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The title compound, [Zn(C2O4)(C5H5N)2]n, was synthesized by the oxidation of penta­erythritol under solvothermal conditions. The backbone of the compound is formed from ZnII oxalate, with two pyridine ligands coordinated to each ZnII ion, giving it hexa­coordination in a slightly distorted octa­hedral environment.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044285/gw2024sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044285/gw2024Isup2.hkl
Contains datablock I

CCDC reference: 663598

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.030
  • wR factor = 0.080
  • Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT369_ALERT_2_B Long C(sp2)-C(sp2) Bond C2 - C2_b ... 1.57 Ang.
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.97 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C1_a ... 1.56 Ang.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.94
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Synthesis of metal organic framework (MOF) structures by the modular approach is an area of intense research activity as potential zeolitic, optoelectronic, magnetic, and conducting materials(Chui et al., 1999; Kiang et al., 1999; Kahn & Martinez, 1998; Lin et al., 1999). While most of these products have been generated utilizing hydro(solvo)thermal techniques, it is often not possible to predict the structures of them with confidence (Evans & Lin, 2001; Ghosh et al., 2004). In this paper, we report our unexpected discovery of the synthesis of a new zinc oxalate coordination polymers by facile oxidation of pentaerythritol acid to oxalic acid under hydro(solvo)thermal conditions.

The structure of the compound consists of infinite one-dimensional zigzag chains where each metal ion is coordinated to two oxalate groups and two pyridine molecules showing hexacoordination with O4N2 donor set (Fig. 1). Coordination geometry around each metal center can be described as slightly distorted octahedral. The two pyridine molecules are similarly oriented with respect to the Zn-oxalate backbone. These infinite zigzag chains pack in the lattice through interdigitization involving the pyridine molecules (Fig. 2).The Zn—O distances range from 2.0935 (15) Å to 2.1365 (16) Å, while the O—Zn—O angles between 78.81 (6)° and 172.80 (6) (Table 1).

Related literature top

For related literature, see: Chui et al. (1999); Evans & Lin (2001); Ghosh et al. (2004); Kahn & Martinez (1998); Kiang et al. (1999); Lin et al. (1999).

Experimental top

The compound was prepared by a solvothermal reaction of pentaerythritol (0.031 g), Zn(NO3)2.6H2O (0.027 g), using a solvent of pyridine (0.475 g). The mixture was sealed in a Pyrex glass tube with ca 10% filling, placed into a stainless-autoclave, and heated at 393 K for 6 days. After cooling naturally to ambient temperature, the products were washed with ethanol, and the yellow block crystals were obtained.

Refinement top

H atoms were positioned geometrically with C—H = 0.93 Å and allowed to ride during subsequent refinement with Uiso(H) = 1.2Ueq(C).

Structure description top

Synthesis of metal organic framework (MOF) structures by the modular approach is an area of intense research activity as potential zeolitic, optoelectronic, magnetic, and conducting materials(Chui et al., 1999; Kiang et al., 1999; Kahn & Martinez, 1998; Lin et al., 1999). While most of these products have been generated utilizing hydro(solvo)thermal techniques, it is often not possible to predict the structures of them with confidence (Evans & Lin, 2001; Ghosh et al., 2004). In this paper, we report our unexpected discovery of the synthesis of a new zinc oxalate coordination polymers by facile oxidation of pentaerythritol acid to oxalic acid under hydro(solvo)thermal conditions.

The structure of the compound consists of infinite one-dimensional zigzag chains where each metal ion is coordinated to two oxalate groups and two pyridine molecules showing hexacoordination with O4N2 donor set (Fig. 1). Coordination geometry around each metal center can be described as slightly distorted octahedral. The two pyridine molecules are similarly oriented with respect to the Zn-oxalate backbone. These infinite zigzag chains pack in the lattice through interdigitization involving the pyridine molecules (Fig. 2).The Zn—O distances range from 2.0935 (15) Å to 2.1365 (16) Å, while the O—Zn—O angles between 78.81 (6)° and 172.80 (6) (Table 1).

For related literature, see: Chui et al. (1999); Evans & Lin (2001); Ghosh et al. (2004); Kahn & Martinez (1998); Kiang et al. (1999); Lin et al. (1999).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SMART [or SAINT-Plus?] (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I) with the atom-labelling scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry code:(i) 2 - x, -1 - y,-z + 1; (ii) -x + 1, -y - 1, -z + 1. H atoms have been omitted.
[Figure 2] Fig. 2. Packing of the zigzag chains through interchain interdigitization of pyridine molecules in the compound. H atoms have been omitted.
catena-poly[µ2-oxalato-κ4O,O':O'',O'''-bis(pyridine-κN)zinc(II)] top
Crystal data top
[Zn(C2O4)(C5H5N)2]F(000) = 632
Mr = 311.59Dx = 1.576 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.4780 (9) ÅCell parameters from 2981 reflections
b = 9.2118 (8) Åθ = 2.5–26.3°
c = 15.0863 (13) ŵ = 1.88 mm1
β = 94.402 (4)°T = 293 K
V = 1313.3 (2) Å3Block, yellow
Z = 40.30 × 0.25 × 0.20 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
2981 independent reflections
Radiation source: fine-focus sealed tube2030 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.067
φ and ω scansθmax = 27.4°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 1212
Tmin = 0.602, Tmax = 0.705k = 1111
15885 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 0.82 w = 1/[σ2(Fo2) + (0.0391P)2 + 0.8316P]
where P = (Fo2 + 2Fc2)/3
2981 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
[Zn(C2O4)(C5H5N)2]V = 1313.3 (2) Å3
Mr = 311.59Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.4780 (9) ŵ = 1.88 mm1
b = 9.2118 (8) ÅT = 293 K
c = 15.0863 (13) Å0.30 × 0.25 × 0.20 mm
β = 94.402 (4)°
Data collection top
Bruker SMART APEX CCD
diffractometer
2981 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
2030 reflections with I > 2σ(I)
Tmin = 0.602, Tmax = 0.705Rint = 0.067
15885 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 0.82Δρmax = 0.53 e Å3
2981 reflectionsΔρmin = 0.33 e Å3
172 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
xyzUiso*/Ueq
Zn10.75084 (3)0.34984 (3)0.504672 (15)0.02915 (10)
O10.56734 (16)0.36565 (17)0.57297 (10)0.0330 (4)
O20.92978 (16)0.36105 (18)0.43119 (9)0.0335 (4)
O30.86912 (16)0.51562 (18)0.57471 (10)0.0359 (4)
O40.63625 (16)0.51363 (18)0.42912 (10)0.0351 (4)
N10.6728 (2)0.1855 (2)0.41113 (12)0.0361 (5)
N20.8342 (2)0.1952 (2)0.60162 (12)0.0340 (5)
C10.4796 (2)0.4570 (2)0.54165 (13)0.0267 (5)
C21.0183 (2)0.4548 (3)0.45843 (12)0.0273 (5)
C30.6379 (3)0.0519 (3)0.43339 (17)0.0508 (7)
H3A0.64330.02760.49340.061*
C40.5940 (4)0.0530 (4)0.37219 (19)0.0663 (9)
H4A0.57030.14560.39070.080*
C50.5860 (3)0.0183 (4)0.28352 (19)0.0618 (9)
H5A0.55580.08650.24070.074*
C60.6231 (4)0.1172 (4)0.25962 (18)0.0606 (9)
H6A0.62010.14300.19990.073*
C70.6655 (3)0.2167 (3)0.32437 (16)0.0481 (7)
H7A0.69000.30970.30700.058*
C80.9477 (3)0.1161 (3)0.58687 (16)0.0474 (7)
H8A0.99030.13060.53400.057*
C91.0050 (3)0.0147 (3)0.64543 (18)0.0575 (8)
H9A1.08350.03910.63170.069*
C100.9457 (3)0.0066 (3)0.72456 (17)0.0512 (7)
H10A0.98310.07440.76560.061*
C110.8304 (3)0.0743 (4)0.74121 (17)0.0556 (8)
H11A0.78750.06260.79420.067*
C120.7781 (3)0.1733 (3)0.67895 (16)0.0473 (7)
H12A0.69950.22790.69140.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02419 (15)0.03332 (17)0.03018 (15)0.00085 (13)0.00355 (10)0.00017 (12)
O10.0294 (9)0.0360 (10)0.0342 (8)0.0041 (8)0.0056 (6)0.0073 (7)
O20.0297 (9)0.0397 (10)0.0317 (7)0.0054 (8)0.0062 (6)0.0067 (7)
O30.0296 (9)0.0446 (11)0.0347 (8)0.0057 (8)0.0107 (7)0.0074 (7)
O40.0274 (9)0.0423 (10)0.0365 (8)0.0053 (8)0.0089 (7)0.0072 (7)
N10.0306 (11)0.0414 (13)0.0364 (10)0.0021 (10)0.0040 (8)0.0064 (9)
N20.0320 (11)0.0376 (12)0.0323 (9)0.0029 (9)0.0015 (8)0.0024 (9)
C10.0236 (12)0.0290 (13)0.0274 (10)0.0011 (10)0.0005 (9)0.0015 (9)
C20.0258 (12)0.0314 (14)0.0245 (10)0.0021 (11)0.0008 (9)0.0026 (9)
C30.0587 (19)0.0557 (19)0.0393 (13)0.0220 (16)0.0127 (12)0.0041 (13)
C40.081 (2)0.056 (2)0.0629 (18)0.0327 (19)0.0142 (17)0.0092 (16)
C50.066 (2)0.069 (2)0.0498 (16)0.0170 (18)0.0022 (14)0.0221 (16)
C60.075 (2)0.066 (2)0.0380 (14)0.0004 (18)0.0093 (14)0.0059 (14)
C70.0603 (18)0.0448 (17)0.0378 (13)0.0016 (15)0.0060 (12)0.0006 (12)
C80.0480 (17)0.0596 (19)0.0356 (12)0.0180 (14)0.0105 (11)0.0063 (12)
C90.0552 (19)0.066 (2)0.0514 (16)0.0291 (16)0.0068 (13)0.0085 (15)
C100.0556 (18)0.0557 (19)0.0414 (14)0.0129 (15)0.0027 (12)0.0137 (13)
C110.0555 (19)0.072 (2)0.0409 (14)0.0116 (17)0.0122 (13)0.0204 (14)
C120.0402 (15)0.063 (2)0.0397 (13)0.0138 (14)0.0107 (11)0.0091 (13)
Geometric parameters (Å, º) top
Zn1—O12.0935 (15)C12—C111.374 (4)
Zn1—O22.0987 (15)C7—C61.377 (4)
Zn1—O32.1269 (16)C10—C111.362 (4)
Zn1—O42.1365 (16)C10—C91.372 (4)
Zn1—N22.1485 (19)C8—C91.369 (4)
Zn1—N12.161 (2)C5—C61.354 (4)
O2—C21.251 (3)C5—C41.372 (4)
O1—C11.250 (3)C4—C31.378 (4)
O4—C1i1.244 (3)C3—H3A0.930
O3—C2ii1.243 (3)C4—H4A0.930
N2—C121.334 (3)C5—H5A0.930
N2—C81.332 (3)C6—H6A0.930
C2—O3ii1.243 (3)C7—H7A0.930
C2—C2ii1.566 (4)C8—H8A0.930
C1—O4i1.244 (3)C9—H9A0.930
C1—C1i1.559 (4)C10—H10A0.930
N1—C31.324 (3)C11—H11A0.930
N1—C71.337 (3)C12—H12A0.930
O1—Zn1—O2172.80 (6)N2—C12—C11123.6 (3)
O1—Zn1—O397.56 (6)N1—C7—C6122.8 (3)
O2—Zn1—O379.08 (6)C11—C10—C9118.0 (3)
O1—Zn1—O478.81 (6)N2—C8—C9123.4 (2)
O2—Zn1—O494.69 (6)C10—C11—C12119.3 (2)
O3—Zn1—O489.14 (7)C6—C5—C4118.6 (3)
O1—Zn1—N289.26 (6)C5—C6—C7119.5 (3)
O2—Zn1—N297.02 (7)C8—C9—C10119.4 (3)
O3—Zn1—N289.18 (7)C3—C4—C5118.8 (3)
O4—Zn1—N2167.63 (6)N1—C3—C4123.4 (2)
O1—Zn1—N196.57 (7)H3A—C3—N1118.67
O2—Zn1—N186.54 (7)H3A—C3—C4118.70
O3—Zn1—N1165.55 (7)H4A—C4—C3120.25
O4—Zn1—N190.68 (7)H4A—C4—C5120.22
N2—Zn1—N193.98 (8)H5A—C5—C4120.69
C2—O2—Zn1114.15 (13)H5A—C5—C6120.71
C1—O1—Zn1114.47 (13)H6A—C6—C5120.35
C1i—O4—Zn1113.00 (13)H6A—C6—C7120.35
C2ii—O3—Zn1113.18 (14)H7A—C7—C6118.22
C12—N2—C8116.4 (2)H7A—C7—N1118.28
C12—N2—Zn1123.04 (15)H8A—C8—N2118.38
C8—N2—Zn1120.56 (16)H8A—C8—C9118.39
O3ii—C2—O2126.43 (19)H9A—C9—C8120.51
O3ii—C2—C2ii117.1 (2)H9A—C9—C10120.52
O2—C2—C2ii116.5 (2)H10A—C10—C9120.59
O4i—C1—O1126.28 (19)H10A—C10—C11120.64
O4i—C1—C1i117.1 (2)H11A—C11—C10120.53
O1—C1—C1i116.6 (2)H11A—C11—C12120.57
C3—N1—C7117.0 (2)H12A—C12—C11118.34
C3—N1—Zn1124.40 (16)H12A—C12—N2118.41
C7—N1—Zn1118.55 (18)
Symmetry codes: (i) x+1, y1, z+1; (ii) x+2, y1, z+1.

Experimental details

Crystal data
Chemical formula[Zn(C2O4)(C5H5N)2]
Mr311.59
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)9.4780 (9), 9.2118 (8), 15.0863 (13)
β (°) 94.402 (4)
V3)1313.3 (2)
Z4
Radiation typeMo Kα
µ (mm1)1.88
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.602, 0.705
No. of measured, independent and
observed [I > 2σ(I)] reflections
15885, 2981, 2030
Rint0.067
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.081, 0.82
No. of reflections2981
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.53, 0.33

Computer programs: SMART (Bruker, 2001), SMART [or SAINT-Plus?] (Bruker, 2001), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Selected geometric parameters (Å, º) top
Zn1—O12.0935 (15)Zn1—O42.1365 (16)
Zn1—O22.0987 (15)Zn1—N22.1485 (19)
Zn1—O32.1269 (16)Zn1—N12.161 (2)
O1—Zn1—O2172.80 (6)O1—Zn1—O478.81 (6)
O1—Zn1—O397.56 (6)O2—Zn1—O494.69 (6)
O2—Zn1—O379.08 (6)O3—Zn1—O489.14 (7)
 

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