The β-diketone 3-(4-cyanophenyl)pentane-2,4-dione crystallizes as the enol tautomer 4-(2-hydroxy-4-oxopent-2-en-3-yl)benzonitrile, C
12H
11NO
2, (I), with an intramolecular O—H
O hydrogen bond [O
O = 2.456 (2) Å]. Reaction of (I) with copper acetate monohydrate in the presence of triethylamine leads to the formation of the copper(II) complex bis[3-(4-cyanophenyl)pentane-2,4-dionato-κ
2O,
O]copper(II), [Cu(C
12H
10NO
2)
2], (II). In the structure of (II), the Cu atom is coordinated by four β-diketonate O atoms in a slightly distorted square-planar geometry, with Cu—O distances in the range 1.8946 (11)–1.9092 (11) Å. The nitrile moieties in (II) make it a candidate for reaction with other metal ions to produce supramolecular structures.
Supporting information
CCDC references: 237904; 237905
3-(4-cyanophenyl)pentane-2,4-dione, (I), was synthesized according to the procedure of Dell'Erba et al. (1991) and crystallized from ether–dichloromethane (4:1 volume ratio). A solution of Hacac-Ph—CN (I) (0.05 g, 0.25 mmol) in ethanol (5 ml) was mixed with Cu(CH3COO)2(H2O) (0.05 g, 0.25 mmol) in H2O (5 ml), and several drops of triethylamine were added. Compound (II) precipitated and was collected in 65% yield. Recrystallization of the crude product from acetonitrile produced crystals suitable for X-ray analysis.
The hydroxy H-atom positional parameters for (I) were refined. All other H atoms were treated as riding in idealized positions, with C—H distances of 0.95–0.98 Å, depending on atom type. A torsional parameter was refined for each methyl group. Methyl group C5 in (I) is disordered, and this group and was modeled as six equally spaced half-occupied positions in the expected torus. Uiso(H) values were taken to be 1.2Ueq of the attached atom (1.5Ueq for hydroxy and methyl atoms).
For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(I) 4-(2-hydroxy-4-oxopent-2-en-3-yl)benzonitrile
top
Crystal data top
C12H11NO2 | F(000) = 424 |
Mr = 201.22 | Dx = 1.329 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1990 reflections |
a = 7.070 (5) Å | θ = 2.5–26.0° |
b = 11.644 (9) Å | µ = 0.09 mm−1 |
c = 12.2430 (11) Å | T = 100 K |
β = 94.035 (3)° | Plate fragment, colorless |
V = 1005.4 (11) Å3 | 0.20 × 0.10 × 0.07 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 1396 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 26.0°, θmin = 2.8° |
ω scans with κ offsets | h = −8→8 |
8931 measured reflections | k = −14→14 |
1969 independent reflections | l = −15→15 |
Refinement top
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0764P)2 + 0.1248P] where P = (Fo2 + 2Fc2)/3 |
1969 reflections | (Δ/σ)max < 0.001 |
140 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C12H11NO2 | V = 1005.4 (11) Å3 |
Mr = 201.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.070 (5) Å | µ = 0.09 mm−1 |
b = 11.644 (9) Å | T = 100 K |
c = 12.2430 (11) Å | 0.20 × 0.10 × 0.07 mm |
β = 94.035 (3)° | |
Data collection top
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 1396 reflections with I > 2σ(I) |
8931 measured reflections | Rint = 0.033 |
1969 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.22 e Å−3 |
1969 reflections | Δρmin = −0.25 e Å−3 |
140 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 > 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.48769 (19) | 0.31127 (11) | 0.99362 (10) | 0.0310 (4) | |
O2 | 0.7718 (2) | 0.42543 (12) | 0.96421 (11) | 0.0335 (4) | |
H2O | 0.670 (4) | 0.367 (2) | 0.9953 (19) | 0.050* | |
