organic compounds
2,2′-Bipyridin-1-ium hemioxalate oxalic acid monohydrate
aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
*Correspondence e-mail: bdziuk@uni.opole.pl
The 10H9N2+·0.5C2O42−·C2H2O4·H2O, consists of a 2,2′-bipyridinium cation, half an oxalate dianion, one oxalic acid and one water molecule. One N atom in 2,2′-bipyridine is unprotonated, while the second is protonated and forms an N—H⋯O hydrogen bond. In the crystal, the anions are connected with surrounding acid molecules and water molecules by strong near-linear O—H⋯O hydrogen bonds. The water molecules are located between the anions and oxalic acids; their O atoms participate as donors and acceptors, respectively, in O—H⋯O hydrogen bonds, which form sheets arranged parallel to the ac plane.
of the title compound, CKeywords: crystal structure; 2,2′-bipyridinium; hydrogen bonds.
CCDC reference: 1864309
Structure description
Hydrogen bonds are one of the most important intermolecular interactions in structural chemistry (Desiraju, 2013). The strong interactions between cations and anions have been studied extensively for use in supramolecular chemistry and crystal engineering. Carboxylic acids, especially in hydrates, form strong interactions that may strongly influence the different forms of structures, usually forming supramolecular synthons (Dziuk et al., 2014a,b, 2017; Braga et al., 2013; Ejsmont & Zaleski, 2006). 2,2′-Bipyridine derivatives are classical bidentate chelating heterocyclic ligands (Steel, 1996) employed in transition metal catalysis and inorganic syntheses (e.g. aluminium-initiated polymerization; Blau, 1888; Mardare & Matyjaszewski, 1994) because of their robust redox stability and ease of functionalization (Kaes et al., 2000). Many complexes with 2,2′-bipyridine have distinctive optical properties and are used in studies of electron and catalysis and supramolecular chemistry (Balzani et al., 2006). Their use as building blocks for the construction of efficient molecular and macromolecular non-linear optical chromophores is an area of great interest (Coe et al., 2005). 2,2′-Bipyridine has been used for more than a century as common chelating ligand in analytical, organometallic and coordination chemistry (Steel, 1996).
The , consists of a 2,2′-bipyridinium cation, half an oxalate anion, one oxalic acid and one water molecule (Fig. 1). The oxalate anion is planar with an inversion center at the mid-point of the C—C bond. One nitrogen atom in the 2,2′-bipyridinium cation is unprotonated while second one is protonated and forms a strong N—H⋯O hydrogen bond. In the crystal, two different types of strong hydrogen bonds are observed: N—H⋯O and O—H⋯O (Table 1, Fig. 2). The anions are connected with the cations and surrounding acid molecules and water molecules by strong near-linear O—H⋯O hydrogen bonds. The water molecules are located between the anions and oxalic acid molecules; their O atoms participate as donors and acceptors, respectively, in O—H⋯O hydrogen bonds, which form sheets arranged parallel to the ac plane.
of the title hydrated salt, (I)Synthesis and crystallization
