Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104001957/fr1457sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104001957/fr1457Iasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104001957/fr1457Ibsup3.hkl |
CCDC references: 235319; 235320
The title compound was isolated from the reaction of copper gluconate and hinokitiol (Aldrich Chemical Company) in a 1:2 molar ratio. An aqueous solution of copper gluconate was added to a solution of hinokitiol in ethanol and the mixture stirred for 1 h. The resulting green precipitate was collected and recrystallized from aqueous ethanol. An assortment of crystal morphologies was immediately evident in the recrystallized product. Both (Ia) and (Ib) crystallize as green–yellow needles, but the two forms have noticeably different physical properties that aid in their identification. Crystals of (Ia) are soft and often distort or split into layers when attempts are made to cut them. Crystals of (Ib) are dichroic, i.e. green–yellow when viewed perpendicular to the 001 face and olive green when viewed perpendicular to the 100 face. The previously published polymorph, (Ic), crystallizes as olive-green multifaceted prisms.
All H atoms were allowed to ride on their respective C atoms, with C—H distances constrained to the SHELXTL default values for the specified functional groups and temperatures. The SHELXTL internal defaults for the tropolone, isopropyl methine and methyl H atoms were 0.93, 0.98 and 0.96 Å for (Ia) at 298 K, and 0.95, 1.00 and 0.98 Å for (Ib) at 200 K, respectively. The Uiso(H) values were se to 1.2Ueq(C) for the tropolone and isopropyl methine H atoms, and 1.5Ueq(C) for the methyl H atoms.
For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SHELXTL (Sheldrick, 1996). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990) for (Ia); SHELXTL for (Ib). For both compounds, program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cu(C10H11O2)2] | Z = 1 |
Mr = 389.92 | F(000) = 203 |
Triclinic, P1 | Dx = 1.404 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.1549 (3) Å | Cell parameters from 6146 reflections |
b = 6.9872 (4) Å | θ = 1.5–27.5° |
c = 13.9097 (8) Å | µ = 1.20 mm−1 |
α = 77.747 (3)° | T = 298 K |
β = 84.255 (3)° | Needle, green–yellow |
γ = 70.508 (3)° | 0.29 × 0.08 × 0.04 mm |
V = 461.30 (5) Å3 |
Nonius KappaCCD diffractometer | 2096 independent reflections |
Radiation source: fine-focus sealed tube | 1541 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω scans; 400 1.0° rotations | θmax = 27.5°, θmin = 1.5° |
Absorption correction: gaussian SHELXTL (Sheldrick, 1996) | h = −6→6 |
Tmin = 0.786, Tmax = 0.955 | k = −8→9 |
6146 measured reflections | l = −17→18 |
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)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0469P)2 + 0.197P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = −0.001 |
2095 reflections | Δρmax = 0.27 e Å−3 |
118 parameters | Δρmin = −0.51 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: heavy-atom method | Extinction coefficient: 0.032 (7) |
[Cu(C10H11O2)2] | γ = 70.508 (3)° |
Mr = 389.92 | V = 461.30 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.1549 (3) Å | Mo Kα radiation |
