Diaqua­bis(picolinato N-oxide-κ2O,O′)zinc(II)

Li, X.-B.; Shang, R.-L.; Sun, B.-W.

doi:10.1107/S1600536807043681

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m131

https://doi.org/10.1107/S1600536807043681

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Diaquabis(picolinato N-oxide-κ²O,O′)zinc(II)

Xiu-Bing Li,^a Run-Ling Shang ^a and Bai-Wang Sun ^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 31 August 2007; accepted 5 September 2007; online 6 December 2007)

In the title compound, [Zn(C₆H₄NO₃)₂(H₂O)₂], the Zn atom is located on a centre of inversion and shows a distorted octahedral coordination geometry. Two aqua ligands occupy the axial positions and four O atoms of the two chelating picolinic acid N-oxide ligands are located in the equatorial plane. Intermolecular hydrogen bonds between aqua ligands and organic ligands link molecules into a two-dimensional arrangement.

Related literature

For related literature, see: Bayot et al. (2006 ); Ciurtin et al. (2003 ); Lawrence et al. (1999 ); Meinrath et al. (2006 ); Shan et al. (2002 ); Steiner (2002 ); Yang et al. (2004 ); Zafar et al. (2000 ).

Experimental

Crystal data

[Zn(C₆H₄NO₃)₂(H₂O)₂]
M_r = 377.63
Monoclinic, P 2₁ /c
a = 6.6837 (5) Å
b = 15.7376 (13) Å
c = 6.9935 (6) Å
β = 115.3700 (10)°
V = 664.67 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.90 mm⁻¹
T = 298 (2) K
0.21 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan CrystalClear (Rigaku, 2005 ) T_min = 0.674, T_max = 0.733
3515 measured reflections
1170 independent reflections
1033 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.149
S = 1.15
1170 reflections
106 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—O3	2.049 (3)
Zn1—O2	2.059 (3)
Zn1—O1W	2.143 (3)

O3—Zn1—O2	86.46 (11)
O3—Zn1—O1Wⁱ	89.79 (11)
O2—Zn1—O1Wⁱ	88.93 (12)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O1ⁱⁱ	0.90	1.98	2.753 (4)	143
O1W—H1WA⋯O1ⁱⁱⁱ	0.90	2.20	2.742 (4)	118
Symmetry codes: (ii) -x, -y+1, -z+1; (iii) x+1, y, z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807043681/er2040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807043681/er2040Isup2.hkl

checkCIF report

Comment top

In the past decade, much 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; Ciurtin et al., 2003; Steiner, 2002; Zafar et al., 2000). Picolinic acid N-oxide (PANO) is one such ligand and several crystal structures of complexes containing the PANO ligand have been reported (Yang et al., 2004; Shan et al., 2002; Lawrence et al., 1999; Meinrath et al., 2006). We report here the synthesis and crystal structure of the title complex, (I) (Fig. 1). In (I), the Zn atom is located on a crystallographic inversion centre and adopts a distorted octahedral coordination geometry. The coordination environment is defined by two pyridine N-oxide oxygen donors and two oxygen donors from the carboxylate groups located in the equatorial plane and two aqua O-atom donors located in the axial positions (Fig. 1). Selected bond lengths and angles are shown in Table 1. Intermolecular O1W—H1WA···O1, O1W—H1WB···O1 hydrogen bonds between water molecules and carboxylate groups connect the molecules of (I) into a two-dimensional network (Table 2 and Fig. 2).

Related literature top

For related literature, see: Bayot et al. (2006); Ciurtin et al. (2003); Lawrence et al. (1999); Meinrath et al. (2006); Shan et al. (2002); Steiner (2002); Yang et al. (2004); Zafar et al. (2000).

Experimental top

All chemicals were obtained from commercial sources and used without further purification. The title compound was prepared by the direct reaction of Zn(OOCCH₃)₂.2H₂O (22.1 mg, 0.1 mmol) and picolinic acid N-oxide (13.9 mg, 0.1 mmol) in water solution. Colourless block-shaped single crystals were obtained by slow evaporation at room temperature for about three weeks.

