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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o68–o69.
Published online 2009 December 9. doi:  10.1107/S1600536809050831
PMCID: PMC2980244

4-(4-Pyrid­yl)pyridinium 3′,4,4′-tricarboxy­biphenyl-3-carboxyl­ate dihydrate

Abstract

In the title compound, C10H9N2 +·C16H9O8 ·2H2O, both the cation and anion possess crystallographically imposed centres of symmetry, causing the nitro­gen-bound H atom in the 4-(4-pyrid­yl)pyridinium cation and the acidic H atom of the carboxyl­ate groups at the 3 and 3′ positions in the anion to be disordered over two positions with equal occupancies. In the crystal packing, the cations, anions and water mol­ecules are connected by O—H(...)O, C—H(...)O and N—H(...)N hydrogen bonds, forming layers parallel to (2An external file that holds a picture, illustration, etc.
Object name is e-66-00o68-efi1.jpg0). These layer are further connected into a three-dimensional supra­molecular network by O—H(...)O hydrogen bonds involving the water mol­ecules as H-atom donors and by weak π–π stacking inter­actions between neighbouring benzene and pyridine rings, with centroid–centroid distances of 3.756 (5) Å.

Related literature

For related structures, see: Wang et al. (2006 [triangle], 2007 [triangle]); Yang et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-00o68-scheme1.jpg

Experimental

Crystal data

  • C10H9N2 +·C16H9O8 ·2H2O
  • M r = 522.46
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00o68-efi2.jpg
  • a = 7.1955 (8) Å
  • b = 8.935 (1) Å
  • c = 9.8847 (11) Å
  • α = 90.7920 (11)°
  • β = 106.4850 (13)°
  • γ = 107.1180 (15)°
  • V = 579.09 (11) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 296 K
  • 0.23 × 0.21 × 0.19 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • 2990 measured reflections
  • 2050 independent reflections
  • 1818 reflections with I > 2σ(I)
  • R int = 0.014

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.112
  • S = 1.03
  • 2050 reflections
  • 180 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050831/rz2388sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050831/rz2388Isup2.hkl

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

Acknowledgments

The authors acknowledge the Chan Xue Yan Cooperative Special Project of Guangdong Province, the Ministry of Science and Technology (project No. 2007A090302046), the Project of Science and Technology of Guangdong Province (project No. 2007A020200002-4) and the Natural Science Foundation of Guangdong Province (No. 9151063101000037) for supporting this work.

supplementary crystallographic information

Comment

In recent years, research on coordination polymers has made considerable progress in the fields of supramolecular chemistry and crystal engineering, because of their intriguing structural motifs and functional properties, such as molecular adsorption, magnetism, and luminescence. In general, hydrogen bonding interactions between ligands are specific and directional. In this context, biphenyl-3,3',4,4'-tetracarboxylic acid and 4,4'-bipyridine are excellent candidates for the construction of three-dimensional network motifs (Wang et al., 2006; Wang et al., 2007; Yang et al., 2007). Recently, we obtained the title compound under hydrothermal conditions and report its crystal structure here.

The asymmetric unit of the title compound contains one half of a monoprotic 4-4'-bipyridinium cation, one half of a 3-3'-4-tricarboxybiphenyl-4'-carboxylato anion and a water molecule, with both cation and anion possessing crystallographically imposed centre of symmetry (Fig. 1). As a result, the H1A nitrogen-bound hydrogen atom in the cation and acidic H2A hydrogen atom in the anion are disordered over two positions with site occupancies of 0.5. Bond lengths and angles are unexceptional. In the crystal packing (Fig. 2), cations, anions and lattice water molecules are linked by intermolecular O—H···O, C—H···O and N—H···N hydrogen bonds (Table 1) into layers parallel to (2 1 0). The layers are further connected into a three-dimensional network by O—H···O hydrogen bonds involving the water molecules as H-donors and by weak π–π stacking interactions involving neighbouring benzene and pyridine rings, with centroid-to-centroid distances of 3.756 (5) Å.

Experimental

A mixture of 4,4'-bipyridine (0.078 g, 0.5 mmol), 4-4'-dicarboxybiphenyl-3-3'dicarboxylic acid (0.165 g; 0.5 mmol), water (10 mL) was stirred vigorously for 30 min and then sealed in a Teflon-lined stainless-steel autoclave (25 mL capacity). The autoclave was heated and maintained at 433K for 3 days, and then cooled to room temperature at 5Kh-1 to obtain colourless block crystals suitable for X-ray analysis.

Refinement

Water H atoms were located in a difference Fourier map and refined with the O–H distance restrained to 0.84 Å and with Uiso(H) = 1.5 Ueq(O). The H atom bound to the N1 nitrogen atom in the cation and the carboxylic H atoms were refined with distance restraints of N–H = 0.90 Å and O–H = 0.90 Å, respectively. The H1A and H2A hydrogen atoms are disordered over two centrosymmetrically related positions and were therefore refined with site occupancies of 0.5. All other H atoms were placed at calculated positions and treated as riding on the parent atoms, with C–H = 0.93Å, and with Uiso(H) = 1.2 Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound showing the atomic-numbering scheme and 50% probability ellipsoids. Only one position of the disordered H atoms in the cation and anion is shown. Symmetry codes: (i) 1-x, 2-y, -z; (ii) 2-x, -y, 1-z; (iii) ...
Fig. 2.
Partial packing diagram of the title compound showing the layered network formed by intermolecular O—H···O, C—H···O and N—H···N hydrogen bonds (dashed lines). ...

Crystal data

C10H9N2+·C16H9O8·2H2OZ = 1
Mr = 522.46F(000) = 272
Triclinic, P1Dx = 1.498 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1955 (8) ÅCell parameters from 2061 reflections
b = 8.935 (1) Åθ = 2.4–28.2°
c = 9.8847 (11) ŵ = 0.12 mm1
α = 90.7920 (11)°T = 296 K
β = 106.4850 (13)°Block, colourless
γ = 107.1180 (15)°0.23 × 0.21 × 0.19 mm
V = 579.09 (11) Å3

Data collection

Bruker APEXII area-detector diffractometer1818 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
graphiteθmax = 25.2°, θmin = 2.2°
[var phi] and ω scanh = −7→8
2990 measured reflectionsk = −10→9
2050 independent reflectionsl = −11→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.112w = 1/[σ2(Fo2) + (0.0562P)2 + 0.2257P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2050 reflectionsΔρmax = 0.32 e Å3
180 parametersΔρmin = −0.25 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.071 (9)

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*/UeqOcc. (<1)
C10.4881 (3)1.01415 (19)0.18864 (18)0.0405 (4)
H10.53181.12300.20950.049*
C20.4740 (2)0.94960 (17)0.05542 (16)0.0321 (4)
C30.4103 (3)0.78512 (18)0.03012 (17)0.0361 (4)
H30.40080.7393−0.05760.043*
C40.3611 (2)0.68843 (17)0.13133 (17)0.0333 (4)
C50.3102 (3)0.51258 (19)0.09704 (18)0.0397 (4)
C60.3725 (2)0.75584 (18)0.26291 (16)0.0344 (4)
C70.3003 (3)0.65386 (19)0.36673 (18)0.0389 (4)
C80.4384 (3)0.91911 (19)0.28990 (18)0.0407 (4)
H80.44900.96500.37790.049*
C90.9236 (3)−0.1318 (2)0.19327 (19)0.0447 (4)
H90.8726−0.22540.13360.054*
C100.9232 (3)−0.13691 (19)0.33220 (18)0.0412 (4)
H100.8722−0.23310.36470.049*
C110.9987 (2)0.00096 (18)0.42445 (17)0.0351 (4)
C121.0714 (3)0.1400 (2)0.3674 (2)0.0490 (5)
H121.12340.23550.42430.059*
C131.0666 (3)0.1367 (2)0.2273 (2)0.0524 (5)
H131.11510.23110.19140.063*
N10.9947 (2)0.00297 (17)0.14119 (15)0.0428 (4)
H1A0.997 (7)0.004 (5)0.049 (2)0.051*0.50
O10.4404 (2)0.44851 (15)0.14281 (16)0.0572 (4)
O30.1949 (2)0.51807 (15)0.33352 (14)0.0596 (4)
O40.3524 (3)0.72538 (16)0.49433 (14)0.0647 (5)
H4A0.30920.66270.54650.097*
O1W0.2145 (3)0.5413 (2)0.66452 (17)0.0799 (6)
H1W0.30040.52900.73560.120*
H2W0.10310.52410.68170.120*
O20.1336 (2)0.43770 (14)0.01377 (15)0.0520 (4)
H2A0.040 (8)0.490 (8)0.001 (8)0.078*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0520 (10)0.0255 (8)0.0388 (9)0.0025 (7)0.0159 (8)−0.0015 (7)
C20.0325 (8)0.0276 (8)0.0339 (8)0.0060 (6)0.0100 (6)0.0017 (6)
C30.0467 (9)0.0279 (8)0.0327 (8)0.0081 (7)0.0141 (7)−0.0006 (6)
C40.0346 (8)0.0277 (8)0.0352 (8)0.0066 (6)0.0102 (6)0.0025 (6)
C50.0549 (10)0.0293 (8)0.0396 (9)0.0115 (8)0.0231 (8)0.0057 (7)
C60.0353 (8)0.0308 (8)0.0339 (8)0.0054 (6)0.0104 (7)0.0027 (6)
C70.0447 (9)0.0324 (8)0.0376 (9)0.0063 (7)0.0152 (7)0.0023 (7)
C80.0526 (10)0.0325 (8)0.0323 (9)0.0041 (7)0.0153 (7)−0.0022 (7)
C90.0530 (11)0.0371 (9)0.0421 (10)0.0122 (8)0.0135 (8)−0.0016 (7)
C100.0513 (10)0.0285 (8)0.0431 (10)0.0093 (7)0.0163 (8)0.0035 (7)
C110.0373 (8)0.0286 (8)0.0391 (9)0.0092 (6)0.0119 (7)0.0039 (6)
C120.0691 (13)0.0293 (9)0.0425 (10)0.0041 (8)0.0190 (9)0.0022 (7)
C130.0714 (13)0.0379 (10)0.0451 (10)0.0079 (9)0.0226 (9)0.0093 (8)
N10.0516 (9)0.0454 (8)0.0332 (8)0.0152 (7)0.0151 (7)0.0064 (6)
O10.0725 (10)0.0442 (7)0.0666 (9)0.0307 (7)0.0254 (7)0.0142 (6)
O30.0830 (10)0.0355 (7)0.0522 (8)−0.0054 (7)0.0330 (7)0.0011 (6)
O40.0976 (11)0.0443 (8)0.0368 (7)−0.0065 (7)0.0266 (7)0.0019 (6)
O1W0.0693 (10)0.0986 (13)0.0630 (10)0.0071 (9)0.0252 (8)0.0340 (9)
O20.0599 (9)0.0273 (6)0.0601 (8)0.0046 (6)0.0146 (7)−0.0086 (6)

Geometric parameters (Å, °)

C1—C81.378 (2)C9—N11.334 (2)
C1—C21.395 (2)C9—C101.375 (3)
C1—H10.9300C9—H90.9300
C2—C31.400 (2)C10—C111.392 (2)
C2—C2i1.488 (3)C10—H100.9300
C3—C41.385 (2)C11—C121.392 (2)
C3—H30.9300C11—C11ii1.489 (3)
C4—C61.397 (2)C12—C131.375 (3)
C4—C51.514 (2)C12—H120.9300
C5—O11.222 (2)C13—N11.334 (2)
C5—O21.277 (2)C13—H130.9300
C6—C81.391 (2)N1—H1A0.921 (18)
C6—C71.484 (2)O4—H4A0.8200
C7—O31.209 (2)O1W—H1W0.8263
C7—O41.307 (2)O1W—H2W0.8370
C8—H80.9300O2—H2A0.911 (19)
C8—C1—C2121.02 (15)C6—C8—H8119.4
C8—C1—H1119.5N1—C9—C10122.24 (16)
C2—C1—H1119.5N1—C9—H9118.9
C1—C2—C3117.26 (15)C10—C9—H9118.9
C1—C2—C2i121.74 (17)C9—C10—C11120.39 (16)
C3—C2—C2i121.00 (17)C9—C10—H10119.8
C4—C3—C2122.24 (15)C11—C10—H10119.8
C4—C3—H3118.9C10—C11—C12116.23 (16)
C2—C3—H3118.9C10—C11—C11ii121.63 (18)
C3—C4—C6119.43 (14)C12—C11—C11ii122.14 (18)
C3—C4—C5117.83 (14)C13—C12—C11120.36 (16)
C6—C4—C5122.62 (14)C13—C12—H12119.8
O1—C5—O2122.14 (16)C11—C12—H12119.8
O1—C5—C4119.75 (16)N1—C13—C12122.31 (17)
O2—C5—C4117.99 (15)N1—C13—H13118.8
C8—C6—C4118.80 (15)C12—C13—H13118.8
C8—C6—C7121.15 (14)C13—N1—C9118.47 (15)
C4—C6—C7119.90 (14)C13—N1—H1A120 (3)
O3—C7—O4123.27 (16)C9—N1—H1A121 (3)
O3—C7—C6122.33 (15)C7—O4—H4A109.5
O4—C7—C6114.33 (14)H1W—O1W—H2W109.1
C1—C8—C6121.24 (15)C5—O2—H2A115 (5)
C1—C8—H8119.4

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···N1iii0.92 (2)1.89 (2)2.814 (3)177 (4)
O4—H4A···O1W0.821.752.5657 (19)176
O1W—H1W···O1iv0.831.862.642 (2)157
O1W—H2W···O3v0.842.032.841 (2)165
O2—H2A···O2vi0.91 (2)1.54 (2)2.446 (3)173 (7)
C3—H3···O1vii0.932.543.270 (2)135
C13—H13···O2viii0.932.573.448 (2)159
C9—H9···O2ix0.932.363.246 (2)160

Symmetry codes: (iii) −x+2, −y, −z; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1; (vi) −x, −y+1, −z; (vii) −x+1, −y+1, −z; (viii) x+1, y, z; (ix) −x+1, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2388).

References

  • Bruker (2005). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, J.-J., Gou, L., Hu, H.-M., Han, Z.-X., Li, D.-S., Xue, G.-L., Yang, M.-L. & Shi, Q.-Z. (2007). Cryst. Growth Des.7, 1514–1521.
  • Wang, X.-L., Qin, C. & Wang, E.-B. (2006). Cryst. Growth Des.6, 439–443.
  • Yang, G.-P., Wang, Y.-Y., Ma, L.-F., Liu, J.-Q., Wu, Y.-P., Wu, W.-P. & Shi, Q.-Z. (2007). Eur. J. Inorg. Chem. pp. 3892–3898.

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