{μ-N,N′-Bis[(E)-4-pyridylmethyl­idene]naphthalene-1,5-diamine}bis­[dichlorido(dimethyl sulfide)platinum(II)]

Abstract

The title dinuclear platinum compound, [Pt₂Cl₄(C₂₂H₁₆N₄)(C₂H₆S)₂], with a long bridging bipyridyl-type ligand, is centrosymmetric and the Pt^II cation shows a slightly distorted square-planar coordination geometry. The Cl ligands are trans to each other, with a Cl—Pt—Cl angle of 178.83 (8)°. The pyridine ring forms a dihedral angle of 48.8 (2)° with the planar PtCl₂SN unit. Within the mol­ecule, the distance between Pt atoms is 20.262 (5) Å and the N⋯N separation between the terminal pyridyl rings is 16.23 (1)Å.

Related literature

For related literature, see: Barnett & Champness (2003 ▶); Costa et al. (2003 ▶); Han & Lee (2004 ▶); Hill et al. (1998 ▶); Huh et al. (2008 ▶) and references therein; Kinnunen et al. (2002 ▶); Leininger et al. (2000 ▶); Min et al. (2006 ▶); Kinnunen et al. (2002 ▶); Leininger et al. (2000 ▶); Min et al. (2006 ▶).

Experimental

Crystal data

• [Pt₂Cl₄(C₂₂H₁₆N₄)(C₂H₆S)₂]

• M _r = 992.62

• Triclinic,

• a = 5.172 (2) Å

• b = 7.2482 (11) Å

• c = 20.728 (3) Å

• α = 91.596 (12)°

• β = 91.974 (19)°

• γ = 97.804 (17)°

• V = 769.0 (3) ų

• Z = 1

• Mo Kα radiation

• μ = 9.59 mm⁻¹

• T = 293 (2) K

• 0.44 × 0.20 × 0.10 mm

Data collection

• Siemens P4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.115, T _max = 0.383

• 3026 measured reflections

• 2696 independent reflections

• 2447 reflections with I > 2σ(I)

• R _int = 0.042

• 3 standard reflections every 97 reflections intensity decay: none

Refinement

• R[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 0.093

• S = 1.05

• 2696 reflections

• 172 parameters

• H-atom parameters constrained

• Δρ_max = 0.73 e Å⁻³

• Δρ_min = −0.96 e Å⁻³

Data collection: XSCANS (Siemens, 1995 ▶); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Pt1—N1	2.057 (6)
Pt1—S1	2.285 (2)
Pt1—Cl2	2.301 (2)
Pt1—Cl1	2.303 (2)

N1—Pt1—S1	175.98 (18)
N1—Pt1—Cl2	88.55 (19)
S1—Pt1—Cl2	95.31 (8)
N1—Pt1—Cl1	90.40 (19)
S1—Pt1—Cl1	85.74 (8)
Cl2—Pt1—Cl1	178.83 (8)

supplementary crystallographic information

Comment

The N-donor linking (exo N-donor bidentate) ligands such as pyrazine, 4,4'-bipyridine, 1,2-bis(4-pyridyl)ethylene, and 1,2-bis(4-pyridyl)ethane are widely used for the synthesis of discrete dinuclear, polynuclear, and coordination network compounds (Leininger et al., 2000; Kinnunen et al., 2002; Costa et al., 2003; Barnett & Champness, 2003). We also reported dinuclear discrete rods, tetranuclear rectangles, and one-dimensional coordination networks of Cp*Rh(III) compounds by employing such ligands, where Cp* is 1,2,3,4,5-pentamethylcyclopentadiene (Han & Lee, 2004). Recently, we reported several novel long bipyridyl-type linking ligands including ligand L and their coordination polymers of several transition metals (Min et al., 2006; Huh et al., 2008). As a continuation of our research, we decided to use ligand L to prepare novel platinum polynuclear or coordination network compounds. The layer diffusion (dichloromethane–benzene) of [Pt(SMe₂)₂Cl₂] with an equimolar amount L with dichloromethane and benzene as solvents gave an unexpected dinuclear [Pt₂L(SMe₂)₂Cl₄] compound. Moreover, the reaction involving 2 equiv of L also gave the same product. The molecular structure of the title compound is shown Fig. 1. The complex molecule is centrosymmetric with the Pt^II ion exhibiting a slightly distorted square-planar coordination geometry. Each Pt atom is coordinated by two trans chloro ligands, one sulfur atom of SMe₂, and pyridine N atom of ligand L. The PtCl₂SN core is essentially planar with the highest displacement of 0.012 (2) Å for the Pt atom. Within the molecule, the distance between Pt atoms is 20.262 (5) Å, and the N···N separation between the terminal pyridyl rings of 16.23 (1) Å is somewhat longer than that of the free ligand (16.0 Å; Min et al., 2006).

Experimental

A dichloromethane solution (7 ml) of L (40 mg, 0.136 mmol) was layered onto the top of a benzene solution (7 ml) of Pt(SMe₂)₂Cl₂ (50 mg, 0.130 mmol) (Hill et al., 1998). Yellow crystals of [Pt₂L(SMe₂)₂Cl₄] formed in 5 days (53 mg, 0.053 mmol, 39%). The title compound is insoluble in common organic solvents. Anal. Calcd for C₂₆H₂₈N₄S₂Cl₂Pt₂ (Mr = 992.62): C 31.46; H 2.84; N, 5.65; S 6.46. Found: C 31.32; H 2.87; N 6.03; S 6.65. IR (KBr, ν, cm^-1): 1620 (s), 1590 (s), 1402 (s), 1378 (m), 1308 (s), 1197 (m), 1036 (m), 983 (m), 811 (m), 659 (m).

Refinement

All H atoms were positioned geometrically, with C—H = 0.93-96 Å and constrained to ride on their parent atoms with U_iso(H)=1.2U_eq(C).

Figures

Fig. 1.

Molecular structure of the title compound showing 50% probability displacement ellipsoids. H atoms are omitted for clarity. Unlabeled atoms are related to labeled atoms by the symmetry operation i = -x + 1, -y + 1, -z + 1.

Crystal data

[Pt2Cl4(C22H16N4)(C2H6S1)2]	Z = 1
Mr = 992.62	F000 = 468
Triclinic, P1	Dx = 2.143 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 5.172 (2) Å	Cell parameters from 21 reflections
b = 7.2482 (11) Å	θ = 4.7–12.5º
c = 20.728 (3) Å	µ = 9.59 mm−1
α = 91.596 (12)º	T = 293 (2) K
β = 91.974 (19)º	Block, yellow
γ = 97.804 (17)º	0.44 × 0.20 × 0.10 mm
V = 769.0 (3) Å3

Data collection

Siemens P4 diffractometer	Rint = 0.042
Radiation source: sealed tube	θmax = 25.1º
Monochromator: graphite	θmin = 2.0º
T = 293(2) K	h = −6→0
ω scans	k = −8→8
Absorption correction: ψ scan(North et al., 1968)	l = −24→24
Tmin = 0.115, Tmax = 0.383	3 standard reflections
3026 measured reflections	every 97 reflections
2696 independent reflections	intensity decay: none
2447 reflections with I > 2σ(I)

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.0492P)2 + 1.8521P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
2696 reflections	Δρmax = 0.73 e Å−3
172 parameters	Δρmin = −0.96 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Pt1	−0.76885 (6)	0.00003 (4)	0.835419 (14)	0.05066 (13)
Cl2	−0.8555 (5)	−0.2416 (3)	0.76008 (12)	0.0684 (5)
Cl1	−0.6804 (6)	0.2461 (3)	0.90917 (11)	0.0783 (7)
S1	−1.0252 (5)	−0.1418 (3)	0.91231 (11)	0.0646 (5)
N1	−0.5382 (12)	0.1450 (8)	0.7698 (3)	0.0477 (13)
N2	0.1135 (13)	0.4034 (9)	0.6076 (3)	0.0539 (15)
C1	−0.3549 (16)	0.0685 (10)	0.7380 (4)	0.0536 (18)
H1	−0.3308	−0.0536	0.7461	0.064*
C2	−0.2008 (16)	0.1659 (11)	0.6934 (4)	0.0545 (18)
H2	−0.0744	0.1100	0.6723	0.065*
C3	−0.2373 (16)	0.3491 (11)	0.6804 (3)	0.0515 (17)
C4	−0.4212 (15)	0.4285 (10)	0.7142 (4)	0.0509 (17)
H4	−0.4454	0.5514	0.7075	0.061*
C5	−0.5705 (15)	0.3241 (11)	0.7584 (4)	0.0505 (16)
H5	−0.6954	0.3784	0.7807	0.061*
C6	−0.0727 (15)	0.4623 (11)	0.6348 (3)	0.0508 (17)
H6	−0.1095	0.5813	0.6260	0.061*
C7	0.2847 (15)	0.5245 (11)	0.5700 (4)	0.0515 (17)
C8	0.3580 (18)	0.7091 (12)	0.5875 (4)	0.060 (2)
H8	0.2830	0.7612	0.6226	0.072*
C9	0.5474 (18)	0.8204 (12)	0.5523 (4)	0.063 (2)
H9	0.5932	0.9456	0.5641	0.076*
C10	0.3377 (16)	0.2520 (11)	0.4981 (4)	0.0577 (19)
H10	0.2125	0.1766	0.5201	0.069*
C11	0.4057 (15)	0.4428 (11)	0.5180 (3)	0.0491 (16)
C12	−1.208 (3)	−0.3570 (17)	0.8815 (7)	0.104 (4)
H12A	−1.3382	−0.3308	0.8502	0.156*
H12B	−1.2914	−0.4229	0.9164	0.156*
H12C	−1.0920	−0.4321	0.8615	0.156*
C13	−0.803 (2)	−0.2317 (17)	0.9678 (5)	0.089 (3)
H13A	−0.6900	−0.1301	0.9888	0.134*
H13B	−0.7003	−0.3103	0.9447	0.134*
H13C	−0.9001	−0.3027	0.9996	0.134*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Pt1	0.0554 (2)	0.04379 (18)	0.05348 (19)	0.00442 (12)	0.01683 (13)	0.00739 (12)
Cl2	0.0754 (14)	0.0514 (10)	0.0776 (13)	0.0024 (9)	0.0253 (11)	−0.0063 (9)
Cl1	0.1031 (18)	0.0645 (13)	0.0607 (12)	−0.0161 (12)	0.0249 (12)	−0.0036 (10)
S1	0.0712 (14)	0.0539 (11)	0.0696 (13)	0.0034 (10)	0.0301 (11)	0.0115 (9)
N1	0.043 (3)	0.048 (3)	0.052 (3)	0.003 (3)	0.008 (3)	0.006 (3)
N2	0.051 (4)	0.065 (4)	0.047 (3)	0.006 (3)	0.013 (3)	0.012 (3)
C1	0.056 (4)	0.043 (4)	0.063 (4)	0.004 (3)	0.020 (4)	0.012 (3)
C2	0.052 (4)	0.058 (4)	0.057 (4)	0.016 (3)	0.017 (3)	0.003 (3)
C3	0.058 (5)	0.057 (4)	0.039 (3)	0.006 (3)	0.012 (3)	0.009 (3)
C4	0.052 (4)	0.049 (4)	0.055 (4)	0.011 (3)	0.015 (3)	0.016 (3)
C5	0.047 (4)	0.058 (4)	0.048 (4)	0.006 (3)	0.014 (3)	0.005 (3)
C6	0.048 (4)	0.060 (4)	0.047 (4)	0.011 (3)	0.009 (3)	0.013 (3)
C7	0.052 (4)	0.059 (4)	0.047 (4)	0.012 (3)	0.016 (3)	0.017 (3)
C8	0.068 (5)	0.061 (5)	0.054 (4)	0.013 (4)	0.022 (4)	0.013 (4)
C9	0.071 (6)	0.056 (5)	0.062 (5)	0.005 (4)	0.018 (4)	0.014 (4)
C10	0.058 (5)	0.055 (4)	0.060 (4)	0.004 (4)	0.017 (4)	0.012 (4)
C11	0.051 (4)	0.055 (4)	0.043 (4)	0.010 (3)	0.011 (3)	0.016 (3)
C12	0.107 (9)	0.083 (7)	0.112 (9)	−0.034 (7)	0.030 (8)	0.018 (7)
C13	0.104 (9)	0.101 (8)	0.066 (6)	0.016 (7)	0.022 (6)	0.026 (5)

Geometric parameters (Å, °)

Pt1—N1	2.057 (6)	C5—H5	0.9300
Pt1—S1	2.285 (2)	C6—H6	0.9300
Pt1—Cl2	2.301 (2)	C7—C8	1.376 (12)
Pt1—Cl1	2.303 (2)	C7—C11	1.420 (11)
S1—C13	1.795 (12)	C8—C9	1.418 (12)
S1—C12	1.799 (12)	C8—H8	0.9300
N1—C1	1.344 (10)	C9—C10i	1.347 (12)
N1—C5	1.357 (10)	C9—H9	0.9300
N2—C6	1.250 (10)	C10—C9i	1.347 (12)
N2—C7	1.427 (9)	C10—C11	1.426 (11)
C1—C2	1.386 (11)	C10—H10	0.9300
C1—H1	0.9300	C11—C11i	1.435 (14)
C2—C3	1.398 (11)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.378 (11)	C12—H12C	0.9600
C3—C6	1.484 (10)	C13—H13A	0.9600
C4—C5	1.392 (10)	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
N1—Pt1—S1	175.98 (18)	N2—C6—H6	118.8
N1—Pt1—Cl2	88.55 (19)	C3—C6—H6	118.8
S1—Pt1—Cl2	95.31 (8)	C8—C7—C11	120.0 (7)
N1—Pt1—Cl1	90.40 (19)	C8—C7—N2	122.0 (7)
S1—Pt1—Cl1	85.74 (8)	C11—C7—N2	117.5 (7)
Cl2—Pt1—Cl1	178.83 (8)	C7—C8—C9	120.2 (8)
C13—S1—C12	99.7 (7)	C7—C8—H8	119.9
C13—S1—Pt1	105.2 (4)	C9—C8—H8	119.9
C12—S1—Pt1	111.4 (4)	C10i—C9—C8	121.2 (8)
C1—N1—C5	118.8 (6)	C10i—C9—H9	119.4
C1—N1—Pt1	122.1 (5)	C8—C9—H9	119.4
C5—N1—Pt1	119.1 (5)	C9i—C10—C11	120.8 (7)
C6—N2—C7	120.3 (7)	C9i—C10—H10	119.6
N1—C1—C2	122.1 (7)	C11—C10—H10	119.6
N1—C1—H1	119.0	C7—C11—C10	122.2 (7)
C2—C1—H1	119.0	C7—C11—C11i	119.2 (9)
C1—C2—C3	119.4 (7)	C10—C11—C11i	118.5 (9)
C1—C2—H2	120.3	S1—C12—H12A	109.5
C3—C2—H2	120.3	S1—C12—H12B	109.5
C4—C3—C2	118.4 (7)	H12A—C12—H12B	109.5
C4—C3—C6	119.7 (7)	S1—C12—H12C	109.5
C2—C3—C6	121.8 (7)	H12A—C12—H12C	109.5
C3—C4—C5	119.8 (7)	H12B—C12—H12C	109.5
C3—C4—H4	120.1	S1—C13—H13A	109.5
C5—C4—H4	120.1	S1—C13—H13B	109.5
N1—C5—C4	121.6 (7)	H13A—C13—H13B	109.5
N1—C5—H5	119.2	S1—C13—H13C	109.5
C4—C5—H5	119.2	H13A—C13—H13C	109.5
N2—C6—C3	122.4 (7)	H13B—C13—H13C	109.5

Symmetry codes: (i) −x+1, −y+1, −z+1.