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

Turgunov, K.; Englert, U.

doi:10.1107/S1600536810041590

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1457

https://doi.org/10.1107/S1600536810041590

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

Kambarali Turgunov ^a ^* and Ulli Englert ^b

^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 ). 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

Crystal data

[CdCl₂(C₈H₆N₂O)₂]
M_r = 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 ) 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[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
Δρ_max = 0.91 e Å⁻³
Δρ_min = −2.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT-Plus (Bruker, 1999 ); data reduction: SAINT-Plus; 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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041590/gk2309Isup2.hkl

checkCIF report

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.

Structure description 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).

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

	Fig. 1. Section of the chain polymer, viewed along the c axis.
	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
M_r = 475.60	D_x = 1.967 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8356 reflections
a = 28.839 (6) Å	θ = 2.3–28.4°
b = 3.7309 (7) Å	µ = 1.71 mm⁻¹
c = 17.846 (4) Å	T = 130 K
β = 123.26 (3)°	Needle, colourless
V = 1605.6 (8) Å³	0.80 × 0.03 × 0.02 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1983 independent reflections
Radiation source: fine-focus sealed tube	1831 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ω scans	θ_max = 28.4°, θ_min = 2.3°
Absorption correction: multi-scan (MULABS; Blessing, 1995)	h = −38→38
T_min = 0.936, T_max = 0.958	k = −4→4
10107 measured reflections	l = −23→23

Refinement top

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.045P)²] where P = (F_o² + 2F_c²)/3
1983 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.91 e Å⁻³
0 restraints	Δρ_min = −2.47 e Å⁻³

Crystal data top

[CdCl₂(C₈H₆N₂O)₂]	V = 1605.6 (8) Å³
M_r = 475.60	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 28.839 (6) Å	µ = 1.71 mm⁻¹
b = 3.7309 (7) Å	T = 130 K
c = 17.846 (4) Å	0.80 × 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)
T_min = 0.936, T_max = 0.958	R_int = 0.081
10107 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Δρ_max = 0.91 e Å⁻³
1983 reflections	Δρ_min = −2.47 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cd1	0.0000	0.41717 (11)	0.2500	0.02822 (14)
Cl1	0.03110 (4)	0.9258 (3)	0.36946 (6)	0.0345 (2)
O1	0.25065 (13)	0.8403 (9)	0.4033 (2)	0.0456 (8)
N1	0.09451 (14)	0.4438 (9)	0.2882 (2)	0.0345 (7)
C2	0.12966 (17)	0.4725 (11)	0.3729 (3)	0.0348 (9)
H2	0.1180	0.4045	0.4102	0.042*
N3	0.18220 (15)	0.5931 (11)	0.4126 (3)	0.0389 (8)
C4	0.20342 (17)	0.7146 (12)	0.3647 (3)	0.0371 (9)
C4A	0.16615 (17)	0.6802 (11)	0.2686 (3)	0.0341 (9)
C5	0.18303 (17)	0.7898 (12)	0.2120 (3)	0.0373 (9)
H5	0.2179	0.8906	0.2359	0.045*
C6	0.14774 (18)	0.7473 (13)	0.1212 (3)	0.0410 (9)
H6	0.1587	0.8181	0.0831	0.049*
C7	0.09534 (19)	0.5976 (13)	0.0859 (3)	0.0406 (9)
H7	0.0718	0.5669	0.0243	0.049*
C8	0.07797 (18)	0.4957 (10)	0.1400 (3)	0.0343 (9)
H8	0.0428	0.3983	0.1151	0.041*
C8A	0.11298 (17)	0.5373 (11)	0.2328 (3)	0.0333 (8)
H3	0.206 (2)	0.609 (13)	0.470 (3)	0.040 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0258 (2)	0.0272 (2)	0.0302 (2)	0.000	0.01445 (17)	0.000
Cl1	0.0353 (5)	0.0325 (5)	0.0343 (5)	0.0002 (4)	0.0182 (4)	0.0008 (4)
O1	0.0363 (16)	0.055 (2)	0.0443 (17)	−0.0100 (14)	0.0211 (14)	−0.0023 (15)
N1	0.0304 (16)	0.0340 (18)	0.0388 (18)	−0.0007 (14)	0.0188 (15)	−0.0008 (15)
C2	0.0326 (19)	0.033 (2)	0.040 (2)	−0.0001 (16)	0.0205 (18)	0.0015 (17)
N3	0.0307 (17)	0.047 (2)	0.0354 (19)	−0.0019 (16)	0.0158 (16)	0.0004 (17)
C4	0.033 (2)	0.035 (2)	0.041 (2)	−0.0013 (17)	0.0192 (18)	−0.0019 (18)
C4A	0.0321 (19)	0.030 (2)	0.040 (2)	−0.0001 (16)	0.0194 (18)	0.0002 (16)
C5	0.033 (2)	0.033 (2)	0.049 (2)	0.0009 (17)	0.0244 (19)	0.0025 (18)
C6	0.044 (2)	0.040 (2)	0.047 (2)	0.003 (2)	0.030 (2)	0.001 (2)
C7	0.042 (2)	0.042 (2)	0.039 (2)	0.004 (2)	0.0231 (19)	−0.0009 (19)
C8	0.034 (2)	0.0256 (19)	0.042 (2)	0.0015 (15)	0.0196 (18)	−0.0011 (15)
C8A	0.0332 (19)	0.0272 (19)	0.041 (2)	0.0031 (16)	0.0217 (18)	0.0010 (16)

Geometric parameters (Å, º) top

Cd1—N1	2.422 (3)	N3—H3	0.87 (5)
Cd1—N1ⁱ	2.422 (3)	C4—C4A	1.445 (6)
Cd1—Cl1ⁱⁱ	2.5714 (11)	C4A—C5	1.402 (6)
Cd1—Cl1ⁱⁱⁱ	2.5714 (11)	C4A—C8A	1.403 (6)
Cd1—Cl1	2.6180 (11)	C5—C6	1.370 (6)
Cd1—Cl1ⁱ	2.6180 (11)	C5—H5	0.9300
Cl1—Cd1^iv	2.5714 (11)	C6—C7	1.396 (6)
O1—C4	1.233 (5)	C6—H6	0.9300
N1—C2	1.283 (6)	C7—C8	1.363 (6)
N1—C8A	1.400 (5)	C7—H7	0.9300
C2—N3	1.350 (5)	C8—C8A	1.397 (6)
C2—H2	0.9300	C8—H8	0.9300
N3—C4	1.373 (6)

N1—Cd1—N1ⁱ	175.31 (17)	C2—N3—H3	124 (3)
N1—Cd1—Cl1ⁱⁱ	95.13 (9)	C4—N3—H3	113 (3)
N1ⁱ—Cd1—Cl1ⁱⁱ	88.22 (9)	O1—C4—N3	120.7 (4)
N1—Cd1—Cl1ⁱⁱⁱ	88.22 (9)	O1—C4—C4A	124.8 (4)
N1ⁱ—Cd1—Cl1ⁱⁱⁱ	95.13 (9)	N3—C4—C4A	114.4 (4)
Cl1ⁱⁱ—Cd1—Cl1ⁱⁱⁱ	89.06 (5)	C5—C4A—C8A	120.5 (4)
N1—Cd1—Cl1	84.90 (9)	C5—C4A—C4	120.2 (4)
N1ⁱ—Cd1—Cl1	91.69 (9)	C8A—C4A—C4	119.4 (4)
Cl1ⁱⁱ—Cd1—Cl1	179.01 (3)	C6—C5—C4A	119.5 (4)
Cl1ⁱⁱⁱ—Cd1—Cl1	91.93 (4)	C6—C5—H5	120.2
N1—Cd1—Cl1ⁱ	91.69 (9)	C4A—C5—H5	120.2
N1ⁱ—Cd1—Cl1ⁱ	84.90 (9)	C5—C6—C7	119.8 (4)
Cl1ⁱⁱ—Cd1—Cl1ⁱ	91.93 (4)	C5—C6—H6	120.1
Cl1ⁱⁱⁱ—Cd1—Cl1ⁱ	179.01 (3)	C7—C6—H6	120.1
Cl1—Cd1—Cl1ⁱ	87.08 (5)	C8—C7—C6	121.3 (4)
Cd1^iv—Cl1—Cd1	91.93 (4)	C8—C7—H7	119.3
C2—N1—C8A	116.8 (4)	C6—C7—H7	119.3
C2—N1—Cd1	112.0 (3)	C7—C8—C8A	120.1 (4)
C8A—N1—Cd1	128.1 (3)	C7—C8—H8	120.0
N1—C2—N3	125.5 (4)	C8A—C8—H8	120.0
N1—C2—H2	117.3	C8—C8A—N1	120.1 (4)
N3—C2—H2	117.3	C8—C8A—C4A	118.8 (4)
C2—N3—C4	122.6 (4)	N1—C8A—C4A	121.1 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^v	0.87 (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]
M_r	475.60
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	130
a, b, c (Å)	28.839 (6), 3.7309 (7), 17.846 (4)
β (°)	123.26 (3)
V (Å³)	1605.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.71
Crystal size (mm)	0.80 × 0.03 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (MULABS; Blessing, 1995)
T_min, T_max	0.936, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	10107, 1983, 1831
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.102, 1.16
No. of reflections	1983
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.87 (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

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