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

Kaluderović, G.N.; Mohamad Eshkourfu, R.O.; Gómez-Ruiz, S.; Mitić, D.; Andelković, K.K.

doi:10.1107/S1600536810010238

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages o904-o905

doi:10.1107/S1600536810010238

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

Goran N. Kaluderović,^a ^* Rabia O. Mohamad Eshkourfu,^b Santiago Gómez-Ruiz,^c Dragana Mitić ^b and Katarina K. Andelković ^b

^aDepartment of Chemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Studentski trg 14, 11000 Belgrade, Serbia, ^bFaculty of Chemistry, University of Belgrade, Studentski trg 16, 11000 Belgrade, Serbia, and ^cDepartamento de Química Inorgánica y Analìtica, E.S.C.E.T., Universidad Rey Juan Carlos, 28933 Móstoles, Madrid, Spain
^*Correspondence e-mail: goran@chem.bg.ac.rs

(Received 24 February 2010; accepted 18 March 2010; online 24 March 2010)

The title salt, C₁₆H₁₈N₆O₂²⁺·2ClO₄⁻·2H₂O, was obtained unintentionally as a major product in the reaction of Zn(ClO₄)₂·6H₂O with the N′,N′²-bis[(1E)-1-(2-pyridyl)ethylidene]ethanedihydrazide (H₂L) ligand. The (H₄L)²⁺ cation lies across a centre of inversion. The pyridiniumimine fragments of (H₄L)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′,N′²-bis[(1E)-1-(2-pyridyl)ethylidene]ethanedihydrazide in reactions with metal ions, see: Anđelković et al. (2005 ); Kelly et al. (2005 ); Sen et al. (2006 ). For hydrogen bonds, see: Bernstein et al. (1995 ); Jeffrey et al. (1985 ).

Experimental

Crystal data

C₁₆H₁₈N₆O₂²⁺·2ClO₄⁻·2H₂O
M_r = 561.3
Monoclinic, P 2₁ /c
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 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.105
S = 0.98
3402 reflections
173 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O6	0.84 (2)	1.86 (2)	2.690 (2)	168 (2)
N1—H1N⋯N2	0.84 (2)	2.32 (2)	2.632 (2)	102 (2)
N3—H3N⋯O5	0.84 (2)	2.36 (2)	3.011 (2)	134 (2)
N3—H3N⋯O1ⁱ	0.84 (2)	2.36 (2)	2.686 (2)	104 (2)
O6—H6A⋯O1	0.82 (2)	2.08 (2)	2.889 (2)	173 (2)
O6—H6B⋯O3ⁱⁱ	0.84 (2)	1.98 (2)	2.809 (2)	171 (2)
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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].

Related literature top

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

Experimental top

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) λ_M = 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.

Computing details top

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

Figures top

	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. Atoms labeled with the suffix "a" are at the symmetry position 1-x, -y, -z.
	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.

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

Crystal data top

C₁₆H₁₈N₆O₂²⁺·2ClO₄⁻·2H₂O	F(000) = 580
M_r = 561.3	D_x = 1.674 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4422 reflections
a = 7.0166 (3) Å	θ = 2.9–32.2°
b = 15.6855 (5) Å	µ = 0.37 mm⁻¹
c = 10.1152 (4) Å	T = 130 K
β = 90.240 (3)°	Plate, colourless
V = 1113.26 (7) Å³	0.4 × 0.3 × 0.2 mm
Z = 2

Data collection top

Oxford Diffraction XcaliburS CCD diffractometer	3402 independent reflections
Graphite monochromator	2504 reflections with I > 2σ(I)
Detector resolution: 16.356 pixels mm^-1	R_int = 0.037
ω scans and ϕ scans	θ_max = 30.5°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −9→10
T_min = 0.875, T_max = 0.929	k = −22→20
12596 measured reflections	l = −12→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0575P)²] where P = (F_o² + 2F_c²)/3
3402 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.69 e Å⁻³
2 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₁₆H₁₈N₆O₂²⁺·2ClO₄⁻·2H₂O	V = 1113.26 (7) Å³
M_r = 561.3	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0166 (3) Å	µ = 0.37 mm⁻¹
b = 15.6855 (5) Å	T = 130 K
c = 10.1152 (4) Å	0.4 × 0.3 × 0.2 mm
β = 90.240 (3)°

Data collection top

Oxford Diffraction XcaliburS CCD diffractometer	3402 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2504 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.929	R_int = 0.037
12596 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	2 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.69 e Å⁻³
3402 reflections	Δρ_min = −0.48 e Å⁻³
173 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	−0.06740 (7)	0.17109 (3)	0.03091 (5)	0.02258 (12)
O1	0.5097 (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)
O5	0.1188 (3)	0.17823 (11)	0.0853 (3)	0.0705 (7)
O6	0.3496 (2)	−0.14953 (9)	0.35088 (15)	0.0285 (3)
N1	0.2466 (2)	−0.01871 (9)	0.50693 (15)	0.0167 (3)
N2	0.3686 (2)	0.03179 (9)	0.27403 (15)	0.0190 (2)
N3	0.4253 (2)	0.05006 (10)	0.14877 (14)	0.0190 (2)
C1	0.2678 (2)	0.06619 (11)	0.48485 (17)	0.0168 (3)
C2	0.2139 (3)	0.12184 (11)	0.58310 (18)	0.0206 (4)
H2	0.2278	0.1815	0.5705	0.025*
C3	0.1395 (3)	0.09094 (12)	0.70044 (18)	0.0226 (4)
H3	0.1008	0.1295	0.7675	0.027*
C4	0.1214 (2)	0.00423 (12)	0.72004 (18)	0.0214 (4)
H4	0.0714	−0.0176	0.8004	0.026*
C5	0.1775 (2)	−0.05004 (11)	0.62031 (17)	0.0193 (4)
H5	0.1672	−0.11	0.632	0.023*
C6	0.3414 (2)	0.09391 (11)	0.35522 (17)	0.0174 (3)
C7	0.3775 (3)	0.18669 (11)	0.3335 (2)	0.0271 (4)
H7A	0.4424	0.1947	0.2488	0.041*
H7B	0.4579	0.2088	0.4052	0.041*
H7C	0.2559	0.2174	0.3323	0.041*
C8	0.4826 (2)	−0.01508 (11)	0.07098 (18)	0.0188 (3)
H1N	0.279 (3)	−0.0545 (14)	0.449 (2)	0.026 (4)*
H3N	0.401 (3)	0.0985 (14)	0.118 (2)	0.026 (4)*
H6A	0.388 (4)	−0.1348 (17)	0.2784 (19)	0.049 (6)*
H6B	0.295 (4)	−0.1971 (13)	0.351 (3)	0.049 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0305 (2)	0.01659 (19)	0.0206 (2)	0.00294 (16)	0.00279 (17)	0.00130 (16)
O1	0.0335 (7)	0.0212 (6)	0.0172 (7)	0.0020 (5)	0.0033 (5)	0.0015 (5)
O2	0.0530 (10)	0.0281 (7)	0.0262 (8)	0.0080 (7)	0.0064 (7)	0.0114 (6)
O3	0.1039 (16)	0.0265 (8)	0.0358 (10)	0.0169 (9)	0.0408 (10)	0.0046 (7)
O4	0.0494 (9)	0.0214 (7)	0.0285 (8)	−0.0010 (6)	0.0064 (7)	−0.0057 (6)
O5	0.0498 (12)	0.0292 (9)	0.132 (2)	−0.0002 (8)	−0.0469 (13)	0.0052 (10)
O6	0.0401 (8)	0.0207 (7)	0.0247 (8)	−0.0045 (6)	0.0116 (6)	−0.0010 (6)
N1	0.0174 (7)	0.0175 (7)	0.0153 (7)	0.0006 (5)	0.0009 (6)	−0.0004 (5)
N2	0.0242 (6)	0.0206 (5)	0.0121 (5)	0.0002 (4)	0.0031 (4)	0.0024 (4)
N3	0.0242 (6)	0.0206 (5)	0.0121 (5)	0.0002 (4)	0.0031 (4)	0.0024 (4)
C1	0.0158 (8)	0.0182 (8)	0.0163 (8)	0.0001 (6)	0.0001 (6)	0.0010 (6)
C2	0.0240 (9)	0.0183 (8)	0.0195 (9)	0.0002 (6)	0.0019 (7)	−0.0013 (6)
C3	0.0258 (9)	0.0258 (9)	0.0161 (9)	0.0000 (7)	0.0011 (7)	−0.0035 (7)
C4	0.0222 (9)	0.0274 (9)	0.0145 (8)	−0.0003 (7)	0.0016 (7)	0.0035 (7)
C5	0.0193 (9)	0.0207 (8)	0.0180 (9)	−0.0016 (6)	−0.0011 (7)	0.0038 (7)
C6	0.0170 (8)	0.0195 (8)	0.0156 (8)	−0.0005 (6)	0.0019 (6)	0.0004 (6)
C7	0.0410 (12)	0.0193 (9)	0.0209 (10)	−0.0028 (8)	0.0097 (8)	0.0014 (7)
C8	0.0192 (8)	0.0219 (8)	0.0151 (8)	−0.0031 (6)	0.0012 (6)	−0.0016 (7)

Geometric parameters (Å, º) top

Cl1—O5	1.4198 (17)	C1—C2	1.377 (2)
Cl1—O4	1.4259 (14)	C1—C6	1.477 (2)
Cl1—O2	1.4309 (14)	C2—C3	1.386 (3)
Cl1—O3	1.4386 (17)	C2—H2	0.95
O1—C8	1.214 (2)	C3—C4	1.381 (3)
O6—H6A	0.815 (17)	C3—H3	0.95
O6—H6B	0.839 (17)	C4—C5	1.379 (3)
N1—C5	1.340 (2)	C4—H4	0.95
N1—C1	1.359 (2)	C5—H5	0.95
N1—H1N	0.84 (2)	C6—C7	1.493 (2)
N2—C6	1.289 (2)	C7—H7A	0.98
N2—N3	1.360 (2)	C7—H7B	0.98
N3—C8	1.352 (2)	C7—H7C	0.98
N3—H3N	0.84 (2)	C8—C8ⁱ	1.532 (4)

O5—Cl1—O4	109.55 (10)	C4—C3—H3	119.9
O5—Cl1—O2	109.96 (11)	C2—C3—H3	119.9
O4—Cl1—O2	111.30 (9)	C5—C4—C3	118.46 (17)
O5—Cl1—O3	108.40 (14)	C5—C4—H4	120.8
O4—Cl1—O3	108.69 (10)	C3—C4—H4	120.8
O2—Cl1—O3	108.87 (9)	N1—C5—C4	120.35 (16)
H6A—O6—H6B	114 (3)	N1—C5—H5	119.8
C5—N1—C1	122.70 (15)	C4—C5—H5	119.8
C5—N1—H1N	116.7 (15)	N2—C6—C1	113.35 (15)
C1—N1—H1N	120.6 (15)	N2—C6—C7	128.13 (17)
C6—N2—N3	118.61 (14)	C1—C6—C7	118.52 (15)
C8—N3—N2	118.15 (15)	C6—C7—H7A	109.5
C8—N3—H3N	122.0 (14)	C6—C7—H7B	109.5
N2—N3—H3N	118.4 (15)	H7A—C7—H7B	109.5
N1—C1—C2	118.18 (16)	C6—C7—H7C	109.5
N1—C1—C6	118.26 (15)	H7A—C7—H7C	109.5
C2—C1—C6	123.53 (16)	H7B—C7—H7C	109.5
C1—C2—C3	120.13 (17)	O1—C8—N3	126.18 (17)
C1—C2—H2	119.9	O1—C8—C8ⁱ	122.6 (2)
C3—C2—H2	119.9	N3—C8—C8ⁱ	111.16 (18)
C4—C3—C2	120.17 (17)

C6—N2—N3—C8	169.62 (16)	N3—N2—C6—C1	176.07 (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—N2	3.3 (2)
N1—C1—C2—C3	−0.3 (3)	C2—C1—C6—N2	−174.65 (17)
C6—C1—C2—C3	177.63 (16)	N1—C1—C6—C7	−175.92 (16)
C1—C2—C3—C4	0.9 (3)	C2—C1—C6—C7	6.1 (3)
C2—C3—C4—C5	−0.5 (3)	N2—N3—C8—O1	−9.0 (3)
C1—N1—C5—C4	1.1 (3)	N2—N3—C8—C8ⁱ	172.93 (16)
C3—C4—C5—N1	−0.5 (3)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O6	0.84 (2)	1.86 (2)	2.690 (2)	168 (2)
N1—H1N···N2	0.84 (2)	2.32 (2)	2.632 (2)	102 (2)
N3—H3N···O5	0.84 (2)	2.36 (2)	3.011 (2)	134 (2)
N3—H3N···O1ⁱ	0.84 (2)	2.36 (2)	2.686 (2)	104 (2)
O6—H6A···O1	0.82 (2)	2.08 (2)	2.889 (2)	173 (2)
O6—H6A···N2	0.82 (2)	2.62 (3)	2.952 (2)	106 (2)
O6—H6B···O3ⁱⁱ	0.84 (2)	1.98 (2)	2.809 (2)	171 (2)
C2—H2···O5	0.95	2.33	3.206 (2)	152
C4—H4···O4ⁱⁱⁱ	0.95	2.50	3.384 (2)	155
C5—H5···O2ⁱⁱ	0.95	2.56	3.460 (2)	157
C7—H7A···N3	0.98	2.49	2.864 (2)	103

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₆O₂²⁺·2ClO₄⁻·2H₂O
M_r	561.3
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	130
a, b, c (Å)	7.0166 (3), 15.6855 (5), 10.1152 (4)
β (°)	90.240 (3)
V (Å³)	1113.26 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.4 × 0.3 × 0.2

Data collection
Diffractometer	Oxford Diffraction XcaliburS CCD diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.875, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	12596, 3402, 2504
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.105, 0.98
No. of reflections	3402
No. of parameters	173
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.48

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O6	0.84 (2)	1.86 (2)	2.690 (2)	168 (2)
N1—H1N···N2	0.84 (2)	2.32 (2)	2.632 (2)	102 (2)
N3—H3N···O5	0.84 (2)	2.36 (2)	3.011 (2)	134 (2)
N3—H3N···O1ⁱ	0.84 (2)	2.36 (2)	2.686 (2)	104 (2)
O6—H6A···O1	0.82 (2)	2.08 (2)	2.889 (2)	173 (2)
O6—H6B···O3ⁱⁱ	0.84 (2)	1.98 (2)	2.809 (2)	171 (2)

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

Acknowledgements

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

References

Anđelković, K., Sladić, D., Bacchi, A., Pelizzi, G., Filipović, N. & Rajković, M. (2005). Transition Met. Chem. 30, 243–250. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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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. Web of Science CSD CrossRef CAS Google Scholar
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Volume 66| Part 4| April 2010| Pages o904-o905

doi:10.1107/S1600536810010238

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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