cis-Dichloridobis(N,N,N′,N′-tetra­methyl­ethane-1,2-diamine)­platinum(II)

Asiri, A.M.; Arshad, M.N.; Ishaq, M.; Alamry, K.A.; Bokhari, T.H.

doi:10.1107/S1600536812048295

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1562

doi:10.1107/S1600536812048295

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cis-Dichloridobis(N,N,N′,N′-tetramethylethane-1,2-diamine)platinum(II)

Abdullah M. Asiri,^a,^b Muhammad Nadeem Arshad,^b ^* Muhammad Ishaq,^a Khalid A. Alamry ^a,^b and Tanveer Hussain Bokhari ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, ^bCenter of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and ^cDepartment of Chemistry, Government College University, Faisalabad 38000, Pakistan
^*Correspondence e-mail: mnachemist@hotmail.com, sthbukhari@yahoo.co.uk

(Received 23 November 2012; accepted 25 November 2012; online 30 November 2012)

In the title complex, [PtCl₂(C₆H₁₆N₂)], the Pt^II atom adopts a distorted cis-PtN₂Cl₂ square-planar coordination geometry. The five-membered chelate ring adopts a twisted conformation. In the crystal, weak C—H⋯Cl hydrogen bonds link the molecules into (001) sheets.

Related literature

For related structures, see: Abellán-López et al. (2012 ); Boyle et al. (2004 ).

Experimental

Crystal data

[PtCl₂(C₆H₁₆N₂)]
M_r = 382.20
Monoclinic, I a
a = 11.8893 (2) Å
b = 6.0207 (1) Å
c = 15.8036 (3) Å
β = 110.549 (2)°
V = 1059.27 (3) Å³
Z = 4
Cu Kα radiation
μ = 28.99 mm⁻¹
T = 296 K
0.22 × 0.21 × 0.07 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas, CCD) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.149, T_max = 1.000
6899 measured reflections
2091 independent reflections
2067 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.116
S = 1.03
2091 reflections
105 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 1.83 e Å⁻³
Δρ_min = −2.02 e Å⁻³
Absolute structure: Flack (1983 ), 1005 Friedel pairs
Flack parameter: −0.02 (2)

Table 1
Selected bond lengths (Å)

Pt1—N1	2.071 (7)
Pt1—N2	2.076 (6)
Pt1—Cl1	2.292 (4)
Pt1—Cl2	2.304 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯Cl1ⁱ	0.96	2.79	3.724 (8)	166
C4—H4A⋯Cl1ⁱⁱ	0.97	2.82	3.596 (7)	137
Symmetry codes: (i) x, y-1, z; (ii) $[x+{\script{1\over 2}}, -y+1, z]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ) and X-SEED (Barbour, 2001 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812048295/hb7001sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048295/hb7001Isup2.hkl

checkCIF report

Comment top

The title compound is structurally related with already reported structures of complexes of the type of [MX2(N–N)] (N–N = chelating nitrongen donor ligand) like cis-diiodido(N,N,N',N' -tetramethylethylenediamine-k²N,N')palladium(II) (Abellán-López, et al. 2012) (II) and cis-dichloro(N,N,N'N'-tetramethyl-1,2-diaminoethane) palladium(II) (Boyle et al. 2004) (III).

In the structure of molecule I shown in Fig. 1, geometry around the Platinum atom is distorted square planer as N1-Pt1-N2 angle is 84.95 (3)° and Pt to its four co-ordinated atoms distances are [Pt-N = 2.071 (7) Å] and [Pt-Cl = 2.30 (5) Å]. The coordinated ligand atoms and Pt(II) are coplanar with r.m.s. deviation of 0.0119 Å. The planes of the two N(CH₃)₂ fragments are twisted at an angle of 12.53(1.05)°. The five membered ring formed by coordination of ligand atoms and metal is nonplaner with r.m.s. deviation of 0.1947 (4)Å and both the halogen atoms (Cl1 & Cl2) are displaced from the least square plane defined by (Pt1/N1/C3/C4/N2) by -0.2216 (1) Å & 0.0425 (1) Å respectively. In the crystal, C—H···Cl interactions link the molecules into (001) sheets (Table 2, Fig. 2).

Related literature top

For related structures, see: Abellán-López, et al. (2012); Boyle et al. (2004).

Experimental top

In a round bottom flask took 50 ml of distilled water, 0.5 ml conc. HCL, 0.036 ml of tetramethylethylenediamine (tmeda) (0.24 mmol) and K₂PtCl₄ (0.24 mmol). Refluxed the mixture for about 2 hrs. The solution was changed to pale yellow, it was allowed to cool to room temperature then kept in refrigerator overnight. Pale yellow needles were formed which were filtered, washed with ethanol then with diethylether and dried on vacuum line.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and X-SEED (Barbour, 2001).

Figures top

	Fig. 1. The molecular structure of title complex with 50% probability thermal ellipsoids.
	Fig. 2. The packing diagram showing hydrogen bonds, drawn using dashed lines. Hydrogen atoms not involved in bonding have been omitted for clarity.

cis-Dichloridobis(N,N,N',N'- tetramethylethane-1,2-diamine)platinum(II) top

Crystal data top

[PtCl₂(C₆H₁₆N₂)]	F(000) = 712
M_r = 382.20	D_x = 2.397 Mg m⁻³
Monoclinic, Ia	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: I -2ya	Cell parameters from 6609 reflections
a = 11.8893 (2) Å	θ = 4.0–74.3°
b = 6.0207 (1) Å	µ = 28.99 mm⁻¹
c = 15.8036 (3) Å	T = 296 K
β = 110.549 (2)°	Cut needle, yellow
V = 1059.27 (3) Å³	0.22 × 0.21 × 0.07 mm
Z = 4

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas, CCD) diffractometer	2091 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2067 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.047
ω scans	θ_max = 74.5°, θ_min = 8.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −14→14
T_min = 0.149, T_max = 1.000	k = −6→7
6899 measured reflections	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.1007P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.116	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 1.83 e Å⁻³
2091 reflections	Δρ_min = −2.02 e Å⁻³
105 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.00105 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1005 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (2)

Crystal data top

[PtCl₂(C₆H₁₆N₂)]	V = 1059.27 (3) Å³
M_r = 382.20	Z = 4
Monoclinic, Ia	Cu Kα radiation
a = 11.8893 (2) Å	µ = 28.99 mm⁻¹
b = 6.0207 (1) Å	T = 296 K
c = 15.8036 (3) Å	0.22 × 0.21 × 0.07 mm
β = 110.549 (2)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas, CCD) diffractometer	2091 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	2067 reflections with I > 2σ(I)
T_min = 0.149, T_max = 1.000	R_int = 0.047
6899 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.116	Δρ_max = 1.83 e Å⁻³
S = 1.03	Δρ_min = −2.02 e Å⁻³
2091 reflections	Absolute structure: Flack (1983), 1005 Friedel pairs
105 parameters	Absolute structure parameter: −0.02 (2)
2 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.

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 > 2sigma(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	0.5018 (3)	0.74348 (4)	0.3050 (2)	0.0267 (2)
Cl1	0.4170 (2)	0.9830 (3)	0.37829 (16)	0.0534 (5)
Cl2	0.3628 (2)	0.8443 (5)	0.16737 (16)	0.0595 (6)
N1	0.6301 (5)	0.6421 (11)	0.4255 (3)	0.0315 (11)
N2	0.5876 (5)	0.5269 (10)	0.2453 (3)	0.0354 (12)
C1	0.5722 (6)	0.5088 (14)	0.4782 (4)	0.0471 (19)
H1A	0.6327	0.4523	0.5318	0.071*
H1B	0.5291	0.3870	0.4420	0.071*
H1C	0.5174	0.6009	0.4949	0.071*
C2	0.6976 (8)	0.828 (2)	0.4835 (5)	0.0472 (18)
H2A	0.6438	0.9147	0.5034	0.071*
H2B	0.7320	0.9203	0.4494	0.071*
H2C	0.7604	0.7687	0.5351	0.071*
C3	0.7209 (7)	0.5022 (14)	0.4027 (4)	0.0481 (18)
H3A	0.7820	0.5970	0.3941	0.058*
H3B	0.7599	0.4007	0.4519	0.058*
C4	0.6581 (7)	0.3734 (14)	0.3176 (5)	0.0483 (16)
H4A	0.7168	0.2957	0.2988	0.058*
H4B	0.6051	0.2640	0.3288	0.058*
C5	0.6643 (9)	0.6529 (18)	0.2053 (6)	0.058 (2)
H5A	0.7253	0.7315	0.2522	0.087*
H5B	0.6157	0.7570	0.1618	0.087*
H5C	0.7014	0.5516	0.1762	0.087*
C6	0.5055 (10)	0.3861 (19)	0.1728 (7)	0.073 (3)
H6A	0.5513	0.2764	0.1549	0.109*
H6B	0.4627	0.4771	0.1218	0.109*
H6C	0.4493	0.3136	0.1948	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.0225 (3)	0.0267 (3)	0.0262 (3)	−0.0006 (2)	0.00272 (17)	0.00193 (19)
Cl1	0.0403 (8)	0.0435 (11)	0.0769 (11)	0.0024 (7)	0.0214 (8)	−0.0180 (9)
Cl2	0.0491 (9)	0.0623 (17)	0.0450 (8)	0.0031 (10)	−0.0111 (6)	0.0197 (10)
N1	0.027 (2)	0.042 (4)	0.020 (2)	−0.002 (2)	0.001 (2)	0.002 (2)
N2	0.036 (2)	0.039 (3)	0.033 (2)	0.005 (2)	0.014 (2)	−0.001 (2)
C1	0.045 (4)	0.056 (5)	0.033 (3)	−0.009 (3)	0.005 (3)	0.013 (3)
C2	0.044 (4)	0.056 (6)	0.033 (4)	−0.025 (4)	0.003 (3)	−0.013 (4)
C3	0.038 (3)	0.061 (5)	0.036 (3)	0.019 (3)	0.002 (3)	0.003 (3)
C4	0.046 (4)	0.046 (4)	0.050 (4)	0.018 (3)	0.014 (3)	0.005 (3)
C5	0.068 (5)	0.064 (7)	0.057 (4)	0.005 (5)	0.040 (4)	0.010 (4)
C6	0.079 (6)	0.069 (7)	0.065 (5)	0.000 (5)	0.019 (4)	−0.037 (5)

Geometric parameters (Å, º) top

Pt1—N1	2.071 (7)	C2—H2B	0.9600
Pt1—N2	2.076 (6)	C2—H2C	0.9600
Pt1—Cl1	2.292 (4)	C3—C4	1.504 (11)
Pt1—Cl2	2.304 (5)	C3—H3A	0.9700
N1—C1	1.488 (7)	C3—H3B	0.9700
N1—C2	1.490 (10)	C4—H4A	0.9700
N1—C3	1.510 (8)	C4—H4B	0.9700
N2—C4	1.480 (9)	C5—H5A	0.9600
N2—C5	1.486 (9)	C5—H5B	0.9600
N2—C6	1.483 (10)	C5—H5C	0.9600
C1—H1A	0.9600	C6—H6A	0.9600
C1—H1B	0.9600	C6—H6B	0.9600
C1—H1C	0.9600	C6—H6C	0.9600
C2—H2A	0.9600

N1—Pt1—N2	84.9 (3)	N1—C2—H2C	109.5
N1—Pt1—Cl1	91.9 (2)	H2A—C2—H2C	109.5
N2—Pt1—Cl1	176.7 (3)	H2B—C2—H2C	109.5
N1—Pt1—Cl2	177.2 (2)	C4—C3—N1	109.2 (5)
N2—Pt1—Cl2	92.3 (2)	C4—C3—H3A	109.8
Cl1—Pt1—Cl2	90.83 (16)	N1—C3—H3A	109.8
C1—N1—C2	108.4 (5)	C4—C3—H3B	109.8
C1—N1—C3	110.1 (6)	N1—C3—H3B	109.8
C2—N1—C3	106.9 (6)	H3A—C3—H3B	108.3
C1—N1—Pt1	109.7 (4)	N2—C4—C3	109.7 (6)
C2—N1—Pt1	114.1 (6)	N2—C4—H4A	109.7
C3—N1—Pt1	107.6 (3)	C3—C4—H4A	109.7
C4—N2—C5	112.4 (6)	N2—C4—H4B	109.7
C4—N2—C6	106.3 (7)	C3—C4—H4B	109.7
C5—N2—C6	107.4 (6)	H4A—C4—H4B	108.2
C4—N2—Pt1	106.0 (4)	N2—C5—H5A	109.5
C5—N2—Pt1	110.2 (5)	N2—C5—H5B	109.5
C6—N2—Pt1	114.5 (5)	H5A—C5—H5B	109.5
N1—C1—H1A	109.5	N2—C5—H5C	109.5
N1—C1—H1B	109.5	H5A—C5—H5C	109.5
H1A—C1—H1B	109.5	H5B—C5—H5C	109.5
N1—C1—H1C	109.5	N2—C6—H6A	109.5
H1A—C1—H1C	109.5	N2—C6—H6B	109.5
H1B—C1—H1C	109.5	H6A—C6—H6B	109.5
N1—C2—H2A	109.5	N2—C6—H6C	109.5
N1—C2—H2B	109.5	H6A—C6—H6C	109.5
H2A—C2—H2B	109.5	H6B—C6—H6C	109.5

N2—Pt1—N1—C1	−111.5 (5)	Cl1—Pt1—N2—C5	−82 (4)
Cl1—Pt1—N1—C1	69.7 (5)	Cl2—Pt1—N2—C5	77.3 (5)
Cl2—Pt1—N1—C1	−108 (5)	N1—Pt1—N2—C6	135.9 (7)
N2—Pt1—N1—C2	126.6 (4)	Cl1—Pt1—N2—C6	157 (4)
Cl1—Pt1—N1—C2	−52.2 (4)	Cl2—Pt1—N2—C6	−43.9 (7)
Cl2—Pt1—N1—C2	130 (5)	C1—N1—C3—C4	85.3 (7)
N2—Pt1—N1—C3	8.3 (5)	C2—N1—C3—C4	−157.2 (7)
Cl1—Pt1—N1—C3	−170.5 (5)	Pt1—N1—C3—C4	−34.3 (8)
Cl2—Pt1—N1—C3	11 (5)	C5—N2—C4—C3	76.8 (8)
N1—Pt1—N2—C4	19.1 (5)	C6—N2—C4—C3	−165.9 (6)
Cl1—Pt1—N2—C4	40 (4)	Pt1—N2—C4—C3	−43.7 (7)
Cl2—Pt1—N2—C4	−160.7 (5)	N1—C3—C4—N2	53.2 (8)
N1—Pt1—N2—C5	−102.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl1ⁱ	0.96	2.79	3.724 (8)	166
C4—H4A···Cl1ⁱⁱ	0.97	2.82	3.596 (7)	137

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

Experimental details

Crystal data
Chemical formula	[PtCl₂(C₆H₁₆N₂)]
M_r	382.20
Crystal system, space group	Monoclinic, Ia
Temperature (K)	296
a, b, c (Å)	11.8893 (2), 6.0207 (1), 15.8036 (3)
β (°)	110.549 (2)
V (Å³)	1059.27 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	28.99
Crystal size (mm)	0.22 × 0.21 × 0.07

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas, CCD) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.149, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6899, 2091, 2067
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.116, 1.03
No. of reflections	2091
No. of parameters	105
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.83, −2.02
Absolute structure	Flack (1983), 1005 Friedel pairs
Absolute structure parameter	−0.02 (2)

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 2012) and X-SEED (Barbour, 2001).

Selected bond lengths (Å) top

Pt1—N1	2.071 (7)	Pt1—Cl1	2.292 (4)
Pt1—N2	2.076 (6)	Pt1—Cl2	2.304 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl1ⁱ	0.96	2.79	3.724 (8)	166
C4—H4A···Cl1ⁱⁱ	0.97	2.82	3.596 (7)	137

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

Acknowledgements

The authors thank the deanship of scientific research at King Abdulaziz University for the support of this research via Research Group Track of grant No. (3-102/428).

References

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