(2,2′-Bipyridine-κ2N,N′)bis­(N-ethyl-N-methyl­dithio­carbamato-κ2S,S′)zinc(II)

Abdul Ghafar, N.A.; Baba, I.; Yamin, B.M.; Ng, S.W.

doi:10.1107/S1600536810002606

metal-organic compounds

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Volume 66| Part 2| February 2010| Page m208

https://doi.org/10.1107/S1600536810002606

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(2,2′-Bipyridine-κ²N,N′)bis(N-ethyl-N-methyldithiocarbamato-κ²S,S′)zinc(II)

Noorul Aisyah Abdul Ghafar,^a Ibrahim Baba,^a Bohari M. Yamin ^a and Seik Weng Ng ^b ^*

^aSchool of Chemical Sciences, Universiti Kebangbaan Malaysia, 43600 Bangi, Malaysia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 19 January 2010; accepted 20 January 2010; online 30 January 2010)

The complete molecule of the title compound, [Zn(C₄H₈NS₂)₂(C₁₀H₈N₂)], is generated by crystallographic twofold symmetry, with the Zn atom lying on the rotation axis; the axis also bisects the central C—C bond of the 2,2′-bipyridine molecule. The metal atom is chelated by two S,S′-bidentate dithiocarbamate anions and the N,N′-bidentate heterocycle, resulting in a distorted cis-ZnN₂S₄ octahedral geometry. The methyl and ethyl groups of the anion are statistically disordered.

Related literature

For other 2,2′-bipyridine adducts of zinc dithioarbamates, see: Ali et al. (2006 ); Deng et al. (2007 ); Jie & Tiekink (2002 ); Lai & Tiekink (2004 ); Manohar et al. (1998 ); Thirumaran et al. (1999 ); Yin et al. (2004 ); Zemskova et al. (1993 ).

Experimental

Crystal data

[Zn(C₄H₈NS₂)₂(C₁₀H₈N₂)]
M_r = 490.02
Orthorhombic, P n a a
a = 16.9478 (7) Å
b = 19.3282 (8) Å
c = 6.6572 (3) Å
V = 2180.70 (16) Å³
Z = 4
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 293 K
0.45 × 0.40 × 0.35 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.548, T_max = 0.618
13725 measured reflections
2513 independent reflections
2252 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.091
S = 1.04
2513 reflections
136 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N2	2.1742 (15)
Zn1—S2	2.5259 (5)
Zn1—S1	2.5261 (6)

N2—Zn1—N2ⁱ	75.24 (8)
S2—Zn1—S1	70.884 (17)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810002606/hb5313sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002606/hb5313Isup2.hkl

checkCIF report

Related literature top

For other 2,2'-bipyridine adducts of zinc dithioarbamates, see: Ali et al. (2006); Deng et al. (2007); Jie & Tiekink (2002); Lai & Tiekink (2004); Manohar et al. (1998); Thirumaran et al. (1999); Yin et al. (2004); Zemskova et al. (1993).

Experimental top

Zinc chloride (10 mmol), ethylmethylamine (20 mmol), carbon disulfide (20 mmol), 2,2'-bipyridine and ammonia (10 ml) were reacted in ethanol (30 ml) at 277 K to produce a white solid. This was collected and recrystallized from ethanol to yield colourless blocks of (I).

Structure description top

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. View of (I) at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder is not shown.

(2,2'-Bipyridine-κ²N,N')bis(N-ethyl-N- methyldithiocarbamato-κ²S,S')zinc(II) top

Crystal data top

[Zn(C₄H₈NS₂)₂(C₁₀H₈N₂)]	F(000) = 1016
M_r = 490.02	D_x = 1.493 Mg m⁻³
Orthorhombic, Pnaa	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2bc	Cell parameters from 6268 reflections
a = 16.9478 (7) Å	θ = 2.4–27.5°
b = 19.3282 (8) Å	µ = 1.52 mm⁻¹
c = 6.6572 (3) Å	T = 293 K
V = 2180.70 (16) Å³	Block, colorless
Z = 4	0.45 × 0.40 × 0.35 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2513 independent reflections
Radiation source: fine-focus sealed tube	2252 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→22
T_min = 0.548, T_max = 0.618	k = −25→24
13725 measured reflections	l = −5→8

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0554P)² + 0.6285P] where P = (F_o² + 2F_c²)/3
2513 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.35 e Å⁻³
14 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Zn(C₄H₈NS₂)₂(C₁₀H₈N₂)]	V = 2180.70 (16) Å³
M_r = 490.02	Z = 4
Orthorhombic, Pnaa	Mo Kα radiation
a = 16.9478 (7) Å	µ = 1.52 mm⁻¹
b = 19.3282 (8) Å	T = 293 K
c = 6.6572 (3) Å	0.45 × 0.40 × 0.35 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2513 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2252 reflections with I > 2σ(I)
T_min = 0.548, T_max = 0.618	R_int = 0.019
13725 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	14 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.04	Δρ_max = 0.35 e Å⁻³
2513 reflections	Δρ_min = −0.22 e Å⁻³
136 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.292606 (17)	0.2500	0.2500	0.03998 (12)
S1	0.27352 (4)	0.14351 (3)	0.03544 (9)	0.05648 (17)
S2	0.19702 (3)	0.16932 (3)	0.42289 (8)	0.04706 (15)
N1	0.16951 (11)	0.05783 (10)	0.2003 (3)	0.0545 (4)
N2	0.39422 (8)	0.21503 (8)	0.4216 (2)	0.0379 (3)
C1	0.20922 (11)	0.11716 (11)	0.2174 (3)	0.0424 (4)
C2	0.18288 (18)	0.00855 (16)	0.0390 (5)	0.0884 (10)	0.50
H2A	0.2286	0.0238	−0.0367	0.106*	0.50
H2B	0.1961	−0.0357	0.0990	0.106*	0.50
C3	0.1206 (3)	−0.0020 (3)	−0.0968 (8)	0.0731 (15)	0.50
H3A	0.1326	−0.0407	−0.1819	0.110*	0.50
H3B	0.1136	0.0387	−0.1775	0.110*	0.50
H3C	0.0729	−0.0113	−0.0237	0.110*	0.50
C2'	0.18288 (18)	0.00855 (16)	0.0390 (5)	0.0884 (10)	0.50
H2'A	0.1652	−0.0364	0.0804	0.106*	0.50
H2'B	0.2382	0.0068	0.0082	0.106*	0.50
H2'C	0.1541	0.0227	−0.0781	0.106*	0.50
C4	0.11331 (16)	0.03509 (15)	0.3511 (4)	0.0725 (7)	0.50
H4A	0.1398	0.0296	0.4775	0.087*	0.50
H4B	0.0908	−0.0083	0.3109	0.087*	0.50
H4C	0.0722	0.0690	0.3644	0.087*	0.50
C4'	0.11331 (16)	0.03509 (15)	0.3511 (4)	0.0725 (7)	0.50
H4'A	0.1228	−0.0134	0.3796	0.087*	0.50
H4'B	0.1228	0.0608	0.4739	0.087*	0.50
C5'	0.0321 (4)	0.0434 (5)	0.2957 (14)	0.114 (3)	0.50
H5'A	−0.0004	0.0154	0.3816	0.171*	0.50
H5'B	0.0249	0.0293	0.1587	0.171*	0.50
H5'C	0.0173	0.0911	0.3100	0.171*	0.50
C6	0.39024 (12)	0.18074 (10)	0.5947 (3)	0.0453 (4)
H6	0.3408	0.1703	0.6470	0.054*
C7	0.45602 (13)	0.16000 (11)	0.6997 (3)	0.0492 (5)
H7	0.4511	0.1362	0.8205	0.059*
C8	0.52930 (13)	0.17520 (11)	0.6222 (3)	0.0512 (5)
H8	0.5748	0.1617	0.6897	0.061*
C9	0.53413 (11)	0.21061 (11)	0.4434 (3)	0.0468 (4)
H9	0.5831	0.2212	0.3882	0.056*
C10	0.46553 (10)	0.23031 (9)	0.3464 (3)	0.0367 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03265 (18)	0.04134 (19)	0.0460 (2)	0.000	0.000	0.00225 (12)
S1	0.0583 (3)	0.0555 (3)	0.0557 (3)	−0.0150 (2)	0.0193 (3)	−0.0093 (2)
S2	0.0409 (3)	0.0566 (3)	0.0437 (3)	−0.0025 (2)	0.00315 (19)	−0.0026 (2)
N1	0.0479 (10)	0.0455 (9)	0.0701 (12)	−0.0080 (8)	0.0102 (9)	−0.0039 (8)
N2	0.0354 (7)	0.0381 (7)	0.0402 (8)	−0.0013 (6)	0.0004 (6)	0.0002 (6)
C1	0.0357 (9)	0.0422 (10)	0.0493 (10)	0.0005 (7)	0.0022 (7)	0.0024 (8)
C2	0.0759 (18)	0.0659 (16)	0.123 (3)	−0.0218 (14)	0.0324 (18)	−0.0391 (18)
C3	0.097 (4)	0.063 (3)	0.059 (3)	0.017 (3)	−0.009 (3)	−0.012 (2)
C2'	0.0759 (18)	0.0659 (16)	0.123 (3)	−0.0218 (14)	0.0324 (18)	−0.0391 (18)
C4	0.0698 (16)	0.0695 (15)	0.0783 (17)	−0.0251 (13)	0.0123 (14)	0.0122 (13)
C4'	0.0698 (16)	0.0695 (15)	0.0783 (17)	−0.0251 (13)	0.0123 (14)	0.0122 (13)
C5'	0.086 (4)	0.124 (6)	0.132 (6)	−0.010 (4)	0.025 (4)	0.026 (5)
C6	0.0455 (10)	0.0459 (10)	0.0444 (10)	−0.0039 (8)	0.0010 (8)	0.0047 (8)
C7	0.0581 (12)	0.0442 (10)	0.0453 (10)	−0.0011 (8)	−0.0068 (9)	0.0067 (9)
C8	0.0490 (11)	0.0497 (11)	0.0549 (12)	0.0086 (9)	−0.0128 (10)	0.0034 (9)
C9	0.0347 (9)	0.0524 (11)	0.0533 (11)	0.0049 (8)	−0.0018 (8)	0.0007 (9)
C10	0.0342 (8)	0.0355 (8)	0.0402 (10)	0.0007 (6)	−0.0008 (7)	−0.0024 (7)

