![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
organic compounds
3-Carboxyquinolin-1-ium-2-carboxylate monohydrate
aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
*Correspondence e-mail: guangbocheujs@yahoo.com.cn
The title compound, C11H7NO4·H2O, contains a 3-carboxyquinolin-1-ium-2-carboxylate (qda) zwitterion and one water molecule. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion dimers, and these dimers are further connected by O—H⋯O hydrogen bonds into a three-dimensional supramolecular architecture. In addition, π–π interactions occur between pyridine and benzene rings from different qda ligands [centroid–centroid distance = 3.749 (1) Å] and the dihedral angles of the –CO2H and –CO2 groups to the quinoline system are 8.47 (3) and 88.16 (6)°, respectively.
Related literature
For background on the use of quinoline carboxylic acid derivatives in metal organic frameworks, see: Dobrzyńska et al. (2004, 2005
); Hu et al. (2007
); Li & Liu (2010
). For background on the role of noncovalent intermolecular interactions, see: Wang et al. (2011
). For related structures, see: Dobrzyńska et al. (2004
); Dobrzyńska & Jerzykiewicz (2008
); Odoko et al. (2001
); Zurowska et al. (2007
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: CrystalClear (Rigaku, 2007); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: CrystalClear (Rigaku, 2007
) and DIAMOND (Brandenburg, 1998
); software used to prepare material for publication: SHELXTL (Sheldrick, 2008
).
Supporting information
10.1107/S1600536812006988/zj2053sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812006988/zj2053Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812006988/zj2053Isup3.cml
The quinoline-2,3-dicarboxylic acid (qda) was purchased commercially and used without further purification. A mixture of ZnCl2 (13.4 mg, 0.1 mmol), and qda (43.8 mg, 0.2 mmol) was dissolved in a 15 mL of water, and the pH was adjusted to 7 by 1 mol L-1 sodium hydroxide solution. Then the mixture was placed in a 25 mL autoclave with Teflon-liner. The autoclave was heated to 433 K and held at this temperature for three days. It was then cooled to room temperature under spontaneous conditions. The colourless block crystals were obtained with a yield of 60 %, however, X-ray crystallographic study shows that this crystal is not zinc complex but the title compound.
All H atoms on C atoms were placed in an ideal position using a riding model th with C—H distances of 0.93 Å and Uiso(H)=1.2Ueq(C). The pyridinium NH and hydroxy H-atoms were located in a difference Fourier map with N—H distance of 0.933 Å and O—H distance of 0.893 Å, and their temperature factors were freely refined. Water hydrogen atoms were also located in a difference Fourier map with a distance restraint to their parent O atoms (0.867 and 0.858 Å, respectively) and Uiso(H)=1.5Ueq(O).
