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This study presents the coordination modes and crystal organization of a calcium-potassium coordination polymer, poly[hexa­aqua­bis([mu]4-4-carboxy­benzene­sulfonato-[kappa]4O1:O1':O1'':O4)bis­([mu]3-4-carboxy­benzene­sulfonato-[kappa]2O1:O1')­calcium(II)­dipotassium(I)], [CaK2(C7H5O5S)4(H2O)6]n, displaying a novel two-dimensional framework. The potassium ion is seven-coordinated by four sulfonate and one carboxyl O atom located on five different acid ligands, two of which are unique, and by two symmetry-independent water O atoms. A pair of close potassium ions share two inversion-related sulfonate O-atom sites to form a dimeric K2O12 unit, which is extended into a one-dimensional array along the a-axis direction. The six-coordinate Ca2+ ion occupies a special position (\overline{1}) at (0, 1\over2, 1\over2) and is surrounded by four sulfonate O atoms from two inversion-related pairs of unique acid monoanions and by two O atoms from aqua ligands. The compound displays a layered structure, with K2O12 and CaO6 polyhedra in the layers and aromatic linkers between the layers. The three-dimensional scaffold is open, with nano-sized channels along the c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109021337/sq3195sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109021337/sq3195Isup2.hkl
Contains datablock I

CCDC reference: 746039

Comment top

Hybrid inorganic–organic layered compounds, in particular organically functionalized metal phosphonates, are extensively studied for their potential applications in chemical separation, gas sorption, sensing and catalysis (Clearfield, 1998; Alberti & Constanino, 1996; Kong et al., 2006; Sharma & Clearfield, 2000; Cabeza et al., 2002). The metal organosulfonates, developed recently as analogous to the metal organophosphonates, are another class of novel materials with interesting functional properties such as guest sorption and ion exchange (Cote & Shimizu, 2003). However, there is no direct structural relationship between arylsulfonates and arylphosphonates, since the metal binding preferences and, therefore, the coordination modes of the relatively soft-base sulfonate group are different (Cote & Shimizu, 2003; Videnova-Adrabinska, 2007). A Cambridge Structural Database (Version 5.30; Allen, 2002) review has revealed 1514 total hits of sulfonate structures containing metal ions, of which 995 contain transition metal ions and 340 contain group IA or IIA metal ions (both transition and IA or IIA metal ions are found in 54 structures). The rest of the structures contain rare earth metal ions (159) or such main group metals as Pb (42), Sb (26), Sn (30), Tl (2), Bi (18), Al [number?] and Ga (3). Direct coordination of the metal ion to the sulfonate group is observed in only 638 compounds (426 d and f metal ion complexes and 143 group IA and IIA complexes). The organic ligand in most of the retrieved structures is endowed with one or more additional functional groups (–SO3H, –COOH, –OH, –CH3 or –NH2). In particular, the sulfoisophthalic, sulfosalicylic and disulfonic acids have been used as versatile ligands. Surprisingly, the sulfobenzoic acids are significantly less well studied (20 hits for 3-sulfobenzoic and 32 hits for 4-sulfobenzoic acids). Up to now only four potassium and/or rubidium, two barium, and one strontium 4-sulfonobenzoate (4sb) structures have been published (Gunderman & Squattrito, 1994; Kariuki & Jones, 1995; Wagner & Merzweiler, 2008; Prochniak & Videnova-Adrabinska, 2009). They all demonstrate layered inorganic regions, linked via the arene rings. So far, mixed IA–IIA compounds of sulfobenzoic acids are not known and herein we report the crystal structure of the first such example, {K2[Ca(4sb)4(H2O)2](H2O)4}n.

The asymmetric unit contains half of a calcium ion, one potassium ion, two unique 4-sulfobenzoic acid monoanions and three different water molecules (Fig. 1). The two crystallographically nonequivalent 4sb ligands are designated as A and B. The calcium ion is six-coordinate with an elongated octahedral geometry and lies in a special position at (0, 1/2, 1/2). The coordination environment of Ca2+ consists of four 4sb ligands, one of which is symmetry unique, and two water molecules. The sulfonate O atoms [O42A, O42Ai, O43B and O43Bi; symmetry codes: (i) -x, -y + 1, -z + 1] act as equatorial ligands and form two pairs of similar bonds (Ca—O42A and Ca—O43B), while the axial aqua ligands (OW1 and OW1i) form a slightly longer bond (Table 1). The coordination environment of K+ includes five 4sb ligands (two A and three B), and two independent water molecules. The potassium ion is seven coordinated via four sulfonate atoms [O41A, O42Bii, O41Aiv and O41B), one carboxylic acid O atom (O11Biii) and two water O atoms (O2W and O3W) [symmetry codes: (ii) -x, -y + 2, -z + 1; (iii) x, y, z - 1; (iv) -x + 1, -y + 2, -z + 1; Table 1]. The coordination geometry of K+ can be described as a distorted monocapped triangular prism, where atoms O41B, O41A, O11Biii and O42Bii form the rectangular face capped by atom O3W (Fig. 1). The dihedral angles between the best fitted planes forming the polyhedron faces are 73.3 (1) and 85.7 (1)° between the capped rectangular face and the triangular faces, and 64.0 (1), 51.8 (1) and 64.2 (1)° between the rectangular faces (Brandenburg, 2008). The close lying potassium ions [the K···K distance is 3.8382 (6) Å] share two of their O-atom sites (O41A and O41Aiv) in order to form a dimeric unit K2O2. Thus, the neighboring inversion-related trigonal prisms become paired to develop the {K2O12} polyhedron.

