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Acta Cryst. (2009). E65, m219-m220    [ doi:10.1107/S1600536809001949 ]

trans-Bis[acetone (2-hydroxybenzoyl)hydrazonato-[kappa]2N',O]bis(pyridine-[kappa]N)zinc(II)

M.-X. Yang, S. Lin, L.-J. Chen and X.-H. Chen

Abstract top

In the title compound, [Zn(C10H11N2O2)2(C5H5N)2], the ZnII atom lies on an inversion centre, and is coordinated in a distorted octahedral geometry by two carbonyl O atoms and two imino N atoms from two anionic bidentate acetone (2-hydroxybenzoyl)hydrazone ligands and by two N atoms from two pyridine molecules. The hydroxyl group acts as a donor, forming an intramolecular O-H...N hydrogen bond.

Comment top

Hydrazones have been attracting much attention by chemists in recent years because of their biological activities, chemical and industrial versatility, and strong tendency to chelate transition metals (Bai et al., 2006; Grove et al., 2004), lanthanide metals (Ma et al., 1989) and main group metals (Gao et al., 1998; Liu & Gao, 1998). In particular, salicyloylhydrazone can be very flexible and finely tuned at the molecular level to take versatile bonding modes. It can act as a bi-, tri-, tetra- and even pentadentate ligand. A number of zinc(II) complexes with salicyloylhydrazone ligands have been studied (Hu et al., 2006; Hu et al., 2007; Li et al., 2006; Samanta et al., 2007; Wu et al., 2006). As an extension of the work on the structural characterization of salicyloylhydrazone complexes, the preparation and crystal structure of the title zinc(II) complex are reported here.

The molecular structure of the title compound is shown in Fig. 1. The ZnII atom lies on an inversion centre and has an axially elongated octahedral coordination geometry. The two carbonyl O atoms and the two imino N atoms make up the equatorial plane and the two N atoms of two pyridine molecules occupy the axial positions at longer distances (Table 1). Double-bond character is present in C7—N1 and C8—N2, as judged from their bond lengths [1.322 (2) and 1.286 (2) Å] (Domiano et al., 1975; Liu et al., 1999; Xiao et al., 2000). The C7—O2 bond length of 1.273 (2) Å approaches the value of 1.263 Å expected for an enolic form of the hydrazone ligand (Chen & Liu, 2004; Wen et al., 2000). The data suggest enolization and deprotonation of the hydrazone groups, which is different from the analogous ZnII complex with the same ligand (Li et al., 2006). There exists an intramolecular O—H···N hydrogen bond (Table 2).

Related literature top

For general background, see: Bai et al. (2006); Gao et al. (1998); Grove et al. (2004); Liu & Gao (1998); Ma et al. (1989). For related structures, see: Chen & Liu (2004); Domiano et al. (1975); Hu et al. (2006, 2007); Li et al. (2006); Liu et al. (1999); Samanta et al. (2007); Wen et al. (2000); Wu et al. (2006); Xiao et al. (2000).

Experimental top

All reagents were commercially available and of analytical grade. To a solution of Zn(CH3COO)2.2H2O (0.110 g, 0.5 mmol) in pyridine (5 ml) was slowly added a suspension of acetone-N-salicyloylhydrazone (0.192 g, 1.0 mmol) in DMF(5 ml). The resulting red solution was stirred for 20 min and then filtered. After standing for 5 d, yellow crystals were separated from the filtrate.

