Acta Cryst. (2009). E65, m1414 [ doi:10.1107/S160053680904255X ]
![[mu]](/logos/entities/mu_rmgif.gif)
3-2-(1H-tetrazol-1-yl)acetato]cadmium(II)]In the title compound, [Cd(C3H3N4O2)2]n, the CdII ion, located on a twofold rotation axis, is six-coordinated by two N atoms [Cd-N = 2.368 (2) Å] and four O atoms [Cd-O = 2.300 (1) and 2.260 (1) Å] from six 2-(1H-tetrazol-1-yl)acetate (L) ligands in a distorted octahedral geometry. The metal centres are connected via the tridentate L ligands into a three-dimensional polymeric structure.
All solvents and chemicals were of analytical grade and were used without further purification. The compound [CdL2]n was synthesized as follows: 2-(1H–tetrazol–1–yl) acetic acid (1.0 mmol) was added to 5 cm3 water and the resulting solution was adjusted pH to 7.0 by NaOH aqueous. Then Cd(NO3)2(0.5 mmol) was added to the above solution, and the mixture was stirred for 30 min and filtered. After two days, colourless single crystals suitable for X-ray analysis were obtained. Anal. Calcd (%) for C6H6CdN8O4: C, 19.66; H, 1.65; N, 30.57. Found (%): C, 19.79; H, 1.45; N, 30.46.
The H atoms were included in calculated positions and treated as riding atoms: C–H = 0.93 Å for the tetrazole and 0.97 Å for the methylene H atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 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).
![[Figure 1]](./cv2629fig1thm.gif)
| Fig. 1. A portion of the crystal structure of (I) showing 30% probability displacement ellipsoids and the atomic labeling [symmetry codes: (i) - x, y, - z + 1/2; (ii) - x, - y + 1, - z; (iii) x, - y + 1, z + 1/2; (iv) x - 1/2, y + 1/2, z; (v) - x + 1/2, y + 1/2, - z + 1/2]. |
![[Figure 2]](./cv2629fig2thm.gif)
| Fig. 2. The crystal packing viewed along the b axis. H atoms omitted for clarity. |
| [Cd(C3H3N4O2)2] | F(000) = 712 |
| Mr = 366.60 | Dx = 2.230 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2016 reflections |
| a = 14.750 (3) Å | θ = 2.4–29.1° |
| b = 8.857 (2) Å | µ = 2.03 mm−1 |
| c = 9.503 (2) Å | T = 293 K |
| β = 118.42 (3)° | Prism, colourless |
| V = 1091.8 (4) Å3 | 0.20 × 0.20 × 0.20 mm |
| Z = 4 |
| Rigaku Mercury CCD diffractometer | 1452 independent reflections |
| Radiation source: fine-focus sealed tube | 1441 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| ω scans | θmax = 29.1°, θmin = 3.2° |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | h = −20→19 |
| Tmin = 0.666, Tmax = 0.673 | k = −12→12 |
| 6805 measured reflections | l = −13→12 |
| 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)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.049 | H-atom parameters constrained |
| S = 0.94 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.8P] where P = (Fo2 + 2Fc2)/3 |
| 1452 reflections | (Δ/σ)max = 0.001 |
| 87 parameters | Δρmax = 0.38 e Å−3 |
| 0 restraints | Δρmin = −0.44 e Å−3 |
| [Cd(C3H3N4O2)2] | V = 1091.8 (4) Å3 |
| Mr = 366.60 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 14.750 (3) Å | µ = 2.03 mm−1 |
| b = 8.857 (2) Å | T = 293 K |
| c = 9.503 (2) Å | 0.20 × 0.20 × 0.20 mm |
| β = 118.42 (3)° |
| Rigaku Mercury CCD diffractometer | 1452 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 1441 reflections with I > 2σ(I) |
| Tmin = 0.666, Tmax = 0.673 | Rint = 0.025 |
| 6805 measured reflections | θmax = 29.1° |
| R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
| wR(F2) = 0.049 | Δρmax = 0.38 e Å−3 |
| S = 0.94 | Δρmin = −0.44 e Å−3 |
| 1452 reflections | Absolute structure: ? |
| 87 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
| Cd1 | 0.0000 | 0.535583 (15) | 0.2500 | 0.01857 (7) | |
| O1 | −0.03228 (9) | 0.34712 (15) | 0.06557 (14) | 0.0254 (2) | |
| O2 | 0.05506 (13) | 0.28052 (17) | −0.06267 (17) | 0.0377 (3) | |
| N3 | 0.25046 (14) | −0.05131 (19) | 0.0670 (2) | 0.0335 (4) | |
| N4 | 0.32460 (13) | 0.02896 (15) | 0.1891 (2) | 0.0257 (3) | |
| C3 | 0.27659 (12) | 0.1113 (2) | 0.24775 (19) | 0.0260 (3) | |
| H3A | 0.3077 | 0.1781 | 0.3332 | 0.031* | |
| N1 | 0.17630 (10) | 0.08377 (16) | 0.16511 (16) | 0.0205 (2) | |
| C1 | 0.03356 (12) | 0.27150 (17) | 0.04894 (17) | 0.0208 (3) | |
| C2 | 0.09014 (12) | 0.15137 (19) | 0.17684 (18) | 0.0222 (3) | |
| H2A | 0.1155 | 0.1969 | 0.2817 | 0.027* | |
| H2B | 0.0418 | 0.0726 | 0.1669 | 0.027* | |
| N2 | 0.16106 (13) | −0.01883 (19) | 0.0519 (2) | 0.0329 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.01602 (10) | 0.02182 (10) | 0.01872 (10) | 0.000 | 0.00896 (7) | 0.000 |
| O1 | 0.0187 (5) | 0.0290 (6) | 0.0235 (5) | 0.0055 (4) | 0.0058 (4) | −0.0047 (4) |
| O2 | 0.0526 (9) | 0.0394 (7) | 0.0324 (7) | 0.0211 (6) | 0.0295 (7) | 0.0158 (6) |
| N3 | 0.0222 (8) | 0.0369 (8) | 0.0392 (9) | 0.0018 (6) | 0.0127 (7) | −0.0138 (6) |
| N4 | 0.0177 (7) | 0.0329 (8) | 0.0255 (7) | 0.0025 (5) | 0.0093 (6) | −0.0021 (5) |
| C3 | 0.0172 (7) | 0.0354 (8) | 0.0217 (7) | 0.0015 (6) | 0.0064 (6) | −0.0056 (6) |
| N1 | 0.0168 (6) | 0.0234 (6) | 0.0203 (6) | 0.0022 (5) | 0.0081 (5) | −0.0005 (5) |
| C1 | 0.0198 (7) | 0.0219 (6) | 0.0182 (6) | 0.0018 (5) | 0.0070 (5) | −0.0005 (5) |
| C2 | 0.0178 (6) | 0.0298 (7) | 0.0212 (7) | 0.0061 (5) | 0.0111 (5) | 0.0048 (6) |
| N2 | 0.0222 (8) | 0.0339 (8) | 0.0397 (10) | −0.0015 (6) | 0.0124 (7) | −0.0153 (7) |
| Cd1—O2i | 2.2595 (14) | N3—N4 | 1.356 (2) |
| Cd1—O2ii | 2.2595 (14) | N4—C3 | 1.311 (2) |
| Cd1—O1 | 2.3000 (13) | N4—Cd1vi | 2.3678 (17) |
| Cd1—O1iii | 2.3000 (13) | C3—N1 | 1.326 (2) |
| Cd1—N4iv | 2.3678 (17) | C3—H3A | 0.9300 |
| Cd1—N4v | 2.3678 (17) | N1—N2 | 1.343 (2) |
| O1—C1 | 1.2502 (19) | N1—C2 | 1.4564 (19) |
| O2—C1 | 1.246 (2) | C1—C2 | 1.530 (2) |
| O2—Cd1ii | 2.2595 (14) | C2—H2A | 0.9700 |
| N3—N2 | 1.289 (2) | C2—H2B | 0.9700 |
| O2i—Cd1—O2ii | 87.75 (8) | C3—N4—Cd1vi | 129.09 (12) |
| O2i—Cd1—O1 | 171.86 (5) | N3—N4—Cd1vi | 124.37 (12) |
| O2ii—Cd1—O1 | 93.23 (6) | N4—C3—N1 | 108.77 (15) |
| O2i—Cd1—O1iii | 93.23 (6) | N4—C3—H3A | 125.6 |
| O2ii—Cd1—O1iii | 171.86 (5) | N1—C3—H3A | 125.6 |
| O1—Cd1—O1iii | 86.94 (7) | C3—N1—N2 | 108.25 (14) |
| O2i—Cd1—N4iv | 98.72 (6) | C3—N1—C2 | 130.32 (14) |
| O2ii—Cd1—N4iv | 83.34 (6) | N2—N1—C2 | 121.34 (14) |
| O1—Cd1—N4iv | 89.42 (5) | O2—C1—O1 | 126.95 (15) |
| O1iii—Cd1—N4iv | 88.52 (5) | O2—C1—C2 | 117.22 (14) |
| O2i—Cd1—N4v | 83.34 (6) | O1—C1—C2 | 115.79 (13) |
| O2ii—Cd1—N4v | 98.72 (6) | N1—C2—C1 | 113.02 (12) |
| O1—Cd1—N4v | 88.52 (5) | N1—C2—H2A | 109.0 |
| O1iii—Cd1—N4v | 89.42 (5) | C1—C2—H2A | 109.0 |
| N4iv—Cd1—N4v | 177.16 (7) | N1—C2—H2B | 109.0 |
| C1—O1—Cd1 | 126.41 (11) | C1—C2—H2B | 109.0 |
| C1—O2—Cd1ii | 125.12 (11) | H2A—C2—H2B | 107.8 |
| N2—N3—N4 | 110.14 (16) | N3—N2—N1 | 106.81 (15) |
| C3—N4—N3 | 106.04 (15) | ||
| O2i—Cd1—O1—C1 | 12.4 (4) | Cd1ii—O2—C1—O1 | 10.9 (3) |
| O2ii—Cd1—O1—C1 | 109.08 (14) | Cd1ii—O2—C1—C2 | −171.73 (11) |
| O1iii—Cd1—O1—C1 | −79.07 (13) | Cd1—O1—C1—O2 | −108.22 (18) |
| N4iv—Cd1—O1—C1 | −167.62 (14) | Cd1—O1—C1—C2 | 74.34 (18) |
| N4v—Cd1—O1—C1 | 10.43 (14) | C3—N1—C2—C1 | 100.0 (2) |
| N2—N3—N4—C3 | 0.1 (2) | N2—N1—C2—C1 | −76.1 (2) |
| N2—N3—N4—Cd1vi | −172.37 (14) | O2—C1—C2—N1 | 11.3 (2) |
| N3—N4—C3—N1 | −0.2 (2) | O1—C1—C2—N1 | −171.02 (14) |
| Cd1vi—N4—C3—N1 | 171.87 (11) | N4—N3—N2—N1 | −0.1 (2) |
| N4—C3—N1—N2 | 0.1 (2) | C3—N1—N2—N3 | 0.0 (2) |
| N4—C3—N1—C2 | −176.36 (15) | C2—N1—N2—N3 | 176.83 (16) |
| Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x, −y+1, −z; (iii) −x, y, −z+1/2; (iv) x−1/2, y+1/2, z; (v) −x+1/2, y+1/2, −z+1/2; (vi) x+1/2, y−1/2, z. |
This work was sponsored by the start-up fund of Henan Agricultural University (grant No. 30700061).
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Multidentate ligands containing rich coordination sites (N and/or O donors) are often employed to produce polymeric networks with structural diversity owing to their various coordination modes (Won et al., 2007; Lee et al., 2005; Du et al., 2007). As ligands with multiple coordination site, tetrazole and its derivatives have been shown to be good organic linker in generation of structurally versatile metal-organic frameworks since it can bridge different metal centers to afford coordination polymers that exhibit extraordinary structural diversity and facile accessibility of functionalized materials (Yang et al., 2009). Here, we report the synthesis and crystal structure of the title compound, (I).
In (I) (Fig. 1), each CdII ion located on a twofold rotation axis is six–coordinated by two tetrazole nitrogen atoms (N4) and four carboxylate group oxygen atoms (O1 and O2) from six distinct ligands. The coordination bond lengths Cd—N and Cd—O are 2.368 (2), 2.300 (1) Å and 2.260 (1) Å, respectively. The coordination geometry around CdII can be described as a distorted octahedron - the CdII coordination angles are in the range 83.34 (6)° - 177.16 (7)°. Each fully deprotonated L ligand serves as a tridentate bridging ligand via one nitrogen atom at the 5-position of the tetrazole ring while the nitrogen atoms at 3,4-positions remain uncoordinated, and two carboxylate O atoms. In this way two metal atoms and two carboxylate form a 8-membered [M2C2O4] metallocyclic ring, the Cd···Cd distance is 4.793 Å. The Cd···Cd distance linked by the bridged L ligand is 8.603 Å. Thus each CdII centers are linked together by six L ligands into a three–dimensional polymeric structure (Fig. 2).