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Layered alkali propano­ates M+(C2H5COO); M+ = Na+, K+, Rb+, Cs+

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aInst. of Physics of the Czech Academy of Sciences, Na Slovance 2, 182 21 Praha 8, Czech Republic
*Correspondence e-mail: fabry@fzu.cz

Edited by M. Weil, Vienna University of Technology, Austria (Received 24 June 2020; accepted 21 August 2020; online 28 August 2020)

The title alkali propano­ates poly[(μ5-propano­ato)alkali(I)], M+(C2H5COO), with alkali/M+ = Na+, K+, Rb+ and Cs+, show close structural similarity, which is manifested by the coordination of the cations by six oxygen atoms in a chessboard motif, forming a bilayer. This bilayer is situated between hydro­phobic layers composed of dangling ethyl chains from the carboxyl­ate groups. Stacking of these two-dimensional sandwiches, which are parallel to (001), forms the title structures. Each metal cation is coordinated by six O atoms in the form of a distorted trigonal prism. One pair of these oxygen atoms belongs to a bridging, bidentately coordinating carboxyl­ate anion, while each of the other four oxygen atoms belongs to different carboxyl­ate groups, which are in a bridging monodentate mode. Despite the close similarity, each of the studied alkali propano­ates crystallizes in a different space group. The atoms are in general positions, except for the cation in K+(C2H5COO), which is situated on a mirror plane. Positional disorder of the methyl groups that are disordered over two positions is present in the Na+ and K+ propano­ates, in contrast to the Rb+ and Cs+ propano­ates. In the Na+ compound, the occupational parameters of the disordered methyl groups are different compared to the K+ compound where they are equal. This difference results in doubling of the a unit-cell parameter of the Na+ compound with respect to that of the K+ compound, otherwise the structures are homeotypic. In Cs+ propano­ate, a disorder of the methyl H atoms is observed.

1. Chemical context

The structures of the alkali propano­ates, M+(C3H5O2), with exception of Li+(C3H5O2) (Martínez Casado et al., 2009[Martínez Casado, F. J., Riesco, M. R., García Pérez, M. V., Redondo, M. I., López-Andrés, S. & Rodríguez Cheda, J. A. (2009). J. Phys. Chem. B, 113, 12896-12902.]), have not been determined so far, despite their assumed simplicity. The structure of the chemically related compound Tl+(C3H5O2) was determined by Martínez Casado et al. (2010[Martínez Casado, F. J., Ramos Riesco, M., da Silva, I., Labrador, A., Redondo, M. I., García Pérez, M. V., López-Andrés, S. & Rodríguez Cheda, J. A. (2010). J. Phys. Chem. B, 114, 10075-10085.]).

[Scheme 1]

On the other hand, the physical properties of some alkali propano­ates, together with related alkanoates, have been studied. Phase transitions were studied in alkali propano­ates together with alkali formates, acetates and butyrates by Ferloni et al. (1975[Ferloni, P., Sanesi, M. & Franzosini, P. (1975). Z. Naturforsch. Teil A, 30, 1447-1457.]) employing differential scanning calorimetry. The lowest-temperature phase transitions in Li, Na, K, Rb and Cs propano­ates take place at 533, 470, 258 (±2), 317 (±2) and 314 K, respectively.

Cingolani et al. (1979[Cingolani, A., Spinolo, G. & Sanesi, M. (1979). Z. Naturforsch. Teil A, 34, 575-578.]) determined the phase-transition temperatures in Li+(C3H5O2), Na+(C3H5O2) and K+(C3H5O2) by conductometric measurements. The determined phase-transition temperatures corresponded well with those reported by Ferloni et al. (1975[Ferloni, P., Sanesi, M. & Franzosini, P. (1975). Z. Naturforsch. Teil A, 30, 1447-1457.]), except for Li+(C3H5O2) where the phase transition was detected at 553 K. Martínez Casado et al. (2009[Martínez Casado, F. J., Riesco, M. R., García Pérez, M. V., Redondo, M. I., López-Andrés, S. & Rodríguez Cheda, J. A. (2009). J. Phys. Chem. B, 113, 12896-12902.]) determined the phase-transition temperature for the Li compound at 549.1 (±0.7) K in the virgin sample. The temperature of this phase transition varied during repeated cooling and heating.

The unit-cell parameters of the title structures have been determined in the past. In addition, Martínez Casado et al. (2009[Martínez Casado, F. J., Riesco, M. R., García Pérez, M. V., Redondo, M. I., López-Andrés, S. & Rodríguez Cheda, J. A. (2009). J. Phys. Chem. B, 113, 12896-12902.]) determined the unit-cell parameters of lithium propano­ate by single-crystal X-ray diffraction at 100, 160 and 298 K. Massarotti & Spinolo (1979[Massarotti, V. & Spinolo, G. (1979). J. Appl. Cryst. 12, 613-614.]) determined the unit-cell parameters for three phases of sodium propano­ate by powder X-ray diffraction. Entry No. 00-042-1901 in the powder diffraction file (PDF-4; Gates-Rector & Blanton, 2019[Gates-Rector, S. & Blanton, T. (2019). Powder Diffr. 34, 352-360.]) is derived from the latter powder data collection at 298 K. Cingolani et al. (1979[Cingolani, A., Spinolo, G. & Sanesi, M. (1979). Z. Naturforsch. Teil A, 34, 575-578.]) determined the unit-cell parameters for three phases of sodium propano­ate and for phases I and II of potassium propano­ate by powder X-ray diffraction but not for the lowest-temperature existing phase III of the latter compound. Massarotti & Spinolo (1980[Massarotti, V. & Spinolo, G. (1980). J. Appl. Cryst. 13, 622-624.]) determined the unit-cell parameters for phases I and II of potassium propano­ate but not for the lowest-temperature existing phase III either. Entries No. 00-042-1856–00-042-1859 in PDF-4 (Gates-Rector & Blanton, 2019[Gates-Rector, S. & Blanton, T. (2019). Powder Diffr. 34, 352-360.]) are derived from the data collection of the latter authors. Massarotti & Spinolo (1980[Massarotti, V. & Spinolo, G. (1980). J. Appl. Cryst. 13, 622-624.]) also determined two phases of Rb propano­ate by powder X-ray diffraction above 317 K, but not phase III existing below this temperature.

