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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2672.
Published online 2009 October 10. doi:  10.1107/S1600536809040215
PMCID: PMC2971367

4,4′-(o-Phenyl­enedioxy­dimethyl­ene)dipyridinium dinitrate

Abstract

The cation of the salt, C18H18N2O2 2+·2NO3 , lies about a twofold rotation axis. The pyridinium ring is almost coplanar with the phenyl­ene ring [dihedral angle between rings = 5.69 (9)°]. The crystal structure shows π–π stacking inter­actions [centroid–centroid distance = 3.70 (1) Å] between the pyridinium rings and the phenyl­ene rings, generating a linear chain structure. The cation also forms two N—H(...)O hydrogen bonds to two nitrate groups.

Related literature

For general background to the title compound, see: Siaw-Lattey et al. (2005 [triangle]); Burchell et al. (2006 [triangle]). For the synthesis, see: Gao et al. (2004 [triangle]). For related structures, see Gao et al. (2006 [triangle], 2009a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2672-scheme1.jpg

Experimental

Crystal data

  • C18H18N2O2 2+·2NO3
  • M r = 418.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2672-efi1.jpg
  • a = 10.364 (6) Å
  • b = 19.7593 (11) Å
  • c = 9.996 (8) Å
  • β = 110.75 (2)°
  • V = 1914.2 (19) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 291 K
  • 0.40 × 0.22 × 0.16 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.955, T max = 0.981
  • 9339 measured reflections
  • 2195 independent reflections
  • 1203 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.144
  • S = 1.03
  • 2195 reflections
  • 140 parameters
  • 18 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 [triangle]); 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: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809040215/ng2647sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040215/ng2647Isup2.hkl

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

Acknowledgments

The authors thank the Specialized Research Funds for Technological Innovative Talent of Harbin (RC2009XK018007) and Heilongjiang University for supporting this study.

supplementary crystallographic information

Comment

Many poly-N-heterocyclic ligands coordinated with transition metal ions can form a variety of topology structures, including macrocycles, polyhedra and linear and helical polymers. Son's group have reported the synthesis of bis(pyridylether) ligand, which reacted with AgNO3, Cu(ClO4)2 and Co(NCS)2 to produce a helical metallopolymer, a bridged dinuclear complex and a monomeric octahedral complex, respectively. Puddephatt's group have investigated a series of silver complexes of two U-shaped bis(amidopyridyl) ligands, which assemble into macrocyclic and one-dimensional chain that are connected further into two- or three-dimensional structures by anion binding and hydrogen bonding. Our group has report three kinds of flexible pyridyl-based ligands in the previous report (Gao et al. 2006; Gao et al. 2009a; Gao et al. 2009b). As a part of our continuing research for bipyridyl aromatic ligands, we report the crystal structure of the title compound here.

In the title compound, the diprotonated 1,2-bis(4-pyridylmethoxy)benzene cation is centrosymmetric. The two terminal pyridyl rings lie in an almost coplane arrangement with the central benzene ring [dihedral angles of 5.69 (9)°]. The dihedral angle between the two pyridyl rings is 10.22 (8)° (Figure 1).

In the crystal packing structure, the πi—πi stacking interactions [distance of 3.70 (1) Å] existing between each spacer benzene ring and two adjacent pyridine rings from different ligands link the ligands into a one-dimensional chain structure. Furthermore, the uncoordinated nitrate anions are stabilized by the C—H···O hydrogen bonds (Figure 2, Table 1).

Experimental

The 1,2-bis(4-pyridylmethoxy)benzene was synthesized by the reaction of o-benzenediol and 4-chloromethylpyridine hydrochloride under nitrogen atmosphere and alkaline condition (Gao et al., 2004; Gao et al., 2006). Colorless block-shaped crystals of the title compound were obtained by slow evaporation of an ethanol solution after several days.

Refinement

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C). N-bond H atoms were located in a difference Fourier map and were refined freely.

Figures

Fig. 1.
The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms. [Symmetry codes: (i) 2 - x, y, 2.5 - z]
Fig. 2.
A partial packing view, showing the one-dimensional chain. Green dashed lines indicate the hydrogen bonds and red dashed lines indicate the πi—πi stacking interactions.

Crystal data

C18H18N2O22+·2NO3F(000) = 872
Mr = 418.36Dx = 1.452 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5255 reflections
a = 10.364 (6) Åθ = 3.0–24.5°
b = 19.7593 (11) ŵ = 0.12 mm1
c = 9.996 (8) ÅT = 291 K
β = 110.75 (2)°Block, brown
V = 1914.2 (19) Å30.40 × 0.22 × 0.16 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer2195 independent reflections
Radiation source: fine-focus sealed tube1203 reflections with I > 2σ(I)
graphiteRint = 0.049
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −13→13
Tmin = 0.955, Tmax = 0.981k = −23→25
9339 measured reflectionsl = −12→12

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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0652P)2 + 0.3119P] where P = (Fo2 + 2Fc2)/3
2195 reflections(Δ/σ)max < 0.001
140 parametersΔρmax = 0.28 e Å3
18 restraintsΔρmin = −0.17 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.
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)

xyzUiso*/Ueq
C10.8168 (3)0.12902 (14)0.7346 (3)0.0648 (7)
H10.78360.11780.63800.078*
C20.8406 (2)0.19528 (14)0.7751 (2)0.0601 (7)
H20.82290.22910.70630.072*
C30.8913 (2)0.21178 (12)0.9188 (2)0.0493 (6)
C40.9127 (3)0.16022 (12)1.0166 (3)0.0600 (7)
H40.94500.16991.11400.072*
C50.8867 (3)0.09496 (13)0.9712 (3)0.0668 (7)
H50.90120.06021.03770.080*
C60.9194 (3)0.28409 (12)0.9634 (2)0.0553 (6)
H6A0.99250.30170.93390.066*
H6B0.83720.31110.91880.066*
C70.9788 (2)0.34991 (10)1.1756 (2)0.0460 (5)
C80.9581 (2)0.41020 (12)1.1024 (3)0.0546 (6)
H80.92990.41041.00310.066*
C90.9797 (3)0.47065 (11)1.1773 (3)0.0580 (6)
H90.96630.51151.12810.070*
N10.8408 (2)0.08066 (13)0.8325 (2)0.0632 (6)
H100.830 (3)0.0347 (17)0.815 (3)0.095 (10)*
N20.7766 (2)−0.08567 (12)0.8502 (2)0.0687 (6)
O10.95913 (17)0.28718 (7)1.11369 (15)0.0572 (5)
O20.8126 (2)−0.05377 (9)0.96265 (19)0.0749 (6)
O30.7935 (2)−0.05844 (11)0.7449 (2)0.0908 (7)
O40.7253 (3)−0.14159 (13)0.8438 (3)0.1233 (10)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0624 (16)0.0818 (19)0.0516 (15)−0.0097 (14)0.0218 (13)−0.0211 (14)
C20.0659 (16)0.0697 (16)0.0447 (13)−0.0076 (13)0.0198 (12)−0.0086 (12)
C30.0474 (12)0.0563 (14)0.0430 (12)0.0003 (11)0.0144 (10)−0.0063 (10)
C40.0729 (16)0.0537 (15)0.0459 (13)0.0010 (12)0.0118 (12)−0.0072 (11)
C50.0736 (18)0.0551 (15)0.0630 (16)0.0005 (13)0.0133 (13)−0.0039 (13)
C60.0699 (15)0.0541 (14)0.0402 (12)0.0008 (12)0.0175 (11)−0.0006 (10)
C70.0501 (12)0.0382 (11)0.0470 (11)0.0006 (10)0.0139 (10)−0.0016 (10)
C80.0631 (15)0.0488 (13)0.0492 (13)−0.0002 (11)0.0164 (11)0.0049 (11)
C90.0645 (15)0.0406 (12)0.0691 (15)0.0020 (12)0.0237 (13)0.0076 (11)
N10.0598 (13)0.0607 (15)0.0666 (15)−0.0034 (11)0.0191 (11)−0.0199 (12)
N20.0808 (16)0.0634 (15)0.0523 (14)0.0062 (12)0.0120 (12)−0.0048 (12)
O10.0859 (11)0.0411 (9)0.0372 (8)−0.0022 (8)0.0125 (7)−0.0021 (6)
O20.1068 (15)0.0618 (11)0.0505 (11)−0.0016 (10)0.0208 (10)−0.0025 (9)
O30.1169 (16)0.1030 (16)0.0543 (12)0.0114 (13)0.0325 (11)−0.0007 (11)
O40.160 (2)0.0758 (15)0.1154 (19)−0.0354 (15)0.0251 (16)−0.0257 (13)

