organic compounds
2-Carboxypyridinium maleate
aDepartment of Physics, Panimalar Engineering College, Chennai 600 123, India, bDepartment of Physics, Presidency College, Chennai 600 005, India, cDepartment of Physics, Aksheyaa College of Engineering, Kancheepuram 603 314, India, and dDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, mohan66@hotmail.com
In the title molecular salt, C6H6NO2+.C4H3O4−, the 2-carboxypyridinium cation is essentially planar with a maximum deviation of 0.003 (3) Å. In the crystal, adjacent cations and anions are linked by an extensive system of weak N—H⋯O, O—H⋯O and C—H⋯O interactions, forming a layer parallel to the ab plane.
Related literature
For details of pyridine and its derivatives, see: Banerjee & Murugavel (2004); Bis et al. (2006). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812041177/rk2380sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041177/rk2380Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812041177/rk2380Isup3.cml
A solution of picolinic acid (0.123 g, 1 mmol) in 10 ml ethanol was added with stirring to a solution of maleic acid (0.116 g, 1 mmol) in 10 ml of distilled water at 303 K. After some time, white precipitate was obtained, which was dissolved in ethanol and colourless block–shaped single crystals were obtained by slow evaporation of the ethanol solution.
H atoms were positioned geometrically and refined using riding model with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C) for aromatic H, N—H = 0.86Å and Uiso(H) = 1.2Ueq(N) for amine H and O—H = 0.82Å and Uiso(H) = 1.5Ueq(O) for hydroxyl H.
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of title compound with atom labels. Displacement ellipsoids are drawn at 30% probability level. H atoms are presented as asmall spheres of arbitrary radius. | |
Fig. 2. The packing of I, viewed down c axis. Intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. |
C6H6NO2·C4H3O4 | F(000) = 496 |
Mr = 239.18 | Dx = 1.534 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4245 reflections |
a = 14.6498 (9) Å | θ = 2.4–28.3° |
b = 10.3976 (8) Å | µ = 0.13 mm−1 |
c = 6.9067 (5) Å | T = 295 K |
β = 100.089 (3)° | Block, colourless |
V = 1035.78 (13) Å3 | 0.24 × 0.20 × 0.16 mm |
Z = 4 |
Bruker Kappa APEXII CCD diffractometer | 2557 independent reflections |
Radiation source: fine-focus sealed tube | 2092 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω– and ϕ–scans | θmax = 28.3°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→18 |
Tmin = 0.970, Tmax = 0.980 | k = −13→13 |
9722 measured reflections | l = −9→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
wR(F2) = 0.199 | w = 1/[σ2(Fo2) + (0.0625P)2 + 1.8972P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
2557 reflections | Δρmax = 0.43 e Å−3 |
155 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (3) |
C6H6NO2·C4H3O4 | V = 1035.78 (13) Å3 |
Mr = 239.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.6498 (9) Å | µ = 0.13 mm−1 |
b = 10.3976 (8) Å | T = 295 K |
c = 6.9067 (5) Å | 0.24 × 0.20 × 0.16 mm |
β = 100.089 (3)° |
Bruker Kappa APEXII CCD diffractometer | 2557 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2092 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.980 | Rint = 0.027 |
9722 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.43 e Å−3 |
2557 reflections | Δρmin = −0.33 e Å−3 |
155 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.57261 (18) | −0.0804 (3) | 0.3125 (4) | 0.0320 (6) | |