Crystals were grown at room temperature by slow evaporation of an aqueous solution containing 2,2′-bipyridine and oxalic acid in a 1:1 stoichiometric ratio.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1864309
https://doi.org/10.1107/S2414314618012191/bt4073sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012191/bt4073Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618012191/bt4073Isup3.cml
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell
CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).C10H9N2+·0.5C2O42−·C2H2O4·H2O | Z = 2 |
Mr = 309.25 | F(000) = 322 |
Triclinic, P1 | Dx = 1.493 Mg m−3 |
a = 7.2618 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.9419 (6) Å | Cell parameters from 4712 reflections |
c = 11.0001 (7) Å | θ = 3.1–26.0° |
α = 85.545 (5)° | µ = 0.12 mm−1 |
β = 86.177 (5)° | T = 293 K |
γ = 75.248 (5)° | Plate, pink |
V = 687.84 (8) Å3 | 0.4 × 0.35 × 0.3 mm |
Oxford Diffraction Xcalibur diffractometer | 2054 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | θmax = 26.0°, θmin = 3.1° |
ω–scan | h = −8→8 |
4712 measured reflections | k = −9→11 |
2648 independent reflections | l = −13→13 |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.089 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.16 e Å−3 |
2648 reflections | Δρmin = −0.15 e Å−3 |
200 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.138 (7) |
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. All H atoms were located in a difference map and set to this position. During refinement they were treated as riding on their parent N, O and C atoms, with and Uiso (H) = 1.2Ueq(C, N, O). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.49365 (11) | 0.08583 (10) | 0.85141 (7) | 0.0386 (2) | |
N1 | 0.27452 (14) | 0.38740 (12) | 0.84585 (10) | 0.0408 (3) | |
H1 | 0.3370 | 0.2997 | 0.8775 | 0.049* | |
C1 | 0.56889 (16) | 0.02093 (13) | 0.94780 (10) | 0.0294 (3) | |
O2 | 0.74212 (11) | −0.01433 (10) | 0.96493 (8) | 0.0465 (3) | |
N2 | 0.38268 (15) | 0.33461 (12) | 1.07479 (10) | 0.0406 (3) | |
C2 | 0.68092 (17) | 0.05604 (14) | 0.56545 (11) | 0.0349 (3) | |
O3 | 0.55452 (14) | 0.17018 (12) | 0.54737 (8) | 0.0594 (3) | |
C3 | 0.80116 (17) | −0.03224 (15) | 0.46116 (10) | 0.0339 (3) | |
O4 | 0.73101 (12) | −0.00942 (11) | 0.67194 (7) | 0.0470 (3) | |
H4 | 0.6457 | 0.0297 | 0.7370 | 0.056* | |
C4 | 0.21997 (17) | 0.50713 (14) | 0.91815 (12) | 0.0389 (3) | |
C5 | 0.11417 (19) | 0.64602 (15) | 0.86672 (15) | 0.0510 (4) | |
H5 | 0.0713 | 0.7310 | 0.9141 | 0.061* | |
O5 | 0.91375 (13) | −0.15528 (11) | 0.47742 (8) | 0.0506 (3) | |
C6 | 0.0722 (2) | 0.65872 (18) | 0.74540 (17) | 0.0589 (4) | |
H6A | 0.0006 | 0.7522 | 0.7113 | 0.071* | |
O6 | 0.76264 (12) | 0.04452 (10) | 0.35664 (7) | 0.0453 (3) | |
H6 | 0.8398 | −0.0028 | 0.2934 | 0.054* | |
C7 | 0.1354 (2) | 0.53431 (19) | 0.67463 (15) | 0.0591 (4) | |
H7 | 0.1098 | 0.5430 | 0.5923 | 0.071* | |
O7 | 0.94612 (12) | −0.06711 (10) | 0.16511 (7) | 0.0440 (3) | |
H7A | 1.0359 | −0.0334 | 0.1317 | 0.053* | |
H7B | 0.8673 | −0.0478 | 0.0991 | 0.053* | |
C8 | 0.2373 (2) | 0.39662 (18) | 0.72765 (14) | 0.0524 (4) | |
H8 | 0.2802 | 0.3104 | 0.6817 | 0.063* | |
C9 | 0.27939 (17) | 0.47844 (14) | 1.04566 (12) | 0.0377 (3) | |
C10 | 0.2316 (2) | 0.59226 (17) | 1.12833 (15) | 0.0546 (4) | |
H10 | 0.1623 | 0.6917 | 1.1047 | 0.066* | |
C11 | 0.2885 (2) | 0.5560 (2) | 1.24680 (16) | 0.0633 (4) | |
H11 | 0.2570 | 0.6305 | 1.3043 | 0.076* | |
C12 | 0.3922 (2) | 0.40849 (19) | 1.27819 (14) | 0.0563 (4) | |
H12 | 0.4313 | 0.3805 | 1.3574 | 0.068* | |
C13 | 0.43656 (19) | 0.30303 (16) | 1.18919 (13) | 0.0481 (4) | |
H13 | 0.5086 | 0.2037 | 1.2104 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0423 (5) | 0.0424 (5) | 0.0235 (4) | 0.0008 (4) | 0.0009 (4) | 0.0047 (4) |
N1 | 0.0347 (6) | 0.0340 (6) | 0.0480 (7) | 0.0002 (5) | −0.0044 (5) | 0.0057 (5) |
C1 | 0.0346 (7) | 0.0280 (6) | 0.0231 (6) | −0.0036 (5) | 0.0005 (5) | −0.0022 (5) |
O2 | 0.0339 (5) | 0.0719 (7) | 0.0328 (5) | −0.0137 (5) | −0.0012 (4) | 0.0040 (4) |
N2 | 0.0397 (6) | 0.0320 (6) | 0.0479 (7) | −0.0060 (5) | −0.0037 (5) | 0.0025 (5) |
C2 | 0.0320 (6) | 0.0421 (7) | 0.0286 (6) | −0.0071 (6) | −0.0025 (5) | 0.0027 (5) |
O3 | 0.0621 (6) | 0.0590 (7) | 0.0374 (6) | 0.0187 (5) | 0.0016 (5) | 0.0013 (5) |
C3 | 0.0303 (6) | 0.0421 (8) | 0.0287 (6) | −0.0083 (6) | −0.0030 (5) | 0.0007 (5) |
O4 | 0.0449 (5) | 0.0603 (6) | 0.0252 (5) | 0.0035 (4) | 0.0024 (4) | 0.0038 (4) |
C4 | 0.0279 (6) | 0.0304 (7) | 0.0561 (9) | −0.0064 (5) | 0.0018 (6) | 0.0043 (6) |
C5 | 0.0404 (7) | 0.0320 (8) | 0.0755 (11) | −0.0041 (6) | −0.0029 (7) | 0.0109 (7) |
O5 | 0.0542 (6) | 0.0474 (6) | 0.0384 (5) | 0.0080 (5) | −0.0009 (4) | −0.0006 (4) |
C6 | 0.0400 (8) | 0.0480 (10) | 0.0833 (12) | −0.0080 (7) | −0.0128 (8) | 0.0285 (8) |
O6 | 0.0493 (5) | 0.0512 (6) | 0.0265 (5) | 0.0015 (4) | 0.0015 (4) | 0.0022 (4) |
C7 | 0.0470 (9) | 0.0685 (11) | 0.0592 (10) | −0.0142 (8) | −0.0145 (7) | 0.0217 (8) |
O7 | 0.0389 (5) | 0.0597 (6) | 0.0311 (5) | −0.0090 (4) | 0.0007 (4) | −0.0025 (4) |
C8 | 0.0464 (8) | 0.0574 (9) | 0.0501 (9) | −0.0077 (7) | −0.0067 (7) | 0.0024 (7) |
C9 | 0.0296 (6) | 0.0324 (7) | 0.0507 (8) | −0.0092 (5) | 0.0029 (5) | 0.0001 (6) |
C10 | 0.0519 (9) | 0.0371 (8) | 0.0727 (11) | −0.0077 (7) | 0.0052 (8) | −0.0087 (7) |
C11 | 0.0676 (10) | 0.0655 (11) | 0.0637 (11) | −0.0268 (9) | 0.0104 (8) | −0.0241 (8) |
C12 | 0.0579 (9) | 0.0687 (11) | 0.0495 (9) | −0.0289 (8) | −0.0027 (7) | −0.0048 (8) |
C13 | 0.0468 (8) | 0.0463 (8) | 0.0518 (9) | −0.0137 (7) | −0.0076 (7) | 0.0051 (7) |
O1—C1 | 1.2569 (13) | C5—H5 | 0.9300 |
N1—C8 | 1.3375 (17) | C6—C7 | 1.371 (2) |
N1—C4 | 1.3453 (17) | C6—H6A | 0.9300 |
N1—H1 | 0.8600 | O6—H6 | 0.9224 |
C1—O2 | 1.2401 (13) | C7—C8 | 1.3733 (19) |
C1—C1i | 1.559 (2) | C7—H7 | 0.9300 |
N2—C13 | 1.3306 (16) | O7—H7A | 0.8379 |
N2—C9 | 1.3402 (15) | O7—H7B | 0.9327 |
C2—O3 | 1.1997 (14) | C8—H8 | 0.9300 |
C2—O4 | 1.2996 (13) | C9—C10 | 1.380 (2) |
C2—C3 | 1.5355 (18) | C10—C11 | 1.383 (2) |
C3—O5 | 1.2007 (14) | C10—H10 | 0.9300 |
C3—O6 | 1.3014 (13) | C11—C12 | 1.373 (2) |
O4—H4 | 0.9417 | C11—H11 | 0.9300 |
C4—C5 | 1.3841 (17) | C12—C13 | 1.378 (2) |
C4—C9 | 1.4791 (19) | C12—H12 | 0.9300 |
C5—C6 | 1.378 (2) | C13—H13 | 0.9300 |
C8—N1—C4 | 123.91 (11) | C3—O6—H6 | 112.1 |
C8—N1—H1 | 118.0 | C6—C7—C8 | 118.73 (15) |
C4—N1—H1 | 118.0 | C6—C7—H7 | 120.6 |
O2—C1—O1 | 125.34 (10) | C8—C7—H7 | 120.6 |
O2—C1—C1i | 118.21 (12) | H7A—O7—H7B | 98.0 |
O1—C1—C1i | 116.44 (12) | N1—C8—C7 | 119.56 (14) |
C13—N2—C9 | 117.25 (12) | N1—C8—H8 | 120.2 |
O3—C2—O4 | 125.59 (12) | C7—C8—H8 | 120.2 |
O3—C2—C3 | 122.43 (11) | N2—C9—C10 | 122.62 (13) |
O4—C2—C3 | 111.97 (10) | N2—C9—C4 | 115.25 (12) |
O5—C3—O6 | 126.36 (12) | C10—C9—C4 | 122.13 (12) |
O5—C3—C2 | 122.97 (11) | C9—C10—C11 | 118.92 (14) |
O6—C3—C2 | 110.67 (11) | C9—C10—H10 | 120.5 |
C2—O4—H4 | 114.2 | C11—C10—H10 | 120.5 |
N1—C4—C5 | 117.27 (13) | C12—C11—C10 | 118.99 (14) |
N1—C4—C9 | 116.89 (11) | C12—C11—H11 | 120.5 |
C5—C4—C9 | 125.84 (13) | C10—C11—H11 | 120.5 |
C6—C5—C4 | 120.14 (15) | C11—C12—C13 | 118.18 (15) |
C6—C5—H5 | 119.9 | C11—C12—H12 | 120.9 |
C4—C5—H5 | 119.9 | C13—C12—H12 | 120.9 |
C7—C6—C5 | 120.36 (13) | N2—C13—C12 | 124.03 (13) |
C7—C6—H6A | 119.8 | N2—C13—H13 | 118.0 |
C5—C6—H6A | 119.8 | C12—C13—H13 | 118.0 |
Symmetry code: (i) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O2ii | 0.84 | 1.99 | 2.8192 (12) | 170 |
N1—H1···O1 | 0.86 | 1.99 | 2.7586 (13) | 148 |
O4—H4···O1 | 0.94 | 1.64 | 2.5795 (11) | 176 |
O4—H4···O2 | 0.94 | 2.62 | 3.2259 (12) | 122 |
O6—H6···O7 | 0.92 | 1.63 | 2.5467 (11) | 169 |
O7—H7B···O2iii | 0.93 | 1.75 | 2.6802 (12) | 174 |
C8—H8···O3 | 0.93 | 2.52 | 3.3132 (18) | 144 |
C10—H10···O7iv | 0.93 | 2.43 | 3.2562 (17) | 148 |
C13—H13···O6v | 0.93 | 2.59 | 3.3876 (16) | 144 |
Symmetry codes: (ii) −x+2, −y, −z+1; (iii) x, y, z−1; (iv) x−1, y+1, z+1; (v) x, y, z+1. |
References
Balzani, V., Bergamini, G., Marchioni, F. & Ceroni, P. (2006). Coord. Chem. Rev. 250, 1254–1266. CrossRef Google Scholar
Blau, F. (1888). Ber. Dtsch. Chem. Ges. 21, 1077–1078. CrossRef Google Scholar
Braga, D., Chelazzi, L., Ciabatti, I. & Grepioni, F. (2013). New J. Chem. 37, 97–104. Web of Science CSD CrossRef CAS Google Scholar
Coe, B. J., Harris, J. A., Brunschwig, B. S., Asselberghs, I., Clays, K., Garín, J. & Orduna, J. (2005). J. Am. Chem. Soc. 127, 13399–13410. CrossRef Google Scholar
Desiraju, G. (2013). J. Am. Chem. Soc. 135, 9952–9967. Web of Science CrossRef CAS PubMed Google Scholar
Dziuk, B., Zarychta, B. & Ejsmont, K. (2014a). Acta Cryst. E70, o852. CSD CrossRef IUCr Journals Google Scholar
Dziuk, B., Zarychta, B. & Ejsmont, K. (2014b). Acta Cryst. E70, o917–o918. CSD CrossRef IUCr Journals Google Scholar
Dziuk, B., Zarychta, B., Ejsmont, K. & Daszkiewicz, Z. (2017). IUCrData, 2, x171390. Google Scholar
Ejsmont, K. & Zaleski, J. (2006). Acta Cryst. E62, o3879–o3880. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Kaes, C., Katz, A. & Hosseini, M. W. (2000). Chem. Rev. 100, 3553–3590. Web of Science CrossRef PubMed CAS Google Scholar
Mardare, D. & Matyjaszewski, K. (1994). Macromolecules, 27, 3, 645–649. Google Scholar
Oxford Diffraction (2008). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Steel, P. J. (1996). Aromatic Biheterocycles: Syntheses, Structures, and Properties. Advances in Heterocyclic Chemistry, Vol. 67, pp. 49–52. New York: Academic Press. Google Scholar
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