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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1457.
Published online 2010 October 23. doi:  10.1107/S1600536810041590
PMCID: PMC3009324

catena-Poly[[bis[quinazolin-4(3H)-one-κN 1]cadmium(II)]-di-μ-chlorido]

Abstract

The asymmetric unit of the title compound, [CdCl2(C8H6N2O)2]n, consists of one mol­ecule of the 3H-quinazolin-4-one ligand, one Cd2+ cation, which is located on a twofold axis, and one chlorido ligand in a general position. The latter bridges metal cations, forming a one-dimensional polymer along the b axis. The Cd(...)Cd distance along the chain is 3.7309 (7) Å. The octa­hedral coordination around the metal is completed by two ligands in a trans axial geometry which coordinate through the N atom in 1 position. Moderately strong classical N—H(...)O hydrogen bonds around crystallographic inversion centers cross-link adjacent polymeric chains.

Related literature

The crystal structure of 3H-pyrimidin-4-one was reported by Vaillancourt et al. (1998 [triangle]). For related Cd(II) coordination polymers, see: Hu & Englert (2002 [triangle]); Hu et al. (2003 [triangle]); Englert & Schiffers (2006a [triangle],b [triangle]); Cao et al. (2008 [triangle]). For a general review of halide-bridged chain polymers, see: Englert (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1457-scheme1.jpg

Experimental

Crystal data

  • [CdCl2(C8H6N2O)2]
  • M r = 475.60
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1457-efi1.jpg
  • a = 28.839 (6) Å
  • b = 3.7309 (7) Å
  • c = 17.846 (4) Å
  • β = 123.26 (3)°
  • V = 1605.6 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.71 mm−1
  • T = 130 K
  • 0.80 × 0.03 × 0.02 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (MULABS; Blessing, 1995 [triangle]) T min = 0.936, T max = 0.958
  • 10107 measured reflections
  • 1983 independent reflections
  • 1831 reflections with I > 2σ(I)
  • R int = 0.081

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.102
  • S = 1.16
  • 1983 reflections
  • 118 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.91 e Å−3
  • Δρmin = −2.47 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT-Plus (Bruker, 1999 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810041590/gk2309sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041590/gk2309Isup2.hkl

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

Acknowledgments

We gratefully acknowledge the DAAD for supporting this study.

supplementary crystallographic information

Comment

The title compound represents the first crystal structure of a complex in which 3H-quinazolin-4-one acts as a ligand; the uncoordinated organic molecule has not been reported neither. The title compound is a chain polymer in which each Cd(II) cation is coordinated by four bridging chloro ligands in the equatorial plane and two monodentate 3H-quinazolin-4-one ligands in the axial positions of a pseudo-octahedron. The chain direction corresponds to the shortest lattice parameter; a section of the polymer is shown in Fig. 1. The metal···nitrogen vector and the metal–halide plane subtend an angle of 84.5 (1)°. The angle N—Cd—Nii (ii:-x, y, 1/2 - z) amounts to 175.3 (2)°, and the dihedral angle between the least squares plane through the ligand and the metal–halide plane to 67.00 (6)°. Tilting of the ligand molecules in this structure is stabilized by intermolecular N—H···O hydrogen bonds around crystallographic inversion centers (Table 1, Fig.2).

Experimental

A solution of 73.33 mg (0.4 mmol) of cadmium (II) chloride in 20 ml of water was added to a solution of 116.92 mg (0.8 mmol) of 3H-quinazolin-4-one in 30 ml of acetone. A precipitate formed immediately which was recovered by filtration. Single crystals suitable for the diffraction experiment were obtained by dissolving this precipitate in a 1:3 water:acetone mixture and slow evaporation at room temperature. The crystals grew as colourless needles.

Refinement

Carbon-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). Nitrogen-bound H atom involved in the intermolecular hydrogen bonding was located by difference Fourier synthesis and refined freely [N—H =0.87 (5) Å].

Figures

Fig. 1.
Section of the chain polymer, viewed along the c axis.
Fig. 2.
Projection of the structure along the b direction.

Crystal data

[CdCl2(C8H6N2O)2]F(000) = 936
Mr = 475.60Dx = 1.967 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8356 reflections
a = 28.839 (6) Åθ = 2.3–28.4°
b = 3.7309 (7) ŵ = 1.71 mm1
c = 17.846 (4) ÅT = 130 K
β = 123.26 (3)°Needle, colourless
V = 1605.6 (8) Å30.80 × 0.03 × 0.02 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer1983 independent reflections
Radiation source: fine-focus sealed tube1831 reflections with I > 2σ(I)
graphiteRint = 0.081
ω scansθmax = 28.4°, θmin = 2.3°
Absorption correction: multi-scan (MULABS; Blessing, 1995)h = −38→38
Tmin = 0.936, Tmax = 0.958k = −4→4
10107 measured reflectionsl = −23→23

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.16w = 1/[σ2(Fo2) + (0.045P)2] where P = (Fo2 + 2Fc2)/3
1983 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.91 e Å3
0 restraintsΔρmin = −2.47 e Å3

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
Cd10.00000.41717 (11)0.25000.02822 (14)
Cl10.03110 (4)0.9258 (3)0.36946 (6)0.0345 (2)
O10.25065 (13)0.8403 (9)0.4033 (2)0.0456 (8)
N10.09451 (14)0.4438 (9)0.2882 (2)0.0345 (7)
C20.12966 (17)0.4725 (11)0.3729 (3)0.0348 (9)
H20.11800.40450.41020.042*
N30.18220 (15)0.5931 (11)0.4126 (3)0.0389 (8)
C40.20342 (17)0.7146 (12)0.3647 (3)0.0371 (9)
C4A0.16615 (17)0.6802 (11)0.2686 (3)0.0341 (9)
C50.18303 (17)0.7898 (12)0.2120 (3)0.0373 (9)
H50.21790.89060.23590.045*
C60.14774 (18)0.7473 (13)0.1212 (3)0.0410 (9)
H60.15870.81810.08310.049*
C70.09534 (19)0.5976 (13)0.0859 (3)0.0406 (9)
H70.07180.56690.02430.049*
C80.07797 (18)0.4957 (10)0.1400 (3)0.0343 (9)
H80.04280.39830.11510.041*
C8A0.11298 (17)0.5373 (11)0.2328 (3)0.0333 (8)
H30.206 (2)0.609 (13)0.470 (3)0.040 (13)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.0258 (2)0.0272 (2)0.0302 (2)0.0000.01445 (17)0.000
Cl10.0353 (5)0.0325 (5)0.0343 (5)0.0002 (4)0.0182 (4)0.0008 (4)
O10.0363 (16)0.055 (2)0.0443 (17)−0.0100 (14)0.0211 (14)−0.0023 (15)
N10.0304 (16)0.0340 (18)0.0388 (18)−0.0007 (14)0.0188 (15)−0.0008 (15)
C20.0326 (19)0.033 (2)0.040 (2)−0.0001 (16)0.0205 (18)0.0015 (17)
N30.0307 (17)0.047 (2)0.0354 (19)−0.0019 (16)0.0158 (16)0.0004 (17)
C40.033 (2)0.035 (2)0.041 (2)−0.0013 (17)0.0192 (18)−0.0019 (18)
C4A0.0321 (19)0.030 (2)0.040 (2)−0.0001 (16)0.0194 (18)0.0002 (16)
C50.033 (2)0.033 (2)0.049 (2)0.0009 (17)0.0244 (19)0.0025 (18)
C60.044 (2)0.040 (2)0.047 (2)0.003 (2)0.030 (2)0.001 (2)
C70.042 (2)0.042 (2)0.039 (2)0.004 (2)0.0231 (19)−0.0009 (19)
C80.034 (2)0.0256 (19)0.042 (2)0.0015 (15)0.0196 (18)−0.0011 (15)
C8A0.0332 (19)0.0272 (19)0.041 (2)0.0031 (16)0.0217 (18)0.0010 (16)

Geometric parameters (Å, °)

Cd1—N12.422 (3)N3—H30.87 (5)
Cd1—N1i2.422 (3)C4—C4A1.445 (6)
Cd1—Cl1ii2.5714 (11)C4A—C51.402 (6)
Cd1—Cl1iii2.5714 (11)C4A—C8A1.403 (6)
Cd1—Cl12.6180 (11)C5—C61.370 (6)
Cd1—Cl1i2.6180 (11)C5—H50.9300
Cl1—Cd1iv2.5714 (11)C6—C71.396 (6)
O1—C41.233 (5)C6—H60.9300
N1—C21.283 (6)C7—C81.363 (6)
N1—C8A1.400 (5)C7—H70.9300
C2—N31.350 (5)C8—C8A1.397 (6)
C2—H20.9300C8—H80.9300
N3—C41.373 (6)
N1—Cd1—N1i175.31 (17)C2—N3—H3124 (3)
N1—Cd1—Cl1ii95.13 (9)C4—N3—H3113 (3)
N1i—Cd1—Cl1ii88.22 (9)O1—C4—N3120.7 (4)
N1—Cd1—Cl1iii88.22 (9)O1—C4—C4A124.8 (4)
N1i—Cd1—Cl1iii95.13 (9)N3—C4—C4A114.4 (4)
Cl1ii—Cd1—Cl1iii89.06 (5)C5—C4A—C8A120.5 (4)
N1—Cd1—Cl184.90 (9)C5—C4A—C4120.2 (4)
N1i—Cd1—Cl191.69 (9)C8A—C4A—C4119.4 (4)
Cl1ii—Cd1—Cl1179.01 (3)C6—C5—C4A119.5 (4)
Cl1iii—Cd1—Cl191.93 (4)C6—C5—H5120.2
N1—Cd1—Cl1i91.69 (9)C4A—C5—H5120.2
N1i—Cd1—Cl1i84.90 (9)C5—C6—C7119.8 (4)
Cl1ii—Cd1—Cl1i91.93 (4)C5—C6—H6120.1
Cl1iii—Cd1—Cl1i179.01 (3)C7—C6—H6120.1
Cl1—Cd1—Cl1i87.08 (5)C8—C7—C6121.3 (4)
Cd1iv—Cl1—Cd191.93 (4)C8—C7—H7119.3
C2—N1—C8A116.8 (4)C6—C7—H7119.3
C2—N1—Cd1112.0 (3)C7—C8—C8A120.1 (4)
C8A—N1—Cd1128.1 (3)C7—C8—H8120.0
N1—C2—N3125.5 (4)C8A—C8—H8120.0
N1—C2—H2117.3C8—C8A—N1120.1 (4)
N3—C2—H2117.3C8—C8A—C4A118.8 (4)
C2—N3—C4122.6 (4)N1—C8A—C4A121.1 (4)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···O1v0.87 (5)1.90 (4)2.762 (5)172 (6)

Symmetry codes: (v) −x+1/2, −y+3/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2309).

References

  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Bruker (1999). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2000). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cao, L., Li, Q. & Englert, U. (2008). J. Chem. Crystallogr.38, 833–836.
  • Englert, U. (2010). Coord. Chem. Rev.254, 537–554.
  • Englert, U. & Schiffers, S. (2006a). Acta Cryst. E62, m194–m195.
  • Englert, U. & Schiffers, S. (2006b). Acta Cryst. E62, m295–m296.
  • Hu, C. & Englert, U. (2002). CrystEngComm, 4, 20–25.
  • Hu, C., Li, Q. & Englert, U. (2003). CrystEngComm, 5, 519–529.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Vaillancourt, L., Simard, M. & Wuest, J. D. (1998). J. Org. Chem.63, 9746–9752.

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