Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010703747X/bm3030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010703747X/bm3030Isup2.hkl |
CCDC reference: 661787
For related literature, see: Etter et al. (1990); Gamez et al. (2004); Grabowski (2004); Kośmider et al. (2004, 2004a, 2004b); Kośmider, Osiecka, Zyner & Ochocki (2005); Kośmider, Wójcik, Osiecka, Bartkowiak, Zyner, Ochocki & Liberski (2005); Ochocki & Zyner (2003); Zyner et al. (1999).
The title compound was prepared by the reaction of two equivalents of 3-aminoflavone with one equivalent of copper(II) perchlorate in water–methanol (1:1 v/v). The reaction mixture was stirred at room temperature for 24 h and the solvent partly removed by evaporation. The resulting solution was cooled and light-blue crystals of (I) suitable for X-ray diffraction analysis appeared after a few days.
Aromatic H atoms were introduced in calculated positions with idealized geometry and refined using rigid body model, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C). The amine H atoms were located in a difference Fourier map and were subsequently refined freely; N—H distances are 0.79 (4) and 0.88 (4) Å.
Data collection: X-AREA (Stoe & Cie, 2000); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).
[Cu(ClO4)2(C15H11NO2)2] | Z = 1 |
Mr = 736.95 | F(000) = 375 |
Triclinic, P1 | Dx = 1.734 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.4957 (6) Å | Cell parameters from 6559 reflections |
b = 11.6909 (14) Å | θ = 1.0–25.0° |
c = 11.7435 (14) Å | µ = 1.04 mm−1 |
α = 103.142 (10)° | T = 193 K |
β = 101.398 (9)° | Needle, light blue |
γ = 98.332 (9)° | 0.25 × 0.08 × 0.06 mm |
V = 705.88 (15) Å3 |
Stoe IPDSII image-plate diffractometer | 2503 independent reflections |
Radiation source: sealed tube | 1851 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 150 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
\j scans | h = −6→6 |
Absorption correction: gaussian (WinGX; Farrugia, 1999) | k = −13→13 |
Tmin = 0.781, Tmax = 0.940 | l = −13→13 |
6559 measured reflections |
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)] = 0.037 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0465P)2] where P = (Fo2 + 2Fc2)/3 |
2503 reflections | (Δ/σ)max = 0.001 |
222 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Cu(ClO4)2(C15H11NO2)2] | γ = 98.332 (9)° |
Mr = 736.95 | V = 705.88 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.4957 (6) Å | Mo Kα radiation |
b = 11.6909 (14) Å | µ = 1.04 mm−1 |
c = 11.7435 (14) Å | T = 193 K |
α = 103.142 (10)° | 0.25 × 0.08 × 0.06 mm |
β = 101.398 (9)° |
Stoe IPDSII image-plate diffractometer | 2503 independent reflections |
Absorption correction: gaussian (WinGX; Farrugia, 1999) | 1851 reflections with I > 2σ(I) |
Tmin = 0.781, Tmax = 0.940 | Rint = 0.048 |
6559 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.40 e Å−3 |
2503 reflections | Δρmin = −0.37 e Å−3 |
222 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.00000 | 0.50000 | 0.50000 | 0.0314 (2) | |
O1 | 0.4445 (4) | 0.79648 (18) | 0.90107 (16) | 0.0312 (7) | |
O4 | −0.0829 (4) | 0.53021 (19) | 0.65687 (17) | 0.0337 (7) | |
N3 | 0.2586 (6) | 0.6506 (3) | 0.5720 (2) | 0.0316 (9) | |
C2 | 0.4412 (6) | 0.7761 (3) | 0.7822 (2) | 0.0277 (9) | |
C3 | 0.2668 (6) | 0.6867 (3) | 0.6992 (2) | 0.0276 (9) | |
C4 | 0.0725 (6) | 0.6154 (3) | 0.7336 (2) | 0.0275 (9) | |
C5 | −0.1327 (6) | 0.5935 (3) | 0.9010 (3) | 0.0320 (10) | |
C6 | −0.1272 (7) | 0.6272 (3) | 1.0209 (3) | 0.0365 (10) | |
C7 | 0.0757 (7) | 0.7109 (3) | 1.1019 (3) | 0.0379 (11) | |
C8 | 0.2704 (7) | 0.7651 (3) | 1.0616 (3) | 0.0351 (10) | |
C9 | 0.2581 (6) | 0.7335 (3) | 0.9387 (2) | 0.0284 (9) | |
C10 | 0.0638 (6) | 0.6471 (3) | 0.8581 (2) | 0.0280 (9) | |
C11 | 0.6457 (6) | 0.8594 (3) | 0.7620 (2) | 0.0290 (9) | |
C12 | 0.8736 (6) | 0.9008 (3) | 0.8496 (3) | 0.0313 (9) | |
C13 | 1.0693 (6) | 0.9773 (3) | 0.8310 (3) | 0.0367 (10) | |
C14 | 1.0397 (7) | 1.0158 (3) | 0.7272 (3) | 0.0402 (11) | |
C15 | 0.8121 (7) | 0.9781 (3) | 0.6421 (3) | 0.0438 (11) | |
C16 | 0.6158 (7) | 0.9009 (3) | 0.6588 (3) | 0.0366 (10) | |
H5 | −0.26850 | 0.53420 | 0.84700 | 0.0380* | |
H6 | −0.26320 | 0.59320 | 1.04950 | 0.0440* | |
H7 | 0.08010 | 0.73090 | 1.18550 | 0.0460* | |
H8 | 0.40880 | 0.82220 | 1.11630 | 0.0420* | |
H12 | 0.89400 | 0.87640 | 0.92220 | 0.0380* | |
H13 | 1.22540 | 1.00360 | 0.89000 | 0.0440* | |
H14 | 1.17530 | 1.06790 | 0.71440 | 0.0480* | |
H15 | 0.79040 | 1.00560 | 0.57130 | 0.0520* | |
H16 | 0.45960 | 0.87600 | 0.59980 | 0.0440* | |
H31 | 0.393 (8) | 0.641 (3) | 0.562 (3) | 0.039 (11)* | |
H32 | 0.191 (7) | 0.701 (3) | 0.538 (3) | 0.047 (11)* | |
Cl1 | −0.29939 (15) | 0.69441 (7) | 0.37206 (6) | 0.0367 (3) | |
O11 | −0.3180 (4) | 0.6212 (2) | 0.4563 (2) | 0.0433 (8) | |
O12 | −0.3383 (5) | 0.6173 (3) | 0.2543 (2) | 0.0570 (10) | |
O13 | −0.4860 (5) | 0.7670 (2) | 0.3754 (2) | 0.0506 (9) | |
O14 | −0.0480 (5) | 0.7669 (2) | 0.4078 (2) | 0.0506 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0335 (4) | 0.0359 (3) | 0.0199 (3) | −0.0034 (3) | 0.0092 (2) | 0.0019 (2) |
O1 | 0.0345 (13) | 0.0369 (12) | 0.0190 (9) | 0.0015 (10) | 0.0061 (8) | 0.0050 (8) |
