Download citation
Download citation
link to html
The structures of the two novel title compounds, Rb2[CrCl5(H2O)], (I), and Cs2[CrCl5(H2O)], (II), have been determined by single-crystal X-ray diffraction. Compounds (I) and (II) crystallize with Pnma and Cmcm symmetry, respectively. In (I), the Cr, three Cl and water O atom lie on a mirror plane; in (II), the Cs, Cr, O and one of the Cl atoms are at sites with m2m symmetry. The chromate anions are in a pseudo-cubic environment of eight Rb+ cations in (I) and in a pseudo-octahedral environment of six Cs+ cations in (II). The structural arrangement correlates with the ranion/rcation radius ratio.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104002987/bc1030sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104002987/bc1030Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104002987/bc1030IIsup3.hkl
Contains datablock II

Comment top

Octahedral chromium(III) complexes have attracted increasing interest in the past decade, following the discovery of their catalytic properties. One application for these complexes is in homogeneous catalysis, where CO and CO2 are converted into organic compounds, such as methanol, at ambient conditions. The conversion into methanol may be of particular importance because it provides a possible way to reduce greenhouse gas emissions (Ogura & Yoshida, 1987). Substitution reactions of ligands are slow in chromium(III) complexes, a fact that corresponds to their considerable stability. Compounds containing the aquapentachlorochromate(III) complex anion, [CrCl5(H2O)]2−, have been described previously (Ogura & Yoshida, 1987) but have not been structurally characterized.

Two novel compounds were synthesized using the Palmer (1954) method and were identified as Rb2[CrCl5(H2O)], (I), and Cs2[CrCl5(H2O)], (II), by single-crystal diffraction. Both structures consist of layers of chromate complexes connected by O—H···Cl hydrogen bonds, as determined directly for (I) (Fig. 1 and Table 3). The position of the H atom could not be determined in (II). Nevertheless, by analogy with the structure of Cs2[FeCl5(H2O)] (Greedan et al., 1980), the short O···Cl distances of 3.380 (5) Å suggest the existence of bifurcated hydrogen bonds in (II) (Fig. 2).

The chromate anions in (I) and (II) occur in different environments; eight Rb+ cations form a pseudo-cubic environment in (I), whereas six Cs+ cations form a pseudo-octahedral environment in (II) (Figs. 3 and 4). Coll et al. (1987) proposed that the ranion/rcation ratio in alkali aquapentachlorometallates determines the structural type. In the present work, the anionic radius is defined by the average octahedral <M—X> distance (X = Cl and O). The correlation between the ionic radius ratio and the structure type is shown in Table 2 for aquapentachlorometallates(III) including Rb2[MCl5(H2O)] (M = Cr, Fe, In and Tl) and Cs2[MCl5(H2O)] (M = Cr, Fe, In, Ir, Rh, Ru and Tl). It is apparent that smaller radius ratios (1.21–1.24) correspond to the Cmcm structure, while larger radius ratios (1.30–1.65) correspond to the Pnma structure.

Experimental top

The title compounds were synthezed according to the method of Palmer (1954). Stoichiometric proportions of ACl salts (A = Rb and Cs) and hexavalent CrO3 were dissolved in 12 M hydrochloric acid (6.0 ml). Ethanol (1.5 ml) was added in small portions. When the exothermal reaction was over, a saturated solution of ACl salt was added. The solution was first evaporated over a flame and, when crystals started to appear, the solution was evaporated over a boiling-water bath. The violet–red products were left to cool in a desiccator over silica gel and were then washed with ethanol. The resulting mixture was dried in an evacuated desiccator over sulfuric acid. Red–violet single crystals were obtained of a size suitable for single-crystal diffraction analysis.

Refinement top

The H-atom position in (I) was located from a Fourier difference map and was refined isotropically without any constraint. The highest peak of residual electron density for (II) is located at (0.0580, −0.0025, 1/4), 0.43 Å from the O atom, and does not correspond to the missing H atom. An attempt to use the H-atom coordinates determined by Greedan et al. (1980) for Cs2[FeCl5(H2O)] led to an unreasonable result.

Computing details top

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The network of [CrCl5(H2O)]2− anions in (I), showing the O—H···Cl hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The network of [CrCl5(H2O)]2− anions in (II), showing probable bifurcated hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. The pseudo-cubic environment of the chromate complex in (I). The Rb, Cr, Cl and O atoms are purple, pink, green and red, respectively.
[Figure 4] Fig. 4. The pseudo-octahedral environment of the chromate complex in (II). The Cs, Cr, Cl and O atoms are grey, pink, green and red, respectively.
(I) Rubidium aquapentachlorochromate(III) top
Crystal data top
Rb2[CrCl5(H2O)]F(000) = 772
Mr = 418.21Dx = 2.915 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 7643 reflections
a = 13.7558 (2) Åθ = 2.4–32.9°
b = 9.7484 (1) ŵ = 12.68 mm1
c = 7.1074 (1) ÅT = 168 K
V = 953.08 (2) Å3Rhombic octahedron, red–violet
Z = 40.10 × 0.06 × 0.03 mm
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
1825 independent reflections
Radiation source: fine-focus sealed tube1465 reflections with I > 2σI
Graphite monochromatorRint = 0.049
ω scansθmax = 32.9°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 2020
Tmin = 0.364, Tmax = 0.702k = 1414
14988 measured reflectionsl = 1010
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) = 0.110All H-atom parameters refined
S = 1.04 w = 1/[σ2(Fo2) + (0.0689P)2 + 0.3749P]
where P = (Fo2 + 2Fc2)/3
1825 reflections(Δ/σ)max < 0.001
53 parametersΔρmax = 0.97 e Å3
0 restraintsΔρmin = 1.87 e Å3
Crystal data top
Rb2[CrCl5(H2O)]V = 953.08 (2) Å3
Mr = 418.21Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 13.7558 (2) ŵ = 12.68 mm1
b = 9.7484 (1) ÅT = 168 K
c = 7.1074 (1) Å0.10 × 0.06 × 0.03 mm
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
1825 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
1465 reflections with I > 2σI
Tmin = 0.364, Tmax = 0.702Rint = 0.049
14988 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.110All H-atom parameters refined
S = 1.04Δρmax = 0.97 e Å3
1825 reflectionsΔρmin = 1.87 e Å3
53 parameters
Special details top

Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with a LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 15 s per frame. A preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement of the position of 5499 reflections with I>10σ(I) after integration of all frames using SAINT (Siemens, 1995).

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
Rb0.14484 (3)0.00050 (3)0.15441 (5)0.02097 (12)
Cr0.11050 (5)0.25000.31095 (10)0.01251 (16)
Cl10.21642 (9)0.25000.56749 (16)0.0231 (2)
Cl20.00625 (8)0.25000.04719 (18)0.0209 (2)
Cl30.24324 (7)0.25000.10841 (15)0.0159 (2)
Cl40.10392 (7)0.00856 (7)0.31936 (13)0.01887 (18)
O0.0063 (3)0.25000.4867 (6)0.0263 (9)
H0.025 (3)0.186 (4)0.531 (6)0.032 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rb0.02048 (19)0.0187 (2)0.0237 (2)0.00088 (11)0.00335 (12)0.00270 (12)
Cr0.0129 (3)0.0097 (3)0.0149 (3)0.0000.0029 (2)0.000
Cl10.0312 (6)0.0228 (5)0.0152 (5)0.0000.0029 (4)0.000
Cl20.0167 (5)0.0183 (5)0.0278 (6)0.0000.0043 (4)0.000
Cl30.0152 (5)0.0156 (5)0.0171 (4)0.0000.0039 (4)0.000
Cl40.0208 (4)0.0109 (3)0.0250 (4)0.0002 (3)0.0058 (3)0.0018 (3)
O0.030 (2)0.0133 (17)0.036 (2)0.0000.0210 (18)0.000
Geometric parameters (Å, º) top
Rb—Cl2i3.2887 (8)Cr—Rbiv4.1384 (7)
Rb—Cl1ii3.2924 (9)Cr—Rbv4.1597 (7)
Rb—Cl3iii3.3358 (8)Cr—Rbvi4.1597 (7)
Rb—Cl33.3593 (8)Cl2—Rbi3.2887 (8)
Rb—Cl23.4133 (9)Cl2—Rbvii3.2887 (8)
Rb—Cl43.4151 (9)Cl2—Rbiv3.4133 (9)
Rb—Cl4iii3.4619 (11)Cl3—Rbv3.3358 (8)
Rb—Cl1iii3.4707 (10)Cl3—Rbvi3.3358 (8)
Rb—Cl4i3.6180 (11)Cl3—Rbiv3.3594 (8)
Rb—Cl4ii3.7833 (10)Cl4—Rbv3.4620 (11)
Rb—Cr4.1384 (7)Cl4—Rbi3.6179 (11)
Rb—Criii4.1596 (7)Cl4—Rbviii3.7832 (10)
Cr—O2.035 (4)Cl1—Rbviii3.2924 (9)
Cr—Cl32.3251 (12)Cl1—Rbix3.2924 (9)
Cr—Cl12.3340 (13)Cl1—Rbv3.4707 (10)
Cr—Cl4iv2.3561 (7)Cl1—Rbvi3.4707 (10)
Cr—Cl42.3561 (7)O—H0.75 (4)
Cr—Cl22.3603 (14)
Cl2i—Rb—Cl1ii151.24 (3)O—Cr—Cl290.45 (13)
Cl2i—Rb—Cl3iii82.50 (2)Cl3—Cr—Cl289.17 (5)
Cl1ii—Rb—Cl3iii95.70 (2)Cl1—Cr—Cl2178.79 (5)
Cl2i—Rb—Cl3131.56 (3)Cl4iv—Cr—Cl289.82 (3)
Cl1ii—Rb—Cl370.98 (2)Cl4—Cr—Cl289.82 (3)
Cl3iii—Rb—Cl3128.685 (12)O—Cr—Rb125.50 (9)
Cl2i—Rb—Cl294.524 (10)Cl3—Cr—Rb54.24 (2)
Cl1ii—Rb—Cl283.59 (2)Cl1—Cr—Rb123.58 (3)
Cl3iii—Rb—Cl2172.54 (3)Cl4iv—Cr—Rb127.89 (3)
Cl3—Rb—Cl258.10 (2)Cl4—Cr—Rb55.61 (2)
Cl2i—Rb—Cl471.73 (3)Cl2—Cr—Rb55.57 (2)
Cl1ii—Rb—Cl4128.46 (2)O—Cr—Rbiv125.49 (9)
Cl3iii—Rb—Cl4126.38 (2)Cl3—Cr—Rbiv54.24 (2)
Cl3—Rb—Cl459.95 (2)Cl1—Cr—Rbiv123.58 (3)
Cl2—Rb—Cl458.37 (2)Cl4iv—Cr—Rbiv55.61 (2)
Cl2i—Rb—Cl4iii128.80 (2)Cl4—Cr—Rbiv127.89 (3)
Cl1ii—Rb—Cl4iii71.70 (3)Cl2—Cr—Rbiv55.57 (2)
Cl3iii—Rb—Cl4iii59.70 (2)Rb—Cr—Rbiv72.327 (15)
Cl3—Rb—Cl4iii69.16 (2)O—Cr—Rbv127.04 (8)
Cl2—Rb—Cl4iii126.61 (2)Cl3—Cr—Rbv53.22 (2)
Cl4—Rb—Cl4iii102.60 (2)Cl1—Cr—Rbv56.54 (3)
Cl2i—Rb—Cl1iii73.97 (3)Cl4iv—Cr—Rbv127.86 (3)
Cl1ii—Rb—Cl1iii128.913 (13)Cl4—Cr—Rbv56.32 (3)
Cl3iii—Rb—Cl1iii57.65 (2)Cl2—Cr—Rbv122.59 (3)
Cl3—Rb—Cl1iii92.01 (2)Rb—Cr—Rbv67.042 (10)
Cl2—Rb—Cl1iii128.15 (3)Rbiv—Cr—Rbv107.458 (16)
Cl4—Rb—Cl1iii70.17 (2)O—Cr—Rbvi127.04 (8)
Cl4iii—Rb—Cl1iii57.29 (2)Cl3—Cr—Rbvi53.22 (2)
Cl2i—Rb—Cl4i57.41 (2)Cl1—Cr—Rbvi56.54 (3)
Cl1ii—Rb—Cl4i96.00 (3)Cl4iv—Cr—Rbvi56.32 (3)
Cl3iii—Rb—Cl4i104.89 (2)Cl4—Cr—Rbvi127.86 (3)
Cl3—Rb—Cl4i125.25 (2)Cl2—Cr—Rbvi122.59 (3)
Cl2—Rb—Cl4i67.87 (2)Rb—Cr—Rbvi107.458 (16)
Cl4—Rb—Cl4i99.45 (2)Rbiv—Cr—Rbvi67.043 (10)
Cl4iii—Rb—Cl4i157.856 (12)Rbv—Cr—Rbvi71.565 (14)
Cl1iii—Rb—Cl4i130.70 (2)Cr—Cl2—Rbi101.53 (3)
Cl2i—Rb—Cl4ii98.76 (3)Cr—Cl2—Rbvii101.53 (3)
Cl1ii—Rb—Cl4ii55.50 (2)Rbi—Cl2—Rbvii95.39 (3)
Cl3iii—Rb—Cl4ii65.55 (2)Cr—Cl2—Rbiv89.66 (3)
Cl3—Rb—Cl4ii126.35 (2)Rbi—Cl2—Rbiv168.33 (4)
Cl2—Rb—Cl4ii108.37 (2)Rbvii—Cl2—Rbiv85.475 (10)
Cl4—Rb—Cl4ii161.74 (3)Cr—Cl2—Rb89.66 (3)
Cl4iii—Rb—Cl4ii95.50 (2)Rbi—Cl2—Rb85.476 (10)
Cl1iii—Rb—Cl4ii123.19 (2)Rbvii—Cl2—Rb168.33 (4)
Cl4i—Rb—Cl4ii62.58 (2)Rbiv—Cl2—Rb91.36 (3)
Cl2i—Rb—Cr100.32 (2)Cr—Cl3—Rbv92.84 (3)
Cl1ii—Rb—Cr94.373 (17)Cr—Cl3—Rbvi92.84 (3)
Cl3iii—Rb—Cr152.47 (2)Rbv—Cl3—Rbvi93.63 (3)
Cl3—Rb—Cr34.167 (19)Cr—Cl3—Rb91.60 (3)
Cl2—Rb—Cr34.77 (2)Rbv—Cl3—Rb86.385 (6)
Cl4—Rb—Cr34.703 (14)Rbvi—Cl3—Rb175.55 (4)
Cl4iii—Rb—Cr99.809 (18)Cr—Cl3—Rbiv91.60 (3)
Cl1iii—Rb—Cr96.49 (2)Rbv—Cl3—Rbiv175.56 (4)
Cl4i—Rb—Cr99.431 (19)Rbvi—Cl3—Rbiv86.386 (6)
Cl4ii—Rb—Cr139.407 (16)Rb—Cl3—Rbiv93.26 (3)
Cl2i—Rb—Criii95.311 (17)Cr—Cl4—Rb89.69 (3)
Cl1ii—Rb—Criii98.99 (2)Cr—Cl4—Rbv89.18 (3)
Cl3iii—Rb—Criii33.94 (2)Rb—Cl4—Rbv83.57 (2)
Cl3—Rb—Criii97.582 (19)Cr—Cl4—Rbi92.86 (3)
Cl2—Rb—Criii153.51 (2)Rb—Cl4—Rbi80.55 (2)
Cl4—Rb—Criii101.936 (19)Rbv—Cl4—Rbi163.97 (3)
Cl4iii—Rb—Criii34.497 (14)Cr—Cl4—Rbviii92.45 (3)
Cl1iii—Rb—Criii34.13 (2)Rb—Cl4—Rbviii161.74 (3)
Cl4i—Rb—Criii137.167 (17)Rbv—Cl4—Rbviii78.33 (2)
Cl4ii—Rb—Criii94.331 (17)Rbi—Cl4—Rbviii117.42 (2)
Cr—Rb—Criii118.990 (16)Cr—Cl1—Rbviii106.40 (3)
O—Cr—Cl3179.61 (13)Cr—Cl1—Rbix106.40 (3)
O—Cr—Cl190.76 (13)Rbviii—Cl1—Rbix95.76 (3)
Cl3—Cr—Cl189.63 (5)Cr—Cl1—Rbv89.33 (3)
O—Cr—Cl4iv87.37 (3)Rbviii—Cl1—Rbv85.269 (9)
Cl3—Cr—Cl4iv92.63 (3)Rbix—Cl1—Rbv163.15 (4)
Cl1—Cr—Cl4iv90.24 (3)Cr—Cl1—Rbvi89.33 (3)
O—Cr—Cl487.37 (3)Rbviii—Cl1—Rbvi163.15 (4)
Cl3—Cr—Cl492.63 (3)Rbix—Cl1—Rbvi85.268 (8)
Cl1—Cr—Cl490.24 (3)Rbv—Cl1—Rbvi88.98 (3)
Cl4iv—Cr—Cl4174.72 (6)Cr—O—H123 (3)
Symmetry codes: (i) x, y, z; (ii) x, y, z+1; (iii) x+1/2, y, z+1/2; (iv) x, y+1/2, z; (v) x+1/2, y, z1/2; (vi) x+1/2, y+1/2, z1/2; (vii) x, y+1/2, z; (viii) x, y, z1; (ix) x, y+1/2, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O—H···Cl4x0.75 (4)2.43 (4)3.171 (2)174 (5)
Symmetry code: (x) x, y, z1.
(II) Caesium aquapentachlorochromate(III) top
Crystal data top
Cs2[CrCl5(H2O)]F(000) = 916
Mr = 513.09Dx = 3.377 Mg m3
Orthorhombic, CmcmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2Cell parameters from 3038 reflections
a = 7.3868 (3) Åθ = 2.4–32.9°
b = 17.1107 (7) ŵ = 9.50 mm1
c = 7.9848 (4) ÅT = 173 K
V = 1009.23 (8) Å3Rhombic octahedron, red–violet
Z = 40.02 × 0.02 × 0.02 mm
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
883 independent reflections
Radiation source: fine-focus sealed tube686 reflections with I > 2σI
Graphite monochromatorRint = 0.078
ω scansθmax = 30.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1010
Tmin = 0.833, Tmax = 0.871k = 2424
7414 measured reflectionsl = 1111
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.050Secondary atom site location: difference Fourier map
wR(F2) = 0.151 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
883 reflectionsΔρmax = 2.88 e Å3
28 parametersΔρmin = 1.40 e Å3
Crystal data top
Cs2[CrCl5(H2O)]V = 1009.23 (8) Å3
Mr = 513.09Z = 4
Orthorhombic, CmcmMo Kα radiation
a = 7.3868 (3) ŵ = 9.50 mm1
b = 17.1107 (7) ÅT = 173 K
c = 7.9848 (4) Å0.02 × 0.02 × 0.02 mm
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
883 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
686 reflections with I > 2σI
Tmin = 0.833, Tmax = 0.871Rint = 0.078
7414 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05028 parameters
wR(F2) = 0.1510 restraints
S = 1.04Δρmax = 2.88 e Å3
883 reflectionsΔρmin = 1.40 e Å3
Special details top