Structure description top

For related literature, see: Bayot et al. (2006); Ciurtin et al. (2003); Lawrence et al. (1999); Meinrath et al. (2006); Shan et al. (2002); Steiner (2002); Yang et al. (2004); Zafar et al. (2000).

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).

Figures top

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

Diaquabis(picolinato N-oxide-κ²O,O')zinc(II) top

Crystal data top

[Zn(C₆H₄NO₃)₂(H₂O)₂]	F(000) = 384
M_r = 377.63	D_x = 1.887 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 6.6837 (5) Å	θ = 7.5–15°
b = 15.7376 (13) Å	µ = 1.90 mm⁻¹
c = 6.9935 (6) Å	T = 298 K
β = 115.370 (1)°	Block, colourless
V = 664.67 (9) Å³	0.21 × 0.18 × 0.16 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1170 independent reflections
Radiation source: fine-focus sealed tube	1033 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 10 pixels mm^-1	θ_max = 25.0°, θ_min = 2.6°
φ and ω scans	h = −7→7
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	k = −18→17
T_min = 0.674, T_max = 0.733	l = −6→8
3515 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0918P)² + 1.2258P] where P = (F_o² + 2F_c²)/3
1170 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[Zn(C₆H₄NO₃)₂(H₂O)₂]	V = 664.67 (9) Å³
M_r = 377.63	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6837 (5) Å	µ = 1.90 mm⁻¹
b = 15.7376 (13) Å	T = 298 K
c = 6.9935 (6) Å	0.21 × 0.18 × 0.16 mm
β = 115.370 (1)°

Data collection top

Bruker SMART CCD diffractometer	1170 independent reflections
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	1033 reflections with I > 2σ(I)
T_min = 0.674, T_max = 0.733	R_int = 0.019
3515 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.15	Δρ_max = 0.56 e Å⁻³
1170 reflections	Δρ_min = −0.90 e Å⁻³
106 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
Zn1	0.5000	0.5000	0.5000	0.0252 (3)
O1W	0.4917 (5)	0.43468 (18)	0.7653 (4)	0.0222 (7)
H1WA	0.6291	0.4170	0.8515	0.033*
H1WB	0.4423	0.4702	0.8365	0.033*
O1	−0.1745 (5)	0.49427 (16)	0.1316 (6)	0.0229 (7)
O2	0.1644 (5)	0.52224 (19)	0.3760 (5)	0.0218 (7)
O3	0.4215 (4)	0.38945 (17)	0.3288 (5)	0.0217 (7)
N1	0.2521 (5)	0.3424 (2)	0.3225 (5)	0.0168 (7)
C1	0.0530 (6)	0.3771 (2)	0.2833 (6)	0.0175 (8)
C2	−0.1198 (7)	0.3240 (3)	0.2650 (7)	0.0232 (9)
H2A	−0.2610	0.3483	0.2384	0.028*
C3	−0.0923 (8)	0.2365 (3)	0.2826 (7)	0.0287 (10)
H3A	−0.2135	0.1999	0.2667	0.034*
C4	0.1137 (8)	0.2034 (3)	0.3249 (7)	0.0273 (10)
H4A	0.1386	0.1432	0.3403	0.033*
C5	0.2825 (7)	0.2572 (3)	0.3436 (7)	0.0234 (9)
H5A	0.4259	0.2341	0.3737	0.028*
C6	0.0146 (6)	0.4725 (3)	0.2616 (6)	0.0177 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0186 (5)	0.0236 (5)	0.0293 (5)	−0.0011 (2)	0.0064 (4)	−0.0029 (3)
O1W	0.0178 (14)	0.0239 (15)	0.0222 (14)	0.0006 (11)	0.0059 (11)	0.0006 (11)
O1	0.0128 (16)	0.0208 (16)	0.0256 (17)	0.0033 (10)	−0.0008 (13)	−0.0021 (11)
O2	0.0118 (14)	0.0176 (13)	0.0289 (16)	−0.0007 (11)	0.0020 (12)	−0.0062 (13)
O3	0.0131 (13)	0.0210 (14)	0.0313 (16)	−0.0047 (11)	0.0099 (12)	−0.0094 (12)
N1	0.0162 (16)	0.0150 (16)	0.0172 (16)	−0.0009 (12)	0.0051 (13)	−0.0036 (13)
C1	0.0165 (19)	0.0163 (19)	0.0172 (19)	0.0014 (15)	0.0048 (16)	−0.0027 (15)
C2	0.019 (2)	0.021 (2)	0.028 (2)	−0.0020 (16)	0.0087 (18)	−0.0012 (17)
C3	0.032 (3)	0.023 (2)	0.032 (2)	−0.0086 (18)	0.015 (2)	−0.0015 (18)
C4	0.039 (3)	0.014 (2)	0.029 (2)	0.0003 (17)	0.014 (2)	−0.0004 (17)
C5	0.027 (2)	0.0164 (19)	0.025 (2)	0.0044 (16)	0.0089 (19)	−0.0026 (16)
C6	0.0146 (19)	0.0186 (19)	0.022 (2)	0.0019 (16)	0.0101 (16)	0.0006 (16)

Geometric parameters (Å, º) top

Zn1—O3ⁱ	2.049 (3)	N1—C1	1.354 (5)
Zn1—O3	2.049 (3)	N1—C5	1.356 (5)
Zn1—O2ⁱ	2.059 (3)	C1—C2	1.386 (6)
Zn1—O2	2.059 (3)	C1—C6	1.520 (5)
Zn1—O1Wⁱ	2.143 (3)	C2—C3	1.389 (6)
Zn1—O1W	2.143 (3)	C2—H2A	0.9600
O1W—H1WA	0.9000	C3—C4	1.381 (7)
O1W—H1WB	0.9001	C3—H3A	0.9601
O1—C6	1.247 (5)	C4—C5	1.371 (6)
O2—C6	1.253 (5)	C4—H4A	0.9597
O3—N1	1.338 (4)	C5—H5A	0.9600

O3ⁱ—Zn1—O3	180.00 (8)	O3—N1—C5	117.3 (3)
O3ⁱ—Zn1—O2ⁱ	86.46 (11)	C1—N1—C5	120.6 (3)
O3—Zn1—O2ⁱ	93.54 (11)	N1—C1—C2	118.9 (4)
O3ⁱ—Zn1—O2	93.54 (11)	N1—C1—C6	121.8 (3)
O3—Zn1—O2	86.46 (11)	C2—C1—C6	119.2 (3)
O2ⁱ—Zn1—O2	180.0	C3—C2—C1	121.1 (4)
O3ⁱ—Zn1—O1Wⁱ	90.21 (11)	C3—C2—H2A	119.6
O3—Zn1—O1Wⁱ	89.79 (11)	C1—C2—H2A	119.3
O2ⁱ—Zn1—O1Wⁱ	91.07 (12)	C2—C3—C4	118.3 (4)
O2—Zn1—O1Wⁱ	88.93 (12)	C2—C3—H3A	120.8
O3ⁱ—Zn1—O1W	89.79 (11)	C4—C3—H3A	120.9
O3—Zn1—O1W	90.21 (11)	C5—C4—C3	119.5 (4)
O2ⁱ—Zn1—O1W	88.93 (12)	C5—C4—H4A	120.2
O2—Zn1—O1W	91.07 (12)	C3—C4—H4A	120.3
O1Wⁱ—Zn1—O1W	180.00 (13)	N1—C5—C4	121.5 (4)
Zn1—O1W—H1WA	109.3	N1—C5—H5A	119.2
Zn1—O1W—H1WB	109.5	C4—C5—H5A	119.4
H1WA—O1W—H1WB	109.5	O2—C6—O1	125.2 (4)
C6—O2—Zn1	126.3 (3)	O2—C6—C1	119.9 (4)
N1—O3—Zn1	119.4 (2)	O1—C6—C1	114.8 (3)
O3—N1—C1	121.9 (3)

O3ⁱ—Zn1—O2—C6	−175.0 (3)	C2—C1—C2—C3	0 (100)
O3—Zn1—O2—C6	5.0 (3)	C6—C1—C2—C3	179.7 (4)
O1Wⁱ—Zn1—O2—C6	94.8 (3)	C1—C2—C3—C2	0 (2)
O1W—Zn1—O2—C6	−85.2 (3)	C2—C2—C3—C4	0.0 (7)
O2ⁱ—Zn1—O3—N1	137.7 (3)	C1—C2—C3—C4	1.8 (7)
O2—Zn1—O3—N1	−42.3 (3)	C2—C3—C4—C5	−1.4 (7)
O1Wⁱ—Zn1—O3—N1	−131.2 (3)	C2—C3—C4—C5	−1.4 (7)
O1W—Zn1—O3—N1	48.8 (3)	O3—N1—C5—C4	−175.5 (4)
Zn1—O3—N1—C1	47.5 (4)	C1—N1—C5—C4	0.4 (6)
Zn1—O3—N1—C5	−136.6 (3)	C3—C4—C5—N1	0.3 (6)
O3—N1—C1—C2	175.7 (3)	Zn1—O2—C6—O1	−154.2 (3)
C5—N1—C1—C2	0.0 (6)	Zn1—O2—C6—C1	28.9 (5)
O3—N1—C1—C2	175.7 (3)	N1—C1—C6—O2	−36.9 (6)
C5—N1—C1—C2	0.0 (6)	C2—C1—C6—O2	142.3 (4)
O3—N1—C1—C6	−5.1 (5)	C2—C1—C6—O2	142.3 (4)
C5—N1—C1—C6	179.2 (4)	N1—C1—C6—O1	145.9 (4)
N1—C1—C2—C2	0.0 (2)	C2—C1—C6—O1	−34.9 (5)
C6—C1—C2—C2	0.00 (6)	C2—C1—C6—O1	−34.9 (5)
N1—C1—C2—C3	−1.1 (6)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O1ⁱⁱ	0.90	1.98	2.753 (4)	143
O1W—H1WA···O1ⁱⁱⁱ	0.90	2.20	2.742 (4)	118

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

Experimental details

Crystal data
Chemical formula	[Zn(C₆H₄NO₃)₂(H₂O)₂]
M_r	377.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.6837 (5), 15.7376 (13), 6.9935 (6)
β (°)	115.370 (1)
V (Å³)	664.67 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.90
Crystal size (mm)	0.21 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan CrystalClear (Rigaku, 2005)
T_min, T_max	0.674, 0.733
No. of measured, independent and observed [I > 2σ(I)] reflections	3515, 1170, 1033
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.149, 1.15
No. of reflections	1170
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.90

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999).

Selected geometric parameters (Å, º) top

Zn1—O3	2.049 (3)	O1—C6	1.247 (5)
Zn1—O2	2.059 (3)	O2—C6	1.253 (5)
Zn1—O1W	2.143 (3)	O3—N1	1.338 (4)

O3—Zn1—O2	86.46 (11)	C6—O2—Zn1	126.3 (3)
O3—Zn1—O1Wⁱ	89.79 (11)	N1—O3—Zn1	119.4 (2)
O2—Zn1—O1Wⁱ	88.93 (12)	O2—C6—O1	125.2 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O1ⁱⁱ	0.90	1.98	2.753 (4)	143.4
O1W—H1WA···O1ⁱⁱⁱ	0.90	2.20	2.742 (4)	118.2

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

Acknowledgements

The authors are grateful to the National Natural Science Foundation of China (project No. 20671019) for financial support.

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