In the present study, the title structures were determined at 240 K, i.e. in the stability region of the known lowest-temperature phases. This means that the temperature regions in which the phases III of K+(C3H5O2) and Rb+(C3H5O2) (Cingolani et al., 1979[Cingolani, A., Spinolo, G. & Sanesi, M. (1979). Z. Naturforsch. Teil A, 34, 575-578.]) exist have been measured. However, the lattice parameters of K+(C3H5O2) reported here are in a fair agreement with the lattice parameters of phase II of K+(C3H5O2), which exists between 258 (±2)–352.5 (±0.6) K (Ferloni et al., 1975[Ferloni, P., Sanesi, M. & Franzosini, P. (1975). Z. Naturforsch. Teil A, 30, 1447-1457.]; Cingolani et al., 1979[Cingolani, A., Spinolo, G. & Sanesi, M. (1979). Z. Naturforsch. Teil A, 34, 575-578.]; Massarotti & Spinolo, 1980[Massarotti, V. & Spinolo, G. (1980). J. Appl. Cryst. 13, 622-624.]). The same holds for the lattice parameters of Rb+(C3H5O2) and phase II of Rb+(C3H5O2), which is reported to exist between 317 (±2) and 564 K by Ferloni et al. (1975[Ferloni, P., Sanesi, M. & Franzosini, P. (1975). Z. Naturforsch. Teil A, 30, 1447-1457.]) and Massarotti & Spinolo (1980[Massarotti, V. & Spinolo, G. (1980). J. Appl. Cryst. 13, 622-624.]), respectively. The reported unit cell of Rb+(C3H5O2) has all the inter­axial angles equal to 90°, in contrast to the present study. PDF-4 entries 00-032-1982–00-032-1984 (Gates-Rector & Blanton, 2019[Gates-Rector, S. & Blanton, T. (2019). Powder Diffr. 34, 352-360.]) are based on the experiments carried out by Massarotti & Spinolo (1980[Massarotti, V. & Spinolo, G. (1980). J. Appl. Cryst. 13, 622-624.]).

No match regarding caesium propano­ate has been found in the Cambridge Structural Database (Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]; version 5.41 from November 2019); however, there is an entry (No. 00-049-2031 in PDF-4; Gates-Rector & Blanton, 2019[Gates-Rector, S. & Blanton, T. (2019). Powder Diffr. 34, 352-360.]) that is attributed to this compound. The corresponding unit-cell volume V = 1355.38 Å3 is close to that observed recently at room temperature in Cs+(C2H5COO)·H2O with V = 1334.25 (4) Å3 (Samolová & Fábry, 2020[Samolová, E. & Fábry, J. (2020). Acta Cryst. E76, 1307-1310.]). Therefore, it can not be excluded that the reported phase in PDF-4 is in fact a hydrate. It should be emphasized that for each particular compound, their reported unit-cell parameters correspond to each other while multiplication of the unit-cell volume takes place in some cases.

Pretransitional phenomena have been observed in some of the title structures, which indicates a complicated structural rearrangement taking place before melting [see also the study of Li+(C3H5O2), Na+(C3H5O2) and K+(C3H5O2) by Cingolani et al. (1979[Cingolani, A., Spinolo, G. & Sanesi, M. (1979). Z. Naturforsch. Teil A, 34, 575-578.]), and the study of Li+(C3H5O2) by Martínez Casado et al. (2009[Martínez Casado, F. J., Riesco, M. R., García Pérez, M. V., Redondo, M. I., López-Andrés, S. & Rodríguez Cheda, J. A. (2009). J. Phys. Chem. B, 113, 12896-12902.])]. Such phenomena are more prominent in the structures with longer hydro­phobic chains, e.g. in butyrates (Duruz & Ubbelohde, 1972[Duruz, J. J. & Ubbelohde, A. R. (1972). Proc. R. Soc. Lond. A, 330, 1-13.]).

It should be mentioned that the crystals in the current study were cooled down instantly from room temperature to 240 K by putting them into a stream of a cooling gas. On the other hand, the measurement was carried out at temperatures not far from the thermodynamic equilibrium in which the room-temperature-grown crystals are assumed to exist. Our experience has shown that cooling down the crystals to very low temperatures does not necessarily mean a better resolution or better quality of the measured data.

An important structural feature of alkali alkanoates M+CnH2n+1COO (n > 2) seems to be their layered arrangement. For example, a layered structure has been observed in Li(C3H5O2) (Martínez Casado et al., 2009[Martínez Casado, F. J., Riesco, M. R., García Pérez, M. V., Redondo, M. I., López-Andrés, S. & Rodríguez Cheda, J. A. (2009). J. Phys. Chem. B, 113, 12896-12902.]) as well as in Li2Cd(C2H5COO)4 (Griffith & Amma, 1992[Griffith, E. A. H. & Amma, E. L. (1992). J. Crystallogr. Spectrosc. Res. 22, 77-81.]), despite the fact that Li+ is coordinated by four oxygen atoms in contrast to the six oxygens in the title structures. On the other hand, the layered structure of Tl(C3H5O2) (Martínez Casado et al., 2010[Martínez Casado, F. J., Ramos Riesco, M., da Silva, I., Labrador, A., Redondo, M. I., García Pérez, M. V., López-Andrés, S. & Rodríguez Cheda, J. A. (2010). J. Phys. Chem. B, 114, 10075-10085.]) is more complicated because it contains three independent Tl+ cations. Two of them (Tl1 and Tl3) are situated in a similar coordination to that in the title structures while Tl2 is situated in a roughly octa­hedral coordination. The presence of more than one symmetry-independent Tl+ cation even in simple structures is quite common. This is the case, for example, in a high-temperature phase of Tl2MoO4 (Friese et al., 1999[Friese, K., Madariaga, G. & Breczewski, T. (1999). Acta Cryst. C55, 1753-1755.]) or in Tl2WO4 (Okada et al., 1979[Okada, K., Ossaka, J. & Iwai, S. (1979). Acta Cryst. B35, 2189-2191.]) where three unique cations are present. Another example of a layered structure where the metal–oxygen sheet is surrounded by hydro­phobic organic layers is potassium palmitate KC16H31O2 (Dumbleton & Lomer, 1965[Dumbleton, J. H. & Lomer, T. R. (1965). Acta Cryst. 19, 301-307.]).

2. Structural commentary

Fig. 1[link]ad show the coordination environments around the central cations, which are situated in general positions except for K+(C2H5COO) where the cation is on a mirror plane (Wyckoff position 2 e). The central cations are surrounded by six oxygens with two of them stemming from the same carboxyl­ate group. The cation–oxygen distances are different; expectedly, the distances from the pair of oxygen atoms belonging to the same carboxyl­ate group are the longest. In the title structures, the angles Ocarboxyl­ateM—Ocarboxyl­ate decrease monotonously in the series M = Na, K, Rb, Cs: 52.39 (5), 45.92 (5), 43.93 (10), 41.28 (8)°. The bond-valence sums (Brese & O'Keeffe, 1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]) of the cations are 1.062 (2), 1.156 (3), 1.109 (5) and 1.042 (4) valence units for the Na, K, Rb, Cs compounds, respectively. The motifs shown in Fig. 1[link]ad are quite similar to those observed in potassium acrylate and potassium methacrylate (Heyman et al., 2020[Heyman, J. B., Chen, C.-H. & Foxman, B. M. (2020). Cryst. Growth Des. 20, 330-336.]) while the unit-cell parameters of the latter compounds also show a close correspondence to those of the title structures.

[Figure 1]
Figure 1
The common structural motifs in the title structures: (a) Na+(C3H5O2), (b) K+(C3H5O2), (c) Rb+(C3H5O2)- and (d) Cs+(C3H5O2). Displacement ellipsoids are shown at the 30% probability level. The cations, O, C and H atoms are shown as green, red, grey ellipsoids and as tiny light-grey spheres, respectively.

The common prominent feature of the title structures is the presence of an oxygen–metal bilayer that is sandwiched by ethyl chains. The layers are aligned parallel to (001), and packing of these layers forms the title structures. The structural motifs in all of the title structures are quite similar, and the structures can be considered as homeotypic (Lima de Faria et al., 1989[Lima-de-Faria, J., Hellner, E., Liebau, F., Makovicky, E. & Parthé, E. (1990). Acta Cryst. A46, 1-11.]). Because of their similarity, overall packing views are given only for the potassium and rubidium propano­ates (Fig. 2[link]a,b) because they represent the structures with positionally disordered and ordered methyl groups, respectively. The unit-cell parameters of the depicted structures are of similar size in contrast to the other structures.

[Figure 2]
Figure 2
The crystal packing of (a) K+(C3H5O2)- and (b) Rb+(C3H5O2). K or Rb, O and C atoms are shown as green, red and grey spheres, respectively. H atoms are omitted for clarity.

The positional disorder observed in the Na and K propano­ates (not in Rb and Cs propano­ates) is worth being discussed in detail. Table 1[link] lists the distances between neighbouring carbon atoms of the methyl­ene and methyl groups. In Rb+(C3H5O2) and Cs+(C3H5O2), these distances are larger than in Na+(C3H5O2) and K+(C3H5O2). This means that shorter distances between the methyl groups seem to be correlated with the observed positional disorder of the methyl groups. The disordered methyl groups are situated in rows, which are aligned parallel to the b axis in Na+(C3H5O2) and K+(C3H5O2). However, the assumed switching by rotation from one disordered position to another should also affect neighbouring rows in the ab plane. A correlated ordering of the ethyl groups is thus expected to take place. This situation is analogous to that observed in BaCa2(C3H5O2)6 where the methyl carbon atoms get as close as 4.05 (2) Å (Stadnicka & Glazer, 1980[Stadnicka, K. & Glazer, A. M. (1980). Acta Cryst. B36, 2977-2985.]). Table 2[link] shows that in the case of Na+(C3H5O2) and K+(C3H5O2), the positional disorder can bring these groups even as close as 2.609 (8) and 2.651 (9) Å, respectively, a value that clearly indicates the impossibility of simultaneous occupation of these sites by both groups. This short value also indicates the presence of thermal fluctuations. These fluctuations would provoke revolution of the ethyl chain to the other, i.e. the disordered site, while causing a domino effect by forcing the other ethyl chains to revolve in order to remove as much repulsion as possible. The torsion angles O1/O2—C1—C2—C3, which are listed in Table 2[link], also throw some light on the observed disorder. They are close to 0 or 180° for the disordered Na and K title compounds in contrast to the ordered Rb and Cs title compounds. The disordered methyl groups are situated in energetically similar or even identical positions in the Na and K compounds, respectively, in contrast to the the Rb and Cs compounds.

Table 1
Cmethyl­ene—Cmethyl­ene, Cmethyl­ene—Cmeth­yl and Cmeth­yl—Cmeth­yl distances (Å) in the title structures

Atoms C2 and C3 correspond to the methyl­ene and methyl atoms, respectively. The note 'disordered' indicates that the second atom belongs to the methyl carbon in a disordered position. For Na(C2H5COO), it is a C3a atom, for K(C2H5COO) it is a C3 atom with the symmetry codes x, xi, xii, xiii.

Compound Inter­action d Note
Na+(C2H5COO)      
  C2—C2i 3.552 (3)  
  C2—C2ii 3.552 (3)  
  C2—C3iii 3.973 (4)  
  C2—C3i 3.994 (4)  
  C2—C3ii 3.703 (4)  
  C2—C3aiv 3.973 (13) disordered
  C2—C3aii 3.723 (14) disordered
  C3—C3v 3.981 (4)  
  C3—C3avi 2.609 (8) disordered
  C3—C3aiv 3.079 (14) disordered
  C3—C3ai 3.547 (16) disordered
  C3—C3aii 3.558 (16) disordered
       
K+(C2H5COO)      
  C2—C2vii 3.907 (6)  
  C2—C2viii 3.907 (6)  
  C2—C3viii 3.982 (8)  
  C2—C3ix 3.993 (7)  
  C2—C3x 3.993 (7) disordered
  C2—C3xi 3.982 (8) disordered
  C3—C3vii 3.907 (11)  
  C3—C3viii 3.907 (11)  
  C3—C3x 2.997 (8) disordered
  C3—C3xii 3.136 (9) disordered
  C3—C3xiii 2.651 (9) disordered
       
Rb+(C2H5COO)      
  C2—C2vii 4.154 (10)  
  C2—C2viii 4.154 (10)  
  C2—C2xiv 4.250 (8)  
  C2—C3viii 4.228 (11)  
  C2—C3xv 4.238 (10)  
  C2—C3xiv 4.268 (9)  
  C3—C3vii 4.154 (13)  
  C3—C3viii 4.154 (13)  
  C3—C3xvi 4.154 (13)  
  C3—C3xvi 3.908 (12)  
  C3—C3xvii 4.035 (11)  
       
Cs+(C2H5COO)      
  C2—C2vii 4.424 (13)  
  C2—C2viii 4.424 (13)  
  C2—C2xviii 4.223 (11)  
  C2—C2xix 4.223 (11)  
  C2—C3vii 4.790 (14)  
  C2—C3viii 4.531 (14)  
  C2—C3xviii 4.258 (12)  
  C2—C3xix 4.114 (12)  
  C3—C3vii 4.424 (16)  
  C3—C3viii 4.424 (16)  
  C3—C3xx 3.882 (13)  
  C3—C3xviii 4.634 (13)  
  C3—C3xxi 3.882 (13)  
  C3—C3xix 4.634 (13)  
Symmetry codes: (i) x − [{1\over 2}], −y + [{3\over 2}], z; (ii) x + [{1\over 2}], −y + [{3\over 2}], z; (iii) −x + [{3\over 2}], y + [{1\over 2}], −z + 2 (iv) −x + [{3\over 2}], y − [{1\over 2}], −z + 2 (v) −x + 2, −y + 1, −z + 2 (vi) x, y − 1, z (vii) x − 1, y, z (viii) x + 1, y, z (ix) −x, y + [{1\over 2}], −z + 2 (x) −x, −y + 1, −z + 2 (xi) x + 1, −y + [{3\over 2}], z (xii) x, −y + [{1\over 2}], z (xiii) x, −y + [{3\over 2}], z (xiv) −x + 2, −y + 2, −z (xv) −x + 1, −y + 2, −z (xvi) −x + 1, −y + 1, −z (xvii) −x + 2, −y + 1, −z (xviii) x − [{1\over 2}], −y + [{3\over 2}], −z + 1 (xix) x + [{1\over 2}], −y + [{3\over 2}], −z + 1 (xx) x − [{1\over 2}], −y + [{1\over 2}], −z + 1 (xxi) x + [{1\over 2}], −y + [{1\over 2}], −z + 1.

Table 2
Torsional angles (°) for the propano­ate fragments in M+(C2H5COO); M+ = Na+, K+, Rb+, Cs+

Compound Atom 1 Atom 2 Atom 3 Atom 4 Angle
Na+(C2H5COO)          
  O1 C1 C2 C3 2.1 (3)
  O2 C1 C2 C3 −178.6 (2)
           
K+(C2H5COO)          
  O1 C1 C2 C3 −0.3 (5)
  O1xiii C1 C2 C3 179.4 (4)
           
Rb+(C2H5COO)          
  O1 C1 C2 C3 −5.1 (8)
  O2 C1 C2 C3 177.0 (5)
           
Cs+(C2H5COO)          
  O1 C1 C2 C3 −16.7 (10)
  O2 C1 C2 C3 165.7 (7)
Symmetry code: (xiii) x, −y + [{3\over 2}], z.

In the studied crystal of Na+(C3H5O2), the refined occupational parameters of the disordered methyl group converged to 0.808 (4) for one and 0.192 (4) for the other orientation. A hypothetical structure of Na(C3H5O2) where no positional disorder occurs would be described in a unit cell with a halved unit-cell parameter a relative to the title structure. The space group of such a hypothetical structure would be P21 instead of P21/a. [The transformation into the halved unit cell can also be carried out according to equation (1) in section 4]. Halving of the unit-cell parameter a would also be caused by a positional disorder in the ratio 0.50:0.50, provided that the blocks with the ordered mol­ecules are sufficiently small. The space-group type of such a hypothetical structure would be P21/m, which is equal to that of the reported structure of K(C3H5O2). The unit-cell parameter a of the title structure Na(C3H5O2) can be halved and transformed into the one that was reported by Massarotti & Spinolo (1979[Massarotti, V. & Spinolo, G. (1979). J. Appl. Cryst. 12, 613-614.]) or Cingolani et al. (1979[Cingolani, A., Spinolo, G. & Sanesi, M. (1979). Z. Naturforsch. Teil A, 34, 575-578.]) for phase III, the known lowest-temperature existing phase (determined by a powder diffraction study). In other words, it seems that the occupational parameters of the disordered ethyl groups can vary in different crystals of Na+(C3H5O2). More probably, because of the repulsion of the methyl groups, the phases, which had been subjected to powder diffraction experiments, rather correspond to the structures described in the space groups P21/m.

3. Synthesis and crystallization

The title compounds were prepared by dissolution of the pertinent alkali carbonates with propionic acid in the respective molar ratio of 1:2 in water. The pH of the solution was adjusted to 6–7 by addition of propionic acid. The solutions were filtered and the excessive amount of water was evaporated at 313 K. Prior to crystallization, which started on the surface of the solution, a more viscous layer seemed to develop. This layer was optically isotropic (no extinction in polarized light), in agreement with the observations for Li(C3H5O2), Na(C3H5O2), and K(C3H5O2) (Cingolani et al., 1979[Cingolani, A., Spinolo, G. & Sanesi, M. (1979). Z. Naturforsch. Teil A, 34, 575-578.]). During the course of the concentration of the solution, crystals also grew at the bottom of the beaker.

For the preparation of Na(C3H5O2), 1.49 g of Na2CO3 and 1.04 g of propionic acid were used before adjustment of the pH to 6–7 by propionic acid; for the preparation of K(C3H5O2), 1.49 g of K2CO3·1.5H2O and 0.67 g of propionic acid were used before adjustment of the pH to 6–7 by propionic acid; for the preparation of Rb(C3H5O2), 1.50 g of Rb2CO3 and 0.48 g of propionic acid were used before adjustment of the pH to 6–7 by propionic acid; for the preparation of Cs(C3H5O2), 1.50 g of Cs2CO3 and 0.34 g of propionic acid were used before adjustment of the pH to 6–7 by propionic acid.

All of the title compounds are hygroscopic. Crystals of Cs(C3H5O2) turned out to be deliquescent, and from the resulting solution the monohydrate Cs(C2H5COO)·H2O crystallized after some time (Samolová & Fábry, 2020[Samolová, E. & Fábry, J. (2020). Acta Cryst. E76, 1307-1310.]). Rb(C2H5COO) also turned out to be deliquescent. K(C2H5COO) was hygroscopic and the hygroscopicity of Na(C2H5COO) (Massarotti & Spinolo, 1979[Massarotti, V. & Spinolo, G. (1979). J. Appl. Cryst. 12, 613-614.]) was confirmed as well.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. Methyl hydrogen atoms were constrained: Cmeth­yl—Hmeth­yl = 0.96 Å while Uiso(Hmeth­yl) = 1.5Ueq(Cmeth­yl). Attached methyl­ene hydrogen atoms were situated at calculated positions and refined under the constraints Cmethyl­ene—Hmethyl­ene = 0.97 Å and Uiso(Hmethyl­ene) = 1.2Ueq(Cmethyl­ene).

Table 3
Experimental details

  [Na(C3H5O2)] [K(C3H5O2)] [Rb(C3H5O2)] [Cs(C3H5O2)]
Crystal data
Mr 96.1 112.2 158.5 206
Crystal system, space group Monoclinic, P21/a Monoclinic, P121/m1 Triclinic, P[\overline{1}] Orthorhombic, P212121
Temperature (K) 240 240 240 240
a, b, c (Å) 7.1048 (4), 5.3003 (3), 11.9035 (7) 3.9070 (17), 5.7872 (17), 11.317 (5) 4.1538 (13), 6.0008 (16), 11.182 (3) 4.4242 (1), 6.2866 (2), 21.4422 (8)
α, β, γ (°) 90, 111.225 (5), 90 90, 94.03 (2), 90 80.038 (10), 81.465 (10), 88.987 (10) 90, 90, 90
V3) 417.85 (4) 255.25 (18) 271.48 (13) 596.38 (3)
Z 4 2 2 4
Radiation type Cu Kα Mo Kα Mo Kα Mo Kα
μ (mm−1) 1.94 0.90 8.99 6.09
Crystal size (mm) 0.44 × 0.17 × 0.04 0.43 × 0.39 × 0.02 0.32 × 0.28 × 0.03 0.36 × 0.31 × 0.03
 
Data collection
Diffractometer Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS
Absorption correction Multi-scan (SADABS; Bruker, 2017[Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2017[Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2017[Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2017[Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.484, 0.934 0.700, 0.982 0.160, 0.762 0.218, 0.848
No. of measured, independent and observed [I > 3σ(I)] reflections 5731, 812, 610 8787, 738, 611 5050, 1568, 963 5255, 1687, 1583
Rint 0.038 0.054 0.069 0.026
(sin θ/λ)max−1) 0.619 0.705 0.706 0.703
 
Refinement
R[F > 3σ(F)], wR(F), S 0.050, 0.136, 3.60 0.051, 0.087, 2.07 0.047, 0.095, 1.36 0.027, 0.069, 1.63
No. of reflections 812 738 1568 1687
No. of parameters 59 37 55 56
No. of restraints 1 0 0 0
H-atom treatment H-atom parameters constrained H-atom parameters constrained H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.48, −0.25 1.41, −0.99 0.88, −0.84 0.64, −0.65
Computer programs: APEX3 (Bruker, 2017[Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2017[Bruker (2017). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SUPERFLIP (Palatinus & Chapuis, 2007[Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790.]), JANA2006 (Petříček et al., 2014[Petříček, V., Dušek, M. & Palatinus, L. (2014). Z. Kristallogr. 229, 345-352.]) and DIAMOND (Brandenburg, 2005[Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).

Na(C3H5O2): It turned out that the ethyl groups are disordered over two positions. The occupational parameters of the methyl groups were refined under the constraint that their sum equal unity, resulting in a 0.808 (4): 0.192 (4) ratio for the methyl groups C3 and C3a. The large unit cell can be transformed into the small unit cell that corresponds to that of K(C3H5O2) by the transformation [a, b, c]small = [a, b, c]large [1/2 0 1/2 / 0 1 0 / 0 0 1] [equation (1)].

K(C3H5O2): The ethyl groups are disordered over two positions due to the crystal symmetry, with occupancies equal to 1/2. The positions of the methyl hydrogens were discerned from the difference electron-density map.

Rb(C3H5O2): The positions of the methyl hydrogen atoms were discerned from the difference electron-density map.

Cs(C3H5O2): The methyl hydrogen atoms are equally disordered over two positions. The refined value of the Flack parameter [0.10 (9)] and its standard uncertainty did not enable the absolute structure to be determined reliably (Flack & Bernardinelli, 2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]).

Supporting information


Computing details top

For all structures, data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2014).

Poly[(µ5-propanoato)sodium(I)] (I) top
Crystal data top
[Na(C3H5O2)]F(000) = 200
Mr = 96.1There have been used diffractions with I/σ(I)>20 for the unit cell determination.
Monoclinic, P21/aDx = 1.527 Mg m3
Hall symbol: -P 2yabCu Kα radiation, λ = 1.54178 Å
a = 7.1048 (4) ÅCell parameters from 3181 reflections
b = 5.3003 (3) Åθ = 8.0–72.6°
c = 11.9035 (7) ŵ = 1.94 mm1
β = 111.225 (5)°T = 240 K
V = 417.85 (4) Å3Plate, colourless
Z = 40.44 × 0.17 × 0.04 mm
Data collection top
Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS
diffractometer
812 independent reflections
Radiation source: IµS micro-focus sealed tube610 reflections with I > 3σ(I)
Helios Cu multilayer optic monochromatorRint = 0.038
φ and ω scansθmax = 72.6°, θmin = 8.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2017)
h = 88
Tmin = 0.484, Tmax = 0.934k = 66
5731 measured reflectionsl = 1414
Refinement top
Refinement on F256 constraints
R[F > 3σ(F)] = 0.050Primary atom site location: charge flipping
wR(F) = 0.136H-atom parameters constrained
S = 3.60Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
812 reflections(Δ/σ)max = 0.007
59 parametersΔρmax = 0.48 e Å3
1 restraintΔρmin = 0.25 e Å3
Special details top

Refinement. The anisotropic displacement parameters of the disordered methyls were constrained: β11[C3a] = β11[C3], β22[C3a] = β22[C3], β33[C3a] = β33[C3], β12[C3a] = -β12[C3], β13[C3a] = β13[C3], β23[C3a] = -β23[C3]. The positions of the methyl hydrogens were discerned in the difference electron density map. The methyl hydrogens were constrained: Cmethyl—Hmethyl = 0.96?Å while Uiso(Hmethyl) = 1.5Ueq(Cmethyl). The methylene carbons were considered to be superimposed possessing the same positional as well as anisotropic displacement parameters with the overall occupational parameter equal to 1. The distances C2-C3 and C2-C3a were restrained to be equal. The attached methylene hydrogens were situated into the calculated positions with the corresponding occupational parameters and refined under the constraints Cmethylene—Hmethylene = 0.97?Å and Uiso(Hmethylene) = 1.2Ueq(Cmethylene). Their occupancies equalled to those of the occupanices of the pertinent methyl.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Na10.58889 (11)0.75057 (15)0.42221 (6)0.0219 (3)
O10.6929 (2)0.5409 (3)0.62475 (11)0.0257 (6)
O20.6933 (2)0.9598 (3)0.62567 (11)0.0272 (6)
C10.7006 (3)0.7495 (4)0.67624 (16)0.0189 (6)
C20.7176 (3)0.7518 (4)0.80791 (18)0.0252 (7)
C30.7313 (5)0.4978 (6)0.8670 (3)0.0366 (10)0.808 (4)
C3a0.732 (2)1.0057 (14)0.8673 (11)0.0366 (10)0.192 (4)
H1c20.8322080.8544120.8548170.0303*0.808 (4)
H2c20.6054130.8457920.8151590.0303*0.808 (4)
H1c2d0.6061480.6576650.8159790.0303*0.192 (4)
H2c2d0.8308040.6477650.8553310.0303*0.192 (4)
H1c30.838530.4019660.8567050.0549*0.808 (4)
H2c30.758140.5202570.9514490.0549*0.808 (4)
H3c30.6059190.4093850.830610.0549*0.808 (4)
H1c3a0.8564061.0859290.8727830.0549*0.192 (4)
H2c3a0.6204311.1088830.8202050.0549*0.192 (4)
H3c3a0.7291430.9841420.9466570.0549*0.192 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na10.0253 (5)0.0146 (5)0.0294 (5)0.0001 (4)0.0142 (3)0.0001 (3)
O10.0323 (8)0.0152 (10)0.0341 (8)0.0011 (6)0.0174 (7)0.0038 (6)
O20.0341 (9)0.0161 (10)0.0361 (8)0.0008 (6)0.0184 (7)0.0045 (6)
C10.0181 (8)0.0150 (9)0.0262 (9)0.0002 (9)0.0111 (7)0.0004 (8)
C20.0245 (9)0.0262 (11)0.0287 (9)0.0003 (11)0.0141 (7)0.0016 (9)
C30.0414 (15)0.0310 (14)0.0433 (14)0.0006 (15)0.0223 (12)0.0091 (13)
C3a0.0414 (15)0.0310 (14)0.0433 (14)0.0006 (15)0.0223 (12)0.0091 (13)
Geometric parameters (Å, º) top
O1—C11.255 (3)C3—H3c30.96
O2—C11.259 (3)C3a—H1c3a0.96
C1—C21.528 (3)C3a—H2c3a0.96
C2—C31.506 (4)C3a—H3c3a0.96
C2—C3a1.506 (9)Na1—O12.5107 (15)
C2—H1c20.97Na1—O1i2.3898 (18)
C2—H2c20.97Na1—O1ii2.4286 (17)
C2—H1c2d0.97Na1—O22.5190 (15)
C2—H2c2d0.97Na1—O2iii2.3944 (19)
C3—H1c30.96Na1—O2iv2.4233 (17)
C3—H2c30.96
O1—C1—O2124.01 (18)C2—C3a—H3c3a109.47
O1—C1—C2118.77 (19)H1c3a—C3a—H2c3a109.47
O2—C1—C2117.21 (19)H1c3a—C3a—H3c3a109.47
C1—C2—C3116.1 (2)H2c3a—C3a—H3c3a109.47
C1—C2—C3a117.1 (5)O1—Na1—O1i121.28 (5)
C1—C2—H1c2109.47O1—Na1—O1ii82.59 (5)
C1—C2—H2c2109.47O1—Na1—O252.39 (5)
C1—C2—H1c2d109.47O1—Na1—O2iii87.29 (5)
C1—C2—H2c2d109.47O1—Na1—O2iv115.92 (6)
C3—C2—C3a126.7 (5)O1i—Na1—O1ii155.01 (5)
C3—C2—H1c2109.47O1i—Na1—O287.20 (6)
C3—C2—H2c2109.47O1i—Na1—O2iii80.15 (6)
C3a—C2—H1c2d109.47O1i—Na1—O2iv95.08 (6)
C3a—C2—H2c2d109.47O1ii—Na1—O2115.64 (6)
H1c2—C2—H2c2101.92O1ii—Na1—O2iii94.93 (6)
H1c2d—C2—H2c2d100.62O1ii—Na1—O2iv78.81 (6)
C2—C3—H1c3109.47O2—Na1—O2iii121.43 (5)
C2—C3—H2c3109.47O2—Na1—O2iv82.98 (5)
C2—C3—H3c3109.47O2iii—Na1—O2iv154.50 (5)
H1c3—C3—H2c3109.47Na1—O1—Na1iii92.91 (6)
H1c3—C3—H3c3109.47Na1—O1—Na1ii97.41 (5)
H2c3—C3—H3c3109.47Na1iii—O1—Na1ii94.99 (6)
C2—C3a—H1c3a109.47Na1—O2—Na1i92.59 (6)
C2—C3a—H2c3a109.47Na1—O2—Na1iv97.02 (5)
O1—C1—C2—C32.1 (3)O2—C1—C2—C3178.6 (2)
Symmetry codes: (i) x+3/2, y+1/2, z+1; (ii) x+1, y+1, z+1; (iii) x+3/2, y1/2, z+1; (iv) x+1, y+2, z+1.
Poly[(µ5-propanoato)potassium(I)] (II) top
Crystal data top
[K(C3H5O2)]F(000) = 116
Mr = 112.2Dx = 1.459 Mg m3
Monoclinic, P121/m1Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 2906 reflections
a = 3.9070 (17) Åθ = 3.6–30.0°
b = 5.7872 (17) ŵ = 0.90 mm1
c = 11.317 (5) ÅT = 240 K
β = 94.03 (2)°Plate, colourless
V = 255.25 (18) Å30.43 × 0.39 × 0.02 mm
Z = 2
Data collection top
Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS
diffractometer
738 independent reflections
Radiation source: IµS micro-focus sealed tube611 reflections with I > 3σ(I)
Quazar Mo multilayer optic monochromatorRint = 0.054
φ and ω scansθmax = 30.1°, θmin = 3.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2017)
h = 55
Tmin = 0.700, Tmax = 0.982k = 88
8787 measured reflectionsl = 1515
Refinement top
Refinement on F220 constraints
R[F > 3σ(F)] = 0.051Primary atom site location: charge flip
wR(F) = 0.087H-atom parameters constrained
S = 2.07Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
738 reflections(Δ/σ)max = 0.002
37 parametersΔρmax = 1.41 e Å3
0 restraintsΔρmin = 0.99 e Å3
Special details top

