PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): m1680.
Published online 2010 November 27. doi:  10.1107/S1600536810048890
PMCID: PMC3011606

Diaqua­dichloridobis[quinazolin-4(1H)-one-κN 3]copper(II)

Abstract

In the title complex, [CuCl2(C8H6N2O)2(H2O)2], the CuII ion is located on an inversion center and is octahedrally coordinated by two N atoms of the 1H-quinazolin-4-one ligand, two chloride ligands and two aqua ligands. The axial Cu—O distances are significantly longer [2.512 (2) Å], than the Cu—N [2.022 (2) Å] and Cu—Cl [2.3232 (4) Å] distances as a result of Jahn–Teller distortion. Aqua ligands are involved in intra- and inter­molecular hydrogen bonding, and N—H(...)O inter­molecular hydrogen bonds are formed between the organic ligands. In addition, weak π–π inter­actions are observed between the benzene rings of the ligand [centroid–centroid distance = 3.678 (1) Å].

Related literature

The crystal structure of pyrimidin-4(3H)-one was reported by Vaillancourt et al. (1998 [triangle]). For a Cd(II) coordination polymer with quinazolin-4(3H)-one, see: Turgunov & Englert (2010 [triangle]). For computational studies of quinazolin-4-one derivatives, see: Bakalova et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1680-scheme1.jpg

Experimental

Crystal data

  • [CuCl2(C8H6N2O)2(H2O)2]
  • M r = 462.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1680-efi1.jpg
  • a = 6.7438 (3) Å
  • b = 18.5328 (8) Å
  • c = 6.7831 (3) Å
  • β = 90.735 (3)°
  • V = 847.69 (6) Å3
  • Z = 2
  • Cu Kα radiation
  • μ = 5.03 mm−1
  • T = 293 K
  • 0.55 × 0.35 × 0.20 mm

Data collection

  • Oxford Diffraction Xcalibur Ruby diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 [triangle]) T min = 0.366, T max = 1.000
  • 5548 measured reflections
  • 1725 independent reflections
  • 1639 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.089
  • S = 1.10
  • 1725 reflections
  • 137 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Bruker, 1998 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810048890/nk2075sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048890/nk2075Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Academy of Sciences of the Republic of Uzbekistan for supporting this study (grant FA–F3–T045).

supplementary crystallographic information

Comment

In solutions, 4-quinazolinone could have in principle three isomers—1H, 3H, and 4-OH, as shown in Figure 1, with preference of 3H-tautomer. Recently, the crystal structure of a CdII coordination complex has been reported, in which 3H-quinazolin-4-one (3H-tautomer) acted as a ligand (Turgunov & Englert, 2010). We now report the structure of a CuII complex in which 1H-quinazolin-4-one (1H-tautomer) acts as a ligand.

In the title compound, CuII ion is located on the inversion center and has an octahedral coordination environment: two ligands coordinated via N atoms in position 3, two chloride ligands and two aqua ligands (Figure 2). The distances between Cu and coordination atoms are the following: d(Cu—N3) = 2.022 (2) Å, d(Cu—Cl) = 2.3232 (4) Å and d(Cu—Ow) = 2.512 (2) Å. Long distances of metal-aqua bonds than other four coordination bonds indicate existence of the Jahn-Teller elongation effect.

Aqua ligands are involved in intramolecular and intermolecular hydrogen bonding. Intramoleculer H-bonding is occurring with carbonyl group of the ligand. An intermolecular H-bonding of aqua and chloride ligands gives raise to chains along [001] (Figure 3). In addition, between ligand and water molecules are formed weak C–H···O hydrogen bonds. Intermolecular N—H···O and N—H···Cl hydrogen bonds formed between the organic and chloride ligands link molecular complexes into hydrogen-bonded chains along [100] (Figure 4; Table 1). Weak π···π ring interactions connect the molecular complexes along [010] and [001] directions. [Cg1···Cg1vi=3.678 (1) Å, where Cg1=C4A–C5–C6–C7–C8–C8A; vi = x, 3/2 - y, 1/2 + z].

Experimental

A solution of 17.05 mg (0.1 mmol) of copper(II) chloride dihydrate in 2 ml of water was added to a solution of 29.23 mg (0.2 mmol) of 3H-quinazolin-4-one in 5 ml of ethanol. The solution allowed to stand at room temperature for one week, after which light-blue crystals were obtained.

Refinement

C-bound H atoms were positioned geometrically and treated as riding on their C atoms, with C—H distances of 0.93 Å (aromatic) and were refined with Uiso(H)=1.2Ueq(C). N-bound H atoms and water H atoms involved in the intermolecular hydrogen bonding were found by difference Fourier synthesis and refined isotropically with a distance restrains of 0.87 (2) and 0.85 (2) Å, respectively [N—H =0.84 (2) Å, O1w—H1w=0.84 (2) Å, O1w—H2w=0.85 (2) Å].

Figures

Fig. 1.
The 3H, 1H and 4-OH tautomers of 4-quinazolinone.
Fig. 2.
The molecular structure of the title complex with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 3.
Crystal packing of the title compound viewed along the a axis, showing the formation of a hydrogen-bonded chain along [001]. Molecular complexes are furhter linked by π–π stacking interactions, formed between ligands, along [010] ...
Fig. 4.
Part of the crystal structure of the title compound showing the formation of a hydrogen-bonded chain along [100].

Crystal data

[CuCl2(C8H6N2O)2(H2O)2]F(000) = 470
Mr = 462.77Dx = 1.813 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybcCell parameters from 4533 reflections
a = 6.7438 (3) Åθ = 4.8–75.3°
b = 18.5328 (8) ŵ = 5.03 mm1
c = 6.7831 (3) ÅT = 293 K
β = 90.735 (3)°Prism, light-blue
V = 847.69 (6) Å30.55 × 0.35 × 0.20 mm
Z = 2

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer1725 independent reflections
Radiation source: Enhance (Cu) X-ray Source1639 reflections with I > 2σ(I)
graphiteRint = 0.040
Detector resolution: 10.2576 pixels mm-1θmax = 77.1°, θmin = 4.8°
ω scansh = −5→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)k = −23→22
Tmin = 0.366, Tmax = 1.000l = −8→8
5548 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089w = 1/[σ2(Fo2) + (0.0535P)2 + 0.3464P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
1725 reflectionsΔρmax = 0.37 e Å3
137 parametersΔρmin = −0.46 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0067 (7)

Special details

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)

xyzUiso*/Ueq
Cu10.00000.50000.50000.02135 (17)
Cl10.20934 (7)0.45671 (2)0.74764 (6)0.02750 (17)
O1−0.12427 (19)0.66628 (7)0.5870 (2)0.0280 (3)
N10.4508 (2)0.65113 (9)0.4461 (2)0.0227 (3)
C20.3358 (3)0.59405 (10)0.4636 (3)0.0229 (4)
H2A0.39360.54900.44580.028*
N30.1427 (2)0.59595 (8)0.5049 (2)0.0209 (3)
C40.0522 (3)0.66252 (9)0.5382 (3)0.0198 (4)
C4A0.1738 (3)0.72721 (10)0.5123 (2)0.0196 (4)
C50.0922 (3)0.79617 (10)0.5345 (3)0.0239 (4)
H5A−0.03990.80140.56930.029*
C60.2088 (3)0.85635 (11)0.5046 (3)0.0288 (4)
H6A0.15400.90220.51670.035*
C70.4101 (3)0.84875 (11)0.4560 (3)0.0311 (4)
H7A0.48710.88970.43630.037*
C80.4945 (3)0.78128 (11)0.4373 (3)0.0276 (4)
H8A0.62780.77640.40640.033*
C8A0.3762 (3)0.72057 (10)0.4656 (2)0.0205 (4)
O1W0.2398 (3)0.46004 (9)0.2416 (2)0.0356 (4)
H1W0.218 (5)0.4172 (11)0.274 (5)0.057 (10)*
H10.570 (3)0.6432 (17)0.417 (5)0.054 (9)*
H2W0.219 (6)0.462 (2)0.118 (3)0.065 (10)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0191 (2)0.0140 (2)0.0308 (3)−0.00062 (12)−0.00334 (16)0.00158 (13)
Cl10.0262 (3)0.0276 (3)0.0286 (3)0.00254 (16)−0.00262 (18)0.00244 (16)
O10.0175 (6)0.0225 (7)0.0441 (8)0.0005 (5)0.0050 (5)−0.0008 (6)
N10.0149 (7)0.0243 (8)0.0290 (8)0.0010 (6)0.0006 (6)0.0016 (6)
C20.0209 (8)0.0190 (8)0.0289 (9)0.0025 (7)−0.0013 (7)0.0001 (7)
N30.0189 (7)0.0161 (7)0.0278 (7)0.0015 (5)−0.0009 (6)0.0013 (6)
C40.0198 (8)0.0170 (8)0.0224 (8)−0.0001 (6)−0.0017 (6)−0.0003 (6)
C4A0.0196 (8)0.0200 (8)0.0191 (7)−0.0005 (6)−0.0020 (6)−0.0002 (6)
C50.0256 (9)0.0208 (9)0.0253 (9)0.0006 (7)−0.0017 (7)−0.0013 (7)
C60.0395 (11)0.0180 (9)0.0287 (9)−0.0010 (8)−0.0041 (8)−0.0005 (7)
C70.0387 (11)0.0230 (10)0.0315 (10)−0.0141 (8)−0.0021 (8)0.0013 (7)
C80.0242 (9)0.0306 (10)0.0280 (9)−0.0088 (8)−0.0003 (7)0.0016 (8)
C8A0.0205 (8)0.0218 (9)0.0192 (7)−0.0024 (7)−0.0027 (6)0.0006 (6)
O1W0.0416 (9)0.0273 (8)0.0380 (9)0.0003 (6)0.0032 (7)−0.0016 (6)

Geometric parameters (Å, °)

Cu1—N32.0221 (15)C4A—C51.400 (3)
Cu1—N3i2.0221 (15)C4A—C8A1.410 (3)
Cu1—Cl12.3232 (4)C5—C61.381 (3)
Cu1—Cl1i2.3232 (4)C5—H5A0.9300
O1—C41.241 (2)C6—C71.409 (3)
N1—C21.318 (2)C6—H6A0.9300
N1—C8A1.389 (2)C7—C81.380 (3)
N1—H10.841 (18)C7—H7A0.9300
C2—N31.336 (2)C8—C8A1.394 (3)
C2—H2A0.9300C8—H8A0.9300
N3—C41.396 (2)O1W—H1W0.837 (18)
C4—C4A1.464 (2)O1W—H2W0.848 (19)
N3—Cu1—N3i180.0C5—C4A—C4120.84 (16)
N3—Cu1—Cl190.40 (4)C8A—C4A—C4120.04 (16)
N3i—Cu1—Cl189.60 (4)C6—C5—C4A119.75 (18)
N3—Cu1—Cl1i89.60 (4)C6—C5—H5A120.1
N3i—Cu1—Cl1i90.40 (4)C4A—C5—H5A120.1
Cl1—Cu1—Cl1i180.0C5—C6—C7120.38 (19)
C2—N1—C8A121.43 (15)C5—C6—H6A119.8
C2—N1—H1116 (2)C7—C6—H6A119.8
C8A—N1—H1122 (2)C8—C7—C6120.79 (17)
N1—C2—N3125.02 (16)C8—C7—H7A119.6
N1—C2—H2A117.5C6—C7—H7A119.6
N3—C2—H2A117.5C7—C8—C8A118.77 (18)
C2—N3—C4119.11 (15)C7—C8—H8A120.6
C2—N3—Cu1116.00 (12)C8A—C8—H8A120.6
C4—N3—Cu1124.80 (12)N1—C8A—C8121.77 (17)
O1—C4—N3121.02 (16)N1—C8A—C4A117.05 (15)
O1—C4—C4A121.77 (16)C8—C8A—C4A121.17 (17)
N3—C4—C4A117.21 (15)H1W—O1W—H2W106 (3)
C5—C4A—C8A119.11 (16)

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1W···O1i0.84 (2)1.92 (3)2.732 (2)162 (3)
O1W—H2W···Cl1ii0.85 (2)2.51 (2)3.355 (2)171 (4)
N1—H1···O1iii0.84 (2)2.39 (3)3.022 (2)133 (3)
N1—H1···Cl1iv0.84 (2)2.63 (3)3.324 (2)140 (3)
C2—H2A···O1W0.932.382.972 (3)121
C7—H7A···O1Wv0.932.573.421 (3)152

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z−1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NK2075).

References

  • Bakalova, S. M., Santos, A. G., Timcheva, I., Kaneti, J., Filipova, I. L., Dobrikov, G. M. & Dimitrov, V. D. (2004). J. Mol. Struct. (THEOCHEM), 710, 229–234.
  • Bruker (1998). XP. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Oxford Diffraction (2007). CrysAlis PRO Oxford Diffraction Ltd, Abingdon, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Turgunov, K. & Englert, U. (2010). Acta Cryst. E66, m1457. [PMC free article] [PubMed]
  • Vaillancourt, L., Simard, M. & Wuest, J. D. (1998). J. Org. Chem.63, 9746–9752.
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography