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

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).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.056
• wR factor = 0.131
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C9
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0070 Ang
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT343_ALERT_2_G Check sp?     Angle Range in Main Residue for ..        C10
PLAT343_ALERT_2_G Check sp?     Angle Range in Main Residue for ..        C12
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          56 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

H atoms were placed at calculated positions and refined as riding atoms, with C—H = 0.93 and N—H = 0.86 Å and with U_iso(H) = 1.2U_eq(C, N).

Computing details

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

	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']

Crystal data

[Zn(C2H3O2)2(C8H7N3)]	F(000) = 648
Mr = 322.58	Dx = 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) Å^3	0.28 × 0.23 × 0.19 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 1.9274P] where P = (Fo^2 + 2Fc^2)/3
2479 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—O4^i	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—O4^i	115.59 (15)	C8—N3—N2	112.7 (4)
O3—Zn1—O4^i	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)
O4^i—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—Zn1^ii	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)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2^iii	0.86	1.93	2.769 (6)	163

Symmetry code: (iii) −x, −y+1, −z+2.