organic compounds
Bis(2,6-diaminopyridinium)–adipate–adipic acid–water (2/1/1/2)
aSamsun Vocational School, Ondokuz Mayıs University, TR-55139 Samsun, Turkey
*Correspondence e-mail: nevzatk@omu.edu.tr
The 5H8N3+·C6H8O42−·C6H10O4·2H2O, consists of aminopyridinium cations, adipate dianions, adipic acid molecules and disordered solvent water molecules [occupancies 0.50 (4) and 0.50 (4)]. Both the adipate and adipic acid are located across inversion centres. Eight-membered hydrogen-bonded rings exist involving aminopyridinium and adipate ions. Adipic acid molecules and adipate anions are linked into zigzag supramolecular chains by O—H⋯O hydrogen bonds.
of the title compound, 2CRelated literature
For general background, see: Lah et al. (2001); Yang et al. (1995); Goswami & Ghosh (1997); Lehn (1990). For related structures, see: Büyükgüngör & Odabaşoğlu (2002, 2006); Odabaşoğlu & Büyükgüngör (2006); Shanmuga Sundara Raj et al., (2000). For synthesis, see: Odabaşoğlu & Büyükgüngör (2006).
Experimental
Crystal data
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Refinement
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Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S1600536807055602/xu2332sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807055602/xu2332Isup2.hkl
The title compound was prepared by as described by Odabaşoğlu & Büyükgüngör (2006), using 2,6-diaminopyridine and adipic acid as starting materials. Crystals were obtained by slow evaporation from an aqueous solution.
The carboxy H atom was located in a difference Fourier map and refined isotropically. Water H atoms were located in a difference map and refined isotropically with O—H and H···H distances restrained to 0.82 (2) and 1.55 (4) Å, respectively. The site occupancies for disordered H5B and H5C was refined to 0.50 (4) and 0.50 (4), respectively. Other H atoms were refined using the riding model approximation, with C—H = 0.93 (aromatic), 0.97 Å (methylene) and N—H = 0.86 Å, Uiso(H) = 1.2Ueq(C,N).
The title crystal is obtained with the reaction of 2-aminopyridine (used in hair and other dyes) and adipic acid (used to
for plasticizers and as food additive). In addition, The cupper(II) complexes of 2-aminopyridinium carboxylates have important properties in the applications of pharmaceuticals, fungicides, oxygen transfer, homogenous hydrogenation, gas occlusion compounds, and solvent extractions processes (Lah et al., 2001; Yang et al., 1995). Hydrogen bonding plays a key role in molecular recognition (Goswami & Ghosh, 1997). The design of highly specific solid-state structure is of considerable significance in organic chemistry due to their important applications in the development of new optical, magnetic and electronic systems (Lehn, 1990). This report concerns the x-ray structure analysis of the title complex. In the structure investigations show that the 2-aminopyridinium ions are linked to the adipate ions by N1—H1···O1 and N3—H3···O2 hydrogen bonds through the formation of cyclic eight-membered hydrogen bonded rings.An ORTEP diagram of (I) with numbering scheme is shown in Fig. 1. The bond lengths and angles in the structure is within the normally expected ranges. Similar C1—N3 and C5—N2 bonds were observed in other 2-aminopyridine containing molecules (Büyükgüngör & Odabaşoğlu, 2002; Odabaşoğlu & Büyükgüngör, 2006; Shanmuga Sundara Raj et al., 2000). Furthermore, these bond angle and length agrees with that similar bond angle and length values of 2,6-diaminopyridinium hydrogen fumarate complex (Büyükgüngör & Odabaşoğlu, 2006).
2-Aminopyridine and derivatives, are protonated in acidic solution. As for mono-aminopyridinium adipate-adipic acid and in some 2-aminopyridine-containing molecules, the bonding of the H atom to the ring N atom of 2-aminopyridine rather than the amine N atom gives an ion for which an additional resonance structure can be written.
The packing of the molecules is shown in Figure 2. In (I), the 2,6-diaminopyridinium ions are linked to the adipate-adipic ions through N—H···O, O—H···O hydrogen bonds (Table 1). The dihedral angles between the aminopyridinium ring and the O1/O2/C9/C10/C11 and O3/O4/C6/C7/C8 groups are 3.31 (7) and 7.25 (8)° respectively.
The H atoms between the water molecules are distorted because of the mutual repulsive interactions. So, H5B and H5C atoms are the same H-atom in the water molecule, and this H-atom makes a flip-flop motion between the two positions with site occupation factors of 0.50 (4) and 0.50 (4), respectively. The other H-atom (H5A) of the water molecule is localized due to the O5—H5A···O4 intermolecular hydrogen bond between adipic acid molecules (Fig. 3).
For general background, see: Lah et al. (2001); Yang et al. (1995); Goswami & Ghosh (1997); Lehn, (1990). For related structures, see: Büyükgüngör & Odabaşoğlu, (2002, 2006); Odabaşoğlu & Büyükgüngör (2006); Shanmuga Sundara Raj et al., (2000). For synthesis, see: Odabaşoğlu & Büyükgüngör (2006).
Data collection: X-AREA (Stoe & Cie, 2002); cell
X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Farrugia, 1997) and PLUTON (Spek, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. An ORTEP-3 drawing of the title compound (I) showing the atomic numbering scheme and 50% probability displacement ellipsoids. | |
Fig. 2. A perspective view of the packing in (I). | |
Fig. 3. The disordered H atoms of water molecules in the crystal structure. |
2C5H8N3+·C6H8O42−·C6H10O4·2H2O | Z = 1 |
Mr = 546.58 | F(000) = 292 |
Triclinic, P1 | Dx = 1.391 Mg m−3 |
Hall symbol: -P 1 | Melting point = 428–429 K |
a = 5.0645 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.6261 (11) Å | Cell parameters from 8371 reflections |
c = 17.702 (3) Å | θ = 2.3–27.9° |
α = 87.861 (11)° | µ = 0.11 mm−1 |
β = 85.169 (11)° | T = 296 K |
γ = 73.323 (11)° | Plate, colourless |
V = 652.55 (18) Å3 | 0.60 × 0.48 × 0.08 mm |
Stoe IPDS 2 diffractometer | 2996 independent reflections |
Radiation source: fine-focus sealed tube | 2261 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.043 |
ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | h = −6→6 |
Tmin = 0.949, Tmax = 0.993 | k = −9→9 |
7575 measured reflections | l = −20→22 |
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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0653P)2 + 0.039P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2996 reflections | Δρmax = 0.21 e Å−3 |
192 parameters | Δρmin = −0.18 e Å−3 |
17 restraints | Extinction correction: SHELXL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.038 (10) |
2C5H8N3+·C6H8O42−·C6H10O4·2H2O | γ = 73.323 (11)° |
Mr = 546.58 | V = 652.55 (18) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.0645 (7) Å | Mo Kα radiation |
b = 7.6261 (11) Å | µ = 0.11 mm−1 |
c = 17.702 (3) Å | T = 296 K |
α = 87.861 (11)° | 0.60 × 0.48 × 0.08 mm |
β = 85.169 (11)° |
Stoe IPDS 2 diffractometer | 2996 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2261 reflections with I > 2σ(I) |
Tmin = 0.949, Tmax = 0.993 | Rint = 0.043 |
7575 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 17 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.21 e Å−3 |
2996 reflections | Δρmin = −0.18 e Å−3 |
192 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 | Occ. (<1) | |
O3 | 1.2490 (2) | 0.92346 (16) | 0.72447 (6) | 0.0543 (3) | |
O4 | 1.5316 (2) | 0.79673 (16) | 0.62672 (5) | 0.0512 (3) | |
C6 | 1.3110 (3) | 0.89651 (18) | 0.65252 (7) | 0.0374 (3) | |
N3 | 1.1687 (3) | 0.4528 (2) | 0.91704 (7) | 0.0546 (4) | |
H3A | 1.0050 | 0.5265 | 0.9243 | 0.066* | |
H3B | 1.2601 | 0.4051 | 0.9552 | 0.066* | |
C2 | 1.5414 (3) | 0.2937 (2) | 0.82983 (8) | 0.0460 (3) | |
H2 | 1.6516 | 0.2374 | 0.8683 | 0.055* | |
C7 | 1.0880 (3) | 1.00201 (19) | 0.60401 (7) | 0.0418 (3) | |
H7A | 1.0818 | 1.1303 | 0.6047 | 0.050* | |
H7B | 0.9120 | 0.9916 | 0.6267 | 0.050* | |
C1 | 1.2800 (3) | 0.41269 (18) | 0.84710 (7) | 0.0378 (3) | |
C11 | 0.1384 (3) | 0.92888 (18) | 0.99095 (7) | 0.0382 (3) | |
H11A | 0.1273 | 0.8107 | 1.0108 | 0.046* | |
H11B | 0.2798 | 0.9613 | 1.0164 | 0.046* | |
O2 | 0.6439 (2) | 0.69564 (16) | 0.93768 (6) | 0.0543 (3) | |
C3 | 1.6345 (3) | 0.2603 (2) | 0.75544 (9) | 0.0501 (4) | |
H3 | 1.8095 | 0.1809 | 0.7438 | 0.060* | |
C8 | 1.1183 (3) | 0.94351 (18) | 0.52225 (7) | 0.0388 (3) | |
H8A | 1.1244 | 0.8154 | 0.5207 | 0.047* | |
H8B | 1.2916 | 0.9562 | 0.4985 | 0.047* | |
C9 | 0.5041 (3) | 0.77673 (18) | 0.88646 (7) | 0.0364 (3) | |
C10 | 0.2239 (3) | 0.91266 (19) | 0.90622 (7) | 0.0388 (3) | |
H10A | 0.0849 | 0.8764 | 0.8812 | 0.047* | |
H10B | 0.2273 | 1.0322 | 0.8862 | 0.047* | |
N1 | 1.1255 (2) | 0.49227 (15) | 0.78902 (6) | 0.0370 (3) | |
H1 | 0.9640 | 0.5662 | 0.7997 | 0.044* | |
C4 | 1.4745 (3) | 0.3419 (2) | 0.69719 (8) | 0.0498 (4) | |
H4 | 1.5402 | 0.3177 | 0.6469 | 0.060* | |
O1 | 0.58652 (19) | 0.75241 (14) | 0.81637 (5) | 0.0438 (3) | |
C5 | 1.2154 (3) | 0.45998 (19) | 0.71505 (7) | 0.0396 (3) | |
N2 | 1.0457 (3) | 0.5462 (2) | 0.66285 (7) | 0.0553 (4) | |
H2A | 0.8862 | 0.6189 | 0.6767 | 0.066* | |
H2B | 1.0960 | 0.5289 | 0.6154 | 0.066* | |
O5 | 1.2848 (3) | 0.4164 (2) | 0.50152 (7) | 0.0631 (4) | |
H4A | 1.373 (4) | 0.865 (3) | 0.7510 (13) | 0.094 (8)* | |
H5A | 1.335 (4) | 0.338 (3) | 0.4684 (11) | 0.076 (6)* | |
H5B | 1.114 (4) | 0.448 (7) | 0.506 (3) | 0.089 (15)* | 0.50 (4) |
H5C | 1.416 (7) | 0.457 (6) | 0.507 (3) | 0.083 (15)* | 0.50 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0458 (6) | 0.0706 (7) | 0.0278 (5) | 0.0149 (5) | −0.0071 (4) | −0.0044 (5) |
O4 | 0.0367 (5) | 0.0684 (7) | 0.0338 (5) | 0.0096 (4) | −0.0053 (4) | −0.0049 (4) |
C6 | 0.0346 (6) | 0.0427 (7) | 0.0292 (6) | −0.0012 (5) | −0.0052 (5) | −0.0017 (5) |
N3 | 0.0456 (7) | 0.0723 (8) | 0.0295 (6) | 0.0086 (6) | −0.0002 (5) | 0.0004 (5) |
C2 | 0.0378 (7) | 0.0526 (8) | 0.0361 (7) | 0.0061 (6) | −0.0075 (5) | 0.0038 (6) |
C7 | 0.0372 (7) | 0.0470 (7) | 0.0322 (6) | 0.0043 (5) | −0.0076 (5) | −0.0020 (5) |
C1 | 0.0358 (6) | 0.0415 (7) | 0.0310 (6) | −0.0029 (5) | −0.0029 (5) | 0.0011 (5) |
