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Acta Cryst. (2009). E65, m143    [ doi:10.1107/S1600536808043973 ]

(2,2'-Bipyridine-[kappa]2N,N')(4-hydroxy-2-oxidobenzaldehyde thiosemicarbazonato-[kappa]3O2,N1,S)zinc(II)

K. W. Tan, C. H. Ng, M. J. Maah and S. W. Ng

Abstract top

The ZnII atom in the title compound, [Zn(C8H7N3O2S)(C10H8N2)], is N,N'-chelated by the heterocycle and N,O,S-chelated by the doubly deprotonated Schiff base ligand in a distorted square-pyramidal environment. O-H...O and N-H...N hydrogen bonds link adjacent molecules into a layer structure.

Related literature top

For the square-pyramidal 1,10-phenanthroline adduct, which exists as a monohydrated DMSO disolvate, see: Tan et al. (2009).

Experimental top

Zinc acetate monohydrate (0.22 g, 1 mmol), 2,4-dihydroxybenzaldehyde thiosemicarbazone (0.21 g, 1 mmol) and 2,2'-bipyridine (0.16 g, 1 mmol) were heated in ethanol (40 ml). The compound that precipitated upon heating for 30 min was collected and recrystallized from DMF.

Refinement top

Hydrogen atoms were placed in calculated positions (C–H 0.95, N–H 0.88, O–H 0.84 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C,N,O).

