supplementary materials


Acta Cryst. (2013). E69, i20    [ doi:10.1107/S1600536813006041 ]

Dipotassium hydrogencarbonate fluoride monohydrate

V. Kahlenberg and T. Schwaier

Abstract top

Single crystals of the title compound, K2(HCO3)F·H2O, were obtained as a secondary product after performing flux synthesis experiments aimed at the preparation of potassium rare earth silicates. The basic building unit of the structure is an [(HCO3)(H2O)F]2- zigzag chain running parallel to [001]. Both types of anions as well as the water molecules reside on mirror planes perpendicular to [010] at y = 0.25 and y = 0.75, respectively. Linkage between the different constituents of the chains is provided by O-H...O and O-H...F hydrogen bonding. The K+ cations are located between the chains and are coordinated by two F and five O atoms in form of a distorted monocapped trigonal prism.

Comment top

In the present paper we describe a previously unknown phase within the multinary system K–(CO3,HCO3,F)–H2O which represents the first example of an alkali metal double salt containing hydrogencarbonate as well as fluoride anions.

Basic building units of the structure are [(HCO3)(H2O)F]2--zigzag-chains running along the [001]-direction. Within the unit cell the chains are located on mirror planes at y = 0.25 and y = 0.75, respectively. As can be seen from Fig. 1, a single water molecule in the chain provides two intermolecular hydrogen bonds with neighboring hydrogencarbonate and fluorine anions. Each fluorine atom in turn is the acceptor of two hydrogen bonds from adjacent H2O and (HCO3)-moieties (Table 1). The C—O bond lengths (1.250 (3)–1.350 (4) Å) and the O—C—O bond angles (114.7 (2)–127.6 (3) °) are in meaningful ranges. The distortions of the hydrogencarbonate group (point group symmetry m) follow the expected trends: the considerably longer C—O3 bond represents the linkage between the central carbon atom and the OH-group, which is also involved in hydrogen bonding. Consequently, the O1—C—O3 and O2—C—O3 angles are significantly smaller than 120°, whereas the O1—C—O2 angle is larger compared with the ideal undistorted case.

The potassium cations are coordinated by two fluorine and five oxygen atoms. The resulting coordination polyhedron can be described as a distorted monocapped trigonal prism (Fig. 2). Bond valence sum calculations were performed for the K+ cations using the bond valence parameters for K—O and K—F of Brown & Altermatt (1985). The resulting value in valence units (v.u.) is 1.10 and thus is reasonably close to the expected value of 1.0 v.u..

A slightly different description of the structure results when anion-centred polyhedra are considered as well. Actually, each F- anion is surrounded by two hydrogen atoms (belonging to a water molecule and a hydrogencarbonate group, respectively) and four additional equatorial potassium atoms in form of a distorted octahedron (Fig. 3). Edge-sharing between adjacent octahedra results in columns running along [010]. The linkage between the octahedral columns with the laterally attached H2O and (HCO3)-groups is realised by O4—H41··· O1 hydrogen bonds (Fig. 4).

To our best knowledge, the present compound represents the first example of an alkali hydrogencarbonate halogenide hydrate. The structure of an alkaline earth hydrogencarbonate chloride hydrate with composition Mg(HCO3)3Cl.6H2O has been reported recently (Dinnebier & Jansen, 2008). However, there are no closer structural relationships between the two phases. On the other hand, anionic chains containing (CO3)/(HCO3)-ions and water molecules have been observed in several other hydrous alkali/ammonium carbonates and hydrogencarbonates such as Na2CO3.H2O (Pritchard & Islam, 2003), K2CO3.1.5H2O (Skakle et al., 2001) and K4H2(CO3)3.1.5H2O (Cirpus & Adam, 1995). Concerning the general shape of the chains, the present compound and (NH4)4[H2(CO3)3].H2O (Margraf et al., 2003) are closely related (Fig. 5). As can be seen from Fig. 6, in both compounds the chains are located on mirror planes.

Only recently, the phase equilibria in the multinary system (Na,K)—(CO3,HCO3,F)—H2O have been studied at different temperatures in the range between 273 and 323 K (Soliev & Nizimov, 2009, 2011, 2012). The authors verified the existence of the following equilibrium solid phases containing potassium, for all of which detailed structural characterizations have been already performed in previous investigations: K2CO3.1.5H2O (Skakle et al., 2001), KHCO3 (Thomas et al., 1974), 2KHCO3.K2CO3.1.5H2O (or K4H2(CO3)3.1.5 H2O) (Cirpus & Adam, 1995) and KF (Broch et al., 1929). On the other hand, potassium carbonate hexahydrate (K2CO3.6H2O) has been identified as the stable hydrate below about 267 K (Hill & Miller, 1927). For potassium fluoride two hydrated forms have been described: KF.2H2O (Preisinger et al., 1994) and KF.4H2O (Beurskens & Jeffrey, 1964). Furthermore, an anhydrous potassium fluoro-carbonate with composition K3F(CO3) was reported (Arlt & Jansen, 1990).

Related literature top

For phase equilibria in the system (Na,K)–(CO3,HCO3,F)–H2O, see: Soliev & Nizimov (2009, 2011, 2012). For structure determinations of phases in the system K–(CO3,HCO3,F)–H2O, see: Arlt & Jansen (1990); Beurskens & Jeffrey (1964); Broch et al. (1929); Cirpus & Adam (1995); Hill & Miller (1927); Preisinger et al. (1994); Skakle et al. (2001); Thomas et al. (1974). For phases related to the title compound, see: Dinnebier & Jansen (2008); Margraf et al. (2003); Pritchard & Islam (2003). For bond-valence parameters, see: Brown & Altermatt (1985). For details of the synthetic procedure, see: Vidican et al. (2003).

Experimental top

Single crystals of K2(HCO3)F.H2O were obtained by chance as a by-product during the preparation of K-REE-silicates (REE is an rare earth element) from a KF flux following the approach of Vidican et al. (2003). After the removal of the platinum crucible the solidified melt cake was immediately crashed in an agate mortar and transferred to a glass slide under a polarizing binocular. Due to the hygroscopic character of potassium fluoride under the given experimental conditions (temperature: 296 K, relative humidity: 43%) deliquescence of the halide became obvious after 30 min. After 2 h, 50 µm sized platy birefringent single crystals were observed in the solution droplets which continued to grow until the solution was completely evaporated. The sample was checked regularly over a period of two weeks. However, no indication for weathering or alteration could be detected. In order to study the compound in more detail a single-crystal of good optical quality showing sharp extinction when imaged between crossed polarizers was selected and mounted on the tip of a glass fibre using nail hardener as glue. A preliminary unit cell determination at ambient temperature using on Oxford Diffraction Gemini Ultra single-crystal diffractometer resulted in a set of lattice parameters that could not be found in the recent WEB-based version of the Inorganic Crystal Structure Database (ICSD). Therefore, we decided to perform a full data collection for structure solution. For the low temperature measurement the crystal was flash-cooled in a 173 (2) K dried air stream generated by an Oxford Cryosystems Desktop Cooler.

Refinement top

Difference Fourier calculations revealed the positions of all missing hydrogen atoms. For the subsequent refinement the positional parameters of the H atoms were optimized with restraints using DFIX 0.84 (2) commands for the O—H distances and DFIX 1.32 (2) commands for the H···H distances (giving H—O—H angles close to 105°).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS for Windows (Dowty, 2011); software used to prepare material for publication: publCIF (Westrip, 2010);.

Figures top
[Figure 1] Fig. 1. Projection of a single [(HCO3)(H2O)F]2- – chain in y = 0.25 parallel to [010]. C—O and O—H bonds are given as thick and thin open lines, respectively. Dashed lines correspond to H···O and H···F hydrogen bonds; thermal ellipsoids have been drawn on the 70% probability level. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, -y + 1, -z + 1; (ix) x - 1, y, z].
[Figure 2] Fig. 2. Side view of the coordination polyhedron around a single K+ cation. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x + 1, -y + 1, -z + 1; (iii) -x + 2, -y + 1, -z +1].
[Figure 3] Fig. 3. Coordination environment around a single F- anion.
[Figure 4] Fig. 4. Projection of edge-sharing anion-centered chains (linked by H2O and HCO3 – moieties) perpendicular to (100). Small blue spheres correspond to the K+ cations.
[Figure 5] Fig. 5. Chains containing carbonate/hydrogencarbonate and water moieties in (a) K2(HCO3)F.H2O and (b) (NH4)4[H2(CO3)3].H2O.
[Figure 6] Fig. 6. Projections of the crystal structures of (a) K2(HCO3)F.H2O and (b) (NH4)4[H2(CO3)3].H2O parallel to the chain directions. Small blue spheres correspond to the K+ cations.
Dipotassium hydrogen carbonate fluoride monohydrate top
Crystal data top
K2(HCO3)F·H2OF(000) = 176
Mr = 176.24standard setting
Monoclinic, P21/mDx = 2.096 Mg m3
Hall symbol: -P 2ybMo Kα radiation, λ = 0.71073 Å
a = 5.4228 (4) ÅCell parameters from 538 reflections
b = 7.1572 (6) Åθ = 2.8–28.5°
c = 7.4539 (7) ŵ = 1.64 mm1
β = 105.121 (9)°T = 173 K
V = 279.28 (4) Å3Plate, colourless
Z = 20.18 × 0.18 × 0.06 mm
Data collection top
Agilent Xcalibur (Ruby, Gemini ultra)
diffractometer
551 independent reflections
Radiation source: Enhance (Mo) X-ray Source475 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
Detector resolution: 10.3575 pixels mm-1θmax = 25.3°, θmin = 2.8°
ω scansh = 56
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 87
Tmin = 0.946, Tmax = 1l = 87
1008 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0329P)2]
where P = (Fo2 + 2Fc2)/3
551 reflections(Δ/σ)max < 0.001
52 parametersΔρmax = 0.31 e Å3
4 restraintsΔρmin = 0.31 e Å3
Crystal data top
K2(HCO3)F·H2OV = 279.28 (4) Å3
Mr = 176.24Z = 2
Monoclinic, P21/mMo Kα radiation
a = 5.4228 (4) ŵ = 1.64 mm1
b = 7.1572 (6) ÅT = 173 K
c = 7.4539 (7) Å0.18 × 0.18 × 0.06 mm
β = 105.121 (9)°
Data collection top
Agilent Xcalibur (Ruby, Gemini ultra)
diffractometer
551 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
475 reflections with I > 2σ(I)
Tmin = 0.946, Tmax = 1Rint = 0.027
1008 measured reflectionsθmax = 25.3°
Refinement top
R[F2 > 2σ(F2)] = 0.028All H-atom parameters refined
wR(F2) = 0.075Δρmax = 0.31 e Å3
S = 1.05Δρmin = 0.31 e Å3
551 reflectionsAbsolute structure: ?
52 parametersFlack parameter: ?
4 restraintsRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
K0.79241 (9)0.50302 (5)0.23529 (7)0.0170 (2)
F0.4966 (3)0.750.0096 (2)0.0164 (5)
O41.1731 (4)0.250.2263 (3)0.0231 (6)
H411.265 (6)0.250.336 (2)0.028*
H421.280 (5)0.250.163 (4)0.028*
O10.4539 (4)0.250.5871 (3)0.0212 (6)
O20.8344 (4)0.250.5210 (3)0.0186 (5)
O30.8172 (4)0.250.8112 (3)0.0182 (5)
H30.708 (5)0.250.868 (4)0.022*
C0.6926 (6)0.250.6289 (4)0.0150 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K0.0181 (3)0.0121 (3)0.0193 (4)0.00008 (16)0.0021 (3)0.00045 (18)
F0.0177 (10)0.0170 (10)0.0140 (10)00.0034 (8)0
O40.0165 (12)0.0340 (14)0.0198 (13)00.0065 (9)0
O10.0168 (12)0.0290 (12)0.0179 (12)00.0046 (9)0
O20.0198 (11)0.0205 (11)0.0171 (12)00.0079 (9)0
O30.0153 (11)0.0262 (12)0.0136 (12)00.0049 (9)0
C0.0195 (17)0.0082 (14)0.0168 (17)00.0037 (14)0
Geometric parameters (Å, º) top
K—Fi2.6816 (11)O4—H420.838 (17)
K—F2.7389 (11)O1—C1.250 (3)
K—O1ii2.7541 (17)O1—Kvii2.7541 (17)
K—O22.7590 (17)O1—Kii2.7541 (17)
K—O42.7599 (17)O2—C1.250 (4)
K—O3iii2.8477 (18)O2—Kvi2.7590 (17)
K—O2iii2.9330 (16)O2—Kiii2.9330 (16)
F—Ki2.6816 (11)O2—Kviii2.9330 (16)
F—Kiv2.6816 (11)O3—C1.350 (4)
F—Kv2.7389 (11)O3—Kiii2.8477 (17)
O4—Kvi2.7599 (17)O3—Kviii2.8477 (17)
O4—H410.838 (17)O3—H30.814 (18)
Fi—K—F82.698 (16)Kvi—O4—H41103.7 (16)
Fi—K—O1ii117.24 (5)K—O4—H41103.7 (16)
F—K—O1ii68.47 (5)Kvi—O4—H42130.3 (11)
Fi—K—O287.60 (4)K—O4—H42130.3 (11)
F—K—O2148.65 (6)H41—O4—H42103 (2)
O1ii—K—O290.17 (5)C—O1—Kvii118.72 (13)
Fi—K—O481.96 (5)C—O1—Kii118.72 (13)
F—K—O4135.97 (6)Kvii—O1—Kii79.86 (6)
O1ii—K—O4153.18 (6)C—O2—Kvi123.79 (11)
O2—K—O471.12 (6)C—O2—K123.79 (11)
Fi—K—O3iii132.40 (6)Kvi—O2—K82.05 (6)
F—K—O3iii80.97 (4)C—O2—Kiii92.42 (14)
O1ii—K—O3iii97.43 (4)Kvi—O2—Kiii141.11 (8)
O2—K—O3iii125.94 (6)K—O2—Kiii89.27 (3)
O4—K—O3iii79.62 (5)C—O2—Kviii92.42 (14)
Fi—K—O2iii172.55 (4)Kvi—O2—Kviii89.27 (3)
F—K—O2iii102.32 (3)K—O2—Kviii141.11 (8)
O1ii—K—O2iii70.01 (5)Kiii—O2—Kviii74.13 (5)
O2—K—O2iii90.73 (3)C—O3—Kiii94.04 (14)
O4—K—O2iii90.63 (5)C—O3—Kviii94.04 (14)
O3iii—K—O2iii44.48 (6)Kiii—O3—Kviii76.74 (6)
Ki—F—Kiv84.96 (4)C—O3—H3106 (2)
Ki—F—Kv177.20 (5)Kiii—O3—H3136.9 (10)
Kiv—F—Kv97.302 (16)Kviii—O3—H3136.9 (10)
Ki—F—K97.302 (16)O1—C—O2127.6 (3)
Kiv—F—K177.20 (5)O1—C—O3117.7 (3)
Kv—F—K80.39 (4)O2—C—O3114.7 (2)
Kvi—O4—K82.01 (6)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1; (iii) x+2, y+1, z+1; (iv) x+1, y+1/2, z; (v) x, y+3/2, z; (vi) x, y+1/2, z; (vii) x+1, y1/2, z+1; (viii) x+2, y1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H41···O1ix0.84 (2)1.89 (2)2.723 (3)176 (3)
O4—H42···Fx0.84 (2)1.87 (2)2.707 (3)177 (3)
O3—H3···Fii0.81 (2)1.72 (2)2.529 (3)174 (4)
Symmetry codes: (ii) x+1, y+1, z+1; (ix) x+1, y, z; (x) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H41···O1i0.838 (17)1.887 (17)2.723 (3)176 (3)
O4—H42···Fii0.838 (17)1.870 (17)2.707 (3)177 (3)
O3—H3···Fiii0.814 (18)1.719 (19)2.529 (3)174 (4)
Symmetry codes: (i) x+1, y, z; (ii) x+2, y+1, z; (iii) x+1, y+1, z+1.
references
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