Aqua­bis(2-methyl-4-oxopyrido[1,2-a]pyrimidin-9-olato)zinc(II) monohydrate

Wei, Y.-F.; Li, Z.-S.; Zhang, H.-H.; Wang, Y.-H.

doi:10.1107/S1600536808039615

metal-organic compounds

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Volume 65| Part 1| January 2009| Page m91

doi:10.1107/S1600536808039615

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Aquabis(2-methyl-4-oxopyrido[1,2-a]pyrimidin-9-olato)zinc(II) monohydrate

Yu-Feng Wei,^a Zhong-Shu Li,^a Huai-Hong Zhang ^a and Yi-Hong Wang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 21 August 2008; accepted 25 November 2008; online 17 December 2008)

The crystal structure of the title compound, [Zn(C₉H₇N₂O₂)₂(H₂O)]·H₂O, involves discrete mononuclear complex molecules. The special positions on the rotation twofold axis are occupied by Zn^II and O atoms of the coordinated and uncoordinated water molecules. The coordination around the Zn^II atom can be described as transitional from trigonal-bipyramidal to square-pyramidal. The two chelating 2-methyl-4-oxopyrido[1,2-a]pyrimidin-9-olate ligands and the coordinated water molecule form the Zn coordination. O—H⋯O hydrogen bonds between the coordinated water molecule and the ligand and between the uncoordinated water molecule and the ligand dominate the crystal packing.

Related literature

For the design and synthesis of self-assembling systems with organic ligands containing N and O donors, see: Bayot et al. (2006 ); Chen et al. (2007 ). For the structures of quinolin-8-ol complexes, see: Wu et al. (2006 ).

Experimental

Crystal data

[Zn(C₉H₇N₂O₂)₂(H₂O)]·H₂O
M_r = 451.73
Orthorhombic, P b c n
a = 7.7670 (16) Å
b = 16.045 (3) Å
c = 14.006 (3) Å
V = 1745.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.46 mm⁻¹
T = 293 (2) K
0.25 × 0.15 × 0.12 mm

Data collection

Rigaku Scxmini 1K CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.752, T_max = 0.831
16899 measured reflections
2005 independent reflections
1470 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.128
S = 1.07
2005 reflections
141 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O2ⁱ	0.72 (4)	2.11 (4)	2.823 (3)	170 (5)
O4—H4B⋯O1ⁱⁱ	0.78 (5)	2.23 (5)	3.008 (4)	176 (6)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808039615/kp2191sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039615/kp2191Isup2.hkl

checkCIF report

Comment top

Considerable attention has been paid to the design and synthesis of self-assembling systems with organic ligands containing N and O donors (Bayot et al., 2006; Chen, et al., 2007). Quinolin-8-ol is one such ligand and several crystal structures of complexes containing it have been reported (Wu et al., 2006). We report here the synthesis and crystal structure of the title complex, (I) (Fig. 1). In (I), the Zn atom is penta-coordinated by two pyridine nitrogen atoms and two oxygen atoms from the hydroxy groups and water molecule (Fig. 1 and Table 1). Intermolecular O—H···O hydrogen bonds (Table 2 and Fig. 2) connect the molecules of (I) define the crystal packing.

Related literature top

For the design and synthesis of

self-assembling systems with organic ligands containing N and O donors, see: Bayot et al. (2006); Chen et al. (2007). For the structures of quinolin-8-ol complexes, see: Wu et al. (2006).

Experimental top

All chemicals used (reagent grade) were commercially available. An aqueous solution (5 ml) of ZnCl₂ (13.6 mg, 0.1 mmol) was added by constant stirring to an ethanol solution (10 ml) containing 2-methyl-9-hydroxylpyrido [1,2-a]pyrimidin-4-one (17.6 mg, 0.1 mmol) then filtered off. After a few days, colourless, well shaped single crystals in the form of prisms deposited in the mother-liquid. They were separated off, washed with cold ethanol and dried in air at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule and the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code A: -x, y, 0.5 - z.]
	Fig. 2. Crystal packing of the compound (I). Hydrogen bonds are shown as dashed lines.