C11 | 0.0341 (6) | 0.0455 (7) | 0.0288 (6) | −0.0018 (5) | −0.0010 (5) | −0.0020 (5) |
O2 | 0.0410 (5) | 0.0729 (7) | 0.0315 (5) | 0.0124 (5) | −0.0062 (4) | 0.0011 (5) |
C3 | 0.0370 (7) | 0.0570 (8) | 0.0419 (7) | 0.0092 (6) | −0.0005 (6) | −0.0042 (6) |
C8 | 0.0343 (6) | 0.0441 (7) | 0.0309 (6) | 0.0016 (5) | −0.0079 (5) | 0.0001 (5) |
C9 | 0.0322 (6) | 0.0426 (6) | 0.0292 (6) | −0.0021 (5) | −0.0027 (5) | −0.0017 (5) |
C10 | 0.0335 (6) | 0.0443 (7) | 0.0311 (6) | 0.0006 (5) | −0.0013 (5) | −0.0006 (5) |
N1 | 0.0298 (5) | 0.0424 (6) | 0.0312 (5) | 0.0016 (4) | −0.0012 (4) | −0.0001 (4) |
C4 | 0.0418 (7) | 0.0618 (9) | 0.0324 (7) | 0.0056 (6) | 0.0021 (6) | −0.0043 (6) |
O1 | 0.0373 (5) | 0.0547 (6) | 0.0274 (5) | 0.0052 (4) | 0.0000 (4) | −0.0023 (4) |
C5 | 0.0366 (6) | 0.0456 (7) | 0.0311 (6) | −0.0032 (5) | −0.0031 (5) | 0.0016 (5) |
N2 | 0.0421 (7) | 0.0760 (9) | 0.0331 (6) | 0.0073 (6) | −0.0075 (5) | 0.0038 (6) |
O5 | 0.0483 (7) | 0.0801 (9) | 0.0503 (7) | 0.0009 (6) | −0.0029 (6) | −0.0218 (6) |
O3—C6 | 1.2955 (15) | C3—C4 | 1.382 (2) |
O3—H4A | 0.829 (17) | C3—H3 | 0.9300 |
O4—C6 | 1.2196 (16) | C8—C8ii | 1.521 (2) |
C6—C7 | 1.5001 (18) | C8—H8A | 0.9700 |
N3—C1 | 1.3252 (17) | C8—H8B | 0.9700 |
N3—H3A | 0.8600 | C9—O1 | 1.2781 (15) |
N3—H3B | 0.8600 | C9—C10 | 1.5199 (16) |
C2—C3 | 1.369 (2) | C10—H10A | 0.9700 |
C2—C1 | 1.3901 (18) | C10—H10B | 0.9700 |
C2—H2 | 0.9300 | N1—C5 | 1.3572 (16) |
C7—C8 | 1.5129 (17) | N1—H1 | 0.8600 |
C7—H7A | 0.9700 | C4—C5 | 1.3806 (18) |
C7—H7B | 0.9700 | C4—H4 | 0.9300 |
C1—N1 | 1.3617 (17) | C5—N2 | 1.3375 (17) |
C11—C11i | 1.524 (2) | N2—H2A | 0.8600 |
C11—C10 | 1.5253 (17) | N2—H2B | 0.8600 |
C11—H11A | 0.9700 | O5—H5A | 0.824 (16) |
C11—H11B | 0.9700 | O5—H5B | 0.824 (19) |
O2—C9 | 1.2332 (16) | O5—H5C | 0.823 (19) |
C6—O3—H4A | 113.2 (17) | C7—C8—H8A | 109.2 |
O4—C6—O3 | 123.06 (12) | C8ii—C8—H8A | 109.2 |
O4—C6—C7 | 123.27 (11) | C7—C8—H8B | 109.2 |
O3—C6—C7 | 113.66 (11) | C8ii—C8—H8B | 109.2 |
C1—N3—H3A | 120.0 | H8A—C8—H8B | 107.9 |
C1—N3—H3B | 120.0 | O2—C9—O1 | 122.48 (11) |
H3A—N3—H3B | 120.0 | O2—C9—C10 | 119.63 (11) |
C3—C2—C1 | 119.16 (13) | O1—C9—C10 | 117.89 (11) |
C3—C2—H2 | 120.4 | C9—C10—C11 | 114.35 (11) |
C1—C2—H2 | 120.4 | C9—C10—H10A | 108.7 |
C6—C7—C8 | 115.81 (10) | C11—C10—H10A | 108.7 |
C6—C7—H7A | 108.3 | C9—C10—H10B | 108.7 |
C8—C7—H7A | 108.3 | C11—C10—H10B | 108.7 |
C6—C7—H7B | 108.3 | H10A—C10—H10B | 107.6 |
C8—C7—H7B | 108.3 | C5—N1—C1 | 122.82 (11) |
H7A—C7—H7B | 107.4 | C5—N1—H1 | 118.6 |
N3—C1—N1 | 117.35 (12) | C1—N1—H1 | 118.6 |
N3—C1—C2 | 124.09 (13) | C5—C4—C3 | 118.80 (13) |
N1—C1—C2 | 118.55 (12) | C5—C4—H4 | 120.6 |
C11i—C11—C10 | 113.06 (13) | C3—C4—H4 | 120.6 |
C11i—C11—H11A | 109.0 | N2—C5—N1 | 117.53 (12) |
C10—C11—H11A | 109.0 | N2—C5—C4 | 123.31 (12) |
C11i—C11—H11B | 109.0 | N1—C5—C4 | 119.16 (12) |
C10—C11—H11B | 109.0 | C5—N2—H2A | 120.0 |
H11A—C11—H11B | 107.8 | C5—N2—H2B | 120.0 |
C2—C3—C4 | 121.51 (13) | H2A—N2—H2B | 120.0 |
C2—C3—H3 | 119.2 | H5A—O5—H5B | 108 (4) |
C4—C3—H3 | 119.2 | H5A—O5—H5C | 107 (4) |
C7—C8—C8ii | 112.10 (13) | H5B—O5—H5C | 140 (5) |
O4—C6—C7—C8 | 14.8 (2) | C11i—C11—C10—C9 | 177.91 (14) |
O3—C6—C7—C8 | −166.16 (13) | N3—C1—N1—C5 | −179.08 (13) |
C3—C2—C1—N3 | 179.15 (16) | C2—C1—N1—C5 | 0.2 (2) |
C3—C2—C1—N1 | −0.1 (2) | C2—C3—C4—C5 | 0.2 (3) |
C1—C2—C3—C4 | −0.1 (3) | C1—N1—C5—N2 | −179.90 (13) |
C6—C7—C8—C8ii | 179.37 (15) | C1—N1—C5—C4 | −0.1 (2) |
O2—C9—C10—C11 | −2.29 (19) | C3—C4—C5—N2 | 179.70 (16) |
O1—C9—C10—C11 | 178.28 (12) | C3—C4—C5—N1 | −0.1 (2) |
Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x+2, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 2.03 | 2.8917 (14) | 175 |
N2—H2A···O4iii | 0.86 | 2.15 | 2.8589 (16) | 139 |
N2—H2B···O5 | 0.86 | 2.25 | 3.0892 (18) | 166 |
N3—H3A···O2 | 0.86 | 1.91 | 2.7729 (16) | 178 |
N3—H3B···O2iv | 0.86 | 2.06 | 2.8936 (17) | 162 |
O3—H4A···O1v | 0.83 (2) | 1.69 (2) | 2.5099 (15) | 171 (3) |
O5—H5A···O4vi | 0.82 (2) | 1.97 (2) | 2.7773 (15) | 165 (2) |
O5—H5B···O5vii | 0.82 (2) | 2.00 (2) | 2.804 (3) | 164 (5) |
O5—H5C···O5vi | 0.82 (2) | 2.01 (2) | 2.819 (3) | 168 (5) |
Symmetry codes: (iii) x−1, y, z; (iv) −x+2, −y+1, −z+2; (v) x+1, y, z; (vi) −x+3, −y+1, −z+1; (vii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | 2C5H8N3+·C6H8O42−·C6H10O4·2H2O |
Mr | 546.58 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 5.0645 (7), 7.6261 (11), 17.702 (3) |
α, β, γ (°) | 87.861 (11), 85.169 (11), 73.323 (11) |
V (Å3) | 652.55 (18) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.60 × 0.48 × 0.08 |
Data collection | |
Diffractometer | Stoe IPDS 2 |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.949, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7575, 2996, 2261 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.118, 1.05 |
No. of reflections | 2996 |
No. of parameters | 192 |
No. of restraints | 17 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.18 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Farrugia, 1997) and PLUTON (Spek, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 2.03 | 2.8917 (14) | 175 |
N2—H2A···O4i | 0.86 | 2.15 | 2.8589 (16) | 139 |
N2—H2B···O5 | 0.86 | 2.25 | 3.0892 (18) | 166 |
N3—H3A···O2 | 0.86 | 1.91 | 2.7729 (16) | 178 |
N3—H3B···O2ii | 0.86 | 2.06 | 2.8936 (17) | 162 |
O3—H4A···O1iii | 0.829 (17) | 1.688 (17) | 2.5099 (15) | 171 (3) |
O5—H5A···O4iv | 0.824 (16) | 1.972 (17) | 2.7773 (15) | 165 (2) |
O5—H5B···O5v | 0.824 (19) | 2.00 (2) | 2.804 (3) | 164 (5) |
O5—H5C···O5iv | 0.823 (19) | 2.01 (2) | 2.819 (3) | 168 (5) |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+2; (iii) x+1, y, z; (iv) −x+3, −y+1, −z+1; (v) −x+2, −y+1, −z+1. |
Acknowledgements
The author acknowledges the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant F.279 of the University Research Fund). The author also thanks Professor Dr O. Büyükgüngör for collection of the X-ray data and Professor Dr M. Odabaşoğlu for the synthesis of the title compound.
References
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The title crystal is obtained with the reaction of 2-aminopyridine (used in hair and other dyes) and adipic acid (used to esters for plasticizers and as food additive). In addition, The cupper(II) complexes of 2-aminopyridinium carboxylates have important properties in the applications of pharmaceuticals, fungicides, oxygen transfer, oxidative addition, homogenous hydrogenation, gas occlusion compounds, and solvent extractions processes (Lah et al., 2001; Yang et al., 1995). Hydrogen bonding plays a key role in molecular recognition (Goswami & Ghosh, 1997). The design of highly specific solid-state structure is of considerable significance in organic chemistry due to their important applications in the development of new optical, magnetic and electronic systems (Lehn, 1990). This report concerns the x-ray structure analysis of the title complex. In the structure investigations show that the 2-aminopyridinium ions are linked to the adipate ions by N1—H1···O1 and N3—H3···O2 hydrogen bonds through the formation of cyclic eight-membered hydrogen bonded rings.
An ORTEP diagram of (I) with numbering scheme is shown in Fig. 1. The bond lengths and angles in the structure is within the normally expected ranges. Similar C1—N3 and C5—N2 bonds were observed in other 2-aminopyridine containing molecules (Büyükgüngör & Odabaşoğlu, 2002; Odabaşoğlu & Büyükgüngör, 2006; Shanmuga Sundara Raj et al., 2000). Furthermore, these bond angle and length agrees with that similar bond angle and length values of 2,6-diaminopyridinium hydrogen fumarate complex (Büyükgüngör & Odabaşoğlu, 2006).
2-Aminopyridine and derivatives, are protonated in acidic solution. As for mono-aminopyridinium adipate-adipic acid and in some 2-aminopyridine-containing molecules, the bonding of the H atom to the ring N atom of 2-aminopyridine rather than the amine N atom gives an ion for which an additional resonance structure can be written.
The packing of the molecules is shown in Figure 2. In (I), the 2,6-diaminopyridinium ions are linked to the adipate-adipic ions through N—H···O, O—H···O hydrogen bonds (Table 1). The dihedral angles between the aminopyridinium ring and the O1/O2/C9/C10/C11 and O3/O4/C6/C7/C8 groups are 3.31 (7) and 7.25 (8)° respectively.
The H atoms between the water molecules are distorted because of the mutual repulsive interactions. So, H5B and H5C atoms are the same H-atom in the water molecule, and this H-atom makes a flip-flop motion between the two positions with site occupation factors of 0.50 (4) and 0.50 (4), respectively. The other H-atom (H5A) of the water molecule is localized due to the O5—H5A···O4 intermolecular hydrogen bond between adipic acid molecules (Fig. 3).