Acta Cryst. (2008). E64, o1641 [ doi:10.1107/S1600536808020357 ]
In the title compound, C11H10NO3+·NO3-·H2O, the planar 8-carboxymethoxyquinolinium cation, the nitrate anion and the water molecule are dimerized by hydrogen bonds into square building-block units, and then further assembled into two-dimensional gently undulating supramolecular layers.
A solution of Cu(NO3)2 (363 mg, 1.00 mmol) in CH3OH (20 ml) was slowly added to a solution of 2-(quinolin-8-yloxy)acetic acid (410 mg, 1.95 mmol) in CH3OH (10 ml). The resultant blue solution was stirred for 2 h at room temperature and then filtered. Colorless crystals suitable for X-ray diffraction were obtained in two day by slow diffusion of diethyl ether into a dilute solution of the title complex in methanol. The assigned structure was substantiated by elemental analysis; calculated for C11H12N2O7: C 46.44, H 4.22, N 9.85%; found: C 46.36, H 4.28, N 9.82%.
The structure was solved using direct methods followed by Fourier synthesis. Non-H atoms were refined anisotropically. All of H atoms except water molecule were placed in idealized positions (C—H = 0.93 or 0.97 Å, O—H = 0.82 Å, N—H = 0.86 Å), forced to ride on the atom to which they are bonded, and were included in the refinement in the riding-model approximation. Uiso values were set equal to 1.5Ueq(parent atom) for methyl H atoms and to 1.2Ueq(parent atom)for all other H atoms. The water H atoms were located in a difference Fourier map, and were refined with distance restraints of O—H = 0.84 (1) and H···H 1.43 (2) Å, but their Uiso values were set equal to 1.5 Ueq(parent atom O).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./rn2043fig1thm.gif)
| Fig. 1. The structure of the title compound (I). The atom-numbering scheme is shown and ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./rn2043fig2thm.gif)
| Fig. 2. A view of the dimerized supramolecular sheet constructed by hydrogen bonding interactions. Symmetry codes i: 1.5-x, 0.5+y, 0.5-z; ii: 2-x, 2-y, 1-z; iii: 0.5+x, 1.5-y, 0.5+z. |
| C11H10NO3+·NO3–·H2O | F000 = 592 |
| Mr = 284.23 | Dx = 1.523 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P2yn | Cell parameters from 1544 reflections |
| a = 5.3577 (5) Å | θ = 2.7–22.5º |
| b = 19.5100 (17) Å | µ = 0.13 mm−1 |
| c = 11.8959 (11) Å | T = 298 (2) K |
| β = 94.663 (3)º | Block, yellow |
| V = 1239.3 (2) Å3 | 0.25 × 0.22 × 0.16 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 2071 independent reflections |
| Radiation source: fine-focus sealed tube | 1376 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.026 |
| T = 298(2) K | θmax = 25.5º |
| φ and ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→6 |
| Tmin = 0.968, Tmax = 0.980 | k = −23→22 |
| 6235 measured reflections | l = −14→13 |
| 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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0466P)2 + 0.237P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max = 0.001 |
| 2071 reflections | Δρmax = 0.14 e Å−3 |
| 189 parameters | Δρmin = −0.16 e Å−3 |
