catena-Poly[[(acetato-κO)[4-(1H-pyrazol-3-yl)pyridine-κN1]zinc]-μ-acetato-κ2O:O′]

Tan, Z.-D.; Tan, F.-J.; Tan, B.; Yi, Z.-W.

doi:10.1107/S1600536811040190

metal-organic compounds

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Volume 67| Part 11| November 2011| Page m1512

doi:10.1107/S1600536811040190

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catena-Poly[[(acetato-κO)[4-(1H-pyrazol-3-yl)pyridine-κN¹]zinc]-μ-acetato-κ²O:O′]

Zheng-De Tan,^a ^* Feng-Jiao Tan,^b Bo Tan ^b and Zhi-Wen Yi ^a

^aCollege of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, People's Republic of China, and ^bThe People's Hospital of Xiangtan County, Xiangtan 411104, People's Republic of China
^*Correspondence e-mail: tzd0517@163.com

(Received 20 August 2011; accepted 29 September 2011; online 12 October 2011)

In the title compound, [Zn(CH₃CO₂)₂(C₈H₇N₃)]_n, the Zn^II atom is coordinated by one N atom from a 4-(1H-pyrazol-3-yl)pyridine ligand and three O atoms from two bridging and one terminal acetate ligands, forming a distorted tetrahedral geometry. The bridging acetate ligands link the Zn atoms into a chain along [001]. N—H⋯O hydrogen bonds and π–π interactions between the pyridine and pyrazole rings [centroid–centroid distance = 3.927 (3) Å] connect the chains into a layer parallel to (011).

Related literature

For background to complexes of 4-(1H-pyrazol-3-yl)pyridine, see: Davies et al. (2005 ). For the synthesis of the ligand, see: Davies et al. (2003 ).

Experimental

Crystal data

[Zn(C₂H₃O₂)₂(C₈H₇N₃)]
M_r = 322.58
Monoclinic, P 2₁ /c
a = 16.371 (3) Å
b = 8.8526 (18) Å
c = 9.5041 (19) Å
β = 94.18 (3)°
V = 1373.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 293 K
0.28 × 0.23 × 0.19 mm

Data collection

Rigaku SCXmini CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.632, T_max = 0.726
11822 measured reflections
2479 independent reflections
1957 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.131
S = 1.06
2479 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—N1	2.026 (4)
Zn1—O1	1.942 (4)
Zn1—O3	1.958 (3)
Zn1—O4ⁱ	1.984 (3)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O2ⁱⁱ	0.86	1.93	2.769 (6)	163
Symmetry code: (ii) -x, -y+1, -z+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: ORTEPII (Johnson, 1976 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811040190/hy2465sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040190/hy2465Isup2.hkl

checkCIF report

Comment top

Pyridine derivatives are an important class of ligands for constructing metal–organic frameworks. 4-(1H-Pyrazol-3-yl)pyridine can be used as pyridine ligand in building coordination compounds (Davies et al., 2005). In the present paper, we report the synthesis and structure of the title compound.

As shown in Fig. 1, the Zn^II atom exhibits a distorted tetrahedral coordination geometry, defined by one N atom from a 4-(1H-pyrazol-3-yl)pyridine ligand and three O atoms from two types of acetate ligands (Table 1). One acetate anion coordinates the Zn atom as a monodentate terminal ligand. The other acetate anion links the Zn atoms via two O atoms, forming a one-dimensional chain along [0 0 1] (Fig. 2). N—H···O hydrogen bonds (Table 2) and π–π interactions between the pyridine and pyrazole rings [centroid–centroid distance = 3.927 (3) Å] connect the chains into a layer parallel to (0 1 1) (Fig. 3).

Related literature top

For background to complexes of 4-(1H-pyrazol-3-yl)pyridine, see: Davies et al. (2005). For the synthesis of the ligand, see: Davies et al. (2003).

Experimental top

4-(1H-Pyrazol-3-yl)pyridine was prepared according to the published method of Davies et al. (2003). An aqueous solution (20 ml) containing zinc acetate (0.1 mmol, 22 mg) and 4-(1H-pyrazol-3-yl)pyridine (0.2 mmol, 29 mg) was stirred for a few minutes in air. Colorless crystals were obtained by allowing the solution to stand at room temperature for a few weeks.

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: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) x, 3/2-y, 1/2+z.]
	Fig. 2. A view of the one-dimensional structure of the title compound along [0 0 1].
	Fig. 3. A view of the layer network. Hydrogen bonds are shown as dashed lines.

catena-Poly[[(acetato-κO)[4-(1H-pyrazol-3- yl)pyridine-κN¹]zinc]-µ-acetato-κ²O:O'] top

Crystal data top

[Zn(C₂H₃O₂)₂(C₈H₇N₃)]	F(000) = 648
M_r = 322.58	D_x = 1.560 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11614 reflections
a = 16.371 (3) Å	θ = 3.2–27.6°
b = 8.8526 (18) Å	µ = 1.80 mm⁻¹
c = 9.5041 (19) Å	T = 293 K
β = 94.18 (3)°	Block, colourless
V = 1373.7 (5) Å³	0.28 × 0.23 × 0.19 mm
Z = 4

Data collection top

Rigaku SCXmini CCD diffractometer	2479 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ω scans	θ_max = 25.2°, θ_min = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −19→19
T_min = 0.632, T_max = 0.726	k = −10→10
11822 measured reflections	l = −11→11

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.063P)² + 1.9274P] where P = (F_o² + 2F_c²)/3
2479 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Zn(C₂H₃O₂)₂(C₈H₇N₃)]	V = 1373.7 (5) Å³
M_r = 322.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.371 (3) Å	µ = 1.80 mm⁻¹
b = 8.8526 (18) Å	T = 293 K
c = 9.5041 (19) Å	0.28 × 0.23 × 0.19 mm
β = 94.18 (3)°

Data collection top

Rigaku SCXmini CCD diffractometer	2479 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1957 reflections with I > 2σ(I)
T_min = 0.632, T_max = 0.726	R_int = 0.068
11822 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.06	Δρ_max = 0.51 e Å⁻³
2479 reflections	Δρ_min = −0.54 e Å⁻³
181 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.34131 (3)	0.68665 (6)	1.02084 (6)	0.0343 (2)
N1	0.2233 (2)	0.7526 (5)	0.9820 (4)	0.0348 (9)
C3	0.0573 (3)	0.8142 (5)	0.9123 (5)	0.0325 (11)
C4	0.0820 (3)	0.6924 (5)	0.9969 (5)	0.0362 (11)
H4	0.0430	0.6294	1.0325	0.043*
C5	0.1635 (3)	0.6647 (6)	1.0280 (5)	0.0372 (12)
H5	0.1784	0.5813	1.0836	0.045*
C1	0.1992 (3)	0.8734 (6)	0.9045 (5)	0.0403 (12)
H1	0.2393	0.9371	0.8736	0.048*
C2	0.1192 (3)	0.9082 (5)	0.8682 (5)	0.0365 (12)
H2	0.1059	0.9938	0.8146	0.044*
N3	−0.1561 (3)	0.7919 (5)	0.8372 (5)	0.0491 (12)
H3	−0.2025	0.7466	0.8393	0.059*
C6	−0.0297 (3)	0.8401 (5)	0.8676 (5)	0.0331 (11)
N2	−0.0849 (3)	0.7342 (5)	0.8937 (5)	0.0454 (11)
C7	−0.0660 (3)	0.9619 (6)	0.7937 (5)	0.0438 (13)
H7	−0.0402	1.0480	0.7624	0.053*
C8	−0.1469 (3)	0.9277 (7)	0.7774 (6)	0.0495 (14)
H8	−0.1880	0.9870	0.7333	0.059*
O3	0.4195 (2)	0.8246 (4)	0.9418 (3)	0.0453 (9)
O1	0.3590 (2)	0.4837 (4)	0.9518 (4)	0.0500 (10)
O2	0.2878 (2)	0.3956 (4)	1.1226 (4)	0.0501 (10)
C9	0.3292 (3)	0.3761 (6)	1.0208 (6)	0.0405 (12)
C10	0.3494 (5)	0.2163 (7)	0.9709 (8)	0.072 (2)
C11	0.4183 (3)	0.8446 (5)	0.8100 (5)	0.0334 (11)
C12	0.4840 (3)	0.9438 (7)	0.7551 (6)	0.0578 (17)
O4	0.3643 (2)	0.7841 (4)	0.7269 (3)	0.0373 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0330 (3)	0.0415 (4)	0.0283 (3)	−0.0030 (3)	0.0026 (2)	−0.0012 (3)
N1	0.035 (2)	0.039 (2)	0.030 (2)	−0.004 (2)	0.0011 (18)	−0.0030 (19)
C3	0.034 (3)	0.034 (3)	0.030 (3)	0.003 (2)	0.005 (2)	−0.005 (2)
C4	0.039 (3)	0.034 (3)	0.036 (3)	−0.004 (2)	0.007 (2)	0.008 (2)
C5	0.040 (3)	0.041 (3)	0.030 (3)	0.003 (2)	0.003 (2)	0.006 (2)
C1	0.040 (3)	0.041 (3)	0.040 (3)	−0.010 (2)	0.004 (2)	0.003 (2)
C2	0.042 (3)	0.032 (3)	0.036 (3)	0.001 (2)	0.005 (2)	0.007 (2)
N3	0.032 (2)	0.053 (3)	0.061 (3)	−0.001 (2)	−0.002 (2)	0.007 (2)
C6	0.037 (3)	0.031 (3)	0.031 (3)	0.000 (2)	0.004 (2)	0.000 (2)
N2	0.034 (3)	0.039 (3)	0.063 (3)	−0.004 (2)	0.003 (2)	0.008 (2)
C7	0.045 (3)	0.043 (3)	0.043 (3)	−0.002 (3)	0.000 (2)	0.010 (3)
C8	0.042 (3)	0.054 (4)	0.052 (3)	0.009 (3)	−0.001 (3)	0.010 (3)
O3	0.048 (2)	0.061 (2)	0.0267 (19)	−0.0171 (18)	0.0011 (15)	0.0038 (17)
O1	0.068 (3)	0.038 (2)	0.046 (2)	−0.0065 (19)	0.0162 (19)	−0.0039 (17)
O2	0.044 (2)	0.046 (2)	0.062 (3)	−0.0055 (18)	0.0122 (19)	0.0023 (19)
C9	0.036 (3)	0.042 (3)	0.042 (3)	−0.004 (2)	−0.008 (2)	−0.001 (3)
C10	0.094 (5)	0.037 (4)	0.086 (5)	0.005 (3)	0.006 (4)	−0.013 (3)
C11	0.036 (3)	0.035 (3)	0.030 (3)	0.002 (2)	0.004 (2)	0.001 (2)
C12	0.047 (3)	0.075 (4)	0.052 (4)	−0.023 (3)	0.005 (3)	0.015 (3)
O4	0.042 (2)	0.044 (2)	0.0258 (17)	−0.0044 (16)	0.0040 (15)	−0.0009 (15)

Geometric parameters (Å, º) top

Zn1—N1	2.026 (4)	N3—C8	1.344 (7)
Zn1—O1	1.942 (4)	N3—N2	1.348 (6)
Zn1—O3	1.958 (3)	N3—H3	0.8600
Zn1—O4ⁱ	1.984 (3)	C6—N2	1.338 (6)
N1—C1	1.341 (6)	C6—C7	1.395 (7)
N1—C5	1.348 (6)	C7—C8	1.356 (7)
C3—C4	1.387 (6)	C7—H7	0.9300
C3—C2	1.398 (7)	C8—H8	0.9300
C3—C6	1.475 (7)	O3—C11	1.264 (6)
C4—C5	1.368 (7)	O1—C9	1.274 (6)
C4—H4	0.9300	O2—C9	1.233 (6)
C5—H5	0.9300	C9—C10	1.536 (8)
C1—C2	1.365 (7)	C11—O4	1.261 (5)
C1—H1	0.9300	C11—C12	1.510 (7)
C2—H2	0.9300

O1—Zn1—O3	109.25 (16)	C3—C2—H2	120.2
O1—Zn1—O4ⁱ	115.59 (15)	C8—N3—N2	112.7 (4)
O3—Zn1—O4ⁱ	102.40 (14)	C8—N3—H3	123.6
O1—Zn1—N1	111.65 (17)	N2—N3—H3	123.6
O3—Zn1—N1	113.05 (16)	N2—C6—C7	111.5 (4)
O4ⁱ—Zn1—N1	104.60 (15)	N2—C6—C3	119.3 (4)
C1—N1—C5	116.5 (4)	C7—C6—C3	129.2 (4)
C1—N1—Zn1	124.6 (3)	C6—N2—N3	103.7 (4)
C5—N1—Zn1	118.7 (3)	C8—C7—C6	105.1 (5)
C4—C3—C2	116.7 (4)	C8—C7—H7	127.4
C4—C3—C6	121.4 (4)	C6—C7—H7	127.4
C2—C3—C6	121.8 (4)	N3—C8—C7	106.9 (5)
C5—C4—C3	120.2 (4)	N3—C8—H8	126.5
C5—C4—H4	119.9	C7—C8—H8	126.5
C3—C4—H4	119.9	C11—O3—Zn1	120.3 (3)
N1—C5—C4	123.1 (5)	C9—O1—Zn1	116.5 (3)
N1—C5—H5	118.4	O2—C9—O1	123.5 (5)
C4—C5—H5	118.4	O2—C9—C10	121.0 (5)
N1—C1—C2	123.9 (5)	O1—C9—C10	115.5 (5)
N1—C1—H1	118.1	O4—C11—O3	121.4 (4)
C2—C1—H1	118.1	O4—C11—C12	121.0 (4)
C1—C2—C3	119.5 (5)	O3—C11—C12	117.6 (4)
C1—C2—H2	120.2	C11—O4—Zn1ⁱⁱ	129.6 (3)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2ⁱⁱⁱ	0.86	1.93	2.769 (6)	163

Symmetry code: (iii) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Zn(C₂H₃O₂)₂(C₈H₇N₃)]
M_r	322.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	16.371 (3), 8.8526 (18), 9.5041 (19)
β (°)	94.18 (3)
V (Å³)	1373.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.80
Crystal size (mm)	0.28 × 0.23 × 0.19

Data collection
Diffractometer	Rigaku SCXmini CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.632, 0.726
No. of measured, independent and observed [I > 2σ(I)] reflections	11822, 2479, 1957
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.131, 1.06
No. of reflections	2479
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.54

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 1999).

Selected bond lengths (Å) top

Zn1—N1	2.026 (4)	Zn1—O3	1.958 (3)
Zn1—O1	1.942 (4)	Zn1—O4ⁱ	1.984 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2ⁱⁱ	0.86	1.93	2.769 (6)	163

Symmetry code: (ii) −x, −y+1, −z+2.

Acknowledgements

The authors acknowledge the Education Department of Hunan Province [Xiang Norimichi (2010).243] for supporting this work.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Davies, G. M., Adams, H. & Ward, M. D. (2005). Acta Cryst. C61, m485–m487. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Davies, G. M., Jeffery, J. C. & Ward, M. D. (2003). New J. Chem. 27, 1550–1553. Web of Science CSD CrossRef CAS Google Scholar
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. 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

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