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The di­chloro­methane disolvate of 4,4'-(azino­di­methyl­ene)­dipyridinium chloranilate, C12H12N42+·C6Cl2O42-·2CH2Cl2, con­sists of one-dimensional hydrogen-bonded molecular tapes that propagate along the [1\overline 20] direction. Both cations and anions lie across centres of inversion. The molecular tapes are planar but do not stack in the expected segregated manner, instead having chloranilate anions sandwiched between azine groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010302050X/bm1542sup1.cif
Contains datablocks I, BM1542

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010302050X/bm1542Isup2.hkl
Contains datablock I

CCDC reference: 226121

Comment top

The metal binding pyridyl group and central chromophore of 4-pyridinealdazine give it the properties needed for use in surface enhanced resonance Raman scattering, and as such it has been used in our laboratories for the detection of explosive traces (McHugh et al., 2002) and to probe the nature of species bound to the surface of silver nanoparticles (Kennedy et al., 2003). These same features also make the azine a candidate for reaction with chloranilic acid. Work by Tomura and co-workers (Zaman et al., 1999, 2000, 2001; Akhtaruzzaman et al., 2002) suggests that a simple acid–base reaction should occur, giving a strongly hydrogen-bonded stucture. We wished to determine what effect, if any, this behaviour? would have on the nature of the chromophore.

Crystals grown using layering methods were shown to be the dichloromethene disolvate of a 1:1 complex, viz. 4,4'-azinodimethyldipyridinium chloranilate, (I), of the starting materials. Two different crystal morphologies, namely red needles and orange plates, were observed; these were found to give identical unit-cell parameters and so were attributed to the same phase. Both the cations and the anions lie on inversion centres (Fig. 1). The bond lengths (Table 2) of the chloranilate ring show that the C—C bonds between the O substituents are almost entirely single in character, whilst the C8—C9 bond has a high proportion of double-bond character, thus supporting the quinone formulation drawn. The geometry of the azine backbone does not seem to be altered by protonation of the pyridyl rings, being essentially identical to that observed in the neutral molecule (Ciurtin et al., 2001) and in AgI complexes (Kennedy et al., 2003). The only difference is a marked widening of the ring

## AUTHOR: Should this be C2—N2—C6 ?

C4—N2—C5 angle from 116.3 to 122.2 (3) ° upon protonation, thus leaving the protonated azine geometrically identical to the state found in its diperchlorate salt (Chen et al., 1997).

The cations and anions are linked by asymmetric bifurcated hydrogen bonds of the R21(5) type to give one-dimensional molecular tapes running along the 1 − 2 0 direction. This agrees with the predictions of earlier work on such chloranilate complexes, although with a N2···O2 distance of 2.584 (4) Å the dominant leg of the hydrogen bond is shorter than those seen previously (Zaman et al., 2001). We note a small electron density peak

## AUTHOR: give height of this peak? of ?.?? eÅ−3 at 1.05 Å from atom O2, suggesting that atom H2N, the H atom involved in this bond, may not exhibit full occupancy of the site bonded to atom N2. Indeed, an alternative model with full isotropic refinement of the H atoms moves atom H2 to a position intermediate between atoms N2 and O2 and gives it a Uiso value 3–4 times larger than those of the other H atoms. This fact may indicate that this strong interaction is based on an equilibrium between N—H···O and N···H—O interactions. The O1—C7 and O2—C8 distances [1.243 (4) and 1.274 (4) Å] indicate that, as expected, the hydrogen bonding is dominated by the group with the most single-bond character. Both the constituents of the molecular tape are planar, and there is an angle of only 5.4 (3)° between the chloranilate and pyridyl ring planes. Zaman et al. (2001) state that such planar tapes should give segregated stacks of donor and acceptor ions. However, in this case, it is clear that (I) stacks with alternate donor and acceptor groups (Fig. 2). As all previous work was based on bipyridyls with carbon backbones, this behaviour may be due to the heteroatomic nature of the azine link between the pyridyl rings. However, no significant azine-to-chloranilate intermolecular interactions are found, and only the Cl atoms form contacts [Cl1···Cl1 = 3.280 (2) Å] that are significantly shorter than the sum of the relevant van der Waals radii (Bondi, 1964).

Experimental top

The title compound was isolated in 80% yield by addition of equimolar solutions of chloranilic acid in acetone and 4-pyridinealdazine in dichloromethane. After stirring for 30 min, the purple product was isolated by filtration as a powder. Suitable crystals were grown over a period of 2 d by careful layering of the acetone solution onto the dichloromethane solution.

## AUTHOR: Purple product here but red crystal later ??

## AUTHOR: Mixtures of acetone and chlorocarbon solvents are potentially ## dangerous due to strongly exothermic acid- or base-catalysed ## reactions (e.g., acetone/chloroform). ## What precautions were taken here?

Refinement top

The sample consisted largely of non-singular fragments. The crystal used was a fragment cut from a larger non-single-crystal, but still many of the peaks were badly split. Although most of the frames could be processed successfully, inclusion of one of the runs degraded the quality of the overall dataset. It has therefore been omitted, leading to a slightly low completeness of 0.973. A l l H atoms were located by difference synthesis but were included in the final model only in calculated positions and in riding modes [Uiso(H) = 1.2Ueq(parent), N—H = 0.88 Å, C—H = 0.99 Å (methylene) and C—H = 0.95 Å (other H atoms)].

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997); COLLECT (Hooft, 1988); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1]
[Figure 2]
Figure 1. Molecular structure of the title compound, with 50% probability displacement ellipsoids. Atoms marked with an asterisk (*) are at the symmetry position (-x, 1 − y, 1 − z).

## AUTHOR: Need to show both dichloromethanes to maintain correct stoichiometry.

Figure 2. Packing diagram of the title compound showing the alternating donor and acceptor groups within each stack. Solvent molecules have been omitted for clarity.
(I) top
Crystal data top
C12H12N42+·C6Cl2O42·2CH2Cl2Z = 1
Mr = 589.07F(000) = 298
Triclinic, P1Dx = 1.641 Mg m3
a = 7.6066 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.7846 (9) ÅCell parameters from 2303 reflections
c = 9.3316 (11) Åθ = 2.9–27.0°
α = 99.918 (4)°µ = 0.76 mm1
β = 95.556 (4)°T = 123 K
γ = 101.534 (5)°Plate fragment, red
V = 596.23 (12) Å30.25 × 0.12 × 0.05 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
1336 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.091
Graphite monochromatorθmax = 27.7°, θmin = 3.0°
ω and ϕ scansh = 99
8528 measured reflectionsk = 1111
2472 independent reflectionsl = 1111
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H-atom parameters constrained
S = 0.98 w = 1/[σ2(Fo2) + (0.0596P)2]
where P = (Fo2 + 2Fc2)/3
2472 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
C12H12N42+·C6Cl2O42·2CH2Cl2γ = 101.534 (5)°
Mr = 589.07V = 596.23 (12) Å3
Triclinic, P1Z = 1
a = 7.6066 (9) ÅMo Kα radiation
b = 8.7846 (9) ŵ = 0.76 mm1
c = 9.3316 (11) ÅT = 123 K
α = 99.918 (4)°0.25 × 0.12 × 0.05 mm
β = 95.556 (4)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1336 reflections with I > 2σ(I)
8528 measured reflectionsRint = 0.091
2472 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.151H-atom parameters constrained
S = 0.98Δρmax = 0.43 e Å3
2472 reflectionsΔρmin = 0.49 e Å3
154 parameters
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.

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 > σ(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
xyzUiso*/Ueq
Cl10.56517 (15)0.45860 (12)0.84601 (12)0.0332 (3)
Cl20.29850 (17)0.98208 (14)0.09629 (14)0.0469 (4)
Cl30.03578 (18)0.70214 (16)0.06592 (16)0.0587 (5)
O10.3588 (4)0.2862 (3)0.3786 (3)0.0291 (7)
O20.4069 (4)0.2547 (3)0.6717 (3)0.0292 (7)
N10.0353 (4)0.4312 (4)0.4867 (4)0.0301 (9)
N20.2834 (4)0.0226 (4)0.5954 (4)0.0290 (9)
H2N0.32420.10980.59370.035*
C10.0727 (5)0.3857 (5)0.6067 (5)0.0309 (11)
H10.05170.44200.69750.037*
C20.2471 (6)0.0236 (5)0.4703 (5)0.0296 (11)
H20.26950.03470.38090.036*
C30.1766 (5)0.1570 (5)0.4698 (5)0.0269 (10)
H30.14720.18880.37980.032*
C40.1492 (5)0.2436 (5)0.6005 (5)0.0279 (11)
C50.1912 (6)0.1913 (5)0.7295 (5)0.0338 (12)
H50.17200.24790.82080.041*
C60.2600 (6)0.0588 (5)0.7248 (5)0.0329 (11)
H60.29130.02440.81300.040*
C70.4228 (5)0.3881 (5)0.4300 (5)0.0259 (10)
C80.4535 (5)0.3717 (5)0.5963 (5)0.0250 (10)
C90.5311 (5)0.4786 (5)0.6554 (4)0.0228 (9)
C100.2607 (6)0.7785 (5)0.0179 (5)0.0385 (12)
H10A0.34370.76320.05620.046*
H10B0.28820.71930.09540.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0433 (7)0.0337 (6)0.0265 (7)0.0197 (5)0.0033 (5)0.0041 (5)
Cl20.0651 (9)0.0430 (8)0.0342 (8)0.0180 (7)0.0100 (7)0.0033 (6)
Cl30.0537 (9)0.0651 (9)0.0481 (9)0.0106 (7)0.0079 (7)0.0117 (7)
O10.0339 (17)0.0294 (16)0.0302 (19)0.0188 (14)0.0041 (15)0.0086 (14)
O20.0340 (17)0.0268 (16)0.0318 (18)0.0187 (13)0.0085 (15)0.0033 (14)
N10.030 (2)0.027 (2)0.038 (3)0.0160 (17)0.0037 (19)0.0066 (18)
N20.033 (2)0.027 (2)0.031 (2)0.0161 (17)0.0070 (19)0.0058 (18)
C10.028 (2)0.028 (2)0.037 (3)0.011 (2)0.004 (2)0.002 (2)
C20.030 (2)0.026 (2)0.032 (3)0.007 (2)0.006 (2)0.003 (2)
C30.026 (2)0.027 (2)0.030 (3)0.0113 (19)0.004 (2)0.007 (2)
C40.027 (2)0.025 (2)0.035 (3)0.0126 (19)0.007 (2)0.006 (2)
C50.042 (3)0.033 (3)0.029 (3)0.018 (2)0.008 (2)0.001 (2)
C60.035 (3)0.038 (3)0.029 (3)0.015 (2)0.001 (2)0.009 (2)
C70.020 (2)0.027 (2)0.031 (3)0.0084 (19)0.005 (2)0.003 (2)
C80.021 (2)0.026 (2)0.030 (3)0.0097 (19)0.005 (2)0.0055 (19)
C90.028 (2)0.025 (2)0.019 (2)0.0141 (19)0.0003 (19)0.0048 (18)
C100.044 (3)0.035 (3)0.040 (3)0.019 (2)0.006 (2)0.006 (2)
Geometric parameters (Å, º) top
Cl1—C91.745 (4)C2—H20.9500
Cl2—C101.766 (4)C3—C41.379 (6)
Cl3—C101.758 (5)C3—H30.9500
O1—C71.243 (4)C4—C51.392 (6)
O2—C81.274 (4)C5—C61.364 (5)
N1—C11.278 (5)C5—H50.9500
N1—N1i1.411 (6)C6—H60.9500
N2—C21.324 (5)C7—C9ii1.424 (5)
N2—C61.340 (5)C7—C81.524 (6)
N2—H2N0.8800C8—C91.368 (5)
C1—C41.474 (5)C9—C7ii1.424 (5)
C1—H10.9500C10—H10A0.9900
C2—C31.383 (5)C10—H10B0.9900
C1—N1—N1i110.6 (4)N2—C6—C5119.8 (4)
C2—N2—C6122.2 (3)N2—C6—H6120.1
C2—N2—H2N118.9C5—C6—H6120.1
C6—N2—H2N118.9O1—C7—C9ii124.7 (4)
N1—C1—C4118.3 (4)O1—C7—C8118.4 (3)
N1—C1—H1120.8C9ii—C7—C8116.9 (4)
C4—C1—H1120.8O2—C8—C9124.2 (4)
N2—C2—C3119.9 (4)O2—C8—C7116.4 (3)
N2—C2—H2120.0C9—C8—C7119.4 (3)
C3—C2—H2120.0C8—C9—C7ii123.7 (4)
C4—C3—C2119.7 (4)C8—C9—Cl1118.9 (3)
C4—C3—H3120.1C7ii—C9—Cl1117.3 (3)
C2—C3—H3120.1Cl3—C10—Cl2111.6 (2)
C3—C4—C5118.3 (3)Cl3—C10—H10A109.3
C3—C4—C1122.2 (4)Cl2—C10—H10A109.3
C5—C4—C1119.6 (4)Cl3—C10—H10B109.3
C6—C5—C4120.0 (4)Cl2—C10—H10B109.3
C6—C5—H5120.0H10A—C10—H10B108.0
C4—C5—H5120.0
N1i—N1—C1—C4179.6 (4)C4—C5—C6—N21.4 (7)
C6—N2—C2—C32.4 (6)O1—C7—C8—O21.5 (6)
N2—C2—C3—C41.8 (6)C9ii—C7—C8—O2178.0 (3)
C2—C3—C4—C51.1 (6)O1—C7—C8—C9177.2 (4)
C2—C3—C4—C1179.3 (4)C9ii—C7—C8—C93.3 (6)
N1—C1—C4—C31.8 (6)O2—C8—C9—C7ii177.8 (4)
N1—C1—C4—C5180.0 (4)C7—C8—C9—C7ii3.6 (7)
C3—C4—C5—C60.9 (7)O2—C8—C9—Cl11.5 (6)
C1—C4—C5—C6179.2 (4)C7—C8—C9—Cl1179.9 (3)
C2—N2—C6—C52.2 (6)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O10.882.392.987 (4)126
N2—H2N···O20.881.762.584 (4)155

Experimental details

Crystal data
Chemical formulaC12H12N42+·C6Cl2O42·2CH2Cl2
Mr589.07
Crystal system, space groupTriclinic, P1
Temperature (K)123
a, b, c (Å)7.6066 (9), 8.7846 (9), 9.3316 (11)
α, β, γ (°)99.918 (4), 95.556 (4), 101.534 (5)
V3)596.23 (12)
Z1
Radiation typeMo Kα
µ (mm1)0.76
Crystal size (mm)0.25 × 0.12 × 0.05
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8528, 2472, 1336
Rint0.091
(sin θ/λ)max1)0.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.151, 0.98
No. of reflections2472
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.49

Computer programs: DENZO (Otwinowski & Minor, 1997); COLLECT (Hooft, 1988), DENZO and COLLECT, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
Cl1—C91.745 (4)N1—N1i1.411 (6)
O1—C71.243 (4)C7—C9ii1.424 (5)
O2—C81.274 (4)C7—C81.524 (6)
N1—C11.278 (5)C8—C91.368 (5)
C1—N1—N1i110.6 (4)O2—C8—C9124.2 (4)
N1—C1—C4118.3 (4)O2—C8—C7116.4 (3)
O1—C7—C9ii124.7 (4)C9—C8—C7119.4 (3)
O1—C7—C8118.4 (3)C8—C9—C7ii123.7 (4)
C9ii—C7—C8116.9 (4)
N1i—N1—C1—C4179.6 (4)N1—C1—C4—C31.8 (6)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O10.882.392.987 (4)126
N2—H2N···O20.881.762.584 (4)155
 

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