| 3 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0044 (12) |
| C11H10NO3+·NO3–·H2O | V = 1239.3 (2) Å3 |
| Mr = 284.23 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 5.3577 (5) Å | µ = 0.13 mm−1 |
| b = 19.5100 (17) Å | T = 298 (2) K |
| c = 11.8959 (11) Å | 0.25 × 0.22 × 0.16 mm |
| β = 94.663 (3)º |
| Bruker SMART CCD area-detector diffractometer | 2071 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1376 reflections with I > 2σ(I) |
| Tmin = 0.968, Tmax = 0.980 | Rint = 0.026 |
| 6235 measured reflections |
| R[F2 > 2σ(F2)] = 0.040 | 3 restraints |
| wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.02 | Δρmax = 0.14 e Å−3 |
| 2071 reflections | Δρmin = −0.16 e Å−3 |
| 189 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.3857 (3) | 1.04106 (6) | 0.31886 (12) | 0.0504 (4) | |
| O2 | 0.7769 (3) | 1.08262 (7) | 0.45561 (14) | 0.0639 (5) | |
| O3 | 0.6421 (3) | 1.19011 (7) | 0.44971 (15) | 0.0717 (5) | |
| H3 | 0.7765 | 1.1975 | 0.4856 | 0.107* | |
| O4 | 0.7649 (4) | 0.21455 (8) | 0.17156 (19) | 0.0945 (7) | |
| O5 | 0.5562 (3) | 0.28962 (8) | 0.07269 (16) | 0.0761 (6) | |
| O6 | 0.4361 (4) | 0.18475 (9) | 0.07206 (17) | 0.0943 (7) | |
| O7 | 0.7613 (3) | 0.94258 (8) | 0.41435 (15) | 0.0697 (5) | |
| H7A | 0.766 (4) | 0.9861 (5) | 0.420 (2) | 0.105* | |
| H7B | 0.893 (3) | 0.9224 (10) | 0.439 (2) | 0.105* | |
| N1 | 0.3815 (3) | 0.90790 (8) | 0.26857 (14) | 0.0478 (5) | |
| H1 | 0.4942 | 0.9259 | 0.3150 | 0.057* | |
| N2 | 0.5863 (4) | 0.22855 (10) | 0.10544 (17) | 0.0595 (5) | |
| C1 | 0.3960 (5) | 0.84190 (10) | 0.24671 (19) | 0.0585 (6) | |
| H1A | 0.5251 | 0.8159 | 0.2820 | 0.070* | |
| C2 | 0.2210 (5) | 0.81128 (12) | 0.1718 (2) | 0.0678 (7) | |
| H2 | 0.2335 | 0.7649 | 0.1552 | 0.081* | |
| C3 | 0.0298 (5) | 0.84926 (12) | 0.1222 (2) | 0.0633 (7) | |
| H3A | −0.0890 | 0.8285 | 0.0719 | 0.076* | |
| C4 | 0.0098 (4) | 0.91954 (11) | 0.14604 (17) | 0.0491 (6) | |
| C5 | −0.1837 (5) | 0.96193 (13) | 0.09874 (19) | 0.0597 (6) | |
| H5 | −0.3112 | 0.9434 | 0.0503 | 0.072* | |
| C6 | −0.1842 (5) | 1.02966 (12) | 0.12375 (19) | 0.0592 (6) | |
| H6 | −0.3134 | 1.0571 | 0.0923 | 0.071* | |
| C7 | 0.0059 (4) | 1.05930 (11) | 0.19611 (18) | 0.0503 (6) | |
| H7 | 0.0039 | 1.1062 | 0.2103 | 0.060* | |
| C8 | 0.1930 (4) | 1.01977 (9) | 0.24550 (16) | 0.0428 (5) | |
| C9 | 0.1954 (4) | 0.94906 (10) | 0.22072 (16) | 0.0415 (5) | |
| C10 | 0.4012 (4) | 1.11253 (9) | 0.34252 (17) | 0.0480 (6) | |
| H10A | 0.2518 | 1.1275 | 0.3764 | 0.058* | |
| H10B | 0.4137 | 1.1380 | 0.2732 | 0.058* | |
| C11 | 0.6279 (4) | 1.12555 (11) | 0.42193 (17) | 0.0482 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0499 (10) | 0.0361 (7) | 0.0612 (9) | 0.0015 (7) | −0.0185 (8) | −0.0028 (6) |
| O2 | 0.0534 (11) | 0.0450 (9) | 0.0881 (11) | 0.0037 (8) | −0.0256 (9) | −0.0097 (8) |
| O3 | 0.0775 (14) | 0.0385 (8) | 0.0930 (13) | −0.0001 (8) | −0.0295 (10) | −0.0109 (8) |
| O4 | 0.0822 (14) | 0.0620 (11) | 0.1291 (16) | 0.0015 (10) | −0.0530 (13) | 0.0185 (11) |
| O5 | 0.0753 (13) | 0.0433 (9) | 0.1048 (13) | 0.0006 (8) | −0.0219 (10) | 0.0184 (9) |
