trans-(Aniline-κN)di­chlorido­(dimethyl sulfoxide-κS)platinum(II)

Wang, W.; Yuan, C.

doi:10.1107/S2414314618003875

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 3| March 2018| x180387

https://doi.org/10.1107/S2414314618003875

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trans-(Aniline-κN)dichlorido(dimethyl sulfoxide-κS)platinum(II)

Weirong Wang ^a and Caixia Yuan ^a ^*

^aInstitute of Molecular Science, Shanxi University, Taiyuan, Shanxi, 030006, People's Republic of China
^*Correspondence e-mail: cxyuan@sxu.edu.cn

Edited by J. Simpson, University of Otago, New Zealand (Received 1 March 2018; accepted 6 March 2018; online 13 March 2018)

In the title compound, [PtCl₂(C₆H₇N)(C₂H₆OS)], the Pt^II ion has an approximately square-planar coordination environment. It binds to the N atom of the aniline ligand and is trans to the S atom of the dimethyl sulfoxide. The two Cl⁻ anions are also in trans positions. In the crystal, molecules are linked by N—H⋯O, C—H⋯Cl and C—H⋯O hydrogen bonds.

Keywords: crystal structure; platinum(II) complex; hydrogen bonding.

CCDC reference: 1827840

Structure description

trans-Platinum(II) complexes attract great attention because such compounds display good cytotoxic activity and have been shown to be able to overcome cisplatin resistance (Sgarbossa et al., 2013 ; Kalinowska-Lis et al., 2008 ). It is therefore of interest to synthesize trans platinum(II) complexes with different structures.

In the title compound (Fig. 1), the platinum atom is in a slightly distorted square-planar coordination environment, which is defined by the N atom of the aniline ligand, the S atom of dimethyl sulfoxide and the two Cl⁻ anions that adopt a trans arrangement. A slight distortion from planarity is indicated with a dihedral angle of 4.39 (11)° between the Cl2–Pt1–S1 and Cl1–Pt1–N1 planes. The Pt1—N1, 2.081 (3) Å, Pt1—S1, 2.2206 (10) Å, and the two Pt—Cl bond distances Pt1—Cl1 2.2894 (11) Å, and 2.2933 (11) Å are normal and comparable to values reported for related Pt^II complexes in the literature (Francisco et al., 2011 ; Rahman et al. 2015 ; Huo et al. 2011 ).

Figure 1
A view of the title compound with 30% probability displacement ellipsoids.

In the crystal, N1—H1B⋯O1 hydrogen bonds, Table 1, form inversion dimers and enclose R₂²(10) rings, Fig. 2. The molecules are further linked by N—H⋯Cl, C—H⋯Cl and C—H⋯O hydrogen bonds, generating a three-dimensional framework (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2ⁱ	0.89	2.78	3.463 (3)	134
N1—H1A⋯Cl2ⁱⁱ	0.89	2.84	3.425 (3)	125
N1—H1B⋯O1ⁱ	0.89	2.05	2.913 (4)	165
C8—H8A⋯O1ⁱⁱⁱ	0.96	2.51	3.424 (6)	158
C8—H8C⋯Cl1^iv	0.96	2.77	3.677 (6)	158
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y, -z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Figure 2
The N—H⋯O hydrogen-bonding interactions between the amine H-atom donors and dimethyl sulfoxide O-atom acceptors in the title compound.

Figure 3
Overall packing of the title compound viewed along the b-axis direction.

Synthesis and crystallization

The complex cis-Pt(DMSO)₂Cl₂ (DMSO = dimethyl sulfoxide) was prepared by a reported method (Kukushkin et al., 1968 ). A solution of aniline (0.1 mmol, 0.009 g) in methanol (10 ml) was added with stirring to a suspension of cis-Pt(DMSO)₂Cl₂ (0.1 mmol, 0.042 g) in methanol (10 ml). The solution was refluxed at 338 K with stirring for 2.5 h under a nitrogen atmosphere, cooled slowly and filtered. The filtrate was kept at room temperature and suitable crystals of the title compound were obtained over a period of two weeks.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[PtCl₂(C₆H₇N)(C₂H₆OS)]
M_r	437.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	15.1308 (7), 16.6636 (8), 10.0062 (5)
β (°)	100.379 (1)
V (Å³)	2481.6 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	11.88
Crystal size (mm)	0.30 × 0.25 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.040, 0.051
No. of measured, independent and observed [I > 2σ(I)] reflections	13004, 2181, 1967
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.043, 1.09
No. of reflections	2181
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.84
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1827840

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618003875/sj4166sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618003875/sj4166Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

trans-(Aniline-κN)dichlorido(dimethyl sulfoxide-κS)platinum(II) top

Crystal data top

[PtCl₂(C₆H₇N)(C₂H₆OS)]	F(000) = 1632
M_r = 437.24	D_x = 2.341 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.1308 (7) Å	Cell parameters from 5286 reflections
b = 16.6636 (8) Å	θ = 2.4–27.3°
c = 10.0062 (5) Å	µ = 11.88 mm⁻¹
β = 100.379 (1)°	T = 296 K
V = 2481.6 (2) Å³	Block, colorless
Z = 8	0.30 × 0.25 × 0.25 mm

Data collection top

Bruker APEXII CCD diffractometer	1967 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2012)	θ_max = 25.0°, θ_min = 1.8°
T_min = 0.040, T_max = 0.051	h = −17→17
13004 measured reflections	k = −19→19
2181 independent reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.043	w = 1/[σ²(F_o²) + (0.020P)² + 0.8P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2181 reflections	Δρ_max = 0.41 e Å⁻³
129 parameters	Δρ_min = −0.84 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pt1	0.39217 (2)	0.34146 (2)	0.14748 (2)	0.02771 (7)
Cl1	0.36154 (9)	0.21751 (7)	0.22668 (12)	0.0532 (3)
Cl2	0.41711 (8)	0.47049 (7)	0.08370 (11)	0.0452 (3)
S1	0.42812 (7)	0.29389 (7)	−0.04301 (10)	0.0355 (3)
O1	0.52497 (18)	0.2944 (2)	−0.0457 (3)	0.0470 (8)
N1	0.3694 (2)	0.3897 (2)	0.3300 (3)	0.0318 (8)
H1A	0.400822	0.434933	0.344778	0.038*
H1B	0.391932	0.355693	0.396038	0.038*
C1	0.2775 (2)	0.4074 (2)	0.3444 (4)	0.0283 (9)
C2	0.2311 (3)	0.4691 (3)	0.2705 (4)	0.0404 (10)
H2	0.257308	0.497612	0.207829	0.048*
C3	0.1460 (3)	0.4882 (3)	0.2904 (5)	0.0501 (12)
H3	0.114762	0.530426	0.242771	0.060*
C4	0.1068 (3)	0.4437 (3)	0.3822 (5)	0.0543 (14)
H4	0.049190	0.456414	0.395805	0.065*
C5	0.1521 (3)	0.3820 (3)	0.4519 (5)	0.0508 (13)
H5	0.125046	0.351931	0.511744	0.061*
C6	0.2378 (3)	0.3637 (3)	0.4343 (4)	0.0421 (11)
H6	0.269067	0.321907	0.483229	0.050*
C7	0.3881 (4)	0.1953 (3)	−0.0826 (5)	0.0609 (15)
H7A	0.417547	0.158835	−0.014625	0.091*
H7B	0.400683	0.180089	−0.169763	0.091*
H7C	0.324459	0.193677	−0.084796	0.091*
C8	0.3738 (4)	0.3477 (3)	−0.1877 (5)	0.0612 (16)
H8A	0.387880	0.323519	−0.268400	0.092*
H8B	0.394203	0.402408	−0.181841	0.092*
H8C	0.310016	0.346455	−0.191259	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.02819 (10)	0.02928 (11)	0.02603 (10)	−0.00066 (7)	0.00590 (6)	0.00100 (7)
Cl1	0.0786 (9)	0.0331 (6)	0.0493 (7)	−0.0117 (6)	0.0152 (6)	0.0038 (5)
Cl2	0.0558 (7)	0.0359 (6)	0.0468 (6)	−0.0025 (5)	0.0168 (5)	0.0111 (5)
S1	0.0331 (6)	0.0451 (7)	0.0280 (5)	0.0024 (5)	0.0048 (4)	−0.0054 (5)
O1	0.0327 (16)	0.071 (2)	0.0384 (17)	0.0042 (16)	0.0093 (13)	−0.0105 (16)
N1	0.0323 (18)	0.036 (2)	0.0274 (17)	−0.0041 (16)	0.0058 (14)	−0.0025 (16)
C1	0.031 (2)	0.027 (2)	0.028 (2)	−0.0034 (17)	0.0082 (17)	−0.0044 (17)
C2	0.042 (3)	0.030 (2)	0.051 (3)	−0.006 (2)	0.012 (2)	0.003 (2)
C3	0.042 (3)	0.041 (3)	0.068 (3)	0.010 (2)	0.010 (2)	0.001 (3)
C4	0.042 (3)	0.058 (4)	0.067 (3)	−0.001 (3)	0.020 (3)	−0.010 (3)
C5	0.043 (3)	0.070 (4)	0.043 (3)	−0.014 (3)	0.018 (2)	0.004 (3)
C6	0.046 (3)	0.043 (3)	0.038 (3)	−0.002 (2)	0.009 (2)	0.006 (2)
C7	0.074 (4)	0.052 (3)	0.058 (3)	−0.008 (3)	0.016 (3)	−0.025 (3)
C8	0.059 (3)	0.093 (5)	0.030 (3)	0.020 (3)	0.005 (2)	0.008 (3)

