PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2834.
Published online 2009 October 23. doi:  10.1107/S1600536809043207
PMCID: PMC2971006

Pyridinium-2-carboxyl­ate–benzene-1,2-diol (1/1)

Abstract

The title compound, C6H5NO2·C6H6O2, crystallizes with one pyridinium-2-carboxyl­ate zwitterion and one mol­ecule of benzene-1,2-diol in the asymmetric unit. The crystal structure is characterized by alternating mol­ecules forming zigzag chains running along the a axis: the mol­ecules are connected by O—H(...)O and N—H(...)(O,O) hydrogen bonds.

Related literature

For co-crystallization experiments, see: Ton & Bolte (2005 [triangle]); Tutughamiarso et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2834-scheme1.jpg

Experimental

Crystal data

  • C6H5NO2·C6H6O2
  • M r = 233.22
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2834-efi1.jpg
  • a = 6.9710 (14) Å
  • b = 6.9855 (14) Å
  • c = 21.806 (4) Å
  • V = 1061.9 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 173 K
  • 0.21 × 0.18 × 0.16 mm

Data collection

  • Stoe IPDSII two-circle diffractometer
  • Absorption correction: none
  • 11928 measured reflections
  • 1196 independent reflections
  • 1105 reflections with I > 2σ(I)
  • R int = 0.081

Refinement

  • R[F 2 > 2σ(F 2)] = 0.096
  • wR(F 2) = 0.197
  • S = 1.23
  • 1196 reflections
  • 155 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]) and SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809043207/ng2670sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043207/ng2670Isup2.hkl

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

supplementary crystallographic information

Comment

The aim of our research is the cocrystallization of two small organic compounds in order to examine the hydrogen bonds formed between hydrogen-bond acceptors and hydrogen-bond donors (Ton & Bolte, 2005; Tutughamiarso et al., 2009). When pyridinecarboxaldehyde and 1,2-dihydroxybenzene were mixed in order to obtain a hydrogen bonded supermolecular complex, it turned out that the aldehyd had been oxidized to the carboxylic acid. The title compound crystallizes with one pyridinium-2-carboxylate zwitterion and one molecule of benzene-1,2-diol in the asymmetric unit. The crystal structure is characterized by alternating molecules forming zigzag chains running along the a axis. The molecules are connected by O—H···N and O—H···O hydrogen bonds.

Experimental

40 mg pyridinecarboxaldehyde and 40 mg 1,2-dihydroxybenzene were diluted in 2 ml diethyl ether in a nitrogen atmosphere. After five weeks a brown precipitate emerged from the mixture. On the surface white crystals has been sedimented, one of which was used for structure determination. It turned out that the pyridinecarboxaldehyde had been oxidized to the carboxylic acid.

Refinement

Hydrogen atoms were located in a difference Fourier map but those bonded to C and O were included in calculated positions [C—H = 0.93 - 0.99 Å] and refined as riding [Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(O,Cmethyl)]. H atoms bonded to N were freely refined. Due to the absence of anomalous scatterers, the absolute structure could not be determined and 808 Friedel pairs were merged.

Figures

Fig. 1.
A view of the molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
Fig. 2.
Part of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C6H5NO2·C6H6O2F(000) = 488
Mr = 233.22Dx = 1.459 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 6345 reflections
a = 6.9710 (14) Åθ = 3.5–24.3°
b = 6.9855 (14) ŵ = 0.11 mm1
c = 21.806 (4) ÅT = 173 K
V = 1061.9 (4) Å3Block, colourless
Z = 40.21 × 0.18 × 0.16 mm

Data collection

Stoe IPDSII two-circle diffractometer1105 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.081
graphiteθmax = 25.8°, θmin = 3.1°
ω scansh = −8→8
11928 measured reflectionsk = −8→8
1196 independent reflectionsl = −26→25

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.096H-atom parameters constrained
wR(F2) = 0.197w = 1/[σ2(Fo2) + (0.0513P)2 + 3.5668P] where P = (Fo2 + 2Fc2)/3
S = 1.23(Δ/σ)max = 0.001
1196 reflectionsΔρmax = 0.44 e Å3
155 parametersΔρmin = −0.34 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.036 (6)

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
O11.1064 (7)0.3802 (7)0.0845 (2)0.0257 (11)
H11.20930.41530.06790.039*
O20.8174 (6)0.1866 (8)0.1466 (2)0.0295 (12)
H20.79940.27560.12140.044*
C11.1455 (9)0.3029 (9)0.1410 (3)0.0200 (13)
C20.9985 (9)0.2048 (10)0.1716 (3)0.0220 (13)
C31.0330 (10)0.1145 (11)0.2274 (3)0.0259 (14)
H30.93320.04600.24730.031*
C41.2160 (10)0.1249 (11)0.2542 (3)0.0303 (16)
H41.23990.06490.29250.036*
C51.3612 (9)0.2231 (10)0.2244 (3)0.0280 (15)
H51.48500.23020.24240.034*
C61.3273 (9)0.3110 (10)0.1686 (3)0.0254 (14)
H61.42840.37770.14870.031*
O110.3875 (7)0.5038 (7)0.0125 (2)0.0307 (12)
O120.6497 (8)0.4131 (10)0.0643 (3)0.0516 (18)
N10.8827 (8)0.5092 (8)−0.0246 (2)0.0222 (12)
H310.90860.49120.01600.027*
C111.0169 (10)0.5516 (10)−0.0666 (3)0.0260 (15)
H111.14790.5226−0.05910.031*
C130.6922 (9)0.5494 (9)−0.0326 (3)0.0208 (13)
C140.6360 (10)0.6404 (9)−0.0853 (3)0.0237 (14)
H140.50490.6725−0.09140.028*
C150.7722 (10)0.6856 (10)−0.1299 (3)0.0275 (15)
H150.73470.7491−0.16650.033*
C160.9629 (10)0.6368 (11)−0.1202 (3)0.0301 (17)
H161.05590.6628−0.15100.036*
C1310.5649 (10)0.4815 (11)0.0200 (3)0.0283 (15)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.015 (2)0.032 (2)0.030 (2)−0.002 (2)0.0002 (18)0.006 (2)
O20.015 (2)0.033 (3)0.041 (3)−0.005 (2)−0.003 (2)0.007 (2)
C10.017 (3)0.015 (3)0.028 (3)−0.007 (3)0.002 (3)−0.001 (3)
C20.017 (3)0.020 (3)0.029 (3)−0.004 (3)0.000 (3)−0.003 (3)
C30.025 (3)0.026 (3)0.027 (3)−0.002 (3)0.006 (3)−0.002 (3)
C40.032 (4)0.034 (4)0.026 (3)0.001 (3)−0.004 (3)0.006 (3)
C50.019 (3)0.035 (4)0.030 (3)0.000 (3)−0.004 (3)−0.003 (3)
C60.019 (3)0.029 (3)0.028 (3)−0.005 (3)0.003 (3)−0.003 (3)
O110.016 (2)0.043 (3)0.033 (2)−0.002 (2)0.002 (2)0.002 (3)
O120.024 (3)0.086 (5)0.044 (3)0.015 (3)0.007 (2)0.033 (3)
N10.019 (3)0.025 (3)0.023 (2)0.004 (3)0.001 (2)0.000 (2)
C110.022 (3)0.022 (3)0.034 (3)0.000 (3)0.005 (3)−0.002 (3)
C130.015 (3)0.015 (3)0.033 (3)−0.001 (2)0.002 (3)0.000 (3)
C140.019 (3)0.025 (3)0.027 (3)0.000 (3)−0.002 (3)0.002 (3)
C150.038 (4)0.021 (3)0.024 (3)−0.001 (3)−0.002 (3)−0.002 (3)
C160.028 (4)0.034 (4)0.028 (3)−0.001 (3)0.004 (3)0.002 (3)
C1310.028 (4)0.028 (3)0.029 (3)0.004 (3)0.003 (3)0.005 (3)