Geometric parameters (Å, º) top

Zn1—N2	2.1742 (15)	C3—H3B	0.9600
Zn1—N2ⁱ	2.1742 (15)	C3—H3C	0.9600
Zn1—S2	2.5259 (5)	C4—H4A	0.9600
Zn1—S2ⁱ	2.5259 (5)	C4—H4B	0.9600
Zn1—S1	2.5261 (6)	C4—H4C	0.9600
Zn1—S1ⁱ	2.5261 (6)	C5'—H5'A	0.9600
S1—C1	1.707 (2)	C5'—H5'B	0.9600
S2—C1	1.712 (2)	C5'—H5'C	0.9600
N1—C1	1.334 (3)	C6—C7	1.376 (3)
N1—C4	1.452 (3)	C6—H6	0.9300
N1—C2	1.453 (3)	C7—C8	1.377 (3)
N2—C6	1.331 (2)	C7—H7	0.9300
N2—C10	1.341 (2)	C8—C9	1.375 (3)
C2—C3	1.405 (5)	C8—H8	0.9300
C2—H2A	0.9700	C9—C10	1.384 (3)
C2—H2B	0.9700	C9—H9	0.9300
C3—H3A	0.9600	C10—C10ⁱ	1.492 (4)

N2—Zn1—N2ⁱ	75.24 (8)	C3—C2—H2A	108.1
N2—Zn1—S2	94.40 (4)	N1—C2—H2A	108.1
N2ⁱ—Zn1—S2	159.93 (4)	C3—C2—H2B	108.1
N2—Zn1—S2ⁱ	159.93 (4)	N1—C2—H2B	108.1
N2ⁱ—Zn1—S2ⁱ	94.40 (4)	H2A—C2—H2B	107.3
S2—Zn1—S2ⁱ	100.22 (3)	N1—C4—H4A	109.5
N2—Zn1—S1	98.35 (4)	N1—C4—H4B	109.5
N2ⁱ—Zn1—S1	93.31 (4)	N1—C4—H4C	109.5
S2—Zn1—S1	70.884 (17)	H5'A—C5'—H5'B	109.5
S2ⁱ—Zn1—S1	99.39 (2)	H5'A—C5'—H5'C	109.5
N2—Zn1—S1ⁱ	93.31 (4)	H5'B—C5'—H5'C	109.5
N2ⁱ—Zn1—S1ⁱ	98.35 (4)	N2—C6—C7	122.96 (18)
S2—Zn1—S1ⁱ	99.39 (2)	N2—C6—H6	118.5
S2ⁱ—Zn1—S1ⁱ	70.884 (17)	C7—C6—H6	118.5
S1—Zn1—S1ⁱ	165.28 (3)	C8—C7—C6	118.6 (2)
C1—S1—Zn1	85.62 (7)	C8—C7—H7	120.7
C1—S2—Zn1	85.53 (7)	C6—C7—H7	120.7
C1—N1—C4	122.2 (2)	C7—C8—C9	118.97 (19)
C1—N1—C2	123.2 (2)	C7—C8—H8	120.5
C4—N1—C2	114.5 (2)	C9—C8—H8	120.5
C6—N2—C10	118.59 (16)	C8—C9—C10	119.40 (19)
C6—N2—Zn1	124.71 (12)	C8—C9—H9	120.3
C10—N2—Zn1	116.70 (12)	C10—C9—H9	120.3
N1—C1—S2	120.88 (16)	N2—C10—C9	121.49 (18)
N1—C1—S1	121.19 (16)	N2—C10—C10ⁱ	115.69 (10)
S2—C1—S1	117.93 (12)	C9—C10—C10ⁱ	122.82 (12)
C3—C2—N1	117.0 (3)

