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Acta Cryst. (2007). E63, m2307    [ doi:10.1107/S1600536807038688 ]

cis-Bis(acetylacetonato)diaquachromium(III) perchlorate monohydrate

N. Arulsamy and J. L. Crawford

Abstract top

The Cr3+ center of the cation present in the title compound, [Cr(C5H7O2)2(H2O)2]ClO4·H2O, assumes a pseudo-octahedral geometry. The uncoordinated water molecule and the perchlorate anion are involved in moderately strong O-H...O hydrogen-bonding interactions with the cation, resulting in a three-dimensional network.

Comment top

Our interest in the title compound, (I), stems from its usefulness as a starting material for the synthesis of mixed ligand bis(acetylacetonato)Cr(III)-amino acidato complexes. We have obtained crystals of (I) as the major product together with the trans isomer from a modified literature procedure (Ogino et al., 1988).

In compound (I), two acetylacetonato ligands and two water molecules bind the Cr3+ center conferring pseudo-octahedral geometry to the metal ion (Fig. 1). The ions and the solvated water molecules are linked through hydrogen bonding. The hydrogen bonding interaction between the ions gives rise to a three-dimensional network as shown in Fig. 2.

Specifically, one of the coordinated water molecules (O1W) is hydrogen bonded to the solvated water molecule (O3W), whereas the other (O2W) is hydrogen bonded to a perchlorate O atom (O7). Each of the two water molecules is hydrogen bonded to a coordinated acetylacetonato anion through one of the O atoms of the latter ligand. In addition, the solvated water molecule (O3W) is also involved in a moderately strong hydrogen bonding with one of the perchlorate O atoms (O8).

Unlike in the structure of the corresponding tetrafluroborate salt (Nakano et al., 2003), the anion in (I) is ordered, possibly a consequence of the hydrogen bonds. The Cr—Oacac bonds are only slightly shorter (ca 0.06 Å) than the two Cr—Oaqua bonds indicating strong bonds with the water molecules as observed in the trans-bis(malonato)(diaqua)chromium(III) (Lemmer et al., 2002) and cis-bis(oxalato)diaquachromium(III) cations (Marinescu et al., 2002).

Related literature top

For synthesis, see: Ogino et al. (1988). Structural features observed for the cation in (I) are comparable to those reported for the cation in the corresponding tetrafluoroborate salt (Nakano et al., 2003). For related literature, see: Lemmer et al. (2002); Marinescu et al. (2002);

Experimental top

Compound (I) was obtained by the ligand exchange reaction of [Cr(acac)3] with water in the presene of perchloric acid by a modified literature procedure (Ogino et al., 1988), as follows: To a suspension of [Cr(acac)3] (6.981 g, 20 mmol) in water (200 ml) were added a solution of HClO4 (3 ml, 70% w/v) in water (50 ml) and ethanol (95%, 50 ml). The mixture was allowed to reflux for 5 d. The reaction mixture was treated following the literature method, rotary evaporated to ca 15 ml and allowed to stand at room temperature overnight. The cis and trans isomers of the complex crystallized as large purple and brown-purple rectangular prisms, respectively. A purple crystal of suitable size was chosen for the X-ray diffraction studies.

Refinement top

The water H atoms were located and refined, with the O—H and H···H distances restrained to 0.84 (1) and 1.37 (2) Å, respectively, and with Uiso(H) = 1.5Ueq(O). Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.96 Å and Uiso(H) = 1.2–1.5Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 2004b); 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 asymmetric unit of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres with arbitrary radii. Hydrogen bonds are represented by dashed lines.
[Figure 2] Fig. 2. The crystal packing of (I), viewed down the a axis.
cis-Bis(acetylacetonato)diaquachromium(III) perchlorate monohydrate top
Crystal data top
[Cr(C5H7O2)2(H2O)2]ClO4·H2OF000 = 836
Mr = 403.71Dx = 1.515 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8910 reflections
a = 9.9811 (3) Åθ = 2.2–24.4º
b = 14.8470 (5) ŵ = 0.85 mm−1
c = 12.0093 (4) ÅT = 296 (2) K
β = 96.036 (2)ºRectangular prism, purple
V = 1769.78 (10) Å30.38 × 0.24 × 0.12 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4051 independent reflections
Radiation source: fine-focus sealed tube2771 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
T = 296(2) Kθmax = 27.5º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004a)		h = −12→12
Tmin = 0.776, Tmax = 0.894k = −19→19
38774 measured reflectionsl = −15→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.158  w = 1/[σ2(Fo2) + (0.0777P)2 + 0.8712P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.013
4051 reflectionsΔρmax = 0.64 e Å−3
230 parametersΔρmin = −0.48 e Å−3
10 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cr(C5H7O2)2(H2O)2]ClO4·H2OV = 1769.78 (10) Å3
Mr = 403.71Z = 4
Monoclinic, P21/nMo Kα
a = 9.9811 (3) ŵ = 0.85 mm−1
b = 14.8470 (5) ÅT = 296 (2) K
c = 12.0093 (4) Å0.38 × 0.24 × 0.12 mm
β = 96.036 (2)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4051 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004a)		2771 reflections with I > 2σ(I)
Tmin = 0.776, Tmax = 0.894Rint = 0.047
38774 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04810 restraints
wR(F2) = 0.158H atoms treated by a mixture of
independent and constrained refinement
S = 1.11Δρmax = 0.64 e Å−3
4051 reflectionsΔρmin = −0.48 e Å−3
230 parameters
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 > 2sigma(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
Cr10.24915 (4)0.50161 (3)0.49777 (3)0.03861 (17)