The compound is lamellar and built of alternating organic and inorganic layers that are connected in an extended three-dimensional structure. The inorganic part consists of K2O12 polyhedra, CaO6 octahedra and CSO3 tetrahedra (A and B). The K2O12 polyhedra are extended into coordination rods along the crystallographic a-axis direction by sharing two pairs of opposite corners with four B tetrahedra. The CaO6 octahedra are located symmetrically between the K2O12 rods and serve to link them via shared corners with both A and B tetrahedra (Fig. 2). Three different voids (one large and two smaller) are generated between the K2O12 polyhedra, CaO6 octahedra and CSO3 tetrahedra. The inorganic layers are arranged one over the other in order to form channels along the c axis, where the arene rings and the water molecules reside.

The topological consideration of the crystal organization is most appropriate for uncovering the connectivity patterns inside the layers, and for revealing the symmetry relationships of the framework. In fact, each sulfonate tetrahedron (A and B) associates one calcium ion with two potassium ions, but the A tetrahedron shares only two O-atom corners, while the B tetrahedron shares three O-atom corners (Fig. 2a). This means that each of the sulfonate groups (A and B) bridges the metal ions in a different coordination manner (η2µ3 and η3µ3). The A group uses a single O-atom site (µ2-O41A) to interlock close potassium ions via an R22(4) coordination motif in order to form the centrosymetric K2O2 dimer unit, and another site (O42A) to monodentately link the K2O2 dimer with the calcium center. The B group uses two O-atom sites (O41B and O42B) to bridge the K2O2 dimers along the a axis, and the third site (O43B) to connect the K2O2 dimer with the Ca center. The K ribbons are generated via two different centrosymmetric ring motifs, alternating along the a axis: the interlocking R22(4) motif, formed via K—O41A and K—O41Aiv bonds, and the bridging R24(8) motif, formed by K—O41B and K—O42Bii bonds. The two K···K distances [3.8382 (6) and 5.828 (1) Å] observed in the crystal structure correspond to the metal center interdistances in these rings. The two-dimensional framework of the inorganic monolayer can be considered as a result of an antiparallel arrangement of potassium ribbons, interweaved at the Ca ions. The interweaving R24(8) motif, closed between the K and Ca ions, is formed via K—O41A, Ca—O42A, Ca—O43B and K—O41B bonds. The motif itself is non-centrosymmetric, but is symmetrically arranged, incorporating both the Ca centers and the geometrical centers of the K2O2 dimers. The resulting two-dimensional network is 4,4-connected and displays large R48(16) nano-sized windows, arranged one over the other along the c axis. The arene rings of the A ligands and two of the water molecules are found here. The third water molecule projects into the centrosymmetric R24(8) motif (Fig. 2b). Numerous intralayer hydrogen bonds, established between the water molecules and the sulfonate O-atom sites, serve to stabilize the two-dimensional coordination network. The O2W—H4W···O43Biv and O3W—H5W···O41Bii hydrogen bonds are extended along the potassium ribbons, whereas the O1W—H2W···O43Avi, O2W—H3W···O43Avii and O3W—H6W···O1Wi interactions crosslink the neighboring ribbons inside the monolayer (for symmetry codes see Table 2). The organic portions of the ligands are arranged outward from both sides of the coordination monolayer and the rings are organized into A and B columns alternating along the b axis. The carboxylic acid site of the B monoanion is used to connect the monolayers in a bridging fashion via the K—O11Biii bond. Thus, the B-ring columns play the role of pillars between the layers, whereas the A rings fit the corridors generated between the pillars (Fig. 3). Three different hydrogen bonds (O12B—H12B···O3Wv, O12A—H12A···O2Wviii and O1W—H1W···O11Av), formed from or toward the carboxylic acid sites of both A and B ligands, additionally bring together the inorganic monolayers. The arene rings formally belonging to adjacent coordination monolayers are intermingled along the [110] direction with an interlayer centroid–centroid CgA···CgB distance of 4.655 (1) Å. The closest CgA···CgA and CgB···CgB interdistances are 4.838 (1) and 4.542 (1) Å with a slippage of 3.371 Å between the adjacent A rings and 3.009 Å between B rings. Y—X···Cg interactions are established between the carbonyl group of the A ligand and the π-electronic system of the adjacent A and B rings [C11A—O11A···CgA = 3.960 (2) Å and C11A—O11A···CgB = 3.663 (2) Å; Spek, 2009]. The overall coordination network is porous with the pores having nano-scle dimensions (8.73 × 10.62 × 12.68 Å).

