Diaqua­bis(5-methyl­pyridine-2-carboxyl­ato-κ2N,O)zinc(II)

Du, L.-C.

doi:10.1107/S1600536808042530

metal-organic compounds

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Volume 65| Part 1| January 2009| Page m106

doi:10.1107/S1600536808042530

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Diaquabis(5-methylpyridine-2-carboxylato-κ²N,O)zinc(II)

Lian-Cai Du ^a ^*

^aCollege of Bioengineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 13 December 2008; accepted 14 December 2008; online 20 December 2008)

In the title compound, [Zn(C₇H₆NO₂)₂(H₂O)₂], the Zn atom (site symmetry $[\overline{1}]$ ) adopts a distorted trans-ZnN₂O₄ octahedral coordination arising from two N,O-bidentate 5-methylpyridine-2-carboxylate ligands and two water molecules. In the crystal structure, molecules form a layered network linked by O—H⋯O hydrogen bonds.

Related literature

For background, see: Hagrman et al. (1998 ); Ranford et al. (1998 ).

Experimental

Crystal data

[Zn(C₇H₆NO₂)₂(H₂O)₂]
M_r = 373.66
Triclinic, $[P \overline 1]$
a = 5.1703 (6) Å
b = 6.4620 (10) Å
c = 12.2781 (14) Å
α = 104.678 (2)°
β = 90.646 (1)°
γ = 109.493 (2)°
V = 372.01 (8) Å³
Z = 1
Mo Kα radiation
μ = 1.68 mm⁻¹
T = 298 (2) K
0.49 × 0.46 × 0.27 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.493, T_max = 0.659
1917 measured reflections
1275 independent reflections
1260 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.15
1275 reflections
108 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.104 (2)
Zn1—O3	2.134 (2)
Zn1—N1	2.116 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱ	0.85	1.88	2.693 (4)	160
O3—H3B⋯O1ⁱⁱ	0.85	1.94	2.757 (3)	160
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x-1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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 global, I. DOI: 10.1107/S1600536808042530/hb2880sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042530/hb2880Isup2.hkl

checkCIF report

Comment top

As part of our efforts to achieve supramolecular transition metal complexes by self-assembly (Ranford, et al., 1998; Hagrman, et al., 1998), we now report on the synthesis and crystal structure of the title compound, (I), (Fig. 1).

The Zn^II centre in (I) is six-coordinate with two O donors of H₂O, and two N,O-bidentate ligands (Table 1). In the crystal packing, the molecules form a layers linked by O—H···O hydrogen bonds (Table 2).

Related literature top

For background, see: Hagrman et al. (1998); Ranford et al. (1998).

Experimental top

A solution of 1.0 mmol 5-methylpyridine-2-carboxylic acid and 1.0 mmol NaOH in 5 ml 95% ethanol was added to a solution of 0.5 mmol Zn(CH₃COO)₂.4H₂O in 5 ml ethanol at room temperature. The mixture was refluxed for 2 h with stirring, then the resulting precipitate was filtered, washed, and dried in vacuo over P₄O₁₀ for 48 h. Colourless blocks of (I) were obtained by slowly evaporating from methanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (I) showing 50% displacement ellipsoids for the non-hydrogen atoms. Symmetry code: (i) 1–x, 1–y, 1–z.

Diaquabis(5-methylpyridine-2-carboxylato-κ²N,O)zinc(II) top

Crystal data top

[Zn(C₇H₆NO₂)₂(H₂O)₂]	Z = 1
M_r = 373.66	F(000) = 192
Triclinic, P1	D_x = 1.668 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1703 (6) Å	Cell parameters from 1975 reflections
b = 6.462 (1) Å	θ = 3.4–27.9°
c = 12.2781 (14) Å	µ = 1.68 mm⁻¹
α = 104.678 (2)°	T = 298 K
β = 90.646 (1)°	Block, colourless
γ = 109.493 (2)°	0.49 × 0.46 × 0.27 mm
V = 372.01 (8) Å³

Data collection top

Bruker SMART CCD diffractometer	1275 independent reflections
Radiation source: fine-focus sealed tube	1260 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→3
T_min = 0.493, T_max = 0.659	k = −6→7
1917 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0603P)² + 0.3083P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
1275 reflections	Δρ_max = 0.63 e Å⁻³
108 parameters	Δρ_min = −0.60 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.094 (11)

Crystal data top

[Zn(C₇H₆NO₂)₂(H₂O)₂]	γ = 109.493 (2)°
M_r = 373.66	V = 372.01 (8) Å³
Triclinic, P1	Z = 1
a = 5.1703 (6) Å	Mo Kα radiation
b = 6.462 (1) Å	µ = 1.68 mm⁻¹
c = 12.2781 (14) Å	T = 298 K
α = 104.678 (2)°	0.49 × 0.46 × 0.27 mm
β = 90.646 (1)°

Data collection top

Bruker SMART CCD diffractometer	1275 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1260 reflections with I > 2σ(I)
T_min = 0.493, T_max = 0.659	R_int = 0.013
1917 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.15	Δρ_max = 0.63 e Å⁻³
1275 reflections	Δρ_min = −0.60 e Å⁻³
108 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	0.0269 (2)
N1	0.4060 (5)	0.5257 (4)	0.6691 (2)	0.0265 (5)
C4	0.3260 (7)	0.5138 (6)	0.8903 (2)	0.0351 (7)
H4	0.2979	0.5079	0.9643	0.042*
O1	0.6819 (4)	0.2811 (3)	0.54326 (17)	0.0298 (5)
O2	0.7442 (5)	0.1369 (4)	0.6842 (2)	0.0399 (6)
O3	0.1258 (4)	0.2198 (4)	0.4350 (2)	0.0368 (5)
H3A	0.1410	0.0905	0.4068	0.044*
H3B	−0.0199	0.2048	0.4683	0.044*
C1	0.6533 (6)	0.2552 (5)	0.6414 (2)	0.0266 (6)
C2	0.4953 (6)	0.3907 (5)	0.7150 (2)	0.0269 (6)
C3	0.4520 (8)	0.3852 (6)	0.8251 (3)	0.0417 (8)
H3	0.5124	0.2887	0.8550	0.050*
C6	0.2809 (6)	0.6541 (5)	0.7341 (3)	0.0309 (6)
H6	0.2175	0.7490	0.7040	0.037*
C5	0.2430 (6)	0.6500 (6)	0.8452 (3)	0.0351 (7)
C7	0.1086 (8)	0.8011 (7)	0.9188 (3)	0.0500 (9)
H7A	−0.0093	0.7186	0.9650	0.075*
H7B	0.0010	0.8473	0.8718	0.075*
H7C	0.2483	0.9337	0.9664	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0346 (3)	0.0309 (3)	0.0229 (3)	0.0191 (2)	0.00841 (19)	0.01007 (19)
N1	0.0300 (12)	0.0281 (12)	0.0253 (12)	0.0143 (10)	0.0049 (10)	0.0083 (10)
C4	0.0477 (18)	0.0513 (19)	0.0163 (13)	0.0286 (15)	0.0102 (12)	0.0108 (13)
O1	0.0357 (11)	0.0321 (11)	0.0293 (11)	0.0209 (9)	0.0098 (8)	0.0089 (9)
O2	0.0559 (14)	0.0394 (12)	0.0369 (12)	0.0323 (11)	0.0035 (10)	0.0111 (10)
O3	0.0337 (11)	0.0298 (11)	0.0486 (13)	0.0161 (9)	0.0117 (10)	0.0067 (10)
C1	0.0274 (13)	0.0224 (13)	0.0306 (15)	0.0109 (11)	0.0018 (11)	0.0052 (11)
C2	0.0304 (14)	0.0264 (13)	0.0252 (14)	0.0119 (11)	0.0036 (11)	0.0066 (11)
C3	0.054 (2)	0.051 (2)	0.0337 (17)	0.0306 (17)	0.0084 (15)	0.0194 (15)
C6	0.0349 (15)	0.0321 (15)	0.0313 (15)	0.0196 (12)	0.0078 (12)	0.0076 (12)
C5	0.0341 (15)	0.0399 (17)	0.0289 (15)	0.0146 (13)	0.0065 (12)	0.0029 (13)
C7	0.054 (2)	0.059 (2)	0.0395 (19)	0.0315 (19)	0.0155 (16)	0.0005 (17)

Geometric parameters (Å, º) top

Zn1—O1	2.104 (2)	O2—C1	1.232 (4)
Zn1—O3	2.134 (2)	O3—H3A	0.8499
Zn1—O1ⁱ	2.104 (2)	O3—H3B	0.8499
Zn1—N1ⁱ	2.116 (2)	C1—C2	1.531 (4)
Zn1—N1	2.116 (2)	C2—C3	1.380 (4)
Zn1—O3ⁱ	2.134 (2)	C3—H3	0.9300
N1—C6	1.334 (4)	C6—C5	1.387 (5)
N1—C2	1.343 (4)	C6—H6	0.9300
C4—C5	1.327 (5)	C5—C7	1.507 (4)
C4—C3	1.338 (5)	C7—H7A	0.9600
C4—H4	0.9300	C7—H7B	0.9600
O1—C1	1.262 (4)	C7—H7C	0.9600

O1—Zn1—O1ⁱ	180.0	Zn1—O3—H3B	121.9
O1—Zn1—N1ⁱ	100.78 (8)	H3A—O3—H3B	110.5
O1ⁱ—Zn1—N1ⁱ	79.22 (8)	O2—C1—O1	126.8 (3)
O1—Zn1—N1	79.22 (8)	O2—C1—C2	117.3 (3)
O1ⁱ—Zn1—N1	100.78 (8)	O1—C1—C2	115.9 (2)
N1ⁱ—Zn1—N1	180.0	N1—C2—C3	120.1 (3)
O1—Zn1—O3ⁱ	89.38 (9)	N1—C2—C1	116.9 (2)
O1ⁱ—Zn1—O3ⁱ	90.62 (9)	C3—C2—C1	123.0 (3)
N1ⁱ—Zn1—O3ⁱ	92.23 (9)	C4—C3—C2	122.3 (3)
N1—Zn1—O3ⁱ	87.77 (9)	C4—C3—H3	118.8
O1—Zn1—O3	90.62 (9)	C2—C3—H3	118.8
O1ⁱ—Zn1—O3	89.38 (9)	N1—C6—C5	121.7 (3)
N1ⁱ—Zn1—O3	87.77 (9)	N1—C6—H6	119.1
N1—Zn1—O3	92.23 (9)	C5—C6—H6	119.1
O3ⁱ—Zn1—O3	180.0	C4—C5—C6	120.9 (3)
C6—N1—C2	117.7 (2)	C4—C5—C7	117.9 (3)
C6—N1—Zn1	130.4 (2)	C6—C5—C7	121.2 (3)
C2—N1—Zn1	111.95 (18)	C5—C7—H7A	109.5
C5—C4—C3	117.3 (3)	C5—C7—H7B	109.5
C5—C4—H4	121.3	H7A—C7—H7B	109.5
C3—C4—H4	121.3	C5—C7—H7C	109.5
C1—O1—Zn1	115.99 (17)	H7A—C7—H7C	109.5
Zn1—O3—H3A	116.6	H7B—C7—H7C	109.5

O1—Zn1—N1—C6	176.5 (3)	C6—N1—C2—C1	−176.5 (2)
O1ⁱ—Zn1—N1—C6	−3.5 (3)	Zn1—N1—C2—C1	2.3 (3)
O3ⁱ—Zn1—N1—C6	86.7 (3)	O2—C1—C2—N1	177.6 (3)
O3—Zn1—N1—C6	−93.3 (3)	O1—C1—C2—N1	−0.9 (4)
O1—Zn1—N1—C2	−2.21 (19)	O2—C1—C2—C3	0.0 (4)
O1ⁱ—Zn1—N1—C2	177.79 (19)	O1—C1—C2—C3	−178.5 (3)
O3ⁱ—Zn1—N1—C2	−92.0 (2)	C5—C4—C3—C2	−0.2 (6)
O3—Zn1—N1—C2	88.0 (2)	N1—C2—C3—C4	−1.1 (5)
N1ⁱ—Zn1—O1—C1	−178.1 (2)	C1—C2—C3—C4	176.4 (3)
N1—Zn1—O1—C1	1.9 (2)	C2—N1—C6—C5	0.0 (4)
O3ⁱ—Zn1—O1—C1	89.7 (2)	Zn1—N1—C6—C5	−178.6 (2)
O3—Zn1—O1—C1	−90.3 (2)	C3—C4—C5—C6	1.3 (5)
Zn1—O1—C1—O2	−179.4 (2)	C3—C4—C5—C7	−178.2 (3)
Zn1—O1—C1—C2	−1.2 (3)	N1—C6—C5—C4	−1.3 (5)
C6—N1—C2—C3	1.2 (4)	N1—C6—C5—C7	178.2 (3)
Zn1—N1—C2—C3	−180.0 (2)

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
O3—H3A···O2ⁱⁱ	0.85	1.88	2.693 (4)	160
O3—H3B···O1ⁱⁱⁱ	0.85	1.94	2.757 (3)	160

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₆NO₂)₂(H₂O)₂]
M_r	373.66
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.1703 (6), 6.462 (1), 12.2781 (14)
α, β, γ (°)	104.678 (2), 90.646 (1), 109.493 (2)
V (Å³)	372.01 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.68
Crystal size (mm)	0.49 × 0.46 × 0.27

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.493, 0.659
No. of measured, independent and observed [I > 2σ(I)] reflections	1917, 1275, 1260
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 1.15
No. of reflections	1275
No. of parameters	108
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.60

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O1	2.104 (2)	Zn1—N1	2.116 (2)
Zn1—O3	2.134 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.85	1.88	2.693 (4)	160
O3—H3B···O1ⁱⁱ	0.85	1.94	2.757 (3)	160

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

Acknowledgements

The author thanks the Science and Technology Foundation of Weifang (2008–19) for a research grant.

References

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