Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038688/ci2419sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038688/ci2419Isup2.hkl |
CCDC reference: 660078
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.005 Å
- R factor = 0.048
- wR factor = 0.158
- Data-to-parameter ratio = 17.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cr1 (4) 4.03 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 10
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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.
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).
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).
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)
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.
[Cr(C5H7O2)2(H2O)2]ClO4·H2O | F(000) = 836 |
Mr = 403.71 | Dx = 1.515 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 8910 reflections |
a = 9.9811 (3) Å | θ = 2.2–24.4° |
b = 14.8470 (5) Å | µ = 0.85 mm−1 |
c = 12.0093 (4) Å | T = 296 K |
β = 96.036 (2)° | Rectangular prism, purple |
V = 1769.78 (10) Å3 | 0.38 × 0.24 × 0.12 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 4051 independent reflections |
Radiation source: fine-focus sealed tube | 2771 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
φ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004a) | h = −12→12 |
Tmin = 0.776, Tmax = 0.894 | k = −19→19 |
38774 measured reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0777P)2 + 0.8712P] where P = (Fo2 + 2Fc2)/3 |
4051 reflections | (Δ/σ)max = 0.013 |
230 parameters | Δρmax = 0.64 e Å−3 |
10 restraints | Δρmin = −0.48 e Å−3 |
[Cr(C5H7O2)2(H2O)2]ClO4·H2O | V = 1769.78 (10) Å3 |
Mr = 403.71 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.9811 (3) Å | µ = 0.85 mm−1 |
b = 14.8470 (5) Å | T = 296 K |
c = 12.0093 (4) Å | 0.38 × 0.24 × 0.12 mm |
β = 96.036 (2)° |
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 = 0.894 | Rint = 0.047 |
38774 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 10 restraints |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.64 e Å−3 |
4051 reflections | Δρmin = −0.48 e Å−3 |
230 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of 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. |
x | y | z | Uiso*/Ueq | ||
Cr1 | 0.24915 (4) | 0.50161 (3) | 0.49777 (3) | 0.03861 (17) | |
O1 | 0.11295 (17) | 0.46012 (14) | 0.38113 (17) | 0.0464 (5) | |
