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The title compound, trans-bis­(3-amino-2-phenyl-4H-1-benzopyran-4-one-κ2N,O4)bis­(perchlorato-κO)copper(II), [Cu(ClO4)2(C15H11NO2)2], is composed of mononuclear units wherein the central CuII cation occupies a crystallographic inversion centre. The cation is coordinated by two bidentate 3-­amino­flavone ligands occupying the equatorial sites and by two perchlorate anions in the apical positions, thereby giving rise to a markedly elongated octa­hedral coordination geometry. Two symmetry-related inter­molecular N—H...O hydrogen bonds link the mol­ecules into chains of rings running parallel to the [100] direction, while intra­molecular N—H...O hydrogen bonds help to determine the orientation of the apical perchlorate anions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010703747X/bm3030sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010703747X/bm3030Isup2.hkl
Contains datablock I

CCDC reference: 661787

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the title complex, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level. Unlabelled atoms are related to labelled atoms by an inversion centre [symmetry code (1 + x, y, z) Please check added text]. Intramolecular N—H···O hydrogen bonds are shown as thin lines.
[Figure 2] Fig. 2. A chain of molecules linked by hydrogen bonds running parallel to [100]. Intermolecular N—H···O interactions are shown as dashed lines. H atoms have been omitted for clarity,except those taking part in hydrogen bonding. [Symmetry code: (i) 1 + x, y, z.]
trans-bis(3-amino-2-phenyl-4H-1-benzopyran-4-one- κ2N,O4)bis(perchlorato-κO)copper(II) top
Crystal data top
[Cu(ClO4)2(C15H11NO2)2]Z = 1
Mr = 736.95F(000) = 375
Triclinic, P1Dx = 1.734 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.4957 (6) ÅCell parameters from 6559 reflections
b = 11.6909 (14) Åθ = 1.0–25.0°
c = 11.7435 (14) ŵ = 1.04 mm1
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
Data collection top
Stoe IPDSII image-plate
diffractometer
2503 independent reflections
Radiation source: sealed tube1851 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
Detector resolution: 150 pixels mm-1θmax = 25.0°, θmin = 1.8°
\j scansh = 66
Absorption correction: gaussian
(WinGX; Farrugia, 1999)
k = 1313
Tmin = 0.781, Tmax = 0.940l = 1313
6559 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: difference Fourier map
wR(F2) = 0.084H 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 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
[Cu(ClO4)2(C15H11NO2)2]γ = 98.332 (9)°
Mr = 736.95V = 705.88 (15) Å3
Triclinic, P1Z = 1
a = 5.4957 (6) ÅMo Kα radiation
b = 11.6909 (14) ŵ = 1.04 mm1
c = 11.7435 (14) ÅT = 193 K
α = 103.142 (10)°0.25 × 0.08 × 0.06 mm
β = 101.398 (9)°
Data collection top
Stoe IPDSII image-plate
diffractometer
2503 independent reflections
Absorption correction: gaussian
(WinGX; Farrugia, 1999)
1851 reflections with I > 2σ(I)
Tmin = 0.781, Tmax = 0.940Rint = 0.048
6559 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.084H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.40 e Å3
2503 reflectionsΔρmin = 0.37 e Å3
222 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.000000.500000.500000.0314 (2)
O10.4445 (4)0.79648 (18)0.90107 (16)0.0312 (7)
O40.0829 (4)0.53021 (19)0.65687 (17)0.0337 (7)
N30.2586 (6)0.6506 (3)0.5720 (2)0.0316 (9)
C20.4412 (6)0.7761 (3)0.7822 (2)0.0277 (9)
C30.2668 (6)0.6867 (3)0.6992 (2)0.0276 (9)
C40.0725 (6)0.6154 (3)0.7336 (2)0.0275 (9)
C50.1327 (6)0.5935 (3)0.9010 (3)0.0320 (10)
C60.1272 (7)0.6272 (3)1.0209 (3)0.0365 (10)
C70.0757 (7)0.7109 (3)1.1019 (3)0.0379 (11)
C80.2704 (7)0.7651 (3)1.0616 (3)0.0351 (10)
C90.2581 (6)0.7335 (3)0.9387 (2)0.0284 (9)
C100.0638 (6)0.6471 (3)0.8581 (2)0.0280 (9)
C110.6457 (6)0.8594 (3)0.7620 (2)0.0290 (9)
C120.8736 (6)0.9008 (3)0.8496 (3)0.0313 (9)
C131.0693 (6)0.9773 (3)0.8310 (3)0.0367 (10)
C141.0397 (7)1.0158 (3)0.7272 (3)0.0402 (11)
C150.8121 (7)0.9781 (3)0.6421 (3)0.0438 (11)
C160.6158 (7)0.9009 (3)0.6588 (3)0.0366 (10)
H50.268500.534200.847000.0380*
H60.263200.593201.049500.0440*
H70.080100.730901.185500.0460*
H80.408800.822201.116300.0420*
H120.894000.876400.922200.0380*
H131.225401.003600.890000.0440*
H141.175301.067900.714400.0480*
H150.790401.005600.571300.0520*
H160.459600.876000.599800.0440*
H310.393 (8)0.641 (3)0.562 (3)0.039 (11)*
H320.191 (7)0.701 (3)0.538 (3)0.047 (11)*
Cl10.29939 (15)0.69441 (7)0.37206 (6)0.0367 (3)
O110.3180 (4)0.6212 (2)0.4563 (2)0.0433 (8)
O120.3383 (5)0.6173 (3)0.2543 (2)0.0570 (10)
O130.4860 (5)0.7670 (2)0.3754 (2)0.0506 (9)
O140.0480 (5)0.7669 (2)0.4078 (2)0.0506 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0335 (4)0.0359 (3)0.0199 (3)0.0034 (3)0.0092 (2)0.0019 (2)
O10.0345 (13)0.0369 (12)0.0190 (9)0.0015 (10)0.0061 (8)0.0050 (8)
O40.0349 (13)0.0373 (12)0.0233 (10)0.0049 (10)0.0089 (9)0.0028 (9)
N30.0327 (18)0.0389 (16)0.0223 (12)0.0029 (14)0.0117 (12)0.0045 (11)
C20.0276 (17)0.0337 (16)0.0229 (13)0.0066 (13)0.0071 (12)0.0085 (12)
C30.0315 (17)0.0312 (16)0.0207 (13)0.0059 (13)0.0078 (12)0.0070 (12)
C40.0295 (17)0.0303 (16)0.0232 (14)0.0044 (13)0.0090 (12)0.0070 (12)
C50.0363 (19)0.0347 (17)0.0253 (14)0.0040 (14)0.0094 (13)0.0088 (13)
C60.042 (2)0.0423 (19)0.0304 (15)0.0087 (16)0.0164 (14)0.0132 (14)
C70.047 (2)0.048 (2)0.0234 (14)0.0145 (17)0.0115 (14)0.0131 (14)
C80.041 (2)0.0401 (18)0.0216 (14)0.0070 (15)0.0067 (13)0.0045 (13)
C90.0287 (17)0.0348 (16)0.0243 (14)0.0066 (14)0.0096 (12)0.0098 (12)
C100.0305 (18)0.0323 (16)0.0223 (14)0.0073 (14)0.0083 (12)0.0072 (12)
C110.0305 (18)0.0261 (15)0.0289 (15)0.0020 (13)0.0098 (13)0.0040 (12)
C120.0330 (18)0.0322 (16)0.0257 (14)0.0054 (14)0.0053 (13)0.0038 (12)
C130.0270 (18)0.0375 (18)0.0421 (18)0.0036 (15)0.0051 (14)0.0078 (14)
C140.040 (2)0.0348 (18)0.0442 (18)0.0003 (15)0.0151 (15)0.0077 (15)
C150.055 (2)0.0398 (19)0.0351 (17)0.0025 (17)0.0114 (15)0.0141 (15)
C160.041 (2)0.0367 (18)0.0274 (15)0.0012 (15)0.0044 (13)0.0081 (13)
Cl10.0342 (5)0.0480 (5)0.0302 (4)0.0053 (4)0.0110 (3)0.0137 (3)
O110.0397 (14)0.0584 (15)0.0438 (13)0.0118 (12)0.0206 (10)0.0269 (11)
O120.0569 (18)0.0786 (19)0.0313 (12)0.0101 (15)0.0178 (11)0.0023 (12)
O130.0462 (16)0.0654 (17)0.0473 (14)0.0267 (13)0.0111 (11)0.0195 (12)
O140.0349 (15)0.0547 (15)0.0617 (16)0.0040 (12)0.0052 (11)0.0279 (13)
Geometric parameters (Å, º) top
Cu1—N31.989 (3)N3—H320.88 (4)
Cu1—O41.952 (2)N3—H310.79 (4)
Cu1—O112.453 (2)C5—C61.366 (4)
Cl1—O111.456 (2)C5—H50.9500
Cl1—O121.426 (3)C6—C71.396 (5)
Cl1—O131.424 (3)C6—H60.9500
Cl1—O141.440 (2)C15—C161.378 (5)
O4—C41.255 (4)C15—C141.380 (5)
O1—C21.358 (3)C15—H150.9500
O1—C91.377 (4)C16—H160.9500
C2—C31.355 (4)C12—C131.381 (4)
C2—C111.470 (4)C12—H120.9500
C10—C91.382 (4)C13—C141.381 (4)
C10—C51.405 (4)C13—H130.9500
C10—C41.437 (4)C9—C81.391 (4)
C4—C31.436 (4)C14—H140.9500
C3—N31.448 (3)C8—C71.382 (5)
C11—C161.394 (4)C8—H80.9500
C11—C121.397 (4)C7—H70.9500
O4—Cu1—N385.2 (1)C7—C6—H6119.6
O4—Cu1—O1183.2 (1)C16—C15—C14120.6 (3)
O11—Cu1—N388.8 (1)C16—C15—H15119.7
C4—O4—Cu1112.18 (18)C14—C15—H15119.7
C2—O1—C9120.6 (2)C15—C16—C11120.2 (3)
C3—C2—O1120.6 (3)C15—C16—H16119.9
C3—C2—C11128.0 (3)C11—C16—H16119.9
O1—C2—C11111.3 (2)C13—C12—C11120.1 (3)
C9—C10—C5118.9 (3)C13—C12—H12119.9
C9—C10—C4118.3 (3)C11—C12—H12119.9
C5—C10—C4122.8 (3)C12—C13—C14120.5 (3)
O4—C4—C3120.7 (2)C12—C13—H13119.8
O4—C4—C10122.2 (3)C14—C13—H13119.8
C3—C4—C10117.1 (3)O1—C9—C10121.7 (2)
C2—C3—C4121.1 (2)O1—C9—C8116.4 (3)
C2—C3—N3125.3 (3)C10—C9—C8121.9 (3)
C4—C3—N3113.5 (2)C15—C14—C13119.6 (3)
C16—C11—C12118.9 (3)C15—C14—H14120.2
C16—C11—C2121.7 (3)C13—C14—H14120.2
C12—C11—C2119.4 (3)C7—C8—C9118.2 (3)
C3—N3—Cu1107.50 (19)C7—C8—H8120.9
C3—N3—H32108 (3)C9—C8—H8120.9
Cu1—N3—H32102 (2)C8—C7—C6120.5 (3)
C3—N3—H31111 (3)C8—C7—H7119.7
Cu1—N3—H31111 (3)C6—C7—H7119.7
H32—N3—H31116 (4)O11—Cl1—O12108.72 (16)
C6—C5—C10119.6 (3)O11—Cl1—O13109.16 (14)
C6—C5—H5120.2O11—Cl1—O14107.70 (14)
C10—C5—H5120.2O12—Cl1—O13110.53 (16)
C5—C6—C7120.8 (3)O12—Cl1—O14109.51 (16)
C5—C6—H6119.6O13—Cl1—O14111.15 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H31···O11i0.79 (4)2.21 (4)2.941 (4)155 (3)
N3—H32···O140.87 (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]
Mr736.95
Crystal system, space groupTriclinic, 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)
V3)705.88 (15)
Z1
Radiation typeMo Kα
µ (mm1)1.04
Crystal size (mm)0.25 × 0.08 × 0.06
Data collection
DiffractometerStoe IPDSII image-plate
diffractometer
Absorption correctionGaussian
(WinGX; Farrugia, 1999)
Tmin, Tmax0.781, 0.940
No. of measured, independent and
observed [I > 2σ(I)] reflections
6559, 2503, 1851
Rint0.048
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.084, 0.96
No. of reflections2503
No. of parameters222
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
Cu1—N31.989 (3)Cl1—O121.426 (3)
Cu1—O41.952 (2)Cl1—O131.424 (3)
Cu1—O112.453 (2)Cl1—O141.440 (2)
Cl1—O111.456 (2)
O4—Cu1—N385.2 (1)O11—Cu1—N388.8 (1)
O4—Cu1—O1183.2 (1)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H31···O11i0.79 (4)2.21 (4)2.941 (4)155 (3)
N3—H32···O140.87 (4)2.17 (4)2.996 (4)160 (3)
Symmetry code: (i) x+1, y, z.
 

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