Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044285/gw2024sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044285/gw2024Isup2.hkl |
CCDC reference: 663598
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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).
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.
H atoms were positioned geometrically with C—H = 0.93 Å and allowed to ride during subsequent refinement with Uiso(H) = 1.2Ueq(C).
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).
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).
[Zn(C2O4)(C5H5N)2] | F(000) = 632 |
Mr = 311.59 | Dx = 1.576 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4780 (9) Å | Cell parameters from 2981 reflections |
b = 9.2118 (8) Å | θ = 2.5–26.3° |
c = 15.0863 (13) Å | µ = 1.88 mm−1 |
β = 94.402 (4)° | T = 293 K |
V = 1313.3 (2) Å3 | Block, yellow |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
Bruker SMART APEX CCD diffractometer | 2981 independent reflections |
Radiation source: fine-focus sealed tube | 2030 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
φ and ω scans | θmax = 27.4°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −12→12 |
Tmin = 0.602, Tmax = 0.705 | k = −11→11 |
15885 measured reflections | l = −19→19 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-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 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
[Zn(C2O4)(C5H5N)2] | V = 1313.3 (2) Å3 |
Mr = 311.59 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.4780 (9) Å | µ = 1.88 mm−1 |
b = 9.2118 (8) Å | T = 293 K |
c = 15.0863 (13) Å | 0.30 × 0.25 × 0.20 mm |
β = 94.402 (4)° |
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 = 0.705 | Rint = 0.067 |
15885 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 0.82 | Δρmax = 0.53 e Å−3 |
2981 reflections | Δρmin = −0.33 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.75084 (3) | −0.34984 (3) | 0.504672 (15) | 0.02915 (10) | |
O1 | 0.56734 (16) | −0.36565 (17) | 0.57297 (10) | 0.0330 (4) | |
O2 | 0.92978 (16) | −0.36105 (18) | 0.43119 (9) | 0.0335 (4) | |
O3 | 0.86912 (16) | −0.51562 (18) | 0.57471 (10) | 0.0359 (4) | |
O4 | 0.63625 (16) | −0.51363 (18) | 0.42912 (10) | 0.0351 (4) | |
N1 | 0.6728 (2) | −0.1855 (2) | 0.41113 (12) | 0.0361 (5) | |
N2 | 0.8342 (2) | −0.1952 (2) | 0.60162 (12) | 0.0340 (5) | |
C1 | 0.4796 (2) | −0.4570 (2) | 0.54165 (13) | 0.0267 (5) | |
C2 | 1.0183 (2) | −0.4548 (3) | 0.45843 (12) | 0.0273 (5) | |
C3 | 0.6379 (3) | −0.0519 (3) | 0.43339 (17) | 0.0508 (7) | |
H3A | 0.6433 | −0.0276 | 0.4934 | 0.061* | |
C4 | 0.5940 (4) | 0.0530 (4) | 0.37219 (19) | 0.0663 (9) | |
H4A | 0.5703 | 0.1456 | 0.3907 | 0.080* | |
C5 | 0.5860 (3) | 0.0183 (4) | 0.28352 (19) | 0.0618 (9) | |
H5A | 0.5558 | 0.0865 | 0.2407 | 0.074* | |
C6 | 0.6231 (4) | −0.1172 (4) | 0.25962 (18) | 0.0606 (9) | |
H6A | 0.6201 | −0.1430 | 0.1999 | 0.073* | |
C7 | 0.6655 (3) | −0.2167 (3) | 0.32437 (16) | 0.0481 (7) | |
H7A | 0.6900 | −0.3097 | 0.3070 | 0.058* | |
C8 | 0.9477 (3) | −0.1161 (3) | 0.58687 (16) | 0.0474 (7) | |
H8A | 0.9903 | −0.1306 | 0.5340 | 0.057* | |
C9 | 1.0050 (3) | −0.0147 (3) | 0.64543 (18) | 0.0575 (8) | |
H9A | 1.0835 | 0.0391 | 0.6317 | 0.069* | |
C10 | 0.9457 (3) | 0.0066 (3) | 0.72456 (17) | 0.0512 (7) | |
H10A | 0.9831 | 0.0744 | 0.7656 | 0.061* | |
C11 | 0.8304 (3) | −0.0743 (4) | 0.74121 (17) | 0.0556 (8) | |
H11A | 0.7875 | −0.0626 | 0.7942 | 0.067* | |
C12 | 0.7781 (3) | −0.1733 (3) | 0.67895 (16) | 0.0473 (7) | |
H12A | 0.6995 | −0.2279 | 0.6914 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02419 (15) | 0.03332 (17) | 0.03018 (15) | −0.00085 (13) | 0.00355 (10) | −0.00017 (12) |
O1 | 0.0294 (9) | 0.0360 (10) | 0.0342 (8) | −0.0041 (8) | 0.0056 (6) | −0.0073 (7) |
O2 | 0.0297 (9) | 0.0397 (10) | 0.0317 (7) | 0.0054 (8) | 0.0062 (6) | 0.0067 (7) |
O3 | 0.0296 (9) | 0.0446 (11) | 0.0347 (8) | 0.0057 (8) | 0.0107 (7) | 0.0074 (7) |
O4 | 0.0274 (9) | 0.0423 (10) | 0.0365 (8) | −0.0053 (8) | 0.0089 (7) | −0.0072 (7) |
N1 | 0.0306 (11) | 0.0414 (13) | 0.0364 (10) | 0.0021 (10) | 0.0040 (8) | 0.0064 (9) |
N2 | 0.0320 (11) | 0.0376 (12) | 0.0323 (9) | −0.0029 (9) | 0.0015 (8) | −0.0024 (9) |
C1 | 0.0236 (12) | 0.0290 (13) | 0.0274 (10) | 0.0011 (10) | 0.0005 (9) | 0.0015 (9) |
C2 | 0.0258 (12) | 0.0314 (14) | 0.0245 (10) | −0.0021 (11) | 0.0008 (9) | −0.0026 (9) |
C3 | 0.0587 (19) | 0.0557 (19) | 0.0393 (13) | 0.0220 (16) | 0.0127 (12) | 0.0041 (13) |
C4 | 0.081 (2) | 0.056 (2) | 0.0629 (18) | 0.0327 (19) | 0.0142 (17) | 0.0092 (16) |
C5 | 0.066 (2) | 0.069 (2) | 0.0498 (16) | 0.0170 (18) | 0.0022 (14) | 0.0221 (16) |
C6 | 0.075 (2) | 0.066 (2) | 0.0380 (14) | −0.0004 (18) | −0.0093 (14) | 0.0059 (14) |
C7 | 0.0603 (18) | 0.0448 (17) | 0.0378 (13) | −0.0016 (15) | −0.0060 (12) | −0.0006 (12) |
C8 | 0.0480 (17) | 0.0596 (19) | 0.0356 (12) | −0.0180 (14) | 0.0105 (11) | −0.0063 (12) |
C9 | 0.0552 (19) | 0.066 (2) | 0.0514 (16) | −0.0291 (16) | 0.0068 (13) | −0.0085 (15) |
C10 | 0.0556 (18) | 0.0557 (19) | 0.0414 (14) | −0.0129 (15) | −0.0027 (12) | −0.0137 (13) |
C11 | 0.0555 (19) | 0.072 (2) | 0.0409 (14) | −0.0116 (17) | 0.0122 (13) | −0.0204 (14) |
C12 | 0.0402 (15) | 0.063 (2) | 0.0397 (13) | −0.0138 (14) | 0.0107 (11) | −0.0091 (13) |
Zn1—O1 | 2.0935 (15) | C12—C11 | 1.374 (4) |
Zn1—O2 | 2.0987 (15) | C7—C6 | 1.377 (4) |
Zn1—O3 | 2.1269 (16) | C10—C11 | 1.362 (4) |
Zn1—O4 | 2.1365 (16) | C10—C9 | 1.372 (4) |
Zn1—N2 | 2.1485 (19) | C8—C9 | 1.369 (4) |
Zn1—N1 | 2.161 (2) | C5—C6 | 1.354 (4) |
O2—C2 | 1.251 (3) | C5—C4 | 1.372 (4) |
O1—C1 | 1.250 (3) | C4—C3 | 1.378 (4) |
O4—C1i | 1.244 (3) | C3—H3A | 0.930 |
O3—C2ii | 1.243 (3) | C4—H4A | 0.930 |
N2—C12 | 1.334 (3) | C5—H5A | 0.930 |
N2—C8 | 1.332 (3) | C6—H6A | 0.930 |
C2—O3ii | 1.243 (3) | C7—H7A | 0.930 |
C2—C2ii | 1.566 (4) | C8—H8A | 0.930 |
C1—O4i | 1.244 (3) | C9—H9A | 0.930 |
C1—C1i | 1.559 (4) | C10—H10A | 0.930 |
N1—C3 | 1.324 (3) | C11—H11A | 0.930 |
N1—C7 | 1.337 (3) | C12—H12A | 0.930 |
O1—Zn1—O2 | 172.80 (6) | N2—C12—C11 | 123.6 (3) |
O1—Zn1—O3 | 97.56 (6) | N1—C7—C6 | 122.8 (3) |
O2—Zn1—O3 | 79.08 (6) | C11—C10—C9 | 118.0 (3) |
O1—Zn1—O4 | 78.81 (6) | N2—C8—C9 | 123.4 (2) |
O2—Zn1—O4 | 94.69 (6) | C10—C11—C12 | 119.3 (2) |
O3—Zn1—O4 | 89.14 (7) | C6—C5—C4 | 118.6 (3) |
O1—Zn1—N2 | 89.26 (6) | C5—C6—C7 | 119.5 (3) |
O2—Zn1—N2 | 97.02 (7) | C8—C9—C10 | 119.4 (3) |
O3—Zn1—N2 | 89.18 (7) | C3—C4—C5 | 118.8 (3) |
O4—Zn1—N2 | 167.63 (6) | N1—C3—C4 | 123.4 (2) |
O1—Zn1—N1 | 96.57 (7) | H3A—C3—N1 | 118.67 |
O2—Zn1—N1 | 86.54 (7) | H3A—C3—C4 | 118.70 |
O3—Zn1—N1 | 165.55 (7) | H4A—C4—C3 | 120.25 |
O4—Zn1—N1 | 90.68 (7) | H4A—C4—C5 | 120.22 |
N2—Zn1—N1 | 93.98 (8) | H5A—C5—C4 | 120.69 |
C2—O2—Zn1 | 114.15 (13) | H5A—C5—C6 | 120.71 |
C1—O1—Zn1 | 114.47 (13) | H6A—C6—C5 | 120.35 |
C1i—O4—Zn1 | 113.00 (13) | H6A—C6—C7 | 120.35 |
C2ii—O3—Zn1 | 113.18 (14) | H7A—C7—C6 | 118.22 |
C12—N2—C8 | 116.4 (2) | H7A—C7—N1 | 118.28 |
C12—N2—Zn1 | 123.04 (15) | H8A—C8—N2 | 118.38 |
C8—N2—Zn1 | 120.56 (16) | H8A—C8—C9 | 118.39 |
O3ii—C2—O2 | 126.43 (19) | H9A—C9—C8 | 120.51 |
O3ii—C2—C2ii | 117.1 (2) | H9A—C9—C10 | 120.52 |
O2—C2—C2ii | 116.5 (2) | H10A—C10—C9 | 120.59 |
O4i—C1—O1 | 126.28 (19) | H10A—C10—C11 | 120.64 |
O4i—C1—C1i | 117.1 (2) | H11A—C11—C10 | 120.53 |
O1—C1—C1i | 116.6 (2) | H11A—C11—C12 | 120.57 |
C3—N1—C7 | 117.0 (2) | H12A—C12—C11 | 118.34 |
C3—N1—Zn1 | 124.40 (16) | H12A—C12—N2 | 118.41 |
C7—N1—Zn1 | 118.55 (18) |
Symmetry codes: (i) −x+1, −y−1, −z+1; (ii) −x+2, −y−1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2O4)(C5H5N)2] |
Mr | 311.59 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.4780 (9), 9.2118 (8), 15.0863 (13) |
β (°) | 94.402 (4) |
V (Å3) | 1313.3 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.88 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.602, 0.705 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15885, 2981, 2030 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.081, 0.82 |
No. of reflections | 2981 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.33 |
Computer programs: SMART (Bruker, 2001), SMART [or SAINT-Plus?] (Bruker, 2001), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Zn1—O1 | 2.0935 (15) | Zn1—O4 | 2.1365 (16) |
Zn1—O2 | 2.0987 (15) | Zn1—N2 | 2.1485 (19) |
Zn1—O3 | 2.1269 (16) | Zn1—N1 | 2.161 (2) |
O1—Zn1—O2 | 172.80 (6) | O1—Zn1—O4 | 78.81 (6) |
O1—Zn1—O3 | 97.56 (6) | O2—Zn1—O4 | 94.69 (6) |
O2—Zn1—O3 | 79.08 (6) | O3—Zn1—O4 | 89.14 (7) |
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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).