Experimental. The data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with a LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 15 s per frame. A preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement of the position of 5499 reflections with I>10σ(I) after integration of all frames using SAINT (Siemens, 1995).

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
Cs10.00000.46927 (6)0.25000.0201 (3)
Cs20.00000.24580 (5)0.25000.0201 (3)
Cr0.50000.61615 (12)0.25000.0093 (4)
Cl10.7222 (3)0.61091 (11)0.4586 (3)0.0213 (4)
Cl20.50000.7510 (2)0.25000.0169 (7)
O0.50000.4955 (5)0.25000.0087 (18)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs10.0278 (6)0.0191 (5)0.0134 (5)0.0000.0000.000
Cs20.0195 (5)0.0125 (4)0.0283 (6)0.0000.0000.000
Cr0.0108 (11)0.0084 (9)0.0088 (9)0.0000.0000.000
Cl10.0220 (10)0.0195 (8)0.0224 (9)0.0045 (7)0.0112 (7)0.0027 (7)
Cl20.0165 (17)0.0101 (13)0.024 (2)0.0000.0000.000
Geometric parameters (Å, º) top
Cs1—Cl1i3.392 (2)Cs2—Cl2xiv3.9934 (2)
Cs1—Cl1ii3.392 (2)Cr—O2.064 (10)
Cs1—Cl1iii3.392 (2)Cr—Cl22.308 (4)
Cs1—Cl1iv3.392 (2)Cr—Cl12.340 (2)
Cs1—Cl1v3.586 (2)Cr—Cl1vi2.340 (2)
Cs1—Cl1vi3.586 (2)Cr—Cl1v2.340 (2)
Cs1—Cl1vii3.586 (2)Cr—Cl1xviii2.340 (2)
Cs1—Cl1viii3.586 (2)Cr—Cs14.4674 (13)
Cs1—Cl2ix3.734 (4)Cr—Cs1xix4.4674 (13)
Cs1—Cs1x4.1286 (5)Cr—Cs2xi4.3841 (12)
Cs2—Cl1iv3.605 (2)Cr—Cs2xvii4.3841 (12)
Cs2—Cl1xi3.605 (2)Cl1—Cs1ii3.392 (2)
Cs2—Cl1xii3.605 (2)Cl1—Cs1xix3.586 (2)
Cs2—Cl1i3.605 (2)Cl1—Cs2xi3.605 (2)
Cs2—Cl1xiii3.665 (2)Cl1—Cs2xx3.666 (2)
Cs2—Cl1xiv3.665 (2)Cl2—Cs2xi3.6938 (2)
Cs2—Cl1xv3.665 (2)Cl2—Cs2xvii3.6938 (2)
Cs2—Cl1xvi3.665 (2)Cl2—Cs1xxi3.734 (4)
Cs2—Cl2xi3.6938 (2)Cl2—Cs2xx3.9934 (2)
Cs2—Cl2xvii3.6938 (2)Cl2—Cs2xxi3.9934 (2)
Cs2—Cl2ix3.9934 (2)O—Cs1xix3.7206 (11)
Cl1i—Cs1—Cl1ii132.29 (7)Cl1iv—Cs2—Cl2xi54.61 (5)
Cl1i—Cs1—Cl1iii86.62 (7)Cl1xi—Cs2—Cl2xi54.61 (5)
Cl1ii—Cs1—Cl1iii74.44 (8)Cl1xii—Cs2—Cl2xi123.99 (6)
Cl1i—Cs1—Cl1iv74.44 (8)Cl1i—Cs2—Cl2xi123.99 (6)
Cl1ii—Cs1—Cl1iv86.62 (7)Cl1xiii—Cs2—Cl2xi117.20 (5)
Cl1iii—Cs1—Cl1iv132.29 (7)Cl1xiv—Cs2—Cl2xi63.99 (5)
Cl1i—Cs1—Cl1v159.74 (5)Cl1xv—Cs2—Cl2xi117.20 (5)
Cl1ii—Cs1—Cl1v66.96 (6)Cl1xvi—Cs2—Cl2xi63.99 (5)
Cl1iii—Cs1—Cl1v107.51 (4)Cl1iv—Cs2—Cl2xvii123.99 (6)
Cl1iv—Cs1—Cl1v104.23 (6)Cl1xi—Cs2—Cl2xvii123.99 (6)
Cl1i—Cs1—Cl1vi107.51 (4)Cl1xii—Cs2—Cl2xvii54.61 (5)
Cl1ii—Cs1—Cl1vi104.23 (6)Cl1i—Cs2—Cl2xvii54.61 (5)
Cl1iii—Cs1—Cl1vi159.74 (5)Cl1xiii—Cs2—Cl2xvii63.99 (5)
Cl1iv—Cs1—Cl1vi66.96 (6)Cl1xiv—Cs2—Cl2xvii117.20 (5)
Cl1v—Cs1—Cl1vi55.36 (7)Cl1xv—Cs2—Cl2xvii63.99 (5)
Cl1i—Cs1—Cl1vii66.96 (6)Cl1xvi—Cs2—Cl2xvii117.20 (5)
Cl1ii—Cs1—Cl1vii159.74 (5)Cl2xi—Cs2—Cl2xvii178.31 (11)
Cl1iii—Cs1—Cl1vii104.23 (6)Cl1iv—Cs2—Cl2ix61.50 (5)
Cl1iv—Cs1—Cl1vii107.51 (4)Cl1xi—Cs2—Cl2ix116.53 (5)
Cl1v—Cs1—Cl1vii94.96 (7)Cl1xii—Cs2—Cl2ix116.53 (5)
Cl1vi—Cs1—Cl1vii69.81 (7)Cl1i—Cs2—Cl2ix61.50 (5)
Cl1i—Cs1—Cl1viii104.23 (6)Cl1xiii—Cs2—Cl2ix130.44 (6)
Cl1ii—Cs1—Cl1viii107.51 (4)Cl1xiv—Cs2—Cl2ix130.44 (6)
Cl1iii—Cs1—Cl1viii66.96 (6)Cl1xv—Cs2—Cl2ix51.64 (5)
Cl1iv—Cs1—Cl1viii159.74 (5)Cl1xvi—Cs2—Cl2ix51.64 (5)
Cl1v—Cs1—Cl1viii69.81 (7)Cl2xi—Cs2—Cl2ix89.981 (1)
Cl1vi—Cs1—Cl1viii94.96 (7)Cl2xvii—Cs2—Cl2ix89.981 (1)
Cl1vii—Cs1—Cl1viii55.36 (7)Cl1iv—Cs2—Cl2xiv116.53 (5)
Cl1i—Cs1—O130.49 (8)Cl1xi—Cs2—Cl2xiv61.50 (5)
Cl1ii—Cs1—O56.52 (9)Cl1xii—Cs2—Cl2xiv61.50 (5)
Cl1iii—Cs1—O130.49 (8)Cl1i—Cs2—Cl2xiv116.53 (5)
Cl1iv—Cs1—O56.52 (9)Cl1xiii—Cs2—Cl2xiv51.64 (5)
Cl1v—Cs1—O49.48 (12)Cl1xiv—Cs2—Cl2xiv51.64 (5)
Cl1vi—Cs1—O49.48 (12)Cl1xv—Cs2—Cl2xiv130.44 (6)
Cl1vii—Cs1—O119.10 (13)Cl1xvi—Cs2—Cl2xiv130.44 (6)
Cl1viii—Cs1—O119.10 (13)Cl2xi—Cs2—Cl2xiv89.981 (1)
Cl1i—Cs1—Oviii56.52 (9)Cl2xvii—Cs2—Cl2xiv89.981 (1)
Cl1ii—Cs1—Oviii130.49 (8)Cl2ix—Cs2—Cl2xiv177.44 (11)
Cl1iii—Cs1—Oviii56.52 (9)O—Cr—Cl2180.000 (1)
Cl1iv—Cs1—Oviii130.49 (8)O—Cr—Cl187.80 (7)
Cl1v—Cs1—Oviii119.10 (13)Cl2—Cr—Cl192.20 (7)
Cl1vi—Cs1—Oviii119.10 (13)O—Cr—Cl1vi87.80 (7)
Cl1vii—Cs1—Oviii49.48 (12)Cl2—Cr—Cl1vi92.20 (7)
Cl1viii—Cs1—Oviii49.48 (12)Cl1—Cr—Cl1vi175.61 (13)
O—Cs1—Oviii166.1 (3)O—Cr—Cl1v87.80 (7)
Cl1i—Cs1—Cl2ix66.14 (4)Cl2—Cr—Cl1v92.20 (7)
Cl1ii—Cs1—Cl2ix66.14 (4)Cl1—Cr—Cl1v89.08 (11)
Cl1iii—Cs1—Cl2ix66.14 (4)Cl1vi—Cr—Cl1v90.75 (11)
Cl1iv—Cs1—Cl2ix66.14 (4)O—Cr—Cl1xviii87.80 (7)
Cl1v—Cs1—Cl2ix132.52 (4)Cl2—Cr—Cl1xviii92.20 (7)
Cl1vi—Cs1—Cl2ix132.52 (4)Cl1—Cr—Cl1xviii90.75 (11)
Cl1vii—Cs1—Cl2ix132.52 (4)Cl1vi—Cr—Cl1xviii89.08 (11)
Cl1viii—Cs1—Cl2ix132.52 (4)Cl1v—Cr—Cl1xviii175.61 (13)
O—Cs1—Cl2ix96.94 (14)O—Cr—Cs2xi122.60 (2)
Oviii—Cs1—Cl2ix96.94 (14)Cl2—Cr—Cs2xi57.40 (2)
Cl1i—Cs1—Cs1x140.03 (4)Cl1—Cr—Cs2xi55.23 (6)
Cl1ii—Cs1—Cs1x55.92 (4)Cl1vi—Cr—Cs2xi127.70 (6)
Cl1iii—Cs1—Cs1x55.92 (4)Cl1v—Cr—Cs2xi127.70 (6)
Cl1iv—Cs1—Cs1x140.03 (4)Cl1xviii—Cr—Cs2xi55.23 (6)
Cl1v—Cs1—Cs1x51.59 (4)O—Cr—Cs2xvii122.60 (2)
Cl1vi—Cs1—Cs1x106.08 (4)Cl2—Cr—Cs2xvii57.40 (2)
Cl1vii—Cs1—Cs1x106.08 (4)Cl1—Cr—Cs2xvii127.70 (6)
Cl1viii—Cs1—Cs1x51.59 (4)Cl1vi—Cr—Cs2xvii55.23 (6)
O—Cs1—Cs1x88.24 (4)Cl1v—Cr—Cs2xvii55.23 (6)
Oviii—Cs1—Cs1x88.24 (4)Cl1xviii—Cr—Cs2xvii127.70 (6)
Cl2ix—Cs1—Cs1x104.76 (3)Cs2xi—Cr—Cs2xvii114.80 (5)
Cl1iv—Cs2—Cl1xi55.04 (6)Cr—Cl1—Cs1ii158.12 (9)
Cl1iv—Cs2—Cl1xii94.30 (7)Cr—Cl1—Cs1xix95.55 (7)
Cl1xi—Cs2—Cl1xii69.39 (6)Cs1ii—Cl1—Cs1xix72.49 (4)
Cl1iv—Cs2—Cl1i69.39 (6)Cr—Cl1—Cs2xi92.54 (7)
Cl1xi—Cs2—Cl1i94.30 (7)Cs1ii—Cl1—Cs2xi104.34 (6)
Cl1xii—Cs2—Cl1i55.04 (6)Cs1xix—Cl1—Cs2xi85.37 (5)
Cl1iv—Cs2—Cl1xiii167.54 (6)Cr—Cl1—Cs2xx96.52 (7)
Cl1xi—Cs2—Cl1xiii112.95 (3)Cs1ii—Cl1—Cs2xx95.17 (5)
Cl1xii—Cs2—Cl1xiii83.11 (4)Cs1xix—Cl1—Cs2xx167.61 (6)
Cl1i—Cs2—Cl1xiii117.82 (3)Cs2xi—Cl1—Cs2xx96.89 (4)
Cl1iv—Cs2—Cl1xiv117.82 (3)Cr—Cl2—Cs2xi90.84 (5)
Cl1xi—Cs2—Cl1xiv83.11 (4)Cr—Cl2—Cs2xvii90.84 (5)
Cl1xii—Cs2—Cl1xiv112.95 (3)Cs2xi—Cl2—Cs2xvii178.31 (11)
Cl1i—Cs2—Cl1xiv167.54 (6)Cr—Cl2—Cs1xxi180.0
Cl1xiii—Cs2—Cl1xiv53.21 (7)Cs2xi—Cl2—Cs1xxi89.16 (5)
Cl1iv—Cs2—Cl1xv112.95 (3)Cs2xvii—Cl2—Cs1xxi89.16 (5)
Cl1xi—Cs2—Cl1xv167.54 (6)Cr—Cl2—Cs2xx88.72 (5)
Cl1xii—Cs2—Cl1xv117.82 (3)Cs2xi—Cl2—Cs2xx90.019 (1)
Cl1i—Cs2—Cl1xv83.11 (4)Cs2xvii—Cl2—Cs2xx90.019 (1)
Cl1xiii—Cs2—Cl1xv78.81 (6)Cs1xxi—Cl2—Cs2xx91.28 (5)
Cl1xiv—Cs2—Cl1xv101.95 (7)Cr—Cl2—Cs2xxi88.72 (5)
Cl1iv—Cs2—Cl1xvi83.11 (4)Cs2xi—Cl2—Cs2xxi90.019 (1)
Cl1xi—Cs2—Cl1xvi117.82 (3)Cs2xvii—Cl2—Cs2xxi90.019 (1)
Cl1xii—Cs2—Cl1xvi167.54 (6)Cs1xxi—Cl2—Cs2xxi91.28 (5)
Cl1i—Cs2—Cl1xvi112.95 (3)Cs2xx—Cl2—Cs2xxi177.44 (11)
Cl1xiii—Cs2—Cl1xvi101.95 (7)Cr—O—Cs1xix96.94 (14)
Cl1xiv—Cs2—Cl1xvi78.81 (6)Cr—O—Cs196.94 (14)
Cl1xv—Cs2—Cl1xvi53.21 (7)Cs1xix—O—Cs1166.1 (3)
Symmetry codes: (i) x1, y+1, z1/2; (ii) x+1, y+1, z+1; (iii) x1, y+1, z+1; (iv) x+1, y+1, z1/2; (v) x+1, y, z; (vi) x+1, y, z+1/2; (vii) x1, y, z+1/2; (viii) x1, y, z; (ix) x1/2, y1/2, z; (x) x, y+1, z+1; (xi) x+1, y+1, z; (xii) x1, y+1, z; (xiii) x+1/2, y1/2, z1; (xiv) x1/2, y1/2, z1; (xv) x+1/2, y1/2, z+1/2; (xvi) x1/2, y1/2, z+1/2; (xvii) x, y+1, z; (xviii) x, y, z+1/2; (xix) x+1, y, z; (xx) x+1/2, y+1/2, z+1; (xxi) x+1/2, y+1/2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaRb2[CrCl5(H2O)]Cs2[CrCl5(H2O)]
Mr418.21513.09
Crystal system, space groupOrthorhombic, PnmaOrthorhombic, Cmcm
Temperature (K)168173
a, b, c (Å)13.7558 (2), 9.7484 (1), 7.1074 (1)7.3868 (3), 17.1107 (7), 7.9848 (4)
V3)953.08 (2)1009.23 (8)
Z44
Radiation typeMo KαMo Kα
µ (mm1)12.689.50
Crystal size (mm)0.10 × 0.06 × 0.030.02 × 0.02 × 0.02
Data collection
DiffractometerSiemens SMART 1K CCD area-detector
diffractometer
Siemens SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Multi-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.364, 0.7020.833, 0.871
No. of measured, independent and
observed (I > 2σI) reflections
14988, 1825, 1465 7414, 883, 686
Rint0.0490.078
(sin θ/λ)max1)0.7650.715
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.110, 1.04 0.050, 0.151, 1.04
No. of reflections1825883
No. of parameters5328
H-atom treatmentAll H-atom parameters refined?
Δρmax, Δρmin (e Å3)0.97, 1.872.88, 1.40

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 2002), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2000).

Selected bond lengths (Å) for (I) top
Rb—Cl2i3.2887 (8)Rb—Cl4i3.6180 (11)
Rb—Cl1ii3.2924 (9)Rb—Cl4ii3.7833 (10)
Rb—Cl3iii3.3358 (8)Cr—O2.035 (4)
Rb—Cl33.3593 (8)Cr—Cl32.3251 (12)
Rb—Cl23.4133 (9)Cr—Cl12.3340 (13)
Rb—Cl43.4151 (9)Cr—Cl4iv2.3561 (7)
Rb—Cl4iii3.4619 (11)Cr—Cl22.3603 (14)
Rb—Cl1iii3.4707 (10)O—H0.75 (4)
Symmetry codes: (i) x, y, z; (ii) x, y, z+1; (iii) x+1/2, y, z+1/2; (iv) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O—H···Cl4v0.75 (4)2.43 (4)3.171 (2)174 (5)
Symmetry code: (v) x, y, z1.
Correlation between space group symmetry and the ranion/rcation ratio. top
CompoundSpace groupranion/rcation*
Rb2[TlCl5(H2O)]5Pnma1.649
Rb2[InCl5(H2O)]3Pnma1.649
Rb2[FeCl5(H2O)]2Pnma1.574
Rb2[CrCl5(H2O)]1Pnma1.550
Cs2[TlCl5(H2O)]5Pnma1.345
Cs2[InCl5(H2O)]3Pnma1.308
Cs2[FeCl5(H2O)]6Cmcm1.239
Cs2[RuCl5(H2O)]8Cmcm1.226
Cs2[IrCl5(H2O)]4Cmcm1.224
Cs2[RhCl5(H2O)]7Cmcm1.218
Cs2[CrCl5(H2O)]1Cmcm1.217
(1) This work (2) O'Connor et al. (1979) (3) Solans et al. (1988) (4) Coll et al. (1987) (5) Vasil'ev et al. (1994) (6) Greedan et al. (1980) (7) Thomas & Stanko (1973) (8) Hopkins et al. (1966) (*) Cation radii for eigt-fold coordination from Shannon (1976)
Selected bond lengths (Å) for (II) top
Cs1—Cl1i3.392 (2)Cs2—Cl2vi3.6938 (2)
Cs1—Cl1ii3.586 (2)Cs2—Cl2iii3.9934 (2)
Cs1—Cl2iii3.734 (4)Cr—O2.064 (10)
Cs2—Cl1iv3.605 (2)Cr—Cl22.308 (4)
Cs2—Cl1v3.665 (2)Cr—Cl12.340 (2)
Symmetry codes: (i) x1, y+1, z1/2; (ii) x+1, y, z; (iii) x1/2, y1/2, z; (iv) x+1, y+1, z1/2; (v) x+1/2, y1/2, z1; (vi) x+1, y+1, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds