxide (Fig. 2). The molecules are stacked in columns along the b axis with a Pt···Pt distance of 4.9508 (5) Å. In the column, intermolecular C—H···O hydrogen bond (Table 2) and weak π-π interactions between adjacent pyridine rings are present, the shortest centroid-centroid distance being 5.153 (4) Å, and the ring planes are parallel and shifted for 3.807 Å. The intramolecular C—H···O and C—H···Cl hydrogen bonds are also observed (Table 2).

Related literature top

For the crystal structure of the title complex with the monoclinic space group P2₁/n, see: Annibale et al. (1986). For details of Pt(IV)–pic complexes, see: Griffith et al. (2005); Kim et al. (2009).

Experimental top

Single crystals of the title complex were unexpectedly obtained by reacting K₂PtCl₄ (0.2000 g, 0.482 mmol) and pyridine-2-carboxylic acid (0.1192 g, 0.968 mmol) in H₂O (10 ml) under reflux for 5 h. Crystals suitable for X-ray analysis were obtained by slow evaporation from a dimethyl sulfoxide solution of the pale yellow reaction product at 80 °C.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title complex, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [Symmetry code: (a) x, 1/2 - y, z].
	Fig. 2. View of the unit-cell contents of the title complex. Hydrogen-bond interactions are drawn with dashed lines.

trans-Chlorido(dimethyl sulfoxide-κS)(pyridine-2-carboxylato-κ²N,O)platinum(II) top

Crystal data top

[Pt(C₆H₄NO₂)Cl(C₂H₆OS)]	F(000) = 800
M_r = 430.77	D_x = 2.588 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3961 reflections
a = 19.5900 (15) Å	θ = 2.7–26.0°
b = 6.9450 (6) Å	µ = 13.11 mm⁻¹
c = 8.1266 (6) Å	T = 200 K
V = 1105.64 (15) Å³	Block, colorless
Z = 4	0.21 × 0.17 × 0.09 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1169 independent reflections
Radiation source: fine-focus sealed tube	1085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −24→23
T_min = 0.631, T_max = 1.000	k = −8→8
6423 measured reflections	l = −7→10

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0345P)² + 1.8204P] where P = (F_o² + 2F_c²)/3
1169 reflections	(Δ/σ)_max = 0.001
89 parameters	Δρ_max = 2.60 e Å⁻³
0 restraints	Δρ_min = −0.79 e Å⁻³

Crystal data top

[Pt(C₆H₄NO₂)Cl(C₂H₆OS)]	V = 1105.64 (15) Å³
M_r = 430.77	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 19.5900 (15) Å	µ = 13.11 mm⁻¹
b = 6.9450 (6) Å	T = 200 K
c = 8.1266 (6) Å	0.21 × 0.17 × 0.09 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1169 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1085 reflections with I > 2σ(I)
T_min = 0.631, T_max = 1.000	R_int = 0.042
6423 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.10	Δρ_max = 2.60 e Å⁻³
1169 reflections	Δρ_min = −0.79 e Å⁻³
89 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.087714 (15)	0.2500	1.04929 (4)	0.01771 (13)
Cl1	0.14026 (11)	0.2500	1.3016 (2)	0.0265 (5)
S1	0.18928 (11)	0.2500	0.9332 (2)	0.0209 (4)
O1	−0.0036 (3)	0.2500	1.1647 (7)	0.0243 (13)
O2	−0.1160 (3)	0.2500	1.1182 (8)	0.0311 (14)
O3	0.1947 (3)	0.2500	0.7524 (8)	0.0353 (15)
N1	0.0258 (3)	0.2500	0.8489 (8)	0.0204 (15)
C1	0.0441 (5)	0.2500	0.6884 (10)	0.029 (2)
H1	0.0911	0.2500	0.6596	0.035*
C2	−0.0051 (5)	0.2500	0.5652 (11)	0.035 (2)
H2	0.0085	0.2500	0.4530	0.042*
C3	−0.0726 (4)	0.2500	0.6045 (12)	0.0274 (19)
H3	−0.1066	0.2500	0.5211	0.033*
C4	−0.0903 (4)	0.2500	0.7672 (12)	0.028 (2)
H4	−0.1372	0.2500	0.7968	0.034*
C5	−0.0410 (4)	0.2500	0.8904 (11)	0.0205 (17)
C6	−0.0570 (4)	0.2500	1.0681 (10)	0.0217 (18)
C7	0.2372 (3)	0.0507 (9)	1.0071 (8)	0.0300 (14)
H7A	0.2145	−0.0694	0.9755	0.045*
H7B	0.2405	0.0577	1.1273	0.045*
H7C	0.2832	0.0539	0.9593	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.0175 (2)	0.02225 (19)	0.0134 (2)	0.000	0.00107 (12)	0.000
Cl1	0.0231 (11)	0.0425 (12)	0.0138 (10)	0.000	−0.0040 (8)	0.000
S1	0.0195 (11)	0.0258 (10)	0.0174 (10)	0.000	0.0024 (8)	0.000
O1	0.018 (3)	0.044 (3)	0.011 (3)	0.000	0.003 (2)	0.000
O2	0.024 (3)	0.047 (4)	0.022 (3)	0.000	0.003 (3)	0.000
O3	0.036 (4)	0.055 (4)	0.015 (3)	0.000	0.016 (3)	0.000
N1	0.023 (4)	0.019 (3)	0.019 (4)	0.000	0.000 (3)	0.000
C1	0.028 (5)	0.049 (5)	0.009 (4)	0.000	0.003 (3)	0.000
C2	0.037 (6)	0.047 (6)	0.020 (5)	0.000	−0.001 (4)	0.000
C3	0.021 (5)	0.038 (5)	0.023 (5)	0.000	−0.006 (4)	0.000
C4	0.023 (5)	0.033 (5)	0.028 (5)	0.000	0.001 (4)	0.000
C5	0.023 (4)	0.013 (3)	0.025 (4)	0.000	−0.002 (4)	0.000
C6	0.019 (4)	0.024 (4)	0.022 (5)	0.000	0.002 (3)	0.000
C7	0.023 (3)	0.029 (3)	0.038 (4)	0.007 (3)	0.005 (3)	0.005 (3)

Geometric parameters (Å, º) top

Pt1—O1	2.020 (5)	C1—H1	0.9500
Pt1—N1	2.031 (7)	C2—C3	1.361 (13)
Pt1—S1	2.202 (2)	C2—H2	0.9500
Pt1—Cl1	2.2945 (19)	C3—C4	1.367 (14)
S1—O3	1.473 (6)	C3—H3	0.9500
S1—C7ⁱ	1.778 (6)	C4—C5	1.390 (13)
S1—C7	1.778 (6)	C4—H4	0.9500
O1—C6	1.308 (10)	C5—C6	1.477 (12)
O2—C6	1.225 (11)	C7—H7A	0.9800
N1—C5	1.352 (10)	C7—H7B	0.9800
N1—C1	1.352 (11)	C7—H7C	0.9800
C1—C2	1.390 (13)

O1—Pt1—N1	81.0 (2)	C3—C2—H2	119.8
O1—Pt1—S1	177.70 (16)	C1—C2—H2	119.8
N1—Pt1—S1	101.31 (19)	C2—C3—C4	118.2 (8)
O1—Pt1—Cl1	88.98 (16)	C2—C3—H3	120.9
N1—Pt1—Cl1	169.97 (19)	C4—C3—H3	120.9
S1—Pt1—Cl1	88.72 (7)	C3—C4—C5	121.4 (8)
O3—S1—C7ⁱ	107.4 (3)	C3—C4—H4	119.3
O3—S1—C7	107.4 (3)	C5—C4—H4	119.3
C7ⁱ—S1—C7	102.3 (5)	N1—C5—C4	119.5 (8)
O3—S1—Pt1	119.5 (3)	N1—C5—C6	116.7 (7)
C7ⁱ—S1—Pt1	109.4 (2)	C4—C5—C6	123.8 (8)
C7—S1—Pt1	109.4 (2)	O2—C6—O1	123.7 (8)
C6—O1—Pt1	115.4 (5)	O2—C6—C5	121.7 (8)
C5—N1—C1	119.8 (7)	O1—C6—C5	114.7 (7)
C5—N1—Pt1	112.2 (6)	S1—C7—H7A	109.5
C1—N1—Pt1	127.9 (6)	S1—C7—H7B	109.5
N1—C1—C2	120.7 (8)	H7A—C7—H7B	109.5
N1—C1—H1	119.6	S1—C7—H7C	109.5
C2—C1—H1	119.6	H7A—C7—H7C	109.5
C3—C2—C1	120.3 (9)	H7B—C7—H7C	109.5

N1—Pt1—S1—O3	0.0	N1—C1—C2—C3	0.000 (2)
Cl1—Pt1—S1—O3	180.0	C1—C2—C3—C4	0.000 (2)
N1—Pt1—S1—C7ⁱ	124.3 (3)	C2—C3—C4—C5	0.000 (2)
Cl1—Pt1—S1—C7ⁱ	−55.7 (3)	C1—N1—C5—C4	0.000 (2)
N1—Pt1—S1—C7	−124.3 (3)	Pt1—N1—C5—C4	180.000 (2)
Cl1—Pt1—S1—C7	55.7 (3)	C1—N1—C5—C6	180.000 (2)
N1—Pt1—O1—C6	0.000 (2)	Pt1—N1—C5—C6	0.000 (2)
Cl1—Pt1—O1—C6	180.000 (2)	C3—C4—C5—N1	0.000 (2)
O1—Pt1—N1—C5	0.000 (1)	C3—C4—C5—C6	180.000 (2)
S1—Pt1—N1—C5	180.000 (1)	Pt1—O1—C6—O2	180.000 (2)
Cl1—Pt1—N1—C5	0.000 (4)	Pt1—O1—C6—C5	0.000 (2)
O1—Pt1—N1—C1	180.000 (1)	N1—C5—C6—O2	180.000 (2)
S1—Pt1—N1—C1	0.000 (1)	C4—C5—C6—O2	0.000 (2)
Cl1—Pt1—N1—C1	180.000 (3)	N1—C5—C6—O1	0.000 (2)
C5—N1—C1—C2	0.000 (2)	C4—C5—C6—O1	180.000 (2)
Pt1—N1—C1—C2	180.000 (1)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3	0.95	2.16	2.995 (11)	145
C2—H2···O1ⁱⁱ	0.95	2.35	3.255 (11)	158
C7—H7A···O2ⁱⁱⁱ	0.98	2.42	3.323 (8)	152
C7—H7B···Cl1	0.98	2.77	3.355 (7)	119

Symmetry codes: (ii) x, y, z−1; (iii) −x, y−1/2, −z+2.

Experimental details

Crystal data
Chemical formula	[Pt(C₆H₄NO₂)Cl(C₂H₆OS)]
M_r	430.77
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	200
a, b, c (Å)	19.5900 (15), 6.9450 (6), 8.1266 (6)
V (Å³)	1105.64 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	13.11
Crystal size (mm)	0.21 × 0.17 × 0.09

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.631, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6423, 1169, 1085
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.065, 1.10
No. of reflections	1169
No. of parameters	89
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.60, −0.79

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Pt1—O1	2.020 (5)	Pt1—S1	2.202 (2)
Pt1—N1	2.031 (7)	Pt1—Cl1	2.2945 (19)

O1—Pt1—N1	81.0 (2)	O1—Pt1—Cl1	88.98 (16)
O1—Pt1—S1	177.70 (16)	N1—Pt1—Cl1	169.97 (19)
N1—Pt1—S1	101.31 (19)	S1—Pt1—Cl1	88.72 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3	0.95	2.16	2.995 (11)	145.3
C2—H2···O1ⁱ	0.95	2.35	3.255 (11)	158.0
C7—H7A···O2ⁱⁱ	0.98	2.42	3.323 (8)	152.2
C7—H7B···Cl1	0.98	2.77	3.355 (7)	119.2

Symmetry codes: (i) x, y, z−1; (ii) −x, y−1/2, −z+2.

Acknowledgements

This work was supported by Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2009–0094056).

References

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