O1W | 0.38847 (19) | 0.54583 (18) | 0.61600 (18) | 0.0569 (6) | |
H1WA | 0.4639 (19) | 0.560 (3) | 0.598 (3) | 0.085* | |
H1WB | 0.387 (3) | 0.547 (3) | 0.6849 (10) | 0.085* | |
O2 | 0.32828 (19) | 0.58155 (14) | 0.39606 (17) | 0.0495 (5) | |
O2W | 0.1230 (2) | 0.59873 (14) | 0.5386 (2) | 0.0586 (6) | |
H2WA | 0.048 (2) | 0.587 (2) | 0.558 (3) | 0.088* | |
H2WB | 0.137 (3) | 0.6545 (8) | 0.541 (4) | 0.088* | |
O3 | 0.17123 (19) | 0.42715 (13) | 0.60618 (16) | 0.0461 (5) | |
O4 | 0.36654 (18) | 0.40495 (13) | 0.45914 (16) | 0.0431 (4) | |
C1 | 0.0035 (4) | 0.4301 (3) | 0.2014 (3) | 0.0719 (10) | |
H1A | 0.0191 | 0.3663 | 0.2049 | 0.108* | |
H1B | 0.0050 | 0.4505 | 0.1257 | 0.108* | |
H1C | −0.0829 | 0.4432 | 0.2261 | 0.108* | |
C2 | 0.1115 (3) | 0.4776 (2) | 0.2757 (3) | 0.0509 (7) | |
C3 | 0.1994 (3) | 0.5354 (2) | 0.2309 (3) | 0.0595 (8) | |
H3 | 0.1903 | 0.5414 | 0.1534 | 0.071* | |
C4 | 0.3003 (3) | 0.5857 (2) | 0.2903 (3) | 0.0510 (7) | |
C5 | 0.3840 (4) | 0.6505 (3) | 0.2314 (3) | 0.0771 (11) | |
H5A | 0.3634 | 0.7110 | 0.2521 | 0.116* | |
H5B | 0.3643 | 0.6433 | 0.1519 | 0.116* | |
H5C | 0.4777 | 0.6386 | 0.2525 | 0.116* | |
C6 | 0.1033 (4) | 0.3005 (2) | 0.7020 (3) | 0.0628 (9) | |
H6A | 0.1092 | 0.3371 | 0.7682 | 0.094* | |
H6B | 0.1378 | 0.2415 | 0.7208 | 0.094* | |
H6C | 0.0110 | 0.2960 | 0.6710 | 0.094* | |
C7 | 0.1845 (3) | 0.3426 (2) | 0.6179 (2) | 0.0441 (6) | |
C8 | 0.2686 (3) | 0.2903 (2) | 0.5606 (3) | 0.0556 (8) | |
H8 | 0.2665 | 0.2285 | 0.5726 | 0.067* | |
C9 | 0.3560 (3) | 0.3215 (2) | 0.4869 (2) | 0.0473 (7) | |
C10 | 0.4473 (4) | 0.2596 (2) | 0.4342 (4) | 0.0744 (11) | |
H10A | 0.4384 | 0.2694 | 0.3548 | 0.112* | |
H10B | 0.4239 | 0.1984 | 0.4493 | 0.112* | |
H10C | 0.5387 | 0.2708 | 0.4644 | 0.112* | |
Cl1 | 0.18174 (9) | 0.84694 (6) | 0.48642 (9) | 0.0702 (3) | |
O5 | 0.2817 (4) | 0.9075 (2) | 0.5349 (3) | 0.1088 (11) | |
O6 | 0.2096 (5) | 0.8157 (3) | 0.3860 (4) | 0.166 (2) | |
O7 | 0.1774 (5) | 0.7744 (2) | 0.5643 (4) | 0.1472 (16) | |
O8 | 0.0575 (4) | 0.8874 (4) | 0.4839 (4) | 0.177 (2) | |
O3W | 0.3564 (3) | 0.5459 (2) | 0.8294 (2) | 0.0920 (9) | |
H3WB | 0.348 (5) | 0.4912 (10) | 0.847 (2) | 0.138* | |
H3WA | 0.428 (3) | 0.565 (3) | 0.864 (4) | 0.138* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.0244 (2) | 0.0459 (3) | 0.0472 (3) | −0.00116 (17) | 0.01153 (18) | 0.00286 (19) |