Geometric parameters (Å, º) top

Pt1—N1	2.081 (3)	C3—C4	1.393 (7)
Pt1—S1	2.2206 (10)	C3—H3	0.9300
Pt1—Cl1	2.2894 (11)	C4—C5	1.358 (7)
Pt1—Cl2	2.2933 (11)	C4—H4	0.9300
S1—O1	1.470 (3)	C5—C6	1.374 (6)
S1—C7	1.770 (5)	C5—H5	0.9300
S1—C8	1.775 (5)	C6—H6	0.9300
N1—C1	1.453 (5)	C7—H7A	0.9600
N1—H1A	0.8899	C7—H7B	0.9600
N1—H1B	0.8900	C7—H7C	0.9600
C1—C6	1.377 (6)	C8—H8A	0.9600
C1—C2	1.382 (6)	C8—H8B	0.9600
C2—C3	1.376 (6)	C8—H8C	0.9600
C2—H2	0.9300

N1—Pt1—S1	175.23 (9)	C2—C3—C4	119.6 (5)
N1—Pt1—Cl1	88.19 (10)	C2—C3—H3	120.2
S1—Pt1—Cl1	94.09 (4)	C4—C3—H3	120.2
N1—Pt1—Cl2	86.79 (10)	C5—C4—C3	120.4 (4)
S1—Pt1—Cl2	91.01 (4)	C5—C4—H4	119.8
Cl1—Pt1—Cl2	174.81 (4)	C3—C4—H4	119.8
O1—S1—C7	107.7 (2)	C4—C5—C6	120.2 (5)
O1—S1—C8	107.4 (2)	C4—C5—H5	119.9
C7—S1—C8	101.4 (3)	C6—C5—H5	119.9
O1—S1—Pt1	114.36 (12)	C5—C6—C1	120.0 (4)
C7—S1—Pt1	113.35 (18)	C5—C6—H6	120.0
C8—S1—Pt1	111.77 (18)	C1—C6—H6	120.0
C1—N1—Pt1	118.6 (2)	S1—C7—H7A	109.5
C1—N1—H1A	107.7	S1—C7—H7B	109.5
Pt1—N1—H1A	107.7	H7A—C7—H7B	109.5
C1—N1—H1B	107.6	S1—C7—H7C	109.5
Pt1—N1—H1B	107.7	H7A—C7—H7C	109.5
H1A—N1—H1B	107.1	H7B—C7—H7C	109.5
C6—C1—C2	120.3 (4)	S1—C8—H8A	109.5
C6—C1—N1	119.6 (4)	S1—C8—H8B	109.5
C2—C1—N1	120.1 (4)	H8A—C8—H8B	109.5
C3—C2—C1	119.5 (4)	S1—C8—H8C	109.5
C3—C2—H2	120.2	H8A—C8—H8C	109.5
C1—C2—H2	120.2	H8B—C8—H8C	109.5

Pt1—N1—C1—C6	112.7 (4)	C2—C3—C4—C5	0.0 (8)
Pt1—N1—C1—C2	−68.9 (4)	C3—C4—C5—C6	1.2 (8)
C6—C1—C2—C3	1.8 (6)	C4—C5—C6—C1	−0.9 (7)
N1—C1—C2—C3	−176.5 (4)	C2—C1—C6—C5	−0.6 (7)
C1—C2—C3—C4	−1.5 (7)	N1—C1—C6—C5	177.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2ⁱ	0.89	2.78	3.463 (3)	134
N1—H1A···Cl2ⁱⁱ	0.89	2.84	3.425 (3)	125
N1—H1B···O1ⁱ	0.89	2.05	2.913 (4)	165
C8—H8A···O1ⁱⁱⁱ	0.96	2.51	3.424 (6)	158
C8—H8C···Cl1^iv	0.96	2.77	3.677 (6)	158

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

Acknowledgements

The authors acknowledge Shao-dong Li for help with the single-crystal X-ray diffraction data collection.

Funding information

Funding for this research was provided by: National Natural Science Foundation of China (grant No. 21471092).

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