The structure of this new mixed dipotassium calcium 4-sulfobenzoic acid compound may be compared with those of the potassium, dipotassium (Gunderman & Squattrito, 1994; Kariuki & Jones, 1995), barium (Wagner & Merzweiler, 2008) and strontium (Prochniak & Videnova-Adrabinska, 2009) compounds of the same ligand. All reported structures display separate organic and inorganic regions, with metal–SO3 units forming the inorganic layers. However both the connectivity patterns inside the inorganic monolayers and the arrangement of the arene rings in the organic regions differ from one structure to another. While the potassium ion is six-coordinate in K(HO2CC6H4SO3).H2O, six- and seven-coordinate in K2(O2CC6H4SO3), and eight-coordinate in K(HO2CC6H4SO3).H2O, the strontium ion is eight-coordinate in [Sr(4sb)2(H2O)3], and the barium ion is nine-coordinate in both Ba(O3SC6H4COO)2.3H2O and Ba(O3SC6H4COO).2H2O. [Note that the chemical formula units of the potassium and barium compounds given in the original papers do not distinguish the crystalline water molecule(s) from the aqua ligand(s) in the crystal structure.] It is obvious that the lack of d-electrons and therefore the lack of crystal field stabilization energy make the geometrical preferences of the metal ion less dominant, which allows for variable coordination environments and different coordination modes. On the other hand the presence of two different ions (K+and Ca2+) dramatically changes the symmetry relations and the connectivity patterns both inside the inorganic monolayers and between them. The irregular coordination geometry of the potassium ion is compensated by the formation of a centrosymmetric dimeric K2O12 unit in order to adapt the symmetry requirements of the frameworks forced by the octahedral geometry of the calcium ion. The effect of this compromise is the formation of nano-size voids in the Ca-K monolayer and a porous three-dimensional structure.

Related literature top

For related literature, see: Alberti & Constanino (1996); Allen & Motherwell (2002); Brandenburg (2008); Cabeza et al. (2002); Clearfield (1998); Cote & Shimizu (2003); Gunderman & Squattrito (1994); Kariuki & Jones (1995); Kong et al. (2006); Sharma & Clearfield (2000); Spek (2009); Videnova-Adrabinska (2007); Wagner & Merzweiler (2008).

Experimental top

The title compound was synthesized by dissolving 4-sulfobenzoic acid, potassium salt (Aldrich; 2.50 mmol) and calcium nitrate tetrahydrate (POCh; 1.25 mmol) in distilled water (3.5 ml). The mixture was sealed in a glass vial and heated at 348 K for 4 h and then slowly cooled at a rate of 1.0 K h-1 to room temperature. Plate-shaped and slightly opaque crystals suitable for X-ray measurements were obtained after the cooling process.

Refinement top

The H atoms of the carboxylic acid groups and the water molecules were observed in difference Fourier maps and their positional parameters refined. One restraint was used for the O2W—H3W distance. The H atoms of the aromatic rings were placed at calculated positions. All H atoms were assigned fixed isotropic displacement parameters correlated with the anisotropic displacement parameters of the atoms to which they are bonded.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit together with the atom assignment. Displacement ellipsoids are shown at the 50% probability level. (The coordination polyhedron of the potassium ion is shown in the inset.) [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x, -y + 2, -z + 1; (iii) x, y, z - 1; (iv) -x + 1, -y + 2, -z + 1.]
[Figure 2] Fig. 2. Two alternative presentations of the inorganic monolayer as (a) a two-dimensional arrangement of corner-sharing K2O12, CaO6 and CSO3 polyhedra and (b) a two-dimensional coordination framework formed from K ribbons, which are interweaved at the Ca ions. R1, R2 are the centrosymmetric ring motifs R22(4) and R24(8) interlinking the potassium ions inside the ribbon; R3 is the noncentrosymmetric R24(8) motif interlinking the calcium and potassium metal centers; and R4 is the nano-sized R48(16) window generated in the framework. The R4 windows are stacked one over the other in order to form nano-sized channels along the c axis. For the sake of clarity, the arene rings and the end-positioned carboxylic acid groups (except the coordinating O11B atom) have been omitted. [Symmetry codes: (ii) -x, -y + 2, -z + 1; (iv) -x + 1, -y + 2, -z + 1.]
[Figure 3] Fig. 3. A side view of three inorganic monolayers demonstrating the interrelation between the organic linkers and the formation of the nanochannels. The arene rings of B monoanions serve as pillars between the monolayers and form the walls of the nanochannels along the c axis. The A arene rings fit in the channels and create corridors between the coordination layers. In order to demonstrate the sizes of the channels the A rings have been omitted from the interior of two channels in the middle part of the figure.
Poly[hexaaquabis(µ4-4-carboxybenzenesulfonato- κ4O1:O1':O1'':O4)bis(µ3-4- carboxybenzenesulfonato- κ2O1:O1')calcium(II)dipotassium(I)] top
Crystal data top
[CaK2(C7H5O5S)4(H2O)6]Z = 1
Mr = 1031.10F(000) = 530
Triclinic, P1Dx = 1.766 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.1321 (2) ÅCell parameters from 13922 reflections
b = 10.0250 (2) Åθ = 2.4–32.7°
c = 12.6802 (3) ŵ = 0.69 mm1
α = 98.474 (2)°T = 183 K
β = 97.472 (2)°Plate, colourless
γ = 105.491 (2)°0.19 × 0.15 × 0.06 mm
V = 969.63 (4) Å3
Data collection top
Oxford Diffraction Model?
diffractometer
5921 independent reflections
Radiation source: Enhance (Mo) X-ray Source4670 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 10.4498 pixels mm-1θmax = 30.5°, θmin = 2.5°
ϕ and ω scansh = 1111
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
k = 1414
Tmin = 0.880, Tmax = 0.960l = 1818
30945 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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095Only H-atom coordinates refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0533P)2 + 0.0236P]
where P = (Fo2 + 2Fc2)/3
5921 reflections(Δ/σ)max = 0.001
301 parametersΔρmax = 0.53 e Å3
1 restraintΔρmin = 0.33 e Å3
Crystal data top
[CaK2(C7H5O5S)4(H2O)6]γ = 105.491 (2)°
Mr = 1031.10V = 969.63 (4) Å3
Triclinic, P1Z = 1
a = 8.1321 (2) ÅMo Kα radiation
b = 10.0250 (2) ŵ = 0.69 mm1
c = 12.6802 (3) ÅT = 183 K
α = 98.474 (2)°0.19 × 0.15 × 0.06 mm
β = 97.472 (2)°
Data collection top
Oxford Diffraction Model?
diffractometer
5921 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
4670 reflections with I > 2σ(I)
Tmin = 0.880, Tmax = 0.960Rint = 0.044
30945 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0381 restraint
wR(F2) = 0.095Only H-atom coordinates refined
S = 1.05Δρmax = 0.53 e Å3
5921 reflectionsΔρmin = 0.33 e Å3
301 parameters
Special details top