| O6 | 0.0987 (16) | 0.0594 (10) | 0.1156 (15) | −0.0244 (11) | −0.0464 (13) | 0.0157 (10) |
| O7 | 0.0638 (12) | 0.0514 (9) | 0.0877 (12) | 0.0058 (8) | −0.0320 (10) | −0.0014 (9) |
| N1 | 0.0471 (12) | 0.0411 (10) | 0.0533 (10) | −0.0052 (9) | −0.0074 (9) | 0.0001 (8) |
| N2 | 0.0587 (14) | 0.0471 (12) | 0.0697 (13) | 0.0000 (11) | −0.0124 (11) | 0.0048 (10) |
| C1 | 0.0633 (17) | 0.0381 (12) | 0.0723 (15) | −0.0001 (11) | −0.0047 (14) | 0.0011 (11) |
| C2 | 0.077 (2) | 0.0438 (13) | 0.0808 (17) | −0.0116 (13) | −0.0052 (15) | −0.0090 (12) |
| C3 | 0.0669 (18) | 0.0577 (14) | 0.0630 (15) | −0.0201 (13) | −0.0083 (14) | −0.0099 (12) |
| C4 | 0.0439 (14) | 0.0542 (13) | 0.0474 (12) | −0.0082 (11) | −0.0059 (11) | −0.0006 (10) |
| C5 | 0.0461 (16) | 0.0749 (17) | 0.0552 (14) | −0.0107 (13) | −0.0143 (12) | −0.0008 (12) |
| C6 | 0.0450 (15) | 0.0719 (16) | 0.0579 (14) | 0.0072 (13) | −0.0120 (12) | 0.0073 (12) |
| C7 | 0.0455 (15) | 0.0474 (12) | 0.0562 (13) | 0.0041 (11) | −0.0061 (12) | 0.0045 (10) |
| C8 | 0.0405 (14) | 0.0433 (12) | 0.0429 (11) | −0.0027 (10) | −0.0068 (11) | 0.0010 (9) |
| C9 | 0.0361 (13) | 0.0434 (11) | 0.0437 (11) | −0.0018 (10) | −0.0038 (10) | 0.0036 (9) |
| C10 | 0.0508 (15) | 0.0347 (11) | 0.0560 (13) | 0.0005 (10) | −0.0102 (11) | 0.0011 (9) |
| C11 | 0.0506 (15) | 0.0400 (12) | 0.0528 (13) | −0.0033 (11) | −0.0038 (11) | −0.0008 (10) |
| O1—C8 | 1.362 (2) | C2—H2 | 0.9300 |
| O1—C10 | 1.424 (2) | C3—C4 | 1.406 (3) |
| O2—C11 | 1.203 (2) | C3—H3A | 0.9300 |
| O3—C11 | 1.303 (2) | C4—C9 | 1.402 (3) |
| O3—H3 | 0.8200 | C4—C5 | 1.407 (3) |
| O4—N2 | 1.219 (2) | C5—C6 | 1.355 (3) |
| O5—N2 | 1.260 (2) | C5—H5 | 0.9300 |
| O6—N2 | 1.218 (2) | C6—C7 | 1.403 (3) |
| O7—H7A | 0.852 (9) | C6—H6 | 0.9300 |
| O7—H7B | 0.841 (9) | C7—C8 | 1.360 (3) |
| N1—C1 | 1.317 (2) | C7—H7 | 0.9300 |
| N1—C9 | 1.368 (2) | C8—C9 | 1.411 (3) |
| N1—H1 | 0.8600 | C10—C11 | 1.498 (3) |
| C1—C2 | 1.377 (3) | C10—H10A | 0.9700 |
| C1—H1A | 0.9300 | C10—H10B | 0.9700 |
| C2—C3 | 1.359 (3) | ||
| C8—O1—C10 | 117.04 (15) | C4—C5—H5 | 120.0 |
| C11—O3—H3 | 109.5 | C5—C6—C7 | 121.5 (2) |
| H7A—O7—H7B | 114.9 (13) | C5—C6—H6 | 119.2 |
| C1—N1—C9 | 122.98 (19) | C7—C6—H6 | 119.2 |
| C1—N1—H1 | 118.5 | C8—C7—C6 | 120.3 (2) |
| C9—N1—H1 | 118.5 | C8—C7—H7 | 119.9 |
| O6—N2—O4 | 121.1 (2) | C6—C7—H7 | 119.9 |
| O6—N2—O5 | 119.9 (2) | C7—C8—O1 | 126.71 (18) |
| O4—N2—O5 | 119.1 (2) | C7—C8—C9 | 118.90 (19) |
| N1—C1—C2 | 120.3 (2) | O1—C8—C9 | 114.39 (17) |
| N1—C1—H1A | 119.9 | N1—C9—C4 | 118.56 (18) |
| C2—C1—H1A | 119.9 | N1—C9—C8 | 120.38 (18) |
| C3—C2—C1 | 119.6 (2) | C4—C9—C8 | 121.06 (19) |
| C3—C2—H2 | 120.2 | O1—C10—C11 | 108.78 (16) |
| C1—C2—H2 | 120.2 | O1—C10—H10A | 109.9 |
| C2—C3—C4 | 120.7 (2) | C11—C10—H10A | 109.9 |
| C2—C3—H3A | 119.6 | O1—C10—H10B | 109.9 |
| C4—C3—H3A | 119.6 | C11—C10—H10B | 109.9 |
| C9—C4—C3 | 117.8 (2) | H10A—C10—H10B | 108.3 |
| C9—C4—C5 | 118.3 (2) | O2—C11—O3 | 124.4 (2) |
| C3—C4—C5 | 123.9 (2) | O2—C11—C10 | 125.03 (19) |
| C6—C5—C4 | 120.0 (2) | O3—C11—C10 | 110.57 (19) |