O1 | 0.0274 (9) | 0.0551 (12) | 0.0573 (12) | −0.0027 (8) | 0.0070 (8) | −0.0001 (9) |
O1W | 0.0329 (10) | 0.0875 (16) | 0.0521 (12) | −0.0158 (11) | 0.0127 (9) | −0.0069 (12) |
O2 | 0.0368 (10) | 0.0561 (12) | 0.0571 (13) | −0.0065 (9) | 0.0117 (9) | 0.0097 (10) |
O2W | 0.0368 (11) | 0.0475 (12) | 0.0960 (17) | −0.0007 (9) | 0.0283 (11) | −0.0014 (12) |
O3 | 0.0376 (10) | 0.0508 (11) | 0.0534 (11) | −0.0018 (9) | 0.0205 (8) | 0.0026 (9) |
O4 | 0.0293 (9) | 0.0504 (11) | 0.0523 (11) | 0.0028 (8) | 0.0172 (8) | 0.0012 (9) |
C1 | 0.060 (2) | 0.091 (3) | 0.064 (2) | −0.0085 (19) | 0.0011 (17) | −0.0121 (19) |
C2 | 0.0413 (15) | 0.0593 (18) | 0.0526 (17) | 0.0090 (14) | 0.0065 (13) | −0.0069 (14) |
C3 | 0.061 (2) | 0.069 (2) | 0.0494 (17) | −0.0020 (17) | 0.0136 (15) | 0.0018 (16) |
C4 | 0.0449 (16) | 0.0539 (17) | 0.0573 (18) | 0.0074 (14) | 0.0198 (14) | 0.0097 (14) |
C5 | 0.072 (2) | 0.088 (3) | 0.075 (2) | −0.008 (2) | 0.0251 (19) | 0.023 (2) |
C6 | 0.066 (2) | 0.065 (2) | 0.0618 (19) | −0.0130 (17) | 0.0282 (16) | 0.0053 (16) |
C7 | 0.0377 (14) | 0.0511 (17) | 0.0449 (15) | −0.0059 (12) | 0.0105 (11) | 0.0021 (12) |
C8 | 0.0567 (18) | 0.0443 (16) | 0.070 (2) | −0.0022 (14) | 0.0236 (15) | −0.0010 (14) |
C9 | 0.0352 (14) | 0.0525 (17) | 0.0547 (17) | 0.0007 (13) | 0.0078 (12) | −0.0051 (14) |
C10 | 0.066 (2) | 0.059 (2) | 0.104 (3) | 0.0101 (18) | 0.040 (2) | −0.012 (2) |
Cl1 | 0.0608 (5) | 0.0566 (5) | 0.0930 (7) | 0.0043 (4) | 0.0079 (4) | −0.0052 (5) |
O5 | 0.121 (3) | 0.087 (2) | 0.115 (2) | −0.035 (2) | 0.000 (2) | −0.0070 (18) |
O6 | 0.173 (4) | 0.198 (4) | 0.139 (3) | −0.079 (4) | 0.076 (3) | −0.095 (3) |
O7 | 0.197 (4) | 0.081 (2) | 0.160 (4) | −0.048 (3) | 0.000 (3) | 0.008 (2) |
O8 | 0.113 (3) | 0.242 (5) | 0.169 (4) | 0.100 (4) | −0.016 (3) | −0.030 (4) |
O3W | 0.097 (2) | 0.119 (2) | 0.0580 (15) | −0.0363 (19) | −0.0006 (14) | 0.0106 (16) |
Cr1—O2 | 1.9306 (19) | C4—C5 | 1.499 (4) |
Cr1—O3 | 1.9327 (19) | C5—H5A | 0.96 |
Cr1—O4 | 1.9396 (19) | C5—H5B | 0.96 |
Cr1—O1 | 1.947 (2) | C5—H5C | 0.96 |
Cr1—O1W | 1.991 (2) | C6—C7 | 1.496 (4) |
Cr1—O2W | 2.009 (2) | C6—H6A | 0.96 |
O1—C2 | 1.291 (4) | C6—H6B | 0.96 |
O1W—H1WA | 0.833 (10) | C6—H6C | 0.96 |
O1W—H1WB | 0.829 (10) | C7—C8 | 1.379 (4) |
O2—C4 | 1.272 (4) | C8—C9 | 1.387 (4) |
O2W—H2WA | 0.830 (10) | C8—H8 | 0.93 |
O2W—H2WB | 0.839 (10) | C9—C10 | 1.483 (4) |
O3—C7 | 1.269 (3) | C10—H10A | 0.96 |
O4—C9 | 1.290 (3) | C10—H10B | 0.96 |
C1—C2 | 1.502 (5) | C10—H10C | 0.96 |
C1—H1A | 0.96 | Cl1—O6 | 1.348 (4) |
C1—H1B | 0.96 | Cl1—O8 | 1.375 (4) |
C1—H1C | 0.96 | Cl1—O5 | 1.421 (3) |
C2—C3 | 1.376 (4) | Cl1—O7 | 1.430 (4) |
C3—C4 | 1.389 (5) | O3W—H3WA | 0.84 (4) |
C3—H3 | 0.93 | O3W—H3WB | 0.84 (1) |
O2—Cr1—O3 | 176.62 (8) | O2—C4—C3 | 123.9 (3) |
O2—Cr1—O4 | 90.34 (8) | O2—C4—C5 | 115.3 (3) |
O3—Cr1—O4 | 91.94 (8) | C3—C4—C5 | 120.8 (3) |
O2—Cr1—O1 | 92.32 (9) | C4—C5—H5A | 109.5 |
O3—Cr1—O1 | 90.21 (9) | C4—C5—H5B | 109.5 |
O4—Cr1—O1 | 89.28 (8) | H5A—C5—H5B | 109.5 |
O2—Cr1—O1W | 86.96 (9) | C4—C5—H5C | 109.5 |
O3—Cr1—O1W | 90.49 (9) | H5A—C5—H5C | 109.5 |
O4—Cr1—O1W | 91.17 (9) | H5B—C5—H5C | 109.5 |
O1—Cr1—O1W | 179.15 (9) | C7—C6—H6A | 109.5 |
O2—Cr1—O2W | 91.26 (9) | C7—C6—H6B | 109.5 |
O3—Cr1—O2W | 86.51 (9) | H6A—C6—H6B | 109.5 |
O4—Cr1—O2W | 178.13 (8) | C7—C6—H6C | 109.5 |
O1—Cr1—O2W | 89.69 (10) | H6A—C6—H6C | 109.5 |
O1W—Cr1—O2W | 89.88 (10) | H6B—C6—H6C | 109.5 |
C2—O1—Cr1 | 125.23 (19) | O3—C7—C8 | 124.3 (3) |
Cr1—O1W—H1WA | 119 (2) | O3—C7—C6 | 115.5 (3) |
Cr1—O1W—H1WB | 129 (2) | C8—C7—C6 | 120.2 (3) |
H1WA—O1W—H1WB | 111.2 (17) | C7—C8—C9 | 126.0 (3) |
C4—O2—Cr1 | 126.8 (2) | C7—C8—H8 | 117.0 |
Cr1—O2W—H2WA | 122 (2) | C9—C8—H8 | 117.0 |
Cr1—O2W—H2WB | 128 (2) | O4—C9—C8 | 124.0 (3) |
H2WA—O2W—H2WB | 110.0 (17) | O4—C9—C10 | 114.5 (3) |
C7—O3—Cr1 | 126.59 (18) | C8—C9—C10 | 121.4 (3) |
C9—O4—Cr1 | 125.53 (17) | C9—C10—H10A | 109.5 |
C2—C1—H1A | 109.5 | C9—C10—H10B | 109.5 |
C2—C1—H1B | 109.5 | H10A—C10—H10B | 109.5 |
H1A—C1—H1B | 109.5 | C9—C10—H10C | 109.5 |
C2—C1—H1C | 109.5 | H10A—C10—H10C | 109.5 |
H1A—C1—H1C | 109.5 | H10B—C10—H10C | 109.5 |
H1B—C1—H1C | 109.5 | O6—Cl1—O8 | 113.7 (3) |
O1—C2—C3 | 124.5 (3) | O6—Cl1—O5 | 112.4 (2) |
O1—C2—C1 | 115.0 (3) | O8—Cl1—O5 | 109.0 (3) |
C3—C2—C1 | 120.5 (3) | O6—Cl1—O7 | 110.5 (3) |
C2—C3—C4 | 126.3 (3) | O8—Cl1—O7 | 104.7 (4) |
C2—C3—H3 | 116.9 | O5—Cl1—O7 | 106.1 (2) |
C4—C3—H3 | 116.9 | H3WB—O3W—H3WA | 108 (2) |
O2—Cr1—O1—C2 | 9.8 (2) | Cr1—O1—C2—C3 | −6.5 (4) |
O3—Cr1—O1—C2 | −172.5 (2) | Cr1—O1—C2—C1 | 174.1 (2) |
O4—Cr1—O1—C2 | −80.6 (2) | O1—C2—C3—C4 | −1.8 (5) |
O2W—Cr1—O1—C2 | 101.0 (2) | C1—C2—C3—C4 | 177.6 (3) |
O4—Cr1—O2—C4 | 80.5 (2) | Cr1—O2—C4—C3 | 4.3 (4) |
O1—Cr1—O2—C4 | −8.8 (2) | Cr1—O2—C4—C5 | −176.3 (2) |
O1W—Cr1—O2—C4 | 171.7 (2) | C2—C3—C4—O2 | 3.1 (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—C8 | 6.4 (4) |
O1—Cr1—O3—C7 | 77.2 (2) | Cr1—O3—C7—C6 | −174.8 (2) |
O1W—Cr1—O3—C7 | −103.3 (2) | O3—C7—C8—C9 | 3.7 (5) |
O2W—Cr1—O3—C7 | 166.8 (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—C9 | 13.0 (2) | Cr1—O4—C9—C10 | 172.3 (2) |
O1—Cr1—O4—C9 | −77.2 (2) | C7—C8—C9—O4 | −2.5 (5) |
O1W—Cr1—O4—C9 | 103.5 (2) | C7—C8—C9—C10 | 176.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 0.83 (1) | 1.96 (2) | 2.791 (3) | 174 (3) |
O1W—H1WB···O3W | 0.83 (1) | 1.79 (1) | 2.616 (3) | 171 (3) |
O2W—H2WA···O1ii | 0.83 (1) | 1.96 (2) | 2.778 (3) | 169 (3) |
O2W—H2WB···O7 | 0.84 (1) | 1.84 (1) | 2.675 (4) | 173 (4) |
O3W—H3WA···O8iii | 0.84 (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. |
Experimental details
Crystal data | |
Chemical formula | [Cr(C5H7O2)2(H2O)2]ClO4·H2O |
Mr | 403.71 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 9.9811 (3), 14.8470 (5), 12.0093 (4) |
β (°) | 96.036 (2) |
V (Å3) | 1769.78 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.85 |
Crystal size (mm) | 0.38 × 0.24 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004a) |
Tmin, Tmax | 0.776, 0.894 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38774, 4051, 2771 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.158, 1.11 |
No. of reflections | 4051 |
No. of parameters | 230 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.64, −0.48 |
Computer programs: APEX2 (Bruker, 2004), APEX2, SHELXTL (Sheldrick, 2004b), SHELXTL.
Cr1—O2 | 1.9306 (19) | Cr1—O1 | 1.947 (2) |
Cr1—O3 | 1.9327 (19) | Cr1—O1W | 1.991 (2) |
Cr1—O4 | 1.9396 (19) | Cr1—O2W | 2.009 (2) |
O2—Cr1—O3 | 176.62 (8) | O4—Cr1—O1W | 91.17 (9) |
O2—Cr1—O4 | 90.34 (8) | O1—Cr1—O1W | 179.15 (9) |
O3—Cr1—O4 | 91.94 (8) | O2—Cr1—O2W | 91.26 (9) |
O2—Cr1—O1 | 92.32 (9) | O3—Cr1—O2W | 86.51 (9) |
O3—Cr1—O1 | 90.21 (9) | O4—Cr1—O2W | 178.13 (8) |
O4—Cr1—O1 | 89.28 (8) | O1—Cr1—O2W | 89.69 (10) |
O2—Cr1—O1W | 86.96 (9) | O1W—Cr1—O2W | 89.88 (10) |
O3—Cr1—O1W | 90.49 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 0.833 (10) | 1.96 (2) | 2.791 (3) | 174 (3) |
O1W—H1WB···O3W | 0.829 (10) | 1.79 (1) | 2.616 (3) | 171 (3) |
O2W—H2WA···O1ii | 0.830 (10) | 1.96 (2) | 2.778 (3) | 169 (3) |
O2W—H2WB···O7 | 0.839 (10) | 1.84 (1) | 2.675 (4) | 173 (4) |
O3W—H3WA···O8iii | 0.84 (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. |
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).