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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 66| Part 8| August 2010| Page o2106
https://doi.org/10.1107/S160053681002800X

3-Nitro-5-(4-pyridinio)benzoate

Xiao-Jun Zhaoa and Cheng-Jun Haoa*

aCollege of Chemistry and Chemical Engineering, Pingdingshan University, Pingdingshan 467000, People's Republic of China
*Correspondence e-mail: haochengjun2008@163.com

(Received 4 July 2010; accepted 14 July 2010; online 24 July 2010)

The title compound, C12H8N2O4, crystallizes as a zwitterion in which the pyridyl N atom is protonated. The dihedral angle between the benzene and pyridinium rings is 27.9 (2)°. In the crystal, N—H⋯O hydrogen bonds link adjacent zwitterions into a three-dimensional structure.

Related literature

The title compound was reacted with MgCl2 under hydrothermal conditions in an attempt to obtain a new coordination polymer as part of our investigation of pyridine caboxylate coordination polymers. For the advantages of hydro­thermal synthesis, see: Feng et al. (2001[Feng, S. H. & Xu, R. R. (2001). Acc. Chem. Res. 34, 239-247.]); Tao et al. (2001[Tao, J., Zhang, X. M., Tong, M. L. & Chen, X. M. (2001). J. Chem. Soc. Dalton Trans. pp. 770-771.]). For the crystal structures of coord­in­ation polymers involving 4-pyridine­carboxyl­ate ligands, see: Lu et al. (2003[Lu, T. B. & Luck, R. L. (2003). Inorg. Chim. Acta, 351, 345-355.]).

[Scheme 1]

Experimental

Crystal data

  • C12H8N2O4

  • Mr = 244.20

  • Orthorhombic, F d d 2

  • a = 16.1215 (14) Å

  • b = 37.126 (3) Å

  • c = 7.1317 (8) Å

  • V = 4268.5 (7) Å3

  • Z = 16

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 298 K

  • 0.46 × 0.17 × 0.09 mm
Data collection

  • Bruker SMART 1000 CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.948, Tmax = 0.990

  • 4377 measured reflections

  • 1023 independent reflections

  • 621 reflections with I > 2σ(I)

  • Rint = 0.110
Refinement

  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.118

  • S = 1.02

  • 1023 reflections

  • 163 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N2—H2⋯O1i 0.86 1.74 2.592 (5) 172
Symmetry code: (i) [-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}].

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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/S160053681002800X/wn2400sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681002800X/wn2400Isup2.hkl

checkCIF report


Comment top

Hydrothermal synthesis has been successful in the preparation of new materials, because problems associated with ligand solubility were minimized and the reactivity of reactants was enhanced during the crystallization process in a heated sealed solution above ambient temperature and pressure (Feng et al., 2001; Tao et al., 2001). Thus, we have reacted 5-(4-pyridyl)-3-nitrobenzoic acid with MgCl2 under hydrothermal conditions in an effort to obtain a new coordination polymer as part of further investigation of pyridine caboxylate coordination polymers (Lu et al., 2003). In fact, no complex was formed, but we report here the crystal structure of the starting organic compound.

In the title compound, C12H8N2O4, the pyridyl N atom is protonated, and the compound is formally a zwitterion. The carboxyl group and the nitro group are approximately coplanar with the aromatic ring (Fig. 1), as indicated by the O2—C1—C2—C3 and O1—C1—C2—C3 torsion angles of 11.1 (8) ° and -170.2 (5) °, respectively; the O3—N1—C4—C3 and O4—N1—C4—C3 torsion angles are 1.0 (7) and -176.9 (5) °, respectively. Furthermore, the dihedral angle between the benzene ring and the pyridine ring is 27.9 (2) °. In the crystal packing, N—H···O hydrogen bonds stabilize the three-dimensional structure.

Related literature top

For the advantages of hydrothermal synthesis, see: Feng et al. (2001); Tao et al. (2001). For the crystal structures of coordination polymers involving 4-pyridinecarboxylate ligands, see: Lu et al. (2003).

Experimental top

A mixture of MgCl2 (0.1 mmol, 0.01g), 5-(4-pyridyl)-3-nitrobenzoic acid (0.1 mmol, 0.025 g) and 10 ml of H2O was loaded in a 20 ml Teflon-lined stainless steel vessel and heated at 303K for 3 days. Colourless crystals were obtained when the solution was slowly cooled to room temperature.

Refinement top

H atoms were placed at calculated positions and were treated as riding on the parent C or N atoms with C—H = 0.93 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C, N). In the absence of significant anomalous scattering Friedel pairs were merged.

Structure description top

Hydrothermal synthesis has been successful in the preparation of new materials, because problems associated with ligand solubility were minimized and the reactivity of reactants was enhanced during the crystallization process in a heated sealed solution above ambient temperature and pressure (Feng et al., 2001; Tao et al., 2001). Thus, we have reacted 5-(4-pyridyl)-3-nitrobenzoic acid with MgCl2 under hydrothermal conditions in an effort to obtain a new coordination polymer as part of further investigation of pyridine caboxylate coordination polymers (Lu et al., 2003). In fact, no complex was formed, but we report here the crystal structure of the starting organic compound.

In the title compound, C12H8N2O4, the pyridyl N atom is protonated, and the compound is formally a zwitterion. The carboxyl group and the nitro group are approximately coplanar with the aromatic ring (Fig. 1), as indicated by the O2—C1—C2—C3 and O1—C1—C2—C3 torsion angles of 11.1 (8) ° and -170.2 (5) °, respectively; the O3—N1—C4—C3 and O4—N1—C4—C3 torsion angles are 1.0 (7) and -176.9 (5) °, respectively. Furthermore, the dihedral angle between the benzene ring and the pyridine ring is 27.9 (2) °. In the crystal packing, N—H···O hydrogen bonds stabilize the three-dimensional structure.

For the advantages of hydrothermal synthesis, see: Feng et al. (2001); Tao et al. (2001). For the crystal structures of coordination polymers involving 4-pyridinecarboxylate ligands, see: Lu et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 structure of the title compound, showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. View of the three-dimensional network constructed by N—H···O hydrogen bonding interactions (dashed lines). H atoms not involved in the hydrogen bonds are omitted for clarity.
3-Nitro-5-(4-pyridinio)benzoate top
Crystal data top
C12H8N2O4F(000) = 2016
Mr = 244.20Dx = 1.520 Mg m−3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 638 reflections
a = 16.1215 (14) Åθ = 2.8–26.3°
b = 37.126 (3) ŵ = 0.12 mm−1
c = 7.1317 (8) ÅT = 298 K
V = 4268.5 (7) Å3Needle, colourless
Z = 160.46 × 0.17 × 0.09 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1023 independent reflections
Radiation source: fine-focus sealed tube621 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.110
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		h = −19→11
Tmin = 0.948, Tmax = 0.990k = −43→43
4377 measured reflectionsl = −8→8
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0406P)2 + 0.170P]
where P = (Fo2 + 2Fc2)/3
1023 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.18 e Å−3
1 restraintΔρmin = −0.22 e Å−3
Crystal data top
C12H8N2O4V = 4268.5 (7) Å3
Mr = 244.20Z = 16
Orthorhombic, Fdd2Mo Kα radiation
a = 16.1215 (14) ŵ = 0.12 mm−1
b = 37.126 (3) ÅT = 298 K
c = 7.1317 (8) Å0.46 × 0.17 × 0.09 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1023 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		621 reflections with I > 2σ(I)
Tmin = 0.948, Tmax = 0.990Rint = 0.110
4377 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0481 restraint
wR(F2) = 0.118H-atom parameters constrained
S = 1.02Δρmax = 0.18 e Å−3
1023 reflectionsΔρmin = −0.22 e Å−3
163 parameters
Special details top

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) top
xyzUiso*/Ueq
N1−0.0034 (3)0.07102 (12)0.9143 (9)0.0630 (15)
N20.3542 (3)−0.05673 (10)0.8083 (7)0.0543 (14)
H20.3836−0.07600.81090.065*
O10.3097 (2)0.13480 (9)0.5977 (7)0.0701 (13)
O20.2043 (2)0.16759 (9)0.7037 (7)0.0731 (14)
O3−0.0420 (2)0.09929 (10)0.9147 (9)0.0919 (17)
O4−0.0331 (2)0.04219 (10)0.9681 (8)0.0856 (17)
C10.2386 (4)0.13874 (13)0.6766 (9)0.0526 (15)
C20.2001 (3)0.10398 (12)0.7393 (8)0.0435 (14)
C30.1187 (3)0.10352 (12)0.7997 (8)0.0486 (15)
H30.08810.12470.80460.058*
C40.0835 (3)0.07138 (12)0.8524 (9)0.0474 (15)
C50.1277 (3)0.03937 (12)0.8486 (8)0.0451 (14)
H50.10200.01790.88220.054*
C60.2104 (3)0.03957 (11)0.7944 (7)0.0403 (12)
C70.2461 (3)0.07216 (11)0.7400 (8)0.0428 (14)
H70.30150.07270.70350.051*
C80.2731 (3)−0.05830 (13)0.7825 (8)0.0508 (15)
H80.2480−0.08070.76850.061*
C90.2244 (3)−0.02788 (12)0.7757 (8)0.0475 (14)
H90.1675−0.03000.75800.057*
C100.2600 (3)0.00589 (12)0.7950 (8)0.0420 (13)
C110.3461 (3)0.00687 (12)0.8235 (9)0.0522 (15)
H110.37340.02880.83780.063*
C120.3890 (3)−0.02476 (13)0.8300 (9)0.0575 (17)
H120.4459−0.02380.85070.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.044 (3)0.056 (3)0.089 (4)0.001 (2)0.002 (3)−0.004 (3)
N20.055 (3)0.036 (2)0.072 (4)0.014 (2)0.003 (3)0.005 (3)
O10.063 (3)0.041 (2)0.106 (4)−0.0047 (18)0.024 (3)0.005 (2)
O20.066 (3)0.0369 (19)0.116 (4)0.0041 (18)0.007 (3)0.011 (3)
O30.063 (2)0.065 (3)0.149 (5)0.020 (2)0.030 (3)0.006 (3)
O40.056 (2)0.058 (2)0.143 (5)−0.009 (2)0.019 (3)0.012 (3)
C10.057 (4)0.035 (3)0.066 (4)−0.003 (3)0.001 (3)0.011 (3)
C20.042 (3)0.032 (2)0.057 (4)−0.001 (2)−0.001 (3)0.000 (2)
C30.046 (3)0.030 (3)0.070 (4)0.003 (2)−0.001 (3)−0.002 (3)
C40.041 (3)0.034 (3)0.067 (4)−0.001 (2)0.000 (3)0.000 (3)
C50.046 (3)0.031 (3)0.058 (4)0.001 (2)0.001 (3)0.003 (3)
C60.040 (3)0.031 (3)0.049 (3)−0.002 (2)−0.001 (3)0.000 (3)
C70.035 (3)0.031 (2)0.061 (4)0.001 (2)0.000 (3)−0.001 (3)
C80.057 (4)0.032 (3)0.063 (4)0.001 (2)−0.003 (3)0.008 (3)
C90.044 (3)0.038 (3)0.060 (4)−0.004 (2)0.001 (3)0.001 (3)
C100.045 (3)0.031 (3)0.051 (4)0.002 (2)0.003 (3)0.003 (2)
C110.051 (3)0.035 (3)0.070 (4)−0.001 (2)0.004 (3)0.004 (3)
C120.049 (3)0.042 (3)0.082 (5)0.005 (3)0.005 (3)0.008 (3)
Geometric parameters (Å, º) top
N1—O31.220 (5)C5—C61.388 (6)
N1—O41.233 (5)C5—H50.9300
N1—C41.469 (7)C6—C71.395 (6)
N2—C121.322 (6)C6—C101.485 (6)
N2—C81.323 (6)C7—H70.9300
N2—H20.8600C8—C91.376 (6)
O1—C11.284 (6)C8—H80.9300
O2—C11.221 (6)C9—C101.386 (6)
C1—C21.500 (6)C9—H90.9300
C2—C31.381 (7)C10—C111.403 (6)
C2—C71.394 (6)C11—C121.364 (6)
C3—C41.374 (6)C11—H110.9300
C3—H30.9300C12—H120.9300
C4—C51.386 (6)
O3—N1—O4123.2 (5)C5—C6—C7118.6 (4)
O3—N1—C4118.6 (5)C5—C6—C10120.8 (4)
O4—N1—C4118.1 (4)C7—C6—C10120.6 (4)
C12—N2—C8118.4 (4)C2—C7—C6121.1 (4)
C12—N2—H2120.8C2—C7—H7119.4
C8—N2—H2120.8C6—C7—H7119.4
O2—C1—O1125.0 (5)N2—C8—C9122.2 (5)
O2—C1—C2121.3 (5)N2—C8—H8118.9
O1—C1—C2113.7 (4)C9—C8—H8118.9
C3—C2—C7119.6 (4)C8—C9—C10120.2 (4)
C3—C2—C1119.8 (4)C8—C9—H9119.9
C7—C2—C1120.7 (4)C10—C9—H9119.9
C4—C3—C2119.3 (4)C9—C10—C11116.6 (4)
C4—C3—H3120.4C9—C10—C6122.6 (4)
C2—C3—H3120.4C11—C10—C6120.8 (4)
C3—C4—C5121.8 (4)C12—C11—C10119.0 (5)
C3—C4—N1119.0 (4)C12—C11—H11120.5
C5—C4—N1119.2 (5)C10—C11—H11120.5
C4—C5—C6119.6 (4)N2—C12—C11123.6 (5)
C4—C5—H5120.2N2—C12—H12118.2
C6—C5—H5120.2C11—C12—H12118.2
O2—C1—C2—C311.2 (9)C3—C2—C7—C62.3 (9)
O1—C1—C2—C3−170.0 (5)C1—C2—C7—C6−178.7 (5)
O2—C1—C2—C7−167.8 (6)C5—C6—C7—C2−0.1 (8)
O1—C1—C2—C710.9 (8)C10—C6—C7—C2−179.8 (5)
C7—C2—C3—C4−2.6 (8)C12—N2—C8—C90.7 (9)
C1—C2—C3—C4178.4 (5)N2—C8—C9—C100.4 (9)
C2—C3—C4—C50.7 (8)C8—C9—C10—C11−0.8 (8)
C2—C3—C4—N1−179.3 (6)C8—C9—C10—C6−178.2 (5)
O3—N1—C4—C30.9 (8)C5—C6—C10—C925.9 (8)
O4—N1—C4—C3−177.2 (6)C7—C6—C10—C9−154.3 (5)
O3—N1—C4—C5−179.0 (6)C5—C6—C10—C11−151.4 (6)
O4—N1—C4—C52.8 (8)C7—C6—C10—C1128.4 (8)
C3—C4—C5—C61.5 (9)C9—C10—C11—C120.2 (9)
N1—C4—C5—C6−178.5 (5)C6—C10—C11—C12177.6 (5)
C4—C5—C6—C7−1.8 (8)C8—N2—C12—C11−1.3 (10)
C4—C5—C6—C10178.0 (5)C10—C11—C12—N20.9 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.861.742.592 (5)172
Symmetry code: (i) −x+3/4, y−1/4, z+1/4.

Experimental details

Crystal data
Chemical formulaC12H8N2O4
Mr244.20
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)298
a, b, c (Å)16.1215 (14), 37.126 (3), 7.1317 (8)
V (Å3)4268.5 (7)
Z16
Radiation typeMo Kα
µ (mm−1)0.12
Crystal size (mm)0.46 × 0.17 × 0.09
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.948, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections		4377, 1023, 621
Rint0.110
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.118, 1.02
No. of reflections1023
No. of parameters163
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.18, −0.22

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.861.742.592 (5)172.4
Symmetry code: (i) −x+3/4, y−1/4, z+1/4.
 

Acknowledgements

The authors acknowledge Pingdingshan University for supporting this work.

References

First citationBruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationFeng, S. H. & Xu, R. R. (2001). Acc. Chem. Res. 34, 239–247.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationLu, T. B. & Luck, R. L. (2003). Inorg. Chim. Acta, 351, 345–355.  Web of Science CSD CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationTao, J., Zhang, X. M., Tong, M. L. & Chen, X. M. (2001). J. Chem. Soc. Dalton Trans. pp. 770–771.  Web of Science CSD CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 8| August 2010| Page o2106
https://doi.org/10.1107/S160053681002800X
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