Data collection: CrystalClear (Rigaku, 2007); cell
CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalClear (Rigaku, 2007) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C11H7NO4·H2O | F(000) = 488 |
Mr = 235.19 | Dx = 1.549 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4018 reflections |
a = 7.5424 (15) Å | θ = 4.0–28.9° |
b = 14.422 (3) Å | µ = 0.13 mm−1 |
c = 9.755 (2) Å | T = 153 K |
β = 108.17 (3)° | Prism, colourless |
V = 1008.3 (4) Å3 | 0.15 × 0.13 × 0.11 mm |
Z = 4 |
Rigaku CCD area-detector diffractometer | 1817 independent reflections |
Radiation source: fine-focus sealed tube | 1547 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.3°, θmin = 4.0° |
ω scans | h = −8→7 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | k = −17→15 |
Tmin = 0.981, Tmax = 1 | l = −8→11 |
4586 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0638P)2 + 0.0617P] where P = (Fo2 + 2Fc2)/3 |
1817 reflections | (Δ/σ)max = 0.001 |
168 parameters | Δρmax = 0.20 e Å−3 |
5 restraints | Δρmin = −0.20 e Å−3 |
C11H7NO4·H2O | V = 1008.3 (4) Å3 |
Mr = 235.19 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5424 (15) Å | µ = 0.13 mm−1 |
b = 14.422 (3) Å | T = 153 K |
c = 9.755 (2) Å | 0.15 × 0.13 × 0.11 mm |
β = 108.17 (3)° |
Rigaku CCD area-detector diffractometer | 1817 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | 1547 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 1 | Rint = 0.020 |
4586 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 5 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.20 e Å−3 |
1817 reflections | Δρmin = −0.20 e Å−3 |
168 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.65319 (19) | 0.09213 (9) | 1.05483 (14) | 0.0216 (3) | |
C2 | 0.67451 (18) | 0.30200 (9) | 1.06906 (15) | 0.0216 (3) | |
C3 | 0.54746 (17) | 0.25508 (9) | 0.93895 (14) | 0.0195 (3) | |
C4 | 0.54008 (17) | 0.15740 (9) | 0.93584 (14) | 0.0194 (3) | |
C5 | 0.31108 (17) | 0.16028 (10) | 0.70347 (14) | 0.0199 (3) | |
C6 | 0.31153 (18) | 0.25796 (9) | 0.70374 (14) | 0.0192 (3) | |
C7 | 0.19098 (18) | 0.30475 (10) | 0.58263 (14) | 0.0231 (3) | |
H7 | 0.1883 | 0.3692 | 0.5804 | 0.028* | |
C8 | 0.07928 (19) | 0.25556 (10) | 0.46975 (16) | 0.0255 (3) | |
H8 | 0.0000 | 0.2867 | 0.3909 | 0.031* | |
C9 | 0.08227 (19) | 0.15775 (10) | 0.47086 (15) | 0.0266 (3) | |
H9 | 0.0054 | 0.1253 | 0.3923 | 0.032* | |
C10 | 0.19651 (19) | 0.10985 (10) | 0.58570 (15) | 0.0254 (3) | |
H10 | 0.1983 | 0.0454 | 0.5858 | 0.031* | |
C11 | 0.43333 (17) | 0.30389 (9) | 0.82448 (14) | 0.0197 (3) | |
H11 | 0.4362 | 0.3684 | 0.8265 | 0.024* | |
O1 | 0.80640 (13) | 0.06645 (7) | 1.04539 (11) | 0.0322 (3) | |
O2 | 0.57317 (13) | 0.06656 (6) | 1.14257 (10) | 0.0241 (3) | |
O3 | 0.75594 (15) | 0.25971 (7) | 1.17666 (11) | 0.0346 (3) | |
N1 | 0.42599 (15) | 0.11485 (8) | 0.82176 (11) | 0.0206 (3) | |
H1A | 0.418 (2) | 0.0503 (15) | 0.8245 (19) | 0.046 (5)* | |
O1W | 0.88294 (16) | 0.02969 (8) | 0.79197 (12) | 0.0380 (3) | |
H1C | 0.987 (2) | 0.0010 (13) | 0.825 (2) | 0.057* | |
H1D | 0.853 (3) | 0.0434 (14) | 0.8685 (19) | 0.057* | |
O4 | 0.68389 (15) | 0.39253 (7) | 1.05383 (12) | 0.0300 (3) | |
H4A | 0.757 (3) | 0.4174 (13) | 1.136 (3) | 0.059 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0257 (7) | 0.0190 (7) | 0.0174 (7) | 0.0003 (5) | 0.0030 (6) | −0.0014 (5) |
C2 | 0.0206 (7) | 0.0246 (7) | 0.0197 (8) | −0.0019 (6) | 0.0061 (6) | 0.0011 (6) |
C3 | 0.0197 (7) | 0.0212 (7) | 0.0184 (7) | −0.0010 (5) | 0.0070 (6) | 0.0002 (5) |
C4 | 0.0184 (7) | 0.0224 (7) | 0.0181 (7) | 0.0003 (5) | 0.0067 (5) | 0.0004 (5) |
C5 | 0.0193 (7) | 0.0224 (7) | 0.0180 (7) | 0.0006 (5) | 0.0060 (5) | 0.0014 (5) |
C6 | 0.0185 (7) | 0.0214 (7) | 0.0183 (7) | 0.0006 (5) | 0.0067 (6) | 0.0002 (5) |
C7 | 0.0234 (7) | 0.0226 (7) | 0.0225 (8) | 0.0031 (6) | 0.0059 (6) | 0.0028 (6) |
C8 | 0.0210 (7) | 0.0319 (8) | 0.0197 (7) | 0.0040 (6) | 0.0006 (6) | 0.0032 (6) |
C9 | 0.0231 (7) | 0.0326 (8) | 0.0209 (7) | −0.0040 (6) | 0.0022 (6) | −0.0049 (6) |
C10 | 0.0280 (8) | 0.0223 (7) | 0.0251 (8) | −0.0034 (6) | 0.0068 (6) | −0.0021 (6) |
C11 | 0.0224 (7) | 0.0183 (7) | 0.0199 (8) | 0.0001 (5) | 0.0087 (6) | 0.0007 (5) |
O1 | 0.0256 (5) | 0.0411 (6) | 0.0285 (6) | 0.0120 (5) | 0.0063 (4) | 0.0085 (5) |
O2 | 0.0345 (6) | 0.0186 (5) | 0.0198 (5) | 0.0016 (4) | 0.0092 (4) | 0.0012 (4) |
O3 | 0.0391 (6) | 0.0319 (6) | 0.0220 (6) | −0.0069 (5) | −0.0061 (5) | 0.0050 (5) |
N1 | 0.0240 (6) | 0.0173 (6) | 0.0193 (6) | 0.0012 (5) | 0.0050 (5) | 0.0010 (4) |
O1W | 0.0426 (7) | 0.0441 (7) | 0.0249 (6) | 0.0210 (5) | 0.0073 (5) | 0.0095 (5) |
O4 | 0.0367 (6) | 0.0217 (5) | 0.0243 (6) | −0.0046 (4) | −0.0011 (5) | −0.0029 (4) |
C1—O1 | 1.2439 (17) | C6—C7 | 1.4170 (18) |
C1—O2 | 1.2470 (17) | C7—C8 | 1.359 (2) |
C1—C4 | 1.5310 (18) | C7—H7 | 0.9300 |
C2—O3 | 1.2038 (16) | C8—C9 | 1.411 (2) |
C2—O4 | 1.3184 (17) | C8—H8 | 0.9300 |
C2—C3 | 1.4929 (18) | C9—C10 | 1.369 (2) |
C3—C11 | 1.3727 (18) | C9—H9 | 0.9300 |
C3—C4 | 1.4098 (19) | C10—H10 | 0.9300 |
C4—N1 | 1.3260 (17) | C11—H11 | 0.9300 |
C5—N1 | 1.3741 (17) | N1—H1A | 0.93 (2) |
C5—C10 | 1.4059 (19) | O1W—H1C | 0.858 (15) |
C5—C6 | 1.409 (2) | O1W—H1D | 0.868 (15) |
C6—C11 | 1.4126 (19) | O4—H4A | 0.89 (2) |
O1—C1—O2 | 128.49 (13) | C8—C7—H7 | 120.0 |
O1—C1—C4 | 115.97 (12) | C6—C7—H7 | 120.0 |
O2—C1—C4 | 115.32 (11) | C7—C8—C9 | 120.75 (13) |
O3—C2—O4 | 124.70 (13) | C7—C8—H8 | 119.6 |
O3—C2—C3 | 121.96 (12) | C9—C8—H8 | 119.6 |
O4—C2—C3 | 113.32 (12) | C10—C9—C8 | 121.03 (13) |
C11—C3—C4 | 118.97 (12) | C10—C9—H9 | 119.5 |
C11—C3—C2 | 122.18 (12) | C8—C9—H9 | 119.5 |
C4—C3—C2 | 118.81 (11) | C9—C10—C5 | 118.53 (13) |
N1—C4—C3 | 119.43 (11) | C9—C10—H10 | 120.7 |
N1—C4—C1 | 114.47 (11) | C5—C10—H10 | 120.7 |
C3—C4—C1 | 126.09 (11) | C3—C11—C6 | 121.18 (13) |
N1—C5—C10 | 120.37 (13) | C3—C11—H11 | 119.4 |
N1—C5—C6 | 118.34 (12) | C6—C11—H11 | 119.4 |
C10—C5—C6 | 121.29 (12) | C4—N1—C5 | 123.95 (12) |
C5—C6—C11 | 118.10 (12) | C4—N1—H1A | 118.0 (11) |
C5—C6—C7 | 118.30 (12) | C5—N1—H1A | 118.0 (11) |
C11—C6—C7 | 123.60 (13) | H1C—O1W—H1D | 104.2 (18) |
C8—C7—C6 | 120.10 (13) | C2—O4—H4A | 109.7 (13) |
O3—C2—C3—C11 | 170.11 (13) | C5—C6—C7—C8 | −0.28 (18) |
O4—C2—C3—C11 | −8.67 (17) | C11—C6—C7—C8 | 179.25 (13) |
O3—C2—C3—C4 | −7.72 (19) | C6—C7—C8—C9 | −0.4 (2) |
O4—C2—C3—C4 | 173.51 (12) | C7—C8—C9—C10 | 0.4 (2) |
C11—C3—C4—N1 | 1.20 (18) | C8—C9—C10—C5 | 0.2 (2) |
C2—C3—C4—N1 | 179.10 (11) | N1—C5—C10—C9 | 179.13 (12) |
C11—C3—C4—C1 | −178.47 (11) | C6—C5—C10—C9 | −0.88 (19) |
C2—C3—C4—C1 | −0.57 (18) | C4—C3—C11—C6 | −0.89 (18) |
O1—C1—C4—N1 | 89.54 (14) | C2—C3—C11—C6 | −178.72 (12) |
O2—C1—C4—N1 | −85.51 (14) | C5—C6—C11—C3 | −0.38 (18) |
O1—C1—C4—C3 | −90.78 (16) | C7—C6—C11—C3 | −179.91 (12) |
O2—C1—C4—C3 | 94.17 (15) | C3—C4—N1—C5 | −0.20 (18) |
N1—C5—C6—C11 | 1.36 (18) | C1—C4—N1—C5 | 179.51 (11) |
C10—C5—C6—C11 | −178.63 (11) | C10—C5—N1—C4 | 178.89 (12) |
N1—C5—C6—C7 | −179.09 (11) | C6—C5—N1—C4 | −1.10 (18) |
C10—C5—C6—C7 | 0.92 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.93 (2) | 1.71 (2) | 2.6392 (16) | 170.7 (17) |
O1W—H1C···O1ii | 0.86 (2) | 1.93 (2) | 2.7589 (16) | 161 (2) |
O4—H4A···O1Wiii | 0.89 (2) | 1.70 (2) | 2.5950 (17) | 175.6 (19) |
O1W—H1D···O1 | 0.87 (2) | 1.90 (2) | 2.7597 (16) | 175 (2) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2; (iii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H7NO4·H2O |
Mr | 235.19 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 153 |
a, b, c (Å) | 7.5424 (15), 14.422 (3), 9.755 (2) |
β (°) | 108.17 (3) |
V (Å3) | 1008.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.15 × 0.13 × 0.11 |
Data collection | |
Diffractometer | Rigaku CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2007) |
Tmin, Tmax | 0.981, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4586, 1817, 1547 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.101, 1.05 |
No. of reflections | 1817 |
No. of parameters | 168 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.20 |
Computer programs: , SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalClear (Rigaku, 2007) and DIAMOND (Brandenburg, 1998), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.93 (2) | 1.71 (2) | 2.6392 (16) | 170.7 (17) |
O1W—H1C···O1ii | 0.858 (15) | 1.934 (16) | 2.7589 (16) | 160.7 (19) |
O4—H4A···O1Wiii | 0.89 (2) | 1.70 (2) | 2.5950 (17) | 175.6 (19) |
O1W—H1D···O1 | 0.868 (15) | 1.895 (16) | 2.7597 (16) | 175 (2) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2; (iii) x, −y+1/2, z+1/2. |
Acknowledgements
The authors are thankful for the support of Jiangsu University for this work.
References
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Dobrzyńska, D., Duczmal, M., Jerzykiewicz, L. B., Warchulska, J. & Drabent, K. (2004). Eur. J. Inorg. Chem. pp. 110–117. Google Scholar
Dobrzyńska, D. & Jerzykiewicz, L. B. (2008). Acta Cryst. E64, m1383–m1384. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dobrzyńska, D., Jerzykiewicz, L. B., Jezierska, J. & Duczmal, M. (2005). Cryst. Growth Des. 5, 1945–1951. Google Scholar
Hu, S., Zhang, S.-H. & Zeng, M.-H. (2007). Acta Cryst. E63, m2565. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, X. L. & Liu, G. Z. (2010). Z. Kristallogr. New Cryst. Struct. 225, 761–762. CAS Google Scholar
Odoko, M., Muranishi, Y. & Okabe, N. (2001). Acta Cryst. E57, m267–m269. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X. L., Zhang, J. X., Liu, G. C. & Lin, H. Y. (2011). J. Solid State Chem. 184, 280–288. Web of Science CSD CrossRef CAS Google Scholar
Zurowska, B., Mrozinski, J. & Ciunik, Z. (2007). Polyhedron, 26, 3085–3091. Web of Science CSD CrossRef CAS 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.
Quinoline carboxylic acid derivatives have been explored in the synthesis of metal organic frameworks due to their abundant coordination modes which lead to the construction of metal organic frameworks with intriguing structures and functional properties (Dobrzyńska et al. 2004; Hu et al. 2007; Dobrzyńska et al. 2005; Li & Liu 2010). It is well known that noncovalent intermolecular interactions such as hydrogen bonding interactions and π–π interactions, play crucial role in the design and construction of supramolecular architecture (Wang et al. 2011). Taking quinoline-2-carboxylic acid for example, the crystal structures of its metal complexes have been determined for several metal ions, including CuII (Zurowska et al. 2007), MnII (Dobrzyńska & Jerzykiewicz, 2008), NiII (Odoko et al. 2001), CoII and FeII (Dobrzyńska et al. 2004). Of these complexes, the magnetic properties of CuII, CoII and FeII complexes have also been investigated. Herein, the structurally similar quinoline-2,3-dicarboxylic acid (qda) is a good choice for constructing a framework with novel physical properties, and the crystal structure of its monohydrate is reported now.
In this report, the title compound was prepared by using quinoline-2,3-dicarboxylic acid (qda) ligand under hydrothermal conditions. The analysis of crystal structure shows that one proton of carboxyl group of qda is transferred to N atom from pyridine ring, and one water molecule exists in the crystal lattice (Fig. 1). As shown in Fig. 2, the N—H···O hydrogen bond (yellow dotted line) links the molecules into dimers, and these dimers are further connected by O–H···O hydrogen bond (black dotted line) to a 3D supramolecular architecture. In addition, the π–π interactions (blue dotted line) occur between pyridine ring and benzene ring from different qda ligands with the distance of 3.749 (1) Å, making the supramolecular network more stable (Fig. 3).