N1 | 0.0985 (3) | 0.67949 (15) | 0.37053 (15) | 0.0403 (5) | |
C1 | 0.2021 (3) | 0.32336 (17) | 0.88139 (17) | 0.0321 (5) | |
H1A | 0.1692 | 0.2579 | 0.9267 | 0.048* | |
H1B | 0.1836 | 0.3023 | 0.8039 | 0.048* | |
H1C | 0.1206 | 0.3888 | 0.8962 | 0.048* | |
C2 | 0.4040 (3) | 0.35524 (15) | 0.90779 (15) | 0.0275 (4) | |
C3 | 0.4987 (3) | 0.43567 (15) | 0.84266 (15) | 0.0263 (4) | |
C4 | 0.6824 (3) | 0.46915 (16) | 0.87613 (16) | 0.0285 (5) | |
C5 | 0.7940 (3) | 0.55509 (18) | 0.81730 (18) | 0.0360 (5) | |
H5A | 0.9189 | 0.5649 | 0.8562 | 0.054* | 0.50 |
H5B | 0.7268 | 0.6288 | 0.8144 | 0.054* | 0.50 |
H5C | 0.8096 | 0.5281 | 0.7427 | 0.054* | 0.50 |
H5D | 0.7180 | 0.5829 | 0.7527 | 0.054* | 0.50 |
H5E | 0.9101 | 0.5191 | 0.7944 | 0.054* | 0.50 |
H5F | 0.8273 | 0.6198 | 0.8662 | 0.054* | 0.50 |
C6 | 0.4002 (3) | 0.48581 (16) | 0.74187 (15) | 0.0268 (4) | |
C7 | 0.3844 (3) | 0.42415 (16) | 0.64429 (15) | 0.0291 (5) | |
H7 | 0.4316 | 0.3478 | 0.6427 | 0.035* | |
C8 | 0.3006 (3) | 0.47256 (16) | 0.54949 (15) | 0.0304 (5) | |
H8 | 0.2913 | 0.4298 | 0.4832 | 0.036* | |
C9 | 0.2301 (3) | 0.58387 (16) | 0.55163 (15) | 0.0290 (5) | |
C10 | 0.2403 (3) | 0.64582 (16) | 0.64914 (16) | 0.0300 (5) | |
H10 | 0.1898 | 0.7213 | 0.6510 | 0.036* | |
C11 | 0.3244 (3) | 0.59677 (16) | 0.74305 (16) | 0.0300 (5) | |
H11 | 0.3309 | 0.6390 | 0.8096 | 0.036* | |
C12 | 0.1552 (3) | 0.63711 (17) | 0.45117 (17) | 0.0320 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0359 (8) | 0.0286 (7) | 0.0281 (7) | 0.0019 (6) | 0.0002 (6) | 0.0040 (6) |
O2 | 0.0336 (8) | 0.0337 (8) | 0.0324 (8) | 0.0024 (6) | −0.0040 (6) | 0.0001 (6) |
N1 | 0.0445 (11) | 0.0397 (10) | 0.0355 (10) | −0.0073 (9) | −0.0045 (8) | 0.0044 (8) |
C1 | 0.0329 (11) | 0.0299 (10) | 0.0336 (10) | −0.0008 (8) | 0.0033 (8) | 0.0055 (9) |
C2 | 0.0338 (11) | 0.0218 (9) | 0.0270 (10) | 0.0043 (8) | 0.0025 (8) | −0.0031 (8) |
C3 | 0.0301 (11) | 0.0224 (9) | 0.0264 (10) | 0.0023 (8) | 0.0019 (8) | −0.0002 (8) |
C4 | 0.0318 (11) | 0.0249 (9) | 0.0290 (10) | 0.0045 (8) | 0.0027 (8) | −0.0035 (8) |
C5 | 0.0326 (11) | 0.0342 (11) | 0.0413 (12) | −0.0037 (9) | 0.0028 (9) | 0.0025 (9) |
C6 | 0.0265 (10) | 0.0255 (10) | 0.0288 (10) | −0.0014 (8) | 0.0038 (8) | 0.0012 (8) |
C7 | 0.0337 (11) | 0.0232 (9) | 0.0305 (10) | −0.0003 (8) | 0.0019 (8) | 0.0012 (8) |
C8 | 0.0354 (11) | 0.0295 (10) | 0.0260 (10) | −0.0055 (9) | 0.0010 (9) | −0.0019 (8) |
C9 | 0.0271 (10) | 0.0306 (10) | 0.0290 (10) | −0.0049 (8) | −0.0001 (8) | 0.0051 (8) |
C10 | 0.0315 (11) | 0.0264 (10) | 0.0320 (10) | 0.0011 (8) | 0.0009 (8) | 0.0030 (8) |
C11 | 0.0356 (11) | 0.0279 (10) | 0.0263 (10) | 0.0013 (8) | 0.0023 (8) | −0.0014 (8) |
C12 | 0.0309 (11) | 0.0318 (11) | 0.0328 (11) | −0.0043 (9) | −0.0014 (9) | 0.0013 (9) |
Geometric parameters (Å, º) top
O1—C2 | 1.276 (2) | C5—H5D | 0.9800 |
O2—C4 | 1.314 (2) | C5—H5E | 0.9800 |
O2—H2O | 1.08 (3) | C5—H5F | 0.9800 |
N1—C12 | 1.150 (3) | C6—C7 | 1.392 (3) |
C1—C2 | 1.489 (3) | C6—C11 | 1.399 (3) |
C1—H1A | 0.9800 | C7—C8 | 1.385 (3) |
C1—H1B | 0.9800 | C7—H7 | 0.9500 |
C1—H1C | 0.9800 | C8—C9 | 1.390 (3) |
C2—C3 | 1.427 (3) | C8—H8 | 0.9500 |
C3—C4 | 1.389 (3) | C9—C10 | 1.392 (3) |
C3—C6 | 1.493 (3) | C9—C12 | 1.444 (3) |
C4—C5 | 1.491 (3) | C10—C11 | 1.380 (3) |
C5—H5A | 0.9800 | C10—H10 | 0.9500 |
C5—H5B | 0.9800 | C11—H11 | 0.9500 |
C5—H5C | 0.9800 | | |
| | | |
C2—O1—H2O | 101.2 (10) | H5B—C5—H5E | 141.1 |
C4—O2—H2O | 104.0 (13) | H5C—C5—H5E | 56.3 |
C2—C1—H1A | 109.5 | H5D—C5—H5E | 109.5 |
C2—C1—H1B | 109.5 | C4—C5—H5F | 109.5 |
H1A—C1—H1B | 109.5 | H5A—C5—H5F | 56.3 |
C2—C1—H1C | 109.5 | H5B—C5—H5F | 56.3 |
H1A—C1—H1C | 109.5 | H5C—C5—H5F | 141.1 |
H1B—C1—H1C | 109.5 | H5D—C5—H5F | 109.5 |
O1—C2—C3 | 120.99 (18) | H5E—C5—H5F | 109.5 |
O1—C2—C1 | 117.42 (17) | C7—C6—C11 | 118.52 (17) |
C3—C2—C1 | 121.53 (17) | C7—C6—C3 | 120.84 (16) |
C4—C3—C2 | 119.00 (17) | C11—C6—C3 | 120.63 (16) |
C4—C3—C6 | 120.40 (17) | C8—C7—C6 | 120.87 (18) |
C2—C3—C6 | 120.58 (17) | C8—C7—H7 | 119.6 |
O2—C4—C3 | 121.28 (18) | C6—C7—H7 | 119.6 |
O2—C4—C5 | 114.57 (18) | C7—C8—C9 | 119.78 (18) |
C3—C4—C5 | 124.14 (18) | C7—C8—H8 | 120.1 |
C4—C5—H5A | 109.5 | C9—C8—H8 | 120.1 |
C4—C5—H5B | 109.5 | C8—C9—C10 | 120.15 (17) |
H5A—C5—H5B | 109.5 | C8—C9—C12 | 119.66 (17) |
C4—C5—H5C | 109.5 | C10—C9—C12 | 120.11 (18) |
H5A—C5—H5C | 109.5 | C11—C10—C9 | 119.56 (18) |
H5B—C5—H5C | 109.5 | C11—C10—H10 | 120.2 |
C4—C5—H5D | 109.5 | C9—C10—H10 | 120.2 |
H5A—C5—H5D | 141.1 | C10—C11—C6 | 121.08 (18) |
H5B—C5—H5D | 56.3 | C10—C11—H11 | 119.5 |
H5C—C5—H5D | 56.3 | C6—C11—H11 | 119.5 |
C4—C5—H5E | 109.5 | N1—C12—C9 | 178.9 (2) |
H5A—C5—H5E | 56.3 | | |
| | | |
O1—C2—C3—C4 | −2.4 (3) | C2—C3—C6—C11 | 101.4 (2) |
C1—C2—C3—C4 | 174.87 (17) | C11—C6—C7—C8 | 1.9 (3) |
O1—C2—C3—C6 | 179.45 (16) | C3—C6—C7—C8 | −177.06 (18) |
C1—C2—C3—C6 | −3.3 (3) | C6—C7—C8—C9 | −0.4 (3) |
C2—C3—C4—O2 | 2.3 (3) | C7—C8—C9—C10 | −1.2 (3) |
C6—C3—C4—O2 | −179.55 (16) | C7—C8—C9—C12 | 175.55 (18) |
C2—C3—C4—C5 | −178.01 (17) | C8—C9—C10—C11 | 1.3 (3) |
C6—C3—C4—C5 | 0.2 (3) | C12—C9—C10—C11 | −175.43 (18) |
C4—C3—C6—C7 | 102.1 (2) | C9—C10—C11—C6 | 0.2 (3) |
C2—C3—C6—C7 | −79.7 (2) | C7—C6—C11—C10 | −1.8 (3) |
C4—C3—C6—C11 | −76.8 (3) | C3—C6—C11—C10 | 177.17 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O1 | 1.08 (3) | 1.44 (3) | 2.456 (2) | 153 (2) |
(II) bis[3-(4-cyanophenyl)pentane-2,4-dionato-
κ2O,
O]copper(II)
top
Crystal data top
[Cu(C12H10NO2)2] | Z = 2 |
Mr = 463.96 | F(000) = 478 |
Triclinic, P1 | Dx = 1.512 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6087 (10) Å | Cell parameters from 6559 reflections |
b = 9.260 (2) Å | θ = 2.5–32.0° |
c = 15.198 (3) Å | µ = 1.11 mm−1 |
α = 91.327 (8)° | T = 100 K |
β = 92.814 (8)° | Fragment, blue-green |
γ = 107.509 (12)° | 0.22 × 0.10 × 0.07 mm |
V = 1019.1 (3) Å3 | |
Data collection top
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 7082 independent reflections |
Radiation source: fine-focus sealed tube | 5681 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans with κ offsets | θmax = 32.1°, θmin = 2.6° |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | h = −10→11 |
Tmin = 0.793, Tmax = 0.927 | k = −13→13 |
31552 measured reflections | l = −22→22 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.023P)2 + 0.7093P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
7082 reflections | Δρmax = 0.44 e Å−3 |
285 parameters | Δρmin = −0.53 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0019 (6) |
Crystal data top
[Cu(C12H10NO2)2] | γ = 107.509 (12)° |
Mr = 463.96 | V = 1019.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6087 (10) Å | Mo Kα radiation |
b = 9.260 (2) Å | µ = 1.11 mm−1 |
c = 15.198 (3) Å | T = 100 K |
α = 91.327 (8)° | 0.22 × 0.10 × 0.07 mm |
β = 92.814 (8)° | |
Data collection top
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 7082 independent reflections |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | 5681 reflections with I > 2σ(I) |
Tmin = 0.793, Tmax = 0.927 | Rint = 0.030 |
31552 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.44 e Å−3 |
7082 reflections | Δρmin = −0.53 e Å−3 |
285 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 > 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 | x | y | z | Uiso*/Ueq | |
Cu1 | 0.30072 (3) | 0.69219 (2) | 0.434532 (12) | 0.01640 (6) | |
O1 | 0.50600 (15) | 0.62536 (14) | 0.41004 (7) | 0.0192 (2) | |
O2 | 0.17323 (15) | 0.60823 (14) | 0.32549 (7) | 0.0190 (2) | |
O3 | 0.07902 (15) | 0.71769 (14) | 0.47396 (7) | 0.0199 (2) | |
O4 | 0.44600 (15) | 0.82044 (13) | 0.52842 (7) | 0.0178 (2) | |
N1 | 0.5919 (2) | 0.15695 (18) | −0.10331 (10) | 0.0281 (3) | |
N2 | 0.0244 (2) | 1.22657 (18) | 0.97707 (10) | 0.0247 (3) | |
C1 | 0.6982 (2) | 0.50069 (19) | 0.34782 (11) | 0.0191 (3) | |
H1A | 0.7994 | 0.5789 | 0.3234 | 0.029* | |
H1B | 0.6763 | 0.4049 | 0.3139 | 0.029* | |
H1C | 0.7310 | 0.4870 | 0.4096 | 0.029* | |
C2 | 0.5258 (2) | 0.54869 (18) | 0.34249 (10) | 0.0160 (3) | |
C3 | 0.4001 (2) | 0.50698 (18) | 0.26789 (10) | 0.0153 (3) | |
C4 | 0.2314 (2) | 0.54150 (18) | 0.26348 (10) | 0.0161 (3) | |
C5 | 0.1034 (2) | 0.5029 (2) | 0.18164 (10) | 0.0194 (3) | |
H5A | −0.0238 | 0.4879 | 0.1978 | 0.029* | |
H5B | 0.1124 | 0.4097 | 0.1530 | 0.029* | |
H5C | 0.1384 | 0.5860 | 0.1409 | 0.029* | |
C6 | 0.4490 (2) | 0.42633 (18) | 0.19088 (10) | 0.0152 (3) | |
C7 | 0.5900 (2) | 0.50294 (19) | 0.13793 (10) | 0.0184 (3) | |
H7 | 0.6568 | 0.6058 | 0.1524 | 0.022* | |
C8 | 0.6342 (2) | 0.43164 (19) | 0.06464 (11) | 0.0195 (3) | |
H8 | 0.7313 | 0.4849 | 0.0297 | 0.023* | |
C9 | 0.5349 (2) | 0.28088 (19) | 0.04277 (11) | 0.0182 (3) | |
C10 | 0.3959 (2) | 0.20118 (19) | 0.09581 (11) | 0.0192 (3) | |
H10 | 0.3300 | 0.0980 | 0.0817 | 0.023* | |
C11 | 0.3550 (2) | 0.27416 (18) | 0.16924 (11) | 0.0181 (3) | |
H11 | 0.2612 | 0.2196 | 0.2055 | 0.022* | |
C12 | 0.5689 (2) | 0.2104 (2) | −0.03774 (11) | 0.0213 (3) | |
C13 | −0.1417 (2) | 0.7632 (2) | 0.56388 (11) | 0.0226 (3) | |
H13A | −0.1795 | 0.8459 | 0.5379 | 0.034* | |
H13B | −0.1551 | 0.7651 | 0.6277 | 0.034* | |
H13C | −0.2197 | 0.6660 | 0.5376 | 0.034* | |
C14 | 0.0572 (2) | 0.78264 (19) | 0.54615 (10) | 0.0169 (3) | |
C15 | 0.2016 (2) | 0.86747 (18) | 0.60544 (10) | 0.0147 (3) | |
C16 | 0.3885 (2) | 0.88461 (18) | 0.59124 (10) | 0.0158 (3) | |
C17 | 0.5394 (2) | 0.9829 (2) | 0.65382 (11) | 0.0203 (3) | |
H17A | 0.5567 | 0.9246 | 0.7048 | 0.030* | |
H17B | 0.5048 | 1.0715 | 0.6738 | 0.030* | |
H17C | 0.6547 | 1.0165 | 0.6235 | 0.030* | |
C18 | 0.1553 (2) | 0.94125 (18) | 0.68629 (10) | 0.0153 (3) | |
C19 | 0.0813 (2) | 1.06172 (19) | 0.67991 (10) | 0.0184 (3) | |
H19 | 0.0593 | 1.0970 | 0.6235 | 0.022* | |
C20 | 0.0393 (2) | 1.13089 (19) | 0.75461 (10) | 0.0189 (3) | |
H20 | −0.0140 | 1.2111 | 0.7493 | 0.023* | |
C21 | 0.0760 (2) | 1.08144 (18) | 0.83754 (10) | 0.0170 (3) | |
C22 | 0.1503 (2) | 0.96118 (19) | 0.84553 (10) | 0.0187 (3) | |
H22 | 0.1747 | 0.9273 | 0.9020 | 0.022* | |
C23 | 0.1879 (2) | 0.89181 (19) | 0.76992 (10) | 0.0179 (3) | |
H23 | 0.2367 | 0.8091 | 0.7751 | 0.021* | |
C24 | 0.0445 (2) | 1.1598 (2) | 0.91583 (10) | 0.0192 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01405 (10) | 0.02094 (11) | 0.01507 (10) | 0.00703 (7) | −0.00001 (7) | −0.00351 (7) |
O1 | 0.0163 (5) | 0.0254 (6) | 0.0175 (5) | 0.0093 (5) | −0.0013 (4) | −0.0056 (5) |
O2 | 0.0161 (5) | 0.0263 (6) | 0.0160 (5) | 0.0091 (5) | −0.0007 (4) | −0.0052 (4) |
O3 | 0.0148 (5) | 0.0282 (7) | 0.0171 (5) | 0.0080 (5) | −0.0004 (4) | −0.0067 (5) |
O4 | 0.0139 (5) | 0.0222 (6) | 0.0174 (5) | 0.0061 (4) | 0.0002 (4) | −0.0044 (4) |
N1 | 0.0288 (8) | 0.0270 (8) | 0.0286 (8) | 0.0088 (7) | 0.0032 (6) | −0.0085 (6) |
N2 | 0.0277 (8) | 0.0267 (8) | 0.0197 (7) | 0.0080 (6) | 0.0035 (6) | −0.0022 (6) |
C1 | 0.0165 (7) | 0.0219 (8) | 0.0206 (7) | 0.0092 (6) | −0.0020 (6) | −0.0030 (6) |
C2 | 0.0141 (7) | 0.0180 (7) | 0.0159 (7) | 0.0049 (6) | 0.0010 (5) | 0.0000 (6) |
C3 | 0.0150 (7) | 0.0159 (7) | 0.0152 (7) | 0.0050 (6) | 0.0014 (5) | −0.0012 (5) |
C4 | 0.0151 (7) | 0.0170 (7) | 0.0157 (7) | 0.0044 (6) | 0.0007 (5) | −0.0002 (6) |
C5 | 0.0160 (7) | 0.0256 (9) | 0.0175 (7) | 0.0086 (6) | −0.0016 (6) | −0.0036 (6) |
C6 | 0.0132 (7) | 0.0178 (7) | 0.0153 (7) | 0.0060 (6) | −0.0003 (5) | 0.0004 (6) |
C7 | 0.0172 (7) | 0.0177 (8) | 0.0188 (7) | 0.0033 (6) | 0.0005 (6) | −0.0035 (6) |
C8 | 0.0167 (7) | 0.0216 (8) | 0.0184 (7) | 0.0032 (6) | 0.0027 (6) | −0.0025 (6) |
C9 | 0.0164 (7) | 0.0205 (8) | 0.0191 (7) | 0.0084 (6) | −0.0008 (6) | −0.0034 (6) |
C10 | 0.0175 (7) | 0.0155 (7) | 0.0241 (8) | 0.0047 (6) | 0.0000 (6) | −0.0026 (6) |
C11 | 0.0157 (7) | 0.0179 (8) | 0.0204 (7) | 0.0045 (6) | 0.0021 (6) | 0.0004 (6) |
C12 | 0.0182 (7) | 0.0205 (8) | 0.0256 (8) | 0.0069 (6) | −0.0003 (6) | −0.0037 (6) |
C13 | 0.0152 (7) | 0.0323 (10) | 0.0193 (8) | 0.0062 (7) | 0.0005 (6) | −0.0065 (7) |
C14 | 0.0164 (7) | 0.0206 (8) | 0.0147 (7) | 0.0074 (6) | 0.0008 (5) | −0.0005 (6) |
C15 | 0.0150 (7) | 0.0176 (7) | 0.0125 (6) | 0.0066 (6) | 0.0006 (5) | 0.0010 (5) |
C16 | 0.0166 (7) | 0.0171 (7) | 0.0143 (7) | 0.0058 (6) | 0.0002 (5) | 0.0013 (5) |
C17 | 0.0164 (7) | 0.0240 (8) | 0.0187 (7) | 0.0038 (6) | 0.0001 (6) | −0.0020 (6) |
C18 | 0.0159 (7) | 0.0165 (7) | 0.0131 (6) | 0.0048 (6) | 0.0000 (5) | −0.0007 (5) |
C19 | 0.0207 (8) | 0.0223 (8) | 0.0140 (7) | 0.0093 (6) | −0.0009 (6) | 0.0001 (6) |
C20 | 0.0201 (7) | 0.0204 (8) | 0.0180 (7) | 0.0088 (6) | 0.0003 (6) | −0.0012 (6) |
C21 | 0.0142 (7) | 0.0189 (8) | 0.0157 (7) | 0.0015 (6) | 0.0023 (5) | −0.0017 (6) |
C22 | 0.0185 (7) | 0.0225 (8) | 0.0148 (7) | 0.0060 (6) | 0.0013 (6) | 0.0021 (6) |
C23 | 0.0188 (7) | 0.0181 (8) | 0.0178 (7) | 0.0070 (6) | 0.0013 (6) | 0.0022 (6) |
C24 | 0.0172 (7) | 0.0226 (8) | 0.0165 (7) | 0.0042 (6) | 0.0014 (6) | −0.0002 (6) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.8946 (11) | C9—C10 | 1.398 (2) |
Cu1—O3 | 1.8954 (11) | C9—C12 | 1.444 (2) |
Cu1—O2 | 1.9028 (11) | C10—C11 | 1.387 (2) |
Cu1—O4 | 1.9092 (11) | C10—H10 | 0.9500 |
O1—C2 | 1.2751 (18) | C11—H11 | 0.9500 |
O2—C4 | 1.2823 (18) | C13—C14 | 1.507 (2) |
O3—C14 | 1.2809 (18) | C13—H13A | 0.9800 |
O4—C16 | 1.2757 (18) | C13—H13B | 0.9800 |
N1—C12 | 1.147 (2) | C13—H13C | 0.9800 |
N2—C24 | 1.148 (2) | C14—C15 | 1.410 (2) |
C1—C2 | 1.506 (2) | C15—C16 | 1.411 (2) |
C1—H1A | 0.9800 | C15—C18 | 1.500 (2) |
C1—H1B | 0.9800 | C16—C17 | 1.508 (2) |
C1—H1C | 0.9800 | C17—H17A | 0.9800 |
C2—C3 | 1.414 (2) | C17—H17B | 0.9800 |
C3—C4 | 1.412 (2) | C17—H17C | 0.9800 |
C3—C6 | 1.495 (2) | C18—C19 | 1.396 (2) |
C4—C5 | 1.508 (2) | C18—C23 | 1.397 (2) |
C5—H5A | 0.9800 | C19—C20 | 1.388 (2) |
C5—H5B | 0.9800 | C19—H19 | 0.9500 |
C5—H5C | 0.9800 | C20—C21 | 1.395 (2) |
C6—C11 | 1.398 (2) | C20—H20 | 0.9500 |
C6—C7 | 1.398 (2) | C21—C22 | 1.397 (2) |
C7—C8 | 1.388 (2) | C21—C24 | 1.446 (2) |
C7—H7 | 0.9500 | C22—C23 | 1.387 (2) |
C8—C9 | 1.396 (2) | C22—H22 | 0.9500 |
C8—H8 | 0.9500 | C23—H23 | 0.9500 |
| | | |
O1—Cu1—O3 | 166.74 (5) | C9—C10—H10 | 120.3 |
O1—Cu1—O2 | 92.44 (5) | C10—C11—C6 | 121.29 (15) |
O3—Cu1—O2 | 89.28 (5) | C10—C11—H11 | 119.4 |
O1—Cu1—O4 | 89.21 (5) | C6—C11—H11 | 119.4 |
O3—Cu1—O4 | 92.28 (5) | N1—C12—C9 | 177.52 (18) |
O2—Cu1—O4 | 166.07 (5) | C14—C13—H13A | 109.5 |
C2—O1—Cu1 | 127.74 (10) | C14—C13—H13B | 109.5 |
C4—O2—Cu1 | 127.54 (10) | H13A—C13—H13B | 109.5 |
C14—O3—Cu1 | 127.52 (10) | C14—C13—H13C | 109.5 |
C16—O4—Cu1 | 127.30 (10) | H13A—C13—H13C | 109.5 |
C2—C1—H1A | 109.5 | H13B—C13—H13C | 109.5 |
C2—C1—H1B | 109.5 | O3—C14—C15 | 124.95 (14) |
H1A—C1—H1B | 109.5 | O3—C14—C13 | 114.10 (14) |
C2—C1—H1C | 109.5 | C15—C14—C13 | 120.95 (14) |
H1A—C1—H1C | 109.5 | C14—C15—C16 | 122.00 (14) |
H1B—C1—H1C | 109.5 | C14—C15—C18 | 119.07 (13) |
O1—C2—C3 | 125.21 (14) | C16—C15—C18 | 118.93 (13) |
O1—C2—C1 | 114.18 (13) | O4—C16—C15 | 125.27 (14) |
C3—C2—C1 | 120.61 (14) | O4—C16—C17 | 114.39 (14) |
C4—C3—C2 | 121.93 (14) | C15—C16—C17 | 120.33 (14) |
C4—C3—C6 | 119.11 (13) | C16—C17—H17A | 109.5 |
C2—C3—C6 | 118.95 (13) | C16—C17—H17B | 109.5 |
O2—C4—C3 | 124.89 (14) | H17A—C17—H17B | 109.5 |
O2—C4—C5 | 113.94 (13) | C16—C17—H17C | 109.5 |
C3—C4—C5 | 121.16 (14) | H17A—C17—H17C | 109.5 |
C4—C5—H5A | 109.5 | H17B—C17—H17C | 109.5 |
C4—C5—H5B | 109.5 | C19—C18—C23 | 118.55 (14) |
H5A—C5—H5B | 109.5 | C19—C18—C15 | 120.97 (13) |
C4—C5—H5C | 109.5 | C23—C18—C15 | 120.48 (14) |
H5A—C5—H5C | 109.5 | C20—C19—C18 | 121.15 (15) |
H5B—C5—H5C | 109.5 | C20—C19—H19 | 119.4 |
C11—C6—C7 | 118.30 (14) | C18—C19—H19 | 119.4 |
C11—C6—C3 | 121.41 (14) | C19—C20—C21 | 119.31 (15) |
C7—C6—C3 | 120.29 (14) | C19—C20—H20 | 120.3 |
C8—C7—C6 | 121.31 (15) | C21—C20—H20 | 120.3 |
C8—C7—H7 | 119.3 | C20—C21—C22 | 120.51 (14) |
C6—C7—H7 | 119.3 | C20—C21—C24 | 119.59 (15) |
C7—C8—C9 | 119.42 (15) | C22—C21—C24 | 119.84 (14) |
C7—C8—H8 | 120.3 | C23—C22—C21 | 119.18 (15) |
C9—C8—H8 | 120.3 | C23—C22—H22 | 120.4 |
C8—C9—C10 | 120.22 (14) | C21—C22—H22 | 120.4 |
C8—C9—C12 | 119.64 (15) | C22—C23—C18 | 121.27 (15) |
C10—C9—C12 | 120.04 (15) | C22—C23—H23 | 119.4 |
C11—C10—C9 | 119.42 (15) | C18—C23—H23 | 119.4 |
C11—C10—H10 | 120.3 | N2—C24—C21 | 177.47 (19) |
| | | |
O3—Cu1—O1—C2 | 95.4 (2) | C7—C8—C9—C12 | 174.37 (15) |
O2—Cu1—O1—C2 | −1.81 (14) | C8—C9—C10—C11 | 1.3 (2) |
O4—Cu1—O1—C2 | −167.98 (14) | C12—C9—C10—C11 | −174.95 (15) |
O1—Cu1—O2—C4 | −3.18 (14) | C9—C10—C11—C6 | 0.6 (2) |
O3—Cu1—O2—C4 | −170.02 (14) | C7—C6—C11—C10 | −1.8 (2) |
O4—Cu1—O2—C4 | 93.4 (2) | C3—C6—C11—C10 | 177.53 (14) |
O1—Cu1—O3—C14 | 87.7 (3) | Cu1—O3—C14—C15 | 9.5 (2) |
O2—Cu1—O3—C14 | −174.74 (14) | Cu1—O3—C14—C13 | −171.22 (11) |
O4—Cu1—O3—C14 | −8.58 (14) | O3—C14—C15—C16 | −2.1 (3) |
O1—Cu1—O4—C16 | −164.22 (14) | C13—C14—C15—C16 | 178.64 (16) |
O3—Cu1—O4—C16 | 2.59 (14) | O3—C14—C15—C18 | 178.14 (15) |
O2—Cu1—O4—C16 | 98.8 (2) | C13—C14—C15—C18 | −1.1 (2) |
Cu1—O1—C2—C3 | 4.9 (2) | Cu1—O4—C16—C15 | 2.8 (2) |
Cu1—O1—C2—C1 | −174.10 (11) | Cu1—O4—C16—C17 | −178.33 (11) |
O1—C2—C3—C4 | −3.3 (3) | C14—C15—C16—O4 | −4.3 (3) |
C1—C2—C3—C4 | 175.68 (15) | C18—C15—C16—O4 | 175.41 (15) |
O1—C2—C3—C6 | 175.63 (15) | C14—C15—C16—C17 | 176.85 (15) |
C1—C2—C3—C6 | −5.4 (2) | C18—C15—C16—C17 | −3.4 (2) |
Cu1—O2—C4—C3 | 5.3 (2) | C14—C15—C18—C19 | −68.1 (2) |
Cu1—O2—C4—C5 | −173.84 (11) | C16—C15—C18—C19 | 112.11 (18) |
C2—C3—C4—O2 | −2.1 (3) | C14—C15—C18—C23 | 112.71 (18) |
C6—C3—C4—O2 | 179.00 (15) | C16—C15—C18—C23 | −67.0 (2) |
C2—C3—C4—C5 | 176.98 (15) | C23—C18—C19—C20 | −0.5 (2) |
C6—C3—C4—C5 | −1.9 (2) | C15—C18—C19—C20 | −179.63 (15) |
C4—C3—C6—C11 | −70.5 (2) | C18—C19—C20—C21 | 1.6 (3) |
C2—C3—C6—C11 | 110.55 (18) | C19—C20—C21—C22 | −1.5 (2) |
C4—C3—C6—C7 | 108.85 (18) | C19—C20—C21—C24 | 175.75 (15) |
C2—C3—C6—C7 | −70.1 (2) | C20—C21—C22—C23 | 0.3 (2) |
C11—C6—C7—C8 | 1.2 (2) | C24—C21—C22—C23 | −176.98 (15) |
C3—C6—C7—C8 | −178.15 (15) | C21—C22—C23—C18 | 0.9 (2) |
C6—C7—C8—C9 | 0.6 (2) | C19—C18—C23—C22 | −0.8 (2) |
C7—C8—C9—C10 | −1.9 (2) | C15—C18—C23—C22 | 178.37 (15) |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C12H11NO2 | [Cu(C12H10NO2)2] |
Mr | 201.22 | 463.96 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 7.070 (5), 11.644 (9), 12.2430 (11) | 7.6087 (10), 9.260 (2), 15.198 (3) |
α, β, γ (°) | 90, 94.035 (3), 90 | 91.327 (8), 92.814 (8), 107.509 (12) |
V (Å3) | 1005.4 (11) | 1019.1 (3) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 1.11 |
Crystal size (mm) | 0.20 × 0.10 × 0.07 | 0.22 × 0.10 × 0.07 |
|
Data collection |
Diffractometer | Nonius KappaCCD (with Oxford Cryostream) diffractometer | Nonius KappaCCD (with Oxford Cryostream) diffractometer |
Absorption correction | – | Multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) |
Tmin, Tmax | – | 0.793, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8931, 1969, 1396 | 31552, 7082, 5681 |
Rint | 0.033 | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 | 0.748 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.138, 1.02 | 0.038, 0.087, 1.04 |
No. of reflections | 1969 | 7082 |
No. of parameters | 140 | 285 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.25 | 0.44, −0.53 |
Selected geometric parameters (Å, º) for (I) topO1—C2 | 1.276 (2) | C2—C3 | 1.427 (3) |
O2—C4 | 1.314 (2) | C3—C4 | 1.389 (3) |
N1—C12 | 1.150 (3) | | |
| | | |
O1—C2—C3 | 120.99 (18) | O2—C4—C3 | 121.28 (18) |
C4—C3—C2 | 119.00 (17) | N1—C12—C9 | 178.9 (2) |
| | | |
C2—C3—C6—C7 | −79.7 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O1 | 1.08 (3) | 1.44 (3) | 2.456 (2) | 153 (2) |
Selected geometric parameters (Å, º) for (II) topCu1—O1 | 1.8946 (11) | O2—C4 | 1.2823 (18) |
Cu1—O3 | 1.8954 (11) | O3—C14 | 1.2809 (18) |
Cu1—O2 | 1.9028 (11) | O4—C16 | 1.2757 (18) |
Cu1—O4 | 1.9092 (11) | N1—C12 | 1.147 (2) |
O1—C2 | 1.2751 (18) | N2—C24 | 1.148 (2) |
| | | |
O1—Cu1—O3 | 166.74 (5) | O3—Cu1—O4 | 92.28 (5) |
O1—Cu1—O2 | 92.44 (5) | O2—Cu1—O4 | 166.07 (5) |
O3—Cu1—O2 | 89.28 (5) | N1—C12—C9 | 177.52 (18) |
O1—Cu1—O4 | 89.21 (5) | N2—C24—C21 | 177.47 (19) |
| | | |
C2—C3—C6—C7 | −70.1 (2) | C14—C15—C18—C19 | −68.1 (2) |
Metal-β-diketonate complexes are of interest for their host–guest chemistry (Soldatov & Ripmeester, 2001) and their application in chemical vapor deposition (CVD) of metal films (Borgharkar et al., 1999; Maverick et al., 2002). Our previous studies of metal-β-diketonate supramolecules (Maverick et al., 1986; 2001) have shown that the metal centers in these supramolecules can bind a variety of different guest molecules, making these kinds of compounds potentially useful in separation and sensors. The structures of 3-(4-cyanophenyl)pentane-2,4-dione (Hacac-C6H4—CN), (I), and its copper(II) complex, (II), are reported here. We are now attempting to utilize coordination of the CN moieties in (II) to other metal atoms in order to construct nanoporous materials.
The structure of (I) is shown in Fig. 1, and selected bond distances and angles are listed in Table 1. It exists as the enol tautomer, which is consistent with the solution NMR study (Dell'Erba et al., 1991). The bond distances, angles and hydrogen bonding distance [2.456 (2) Å] for O1···O2 are comparable to those reported in other 3-phenylpentane-2,4-dione derivatives (Emsley et al., 1989). The dihedral angle between the β-diketone plane and the phenyl ring is 78.28 (4)°, and the H atoms on methyl group C5 are disordered over two sets of sites.
Although the two β-diketonate moieties are almost coplanar with the Cu atom, they make an angle of 24.74 (6) ° with each other. This represents a twisting distortion of the two ligands, away from square–planar and towards tetrahedral geometry. Few four-coordinate copper(II) β-diketonate complexes show this type of distortion; of 59 such compounds for which coordinates were available in the Cambridge Structural Database (Allen et al., 1979), eight showed a noticeable amount (refcodes BIBFIB10, CAXRUO, JOXGIM, NILMUQ, PENTUX, SOJXIY01, TIRGIK, and ZUVSOY). The analogous dihedral angles for these structures range from 4.33 to 24.5 °, the largest value being for JOXGIM. In the case of BIBFIB10 (20.2 °), the distortion at the Cu atom is probably attributable to ring strain, which results from the Pt atom linking its two phosphino-β-diketone ligands. In the other structures, there are no obvious intermolecular interactions causing the distortions.
The average Cu—O distance in II [1.900 (6) Å] is slightly shorter than those found in two other copper(II) cyano-β-diketone complexes, viz. Cu(acac-CN)2 [1.920 (2) Å; Angelova et al., 1989] and Cu(dpm-CN)2 [1.924 (3) Å; Silvernail et al., 2001]. The dihedral angles between the β-diketone planes and phenyl rings are 71.07 (5) (O1, O2 and C1–C5/C6–C11) and 67.54 (5)° (O3, O4 and C13–C17/C18–C23). The intramolecular N1···N2 distance is 20.286 (2) Å, making (II) a very long building block for construction of nanometer-sized porous materials.
It is of interest to compare the packing of Cu(acac-Ph—CN)2 with other related metal-β-diketonate building blocks. Unlike bis(3-(4-pyridyl) pentane-2,4-dionato)copper(II), which crystallizes in two- and three-dimensional metal-organic frameworks because of intermolecular Cu···N coordination (Turner et al., 1997; Chen et al., 2003), Cu(acac-Ph—CN)2 is a molecular solid without any intermolecular Cu···N(C) coordination. In addition to the present Cu(acac-Ph—CN)2 structure, structures have been reported for three other bis(cyano-β-diketonato)M(II) compounds. In the structure of Cu(acac-CN)2 (Angelova et al., 1989), a fifth coordination site at the Cu atom is occupied by an N atom from an adjacent Cu(acac-CN)2 group, leading to the formation of one-dimensional Cu(acac-CN)2 chains. On the other hand, in the structures of Cu(dpm-CN)2 (Silvernail et al., 2001) and Co(acac-CN)2 (Angelova et al., 1991), nitrile N atoms occupy both the fifth and sixth coordination sites, forming two-dimensional (Cu(dpm-CN)2) and three-dimensional (Co(acac-CN)2) frameworks. These structural variations occur mainly because metal–nitrile coordination is weak. Thus slight changes in the β-diketone ligands and metal centers can cause substantial changes in intermolecular interactions in the crystal. We are now exploring the use of these metal-functionalized-β-diketonate `building blocks' in construction of nanometer-sized porous materials.