Aquabis(2-methyl-4-oxopyrido[1,2-a]pyrimidin-9-olato)zinc(II) monohydrate top

Crystal data top

[Zn(C₉H₇N₂O₂)₂(H₂O)]·H₂O	F(000) = 928
M_r = 451.73	D_x = 1.719 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 13380 reflections
a = 7.7670 (16) Å	θ = 3.0–27.6°
b = 16.045 (3) Å	µ = 1.46 mm⁻¹
c = 14.006 (3) Å	T = 293 K
V = 1745.4 (6) Å³	Prism, colourless
Z = 4	0.25 × 0.15 × 0.12 mm

Data collection top

Rigaku Scxmini 1K CCD area-detector diffractometer	2005 independent reflections
Radiation source: fine-focus sealed tube	1470 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 8.192 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
Thin–slice ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −20→20
T_min = 0.752, T_max = 0.831	l = −18→18
16899 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0591P)² + 2.2542P] where P = (F_o² + 2F_c²)/3
2005 reflections	(Δ/σ)_max < 0.001
141 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Zn(C₉H₇N₂O₂)₂(H₂O)]·H₂O	V = 1745.4 (6) Å³
M_r = 451.73	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 7.7670 (16) Å	µ = 1.46 mm⁻¹
b = 16.045 (3) Å	T = 293 K
c = 14.006 (3) Å	0.25 × 0.15 × 0.12 mm

Data collection top

Rigaku Scxmini 1K CCD area-detector diffractometer	2005 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1470 reflections with I > 2σ(I)
T_min = 0.752, T_max = 0.831	R_int = 0.070
16899 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.50 e Å⁻³
2005 reflections	Δρ_min = −0.56 e Å⁻³
141 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
C1	−0.0089 (4)	0.1222 (2)	0.4495 (2)	0.0220 (7)
C2	−0.1741 (4)	0.0991 (2)	0.4103 (2)	0.0242 (7)
C3	−0.2932 (5)	0.0659 (2)	0.4714 (3)	0.0290 (8)
H3A	−0.4012	0.0508	0.4484	0.035*
C4	−0.2541 (5)	0.0543 (2)	0.5686 (2)	0.0301 (8)
H4A	−0.3366	0.0317	0.6092	0.036*
C5	−0.0987 (5)	0.0754 (2)	0.6036 (2)	0.0308 (8)
H5A	−0.0747	0.0668	0.6680	0.037*
C6	0.1875 (5)	0.1347 (2)	0.5853 (2)	0.0287 (8)
C7	0.3026 (5)	0.1688 (2)	0.5193 (3)	0.0301 (8)
H7A	0.4105	0.1859	0.5402	0.036*
C8	0.2616 (4)	0.1779 (2)	0.4246 (2)	0.0240 (7)
C9	0.3867 (5)	0.2129 (2)	0.3541 (3)	0.0332 (9)
H9A	0.3346	0.2143	0.2920	0.050*
H9B	0.4877	0.1784	0.3523	0.050*
H9C	0.4182	0.2684	0.3729	0.050*
N1	0.1066 (4)	0.15560 (17)	0.39001 (19)	0.0230 (6)
N2	0.0251 (3)	0.10953 (18)	0.54498 (19)	0.0235 (6)
O1	−0.1984 (3)	0.11255 (17)	0.31857 (17)	0.0322 (6)
O2	0.2095 (4)	0.12461 (18)	0.67183 (17)	0.0383 (7)
Zn1	0.0000	0.16492 (4)	0.2500	0.0259 (2)
O3	0.0000	0.2946 (3)	0.2500	0.0420 (10)
O4	−0.5000	−0.0113 (3)	0.7500	0.0529 (12)
H4B	−0.420 (7)	−0.038 (4)	0.765 (4)	0.08 (2)*
H3B	0.069 (6)	0.320 (3)	0.232 (3)	0.046 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0236 (16)	0.0234 (15)	0.0189 (15)	0.0037 (15)	0.0017 (14)	−0.0002 (12)
C2	0.0215 (17)	0.0284 (18)	0.0225 (17)	0.0009 (14)	0.0003 (14)	0.0009 (14)
C3	0.0224 (17)	0.037 (2)	0.0275 (18)	−0.0033 (15)	0.0014 (15)	0.0022 (15)
C4	0.0279 (19)	0.037 (2)	0.0254 (18)	−0.0065 (16)	0.0099 (15)	0.0032 (16)
C5	0.035 (2)	0.038 (2)	0.0197 (16)	−0.0017 (17)	0.0052 (16)	0.0021 (15)
C6	0.0291 (19)	0.0329 (19)	0.0241 (17)	0.0021 (16)	−0.0055 (15)	−0.0049 (15)
C7	0.0211 (17)	0.036 (2)	0.0335 (18)	−0.0014 (15)	−0.0031 (15)	−0.0063 (16)
C8	0.0206 (16)	0.0242 (17)	0.0273 (17)	0.0008 (13)	0.0030 (14)	−0.0064 (14)
C9	0.030 (2)	0.040 (2)	0.0295 (18)	−0.0102 (17)	0.0041 (16)	−0.0066 (16)
N1	0.0222 (15)	0.0285 (15)	0.0185 (13)	−0.0024 (12)	0.0024 (11)	−0.0012 (11)
N2	0.0234 (16)	0.0295 (15)	0.0177 (13)	0.0005 (12)	0.0015 (11)	−0.0008 (11)
O1	0.0234 (13)	0.0505 (16)	0.0228 (12)	−0.0071 (12)	−0.0026 (10)	0.0072 (11)
O2	0.0387 (16)	0.0545 (17)	0.0218 (13)	−0.0045 (14)	−0.0078 (11)	0.0000 (12)
Zn1	0.0240 (3)	0.0347 (3)	0.0191 (3)	0.000	0.0024 (2)	0.000
O3	0.040 (2)	0.032 (2)	0.054 (3)	0.000	0.021 (2)	0.000
O4	0.046 (3)	0.059 (3)	0.054 (3)	0.000	0.000 (3)	0.000

Geometric parameters (Å, º) top

C1—N1	1.336 (4)	C7—C8	1.372 (5)
C1—N2	1.378 (4)	C7—H7A	0.9300
C1—C2	1.444 (5)	C8—N1	1.346 (4)
C2—O1	1.316 (4)	C8—C9	1.494 (5)
C2—C3	1.368 (5)	C9—H9A	0.9600
C3—C4	1.408 (5)	C9—H9B	0.9600
C3—H3A	0.9300	C9—H9C	0.9600
C4—C5	1.346 (5)	N1—Zn1	2.134 (3)
C4—H4A	0.9300	O1—Zn1	2.001 (2)
C5—N2	1.379 (4)	Zn1—O1ⁱ	2.001 (2)
C5—H5A	0.9300	Zn1—O3	2.081 (4)
C6—O2	1.234 (4)	Zn1—N1ⁱ	2.134 (3)
C6—C7	1.398 (5)	O3—H3B	0.72 (4)
C6—N2	1.440 (4)	O4—H4B	0.78 (5)

N1—C1—N2	122.4 (3)	C8—C9—H9A	109.5
N1—C1—C2	117.5 (3)	C8—C9—H9B	109.5
N2—C1—C2	120.1 (3)	H9A—C9—H9B	109.5
O1—C2—C3	125.2 (3)	C8—C9—H9C	109.5
O1—C2—C1	117.2 (3)	H9A—C9—H9C	109.5
C3—C2—C1	117.6 (3)	H9B—C9—H9C	109.5
C2—C3—C4	120.7 (3)	C1—N1—C8	118.9 (3)
C2—C3—H3A	119.7	C1—N1—Zn1	109.9 (2)
C4—C3—H3A	119.7	C8—N1—Zn1	131.2 (2)
C5—C4—C3	120.9 (3)	C1—N2—C5	120.2 (3)
C5—C4—H4A	119.6	C1—N2—C6	120.5 (3)
C3—C4—H4A	119.6	C5—N2—C6	119.3 (3)
C4—C5—N2	120.5 (3)	C2—O1—Zn1	115.3 (2)
C4—C5—H5A	119.7	O1—Zn1—O1ⁱ	130.33 (16)
N2—C5—H5A	119.7	O1—Zn1—O3	114.83 (8)
O2—C6—C7	127.8 (4)	O1ⁱ—Zn1—O3	114.83 (8)
O2—C6—N2	118.0 (3)	O1—Zn1—N1ⁱ	96.48 (10)
C7—C6—N2	114.2 (3)	O1ⁱ—Zn1—N1ⁱ	80.11 (10)
C8—C7—C6	122.2 (3)	O3—Zn1—N1ⁱ	94.02 (7)
C8—C7—H7A	118.9	O1—Zn1—N1	80.11 (10)
C6—C7—H7A	118.9	O1ⁱ—Zn1—N1	96.48 (10)
N1—C8—C7	121.8 (3)	O3—Zn1—N1	94.02 (7)
N1—C8—C9	116.4 (3)	N1ⁱ—Zn1—N1	171.96 (15)
C7—C8—C9	121.8 (3)	Zn1—O3—H3B	125 (4)

N1—C1—C2—O1	0.1 (5)	N1—C1—N2—C6	2.0 (5)
N2—C1—C2—O1	−179.8 (3)	C2—C1—N2—C6	−178.2 (3)
N1—C1—C2—C3	−179.2 (3)	C4—C5—N2—C1	−0.2 (5)
N2—C1—C2—C3	0.9 (5)	C4—C5—N2—C6	177.5 (3)
O1—C2—C3—C4	−179.8 (3)	O2—C6—N2—C1	177.5 (3)
C1—C2—C3—C4	−0.6 (5)	C7—C6—N2—C1	−2.0 (5)
C2—C3—C4—C5	−0.1 (6)	O2—C6—N2—C5	−0.1 (5)
C3—C4—C5—N2	0.5 (6)	C7—C6—N2—C5	−179.7 (3)
O2—C6—C7—C8	−178.9 (4)	C3—C2—O1—Zn1	178.4 (3)
N2—C6—C7—C8	0.6 (5)	C1—C2—O1—Zn1	−0.9 (4)
C6—C7—C8—N1	1.1 (5)	C2—O1—Zn1—O1ⁱ	91.1 (2)
C6—C7—C8—C9	−178.7 (3)	C2—O1—Zn1—O3	−88.9 (2)
N2—C1—N1—C8	−0.2 (5)	C2—O1—Zn1—N1ⁱ	173.6 (2)
C2—C1—N1—C8	179.9 (3)	C2—O1—Zn1—N1	0.9 (2)
N2—C1—N1—Zn1	−179.5 (2)	C1—N1—Zn1—O1	−0.8 (2)
C2—C1—N1—Zn1	0.7 (4)	C8—N1—Zn1—O1	−179.9 (3)
C7—C8—N1—C1	−1.3 (5)	C1—N1—Zn1—O1ⁱ	−130.7 (2)
C9—C8—N1—C1	178.5 (3)	C8—N1—Zn1—O1ⁱ	50.2 (3)
C7—C8—N1—Zn1	177.8 (2)	C1—N1—Zn1—O3	113.7 (2)
C9—C8—N1—Zn1	−2.4 (4)	C8—N1—Zn1—O3	−65.4 (3)
N1—C1—N2—C5	179.6 (3)	C1—N1—Zn1—N1ⁱ	−66.3 (2)
C2—C1—N2—C5	−0.6 (5)	C8—N1—Zn1—N1ⁱ	114.6 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2ⁱⁱ	0.72 (4)	2.11 (4)	2.823 (3)	170 (5)
O4—H4B···O1ⁱⁱⁱ	0.78 (5)	2.23 (5)	3.008 (4)	176 (6)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₉H₇N₂O₂)₂(H₂O)]·H₂O
M_r	451.73
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	7.7670 (16), 16.045 (3), 14.006 (3)
V (Å³)	1745.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.46
Crystal size (mm)	0.25 × 0.15 × 0.12

Data collection
Diffractometer	Rigaku Scxmini 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.752, 0.831
No. of measured, independent and observed [I > 2σ(I)] reflections	16899, 2005, 1470
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.07
No. of reflections	2005
No. of parameters	141
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.56

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2ⁱ	0.72 (4)	2.11 (4)	2.823 (3)	170 (5)
O4—H4B···O1ⁱⁱ	0.78 (5)	2.23 (5)	3.008 (4)	176 (6)

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

References

Bayot, D., Degand, M., Tinant, B. & Devillers, M. (2006). Inorg. Chem. Commun. 359, 1390–1394. CAS Google Scholar
Chen, K., Zhang, Y.-L., Feng, M.-Q. & Liu, C.-H. (2007). Acta Cryst. E63, m2033. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, H., Dong, X.-W., Liu, H.-Y. & Ma, J.-F. (2006). Acta Cryst. E62, m281–m282. Web of Science CSD CrossRef IUCr Journals Google Scholar

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