C2 | 0.6336 (2) | −0.1778 (3) | 0.3751 (5) | 0.0389 (7) | |
H2 | 0.6170 | −0.2628 | 0.3454 | 0.047* | |
C3 | 0.7201 (2) | −0.1492 (3) | 0.4825 (5) | 0.0438 (7) | |
H3 | 0.7618 | −0.2149 | 0.5261 | 0.053* | |
C4 | 0.7440 (2) | −0.0230 (3) | 0.5246 (5) | 0.0412 (7) | |
H4 | 0.8020 | −0.0027 | 0.5963 | 0.049* | |
C5 | 0.6817 (2) | 0.0725 (3) | 0.4599 (5) | 0.0401 (7) | |
H5 | 0.6971 | 0.1582 | 0.4869 | 0.048* | |
N1 | 0.59856 (15) | 0.0413 (2) | 0.3575 (4) | 0.0342 (5) | |
H1 | 0.5599 | 0.1021 | 0.3187 | 0.041* | |
C6 | 0.47635 (19) | −0.1001 (3) | 0.1946 (4) | 0.0346 (6) | |
C7 | 0.79780 (19) | 0.0490 (3) | 0.0421 (4) | 0.0354 (6) | |
C8 | 0.8827 (2) | −0.0055 (3) | 0.1646 (5) | 0.0373 (6) | |
H8 | 0.8762 | −0.0878 | 0.2130 | 0.045* | |
C9 | 0.9664 (2) | 0.0462 (3) | 0.2149 (5) | 0.0388 (7) | |
H9 | 1.0084 | −0.0061 | 0.2955 | 0.047* | |
C10 | 1.0058 (2) | 0.1714 (3) | 0.1674 (5) | 0.0401 (7) | |
O1 | 0.45516 (17) | −0.2082 (2) | 0.1321 (4) | 0.0566 (7) | |
O2 | 0.42766 (14) | 0.0007 (2) | 0.1721 (4) | 0.0453 (6) | |
H2A | 0.3766 | −0.0161 | 0.1075 | 0.068* | |
O3 | 0.72935 (14) | −0.0300 (2) | 0.0195 (4) | 0.0446 (6) | |
O4 | 0.79341 (16) | 0.1568 (2) | −0.0311 (4) | 0.0601 (8) | |
O5 | 0.95136 (17) | 0.2604 (2) | 0.0741 (4) | 0.0559 (7) | |
H5A | 0.8978 | 0.2340 | 0.0523 | 0.084* | |
O6 | 1.08852 (16) | 0.1899 (3) | 0.2139 (4) | 0.0580 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0282 (13) | 0.0299 (13) | 0.0366 (14) | −0.0020 (10) | 0.0024 (10) | 0.0014 (11) |
C2 | 0.0389 (15) | 0.0262 (13) | 0.0493 (17) | 0.0000 (11) | 0.0014 (13) | 0.0055 (12) |
C3 | 0.0374 (15) | 0.0392 (16) | 0.0514 (18) | 0.0078 (13) | −0.0014 (13) | 0.0081 (14) |
C4 | 0.0284 (13) | 0.0471 (17) | 0.0440 (17) | −0.0014 (12) | −0.0051 (12) | −0.0031 (13) |
C5 | 0.0310 (14) | 0.0349 (15) | 0.0518 (18) | −0.0029 (11) | 0.0001 (12) | −0.0068 (13) |
N1 | 0.0270 (11) | 0.0274 (11) | 0.0458 (14) | 0.0014 (9) | −0.0005 (10) | 0.0004 (10) |
C6 | 0.0270 (13) | 0.0327 (14) | 0.0417 (15) | −0.0060 (10) | −0.0003 (11) | 0.0041 (11) |
C7 | 0.0295 (13) | 0.0331 (14) | 0.0426 (15) | 0.0006 (11) | 0.0031 (11) | −0.0015 (12) |
C8 | 0.0358 (14) | 0.0296 (13) | 0.0451 (16) | 0.0011 (11) | 0.0029 (12) | 0.0029 (12) |
C9 | 0.0352 (14) | 0.0320 (14) | 0.0452 (17) | 0.0020 (11) | −0.0041 (12) | 0.0017 (12) |
C10 | 0.0378 (15) | 0.0350 (15) | 0.0459 (17) | −0.0054 (12) | 0.0024 (13) | −0.0057 (13) |
O1 | 0.0479 (13) | 0.0352 (12) | 0.0781 (18) | −0.0090 (10) | −0.0125 (12) | −0.0019 (12) |
O2 | 0.0261 (10) | 0.0393 (12) | 0.0648 (15) | −0.0008 (9) | −0.0079 (9) | −0.0009 (10) |
O3 | 0.0323 (10) | 0.0425 (12) | 0.0555 (14) | −0.0055 (9) | −0.0018 (9) | 0.0043 (10) |
O4 | 0.0395 (12) | 0.0409 (13) | 0.092 (2) | −0.0009 (10) | −0.0120 (12) | 0.0193 (13) |
O5 | 0.0458 (13) | 0.0373 (12) | 0.0786 (18) | −0.0083 (10) | −0.0054 (12) | 0.0109 (12) |
O6 | 0.0378 (12) | 0.0526 (15) | 0.0787 (19) | −0.0125 (11) | −0.0037 (12) | −0.0083 (13) |
C1—N1 | 1.342 (4) | C6—O2 | 1.261 (3) |
C1—C2 | 1.370 (4) | C7—O4 | 1.227 (4) |
C1—C6 | 1.514 (4) | C7—O3 | 1.284 (3) |
C2—C3 | 1.384 (4) | C7—C8 | 1.488 (4) |
C2—H2 | 0.9300 | C8—C9 | 1.328 (4) |
C3—C4 | 1.376 (5) | C8—H8 | 0.9300 |
C3—H3 | 0.9300 | C9—C10 | 1.484 (4) |
C4—C5 | 1.369 (4) | C9—H9 | 0.9300 |
C4—H4 | 0.9300 | C10—O6 | 1.213 (4) |
C5—N1 | 1.336 (4) | C10—O5 | 1.315 (4) |
C5—H5 | 0.9300 | O2—H2A | 0.8200 |
N1—H1 | 0.8600 | O5—H5A | 0.8200 |
C6—O1 | 1.224 (4) | ||
N1—C1—C2 | 118.8 (2) | O1—C6—O2 | 128.0 (3) |
N1—C1—C6 | 116.8 (2) | O1—C6—C1 | 117.9 (3) |
C2—C1—C6 | 124.4 (3) | O2—C6—C1 | 114.0 (2) |
C1—C2—C3 | 119.7 (3) | O4—C7—O3 | 123.4 (3) |
C1—C2—H2 | 120.1 | O4—C7—C8 | 124.1 (3) |
C3—C2—H2 | 120.1 | O3—C7—C8 | 112.5 (3) |
C4—C3—C2 | 119.5 (3) | C9—C8—C7 | 129.5 (3) |
C4—C3—H3 | 120.2 | C9—C8—H8 | 115.2 |
C2—C3—H3 | 120.2 | C7—C8—H8 | 115.2 |
C5—C4—C3 | 119.5 (3) | C8—C9—C10 | 132.4 (3) |
C5—C4—H4 | 120.3 | C8—C9—H9 | 113.8 |
C3—C4—H4 | 120.3 | C10—C9—H9 | 113.8 |
N1—C5—C4 | 119.4 (3) | O6—C10—O5 | 120.7 (3) |
N1—C5—H5 | 120.3 | O6—C10—C9 | 119.4 (3) |
C4—C5—H5 | 120.3 | O5—C10—C9 | 120.0 (3) |
C5—N1—C1 | 123.1 (2) | C6—O2—H2A | 109.5 |
C5—N1—H1 | 118.5 | C10—O5—H5A | 109.5 |
C1—N1—H1 | 118.5 | ||
N1—C1—C2—C3 | 0.0 (5) | C2—C1—C6—O1 | −8.5 (5) |
C6—C1—C2—C3 | −179.9 (3) | N1—C1—C6—O2 | −7.8 (4) |
C1—C2—C3—C4 | −0.3 (5) | C2—C1—C6—O2 | 172.1 (3) |
C2—C3—C4—C5 | 0.2 (5) | O4—C7—C8—C9 | −1.2 (6) |
C3—C4—C5—N1 | 0.2 (5) | O3—C7—C8—C9 | 178.2 (3) |
C4—C5—N1—C1 | −0.6 (5) | C7—C8—C9—C10 | −1.2 (6) |
C2—C1—N1—C5 | 0.5 (5) | C8—C9—C10—O6 | −171.4 (4) |
C6—C1—N1—C5 | −179.7 (3) | C8—C9—C10—O5 | 8.0 (6) |
N1—C1—C6—O1 | 171.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.28 | 2.639 (3) | 105 |
O5—H5A···O4 | 0.82 | 1.73 | 2.540 (3) | 168 |
N1—H1···O1i | 0.86 | 2.02 | 2.725 (3) | 139 |
O2—H2A···O3ii | 0.82 | 1.71 | 2.463 (3) | 152 |
C2—H2···O2iii | 0.93 | 2.54 | 3.462 (4) | 170 |
C3—H3···O6iv | 0.93 | 2.59 | 3.221 (4) | 125 |
C5—H5···O4v | 0.93 | 2.40 | 3.251 (4) | 152 |
C8—H8···O6vi | 0.93 | 2.40 | 3.285 (4) | 158 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y, −z; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, −y, −z+1; (v) x, −y+1/2, z+1/2; (vi) −x+2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H6NO2·C4H3O4 |
Mr | 239.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 14.6498 (9), 10.3976 (8), 6.9067 (5) |
β (°) | 100.089 (3) |
V (Å3) | 1035.78 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.24 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.970, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9722, 2557, 2092 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.199, 1.10 |
No. of reflections | 2557 |
No. of parameters | 155 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.33 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.28 | 2.639 (3) | 105 |
O5—H5A···O4 | 0.82 | 1.73 | 2.540 (3) | 168 |
N1—H1···O1i | 0.86 | 2.02 | 2.725 (3) | 139 |
O2—H2A···O3ii | 0.82 | 1.71 | 2.463 (3) | 152 |
C2—H2···O2iii | 0.93 | 2.54 | 3.462 (4) | 170 |
C3—H3···O6iv | 0.93 | 2.59 | 3.221 (4) | 125 |
C5—H5···O4v | 0.93 | 2.40 | 3.251 (4) | 152 |
C8—H8···O6vi | 0.93 | 2.40 | 3.285 (4) | 158 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y, −z; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, −y, −z+1; (v) x, −y+1/2, z+1/2; (vi) −x+2, y−1/2, −z+1/2. |
Acknowledgements
The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.
References
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Pyridine and its derivatives are some of the most frequently used synthons in supramolecular chemistry based on hydrogen bonds (Banerjee & Murugavel, 2004; Bis et al., 2006). We herewith report the molecular and crystal structures of the title compound, I, which belongs to this class of compounds.
The asymmetric unit of I, (Fig. 1), contains a 2–carboxypyridinium cation and a malonate anion. The bond lengths (Allen et al., 1987) and angles are within the normal range. The crystal structure exhibit weak intermolecular N—H···O, O—H···O and C—H···O (Table 1 & Fig. 2) interactions.