PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): m208.
Published online 2010 January 30. doi:  10.1107/S1600536810002606
PMCID: PMC2979959

(2,2′-Bipyridine-κ2 N,N′)bis­(N-ethyl-N-methyl­dithio­carbamato-κ2 S,S′)zinc(II)

Abstract

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 [triangle]); Deng et al. (2007 [triangle]); Jie & Tiekink (2002 [triangle]); Lai & Tiekink (2004 [triangle]); Manohar et al. (1998 [triangle]); Thirumaran et al. (1999 [triangle]); Yin et al. (2004 [triangle]); Zemskova et al. (1993 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m208-scheme1.jpg

Experimental

Crystal data

  • [Zn(C4H8NS2)2(C10H8N2)]
  • M r = 490.02
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m208-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.091
  • S = 1.04
  • 2513 reflections
  • 136 parameters
  • 14 restraints
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.22 e Å−3

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

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002606/hb5313Isup2.hkl

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

Acknowledgments

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.

supplementary crystallographic information

Experimental

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).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The methyl group is disordered with respect to the ethyl group. Both were refined as ethyl groups, but the methyl carbon atoms were refined with 0.5 occupancy each. The carbon-carbon distance was restrained to 1.50±0.01 Å; the anisotorpic temperature factors of the half-occupancy atoms were restrained to be nearly isotropic.

Figures

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

Crystal data

[Zn(C4H8NS2)2(C10H8N2)]F(000) = 1016
Mr = 490.02Dx = 1.493 Mg m3
Orthorhombic, PnaaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2bcCell parameters from 6268 reflections
a = 16.9478 (7) Åθ = 2.4–27.5°
b = 19.3282 (8) ŵ = 1.52 mm1
c = 6.6572 (3) ÅT = 293 K
V = 2180.70 (16) Å3Block, colorless
Z = 40.45 × 0.40 × 0.35 mm

Data collection

Bruker SMART APEX CCD diffractometer2513 independent reflections
Radiation source: fine-focus sealed tube2252 reflections with I > 2σ(I)
graphiteRint = 0.019
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −20→22
Tmin = 0.548, Tmax = 0.618k = −25→24
13725 measured reflectionsl = −5→8

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0554P)2 + 0.6285P] where P = (Fo2 + 2Fc2)/3
2513 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.35 e Å3
14 restraintsΔρmin = −0.22 e Å3

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

xyzUiso*/UeqOcc. (<1)
Zn10.292606 (17)0.25000.25000.03998 (12)
S10.27352 (4)0.14351 (3)0.03544 (9)0.05648 (17)
S20.19702 (3)0.16932 (3)0.42289 (8)0.04706 (15)
N10.16951 (11)0.05783 (10)0.2003 (3)0.0545 (4)
N20.39422 (8)0.21503 (8)0.4216 (2)0.0379 (3)
C10.20922 (11)0.11716 (11)0.2174 (3)0.0424 (4)
C20.18288 (18)0.00855 (16)0.0390 (5)0.0884 (10)0.50
H2A0.22860.0238−0.03670.106*0.50
H2B0.1961−0.03570.09900.106*0.50
C30.1206 (3)−0.0020 (3)−0.0968 (8)0.0731 (15)0.50
H3A0.1326−0.0407−0.18190.110*0.50
H3B0.11360.0387−0.17750.110*0.50
H3C0.0729−0.0113−0.02370.110*0.50
C2'0.18288 (18)0.00855 (16)0.0390 (5)0.0884 (10)0.50
H2'A0.1652−0.03640.08040.106*0.50
H2'B0.23820.00680.00820.106*0.50
H2'C0.15410.0227−0.07810.106*0.50
C40.11331 (16)0.03509 (15)0.3511 (4)0.0725 (7)0.50
H4A0.13980.02960.47750.087*0.50
H4B0.0908−0.00830.31090.087*0.50
H4C0.07220.06900.36440.087*0.50
C4'0.11331 (16)0.03509 (15)0.3511 (4)0.0725 (7)0.50
H4'A0.1228−0.01340.37960.087*0.50
H4'B0.12280.06080.47390.087*0.50
C5'0.0321 (4)0.0434 (5)0.2957 (14)0.114 (3)0.50
H5'A−0.00040.01540.38160.171*0.50
H5'B0.02490.02930.15870.171*0.50
H5'C0.01730.09110.31000.171*0.50
C60.39024 (12)0.18074 (10)0.5947 (3)0.0453 (4)
H60.34080.17030.64700.054*
C70.45602 (13)0.16000 (11)0.6997 (3)0.0492 (5)
H70.45110.13620.82050.059*
C80.52930 (13)0.17520 (11)0.6222 (3)0.0512 (5)
H80.57480.16170.68970.061*
C90.53413 (11)0.21061 (11)0.4434 (3)0.0468 (4)
H90.58310.22120.38820.056*
C100.46553 (10)0.23031 (9)0.3464 (3)0.0367 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.03265 (18)0.04134 (19)0.0460 (2)0.0000.0000.00225 (12)
S10.0583 (3)0.0555 (3)0.0557 (3)−0.0150 (2)0.0193 (3)−0.0093 (2)
S20.0409 (3)0.0566 (3)0.0437 (3)−0.0025 (2)0.00315 (19)−0.0026 (2)
N10.0479 (10)0.0455 (9)0.0701 (12)−0.0080 (8)0.0102 (9)−0.0039 (8)
N20.0354 (7)0.0381 (7)0.0402 (8)−0.0013 (6)0.0004 (6)0.0002 (6)
C10.0357 (9)0.0422 (10)0.0493 (10)0.0005 (7)0.0022 (7)0.0024 (8)
C20.0759 (18)0.0659 (16)0.123 (3)−0.0218 (14)0.0324 (18)−0.0391 (18)
C30.097 (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)
C40.0698 (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)
C60.0455 (10)0.0459 (10)0.0444 (10)−0.0039 (8)0.0010 (8)0.0047 (8)
C70.0581 (12)0.0442 (10)0.0453 (10)−0.0011 (8)−0.0068 (9)0.0067 (9)
C80.0490 (11)0.0497 (11)0.0549 (12)0.0086 (9)−0.0128 (10)0.0034 (9)
C90.0347 (9)0.0524 (11)0.0533 (11)0.0049 (8)−0.0018 (8)0.0007 (9)
C100.0342 (8)0.0355 (8)0.0402 (10)0.0007 (6)−0.0008 (7)−0.0024 (7)

Geometric parameters (Å, °)

Zn1—N22.1742 (15)C3—H3B0.9600
Zn1—N2i2.1742 (15)C3—H3C0.9600
Zn1—S22.5259 (5)C4—H4A0.9600
Zn1—S2i2.5259 (5)C4—H4B0.9600
Zn1—S12.5261 (6)C4—H4C0.9600
Zn1—S1i2.5261 (6)C5'—H5'A0.9600
S1—C11.707 (2)C5'—H5'B0.9600
S2—C11.712 (2)C5'—H5'C0.9600
N1—C11.334 (3)C6—C71.376 (3)
N1—C41.452 (3)C6—H60.9300
N1—C21.453 (3)C7—C81.377 (3)
N2—C61.331 (2)C7—H70.9300
N2—C101.341 (2)C8—C91.375 (3)
C2—C31.405 (5)C8—H80.9300
C2—H2A0.9700C9—C101.384 (3)
C2—H2B0.9700C9—H90.9300
C3—H3A0.9600C10—C10i1.492 (4)
N2—Zn1—N2i75.24 (8)C3—C2—H2A108.1
N2—Zn1—S294.40 (4)N1—C2—H2A108.1
N2i—Zn1—S2159.93 (4)C3—C2—H2B108.1
N2—Zn1—S2i159.93 (4)N1—C2—H2B108.1
N2i—Zn1—S2i94.40 (4)H2A—C2—H2B107.3
S2—Zn1—S2i100.22 (3)N1—C4—H4A109.5
N2—Zn1—S198.35 (4)N1—C4—H4B109.5
N2i—Zn1—S193.31 (4)N1—C4—H4C109.5
S2—Zn1—S170.884 (17)H5'A—C5'—H5'B109.5
S2i—Zn1—S199.39 (2)H5'A—C5'—H5'C109.5
N2—Zn1—S1i93.31 (4)H5'B—C5'—H5'C109.5
N2i—Zn1—S1i98.35 (4)N2—C6—C7122.96 (18)
S2—Zn1—S1i99.39 (2)N2—C6—H6118.5
S2i—Zn1—S1i70.884 (17)C7—C6—H6118.5
S1—Zn1—S1i165.28 (3)C8—C7—C6118.6 (2)
C1—S1—Zn185.62 (7)C8—C7—H7120.7
C1—S2—Zn185.53 (7)C6—C7—H7120.7
C1—N1—C4122.2 (2)C7—C8—C9118.97 (19)
C1—N1—C2123.2 (2)C7—C8—H8120.5
C4—N1—C2114.5 (2)C9—C8—H8120.5
C6—N2—C10118.59 (16)C8—C9—C10119.40 (19)
C6—N2—Zn1124.71 (12)C8—C9—H9120.3
C10—N2—Zn1116.70 (12)C10—C9—H9120.3
N1—C1—S2120.88 (16)N2—C10—C9121.49 (18)
N1—C1—S1121.19 (16)N2—C10—C10i115.69 (10)
S2—C1—S1117.93 (12)C9—C10—C10i122.82 (12)
C3—C2—N1117.0 (3)
N2—Zn1—S1—C192.98 (8)C2—N1—C1—S2−174.1 (2)
N2i—Zn1—S1—C1168.53 (8)C4—N1—C1—S1−178.68 (19)
S2—Zn1—S1—C11.19 (7)C2—N1—C1—S16.0 (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—S11.87 (11)
N2—Zn1—S2—C1−98.50 (8)Zn1—S1—C1—N1178.01 (18)
N2i—Zn1—S2—C1−40.79 (14)Zn1—S1—C1—S2−1.87 (11)
S2i—Zn1—S2—C195.31 (7)C1—N1—C2—C3−114.6 (4)
S1—Zn1—S2—C1−1.18 (7)C4—N1—C2—C369.8 (4)
S1i—Zn1—S2—C1167.40 (7)C10—N2—C6—C7−0.3 (3)
N2i—Zn1—N2—C6179.12 (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—C6118.46 (16)C6—C7—C8—C90.2 (3)
S1—Zn1—N2—C6−89.64 (15)C7—C8—C9—C100.3 (3)
S1i—Zn1—N2—C681.35 (15)C6—N2—C10—C90.7 (3)
N2i—Zn1—N2—C10−0.03 (10)Zn1—N2—C10—C9179.93 (14)
S2—Zn1—N2—C10162.50 (13)C6—N2—C10—C10i−179.12 (19)
S2i—Zn1—N2—C10−60.7 (2)Zn1—N2—C10—C10i0.1 (3)
S1—Zn1—N2—C1091.21 (13)C8—C9—C10—N2−0.7 (3)
S1i—Zn1—N2—C10−97.80 (13)C8—C9—C10—C10i179.1 (2)
C4—N1—C1—S21.2 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5313).

References

  • Ali, B. F., Al-Sou’od, K. A., Al-Far, R. & Judeh, Z. (2006). Struct. Chem.17, 423–429.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2000). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Deng, Y.-H., Liu, J., Li, N., Yang, Y.-L. & Ma, H.-W. (2007). Huaxue Xuebao, 65, 2868–2874.
  • Jie, Q. & Tiekink, E. R. T. (2002). Main Group Met. Chem.25, 317–318.
  • Lai, C. S. & Tiekink, E. R. T. (2004). Appl. Organomet. Chem.18, 197–198.
  • Manohar, A., Venkatachalam, V., Ramalingam, K., Thirumaran, S., Bocelli, G. & Cantoni, A. (1998). J. Chem. Crystallogr.28, 861–866.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Thirumaran, S., Ramalingam, K., Bocelli, G. & Cantoni, A. (1999). Polyhedron, 18, 925–930.
  • Westrip, S. P. (2010). publCIF In preparation.
  • Yin, H.-D., Wang, C.-H. & Xing, Q.-J. (2004). Indian J. Chem. Sect. A, 43, 1911–1914.
  • Zemskova, S. M., Glinskaya, L. A., Durasov, V. B., Klevtsova, R. F. & Larionov, S. V. (1993). Zh. Strukt. Khim.34, 155–157.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography