metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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catena-Poly[[bis­[quinazolin-4(3H)-one-κN1]cadmium(II)]-di-μ-chlorido]

aS.Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences of Uzbekistan, Mirzo Ulugbek Str., 77, Tashkent 100170, Uzbekistan, and bInstitute of Inorganic Chemistry, RWTH Aachen, Landoltweg 1, D-52056 Aachen, Germany
*Correspondence e-mail: kk_turgunov@rambler.ru

(Received 12 October 2010; accepted 15 October 2010; online 23 October 2010)

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[Vaillancourt, L., Simard, M. & Wuest, J. D. (1998). J. Org. Chem. 63, 9746-9752.]). For related Cd(II) coordination polymers, see: Hu & Englert (2002[Hu, C. & Englert, U. (2002). CrystEngComm, 4, 20-25.]); Hu et al. (2003[Hu, C., Li, Q. & Englert, U. (2003). CrystEngComm, 5, 519-529.]); Englert & Schiffers (2006a[Englert, U. & Schiffers, S. (2006a). Acta Cryst. E62, m194-m195.],b[Englert, U. & Schiffers, S. (2006b). Acta Cryst. E62, m295-m296.]); Cao et al. (2008[Cao, L., Li, Q. & Englert, U. (2008). J. Chem. Crystallogr. 38, 833-836.]). For a general review of halide-bridged chain polymers, see: Englert (2010[Englert, U. (2010). Coord. Chem. Rev. 254, 537-554.]).

[Scheme 1]

Experimental

Crystal data
  • [CdCl2(C8H6N2O)2]

  • Mr = 475.60

  • Monoclinic, C 2/c

  • 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[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.936, Tmax = 0.958

  • 10107 measured reflections

  • 1983 independent reflections

  • 1831 reflections with I > 2σ(I)

  • Rint = 0.081

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3⋯O1i 0.87 (5) 1.90 (4) 2.762 (5) 172 (6)
Symmetry code: (i) [-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1].

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 1999[Bruker (1999). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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].

Structure description top

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).

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

Computing details top

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

Figures top
[Figure 1] Fig. 1. Section of the chain polymer, viewed along the c axis.
[Figure 2] Fig. 2. Projection of the structure along the b direction.
catena-Poly[[bis[quinazolin-4(3H)-one-κN1]cadmium(II)]- di-µ-chlorido] top
Crystal data top
[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 top
Bruker SMART APEX
diffractometer
1983 independent reflections
Radiation source: fine-focus sealed tube1831 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.081
ω scansθmax = 28.4°, θmin = 2.3°
Absorption correction: multi-scan
(MULABS; Blessing, 1995)
h = 3838
Tmin = 0.936, Tmax = 0.958k = 44
10107 measured reflectionsl = 2323
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.16 w = 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
Crystal data top
[CdCl2(C8H6N2O)2]V = 1605.6 (8) Å3
Mr = 475.60Z = 4
Monoclinic, C2/cMo Kα radiation
a = 28.839 (6) ŵ = 1.71 mm1
b = 3.7309 (7) ÅT = 130 K
c = 17.846 (4) Å0.80 × 0.03 × 0.02 mm
β = 123.26 (3)°
Data collection top
Bruker SMART APEX
diffractometer
1983 independent reflections
Absorption correction: multi-scan
(MULABS; Blessing, 1995)
1831 reflections with I > 2σ(I)
Tmin = 0.936, Tmax = 0.958Rint = 0.081
10107 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.16Δρmax = 0.91 e Å3
1983 reflectionsΔρmin = 2.47 e Å3
118 parameters
Special details top

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) top
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) top
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, º) top
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, y1, z+1/2; (iii) x, y1, z; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1v0.87 (5)1.90 (4)2.762 (5)172 (6)
Symmetry code: (v) x+1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formula[CdCl2(C8H6N2O)2]
Mr475.60
Crystal system, space groupMonoclinic, C2/c
Temperature (K)130
a, b, c (Å)28.839 (6), 3.7309 (7), 17.846 (4)
β (°) 123.26 (3)
V3)1605.6 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.71
Crystal size (mm)0.80 × 0.03 × 0.02
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(MULABS; Blessing, 1995)
Tmin, Tmax0.936, 0.958
No. of measured, independent and
observed [I > 2σ(I)] reflections
10107, 1983, 1831
Rint0.081
(sin θ/λ)max1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.102, 1.16
No. of reflections1983
No. of parameters118
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.91, 2.47

Computer programs: SMART (Bruker,2000), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.87 (5)1.90 (4)2.762 (5)172 (6)
Symmetry code: (i) x+1/2, y+3/2, z+1.
 

Acknowledgements

We gratefully acknowledge the DAAD for supporting this study.

References

First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationBruker (1999). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2000). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCao, L., Li, Q. & Englert, U. (2008). J. Chem. Crystallogr. 38, 833–836.  Web of Science CSD CrossRef CAS Google Scholar
First citationEnglert, U. (2010). Coord. Chem. Rev. 254, 537–554.  Web of Science CrossRef CAS Google Scholar
First citationEnglert, U. & Schiffers, S. (2006a). Acta Cryst. E62, m194–m195.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationEnglert, U. & Schiffers, S. (2006b). Acta Cryst. E62, m295–m296.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationHu, C. & Englert, U. (2002). CrystEngComm, 4, 20–25.  CSD CrossRef Google Scholar
First citationHu, C., Li, Q. & Englert, U. (2003). CrystEngComm, 5, 519–529.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationVaillancourt, L., Simard, M. & Wuest, J. D. (1998). J. Org. Chem. 63, 9746–9752.  Web of Science CSD CrossRef CAS Google Scholar

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