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The crystal structure of the double salt hydro­nium penta­aqua­copper(II) triperchlorate, (H3O)[Cu(H2O)5](ClO4)3, has been determined at 180 K. In space group P3221, the structure contains a square-pyramidal [Cu(H2O)5]2+ moiety with its basal plane capped by one edge of a perchlorate anion, so that CuII exhibits [5+2] coordination. Both cations and one of the anions lie on twofold rotation axes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803014272/br6106sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803014272/br6106Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 180 K
  • Mean [sigma](Cl-O) = 0.007 Å
  • H-atom completeness 77%
  • R factor = 0.045
  • wR factor = 0.111
  • Data-to-parameter ratio = 13.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

PLATON alerts of the form PLAT_7?? have been detected for an inorganic
structure. These tests are under development  for inorganics and
comments are welcomed. It is not necessary to supply a data
validation response form for these alerts at this time.


Amber Alert Alert Level B:
CHEMS_01 Alert B The sum formula contains elements in the wrong order. H precedes Cl Sequence must be C, H, then alphabetical. PLAT_731 Alert B Bond Calc 0.88(5), Rep 0.890(10) ...... 5.00 su-Rat O1 -H1A 1.555 1.555 PLAT_731 Alert B Bond Calc 0.88(5), Rep 0.890(10) ...... 5.00 su-Rat O1 -H1B 1.555 1.555 PLAT_731 Alert B Bond Calc 0.88(6), Rep 0.880(10) ...... 6.00 su-Rat O2 -H2A 1.555 1.555 PLAT_731 Alert B Bond Calc 0.89(7), Rep 0.880(10) ...... 7.00 su-Rat O2 -H2B 1.555 1.555 PLAT_732 Alert B Angle Calc 110(11), Rep 110.4(18) ...... 6.11 su-Rat H2A -O2 -H2B 1.555 1.555 1.555 PLAT_735 Alert B D-H Calc 0.88(5), Rep 0.890(10) ...... 5.00 su-Rat O1 -H1B 1.555 1.555 PLAT_735 Alert B D-H Calc 0.88(5), Rep 0.890(10) ...... 5.00 su-Rat O1 -H1A 1.555 1.555 PLAT_735 Alert B D-H Calc 0.88(6), Rep 0.880(10) ...... 6.00 su-Rat O2 -H2A 1.555 1.555 PLAT_735 Alert B D-H Calc 0.89(7), Rep 0.880(10) ...... 7.00 su-Rat O2 -H2B 1.555 1.555
Yellow Alert Alert Level C:
PLAT_731 Alert C Bond Calc 1.413(13), Rep 1.412(6) ...... 2.17 su-Rat CL2 -O8 1.555 5.555 PLAT_731 Alert C Bond Calc 0.88(3), Rep 0.870(10) ...... 3.00 su-Rat O3 -H3A 1.555 1.555 PLAT_732 Alert C Angle Calc 109(6), Rep 109.0(17) ...... 3.53 su-Rat H1A -O1 -H1B 1.555 1.555 1.555 PLAT_735 Alert C D-H Calc 0.88(3), Rep 0.870(10) ...... 3.00 su-Rat O3 -H3A 1.555 1.555 PLAT_736 Alert C H...A Calc 2.44(7), Rep 2.44(3) ...... 2.33 su-Rat H2A -O4 1.555 1.655 General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:H13 Cl3 Cu1 O18 Atom count from the _atom_site data: H10 Cl3 Cu1 O18 CELLZ_01 From the CIF: _cell_formula_units_Z 3 From the CIF: _chemical_formula_sum H13 Cl3 Cu O18 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff H 39.00 30.00 9.00 Cl 9.00 9.00 0.00 Cu 3.00 3.00 0.00 O 54.00 54.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? REFLT_03 From the CIF: _diffrn_reflns_theta_max 26.36 From the CIF: _reflns_number_total 1610 Count of symmetry unique reflns 940 Completeness (_total/calc) 171.28% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 670 Fraction of Friedel pairs measured 0.713 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
10 Alert Level B = Potential problem
5 Alert Level C = Please check

Comment top

The perchlorate salt of CuII is most commonly isolated as the green–blue hexahydrate [Cu(H2O)6](ClO4)2, containing a Jahn–Teller-distorted octahedral hexaaquacopper(II) cation (Mani & Ramaseshan, 1961; Gallucci & Gerkin, 1989). We report here the crystal structure of a double salt, (H3O)[Cu(H2O)5](ClO4)3, incorporating pentaaquacopper(II) and a hydronium cation. In space group P3221, the axial Cu—OH2 vector of the square-pyramidal [Cu(H2O)52+] moiety is sited on a crystallographic twofold axis. The opposite face [O8i and O8ii; symmetry codes: (i) 1 + x, y, z; (ii): 1 + x-y, −y, 1/3 − z] of the basal plane is capped by one edge of a perchlorate anion, which is also sited on the twofold axis (Fig. 1). This gives rise to two additional Cu—O contacts of 3.305 (10) Å, so that the coordination arrangement around Cu2+ may be described as [5 + 2].

[5 + 2] coordination geometry is rare in CuII salts. The structures of other reported tetra-, penta- and hexaaquacopper(II) complexes show predominantly distorted octahedral geometry about Cu2+, either with six water ligands or a combination of water ligands and oxo donors from oxoanions (see, for example, Kennard et al., 1985; Manojlovic-Muir et al., 1999; Couldwell et al., 1978). Most notably, the comparable sulfate [Cu(H2O)5](SO4) contains Jahn–Teller-distorted octahedral [Cu(H2O)4(O)2] units, in which both axial sites are occupied by vertices of SO42− anions that bridge between two octahedral moieties (Beevers & Lipson, 1934; Baur & Rolin, 1972; Bacon & Curry, 1962; Varghese & Maslen, 1985). The fifth water molecule in the formula unit is uncoordinated. It is notable in the title compound that the displacement parameters of O8, O2 and O3 suggest some degree of disorder (static or dynamic) towards a distorted octahedral coordination geometry about Cu2+. It is possible that the [5 + 2] geometry is an averaged representation of local distorted octahedral arrangements. Apparent anomalies in the octahedral coordination geometries of Cu2+ have been discussed recently by Persson et al. (2002).

Experimental top

The title compound was isolated as a by-product of an attempted complexation of CuII by the polyol erythritol. A mixture of 0.2705 g (2.22 mmol) erythritol was dissolved in 8 ml me thanol by warming and vigorous stirring. The solution was cooled to room temperature and 0.4114 g (1.11 mmol) Cu(ClO4)2·6H2O was added. A 1 M solution of diethylamine in ethanol was diffused into this solution (vapour diffusion) and blue crystals of the title compound appeared after several months storage at room temperature.

Refinement top

H atoms associated with the water molecules of the [Cu(H2O)5]2+ moiety were located in difference Fourier maps and refined with O—H distances restrained to be 0.88 (1) Å and H···H distances restrained to be 1.44 (1) Å, ensuring a chemically reasonable geometry. Their displacement parameters were constrained so that Uiso(H) = 1.2Ueq(O). H atoms associated with the hydronium cation (sited on a twofold axis) were not apparent from difference Fourier maps, and were omitted from the final structure model. The hydronium atom occupies a cavity between eight potential hydrogen-bond acceptors, so that the H atoms are almost certainly disordered.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular units in the title compound, showing displacement ellipsoids at the 50% probability level. H atoms have been omitted from the hydronium cation (O100). Symmetry codes (i), (ii) and (iii) are as given in Table 1.
Hydronium pentaaquacopper(II) triperchlorate top
Crystal data top
(H3O)[Cu(H2O)5](ClO4)3Dx = 1.992 Mg m3
Mr = 470.99Mo Kα radiation, λ = 0.7107 Å
Trigonal, P3221Cell parameters from 2728 reflections
Hall symbol: P 32 2"θ = 2.3–26.0°
a = 10.1659 (7) ŵ = 1.99 mm1
c = 13.1601 (9) ÅT = 180 K
V = 1177.83 (14) Å3Block, blue
Z = 30.30 × 0.15 × 0.10 mm
F(000) = 711
Data collection top
Bruker SMART 1000 CCD
diffractometer
1610 independent reflections
Radiation source: fine-focus sealed tube1348 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
thin–slice ω scansθmax = 26.4°, θmin = 3.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1212
Tmin = 0.646, Tmax = 0.826k = 1112
7204 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Only H-atom coordinates refined
wR(F2) = 0.111 w = 1/[σ2(Fo2) + (0.0515P)2 + 2.6785P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1610 reflectionsΔρmax = 0.58 e Å3
118 parametersΔρmin = 0.55 e Å3
8 restraintsAbsolute structure: Flack (1983), 671 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (3)
Crystal data top
(H3O)[Cu(H2O)5](ClO4)3Z = 3
Mr = 470.99Mo Kα radiation
Trigonal, P3221µ = 1.99 mm1
a = 10.1659 (7) ÅT = 180 K
c = 13.1601 (9) Å0.30 × 0.15 × 0.10 mm
V = 1177.83 (14) Å3
Data collection top
Bruker SMART 1000 CCD
diffractometer
1610 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
1348 reflections with I > 2σ(I)
Tmin = 0.646, Tmax = 0.826Rint = 0.050
7204 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045Only H-atom coordinates refined
wR(F2) = 0.111Δρmax = 0.58 e Å3
S = 1.04Δρmin = 0.55 e Å3
1610 reflectionsAbsolute structure: Flack (1983), 671 Friedel pairs
118 parametersAbsolute structure parameter: 0.02 (3)
8 restraints
Special details top

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
Cu10.70337 (9)0.00000.16670.0232 (2)
Cl10.17902 (18)0.54783 (16)0.14489 (10)0.0294 (3)
Cl20.0840 (2)0.00000.16670.0328 (5)
O10.8015 (6)0.1870 (6)0.0803 (4)0.0546 (13)
H1A0.751 (6)0.185 (9)0.025 (3)0.066*
H1B0.9000 (17)0.238 (8)0.067 (4)0.066*
O20.7775 (13)0.1245 (8)0.2906 (5)0.139 (4)
H2A0.848 (12)0.220 (5)0.281 (9)0.166*
H2B0.740 (14)0.112 (13)0.353 (4)0.166*
O30.4752 (7)0.00000.16670.104 (4)
H3A0.467 (2)0.0813 (17)0.173 (9)0.125*
O40.0663 (5)0.4543 (5)0.2197 (3)0.0448 (12)
O50.1916 (8)0.6937 (6)0.1465 (4)0.0688 (19)
O60.1263 (8)0.4798 (7)0.0462 (4)0.0722 (17)
O70.3184 (6)0.5568 (8)0.1644 (5)0.0780 (19)
O80.0735 (12)0.1327 (11)0.1774 (5)0.118 (3)
O90.1730 (6)0.0179 (5)0.0797 (3)0.0469 (12)
O1000.3280 (5)0.3280 (5)0.00000.0440 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0238 (3)0.0229 (5)0.0227 (4)0.0114 (3)0.0036 (2)0.0071 (4)
Cl10.0287 (8)0.0273 (7)0.0307 (6)0.0129 (6)0.0003 (6)0.0033 (5)
Cl20.0326 (8)0.0484 (13)0.0227 (10)0.0242 (7)0.0016 (4)0.0032 (9)
O10.047 (3)0.055 (3)0.050 (3)0.016 (3)0.000 (2)0.001 (2)
O20.220 (11)0.055 (4)0.052 (4)0.002 (5)0.001 (5)0.021 (3)
O30.036 (3)0.083 (6)0.208 (12)0.042 (3)0.051 (4)0.101 (8)
O40.047 (3)0.044 (3)0.045 (3)0.024 (2)0.010 (2)0.008 (2)
O50.114 (5)0.040 (3)0.062 (3)0.047 (3)0.018 (3)0.005 (3)
O60.084 (4)0.079 (4)0.037 (2)0.028 (3)0.004 (3)0.018 (3)
O70.032 (3)0.092 (5)0.113 (5)0.032 (4)0.004 (3)0.005 (4)
O80.239 (10)0.180 (8)0.056 (3)0.196 (8)0.022 (5)0.016 (5)
O90.064 (3)0.039 (2)0.036 (2)0.024 (2)0.017 (2)0.0052 (19)
O1000.042 (3)0.042 (3)0.043 (3)0.018 (3)0.0010 (13)0.0010 (13)
Geometric parameters (Å, º) top
Cu1—O21.969 (6)Cl1—O41.449 (5)
Cu1—O2i1.969 (6)Cl2—O8i1.412 (6)
Cu1—O1i2.001 (5)Cl2—O81.412 (6)
Cu1—O12.001 (5)Cl2—O9i1.413 (4)
Cu1—O32.320 (7)Cl2—O91.413 (4)
Cu1—O8ii3.305 (10)O1—H1A0.89 (1)
Cu1—O8iii3.305 (10)O1—H1B0.89 (1)
Cl1—O71.398 (5)O2—H2A0.88 (1)
Cl1—O51.423 (5)O2—H2B0.88 (1)
Cl1—O61.443 (5)O3—H3A0.87 (1)
O2—Cu1—O2i172.9 (8)O8ii—Cu1—O8iii41.7 (3)
O2—Cu1—O1i89.2 (3)O7—Cl1—O5111.7 (4)
O2i—Cu1—O1i90.7 (3)O7—Cl1—O6108.5 (4)
O2—Cu1—O190.7 (3)O5—Cl1—O6109.3 (4)
O2i—Cu1—O189.2 (3)O7—Cl1—O4111.2 (3)
O1i—Cu1—O1177.3 (3)O5—Cl1—O4107.7 (3)
O2—Cu1—O393.5 (4)O6—Cl1—O4108.4 (3)
O2i—Cu1—O393.5 (4)O8i—Cl2—O8112.8 (9)
O1i—Cu1—O391.34 (17)O8i—Cl2—O9i107.9 (3)
O1—Cu1—O391.34 (17)O8—Cl2—O9i109.3 (4)
O2—Cu1—O8ii73.2 (4)O8i—Cl2—O9109.3 (4)
O2i—Cu1—O8ii100.0 (4)O8—Cl2—O9107.9 (3)
O1i—Cu1—O8ii104.2 (2)O9i—Cl2—O9109.7 (4)
O1—Cu1—O8ii73.2 (2)Cu1—O1—H1A116 (5)
O3—Cu1—O8ii159.15 (13)Cu1—O1—H1B123 (5)
O2—Cu1—O8iii100.0 (4)H1A—O1—H1B109.0 (17)
O2i—Cu1—O8iii73.2 (4)Cu1—O2—H2A116 (8)
O1i—Cu1—O8iii73.2 (2)Cu1—O2—H2B132 (8)
O1—Cu1—O8iii104.2 (2)H2A—O2—H2B110.4 (18)
O3—Cu1—O8iii159.15 (13)Cu1—O3—H3A124.5 (11)
Symmetry codes: (i) xy, y, z+1/3; (ii) x+1, y, z; (iii) xy+1, y, z+1/3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O6ii0.89 (1)2.40 (5)3.184 (8)148 (7)
O1—H1A···O5iv0.89 (1)2.34 (3)3.188 (7)161 (6)
O2—H2A···O4ii0.88 (1)2.44 (3)3.299 (10)165 (11)
O2—H2B···O7v0.88 (1)2.58 (7)3.343 (11)145 (10)
O3—H3A···O5vi0.87 (1)2.16 (1)3.017 (7)168 (2)
Symmetry codes: (ii) x+1, y, z; (iv) y, x, z; (v) x+1, x+y, z+2/3; (vi) xy+1, y+1, z+1/3.

Experimental details

Crystal data
Chemical formula(H3O)[Cu(H2O)5](ClO4)3
Mr470.99
Crystal system, space groupTrigonal, P3221
Temperature (K)180
a, c (Å)10.1659 (7), 13.1601 (9)
V3)1177.83 (14)
Z3
Radiation typeMo Kα
µ (mm1)1.99
Crystal size (mm)0.30 × 0.15 × 0.10
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.646, 0.826
No. of measured, independent and
observed [I > 2σ(I)] reflections
7204, 1610, 1348
Rint0.050
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.111, 1.04
No. of reflections1610
No. of parameters118
No. of restraints8
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.58, 0.55
Absolute structureFlack (1983), 671 Friedel pairs
Absolute structure parameter0.02 (3)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—O21.969 (6)Cu1—O32.320 (7)
Cu1—O2i1.969 (6)Cu1—O8ii3.305 (10)
Cu1—O1i2.001 (5)Cu1—O8iii3.305 (10)
Cu1—O12.001 (5)
O2—Cu1—O2i172.9 (8)O2—Cu1—O8ii73.2 (4)
O2—Cu1—O1i89.2 (3)O2i—Cu1—O8ii100.0 (4)
O2i—Cu1—O1i90.7 (3)O1i—Cu1—O8ii104.2 (2)
O1i—Cu1—O1177.3 (3)O3—Cu1—O8ii159.15 (13)
O2—Cu1—O393.5 (4)O8ii—Cu1—O8iii41.7 (3)
O1i—Cu1—O391.34 (17)
Symmetry codes: (i) xy, y, z+1/3; (ii) x+1, y, z; (iii) xy+1, y, z+1/3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O6ii0.89 (1)2.40 (5)3.184 (8)148 (7)
O1—H1A···O5iv0.89 (1)2.34 (3)3.188 (7)161 (6)
O2—H2A···O4ii0.88 (1)2.44 (3)3.299 (10)165 (11)
O2—H2B···O7v0.88 (1)2.58 (7)3.343 (11)145 (10)
O3—H3A···O5vi0.87 (1)2.16 (1)3.017 (7)168 (2)
Symmetry codes: (ii) x+1, y, z; (iv) y, x, z; (v) x+1, x+y, z+2/3; (vi) xy+1, y+1, z+1/3.
 

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