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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 11| November 2009| Page o2672
https://doi.org/10.1107/S1600536809040215

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

Ping Zou,a Shuang Zhang,b Ying Liu,b Jun Qiaob and Jin-Sheng Gaob*

aCollege of Life Science, Sichuan Agricultural University, Ya'an 625014, People's Republic of China, and bCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
*Correspondence e-mail: hgf1000@163.com

(Received 22 September 2009; accepted 2 October 2009; online 10 October 2009)

The cation of the salt, C18H18N2O22+·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[Siaw-Lattey, C., Zhang, H.-M. & Son, D.-Y. (2005). Polyhedron, 24, 785-790.]); Burchell et al. (2006[Burchell, T.-J., Eisler, D.-J. & Puddephatt, R.-J. (2006). Cryst. Growth Des. 6, 974-982.]). For the synthesis, see: Gao et al. (2004[Gao, C.-M., Cao, D. & Zhu, L. (2004). Photogr. Sci. Photochem. 22, 103-107.]). For related structures, see Gao et al. (2006[Gao, J.-S., Liu, Y., Hou, G.-F., Yu, Y.-H. & Yan, P.-F. (2006). Acta Cryst. E62, o5645-o5646.], 2009a[Gao, J.-S., Liu, Y., Zhang, S., Hou, G.-F. & Yan, P.-F. (2009a). Acta Cryst. E65, o2432.],b[Gao, J.-S., Liu, Y., Zhang, S., Zuo, D.-F. & Hou, G.-F. (2009b). Acta Cryst. E65, o2457.]).

[Scheme 1]

Experimental

Crystal data

  • C18H18N2O22+·2NO3−

  • Mr = 418.36

  • Monoclinic, C 2/c

  • 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.955, Tmax = 0.981

  • 9339 measured reflections

  • 2195 independent reflections

  • 1203 reflections with I > 2σ(I)

  • Rint = 0.049
Refinement

  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H10⋯O2 0.92 (3) 2.34 (3) 3.017 (3) 130 (2)
N1—H10⋯O3 0.92 (3) 1.96 (3) 2.873 (3) 170 (3)

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040215/ng2647Isup2.hkl

checkCIF report


Comment top

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).

Related literature top

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

Experimental top

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 top

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.

Structure description top

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).

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

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] 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]
[Figure 2] 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.
4,4'-(o-Phenylenedioxydimethylene)dipyridinium dinitrate top
Crystal data top
C18H18N2O22+·2NO3−F(000) = 872
Mr = 418.36Dx = 1.452 Mg m−3
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 mm−1
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 top
Rigaku R-AXIS RAPID
diffractometer		2195 independent reflections
Radiation source: fine-focus sealed tube1203 reflections with I > 2σ(I)
Graphite monochromatorRint = 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 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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 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 Å−3
18 restraintsΔρmin = −0.17 e Å−3
Crystal data top
C18H18N2O22+·2NO3−V = 1914.2 (19) Å3
Mr = 418.36Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.364 (6) ŵ = 0.12 mm−1
b = 19.7593 (11) ÅT = 291 K
c = 9.996 (8) Å0.40 × 0.22 × 0.16 mm
β = 110.75 (2)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2195 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1203 reflections with I > 2σ(I)
Tmin = 0.955, Tmax = 0.981Rint = 0.049
9339 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05518 restraints
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.28 e Å−3
2195 reflectionsΔρmin = −0.17 e Å−3
140 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
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) top
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, º) top
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 code: (i) −x+2, y, −z+5/2.
Hydrogen-bond geometry (Å, º) top
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)

Experimental details

Crystal data
Chemical formulaC18H18N2O22+·2NO3−
Mr418.36
Crystal system, space groupMonoclinic, C2/c
Temperature (K)291
a, b, c (Å)10.364 (6), 19.7593 (11), 9.996 (8)
β (°) 110.75 (2)
V (Å3)1914.2 (19)
Z4
Radiation typeMo Kα
µ (mm−1)0.12
Crystal size (mm)0.40 × 0.22 × 0.16
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.955, 0.981
No. of measured, independent and
observed [I > 2σ(I)] reflections		9339, 2195, 1203
Rint0.049
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.144, 1.03
No. of reflections2195
No. of parameters140
No. of restraints18
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.28, −0.17

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
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)
 

Acknowledgements

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

References

First citationBurchell, T.-J., Eisler, D.-J. & Puddephatt, R.-J. (2006). Cryst. Growth Des. 6, 974–982.  Web of Science CSD CrossRef CAS Google Scholar
 First citationGao, C.-M., Cao, D. & Zhu, L. (2004). Photogr. Sci. Photochem. 22, 103–107.  CAS Google Scholar
 First citationGao, J.-S., Liu, Y., Hou, G.-F., Yu, Y.-H. & Yan, P.-F. (2006). Acta Cryst. E62, o5645–o5646.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationGao, J.-S., Liu, Y., Zhang, S., Hou, G.-F. & Yan, P.-F. (2009a). Acta Cryst. E65, o2432.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationGao, J.-S., Liu, Y., Zhang, S., Zuo, D.-F. & Hou, G.-F. (2009b). Acta Cryst. E65, o2457.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationRigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSiaw-Lattey, C., Zhang, H.-M. & Son, D.-Y. (2005). Polyhedron, 24, 785–790.  Web of Science CSD CrossRef CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 11| November 2009| Page o2672
https://doi.org/10.1107/S1600536809040215
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