The four carbon atoms of one of the two rings of the 2,2'-bipyridine molecule showed somewhat large anisotropic temperature factors. These were restrained to be nearly isotropic.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid (Barbour, 2001) plot of Zn(C8H7N3O2S)(C10H8N2) at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.
(2,2'-Bipyridine-κ2N,N')(4-hydroxy-2-oxidobenzaldehyde thiosemicarbazonato-κ3O2,N1,S)zinc(II) top
Crystal data top
[Zn(C8H7N3O2S)(C10H8N2)]F(000) = 880
Mr = 430.78Dx = 1.558 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3053 reflections
a = 16.1256 (4) Åθ = 2.3–26.2°
b = 7.0478 (2) ŵ = 1.48 mm−1
c = 17.6387 (5) ÅT = 100 K
β = 113.646 (2)°Prism, yellow
V = 1836.33 (9) Å30.10 × 0.04 × 0.02 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		4191 independent reflections
Radiation source: fine-focus sealed tube2919 reflections with I > 2σ(I)
graphiteRint = 0.086
ω scansθmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→20
Tmin = 0.867, Tmax = 0.971k = −9→9
15773 measured reflectionsl = −21→22
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.195H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.1071P)2 + 3.3408P]
where P = (Fo2 + 2Fc2)/3
4191 reflections(Δ/σ)max = 0.001
245 parametersΔρmax = 0.88 e Å−3
24 restraintsΔρmin = −0.96 e Å−3
Crystal data top
[Zn(C8H7N3O2S)(C10H8N2)]V = 1836.33 (9) Å3
Mr = 430.78Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.1256 (4) ŵ = 1.48 mm−1
b = 7.0478 (2) ÅT = 100 K
c = 17.6387 (5) Å0.10 × 0.04 × 0.02 mm
β = 113.646 (2)°
Data collection top
Bruker SMART APEX
diffractometer		4191 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2919 reflections with I > 2σ(I)
Tmin = 0.867, Tmax = 0.971Rint = 0.086
15773 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.195Δρmax = 0.88 e Å−3
S = 1.04Δρmin = −0.96 e Å−3
4191 reflectionsAbsolute structure: ?
245 parametersFlack parameter: ?
24 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.26010 (4)0.61341 (9)0.78222 (4)0.0186 (2)
S10.35671 (10)0.8297 (2)0.75159 (9)0.0239 (3)
O10.1393 (2)0.4912 (5)0.7423 (2)0.0221 (8)
O2−0.0804 (3)−0.0017 (6)0.6388 (2)0.0238 (8)
H2−0.09410.03250.67800.036*
N10.2953 (3)0.4436 (7)0.7058 (3)0.0213 (10)
N20.3774 (3)0.4754 (7)0.6981 (3)0.0226 (10)
N30.4867 (3)0.6892 (7)0.7112 (3)0.0276 (11)
H310.51350.60210.69320.033*
H320.51070.80290.72420.033*
N40.3299 (3)0.4781 (7)0.8970 (3)0.0276 (11)
N60.2340 (3)0.7942 (6)0.8656 (3)0.0186 (9)
C10.1130 (4)0.3300 (8)0.7005 (3)0.0198 (11)
C20.0305 (3)0.2459 (8)0.6918 (3)0.0192 (11)
H2A−0.00490.30530.71700.023*
C3−0.0009 (4)0.0790 (8)0.6476 (3)0.0199 (11)
C40.0493 (4)−0.0115 (8)0.6105 (3)0.0250 (12)
H40.0276−0.12480.57980.030*
C50.1305 (4)0.0642 (8)0.6187 (3)0.0246 (12)
H50.16440.00170.59270.030*
C60.1660 (3)0.2315 (7)0.6641 (3)0.0182 (10)
C70.2514 (4)0.2930 (8)0.6672 (3)0.0210 (11)
H70.27880.21800.63880.025*
C80.4083 (4)0.6481 (8)0.7189 (3)0.0233 (12)
C90.3807 (6)0.3222 (11)0.9082 (5)0.0486 (19)
H90.38520.26320.86150.058*
C100.4268 (7)0.2446 (14)0.9857 (5)0.068 (3)
H100.46310.13460.99240.082*
C110.4195 (6)0.3282 (13)1.0529 (5)0.059 (2)
H110.45030.27521.10650.071*
C120.3680 (5)0.4878 (11)1.0429 (4)0.0390 (16)
H120.36280.54801.08900.047*
C130.3235 (4)0.5594 (9)0.9635 (3)0.0246 (12)
C140.2655 (4)0.7348 (8)0.9444 (3)0.0235 (12)
C150.2450 (5)0.8306 (10)1.0037 (4)0.0345 (15)
H150.26720.78611.05920.041*
C160.1917 (5)0.9915 (11)0.9804 (4)0.0429 (18)
H160.17541.05731.01940.051*
C170.1624 (5)1.0556 (9)0.9000 (4)0.0356 (15)
H170.12761.16840.88310.043*
C180.1848 (4)0.9525 (8)0.8448 (4)0.0242 (12)
H180.16430.99610.78930.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0165 (3)0.0207 (3)0.0182 (3)0.0020 (2)0.0065 (2)0.0029 (2)
S10.0208 (7)0.0196 (7)0.0340 (8)0.0012 (5)0.0139 (6)0.0039 (5)
O10.0178 (19)0.021 (2)0.028 (2)−0.0017 (15)0.0101 (16)−0.0024 (16)
O20.0186 (19)0.027 (2)0.025 (2)−0.0039 (16)0.0079 (16)−0.0022 (16)
N10.018 (2)0.026 (2)0.021 (2)−0.0014 (19)0.0095 (19)0.0022 (18)
N20.014 (2)0.030 (3)0.024 (2)−0.0033 (19)0.0094 (19)−0.002 (2)
N30.022 (2)0.025 (2)0.043 (3)−0.006 (2)0.021 (2)−0.005 (2)
N40.027 (3)0.033 (3)0.024 (2)0.009 (2)0.012 (2)0.012 (2)
N60.016 (2)0.019 (2)0.019 (2)0.0003 (17)0.0052 (18)0.0038 (17)
C10.020 (3)0.019 (3)0.019 (3)0.002 (2)0.007 (2)0.004 (2)
C20.016 (2)0.024 (3)0.018 (2)0.002 (2)0.007 (2)0.002 (2)
C30.015 (2)0.023 (3)0.018 (2)0.001 (2)0.002 (2)0.006 (2)
C40.027 (3)0.026 (3)0.022 (3)−0.002 (2)0.010 (2)0.000 (2)
C50.024 (3)0.028 (3)0.023 (3)0.003 (2)0.010 (2)−0.003 (2)
C60.018 (3)0.018 (3)0.018 (2)0.002 (2)0.006 (2)0.0031 (19)
C70.022 (3)0.025 (3)0.018 (3)0.000 (2)0.009 (2)−0.001 (2)
C80.022 (3)0.026 (3)0.025 (3)0.001 (2)0.013 (2)0.003 (2)
C90.059 (4)0.049 (4)0.048 (4)0.032 (4)0.032 (4)0.022 (3)
C100.085 (6)0.075 (5)0.054 (5)0.054 (5)0.037 (4)0.031 (4)
C110.065 (5)0.076 (5)0.039 (4)0.037 (4)0.024 (4)0.032 (4)
C120.039 (4)0.051 (4)0.032 (3)0.010 (3)0.019 (3)0.015 (3)
C130.020 (3)0.031 (3)0.021 (3)0.000 (2)0.006 (2)0.007 (2)
C140.022 (3)0.027 (3)0.019 (3)−0.007 (2)0.005 (2)−0.003 (2)
C150.042 (4)0.036 (4)0.021 (3)0.001 (3)0.008 (3)−0.007 (2)
C160.053 (5)0.041 (4)0.029 (3)0.004 (3)0.011 (3)−0.014 (3)
C170.040 (4)0.028 (3)0.034 (3)0.010 (3)0.010 (3)−0.002 (3)
C180.020 (3)0.023 (3)0.023 (3)−0.001 (2)0.002 (2)−0.001 (2)
Geometric parameters (Å, °) top
Zn1—O11.983 (4)C4—C51.367 (8)
Zn1—N12.045 (5)C4—H40.9500
Zn1—N42.109 (5)C5—C61.412 (8)
Zn1—N62.112 (5)C5—H50.9500
Zn1—S12.3911 (15)C6—C71.423 (7)
S1—C81.746 (6)C7—H70.9500
O1—C11.329 (7)C9—C101.381 (10)
O2—C31.354 (6)C9—H90.9500
O2—H20.8400C10—C111.370 (12)
N1—C71.306 (7)C10—H100.9500
N1—N21.403 (6)C11—C121.367 (10)
N2—C81.310 (7)C11—H110.9500
N3—C81.355 (7)C12—C131.387 (8)
N3—H310.8800C12—H120.9500
N3—H320.8800C13—C141.505 (8)
N4—C91.338 (8)C14—C151.393 (8)
N4—C131.346 (8)C15—C161.382 (10)
N6—C181.333 (7)C15—H150.9500
N6—C141.340 (7)C16—C171.380 (9)
C1—C21.408 (7)C16—H160.9500
C1—C61.437 (7)C17—C181.373 (9)
C2—C31.389 (8)C17—H170.9500
C2—H2A0.9500C18—H180.9500
C3—C41.385 (8)
O1—Zn1—N190.29 (16)C6—C5—H5118.7
O1—Zn1—N4102.37 (18)C5—C6—C7116.2 (5)
N1—Zn1—N4100.70 (19)C5—C6—C1118.6 (5)
O1—Zn1—N693.82 (16)C7—C6—C1125.1 (5)
N1—Zn1—N6175.77 (18)N1—C7—C6125.5 (5)
N4—Zn1—N677.46 (19)N1—C7—H7117.2
O1—Zn1—S1146.42 (12)C6—C7—H7117.2
N1—Zn1—S181.14 (13)N2—C8—N3115.8 (5)
N4—Zn1—S1111.10 (15)N2—C8—S1126.5 (4)
N6—Zn1—S195.92 (13)N3—C8—S1117.6 (4)
C8—S1—Zn192.73 (19)N4—C9—C10121.7 (7)
C1—O1—Zn1128.1 (3)N4—C9—H9119.1
C3—O2—H2109.5C10—C9—H9119.1
C7—N1—N2114.5 (5)C11—C10—C9119.2 (7)
C7—N1—Zn1125.7 (4)C11—C10—H10120.4