| C6—C5—H5 | 120.0 | ||
| C9—N1—C1—C2 | 0.8 (3) | C1—N1—C9—C4 | 0.8 (3) |
| N1—C1—C2—C3 | −1.4 (4) | C1—N1—C9—C8 | −178.5 (2) |
| C1—C2—C3—C4 | 0.4 (4) | C3—C4—C9—N1 | −1.7 (3) |
| C2—C3—C4—C9 | 1.1 (3) | C5—C4—C9—N1 | 178.85 (19) |
| C2—C3—C4—C5 | −179.4 (2) | C3—C4—C9—C8 | 177.63 (19) |
| C9—C4—C5—C6 | 1.5 (3) | C5—C4—C9—C8 | −1.8 (3) |
| C3—C4—C5—C6 | −177.9 (2) | C7—C8—C9—N1 | 179.70 (19) |
| C4—C5—C6—C7 | 0.3 (4) | O1—C8—C9—N1 | −0.3 (3) |
| C5—C6—C7—C8 | −1.8 (3) | C7—C8—C9—C4 | 0.4 (3) |
| C6—C7—C8—O1 | −178.6 (2) | O1—C8—C9—C4 | −179.64 (18) |
| C6—C7—C8—C9 | 1.4 (3) | C8—O1—C10—C11 | −178.52 (17) |
| C10—O1—C8—C7 | −3.3 (3) | O1—C10—C11—O2 | 3.0 (3) |
| C10—O1—C8—C9 | 176.72 (17) | O1—C10—C11—O3 | −177.08 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O7 | 0.86 | 1.81 | 2.652 (2) | 166 |
| O7—H7B···O5i | 0.841 (9) | 2.610 (18) | 3.140 (2) | 122.3 (19) |
| O7—H7B···O2ii | 0.841 (9) | 2.085 (16) | 2.852 (2) | 152 (2) |
| O7—H7A···O1 | 0.852 (9) | 2.52 (2) | 2.943 (2) | 111.6 (18) |
| O7—H7A···O2 | 0.852 (9) | 1.929 (11) | 2.776 (2) | 172 (3) |
| O3—H3···O6iii | 0.82 | 2.63 | 3.192 (2) | 127 |
| O3—H3···N2iii | 0.82 | 2.55 | 3.301 (3) | 154 |
| O3—H3···O5iii | 0.82 | 1.77 | 2.587 (2) | 175 |
| Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y+2, −z+1; (iii) x+1/2, −y+3/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O7 | 0.86 | 1.81 | 2.652 (2) | 166 |
| O7—H7B···O5i | 0.841 (9) | 2.610 (18) | 3.140 (2) | 122.3 (19) |
| O7—H7B···O2ii | 0.841 (9) | 2.085 (16) | 2.852 (2) | 152 (2) |
| O7—H7A···O1 | 0.852 (9) | 2.52 (2) | 2.943 (2) | 111.6 (18) |
| O7—H7A···O2 | 0.852 (9) | 1.929 (11) | 2.776 (2) | 172 (3) |
| O3—H3···O6iii | 0.82 | 2.63 | 3.192 (2) | 127 |
| O3—H3···N2iii | 0.82 | 2.55 | 3.301 (3) | 154 |
| O3—H3···O5iii | 0.82 | 1.77 | 2.587 (2) | 175 |
| Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y+2, −z+1; (iii) x+1/2, −y+3/2, z+1/2. |
The work was supported by the National Natural Science Foundation of China (grant No. 20772037)and the NSF of Guangdong Province, China (grant No. 06025033).
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Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
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Das, V. G. K., Wei, C., Ng, S. W. & Mak, T. C. W. (1987). J. Organomet. Chem. 322, 33–47.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
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Wang, Y.-H. & Lu, F. (2004). Acta Cryst. C60, m557–m559.
There are no reports of the title compound but there are several reports on metal compounds involving the ligand 2-(quinolin-8-yloxy)acetate and its derivatives (Czugler & Kalman, 1981; Das et al., 1987; Wang & Lu, 2004; Song et al., 2004). The title compound (Scheme I) contains one cation, one nitrate anion and one water molecule (Fig.1).
Fig. 2 shows that the cation, the nitrate anion and water molecule are dimerized by the hydrogen bonds (Table 1) into stable square building block units, and then further assembled into 2D supramolecular layers which are gently undulating.