Geometric parameters (Å, °)

C1—N11.326 (4)C6—H6B0.9700
C1—C21.367 (4)C7—O11.368 (2)
C1—H10.9300C7—C81.375 (3)
C2—C31.383 (3)C7—C7i1.394 (4)
C2—H20.9300C8—C91.386 (3)
C3—C41.375 (3)C8—H80.9300
C3—C61.494 (3)C9—C9i1.362 (5)
C4—C51.362 (3)C9—H90.9300
C4—H40.9300N1—H100.92 (3)
C5—N11.327 (3)N2—O41.218 (3)
C5—H50.9300N2—O21.226 (3)
C6—O11.411 (3)N2—O31.249 (3)
C6—H6A0.9700
N1—C1—C2120.3 (2)C3—C6—H6B110.1
N1—C1—H1119.8H6A—C6—H6B108.4
C2—C1—H1119.8O1—C7—C8125.0 (2)
C1—C2—C3119.7 (2)O1—C7—C7i115.02 (11)
C1—C2—H2120.1C8—C7—C7i119.93 (14)
C3—C2—H2120.1C7—C8—C9119.6 (2)
C4—C3—C2118.1 (2)C7—C8—H8120.2
C4—C3—C6122.1 (2)C9—C8—H8120.2
C2—C3—C6119.8 (2)C9i—C9—C8120.45 (14)
C5—C4—C3120.1 (2)C9i—C9—H9119.8
C5—C4—H4120.0C8—C9—H9119.8
C3—C4—H4120.0C1—N1—C5121.4 (2)
N1—C5—C4120.4 (3)C1—N1—H10126 (2)
N1—C5—H5119.8C5—N1—H10112 (2)
C4—C5—H5119.8O4—N2—O2120.0 (3)
O1—C6—C3108.15 (19)O4—N2—O3122.4 (3)
O1—C6—H6A110.1O2—N2—O3117.6 (2)
C3—C6—H6A110.1C7—O1—C6117.47 (17)
O1—C6—H6B110.1

Symmetry codes: (i) −x+2, y, −z+5/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H10···O20.92 (3)2.34 (3)3.017 (3)130 (2)
N1—H10···O30.92 (3)1.96 (3)2.873 (3)170 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2647).

References

  • Burchell, T.-J., Eisler, D.-J. & Puddephatt, R.-J. (2006). Cryst. Growth Des.6, 974–982.
  • Gao, C.-M., Cao, D. & Zhu, L. (2004). Photogr. Sci. Photochem.22, 103–107.
  • Gao, J.-S., Liu, Y., Hou, G.-F., Yu, Y.-H. & Yan, P.-F. (2006). Acta Cryst. E62, o5645–o5646.
  • Gao, J.-S., Liu, Y., Zhang, S., Hou, G.-F. & Yan, P.-F. (2009a). Acta Cryst. E65, o2432. [PMC free article] [PubMed]
  • Gao, J.-S., Liu, Y., Zhang, S., Zuo, D.-F. & Hou, G.-F. (2009b). Acta Cryst. E65, o2457. [PMC free article] [PubMed]
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalClear Rigaku/MSC Inc., The Woodlands, Texas, USA.
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  • Siaw-Lattey, C., Zhang, H.-M. & Son, D.-Y. (2005). Polyhedron, 24, 785–790.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography