trans-Diamminebis(1,2-di­cyano­ethene-1,2-di­thiol­ato)platinum(IV)

Siddiqui, M.J.; Nesterov, V.V.; Steidle, M.T.; Smucker, B.W.

doi:10.1107/S2414314620009803

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 7| July 2020| x200980

https://doi.org/10.1107/S2414314620009803

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trans-Diamminebis(1,2-dicyanoethene-1,2-dithiolato)platinum(IV)

Mahaa J. Siddiqui,^a Volodymyr V. Nesterov,^b Matthew T. Steidle ^a and Bradley W. Smucker ^a ^*

^aAustin College, 900 N Grand, Sherman, TX 75090, USA, and ^bDepartment of Chemistry, University of North Texas, 1508 W. Mulberry, Denton, TX, 76201, USA
^*Correspondence e-mail: bsmucker@austincollege.edu

Edited by R. J. Butcher, Howard University, USA (Received 3 July 2020; accepted 17 July 2020; online 28 July 2020)

The title compound, [Pt(C₄N₂S₂)₂(NH₃)₂], represents an octahedral platinum(IV) complex with two trans-ammine and two mnt (mnt = 1,2-dicyanoethene-1,2-dithiolato) ligands. The Pt—N and Pt—S distances are consistent with those in other platinum(IV) complexes. As a result of a slight canting of the coordination of the mnt ligand to the platinum(IV) atom, the nitrile nitrogen atoms are positioned suitably to hydrogen-bond with adjacent ammines.

Keywords: crystal structure; platinum(IV); dithiolene.

CCDC reference: 2017151

Structure description

The neutral title complex contains two ammine and two mnt ligands forming an octahedral platinum(IV) complex. The C—S distances of 1.747 (3) and 1.744 (3) Å and the C=C distance of 1.358 (4) Å support the ene-1,2-dithiolate form of the mnt ligand (Güntner et al., 1989 ; Chandrasekaran et al., 2014 ). The two ammine ligands are trans with a Pt—N bond length of 2.055 (2) Å, which is consistent with the Pt—N distances in other platinum(IV) complexes of 2.056 (9) (Fanwick & Huckaby, 1982 ) and 2.053 (5) Å (Brawner et al., 1978 ). The Pt—S distances of 2.3434 (8) and 2.3461 (7) Å are longer than in square-planar platinum complexes with mnt such as the Pt^II—S distances of 2.290 and 2.282 Å in [Pt(mnt)₂]²⁻ (Günter et al., 1989) or the Pt^III—S distance of 2.262 Å in [Pt(mnt)₂]⁻ (Mochida et al., 2010 ). This longer Pt—S bond is comparable, however, with the Pt—S distance of 2.3619 Å found in a similar octahedral platinum(IV) complex with two dithiolene and two trans phosphine ligands (Chandrasekaran et al., 2014). The coordination of the mnt ligands is slightly canted from the platinum(IV) atom, which allows for hydrogen bonding between the nitrile nitrogen atoms and adjacent ammines (Fig. 1, Table 1). These interactions lead to the formation of a three-dimensional network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.89	2.16	3.016 (3)	160
N3—H3B⋯S2ⁱⁱ	0.89	2.73	3.610 (3)	171
N3—H3C⋯N1ⁱⁱⁱ	0.89	2.26	3.011 (3)	142
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
Displacement ellipsoid plot 50% probability of all non-H atoms showing N—H hydrogen bonding between nitrile nitrogen atoms and hydrogen atoms on adjacent ammines. Symmetry codes: (i) −x, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .

Synthesis and crystallization

A solution of 13.9 mg (7.46 × 10 ⁻⁵mol) of Na₂mnt dissolved in 10 mL of water was combined with a solution of 25 mg (7.48 × 10⁻⁵ mol) of tetraammineplatinum(II) chloride dissolved in 25 mL of water, and stirred for 2 h in air. The solvent was removed using a vacuum oven to give 26.5 mg of a brown product isolated [¹H NMR (d-DMSO) 4.23ppm]. Light-orange crystals of the title compound were grown by liquid diffusion of diethyl ether into a methanol solution of the synthesized product in a tall, narrow tube that was covered with parafilm. The platinum(II) dithiolene complex is presumed to oxidize to the ammine-stabilized octahedral platinum(IV) dithiolene compound via air, demonstrating a synthetic route toward stable neutral Pt^IV dithiolene complexes (Geiger et al., 2001 ).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	[Pt(C₄N₂S₂)₂(NH₃)₂]
M_r	509.52
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.1778 (3), 7.7700 (4), 14.8862 (7)
β (°)	95.935 (4)
V (Å³)	710.73 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	10.45
Crystal size (mm)	0.05 × 0.02 × 0.01

Data collection
Diffractometer	Rigaku XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.509, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8027, 1556, 1375
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.038, 1.05
No. of reflections	1556
No. of parameters	89
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.54
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2017151

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620009803/bv4032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620009803/bv4032Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

trans-Diamminebis(1,2-dicyanoethene-1,2-dithiolato)platinum(IV) top

Crystal data top

[Pt(C₄N₂S₂)₂(NH₃)₂]	F(000) = 476
M_r = 509.52	D_x = 2.381 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1778 (3) Å	Cell parameters from 5207 reflections
b = 7.7700 (4) Å	θ = 2.7–29.7°
c = 14.8862 (7) Å	µ = 10.45 mm⁻¹
β = 95.935 (4)°	T = 100 K
V = 710.73 (6) Å³	Plate, clear light orange
Z = 2	0.05 × 0.02 × 0.01 mm

Data collection top

Rigaku XtaLAB Synergy, Dualflex, HyPix diffractometer	1556 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	1375 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
Detector resolution: 10.0000 pixels mm^-1	θ_max = 27.1°, θ_min = 2.8°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	k = −9→9
T_min = 0.509, T_max = 1.000	l = −18→19
8027 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.017	H-atom parameters constrained
wR(F²) = 0.038	w = 1/[σ²(F_o²) + (0.0154P)² + 0.3678P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1556 reflections	Δρ_max = 0.62 e Å⁻³
89 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints

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	0.500000	0.500000	0.500000	0.00819 (6)
S1	0.62740 (13)	0.46855 (9)	0.35800 (5)	0.01208 (16)
S2	0.20123 (12)	0.65846 (10)	0.43437 (5)	0.01294 (16)
N1	0.4195 (5)	0.4964 (3)	0.1195 (2)	0.0179 (6)
N2	−0.0905 (4)	0.7217 (3)	0.20727 (17)	0.0182 (6)
N3	0.3182 (4)	0.2794 (3)	0.47944 (16)	0.0125 (5)
H3A	0.283811	0.263528	0.420476	0.015*
H3B	0.197076	0.289137	0.506596	0.015*
H3C	0.395109	0.189825	0.502333	0.015*
C1	0.4056 (5)	0.5506 (4)	0.2889 (2)	0.0110 (6)
C2	0.2301 (5)	0.6263 (4)	0.32026 (18)	0.0116 (6)
C3	0.4129 (5)	0.5226 (3)	0.1948 (2)	0.0120 (6)
C4	0.0516 (5)	0.6804 (4)	0.25742 (19)	0.0124 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.00671 (9)	0.01158 (10)	0.00598 (9)	0.00083 (6)	−0.00073 (6)	0.00050 (6)
S1	0.0099 (4)	0.0183 (4)	0.0079 (3)	0.0023 (3)	0.0005 (3)	0.0006 (3)
S2	0.0104 (3)	0.0193 (4)	0.0088 (3)	0.0045 (3)	−0.0006 (3)	0.0021 (3)
N1	0.0231 (16)	0.0163 (15)	0.0136 (14)	0.0000 (11)	−0.0009 (12)	0.0000 (10)
N2	0.0171 (14)	0.0228 (15)	0.0143 (13)	0.0030 (12)	−0.0008 (11)	0.0019 (11)
N3	0.0099 (13)	0.0157 (13)	0.0117 (12)	0.0002 (10)	−0.0008 (10)	0.0027 (10)
C1	0.0123 (15)	0.0119 (14)	0.0085 (14)	−0.0017 (12)	−0.0010 (12)	0.0009 (11)
C2	0.0136 (15)	0.0119 (15)	0.0086 (14)	−0.0020 (12)	−0.0028 (11)	0.0024 (11)
C3	0.0149 (16)	0.0076 (15)	0.0124 (16)	0.0001 (11)	−0.0035 (12)	0.0008 (11)
C4	0.0135 (15)	0.0111 (15)	0.0127 (14)	−0.0019 (12)	0.0014 (12)	−0.0002 (12)

Geometric parameters (Å, º) top

Pt1—S1ⁱ	2.3434 (8)	N1—C3	1.143 (4)
Pt1—S1	2.3434 (8)	N2—C4	1.138 (4)
Pt1—S2	2.3461 (7)	N3—H3A	0.8900
Pt1—S2ⁱ	2.3461 (7)	N3—H3B	0.8900
Pt1—N3ⁱ	2.055 (2)	N3—H3C	0.8900
Pt1—N3	2.055 (2)	C1—C2	1.358 (4)
S1—C1	1.747 (3)	C1—C3	1.423 (4)
S2—C2	1.744 (3)	C2—C4	1.433 (4)

S1ⁱ—Pt1—S1	180.0	C2—S2—Pt1	100.09 (10)
S1ⁱ—Pt1—S2	89.87 (3)	Pt1—N3—H3A	109.5
S1—Pt1—S2ⁱ	89.87 (3)	Pt1—N3—H3B	109.5
S1—Pt1—S2	90.13 (3)	Pt1—N3—H3C	109.5
S1ⁱ—Pt1—S2ⁱ	90.13 (3)	H3A—N3—H3B	109.5
S2ⁱ—Pt1—S2	180.0	H3A—N3—H3C	109.5
N3ⁱ—Pt1—S1ⁱ	90.46 (7)	H3B—N3—H3C	109.5
N3—Pt1—S1ⁱ	89.54 (7)	C2—C1—S1	124.1 (2)
N3—Pt1—S1	90.46 (7)	C2—C1—C3	120.8 (3)
N3ⁱ—Pt1—S1	89.54 (7)	C3—C1—S1	114.9 (2)
N3ⁱ—Pt1—S2	91.06 (7)	C1—C2—S2	124.2 (2)
N3—Pt1—S2ⁱ	91.06 (7)	C1—C2—C4	119.4 (3)
N3—Pt1—S2	88.94 (7)	C4—C2—S2	116.4 (2)
N3ⁱ—Pt1—S2ⁱ	88.94 (7)	N1—C3—C1	178.5 (3)
N3—Pt1—N3ⁱ	180.0	N2—C4—C2	179.3 (3)
C1—S1—Pt1	100.20 (11)

Pt1—S1—C1—C2	6.6 (3)	S1—C1—C2—S2	1.7 (4)
Pt1—S1—C1—C3	−169.3 (2)	S1—C1—C2—C4	−176.5 (2)
Pt1—S2—C2—C1	−8.8 (3)	C3—C1—C2—S2	177.4 (2)
Pt1—S2—C2—C4	169.4 (2)	C3—C1—C2—C4	−0.8 (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
N3—H3A···N2ⁱⁱ	0.89	2.16	3.016 (3)	160
N3—H3B···S2ⁱⁱⁱ	0.89	2.73	3.610 (3)	171
N3—H3C···N1^iv	0.89	2.26	3.011 (3)	142

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

Funding information

We are grateful of the Welch Foundation (AD-0007) for a department grant supporting undergraduate research and the NSF MRI for a Jeol ECZ-400 NMR at Austin College (CHE-1725651) and a Rigaku XtaLAB Synergy-S X-ray diffractometer at UNT (CHE-1726652).

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