N2—Zn1—S1—C1	92.98 (8)	C2—N1—C1—S2	−174.1 (2)
N2ⁱ—Zn1—S1—C1	168.53 (8)	C4—N1—C1—S1	−178.68 (19)
S2—Zn1—S1—C1	1.19 (7)	C2—N1—C1—S1	6.0 (3)
S2ⁱ—Zn1—S1—C1	−96.46 (7)	Zn1—S2—C1—N1	−178.01 (18)
S1ⁱ—Zn1—S1—C1	−49.05 (7)	Zn1—S2—C1—S1	1.87 (11)
N2—Zn1—S2—C1	−98.50 (8)	Zn1—S1—C1—N1	178.01 (18)
N2ⁱ—Zn1—S2—C1	−40.79 (14)	Zn1—S1—C1—S2	−1.87 (11)
S2ⁱ—Zn1—S2—C1	95.31 (7)	C1—N1—C2—C3	−114.6 (4)
S1—Zn1—S2—C1	−1.18 (7)	C4—N1—C2—C3	69.8 (4)
S1ⁱ—Zn1—S2—C1	167.40 (7)	C10—N2—C6—C7	−0.3 (3)
N2ⁱ—Zn1—N2—C6	179.12 (19)	Zn1—N2—C6—C7	−179.41 (16)
S2—Zn1—N2—C6	−18.34 (15)	N2—C6—C7—C8	−0.2 (3)
S2ⁱ—Zn1—N2—C6	118.46 (16)	C6—C7—C8—C9	0.2 (3)
S1—Zn1—N2—C6	−89.64 (15)	C7—C8—C9—C10	0.3 (3)
S1ⁱ—Zn1—N2—C6	81.35 (15)	C6—N2—C10—C9	0.7 (3)
N2ⁱ—Zn1—N2—C10	−0.03 (10)	Zn1—N2—C10—C9	179.93 (14)
S2—Zn1—N2—C10	162.50 (13)	C6—N2—C10—C10ⁱ	−179.12 (19)
S2ⁱ—Zn1—N2—C10	−60.7 (2)	Zn1—N2—C10—C10ⁱ	0.1 (3)
S1—Zn1—N2—C10	91.21 (13)	C8—C9—C10—N2	−0.7 (3)
S1ⁱ—Zn1—N2—C10	−97.80 (13)	C8—C9—C10—C10ⁱ	179.1 (2)
C4—N1—C1—S2	1.2 (3)

Symmetry code: (i) x, −y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₄H₈NS₂)₂(C₁₀H₈N₂)]
M_r	490.02
Crystal system, space group	Orthorhombic, Pnaa
Temperature (K)	293
a, b, c (Å)	16.9478 (7), 19.3282 (8), 6.6572 (3)
V (Å³)	2180.70 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.45 × 0.40 × 0.35

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.548, 0.618
No. of measured, independent and observed [I > 2σ(I)] reflections	13725, 2513, 2252
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.091, 1.04
No. of reflections	2513
No. of parameters	136
No. of restraints	14
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.22

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) top

Zn1—N2	2.1742 (15)	Zn1—S1	2.5261 (6)
Zn1—S2	2.5259 (5)

N2—Zn1—N2ⁱ	75.24 (8)	S2—Zn1—S1	70.884 (17)

Symmetry code: (i) x, −y+1/2, −z+1/2.

Acknowledgements

We thank Universiti Kebangsaan Malaysia (UKM-GUP-NBT-08-27-111 and 06-01-02-SF0539) and the University of Malaya for supporting this study.

References

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