Experimental. Absorption correction: CrysAlis RED (Oxford Diffraction, 2008). Version 1.171.32.15 (realese 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008, 16:37:18) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. (Oxford Diffraction, 2008)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ca0.00000.50000.50000.01992 (11)
K0.31787 (5)1.04069 (4)0.40999 (3)0.02490 (10)
S41A0.35559 (5)0.65053 (4)0.37099 (3)0.01508 (9)
O42A0.17893 (15)0.57405 (13)0.37756 (10)0.0267 (3)
O43A0.47802 (17)0.57937 (14)0.41193 (11)0.0296 (3)
O41A0.40558 (17)0.79816 (12)0.41988 (10)0.0248 (3)
O11A0.25945 (17)0.55155 (14)0.17345 (10)0.0291 (3)
O12A0.53019 (17)0.69630 (14)0.12608 (11)0.0280 (3)
H12A0.512 (3)0.693 (2)0.193 (2)0.042*
C1A0.3815 (2)0.62672 (16)0.01333 (13)0.0167 (3)
C2A0.5234 (2)0.70667 (17)0.09216 (14)0.0206 (3)
H2A0.62720.75620.07120.025*
C3A0.5135 (2)0.71403 (18)0.20053 (14)0.0211 (3)
H3A0.61020.76880.25420.025*
C4A0.3616 (2)0.64097 (15)0.23109 (13)0.0150 (3)
C5A0.2194 (2)0.56056 (17)0.15323 (14)0.0205 (3)
H5A0.11550.51140.17420.025*
C6A0.2314 (2)0.55312 (18)0.04492 (14)0.0216 (3)
H6A0.13560.49680.00870.026*
C11A0.3833 (2)0.61969 (17)0.10450 (14)0.0192 (3)
S41B0.10972 (6)0.83869 (4)0.63692 (3)0.01957 (10)
O41B0.22528 (18)0.96682 (12)0.61825 (11)0.0305 (3)
O43B0.17007 (18)0.71542 (12)0.60756 (10)0.0277 (3)
O42B0.07007 (18)0.81148 (15)0.58693 (11)0.0353 (3)
O11B0.25169 (17)0.95045 (14)1.18416 (10)0.0283 (3)
O12B0.02384 (17)0.81432 (14)1.14191 (11)0.0286 (3)
H12B0.005 (3)0.828 (2)1.213 (2)0.043*
O1W0.19325 (16)0.42311 (12)0.61428 (10)0.0201 (2)
H1W0.218 (3)0.465 (2)0.6759 (19)0.030*
H2W0.278 (3)0.406 (2)0.5964 (18)0.030*
O2W0.48191 (18)1.28956 (13)0.33412 (11)0.0259 (3)
H3W0.463 (3)1.351 (2)0.3688 (18)0.039*
H4W0.577 (3)1.283 (2)0.350 (2)0.039*
O3W0.01468 (18)0.84578 (14)0.35085 (11)0.0259 (3)
H5W0.077 (3)0.896 (2)0.3729 (19)0.039*
H6W0.058 (3)0.765 (2)0.3658 (19)0.039*
C1B0.1174 (2)0.87436 (16)0.99832 (13)0.0177 (3)
C2B0.0341 (2)0.80257 (17)0.92490 (14)0.0221 (3)
H2B0.13620.75890.95030.027*
C3B0.0363 (2)0.79475 (18)0.81454 (14)0.0225 (3)
H3B0.14010.74690.76430.027*
C4B0.1136 (2)0.85708 (16)0.77813 (13)0.0175 (3)
C5B0.2660 (2)0.92976 (17)0.85057 (14)0.0224 (3)
H5B0.36840.97230.82500.027*
C6B0.2659 (2)0.93906 (18)0.96071 (14)0.0227 (4)
H6B0.36850.99021.01100.027*
C11B0.1243 (2)0.88514 (17)1.11725 (14)0.0200 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ca0.0146 (2)0.0292 (2)0.0134 (2)0.00054 (18)0.00313 (18)0.00829 (18)
K0.0292 (2)0.02181 (17)0.0204 (2)0.00346 (14)0.00027 (16)0.00538 (14)
S41A0.01562 (19)0.01855 (17)0.01196 (19)0.00400 (14)0.00518 (14)0.00514 (14)
O42A0.0202 (6)0.0366 (7)0.0177 (6)0.0034 (5)0.0092 (5)0.0042 (5)
O43A0.0332 (7)0.0440 (8)0.0239 (7)0.0232 (6)0.0110 (6)0.0176 (6)
O41A0.0343 (7)0.0198 (5)0.0177 (6)0.0033 (5)0.0071 (5)0.0018 (5)
O11A0.0294 (7)0.0375 (7)0.0139 (6)0.0003 (6)0.0029 (5)0.0032 (5)
O12A0.0241 (7)0.0432 (7)0.0146 (6)0.0022 (6)0.0068 (5)0.0100 (6)
C1A0.0193 (8)0.0192 (7)0.0130 (8)0.0058 (6)0.0061 (6)0.0045 (6)
C2A0.0169 (8)0.0270 (8)0.0160 (8)0.0005 (6)0.0059 (6)0.0064 (6)
C3A0.0179 (8)0.0269 (8)0.0136 (8)0.0018 (6)0.0029 (6)0.0037 (6)
C4A0.0169 (7)0.0168 (7)0.0123 (7)0.0047 (6)0.0055 (6)0.0040 (6)
C5A0.0171 (8)0.0252 (8)0.0171 (8)0.0002 (6)0.0063 (6)0.0052 (6)
C6A0.0170 (8)0.0286 (8)0.0150 (8)0.0009 (6)0.0015 (6)0.0033 (7)
C11A0.0210 (8)0.0229 (7)0.0157 (8)0.0076 (6)0.0056 (6)0.0054 (6)
S41B0.0276 (2)0.01722 (18)0.0131 (2)0.00427 (15)0.00565 (16)0.00277 (14)
O41B0.0452 (8)0.0200 (6)0.0224 (7)0.0007 (5)0.0111 (6)0.0064 (5)
O43B0.0421 (8)0.0213 (6)0.0228 (7)0.0108 (5)0.0145 (6)0.0036 (5)
O42B0.0309 (8)0.0544 (9)0.0173 (7)0.0086 (6)0.0012 (6)0.0060 (6)
O11B0.0277 (7)0.0364 (7)0.0158 (6)0.0026 (5)0.0010 (5)0.0041 (5)
O12B0.0268 (7)0.0398 (7)0.0158 (6)0.0020 (6)0.0074 (6)0.0062 (6)
O1W0.0206 (6)0.0208 (6)0.0177 (6)0.0055 (5)0.0034 (5)0.0009 (5)
O2W0.0290 (7)0.0274 (6)0.0188 (7)0.0028 (6)0.0068 (6)0.0041 (5)
O3W0.0344 (8)0.0231 (6)0.0204 (7)0.0044 (5)0.0094 (6)0.0086 (5)
C1B0.0208 (8)0.0180 (7)0.0155 (8)0.0066 (6)0.0052 (6)0.0034 (6)
C2B0.0203 (8)0.0253 (8)0.0181 (9)0.0017 (6)0.0050 (7)0.0039 (7)
C3B0.0214 (9)0.0258 (8)0.0163 (8)0.0005 (7)0.0034 (7)0.0026 (7)
C4B0.0235 (8)0.0155 (7)0.0142 (8)0.0064 (6)0.0051 (6)0.0024 (6)
C5B0.0212 (8)0.0266 (8)0.0183 (9)0.0029 (7)0.0070 (7)0.0047 (7)
C6B0.0167 (8)0.0306 (9)0.0172 (9)0.0027 (7)0.0013 (7)0.0021 (7)
C11B0.0220 (8)0.0225 (8)0.0176 (8)0.0086 (6)0.0048 (7)0.0049 (6)
Geometric parameters (Å, º) top
Ca—O42A2.3300 (11)C4A—C5A1.390 (2)
Ca—O42Ai2.3300 (11)C5A—C6A1.382 (2)
Ca—O43B2.3415 (13)C5A—H5A0.9500
Ca—O43Bi2.3415 (13)C6A—H6A0.9500
Ca—O1Wi2.3554 (13)S41B—O41B1.4463 (12)
Ca—O1W2.3554 (13)S41B—O42B1.4522 (14)
K—O41A2.7256 (12)S41B—O43B1.4637 (12)
K—O42Bii2.8031 (15)S41B—C4B1.7681 (17)
K—O11Biii2.8078 (13)O42B—Kii2.8031 (15)
K—O3W2.8128 (14)O11B—C11B1.211 (2)
K—O41Aiv2.8446 (13)O11B—Kv2.8078 (13)
K—O2W2.8623 (13)O12B—C11B1.326 (2)
K—O41B2.9807 (13)O12B—H12B0.87 (2)
K—H4W3.03 (2)O1W—H1W0.80 (2)
K—H5W3.09 (2)O1W—H2W0.80 (2)
S41A—O41A1.4432 (12)O2W—H3W0.770 (16)
S41A—O42A1.4561 (12)O2W—H4W0.79 (2)
S41A—O43A1.4573 (13)O3W—H5W0.84 (2)
S41A—C4A1.7702 (16)O3W—H6W0.85 (2)
O41A—Kiv2.8446 (13)C1B—C6B1.389 (2)
O11A—C11A1.214 (2)C1B—C2B1.391 (2)
O12A—C11A1.3222 (19)C1B—C11B1.489 (2)
O12A—H12A0.83 (2)C2B—C3B1.388 (2)
C1A—C6A1.388 (2)C2B—H2B0.9500
C1A—C2A1.394 (2)C3B—C4B1.383 (2)
C1A—C11A1.488 (2)C3B—H3B0.9500
C2A—C3A1.379 (2)C4B—C5B1.391 (2)
C2A—H2A0.9500C5B—C6B1.386 (2)
C3A—C4A1.392 (2)C5B—H5B0.9500
C3A—H3A0.9500C6B—H6B0.9500
O42A—Ca—O42Ai180.000 (1)C6A—C1A—C2A119.42 (15)
O42A—Ca—O43B82.09 (4)C6A—C1A—C11A118.36 (15)
O42Ai—Ca—O43B97.91 (4)C2A—C1A—C11A122.21 (14)
O42A—Ca—O43Bi97.91 (4)C3A—C2A—C1A120.15 (15)
O42Ai—Ca—O43Bi82.09 (4)C3A—C2A—H2A119.9
O43B—Ca—O43Bi180.0C1A—C2A—H2A119.9
O42A—Ca—O1Wi81.21 (4)C2A—C3A—C4A119.84 (16)
O42Ai—Ca—O1Wi98.79 (4)C2A—C3A—H3A120.1
O43B—Ca—O1Wi100.64 (4)C4A—C3A—H3A120.1
O43Bi—Ca—O1Wi79.36 (4)C5A—C4A—C3A120.55 (15)
O42A—Ca—O1W98.79 (4)C5A—C4A—S41A121.00 (11)
O42Ai—Ca—O1W81.21 (4)C3A—C4A—S41A118.44 (12)
O43B—Ca—O1W79.36 (4)C6A—C5A—C4A119.05 (14)
O43Bi—Ca—O1W100.64 (4)C6A—C5A—H5A120.5
O1Wi—Ca—O1W180.0C4A—C5A—H5A120.5
O41A—K—O42Bii149.91 (4)C5A—C6A—C1A120.98 (16)
O41A—K—O11Biii85.92 (4)C5A—C6A—H6A119.5
O42Bii—K—O11Biii95.53 (4)C1A—C6A—H6A119.5
O41A—K—O3W80.80 (4)O11A—C11A—O12A123.79 (16)
O42Bii—K—O3W71.24 (4)O11A—C11A—C1A122.48 (15)
O11Biii—K—O3W71.91 (4)O12A—C11A—C1A113.71 (15)
O41A—K—O41Aiv92.92 (3)O41B—S41B—O42B114.21 (8)
O42Bii—K—O41Aiv104.53 (4)O41B—S41B—O43B112.44 (8)
O11Biii—K—O41Aiv139.97 (4)O42B—S41B—O43B110.72 (8)
O3W—K—O41Aiv147.36 (4)O41B—S41B—C4B107.41 (8)
O41A—K—O2W131.48 (4)O42B—S41B—C4B106.39 (8)
O42Bii—K—O2W77.60 (4)O43B—S41B—C4B104.99 (7)
O11Biii—K—O2W76.95 (4)S41B—O41B—K128.98 (7)
O3W—K—O2W132.82 (4)S41B—O43B—Ca125.24 (8)
O41Aiv—K—O2W74.15 (4)S41B—O42B—Kii136.05 (8)
O41A—K—O41B75.94 (4)C11B—O11B—Kv134.89 (11)
O42Bii—K—O41B86.25 (4)C11B—O12B—H12B104.6 (16)
O11Biii—K—O41B144.71 (4)Ca—O1W—H1W115.1 (15)
O3W—K—O41B75.43 (4)Ca—O1W—H2W122.7 (16)
O41Aiv—K—O41B71.98 (4)H1W—O1W—H2W109 (2)
O2W—K—O41B137.15 (4)K—O2W—H3W106.5 (18)
O41A—K—H4W118.1 (4)K—O2W—H4W94.4 (17)
O42Bii—K—H4W91.7 (4)H3W—O2W—H4W115 (2)
O11Biii—K—H4W80.7 (5)K—O3W—H5W101.2 (16)
O3W—K—H4W145.7 (5)K—O3W—H6W132.4 (16)
O41Aiv—K—H4W64.7 (5)H5W—O3W—H6W106 (2)
O2W—K—H4W15.1 (4)C6B—C1B—C2B119.70 (15)
O41B—K—H4W134.5 (5)C6B—C1B—C11B118.81 (15)
O41A—K—H5W94.5 (4)C2B—C1B—C11B121.48 (15)
O42Bii—K—H5W56.5 (4)C3B—C2B—C1B120.05 (15)
O11Biii—K—H5W80.0 (4)C3B—C2B—H2B120.0
O3W—K—H5W15.6 (4)C1B—C2B—H2B120.0
O41Aiv—K—H5W139.8 (4)C4B—C3B—C2B119.62 (16)
O2W—K—H5W125.6 (4)C4B—C3B—H3B120.2
O41B—K—H5W71.7 (4)C2B—C3B—H3B120.2
H4W—K—H5W140.5 (6)C3B—C4B—C5B121.01 (15)
O41A—S41A—O42A113.94 (8)C3B—C4B—S41B118.66 (13)
O41A—S41A—O43A112.39 (8)C5B—C4B—S41B120.31 (12)
O42A—S41A—O43A110.88 (8)C6B—C5B—C4B118.90 (15)
O41A—S41A—C4A106.96 (7)C6B—C5B—H5B120.6
O42A—S41A—C4A105.83 (7)C4B—C5B—H5B120.6
O43A—S41A—C4A106.24 (7)C5B—C6B—C1B120.70 (16)
S41A—O42A—Ca142.63 (8)C5B—C6B—H6B119.7
S41A—O41A—K142.44 (8)C1B—C6B—H6B119.7
S41A—O41A—Kiv130.48 (7)O11B—C11B—O12B123.69 (16)
K—O41A—Kiv87.08 (3)O11B—C11B—C1B123.68 (15)
C11A—O12A—H12A105.1 (17)O12B—C11B—C1B112.63 (15)
O41A—S41A—O42A—Ca65.38 (15)C6A—C1A—C11A—O12A178.24 (15)
O43A—S41A—O42A—Ca62.59 (15)C2A—C1A—C11A—O12A0.4 (2)
C4A—S41A—O42A—Ca177.39 (12)O42B—S41B—O41B—K63.81 (12)
O43B—Ca—O42A—S41A35.10 (13)O43B—S41B—O41B—K63.45 (12)
O43Bi—Ca—O42A—S41A144.90 (13)C4B—S41B—O41B—K178.47 (8)
O1Wi—Ca—O42A—S41A137.22 (14)O41A—K—O41B—S41B57.06 (10)
O1W—Ca—O42A—S41A42.78 (14)O42Bii—K—O41B—S41B98.48 (10)
O42A—S41A—O41A—K58.55 (13)O11Biii—K—O41B—S41B4.19 (15)
O43A—S41A—O41A—K174.25 (10)O3W—K—O41B—S41B26.90 (10)
C4A—S41A—O41A—K58.02 (13)O41Aiv—K—O41B—S41B154.92 (11)
O42A—S41A—O41A—Kiv121.76 (9)O2W—K—O41B—S41B165.71 (8)
O43A—S41A—O41A—Kiv5.45 (11)O41B—S41B—O43B—Ca131.12 (8)
C4A—S41A—O41A—Kiv121.67 (9)O42B—S41B—O43B—Ca2.03 (11)
O42Bii—K—O41A—S41A54.15 (16)C4B—S41B—O43B—Ca112.41 (9)
O11Biii—K—O41A—S41A39.85 (12)O42A—Ca—O43B—S41B110.27 (9)
O3W—K—O41A—S41A32.46 (12)O42Ai—Ca—O43B—S41B69.73 (9)
O41Aiv—K—O41A—S41A179.76 (14)O1Wi—Ca—O43B—S41B30.82 (9)
O2W—K—O41A—S41A108.43 (12)O1W—Ca—O43B—S41B149.18 (9)
O41B—K—O41A—S41A109.63 (12)O41B—S41B—O42B—Kii54.39 (13)
O42Bii—K—O41A—Kiv126.09 (7)O43B—S41B—O42B—Kii177.47 (9)
O11Biii—K—O41A—Kiv139.91 (4)C4B—S41B—O42B—Kii63.92 (12)
O3W—K—O41A—Kiv147.77 (4)C6B—C1B—C2B—C3B0.5 (2)
O41Aiv—K—O41A—Kiv0.0C11B—C1B—C2B—C3B179.84 (15)
O2W—K—O41A—Kiv71.33 (5)C1B—C2B—C3B—C4B0.9 (3)
O41B—K—O41A—Kiv70.61 (4)C2B—C3B—C4B—C5B1.1 (3)
C6A—C1A—C2A—C3A0.9 (2)C2B—C3B—C4B—S41B177.17 (13)
C11A—C1A—C2A—C3A177.67 (15)O41B—S41B—C4B—C3B146.59 (13)
C1A—C2A—C3A—C4A0.2 (3)O42B—S41B—C4B—C3B23.90 (15)
C2A—C3A—C4A—C5A0.1 (3)O43B—S41B—C4B—C3B93.53 (14)
C2A—C3A—C4A—S41A178.85 (13)O41B—S41B—C4B—C5B35.08 (15)
O41A—S41A—C4A—C5A127.22 (13)O42B—S41B—C4B—C5B157.78 (14)
O42A—S41A—C4A—C5A5.39 (15)O43B—S41B—C4B—C5B84.80 (14)
O43A—S41A—C4A—C5A112.55 (14)C3B—C4B—C5B—C6B0.0 (2)
O41A—S41A—C4A—C3A53.88 (15)S41B—C4B—C5B—C6B178.28 (13)
O42A—S41A—C4A—C3A175.71 (13)C4B—C5B—C6B—C1B1.4 (3)
O43A—S41A—C4A—C3A66.35 (15)C2B—C1B—C6B—C5B1.7 (3)
C3A—C4A—C5A—C6A0.6 (2)C11B—C1B—C6B—C5B178.98 (15)
S41A—C4A—C5A—C6A178.31 (13)Kv—O11B—C11B—O12B12.9 (3)
C4A—C5A—C6A—C1A1.3 (3)Kv—O11B—C11B—C1B167.80 (11)
C2A—C1A—C6A—C5A1.5 (3)C6B—C1B—C11B—O11B1.8 (3)
C11A—C1A—C6A—C5A177.19 (15)C2B—C1B—C11B—O11B177.47 (16)
C6A—C1A—C11A—O11A0.5 (2)C6B—C1B—C11B—O12B177.56 (15)
C2A—C1A—C11A—O11A179.14 (16)C2B—C1B—C11B—O12B3.1 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+2, z+1; (iii) x, y, z1; (iv) x+1, y+2, z+1; (v) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O11Av0.80 (2)1.93 (2)2.7248 (18)175 (2)
O1W—H2W···O43Avi0.80 (2)1.97 (2)2.7425 (18)161 (2)
O2W—H3W···O43Avii0.77 (2)2.24 (2)2.9374 (19)152 (2)
O2W—H4W···O43Biv0.79 (2)2.06 (2)2.846 (2)175 (2)
O3W—H5W···O41Bii0.84 (2)2.06 (2)2.880 (2)163 (2)
O3W—H6W···O1Wi0.85 (2)1.99 (2)2.8281 (17)171 (2)
O12A—H12A···O2Wviii0.83 (2)1.83 (3)2.6531 (18)168 (2)
O12B—H12B···O3Wv0.87 (2)1.75 (3)2.6104 (18)168 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+2, z+1; (iv) x+1, y+2, z+1; (v) x, y, z+1; (vi) x+1, y+1, z+1; (vii) x, y+1, z; (viii) x+1, y+2, z.

Experimental details

Crystal data
Chemical formula[CaK2(C7H5O5S)4(H2O)6]
Mr1031.10
Crystal system, space groupTriclinic, P1
Temperature (K)183
a, b, c (Å)8.1321 (2), 10.0250 (2), 12.6802 (3)
α, β, γ (°)98.474 (2), 97.472 (2), 105.491 (2)
V3)969.63 (4)
Z1
Radiation typeMo Kα
µ (mm1)0.69
Crystal size (mm)0.19 × 0.15 × 0.06
Data collection
DiffractometerOxford Diffraction Model?
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.880, 0.960
No. of measured, independent and
observed [I > 2σ(I)] reflections
30945, 5921, 4670
Rint0.044
(sin θ/λ)max1)0.714
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.095, 1.05
No. of reflections5921
No. of parameters301
No. of restraints1
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.53, 0.33

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008), publCIF (Westrip, 2009).

Selected bond lengths (Å) top
Ca—O42A2.3300 (11)K—O42Bii2.8031 (15)
Ca—O42Ai2.3300 (11)K—O11Biii2.8078 (13)
Ca—O43B2.3415 (13)K—O3W2.8128 (14)
Ca—O43Bi2.3415 (13)K—O41Aiv2.8446 (13)
Ca—O1Wi2.3554 (13)K—O2W2.8623 (13)
Ca—O1W2.3554 (13)K—O41B2.9807 (13)
K—O41A2.7256 (12)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+2, z+1; (iii) x, y, z1; (iv) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O11Av0.80 (2)1.93 (2)2.7248 (18)175 (2)
O1W—H2W···O43Avi0.80 (2)1.97 (2)2.7425 (18)161 (2)
O2W—H3W···O43Avii0.770 (16)2.236 (18)2.9374 (19)152 (2)
O2W—H4W···O43Biv0.79 (2)2.06 (2)2.846 (2)175 (2)
O3W—H5W···O41Bii0.84 (2)2.06 (2)2.880 (2)163 (2)
O3W—H6W···O1Wi0.85 (2)1.99 (2)2.8281 (17)171 (2)
O12A—H12A···O2Wviii0.83 (2)1.83 (3)2.6531 (18)168 (2)
O12B—H12B···O3Wv0.87 (2)1.75 (3)2.6104 (18)168 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+2, z+1; (iv) x+1, y+2, z+1; (v) x, y, z+1; (vi) x+1, y+1, z+1; (vii) x, y+1, z; (viii) x+1, y+2, z.
 

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