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

Huh, H.S.; Lee, S.W.

doi:10.1107/S1600536808024914

metal-organic compounds

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Volume 64| Part 9| September 2008| Page m1138

doi:10.1107/S1600536808024914

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

Hyun Sue Huh ^a and Soon W. Lee ^a ^*

^aDepartment of Chemistry (BK21), Sungkyunkwan University, Natural Science Campus, Suwon 440-746, Republic of Korea
^*Correspondence e-mail: soonwlee@skku.edu

(Received 4 July 2008; accepted 3 August 2008; online 9 August 2008)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.036
wR(F²) = 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

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)

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024914/gk2157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024914/gk2157Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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).

Computing details top

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

Figures top

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.

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

Crystal data top

[Pt₂Cl₄(C₂₂H₁₆N₄)(C₂H₆S)₂]	Z = 1
M_r = 992.62	F(000) = 468
Triclinic, P1	D_x = 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 = 4.7–12.5°
c = 20.728 (3) Å	µ = 9.59 mm⁻¹
α = 91.596 (12)°	T = 293 K
β = 91.974 (19)°	Block, yellow
γ = 97.804 (17)°	0.44 × 0.20 × 0.10 mm
V = 769.0 (3) Å³

Data collection top

Siemens P4 diffractometer	2447 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 25.1°, θ_min = 2.0°
ω scans	h = −6→0
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.115, T_max = 0.383	l = −24→24
3026 measured reflections	3 standard reflections every 97 reflections
2696 independent reflections	intensity decay: none

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0492P)² + 1.8521P] where P = (F_o² + 2F_c²)/3
2696 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.96 e Å⁻³

Crystal data top

[Pt₂Cl₄(C₂₂H₁₆N₄)(C₂H₆S)₂]	γ = 97.804 (17)°
M_r = 992.62	V = 769.0 (3) Å³
Triclinic, P1	Z = 1
a = 5.172 (2) Å	Mo Kα radiation
b = 7.2482 (11) Å	µ = 9.59 mm⁻¹
c = 20.728 (3) Å	T = 293 K
α = 91.596 (12)°	0.44 × 0.20 × 0.10 mm
β = 91.974 (19)°

Data collection top

Siemens P4 diffractometer	2447 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.042
T_min = 0.115, T_max = 0.383	3 standard reflections every 97 reflections
3026 measured reflections	intensity decay: none
2696 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.05	Δρ_max = 0.73 e Å⁻³
2696 reflections	Δρ_min = −0.96 e Å⁻³
172 parameters

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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Pt₂Cl₄(C₂₂H₁₆N₄)(C₂H₆S)₂]
M_r	992.62
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.172 (2), 7.2482 (11), 20.728 (3)
α, β, γ (°)	91.596 (12), 91.974 (19), 97.804 (17)
V (Å³)	769.0 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	9.59
Crystal size (mm)	0.44 × 0.20 × 0.10

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.115, 0.383
No. of measured, independent and observed [I > 2σ(I)] reflections	3026, 2696, 2447
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.093, 1.05
No. of reflections	2696
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.96

Computer programs: XSCANS (Siemens, 1995), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

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

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

References

Barnett, S. A. & Champness, N. R. (2003). Coord. Chem. Rev. 246, 145–168. Web of Science CrossRef CAS Google Scholar
Costa, P. M. F. J., Mora, M., Calhorda, M. J., Felix, V., Ferreira, P., Drew, M. G. B. & Wadepohl, H. (2003). J. Organomet. Chem. 687, 57–68. Web of Science CSD CrossRef CAS Google Scholar
Han, W. S. & Lee, S. W. (2004). Dalton Trans. pp. 1656–1663. Google Scholar
Hill, G. S., Irwin, M. J., Levy, C. J., Rendina, L. M. & Puddephatt, R. J. (1998). Inorg. Synth. 32, 149–153. CrossRef CAS Google Scholar
Huh, S. H., Yun, H. J. & Lee, S. W. (2008). Inorg. Chim. Acta, 361, 2101–2108 . Web of Science CSD CrossRef CAS Google Scholar
Kinnunen, T.-J. J., Haukka, M., Pesonen, E. & Pakkanen, T. A. (2002). J. Organomet. Chem. 655, 31–38. Web of Science CSD CrossRef CAS Google Scholar
Leininger, S., Olenyuk, B. & Stang, P. J. (2000). Chem. Rev. 100, 853–908. Web of Science CrossRef PubMed CAS Google Scholar
Min, D., Cho, B.-Y. & Lee, S. W. (2006). Inorg. Chim. Acta, 359, 577–584. CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1995). XSCANS User's Manual. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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