Geometric parameters (Å, °)

O1—C11.374 (8)O11—C1311.257 (8)
O1—H10.8397O12—C1311.229 (9)
O2—C21.381 (7)N1—C111.342 (9)
O2—H20.8392N1—C131.368 (8)
C1—C21.401 (9)N1—H310.9123
C1—C61.404 (9)C11—C161.365 (10)
C2—C31.391 (9)C11—H110.9500
C3—C41.405 (9)C13—C141.370 (9)
C3—H30.9500C13—C1311.526 (9)
C4—C51.384 (10)C14—C151.396 (10)
C4—H40.9500C14—H140.9500
C5—C61.383 (9)C15—C161.389 (10)
C5—H50.9500C15—H150.9500
C6—H60.9500C16—H160.9500
C1—O1—H1109.4C11—N1—H31123.7
C2—O2—H2109.1C13—N1—H31110.1
O1—C1—C2118.3 (5)N1—C11—C16119.3 (7)
O1—C1—C6123.2 (5)N1—C11—H11120.4
C2—C1—C6118.5 (6)C16—C11—H11120.4
O2—C2—C3117.5 (6)N1—C13—C14118.6 (6)
O2—C2—C1121.7 (6)N1—C13—C131113.9 (6)
C3—C2—C1120.7 (6)C14—C13—C131127.4 (6)
C2—C3—C4119.8 (6)C13—C14—C15119.7 (6)
C2—C3—H3120.1C13—C14—H14120.2
C4—C3—H3120.1C15—C14—H14120.2
C5—C4—C3119.6 (6)C16—C15—C14119.4 (6)
C5—C4—H4120.2C16—C15—H15120.3
C3—C4—H4120.2C14—C15—H15120.3
C6—C5—C4120.5 (6)C11—C16—C15120.0 (7)
C6—C5—H5119.8C11—C16—H16120.0
C4—C5—H5119.8C15—C16—H16120.0
C5—C6—C1120.9 (6)O12—C131—O11128.6 (7)
C5—C6—H6119.6O12—C131—C13115.6 (6)
C1—C6—H6119.6O11—C131—C13115.8 (6)
C11—N1—C13123.0 (6)
O1—C1—C2—O2−0.7 (10)C11—N1—C13—C14−1.3 (10)
C6—C1—C2—O2−178.3 (6)C11—N1—C13—C131177.8 (6)
O1—C1—C2—C3176.4 (6)N1—C13—C14—C151.5 (9)
C6—C1—C2—C3−1.2 (10)C131—C13—C14—C15−177.4 (6)
O2—C2—C3—C4178.6 (6)C13—C14—C15—C160.2 (10)
C1—C2—C3—C41.4 (10)N1—C11—C16—C152.5 (11)
C2—C3—C4—C5−0.8 (11)C14—C15—C16—C11−2.3 (11)
C3—C4—C5—C60.1 (11)N1—C13—C131—O125.1 (9)
C4—C5—C6—C10.1 (11)C14—C13—C131—O12−176.0 (7)
O1—C1—C6—C5−177.0 (6)N1—C13—C131—O11−175.2 (6)
C2—C1—C6—C50.5 (10)C14—C13—C131—O113.7 (10)
C13—N1—C11—C16−0.8 (10)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O11i0.841.842.655 (6)163
O2—H2···O120.841.892.662 (7)153
N1—H31···O120.912.162.617 (7)110
N1—H31···O10.912.182.984 (7)147

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2670).

References

  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Stoe & Cie (2001). X-AREA and X-RED Stoe & Cie, Darmstadt, Germany.
  • Ton, Q. C. & Bolte, M. (2005). Acta Cryst. E61, o1406–o1407.
  • Tutughamiarso, M., Bolte, M. & Egert, E. (2009). Acta Cryst. C65, o574–o578. [PubMed]

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