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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o904–o905.
Published online 2010 March 24. doi:  10.1107/S1600536810010238
PMCID: PMC2983988

2,2′-{1,1′-[2,2′-Oxalylbis(hydrazin-2-yl-1-yl­idene)]diethyl­idyne}dipyridinium bis­(perchlorate) dihydrate

Abstract

The title salt, C16H18N6O2 2+·2ClO4 ·2H2O, was obtained unintentionally as a major product in the reaction of Zn(ClO4)2·6H2O with the N′,N2-bis­[(1E)-1-(2-pyrid­yl)ethyl­idene]ethanedihydrazide (H2 L) ligand. The (H4 L)2+ cation lies across a centre of inversion. The pyridiniumimine fragments of (H4 L)2+ adopt syn orientations. Intra­molecular N—H(...)N and N—H(...)O hydrogen bonds lead to the formation of S(5) motifs. In the crystal, neighbouring cations are connected by π–π inter­actions between pyridinium units with a centroid–centroid distance of 3.600 (1) Å. Moreover, the crystal components are assembled into two-dimensional layers via N—H(...)O and O—H(...)O hydrogen bonds, with no direct hydrogen-bonding inter­actions between cations.

Related literature

For the use of N′,N2-bis­[(1E)-1-(2-pyrid­yl)ethyl­idene]ethane­dihydrazide in reactions with metal ions, see: Anđelković et al. (2005 [triangle]); Kelly et al. (2005 [triangle]); Sen et al. (2006 [triangle]). For hydrogen bonds, see: Bernstein et al. (1995 [triangle]); Jeffrey et al. (1985 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o904-scheme1.jpg

Experimental

Crystal data

  • C16H18N6O2 2+·2ClO4 ·2H2O
  • M r = 561.3
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o904-efi1.jpg
  • a = 7.0166 (3) Å
  • b = 15.6855 (5) Å
  • c = 10.1152 (4) Å
  • β = 90.240 (3)°
  • V = 1113.26 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.37 mm−1
  • T = 130 K
  • 0.4 × 0.3 × 0.2 mm

Data collection

  • Oxford Diffraction XcaliburS CCD diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 [triangle]) T min = 0.875, T max = 0.929
  • 12596 measured reflections
  • 3402 independent reflections
  • 2504 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.105
  • S = 0.98
  • 3402 reflections
  • 173 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.69 e Å−3
  • Δρmin = −0.48 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010238/gk2261sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010238/gk2261Isup2.hkl

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

Acknowledgments

This work was supported by the Ministry of Science and Technological Development of the Republic of Serbia (grant 142026).