O10.11295 (17)0.46012 (14)0.38113 (17)0.0464 (5)
O1W0.38847 (19)0.54583 (18)0.61600 (18)0.0569 (6)
H1WA0.4639 (19)0.560 (3)0.598 (3)0.085*
H1WB0.387 (3)0.547 (3)0.6849 (10)0.085*
O20.32828 (19)0.58155 (14)0.39606 (17)0.0495 (5)
O2W0.1230 (2)0.59873 (14)0.5386 (2)0.0586 (6)
H2WA0.048 (2)0.587 (2)0.558 (3)0.088*
H2WB0.137 (3)0.6545 (8)0.541 (4)0.088*
O30.17123 (19)0.42715 (13)0.60618 (16)0.0461 (5)
O40.36654 (18)0.40495 (13)0.45914 (16)0.0431 (4)
C10.0035 (4)0.4301 (3)0.2014 (3)0.0719 (10)
H1A0.01910.36630.20490.108*
H1B0.00500.45050.12570.108*
H1C−0.08290.44320.22610.108*
C20.1115 (3)0.4776 (2)0.2757 (3)0.0509 (7)
C30.1994 (3)0.5354 (2)0.2309 (3)0.0595 (8)
H30.19030.54140.15340.071*
C40.3003 (3)0.5857 (2)0.2903 (3)0.0510 (7)
C50.3840 (4)0.6505 (3)0.2314 (3)0.0771 (11)
H5A0.36340.71100.25210.116*
H5B0.36430.64330.15190.116*
H5C0.47770.63860.25250.116*
C60.1033 (4)0.3005 (2)0.7020 (3)0.0628 (9)
H6A0.10920.33710.76820.094*
H6B0.13780.24150.72080.094*
H6C0.01100.29600.67100.094*
C70.1845 (3)0.3426 (2)0.6179 (2)0.0441 (6)
C80.2686 (3)0.2903 (2)0.5606 (3)0.0556 (8)
H80.26650.22850.57260.067*
C90.3560 (3)0.3215 (2)0.4869 (2)0.0473 (7)
C100.4473 (4)0.2596 (2)0.4342 (4)0.0744 (11)
H10A0.43840.26940.35480.112*
H10B0.42390.19840.44930.112*
H10C0.53870.27080.46440.112*
Cl10.18174 (9)0.84694 (6)0.48642 (9)0.0702 (3)
O50.2817 (4)0.9075 (2)0.5349 (3)0.1088 (11)
O60.2096 (5)0.8157 (3)0.3860 (4)0.166 (2)
O70.1774 (5)0.7744 (2)0.5643 (4)0.1472 (16)
O80.0575 (4)0.8874 (4)0.4839 (4)0.177 (2)
O3W0.3564 (3)0.5459 (2)0.8294 (2)0.0920 (9)
H3WB0.348 (5)0.4912 (10)0.847 (2)0.138*
H3WA0.428 (3)0.565 (3)0.864 (4)0.138*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.0244 (2)0.0459 (3)0.0472 (3)−0.00116 (17)0.01153 (18)0.00286 (19)
O10.0274 (9)0.0551 (12)0.0573 (12)−0.0027 (8)0.0070 (8)−0.0001 (9)
O1W0.0329 (10)0.0875 (16)0.0521 (12)−0.0158 (11)0.0127 (9)−0.0069 (12)
O20.0368 (10)0.0561 (12)0.0571 (13)−0.0065 (9)0.0117 (9)0.0097 (10)
O2W0.0368 (11)0.0475 (12)0.0960 (17)−0.0007 (9)0.0283 (11)−0.0014 (12)
O30.0376 (10)0.0508 (11)0.0534 (11)−0.0018 (9)0.0205 (8)0.0026 (9)
O40.0293 (9)0.0504 (11)0.0523 (11)0.0028 (8)0.0172 (8)0.0012 (9)
C10.060 (2)0.091 (3)0.064 (2)−0.0085 (19)0.0011 (17)−0.0121 (19)
C20.0413 (15)0.0593 (18)0.0526 (17)0.0090 (14)0.0065 (13)−0.0069 (14)
C30.061 (2)0.069 (2)0.0494 (17)−0.0020 (17)0.0136 (15)0.0018 (16)
C40.0449 (16)0.0539 (17)0.0573 (18)0.0074 (14)0.0198 (14)0.0097 (14)
C50.072 (2)0.088 (3)0.075 (2)−0.008 (2)0.0251 (19)0.023 (2)
C60.066 (2)0.065 (2)0.0618 (19)−0.0130 (17)0.0282 (16)0.0053 (16)
C70.0377 (14)0.0511 (17)0.0449 (15)−0.0059 (12)0.0105 (11)0.0021 (12)
C80.0567 (18)0.0443 (16)0.070 (2)−0.0022 (14)0.0236 (15)−0.0010 (14)
C90.0352 (14)0.0525 (17)0.0547 (17)0.0007 (13)0.0078 (12)−0.0051 (14)
C100.066 (2)0.059 (2)0.104 (3)0.0101 (18)0.040 (2)−0.012 (2)
Cl10.0608 (5)0.0566 (5)0.0930 (7)0.0043 (4)0.0079 (4)−0.0052 (5)
O50.121 (3)0.087 (2)0.115 (2)−0.035 (2)0.000 (2)−0.0070 (18)
O60.173 (4)0.198 (4)0.139 (3)−0.079 (4)0.076 (3)−0.095 (3)
O70.197 (4)0.081 (2)0.160 (4)−0.048 (3)0.000 (3)0.008 (2)
O80.113 (3)0.242 (5)0.169 (4)0.100 (4)−0.016 (3)−0.030 (4)
O3W0.097 (2)0.119 (2)0.0580 (15)−0.0363 (19)−0.0006 (14)0.0106 (16)
Geometric parameters (Å, °) top
Cr1—O21.9306 (19)C4—C51.499 (4)
Cr1—O31.9327 (19)C5—H5A0.96
Cr1—O41.9396 (19)C5—H5B0.96
Cr1—O11.947 (2)C5—H5C0.96
Cr1—O1W1.991 (2)C6—C71.496 (4)
Cr1—O2W2.009 (2)C6—H6A0.96
O1—C21.291 (4)C6—H6B0.96
O1W—H1WA0.833 (10)C6—H6C0.96
O1W—H1WB0.829 (10)C7—C81.379 (4)
O2—C41.272 (4)C8—C91.387 (4)
O2W—H2WA0.830 (10)C8—H80.93
O2W—H2WB0.839 (10)C9—C101.483 (4)
O3—C71.269 (3)C10—H10A0.96
O4—C91.290 (3)C10—H10B0.96
C1—C21.502 (5)C10—H10C0.96
C1—H1A0.96Cl1—O61.348 (4)
C1—H1B0.96Cl1—O81.375 (4)
C1—H1C0.96Cl1—O51.421 (3)
C2—C31.376 (4)Cl1—O71.430 (4)
C3—C41.389 (5)O3W—H3WA0.84 (4)
C3—H30.93O3W—H3WB0.84 (1)
O2—Cr1—O3176.62 (8)O2—C4—C3123.9 (3)
O2—Cr1—O490.34 (8)O2—C4—C5115.3 (3)
O3—Cr1—O491.94 (8)C3—C4—C5120.8 (3)
O2—Cr1—O192.32 (9)C4—C5—H5A109.5
O3—Cr1—O190.21 (9)C4—C5—H5B109.5
O4—Cr1—O189.28 (8)H5A—C5—H5B109.5
O2—Cr1—O1W86.96 (9)C4—C5—H5C109.5
O3—Cr1—O1W90.49 (9)H5A—C5—H5C109.5
O4—Cr1—O1W91.17 (9)H5B—C5—H5C109.5
O1—Cr1—O1W179.15 (9)C7—C6—H6A109.5
O2—Cr1—O2W91.26 (9)C7—C6—H6B109.5
O3—Cr1—O2W86.51 (9)H6A—C6—H6B109.5
O4—Cr1—O2W178.13 (8)C7—C6—H6C109.5
O1—Cr1—O2W89.69 (10)H6A—C6—H6C109.5
O1W—Cr1—O2W89.88 (10)H6B—C6—H6C109.5
C2—O1—Cr1125.23 (19)O3—C7—C8124.3 (3)
Cr1—O1W—H1WA119 (2)O3—C7—C6115.5 (3)
Cr1—O1W—H1WB129 (2)C8—C7—C6120.2 (3)
H1WA—O1W—H1WB111.2 (17)C7—C8—C9126.0 (3)
C4—O2—Cr1126.8 (2)C7—C8—H8117.0
Cr1—O2W—H2WA122 (2)C9—C8—H8117.0
Cr1—O2W—H2WB128 (2)O4—C9—C8124.0 (3)
H2WA—O2W—H2WB110.0 (17)O4—C9—C10114.5 (3)
C7—O3—Cr1126.59 (18)C8—C9—C10121.4 (3)
C9—O4—Cr1125.53 (17)C9—C10—H10A109.5
C2—C1—H1A109.5C9—C10—H10B109.5
C2—C1—H1B109.5H10A—C10—H10B109.5
H1A—C1—H1B109.5C9—C10—H10C109.5
C2—C1—H1C109.5H10A—C10—H10C109.5
H1A—C1—H1C109.5H10B—C10—H10C109.5
H1B—C1—H1C109.5O6—Cl1—O8113.7 (3)
O1—C2—C3124.5 (3)O6—Cl1—O5112.4 (2)
O1—C2—C1115.0 (3)O8—Cl1—O5109.0 (3)
C3—C2—C1120.5 (3)O6—Cl1—O7110.5 (3)
C2—C3—C4126.3 (3)O8—Cl1—O7104.7 (4)
C2—C3—H3116.9O5—Cl1—O7106.1 (2)
C4—C3—H3116.9H3WB—O3W—H3WA108 (2)
O2—Cr1—O1—C29.8 (2)Cr1—O1—C2—C3−6.5 (4)
O3—Cr1—O1—C2−172.5 (2)Cr1—O1—C2—C1174.1 (2)
O4—Cr1—O1—C2−80.6 (2)O1—C2—C3—C4−1.8 (5)
O2W—Cr1—O1—C2101.0 (2)C1—C2—C3—C4177.6 (3)
O4—Cr1—O2—C480.5 (2)Cr1—O2—C4—C34.3 (4)
O1—Cr1—O2—C4−8.8 (2)Cr1—O2—C4—C5−176.3 (2)
O1W—Cr1—O2—C4171.7 (2)C2—C3—C4—O23.1 (5)
O2W—Cr1—O2—C4−98.5 (2)C2—C3—C4—C5−176.3 (3)
O4—Cr1—O3—C7−12.1 (2)Cr1—O3—C7—C86.4 (4)
O1—Cr1—O3—C777.2 (2)Cr1—O3—C7—C6−174.8 (2)
O1W—Cr1—O3—C7−103.3 (2)O3—C7—C8—C93.7 (5)
O2W—Cr1—O3—C7166.8 (2)C6—C7—C8—C9−175.1 (3)
O2—Cr1—O4—C9−169.5 (2)Cr1—O4—C9—C8−8.3 (4)
O3—Cr1—O4—C913.0 (2)Cr1—O4—C9—C10172.3 (2)
O1—Cr1—O4—C9−77.2 (2)C7—C8—C9—O4−2.5 (5)
O1W—Cr1—O4—C9103.5 (2)C7—C8—C9—C10176.8 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O4i0.833 (10)1.96 (2)2.791 (3)174 (3)
O1W—H1WB···O3W0.829 (10)1.79 (1)2.616 (3)171 (3)
O2W—H2WA···O1ii0.830 (10)1.96 (2)2.778 (3)169 (3)
O2W—H2WB···O70.839 (10)1.84 (1)2.675 (4)173 (4)
O3W—H3WA···O8iii0.84 (4)1.96 (2)2.770 (5)161 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x+1/2, −y+3/2, z+1/2.
Selected geometric parameters (Å, °) top
Cr1—O21.9306 (19)Cr1—O11.947 (2)
Cr1—O31.9327 (19)Cr1—O1W1.991 (2)
Cr1—O41.9396 (19)Cr1—O2W2.009 (2)
O2—Cr1—O3176.62 (8)O4—Cr1—O1W91.17 (9)
O2—Cr1—O490.34 (8)O1—Cr1—O1W179.15 (9)
O3—Cr1—O491.94 (8)O2—Cr1—O2W91.26 (9)
O2—Cr1—O192.32 (9)O3—Cr1—O2W86.51 (9)
O3—Cr1—O190.21 (9)O4—Cr1—O2W178.13 (8)
O4—Cr1—O189.28 (8)O1—Cr1—O2W89.69 (10)
O2—Cr1—O1W86.96 (9)O1W—Cr1—O2W89.88 (10)
O3—Cr1—O1W90.49 (9)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O4i0.833 (10)1.96 (2)2.791 (3)174 (3)
O1W—H1WB···O3W0.829 (10)1.79 (1)2.616 (3)171 (3)
O2W—H2WA···O1ii0.830 (10)1.96 (2)2.778 (3)169 (3)
O2W—H2WB···O70.839 (10)1.84 (1)2.675 (4)173 (4)
O3W—H3WA···O8iii0.84 (4)1.96 (2)2.770 (5)161 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x+1/2, −y+3/2, z+1/2.
Acknowledgements top

The authors thank the College of Arts and Sciences, University of Wyoming, for financial support (Basic Research Grant).

references
References top

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Sheldrick, G. M. (2004b). SHELXTL. Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA.