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

The structure of the trans-Pt(NH₃)₂(mnt)₂ complex has Pt—N and Pt—S distances that are are consistent with those in other platinum(IV) complexes. The nitrile nitro­gen atoms are positioned suitably to hydrogen bond with adjacent ammines.

Abstract

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.

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.

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 −  , −z +  ; (ii) x, −y +  , z +  .

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) ; (ii) ; (iii) .

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 ▸)
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[F 2 > 2σ(F 2)], wR(F 2), S	0.017, 0.038, 1.05
No. of reflections	1556
No. of parameters	89
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.62, −0.54

Computer programs: CrysAlis PRO (Rigaku OD, 2019 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Supplementary Material

CCDC reference: 2017151

Additional supporting information: crystallographic information; 3D view; checkCIF report

full crystallographic data

Crystal data

[Pt(C4N2S2)2(NH3)2]	F(000) = 476
Mr = 509.52	Dx = 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

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	Rint = 0.034
Detector resolution: 10.0000 pixels mm-1	θmax = 27.1°, θmin = 2.8°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	k = −9→9
Tmin = 0.509, Tmax = 1.000	l = −18→19
8027 measured reflections

Refinement

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(Fo2) + (0.0154P)2 + 0.3678P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1556 reflections	Δρmax = 0.62 e Å−3
89 parameters	Δρmin = −0.54 e Å−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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···N1iv	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 Statement

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).