Refinement. There have been discarded the following diffractions for which |Iobs-Icalc|>10σ(Iobs): 4 5 2, 5 1 3, -2 7 3, 5 1 4, 5 2 4, 4 4 4, -2 7 4, 5 1 5, 4 1 9, -2 5 9, -2 6 9, 0 0 11, 2 4 11, 3 0 12, -2 4 13, -2 3 14, -1 2 15

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
K10.25348 (15)0.750.40739 (6)0.0273 (2)
O10.2622 (4)0.5584 (2)0.63882 (14)0.0333 (5)
C10.2293 (6)0.750.6884 (3)0.0255 (9)
C20.1418 (8)0.750.8173 (3)0.0426 (12)
C30.1000 (18)0.5210 (11)0.8750 (5)0.071 (3)0.5
H1c20.3103840.8407910.8640350.0511*0.5
H2c20.0620220.8426730.8255070.0511*0.5
H1c30.147970.5360580.9590280.106*0.5
H2c30.1311480.4675360.8588670.106*0.5
H3c30.2563480.4119720.8443140.106*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K10.0258 (3)0.0185 (3)0.0381 (4)00.0057 (2)0
O10.0381 (8)0.0194 (8)0.0433 (10)0.0006 (6)0.0083 (7)0.0024 (6)
C10.0175 (12)0.0246 (15)0.0346 (18)00.0021 (11)0
C20.0468 (19)0.045 (2)0.037 (2)00.0110 (15)0
C30.101 (5)0.071 (5)0.043 (4)0.003 (4)0.020 (3)0.015 (3)
Geometric parameters (Å, º) top
O1—C11.253 (2)C3—H1c30.96
C1—C21.521 (5)C3—H2c30.96
C2—C31.492 (6)C3—H3c30.96
C2—C3i1.492 (6)K1—O12.842 (3)
C2—H1c20.97K1—O1ii2.715 (2)
C2—H1c2i0.97K1—O1iii2.679 (2)
C2—H2c20.97K1—O1iv2.715 (2)
C2—H2c2i0.97K1—O1v2.679 (2)
C3—H1c2i1.1598K1—O1i2.842 (3)
C3—H2c2i1.1347
O1—C1—O1i124.4 (3)C2—C3—H2c3109.47
O1—C1—C2117.80 (14)C2—C3—H3c3109.47
O1i—C1—C2117.80 (14)O1—K1—O1ii113.24 (5)
C1—C2—C3117.3 (3)O1—K1—O1iii118.48 (5)
C1—C2—C3i117.3 (3)O1—K1—O1iv83.21 (5)
C1—C2—H1c2109.47O1—K1—O1v87.54 (5)
C1—C2—H1c2i109.47O1—K1—O1i45.92 (5)
C1—C2—H2c2109.47O1ii—K1—O1iii92.81 (5)
C1—C2—H2c2i109.47O1ii—K1—O1iv82.22 (5)
C3—C2—C3i125.4 (4)O1ii—K1—O1v157.68 (6)
C3—C2—H1c2109.47O1ii—K1—O1i83.21 (5)
C3—C2—H1c2i51.01O1iii—K1—O1iv157.68 (6)
C3—C2—H2c2109.47O1iii—K1—O1v83.55 (5)
C3—C2—H2c2i49.52O1iii—K1—O1i87.54 (5)
C3i—C2—H1c251.01O1iv—K1—O1v92.81 (5)
C3i—C2—H1c2i109.47O1iv—K1—O1i113.24 (5)
C3i—C2—H2c249.52O1v—K1—O1i118.48 (5)
C3i—C2—H2c2i109.47K1—O1—K1vi96.79 (5)
C3i—C2—H1c2i109.47K1—O1—K1vii92.46 (5)
C3i—C2—H2c2i109.47K1vi—O1—K1vii92.81 (5)
C2—C3—H1c3109.47
O1—C1—C2—C30.3 (5)O1—C1—C2—C3i179.4 (4)
Symmetry codes: (i) x, y+3/2, z; (ii) x, y+1/2, z+1; (iii) x+1, y+1/2, z+1; (iv) x, y+1, z+1; (v) x+1, y+1, z+1; (vi) x, y1/2, z+1; (vii) x+1, y1/2, z+1.
Poly[(µ5-propanoato)rubidium(I)] (III) top
Crystal data top
[Rb(C3H5O2)]Z = 2
Mr = 158.5F(000) = 152
Triclinic, P1There have been used diffraction with I/σ(I)>20
Hall symbol: -P 1Dx = 1.939 Mg m3
a = 4.1538 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.0008 (16) ÅCell parameters from 2269 reflections
c = 11.182 (3) Åθ = 4.2–29.0°
α = 80.038 (10)°µ = 8.99 mm1
β = 81.465 (10)°T = 240 K
γ = 88.987 (10)°Plate, colourless
V = 271.48 (13) Å30.32 × 0.28 × 0.03 mm
Data collection top
Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS
diffractometer
1568 independent reflections
Radiation source: X-ray tube963 reflections with I > 3σ(I)
Quazar Mo multilayer optic monochromatorRint = 0.069
φ and ω scansθmax = 30.1°, θmin = 3.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2017)
h = 55
Tmin = 0.160, Tmax = 0.762k = 78
5050 measured reflectionsl = 1515
Refinement top
Refinement on F220 constraints
R[F > 3σ(F)] = 0.047Primary atom site location: charge flipping
wR(F) = 0.095H-atom parameters constrained
S = 1.36Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
1568 reflections(Δ/σ)max = 0.004
55 parametersΔρmax = 0.88 e Å3
0 restraintsΔρmin = 0.84 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Rb10.73165 (12)0.71678 (9)0.60411 (5)0.03307 (18)
O10.7845 (8)0.6143 (6)0.3502 (3)0.0379 (13)
O20.7998 (9)0.9829 (6)0.3534 (3)0.0410 (14)
C10.7720 (11)0.8167 (9)0.3016 (4)0.0285 (17)
C20.7054 (16)0.8726 (13)0.1694 (6)0.063 (3)
C30.689 (2)0.6740 (14)0.1052 (6)0.084 (4)
H1c20.8676010.9799950.1220340.0757*
H2c20.5058050.9584620.1665360.0757*
H1c30.6693260.7271280.0205630.1263*
H2c30.8835740.5864030.110310.1263*
H3c30.5033360.5814960.1436730.1263*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rb10.0334 (3)0.0197 (3)0.0471 (3)0.00058 (18)0.0087 (2)0.00620 (19)
O10.048 (2)0.0192 (19)0.048 (2)0.0005 (17)0.0131 (17)0.0039 (16)
O20.047 (2)0.022 (2)0.056 (2)0.0019 (18)0.0091 (19)0.0106 (17)
C10.022 (2)0.027 (3)0.036 (3)0.003 (2)0.003 (2)0.003 (2)
C20.071 (5)0.062 (5)0.057 (4)0.002 (4)0.024 (4)0.001 (4)
C30.134 (8)0.079 (6)0.049 (4)0.013 (6)0.031 (5)0.022 (4)
Geometric parameters (Å, º) top
Rb1—O12.984 (4)O2—C11.253 (7)
Rb1—O1i2.877 (4)C1—C21.523 (8)
Rb1—O1ii2.839 (4)C2—C31.502 (11)
Rb1—O22.953 (4)C2—H1c20.97
Rb1—O2iii2.862 (4)C2—H2c20.97
Rb1—O2iv2.820 (4)C3—H1c30.96
Rb1—C13.312 (5)C3—H2c30.96
O1—C11.245 (6)C3—H3c30.96
O1—C1—O2125.5 (5)O1—Rb1—O243.93 (10)
O1—C1—C2118.7 (5)O1—Rb1—O2iii109.85 (11)
O2—C1—C2115.7 (5)O1—Rb1—O2iv116.72 (10)
C1—C2—C3115.7 (6)O1i—Rb1—O1ii93.20 (10)
C1—C2—H1c2109.47O1i—Rb1—O2112.60 (11)
C1—C2—H2c2109.47O1i—Rb1—O2iii82.45 (10)
C3—C2—H1c2109.47O1i—Rb1—O2iv160.59 (10)
C3—C2—H2c2109.47O1ii—Rb1—O2116.19 (10)
H1c2—C2—H2c2102.39O1ii—Rb1—O2iii160.58 (10)
C2—C3—H1c3109.47O1ii—Rb1—O2iv83.87 (11)
C2—C3—H2c3109.47O2—Rb1—O2iii82.76 (10)
C2—C3—H3c3109.47O2—Rb1—O2iv85.67 (11)
H1c3—C3—H2c3109.47O2iii—Rb1—O2iv93.94 (11)
H1c3—C3—H3c3109.47Rb1—O1—Rb1i97.75 (10)
H2c3—C3—H3c3109.47Rb1—O1—Rb1ii91.85 (10)
O1—Rb1—O1i82.25 (10)Rb1—O1—O267.30 (14)
O1—Rb1—O1ii88.15 (10)Rb1i—O1—Rb1ii93.20 (10)
O1—C1—C2—C35.1 (8)O2—C1—C2—C3177.0 (5)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y+1, z+1; (iii) x+1, y+2, z+1; (iv) x+2, y+2, z+1.
Poly[(µ5-propanoato)caesium(I)] (IV) top
Crystal data top
[Cs(C3H5O2)]There have been used diffractions with I/σ(I)>20 for the unit cell determination.
Mr = 206Dx = 2.294 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5792 reflections
a = 4.4242 (1) Åθ = 3.4–30.0°
b = 6.2866 (2) ŵ = 6.09 mm1
c = 21.4422 (8) ÅT = 240 K
V = 596.38 (3) Å3Plate, colourless
Z = 40.36 × 0.31 × 0.03 mm
F(000) = 376
Data collection top
Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS
diffractometer
1687 independent reflections
Radiation source: X-ray tube1583 reflections with I > 3σ(I)
Quazar Mo multilayer optic monochromatorRint = 0.026
φ and ω scansθmax = 30.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2017)
h = 65
Tmin = 0.218, Tmax = 0.848k = 87
5255 measured reflectionsl = 2925
Refinement top
Refinement on F2Primary atom site location: charge flipping
R[F > 3σ(F)] = 0.027H-atom parameters constrained
wR(F) = 0.069Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 1.63(Δ/σ)max = 0.034
1687 reflectionsΔρmax = 0.64 e Å3
56 parametersΔρmin = 0.65 e Å3
0 restraintsAbsolute structure: 652 of Friedel pairs used in the refinement
35 constraintsAbsolute structure parameter: 0.10 (9)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cs10.73026 (5)0.64992 (4)0.191271 (13)0.04419 (9)
O10.7580 (11)0.4754 (5)0.32881 (17)0.0553 (11)
O20.7650 (9)0.8283 (5)0.32818 (19)0.0571 (11)
C10.7947 (8)0.6530 (7)0.3549 (2)0.0406 (11)
C20.891 (2)0.6550 (12)0.4209 (3)0.095 (3)
H1c20.7937210.7718810.4424280.1141*
H2c21.09770.7064570.4236120.1141*
C30.861 (3)0.4595 (15)0.4580 (3)0.099 (3)
H1c30.9433190.4824520.4988660.1485*0.5
H2c30.6506160.4228290.4615520.1485*0.5
H3c30.9675490.3457460.4379250.1485*0.5
H1c3d0.8338610.3401460.4306610.1485*0.5
H2c3d1.0393650.4391140.4826750.1485*0.5
H3c3d0.6882580.4717680.4850080.1485*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs10.04135 (14)0.02910 (13)0.06212 (18)0.00031 (11)0.00274 (13)0.00140 (11)
O10.065 (2)0.0295 (15)0.0712 (19)0.0046 (16)0.007 (2)0.0016 (13)
O20.061 (2)0.0317 (15)0.079 (2)0.0006 (18)0.0072 (18)0.0051 (14)
C10.0336 (18)0.0278 (16)0.060 (2)0.0039 (19)0.0030 (16)0.0009 (18)
C20.147 (7)0.059 (4)0.079 (5)0.009 (5)0.030 (5)0.001 (4)
C30.147 (8)0.089 (5)0.061 (4)0.013 (6)0.008 (5)0.019 (4)
Geometric parameters (Å, º) top
Cs1—O13.149 (4)C2—H2c20.97
Cs1—O1i3.006 (4)C2—C31.471 (11)
Cs1—O1ii3.082 (4)H1c2—H2c21.4631
