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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): m219–m220.
Published online 2009 January 23. doi:  10.1107/S1600536809001949
PMCID: PMC2968143

trans-Bis[acetone (2-hydroxy­benzo­yl)hydrazonato-κ2 N′,O]bis­(pyridine-κN)zinc(II)

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0m219-scheme1.jpg

Experimental

Crystal data

  • [Zn(C10H11N2O2)2(C5H5N)2]
  • M r = 605.99
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m219-efi1.jpg
  • a = 7.8225 (8) Å
  • b = 10.0381 (10) Å
  • c = 18.8201 (18) Å
  • β = 96.21 (4)°
  • V = 1469.1 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.88 mm−1
  • T = 293 (2) K
  • 0.35 × 0.26 × 0.15 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: none
  • 13028 measured reflections
  • 3282 independent reflections
  • 2334 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.097
  • S = 0.98
  • 3282 reflections
  • 188 parameters
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.33 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001949/hy2173sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001949/hy2173Isup2.hkl

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

Acknowledgments

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).

supplementary crystallographic information

Comment

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).

Experimental

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

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.

Figures

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.]

Crystal data

[Zn(C10H11N2O2)2(C5H5N)2]F(000) = 632
Mr = 605.99Dx = 1.370 Mg m3
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 mm1
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

Rigaku R-AXIS RAPID diffractometer2334 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

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 = 0.98w = 1/[σ2(Fo2) + (0.058P)2] where P = (Fo2 + 2Fc2)/3
3282 reflections(Δ/σ)max < 0.001
188 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = −0.33 e Å3

Special details

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)

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)

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, °)

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, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.991.612.535 (2)154

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2173).

References

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