Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

Hennings, E.; Schmidt, H.; Voigt, W.

doi:10.1107/S1600536814024532

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Volume 70| Part 12| December 2014| Pages 489-493

doi:10.1107/S1600536814024532

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Crystal structures of Ca(ClO₄)₂·4H₂O and Ca(ClO₄)₂·6H₂O

Erik Hennings,^a Horst Schmidt ^a ^* and Wolfgang Voigt ^a

^aTU Bergakademie Freiberg, Institute of Inorganic Chemistry, Leipziger Strasse 29, D-09596 Freiberg, Germany
^*Correspondence e-mail: horst.schmidt@chemie.tu-freiberg.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 15 October 2014; accepted 7 November 2014; online 15 November 2014)

The title compounds, calcium perchlorate tetrahydrate and calcium perchlorate hexahydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetrahydrate consists of one Ca²⁺ cation eightfold coordinated in a square-antiprismatic fashion by four water molecules and four O atoms of four perchlorate tetrahedra, forming chains parallel to [01-1] by sharing corners of the ClO₄ tetrahedra. The structure of the hexahydrate contains two different Ca²⁺ cations, each coordinated by six water molecules and two O atoms of two perchlorate tetrahedra, forming [Ca(H₂O)₆(ClO₄)]₂ dimers by sharing two ClO₄ tetrahedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO₄ tetrahedra. O—H⋯O hydrogen bonds between the water molecules as donor and ClO₄ tetrahedra and water molecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO₄)₂·6H₂O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures.

Keywords: crystal structure; low-temperature salt hydrates; perchlorate hydrates; calcium salts; Mars minerals.

CCDC references: 1033323; 1033324

1. Chemical context

Since the detection of perchlorates on Mars during the Phoenix Mission (Chevrier et al., 2009 ), interest in these salts, and especially their hydrates, has risen considerably (Kim et al., 2013 ; Quinn et al., 2013 ; Kerr, 2013 ; Davila et al., 2013 ; Schuttlefield et al., 2011 ; Navarro-González et al., 2010 ; Marion et al., 2010 ). To gain more knowledge about the behavior of salts and salt hydrates, it is essential to determine the corresponding phase diagrams. For calcium perchlorate, this was performed by several authors (Marion et al., 2010; Pestova et al., 2005 ; Dobrynina, 1984 ; Lilich & Djurinskii, 1956 ; Nicholson & Felsing, 1950 ; Willard & Smith, 1923 ) for different concentration areas with different results. The stable salt hydrate phase at room temperature in this system is calcium perchlorate tetrahydrate. At lower temperatures, a higher hydrated phase, i.e. the hexahydrate, occurs as the stable phase.

2. Structural commentary

The Ca²⁺ cation in Ca(ClO₄)·4H₂O is coordinated by four water molecules (O1, O2, O7, O8) and four O atoms from two pairs of symmetry-related perchlorate tetrahedra as shown in Fig. 1a. The resulting coordination polyhedron is a distorted square anti-prism (Fig. 1b). The Ca—O bond lengths involving the water molecules range from 2.3284 (17) to 2.4153 (16) Å and are considerably shorter than the Ca—O bond lengths involving the perchlorate O atoms [2.5417 (16) to 2.5695 (17) Å].

Figure 1
(a) The principle building block in the structure of Ca(ClO₄)₂·4H₂O and (b) the square anti-prismatic coordination of Ca²⁺. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 − x, −y, 1 − z; (ii) 1 − x, 1 − y, 2 − z.]

The two different Ca²⁺ cations in Ca(ClO₄)·6H₂O are each coordinated by six water molecules and two perchlorate tetrahedra (Fig. 2). Again, the bond lengths between the cations and water molecules [2.319 (6)–2.500 (6) Å] are shorter than those to the perchlorate groups. For the latter, one of the two distances for each of the Ca²⁺ cations is by 0.5 Å markedly longer than the other (∼3.07 versus ∼2.53 Å). Nevertheless, according to the bond-valence model (Brown, 2002 ), the longer bond contributes ca. 0.05 valence units to the overall bond-valence sum and hence should not be neglected. If this longer bond is considered to be relevant, again a square anti-prismatic coordination polyhedron is realised for both Ca²⁺ cations, however with a much greater distortion. Two perchlorate tetrahedra in the hexahydrate are shared between two Ca²⁺ ions, leading to the formation of [Ca(H₂O)₆(ClO₄)]₂ dimers oriented in layers parallel to (001).

Figure 2
The principle building blocks in the structure of Ca(ClO₄)₂·6H₂O. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

The perchlorate tetrahedra in the structure of Ca(ClO₄)·4H₂O are shared between two adjacent Ca²⁺ ions, forming chains extending parallel to [01 $[\overline{1}]$ ] (Fig. 3) whereby each Ca²⁺ ion is connected along the chain on one side with a pair of Cl1 perchlorate tetrahedra, and on the opposite side with a pair of Cl2 perchlorate tetrahedra. The chains are arranged in sheets parallel to (0 $[\overline{1}]$ 1) and are linked by O—H⋯O hydrogen bonds into a three-dimensional network with similar O⋯O distances between the water molecules and the perchlorate tetrahedra (Table 1).

Table 1
Hydrogen-bond geometry (Å, °) for Ca(ClO₄)₂·4H₂O

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O11ⁱ	0.82 (1)	2.11 (2)	2.888 (2)	158 (3)
O1—H1A⋯O3ⁱⁱ	0.82 (1)	2.13 (1)	2.947 (2)	174 (3)
O2—H2A⋯O11ⁱⁱⁱ	0.82 (1)	2.17 (2)	2.947 (2)	159 (3)
O2—H2B⋯O4^iv	0.82 (1)	2.02 (1)	2.830 (2)	172 (3)
O7—H7B⋯O4	0.81 (1)	2.22 (2)	2.924 (2)	146 (3)
O7—H7A⋯O1ⁱⁱⁱ	0.82 (1)	2.06 (1)	2.870 (2)	172 (3)
O8—H8A⋯O4^v	0.82 (1)	2.33 (3)	2.986 (2)	137 (4)
O8—H8B⋯O2^vi	0.82 (1)	2.14 (1)	2.950 (2)	169 (5)
Symmetry codes: (i) -x, -y, -z+1; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y-1, z; (v) -x+1, -y+1, -z+2; (vi) x-1, y, z.

Figure 3
Formation of sheets and interconnection of chains via hydrogen bonds in Ca(ClO₄)₂·4H₂O. Only the strongest hydrogen bonds are shown, represented by dashed lines.

In addition to the two coordinating perchlorate tetrahedra in Ca(ClO₄)·6H₂O, two `free' perchlorate tetrahedra are present in the crystal structure. These `free' ClO₄ tetrahedra are arranged in sheets and alternate with the [Ca(H₂O)₆(ClO₄)]₂ sheets along [001] (Fig. 4). The `free' perchlorate tetrahedra are connected to the dimers via O—H⋯O hydrogen bonds, as shown in Fig. 4. The dimers are additionally connected through further O—H⋯O hydrogen bonds (Table 2) into a three-dimensional network (Fig. 5).

Table 2
Hydrogen-bond geometry (Å, °) for Ca(ClO₄)₂·6H₂O

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O15	0.84 (2)	2.07 (3)	2.887 (10)	164 (8)
O1—H1B⋯O5ⁱ	0.84 (2)	2.25 (5)	2.915 (7)	136 (6)
O1—H1B⋯O16ⁱ	0.84 (2)	2.44 (5)	3.132 (10)	140 (6)
O2—H2A⋯O23ⁱⁱ	0.84 (2)	2.03 (2)	2.856 (9)	169 (7)
O2—H2B⋯O26ⁱⁱⁱ	0.84 (2)	2.14 (3)	2.932 (8)	155 (6)
O3—H3A⋯O12^iv	0.84 (2)	2.07 (2)	2.899 (8)	168 (8)
O3—H3B⋯O19ⁱⁱⁱ	0.84 (2)	2.15 (3)	2.934 (8)	156 (7)
O4—H4A⋯O27	0.84 (2)	2.28 (3)	3.074 (11)	158 (8)
O4—H4B⋯O28ⁱⁱⁱ	0.84 (2)	2.36 (3)	3.177 (10)	163 (8)
O5—H5A⋯O2^iv	0.84 (2)	1.98 (3)	2.783 (8)	159 (7)
O5—H5B⋯O19	0.84 (2)	2.20 (5)	2.903 (9)	142 (6)
O6—H6A⋯O8^v	0.84 (2)	2.18 (4)	2.925 (7)	149 (7)
O6—H6B⋯O19	0.84 (2)	2.08 (3)	2.891 (10)	162 (8)
O7—H7A⋯O23^vi	0.84 (2)	2.29 (4)	3.042 (9)	149 (6)
O7—H7B⋯O24^vii	0.84 (2)	2.50 (5)	3.199 (9)	141 (6)
O7—H7B⋯O27^viii	0.84 (2)	2.57 (5)	3.242 (11)	138 (6)
O8—H8A⋯O10^ix	0.84 (2)	2.08 (4)	2.805 (8)	145 (6)
O8—H8B⋯O15	0.84 (2)	2.07 (3)	2.879 (9)	162 (7)
O9—H9A⋯O27^x	0.84 (2)	2.06 (3)	2.865 (10)	161 (7)
O9—H9B⋯O21^vi	0.84 (2)	2.23 (5)	2.962 (10)	145 (7)
O10—H10A⋯O21^vii	0.84 (2)	2.12 (3)	2.930 (9)	163 (7)
O10—H10B⋯O28^x	0.84 (2)	2.10 (3)	2.902 (10)	162 (7)
O11—H11A⋯O9^ix	0.84 (2)	2.14 (4)	2.893 (9)	150 (7)
O11—H11B⋯O15^xi	0.84 (2)	2.11 (3)	2.915 (9)	161 (7)
O12—H12A⋯O26	0.84 (2)	2.35 (5)	2.995 (9)	135 (6)
O12—H12A⋯O20	0.84 (2)	2.40 (4)	3.102 (9)	142 (6)
O12—H12B⋯O24ⁱⁱ	0.84 (2)	2.03 (2)	2.861 (9)	171 (7)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y, z]$ ; (ii) x+1, y-1, z; (iii) x, y-1, z; (iv) $[x-{\script{1\over 2}}, -y, z]$ ; (v) $[x-{\script{1\over 2}}, -y+1, z]$ ; (vi) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (vii) $[-x+1, -y+2, z-{\script{1\over 2}}]$ ; (viii) $[-x+2, -y+1, z-{\script{1\over 2}}]$ ; (ix) $[x+{\script{1\over 2}}, -y+1, z]$ ; (x) $[-x+{\script{3\over 2}}, y, z-{\script{1\over 2}}]$ ; (xi) x, y+1, z.

Figure 4
Formation of perchlorate-bridged dimers in Ca(ClO₄)₂·6H₂O and location of `free' perchlorate tetrahedra in the gaps between the dimers (highlighted in dark green). Only the strongest hydrogen bonds are shown, represented by dashed lines.

Figure 5
Formation of layers parallel to (001) in Ca(ClO₄)₂·6H₂O. Only the strongest hydrogen bonds are shown, represented by dashed lines.

4. Database survey

For crystal structures of other M(ClO₄)₂·4H₂O phases, see: Robertson & Bish (2010 ; M = Mg); Hennings et al. (2014 ; Sr); Solovyov (2012 ; Mg); Johansson (1966 ; Hg). For crystal structures of other M(ClO₄)₂·6H₂O phases, see: Ghosh et al. (1997 ; M = Ni, Zn); Ghosh & Ray (1981 ; Fe); Johansson et al. (1978 ; Hg); Mani & Ramaseshan (1961 ; Cu); Johansson & Sandström (1987 ; Cd); Gallucci & Gerkin (1989 ; Cu); West (1935 ; Mg).

5. Synthesis and crystallization

Ca(ClO₄)₂·4H₂O was crystallized from an aqueous solution of 62.96 wt% Ca(ClO₄)₂ at 273 K after one day and Ca(ClO₄)₂·6H₂O from an aqueous solution of 57.55 wt% Ca(ClO₄)₂ at 238 K after one week. For the preparation of these aqueous solutions, Ca(ClO₄)₂·4H₂O (Acros Organics, p.A.) was used. The Ca²⁺ content was analysed via complexometric titration with EDTA. The crystals remain stable in the saturated aqueous solution over at least four weeks.

The samples were stored in a freezer or a cryostat at low temperatures. The crystals were separated and embedded in perfluorinated ether for X-ray analysis.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms of each structure were placed in the positions indicated by difference Fourier maps. For Ca(ClO₄)₂·4H₂O, distance restraints were applied for all water molecules, with O—H and H—H distance restraints of 0.82 (1) and 1.32 (1) Å, respectively. For Ca(ClO₄)₂·6H₂O, U_iso values were set at 1.2U_eq(O) using a riding-model approximation. Distance restraints were applied for that structure for all water molecules, with O—H and H—H distance restraints of 0.84 (2) and 1.4 (2) Å, respectively. Ca(ClO₄)₂·6H₂O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1.

Table 3
Experimental details

	Ca(ClO₄)₂·4H₂O	Ca(ClO₄)₂·6H₂O
Crystal data
M_r	311.04	347.08
Crystal system, space group	Triclinic, P $[\overline{1}]$	Orthorhombic, Pca2₁
Temperature (K)	200	180
a, b, c (Å)	5.4886 (11), 7.8518 (15), 11.574 (2)	10.9603 (4), 7.9667 (7), 26.7735 (18)
α, β, γ (°)	99.663 (16), 90.366 (16), 90.244 (16)	90, 90, 90
V (Å³)	491.71 (17)	2337.8 (3)
Z	2	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.24	1.06
Crystal size (mm)	0.04 × 0.03 × 0.02	0.38 × 0.31 × 0.08

Data collection
Diffractometer	Stoe IPDS2	Stoe IPDS2
Absorption correction	Integration Coppens (1970 )	Integration (Coppens, 1970)
T_min, T_max	0.644, 0.789	0.684, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	2659, 2636, 2529	15755, 5326, 4919
R_int	0.074	0.062
(sin θ/λ)_max (Å⁻¹)	0.686	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.20	0.042, 0.113, 1.09
No. of reflections	2636	5326
No. of parameters	168	380
No. of restraints	12	37
H-atom treatment	All H-atom parameters refined	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.75	0.41, −0.67
Absolute structure	–	Refined as an inversion twin
Absolute structure parameter	–	0.45 (9)
Computer programs: X-AREA and X-RED (Stoe & Cie, 2009 ), SHELXS97 and SHELXL2012 (Sheldrick, 2008 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1033323; 1033324

Crystal structure: contains datablocks CaClO4_4H2O_200K, CaClO4_6H2O_180K. DOI: 10.1107/S1600536814024532/wm5079sup1.cif

Structure factors: contains datablock CaClO4_4H2O_200K. DOI: 10.1107/S1600536814024532/wm5079CaClO4_4H2O_200Ksup2.hkl

Structure factors: contains datablock CaClO4_6H2O_180K. DOI: 10.1107/S1600536814024532/wm5079CaClO4_6H2O_180Ksup3.hkl

Supporting information file. DOI: 10.1107/S1600536814024532/wm5079CaClO4_4H2O_200Ksup4.cml

Supporting information file. DOI: 10.1107/S1600536814024532/wm5079CaClO4_6H2O_180Ksup5.cml

checkCIF report

Chemical context top

Since the detection of perchlorates on Mars during the Phoenix Mission (Chevrier et al., 2009), interest in these salts, and especially their hydrates, has risen considerably (Kim et al., 2013; Quinn et al., 2013; Kerr, 2013; Davila et al., 2013; Schuttlefield et al., 2011; Navarro-González et al., 2010; Marion et al., 2010). To gain more knowledge about the behavior of salts and salt hydrates, it is essential to determine the corresponding phase diagrams. For calcium perchlorate, this was performed by several authors (Marion et al., 2010; Pestova et al., 2005; Dobrynina, 1984; Lilich & Djurinskii, 1956; Nicholson & Felsing, 1950; Willard & Smith, 1923) for different concentration areas with different results. The stable salt hydrate phase at room temperature in this system is calcium perchlorate tetrahydrate. At lower temperatures, a higher hydrated phase, i.e. the hexahydrate, occurs as the stable phase.

Structural commentary top

The two different Ca²⁺ cations in Ca(ClO₄)·6H₂O are each coordinated by six water molecules and two perchlorate tetrahedra (Fig. 2). Again, the bond lengths between the cations and water molecules [2.319 (6)–2.500 (6) Å] are shorter than those to the perchlorate groups. For the latter, one of the two distances for each of the Ca²⁺ cations is by 0.5 Å markedly longer than the other (~3.07 versus ~2.53 Å). Nevertheless, according to the bond-valence model (Brown, 2002), the longer bond contributes ca. 0.05 valence units to the overall bond-valence sum and hence should not be neglected. If this longer bond is considered to be relevant, again a square anti-prismatic coordination polyhedron is realised for both Ca²⁺ cations, however with a much greater distortion. Two perchlorate tetrahedra in the hexahydrate are shared between two Ca²⁺ ions, leading to the formation of [Ca(H₂O)₆(ClO₄)]₂ dimers oriented in layers parallel to (001).

Supramolecular features top

The perchlorate tetrahedra in the structure of Ca(ClO₄)·4H₂O are shared between two adjacent Ca²⁺ ions, forming chains extending parallel to [011] (Fig. 3) whereby each Ca²⁺ ion is connected along the chain on one side with a pair of Cl1 perchlorate tetrahedra, and on the opposite side with a pair of Cl2 perchlorate tetrahedra. The chains are arranged in sheets parallel to (011) and are linked by O—H···O hydrogen bonds into a three-dimensional network with similar O···O distances between the water molecules and the perchlorate tetrahedra (Table 1).

In addition to the two coordinating perchlorate tetrahedra in Ca(ClO₄)·6H₂O, two `free' perchlorate tetrahedra are present in the crystal structure. These `free' ClO₄ tetrahedra are arranged in sheets and alternate with the [Ca(H₂O)₆(ClO₄)]₂ sheets along [001] (Fig. 4). The `free' perchlorate tetrahedra are connected to the dimers via O—H···O hydrogen bonds, as shown in Fig. 4. The dimers itself are additionally connected through further O—H···O hydrogen bonds (Table 2) into a three-dimensional network (Fig. 5).

Database survey top

For crystal structures of other MClO₄·4H₂O phases, see: Robertson et al. (2010; M = Mg); Hennings et al. (2014; Sr); Solovyov (2012; Mg); Johansson (1966; Hg). For crystal structures of other MClO₄·6H₂O phases, see: Ghosh et al. (1997; M = Ni, Zn); Ghosh et al. (1981; Fe); Johansson et al. (1978; Hg); Mani et al. (1961; Cu); Johansson et al. (1987; Cd); Gallucci et al. (1989; Cu); West (1935; Mg).

Synthesis and crystallization top

The samples were stored in a freezer or a cryostat at low temperatures. The crystals were separated and embedded in perfluorinated ether for X-ray analysis.

Refinement top

Related literature top

For related literature, see: Brown (2002); Chevrier et al. (2009); Davila et al. (2013); Dobrynina (1984); Gallucci & Gerkin (1989); Ghosh & Ray (1981); Ghosh et al. (1997); Hennings et al. (2014); Johansson (1966); Johansson & Sandström (1978, 1987); Kerr (2013); Kim et al. (2013); Lilich & Djurinskii (1956); Mani & Ramaseshan (1961); Marion et al. (2010); Navarro-González, Vargas, de la Rosa, Raga & McKay (2010); Nicholson & Felsing (1950); Pestova et al. (2005); Quinn et al. (2013); Robertson & Bish (2010); Schuttlefield et al. (2011); Solovyov (2012); West (1935); Willard & Smith (1923).

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA(Stoe & Cie, 2009); data reduction: X-RED (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

(a) The principle building block in the structure of Ca(ClO₄)₂·4H₂O and (b) the square anti-prismatic coordination of Ca²⁺. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1-x, -y, 1-z; (ii) 1-x, 1-y, 2-z.]

The principle building blocks in the structure of Ca(ClO₄)₂·6H₂O. Displacement ellipsoids are drawn at the 50% probability level.

Formation of sheets and interconnection of chains via hydrogen bonds in Ca(ClO₄)₂·4H₂O. Only the strongest hydrogen bonds are shown, represented by dashed lines.

Formation of perchlorate-bridged dimers in Ca(ClO₄)₂·6 H₂O and location of `free' perchlorate tetrahedra in the gaps between the dimers (highlighted in dark green). Only the strongest hydrogen bonds are shown, represented by dashed lines.

Formation of layers parallel to (001) in Ca(ClO₄)₂·6H₂O. Only the strongest hydrogen bonds are shown, represented by dashed lines.

(CaClO4_4H2O_200K) Calcium perchlorate tetrahydrate top

Crystal data top

Ca(ClO₄)₂·4H₂O	Z = 2
M_r = 311.04	F(000) = 316
Triclinic, P1	D_x = 2.101 Mg m⁻³
a = 5.4886 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8518 (15) Å	Cell parameters from 26892 reflections
c = 11.574 (2) Å	θ = 1.8–29.6°
α = 99.663 (16)°	µ = 1.24 mm⁻¹
β = 90.366 (16)°	T = 200 K
γ = 90.244 (16)°	Plate, colourless
V = 491.71 (17) Å³	0.04 × 0.03 × 0.02 mm

Data collection top

Stoe IPDS-2 diffractometer	2636 independent reflections
Radiation source: fine-focus sealed tube	2529 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.074
Detector resolution: 6.67 pixels mm^-1	θ_max = 29.2°, θ_min = 1.8°
rotation method scans	h = −6→7
Absorption correction: integration Coppens (1970)	k = −10→10
T_min = 0.644, T_max = 0.789	l = −15→15
2659 measured reflections

Refinement top

Refinement on F²	12 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	All H-atom parameters refined
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0427P)² + 0.6952P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max = 0.001
2636 reflections	Δρ_max = 0.36 e Å⁻³
168 parameters	Δρ_min = −0.75 e Å⁻³

Crystal data top

Ca(ClO₄)₂·4H₂O	γ = 90.244 (16)°
M_r = 311.04	V = 491.71 (17) Å³
Triclinic, P1	Z = 2
a = 5.4886 (11) Å	Mo Kα radiation
b = 7.8518 (15) Å	µ = 1.24 mm⁻¹
c = 11.574 (2) Å	T = 200 K
α = 99.663 (16)°	0.04 × 0.03 × 0.02 mm
β = 90.366 (16)°

Data collection top

Stoe IPDS-2 diffractometer	2636 independent reflections
Absorption correction: integration Coppens (1970)	2529 reflections with I > 2σ(I)
T_min = 0.644, T_max = 0.789	R_int = 0.074
2659 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	12 restraints
wR(F²) = 0.089	All H-atom parameters refined
S = 1.20	Δρ_max = 0.36 e Å⁻³
2636 reflections	Δρ_min = −0.75 e Å⁻³
168 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ca1	0.51082 (7)	0.23667 (5)	0.75582 (3)	0.01027 (10)
Cl1	0.24098 (7)	−0.16433 (5)	0.55712 (4)	0.00941 (11)
Cl2	0.32358 (8)	0.67561 (5)	0.92062 (4)	0.01142 (11)
O2	0.7504 (3)	−0.01296 (18)	0.76729 (13)	0.0139 (3)
O1	0.2602 (3)	0.38606 (19)	0.63310 (12)	0.0138 (3)
O3	0.4297 (3)	−0.2742 (2)	0.58913 (14)	0.0186 (3)
O4	0.5616 (3)	0.7400 (2)	0.89554 (15)	0.0212 (3)
O10	0.2625 (3)	−0.1487 (2)	0.43554 (13)	0.0178 (3)
O11	0.0048 (3)	−0.2367 (2)	0.57611 (13)	0.0169 (3)
O9	0.2594 (3)	0.00467 (19)	0.62752 (14)	0.0182 (3)
O5	0.2746 (3)	0.7265 (2)	1.04351 (13)	0.0205 (3)
O8	0.2156 (3)	0.1319 (2)	0.86975 (14)	0.0203 (3)
O7	0.7938 (3)	0.4545 (2)	0.74134 (15)	0.0209 (3)
O6	0.3224 (3)	0.48966 (18)	0.89187 (14)	0.0177 (3)
O12	0.1399 (3)	0.7434 (2)	0.85344 (17)	0.0290 (4)
H2B	0.683 (6)	−0.078 (3)	0.806 (2)	0.033 (9)*
H1A	0.317 (6)	0.477 (2)	0.618 (2)	0.025 (8)*
H2A	0.788 (6)	−0.072 (3)	0.7045 (15)	0.031 (9)*
H7A	0.931 (3)	0.444 (4)	0.714 (3)	0.033 (9)*
H7B	0.792 (6)	0.541 (3)	0.791 (2)	0.040 (10)*
H8B	0.087 (5)	0.083 (6)	0.848 (3)	0.077 (16)*
H1B	0.219 (6)	0.328 (3)	0.5705 (15)	0.026 (8)*
H8A	0.196 (7)	0.179 (5)	0.9380 (15)	0.058 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.00953 (17)	0.00980 (17)	0.01102 (17)	−0.00055 (12)	−0.00070 (12)	0.00046 (12)
Cl1	0.00864 (19)	0.01026 (19)	0.00859 (19)	−0.00147 (14)	−0.00038 (13)	−0.00050 (14)
Cl2	0.0136 (2)	0.00949 (19)	0.0102 (2)	0.00073 (14)	−0.00324 (15)	−0.00092 (14)
O2	0.0161 (7)	0.0134 (6)	0.0121 (6)	0.0015 (5)	0.0011 (5)	0.0018 (5)
O1	0.0149 (6)	0.0131 (6)	0.0129 (6)	−0.0014 (5)	−0.0024 (5)	0.0006 (5)
O3	0.0151 (7)	0.0190 (7)	0.0226 (8)	0.0042 (6)	−0.0026 (6)	0.0062 (6)
O4	0.0218 (8)	0.0199 (7)	0.0220 (8)	−0.0058 (6)	0.0042 (6)	0.0039 (6)
O10	0.0210 (7)	0.0236 (7)	0.0094 (6)	0.0030 (6)	0.0031 (5)	0.0040 (5)
O11	0.0119 (6)	0.0209 (7)	0.0172 (7)	−0.0079 (5)	0.0007 (5)	0.0013 (6)
O9	0.0177 (7)	0.0133 (7)	0.0201 (7)	−0.0032 (5)	−0.0029 (5)	−0.0072 (5)
O5	0.0185 (7)	0.0267 (8)	0.0128 (7)	0.0025 (6)	0.0015 (5)	−0.0071 (6)
O8	0.0193 (7)	0.0199 (7)	0.0188 (7)	−0.0092 (6)	0.0044 (6)	−0.0055 (6)
O7	0.0168 (7)	0.0175 (7)	0.0251 (8)	−0.0064 (6)	0.0063 (6)	−0.0062 (6)
O6	0.0226 (7)	0.0085 (6)	0.0203 (7)	0.0012 (5)	0.0008 (6)	−0.0029 (5)
O12	0.0314 (9)	0.0213 (8)	0.0347 (10)	0.0029 (7)	−0.0216 (8)	0.0065 (7)

Geometric parameters (Å, º) top

Ca1—O8	2.3284 (17)	Cl1—O10	1.4385 (15)
Ca1—O7	2.3329 (17)	Cl1—O9	1.4387 (15)
Ca1—O2	2.3866 (15)	Cl1—O11	1.4461 (15)
Ca1—O1	2.4153 (16)	Cl2—O12	1.4274 (16)
Ca1—O10ⁱ	2.5417 (16)	Cl2—O5	1.4388 (15)
Ca1—O9	2.5439 (16)	Cl2—O6	1.4420 (15)
Ca1—O6	2.5463 (16)	Cl2—O4	1.4473 (17)
Ca1—O5ⁱⁱ	2.5695 (17)	O10—Ca1ⁱ	2.5417 (16)
Cl1—O3	1.4365 (15)	O5—Ca1ⁱⁱ	2.5695 (17)

O8—Ca1—O7	146.78 (6)	O7—Ca1—O5ⁱⁱ	78.03 (6)
O8—Ca1—O2	89.06 (6)	O2—Ca1—O5ⁱⁱ	70.60 (5)
O7—Ca1—O2	104.79 (6)	O1—Ca1—O5ⁱⁱ	142.78 (5)
O8—Ca1—O1	100.92 (6)	O10ⁱ—Ca1—O5ⁱⁱ	122.42 (5)
O7—Ca1—O1	84.26 (6)	O9—Ca1—O5ⁱⁱ	136.94 (6)
O2—Ca1—O1	146.29 (5)	O6—Ca1—O5ⁱⁱ	70.75 (5)
O8—Ca1—O10ⁱ	140.33 (6)	O3—Cl1—O10	110.02 (9)
O7—Ca1—O10ⁱ	72.75 (6)	O3—Cl1—O9	110.18 (10)
O2—Ca1—O10ⁱ	70.60 (5)	O10—Cl1—O9	109.06 (10)
O1—Ca1—O10ⁱ	81.78 (5)	O3—Cl1—O11	109.83 (9)
O8—Ca1—O9	70.75 (6)	O10—Cl1—O11	109.13 (9)
O7—Ca1—O9	140.80 (6)	O9—Cl1—O11	108.59 (9)
O2—Ca1—O9	79.34 (5)	O12—Cl2—O5	109.54 (11)
O1—Ca1—O9	73.95 (5)	O12—Cl2—O6	109.31 (10)
O10ⁱ—Ca1—O9	72.18 (5)	O5—Cl2—O6	109.33 (10)
O8—Ca1—O6	71.00 (6)	O12—Cl2—O4	110.57 (11)
O7—Ca1—O6	79.25 (6)	O5—Cl2—O4	108.97 (10)
O2—Ca1—O6	139.24 (5)	O6—Cl2—O4	109.09 (10)
O1—Ca1—O6	73.94 (5)	Cl1—O10—Ca1ⁱ	147.22 (10)
O10ⁱ—Ca1—O6	144.46 (5)	Cl1—O9—Ca1	150.03 (10)
O9—Ca1—O6	123.19 (5)	Cl2—O5—Ca1ⁱⁱ	140.90 (10)
O8—Ca1—O5ⁱⁱ	78.49 (6)	Cl2—O6—Ca1	142.92 (10)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O11ⁱⁱⁱ	0.82 (1)	2.11 (2)	2.888 (2)	158 (3)
O1—H1A···O3^iv	0.82 (1)	2.13 (1)	2.947 (2)	174 (3)
O2—H2A···O11^v	0.82 (1)	2.17 (2)	2.947 (2)	159 (3)
O2—H2B···O4^vi	0.82 (1)	2.02 (1)	2.830 (2)	172 (3)
O7—H7B···O4	0.81 (1)	2.22 (2)	2.924 (2)	146 (3)
O7—H7A···O1^v	0.82 (1)	2.06 (1)	2.870 (2)	172 (3)
O8—H8A···O4ⁱⁱ	0.82 (1)	2.33 (3)	2.986 (2)	137 (4)
O8—H8B···O2^vii	0.82 (1)	2.14 (1)	2.950 (2)	169 (5)

Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x, −y, −z+1; (iv) x, y+1, z; (v) x+1, y, z; (vi) x, y−1, z; (vii) x−1, y, z.

(CaClO4_6H2O_180K) Calcium perchlorate hexahydrate top

Crystal data top

Ca(ClO₄)₂·6H₂O	D_x = 1.972 Mg m⁻³
M_r = 347.08	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 17254 reflections
a = 10.9603 (4) Å	θ = 2.9–29.6°
b = 7.9667 (7) Å	µ = 1.06 mm⁻¹
c = 26.7735 (18) Å	T = 180 K
V = 2337.8 (3) Å³	Plate, colourless
Z = 8	0.38 × 0.31 × 0.08 mm
F(000) = 1424

Data collection top

Stoe IPDS-2 diffractometer	5326 independent reflections
Radiation source: fine-focus sealed tube	4919 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.5°, θ_min = 1.5°
rotation method scans	h = −15→15
Absorption correction: integration (Coppens, 1970)	k = −11→9
T_min = 0.684, T_max = 0.923	l = −37→37
15755 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	Only H-atom coordinates refined
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0687P)² + 2.3411P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.113	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.41 e Å⁻³
5326 reflections	Δρ_min = −0.67 e Å⁻³
380 parameters	Absolute structure: Refined as an inversion twin
37 restraints	Absolute structure parameter: 0.45 (9)

Crystal data top

Ca(ClO₄)₂·6H₂O	V = 2337.8 (3) Å³
M_r = 347.08	Z = 8
Orthorhombic, Pca2₁	Mo Kα radiation
a = 10.9603 (4) Å	µ = 1.06 mm⁻¹
b = 7.9667 (7) Å	T = 180 K
c = 26.7735 (18) Å	0.38 × 0.31 × 0.08 mm

Data collection top

Stoe IPDS-2 diffractometer	5326 independent reflections
Absorption correction: integration (Coppens, 1970)	4919 reflections with I > 2σ(I)
T_min = 0.684, T_max = 0.923	R_int = 0.062
15755 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	Only H-atom coordinates refined
wR(F²) = 0.113	Δρ_max = 0.41 e Å⁻³
S = 1.09	Δρ_min = −0.67 e Å⁻³
5326 reflections	Absolute structure: Refined as an inversion twin
380 parameters	Absolute structure parameter: 0.45 (9)
37 restraints

Special details top

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ca1	0.87471 (15)	0.02736 (19)	0.29261 (6)	0.0110 (3)
Ca2	0.87640 (16)	0.47462 (18)	0.07672 (6)	0.0112 (3)
Cl3	0.7770 (2)	0.50239 (14)	0.39582 (8)	0.0102 (5)
Cl4	0.79753 (11)	0.06649 (15)	0.13985 (8)	0.0110 (2)
Cl1	0.95348 (11)	0.43473 (15)	0.22917 (8)	0.0109 (2)
Cl2	0.0260 (2)	0.99991 (14)	0.47324 (8)	0.0128 (5)
O5	0.7128 (5)	0.2189 (8)	0.2859 (2)	0.0169 (11)
H5B	0.714 (6)	0.295 (6)	0.264 (2)	0.020*
H5A	0.660 (5)	0.209 (10)	0.3081 (19)	0.020*
O3	0.7416 (5)	−0.1972 (7)	0.2841 (2)	0.0185 (12)
H3A	0.672 (3)	−0.190 (10)	0.296 (3)	0.022*
H3B	0.752 (7)	−0.274 (6)	0.263 (2)	0.022*
O7	0.9726 (7)	0.4844 (6)	−0.0075 (3)	0.0162 (14)
H7B	0.995 (7)	0.557 (7)	−0.028 (2)	0.019*
H7A	0.989 (6)	0.406 (6)	−0.027 (2)	0.019*
O8	1.0380 (5)	0.2796 (7)	0.0823 (2)	0.0132 (10)
H8A	1.094 (4)	0.245 (8)	0.064 (2)	0.016*
H8B	1.013 (6)	0.186 (4)	0.093 (2)	0.016*
O6	0.7539 (4)	0.6064 (6)	0.13676 (16)	0.0190 (8)
H6B	0.761 (7)	0.565 (10)	0.1655 (14)	0.023*
H6A	0.684 (3)	0.648 (9)	0.133 (3)	0.023*
O1	0.9967 (4)	−0.1049 (6)	0.23219 (17)	0.0186 (8)
H1A	0.987 (7)	−0.060 (10)	0.2041 (15)	0.022*
H1B	1.0726 (17)	−0.118 (9)	0.232 (3)	0.022*
O2	0.9964 (5)	−0.1849 (7)	0.3393 (2)	0.0119 (11)
H2A	1.007 (7)	−0.184 (9)	0.3702 (7)	0.014*
H2B	0.967 (6)	−0.281 (4)	0.335 (2)	0.014*
O4	0.7803 (9)	0.0171 (8)	0.3739 (3)	0.0262 (18)
H4B	0.793 (8)	−0.068 (6)	0.392 (3)	0.031*
H4A	0.795 (7)	0.093 (7)	0.395 (2)	0.031*
O15	0.9234 (8)	0.0045 (5)	0.1339 (4)	0.0152 (16)
O14	0.7230 (8)	−0.0046 (5)	0.1019 (3)	0.0194 (18)
O19	0.8302 (8)	0.4971 (5)	0.2349 (3)	0.0142 (15)
O20	1.0316 (9)	0.5052 (6)	0.2678 (4)	0.027 (2)
O26	0.8567 (9)	0.5044 (5)	0.3525 (3)	0.0215 (19)
O12	1.0148 (5)	0.2008 (7)	0.3398 (2)	0.0129 (11)
H12B	1.034 (7)	0.189 (9)	0.3699 (10)	0.016*
H12A	1.006 (6)	0.303 (3)	0.334 (2)	0.016*
O16	0.7540 (9)	0.0215 (7)	0.1877 (3)	0.0234 (15)
O21	0.1020 (10)	0.9989 (6)	0.5168 (3)	0.026 (2)
O28	0.7947 (7)	0.6558 (9)	0.4237 (3)	0.0231 (15)
O27	0.8080 (7)	0.3589 (9)	0.4260 (3)	0.0260 (16)
O23	0.0566 (6)	0.8560 (8)	0.4423 (3)	0.0183 (13)
O24	0.0519 (7)	1.1496 (9)	0.4444 (3)	0.0212 (14)
O18	0.9975 (9)	0.4783 (7)	0.1797 (3)	0.0223 (14)
O13	0.7991 (3)	0.2473 (5)	0.13424 (18)	0.0150 (8)
O17	0.9520 (4)	0.2544 (5)	0.23441 (19)	0.0158 (8)
O9	0.7381 (6)	0.2976 (8)	0.0297 (2)	0.0171 (12)
H9A	0.721 (7)	0.338 (8)	0.0016 (13)	0.021*
H9B	0.753 (7)	0.195 (3)	0.025 (3)	0.021*
O22	−0.0976 (9)	0.9933 (7)	0.4886 (5)	0.034 (2)
O25	0.6508 (8)	0.4900 (7)	0.3824 (5)	0.034 (2)
O10	0.7580 (5)	0.6907 (7)	0.0295 (2)	0.0139 (11)
H10B	0.746 (7)	0.658 (8)	0.0002 (11)	0.017*
H10A	0.783 (6)	0.789 (4)	0.025 (2)	0.017*
O11	1.0097 (5)	0.7020 (8)	0.0838 (3)	0.0192 (12)
H11A	1.079 (3)	0.736 (9)	0.075 (3)	0.023*
H11B	0.987 (7)	0.799 (4)	0.092 (3)	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0083 (6)	0.0090 (5)	0.0157 (7)	0.0010 (5)	0.0018 (4)	−0.0005 (7)
Ca2	0.0095 (6)	0.0084 (5)	0.0155 (7)	0.0010 (5)	0.0021 (4)	0.0016 (7)
Cl3	0.0096 (11)	0.0097 (11)	0.0113 (11)	−0.0005 (4)	0.0016 (10)	0.0004 (4)
Cl4	0.0127 (5)	0.0095 (6)	0.0108 (5)	−0.0007 (4)	0.0020 (4)	0.0012 (5)
Cl1	0.0124 (6)	0.0080 (6)	0.0122 (5)	−0.0018 (4)	0.0019 (4)	0.0008 (5)
Cl2	0.0180 (13)	0.0098 (11)	0.0105 (11)	−0.0001 (4)	0.0016 (11)	0.0002 (4)
O5	0.015 (2)	0.015 (2)	0.020 (2)	0.0012 (19)	0.0022 (19)	0.0054 (19)
O3	0.019 (3)	0.013 (2)	0.024 (2)	−0.007 (2)	0.007 (2)	−0.0047 (18)
O7	0.022 (3)	0.019 (3)	0.008 (3)	0.0018 (18)	0.009 (2)	−0.0048 (16)
O8	0.011 (2)	0.0077 (19)	0.020 (2)	0.0033 (17)	0.0061 (18)	−0.0006 (17)
O6	0.0201 (19)	0.024 (2)	0.0130 (16)	0.0123 (17)	0.0008 (17)	0.0029 (18)
O1	0.0196 (19)	0.021 (2)	0.0151 (17)	0.0079 (17)	0.0003 (17)	0.0028 (18)
O2	0.017 (2)	0.009 (2)	0.009 (2)	−0.0002 (19)	−0.0009 (17)	0.0010 (17)
O4	0.033 (4)	0.023 (3)	0.023 (4)	0.000 (2)	0.008 (3)	0.006 (2)
O15	0.014 (4)	0.010 (3)	0.022 (4)	0.0049 (13)	−0.001 (3)	−0.0002 (14)
O14	0.019 (4)	0.019 (4)	0.021 (4)	−0.0067 (15)	0.000 (3)	−0.0045 (15)
O19	0.013 (4)	0.019 (3)	0.011 (3)	0.0049 (14)	0.007 (3)	0.0011 (13)
O20	0.027 (5)	0.023 (4)	0.033 (5)	−0.0106 (18)	−0.016 (4)	−0.0050 (18)
O26	0.034 (5)	0.011 (3)	0.020 (4)	−0.0004 (16)	0.014 (4)	0.0002 (14)
O12	0.016 (2)	0.011 (2)	0.013 (2)	0.0011 (19)	−0.0010 (17)	0.0021 (18)
O16	0.027 (3)	0.022 (2)	0.021 (3)	0.001 (2)	0.015 (2)	0.011 (2)
O21	0.035 (5)	0.029 (4)	0.013 (4)	0.0009 (18)	−0.010 (4)	0.0018 (15)
O28	0.037 (4)	0.011 (3)	0.021 (3)	−0.004 (2)	0.002 (3)	−0.005 (2)
O27	0.042 (4)	0.017 (3)	0.019 (3)	0.008 (3)	0.003 (3)	0.008 (3)
O23	0.027 (3)	0.014 (3)	0.015 (3)	0.002 (2)	0.001 (2)	−0.006 (2)
O24	0.034 (3)	0.012 (3)	0.017 (3)	−0.003 (2)	−0.006 (2)	0.008 (2)
O18	0.025 (3)	0.027 (2)	0.015 (3)	0.001 (2)	0.012 (2)	0.002 (2)
O13	0.0195 (19)	0.0081 (18)	0.017 (2)	0.0011 (14)	0.0007 (15)	0.0020 (15)
O17	0.0197 (19)	0.0074 (17)	0.020 (2)	−0.0009 (15)	−0.0007 (15)	0.0014 (16)
O9	0.025 (3)	0.011 (2)	0.016 (2)	−0.003 (2)	−0.003 (2)	0.0006 (19)
O22	0.024 (5)	0.032 (4)	0.044 (6)	0.0013 (19)	0.013 (4)	0.000 (2)
O25	0.010 (4)	0.038 (4)	0.054 (6)	−0.0011 (19)	−0.014 (4)	0.004 (2)
O10	0.012 (2)	0.014 (2)	0.016 (2)	0.0008 (19)	0.0021 (18)	0.0005 (18)
O11	0.016 (3)	0.015 (2)	0.027 (2)	−0.002 (2)	0.000 (2)	−0.0030 (19)

Geometric parameters (Å, º) top

Ca1—O3	2.319 (6)	Cl3—O25	1.432 (9)
Ca1—O5	2.347 (6)	Cl3—O27	1.440 (7)
Ca1—O1	2.349 (5)	Cl3—O28	1.446 (7)
Ca1—O4	2.412 (9)	Cl3—O26	1.452 (9)
Ca1—O12	2.421 (6)	Cl4—O16	1.414 (8)
Ca1—O2	2.490 (6)	Cl4—O14	1.421 (8)
Ca1—O17	2.533 (5)	Cl4—O13	1.449 (4)
Ca1—O16	3.104 (9)	Cl4—O15	1.474 (8)
Ca2—O11	2.335 (6)	Cl1—O17	1.444 (4)
Ca2—O6	2.343 (5)	Cl1—O19	1.448 (8)
Ca2—O8	2.360 (5)	Cl1—O18	1.451 (8)
Ca2—O9	2.423 (6)	Cl1—O20	1.455 (9)
Ca2—O7	2.491 (7)	Cl2—O22	1.416 (10)
Ca2—O10	2.500 (6)	Cl2—O21	1.433 (10)
Ca2—O13	2.523 (4)	Cl2—O24	1.449 (7)
Ca2—O18	3.061 (9)	Cl2—O23	1.453 (7)

O3—Ca1—O5	91.1 (3)	O7—Ca2—O10	74.9 (2)
O3—Ca1—O1	86.81 (19)	O11—Ca2—O13	135.8 (2)
O5—Ca1—O1	132.0 (2)	O6—Ca2—O13	73.17 (15)
O3—Ca1—O4	78.0 (2)	O8—Ca2—O13	75.00 (17)
O5—Ca1—O4	76.5 (3)	O9—Ca2—O13	71.91 (17)
O1—Ca1—O4	148.3 (2)	O7—Ca2—O13	135.81 (17)
O3—Ca1—O12	152.9 (2)	O10—Ca2—O13	128.95 (17)
O5—Ca1—O12	98.5 (2)	O11—Ca2—O18	69.4 (2)
O1—Ca1—O12	104.72 (19)	O6—Ca2—O18	68.03 (19)
O4—Ca1—O12	79.7 (3)	O8—Ca2—O18	67.9 (2)
O3—Ca1—O2	82.1 (2)	O9—Ca2—O18	138.2 (2)
O5—Ca1—O2	152.3 (2)	O7—Ca2—O18	129.2 (3)
O1—Ca1—O2	74.68 (18)	O10—Ca2—O18	132.42 (19)
O4—Ca1—O2	75.8 (2)	O13—Ca2—O18	66.58 (17)
O12—Ca1—O2	77.7 (2)	O25—Cl3—O27	108.3 (5)
O3—Ca1—O17	134.5 (2)	O25—Cl3—O28	108.5 (5)
O5—Ca1—O17	75.01 (18)	O27—Cl3—O28	110.4 (5)
O1—Ca1—O17	72.92 (15)	O25—Cl3—O26	112.4 (7)
O4—Ca1—O17	136.29 (19)	O27—Cl3—O26	108.3 (4)
O12—Ca1—O17	72.61 (17)	O28—Cl3—O26	108.8 (4)
O2—Ca1—O17	127.91 (18)	O16—Cl4—O14	110.7 (5)
O3—Ca1—O16	68.4 (2)	O16—Cl4—O13	110.5 (3)
O5—Ca1—O16	67.5 (2)	O14—Cl4—O13	109.2 (3)
O1—Ca1—O16	67.2 (2)	O16—Cl4—O15	109.2 (5)
O4—Ca1—O16	129.3 (3)	O14—Cl4—O15	109.1 (5)
O12—Ca1—O16	138.63 (19)	O13—Cl4—O15	108.1 (3)
O2—Ca1—O16	132.21 (19)	O17—Cl1—O19	108.7 (3)
O17—Ca1—O16	66.22 (16)	O17—Cl1—O18	109.3 (3)
O11—Ca2—O6	87.4 (2)	O19—Cl1—O18	109.0 (5)
O11—Ca2—O8	92.1 (3)	O17—Cl1—O20	108.8 (3)
O6—Ca2—O8	133.0 (2)	O19—Cl1—O20	110.0 (5)
O11—Ca2—O9	152.3 (2)	O18—Cl1—O20	111.1 (5)
O6—Ca2—O9	105.0 (2)	O22—Cl2—O21	108.6 (7)
O8—Ca2—O9	96.8 (2)	O22—Cl2—O24	111.9 (4)
O11—Ca2—O7	77.6 (2)	O21—Cl2—O24	108.9 (4)
O6—Ca2—O7	148.20 (18)	O22—Cl2—O23	110.9 (4)
O8—Ca2—O7	76.1 (2)	O21—Cl2—O23	108.9 (4)
O9—Ca2—O7	79.2 (2)	O24—Cl2—O23	107.5 (5)
O11—Ca2—O10	80.3 (2)	Cl4—O16—Ca1	132.3 (5)
O6—Ca2—O10	75.00 (17)	Cl1—O18—Ca2	132.5 (5)
O8—Ca2—O10	151.0 (2)	Cl4—O13—Ca2	141.3 (3)
O9—Ca2—O10	79.2 (3)	Cl1—O17—Ca1	140.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O15	0.84 (2)	2.07 (3)	2.887 (10)	164 (8)
O1—H1B···O5ⁱ	0.84 (2)	2.25 (5)	2.915 (7)	136 (6)
O1—H1B···O16ⁱ	0.84 (2)	2.44 (5)	3.132 (10)	140 (6)
O2—H2A···O23ⁱⁱ	0.84 (2)	2.03 (2)	2.856 (9)	169 (7)
O2—H2B···O26ⁱⁱⁱ	0.84 (2)	2.14 (3)	2.932 (8)	155 (6)
O3—H3A···O12^iv	0.84 (2)	2.07 (2)	2.899 (8)	168 (8)
O3—H3B···O19ⁱⁱⁱ	0.84 (2)	2.15 (3)	2.934 (8)	156 (7)
O4—H4A···O27	0.84 (2)	2.28 (3)	3.074 (11)	158 (8)
O4—H4B···O28ⁱⁱⁱ	0.84 (2)	2.36 (3)	3.177 (10)	163 (8)
O5—H5A···O2^iv	0.84 (2)	1.98 (3)	2.783 (8)	159 (7)
O5—H5B···O19	0.84 (2)	2.20 (5)	2.903 (9)	142 (6)
O6—H6A···O8^v	0.84 (2)	2.18 (4)	2.925 (7)	149 (7)
O6—H6B···O19	0.84 (2)	2.08 (3)	2.891 (10)	162 (8)
O7—H7A···O23^vi	0.84 (2)	2.29 (4)	3.042 (9)	149 (6)
O7—H7B···O24^vii	0.84 (2)	2.50 (5)	3.199 (9)	141 (6)
O7—H7B···O27^viii	0.84 (2)	2.57 (5)	3.242 (11)	138 (6)
O8—H8A···O10^ix	0.84 (2)	2.08 (4)	2.805 (8)	145 (6)
O8—H8B···O15	0.84 (2)	2.07 (3)	2.879 (9)	162 (7)
O9—H9A···O27^x	0.84 (2)	2.06 (3)	2.865 (10)	161 (7)
O9—H9B···O21^vi	0.84 (2)	2.23 (5)	2.962 (10)	145 (7)
O10—H10A···O21^vii	0.84 (2)	2.12 (3)	2.930 (9)	163 (7)
O10—H10B···O28^x	0.84 (2)	2.10 (3)	2.902 (10)	162 (7)
O11—H11A···O9^ix	0.84 (2)	2.14 (4)	2.893 (9)	150 (7)
O11—H11B···O15^xi	0.84 (2)	2.11 (3)	2.915 (9)	161 (7)
O12—H12A···O26	0.84 (2)	2.35 (5)	2.995 (9)	135 (6)
O12—H12A···O20	0.84 (2)	2.40 (4)	3.102 (9)	142 (6)
O12—H12B···O24ⁱⁱ	0.84 (2)	2.03 (2)	2.861 (9)	171 (7)

Symmetry codes: (i) x+1/2, −y, z; (ii) x+1, y−1, z; (iii) x, y−1, z; (iv) x−1/2, −y, z; (v) x−1/2, −y+1, z; (vi) −x+1, −y+1, z−1/2; (vii) −x+1, −y+2, z−1/2; (viii) −x+2, −y+1, z−1/2; (ix) x+1/2, −y+1, z; (x) −x+3/2, y, z−1/2; (xi) x, y+1, z.

Hydrogen-bond geometry (Å, º) for (CaClO4_6H2O_180K) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O15	0.841 (15)	2.07 (3)	2.887 (10)	164 (8)
O1—H1B···O5ⁱ	0.838 (15)	2.25 (5)	2.915 (7)	136 (6)
O1—H1B···O16ⁱ	0.838 (15)	2.44 (5)	3.132 (10)	140 (6)
O2—H2A···O23ⁱⁱ	0.836 (15)	2.03 (2)	2.856 (9)	169 (7)
O2—H2B···O26ⁱⁱⁱ	0.843 (15)	2.14 (3)	2.932 (8)	155 (6)
O3—H3A···O12^iv	0.838 (15)	2.07 (2)	2.899 (8)	168 (8)
O3—H3B···O19ⁱⁱⁱ	0.838 (15)	2.15 (3)	2.934 (8)	156 (7)
O4—H4A···O27	0.841 (15)	2.28 (3)	3.074 (11)	158 (8)
O4—H4B···O28ⁱⁱⁱ	0.841 (15)	2.36 (3)	3.177 (10)	163 (8)
O5—H5A···O2^iv	0.837 (15)	1.98 (3)	2.783 (8)	159 (7)
O5—H5B···O19	0.838 (15)	2.20 (5)	2.903 (9)	142 (6)
O6—H6A···O8^v	0.837 (15)	2.18 (4)	2.925 (7)	149 (7)
O6—H6B···O19	0.840 (15)	2.08 (3)	2.891 (10)	162 (8)
O7—H7A···O23^vi	0.837 (15)	2.29 (4)	3.042 (9)	149 (6)
O7—H7B···O24^vii	0.840 (15)	2.50 (5)	3.199 (9)	141 (6)
O7—H7B···O27^viii	0.840 (15)	2.57 (5)	3.242 (11)	138 (6)
O8—H8A···O10^ix	0.837 (15)	2.08 (4)	2.805 (8)	145 (6)
O8—H8B···O15	0.838 (15)	2.07 (3)	2.879 (9)	162 (7)
O9—H9A···O27^x	0.838 (15)	2.06 (3)	2.865 (10)	161 (7)
O9—H9B···O21^vi	0.840 (15)	2.23 (5)	2.962 (10)	145 (7)
O10—H10A···O21^vii	0.840 (15)	2.12 (3)	2.930 (9)	163 (7)
O10—H10B···O28^x	0.836 (15)	2.10 (3)	2.902 (10)	162 (7)
O11—H11A···O9^ix	0.841 (15)	2.14 (4)	2.893 (9)	150 (7)
O11—H11B···O15^xi	0.841 (15)	2.11 (3)	2.915 (9)	161 (7)
O12—H12A···O26	0.837 (15)	2.35 (5)	2.995 (9)	135 (6)
O12—H12A···O20	0.837 (15)	2.40 (4)	3.102 (9)	142 (6)
O12—H12B···O24ⁱⁱ	0.838 (15)	2.03 (2)	2.861 (9)	171 (7)

Hydrogen-bond geometry (Å, º) for (CaClO4_4H2O_200K) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O11ⁱ	0.819 (10)	2.113 (15)	2.888 (2)	158 (3)
O1—H1A···O3ⁱⁱ	0.823 (10)	2.127 (10)	2.947 (2)	174 (3)
O2—H2A···O11ⁱⁱⁱ	0.822 (10)	2.166 (16)	2.947 (2)	159 (3)
O2—H2B···O4^iv	0.818 (10)	2.018 (11)	2.830 (2)	172 (3)
O7—H7B···O4	0.812 (10)	2.215 (18)	2.924 (2)	146 (3)
O7—H7A···O1ⁱⁱⁱ	0.817 (10)	2.059 (10)	2.870 (2)	172 (3)
O8—H8A···O4^v	0.822 (10)	2.33 (3)	2.986 (2)	137 (4)
O8—H8B···O2^vi	0.820 (10)	2.140 (13)	2.950 (2)	169 (5)

Symmetry codes: (i) −x, −y, −z+1; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y−1, z; (v) −x+1, −y+1, −z+2; (vi) x−1, y, z.

Experimental details

	Ca(ClO₄)₂·4H₂O	Ca(ClO₄)₂·6H₂O
Crystal data
M_r	311.04	347.08
Crystal system, space group	Triclinic, P1	Orthorhombic, Pca2₁
Temperature (K)	200	180
a, b, c (Å)	5.4886 (11), 7.8518 (15), 11.574 (2)	10.9603 (4), 7.9667 (7), 26.7735 (18)
α, β, γ (°)	99.663 (16), 90.366 (16), 90.244 (16)	90, 90, 90
V (Å³)	491.71 (17)	2337.8 (3)
Z	2	8
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	1.24	1.06
Crystal size (mm)	0.04 × 0.03 × 0.02	0.38 × 0.31 × 0.08

Data collection
Diffractometer	Stoe IPDS2 diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Integration Coppens (1970)	Integration (Coppens, 1970)
T_min, T_max	0.644, 0.789	0.684, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	2659, 2636, 2529	15755, 5326, 4919
R_int	0.074	0.062
(sin θ/λ)_max (Å⁻¹)	0.686	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.20	0.042, 0.113, 1.09
No. of reflections	2636	5326
No. of parameters	168	380
No. of restraints	12	37
H-atom treatment	All H-atom parameters refined	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.75	0.41, −0.67
Absolute structure	?	Refined as an inversion twin
Absolute structure parameter	?	0.45 (9)

Computer programs: X-AREA (Stoe & Cie, 2009), X-AREA(Stoe & Cie, 2009), X-RED (Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), SHELXL2012 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brown, I. D. (2002). In The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. Oxford University Press. Google Scholar
Chevrier, V. F., Hanley, J. & Altheide, T. S. (2009). Geophys. Res. Lett. 36, 1–6. Google Scholar
Coppens, P. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 255–270. Copenhagen: Munksgaard. Google Scholar
Davila, A. F., Willson, D., Coates, J. D. & McKay, C. P. (2013). Int. J. Astrobiology, 12, 321–325. Web of Science CrossRef CAS Google Scholar
Dobrynina, T. A. (1984). Zh. Neorg. Khim. 29, 1818–1822. CAS Google Scholar
Gallucci, J. C. & Gerkin, R. E. (1989). Acta Cryst. C45, 1279–1284. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ghosh, S., Mukherjee, M., Seal, A. & Ray, S. (1997). Acta Cryst. B53, 639–644. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ghosh, M. & Ray, S. (1981). Z. Kristallogr. 155, 129–137. CrossRef CAS Web of Science Google Scholar
Hennings, E., Schmidt, H. & Voigt, W. (2014). Acta Cryst. E70, 510–514. CSD CrossRef IUCr Journals Google Scholar
Johansson, G. & Sandström, M. (1978). Acta Chem. Scand. 32, 109–113. CrossRef Web of Science Google Scholar
Johansson, G., Sandström, M., Maartmann-Moe, K., Maberg, O., Scheie, A. & Louër, D. (1987). Acta Chem. Scand. Ser. A, 41, 113–116. CrossRef Web of Science Google Scholar
Johansson, G., Wallmark, I., Bergson, G., Ehrenberg, L., Brunvoll, J., Bunnenberg, E., Djerassi, C. & Records, R. (1966). Acta Chem. Scand. 20, 553–562. CrossRef CAS Web of Science Google Scholar
Kerr, R. A. (2013). Science, 340, 138. Google Scholar
Kim, Y. S., Wo, Y. S., Maity, S., Atreya, S. K. & Kaiser, R. I. (2013). J. Am. Chem. Soc. 135, 4910–4913. Web of Science CrossRef CAS PubMed Google Scholar
Lilich, L. S. & Djurinskii, B. F. (1956). Zh. Obshch. Khim. 26, 1549–1553. CAS Google Scholar
Mani, N. V. & Ramaseshan, S. (1961). Z. Kristallogr. 115, 97–109. CrossRef CAS Google Scholar
Marion, G. M., Catling, D. C., Zahnle, K. J. & Claire, M. W. (2010). Icarus, 207, 678–685. Web of Science CrossRef Google Scholar
Navarro-González, R., Vargas, E., de la Rosa, J., Raga, A. C. & McKay, C. P. (2010). J. Geophys. Res. 115, 1–11. Google Scholar
Nicholson, D. E. & Felsing, W. A. (1950). J. Am. Chem. Soc. 72, 4469–4471. CrossRef CAS Web of Science Google Scholar
Pestova, O. N., Myund, L. A., Khripun, M. K. & Prigaro, A. V. (2005). Russ. J. Appl. Chem. 78, 409–413. Web of Science CrossRef CAS Google Scholar
Quinn, R. C., Martucci, H. F. H., Miller, S. R., Bryson, C. E., Grunthaner, F. J. & Grunthaner, P. J. (2013). Astrobiology, 13, 515–520. Web of Science CrossRef CAS PubMed Google Scholar
Robertson, K. & Bish, D. (2010). Acta Cryst. B66, 579–584. Web of Science CrossRef IUCr Journals Google Scholar
Schuttlefield, J. D., Sambur, J. B., Gelwicks, M., Eggleston, C. M. & Parkinson, B. A. (2011). J. Am. Chem. Soc. 133, 17521–17523. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Solovyov, L. A. (2012). Acta Cryst. B68, 89–90. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (2009). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
West, C. D. (1935). Z. Kristallogr. 91, 480–493. CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Willard, H. H. & Smith, G. F. (1923). J. Am. Chem. Soc. 45, 286–297. CrossRef CAS Google Scholar

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Volume 70| Part 12| December 2014| Pages 489-493

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