(2,2′-Bi­pyridine)(1,2-di­cyano­ethene-1,2-di­thiol­ato)platinum(II)

Nesterov, V.N.; Hu, J.; Reinheimer, E.W.; Smucker, B.W.

doi:10.1107/S2414314619001585

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 1| January 2019| x190158

https://doi.org/10.1107/S2414314619001585

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(2,2′-Bipyridine)(1,2-dicyanoethene-1,2-dithiolato)platinum(II)

Vladimir N. Nesterov,^a Jiandu Hu,^b Eric W. Reinheimer ^c and Bradley W. Smucker ^b ^*

^aUniversity of North Texas, 1155 Union Circle, Denton, TX 76203-5070, USA, ^bAustin College, 900 N Grand, Sherman, TX 75090, USA, and ^cRigaku Oxford Diffraction, 9009 New Trails Dr., The Woodlands, TX 77381, USA
^*Correspondence e-mail: bsmucker@austincollege.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 January 2019; accepted 28 January 2019; online 31 January 2019)

In the crystal structure of the title complex, [Pt(C₄N₂S₂)(C₁₀H₈N₂)], the complex molecules pack as head-to-tail/inversion dimers, which are stabilized by HOMO–LUMO interactions and a Pt⋯Pt distance of 3.6625 (8) Å. The dimers are linked by C—H⋯N hydrogen bonds, forming layers parallel to the (101) plane.

Keywords: crystal structure; platinum(II); diimine dithiolate; Pt⋯Pt interaction; hydrogen bonding.

CCDC reference: 1894191

Structure description

Since Eisenberg's initial report on luminescent platinum(II) diimine dithiolate complexes (Zuleta, et al. 1989 ), this class of compounds has been utilized in areas such as dye-sensitized solar cells (Islam et al., 2001 ; Geary et al., 2005 ), photosplitting of water (Zhang et al., 2007 , Zarkadoulas et al., 2012 ) and non-linear optics (Cummings et al., 1997 ). X-ray structures of platinum(II)dithiolate complexes with modified bipyridine ligands are common in papers such as those describing the photophysical properties (Lazarides et al., 2011 ), reaction kinetics (Stace et al., 2016 ), or charge-transfer properties (Smucker et al., 2003 ; Browning et al., 2014 ) of these compounds. The crystal structure of one of the initial complexes, Pt(2,2′-bpy)(mnt), which inspired many variations, has heretofore not been published. This paper remedies the absence in the literature.

The title compound crystallized in the centrosymmetric monoclinic space group P2₁/n and contains a single molecule of Pt(2,2′-bpy)(mnt) as the contents of its asymmetric unit (Fig. 1). The platinum(II) atom has a square-pyramidal coordination sphere and the Pt—N and Pt—S bond distances (Table 1) are typical for M(diimine)(dithiolate) molecules. Within the complex there are short C—H⋯S interactions present (Fig. 1 and Table 2).

Table 1
Selected Pt—N and Pt—S bond lengths (Å)

Bond	Bond length
Pt1—S1	2.2487 (16)
Pt1—S2	2.2425 (17)
Pt1—N1	2.035 (5)
Pt1—N2	2.048 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯S1	0.94	2.67	3.260 (8)	121
C10—H10⋯S2	0.94	2.65	3.245 (6)	121
C2—H2⋯N3ⁱ	0.94	2.58	3.346 (10)	139
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
A view of the molecular structure of the title compound, with atom labeling. Displacement ellipsoids are drawn at the 50% probability level. The short intramolecular C—H⋯S contacts are shown as dashed lines (Table 2

The structure contains head-to-tail (inversion) dimers of Pt(2,2′-bpy)(mnt), as shown in Fig. 2. Intradimer integrity is maintained via HOMO–LUMO interactions whereby the former (of mixed metal/dithiolate molecular orbital character) overlaps with the latter (of primarily chelating diimine ligand character) (Cummings & Eisenberg, 1996 ) at a distance (C2—C12ⁱ) of 3.408 (9) Å (see Fig. 2). Additional integrity within the dimer is also maintained via contacts between the divalent platinum atoms at a distance of 3.6625 (8) Å.

Figure 2
A view of the inversion dimer of the title compound with select Pt1⋯Pt1ⁱ and C2⋯C12ⁱ/C12⋯C2ⁱ distances in Å [symmetry code: (i) = −x + 1, −y + 1, −z + 1].

Neighboring dimers of Pt(2,2′-bpy)(mnt) are linked by C—H⋯N hydrogen bonds (Table 2), forming layers parallel to the (101) plane, as shown in Fig. 3. Given the displacement of the two molecules from the different dimers relative to one another (∼2.8 Å), interdimer structural integrity is not maintained by secondary Pt⋯Pt interactions. Rather, interactions between the π-electron density of the 2,2′-bipyridine ligand from one molecule and the empty d_z² orbital from a platinum atom of the second are more likely. Weak π–π interactions may also be providing additional stability as the centroid-to-centroid distance between neighboring pyridyl rings was measured at 4.247 (4) Å, a distance close to the upper limit typical of such interactions (4.2 Å; Browning et al., 2014).

Figure 3
A view along the a axis of the crystal packing of the title compound. Hydrogen bonds (Table 2

) and Pt⋯Pt interactions are shown as dashed lines.

Synthesis and crystallization

The title compound was synthesized according to published procedures (Zuleta et al., 1990 ). Orange needles of Pt(2,2′-bpy)(mnt) resulted from the ambient cooling of a narrow glass tube containing a warm saturated DMF solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[Pt(C₄N₂S₂)(C₁₀H₈N₂)]
M_r	491.45
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	220
a, b, c (Å)	10.087 (3), 7.349 (2), 19.442 (6)
β (°)	101.276 (6)
V (Å³)	1413.4 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	10.22
Crystal size (mm)	0.12 × 0.05 × 0.01

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.007, 0.029
No. of measured, independent and observed [I > 2σ(I)] reflections	18409, 3118, 2556
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 1.05
No. of reflections	3118
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.09, −1.19
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1894191

Crystal structure: contains datablocks I, GLOBAL. DOI: https://doi.org/10.1107/S2414314619001585/su4170sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619001585/su4170Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(2,2'-Bipyridine)(1,2-dicyanoethene-1,2-dithiolato)platinum(II) top

Crystal data top

[Pt(C₄N₂S₂)(C₁₀H₈N₂)]	F(000) = 920
M_r = 491.45	D_x = 2.310 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.087 (3) Å	Cell parameters from 8369 reflections
b = 7.349 (2) Å	θ = 2.5–27.1°
c = 19.442 (6) Å	µ = 10.22 mm⁻¹
β = 101.276 (6)°	T = 220 K
V = 1413.4 (8) Å³	Needle, orange
Z = 4	0.12 × 0.05 × 0.01 mm

Data collection top

Bruker APEXII CCD diffractometer	2556 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
φ and ω scans	θ_max = 27.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
T_min = 0.007, T_max = 0.029	k = −9→9
18409 measured reflections	l = −24→24
3118 independent reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0442P)²] where P = (F_o² + 2F_c²)/3
3118 reflections	(Δ/σ)_max = 0.002
190 parameters	Δρ_max = 2.09 e Å⁻³
0 restraints	Δρ_min = −1.19 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	0.43643 (2)	0.70734 (3)	0.53458 (2)	0.03903 (10)
S1	0.51148 (16)	0.6436 (2)	0.64868 (8)	0.0470 (3)
S2	0.22499 (16)	0.6416 (2)	0.54649 (8)	0.0469 (3)
N1	0.6216 (5)	0.7728 (7)	0.5150 (3)	0.0396 (10)
N2	0.3858 (5)	0.7650 (6)	0.4297 (3)	0.0392 (10)
C7	0.4693 (7)	0.8661 (10)	0.3301 (3)	0.0522 (15)
H7	0.542164	0.904905	0.310168	0.063*
C9	0.2366 (8)	0.7948 (10)	0.3194 (4)	0.0572 (17)
H9	0.149274	0.782025	0.292112	0.069*
C1	0.6228 (7)	0.8192 (7)	0.4475 (3)	0.0420 (13)
C4	0.8613 (7)	0.8111 (10)	0.5421 (4)	0.0558 (17)
H4	0.942142	0.808236	0.575644	0.067*
C5	0.7390 (7)	0.7732 (9)	0.5608 (4)	0.0492 (14)
H5	0.738405	0.746376	0.608044	0.059*
C2	0.7416 (7)	0.8605 (9)	0.4255 (4)	0.0522 (15)
H2	0.740318	0.893202	0.378586	0.063*
C10	0.2615 (7)	0.7526 (10)	0.3897 (3)	0.0499 (15)
H10	0.189427	0.714035	0.410351	0.060*
C6	0.4905 (7)	0.8193 (8)	0.4000 (3)	0.0421 (13)
C8	0.3413 (8)	0.8561 (11)	0.2894 (3)	0.0587 (17)
H8	0.325677	0.890471	0.241974	0.070*
C14	0.1239 (7)	0.5176 (11)	0.6564 (3)	0.0565 (17)
N3	0.4007 (7)	0.4658 (11)	0.8047 (3)	0.0749 (19)
N4	0.0271 (7)	0.4718 (11)	0.6732 (3)	0.0722 (18)
C11	0.3675 (7)	0.5754 (9)	0.6776 (3)	0.0501 (15)
C12	0.2442 (7)	0.5745 (9)	0.6334 (3)	0.0494 (15)
C13	0.3842 (7)	0.5158 (10)	0.7483 (3)	0.0550 (16)
C3	0.8621 (7)	0.8531 (10)	0.4734 (4)	0.0537 (15)
H3	0.944232	0.876651	0.459047	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.04558 (14)	0.04030 (14)	0.03045 (13)	−0.00093 (10)	0.00560 (9)	−0.00120 (9)
S1	0.0534 (8)	0.0553 (9)	0.0311 (7)	−0.0029 (7)	0.0052 (6)	0.0021 (6)
S2	0.0495 (8)	0.0539 (9)	0.0372 (7)	−0.0007 (7)	0.0080 (6)	0.0017 (7)
N1	0.045 (3)	0.038 (2)	0.034 (2)	−0.001 (2)	0.005 (2)	−0.0028 (19)
N2	0.045 (3)	0.036 (2)	0.035 (2)	−0.002 (2)	0.004 (2)	−0.0001 (19)
C7	0.067 (4)	0.049 (3)	0.041 (3)	−0.004 (3)	0.011 (3)	0.006 (3)
C9	0.057 (4)	0.068 (5)	0.042 (4)	−0.003 (3)	−0.002 (3)	0.007 (3)
C1	0.057 (3)	0.032 (3)	0.037 (3)	−0.001 (2)	0.009 (3)	−0.005 (2)
C4	0.047 (4)	0.063 (5)	0.054 (4)	−0.008 (3)	0.003 (3)	−0.003 (3)
C5	0.051 (3)	0.056 (4)	0.038 (3)	−0.001 (3)	0.001 (3)	−0.003 (3)
C2	0.061 (4)	0.046 (3)	0.053 (4)	−0.004 (3)	0.019 (3)	−0.010 (3)
C10	0.047 (3)	0.062 (4)	0.039 (3)	0.000 (3)	0.002 (3)	0.003 (3)
C6	0.052 (3)	0.037 (3)	0.037 (3)	−0.005 (2)	0.008 (2)	−0.001 (2)
C8	0.073 (4)	0.063 (4)	0.037 (3)	0.001 (4)	0.002 (3)	0.007 (3)
C14	0.063 (4)	0.065 (5)	0.042 (3)	−0.004 (3)	0.012 (3)	−0.007 (3)
N3	0.087 (5)	0.092 (5)	0.047 (3)	0.002 (4)	0.016 (3)	0.008 (3)
N4	0.070 (4)	0.090 (5)	0.062 (4)	−0.016 (4)	0.026 (3)	−0.003 (4)
C11	0.062 (4)	0.055 (4)	0.034 (3)	−0.004 (3)	0.012 (3)	−0.003 (3)
C12	0.059 (4)	0.048 (4)	0.041 (3)	−0.004 (3)	0.011 (3)	−0.005 (3)
C13	0.061 (4)	0.059 (4)	0.045 (4)	−0.002 (3)	0.012 (3)	0.000 (3)
C3	0.049 (3)	0.055 (4)	0.058 (4)	−0.010 (3)	0.013 (3)	−0.010 (3)

Geometric parameters (Å, º) top

Pt1—S1	2.2487 (16)	C1—C2	1.383 (9)
Pt1—S2	2.2425 (17)	C1—C6	1.467 (9)
Pt1—N1	2.035 (5)	C4—H4	0.9400
Pt1—N2	2.048 (5)	C4—C5	1.381 (10)
S1—C11	1.731 (7)	C4—C3	1.373 (10)
S2—C12	1.734 (6)	C5—H5	0.9400
N1—C1	1.359 (8)	C2—H2	0.9400
N1—C5	1.335 (8)	C2—C3	1.381 (10)
N2—C10	1.343 (8)	C10—H10	0.9400
N2—C6	1.358 (8)	C8—H8	0.9400
C7—H7	0.9400	C14—N4	1.139 (9)
C7—C6	1.378 (9)	C14—C12	1.436 (9)
C7—C8	1.378 (10)	N3—C13	1.137 (9)
C9—H9	0.9400	C11—C12	1.367 (9)
C9—C10	1.377 (9)	C11—C13	1.421 (9)
C9—C8	1.377 (10)	C3—H3	0.9400

S2—Pt1—S1	89.82 (6)	N1—C5—C4	123.1 (6)
N1—Pt1—S1	95.12 (15)	N1—C5—H5	118.5
N1—Pt1—S2	175.05 (14)	C4—C5—H5	118.5
N1—Pt1—N2	79.9 (2)	C1—C2—H2	120.5
N2—Pt1—S1	174.88 (14)	C3—C2—C1	119.0 (6)
N2—Pt1—S2	95.18 (15)	C3—C2—H2	120.5
C11—S1—Pt1	103.8 (2)	N2—C10—C9	121.8 (7)
C12—S2—Pt1	103.6 (2)	N2—C10—H10	119.1
C1—N1—Pt1	114.9 (4)	C9—C10—H10	119.1
C5—N1—Pt1	127.0 (4)	N2—C6—C7	120.6 (6)
C5—N1—C1	118.0 (6)	N2—C6—C1	114.9 (5)
C10—N2—Pt1	125.8 (4)	C7—C6—C1	124.5 (6)
C10—N2—C6	119.3 (5)	C7—C8—H8	120.5
C6—N2—Pt1	114.9 (4)	C9—C8—C7	119.0 (6)
C6—C7—H7	120.0	C9—C8—H8	120.5
C6—C7—C8	120.0 (6)	N4—C14—C12	178.4 (7)
C8—C7—H7	120.0	C12—C11—S1	121.0 (5)
C10—C9—H9	120.4	C12—C11—C13	121.9 (6)
C10—C9—C8	119.2 (7)	C13—C11—S1	117.1 (5)
C8—C9—H9	120.4	C14—C12—S2	116.5 (5)
N1—C1—C2	121.8 (6)	C11—C12—S2	121.7 (5)
N1—C1—C6	115.4 (5)	C11—C12—C14	121.7 (6)
C2—C1—C6	122.9 (6)	N3—C13—C11	178.1 (9)
C5—C4—H4	120.7	C4—C3—C2	119.6 (6)
C3—C4—H4	120.7	C4—C3—H3	120.2
C3—C4—C5	118.6 (7)	C2—C3—H3	120.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···S1	0.94	2.67	3.260 (8)	121
C10—H10···S2	0.94	2.65	3.245 (6)	121
C2—H2···N3ⁱ	0.94	2.58	3.346 (10)	139

Symmetry code: (i) x+1/2, −y+3/2, z−1/2.

Selected Pt—N and Pt—S bond lengths (Å) top

Bond	Bond length
Pt1—S1	2.2487 (16)
Pt1—S2	2.2425 (17)
Pt1—N1	2.035 (5)
Pt1—N2	2.048 (5)

Acknowledgements

X-ray data were collected at the University of North Texas using a Bruker APEXII CCD diffractometer.

Funding information

Funding for this research was provided by: Welch Foundation (grant No. AD-0007).

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