supplementary crystallographic information

Comment

N',N'2-Bis[(1E)-1-(2-pyridyl)ethylidene]ethanedihydrazide (H2L) is usually used for the preparation of metal complexes (Anđelković et al. 2005; Kelly et al. 2005; Sen et al., 2006). However, only two complexes, polynuclear complex of Cu(II) and mononuclear complex of Ni(II), with ligand H2L have been obtained and characterized so far (Sen et al., 2006). These complexes have been prepared by direct reaction of M(AcO)2 [M = Cu(II) and Ni(II)] with H2L in 2-propanol/H2O (Sen et al., 2006). However, in the reactions of H2L with Cu(NO3)2.3H2O or Cu(ClO4)2.6H2O in MeOH/H2O, hydrolysis at the hydrazide moiety occurred affording the formation of the binuclear Cu(II) complex with 2-acetylpyridine hydrazone in which oxalate ion serves as a bridge between two metal centers (Kelly et al., 2005). Similarly, hydrolysis of H2L took place in the reaction with Fe(ClO4)3.6H2O in water, with simultaneous reduction of Fe(III) to Fe(II) by oxalic fragment affording formation of mononuclear Fe(II) complex with 2-acetylpyridine hydrazone (Anđelković et al., 2005). The cited studies show that direct synthetic reactions of metal ions with the ligand H2L may be very intricate and often lead to accidental products. The title salt, (I), was obtained unintentionally as a major product in direct reaction of Zn(ClO4)2.6H2O with the ligand N',N'2-bis[(1E)-1-(2-pyridyl)ethylidene]ethanedihydrazide (H2L). The cation (H4L)2+ lies at the center of inversion at 1/2, 0, 0. The numbering scheme of (I) is given in Fig. 1. The C8—O1 bond distance of 1.214 (2) Å is consistent with the carbon–oxygen double bonding. The N3—C8 [1.352 (2) Å] and N2—C6 [1.289 (2) Å] bond distances indicate single and double CN bonding, respectively . The cation deviates from planarity. The distance between the mean plane defined by C1-C6,C8,N1-N3 atoms and that defined by respective symmetry related atoms is 0.223 Å. The structure of (I) is stabilized by intramolecular and intermolecular hydrogen bonds and their geometrical details are listed in Table 1. The s-trans conformation of the cation is stabilized by N–H···O hydrogen bonds (Fig. 1, Table 1). The torsion angle O1—C8—C8a—O1a [atoms labeled with the suffix "a" are at symmetry position 1–x, –y, –z] is 180°. The syn orientations of the pyridiniumimine fragments are stabilized by the N—H···N intramolecular hydrogen bonds. The torsion angle N1—C1—C6—N2 is 3.3 (2)°. The intramolecular hydrogen bonds (N–H···O and N—H···N) lead to formation of S(5) motifs (Fig. 1.) (Bernstein et al., 1995). In the crystal structure all residues participate in the intermolecular hydrogen bonding (Fig. 2.). Solvent water molecule acts as a double donor [to O1 and O3 at –x, y – 1/2, –z + 1/2] and a single acceptor. The pyridinium and hydrazone nitrogens serve as double hydrogen bond donors with one component intra and the other intermolecular. As suggested by Jeffrey et al., 1985, this type of H-bond is called three-center. Perchlorate groups and water molecules mediate in joining together the cation molecules (Fig. 2.). Each cation is H-bonded to two perchlorate groups and two water molecules. The oxygen atoms (O3 and O5) from perchlorate group serve as H-bond acceptors. The O5 accepts hydrogen from hydrazone nitrogen and O3 from water molecule. The other hydrogen from water molecule is being donated to carbonyl oxygen (O1) of cation molecule. This system of H-bond interactions spreads in two-dimensions parallel to (1 0 2). The heteroaromatic rings of the neighbouring cations are involved in π–π interactions (Fig. 3). The aromatic rings are found to be parallel-displaced. Namely, the distance between the centers of gravity of aromatic rings (C1—C5,N1) and (C1b—C5b,N1b) [atoms labeled with the suffix "b" are at symmetry position –x, –y, 1–z] is 3.600 (1) Å with the center of gravity displaced distance of 1.502 Å. Cation molecules connected by π–π interactions between pyridinium units extend in a stairs-like manner along [101].

Experimental

Zn(ClO4)2.6H2O (0.32 g, 0.85 mmol) and H2L (0.27 g, 0.85 mmol) were suspended in MeOH (30 cm3). To the light yellow suspension 4–5 drops of HClO4 were added and the resulting yellow solution was refluxed for 1 h at 338 K. Upon cooling to room temperature and filtration, a light yellow microcrystalline product was obtained. Yield: 56%; mp. 511–513 K; molar conductivity (DMF, 1.10 –3 mol dm–3) λM = 160 Ω–1cm2 mol–1. Solubility: insoluble in water and ethanol, soluble in acetonitrile and dimethylsulfoxide. The molar conductivity of a DMF solution of the ligand salt (1.10 –3 mol dm–3) was measured at room temperature on a Jenway-4009 digital conductivity meter.

Refinement

The H atoms connected to C atoms were positioned geometrically (C—H = 0.95 - 0.98 Å) and treated as riding on their carrier atoms with Uiso(H) = 1.2Ueq(C). H atoms at nitrogen were found in electron-density difference maps and refined freely. In order to adjust distances of hydrogen atoms of water molecule DFIX instruction was used with the target value of 0.84 (2) Å (O6—H). The crystal was pseudomerohedrally twinned with the twin law (1 0 0 0 -1 0 0 0 -1) in the reciprocal space. The refinement gave with the 6 % content of the minor component.

Figures

Fig. 1.
The numbering scheme in the title compound. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular hydrogen bonds(N—H···O and N—H···N) are shown with dashed lines. ...
Fig. 2.
Packing diagram of the title compound showing 2D assembly parallel to (1 0 2) generated by hydrogen bonding. Hydrogen atoms, except those involved in hydrogen bonding, are omitted for clarity.
Fig. 3.
Packing diagram of the title compound showing 1D assembly parallel to [–1 0 1] generated by stacking interactions of the pyridinium fragments. View along b-axis.

Crystal data

C16H18N6O22+·2ClO4·2H2OF(000) = 580
Mr = 561.3Dx = 1.674 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4422 reflections
a = 7.0166 (3) Åθ = 2.9–32.2°
b = 15.6855 (5) ŵ = 0.37 mm1
c = 10.1152 (4) ÅT = 130 K
β = 90.240 (3)°Plate, colourless
V = 1113.26 (7) Å30.4 × 0.3 × 0.2 mm
Z = 2

Data collection

Oxford Diffraction XcaliburS CCD diffractometer3402 independent reflections
graphite2504 reflections with I > 2σ(I)
Detector resolution: 16.356 pixels mm-1Rint = 0.037
ω scans and [var phi] scansθmax = 30.5°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)h = −9→10
Tmin = 0.875, Tmax = 0.929k = −22→20
12596 measured reflectionsl = −12→14

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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 0.98w = 1/[σ2(Fo2) + (0.0575P)2] where P = (Fo2 + 2Fc2)/3
3402 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.69 e Å3
2 restraintsΔρmin = −0.48 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
Cl1−0.06740 (7)0.17109 (3)0.03091 (5)0.02258 (12)
O10.5097 (2)−0.08816 (8)0.10597 (12)0.0239 (3)
O2−0.0958 (2)0.23504 (9)−0.06811 (15)0.0357 (4)
O3−0.2032 (3)0.18404 (10)0.13518 (17)0.0553 (6)
O4−0.0935 (2)0.08764 (8)−0.02205 (14)0.0331 (3)
O50.1188 (3)0.17823 (11)0.0853 (3)0.0705 (7)
O60.3496 (2)−0.14953 (9)0.35088 (15)0.0285 (3)
N10.2466 (2)−0.01871 (9)0.50693 (15)0.0167 (3)
N20.3686 (2)0.03179 (9)0.27403 (15)0.0190 (2)
N30.4253 (2)0.05006 (10)0.14877 (14)0.0190 (2)
C10.2678 (2)0.06619 (11)0.48485 (17)0.0168 (3)
C20.2139 (3)0.12184 (11)0.58310 (18)0.0206 (4)
H20.22780.18150.57050.025*
C30.1395 (3)0.09094 (12)0.70044 (18)0.0226 (4)
H30.10080.12950.76750.027*
C40.1214 (2)0.00423 (12)0.72004 (18)0.0214 (4)
H40.0714−0.01760.80040.026*
C50.1775 (2)−0.05004 (11)0.62031 (17)0.0193 (4)
H50.1672−0.110.6320.023*
C60.3414 (2)0.09391 (11)0.35522 (17)0.0174 (3)
C70.3775 (3)0.18669 (11)0.3335 (2)0.0271 (4)
H7A0.44240.19470.24880.041*
H7B0.45790.20880.40520.041*
H7C0.25590.21740.33230.041*
C80.4826 (2)−0.01508 (11)0.07098 (18)0.0188 (3)
H1N0.279 (3)−0.0545 (14)0.449 (2)0.026 (4)*
H3N0.401 (3)0.0985 (14)0.118 (2)0.026 (4)*
H6A0.388 (4)−0.1348 (17)0.2784 (19)0.049 (6)*
H6B0.295 (4)−0.1971 (13)0.351 (3)0.049 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0305 (2)0.01659 (19)0.0206 (2)0.00294 (16)0.00279 (17)0.00130 (16)
O10.0335 (7)0.0212 (6)0.0172 (7)0.0020 (5)0.0033 (5)0.0015 (5)
O20.0530 (10)0.0281 (7)0.0262 (8)0.0080 (7)0.0064 (7)0.0114 (6)
O30.1039 (16)0.0265 (8)0.0358 (10)0.0169 (9)0.0408 (10)0.0046 (7)
O40.0494 (9)0.0214 (7)0.0285 (8)−0.0010 (6)0.0064 (7)−0.0057 (6)
O50.0498 (12)0.0292 (9)0.132 (2)−0.0002 (8)−0.0469 (13)0.0052 (10)
O60.0401 (8)0.0207 (7)0.0247 (8)−0.0045 (6)0.0116 (6)−0.0010 (6)
N10.0174 (7)0.0175 (7)0.0153 (7)0.0006 (5)0.0009 (6)−0.0004 (5)
N20.0242 (6)0.0206 (5)0.0121 (5)0.0002 (4)0.0031 (4)0.0024 (4)
N30.0242 (6)0.0206 (5)0.0121 (5)0.0002 (4)0.0031 (4)0.0024 (4)
C10.0158 (8)0.0182 (8)0.0163 (8)0.0001 (6)0.0001 (6)0.0010 (6)
C20.0240 (9)0.0183 (8)0.0195 (9)0.0002 (6)0.0019 (7)−0.0013 (6)
C30.0258 (9)0.0258 (9)0.0161 (9)0.0000 (7)0.0011 (7)−0.0035 (7)
C40.0222 (9)0.0274 (9)0.0145 (8)−0.0003 (7)0.0016 (7)0.0035 (7)
C50.0193 (9)0.0207 (8)0.0180 (9)−0.0016 (6)−0.0011 (7)0.0038 (7)
C60.0170 (8)0.0195 (8)0.0156 (8)−0.0005 (6)0.0019 (6)0.0004 (6)
C70.0410 (12)0.0193 (9)0.0209 (10)−0.0028 (8)0.0097 (8)0.0014 (7)
C80.0192 (8)0.0219 (8)0.0151 (8)−0.0031 (6)0.0012 (6)−0.0016 (7)

Geometric parameters (Å, °)

Cl1—O51.4198 (17)C1—C21.377 (2)
Cl1—O41.4259 (14)C1—C61.477 (2)
Cl1—O21.4309 (14)C2—C31.386 (3)
Cl1—O31.4386 (17)C2—H20.95
O1—C81.214 (2)C3—C41.381 (3)
O6—H6A0.815 (17)C3—H30.95
O6—H6B0.839 (17)C4—C51.379 (3)
N1—C51.340 (2)C4—H40.95
N1—C11.359 (2)C5—H50.95
N1—H1N0.84 (2)C6—C71.493 (2)
N2—C61.289 (2)C7—H7A0.98
N2—N31.360 (2)C7—H7B0.98
N3—C81.352 (2)C7—H7C0.98
N3—H3N0.84 (2)C8—C8i1.532 (4)
O5—Cl1—O4109.55 (10)C4—C3—H3119.9
O5—Cl1—O2109.96 (11)C2—C3—H3119.9
O4—Cl1—O2111.30 (9)C5—C4—C3118.46 (17)
O5—Cl1—O3108.40 (14)C5—C4—H4120.8
O4—Cl1—O3108.69 (10)C3—C4—H4120.8
O2—Cl1—O3108.87 (9)N1—C5—C4120.35 (16)
H6A—O6—H6B114 (3)N1—C5—H5119.8
C5—N1—C1122.70 (15)C4—C5—H5119.8
C5—N1—H1N116.7 (15)N2—C6—C1113.35 (15)
C1—N1—H1N120.6 (15)N2—C6—C7128.13 (17)
C6—N2—N3118.61 (14)C1—C6—C7118.52 (15)
C8—N3—N2118.15 (15)C6—C7—H7A109.5
C8—N3—H3N122.0 (14)C6—C7—H7B109.5
N2—N3—H3N118.4 (15)H7A—C7—H7B109.5
N1—C1—C2118.18 (16)C6—C7—H7C109.5
N1—C1—C6118.26 (15)H7A—C7—H7C109.5
C2—C1—C6123.53 (16)H7B—C7—H7C109.5
C1—C2—C3120.13 (17)O1—C8—N3126.18 (17)
C1—C2—H2119.9O1—C8—C8i122.6 (2)
C3—C2—H2119.9N3—C8—C8i111.16 (18)
C4—C3—C2120.17 (17)
C6—N2—N3—C8169.62 (16)N3—N2—C6—C1176.07 (14)
C5—N1—C1—C2−0.7 (2)N3—N2—C6—C7−4.8 (3)
C5—N1—C1—C6−178.72 (16)N1—C1—C6—N23.3 (2)
N1—C1—C2—C3−0.3 (3)C2—C1—C6—N2−174.65 (17)
C6—C1—C2—C3177.63 (16)N1—C1—C6—C7−175.92 (16)
C1—C2—C3—C40.9 (3)C2—C1—C6—C76.1 (3)
C2—C3—C4—C5−0.5 (3)N2—N3—C8—O1−9.0 (3)
C1—N1—C5—C41.1 (3)N2—N3—C8—C8i172.93 (16)
C3—C4—C5—N1−0.5 (3)

Symmetry codes: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O60.84 (2)1.86 (2)2.690 (2)168 (2)
N1—H1N···N20.84 (2)2.32 (2)2.632 (2)102 (2)
N3—H3N···O50.84 (2)2.36 (2)3.011 (2)134 (2)
N3—H3N···O1i0.84 (2)2.36 (2)2.686 (2)104 (2)
O6—H6A···O10.82 (2)2.08 (2)2.889 (2)173 (2)
O6—H6A···N20.82 (2)2.62 (3)2.952 (2)106 (2)
O6—H6B···O3ii0.84 (2)1.98 (2)2.809 (2)171 (2)
C2—H2···O5iii0.952.333.206 (2)152
C4—H4···O4iv0.952.503.384 (2)155
C5—H5···O2ii0.952.563.460 (2)157
C7—H7A···N30.982.492.864 (2)103

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2261).

References

  • Anđelković, K., Sladić, D., Bacchi, A., Pelizzi, G., Filipović, N. & Rajković, M. (2005). Transition Met. Chem.30, 243–250.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Jeffrey, G. A., Małuszyńska, H. & Mitra, J. (1985). Int. J. Biol. Macromol.7, 336–348.
  • Kelly, T. L., Milway, V. A., Grove, H., Niel, V., Abedin, T. S. M., Thompson, L. K., Zhao, L., Harvey, R. G., Miller, D. O., Leech, M., Goeta, A. E. & Howard, J. A. K. (2005). Polyhedron, 24, 807–821.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Oxford Diffraction (2009). CrysAlis PRO Oxford Diffraction Ltd, Yarnton, England.
  • Sen, S., Choudhury, C. R., Talukder, P., Mitra, S., Westerhausen, M., Kneifel, A. N., Desplanches, C., Daro, N. & Sutter, J.-P. (2006). Polyhedron, 25, 1271–1278.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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