N2—N1—Zn1119.5 (3)C9—C10—H10120.4
C8—N2—N1112.9 (5)C10—C11—C12120.0 (7)
C8—N3—H31120.0C10—C11—H11120.0
C8—N3—H32120.0C12—C11—H11120.0
H31—N3—H32120.0C11—C12—C13118.1 (7)
C9—N4—C13118.5 (5)C11—C12—H12121.0
C9—N4—Zn1124.9 (5)C13—C12—H12121.0
C13—N4—Zn1116.5 (4)N4—C13—C12122.4 (6)
C18—N6—C14118.9 (5)N4—C13—C14114.3 (5)
C18—N6—Zn1125.2 (4)C12—C13—C14123.2 (6)
C14—N6—Zn1115.8 (4)N6—C14—C15121.5 (6)
O1—C1—C2119.8 (5)N6—C14—C13115.6 (5)
O1—C1—C6123.2 (5)C15—C14—C13122.9 (5)
C2—C1—C6117.0 (5)C16—C15—C14118.7 (6)
C3—C2—C1122.2 (5)C16—C15—H15120.6
C3—C2—H2A118.9C14—C15—H15120.6
C1—C2—H2A118.9C17—C16—C15119.3 (6)
O2—C3—C4117.3 (5)C17—C16—H16120.3
O2—C3—C2122.4 (5)C15—C16—H16120.3
C4—C3—C2120.3 (5)C18—C17—C16118.5 (6)
C5—C4—C3119.2 (5)C18—C17—H17120.8
C5—C4—H4120.4C16—C17—H17120.8
C3—C4—H4120.4N6—C18—C17123.0 (5)
C4—C5—C6122.6 (5)N6—C18—H18118.5
C4—C5—H5118.7C17—C18—H18118.5
O1—Zn1—S1—C8−95.8 (3)C4—C5—C6—C1−2.5 (8)
N1—Zn1—S1—C8−18.8 (2)O1—C1—C6—C5−178.1 (5)
N4—Zn1—S1—C879.3 (2)C2—C1—C6—C53.3 (7)
N6—Zn1—S1—C8158.1 (2)O1—C1—C6—C7−0.7 (8)
N1—Zn1—O1—C115.3 (4)C2—C1—C6—C7−179.2 (5)
N4—Zn1—O1—C1−85.8 (4)N2—N1—C7—C6−178.8 (5)
N6—Zn1—O1—C1−163.8 (4)Zn1—N1—C7—C67.3 (8)
S1—Zn1—O1—C189.5 (5)C5—C6—C7—N1180.0 (5)
O1—Zn1—N1—C7−13.1 (5)C1—C6—C7—N12.5 (9)
N4—Zn1—N1—C789.5 (5)N1—N2—C8—N3−178.7 (5)
S1—Zn1—N1—C7−160.5 (5)N1—N2—C8—S1−1.0 (7)
O1—Zn1—N1—N2173.2 (4)Zn1—S1—C8—N217.3 (5)
N4—Zn1—N1—N2−84.1 (4)Zn1—S1—C8—N3−165.0 (4)
S1—Zn1—N1—N225.8 (4)C13—N4—C9—C10−0.5 (12)
C7—N1—N2—C8163.9 (5)Zn1—N4—C9—C10178.0 (7)
Zn1—N1—N2—C8−21.8 (6)N4—C9—C10—C110.7 (15)
O1—Zn1—N4—C992.1 (6)C9—C10—C11—C12−0.8 (16)
N1—Zn1—N4—C9−0.5 (6)C10—C11—C12—C130.6 (13)
N6—Zn1—N4—C9−176.7 (6)C9—N4—C13—C120.3 (10)
S1—Zn1—N4—C9−85.1 (6)Zn1—N4—C13—C12−178.3 (5)
O1—Zn1—N4—C13−89.4 (4)C9—N4—C13—C14179.5 (6)
N1—Zn1—N4—C13177.9 (4)Zn1—N4—C13—C140.9 (6)
N6—Zn1—N4—C131.8 (4)C11—C12—C13—N4−0.4 (10)
S1—Zn1—N4—C1393.4 (4)C11—C12—C13—C14−179.5 (7)
O1—Zn1—N6—C18−78.4 (4)C18—N6—C14—C152.6 (8)
N4—Zn1—N6—C18179.8 (5)Zn1—N6—C14—C15−173.4 (5)
S1—Zn1—N6—C1869.4 (4)C18—N6—C14—C13−177.6 (5)
O1—Zn1—N6—C1497.3 (4)Zn1—N6—C14—C136.4 (6)
N4—Zn1—N6—C14−4.6 (4)N4—C13—C14—N6−4.9 (7)
S1—Zn1—N6—C14−114.9 (4)C12—C13—C14—N6174.3 (6)
Zn1—O1—C1—C2167.2 (4)N4—C13—C14—C15174.9 (6)
Zn1—O1—C1—C6−11.3 (7)C12—C13—C14—C15−5.9 (9)
O1—C1—C2—C3179.0 (5)N6—C14—C15—C16−0.7 (10)
C6—C1—C2—C3−2.4 (8)C13—C14—C15—C16179.5 (6)
C1—C2—C3—O2−179.6 (5)C14—C15—C16—C17−1.7 (11)
C1—C2—C3—C40.3 (8)C15—C16—C17—C182.3 (11)
O2—C3—C4—C5−179.3 (5)C14—N6—C18—C17−2.0 (9)
C2—C3—C4—C50.7 (8)Zn1—N6—C18—C17173.5 (5)
C3—C4—C5—C60.4 (9)C16—C17—C18—N6−0.5 (10)
C4—C5—C6—C7179.9 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.841.852.625 (5)153
N3—H32···N2ii0.882.152.936 (7)148
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.841.852.625 (5)153
N3—H32···N2ii0.882.152.936 (7)148
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2.
Acknowledgements top

The authors thank the Ministry of Science and Technology (grant No. ESc 02-02-11-SF0033) for supporting this study; KWT thanks the Ministry of Higher Education for an SLAI scholarship.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tan, K. W., Ng, C. H., Maah, M. J. & Ng, S. W. (2009). Acta Cryst. E65, m61–m62.

Westrip, S. P. (2009). publCIF. In preparation.