Bis(O-ethyl dithio­carbonato-κ2S,S′)bis­(pyridine-3-carbonitrile-κN1)nickel(II)

Kapoor, S.; Kour, R.; Sachar, R.; Kant, R.; Gupta, V.K.; Kapoor, K.

doi:10.1107/S1600536811053475

metal-organic compounds

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Volume 68| Part 1| January 2012| Page m58

doi:10.1107/S1600536811053475

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Bis(O-ethyl dithiocarbonato-κ²S,S′)bis(pyridine-3-carbonitrile-κN¹)nickel(II)

Sanjay Kapoor,^a Ramandeep Kour,^b Renu Sachar,^a Rajni Kant,^b ^* Vivek K. Gupta ^b and Kamini Kapoor ^b

^aDepartment of Chemistry, University of Jammu, Jammu Tawi 180 006, India, and ^bX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India
^*Correspondence e-mail: rkvk.paper11@gmail.com

(Received 28 November 2011; accepted 12 December 2011; online 17 December 2011)

The Ni²⁺ ion in the title complex, [Ni(C₃H₅OS₂)₂(C₆H₄N₂)₂], is in a strongly distorted octahedral coordination environment formed by an N₂S₄ donor set, with the Ni²⁺ ion located on a centre of inversion. In the crystal, weak C—H⋯S and C—H⋯N interactions are observed.

Related literature

For related structures, see: Tiekink & Haiduc (2005 ); Dakternieks et al. (2006 ); Hill & Tiekink (2007 ); Hogarth et al. (2009 )

Experimental

Crystal data

[Ni(C₃H₅OS₂)₂(C₆H₄N₂)₂]
M_r = 509.31
Monoclinic, P 2₁ /c
a = 6.7302 (2) Å
b = 18.8959 (5) Å
c = 8.7242 (2) Å
β = 95.916 (2)°
V = 1103.58 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 293 K
0.3 × 0.3 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.728, T_max = 1.000
18847 measured reflections
1930 independent reflections
1723 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.060
S = 1.07
1930 reflections
134 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N1	2.1273 (17)
Ni1—S1	2.4335 (5)
Ni1—S2	2.4450 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯S2ⁱ	0.97	2.85	3.455 (2)	121
C10—H10C⋯N2ⁱⁱ	0.96	2.65	3.595 (4)	169
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+2.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053475/gk2438sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053475/gk2438Isup2.hkl

checkCIF report

Comment top

Xanthates (O-alkyl/aryl dithiocarbonates) have been known for a long time and many adducts of metal xanthates with different ligands have been prepared and studied in the last several decades. Adducts of transition metal xanthates with N-donor ligands are well represented in the literature, the most extensively studied being those of nickel(II). Nitrogen containing adducts of nickel(II) xanthates are known to adopt a variety of supramolecular assemblies (Tiekink & Haiduc, 2005). The Ni atom in (I) is located on a center of inversion and exists within a trans-N2S4 donor set that defines an approximately octahedral coordination geometry. The chelating xanthate ligand forms essentially equivalent Ni—S bond distances; this equivalence is reflected in the parameters defining the xanthate ligand. The bond angles around the Ni atom are in the range of 73.83 (2) to 180.00 (3)°. The Ni—S bond lengths, Ni1—S1 = 2.4335 (5); Ni1—S2 = 2.4450 (6) Å, are in good agreement with those reported for other Ni-dithiocarbonato complexes (Tiekink & Haiduc, 2005; Dakternieks et al., 2006; Hill & Tiekink, 2007; Hogarth et al., 2009). Molecules in the unit cell are packed together to form well defined layers. While no classical hydrogen bonds are present, the C—H···S and C—H···N hydrogen bonds (Table 1) play important role in stabilizing the crystal structure.

Related literature top

For related structures, see: Tiekink & Haiduc (2005); Dakternieks et al. (2006); Hill & Tiekink (2007); Hogarth et al. (2009)

Experimental top

The title complex was prepared by stirring the parent nickel(II) ethylxanthate (0.781g,0.0026 mol.) with 3-cyanopyridine(0.541g, 0.0052 mol.) in acetone(60 ml) for one hour. Green crystals of (I) were isolated by the slow evaporation of the resulting solution of the complex.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. ORTEP view of the molecule with displacement ellipsoids drawn at the 30% probability level. Unlabeled atoms are generated by the symmetry operation -x, 1-y, 1-z.
	Fig. 2. The packing arrangement of molecules viewed down the a axis.

Bis(O-ethyl dithiocarbonato-κ²S,S')bis(pyridine-3-carbonitrile- κN¹)nickel(II) top

Crystal data top

[Ni(C₃H₅OS₂)₂(C₆H₄N₂)₂]	F(000) = 524
M_r = 509.31	D_x = 1.533 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10361 reflections
a = 6.7302 (2) Å	θ = 3.6–29.0°
b = 18.8959 (5) Å	µ = 1.28 mm⁻¹
c = 8.7242 (2) Å	T = 293 K
β = 95.916 (2)°	Hexagonal plate, green
V = 1103.58 (5) Å³	0.3 × 0.3 × 0.1 mm
Z = 2

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1930 independent reflections
Radiation source: fine-focus sealed tube	1723 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 16.1049 pixels mm^-1	θ_max = 25.0°, θ_min = 3.7°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −22→22
T_min = 0.728, T_max = 1.000	l = −10→10
18847 measured 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0208P)² + 0.7659P] where P = (F_o² + 2F_c²)/3
1930 reflections	(Δ/σ)_max = 0.001
134 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Ni(C₃H₅OS₂)₂(C₆H₄N₂)₂]	V = 1103.58 (5) Å³
M_r = 509.31	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7302 (2) Å	µ = 1.28 mm⁻¹
b = 18.8959 (5) Å	T = 293 K
c = 8.7242 (2) Å	0.3 × 0.3 × 0.1 mm
β = 95.916 (2)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1930 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	1723 reflections with I > 2σ(I)
T_min = 0.728, T_max = 1.000	R_int = 0.036
18847 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.07	Δρ_max = 0.23 e Å⁻³
1930 reflections	Δρ_min = −0.22 e Å⁻³
134 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
Ni1	0.0000	0.5000	0.5000	0.02943 (12)
S1	0.33453 (8)	0.46692 (3)	0.60894 (6)	0.03356 (14)
S2	0.03241 (8)	0.54100 (3)	0.23794 (7)	0.03737 (15)
O1	0.3099 (2)	0.42097 (8)	0.89474 (17)	0.0404 (4)
N1	0.0499 (3)	0.60555 (9)	0.5796 (2)	0.0340 (4)
N2	−0.3300 (4)	0.76898 (12)	0.8455 (3)	0.0691 (7)
C2	−0.0808 (3)	0.63914 (11)	0.6579 (3)	0.0368 (5)
H2	−0.1910	0.6143	0.6856	0.044*
C3	−0.0591 (3)	0.71000 (12)	0.6999 (3)	0.0401 (5)
C4	0.1050 (4)	0.74716 (13)	0.6592 (3)	0.0484 (6)
H4	0.1222	0.7947	0.6846	0.058*
C5	0.2413 (4)	0.71212 (13)	0.5805 (3)	0.0469 (6)
H5	0.3542	0.7354	0.5532	0.056*
C6	0.2086 (3)	0.64182 (12)	0.5425 (3)	0.0383 (5)
H6	0.3014	0.6186	0.4885	0.046*
C7	−0.2097 (4)	0.74323 (13)	0.7818 (3)	0.0497 (6)
C8	0.2162 (3)	0.44638 (11)	0.7649 (2)	0.0319 (5)
C9	0.5252 (3)	0.41173 (13)	0.9032 (3)	0.0446 (6)
H9A	0.5889	0.4561	0.8807	0.054*
H9B	0.5583	0.3767	0.8285	0.054*
C10	0.5962 (4)	0.38776 (14)	1.0625 (3)	0.0520 (6)
H10A	0.5554	0.4213	1.1357	0.078*
H10B	0.7392	0.3842	1.0732	0.078*
H10C	0.5395	0.3423	1.0810	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0264 (2)	0.0265 (2)	0.0358 (2)	0.00092 (15)	0.00515 (15)	0.00119 (16)
S1	0.0274 (3)	0.0369 (3)	0.0373 (3)	0.0017 (2)	0.0078 (2)	0.0051 (2)
S2	0.0275 (3)	0.0441 (3)	0.0418 (3)	0.0007 (2)	0.0097 (2)	0.0045 (2)
O1	0.0312 (8)	0.0509 (10)	0.0392 (9)	0.0036 (7)	0.0040 (7)	0.0093 (7)
N1	0.0334 (10)	0.0296 (9)	0.0387 (10)	0.0001 (8)	0.0028 (8)	0.0021 (8)
N2	0.0700 (17)	0.0489 (14)	0.0917 (19)	0.0032 (12)	0.0249 (14)	−0.0198 (13)
C2	0.0360 (12)	0.0332 (12)	0.0412 (13)	−0.0003 (9)	0.0035 (10)	−0.0004 (10)
C3	0.0443 (13)	0.0338 (12)	0.0412 (13)	0.0033 (10)	0.0001 (10)	−0.0040 (10)
C4	0.0590 (16)	0.0314 (12)	0.0535 (15)	−0.0084 (11)	−0.0004 (12)	−0.0019 (11)
C5	0.0466 (14)	0.0411 (13)	0.0531 (15)	−0.0124 (11)	0.0061 (11)	0.0036 (12)
C6	0.0351 (12)	0.0371 (12)	0.0424 (13)	−0.0012 (9)	0.0033 (10)	0.0038 (10)
C7	0.0561 (16)	0.0361 (13)	0.0565 (16)	−0.0024 (12)	0.0042 (13)	−0.0096 (12)
C8	0.0306 (11)	0.0294 (11)	0.0357 (11)	−0.0003 (9)	0.0028 (9)	0.0021 (9)
C9	0.0341 (12)	0.0503 (14)	0.0488 (14)	0.0072 (10)	0.0013 (10)	0.0061 (11)
C10	0.0525 (15)	0.0469 (15)	0.0536 (15)	0.0075 (12)	−0.0082 (12)	0.0037 (12)

Geometric parameters (Å, º) top

Ni1—N1	2.1273 (17)	C3—C7	1.442 (3)
Ni1—S1	2.4335 (5)	C4—C5	1.372 (3)
Ni1—S2	2.4450 (6)	C4—H4	0.9300
S1—C8	1.691 (2)	C5—C6	1.381 (3)
S2—C8ⁱ	1.688 (2)	C5—H5	0.9300
O1—C8	1.328 (2)	C6—H6	0.9300
O1—C9	1.454 (3)	C9—C10	1.493 (3)
N1—C2	1.329 (3)	C9—H9A	0.9700
N1—C6	1.336 (3)	C9—H9B	0.9700
N2—C7	1.138 (3)	C10—H10A	0.9600
C2—C3	1.392 (3)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C4	1.385 (3)

N1ⁱ—Ni1—N1	180.00 (3)	C2—C3—C7	119.3 (2)
N1ⁱ—Ni1—S1	89.73 (5)	C5—C4—C3	118.4 (2)
N1—Ni1—S1	90.27 (5)	C5—C4—H4	120.8
N1ⁱ—Ni1—S1ⁱ	90.27 (5)	C3—C4—H4	120.8
N1—Ni1—S1ⁱ	89.73 (5)	C4—C5—C6	119.1 (2)
S1—Ni1—S1ⁱ	180.0	C4—C5—H5	120.5
N1ⁱ—Ni1—S2ⁱ	88.96 (5)	C6—C5—H5	120.5
N1—Ni1—S2ⁱ	91.04 (5)	N1—C6—C5	123.1 (2)
S1—Ni1—S2ⁱ	73.831 (18)	N1—C6—H6	118.4
S1ⁱ—Ni1—S2ⁱ	106.169 (18)	C5—C6—H6	118.4
N1ⁱ—Ni1—S2	91.04 (5)	N2—C7—C3	179.3 (3)
N1—Ni1—S2	88.96 (5)	O1—C8—S2ⁱ	116.53 (15)
S1—Ni1—S2	106.169 (18)	O1—C8—S1	123.21 (15)
S1ⁱ—Ni1—S2	73.831 (18)	S2ⁱ—C8—S1	120.26 (12)
S2ⁱ—Ni1—S2	180.0	O1—C9—C10	107.76 (19)
C8—S1—Ni1	83.10 (7)	O1—C9—H9A	110.2
C8ⁱ—S2—Ni1	82.80 (7)	C10—C9—H9A	110.2
C8—O1—C9	118.02 (17)	O1—C9—H9B	110.2
C2—N1—C6	117.86 (19)	C10—C9—H9B	110.2
C2—N1—Ni1	121.65 (14)	H9A—C9—H9B	108.5
C6—N1—Ni1	120.33 (15)	C9—C10—H10A	109.5
N1—C2—C3	122.5 (2)	C9—C10—H10B	109.5
N1—C2—H2	118.7	H10A—C10—H10B	109.5
C3—C2—H2	118.7	C9—C10—H10C	109.5
C4—C3—C2	119.0 (2)	H10A—C10—H10C	109.5
C4—C3—C7	121.7 (2)	H10B—C10—H10C	109.5

N1ⁱ—Ni1—S1—C8	−88.58 (9)	C6—N1—C2—C3	0.8 (3)
N1—Ni1—S1—C8	91.42 (9)	Ni1—N1—C2—C3	−174.57 (16)
S2ⁱ—Ni1—S1—C8	0.42 (7)	N1—C2—C3—C4	−0.1 (3)
S2—Ni1—S1—C8	−179.58 (7)	N1—C2—C3—C7	178.6 (2)
N1ⁱ—Ni1—S2—C8ⁱ	90.39 (9)	C2—C3—C4—C5	−0.9 (4)
N1—Ni1—S2—C8ⁱ	−89.61 (9)	C7—C3—C4—C5	−179.6 (2)
S1—Ni1—S2—C8ⁱ	−179.58 (7)	C3—C4—C5—C6	1.2 (4)
S1ⁱ—Ni1—S2—C8ⁱ	0.42 (7)	C2—N1—C6—C5	−0.5 (3)
S1—Ni1—N1—C2	−130.63 (16)	Ni1—N1—C6—C5	174.93 (18)
S1ⁱ—Ni1—N1—C2	49.37 (16)	C4—C5—C6—N1	−0.5 (4)
S2ⁱ—Ni1—N1—C2	−56.80 (16)	C9—O1—C8—S2ⁱ	−177.93 (16)
S2—Ni1—N1—C2	123.20 (16)	C9—O1—C8—S1	1.2 (3)
S1—Ni1—N1—C6	54.10 (16)	Ni1—S1—C8—O1	−179.72 (18)
S1ⁱ—Ni1—N1—C6	−125.90 (16)	Ni1—S1—C8—S2ⁱ	−0.67 (12)
S2ⁱ—Ni1—N1—C6	127.93 (16)	C8—O1—C9—C10	176.01 (19)
S2—Ni1—N1—C6	−52.07 (16)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···S2ⁱⁱ	0.97	2.85	3.455 (2)	121
C10—H10C···N2ⁱⁱⁱ	0.96	2.65	3.595 (4)	169

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

Experimental details

Crystal data
Chemical formula	[Ni(C₃H₅OS₂)₂(C₆H₄N₂)₂]
M_r	509.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.7302 (2), 18.8959 (5), 8.7242 (2)
β (°)	95.916 (2)
V (Å³)	1103.58 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.28
Crystal size (mm)	0.3 × 0.3 × 0.1

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)
T_min, T_max	0.728, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	18847, 1930, 1723
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.060, 1.07
No. of reflections	1930
No. of parameters	134
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.22

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Selected bond lengths (Å) top

Ni1—N1	2.1273 (17)	Ni1—S2	2.4450 (6)
Ni1—S1	2.4335 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···S2ⁱ	0.97	2.85	3.455 (2)	121
C10—H10C···N2ⁱⁱ	0.96	2.65	3.595 (4)	169

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

Acknowledgements

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. He is also thankful to the UGC for research funding under research project F.No. 37?4154/2009 (J&K) (SR).

References

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