Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615015430/eg3188sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015430/eg31881sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015430/eg31882sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015430/eg31883sup4.hkl |
CCDC references: 1419428; 1419427; 1419426
Chemical and steric constraints imposed by the crystal lattice often result in the stabilization of peculiar and unusual molecular and coordination geometries, such as perfectly tetrahedral CuX_{4}^{2-} (X = Cl, Br) anions in high-symmetry lattice clathrates (Kahwa et al., 1992), or, in contrast, tetragonal distortion of Ni^{2+} octahedra in La_{2}NiO_{4} (Brown, 1992). These effects may be referred to as `pressure of the crystal environment', but their prediction, evaluation and utilization for crystal design are not straightforward. From this point of view, univalent metal complexes with the macrocyclic polyether 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) can be regarded as especially suitable and structurally simple molecular models. It is well known that large cations, such as Rb^{+}, Cs^{+}, Tl^{+} and NH_{4}^{+}, do not fit the size of the 18-crown-6 cavity (Steed, 2001). In their crystal structures, they usually reside above the ligand plane, with the most significant deviations (up to d = 2.40 Å) observed for the largest caesium cations (Domasevitch et al., 1997). In fact, the importance of ion-dipole interactions with the counteranions is particularly dominant for the present systems, which appear to be very sensitive to the crystal environment (Steed, 2001). The forced centrosymmetric structure of the [M(18-crown-6)]^{+} group, with the large metal cation situated exactly in the centre of the ligand cavity, may presumably be constrained with a set of equivalent supramolecular interactions from both axial sides. The usefulness of this approach was suggested by the structure of coordination chains –([M(18-crown-6)]-A–)_{n}– supported by centrosymmetric singly charged anionic linkers. A series of such compounds, based upon hydrogen oximate anions [H{ONC(CN)—R}_{2}]^{-} (R = COPh, benzothiazol-2-yl), revealed the first examples for a perfect fit of Rb^{+}, Tl^{+} and NH_{4}^{+} cations inside the 18-crown-6 cavity (Domasevitch et al., 1996, 1998; Ponomarova & Domasevitch, 2002). The inorganic tetrachloridoaurate(III) anion [AuCl_{4}]^{-} could also be applied: it stabilizes the centrosymmetric structure of [Rb(18-crown-6)]^{+} (with the Rb^{+} cation equally disordered above and below the ligand plane at d = 0.40 Å), being integrated within {[Rb(18-crown-6)][AuCl_{4}]}_{n} chains (Manskaya et al., 1998).
These observations raise further interest in the structure of the caesium systems. Due to the large ionic radius of Cs^{+} (1.67 Å), they exhibit no isomorphism with the related complexes of lighter alkali metal and ammonium ions, and thus the centrosymmetric structure of [Cs(18-crown-6)]^{+} does not appear to have been considered. In the present work, we illustrate this very uncommon possibility, with a rational combination of cationic and anionic counterparts of the structure. As was revealed by the prototypic structures of the oxonium compounds, [H_{3}O(18-crown-6)][SbCl_{6}] (Neumüller et al., 1994) and [H_{3}O(18-crown-6)][TaCl_{6}] (Bulychev & Bel'sky, 1995), singly charged octahedral hexachloridometallate anions [M^{V}Cl_{6}]^{-} are complementary with [H_{3}O(18-crown-6)]^{+} from the point of view of charge and local symmetry, and they generate infinite stacks with [H_{3}O(18-crown-6)]^{+} embedded between pairs of inversion-related anions. Following this structural paradigm, we have prepared a series of new compounds, [M(18-crown-6)][SbCl_{6}] [M = Rb, (1), Cs, (2), and NH_{4}, (3)] and here report their structures.
The hexachloridoantimonate(V) complexes [M(18-crown-6)][SbCl_{6}] were prepared by reacting M[SbCl_{6}] [M = Rb, Cs and NH_{4}] and 18-crown-6 in dimethylformamide (DMF) solutions. Thus, a solution of RbCl (1.706 g, 14.1 mmol) in warm HCl (30%, 10 ml) was added to a 0.98 M solution (14.3 ml) of SbCl_{5} in 30% HCl. The colourless precipitate of Rb[SbCl_{6}] (5.33 g, 90%) was filtered off, washed with 30% HCl (5 ml) and dried. A solution of this material (0.290 g, 0.69 mmol) in warm DMF (5 ml) was added to a solution of 18-crown-6 (0.185 g, 0.70 mmol) in DMF (5 ml) with stirring. The colourless crystalline product, [Rb(18-crown-6)][SbCl_{6}], (1), was filtered off, washed with DMF (5 ml) and dried in vacuo. Large colourless prism crystals of the complex grew from the DMF filtrate over a period of 2 d (combined yield 0.305 g, 65%). The isomorphous complexes [Cs(18-crown-6)][SbCl_{6}], (2), and [NH_{4}(18-crown-6)][SbCl_{6}], (3) (both also colourless prisms), were prepared in a similar fashion starting with the caesium and ammonium chlorides, respectively.
Elemental analysis, calculated for (1): C 21.06, H 3.54; found: C 20.92, H 3.60%; calculated for (2): C 19.70, H, 3.31; found: C 19.91, H 3.47%; calculated for (3): C 23.37, H 4.58, N 2.27; found: C 23.51, H 4.64, N 2.03%.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located from difference Fourier maps but refined as riding, with C—H = 0.98 Å and ammonium N—H = 0.90 Å, and with U_{iso}(H) = 1.2U_{eq}(C) or 1.5U_{eq}(N). In all three structures, the metal (Rb and Cs) and ammonium cations are disordered about a centre of inversion. The corresponding Rb, Cs and N atoms were freely refined with anisotropic displacement parameters and with occupancy factors of 0.5. Tentative structure solutions in the noncentrosymmetric subgroup R3 did not provide ordered models, and the subsequent refinements equally suggested disorder of the cations above and below the 18-crown-6 plane.
In the isomorphous compounds (1)–(3) (Table 1), the hexachloridoantimonate(V) anions reside on a 3 axis, with the central Sb atoms situated on a centre of inversion. The [M(18-crown-6)]^{+} groups are also centrosymmetric and located about a 3 axis; it passes through the centroid of the 18-crown-6 molecule which lies on a centre of inversion. In all three structures, the crown ether adopts the D_{3d} conformation, with 1/6 of the molecule being symmetrically independent. All O—C—C—O torsion angles are gauche, whereas all C—O—C—C angles are trans, and the sequence of torsion angles is [(tg^{+}t)(tg^{-}t)]_{3}. This geometry is identical to that observed for centrosymmetric metal ion complexes of 18-crown-6 (Bajaj & Poonia, 1988).
The Rb^{+} [in (1)], Cs^{+} [in (2)] and NH_{4}^{+} [in (3)] cations reside on a 3 axis and appear to be disordered about a centre of inversion, above and below the mean plane defined by the six O atoms of the 18-crown-6 ligand. Inside the ligand cavity, the Rb^{+} and Cs^{+} cations form six nearly equidistant bonds with donor O atoms (Fig. 1), whereas the ammonium cation is held there by three equivalent moderately strong hydrogen bonds [N···O = 2.928 (3) Å and N—H···O = 162°] (Fig. 2). These bonds are very similar to those found for [NH_{4}(18-crown-6)][PF_{6}] (Wu & Wu, 2010).
In spite of the fact that the positions of the metal and, in the case of ammonium, of the N atom do not coincide with the centre of the crown ether cavity, the corresponding deviations are only minor and amount to d = 0.4808 (13) Å for Rb^{+}, 0.515 (8) Å for NH_{4}^{+} and 0.9344 (8) Å for Cs^{+}. These numbers are significantly smaller than typical values observed earlier. For example, in [NH_{4}(18-crown-6)]^{+} compounds the essential size mismatch of the components is commonly reflected by pronounced dislocations of the ammonium cation from the ring centroid, such as d = 1.03 Å for the hydrogen sulfate complex (Braga et al., 2007) and d = 0.98 Å for the hydrated bromide complex (Nagano et al., 1978). The forced geometry of the NH_{4}^{+} cation exactly inside the 18-crown-6 cavity has only one precedent (Ponomarova & Domasevitch, 2002), while the centrosymmetric structure of the [Cs(18-crown-6)]^{+} aggregate is entirely unprecedented. In (2), the deviation of the caesium cation from the ring centroid is much smaller than the characteristic values of 1.50–2.40 Å (Steed, 2001; Domasevitch et al., 1997) and even smaller than the previous lower limit of 1.18 Å for the η^{2}-fluorenyl complex (Neander et al., 2000). The forced geometry of the [M(18-crown-6)]^{+} groups is also reflected in unusually short coordination bonds [for (1), Rb—O = 2.839 (2) and 2.917 (2) Å; for (2), Cs—O = 2.939 (2) and 3.091 (2) Å], which may be compared with typical values for 18-crown-6 complexes in the ranges 2.92–3.13 and 3.05–3.35 Å, respectively (Bajaj & Poonia, 1988; Steed, 2001). The location of the large cations almost in the centre of the 18-crown-6 cavity is facilitated by a certain conformational flexibility of the ligand. In all three cases, the torsion angles O—C—C—O exceed the standard for 18-crown-6 molecule values of 66° (Bajaj & Poonia, 1988), with the maximum value observed for the complex of the largest cation, Cs^{+} [70.0 (4)° in (1), 70.9 (4)° in (2) and 68.8 (3)° in (3)].
The supramolecular structures of these three compounds are completely uniform. They arrange in infinite linear chains along the c axis in which [M(18-crown-6)]^{+} and [SbCl_{6}]^{-} groups alternate (Figs. 3 and 4). The shortest contacts between the chains, formed by each of the six Cl atoms of the anion, indicate very weak C–H···Cl hydrogen bonds [for (2), C1···Cl1^{vi} = 3.805 (3) Å; C1—H···Cl1^{vi} = 130°; symmetry code: (vi) 2/3 - x + y, 1/3 - x, 1/3 + z]. Inter-ion bonding within the chains is at first sight counterintuitive: the shortest contacts with the Cl atoms are observed for the largest Cs cations. The three symmetrically equivalent Cs1—Cl1 separations [3.5938 (12) Å] in (2) agree well with the standard value in the CsCl structure [3.56 Å; Wells, 1991], but the corresponding Rb1—Cl1 distances in (1) are significantly longer [3.7353 (16) Å, versus 3.28 Å in RbCl]. This parallels the weak interactions in the NH_{4}^{+} complex, (3): strong inter-ion hydrogen bonds do not exist, and the distal N—H···[SbCl_{6}]^{-} contacts [N1···Cl1 = 3.746 (7) Å and N1—H···Cl1 = 140°] can be ascribed either to a very weak trifurcated hydrogen bond or to dispersion forces (Fig. 2). It is worth noting that the chain periodicity for all three structures (half of the lattice parameter c) is very similar and insensitive to the nature of the encapsulated cation. This is primarily caused by tight packing of the 18-crown-6 units and the bulky [SbCl_{6}]^{-} anions, resulting in uniform inter-ion separations for (1)–(3). Therefore, when passing from Cs^{+} to Rb^{+}, the slightly larger deviation of the metal cation from the mean plane through the 18-crown-6 ring leads to shorter ion-dipole bonding with the anions, as demonstrated by structures (1) and (2). The [SbCl_{6}]^{-} anions play a crucial role in sustaining such stacks, since the structures of closely related singly charged octahedral hexafluorophosphates are completely different: stronger ion-dipole interactions or hydrogen bonding with the more electronegative F atoms results in significant displacement of the cations from the ligand cavity, disintegration of the stacks and generation of molecular arrays, for example in [Tl(18-crown-6)][PF_{6}] (Liu, 2003) and [NH_{4}(18-crown-6)][PF_{6}] (Wu & Wu, 2010).
The supramolecular structures presented here are likely predetermined by a perfect match between charge, shape, size and symmetry of the [M(18-crown-6)]+ and [SbCl_{6}]^{-} components which facilitates favourable and very tight packing. This idea is supported by their unusually high packing indices of 77.8% [in (1)] and 76.4% [in (2)], as calculated by PLATON (Spek, 2009), assuming ordered positions of the cations at the centre of the 18-crown-6 cavity. The encapsulated cations thus appear in a constrained crystal environment: the behaviour of the large caesium cation towards the 18-crown-6 ligand in (2) is unprecedented and similar to that of the common K^{+}, Rb^{+} and NH_{4}^{+} systems. This is best illustrated by the isomorphism of the Rb^{+}, NH_{4}^{+} and Cs^{+} derivatives (1)–(3). The previously reported oxonium complexes [H_{3}O(18-crown-6)][SbCl_{6}] (Neumüller et al., 1994) and [H_{3}O(18-crown-6)][TaCl_{6}] (Bulychev & Bel'sky, 1995) afford closely related structures, even without any strong interactions between the cationic and anionic residues: all three H atoms of the oxonium cations are bonded to crown ether O acceptors and not accessible for intermolecular bonding. This relationship provides the first example of isomorphism between caesium and oxonium 18-crown-6 complexes. It is even more interesting that the product obtained via reduction of perrhenate in a liquid clathrating medium (18-crown-6/H_{2}O/HCl) is also isomorphous (Barbour et al., 1996). This finding suggests that crystallization affords the compound [H_{3}O(18-crown-6)][ReCl_{6}], containing the unusual [Re^{V}Cl_{6}]^{-} anion (Arp & Preetz, 1994), rather than the originally assumed [H_{3}O(18-crown-6)]_{2}[Re^{IV}Cl_{6}], with `remarkably short Re—Cl bonds' (Barbour et al., 1996). The stabilization of the partially reduced chloridorhenate(V) anion may also be related to the specific and favourable supramolecular structure reported here, predetermining the very low solubility of the solid. The [M^{I}(18-crown-6)][M^{V}Cl_{6}] lattice can thus be proposed as a suitable form for the synthesis and isolation of unstable or unusual hexachloridometallate(V) (M = Re, W, U etc.) derivatives.
In brief, the present study is important for new structural features of 18-crown-6 complexes, in particular those formed by the large caesium cation, as well as for providing reliable chemical targets for the evaluation of unusual molecular geometries constrained in the specific crystal environment.
For related literature, see: Arp & Preetz (1994); Bajaj & Poonia (1988); Barbour et al. (1996); Braga et al. (2007); Brown (1992); Bulychev & Bel'sky (1995); Domasevitch et al. (1996, 1997, 1998); Kahwa et al. (1992); Liu (2003); Manskaya et al. (1998); Nagano et al. (1978); Neander et al. (2000); Neumüller et al. (1994); Ponomarova & Domasevitch (2002); Spek (2009); Steed (2001); Wells (1991); Wu & Wu (2010).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994) for (1), (3); APEX2 (Bruker, 2008) for (2). Cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994) for (1), (3); SAINT (Bruker, 2008) for (2). Data reduction: XCAD4 (Harms & Wocadlo, 1995) for (1), (3); SAINT (Bruker, 2008) for (2). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999). Software used to prepare material for publication: WinGX (Farrugia, 2012) for (1), (2); SHELXL97 (Sheldrick, 2008) for (3).
[Rb(C_{12}H_{24}O_{6})]·[SbCl_{6}] | D_{x} = 1.963 Mg m^{−}^{3} |
M_{r} = 684.23 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 24 reflections |
a = 14.1011 (10) Å | θ = 12.1–17.8° |
c = 10.0850 (9) Å | µ = 4.00 mm^{−}^{1} |
V = 1736.7 (2) Å^{3} | T = 223 K |
Z = 3 | Prism, colourless |
F(000) = 1002 | 0.26 × 0.22 × 0.20 mm |
Enraf–Nonius CAD4 diffractometer | 635 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | R_{int} = 0.073 |
Graphite monochromator | θ_{max} = 25.2°, θ_{min} = 2.6° |
non–profiled ω–2θ scans | h = −16→16 |
Absorption correction: ψ scan (North et al., 1968) | k = −16→16 |
T_{min} = 0.423, T_{max} = 0.502 | l = −10→12 |
2016 measured reflections | 3 standard reflections every 120 min |
697 independent reflections | intensity decay: none |
Refinement on F^{2} | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F^{2} > 2σ(F^{2})] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F^{2}) = 0.065 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ^{2}(F_{o}^{2}) + (0.0186P)^{2}] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
697 reflections | (Δ/σ)_{max} < 0.001 |
42 parameters | Δρ_{max} = 0.35 e Å^{−}^{3} |
0 restraints | Δρ_{min} = −0.42 e Å^{−}^{3} |
[Rb(C_{12}H_{24}O_{6})]·[SbCl_{6}] | Z = 3 |
M_{r} = 684.23 | Mo Kα radiation |
Trigonal, R3 | µ = 4.00 mm^{−}^{1} |
a = 14.1011 (10) Å | T = 223 K |
c = 10.0850 (9) Å | 0.26 × 0.22 × 0.20 mm |
V = 1736.7 (2) Å^{3} |
Enraf–Nonius CAD4 diffractometer | 635 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | R_{int} = 0.073 |
T_{min} = 0.423, T_{max} = 0.502 | 3 standard reflections every 120 min |
2016 measured reflections | intensity decay: none |
697 independent reflections |
R[F^{2} > 2σ(F^{2})] = 0.026 | 0 restraints |
wR(F^{2}) = 0.065 | H-atom parameters constrained |
S = 1.05 | Δρ_{max} = 0.35 e Å^{−}^{3} |
697 reflections | Δρ_{min} = −0.42 e Å^{−}^{3} |
42 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | U_{iso}*/U_{eq} | Occ. (<1) | |
Sb1 | 0.0000 | 0.0000 | 0.0000 | 0.02973 (17) | |
Rb1 | 0.0000 | 0.0000 | 0.45233 (13) | 0.0483 (4) | 0.50 |
Cl1 | 0.15794 (7) | 0.07923 (8) | 0.13513 (9) | 0.0523 (3) | |
O1 | 0.22441 (17) | 0.16174 (17) | 0.5233 (2) | 0.0412 (6) | |
C1 | 0.2971 (3) | 0.1260 (3) | 0.4783 (4) | 0.0438 (8) | |
H1A | 0.3721 | 0.1783 | 0.5059 | 0.053* | |
H1B | 0.2953 | 0.1216 | 0.3813 | 0.053* | |
C2 | 0.2621 (3) | 0.0152 (3) | 0.5368 (3) | 0.0437 (8) | |
H2A | 0.3183 | −0.0049 | 0.5206 | 0.052* | |
H2B | 0.2522 | 0.0167 | 0.6329 | 0.052* |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
Sb1 | 0.0274 (2) | 0.0274 (2) | 0.0344 (3) | 0.01370 (10) | 0.000 | 0.000 |
Rb1 | 0.0288 (3) | 0.0288 (3) | 0.0874 (10) | 0.01439 (17) | 0.000 | 0.000 |
Cl1 | 0.0416 (5) | 0.0493 (5) | 0.0630 (6) | 0.0206 (4) | −0.0192 (4) | −0.0097 (4) |
O1 | 0.0317 (11) | 0.0344 (12) | 0.0563 (14) | 0.0156 (10) | 0.0081 (10) | 0.0068 (10) |
C1 | 0.0249 (16) | 0.0460 (19) | 0.056 (2) | 0.0143 (15) | 0.0017 (14) | −0.0084 (17) |
C2 | 0.0366 (18) | 0.053 (2) | 0.0489 (18) | 0.0274 (17) | −0.0064 (15) | −0.0063 (16) |
Sb1—Cl1^{i} | 2.3617 (8) | Rb1—O1^{v} | 2.917 (2) |
Sb1—Cl1 | 2.3617 (8) | Rb1—Cl1^{ii} | 3.7353 (16) |
Sb1—Cl1^{ii} | 2.3617 (8) | Rb1—Cl1 | 3.7353 (16) |
Sb1—Cl1^{iii} | 2.3617 (8) | Rb1—Cl1^{v} | 3.7353 (16) |
Sb1—Cl1^{iv} | 2.3617 (8) | O1—C2^{vii} | 1.422 (4) |
Sb1—Cl1^{v} | 2.3617 (8) | O1—C1 | 1.424 (4) |
Rb1—O1^{vi} | 2.839 (2) | C1—C2 | 1.504 (5) |
Rb1—O1^{vii} | 2.839 (2) | C1—H1A | 0.9800 |
Rb1—O1^{viii} | 2.839 (2) | C1—H1B | 0.9800 |
Rb1—O1 | 2.917 (2) | C2—H2A | 0.9800 |
Rb1—O1^{ii} | 2.917 (2) | C2—H2B | 0.9800 |
Cl1^{i}—Sb1—Cl1 | 180 | O1^{v}—Rb1—Cl1^{ii} | 110.28 (5) |
Cl1^{i}—Sb1—Cl1^{ii} | 89.97 (4) | O1^{vi}—Rb1—Cl1 | 124.94 (6) |
Cl1—Sb1—Cl1^{ii} | 90.03 (4) | O1^{vii}—Rb1—Cl1 | 86.21 (5) |
Cl1^{i}—Sb1—Cl1^{iii} | 90.03 (4) | O1^{viii}—Rb1—Cl1 | 73.47 (5) |
Cl1—Sb1—Cl1^{iii} | 89.97 (4) | O1—Rb1—Cl1 | 74.04 (5) |
Cl1^{ii}—Sb1—Cl1^{iii} | 89.97 (4) | O1^{ii}—Rb1—Cl1 | 110.28 (5) |
Cl1^{i}—Sb1—Cl1^{iv} | 90.03 (4) | O1^{v}—Rb1—Cl1 | 124.00 (5) |
Cl1—Sb1—Cl1^{iv} | 89.97 (4) | Cl1^{ii}—Rb1—Cl1 | 53.13 (3) |
Cl1^{ii}—Sb1—Cl1^{iv} | 180 | O1^{vi}—Rb1—Cl1^{v} | 86.21 (5) |
Cl1^{iii}—Sb1—Cl1^{iv} | 90.03 (4) | O1^{vii}—Rb1—Cl1^{v} | 73.47 (5) |
Cl1^{i}—Sb1—Cl1^{v} | 89.97 (4) | O1^{viii}—Rb1—Cl1^{v} | 124.94 (6) |
Cl1—Sb1—Cl1^{v} | 90.03 (4) | O1—Rb1—Cl1^{v} | 110.28 (5) |
Cl1^{ii}—Sb1—Cl1^{v} | 90.03 (4) | O1^{ii}—Rb1—Cl1^{v} | 124.00 (5) |
Cl1^{iii}—Sb1—Cl1^{v} | 180 | O1^{v}—Rb1—Cl1^{v} | 74.04 (5) |
Cl1^{iv}—Sb1—Cl1^{v} | 89.97 (4) | Cl1^{ii}—Rb1—Cl1^{v} | 53.13 (3) |
O1^{vi}—Rb1—O1^{vii} | 119.261 (16) | Cl1—Rb1—Cl1^{v} | 53.13 (3) |
O1^{vi}—Rb1—O1^{viii} | 119.261 (16) | Sb1—Cl1—Rb1 | 94.16 (3) |
O1^{vii}—Rb1—O1^{viii} | 119.261 (17) | C2^{vii}—O1—C1 | 112.0 (3) |
O1^{vi}—Rb1—O1 | 160.83 (5) | C2^{vii}—O1—Rb1^{vi} | 116.14 (19) |
O1^{vii}—Rb1—O1 | 59.728 (14) | C1—O1—Rb1^{vi} | 116.98 (18) |
O1^{viii}—Rb1—O1 | 59.728 (14) | C2^{vii}—O1—Rb1 | 106.74 (18) |
O1^{vi}—Rb1—O1^{ii} | 59.728 (14) | C1—O1—Rb1 | 109.66 (18) |
O1^{vii}—Rb1—O1^{ii} | 160.83 (5) | O1—C1—C2 | 108.8 (3) |
O1^{viii}—Rb1—O1^{ii} | 59.728 (14) | O1—C1—H1A | 109.9 |
O1—Rb1—O1^{ii} | 114.18 (4) | C2—C1—H1A | 109.9 |
O1^{vi}—Rb1—O1^{v} | 59.728 (14) | O1—C1—H1B | 109.9 |
O1^{vii}—Rb1—O1^{v} | 59.728 (14) | C2—C1—H1B | 109.9 |
O1^{viii}—Rb1—O1^{v} | 160.83 (5) | H1A—C1—H1B | 108.3 |
O1—Rb1—O1^{v} | 114.18 (4) | O1^{viii}—C2—C1 | 108.5 (3) |
O1^{ii}—Rb1—O1^{v} | 114.18 (4) | O1^{viii}—C2—H2A | 110.0 |
O1^{vi}—Rb1—Cl1^{ii} | 73.47 (5) | C1—C2—H2A | 110.0 |
O1^{vii}—Rb1—Cl1^{ii} | 124.94 (6) | O1^{viii}—C2—H2B | 110.0 |
O1^{viii}—Rb1—Cl1^{ii} | 86.21 (5) | C1—C2—H2B | 110.0 |
O1—Rb1—Cl1^{ii} | 124.00 (5) | H2A—C2—H2B | 108.4 |
O1^{ii}—Rb1—Cl1^{ii} | 74.04 (5) | ||
Cl1^{ii}—Sb1—Cl1—Rb1 | −45.014 (18) | O1^{v}—Rb1—O1—C2^{vii} | −55.4 (2) |
Cl1^{iii}—Sb1—Cl1—Rb1 | −134.986 (18) | Cl1^{ii}—Rb1—O1—C2^{vii} | 84.11 (19) |
Cl1^{iv}—Sb1—Cl1—Rb1 | 134.986 (18) | Cl1—Rb1—O1—C2^{vii} | 65.15 (18) |
Cl1^{v}—Sb1—Cl1—Rb1 | 45.014 (18) | Cl1^{v}—Rb1—O1—C2^{vii} | 25.6 (2) |
O1^{vi}—Rb1—Cl1—Sb1 | 17.33 (7) | O1^{vi}—Rb1—O1—C1 | 116.1 (2) |
O1^{vii}—Rb1—Cl1—Sb1 | −106.12 (5) | O1^{vii}—Rb1—O1—C1 | −151.4 (3) |
O1^{viii}—Rb1—Cl1—Sb1 | 131.83 (6) | O1^{viii}—Rb1—O1—C1 | 23.52 (18) |
O1—Rb1—Cl1—Sb1 | −165.69 (5) | O1^{ii}—Rb1—O1—C1 | 49.1 (2) |
O1^{ii}—Rb1—Cl1—Sb1 | 83.92 (6) | O1^{v}—Rb1—O1—C1 | −176.96 (18) |
O1^{v}—Rb1—Cl1—Sb1 | −56.97 (6) | Cl1^{ii}—Rb1—O1—C1 | −37.4 (2) |
Cl1^{ii}—Rb1—Cl1—Sb1 | 33.987 (5) | Cl1—Rb1—O1—C1 | −56.4 (2) |
Cl1^{v}—Rb1—Cl1—Sb1 | −33.987 (5) | Cl1^{v}—Rb1—O1—C1 | −95.9 (2) |
O1^{vi}—Rb1—O1—C2^{vii} | −122.41 (19) | C2^{vii}—O1—C1—C2 | −175.1 (2) |
O1^{vii}—Rb1—O1—C2^{vii} | −29.86 (17) | Rb1^{vi}—O1—C1—C2 | −37.4 (3) |
O1^{viii}—Rb1—O1—C2^{vii} | 145.0 (2) | Rb1—O1—C1—C2 | −56.8 (3) |
O1^{ii}—Rb1—O1—C2^{vii} | 170.62 (16) | O1—C1—C2—O1^{viii} | 70.0 (4) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+y, −x, z; (iii) y, −x+y, −z; (iv) x−y, x, −z; (v) −y, x−y, z; (vi) −x, −y, −z+1; (vii) x−y, x, −z+1; (viii) y, −x+y, −z+1. |
[Cs(C_{12}H_{24}O_{6})]·[SbCl_{6}] | D_{x} = 1.999 Mg m^{−}^{3} |
M_{r} = 731.67 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 3557 reflections |
a = 14.0782 (10) Å | θ = 2.5–28.0° |
c = 10.6230 (8) Å | µ = 3.29 mm^{−}^{1} |
V = 1823.4 (3) Å^{3} | T = 223 K |
Z = 3 | Prism, colourless |
F(000) = 1056 | 0.20 × 0.17 × 0.16 mm |
Bruker APEX2 area-detector diffractometer | 972 independent reflections |
Radiation source: fine-focus sealed tube | 867 reflections with I > 2σ(I) |
Graphite monochromator | R_{int} = 0.038 |
ω scans | θ_{max} = 28.0°, θ_{min} = 2.5° |
Absorption correction: numerical face-indexed (SADABS; Bruker, 2008) | h = −18→12 |
T_{min} = 0.559, T_{max} = 0.621 | k = −18→18 |
3557 measured reflections | l = −13→13 |
Refinement on F^{2} | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F^{2} > 2σ(F^{2})] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F^{2}) = 0.079 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ^{2}(F_{o}^{2}) + (0.0332P)^{2} + 4.4375P] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
972 reflections | (Δ/σ)_{max} < 0.001 |
42 parameters | Δρ_{max} = 1.49 e Å^{−}^{3} |
0 restraints | Δρ_{min} = −0.53 e Å^{−}^{3} |
[Cs(C_{12}H_{24}O_{6})]·[SbCl_{6}] | Z = 3 |
M_{r} = 731.67 | Mo Kα radiation |
Trigonal, R3 | µ = 3.29 mm^{−}^{1} |
a = 14.0782 (10) Å | T = 223 K |
c = 10.6230 (8) Å | 0.20 × 0.17 × 0.16 mm |
V = 1823.4 (3) Å^{3} |
Bruker APEX2 area-detector diffractometer | 972 independent reflections |
Absorption correction: numerical face-indexed (SADABS; Bruker, 2008) | 867 reflections with I > 2σ(I) |
T_{min} = 0.559, T_{max} = 0.621 | R_{int} = 0.038 |
3557 measured reflections |
R[F^{2} > 2σ(F^{2})] = 0.031 | 0 restraints |
wR(F^{2}) = 0.079 | H-atom parameters constrained |
S = 1.09 | Δρ_{max} = 1.49 e Å^{−}^{3} |
972 reflections | Δρ_{min} = −0.53 e Å^{−}^{3} |
42 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | U_{iso}*/U_{eq} | Occ. (<1) | |
Sb1 | 0.0000 | 0.0000 | 0.0000 | 0.04589 (17) | |
Cs1 | 0.0000 | 0.0000 | 0.41204 (7) | 0.04685 (19) | 0.50 |
Cl1 | 0.15971 (7) | 0.08080 (8) | 0.12770 (9) | 0.0624 (2) | |
O1 | 0.22671 (17) | 0.16479 (17) | 0.5230 (2) | 0.0509 (5) | |
C1 | 0.2980 (3) | 0.1282 (3) | 0.4785 (4) | 0.0598 (9) | |
H1A | 0.3736 | 0.1807 | 0.5030 | 0.072* | |
H1B | 0.2947 | 0.1238 | 0.3864 | 0.072* | |
C2 | 0.2651 (3) | 0.0180 (3) | 0.5325 (3) | 0.0573 (8) | |
H2A | 0.3224 | −0.0006 | 0.5159 | 0.069* | |
H2B | 0.2561 | 0.0191 | 0.6238 | 0.069* |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
Sb1 | 0.03376 (18) | 0.03376 (18) | 0.0702 (3) | 0.01688 (9) | 0.000 | 0.000 |
Cs1 | 0.0368 (2) | 0.0368 (2) | 0.0669 (4) | 0.01840 (11) | 0.000 | 0.000 |
Cl1 | 0.0455 (4) | 0.0536 (5) | 0.0851 (6) | 0.0226 (4) | −0.0127 (4) | −0.0058 (4) |
O1 | 0.0400 (11) | 0.0424 (11) | 0.0690 (14) | 0.0196 (9) | 0.0055 (9) | 0.0037 (10) |
C1 | 0.0316 (14) | 0.0510 (18) | 0.090 (3) | 0.0158 (13) | 0.0052 (14) | −0.0048 (16) |
C2 | 0.0401 (15) | 0.060 (2) | 0.077 (2) | 0.0295 (15) | −0.0077 (15) | −0.0099 (17) |
Sb1—Cl1^{i} | 2.3732 (8) | Cs1—O1^{iii} | 3.091 (2) |
Sb1—Cl1 | 2.3732 (8) | Cs1—Cl1^{iii} | 3.5938 (12) |
Sb1—Cl1^{ii} | 2.3731 (8) | Cs1—Cl1^{ii} | 3.5938 (12) |
Sb1—Cl1^{iii} | 2.3732 (8) | Cs1—Cl1 | 3.5938 (12) |
Sb1—Cl1^{iv} | 2.3732 (8) | O1—C1 | 1.419 (4) |
Sb1—Cl1^{v} | 2.3732 (8) | O1—C2^{vii} | 1.421 (4) |
Cs1—O1^{vi} | 2.939 (2) | C1—C2 | 1.494 (5) |
Cs1—O1^{vii} | 2.939 (2) | C1—H1A | 0.9800 |
Cs1—O1^{viii} | 2.939 (2) | C1—H1B | 0.9800 |
Cs1—O1 | 3.091 (2) | C2—H2A | 0.9800 |
Cs1—O1^{ii} | 3.091 (2) | C2—H2B | 0.9800 |
Cl1^{i}—Sb1—Cl1 | 180 | O1^{iii}—Cs1—Cl1^{iii} | 80.52 (4) |
Cl1^{i}—Sb1—Cl1^{ii} | 89.43 (3) | O1^{vi}—Cs1—Cl1^{ii} | 93.13 (5) |
Cl1—Sb1—Cl1^{ii} | 90.57 (3) | O1^{vii}—Cs1—Cl1^{ii} | 80.18 (5) |
Cl1^{i}—Sb1—Cl1^{iii} | 89.43 (3) | O1^{viii}—Cs1—Cl1^{ii} | 135.04 (5) |
Cl1—Sb1—Cl1^{iii} | 90.57 (3) | O1—Cs1—Cl1^{ii} | 117.14 (4) |
Cl1^{ii}—Sb1—Cl1^{iii} | 90.57 (3) | O1^{ii}—Cs1—Cl1^{ii} | 80.52 (4) |
Cl1^{i}—Sb1—Cl1^{iv} | 90.57 (3) | O1^{iii}—Cs1—Cl1^{ii} | 132.09 (5) |
Cl1—Sb1—Cl1^{iv} | 89.43 (3) | Cl1^{iii}—Cs1—Cl1^{ii} | 55.97 (2) |
Cl1^{ii}—Sb1—Cl1^{iv} | 89.43 (3) | O1^{vi}—Cs1—Cl1 | 135.04 (5) |
Cl1^{iii}—Sb1—Cl1^{iv} | 180 | O1^{vii}—Cs1—Cl1 | 93.13 (5) |
Cl1^{i}—Sb1—Cl1^{v} | 90.57 (3) | O1^{viii}—Cs1—Cl1 | 80.18 (5) |
Cl1—Sb1—Cl1^{v} | 89.43 (3) | O1—Cs1—Cl1 | 80.52 (4) |
Cl1^{ii}—Sb1—Cl1^{v} | 180 | O1^{ii}—Cs1—Cl1 | 132.09 (4) |
Cl1^{iii}—Sb1—Cl1^{v} | 89.43 (3) | O1^{iii}—Cs1—Cl1 | 117.14 (4) |
Cl1^{iv}—Sb1—Cl1^{v} | 90.57 (3) | Cl1^{iii}—Cs1—Cl1 | 55.97 (2) |
O1^{vi}—Cs1—O1^{vii} | 114.67 (3) | Cl1^{ii}—Cs1—Cl1 | 55.97 (2) |
O1^{vi}—Cs1—O1^{viii} | 114.67 (3) | Sb1—Cl1—Cs1 | 92.05 (3) |
O1^{vii}—Cs1—O1^{viii} | 114.67 (3) | C1—O1—C2^{vii} | 113.2 (3) |
O1^{vi}—Cs1—O1 | 144.00 (4) | C1—O1—Cs1^{vi} | 118.54 (17) |
O1^{vii}—Cs1—O1 | 57.398 (13) | C2^{vii}—O1—Cs1^{vi} | 118.79 (18) |
O1^{viii}—Cs1—O1 | 57.398 (13) | C1—O1—Cs1 | 104.64 (18) |
O1^{vi}—Cs1—O1^{ii} | 57.398 (13) | C2^{vii}—O1—Cs1 | 101.95 (17) |
O1^{vii}—Cs1—O1^{ii} | 57.398 (13) | O1—C1—C2 | 109.9 (3) |
O1^{viii}—Cs1—O1^{ii} | 144.00 (4) | O1—C1—H1A | 109.7 |
O1—Cs1—O1^{ii} | 106.36 (5) | C2—C1—H1A | 109.7 |
O1^{vi}—Cs1—O1^{iii} | 57.398 (13) | O1—C1—H1B | 109.7 |
O1^{vii}—Cs1—O1^{iii} | 144.00 (4) | C2—C1—H1B | 109.7 |
O1^{viii}—Cs1—O1^{iii} | 57.398 (13) | H1A—C1—H1B | 108.2 |
O1—Cs1—O1^{iii} | 106.36 (5) | O1^{viii}—C2—C1 | 109.4 (3) |
O1^{ii}—Cs1—O1^{iii} | 106.36 (5) | O1^{viii}—C2—H2A | 109.8 |
O1^{vi}—Cs1—Cl1^{iii} | 80.18 (5) | C1—C2—H2A | 109.8 |
O1^{vii}—Cs1—Cl1^{iii} | 135.04 (5) | Cs1^{vi}—C2—H2A | 163.2 |
O1^{viii}—Cs1—Cl1^{iii} | 93.13 (5) | O1^{viii}—C2—H2B | 109.8 |
O1—Cs1—Cl1^{iii} | 132.09 (4) | C1—C2—H2B | 109.8 |
O1^{ii}—Cs1—Cl1^{iii} | 117.14 (4) | H2A—C2—H2B | 108.2 |
Cl1^{ii}—Sb1—Cl1—Cs1 | 45.286 (18) | O1^{iii}—Cs1—O1—C1 | 62.2 (2) |
Cl1^{iii}—Sb1—Cl1—Cs1 | −45.286 (18) | Cl1^{iii}—Cs1—O1—C1 | −29.8 (2) |
Cl1^{iv}—Sb1—Cl1—Cs1 | 134.714 (18) | Cl1^{ii}—Cs1—O1—C1 | −97.16 (19) |
Cl1^{v}—Sb1—Cl1—Cs1 | −134.714 (18) | Cl1—Cs1—O1—C1 | −53.48 (19) |
O1^{vi}—Cs1—Cl1—Sb1 | 19.85 (7) | O1^{vi}—Cs1—O1—C2^{vii} | −123.11 (19) |
O1^{vii}—Cs1—Cl1—Sb1 | −110.42 (5) | O1^{vii}—Cs1—O1—C2^{vii} | −35.26 (18) |
O1^{viii}—Cs1—Cl1—Sb1 | 135.07 (5) | O1^{viii}—Cs1—O1—C2^{vii} | 149.0 (2) |
O1—Cs1—Cl1—Sb1 | −166.63 (5) | O1^{ii}—Cs1—O1—C2^{vii} | −66.6 (2) |
O1^{ii}—Cs1—Cl1—Sb1 | −63.09 (6) | O1^{iii}—Cs1—O1—C2^{vii} | −179.66 (18) |
O1^{iii}—Cs1—Cl1—Sb1 | 89.76 (5) | Cl1^{iii}—Cs1—O1—C2^{vii} | 88.40 (19) |
Cl1^{iii}—Cs1—Cl1—Sb1 | 34.486 (4) | Cl1^{ii}—Cs1—O1—C2^{vii} | 21.0 (2) |
Cl1^{ii}—Cs1—Cl1—Sb1 | −34.486 (4) | Cl1—Cs1—O1—C2^{vii} | 64.68 (19) |
O1^{vi}—Cs1—O1—C1 | 118.73 (19) | C2^{vii}—O1—C1—C2 | −175.0 (2) |
O1^{vii}—Cs1—O1—C1 | −153.4 (2) | Cs1^{vi}—O1—C1—C2 | −28.9 (3) |
O1^{viii}—Cs1—O1—C1 | 30.87 (18) | Cs1—O1—C1—C2 | −64.8 (3) |
O1^{ii}—Cs1—O1—C1 | 175.27 (18) | O1—C1—C2—O1^{viii} | 70.9 (4) |
Symmetry codes: (i) −x, −y, −z; (ii) −y, x−y, z; (iii) −x+y, −x, z; (iv) x−y, x, −z; (v) y, −x+y, −z; (vi) −x, −y, −z+1; (vii) x−y, x, −z+1; (viii) y, −x+y, −z+1. |
[(NH_{4})(C_{12}H_{24}O_{6})]·[SbCl_{6}] | D_{x} = 1.750 Mg m^{−}^{3} |
M_{r} = 616.80 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 24 reflections |
a = 14.1069 (9) Å | θ = 12.6–17.2° |
c = 10.1908 (8) Å | µ = 1.89 mm^{−}^{1} |
V = 1756.3 (2) Å^{3} | T = 223 K |
Z = 3 | Prism, colourless |
F(000) = 924 | 0.25 × 0.23 × 0.18 mm |
Enraf–Nonius CAD4 diffractometer | 673 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | R_{int} = 0.037 |
Graphite monochromator | θ_{max} = 25.3°, θ_{min} = 2.6° |
non–profiled ω–2θ scans | h = −16→16 |
Absorption correction: ψ scan (North et al., 1968) | k = −16→16 |
T_{min} = 0.682, T_{max} = 0.764 | l = −11→12 |
2227 measured reflections | 3 standard reflections every 120 min |
708 independent reflections | intensity decay: none |
Refinement on F^{2} | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F^{2} > 2σ(F^{2})] = 0.022 | Hydrogen site location: difference Fourier map |
wR(F^{2}) = 0.056 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ^{2}(F_{o}^{2}) + (0.0283P)^{2} + 1.1402P] where P = (F_{o}^{2} + 2F_{c}^{2})/3 |
708 reflections | (Δ/σ)_{max} < 0.001 |
42 parameters | Δρ_{max} = 0.36 e Å^{−}^{3} |
0 restraints | Δρ_{min} = −0.44 e Å^{−}^{3} |
[(NH_{4})(C_{12}H_{24}O_{6})]·[SbCl_{6}] | Z = 3 |
M_{r} = 616.80 | Mo Kα radiation |
Trigonal, R3 | µ = 1.89 mm^{−}^{1} |
a = 14.1069 (9) Å | T = 223 K |
c = 10.1908 (8) Å | 0.25 × 0.23 × 0.18 mm |
V = 1756.3 (2) Å^{3} |
Enraf–Nonius CAD4 diffractometer | 673 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | R_{int} = 0.037 |
T_{min} = 0.682, T_{max} = 0.764 | 3 standard reflections every 120 min |
2227 measured reflections | intensity decay: none |
708 independent reflections |
R[F^{2} > 2σ(F^{2})] = 0.022 | 0 restraints |
wR(F^{2}) = 0.056 | H-atom parameters constrained |
S = 1.14 | Δρ_{max} = 0.36 e Å^{−}^{3} |
708 reflections | Δρ_{min} = −0.44 e Å^{−}^{3} |
42 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F^{2} against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^{2}, conventional R-factors R are based on F, with F set to zero for negative F^{2}. The threshold expression of F^{2} > σ(F^{2}) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^{2} are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | U_{iso}*/U_{eq} | Occ. (<1) | |
Sb1 | 0.0000 | 0.0000 | 0.0000 | 0.03190 (15) | |
Cl1 | 0.15828 (5) | 0.07881 (6) | 0.13460 (7) | 0.0534 (2) | |
O1 | 0.22474 (13) | 0.06313 (13) | 0.52237 (17) | 0.0426 (4) | |
N1 | 0.0000 | 0.0000 | 0.4495 (8) | 0.0469 (19) | 0.50 |
H1 | 0.0000 | 0.0000 | 0.3611 | 0.070* | 0.50 |
H2 | 0.0694 | 0.0323 | 0.4789 | 0.070* | 0.50 |
C1 | 0.2472 (2) | −0.0156 (2) | 0.4643 (3) | 0.0461 (6) | |
H1A | 0.3233 | 0.0045 | 0.4814 | 0.055* | |
H1B | 0.2367 | −0.0171 | 0.3691 | 0.055* | |
C2 | 0.1716 (2) | −0.1260 (2) | 0.5210 (3) | 0.0462 (6) | |
H2A | 0.1942 | −0.1782 | 0.4929 | 0.055* | |
H2B | 0.1746 | −0.1220 | 0.6171 | 0.055* |
U^{11} | U^{22} | U^{33} | U^{12} | U^{13} | U^{23} | |
Sb1 | 0.03064 (17) | 0.03064 (17) | 0.0344 (2) | 0.01532 (8) | 0.000 | 0.000 |
Cl1 | 0.0455 (4) | 0.0526 (4) | 0.0598 (4) | 0.0228 (3) | −0.0171 (3) | −0.0090 (3) |
O1 | 0.0365 (9) | 0.0382 (8) | 0.0517 (10) | 0.0178 (7) | 0.0061 (7) | 0.0003 (7) |
N1 | 0.033 (2) | 0.033 (2) | 0.074 (5) | 0.0167 (10) | 0.000 | 0.000 |
C1 | 0.0356 (12) | 0.0528 (15) | 0.0536 (15) | 0.0250 (11) | −0.0006 (10) | −0.0075 (12) |
C2 | 0.0462 (14) | 0.0483 (14) | 0.0553 (15) | 0.0320 (12) | −0.0090 (11) | −0.0060 (11) |
Sb1—Cl1 | 2.3707 (6) | N1—H1 | 0.9000 |
Sb1—Cl1^{i} | 2.3707 (6) | N1—H2 | 0.9000 |
Sb1—Cl1^{ii} | 2.3707 (6) | C1—C2 | 1.495 (4) |
Sb1—Cl1^{iii} | 2.3707 (6) | C1—H1A | 0.9800 |
Sb1—Cl1^{iv} | 2.3707 (6) | C1—H1B | 0.9800 |
Sb1—Cl1^{v} | 2.3707 (6) | C2—H2A | 0.9800 |
O1—C2^{vi} | 1.422 (3) | C2—H2B | 0.9800 |
O1—C1 | 1.426 (3) | ||
Cl1—Sb1—Cl1^{i} | 180 | C2^{vi}—O1—C1 | 112.75 (18) |
Cl1—Sb1—Cl1^{ii} | 89.88 (3) | H1—N1—H2 | 109.5 |
Cl1^{i}—Sb1—Cl1^{ii} | 90.12 (3) | O1—C1—C2 | 109.3 (2) |
Cl1—Sb1—Cl1^{iii} | 90.12 (3) | O1—C1—H1A | 109.8 |
Cl1^{i}—Sb1—Cl1^{iii} | 89.88 (3) | C2—C1—H1A | 109.8 |
Cl1^{ii}—Sb1—Cl1^{iii} | 90.12 (3) | O1—C1—H1B | 109.8 |
Cl1—Sb1—Cl1^{iv} | 90.12 (3) | C2—C1—H1B | 109.8 |
Cl1^{i}—Sb1—Cl1^{iv} | 89.88 (3) | H1A—C1—H1B | 108.3 |
Cl1^{ii}—Sb1—Cl1^{iv} | 180 | O1^{vii}—C2—C1 | 109.2 (2) |
Cl1^{iii}—Sb1—Cl1^{iv} | 89.88 (3) | O1^{vii}—C2—H2A | 109.8 |
Cl1—Sb1—Cl1^{v} | 89.88 (3) | C1—C2—H2A | 109.8 |
Cl1^{i}—Sb1—Cl1^{v} | 90.12 (3) | O1^{vii}—C2—H2B | 109.8 |
Cl1^{ii}—Sb1—Cl1^{v} | 89.88 (3) | C1—C2—H2B | 109.8 |
Cl1^{iii}—Sb1—Cl1^{v} | 180 | H2A—C2—H2B | 108.3 |
Cl1^{iv}—Sb1—Cl1^{v} | 90.12 (3) | ||
C2^{vi}—O1—C1—C2 | 176.61 (17) | O1—C1—C2—O1^{vii} | 68.8 (3) |
Symmetry codes: (i) −x, −y, −z; (ii) −y, x−y, z; (iii) x−y, x, −z; (iv) y, −x+y, −z; (v) −x+y, −x, z; (vi) x−y, x, −z+1; (vii) y, −x+y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···O1 | 0.90 | 2.06 | 2.928 (3) | 162 |
N1—H1···Cl1 | 0.90 | 3.01 | 3.746 (7) | 140 |
C2—H2A···Cl1^{viii} | 0.98 | 3.09 | 3.798 (3) | 130 |
Symmetry code: (viii) x−y+1/3, x−1/3, −z+2/3. |
Experimental details
(1) | (2) | (3) | |
Crystal data | |||
Chemical formula | [Rb(C_{12}H_{24}O_{6})]·[SbCl_{6}] | [Cs(C_{12}H_{24}O_{6})]·[SbCl_{6}] | [(NH_{4})(C_{12}H_{24}O_{6})]·[SbCl_{6}] |
M_{r} | 684.23 | 731.67 | 616.80 |
Crystal system, space group | Trigonal, R3 | Trigonal, R3 | Trigonal, R3 |
Temperature (K) | 223 | 223 | 223 |
a, c (Å) | 14.1011 (10), 10.0850 (9) | 14.0782 (10), 10.6230 (8) | 14.1069 (9), 10.1908 (8) |
V (Å^{3}) | 1736.7 (2) | 1823.4 (3) | 1756.3 (2) |
Z | 3 | 3 | 3 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm^{−}^{1}) | 4.00 | 3.29 | 1.89 |
Crystal size (mm) | 0.26 × 0.22 × 0.20 | 0.20 × 0.17 × 0.16 | 0.25 × 0.23 × 0.18 |
Data collection | |||
Diffractometer | Enraf–Nonius CAD4 diffractometer | Bruker APEX2 area-detector diffractometer | Enraf–Nonius CAD4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | Numerical face-indexed (SADABS; Bruker, 2008) | ψ scan (North et al., 1968) |
T_{min}, T_{max} | 0.423, 0.502 | 0.559, 0.621 | 0.682, 0.764 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2016, 697, 635 | 3557, 972, 867 | 2227, 708, 673 |
R_{int} | 0.073 | 0.038 | 0.037 |
(sin θ/λ)_{max} (Å^{−}^{1}) | 0.599 | 0.660 | 0.602 |
Refinement | |||
R[F^{2} > 2σ(F^{2})], wR(F^{2}), S | 0.026, 0.065, 1.05 | 0.031, 0.079, 1.09 | 0.022, 0.056, 1.14 |
No. of reflections | 697 | 972 | 708 |
No. of parameters | 42 | 42 | 42 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρ_{max}, Δρ_{min} (e Å^{−}^{3}) | 0.35, −0.42 | 1.49, −0.53 | 0.36, −0.44 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), APEX2 (Bruker, 2008), SAINT (Bruker, 2008), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 2012).
Sb1—Cl1 | 2.3617 (8) | Rb1—O1 | 2.917 (2) |
Rb1—O1^{i} | 2.839 (2) | Rb1—Cl1 | 3.7353 (16) |
Cl1—Sb1—Cl1^{ii} | 90.03 (4) | O1—Rb1—O1^{ii} | 114.18 (4) |
O1^{iii}—Rb1—O1^{i} | 119.261 (16) | O1—Rb1—Cl1 | 74.04 (5) |
O1^{iii}—Rb1—O1 | 160.83 (5) | O1^{ii}—Rb1—Cl1 | 110.28 (5) |
O1^{i}—Rb1—O1 | 59.728 (14) | Cl1^{ii}—Rb1—Cl1 | 53.13 (3) |
C2^{iv}—O1—C1—C2 | −175.1 (2) | O1—C1—C2—O1^{i} | 70.0 (4) |
Symmetry codes: (i) y, −x+y, −z+1; (ii) −x+y, −x, z; (iii) −x, −y, −z+1; (iv) x−y, x, −z+1. |
Sb1—Cl1 | 2.3732 (8) | Cs1—O1 | 3.091 (2) |
Cs1—O1^{i} | 2.939 (2) | Cs1—Cl1 | 3.5938 (12) |
Cl1—Sb1—Cl1^{ii} | 90.57 (3) | O1—Cs1—O1^{ii} | 106.36 (5) |
O1^{iii}—Cs1—O1^{i} | 114.67 (3) | O1—Cs1—Cl1 | 80.52 (4) |
O1^{iii}—Cs1—O1 | 144.00 (4) | O1^{ii}—Cs1—Cl1 | 117.14 (4) |
O1^{i}—Cs1—O1 | 57.398 (13) | Cl1^{ii}—Cs1—Cl1 | 55.97 (2) |
C2^{iv}—O1—C1—C2 | −175.0 (2) | O1—C1—C2—O1^{i} | 70.9 (4) |
Symmetry codes: (i) y, −x+y, −z+1; (ii) −x+y, −x, z; (iii) −x, −y, −z+1; (iv) x−y, x, −z+1. |
Sb1—Cl1 | 2.3707 (6) | ||
Cl1—Sb1—Cl1^{i} | 89.88 (3) | ||
C2^{ii}—O1—C1—C2 | 176.61 (17) | O1—C1—C2—O1^{iii} | 68.8 (3) |
Symmetry codes: (i) −x+y, −x, z; (ii) x−y, x, −z+1; (iii) y, −x+y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···O1 | 0.90 | 2.06 | 2.928 (3) | 162 |
N1—H1···Cl1 | 0.90 | 3.01 | 3.746 (7) | 140 |
C2—H2A···Cl1^{iv} | 0.98 | 3.09 | 3.798 (3) | 130 |
Symmetry code: (iv) x−y+1/3, x−1/3, −z+2/3. |
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