O4 | 0.0349 (13) | 0.0373 (12) | 0.0233 (10) | −0.0049 (10) | 0.0089 (9) | 0.0028 (9) |
N3 | 0.0327 (18) | 0.0389 (16) | 0.0223 (12) | 0.0029 (14) | 0.0117 (12) | 0.0045 (11) |
C2 | 0.0276 (17) | 0.0337 (16) | 0.0229 (13) | 0.0066 (13) | 0.0071 (12) | 0.0085 (12) |
C3 | 0.0315 (17) | 0.0312 (16) | 0.0207 (13) | 0.0059 (13) | 0.0078 (12) | 0.0070 (12) |
C4 | 0.0295 (17) | 0.0303 (16) | 0.0232 (14) | 0.0044 (13) | 0.0090 (12) | 0.0070 (12) |
C5 | 0.0363 (19) | 0.0347 (17) | 0.0253 (14) | 0.0040 (14) | 0.0094 (13) | 0.0088 (13) |
C6 | 0.042 (2) | 0.0423 (19) | 0.0304 (15) | 0.0087 (16) | 0.0164 (14) | 0.0132 (14) |
C7 | 0.047 (2) | 0.048 (2) | 0.0234 (14) | 0.0145 (17) | 0.0115 (14) | 0.0131 (14) |
C8 | 0.041 (2) | 0.0401 (18) | 0.0216 (14) | 0.0070 (15) | 0.0067 (13) | 0.0045 (13) |
C9 | 0.0287 (17) | 0.0348 (16) | 0.0243 (14) | 0.0066 (14) | 0.0096 (12) | 0.0098 (12) |
C10 | 0.0305 (18) | 0.0323 (16) | 0.0223 (14) | 0.0073 (14) | 0.0083 (12) | 0.0072 (12) |
C11 | 0.0305 (18) | 0.0261 (15) | 0.0289 (15) | 0.0020 (13) | 0.0098 (13) | 0.0040 (12) |
C12 | 0.0330 (18) | 0.0322 (16) | 0.0257 (14) | 0.0054 (14) | 0.0053 (13) | 0.0038 (12) |
C13 | 0.0270 (18) | 0.0375 (18) | 0.0421 (18) | 0.0036 (15) | 0.0051 (14) | 0.0078 (14) |
C14 | 0.040 (2) | 0.0348 (18) | 0.0442 (18) | 0.0003 (15) | 0.0151 (15) | 0.0077 (15) |
C15 | 0.055 (2) | 0.0398 (19) | 0.0351 (17) | −0.0025 (17) | 0.0114 (15) | 0.0141 (15) |
C16 | 0.041 (2) | 0.0367 (18) | 0.0274 (15) | −0.0012 (15) | 0.0044 (13) | 0.0081 (13) |
Cl1 | 0.0342 (5) | 0.0480 (5) | 0.0302 (4) | 0.0053 (4) | 0.0110 (3) | 0.0137 (3) |
O11 | 0.0397 (14) | 0.0584 (15) | 0.0438 (13) | 0.0118 (12) | 0.0206 (10) | 0.0269 (11) |
O12 | 0.0569 (18) | 0.0786 (19) | 0.0313 (12) | 0.0101 (15) | 0.0178 (11) | 0.0023 (12) |
O13 | 0.0462 (16) | 0.0654 (17) | 0.0473 (14) | 0.0267 (13) | 0.0111 (11) | 0.0195 (12) |
O14 | 0.0349 (15) | 0.0547 (15) | 0.0617 (16) | −0.0040 (12) | 0.0052 (11) | 0.0279 (13) |
Cu1—N3 | 1.989 (3) | N3—H32 | 0.88 (4) |
Cu1—O4 | 1.952 (2) | N3—H31 | 0.79 (4) |
Cu1—O11 | 2.453 (2) | C5—C6 | 1.366 (4) |
Cl1—O11 | 1.456 (2) | C5—H5 | 0.9500 |
Cl1—O12 | 1.426 (3) | C6—C7 | 1.396 (5) |
Cl1—O13 | 1.424 (3) | C6—H6 | 0.9500 |
Cl1—O14 | 1.440 (2) | C15—C16 | 1.378 (5) |
O4—C4 | 1.255 (4) | C15—C14 | 1.380 (5) |
O1—C2 | 1.358 (3) | C15—H15 | 0.9500 |
O1—C9 | 1.377 (4) | C16—H16 | 0.9500 |
C2—C3 | 1.355 (4) | C12—C13 | 1.381 (4) |
C2—C11 | 1.470 (4) | C12—H12 | 0.9500 |
C10—C9 | 1.382 (4) | C13—C14 | 1.381 (4) |
C10—C5 | 1.405 (4) | C13—H13 | 0.9500 |
C10—C4 | 1.437 (4) | C9—C8 | 1.391 (4) |
C4—C3 | 1.436 (4) | C14—H14 | 0.9500 |
C3—N3 | 1.448 (3) | C8—C7 | 1.382 (5) |
C11—C16 | 1.394 (4) | C8—H8 | 0.9500 |
C11—C12 | 1.397 (4) | C7—H7 | 0.9500 |
O4—Cu1—N3 | 85.2 (1) | C7—C6—H6 | 119.6 |
O4—Cu1—O11 | 83.2 (1) | C16—C15—C14 | 120.6 (3) |
O11—Cu1—N3 | 88.8 (1) | C16—C15—H15 | 119.7 |
C4—O4—Cu1 | 112.18 (18) | C14—C15—H15 | 119.7 |
C2—O1—C9 | 120.6 (2) | C15—C16—C11 | 120.2 (3) |
C3—C2—O1 | 120.6 (3) | C15—C16—H16 | 119.9 |
C3—C2—C11 | 128.0 (3) | C11—C16—H16 | 119.9 |
O1—C2—C11 | 111.3 (2) | C13—C12—C11 | 120.1 (3) |
C9—C10—C5 | 118.9 (3) | C13—C12—H12 | 119.9 |
C9—C10—C4 | 118.3 (3) | C11—C12—H12 | 119.9 |
C5—C10—C4 | 122.8 (3) | C12—C13—C14 | 120.5 (3) |
O4—C4—C3 | 120.7 (2) | C12—C13—H13 | 119.8 |
O4—C4—C10 | 122.2 (3) | C14—C13—H13 | 119.8 |
C3—C4—C10 | 117.1 (3) | O1—C9—C10 | 121.7 (2) |
C2—C3—C4 | 121.1 (2) | O1—C9—C8 | 116.4 (3) |
C2—C3—N3 | 125.3 (3) | C10—C9—C8 | 121.9 (3) |
C4—C3—N3 | 113.5 (2) | C15—C14—C13 | 119.6 (3) |
C16—C11—C12 | 118.9 (3) | C15—C14—H14 | 120.2 |
C16—C11—C2 | 121.7 (3) | C13—C14—H14 | 120.2 |
C12—C11—C2 | 119.4 (3) | C7—C8—C9 | 118.2 (3) |
C3—N3—Cu1 | 107.50 (19) | C7—C8—H8 | 120.9 |
C3—N3—H32 | 108 (3) | C9—C8—H8 | 120.9 |
Cu1—N3—H32 | 102 (2) | C8—C7—C6 | 120.5 (3) |
C3—N3—H31 | 111 (3) | C8—C7—H7 | 119.7 |
Cu1—N3—H31 | 111 (3) | C6—C7—H7 | 119.7 |
H32—N3—H31 | 116 (4) | O11—Cl1—O12 | 108.72 (16) |
C6—C5—C10 | 119.6 (3) | O11—Cl1—O13 | 109.16 (14) |
C6—C5—H5 | 120.2 | O11—Cl1—O14 | 107.70 (14) |
C10—C5—H5 | 120.2 | O12—Cl1—O13 | 110.53 (16) |
C5—C6—C7 | 120.8 (3) | O12—Cl1—O14 | 109.51 (16) |
C5—C6—H6 | 119.6 | O13—Cl1—O14 | 111.15 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H31···O11i | 0.79 (4) | 2.21 (4) | 2.941 (4) | 155 (3) |
N3—H32···O14 | 0.87 (4) | 2.17 (4) | 2.996 (4) | 160 (3) |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(ClO4)2(C15H11NO2)2] |
Mr | 736.95 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 193 |
a, b, c (Å) | 5.4957 (6), 11.6909 (14), 11.7435 (14) |
α, β, γ (°) | 103.142 (10), 101.398 (9), 98.332 (9) |
V (Å3) | 705.88 (15) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.04 |
Crystal size (mm) | 0.25 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Stoe IPDSII image-plate diffractometer |
Absorption correction | Gaussian (WinGX; Farrugia, 1999) |
Tmin, Tmax | 0.781, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6559, 2503, 1851 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.084, 0.96 |
No. of reflections | 2503 |
No. of parameters | 222 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.37 |
Computer programs: X-AREA (Stoe & Cie, 2000), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and WinGX (Farrugia, 1999).
Cu1—N3 | 1.989 (3) | Cl1—O12 | 1.426 (3) |
Cu1—O4 | 1.952 (2) | Cl1—O13 | 1.424 (3) |
Cu1—O11 | 2.453 (2) | Cl1—O14 | 1.440 (2) |
Cl1—O11 | 1.456 (2) | ||
O4—Cu1—N3 | 85.2 (1) | O11—Cu1—N3 | 88.8 (1) |
O4—Cu1—O11 | 83.2 (1) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H31···O11i | 0.79 (4) | 2.21 (4) | 2.941 (4) | 155 (3) |
N3—H32···O14 | 0.87 (4) | 2.17 (4) | 2.996 (4) | 160 (3) |
Symmetry code: (i) x+1, y, z. |
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Flavonoids have been shown to possess a variety of biological activities including antitumour, antioxidative, antiviral, antibacterial and antimutagenic properties (Kośmider, Osiecka et al., 2004; Kośmider, Zyner et al., 2004a). This biological relevance of the flavanone system initiated the synthesis of a new analogue of cisplatin, cis-bis(3-aminoflavone)dichloroplatinum(II) (Ochocki & Zyner, 2003), for which a possible application as an antitumour agent is conceived (Kośmider, Zyner et al., 2004b; Kośmider, Osiecka et al., 2005; Kośmider, Wójcik et al., 2005). This compound exhibits significant antitumour activity in the development of murine leukaemia L1210 (Zyner et al., 1999). Given the biological activity of flavonoid derivatives involving a metal ion, we decided to synthesize the title new complex, (I), of the 3-aminoflavone ligand, choosing CuII as the metal ion because its complexes are considered to be potent antitumour agents (Gamez et al., 2004).
The X-ray crystallographic study of (I) presented here was undertaken in order to determine the coordination number of the central CuII ion, and to obtain detailed information about the molecular structure and coordination geometry of the complex. We were interested in the potential binding sites of the 3-aminoflavone ligand, in particular whether the N or O atoms, or both, are attached to the metal centre. Moreover, it was our intention to determine whether, in the absence of other potential ligands, the perchlorate anion participates in coordination to the central CuII atom.
Fig. 1 shows a displacement ellipsoid plot of compound (I) with the atom-labelling scheme. Atom Cu1 lies on a crystallographic inversion centre and is six-coordinate: it is chelated by atoms N3 and O4 of two bidentate 3-amionoflavone ligands and by two perchlorate anions. The 3-amionoflavone ligands are bound to the CuII centre in a mutually trans fashion. As a result of chelation, two inversion-related five-membered rings are formed [Cu1/N3/C3/C4/O4 and Cu1/N3i/C3i/C4i/O4i; symmetry code: (i) 1 + x, y, z Please check added text] which, together with the benzopyran systems, generate the main equatorial plane of the molecule. The geometric parameters around atom Cu1 (Table 1) indicate a significant deformation from octahedral geometry towards a tetragonal bipyramid, in which the two perchlorate atoms O11 and O11i occupy the apical positions.
The phenyl substituents defined by atoms C11–C16 and C11i–C16i lie out of the equatorial plane defined by atoms Cu1, O4, N3, O1 and C2–C10 and the symmetry-related atoms of the same molecule. The dihedral angle between this plane and least-squares phenyl plane is 39.6 (1)°.
The protonated atom N3 of the amino group is hydrogen bonded to the O atoms of the two perchlorate anions, leading to the formation of one intramolecular and one intermolecular interaction. As a result of the N3—H31···O14 hydrogen bond (Fig. 2, Table 2), there is an intramolecular S(6) ring motif (Etter et al., 1990). This interaction plays an important role in stabilizing the orientation of the apical perchlorate anions.
The effects of the intermolecular hydrogen-bonding network are more complex. N3—H32···O11 hydrogen bonds connect molecules related by translation along the a axis of the unit cell, forming a chain motif with graph-set symbol C(4) and an R22(8) ring pattern. When both types of hydrogen bonds are considered, the complete notation is C(4)[S(6)][R22(8)].
The variations in bond length for the perchlorate anion are worth mentioning. The longest, at 1.456 (2) Å, is for Cl—O11, corresponding to the O atom which is involved in coordination to the metal centre. Of the remaining three Cl—O bonds, the longest is Cl1—O14 [1.440 (2) Å], where atom O14 participates in the intramolecular hydrogen bond. These obserations are consistent with bond valence (BV) number rules, namely that covalent bonds become longer when atoms are involved in intermolecular interactions (Grabowski, 2004). In comparison, the two shortest Cl—O distances (Cl1—O12 and Cl1—O13) are the same length within one s.u.