b = 6.9872 (4) Å | µ = 1.20 mm−1 |
c = 13.9097 (8) Å | T = 298 K |
α = 77.747 (3)° | 0.29 × 0.08 × 0.04 mm |
β = 84.255 (3)° |
Nonius KappaCCD diffractometer | 2096 independent reflections |
Absorption correction: gaussian SHELXTL (Sheldrick, 1996) | 1541 reflections with I > 2σ(I) |
Tmin = 0.786, Tmax = 0.955 | Rint = 0.064 |
6146 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.27 e Å−3 |
2095 reflections | Δρmin = −0.51 e Å−3 |
118 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. The observed Cu(1)···C(n) distances are 3.768 (3), 3.911 (3), 3.956 (3), 3.800 (3), 3.612 (3), 3.530 (3) and 3.586 (3) Angstroms for n = 1–7, respectively. The stacking distance (i.e., the distance between the least-squares planes through neighboring molecules) is 3.336 (1) Angstroms. The Cu(1) atom is also 3.336 (1) Angstroms off of the centroid defined by the atoms [C(1),C(4),C(5),C(6),C(7)]. This metal···centroid distance falls within the range of distances (i.e., 3.25–3.55 Angstroms) seen for longer-range non-covalent Cu(II)···arene contacts [see Mascal, M.; Kerdelhue, J.-L.; Blake, A. J.; Cooke, P. A.; Mortimer, R. J.; Teat, S. J. European Journal of Inorganic Chemistry 2000, 485–490]. The Cu···Cu distance between neighboring molecules within a stack is 5.1549 (3) Angstroms, i.e., the length of the a axis. The angle between the Cu···Cu vector and the least-squares plane through any molecule in a stack is 40.33 (3) degrees. The molecules do not stack directly on top of one another. A slippage of 3.930 (1) Angstroms is observed. Weak inter-stack C—H···O interactions may also be present. The following distances (in Angstroms) and angles (in degrees) are noted: C(6)—H(6) 0.93 H(6)···O2 (1 − x, −y, 2 − z) 2.51 C(6)···O2 (1 − x, −y, 2 − z) 3.348 (4) C(6)—H(6)···O2 (1 − x, −y, 2 − z) 150.4 The van der Waals radii for C, H and O are 1.70, 1.20 and 1.52 Angstroms, respectively. The H···O distance of 2.51 Angstroms is less than the sum of the H and O radii (i.e., 1.20 + 1.52 = 2.72 Angstroms). The C···O distance of 3.348 (4) is just slightly larger than the sum of the C and O radii (i.e., 1.70 + 1.52 = 3.22 Angstroms). The involvement of the O(2) atoms in these weak inter-stack interactions may be part of the reason why non-equivalent Cu—O bonds are observed. Each trans-bis(3-isopropyl-7-oxocyclohepta-1,3,5-trienolato)copper(II) molecule is essentially planar. The r.m.s. deviation of atoms from a least-squares plane through the molecule (excluding the isopropyl atoms is 0.017 (2) Angstroms. The maximum deviation from that plane is 0.034 (2) Angstroms for the O(2) atom. The interplanar angle between the CuO4 coordination plane and each C7O2 ligand plane is 178.3 (1) degrees, i.e., the molecule is folded very, very slightly along the O(1)···O(2) and O(1) (-x, 1 − y, 2 − z)···O(2) (-x, 1 − y, 2 − z) vectors. |
Refinement. Refinement on F2 for ALL reflections except for 1 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | ||
Cu1 | 0.0000 | 0.5000 | 1.0000 | 0.0568 (3) | |
O1 | 0.1550 (4) | 0.6439 (3) | 0.8888 (2) | 0.0584 (5) | |
O2 | 0.3359 (4) | 0.2814 (3) | 0.9917 (2) | 0.0613 (6) | |
C1 | 0.3933 (6) | 0.5318 (4) | 0.8600 (2) | 0.0486 (7) | |
C2 | 0.5254 (6) | 0.6159 (5) | 0.7781 (2) | 0.0553 (7) | |
H2 | 0.4250 | 0.7501 | 0.7494 | 0.066* | |
C3 | 0.7790 (6) | 0.5386 (5) | 0.7304 (2) | 0.0529 (7) | |
C4 | 0.9689 (6) | 0.3433 (5) | 0.7571 (2) | 0.0596 (8) | |
H4 | 1.1307 | 0.3162 | 0.7187 | 0.072* | |
C5 | 0.9517 (7) | 0.1836 (5) | 0.8325 (2) | 0.0617 (8) | |
H5 | 1.1036 | 0.0642 | 0.8367 | 0.074* | |
C6 | 0.7460 (6) | 0.1729 (5) | 0.9023 (2) | 0.0602 (8) | |
H6 | 0.7777 | 0.0461 | 0.9451 | 0.072* | |
C7 | 0.4956 (6) | 0.3238 (4) | 0.9189 (2) | 0.0501 (7) | |
C8 | 0.8502 (7) | 0.6808 (6) | 0.6402 (3) | 0.0675 (9) | |
H8 | 1.0460 | 0.6193 | 0.6240 | 0.081* | |
C9 | 0.8097 (9) | 0.8972 (6) | 0.6569 (3) | 0.0845 (11) | |
H9A | 0.9002 | 0.8879 | 0.7155 | 0.127* | |
H9B | 0.6165 | 0.9692 | 0.6640 | 0.127* | |
H9C | 0.8867 | 0.9709 | 0.6016 | 0.127* | |
C10 | 0.6896 (10) | 0.6872 (8) | 0.5524 (3) | 0.0949 (13) | |
H10A | 0.7260 | 0.5491 | 0.5419 | 0.142* | |
H10B | 0.7456 | 0.7687 | 0.4947 | 0.142* | |
H10C | 0.4961 | 0.7477 | 0.5656 | 0.142* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0534 (3) | 0.0577 (4) | 0.0546 (4) | −0.0146 (2) | 0.0048 (2) | −0.0090 (3) |
O1 | 0.0519 (11) | 0.0543 (13) | 0.0580 (13) | −0.0079 (10) | 0.0088 (9) | −0.0070 (10) |
O2 | 0.0574 (12) | 0.0581 (13) | 0.0591 (13) | −0.0143 (10) | 0.0058 (10) | −0.0021 (10) |
C1 | 0.0482 (15) | 0.048 (2) | 0.048 (2) | −0.0125 (13) | −0.0008 (12) | −0.0110 (13) |
C2 | 0.051 (2) | 0.051 (2) | 0.056 (2) | −0.0100 (13) | 0.0021 (14) | −0.0060 (14) |
C3 | 0.053 (2) | 0.056 (2) | 0.052 (2) | −0.0199 (14) | 0.0007 (13) | −0.0126 (14) |
C4 | 0.054 (2) | 0.062 (2) | 0.063 (2) | −0.0153 (15) | 0.0072 (14) | −0.021 (2) |
C5 | 0.057 (2) | 0.052 (2) | 0.068 (2) | −0.0086 (14) | 0.005 (2) | −0.014 (2) |
C6 | 0.060 (2) | 0.050 (2) | 0.063 (2) | −0.0109 (14) | −0.0004 (15) | −0.0047 (15) |
C7 | 0.051 (2) | 0.048 (2) | 0.049 (2) | −0.0147 (13) | −0.0018 (13) | −0.0082 (13) |
C8 | 0.058 (2) | 0.076 (2) | 0.062 (2) | −0.020 (2) | 0.010 (2) | −0.008 (2) |
C9 | 0.096 (3) | 0.076 (3) | 0.080 (3) | −0.038 (2) | 0.006 (2) | 0.000 (2) |
C10 | 0.110 (3) | 0.120 (4) | 0.055 (2) | −0.043 (3) | 0.006 (2) | −0.010 (2) |
Cu1—O2i | 1.901 (2) | C5—C6 | 1.374 (4) |
Cu1—O2 | 1.901 (2) | C5—H5 | 0.93 |
Cu1—O1 | 1.915 (2) | C6—C7 | 1.402 (4) |
Cu1—O1i | 1.915 (2) | C6—H6 | 0.93 |
O1—C1 | 1.295 (3) | C8—C9 | 1.520 (5) |
O2—C7 | 1.289 (4) | C8—C10 | 1.527 (5) |
C1—C2 | 1.391 (4) | C8—H8 | 0.98 |
C1—C7 | 1.460 (4) | C9—H9A | 0.96 |
C2—C3 | 1.395 (4) | C9—H9B | 0.96 |
C2—H2 | 0.93 | C9—H9C | 0.96 |
C3—C4 | 1.387 (4) | C10—H10A | 0.96 |
C3—C8 | 1.523 (4) | C10—H10B | 0.96 |
C4—C5 | 1.380 (5) | C10—H10C | 0.96 |
C4—H4 | 0.93 | ||
O2i—Cu1—O2 | 180.0 | C5—C6—H6 | 115.0 |
O2i—Cu1—O1 | 96.30 (9) | C7—C6—H6 | 115.0 |
O2—Cu1—O1 | 83.70 (9) | O2—C7—C6 | 119.3 (3) |
O2i—Cu1—O1i | 83.70 (9) | O2—C7—C1 | 115.0 (3) |
O2—Cu1—O1i | 96.30 (9) | C6—C7—C1 | 125.7 (3) |
O1—Cu1—O1i | 180.0 | C9—C8—C3 | 113.7 (3) |
C1—O1—Cu1 | 113.0 (2) | C9—C8—C10 | 111.4 (3) |
C7—O2—Cu1 | 113.5 (2) | C3—C8—C10 | 109.9 (3) |
O1—C1—C2 | 118.9 (3) | C9—C8—H8 | 107.1 |
O1—C1—C7 | 114.7 (3) | C3—C8—H8 | 107.1 |
C2—C1—C7 | 126.4 (3) | C10—C8—H8 | 107.1 |
C1—C2—C3 | 132.7 (3) | C8—C9—H9A | 109.5 |
C1—C2—H2 | 113.7 | C8—C9—H9B | 109.5 |
C3—C2—H2 | 113.7 | H9A—C9—H9B | 109.5 |
C4—C3—C2 | 125.8 (3) | C8—C9—H9C | 109.5 |
C4—C3—C8 | 117.4 (3) | H9A—C9—H9C | 109.5 |
C2—C3—C8 | 116.8 (3) | H9B—C9—H9C | 109.5 |
C5—C4—C3 | 129.2 (3) | C8—C10—H10A | 109.5 |
C5—C4—H4 | 115.4 | C8—C10—H10B | 109.5 |
C3—C4—H4 | 115.4 | H10A—C10—H10B | 109.5 |
C6—C5—C4 | 130.3 (3) | C8—C10—H10C | 109.5 |
C6—C5—H5 | 114.8 | H10A—C10—H10C | 109.5 |
C4—C5—H5 | 114.8 | H10B—C10—H10C | 109.5 |
C5—C6—C7 | 129.9 (3) | ||
O2i—Cu1—O1—C1 | −177.9 (2) | C4—C5—C6—C7 | −1.9 (6) |
O2—Cu1—O1—C1 | 2.1 (2) | Cu1—O2—C7—C6 | −177.7 (2) |
O1—Cu1—O2—C7 | −2.4 (2) | Cu1—O2—C7—C1 | 2.3 (3) |
O1i—Cu1—O2—C7 | 177.6 (2) | C5—C6—C7—O2 | −177.6 (3) |
Cu1—O1—C1—C2 | 178.2 (2) | C5—C6—C7—C1 | 2.4 (5) |
Cu1—O1—C1—C7 | −1.4 (3) | O1—C1—C7—O2 | −0.5 (4) |
O1—C1—C2—C3 | 178.9 (3) | C2—C1—C7—O2 | 179.8 (3) |
C7—C1—C2—C3 | −1.5 (5) | O1—C1—C7—C6 | 179.5 (3) |
C1—C2—C3—C4 | 0.4 (5) | C2—C1—C7—C6 | −0.2 (5) |
C1—C2—C3—C8 | 179.3 (3) | C4—C3—C8—C9 | −131.5 (3) |
C2—C3—C4—C5 | 1.5 (5) | C2—C3—C8—C9 | 49.5 (4) |
C8—C3—C4—C5 | −177.5 (3) | C4—C3—C8—C10 | 102.8 (3) |
C3—C4—C5—C6 | −0.7 (6) | C2—C3—C8—C10 | −76.2 (4) |
Symmetry code: (i) −x, −y+1, −z+2. |
[Cu(C10H11O2)2] | F(000) = 406 |
Mr = 389.92 | Dx = 1.457 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 23670 reflections |
a = 8.7410 (2) Å | θ = 2.4–27.5° |
b = 6.7470 (1) Å | µ = 1.25 mm−1 |
c = 15.3448 (4) Å | T = 200 K |
β = 100.800 (1)° | Needle, green–yellow |
V = 888.94 (3) Å3 | 0.22 × 0.12 × 0.05 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 2040 independent reflections |
Radiation source: fine-focus sealed tube | 1591 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ω scans; 800 1.0° rotations | θmax = 27.5°, θmin = 2.4° |
Absorption correction: gaussian SHELXTL (Sheldrick, 1996) | h = −11→11 |
Tmin = 0.794, Tmax = 0.948 | k = −8→7 |
23670 measured reflections | l = −19→19 |
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) = 0.112 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0549P)2 + 1.192P] where P = (Fo2 + 2Fc2)/3 |
2040 reflections | (Δ/σ)max < 0.001 |
117 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.83 e Å−3 |
[Cu(C10H11O2)2] | V = 888.94 (3) Å3 |
Mr = 389.92 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.7410 (2) Å | µ = 1.25 mm−1 |
b = 6.7470 (1) Å | T = 200 K |
c = 15.3448 (4) Å | 0.22 × 0.12 × 0.05 mm |
β = 100.800 (1)° |
Nonius KappaCCD diffractometer | 2040 independent reflections |
Absorption correction: gaussian SHELXTL (Sheldrick, 1996) | 1591 reflections with I > 2σ(I) |
Tmin = 0.794, Tmax = 0.948 | Rint = 0.076 |
23670 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.70 e Å−3 |
2040 reflections | Δρmin = −0.83 e Å−3 |
117 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. In both the Triclinic Form Ia and the Monoclinic Form Ib, the copper atoms are involved in weak apical interactions with pi-electrons from neighboring molecules above and below the CuO4 equatorial planes. The interaction in the Triclinic Form Ia involves an extented pi-system of electron density, while the interaction in the Monoclinic Form Ib is best described as involving pi-electron density predominantly in the vicinity of one C—C bond unit in particular, i.e., C(4)—C(5). The observed Cu(1)···C(4) and Cu(1)···C(5) distances are 3.277 (3) and 3.321 (3) Angstroms, respectively. The stacking distance (i.e., the distance between the least-squares planes through neighboring molecules) is 3.235 (2) Angstroms, and the distance of the Cu(1) atom to the centroid of the C(4)—C(5) bond is 3.226 (2) Angstroms. These distances are consistent with the presence of a weak contact between the Cu(1) atom and the cycloheptatriene ring. Distances ranging from 3.25 to 3.55 Angstroms have been observed for longer-range non-covalent Cu(II)···arene contacts [see Mascal, M.; Kerdelhue, J.-L.; Blake, A. J.; Cooke, P. A.; Mortimer, R. J.; Teat, S. J. European Journal of Inorganic Chemistry 2000, 485–490]. The Cu···Cu distance between neighboring molecules within a stack is 6.7470 (1) Angstroms, i.e., the length of the b axis. The angle between the Cu···Cu vector and the least-squares plane through any molecule in a stack is 28.65 (3) degrees. The molecules do not stack directly on top of one another. A slippage of 5.921 (2) Angstroms is observed. Each trans-bis-(3-isopropyl-7-oxocyclohepta-1,3,5-trienolato)copper(II) molecule in Monoclinic Form Ib is essentially planar; although less so than in the Triclinic Form Ia and in the Monoclinic Form Ic. The r.m.s. deviation of atoms from the least-squares plane through the molecule (excluding the isopropyl atoms) is 0.071 (2) Angstroms. The maximum deviation from that plane is 0.114 (2) Angstroms for the O(2) atom. The interplanar angle between the CuO4 coordination plane and each C7O2 ligand plane is 172.9 (1) degrees, i.e., each molecule exhibits a slight fold along the O(1)···O(2) and O(1) (1 − x, −y, −z)···O(2) (1 − x, −y, −z) vectors. Hence, the molecules in this new Monoclinic Form Ib are slightly more bent compared to those in the Triclinic Form Ia [178.3 (1) degrees] and in the published Monoclinic Form Ic [178.9 (2) degrees] of trans-bis-(3-isopropyl-7-oxocyclohepta-1,3,5-trienolato)copper(II). |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | ||
Cu1 | 0.5000 | 0.0000 | 0.0000 | 0.0310 (2) | |
O1 | 0.3455 (2) | 0.1528 (3) | 0.04383 (14) | 0.0344 (5) | |
O2 | 0.6402 (2) | 0.1973 (3) | 0.05823 (14) | 0.0353 (5) | |
C1 | 0.4003 (3) | 0.3156 (4) | 0.0817 (2) | 0.0287 (6) | |
C2 | 0.2971 (3) | 0.4494 (5) | 0.1098 (2) | 0.0313 (6) | |
H2 | 0.1925 | 0.4036 | 0.1005 | 0.038* | |
C3 | 0.3176 (3) | 0.6367 (4) | 0.1489 (2) | 0.0293 (6) | |
C4 | 0.4592 (3) | 0.7363 (4) | 0.1735 (2) | 0.0320 (6) | |
H4 | 0.4537 | 0.8617 | 0.2010 | 0.038* | |
C5 | 0.6064 (3) | 0.6766 (4) | 0.1633 (2) | 0.0332 (6) | |
H5 | 0.6874 | 0.7675 | 0.1854 | 0.040* | |
C6 | 0.6548 (3) | 0.5058 (4) | 0.1261 (2) | 0.0289 (6) | |
H6 | 0.7632 | 0.4996 | 0.1255 | 0.035* | |
C7 | 0.5691 (3) | 0.3414 (4) | 0.0894 (2) | 0.0290 (6) | |
C8 | 0.1710 (3) | 0.7408 (4) | 0.1658 (2) | 0.0339 (6) | |
H8 | 0.2033 | 0.8724 | 0.1932 | 0.041* | |
C9 | 0.0943 (4) | 0.6255 (5) | 0.2314 (2) | 0.0407 (7) | |
H9A | 0.0007 | 0.6960 | 0.2408 | 0.061* | |
H9B | 0.1674 | 0.6133 | 0.2879 | 0.061* | |
H9C | 0.0654 | 0.4932 | 0.2076 | 0.061* | |
C10 | 0.0566 (4) | 0.7796 (5) | 0.0790 (2) | 0.0459 (8) | |
H10A | −0.0291 | 0.8628 | 0.0910 | 0.069* | |
H10B | 0.0149 | 0.6533 | 0.0534 | 0.069* | |
H10C | 0.1107 | 0.8476 | 0.0372 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0314 (3) | 0.0285 (3) | 0.0332 (3) | 0.0006 (2) | 0.0061 (2) | −0.0039 (2) |
O1 | 0.0314 (10) | 0.0287 (11) | 0.0431 (11) | −0.0024 (8) | 0.0069 (8) | −0.0068 (9) |
O2 | 0.0310 (10) | 0.0372 (12) | 0.0381 (11) | 0.0012 (9) | 0.0072 (8) | −0.0075 (9) |
C1 | 0.0296 (14) | 0.0278 (15) | 0.0289 (13) | −0.0019 (11) | 0.0057 (11) | 0.0003 (11) |
C2 | 0.0258 (13) | 0.033 (2) | 0.0351 (14) | −0.0017 (11) | 0.0052 (11) | −0.0018 (12) |
C3 | 0.0322 (14) | 0.0248 (14) | 0.0300 (13) | 0.0014 (11) | 0.0035 (11) | 0.0021 (11) |
C4 | 0.0371 (15) | 0.0260 (15) | 0.0321 (14) | −0.0030 (12) | 0.0045 (12) | −0.0018 (11) |
C5 | 0.0315 (14) | 0.034 (2) | 0.0331 (15) | −0.0067 (12) | 0.0023 (11) | −0.0027 (12) |
C6 | 0.0233 (12) | 0.032 (2) | 0.0308 (14) | −0.0008 (11) | 0.0048 (10) | −0.0002 (11) |
C7 | 0.0300 (13) | 0.032 (2) | 0.0250 (13) | 0.0012 (11) | 0.0047 (10) | 0.0023 (11) |
C8 | 0.0339 (15) | 0.0244 (15) | 0.043 (2) | 0.0024 (11) | 0.0054 (12) | −0.0033 (12) |
C9 | 0.040 (2) | 0.036 (2) | 0.048 (2) | 0.0049 (13) | 0.0133 (14) | −0.0017 (14) |
C10 | 0.039 (2) | 0.047 (2) | 0.050 (2) | 0.0132 (15) | 0.0051 (15) | 0.009 (2) |
Cu1—O2i | 1.913 (2) | C5—C6 | 1.387 (4) |
Cu1—O2 | 1.913 (2) | C5—H5 | 0.95 |
Cu1—O1 | 1.918 (2) | C6—C7 | 1.397 (4) |
Cu1—O1i | 1.918 (2) | C6—H6 | 0.95 |
O1—C1 | 1.292 (3) | C8—C9 | 1.523 (4) |
O2—C7 | 1.293 (3) | C8—C10 | 1.531 (4) |
C1—C2 | 1.400 (4) | C8—H8 | 1.00 |
C1—C7 | 1.468 (4) | C9—H9A | 0.98 |
C2—C3 | 1.396 (4) | C9—H9B | 0.98 |
C2—H2 | 0.95 | C9—H9C | 0.98 |
C3—C4 | 1.397 (4) | C10—H10A | 0.98 |
C3—C8 | 1.526 (4) | C10—H10B | 0.98 |
C4—C5 | 1.385 (4) | C10—H10C | 0.98 |
C4—H4 | 0.95 | ||
O2i—Cu1—O2 | 180.0 | C5—C6—H6 | 115.0 |
O2i—Cu1—O1 | 96.10 (8) | C7—C6—H6 | 115.0 |
O2—Cu1—O1 | 83.90 (8) | O2—C7—C6 | 119.2 (2) |
O2i—Cu1—O1i | 83.90 (8) | O2—C7—C1 | 115.2 (2) |
O2—Cu1—O1i | 96.10 (8) | C6—C7—C1 | 125.6 (3) |
O1—Cu1—O1i | 180.0 | C9—C8—C3 | 111.4 (2) |
C1—O1—Cu1 | 112.9 (2) | C9—C8—C10 | 111.4 (3) |
C7—O2—Cu1 | 112.7 (2) | C3—C8—C10 | 111.3 (2) |
O1—C1—C2 | 118.7 (2) | C9—C8—H8 | 107.5 |
O1—C1—C7 | 114.8 (2) | C3—C8—H8 | 107.5 |
C2—C1—C7 | 126.5 (3) | C10—C8—H8 | 107.5 |
C3—C2—C1 | 132.7 (3) | C8—C9—H9A | 109.5 |
C3—C2—H2 | 113.7 | C8—C9—H9B | 109.5 |
C1—C2—H2 | 113.7 | H9A—C9—H9B | 109.5 |
C2—C3—C4 | 126.0 (3) | C8—C9—H9C | 109.5 |
C2—C3—C8 | 116.5 (2) | H9A—C9—H9C | 109.5 |
C4—C3—C8 | 117.5 (3) | H9B—C9—H9C | 109.5 |
C5—C4—C3 | 128.6 (3) | C8—C10—H10A | 109.5 |
C5—C4—H4 | 115.7 | C8—C10—H10B | 109.5 |
C3—C4—H4 | 115.7 | H10A—C10—H10B | 109.5 |
C4—C5—C6 | 130.5 (3) | C8—C10—H10C | 109.5 |
C4—C5—H5 | 114.7 | H10A—C10—H10C | 109.5 |
C6—C5—H5 | 114.7 | H10B—C10—H10C | 109.5 |
C5—C6—C7 | 130.1 (3) | ||
O2i—Cu1—O1—C1 | −174.0 (2) | C4—C5—C6—C7 | −1.4 (5) |
O2—Cu1—O1—C1 | 6.0 (2) | Cu1—O2—C7—C6 | −173.9 (2) |
O1—Cu1—O2—C7 | −6.4 (2) | Cu1—O2—C7—C1 | 5.7 (3) |
O1i—Cu1—O2—C7 | 173.6 (2) | C5—C6—C7—O2 | −180.0 (3) |
Cu1—O1—C1—C2 | 174.6 (2) | C5—C6—C7—C1 | 0.5 (5) |
Cu1—O1—C1—C7 | −4.6 (3) | O1—C1—C7—O2 | −0.7 (4) |
O1—C1—C2—C3 | −177.2 (3) | C2—C1—C7—O2 | −179.8 (3) |
C7—C1—C2—C3 | 1.8 (5) | O1—C1—C7—C6 | 178.8 (3) |
C1—C2—C3—C4 | −2.9 (5) | C2—C1—C7—C6 | −0.3 (5) |
C1—C2—C3—C8 | 177.1 (3) | C2—C3—C8—C9 | 63.0 (3) |
C2—C3—C4—C5 | 1.7 (5) | C4—C3—C8—C9 | −117.0 (3) |
C8—C3—C4—C5 | −178.2 (3) | C2—C3—C8—C10 | −62.1 (3) |
C3—C4—C5—C6 | 0.5 (5) | C4—C3—C8—C10 | 117.9 (3) |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
(Ia) | (Ib) | |
Crystal data | ||
Chemical formula | [Cu(C10H11O2)2] | [Cu(C10H11O2)2] |
Mr | 389.92 | 389.92 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 298 | 200 |
a, b, c (Å) | 5.1549 (3), 6.9872 (4), 13.9097 (8) | 8.7410 (2), 6.7470 (1), 15.3448 (4) |
α, β, γ (°) | 77.747 (3), 84.255 (3), 70.508 (3) | 90, 100.800 (1), 90 |
V (Å3) | 461.30 (5) | 888.94 (3) |
Z | 1 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.20 | 1.25 |
Crystal size (mm) | 0.29 × 0.08 × 0.04 | 0.22 × 0.12 × 0.05 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Gaussian SHELXTL (Sheldrick, 1996) | Gaussian SHELXTL (Sheldrick, 1996) |
Tmin, Tmax | 0.786, 0.955 | 0.794, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6146, 2096, 1541 | 23670, 2040, 1591 |
Rint | 0.064 | 0.076 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.107, 1.07 | 0.048, 0.112, 1.12 |
No. of reflections | 2095 | 2040 |
No. of parameters | 118 | 117 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.51 | 0.70, −0.83 |
Computer programs: COLLECT (Nonius, 1998), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN and SHELXTL (Sheldrick, 1996), SHELXS86 (Sheldrick, 1990), SHELXTL.
Iaa | Iba | Icb | |
Cu1-O1 | 1.915 (2) | 1.918 (2) | 1.900 (2) |
Cu1-O2 | 1.901 (2) | 1.913 (2) | 1.904 (2) |
O1-C1 | 1.295 (3) | 1.292 (3) | 1.296 (5) |
O2-C7 | 1.289 (4) | 1.293 (3) | 1.293 (5) |
O1-Cu1-O2 | 83.70 (9) | 83.90 (8) | 83.84 (13) |
Cu1-O1-C1 | 113.0 (2) | 112.9 (2) | 113.5 (3) |
Cu1-O2-C7 | 113.5 (2) | 112.7 (2) | 113.5 (3) |
Notes: (a) this work; (b) Barret et al. (2002); |
Metal complexes of tropolone derivatives have engaged the interest of researchers in such diverse areas as material science and medicinal chemistry. Some of that interest has been focused on hinokitiol (β-thujaplicin), a tropolone and natural product first isolated from Chamaecyparis taiwanensis (Nozoe, 1936). Hinokitiol and its metal complexes have since been shown to exhibit a wide variety of biological activities, e.g. antibacterial, antifungal and antiviral activities among others (Miyamoto et al., 1998; Arima et al., 2003; Morita et al., 2003). Hinokitiol complexes of Cu, Zn and Sn have also been reported to be effective in oral care formulations (Creeth et al., 2000), and the structures of a Cu hinokitiol monomer and of a modification containing both monomers and dimers have been published as a part of those studies (Barret et al., 2002). We have observed, however, that the reported monomer, i.e. trans-bis(hinokitiolato)copper(II), actually exists in a number of additional polymorphic forms. A triclinic form, (Ia), and a new monoclinic form, (Ib), have been obtained from ethanol–water solutions and are reported here. The previously published monoclinic form, (Ic), was obtained from ethanol. Views of (Ia) and (Ib) are given in Fig. 1, and selected distances and angles are summarized in Table 1.
Form (Ia) crystallizes in the triclinic space group P1, while forms (Ib) and (Ic) crystallize in the monoclinic space group P21/c. In all three forms, the Cu atoms reside on centers of crystallographic inversion symmetry and have square-planar coordination geometries. The Cu—O bonds in (Ia) are statistically non-equivalent, while those in (Ib) are equivalent. The Cu—O bonds in (Ic) are also equal in length, albeit significantly shorter than those observed in (Ib). Comparable equivalent and non-equivalent Cu—O bonds have been observed in related Cu–tropolonato complexes (Hasegawa et al., 1997; Chipperfield et al., 1998) and in Cu complexes involving α- or β-hydroxy ketone ligands (Lim et al., 1994; Odoko et al., 2002). The O—Cu—O bite angles for the chelating hinokitiolato ligands in all three polymorphs are also statistically equivalent.
Trans-bis(hinokitiolato)copper(II) is essentially a planar molecule. The r.m.s. deviation of atoms from a least-squares plane through the molecule (excluding the isopropyl atoms) is 0.017 (2) Å for (Ia) and 0.071 (2) Å for (Ib). The less planar nature of (Ib) is visible in Fig. 2 as a slight folding of the molecule along the O1···O2 and O1i···O2i vectors [the interplanar angle between the CuO4 coordination plane and each tropolone ligand plane is 172.9 (1)°]. In contrast, (Ia) and (Ic) are essentially planar, with corresponding interplanar angles of 178.3 (1) and 178.9 (2)°, respectively. These conformational differences in the trans-bis(hinokitiolato)copper(II) molecules are attributed to packing forces.
The packings of trans-bis(hinokitiolato)copper(II) molecules in (Ia) and (Ib) share a number of similarities (Fig. 2) but differ completely from that observed in the previously published (Ic). Most notably, the molecules in (Ia) and (Ib) pack into extended columns or stacks, while those in (Ic) do not. Consequently, the Cu atoms in (Ia) and (Ib) are pseudo-six-coordinate, with weak apical interactions, while the Cu atoms in (Ic) are formally four-coordinate. Interestingly, the apical interactions in (Ia) and (Ib) also differ. The apical interactions in (Ia) are best described as involving π-electron densities distributed over the C1—C7—C6—C5—C4 portion of neighboring hinokitiolato ligands, while the apical interactions in (Ib) involve only the C4—C5 edge of neighboring molecules. The Cu atom is 3.336 (1) Å from the centroid defined by atoms C1, C4, C5, C6 and C7 atoms in (Ia), and 3.226 (2) Å from the centroid of the C4—C5 bond in (Ib). These distances are comparable to values [3.25–3.55 Å] observed for longer-range non-covalent CuII···arene contacts (Mascal et al., 2000).
Thus, the packing and stacking of molecules in (Ia) and (Ib) are consistent with the presence of weak apical η5 and η2 Cu–olefin π interactions, respectively. The distance between the least-squares planes through adjacent molecules, or stacking distance, is 3.336 (1) Å for (Ia) and 3.235 (2) Å for (Ib), and the Cu···Cu distances between neighboring molecules within the stacks are 5.1549 (3) Å for (Ia) and 6.7470 (1) Å for (Ib), i.e. a unit translation in the crystallographic a and b directions, respectively. Furthermore, as shown in Fig. 2, the molecules do not stack directly on top of one another, but instead slide over each other by 3.930 (1) and 5.921 (2) Å in (Ia) and (Ib), respectively.
The triclinic form also differs from (Ib) in that there are weak interstack C—H···O hydrogen-bonding interactions present in (Ia). The C6—H6, H6···O2ii and C6.·O2ii distances are 0.93, 2.51 and 3.348 (4) Å, respectively, and the C6—H6···O2ii angle is 150.4° [symmetry code: (ii) 1 − x, −y, 2 − z]. Whether these hydrogen-bonding interactions contribute to the non-equivalence of the Cu—O bonds in (Ia) is not known at this time.