Refinement top

H atoms bonded to C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) and 0.96 (CH3) Å and with Uiso(H) = xUeq(C), where x=1.2 for aromatic and 1.5 for methyl H atoms. H atom of the hydroxyl group was located in difference Fourier map and refined isotropically with its coordinates fixed.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) 1 - x, -y, -z.]
trans-Bis[acetone (2-hydroxybenzoyl)hydrazonato-κ2N',O]bis(pyridine- κN)zinc(II) top
Crystal data top
[Zn(C10H11N2O2)2(C5H5N)2]F(000) = 632
Mr = 605.99Dx = 1.370 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3282 reflections
a = 7.8225 (8) Åθ = 2.3–27.5°
b = 10.0381 (10) ŵ = 0.88 mm−1
c = 18.8201 (18) ÅT = 293 K
β = 96.21 (4)°Block, yellow
V = 1469.1 (3) Å30.35 × 0.26 × 0.15 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2334 reflections with I > 2σ(I)
Radiation source: 18 kW rotation anodeRint = 0.034
graphiteθmax = 27.5°, θmin = 2.3°
ω scansh = 0→10
13028 measured reflectionsk = 0→13
3282 independent reflectionsl = −24→24
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 0.98 w = 1/[σ2(Fo2) + (0.058P)2]
where P = (Fo2 + 2Fc2)/3
3282 reflections(Δ/σ)max < 0.001
188 parametersΔρmax = 0.38 e Å−3
0 restraintsΔρmin = −0.33 e Å−3
Crystal data top
[Zn(C10H11N2O2)2(C5H5N)2]V = 1469.1 (3) Å3
Mr = 605.99Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.8225 (8) ŵ = 0.88 mm−1
b = 10.0381 (10) ÅT = 293 K
c = 18.8201 (18) Å0.35 × 0.26 × 0.15 mm
β = 96.21 (4)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2334 reflections with I > 2σ(I)
13028 measured reflectionsRint = 0.034
3282 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.097Δρmax = 0.38 e Å−3
S = 0.98Δρmin = −0.33 e Å−3
3282 reflectionsAbsolute structure: ?
188 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.50000.00000.00000.04214 (12)
O10.4610 (2)0.49143 (15)0.11896 (11)0.0690 (5)
H10.51710.42150.09260.113 (11)*
O20.35166 (17)0.09309 (14)0.06705 (8)0.0492 (3)
N10.5358 (2)0.27234 (16)0.06295 (8)0.0423 (4)
N20.6294 (2)0.19207 (16)0.02003 (8)0.0433 (4)
N30.6638 (2)−0.09222 (17)0.09654 (9)0.0469 (4)
C10.2948 (2)0.2914 (2)0.12902 (10)0.0435 (4)
C20.3302 (3)0.4273 (2)0.14421 (11)0.0525 (5)
C30.2284 (4)0.4958 (3)0.18860 (14)0.0694 (7)
H3A0.24840.58590.19770.083*
C40.1004 (4)0.4326 (3)0.21861 (15)0.0755 (8)
H4A0.03720.47900.24960.091*
C50.0628 (4)0.3007 (3)0.20383 (15)0.0753 (7)
H5A−0.02670.25870.22370.090*
C60.1600 (3)0.2321 (2)0.15905 (12)0.0567 (5)
H6A0.13420.14330.14870.068*
C70.3987 (2)0.21174 (19)0.08292 (10)0.0397 (4)
C80.7671 (3)0.2453 (2)0.00115 (12)0.0511 (5)
C90.8255 (3)0.3833 (2)0.02229 (16)0.0741 (7)
H9A0.74570.42260.05150.111*
H9B0.83080.4364−0.01980.111*
H9C0.93740.37920.04870.111*
C100.8761 (3)0.1689 (3)−0.04426 (17)0.0835 (9)
H10A0.82620.0826−0.05430.125*
H10B0.98930.1587−0.01950.125*
H10C0.88330.2159−0.08830.125*
C110.7532 (3)−0.0149 (2)0.14528 (13)0.0584 (6)
H11A0.74480.07710.14010.070*
C120.8567 (3)−0.0653 (3)0.20266 (13)0.0659 (7)
H12A0.9172−0.00820.23520.079*
C130.8699 (3)−0.2014 (3)0.21143 (13)0.0647 (6)
H13A0.9398−0.23800.24960.078*
C140.7773 (3)−0.2813 (2)0.16238 (13)0.0624 (6)
H14A0.7824−0.37350.16670.075*
C150.6764 (3)−0.2228 (2)0.10655 (12)0.0549 (5)
H15A0.6134−0.27810.07390.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.04131 (17)0.03917 (18)0.04726 (19)−0.01003 (14)0.01086 (12)−0.00788 (15)
O10.0754 (11)0.0435 (8)0.0881 (12)−0.0109 (8)0.0086 (10)−0.0158 (9)
O20.0496 (7)0.0406 (7)0.0606 (9)−0.0129 (6)0.0201 (6)−0.0087 (7)
N10.0429 (8)0.0400 (8)0.0437 (8)−0.0079 (7)0.0031 (7)−0.0041 (7)
N20.0410 (8)0.0441 (9)0.0447 (9)−0.0106 (7)0.0046 (7)−0.0030 (7)
N30.0466 (9)0.0486 (10)0.0449 (9)−0.0068 (8)0.0024 (7)−0.0018 (8)
C10.0495 (10)0.0437 (10)0.0360 (9)0.0032 (9)−0.0008 (8)−0.0007 (8)
C20.0589 (12)0.0486 (12)0.0476 (12)0.0048 (11)−0.0056 (10)−0.0054 (10)
C30.0841 (17)0.0553 (14)0.0669 (15)0.0167 (14)−0.0013 (13)−0.0165 (13)
C40.0821 (18)0.0784 (19)0.0683 (16)0.0286 (16)0.0177 (14)−0.0098 (14)
C50.0811 (17)0.0750 (18)0.0756 (17)0.0154 (15)0.0344 (14)0.0028 (14)
C60.0617 (13)0.0532 (13)0.0582 (13)0.0043 (11)0.0201 (10)0.0016 (11)
C70.0435 (9)0.0391 (9)0.0355 (9)−0.0050 (8)−0.0003 (7)−0.0001 (8)
C80.0447 (10)0.0505 (12)0.0587 (12)−0.0168 (9)0.0076 (9)0.0020 (10)
C90.0645 (14)0.0572 (15)0.102 (2)−0.0289 (12)0.0137 (14)0.0001 (14)
C100.0660 (15)0.0813 (19)0.111 (2)−0.0259 (14)0.0433 (15)−0.0134 (17)
C110.0641 (13)0.0516 (13)0.0571 (13)−0.0078 (11)−0.0041 (11)−0.0051 (10)
C120.0678 (15)0.0684 (16)0.0573 (14)−0.0087 (13)−0.0130 (12)−0.0074 (12)
C130.0652 (14)0.0717 (16)0.0536 (13)−0.0039 (13)−0.0107 (11)0.0098 (12)
C140.0699 (15)0.0526 (13)0.0626 (14)−0.0059 (12)−0.0032 (12)0.0078 (12)
C150.0588 (12)0.0526 (12)0.0511 (12)−0.0104 (11)−0.0039 (10)−0.0007 (10)
Geometric parameters (Å, °) top
Zn1—O2i2.0319 (14)C4—H4A0.9300
Zn1—O22.0319 (14)C5—C61.379 (3)
Zn1—N22.1912 (16)C5—H5A0.9300
Zn1—N2i2.1912 (16)C6—H6A0.9300
Zn1—N3i2.3013 (18)C8—C101.485 (3)
Zn1—N32.3013 (18)C8—C91.498 (3)
O1—C21.338 (3)C9—H9A0.9600
O1—H10.99C9—H9B0.9600
O2—C71.273 (2)C9—H9C0.9600
N1—C71.322 (2)C10—H10A0.9600
N1—N21.402 (2)C10—H10B0.9600
N2—C81.286 (2)C10—H10C0.9600
N3—C151.326 (3)C11—C121.374 (3)
N3—C111.339 (3)C11—H11A0.9300
C1—C61.384 (3)C12—C131.379 (4)
C1—C21.415 (3)C12—H12A0.9300
C1—C71.485 (3)C13—C141.369 (3)
C2—C31.396 (3)C13—H13A0.9300
C3—C41.359 (4)C14—C151.375 (3)
C3—H3A0.9300C14—H14A0.9300
C4—C51.378 (4)C15—H15A0.9300
O2i—Zn1—O2180.00 (6)C6—C5—H5A120.5
O2i—Zn1—N2103.14 (6)C5—C6—C1122.0 (2)
O2—Zn1—N276.86 (6)C5—C6—H6A119.0
O2i—Zn1—N2i76.86 (6)C1—C6—H6A119.0
O2—Zn1—N2i103.14 (6)O2—C7—N1125.93 (18)
N2—Zn1—N2i180.00 (9)O2—C7—C1118.57 (17)
O2i—Zn1—N3i90.07 (6)N1—C7—C1115.49 (17)
O2—Zn1—N3i89.93 (6)N2—C8—C10119.64 (19)
N2—Zn1—N3i89.38 (6)N2—C8—C9123.4 (2)
N2i—Zn1—N3i90.62 (6)C10—C8—C9116.92 (19)
O2i—Zn1—N389.93 (6)C8—C9—H9A109.5
O2—Zn1—N390.07 (6)C8—C9—H9B109.5
N2—Zn1—N390.62 (6)H9A—C9—H9B109.5
N2i—Zn1—N389.38 (6)C8—C9—H9C109.5
N3i—Zn1—N3180.00 (10)H9A—C9—H9C109.5
C2—O1—H1103.6H9B—C9—H9C109.5
C7—O2—Zn1113.95 (12)C8—C10—H10A109.5
C7—N1—N2112.91 (15)C8—C10—H10B109.5
C8—N2—N1115.16 (17)H10A—C10—H10B109.5
C8—N2—Zn1134.68 (15)C8—C10—H10C109.5
N1—N2—Zn1110.16 (11)H10A—C10—H10C109.5
C15—N3—C11116.73 (19)H10B—C10—H10C109.5
C15—N3—Zn1122.43 (14)N3—C11—C12123.0 (2)
C11—N3—Zn1120.83 (15)N3—C11—H11A118.5
C6—C1—C2118.3 (2)C12—C11—H11A118.5
C6—C1—C7119.76 (18)C11—C12—C13119.3 (2)
C2—C1—C7121.98 (19)C11—C12—H12A120.4
O1—C2—C3118.9 (2)C13—C12—H12A120.4
O1—C2—C1122.2 (2)C14—C13—C12118.2 (2)
C3—C2—C1119.0 (2)C14—C13—H13A120.9
C4—C3—C2120.8 (2)C12—C13—H13A120.9
C4—C3—H3A119.6C13—C14—C15118.9 (2)
C2—C3—H3A119.6C13—C14—H14A120.6
C3—C4—C5121.0 (3)C15—C14—H14A120.6
C3—C4—H4A119.5N3—C15—C14123.9 (2)
C5—C4—H4A119.5N3—C15—H15A118.0
C4—C5—C6118.9 (3)C14—C15—H15A118.0
C4—C5—H5A120.5
Symmetry codes: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.991.612.535 (2)154
Table 1
Selected geometric parameters (Å) top
Zn1—O22.0319 (14)Zn1—N32.3013 (18)
Zn1—N22.1912 (16)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.991.612.535 (2)154
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (grant No. 20771024), the Natural Science Foundation of Fujian Province (grant No. 2008 J0142) and the Foundation of the State Key Laboratory of Structural Chemistry (grant No. 070032).

references
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