Cs1—O23.146 (4)C3—H1c30.96
Cs1—O2iii3.010 (4)C3—H2c30.96
Cs1—O2iv3.041 (4)C3—H3c30.96
O1—C11.260 (5)C3—H1c3d0.96
O2—C11.249 (5)C3—H2c3d0.96
C1—C21.477 (9)C3—H3c3d0.96
C2—H1c20.97
O1—Cs1—O1i113.53 (11)O1—C1—O2124.3 (4)
O1—Cs1—O1ii109.49 (11)O1—C1—C2118.0 (5)
O1—Cs1—O241.28 (8)O2—C1—C2117.6 (5)
O1—Cs1—O2iii85.64 (11)C1—C2—H1c2109.47
O1—Cs1—O2iv82.42 (11)C1—C2—H2c2109.47
O1i—Cs1—O1ii93.22 (11)C1—C2—C3119.0 (6)
O1i—Cs1—O285.76 (9)H1c2—C2—H2c297.9
O1i—Cs1—O2iii85.08 (10)H1c2—C2—C3109.47
O1i—Cs1—O2iv163.83 (10)H2c2—C2—C3109.47
O1ii—Cs1—O281.83 (9)C2—C3—H1c3109.47
O1ii—Cs1—O2iii164.00 (10)C2—C3—H2c3109.47
O1ii—Cs1—O2iv83.26 (10)C2—C3—H3c3109.47
O2—Cs1—O2iii113.84 (10)C2—C3—H1c3d109.47
O2—Cs1—O2iv109.21 (10)C2—C3—H2c3d109.47
O2iii—Cs1—O2iv93.95 (9)C2—C3—H3c3d109.47
Cs1—O1—Cs1iii94.31 (11)H1c3—C3—H2c3109.47
Cs1—O1—Cs1iv97.42 (11)H1c3—C3—H3c3109.47
Cs1iii—O1—Cs1iv93.22 (9)H2c3—C3—H3c3109.47
Cs1—O2—Cs1i94.28 (11)H1c3d—C3—H2c3d109.47
Cs1—O2—Cs1ii98.33 (11)H1c3d—C3—H3c3d109.47
Cs1i—O2—Cs1ii93.95 (9)H2c3d—C3—H3c3d109.47
O1—C1—C2—C316.7 (10)O2—C1—C2—C3165.7 (7)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+2, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x+2, y1/2, z+1/2.
Torsional angles (°) for the propanoate fragments in M+(C2H5COO)-; M+ = Na+, K+, Rb+, Cs+ top
CompoundAtom 1Atom 2Atom 3Atom 4Angle
Na+(C2H5COO)-
O1C1C2C32.1 (3)
O2C1C2C3-178.6 (2)
K+(C2H5COO)-
O1C1C2C3-0.3 (5)
O1xiiiC1C2C3179.4 (4)
Rb+(C2H5COO)-
O1C1C2C3-5.1 (8)
O2C1C2C3177.0 (5)
Cs+(C2H5COO)-
O1C1C2C3-16.7 (10)
O2C1C2C3165.7 (7)
Symmetry code: (xiii) x, -y + 3/2, z.
Cmethylene—Cmethylene, Cmethylene—Cmethyl and Cmethyl—Cmethyl distances (Å) in the title structures top
Atoms C2 and C3 correspond to the methylene and methyl atoms, respectively. The note 'disordered' indicates that the second atom belongs to the methyl carbon in a disordered position. For Na(C2H5COO), it is a C3a atom, for K(C2H5COO) it is a C3 atom with the symmetry codes x, xi, xii, xiii.
CompoundInteractiondNote
Na+(C2H5COO)-
C2—C2i3.552 (3)
C2—C2ii3.552 (3)
C2—C3iii3.973 (4)
C2—C3i3.994 (4)
C2—C3ii3.703 (4)
C2—C3aiv3.973 (13)disordered
C2—C3aii3.723 (14)disordered
C3—C3v3.981 (4)
C3—C3avi2.609 (8)disordered
C3—C3aiv3.079 (14)disordered
C3—C3ai3.547 (16)disordered
C3—C3aii3.558 (16)disordered
K+(C2H5COO)-
C2—C2vii3.907 (6)
C2—C2viii3.907 (6)
C2—C3viii3.982 (8)
C2—C3ix3.993 (7)
C2—C3x3.993 (7)disordered
C2—C3xi3.982 (8)disordered
C3—C3vii3.907 (11)
C3—C3viii3.907 (11)
C3—C3x2.997 (8)disordered
C3—C3xii3.136 (9)disordered
C3—C3xiii2.651 (9)disordered
Rb+(C2H5COO)-
C2—C2vii4.154 (10)
C2—C2viii4.154 (10)
C2—C2xiv4.250 (8)
C2—C3viii4.228 (11)
C2—C3xv4.238 (10)
C2—C3xiv4.268 (9)
C3—C3vii4.154 (13)
C3—C3viii4.154 (13)
C3—C3xvi4.154 (13)
C3—C3xvi3.908 (12)
C3—C3xvii4.035 (11)
Cs+(C2H5COO)-
C2—C2vii4.424 (13)
C2—C2viii4.424 (13)
C2—C2xviii4.223 (11)
C2—C2xix4.223 (11)
C2—C3vii4.790 (14)
C2—C3viii4.531 (14)
C2—C3xviii4.258 (12)
C2—C3xix4.114 (12)
C3—C3vii4.424 (16)
C3—C3viii4.424 (16)
C3—C3xx3.882 (13)
C3—C3xviii4.634 (13)
C3—C3xxi3.882 (13)
C3—C3xix4.634 (13)
Symmetry codes: (i) x - 1/2, -y + 3/2, z; (ii) x + 1/2, -y + 3/2, z; (iii) -x + 3/2, y + 1/2, -z + 2 (iv) -x + 3/2, y - 1/2, -z + 2 (v) -x + 2, -y + 1, -z + 2 (vi) x, y - 1, z (vii) x - 1, y, z (viii) x + 1, y, z (ix) -x, y + 1/2, -z + 2 (x) -x, -y + 1, -z + 2 (xi) x +1, -y + 3/2, z (xii) x, -y + 1/2, z (xiii) x, -y + 3/2, z (xiv) -x + 2, -y + 2, -z (xv) -x + 1, -y + 2, -z (xvi) -x + 1, -y + 1, -z (xvii) -x + 2, -y + 1, -z (xviii) x - 1/2, -y + 3/2, -z + 1 (xix) x + 1/2, -y + 3/2, -z + 1 (xx) x - 1/2, -y + 1/2, -z + 1 (xxi) x + 1/2, -y + 1/2, -z + 1.
 

Acknowledgements

Dr Ivana Císařová from the Faculty of Science is thanked for generous measurement of the samples.

Funding information

Funding for this research was provided by: Ministry of Education of the Czech Republic (grant No. NPU I---LO1603).

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